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

The Western Amazon maintains large tracts of intact tropical moist
forest, and is also home to indigenous ethnic groups, including some
of the world's last uncontacted peoples living in voluntary isolation. Be-
neath this highly diverse and remote environment are large reserves of
oil and gas, some of which have been exploited since the 1930s (Finer
et al., 2008; Orta-Martínez and Finer, 2010). This situation, which affects
most of the global tropical rainforests in Southeast Asia, Central Africa
and South America, has been argued to pose significant risks to biodi-
versity and threatened species (Butt et al., 2013). Nevertheless, there
are few scientific publications that describe the chemical pollution im-
pact of oil extraction activities in the Amazon. As a consequence, societal
debates, and governmental and local actions set up to minimize the risk
of oil extraction activities are arguably taking place without much factu-
al scientific knowledge.
In this paper we focus on the Northern Peruvian Amazon (Fig. 1),
where oil has been extracted since 1971 (Finer and Orta-Martínez,
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)
(Orta-Martínez and Finer, 2010). Over the years repeated concerns have
been expressed on the practices of the oil industry, and their negative
consequences for the environment and the welfare of local indigenous
populations (Goldman et al., 2007; Kimerling, 1991; Orta-Martínez
et al., 2007). As a result, in 2013 and 2014 the Peruvian government de-
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-
tected among the indigenous population of the Corrientes River (Orta-
linking the occurrence of petrogenic hydrocarbon compounds in river
water or sediments with the well documented occurrence of oil spills.
As far as we are aware, only one published scientific study has linked
the occurrence of polycyclic aromatic hydrocarbons (PAH) in river
water and sediments with oil-related activities in the Peruvian Amazon
(Reátegui-Zirena et al., 2014).
In here, we describe the occurrence of petrogenic hydrocarbon pol-
lution in soils and sediments from sites accessed regularly by the local
indigenous populations for subsistence hunting or fishing. These are in
the vicinity (i.e. from tens of meters to a few kilometers) of oil infra-
structure from the most important oil producing block (formerly la-
belled 1AB and at present 192; extending over 512,347 ha) in the
Corrientes, Tigre and Pastaza basins in Peru. The cumulative production
of the block (1972–2015) is 709 million barrels of oil from 247 wells in
13 fields (Ministerio de Energía y Minas de Perú, 2015). The oil block
was drawn across the ancestral territories of the Achuar, Quechua and
Kichwa indigenous peoples (Orta-Martínez et al., 2007).
2. Methods
2.1. Sample collection
Eight samples (see locations in Fig. 1; Table 1) were soils collected
from mineral licks (also known as clay or salt licks), which are wildlife
Table 1
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).
1012 A. Rosell-Melé et al. / Science of the Total Environment 610–611 (2018) 1010–1019
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activity hotspots where mammals and birds congregate to consume soil
(i.e. geophagy) or drink water (Blake et al., 2011; Bravo et al., 2010;
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
known locally as collpas, and occur naturally (sampling sites CN1–3,
where CN stands for natural collpa). In a number of sites (CA1–5,
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-
frastructure (i.e. sump tanks and produced water dumping sites). Soil
samples were retrieved using a hand Auger soil sampler. They resulted
from the combination and homogenization of 3 samples taken between
0 and 20 cm depth and a 10 × 10 cm section (after removing overlaying
leaf litter) separated by several meters in each area. The soils were
stored in plastic bags and transported at ambient temperature, until
being placed in the freezer once samples arrived at the laboratory.
We also collected three sediment samples (S1–3) to explore the oc-
currence of pollution in aquatic settings. Sample S1 was retrieved on the
bank of an abandoned meander of the Corrientes river, which devel-
oped into an oxbow lake, ca. 4 km downstream (geographical distance)
from any oil infrastructure. Sample S2 was obtained from the bank at
the mouth of the Huayurí River, a tributary of the Corrientes River,
and ca. 6 km downstream (geographical distance) from any oil infra-
structure. Sample S3 was retrieved from a wetland located a few meters
away from a major pipeline (known locally as shipping line, which
carries all the oil from the Corrientes and Tigre basins towards the Pas-
taza basin). All three sediment samples are located downstream from
abandoned produced water dumping sites, and are used locally for fish-
ing. Sediment samples were obtained using a metacrilate tube (10 cm
diameter), which was pressed by hand into the sediment, capped and
then manually pulled upwards to extract the sediment. The top 10 cm
were stored in plastic bags, and transported at ambient temperature
until being placed in the freezer once samples arrived at the laboratory.
2.2. Chemical analyses
Approximately 5 g of dry sediment or soil were extracted with 10 mL
of trace analysis grade n-hexane–acetone (1:1, v/v) (Merck, Darmstadt,
Germany) in the ultrasonic bath for 15 min. The extraction process was
repeated three times. The extracts were fractionated by adsorption
chromatography with glass columns containing 1 g of silica (Scharlau,
Barcelona, Spain) and 1 g of aluminium oxide (Sigma–Aldrich, St.
Louis, USA) previously activated at 110 °C and deactivated 5% with ul-
trapure water (Milli-Q/Millipore, Cork, Ireland) and 1 g of sodium sul-
phate (Merck, Darmstadt, Germany). Two fractions were collected: F1,
corresponding to aliphatic hydrocarbons, eluting 2.5 mL of n-hexane;
and F2, corresponding to polycyclic aromatic hydrocarbons (PAHs),
adding 10 mL of n-hexane–dichloromethane (2:1, v/v). The extracts
were concentrated first by rotary evaporation and finally with a gentle
stream of N2 to near dryness.
The identification of oil biomarkers was carried out in an Agilent
7890A gas chromatograph (GC) coupled to an Agilent 5975C mass spec-
trometer (MS) operated in electron impact ionization mode (70 eV),
and equipped with a DB-1 capillary column (J&W Scientific, CA, USA)
and a guard column. The GC injector was operated in splitless mode.
