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Chemie der Erde 73 (2013) 555563

Contents lists available at ScienceDirect

Chemie der Erde

journal homepage: www.elsevier.de/chemer

Use of biomarkers indices in a sediment core to evaluate potential

pollution sources in a subtropical reservoir in Brazil
Juan Snez a, , Sandro Froehner b , Filipe Falco b
a
b

Graduate Program in Water Resources and Environmental Engineering, Federal University of Parana, 81531-990 Curitiba, Parana, Brazil
Environmental Engineering Department, Federal University of Parana, 81531-990 Curitiba, Parana, Brazil

a r t i c l e

i n f o

Article history:
Received 29 November 2012
Accepted 24 July 2013
Keywords:
Biogenic decomposition
Biomarkers
Carbon preference index
n-Alkanes
PAHs
Organic matter
Sediment pollution
Subtropical reservoir

a b s t r a c t
The presence of PAHs, n-alkanes, pristane, and phytanes in core sediment from the Vossoroca reservoir (Parana, southern Brazil) was investigated. The total concentration of the 16 PAHs varied from
15.5 to 1646 g kg1 . Naphthalene was present in all layers (3.3474.0 g kg1 ). The most abundant and dominant n-alkanes were n-C15 and n-C36 , with average concentrations of 198.1 46.8 and
522.9 167.7 g kg1 , respectively. Lighter n-alkanes were distributed more evenly through the layers
and showed less variation, specially n-C9 , n-C12 , and n-C18 , with average concentrations of 14.6 3.0,
31.6 1.9, and 95.0 5.2 g kg1 , respectively; heavier n-alkanes were more unevenly distributed.
The study of the biomarker ratios indicates a slight inuence from the nearby Highway BR 376: deposit
of sediments coming from the pavement and sources of pyrolytic origin from the heavy trafc of vehicles
and a gas station close to the sample point. In addition to this, the n-alkanes ratio analysis indicates that the
region receives signicant contribution from higher plants, with low contribution from autochthonous
organic matter origin. Identied PAHs suggest pyrogenic sources formed during the pyrolysis of fossil
fuels and direct inuence from the heavy trafc from the nearby highway. The DBahA was found to be
related to the contribution of particulate pavement, but only in signicant concentrations after 15 cm
depth. Sediment fractions seem to be oxic, and the absence of phytane can be explained by several
periods of bioturbation and tidal. In general, when compared with other studied sediments, the area
seems low-polluted.
2013 Elsevier GmbH. All rights reserved.

1. Introduction
The role of sediments in aquatic ecosystems is indispensible.
This environmental matrix can store nutrients, organic matter, and
pollutants, sometimes replacing these substances in the water column. Despite the importance of their role, since the middle of the
last century, sediments have been subjected to degradation and
heavy pollution from diverse toxic chemicals like pesticides, heavy
metals, endocrine disruptors, polychlorinated biphenyl (PCBs),
polycyclic aromatic hydrocarbons (PAHs), aliphatic hydrocarbons
(AHC) from fuel and derivates, partly due to rise in oil consumption
and a heavy use of chemicals in our modern society, altering their

Abbreviations: CPI, carbon preference index; HMW, high molecular weight;

LMW, low molecular weight; Paq , proportion of aquatic plants; TARHC , terrigenous
aquatic ratio hydrocarbon.
Corresponding author at: Graduate Program in Water Resources and Environmental Engineering, Federal University of Parana, Caixa Postal 19011, Jardim das
Amricas, CEP 81531-990 Curitiba, Parana, Brazil. Tel.: +55 41 33613210;
fax: +55 41 33613143.
E-mail address: sanez.juan@gmail.com (J. Snez).
0009-2819/$ see front matter 2013 Elsevier GmbH. All rights reserved.
http://dx.doi.org/10.1016/j.chemer.2013.07.005

natural function within ecosystems (examples Chen et al., 2004;

Venturini et al., 2008; Froehner et al., 2009; de Souza et al., 2011).
The quality of the sediments may be evaluated through the
content of AHC and PAHs, which are the two major classes of compounds found in oil. Therefore, they are used as chemical markers
to identify potential sources of environmental pollution from crude
oil, gasoline, and diesel (Yunker et al., 1999; Savinov et al., 2003;
Lee et al., 2005; Liu et al., 2008; Froehner et al., 2012). Of these,
the PAHs may enter the environment from different sources such
as pyrolytic, petrogenic, oil spills, and biogenic processes. Pyrolytic
origin is attributed to incomplete combustion of recent and fossil organic matter (Yunker et al., 2002a) at higher temperatures
whereas in the petrogenic process, organic matter matures slowly
under geochemical gradient (Wan et al., 2005). The contribution of
PAHs by microorganisms is considered small and has not yet been
fully described (Soclo et al., 2000; Bzdusek et al., 2004; Opuene
et al., 2007).
Ratios between some PAHs assisted in the investigation of possible sources of petrogenic or pyrolytic PAHs sources. Stable isomers
usually originate from petrogenic sources, while unstable isomers
are of pyrolytic origin (Budzinski et al., 1997; Yunker et al., 2002a,b).
The presence of high concentrations of PAHs having more than four

