Marine Pollution Bulletin 154 (2020) 111087

Contents lists available at ScienceDirect

Marine Pollution Bulletin

journal homepage: www.elsevier.com/locate/marpolbul

Baseline

Organic contaminants and trace metals in the western South Atlantic upper
continental margin: Anthropogenic influence on mud depocenters
Felipe R. Santos⁎, Patricia A. Neves, Bianca S.M. Kim, Satie Taniguchi, Rafael
A. Lourenço, Cristian T. Timoszczuk, Basílio M.T. Sotão, Rosalinda C. Montone,
Rubens C.L. Figueira, Michel M. Mahiques, Márcia C. Bícego

Instituto Oceanográfico, Universidade de São Paulo, 05508-120 Praça do

Oceanográfico, 191 São Paulo, SP, Brazil

A R T I C L E I N F O

Keywords:
Mud depocenters
Polycyclic aromatic hydrocarbons Organochlorine compounds Brazilian continental
margin Sediment
A B S T R A C T

Trace metals, dichloro-diphenyl-trichloroethane (DDTs), polychlorinated biphenyls

(PCBs), and polycyclic aro- matic hydrocarbons (PAHs) were quantified in surface
sediments from mud depocenters located in the western South Atlantic upper
continental margin. There was no anthropogenic trace metal pollution observed,
and the higher As values were attributed to high CaCO3 content in the area. The
results indicate PCB sources associated with long-range atmospheric transport in
addition to past DDT use for agriculture and pest control. PAHs were mainly
originated from biomass and fossil fuel combustion, and their distribution is
in alignment with the riverine runoff influence in southern region, which is
transported towards the northern regions by coastal currents. Higher
concentrations of 2–3 ring PAHs and DDTs in shallow and northern stations
indicate a coastal influence. This work presents baseline information on the
extent of anthropogenic influence in mud depocenters located in the western South
Atlantic upper continental margin, showing these locations as potential source to
sink of anthropogenic contaminants.

Trace metals, PAHs, PCBs and DDTs are widely distributed into coastal
environments and can reach marine ecosystems through fluvial transport, direct
input through the discharge of domestic and industrial effluents, continental
drainage and atmospheric fallout (dry or wet deposition) (Mitra et al.,
2019; Combi et al., 2019; Barhoumi et al.,
2019). Due to their hydrophobic nature, these compounds tend to as- sociate
with suspended particles and be subsequently deposited in se- diments, which may
act as the ultimate sink and carrier of these com- pounds (Stogiannidis and
Laane, 2015). The most sensitive marine ecosystems are those located near
the coast, such as the continental margins, where ~80% of the whole
planet's sediment can be found (Kennett, 1982).
Continental margins are dynamic and complex environments, and they play a key
role in the transport and storage of organic and in- organic material in
the ocean, acting as sinks and secondary sources of terrestrially derived
materials (Salvadó et al., 2019). As a result, sedi- ments loaded with
anthropogenically-derived materials may indicate the magnitude of the
anthropogenic activities developed on the con- tinent (Ya et al., 2017). Several
authors described muddy deposits in these areas as the destination of organic
and inorganic compounds from continental sources (Deng et al., 2013; Mahiques et
al., 2015; Cai et al.,
2016; Tamburrino et al., 2019).
Over the last century, the Brazilian population has increased from
27 to 210 million, with 25% of the population living in the coastal zone and >
50% in the south and southeast regions (IBGE, 2011; Andrés et al., 2018).
The land area adjacent to the western South Atlantic continental margin
presents highly populated cities, intense harbor activities and an industrial
complex with significant oil refining, pet- rochemical, and other industries.
Despite several studies focused on the coastal and estuarine environments in
these areas, (Bícego et al., 2006; Martins et al., 2011; Frena et al., 2017;
Souza et al., 2018), few works have been conducted in the continental margin,
although the possibility of these compounds reaching this region has been
reported (Mahiques et al., 2015).
Therefore, the present study aims to assess the influence of an- thropogenic
activities registered in superficial sediments from mud depocenters located at
the western South Atlantic upper continental margin by the evaluation of
organic contaminants such as DDTs, PCBs, PAHs and trace metals. It should be
highlighted that the present study is the first of its kind to investigate
anthropogenic compounds in marine sediment on such a large scale in Brazil.
The study area corresponds to the South and Southeast Brazilian

⁎ Corresponding author.
E-mail address: feliperod@usp.br (F.R. Santos).

