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0025-326X/$ - see front matter � 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpolbul.2004.11.031
Heavy metals in surficial coastal sediments of the Ligurian Sea
R.M. Bertolotto a,*, B. Tortarolo c, M. Frignani b, L.G. Bellucci b, S. Albanese a,C. Cuneo a, D. Alvarado-Aguilar b, M.R. Picca a, E. Gollo c
a Agenzia Regionale Protezione Ambiente Ligure (ARPAL), Direzione Scientifica, P.za Vittoria 15, 16121 Genova, Italyb CNR, Istituto di Scienze Marine, Sezione di Geologia Marina, Via Gobetti 101, 40129 Bologna, Italy
c Agenzia Regionale Protezione Ambiente Ligure (ARPAL), Dipartimento di Genova, V. Montesano 5, 16121 Genova, Italy
The coastal area of the Ligurian Sea is densely popu-lated and characterised by the presence of a variety of
economic activities, such as harbours, industrial plants
and tourism facilities which are likely to release heavymetals into the environment. By measuring concentra-
tions of heavy metals in bottom sediments, insight can
be provided on the sources, mechanisms of transport
and distribution, sites of accumulation, as well as on
the quality of the environment and the potential threats
to marine organisms and human beings.
* Corresponding author. Tel.: +39 010 57633234; fax: +39 010
57633224.
E-mail address: [email protected] (R.M. Bertolotto).
348 Baseline / Marine Pollution Bulletin 50 (2005) 344–359
Fig.1.Studyareaandsamplinglocations.ThefourprovincesoftheLiguriaRegionare
indicated.Ateach
location,threesamplesweretaken
at500,700and1000m
offshore,respectively.The
histograms(logarithmic
scale)compare
concentrationsofAs,Cr,Pb,CuandZn.GeistheabbreviationofGenova.
Baseline / Marine Pollution Bulletin 50 (2005) 344–359 349
Cosma et al. (1979) analysed Cr, Cu, Mn and Ni in 56
surficial samples collected in the coastal area of the Lig-
urian Sea from Andora to Arenzano (NE of Cogoleto in
Fig. 1) as well as in ten creeks flowing into the study
area. Only Cr and Ni showed concentrations higher
than expected, with a decreasing pattern from the coastto offshore. The higher values of these two elements
were clearly related to transport from Teiro, Arrestra
and Lerone creeks. Besides its natural origin from rock
formations, Cr in the Lerone creek was enriched by the
wastes of a chemical plant located at its mouth (from
1562, upstream, to 9830 lg g�1). High loads of Ni in
the area east of Cogoleto (Fig. 1) could be related to
the creeks that cross basic and ultrabasic rocks (Cosmaet al., 1979). Cu and Mn did not show any significant
anthropogenic enrichment in sediments of the area.
The maximum values were 1797, 135, 2336 and
490 lg g�1 for Cr, Cu, Mn and Ni, respectively.
Later, Cosma et al. (1982) examined a series of sedi-
ments (14 sites), five of which were located adjacent to
Genova, an area with high inputs of both industrial
and municipal wastes. Their results clearly showedanthropogenic inputs of Cr, Cu and Pb in the area of
Genova, whereas the other locations (Andora, Savona,
Chiavari, Manarola) were characterised by a significant
correlation of metals with Fe, and hence with the detri-
tal fraction. Cd and Ni concentrations appeared to be
unaffected by anthropogenic inputs. Samples offshore
of Genova were also characterised by relatively high
loads of organic carbon (2.01–2.78%). Maximum valuesfound in this study were 302, 91.3 and 250 lg g�1 for Cr,
Cu and Pb, respectively. Further data concerning the
distribution of heavy metals in sediments offshore of
Genova-Voltri, Savona and Imperia, down to a water
depth of 50 m, were provided by Picollo et al. (2000).
The authors found very high concentrations of Cr near
the mouths of water courses in the area of Genova-Vol-
tri. These values (40–460 lg g�1) were considered as nat-ural, due to the presence of basic rocks in river basins.
