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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.
*
0025-326X/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpolbul.2004.10.009
186
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.
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-
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).
188
Table 1
Average content of metals in studied soils and sediments in comparison with results of other studies
Matrice (local)
a
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
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.
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).
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
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***
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*
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
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
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
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).
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.
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
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