66 PDF

Download as pdf or txt
Download as pdf or txt
You are on page 1of 10

Marine Pollution Bulletin 50 (2005) 185194

www.elsevier.com/locate/marpolbul

Heavy metal contamination in coastal sediments and soils near


the Brazilian Antarctic Station, King George Island
Isaac R. Santos a, Emmanoel V. Silva-Filho a,*, Carlos E.G.R. Schaefer b,
Manoel R. Albuquerque-Filho b, Lucia S. Campos c
a

Departamento de Geoqumica, Universidade Federal Fluminense, 24020-007 Niteroi-RJ, Brazil


b
Departamento de Solos, Universidade Federal de Vicosa, 36570-000 Vicosa-MG, Brazil
Departamento de Zoologia, Universidade Federal do Rio de Janeiro, Ilha do Fundao, 21949-900 Rio de Janeiro-RJ, Brazil

Abstract
This paper investigates the natural and anthropogenic processes controlling sediment chemistry in Admiralty Bay, King George
Island, Antarctica, emphasizing the area aected by the Brazilian Antarctic Station Comandante Ferraz (Ferraz). Total and bioavailable concentrations of sixteen elements were determined in 32 sediment and 14 soils samples. Factor analysis allowed us to distinguish three groups of samples: (1) Ferraz sediments, with higher content of total trace metals and organic matter; (2) control
sediments, with intermediate characteristics; (3) Ferraz soils, with higher bioavailability of most metals due to its oxidizing condition
and low organic matter content. Major elements such as Fe, Al, Ca and Ti presented similar levels in all three groups. Enrichment
factor calculations showed that paints, sewage and petroleum contamination enhanced metal concentrations in Ferraz surface sediments as follows: B, Mo, and Pb (>90%); V and Zn (7080%); Ni, Cu, Mg, and Mn (3040%). Despite evidence of contamination in
these sediments, the low bioavailability, probably caused by iron-sulde, indicates small environmental risks.
2004 Elsevier Ltd. All rights reserved.
Keywords: Antarctica; Pollution; Trace metals; Coastal environment; Bulk fraction; Ferraz Station

1. Introduction
Despite being the most isolated continent, Antarctica
is not free from deleterious human impacts. Anthropogenic pollution can reach the polar regions through
atmosphere circulation, e.g., organochlorines and metals
such as Pb and Hg; and sea currents, e.g., plastic (Santos
et al., 2004). Increasing human activities in Antarctica
after the International Geophysical Year (195758) has
caused several pollution problems, mainly near scientic
stations. These problems have led to the implementation
of strict environmental protocols, with the aim of preventing pollution.
*

Corresponding author. Tel./fax: +55 21 27174189.


E-mail address: geoemma@vm.u.br (E.V. Silva-Filho).

0025-326X/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpolbul.2004.10.009

Antarctic ecosystem is particularly sensitive to


anthropogenic modications. Ice-free land occupies
<2% of the continent, but most of the human and terrestrial biological activities are concentrated in these areas
(Campbell and Claridge, 1987). Furthermore, natural
environmental stresses and some characteristics of Antarctic marine biota, such as low capacity of larval dispersion, narrow reproductive season, low fecundity,
and low growth rates during crucial developmental
stages (King and Riddle, 2001; Smith and Simpson,
1995), make it highly susceptible to human impact and
sensitive to environmental contamination.
Heavy metals naturally occur in the earth crust. However human activities have introduced high loads of
these elements in the environment, making the dierentiation of natural and anthropogenic contributions

186

I.R. Santos et al. / Marine Pollution Bulletin 50 (2005) 185194

dicult. Sediments provide a temporally integrated indication of the aquatic environment condition and act as a
major reservoir for metals (Caccia et al., 2003), though
some sediments can also act as a source of contaminants
(Adams et al., 1992; Burton Jr. and Scott, 1992). Furthermore, sediments have high physical-chemical stability and their characteristics usually represent the average
condition of the system, often being representative of
the average water quality (Forstner and Wittman,
1983; Salomons and Forstner, 1984). Soils, along with
rocks, are the terrigenous sources of elements to adjacent sediments and can indicate local hot spots.
The Protocol to the Antarctic Treaty on Environmental Protection recognizes the importance of scientic
monitoring and continuous assessment of the impacts
of ongoing activities in Antarctica (Champ et al.,
1992). Yet, these kinds of studies are still incipient in
most scientic bases. The understanding of local pollution processes concerning heavy metals in soils and sediments is particularly scarce in Antarctica (Ciaralli et al.,
1998; Claridge et al., 1995; Kennicutt et al., 1995; Lenihan, 1992; Lenihan et al., 1990; Merlin et al., 1989;
Sheppard et al., 2000; Webster et al., 2003). The only
study on heavy metals in sediments of Admiralty Bay
showed no evidence of pollution due to the human presence in this region (Gomes, 1999), but sampling was
small. The aim of this paper is to investigate the naturally and anthropogenic processes controlling sediment
chemistry in Admiralty Bay (AB), King George Island
(KGI), Antarctica. Emphasis is given on heavy metal
contamination in the region aected by Brazilian research and logistical activities in Keller Peninsula.