In addition, further information was provided by
ENEA (1989), ARPAL (1999) and Bertolotto et al.
(2003b). On the request of local authorities, the area
of Zinola-Vado Ligure, which is particularly interesting
because of the influence of an oil-burning power plant,
received a considerable attention. Additionally, Bertol-
otto et al. (2003b) provided some chronological infor-
mation. The purpose of the present study was to
determine distribution, degree of contamination, sources
and potential toxicological significance of heavy metals
in surficial sediments along the entire coast of the Ligu-
rian Sea.Sampling was carried out in 1999 at 75 stations with-
in the 25 localities shown in Fig. 1. Three samples were
collected along transects at 500, 700 and 1000 m from
the shoreline at each location. A Van Veen grab was
used, whose penetration was typically 10–20 cm. We
selected for analysis only the topmost sediment (2 cm)
that was carefully removed with a plastic spoon and
transferred to plastic vessels. Samples were stored at�18 �C before analysis.
As, Cd, Cr, Hg, Pb, Cu and Zn were determined. Ali-
quots of 0.5–1 g of homogenised wet sediments were
placed in Teflon bombs and treated with 3 mL of HCl,
9 mL of HNO3 and 2 mL of HF in that order. After
each addition, samples were left to rest for 15–20 min.
The bombs were then treated in a microwave oven for
the following cycle: 5 min at 250 W, 5 min at 400 W,5 min at 600 W and finally 5 min at 250 W. After cool-
ing, solutions were transferred to 25 mL flasks and
taken to volume. Blanks were prepared using the same
procedure without sediment. Metals were analysed by
AAS using either graphite furnace (Cd) or flame (Al,
Cr, Cu, Fe, Pb, Zn) according to the expected concen-
trations. Hg and As were determined by flameless
AAS. All analyses were carried out following IRSA(1986, modified: see ICRAM, 2001) recommendations.
Hexavalent chromium was also determined according
to IRSA (1986), but it was absent in all samples. Preci-
sion and accuracy were tested by analysing several
times the MESS2 Certificated Material (NRC, Canada).
Results, reported in Table 1, were not corrected for
recovery.
Organic carbon (OC) and total nitrogen (TN) weredetermined by a CHN analyser, after elimination of
carbonates using HCl in a silver capsule. Errors were
typically 2% for OC, and 3% for TN. Grain size
analyses were carried out at the University of Genoa;
after elimination of the organic fraction with H2O2,
wet sieving was used to separate sand from the fine
fractions. Silt and clay fractions were determined using
Table 1
Data quality: analyses of the MESS-2 certified standard (NRC, Canada)
Metal MESS-2 (lg g�1) Average (lg g�1) Standard deviation Percent recovery Detection limits (lg g�1)
As 21.5 23.0 ±1.6 107 0.038
Cd 0.24 0.20 ±0.01 83 0.004
Cr 114 102.2 ±10.2 90 0.019
Cu 41.3 32.7 ±1.3 79 0.057