The GC oven temperature program started at 60 °C (held for 1 min)
then increased to 320 °C at a rate of 4 °C min−1 and held for 22 min. In-
jector, transfer line, and ion source temperatures were 310 °C, 320 °C
and 250 °C respectively. Helium was used as the carrier gas at constant
flow of 2 mL min−1. The MS was used in both scan mode and single ion
mass mode at a time, monitoring m/z = 71 for the n-alkanes, m/z = 191
for the pentacyclic triterpanes (hopanes), and m/z = 217–218 for the
steranes. The shorthand notion of compounds identified in Figs. 2–4
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.
1013
are shown in Table 2, which have also been used to calculate the bio-
marker diagnostic rations in Table 3.
3. Results and discussion
3.1. Identification of petrogenic inputs
We have targeted the analysis of n-alkane distributions and the
identification of unresolved complex mixture (UCM) of hydrocarbons,
steranes and hopanes, whose presence in environmental samples indi-
cates the occurrence of oil derived products (Volkman et al., 1997;
Wang et al., 2006). These compounds are typically found in high con-
centrations in crude oils and petroleum products, including lubricating
oils, asphalt and heavy residual oils, and are particularly useful to define
the identity of the spilled product in environmental forensics, when the
petrogenic substance is severely weathered (Aeppli et al., 2014; Wang
et al., 1999, 2013; Wang and Stout, 2010). Steranes and hopanes are
formed during diagenesis and catagenesis of organic matter from the
precursor steroids or hopanoids. They are also more resistant to biotic
and abiotic degradation than other compounds typically found in oils,
such as n-alkanes and PAHs, which have also significant modern sources
in tropical environments (Krauss et al., 2005; Volkman et al., 1997;
Wilcke, 2007; Wilcke et al., 2000, 2002).
The analysis of n-alkane distributions is a relatively fast and simple,
and can offer a first line of evidence to determine the presence of oil in-
puts in an environmental sample. In the case of petrogenic inputs, the
distribution of n-alkanes would show a predominance of odd over
even carbon atoms chain lengths (i.e. compound preference index or
CPI). The CPI values for most oils and petroleum products are close to
1, while n-alkanes from the epicuticular wax in vascular plants have
higher CPI values, that are generally between 2 and 12 (Wang et al.,
2009). According to these criteria, the n-alkanes distribution in only
one sample (CA5) would provide conclusive evidence of the presence
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
light hydrocarbons and is dominated by high molecular weight com-
pounds (the continuous distribution of n-alkanes range from C37–C53).
In contrast, all the other samples are dominated by inputs of n-alkanes
from higher plants, as indicated by the odd over even predominance
of the carbon chain lengths (i.e. CPIs value higher than 1, closer to values
present in uncontaminated soils, see Table 3). The most abundant n-
alkanes, at which the distributions peak, is either the C29 or C31 n-
alkane, which is typical from higher plants inputs. A much weaker
petrogenic n-alkane distribution with no odd-even predominance is
also apparent in the samples (except those from natural collpas CN1–
3), starting at relatively light carbon chains (C14–C16), and extending
until heavy n-alkanes, which is particularly apparent in sample S2
(Fig. 2). However, short-chain n-alkanes could also be attributed to in-
puts from phytoplankton (Volkman et al., 1997).
Another piece of evidence to assert the occurrence of petroleum con-
tamination in the samples can be the presence of a UCM of hydrocar-
bons, which shows up as a baseline rising in the gas chromatogram
(Farrington and Quinn, 1973; Farrington et al., 2015). In most studies
the UCM is interpreted as indication of petroleum pollution, namely
biodegraded oil or lubricants. There are also indications that in some in-
stances it may derive from natural inputs or bacterial reworking of nat-
ural lipids in situ or during storage, but it is unlikely to be significant in
areas affected by human activities and the occurrence of spills (White
et al., 2013). The occurrence of a UCM in the samples is only clear in
sample CA5 (Fig. 2). Sample S2 also presents a slightly raised baseline,
and displays a double distribution of n-alkanes, from natural origin
and petrogenic.
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
Conversely, all samples from anthropogenic mineral licks (CA1–5)
and the sediments investigated contained traces of steranes and
hopanes (Figs. 2 and 3; Table 3), while none of the natural mineral
licks soils (CA1–3) contained traces of these compounds. In the samples
with hopanes, the 17α(H),21β(H)-stereochemistry predominate
(Fig. 2), indicating a substantial contribution from petroleum (Sakari
et al., 2010; Volkman et al., 1997; Wang et al., 2007). No ββ-isomers
were detected, and thus we can exclude significant inputs of hopanes
from modern living organisms. Thus, in samples with mature organic
matter contents the hopanes are generally composed of three
sterioisomeric series, namely 17α(H),21β(H)-Hopanes,
17β(H),21β(H)-Hopanes and 17β(H),21α(H)-Hopanes. In organically
mature samples, the αβ epimeric isomers in the C27–C35 range have a
greater thermodynamic stability in comparison to the βα and ββ iso-
mers, and are typical of petroleum. In contrast, ββ-isomers are also
commonly found in living organisms (Volkman et al., 1997). Conse-
quently, in modern samples with petrogenic inputs all three isomers
(αβ, βα, and ββ) may be found.
The steranes in petroleum, as they are derived from sterols, occur as
the C27, C28 and C29 homologous series in different proportions which
reflect the carbon number distribution of the sterols in the precursor or-
ganic matter in the source rocks for these oils (Wang and Stout, 2010).
