Marine Chemistry 119 (2010) 44–51

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Marine Chemistry
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / m a r c h e m

Evaluation of the influence of black carbon on the distribution of PAHs in sediments

from along the entire Swedish continental shelf
Laura Sánchez-García a,⁎, Ingemar Cato b, Örjan Gustafsson a
a
Department of Applied Environmental Science (ITM), Stockholm University, SE-106 91 Stockholm, Sweden
b
Geological Survey of Sweden (SGU), P.O. Box 670, SE-751 28 Uppsala, Sweden and Department of Earth Sciences, Göteborg University, P.O. Box 460, SE-405 30 Göteborg, Sweden

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

Article history: A growing literature proposes that combusted-derived black carbon (BC) dominates the sorption and, by
Received 8 June 2009 inference, the environmental distribution and bioavailability of many hydrophobic pollutant classes. There is
Received in revised form 16 December 2009 a paucity of studies simultaneously evaluating the distribution of both BC geosorbents and pollutant sorbates
Accepted 18 December 2009
in the actual field. Here, 120 surface sediments collected by the Geological Survey of Sweden along the
Available online 6 January 2010
2000 km continental shelf along the Swedish coast facilitated evaluation of the relative influences of BC and
non-BC organic carbon (OC) on the spatial distribution of polycyclic aromatic hydrocarbons (PAHs).
Keywords:
Black carbon
The sum of 15 out of the 16 EPA PAHs ranged from 0.12 to 9.6 μg/g dry weight (dw), with the highest levels
Polycyclic aromatic hydrocarbons being found in the southern half of the Swedish Shelf (SS) area and in the vicinity of larger cities (Stockholm,
Sorption Göteborg, Malmö and Umeå). Source-diagnostic PAH ratios such as ANT/(PHE + ANT), FLT/(FLT + PYR), BaA/
Marine sediments (BaA + BPE), IPY/(IPY + BPE), CombPAH/ΣPAH and LMW/HMW suggested that pyrogenic sources are
dominating the load of PAHs in Swedish Baltic and North Sea sediments. The sediment TOC was 4.8–168 mg/
gdw (median 43 mg/gdw), while a BC concentration of 0.6–18 mg/gdw (median 1.8 mg/gdw) yielded BC:
TOC ratios spanning a wide range of 1.7–47% (median 4.6%).
Empirical distribution function tests indicated that the use of linear regression statistics was inappropriate.
Instead, evaluation with the non-parametric Spearman function yielded higher correlation coefficient (rS) for
total PAHs versus BC (0.54, p b 0.01) than versus either TOC (0.28, p b 0.01) or OC (TOC-BC; 0.26, p b 0.01).
The results from this field study, encompassing an order of magnitude more observations than any previous
sediment study, constitute a broad field manifestation of the importance of BC in affecting the distribution of
planar aromatic pollutants in aquatic environments.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction
Many polycyclic aromatic hydrocarbons (PAHs) have been
classified as “Priority Pollutants” by the US Environmental Protection
Agency (USEPA, 1985), due to their ubiquity, persistence, bioaccu-
mulation and mutagenetic potentials. The sorption of PAHs and other
hydrophobic organic chemicals (HOCs) to suspended particles and
sediments is a key process affecting their fate, transport and eco-
toxicological risks in the marine environment (Schwarzenbach et al.,
2003). Over the past decade, a new dual-mode sorption concept has
evolved for nonpolar chemicals, which holds that the sedimentary
concentration is a result of not only absorption into amorphous
organic carbon (AOC) but rather in many situations appears to be
dominated by extensive adsorption onto condensed carbonaceous
geosorbents (CG) (Pignatello and Xing, 1996; Gustafsson et al, 1997;
Huang et al, 1997; Accardi-Dey and Gschwend, 2002; Persson et al.,
⁎ Corresponding author. Tel.: +46 8 6747339; fax: +46 8 6747638.
E-mail address: laura.sanchez@itm.su.se (L. Sánchez-García).
2002; Cornelissen et al, 2005). Black carbon (BC) particles, highly
condensed residues and products of incomplete combustion, appear
to be a particularly important form of CG.
Nonlinear adsorption onto CG such as BC has been detailed in
laboratory sorption experiments, particularly for PAHs (e.g. Bucheli and
Gustafsson, 2000; Accardi-Dey and Gschwend, 2002; Jonker and
Koelmans, 2002; Kleineidam et al, 2002; Ghosh et al., 2001; Cornelissen
and Gustafsson, 2004; Zimmerman et al., 2004; Hawthorne et al, 2007)
and also for other HOCs (e.g. Cornelissen et al, 1998; Bärring et al, 2002;
Jonker and Koelmans, 2002; Braida et al, 2003; Cornelissen et al, 2005;
Lohmann et al., 2005). While these findings from laboratory-spiked
studies have been extrapolated to propose that this is also an important
process in the marine systems, there are far fewer studies that have
investigated the actual influence of BC on PAH distribution in the real
environment. To date, there are only a few limited studies that have
used field data to test whether the abundance of BC or organic carbon
(OC, defined as total organic carbon, TOC, minus BC) in sediments are
best able to explain the environmental/geographical distribution
patterns of PAHs and other planar HOCs in the marine environment
(e.g., Gustafsson and Gschwend, 1997; Persson et al, 2002; Tsapakis