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J. Snez et al. / Chemie der Erde 73 (2013) 555563

aromatic rings is indicative of the formation of the compounds

during pyrolysis of fossil fuels (Gogou et al., 2000). The distribution of PAHs depends on the temperature of the pyrolytic reaction
that yields products governed by thermodynamic properties at low
temperatures (catagenesis) and by kinetic characteristics (Yunker
et al., 1999, 2002a) at elevated temperatures (pyrolysis).
An important group belonging to the AHC is the n-alkane hydrocarbons, which are linear, unbranched chains with saturated bonds,
that may be synthesized by most living organisms: terrestrial
(bacteria and higher plants) or aquatic (phytoplankton and zooplankton). Higher plants retain water in their leaves by synthesizing
epicuticular waxes having long-chain n-alkanes ranging from nC25 to n-C35 , while algae synthesize short-chain n-alkanes ranging
from n-C15 to n-C21 . n-Alkanes dominate the group of saturated
organic compounds present in the organic matter fraction of sediments. In both terrestrial and aquatic organisms, the synthesis of
n-alkanes having odd number of carbons is predominant (Volkman
et al., 1980), which may be rationalized from their biosynthetic
pathway involving enzymatic decarboxylation from fatty acids
generally having an even number of carbon atoms (Killops and
Killops, 2005). Natural sources of n-alkanes from continental origin are mainly cuticular wax derivatives of vascular plants, such
as mangroves. The n-alkanes present in petroleum do not show
any predominance with respect to the number of carbons in their
chains and cannot be related, which may be used as an indicative of contamination (Simoneit, 1993). Anthropogenic sources are
mainly associated with industrial processes, pyrolysis of fossil fuels,
oil spills and derivatives and their presence in lake sediments is
mainly attributed to biogenic sources that originate from two major
groups of plants, divided according to their biochemical composition (Lichtfouse et al., 1997) as non-vascular plants, with little or
no cellulose and lignin, with high protein content and rich in nitrogen (e.g. phytoplankton) and vascular plants having a large content
of woody tissue, with abundant hydrocarbon waxes (e.g. grasses,
shrubs, trees and ground emergent macrophytes in lakes).
In the last decade, several studies involving the quantication of
n-alkanes for reconstruction of environmental conditions and past
scenarios in marine and lacustrine environments (e.g. de Souza,
2011; Froehner et al., 2012) were carried out. Ratios of n-alkanes
were used to identify sources of organic matter and petrogenic contamination from anthropogenic activity in sediments in the aquatic
environment (i.e. Bray and Evans, 1961; Colombo et al., 1989;
Steinhauer and Boehm, 1992; Bourbonniere and Meyers, 1996).
The principal objective of this study is to determine the content
of PAHs and n-alkanes in a sediment core and to evaluate important
related biomarker indices, in order to assess the potential sources of
pollution. Furthermore, the extent of the organic matter produced
by the aquatic system itself as against terrigenous contribution in
the sediments would also be evaluated. These results accompanied
by other related investigations, could help understand the impact
of neighboring human activities on the sediments of the Vossoroca
reservoir.

2. Methods
2.1. Study area
The Vossoroca reservoir spanning over a 5.1 km2 ooded area,
is located in the central region of the First Parana Plateau in the
Serra do Mar region, 80 km from Curitiba, the capital of the Parana
State, in southern Brazil. The reservoir comes under the Environmental Protection Area of Guaratuba and is surrounded by steep
areas covered with vegetation and includes a few marshy stretches.
The impoundment is part of Vossorocas Chamine Hydroelectric
Complex installed on the So Joo River, under the municipality of