https://doi.org/10.1016/j.marpolbul.2020.111087
Received 9 December 2019; Received in revised form 12 March 2020; Accepted 16
March 2020
Available online 26 March 2020
0025-326X/ © 2020 Elsevier Ltd. All rights reserved.
F.R. Santos, et al.
Marine Pollution Bulletin 154 (2020) 111087

continental margin (25 to 33° S), with shelf widths ranging from
100 km to 230 km and declivities between 1:600 and 1:1300
(Zembruscki, 1979). Mud depocenters in this region can be found from the 50 m
isobaths towards the outer shelf. These deposit formation results from
variations in sea-level and tectonic setting; regional climate system; riverine
sediment type and intensity input, and regional to local shelf hydrodynamics
processes (Mahiques et al., 2015 and references).
The three main coastal economic sectors in the continent bordering the study
area (tourism, harbor and industrial activity) are con- centrated in the
shoreland, as well as a dense urban population located within 100 km of the
coast (Andrés et al., 2018). These areas present the largest commercial
harbor in Latin America and the most important metallurgical and petrochemical
industry in Brazil, located in São Paulo state (Martins et al., 2011); in
addition to an important harbor for grain export (Marone et al., 2000), and
other products such as fertilizers, minerals, and petroleum derivatives in
Paraná State (Choueri et al.,
2009); the coal, textile and ceramics industry in Santa Catarina state
(Andrés et al., 2018); and the oil refinery and terminal, fertilizer-pro-
ducing plants and fishery industries in the coastal area of Rio Grande do Sul
(Martins et al., 2007).
Twenty-nine surface sediment samples (1 cm of undisturbed surface sediment) were
collected using a multi-corer sampler (MUC) in mud depocenters located along the
Brazilian south and southeast continental margin during two cruises onboard the
RV “Alpha Crucis” (June 2017 and January 2019) (Fig. 01; Table 01S).
The samples were stored in precleaned aluminum containers for organic
analysis and polyethylene containers for metal analysis. All samples were
conditioned at low temperatures (−20 °C) and freeze- dried prior to further
analysis.
The sediment grain size was determined on a Malvern 2000 ana- lyzer after
the removal of organic matter and carbonates using hy- drogen peroxide
and hydrochloric acid, respectively. Total organic carbon (TOC) was
analyzed on an Elemental Combustion System (Costech Instruments) coupled to
an Isotope Ratio Mass Spectrometer (Thermo Scientific) (EA-IRMS).
The sediment samples were submitted to a partial digestion tech- nique according
to W 846 US EPA 3050b (USEPA, 1996). Al, As, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn,
Ni, P, Pb, Sc, Sr, V and Zn were analyzed by inductively coupled plasma optical
emission spectrometry (ICP-OES). For quality assurance and quality control
(QA/QC), a certified reference material (RM - Metals in Soils SQC001; Lot
LRAA0982) and an analy- tical blank underwent the same analytical procedure
(Table 02S). All elements were within 70–111% of the recovery in the RM, and no
peaks interfered with the analyses of target elements in the analytical blank.
The organic compounds analyzed in this study and their abbrevia- tions are
shown in Table 03S. Twenty grams of freeze-dried sediment samples were
spiked with a surrogate standard mixture containing deuterated PAHs (d8-
naphthalene, d10-acenaphthene, d10-phenan- threne, d12-chrysene and d12-perylene)
and PCBs 103 and 198, and extracted in a Soxhlet system with 80 mL of n-
hexane/dichloromethane (1/1; v/v) for 8 h.
The obtained extracts were purified by adsorption chromatographic column
containing 3.2 g of alumina (5% water deactivated) and eluted with 20 mL of n-
hexane/dichloromethane 30% (v/v).
Organic compound identifications and quantifications were con- ducted in a gas
chromatograph (Agilent Technologies 7010B) coupled to a mass spectrometer with
triple quadrupole (GC/MS/MS) operating in multiple reaction monitoring (MRM).

Fig. 01. Map of the study area showing the sediment sampling locations in the
South and Southeast Brazilian Continental Margin mud depocenters.

