State of Knowledge Review of Fate and Effect of Oil
in the Arctic Marine Environment
2011
A report prepared for the National Energy Board of Canada
by
K. Lee 1 , M. Boudreau 2 , J. Bugden 1 , L. Burridge 3 , S.E. Cobanli 1 , S. Courtenay 2 , S. Grenon 4 , B. Hollebone 5 , P. Kepkay 1 , Z. Li 1 , M. Lyons 2 , H. Niu 1 , T.L. King 1 , S. MacDonald 5 , E.C. McIntyre 1 , B. Robinson 1 , S.A. Ryan 1 and G. Wohlgeschaffen 1
1 Centre for Offshore Oil, Gas and Energy Research (COOGER), Fisheries and Oceans Canada, Bedford Institute of Oceanography, P.O. Box 1006, Dartmouth, Nova Scotia, Canada, B2Y 4A2 2 Fisheries and Oceans Canada, Gulf Fisheries Centre, P.O. Box 5030, Moncton, New Brunswick, E1C 9B6 3 Fisheries and Oceans Canada, St. Andrews Biological Station, 531 Brandy Cove Road, St. Andrews, New Brunswick, Canada, E5B 2L9 4 Triox Environmental Emergencies, 4839 Garnier, Montral, Qubec, Canada, H2J 3S8 5 Emergencies Science and Technology Section, Environment Canada, 335 River Road, Ottawa, Ontario, Canada, K1A 0H3
i TABLE OF CONTENTS
List of Figures................................................................................................................................ iv List of Tables .................................................................................................................................. v List of Acronyms ........................................................................................................................... vi Executive Summary........................................................................................................................ 1 1. Introduction................................................................................................................................. 4 1. Introduction................................................................................................................................. 4 2. Characterization and Classification of Crude Oil ....................................................................... 9 2.1 Physical and Chemical Properties......................................................................................... 9 2.2 Significance of Oil Properties in Oil Spill Response.......................................................... 12 2.3 Canadian Arctic Offshore Crude Oils................................................................................. 13 3. Oil Spills in Arctic Waters........................................................................................................ 17 3.1 International Concerns and Governance............................................................................. 17 3.2 Behaviour and Fate of Oil................................................................................................... 18 Oil in Ice-Free Waters .......................................................................................................... 19 Oil in Ice Covered Waters..................................................................................................... 22 3.3 Factors Influencing Oil Behaviour...................................................................................... 24 Spreading in Broken Ice........................................................................................................ 24 Movement on Ice................................................................................................................... 27 Movement Under Ice............................................................................................................. 27 Movement Through Ice ......................................................................................................... 29 Adsorption to Snow............................................................................................................... 31 3.4 Factors Influencing Oil Fate (Weathering) ......................................................................... 32 Evaporation........................................................................................................................... 32 Dissolution............................................................................................................................ 33 Dispersion............................................................................................................................. 34 Emulsification ....................................................................................................................... 35 Photo-Oxidation.................................................................................................................... 38 Biodegradation ..................................................................................................................... 39 Formation of Oil-Mineral Aggregates.................................................................................. 44 Sedimentation........................................................................................................................ 46 4. Oil Spills in Canada from Offshore Oil and Gas Activities...................................................... 47 4.1 Oil Types from Vessel Operations...................................................................................... 50 4.2 Oil Types from Oil Platform Operations ............................................................................ 51 Crude Oil from Drilling Activities ........................................................................................ 52 Petroleum Products used in Operations............................................................................... 52 4.3 Overview of Oil Spill Risks in the Canadian Arctic........................................................... 52 Defining Risk......................................................................................................................... 52 Incidents from Vessel Operation........................................................................................... 54 Incidents from Oil Platform Operations............................................................................... 57 4.4 Modelling Spill Scenarios and Oil Behaviour .................................................................... 62 Scenario for Spills of Crude Oil............................................................................................ 63 Scenario for Spills of Intermediate Fuel Oil......................................................................... 66 Scenario for Spills of Marine Gasoil .................................................................................... 67 Scenario for Spills of Aviation Fuel (Jet Fuel) ..................................................................... 69 Recommendations from Modelling Exercises....................................................................... 70 5. Offshore Arctic Oil Spill Response Options............................................................................. 72 5.1 Development of Policies, Regulations and Capacity.......................................................... 72 5.2 Mechanical Containment and Recovery............................................................................. 74 5.3 In situ Burning .................................................................................................................... 76 5.4 Chemical Dispersion........................................................................................................... 79 5.5 Oil-Mineral Aggregates ...................................................................................................... 82 5.6 Bioremediation.................................................................................................................... 85 5.7 Natural Attenuation............................................................................................................. 89 6. Biological Effects of Oil ........................................................................................................... 91 6.1 Oil Toxicity in the Arctic.................................................................................................... 91 6.2 Routes of Exposure............................................................................................................. 93 6.3 Bioaccumulation, Biomonitoring and Toxicity Assessment .............................................. 95 6.4 The Arctic Food Web.......................................................................................................... 98 6.5 Effects on Arctic Sea Ice Communities............................................................................ 100 6.6 Effects of Oil on Arctic Biota ........................................................................................... 103 Bacteria............................................................................................................................... 103 Phytoplankton and Macroalgae.......................................................................................... 104 Salt Marsh Vegetation......................................................................................................... 107 Zooplankton ........................................................................................................................ 108 Fish ..................................................................................................................................... 112 Benthic Invertebrates.......................................................................................................... 126 Mammals............................................................................................................................. 137 7. Arctic Oil Spill Field Trials .................................................................................................... 150 7.1 Balaena Bay experiment 1974 - 1975 (Norcor)................................................................ 150 Balaena Bay Revisited: 1981.............................................................................................. 152 7.2 Baffin Island Oil Spill Experiment (BIOS) ...................................................................... 154 Nearshore Study.................................................................................................................. 155 Shoreline Study ................................................................................................................... 158 BIOS Revisited .................................................................................................................... 160 7.3 Field Trials in Svalbard, Norway...................................................................................... 162 Early Field Studies on Oil Bioremediation......................................................................... 162 In Situ Treatment of Oiled Sediment Shorelines (ITOSS) Program................................... 162 7.4 Field Trial Projects on Arctic Oil Spills in Ice ................................................................. 165 7.5 Field Trials on Enhanced Oil Dispersion with Mineral Fines .......................................... 169 7.6 Monitoring Arctic Offshore Oil and Gas Operations ....................................................... 169 7.7 Future Oil Spill Field Trials in the Arctic......................................................................... 170 8. Operational Waste Discharges................................................................................................ 174 8.1 Produced Water................................................................................................................. 174 Chemical Composition........................................................................................................ 175 Petroleum Hydrocarbons.................................................................................................... 176 Environmental Concerns over Discharges ......................................................................... 177 Fate following Discharge into the Ocean........................................................................... 179 Environmental Effects of Discharges.................................................................................. 179 Effects on Water-Column Organisms ................................................................................. 180 Accumulation and Effects in Sediments .............................................................................. 180 ii Aquatic Toxicity .................................................................................................................. 181 Bioaccumulation and Biomarkers as Evidence of Exposure .............................................. 183 Alteration of Trophic Level Dynamics by Produced Water................................................ 186 Ecological Risk of Produced Water Discharges................................................................. 187 Produced Water Treatment................................................................................................. 188 Environmental Effects Monitoring and Research Needs .................................................... 189 8.2 Drilling Muds.................................................................................................................... 191 Arctic Marine Food Webs and Toxicity.............................................................................. 193 9. Case Study: The Exxon Valdez Oil Spill................................................................................. 195 9.1 Fate of the Oil ................................................................................................................... 197 9.2 Effects of the Oil ............................................................................................................... 200 Bioavailability..................................................................................................................... 200 Shoreline Flora and Fauna................................................................................................. 200 Invertebrates ....................................................................................................................... 202 Fish ..................................................................................................................................... 202 Birds.................................................................................................................................... 203 Marine Mammals................................................................................................................ 204 9.3 Present Status of Injured Resources and Services ............................................................ 205 9.4 Lessons Learned and Issues to Consider .......................................................................... 208 10. Future Research Needs ......................................................................................................... 209 10.1 Oil Detection................................................................................................................... 209 10.2 Oil Fate and Behaviour ................................................................................................... 209 10.3 Biological Effects............................................................................................................ 210 10.4 Mechanical Recovery................................................................................................. 210 10.5 In Situ Burning................................................................................................................ 211 10.6 Enhanced Dispersion ...................................................................................................... 211 10.7 Biodegradation and Natural Attenuation ........................................................................ 211 10.8 Development of Predictive Models ................................................................................ 212 10.9 Field Trials...................................................................................................................... 212 11. Acknowledgements............................................................................................................... 213 References................................................................................................................................... 214 Appendix 1.................................................................................................................................. 257
iii List of Figures
Figure 1 Since 1980 industry has increased the recovery of oil from the offshore sector to meet global demand as land-based oil reserves declined. There is a greater risk of spills and damage as operations expand into the frontier regions including the deep waters off the continental shelf and the Arctic (Sandrea and Sandrea, 2007). .............................................. 4 Figure 2 The significance of the oil and gas industry to Canadas GDP in 2006........................... 5 Figure 3 Norman Wells crude oil dynamic viscosity as a function of temperature; data from Environment Canadas Oil Properties database (Environment Canada, 2001a). ................. 11 Figure 4 Physical, chemical and biological processes affecting the fate and behaviour of spilled oil (ITOPFL, 2002). .............................................................................................................. 20 Figure 5 Oil and ice interaction processes (Bobra and Fingas, 1986). ......................................... 23 Figure 6 Canadian Arctic (source: Solar Navigator, 2011, http://www.solarnavigator.net). ....... 47 Figure 7 Exploration parcels of Cairn Energy in the Greenland offshore (Cairn, 2011).............. 49 Figure 8 Accidents by ship type; OBO = other bulk operations (source: Transportation Safety Board of Canada). ................................................................................................................. 54 Figure 9 Types of accidents (Source: Transportation Safety Board of Canada). ......................... 55 Figure 10 Canadian Arctic shipping routes. ................................................................................. 56 Figure 11 Number of spills per year in Nova Scotia from offshore operations............................ 58 Figure 12 Number of spills per year in Newfoundland-Labrador from offshore operations........ 58 Figure 13 Total spill volume in litres per year off Nova Scotia. .................................................. 59 Figure 14 Total spill volume in litres per year off Newfoundland. .............................................. 60 Figure 15 Oil budget for a spill of 4000 m 3 of Amauligak crude oil as calculated by ADIOS2. . 64 Figure 16 Predicted change in viscosity for Amauligak crude oil as calculated by ADIOS2. ..... 65 Figure 17 Predicted change in density for Amauligak crude oil as calculated by ADIOS........... 65 Figure 18 Oil budget for a spill of 1000 m 3 of IFO 180 as calculated by ADIOS2. .................... 66 Figure 19 Predicted change in viscosity for IFO 180 as calculated by ADIOS2. ........................ 67 Figure 20 Oil budget for a spill of 100 m 3 of MGO as calculated by ADIOS2............................ 68 Figure 21 Oil budget for a spill of 10 m 3 of jet fuel as calculated by ADIOS2............................ 69 Figure 22 The Arctic Food Web (ACIA, 2004)............................................................................ 98 Figure 23 Energy flow above trophic level 1 from phytoplankton and pelagic detritus in red, or benthic detritus in blue, and proportional shades in between. Top panel: eastern Bering Sea shelf; bottom panel: western Bering Sea shelf. Box and text size are proportional to log 10 of biomass for the compartment; area of each link proportional to volume of flow (Aydin et al., 2002). .............................................................................................................................. 99
iv List of Tables
Table 1 Canadian Arctic oils (Drummond, 2006). ...................................................................... 15 Table 2 Vessel types operating in Arctic waters and oil types carried onboard. .......................... 50 Table 3 Reported vessel accidents in the Canadian Arctic. .......................................................... 57 Table 4 Historical large oil spills in barrels (bbl) from offshore well blowouts (source: Oil Spill Intelligence Report database)................................................................................................ 61 Table 5 Valued ecosystem components (VEC) of various Arctic regions at risk from oil spills (INAC, 2010; Word and Perkins, 2011). .............................................................................. 92 Table 6 Food web functional group and acute toxicity LC 50 (95% confidence interval) using 2- methyl naphthalene for co-inhabiting Arctic species (Camus et al., 2010; Carroll et al., 2010). .................................................................................................................................... 96 Table 7 Experimental crude oil spills of a few barrels to hundreds of barrels conducted in sea ice, regardless of latitude (Dickins, 2011). ................................................................................ 166 Table 8 Spreading comparison for a 1600 m 3 (10,000 bbl) crude oil spill (SL Ross Environmental Research Ltd. et al., 2010). ........................................................................ 167 Table 9 Concentration ranges (mg/L or parts per million) of several classes of naturally- occurring metals and organic chemicals in produced water world-wide (Neff, 2002)....... 176 Table 10 National permissible concentrations of total oil and grease in produced water destined for ocean disposal (Veil, 2006). .......................................................................................... 188 Table 11 Summary of produced water treatment systems used by three Arctic oil and gas installations; adapted from Hawboldt et al. (2010)............................................................. 189 Table 12 Status in 2010 of resources and services injured by the Exxon Valdez oil spill in 1989. Human services are those which were negatively impacted because of their connection with impacted resources (EVOS Trustee Council, 2010). .......................................................... 207 Table 13 Sources of peer-reviewed biological effects data from Camus et al. (Camus et al., 2008) with additional references added. ....................................................................................... 257
v List of Acronyms AhR aryl hydrocarbon receptor AL Arabian light, crude oil ANS Alaska North Slope, crude oil API American Petroleum Institute BaP benzo[a]pyrene BIOS Baffin Island Oil Spill Project BTEX benzenes, toluenes, ethylbenzenes, xylenes CCG Canadian Coast Guard CEWAF chemically enhanced water accommodated fraction CNLOPB Canada-Newfoundland and Labrador Offshore Petroleum Board CNSOPB Canada-Nova Scotia Offshore Petroleum Board CYP1A cytochrome P4501A, an enzyme system used as a biomarker for detecting biological effects of xenobiotics DE dispersant effectiveness DGGE denaturing gradient gel electrophoresis DOR dispersant-to-oil ratio dpm disintegrations per minute (a measure of radioactivity) DWH BP Macondo MC 252 Deepwater Horizon spill in the Gulf of Mexico, April 2010 EROD ethoxyresorufin-O-deethylase EVCO Exxon Valdez crude oil; the oil specifically from this spill EVOS Exxon Valdez oil spill GC/MS gas chromatography-mass spectrometry GST glutathione S-transferase IFO intermediate fuel oil IMO International Maritime Organization ISB in situ burning ITOSS In situ Treatment of Oiled Sediment Shorelines JIP Joint Industry Program LC 50
lethal concentration 50: the concentration of a toxicant that kills 50% of the test organisms in an acute toxicity test MESA medium South American, crude oil MGO marine gasoil or marine diesel OBM oil-based mud OMA oil-mineral aggregates PAH polycyclic aromatic hydrocarbon PEC predicted environmental concentration PNEC predicted no effect concentration ppt parts per thousand; often used as units of salinity PWS Prince William Sound ROS reactive oxygen species vi SBM synthetic-based mud SPM suspended particulate matter TOSC total oxyradical scavenging capacity TPAH total polycyclic aromatic hydrocarbons TPH total petroleum hydrocarbons UV ultraviolet light (10 nm to 400 nm) VEC valued ecosystem component WAF water accommodated fraction WBM water-based drilling muds
vii 1 Executive Summary
The improvement of policies and regulations for spill response/remediation technologies, and contingency plans for marine environmental protection to address the anticipated growth of Canadas offshore petroleum industry in the North will require the best available information on the factors and processes influencing the fate and effects of oil released into the marine environment. As the result of past interests in the development of oil and gas resources in the Canadian Arctic, as well as studies by other northern countries, a vast amount of basic information exists to fulfill our need for science based advice to support environmental risk assessments. However, this review of emerging environmental concerns has also identified a number of knowledge gaps that should be addressed to ensure the protection of our marine habitat and its living resources within the Arctic.
The risk of having an oil spill in Canadian Arctic waters is anticipated to increase because of community growth that will increase marine traffic and industrial development including offshore oil exploration and production. A range of petroleum hydrocarbon fluids from crude oils to refined products will be transported within the Arctic. Of these, crude oil will likely be the largest source of petroleum hydrocarbons transported. While the quantities of a spill from a tanker may be large, the probability of a spill occurring is low based on the current information available from historical records. Nevertheless, response measures must be considered within contingency plans for a worst-case challenging situation such as a deep-well blowout in the Arctic in the presence of ice.
A combination of laboratory, mesocosm and field studies have shown that the physico-chemical properties of oil, temperature and the presence or absence of ice will influence the fate and behaviour of oil spilled in the environment as well as the effectiveness of spill response operations. For example, due to reduced rates of evaporative loss under cold temperature conditions, oil will retain its viscosity and remain more persistent in Arctic waters. On the other hand, there can also be some advantages to consider when oil is spilled in ice infected waters. The decrease in oil evaporation may retain an oils flash point and viscosity providing an ideal environment for in situ burning (ISB). The results of recent field tests have also demonstrated that the inhibition of oil-weathering processes (natural, physical and chemical processes that oil undergoes following its release into the environment) in ice and cold temperatures prolonged the window of opportunity for the application of chemical oil dispersants as a spill response strategy. In addition to active oil spill response strategies, there is also a renewed interest in the potential rates of natural recovery in the Arctic following oil spill events. This is largely due to advances in the application of biotechnology techniques in microbial ecology that have highlighted the significance of natural oil biodegradation rates by indigenous bacteria and the influence of suspended particulate material on the dispersion and biodegradation rates of residual oil.
In terms of the development of predictive models on the fate, behaviour and effects of oil on various components of the Arctic ecosystem, while there is a considerable amount of existing data, the results from experimental studies are largely anecdotal or empirical in nature. As a result, there is limited data of use for the development of integrated risk assessment models that fully take into account the numerous physical, chemical and biological processes within the Arctic ecosystem.
A multitude of biological effects have been observed in toxicological studies with oil with a range of biota covering multiple trophic levels. In the Arctic, seasonal aggregations of animals, such as marine mammals in open areas of sea ice, seabirds at breeding colonies or feeding sites, or fish at spawning time may be particularly vulnerable to oil spills. For example, an oil spill in the spawning areas of polar cod could severely reduce a year-class of the population. Appendix 1, Table 13, provides peer-reviewed biological effects data from an extensive review by Camus et al. (2008), to which additional references have been added. There has been a shift in biological effect studies from acute studies focused on mortality as the end-point to that of chronic responses associated with much lower exposure levels and their effect on the long-term health, growth and reproduction of the target organisms. With the implementation of ecosystem based management by regulators, future studies must include consideration of biological effects on population, and on community structure and function.
2 Interpretation of the data collected for environmental risk assessments is challenging as the exposure conditions in past scientific studies (e.g. dosage and exposure time) are frequently outside of the range observed in the field following actual spill events. Furthermore, as illustrated by a case study following the Exxon Valdez spill in Prince William Sound, Alaska, a consensus on the levels of environmental impacts have not been achieved due to a number of confounding factors including different approaches to natural resource damage assessment, the lack of pre- spill baseline information, and reported high levels of natural variation in population numbers and community structure.
To address the knowledge gaps identified in this review, additional scientific research in Canadian Arctic waters, including the conduct of large-scale field trials, should be conducted on: 1) the behaviour, transport and fate of oil spilled in the Canadian Arctic; methodologies to monitor acute and chronic biological effects and recovery on multi-trophic level valued ecosystem components; and 3) the development, application and validation of oil spill countermeasures including natural recovery (natural attenuation). To optimize the use of scientific expertise and resources, the reseach program would contribute towards an international pan-Arctic global effort involving both government and non-governmental organizations including academia and the private sector.
Suggested Citation: Lee, K., M. Boudreau, J. Bugden, L. Burridge, S.E. Cobanli, S. Courtenay, S. Grenon, B. Hollebone, P. Kepkay, Z. Li, M. Lyons, H. Niu, T.L. King, S. MacDonald, E.C. McIntyre, B. Robinson, S.A. Ryan and G. Wohlgeschaffen. 2011. State of Knowledge Review of Fate and Effect of Oil in the Arctic Marine Environment 2011. National Energy Board of Canada, Ottawa, ON. 267 pp.
3 1. Introduction
Despite rapid advances in the development of ocean renewable energy technologies, such as offshore wind and tidal energy, Canada and the world will remain dependent on petroleum hydrocarbons to meet future energy needs over the next few decades. With traditional hydrocarbon reserves in the Western Canada Basin and other areas being depleted, exploration and production operations within the oil and gas industry have shifted towards frontier regions in the offshore and Arctic (Figure 1). Based on current analysis, it is evident that the bulk of our newly discovered petroleum reserves and the best prospects for future discoveries will lie under water rather than on land. The future of Canadas offshore oil and gas production may also rely to a substantial extent on finds in deeper more distant locations on the outer continental shelf.
Figure 1 Since 1980 industry has increased the recovery of oil from the offshore sector to meet global demand as land-based oil reserves declined. There is a greater risk of spills and damage as operations expand into the frontier regions including the deep waters off the continental shelf and the Arctic (Sandrea and Sandrea, 2007).
Ocean sector activities related to Canadas oil and gas industry provide major socio-economic benefits to Canada; $17.7B in direct GDP in 2006. This was linked to the direct generation of over 171,340 jobs (Figure 2). 4
Figure 2 The significance of the oil and gas industry to Canadas GDP in 2006.
Among the greatest uncertainties in future energy supply, and a subject of considerable environmental concern, is the amount of oil and gas yet to be found in the Arctic. The Arctic is estimated to contain between 44 and 157 billion barrels of undiscovered recoverable oil. In addition, the Arctic is gas-prone with an estimated 770 to 2990 trillion cubic feet of undiscovered conventional natural gas (Bird et al., 2008). By using a probabilistic, geology-based methodology, the United States Geological Survey examined the area north of the Arctic Circle and concluded that about 30% of the worlds undiscovered gas and 13% of the worlds undiscovered oil may be found there, mostly offshore under less than 500 metres of water. Undiscovered natural gas is three times more abundant than oil in the Arctic and is largely concentrated in Russia (Gautier et al., 2009). Thus, the Arctic continental shelves constitute one of the worlds largest remaining prospective areas. To date, the remoteness and technical difficulty presented by the Arctic, coupled with abundant low-cost petroleum in other regions of the world, ensured that little exploration of the Arctic offshore reserves occurred. Even where offshore wells have been drilled, in the Mackenzie Delta, the Barents Sea, the Sverdrup Basin, and offshore Alaska, most of the resulting discoveries remain undeveloped.
Previous exploration activities by Imperial Oil Limited, Dome Petroleum Limited, Gulf Canada Resources Limited, and Panarctic Oils Limited between 1960 and 1980 have verified the presence of significant oil and gas finds in Canadas Arctic waters (SL Ross Environmental 5 Research Ltd. et al., 2010). The Drake F76 program (Panarctic Oils Limited) at a water depth of 55 m, approximately 1200 m offshore of Drake Point on the Sabine Peninsula of Melville Island was the first offshore floating ice platform within Canada. The well at this facility with under- the-ice subsea tree and subsea diverless connections of flowlines and controls (Bomba and Brown, 2011) has proven the feasibility of offshore gas production in the Arctic region. The Drake F76 program has been a showcase for advances in technologies and continues production today.
With the rising prices and increased global demand for oil has come renewed interest in the extraction of petroleum hydrocarbons in the Arctic, with the attendant concerns over sovereignty, energy security, and advances in technology. Indeed, consideration has been recently given to exploration and production in the deepwater Arctic environment of the U.S. Beaufort Sea (Pilisi et al., 2011) by the use of winterized drill-ships constructed of material able to withstand the ice, or an icebreaker converted into a drilling vessel. Increases in oil and gas exploration and production activities in frontier regions would result in an increased risk of operational and accidental releases of petroleum hydrocarbons due to the expansion of drilling operations, marine support and shipping operations including that of pipelines. This risk is further compounded in the Arctic environment due to environmental challenges including the interference of ice, cold temperatures, isolated locations, high winds, and low visibility especially during the winter when there are limited daylight hours. It is also important to note that the availability of oil spill response personnel, and logistics for waste containment and disposal in spill response operations, are issues in the Arctic. Furthermore, residents of communities in Canadas Arctic are concerned over the effects of oil spills on indigenous species and their habitat, as well as the effectiveness of existing oil spill response strategies that were not originally designed for use in the North.
Due to the anticipated increase in both offshore oil and gas activities and onshore developments (e.g. community growth, mining industry, etc.) in the Canadian Arctic, and the recent BP Macondo MC 252 Deepwater Horizon spill (DWH) in the Gulf of Mexico in April 2010, more stringent government policies and regulations for environmental protection are being considered. A primary emphasis of environmental oversight is that of protecting the environment from 6 accidental spills. This includes all spills ranging from the small, repeated discharges linked to routine exploration, production, processing and transport operations, to that of a catastrophic spill of national or international significance. Within this context there is a demand to understand the factors and processes influencing the fate and effects of oil released into the marine environment. This information is essential for the development of improved spill response and remediation technologies, and contingency plans.
To support a public review of Arctic safety and environmental offshore drilling requirements the National Energy Board of Canada is looking for the best available information. This report has been generated by the Centre for Offshore Oil, Gas and Energy Research, which is a Centre of Expertise within the Science Branch of the Department of Fisheries and Oceans Canada, to provide scientific facts and information on the fate and effects of oil in the Arctic marine environment. The scope of the project includes: review of the properties of oil that have been, or are likely to be discovered in the Arctic, and the identification of chemical parameters that influence oil fate and effects in the Canadian Arctic offshore or nearshore environment; reporting on the fate and effect of oil that could be released as a result of accident, mishap (including oil or fuel that would be in support of operational offshore oil and gas drilling activities), or a well that becomes out of control; review of relevant reports providing knowledge about the fate and effect of oil spills in Arctic waters and information on the fate and effects of the Exxon Valdez spill in the Gulf of Alaska; incorporation of experience and knowledge from previous field studies relevant to offshore oil and gas drilling in the Canadian Arctic; identification of knowledge gaps that may influence the safety of offshore drilling operations and the protection of the environment; and recommendations for future research.
To meet the above study objectives, this review is structured in several sections. Chapter 1, following the Introduction, is focused on the characterization and classification of crude oils based on physical properties that influence the significance of oil fate and behavior in the 7 environment as well as the success of oil spill response strategies. A section of the chapter describes the characteristics of the crude oils which we anticipate to be recovered within the offshore Arctic regions of Canada during production operations in the future. Chapter 2 provides an overview of current observations and scientific findings on the fate and behavior of oil spilled in Arctic waters. Detailed information is provided on the influence of environmental conditions such as ice-cover. Chapter 3 covers the subject of oil spills in the Canadian Arctic. The potential sources of accidental and operational releases in Canadian Arctic waters are described with risk analysis based on the probability and consequences of various spill scenarios that may occur during anticipated future operations. Chapter 4 provides an overview of the current oil spill response technologies available for use in the Arctic environment. Emphasis is given to emerging technologies currently being developed for specific use in ice-infested waters. Chapter 5 provides a comprehensive review on the biological effects of oil spilled in Arctic waters. This chapter covers topics such as routes of exposure, bioaccumulation, environmental effects monitoring, potential changes on community structure and trophic level dynamics. Sub-sections cover the effects of oil on various groups of organisms ranging from bacteria at the base of the food web to the top predators such as polar bears and whales. Information is provided on the environmental significance of valued ecosystem components (VECs) in Canadian Arctic waters (e.g. polar cod) and their sensitivity to contaminant hydrocarbons. Chapter 6 covers the sources of the various types of petroleum hydrocarbons that may be released into the Arctic marine environment from operational activities. The potential environmental impacts associated with the discharge of production waters and drilling muds are discussed. Chapter 7 describes the results of experimental field trials conducted in the Arctic which have provided essential information on the fate and behavior of oil in the environment as well as a platform for the development and validation of oil spill countermeasures. A discussion on the need for additional field trials to advance our scientific and technical knowledge is given. Chapter 8 provides a case study on the impact of the oil spilled in Prince William Sound (PWS) from the grounding of the tanker Exxon Valdez, oil spill response operations and the current controversy among various parties over the extent of habitat recovery. Based on the information in this report, a list of future research needs is presented in the final chapter to address the knowledge gaps that have been identified.
8 2. Characterization and Classification of Crude Oil
2.1 Physical and Chemical Properties
Crude oils are complex mixtures comprised of hundreds to thousands of individual compounds. However, the hydrocarbon content of crude oil can be separated into four main classes: saturates, aromatics, resins (includes waxes), and asphaltenes (Fingas, 2010; Hannisdal et al., 2007). For quantitative analysis, gas chromatography-mass spectrometry (GC/MS) can be used to characterize the individual components of saturates, aromatics and biomarkers in crude oil, while the resin and asphaltene content is usually measured using thin layer chromatography coupled to flame ionization detection, or TLC-FID (Obermajer et al., 2010).
The chemical composition of crude oil influences its physical properties, which impact its fate and transport properties on release into the marine environment. For example, a high content of resins and asphaltenes will increase the viscosity making it less mobile. Crude oil chemical composition can also affect the rate of biodegradation where microbial attack has generally been ranked in the following order of decreasing susceptibility: saturates > aromatics > resins > asphaltenes (Leahy and Colwell, 1990). Crude oils also contain a number of compounds referred to as biomarkers, such as steranes and hopanes, which are persistent and less susceptible to microbial attack. Since every crude oil has a unique biomarker profile, quantification of these compounds provides a means for the identification of the origin of unknown oils in spill response operations, provided that a database of oil biomarker profiles exists (Wang and Fingas, 1995). In addition, other chemical components that are susceptible to biodegradation can be normalized to these biomarkers to determine if changes in oil composition are linked to physical processes or biodegradation (Prince et al., 2003b).
Physical properties, which are dependant on the chemical properties, can be used to characterize crude oils. The main oil properties to take into consideration in an Arctic oil spill scenario, since they are temperature dependant, include the American Petroleum Institute (API) gravity values, viscosity, pour point, distillation characteristics, surface tension, flash point, and weathering 9 (ITOPFL, 2002; Payne et al., 1991; Shata, 2010). Definitions for these parameters are provided here to better illustrate their significance in describing the physical properties of oil. The specific gravity of oil is its density compared to seawater which is on average 1.025 g/mL. Most oils have a specific gravity <1.0 g/mL; therefore, they float on seawater. The API gravity scale is used to describe the specific gravity of crude oil and it is determined as (ASTM International, 2006; ITOPFL, 2002): API = 141.5/(specific gravity) - 131.5 Crude oils are classified as light, medium or heavy according to their API gravity (ITOPFL, 2002). Light crudes have an API gravity >31, medium oils have an API gravity between 22 and 31, and heavy oils have an API gravity <22. Viscosity of oil is its resistance to flow (Shata, 2010). A viscometer measures in units of centipoises (cP) for dynamic viscosity, or centistokes (cSt) for kinematic viscosity. Viscosity is governed by the chemical composition of oil. The higher the content of the lighter components such as saturates and a lesser amount of asphaltenes, the lower the viscosity (Fingas, 2010). When oil is spilled at sea it will spread over the sea surface. Oil that flows readily at high temperatures can become a viscous mass at low temperatures (Fingas, 2010). Spreading is greatly dependant on the viscosity of the oil, where viscosity increases thus: light oil > medium oil > heavy oil. Temperature can affect viscosity (Figure 3). As the temperature falls, oil becomes more viscous (less mobile) and persistent in the marine environment (Brandvik and Leirvik, 2008). In some cases, the rheological properties (deformation and flow) of heavy oil can be altered using lighter fuels (Elasheva et al., 2001; Schmidt et al., 2005). This process increases the commercial value of heavy oils and decreases the viscosity, which improves mobility of the oil during transport (Elasheva et al., 2001; Schmidt et al., 2005). 10 0 1 2 3 4 5 6 7 8 9 10 0 5 10 15 20 25 30 Temperature ( C) C e n t i P o i s e
Figure 3 Norman Wells crude oil dynamic viscosity as a function of temperature; data from Environment Canadas Oil Properties database (Environment Canada, 2001a).
Pour point is the temperature below which oil will not flow (ITOPFL, 2002). The waxy (resins) and asphaltenic components affect the pour point of oil. As the temperature of the oil decreases, the wax components crystallize. This is often referred to as the cloud point. This process hinders the flow of oil until it eventually changes from a liquid to a semi-solid at the pour point (ITOPFL, 2002). The pour point is used to evaluate the flow of crude oil at low temperatures (Zhang and Liu, 2008). Distillation characteristics (evaporation) of crude oils describe their volatility (ITOPFL, 2002). As the temperature increases the low boiling point components, i.e. benzene, toluene, ethylbenzene and xylenes, begin to evaporate or distil. Evaporation loss by weight or volume is logarithmic with time for multi-component mixtures (Bobra, 1992; Fingas, 1994; Fingas, 1999). The waxy and asphaltenic components of crude oil will not distil under ambient conditions and remain persistent for extended periods in the environment. Evaporation can change the physical and chemical composition of fresh crude oil. Surface tension is the amount of pressure necessary to break the surface of a liquid. The oil/water interfacial tension is the force of attraction between the surface molecules of the oil and the water (Shata, 2010). The lower the interfacial tension at the seawater-oil interface, the greater the extent of oil spreading (Fingas, 2010; Fingas and Hollebone, 2003; 11 The flash point is the lowest temperature at which an oil will ignite (Brandvik and Leirvik, 2008; Shata, 2010). This property is dependant on oil composition, in particular the volatile components. The volatiles are generally lost due to evaporation; however, this process is temperature dependant. In cold water, evaporation of oil is slow and the volatiles remain. Fresh crude oils normally have a low flash point from -40 to 30C (Brandvik and Leirvik, 2008). If the flash point of crude oil is close to or lower than sea temperature then there is a risk of fire or explosion hazard (Brandvik and Leirvik, 2008). Weathering describes a series of natural physical and chemical changes that oil undergoes following its release into the environment. Weathering of oil depends on the type of oil (physical and chemical properties), environmental conditions (wind, waves, temperature and sunlight), the properties of seawater (salinity, temperature) and the presence of biodegrading microbes such as bacteria (Brandvik and Leirvik, 2008). The main environmental processes that encourage weathering are oxidation, dispersion, dissolution and sedimentation, and evaporation which lead to the disappearance of oil from the sea surface (see Section 3.2 Behaviour and Fate of Oil).
2.2 Significance of Oil Properties in Oil Spill Response
Oil properties will directly affect the fate and behaviour of oil spilled in the environment as well as the effectiveness of spill response operations. Crude oil would be presumably more persistent in Arctic waters because evaporation is slow, and spilled oil can become trapped under ice making it less accessible to oil degrading bacteria and decreased weathering (Leahy and Colwell, 1990; Shata, 2010). At low temperatures oil becomes more viscous, the toxic short chain volatiles remain intact and their solubility decreases, slowing the biodegradation process (Leahy and Colwell, 1990). Environmental conditions in the Arctic may hamper the efficacy of current oil spill response operations. The presence of ice may dampen the wave energy within ice floes to a level below that required for effective chemical dispersion, precluding the use of chemical dispersants as a spill response option (Deshpande et al., 2005; Shata, 2010). In addition, the physical properties controlling dispersant effectiveness, namely the lowering of the surface 12 tension of seawater permitting oil to be broken into small droplets with wave energy, are less effective in Arctic waters since surface tension and oil viscosity both increase with decreasing temperature. The result is a thicker oil slick requiring more wave energy to disperse (Deshpande et al., 2005; Glover and Dickins, 1999). On the other hand, there can also be some advantages to consider when oil is spilled in ice infested waters (Shata, 2010). In areas where ice cover provides boundaries, oil dispersants may be used as herding agents where they are sprayed around the periphery of thin oil slicks, thus contracting the oil into a thicker slick (SL Ross Environmental Research, 2010). The colder waters and increased thickening (viscosity) of the oil decreases evaporation with the volatile components remaining in the oil, which maintains a low flash point (Glover and Dickins, 1999; Shata, 2010). This provides an ideal environment for in situ burning (Shata, 2010). In cold environmental conditions, oil persists longer, increasing the time window for mechanical oil spill recovery operations and the application of other remediation technologies (Shata, 2010). The formation of emulsions, where seawater becomes suspended in oil, occurs slowly under ice cover due to damping of the waves (Shata, 2010). Where emulsions occur, the selection of the appropriate spill response countermeasure will be largely dependent on the process that stabilizes the emulsion (Friberg, 2007). In the event of a deep sea well-head blowout such as the DWH, both pressure and temperature would influence the subsequent fate and effect of the crude oil released (Leahy and Colwell, 1990).
2.3 Canadian Arctic Offshore Crude Oils
Northern Canada is potentially rich in oil and gas resources. Indeed, oil and gas has been discovered in Baffin Bay, the Arctic Islands, the Mainland Territories, and the Beaufort- Mackenzie Basin (Drummond, 2006). A total of 1544 wells were drilled in the Canadian Arctic prior to 2004, and of these, 944 were exploratory (Drummond, 2006). There is an enormous global demand for energy resources, and given our national demand for energy and potential economic gains for Canada, the recovery of petroleum resources in the Arctic is now a priority issue shared by government and industry. In order to assess the potential environmental impacts from the production and transport of crude oil in Arctic waters, it is important to identify and classify crude oils from the area to provide the information required for risk assessment and spill response operations in the event that an accidental spill should occur. 13
In Northern Canada, a variety of oils have been identified for commercial production. These oils are listed in Table 1. The origin of crude oils can greatly affect their physical and chemical properties. Crude oils from the Arctic have been classified according to their API gravity values with the aid of Environment Canadas database on oil properties (Environment Canada, 2001a; Jokuty, 2001). Further information can be obtained from the database (Environment Canada, 2001a), which contains information on 450 oils. There is also a Spilltox database containing toxicity data on over 30 crude oils (Environment Canada, 2001b). The hydrocarbon content of crude oils can vary depending on the origin of the oil. Hydrocarbon content affects the physical properties of Arctic oils, which for the most part determine the fate, effects, and transport of spilled oil at sea.
There is considerable interest in defining the composition of a reference surrogate oil for use in predictive numerical models on the fate, transport and effects of oil spills in the Arctic for risk assessment purposes. Most of the crude oils harvested in the Arctic Region have an API gravity greater than 22; therefore, it is recommended that a light or medium grade oil be selected from the list in Table 1 to model the environmental impacts of an accidental oil spill in cold Arctic waters. Based on the chemical composition of the crude oils found in the Arctic Region, Atkinson crude has the highest aromatic content (Table 1). Unfortunately, as noted in the table, the level of information on the chemical content for many of the crude oils recovered in the Arctic is limited. Crude oil toxicity to marine life is associated with its aromatic content, namely the polycyclic aromatic hydrocarbon (PAH) compounds containing 1-3 rings in the chemical structure, and their alkylated homologues (Miller et al., 1982; Van den Heuvel Greve and Koopmans, 2007). Based on the toxicity classification scheme by Van den Heuvel Greve and Koopmans (2007), the three crude oil classes (light, medium and heavy) can be defined as follows. 1. Light crude oil (low density, high toxicity): API gravity > 40 2. Medium crude oil (medium density, medium toxicity): 28 < API gravity < 40 3. Heavy crude oil (high density, low toxicity): API gravity < 28 14 Table 1 Canadian Arctic oils (Drummond, 2006). Hydrocarbon Groups (%weight) 1 Origin Well API 1
gravity Class S A R A Beaufort Sea Adgo 16.8 heavy 89 19 1 1 Beaufort Sea Amauligak 27.4 medium 90 9 1 Beaufort Sea Atkinson 23.7 medium 46 36 15 3 Beaufort Sea Issungnak 35.0 light 92 3 0 0 Beaufort Sea Koakoak 29.5 medium NA NA NA NA Beaufort Sea Kopanoar 25.7 a medium NA NA NA NA Beaufort Sea Nektoralik 24.5 medium NA NA NA NA Beaufort Sea Nerlerk 23.9 medium NA NA NA NA Beaufort Sea Tarsiut 30.1 medium 92 7 0 0 Beaufort Sea Ukalerk 45.7 light NA NA NA NA Beaufort Sea Uviluk 29.4 medium NA NA NA NA Northwest Territories Bent Horn 41.3 light 94 5 7 0 Northwest Territories Bent Horn A-02 41.5 light NA NA NA NA Northwest Territories Norman Wells 38.4 light 86 11 3 1 Beaufort Sea Adlaktok P-09 b 30 light NA NA NA NA MacKenzie Delta Garry P-04 b 45 light NA NA NA NA MacKenzie Delta Hansen G-07 b 22-57 light - medium NA NA NA NA Beaufort Sea Isserk I-15 b 20-21 heavy NA NA NA NA MacKenzie Delta Kugpik O-13 b 45-49 light NA NA NA NA MacKenzie Delta Mayogiak J-17 b 33 light NA NA NA NA Beaufort Sea Nipterk L-19 b 18-21 heavy NA NA NA NA Beaufort Sea Nipterk P-32 b 29 medium Beaufort Sea Pitsiulak A-0 b 30 light - medium NA NA NA NA MacKenzie Delta Tuk J-29 b 32 light NA NA NA NA MacKenzie Delta W. Atkinson L-17 b 27 medium NA NA NA NA 1 Environment Canada oil properties database, 2001 a calculated from specific gravity b peer communication AEB NA - not available
In this case, it is important to note that reported API gravity values used to classify the oils do not conform to that defined by the American Petroleum Institute (ITOPFL, 2002). SINTEF critically reviewed the classification provided and reported that it was not fit for operational purposes as the heavy oil was more toxic than light oil (Van den Heuvel Greve and Koopmans, 15 2007). In contrast, data taken from Environment Canadas Spilltox database supported this classification system (Van den Heuvel Greve and Koopmans, 2007). While API gravity values aid in the classification of crude oils, the chemical composition of the oil is crucial for environmental risk analysis since a high aromatic content may be an indicator of toxicity. Both parameters provide essential information for the assessment of the potential impacts that a spill will have in Arctic marine waters. Based on current information, the fate, effects and transport of an accidental oil spill in cold Arctic waters can be adequately assessed using either light or medium grade oils, such as Atkinson crude, as a surrogate to assess environmental impacts and the efficacy of various oil spill remediation technologies. 16
17 3. Oil Spills in Arctic Waters
3.1 International Concerns and Governance
For the past 40 years the potential for pollution of the sea by accidental releases of oil has been a concern of many national governments and other organizations. Despite advances in technology and the implementation and enforcement of appropriate regulations and good working practices, an expansion of shipping activity, and oil exploration and production will increase the risk of an accidental oil spill. While we can minimize this risk, we cannot totally eliminate it. The recent Arctic Marine Shipping Assessment Report completed under the leadership of the Arctic Council Ministers Working Group on Protection of the Arctic Marine Environment has provided an overview of ships and their infrastructure needs, and impacts in the Arctic Ocean (Fretheim et al., 2011).
Contrary to that anticipated for offshore oil and gas exploration and production facilities, the majority of marine traffic operations will occur in Arctic waters that are either permanently or seasonally open. Nearly all current shipping activities take place on the periphery of the Arctic Ocean, away from permanent or drifting ice. In other areas of the Arctic which have seasonal ice cover, nearly all vessel activity occurs when and where the ice has melted or is melting so that icebreakers are not required for assistance. The changing climate in the Arctic region is also leading to a reduction in ice coverage that may increase the frequency of marine shipping traffic and the risk of accidental oil spills.
The Arctic Marine Shipping Assessment reaffirmed the Arctic states view that the United Nations Convention on the Law of the Sea remains the legal framework that influences and guides current and future governance of the Arctic Ocean and also acknowledged that the International Maritime Organization is the lead, and appropriate, UN body that can focus on marine safety and environmental protection measures for the global maritime industry, including operations in the Arctic. The Behaviour of oil and other Hazardous Substances in Arctic waters project under the auspices of the Arctic Council has gathered and synthesized the current
knowledge and expertise on the behaviour of oil and other hazardous and noxious substances released into Arctic waters resulting from accidental spills (Bjerkemo, 2011). The project promoted the development and use of technologies and working methods to improve our international capability to respond to accidents involving the spill of potential toxic contaminants.
3.2 Behaviour and Fate of Oil
Various chemical and physical processes govern the fate and behaviour of oil following a spill in the environment. It is important to note that the presence of seasonal ice has a significant effect on oil weathering in the Arctic. It is thus important to distinguish the fate and behaviour of oil during the winter season when ice is generally present, from when ice is absent or less concentrated during the spring-summer season.
Weathering processes will change the oil and affect its properties and behaviour. Oil type and environmental conditions such as temperature, sea state, winds, and other factors play an important role in how the oil will weather over time. In some cases, these processes will contribute to the natural removal of oil from the environment while in others they will contribute towards the persistence of residual oil. Knowledge of oil behaviour is essential for the identification of efficient response strategies at the time of a spill.
Work through the 1970s and 1980s largely focussed on questions related to oil behaviour and the capture of oil under ice following a large blowout. Comprehensive reviews noted that during this period, six full-scale field trials, twelve small-scale laboratory studies of oil and gas under static ice, six studies of water current transport of oil under ice, and nine studies of oil on new ice- growth were conducted (Dickins, 1994; Fingas and Hollebone, 2003). The majority of these studies produced empirical relationships of oil spreading behaviour. The primary results were that the oil spreading under ice was much slower than on the water surface alone and that the extent was governed mostly by the shape of the under-ice surface. During the last two decades, laboratory and mesocosm (including wave tank) studies, field tests and modelling efforts, have been expanded to provide insights on the interactions that occur when oil, and oil and gas 18
mixtures are discharged in waters where ice is present. Much has also been learned from spill response operations following accidental spills in ice-infested environments. A number of literature reviews on the fate and behaviour of oil in icy waters have been compiled over the past 20 years (Fingas, 1992; Dickins, 1994; Reed et al., 1999; Fingas and Hollebone, 2003; Gjsteen et al., 2003; Yapa and Dasanayaka, 2006; Brandvik, 2007; Khelifa, 2010; SL Ross Environmental Research, 2010; Dickins, 2011). This review and that of Drozdowski et al. (2011) summarize the current state-of-knowledge from studies to date, and how they might be used to predict the behaviour of oil spills in the Arctic.
Oil in Ice-Free Waters
Ice coverage in the Arctic in most areas is seasonal. Generally, ice formation will take place around September to October, and will start melting and breaking up around April to May. During the summer months many areas are either free of ice or with ice concentrations of less than 10% (drift ice). There are many possible scenarios in which an oil spill can occur, such as sub-sea blowout, sub-sea pipeline leaks, oil tanker grounding or collision incidents, crude oil leaking during loading and unloading, and bunker fuel releases. The fate and behaviour of oil spilled in open water (ice-free) conditions has been extensively studied and described in many forums and review papers (Huang, 1983; IMO (International Maritime Organisation), 1988; ITOPFL, 1986; Reed et al., 1999; Spaulding, 1988; Yapa and ASCE Task Committee on Modelling of Oil Spills, 1996).
Oil behaviour in ice-free Arctic waters is similar to oil behaviour at lower latitudes. The main processes affecting oil behaviour in ice-free waters are summarized in Figure 4. As soon as oil is spilled into the environment, it starts spreading on the sea surface, forming a thin layer. The speed and extent at which the oil spreads will depend largely on its viscosity and on the quantity spilled. Low viscosity oil will spread faster than high viscosity oil. Most crude oils discovered so far in the Canadian Arctic are of medium viscosity. Low Arctic summer temperatures might contribute to elevated oil viscosity and reduced spreading.
19
Once oil spreads and forms thin oil slicks, these start to fragment into smaller slicks or narrow bands (windrows) under the influence of winds, waves and currents. At the same time, volatile components evaporate into the atmosphere. Warm temperatures, high wind speeds and rough seas will increase the rate of evaporation. Spreading and evaporation share a close relationship. As oil spreads, the surface area of the slick will increase, increasing the evaporation rate. Generally, refined products of low viscosity such as diesel or aviation fuel will evaporate more rapidly than most crude oils. During the season in which Arctic waters are free of ice, low water temperature still plays a significant role in determining the oil weathering rate. Colder temperatures increase the viscosity of the oil, which affects spreading and dispersion but also reduces the evaporation rate. In these conditions, an oil spill in ice-free water will behave as it would in warmer conditions, but with a reduced weathering rate.
Figure 4 Physical, chemical and biological processes affecting the fate and behaviour of spilled oil (ITOPFL, 2002).
Natural dispersion will occur when turbulence generated by waves is sufficient to break up the oil slick into small droplets of various sizes. These become entrained into the water column where they mix in the upper layer and become diluted by the turbulent energy of the sea. Eventually, these dispersed droplets are biodegraded by microbial organisms. However, in order for this process to occur on a significant scale, oil droplets must average < 70 m diameter in size, as larger droplets will recoalesce, come out of suspension and form a slick, which reduces 20
the surface area of the oil available to microbial attack. This process is largely dependent on oil viscosity and sea state. Natural dispersion is more likely to happen with low oil viscosity (usually Group 2 oil, API gravity > 40) and a sea state generating small breaking waves.
Biodegradation is the process by which microorganisms already present in the sea will use oil as a carbon source and metabolize petroleum compounds. Biodegradation is a significant weathering process when the oil is either dispersed into small droplets or broken up in a very thin film. It is not a significant process when oil is highly viscous, remaining in thick slicks, or when emulsification has taken place. It mainly occurs with light to medium oils in which hydrocarbon chains are relatively short. Heavier oils with high wax or asphaltene content are difficult to biodegrade. Biodegradation is a relatively slow process that necessitates the presence of microorganisms, nutrients and oxygen. The rates are usually assumed to be slow in cold water environments based on the majority of past microbiological studies. However, recent studies under low temperature conditions including the Arctic, ice infested waters, and at deep ocean depths (Hazen et al., 2010; Lee et al., 2011c; Lee et al., 2011d) have also shown significantly rapid oil biodegradation rates.