2. Materials and methods


2.1. Site description
The Brazilian Antarctic Station Comandante Ferraz
(hereafter called just Ferraz) started operating in 1984.
Nowadays, it shelter nearly 15 people during the winter
months (MarchNovember) and up to 48 people during
the summer season, when research activities are intensied. At Ferraz Station, the organic matter is removed
from the sewage (secondary treatment) and all environmental regulations of the Madrid Protocol (such as
environmental monitoring and garbage disposal) are
respected.
Admiralty Bay is a fjord in the King George Island,
which is located approximately at 63 S in the South
Shetlands Islands. This bay has an area of 131 km2
and maximum depth of 530 m (Rakusa-Suszczewski,
1980). The South Shetlands Islands expose volcanic
and plutonic rocks of Early Cretaceous to Early Miocene age, which are related to the subduction of the
SE-Pacic oceanic crust underneath the Antarctic Con-

tinent. Mac volcanic rocks (i.e. basalts, basalt-andesites and andesites) are the dominant lithologies.
Rhyiolite and dacite are less abundant (Groeneweg
and Beunk, 1992; Machado et al., 1998, 2001; Pride
et al., 1990; Schaefer et al., 2004).
2.2. Sampling
Surface sediment samples (top 2 cm) and soil (top
10 cm) were collected during the summer of 2002/2003,
in the 21st Brazilian Antarctic Expedition. Surface soil
samples (n = 14) were collected in the marine terrace in
front of the Ferraz Station. Coastal sediment samples
(n = 32) were collected with a Van Veen grab in transects
(Fig. 1) normal to the coast at depths of 20, 30 and 60 m
as follows: CF 1 (in front of Ferraz fuel tanks); CF 2 (in
front of Ferraz helicopter landing area and sewage outfall); CF 3 (in front of Ferraz Chemical module); MP (in
front of the Peruvian Machu Picchu Station); HE (at
Hennequin Point). Two additional sediment samples
were collected at Botany Point (BP) at 18.5 m depth.
Samples were collected at the beginning (November
and December of 2002) and at the end of summer season
(January and February of 2003) in order to evaluate
possible temporal variability caused by the increase in
research and logistical activities at the Brazilian Antarctic Station during the summer.
2.3. Analysis
In the laboratory, samples were dried (<40 C) and
ground for chemical analysis. Organic matter (OM)
was determined by calcination (450 C, 24 h). Total metals were extracted with an adaptation of methods extensively used in literature (Bettinelli et al., 2000; Windom
et al., 1989). Approximately 1 g of each sample was digested with aqua-regia and hydrouoric acid in a Teon
bomb during 1 h at 120 C. After cooling, bombs were
opened and heated again until almost dry. Extract recuperation was done with HCl 0.5 M. The samples were
then analysed by ICP-OES (Perkin-Elmer), some in triplicate. All reagents used were Suprapur Merck and
water was Milli-Q. International Certied Reference
Material (Estuarine sedimentNIST 1646a) and blanks
were included in the set of samples to check the precision
and accuracy of the analysis. Results of certied sediment analysis showed satisfactory analytical accuracy,
varying between 85% for Ni and 104% for Ba. The precision of the analytical procedures (calculated as standard deviations of triplicates) were better than 8%,
with the exception of Pb (11%) and Ni (12%), all considered satisfactory.
In order to quantify the labile or bioavailable forms
of metals in relation to total metals, 1 g of the sediment
sample was extracted for 2 h with 10 ml of 1 M HCl
(Luoma and Bryan, 1981; Szefer et al., 1998). This tech-

I.R. Santos et al. / Marine Pollution Bulletin 50 (2005) 185194

187

Fig. 1. Study area. (A) Antarctic Peninsula; (B) King George island; (C) Admiralty Bay; and (D) detail of coastal sediment sampling points in Keller
peninsula near Ferraz Station.

nique determines the fraction of metals associated to Feand Mn-oxides and therefore allows measurement of
bioavailable forms of metals in sediments. This extraction procedure has been extensively used because high
correlations between metals in benthic organisms and
1 M HCl extracted metals in surface sediments are often
found (Bryan and Langston, 1992).
Since there are no important point contaminant
sources for the sediments collected in BP, MP, and
HE, these points were called controls. In this paper,
the concentrations of the variables under study were
compared in sediments theoretically contaminated (in
front of Ferraz) with control sites through t-test for
independent samples. Outlier values were identied
throughout test of Grubbs (Sokal and Rohlf, 1981).
Here, the outlying values were deleted and then replaced
by the highest values in datasets after deletion (Zhang
et al., 1998). After outlier replacement, all variables
passed in the normality test of KolmogorovSmirnov.
Pearsons correlation coecients were used for testing
dependency between two variables. A signicance level
of p < 0.01 was used throughout the study. Principal
Component Analysis followed traditional methods
(Wenchuan et al., 2001).

3. Results and discussion


3.1. Heavy metal distribution
Table 1 shows the average concentrations of total
metals in soils and coastal sediments in comparison with
several reference values. No important temporal (beginning and end of summer) and depth-related variability
of metal concentrations in sediments were observed,
therefore data presented is a mean of the two temporal
samplings. In comparison with the earth crust (Wedepohl, 1995), the high levels of cooper, in the studied

soils and sediments, is of major environmental concern.