Pb 23.1 23.5 ±1.2 102 0.038
Hg 0.092 0.088 ±0.01 96 0.002
Zn 156 142 ±6.2 91 0.380
350 Baseline / Marine Pollution Bulletin 50 (2005) 344–359
Table 2
Analytical data
Sampling site Distance Al As Cd Cr Cu Fe Hg Pb Zn OC Fines
Mortola 500 1100 6.3 1.13 10 3.3 4100 0.07 30 13 0.062 3.59
Mortola 700 610 12.2 0.10 17 6.8 9600 0.10 37 54 0.465 67.8
Mortola 1000 830 10.2 0.18 22 9.2 11600 0.09 40 65 0.616 82.7
Bordighera 500 1100 8.6 0.22 19 6.4 12900 0.03 29 51 0.133 3.45
Bordighera 700 900 9.6 0.16 19 6.4 10600 0.06 26 58 0.137 7.64
Bordighera 1000 1300 6.9 0.19 32 12.6 16400 0.06 32 66 0.376 34.6
Sanremo 500 1300 6.8 0.10 8 21.3 8400 0.04 56 35 0.097 1.03
Sanremo 700 1500 6.9 0.08 8 5.1 7900 0.05 23 31 0.070 4.25
Sanremo 1000 2400 5.0 0.12 10 4.8 7800 0.02 24 26 0.112 18.5
Arma di Taggia 500 2600 5.8 0.06 17 5.5 9100 0.03 19 36 0.109 3.81
Arma di Taggia 700 410 5.7 0.06 11 5.7 22900 0.06 17 28 0.084 2.27
Arma di Taggia 1000 8300 12.0 0.04 32 10.6 15900 0.07 28 67 0.400 55.5
Imperia 500 1800 8.1 0.19 26 7.8 10900 0.32 1.7 39 0.126 19.9
Imperia 700 1200 7.4 0.07 27 6.7 12000 0.13 1.2 40 0.177 23.8
Imperia 1000 1500 7.5 0.13 26 7.9 11700 0.07 1.3 39 0.152 11.4
Andora 500 320 12.4 0.05 14 4.6 9200 0.09 18 37 0.079 2.76
Andora 700 1200 12.8 0.05 18 6.1 9200 0.12 24 61 0.088 2.13
Andora 1000 1000 14.3 0.05 15 4.9 11000 0.10 20 49 0.094 2.19
Isola Gallinara 500 1700 10.0 0.07 40 20.0 24700 0.13 20 93 0.128 8.48
Isola Gallinara 700 2300 9.3 0.07 40 13.3 24900 0.20 20 87 0.142 7.19
Isola Gallinara 1000 4900 8.3 0.03 45 19.1 25100 0.06 19 83 0.365 25.8
Borghetto S.S. 500 830 13.0 0.07 27 10.0 10000 0.20 17 87 0.147 9.56
Borghetto S.S. 700 630 16.1 0.10 27 10.0 13000 0.10 17 70 0.147 17.7
Borghetto S.S. 1000 430 13.0 0.07 25 10.8 14000 0.11 18 72 0.149 16.6
Finale Ligure 500 4500 17.7 0.05 13 5.1 11300 0.03 18 48 0.064 8.54
Finale Ligure 700 3800 19.0 0.11 11 3.8 14600 0.04 15 57 0.062 3.60
Finale Ligure 1000 6200 15.0 0.04 26 8.6 17300 0.04 24 66 0.236 27.5
Zinola 500 5500 20.4 0.07 44 14.6 24800 0.2 47 190 0.173 23.8
Zinola 700 4900 19.7 0.11 54 25.4 31400 0.45 62 210 1.168 86.2
Zinola 1000 3500 21.8 0.12 78 43.7 39000 0.47 78 210 1.538 83.3
Albisola Marina 500 4300 6.9 0.05 6.9 2.3 4500 0.32 23 32 0.055 2.07
Albisola Marina 700 3700 20.0 0.09 320 46.8 49600 0.25 81 170 1.154 64.7
Albisola Marina 1000 3700 19.2 0.10 320 46.5 49000 0.27 83 180 1.100 54.9
Cogoleto 500 240 16 0.05 2000 23 67100 0.18 55 170 0.175 15.7
Cogoleto 700 630 17 0.04 2700 27 66500 0.23 58 160 0.176 12.3
Cogoleto 1000 550 29 0.08 3300 42 69300 0.23 80 260 0.929 56.4
Genova-Voltri 500 4800 15 0.46 590 25 48900 0.05 28 100 0.175 14.5
Genova-Voltri 700 2100 16 0.03 540 25 43200 0.09 38 120 0.266 28.9
Genova-Voltri 1000 1500 16 0.07 500 38 43000 0.31 55 160 0.288 59.3
Genova-Polcevera 500 9000 12 0.13 190 55 39400 0.21 73 210 1.190 72.8
Genova-Polcevera 700 2900 8.8 0.06 120 48 29000 0.42 73 240 1.913 88.3
