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Science of the Total Environment 610–611 (2018) 1010–1019

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Science of the Total Environment

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Short Communication

Oil pollution in soils and sediments from the Northern Peruvian Amazon
Antoni Rosell-Melé a,b,⁎, Núria Moraleda-Cibrián a, Mar Cartró-Sabaté a, Ferran Colomer-Ventura a,
Pedro Mayor c,d,e, Martí Orta-Martínez a,f,g,⁎
a
Institute of Environmental Science and Technology, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain
b
ICREA, 08010 Barcelona, Spain
c
Dept. Sanitat i Anatomia Animals, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain
d
FUNDAMAZONIA, Iquitos, Loreto, Peru
e
Programa de Pós-Graduação em Saúde e Produção Animal na Amazônia, Universidade Federal Rural da Amazônia, Belém, CEP 66077-901, Brazil
f
International Institute of Social Studies, Erasmus University Rotterdam, The Hague, The Netherlands
g
Instituto de Geografía, Universidad San Francisco de Quito, Quito, Ecuador

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Occurrence of petrogenic hydrocarbon


pollution in soils and sediments from
NW Amazon
• Pollution is identified from the presence
of steranes and hopanes.
• Petrogenic hydrocarbons in hunting or
fishing areas of local indigenous inhabi-
tants
• Source of hydrocarbons are the local oil
extraction activities.
• Wildlife and local human populations
are exposed to oil via the ingestion of
soil.

a r t i c l e i n f o a b s t r a c t

Article history: Oil has been extracted from the Northern Peruvian Amazon for over four decades. However, few scientific studies
Received 29 May 2017 have assessed the impacts of such activities in the environment and health of indigenous communities in the re-
Received in revised form 23 July 2017 gion. We have investigated the occurrence of petrogenic hydrocarbon pollution in soils and sediments from areas
Accepted 23 July 2017
favoured as hunting or fishing grounds by local indigenous inhabitants. The study was conducted in one of the
Available online xxxx
most productive oil blocks in Peru, located in the headwaters of the Amazon river. Soils and river sediments, in
Editor: Kevin V. Thomas the vicinity of oil extraction and processing infrastructure, contained an oil pollution signature as attested by
the occurrence of hopanes and steranes. Given the lack of any other significant source of oil pollution in the re-
Keywords: gion, the sources of hydrocarbons are likely to be the activities of the oil industry in the oil block, from voluntary
Oil pollution discharges or accidental spills. Spillage of produced water was commonplace until 2009. Moreover, petrogenic
Amazon compounds were absent in control samples in sites far removed from any oil infrastructure in the oil block.
Soils Our findings suggest that wildlife and indigenous populations in this region of the Amazon are exposed to the in-
Sediments gestion of oil polluted soils and sediments. The data obtained supports previous claims that the local spillage of oil
Steranes
and produced waters in the water courses in the Corrientes and Pastaza basins could have eventually reached the
Hopanes
main water course of the Amazon.
© 2017 Elsevier B.V. All rights reserved.

⁎ Corresponding authors at: Institute of Environmental Science and Technology, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain.
E-mail addresses: antoni.rosell@uab.cat (A. Rosell-Melé), marti.orta@uab.cat (M. Orta-Martínez).
A. Rosell-Melé et al. / Science of the Total Environment 610–611 (2018) 1010–1019 1011

Fig. 1. Map of the study area and approximate location of the samples analyzed in this study.