They have a number of isomeric forms with different stereochemistries
at positions 5, 14, 17, 20 and 24. These are the type of distributions
found in the samples from the Corrientes and Pastaza basins (Fig. 4),
which further confirms the occurrence of petrogenic inputs to some of
the soils and sediments investigated. The relative higher abundance of
the higher molecular weight homologues may indicate that the oil sig-
natures are substantially weathered (Wang et al., 2007). For instance,
samples CA1, CA5 and S3 (Fig. 4) display a profile of degraded steranes
where the 20(R + S) αββ C29 (R + S) N C28 (R + S) N C27 (R + S). This
trend is not so clear for sample S1, where C27 bbR N C29 bbR N C29 bbS
N C28 bbS N C28 bbR N C27 bbS and the sample S2 which follows this pat-
tern: C29 bbS N C28 bbR N C29 bbR N C27 bbR N C28 bbS N C27 bbS.
In summary, it is apparent that if the study had been limited to the
analysis of n-alkane distribution and the occurrence of UCMs,
petrogenic pollution would have only been conclusive in one out of
the 11 samples. Nevertheless, the occurrence of sterane and hopanes
in 75% of the samples, i.e. those soils retrieved from anthropogenic min-
eral licks and sediments located in the vicinity or downstream - up to
6 km - of the oil infrastructure, points at the widespread occurrence of
petroleum derived products within the oil block in various river
catchments.
3.2. Sources of petrogenic inputs
In the marine environment, the occurrence of petrogenic hydrocar-
bons is ubiquitous as it derives from natural as well as anthropogenic
sources, and thus it is unrealistic to expect a complete absence of hydro-
carbons from a “clean” environment (Kingston, 2002). In a continental
setting, oil is not as easily dispersed as in the marine environment
(Prince et al., 2003). Thus, while ocean currents and biogeochemical
processes will disperse oil effectively from a given point source, in rivers
is bound to be dispersed and transported downstream along the river
course, and mixed throughout the water column and deposited in the
bottom sediments (Goeury et al., 2014). In soils and wetlands, which
are low energy environments, the majority of the hydrocarbons in the
oil will stay near the spillage point, and natural weathering will be the
main process that will gradually remove the oil from the deposition
site. Consequently, the occurrence of petrogenic compounds in the sam-
ples discussed in here can only be derived from local sources, or up-
stream sources in the case of fluvial sediments.
Presumably, to most people the area studied is extremely remote, if
one considers that it is only accessible by boat (3–5 days upstream trav-
el time from the city of Iquitos, which in itself is only accessible by boat
or plane), or by plane using the private (oil-company owned) airfield in
1015
the settlement of Andoas (Fig. 1). The local inhabitants have predomi-
nantly a subsistence economy dependent on fishing, hunting and slash
and burn agriculture. The only significant industrial activity is the one
carried out by the oil industry, which also provides employment to
some of the local inhabitants. At first, the crude petroleum was
transported by cargo ship to Iquitos, but from 1978 onwards, oil has
been pumped directly through the North Peruvian Oil Pipeline from
the area to the Bayovar refinery on the Pacific coast (Orta-Martínez
et al., 2007). Processing of the crude oil and waste products is, however,
undertaken locally, in the oil block. Most samples were located near
central production facilities or sump tanks (Fig. 1 and Table 1). The latter
are designed to contain oil overflowing from a well due to unexpected
increases in pressure. However, in the study area oil is rarely recovered
from these tanks, and it overflows with the regular heavy tropical rain-
falls when the tanks are uncovered (Orta-Martínez et al., 2007). In addi-
tion, oil produced waters were discharged untreated to the local rivers
until January 2008 in Block 1AB, and the reinjection of the formation
waters into the oil wells was not generalized until the end of 2009
(Comisión de Pueblos Andinos Amazónicos y Afroperuanos Ambiente
y Ecología, 2013). Most of the waste generated from oil extraction is
composed of produced waters, which amount in average to 70% of the
liquid fluids extracted from a well (Fakhru'l-Razi et al., 2009). The cu-
mulative water production of the block 1AB until April 2012 was
6.5 billion barrels, which represents a water cut of 96% (Perú Petro,
2015). Production water contains a very high concentrations of salts
(denser than seawater), hydrocarbons and heavy metals
(Fakhru'l-Razi et al., 2009; Neff et al., 2011). The production waters
from the Northern Peruvian (Marañon) oil basin can vary considerably
in salinity from brines with values of up to 200,000 mg L−1 of total dis-
solved solids (TDS) to saline waters of 19,000 mg L− 1 TDS (Barson,
2002; Sofer et al., 1986), while natural riverine NaCl concentration is
about 3 mg L−1 (Meybeck and Helmer, 1989).
Another likely source of petrogenic pollution in the local waterways
is the emissions from off board two stroke engines in canoes, and diesel
engines in large transport ships. The former is chiefly used by local in-
habitants, while the latter are employed chiefly by the oil industry as
supply ships, and to transport oil. We do not have any figures, but we
speculate that the emissions from lubricant oils and petrol derived
from transport by local populations over the years must be negligible
in comparison to the oil industry emissions from transport, discharges
and spills. Obviously, they would only pollute local rivers, not soils
and wetland sediments such as those analyzed in here. We consider
also as negligible in a regional context the petrogenic emissions derived
from local settlements to generate electricity (given the sparse number
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
(Fig. 1). Consequently, given the issues outlined above, it seems a plau-
sible hypothesis that any petrogenic inputs in the samples are derived
from the activities of the oil industry in the area, mainly from voluntary
discharges or accidental spills of produced water and oil over the years.
In fact, oil wells and pipelines on land are the regular source of spillages
and contamination on continental environments worldwide (Service
et al., 2012).
Moreover, those samples where no petrogenic biomarkers were de-
tected are those located in sites far removed from any of the existing oil
infrastructure. In these sites, the mineral licks have developed naturally,
not by the agency of any anthropic activity. In contrast, samples CA1–5
were retrieved from mineral licks created after the construction of oil
infrastructure. Some of these places received the overflows of sump
tanks (CA1 and CA2) or were located in the area of influence of a pro-
duced water or oil dumping site (CA3–5). Consequently, we attribute
the petrogenic signatures of the soils to inputs from the nearby
infrastructure.