Genova-Polcevera 1000 2700 13 0.62 260 70 47800 0.28 90 250 1.702 75.9
Genova-P.ta Vagno 500 930 9.9 0.09 68 25 19200 0.40 80 120 0.370 11.2
Genova-P.ta Vagno 700 990 8.9 0.10 64 25 19100 0.35 80 130 1.038 12.0
Genova-P.ta Vagno 1000 610 15 0.15 67 44 19200 0.41 91 180 1.453 63.4
Camogli 500 590 9.0 0.14 32 9.2 13800 0.07 39 25 0.365 6.80
Camogli 700 520 12 0.11 25 6.8 14700 0.11 27 45 0.186 7.24
Camogli 1000 920 12 0.28 25 6.9 15000 0.18 25 46 0.191 7.33
S. Margherita Ligure 500 950 13 0.09 77 15 15100 0.09 62 77 0.250 32.5
S. Margherita Ligure 700 540 12 0.12 74 33 24100 0.21 54 110 1.050 81.7
S. Margherita Ligure 1000 1160 9.2 0.14 96 41 29800 0.14 51 130 1.066 94.3
Chiavari 500 860 7.9 0.64 220 34 38300 0.08 41 140 0.196 9.44
Chiavari 700 1300 9.1 0.54 230 30 40200 0.03 30 130 0.158 11.2
Chiavari 1000 1200 12 0.16 140 29 36000 0.06 32 110 0.610 26.8
Riva Trigoso 500 1500 7.9 0.68 560 68 43100 0.08 45 120 0.081 4.77
Riva Trigoso 700 1500 11 0.16 380 66 36700 0.08 41 74 0.134 14.4
Riva Trigoso 1000 1100 12 0.99 330 74 36800 0.11 37 140 0.524 24.2
Deiva Marina 500 3100 6.8 0.08 23 15 20300 0.03 21 63 n.r. 0.54
Deiva Marina 700 5900 10 0.17 370 23 33000 0.04 33 94 0.763 32.0
Deiva Marina 1000 8000 12 0.16 330 27 33200 0.04 40 97 0.051 45.6
Punta Mesco 500 8800 6.4 0.08 34 3.8 9300 0.11 15 53 0.385 4.49
Punta Mesco 700 7800 9.1 0.05 71 14 20500 0.09 23 78 0.716 34.9
Punta Mesco 1000 7700 14 0.06 140 25 30400 0.08 31 110 0.108 94.2
(continued on next page)
Baseline / Marine Pollution Bulletin 50 (2005) 344–359 351
a Coulter Counter particle size analyser. All concentra-
tions were calculated on a dry weight basis. Water con-
tents were measured by drying known amounts of
sediment at 105 �C until constant weight (usually
overnight).
Metal concentrations are listed in Table 2, whereas
Fig. 1 shows the concentrations of As, Cr, Cu, Pb, Zn
and their proportions in the most contaminated samplefrom each transect. As, Cr and Hg distributions along
the Ligurian coast are displayed in Fig. 2. These results
show that all metals are subject to wide variability. Even
Al and Fe, which are considered mostly components of
sediment particles and hence naturally occurring, are
characterised by peak concentrations that are 50 and
17 times higher than the minimum values, respectively.
Low Al values ranged between 240 and 2600 lg g�1.Concentrations became relatively high (3500–
6000 lg g�1) at Isola Gallinara (1000 m), Finale Ligure,
Zinola, Albisola Marina and Manarola, and results at
Arma di Taggia, Genova-Polcevera, Deiva Marina,
Punta Mesco, Punta S. Pietro, La Spezia and Marinella
were close to 8000 lg g�1 or higher. Interestingly, Al
values showed no relationship with other metals and
sediment characteristics (Table 3). This suggests thatthere may be significant anthropogenic sources of Al
to the coastal area.
