Marine Pollution Bulletin 95 (2015) 155–165

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Marine Pollution Bulletin

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

PAHs in the Ría de Arousa (NW Spain): A consideration of PAHs sources

and abundance
Begoña Pérez-Fernández a,b, Lucía Viñas a,⇑, M. Ángeles Franco a, Jesica Bargiela a
a
Instituto Español de Oceanografía, Centro Oceanográfico de Vigo, Cabo Estay – Canido, 36390 Vigo, Spain
b
Campus do Mar, Universidade de Vigo, 36310 Vigo, Spain

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

Article history: Analysis of 35 parental and alkylated homologues of PAHs (Polycyclic Aromatic Hydrocarbons) was car-
Received 13 October 2014 ried out in eleven marine sediment samples collected along a central transect in the biggest Galician ría.
Revised 30 March 2015 The samples were collected using a box-core dredge and, after freeze-drying, were kept frozen until anal-
Accepted 11 April 2015
ysis. The sediments were extracted by PLE (Pressurized Liquid Extraction) procedure and the quantifica-
Available online 7 May 2015
tion of PAHs was performed using gas chromatography coupled to mass spectrometry (GC–MS) with the
aid of deuterated PAH internal standards. The total concentration of studied PAHs (R35PAHs) ranged from
Keywords:
44.8 to 7901 ng g1 dry weight (d.w.). The highest PAH concentrations were found in sediments collected
PAHs
Sediments
near the harbour (7901 ng g1) and the cleanest positions were located in the outer zone of the ría.
Sources To date, these results are the first data presented in the area so they could be used for regular moni-
Alkylated PAHs toring and control of future pollution episodes.
Toxicology Ó 2015 Elsevier Ltd. All rights reserved.
Spain

1. Introduction economic development of this community. In particular, the Ría

One of the most complex littoral environments of the Iberian
Peninsula can be found in Galicia, the longest coastline
(1720 km) with very special geological formations, the Galician
estuaries, named ‘‘rías’’ by Von Richthofen in 1886 (Mendez and
Vilas, 2005). From a geological point of view, Ría de Arousa has a
large number of islands and islets among which Arousa Island,
inside the estuary, and Sálvora, near its mouth, are the most impor-
tant ones. Two rivers create the drainage system of the ría; these
are rivers Ulla and Umia. The river Ulla flows into the head of the
ría and the river Umia flows into the bay that forms the peninsula
of El Grove within Cambados coast (Rodríguez-García, 2008).
These formations constitute a highly productive ecosystem due
to coastal upwelling of deep, nutrient rich water, which generally
occurs between May and September, providing the perfect condi-
tions for a thriving aquaculture exploitation (Blanton et al.,
1987). Starting in the late 1940s with the settling of the firsts mus-
sels’ rafts in the Ría de Arousa, the mussels’ productivity has
increased, according to the last publications from the Regulatory
Council, up to a production of over 200  106 kg year1 in 2012.
Mussel culture in the area is, therefore, of great economic and
social importance generating about 11,500 direct and 7000 indirect
jobs, becoming a strategic sector in the present and future
⇑ Corresponding author.
E-mail address: lucia.vinas@vi.ieo.es (L. Viñas).
de Arousa has both the biggest area (230 km2) among the
Galician rías and the biggest number of mussel rafts (2292) almost
70% of the total rafts in Galicia (www.mexillondegalicia.org).
Moreover, coastal and estuarine areas are the most sensitive
places to the impacts caused by pollution and that is the reason
for the setting, in 1999, of a monitoring programme carried out
by the Spanish Institute of Oceanography that checks the environ-
mental conditions of these areas. This program has identified some
stations as the most polluted in Galicia which are, in order of
decreasing amount, Ría de Coruña, Ría de Vigo, Ría de Pontevedra
and Ría de Arousa. In 2002 the Prestige oil spill reached the
Galician coast increasing the pollution concern in the area.
So, the study of PAHs in Ría de Arousa is of paramount interest.
On one hand because of the economic implications that it can have
in terms of mussels’ production and, on the other hand, due to the
high sensibility of the area as it has already suffered some PAH
inputs probably caused by the nearby populations and the intense
maritime traffic.
In addition, and unlike other rías that have been deeply studied
(García et al., 2013; Viñas et al., 2009), the Ría de Arousa has scar-
cely been investigated (Prego and Cobelo-García, 2003; Otero et al.,
2005) and the work presented here is, as far as we know, the first
study of PAHs in Arousa’s marine sediments.
Polycyclic aromatic hydrocarbons are a diverse group of aro-
matic compounds containing two or more fused arene structures.
Some of them are classified as priority pollutants by the United