Tijucas do Sul, Parana State. The dam is intended to retain water in

order to generate electricity in the Chamine Plant, located 12 km
upstream of the Salto do Meio reservoir (Silveira, 2005; Kantek
et al., 2009).
The topography of the region is very rugged having domain of
Combisol type of soil shallow soils, drainage and limited agricultural use. The native vegetation is preserved and has a biodiversity
typical of the Atlantic Forest (Forest ombrophilous Montana), with
presence of Araucaria Forest. The type of climate is Cfb Humid
Subtropical mesothermal, with cool summers and frequent frosts,
with no dry season. The annual temperature averages less than
22 C in the warmer months and below 18 C in the colder months
while the annual average temperature is 17 C. Rainfall is between
1330 and 1400 mm and the relative humidity is 85%. The hydric
index is between 60 and 100, without water decit. The So Joo
River is the main tributary of the reservoir, and ows across urban
regions and areas predominantly covered by rainforests.
The reservoir shows thermal stratication and dissolved oxygen
in warm periods and destratication in low temperature months,
with characteristics of hypoxia most of the time. The reservoir
has a natural tendency to cyanobacteria blooms. High density of
these organisms is favored due to higher temperatures in the upper
layers of the reservoir, column stratication of water and high residence time in the reservoir (121 days, lentic environment). Local
cyanobacteria predominate over other groups of phytoplankton
algae.
Commercial agriculture, not signicant in the region, is
restricted to small portions where the soil can meet the high expectations of productivity and transportation is facilitated. The tourism
activity (leisure farms with open barbeques, boats, sheries, etc.)
is a growing activity (de Souza, 2011).
2.2. Sampling and sample treatment
The sampling site was located in the proximity of the BR 376
highway (Rod. Henrique Herwig) leading to the Vossoroca reservoir, 5 m to the left of the road, which passes over the reservoir
(Fig. 1). The level of the reservoir was low due to a long drought
period. The sample was collected in a 2 m PVC tube having a 3 in.
diameter. A sediment core of 50 cm was collected that had very
pasty consistency. The core was frozen and subsequently fractionated into 5 cm pellets. Each fraction was separately dried in an oven
at 40 C. The dried sediment was ground with a mortar and pestle
aid.
Sedimentation rate was calculated in the order of 0.0375 m/year
at an error of 10%, giving approximately 1.3 years for every 5 cm of
deposition.
2.3. Analysis
The methodology used by Froehner et al. (2011) was followed
with some minor modications. Upon drying the pellets, each one
was homogenized and sieved. In a 50-mL beaker, 10 g of a dried and
sieved sample was placed, to which 20 mL of hexane was added.
Further, the beaker was placed in an ultrasound bath for 15 min in
order to extract the analyte from the sediment. The supernatant
and remaining solvent were ltered and separated and procedure
was repeated with 20 mL of 1:1 hexane:dichloromethane followed
by extraction with 20 mL of dichloromethane. The three extracts
were mixed and the solvent was distilled out on a rotary evaporator until dryness. 3 mL of hexane was added to the dried extract
that was stirred for a few seconds with ultrasound. Then, the solution was added to a previously conditioned column for cleaning up
with hexane and dichloromethane. Each fraction was again evaporated until dryness in a rotary evaporator and redissolved in 1 mL

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J. Snez et al. / Chemie der Erde 73 (2013) 555563

557

Fig. 1. Brazil map showing the localization of the Parana State and the Vossoroca Reservoir (a). Part of the Vossoroca Reservoir showing the Highway BR 375, the sampling
site (arrow) and, in the circle, the gas station (b).

of dichloromethane. Then, the solution was placed in a vial for its

analysis by GC with FID.
3. Results and discussion
3.1. PAHs
Sixteen standard PAHs were analyzed (Table 1) of which
six compounds, namely, acenaphthene, benzo[a]anthracene,
benzo[k]uoranthene, benzo[a]pyrene, indene[1,2,3-cd]pyrene
and benzo[ghi]perylene, were not detected in any fraction of the
sediment core. Fluorene was only detected in the 4550 cm fraction. Naphthalene was present in all the layers (3.3474.0 g kg1 ),
followed by anthracene (1.4610.0 g kg1 ) and followed by uoranthene (4.8414.9 g kg1 ) having two, three and four benzene

rings respectively. The last one is mainly from a pyrolytic source,

while the rst two are from petroleum. The total concentration
of the 16 PAHs (PAH) varied from 15.5 to 1,646 g kg1 within
the 510 cm and 3035 cm layers, respectively. In general, with
some exceptions, concentration of individual PAHs was very
low in comparison to those found in urban and industrialized
regions (e.g. Colombo et al., 1989; Doskey and Andren, 1991;
Medeiros and Bcego, 2004; Lee et al., 2005; Banger et al., 2010).
The upper layers, between 0 and 15 cm contained relatively
low to medium concentrations of PAHs (15.5122 g kg1 ),
while the lower layers between 15 and 50 cm comprised of
medium to high (2151646 g kg1 ) concentrations of PAHs.
An interesting feature was the dominance of naphthalene, acenaphthylene, anthracene and uoranthene (8.260.8%), possibly
from unburned fossil fuels in the fresh topmost layer (015 cm)

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J. Snez et al. / Chemie der Erde 73 (2013) 555563