0304-4203/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.marchem.2009.12.005
 L. Sánchez-García et al. / Marine Chemistry 119 (2010) 44–51 45

et al., 2003; Persson et al, 2005; Sundelin et al., 2004; Oen et al, 2006).
While results have been somewhat mixed, most studies have found that
BC is better than OC at explaining the environmental PAH distribution.
However, these real-field results are all based on low number of obser-
vations (generally, n b 10 marine sediments) covering only local-
regional scales (10–100 km). Hence, to shed light on what sediment
descriptor best describes the fate and transport of HOCs such as PAHs in
the marine environment, the objective of the current work is to perform
an evaluation of the correlation of PAHs vs. either BC or OC on a much
larger scale (100s–1000s km) and on an order of magnitude larger
database of observations (n = 120) than previous marine studies. The
extensive investigations of the exclusive economic zone (EEZ) of the
Swedish continental shelf performed by the Geological Survey of
Sweden (SGU) allowed us the opportunity for this large-scale field test.
2. Materials and methods
2.1. Study area and sediment sampling
Sediment cores of about 70 cm length were retrieved by SGU
from about 530 locations of the Swedish Shelf (SS) area between 1995
and 2006 using a Gemini gravity corer (Niemistö, 1974) as part of the
Swedish marine geological mapping progamme. 120 near-surface
samples were selected for the present project (Fig. 1). These sampling
sites are distributed throughout nine marine provinces previously
established based on geophysical constraints [Skagerrak/Göteborg
Archipelago (SK/GB); Kattegatt/Öresund (K/Ö); Arcona Sea (AS); Hanö
Bay–Southern Baltic Proper (HSB); Northern Baltic Proper (NBP);
Stockholm Archipelago (Sthlm); Southern Bothnian Sea (SB); Northern
Bothnian Sea (NB) and Bothnian Bay (BB) (Havsområdesregister,
1993), with slight modifications. Between 8 and 14 samples were
collected from each province (30 in the case of Sthlm). The 0–2 cm
section of each extruded sediment was analyzed in this study. The frozen
sediments were transported in coolers to the laboratory where they
were stored at −20 °C until further analysis.
A wide variety of urban and industrial activities are heteroge-
neously distributed along the Swedish coast. In Sweden, the industry
sector currently is represented by engineering industry (52% of the
total production), forest products (20%), chemical industry (15%),
food processing (7%) and iron and steel (5%) (Swedish Institute,
2006). Heavy industry including metal smelters, electrical engineer-
ing, high-quality steel industry and transport equipment (Näf et al,

Fig. 1. Map showing the location of the 120 marine sediments sampled from the nine provinces of the Swedish Shelf area, which are abbreviated as: SK/GB = Skagerrak/Göteborg
Archipelago; K/Ö = Kattegatt/Öresund; AS = Arcona Sea; HSB = Hanö Bay–Southern Baltic Proper; NBP = Northern Baltic Proper; Sthlm = Stockholm Archipelago; SB = Southern
Bothnian Sea; NB = Northern Bothnian Sea and BB = Bothnian Bay. Note that the limited resolution of the graphic program to represent the coastline may mislead to interpret that
some samples were collected from land, although all the 120 sediments were retrieved from the sea.
46 L. Sánchez-García et al. / Marine Chemistry 119 (2010) 44–51

Fig. 2. Plot of median and interquartile (3rd and 1st quartiles) range of BC (mg/gdw) and ΣPAHs (μg/gdw) in the nine provinces of the Swedish Shelf, going from the Norwegian to
the Finnish borders. The numbers above the bars indicate the number of unique sites in each province.