Emulsification is another process that is likely to occur as oil slicks are drifting on the sea surface. With the turbulent energy from waves, some oils will take up water droplets to form an emulsion of water in oil. Emulsification usually forms in oil with a nickel or vanadium concentration greater than 15 ppm, or an asphaltene content of more than 0.5%. However, the most significant factor will be the presence of waves usually generated by a sea state of Beaufort 3 or above. Emulsions are usually very viscous and increase in volume up to four times the volume of the original oil. They are also very persistent since other weathering processes are greatly reduced once they are formed.
The weathering processes summarized in the preceding paragraphs occur as soon as oil is spilled. Their relative importance varies mainly according to oil type and weather conditions. Oxidation, dissolution and sedimentation can also take place during an oil spill, but in most cases, these particular weathering processes play a limited role in the ultimate fate of oil. Sedimentation is more likely to happen in the nearshore environment where oil becomes associated with 21
suspended particulate material including sediments which would facilitate its transport to the seabed. Dissolution is likely to happen with light oils or refined products as these products have a higher concentration of light compounds that are soluble.
Oil in Ice Covered Waters
All of the scenarios that occur in open water conditions could occur in locations where ice is present; therefore, oil could be released under ice cover from a sub-sea leak or blowout, or onto the ice surface (for example from a platform blowout), or in waters with ice floes. Numerous field and laboratory research projects have been conducted since the 1980s to study oil weathering in ice-covered waters. These have shown that oil is subjected to the same weathering processes mentioned in the previous section. Because of the cold temperatures, oil viscosity will generally increase for all oil types; however, interaction of oil with ice will affect the rate at which these processes are taking place. Natural dispersion and emulsification are largely dependent on wave energy in order to take place. The presence of ice will have a significant impact, as short waves will be damped by ice floes, greatly reducing the rates of natural dispersion and emulsification. In water with an ice coverage greater than 60%, the ice may effectively contain and reduce oil movement, and thus protect sensitive shoreline resources. Evaporation and biodegradation still take place in ice-covered water, but the low temperatures usually associated with the presence of ice reduce the rate at which they occur.
Direct interaction of oil with ice affects its behaviour. Figure 5 summarizes the multiple ways oil can interact with ice. The presence of ice greatly complicates the possible fate of oil spilled in Arctic waters. The behaviour of oil in ice is complex, and the difficulties in modelling the physics of ice formation and movement on scales of metres are magnified when the uncertainties of oil behavior are added. If oil is spilled on ice, evaporative loss will be the main weathering process as spreading will be limited by ice surface roughness and by absorption into snow. Because of this, oil accumulations on the ice surface are expected to be limited in area and fairly thick. For lighter oil types, absorption by snow could be a significant process depending on the quantity of snow on the ice surface.
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Figure 5 Oil and ice interaction processes (Bobra and Fingas, 1986).
Oil spilled under the ice is subject to various processes (Figure 5). In most cases, oil will drift under the ice layer because of the currents and movement of the ice floes and will eventually accumulate in naturally formed reservoirs due to ice roughness. These will vary in size but significant quantities of oil could be trapped under the ice in this manner. Some of the oil could be dislodged by currents and continue to drift under the ice. Several studies have set the threshold for movement of oil under ice at 0.5 kt (26 cm/s). Oil can become encapsulated within the ice structure in winter conditions when new ice is being formed. In some cases, this process can happen rapidly (within 18 to 72 h) once oil is trapped under the ice. It is important to note that oil weathering processes are inhibited by the encapsulation of oil. In springtime with melting and warming of the ice sheet, encapsulated and trapped oil can migrate vertically through brine channels and reach the surface of the ice to form pools of fresh oil. The rate of vertical migration largely depends on the number of brine channels in the ice sheet and the oil viscosity.
The lower oil weathering rate generally observed in ice-covered waters could represent an advantage for response effectiveness in some spill scenarios. Reduced spreading in icy 23
conditions could increase the window of opportunity for certain response techniques (chemical oil dispersant applications, for example) and be a significant advantage in the Arctic, since residual oil would remain in an unweatherd state longer than it would under ice-free conditions. However, the presence of ice in itself represents a great operational difficulty that can offset the advantages provided by the reduced weathering rate.
3.3 Factors Influencing Oil Behaviour
Numerous field, laboratory and tank studies have been conducted over the past 30 years on the behaviour of crude oils and refined products (including fuel oils) spreading in, on, and under ice. A good understanding of the basic processes controlling the behaviour of fresh and weather oil, and the development of numerical models to describe their time-series changes have been gained from these efforts, and are reviewed by Lewis (2000), Fingas (2003), Yapa et al. (2006) and Drozdowski et al. (2011).
Spreading in Broken Ice
An oil spill on a calm water surface spreads by gravity and is resisted by inertia, viscosity, and surface tension until the slick reaches a thickness of approximately 0.1 mm (NRC, 2005). As noted previously, the spreading speed is determined by many factors. Light crude oil spreads much faster than heavy fuel oil, and wind, waves and currents can significantly increase the rate of spreading. A rough sea with high mixing energy will significantly enhance this effect.
In cold regions, the spreading of oil can be significantly affected by the presence of snow and ice. In broken ice, oil is assumed to move at the water surface, flowing around any ice present. Oil can pile up and thicken around ice flows, and if sufficiently confined, may begin to flow under the ice at the ice-water interface. It has been noted that for ice concentrations less than 30%, oil behaves as in open water (Deslauriers, 1979; ITG, 1983; SL Ross Environmental Research Ltd. and DF Dickins Associates LLC., 1987; Venkatesh et al., 1990). For ice concentrations greater than 30%, the oil is found to drift with ice. The equilibrium oil thickness in slush or brash ice (accumulations of the wreckage of other forms of ice made up of fragments 24
not more than 2 m across) is nearly four times that on cold water, which itself is very different from that on warm water. As a result, the oil-contaminated area at higher ice concentration is several orders of magnitude smaller.
In tank tests, Martin et al. (1976) observed that both diesel oil and Prudhoe Bay crude oil surfaced readily when poured into grease ice and slush, and they calculated an equilibrium thickness of 1 mm for diesel oil in a mixture of pancake and grease ice. Sayed and Lset (1993), studying the spreading of oil on water and among brash ice in moderate to high concentrations, showed that the ice confined the oil to between 5/10 and 8/10 of surface coverage, increasing the slick thickness and limiting the final equilibrium extent of the oil. A modified Fay equation for spreading based on the results of small field spills represents the most suitable analysis to date. In brash ice, spreading rates decrease with increasing ice concentrations and the presence of slush ice strongly reduces the spreading, but the effect is small for ice concentrations below 20 30% (Gjsteen and Lset, 2004). Increased motion in the ice cover resulted in increased spreading rates, and this effect was especially pronounced in the presence of slush. Decreased spreading rates due to increased oil viscosity were also observed.
In terms of developing predictive models, Gjsteen and Lset (2004) measured spreading rates of marine fuel oils in slush and frazil ice with different wave energies. It was clear that the presence of broken ice significantly slowed oil spreading. Gjsteen (2004) developed a mathematical model using Newtonian viscosity to predict the spreading of oils over water and slush ice, and found good agreement with the lab data of Sayed and Lset (1993). The model was reportedly coupled to a discrete-element ice model. Hara et al. (2008) developed a model for flow of oil through a broken ice field, and included a specific term for the critical thickness of oil which will begin to flow under the ice, rather than through the broken ice field, dependent on the oil and water densities and the oil-ice-water interfacial tension. This model has not yet been tested.
Lewis (2000) concluded that at lower ice coverage (< 30%), the oil and ice will move at different rates under the influence of wind. The influence of wind on an oil slick is to increase the movement of the slick by approximately 3%, while ice floes tend to move the slick faster (4.5 to 25
6%). At ice concentrations greater than 50%, oil drifts with ice at speeds from 4 to 7% and the rate decreases as the ice concentration increases.
Field experimental data on oil spreading under various broken ice conditions (4/10, 5/10 and > 9/10 coverage) has been reported (Buist and Bjerkelund, 1986). With increased coverage of brash ice, oil spreading was dramatically reduced. A phenomenon described as lead pumping was reported to redistribute oil from the water to the ice surface under dynamic conditions. The effects of lead closure rates on the vertical movement of oil were studied by MacNeil and Goodman (1987) in an outdoor basin. It was observed that oil was forced under the ice when a lead closed slowly. At high closure rates (above 12 cm/s) most of the oil was forced to the top surface of the ice.
Weerasuriya and Yapa (1993) and Yapa and Belaskas (1993) experimented with spreading of oil under and over simulated broken ice fields in small tanks. Based on the laboratory observations it was concluded that the behaviour of oil spilled under a fragmented ice cover depends on the type of ice cover. While oil may penetrate completely through one type of cover, it may not penetrate another.
In 1993, numerous authors reported on test tank experiments and a subsequent experimental spill of North Sea crude in the Barents Sea marginal ice zone off the coast of Norway (Jensen, 1994; Reed and Aamo, 1994; Singsaas et al., 1994). High concentrations of pack ice (90% initially, declining to 75% at the end of the experiment) kept the oil thick and immobile for days which, in combination with cold temperatures and the damping of wave action by the ice, significantly slowed oil weathering processes (evaporation, natural dispersion and emulsification). Brandvik (2006a) presents a comparison between the results obtained from the experimental spill in pack ice with a similar experimental spill in open water.
26
Movement on Ice
The spreading of oil on ice is more similar to spreading of oil on land than on the sea, and the slick is much thicker (Lewis, 2000). The spreading rate for oil on ice is determined by the oil density and viscosity as well as the roughness of the surface over which the oil is spreading. Discrete ice deformation (rafting, rubble, pressure ridge) may lead to a contained, thick, oil pool. Glaeser and Vance (1971) is probably the earliest reference to oil spills on ice. It was found in their study that the ice surface adsorbed the oil to a saturation level of about 25% and the degree of spreading is a function of spill volume and spreading time. Spreading is also affected by temperature (Chen et al., 1976). There was no spreading below -19 o C and warm oil spread more rapidly. Another early study on oil spreading on ice concluded that gravity is the only important spreading force and the final radius is only a function of time (McMinn and Golden., 1973). Additional new papers have been written on oil spill spreading on ice (Brandvik and Faksness, 2009; Dickins et al., 2011; Jaraula et al., 2008; Peishi et al., 2011; Wang et al., 2008).
Movement Under Ice
Oil pooling immediately underneath the ice layer has been observed in laboratory experiments (Payne et al., 1991) and field trials (Dickins et al., 2008). A site specific study (Ramseier and Rene, 1973) showed that with water currents near the North Pole, the oil spreading rate under ice was 800 cm/day. Chen et al. (1976) observed the spreading of oil under a freshwater ice sheet in a small test tank and found that the radius of oil is affected by the water density, water or oil viscosity, time, and volume rate of oil flow to the slick. If oil is in direct contact with the underside of the ice, oil viscosity is important. The spreading rate was proportional to the power of the elapsed time in the absence of current. In the presence of strong current, oil droplets travelled some distance before rising, and many droplets did not adhere to the ice (Fingas and Hollebone, 2003).
It was reported that the effect of an ambient current on oil transport under ice is much greater than effects due to forces such as buoyancy, viscosity, and interfacial tension (Uzuner et al., 27
1979). However, some have argued that buoyancy and viscosity are the dominant forces for oil spreading under ice (Yapa and Belaskas, 1993; Yapa and Chowdhury, 1990).
Buist et al. (1981) studied the behaviour of oil and gas release under ice in the Beaufort Sea. It was observed that oil broke into droplets as the oil and gas mixture left the discharge pipe due to turbulence. As the gas rose out of the jet stream it quickly collected in a pocket under the ice. For the under-ice oil and gas injection study at a gas to oil ratio of 150:1, it was observed that oil rose in the form of pendent drops of 1 or 2 cm in diameter. With currents of 14 cm/s in the flume tank, oil began to migrate downstream. Another study involving gas as well as oil under ice is the work done by Purves (1978). For a 60:1 ratio of gas to oil released under ice in a test tank, it was found that the presence of gas helped the oil to spread more rapidly and thinner.
It was summarized by Fingas and Hollebone (2003) that in low currents, the oil released under ice will spread upon reaching the under ice surface due to combined actions of buoyancy, viscosity and surface tension. A number of force-balance models have been developed to predict spreading under a smooth ice bottom (reviewed in Fingas and Hollebone 2003). However, in practice, sea-ice is characterized by significant under-ice roughness, and the final under-ice configuration is determined by the under-ice roughness and topography. Oil has been observed to spread systematically, filling the nearest under-ice depressions first before overflowing into the next depression. Malcolm and Cammaert (1981) calculated the pool thickness of crude oil under ice in sea water, and the thickness ranged from 4.27 to 10.63 mm for interfacial tension ranging from 10 to 30 dynes/cm. Local ice conditions are much more important to the final oil disposition than microscale spreading behaviour. A volumetric analysis is considered to be the most effective approach for predicting the spread of large oil and gas discharges under an ice sheet, and several general spreading models have utilized this method. The key parameters are oil and gas volumes, under-ice storage capacity, and potential for gas expansion.
Oil under stationary or land-fast ice spreads according to not just the fluid property factors, but is also governed by currents and the under-ice topography. Several field observations have noted that, in the absence of small currents, the deposition and spreading of oil under continuous ice is largely governed by the shape of the under-ice surface. An early approach to estimating the oil 28
volume holding capacity of ice for oil was to estimate the volume above the mean draft level of the under-ice surface. Based on measurements of under-ice topography (Goodman et al., 1987; Kovacs et al., 1981), this geometric filling approach implied that oil spills under ice would be confined to a much smaller area than spills in open water (Dickens et al., 2008). Note that these models considered the final geometric holding capacity of the under-ice topography only, and do not consider the oil spreading dynamics.
Early field observations of oil spilled under ice in Beaufort Sea had indicated that oil under a smooth continuous ice surface would spread to an equilibrium thickness of approximately 1 cm (Dome Petroleum Ltd., 1981; NORCOR Engineering & Research Ltd, 1975). This quality was confirmed in a series of observations of oils spilled under smooth ice (Rytkonen et al., 1998): the oil spreading speed was dependent on oil viscosity and the oils spread to an equilibrium thickness of 7 mm to 14 mm, independent of viscosity. This minimum equilibrium thickness concept was key to a new model for the spreading of oil under ice proposed by Wilkinson et al. (2007a; 2007b), which included the oil-filling dynamics driven by gravity-controlled motion under the ice cover. They found that the oil pooled in much lower areal concentrations than geometric volume factors predicted, spreading to cover an area 14 times greater than predicted by a mean-volume filling approach. This new theoretical approach did not incorporate hydrodynamic currents or oil plume spreading during rise to the ice sheet, which would be expected to further increase spill area. While the approach provides a physics-based process model for spreading under continuous ice, it remains to be validated by experimental observations.
In terms of knowledge gaps, a particular area that requires much more research is the movement of spilled oil under old, multi-year ice. Old ice would be encountered in deeper water and off Greenland which are locations for future oil and gas exploration (Cairn, 2011; Dickins, 2011).
Movement Through Ice
Oil released under a first year ice sheet rapidly became encapsulated and remained in place until February and March when it began to migrate through former brine channels to the surface 29
(NORCOR Engineering & Research Ltd, 1975). The rate of encapsulation depends on the air- ice-water temperature gradient, the under-ice topography, and the volume and properties of the trapped oil (Fingas and Hollebone, 2003). The observed vertical movement length in March was only about 20 cm but increased significantly in April. Similarly, it was observed that oil started appearing on the surface in early June from a test release done in December (Buist et al., 1981). In anecdotal data reported by early field trials, NORCOR Engineering and Research Ltd. (1975), Dome Petroleum Ltd. (1981) and Buist et al. (1983) all reported that oil or emulsions were trapped within 24 hours, and sometimes within four hours (Buist et al., 1983). Numerical models based on heat flow across the oil and gas lens generally predict that the ice growth beneath the lens will be reduced (as the thermal conductivity of the oil is less than that of the ice for most field situations). However, no measurable difference in thickness between oiled and unoiled ice was observed in the NORCOR or Dome Petroleum field spills. This may be attributable to natural variation in snow cover which produces variations in ice thickness greater than those which could be induced by the oil. Unless very thick pools are involved, the effect of encapsulated oil on subsequent ice growth beneath the lens will probably be minimal.
The available field and laboratory test data show that the encapsulated oil will be released in the spring as the ice sheet deteriorates. Oil escapes from the ice sheet by a combination of two general processes: vertical rise of the oil through the brine channels in the ice, and ablation of the ice surface down to the oil lens in the ice. For a combined oil and gas spill, the gas will be released in advance of the oil. Both release processes have been observed to occur in the field. The relative quantities of oil released depend on several factors including the depth of the oil lens in the ice, the rate of brine channel opening and the configuration of the oil in the ice, whether as discrete droplets or pools of oil.
Of the field spills conducted to date under first-year sea ice, encapsulated oil was released in the next melt season. Data on release from multi-year ice is limited to one series of small-scale field spills. This study indicated oil rises quickly to the surface through cracks, but persists for at least two melt seasons and possibly five on the surface of the ice because multi-year ice is thicker and the brine channels may be discontinuous.
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Russian researchers conducted experiments on oil spilled under ice floes similar to those found in the Sea of Okhotsk (Ohtsuka et al., 2001; Ohtsuka et al., 1999). These authors found that oil progressively filled the cavities on the bottom of the ice floes. Less than 1% of the oil permeated through a 7-10 cm thick floe of pancake ice. Faskness and Brandvik (2005) report a series of experiments involving freezing lenses of oil at differing depths to examine the migration of PAHs, the water-soluble components from six different crude oils, over a winter field season. They found that oil compounds (but not the whole oil) diffused through the ice sheet forming a concentration gradient to the bottom of the sheet, but at concentrations that were very low (less than 6 ppb) at the water interface.
The movement of oil through multi-year ice has been reported by Comfort and Purves (1982). It was observed that most of the oil placed under multi-year ice migrated to the surface after one year and no oil remained at the study site after five years.
Adsorption to Snow
The earliest study of oil spill processes in snow can be traced back to McMinn (1972) who conducted experimental spills of Prudhoe Bay crude oil on Arctic snow and ice. Oil adsorbed to snow to form a fairly stable mulch (Buist et al., 1987; McMinn, 1972). The adsorbed amount was 20% and 25% in the case of McMinn (1972) and Buist et al. (1987) respectively.
Oil spilled onto snow may also flow downward to the ice layer, and then creep onward beneath the snow layer. A comparison of theoretical equations (Belore and Buist, 1988) with experimental data (Glaeser and Vance, 1971; McMinn, 1972) indicates that the initial spreading of instantaneous spills on snow or ice is governed by the gravity-inertia regime, but spreading reverts to the gravity-viscosity regime. The horizontal flow of oil in snow at an impermeable layer was a function of snow properties (void ratio, specific permeability), dynamic viscosity of the oil, and time. Nelson and Allen (1982) observed that oil soaks into snow more thoroughly if the air temperature is higher (4 o C) and the snow softer. Bech and Sveum (1991) observed that oil soaks through the snow and spreads out. The containment of diesel fuel by snow is reported by Allen (1978). 31
3.4 Factors Influencing Oil Fate (Weathering)
Changes to oil properties following its release into the environment have received considerable attention as it influences the behaviour of the oil. The properties that are altered during oil exposure, thus defining the fate of oil include density, viscosity, surface and interfacial tensions, and water content. Typical weathering processes include evaporation to the air, dissolution in water, emulsification with water to form water-in-oil gels, photodegradation and dispersion of oil into water.
Singsaas et al. (1994) found that the rates of evaporation, dispersion and emulsification were all significantly retarded in the broken ice found in leads. They reported that the primary factors reducing the weathering rate when compared to open water and temperate conditions were wave- damping, limited spreading of oil bounded by sea ice, and temperature.
Evaporation
Evaporation is the most important and rapid of all weathering processes, and it accounts for the loss of 20-50% of many crude oils, 75% or more of refined petroleum products, and 10% or less of residual fuel oils (NRC, 2003; NRC, 2005). Immediate surface evaporation results in losses of small alkanes (C 5 -C 10 ), and monoaromatic compounds like BTEX (benzenes, toluenes, ethylbenzenes, xylenes). Several experiments with refined gasoline and diesel (Ivanov et al., 2005; Serova, 1992) have found nearly complete evaporation on the surface of ice during the summer season.
Payne et al. (1991) observed that under spring and summer conditions simulated in wave tank systems, all compounds with vapour pressures greater than C 11 -alkanes were lost within nine days. The evaporation of oil on ice in winter is slower, but eventually the oil will evaporate to approximately the same degree as it would if spilled on the water in summer. Since evaporation is a surface phenomenon, the evaporation rate can be significantly influenced by the oil film 32
thickness as a result of spreading. The rate of evaporation is also increased by strong winds, rough seas and higher air temperature.
The effects of snow on evaporation have been discussed by Belore and Buist (1988). It was observed in their experiments that oil in a control tray (no snow) experienced the greatest evaporative loss. Of the ones with snow, the uncompacted snow had the highest evaporative loss. Increasing snow density and thickness reduced evaporation.
Brandvik and Faksness (2009) studied evaporative loss of a light oil (fresh Statfjord crude) under three different ice coverage levels at various surface current and wave height conditions with different air temperatures (-15 to about -5 o C). They reported that evaporative loss for open water, 30% ice coverage, and 90% ice coverage was 30%, 25%, and 19%, respectively. The difference in evaporative loss was mainly due to the different film thicknesses. Ice concentration also affects pour point and flash point. They also found that the viscosity change due to evaporation was minor, but changes in viscosity due to water-in-oil emulsion were significant.
In freezing waters during ice formation, layers of ice platelets can form to cover the oil surface and cause encapsulation of oil among ice crystals. In this case, the spill will remain entrapped within the columnar ice until a thaw cycle is initiated. During and after oil encapsulation within ice in a flow-through system, the concentration of dissolved components and dispersed oil droplets in the water column was effectively diluted to background levels within several days (Payne et al., 1991).
Dissolution
Compounds of low molecular weight in an oil slick are subject to two competing processes: dissolution into the surrounding water and evaporation into the atmosphere. For surface spills, true dissolution of individual components from the slick is not considered significant in terms of the overall mass balance of an oil spill (NRC, 2003; NRC, 2005). Dissolution of individual components is important, however, when considering the potential for biological impacts. 33
Dissolution of volatile and semi-volatile components of oil from a deepwater blowout oil spill can be significant.
The dissolution of water soluble components through sea ice has been studied by performing laboratory experiments and field trials dealing with oil encapsulated in ice (Faksness and Brandvik, 2008a; Faksness and Brandvik, 2008b). By freezing six oils (five crude oils and a heavy fuel oil) into sea ice in winter and quantifying the migration of water soluble components from the oil into the ice, it was found that the content of water soluble compounds in the ice decreased with ice depth, and the concentrations changed as a function of time, confirming that the water soluble components had been transported from the overlying oil through the brine channels in the ice to the underlying water. The field experiments showed that not only ice thickness, but also air temperature prior to an oil spill, are important for the distribution of water soluble components in ice. At relatively high air temperatures, ice has higher porosity, and the majority of the water soluble components will leak out more quickly. Conversely, if a spill occurs during extremely cold conditions, the ice is less porous and water soluble components are released at a slower rate, resulting in a longer exposure period of toxic components to ice- dwelling (sympagic) organisms.
Dispersion
Under turbulent hydrodynamic regimes, a surface oil slick can be entrained in the water as small oil droplets that are dissipated and diluted in the water column (Delvigne and Sweeney, 1988; Fraser and Wicks III, 1995; Lee et al., 2001). This is a natural process that is beneficial to oil spill cleanup, because oil in the form of small droplets with a higher surface to volume ratio is biodegraded more rapidly. Furthermore, the formation of oil droplets enhances interaction with suspended particulate material. Waves create eddies of different sizes cascading to the smallest size class where the energy is dissipated ultimately into heat under the influence of viscosity. The steep velocity gradients of the small eddies are of major importance for shearing off of droplets from the slick and for the collision probability of droplets, whereas the large eddies are primarily responsible for the diffusive transport of the oil droplets.
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The entrainment rate of oil depends upon the properties of oil such as viscosity, the oil-water interfacial tension, and the surface energy breaking rate. As the slick weathers, the oils physico- chemical properties change. Viscosity, in particular, can increase by orders of magnitude during the uptake of water into the slick to form a water-in-oil emulsion. The entrainment rate also depends upon the fraction of the sea surface hit by breaking waves per unit time, which in turn is a function of wind speed. Stochmal and Gurgul (1992) found that oil in water dispersions separated 3.5 times more slowly at near-freezing temperatures (1C) than at 15C.
Emulsification
Water-in-oil emulsion, commonly called chocolate mousse, is formed by dispersion inversion or by water drop entrainment. Emulsification competes with oil-in-water dispersion (dispersed oil). Water-in-oil emulsion is an important weathering process, especially in the early stages of an oil spill, which alters the oil composition and behaviour. Emulsification increases the volume of the slick and reduces the biodegradation rate. The formation of stable water-in-oil emulsions has a negative impact on the success of various oil spill cleanup efforts, including increased volume for containment, lowered combustibility for ISB, and increased viscosity so that chemical dispersion is more difficult. Rapid emulsion formation also diminishes the rates of evaporation and dissolution, retaining more toxic low molecular aromatic compounds in the residual oil.
The rate and extent of the formation of water-in-oil emulsion are dependent upon oil properties, the turbulence energy level, and environmental conditions. Weathering caused by evaporation in water-in-oil emulsions of crude oil occurs to a significant extent in a matter of 12 to 24 h at sea surface temperatures above 10C (Daling et al., 1997; Lewis et al., 1995). Weathering of Brage crude oil, as water-in-oil emulsions in a meso-scale flume at 13C, reached a maximum water content (80%) within 4 h and emulsion viscosity steadily increased during the initial 70 h (Lewis et al., 1995). The corresponding chemical dispersability of the weathered oil dropped drastically within the first 12 to 24 h.
When oils are released into ice-covered waters, ice formation may dramatically alter the rates and relative importance of the different weathering processes. Oil released into a growing slush 35
ice field during late fall or early winter may be subject to stranding on the upper ice pan surfaces and rapid water-in-oil emulsification, followed by partial density-mediated submersion and incorporation into the ice canopy (Payne et al., 1991). For the oil on the upper ice surface of pans and smaller floes, diffusion-controlled evaporation predominates. For the portion of oil that remains in the ice-water matrix, emulsification may occur rapidly before significant evaporation and dissolution can occur, affecting the overall mass balance of the oil slick. Oil from a subsurface release under an existing ice canopy is subject to encapsulation before evaporative weathering, although dissolution has been demonstrated.
Brandvik and Faksness (2009) describe oil weathering experiments with a light naphthenic crude in broken ice (0%, 30% and 90% coverage) in an outdoor race-track flume cut in the ice. They reported that the weathering of spilled oil was reduced with increasing ice coverage. The formation of water-in-oil emulsions was reduced by wave damping by the ice. Ice confined the oil, increasing thicknesses and reducing available surface area. This geometric effect slowed evaporation at the highest ice coverage and reduced emulsification. At low ice cover, little difference in emulsification, monitored by viscosity increase and water-uptake, was observed from oil in open water. The effect of ice on water-in-oil emulsification (38-41% water content) between open water and 30% ice cover was found to be small and probably insignificant, but the difference with 90% ice cover (20% water content) was large (Brandvik and Faksness, 2009). In comparison, weathering of Statfjord oil in the open water without any slush ice can reach a water uptake of 75-85%.
Buist et al. (1983) placed a water-in-oil emulsion under first year ice in the Southern Beaufort Sea and the emulsion became encapsulated within 48 h. Unlike oil which can migrate to the surface through brine channels (Buist et al., 1981), the emulsion only appeared on the surface during ice melt.
The weathering and fate of water-in-oil emulsifications of four Alaskan crude oils, namely ANS, Endicott, Kuparuk and Northstar, in pack ice meso-scale and large-scale wave tanks, were evaluated in a three-year program of laboratory and test-tank trials (Buist et al., 2009). Empirical relationships based on oil properties for evaporation of oil on water, in broken ice and in snow; 36
equilibrium spreading thickness on water; equilibrium spreading thickness on ice; the extent of oil spreading on ice; the extent of oil spreading in snow; and the critical current velocity which results in stripping of oil from under-ice surfaces were reported. The researchers were unable to develop quantitative relationships for the rate or probability of emulsion formation in broken ice and the rate of appearance of oil encapsulated in ice during spring melt. Very little emulsification occurred with oils under the low wave energy that was tested. Emulsion formation was impeded by wax precipitation in the test oils, interfering with the uptake of water to form a stable emulsion. This caused the oils to become non-Newtonian fluids, which, as well as reducing emulsion formation, also greatly reduced spreading of the oil on water, on ice and through snow. The wax matrix of the oils, gelled by the low temperature, reduced the evaporation rate of the oil, which Buist et al. (Buist et al., 2009) suggested could be modeled as a lowered mass transfer term in the evaporation equation.
Most oils formed high water content (80%) emulsions under the high wave conditions that were tested (Buist et al., 2009). The emulsions formed more rapidly in higher ice concentrations. This is consistent with the conclusions reached by Payne et al. (1991), but in conflict with the results of Brandvik & Faksness (2009), probably due to the differences of the surface energy levels and the ice morphologies of these test systems.
Brandvik and Faksness (2009) hypothesized that weathering processes strongly influenced by cold temperatures may extend the operational time window for several contingency methods in comparison to similar treatment of oil spills in open water. Such processes include reduced oil spreading (caused by ice coverage and weakened wave action), decreased water uptake (owing to less oil-water interaction), less evaporation, and slower changes in viscosity and pour point in dense ice conditions. All these factors can potentially open up a wider window of opportunity for dispersant and in situ burn (ISB) treatments.
Brandvik et al. (2010a) subsequently reported improvements to the SINTEF oil weathering model as a result of studies carried out under the joint industry program (JIP). In a series of experiments conducted in a permanent race-track flume and in field trials in a temporary in-ice flume similar to the design used in their previous work (Brandvik and Faksness, 2009), and in 37
trial spills into natural pack ice, they evaluated oil evaporation, emulsification, viscosity increase, water uptake and natural dispersion for five oils from the North Sea. They found that the various weathering processes were highly dependent on the initial oil composition and properties. Similar to their earlier results, they reported that oil in open water and low ice conditions weathered most quickly, while oil in high ice cover had only slight increases in viscosity, low water uptake and small evaporative losses. They suggested that a combination of wave dampening reducing the shear experienced by the oil, and herding by the ice, greatly reduces the rate of change of an oil in Arctic ice-infested waters.
Photo-Oxidation
Photo-oxidation and biodegradation are two very important transformation processes that occur with petroleum products that are released into the marine environment (Dutta and Harayama, 2000; Garrett et al., 1998; Prince et al., 2003b). Experiments with refined gasoline and diesel (Ivanov et al., 2005; Serova, 1992) on the surface of ice during the summer season showed that, due to longer exposure times, photo-oxidation is a much more important process for oil degradation in the Arctic than in more temperate climates. Despite some reservations over the toxicity of products formed (Lee, 2003; Maki et al., 2001), photo-oxidation of crude oil by natural sunlight may provide an opportunity for the introduction of novel procedures for the remediation of marine oil spills. Garret et al. (1998) demonstrated that photo-oxidation and biodegradation have opposite effects on aromatic hydrocarbons in crude oils. Whereas microbial degradation and evaporation/dissolution result in the depletion of unsubstituted aromatic compounds relative to their alkylated homologues, photo-oxidation selectively degrades the alkylated aromatic compounds (Prince, 1993; Prince and Clark, 2004). Nevertheless, since neither photochemistry nor biodegradation affect the levels of hopanes and other biomarkers to a significant extent, referencing the PAHs to hopane or a similar conserved marker can reveal the extent of degradation.
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Biodegradation
Many microorganisms that are ubiquitous in nature have the capacity to utilize petroleum hydrocarbons as the sole source of carbon and energy (Atlas, 1981; Head et al., 2006). A wide variety of bacterial and fungal genera exhibit the capacity to degrade hydrocarbons. Many hydrocarbon degrading microorganisms have been isolated from a variety of marine environments (Atlas, 1984; Leahy and Colwell, 1990; ZoBell, 1973). Recently, Prince et al. (2010b; 2010a) published a list of 181 genera of bacteria, 163 genera of filamentous fungi and yeast, and 22 genera of algae that are able to degrade hydrocarbons by metabolizing them in order to grow. These findings are not surprising considering the fact that marine microorganisms have long been exposed to significant quantities of petroleum hydrocarbons from natural seepages.
From 1990 to 1999, approximately 600,000 tons of petroleum were released into the worlds oceans per year from natural seepages alone (NRC, 2003; Stout and Wang, 2008). Biodegradation by microbial communities is the major process controlling the weathering and eventual removal of oil from natural seeps that enters the marine environment (Atlas, 1995; Atlas and Bartha, 1992; Leahy and Colwell, 1990). Bacteria are the predominant hydrocarbon degraders in the marine environment, with a global distribution from tropical environments to extremely cold Antarctic and Arctic environments (Head et al., 2006; Venosa and Zhu, 2003). They are normally present in small numbers in pristine environments, but these oil degrading microbes can be selected and multiply rapidly upon the introduction of oil (Atlas, 1995).
Biodegradation rates have been shown to be the highest for saturates, followed by light aromatics, with high-molecular-weight aromatics and polar compounds exhibiting extremely low biodegradation rates (Prince, 2010c). Co-metabolism plays an important role in oil biodegradation and may require microbial consortia or syntrophic interspecies cooperation (McInerney et al., 2008). Many complex branched, cyclic, and aromatic hydrocarbons, which otherwise would not be biodegraded individually, can be oxidized through co-metabolism in an oil mixture due to the abundance of other substrates that can be metabolized easily within the oil (Atlas, 1981). 39
Microorganisms are known to produce extracellular biosurfactants to promote the formation of oil-in-water emulsions that aid in the uptake and subsequent degradation of hydrocarbons (Desai and Banat, 1997). The hydrophilic and hydrophobic components within the biosurfactants emulsify hydrophobic hydrocarbons, and allow for transport into the hydrophilic intracellular space for biodegradation (Southam et al., 2001). In addition, the fatty acid moieties of biosurfactants promote the growth of microorganisms on the surface of oil droplets (Rosenberg et al., 1979). Nikolopoulou and Kalogerakis (2008) reported that the use of rhamnolipid biosurfactants increased removal of weathered petroleum hydrocarbons (96% removal of C19 C34 n-alkanes within a period of 18 days) and reduced the lag phase prior to the onset of biodegradation. Saeki et al. (2009) showed that addition of biosurfactant JE1058BS to seawater stimulated the degradation of weathered crude oil (ANS 521) by stimulating the activity of the indigenous marine bacteria and facilitating the removal of crude oil from the surface of contaminated marine sediments.
Field studies have shown that active microorganisms living in low-temperature environments are dominated by two groups: psychrophilic and psychrotolerant, which are sometimes called psychrotrophic (Atlas, 1984). As defined by Morita (1975), psychrophiles experience optimum growth at less than 15C, with a maximum growth temperature below 20C and a minimum growth temperature at or below 0C. Recent studies on pelagic bacteria in the coastal Alaskan Arctic, Chukchi Sea, showed that psychrophiles were numerically dominant over psychrotolerant organisms regardless of the nutrient status or algal bloom conditions of their surrounding waters (Connelly et al., 2006). Despite living at these low temperatures, psychrophiles often have metabolic rates comparable to those displayed by the mesophiles adapted to more moderate temperatures. For example, Delille et al. (2009) reported that a temperature of 4C in the Antarctic had little effect on biodegradation efficiency and that the nutrients, nitrogen and phosphorus, were the limiting factors. Results obtained by Siron et al. (1995) indicated that the temperature threshold for observing significant oil biodegradation was around 0C.
Decreases in solubility associated with low temperatures were considered to be a causal factor for the cases of observed recalcitrance of hydrophobic compounds in cold-water and Arctic 40
conditions. However, recent reports have indicated that some bacteria may have adapted to the low solubility of hydrophobic environmental chemicals (Deppe et al., 2005; Wick et al., 2002). Indeed there is now evidence that hydrocarbon-degrading microbes may have novel uptake mechanisms that enable them to degrade hydrocarbons at rates that exceed their rates of dissolution in the aqueous phase (Leahy and Colwell, 1990; Thomas et al., 1986).
Throughout the world, the salinity of seawater averages about 3.5%. Salinity variations, albeit small, are mainly caused by such factors as melting of ice, inflow of river water, evaporation, rain, snowfall, wind, wave action, and ocean currents that cause horizontal and vertical mixing of the saltwater (Lagerloef et al., 1995). Most marine species have an optimum salinity range of 2.53.5% (ZoBell, 1973) and species living in the transition environments are well adapted to fluctuations in salinity. Microorganisms requiring salt for growth are referred to as halophiles. Whereas halophilic hydrocarbon-metabolizing bacteria perform well in this salinity range, there have been reports of the isolation of bacteria capable of degrading hydrocarbons above a salinity of 3.5%. Bertrand et al. (1990) reported the isolation from a salt march of an extremely halophilic archaea bacterium capable of degrading hydrocarbons in 3.5 M NaCl (20.4%), but not below 1.8 M NaCl (10.5%). Diaz et al. (2008) reported the isolation of a bacterial consortium, which mainly included members of the genera Marinobacter, Erwinia and Bacillus, from a crude oil sample from the Cormorant field in the North Sea. This consortium was able to metabolize petroleum hydrocarbons in a salinity range from 0 to 22% NaCl. Total oil degradation ranged from 48% to 75%, with the greater degradation occurring at the lower salinities.
At the sea surface, wind and wave action maintain a constant supply of oxygen, thus aerobic catabolism of hydrocarbons is usually the preferred biochemical pathway (Leahy and Colwell, 1990). Oxygen may become limiting in subsurface sediments and anoxic zones of water columns. Oxygen limitation is also a concern for most fine-grained marine shorelines, freshwater wetlands, mudflats and salt marshes (Venosa et al., 2002; Venosa and Zhu, 2003). It is commonly believed that biodegradation rates under anaerobic conditions are almost negligible, while aerobic biodegradation of hydrocarbons occurs rapidly. However, the importance of anaerobic biodegradation should not be underestimated as it has been shown to be a major process under certain conditions. In anoxic marine sediments, reductions of sulphate, Mn(IV) 41
and Fe(III) are the primary terminal electron-accepting processes (Canfield et al., 2005; Finke et al., 2007). Results obtained by Coates et al. (1997) revealed that hydrocarbon degradation coupled with sulphate reduction prevails in marine anoxic sediments. Information on how to enhance microbial growth and biodegradation performance in anoxic marine sediments is still limited and requires further study.
McFarlin et al. (2011a; 2011c) set out to determine the ability of indigenous microbes to biodegrade crude oil in marine waters of the Beaufort and Chukchi Seas. Fresh and weathered Alaska North Slope crude oil was tested with and without Corexit 9500. Biodegradation was significant in all treatments at -1 to 2C, and dispersal with Corexit enhanced it. Degradation at 2C of 10 mg/L fresh crude was 37%. When chemically dispersed with 5% Corexit it was 56%, and chemically dispersed with the addition of 0.5% Bushnell Haas was 66%. In the case of 12 mg/L of 20% weathered crude at -1C with 0.5% Bushnell Haas and without Corexit, biodegradation was 46%, whereas with chemical dispersion it was 55%. Clearly, fresh crude oil was more effectively biodegraded than the weathered.
With recent advances in analytical methods such as genomics, we are now able to determine the potential of whole microbial communities for oil biodegradation at low temperatures. New evidence as a result of advances in biotechnology (i.e. metagenomics) are now suggesting that oil in the Arctic may be degraded at higher rates by indigenous organisms (that are adapted to their environment) than previously thought. This is not surprising based on the fact that natural oil seeps occur in the worlds oceans including the Arctic. Studies have shown that elevated concentrations of hydrocarbons in the environment increase catabolic-gene copy numbers among the microbial community (Heiss-Blanquet et al., 2005; Stapleton and Sayler, 2000; Whyte et al., 2002).
Although various chemical and microbiological aspects of petroleum oil degradation in marine systems have been relatively well studied in Arctic regions (Boehm et al., 1987; Haines and Atlas, 1982; Hodson et al., 2002; Owens, 1994), there is a general lack of knowledge concerning the diversity or abundance of the oil-degrading bacteria in relation to the extant hydrocarbon pollution. The recent DWH spill has highlighted the importance of oil degradation in the 42
recovery of marine ecosystems impacted by crude oil spills. Hazen et al. (2010) reported that the disappearance of residual oil in the Gulf of Mexico from the DWH spill was associated microbial degradation processes based on the results of metagenomics. Temperature did not appear to be a major limiting factor as significant rates of oil degradation were observed within the subsea plume of dispersed oil at a depth of 1300 m (temperature below 4 o C). There is a need for studies using advanced genomic techniques to assess the significance of natural oil degradation processes in the Arctic marine environment. Compared to the amount of knowledge of the diversity of oil catabolic genes and levels of expression in oil-contaminated soils (Luz et al., 2004; Whyte et al., 1997; Whyte et al., 2002), our understanding of this diversity in Arctic marine systems is practically nil.
Unlike oil spills occurring at the sea surface, during the DWH spill, petroleum hydrocarbons experienced a prolonged, buoyancy-driven ascent through the 1500 m water column (Hazen et al., 2010). Consequently a unique set of processes affected the released hydrocarbons during their trajectory in the deep sea. Some oil and gas never reached the sea surface, but instead formed hydrocarbon-rich plumes within the cold waters present at ~1100 m depth, supporting an active deep-sea microbial community (Hazen et al., 2010; Valentine et al., 2010). This demonstrates the importance of interwoven chemical, physical and biological processes in regulating the transport and fate of hydrocarbons in the deep marine environment. It would be difficult to disentangle the role of natural processes from the effects of countermeasures such as the use of dispersants when considering such questions as, How might droplet size from dispersant applications affect biodegradation? Nevertheless, oil in the water column and on the surface can be evaporated, biodegraded, diluted and dispersed. Significant evidence has shown that gases have already biodegraded (Hazen et al., 2010).
There are new papers on the biodegradation of oil spills in cold water (Brakstad and Bonaunet, 2006; Brakstad et al., 2004; Brakstad et al., 2008; McFarlin et al., 2011b), in Arctic soil and shorelines (Greer et al., 2010; Labbe et al., 2007; Margesin et al., 2003; Whyte et al., 2001; Whyte et al., 2002; Whyte et al., 1999; Yergeau et al., 2009), and the persistence of oil in Arctic shorelines (Boehm et al., 2007a; Boehm et al., 2008; Boehm et al., 2007b; Boufadel and Bobo, 43
2011; Boufadel et al., 2010; Guo et al., 2010; Li and Boufadel, 2010; Neff et al., 2006a; Neff et al., 2011; Page et al., 2010; Page et al., 2002; Page et al., 2006; Xia and Boufadel, 2010).
Formation of Oil-Mineral Aggregates
Biodegradation of oil can be stimulated when the surface area of oil available for microbial attack is increased (Prince, 1993). Swannell and Daniel (1999) adapted a technique (Delvigne and Sweeney, 1988) to measure droplet sizes that allow for the determination of microbial colonization of small droplets. Their results showed that many dispersed oil droplets were colonized by bacteria and that substantial biodegradation took place after only 28 days of dispersant addition to the microcosms. The increase in surface area amenable to bacterial colonization occurs by the formation of an oil-in-water emulsion, where the oil is dispersed in small droplets into the water column, which is promoted by the use of dispersants (Desai and Banat, 1997). There has been much interest in recent years in the fate of oil droplets suspended in the water column (Khelifa and Brown, 2010; Payne et al., 2003b; Stoffyn-Egli and Lee, 2002). The mechanisms for the dispersion of oil into water as fine droplets are not well understood and are one of the large unknowns for predicting oil spill behaviour. In the natural environment, oil particles do not remain for long as discrete particles. They either recombine or coalesce, rising back to the surface, or they can attract and incorporate suspended particulate matter (SPM) from the water column (Owens and Lee, 2003) to form oil-mineral aggregates (OMA). These aggregations are known by many other names in the literature: oil-suspended particulate matter aggregates, clay-oil flocs, OMAs, and oil-fines interactions, to name a few.
Huang and Elliot (1977) described a process of clay-oil flocculation in which very fine particles (alumina, silica, kaolinite) tended to adhere to oil droplets and prevent further coalescence of the oil. Bassin and Ichiye (1977) showed that oils and clays form spontaneous association colloids or colloidal electrolytes in the presence of dissolved salts. An OMA is composed of an oil droplet coated with these kinds of fine particles. Typical sizes range from a few to several hundred microns. The formation of OMA stabilizes the oil-water interface, with the SPM acting as a surfactant. As stable particles this thermodynamically favours droplet formation and enhances dispersion of oil into the water column. 44
The typical SPM that encourage OMA formation are clay and silicate particles suspended in the water column, either from surface water outflows or from sediment stirred up from the bottom, such as in beach surf. As mineral particles are much more dense (typically 2-4 times) than the oil to which they are attached, OMA are less buoyant than naked oil droplets, and tend to sink. Because the OMA are stable, the oil droplets do not tend to shed the particles and thus cannot recoalesce to form a surface slick. This process of stabilizing oil droplets with fine clay particles has formed the basis of an oil spill remediation strategy based on the dispersion of oil trapped within shoreline sediments (Bragg and Yang, 1995; Lee et al., 2003; Lunel et al., 1996; Owens, 1999). Nutrient-bearing treatment products that promote OMA formation to enhance oil biodegradation are also being engineered for application to open-water marine oil spills (Kjeilen- Eilertsen et al., 2011).
Recent studies for the Canadian Coast Guard (Cloutier et al., 2005; Khelifa et al., 2005a), have shown that OMA can form at near-freezing temperatures in seawater. With high-mixing energy applied, the OMA readily form more than half within the first 10 minutes. Within 40 minutes of turbulence, most of the free oil had converted fully to OMA. These laboratory results were reconfirmed on a larger scale in a meso-scale basin (Blouin and Lee, 2007; Cloutier and Doyon, 2008) containing brackish water (18) with slush ice and broken ice. With strong turbulent mixing, OMA particles formed readily in slush (mixed snow) ice and broken ice. Almost all of the resulting particles were less than 1 mm in diameter. A mixing time varying between 20 and 30 minutes was sufficient to disperse about 50% of the spilled oil.
These trials were reproduced at full scale in January 2008, by the Canadian Coast Guard icebreaker Martha Black, in the St. Lawrence River near Matane, Quebec. The icebreakers propeller was used to create OMA in real ice conditions (Lee et al., 2009c). Several trials of 200 litres of fuel oil were mixed with chalk fines by the propeller of the icebreaker. The oil was seen to be dispersed into the water column and did not resurface. A control test with no added particles was observed to produce significant resurfacing oil. Samples collected from the water column were confirmed by optical fluoro-microscopy to have OMA particles present. Water 45
samples taken back to the laboratory for tracking biodegradation revealed that more than half of the total petroleum hydrocarbons (TPH) had been degraded after 56 days of incubation at 0.5C.
In further support of the concept of enhanced oil degradation by the formation of OMA, other studies have shown that the adhesion of microbial cells to surfaces or particles offers protection against physico-chemical stress and promotes increased catabolic potential compared to suspended populations (Baror, 1990; Diaz, 2008). Diaz et al. (2008) showed that when the salinity of the culture medium was over 20 g/L, a consortium of bacteria immobilized on polypropylene fibers significantly enhanced the biodegradation rate of crude oil compared with free-living cells. The authors concluded that through diffusion limitation the biofilm offered a protective effect against salinity stress and toxicity, and that the oleophilic carrier increased the oil availability for microbial attack. Brakstad and Bonaunet (2006) showed that oil adsorbed to hydrophobic Fluortex fabrics was quickly utilized by a bacterial biofilm that formed on the fabrics in seawater at the freezing point (0C). With the use of these types of adsorbents, not only is spilled oil physically eliminated, but also biodegradation in challenging environments is stimulated when cells form a biofilm on the hydrophobic surfaces.
Sedimentation
Most oils do not sink as their specific gravity is less than that of seawater. However, when suspended particulate material including fine sedimentary material interacts with oil, the conglomerate formed may be negatively buoyant. This natural process may occur in nearshore environments with a high suspended particle load such as that associated with glacial tills in the Arctic. Oil sedimentation is usually considered to be disadvantageous for the overall removal of oil from the environment, because oil in the sediment phase tends to be limited by oxygen supply, and it is well known that anaerobic biodegradation of hydrocarbons is a slow, poorly understood process.
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4. Oil Spills in Canada from Offshore Oil and Gas Activities
The United States Geological Survey estimates the Arctic to contain nearly ninety billion barrels of oil of which nearly 10 billion is in the Amerasia Basin, an area that includes the Beaufort Sea (Figure 6). The focus on oil exploration in the Canadian Beaufort began in the late 1960s and early 1970s following successful exploration of Alaskas Prudhoe Bay (Matthews, 2011), and from 1972 to 1989, 33 wells were drilled from artificial islands in shallow water. Between 1976 and 1989, drill-ships established another 31 wells for a total of 86 in waters up to 60 m deep, with the only oil production occurring near the end of this period amounting to about 300,000 barrels of oil (Matthews, 2011).