It is related to the widespread mineralization of calcopirite in the volcanic rocks of the area (Machado et al.,
2001), and not necessarily related to anthropogenic contamination. Cr and Fe concentrations were higher than
sediments of Collins Harbour, KGI (Ahn et al., 1996),
though extraction techniques were dierent.
In relation to local rocks (Groeneweg and Beunk,
1992; Machado et al., 1998, 2001) concentrations of
most elements were similar, with the exception of Sr,
Mg, Ca, and Ba, which are higher in rocks probably
due to the dissolution processes in subaqueous sediments. The heavy metal contents indicate the inuences
from the geochemical weathering of terrigenous sources
on Admiralty Bay rocks. The results of the only previous study on Admiralty Bay sediments (Gomes, 1999)
were also similar to the results presented here, with the
exception of Ni.
Principal Component Analysis (PCA) was applied for
evaluating the hypothesis of a geographical separation
of sampling points. Three groups of samples with dierent physical-chemical properties and geographical distribution were clearly separated (Fig. 2). Group 1 is
formed by sediment samples collected in front of Ferraz
Station. These samples had higher OM and trace elements content. In Group 2 control sediment samples
were tted, characterized by lower content of total trace
elements and ne-grained sediments. Group 3 was
formed by CF soil samples, having coarser grains and
less organic matter compared with the other groups.
In fact, total B, Cu, Pb, V, Zn, OM and ne-grained
sediments presented higher content in CF sediments (ttest; p < 0.01). Sr was the only element with higher values in the control sediment samples (Table 1 and Fig. 3).
For the major elements Al, Fe, Ca, and Ti there were no
dierences between Ferraz and the control sediment
sampling points. Titanium, probably as ilmenite, is one
of the most stable elements in the aquatic environment

188

I.R. Santos et al. / Marine Pollution Bulletin 50 (2005) 185194

Table 1
Average content of metals in studied soils and sediments in comparison with results of other studies
Matrice (local)
a

Ferraz sediments (AB, KGI)


Control sediments (AB, KGI)a
Ferraz soils (AB, KGI)a
Sediments (Collins Harbour, KGI)b
Sediments (McMurdo Station)c
Sediments (AB, KGI)d
Sediments (Intertidal area, KGI)e
Sediments (Ross Sea)f
Soils (near Lake Vanda)g
Sediments (Terra Nova Bay)h
Vulcanic Rocks (KGI)i
Vulcanic Rocks (AB, KGI)j
Rocks (Global average)k

Al

Ba

Ca

3.16
3.02
3.44

243
136
89

41
75
109

0.58
0.68
0.48

Cr
31
35
40
7.6

5.44
28

5.61
5.18
4.77
7.96

2.6
47.0

Cu
92
67
44
77
11
68
52
25
28

20.3

11

198
333
584

7.27
5.72
3.85

126

111
25

Fe

Mg

6.47
6.88
6.15
2.42

0.14
0.11
0.12

Mn

Mo

624
527
442
640

1.5
0.7
2.1

6.28
2.37

280

46.2

1.00
1.64
2.92
2.79
4.32

104
359
1100
1500
716

2.65
2.20
2.20

1.1

Ni

Pb

Sr

Ti

Zn

10.1
7.9
5.1
15.4
68.0
41.3
11.5
23.0
11.2
6.3
60.7
12.5
56.0

10.5
5.5
11.5
8.7
7.0
14.9
121.0
15.0
3.9
20.7

63
121
118

0.58
0.58
0.58

204
127
91

344

0.04

82
49

89
52
52
69
32
60
47
50
24
42

542
583
333

0.56
0.64
0.4

7.7
14. 8

107
98

66
65

Values in mg/Kg, except Al, Ca, Mg, Fe and Ti, in %.


a
This Study.
b
Ahn et al. (1996)
c
Lenihan et al. (1990).
d
Gomes (1999).
e
Alam and Sadiq (1993).
f
Merlin et al. (1989).
g
Webster et al. (2003).
h
Ciaralli et al. (1998).
i
Machado et al. (2001).
j
Groeneweg and Beunk (1992).
k
Wedepohl (1995).

3.2. Geochemical carrier

Factor 2

-1

-2

-3

Ferraz Sediments
Control Sediments
Ferraz Soils

-4
-2

-1

Factor 1
Fig. 2. Factor scores obtained from principal component analysis.

and together with Al represent the most important indicators of detrital origin (Karageorgis et al., 1998). Thus,
little variation in Al and Ti among the dierent sampling
groups indicates that lithological sources are basically
the same, and dierent loads of most trace metals
cannot be explained solely by natural geochemical
signatures.

In the absence of a sequential extraction of metals in


sediments, statistical procedures can be used for making
inferences on the most important geochemical carrier.
Organic matter, sulde, carbonate, iron oxyhydroxide
and ne-grained sediments have been considered the
main metallic scavenger and/or geochemical carriers in
sediments (Salomons and Forstner, 1984). Pearsons
correlation coecients were calculated for evaluating
the dependency of metals in relation to Al, Fe, Ca,
OM, and grain size for the three groups of samples (Table 2). Pearsons correlations for all samples could not
be calculated because scatter plots (Fig. 3) and PCA
(Fig. 2) clearly formed dierent populations of samples,
which would lead to inconsistent interpretation.
With the exception of the strong relationships between Zn, Pb and ne-grained sediments in Ferraz soils,
Pearsons coecients did not show good correlations between metals and OM and ne-grained sediments
(<0.062). This was unexpected, since trace element concentrations usually increase as grain size decreases, due
to the higher ability of the ne particles to collect both
transition and heavy metals. Fine-grained sediments
have a greater surface area and provide a more ecient
environment for the adsorption of metals. Organic matter is also considered a good metallic scavenger (Wasserman et al., 1998).
Although elemental correlations are dierent between
sampling groups, it is possible to identify two main cat-

I.R. Santos et al. / Marine Pollution Bulletin 50 (2005) 185194


140

20
16

100

Ni (mg/Kg)

Cu (mg/Kg)

120

80
60
40

0
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5

Fe (%)

Fe (%)

120

300

100

250

80

200

60
40
20

150
100
50
0
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5

0
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5

Fe (%)