2
F.R. Santos, et al.
Marine Pollution Bulletin 154 (2020) 111087

The samples were injected in pulsed splitless mode in a capillary column

coated with a 5% phenyl-substituted dimethylpolysiloxane phase (length = 30
m, ID = 0.25 mm, film thickness = 0.25 μm). The injected volume was 1 μL, and
helium was used as carrier gas (constant flow of 1.2 ml min−1). Oven temperature
ramps for PAHs, DDTs and PCBs were programmed as follows: 50 °C for 1 min,
increased at
20 °C min−1 to 200 °C, then at 10 °C min−1 to 300 °C, with a final hold
of 5 min. The interface, source and quadrupole temperatures were
300 °C, 300 °C and 150 °C, respectively.
Quantification was based on a nine-level analytical curve, with a correlation
coefficient ≥ 0.995, following the internal standard method (p-terphenyl-d14
for PAHs, and TCMX for DDTs and PCBs). Quantification limits (QL) were
assigned as the lowest quantifiable concentration of the analytical curve,
and they were 0.002 ng g−1 for DDTs, 0.001 ng g−1 for PCBs and 0.006 ng
g−1 for PAHs, where the concentration values below this limit were rejected.
All data were subject to a rigorous QA/QC, based on the analysis of procedural
blanks, surrogate recovery, spiked-blanks, spiked-samples and duplicate analysis
of certified reference material (IAEA-417, International Atomic and Energy Agency -
Monaco). Procedural blanks presented no interfering peaks. The global surrogate
recoveries ranged from 55 to 92%. Spiked blank and sample standard recovery
varied from 63 to 110% and 76 to 101%, respectively. Measured concentra-
tions of target PAHs, PCBs and DDTs in IAEA-417 ranged from 70 to
104% and 68 to 87% of the certified values, with 87% of the analyzed compounds
in concentrations within the aforementioned range.
Before performing the principal component analysis (PCA), the variables were
tested for normality by the Shapiro Wilk test and homoscedasticity by the Cochran
test. The data were standardized (x - μ = σ), and the nondetectable values were
reassigned as half of the QL values (Zar, 2007). Principal components were
rotated using the Var- imax rotation method. Only the variables with loading
values > 0.7 were considered for data interpretation. Statistical analysis
including the Pearson correlation and principal component analysis were per-
formed using Statistica v. 12.5 software.
Due to the large area approached in this study and based on the
geographical location and results, which showed different sources of
contaminants, transport pathways and compound concentrations, especially for DDTs
and PAHs, the study area was divided into three regions: North (stations
#367 to #378); Central (stations #579 to
#584#) and the South (stations #556 to #576) regions (Fig. 01).
Trace metal total concentrations ranged from 28,124 to
172,104 mg kg−1, at stations #566 and #581, respectively, and pre- sented
individual values varying from non-detected (Cd) to
3157–48,687 mg kg−1 dw (Al) (Table 04S). In comparison to other
studies on the Brazilian coast, such as the Santos and São Vicente es-
tuarine systems (Kim et al., 2019), Paranaguá Estuarine system (e.g., Choueri
et al., 2009) and Araçá Bay (Kim et al., 2018), the mean trace metal were
relatively low.
No clear differentiation regarding trace metal spatial distribution was found,
although decreasing concentrations from the coast towards the ocean were
observed. Usually, values of potentially harmful ele- ments in continental shelf
sediments tend to present lower concentra- tions than coastal zones due to
dispersion and distance from the source. This tendency was observed for all
trace elements, except As levels, which showed the highest level on samples
#580 and #581, which are located next to the slope.
Station #564 presented 2-fold higher contents of As than the other samples.
Mirlean et al. (2003) reported high concentrations of this metalloid in the
freshwater system of Patos Lagoon attributed to ac- tivities of the
fertilizer industry, contributing to arsenic pollution. Sta- tion #372 is the
nearest station to the coast located in front of the Itajaí- Açu estuary and
shallower than the others. This estuarine system has great economic importance
due to the presence of Itajaí Harbor, in- dustries and urban, touristic and
dredging activities (Frena et al., 2017). It was distinct from all other areas,
and presented concentrations in
mg kg−1 approximately 2-fold higher compared to the other areas,
increasing the standard deviation especially for As (15), Cr (29), Cu (20), Ni
(17), Pb (19) and Zn (92).
The trace metals Al, Fe and Sc are conservative elements and may be considered to
be reliable particle-size proxy elements (Kim et al., 2016). These element
correlations with TOC and %Mud (silt + clay) levels indicate these values as
related to the background values (Table 05S).
Pearson's correlation was performed among all elements. The low and not
significant (α = 0.01) correlation between Fe (r = 0.29; p < .01) and Al (r =
0.07; p < .01) indicates that As is not linked to the clay mineral lattice, but
to P (r = 0.74; p < .01) and carbonates, represented by the strong correlation
with Ca (r = 0.71; p < .01) and Sr (r = 0.62; p < .01) (Table 05S). Studies
report the ability of cal- careous bioclastic material to scavenge As from the
water column and retain it in the sediment (Mirlean et al., 2011). However, the
extent of arsenates sorption on carbonates is still unknown, the adsorption of
phosphates on calcites and aragonites, and the relationship between As and
phosphatic materials have been reported (Millero et al., 2001).
Trace metal As is largely discussed in Brazil since it appears that
continental rocks, as well as coastal and marine sediments are enriched in As
(Mirlean et al., 2012; Kim et al., 2016; Kim et al., 2018). The As levels found
in this study were higher than the established threshold level by the
Brazilian National Council for the Environment (CONAMA) (19 mg kg−1), as well as
Canadian regulation (CCME, 2001), with va- lues above the ISQG in central and
north region stations. Studies have reported that an increase in As appears
to occur from terrestrial to marine environments in other parts of the world
(Reimann et al., 2009). Our results indicate that the studied continental margin,
especially the mud depocenter areas, is an important sink of As.
The total concentrations of PCBs (∑50PCBs) and DDTs (∑6DDTs), as well as the
concentrations of low molecular weight (LMW; 2–3 rings), high molecular weight
(HMW; 4–6 rings), alkyl and total PAH con- centrations (∑31PAHs), except
perylene, are given in Fig. 02. The ma- jority of the organic contaminants
(84%) were detected in all analyzed samples. The presence of these
anthropogenic compounds along the entire study area indicates that the region
is subject to the effects of human activities.
∑50PCBs ranged from 0.41 ng g−1 to 5.09 ng g−1 dw (Fig. 02A;
Table 04S), with a mean value of 2.33 ± 1.18 ng g−1, and the highest
concentration at station #372. These results are similar to those found in areas
with an absence of local PCB sources, such as the East China Sea continental
shelf (Cai et al., 2016) and the Paranaguá estuarine system (Combi et al.,
2013).
The use of PCBs was restricted in the 1980s in Brazil, and there are no records
of these compounds production in the country; although, PCBs were still in
use in Brazil at the end of the 2000s. These com- pounds in the
environment are commonly related to deactivated elec- trical transformers
containing oil with PCBs used in power plants (Penteado and Vaz, 2001;
Almeida et al., 2007).
In general, the ∑50PCBs spatial distribution was similar along the study
area, showing no significant difference between the North (2.67 ± 1.35
ng g−1), Central (1.84 ± 1.32) and South (2.30 ±
1.04 ng g−1) regions (p > .05, ANOVA) (Fig. 02A). Likewise, ∑50PCBs depth
distribution presented similar values in grouped samples from shallow (0–80
m), intermediate (80–160 m) and deep (> 300 m) sta- tions (Fig. 03A).
Considering the large geographical area studied, the spatial and depth
distribution may indicate a similar and diffuse pre- dominant source of PCBs
associated with long-range transport process.
The PCB congener contribution showed the predominance of pen- tachlorobiphenyls
(mainly PCB-101, 110, 95, 118), followed by tetra- chlorobiphenyls (such as
PCB-52, 70 and 44) and hexachlorobiphenyls (predominance of PCB-138 and 153),
contributing with 39, 33 and 16% to the ∑50PCBs, respectively (Fig. 04A). A slight
difference in the pro- portions of the chlorine number could be observed in the
North region stations, showing a similar or opposite proportion of those groups
(30% for 5Cl, 33% for 4Cl and 13% for 6Cl).