In relation to the sediment samples, sample site S3 lies underneath a
major oil pipeline in a wetland. Ruptures of such pipelines are a com-
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
However, we speculate that the origin of the hydrocarbons may be re-
lated to the fact that the site is located in an area that formerly received
the discharges of produced waters. These discharges drain into a flood
plain that it is crossed by the oil pipeline where sample S3 was retrieved
from and formed a large artificial pool that it is still visible by satellite
next to the sampling point (e.g. visible on Google Earth, see coordinates
in Table 1). Similarly, sample S2 is also located 8,7 km downstream from
another disposal site of produced waters. In contrast, sample S1 are sed-
iments deposited by river waters in areas that and are not adjacent to
any major oil infrastructure (i.e. oil production facilities). At this stage,
we speculate that the oil inputs might derive from former spills that oc-
curred in the Huayuri Norte oil wells, which are upstream and relatively
close to the site (7,5 km upstream). Sediments with petrogenic signa-
tures may have been redeposited in the wet season, when the water
levels in the Corrientes rise by several meters and flood all the adjacent
lands to the river. The river may transport downstream resuspended
sediment loaded with sediments from contaminate lands upstream.
These can be expected to eventually reach the Tigre and Marañón rivers,
which are likely to receive also petrogenic inputs from extraction activ-
ities in the oil block 8 (Reátegui-Zirena et al., 2014), and eventually
reach the Amazon river as already reported for dissolved chemical
loads (Moquet et al., 2014; Yusta-Garcia et al., 2017).
The oils in the region are derived from Cretaceous reservoirs and de-
rive from the Chonta formation source rock and the Vivian formation
reservoir (Perupetro report, 2009). However, there is insufficient infor-
mation in the scientific literature or freely available as public reports to
ascertain the chemical fingerprints of the oils in the oil block studied.
The scarce information we have obtained on the chemical fingerprints
of oil extracted across the region suggest that they have significantly
different biomarker fingerprints (Core Laboratories Inc, 1999; Sofer
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
ratios with those shown in Table 3, and from an environmental forensics
perspective establish the sources of the petrogenic inputs in the
samples. The wide range of values of the diagnostic biomarker ratios
we have measured suggest, nevertheless, that the oil signatures derive
from different type of oils, or spills at different times with varying
degree of weathering.
3.3. Health and conservation implications
The presence of oil infrastructure per se is known to lead to a
wide range of environmental impacts (Hinte et al., 2007). Oil spilled
on terrestrial environments will undergo volatilization and biodegrada-
tion. On soils, a significant fraction will infiltrate vertically into the
subsurface, penetrate the soil micropores and remain in the soil matrix
for years (Dutta and Harayama 2001; Liang et al. 2009). The remaining
refractory oil fractions, such as high molecular weight hydrocarbons,
resins and polar fractions have attracted significant concerns regarding
their mutagenic and carcinogenic potentials and their ability to
bioaccumulate (Hoff et al., 2007; Yavari et al., 2015). The effect of the
spilled oil on the land ecosystems is therefore expected to be acute,
and the natural recovery of polluted soils slow (Ebuehi et al., 2005;
Vinson et al., 2008; Yavari et al., 2015). The unintentional or intentional
ingestion of polluted soil is also a potential route of exposure for both
humans and wildlife (Beyer and Fries, 2003; Irvine et al., 2014; U.S.
Environmental Protection Agency, 2011).
On aquatic systems, the presence of oil also poses a significant
threat to aquatic life, as toxic effects cascade across trophic levels,
affecting phytoplankton, zooplankton, fish, aquatic birds, mammals,
and benthic organisms (see review in Perhar and Arhonditsis, 2014).
This is partly a consequence of the solubility of oil components which
can be inversely related to salinity, and thus is enhanced in freshwater
(Whitehouse, 1984), as well as the reduced diffusion of oxygen into
water. Moreover, the myriad of fish species in Amazon rivers that are
1017
adapted to explore the water-air interface to breathe and feed are
particularly vulnerable to the physical occurrence of the oil spills
(Kochhann et al., 2015).
In our study, the collection of the samples from mineral licks and
river sediments was motivated by the claims by local indigenous
hunters and indigenous environmental monitors that the game hunted
for subsistence, and organisms collected from rivers or wetlands often-
times smelled of and were smeared with oil. We have now shown that
oil is indeed present in soils from mineral licks in the vicinity of infra-
structure, and in sediments from aquatic settings. Animals visiting min-
eral licks may consume up to 30% of soil as part of their diet (Beyer and
Fries, 2003). Wildlife in tropical rainforests are bound to ingest soil and
water from these oil polluted sites, and could be a source of exposure to
petrogenic compounds for human communities that rely on subsistence
hunting and fishing. The health effect that the ingestion of oil-polluted
soil by Amazonian frugivorous and herbivores may have on wildlife
and human population has not yet been studied. In fact, health effects
among people residentially exposed to upstream oil industry contami-
nants have been poorly studied around the world (O'Callaghan-Gordo
et al., 2016). However, it is acknowledged that the inadvertent ingestion
of contaminated soil and sediments can be a major pathway for chemi-
cal exposure to humans with a subsistence diet (Doyle et al., 2012;
Irvine et al., 2014). In indigenous communities elsewhere, the human
soil ingestion rate was of several hundreds of mg per day (Irvine et al.,
2014; U.S. Environmental Protection Agency, 2011). Consequently, our
results suggest that oil activities could potentially result in bioaccumu-
lation and biomagnification of oil chemicals, and could be hazardous
for the conservation of top predators in the tropical rainforests, and
for the health of local indigenous peoples that have a subsistence
economy.
4. Conclusions
Soils and river sediments, in the vicinity or downstream, respective-
ly, from oil extraction and processing infrastructure in the rainforests of
the Northern Peruvian Amazon contain an oil pollution signature. This is
not an unexpected finding in a worldwide context given that the oil in-
dustry infrastructure commonly has a significant environmental impact
in the surrounding lands, be it during extraction, processing, transport
and distribution processes.