Sverdrup Basin Figure 6 Canadian Arctic (source: Solar Navigator, 2011, http://www.solarnavigator.net).
Devon Energy in December 2005 drilled the exploratory offshore natural gas well, Paktoa C-60, in 13 m of water in the MacKenzie delta, and completed it in 2006 (Energytoday, 2010; Lunan, 2005); however, no information was released for competitive reasons. Since then, no exploratory drilling has occurred in the Canadian Beaufort region, although BP has commenced seismic 47
testing of the sea floor (Energytoday, 2010). In the Beaufort Sea and MacKenzie delta a total of 295 wells have been drilled between 1965 and 2009 (Hawkins, 2010).
Resources in the Sverdrup Basin (Figure 6) are estimated at 19.8 trillion cubic feet of gas (CGPC, 2006) and 1.9 billion barrels of oil (Chen et al., 2000). Climate change has already impacted the ice cover in the Sverdrup Basin, such that it there might be a point in time when neither the use of ice platforms nor conventional offshore drilling techniques would be feasible (Meneley, 2008).
Baffin Bay and Davis Strait (Figure 6) are shared with Greenland and may hold up to 18 billion barrels of oil (Edmonton Journal, 2010). Three wells were drilled in Canadian waters offshore of southern Baffin Island: Hekja O-71, Raleigh N-l 7 and Gjoa G-37 (INAC, 1995). Five wells (dry and abandoned) were drilled in Danish waters on the west Greenland Shelf in Davis Strait, approximately 500 km to the northeast (Figure 6), at the southern entrance to Baffin Bay, in 1976-77 (INAC, 1995). One well was drilled in the Strait in 2000 (Cairn, 2011).
Cairn Energy PLC of Scotland has been drilling in the Greenland waters of Baffin Bay since the summer of 2010 (CBC, 2011). Three exploratory wells were completed in 2010 in the Sigguk block, offshore West Greenland in 300-500 m of water (Cairn, 2011). As of 3 June 2011, drilling in Davis Strait has commenced on the AT-7 well, Atammik Block, about 160 kilometres offshore of Nuuk (Figure 7), and the LF-7 well in the Lady Franklin Block about 300 km offshore of Nuuk (Figure 7). The AT-7 and LF-7 prospects are at water depths of 905 and 989 m respectively (Cairn, 2011). Another 2 are scheduled for the summer of 2011: one in each of the Napariaq and Eqqua blocks in the southern Baffin Bay west Disko area (Figure 7). It is anticipated that these 4 wells, located at subsurface depths between 2500 and 4750 m, will produce 3.2 billion barrels of oil equivalent. It is hoped that oil will be the product, but it could be gas. The uncertainty reflects the lack of data in this frontier (Cairn, 2011). 48
Figure 7 Exploration parcels of Cairn Energy in the Greenland offshore (Cairn, 2011).
As of June 2011, there are no reported marine oil spills in the Beaufort Sea, Sverdrup Basin, Baffin Bay or Davis Strait. Over the past 40 years, there have been no recorded oil spills caused by an offshore well blowout in the U.S. Alaskan or Canadian Arctic marine waters.
Increasing oil exploration activities in northern latitudes in the context of the recent blowout of the DWH well have increased concerns over the safety of operations in the Arctic. Oil exploration activities are complex and they require the involvement of various types of equipment such as rigs, vessels and aircraft to support operations. The complexity and risk of such operations is compounded in the Arctic by the presence of ice, cold temperatures and by the lack of daylight during certain periods of the year. These difficult conditions are challenging for any operations conducted in this region and are increasing the probability of having an oil spill in the Arctic.
This section describes the current knowledge on the various types of oils that could be released in the Canadian Arctic in case of an incident during oil exploration activities. Using simple scenarios, we will describe some of the environmental risks from their release and how their behaviour could impact response options.
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4.1 Oil Types from Vessel Operations
The type of vessels currently operating in the Arctic and a general list of petroleum hydrocarbon based fuels and other products including lubricants that they typically carry are summarized in Table 2. To be prepared for a spill, it is important to understand the types of products that may be
Table 2 Vessel types operating in Arctic waters and oil types carried onboard. Oil Type Vessel Type Transported as Fuel Transported as Cargo Examples of Tank Capacity Tankers Bunker C, Intermediate Fuel Oil (IFO) Crude, Bunker C, IFO, Diesel, Gasoline Range: 92 000m 3 (total cargo tanks) to 12 000m 3 (1 tank) Supply and anchor handling ships Marine Gasoil (MGO) Low Sulphur Diesel (LSD), oil based mud, glycol, mineral oil Range: 570 m 3 (total fuel tanks) to 80 m 3 (1 tank) Tugs/Barges MGO Gasoline, Bunker C Tug range: 300 m 3 (total fuel tank) to 75 m 3 (1 tank)
Barge range: 1383 m 3 (total cargo tanks) to 170 m 3 (1 tank) Cargo/Fuel IFO Diesel Range: 24 309 m 3 (total cargo tank) to 3000 m 3 (1 tank) Icebreakers MGO Aviation fuel
Range: 4800 m 3 (total fuel tanks) to 400 m 3 (1 tank) Cruise ships IFO, Diesel None Range: 4800 m 3 (total fuel tanks) to 400 m 3 (1 tank) Fishing vessels MGO
Range: 220 m 3 (total fuel tank) to 35 m 3 (1 tank) Re-supply ships (community) Diesel IFO, Gasoline 17 207 m 3 (total cargo tank) to 2800 m 3 (1 tank) Military MGO Aviation fuel
Unknown Research Diesel Aviation fuel
Range: 4800 m 3 (total fuel tanks) to 400 m 3 (1 tank) 50
released and potential volumes. The following is based on past marine traffic in the Canadian Arctic. These numbers will obviously increase as more traffic enters these waters for oil or mining development and does not include rigs and platforms, which would introduce additional spill potential. The carriage of crude oil by tanker would also increase the volume of product as well as the risk.
All of these vessels are also transporting an unknown amount of hydraulic oil, lube oil, and waste oil onboard as a result of the operation of various pieces of equipment such as cranes, derricks, thrusters, winches and lifts. However, the quantities of these types of oil are likely to be at a maximum of 1 m 3 . Ships will also generate oily water during their operation. This must be retained on board until it can be discharged ashore (bilge water, contaminated ballast water, waste oil and tank washings). Some oil will be released by being passed through the ships oily water separator but these releases will not exceed 15 ppm in Arctic waters, the normal limit for most equipment. Another potential source of discharge from ships are the tail shaft seals, which may leak when the seals become deformed by the formation and expansion of ice. An accidental release of these oils would not represent a significant risk because of the small quantities involved, but the consequent increased possibility of reduced thrust and engine failure, leading to grounding and collision, increases the risk of a serious oil spill.
4.2 Oil Types from Oil Platform Operations
Oil platforms are complex structures used to either conduct exploratory drilling or extract and process oil or gas before it is transported to refineries or oil depots. Two potential sources for an oil spill include crude oil from drilling activities and oil used for the operation of equipment.
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Crude Oil from Drilling Activities
Crude oils that have been discovered in the Canadian Arctic are listed in (Table 1). Most of these oils are generally considered medium to light oils and could be spilled during drilling activities, as a result of a well blowout or during transport by tankers. While the probability of a spill is low, depending on the characteristics of the formation being exploited, the potential quantities spilled could be very high as demonstrated during the recent DWH blowout, and the PTTEP Montara West Atlas spill in the Timor Sea in August 2009.
Petroleum Products used in Operations
Various types of equipment using oil are found on platforms such as generators, cranes, engines, etc. These all use oil products either as fuel or for lubrication. In most cases, diesel fuel, engine oil and hydraulic oil are the main oil types necessary for platform operation. Stored quantities of these, particularly for engine and hydraulic oil, are likely to be limited. Diesel is often used for power generation and might be found in larger quantities ranging from approximately 100 m 3 to 200 m 3 . Helicopter operations to transport personnel and equipment require the storage of aviation gas in small amounts on the platform as well, generally less than 10 m 3 .
4.3 Overview of Oil Spill Risks in the Canadian Arctic
Defining Risk
The many interpretations of the term risk has led to different approaches to risk management in different fields (Hubbard, 2009). Examples include the following. The ISO 31000 (2009)/ISO Guide 73 definition of risk is the effect of uncertainty on objectives. In this definition, uncertainties include events which may or may not happen, and uncertainties caused by a lack of information or ambiguity. This definition also includes both negative and positive impacts on objectives. 52
Risk can be seen as relating to the probability of uncertain future events. For example, according to Factor Analysis of Information Risk, risk is the probable frequency and probable magnitude of future loss (Jones, 2005). OHSAS (Occupational Health and Safety Advisory Services: OHSAS 18001:2007) defines risk as the product of the probability of a hazard resulting in an adverse event, multiplied by the severity of the event.
In statistics, the notion of risk is often modelled as the expected value of some outcome seen as undesirable. This combines the probabilities of various possible events and some assessment of the corresponding harms into a single value. In a formula that can be used in the simple case of a binary possibility (accident or no accident), risk is then:
Risk = (probability of the accident occurring) (expected loss in case of the accident).
Understanding the risks associated with an activity requires (1) the ability to predict the likelihood or probability of such an event occurring, and (2) the ability to anticipate the potential adverse consequences of such an event. The magnitude of accidental releases of oil may range from small spills associated with pipes, tanks or vessels to a catastrophic well blowout. Based on historical records from Canadian and global databases maintained by regulators and industry, very large oil spills or blowouts are low probability events, but the consequences may be disastrous.
The risk of oil spills in the Arctic is anticipated to increase due to global climate change that may eventually lead to year round marine transport via the North West passage and the expansion of industrial developments, and the expansion of exploration drilling outside of the traditional summer open water period as operations become more technically feasible with advances in marine technology including the support of novel ice management. Should an event occur, it is important to note that all Arctic oil spill countermeasures are hampered by the harsh environment, poor access and a lack of nearby support facilities (Sergy and Blackall, 1987).
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Incidents from Vessel Operation
Shipping incident statistics from the Transportation Safety Board of Canada provide a better understanding of the potential risks of having a spill from vessels operating in the Arctic. In 2009 in Canadian waters, the most common type of vessel to have reported marine accidents were fishing vessels, which outnumber the other vessel types and make up over half of the total number of Canadian registered vessels (Figure 8). Fishing vessels are followed by tugs and barges, and then bulk carrier and other bulk operations in the number of accidents.
Figure 8 Accidents by ship type; OBO = other bulk operations (source: Transportation Safety Board of Canada).
The most common cause of vessel accidents in Canadian waters since 2004 has been grounding (Figure 9). This is followed by striking and fire/explosions. All of these categories have the potential for causing a release of product.
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Figure 9 Types of accidents (Source: Transportation Safety Board of Canada).
There are less vessel accidents reported in the Arctic region than in all other regions of Canada (Table 3); however, there is also less traffic (Figure 10). The number of accidents will likely increase as shipping increases in the Arctic region. Tugs, barges and cargo vessels reported the most shipping accidents in the Arctic since 2000.
The most common reason for ship source spills in the Arctic is oil transfers by hose, which is unlikely to cause a very large spill because of preventive systems in place during transfer operations. Other likely causes would be spills due to major accidents that will cause hull damage such as groundings because of poor nautical charts or difficult navigation and striking especially with multi-year ice. For vessels currently operating in the Canadian Arctic, the most significant threat is from oil tanker operation where potential spill quantities could be significant, i.e. in the range of 3000 to 4000 m 3 (if one cargo tank was breached) while spills from cruise ships and icebreakers would be in the range of 1000 m 3 . Supply vessels, which are used extensively during oil drilling exploration projects, represent a lesser threat because of limited fuel storage capacity with a range of 300 to 600 m 3 and also because of the less persistent fuel type, such as marine gasoil (MGO) or marine diesel, that they usually transport. 55
Oil platform operations present a variety of spill risks. Accidental petroleum discharges from platforms contribute 0.07% of the total petroleum input to the worlds oceans (NRC, 2003). Well blowout is the most significant spill risk. This could spill large quantities of crude oil as was demonstrated by the IXTOC I in 1979 and DWH in 2010. However, these incidents are rare especially in Arctic waters where production and exploration activities are far less prevalent than in more temperate climates. Operational spills are more common and these typically include releases of crude, diesel, hydraulic and lube oil. Based on statistics from the Canada-Nova Scotia Offshore Petroleum Board (CNSOPB) and Canada-Newfoundland and Labrador Offshore Petroleum Board (CNLOPB), the source of most spills that are in excess of 150 L are flaring, transfer operations, leaks in fittings and valves or from the riser slip joint. Except for the Uniacke G-72 gas blowout near Sable Island in 1984, which discharged some 1,500 barrels of condensate into the marine environment, Canada has never experienced an offshore well blowout involving discharges of petroleum oil.
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Statistics from Nova Scotia and Newfoundland-Labrador provide an indication of the frequency of spills and the quantities potentially involved from platform operations. Few spills are recorded every year from offshore operations in both provinces as shown by Figure 11 and Figure 12. The majority of spills that have occurred are less than 150 L. These small spills outnumber larger spills (>150 L) by 4 to 1 in Newfoundland-Labrador, and 9 to 1 in Nova Scotia. The most common sources for small spills are hoses, leaks from stern tubes and thrusters, and drain systems.
Figure 11 Number of spills per year in Nova Scotia from offshore operations.
Figure 12 Number of spills per year in Newfoundland-Labrador from offshore operations. 58
From January, 1994, to August, 2002, five oil spills, including spills of synthetic oil-based drilling mud, occurred during exploration drilling on the Scotia Shelf that resulted from exploration and production activities (CNSOPB, 2010). In the Newfoundland and Labrador offshore petroleum region, in 2004, a 1000 bbl crude oil spill occurred from the Terra Nova platform due to equipment failure. While there were 296 spill events associated with exploration and production activities in the Newfoundland and Labrador region from 1997 and 2007, the total volume of hydrocarbons released was less than 1200 bbl (CNLOPB, 2010). Figure 13 and Figure 14 provide an indication of spilled quantities from offshore operations. Between 1997 and 2011 the total volume of combined product spilled during offshore operations in Newfoundland- Labrador was 454,681 L, and 555,239 L in Nova Scotia between 1999 and 2010. Spill volumes increased during periods of development and production.
Figure 13 Total spill volume in litres per year off Nova Scotia.
Records show that the number of operational and accidental spills and the quantities released on a yearly basis from offshore activities currently operating on the east coast of Canada are fairly low and limited.
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Figure 14 Total spill volume in litres per year off Newfoundland.
The rate of blowouts is very low in the oil exploration and development industry. For example, in the Gulf of Mexico from 1979 through to 1998 there were 19,821 wells drilled, with 118 wells resulting in uncontrolled flows or blowouts. This results in a 0.6% occurrence rate of blowouts for the region during this time. Furthermore, the majority of reported events involved the diversion of gas. Due to differences in defining a blowout, the American Petroleum Institute (2009) states that there has only been 17 marine well blowouts in the U.S. since 1964, which resulted in a total of 249,000 bbl spilled. The largest of these blowouts occurred from the Alpha Well 21 off Santa Barbara, California, which spilled 100,000 bbl. In general, spill volumes have been small, with 50% of the well blowouts involving 400 bbl of oil or less. With advances in technology and improved operational safety measures, data from U.S. operations has indicated a decrease in combined spill volumes from offshore supply vessels, pipelines, and platforms, from 30,400 bbl y -1 (from 1969-1977) to 3,900 bbl y -1 (from 1998-2007), resulting in an 87% reduction in the average annual spill volume since the 1970s (American Petroleum Institute, 2009). Historical spill and blowout events support the prediction of a low probability of spill and blowout occurrence for new oil and gas drilling exploration and production activities (Table 4).
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Table 4 Historical large oil spills in barrels (bbl) from offshore well blowouts (source: Oil Spill Intelligence Report database). Offshore Region Spill Size (bbl) Year Type of Activity Mexico (IXTOC I) 3,000,000 1979 Exploratory Drilling Dubai 2,000,000 1973 Development Drilling Mexico 247,000 1986 Work over Nigeria 200,000 1980 Development Drilling North Sea/Norway 158,000 1977 Work over Iran 100,000 1980 Development Drilling U.S.A., Santa Barbara 77,000 1969 Production Saudi Arabia 60,000 1980 Exploratory Drilling Mexico 56,000 1987 Exploratory Drilling U.S.A., S. Timbalier 26 53,000 1970 Wireline U.S.A., Main Pass 41 30,000 1970 Production U.S.A., Timbalier Bay/Greenhill 11,500 1992 Production Trinidad Development 10,000 1973 Drilling
The Canada-Nova Scotia Offshore Petroeum Board has predicted a 1-in-1800 chance per year of having any sort of deep water blowout off the Continental Shelf during exploratory drilling, with the probability of shallow water gas blowouts without a release of oil having a three to four times higher possibility of occurrence (Hurley and Ellis, 2004). Hurley and Ellis (Hurley and Ellis, 2004) provided expected frequencies of exploration well blowouts based on the historical frequency of blowouts per wells drilled. They calculated that the predicted frequency of an extremely large blowout (>150,000 bbl) was one every 17,500 years. The frequency of a very large spill (>10,000 bbl) was one every 5800 years, and of a large spill (>1000 bbl) was one every 4400 years.
Based on statistical data from the offshore of Nova Scotia, presented by Hurley and Ellis (2004), the highest frequencies of oil spills are for the smaller, platform-based spills. Spills that are less than one barrel in size may occur once every two years. Oil spills during exploration, which are 61
larger than one barrel but less than 50 bbl, have an approximately 1-in-10 or 1-in-20 chance of occurrence per year. In fact, the CNSOPB concluded that their original prediction of 0.5 spills per year for the Sable Offshore Energy Project was largely accurate when compared with the observed spill occurrence of 0.57 spills per year.
The stasticical data from all of these offshore oil and gas sites provide an indication of the likelihood of having spills in the Arctic from exploration and production activities. We can see that spills are limited in both number and size. While there are advances in technology and regulations for the safety of operations, recognition must be given to the unique challenges for offshore oil and gas exploration and production operations in the Arctic environment. Although a significant spill of crude oil resulting from a well blowout has never been recorded in Canada, it remains a threat that cannot be overlooked.
4.4 Modelling Spill Scenarios and Oil Behaviour
Predictive models of spill scenarios have been developed to illustrate the expected behaviour of the most commonly used oil in the Canadian Arctic. From the information obtained it is evident that spills of crude oil, intermediate fuel oil (IFO), aviation fuel and MGO are the most likely to be spilled in quantities that would require some sort of response to take place. We recognize that other oils such as lube oil and hydraulic oil can also be spilled but in quantities that would be minimal and therefore not requiring any specific response other than monitoring.
The Automated Data Inquiry for Oil Spills (ADIOS2) software package is an oil weathering model provided by the National Oceanic and Atmospheric Administration (http://response.restoration.noaa.gov/adios). The ADIOS2 database includes estimates of the physical properties of oils and products compiled from different sources, including industry, Environment Canada, and the U.S. Department of Energy. The model uses mathematical equations and information from the database to predict changes over time in the density, viscosity, and water content of an oil or product, the rate at which it evaporates from the sea surface and disperses into the water, and the rate at which an oil-in-water emulsion may form. Output of the model in graphical and textual format can be used to address questions that 62
typically arise during spill response and cleanup. For example, by predicting change in oils viscosity (resistance to flow) over time, ADIOS2 can provide information on whether chemical oil dispersants can be used with success. For comparative purposes, oil weathering scenarios were prepared using ADIOS2 software in the following subsections of this report with a water temperature set at 0C and wind speed of 5m/s which correspond to a moderate breeze or a Beaufort 4 sea state. The ADIOS2 model cannot compute for oil-ice interaction, which is a significant limitation when evaluating behaviour in Arctic conditions. However, even with this limitation in mind, this model provides enough information to evaluate the expected behaviour of oil during specific spill scenarios.
Scenario for Spills of Crude Oil
One of the most plausible scenarios for a crude oil spill in the Canadian Arctic is that associated with tanker operations. This scenario is more likely to happen than a catastrophic well blowout as tankers have to transit waters with many navigational hazards such as the presence of ice floes and constant darkness at certain times of the year. To look at the potential behaviour of crude oil, we considered a spill of 4000 m 3 of Amauligak crude oil over a one-hour period from a tanker as a result of a collision with ice or any other structures. This quantity is representative of the loss of one tank from a typical tanker currently operating in the Canadian Arctic.
From the ADIOS2 weathering model, we can see that a small proportion of this oil would evaporate and disperse (approximately 20%) within the first 36 hours leaving most of the spilled oil to be recovered during the response (Figure 15). However, during the same period the viscosity (Figure 16) and the density (Figure 17) of this oil are also increasing significantly thus reducing the window of opportunity available for some response techniques such as dispersant application. With a kinematic viscosity above 10,000 cSt and a density slightly above 1.00 after 36 hours it is possible that this oil would be slightly submerged and non-dispersible. In that case, only mechanical skimmers and pumps might be available as cleanup options. Given the logistical challenges of responding in the Arctic, it would be very difficult to have an efficient response for a spill of this type. As mentioned before, oil-ice interactions are not considered by ADIOS2 in its calculation. However, it can be assumed that in ice conditions and very cold air temperatures, 63
less oil would be naturally dispersed and viscosity and density would be higher, increasing the difficulties in mounting an at-sea response. In a scenario such as this one, oil would likely drift with sea currents and mix with ice floes before reaching the shoreline where recovery efforts could be conducted in a more efficient manner. It is obvious that a well blowout spilling large quantities of this oil over a long period of time would cause substantial difficulties. However, once response equipment was on location, it is possible that response efforts could become efficient, as fresh oil would be constantly rising to the surface, maintaining the window of opportunity for successful operations. In spite of this, logistical challenges such as waste management, and health and safety issues would be very difficult to overcome.
Figure 15 Oil budget for a spill of 4000 m 3 of Amauligak crude oil as calculated by ADIOS2.
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Figure 16 Predicted change in viscosity for Amauligak crude oil as calculated by ADIOS2.
Figure 17 Predicted change in density for Amauligak crude oil as calculated by ADIOS
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Scenario for Spills of Intermediate Fuel Oil
Tankers and cargo ships, among others, currently operating in the Arctic use IFO as their propulsion fuel. IFO is a heavier oil with a pour point of -10C which could be a problem in Arctic conditions as this oil could become semi solid at temperatures commonly observed in the North. IFO could be released into the environment through hull damage in a collision. By way of example in which a severe collision released approximately 1000 m 3 of IFO 180, using the ADIOS2 weathering model, most of the oil (87%) would remain in the environment and weathering processes would have little effect on this oil (Figure 18).
Figure 18 Oil budget for a spill of 1000 m 3 of IFO 180 as calculated by ADIOS2.
Natural dispersion and evaporation are marginal weathering processes with this type of oil especially in cold water environments such as the Arctic. Recovery of this oil would be necessary using mechanical techniques, as dispersants would not be efficient given the high kinematic viscosity that is well above 10,000 cSt at the time of the spill, and reaching more than 50,000 cSt after a few days (Figure 19). High viscosity coupled with low Arctic temperatures 66
would make any recovery efforts using pumps and skimmers very difficult due to freeze up of water intakes and flow rate issues with the equipment. Similar to a spill of crude oil, most of the IFO would likely drift with ice and sea currents and eventually reach the shoreline where further recovery could be attempted.
Figure 19 Predicted change in viscosity for IFO 180 as calculated by ADIOS2.
Scenario for Spills of Marine Gasoil
Many ships currently operating in the Canadian Arctic also use marine gasoil (MGO) as propulsion fuel. This fuel is also used by platforms mainly for power generation. Most vessels using MGO are smaller vessels such as supply ships and icebreakers. MGO is a light oil with an API gravity of approximately 31 and a pour point of -12C. Spills of MGO are likely to be caused by collision between a vessel and ice floes or other structures. However, as opposed to crude oil and IFO spills, the quantities involved are likely to be smaller since the types of vessels currently using this fuel have less tonnage than ships using other fuels. A plausible scenario 67
would be damage to the hull resulting in the release of 100 m 3 of MGO from one of the fuel tanks onboard a vessel. The oil budget calculated with ADIOS2 indicates that the combined processes of natural dispersion and evaporation would weather most of the spilled MGO (Figure 20). It is also likely that a proportion of this oil would be easily absorbed by snow (if spilled on ice) as its viscosity remains well below 10,000 cSt (reaching a maximum of approximately 50,000 cSt) even in Arctic conditions. The low viscosity keeps this oil amenable to most response techniques such as dispersants and mechanical recovery, therefore representing less of an operational challenge when compared to crude oil or IFO. Recovery of this type of spill would likely be easier but would still remain particularly difficult given the Arctic setting. This expected behaviour is one of the reasons why Norway has made it mandatory for all ship traffic in its northern regions to use MGO as fuel in order to minimize the consequences of an accidental spill.
Figure 20 Oil budget for a spill of 100 m 3 of MGO as calculated by ADIOS2
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Scenario for Spills of Aviation Fuel (Jet Fuel)
Jet fuel is very light oil primarily used for air travel and support operations to transport personnel and equipment throughout the Arctic. It has an API gravity of 43. Stored quantities on platforms or on icebreakers are generally of a maximum of 10 m 3 (although significantly larger quantities may be transported via cargo ship as indicated in Table 2). For discussion purposes, if 10 m 3 of jet fuel is spilled from a storage tank into the sea, ADIOS2 modelling shows that this very light oil would be entirely dispersed and evaporated within the first 12-20 hours after release into the water (Figure 21). If it was spilled on ice and snow, a similar pattern would be expected as evaporation would be the primary weathering process. Even if evaporation on ice would likely be slower than on water, the ultimate fate of that spill would be similar. Because of this behaviour, jet fuel spills do not represent a significant environmental issue due to the very low persistence of that oil. In dealing with a response to such a spill it is unlikely that significant recovery efforts would be required other than possibly using absorbents in the vicinity of specific environmental sensitivities. Monitoring of natural attenuation (natural recovery) would be the spill response strategy.
Figure 21 Oil budget for a spill of 10 m 3 of jet fuel as calculated by ADIOS2. 69
Recommendations from Modelling Exercises
These models of various scenarios illustrate to some degree the risk involving an oil spill because of increasing oil exploration and production activities in the Canadian Arctic. Increased vessel traffic of multiple ship types and drilling operations would be the likely sources of spills. With these activities, many different oil types will be transiting the Arctic either as fuel for ships and equipment or as cargo for tankers. Crude oil is likely to be the most transported oil in this region using large tankers. The potential quantities from a spill could be quite significant and pose serious challenges to those in charge of responding to such an incident because of the logistical issues of working in the Arctic and the presence of ice. A catastrophic event such as a well blowout would bring supplemental challenges and difficulties because of the potential quantities involved and the extent of such a spill. However, the most likely event resulting in an oil spill in the Arctic is a collision between a ship and ice floes, another ship, or any other structures in the region. A breach in the hull could release fuel and cargo into the environment in significant quantities. It is also apparent that a spill of IFO would represent a greater threat to the environment because of its high persistence and high viscosity rendering response very difficult. Crude oils found in the Canadian Arctic are for the most part medium to light crudes and their relative persistence in the environment is less than IFO.
As noted previously, oil behaviour in the Arctic is mainly guided by the presence or absence of ice and by the low temperatures. In the absence of ice, oil will behave as it would at lower latitudes with well-known processes such as natural dispersion, spreading, evaporation and emulsification taking place over time. Many studies conducted world-wide have documented well how these processes occur, changing the behaviour of oil and having a direct impact on response methods that can be used during a spill. In the case of spills in ice covered waters similar processes are take place but are directly affected by ice. Usually, oil-weathering processes are slowed by ice and cold temperatures prolonging the window of opportunity for some response techniques such as dispersants. Over the last 40 years many research projects have been conducted to document the behaviour of oil with different ice coverage and the efficiency of oil spill response techniques in Arctic conditions (See Section 3. Oil Spills in Arctic Waters). These studies have provided us with a good understanding of how oil will behave and 70
how efficient most response techniques would be in Arctic conditions. In the context of the Canadian Arctic, we have identified four areas where some research could be undertaken. 1) Oil behaviour in a subsea release Little information exists on oil behaviour in the Arctic in the case of a subsea release such as a well blowout. This would assist responders in better understanding how the oil would behave under such circumstances and adjust response plans and methods accordingly. 2) Hydrographic data and drifting models (Drozdowski et al., 2011) Better hydrographic data in the Canadian Arctic should be collected and integrated with oil spill trajectory models that would take into consideration the presence and the influence of various ice coverage on drifting oil. 3) Improving oil weathering models to include Arctic conditions and oil-ice interaction Very few oil weathering models take into consideration the oil-ice interaction and the effect of Arctic conditions on oil weathering. To our knowledge, only two models exist that consider the influence of ice on weathering processes. Arctic conditions and oil-ice interactions should be integrated into mainstream oil modelling software to ensure easy access of the information to oil spill responders. 4) Improving detection of oil in or under ice Even after many years of research, detection of oil in or under ice is still a partially resolved issue. Research into this area should continue in order to provide more efficient methodologies for responders.
As production and exploration in the Canadian Arctic is potentially increasing in the coming years, many challenges remain to be able to efficiently respond in northern environments. Although oil fate and behaviour processes are relatively well known there is still a need for more detailed assessments in order to provide on-scene commanders and responders with a better understanding of the behaviour of the oil released and applicable strategies in Arctic conditions. 71
5. Offshore Arctic Oil Spill Response Options
5.1 Development of Policies, Regulations and Capacity
Governments of Arctic coastal states require industry to ensure a high level of environmental protection. For example, a number of preventive measures related to maritime safety and oil spill response have been implemented in the Norwegian part of the Barents Sea (Ly and Bjerkemo, 2011) where measures in surveillance, monitoring, maritime infrastructure and services have been established along with oil spill response measures. In the United States, from 1993 to 2009, the Bureau of Ocean Energy Management, Regulation, and Enforcement (formerly the Minerals Management Service) initiated and conducted 31 projects related to improving the equipment (Mullin, 2011), technologies and methodologies for the prompt identification and removal of oil in Arctic environments and to provide regulators with the scientific data necessary to support regulatory decisions pertaining to permitting and approving plans, safety and pollution inspections, enforcement actions, training requirements, and emergency response. In Canada, national core funding for environmental research in the Arctic related to the development of offshore oil and gas activities and spill response countermeasures has been supported by Natural Resources Canada under the Program of Energy Research and Development and the Environmental Sciences Research Funds.
The United States Coast Guards current capacity to mount an effective and timely response to a major oil spill in the Arctic Ocean is limited (Lally, 2011). Currently, the U.S. Coast Guard surface assets suited to respond to an oil spill are typically at least seven days away. If conditions require an icebreaker escort, the response time could be 10 days or more. To meet the many challenges present in the Arctic, all oil spill response technologies need to be considered as response options including mechanical equipment, ISB, and chemical dispersants.
The Canadian Coast Guard (CCG) has a responsibility to monitor the effectiveness of the private sector response to ship-source spills in Canadian waters, assume control of the incident if necessary or deploy CCG resources to respond to spills for which the polluter is unknown, 72
unwilling or unable to respond. With the resources available, the CCG undertakes activities to help prepare Arctic communities to respond to major pollution incidents. A National Response Team, comprised of all CCG emergency response personnel and assets, is in place to provide a coordinated national response to a marine pollution incident. The CCG also provides training in the Arctic on how to effectively respond to emergencies. Communities are provided with containment packs to support response capabilities. Basline studies in physical, chemical, geological and biological oceanography for emerging oil and gas exploration and development operations in the Canadian Arctic are supported by both industry and academia under the Arctic Net Centre of Excellence which has a mandate to translate our growing knowledge on the changing Arctic into impact assessments, national policies and adaptation strategies.
The complexity of Arctic oil spill response operations is compounded by prolonged periods of darkness, cold temperatures, environmental sensitivities, indigenous peoples and their culture, distant infrastructure and remoteness, the presence of seasonal dynamic sea ice offshore, and the generally high cost of doing business (Engelhardt, 1994; Velez et al., 2011). Oil spill response in ice-free seasons can be comparable to the response in other parts of the world, with the exception of working in lower temperatures and extended daylight hours. Conventional oil spill containment and mechanical recovery systems used in temperate waters are often constrained by the presence of ice. In monitoring and risk assessments, remote sensing capacity is limited, and the modelling of the fate of oil is complicated by a lack of adequate, detailed knowledge of under-ice currents. While ice cover can hamper the access of responders to the oil, it can also restrict the movement of oil on the sea surface and thus be considered an asset to certain countermeasure applications such as in situ burning (ISB).
The first Norwegian oil field in the subarctic Barents Sea region will start production in 2013, and crude oil transport along the environmentally vulnerable coast is increasing. A collaborative program between industry representatives and national oil spill responders has recently been established in Norway to addresses the publics demand for improved oil spill response technologies for use in northern waters. The program includes 18 technical challenges divided into four categories: (1) offshore oil spill recovery, (2) dispersant application technology, (3) remote sensing technology, and (4) coastal and shoreline response. 73
Shell has undertaken different steps to implement best practices during the preparation for exploratory drilling in the Alaskan Beaufort Sea and Chukchi Sea (Broje et al., 2011). Spill prevention measures include continuous 24 hour monitoring of drilling activities through a real time operation centre, advanced weather monitoring and forecasting and mechanical barriers. Comprehensive contingency planning incorporates Arctic-capable response equipment, on-site oil spill response vessels, as well as offshore, nearshore, and on-shore response strategies. A dedicated Science Program is established to collect environmental baseline data (metocean, ice, biological, and shoreline) and continued ecosystem-based monitoring and assessment, and research and development of spill response techniques and advancement. Stakeholders are engaged with communities along the Alaska North Slope and marine mammal subsistence user groups.
5.2 Mechanical Containment and Recovery
Responses to spills from vessels, blowouts and pipelines include controlling slicks at source and removing oil that escapes initial containment. The objective of both operations is to minimize the spreading of spilled oil and adverse environmental impacts. Containment booms and skimmers are deployed in either a mobile or stationary mode to intercept, control and recover oil on the sea surface. When responding to an oil spill in Arctic conditions, the first step is to identify the physical properties of the oil, particularly, the pour point. If the pour point is 5 to 10 degrees above the water temperature, there is a strong possibility that the oil has already solidified. Nets and other collection devices may be required for recovery. If the pour point of the oil is below the water temperature and if currents and wind conditions allow, then booms and skimmers may be applicable for use.
Response to spills in broken ice frequently requires strategies to deal with the moving ice. Factors to consider are dramatic changes in ice concentration, frequent wind shift in direction and speed, changing relative position of oil and ice, short daylight periods, diminished vessel mobility and restricted operations due to the very cold temperatures (Solsberg et al., 2002). Ice management techniques in the freeze-and-thaw seasons should also be part of the oil spill 74
response planning for a particular region. The major challenges are the development of equipment for better detection and collection of oil spills in darkness and low visibility, icing of the oil spill response equipment, and the human factor due to the low temperatures and harsh weather (Juurmaa, 2006).
In Finland, mechanical recovery is preferred due to recommendations of the Baltic Marine Environment Protection Commission, where chemical agents and ISB can be used only in special and restricted circumstances (Lampela and Jolma, 2011). The methods and techniques developed for application on specialized response vessels are based mainly on brush skimmer technology and separation of oil from ice in the water, thus avoiding the energy needed to lift oily ice blocks from surface water for cleaning operations. Despite technological advances mchanical recovery in ice-covered waters operate at lower efficiencies when sea ice is present, due to challenges such as limited access to the oil, icing, freezing, and jamming of equipment. In ice conditions, the use of brushdrum, brush adaptors, brush pack skimmers and rope mop concepts comprise the best choices for dealing with oil spills. Disc, drum and rope mop skimmers can remove light and medium viscosity oils. Brush and belt skimmers can collect heavy oils. The use of skimmers in broken ice is considered more appropriate for small batch removals rather than to contain and remove a large spill. The recovered fluid is expected to contain a significant amount of slurry and slush ice, and therefore may take additional storage capacity.
While ice can act as an effective oil barrier, snow may be an effective oil sorbent. Equipment and manual methods can be used to mix and remove large quantities of oiled snow, although this mixture usually will have low oil content. Barriers made of snow can contain and prevent further spreading of oil. As diesel or other light oils can penetrate snow, an impermeable boom or snow barrier can be constructed by spraying accumulations of snow with water to form ice. Collected oil can be pumped to storage, where another pump or skimmer can be used to remove it. Under ice, oil tends to accumulate in naturally occurring surface depressions, so that trenches or holes can be cut to gain access to the oil and pump it to storage. Rope mop skimmers can be deployed under the ice, or the oil can be dealt with effectively when it surfaces in the spring. If conditions are favorable, ISB can be attempted.
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Pumping and vacuum systems have been used more often to remove deposits of non-floating oil; however, these systems are more suited for thick deposits of liquid and semi-liquid oil close to shorelines and in water with good visibility. Operation costs are usually higher and the method is slow compared to conventional cleaning. Cold water temperatures increase oil viscosity and reduce dive times, which increases cost and cleaning time. The effectiveness of pumps may be decreased by the presence of sunken debris, medium-sized or larger rocks, rocky bathymetric irregularities, or silt and fine sediments in the recovery area.
Under ideal conditions, physical recovery of spilled oil can be expected to achieve a maximum recovery rate of 30% (NRC, 1989), and this could be much lower in cold water and Arctic environments (Engelhardt, 1994). While improvements are being made on the design of equipment for the recovery of oil under Arctic conditions, emphasis is now being placed on in situ methodologies that require fewer response personnel and do not require the storage, transport and disposal of waste.
5.3 In situ Burning
In situ burning (ISB) seeks to destroy oil through the combustion of ignitable components. This technique is subject to limitations such as the need for specialized oil booms, concerns over the generation of smoke and potential toxic by-products, operational constraints linked to sea-state, and the combustibility of the oil. Based on the limited information published to date, ISB has not been considered to be a first choice response strategy such as containment and mechanical recovery, due to potential ecological and human health and safety concerns. However, its reported success in the removal of approximately 5% of bulk surface oil following the DWH spill has dramatically increased interest in its potential use (Federal Interagency Solutions Group, 2010). At present, research emphasis for ISB is on attaining higher efficiencies in emulsion burning, refinement of towing manoeuvres, burn enhancement and extinguishing techniques, burn equipment evaluations, smoke plume modelling, assessments of potential environmental effects, training of ISB personnel, and research to extend the window of opportunity through the use of chemical emulsion breakers.
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Oil spills on water can be burned if the oil layer is thick enough and an adequate ignition system is available (Fingas et al., 1995). Burning oil within transition seasons appears to be a practical response option. In drift ice, oil spills can rapidly spread to become too thin to ignite. Fire booms are required to collect the slick and keep it thick in open water. Burning oil on solid ice or on snow is usually feasible within 2 - 5 days following a spill on ice or within several months if the oil has spilled in or under ice.
Burning oil in a broken ice field is dependent on how well the oil is contained by ice. Brash, frazil or slush ice will accumulate with the oil against the edges of larger floes and control the thickness of oil in a given area (Potter and Buist, 2008). Burning efficiency can be about 50% in calm conditions and 33% with waves (Buist et al., 2003). Cold-water herders can also be used to thicken a thin oil slick in the presence of brash or slush ice. However, the presence of frazil ice restricts the spreading of oil and reduces herder effectiveness. Short, choppy waves may cause a herded slick to break up. Hydrophilic emulsion breakers are most effective when used in a confined environment.
The use of herding surfactants may also facilitate the containment and burning efficiency of a slick. Herding agents are usually applied in the periphery of an oil slick to change the balance of interfacial forces acting on the slick edge and allow the interfacial tensions to contract the oil into thicker layers. New herding agents are of low toxicity and the main surface-active ingredients of successful herders are not soluble in water and are not intended to enter the water column, only to float on the surface (Buist et al., 2008). A series of mid-scale testing was conducted at different locations to examine the concept of using herding agents to thicken oil slicks among loose pack ice for the purpose of ISB (Buist et al., 2008; Buist et al., 2006). Field experiments were performed off Svalbard in May, 2008 to test the ability of a non-proprietary hydrocarbon- based cold water herding agent (USN) to burn oil in drift ice (Buist et al., 2011). Experiments were also carried out in a laboratory and large-scale refrigerated test tank to determine if a new generation of fluorosurfactants or silicon-based surfactants are more effective than USN. In these experiments, which included field trials, a larger number of tests were done in open water conditions and the data indicated that the herders also worked efficiently in quiescent open water (Buist and Nedwed., 2011). These results suggested that potential exists for the use of ISB 77
herding agents as an effective and rapid response option in open Arctic waters and remote temperate regions.
Research has been directed to the study of potential environmental effects caused by ISB. It has been demonstrated that the temperature at the slick-water interface is never more than the boiling point of the water and usually remains close to the ambient temperature (Buist, 2003). There is a steep temperature gradient across the thickness of the slick. The slick surface is very hot (350 500C) but the oil just beneath it is near ambient temperature. Fingas et al. (2005) analyzed the soot resulting from the burning of heavy oils and an emulsion of bitumen. The residues are mainly resins and asphaltenes not burned in the fire and the enriched pyrogenic PAH derived from the petrogenic PAH of the oil. Resultant PAH concentrations correlated inversely with burning efficiency. Thus, attaining higher burning efficiencies reduces the amount of pyrogenic PAH in the soot.
The fate and behaviour of the burn residue has also been investigated (Gunette et al., 1995). Experiments conducted in a circulating flume to investigate the ignition, combustion and residue remaining from continuous burning of weathered emulsified Statfjord crude showed that most of the burn residue remained buoyant and the lost residue was usually found submerged about 30 cm below the water surface. Further experiments with eight different oil types revealed that the quantity of the burn residue that remained buoyant and the portion of it that sank were dependent on oil type (Buist et al., 1995). While residues of thicker, heavy oil slicks and weathered crude may sink in freshwater and saltwater upon cooling to ambient temperature, burn residues of lighter oils may not sink.
Predicting ignitability of oil spills as a function of oil type and weathering was identified as a need to make ISB more operational (Brandvik and Faksness, 2009). SINTEF researchers constructed a small-scale laboratory burning cell to perform controlled experimental burns of weathered and emulsified oil on a 100 mL scale (Brandvik et al., 2010c). The laboratory cell has been verified against large-scale field ISB experiments and the results of the limits of ignitability from both experiments correlated well. The burning cell has been used to generate a comprehensive dataset with ignitability and burning efficiency as a function of oil type, ice 78
conditions and degree of weathering (Brandvik et al., 2010b). These data are used to develop and calibrate an algorithm that is implemented in the SINTEF Oil Weathering model, and to predict ignitability for oil spills. It is expected that this will enable more reliable predictions to be made within the operational window of opportunity for use of ISB as a function of weathering.
Ignition promoters and emulsion breaking chemicals can also be used to increase the ignitability of a slick. Studies have been conducted to develop a more complete understanding of the use of emulsion breakers injected into an oil spill recovery system at both the lab-scale, and the large- scale such as at the Ohmsett wave tank (SL Ross Environmental Research Ltd., 2002).
5.4 Chemical Dispersion
In cold temperatures, as the oil becomes more viscous, it becomes more difficult to disperse. On the other hand, dispersed oil droplets will re-coalesce at a slower rate at low temperatures, and leaching of the surfactant from oil would also be slower. These factors favour enhanced chemical dispersion. Different oil types have different potential for chemical dispersion in cold waters. While heavy oils have been considered out of range for effective dispersant use, the latest generation of improved dispersants appears to be effective with oils having a viscosity approaching 10,000 cSt (Colcomb et al., 2005; Fiocco et al., 1999).
Dispersion of fresh and weathered Alaska North Slope (ANS) crude oil in nearly freezing water has been demonstrated (Belore et al., 2009). Corexit 9500 and Corexit 9527 were both effective in dispersing fresh and weathered Alaskan oils in large-scale wave tank tests completed at the Ohmsett facility in the winter, with 85-99% dispersant effectiveness (DE) and 50-90% droplet size corrected DE. There was no apparent difference in DE on fresh and weathered oil within the relatively narrow range of viscosities tested. These results demonstrate that chemical dispersants can be effective on oils in near-freezing water and under energetic, breaking wave conditions. In the laboratory, it has been reported that tests run with three dispersants at 0 and 20C showed slight differences in volume mean diameter of dispersed LAGO medium crude oil droplets, depending on dispersant composition and energy input (Byford et al., 1984).
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The limiting oil viscosity for chemical dispersion of oil spills under simulated sea conditions in the large outdoor wave tank at Ohmsett, New Jersey, has been determined (Trudel et al., 2010). DE tests were completed using crude oils with dynamic viscosities ranging from 67 to 40,100 cP at test temperatures of 15 and 27C. Tests produced an effectiveness-viscosity curve with three phases when oil was treated with Corexit 9500 at a dispersant to oil ratio of 1:20. The dynamic oil viscosity that limited chemical dispersion under simulated at-sea conditions was in the range of 18,690 to 33,400 cP. Visual observations and measurements of oil concentrations and droplet size distributions in the water under treated and control slicks correlated well with direct measurements of effectiveness.
Heavy fuel oils, characterized by having a high proportion of polar fractions and diminished evaporative fractions, are usually more viscous than unrefined crude oils, and tend to be more difficult to disperse. Therefore, field responses to heavy fuel oil spills are more challenging than the treatment of light and median crude oil spills.
The influence of temperature and wave conditions on the effectiveness of two commercial dispersants with a heavy fuel oil were studied using a flow-through experimental wave tank (Li et al., 2010). This study demonstrated that there was a strong effect of seawater temperature on the DE of the IFO180 using Corexit 9500 and SPC 1000 within a narrow window from 10 to 17C. The effect of mixing energy from breaking wave conditions agrees with results from field trials (Colcomb et al., 2005) and large-scale tank testing (Trudel et al., 2005) of DE for heavy fuel oil. The observed temperature and wave effects were also consistent with laboratory baffled flask tests of dispersed heavy fuel oil (Srinivasan et al., 2007).
In the presence of ice, an obvious limiting factor is the relatively calm sea state that may not be able to deliver sufficient mixing energy for the dispersant to take effect in a cold environment. A possible solution is to provide mixing energy using propeller wash from an ice-breaker. This has been evaluated by a number of field programs (Nedwed et al., 2007; Spring et al., 2006) to demonstrate the potential effectiveness of the technique to enhance dispersion efficiency in ice- infested waters. A more recent field trial has demonstrated the effectiveness of physical 80
dispersion of oil in ice infested waters, by combining the energy input from ice-breaker propeller wash with the addition of mineral fines (Lee et al., 2011c).
A new silicone-based agent has been engineered to spread viscous oil to an extremely thin sheen (Nedwed et al., 2011b). A stable water-in-oil emulsion could be treated to spread to a thickness that was visually undetectable. This new response approach could reduce the impacts of offshore marine oil spills by promoting rapid spreading of the oil, which increases evaporation rates, breaks emulsions, and potentially enhances natural dispersion such that the impact and toxicity of a spill is reduced. It would be useful under Arctic conditions if it proves to operate at temperatures below 0C.
A new gel dispersant has been tested that has the consistency of warm honey, contains more than 85% active ingredient, and is positively buoyant, cohesive, persistent and oleophilic (Nedwed et al., 2011a). This new dispersant specifically designed for use in Arctic temperatures, and on viscous oils, expands the window of opportunity for successful response operations.
From an ecological perspective of the hydrocarbon biodegradation consortium, chemical dispersants may complement the naturally produced bio-surfactant of primary oil-degrading microorganisms, with both sharing the same function of dispersing oil into small droplets that offer a larger surface area for microbial attack. However, uncertainties exist in terms of DE of different oil types at low temperature and ice-infested waters as well as the persistence and biological effects of the dispersed oil. Development and performance evaluation of new dispersants for use in cold waters is required. Understanding the behaviour and environmental impact of chemically dispersed oil in Arctic waters are essential. Research is also needed to understand the long-term fate of chemically dispersed oil, including long-term effects of biodegradation and photo-oxidation. The research requires full-scale field trials that include tracking and monitoring techniques. The development of operational guidelines requires investigations with various types of oil and oil dispersant formulations. In addition, a framework for comparative net environment benefit analysis is needed to assess the different oil spill response and treatment options.
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5.5 Oil-Mineral Aggregates
Dispersed oil droplets that are suspended in the water column may interact with suspended particulate material (SPM), mineral fines in particular, to form oil-mineral aggregates (OMA). Studies of OMA formation have demonstrated that both mineral fines and organic particles can stabilize oil droplets within the water column under a variety of environmental conditions (Bragg and Yang, 1995; Delvigne et al., 1987; Lee, 2002; Lee and Stoffyn-Egli, 2001; Lee et al., 2003; Lee et al., 1996; Muschenheim and Lee, 2002; Omotoso et al., 2002). Various types of aggregates can be formed depending on the physico-chemical properties of the particles, the type of oil, and environmental conditions (Lee et al., 1998; Muschenheim and Lee, 2002; Stoffyn-Egli and Lee, 2002). OMA formation has been observed at numerous field sites from the rivers of Bolivia (Lee and Stoffyn-Egli, 2001; Lee et al., 2002) to the shores of Svalbard Island in the high Arctic (Owens et al., 2003). The occurrence of OMA covers the range of natural variance for temperature, salinity, oil types and mineral composition. This is a natural process that has been observed in cold water and Arctic conditions as, for example, clay-oil flocculation in nearshore waters in Alaska, and the interaction of glacial till with oil in the Beaufort Sea. Controlled laboratory experiments (Cloutier et al., 2002; Khelifa et al., 2005b; Lee et al., 1997; Omotoso et al., 2002; Stoffyn-Egli and Lee, 2002) and shoreline field trials (Lee et al., 1997; Lunel et al., 1997; Owens et al., 1995; Owens and Lee, 2003) have both demonstrated that OMA enhance the natural dispersion of oil spilled in the environment and reduce its environmental persistence. Previous research has demonstrated that the formation of OMA has significant potential to enhance oil dispersion and dilution.