Fe (%)

25

900

20

750

Mn (mg/Kg)

Pb (mg/Kg)

7 7

0
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5

V (mg/Kg)

Zn (mg/Kg)

12

20

15
10
5

600
450
300
150
0

0
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5

4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5

Fe (%)

Fe (%)

9000

450

7500

375

6000

300

B (mg/Kg)

Ti (mg/Kg)

189

4500
3000
1500

225
150
75

0
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5

0
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5

Fe (%)

Fe (%)

Fig. 3. Scatter plots of iron and other metals. CirclesFerraz sediments; SquaresControl sediments; TrianglesFerraz soils.

egories of elements with similar behaviour. The rst category was clearly composed by Fe and metals such Cu,
B, Ti, Pb, V, and Zn. These elements showed high positive correlation with Fe mainly in the Ferraz sediments,
indicating the existence of a FeMn oxyhydroxide and/or
an iron sulde factors (depending on the prevailing redox conditions), which attracts a substantial part of
trace elements. Concentrations of Mn, Ni, Cr, and Ba
depend either on iron or calcium. In Ferraz sediments,
these metals had stronger correlations with iron, while
in control sediments Cr, Mn and Ni correlated better
with calcium (Table 2).

The adsorption of metals in FeMn oxyhydroxides is


a common phenomenon in marine sediments (Calvert,
1976). The oxides are observed either as coatings on
the clay-minerals or as individual particles. However,
this behaviour is normally observed in very weathered
environments, whilst trace metals entering Admiralty
Bay will probably be removed as suldes in the coastal
anoxic sediments, likewise in other Antarctic ecosystems
(Green et al., 1989; Webster et al., 2003). This hypothesis is supported by prevalence of reducing conditions in
sediments (authors unpublished data), abundance of
iron-sulde minerals (pyrite/calcopyrite; Pride et al.,

190

Table 2
Pearson correlation coecients between variables for Ferraz sediment samples (n = 18); control sediments (n = 14); and Ferraz soils (n = 14)

Al
Al
B
Ba
Ca
Cr
Cu
Fe
Mg
Mn
Mo
Ni
Pb
Sr
Ti
V
Zn
OM
*

Ca

Control sediments (n = 14)

Fe
***

0.60

OM

<0.062 mm

Al

Ca

0.52**
0.45*

0.46
0.48**
0.48**

**

**

OM

0.45
0.42*

0.52

0.48**
0.60***
0.87***

0.47

0.74

***

**

0.55
0.50**

p < 0.1.
**
p < 0.05.
***
p < 0.01.

0.58**

***

0.88

***

0.68

0.63***

0.53*

**

0.46
0.50**

0.84
0.57**
0.91***
***

0.49

Ca

0.79***
0.84***
0.84***

0.59**

0.42

0.88
0.55**
0.60**
0.70***

Fe

OM

<0.062 mm

**

0.51*
0.61**

0.54**

**

0.58
0.79***

0.60**
0.49*

***

0.54**
0.43*

Al

0.61
0.69***
0.55**

0.42*
0.58

<0.062 mm

0.51*
0.60***

Ferraz soils (n = 14)

Fe

0.67

0.75***

**

0.51*
0.84***
0.49*
0.79***
0.87***
0.81***

**

0.59

0.75***
0.56**

0.64

0.57**

0.65**

0.52*

0.54**
0.76***
0.91***
0.63

**

0.77***

**

0.48*
0.50*
0.72***
0.54**
0.48*

0.79***
0.54**

0.61**
0.48*
0.49*

I.R. Santos et al. / Marine Pollution Bulletin 50 (2005) 185194

Ferraz sediments (n = 18)

I.R. Santos et al. / Marine Pollution Bulletin 50 (2005) 185194

1990; Schaefer et al., 2004) in local rocks and higher organic content in sediments in front of Ferraz Station,
which favors iron suldes formation to the detriment
of FeMn oxyhydroxides. Furthermore, predominance
of physical weathering in the Antarctic environment
do not favor the formation of secondary minerals, like
clays (Campbell and Claridge, 1987), decreasing relative
importance of aluminum on controlling heavy metals
distribution patterns.
The second category of elements was formed by Al,
Ca, Sr, and Mg. These elements have strong interdependency in Ferraz soils and sediments, indicating a common lythogenic source and the occurrence of CaAl
minerals, like plagioclases (Machado et al., 2001).
Molybdenum is the only element without any strong
(p < 0.01) correlation with other elements in Ferraz soils
and sediments and has a higher enrichment factor indicating that anthropogenic inputs control its distribution,
rather than natural inputs, as described ahead.

191

Wijsman et al., 2002). With increasing concentrations of


organic matter in the sediment, the relative importance
of sulfate reduction usually increases (Clark et al.,
1998; Wijsman et al., 2001). Hence, the observed higher
organic content of Ferraz sediments favors the occurrence of reducing environments and sulde formation,
decreasing bioavailability of metals.
The percentages of easily extractable metals in Admiralty Bay sediments are usually low in comparison with
other environments, with the exception of Aluminum. In
sediments of the Baltic Sea, for example, Cd, Pb and Zn
(>70%) were eciently leached out with HCl 1 M; Cu,
Cr, Mn, Ca, Sr and Mg were less eciently leached
(60%); and Al poorly leached (4%) (Szefer et al.,
1995). The only previous study on ratios between total
and easily extractable metals for Antarctica was conducted in Terra Nova Bay (Ciaralli et al., 1998). These
authors extracted with 0.5 N HCl 3.5% (Fe) to 35.4%
(Zn) of total metals, but these results are not comparable due to dierent extraction techniques employed.

