.

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SPE28740 Variance in Environmental Research and Use.

R.P. Jachnik, SPEMetnbe, Baker Hughes INTEQ

Legislation.

Cause and

Effect

on Drilling

Fluid

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Abstract Drilling Fluids are presently bdergoing a petiod if pronounced change. A significant proportion of new developments me due TO legislation. adopted .within the last ten to fifteen years-by the Paris Commission (Parcom) involving the Nocth Sea countries, and The United States Environmental Protection Agen$y (EPA}. The environmental rules _{nd laws passed by countries that are mentbers. of these respective organisations spdfy whai is: acceptable or not in environmental terms. Data will be presented to show that a uniform or consensus approach to the selection of environmental criteria for the offshore. oil industry appears to be lacking, with an ensuing effect on product research, mud system development and focus. Introduction The last 13 years in particular have seen both significant changes and an increase in the number of environmental regulations relating to the marine discharge of drilling and completion fluid chemicals Znd wastes. Both .Parco.m and the EPA have independently adopted test protocols, and legislation. aimed at minirnising toxic discharge and hence, by iinfere me, environmental impact. These two main regulatory bodies cover the bulk of western offshore drilling and so set precedents and standards for other countries to examine and possibly adopt. Circumvention of the environmental learning curve by other countries is quite feasible provided that a full appreciation of the result: of environmental impact studies is correctly balanced against the desire for sustainable economic developmem. 1 The history of environmental legislation, particularly in the Parcom area, shows that toxicity tests have become more stringent. Other tests including aerobic biodegradability and log .Pow (the partition co-efficient between n-octaol ahd water which is supposed to reflect bioaccwnulation) have also been introduced. Member cotintries within Parcom have adopted some divergent standards. as they work towards achieving common Parcom goals. Consistency between ,.~signatory countries has been lacking and this appears to be the current status.z

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Refermces ad illustrations m end of paper

683

Variance

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Legislation.

Cause and Effect on Drilling Fluid Research and Use.

SPE 28740

Nevertheless, the Parcom counthes are working towards a common con.aensus. based on a.genuine desire for harmonisation. Emphasis is being placed on the implementation of an environmental risklhazard evaluation model (Chemical Hazard Assessment and Risk Management CHARM) for each product (and possibly mud system).3 Risk assessment is not without its. own problems however, as others have poirited out.4 In the USA Gulf Coast area, the Mysicfops;s bahia shrimp test was adopted in 1986 as the sole requirement for toxicity testing and put forward as a fair and relatively inexpensivetest. It is still the main arbiter of a good or bad drilling fluid product or system.5 None of the en.virorimenta! tests for drilling fluid products and systems specified by Parcom are presently being used in the. USA and Mysid. shrimp LC50 Values from the USA, performed on any of the generic muds. (usually # 7] are no longer valid for North Sea. classification. While the EPA does use risk assessment in some areas of its jurisdiction it appears riot to utilise this tool in the evaluation of mud products and systems, preferring to encourage-the voluntav. imPlemept?ti?.n . . of pollution prevetitton and waste minimisation programs in E &. P operations.e As J.C. Reis points out, environmental protection requires a serious commitmen~ toward protecting the environment in all activities, regardless of the. regulations7 However, experience in the harsh world of economic reality and competitiveness has demonstrated that this approach does not often achieve its intended goal. Regulations. =ap.pea[ to. .be. l.be. onlY _ W?Y tO achie~e miikiial. environmental impact, yet up to now, they have not all been framed in a logical or sensible way. This non harmonisation of acceptable environmental factors and standards8 h~.s. meant that for a servics company operating globally, consistency in both product and fluids system research has been laCkiIW. The operating priorities of. an active area can take precedence_ over other requirernetits and sensible long-term research. As a result, products and systems have been researched, formulated, even marketed, only to fjnd that they infringe some environmental criteria on one tide of the Atlantic or the other..

This process is costly to both service companies and operators, as well as being environmentally inconsistent. Changes in Test Goal Posts . Requirements: - The Moving

A previous paper has doc.umentecl the various environmental testing of drilling fluid products and systems that are required from an internatiofi-al perspective. Since this was written and published in late 199o,. several changes have taken place European scene, which particularly on the demonstrate several points. 1) Marine environmental research is an ongoing subject. The drilling service companies, oil industry and ultimately the consumer are paying for it. 2) The criteria of what is termed environmentally acceptable has become both harshar and at the same time more nebulous. Table 1 lists the test species and physicoichemical. tests as agreed by all parties to Parcom, early in 1994. This list is only valid for new products or old. products that need updated testing. Synthetics, the additives which go into these systems as well as products that have high Log Pow or low ready biodegradation require further tests. [Table 2) It is worth noting that from 1990 alone, the sedimentary reworker test has introduced the Heart urchin Echinocardium cordata iii Holland, the bivalve Abra alba in Norway and the amphipod shrimp Corophium volutato:ip the UK. None of these teSt.S are without _some inconvenience and difficulty. ..However, following g recent ring test all pa flies have now agreed to use Corophium volutator as the sedimentary reworker test species. The testing protocols were based on ASTM methods originally researched by the EPA! Obtaining the species ina good condition at the required time for the testing Laboratory is not easy. Laboratory culture is presently impractical. Despite the significant changes since 1990,. .&id attempts at harmonisation, regulatory agencies are still taking different views as to what is acceptable for dkcharge in their area.

684

SPE .28740 ..

Richard P. Jachnik _._. ...