3
F.R. Santos, et al.
Marine Pollution Bulletin 154 (2020) 111087
6 A South

Central

North
6 25%~75%
A Range within 1.5IQR
Median Line
4 Mean

0
0 - 80 m 80 - 160 m > 300 m

0
1,0 B
0,8

0,6

0,4

0,2

0,0

South

Central

North
B
0,4

0,2

0,0
300 C

200
0 - 80 m 80 - 160 m > 300 m

250 C

200

150

100

50

South Central

2 - 3 ring PAHs
4 - 6 ring PAHs
Alkyl PAHs

North

100

200

100

0 - 80 m 80 - 160 m > 300 m

D
300 D
250
200
150
100
50
0
South
Central
North

150 E

100
50

0 - 80 m 80 - 160 m > 300 m

Stations

Fig. 02. Concentrations, in ng g−1 dry weight, of: A. ∑50PCBs; B. ∑6DDTs; C.

2–3 ring PAH, 4–6 ring PAH, alkyl PAHs; and E. ∑31PAH.

The presence of relatively higher percentages of lighter PCBs (2- and

3- atoms of chlorine) and heavier PCBs (6-, 7- and 8- atoms of chlorine)
indicates different sources other than those related to atmospheric
transport input. Studies have reported that areas distant from PCB sources
usually present a predominance of lighter congeners (1–5 Cl), associated with
long-range transport (Ma et al., 2015; Neves et al.,
2018).
Station #378 showed similar concentrations of hexa-(21%), tetra- (25%) and
pentachlorobiphenyls (21%), which is different from other sites; this, can be
attributed to the influence of the Santos – São Vicente estuarine complex, one of
the largest industrial areas of South America. The waters from this estuarine
system flow out of Santos Bay and the local accumulation of PCBs is impaired
because of the predominant currents, an effective conveyor system from the south
towards the north (Castro and Miranda, 1998).
∑6DDT varied from 0.08 to 0.83 ng g−1 dw, presenting a mean value
of 0.11 ± 0.17 ng g−1 and higher concentrations in the North region
(#372) (Fig. 02 B; Table 04S). ∑6DDT found in this study were on the same scale
as those reported in sediment cores of the East China Sea continental shelf
(Cai et al., 2016) and in sediment cores from the North Pacific to the Arctic
Ocean (Ma et al., 2015) (Table 06S).
0
0 - 80 m 80 - 160 m > 300 m

Fig. 03. Concentrations of A. ∑50PCBs; B. ∑6DDTs; C. ∑31PAHs; D. 2–3 ring PAH;

and E. 4–6 ring PAH in grouped samples in shallow (0–80 m), inter- mediate
(80–160 m), and deep (> 300 m) water regions.