1992), is mainly developed in North Sweden. More intense combus-
tion activities (fossil fuel or biomass burning) for heating and
industry, together with denser automobile industry and road net-
works, are located in South Sweden (National Atlas of Sweden, 1998;
National Land Survey of Sweden, 2001). The principal urban areas are
located in Sthlm (Stockholm: 1.9 Mill. inhab.), SK/GB (Göteborg: 0.88
Mill. inhab.) and VH/ÖS (Malmö: 0.60 Mill. inhab.) (Statistics Sweden,
2006). The expected age of the samples are only a few years, which
lead us to consider these samples as modern and influenced by
anthropogenic period.
2.2. Quantification of PAHs
About 30 g of sediment was Soxhlet-extracted in portions of 15 g,
with acetone and hexane in two steps of 24 h each (first with 10%
acetone/aqueous volume, then with 5%). Internal standards (ß, ß-
binaftyl) were added to the acetone extract, which was diluted
twofold with 2% Na2SO4 in H2O to reduce emulsions and extracted
twice with pentane/ether 9:1. The hexane extract was washed with
2% Na2SO4 and the organic phases were then combined for the PAH
analysis.
Prior to instrumental analysis, the sample extract was fractionated
on a 10% deactivated silica gel column (70 mm long, 0.5 mm i. d.)
using 15 mL pentane, to isolate the PAH and produce a cleaner extract.
The recovery of this clean-up process was about 70–90%. The
determination of the PAH components was carried out using high
performance liquid chromatography (HPLC, Varian Prostar 240,
M410) with a C18-column and a particle size of 5 μm (Chromosphere
PAH 100* 3 mm, Chrompack, Holland). A linear gradient elution
program was used, starting with acetonitrile/water 50:50 and ending

Fig. 3. Concentration (μg/gdw) and relative contribution (%) of different PAH size classes in the sediments. The box plot depicts the median values, together with the lower and upper
quartiles. NAP: naphthalene, ANA: acenaphthene, FLU: fluorene, PHE: phenanthrene, ANT: anthracene, FLT: fluoranthene, PYR: pyrene, BaA: benzo[a]anthracene, CHR: chrysene,
BbF: benzo[b]fluoranthene, BkF: benzo[k]fluoranthene, BaP: benzo[a]pyrene, IPY: indeno[1,2,3-cd]pyrene, DBA: dibenzo[a,h]anthracene and BPE: benzo[ghi]perylene.
 L. Sánchez-García et al. / Marine Chemistry 119 (2010) 44–51 47

with 100% acetonitrile (Rathburne HPLC grade) at a flow rate of
1 mL min− 1. A fluorescence detector (Varian 9075, or Varian Prostar
363 before 2005) with a wavelength program optimized for each PAH
was used for detection. The peak heights were registered with a
chromatographic system from Varian (Star).
The individual PAH concentrations were quantified using the
certified external standard (NIST 1647d, SRM) and extraction blanks
were analyzed in parallel to the samples. The concentrations of the
individual PAHs in the blank (ca. 1–5% naphthalene, acenaphthene
and phenanthrene) were used for correction of background analyses
and adjusted for losses during the analytical work-up using the inter-
nal standard. The recovery for individual samples varied between 70
and 90%. As an additional quality control procedure, the reference
material NIST 1944 (New York/New Jersey Waterway Sediment, SRM)
was analyzed together with the samples.
The concentrations of 15 of the 16 EPA PAHs [naphthalene (NAP),
acenaphthene (ANA), fluorene (FLU), phenanthrene (PHE), anthracene
(ANT), fluoranthene (FLT), pyrene (PYR), benzo[a]anthracene (BaA),
chrysene (CHR), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene
(BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd]pyrene (IPY), dibenzo[a,h]
anthracene (DBA) and benzo[ghi]perylene (BPE)] was calculated by
comparison to the certified standard (NIST, SRM 1647d) (Brorström-
Lundén et al, 1994; Brorström-Lundén, 1995). The analyses were
ordered by SGU and performed by the Swedish Environmental
Research Institute (IVL), which is accredited as a testing laboratory
by the Swedish Board for technical Accreditation (SWEDAC).
2.3. Quantification of TOC and BC
TOC contents were determined by subjecting dry and ground
sediments to in situ microacidification (1 M HCl) followed by quan-
tification with catalytic combustion elemental analysis as detailed
previously (Gustafsson et al., 1997). The main part of the TOC data
were analyzed by MicroKemi Ltd (Uppsala, Sweden) and made
available to us by SGU. The BC was analyzed with a chemothermal
oxidation method at 375 °C (CTO-375 method), as described in
Gustafsson et al (1997 and 2001) and Elmquist et al. (2004). This
technique has been widely employed in the environmental and