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In contrast to the significant environmental! changes affecting drilling fluid discharge in the Parcom countries, in the Gulf Coast, change has been minimal .- Discharge of-;iy drilling waste w% three miles of land, in areas of biological concern or in marine sanctuaries ii no Ioriger permitted. The rules regarding no free oil [as measured by a static sheen test] and a discharge rate for wastes controlled at a maximum 1,000 bbllhour have not changed. Some additional restrictions on the maximum allowable content of heavy metals in Barite have reduced permissible levels down to 3 mglkg for cadmium and 1 rnglkg for mercury. Several examples where a product is acceptable on one side of the Atlantic but not on both will now be described. Table 3 documents the costs .of environmental compliance for aproduct on either side of the Atlantic. Table 4 documents the costs that are incurred in testing-new synthetic organic alternatives. Areas of Conflict: Example A : Inorganic Salt.

-.

In 1992, the 19th meeting of the technical working group advising Parcom 15 listed Chemicals/Products which. @ not require further testing for offshore use or discharge. This is known as the Parcom Green List (Annex 3, List A). The list icldes potassium chloride salt in any quantity. - this list includes natural constituents of sea water. From experience of their use they pose little harm to the environment. To quote from a recent paper,l a most regulatory authorities recognise that toxic impacts result from M a low LC50 Q a Iangthy exposure. The EPA. [Unbke F%COM] recognises the fact that large OIWIW discharge of water based drilling mud even with an acceptable toxicity limit can have a deleterious (if only transient) effect. However, soluble materials such as KCI when discharged into the marine environment undargo a natural di[utio.n within 96 hours to concentration levels much lower than that obtained with a 9:1 dilution in the EPA Mysid test. The author feels. that a dilution effect should be calculated for saturated sodium chloride to achieve a NOEC [No observed effect concentration) for NaCl to both algae and planktonic crustaceans. A factor could then be applied to all water soluble materials both inorganic and organic. Only the ca a true appreciation of both the dilution effect of the sea and the product or mud systems toxicity be taken into accomt made on and responsible decisions acceptable discharge levels. (This would axclude current effects.) Example B: Formulated Product A. ..

Potassium chloride (KCI) is an essential part of Mg-hly inhibhe.d water base muds for shale drilling and many examples of its efficacy exist iri the Literature. s,l 0 This includes the netiest generation KCI polymer muds which utilise glycol ethers in their formulation and have dilution rates comparable to oil base muds. 1l.,l~13 KCI is used in varying &centratios usually from 8 to 20% by weight in many mud formulations universally - except the USA offshore areas. At concentrations greater than 3% when tested in generic mud # .7, potassium chloride is ,ToxicS,. 96 hr LC50 16v61s then fall below the acceptable threshold of 30,000 ppm in the suspended particulate phase (SPP. ) But is potissiurn chloride really toxic when discharged into the offshore marine environment? (It should be noted here that marine environments can vary widaly from shallow estuarine areas to open ocean. Areas close to land or sensitive areas such as fish spawning g-rounds will always be more strictly regulated for a variety of reasons.) A template for managing exploration activities in inshore Parcom waters has been pmpmsaf. 14

This Differential Sticking Preventative additiw has been very successful in drilling depleted sands along the US Gulf Coast since its introduction about four years ago. Actual case histories and description of the mode of action of the product are described elsewhere.l 7 The material, at 3 Y. by vokme in geleric mud #7, has a USA Mysid shrimp toxicity of >1,000,000 SPP and its use is not restricted in the main Gulf Coast area.

685

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Legislation.

Cause and Effect on Drilling Fluid Research and Use.

SPE 28740

Individual countries of Parcom differ in their views on the use of either Asphalt or Gilsonite in formulated products. The Dutch have historically taken the hardest line; with the UK accepting a particular Gilsonite following a series of expensive tests run by a vendor. The latest draft PARCOM position (8-11 February 1994) states the following sub&ances/preparations shall not be: discharged from offshore installations in the maritime area - Sulphonated polymers derived from. asphalt. Polymers with Gilsonite - Polyethers. in aromatic solvents.., (Reservations were noted from D.erimark, Norway and the UK.) Toxicity bands are similar between the UK and Dutch national schemes. The threshold levels for LC50 concentrations in mg/1 are based on a log scale (1 -10, 10-100, 100-1000 etc). Under the current UK scheme a product will be placed in a fixed category whereas no specific category is given by the Dutch scheme. The latter is. preferable, since after other factom such as, biodegradation are taken into acccmnt, permission for use is either granted or withheld. In the UK scheme the product is assigned a category which then determines the quantity of product that can be discharged. A 950 mgll res.u[t is in a different category (1) to an 1050, mgll result (0), laboratory these differences are within yet repeatability and statistically insignificant. A revised scheme for the UK .due. to be published in 1993 has not appeared at the time of writing. In the draft proposals, category O products were given 5 years until a retest (in full, to the more complete Parcom Both agreed requirements) was necessary. Sulphonated Asphalt and a Gilsonite presently have a category zeru in the UK. The latter was assigned to a particular Gilsonite following tests on hot-rolled samples in sea water. These included Log Pow and oyster embryci/larvae [Crassostrea g;gas] tests which were conducted in late 1992. If tt,e latest Parcom draft proposals become law, then Gi[sonite and products based. on .Asphalt have a short life span for discharge into the North Sea. The Gilsonite producer will then have contributed to marine environmental research for little commercial gain. Our company has detided not to have formulated product A environmentally tested for use in the North Sea.