DDT was introduced in Brazil in the 1940s as a solution for malaria control and
against harmful organisms in crops and livestock. In 1985, the employment of
these compounds was restricted for agricultural purposes and in the mid-1990s,
the use for vector control was reduced. In subsequent years, DDT production and
importation were radically reduced; yet, only in 2009 was its manufacture,
importation, exporta- tion, storage, marketing and use for any purpose
prohibited in Brazil (Ferreira et al., 2011; UNEP, 2012).
∑6DDT concentrations presented a marked spatial distribution, showing a
significant difference between the regions (p < .05, ANOVA) and presenting
higher concentrations in the North (0.318 ±
0.24 ng g−1), followed by the South (0.031 ± 0.018 ng g−1) and
Central regions (0.025 ± 0.016 ng g−1) (Fig. 02A). The highest con-
centration found in station #372 was located in front of Santa Catarina State.
Santa Catarina coastal area was severely affected by malaria in the past, and
diverse control methods were used, including the use of DDT on a large scale (São
Thiago, 2003). Moreover, Rizzi et al. (2017) reported higher concentrations of
DDT (122 ng g−1) in sediment from Babitonga Bay located in Santa Catarina state.

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Marine Pollution Bulletin 154 (2020) 111087
100

80

60

40

20

0
100

80

60

40

20

0
100

80

60

40

20

0
South Central North
A

South Central North

B

South Central North

C
Stations

8Cl
7Cl
6Cl
5Cl
4Cl
3Cl
2Cl

DDE, o,p' DDD, o,p' DDT, o,p' DDE, p,p' DDD, p,p' DDT, p,p'

6-ring
5-ring
4-ring
3-ring
2-ring
and 131.0 ng g−1, while the 2–3 ring PAH ranged from 1.51 to
44.9 ng g−1. The alkyl PAH concentrations varied from 6.64 to 234.50 (Fig. 02C).
The ∑31PAH values found in this study are comparable to those observed in
the Coast of Weihai, China (Zhang et al., 2016) and São Paulo Bight with
its continental shelf, Brazil (Mahiques et al., 2015). Compared to the fluvial-
estuarine systems in adjacent continental areas, such as Patos Lagoon (Medeiros et
al., 2005), La Plata River (Colombo et al., 2006) and Santos estuary (Bícego
et al., 2006), the ∑31PAH concentrations were relatively lower in this study
(Table 07S).
The ∑31PAH presented a similar spatial distribution and no sig- nificant
difference between the North, Central and South regions (p > .05,
ANOVA) (Fig. 02D). However, the South region stations showed 4–6 ring PAH
concentrations two to seven-fold times higher than alkyl- and 2–3 ring
PAHs, while samples collected on the North region presented similar
concentrations between 4–6 ring, 2–3 ring and alkyl PAHs (Fig. 02C). Therefore,
significant differences in spatial dis- tribution were observed for alkyl-,
2–3 ring and 4–6 ring PAHs (p < .05, ANOVA), caused mainly by a
northward decreasing con- tribution of 5- and 6- ring PAHs, followed by an
increase in 2-ring parental and alkyl PAHs, mainly C1-, C2- and C3-Naph (Fig.
04C). The decreasing pattern of the 2–3 ring PAHs towards deepest stations may
indicate an input influence from coastal areas (Fig. 02C). The 4–6 ring PAHs
presented a similar depth distribution, which may indicate a predominant
singular source, possibly related to hydrodynamic com- ponents and the
transport of these compounds, affecting the entire study area.
The predominance of 4–6 ring PAHs may indicate fossil fuel and biomass
combustion as the predominant sources (Barhoumi et al.,
2019). However, the physicochemical properties of these compounds allow them
to remain for more extended periods in environmental conditions, rather than
2–3 ring PAHs, and they are also easily adsorbed onto the surface of fine
particles (Lin et al., 2013).
The relatively higher concentrations of 4–6 ring PAHs in the study
Fig. 04. Relative percentage contributions of A. PCBs; B. DDTs; C. PAHs along the
Mud depocenters of the South and Southeast Brazilian Continental Margin.