The hydrocarbons in sediments in the water courses of the Corrien-
tes and Pastaza basins could have eventually reached the main water
course of the Amazon, as already noted for other chemical components
present in produced waters (Moquet et al., 2014; Yusta-Garcia et al.,
2017). In contrast, spillages in soils are likely to have a local impact.
However, such an impact is compounded in the oil block investigated
because the localities where oil was spilled may be the feeding grounds
of local fauna (i.e. salt licks or mineral licks), and in turn focal hunting
spots of the local indigenous inhabitants. Similarly, we show that
areas used locally for fishing also contain an oil pollution fingerprint.
These findings suggest that wildlife in an oil producing region of the
Amazon are exposed to the ingestion of oil polluted soils and sediments,
that may reach the human food chain. This exposure to oil contaminat-
ed foodstuffs may extend beyond the area of study as fish and wild meat
are also sold in local and regional food markets, like the ones in the city
of Iquitos.
Our study further illustrates how remote natural areas also contain
yet another ubiquitous anthropogenic footprint. The oil industry, in
the far reaches of the Amazon, has contributed to the expansion of an-
thropogenic contaminants from industrial centres to the most remote
areas. The practices and the expansion of the oil industry to the remain-
ing wilderness and biodiversity hotspots in the planet seem at odds
with any efforts to conserve them. Moreover, the ends of the continuum
of human impact in the environment may be closer than is usually en-
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
30d 15α-Methyl-17α(H)-27-norhopane (diahopane) 191 References
29ba 17β(H),21α(H)-30-normoretane (normoretane) 191
Aeppli, C., Nelson, R.K., Radović, J.R., Carmichael, C.A., Valentine, D.L., Reddy, C.M., 2014.
30ab 17α(H),21β(H)-30-hopane 191
Recalcitrance and degradation of petroleum biomarkers upon abiotic and biotic nat-
30ba 17β(H),21α(H)-hopane (moretane) 191 ural weathering of Deepwater Horizon oil. Environ. Sci. Technol. 48:6726–6734.
31abS 17α(H),21β(H),22S-homohopane 191 http://dx.doi.org/10.1021/es500825q.
31abR 17α(H),21β(H), 22R-homohopane 191 Anticona, C., Bergdahl, I.A., Lundh, T., Alegre, Y., Sebastian, M.S., 2011. Lead exposure in in-
30G Gammacerane 191 digenous communities of the Amazon basin, Peru. Int. J. Hyg. Environ. Health 215:
32abS 17α(H),21β(H), 22S-bishomohopane 191 59–63. http://dx.doi.org/10.1016/j.ijheh.2011.07.003.
32abR 17α(H),21β(H), 22R-bishomohopane 191 Anticona, C., Bergdahl, I.A., San Sebastian, M., 2012. Lead exposure among children from
native communities of the Peruvian Amazon basin. Rev. Panam. Salud Publica 31,
33abS 17α(H),21β(H), 22S-trishomohopane 191
296–302.
33abR 17α(H),21β(H), 22R-trishomohopane 191 Barson, D., 2002. Marañon Basin Petroleum Hydrogeology Study. Rep. by. Rakhit Pet. Con-
34abS 17α(H),21β(H), 22S-tetrakishomohopane 191 sult. Ltd., pp. 1–27.
34abR 17α(H),21β(H), 22R-tetrakishomohopane 191 Beyer, W.N., Fries, G.F., B. Jr., G.A., C., J., 2003. Chapter 6. Toxicological significance of soil
35abS 17α(H),21β(H), 22S-pentakishomohopane 191 ingestion by wild and domestic animals. In: Hoffman, D.J., Rattner, B.A., Burton Jr.,
35abR 17α(H),21β(H), 22R-pentakishomohopane 191 G.A., Cairns Jr., J. (Eds.), Handbook of Ecotoxicology. Lewis Publishers, Boca Raton,
27dbS 13β(H),17α(H),20S-cholestane (diasterane) 217 FL:pp. 151–166 http://dx.doi.org/10.1201/9781420032505.ch6.
27dbR 13β(H),17α(H),20R-cholestane (diasterane) 217 Blake, J.G., Mosquera, D., Guerra, J., Loiselle, B.A., Romo, D., Swing, K., 2011. Mineral licks as
diversity hotspots in lowland forest of eastern Ecuador. Diversity 3:217–234. http://
DIA27S 13α(H),17β(H)-20S-cholestane (diasterane) 217
dx.doi.org/10.3390/d3020217.
DIA27R 13α(H),17β(H)-20R-cholestane (diasterane) 217 Bravo, A., Harms, K.E., Emmons, L.H., 2010. Preference for collpa water by frugivorous bats
27aaS 5 α(H),14 α(H),17α(H)-20S-cholestane 217 (Artibeus): an experimental approach. Biotropica 42:276–280. http://dx.doi.org/
27bbR 5α(H),14β(H),17β(H),20R-cholestane 217 10.1111/j.1744-7429.2010.00639.x.
27bbS 5α(H),14β(H),17β(H),20S-cholestane 218 Brightsmith, D.J., Munoz-Najar, R.A., 2004. Avian geophagy and soil characteristics in
27aaR 5α(H),14α(H),17α(H),20R-cholestane 218 southeastern Peru. Biotropica 36:534–543. http://dx.doi.org/10.1111/j.1744-
28bbR 24-Methyl-5α(H),14β(H),17β(H),20R-cholestane 218 7429.2004.tb00348.x.
Butt, N., Beyer, H., Bennett, J., Biggs, D., 2013. Biodiversity risks from fossil fuel extraction.
28bbS 24-Methyl-5α(H),14β(H),17β(H),20S-cholestane 218
Science 342, 425–426.
