Advances in Environmental Research 6 Ž2001.

29᎐43

Spatial and seasonal variations of major, minor and

trace elements in Antarctic seawater. Chemometric
investigation of variable and site correlations

Ornella Abollino a , Maurizio Aceto b, Carmela La Gioiaa ,

Corrado Sarzanini a , Edoardo Mentasti a,U
a
Department of Analytical Chemistry, Uni¨ ersity of Torino, Via P. Giuria 5, 10125 Turin, Italy
b
Department of Science and Ad¨ anced Technologies, Uni¨ ersity of East Piedmont, Corso Borsalino 54, 15100 Alessandria,
Italy

Abstract

The concentrations of fourteen elements in seawater collected during the 1994᎐95 and 1995᎐96 Italian expeditions
to Antarctica were determined by stripping voltammetry or atomic spectroscopy. The results obtained are discussed
as a function of the sampling period and location. Heavy metal concentrations for samples collected during the
1993᎐94 campaign are also reported. Dissolved levels of major, minor and trace elements were found to decrease
after pack ice melting because of water dilution and bioaccumulation, the latter being particularly relevant for heavy
metal concentrations. The elaboration by chemometric multivariate techniques allowed identification of two groups
of samples, respectively, collected before and after pack ice melting, and to find correlations among variables, such as
alkaline-earth metals. 䊚 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Seawater; Heavy metals; Traces, Pack ice; Chemometrics

1. Introduction groups, namely: Ži. major components ŽNa, K, Ca, Mg.,

The relative composition of seawater, at least for
major and minor components, is approximately con-
stant throughout the planet, despite spatial and tem-
poral variabilities, owing to efficient water mixing
mechanisms and to the action of biogeochemical cycles
by which a balance between material input and output
is maintained ŽLibes, 1992; Stumm and Morgan, 1996..
Metals present in seawater can be divided into three
U ment and the natural processes involving the hydro-
Corresponding author. Tel.: q39-011-6707625; Fax: q39-
011-6707615.
E-mail address: mentasti@ch.unito.it ŽE. Mentasti..
with millimolar concentration levels; Žii. minor compo-
nents such as Ba, Li, Sr, whose concentrations are in
the ␮molrly1 range; other minor components are B
and Si; Žiii. trace and ultratrace components, such as
heavy metals, having concentrations from approxi-
mately 10y9 M down to pmol ly1.
The aim of this paper is the investigation of major,
minor and trace element content in the waters of the
Ross Sea ŽAntarctica.. The virtual absence of anthro-
pogenic activities makes Antarctica an ideal site to
study the behaviour of chemical species in the environ-
sphere, atmosphere, lithosphere and biosphere. An-
other reason for studying the Antarctic area is the

1093-0191r01r$ - see front matter 䊚 2001 Elsevier Science Ltd. All rights reserved.
PII: S 1 0 9 3 - 0 1 9 1 Ž 0 1 . 0 0 0 6 8 - X
30 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43
influence of polar regions on the global planetary
processes such as climate or water and air circulation.
There are relatively few data on inorganic elements in
the waters surrounding Antarctica, although, some in-
formation on heavy metals is available. Dissolved and
suspended Cd, Cu, Ni, Fe, Pb and Zn were determined
at different depths in the Weddell Sea ŽWesterlund and
Ohman, 1991a,b.. The distribution of cadmium
ŽLoscher et al., 1998., iron Žde Jong et al., 1998., nickel,
copper and zinc ŽLoscher, 1999. and their relationships
with nutrients in the Polar Front in the Atlantic sector
of the Southern Ocean were investigated. The bio-
geochemistry of iron was also studied in the Pacific and
Australian sectors of the Southern Ocean Žde Baar et
al., 1999; Sohrin et al., 2000.. The distribution of heavy
metals ŽCd, Cu, Fe, Mn, Ni and Zn. was determined in
the Ross Sea ŽAbollino et al., 1995; Frache et al., 1997.
and the speciation of cadmium, lead and copper was
investigated as well ŽCapodaglio et al., 1998.. Iron and
manganese were measured in the Polynya Region of
the southern Ross Sea ŽSedwick et al., 2000..
The present authors have been involved in the Ital-
ian investigation programme on Antarctica Ž‘Pro-
gramma Nazionale di Ricerche in Antartide’, PNRA.
since 1987. The results reported here refer to the
1993᎐94, 1994᎐95 and 1995᎐96 expeditions in the Ross
Sea.
The 1993᎐94 samples are from coastal seawater col-
lected in the same site at two different depths before
ŽNovember. and after ŽJanuary. ice pack melting. Dur-
ing the 1995᎐96 campaign coastal seawater was col-
lected in December 1995 and January 1996, respec-
tively, before and after pack ice melting. In the 1994᎐95
expedition, open seawater was collected during two
different periods of the Antarctic summer, i.e. Novem-
ber᎐December and January᎐February. Attention was
focused on fourteen analytes, namely Cd, Cu, Fe, Mn,
Ni, Na, Ca, K, Mg, B, Ba, Li, Si, Sr, for the 1994᎐95
and 1995᎐96 samples, and on heavy metals ŽCd, Cu, Fe,
Mn, Ni. for the 1993᎐94 ones. The results obtained
were treated with different statistical procedures.
Among the investigated parameters, the most mean-
ingful from the environmental point of view are heavy
metals, since they are potentially toxic and their pres-
ence at anomalous values can be an index of pollution.
As an example, industrial pollution from terrestrial
areas is reflected in trace metal concentrations in
coastal and semi-open seawater in Japan ŽYabutani et
al., 2000.. Water pollution in the Gulf of Valencia
ŽWestern Mediterranean . was assessed by determina-
tion of heavy metals together with other contamination
markers, such as microbiological agents ŽMorales et al.,
1999.. Trace metal distribution was also investigated in
the Arctic Ocean ŽYeats and Westerlund, 1991; Lockart
et al., 1992.. Four out of the five investigated metals,
namely copper, iron, manganese and nickel, are essen-
tial to life, because of their role in enzyme systems for
many biochemical processes, and become toxic at high
concentration. On the other hand, cadmium has no
known biological function and is toxic at low levels.
The bioaccumulation of heavy metals initiates with
complexation by chelating groups present on the exter-
nal surface of the organism. Enrichment factors, i.e.
ratios between metal concentrations in organisms to
the ones in seawater, are of the order of 10 3 ᎐10 4 and
can be as high as 10 5 ŽLibes, 1992.. Bioaccumulation
affects the concentration of both essential and toxic
metals; for instance the enrichment factor for lead in
plankton is 41 000, compared with 17 000 for copper
and 87 000 for iron ŽLibes, 1992.. Cadmium, whose
enrichment factor is 910, has a nutrient-type distribu-
tion in seawater, like some essential elements such as
Zn and Ni, because of its involvement in the cycle of
biologically derived particulate matter ŽGrasshoff et al.,
1999.. Moreover, metal complexation in the organism
tissues is a defence mechanism to decrease their toxic-
ity. The biogeochemical cycles of heavy metals have
been extensively studied Žsee for instance Libes, 1992;
Donat and Bruland, 1995; Stumm and Morgan, 1996..
Much attention was devoted to iron, owing to its bio-
logical and geochemical importance and its complex
chemistry ŽSedwick et al., 1997; Gordon et al., 1998;
Nolting et al., 1998; Johnson et al., 1999.. Other inves-
tigations regarded for instance aluminium ŽChou and
Wollast, 1997., cadmium and copper ŽMuller, 1996;
Camusso et al., 1998., manganese ŽMinakawa et al.,
1996; Sedwick et al., 1997. and nickel ŽCamusso et al.,
1998..
The knowledge of the concentrations of the other
considered species is also of significance for a better
characterization of the waters under study and for their
involvement in the bio-physico-chemical phenomena
controlling the composition of seawater. Moreover, few
analytical data are available in the literature for
Antarctica, owing to difficulties and high costs of sam-
pling. Therefore, even information on major and minor
metals is of interest in order to have a broader data set
on this remote continent and to be able to make
comparisons with other sites in the world.
The results obtained are discussed in their connec-
tion with the biogeochemical cycle occurring in the
Antarctic Ocean, with particular attention to the seaso-
nal changes in water composition.
2. Experimental
2.1. Sample collection and pre-treatment
Samples were collected with PTFE-coated Go-Flo
bottles or with a submersible Teflon pump and were
 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43 31