In the natural environment the oil and SPM can interact to form aggregates. The formation of aggregates between mineral fines, like clays, and oil has been studied in the past, and enhancement of the process has been used as an operational shoreline cleaning strategy under the name of surf-washing. When linked with SPM, the dispersed plume is stabilized and the tendency for oil to coalesce at the surface is reduced because oil behaviour follows SPM behaviour.
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Numerical models support the hypothesis that OMA can form rapidly (Hill et al., 2002; Khelifa et al., 2003a) as long as sufficient mixing-energy is available. Detailed chemical analysis of samples recovered from coastal waters following surf-washing operations after the Sea Empress spill in the United Kingdom conclusively demonstrated that OMA formation enhanced the biodegradation rates of the residual oil (Colcomb et al., 1997; Lee et al., 1997) because the stabilization of oil droplets by mineral fines increased the oil-water interface where microbial biodegradation primarily occurs, and operates optimally. Thus, this remediation process not only dilutes oil spilled into the environment, but it may also effectively eliminate many components of environmental concern. In terms of protection of fisheries and fish habitat, OMA formation and dispersion will minimize environmental impacts. For example, field studies in Svalbard, Norway, demonstrated that OMA within the immediate vicinity of the spill site were dispersed to levels below regulatory toxicity threshold limits (Owens et al., 2003).
Recent studies have specifically focused on the potential application of mineral fines to facilitate OMA production as an operational marine oil spill countermeasure. Laboratory experiments have delineated the effects of factors such as mineral type, physico-chemical properties of oil and mineral fines, and the co-presence of chemical dispersants on the morphology and vertical transport of OMA (Lee et al., 2009b; Zhang et al., 2009). Wave tank studies have shown that chemical dispersants and mineral fines have a synergistic effect on the dispersion of crude oil (Li et al., 2007). These recent wave tank studies have repeatedly demonstrated the synergistic effects of mineral fines and chemical dispersants on dispersion of different oil types under both breaking wave and regular wave conditions (Lee et al., 2009a; Lee et al., 2008; Lee et al., 2009b; Li et al., 2009a; Li et al., 2009b; Li et al., 2009c).
An oil spill response technique in ice-infested waters based on the application a slurry of mineral fines mixed by propeller-wash to form OMA has been proposed (Lee et al., 2011c). The process promotes the physical dispersion of stabilized oil droplets into the water column which support higher rates of oil degradation by natural bacterial consortia. To validate the operational effectiveness of this technique a controlled oil spill experiment was conducted from a Canadian Coast Guard ice-breaker in the St. Lawrence Estuary offshore of Matane, Quebec, Canada. Time-series changes in oil concentrations were monitored to quantify dispersion effectiveness. 83
Field samples were also recovered for laboratory microcosm studies on the biodegradation of petroleum hydrocarbons by monitoring CO 2 production and the depletion of specific hydrocarbon components. Detailed chemical analysis by GC/MS with hopane normalization showed that more than 60% of the total petroleum hydrocarbons, 75-88% of total alkanes, and 55-65% total polycyclic aromatic hydrocarbons (TPAH), were degraded after 56 days of incubation at 0.5C. The alkylated PAH was degraded to a greater extent following the addition of mineral fines. This technique offers several operational advantages as a spill countermeasure for use under Arctic conditions such as reduced numbers of personnel required for its application, no need for waste disposal sites, and cost effectiveness.
It has been reported previously by researchers at Cedre, France, that the addition of a dispersant to water containing SPM enhances OMA formation (Guyomarch et al., 2002). This is attributed to the fact that OMA formation usually follows the generation of micron-scale oil droplets which then interact with mineral fines. Furthermore, ongoing preliminary research at Cedre to assess the impact of chemically and mechanically dispersed oil (Discobiol program) has demonstrated that the presence of SPM in the form of silt reduces the toxicity of the dispersed oil, since aggregate formation may bind the oil in a matrix and reduce its bioavailability. In addition, environmental risk assessment mathematical models have been useful for simulating the transport of oil as a result of OMA formation in aquatic environments and predicting the potential risks to the pelagic and benthic ecosystems (Lee et al., 2009c).
A combined application of chemical dispersant and mineral fines to combat oil in low temperatures and low energy environments in the Arctic has great potential to be an effective cold water in situ oil spill response. In light of the fact that hydrocarbon biodegradation in the environment is often limited by nutrients such as nitrogen and phosphorus (Atlas and Bartha, 1972), the use of nutrient-enriched mineral fine particles, such as natural phosphorus-rich minerals, should also be considered. As an integrated bioremediation process, the effects of chemical dispersants and nutrient-enriched mineral fines on biodegradation of dispersed oil in seawater should be evaluated. Although very unlikely to cause significant sinking of oil because of current flow in the field, the possibility exists for increased sedimentation of oil to marine sediments by the use of dense mineral fine particles or the interaction of dispersed oil with 84
natural SPM. The effects of chemical dispersants and nutrient-enriched mineral fines on anoxic biodegradation of hydrocarbons, including alkanes and aromatics, coupled with terminal electron accepting processes, such as sulphate, nitrate, and iron reduction, would also be of interest.
5.6 Bioremediation
Bioremediation aims to accelerate the natural biodegradation process of petroleum hydrocarbons. Natural selection of oil degrading microorganisms in polar areas results from the natural seeps of petroleum (Landes, 1973). Hydrocarbons are ubiquitous in marine systems, originating from natural seeps of oil and natural gas deposits, marine oil transportation accidents and operational discharges (Yakimov et al., 2007). Globally hundreds of millions of litres of hydrocarbons enter the environment from both natural and anthropogenic sources every year.
Marine hydrocarbon-degrading bacteria were identified almost a century ago. Aerobic bacteria that degrade hydrocarbons are increasingly recognized as key players in the removal of hydrocarbons from oil-polluted marine environments (Head et al., 2006). Anaerobic biodegradation of several classes of petroleum hydrocarbons, including alkanes and mono and polycyclic aromatic compounds have been demonstrated in recent studies (So et al., 2003; Townsend et al., 2003; Widdel and Rabus, 2001). In the light of these findings, future research and development in Arctic oil spill bioremediation should also give some consideration towards in situ methods that employ the biological degradation of hydrocarbon contaminants with minimal mechanical containment and recovery of oily wastes, their transportation, or disposal.
Numerous laboratory and field studies at subzero temperatures have demonstrated the significant biodegradation potential of petroleum hydrocarbons in the Arctic (Bragg et al., 1994; Brakstad et al., 2008; Lee et al., 2009d; Prince et al., 2003a; Sveum and Ladousse, 1989). Biodegradation of many components of petroleum hydrocarbons by indigenous, cold-adapted microorganisms at low temperatures in Arctic, alpine, and Antarctic soils has been reported (Whyte et al., 2001). Much work has been focused on the bioremediation of contaminated soils in the Canadian high Arctic, where fuel used for transportation, electricity and heating has frequently spilled or leaked from tanks and pipelines (Mohn and Stewart, 2000; Whyte et al., 2001; Whyte et al., 2002; 85
Yergeau et al., 2009). Because the remoteness and unique character of these sites preclude conventional physico-chemical technologies for soil treatment, bioremediation is often the only feasible cleanup option.
Marine waters including those of the Arctic usually have low concentrations of nitrogen and phosphorus that limit the biodegradation of hydrocarbons (Prince, 1993). Addition of fertilizers has been reported to stimulate the extent of biodegradation in the field (Bragg et al., 1994; Prince, 1993; Prince et al., 2003a; Swannell et al., 1996; Venosa et al., 2002). In the case of the Exxon Valdez oil spill, fertilizer amendments increased the rates of biodegradation by three to five times (Atlas, 1995).
Different nutrient products have shown variable effectiveness, depending on their nature, the properties of the oil, and the characteristics of the contaminated environments. Application protocols for bioremediation (form and type of fertilizer or type and frequency of application) must be specifically tailored to account for differences in environmental parameters, including oil characteristics, at each contaminated site (Boufadel et al., 1999; Venosa et al., 1996; Wrenn et al., 2006; Wrenn et al., 1994; Wrenn et al., 1997a; Wrenn et al., 1997b).
Bioremediation efforts have been carried out mainly on shorelines and in wetlands, rather than offshore, because effective treatment of an oil spill is likely to take longer than the period for the slick to reach the coast (NRT Science & Technology Committee, 2000), and because of the difficulty of maintaining elevated nutrient concentrations in an open system subject to rapid dilution (Leahy and Colwell, 1990). Delille et al. (1998) investigated the potential use of an oleophilic nutrient formulation in Antarctic coastal seawater. An order of magnitude increase in bacterial microflora occurred in seawater after it was contaminated with Arabian light crude oil. The addition of the oleophilic fertilizer, INIPOL EAP 22, designed to maintain elevated nutrient levels around the oil, clearly enhanced the growth of both saprophytic and hydrocarbon-utilizing microflora. Chemical analysis of the residual hydrocarbon fractions confirmed that fertilizer application increased the rate of oil biodegradation.
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Significant advances have been made in the development of molecular techniques for detecting microbial pollutant degrading genes in environmental samples without the need for cultivation of the bacteria themselves. Catabolic genotypes involved in the degradation of representative fractions of petroleum hydrocarbons, including n-alkanes, aromatics, and PAHs, are reported to be widespread in Arctic soils and Alaskan sediments (Margesin et al., 2003). Applying biotechnological methods in bioremediation studies can determine the prevalence and composition of specific hydrocarbon degrading populations, and thus aid in assessing the biotreatability of contaminants, and in monitoring the effects on specific population dynamics during the remediation process. A recent study on prevalence of alkane mono-oxygenase genes in Arctic and Antarctic hydrocarbon contaminated and pristine soils indicated that Rhodococcus spp. may be the predominant alkane-degrading bacteria of the tested genotypes in polar soils. Pseudomonas populations may become enriched following hydrocarbon contamination, whereas Acinetobacter spp. are not a predominant member of the polar alkane degradative consortia (Whyte et al., 2002). The ability to determine the alkane degradative composition of a microbial community also helps to develop appropriate bioremediation strategies for a particular contaminated site. For example, the presence of large numbers of alkane degradative Rhodococcus spp., known to produce at the cell-surface biosurfactants with activity at cold temperatures, and to directly adhere to solid alkanes at low temperatures (Whyte et al., 1999), would eliminate the need to incorporate a surfactant treatment as part of an Arctic bioremediation strategy.
Bioaugmentation consists of the addition of known oil degraders that are not native to the contaminated sites to supplement the existing microbial population (Bartha, 1986). Bioaugmentation approaches have been proposed in situations where the indigenous microbial population may not be capable of degrading the wide range of potential substrates present in complex mixtures such as petroleum, where they may be in a stressed state as a result of the recent exposure to the spill, where the indigenous hydrocarbon-degrading population is too small to maintain a high enough decontamination rate, or where seeding is required to reduce the lag period in growth prior to the onset of the bioremediation process (Forsyth et al., 1995). However, bioremediation field trials in open water environments have consistently shown that 87
bioaugmentation provides little or no benefit to treatment of the spilled oil (Lee et al., 2005b; Nichols and Venosa, 2008).
In contrast to terrestrial hydrocarbon degraders which tend to be metabolically versatile and utilize a large range of organic substrates, their marine counterparts are highly specialized obligate hydrocarbon utilizers, who play significant, global roles in the natural cleansing of oil pollution in marine systems (Yakimov et al., 2007). The marine hydrocarbon-degrading microorganisms have the capacity to efficiently degrade hydrocarbons (Harayama et al., 2004; Head et al., 2006). The toxic components of dispersed oil are eventually removed through biodegradation and other attenuation processes, such as irreversible absorption to suspended sediments.
Traditional bioremediation studies focused on the microorganisms that directly degrade the contaminants. However, these microorganisms only form part of an ecological system consortium (Head et al., 2006), which involves many direct and indirect interactions with other community members and the environment, and therefore oil degradation processes are influenced by environmental variables such as nutrient availability or physico-chemical parameters. Such interactions of oil-degrading microorganisms with the environment include competition for limiting nutrients, predation by protozoa, lysis by phages and cooperative interactions to increase contaminant degradation.
The common criterion for decommissioning a contaminated site is based on oil chemistry, and therefore most previous studies for monitoring bioremediation of hydrocarbon contaminated matrices (soils, sediments, and waters) focused on chemistry, including target hydrocarbon components, water quality parameters, and metabolic activities of microbial processes, such as respiration, enzyme activities, and microbial counts (Margesin et al., 2003; Whyte et al., 2001). Insights into the ecological structures and functions and understanding of the dynamics of the microbial communities involved in the oil biodegradation process will facilitate design of more efficient bioremediation techniques (Whyte et al., 2002; Yergeau et al., 2009). The development and optimization of in situ bioremediation strategies requires better knowledge of the impact that hydrocarbon contaminants have on marine microbial communities, which are the most important 88
oil-degrading groups in the open seas, sediments and shorelines of the Arctic region (Greer et al., 2010). Greater insight into metagenomics the study of microbial genome fragments recovered from environmental samples in contrast to genomes that are isolated from clone cultures that sustain the catabolic function, transformation and mineralization of petroleum hydrocarbons is also necessary (George et al., 2010). Moreover, understanding the interaction of microbial communities and hydrocarbon pollutants helps to assess the potential recovery of contaminated areas and to increase the opportunities for successful design and implementation of bioremediation treatment.
5.7 Natural Attenuation
Monitoring natural recovery of oil relewased into the environment should also be considered an operational response option under some circumstances. Natural seepage of petroleum hydrocarbons is known to occur in the Arctic (Grant et al., 1986) and this prior exposure through chronic or single events influences the number of hydrocarbon-degrading microbes (Delille et al., 1997; Delille and Delille, 2000; Langworthy et al., 1998). One study of oil in Antarctic ice and the effects on the bacterial population showed increases in hydrocarbon-degrading bacterial populations in response to contamination (Delille et al., 1997). More recently, considerable changes in bacterial populations within Arctic sea ice following exposure to hydrocarbons was demonstrated, whereby diversity decreased and there were clear indications of hydrocarbon degradation (Brakstad et al., 2008). Additional studies are required to substantiate these observations and gain a better understanding of the overall degradation activity and the microbial populations involved in the degradation of hydrocarbons in ice. Studies are required to address the ice-water interface, where considerable amounts of hydrocarbon would be expected to pool and thus be exposed to the high densities of bacteria found near that interface.
Until recently little attention has been given to improve our understanding of oil in ice interactions and the ecological significance of microbial degradation activity of the residual oil. While the potential biodegradation of oil in Arctic waters and within ice has been reported to be extremely slow based on laboratory culture studies, recent respirometry and genomic studies suggest significant rates of hydrocarbon degradation. The brine channel walls within sea ice 89
provide a large surface area that could be colonized by bacteria and algae and used for protistan attachment and grazing (Krembs et al., 2000). At 2C, it was estimated that between 6 and 41% of the brine channel surface area could be covered by microorganisms which is considerably higher than the total surface area of soil where <1% is covered by microorganisms. Recently the presence of microbes in the brine pore spaces of sea ice was confirmed (Junge et al., 2001) along with their interaction and activity on the surfaces (Junge et al., 2004). Microbes have clearly adapted to this environment, for bacterial strains readily isolated from sea ice have been found to be cold-adapted, halotolerant species (Brown and Bowman, 2001; Junge et al., 2002). In the Gulf of Mexico, recent studies have also reported very short half-lives for the dispersed oil within the plume observed in the low temperature water recovered from a depth of ~1300 m (Hazen et al., 2010). In terms of Arctic oil spill response, there is a need to understand natural degradation rates for oil associated with ice. 90
6. Biological Effects of Oil
6.1 Oil Toxicity in the Arctic
Arctic marine ecosystems exhibit a number of unique characteristics in terms of habitat, and community structure and function including (Camus et al., 2008): permanently or seasonally ice covered waters; seasonal and spatial fluctuations in primary production characterized by intense inputs followed by long periods of limited availability; multiple sources of primary production (ice algae, phytoplankton, benthic microalgae, bacterial colonization of organic detritus); relatively simple food web structure and short food chains; strong pelagic-benthic coupling; prevalence of large predators; long-lived and slow growing organisms; high lipid content of organisms (energy storage strategy).
Marine oil spills may occur during any phase of oil extraction, storage and transportation (WWF, 2007). As described in Section 3.4 Factors Influencing Oil Fate (Weathering), the lower water temperatures in the Arctic may reduce oil degradation rates, while extended periods of darkness and light which influence the breakdown of photosensitive components of oil and the presence of ice and harsh weather conditions may hamper cleanup operations. All of these factors affect the concentration and persistence of oil and spill treating agents potentially used in response operations. The concentration and exposure time of these compounds influences the subsequent risk to Arctic biota.
Of greatest concern is the biological impact on species considered to be valued ecosystem components (VECs) - elements of the ecosystem having scientific, social, cultural, economic, historical, archaeological or aesthetic importance, determined on the basis of cultural ideals or 91
scientific concern (Forbes, 2011). The vulnerability of a VEC is considered in its relationship with anthropogenic, biotic and environmental drivers (Table 5).
Table 5 Valued ecosystem components (VEC) of various Arctic regions at risk from oil spills (INAC, 2010; Word and Perkins, 2011). VEC Reason Barents Sea Beaufort Chukchi Copepod, Calanus glacialis Significant Tier II food web prey of invertebrates, fish, marine mammals and seabirds
Polar cod, Boreogadus saida Keystone Tier III food web species, predator of lower trophic levels, and prey of fish, marine mammals and seabirds
Sculpin, Myoxocephalus sp Marine and estuarine sculpin, important primary carnivore and Tier III food web prey of fish, marine mammals and seabirds
Harp seal Commercial value, interaction with fish stocks Ringed seal Important prey for polar bear and Arctic fox (Vulpes lagopus)
Bearded seal Possible indicator of benthic contamination (feeds on bivalves and benthic invertebrates
Right whale Endangered Minke whale Commercial value Humpback whale (Megaptera novaeangleae) High international profile Bowhead whale Endangered, cultural value Beluga whale Near threatened Polar bear Extreme sensitivity to petroleum intoxication, high international profile, status: vulnerable
Capelin (Mallotus villosus) Commercial value, important prey of cod, seals, whales
Scallop Commercial value, prey of bearded seal, possible oil spill indicator species
Recreational seal hunt Cultural value Fast-ice ecosystem A petroleum spill would disperse slowly
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A number of comprehensive studies have been published describing biological components within various Arctic systems. For example, Gulliksen and Lnne (1991) recorded sea ice faunal assemblages with invertebrates and fish both in the Arctic and Antarctic. Ikvalko and Gerdes (2004) gathered data from 91 different sources for the survey of the diversity of Arctic sea ice biota. Arndt and Swadling (2006) provide information on distribution, diet and life history strategies of crustaceans in Arctic and Antarctic sea ice. Iken et al. (2005) investigated the food web structure of the Canada Basin in the high Arctic. Organisms of all habitats, sympagic (ice- associated), pelagic and benthic were investigated. Rand and Logerwell (2011) performed a demersal trawl survey of benthic fish and invertebrates in the Beaufort Sea. Darnis et al. (2008) investigated sea ice and the onshore-offshore gradient in pre-winter zooplankton assemblages in the southeastern Beaufort Sea. Hopcroft et al. (2005) sampled zooplankton communities of the Canada Basin. Bluhm et al. (2005) investigated the macro-benthic and mega-benthic communities in the Canada Basin. Despite this level of effort for basic knowledge, Pegau (2011) suggests there is limited knowledge of the biological communities that might be at risk from oil spills. Little is known about the effects of hydrocarbons on the biology of the Arctic compared to temperate areas and less is known about the effects of oil in ice. Furthermore, this is compounded by ongoing changes in the Arctic ecosystem. Along with global climate change which is modifying ice coverage in the Arctic, the impact of ocean acidification in the Arctic might alter the sensitivity of organisms such as molluscs, crustaceans, echinoderms, encrusting algae, and certain types of marine phytoplankton to toxic compounds (NOAA, 2010).
6.2 Routes of Exposure
Little is known about the responses of organisms living between -1.88C and 5C (Camus et al., 2002a; Camus et al., 2002b). The low temperatures of Arctic regions may alter the behaviour of oil as oil dissolution is temperature dependent (Payne et al., 2001b), as discussed in Section 3.3 Factors Influencing Oil Behaviour. Marine organisms living at low temperatures, with the seasonal presence of sea ice, strong seasonal changes and low food availability have developed specific physiological adaptations such as high lipid content, low production/biomass ratio, anti- 93
freeze mechanisms and low metabolic rates (Weslawski et al., 1988). Four main routes through which organisms can be exposed to oil or petroleum compounds resulting from a spill are: direct contact, or when an organism becomes coated; ingestion by eating or drinking; inhalation of vapour, mist, or spray; and absorption directly through its skin or respiratory membranes.
Oil affects aquatic biota by one of three means (Albers, 2002): physically as by smothering animals, coating them or reducing light transmission; by altering habitat characteristics such as changing pH, reducing dissolved oxygen or reducing available food; by acting as a toxicant.
Generally, PAHs are considered the source of toxic effects of oil (Albers, 2002). In water the toxicity increases with the molecular weight of the aromatic to a limit of molecular weight 202. Beyond this limit water solubility decreases as does toxicity (Albers, 2002). The toxic action of PAHs is related to their ability to interfere with cellular membrane function, and PAH metabolites may also bind to cellular proteins and DNA (Albers, 2002). Background concentrations of PAHs in water are very low much below toxic thresholds. However, during oil spills, concentrations may be higher than threshold values. PAH concentrations in sediment are much higher than those observed in water but bioavailability is limited, thus reducing the toxic potential (Albers, 2002).
Biota that can be affected occupy various habitats within an ecosystem (Boyd et al., 2001). Surface dwellers such as birds, marine mammals and reptiles are subject to risk from exposure to oil floating on the sea surface. Pelagic inhabitants of the water column, like fish and plankton, are typically at lower risk although natural, chemical or enhanced dispersion of the oil can temporarily increase their risk. Benthic creatures living on and in the sediments, such as crabs, bivalves, and plants, are at risk from oil that sinks or is in contact with the sediment. Intertidal biota like crabs, bivalves, anemones and algae, are at high risk of exposure if the spill reaches the shore. 94
For the purpose of natural resource damage assessment, Logerwell and Baker (2011) consider three habitats that could be impacted by spilled oil in the Arctic: neustonic, pelagic and benthic. The neuston layer could be directly impacted by the release of surface oil. Oil released from the seabed is expected to primarily impact both benthic and pelagic habitats. Surface oil that becomes entrained could impact the pelagic habitat. If the entrained oil becomes associated with suspended particulate material (Lee et al., 2011c), the residual oil may sink and impact benthic organisms. Both surface slicks and entrained oil can also impact shorelines as reported during the Baffin Island Oil Spill (BIOS) project.
Biota associated with the Arctic neuston that could be potentially impacted include ice algae, phytoplankton, zooplankton and ice invertebrates, ichthyoplankton, pelagic fish and crustaceans, seabirds, anadromous fish, and polar bears (Logerwell and Baker, 2011). Neustonic, pelagic and benthic inhabitants that could potentially suffer impact are sea ducks, gray whales, walrus and seals, while the benthic members that could be impacted are bivalves, polychaetes, macroalgae, demersal fish, subtidal invertebrates, shorebirds, saltmarsh vegetation and caribou which feed on grasses and sedges in salt marshes (Logerwell and Baker, 2011).
6.3 Bioaccumulation, Biomonitoring and Toxicity Assessment
Bioaccumulation of hydrocarbons is a concern with shellfish as it can cause tainting, but it is generally not thought to affect fish or mammals because they are able to metabolize hydrocarbons (Boyd et al., 2001). Contaminated shellfish can depurate (excrete) hydrocarbons when moved to clean seawater. Finfish can metabolize oil within several days after exposure.
During a large-scale field experiment in the marginal ice zone of the Barents Sea, 7,000 L of fresh Troll crude were released between the ice floes (Faksness et al., 2010). The oil was not contained except by the floes. The water accommodated fraction (WAF) was of particular interest because most of the toxicity from a slick is attributed to its semi-volatile organic compounds consisting of naphthalenes, phenanthrenes, dibenzothiophenes and phenols. Water samplers were deployed approximately 3 m below the ice for risk assessment analysis. The 95
concentration of total extractable hydrocarbons in the water from large volume samplers was 4- 32 ppb, and the concentration of water soluble components from semi-permeable membrane devices was 0.6 (background) to 4 ppb. A hazard index, an estimate of the hazard of dissolved oil in the water column from the spill, was calculated from the ratio of the estimated LC 50 of individual components to the measured concentrations that organisms experience (Faksness et al., 2010). Results of WAF data obtained from the large water samplers and semi-permeable membrane devices gave an HI from 0.0004 to 0.11, indicating that the risk of acute toxicity was very low. Conversely, the HI for the Corexit 9500 chemically enhanced water accommodated fraction (CEWAF) ranged from about 1.4 to 4.7 indicating acute risk (Faksness et al., 2010).
Biomonitoring tools for use in risk assessment in the Arctic are being developed (Camus et al., 2010). An environmental impact factor is being used in risk assessment to provide a quantitative estimate of ecological risk for a region. The environmental impact factor is based on the ratio of the predicted environmental concentration (PEC) to the predicted no effect concentration (PNEC). The PNEC is obtained using LC 50 toxicity data (Table 6) from testing the species of concern with the pollutant of interest, and an assessment factor may be added depending on the quality of the empirical data. Usually, the most sensitive species (having the lowest LC 50 value) is used. If PEC/PNEC < 1, no risk reduction is needed; whereas if PEC/PNEC 1, the risk is unacceptable and measures must be implemented by the operator to reduce it (Camus et al., 2010).
Table 6 Food web functional group and acute toxicity LC 50 (95% confidence interval) using 2-methyl naphthalene for co-inhabiting Arctic species (Camus et al., 2010; Carroll et al., 2010). Species Common Name Functional Group 96 h LC 50 (mg/L) Acemaea tessulata Limpet grazer 0.35 (0.30-0.42) Strongylocentrotus droebachiensis green sea urchin grazer 0.68 (0.62-0.74) Boreogadus saida polar cod predator 0.80 (0.53-1.21) Littorina littorea Periwinkle grazer 1.23 (0.83 1.83) Gammarus sp. Amphipod scavenger 1.34 (1.08-1.67) Pandalus borealis Shrimp opportunist 1.56 (1.31-1.86) Sclerocragnon sp. Shrimp opportunist 1.70 (1.46-1.97) Anonyx nugax Amphipod scavenger/predator 1.92 (1.48-2.48) Chlamys islandica Arctic scallop filter feeder 2.75 (1.17-6.47) Margarites helicina Snail grazer 5.01 (4.14-6.07) Nymphon gracile sea spider predator/scavenger 5.42 (4.23-6.95)
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Camus et al. (2010) posed the following questions. Are available toxicity data for non-Arctic species representative of Arctic species? Does the use of data for temperate species provide sufficient protection for Arctic ecosystems? What are the uptake rates, body burdens, and depuration rates for Arctic species?
Biomarkers are quantifiable responses in an organism that often indicate stress due to one or more environmental stimuli. Biomarkers that can be used are based on various biological activities such as gene expression, protein synthesis, antibody production, changes in blood chemistry, frequency of a particular deformity, or some other morphological or biochemical change. For example, one of the most widely used biomarkers is ethoxyresorufin-O-deethylase (EROD) induction. The EROD assay monitors the induction of the cytochrome P4501A enzyme system (CYP1A) which metabolizes xenobiotics, and is a widely used biomarker for exposure of wildlife to substances that bind the aryl hydrocarbon receptor (AhR). EROD is induced in fish in the presence of xenobiotics including PAHs (Hodson et al., 1991). For certain biomarkers, a change in the biomarker is a toxic response. However, it is important to note that induction of (a change in) the CYP1A system is not a toxic response, but an indication that the organism is responding to a xenobiotic compound.
Some of the biomarkers that have been examined for polar cod include CYP1A, EROD, glutathione S-transferase (GST), bile metabolites and DNA adducts by the comet assay (Nahrgang et al., 2010a; Nahrgang et al., 2010b; Nahrgang et al., 2009; Nahrgang et al., 2010c; Nahrgang et al., 2010d). The lysosomal membrane stability test was a suggested addition to the battery of biomarkers that could be used in risk assessment and monitoring. Baseline levels were low and did not mask the effect of contaminant induction; however, natural variation in baselines for an organism can change seasonally according to such things as general health, biological activity and maturity, and this is an area requiring further research (Camus et al., 2010). In addition to this, the lipid content of Arctic organisms, and their metabolic kinetics determine the uptake, accumulation and depuration of lipophilic toxins such as PAHs.
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Recently, a more ecosystem-relevant approach has been to use a species sensitivity distribution rather than the toxicity data for the single, most sensitive species (Carroll et al., 2010). The Arctic and temperate species sensitivity distributions based on LC 50 values were found to be comparable within the 95% confidence limits. It was concluded that the data obtained for temperate species can be applied to Arctic species (Carroll et al., 2010). This conclusion is similar to that for Atlantic and Pacific herring. The toxicity data for Atlantic herring embryo response to dispersed oil can be used for Pacific herring (Lee et al., 2011b).
6.4 The Arctic Food Web
Figure 22 and Figure 23 are schematics of typical Arctic food webs. While appearing very complex, Arctic food webs are considered to be simpler than those in temperate climates (Camus et al, 2008). Camus et al. (2008) reviewed ecotoxicological studies relating to Arctic systems. They concluded that adult Arctic organisms are relatively resistant to oil compared to temperate organisms; Arctic communities may be more vulnerable to oil pollution than temperate ones; and early life stages of organisms appear to be highly sensitive to oil compounds.
Figure 22 The Arctic Food Web (ACIA, 2004). 98
Figure 23 Energy flow above trophic level 1 from phytoplankton and pelagic detritus in red, or benthic detritus in blue, and proportional shades in between. Top panel: eastern Bering Sea shelf; bottom panel: western Bering Sea shelf. Box and text size are proportional to log 10 of biomass for the compartment; area of each link proportional to volume of flow (Aydin et al., 2002).
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6.5 Effects on Arctic Sea Ice Communities
Arctic sea ice covers significant portions of the northern hemispheres oceans: approximately 7 10 6 km 2 in during the summer, and about twice as much area in the winter (ArcOD, 2010). Sea ice occurs in various configurations such as thin or nilas pancake ice, ridged first-year and multi-year ice, and pack ice. Multi-year ice found in deep basins can be up to 2-3 m thick.
Arctic sea ice forms at a freezing point of about -1.9C, since the salinity is usually about 33 parts per thousand (ppt). As ice crystals grow in the water during the autumn season, small ice platelets begin to accumulate at the ocean surface, and inter-link to form a porous structure of ice crystals filled with liquid referred to as brine. The ice-specific ecosystem at the ice-water interface and brine channels (which range in diameter from microns to a few centimetres while the temperature remains above -5C) includes bacteria, viruses, unicellular algae, diatom chains, worms and crustaceans that form the base of the Arctic food web (Bowman and Deming, 2010; Deming, 2010; Krembs and Deming, 2011).
Temperature controls the physical and chemical aspects of ice. As the temperature drops, the ice becomes more solid with a corresponding reduction in porosity and smaller brine channels, accompanied by an increase in salinity of the brine. Winter temperatures can range from -35C at the surface to -2C at the bottom of the ice floe. Salinity can reach 250 ppt.
Sea ice also provides a critical habitat for photosynthetic algae and a nursery ground for invertebrates and fish within the Arctic ecosystem. When the ice melts in spring and summer, excretions of metabolic products and debris from dying cells that accumulated over the winter are released into the water along with organisms (Michel et al., 2002). The excretion of metabolic products and debris from dying cells can become incorporated into the cryopelagic food web, or become deposited on the surface of the sediment to contribute to the benthic food web. At the peak production of ice algae in spring, the solid ice transforms into pack ice with individual floes that transport organisms, sediment and anthropogenic pollutants over thousands of kilometres before they melt and discharge their contents into the water (Krembs and Deming, 2011).
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Sympagic algae and phytoplankton are considered the most important primary producers in the Arctic, capturing the energy of sunlight via photosynthesis. In the lower sections of ice, algal blooms make up about 57% of the Arctic primary productivity (Gosselin et al., 1997). Epontic algae such as the diatoms, Nitzschia grunowii and N. frigida (Cross, 1982b), grow on the underside of the ice, beginning each spring as sunlight returns. Many ice-dwelling organisms accumulate organic molecules including lipids that act as internal antifreeze. Organic compounds exuded by the microbes have been shown to cause the ice to become sculpted (Krembs et al., 2011; Raymond and Knight, 2003), facilitating the attachment and growth of algae that utilize the nutrients locked in the brine channels. The algal diatom, Melosira arctica, can form filaments several metres long extending into the water column. Zooplankton grazers such as Apherusa glacialis, Gammarus wilkitzkii and Onisirnus glacialis feed on diatoms and are protected in the sculpted ice channels. Protozoans and metazoans, especially turbellarians, nematodes, crustaceans and rotifers, can be abundant in all ice types throughout the year (ArcOD, 2010). On the underside of ice floes Calanoid copepods and amphipods (e.g. Parathemisto) that graze on the ice algae are often observed at densities of up to several hundred individuals per square metre. Polar cod (Boreogadus saida) feed on the amphipods, copepods and zooplankton, and are in turn eaten by seabirds and marine mammals (Bradstreet and Cross, 1982). The polar cod, B. saida, is often called Arctic cod, but there is another species, Arctogadus glacialis, which is also called Arctic cod. A. glacialis is a deepwater gadid lacking barbels, that is found between 85 and 72 latitude north in the western Arctic basin, and along the northeastern and northwestern coasts of Greenland. For the purpose of this report, B. saida will be referred to as polar cod.
Due to the reluctance of conducting large-scale in situ oil spill experiments in marine areas where surface ice is prevalent, comprehensive knowledge of the effects that oil has on sympagic biological communities is largely incomplete (Pegau, 2008), so in many cases, oil spill researchers must infer oil-in-ice effects based on experiments which were conducted in ice-free conditions. Pegau (2008) further states that ice environments are very different from typical marine environments, and that caution must be used when extrapolating effects to the ice environment.
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Brackstad et al. (2008) noted that although concentrations of specific oil-degrading prokaryotes seem to remain static, total counts of heterotrophic bacteria were higher in ice that was contaminated with oil. Further, bacterial populations in contaminated ice were quickly dominated by a few microbes, while clean ice communities were more heterogeneous.
The vast majority of the biological activity associated with sea ice is located along the bottom boundary of the ice (the epontic community) and is primarily composed of microscopic phototrophic algae, with yearly maximum algal concentrations being found during the spring. Current evidence clearly suggests that direct contact between algal species and oil can lead to death, but that certain species of diatoms seem to have a higher degree of resistance to oil exposure (possibly due to their silica shell or frustule) than other plankton groups and tend to recover most quickly following exposure (Pegau, 2008). Overall, the effects of oil on the primary productivity of algal communities associated with ice seems to be negative, but at very low oil concentrations, primary productivity may actually be increased it is thought that this might be due to suppressed grazing, or increased supply of micronutrients from the oil (Cross, 1982a; Cross and Martin, 1987). While large quantities of oil on the ice surface can effectively block light from reaching the epontic primary producers, moderate amounts of oil tend not to affect the light field any more than natural variations in snow depth and ice thickness (Cross and Martin, 1983).
Some meiofaunal communities at risk of getting stuck in oil, or ingesting it either directly or through their prey, have not been shown to actively avoid oil, making them highly susceptible to its effects. Amphipods have shown different mortality rates in the presence of crude oil depending on species, life stage, and the nature of the oil to which they were exposed (Pegau, 2008). While copepods and polychaetes show some sensitivity to dispersed oil, little response is observed when exposed to fresh or solidified oil, and nematode populations are largely unaffected by the presence of oil in any form (Pegau, 2008).
Laboratory generated WAF from crude oil was used to expose gravid female G. wilkitzkii ice amphipod gammarids (in embryonic developmental stages 3 to 9) for 30 days in a continuous flow system (Camus and Olsen, 2008). The TPAH concentration decreased with time, from 55 to 102
8 ppm in the high dose, from 10 to 2 ppm in the medium dose, and from 5 to 1 ppm in the low dose. The females used in the different treatments were in similar stages, had similar weight and similar numbers of embryos, which were scored for aberrations. Aberrations were significantly higher in the 55 ppm TPAH group. Many of these embryos had a wide gap between the membrane and foetus, which might have been caused by PAH exposure. Aberrations in the 10 and 5 ppm treatments were not significantly different from the control. The study showed that embryo development can be impaired by exposure to WAF having a TPAH concentration of 55 ppm.
Using the same continuous flow oil exposure system, sea ice amphipods were examined for cellular energy allocation (Olsen et al., 2008). This biomarker is measured by assessment of the protein, carbohydrate and lipid content of individuals, as well as their electron transport system, to calculate an energy budget. Protein levels were significantly higher (p = 0.02) in the animals subjected to the medium dose. This might indicate sublethal stress causing a shift in protein metabolism; however, negative cellular energy allocation values indicated that more energy was being consumed than stored, suggesting that the experimental animals (including the controls) were under stress during the manipulation.
6.6 Effects of Oil on Arctic Biota
Bacteria
Studies on the effects of chemically dispersed oil and hydrocarbon biodegradation have been conducted with natural phytoplankton and bacteria in mesocosms under cold temperature conditions. Atlas et al. (1976) showed that bacterial populations increased under oil slicks experimentally floated in Prudhoe Bay, Alaska, in large part due to oil degrading Pseudomonas spp., but species diversity appeared to be unaffected. Siron et al. (1993) noted a marked increase of both density and proportion of oil-degrading bacteria observed two days after the oil addition that suggested the potential capability of the indigenous bacterial community to adapt to an oil 103
spill event. However, under such extremely icy conditions, the biodegradation of the dispersed oil was reduced and only the aliphatic hydrocarbon fraction was slightly degraded.
Peterson and Dahllff (2007) studied the phototoxicity of pyrene to bacteria in Arctic sediment. Their results indicated that shallow Arctic marine areas might be affected by phototoxicity if concentrations of oil components in the sediments increase. The impact of crude oil on changes in bacterial communities of Arctic sea ice has also been studied by Gerdes et al. (2005). They reported a strong shift in community composition to a population dominated by -proteobacteria in sea ice and melt pool samples incubated with crude oil. Similar research by Brakstad et al. (2008) looking at in-ice bacterial community response to North Sea paraffinic oil showed that over the 112 day experiment, oil-contaminated ice cores showed stimulated bacterial growth, but decreased bacterial diversity which was evident from fewer bands in the denaturing gradient gel electrophoresis, DGGE. In these contaminated cores, the microbial community became predominated by Gammaproteobacteria related to the genera Colwellia, Marinomonas, and Glaciecola, while populations in clean ice cores showed more heterogeneous populations. Through additional chemical analysis used to assess n-C17/Pristane and naphthalene/phenanthrene ratios in the ice cores, Brakstad et al. (2008) were also able to show signs of slow oil biodegradation, primarily in the deeper parts of the ice where low hydrocarbon concentrations were found.
Phytoplankton and Macroalgae
Pelagic organisms in the water column include unicellular phytoplankton species of diatoms, dinoflagellates, and protists. When the water column does not support phytoplankton growth, the ice algae and associated invertebrates become the main forage for polar cod, which are a primary food source for seabirds and marine mammals.
Field and laboratory tests have shown that primary production (photosynthesis) is reduced in the immediate area of an oil spill, but recruitment of phytoplankton from nearby, unaffected areas happens quickly (Percy et al., 1985). In the presence of low concentrations of oil, some phytoplankton species of the Beaufort sea (especially green algae) showed increased growth, and 104
at the Balaena Bay experimental oil spill site, diatom growth appeared to be enhanced (Percy et al., 1985). The dispersant, Corexit, affected the plants in the same way as the oil did. Macroalgae in the intertidal zone usually survive a single, short-term spill event, but die under chronic exposure, while salt marsh plants are more fragile (Percy et al., 1985).
Reports of benthic macroalgae (seaweeds) in the sublittoral zone of the Arctic include three species of Chlorophyta, 14 species of Phaeophyta, and 11 species of Rhodophyta (Hamel and Mercier, 2005). Research by Stepaniyan (2008) shows that species of benthic macroalgae can exhibit varying responses to the presence of oil. In these studies it was found that brown algae such as Lamanaria saccharina and Fucus vesiculosus were largely unaffected by crude oil, while other species such as Ascophyllum nodosum and red algae Porphyra umbilicalis and Palmaria palmate exhibited a decrease in growth rate at oil concentrations of 5-10 mg/L. Photosynthetic activity decreased with increases in the concentration of oil in all species of macroalgae studied other than Ascophyllum nodosum, which experienced an increase in photosynthetic activity when exposed to oil. It is believed that these differences in response could be related to structural differences between these species of macroalgae, and in all cases, observed effects diminished accordingly when oil exposure was reduced or removed.
Whereas the PAH, pyrene, was shown to increase nutrient uptake in bacteria, the findings of Olsen et al. (2007) and Stepaniyan (2008), supported by Petersen and Dahllf (2007), found that the presence of pyrene reduced the photosynthetic rate and nutrient uptake of the benthic algal community.
Hsiao (1978) examined the growth of marine Arctic phytoplankton exposed to crude oils. Four unialgal cultures (diatoms Chaetoceros septentrionalis, Navicula bahusiensis, Nitzschia delicatissima, and green flagellate Chlamydomonas pulsatilla) were randomly selected from a collection of southern Beaufort Sea isolates and maintained on incubator shakers at 200 rpm and 0, 5 and 10C under continuous light, in artificial ASP 2 seawater amended with 1.26 g/mL Na 2 MoO 4 2H 2 O and 192 g/mL NaHCO 3 . Three northern crude oils (Atkinson Point, Norman Wells and Pembina) and one southern crude (Venezuela) were added in volumes of 2, 20, 200 and 2000 L directly to 200 mL of 4.8 10 4 cells/mL of each algal suspension to make test 105
concentrations of 10, 100, 1000 and 10,000 ppm. No chemical dispersant was used and controls contained no oil. Algal growth was assessed every two days by cell enumeration on a Neubauer haemocytometer. Exponential growth rate and generation time were determined. Survival was determined on the basis of pigmentation and motility after ten days of exposure to 10 ppm of the four crude oils at 10C.
Survival of the green flagellate, C. pulsatilla, within the first two days of exposure was 44-68%, which increased with increased exposure time. Growth rate and generation time were not significantly different among the various oils at 10 ppm, although growth was slightly stimulated by Norman Wells and Pembina crudes at 0C. Survival of C. septentrionalis after two days ranged from about 50-90% and decreased continuously thereafter. Survival also decreased sharply with increasing concentration of all oils and growth inhibition increased with increasing exposure time. Survival of N. bahusiensis and N. delicatissima was significantly reduced with increased exposure time, and growth inhibition increased with increased time, temperature and oil concentration.
In general, lethality of the crude oils to the phytoplankton varied with species, oil, temperature and length of exposure. The diatoms (C. septentrionalis, N. bahusiensis, N. delicatissima) were inhibited by a 10 ppm concentration of oil after ten days of exposure at 10C. Longer exposure at 100 ppm, 5 and 10C, caused greater inhibition than at 0C, the diatoms suffering the most. N. delicatissima was the most sensitive, followed by N. bahusiensis and C. septentrionalis. C. pulsatilla (green alga) was the most tolerant. It was able to recover and grow after exposure (unlike the diatoms), with no mortality observed under any of the test conditions. Arctic waters are dominated by diatoms and flagellates, and an oil spill in a habitat occupied by these algal species could result in an overabundance of the green alga (Hsiao, 1978).
The same four crude oils were used to test the effect of the water accommodated fraction (WAF) and chemically enhanced water accommodated fraction (CEWAF, using Corexit dispersant) on natural populations of phytoplankton from the Beaufort Sea and Eskimo Lakes, and on the macrophytic sporophyte seaweeds, Laminaria saccharina and Phyllophora truncata (Hsiao et al., 1978). Results with showed that pimary production by phytoplankton was variously 106
stimulated or inhibited for Beaufort Sea samples at 10 ppm crude. Atkinson Point crude caused about 10% inhibition. The other three WAFs resulted in mean stimulation: Norman Wells, 2%; Pembina, 18%; Venezuela, 8%. For the WAF/CEWAF comparison using phytoplankton assemblages from the Eskimo Lakes, CEWAF caused more inhibition and less stimulation than the WAF, except for Pembina, which showed a mean stimulation of about 8% as CEWAF compared with 10% inhibition as WAF. The authors suggested that the general increase in toxicity of the CEWAF might have been due to the dispersant making the lighter ends and aromatic compounds more available for uptake. Corexit alone caused an average stimulation in photosynthesis of about 18%.
Photosynthesis was consistently inhibited in both macrophytes by all the oils, especially Venezuela crude. Laminaria was most sensitive. The authors note that these results were consistent with those of Hood et al. (1973) who found that 7 ppm of Prudhoe Bay crude inhibited photosynthesis in L. saccharina, Cladophora stimpsonii and Ulva fenestrata. It is suggested that inhibition might be a result of impaired cellular permeability, chlorophyll destruction, chloroplast membrane disruption, accumulation of end products, and blocking of gas exchange (Hsiao et al., 1978).
Salt Marsh Vegetation
Salt marsh plant species of the Arctic that could be impacted by oil spills include the sedges Carex glareosa, C. subspathacea and Eleocharis acicularis; grasses Festuca rubra, Calamagrostis deschampsioides, Puccinella phryganoides; dicotyledons Primula stricta, Stellaria longipes, Parnassia palustris, Chrysanthemum arcticum, Ranunculus cymbalaria; submerged macrophytes Myriophyllum exalbescens and Potamogeton filiformis; mares tail (Hippuris tetraphylla); and low willow shrubs (Logerwell and Baker, 2011).
At Balaena Bay, the experimental oil spill significantly reduced the photosynthetic activity of salt marsh macrophytes and algae by up to 90%, and researchers felt that coastal salt marsh areas, which are important feeding grounds for birds, and nurseries to fish and invertebrates, 107
would be more likely to suffer permanent damage from a spill than a rocky coast (Percy et al., 1985).
Slow recovery of vegetation in colder climates has been attributed to the low temperature (which also reduces the length of the growing season), the high organic peaty soil, sheltered location, and the type of oil spilled which is often fuel oils (NRC, 2003).
Zooplankton
In the Chukchi Sea, between Siberia and Alaska, copepods comprise the most abundant group of Arctic zooplankton along with krill (euphausids) and the meroplanktonic larvae of barnacles and bivalves (ArcOD, 2010; Logerwell and Baker, 2011). There are also the more fragile gelatinous forms which are often underestimated by present sampling techniques, and whose trophic importance is not well known (ArcOD, 2010). Other types of zooplankton include jellyfish, larval finfish (ichthyoplankton comprising about 23 taxa in the Chukchi, dominated by polar cod, Bering flounder and yellowfin sole), and the larvae of many bottom-dwelling invertebrates (Logerwell and Baker, 2011). The zooplankters of the Beaufort Sea are similar to those of the Chukchi Sea, with larvaceans, chaetognaths (tube-like carnivores with a transparent cuticle about 2 to 120 mm), copepods and barnacle larvae in abundance, and polar cod dominating the ichthyoplankton (Logerwell and Baker, 2011).
Relatively little effort has been directed towards studying effects of acute oil spills on zooplankton. A reduction in zooplankton concentrations in a critical area and time period could have significant effects on a large, economically important fish stock. The planktonic life stages (eggs, larval and post-larvae) of cod cohorts are considered the most susceptible to oil spill effects as they have low mobility, restricted horizontal distribution and shallow vertical distribution (Stige et al., 2011). The effects of oil on Calanus finmarchicus, a temperate-boreal copepod found in sub-Arctic waters, and Calanus glacialis, a true cold water Arctic species, were compared. The two species are adapted to 10C and 2C, respectively. They were compared on the basis of acute lethality (LC 50 ), lipid content and the WAF-mediated induction of the gene encoding glutathione S-transferase (GST). LC 50 values
differed between the two 108
species and the Arctic copepod appeared less sensitive than the temperate-boreal species. Lipid- rich copepods survived longer than lipid-poor copepods at the same exposure concentrations. Both species showed trends in GST expression that were dependent on concentration and exposure time. The Arctic copepod appeared to respond more slowly and with a lower intensity. The differences were attributed to the colder temperature rather than inherent differences between the Arctic and temperate species (Hansen et al., 2011). Hjorth and Nielsen (2011) also performed a comparative assessment of faecal pellet production, egg production, and hatching success in Greenland Calanus finmarchicus and Calanus glacialis populations when exposed to oil. During this study the two copepod species were exposed to daily nominal pyrene concentrations of 0, 0.01, 0.1, 1, 10 and 100 nM at water temperatures of 0.5, 5, and 8C for 9 (C. finmarchicus) and 7 days (C. glacialis). While hatching success in both species was unaffected by pyrene exposure, results showed that in C. finmarchicus, faecal pellet production decreased with increased temperature and pyrene concentrations, while C. glacialis showed no negative effect to pyrene over 7 days. Egg production in C. finmarchicus was also negatively affected by pyrene at all temperatures while C. glacialis only showed a dose-dependant decrease in egg production to pyrene at a temperature of 0.5C.