http://dx.doi.org/10.1016/j.marpolbul.2015.04.028
0025-326X/Ó 2015 Elsevier Ltd. All rights reserved.
156 B. Pérez-Fernández et al. / Marine Pollution Bulletin 95 (2015) 155–165
States Environmental Protection Agency (U.S. EPA, 2002) and they
are known to exert acutely toxic effects and/or present mutagenic,
teratogenic, or carcinogenic properties.
They are ubiquitous organic contaminants formed by the
incomplete/inefficient combustion of organic material, diagenesis
and biosynthesis (Boitsov et al., 2009; Wang et al., 2007;
Budzinski et al., 1997). The PAHs can reach the environment from
various sources that include domestic, mobile, industrial, agricul-
tural and natural inputs (Ravindra et al., 2008). Domestic emissions
include primarily the combustion of wood, oil or coal and will be
noticed in urban areas specifically during winter. Mobile sources
include the emissions from all type of vehicles. In urban areas
emissions from vehicle exhaust are the largest contributors and
in coastal areas emissions from shipping are also significant.
Aluminium production, cement manufacture, waste incineration
and petrochemical industries have been included as the most
important industrial sources of PAHs. Burning of agricultural
wastes and forest fires contribute to the emissions of PAHs but
the uncertainty associated with these activities makes this type
of emissions difficult to quantify. Other minor sources known as
natural ones include the non-anthropogenic burning of forests, vol-
canic eruptions and cosmic dust.
PAHs have a low water solubility and hydrophobic nature and
so they tend to be associated with inorganic and organic material
in suspended solids and sediments (Webster et al., 2001). In gen-
eral, most PAHs (with the exception of some low-molecular weight
compounds, such as naphthalene) will be strongly adsorbed to par-
ticulate matter and biota in the aquatic environment.
Different feeding modes will have an impact on the exposure
degree of organisms to contaminants. Filter feeding animals, such
as mussels, can accumulate high levels of PAHs and other contam-
inants due to their high filtration rate and besides, due to their low
metabolization capacity they even bioaccumulate them (Douben,
2003; Ruiz et al., 2011).
Besides the usual parent PAHs compounds included in most
works, we have also analysed alkylated naphthalenes, phenanthre-
nes, chrysenes and dibenzothiophenes that show an increase in
hydrophobicity and bioaccumulation. So in this work, the abun-
dance of parent and alkylated PAHs and their possible sources
are investigated; up to 35 individual compounds were analysed
and the total amount present in sediments as long as their possible
sources are presented and discussed.
2. Materials and methods
2.1. Chemicals and reagents
Suprasolv grade acetone, hexane, silica gel (0.063–0.2 mm), neu-
tral alumina (70–230 mesh) and anhydrous sodium sulphate for
analysis were obtained from Merck (Darmstadt, Germany). A stan-
dard mixture of PAH deuterated containing: naphthalene-d8, biphe-
nyl-d10, anthracene-d10, dibenzpthiophene-d8, pyrene-d10 and
benz[a]pyrene-d12 was obtained from CIL (Massachusetts, USA). A
PAH mixture containing Naphthalene, Biphenyl, 2-
Methylnaphthalene, 1-Methylnaphthalene, 2,3-Dimethylnaphthalene,
Acenaphthylene, Acenaphthene, 2,3,6-Trimethylnaphthalene,
Fluorene, Dibenzothiophene, Phenanthrene, Anthracene, 4-
Methyldibenzothiophene, 2-Methylphenanthrene, 2,8-
Dimethyldibenzothiophene, 1,6-Dimethylphenanthrene, Fluoranthene,
2,4,7-Trimethyldibenzothiophene, Pyrene, 1,2,8-Trimethyl-
phenanthrene, 1-Methylpyrene, Benzo(c)phenanthrene,
Benz(a)anthracene, Triphenylene, Chrysene, 2-Methylchrysene,
7,12-DimethylB(a)anthracene, Benzo(b)fluoranthene, Benzo(k)
fluoranthene, Benzo(e)pyrene, Benzo(a)pyrene, Perylene,
Indeno(1,2,3-c,d)pyrene, Dibenzo(a,h)anthracene, Benzo (g,h,i)
perylene was prepared from mixtures from CPA Chem (Bulgaria)
and Chiron (Trondheim, Norway).
2.2. Study area and sampling procedure
The sampling positions were carefully conceived to describe the
Ría de Arousa and the sediments were collected on a transect from
river Ulla to the outer of the ría.
The great number of mussels rafts culture areas were also taken
into account, avoiding sampling under and/or close to them. The
production of biodeposits from the rafts may reach up to
190 kg day1 per mussel raft. Mussels’ biodeposits can perturb
the sediments grain distribution and also its organic content.
Sampling was carried out aboard the R/V José María Navaz during
the 2011 spring period and the sampling sites can be seen in Fig. 1.
Sediments were collected with a box corer dredge and the sur-
face layer was immediately sampled and frozen on board and then
freeze-dried and homogenized in the laboratory. The stations
depths varied between 5.30 and 77.0 m; this and other sample fea-
tures are shown in Table 1.
2.3. Sample extraction and analysis
Pressurized liquid extraction (Accelerated Solvent Extraction
(ASE) ASE™ 350, Thermo Scientific™ Dionex™, Sunnyvale, CA
USA) was used to prepare the samples by means of the following
procedure listed in Table 2: 3 g of the freeze-dried sediment
together with diatomaceous earth were loaded in ASE cells and
were spiked with a mixture of six deuterated PAHs (naphthalene-
d8, biphenyl-d10, anthracene-d10, dibenzpthiophene-d8, pyrene-
d10 and benzo[a]pyrene-d12) and extracted with hexane–acetone
(1:1) in a 22 mL stainless steel extraction cell. Extraction was per-
formed at 100 °C for 10 min in 2 cycles. The recovered extracts were
treated overnight with recently activated copper for elemental sul-
phur removal and then carefully evaporated to 1 mL for further
cleaning through an alumina column and finally evaporated again
to 1 mL to obtain the suitable extract to be analysed.
The analytical characterization of PAHs was performed by a GC/
MS Thermo mod DSQ II (Thermo Electron Corporation, Austin, TX
USA). The GC (TRACE GC Ultra) was equipped with a 0.25 mm
internal diameter, 60 m fused silica capillary column with a 5%
phenylsubtituted methylpolysiloxane phase (0.25 lm film thick-
ness) (DB-5 MS, J&W Scientific Folsom, CA) and helium was used
as carrier gas. The temperature operating conditions were: held
at 50 °C for 3 min ramped to 200 °C at 6 °C/min and finally to
315 °C at 4 °C/min holding that temperature for 15 min. The sam-
ple was injected using an on-column injection system and the
purge valve was activated 30 s after the injection. Transfer line
and ion source temperatures were held at 280 °C and 220 °C,
respectively. The MS was operated in the electron impact (EI) mode
at 70 eV and the spectrum divided into 8 SIM windows, each
scanned for up to 7 molecular masses, previously optimized, for
the corresponding analytes and the deuterated internal standards
eluting in this windows.
2.4. Quality assurance and quality control (QA/QC) of analysis
Replicate measurements were done for all collected samples in
each station. Reagents blank and recovery procedures were anal-
ysed simultaneously for every batch of samples.
Average recovery of PAHs ranged from 55% to 114%. The
method detection limits for individual PAHs was calculated to be
from 0.25 to 2.62 ng g1 d.w. according to the analytical method.
Quantitation of parent and alkylated PAH reported in Table 3
was recovery corrected sample by sample with the corresponding
deuterated compounds with Xcalibur software package.
 B. Pérez-Fernández et al. / Marine Pollution Bulletin 95 (2015) 155–165 157