Example Following

C: Formulated some extensive

Product

B: by our Houston

research

(USA) research group, a product based on a high molecular. weight polypropylene glycol was toxicity tested in the USA and marketed in 198918. ...The Mysid Shrimp LC~O test for 5% by volume of the product in generic mud # 7 gives results of around 510,000 ppm for the SPP, with field muds ranging from 900,000 ?O 1,000,000 ppm. (Muds containing the product pass the EPA sheen test and in the field had <52 mgll extractable hydrocarbons based on a solvent (Freon) extraction method, so satisfying the Environmental critec~.a of the Department of Conservation in Alaska.) When thk product was tested in The Netherlands results in Table 5 were obtained. The product was voluntarily withdrawn the

~~~ =

from market

in The Netherlands after two technically successful field trials, (one, a record depth horizontal well). This followed comments from the State Supervision of Mines (SSM) who objected both to the low biodegradability in sea water, as well as literature . references to very slow biodegradation rates of the particular polyglycol ;n fresh water tests. A low sedimentary reworker test result for the product was also obtained. In the UK the product was classified 2 under the CNS scheme, primarily on the basis of the result obtained with the gammarid shrimp. This category level means that prior permission has to be obtained.. if dkcharge is to exceed 10 tons per year (approximately 55 drums] per point source, thus effectively limiting use of the product, as some operators are reluctant to seek permission. (It could be refused.) All operators in the UK try to utilise the products with the lowest category under the CN.S to demonstrate their part in being more environmentally aware. It. is a. known fact that some products are presently characterised incorrectly on the basis of genuine mistakes or inadequate data. The current scheme does nol seem relevant.. compared to present Parcom guFiielines, as the majority of produ.cls were categorised on the basis of cmly toxicity tests, many of which were carried out under protocols and by laboratories which are no longer recognised.

._.

686

SPE 2874o

Richard P. Jachnik

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Example protocols. D: Toxicity Results with

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different hl the inner zom?, anaerObjc conditions ~d hydroca~bon levels over 1000 times background levels existed. Opportunistic species peaked between the end of the inner zone and the next outer zone. Only at distances of 4000 m from the pile centre could no benthic effects be seen. In 1888, reports were presented on furtherstudies conducted on mineral oil mud waste discharges.22 This showed thg: total oil concetratio~ i the northern North Sea [Shetland Basin) could reach 10,000 ppm beneath platforms. 3000m away, this level could fluctuate from 1 to 300 ppm. The evidence by then had accumulated whereby North Sea member states began to enforce stricter rules on discharge. These were initially aimed at reducing the oil content on cuttings. Some authors puhiished data which showed that other losses could acc6unt foranextra30to 50% on top of the oil mud 1.oston cuttings .23.24 In effons to better understand the agglomeration of cuttings into piles and the distribution of waste. on the seabed, studies were ccmducted and Umerica[ simulation models proposed.25 since Parcom ins;sted on lower ad [ower oil contents cm cuttings, the operating companies under the E&P Forum, instigated rasearch into the physical and biological effects cm tha seabed of ~treated mineral oil mud cuttings and those which had been treated by a variety of cuttings cleaning techniques and exhibited Iowsr oil mud on cuttings contents.26,27 The research found that thermally processed cuttings with oil levels of <17. (equivalent to 1.5% oil mud} had no more adverse effect than the controls and that sediment oil concentrations of less than 1000ppm did not create long term or significant impact. Parcom participants have now eventually agreed to regulate the. oil content on cuttings to <Ih, effectively leading to a complete ban on mineral oil mud discharges as cuttings cleaning technology has not yet economically reached this level. Discharges from water baae muds have aISO bee monitored both from single well sites and in areas where appraisal and development drilling as well. as field operations have been conducted. The results

During the course of R & D work on various types of possible synthetic organic fluids snd associated environmental testing of other products it was found that several materials would pass or fail the accepted criteria either on one side of the Atlantic or the other. Examples of Table 6. Mineral some of these materials . are given in

Oil Muds

and Synthetic The Fads.

Oil Muds.

A: Mineral

oil Muds:

In the early 198.0s toxicity tests in the UK showed that Dieseroil muds were toxic to the brow shrimp species otherwise knowri as Crangon crangon. This test species. was favoured at that tima by the UK Ministry of Agriculture Fisheriis and FoOd (MAFF) who advise the UK government on toxicological and relsted matters. A specific test technique was established with the advent of mineral oils. In this test diesel muds had typical 96Hr LC50% of 65 .to 180 mgll. For the most severely hydrogenated mineral oils in use at the end of the 1980s, this number was in excess of 1000 mgll mud. (Tab~e 7) Crangon crangqn was superseded by the Parcom agreed species in the UK during 1992. The reason for. its decline was lack of sensitivity. This attention to the decrease i toxicity was WeII illustrated in several papers which were published up to 1984.1 ,zo These highlighted the toxicological ad technical advantages of mineral 011 ovg diesel as .a basis for oil based muds. IT was not until the seminal papsr published by. Davies et al ii October 198421 where it was shown that the discharge of cuttings and associated wastes from drilling with mineral oil based muds still had a significant envirornental impact. Mineral oil mud discharges exhibited au greatly impoverished benthos in the close proximity to the point of discharge, snd this zone extended out some 200m to 2000m from the pile centre, depending on oceanographic characteristics, operational history etc.