Although the majority of zooplankton toxicology work has been conducted on species found in temperate climates, results are often used to infer the response of Arctic species under similar conditions (Hansen et al., 2011). Research by Jensen and Carroll (2010) shows that in many cases, direct links cannot, and should not be drawn between temperate zooplankton species and their more northern cousins. As they point out, Arctic zooplankton species typically have longer life spans which can lead to increased duration of oil exposure, and contain much higher lipid concentrations allowing them to survive for long periods of time without food. These and other differences between temperate and Arctic zooplankton species should be a clear indication that research focused on Arctic species must be conducted to investigate the effects of oil spills on zooplankton populations.
The lethal toxicity of Norman Wells crude to the jellyfish, Halitholus cirratus, exposed to 2 mL/L was 100% mortality, while mortality for the copepod, Calanus hyperboreas, was only about 10% (Percy et al., 1985). This concentration was used as a worst case scenario. Exposure 109
to Atkinson Point crude caused 30% mortality to H. cirratus, but did not kill C. hyperboreas, whereas exposure to Pembina crude caused 100% mortality in H. cirratus but only 35% to C. hyperboreas. The jellyfish lost its ability to swim due to narcosis induced by the oils. This narcosis was reversible by transferring the animal to clean seawater, as long as the oil dosage was light to medium. The results highlighted the variation in response to different crude oils that is dependent upon oil chemistry.
Results of studies looking at the effects of crude oil WAF on the copepods Calanus finmarchicus (temperate) and Calanus glacialis (Arctic) show that both species are significantly affected by the presence of oil, although in different ways (Hansen et al., 2011; Jensen and Carroll, 2010). Experiments conducted with Calanus finmarchicus show that adult feeding success decreased in the presence of WAF. Studies of Calanus glacialis show that while faecal pellet and egg production in females was initially unaffected by exposure to WAF due in part to their more extensive energy stores, egg hatching success was significantly reduced.
Toxicity tests with the Arctic copepod, Calanus glacialis were conducted by (McFarlin et al., 2011c; 2011d) using WAF and CEWAF prepared from fresh Alaskan North Slope (ANS) crude oil using a modification of a spiked exposure/continuous flow protocol (Aurand and Coelho, 2005), designed to simulate site-specific conditions of Arctic open waters. The Corexit 9500 dispersant was also tested for its toxicity. Biodegradation of chemically and physically dispersed fresh and weathered ANS petroleum was measured by CO 2 production in a respirometer and by GC/MS analysis. Results indicated that the WAF generated under a low energy regime did not have a sufficiently high concentration of TPH to be toxic to the copepod; however, under high mixing energy, the WAF LC 50 as TPH for Calanus was >3.7 mg/L. The CEWAF LC 50 values as TPH for early and late season copepods were 22 mg/L and 62 mg/L respectively (McFarlin et al., 2011c; 2011d).
According to a simulation model for northeast Arcto-Norwegian cod (Gadus morhua) using empirical data, recruitment was highly sensitive to reduction of zooplankton biomass in zones of cod larvae (Stige et al., 2011). Zooplankton, particularly the dominant copepod Calanus 110
finmarchicus, are major prey for the cod larvae and the biomass could be reduced by oil spills, but this is an area requiring study.
Although cod eggs and larvae are affected by 2.5 g/L TPAH (Brude et al., 2010; Stige et al., 2011), it is uncertain how this concentration would affect zooplankton biomass, since C. finmarchicus may be less susceptible to oil components than cod larvae (Stige et al., 2011), and the later stages of Calanus can survive exposure to PAH WAF at 3.5-10 g/L, although at 10 g/L hatching success of C. glacialis was lower, and at 7 g/L C. finmarchicus exhibited reduced feeding (Jensen and Carroll, 2010). C. finmarchicus showed inhibition of feeding and egg production on exposure to 20 but not 2 g/L pyrene, a relatively low toxicity PAH (Jensen et al., 2008). Reduction in copepod nauplii, the main food items for larvae of Arcto-Norwegian cod, G. morhua (Ellertsen et al., 1989), and polar cod, B. saida (Drolet et al., 1991), during their first months of life, could significantly impact cod recruitment; however, we have not found any published studies on the direct effects of PAH exposure to nauplii.
The synergistic effect of ultraviolet (UV) sunlight and 2 g/L TPAH from ANS crude caused photoenhanced toxicity and mortality in Calanus marshallae and Metridia okhotensis, North Pacific copepods (Duesterloh et al., 2002). The interaction of the PAHs and UV radiation was highly significant (p < 0.005). Other effects were impaired swimming, and lipid sac discoloration. There was 80-100% mortality and morbidity of C. marshallae exposed to UV and oil compared to less than 10% effect in oil-only or UV only. For M. okhotensis, 100% mortality occurred in the UV and oil treatment, 43% mortality and 27% morbidity in the UV-only treatment, and less than 5% effect in the oil-only treatment. Bioaccumulation factors were about 8000 for C. marshallae and 2000 for M. okhotensis. Whether bioaccumulation occurs in fish feeding on affected copepods, or how the fish might be affected, is not known.
A laboratory study of ISB of a slick of Norwegian Troll crude showed 33% immobility of C. finmarchicus kept for 96 h in water recovered from under the burn, when the slick was burned immediately (Faksness et al., 2011). When the slick was left for two days and then burned, there was only 19% immobilization. Mortality in either treatment was less than 50%.
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Fish
Arctic seas and adjacent waters contain over 400 species of finfish including marine, diadromous, anadromous and freshwater fish that frequent brackish waters (ArcOD, 2010; Logerwell and Baker, 2011). Of these, approximately 240 species are marine. Common to the Chukchi and Beaufort Seas are capelin, Pacific herring and rainbow smelt. The dominant Arctic families are cods (Arctic, Pacific and saffron), eelpouts, snailfish, sculpins (shorthorn and staghorn), flatfish (Bering flounder, starry flounder, Alaska plaice, yellowfin sole and Greenland turbot) and salmonids. Commercial fisheries do not exist in the high Arctic because traditional methods of collecting fish by trawls do not work well in ice-covered waters. The lack of high- Arctic fisheries catch and by-catch data is a void of basic knowledge (ArcOD, 2010).
Certain species live near the underside of the ice and are noted for having antifreeze compounds in their blood. Most live on or near the bottom. Small fish feed on ice algae and zooplankton. Polar cod (Boreogadus saida) use the underside of the ice as a nursery (Krembs and Deming, 2011). The amphipods dwelling on the underside of the ice as well as planktonic copepods are the major prey for B. saida, which are themselves a key prey of seals, birds and whales (ArcOD, 2010) in the Arctic food web (Figure 23). The polar cod (P. cod in Figure 23), is the most northerly distributed gadid, occurring roughly between 60N and the North Pole, nearshore as well as offshore.
Factors affecting the toxicity of oil spills to fish populations include the physical state of the ocean (especially mesoscale circulation), distribution of spawning sites, length of the spawning season, time of the spill, trophic effects, and chronic sublethal effects of persistent residues (Hjermann et al., 2007). Fish are able to metabolize hydrocarbons fairly quickly therefore bioaccumulation is not thought to affect them (Boyd et al., 2001).
Existing studies on the effects of oil on fish have been largely focused on commercial species such as Atlantic cod, salmon and herring. Stige et al. (2011) noted that juvenile and adult cod are highly mobile and widely distributed, therefore it is unlikely that they would be impacted at the population level by spilled oil. Hjermann et al. (2007) stated that although there is little evidence 112
to date that oil spills have a significant impact on fish stocks, this does not mean that fish stocks cannot be significantly affected by oil spills. The authors noted that the vast majority of the data on large spills comes from temperate and subtropical environments where biological activity is high, ecosystems are complex, and fish tend to spawn for longer period of time compared to species found in the Arctic. Although adult fish are largely able to detect and avoid oil, fish eggs and larvae are not, which means that temporal and spatial spawning characteristics of Arctic fish species are of primary importance. Short and intense spawning seasons and relatively limited (although highly concentrated) distribution of eggs and larvae in the Arctic result in increased susceptibility to the detrimental effects of oil spills. There is also evidence that certain juvenile fish species found in the Arctic such as the polar cod are highly susceptible to decreased zooplankton production as a result of an oil spill (Stige et al., 2011).
Biochemical biomarkers have been frequently used to monitor stress response in fish exposed to petroleum hydrocarbons. Eggs, larvae and juveniles (the most susceptible life stages of fish due to their low mobility and restricted distribution) of Atlantic cod (G. morhua) were exposed to the WAF of North Sea Statfjord B crude oil (40-300 g/L) for 1-6 weeks (Stige et al., 2011) to examine the CYP1A response using an antibody indirect ELISA technique (Goksyr et al., 1991). Monoaromatics (benzenes, toluene and xylenes) dominated the WAF. Exposures that began with the eggs and continued through hatching to larvae showed that induction of CYP1A did not occur during the first days following hatch. After about five days, larvae showed a dose- response induction of CYP1A. Even the low 40 g/L level, which is reasonable for actual spill concentrations, elicited induction. Although petroleum hydrocarbons can accumulate in fish eggs and be transferred to the resulting larvae (Solbakken et al., 1984) the CYP1A system was not immediately induced in the hatchlings (Goksyr et al., 1991). Wong et al. (2011) showed that production water from Canadian east coast platforms can affect fertilization and hatching success in cod eggs but only at high concentrations.
Lyons et al. (2011) measured hepatic ethoxyresorufin O-deethylase (EROD) activity in the Atlantic cod (G. morhua) and showed that water temperature affected the temporal response as well as the absolute level of EROD activity in livers of fish exposed to CEWAF. Fish exposed to CEWAF at 2C showed lower EROD induction than fish exposed at 7C or 10C. The EROD 113
response was also detectable more quickly at the higher temperatures than at 2C. Short-term exposure of juvenile Atlantic cod to WAF and to CEWAF prepared with chemical oil dispersant formulations significantly increased EROD activity (Lee et al., 2011b). Maximum EROD induction occurred at 24 hours post-exposure and remained elevated over the next 48 hours compared to controls. As expected, oil dispersants which elevated the concentrations of oil in the water induced higher levels of EROD activity.
Two studies have examined EROD inducibility in the anadromous species, Arctic charr (Salvelinus alpinus). Jrgensen and Wolkers (1999) measured hepatic EROD activity in winter- and summer-acclimated charr at two temperatures, 1 and 10C. Strong EROD induction was observed 2, 6, 12 and 23 days following one oral dose of 60 mg benzo[a]pyrene (BaP) per kg body weight. Induction was delayed and prolonged in the lower temperature group but showed comparable levels of induction. The magnitude of induction was seven times greater in the summer experiments than the winter ones. The authors concluded that Arctic charr are a suitable species for oil and gas monitoring in the Arctic. This conclusion was supported by Jonsson et al. (2003) who also reported strong EROD induction in gill filaments of Arctic charr, but not spotted wolfish (Anarhichas minor), following a 48-hour exposure to the model PAH, -naphthoflavone. The results of these studies suggest that Arctic charr may indeed be a good indicator species, and EROD induction a good biomarker for monitoring Arctic petroleum impacts.
Three consecutive year classes (1990-1992) of pink salmon fry (Oncorhynchus gorbuscha) that had been exposed for ten days to seawater containing either 2554 g/L or 178349 g/L of WAF North Slope crude oil were released into the Pacific Ocean where they completed their life cycle (Birtwell et al., 1999). The WAF was composed primarily of monoaromatics. Preliminary tests revealed that concentrations higher than the exposure solutions were acutely lethal to the fry (96-h LC 50 = 1 to 2.8 mg/L). There had been no effect from the exposures on the survival and growth of the fry before their release. The fish were tagged, and adults that returned to their natal river in British Columbia did not show any detectable deleterious effect on growth or survival compared to unexposed controls.
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Pink salmon embryos are sensitive to 1-20 ppb PAH (Carls et al., 2001b; Heintz et al., 1999) showing abnormalities comparable to Pacific herring embryos (edema, damage to skeleton, fins and chromosomes). The effects apparently are cumulative across the life stages of an individual resulting in a 50% mortality before being able to reproduce (Carls et al., 2001b). Pink salmon incubated in oiled gravel that amounted to TPAH exposure of 5 and 19 mg/L (low and high dose) were not found to stray from their natal stream any more than controls which had been incubated in unoiled gravel (Wertheimer et al., 2000). The tagged fish in the exposed groups were found straying with frequencies of 0.030 and 0.025 for the low and high dose treatments respectively. The control fish strayed with a frequency of 0.023. Differences among treatments were not statistically significant. Their results do not support the hypothesis that oil exposure of embryos in intertidal spawning grounds was responsible for the high rates of straying of wild stock pink salmon that were observed in PWS after the Exxon Valdez oil spill (Wertheimer et al., 2000). Nevertheless, there is a burden of evidence that points to oil from the spill causing elevated embryo mortalities and elevated CYP1A levels in larvae from streams oiled by the spill (Carls et al., 2001b).
PAHs are known as the most toxic constituents of oil and petroleum related-products (Carls et al., 2001b; Heintz et al., 1999). Fish embryos exposed to PAHs have shown mortality, edema, haemorrhaging, cardiac disruption and deformities all of which seem to be due to high bioaccumulation and limited biotransformation. Weathered oil retains the heavier 3 and 4-ring PAHs. In low 0.4 part per billion (ppb) TPAH concentrations, these have been shown to cause increased mortality, abnormalities, poor swimming, decreased incubation time and reduced length-at-hatch in Pacific herring eggs exposed for four or 16 days (Carls et al., 1999). Edema and defects in chromosomes, skeleton and finfolds were observed.
Barron et al. (2004) tested mechanistic models for the chronic toxicity of complex mixtures of PAHs in Pacific herring (Clupea pallasi) and pink salmon (O. gorbuscha) embryos from southeast Alaska. The four models tested were: narcosis, AhR agonism, alkyl phenanthrene toxicity, combined toxicity. Of these models the alkyl phenanthrenes were the primary cause of early life stage sublethal toxicity in both species tested. This model predicted toxicity with 67- 80% accuracy. Naphthalenes were primarily associated with narcosis which contributed most to 115
embryo mortality. Because of very low concentrations of potent AhR agonists, these PAHs did not contribute significantly to early life toxicity. It was concluded that the alkyl phenanthrene (C2 to C4) component of complex PAH mixtures can be used to predict significant toxic effects to early life stages of pink salmon and Pacific herring, but the model predictions did not account for exposure time due to limitations in the data (Barron et al., 2004). Although the alkyl phenanthrene model was a good predictor of toxicity, the authors recommend the use of TPAHs to quantify exposure until these mechanistic models can be tested further.
Toxic effects on embryos have been found to be associated with the concentrations of alkyl PAH (Hodson et al., 2007) which comprise more than 90% of the TPAH in petroleum. TPAH has been recommended for continued use as a metric of exposure, because although it is simple and does not depend on the differences in PAH composition or differences in potency, TPAH values were found to correlate well with toxic effects observed in pink salmon and Pacific herring (Barron et al., 2004).
Osmoregulatory function of the gills and cellular volume regulation were measured in European flounder (Platichthys flesus) from Oslofjord, Norway, exposed to lethal or sublethal concentrations of dispersant alone (Corexit 9527) or a dispersant-to-oil ratio (DOR) of 1:1, mixed with North Sea crude (Baklien et al., 1986). The concentrations tested in the 14 day sublethal experiment were 20 ppm of Corexit alone or a DOR of 10 ppm:10 ppm crude. For the 96 hour lethality study, 80 ppm Corexit alone was used, or a 40 ppm:40 ppm crude oil mixture. In addition to survival, the following blood parameters were measured: osmolality, haematocrit, plasma Na, plasma K, plasma Ca, plasma Mg, plasma Cl, plasma protein and plasma total free ninhydrin positive substances. The lethality study produced approximately 50% mortality. Blood parameters in fish surviving the oil-dispersant mixture were all significantly elevated as were most parameters in the dispersant exposure alone (except for haematocrit, plasma K or plasma Cl). However, exposure to sublethal concentrations of the dispersant or the oil-dispersant mixture did not significantly elevate these blood parameters indicating that these stress factors only become elevated prior to death and are consequently not good biomarkers for sublethal testing (Baklien et al., 1986). It should also be noted that a DOR of 1:1 is not the currently recommended dosage for field applications, but rather 1:20. 116
Oil related pathologies were also assessed by Lukin et al. (2011) in two species of freshwater fish in sub-Arctic Russia. These authors studied the health of these fish in the Pechora River which received a multitude of pollutants including chronic oil spills such as from the largest oil spill in Russian modern history (ca. 100 000 tons) in 1994. The objective of this study was to evaluate the use of histopathological abnormalities in fish as an indicator of environmental quality. These abnormalities were measured in the gills, liver and kidneys of ide (Leuciscus idus) and whitefish (Coregonus lavuretus). Results indicated that these lesions were caused by direct toxicant effects and secondary stress effects (parasitism). The authors concluded that the impacts observed in these fish were caused by both acute (short-term) and chronic (long-term) exposures to pollutants in the Pechora River. Of the two species tested, whitefish appeared to be the more suitable indicator. The authors noted that while these histopathological lesions have been observed in other studies, and could be caused by a variety of contaminants, some were directly linked to oil contamination in the river. It has been suggested that the migration of petroleum hydrocarbons from a spill into brackish waters of Arctic estuaries would increase the risk of impacts since oils seem to be more toxic in freshwater than saltwater (ESL Environmental Sciences Limited, 1982).
Pacific sand lance (Ammodytes hexapterus) are an important benthic fish that form a link between the zooplankton and upper trophic levels of the Arctic food web (Moles and Wade, 2001). The larvae serve as prey for salmon, while groundfishes feed on both the larvae and adults. The sand lance is also an important prey of Arctic birds and mammals. Adults collected from southeast Alaska were exposed to weathered ANS crude oil contaminated sediments for three months at sediment concentrations of 10 and 61 g TPH/g (Moles and Wade, 2001). Superoxide production, phagocytic function and gill parasites (Gyrodactylus sp.) were quantified at the end of the exposure period. Fish produce superoxides to catabolize compounds that result from the phagocytic action of leucocytes. Moles and Wade (2001) found that sand lance exposed to the lower concentration (10 g TPH/g) had increased superoxide production and phagocytic activity, with a corresponding decrease in the presence of the parasitic trematode, Gyrodactylus sp. In the other treatment using 61 g TPH/g, the sand lance exhibited decreases in both superoxide production and phagocytosis (decreased immune response), with an increase in 117
occurrence and abundance of Gyrodactylus. The differences were statistically significant (p < 0.05). These authors suggested that low levels of oil may stimulate the immune system which results in lower numbers of gill parasites, but higher concentrations may overwhelm the immune system resulting in higher levels of infection. These low concentrations of TPH are similar to what can be expected in subtidal regions following an oil spill. Increases in Gyrodactylus were also found in Atlantic cod exposed for four months to crude oil WAF (Khan and Kiceniuk, 1988).
Phototoxicity is emerging as an issue of concern as the toxicity of PAH and weathered oil has been reported to increase with a factor of 2 to over 1000 in the presence of sunlight (Barron et al., 2003). There are extended periods of light and darkness in the Arctic. The consequences of these extreme shifts in photoperiod on biological effects have not been studied to any extent. Many species at the lower end of the food chain are most prevalent during periods of extended daylight hours. It is possible a spill of oil during the Arctic summer would not only affect a large number of species but the toxicity of the oil could be increased by the production of toxic products of photodegradation.
Photo-enhanced toxicity of WAF and Corexit 9527 CEWAF of weathered ANS crude oil was studied in eggs and larvae of Pacific herring (C. pallasi) from Sitka Sound, Alaska (Barron et al., 2003). At test concentrations below 50 mg TPAH/L, median values for LC 50 and for the effective concentration affecting 50% of test organisms decreased with time after initial oil exposure, and brief exposure to sunlight for 2.5 hours on each of two days significantly increased toxicity 1.5 to 48 fold. Ultraviolet radiation-A (400 nm - 315 nm) treatments combined with sunlight induced the greatest phototoxicity. The toxicity of chemically dispersed oil which accelerated PAH dissolution into the aqueous phase was also significantly more toxic in sunlight. For chemical dispersion exposures, the 96-hour no-observed-effect concentration in the presence of UV-A and sunlight was 0.2 mg TPAH /L. Hence, weathered ANS is phototoxic and UV can be a significant and causative factor in the mortality of early life stages of herring exposed to oil and chemically dispersed oil. Barron et al. (2003) noted that most studies do not consider the effects of phototoxicity and therefore may underestimate potential impacts of spilled oil. 118
Phototoxicity can be particularly important for pelagic species such as herring which inhabit the photic zone and have translucent eggs and larvae, which allow UV penetration.
Weathered crude oil can cause immunosuppression and viral haemorrhagic septicemia in Pacific herring (Hjermann et al., 2007). It is suspected that this was a factor in the collapse of the Pacific herring industry following the Exxon Valdez spill, when the 1989 year class was exposed to oil at the egg stage, and subsequently displayed a high incidence of viral haemorrhagic septicemia as well as extremely low survival to spawning age.
In Pacific herring embryos from central Puget Sound, Washington, the primary target of crude oil toxicity is the heart (Incardona et al., 2009). Pacific herring exposed to effluent from oiled gravel columns showed defects in the heart rate and rhythm as soon as regular heart rhythm could be observed (five days post-fertilization). This cardiac dysfunction was produced at low PAH tissue burdens of only 0.8 mol/kg (total tricyclics). Consequently, for oil related impacts, the authors recommended biomarkers which related to cardiac performance such as CYP1A or levels of fluorescent aromatic compounds in bile.
Exposure to 2 mL/L of Norman Wells crude resulted in 100% mortality of the juvenile stage of the fourhorn sculpin, Myoxocephalus sp. (Percy et al., 1985). In addition to the immediate mortality effects associated with contact between fish and oil, perhaps a more worrying issue is potentially longer lasting sublethal effects. Studies show that ingestion and absorption of oil by B. saida, which is highly possible since they feed on epontic biota that could accumulate oil from pooled oil under the ice, imposes a significant metabolic burden on exposed individuals which is readily detectable through the analysis of various types of biomarker responses (Christiansen et al., 2010; Jonsson et al., 2010; Nahrgang et al., 2010b; Nahrgang et al., 2009; Nahrgang et al., 2010d).
Much of the research involving potential impacts of oil and gas related activities in the Arctic region has focused on polar cod (B. saida). Baseline knowledge and toxicological studies on this species provide useful information on its potential use in future biomonitoring programs for the Arctic oil and gas industry for these reasons: the Arctic food web is relatively simple and 119
seasonal; these cod have a circumpolar distribution; and baseline levels of bile PAH-metabolites and liver EROD were found to be very low but highly responsive to petrogenic exposure. Polar cod were recommended as an indicator species by the Arctic Monitoring and Assessment Programme (AMAP, 2008; Stange and Klungsr, 1997) because of its low trophic level diet (zooplankton) and its short lifespan, which provides a better indication of immediate conditions. Furthermore, water column monitoring near oil installations in the Norwegian Sea and the Grand Banks have utilized its temperate counterpart, the Atlantic cod (G. morhua), to quantify environmental effects of their effluent, produced water.
It is important to determine differences in sensitivities within the Gadidae family because fish inhabiting sub-Arctic and Arctic regions may be more sensitive to chemical insult as a consequence of their adaptations to survival in freezing waters (Christiansen et al., 2010). Because of these adaptations, Arctic fish may be particularly at risk from additional stressors such as petroleum activities. Hjermann et al. (2007) also noted that, because of low water temperatures, the physical and biological processes involved in oil degradation may be slower in Arctic waters, hence increasing the duration of exposure to oil. These authors also point out that the simplicity of polar ecosystems renders them more vulnerable to collapse if there are changes to some of the keystone species. It is hypothesized that decreased recruitment of polar cod is likely to be the major impact on the cod stocks of an oil spill in the Arctic (Logerwell and Baker, 2011). Because it is a keystone species, the effects of cod mortality, reduced recruitment and reduced production are expected to cause changes in community structure, trophic alterations due to reduced prey for dependent species and less food for humans.
Polar cod (B. saida) and larval sculpin (Myoxocephalus sp.) were exposed to WAF and CEWAF of fresh ANS using a spiked exposure regime to simulate an oil spill. Oil was added at a given concentration followed by dilution with a continuous flow of clean seawater (McFarlin et al., 2011c; 2011d). The exposures with oil and the chemical dispersant Corexit 9500 were conducted in open systems to permit the evaporation of volatile organic compounds that would normally occur. Biodegradation of chemically and physically dispersed fresh and weathered ANS was measured by CO 2 production in a respirometer and by GC/MS analysis. WAF generated under a low energy regime was toxic to the cod and larval sculpin (LC 50 = 1.6 and 2.2 120
mg TPH/L respectively). Under high mixing energy, the WAF LC 50 for polar cod was 3.3 mg TPH/L. The CEWAF LC 50 for cod was 55 mg TPH/L, and 27 mg TPH/L for the larval sculpin.
Effects of produced water on Atlantic cod living in the Norwegian Sea have been monitored using PAH biomarkers (Hylland, 2006). Nahrgang et al. (2010b; 2009; 2010c; 2010d) examined the applicability of these biomarkers to polar cod in a series of experiments. Polar cod were exposed to BaP by intraperitoneal injection (Nahrgang et al., 2009). PAH biomarkers tested for gene transcription analyses included -Actin, CYP1A-1, AhR-2, pi-class homolog of glutathione S-transferase (GST), Cu/Zn-superoxide dismutase, Mn-superoxide dismutase, catalase and glutathione peroxidase. Protein analyses included microsomal CYP1A, cytosolic GST and catalase proteins. EROD was also quantified. All biomarkers were successfully measured in polar cod but enzyme activities were the least reliable.
To further determine the applicability of these biomarkers to complex mixtures such as oil, and through more realistic exposure conditions, Nahrgang et al. (2010b) exposed polar cod to environmentally relevant concentrations of WAF of North Sea crude oil using oiled rock columns. Molecular and biochemical biomarkers tested were similar to those in the Nahrgang et al. (2009) study. The most responsive biomarkers were CYP1A-1 mRNA expression and EROD activity. The authors recommended that GST-mRNA expression and GST enzyme activity be used as complementary biomarkers, while the antioxidant defense biomarkers were deemed inappropriate for monitoring purposes. EROD and GST induction were delayed and were still elevated after 2 weeks of depuration.
Nahrgang et al. (Nahrgang et al., 2010c; Nahrgang et al., 2010d) also tested the response of the suite of molecular biomarkers following a dietary exposure to North Sea crude oil. Polar cod from Rijpfjorden, Svalbard, were fed for four weeks a diet of pelagic amphipod (Themisto libellula) blended with gelatine powder and North Sea crude oil for final concentrations of 0.5 and 2 mg crude/g. This was followed by two weeks of depuration, being fed the control diet of T. libellula blended with gelatine alone. The diet having concentrations of 0.1, 18.0 and 43.3 g TPAH/g in the control, low dose and high dose respectively, was readily received by the cod. Expression of the mRNA for CYP1A-1 in the exposed fish was strongly induced, up to 60 that 121
of the control for the high dose from two to four weeks, and returned to normal after the two- week depuration. Expression of mRNA for the cytosolic pi-class homologue of GST followed a similar pattern only for the high treatment (3 the control and returning to normal). Expression of antioxidant genes showed no difference from controls over the course of the experiment. Liver EROD increased by a factor of 10-12 in low and high treatments (about 30-50 pmol/min/mg protein), and falling during the two weeks of depuration to normal (about 2-4 pmol/min/mg protein) for the low treatment, but remaining significantly above normal for the high oil treatment (about 8 pmol/min/mg protein). Synchronous flourescence scan spectrometry of the bile in exposed fish indicated the presence of PAH metabolites of naphthalene, pyrene and BaP in a dose-dependent manner, with maxima at week two, decreasing by week four, and returning to control levels after two weeks of depuration. Responses of the molecular biomarkers were similar to those observed following the WAF exposure leading to similar conclusions on the usefulness of the various biomarkers tested. The similarity in the results of these studies demonstrates the consistency of the response of these molecular biomarkers and validates their use for biomonitoring studies.
High levels of BaP in water-exposed B. saida have been found partitioned into gills, olfactory organ, kidney, skin, intestinal mucosa and liver (Ingebrigtsen et al., 2000). The highest concentration was found in the bile. Partitioning occurred in epithelial cells in which CYP1A activity takes place (Jnsson et al., 2003). Uptake of radioactive 3 H-BaP (mixed with unlabelled BaP to give a concentration of 1 L/L) was predominantly from the water through the gills, metabolism principally occurred in the liver, and excretion of metabolite was by way of bile (Ingebrigtsen et al., 2000).
The cod accumulated BaP at -1C, which is not unusual since these fish have a very high assimilation efficiency of about 80% (Hop et al., 1997) and long gastric half times ranging from 36 hours to 12 or 13 days at -1.4 to -0.5C (Hop and Tonn, 1998). The gastric evacuation rates for polar cod are much longer than for Atlantic cod (about 13 hours). Evacuation rates for starved polar cod are even longer (Hop and Tonn, 1998). In spite of the slow evacuation rates, food contaminated with oil (and PAH) was evacuated in less than two weeks, with complete excretion of PAH metabolites from the bile (Nahrgang et al., 2010c). 122
Digestive processes are slower at sub-zero temperatures and this might limit daily food intake when food is abundant (Hop and Tonn, 1998). Polar cod have slow growth rates (0.15-0.25% body weight per day, although this is faster than snailfishes), so the high annual production of these fish is mainly because of their high growth efficiency and large standing crop (Hop et al., 1997). These cod grow faster on Calanus copepods than on Themisto amphipods, and their high growth and assimilation efficiencies at low temperatures makes them efficient converters of energy between the zooplankton trophic level and the higher trophic levels of marine birds and mammals (Hop and Tonn, 1998; Hop et al., 1997).
To further validate the use of polar cod as an indicator species, Nahrgang et al (2010d) measured EROD activity in gills and liver following dietary and waterborne exposures. This was the first study to measure EROD activity in gills of polar cod, one of the primary tissues to uptake pollutants (Ingebrigtsen et al., 2000). EROD levels in both the gills and the liver were significantly increased by both exposure routes, were dose-dependant, and were higher in the liver than the gills. Time of exposure was indicated better by the gills than liver but the response threshold was higher with gill tissue which could prove problematic for field monitoring of low PAH levels and particularly in the presence of potential environmental confounding factors (Nahrgang et al., 2010d).
The biochemical biomarker CYP1A has also been examined in polar cod (George et al., 1995). Because CYP1A induction has been shown to be reduced or absent at low temperatures the authors questioned the validity of this biomarker for cold Arctic regions. However, CYP1A can be induced at 0-6C in male and female polar cod during sexual maturation, by -naphthoflavone or crude Oseberg C mineral oil (George et al., 1995). Polar cod (B. saida) from the Barents Sea and off Svalbard were kept at 3-6C and fed a diet contaminated with 0.2 mg/g crude oil for 52 days. At sexual maturity, the females showed diminished CYP1A activity, which has been demonstrated in many other fish species. Following a three-week depuration, the fish were sacrificed for EROD analysis. Controls at the start of the experiment ranged from 28-31 pmol/min/mg protein. Sexually mature females at 72 days had an EROD activity of 8 2 pmol/min/mg protein. EROD activity for exposed males at 72 days was 132 14 compared to 123
females which measured 42 6 pmol/min/mg protein. The study showed that sexual maturation in female polar cod does not suppress the CYP1A system. In spite of the fish having ceased feeding three weeks prior to the end of the experiment (the depuration phase) because they naturally do this in preparation for spawning, they continued to assimilate the ingested food (up to two weeks before clearance at low ambient temperatures), and therefore the inductive effect of the oil in the diet was prolonged (George et al., 1995). This study clearly demonstrated that the CYP1A enzyme system was induced by common inducers in both males and females during their sexual maturation at a temperature of 0C. Christiansen and George (1995) also showed that crude oil dietary exposure did not impair the overall feed intake of exposed polar cod, despite growth reduction in exposed fish.
Whole body metabolism, inferred from oxygen consumption rates (respirometry), of polar cod exposed acutely for about 60 minutes and chronically for 4 weeks to the WAF of North Sea petroleum was tested by Christiansen et al. (2010). This biomarker reflects the stress and bioenergetic costs of petroleum exposure. The authors expected oxygen consumption to increase in exposed cod but both chronic and acute exposure actually resulted in reduced routine metabolism. A review included in this paper demonstrated the variability (increase, decrease and non-response) of this biomarker among fish species, indicating the necessity of species-specific calibration.
Another potential biomarker, DNA adducts, are pieces of DNA covalently bonded to carcinogenic chemicals. Because DNA adducts can be caused by PAH exposure, Aas et al. (2003) established baseline levels of DNA adducts in the livers of 11 Arctic and sub-Arctic fish species, including polar cod, from pristine areas. The technique employed in this study (the nuclease P1 version of 32 P-postlabelling) was selected because it can detect DNA adducts caused by PAHs. In all species, DNA adduct levels were undetectable. Laboratory exposure to BaP and to crude oil caused the induction of DNA adducts in polar cod, which validated the use of this biomarker and the nuclease P1 version of the 32 P-postlabelling technique as a tool in oil and gas monitoring studies.
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Polar cod (B. saida) from Svalbard were exposed for two weeks to 1 mg/L dispersed, crude Statfjord A, in a continuous flow system (Jonsson et al., 2010). The WAF was analyzed for 26 PAH species (EPA 610 protocol) and was primarily composed of 2 and 3-ring PAHs. The sum of these was 19.9 g/L, while the concentration of the 2-ring PAHs ranged from 1.28 to 6.79 g/L, and for 3-ring was 0.005 to 0.408 g/L. Examination of exposed fish revealed BaP-type metabolites in bile, indicating metabolism of PAHs. The 5-ring PAHs had been bioconcentrated from the water into the fish. Control fish were found to have very low levels of bile PAH- metabolites, in the range of 1899-1940 ng/g for the sum of the means of naphthalenes, phenanthrenes and pyrene, compared to exposed fish that had a mean sum of about 202,000 ng/g. The highest EROD liver activity in control fish was 5.7 pmol/min/mg protein, while in the exposed group, the values ranged from 9.5-80.7 pmol/min/mg. Hepatic DNA-adducts (DNA bound to a carcinogen) were low in control cod (mean of about 0.4 nmol adducts/mol normal nucleotides) compared with the exposure group (12.2 3.5 nmol adducts/mol normal nucleotides), indicating that exposed fish could potentially suffer genotoxic effects and therefore, cancer. EROD and DNA-adduct values were highly correlated, which is grounds for using the EROD assay alone instead of the more complex DNA-adduct assay. PAH-metabolites in the bile and CYP1A induction (EROD) in the liver of polar cod were suggested as useful biomarkers (Jonsson et al., 2010).
Xenobiotic excretion patterns of polar cod were described by Christiansen et al. (1995). In fish, foreign chemicals are primarily excreted via urine and bile. Xenobiotics and their metabolites excreted via urine are filtered in the glomerulus and secreted by tubular transport within the kidney. Unlike most fish species, including Atlantic cod, polar cod display a complete absence of the glomerular apparatus. Consequently, Atlantic cod excreted an inert, model polysaccharide solely in the urine while polar cod excreted it in the bile.
To our knowledge only one study has reported acute toxicity concentrations of oil for polar cod (Carls and Korn, 1985). The reported LC 50 was 1.6 ppm total aromatic hydrocarbons in WAF of Cook Inlet crude oil, reaching a stable LC 50 after five days exposure. Polar cod responded most quickly and proved most sensitive among six Arctic species tested which included three species of amphipod, a mysid, and a sculpin. Polar cod were also most sensitive to the aromatic 125
reference toxicant, and constituent of Cook Inlet crude oil, naphthalene with an 8 day LC 50 of 1.35 ppm.
Also lacking is information on effects of oil (or PAH) exposure on the embryonic and larval stages of polar cod. Because these ichthyoplanktonic life stages have limited mobility, they are most vulnerable to localized environmental insult, such as oil spills or an influx of produced water. Early life stages, being periods of rapid development and morphological re-organization, are particularly sensitive to chemical exposure (Weis and Weis, 1989). Adults spawn under the ice in nearshore waters from November to March and the buoyant eggs remain at the surface until hatch, after which the young-of-the-year larvae continue to reside near the surface to feed for several months (Sekerak, 1982). Exposure routes would be adsorption (direct contact), absorption through skin and gill membranes, and ingestion. There are no field data for egg and larval exposure, and few laboratory studies have been done (Logerwell and Baker, 2011). This knowledge gap is significant, since polar cod can be considered a keystone species (Figure 23).
As noted by Hjermann et al. (2007), some species of fish in the Arctic such as Atlantic cod and herring, are close to their climatic boundary and environmental conditions in these habitats may limit their spawning season to short, intensive and localized spawning events. Consequently, these populations may be at greater risk if a spill were to occur during their spawning season. In addition to the morphological and genetic abnormalities that PAHs are known to cause, they might also be responsible for disruption of complex behaviour such as predator avoidance, and reproductive and social behaviour in adult fish which have been exposed to PAHs during their early life stages (Hjermann et al., 2007).
Benthic Invertebrates
Dead ice algae falls off the under surface of ice and sinks, along with other dead organisms and fecal pellets, providing food for a complex benthic ecosystem on the aphotic sea floor that is home to over 90% of the approximately 5000 species of Arctic marine invertebrates (ArcOD, 2010). On the continental shelves, crustaceans (amphipods, sand fleas, crabs), polychaetes (bristle worms) and bivalves (clams and mussels) dominate the sediment infauna (ArcOD, 2010; 126
Blanchard et al., 2010). The larger epibenthic animals are usually dominated by brittle stars with up to several hundred individuals per square metre. Other epifauna include sea cucumbers, gastropods, ascidians, sponges, bryozoans, hydrozoans, shrimp, starfish, sea anemones, sea urchins and hermit crabs.
Food supply rather than water temperature is the limiting factor for the Arctic benthic community (ArcOD, 2010). In certain of the shelf areas such as the Chukchi and Bering Seas, the benthos consists of an abundant and diverse community (Logerwell and Baker, 2011) including large worms, bivalves and amphipods which are prey for gray whales, bearded seals and walruses (Blanchard et al., 2010). These macrofauna are supplied mainly by pelagic and ice- edge sources (Figure 22) such as senescent phytoplankton (Aydin et al., 2002). Food availability and benthic biomass in deep Arctic basins are much lower, although the major animal groups, comprising about 350-400 species, are similar to those of shelf regions.
The BIOS Project in the Canadian Arctic provided an opportunity to collect nearshore benthos data systematically from the same area over a four-year period (Snow et al., 1987). Chemically dispersed and undispersed crude oil was spilled in shallow bays. Bivalve molluscs, Mya truncata and Macoma calcarea, were examined for histopathological and biochemical responses. Mya truncata (blunt gaper edible saltwater clam) were collected for biochemical analysis immediately before, immediately after and two weeks after the simulated spills. Concentrations in the clam tissues of glucose, glycogen, trehalose, total lipid and free amino acids were measured. The results of the biochemical analyses indicate that Mya from the bays were not severely stressed by either dispersed oil or oil alone. It was concluded that the acute effects of dispersed oil are greater than those of undispersed oil, but effects of undispersed oil on infaunal molluscs develop more slowly and persist longer than those from dispersed oil (Neff et al., 1987). Humphrey et al. (1987) examined the fate of chemically dispersed and untreated crude oil in Arctic benthic bivalves and urchins. Physiological parameters measured in bivalves exposed to oil included elements of scope for growth, activity of aspartate aminotransferase and glucose-6-phosphate dehydrogenase. Dose-response relationships between physiological rates and hydrocarbon body burden were apparent. Depuration of the stored hydrocarbons occurred during the experimental 127
recovery period. Furthermore, in vivo biodegradation of hydrocarbons was indicated in the bivalves.
Presently, there have been no surveys of the Arctic salt marsh benthos. Benthic communities of the intertidal zone are at risk of direct oiling, which in addition to the toxicity of the WAF containing organic compounds, can simply smother the biota (NRC, 2003). The subtidal benthos consists of oligochaetes, midge larvae, amphipods and isopods (Logerwell and Baker, 2011). In both the intertidal and subtidal zones, the most sensitive organisms tend to be the crustaceans (Dean and Jewett, 2001; NRC, 2003). Residual Exxon Valdez oil in the intertidal zone of Latouche and Evans Islands is suspected to be putting the intertidal invertebrates and other species at risk, but effects have not been examined; however, oil under the soft sediments of mussel beds that have resulted in PAH-contaminated mussels indicates the bioavailability of the residual oil, and the potential for contamination of higher trophic level species that feed upon mussels (Carls et al., 2001a).
Two polychaetes species, Capitella capitata and Cirratulus cirratus, which inhabit sediments of the Beaufort Sea are resistant to pollution in general, more specifically, are resistant to effects from fuel oil (ESL Environmental Sciences Limited, 1982; George, 1971). C. capitata has been shown to accumulate and metabolize benz[a]anthracene, and this metabolic pathway can be induced by exposure to oiled sediments (Forbes et al., 2001).
The gammarid amphipod, Gammarus setosus, common to the intertidal zone of Svalbard, exhibited about 60% less stability of lysosomal membranes when exposed to chemically dispersed, naphthenic rich Norwegian crude oil (Troll) for 12 d (Faksness et al., 2011). This is an indicator of stress. Lipids in the gammarids suffered peroxidation by day 12 in WAF and CEWAF treatments, but the animals recovered after another 13 days in the flow-through system. The mean body burdens of semi-volatile organic compounds from WAF and chemically dispersed treatments were about 1.8 and 5.6 g/g respectively on day 12, decreasing to about 0.25 and 0.6 g/g by day 25. The authors state that differences in response between temperate and Arctic benthic communities is likely due to different community structure, sensitivity of individual taxa, and different contamination history of the two areas. 128
Typical biomarker responses developed for temperate species may be affected at cold temperatures. Olsen et al. (2007) looked at benthic community response to petroleum-associated components in Arctic versus temperate marine sediments. In addition to a control, two oil concentrations were used for the study. After 21 days of incubation, significantly higher sediment oxygen demand was measured in the Arctic high oil concentration (1.6 mL oil/kg) sediment cores, and sediment cores injected with drill cuttings, compared to Arctic control cores. In the temperate cores no significant differences were seen. The variance in response was likely related to differences in the benthic community structures, sensitivity of individual taxa to oil- related compounds and contamination history of the two areas.
Alterations in the energy budget of a bivalve, Liocyma fluctuosa, and two Arctic amphipods, Gammarus setosus and Onisimus litoralis, exposed to oil-related compounds were investigated (Olsen et al., 2007). The cellular energy allocation biomarker measures the energy budget of organisms by biochemically assessing changes in carbohydrates, protein and lipid content as well as the electron transport system activity. Significantly lower cellular energy allocation values and higher electron transport system activity as the cellular aspect of respiration were observed in Gammarus setosus subjected to WAF of crude oil and drill cuttings compared to controls. Higher cellular energy allocation value and lower cellular respiration were observed in Onisimus litoralis exposed to drill cuttings compared to controls. No difference in the energy budget of Liocyma fluctuosa was observed between treatments. Different responses to oil-related compounds between the three test species were likely the result of differences in feeding and burrowing behaviour and species-specific sensitivity to petroleum-related compounds (Olsen et al., 2007).
Studies on the effects of oil pollution on the sea ice amphipod G. wilkitzkii have taken place because of increased petroleum related activity in the Barents Sea of the European Arctic. Hatlen et al. (2009) exposed the amphipods to a low and high dose of the WAF of oil for 36 days and for 113 days, and saw a dose-related significant increase in respiration rate. Sublethal effects were seen for the low dose group using the biomarkers malondialdehyde and total oxyradical scavenging capacity (TOSC). Cellular energy allocation was measured in sea ice amphipods 129
after a one month exposure to a high, medium or low dose of WAF of oil. Significantly higher protein content was observed in the medium dose compared to controls. The total energy budget was not affected in G. wilkitzkii (Olsen et al., 2008). Camus and Olsen (2008) exposed female G. wilkitzkii to a high, medium and low dose of WAF of crude oil for 30 days and their embryos were scored for abnormalities. The frequency of embryo aberrations was significantly higher in the high-dose compared to controls.
The amphipod Boeckosimus affinis, widespread in the North American Arctic, was exposed to the WAF of Prudhoe Bay crude oil and survival, movement and food search success was monitored. Mortality was correlated to the strength of the solution and chronic exposures were more detrimental than one-time exposures. Movement and time spent moving decreased as the concentration of WAF increased in the chronic exposure experiments. Animals that were exposed once moved less distance but the time spent moving was not decreased. Feeding success of the amphipods was also reduced after exposure to the WAF of crude oil but animals exposed just once showed recovery in feeding success after removal of the pollutant (Busdosh, 1981). The Arctic amphipods Gammarus zaddachi and Boeckosimus affinis, the dominant amphipod species in coastal pond and marine lagoon ecosystems were exposed to Arctic diesel and the WAF of Prudhoe Bay crude oil in bioassays. Mortality and respiration, sensitive indicators of an animals physiological and metabolic state were measured. It was determined that spills of crude oil or refined oils in the Arctic are likely to cause large-scale mortality in the region of the spill, resulting in serious ecological changes in decomposition processes and food-web relationships (Busdosh and Atlas, 1977).
Gammarus oceanicus, sympagic amphipods, were collected from the tidal zone in Kongsfjorden, Svalbard, and exposed in the laboratory to WAF, CEWAF and emulsion (a constantly mixed test tank of CEWAF) of Statfjord A+B crude oil, and the dispersants Finasol OSR-5 and OSR-12 (Aunaas et al., 1991). The DOR was 1:1 using Finasol OSR-12 and 1:10 using Finasol OSR-5 according to the manufacturers recommendations. Test concentrations in the sublethal exposure experiments were based on preliminary acute toxicity experiments to establish LC 50 values, and using concentrations that fell within the LC 50 range of 0-10%. The concentrations of WAF were 20% for crude oil, 10% for OSR-5 and the crude oil + OSR-5, and 100% for OSR-12 and crude 130
+ OSR-12. The concentrations used in sublethal exposures to water emulsions were 30 mg/L crude oil, 20 mg/L Finasol OSR-5, 300 mg/L Finasol OSR-12, 200 mg crude oil + 20 mg OSR-5 per litre seawater, and 100 mg crude oil + 100 mg OSR-12 per litre seawater.
Finasol OSR-5 WAF induced the highest mortality, followed by CEWAF with this dispersant. Crude oil WAF alone was less toxic. Finasol OSR-12 plus crude (CEWAF), and WAF of Finasol OSR-12 alone, caused only moderate mortality. The OSR-12 dispersant was less toxic than OSR-5. Adding Finasol OSR-12 to the crude oil caused a reduction in the mortality of the amphipods compared with amphipods exposed to the WAF and the water emulsion of crude oil alone. This reduction in toxicity with the dispersant was attributed to a corresponding reduction in the mole fraction of toxic oil components in the mixture.
Exposure to sublethal concentrations of WAF increased the respiratory rates of the amphipods in most cases (Aunaas et al., 1991). WAF slightly increased the concentrations of sodium in the haemolymph and whole organism. Some WAF exposures resulted in a significant increase in the water content of the amphipods, perhaps because there was an increase in membrane permeability to water and ions. The increased respiration probably occurred as part of the corresponding osmoregulation process.
Exposure to sublethal concentrations of water emulsions led to reduced respiration (probably from oil droplet adherence to gill membranes, thereby reducing oxygen diffusion), and increased concentrations of sodium in the haemolymph and the organism as a whole (Aunaas et al., 1991). The decrease in total free amino acid concentration in these amphipods was ascribed to volume regulation of swollen cells, and reduced co-transport of sodium and free amino acids from the haemolymph and into the cells.
Exposure to 2 mL/L of Norman Wells crude resulted in a range of mortalities to amphipods (Onisimus affinis, 85%; Corophium clarencense, 58%; Atylus carinatus, 7%) but isopods (Mesidotea entomon, M. sibirica, M. sabini) experienced less than 1% mortality (Percy et al., 1985). In fact isopods were unaffected by direct contact with the oil. The metabolism of amphipods was inhibited in low oil concentrations, but stimulated by high concentrations. 131
Contaminated sediments were acutely toxic to the amphipod O. affinis, but another species was unaffected. The barnacle, Balanus crenatus, suffered approximately 74% mortality under the same exposure regime. From the data, it was concluded that a severe spill would eliminate sensitive species and allow other resistant ones to survive and dominate in the short-term due to reduced competition. Epifauna that are unable to escape would suffer immediate effects from WAF, and the worst affected in the long-term would be the infauna if the oil enters the sediments.
A temperate species, the Arctic spider crab (Hyas araneus), was exposed to PAHs via sediment and injection. After two weeks of exposure, heart rate showed a significant increase compared to controls. Respiration was not affected by either oil treatment. The basal oxygen consumption of control Hyas araneus was lower than reported in those living in temperate water. Results indicated that although decreased uptake and metabolism of oil compounds into reactive oxygen species (ROS) was mainly due to the low temperature reducing the bioavailability of PAHs, the relatively low metabolic rate of Arctic Hyas araneus was also implicated (Camus et al., 2002a). Two cellular endpoints, haemocyte counts and protein levels, were significantly elevated following the dispersed oil exposure. Cell membrane stability and phagocytosis demonstrated a significant reduction. These results indicate alterations in the immune endpoints measured but they appear reversible upon removal of the stressor.