Table 1
Individual concentration (g kg1 dry sediment) and important indices of PAHs in the sediment core layers.
Sediment core layer (cm)

Naphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Chrysene
Benzo[a]anthracene
Benzo[b]uoranthene
Benzo[k]uoranthene
Benzo[a]pyrene
Indene[1,2,3-cd]pyrene
Benzo[ghi]perylene
Dibenzo[ah]anthracene
PAHs
Ant/Ant+Phe
Flt/Flt+Pyr
BaA/BaA+Chry
IP/IP+BghiP
Phe/Ant
Flt/Pyr
BaA/Chry
LMW/HMW

05

510

1015

1520

2025

2530

3035

3540

4045

4550

74.0
37.7
bdl
bdl
bdl
10.0
bdl
bdl
bdl
bdl
bdl
bdl
bdl
bdl
bdl
bdl
122
1

5.95
bdl
bdl
bdl
bdl
4.71
4.84
bdl
bdl
bdl
bdl
bdl
bdl
bdl
bdl
bdl
15.5
1
1

74.0
37.7
bdl
bdl
bdl
10.0
bdl
bdl
bdl
bdl
bdl
bdl
bdl
bdl
bdl
bdl
122
1

4.29
36.5
bdl
bdl
bdl
bdl
8.94
bdl
6.84
bdl
158
bdl
bdl
bdl
bdl
bdl
215

6.67
bdl
bdl
bdl
bdl
6.27
6.86
bdl
bdl
bdl
bdl
bdl
bdl
bdl
bdl
1627
1646
1
1

4.22
bdl
bdl
bdl
4.41
bdl
8.83
6.63
7.46
bdl
137
bdl
bdl
bdl
bdl
1269
1438

1
0

3.78
bdl
bdl
bdl
3.83
1.52
9.68
bdl
6.40
bdl
bdl
bdl
bdl
bdl
bdl
1028
1053
0.284
1
0

28.2
bdl
bdl
bdl
bdl
8.51
bdl
bdl
9.7
bdl
488
bdl
bdl
bdl
bdl
bdl
534
1

3.34
35.2
bdl
bdl
6.45
1.46
14.9
13.2
1.43
bdl
101.8
bdl
bdl
bdl
bdl
783
961
0.1847
0.529
0

0.571
0

6.76
bdl
bdl
5.17
6.55
9.13
9.87
8.48
1.68
bdl
211
bdl
bdl
bdl
bdl
bdl
259
0.582
0.537
0

2.515

1.331
0
0.133

0.718
1.164
0

4.414
1.127
0
0.227

0
0.0245

0.012

bdl, below detection limit.

a
Calculations not made due to being divided by zero.

which was in contrast to the overbearing presence of PAHs having four and ve aromatic rings and a pyrolytic origin, namely,
benzo[b]uoranthene (9.698.8%) and dibenzo[a,h]anthracene
(81.598.8%) in the lower layers (1550 cm).
While stable isomers are usually produced from petrogenic
sources, the unstable isomers are of pyrogenic origin (Budzinski
et al., 1997) and the predominance of high concentrations of PAHs
having more than four aromatic rings points to their formation
during pyrolysis of fossil fuels (Gogou et al., 2000).
Interestingly, in all layers where it was possible to evaluate
the ratios of PAHs (Yunker et al., 2002a, 2002b), the values indicated a pyrolytic origin (Gschwend and Hites, 1981; Soclo et al.,
2000). The An/An+Phe, Flt/Flt+Pyr, and Flt/Pyr indices showed values above 0.10, 0.5 and 1, respectively. Meanwhile, the Phe/Ant
and LMW/HMW presented ratios below 10 and 1, respectively. In
contrast, the BaA/BaA+Chry and BaA/Chry presented ratios below
20 and 0.4, more specically zero values in both the cases, which
suggests petrogenic origin of PAHs (Gschwend and Hites, 1981;
Yunker et al., 2002a, 2002b). Notably, BaA was not detected (values below the detection limit). Further, the prepared crossplots
between Ant/Ant+Phe and Phe/Ant vs. Flt/Flt+Pyr ratios (Fig. 2)
revealed that, in general, sources of PHAs were of pyrolytic origin with a possible small contribution of petroleum (4045 cm)
(Gschwend and Hites, 1981; Yunker et al., 2002a, 2002b; Bcego
et al., 2006).
Froehner et al. (2012) studied the presence of PAHs in the surcial sediments in the Vossoroca Reservoir. On comparing the PAHs
concentration with our research, some interesting ndings showed
up. Acenaphthene, benzo[a]anthracene, benzo[k]uoranthene,
benzo[a]pyrene, indene[1,2,3-cd]pyrene and benzo[ghi]perylene
were present in all samples the values for which from our research
were below detection limit and were not present in any layer. Similarly, uorene was present only in the deeper core (4550 cm),
although it occurred in all samples studied by Froehner et al.
In general, the values for other PAHs, particularly in sediments
close to the bridge, were several times higher than those found
in our sediment core layers, indicating possible degradation over