687

Variance

in Environmental

Legislation.

Cause and Effect on Drilling Fluid Research and Use

SPE 28740 ... . ,.

show that while smothering can occur, recovery takes place quite quickly and long-term environmental effects are minor. 28,29,30 ~ . .=:=- (Judicious use of the chemicals in modern watei base. muds could probably further lessen environmental effe.ct3.) Why do mineral oil muds not degrade as quickly as first hoped and why do they cause a paucity in benthic faunas with resulting long term effects?sl Severely hydrogenated mineral oils contain <1 % aromatic hydrocarbons, and between 20 and 40% by weight cYclic hydrocarbons (naphthenes), the remainder being paraffins. The molecular size varies ,from C12 to. C16. Some combination of molecules can exist and it is importarit to rr%lise tfiat mineral oils can exhibit a wide variation in aromatic conterit aid chemical make-up. A mineral oil mud similar to the Parcom ring test fluid, (Carbosea DMA) wis biodegradability tested using a shake flask method adapted for seawater. Inoculum was natural seawater concentrated 10 times. The alkanes degraded in 3 days, the rest in. about 7 days.32 No detectable aromatics, (<0.1%) were found in the n-pentane extracted sample. Principal components from the extraction were C12-Cq7 alkanes (5096} the rest being branched alkanes and olefins [the latter probably coming from the. surfactants). This test was conducted on extracts of the organic phase in effectively a dilute medium, at a laboratory temperature. of 18 C. However, on the seafloor, Ihe conditions are usually dark with a temperature of about 4C. Discharge of oil mud on cuttings results in the material sinking quickly to the seafloor as the cuttings density significantly exceeds that of sea water. The mud contains droplets of a concentrated brine (calcium chloride) as the internal phase. These droplets are tightly bound with surfactants. Transference by osmosis33 of sea water to the shale and internal phase droplets allows the cuttings to swell slightly and partially hydrate. The surface .Iayer of the. oil mud is also rendered water wet and so the cuttings become stickier, and a9910 merate paste. fOrming what others have termed a

SU/faCe tanks under controlled ccmdjtjons favourab[i for the process. Several factors discriminate against- - the ease of biological degradation. These are: A). Change in temperature. For every 10C decrease in temperature, the rate of degradation can be halved. (or even greater if below 5 C) B). Concentrations of biodegrading bacteria of the right type are much lower in the marine environment than in inoculum. Cl. Lack of nutrients such as phosphates or nitrates to feed the growth of bacteria. Bacterial growth on mineral oil mud can also be severely limited due to D). A higher brine concentration ~f the internal phase than sea water. E). A high alkalinity of the organic phase, although this will decrease with time. The sticky agglomerated mass of cuttings become impervious to flow of oxygenated sea water. Anaerobic conditions develop within the main mass which has to rely on an adequate source of anaerobic bacteria for significant degradation. to occur. Many surfactants used in oil muds contain amine-groups. Th& degradation pathway of these materials in the cirganic phase probably involves sulpha~e reducing bacteria35 which rely cm a source of sulphate (mi9rati0n or diffusion of sea water through the pile) to encourage anaerobic degradation. Dilution is a pre-requisite for aerobic degradation i laboratory tests. On its passage to the seafloor the now extremely viscous oil mud on the cuttings does not undergo this dilution effect. Aerobic biological degradation will have its greatest stimulus at the edges of the discharge area, where dilution effects are greater and rcilling, reworking of cuttings with sediment can occur. Log Pow for mineral oils is usually in the range 3 to 6, i.e. the area of bioaccumulation. While bioaccumulation has been detected in fish caught in the vicinity of platforms and from various areas of the North Sea, tests from 1985 up to the present have shown that taint [as determined by fish tasting] is not a brobl&m.36

Other experts in the art of microbial degradation34 have found difficulty in degrading mineral oil mud in

688

I 1

SPE 28740

Richard P. Jachnik . . What are the environmental

7 ... ... .. . ..... .. . . .=-

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Synthetics advantages?