immediately filtered through 0.45 ␮m membrane filters,
transferred into previously cleaned polyethylene bot-
tles, and kept frozen during transportation and storage
in our laboratory.
The samples were defrosted and acidified with con-
centrated ultrapure nitric acid Ž1 ml ly1 . at least 1 day
before analysis, in order to allow chemical equilibra-
tion.
The Italian expeditions to Antarctica were per-
formed in the period of the year when pack ice melting
occurs. Table 1 reports the relevant sampling details,
such as latitude, longitude and date of sampling, for
the investigated seawater samples. Samples 1᎐4 are
from coastal seawater collected in Wood Bay
Ž74⬚22⬘.120 S, 165⬚24⬘.058 E. during the 1993᎐94 expe-
dition on the water surface Ž1, 3. and at 350 m depth
Ž2, 4. before Ž1, 2. and after Ž3, 4. pack ice melting.
Samples 5᎐24 were collected during the 1994r95 expe-
dition off-shore in the Ross Sea at a depth of 30 m,
between 71⬚30⬘ S and 78⬚07⬘ S in latitude, 165⬚48⬘ E
and 179⬚60⬘ E in longitude; in particular, samples 5᎐14
were collected in the early period of the Antarctic

Table 1
Geographical location and date of sampling for seawater collected during the Italian expeditions to Antarctica in 1994r95 and
1995r96 a

Sample Sampling Date of sampling Latitude, S Longitude, E

no. site code
1993᎐94 campaign
1 ᎐ 19-11-1993 74⬚22⬘.120 165⬚24⬘.058
2 ᎐ 19-11-1993 74⬚22⬘.120 165⬚24⬘.058
3 ᎐ 09-01-1994 74⬚22⬘.120 165⬚24⬘.058
4 ᎐ 09-01-1994 74⬚22⬘.120 165⬚24⬘.058

1994᎐95 campaign
5 1-X 17-11-1994 75⬚28⬘.920 174⬚57⬘.147
6 2-X 15-12-1994 74⬚58⬘.757 167⬚59⬘.139
7 3-X 19-11-1994 76⬚36⬘.689 169⬚25⬘.971
8 4-X 20-11-1994 75⬚25⬘.322 175⬚00⬘.645
9 5-X 22-11-1994 74⬚45⬘.308 175⬚01⬘.868
10 6-X 01-12-1994 73⬚54⬘.549 171⬚40⬘.639
11 7-X 02-12-1994 72⬚25⬘.864 174⬚56⬘.149
12 8-X 03-12-1994 73⬚27⬘.144 175⬚00⬘.904
13 9-X 08-12-1994 72⬚30⬘.211 177⬚01⬘.165
14 10-X 14-12-1994 74⬚42⬘.233 172⬚00⬘.797
15 Z-8 23-01-1995 77⬚28⬘.381 176⬚44⬘.559
16 Z-20 24-01-1995 78⬚06⬘.999 168⬚28⬘.167
17 Z-23 25-01-1995 77⬚32⬘.729 165⬚48⬘.398
18 Z-29 26-01-1995 77⬚31⬘.441 170⬚51⬘.441
19 Z-34 27-01-1995 78⬚00⬘.622 177⬚04⬘.910
20 Z-56 30-01-1995 77⬚16⬘.048 175⬚09⬘.345
21 Z-67 31-01-1995 76⬚30⬘.203 176⬚12⬘.829
22 Z-86 03-02-1995 75⬚10⬘.435 175⬚59⬘.313
23 Z-97 08-02-1995 72⬚40⬘.130 179⬚59⬘.970
24 Z-106 11-02-1995 71⬚29⬘.535 172⬚40⬘.812