The distribution of Fe (4100–49600 lg g�1) was dif-
ferent from Al, with high values between Zinola and
Genova-Polcevera, S. Margherita Ligure and Punta
Mesco, and also Punta S. Pietro and Marinella. Table
3 shows that there is a relationship between Fe and
As, Cr, Cu and Zn. Fe, however, shows no correlationwith the measured sediment characteristics, i.e. OC con-
tent and grain size (Table 3).
Most values of As lay between 4.0–16 lg g�1, but
higher concentrations were found between Borghetto
S.S. and Genova-Voltri with a peak value at Cogoleto,
1000 m offshore.
Cd concentrations were generally low (0.03–
0.28 lg g�1), although their distribution shows six dis-
tinct peaks (0.42–1.13 lg g�1) at Mortola, Genova-Vol-
tri, Genova-Polcevera, Chiavari, Riva Trigoso and
Punta S. Pietro.
Cu concentrations were also generally low (2.3–
27 lg g�1) but peak values, up to 74 lg g�1, were found
at Genova-Polcevera and Riva Trigoso, with relatively
high contents in the area between Zinola and Genova-
Voltri, and in the transects of Genova-Punta Vagno,S. Margherita Ligure, Chiavari and La Spezia.
Hg showed peak values at Imperia (500 m), Zinola
(700 m), Cogoleto, Genova-Polcevera, Genova-Punta
Vagno, Punta S. Pietro and La Spezia. The maximum
(0.5 lg g�1) was approximately 24 times higher than
the minimum values. Bertolotto et al. (2003b) found
higher concentrations (1.9–5.8 lg g�1) in the area of
Zinola-Vado Ligure.Pb distribution is similar to Hg, except that there is
no evident Pb contamination at Imperia, and that max-
imum concentrations were found at Punta S. Pietro and
La Spezia (150 lg g�1). The pattern of Zn is very similar
to that of Pb, with a high correlation coefficient
(r = 0.874; Table 3). Maxima are approximately 10
and 47 times the minimum values for Pb and Zn,
respectively.Cr appears to be potentially the most dangerous pol-
lutant, with concentrations of 2000–3200 lg g�1 at
Cogoleto. These results confirm the findings by Cosma
et al. (1979) who measured up to 9830 and 1797 lg g�1
in the Lerone Creek and in the coastal area, respectively.
At this locality, the concentrations increase offshore, in
accordance with the reduction of grain size. Relatively
high values, over a background of 6.9–120 lg g�1, werefound at Albisola Marina, Genova-Voltri, Riva Trigoso
and Deiva Marina: 320, 590, 560 and 360 lg g�1,
respectively.
Bertolotto et al. (2003a) stated that the hydrodynam-
ics of the area drives sediment grain size in such a way
that the content of fine particles (silt plus clay) increases
going offshore: average values are 15.70% at 500 m,
31.90% at 700 m, and 46.34% at 1000 m. The maximum
Table 2 (continued)
Sampling site Distance Al As Cd Cr Cu Fe Hg Pb Zn OC Fines
Manarola 500 2600 4.0 0.22 120 13 18900 0.09 18 67 0.168 2.97
Manarola 700 4100 4.2 0.05 120 14 20200 0.09 23 70 0.107 3.34
Manarola 1000 360 4.4 0.05 110 15 20200 0.10 20 69 0.602 3.73
Punta S. Pietro 500 12000 13 0.44 120 30 32600 0.34 150 460 0.504 98.3
Punta S. Pietro 700 8200 12 0.42 110 24 31400 0.10 31 100 0.116 77.4
Punta S. Pietro 1000 580 8.7 0.17 46 12 13900 0.12 29 66 0.510 96.1
La Spezia 500 2700 13 0.17 90 23 31200 0.11 25 99 0.579 21.2
La Spezia 700 1800 15 0.09 96 32 32200 0.23 150 610 0.594 96.1
La Spezia 1000 7100 11 0.06 100 28 31000 0.15 59 170 0.191 88.9
Marinella 500 940 22 0.06 100 22 37300 0.13 25 110 0.286 10.6
Marinella 700 3200 9.9 0.06 90 17 27400 0.09 23 81 0.166 10.7
Marinella 1000 7700 12 0.11 150 14 29600 0.06 23 89 0.524 9.37
Metal concentrations are in lg g�1, whereas OC and fine sediment contents are in %. The distance of the samples from the coast is in m.