Arctic scallops could be used as sentinel species in the Arctic in addition to the common blue mussel, Mytilus edulis. The common blue mussel extended its distribution recently to the Svalbard Archipelago, where it was discovered at Sagaskjret, Isfjorden (Berge et al., 2005). The population seems to be young, having become established during the summer or autumn of 2002 from larvae transported to Spitsbergen by the West Spitsbergen Current. Horse mussels (Mytilus trossulus) were collected at Barrow, Alaska, during the 1990s (Feder et al., 2003).
Camus et al. (2002b) injected Chlamys islandica adductor muscle with BaP every 24 hours for four days. TOSC in the digestive gland was significantly reduced in exposed groups indicating a depletion in oxyradical molecular scavengers. The antioxidant defences appeared to be overwhelmed by the reactive oxygen species as the plasma membranes of haemocytes were 132
destabilized. The data indicate that ROS were produced by Arctic scallops via the metabolization of BaP at 2C.
Biomarker responses in the blunt gaper clam, Mya truncata, exposed to sediments contaminated with PAHs have been studied. After two weeks of exposure to sediments contaminated with crude oil TOSC showed no change. The high TOSC value of Mya truncata (control group) is thought to efficiently protect biomolecules with a low turnover rate in a low food availability environment. Respiration rate of control and PAH-exposed Mya truncata was similar and relatively low as is typical in polar bivalves, reflecting a strategy to minimize energy expenditure to cope with nine months of starvation. In the exposed bivalves, the haemocyte cellular membranes were significantly destabilized compared to controls. Bioaccumulation of PAH by Mya truncata was low with mainly uptake of low molecular weight compounds (two and three ring molecules). A combination of low metabolic rate and reduced solubility of the oil compound at low temperature probably were the reasons for the low uptake (Camus et al., 2003). Supporting these observations, a separate study by Hannam et al. (2009) has shown that the presence of dispersed oil triggers a significant immune response, ultimately reducing immune function in the Arctic scallop, Chlamys islandica.
C. islandica collected by divers from Porsanger, Norway, and exposed to sublethal dispersed Ekofisk crude oil (low of 0.06 and high of 0.25 mg/L; 4 0.5C) in continuous flow for either seven or 15 days, followed by seven days recovery in clean seawater had significantly altered blood and cell biochemistry (Hannam et al., 2009). The sum of the PAHs during exposure were about 0.509 and 2.55 g/L for low and high treatment tanks, respectively, consisting mostly of naphthalene and its alkyl homologues. Body burden of summed PAHs was 3.36 and 5.70 g/g for low and high treatments respectively. Bioaccumulated priority PAHs in the tissues included fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b,j]fluoranthene and benzo[b,j,k]fluoranthene. The concentrations of these in the experimental seawater were below the detection limit, so bioconcentration factors could not be calculated. The bioconcentration factors that could be calculated for individual priority PAHs ranged from 169 for naphthalene to 5430 for phenanthrene. Scallops clearly could bioaccumulate toxins from residual oil buried in 133
sediments since they tend to be slower at depuration than other bivalves (Hannam et al., 2009; Wohlgeschaffen et al., 1992).
In the high treatment, haemocyte counts (16.9 10 6 /mL compared with 11.1 10 6 /mL for controls) were significantly (p < 0.01) elevated and did not return to control levels over the seven-day recovery period. Protein levels were significantly (p < 0.01) elevated to a maximum of 2.39 mg/mL in the low treatment after seven days. This level returned to control values (1.36- 1.46 mg/mL) during recovery. Hannam et al. (2009) suggest that the increase in haemocytes might reflect a response to immune stress, but might also be an increase in blood cell production triggered by the PAH-mediated lysis of lysosome enriched haemocytes. The latter mechanism would explain the increase in plasma protein that was observed, although this protein increase might also be a result of stress-induced blood enzyme synthesis.
There were significant reductions in cell membrane stability (p < 0.001) and phagocytosis (p < 0.01). Membrane stability did not show a drop until after 15 days of exposure, when stability in the low treatment fell to 66% of controls and in the high treatment, 40%. Exposure time and treatment were statistically significant factors. The scallops recovered during the depuration period. Membrane stability is important for proper cellular function and is known to be disrupted by PAHs. Consequently, the activity of the lysosomes in detoxifying xenobiotics can be compromised. Membrane damage could also occur from ROS generated during metabolism of xenobiotics. The ROS cause direct damage by lipid peroxidation.
Phagocytic activity was significantly altered by exposure time and treatment. After 15 days, phagocytosis in the high treatment was 16.2 10 6 particles/mg protein compared to about 30 10 8 particles/mg protein for controls. This response also returned to normal after the seven-day depuration period. Tests in vitro of the effects of PAHs on haemocyte and haemolymphatic parameters in the Pacific oyster (Crassostrea gigas) using field concentrations (10 7 and 10 9 mg/mL) observed in the Marennes-Oleron Basin, France, and high concentrations (10 3 and 10 5 mg/mL) seen during oil spills have shown that fluorene, pyrene and heavy fuel oil significantly decreased phagocytosis (Bado-Nilles et al., 2008). The percentage of lysosomes and the percentage of phenoloxidase activity increased from dibenz[a,h]anthracene and 134
benzo[b]fluoranthene exposure, respectively. Modulation of immune parameters in the Pacific oyster by PAHs suggested that PAH pollution may be related to enhanced susceptibility to diseases.
Mean alkaline phosphatase activity ranged from 3.4-5.8 U/mg protein for all the animals and was not significantly affected by exposure or treatment throughout the experiment (Hannam et al., 2009). This enzyme works to breakdown foreign material. It was uncertain why these levels were unaffected by dispersed oil.
Although all immunological changes in C. islandica normalized during recovery, the impact of long-term continuous exposure remains unknown, but could result in increased susceptibility to disease, and ultimately, increased mortality and decreased survival (Hannam et al., 2009). Recovery from such damage is likely to be much slower in the Arctic due to the low growth rates, higher generation turnover times and increased age at maturation that are typical of Arctic organisms. The test concentrations had been chosen based on the OSPAR produced water discharge limit of 30 mg/L oil, and represent 120-500 dilution of this limit.
C. islandica were exposed in the laboratory to weathered North Sea crude oil WAF for 21 days at 8 1C in a simulated oil spill (Hannam et al., 2010). In this acute exposure, the maximum sum of the 16 EPA priority PAHs and the alkyl homologues of naphthalene, chrysene, dibenzothiophene, phenanthrene and anthracene was 163 g/L which decreased over the 21 days to about 8% of the maximum. By day 21, 50 of the initial 80 exposed scallops had survived, but there were no mortalities in the control group. The condition index, calculated as the percentage of dry weight of tissue (g) divided by shell length (mm), was significantly depressed from days 2-14, then returned to normal. Immune function and oxidative stress were examined. Haemocyte count significantly increased upon initial exposure, then fell below controls by day four, and by day seven rose again to become indistinguishable from control values. The rebound was likely due to the proliferation of these cells after PAH concentrations continued to decline. It is clear that haemocyte count varies with exposure time and concentration (Hannam et al., 2010; Hannam et al., 2009).
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Phagocytosis initially increased, then became inhibited by day two and afterward to 41-57% of control values. The inhibition may have been due to the large amount of energy required for this activity, which cannot be continuously supplied for an extended period, as well as PAHs causing the membrane to become less flexible and therefore less efficient at phagocytosis (Hannam et al., 2010). There was a decrease in cytotoxic ability, measured as the lytic ability of haemocytes, but it was not statistically significant. Cell membrane stability was significantly impaired. Under oxidative stress, there was a significant reduction in glutathione levels, probably due to an overwhelming metabolic production of ROS. The drop in glutathione was accompanied by lipid peroxidation and consequently membrane instability. Following the exposure, immune function did not recover, showing that these scallops can suffer sublethal effects from oil exposure even though acute effects might be brief.
Hutcheson and Harris (1982) studied the blunt gaper (M. truncata) and the northern astarte clam (Astarte borealis). M. truncata were exposed to 10, 25 and 50% WAF of Venezuelan Lago Medio crude oil (2.1 mg/L total hydrocarbons, 96 h). A. borealis were exposed to WAF of the weathered crude at 25% (0.95 mg TPH/L) and 50% (1.8 mg TPH/L) concentrations for 96 hours. The energy that could be allocated to growth and reproduction once maintenance metabolic needs are met (scope for growth) was determined for the clams after 96 hours and again 14 days later after depuration in clean seawater. Scope for growth has been used as a response indicator and also as a monitoring tool after oil spills in temperate regions.
Scope for growth in M. truncata decreased (deficit in growth energy) in all treatments relative to controls after exposure. The negative energy balance was a result of respiration exceeding assimilation. The 10% WAF group had the greatest deficit in growth energy, indicating that the decrease in scope for growth was independent of dose. Increased respiratory demands accounted for the decreased scope for growth, and the clams did not recover to normal metabolic levels even after 14 days of depuration.
For A. borealis, after exposure to the weathered crude WAF, there was no marked change in scope for growth at the 25% concentration; however, at 50% (1.8 mg/L), the scope for growth decreased by 220%. CEWAF of the weathered oil was also prepared using Corexit 9527 at a 136
1:10 DOR. CEWAF did not cause a significant change in the scope for growth at a nominal oil concentration of 0.5 mg/L, but weakened energy balance was noted at 1.6 mg/L, and there was a 57% reduction in scope for growth in 3 mg/L. WAF (1.8 mg/L) was more toxic than CEWAF (3 mg/L). Some recovery of energy balance in the group exposed to 3 mg/L CEWAF occurred after the 14-day depuration period, but it was insufficient for a positive scope for growth.
It was concluded that the reductions in scope for growth in this experiment were the result of slightly depressed assimilation rates coupled with increased respiration rates, and WAF was more toxic to A. borealis than CEWAF (Hutcheson and Harris, 1982). Arctic marine invertebrates common in the nearshore benthic ecosystem have developed various adaptations and traits to cope in the unique Arctic environment. Bivalves have adapted reproductive strategies that lead to maximum survival of offspring, slow growth rates and long life spans, plus metabolic adaptations that will encourage energy production under low thermal regimes. These important traits help Arctic species survive the challenges of a cold environment.
Brandvik et al. (2006b) report that water taken from beneath an in situ burn was found to be non- toxic to bivalve larvae and juvenile fin fish. In addition, the WAF from weathered Alberta sweet mixed blend, and the WAF from its ISB residue during the Newfoundland Offshore Burn Experiment was found to be non-toxic to three-spine stickleback (Gasterosteus aculeatus) and the gametes of the white sea urchin Lytechinus pictus (Blenkinsopp et al., 1996). The fish tests were for 96 hours with lethality as the end-point. The urchin test was of 20 minute duration and the end-point was inhibition of fertilization. GC/MS analysis showed low levels of volatile hydrocarbons with a maximum concentration of 1.1 g/mL.
Mammals
Several species of seals and whales are found in the Arctic Ocean including harp seals (Phoca groenlandica) that consume fish living just under the ice; bowhead whales (Balaena mysticetus) that filter small zooplankton through their baleen; ringed seals (Phoca hispida) that are ice obligate and eat amphipods, mysids, euphausids, shrimp, polar cod, and small fish like smelt, herring and capelin; narwhals (Monodon monoceros), beluga whales (Delphinapterus leucas), 137
ribbon seals (Phoca fasciata) and hooded seals (Cystophora cristata) that all hunt larger fish, including polar cod, and squid; spotted seals (Phoca largha) and bearded seals (Erignathus barbatus ice obligate) that feed on benthic fish and invertebrates; and walrus (Odobenus rosmarus) and gray whales (Eschrichtius robustus) that feed extensively on benthic invertebrates (infaunal and epifaunal). The effects of oil on these mammals can occur through direct contact, ingestion and inhalation.
Although grey seals (Halichoerus grypus) are not native to the Arctic, the effects of an oil spill on nursing mothers and newborn pups might provide some insight into effects of oiling in general upon seals. Oil stranded onshore of Pembrokeshire, Wales, in 1974 occurred at the time of grey seal pupping, and 25 of 62 pups were oiled (Davis and Anderson, 1976). Adults were also oiled but the number could not be accurately counted. Oiled mothers transferred the oil from their fur to the young during nursing. The percentage of mortality of both oiled and unoiled pups from the contaminated beach was high in comparison to other unoiled beaches. Two of the oiled pups were unable to swim, and drowned when washed off the beach. Behaviour of the seals appeared unaffected by oiling (Davis and Anderson, 1976); however, the peak weight of oiled pups was significantly lower than unoiled (t = 3.07, p < 0.01). Normal pups ingested little or no oil during the 14 to 17 day lactation period.
Ingestion of oil has been the cause of death of grey and harbour (or common, Phoca vitulina) seals (Griffiths et al., 1987). The northern fur seal (Callorhinus ursinus) is an eared seal found along the north Pacific Ocean, the Bering Sea and the Sea of Okhotsk, and oiling of this animal is expected to have serious consequences (Griffiths et al., 1987) since even a small amount of oiling of the fur of sub-adults caused a significant increase in conductance from 26 to as much as 53 W/m 2 /C (Kooyman et al., 1977). Increased conductance translates to decreased thermal resistance (insulation). Oiling of a pups fur caused conductance to increase from 40 to 54 W/m 2 /C (Kooyman et al., 1977). Live animals tend to groom, and this behaviour in a live, oiled animal might cause the increase in conductance to be less.
Griffiths et al. (1987) described possible effects of spilled oil to various Arctic pinnipeds. Harbour seal (P. vitulina) pups swim within a few days of birth but nurse for almost a month and 138
could become fouled, putting them at risk of physical impediment and drowning. Lactating mothers could become fouled during their daily excursions for food and likely transfer oil to the fur of pups during suckling (as was noted for grey seals). Depletion of crustacea and invertebrates could threaten young first-year seals. Oil spill countermeasure activities could cause the seals to abandon haul-out sites. Harp seals risk becoming fouled and younger seals that feed in the upper water column could suffer from reduced prey. Hooded seals are migratory and will probably not be affected much by a spill. Their pups do not have lanugo (fine hair) at birth, and gain blubber rapidly so the reduced thermal resistance caused by oiling would likely not be a factor. Bearded seal pups are born with adult fur, not lanugo, so oil fouling would be a problem, but they do gain blubber rapidly so that thermal resistance would probably not be compromised. There is little likelihood that adult bearded seals would become severely oiled as they frequent open pack ice; however, if high concentrations of dispersed oil are encountered down to the 50 m diving limit of this species it could pose a threat to their survival.
Ringed seals are the smallest and most numerous of the Arctic phocids, and are important to Arctic peoples as a source for food as well as income. They inhabit fast-ice (ice that is fastened to the coastline) during the late spring breeding season in areas where there is little ice movement. This makes their risk of oil fouling small, so long as the oil does not migrate appreciably under the fast-ice. If a spill were to occur within the fast-ice, there is a high risk of the adults transporting oil on their fur to the lair and transferring it to the pups. The risk would be most severe during the pupping season while the pups have their lanugo which usually lasts for 4-6 weeks after birth (Kelly et al., 2010). Some breed on permanent pack ice which adults regularly occupy during late summer through winter to early spring. Oil in drifting pack ice would cause fouling of adults.
Immersion of six ringed seals in a 1 cm thick slick of Norman Wells crude for 24 h at about 8C followed by removal to clean seawater caused eye problems and minor kidney and possibly liver lesions, but no permanent damage was observed (Engelhardt et al., 1977). Ringed seals suffered eye irritation, lesions, severe conjunctivitis, swollen nictitating membranes and evidence of corneal erosions and ulcers (Geraci and Smith, 1976). Eye damage in seals might be a common result of oil exposure. Analysis for hydrocarbons after two and six or seven days of exposure 139
showed 1-11 g/g in the blood, 1-4 g/g in blubber, 1-2 g/g in brain tissue, 2-5 g/g in the kidney, 1-8 g/g in the liver, 1 g/g in lung samples and 1-14 g/g in skeletal muscle. Urine and bile had the highest concentrations (39 and 58 g/g respectively) two days after oiling, and these were the major excretory pathways for oil metabolites. Oil in the brain correlated with neurological symptoms early in the exposure.
Three ringed seals died within 7l minutes that were transported to the University of Guelph and had oil added to their pool (Geraci and Smith, 1976). In this case, haematologic and blood chemistry analyses indicated that the cause of death was the stress of captivity exacerbated by oil exposure.
In an ingestion study, five ringed seals were fed over five days with 5mL/d of Norman Wells crude oil as 1 mL capsules inserted into their fish food (Engelhardt et al., 1977; Geraci and Smith, 1976). Blood samples for chemistry and haematology were taken prior to the ingestion of oil as well as four weeks after. Three of the four animals had appreciably higher levels of creatine phosphokinase after ingestion. This was the only measured blood parameter that changed. Another ingestion study using radiolabelled 3 H-benzene in the oil capsules fed at the same rate was used to trace metabolism of the ingested oil in blood and plasma up to 23 days after feeding (Engelhardt et al., 1977). A peak of about 22-39 disintegrations per minute (dpm) activity in the blood occurred at day 2 which rapidly declined to about 6-12 dpm by day 7. Plasma activity peaked at about 15-32 dpm on day 4, declining to 4-10 dpm by day 7. All blubber, liver and muscle tissues showed elevated activity (0.65-9.77 dpm) on day 2, declining by day 28.
A high level ingestion dose was carried out on fasting two to three-week old harp seal pups in two groups of seven (Geraci and Smith, 1976). Each group consisted of one control and six experimental animals. Blood was drawn for chemistry and hematology prior to feeding. One group was fed a single dose of 75 mL Norman Wells crude oil, and the other a single dose of 25 mL. Blood was drawn from the animals every two days over the ten-day period prior to sacrificing. Oil was noted on the anus and hind flippers 1.5 hours after feeding. The only difference noted in the oiled animals was a period of six to eight hours of restlessness 140
immediately after being given the dosage and one animal that had received a 75 mL dose was at first unresponsive to manipulation. Specimens in the high-dose administration showed a sorbital dehydrogenase peak of high activity 48 hours after feeding, reflecting transient liver damage. The study demonstrated that a single dose of up to 75 mL of Norman Wells crude oil (which is similar to Beaufort Sea oil being light, highly volatile, and of low viscosity) does not cause irreversible damage to harp seal pups. Oil effects on the liver and kidney of seals could be significant in the field where animals would be exposed for several weeks (Griffiths et al., 1987).
Walrus are gregarious, so groups of them would become fouled by a spill on pack ice or coastal haul-outs. Any spill affecting benthic invertebrates will affect local walrus as these constitute their prey. Walrus skin is very thick and is a good insulator with a conductance value of only 15 W/m 2 /C (Kooyman et al., 1977), so it would likely not be affected by oiling.
Griffiths et al. (1987) cite a publication entitled, Report of the Task Force - Operation Oil (Clean-up of the Arrow oil spill in Chedabucto Bay) to the Minister of Transport, Volume II that documented seals appearing to show considerable pain and suffering from contacting the oil. The primary mode of death for these seals seemed to be suffocation. Griffiths et al. (1987) note that if the animals were indeed displaying a pain reaction to the oil, it would likely be from oiling of the eyes by the volatile components of the fresh crude. Other health risks to seals include skin irritation, disorientation, lethargy, conjunctivitis, corneal ulcers, and liver legions (Kelly et al., 2010).
Engelhardt (1983) reviewed the toxicity responses to petroleum shown by whales, seals, sea otters (Enhydra lutris) and polar bears (Ursus maritimus). Ringed seals birth and nurse in subnivean lairs which might pose a particularly high risk of oil exposure, in addition to their use of ice pockets for breathing on long excursions beneath ice. Both situations increase the risk of oil inhalation and coating. Seals and sea otters do not generally avoid oil, and so become coated. Grey and harbour seal deaths have been associated with oil coating from the Kurdistan spill (Parsons et al., 1980). In an accidental spill of Bunker C and No. 2 fuel oil from Regal Sword, humpback whales (Megaptera novaeangliae), fin whales (Balaenoptera physalus) and white- 141
sided dolphins (Lagenorhynchus acutus) were observed feeding at and below the surface, apparently unperturbed by the slick (Goodale et al., 1981).
A brief review of petroleum hydrocarbon effects on blood chemistry in mammals is provided by ritsland et al. (1981). By way of example, they report that naphthalene inhibits cation transport and thereby can effect a change in electrolytic balance. Increases in bilirubin (free or conjugated), hypercholesterolemia, hyperuremia and elevated serum creatinine can result from hydrocarbon toxicity. Changes in blood serum enzymes can be indicative of tissue lesions, especially of the liver which is often the organ of focus in toxicity studies. Benzene can disrupt leucocyte formation, as evidenced by upset of leucocytic enzymes including alkaline phosphatase, and is known to cause haematopoietic problems. It generally causes the release of immature erythrocytes destined for haemolysis either by inhibition of haeme synthesis, influencing the production of fetal haemoglobin, and Heinz bodies. Naphthalene poisoning is also evident by the formation of Heinz bodies and haemolysis. The resultant peripheral haemolysis can drive the haematopoietic system to release more immature or less viable erythrocytes which again will be destroyed and released as bilirubin.
General effects of an oil spill on cetaceans and points to consider given by Griffiths et al. (1987) are as follows. Right whales migrate through ice by way of leads. They habitually skim the water surface for food which makes them susceptible to oil ingestion. Sei whales (Balaenoptera borealis) are a warm water migratory species that stay clear of pack ice, but feed similarly to right whales and therefore run a similar risk. Humpbacks, on the other hand, feed below the surface, and do not feed during migration, reducing the risk of oil ingestion. When migrating through the Barents Sea, these whales follow the coastline which would expose them to external oil contamination if a spill were to occur there. Blue whales (B. musculus) are found in the Barents Sea to Svalbard. They feed primarily on krill, so any contamination of krill has potential to contaminate feeding blue whales. Fin (B. physalus) and minke (B. acutorostrata) whales are at low risk of suffering effects from an oil spill either to themselves or to their prey, as they feed subsurface on both krill and fish, unless, as stated previously, the krill themselves are contaminated. Sperm whales (Physeter catodon) feed at great depths, and those found in the Arctic are usually solitary males. They are at low risk of effects from oil spills. Other species at 142
low risk from spills are the killer (Orcinus orca), northern bottlenose (Hyperoodon ampullatus) and beluga (Delphinapterus leucas) whales, the common porpoise (Phocaena phocaena), and the Pacific white sided (or white beaked) dolphin (Lagenorhynchus acutus).
Gray whales forage in the Chukchi and western Beaufort Seas, with occasional records in the Canadian Beaufort Sea (Logerwell and Baker, 2011). It is not known whether gray whales are able to detect surface oil from a spill, and in fact, during the Exxon Valdez spill, they were observed to swim through the slick (Moore and Clarke, 2002). There was also one observation of a whale lying in the surface oil, for unknown reasons. Gray whales probably experience irritation to their eyes and tactile hair follicles from oil contact, but there is no evidence to show that effects on skin tissue are long lasting (Geraci, 1990). It is more likely that oil might aggravate broken areas of skin, or damage areas with barnacle growth, leading to bacterial infection (Moore and Clarke, 2002); however, experimental skin exposure of a stranded sperm whale (Physeter catodon) to gasoline (Geraci and Aubin., 1982) for 17 hours caused erosion and severe damage likely because it removed natural oils. Experimental lesions purposely contaminated with crude oil and petrol did not delay normal healing. Sperm whale skin biopsies that were treated with 0600 M of -naphthoflavone, a known CYP1A inducer, were tested for levels of CYP1A induction in the endothelium, in smooth muscle, and in fibroblasts (Godard et al., 2004). Significant (p = 0.05) concentration-dependent increases in CYP1A staining in response to - naphthoflavone treatment were found in cells of the endothelium and smooth muscle. This inducibility of the CYP1A system in cetaceans suggests that they may be able to transfer, metabolize and detoxify hydrocarbons.
The epidermis of cetaceans acts as a barrier against molecular antigens, and lacks Langerhans cells which might otherwise cause oil to elicit an immune response (Geraci and St. Aubin, 1985). This might explain why gray whales were observed to swim through oil slicks apparently unperturbed. It is unlikely that cetaceans would be exposed to fresh, unweathered, crude oil for extended periods. The number of mortalities due to a spill would likely be low, while the number of individuals suffering significant irritation might be high (Griffiths et al., 1987).
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Although oil can adsorb to the baleen, it can be removed with the continual flushing of seawater (Geraci and St. Aubin, 1985). Heavy oils like Bunker C were found to clog the baleen of fin (Balaenoptera physalus), sei (Balaenoptera borealis) and humpback (Megaptera novaeangliae) but not gray whales, and reduce water flow, which could conceivably interfere with normal feeding. At 15C, heavier oils could persist on the fibers of fin and gray whales for 15 to 20 hours, while lighter oils were cleared from the baleen plate within one hour. Geraci and St Aubin (1985) concluded that the level of fouling tested would not normally impair flow rate or feeding.
Whereas the risk of oil contamination through ingestion of benthic prey contaminated with dispersed oil has been suggested (Neff, 1990), there has been no evidence to support this (Geraci, 1990). However, Geraci and St. Aubin (1985) found low levels (<7 g/g wet weight) of naphthalene in mysticetes (fin, sei and minke) and pinnipeds (Phoca vitulina, H. grypus, E. barbatus, 0. rosmarus). The highest levels were found in beluga (6.3-21.1 g/g) and narwhal blubber (10.5-17.9 g/g). Bowhead whales and bearded seals that are harvested for subsistence on the Alaskan North Slope have not been found to have PAHs (OHara and OShea, 2005). This lack of detectable PAHs underscores that it is necessary to establish biochemical and histological indicators in marine mammals, since they do not bioaccumulate these chemicals, unlike polychlorinated biphenyls and other organochlorines.
In an unpublished study (Fraker, 1984), gray whales seemingly respired more rapidly on surfacing, and surfaced less frequently while passing through a region off the California coast that has natural subsea oil seeps, but the differences in behaviour were slight and not statistically evaluated. Whales could inhale toxic vapour from a fresh spill, which has more potential to cause harm to respiratory membranes than any vapour from oil that has weathered for two to four hours. However, the impact would likely only affect individual animals that have been weakened by parasites or adrenal dysfunction (Fraker, 1984).
Bowhead whales could be at high risk of oil ingestion if they were to feed on contaminated zooplankton. It has been found that food organisms of this whale can accumulate hydrocarbons if they reside in an oil contaminated environment (Malins, 1977). There appears to be little or no 144
possibility of a whale aspirating ingested oil that becomes regurgitated because of an anatomical adaptation of the larynx peculiar to cetaceans that prevents aspiration (Geraci and Aubin., 1982).
It is unknown what the effects are of prolonged inhalation of crude oil vapours by marine mammals. This is a knowledge gap that might be significant considering the migration of cetaceans to the Arctic during the spring and summer months. In terms of exposure, the reduction in sea ice might lead to increased range of migrant cetaceans such as fin, humpback, minke (Balaenoptera acutorostrata), gray and killer (Orcinus orca) whales which now can be found in the Barents and Bering seas (Moore and Huntington, 2008).
In addition to effects mentioned above, exposure of marine mammals to oil can result in oiling of eyes and skin, and although they are considered to be less affected from fouling by oil as compared with other animals (e.g. seabirds), a spill in a location where mammals serendipitously occur, whether for migration, feeding, breeding, or otherwise, has the potential to affect a population (stock) or isolated group (Huntington, 2009).
Residual oil from the Exxon Valdez has been implicated as the cause for high mortality rates among sea otters (Enhydra lutris kenyoni) in Prince William Sound; the otters showing elevated levels of CYP1A that suggest continued low-level oil exposure (Monson et al., 2000). The European sea otter subspecies (Enhydra lutris lutris) is found on the Kamchatka Peninsula and Commander Islands of Russia, adjacent to the Barents Sea, and as with the kenyoni subspecies, they are on the International Union for Conservation of Nature red list as endangered (IUCN Otter Specialist Group, 2010). A small population of E. l. lutris was reported in Finmark, Norway (Griffiths et al., 1987). Not much is known of the biology of this otter which feeds on fish, clams, crabs and urchins along the beaches and up to about 100 m offshore (Griffiths et al., 1987). The otter does not have blubber but relies on its thick fur for insulation (IUCN Otter Specialist Group, 2010), making it vulnerable to fouling with oil which is a leading cause of death for oiled individuals (Griffiths et al., 1987). There is also the danger of harmful effects through ingestion of contaminated food. The sea otter can be used as a sentinel species for habitat health monitoring (IUCN Otter Specialist Group, 2010).
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Harris et al. (2011) analyzed blood samples from 29 live-captured sea otters (E. lutris) in British Columbia, as well as their invertebrate prey, for alkanes and PAHs. Hydrocarbon concentrations in sea otters were similar between areas and among age and sex classes. Biomagnification factors (ratio of otter to prey) suggested that metabolism plays a significant role in bioaccumulation. Most PAHs did not biomagnify, but some higher alkylated 3-ring and 4-ring PAHs did, even when concentrations of PAHs in dietary prey were low, as a consequence of the otters extreme consumption rates (up to 25% of their body weight per day). The estimated body burdens for the sum of PAHs was 5120 3600 g (alkyl PAHs = 89 7%) for males, and 3710 2560 g (alkyl PAHs = 84 10%) for females.
Oiling with Prudhoe Bay crude of the pelts of adult sea otter (E. lutris) caused only a slight increase in conductance from 22-26 W/m 2 /C to 26-29 W/m 2 /C; however, for a pups pelt, conductance increased from 7 to 15 W/m 2 /C (Kooyman et al., 1977). It should be noted that if an oiled animal were to groom its pelt, the increase in conductance might be less severe. Also, Prudhoe Bay is a light crude oil that did not cause the fur to clump. Costa and Kooyman (1982) found that an average of 17% oiling of the fur of live E. lutris with Prudhoe Bay crude increased metabolic oxygen consumption by 41% from an average of 16.0 mL O 2 /kg/min at 15C prior to oiling to 22.2 mL O 2 /kg/min. Curiously, after washing, metabolism increased 106% to 32.6 mL O 2 /kg/min. Two of the experimental animals experienced shivering, one of which subsequently died of pneumonia, which suggests that should these animals be cleaned of oil following a spill (very expensive considering the animals would have to be housed at 20C for about a week to groom), they risk dying of complications including pneumonia and hypothermia (Griffiths et al., 1987). The authors feel that grooming is necessary to maintain the furs water repellence and insulation. Oiling caused the fur to clump resulting in the loss of the air layer that is usually trapped between fur and skin and prevents water penetration. It is not known if the oiling and washing procedure had irritated the skin to cause increased peripheral circulation and heat loss.
Kooyman (1977) found that conductance of a bearded seal (E. barbatus) pelt was unaffected by oiling with Prudhoe Bay crude. Mammals that depend on their fur for insulation rather than blubber tend to increase their metabolism in response to oiling. The oil causes an increase in conductance of the pelt and corresponding cooling of the skin. Although the peripheral 146
temperature decreases, there is a compensatory increase in metabolism that allows the animal to maintain its core temperature (Engelhardt, 1983).
Polar bear (Ursus maritimus) are considered an ice-obligate species, spending most of their time on the ice where they hunt, rest, and bear young (Moore and Huntington, 2008). They are a top predator of the Arctic Ocean food web consuming mostly ringed and bearded seals, but they will also eat belugas, narwhals, walrus, harbour seals, reindeer (Rangifer tarandus), and birds (Laidre et al., 2008). For the Svalbard polar bear population it was estimated in 1983 that a take of two males per female at a rate of 54 animals per year, would not endanger the population (Ritsland and Schweinsburg, 1983). This could apply to a reduction of the population due to an oil spill, but the calculation must be reiterated using current population statistics.
Oil readily adheres to the fur of polar bears (Ritsland et al., 1981). An experimental exposure (by enticing bears with seal blubber to enter a seawater pool) of three polar bears for 15-50 min to a 1 cm thick slick of Midale crude oil (Ritsland et al., 1981) led to the appearance of petroleum in most tissues due mainly due to ingestion while grooming, followed by skin absorption and inhalation. The animals avoided swimming in the oiled pool. The two bears that had been exposed for 30 and 50 minutes died one month later. Liquid samples of whole blood, plasma, bile, urine and vomitus were obtained, in addition to tissue samples of liver, kidney, skeletal and heart muscle, brain, spleen, subcutaneous fat, mesenteric fat, marrow and lung. The fur of one bear was sampled. The amount of oil calculated to have adsorbed to the fur was 9-27 kg, and a bear crossing an oiled lead would be expected to have its fur rapidly and heavily contaminated. Physical removal of the oil by the bears was mostly limited to grooming. All bears began shivering within eight hours of oil exposure, and all vomited more than once within 12 hours of oil ingestion. Separate pelts that were tested showed an increase by factors of two to four in conductance (decreased insulative capacity) following oiling. Slight increases in skin temperature were noted and could not be specifically attributed to the direct oil coating or to the ingested oil, but were likely a compensatory response to the loss of insulative capacity. Solar heating of the skin due to oiling increased by 28%. The first 12 hours during an oil spill would be critical to dealing with contaminated polar bears.
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Immediately after exposure, oil was present in the vomitus at a concentration of 520-605 mL/kg and in feces at 46-90% by volume or weight. The main route for hydrocarbon excretion was by way of feces. Urine samples had concentrations as high as 714 L/L, and 27-42 L/L three to four weeks post exposure. Urine was another major excretory route of oil. Of the tissue samples, the highest hydrocarbon levels were found in the bone marrow (471 L/kg), kidney (200 L/kg), and brain (325 L/kg). Liver, lung, skeletal and heart muscle had decreasing levels in that order. Oil was undetectable in the fat samples.
Haematocrit values declined from 45-56% to 14-30% at the end of the experiment. The maxima in erythrocyte count decline was 6-8 10 6 /L. Values of other parameters including mean cell volume, mean cell haemoglobin, and mean cell haemoglobin concentration also declined. Leukocyte counts initially increased, but thereafter, changes were inconsistent. Serum sodium decreased in two of the three bears, while calcium increased in all exposed bears. Levels of lactate dehydrogenase increased after exposure. Total bilirubin increased from control levels of 0-0.8 mg/dL, rising as high as 4-19 mg/dL. Serum protein also rose, and cholesterol was high in all three bears from the second to fifth week post-oiling. The normal level of blood urea nitrogen was 4-33 mg/dL, which initially showed a slight decline and then rose to about 150 mg/dL near the end of the experiment. Creatinine also increased from control values of 0.7-2.5 mg/dL to about 13 mg/dL. In summary, the bears showed evidence of severe anemia from suppressed haematopoiesis (from the myelotoxicity of benzene) and from haemolysis, due to the oiling, although the white blood cell counts were not conclusively altered by the oil. Sodium and phosphate showed definite imbalances attributable to oil exposure. All three bears showed biochemical and pathological evidence (lesions of the gastrointestinal tract, nephrosis) of kidney failure from oiling. Hepatotoxicity was minimal. ritsland et al. (1981) concluded that the polar bear is a potentially greatly impacted species when exposed to oil spills. The surviving polar bear was treated and nursed back to health over a period of several months. This would be a great expense if many individuals were severely fouled by a major oil spill in the Arctic. Cleaning oiled marine mammals could require weeks of humane confinement and the use of antibiotics, tranquilizers and other drug therapy (Griffiths et al., 1987).
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Any model predicting the consequences of oil fouling must account for the season, the productivity of the area, and the variable health status of the target population (Geraci and Smith, 1976). The difficulty in assessing toxicosis in marine mammals lies in the fact that body burdens of contaminants and declines in populations have rarely been linked directly to a source, and especially not for petroleum hydrocarbons. The main reasons for this lack of evidence are (OHara and OShea, 2005): lack of understanding of marine mammal health and physiology; reliance on extrapolation of historical, unrelated species data; reliance on tissue residues; ethical aspects of studying mammals; experimental designs that lack statistical power; correlations and associations of chemicals with effects rather than clear mechanisms; lack of effective monitoring and funding.
The assessment of potential toxicity must be multidisciplinary, begin with measurements of contaminants in the environment and organisms, and scale up to populations, species and ecosystem levels (OHara and OShea, 2005). The measurements of chemicals should include congener or isomer concentrations, oxidation states and metabolites. These will help to examine questions of bioaccumulation, biomagnification, toxin kinetics and transformations at the molecular, cellular and tissue levels in sickly individuals compared with healthy specimens obtained through stranding, by-catch, hunted, or catch and release. This would, in turn, help to evaluate the impact on, and epidemiology of individuals, populations, species and so forth. Studies need to be long-term, and designed for rigorous statistical analysis. In this way, exposure to chemicals could be linked to effects observed in mammals. Among the species suggested for monitoring by the 1998 Marine Mammal Commission were these Arctic ones: harbor seals, grey seals, beluga, bowhead and minke whales, sea otters, walruses, polar bears. Mitigation of contaminant effects in the Arctic will require international collaboration and global management in order to provide adequate protection of circumpolar biota (OHara and OShea, 2005). Recommendations for marine mammal scientific research, policy, and supportive infrastructure are given by OHara and OShea (2005).
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7. Arctic Oil Spill Field Trials
Much of what we have learned about the behaviour of oil in Arctic and ice-infested waters has been linked to a number of limited field experiments involving controlled releases of fresh and emulsified crude oil for research purposes. The Canadian governments approval of exploratory drilling operations in the Canadian Beaufort Sea in the 1970s motivated a number of programs to study oil spill countermeasures and study the fate and effects of oil and spill response technologies in offshore cold water and Arctic environments.
7.1 Balaena Bay experiment 1974 - 1975 (Norcor)
One of the first large-scale oil spill experiments occurred in 1974-75 in the Canadian Arctic in Balaena Bay, a small bay 20 km to the southwest of Cape Parry (70 02 N, 124 53 W), NWT. This study was conducted with the principal objective to assess the impact of an offshore oil well blowout on the thermal regime of the Beaufort Sea, and to develop potential countermeasure techniques. The Balaena Bay experiment was designed to generate fundamental data on the interaction of crude oil with Arctic sea ice (NORCOR Engineering & Research Ltd, 1975). These experiments were the first to study all aspects of oil in ice behaviour, including spreading under ice, encapsulation, progressive vertical migration as the ice warmed, spreading on surface melt pools in the spring, and weathering (Dickins, 2011). Oil spill countermeasures, namely in situ burning (ISB) and mechanical cleanup (booms, skimmers, pumps, sorbents and beehive burners) were conducted near the end of the experiment once the ice had melted. A smaller component of the project was to measure the biological impact of the spills and possible relevance to other areas. A follow-up chemical/biological study was conducted in 1981 to assess the degree of environmental impact as a result of the experimental oil spills (Dickins and Hellebust, 1981).
During the conduct of the study, two crude oils (Norman Wells and Swan Hills) were injected in nine separate discharges under the ice inside large Fabrene containment skirts at various stages of ice growth and depletion from October 1974 to May 1975. In addition to the contained spills, two additional spills were carried out 30 km off shore where oil was allowed to spread freely in 150
the presence of a 10 cm/s current and movement documented by divers and underwater camera footage. A total of 54.4 m 3 were spilled in eleven separate discharges (NORCOR Engineering & Research Ltd, 1975). The test areas were continually monitored and oil, water and ice samples were recovered for laboratory analysis.
In May of 1975, oil started to appear on the ice surface after migrating naturally through brine channels within the sea ice. Most of the oil rose to the surface and lay in large pools and these pools were successfully burned. Oil residue was shovelled off the ice until the ice began to disintegrate. As the ice cover was broken, it grounded on the shore where the remaining residue, mainly in the form of tarry clumps and balls was swept up (5 m 3 from the ice and 0.6 m 3 from the shore). The bulk of the spilled oil (> 85%) was evaporated (10 m 3 ) or burned (27 m 3 ).
Oil that was experimentally released rose to the surface and upon striking the underside of the ice, radiated outward, progressively filling depressions in the sheet. Within a matter of hours of oil contacting the ice, it became encapsulated and once entrapped was stabilized with little evidence of degradation or weathering through the winter months. With the onset of spring and upon exposure to increased solar radiation and air temperatures, the oil began to migrate upwards and at the surface saturated the snow cover, reducing albedo, hence accelerating the process. Oiled areas were free of ice one to three weeks earlier than unoiled areas. This study gave sufficient information on the behaviour of oil in stationary first-year ice, and on spill countermeasures to be employed, but further work was needed on the entrainment and migration of oil in second and multi-year ice, the effects on an oil slick on sea ice formation (particularly under dynamic conditions), and long-term fate and impact of unrecovered oil. ISB was found to be most efficient and effective with a minimum film thickness of 0.5 cm required to sustain combustion. Manual recovery of the oil was costly and labour intensive. Detailed physical and biological studies were conducted prior to the first discharge of oil. Salinity and temperature profiling and dissolved hydrocarbon content were measured throughout the year.
Controlled spills of 40 50 L (20 L/m 2 ) of fresh and weathered Norman Wells crude oil were conducted on uncontaminated salt marsh areas on the northwest side of the Bay by Dr. J. Hellebust (Department of Botany, University of Toronto). Observations of the sites six weeks 151
after the spill showed that vegetation was extensively killed by both fresh and weathered crude, with the exception of scurvy weed (Cochlearia officinalis) which appeared surprisingly resistant to the very high levels of crude oil applied. Only marsh plants above the water line at the time of oiling were affected by the spill. Toxicity experiments were conducted with fresh and weathered crude collected from the under-ice oil experiments with freshly collected phytoplankton and zooplankton samples from Balaena Bay. Young stages of the jelly fish (Cyanea capillata) were very sensitive to both fresh and weathered crude oil.
Results from the Balaena Bay study provided evidence of limited environmental damage from and oil spill during the winter as the oil was effectively trapped in or under the ice. In most cases, little effect was noted on phytoplankton and no effect on zooplankton and benthic organisms. This was attributed to the very effective cleanup of the weathered crude oil before the breakup of the ice. There were no significant impacts on zooplankton or phytoplankton populations. The overall conclusion for the study was that there was no evidence of oil in the water column or deleterious effects on the marine ecosystem with the exception of very light oiling of the shingles of the tidal zones over about 900 m of shoreline. It was estimated that after mechanical removal, burning, and physical degradation, only 1 m 3 of residual oil remained on the site at the end of 1975.
Balaena Bay Revisited: 1981
The Balaena Bay site was revisited in 1981 to verify if the no environmental effects still applied after six years (Dickins and Hellebust, 1981). The original biological and chemical data collected were insufficient in quantity and definition to provide an adequate baseline, so an independent study strategy was developed, involving comparison of benthic histopathology and population between stations both within and outside the impacted areas in 1974. Field sampling and analysis programs were designed to evaluate any long-term effects on both benthic and seashore organisms and to provide data on any oil residues still present. Benthic, beach and salt marsh sediments were sampled and analyzed for non-polar and polyaromatic hydrocarbons. Histopathological studies were conducted on the clam Macoma calcerea and the polychaete 152
Pectinaria hyperborean, and the benthic community was assessed as well as vegetation in the contaminated area.
After six years, weathered oil residues were found coating rocks in a narrow strip of intertidal zone. Petrogenic hydrocarbons were still detectable in the beach sediments and at the salt marsh spill site but not in the benthic or salt marsh control station sediments. The total volume remaining was estimated at 0.2 m 3 with coverage ranging from 0.1 to 5% in the worst areas. The heavily oiled salt marsh experimental sites showed grass recovery rates of less than 13% with about 5% of the original concentration remaining in the upper soil layers. The oiled plots showed a definite recovery of the higher dominant marsh grass, Puccinellia phryganoides, about 13% in weathered crude oil plots, and 3.5% in fresh crude oil plots, while little recovery was found for the subdominant Wilhelmsia physodes. A very active blue-green micro-algal flora developed in both the oiled plots. No measurable effects were found on the moss and algal marsh zones which were not directly covered, but closely adjacent within 30 cm of the applied oil. Approximately 5% of the applied crude oil remained in the salt marsh soil at the spill sites. Areas covered with 1 to 10 mm of crude oil residues showed little vegetation, however some algae, lichens and the macrophyte, Cochlearia officianalis, were observed growing in close proximity to the oil residues. Amphipods were also seen in close proximity with crude oil residues in salt marsh depressions containing seawater. In conclusion, there appeared to be little or no toxic effects to algal photosynthesis or marine invertebrate behaviour by the oil residues, which covered a relatively small area of the shoreline near the spill sites. However, the residual oil appeared to be unsuitable substrate for algal or higher plant growth with the exception of blue-green algae.
The only statistically significant difference in the health and condition of polychaetes and bivalves from the oil spill control sites was the minimal reproductive development observed in animals from the oil spill site, with the possible cause of this attributed to some natural and/or anthropogenic stress in the environment. Differences were seen in the benthic communities found at the control stations and the oil spill. Final conclusions were that overall impact of the spill was small (Dickins and Hellebust, 1981).
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7.2 Baffin Island Oil Spill Experiment (BIOS)
The BIOS conducted multidisciplinary experimental oil spill field studies over a four year period (May 1980 and August 1983) in the Canadian Arctic at a field site located near Cape Hatt on a small peninsula of northern Baffin Island, Northwest Territories (now Nunavut), Canada, 65 km southwest of the community of Pond Inlet. The experimental design and overall results have been summarized (Sergy and Blackall, 1987), and details of various components of the study can be found as individual papers in a dedicated volume of the journal, Arctic (Volume 40, Supplement 1). Information obtained from the study was intended for planning, approval and operational phases of hydrocarbon development in the Arctic.
The primary objectives of the BIOS project were to determine if the use of chemical oil dispersants in the Arctic nearshore would reduce or increase the environmental effects of spilled oil and to determine the relative effectiveness of other shoreline protection and cleanup techniques. The secondary objective was to determine the chemical and physical fate of oil in the Arctic nearshore and shoreline areas (Sergy and Blackall, 1987).
There were two separate but complementary studies, each involving a controlled release of crude oil. The nearshore study compared the consequences of dispersing an oil slick close to shore with the option of allowing the oil to beach and leaving it to natural attenuation (self-cleaning). The study compared the fate and effects of a short-term high concentration of dispersed oil with the fate and effects of a long-term low level release of oil stranded on the shoreline. The shoreline study evaluated the technological cleanup of beached oil. Findings on oil fate and persistence were used to compare the relative effectiveness of promising Arctic shoreline cleanup techniques against a benchmark of natural self-cleaning processes (Sergy and Blackall, 1987).
Three bays of similar coastal morphology and sedimentology were selected as test areas (Semples, 1987). Studies on climate, ice conditions, geomorphology and oceanography were conducted and document the physical features of the area and discuss them in relation to regional conditions (Buckley et al., 1987; Dickins et al., 1987; Meeres, 1987; Semples, 1987).
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In the first year of the study (1980), physical, biological and chemical baseline data were collected and analyzed. Two experimental oil spills were conducted the second year (1981), where one chemically dispersed oil spill would impact one bay and a second untreated oil spill would impact a similar bay. Sampling was repeated in the third and fourth years to document the long-term fate and effects of the spill. Baseline studies of petroleum residues in the sediments (Cretney et al., 1987b) and waters (Cretney et al., 1987c) were measured and found to be in the low to sub-microgram per gram and microgram per litre concentration range as might be found anywhere on Earth. Prior to the spill of oil, Cretney et al. (1987a) also measured tissue hydrocarbons in a variety of Arctic marine species and were found to be low (ng/g) with origins from combustion products.
Nearshore Study
Two experimental discharges of 15 m 3 of weathered (8% by weight) sweet medium crude oil (Venezuela Lagomedio) were released at each site, over a period of six hours or half a tide cycle. Corexit 9527 was the dispersant used in an oil/dispersant ratio of 10:1. The oil and dispersant were selected based on a reasonable data base existing for both. The surface slick release began at high tide and under influence of an onshore wind. Oil was carried up on the beach by wind and wave action as the tide receded. The test area was boomed to prevent contamination at the beginning of the experiment and remained in place for several weeks to capture any oil sheen redistributed by the tides. Oil remaining on the surface was collected with skimmers after a full tidal cycle. Oil was dispersed using a sub-sea diffuser pipe through which the oil/seawater/dispersant was released. The chemically dispersed oil caused a variety of conditions. The sub-sea discharge caused benthic organisms to be exposed to abnormally high concentrations of toxic aromatic hydrocarbons. Oil was also introduced at greater water depths than would likely be the case of a surface oil slick dispersed at the surface in the Arctic. In many coastal Arctic areas, the often present and well-pronounced pycnocline would suppress the downward mixing of oil to the productive benthos.
The beach could not retain all of the oil that reached the shoreline and as a result, one third of the spilled oil was recovered in cleanup activities on the water, one third was evaporated and the 155
remaining was stranded in the intertidal zone. The stranded oil was subject to natural cleaning processes during approximately six months of open water periods from 1981 to 1983. Over this time, the surface oil cover was reduced by approximately half, whereas estimates indicated that 80% of the oil initially stranded (5.3 m 3 ) was removed. It was concluded that oil was removed in substantial quantities from the intertidal zone even in such a low-energy Arctic environment (Owens et al., 1987a).
There was no major large-scale mortality of benthic infauna to either oil release. Multivariate analyses showed no significant change in infaunal community structure, and effects attributable were found in three of 72 univariate analyses of density, biomass or size data for individual taxa (Cross et al., 1987a; Cross and Thomson, 1987). A progressive decrease in the condition of the filter-feeding bivalve Serripes groenlandicus in the reference bay several kilometres away from the dispersed oil release was the result of exposure to dilute dispersed oil for several days. A similar effect on condition in the surface deposit-feeding bivalve Macoma calcaerea was apparently caused by relatively low oil concentrations in the sediments of the dispersed and surface oil release bays. Decreases in density of the polychaete Spio spp. indicated that oil in the sediments of the surface oil release and dispersed oil release bays affected reproductive processes. Bivalve and polychaete effects were still evident two years after the spill (Cross and Martin, 1983).