The use of synthetic oil based muds within the last two years has mushroomed, as a direct response to stricter environmental legislation related to the discharge of cuttings contaminated with mineral oil. Following a review of the literature, coupled with the testing we have conducted it is possible to draw several conclusions. 1i. [f an organic is strongly water insoluble, no toxic effects will be seen using the Parcom agreed toxicity testing protocols for either algae or mid water species. (This includes mineral oils) 2). Some muds prepared with synthetic organics are much less koxic to sedimentary reworkers thm mineral oil mud. e.g. Ester( Table 8). The US Mysi.d test indicates greater toxicity if the material contains organics with a chain length of Cl 4 or ie.ss. The chain can be branched, saturated or unsaturated. Similar responses appear with the reworker sedimentary Corophium voluta tor. Consequently a mineral oil based on hydrocarbon molecules larger than Cl 5 should also show low sedimentary reworker toxicity. 3). 8iodejradation values .ca-n vary widelY3Q3s depending on the synthetic used. An ether (diisodecy lether] shows less aerobic biodegradation than mineral oils. Some Polyalphaole fins are a[so slow to biodegrade depending on their degree of brachig and level of saturation. Esters show both high aerobic biodegradation and. good anaerobic degradation rates in the laboratory .40 Laboratory tests for mid water crustaceans, surface algae and biodegradability do. not correlate well when testing oil or synthetic oil muds [which both contain surfactants, amine Ignites, organoclays and polymers) as these muds are quite viscous and denser than sea water. Anaerobic biodegradation tests utilise a consortium of methanogenic bacteria. These bacteria in. themselves are inhibited by the sulphate in sea water. The relevance of this test has therefore to be questioned. 4). Log Pow is indicative of bioeccumulbtion ~nly when a linear correlation exists between log Pow and log BCF (bioconcentratio n). The relationship is not valid in the case of supedipophiles where a 109 Pow Of,

>6 can lead to a decline in log BCF.41 Log Pow values for synthetics can vary widely. A high Log P will not show bioaccumulation in laboratory tests fw 2, but due to the large bulky branched molecule, biodegradation rates will also be low. it is interesting to note that either the EpA Or Parcom have set synthetic oil on cuttings limits to discharges. In the USA, cuttings from drilling with synthetic invert emulsion muds are being discharged under water based mud criteria. Measurement of synthetic content on cuttings is being recorded by some companies and numbers from 80A to 17% by weight are typical for a variety of synthetic systems. Therefore the amount of organic material arriving on the sea floor is similar to what it was in 1984. Smothering of the benthos and organic enrichment will therefore predominate in the short term, leading to atia<robic conditions inside the cuttings pile, Anaerobic degradation, if it occurs, will be slow unless there is an ample supply of both bacteria and seawater. Since the main difference between any synthetic and a mineral oil based on molecules larger than Cl 6 appears to be the rate of anaerobic degradation in the ECETOC 28 day test, synthetic mud can be expected to remain in a similar state in the cmtings pila as mineral oil mud. At the extremities of the cuttings pile, those systems with high aerobic biodegradation levels [esters et al) could be expected to degrade more quickly than present mineral oil or similar systems. However, rapid aerobic degradation of the ester systems could pose a short term threat to benthic fauna through reduction of available dissolved oxygen on and near seafloor sediments. Parcom authorities are presently insisting on seabed surveys before pronouncing on the future of any synthetic mud. It is abundantly clear however, that compared to cuttings re-injection, the hoped for thermal process42, or use of benign water based mud designs, synthetic oil muds do pose a greater element of environmental risk. The term conceived for them at their inception was perhaps more apt than realised - some are indead Psaudo-Oil muds.

6a9

Variance

in Environmental

Legislation. Cause and Effect on Drilling Fluid Research and Use

Si?E.28740-

While the envimnmenta!. agencies slowly come to grips with the tec.h.nological advances in replacements for mineral oil muds, some authors offer arguments on the benefits of synthetic oil mud sy~tem~,43 CIo~e examination .of the fat@ hOwever, reveals that the environmental benefits of synthetic systems not only are variable, but also minimal. As can be seen from the tables of both costs. involved and current synthetic prices, large amounts of money are being spent and even more importamly, large amounts of research time are. being employed on products arid mud systems which offer dubious environmental benefits. Conclusions 1). Significant differences exist between what, termed environmentally acceptable for discharge the US Gulf Coast and the North Sea. is. in

2}. The drilling. fluids sector (iriCiUdin9 Oroduct suppliers) is spending large sums of money to comply with variances in envimfitienta[ rules pertaining to the offshore industry, which may ultimately reduce the umber of new products being brought to the market. 3). A common, world consensus is required in the future to ensure adequate protection of the offshore marine envirohmeiit. This will he!p minimise the number of tests and resulting costs, thus allowing research to focus on both the technical and associated environmental challenges facing the industry. Consistent iiidustrial development would be stimulated with such an approach. Acknowledgements The author would like to thank Baker Hughes [NTEQ management for permission to publish this paper. Special thanks go to Cheryl Stark, Ron Bland, David Marshall, lain Whyte and Bruce Ewen who reviewed the manuscript and offered valuable comments ... References 1. Meijer, K. and K. Krijt. implications of The Netherlands Environmental Policy for Offshore Mining. SPE 23339. First International Conference