1995᎐96 campaign
25 10 24-01-1996 74⬚40⬘.2 164⬚06⬘.5
26 11 25-01-1996 74⬚40⬘.1 164⬚17⬘.5
27 13 26-01-1996 74⬚39⬘.6 164⬚13⬘.5
28 14 26-01-1996 74⬚40⬘.2 164⬚10⬘.1
29 15 28-01-1996 74⬚41⬘.2 164⬚06⬘.0
30 8 23-01-1996 74⬚39⬘.0 164⬚09⬘.5
31 16 31-01-1996 74⬚41⬘.2 164⬚16⬘.4
32 17 31-01-1996 74⬚42⬘.4 164⬚11⬘10
33 20 02-02-1996 74⬚41⬘.3 164⬚25⬘.0
34 21 02-02-1996 74⬚42⬘.1 164⬚20⬘.0
a
Samples 1᎐2, 5᎐14 and 25᎐30 were collected before pack melting; samples 3᎐4, 15᎐24 and 31᎐34 were collected after pack
melting. Samples 1,3: surface water; samples 2,4: water collected at 350 m depth.
32 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43
summer, in the presence of pack ice, whereas samples
15᎐24 were collected later, after the melting of most of
the pack and in the presence of strong biological activ-
ity ŽLibes, 1992.. Samples 25᎐34 are from coastal sur-
face water collected during the 1995r96 campaign in
Gerlache Inlet Žbetween 74⬚39⬘ S and 74⬚42⬘ S in
latitude, 164⬚06⬘ E and 164⬚25⬘ E in longitude., a small
bay close to the Italian Station in Antarctica, before
Ž25᎐30. and after Ž31᎐34. melting.
2.2. Reagents and instrumentation
High purity water from a Milli-Q apparatus was used
throughout.
Ultrapure acids and ammonia were obtained by
sub-boiling distillation in a quartz still ŽK. Kurner,
Rosenheim, Germany..
A Mettler Delta 320 pH-meter equipped with a
combined glass-calomel electrode was used for pH
measurements.
Voltammetric determinations were performed with a
PAR 384B voltammetric analyser equipped with a
hanging mercury drop electrode ŽHMDE., a platinum
counter electrode and a AgrAgCl reference electrode,
driven by PC via dedicated software.
The electrothermal atomic absorption spectrometer
was a Perkin-Elmer 5100 with Zeeman-effect back-
ground correction equipped with an HGA 600 graphite
furnace, an AS-60 autosampler and interfaced to a
personal computer for the execution of analysis and
data collection. Pyrocoated graphite tubes were used
throughout. The autosampler arm was modified in or-
der to accommodate a preconcentration column packed
with silica C 18 Ž40᎐63 mesh, Merck. ŽPorta et al., 1991..
The column was connected to a home-made precon-
centration apparatus consisting of a Gilson Minipuls 2
peristaltic pump and a Rheodyne valve.
The inductively coupled plasma atomic emission
spectrometer was a Varian Liberty 100 equipped with a
V-groove nebulizer, a Sturman᎐Masters spray chamber
and operated in a sequential fashion.
Standard metal solutions were prepared from con-
centrated stock solutions ŽMerck Titrisol.. Acetonitrile,
ammonium pyrrolidine dithiocarbamate ŽAPDC., 1-
nitroso-2-naphthol Ž1N-2N., boric acid and hydroxylam-
monium chloride were purchased from Merck; pipera-
zine-NN⬘-bis-2-ethanesulfonic acid ŽPIPES., 4-Ž2-hy-
droxyethyl.piperazine-1-ethanesulfonic acid ŽHEPES.
and 8-hydroxyquinoline were Fluka products; dimethyl-
glyoxime ŽDMG. was obtained from Aldrich. Am-
monium acetate buffer was obtained by mixing volumes
of acetic acid and ammonia required to obtain the
desired pH.
Trace metal determinations were performed in a
controlled atmosphere laboratory equipped with lami-
nar flow hoods in which sample and reagent handling
was carried out.
2.3. Procedures
The following methods were used.
2.3.1. Determination of cadmium and copper
Cd and Cu in the samples collected in 1993᎐94 and
1994᎐95 were determined by electrothermal atomic
absorption spectroscopy coupled with on-line precon-
centration ŽPRECrETAAS. according to a previously
developed procedure ŽPorta et al., 1991; Abollino et al.,
1995.. The analytes were complexed on line with APDC
Žbuffered with NH 4 Ac., retained on the microcolumn
and directly eluted into the furnace with CH 3 CN.
The samples collected in the subsequent campaign
were analysed by adsorptive cathodic stripping vol-
tammetry ŽACSV. according to previously described
procedures ŽAbollino et al., 1995.. The samples were
buffered at pH 7.7 with HEPES᎐NH 3 and the analytes
were complexed with 8-hydroxyquinoline. Deposition
potential was y0.30 V for Cu and y1.10 V Žstart
potential y0.30 V. for Cd. Deposition time was 120 s
for Cu and 180 s for Cd.
2.3.2. Determination of iron
Fe was determined by ACSV with 1N-2N and
PIPES-NH 3 buffer ŽpH 6.9. and hydroxylammonium
chloride as reducing agent. The deposition potential
was ᎐0.20 V and the deposition time was 120 s Žvan den
Berg et al., 1991..
2.3.3. Determination of manganese
Mn was determined by PRECrETAAS after on-line
complexation with OX at pH 9.0.
2.3.4. Determination of nickel
Ni was determined by ACSV with DMG and boric
acid᎐NH 3 buffer ŽpH 8.3.. The deposition potential
was y0.70 V and the deposition time 120 s ŽAbollino
et al., 1995..
2.3.5. Determination of B, Ba, Ca, K, Li, Mg, Na,
Si, Sr
Major and minor elements were determined by in-
ductively coupled plasma atomic emission spectrometry
in the samples as such ŽB, Ba, Li, Si., after 100- ŽCa,
Mg, K. and 1000- ŽNa. fold dilution.
Voltammetric potential scans were performed in the
square wave mode Žfrequency 100 Hz, scan increment 2
mV, pulse height 20 mV..
 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43 33

Table 2 two unsupervised whierarchical cluster analysis ŽHCA.