3.3. Heavy metal bioavailability


3.4. Contamination processes
Ratios between 1 M HCl extracted metals and total
concentrations (hereafter called bioavailable:total ratio)
are presented in Fig. 4. Results clearly show an increase
of bioavailability of heavy metals in soils in comparison
to sediments. This could be explained by possible dierent redox properties of soils and sediments. Soils are oxidizing environments, favoring the occurrence of FeMn
oxides in relation to iron suldes, therefore increasing
the relative contribution of easily extractable metals.
Sediments, on the other hand, are probably more reduced and iron occurs predominantly as sulde complexes, decreasing its bioavailability and, consequently,
the eciency of the 1 M HCl extraction procedure. In
fact, metal sulde complexes have low solubility in natural waters and their formation is very important to
metal bioavailability/toxicity reduction in the aquatic
environment (Clark et al., 1998; Fernandes, 1997).
Sulfur and iron cycling in surface sediments is largely
inuenced by sedimentation rates, organic matter supply, availability of sulfate and reactive iron, and oxygen
concentrations in the bottom waters (Billon et al., 2001;

Bioavailable:total (%)

90

Ferraz Sediments
Control Sediments
Ferraz Soils

80
70
60
50
40
30
20
10
0
Al

Ba

Cr

Cu

Fe

Mn

Mo

Ni

Pb

Ti

Zn

Fig. 4. Average percentage and standard deviation of total metal


content extracted with 1 M HCl for three groups of samples.

The possibility of sediment contamination was assessed through the calculation of the metal enrichment
factor (EF), which is the observed metal/normalizer
ratio in the sample divided by the metal/normalizer ratio
reported for a reference material (Salomons and Forstner, 1984; Zhang, 1995). Metals such as Al, Li and Fe
have been largely used as geochemical normalizers (Daskalakis and OConnor, 1995; Niencheski et al., 2002). In
this work, Fe and Al were tested as normalizers and the
earth crust average as reference value (Wedepohl, 1995).
In relation to Aluminum, the use of iron as geochemical normalizer seems to be more adequate because (1) it
shows better correlation with most elements (Table 2),
suggesting that iron is the main geochemical carrier in
the studied sediments; (2) the common disadvantages
of using iron as normalizer probably do not occur in
the studied surface sediments; and (3) aluminum occurs
at lower levels in the studied sediments in relation to
earth crust values, generating unrealistic enrichment factors. The main limitation of using iron as a geochemical
normalizer is the possibility of anthropogenic input of
this element (Niencheski et al., 2002), as well as its redox
sensitivity, which is a limiting factor for its application
in sediment cores (Wasserman et al., 2001). The use of
statistical procedures for determining the main geochemical carrier in sediments and choosing the best
geochemical normalizer has also been done by other
authors (Liu et al., 2003).
Enrichment factor calculations using average earth
crust as reference and iron as a geochemical normalizer
showed elevated values for Ferraz sediments (Fig. 5).
When t-test was applied for comparing EF of the studied
elements between control and Ferraz sediments, the

192

I.R. Santos et al. / Marine Pollution Bulletin 50 (2005) 185194

Enrichment Factor

20

2.5

3.0
2.5

16

2.0

2.0

12

0.5

Ferraz Sediments
Control Sediments
Ferraz Soils

0.4

1.5

0.3

1.0

0.2

0.5

0.1

1.5
8
1.0
4

0.5
0.0

0.0
Cu

0.0
Mo

Ti

Zn

Mg

Mn

Pb

Al

Ba

Ca

Cr

Ni

Sr

Fig. 5. Average and standard deviation of enrichment factor of metals for three groups of samples. Values normalized by iron and using earth crust
average as reference (Wedepohl, 1995).

results were similar to those of the raw data. The EF of


B, Cu, Mg, Mn, Pb, V and Zn were higher in Ferraz sediments, while Ba and Sr were higher in control sediments.
Control sediments have no important local anthropogenic contamination sources, have similar geochemical
properties (i.e. major element content) compared with
Ferraz sediments, and other works (e.g. Pride et al.,
1990; Groeneweg and Beunk, 1992) did not show any
special kind of mineralization near Ferraz Station. Taking into account these characteristics and in the absence
of other reference values, such as sediment core data, the
average elemental concentrations of control sediments
may represent background levels of Admiralty Bay,
and could be used for estimating the role played by Ferraz Station activities in changing metal levels of its adjacent sediments.
Fig. 6 shows average enrichment factors for metals in
Ferraz sediments using average metallic values of control
sediments as reference. It demonstrates an enrichment of
several metals, which could not be attributed to natural
characteristics. Based on this gure, it is possible to estimate that after 19 years of activities, Ferraz Station has
increased natural metal concentration in adjacent surface
sediments as follows: B, Mo, and Pb (>90%); V and Zn
(7080%); Ni, Cu, Mg, and Mn (3040%). For other metals there were no indications of anthropogenic input. Despite evidence of contamination in these sediments, low

bioavailability indicates minimum environmental risks.