on Health, Safety and Environment. The Hague, The Nethedands:10 -14 November 1991: Hayward, P.A. The Emerging EnvironrnentaI 2. Movement In EuroPe. SPE 22607. 66th Annual Technical Conference and Exhibition of SPE. Dallas, Texas: October 6-9 19.91: GOP-PARCOM, Eighteenth Meeting of the 3. Working Group onOil Pollution. 1994, PARCOM: Gordon, R. D. and J .L. Cayias. An Approach 4. To Resolve Uncertainty in Quantitative Risk Assessment. SPE 25959. SPE/EPA Exploration & Production Conference. San Antonio, Texas, USA710 March 1893:: Jones, F.V. and A.J.J. Leuterman. Alternate 5... Environniental Testing of Drilling Fluids: An International Petsective. SPE 20889. Europec 90. The Hague, The Nethedands:22.24 October 199!3: Derkies, D.L. and S.H. Souders. Pollution 6. Prevention and Waste iVlinim7zation Oppommities for Exploration and Production Operations. SPE 25934. SPELEPA Exploration & Production Environmental Con ference. San .Antonio, Texas, USA:7-I O March 1993: Reis, J.C. An OveMiew of the Environmental 7. issues Facina the Uostream Petroleum fndustrv. SPE 26366. 68;h An;ual Technical Conference and Exhibition of SPE. Houston, Texas, uSA:3-6 October 1993: B. Armstrong, K.E. Environmental Guidelines tZr Worldwide Exploration and Production Activities: Do They Make Sense?. SPE 23319. First International Conference on Health, Safety and Environment. The Ha9ue; The Netherlands: 10-14 November 19.91: Steiger, R. P., Fundamentals and Use of 9. Potassium/Polymer Drilling Fluids To Minimize Drilling and Completion Problems Associated With Hydra tatde C/ays. Petroleum Technology, 1982. (August 1982). 10. Bol, G .M. The Effect of Various Polymers and Salts on Borehole and Cutting Stability in Wafer8&e Shale Drilling F!uids . IADCISPE 14802. /ADC/.SPE Drilling Con ference. Dallas, Texas, USA:February 10-12, 1986: Dring, l., R. Jachnik, and W. Wise. The 11. North Sea After 017 Muds. Where Now?. 6th Annual Offshore Drilling Technology Conference. Aberdeen, Scotland:25/26 November 1992: Downs, J. D., et al. TAME: A New Concepr 12. in Water-8ased Drilling Fluids for Shales. SPE 26699. Offshore European Conference. Aberdeen, Scotland:7-1 O September 1993:

690

13. Twynam, A. J., P.A. Caldwell, ,and K. Meads. GIycoi-Enhanced Water-Based Muds: Case History To Demonstrate Improved Dril[ing Efficiency in Tectonically Stressed Shales. lADC/SPE 27451. lAOC/SPE Drilling Conference. Dallas, Texas, USA: I 5-18 February 1994: Kearns, J. and J.G. Parker... u@fl?@f19 14. Exploration Activitim in Erii%onmental[y Sensitive Inshore Waters. .SPE 26749. Offshore European Scotland:7-1 O._ September Conference. Aberdeen, 1993: 15. Parcom, ed. Discharges of Oil from Offshore Installations. 1992, Oslo & Paris Commissions: . D..D and .~.___. Eansal M. .._ 16. Caudle, Environmental Considerations in, _.Production Chemical Usage. SPE26070. SPE/EPA Exploration& Production Environmental Conference. San. Antonio, Texas, USA:7-10 March 1993:. 17. Bland, R. G., W.T. Micho,, and H. J.. Howa[d.. Appl~cation of New Giycol/Resin Differential Sticking Preventative; SPE 2459T. ~~th Annual Technical Conference and Exhibitionof SPE. Washington, DC, USA: October 4-71992 18. Enright, D. P., W.M, .Dye,...ndnd. F.M. Smith. An En vironmentaily Safe Water-Based Alternative to 03 Muds. SPE71ADC 21937. SPE/lADC Drilling Conference. Amsterdam, Netherlands:l 1-14 March 1991: 19. Hinds, A.A. and W.R. Ciernents. New Oil Mud Passes Environmental T~sts.. SPE 117.z. 57th Annual Fall Technical Conference of SPWAIME. New Orleans, LA.: September 26-29, 1982: 20. Hinds, A. A., S.P.T. Smith, and E.K. Morton. A Comparison 07 the Pefforman@< Cost and Environmeritd Hf..cts of D@ssABas@d and LowToxicity Oil Mud Systems. SPE 11.69 t. Offshore Europe. Aberdeen, Scotland: 1983: 21. Davies, J .M., et al., Environment tal Effects of the Use of 01-Based Driiling Miids in the North Sea. Marine Pollution Bulletin, 1984. Na. 1.5(10): p. 363. 370. 21 T. Dixon, i. M. T., ~perimental application of oil-based muds 8nd cuttings to seabed sediments; in Fate and Effect of Oil in Marine Ecosystems, J. Kuiper and W. J.V.d. Brink, Editor. 1987, Martinus Nijhoff: Dordcecht. p. 133-150. ,, . . .. ; Various; 22. Fate and Effects / Marine. International Conference on Drilling Wastes. CMga~, Alberta, Canada:April 5-81988: 23. Jachnik, R.P. and D.S. Marshall. Optimizing Oil Muds for Offshore Orilling and Lower

Environmental [mpact. 2 ist Annual OTC. Houston, Texas, USA May 1-41989: 24. ,., Kingston, P. F., The North Ssa 01 and Gas Industry and th~ E@imflment, in Oil Gas European Magazine. 1991, 25. McFarlane, K. and V.T. Nguyen. The Deposition of Cuttings on the Seabed. SPE 23372. First International Conference on Health, Safety and Environment. The Hague, The Nethedands:T 0-14 November 7991: 26. Minton, R.C., et al. The Physical and Biological @8ct of Processed Oil Drill Cuttings: E & P Forum Joint Study. SPE 26750. Offshore EuroDea-n Conference. Aberdeen, ScotIand:7-10 Septmber 1993: .. 27: F.5rum, E.&. P., The Physical and Biological Effects. of Processed Oily Drill Cuttings. 1993, The Oil Industry International Exploration and Production Forum: , 28. Hartley, J.P. and J.h4. Addy. %wironinentai Effects of Noflh Sea Drilling. Discharges. - New Information and New Initiatives. .3rd Annual Offshore LM7iing Technology Conference. Aberdeen, Scotland:29130 November 1989: 29, Dam, R. and M. Muld.er, A Study on Possible Environmental Effects of a WBM Cutting Discharge in the North Sea One Year after Termination of D@ling. ?993, Nederiands Instituut v.oor Onderzoek der Zee%apport 1993-5 30. Daan, R. and M. Mulder, *A Study on Possible .Short-Term Environmental Effects of WBM Cutting Dkcharges in the Frisian Front Area (North S&al. 1993, Nederkmds Instituut voor Onderzoek der Zee:Rapport 1993-16 31. Da.an, R. and M. Mulder, Long Term Effects of OBM Cutting Discharges at a Drilling Site on the Dutch Continental Shelf. 1993, Nederiands Instituut voor Onderzoek der Zee:Rapport f 993-15 Valk, 32. v.d. F. and P. G,. Wester, Biodegradability of the 017Y. Constituents of 08 Mud< in Seawater!,.. 1988, RIVO: (Milpark Internal Report)_ 33. Hale, A. H., F.K. Mody, and D.P. Salisbury, The [nfiuence of Chemical Potential on Wellbore Stability. SPEDE, 1993. 8, no 3( September 1993): p. 207-215. 34. Thurman, N.P. and M.T. Heydeman. A Microbial Approach to Cleentng Used Oil-Based Orilling Muds. SPE 23061. Offshore Europe Conference. Aberdeen, Scotland:3-6 September 1991:

,:

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Legislation. Cause and Effect on Drilling Fluid Research and Use

SPE 28740 ,,. . ,.,,.,.

35. Schink, B., A. Brune, and S. Schnell, Anaerobic Degrada don of Arornat?c Compounds, in A4icmbii+l Degadaiion of Natural Products, G. Winklemann, Editor. 1992, .VCH: p. 219-242. 36. Davies, J.M. and P.F. Kingston, Sources of Environrneri=IDisturbance Associated with Offshore Oil and Gas Developments; in North Sea Oil and the Environment, W. Cairns, Editor. 1992, Elsevier. Applied Scienc~ p. 417-440. 37. Bland, R, G., er al. Biodegr~dation ~nd Drilling Fluid Chemicals! SPE/lADC .25754. SPWMDC Drilling Conference. Amsterdam, The Netherlands:23-25 February, 1993: . 38. James, R;W. and B. .Helland. The G~e?ter Ekof& Area: Addressing DriiJjng Fluid Challenges with Envir%nmi%Zal Justifications. SPE 25044, European Petr@um Conference. Cannes, France: 16: 1B November 1992: 39. Peresich, R., B.R. Burrell, and G. Pren~ce Development and Field Trial of a Biodegradable Invert Emulsion Fluid. ,SPE/lADC 21935. SPE/lADC Drilling Conference. Amsterdam, The Netherlands:l 174 March 1991: OSARS of Bioconcentration: 40. Nendza, M., log Po w/{og BCF Validity Assessment of Correlations, in Bioacc.urntilation in Aquatic Systems, R. Nagel and R. Loskill, Editor. 199?, VCH: P. .+3-.66. 41. Rushing, J. H., M.A. Churan, and F.V. Jones. Bjoaccurnti/a?,5n from_Mieral Oil- wet and Synthetic Liquid- Wet Cuttings in an Estuarine Fish, Funduius grandis. SPE 23350. FitW lnterpational Conference on Health, Safety and Environment. The Hague, The Netherlands:l O-14 November 1991: Atkins, M. Torbed Project. Update;. The 42. Prevention of Oil Discharge From Drlling Operations The Options. Aberdeen, Scotland:1 5-16 June 1994. Candler, J. E., J.H. Rushing, and A.J.J. 43. Leuterma.n. Synthetic-Based Mud Systems Offer Envirdtirnentaf Benefits Over Traditional Mud Systems. SPE 25993. SPE/EPA Exploration & Production Environmental Conference .San Antonio, Texas, USA:7-10 March 1993:

692

SPE 28740

I%chard P. Jachnik _ ... ..:.

11 . . .. . . ..-

Table

Present PARCOMTest Species and Requirements: -( Harmonisation 1994.) To be conducted under OECD principles of Good Laboratory Practice. (Certified system;)

Test Species:

Mid-Water - Planktonic Crustacean - Acartia tonsa.

Sedimentary

Re-worker

- Amphipod

Shrimp - Coro~h;um volutaror.

One National Authority in Particular decided to demand retro testing of products already tested to similar species that were in agreed use prior tb this Harmonisation! This is in spite of a ring test showing very little difference in the results of the biocides tested to p[anktonic species. Sedimentary reworkBr results on discontinued species are to remain valid. The species now dropped are as follows: Algae P[anktonic. Crustaceans:

Phaedodactylum tricornutum.- HoIland/UK. Chaetogammarus matinus. - Holland. 7isbe battagliai.- UK. &lysidops;s bahia.- Several. Crangon crangon.- UK. Balanus fmprovisus - Norway. MytiYusedulis -. Norway.
Abm .?Ib.s. - Norway. Echinocardium cordatum. Arenicola marina. - UK. - Holland.

Sedimentary Reworkec

Mwi[us (the blue mu=ei) has been dropped as a sedimental reworker &pe but Is to be kept as a species to measure bioconcentration. ( Many marine s .e.cie$ have beemused by researchers comparing the efficts of diesel and mineral oil mud and cuttings on seabed sediments. 29i?31) In addition to the above three tests the UK is promotimg the benefits of a fish larval test, which is piix?e.nily being ring tested. Other Tests:

Log Pow (Partition coefficient Aerobic 6iodegradabilitV

of n-octanollwater).

OECD 117.

Preferred result is <3.

An OECD approved method. There is some variation here. Holland prefers the OECO 306 test (28 day shake f Iask method} in Natural seawater. usually required on Synthetic mud systems. Ecetoc 28 test to ISO guideline.11 273.

Anaerobic

Siodegredation:

693

12

Variance in Environmental

Legislation. Cause and Effect on Drilling Fluid Research and Use

SPE 28740

Table

2-

Other

Product

Testing

Costs
eg:

(These tests could be required by individual Parcom members, depending on results in Table 6 and nature of substance synthetic] Costs obtained from various laboratories. Again dkcmnts are available for larger number% of samples. T&ztiTY P& Fish: larval Turbot 48 hr LC50 Crassostrea gigs% Embryo/larval development. Bioaccumulation.test: 81ue Mussel.3.O day (Water phase only at moment-hence high cost) Marine Bodis Test 28 day Inherant biodegradability-Zahn Anaerobic We[lens OECD 3028 Test to Ec.etoc 28. (uP to S weeks) OECD 305 ~ Castin $ 2100 to 2900 2200 22,000 1400
to

4500 ..,:

5900
10,500..

Table

3-

Product

Testing

Costs

Costs in US $ at current exchange rates associated with testimg to the approved protocols. For the Parcmn figwes, aerages were taken from a UK, Norwegian and Outch Testhg Laboratory all approved to GLP standard, Test TYP$ Mysidopsis bahia US protocol. : Cost per single test $ 650 300 650 2118 1649 2700 1681 767 8915