28aaR 24-Methyl-5α(H),14α(H),17α(H),20R-cholestane 217 Comisión de Pueblos Andinos Amazónicos y Afroperuanos Ambiente y Ecología, 2013.
29aaS 24-Ethyl-5α(H),14α(H),17α(H),20S-cholestane 217 Informe final del grupo de trabajo sobre la situación indígena de las cuencas de los
29bbR 24-Ethyl-5α(H),14β(H),17β(H),20R-cholestane 218 ríos Tigre, Pastaza, Corrientes y Marañón. 2012–2013. Congreso de la República,
29bbS 24-Ethyl-5α(H),14β(H),17β(H),20S-cholestane 218 Lima, Perú.
29aaR 24-Ethyl-5α(H),14α(H),17α(H),20R-cholestane 217 Core Laboratories Inc, 1999. Final Report Volume 1: Geochemical Evaluation of Oils and
Source Rocks and Oil-source Rock Correlations, Sub-Andean basins, Peru.
Doyle, J.R., Blais, J.M., Holmes, R.D., White, P.A., 2012. A soil ingestion pilot study of a pop-
ulation following a traditional lifestyle typical of rural or wilderness areas. Sci. Total
Acknowledgments Environ. 424:110–120. http://dx.doi.org/10.1016/j.scitotenv.2012.02.043.
Dutta, T.K., Harayama, S., 2001. Biodegradation of n-alkylcycloalkanes and n-
alkylbenzenes via new pathways in Alcanivorax sp. strain MBIC 4326. Appl. Environ.
We appreciate the support of local indigenous communities and the Microbiol. 67, 1970–1974.
indigenous federations of the Pastaza and Corrientes River basins Ebuehi, O., Abibo, I., Shekwolo, P., Sigismund, K., Adoki, A., Okoro, I., 2005. Remediation of
crude oil contaminated soil by enhanced natural attenuation technique. J. Appl. Sci.
(FEDIQUEP and FECONACO, respectively). This work was supported by Environ. Manag. 9, 103–106.
the Fundació Autònoma Solidaria from Autonomous Barcelona Univer- Emmons, L.H., Stark, N.M., 1979. Elemental composition of a natural mineral lick in Ama-
sity (Grant no. FSXXX-18), and the Rufford Foundation (13651-1). zonia. Biotropica 11:311–313. http://dx.doi.org/10.2307/2387925.
Fakhru'l-Razi, A., Pendashteh, A., Abdullah, L.C., Biak, D.R.A., Madaeni, S.S., Abidin, Z.Z.,
Orta-Martínez benefited from the financial support of the Marie Curie 2009. Review of technologies for oil and gas produced water treatment. J. Hazard.
Mater. 170:530–551. http://dx.doi.org/10.1016/j.jhazmat.2009.05.044.
Farrington, J.W., Quinn, J.G., 1973. Petroleum hydrocarbons in Narragansett Bay in sedi-
Table 3
ments and clams. Estuar. Coast. Mar. Sci. 1, 71–79.
Biomarker ratios derived from the relative abundances of n-alkanes, hopanes and steranes Farrington, J.W., Quinn, J.G., Farrington, J.W., Edu, J., Quinn, J.G., 2015. “Unresolved com-
in the samples. Cx max: most abundant n-alkane; CPI: Carbon Preference Index, see main plex mixture” (UCM): a brief history of the term and moving beyond it. Mar. Pollut.
text for definition; Pr: pristane; Ph: phytane; C17 and C18: n-alkanes with 17 or 18 carbon Bull. 96:29–31. http://dx.doi.org/10.1016/j.marpolbul.2015.04.039.
atoms, respectively. See Table 2 for chemical compound abbreviations. Finer, M., Orta-Martínez, M., 2010. A second hydrocarbon boom threatens the Peruvian
Amazon: trends, projections, and policy implications. Environ. Res. Lett. 5:14012.
CA1 CA2 CA3 CA4 CA5 S1 S2 S3 http://dx.doi.org/10.1088/1748-9326/5/1/014012.
Finer, M., Jenkins, C.N., Pimm, S.L., Keane, B., Ross, C., 2008. Oil and gas projects in the
Cx max C29 C31 C22 C17 C46 C29 C29 C31 Western Amazon: threats to wilderness, biodiversity, and indigenous peoples. PLoS
CPI 9.29 6.62 1.13 3.42 – 5.43 4.93 7.88 One 3, e2932. http://dx.doi.org/10.1371/journal.pone.0002932.
C17/Pr 0.45 0.31 0.87 25.38 0.06 4.66 0.38 0.07 Goeury, C., Hervouet, J., Baudin-bizien, I., Thovenet, F., 2014. A Lagrangian/Eulerian oil
C18/Ph 0.45 0.14 0.90 71.79 0.12 1.83 0.49 0.20 spill model for continental waters. J. Hydraul. Res. 52, 36–48.
Pr/Ph 1.20 1.05 1.03 3.46 1.00 0.41 1.18 0.92 Goldman, E.S., La Torre López, L., Lya Ramos, M., 2007. A Legacy of Harm. Occidental Pe-
27Ts/30ab 0.30 0.17 0.20 0.18 – 0.14 0.26 – troleum in Indigenous Territory in the Peruvian Amazon. Earth Rights International,
Racimos de Ungurahui. Amazon Watch, Lima.
27Tm/30ab 0.28 0.18 0.27 0.34 – 0.19 0.29 –
Hinte, T. Van, Gunton, T.I., Day, J.C., 2007. Evaluation of the assessment process for major
28ab/30ab – 0.09 1.06 0.99 – – 0.16 0.77 projects: a case study of oil and gas pipelines in Canada. Impact Assess. Proj. Apprais.
29ab/30ab 4.52 0.94 0.52 0.72 0.62 1.12 0.67 0.78 5517:123–137. http://dx.doi.org/10.3152/146155107X204491.