1. Introduction However, there is not any reported environmental forensic evidence


linking the occurrence of petrogenic hydrocarbon compounds in river
The Western Amazon maintains large tracts of intact tropical moist water or sediments with the well documented occurrence of oil spills.
forest, and is also home to indigenous ethnic groups, including some As far as we are aware, only one published scientific study has linked
of the world's last uncontacted peoples living in voluntary isolation. Be- the occurrence of polycyclic aromatic hydrocarbons (PAH) in river
neath this highly diverse and remote environment are large reserves of water and sediments with oil-related activities in the Peruvian Amazon
oil and gas, some of which have been exploited since the 1930s (Finer (Reátegui-Zirena et al., 2014).
et al., 2008; Orta-Martínez and Finer, 2010). This situation, which affects In here, we describe the occurrence of petrogenic hydrocarbon pol-
most of the global tropical rainforests in Southeast Asia, Central Africa lution in soils and sediments from sites accessed regularly by the local
and South America, has been argued to pose significant risks to biodi- indigenous populations for subsistence hunting or fishing. These are in
versity and threatened species (Butt et al., 2013). Nevertheless, there the vicinity (i.e. from tens of meters to a few kilometers) of oil infra-
are few scientific publications that describe the chemical pollution im- structure from the most important oil producing block (formerly la-
pact of oil extraction activities in the Amazon. As a consequence, societal belled 1AB and at present 192; extending over 512,347 ha) in the
debates, and governmental and local actions set up to minimize the risk Corrientes, Tigre and Pastaza basins in Peru. The cumulative production
of oil extraction activities are arguably taking place without much factu- of the block (1972–2015) is 709 million barrels of oil from 247 wells in
al scientific knowledge. 13 fields (Ministerio de Energía y Minas de Perú, 2015). The oil block
In this paper we focus on the Northern Peruvian Amazon (Fig. 1), was drawn across the ancestral territories of the Achuar, Quechua and
where oil has been extracted since 1971 (Finer and Orta-Martínez, Kichwa indigenous peoples (Orta-Martínez et al., 2007).
2010). The region has become the most productive in Peru, with 67% of
the national oil production at its peak in 1982 (oil blocks 1AB and 8/8X) 2. Methods
(Orta-Martínez and Finer, 2010). Over the years repeated concerns have
been expressed on the practices of the oil industry, and their negative 2.1. Sample collection
consequences for the environment and the welfare of local indigenous
populations (Goldman et al., 2007; Kimerling, 1991; Orta-Martínez Eight samples (see locations in Fig. 1; Table 1) were soils collected
et al., 2007). As a result, in 2013 and 2014 the Peruvian government de- from mineral licks (also known as clay or salt licks), which are wildlife
clared the environmental and health state of emergency in areas of the
oil blocks of the Corrientes, Marañón, Pastaza and Tigre basins.
A cause for concern has been the high blood levels of lead (Pb) de- Table 1
tected among the indigenous population of the Corrientes River (Orta- Locations and codes of samples analyzed in this study.

Martínez et al., 2007). Initially, no association was established with Code Type UTM coordinates Catchment
the activities of the oil industry in the area, given that Pb values in envi- CN1 Collpa in a seismic survey site 18M 368240 9684409 Corrientes
ronmental samples were found to be relatively low (Anticona et al., CN2 Remote collpa 18M 329303 9696322 Pastaza
2011, 2012). However, a meta-analysis of chemical data from govern- CN3 Remote collpa 18M 371420 9679240 Corrientes
mental institutions and oil companies reports has proved that the CA1 Collpa next to an oil well 18M 336588 9701714 Pastaza
CA2 Collpa in a dripping well 18M 350590 9679070 Pastaza
dumping of produced or formation waters (i.e. water found in the
CA3 Collpa next to an oil well 18M 333793 9702125 Pastaza
same formations as oil and gas) increased lead concentrations, among CA4 Collpa with an oil spill 18M 370415 9741077 Corrientes
other heavy metals, in rivers of the region (Yusta-Garcia et al., 2017). CA5 Soil next to oil well 18M 360589 9729626 Corrientes
Oil extraction activity concentrated in the Corrientes and Tigre rivers S1 Oxbow lake 18M 366037 9716548 Corrientes
has also been linked with an increase in the fluxes of dissolved sodium S2 River bank 18M 366161 9716211 Huayurí-Corrientes
S3 Wetland 18M 342283 9691094 Pastaza
(Na) and chloride (Cl) in the Amazon River (Moquet et al., 2014).
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A. Rosell-Melé et al. / Science of the Total Environment 610–611 (2018) 1010–1019 1013