Blanks and detection limits Žvalues in nM for Cd, Cu, Fe, Mn, and principal component analysis ŽPCA.x and one su-
Ni, ␮M for the other elements.. The detection limits were pervised wdiscriminant analysis ŽDA.x ŽMassart et al.,
calculated as three times the standard deviation of the blanks
1988.. Each campaign was treated separately, consider-
except for Ca, K, Ba, Li, Si, Sr Žfor these elements the
ing only samples belonging to that campaign.
detection limit coincides with the instrumental limit.
HCA was used to check similarities between sam-
Element Blank Detection limit ples. The procedure was run applying Ward’s method
of agglomeration and squared Euclidean distance as
Cd 0.09 ŽACSV. 0.06 ŽACSV. similarity measure. All variables were standardized.
0.06 ŽPRECrETAAS. 0.04 ŽPRECrETAAS. PCA was used to allow an easy representation of
Cu 0.71 ŽACSV. 0.33 ŽACSV. samples in a two-dimensional diagram. The first three
0.60 ŽPRECrETAAS. 0.22 ŽPRECrETAAS.
PCs were extracted and utilized in bivariate plots;
Fe 0.93 0.57
loadings too were considered, to evaluate correlations
Mn 0.24 0.15
Ni 0.75 0.16 between variables Ži.e. metal concentrations ..
Na 0.26 0.06 To use the DA method, two classes were defined a
Ca - 0.15 0.15 priori for each campaign, considering samples collected
K - 0.51 0.51 before or after pack dissolution. Univariate ANOVA
Mg 0.03 8 ⭈ 10y3 was used to calculate F-ratios and find variables with
Ba 8 ⭈ 10y4 5 ⭈ 10y4 higher discriminating power. One canonical discrimi-
B 6.01 1.09 nant function was obtained and probabilities of class
Li - 0.09 0.09 membership were calculated for all samples.
Si 0.25 0.18
Sr 3 ⭈ 10y4 2 ⭈ 10y4

3. Results and discussion

All concentrations were evaluated with the standard
addition method and are the average of three indepen-
dent determinations corrected for blank values. The
latter are reported in Table 2 together with the detec-
tion limits. In the case of heavy metals, detection limits
are mainly influenced by contaminations, which easily
occur at nanomolar levels, even if great care is adopted
in order to minimize them. The sensitivity of both
ACSV and PRECrGFAAS would allow detection at
lower concentrations. The greatest contribution to the
blanks was found to derive from nitric acid. The rela-
tive standard deviations were typically 10% for Cd
ŽACSV., Cu, Ni, 5% for Cd ŽPRECrETAAS. and Mn,
15% for Fe, 3% or lower for all other analytes. The
accuracy of the procedures for Cd, Cu, Fe and Ni
determination had been tested in a previous work on
Antarctic seawater ŽAbollino et al., 1995. in which the
same sample had been analysed both by ACSV and
PRECrETAAS: the results obtained were similar, dif-
fering by no more than 10%. The accuracy of the
ACSV procedure for iron had also been tested by
analysis of certified seawater Žvan den Berg et al.,
1991..
2.4. Multi¨ ariate techniques
To verify the existence of relationships between the
samples, some pattern recognition methods were used,
The seawater samples investigated have different
origins from the point of view of the collection site
andror period. In fact, during most of the year the
Ross Sea is to a great extent ice covered. The thickness
of the pack ice is approximately 2᎐4 m and it reaches a
maximum extension of 2 = 10 7 km2 in September. Dur-
ing spring and summer the pack ice starts melting and
is decreased by more than 80% in March. Therefore, a
large volume of water is released into the ocean, giving
rise to physical as well as chemical effects.
Tables 3 and 4 report the concentrations of the
investigated analytes in the samples. Concentration
ranges and average values are presented in Tables 5
and 6. Some outliers were excluded from the calcula-
tions. In particular sample 30, probably contaminated
with heavy metals, and 28 Žboth from 1995᎐96 cam-
paign, collected after pack melting., with a much lower
content of the other analytes, were excluded from the
calculations of the averages for heavy metal and major
and trace elements respectively. Samples 17 and 19,
characterized by an anomalous sodium content Žwhose
source remains unexplained., were not considered in
the calculation of the mean sodium concentration.
The results obtained provide insight into the ele-
ments behaviour and their temporal variability. They
will be discussed also in the light of the global bio-
geochemical cycle in which the investigated analytes
are involved. The following acronyms will be used
hereafter to describe sample identities: before pack
melting ŽBPM. and after pack melting ŽAPM..
34 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43

Table 3
Major and minor element concentrations in Ross Sea Žvalues in mM for Na, Ca, K, Mg, B, ␮M for Li, Si, Sr, nM for Ba. a

Sample Na Ca K Mg Ba B Li Si Sr

1994᎐95 campaign
5 461 10.50 11.25 61.78 51 0.32 17 59 89
6 478 12.05 10.46 61.00 73 0.45 29 74 95
7 452 12.15 11.12 62.44 160 0.47 27 67 95
8 467 8.46 9.23 51.21 138 0.42 29 74 72
9 465 10.15 10.46 55.98 124 0.47 26 72 80
10 435 11.60 10.20 58.98 73 0.40 19 62 87
11 435 11.98 12.07 70.66 73 0.40 26 65 103
12 458 12.52 13.32 72.10 73 0.42 22 64 105
13 437 10.55 10.23 57.13 73 0.41 26 68 84
14 461 11.65 12.45 71.32 116 0.45 26 72 100
15 437 7.73 7.95 42.24 73 0.33 20 42 67
16 431 13.25 14.12 72.72 138 0.38 23 46 107
17 528 12.20 10.20 59.64 124 0.45 29 49 92
18 449 10.28 9.05 49.77 73 0.29 13 46 82
19 521 8.88 8.90 48.70 87 0.41 20 59 74
20 448 9.03 7.77 46.15 73 0.39 27 55 75
21 429 8.58 9.08 48.00 80 0.44 26 58 72
22 448 6.76 6.47 37.10 73 0.28 13 38 60
23 473 10.70 12.04 62.64 87 0.40 23 57 92
24 468 9.90 10.00 56.47 80 0.41 27 73 82

1995᎐96 campaign
25 448 10.18 9.41 55.32 66 0.40 26 60 88
26 456 10.13 9.85 55.40 80 0.40 24 58 86
27 439 9.88 9.92 55.28 66 0.37 30 63 84
28 402 7.04 7.16 40.56 87 0.31 19 54 74
29 439 9.31 9.23 57.38 66 0.44 23 63 80
30 440 10.15 9.36 55.24 73 0.41 27 61 87
31 461 10.30 8.82 57.91 73 0.46 26 60 88
32 440 9.08 8.44 49.48 95 0.36 26 56 81
33 454 10.38 9.10 47.47 73 0.40 29 67 89
34 452 9.86 9.44 55.61 80 0.34 20 57 87
a
Samples 5᎐14 and 25᎐30 were collected before ice pack melting; samples 15᎐24 and 31᎐34 were collected after pack melting.