Fig. 1. Sediment sampling locations in Ría de Arousa.

Table 1 were used as internal reference materials obtaining satisfactory

Sampling points location and characteristics. results.
Code Coordinates Depth of water <63 lm T.O.C.
(m) (%) (%)
3. Results and discussion
AR02 42°37.4200 N 8°48.1000 W 5.30 46.0 2.98
AR04 42°36.6100 N 8°49.9000 W 14.5 53.7 3.03
AR12 42°34.8800 N 8°53.4000 W 45.0 61.9 2.81 3.1. Organic carbon and particle size analysis
AR14 42°34.1800 N 8°54.7700 W 53.0 68.6 2.20
AR18 42°32.8800 N 8°55.6600 W 68.0 50.4 2.10 Organic carbon content was determined using an elemental
AR21 42°31.8500 N 8°56.4000 W 50.0 86.5 3.47
AR24 42°30.8100 N 8°57.3800 W 53.0 39.5 2.00
analyser (model 2400 series II, CHNS/O, Perkin Elmer, Inc,
AR27 42°29.6500 N 8°57.9500 W 61.3 22.2 0.74 Shelton, USA). Sediment samples were ground in an agate mortar
AR29 42°28.1400 N 8°58.5000 W 58.0 9.28 0.59 and then treated with hydrochloric acid 25% to remove inorganic
AR31 42°26.5000 N 8°59.0000 W 68.0 82.6 – carbon.
AR32 42°25.5000 N 8°59.7300 W 77.0 2.28 0.50
The sediment fraction was determined by wet sieving on a
63 lm sieve to obtain two grain-size fractions, <63 lm and
>63 lm. The results are listed in Table 1.
Table 2 Fig. 2 shows the relationship between %TOC with the sum of
Conditions used for Accelerated Solvent Extraction (ASE). PAHs. Although the relationship between organic matter and
Parameter Value PAH concentrations is widely established, some exceptions have
Solvent Acetone:hexane (1:1)
been reported (Guinan et al., 2001; Franco et al., 2006;
Temperature 100 °C Cavalcante et al., 2009; Chen and Chen, 2011) and the present sam-
Static time 10 min ples show a poor correlation (r2 = 0.376) between the PAH content
Flush volume 60% and the organic matter content.
Purge time 100 s
This lack of correlation can have two different explanations
Number of cycles 2
(León et al., 2014); firstly a situation of not equilibrium between
the PAHs and the sedimentary organic matter due to a recent input
and secondly a masking event as a consequence of an organic mat-
A minimum of five PAH mixture standards were run on the ter enrichment suffered in the area due to the aquaculture indus-
same day of the samples analysis to build the linear regression try. In the studied watershed there are an important number of
curves by plotting the peak area ratios versus each PAH concentra- mussels’ rafts and so their shells and excrements will modified
tions; the obtained correlation coefficient has to be at least P0.99 the organic matter content and the equilibrium will hardly be
to be acceptable. achieved.
Four different sediments used in the lab to participate in inter- An improvement in the relationship RPAHs–%TOC can be
calibration exercises organised by Quality Assurance of reached by considering three outliers; when samples AR02, AR04
Information for Marine Environmental Monitoring (QUASIMEME) and AR21 are not taken into account the correlation improves to
158 B. Pérez-Fernández et al. / Marine Pollution Bulletin 95 (2015) 155–165