352 Baseline / Marine Pollution Bulletin 50 (2005) 344–359
contents of fines characterise sediments from the tran-
sect of Punta S. Pietro at 500 and 1000 m offshore
(98.31% and 96.11%, respectively). Silt is always prepon-
derant over clay, which never exceeds 9.16%. Further-
more, the contents of fine particles and OC in
sediments are strictly correlated (Table 3). The distribu-
tion of polycyclic aromatic hydrocarbons (Bertolotto
et al., 2003a), strong hydrophobic chemicals, shows that
0
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ERL
ERM
Fig. 2. Distributions of As, Cr and Hg along the Ligurian coast. ERL and ERM levels are indicated. Ge is the abbreviation of Genova.
Baseline / Marine Pollution Bulletin 50 (2005) 344–359 353
maxima generally correspond to the more distal sam-
ples, which are often finer than the others. On the con-
trary, as they are less closely linked to grain size,
maximum concentrations of metals are more wide-
spread: only Pb and Zn display a significant correlation
with the silt component. This evidence suggests that the
presence of metals in these sediments is a function of the
relative importance of point sources.Regarding Cr, maximum concentrations appear to be
very high. In order to evaluate the concentration of
other metals, we used the data of Bellucci et al. (2002)
and Bellucci and Frignani (unpublished) relative to sur-
ficial sediments of the Venice Lagoon. Table 4 shows
that the ranges of concentrations in Ligurian Sea sedi-
ments are wide as a result of a variety of environments
and inputs. Furthermore, in the present samples, Hg isrelatively low even if further data show the presence of
higher values in the area of Zinola-Vado Ligure (AR-
PAL, 1999; Bertolotto et al., 2003b). Cr, Cu, Pb and
Zn reach high concentrations, especially Cr which is
two order of magnitude higher than in reference samples
(Table 3).
High metal concentrations correspond to transects
located in front of the urban centre of Genova. TheBisagno Torrent, which crosses a densely populated
and industrialised area, flows very close to Genova-
Punta Vagno. Here, the passage of ferries, holiday
cruisers and container ships entering the Port of
Genova is frequent. A coal-burning power plant is
located in the vicinity, and Genova-Punta Vagno
hosts one of the most important treatment plants of
the city (300000 equivalent inhabitants). A further
example is the transect at Genova-Polcevera, located
in front of the homonymous torrent that drains an area
of maximum industrial concentration with steelworks,refineries, other minor industrial plants with high
pollution potential, and a treatment plant (125000
equivalent inhabitants). Nearby there is the oil termi-
nal of Genova Multedo, in which there are four refin-
eries and plants for mixing and treatment of oil
products.
At Zinola-Vado Ligure, the relatively high values of
Pb could be due to the production of paints and glazing.The presence of As, Hg, Cu and Zn can be related to
chemical and electronic processes. The concentrations
of Al, higher than in other areas, could be ascribed to
waste treatment plants, but also to the production of
electrodes and other electronic components.
The dramatic Cr contamination and the high values
of As, Hg, Pb and Zn in the area of Cogoleto have an
industrial origin. In particular, Cr is derived from a fac-tory located in the province of Genoa and affecting the
towns of Cogoleto and Arenzano, close to the Lerone
Creek. This plant dates back to the beginning of the
20th century and has been producing chromium salts
from chromite. Over nearly a century, specific products
were sodium dichromate, chromic acid, basic chromium
sulphate and vitamin K (from 1970).