Molybdenum is closely related with redox conditions in
marine sediments. While it is conservative in the oxygenated ocean, it accumulates in anoxic sediments (Bertine,
1972; Francois, 1988). Thus, enrichment of Mo may be
due to human input associated with redox conditions of
sedimentary environment.
Relationships between Zn and Pb with ne-grained
particles in Ferraz soils associated with its high bioavailability (mainly for Pb) suggest local contamination.
However, the absence of control soil samples make the
assessment of Ferraz soils contamination dicult.
The possible anthropogenic sources of metals for Ferraz sediments are petroleum contamination, sewage disposal and paints. Studies concerning hydrocarbon
(Bcego et al., 1998) and wastewater (Martins et al.,
2002) contamination in sediments near Ferraz Station
have shown low and localized levels of pollution, similar
to our results. Several metals (V, Ni, Zn, Cu, Cr, Pb, Ba,
among others) have been associated with petroleum
contamination (Alam and Sadiq, 1993; Caccia et al.,
2003). Paints are also another possible source of metals,
such as Pb and Cu (Webster et al., 2003), and it is very
likely that the structure of the helicopter landing area
contributes to the increase of these elements in Ferraz
sediments. In McMurdo Sound region, crushed batteries, scattered rubbish and buildings are point sources

Enrichment Factor

Al

Ba

Ca

Cr

Cu

Fe

Mg Mn Mo

Ni

Pb

Sr

Ti

Zn

Fig. 6. Average and standard deviation enrichment factor of metals in Ferraz sediments. Values were normalized by concentrations of Control
sediments.

I.R. Santos et al. / Marine Pollution Bulletin 50 (2005) 185194

of metals (Pb, Zn and Cu) in soils, while burning fuel


results in widespread contamination of lead (Claridge
et al., 1995). Sewage has also been considered an important source of metals both for lower latitude and
Antarctic regions. Near the McMurdo Station, for
example, higher concentrations of metals were observed
in sediments around the sewage outfall (Kennicutt et al.,
1995; Lenihan, 1992).

4. Conclusions
In this paper, soil and coastal sediments of Admiralty
Bay were characterized in reference to heavy metal concentrations, serving as basis for environmental monitoring programmes in the region. In general, our results
agree with other Antarctic sediments and rocks from
King George Island. Factor analysis allowed us to
distinguish three groups of samples: (1) Ferraz Station
sediments, with higher total metals and organic matter
content; (2) control sediments, with intermediate characteristics; and (3) Ferraz soils, with higher bioavailability of most metals due to its oxidizing condition,
low organic matter content and coarser grains.
Statistical procedures indicated iron as the main geochemical carrier in the studied sediments therefore iron
is preferred as a geochemical normalizer for enrichment
factor calculations. Sewage disposal, paint residues from
buildings and/or petroleum are probably the sources of
trace metals enrichment in sediments collected near Ferraz Station. On the other hand, anthropogenic input of
organic matter to sediments favors sulde formation
and reduction of metal bioavailability, consequently
decreasing adverse eects on local biota. The relatively
low availability of metals in Ferraz sediments appears
to counteract the local enrichment of most metals.
The small area of contaminated sediments and low
bioavailability of heavy metals suggest that this would
not adversely aect Antarctic benthic marine organisms.
Furthermore, contamination levels are lower than other
Antarctic Research Stations and industrialized regions.
Continuous environmental monitoring, determination
of local background through sediment cores, transference rates to biota, and further ecotoxicological studies
are essential for identifying and preventing pollution in
Admiralty Bay.

Acknowledgments
This paper is part of CRIOSSOLOS and GEAMB
projects (grants 55.03682002 and 55.0356/20029
respectively) supported by the Brazilian Antarctic Programme (PROANTAR) through the Brazilian National
Research Council (CNPq), Ministry of Environment,
and the Brazilian Navy. Many thanks to Christian

193

Sanders, Julio Wasserman and an anonymous reviewer


for useful suggestions.

References
Adams, W.J., Kimerle, R.A., Barnett Jr., R.A., 1992. Sediment quality
and aquatic life assessment. Environmental Science and Technology 26, 18651875.
Ahn, I.-Y., Lee, S.H., Kim, K.T., Shim, J.H., Kim, D.-Y., 1996.
Baseline heavy metal concentrations in the antarctic clam, Laternula elliptica in Maxwell Bay, King George Island, Antarctica.
Marine Pollution Bulletin 32, 592598.
Alam, I.A., Sadiq, M., 1993. Metal concentrations in antarctic
sediment samples collected during the Trans-Antarctica 1990
expedition. Marine Pollution Bulletin 26, 523527.
Bertine, K., 1972. The deposition of molybdenum in anoxic waters.
Marine Chemistry 1, 4353.
Bettinelli, M., Beone, G.M., Spezia, S., Ba, C., 2000. Determination
of heavy metals in soils and sediments by microwave-assisted
digestion and inductively coupled plasma optical emission spectrometry analysis. Analytica Chimica Acta 424, 289296.
Bcego, M.C., Zanardi, E., Ito, R.G., Weber, R.R., 1998. Hydrocarbons in surface sediments of Admiralty Bay, King George Island,
Antarctica. Pesquisa Antartica Brasileira 3, 1521.
Billon, G., Ouddane, B., Boughriet, A., 2001. Chemical speciation of
sulfur compounds in surface sediments from three bays (Fresnaye,
Seine and Authie) in northern France, and identication of some
factors controlling their generation. Talanta 53, 971981.
Bryan, G.W., Langston, W.J., 1992. Bioavailability, accumulation and
eects of heavy metals in sediments with special reference to United
Kingdom estuaries: a review. Environmental Pollution 76, 89131.
Burton Jr., G.A., Scott, K.J., 1992. Sediment toxicity evaluation, their
niche in ecological assessment. Environmental Science and Technology 26, 20682075.
Caccia, V.G., Millero, F.J., Palanques, A., 2003. The distribution of
trace metals in Florida Bay sediments. Marine Pollution Bulletin
46, 14201433.
Calvert, S.E., 1976. The mineralogy and geochemistry of near-shore
sediments. In: Riley, J.P., Chester, R. (Eds.), Chemical Oceanography. Academic Press, NewYork, pp. 187280.
Campbell, I.B., Claridge, G.G.C., 1987. Antarctica: Soils, Weathering
Processes and Environment. Elsevier, Amsterdam.
Champ, M.A., Flemer, D.A., Landers, D.H., Ribic, C., DeLaca, T.,
1992. The roles of monitoring and research in polar environments:
a perspective. Marine Pollution Bulletin 25, 220226.
Ciaralli, L., Giordano, R., Lombardi, G., Beccaloni, E., Sepe, A.,
Costantini, S., 1998. Antarctic marine sediments: distribution of
elements and textural characters. Microchemical Journal 59, 77
88.
Claridge, C.G.C., Campbell, I.B., Powel, H.K.J., Amim, Z.H., Balks,
M.R., 1995. Heavy metal contamination in some soils of the
McMurdo Sound region, Antartica. Antarctic Science 7, 914.
Clark, M.W., McConchie, D., Lewis, D.W., Saenger, P., 1998. Redox
stratication and heavy metal partitioning in Avicennia-dominated
mangrove sediments: a geochemical model. Chemical Geology 149,
147171.
Daskalakis, K.D., OConnor, T.P., 1995. Distribution of chemical
concentrations in US coastal and estuarine sediment. Marine
Environmental Research 40, 381398.
Fernandes, H.M., 1997. Heavy metal distribution in sediments and
ecological risk assessment: The role of diagenetic processes in
reducing metal toxicity in bottom sediments. Environmental
Pollution 97, 317325.
Forstner, U., Wittman, G.T.W., 1983. Metal Pollution in the Aquatic
Environment. Springer-Verlag, Berlin.