activity hotspots where mammals and birds congregate to consume soil are shown in Table 2, which have also been used to calculate the bio-
(i.e. geophagy) or drink water (Blake et al., 2011; Bravo et al., 2010; marker diagnostic rations in Table 3.
Brightsmith and Munoz-Najar, 2004; Emmons and Stark, 1979). It is
well documented that mineral licks are also favoured as subsistence
hunting grounds by local inhabitants (Blake et al., 2011). They are 3. Results and discussion
known locally as collpas, and occur naturally (sampling sites CN1–3,
where CN stands for natural collpa). In a number of sites (CA1–5, 3.1. Identification of petrogenic inputs
where CA stands for anthropic collpa), the mineral licks can be consid-
ered to be anthropogenic as they developed at discharge points of oil in- We have targeted the analysis of n-alkane distributions and the
frastructure (i.e. sump tanks and produced water dumping sites). Soil identification of unresolved complex mixture (UCM) of hydrocarbons,
samples were retrieved using a hand Auger soil sampler. They resulted steranes and hopanes, whose presence in environmental samples indi-
from the combination and homogenization of 3 samples taken between cates the occurrence of oil derived products (Volkman et al., 1997;
0 and 20 cm depth and a 10 × 10 cm section (after removing overlaying Wang et al., 2006). These compounds are typically found in high con-
leaf litter) separated by several meters in each area. The soils were centrations in crude oils and petroleum products, including lubricating
stored in plastic bags and transported at ambient temperature, until oils, asphalt and heavy residual oils, and are particularly useful to define
being placed in the freezer once samples arrived at the laboratory. the identity of the spilled product in environmental forensics, when the
We also collected three sediment samples (S1–3) to explore the oc- petrogenic substance is severely weathered (Aeppli et al., 2014; Wang
currence of pollution in aquatic settings. Sample S1 was retrieved on the et al., 1999, 2013; Wang and Stout, 2010). Steranes and hopanes are
bank of an abandoned meander of the Corrientes river, which devel- formed during diagenesis and catagenesis of organic matter from the
oped into an oxbow lake, ca. 4 km downstream (geographical distance) precursor steroids or hopanoids. They are also more resistant to biotic
from any oil infrastructure. Sample S2 was obtained from the bank at and abiotic degradation than other compounds typically found in oils,
the mouth of the Huayurí River, a tributary of the Corrientes River, such as n-alkanes and PAHs, which have also significant modern sources
and ca. 6 km downstream (geographical distance) from any oil infra- in tropical environments (Krauss et al., 2005; Volkman et al., 1997;
structure. Sample S3 was retrieved from a wetland located a few meters Wilcke, 2007; Wilcke et al., 2000, 2002).
away from a major pipeline (known locally as shipping line, which The analysis of n-alkane distributions is a relatively fast and simple,
carries all the oil from the Corrientes and Tigre basins towards the Pas- and can offer a first line of evidence to determine the presence of oil in-
taza basin). All three sediment samples are located downstream from puts in an environmental sample. In the case of petrogenic inputs, the
abandoned produced water dumping sites, and are used locally for fish- distribution of n-alkanes would show a predominance of odd over
ing. Sediment samples were obtained using a metacrilate tube (10 cm even carbon atoms chain lengths (i.e. compound preference index or
diameter), which was pressed by hand into the sediment, capped and CPI). The CPI values for most oils and petroleum products are close to
then manually pulled upwards to extract the sediment. The top 10 cm 1, while n-alkanes from the epicuticular wax in vascular plants have
were stored in plastic bags, and transported at ambient temperature higher CPI values, that are generally between 2 and 12 (Wang et al.,