Our observations also suggest that: (1) the high metalconcentrations at the transect of Genova-Voltri are
mostly natural (ophiolites) and only in part due to the
harbour activities; (2) Genova-Polcevera is a very devel-
oped industrial area, with particularly high Zn contam-
ination; (3) the secondary maxima of Cr at Riva Trigoso
and Deiva Marina may be attributed to past and current
industrial activities in the area; and (4) Punta S. Pietro
and La Spezia host chemical plants and industries for
Table 3
Correlations (Pearson�s linear coefficient, r) between metal concentrations and between metals and grain size
Al Fe As Cd Cr Hg Pb Cu Zn TOC Silt Clay
Fe 0.097
As 0.064 0.536
Cd �0.043 0.136 �0.149
Cr �0.134 0.722 0.454 �0.016
Hg 0.014 0.266 0.356 �0.085 0.132
Pb 0.150 0.465 0.368 0.100 0.238 0.618
Cu 0.052 0.699 0.284 0.373 0.289 0.39 0.581
Zn 0.235 0.539 0.417 0.084 0.263 0.539 0.874 0.54
TOC 0.169 0.387 0.325 �0.001 0.074 0.637 0.628 0.616 0.519
Silt 0.328 0.313 0.326 �0.011 0.04 0.465 0.616 0.448 0.611 0.72
Clay 0.123 0.01 0.055 �0.066 �0.098 0.056 0.293 0.146 0.238 0.367 0.493
Silt+Clay 0.326 0.306 0.32 �0.013 0.035 0.456 0.615 0.444 0.607 0.72 0.999 0.527
Significance limits are 0.532 (95%) and 0.661 (99%).
Table 4
Comparison between data from the Ligurian Sea and the Venice
Lagoon
Metal Ligurian Sea Venice Lagoon
surficial sediments
As 4.0–29 4.50–14.5
Cd 0.03–1.13 0.24–2.83
Cr 6.9–3300 14.2–33
Cu 2.3–74 10.2–65.6
Pb 15–150 10.0–64.9
Hg 0.02–0.47 0.12–2.30
Zn 13–610 61.7–415
Values are in lg g�1.
354 Baseline / Marine Pollution Bulletin 50 (2005) 344–359
metal treatments and electroplating, as well as harbourand shipbuilding activities, that may justify some high
values in nearby sediments.
Mean ERL quotients were calculated for each sample
by dividing the concentrations of the individual metals
by their respective ERL guidelines (NOAA, 1999; both
values are in lg g�1 dry weight), summing these quo-
tients and dividing by the number of analysed metals
(Long et al., 1998; McCready et al., 2000). This methodassumes additivity of toxic effects, and provides a useful
means of ranking sites that have multiple contaminants
(Long and MacDonald, 1998). Fig. 3 shows that, among
our 75 samples, 31 (41.3%) have mean ERL quotients
higher than or close to 1. Most of these values lie be-
tween 1 and 2, although three range between 4.3 and
7.2 because of the high Cr concentrations. Adverse bio-
logical effects are likely to occur only occasionally (Longet al., 1998) at the locations with mean ERL quotient
P > 1.0, from Zinola to Genova-Punta Vagno, and atRiva Trigoso, Deiva Marina, Punta San Pietro and La
Spezia.
Mean ERM quotients were also calculated using the
respective guidelines (NOAA, 1999). Only three samples
(at Cogoleto) have a value close to 1 or higher (up to
1.57), which implies a relatively high to very high prob-
ability of adverse biological effects (Long and MacDon-
ald, 1998; McCready et al., 2000), at least as far as heavymetals are concerned.
Acknowledgements
This study was funded by the Regione Liguria. The
authors wish to thank M. Costa of R.S.T.A. for his help
in sampling and U. Gasparino for data processing. Thispaper is contribution no. 1440 of the Institute of Marine
0
1
2
3
4
5
6
7
8
Mor
tola
Bordigh
era
Sanre
mo
Arma di
Taggia
Impe
ria
Andor
a
Isola
Gallina
ra
Borghe
ttoS.S
.