The sub-surface release of the oil resulted in short-term relatively high oil concentrations in waters of the two adjacent bays and oil in the water could be detected below 1 m in the untreated oil release. Immediately after the spill, divers observed narcosis in urchins and starfish. Overall, there were no major effects of oil release on densities of epibenthic crustaceans and amphipods. Minor effects attributable to the untreated oil included depth distribution of Anonyx juveniles, and dispersed oil in the water column apparently had a delayed adverse effect on reproduction in the amphipod family, Stenothoidae (Cross et al., 1987a).
Biomass, number of species, and reproductive condition of the dominant understory macroalgae at 3 m depth did not seem to be adversely affected by either oil in sub-tidal sediments or by chemically dispersed oil in the water column. The lack of major effects on macroalgae may have 156
been partly attributable to the lack of effects on herbivores and the vegetative mode of reproduction in the dominant macroalgal species (Cross, 1987).
Bacterial numbers and microheterotrophic activity (uptake of glutamic acid) were monitored in the water column and sediments of selected bays between 1981 and 1983 prior to and after the spill (Bunch, 1987; Bunch, 1984; Bunch et al., 1983). Dissolved organic carbon and inorganic nutrients were measured in the water column. Total organic carbon was measured in the sediments. At the concentrations of oil released into the water by the surface and dispersed oil releases, the effect on measured bacterial activity was transient and minimal. No changes in bacterial activity in the sediments could be ascribed to either oil release. Bacterial numbers were not affected by the oil releases. The Corexit 9527 significantly altered kinetic parameters in laboratory experiments, but was not seen in field conditions where the concentration of dispersant was three orders of magnitude lower. Oil-degrading capacity was determined in the water and sediments of all bays and did not appear to be altered by the oil releases. The effects of the surface slick or the dispersion into the water column would be inconsequential or marginally deleterious to bacterial numbers or the microheterotrophic uptake of glutamic acid (Bunch, 1987).
The natural biological degradation of oil was compared with microbial action enhanced by the artificial application of nutrients in three oiled plots in the Arctic backshore sediments (Eimhjellen and Josefson, 1984). The effects of the addition of artificial fertilizer were positive but varied depending on the geomorphological conditions of the beach. In fine sediments there was a 1-100 times increased level of oil degrading bacteria relative to unfertilized controls over a two-year period. Biodegradation rates were enhanced three to five times for the alkane fraction of the oil. The effects of fertilizer addition on coarse sediment were marginal. Mechanical mixing of oil and fertilizer into the sediment gave further improvement in biological degradation in spite of lower levels of oil-degrading bacteria. Sergy and Blackall (1987) noted that the biological impacts were relatively minor. All short-term effects were temporary and apparently without serious consequence. There were no measured biological effects in the intertidal zone due to the absence of Arctic intertidal life. The intertidal zones in more temperate regions are more vulnerable to the effects of an oil spill. 157
The BIOS study was successful in achieving conditions to determine oil fate and effects that would be relevant to future Arctic oil spills. The countermeasure options, chemical dispersion and natural shoreline restoration were assessed and compared in an intertidal and subtidal habitat common in the eastern and high Arctic. Biological impacts from both spills were relatively minor and effects were short-term. After two years of post-spill monitoring, there was no evidence of large-scale mortality of subtidal benthic biota attributable to either the chemically dispersed oil or the oil contaminated beach. Infauna, epifauna and microalgae populations and community structure showed few changes (Cross et al., 1987a; Cross and Thomson, 1987; Cross et al., 1987b).
Shoreline Study
The shoreline study evaluated options for enhancing the cleanup of oiled shorelines by comparing the methods to natural self-cleaning. The shoreline study required the use of several sections of coastline with different beach materials and exposure to wave and tide action. A large embayment on the east coast of Cape Hatt (Z lagoon) was selected as the site for the shoreline countermeasure experiments. The location was sufficiently distant from the other BIOS experimental oil releases to preclude the possibility of cross contamination. The study sites provided a representative range of high, intermediate and low-energy wave environments, and energy levels at the shoreline are directly related to local fetch characteristics (Owens and Robson, 1987). Small plots (20 - 40 m 2 ) were used in the intertidal and backshore zones of the test beaches. Two control plots each 40 m 2 were laid down in 1980 in the upper intertidal zone. Consistency was maintained in the type, quantity and method of application of the oil. Emulsified and non-emulsified Lagomedio crude oil of the same stock used in the nearshore study were applied in paired plots. After application of oil to the beach, the plots were left for 24 hours prior to the initiation of cleanup tests to simulate minimal response time.
The intertidal plots were oiled to their maximum holding capacity, as evidenced by the migration of surplus oil down the beach face. Wave energy was the dominant factor in removal of oil from exposed beaches (99% in 48 hours). On a partially exposed beach, the majority of oil was 158
removed within the first open water season (40 days) and by the end of the second season, less than 0.05% remained. On the sheltered beaches, the rising tides removed large quantities of oil during the first two days after which relatively stable conditions prevailed. Oil was less persistent on the fine-grained sediments than on the pebble-cobble beaches. The back shore plots were not affected by marine processes and climate and soil conditions played a major role in the fate of the oil.
Weathering and biodegradation altered the composition of the oil. The beach cleaning methods evaluated are summarized in Owens et al. (1987b). Techniques evaluated were based on the operational realities of the eastern Canadian Arctic. Small labour force and the impracticability of disposing of large volumes of contaminated materials were the primary limiting factors, therefore the emphasis was placed on the selection of techniques that would either have low labour or simple waste disposal requirement. The methods chosen were in situ combustion using an incendiary device, mechanical mixing of contaminated sediments, application of chemical surfactants to disperse stranded oil (BP1100X and Corexit 7664) and application of a solidifying agent to the stranded oil.
The natural fate and persistence of oil was examined to determine the rates and physical factors influencing the self cleaning process (Owens and Robson, 1987). Neither the incendiary device nor the low-pressure flushing techniques proved to be effective, whereas over the short period of testing (5-6 weeks), mixing and chemical dispersion demonstrated a potential to mitigate the effects of beach contamination or accelerate the removal of the stranded oil (Owens et al., 1987a). Both produced an immediate reduction in the quantity of oil on the beach surface. Chemical solidification was effective in stabilizing the oil but very labour intensive. The BIOS project results provided no major ecological reasons to prohibit the use of chemical dispersants on oil slicks in nearshore areas. Despite unusually severe exposure to chemically dispersed oil the impact on a typical shallow-water benthic habitat was not of major ecological consequence.
Chemical dispersants may be the only alternative in situations where the immediate protection of shoreline and nearshore habitats is of primary importance or where a shoreline cleanup operation is environmentally less desirable. There was no strong ecological reason for the cleanup of oil 159
stranded on Arctic shorelines, except where wildlife is present or their critical habitat is threatened, or areas of human use. Oil residues do persist for long periods on low-energy beaches and backshore areas and in near-by sea-bed sediments. Arctic beaches can be cleaned by oil by natural processes, especially in low priority shorelines, such as Cape Hatt. Response can be directed towards areas of greater importance and sensitivity, such as shores adjacent to communities, wildlife breeding and staging areas, and traditional hunting and fishing camps. Dispersant washing and mechanical mixing may be desirable countermeasures in areas where wildlife frequent the shoreline to reduce contact with the oil. Dispersant washing may also prevent the formation of oil-sediment consolidation (asphalt pavement).
BIOS Revisited
Following the experimental application of oil in August of 1981, the BIOS site was revisited and field studies were conducted in subsequent years (1982, 1983, 1985, 1987, 1989, 1993, 2001) in experimental beach, Bay 11, which was left to weather naturally. Systematic documentation of changes in the distribution, quantity and character of the oil through time has been done (Owens, 1994; Owens et al., 2002; Prince et al., 2002). In 1985, sediment samples and benthic biota were collected in two of the BIOS study bays, one used for surface oil release and the other the reference site (Cross and Humphrey, 1987). Hydrocarbons were still present in subtidal sediment samples four years after the oil releases but the oil content in sediments appeared to have stabilized between 1983 and 1985. Hydrocarbons remaining were predominantly biogenic in all samples from the reference bay and in most samples from the oiled bay. Weathering indices indicated that any oil present in both bays was highly weathered. Low levels of oil remained in 3 benthic species with concentrations higher in the oiled bay than the reference bay. Oil concentration increased between 1983 and 1985 in tissues of the bivalve Serripes groenlandicus from the surface oil release bay and in tissues of the bivalve Macoma calcarea and sea urchin Strongylocentrotus droebachiensis from the reference bay. Both biogenic and highly weather petrogenic hydrocarbons were detected using gas chromatographic analyses. Benthic organisms appeared to be taking up more polar weathered residues present in the water column or remaining in the sediments. There was no evidence of oil-related effects on mean size data or size frequency distributions in three bivalve species. 160
Owens (1994), reported in 1989 an approximately 80% decrease in the total oiled area. Prince et al. (2002), revisited the site of the BIOS in August of 2001, twenty years after the original experiment was conducted to report on the chemical composition of the oil. The vast majority of the original oil was gone, but small patches remained with an estimated <0.5% of the original coverage area. This is a low-energy level beach, and gross physical loss of oil by heavy wave action was an unlikely mechanism to explain the gradual loss of oil. Oil-mineral fines interaction could explain the loss (Owens, 1994).
Samples collected by Prince et al. (2002) remained essentially unaltered despite 20 years of exposure to the elements while others showed that photo-oxidation and biodegradation played an important role in removing the majority of the components of the oil. Prince et al. (2002) used the conserved biomarker 17(H)21(H)hopane (Prince et al., 1994) to show in a sample collected from the intertidal zone that more than 87% of the initial hydrocarbons present were biodegraded, including a significant proportion of initial chrysene and alkylated congeners. Other samples from the surface of the intertidal zone were extensively depleted of chrysenes suggesting photo-oxidative losses. While some samples were extensively biodegraded, others remained essentially unaltered. Samples above high tide were the least biodegraded. This was attributed to the lack of nutrients for microbial growth as their position on the beach had them rarely inundated with water.
Prince et al. (2002) concluded that biodegradation can be a major fate of spilled crude oil on an Arctic beach, even though biological processes are probably restricted to an average of only 63 ice-free days per year (Dickins, 1987). Biodegradation can still occur at low temperatures by indigenous microorganisms (Eriksson et al., 2001) and a more important limitation may instead be the availability of the necessary trace elements for microbial growth. This in turn suggests that a bioremediation strategy that would stimulate oil biodegradation, as has been shown in Spitsbergen (Prince et al., 1999). The fate of the residual oil that does not leave the shorelines by physical transport will eventually be biodegraded, but this will continue to be severely limited by the availability of trace nutrients required for microbial growth.
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7.3 Field Trials in Svalbard, Norway
Early Field Studies on Oil Bioremediation
In 1976, one of the first shore-line field trials to assess the feasibility of bioremediation as an oil spill countermeasure was conducted in Spitsbergen (Svalbard), Norway using inorganic fertilizers as the bioremediation agent (Sendstad, 1980; Sendstad et al., 1984). Unweathered Forcados crude (10 L/m 2 ) was spread on two test sites and the oil was treated with a commercially available fertilizer at an application rate of 1.2 % (wt/vol). The fertilizer stimulated oil biodegradation with a 3 fold increase in microbial respiration rate until 1979. By the end of 1983, the oil on the unfertilized control plot biodegraded to a degree similar to the fertilized plot.
In Situ Treatment of Oiled Sediment Shorelines (ITOSS) Program
The ITOSS program was initiated in Svalbard, Norway in 1997 at a site located located on the Van Mijenfjord, approximately 40 km from the open ocean at approximately 77 56 N and 16 43 E (Sergy, 1999; Sergy et al., 1998). While the purpose of this study and the BIOS program was to better understand in situ shoreline cleanup options, many of the results are applicable to the natural fates of oil on shorelines in general. A series of experimental oil spill studies were conducted on a number of shoreline locations to to quantify the effectiveness of selected in situ shoreline treatment methods to accelerate the natural processes that remove oil stranded on mixed sediment beaches and to investigate the processes that naturally remove stranded oil, such as wave-induced mechanical abrasion and the interaction between oil and fine mineral particles (Owens et al., 2003).
The experimental design of the field trials is described by Gunette et al. (2003). At each of three distinct shoreline sites (exposed to different energy levels), treatment test plots and control plots were established within a continuous stretch of oiled shoreline ranging from 40 to 143 m long. A total of 5500 L of intermediate fuel oil (IFO 30) was deposited along a 3 m wide swath in the upper intertidal zone of each site, the location where oil would be expected to strand in the event 162
of a spill. Approximately one week after oiling, a different treatment technique was applied to each plot. The treatment techniques included sediment relocation (surf washing), mixing (tilling), bioremediation (fertilizer application) and bioremediation combined with mixing. One plot at each site was monitored for natural attenuation. The quantity of oil removed from the plots was measured six times up to 60 days post-treatment and then again one year later. Changes in the physical character of the beach, oil penetration movement of oil to the subtidal environment, toxicity and biodegradation were monitored over the 400 day period.
Sediment relocation of the oiled shoreline significantly accelerated the rate of oil removal (Owens et al., 2003) and reduced oil persistence by at least one year in the sheltered wave energy environment where oil was stranded on the beach in the upper intertidal and supratidal zones, above the level of normal wave activity. Sediment relocation accelerated the short-term rate (weeks) of oil loss from the intertidal sediments on the relatively low wave-energy shoreline, where the stranded oil was located in the zone of wave action.
Oil-mineral aggregation (OMA) formation played a significant role on the effectiveness of the in situ shoreline treatment options of natural attenuation (natural recovery) and sediment relocation (surf washing). At both sand and pebble beach sites, the amount of oil remaining in the experimental plots was dramatically reduced within five days after sediment relocation treatments. Time-series microscopy and image analysis of breaker zone water samples demonstrated that OMA formation occurred naturally on the oiled beaches at both sites and was accelerated by the sediment relocation procedure. Oil in OMA does not adhere to surfaces and is thus more easily removed from mixed sediments. OMA have considerably more buoyancy than mineral particles and can therefore be transported much further before settling to the bottom. The increased surface/volume ratio facilitates weathering processes, in particular biodegradation (Lee et al., 2003). Procedures developed in this experiment to support the use of sediment relocation as an operational spill response option and a guidance document were developed to identify the extent of OMA formation (Stoffyn-Egli and Lee, 2002). No toxic effects were detectable in adjacent coastal waters and sediments at either experimental site as a result of these inherent dispersion processes and of documented oil biodegradation (Lee et al., 2003).
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Mixing and tilling did not clearly contribute to removal of oil within the intertidal sediments (Owens et al., 2003). The changes in total oil loading caused by treatment were small and unlikely to have accelerated natural recovery. Results suggested that mixing/tilling made the shoreline sediment more permeable to seawater and air for at least ten days after tilling, which could lead to enhance microbial activity (Prince et al., 1999).
Oil biodegradation was observed in the intertidal sediments (Prince et al., 2003a) and increased by the application of soluble slow-release fertilizers. Fertilizer application to the surface of the beach delivered nutrients to the oiled sediment beneath the beach surface. Fertilizer application was followed by increased oxygen consumption, increased carbon dioxide evolution from the beach, increased microbial biomass, and significantly greater biodegradation of oil on the plots that had received fertilizer. Changes in the chemical composition of the oil demonstrated that the biodegradation rate was doubled.
The rate of removal by natural processes of oil stranded in the active intertidal zones in the initial ten days after oiling was rapid. After ten days, the removal rate slowed dramatically and oil residue levels did not significantly change for some months. Four to five percent of the original oil still remained in the active intertidal zone after one year (Owens et al., 2003). Oil placed in the supratidal zone penetrated deeply into the coarse grain pebble sediments. About 30% of the oil was lost in the first five days, but no further reduction occurred over the next year and significant quantities remained, despite the relatively high local wave energy on this beach.
The in situ treatment applied during the Svalbard field trails had a distinct and verifiable effect on the rate of oil removal from intertidal sediments. Oil persistence was reduced and secondary effects appeared minimal as sediment location did not elevate toxicity in the nearshore environment to unacceptable levels nor did the treatment methods result in significant alongshore or offshore sediment oiling. Sediment relocation accelerated the removal of oil from the shoreline through the formation of OMA (Owens et al., 2003). Sediment relocation can be used: when sediment is stranded high on a beach above the zone of normal wave activity; when oil has penetrated deeply into beach sediments below the zone of normal sediment reworking; when natural attenuation would take an unacceptable length of time; when bulk oil has been removed 164
and cleaning or polishing of the remaining residue is desirable (high amenity beaches); prior to storm events to expose oiled sediments; when in situ techniques are appropriate because sediment removal is undesirable due to a lack of natural replenishment, or because waste transfer or disposal is an issue; or where there are logistical constraints in remote or inaccessible locations.
7.4 Field Trial Projects on Arctic Oil Spills in Ice
Dickins (2011) has provided an excellent overview of the history of research into the behaviour of oil spills in ice covered waters and summarized what has been learned about the behaviour of oil in ice from actual field experiments involving deliberate crude oil spills for research purposes (Table 7).
As noted by Dickins (2011), experimental oil spills in ice began in the early 1970s and involved fresh and emulsified crude oil spilled under solid ice. The first controlled oil spill in pack ice was conducted by the contractors SL Ross & DF Dickins off the coast of Cape Breton in 1986. Crude oil was spilled in pack ice to investigate the physical and chemical fate of spilled oil in the tested ice conditions. This was followed by a number of focused studies on specific topics as described below.
The most recent and certainly the most extensive Arctic oil spill research program has been the SINTEF Oil in Ice JIP carried out between 2006 and 2009, with the field trials component having been conducted in the Norwegian Barents Sea between 2008 and 2009 (www.sintef.no/Projectweb/JIP-Oil-In-Ice/). This JIP covered a number of subjects of interest to industry, stakeholders and regulators. Large-scale field experiments in the Barents Sea Oil distribution and bioavailability Fate and behaviour of oil spills in ice ISB of oil spills in ice Mechanical recovery of oil spills in ice 165
Use of dispersants and chemical herders on oil spills in ice Oil spill response guide
Table 7 Experimental crude oil spills of a few barrels to hundreds of barrels conducted in sea ice, regardless of latitude (Dickins, 2011). Project Year Reference Location Environment Spills Size Cleanup Behavior of oil spills in the Arctic 1970 Glaeser and Vance, 1971 Chukchi on and under fast ice 1-2 bbl/5 spills burning Crude Oil Behavior on Arctic Winter Ice 1971 McMinn, 1972 U.S. Arctic on fast ice 3 spills on snow not known Interaction of Crude Oil with Arctic Sea Ice 1974/75 Norcor, 1975 Canada Beaufort under fast ice 340 bbl/9 spills burning, mechanical Oil Behavior Under MY Ice 1978-82 Comfort et al., 1983 Canada High Arctic under old ice 11 bbl/ single spill none Oil and Gas Under Sea Ice 1979/80 Dickins and Buist, 1981 Canada Beaufort under fast ice 116 bbl/3 spills burning Oil Migration in Solid Sea Ice 1979/80 Nelson and Allen, 1982 U.S. Beaufort under fast ice 18 spills of 1.5 to 18 gal each mechanical Interaction of Crude Oil with Solid First-year Ice 1980/81 Nelson and Allen, 1982 U.S. Beaufort on fast ice 3 spills sprayed onto snow 6 bbl each burning, mechanical Emulsions in Ice 1982 Buist et al., 1983 Canada Beaufort under fast ice 100 gal/2 spills burning Experimental Spills of Crude Oil in Pack Ice 1986 Buist and Dickins, 1987 Canada East Coast (Nova Scotia) between floes and in leads in pack ice 18 bbl/3 spills burning Marginal Ice Zone Experiment 1993 Singsaas et al. 1994; Vefsnmo and Johannessen, 1994 Barents Sea 75N between floes and in leads in pack ice 164 bbl none Svalbard Experimental Spill 2006 Brandvik et al, 2006; Dickins et al., 2008a Svalbard under fast ice 21 bbl burning Oil in Ice Field Experiment 08 2008 Sorstrom et al., 2010 Barents Sea 78N in openings within pack ice 5 bbl/2 spills burning, herders Oil in Ice Field Experiment 09 2009 Sorstrom et al., 2010 Barents Sea 78N between floes in close pack ice 110 bbl/5 main spills burning, dispersants
The SINTEF field trials also demonstrated the importance of being able to validate small-scale tank tests and meso-scale experiments with large-scale field trials and allowed researchers to 166
document the fate and behavior of spilled oil over time, albeit a relatively short time frame of approximately two years (Brandvik and Faksness, 2009).
Trials to test the differences of spreading oil in open water and ice demonstrated that in most situations, the presence of ice slowed the rate of spreading and oil was contained in a small area (Table 8). A batch crude oil spill measuring 1600 m 3 (10,000 bbl) was carried out and final average thickness and final area of the spilled oil was very different between open water and ice- covered conditions. Oil spilled in ice conditions was significantly thicker than in open water, and the final area of spilled oil was much wider in open water. These findings have implications for response times and decision making during recovery. Oil contained in ice and snow will be thicker and more easily burned or otherwise recovered.
Table 8 Spreading comparison for a 1600 m 3 (10,000 bbl) crude oil spill (SL Ross Environmental Research Ltd. et al., 2010). On Smooth Ice Open Water Under Solid Mid-Winter Ice Ice Snow Final average oil thickness (mm) 0.016 40 to 90 a 3 40 Final area (ha) 10,000 7 to 70 b 50 4 a Maximum pool depth under ice depends on depth of under-ice depressions, which grow deeper as ice grows in winter b The range reflects the variable processes involved: final contaminated area depends on the available volume of under-ice depressions and how they fill with oil
The conduct of large-scale field experiments has overwhelmingly demonstrated how natural containment, reduced wave action and relatively slow weathering in the Arctic environment can aid in spill response scenarios due in large part to the presence of ice and cold water. The findings of these unique aspects of oil fate and behaviour following its release in the Arctic environment extend the window of opportunity for mobilizing response activities and can enhance the effectiveness of certain response measures such as ISB and skimming. However, the unique Arctic environment poses challenges for traditional mechanical cleanup methods, further reason to increase field trials and develop appropriate technologies.
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Encouraging results have come from experimental oil spills that support further research and probable exploration in the Arctic. Low water and air temperatures in addition to ice-covered waters generally result in greater oil equilibrium thickness due to smaller contaminated areas and reduced spreading rates (Dickins et al., 2000; Singsaas et al., 1994; Vefsnmo and Johannessen, 1994). Ignitability is enhanced in cold temperatures and ice due to the greater persistence of lighter and more volatile components of petroleum hydrocarbons(Srstrm et al., 2010). Ice has a dampening effect on waves; therefore, the sea conditions in areas of the Arctic may be significantly less severe than most open ocean areas around the world, thus allowing for easier marine operations (Dickins, 2011). Ice can naturally contain spilled oil and act as a barrier to spreading. The natural herding properties of oil then enhance the effectiveness of ISB by thickening the slick (Dickins, 2011; Srstrm et al., 2010). High ice concentrations (7/10 or more) tend to immobilize and encapsulate most spilled oil quite rapidly, particularly from a subsea blowout (Dickins, 2011). Ice encapsulated oil is effectively isolated from weathering (evaporation, dispersion, emulsification) and allows for a longer window of opportunity to carry out cleanup activities. Effective combustion at a later date is possible as the oil remains unweathered. Most of the Arctic shoreline has a fringe of fast ice which acts as an effective natural barrier against oil contamination on the coastline (Dickins, 2011).
Some response challenges and limitations have also been identified in the field trials. Oil trapped on or under ice in moving pack ice is difficult to assess as crews cannot maintain continuous operations with immediate means of evacuation. Skimming operations can be hindered due to the slow spreading and flow of oil in leads and openings in pack ice. Moving vessels during response operations can cause rapid spreading of oil, creating a thinner, less easily recoverable or ignitable slick. Crude oils with pour points of 0C or less tend to gel.
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7.5 Field Trials on Enhanced Oil Dispersion with Mineral Fines
Field tests were conducted by the Canadian Coast Guard (Lee et al., 2011c) in the St. Lawrence Estuary in the winter of 2008 to assess the feasibility of an oil spill response technique in ice- infested waters based on the application of fine minerals in a slurry with mixing by propeller- wash to promote the formation of OMA. This process promotes the physical dispersion of mineral-fine stabilized oil droplets into the water column which are subsequently diluted below toxicity threshold limits and biodegraded by natural bacteria. Following the release of the test crude oil and the application of experimental treatments, time-series changes in oil concentrations were monitored to quantify dispersion effectiveness. Field samples were also recovered for laboratory microcosm studies on the biodegradation of petroleum hydrocarbons, by monitoring O 2 consumption and CO 2 production (Micro-Oxymax Respirometer), and depletion of specific hydrocarbon components. The GC/MS data shows that with hopane normalization, more than 60% total petroleum hydrocarbon, 75 to 88% of total alkanes, and 55 to 65% TPAHs were degraded after 50 days incubation at low temperature (0.5 o C). The alkylated PAH was degraded to a greater extent in the presence of clay minerals than in their absence. These field and laboratory studies suggest that the proposed remediation strategy can be an environmentally acceptable and cost-effective means to combat oil spill in ice-infested waters. In terms of the Arctic, this technique offers several operational advantages including reduced numbers of personnel required for its application, the lack of need for waste disposal sites, and cost effectiveness.
7.6 Monitoring Arctic Offshore Oil and Gas Operations
Monitoring of the hydrocarbon impact of the Northstar and Liberty oil prospects began in 1999 as the Arctic Nearshore Impact Monitoring in the Development Area program, under the auspices of the Minerals Management Service (now the Bureau of Ocean Energy Management, Regulation and Enforcement), and continues as part of a long-term program to assess potential spatial and temporal changes related to oil development and production near their associated sites (Brown et al., 2011). Annual field surveys of sediment chemistry in the nearshore Beaufort 169
Sea examined PAHs, saturated hydrocarbons, steranes and triterpanes, metals, grain size, total organic carbon, and radionuclides for age-dating. In general, the results indicate that no significant contaminant inputs from Northstar development activities occurred, and that any observed changes were within the bounds of natural variability for the study area. The monitoring, analytical and interpretive methods are believed to be sufficiently sensitive to detect changes that might occur from new input sources.
7.7 Future Oil Spill Field Trials in the Arctic
In light of the recent Deepwater Horizon blowout, fears expressed by the public of an accidental oil spill in the Arctic environment may temper future exploration and development initiatives. While some interest groups claim that industry has little or no experience in responding effectively to Arctic oil spills, during the last two decades there have been a number of new oil spill countermeasure technologies developed and tested in the laboratory. Some techniques such as ISB that were used in the Gulf of Mexico are now being accepted as proven procedures for operational use. There now is a need to have validated oil spill response tools for use in the Arctic to address the requirements of contingency plans and to support oil spill responders. Field trials on Arctic oil spill countermeasures are required. For environmental relevance, efficacy studies on oil spill countermeasures cannot be conducted in the laboratory and mesocosm-scale test facilities alone.
There is a need for government regulators to support the scientific communitys request to undertake large-scale controlled oil spills in the Arctic to support the development and validation of strategies for the protection of the marine environment that will be used in future contingency plans for Arctic offshore drilling operations. The operational effectiveness of numerous new oil spill cleanup technologies and response strategies remains largely unknown. Proof-of-concept and operational guidelines must be established before they are accepted by the oil spill response community. Typically, the only opportunity for oil spill countermeasure techniques to prove their capabilities is during an actual accidental spill (spill of opportunity). Unfortunately, when such events occur, the main focus of the activities is to recover the oil or prevent it from harming wildlife or sensitive environmental areas and generally not on proving the effectiveness of the 170
different techniques employed. To complicate the situation further, regulators have been very reluctant to accept the use of alternative countermeasure techniques, other than mechanical recovery due to the lack of evidence for their performance under field conditions.
The results of the SINTEF JIP field experiments in 2008 and 2009 have recently been very well received by a wide range of stakeholders, with these exceptions: the fact that only a limited number of stakeholders witnessed the work, only one sea ice scenario was included, and only a single location was covered. The scientific and oil response community have agreed that the conduct of large-scale tank tests and field experiments is essential for improving our knowledge and expertise in Arctic oil spill countermeasures.
Field testing for operational improvements and field demonstrations (with equipment deployment) both have a role in illustrating the commitment of the oil and gas industry and government regulators to insure the availability of an effective response capability in the Arctic. To ensure better cost efficiency, equipment practice and demonstrations could be conducted in conjunction with scientific experiments. Due to the global need for this information by nations with Arctic interests and the costs involved for these studies in the Arctic environment, a study of this magnitude should be cost-shared and managed under a collaborative international program. To optimize the use of resources, collaborative multidisciplinary research needs to be promoted. For example, tests on mechanical recovery with skimmers could follow field tests. Validation of tracking and surveillance trials including remote sensing technologies can be coordinated with the release of oil and subsequent oil behaviour tests.
Arctic field trials will provide an experimental framework to evaluate a number of issues of concern, including these: remote sensing systems to detect, monitor and map the transport and spreading of oil in ice and below ice; weathering of oil in cold water/Arctic conditions; development and verification of oil-in-ice drift and fate models; improved mechanical response such as skimmers, pumping systems for viscous oils, and the removal of oil from ice and water; 171
ISB in broken ice (development of fire booms, chemical herding agents, and ignition systems); oil dispersion enhancement by chemical dispersants/enhanced OMA formation (focus on effectiveness, identification of controlling factors and development of application guidelines; bioremediation of oil stranded on shorelines; characterization of water soluble components and biological effects (toxicity) on Arctic species; development of operational end-points for spill cleanup operations.
Results from recent field trials provide proof that carefully planned and executed experimental spills can be carried out safely with no harm to the environment (Dickins, 2011; Lee et al., 2011c; Srstrm et al., 2010). Unless methodologies can be validated in the field, they will not be fully accepted by the oil responders, regulators and the public as operational tools. The conduct of an international program to undertake field trials to support oil spill countermeasure research fits in with the Government of Canadas Northern Strategy Framework, promotes northern science and research, reinforces circumpolar cooperation, strengthens partnerships, and encourages environmental protection. Potential participants include Canada, the United States, Norway, France, Denmark, Sweden and Russia.
In terms of a location for field trials in the Arctic, there is a need to coordinate the conduct of field trials in Canadian Arctic waters as the public does not fully accept data from other regions of the world due to the perception that environmental conditions and sensitivity of indigenous biota are different between geographical regions. This would require the coordination and conduct of controlled oil spill release experiments in Canadian waters to validate emerging techniques for oil spill response in Arctic marine waters with and without ice cover.
The Canadian Arctic is a unique environment, with hydrology, ecosystems and ice behaviour which each pose challenges to understanding the behaviour of pollutants in the high North. The presence of ice, the unique physical environments, and the fragility of the ecosystems reduce the applicability of our knowledge of oil behaviour in temperate climates. 172
There is a considerable corpus of experimental data, but many of the results are anecdotal or empirical in nature. As such, particularly for the historical trials of the earlier decades, it is not easy to abstract these observations into behavioural models. This is changing with some of the more systematic recent studies, but there remain notably large gaps (Khelifa, 2010) between the research that has been accomplished and a basic understanding of the physical processes at work. Empirical relations are often useful rules of thumb, but they have limited extensibility and applicability to conditions other than those of the original experiment.
Current modelling capabilities for oil in ice are approximately two decades old and are typically derived from open water models with factors included to account for the presence of ice. Basic ice physics and behaviour are generally not captured in the analytical models.
Understanding of the weathering processes experienced by oil in the Arctic environment is incomplete. Certain processes such as evaporation, biodegradation and emulsification, are strongly affected by temperature. Many oils also have non-linear transition points (pour points) in the range of Arctic temperatures, which have dramatic effects on oil behaviour, as seen in the work by Buist et al. (2009).
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8. Operational Waste Discharges
Two potential sources of petroleum hydrocarbons in the Arctic marine environment from offshore oil and gas activities include produced water and drilling muds and fluids. A comprehensive review on the potential impacts of Canadian east coast offshore oil and gas exploration and production activities, including the discharge of operational wastes, has recently been released by Fisheries and Oceans Canada (Lee et al., 2011a).
8.1 Produced Water
Produced water is the largest volume waste stream generated by offshore oil and gas activities. It consists of formation water from the oil-bearing substrata brought to the surface with the oil and gas, along with seawater injected into the reservoir to maintain wellhead pressure during production, and in some cases condensed water (Ayers and Parker, 2001; Patin, 1999). Produced water is usually hot saline water that contains a mixture of both organic and inorganic compounds that are naturally present in the geologic formation, as well as treatment chemicals used during drilling, production, stimulation and oil-water separation processes (Hawboldt 2010).
In 2003, an estimated 667 million metric tons of produced water were discharged offshore throughout the world, including 21.1 million tons to offshore waters of North America, mostly the U.S. Gulf of Mexico, and 358-419 million tons to offshore waters of Europe, mostly the North Sea (OGP, 2004; OGP, 2005). These are underestimates of actual discharges, because reporting of production to OGP (2004) ranged from 11 percent to 99 percent in the seven regions of the world monitored. In terms of discharge capacity, it is generally reported that the total amount of water produced from gas fields is much smaller than from oil production fields. While many gas fields discharge less than 10 m 3 of produced water per day, most oil fields discharge hundreds or even thousands of cubic metres of produced water per day (OGP, 2002).
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Considerable concern has recently been raised over the disposal of produced water from production operations as its release is continuous, in comparison to the episodic release of contaminants associated with the disposal of muds and fluids during the drilling of exploration and production wells.
The principal alternative to ocean discharge of treated produced water is underground injection. However, the feasibility of this practice at offshore installations is dependent on a number of site-specific factors including access to a suitable disposal formation, chemical interactions that may result in precipitates that can plug the receiving formation, and cost. Furthermore, the net environmental benefit of reinjection must be considered. On the basis of energy requirements, it is estimated that 2.6-4.3g of CO 2 emissions are produced for each litre of produced water reinjected into a sub-surface well (Shaw et al., 1999).
Chemical Composition
Produced water is a complex mixture of organic and inorganic chemicals in both dissolved and particulate phases (Table 9). The physical and chemical properties of produced water vary widely depending on the age, depth, and geochemistry of the hydrocarbon-bearing formation as well as the chemical composition of the oil and gas phases in the reservoir. Furthermore, since no two produced waters are alike, region specific studies may need to be conducted to address the environmental risks from its discharge.
In Table 9, many of the high values reported for metals may be anomalous due to matrix interferences from high concentrations of dissolved salts in produced water (Neff, 1987). The highest values are extremely rare and concentrations of most constituents in most produced waters, measured by modern, accurate analytical methods, fall into the lower part of the range. 175
Table 9 Concentration ranges (mg/L or parts per million) of several classes of naturally-occurring metals and organic chemicals in produced water world-wide (Neff, 2002). Organic Chemicals Concentration Range Total organic carbon (0.1 >11,000 Total saturated hydrocarbons 17 30 Total benzene, toluene, ethylbenzene, and xylenes (BTEX) 0.068 578 Total polycyclic aromatic hydrocarbons (PAH) 0.04 3.0 Total steranes/triterpanes 0.14 0.175 Total phenols (primarily C0-C5-phenols) 0.4 23 Total organic acids 0.001 10,000 Inorganic Chemicals Salinity (mostly sodium and chloride) <2000 - > 300,000 Sulfate 1.0 8,000 Sulfide 0 - 140 Nitrate 0.6 15.8 Ammonia 14 246 Orthophosphate 0.1 6.6 Arsenic 0.000004 0.32 Barium 0.001 2,000 Cadmium 0.0000005 0.49 Chromium 0.000001 0.39 Copper 0.000001 55 Iron 0.0001 465 Lead 0.000001 18 Manganese 0.0002 7.0 Mercury 0.000001 0.075 Nickel 0.000001 1.67 Zinc 0.000005 200 Total radium (pCi/L) 0 5,150
Petroleum Hydrocarbons
Petroleum hydrocarbons in both dissolved and dispersed (oil droplets) form are the organic components of greatest environmental concern in produced water. Current regulatory guidelines for produced water discharge in Canada are based on petroleum hydrocarbon content. In Canada, the hydrocarbon content of produced water must be reduced to acceptable levels under the 2002 Offshore Waste Treatment Guidelines prior to discharge into the ocean. The minimum regulated standard for the treatment and disposal of wastes associated with the routine operations of offshore drilling and production installations in Canada is 30 mg/L as a 30-day weighted average of oil in the discharge, coupled with a 24-hour arithmetic average not to exceed 60 mg/L.
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Existing oil-water separators such as hydrocyclones are quite efficient in removing the oil droplets within produced water. Thus, the petroleum hydrocarbons discharged to the ocean are typically low molecular weight aromatic hydrocarbons and smaller amounts of saturated hydrocarbons that are found within the dissolved phase of the produced water. Since there are no cleanup procedures that are 100% effective, treated produced water still contains some dispersed oil as droplets ranging in size from 1 to 10 m (Johnsen et al., 2004).
The most abundant hydrocarbons in produced water are the one-ring aromatic hydrocarbons, BTEX and low molecular weight saturated hydrocarbons. BTEX may be present in produced water from different sources at concentrations as high as 600 mg/L (Table 9). Benzene often is the most abundant BTEX compound in produced water, followed by toluene. Because BTEX is extremely volatile, it is lost rapidly during produced water treatment by air stripping and during initial mixing of the plume in the ocean (Terrens and Tait, 1996). PAHs are the petroleum hydrocarbons of greatest environmental concern in produced water because of their toxicity and persistence in the marine environment (Neff, 1987; Neff, 2002). Concentrations of TPAH in produced water typically range from about 0.04 to 3.0 mg/L and mainly consist of 2 and 3-ring PAHs such as naphthalene, phenanthrene, and their alkyl homologues. Higher molecular weight, 4 through 6-ring PAHs rarely are detected in properly treated produced water. When present, they are associated primarily with dispersed oil droplets (Johnsen et al., 2004).
Environmental Concerns over Discharges
Hawboldt et al. (2010) has recently raised concern over the potential impacts of produced water discharges in the Arctic. While the quantity of oil discharged may be small, due to the sensitivity of the Arctic environment there is concern that local impacts could have farther reaching effects, especially with expansion of oil and gas development in the future. The harsh conditions of the Arctic environment result in specific challenges when dealing with the discharge of oil through produced water effluents. Sea water temperatures in the Arctic range from -1 to 1C in the winter to 5 to 10C in the summer. The three most important mechanisms when looking at the discharge of petroleum hydrocarbons and other produced water contaminants are dilution, biodegradation and evaporation. However, in cold water both 177
biodegradation and evaporation rates are significantly reduced. Slower natural contaminant reduction rates increase the probability of exposure and thus toxic effects. In addition, contaminants that would normally dissolve in warmer waters may exist in a dispersed or less soluble state in colder Arctic waters, further reducing their biodegradation and vaporization rates. The discharge of hot produced water into cold receiving water may also result in a plume which rises to the surface forming a sheen. Sheen formation is also more likely in the Arctic since oil in produced water tends to stay in the dispersed phase rather than the dissolved phase due to reduced solubility. The presence of a surface sheen may result in physical impacts on marine organisms such as gill smothering in fish as well as oiling of seabirds and marine mammals.
The presence of ice can affect the fate of oil released into the environment in a number of ways. Ice floating at the surface traps and accumulates dispersed oil. Ice prevents oil from mixing and being diluted and thus oil may concentrate in one location, intensifying local impacts. Ice also reduces the amount of open surface water and thus vaporization rates are reduced. There are a number of sympagic species that may be at risk from the discharge of produced water, such as fish that lay their eggs directly under the sea ice. These eggs or fish larvae can be harmed by exposure to dispersed oil or by the lack of food such as plankton.
Due to the extreme climatic conditions in the Arctic, there are relatively few species resulting in low biodiversity. Since food chains are relatively simple, an input of hydrocarbons which directly affects one species may eventually impact the entire food chain. Migration of animals into the Arctic region are a significant factor that determines the vulnerability of Arctic marine ecosystems. There are a number of species that migrate to the Arctic for wintering, breeding, feeding and molting. The consequence of the congregation of animals means that a small amount of oil in a specific region may have significant ecological consequences. In addition, the long seasonal changes in the Arctic results in a reduced period of productivity in the spring and summer, which increases the risk of impacts from oily discharge. Reduced sunlight during the Arctic winter could affect the removal of contaminants from the system since photo-oxidation rates would be reduced.
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Fate following Discharge into the Ocean
Treated produced waters from offshore platforms are typically discharged above or below the sea surface once regulatory compliance concentrations are achieved. The location of subsurface discharge pipes may range in depth from 10 to 100 m. Saline produced waters are usually as dense, or more dense, than seawater and disperse below the sea surface, diluting rapidly upon discharge into well-mixed marine waters. Low salinity produced water may form a plume on the sea surface and dilute more slowly (Nedwed et al., 2004). Dispersion modelling studies of the fate of produced water differ in specific details, but all predict a rapid initial dilution of discharge by 30 to 100-fold within the first few tens of metres of the outfall. This is followed by a slower rate of dilution at greater distances (Brandsma and Smith, 1996; Smith et al., 2004; Strmgren et al., 1995; Terrens and Tait, 1993). Factors that affect the rate of dilution of produced water include discharge rate and height above or below the sea surface, ambient current speed, turbulent mixing regime, water column stratification, water depth, difference in density (as determined by temperature and total dissolved solids concentration), and difference in chemical composition between the produced water and ambient seawater.
Environmental Effects of Discharges
Based on the concentrations of toxic chemicals in most produced waters and predicted dispersion rates for sites of concern, it is envisioned that there would be only limited potential for acute toxicity beyond the immediate vicinity of rig sites. This is attributed to the sensitivity of the biotests (primarily regulatory acute toxicity assays) and the rapid dispersion of the process stream (Lee et al., 2005a). However, Holdway (2002) noted that to fully assess the potential impact of produced water discharges, the chronic impacts associated with long-term exposures must be quantified. Continual long-term chronic exposure may cause sublethal changes in organisms including decreased community and genetic diversity, lower reproductive success, decreased growth and fecundity, respiratory problems, behavioural and physiological disorders, decreased developmental success and endocrine disruption.
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Effects on Water-Column Organisms
Harmful biological effects in pelagic communities near open ocean produced water discharges are expected to be minimal and localized, because of the rapid dilution and dispersion rates. However, some produced waters contain chemicals that are toxic to sensitive marine species, even at low concentrations. When discharge is in shallow, enclosed coastal waters, or when discharge is of a low density in an area with low water turbulence and current speeds, concentrations of produced water chemicals may remain high long enough to cause ecological harm (Neff, 2002). The chemicals of greatest environmental concern in produced water, because of their potential for bioaccumulation and toxicity, are metals and hydrocarbons. Highly alkylated phenols (octyl and nonyl-phenols), though well known endocrine disruptors, have not been detected in produced water at high enough concentrations to cause significant harm to water column animals following initial dilution. It has been proposed that elevated nutrient (nitrate, phosphate, ammonia, organic acids) concentrations may stimulate microbial and phytoplankton growth in the receiving waters (Khelifa et al., 2003b; Rivkin et al., 2000). Some production treatment chemicals are toxic. If they occur at high concentrations in produced water, the discharge could cause localized harm.
Accumulation and Effects in Sediments
If water depths are shallow, some metals and higher molecular weight aromatic and saturated hydrocarbons may accumulate in sediments near produced water discharges (Means et al., 1990; Neff et al., 1989; Rabalais et al., 1991) possibly harming bottom living biological communities. In well-mixed estuarine and offshore waters, elevated concentrations of saturated hydrocarbons and PAH in surficial sediments may be observed out to a few hundred metres from a high- volume produced water discharge. The concentrations of PAH in sediments near offshore produced water discharges are related to the volume and density of produced water discharged, the PAH concentration in it, water depth, and local mixing regimes. PAHs in sediments near offshore platforms also may come from drilling discharges, particularly if oil based drilling muds are used (Neff, 2005).
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Barium, iron, and manganese are the metals most enriched in produced waters compared to their concentrations in natural seawater. A phase transition typically occurs following the release of produced water. The metals tend to precipitate out rapidly when produced water is discharged to well-oxygenated surface waters that are high in sulphate. These particulate metals tend to settle slowly out of the water column and accumulate to slightly elevated concentrations in surficial sediments over a large area around the produced water discharge (Lee et al., 2005a; Neff, 2002). In addition, the transport and concentration of inorganic constituents within produced water (e.g. metals) to the surface microlayer may be promoted by the interaction between residual oil droplets and metal precipitates (Lee et al., 2005a). Toxicity assessment using the Microtox Test, a regulatory bioassay protocol based on inhibition of a primary metabolic function of a bioluminescent bacterium, showed that unfiltered samples containing metal precipitates generally had higher toxicity levels than filtered samples (Azetsu-Scott et al., 2007). Current results from regulatory environmental effects monitoring programs generally show that natural dispersion processes appear to control the concentrations of toxic metals in the water column and sediments just slightly above natural background concentrations.
Aquatic Toxicity
Information on the toxicity of produced water on Arctic species is limited. Thus our assessment of environmental risk from produced water discharges in the Arctic is primarily linked to studies in other locations around the globe. As the concentration and composition of produced water constituents may vary from one geological formation to another, and species sensitivity may vary, it is recommended that site specific studies be conducted within the Arctic in the future as the need arises.
Most treated produced water has a low to moderate toxicity. A small number of produced waters are moderately toxic to mysids (a small shrimp-like crustacean) and sheepshead minnows (Cyprinodon variegatus), with acute and chronic toxicities less than 0.1% (1,000 mg/L) produced water. A few produced waters are practically nontoxic with acute and chronic toxicities higher than 35 or 40%. Most produced waters have moderate toxicities, with acute and chronic toxicities between about 2 and 10% for mysids and 5 to 20% for sheepshead minnows. Based on 181
earlier toxicity studies for produced waters from the Gulf of Mexico, Neff (1987) reported that nearly 52% of all LC 50 concentrations were greater than 10% produced water, 37% were between one and 9.9%, and 11% were less than one percent. These toxicity threshold limits are consistent with those reported for Atlantic Canada. Mixed function oxidase enzyme activity was highly induced in the liver, gills and heart of juvenile cod exposed to 5% produced water for 72 hours (Andrews et al., 2007). Histological changes were observed in the gills of fish exposed to relatively high levels of produced water. In studies with Calanus finmarchicus, a major prey species for fish in the North West Atlantic, no differences in mortality were found between control and experimental animals exposed to 5% produced water for 48 hours (Payne et al., 2001a).
In a comprehensive study on the acute effects of produced water recovered from a Scotian Shelf offshore well on the early life stages of haddock (Melanogrammus aeglefinus), lobster (Homarus americanus) and sea scallop (Placopecten magellanicus) in terms of survival, growth and fertilization success, Querbach et al. (2005) noted that fed, stage I lobster larvae were the most sensitive with an observed LC 50 of 0.9%. Feeding stage haddock larvae and scallop veligers were the least sensitive with LC 50 values of 20 and 21% respectively. In terms of chronic responses, the average size of scallop veligers was significantly reduced after exposure to produced water concentrations greater than 10%.
There are poorly characterized species differences in the toxicity of produced waters to marine organisms. When bioassays were performed with two or more marine taxa and the same sample of produced water, crustaceans were generally more sensitive than fish (Jacobs et al., 1992; Louisiana Dept. of Environmental Quality, 1990; Neff, 1987; Terrens and Tait, 1993).
Gamble et al. (1987) introduced produced water at a concentration equivalent to a 400 to 500- fold dilution of the effluent (expected within 0.5 to 1.0 km from the Auk and Forties platforms in the North Sea) into 300 m 3 mesocosm tanks containing natural assemblages of phytoplankton, zooplankton, and larval fish. Bacterial biomass increased but phytoplankton production and larval fish survival were unaffected. However, early life stages of copepods were sensitive to the produced water and suffered large mortalities. The decrease in zooplankton abundance resulted 182
in an increase in the standing stock of phytoplankton and a reduction in the growth rates of the fish larvae. In other mesocosm studies summarized by Stephenson et al. (1994), larval molluscs and polychaete worms also were adversely affected. These mesocosm studies show that low concentrations of produced water may have subtle effects on marine planktonic communities. However, it should be pointed out that mesocosm studies represent conservative, worst-case exposure scenarios, because produced water chemicals in the mesocosm enclosures do not degrade and dilute as rapidly as they do in well-mixed ocean environments.
Bioaccumulation and Biomarkers as Evidence of Exposure
As mentioned earlier, biomarkers are quantifiable responses in an organism that often indicate stress due to one or more environmental stimuli. Biomarkers that can be used are based on various biological activities such as gene expression, protein synthesis, antibody production, changes in blood chemistry, frequency of a particular deformity, or some other morphological or biochemical change. Changes in a biomarker are not necessarily a toxic response, but an indication that the organism is responding to a xenobiotic compound. The effect of PAHs has been determined in numerous studies conducted in the laboratory and field using endpoints based on biochemical, histopathological, immunological, genetic, reproductive and developmental parameters (Payne et al., 2003a). Concentrations of PAHs were measured in the water column and in blue mussels (Mytilus edulis) deployed at different distances from production platforms in the Norwegian sector of the North Sea (Durell et al., 2006; Johnsen et al., 1998; Neff et al., 2006b; Re Utvik et al., 1999). Direct measurements of PAH in the water gave inconsistent results, because concentrations were too low and variable. However, the mussels did bioaccumulate PAHs from the water, and concentrations decreased with distance down-current from platforms.