In house - m GLP required. .._ .._.

each Ran@in.der for above. Total US cost per product Ske/etonema costatum

72 hr LC50

Acwtia tonsa 48 hr Corophium votutator 10 day biodegradability OECD 301 F LoE/ Pow OECO 117 Total Parcom Fst Per. PrOdU?t

Several factors cmfwe ZCtual costs. Prices fluctuate widely bitwem testimg laboratories. Most laboratories offer discounts on bulk volume. Costs for ten products to 8//of the above Parcom tests can be reduced from 20 to 5S% ! Unfortunately in research, it is not always possible to test ten products at one time. Obviously no biodegradation test is required for inorganic materials. Where a high Log Pow or a low biodegradable result is obtained some Parcom authorities desire a bioaccumulation orinherant biodegradability test. Some are requiring that where a sedimentary reworker test is required (synthetic organics) then an anasrobic biodegradation test is also required. Some authorities have indicated that if the product is surface active, then log Pow does not need to be run provided the substance is termed readilv biodegradable.

694

,..

SPE 28740 ..=..-

Richard P. Jachnik . .. .

13,. . . .. .-.. ----.-, . . .- :.. ..:. .:

Table

4-

Synthetic

System.

Environmental

Testing

Costs

In the USA, each new product has to have a Mysid shrimp test in a generic mud. Area USA. For a new synthetic system with 2 emulsifiers, wetting agent, organoclay, and base synthetic.
1

Dollars Total Costin tJS.,

3250

Parcom.

(as per table 6. minimum data set} test and bioaccumulation

31,415

Add anaerobic

Table . Formulated
Environmental

5 Product B

Data c.btaimd In the Netherlands

Algae: phaeodactytum

tricomutum:

EBC50 72 hr (Gro tih

Inhibition)

504 M9// 760 mg/!

ERC502&72 hr (Growth rate reduction) NOEC gi 180 mg/l; gr 320 mgfl. Crustacean: Chaetogamma&s ma%us: 96.hrLC5058. 7 mg/f.

Log {Pow): Main Peak < ~

minor peak 4.

Seawater

Biodegradability: (Now OECO 306). 120A at 1ull~c.once&6&. 5h at 3 j.dil concentration, iii the test.

COO 2046

rng oxygemmI

No toxicity to the organism,>

Formulated Potassium Chloride polymer mud containing

Product B. Seawater Siodegmdability: < 10% degradation at either 40 PIA or 100 Pill concentration.

COD determined

to be 56 mg oxygenhnl.

No toxicity to the organismas in the test. A Sedimentary reworker test was m o field mud. This contained 3% of product B by VOIUIIW and a wawr soibl~ Sutiactint at 0.5% by volmne which is know to be toxic, Thela~er caused some problems in ca)ctdeding the true effect of product B, but the 14 day NOEC for the mud was calculated to be 1.8 glkg sedimem and 0.1 g/kg sediment for the product alone.

695

14

Variance in Environmental

Legislation. Cause and Effect of Drilling Fluid Research and Use

SPE 28740 -----

Table differences Zki@iance:

6 tirOtO.c~ls fOr Mysids.

~6~t @jifi ! in

in Toxicity Results using EPA and Parcom (1992) Parcom I 992

Mysidops;s Mysidopsis Acwtia Acart;a mgil ,4cwtia

r:. ,. ,::., !::::tf:!:

Butanol

fio~cot.
ppm

EPA Pmwcol. MYskfOP*$ti~tiii

30030-1 Generic WJJIJ 7. ppm 48Hr

3 mol Ethoxylated

bahia 9ehr LC50 > 1000_PPm bahia 96hr LC5 0121 hr LCSO >3200 48 hr LC50

range finder

.3 mol Propoxylated Butanol 3 mol Propoxylated Methanol

30,000-100,000

ppm 48Hr range finder

fvlysidopsis bahia 96hr LC50 >1000 tmsa48 tonsa:

ppm

10,000-30,000

ppm 96Hr rangefinder

to 100,000

c1 i Linear.AlkYl eenz@ne
OlefinType 1 (with some C14) Fluid

mg/1

<10,000 ppm mud 1:30,000 ppm mud 2. 96Hr range finder 240,000-308,000 260,000-320,000

>.10,000

ppm. 10 ppg Mud in Gen 7 ppm at 5% in Gen 7 ppm at

Glycol Emulsion Spotting PHPA 100% Sodium Lignosulphonate

tonsa: 48hr LC50 325 mg/1

Ac.wtia tonsa: 48hr LC50 493 mgil mg/1 Skeletonema: 72 hr ECrjO >1000 Polymer Acartia ronsa: 48hr LC50 1451 mg/1 mgll Skeletonemx 72hr EC5 0550

From 225,000 ppm to > 1,000,000 2 and 1 ppb . Different muds. 586,000 ppm at 10ppb in Generic 7.

Table
Toxicity

7
DMA prepared with mineral Oil Shel[sOl DMA content) .,

results of the Paxcom ring test oil mud Ca,b=ea ( <0.5% aromatics

,.sp!+ms:.. ....:.:, ,,, ,.

Ske/etonema costatum Crangon crangon Chaetogammarus marinus Echinocardium cordatum Bath yporea sarsi

:,...Para.rneter
Ec~~ 86 hr LC50 10 day LC50 21 day LC50 10 day LC60

Twitt
3452 >1800 mgil mg/1

180 mgll 133 mglkg sediment.

A400 mg/kg sediment.

696

Table Results for several different

8 Synthetic materials. ResiIlt >1 OOOmg/1 >3200 mgll ,.

;,;: :

,~ynthetic

,,,:,..,..:,,

T&WSpecies Skeletonema costatum NOEC

Parameter

C,, Linear Benzene ,, !,

Alkyl ,7 ,, ,!

Blended Ester A

Acarda tonsa Ecetoc 28 Corophium volutator Echinocardium cordatum ,, ,,

48 hr LC50 Anaerobic degradation 10 day LCq 14 day LC5n . ,,

63-87% at 40 mg/1 452 mg/kg sediment <<320 mglkg sediment 1220. mglkg sediment. Toxic effects not complete.. NOEC 320 mg/kg 9246 mg/kg sediment 6001 mglkg sediment S21 mglkg sediment >6 >1,000,000 ppm. mud in Generic 7.

Ester B Blended Ester C O[efin Type 1 (with some

Corophium volutator ,, ,, !,

10 day LC50 ,, ,, ,, ,, Log Pow 96 hr LC50

C,4)
!! Olefin Type C16+ only] 2

!, (with

OECD 117 Mysidopsis bahia

dense

NB: The log Pow was obtained by the HPLC method. No elution from the column was obtained after 90 minutes, hence it was assumed that log P~w is >6. However, the material could also be very insoluble in both water and n octanol!

Table

Cost of Organics in $ per Metric Ton organic.

Mineral oil

~~ , ,

$ C&t per Metdc tan / $ Costper barrel 1 nis 379151 1321 962/129/811 1924 125a I 1623

Cheapest Water Insoluble Synthetic Most Expensive Water Insoluble Synthetic

697