until being placed in the freezer once samples arrived at the laboratory. 2009). According to these criteria, the n-alkanes distribution in only
one sample (CA5) would provide conclusive evidence of the presence
2.2. Chemical analyses of oil products (Fig. 2, Table 1). The n-alkane fingerprint of this sample
indicates that the oil was heavily weathered as the distribution lacks
Approximately 5 g of dry sediment or soil were extracted with 10 mL light hydrocarbons and is dominated by high molecular weight com-
of trace analysis grade n-hexane–acetone (1:1, v/v) (Merck, Darmstadt, pounds (the continuous distribution of n-alkanes range from C37–C53).
Germany) in the ultrasonic bath for 15 min. The extraction process was In contrast, all the other samples are dominated by inputs of n-alkanes
repeated three times. The extracts were fractionated by adsorption from higher plants, as indicated by the odd over even predominance
chromatography with glass columns containing 1 g of silica (Scharlau, of the carbon chain lengths (i.e. CPIs value higher than 1, closer to values
Barcelona, Spain) and 1 g of aluminium oxide (Sigma–Aldrich, St. present in uncontaminated soils, see Table 3). The most abundant n-
Louis, USA) previously activated at 110 °C and deactivated 5% with ul- alkanes, at which the distributions peak, is either the C29 or C31 n-
trapure water (Milli-Q/Millipore, Cork, Ireland) and 1 g of sodium sul- alkane, which is typical from higher plants inputs. A much weaker
phate (Merck, Darmstadt, Germany). Two fractions were collected: F1, petrogenic n-alkane distribution with no odd-even predominance is
corresponding to aliphatic hydrocarbons, eluting 2.5 mL of n-hexane; also apparent in the samples (except those from natural collpas CN1–
and F2, corresponding to polycyclic aromatic hydrocarbons (PAHs), 3), starting at relatively light carbon chains (C14–C16), and extending
adding 10 mL of n-hexane–dichloromethane (2:1, v/v). The extracts until heavy n-alkanes, which is particularly apparent in sample S2
were concentrated first by rotary evaporation and finally with a gentle (Fig. 2). However, short-chain n-alkanes could also be attributed to in-
stream of N2 to near dryness. puts from phytoplankton (Volkman et al., 1997).
The identification of oil biomarkers was carried out in an Agilent Another piece of evidence to assert the occurrence of petroleum con-
7890A gas chromatograph (GC) coupled to an Agilent 5975C mass spec- tamination in the samples can be the presence of a UCM of hydrocar-
trometer (MS) operated in electron impact ionization mode (70 eV), bons, which shows up as a baseline rising in the gas chromatogram
and equipped with a DB-1 capillary column (J&W Scientific, CA, USA) (Farrington and Quinn, 1973; Farrington et al., 2015). In most studies
and a guard column. The GC injector was operated in splitless mode. the UCM is interpreted as indication of petroleum pollution, namely
The GC oven temperature program started at 60 °C (held for 1 min) biodegraded oil or lubricants. There are also indications that in some in-
then increased to 320 °C at a rate of 4 °C min−1 and held for 22 min. In- stances it may derive from natural inputs or bacterial reworking of nat-
jector, transfer line, and ion source temperatures were 310 °C, 320 °C ural lipids in situ or during storage, but it is unlikely to be significant in
and 250 °C respectively. Helium was used as the carrier gas at constant areas affected by human activities and the occurrence of spills (White
flow of 2 mL min−1. The MS was used in both scan mode and single ion et al., 2013). The occurrence of a UCM in the samples is only clear in
mass mode at a time, monitoring m/z = 71 for the n-alkanes, m/z = 191 sample CA5 (Fig. 2). Sample S2 also presents a slightly raised baseline,
for the pentacyclic triterpanes (hopanes), and m/z = 217–218 for the and displays a double distribution of n-alkanes, from natural origin
steranes. The shorthand notion of compounds identified in Figs. 2–4 and petrogenic.