time. Comparison of the ratios between PAHs with those reported

by Froehner et al., revealed similar conclusions where the main
sources of PAHs are of pyrolytic origin, especially emissions from
vehicles that cross the bridge. In accordance to literature values, the
dibenzo[a,h]anthracene concentrations were relatively high which
could be attributed to coal tar pavement, considering that the sample site was close to a heavily transited road.
Additionally, there was no report of any important episode of
oil spill registered close to the area of study; however, the sampling site being located close to a highway, soot, exhaust gases, oil
and petroleum leaks and dust from worn out tires may reach the
site close to the reservoir. The studied zone is not an industrialized
one; the main activities are subsistence farming and tourism for
leisure (like the burning of coal for barbecues), although these activities are neither extensive nor intensive. In summary, an apparent
predominance of pyrolytic PAHs was observed in the lower layers, while apparently unburned fossil fuels prevailed in the upper
layers.
3.2. n-Alkanes
n-Alkanes bearing eight to forty carbon atoms were evaluated
and their concentrations have been presented in Table 2. n-C8 and
n-C10 alkanes were not detected in any layer. n-C15 and n-C36 were
the most abundant and dominant n-alkanes averaging 198 46.8
and 523 168 g kg1 , respectively in the core while other prominent ones were n-C18 and n-C32 . In general, the heavier n-alkanes
prevailed, in concentration and abundance, over the lighter ones
and, although not very clear, odd n-alkanes were slightly dominant
over even n-alkanes. Distribution proles of these compounds have
been shown in Fig. 3.
In Fig. 3, each bar representing a particular chain-length is the
concentration of the specic n-alkane in that layer, from upper
(left) to lower (right) layers. The lighter n-alkanes were distributed
more evenly through the layers, particularly n-C9 , n-C12 and
n-C18 showed less variation, averaging 14.6 3.0, 31.6 1.9 and
95.0 5.2 g kg1 , respectively, in the core whereas the heavier

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559

Fig. 2. Crossplots of the values Ant/Ant+Phe and Phe/Ant ratios against Flt/Flt+Py ratio for all the layers of the core sediment.

n-alkanes presented a more odd distribution. The predominance

of n-alkanes (Table 3) like n-C36 , as well as alkanes of carbon chain
greater than 35, was also observed in bitumen compounds that
act as a binder substance on the pavement, and can therefore be,
characteristic of both sources. It is noteworthy that high concentrations of n-C36 in the sediment in comparison to other chain
lengths suggest that the impact is primarily due to the contribution of the pavement. On the other hand, n-C15 is associated
with aquatic algae, plankton and photosynthetic bacteria (Cranwell
et al., 1987; Doskey and Andren, 1991) and n-C31 to related grasses

(Cranwell, 1973). Although less abundant, contributions from

n-C27 , n-C29 and n-C31 alkanes were noted and possibly arose from
waxes of higher plants growing nearby (Eglinton and Hamilton,
1963, 1967; Cranwell, 1973; Cranwell et al., 1987; Rieley et al.,
1991; Meyers, 2003), n-C23 probably from oating and submerged
plants (Cranwell, 1984; Ficken et al., 2000), and n-C18 from indigenous sources, such as bacterial degradation of algae and detritus
(Elias et al., 1997; Ekpo et al., 2005).
Analysis of the Carbon Preference Index (CPI) values in the
core revealed that they ranged between 0.35 and 3.99. CPIs values

Fig. 3. Chain-length distribution of n-alkanes from the sediment core. Each bar, for a determined chain-length, is the concentration of this specic n-alkane in that layer,
from upper (left) to lower (right) layers. The arrow indicates a bar out of scale, in this case the concentration is 1514 g kg1 (510 cm).

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Table 2
n-Alkane concentrations (g kg1 dry sediment) in the layers of the sediment core from the Vossoroca Reservoir.
Sediment core layer (cm)

Prystane
Phytane
n-C8
n-C9
n-C10
n-C11
n-C12
n-C13
n-C14
n-C15
n-C16
n-C17
n-C18
n-C19
n-C20
n-C21
n-C22
n-C23
n-C24
n-C25
n-C26
n-C27
n-C28
n-C29
n-C30
n-C31
n-C32
n-C33
n-C34
n-C35
n-C36
n-C37
n-C38
n-C39
n-C40
n-Alkanes
Odd/even
TARHC
CPI
Pr/Ph
Pr/n-C17
Ph/n-C18
LMW/HMW
Paq