Fig. 4. Source apportionment using diagnostic PAHs ratios: a) benzo[a]anthracene to benzo[a]anthracene plus chrysene (BaA/[BaA + CHR]) ratio versus combustion PAHs (sum of
FLT, PYR, BaA, CHR, BbF, BkF, BaP, IPY and BPE) to total PAHs (combPAH/SumPAH); b) fluoranthene to fluoranthene plus pyrene (FLT/[FLT + PYR]) versus anthracene to anthracene
plus phenanthrene (ANT/[ANT + PHE]) ratio. The symbols used in this figure are the same as those described in Fig 3. GDC: gasoline, diesel and crude oil; GWC: grass, wood and coal.
The end-member values for the different source-diagnostic ratios are presented in Table S2.
48 L. Sánchez-García et al. / Marine Chemistry 119 (2010) 44–51
biogeosciences (e.g. Middelburg et al, 1999; Accardi-Dey and
Gschwend, 2002; Reddy et al, 2002; Elmquist et al, 2008; Gustafsson
et al, 2009) and has compared favorably in intercomparison exercises
(e.g., Currie et al, 2002; Hammes et al, 2007). Briefly, small samples (in
order to prevent charring) of dry and finely ground sediment (ca.
10 mg) were heated at 375 °C, in Ag capsules (5 × 9 mm, Säntis
Analytical AB, Uppsala, Sweden), for 18 h under a constant air flow
(200 ml min− 1). The residual carbon content was determined as BC,
after in situ microacidification as described above, with an isotope
ratio mass spectrometer (Europa Hydra 20/20, Stable Isotope Facility,
UC Davis, USA). The limit of quantification (LOQ; defined as the mean
blank value plus 10 times the standard deviation) in this study was
3.3 μg BC per capsule. Due to the lack of standards with certified BC
concentrations, the accuracy of the method has been assessed
elsewhere (e.g. Currie et al., 2002; Gustafsson et al, 2001; Louchouarn
et al., 2007; Hammes et al., 2007) by measuring different BC-
containing NIST standard reference materials with the CTO-375
method. Based on replicate analyses of the certified reference material
SRM-1649a the precision of the method ranges from 3 to 6% (Currie
et al., 2002; Gustafsson et al, 2001).
2.4. Statistical treatment of data
While a log-normal distribution is frequently a priori assumed for
environmental contaminant concentrations, it is recommended that
one specifically evaluates what function best describes a new data set
in order to employ appropriate functions for deriving the statistical
descriptors (e.g., Parkhurst, 1988). Here, the data population for each
marine province and for the whole set was plotted as different
distributions. The relative goodness-of-fit of different distribution
functions were evaluated with an Anderson–Darling (AD) statistic
test using a statistics software package (Minitab ver. 15). None of the
tested distributions (normal, log-normal, logistic, loglogistic, extreme
value, Weibull and exponential) described properly our PAH data.
Hence, the Spearman's rank correlation coefficients (rs) was selected
for the statistical analysis, given the non-parametric character of this
coefficient (i.e., its correlation is based on ranking the two variables
and so does not rely on assumptions that the data are drawn from a
given probability distribution). The statistical software package Stata
(ver. 10, StataCorp LP) was used for the statistical treatment of the
Fig. 5. ΣPAHs (μg/gdw) as a function of BC (mg/gdw) in the 120 marine sediments of the entire Swedish Shelf area. The dashed ellipse includes samples with unusually high PAH/BC
values from the Northern Bothnian Sea (NB) region, which is known for large PAH concentrations from a major aluminum smelter industry (e.g., 24).
data, because of the accurate p-values it provides for the Spearman's
coefficient. Due to the low number of observations considered in most
of the areas, Monte Carlo permutations were applied to obtain
corrected p-values, except for Sthlm and the combined set of
observations, since both had larger data populations (n = 30 and
n = 120, respectively).
3. Results and discussion
3.1. PAH distribution in the marine sediments
Total PAHs (ΣPAH, the sum of the 15 PAHs aforementioned) were
found in the SS sediments in the concentration range 0.12–9.6 μg/gdw
(0.901.28 Q0.75
0.53 μg/gdw, as medianQ0.25, where superscript and subscript
represent the first and third quartiles, respectively) (Fig. 2) and
showed spatial variations among the different coastal areas. The
highest levels were observed in the southern regions followed by NB
and Sthlm (Fig. 2 and Table S1). The population density is highest in
the south, including the three biggest cities (Stockholm in Sthlm;
Göteborg in SK/GB and Malmö in VH/ÖS), with most of the industrial
activities. The enhanced concentration described in the Göteborg area
is in accordance with observations reported by Cato (1997), which
were based on a data set of 92 surface samples retrieved in the
Skagerrak and Kattegat areas in 1987–1992. Results from the offshore
areas show the most enhanced concentrations in the southern and
central Baltic Proper and Skagerrak (Cato, 2008). Non-point emissions
from these populated regions, combined with specific point sources,
may explain the spatial distribution of PAH concentrations. For
instance, the maximum level of PAHs (9.59 μg/gdw) was measured
outside Stockholm and the second highest (8.42 μg/kg dw) was
registered outside the aluminum smelter located in Sundsvall (NB)
(Table S1).
The most abundant of the measured PAHs were IPY, BbF, BPE and
FLT each with a median concentration around 0.1 μg/gdw and
representing 18%, 17%, 13% and 11% of the total sum of PAHs,
respectively (Fig. 3, Table S1). Similar results (19%, 19%, 13% and 9%
respectively) were found by Cato (1997). In general, the concentra-
tions of higher molecular weight PAHs (4 and 5/6 rings) dominated
over the lighter PAHs (2 and 3 rings) (Fig. 3). Thus, whereas the 4-
(PYR, BaA, CHR, BbF and BkF) and 5/6-ring compounds (BaP, DBA, BPE
 L. Sánchez-García et al. / Marine Chemistry 119 (2010) 44–51 49