PAH residues in mussel tissues were used to estimate PAH concentrations in surface waters (Neff and Burns, 1996). Surface water TPAH concentrations ranged from 0.025 to 0.35 g/L (parts per billion) within 1 km of platforms and reached background levels of 0.004-0.008 g/L within 5-10 km of discharge, which is equivalent to about a 100,000-fold dilution of the PAH concentration in the discharged water. Dilution modelling showed that most of the produced 183
water plume was restricted to the upper 15 to 20 m of the water column. Dilution was very rapid. The Dose-related Risk and Effect Assessment Model predicted that the concentrations of PAH and other chemicals in the produced water plume exhibited wide cyclic concentration variations due to tidal and wind-driven current flows. Because of rapid dilution and fluctuating water- column concentrations, the model predicted that potentially toxic concentrations and contact times of PAH would not occur even in the near-field.
Brseth and Tollefsen (2004) found that concentrations of metals and PAH in soft tissues of the caged mussels correlated well with distance from the discharge, with highest body burdens in mussels closest to the platform. The PAH assemblage in mussel tissues was dominated by alkyl homologues of naphthalene, phenanthrene, and dibenzothiophene, indicating that the PAHs were from petroleum, likely from the produced water discharge. Biomarker responses in the mussels provided equivocal evidence of exposure to produced water chemicals. The authors concluded that mussels and cod deployed near a discharge probably were exposed to low concentrations of produced water chemicals, below levels that might represent a health risk to water-column organisms.
Elevated mixed function oxidase enzyme levels have been noted in fish larvae collected downstream of the Hibernia field on the Grand Banks of Canada (Payne et al., 2003a). However, induction may only be occurring near the well site with the induced larvae being transported downstream by currents. Petro-Canada and Husky Energy have performed biomarker studies with American plaice (Hippoclossoides platessoides) collected in the vicinity of the Terra Nova and the White Rose offshore developments on the Grand Banks of Newfoundland (DeBlois et al., 2005; Husky Energy, 2005). These studies showed that the overall health of the American plaice was similar to the health of American plaice collected at distant reference sites. American plaice are demersal (bottom-living) fish and may not have been exposed to the produced water plume in the upper water column.
As part of the Biological Effects of Contaminants in Pelagic Ecosystems Program, bioaccumulation and several biomarkers were measured in wild and caged marine animals along a transect away from the Statfjord Platform in the North Sea (Hylland, 2006). Produced water 184
discharge is 74,100 m 3 /day from three platforms in the Statfjord field (Durell et al., 2006), among the highest discharge rates of any offshore field in the world. Frlin and Hylland (2006) measured EROD activity and bile metabolites in juvenile cod caged at several distances down- current from one of the discharges. There were no significant trends in EROD activity in male and female cod with distance from the discharge, though there was a trend for EROD activity in female cod to increase with distance from the discharge, a trend opposite the expected one. In spite of this, concentrations of alkylnaphthalene metabolites in fish bile were highest in cod near the platform and decreased with distance from the platform. Alkylnaphthalenes are abundant in produced water. There were no distance trends in concentrations of other PAH metabolites in cod bile. The authors concluded that the cod were exposed to low levels of PAH from the produced water discharges, but exposure levels were well below those that would pose a health risk to fish living near the platforms.
A recent study by Hamoutene et al. (2010) investigated the effects of produced water on cod immunity, feeding and general metabolism by exposing fish to diluted produced water at concentrations of 0, 100 and 200 ppm for 76 days. No significant differences were observed in weight gain or food intake. Similarly, serum metabolites, whole blood fatty acid percentages, and mRNA expression of an appetite-regulating factor (cocaine and amphetamine regulated transcript) in the brain remained unchanged between groups. Other than an irritant-induced alteration in gill cells found in treated cod, resting immunity and stress response were not affected by produced water. Changes in enzymatic activity of catalase and lactate dehydrogenase were observed in livers but not in gills, suggesting an effect on oxidative metabolism subsequent to hepatic detoxification processes. To evaluate potential effects of produced water discharges on cod immunity, fish from the three groups were challenged by injection of Aeromonas salmonicida lipopolysaccharides at the end of exposure. The lipopolysaccharide injection affected respiratory burst activity of head-kidney cells, and circulating white blood cells ratios, and increased serum cortisol in all groups. The most pronounced changes were seen in the group exposed to the highest dose of produced water (200 ppm).
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Alteration of Trophic Level Dynamics by Produced Water
A modelling study was carried out to assess potential perturbations in food web structure and energy flow due to the discharge of produced water (Rivkin et al., 2000). The model predicted significant increases in productivity and sedimentation fluxes over large spatial domains in response to produced water derived ammonia and dissolved organic carbon.
Bacteria have very short generation times and respond rapidly to environmental changes. As bacteria are involved in primary processes including the production of carbon, nutrient cycling, biodegradation and biotransformation of contaminants their use in environmental effects monitoring programs has been recommended (Lee and Tay, 1998; Wells et al., 1998). Studies by Anderson et al. (2000) with naturally occurring bacteria indicated the potential for produced water to both inhibit (short-term exposure at high concentrations) and enhance bacterial growth (lower concentrations over an extended period).
In a recent study by Yeung et al. (2010) changes in indigenous microbial community structures in response to the discharge of produced water from an offshore platform on the Grand Banks of Canada were monitored by DGGE. The DGGE results showed that the production water did not have a detectable effect on the bacterial populations in the surrounding water. Cluster analysis showed greater than 90% similarity for all near surface water (2 m) samples, approximately 86% similarity for all the 50 m and near bottom samples, and approximately 78% similarity for the whole water column from top to bottom across a 50 km range, based on two consecutive yearly sampling events. However, there were distinct differences in the composition of the bacterial communities within the produced water compared to seawater near the production platform (~50% similar), indicating that the effect from produced water may be restricted to the region immediately adjacent to the platform. Specific microorganisms (Thermoanaerobacter of the eubacteria, and Thermococcus and Archaeoglobus of the archaea) were detected as significant components of the produced water. These particular signature microorganisms may be useful as markers to monitor the dispersion of produced water into the surrounding ocean.
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Ecological Risk of Produced Water Discharges
The Norwegian oil and gas industry advocates ecological risk assessment as the basis for managing produced water discharges to the North Sea. Neff et al. (2006b) compared estimates of ecological risks of PAHs from produced water to pelagic communities based on data from hydrocarbon residues in soft tissues of blue mussels (M. edulis) deployed for a month near offshore platforms and based on predictions of the Dose-related Risk and Effect Assessment Model. The study was performed near produced water discharges in the Tampen and Ekofisk Regions of the Norwegian Sector of the North Sea. Because PAHs are considered the most important contributors to the ecological hazard posed by produced water discharges, comparisons focused on this group of compounds. The two methods ranked stations at different distances from produced water discharges in the same order and both identified 2 and 3-ring PAHs as the main contributors to the ecological risk. Neither method identified a significant ecological risk of PAH in the upper water column of the oil fields.
Due to chemical kinetic reactions that occur following the release of produced water in an anoxic state into the open ocean, it has been suggested that the toxicity of produced water may change over time following its discharge (Lee et al., 2005a). The significance of this process is clearly illustrated in controlled dose-response experiments using natural microbial populations as the test organisms. A typical toxicity dose-response curve (initial increase in productivity at low concentrations of produced water due to addition of nutrients, followed by inhibition above a threshold value) was observed with fresh produced water, that is, process water that has been treated but not discharged. However, following aeration for 44 hours (to simulate equilibration in the ocean following discharge) additions of the produced water over the same concentration gradient elicited a stimulatory response. The difference after aeration was attributed to the loss of low molecular weight hydrocarbons, and the precipitation of hydrolysis metals that may have sequestered toxic metals and other chemicals. These results imply that accurate comparisons of toxicological studies with similar endpoints (e.g., LC 50 ) cannot be made unless sample collection and handling protocols are standardized prior to toxicity testing.
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Produced Water Treatment
Most environmental regulatory agencies in countries that have significant offshore oil and gas production place limits on the concentrations of petroleum (usually measured as total oil and grease) that can be present in produced water destined for ocean discharge. Table 10 gives examples of limits on oil and grease imposed by different countries.
Table 10 National permissible concentrations of total oil and grease in produced water destined for ocean disposal (Veil, 2006). Country Monthly Average (mg/L) Daily Maximum (mg/L) Canada 30 60 USA 29 42 OSPAR (NE Atlantic) 30 --- Mediterranean Sea 40 100 Western Australia 30 50 Nigeria 40 72 Brazil --- 20
Produced water intended for ocean disposal usually is treated on the platform or at a shore treatment facility to meet these regulatory limits. The objectives of oil-water-gas treatment on an offshore platform are to produce stabilized crude oil and gas for pipeline or tanker transport to shore facilities, and to generate a produced water that meets discharge requirements (if discharged to the ocean) or is suitable for reinjection into the producing formation or another geologic formation (Bothamley, 2004).
Within Canada, the formulation of regulatory guideline values for produced water discharge is an adaptive process that promotes the development of improved environmental effects monitoring programs that takes into consideration the level of environmental risk, and the best available technology for mitigative measures and socio-economic benefits. Currently, waste discharges in the Arctic are subject to strict regulatory standards, with the U.S. and Norway having more mature regulatory systems compared to Russia, Greenland and Iceland (Hawboldt et al., 2010). A summary of the treatment systems used in three Arctic regions (Beaufort Sea in Alaska, Norwegian Barents Sea, and Sakhalin Island in Russia) can be found in Table 11. In all cases the 188
projects have adopted a zero-discharge limit. Although re-injection is a common practice, it is associated with high energy usage and the creation of large amounts of air emissions. To meet the future challenges for the treatment and disposal of produced water in the Arctic and the establishment of improved regulatory guidelines, new technologies will need to be developed and implemented.
Table 11 Summary of produced water treatment systems used by three Arctic oil and gas installations; adapted from Hawboldt et al. (2010). Installation/Oil and Gas Field Water Depth (m) Treatment Technology BP Northstar/North Slope Alaska 12 A single well was drilled and used for disposal of all waste streams, including produced water and drill cuttings. Norwegian Barents Sea ~400 Existing operations are required to dispose of produced water through re-injection. No new oil and gas development is permitted due to environmental concerns. Piltum-Astokhskoye/Sakhalin Island, Russia (12-15km offshore) 1900-2500 Produced water is treated and used as a supplement of the primary source seawater. Azeri Chirag Gunashli/Azerbaijan, Russia 125-175 An electrostatic coalescer is used to separate 95% of the produced water which is re-injected into the geologic formation. The remaining 5% is transported back to shore for further treatment.
Environmental Effects Monitoring and Research Needs
The general consensus of the scientific community is that any effects of produced water on individual development sites in the open ocean are likely to be minor (Lee and Neff, 2009). The toxicity threshold limits for acute effects are not likely to occur beyond the immediate vicinity of the discharge pipe due to the effectiveness of natural dispersion processes driven by tides, currents and wind. However, unresolved questions regarding aspects of produced water composition, its fate and potential effect on the ecosystem remain. The effects of chronic toxicity may only become evident after monitoring several life stages or generations. It is important to 189
acknowledge the consequences of long-term effects from offshore oil and gas facilities that may have a 15-20 year lifecycle. Furthermore, cumulative effects linked to future expansion of production operations must be considered. It is evident that additional information is needed to improve the accuracy of existing risk assessment models for produced water discharge. Multidisciplinary scientific studies are needed under an ecosystem based management approach to provide information on the environmental fates (dispersion, precipitation, biological and abiotic transformation) and effects of chronic, low-level exposures of the different chemicals in produced water.
Numerical models need to be improved to better predict the fate and effects of chemical constituents in produced water plumes that are rapidly dispersed. There is a need to develop improved sample recovery and analytical techniques to support model validation needs. At present many of the potential contaminants of concern in produced water cannot be detected in the open ocean environment with standard analytical protocols. The future development of high efficiency, cost-effective produced water treatment technologies is dependent on the identification and monitoring of the primary target constituents of environmental concern (e.g., PAH, phenols, metals).
For a comprehensive protection plan, there is a need to support the development of improved monitoring protocols to provide early warning of any potential problems related to sediment and water quality (such as primary productivity), fish quality and fish health. Development of real- time monitoring systems (contaminant specific sensors and data-transfer technologies) will enhance our capacity to manage the ocean and its living resources. In consideration of natural perturbations currently occurring within the ocean (e.g., climate change) and the impacts potentially associated with other users of the oceans (marine transport, fisheries, etc.), an ecosystem based integrated management approach must be taken to fully evaluate the risks of produced water discharge into the oceans.
Interpretation of ecological risk from biological effect studies based on biomarker techniques remains a challenge. Biomarkers may be used to indicate that 1) an organism has been exposed to a specific chemical or group of chemicals; 2) an organism is affected by a contaminant and 190
responding to it; and 3) the organism has been damaged. However, as discussed by Gray (2002) in an editorial comment entitled, Perceived and real risks: Produced Water from oil extraction, the question at the site of concern is, What is the risk to populations in the field?
8.2 Drilling Muds
Drilling muds are used by the offshore oil and gas industry to cool and lubricate the drill bit, to balance subsurface hydrostatic pressure, and to carry drill cuttings up to the surface through drilling pipes. Drilling muds typically contain a base fluid (water-based, oil-based, or synthetic- based), barite or bentonite (weighting agent), and chemical additives (emulsifiers, biocides, lubricants, wetting agents, corrosion inhibitors, surfactants) to enhance the muds operational properties (GESAMP, 1993). On the drill rig, the cuttings and muds are separated to recycle the muds while the cuttings once treated may or may not be discharged into the sea. Once discharged, drilling muds and cuttings undergo a number of physico-chemical processes in marine environments: (1) advection, (2) dispersion, (3) aggregation, (4) settling, (5) deposition, (6) consolidation, (7) erosion, (8) re-suspension, (9) re-entrainment, and (10) change in bed elevation. The relative impacts of these processes on the fate of drilling wastes in marine environments depend on the characteristics of drilling wastes and physical variables of the water body such as water depth, currents (tidal and residual), waves and storms.
The biological effects of drilling wastes generally can be thought of as being caused primarily by (1) chemical toxicity from hazardous pollutants and biodegradation products; (2) organic enrichment of the seabed that may result in anoxic conditions; (3) physical smothering due to accumulation; and (4) physical effects on tissues (causing reduction in growth and reproduction) due to chronic exposure to very low concentrations of the drilling mud compounds bentonite and barite (Cranford, 2006).
Most drilling of offshore oil and gas wells in the North Sea, the Gulf of Mexico and other offshore production areas is achieved with water-based drilling muds (WBM). This is due to strict regulations on discharges of oil-based mud (OBM) and synthetic-based mud (SBM) as a result of their potential environmental impacts. SBM were designed to be less toxic and more 191
environmentally friendly than OBM. The use of SBM over WBM comes with concerns over the risk of organic enrichment and the potential persistence of synthetic-based fluid biodegradation products. However, these risks must be weighed against the higher levels of turbidity and metal contaminations associated with bulk WBM disposal. Veil et al. (1995) noted that WBM use typically generates between 1100 and 2000 cubic metres of muds and cuttings depending on the depth and diameter of the well compared to 300-1300 cubic metres for SBM.
Although they were first used in the North Sea, the use of SBM in the North Sea has been curtailed since 2001 when the OSPAR Commission (a consortium of fifteen Governments of the western coasts and catchments of Europe, together with the European Community cooperated to protect the marine environment of the Northeast Atlantic) stated that the discharge into the sea of cuttings contaminated with synthetic fluids shall only be authorized in exceptional circumstances. WBM, but not OBM or SBM, may be permitted for ocean discharge into European offshore waters provided that they do not contain hazardous chemicals. All drilling mud chemicals intended for offshore disposal must be tested for toxicity, bioaccumulation and biodegradability. Norway recently introduced a zero harmful discharge policy. Although this was mainly intended for produced water discharges, it was extended to drilling wastes as well. However, the Norwegian government is re-evaluating the discharge of WBM since it may be less environmentally harmful than the alternative disposal practices. Both WBM and SBM cuttings, but not OBM cuttings, also are permitted for discharge into offshore waters of the U.S. Gulf of Mexico, with requirements of the SBM material registered as biodegradable under anaerobic conditions with indigenous microorganisms.
Current regulations in Canada (NEB et al., 2002) stipulate recovery and onshore disposal of the cuttings generated using OBM. SBM remaining from a drilling mud change-over or drilling program completion should be recovered and recycled, re-injected down-hole, or transferred to shore. The cuttings produced with WBM are allowed to be discharged into the sea as well as those produced with SBM following treatment with the best available technology. Best available technology in some offshore regions internationally is believed to be capable of achieving a concentration of 6.9 g/100 g oil on wet solids. This discharge limit may be modified in individual circumstances where more challenging formations and drilling conditions are 192
experienced or areas of increased environmental risk are identified. It is anticipated that performance will improve in the future as further advancements in technology and operating procedures evolve.
Arctic Marine Food Webs and Toxicity
There is evidence that trophic level dynamics in the Arctic may diminish the toxic effects of drilling muds. Arctic marine food webs are relatively simple compared to those in more temperate climates. Metals and hydrocarbons are not likely to enter the food web or bioaccumulate up the trophic levels. A number of short-term and long-term toxicity tests have been performed on whole WBM as well as WBM ingredients with a wide variety of freshwater and marine plants and animals, including many species from Arctic and cold-water environments of Alaska, Canada and Norway. WBM containing ingredients permitted by current U.S. effluent guidelines or on OSPARs PLONOR list (List of Substances/Preparations Used and Discharged Offshore That Are Considered to Pose Little or No Risk to the Environment) were non-toxic to all species. A number of microcosm and mesocosm experiments have confirmed that WBM cuttings have no effects, or minimal and short-lived effects on zooplankton and benthic communities. The lack of bioaccumulation or toxicity of WBM indicates their effects are highly localized within close proximity of the discharge point, and are not being exported to the food web.
No measurable adverse effects of routine WBM discharges on the water column environment have been reported, because most are small amounts discharged intermittently over the course of several months (Neff, 2005; NRC, 1983). When ecological effects are detected, it is often due to physical disturbances caused by elevated concentrations of suspended particles in the water column which may clog the gills or digestive tract of zooplankton or benthic filter-feeding invertebrates. Drilling wastes may also bury some sessile or low mobility benthic species. By changing the sediment grain size and texture it may make the substrate unsuitable for certain native species. The biodegradation of settled organic material in the WBM may also stimulate bacterial growth leading to a depletion of oxygen. Overall, these processes may cause changes in 193
species abundance, composition and diversity of the benthic community, although it is rare for this to occur in sediments near WBM discharges.
It is known that the rate of benthic recovery depends on the thickness of the mud and cuttings that accumulate on the sea floor, but recovery might also be slower in cold water environments compared to more temperate locations. In general, the physical disturbances to the water column and sediments from SBM discharges are similar in character and magnitude to the disturbances caused by natural processes such as storms, and inputs of suspended sediments from Arctic rivers during spring breakup and ice scour. Arctic species are well adapted to seasonal disturbances and will recover rapidly from the relatively brief and intermittent disturbances associated with exploratory drilling operations. 194
9. Case Study: The Exxon Valdez Oil Spill
The Exxon Valdez ran aground on Bligh Reef, Prince William Sound (PWS) on March 24, 1989, and released approximately 42 million litres of ANS crude oil into the coastal marine environment (Spies et al., 1996). Of this, approximately 40% washed ashore (Gilfillan et al., 2000) and 783 km of coastline were oiled (Neff et al., 1995). The Alaskan coast is known for its rich marine life of seabirds, marine mammals, whales and seals, as well as supporting a multi- million dollar fishery of pink salmon, pacific herring and groundfish. The rugged coastline is also a backdrop for tourism which, along with the fishery, is a key component of the Alaskan economy (Spies et al., 1996). The immediate impact of the spill was the death of about 250,000 sea birds, 22 killer whales, 2800 sea otters, 300 harbour seals, and untold numbers of fish eggs (Guterman, 2009).
Several strategies were employed to treat the Exxon Valdez crude oil (EVCO). Some beaches were left untreated while others subjected to cleanup. Initially, oil was removed from the shoreline with aggressive washing techniques, but eventually less destructive methods were used (Wells et al., 1995). Cleanup methods included low pressure warm-water washes, high pressure hot water washes, the dispersant Corexit 7664, and the beach cleaner Corexit 9580 M2. While all treatments were suspected of causing some deleterious effects, the most damaging was application of high pressure hot water, with the areas subjected to this treatment exhibiting impacts six years after the spill (Lees et al., 1996).
General reviews of the effects of the Exxon Valdez oil spill (EVOS) have been published at regular intervals (Paine et al., 1996; Peterson, 2001), with the most recent of by Peterson et al. (2003) and Harwell and Gentile (2006). Peterson et al. (2003) stated that as of 2003, there were detectable effects of the EVOS on the PWS ecosystem, but that they were no longer the result of acute toxicity. Chronic exposure to sublethal concentrations of EVCO was now the concern, and these effects were being observed in many species in PWS. The authors stated that there had been a paradigm shift, moving away from the effects of short-term acute toxicity on individual species to an ecosystem-based synthesis of short and long-term impacts. Harwell and Gentile (2006) examined about 500 peer-reviewed articles in order to assess whether the marine 195
ecosystem had recovered by 2006. They applied the concept of a VEC, including birds (bald eagles, harlequin ducks), marine mammals (otters, orcas, seals), invertebrates (clams, mussels) and other components referred to as higher levels of organization (e.g. intertidal and subtidal communities, the trophic structure of PWS, and water quality). By examining the literature on effects related to VECs, they came to the conclusion that although the EVOS and associated cleanup had profoundly affected the ecosystem from the time of the spill until a few months to a few years later, longer lasting effects were masked by anthropogenic stressors in PWS that were not associated with the EVOS.
The long-term impacts of the EVOS are still in dispute. While the waters of PWS are now clear and shorelines bristle with life, oil still lingers, hidden beneath rocks and below the surface of beaches (Guterman, 2009). To date, the controversial environmental assessment studies following the incident have been the longest, largest and most expensive ever done. Consensus has not been reached between various parties of government, the public and industry over the level of long-term effects and their environmental significance. Much of the dispute revolves around whether or not industry should be held responsible for funding additional monitoring, research and remediation operations (Guterman, 2009; Landis, 2007). The problem with quantifying impact assessment, toxicity, and recovery of an ecosystem is that all three processes depend on a number of factors (Shigenaka, 2005) that are influenced by the investigator, the metrics used, the benchmarks for determining what is affected, and the statistical approached employed. As a result, any definitive answer to a question like, Has the PWS ecosystem recovered from the EVOS? would be next to impossible to achieve. In addition, the definition of recovery is problematic. Peterson et al. (2003) seem to regard it as synonymous with a return to pre-spill conditions, while Harwell and Gentiles (2006) utilization of a more value-driven approach is based on the assumption that an ecosystem will reach equilibrium (Landis, 2007). In actuality, there are many definitions available (Parker and Wiens, 2005). Inevitably a bias a will develop, depending on which definition is chosen, as this will be a policy-driven process (Landis, 2007).
The chemistry, toxicity and fate of EVCO, plus the effect on birds, mammals, fish, invertebrates, and the intertidal zones for the first several years after the spill has been well documented. Books 196
such as Proceedings of the Exxon Valdez Oil Spill Symposium (Rice et al., 1996) and Exxon Valdez Oil Spill: Fate and Effects in Alaskan Waters (Wells et al., 1995) cover the topics well, and several reviews (Harwell and Gentile, 2006; Paine et al., 1996; Peterson, 2001; Peterson et al., 2003) are good summaries of fate and effects up to the time they were published.
9.1 Fate of the Oil
Fractionation of the spilled oil started soon after its release from the hull of the Exxon Valdez. Physical, chemical and biological processes sub-divided the oil into components that travelled at different rates depending on their chemical properties and environmental conditions (Spies et al., 1996). Volatile components evaporated as the slick was transported by wind and waves. Three days after the spill, a storm occurred in PWS, which further fractionated the oil through evaporation, dissolution, physical dispersion, emulsification, adsorption onto suspended particles and grounding on the shoreline (Spies et al., 1996).
Residual oil continues to be detected on beaches in PWS. Short et al. (2004) discovered oil on 71 of 91 beaches randomly selected according to their oiling history in 2001, and arrived at a conservative estimate of 55,600 kg of EVCO remaining sub-surface, putting the beaches where the oil still resides at continued risk of biological exposure. This estimate of residual oil has been supported by the calculations of (Pella and Maselko, 2007) who estimated that PWS had 41,000 m 2 of surface oiled areas and 71,000 m 2 of sub-surface oiled area in 2001, representing approximately 50,000 kg of oil. Taylor and Reimer (2008) found EVCO present in and on 39 beaches using the shoreline cleanup assessment team field observation program procedures. The oil was detected as asphalt pavements in the upper intertidal to supratidal zones, while subsurface oil persisted as an approximately 3 cm thick band about 5-10 cm below a pebble and gravel veneer. They also discovered that at six previously oiled sites there was no longer any oil detected and concluded that, based on their calculations, only 0.5% of the shorelines of PWS contained residual oil. They postulated that the persistence of the oil was due to it being incorporated into finer sediments, isolating the oil from active weathering in shoreline wave shadows with limited wave action (Taylor and Reimer, 2008).
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Exxon-funded researchers did not dispute the presence of residual EVCO in PWS. They did, however, question the amount and the condition in which it is found. By 1992, the area occupied by sub-surface oil was estimated to be about 12,000 m 2 (Neff et al., 1995). In addition, a more recent study (Boehm et al., 2008) of 22 sites that had been most heavily oiled in 1989 concluded that in over 90% of the samples collected, there was no oil. In addition, those samples that still contained EVCO were characterized by heavily (>70%) weathered oil that was located in mid to upper intertidal zones (Boehm et al., 2008), away from areas of biological activity. Boehm et al. (2008) concluded that most of the biologically-available oil in PWS had been eliminated through natural weathering. This idea was disputed by (Short et al., 2006) who discovered residual EVCO on 14 shorelines, with most of the oil located near the mid-intertidal zone and about half of the sub-surface oil located in the lower intertidal zone rich in biological activity. As a result, they stated that there was a significant likelihood of sea otters and harlequin ducks encountering sub-surface oil.
The conditions contributing to the creation of persistent EVCO on PWS beaches have been investigated in detail. Beaches exposed to oil mousse, an emulsion of EVCO and water (see Section 3.4 Factors Influencing Oil Fate (Weathering), Emulsification), contained persistent oil (Short et al., 2007), while beaches that were not exposed to the mousse did not have as much residual oil (Irvine et al., 2006). Oil mousse appeared to resist weathering, resulting in the prolongation of the effect of toxic PAHs (Short et al., 2007) and was compositionally similar to 11-day old EVCO (Irvine et al., 2006). In addition, physical processes associated with persistent oil included boulder armour, where finer sediments trapped beneath boulder lags resulted in the persistence of lightly-weathered oil in a high-energy environment (Irvine et al., 2006). Added to this, a permeable surface sediment can act as a temporary storage layer, and then funnel oil to more permanent storage in underlying low-permeability sediment when the water table drops (Xia et al., 2010). This lower layer in which the oil can become isolated exhibits nearly anoxic conditions, reducing the possibility of biodegradation or weathering (Li and Boufadel, 2010). When combined with tide-induced exchange of groundwater in mid-intertidal to high intertidal zones, this would result in the persistence of oil in low intertidal regions (Xia et al., 2010).
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Subsurface oil from EVOS still exists in scattered patches within shoreline sediments of low permeability (Boehm et al., 2011). The oil in these sediments is protected from weathering (erosion, dissolution, biodegradation) because of surface boulder and cobble armour. As such, the oil is not accessible or bioavailable to wildlife that forage on the shore (Boehm et al., 2011). This is also the reason why PAH levels in the water of shorelines identified as having the most residual oil are similar to background: the trapped oil is found in sediment that is 100 to 1000 times less permeable than the surrounding sediment (Pope et al., 2011). Laboratory experiments showed that there was limited contact between groundwater and oiled sediments, and if any PAH entered the aqueous phase, it would be readily washed out and diluted by tidal action (Pope et al., 2011).
Geospatial models have been used to locate where subsurface oil from the Exxon Valdez is most likely to persist after 19 years following the spill (Michel et al., 2011). Field data collected from 314 sites (2001 to 2007) were used to identify geomorphologic and hydrologic factors involved in the persistence of the subsurface oil. The relationships between the data and the physical factors controlling oil persistence were not clearly understood in all cases. The results indicated several unsurveyed shoreline locations as potentially having subsurface oil, which could be quantitatively prioritized for investigation.
Samples of beach substrate containing subsurface 19 year-old oil from EVOS were tested in microcosms for biodegradability (Venosa et al., 2010). With nutrient amendment, oil in the substrate was found to be significantly (p < 0.01) more biodegradable than natural attenuation, no matter what the degree of weathering. The reason that the subsurface oil had persisted was predominantly due to a lack of oxygen in the interstices of the sediment from where the oil was retrieved. Nitrogen was found to be a secondary factor limiting biodegradation. Biologically available nitrogen is often relatively low in marine environments, and hydrocarbon loadings of >10 ppm in a closed laboratory microcosm will likely result in low rates and extent of biodegradation (Lee et al., 2011d). This was overcome by the addition of nutrients. Biodegredation occurred in the natural attenuation microcosms because of the high concentrations of nitrogen in the substrate, and the aerobic test conditions (Venosa et al., 2010).
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9.2 Effects of the Oil
Bioavailability
One important question concerning the residual oil is whether or not it poses a hazard to the environment. If the remaining oil is biologically inert, meaning that it is either no longer releasing compounds, or any compounds that are released are non-toxic, then it is considered to be biologically unavailable. PAHs are considered to be the primary source of stranded oil toxicity, especially those of higher molecular weight. The exposure of intertidal animals to bioavailable PAHs from residual EVOS oil was first noted by (Roberts et al., 1999), and continued to be observed over the next decade (Deepthike et al., 2009; Springman et al., 2008; Thomas et al., 2007). Venosa et al. (2010) have demonstrated that 19-year-old weathered EVCO can still be biodegraded. The fact that this oil is still biodegradable could be due to several factors including the absence of biodegrading bacteria, an electron acceptor, and nutrients necessary to facilitate microbial degradation in the zones where the oil is trapped. The significance of these observations have been questioned by other scientists who contend that the oil remaining from the EVOS is buried below zones frequented by the biota, or is weathered to the extent that the residues exude PAHs at low concentrations (Boehm et al., 2007a; Neff et al., 2006a), or release PAHs that are not toxic (Page et al., 2002). These scientists also contend that PAHs from the EVOS residual oil are now at such low levels (Neff et al., 2006a), that they are masked by PAHs released by non-EVOS sources (Page et al., 1996; Page et al., 2006). This contention is supported by the results from the Long-Term Environmental Monitoring Program, indicating that TPAH concentrations in the PWS ecosystem are now at background levels (Payne et al., 2008).
Shoreline Flora and Fauna
Peterson et al. (2003) reported that clams and other invertebrates living in subtidal and intertidal areas in PWS with contaminated sediments remained contaminated for more than a decade. However, recent literature (later than 2004) cannot be found on the response of the PWS ecosystem to EVCO, and even though the initial stranding of oil on the shoreline had an effect on 200
the biology of the infauna, epifauna and macroalgae (Dean and Jewett, 2001; Driskell et al., 1996), it was the methods used for shoreline cleanup (primarily high-pressure, hot water washing) which had the most devastating effect. The cleanup methods resulted in thermal shock in the intertidal zone (Driskell et al., 1996; Lees et al., 1996). All sites in PWS exhibited signs of recovery by the early 1990s (Driskell et al., 1996; Gilfillan et al., 1995a; Gilfillan et al., 1995b; Houghton et al., 1995). However, the recovery of cleaned sites lagged behind sites that were left to natural attenuation (Driskell et al., 1996; Lees et al., 1996; Skalski et al., 2001). Habitat- specific recovery of shallow, subtidal communities following the EVOS were investigated (Dean and Jewett, 2001). Impacts were greatest in sheltered bays that were subject to heavy oiling.
In subtidal areas of eelgrass (Zostera marina), the long-term effects of EVOS were identified as decreased mean density of shoots and flowering shoots (Dean et al., 1998). Over a period of up to 10 years after the spill, impacts were greatest in nearshore, subtidal (<11 m deep) communities of sheltered bays that had been heavily oiled, in which it was observed that the effects of oiling and cleanup were more pronounced on the eelgrass beds than in kelp habitats comprised mostly of Agarum clathratum and Laminaria saccharina (Dean and Jewett, 2001). One year after the spill, concentrations of TPAHs were higher in the eelgrass beds than among the kelp. Also, there were more groups of organisms at lower densities in eelgrass than in kelp beds in the oiled sites compared with control sites.
Dean and Jewett (2001) noted that recovery was slower for eelgrass than kelp, with approximately 80% of the impacted groups of organisms in eelgrass beds appearing unrecovered in 1995, while most of the impacted groups in kelp beds recovered in two years. It was suggested that the protracted recovery of the eelgrass beds was probably because of them having more sensitive species such as crustaceans, in addition to the higher concentration of TPAHs, and the persistence of the oil within the sheltered, soft sediments as opposed to the sand and boulder substrate of the kelp beds.
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Invertebrates
Both mussels and clams are sources of food for foraging sea otters and harlequin ducks, and mussels were used as part of the Long-Term Environmental Monitoring Program. The program was started in 1993 to assess the presence of lingering oil (as PAHs and saturated hydrocarbons) in the tissues of mussels from sites in PWS and the Gulf of Alaska. Prolonged effects of PAH exposure on mussels were still detectable in 2002 (Thomas et al., 2007), but have subsequently been judged to be at background levels since 2004 (Boehm et al., 2004; Payne et al., 2008; Reynolds and Braman, 2009), presenting no further risk to foraging sea otters or harlequin ducks (Neff et al., 2011).
Fish
The long-term effects of the EVOS on fish in PWS are the subject of ongoing dispute. Initial effects on fish species were thought to be the result of reduction in the number of adult fish returning to PWS in later years due to oiling of juveniles (Geiger et al., 1996; Willette, 1996) or exposure of embryos or larvae to oil or its residues (Brown et al., 1996; Carls and Thedinga, 2010; Rice et al., 2001). Benthic fish species appeared to suffer less with reports of no pervasive deleterious effects (Armstrong et al., 1995), although some studies reported exposure to organic contaminants through activation of the CYP1A gene in subtidal fish species through 1991 (Collier et al., 1996). Pelagic fish displayed no CYP1A induction from 1999-2000 (Huggett et al., 2003).
Pacific herring (Clupea pallasi), a major commercial species in PWS, suffered a severe decline in 1993. Some attributed this to a poor phytoplankton bloom in 1992 (leaving the fish hungry and vulnerable to disease), while others attributed the population crash to the spill (Guterman, 2009; Thorne and Thomas, 2008) through mechanisms such as the sensitivity of embryos to oil (Carls et al., 2000) and cardiotoxic effects (Incardona et al., 2009).
The other commercial species examined for effects from the EVOS was the pink salmon (Oncorhynchus gorbuscha). The mechanism of damage to this fish is thought to have been 202
through exposure of eggs and embryos to toxic PAHs released from oil residues in areas where the salmon spawn (Carls and Thedinga, 2010; Heintz et al., 1999). Principal issues concerning continued effects from exposure to PAHs from EVCO residues are that PAH concentrations in PWS represent ambient background levels (Payne et al., 2008), being below that which cause effects in pink salmon embryos (Brannon et al., 2006a; Brannon et al., 2007; Brannon et al., 2006b) and that residues from EVOS are not the only sources of PAH in PWS (Burns et al., 1997; Huggett et al., 2006; Page et al., 1996; Page et al., 2006; Payne et al., 2008; Roberts et al., 2006).
Birds
Bird mortalities due to EVCO were in the hundreds of thousands due to direct oiling from floating oil (Esler and Iverson, 2010; Iverson and Esler, 2010). The long-term effects (chronic, sublethal) mentioned in the review of Peterson et al. (Peterson et al., 2003) are the cause of continued debate.
Harlequin ducks (Histrionicus histronicus) were studied extensively due to their close association to marine intertidal habitats and their feeding on benthic invertebrates that can bioaccumulate oil residues. This made the ducks particularly vulnerable to the effects of residual oil (Iverson and Esler, 2010). While an estimated 25% of the PWS duck population died as a result of acute exposure during the immediate aftermath of the spill (Iverson and Esler, 2010), 74% of ducks collected in 1989 and 1990 were found to have hydrocarbon metabolites in their systems, implying further lethal or sublethal damages (Esler et al., 2002).
Researchers found that while the survival rates of harlequin duck populations from oiled and unoiled areas were indistinguishable from one another 11-14 years after the EVOS (Esler and Iverson, 2010; Iverson and Esler, 2010), results from application of the biomarker CYP1A indicate that the ducks continued to be exposed to oil residues up to 20 years after the spill (Esler et al., 2010).
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The continued exposure of ducks to oil residues from the Exxon Valdez is disputed. In 1995, the effects of naturally weathered EVCO were tested on mallard ducks (Anas platyrhynchos), with deleterious effects noted only at the highest concentrations. This indicated that weathered oil was substantially less toxic to mallard ducks and their developing embryos than unweathered oil (Stubblefield et al., 1995). After considering the PWS ecosystem as a whole, Wiens (2007) concluded that it was highly unlikely that residual oil from the EVOS was continuing to have an effect on harlequin ducks through the food web (ingestion of contaminated mussels). In addition, given the possibility that only a small percentage of PWS shoreline contains residual oil, the likelihood of wildlife coming in contact with the oil is remote (Neff et al., 2011). Finally, other researchers have noted that the induction of the CYP1A gene in harlequin ducks and sea otters can occur through exposure to other contaminants such as polychlorinated biphenols, and not just oil residues (Huggett et al., 2006; Neff et al., 2011; Ricca et al., 2010). This assertion has been counter-balanced by (Short et al., 2008), who found that the only source of CYP1A- inducing contaminants in rainbow trout was from oil residues remaining after the EVOS.
Marine Mammals
A tally of mortalities from the EVOS on marine mammals yielded a body count of 1011 sea otters, 19 harbour seals, 12 Steller sea lions, and 37 cetaceans. The numbers were considered misleading due to the fact that, in all likelihood, not all victims were found, and not all died due to the effects of EVCO (St. Aubin and Geraci, 1994). Other estimates suggested that up to 2800 sea otters and at least 302 harbour seals died in PWS (Peterson, 2001). During the few years following the spill, the deleterious effects of EVCO on marine mammals were primarily due to direct oiling, inhalation of fumes, or direct ingestion of oil rather than any prolonged exposure through feeding on contaminated food (von Ziegesar et al., 1994).
Continued long-term effects of EVCO residues have been most closely followed in sea otters (Enhydra lutris). Similar to harlequin ducks, sea otters can come into contact with buried oil through foraging and exposure to contaminated prey (Peterson, 2001; Short et al., 2006). As with harlequin ducks, the principal biomarker is CYP1A gene expression (Bodkin et al., 2002). CYP1A induction was observed in sea otters until 1998, in contrast to the expression of the 204
CYP1A gene as EROD activity in harlequin ducks as late as 2009. The long-term effects are questioned by a number of scientists who contend that the incidence of residual oil on the shores of PWS is low, and consequently the likelihood of sea otters contacting residual oil or contaminated food is also low (Boehm et al., 2007b; Neff et al., 2011).
Effects on cetaceans (whales, dolphins and porpoises) were difficult to document directly. There was no observable effect from the EVOS on the population of humpback whales (von Ziegesar et al., 1994). In the case of killer whales (Orcinus orca), they did not avoid the oiled areas or avoid surfacing in oil slicks resulting in the likelihood for contact with surface oil and the consumption of oiled prey (Matkin et al., 1994). While it was noticed after the spill that 14 members of one pod were missing, death directly attributable to exposure to EVCO could not be proven (St. Aubin and Geraci, 1994).
The only cetacean group that continued to be monitored over the long-term was the killer whale pods studied immediately post-spill (Matkin et al., 2008). Two killer whale pods were tracked five and then 16 years after the spill. During the 16 years, neither pod had returned to their pre- spill populations. One pod, (identified as AT1, which lost nine members) is feared to be on the brink of extinction due to the loss of reproductive females. The other (AB) appears to be recovering, but at a slow rate.
9.3 Present Status of Injured Resources and Services
The 2010 update on injured resources and services (EVOS Trustee Council, 2010) provides the current status of resources and services affected by the EVOS. The list is not comprehensive, but gives an account of selected items that were identified for the Restoration Plan, and was used for directing public restoration funds (Table 12). Although the recovery goal is for a resource to be ameliorated to a condition that it would have been had the spill not occurred, this might not be possible because of changes in the environment that have occurred irrespective of the spill.
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The categories for recovery status are as follows and are taken directly from the EVOS Trustee Council (2010) publication. Not Recovering: Resources that are Not Recovering continue to show little or no clear improvement from injuries stemming from the oil spill. Recovery objectives have not been met. Recovering: Recovering resources are demonstrating substantive progress toward recovery objectives, but are still adversely affected by residual impacts of the spill or are currently being exposed to lingering oil. The amount of progress and time needed to attain full recovery varies depending on the species. Recovered: Recovery objectives have been met, and the current condition of the resource is not related to residual effects of the oil spill. Very Likely Recovered: While there has been limited scientific research on the recovery status of these resources in recent years, prior studies suggest that there had been substantial progress toward recovery in the decade following the spill. In addition so much time has passed since any indications of some spill injury, including exposure to oil, it is unlikely that there are any residual effects of the spill. Recovery Unknown: For resources in the unknown category, data on life history or the extent of injury from the spill is limited. Moreover, given the length of time since the spill, it is unclear if new or further research will provide information that will help in comprehensively assessing the original injury of determining the residual effects of the spill such that a better evaluation of recovery can occur.
The recovery objectives are described as, Specific, measurable parameters that, when achieved, signal the recovery of an injured resource or service. 206
Table 12 Status in 2010 of resources and services injured by the Exxon Valdez oil spill in 1989. Human services are those which were negatively impacted because of their connection with impacted resources (EVOS Trustee Council, 2010). RESOURCE STATUS Archaeological Resources Recovered Bald Eagles Recovered Barrow's Goldeneye Recovering Black Oystercatchers Recovering Clams Recovering Common Loons Recovered Common Murres Recovered Cormorants Recovered Cuffhroat Trout Very likely recovered Designated Wilderness Recovering Dolly Varden Recovered Harbour Seals Recovered Harlequin Ducks Recovering lntertidal Communities Recovering Killer Whales resident AB pod Recovering Killer Whales AT1 population Not recovering Kittlitz's Murrelets Unknown Marbled Murrelets Unknown Mussels Recovering Pacific Herring Not recovering Pigeon Guillemots Not recovering Pink Salmon Recovered River Otters Recovered Rockfish Very likely recovered Sea Otters Recovering Sediments Recovering Sockeye Salmon Recovered Subtidal Communities Very likely recovered HUMAN SERVICES Commercial Fishing Recovering Passive Use Recovering Recreation and Tourism Recovering Subsistence Recovering
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9.4 Lessons Learned and Issues to Consider
It appears that the opinions of scientists representing the public sector and government on the recovery of the PWS ecosystem diverged quickly from those held by industry stakeholders soon after the spill. While all parties acknowledged the immediate, acute effects on many species of birds, sea mammals, invertebrates and shoreline flora, one party concluded that effects were inconsequential anywhere from a few months to a few years post-spill while the other concluded that the effects had shifted from being acute (causing mortalities), to chronic, long-term, sublethal effects which persisted decades after the spill. This difference in opinion is largely the result of differences in the definitions and monitoring endpoints for PWS ecosystem recovery (Parker and Maki, 2003; Parker and Wiens, 2005; Skalski et al., 2001); incomplete baseline studies of the ecosystem prior to oil exploration; natural variation, for example Eckert (2009) noted an average temporal variability of 85% (1 to 447%) in a time series spanning more than 2 years of 226 species (birds, mammals, fish, algae and invertebrates) in the Gulf of Alaska from sites that had never been oiled, which makes it difficult to assess impacts of the EVOS; PAH sources in PWS in addition to the EVOS (Deepthike et al., 2009; Page et al., 1996; Page et al., 2010); and normative science, which is the application of scientific results in a piecemeal and selective manner to support pre-existing policy rather than using the whole suite of results to develop new policy.
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10. Future Research Needs
There are a number of identified areas for future research to improve our understanding of the fate and effects of oil spills in the Arctic and the efficacy of oil spill response protocols.
10.1 Oil Detection
Effective application of oil spill countermeasures is dependent on our ability to detect and track oil both in and under ice cover. There is a need to improve methodologies to locate and assess extent of oil within an ice field to improve on simple daylight visual capability. Proposed programs for sensor development and validation include technologies such as laser fluorosensor for exposed spills between floes and on ice, and ground-penetrating radar for oil under ice, including rough ice.
10.2 Oil Fate and Behaviour
Due to the recent blowout in the Gulf of Mexico, and the intent for deep-sea recovery of petroleum resources within the Arctic there is much interest to improve our knowledge on the fate and behaviour of oil released from a sub-sea blowout. Furthermore, higher resolution oceanographic meta-data (metocean data) is now required for the development of integrated oil spill trajectory models to support Arctic operations. There is also a need to understand the influence of environmental variables such as the presence and the influence of various levels of ice coverage on drifting oil and the interaction of oil with suspended particulate material to form OMA. The development of predictive operational models relies upon the quality of available data on spreading, advection, evaporation, emulsification, natural dispersion, oil-mineral particle interaction, dissolution, and biodegradation.
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10.3 Biological Effects
For comparative purposes and to support future natural resource damage assessment procedures, there is a need to develop standardized protocols for toxicity testing. Risk assessments will require a toxicity database for valued ecosystem components (VECs). There is a need to conduct pre-production assessments of native populations and habitat characteristics to establish baseline conditions at future sites slated for exploration and production. In terms of environmental effects monitoring, our focus should be shifted from acute to sublethal effect studies focusing on key polar species and features including sensitive life stages. There is an identified need for studies on temperature and its affect on the metabolism of cold-blooded organisms which may alter biochemical responses, and studies on the life histories of Arctic organisms to determine differences in the timing of exposure to oil. The solar regime in the high Arctic supports investigation on the influence of photodegradation processes on oil toxicity. While oil spill response protocols have been developed for the Arctic, there is a need to understand the consequences of the technologies such as oil spill treatment agents. Integration of toxicity data and the development of predictive risk assessment models are essential for the development and application of predictive risk assessment models.
10.4 Mechanical Recovery
Improvements in mechanical recovery are highly dependent on improving the oil encounter rate. Emphasis has been on improving skimmer effectiveness in cold, icy conditions, the development of tactics for shallow water and overflood conditions, the use of chemical herders, and oil deflection techniques. Field trials are required to test mechanical recovery systems in a full-scale ice field with representative thick ice, including effects of vessel-ice interactions, and weather conditions. There is also a need to find a solution for the disposal of recovered oily wastes.
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10.5 In Situ Burning
In situ burning has now been validiated to be an operational oil spill response following its recent demonstration in the Gulf of Mexcico. There is a need for the development of operational guidelines for future use of the technology. Several reseach priority areas have been identified including the testing of chemical herders to enhance ignitability of oil in loose pack ice conditions; improvement of fire boom reliability; investigation of the fate and toxicity of burn residues to marine species; and the improvement of ignition systems (e.g. plasma torch).
10.6 Enhanced Dispersion
Dispersion of spilled oil and ISB are considered the spill response countermeasures holding the most promise of success under Arctic conditions. There is a need to develop operational guidelines for traditional product formulations and methods currently in use, and to assess the efficacy of improved cold water or low salinity chemical dispersant formulations. Research, involving full-scale field trials that include tracking and monitoring techniques, is needed to elucidate the long-term fate and effects of chemically dispersed oil. Sub-surface injection of chemical oil dispersants at the wellhead requires the development of application systems. The significance of OMA formation in spill response operations both in open water, within ice floes, and on shoreline environments (such as surf-washing) requires further study.
10.7 Biodegradation and Natural Attenuation
There is a need to fully understand the chemical and biological processes controlling the rates of natural and enhanced recovery associated with microbial degradation of oil, with a view towards developing in situ methods of biodegradation with minimal mechanical containment and recovery of oily wastes, their transportation, or disposal. There is a need for studies using advanced genomic techniques to assess the significance of natural oil degradation processes in 211
the Arctic marine environment. Our level of knowledge concerning the diversity of oil catabolic genes and levels of expression in Arctic marine systems is practically nil.
10.8 Development of Predictive Models
Improvements in predictive modelling are required to understand the fate, transport and effects of oil released in the Arctic to support future risk assessment needs. The models will require real-time high resolution meta-data of oceanographic properties to provide emergency response support.
10.9 Field Trials The consensus of the international scientific community is that field trials are needed to advance our development of currently emerging oil spill countermeasures for use in the Arctic such as ISB, chemical oil dispersants, herders and enhanced OMA dispersion. It is recommended that field trials be conducted under varying spill scenarios and environmental conditions, particularly spill thickness and volume, blowout compared to batch-type release, tanker release, sub-sea pipeline release. Experimental parameters for ice conditions should include ice thickness, concentration, brash ice, marginal ice, dynamic pack ice, sea state, shallow and deep water. There is also an interest to evaluate the use of azimuth drive icebreakers to provide mixing energy and to control the spreading of oil in ice fields. Field trials will also provide a means for the training of oil spill personnel, an opportunity to test various surveillance techniques and to validate oil spill trajectory models.
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11. Acknowledgements
The authors thank Dr. Lionel Camus for providing recent sources of information from his laboratory (Akvaplan niva, Norway), on the sensitivity of Arctic marine organisms to petroleum hydrocarbons. The views expressed in this report are those of the authors and do not necessarily represent the opinions or positions of the National Energy Board of Canada which sponsored this independent review.
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