3.1. Major elements
The results obtained in the present study for major
elements ŽTables 3 and 5. show that the concentrations
of Ca, K and Mg decrease after pack melting, as
expected because of the water dilution effect. The
sodium content in the 1994᎐95 samples decreased as
well, whereas it slightly increased in the 1995᎐96 sam-
ples. Such an increase cannot be clearly interpreted: it
might be due to an input from the ice, which could
have trapped some impurities during freezing.
As to spatial distribution, concentrations were usu-
ally lower in the Gerlache Inlet than in the open Ross
Sea. This trend cannot be attributed to river run-off, as
in other coastal areas in the world, since real water
streams are nearly absent in Antarctica.
The concentrations of the major metals found in this
study are in good agreement with the typical values for
seawaters with salinity 35, Ž460 mM for Na, 10.28 mM
for Ca, 10.20 mM for K, 53.06 mM for Mg. ŽLibes,
1992; Stumm and Morgan, 1996.; the same applies to
the considered minor and trace elements, whose be-
haviour will be discussed below. This confirms the
statement on the constancy of seawater relative compo-
sition connected to the element biogeochemical cycle.
The average sodium concentrations in the investi-
gated areas were slightly lower than the typical value of
468 mM, owing to the lower salinity. Ca, K and Mg
average concentrations in the open Ross Sea before
pack melting are higher than the typical ones, and
lower in most other cases.
Major elements in seawater exhibit conservative be-
haviour. The consequence of physical control of their
concentrations is that the proportions among conserva-
tive species are constant even if their single concentra-
tions may change Žrule of constant proportion. ŽLibes,
 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43 35

Table 4 were excluded from the mean, relative standard devia-

Heavy metal concentrations ŽnM. in Ross Seaa tions would decrease from 23.8 to 12.6, 20.2 to 11.8,
20.6 to 11.3% Žrespectively, for NarK, NarCa, NarMg
Sample Cd Cu Fe Mn Ni
in the 1994᎐95 samples before pack melting. and from
11.7 to 9.7, 14.1 to 8.4, 12.4 to 10.2% Žfor the same
1993᎐94 campaign
1 0.48 2.2 18.6 0.8 4.6 ratios after pack melting.. In these conditions, the
2 0.58 4.0 21.9 0.8 9.3 highest deviation would be 12.6% and most values
3 0.31 0.4 2.95 ᎐ 4.2 would be below 10%. We decided anyway to include
4 0.36 1.3 10.4 1.8 6.6 the three samples in the calculations reported in Table
7, because we cannot make a hypothesis on the causes
1994᎐95 campaign of their difference from the other ones: further investi-
5 0.72 0.5 1.8 0.4 4.0 gations in the area would be required to understand
6 0.86 2.7 4.0 1.0 6.4 the behaviour of the considered analytes. We also
7 0.80 3.3 3.6 2.2 6.4 calculated the same ratios from data reported by other
8 0.79 4.8 2.5 0.6 5.3 authors for the Ross Sea ŽPapoff et al., 1991., and we
9 0.54 2.5 1.8 1.2 4.9
found relative standard deviations ranging from 3.5 to
10 0.98 3.6 4.2 0.4 9.0
21%, most being approximately 10%, i.e. similar to the
11 0.57 4.3 6.3 0.5 5.3
12 0.55 2.9 2.7 1.6 7.0 ones found in this study.
13 0.93 0.7 7.1 0.6 7.2 In general, the variability of the ratios is due to both
14 0.60 3.4 2.8 0.2 6.7 analytical variability Žalways present in any set of analy-
15 0.12 0.8 0.6 0.4 5.5 sis. and to the characteristics of polar water, suggesting
16 0.15 1.4 1.7 0.2 5.8 that the behaviour is not purely conservative.
17 0.08 0.7 1.1 0.6 4.6
18 0.28 1.7 2.7 0.6 3.3
3.2. Minor elements
19 0.11 0.6 0.7 0.3 5.4
20 0.32 2.7 0.9 0.2 4.6
21 0.67 2.3 1.1 0.4 1.9 As Tables 3 and 5 show, minor element concentra-
22 0.20 0.9 1.2 0.3 3.0 tions in the open Ross Sea Ž1994᎐95 expedition. de-
23 0.92 1.4 0.8 0.2 8.0 creased after pack ice melting: this behaviour is due
24 0.43 1.8 2.4 0.5 5.3 both to the input of freshwater and to the biological
uptake. This decrease occurred only for three ele-
1995᎐96 campaign ments, and to a limited extent, in Gerlache Inlet
25 0.55 1.6 1.7 1.1 4.4 Ž1995᎐96 campaign.: the reason for this different trend
26 0.42 1.4 3.7 1.5 3.8 is not clear, and a larger sample set would be required
27 0.67 1.2 1.2 1.4 3.6 to explain it.
28 0.39 2.3 3.4 0.9 4.0
All considered analytes are used by organisms as
29 0.35 4.3 3.5 1.6 2.6
constituents of their physical structure and for
30 0.89 7.4 ᎐ 22.9 10.5
31 0.55 3.1 4.2 0.2 3.6 metabolic processes. The behaviour of minor elements
32 0.34 2.2 2.1 0.4 3.1 in the sea biogeochemical cycle differs according to
33 0.36 2.6 2.8 1.2 2.6 their chemical and biological properties: in particular
34 0.38 2.4 1.7 1.0 3.8 Li and B are conservative elements, while Si and Ba
a are recycled Žnutrient-type . elements and Sr is depleted
Samples 1᎐2, 5᎐14 and 25᎐30 were collected before pack
by biological activity.
melting; samples 3᎐4, 15᎐24 and 31᎐34 were collected after
pack melting. Samples 1,3: surface water; samples 2,4: water Concentrations in the Gerlache Inlet were generally
collected at 350 m depth. slightly lower than in the open sea before pack melting,
whereas the opposite trend was observed after thawing.
The minor element concentrations in the investi-
1992.. One of the few exceptions to this rule is the gated areas were similar to the typical ones Ž100 nM
formation of sea-ice, in which not all ions are included for Ba, 0.42 mM for B, 25 ␮M for Li, 100 ␮M for Si, 90
to the same extent. Table 7 shows that the ratios ␮M for Sr. ŽLibes, 1992; Stumm and Morgan, 1996., Si
among major ions in the present study have standard excluded, and are in agreement with the findings of
deviations up to 24% for the 1994᎐95 data and to 9% other researchers for the same area ŽPapoff et al.,
for the 1995᎐96 data. Such variability, which seems 1991..
fairly high, is mainly due to the presence of a few Sample 28 Ž1995᎐96, BPM. had the lowest concen-
samples Ž8, 1994᎐95 BPM; 16 and 22, 1994᎐95 APM. trations of most of the considered analytes, including
characterized by the presence of a high Ž16. or low Ž8 major elements; there is no reason why the correspond-
and 22. content of K, Ca and Mg. If these samples ing site should have any peculiarity, such as the pres-
36 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43