∑6DDT depth distribution also presented a difference between shallow and

intermediate/deep stations, showing a decreasing trend with increasing depth
(Fig. 03B). This behavior is commonly associated with compounds related to a
predominant continental source, and due to dispersion and distance from its
origin, tends to present decreasing concentrations from coastal areas towards
the ocean.
p,p′-DDE, p,p′-DDT and p,p′-DDD were dominant in the sediment samples,
presenting a mean percentage contribution of 50.2%, 22.5% and 21.6%,
respectively (Fig. 04B). DDT ratios (p,p′-DDT/p,p′- DDE + p,p′-DDD) were
lower than 1 in the whole studied mud depo- center area, 0.21 ± 0.11 in
the shallow area, 0.38 ± 0.15 in the intermediate area, and 0.49 ± 0.36
in the deepest area, indicating no recent input. Even at low concentrations,
the presence of p,p′-DDT in its original form could be attributed to illegal
applications or dumpsites, especially in the North and coastal region stations. In
addition, DDT can be introduced as residues of contamination by pesticides, such
as di- cofol (D'Amato et al., 2002).
The total concentration of the 32 parental and alkyl-substituted PAHs (TPAH)
varied from 24.1 to 453.6 ng g−1 dw, with a mean value of 163.0 ± 97.8 ng g−1
(Table 04S). Perylene (Per) was the compound with the highest relative
contribution, accounting for mean TPAH contribution of 27%. Because perylene can
also be naturally synthe- sized pre- and post- sediment deposition
(Venkatesan, 1988; Silliman et al., 1998; Jiang et al., 2000), it will be
discussed separately.
The PAH concentrations, excluding perylene (∑31PAH), ranged from
20.7 to 286.6 ng g−1 (Fig. 02D), with the highest concentrations found
at station #372, as observed for ∑50PCBs and ∑6DDTs, followed by station
#370. The 4–6 ring PAH concentrations ranged between 13.1
area South region may be related to the higher riverine influence in this area,
especially from the La Plata River, suggesting that these com- pounds, with
a predominant pyrolytic origin, reach the marine en- vironment mainly by
contaminated sediments related to riverine dis- charge. The La Plata River plume
is the primary source of terrigenous sediments to the continental shelf between
38°S and 27°S (Nagai et al.,
2014) and its sediments are transported by the Brazilian Coastal Cur- rent
(BCC) northward through the south and southeast Brazilian con- tinental shelf
until the river's influences decrease towards lower lati- tudes (Souza and
Robinson, 2004; Möller et al., 2008; Nagai et al.,
2014).
To differentiate between combustion and petroleum sources, the ratios C0/(C0 +
C1)Flt/Phen, C0/(C0 + C1)Phen/Aant were plotted with Ant/(Ant + Phe); and to
discriminate petroleum combustion from other types of combustion, the
BaA/(BaA + Chr) and IcdP/ (IcdP + BghiP) ratios were plotted with
Flu/(Flu + Pyr) (Fig. 05; Yunker et al., 2002; Lin et al., 2017; Santos et
al., 2019).
In the cross-plots of C0/(C0 + C1)Phen/Ant and C0/(C0 + C1)Flt/Pyr vs Ant/(Ant
+ Phe), the South region presented almost all stations indicating PAHs
derived from combustion sources, except stations
#576, #568 and #570. Central region stations indicated a mixed source of
combustion and petroleum. North region showed no distinct pattern, which may
also indicate mixed sources between these regional stations.
The cross plots of BaA/(BaA + Chr) and IcdP/(IcdP + BghiP) vs Flu/(Flu + Pyr)
showed no apparent pattern of a singular source along the study area or
between the regions. These ratios may suggest that PAH compounds underwent
different degradation pathways from source formation to sediment deposition
(Zhang et al., 2005).
To clarify the multiple sources of PAH contamination, a principal component
analysis (PCA) was performed. The methyl-substituted iso- mers of Naph, Flu,
Phen, Dibenz, Pyr and Chry were not individualized and were grouped as
methylnaphthalenes (C-Naph), methylfluorene(C-

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F.R. Santos, et al.
Marine Pollution Bulletin 154 (2020) 111087

0,9

Petroleum Combustion
South region Central region North region

Petroleum

Petroleum combustion
Grass, wood and coal combustion

0,8

0,7

0,6

0,5

0,4

0,9

0,8
A
0,06 0,08 0,10 0,12 0,14 0,16 0,18 0,20

B
0,6

0,5

0,4

0,3

0,2

0,1

0,45

0,40

0,35
C

0,2 0,3 0,4 0,5 0,6

0,7

0,30

0,6

0,5

0,4
0,06 0,08 0,10 0,12 0,14 0,16 0,18 0,20
Ant/(Ant+Phen)
0,25

0,20

0,15

0,10

0,2 0,3 0,4 0,5 0,6

Flt/(Flt+Pir)

Fig. 05. PAH ratios cross plots. Left ratios: (A) An/(Ant+Phen) vs. C0/C0 +
C1 for the phenanthrene/anthracene (Phen/Ant) and (B) C0/ C0 + C1 for the
fluoranthene/pyrene (Flt/Pyr); right ratios (C) Flt/Flt + Pyr vs. IcdP/(IcdP +
BghiP) and (D) BaA/(BaA/Chry).