05

510

1015

1520

2025

2530

3035

3540

4045

4550

46.6
bdl
bdl
13.1
bdl
3.21
36.7
19.4
42.8
253
65.9
bdl
102
10.9
7.00
105
11.8
bdl
1.40
bdl
544
1.90
29.3
4.54
1.30
530
181
130
72.6
6.82
491
bdl
11.0
bdl
50.6
2725
0.65
2.034
0.842

31.5
bdl
bdl
13.1
bdl
2.67
30.5
63.3
52.4
200
40.2
24.3
97.0
20.4
13.7
9.19
16.3
bdl
22.9
11.0
44.8
61.2
20.1
6.85
196
75.9
530
266
1514
7.69
431
bdl
38.7
bdl
54.1
386
0.25
0.587
0.35

21.7
bdl
bdl
13.0
bdl
3.40
29.4
83.5
35.6
229
31.3
bdl
bdl
7.99
4.23
10.9
5.88
bdl
17.9
7.61
18.6
9.00
12.9
23.6
1.72
109
33.9
44.7
6.32
296
284
bdl
bdl
0.12
42.4
1363
1.60
0.599
2.462

22.8
bdl
bdl
22.3
bdl
3.55
31.9
1.02
60.4
135
102
19.0
102
22.1
3.00
2.69
10.2
bdl
36.0
bdl
27.2
44.2
24.1
49.4
28.7
16.0
124
98.7
2.86
24.0
484
196
4.01
bdl
1.98
1676
0.61
0.622
0.936

20.4
bdl
bdl
bdl
bdl
5.50
31.7
1.47
95.2
127
19.1
15.68
100
11.4
1.42
bdl
13.6
97.2
10.1
bdl
39.4
55.7
35.0
97.7
45.6
1.55
322
195
905
22.3
827
14.8
14.9
194
0.41
3300
0.34
1.008
0.518

33.9
7.61
bdl
15.1
bdl
3.17
31.3
85.9
47.5
140
18.6
bdl
90.7
1.46
97.7
55.0
10.6
50.4
37.2
bdl
28.3
2.10
23.0
289
17.8
599
203
99.3
2.89
80.6
709
14.0
3.21
bdl
41.7
2797
1.05
6.29
3.399
4.5

30.4
bdl
bdl
13.0
bdl
2.83
31.3
0.92
37.3
218
62.3
bdl
89.8
19.0
7.5
2.93
14.6
55.1
13.6
8.79
35.9
107
5.07
164
24.5
89.0
213
117
6.07
0.63
613
18.6
bdl
bdl
bdl
1970
0.71
1.518
1.681

29.2
2.87
bdl
14.4
bdl
3.80
31.5
72.0
36.8
216
23.5
bdl
90.7
11.2
4.87
23.2
8.71
31.1
24.5
0.31
16.8
42.3
5.85
38.2
13
157
64.2
52.4
94.9
91.0
337
9.64
10.3
bdl
5.92
1530
0.99
1.044
1.91
10.2

30.4
bdl
bdl
13.0
bdl
2.83
31.3
0.92
37.3
218
62.3
bdl
89.8
19.0
7.50
2.93
14.6
55.1
13.6
8.79
35.9
107
5.07
164
24.5
89.0
213
117
6.07
0.63
613
18.6
bdl
bdl
bdl
1970
0.71
1.518
1.681

19.4
1.55
bdl
14.3
bdl
12.3
30.3
2.50
35.9
245
23.5
bdl
93.5
10.7
5.60
27.7
6.78
18.0
2.70
2.80
14.2
22.6
10.8
39.7
7.98
18.3
48.0
70.6
bdl
39.6
440
1.16
bdl
bdl
13.4
1259
0.72
0.315
1.869
12.5

1.296
0
0.406
0.117

0.017
1.438
0.264

0.032
0.953
0.139

0
0.511
0.202

1.299
0
0.407
0.495

1.201
0
0.962
0

0.084
0.341
0.054

0
0.511
0.202

0
0.325
0

1.322
0.054

bdl, below detection limit.

a
Calculations not made due to being divided by zero.

lower than 1 were reported for 510, 3035 and 3540 cm layers
showing a value of 0.35, 0.936 and 0.518, respectively. The
remaining layers showed values above 1 but below 4 which generally suggest oil dominance in the n-alkanes over biogenic sources
like higher plants plausibly due to contamination from the petrol
station located upstream. The CPI calculated for the 1030 cm

layers suggests involvement of n-alkanes of higher terrestrial plants

and oil. The CPI plot (Fig. 4) showed low values for the upper
layers, while peaking at 1015 cm until the values drop consistently till layer 3540 cm after which another peak for the
highest value occurs, before nally dropping again for the 4550 cm
layer.