Table 3
List and concentrations of PAHs measured in sediments as ng g1 in dry sediments.

Compound Compound acronym Mean Max Min

Naphthalene Naph 15.1 ± 12.3 35.9 0.8
Biphenyl Biph 12.4 ± 8.3 27.5 1.7
2-Methylnaphthalene 2-MNaph 6.1 ± 3.5 11.9 1.0
1-Methylnaphthalenea C1-Naph 1-MNaph 7.5 ± 4.6 14.5 1.5
2,3-Dimethylnaphthalenea C2-Naph 2,3-MNaph 3.0 ± 2.3 7.2 <LOD
Acenaphthylene Acy 2.7 ± 3.4 10.1 <LOD
Acenaphthene Ace 4.3 ± 4.2 12.1 <LOD
2,3,6-Trimethylnaphthalenea C3-Naph 2,3,6-MNaph 3.3 ± 3.3 11.5 0.6
Fluorene Flu 13.0 ± 15.8 47.0 0.7
Dibenzothiophene DBT 12.9 ± 15.7 44.0 0.3
Phenanthrene Phe 128.3 ± 170.0 512.6 3.3
Anthracene Ant 3853.8.3 ± 169.1 1.6
4-Methyldibenzothiophenea C1-DBT 4-MDBT 9.7 ± 11.9 38.3 0.6
2-Methylphenanthrenea C1-Phe/Ant 2-MPhe 34.8 ± 48.3 155.0 1.1
2,8-Dimethyldibenzothiophenea C2-DBT 2,8-MDBT 10.3 ± 16.9 55.6 0.5
1,6-Dimethylphenanthrenea C2-Phe/Ant 1,6-MPhe 10.2 ± 15.1 51.1 0.4
Fluoranthene Fla 328.5 ± 469.1 1277.7 4.6
2,4,7-Trimethyldibenzothiophene aC3-DBT 2,4,7-MDBT 2.5 ± 2.0 6.4 <LOD
Pyrene Pyr 249. ± 358.9 974.3 1.7
1,2,8-Trimethylphenanthrenea C3-Phe/Ant 1,2,8-MPhe 1.6 ± 1.4 4.6 <LOD
1-Methylpyrenea C1-Fla/Pyr 1-MPyr 13.1 ± 20.2 63.7 <LOD
Benzo(c)phenanthrene BcPhe 22.7 ± 32.2 96.3 <LOD
Benz(a)anthracene BaA 163.0 ± 252.4 770.9 0.6
Triphenylene Triph 136.1 ± 187.1 561.2 0.7
Chrysene Chry
2-Methylchrysenea C1-B(a)A/Chry 2-MChry 25.5 ± 36.0 112.9 <LOD
7,12-DimethylB(a)Aa C2-B(a)A/Chry 7,12-MBaA 3.6 ± 3.2 10.6 0.5
Benzo(b)fluoranthene BbF 240.0 ± 331.6 893.8 1.2
Benzo(k)fluoranthene BkF 97.6 ± 131.3 364.9 1.3
Benzo(e)pyrene BeP 115.9 ± 160.0 436.4 0.8
Benzo(a)pyrene BaP 148.6 ± 220.1 592.2 0.8
Perylene Per 52.3 ± 62.3 184.0 <LOD
Indeno (1,2,3-c,d)pyrene IP 80.1 ± 102.0 295.2 0.6
Dibenzo(a,h)anthracene DBahA 28.6 ± 38.3 103.5 0.7
Benzo(g,h,i)perylene BghiPer 77.8 ± 97.3 281.0 0.9
a
Identified a target compound used to integrate the defined group.

The relationship RPAHs versus %<63 lm is presented in Fig. 3.

In this case a good relationship is only achieved when samples
AR02, AR04, AR21 and AR31 are left out of the representation.
This lack of correlation is in line with the idea that the variability
in total PAHs appeared to be driven by other factors, such as the
proximity of sampling sites to input sources, rather than sediment
properties (Martínez-Lladó et al., 2007; Kucklick et al., 1997).