Fig. 2. Distribution of n-alkanes in samples (a) CA1, (b) S3, (c) CA5, (d) S1, (e) S2. Data obtained by plotting the ion at m/z 71. Peak identities refer to the n-alkanes carbon numbers. Pr:
pristane; Ph: phytane; IS: internal standard.
1014 A. Rosell-Melé et al. / Science of the Total Environment 610–611 (2018) 1010–1019

Fig. 3. Distribution of hopanes in samples (a) CA1, (b) S3, (c) CA5, (d) S1, (e) S2. Data obtained by plotting the ion at m/z 191. See Table 2 for abbreviation of peak identities.
A. Rosell-Melé et al. / Science of the Total Environment 610–611 (2018) 1010–1019 1015

Conversely, all samples from anthropogenic mineral licks (CA1–5) the settlement of Andoas (Fig. 1). The local inhabitants have predomi-
and the sediments investigated contained traces of steranes and nantly a subsistence economy dependent on fishing, hunting and slash
hopanes (Figs. 2 and 3; Table 3), while none of the natural mineral and burn agriculture. The only significant industrial activity is the one
licks soils (CA1–3) contained traces of these compounds. In the samples carried out by the oil industry, which also provides employment to
with hopanes, the 17α(H),21β(H)-stereochemistry predominate some of the local inhabitants. At first, the crude petroleum was
(Fig. 2), indicating a substantial contribution from petroleum (Sakari transported by cargo ship to Iquitos, but from 1978 onwards, oil has
et al., 2010; Volkman et al., 1997; Wang et al., 2007). No ββ-isomers been pumped directly through the North Peruvian Oil Pipeline from
were detected, and thus we can exclude significant inputs of hopanes the area to the Bayovar refinery on the Pacific coast (Orta-Martínez
from modern living organisms. Thus, in samples with mature organic et al., 2007). Processing of the crude oil and waste products is, however,
matter contents the hopanes are generally composed of three undertaken locally, in the oil block. Most samples were located near
sterioisomeric series, namely 17α(H),21β(H)-Hopanes, central production facilities or sump tanks (Fig. 1 and Table 1). The latter
17β(H),21β(H)-Hopanes and 17β(H),21α(H)-Hopanes. In organically are designed to contain oil overflowing from a well due to unexpected
mature samples, the αβ epimeric isomers in the C27–C35 range have a increases in pressure. However, in the study area oil is rarely recovered
greater thermodynamic stability in comparison to the βα and ββ iso- from these tanks, and it overflows with the regular heavy tropical rain-
mers, and are typical of petroleum. In contrast, ββ-isomers are also falls when the tanks are uncovered (Orta-Martínez et al., 2007). In addi-
commonly found in living organisms (Volkman et al., 1997). Conse- tion, oil produced waters were discharged untreated to the local rivers
quently, in modern samples with petrogenic inputs all three isomers until January 2008 in Block 1AB, and the reinjection of the formation
(αβ, βα, and ββ) may be found. waters into the oil wells was not generalized until the end of 2009
The steranes in petroleum, as they are derived from sterols, occur as (Comisión de Pueblos Andinos Amazónicos y Afroperuanos Ambiente
the C27, C28 and C29 homologous series in different proportions which y Ecología, 2013). Most of the waste generated from oil extraction is
reflect the carbon number distribution of the sterols in the precursor or- composed of produced waters, which amount in average to 70% of the
ganic matter in the source rocks for these oils (Wang and Stout, 2010). liquid fluids extracted from a well (Fakhru'l-Razi et al., 2009). The cu-
They have a number of isomeric forms with different stereochemistries mulative water production of the block 1AB until April 2012 was
at positions 5, 14, 17, 20 and 24. These are the type of distributions 6.5 billion barrels, which represents a water cut of 96% (Perú Petro,
found in the samples from the Corrientes and Pastaza basins (Fig. 4), 2015). Production water contains a very high concentrations of salts
which further confirms the occurrence of petrogenic inputs to some of (denser than seawater), hydrocarbons and heavy metals
the soils and sediments investigated. The relative higher abundance of (Fakhru'l-Razi et al., 2009; Neff et al., 2011). The production waters
the higher molecular weight homologues may indicate that the oil sig- from the Northern Peruvian (Marañon) oil basin can vary considerably
natures are substantially weathered (Wang et al., 2007). For instance, in salinity from brines with values of up to 200,000 mg L−1 of total dis-
samples CA1, CA5 and S3 (Fig. 4) display a profile of degraded steranes solved solids (TDS) to saline waters of 19,000 mg L− 1 TDS (Barson,