31abS/30ab 0.44 0.52 0.31 0.32 0.35 0.67 0.56 0.50 Hoff, D., Smith, P.N., Cobb, G.P., Mcmurry, S.T., Rainwater, T.R., Reynolds, K.D., 2007. Con-
27dbR/27dbS 1.01 0.66 0.73 0.74 1.14 0.73 0.62 0.75 taminant exposure in terrestrial vertebrates. Environ. Pollut. 150:41–64. http://
29aaS/29aaR 1.32 1.51 1.15 1.13 1.15 0.90 1.23 0.64 dx.doi.org/10.1016/j.envpol.2007.06.009.
29bb(S + R)/29aa(S + R) 3.62 1.14 1.27 1.24 1.64 0.98 1.14 1.99 Irvine, G., Doyle, J.R., White, P.A., Blais, J.M., 2014. Soil ingestion rate determination in a
27bb(S + R)/29aa(S + R) 0.10 0.44 1.00 0.69 0.46 0.84 0.82 0.73 rural population of Alberta, Canada practicing a wilderness lifestyle. Sci. Total Envi-
ron. 470–471:138–146. http://dx.doi.org/10.1016/j.scitotenv.2013.09.037.
 A. Rosell-Melé et al. / Science of the Total Environment 610–611 (2018) 1010–1019
Kimerling, J., 1991. Amazon Crude. Natural Resource Defense Council, New York.
Kingston, P.F., 2002. Long-term environmental impact of oil spills. Spill Sci. Technol. Bull.
7, 53–61.
Kochhann, D., Jardim, M.M., Xochilt, F., Domingos, V., Val, A.L., 2015. Biochemical and be-
havioral responses of the Amazonian fish Colossoma macropomum to crude oil: the ef-
fect of oil layer on water surface. Ecotoxicol. Environ. Saf. 111:32–41. http://
dx.doi.org/10.1016/j.ecoenv.2014.09.016.
Krauss, M., Wilcke, W., Martius, C., Bandeira, A.G., Garcia, M.V.B., Amelung, W., 2005. At-
mospheric versus biological sources of polycyclic aromatic hydrocarbons (PAHs) in a
tropical rain forest environment. Environ. Pollut. 135:143–154. http://dx.doi.org/
10.1016/j.envpol.2004.09.012.
Liang, Y., Zhang, X., Dai, D., Li, G., 2009. Porous biocarrier enhanced biodegradation of
crude oil contaminated soil. Int. Biodeterior. Biodegrad. 63, 80–87.
Meybeck, M., Helmer, R., 1989. The quality of rivers: from pristine stage to global pollu-
tion. Palaeogeogr. Palaeoclimatol. Palaeoecol. 75:283–309. http://dx.doi.org/
10.1016/0031-0182(89)90191-0.
Ministerio de Energía y Minas de Perú, 2015. Anuario Estadístico de Hidrocarburos
(Lima).
Mittermeier, R.A., Mittermeier, C.G., Brooks, T.M., Pilgrim, J.D., Konstant, W.R., da Fonseca,
G.A.B., Kormos, C., 2003. Wilderness and biodiversity conservation. Proc. Natl. Acad.
Sci. 100:10309–10313. http://dx.doi.org/10.1073/pnas.1732458100.
Moquet, J.-S., Maurice, L., Crave, A., Viers, J., Arevalo, N., Lagane, C., Lavado-casimiro, W.,
Guyot, J., 2014. Cl and Na fluxes in an Andean Foreland Basin of the Peruvian Amazon:
an anthropogenic impact. Aquat. Geochem. 20:613–637. http://dx.doi.org/10.1007/
s10498-014-9239-6.
Neff, J.M., Lee, K., DeBlois, E., 2011. Produced water: overview of composition, fates, and
effects. In: Lee, K., Neff, J.M. (Eds.), Produced Water. Environmental Risks and Ad-
vances in Mitigation Technologies. Springer Berlin/Heidelberg http://dx.doi.org/
10.1007/978-1-4614-0046-2.
O'Callaghan-Gordo, C., Orta-Martínez, M., Kogevinas, M., 2016. Health effects of non-
occupational exposure to oil extraction. Environ. Health 15:56. http://dx.doi.org/
10.1186/s12940-016-0140-1.
Orta-Martínez, M., Finer, M., 2010. Oil frontiers and indigenous resistance in the Peruvian
Amazon. Ecol. Econ. 70:207–218. http://dx.doi.org/10.1016/j.ecolecon.2010.04.022.
Orta-Martínez, M., Napolitano, D.A., MacLennan, G.J., O'Callaghan, C., Ciborowski, S.,
Fabregas, X., Orta-Martinez, M., O'Callaghan, C., 2007. Impacts of petroleum activities
for the Achuar people of the Peruvian Amazon: summary of existing evidence and re-
search gaps. Environ. Res. Lett. 2:45006. http://dx.doi.org/10.1088/1748-9326/2/4/
045006.
Perhar, G., Arhonditsis, G.B., 2014. Aquatic ecosystem dynamics following petroleum hy-
drocarbon perturbations: a review of the current state of knowledge. J. Great Lakes
Res. 40:56–72. http://dx.doi.org/10.1016/j.jglr.2014.05.013.
Perú Petro, 2015. Licitación Pública Internacional para otorgar Contrato de Licencia para la
Explotación de Hidrocarburos en el Lote 192 (Lima).
Prince, R.C., Garrett, R.M., Bare, R.E., Grossman, M.J., Townsend, T., Suflita, J.M., Lee, K.,
Owens, E.H., Sergy, G.A., Braddock, J.F., Lindstrom, J.E., Lessard, R.R., 2003. The roles
of photooxidation and biodegradation in long-term weathering of crude and heavy
fuel oils. Spill Sci. Technol. Bull. 8:145–156. http://dx.doi.org/10.1016/S1353-
2561(03)00017-3.