3.2. PAHs concentrations

In the present study thirty-five PAH compounds were studied in

Fig. 2. Relationship between RPAHs and organic carbon content of Ría de Arousa
sediments.
r2 = 0.9262. These three samples are, among the studied ones, the
closest to direct organic inputs; AR02 and AR04 are the closest to
the river Ulla so, directly influenced by its discharges and AR21
could be influenced by rafts and their residues.
all sediment samples collected from Ría de Arousa. Among these 35
PAHs there are the sixteen U.S. EPA priority PAH compounds. All
the individual PAHs values in this study are tabulated (Table 3)
as mean, maximum and minimum. Concentrations of R35PAH
and R16PAH found in samples are displayed in Fig. 4.
Using either of the indicators is easily identify a perfect distri-
bution from the inner to the outer area of the studied ría; as
expected the PAHs amount decrease as we move from the inner
ría to the open sea.
AR02, placed in the inner part of the ría close to the mouth of
the River Ulla, infer the highest RPAH, this fact may be attributed
to river contributions from nearby populations. The biggest
decrease between two samples take place in the inner part of the
ría; e.g. comparing sample AR02 and AR12 it was found a fourfold
decrease in the concentration and the same situation takes place
between sample AR04 and AR14.
The lowest concentration was found in AR32 that it is away
from the coast and therefore less affected by human contributions.
R35PAH concentrations were in the range of 44.8–7901 ng g1
d.w., with the mean value 2099 ng g1 d.w. As 16 PAH defined by
 B. Pérez-Fernández et al. / Marine Pollution Bulletin 95 (2015) 155–165 159

Table 4
Ranges of PAH from different studies.

Area Range RPAHs References

(ng g1 d.w.)
S. Carolina Estuary, USA 33–9600 Kucklick et al. (1997)
(R28PAHs)
NW Mediterranean Sea, 119–1720 Benlahcen et al. (1997)
Spain (R14PAHs)
Gironde Estuary, France 19–4888 Budzinski et al. (1997)
(R17PAHs)
Mediterranean Sea, Spain 30–870 Baumard et al. (1998)
(R12PAHs)
England and Wales 25–37,110 Woodhead et al. (1999)
(R13PAHs)
Benin (R14PAHs) 25–1450 Soclo et al. (2000)
France(R14PAHs) 4–855 Soclo et al. (2000)
Pearl River, China 10.8–2432 Mai et al. (2002)
(R16PAHs)
Michigan Lake, USA 5.2–9790 Kannan et al. (2005)
(R7PAHs)
Galicia continental shelf, 0.9–422 Franco et al. (2006)
Spain (R13PAHs)
Ria de Vigo, Spain 29–3203 Viñas et al. (2009)
(R13PAHs)
SW Barent Sea, Norway 58.8–326 Boitsov et al. (2009)
(R30PAHs)
Norwegian Sea, Norway 9.5–2496 Boitsov et al. (2013)
(R30PAHs)
Ría de Arousa, Spain 45–7901 Present work
(R35PAHs)
Ría Arousa, Spain 23–6647 Present work
Fig. 3. Relationship between RPAHs and particle size (%<63 lm) of Ría de Arousa (R16PAHs)
sediments.

EPA are more commonly determined and more published data

R16PAH are available, this parameter has also been calculated
and shown in Table 4. Concentration of PAHs in Ría de Arousa sed-
iments were higher than in Galician continental shelf sediments
but lower than those in Michigan Lake in USA and S. Carolina
Estuary, USA.
Focusing on the PAH composition, Fla and Pyr were the most
abundant PAH in all collected sediments except from AR32. On
the other hand methylated compounds and Acy were the less
abundant PAHs. Similar PAH distribution patterns were previously
reported in sediments from the Galician coast (Viñas Diéguez et al.,
2002) the Mediterranean Sea (Baumard et al., 1998) and the
Milwaukee Harbour, USA (Ghosh et al., 2000). According to this
general PAH distribution, sediments contain a prevailing contribu-
tion of pyrolytic compounds (Fla, Pyr and heavier PAHs) (Colombo
et al., 2006).
Low molecular weight (LMW) PAH such as Acy, 1-MNaph and
Biph were among the most abundant PAH in AR32, the situation
Fig. 4. PAH concentrations in the studied samples as sum of 35 PAHs and 16 EPA
PAHs expressed in ng g1 d.w.
of this sample out of the bay far away from city runoffs make it
the cleanest sample with low values for all PAH studied. It can
be concluded that the relative high amount of LMW PAHs can be
related with petrogenic inputs due to unscrupulous or direct dis-
posal of diesel oil and other unburned fuel from boats. (Nasher
et al., 2013; Vane et al., 2014; Monikh et al., 2014; Kim et al., 2008).
3.3. Assessment of sediment quality using biological thresholds
To assess sediment quality, PAH levels in sediments were com-
pared with background assessment concentrations (BAC) defined
in relation to the background concentrations (BCs) and some other
effects-based sediment guideline values.
BACs were developed by the OSPAR Convention (OSPAR, 2009)
for testing whether concentrations are near background levels and
were used to prepare the Quality Status Report 2010 (QSR2010).
The values detailed in Table 4 are not normalised to TOC and were
compared to the non-normalised BAC defined for Spain in the
reference.
All PAH evaluated in samples AR02, AR04, AR12, AR14, AR18,
AR21, AR24 and AR27 were above the defined BAC. The cleanest
samples were AR29, 31 and 32. AR32 infer values below BAC for
all PAH determined. In AR29 only Ant exceed this value and
AR31 display higher concentration than the BAC for Phe and Ant.
ERLs and ERMs were first calculated by NOAA (NOAA, 1999)
using existing toxicity data compiled from completed toxicity
assays. The available data was ranked and then the 10th percentile
of the ranked data is identified as the Effects Range-Low (ERL) and
is considered indicative of concentrations below which adverse
effects rarely occur. The 50th percentile of the ranked data is iden-
tified as the Effects Range-Median (ERM), and is indicative of con-
centrations above which adverse effects frequently occur.
These ERL and ERM values formulated by Long et al. (1995)
have been widely used to characterize toxic levels of chemicals
in marine and freshwater sediment.
160 B. Pérez-Fernández et al. / Marine Pollution Bulletin 95 (2015) 155–165