where the 20(R + S) αββ C29 (R + S) N C28 (R + S) N C27 (R + S). This 2002; Sofer et al., 1986), while natural riverine NaCl concentration is
trend is not so clear for sample S1, where C27 bbR N C29 bbR N C29 bbS about 3 mg L−1 (Meybeck and Helmer, 1989).
N C28 bbS N C28 bbR N C27 bbS and the sample S2 which follows this pat- Another likely source of petrogenic pollution in the local waterways
tern: C29 bbS N C28 bbR N C29 bbR N C27 bbR N C28 bbS N C27 bbS. is the emissions from off board two stroke engines in canoes, and diesel
In summary, it is apparent that if the study had been limited to the engines in large transport ships. The former is chiefly used by local in-
analysis of n-alkane distribution and the occurrence of UCMs, habitants, while the latter are employed chiefly by the oil industry as
petrogenic pollution would have only been conclusive in one out of supply ships, and to transport oil. We do not have any figures, but we
the 11 samples. Nevertheless, the occurrence of sterane and hopanes speculate that the emissions from lubricant oils and petrol derived
in 75% of the samples, i.e. those soils retrieved from anthropogenic min- from transport by local populations over the years must be negligible
eral licks and sediments located in the vicinity or downstream - up to in comparison to the oil industry emissions from transport, discharges
6 km - of the oil infrastructure, points at the widespread occurrence of and spills. Obviously, they would only pollute local rivers, not soils
petroleum derived products within the oil block in various river and wetland sediments such as those analyzed in here. We consider
catchments. also as negligible in a regional context the petrogenic emissions derived
from local settlements to generate electricity (given the sparse number
3.2. Sources of petrogenic inputs and the small size of settlements, and that they often only operate a few
hours a day), and from motorized transport in the existing dirt roads
In the marine environment, the occurrence of petrogenic hydrocar- (Fig. 1). Consequently, given the issues outlined above, it seems a plau-
bons is ubiquitous as it derives from natural as well as anthropogenic sible hypothesis that any petrogenic inputs in the samples are derived
sources, and thus it is unrealistic to expect a complete absence of hydro- from the activities of the oil industry in the area, mainly from voluntary
carbons from a “clean” environment (Kingston, 2002). In a continental discharges or accidental spills of produced water and oil over the years.
setting, oil is not as easily dispersed as in the marine environment In fact, oil wells and pipelines on land are the regular source of spillages
(Prince et al., 2003). Thus, while ocean currents and biogeochemical and contamination on continental environments worldwide (Service
processes will disperse oil effectively from a given point source, in rivers et al., 2012).
is bound to be dispersed and transported downstream along the river Moreover, those samples where no petrogenic biomarkers were de-
course, and mixed throughout the water column and deposited in the tected are those located in sites far removed from any of the existing oil
bottom sediments (Goeury et al., 2014). In soils and wetlands, which infrastructure. In these sites, the mineral licks have developed naturally,
are low energy environments, the majority of the hydrocarbons in the not by the agency of any anthropic activity. In contrast, samples CA1–5
oil will stay near the spillage point, and natural weathering will be the were retrieved from mineral licks created after the construction of oil
main process that will gradually remove the oil from the deposition infrastructure. Some of these places received the overflows of sump
site. Consequently, the occurrence of petrogenic compounds in the sam- tanks (CA1 and CA2) or were located in the area of influence of a pro-
ples discussed in here can only be derived from local sources, or up- duced water or oil dumping site (CA3–5). Consequently, we attribute
stream sources in the case of fluvial sediments. the petrogenic signatures of the soils to inputs from the nearby
Presumably, to most people the area studied is extremely remote, if infrastructure.
one considers that it is only accessible by boat (3–5 days upstream trav- In relation to the sediment samples, sample site S3 lies underneath a
el time from the city of Iquitos, which in itself is only accessible by boat major oil pipeline in a wetland. Ruptures of such pipelines are a com-
or plane), or by plane using the private (oil-company owned) airfield in mon cause of spills worldwide (Perhar and Arhonditsis, 2014).
1016 A. Rosell-Melé et al. / Science of the Total Environment 610–611 (2018) 1010–1019