Flu), methylphenanthrene (C-Phen), methyldibenzothiophene (C- Dibenz),

methylpyrene (C-Pyr) and methylchrysene (C-Chry), respec- tively. Perylene
presented a small contribution to the factors during a preliminary analysis.
Therefore, it was excluded from the PCA.
Three factors with eigenvalues > 1 were observed, accounting for
82.3% of the total variance (Table 01).
The rotated Factor 1 explained 48.5% of the total variance and was positively
loaded by Ant, Flt, Pyr, BaA, Chry, C-Chry, BbF, BkF, BaP, BeP, DahA, IcdP and
BghiP. BbF and BkF were reported as tracers of diesel combustion, although IcdP
and BghiP were observed in both, diesel and gasoline combustion (Ollivon et
al., 1999; Zuo et al., 2007; Liu et al., 2009). Therefore, the Factor 1 PAH
profile is indicative of fossil fuel combustion sources.
The rotated Factor 2 explained 26.2% of the total variance and was positively
loaded by Flu, C-Flu, Phen, C-Phen, Dibenz, C-Dibenz and C- Pyr. Positive and
significant loadings of Phen and Dibenz may be as- sociated with coal
combustion (Liu et al., 2009), while the presence of C-Phen and C-Pyr could be
related to wood and coal combustion (Oros and Simoneit, 2000; Fine et al.,
2001). Based on this interpretation, Factor 2 represents sources of biomass
combustion.
The rotated Factor 3 explained 7.6% of the total variance and pre- sented
Naph, C-Naph, Acy and Ace as positively loaded values. This factor indicates
petrogenic PAH sources and could be mainly associated with oil spills from
vessels and leakage of crankcase and lubrication oil of intensive shipping
activities, in addition to urban runoff of industrial activities (Yunker et al.,
1999).
Table 01
Loadings factors of PAHs after varimax rotation.

PAHs Factor 1 Factor

2 Factor 3

Naphthalene 0.17 0.17

0.75
C-Naphthalene −0.15 0.43
0.80
Acenaphtylene 0.01 0.17
0.96
Acenaphtene −0.37 0.28
0.73
Fluorene 0.53 0.73
−0.14
C-Fluorene −0.14 0.72
0.48
Phenanthrene 0.47 0.71
0.28
C-Phenanthrene −0.15 0.93
0.11
Anthracene 0.79 0.54
0.16
Dibenzothiophene −0.19 0.92
0.12
C-Dibenzothiophene 0.45 0.75
0.14
Fluoranthene 0.92 0.20
0.00
Pyrene 0.78 0.25
−0.10
C-Pyrene 0.23 0.84
0.17
Benz[a]anthracene 0.82 0.07
−0.09
Chrysene 0.95 0.10
0.00
C-Chrysene 0.70 0.28
0.26
Benzo[b]fluoranthene 0.97 −0.05
−0.02
Benzo[k]fluoranthene 0.97 −0.06
−0.10
Benzo[e]pyrene 0.96 −0.09
0.17
Benzo[a]pyrene 0.90 −0.17
0.00
Dibenz[ah]anthracene 0.96 −0.03
−0.06
Indeno[123 cd]pyrene 0.95 −0.08
0.07
Benzo[ghi]perylene 0.95 −0.03
−0.05
Eigenvalue 11.63 6.29
1.82
% of variance 48.49 26.21
7.61
Cumulative % 48.49 74.70
82.32
The majority of South region stations presented positive values for
Factor 1, as well as station #370 in North region, indicating its source as
related to fossil fuel emissions from land transportation introduced into
marine sediment mainly via fluvial transport. Factor 2 presented positive score
values for North region suggesting a stronger influence of
Estimated source Fossil fuel combustion

Loadings > 0.70 in bold.

Biomass combustion
Petroleum

6
F.R. Santos, et al.
Marine Pollution Bulletin 154 (2020) 111087

South region

-1

-1

-1
Central region North region
Stations
the TPAHs. Relatively higher Per concentrations and percentual con- tributions
were found near coastal stations with higher terrestrial in- fluence such
as, #564 followed by #372. Station #564 is located at the mouth of Patos
Lagoon, while #372 is near the Itajaí-açu river estuary (Santa Catarina state).
Ratio values of Per relative abundance to other quantified 5-ring PAHs
(%Per/ΣPAH5) > 10% indicate predominantly natural sources, while values < 10%
are likely to represent anthropogenic inputs (Venkatesan, 1988; Hu et al.,
2014). In this study, %Per/ΣPAH5 ranged from 33.7 to 90.5%, suggesting that
Per along the study area is from natural sources. Furthermore, no significant
correlation was observed between Per and ∑31PAH concentrations (r2 = 0.36, p <
.01), which matches with non-anthropogenic sources of Per. The correlation
be- tween Per and 2–3 ring PAHs was also low (r2 = 0.12, p < .01), while for 4–6
ring PAHs, it was significant (r2 = 0.68, p < .01) due to either the source
characteristics resemblance and/or the same input or mi- gration pathway (e.g.
river input) caused by the similar high sorption affinity nature (Lin et al.,
2002; Hu et al., 2014; Xue et al., 2016).
The grain-size results ranged from 0.1 to 83.8% of sand, non-de- tected
to 31.6% of clay and 16.1 to 85.0% of silt, with a clear pre- dominance
of silt in the majority of the stations. The TOC content was in the range of
0.23% and 1.82% (Fig. 07), with a mean value of
1.02 ± 0.49%. Both sediment parameters showed no marked variation for spatial
and depth distribution, although the central region presented a lower mean value
(0.63%) when compared with south (1.7%) and north (1.05%) regions.
In Table 08S, Pearson's correlation analysis showed a higher cor- relation of
∑31PAH, 4–6 ring PAHs and Perylene concentrations with TOC content and grain
size in South and Central regions; moreover the PCB and DDT correlations were
significant only in the Central area, indicating that the TOC levels play
an important role in the con- taminant distribution of these regions. North
region showed no corre-