194

I.R. Santos et al. / Marine Pollution Bulletin 50 (2005) 185194

Francois, R., 1988. A study on the regulation of the concentrations of


some trace elements (Rb, Sr, Zn, Pb, Cu, V, Cr, Ni, Mn and Mo) in
Saanich Inlet sediments, British Columbia, Canada. Marine
Geology 83, 285308.
Gomes, M.S., 1999. Determinacao de elementos metalicos em
sedimentos antarticos. M.Sc. Thesis, Universidade de Sao Paulo.
Green, W.J., Ferdelman, T.G., Caneld, D.E., 1989. Metal dynamics
in Lake Vanda (Wright Valley, Antarctica). Chemical Geology 76,
8594.
Groeneweg, W.J., Beunk, F.F., 1992. The petrography and geochemistry of the King George Island supergroup and Admiralty Bay
group volcanics, South Shetland Islands. In: Lopez-Martinez, J.
(Ed.), Geologia de la Antartida Occidental, pp. 4660. Salamanca:
III Congreso Geologico de Espana y VIII Congresso Latinoamericano de Geologia.
Karageorgis, A., Anagnostou, C., Sioulas, A., Chronis, G., Papathanassiou, E., 1998. Sediment geochemistry and mineralogy in Milos
bay, SW Kyklades, Aegean Sea, Greece. Journal of Marine
Systems 16, 269281.
Kennicutt, M.C., Mcdonald, S.J., Sericano, J.L., Boothe, P., Oliver, J.,
Safe, S., Presley, B.J., Li, H., Wolfe, D., Wade, T.L., Crockett, A.,
Bockus, D., 1995. Human contamination of the Marine EnvironmentArthur Harbor and McMurdo Sound, Antarctica. Environmental Science and Technology 29, 12791287.
King, C.K., Riddle, M.J., 2001. Eects of metal contaminants on the
embryonic and larval development of the common Antarctic sea
urchin Sterechinus neumayeri (Meissner). Marine Ecology Progress
Series 215, 143154.
Lenihan, H.S., 1992. Benthic marine pollution around McMurdo
Station, Antarctica: A summary of ndings. Marine Pollution
Bulletin 25, 318323.
Lenihan, H.S., Oliver, J.S., Oakden, J.M., Stephenson, M.D., 1990.
Intense and localized benthic marine pollution around McMurdo
Station, Antarctica. Marine Pollution Bulletin 21, 422430.
Liu, W.X., Li, X.D., Shen, Z.G., Wang, D.C., Wai, O.W.H., Li, Y.S.,
2003. Multivariate statistical study of heavy metal enrichment in
sediments of the Pearl River Estuary. Environmental Pollution 121,
377388.
Luoma, S.N., Bryan, G.W., 1981. A statistical assessment of the forms
of trace metals in oxidized estuarine sediments employing chemical
extractants. The Science of the Total Environment 17, 165196.
Machado, A., Chemale Jr., F., Lima, E.F., Figueiredo, A.M.G., 1998.
Petrologia das rochas vulcanicas da Pennsula Fildes, Ilha Rei
George, Antartica. Pesquisas em Geociencias 25, 3542.
vila, J.N., 2001.
Machado, A., Lima, E.F., Chemale Jr., F., Liz, J.D., A
Qumica mineral de rochas vulcanicas da Pennsula Fildes (Ilha Rei
George), Antartica. Revista Brasileira de Geociencias 31, 299306.
Martins, C.C., Venkatesan, M.I., Montone, R.C., 2002. Sterols and
linear alkylbenzenes in marine sediments from Admiralty Bay,
King George Island, South Shetland Islands. Antarctic Science 14,
244252.
Merlin, O.H., Salvador, G.L., Vitturi, L.M., Pistolato, M., Rampazzo,
G., 1989. Preliminary results on trace element geochemistry of
sediments from the ross sea, Antarctica. Bolletino di Oceanologia
Teorica ed Aplicata 7, 97108.
Niencheski, L.F.H., Baraj, B., Franca, R.G., Mirlean, N., 2002.
Lithium as a normalizer for assessment of anthropogenic metal
contamination of sediments of the southern area of Patos Lagoon.
Aquatic Ecosystem Health and Management 5, 473483.
Pride, D.E., Cox, C.A., Moody, S.V., Conelea, R.R., Rosen, M.A.,
1990. Investigation of mineralization in the South Shetland Islands,
Gerlache Strait, and Anvers Island, Northern Antarctic Peninsula.
Antarctic Research Series 51, 6994.
Rakusa-Suszczewski, S., 1980. Environmental conditions and functioning of Admiralty Bay (South Shetland Islands) as part of the
near shore Antarctic ecosystem. Polish Polar Research 1, 1127.