Table 1 areas, including the urban nuclei with denser road networks, showed
Spearman correlations of the total and individual PAHs versus BC, TOC and OC. somewhat higher BaP/BPE ratios (medians of AH= 0.63, Sthlm = 0.69,
ΣPAH p-value PHE p-value PYR p-value BaA p-value BaP p-value SK/GB = 0.60 and NB= 0.68; Table S2). In those regions, the leakage
of refined products and vehicle exhaust might explain the higher
BC 0.54 b 0.01 0.36 b0.01 0.50 b 0.01 0.53 b 0.01 0.54 b0.01
TOC 0.28 b 0.01 0.09 0.33 0.21 b 0.05 0.21 b 0.05 0.24 b0.01 petrogenic signatures.
OC 0.26 b 0.01 0.07 0.44 0.18 b 0.05 0.19 b 0.05 0.22 b0.05
3.2. TOC and BC concentrations: relationships with PAHs

and IPY) represented each 41% of the sum of PAHs, the lighter PAHs
were only 2% (2-rings: NAP, ANA and FLU) and 16% (3 rings: PHE, ANT
and FLT) of the total. Similarly, Cato (1997) reported 86% of 4/5/6-ring
compounds and 14% of 3-rings compounds of the Σ11 PAHs in
Skagerrak and Kattegat surface sediments. Although the lower levels
of lighter PAHs in the sediments could be attributed to biodegradation
and desorption of low molecular weight PAHs (especially NAP and
ANA) during transport and deposition (Brown and Maher, 1992; Mai
There are many factors affecting PAH levels in sediments, such as
chemical properties of the compounds, composition of sediment,
depositional patterns and partitioning processes. In the present work,
the relative abilities of BC and TOC to statistically explain the
distribution of PAHs in marine sediments was investigated. The TOC
concentration in the nine provinces was measured to range from 4.8
to 168 mg/gdw (4357 32 mg/gdw), whereas BC levels varied from 0.6 to
17.7 mg/gdw (1.82.61.3 mg/gdw; Table S1). BC thus amounted to 4.63.4%
6.1