Fig. 06. Stations factor scores obtained by PCA analysis of South and Southeast
Brazilian Continental Margin Mud depocenters.

biomass combustion in this area, except for stations #369 and #370. Factor 3
presented positive values for stations #370 and #372, in- dicating the
presence of petroleum-related PAHs in these stations (Fig. 06).
Per concentrations ranged from 3.3 to 285.8 ng g−1 dw, with a
mean value of 49.8 ± 53.4 ng g−1, and accounted for 8.1 to 63.0% of
lation between the sediment compositional parameters and the con- taminants.
These results may be explained by the complex processing of the contaminant input,
especially due to the different pollution trans- port pathways in this region,
with the contaminant distribution more related to anthropogenic input rather
than sediment characteristics.
This study reports the first comprehensive and detailed evaluation of trace
metals, PAHs, PCBs and DDTs in surface sediments along the western South
Atlantic upper continental margin. Although in low concentrations, the levels
found for the analyzed organic contaminants were higher or in the same magnitude
of values reported for coastal and

100

80

60
South
Central
North
2,0
1,8
1,6
1,4
1,2
1,0
0,8
0,6
0,4
0,2

Clay Silt Sand

40

20

Stations

Fig. 07. Total Organic carbon (TOC) and sediment grain-size in the Brazilian
south and southeast continental margin.

7
F.R. Santos, et al.
Marine Pollution Bulletin 154 (2020) 111087

continental environments. Therefore, these results indicate that mud depocenter

regions are key areas for the monitoring of these anthro- pogenic
substances final destination. Trace metal levels showed an absence of
anthropogenic pollution, with high values of As attributed to high CaCO3 content.
Organic contaminants exhibited relatively high spatial and depth
distribution variabilities, with the highest con- centrations in North
region, near industrial, harbor and densely popu- lated areas. The presence
of a significant spatial and depth difference distribution indicates coastal
influence input for DDTs, while the lack of difference in PCBs, associated with
the predominance of low chlori- nated compounds, reflects their long-range
transport and relatively low, but not absent, local environmental influence. PAH
sources and dis- tribution indicated that pyrogenic influence from industrial
and urban activities are directly related to the higher river runoff in
southern re- gions and its transport by coastal currents towards northern
regions, while petrogenic PAHs are related to coastal activities, such as
intensive shipping and industrial activities. It is important to highlight the
im- portance of the multivariate analysis to understand the patterns of PAH
distribution, as well as to provide more detailed and valid source ap-
portionment results.

CRediT authorship contribution statement

Felipe R. Santos:Conceptualization, Formal analysis, Writing - original draft,

Writing - review & editing, Visualization.Patricia A. Neves:Conceptualization,
Investigation, Data curation, Writing - re- view & editing.Bianca S.M.
Kim:Conceptualization, Investigation, Data curation, Writing - review &
editing.Satie Taniguchi: Conceptualization, Investigation, Resources, Writing -
review & editing, Project administration, Funding acquisition.Rafael A.
Lourenço:Conceptualization, Investigation, Resources, Writing - re- view &
editing, Project administration, Funding acquisition. Cristian T.
Timoszczuk:Conceptualization, Formal analysis, Data curation.Basílio M.T.
Sotão:Conceptualization, Formal analysis, Data curation.Rosalinda C.
Montone:Conceptualization, Investigation, Resources, Writing - review &
editing, Project administration, Funding acquisition.Rubens C.L.
Figueira:Conceptualization, Investigation, Resources, Writing - review &
editing, Project ad- ministration, Funding acquisition.Michel M. Mahiques:
Conceptualization, Investigation, Resources, Writing - review & editing,
Project administration, Funding acquisition.Márcia C. Bícego:Conceptualization,
Investigation, Resources, Data curation, Writing - original draft, Writing
- review & editing, Supervision, Project administration, Funding acquisition.

Declaration of competing interest

None.

Acknowledgments

Financial support was provided by the São Paulo Science

Foundation (FAPESP), grants 2015/17763-2 and 2016/18348-1. Thanks are
due to the crew and researchers on board RV Alpha Crucis.

Appendix A. Supplementary data

Supplementary data to this article can be found online at https://

doi.org/10.1016/j.marpolbul.2020.111087.

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