Table 5
Major and minor element ranges and average values Žvalues in mM for Na, Ca, K, Mg, B, ␮M for Li, Si, Sr, nM for Ba. a

Sample set Na Ca K Mg Ba B Li Si Sr

1994᎐95 campaign
Mean 5᎐14 455 11.16 11.08 62.26 95 0.42 25 68 91
Median 5᎐14 460 11.63 10.79 61.39 73 0.42 26 67 92
Range 5᎐14 435᎐478 8.46᎐12.52 9.23᎐13.32 51.21᎐72.10 51᎐160 0.32᎐0.47 17᎐29 59᎐74 72᎐105
Mean 15᎐24 448 9.73 9.56 52.34 89 0.38 22 52 80
Median 15᎐24 448 9.47 9.07 49.24 80 0.39 23 52 79
Range 15᎐24 429᎐473 6.76᎐13.25 6.47᎐14.12 37.10᎐72.72 73᎐138 0.28᎐0.45 13᎐29 38᎐73 60᎐107

1995᎐96 campaign
Mean 25᎐30 444 9.93 9.55 55.73 70 0.40 26 61 85
Median 25᎐30 440 10.13 9.41 55.32 66 0.40 26 61 86
Range 25᎐30 439᎐456 9.31᎐10.18 9.23᎐9.92 55.24᎐57.38 66᎐80 0.37᎐0.44 23᎐30 58᎐63 80᎐88
Mean 31᎐34 452 9.91 8.95 52.62 80 0.39 25 59 86
Median 31᎐34 453 10.08 8.96 52.55 77 0.38 26 58 87
Range 31᎐34 440᎐461 9.08᎐10.38 8.44᎐9.44 47.47᎐57.91 73᎐95 0.34᎐0.46 20᎐29 56᎐67 81᎐89
a
Samples 5᎐14 and 25᎐30 were collected before pack ice melting; samples 15᎐24 and 31᎐34 were collected after pack melting

ence of currents, since it is close to other ones: possibly
it was collected while some of the pack was melting, so
that it contains a higher percentage of freshwater. Also
some of the 1994᎐95 samples, e.g. 5 ŽBPM., 12 ŽBPM.,
17 ŽAPM. and 22 ŽAPM., are characterized by lower or
higher values for many of the investigated parameters,
with respect to the other samples of the same set.
3.3. Hea¨ y metals
The five investigated metals, namely cadmium, cop-
per, iron, nickel and manganese, have different bio-
geochemical characteristics. They have been classified
ŽDonat and Bruland, 1995. as recycled ŽCd, Ni., scav-
enged ŽMn., and both recycled and scavenged ŽCu, Fe..
Moreover, the behaviour of Mn and Fe is strongly
influenced by their chemical properties, such as the
tendency to form oxides and hydroxides and to exist in
different redox states.
The data shown in Tables 4 and 6 can be related to
the sampling period, as observed for major and minor
elements. As for the 1994᎐95 expedition, trace heavy
metal concentrations in samples 5᎐14 ŽBPM. were
generally higher than those found in samples 15᎐24
ŽAPM.. During the Antarctic spring and summer, ice
melting and phytoplankton bloom, with consequent

Table 6
Heavy metal ranges and average values ŽnM. a

Sample set Cd Cu Fe Mn Ni

1994᎐95 campaign
Mean 5᎐14 0.73 2.9 3.7 0.9 6.2
Median 5᎐14 0.76 3.1 3.3 0.6 6.4
Range 5᎐14 0.54᎐0.98 0.5᎐4.8 1.8᎐7.1 0.2᎐2.2 4.0᎐9.0
Mean 15᎐24 0.33 1.4 1.3 0.4 4.8
Median 15᎐24 0.24 1.4 1.1 0.4 4.9
Range 15᎐24 0.08᎐0.92 0.6᎐2.7 0.6᎐2.7 0.2᎐0.6 1.9᎐8.0

1995᎐96 campaign
Mean 25᎐29 0.48 2.2 2.7 1.3 3.7
Median 25᎐29 0.42 1.6 3.4 1.5 3.8
Range 25᎐29 0.35᎐0.67 1.2᎐4.3 1.2᎐3.7 0.9᎐1.6 2.6᎐4.4
Mean 31᎐34 0.41 2.6 2.7 0.7 3.3
Median 31᎐34 0.37 2.5 2.4 0.7 3.4
Range 31᎐34 0.34᎐0.55 2.2᎐3.1 1.7᎐4.2 0.2᎐1.2 2.6᎐3.8
a
Samples 5᎐14 and 25᎐30 were collected before pack ice melting; samples 15᎐24 and 31᎐34 were collected after pack melting.
 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43 37