Reátegui-Zirena, E.G., Stewart, P.M., Whatley, A., Chu-Koo, F., Sotero-Solis, V.E., Merino-
Zegarra, C., Vela-Paima, E., 2014. Polycyclic aromatic hydrocarbon concentrations,
mutagenicity, and Microtox® acute toxicity testing of Peruvian crude oil and oil-
contaminated water and sediment. Environ. Monit. Assess. 186:2171–2184. http://
dx.doi.org/10.1007/s10661-013-3527-2.
Sakari, M., Zakaria, M.P., Mohamed, C.A.R., Lajis, N.H., Chandru, K., Bahry, P.S., Mokhtar,
M.B., Shahbazi, A., 2010. Urban vs. marine based oil pollution in the Strait of Johor,
Malaysia: a century record. Soil Sediment Contam. 19:644–666. http://dx.doi.org/
10.1080/15320383.2010.515630.
1019
Service, C.N., Nelson, T.A., Paquet, P.C., Mclnnes, W.S.S., Chris, T., Service, C.N., 2012. Pipe-
lines and parks: evaluating external risks to protected areas from the proposed
Northern Gateway Oil Transport Project. Nat. Areas J. 32, 367–376.
Sofer, Z., Zumberge, J.E., Lay, V., 1986. Stable carbon isotopes and biomarkers as tools in
understanding genetic relationship, maturation, biodegradation, and migration of
crude oils in the Northern Peruvian Oriente (Maranon) Basin. Org. Geochem. 10:
377–389. http://dx.doi.org/10.1016/0146-6380(86)90037-9.
U.S. Environmental Protection Agency, 2011. Chapter 5. Soil and dust ingestion. Exposure
Factors Handbook: 2011 Edition. National Center for Environmental Assessment,
Washington, DC.
Vinson, M.R., Dinger, E.C., Kotynek, J., Dethier, M., 2008. Effects of oil pollution on aquatic
macroinvertebrate assemblages in Gabon wetlands. Afr. J. Aquat. Sci. 33:261–268.
http://dx.doi.org/10.2989/AJAS.2008.33.3.9.621.
Volkman, J.K., Revill, A.T., Murray, A.P., 1997. In: Eganhouse, R.P. (Ed.), Applications of bio-
markers for identifying sources of natural and pollutant hydrocarbons in aquatic en-
vironments. ACS Symposium Series. ACS:pp. 110–132 http://dx.doi.org/10.1021/bk-
1997-0671.ch008.
Wang, Z., Stout, S., 2010. Oil Spill Environmental Forensics: Fingerprinting and Source
Identification. Academic Press, London.
Wang, Z., Fingas, M., Page, D.S., 1999. Oil spill identification. J. Chromatogr. A 843:
369–411. http://dx.doi.org/10.1016/S0021-9673(99)00120-X.
Wang, Z., Stout, S.A., Fingas, M., 2006. Forensic fingerprinting of biomarkers for oil spill
characterization and source identification. Environ. Forensic 7:105–146. http://
dx.doi.org/10.1080/15275920600667104.
Wang, Z., Yang, C., Fingas, M., Hollebone, B., Yim, U.H., Oh, J.R., 2007. Petroleum biomarker
fingerprinting for oil spill characterization and source identification. In: Wang, Z.,
Stout, S.A. (Eds.), Oil Spill Environmental Forensics. Academic Press, London.
Wang, Z., Yang, C., Kelly-Hooper, F., Hollebone, B.P., Peng, X., Brown, C.E., Landriault, M.,
Sun, J., Yang, Z., 2009. Forensic differentiation of biogenic organic compounds from
petroleum hydrocarbons in biogenic and petrogenic compounds cross-
contaminated soils and sediments. J. Chromatogr. A 1216:1174–1191. http://
dx.doi.org/10.1016/j.chroma.2008.12.036.
Wang, C., Gao, X., Sun, Z., Qin, Z., Yin, X., He, S., 2013. Evaluation of the diagnostic ratios for
the identification of spilled oils after biodegradation. Environ. Earth Sci. 68:917–926.
http://dx.doi.org/10.1007/s12665-012-1792-y.
White, H.K., Xu, L., Hartmann, P., Quinn, J.G., Reddy, C.M., 2013. Unresolved complex mix-
ture (UCM) in coastal environments is derived from fossil sources. Environ. Sci.
Technol. 47:726–731. http://dx.doi.org/10.1021/es3042065.
Whitehouse, B.G., 1984. The effects of temperature and salinity on the aqueous solubility
of polynuclear aromatic hydrocarbons. Mar. Chem. 14, 319–332.
Wilcke, W., 2007. Global patterns of polycyclic aromatic hydrocarbons (PAHs) in soil.
Geoderma 141:157–166. http://dx.doi.org/10.1016/j.geoderma.2007.07.007.
Wilcke, W., Amelung, W., Martius, C., Garcia, M.V.B., Zech, W., 2000. Biological sources of
polycyclic aromatic hydrocarbons (PAHs) in the Amazonian rain forest. J. Plant Nutr.
Soil Sci. 163, 27–30.
Wilcke, W., Krauss, M., Amelung, W., 2002. Carbon isotope signature of polycyclic aromat-
ic hydrocarbons (PAHs): evidence for different sources in tropical and temperate en-
vironments? Environ. Sci. Technol. 36:3530–3535. http://dx.doi.org/10.1021/
es020032h.
Yavari, S., Malakahmad, A., Sapari, N., 2015. A review on phytoremediation of crude oil
spills. Water Air Soil Pollut. 226:279. http://dx.doi.org/10.1007/s11270-015-2550-z.
Yusta-Garcia, R., Orta-Martínez, M., Mayor, P., Gonzalez-Crespo, C., Rosell-Mele, A., 2017.
Water contamination from oil extraction activities in Northern Peruvian Amazonian
rivers. Environ. Pollut. 225:370–380. http://dx.doi.org/10.1016/j.envpol.2017.02.063.