et al, 2001), the fingerprint of some PAH ratios (see below) yielded
additional diagnostic information pertaining to sources.
PAH ratios are widely used to diagnose sources (e.g. Gschwend
and Hites, 1981; Budzinski et al, 1997; Lima et al, 2005). Different
diagnostic ratios were employed in this study (ANT/[PHE + ANT], FLT/
[FLT + PYR], BaA/[BaA + BPE], IPY/[IPY + BPE] and CombPAH/ΣPAH;
for description see Table S2), which allow us to distinguish pyrogenic
versus petrogenic origin (Yunker et al., 2002 Hwang et al., 2003) .
Except for a few cases showing values of mixed signature (mainly
ANT/[PHE + ANT), the ratios spanned ranges, which point predomi-
nantly to high-temperature processes (Table S2). A cross-plot of BaA/
(BaA + BPE) and CombPAH/ΣPAH indicated typical pyrogenically
derived signatures (Fig. 4a), from fossil fuel combustion, according
to FLT/[FLT + PYR] versus IPY/[IPY + BPE] signatures (Fig. 4b).
The complete set of sediments produced LMW/HMW (lower to
higher molecular weight) PAH ratios lower than 1 (Table S2)
suggestive of pyrogenic sources (Soclo et al, 1999). The dominance
of low LMW/HMW ratios (0.01 to 0.29; Table S2), together with the
strong positive correlation (rS = 0.93) between the pyrogenic BaP
(Magi et al, 2002) and the sum of the rest of the PAHs (ΣPAH-BaP),
enables us to confirm a dominant combustion source of the PAHs at a
significant level (p = 0.000001). In concert, low BaP/BPE ratios
(median 0.53) (Table S2) pointed to pyrogenic sources other than
traffic for a majority of the samples (Pandey et al, 1999). Only some
of the TOC levels, varying all the values of BC from 1.7 to 47.1% TOC).
The BC measurements obtained here agrees with previous data
collated in (Cornelissen et al, 2005) and references included in that
study. Therein, TOC-normalized BC for around 300 sediments from
different locations around the world was median 9% (quartile range
5–18%), as quantified by the same CTO-375 method.
Sediments with higher BC contents (NBP N HSB N AS N Sthlm N K/
Ö N SK/GB) generally also contained enhanced values of PAHs
(AS N HSB N K/Ö N NBP N SK/GB N NB N Sthlm) (Fig. 2). The corollary is
that lower BC contents were also generally observed as PAH levels
decreased (i.e. SB and BB; Fig. 2 and Table S1). This trend suggests a
coupling between BC and PAH, as described previously for soils
(Bucheli et al, 2004; Nam et al, 2008) and small data set, sediment
studies (e.g., Gustafsson and Gschwend, 1997; Persson et al, 2002;
Oen et al, 2006). Statistically significant positive correlations for PAHs
versus BC were observed here when the non-parametric Spearman
correlation analysis was applied to the 120 sediment samples
(rs = 0.54, p-value b 0.01; Fig. 5). In contrast, lower correlation coef-
ficients were obtained for ΣPAH versus TOC (rs = 0.28; p b 0.01), or OC
(rs = 0.26; p b 0.01) (Table 1). These results suggest a strong rela-
tionship between PAHs and BC, as opposed to some other previous
works which reported stronger associations of PAHs or other HOCs to
TOC (e.g. Jones et al, 1989; Wilcke and Amelung, 2000; Meijer et al,
2003). Therefore, in contrast to amorphous OC being the principal