Based upon these values the United States Environmental 7000.0

Protection Agency (EPA) defines three different categories for eval-
6000.0
uating contaminant level within estuaries: ‘‘good’’ for zero ERL
exceedances, ‘‘intermediate’’ if there are ERL exceedances but zero 5000.0
ERM exceedances, and ‘‘poor’’ for any ERM exceedance (U.S. EPA, 4000.0
2012). Total TEQ
ERL and ERMs are available for the PAHs present in Table 5, and 3000.0
suma 16 PAH
the studied samples were classified based on it. For 82% of the sam- 2000.0
ples, individual PAHs did not exceed ERL and these stations will be
classified as ‘‘good’’; for samples AR02 and AR04 some PAH (Flu, 1000.0

Phe, Ant, Fla, Pyr, BaA, Chry/Triph, BaP, IP, DBahA, BghiPer and
C1-Naph) showed values above ERL but in all cases below ERM
which indicates that biological effects would occur occasionally.
No samples contained PAHs whose concentrations exceed ERM
and so no ‘‘poor’’ condition is identified in the area.
3.4. Sediment potential toxicity based on carcinogenic PAHs
Among the studied PAH, seven of them have been classified as
probable human carcinogens: BaP, BaA, Chry, BbF, BkF, DBahA,
and IP (Guo et al., 2011; Peters et al., 1999).
An easy approach to assess sediment toxicity based on this car-
cinogenic PAHs was defined in 1995 by Long and implemented to
0.0
Fig. 5. Sum of 16 PAHs (ng g1) and total TEQ in the studied samples.
classify sediments at Langkawi Island, Malaysia by Long et al.
(1995) and Nasher et al. (2013). These authors define an ERLcarc
of 1373 ng g1 and an ERMcarc of 8410 ng g1. The sum concentra-
tions of PAHcarc in the sediments of Ría de Arousa ranged from 5.95
to 3524 ng g1 d.w., with a mean concentration of 893.9 ng g1
d.w. These results are lower than the ERM value defined, and only
two samples, AR02 and AR04, are above this value but below the
ERL defined.

Table 5
Sediment quality classification. BC, BAC, ERL and ERM expressed in ng g1.

Compound QSR2010a SQCb Stations (S)

BC BAC ERL ERM n° of S < ERL >ERL and <ERM
Naphthalene – – 160 2100 11 –
Acenaphthylene – – 44 640 11 –
Acenaphthene – 16 500 11 –
Fluorene – 19 540 9 AR02, AR04
Dibenzothiophene – 190 1200 11 –
Phenanthrene 4.0 7.3 240 1500 9 AR02, AR04
Anthracene 1.0 1.8 85 1100 9 AR02, AR04
Fluoranthene 7.5 14.4 600 5100 9 AR02, AR04
Pyrene 6.0 11.3 665 2600 9 AR02, AR04
Benz[a]anthracene 3.5 7.1 261 1600 9 AR02, AR04
Chrysene/Triph 4.0 8.0 384 2800 9 AR02, AR04
Benzo[a]pyrene 4.0 8.2 430 1600 9 AR02, AR04
Indeno[123-cd]pyrene 4.0 8.3 240 950 9 AR02, AR04
Dibenzo(a,h)anthracene – 63 260 9 AR02, AR04
Benzo[ghi]perylene 3.5 6.9 85 330 9 AR02, AR04
C1-naphthalene – – 155 1450 11 –
C2-naphthalene – – 150 1450 11 –
C1-phenanthrene – – 170 2000 9 AR02, AR04
C2-phenanthrene – – 200 2500 10 AR02
C1-dibenzothiophene – – 85 600 11 –
a
OSPAR, 2010. Quality Status Report 2010. OSPAR Commission. London.
b
SQC: Sediment Quality Criteria.

Table 6
Sediment potential toxicity classification.