Fig. 4. Distribution of steranes in samples (a) CA1, (b) S3, (c) CA5, (d) S1, (e) S2. Data obtained by plotting the ions at m/z 217 and 218. See Table 2 for abbreviation of peak identities.
A. Rosell-Melé et al. / Science of the Total Environment 610–611 (2018) 1010–1019 1017

However, we speculate that the origin of the hydrocarbons may be re- adapted to explore the water-air interface to breathe and feed are
lated to the fact that the site is located in an area that formerly received particularly vulnerable to the physical occurrence of the oil spills
the discharges of produced waters. These discharges drain into a flood (Kochhann et al., 2015).
plain that it is crossed by the oil pipeline where sample S3 was retrieved In our study, the collection of the samples from mineral licks and
from and formed a large artificial pool that it is still visible by satellite river sediments was motivated by the claims by local indigenous
next to the sampling point (e.g. visible on Google Earth, see coordinates hunters and indigenous environmental monitors that the game hunted
in Table 1). Similarly, sample S2 is also located 8,7 km downstream from for subsistence, and organisms collected from rivers or wetlands often-
another disposal site of produced waters. In contrast, sample S1 are sed- times smelled of and were smeared with oil. We have now shown that
iments deposited by river waters in areas that and are not adjacent to oil is indeed present in soils from mineral licks in the vicinity of infra-
any major oil infrastructure (i.e. oil production facilities). At this stage, structure, and in sediments from aquatic settings. Animals visiting min-
we speculate that the oil inputs might derive from former spills that oc- eral licks may consume up to 30% of soil as part of their diet (Beyer and
curred in the Huayuri Norte oil wells, which are upstream and relatively Fries, 2003). Wildlife in tropical rainforests are bound to ingest soil and
close to the site (7,5 km upstream). Sediments with petrogenic signa- water from these oil polluted sites, and could be a source of exposure to
tures may have been redeposited in the wet season, when the water petrogenic compounds for human communities that rely on subsistence
levels in the Corrientes rise by several meters and flood all the adjacent hunting and fishing. The health effect that the ingestion of oil-polluted
lands to the river. The river may transport downstream resuspended soil by Amazonian frugivorous and herbivores may have on wildlife
sediment loaded with sediments from contaminate lands upstream. and human population has not yet been studied. In fact, health effects
These can be expected to eventually reach the Tigre and Marañón rivers, among people residentially exposed to upstream oil industry contami-
which are likely to receive also petrogenic inputs from extraction activ- nants have been poorly studied around the world (O'Callaghan-Gordo
ities in the oil block 8 (Reátegui-Zirena et al., 2014), and eventually et al., 2016). However, it is acknowledged that the inadvertent ingestion
reach the Amazon river as already reported for dissolved chemical of contaminated soil and sediments can be a major pathway for chemi-
loads (Moquet et al., 2014; Yusta-Garcia et al., 2017). cal exposure to humans with a subsistence diet (Doyle et al., 2012;
The oils in the region are derived from Cretaceous reservoirs and de- Irvine et al., 2014). In indigenous communities elsewhere, the human
rive from the Chonta formation source rock and the Vivian formation soil ingestion rate was of several hundreds of mg per day (Irvine et al.,
reservoir (Perupetro report, 2009). However, there is insufficient infor- 2014; U.S. Environmental Protection Agency, 2011). Consequently, our
mation in the scientific literature or freely available as public reports to results suggest that oil activities could potentially result in bioaccumu-
ascertain the chemical fingerprints of the oils in the oil block studied. lation and biomagnification of oil chemicals, and could be hazardous
The scarce information we have obtained on the chemical fingerprints for the conservation of top predators in the tropical rainforests, and
of oil extracted across the region suggest that they have significantly for the health of local indigenous peoples that have a subsistence
different biomarker fingerprints (Core Laboratories Inc, 1999; Sofer economy.
et al., 1986). Consequently, at this stage we have not been able to
establish the chemical composition of the putative sources of the
biomarkers in our samples and compare their biomarker diagnostic 4. Conclusions
ratios with those shown in Table 3, and from an environmental forensics
perspective establish the sources of the petrogenic inputs in the Soils and river sediments, in the vicinity or downstream, respective-
samples. The wide range of values of the diagnostic biomarker ratios ly, from oil extraction and processing infrastructure in the rainforests of