Finale
Ligur
e
Zinola
Albisola
Marina
Cogolet
o
Ge-Volt
ri
Ge-Polc
ever
a
Ge-Pta
. Vag
no
Camog
li
S. Mar
gherit
a Lig.
Chiava
ri
RivaTrig
oso
Deiva M
arina
Punta
Mes
co
Man
arola
Punta
S. Pietro
LaSpe
zia
Mar
inella
ERL
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
Mortol
a
Bordig
hera
Sanre
mo
Arma
diTa
ggia
Impe
ria
Andor
a
Isola
Gallina
ra
Borgh
etto
S.S.
Finale
Ligur
e
Zinola
Albiso
laM
arina
Cogole
to
Ge-Volt
ri
Ge-Polc
ever
a
Ge-Pta
. Vag
no
Camog
li
S. Mar
gher
itaLig
.
Chiava
ri
RivaTrig
oso
Deiva M
arina
Punta
Mes
co
Manar
ola
Punta
S. Piet
ro
LaSpe
zia
Marine
lla
ERM
Fig. 3. ERL and ERM mean quotients in 75 samples from the coastal zone of the Ligurian Sea fromMortola (to the west) to Marinella (to the east).
Samples along the same transect are listed from 500 to 1000 m offshore, in that order. Ge is the abbreviation of Genova.
Baseline / Marine Pollution Bulletin 50 (2005) 344–359 355
Sciences, Section of Marine Geology, CNR, Bologna,
Italy.
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Brominated diphenyl ethers in the blubber of twelve speciesof marine mammals stranded in the UK
Robin J. Law *, Colin R. Allchin, Lissaa K. Mead
Centre for Environment, Fisheries and Aquaculture Science, CEFAS Burnham Laboratory, Chemistry Department,
Remembrance Avenue, Burnham on Crouch, Essex CM0 8HA, UK
Polybrominated diphenyl ethers are a group of flameretardant compounds which have been widely used in
recent years. Increasing evidence of their environmental
persistence and potential for effects has led to the pro-
duction and use of the most environmentally mobile
polybrominated diphenyl ether (PBDE) formulations
being curtailed within the EU and to a call for them
to be added to the list of persistent organic pollutants
(POPs) listed within the Stockholm Convention whichcame into force during 2004 (Tanabe, 2004).
Marine mammal blubber samples were collected
within the UK Marine Mammal Strandings Programme
and derive from 34 animals stranded between 1992 and
2002. Post-mortem studies followed strict protocols and
tissues selected for analysis came from animals assessed
as freshly dead, slightly or moderately decomposed
(Law, 1994). These comprised 9 bottlenose dolphinsTursiops truncatus, 9 Sowerby�s beaked whales Mesopl-
odon bidens, 5 killer whales Orcinus orca, 2 pygmy sperm
whales Kogia breviceps, two hooded seals Cystophora
cristata, and 1 each of Cuvier�s beaked whale Ziphius
cavirostris, the fin whale Balaenoptera physalus, the sei
whale Balaenoptera borealis, the minke whale Balaenop-
tera acutorostrata, the northern bottlenose whale
Hyperoodon ampullatus, the humpback whale Megap-
tera novaeangliae and Risso�s dolphin Grampus griseus.
Details are given in Table 1.
Most of the bottlenose dolphins came from the coast-
al Moray Firth population, and would have fed on a
wide variety of fishes, squid and octopi. Cuvier�s and
Sowerby�s beaked whales feed in deep offshore waters,
taking fish and squid. Risso�s dolphins feed on the steep
upper continental slope and on the shelf, presumablyin response to the availability of their preferred prey,
squid. The northern bottlenose whale feeds in deep
water, eating squid (particularly Gonatus fabricii).
* Corresponding author. Tel.: +44 1621 787271; fax: +44 1621
784989.
E-mail address: [email protected] (R.J. Law).
356 Baseline / Marine Pollution Bulletin 50 (2005) 344–359