Area RCPAHs ng g1 d.w. Total TEQ ng g1 d.w. Data References
Vardø harbour, Barents Sea 870–1412 472–733 Konieczny (1996) Savinov et al. (2003)
Vadsø harbour, Barents Sea 68–124 40–66 Konieczny (1996) Savinov et al. (2003)
Jarfjord, Barents Sea 30–70 19–35 Konieczny (1996) Savinov et al. (2003)
Korsfjord, Barents Sea 30–134 18–60 Konieczny (1996) Savinov et al. (2003)
Kola Bay, Barents Sea 240–1211 71–583 Iljin et al. (1997) Savinov et al. (2003)
Guba Pechenga, Barents Sea 63–864 18–300 Savinov et al. (2003) Savinov et al. (2003)
Meiliang Bay, China 621–2737 94–856 Qiao et al. (2006) Qiao et al. (2006)
Naples Harbour (industrial area) 3–6316 4–4723 Sprovieri et al. (2007) Chen and Chen (2011)
Naples Harbour (external area) 3–4190 2–1629 Sprovieri et al. (2007) Chen and Chen (2011)
Naples Harbour (touristic area) 3–9879 10–2250 Sprovieri et al. (2007) Chen and Chen (2011)
Kaohsiung Harbor, Taiwan 256–8067 55–1964 Chen and Chen (2011) Chen and Chen (2011)
Langkawi Island, Malaysia 270–744 76.3–174.6 Nasher et al. (2013) Nasher et al. (2013)
Ría Arousa (Inner) 446–3524 92–820 Present study Present study
Ría Arousa (Outer) 5.95–374 1.2–79 Present study Present study
 B. Pérez-Fernández et al. / Marine Pollution Bulletin 95 (2015) 155–165 161

Fig. 6. a–c: PAH cross-plots for Arousa sediments.

Another more acute and widely used assessment method is the seven carcinogenic PAHs, BaP is the only one having suffi-
based on toxic equivalent factors (TEFs). This assessment method ciently toxicological data for derivation of a carcinogenic factor
focuses on previously defined seven carcinogenic PAHs. Among (Peters et al., 1999). For other carcinogenic PAH components,
162 B. Pérez-Fernández et al. / Marine Pollution Bulletin 95 (2015) 155–165

Fig. 7. Different ratios between alkylated and parent PAH for the collected samples.
 B. Pérez-Fernández et al. / Marine Pollution Bulletin 95 (2015) 155–165 163

TEFs were used for quantification (Nadal et al., 2004). The TEF 40
defined according to the USEPA, are listed in Table 6 (Nisbet and
LaGoy, 1992; Law et al., 2002) and the total BaP equivalent quo-
30
tient (TEQ) for seven carcinogenic PAH components can be calcu-
lated by the following equation: % Per/5-ringPAH
20
TEQ carc ¼ RCi  TEFi carc

where Ci is the concentration of individual PAH and TEFi is the cor-

10
responding TEF.
Total TEQcarc values calculated for samples, and compared with
R16PAH in Fig. 5, varied from 1.19 ng g1 to 819.6 ng g1 d.w., with 0
an average of 206.8 ng g1 d.w. The maximum total TEQcarc value AR02 AR04 AR12 AR14 AR18 AR21 AR24 AR27 AR29 AR31 AR32
was found at AR02 and AR04 stations.
Fig. 8. Ratio per concentration versus all 5 ring PAH addition.
The average levels of RPAHscarc and Total TEQ found in sedi-
ments from inner Ría de Arousa were lower than in sediments from
Naples harbour (Italy) and Kaohsiung Harbor (Taiwan), but were
higher than in Korsfjord, Vardø and Vadsø harbour (Norway).
PAH contamination level in the external area of Ría de Arousa
was similar to those found in unpolluted sediments of Jarfjord
and lower than in sediments from Langkawi Island (Malaysia)
(Table 6).

3.5. Hydrocarbon source identification

To investigate the origin of PAHs (Tobiszewski and Namiesnik,

2012), and identify separately petrogenic from pyrolytic inputs,
three different diagnostic ratios, as can be seen in Fig. 6a–c, based
on isomeric relations were used: Ant/(Ant + Phe), IP/(IP + BghiPer)
and BaA/(BaA + Chry) ratios plotted against Fla/(Fla + Pyr).
The first ratio used in this work Ant/(Ant + Phe) versus Fla/ Fig. 9. BaP concentration in ng g1 d.w. in all selected samples.