we have measured suggest, nevertheless, that the oil signatures derive the Northern Peruvian Amazon contain an oil pollution signature. This is
from different type of oils, or spills at different times with varying not an unexpected finding in a worldwide context given that the oil in-
degree of weathering. dustry infrastructure commonly has a significant environmental impact
in the surrounding lands, be it during extraction, processing, transport
3.3. Health and conservation implications and distribution processes.
The hydrocarbons in sediments in the water courses of the Corrien-
The presence of oil infrastructure per se is known to lead to a tes and Pastaza basins could have eventually reached the main water
wide range of environmental impacts (Hinte et al., 2007). Oil spilled course of the Amazon, as already noted for other chemical components
on terrestrial environments will undergo volatilization and biodegrada- present in produced waters (Moquet et al., 2014; Yusta-Garcia et al.,
tion. On soils, a significant fraction will infiltrate vertically into the 2017). In contrast, spillages in soils are likely to have a local impact.
subsurface, penetrate the soil micropores and remain in the soil matrix However, such an impact is compounded in the oil block investigated
for years (Dutta and Harayama 2001; Liang et al. 2009). The remaining because the localities where oil was spilled may be the feeding grounds
refractory oil fractions, such as high molecular weight hydrocarbons, of local fauna (i.e. salt licks or mineral licks), and in turn focal hunting
resins and polar fractions have attracted significant concerns regarding spots of the local indigenous inhabitants. Similarly, we show that
their mutagenic and carcinogenic potentials and their ability to areas used locally for fishing also contain an oil pollution fingerprint.
bioaccumulate (Hoff et al., 2007; Yavari et al., 2015). The effect of the These findings suggest that wildlife in an oil producing region of the
spilled oil on the land ecosystems is therefore expected to be acute, Amazon are exposed to the ingestion of oil polluted soils and sediments,
and the natural recovery of polluted soils slow (Ebuehi et al., 2005; that may reach the human food chain. This exposure to oil contaminat-
Vinson et al., 2008; Yavari et al., 2015). The unintentional or intentional ed foodstuffs may extend beyond the area of study as fish and wild meat
ingestion of polluted soil is also a potential route of exposure for both are also sold in local and regional food markets, like the ones in the city
humans and wildlife (Beyer and Fries, 2003; Irvine et al., 2014; U.S. of Iquitos.
Environmental Protection Agency, 2011). Our study further illustrates how remote natural areas also contain
On aquatic systems, the presence of oil also poses a significant yet another ubiquitous anthropogenic footprint. The oil industry, in
threat to aquatic life, as toxic effects cascade across trophic levels, the far reaches of the Amazon, has contributed to the expansion of an-
affecting phytoplankton, zooplankton, fish, aquatic birds, mammals, thropogenic contaminants from industrial centres to the most remote
and benthic organisms (see review in Perhar and Arhonditsis, 2014). areas. The practices and the expansion of the oil industry to the remain-
This is partly a consequence of the solubility of oil components which ing wilderness and biodiversity hotspots in the planet seem at odds
can be inversely related to salinity, and thus is enhanced in freshwater with any efforts to conserve them. Moreover, the ends of the continuum
(Whitehouse, 1984), as well as the reduced diffusion of oxygen into of human impact in the environment may be closer than is usually en-
water. Moreover, the myriad of fish species in Amazon rivers that are visaged (Mittermeier et al., 2003).
1018 A. Rosell-Melé et al. / Science of the Total Environment 610–611 (2018) 1010–1019

Table 2 Actions (REA agreement N° 289374 - ENTITLE), the ‘Conflict and Coop-
Abbreviations and chemical notation of steranes and hopanes analyzed in the samples, as eration Organisation over Natural Resources in Developing Countries’
well as the fragment m/z in the spectrometric analysis used to identify them and generate
the plots in Figs. 3 and 4.
program of The Netherlands for Scientific Research (NWO) and the ‘In-
ternational Initiative for Impact Evaluation’ (3ie).
Abbreviation Name m/z

C28 (22R) C28 Tricyclic terpane 191 Appendix A. Supplementary data


C28 (22S) C28 Tricyclic terpane 191
C29 (22R) C29 Tricyclic terpane 191
Supplementary data associated with this article can be found in the
C29 (22S) C29 Tricyclic terpane 191
27Ts 18α(H)-22,29,30-trisnorhopane 191 online version, at http://dx.doi.org/10.1016/j.scitotenv.2017.07.208.
27Tm 17α(H)-22,29,30-trisnorhopane 191 These data include the Google map of the most important areas de-
28ab 17α(H),21β(H)-28,30-bisnorhopane 191 scribed in this article.
29ab 17α(H),21β(H)-30-norhopane 191
29Ts 18α(H)-30-norneohopane 191
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