Fig. 4. Variation of total n-alkanes concentration, odd/even n-alkanes ratio, terrigeneous/aquatic n-alkanes (TARHC ), Carbon Preference Index (CPI), low molecular weight
and high molecular weight n-alkanes ratio (LMW/HMW), and proportion of aquatic plants (Paq ) ratios along the depth prole compared to the deposition time.

Author's personal copy

J. Snez et al. / Chemie der Erde 73 (2013) 555563
Table 3
Distribution of predominant n-alkanes through the layers of the core sediment.
Depth (cm)

Predominant n-alkane chain

05
510
1015
1520
2025

n-C15
n-C15
n-C13
n-C15
n-C13
n-C36
n-C15
n-C15
n-C15
n-C15
n-C15

2530
3035
3540
4045
4550

(15.8%), n-C26 (19.0%), n-C31 (15.6%), n-C36 (12.5%)

(9.9%), n-C32 (12%), n-C34 (32.3%), n-C36 (8.7%)
(11.1%), n-C15 (26.2%), n-C35 (14.2%), n-C36 (13.3%).
(29.8%), n-C18 (9.0%), n-C36 (21.8%)
(8.5%), n-C15 (22.0%), n-C18 (7.3%), n-C31 (7.5%),
(14.0%)
(18.8%), n-C29 (7.1%), n-C32 (8.4%), n-C36 (21.6%)
(13.4%), n-C16 (9.4%), n-C18 (8.0%), n-C36 (19.5%)
(7.6%), n-C32 (8.8%), n-C34 (23.3%), n-C36 (20.2%)
(8.9%), n-C29 (9.3%), n-C31 (18.0%), n-C36 (18.5%)
(18.8%), n-C29 (7.1%), n-C32 (8.4%), n-C36 (21.6%)

The ratio of hydrocarbons for terrigenous and aquatic sources

(TARHC = n-C27 + n-C29 + n-C31 /n-C15 + n-C17 + n-C19 ) is associated
with the ratio of long-chain hydrocarbons and short-chain hydrocarbons (Bourbonniere and Meyers, 1996; Tenzer et al., 1999). High
TARHC values suggest increased external supply or drainage basin,
organic matter source soil and vegetation ground, compared to
the internal source of organic matter, pertaining to the aquatic
ora (Meyers, 1997; Tenzer et al., 1999). The external source of
organic matter from terrestrial plants is reected in the higher
concentration of n-alkanes with respect to the internal supply of
water sources, which may result in an unbalanced weight of TARHC
(Bourbonniere and Meyers, 1996; Meyers, 1997; Peters et al., 2005).
TARCHC ranged from 0.35 to 3.39, indicating a dominance of
terrigenous organic matter through the layers with only layers
between 5 and 20 cm and 3035 cm presented an aquatic inuence on the organic matter. It was observed that the upper layers
namely, between 5 and 20 cm, display higher aquatic inuence than
the lower layers pertaining to 20 and 50 cm (except 3035 cm); terrigenous material has a tendency to resist further degradation, in
contrast to material of aquatic origin owing to the longer carbon
chains leading to more apolarity and consequently greater persistence. The non-homogeneity between the origin of the organic
matter could be related to variations in rainfall as the main
inuence on the distribution dynamics, whereas the terrigenous
material may be transported to the reservoir as a runoff resulting
from the rainfall. Thus, the higher TARHC values in this study are
related to the high values of n-C31 , indicative of the presence of
grasses, which suggests periods of grass pruning and subsequently
entering into the water body and further sediment deposition.
Ratio of low molecular weight and high molecular weight
of n-alkanes (LMW/HMW), analogous to the CPI index, indicates sources of n-alkanes and possible contamination with
oil, LMW/HMW = n-Ci /n-Cj (i = 13,14,. . .,20; j = 21,22,. . .,33)
(Volkman et al., 1980; Colombo et al., 1989). The indices showed
values much below 1 for upper (010 cm) and bottom layers
(3550 cm), indicating aquatic fauna, higher plants and non photosynthetic bacterial sources (Gearing et al., 1976; Colombo et al.,
1989; Commendatore et al., 2000). LMW/HMW values close to one
were found for 2025 and 3035 cm layers, which indicate possible
algae, plankton, and crude oil sources. Layers between 10 and 20 cm
reported values 1.3 and 1.4 respectively, which suggests recent
contamination by oil and degraded oil as a source of n-alkanes.
Ficken et al. (2000) correlated n-alkanes having average (n-C23
and n-C25 ) and long carbon chains (n-C29 and n-C31 ) with origin and proportion of submerged/oating aquatic plants versus
emergent and terrestrial plant sources in lake sediments, the
measure of which is given by the proportion of aquatic plants
(Paq = n-C23 + n-C25 /n-C23 + n-C25 + n-C29 + n-C31 ). The core prole
presented a mixed pattern. However, a dominance of emergent
macrophytes at 510, 1530, and 4550 cm layers was observed,
where Paq values occurred between 0.1 and 0.4. The dominance