(Fla + Pyr) has further capacity to distinguish fuel combustion from

grass/wood and coal combustion. In our case the studied sediment
other PAHs, relative to penta-aromatic isomers and relative to
fitting the upper right quadrant with Ant/(Ant + Phe) higher than
non-alkylated PAHs allow us to identify the principal source
0.1 and Fla/(Fla + Pyr) higher than 0.5 corresponding to biomass
(Barakat et al., 2011; Budzinski et al., 1997; Agbozu and Opuene,
and coal combustion.
2009). In 73% of the studied points in the current research, pery-
The second double ratio plot supplies more information adding
lene contributes less than 6% to the total PAH burden and it was
a mixed source for samples with BaA/(BaA + Chry) values between
found that Per means about 2–4% to the total non-alkylated
0.2 and 0.35. Sample AR31 is part of this cluster pointing out the
PAHs, both are typical values for pyrolytic sources. The concentra-
possible presence of other sources than combustion ones or just
tion of Per relative to the penta-aromatic isomer (Fig. 8) also indi-
arisen the problem of using some ratios when the concentration
cates a pyrolytic origin of this compound for most of the locations
values are very low.
with values around 10%, being a value bigger than 20% the thresh-
Similar to other mass ratios, IP/(IP + BghiPer) rejects the idea of
old for diagenetic source (Liu et al., 2008).
petroleum sources as all samples present IP/(IP + BghiPer) ratio
This indicator (Per ratio) could be of great interest to identify
>0.2.
pristine area, and to point out valuable stations to calculate BC val-
In addition, the parent PAH and the alkyl PAH ratios are useful
ues for this region.
for source distinction as the presence of higher concentration of
Pyrolytic PAH can have their origin in different processes: com-
alkyl homologues than parent compounds indicates a petroleum
bustion of organic matter, combustion fossil fuel, vehicular engine
source (Elmquist et al., 2007). In this study MPhe/Phe, MPyr/Pyr,
combustion, smelting, waste incinerators, forest fires and coal
MChry/Chry and MPAH/PAH were calculated (Fig. 7). Values smal-
combustion. Major sources of PAH will vary from place to place
ler than 0.4, 0.5, 1 and 0.8 respectively are associated with exclu-
depending on the main developed activities; e.g. in urban areas
sively pyrolytic sources and values bigger than 2.5, 0.9, 2.5 and
with dense traffic, emissions are dominated by fossil fuel burning.
2.5 are indicative of petrogenic sources (Saha et al., 2009).
These processes can be characterized by significant quantities of
These PAH ratios clearly support the conclusion that mixed
BaP as it has been identified in higher percentages in vehicular
sources are the main contributors to the studied sediments con-
exhaust (Boitsov et al., 2009; Xu et al., 2014; Zhang et al., 2012).
tamination. Apart from this general conclusion AR29, AR31 and
On the other hand, small quantities of BaP as encountered in sam-
AR32 display certain petrogenic evidences but this can be due to
ples AR29, AR31 and AR32 (Fig. 9), which are away from urban
a misinterpretation of the ratios when the concentration values
influence, reveal an important diagenetic contribution.
are very low, as it happen in these ‘‘clean’’ stations.
One more source can be found in the PAH fingerprint; apart
from pyrolytic or petrogenic source, PAHs can be formed during 4. Conclusions
diagenetic processes, i.e. the formation of sediments from organic
material (Tobiszewski and Namiesnik, 2012). Per has been Arousa sediments were characterized and their possible sources
described as a good marker to identify these three sources as it and potential toxicologic significance have been identified. General
can have three different origins (Baumard et al., 1998). Studying parameters as grain size distribution and COT were first deter-
three different ratios such as the concentration of Per relative to mined. Values vary from 2.3% to 86.5% of particles <63 lm and
164 B. Pérez-Fernández et al. / Marine Pollution Bulletin 95 (2015) 155–165
from 0.5% to 3.5% for COT. Sediments can be classified on its basis
but no clear relationship between these variables and the PAH con-
centrations was subsequently found.
In terms of total PAH a clear gradient can be identified: sedi-
ments get cleaner from the river Ulla mouth to the outer zone of
the ría, all identified PAH exhibit the same trend.
Sediment quality and carcinogenic risk assessment was per-
formed using biological thresholds (ERLcarc and ERMcarc) and
potential toxicity based on toxic equivalent factors of carcinogenic
PAHs (TEF); both statistics point at samples AR02 and AR04 as the
most polluted but the effects seem to be restricted to a few kilome-
tres along the coast and none would be rated as in poor condition
by EPA categories.
As a conclusion from the research, the watershed can be defined
as moderate polluted and indications of the principal contamina-
tions sources have been reached. The vehicular emission and bio-
mass and domestic coal combustion were the main source
categories for most samples with the exception of AR29, AR31
and AR32 where diagenetic sources become more recognizable.
Besides this, from now on a baseline data are ready for use. Data
from all the stations will be valuable for assessing future events of
PAHs contamination in coastal sediments and the cleanest stations
data (AR29, AR31 and AR32) are crucial to be used as background
levels in coastal marine pollution monitoring, in general, and of the
Spanish Northern continental shelf, in particular.
Acknowledgments
The authors wish to thank the personal of IEO: Maria López
Rodríguez and Gerardo Fernández Carrera as well as the officers
and crew of R/V José María Navaz for the collection of samples.
The study has been funded by a Fund Management Agreement
between the IEO and the Spanish Ministry of Agriculture, Food an
Environment (2010–2012).
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