Fig. 6. Non-parametric Spearman correlation coefficients of BC (mg/gdw) versus ΣPAH (μg/gdw) and four ubiquitous individual PAHs in the nine provinces. To delineate, dashed
lines divide regression results into groups of weak (rS b 0.33), median (0.34 b rS b 0.66) and strong (rS N 0.67) correlations. The numbers of asterisks above each bar indicate the
significance level of each derived Spearman coefficient (***: p b 0.01; **: p b 0.05; *: p b 0.1). In the SK/GB province the rs for ΣPAHs, PHE and BaP are negative and not significant
(p N 0.1). The acronym TOT* refers to the correlation measured on the total set of sediments excluding those from GB/SK.
50 L. Sánchez-García et al. / Marine Chemistry 119 (2010) 44–51
factor controlling sorption of HOCs in soils and sediments (Chiou et al,
1979; Karickhoff, 1980), the results here instead suggest that BC
concentrations control the distribution of PAHs in marine sediments.
A positive correlation was also generally observed between indi-
vidual PAHs and BC (Fig. 6). The strongest associations were dis-
played in K/Ö, NB, AS and HSB, showing rs of 0.83 (p b 0.05), 0.73
(p b 0.01), 0.64 (p b 0.05) and 0.63 (p b 0.05) for the sum of PAHs.
Generally strong positive PAH–BC relationships existed for most areas
(Fig. 6), except for SK/GB, which showed no significant correlations of
BC to either individual or total PAHs. This region contains the highest
salinity among the nine SS provinces and registered the lowest
median BC values. It is plausible that the BC levels in this province are
underestimated as the presence of chloride ions in standard materials
subjected to oxidation tests have previously been demonstrated to
enhance degradation of BC during the thermal-oxidation treatment
(Elmquist et al, 2004). Enhanced overall correlation is obtained
when the relationship between BC and PAHs is tested after excluding
the SK/GB sediments (TOT* = TOT − SK/GB; Fig. 6). In contrast,
weaker correlations were observed between PAHs and OC (e.g.,
PHE: rs = 0.07, p b 0.5; PYR: rs = 0.18, p b 0.05; BaA: rs = 0.19, p b 0.05;
BaP: rs = 0.22, p b 0.05). These results are consistent with dominance
of adsorption of PAHs to BC in marine coastal sediments (Gustafsson
et al, 1997). Thus, the PAH distribution along this extensive coastal
system is best explained by association with the carbonaceous
geosorbent sub fraction of the marine sediments.
The PAH-to-BC mass ratio (mg/g) was calculated to allow for a
crude assessment of the form of association of PAHs onto the
carbonaceous surface of the sediment BC. The ratio varied from 0.06
to 4.16 mg/g (0.470.63
0.32 mg/g; Table S1), which is near the low end of
maximum site sorption capacities (Qmax) reported from laboratory-
based sorption isotherms (Bucheli and Gustafsson, 2000; Cornelissen
and Gustafsson, 2004; Van Noort et al, 2004), which ranges from 0.5 to
19 mg PAH/g BC. The PAH-to-BC ratios of the nine provinces were
positively correlated with the PAH-vs.-BC Spearman coefficient
(rs = 0.58, p b 0.1), which denotes a concordance between the co-
distribution of PAHs and BC in the environment and sorption
capacities. These field-based findings confirm the importance of BC
geosorbents for the environmental behavior and distribution of
contaminants like PAHs. Given the considerable influence of strong
PAH–BC associations on the bioavailability of these organic con-
taminants in aquatic systems, the results obtained here highlight the
relevance of taking these sorption processes into account in the
establishment of sediment quality criteria.
4. Summary
To increase our understanding of the role of BC in explaining the
environmental distribution of organic pollutants such as PAHs, 120
marine sediments collected from outside the 2000 km long coast of
the Swedish Continental Shelf were here investigated. At the N99%
confidence limit, a much higher positive correlation coefficient was
observed for PAHs with BC (rS = 0.54) than with TOC (rS = 0.28) or OC
(rS = 0.26). Hence, BC is a better descriptor than other OM forms of
the geospatial distribution of the PAHs in the marine environment.
Further, the coupling between PAH-to-BC ratios and PAH-vs.-BC (non-
parametric Spearman coefficient of rS = 0.58, p b 0.1) supported the
environmental co-distribution of PAHs and BC. These observations,
encompassing an order of magnitude larger sedimentary data set than
previous studies, are a broad field manifestation of the importance of
BC association for the distribution of PAH in aquatic environments.
Acknowledgements
We thank Martin Kruså for technical assistance. This work was
primarily supported by a grant from the Geological Survey of Sweden
(SGU, contract no. 60-1341/2006). Data on PAHs and TOC were kindly
put to our disposal by SGU. The authors Ö.G. and L.S-G. also
acknowledge an Academy Research Fellow grant from the Swedish
Royal Academy of Sciences and an EU Marie Curie grant (contract no.
PIEF-GA-2008-220424), respectively.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.marchem.2009.12.005.
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