Table 7
Ratios among major ions Žrelative standard deviations in parentheses . a

Sample set NarK NarCa NarMg KrCa KrMg MgrCa

1994᎐95 campaign
Average 5᎐14 41.5 41.3 7.4 1.00 0.18 5.6
Ž11.7. Ž14.1. Ž12.4. Ž8.4. Ž3.1. Ž7.3.
Range 5᎐14 34.4᎐50.6 36.3᎐55.1 6.2᎐9.1 0.86᎐1.09 0.17᎐0.19 5.1᎐6.1
Average 15᎐24 49.4 48.8 9.0 0.98 0.18 5.4
Ž23.7. Ž20.2. Ž20.5. Ž9.8. Ž4.9. Ž6.2.
Range 15᎐24 30.5᎐69.3 32.5᎐66.3 5.9᎐12.1 0.84᎐1.12 0.17᎐0.19 4.8᎐5.8

1995᎐96 campaign
Average 25᎐30 46.5 44.8 8.0 0.96 0.17 5.6
Ž2.9. Ž3.3. Ž2.7. Ž4.0. Ž4.3. Ž5.5.
Range 25᎐30 44.3᎐47.6 43.3᎐47.2 7.6᎐8.2 0.92᎐1.00 0.16᎐0.18 5.4᎐6.2
Average 31᎐34 50.5 45.7 8.6 0.90 0.17 5.3
Ž4.1. Ž4.41. Ž8.6. Ž5.1. Ž9.4. Ž9.5.
Range 31᎐34 47.9᎐52.2 43.8᎐48.4 8.0᎐9.6 0.86᎐0.96 0.15᎐0.19 4.6᎐5.6

Typical
Average 45.9 45.6 8.8 0.99 0.19 5.2
a
Samples 5᎐14 and 25᎐30 were collected before pack ice melting; samples 15᎐24 and 31᎐34 were collected after pack melting.

high biological productivity and bioaccumulation
phenomena, give rise to a decreased concentration of
dissolved metals. Similar results for Antarctic seawaters
were found by other authors ŽFrache et al., 1997;
Scarponi et al., 1997. and are in agreement with the
expected behaviour for biolimiting species ŽWong et al.,
1983.. The described trend was found for most heavy
metals in the 1995᎐96 samples as well. In this case
presumably the contribution of pack melting had a
more significant role in water dilution, since the sam-
ples were collected close to the water surface. The
concentrations found in the 1993᎐94 samples, even
though there was a small number of samples, confirm
the seasonal trend discussed. The lower heavy metal
levels present after pack melting in sub-surface water
can be due to bioaccumulation and dilution pheno-
mena; however, deep waters are less influenced by
dilution, so the seasonal decrease in concentration
could mainly be due to metal uptake by organisms
living at those depths. The metal content in samples 1
and 3 ŽBPM, respectively collected at the surface and
at a depth of 350 m. was lower than in samples 2 and 4
ŽAPM, respectively, collected at the surface and at a
depth of 350 m.: of course a depth profile cannot be
drawn from two points, but the results confirm the
surface depletion and deep water enrichment processes
due to both bioaccumulation and debris regeneration.
The effect of biological uptake on heavy metal con-
centrations is more relevant than on major and minor
elements, owing to their lower dissolved level: corre-
spondingly, their relative decrease after pack melting is
higher than for the other investigated species, con-
firming that the seasonal behaviour observed is due not
only to water dilution but also to biological uptake.
Even if the main source of heavy metals in seawater
is input from rivers, other sources are important for
specific elements, such as atmospheric deposition for
arsenic and lead and hydrothermal circulation for man-
ganese and iron. In the Antarctic continent rivers are
almost absent, so the metal content in seawater derives
from mixing with other waters Žsee below. and ice
erosion of the coast. Heavy metals in the particulate
phase are also released during pack ice melting ŽFrache
et al., 1997.. The main output removal is particle scav-
enging, i.e. uptake by particles Žvia adsorption or pre-
cipitation. followed by their sedimentation. In particu-
lar, manganese and iron have a strong tendency to
form insoluble oxides, which eventually sink and whose
accumulation gives rise to Fe-Mn nodules.
The maximum and average heavy metal concentra-
tions in the 1995᎐96 samples in the presence of pack
ice were generally lower than the corresponding values
for the 1994᎐95 campaign, whereas the reverse is true
after thawing. Since the Gerlache Inlet is close to the
Italian station, the low metal concentrations found
suggest that human activities in the station did not
cause contamination of the seawater. Also, the con-
tribution from rock weathering seems not to cause a
meaningful increase in the heavy metal levels along the
coast.
An attempt was made to evaluate the validity of our
hypotheses, and investigate whether heavy metals be-
have like major elements with respect to pack melting,
by comparing the extent of their variation Žbefore and
38 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43

Table 8
Typical heavy metal concentrations ŽnM. Žranges and means. in seawaters ŽLibes, 1992; Grasshoff et al., 1999.

Element Cd Cu Fe Mn Ni

Typical range 0.001᎐1 0.5᎐4.5 0.02᎐1 0.08᎐3 2᎐12

Typical mean 0.7 4 1 0.5 8

after water dilution. with that of the latter, whose
behaviour is closer to a conservative one. The ratio of
the sum of Na, K, Ca and Mg concentrations to the
concentration of each heavy metal was computed. The
averages of such ratios have large relative standard
deviations, typically from 24 to 60%: as a first approxi-
mation it can be confirmed that the metals are influ-
enced by different factors than major elements, and
their behaviour is far from conservative, since their
variations from sample to sample do not seem to follow
the same trend as major elements.
The observed heavy metal ranges and mean concen-
trations are in agreement with typical mean literature
values, shown in Table 8, confirming that Antarctic
seawater has no peculiarities from the point of view of
inorganic composition.
It is interesting to remark that the heavy metal levels
in the sea are not significantly different from the mean
oceanic ones, whereas their concentrations in the con-
tinent, e.g. in soils or lake waters, are lower than
typical ones ŽMentasti et al., 1998., owing to the virtual
absence of anthropogenic activities. This happens be-
cause the water circulation and the biogeochemical
cycle described above ensure approximately constant
levels of solutes. In fact it must be recalled that
Antarctic waters are not isolated from the rest of the
oceans. The presence of thermohaline circulation and
other oceanic currents, together with other mixing
mechanisms cause ocean waters to mix in a time range
of approximately 10 3 years. From the environmental
point of view, obviously water motion has the effect of
transporting pollutants to areas far away from the point