561

of terrestrial plants was found for the layers 05, 1015, and
4045 cm, having values lower than 0.1. Only the 3540 cm layer
reported a Paq value between 0.4 and 1, indicating dominance of
submerged and oating macrophytes.
3.3. Isoprenoids
Pristane (2,6,10,14-tetramethyilpenthadecano) and phytane
(2,6,10,14-tetramethylhexadecano) are present in most sources of
petroleum, usually as a major constituent within a much wider
range of isoprenoid alkanes (NCR, 1985). The pristane/phytane
(Pr/Ph) relationship is considered a biomarker indicator of oxicity and anoxia and its use is based on the differential reaction of
phytol, the parent compound mainly derived from the side chain
of chlorophylls. Under oxic conditions, phytol is decarboxylated to
pristane while in a reducing environment, phytol tends to form predominantly phytane. Risatti et al. (1984) stated that methanogenic
bacteria, present in anoxic conditions, are an important source of
phytane.
In the present study, phytane was detected in layers beneath the
zone of bioturbation, but only in the 1520, 2025, and 4045 cm
fractions at a concentration of 1.55, 2.87 and 7.61 g kg1 , respectively (Table 2). The concentrations were less than that of pristane
and its closely eluting alkane, n-C18 . In contrast, pristane, averaging
28.6 8.2 g kg1 in the core, showed up in all fractions and ranged
between 19.4 g kg1 (1520 cm) and 46.6 g kg1 (05 cm), the
last fraction being the bioturbation zone and being more oxidic.
This dominance of pristane over phytane could indicate the priority of the conversion of phytol into pristane, a characteristic at
oxidic conditions. Measurement of Pr/Ph ratio was possible only in
the layers where phytane was present which were 12.5 (1520 cm),
10.2 (2025 cm) and 4.5 (4045 cm). In uncontaminated sediments
this ratio usually lies between 3 and 5 (Steinhauer and Boehm,
1992). The absence of phytane may be explained by several periods
of bioturbation and tidal as the sample was collected close to the
shoreline of the reservoir, which is subjected to seasonal tidal and
periods of oxidic conditions.
The ratios Pr/n-C17 and Ph/n-C18 were applied to the study of
contaminated areas. Due to the microbial preference, both the isoprenoids are degraded more slowly than their associated n-alkane,
thus high ratios of >2 indicating contribution of recent oil, whilst
lower values pertaining to previously degraded residues (Colombo
et al., 1989). Although the area has not been subjected to oil spills,
the reservoir is in direct line of inuence of a gas station situated
along the road, about 900 m from the sampling point such that it
may have been subjected to contamination by leakages rendering
the ratios useful. The ratio Ph/n-C18 reported no signicant values,
as a result of low or absent levels of phytane while it was possible to calculate Pr/n-C17 ratios of only fractions 510, 3035 and
3540 cm. They showed values higher than 1 but lower than 2, possibly due to prior degraded waste while higher ratios could indicate
contamination.
4. Conclusions
The studied area showed signicant inuence from the highway,
with sediment deposit originating from the pavement, and suggesting sources of pyrolytic origin from the heavy trafc of vehicles from
the BR 376 highway and a gas station closer to the sample point. An
analysis of n-alkanes indicated that the region receives signicant
contribution from higher plants, with low contribution originating from autochthonous organic matter. Identied PAHs suggested
predominance of pyrogenic sources, formed during the pyrolysis of
fossil fuels, a direct inuence from the heavy highway trafc closeby. Detected DBahA, contributed by particulate pavement, occurs

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562

J. Snez et al. / Chemie der Erde 73 (2013) 555563

in signicant concentrations only below 15 cm depth. Sediments

appear to be toxic and the absence of phytane can be due to several periods of bioturbation and tidal, the sample being collected
close to the shoreline. In general, on being compared with other
sediments cores, the area seems to be less polluted.
Acknowledgments
We thank Luis Carlos Barbosa for helping us in the eld work and
Dr. Cristovo Fernandes for the sediment rate data. Sandro Froehner
thanks the National Council of Technological and Scientic Development (CNPq) grants 300448/2009-0 and 471183/2010-5. Juan
Snez thanks the Support Program for the Restructuring and Expansion of Federal Universities (UFPR/Reuni) for the post doctorate
fellowship grant. The authors would like to thank the anonymous reviewers for their comments that helped improve the
manuscript.
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