Salomons, W., Forstner, U., 1984. Metals in the Hydrocycle. SpringerVerlag, Berlin.
Santos, I.R., Schaefer, C.E., Silva-Filho, E.V., Albuquerque, M.,
Albuquerque-Filho, M.R., 2004. Contaminantes antropicos em
ecossistemas antarticos: estado-de-arte. In: Schaefer, C.E., Francelino, M.R., Simas, F.B., Albuquerque-Filho, M.R. (Eds.), Ecossistemas costeiros e monitoramento ambiental da Antartica
Martima: Baa do Almirantado, Ilha Rei George. NEPUT,
Vicosa, pp. 95106.
Schaefer, C.E., Francelino, M.R., Simas, F.N., Costa, L.M., 2004.
Geologia e Geotectonica da Pennsula Keller, Antartica martima.
In: Schaefer, C.E., Francelino, M.R., Simas, F.N., AlbuquerqueFilho, M.R. (Eds.), Ecossistemas costeiros e monitoramento
ambiental da Antartica martima, Baa do Almirantado, Ilha Rei
George. NEPUT, Vicosa, pp. 713.
Sheppard, D.S., Claridge, G.G.C., Campbell, I.B., 2000. Metal
contamination of soils at Scott Base, Antarctica. Applied Geochemistry 15, 513530.
Smith, S.D.A., Simpson, R.D., 1995. Eects of the Nella Dam oil spill
on the fauna of Durvillaea antarctica holdfasts. Marine Ecology
Progress Series 121, 7389.
Sokal, R.R., Rohlf, F.J., 1981. Biometry 2. W.H. Freeman and
Company, New York.
Szefer, P., Geldon, J., Ali, A.A., Paez Osuna, F., Ruiz-Fernandes,
A.C., Guerrero Galvan, S.R., 1998. Distribution and association of
trace metals in soft tissue and byssus of mytella strigata and other
benthal organisms from Mazatlan Harbour, mangrove lagoon of
northwest coast of mexico. Environment International 24, 359374.
Szefer, P., Glasby, G.P., Pempkowiak, J., Kaliszan, R., 1995.
Extraction studies of heavy-metal pollutants in surcial sediments
from the Southern Baltic Sea o Poland. Chemical Geology 120,
111126.
Wasserman, J.C., Figueiredo, A.M.G., Pellegatti, F., Silva-Filho, E.V.,
2001. Elemental composition of sediment cores from a mangrove
environment using neutron activation analysis. Journal of Geochemical Exploration 72, 129146.
Wasserman, J.C., Oliveira, F.B.L., Bidarra, M., 1998. Cu and Fe
associated with humic acids in sediments of a tropical coastal
lagoon. Organic Geochemistry 28, 813822.
Webster, J., Webster, K., Nelson, P., Waterhouse, E., 2003. The
behaviour of residual contaminants at a former station site,
Antarctica. Environmental Pollution 123, 163179.
Wedepohl, K.H., 1995. The composition of the continental crust.
Geochimica et Cosmochimica Acta 59, 12171232.
Wenchuan, Q., Dickman, M., Sumin, W., 2001. Multivariate analysis
of heavy metal and nutrient concentrations in sediments of Taihu
Lake, China. Hydrobiologia 450, 8389.
Wijsman, J.W.M., Herman, P.M.J., Middelburg, J.J., Soetaert, K.,
2002. A model for early diagenetic processes in sediments of the
continental shelf of the Black sea. Estuarine, Coastal and Shelf
Science 54, 403421.
Wijsman, J.W.M., Middelburg, J.J., Herman, P.M.J., Bottcher, M.E.,
Heip, C.H.R., 2001. Sulfur and iron speciation in surface sediments
along the northwestern margin of the Black sea. Marine Chemistry
74, 261278.
Windom, H., Schropp, S.J., Calder, F.D., Ryan, J.D., Smith, R.G.,
Burney, l.C., Lewis, F.G., Rawlinson, C.H., 1989. Natural trace
metal concentrations in estuarine and coastal marine sediments of
the Southeastern United States. Environmental Science and Technology 23, 314324.
Zhang, C., Selinus, O., Schedin, J., 1998. Statistical analyses for heavy
metal contents in till and root samples in an area of Southeastern
Sweden. The Science of the Total Environment 212, 217232.
Zhang, J., 1995. Geochemistry of trace metals from chinese river/
estuary systems: An overview. Estuarine, Coastal and Shelf Science
41, 631658.

You might also like