Fig. 1. Dendrogram ŽWard’s method. for 1994᎐95 samples. Samples 5᎐14 were collected before pack ice melting; samples 15᎐24
were collected after pack melting.
 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43
of input. Therefore, even if Antarctica is not directly
affected by anthropic activities, it is not free from the
risk of pollution.
A feature of the area studied is the presence of Ross
Ice Shelf, which is a source of cold water that is then
transported to lower latitudes. It is impossible to evalu-
ate the effect of such water flow, and of the other
hydrological characteristics of the area, on the element
distribution found in this study. The sea-depth is known
for samples 15᎐24 Ž1994᎐95, APM. and varies from
442 to 1990 m: no apparent relationship was found
between this parameter Žwhich in turn influences water
circulation . and analyte concentrations.
3.4. Spatial ¨ ariability
The spatial variability of the 1994᎐95 data was inves-
tigated. If analyte concentrations are plotted vs. longi-
tude and Žin separate plots. latitude, no meaningful
trend or regularity is observed in the spatial distribu-
tion within the two groups of samples collected before
Ž5᎐14. and after Ž15᎐24. thawing. As Table 1 shows,
many specimens of the group 5᎐14 came from lower
latitudes andror longitudes than most of the ones of
group 15᎐24. Therefore, if the 20 samples are con-
sidered together, an apparent trend of decreasing con-
Fig. 2. Biplot obtained by PCA for 1994᎐95 samples. Samples 5᎐14 were collected before pack ice melting; samples 15᎐24 were
collected after pack melting.
39
centration with increasing value of the co-ordinates can
be observed in the above-cited plots. In our opinion
such a decrease is mainly due to the different period,
rather than the different place, of collection, for sev-
eral reasons: Ži. the few samples of one group with
similar latitude or longitude to the ones of the other
group, in most cases follow the expected behaviour as a
function of the collection time Ži.e. the concentrations
in samples collected after pack melting are usually
smaller than the ones in the nearby samples collected
before thawing and vice-versa.; Žii. no analogy is
observed if a map of the geographical sample location
Ži.e. latitude vs. longitude. is compared with the den-
drogram and PCA plot, described below, reported in
Figs. 1 and 2 respectively Ži.e. clusters in the dendro-
gram or points with similar scores in the plot do not
correspond to samples with nearby co-ordinates.; Žiii. if
a significant effect of space distribution were present, it
would be observed also within each sample group Žbut
this is not the case, as remarked above..
3.5. Chemometric in¨ estigation
Pattern recognition techniques were applied to the
results obtained in order to gain insight into the rela-
tionships among the samples and the variables and to
 40
O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43
Table 9
Univariate F-ratios for the investigated elements Žreference value: 4.49 at a confidence level of 95%.

Variable Na Ca K Mg Ba B Li Si Sr Cd Cu Fe Mn Ni
1994᎐95 F-ratio 0.928 4.530 2.896 5.523 0.545 5.018 2.202 15.830 3.620 10.980 5.385 11.014 5.113 3.880
 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43
obtain a visual bi-dimensional representation of the
multi-dimensional data set. Data from the 1993᎐94
campaign were not considered because of their limited
number.
As to the 1994᎐95 samples, samples 17 and 19 were
excluded from the elaboration because of their
anomalous sodium content. Cluster analysis shows a
good separation between samples collected before and
after pack disaggregation. As Fig. 1 shows, two distinct
groups are clearly identified, with some exceptions.
PCA confirms this observation. The first two PCs
account for 61% of variability; adding the third PC
brings this value to 71.2%. Fig. 2 shows the biplot of
loading and scores for PC1 vs. PC2. No further useful
information was obtained considering PC3. The values
of the scores allow identification of two groups, corre-
sponding to the samples collected before and after
pack melting, confirming that there is a difference
between the two situations. Samples 5 ŽBPM. and 16
ŽAPM. are located apart from their respective sets,
because of a lower heavy metal content Žsample 5. and
a lower sodium but higher alkaline-earth element con-
centration Žsample 16.. Sample 23 ŽAPM. has a high
resemblance with 10 and 13 Žboth BPM., because of its
content in cadmium and nickel. A clear similarity is
also observed for sample pairs 20᎐21 ŽAPM. and 11᎐12
ŽBPM.. Sample 22 ŽAPM. stands out for its low content
of major Žexcept Na. and minor elements. The negative
value of PC2 for sample 8 and, to a lesser extent,
sample 9 Žboth BPM. in the plot is due to their
relatively high sodium content and low concentrations
of Ca, K, Mg, Sr. Sample 13 is characterized by a
relatively high iron content. Generally, PC2 for most
samples is between y2 and q2 Žin many cases being in
the range y1 to q1., whereas the values of PC1 are
more broadly distributed, ranging from q4 to y6.
If Figs. 1 and 2 are compared, the within-group
clustering identified by HCA and the similarities shown
by PCA have some analogies and differences, arising
from the different methods of data treatment of the
two techniques. For instance sample 16 ŽAPM., which
stands alone in the dendrogram, is also far from the
other samples of its group in the biplot. Samples 20 and
21 Žboth APM. are found to be similar with both
methods. However, the sample pairs 11᎐12 and 10᎐23,
which are close in the PCA plot, are not tightly clus-
tered in the dendrogram. Other sub-groups present in
the latter Že.g. 22᎐15, 18᎐5, 6᎐14, 10᎐13. correspond to
objects with a similar value of either PC1 or PC2, but
not so close on the biplot.
The variable loadings, showing the correlation among
the considered elements, are in all cases positive for
PC1: therefore an increase in any variable causes an
increase in PC1. This component might account for
some phenomenon acting in the same direction on the
concentration of all analytes, such as some physical
41
effect, like dilution or the presence of underwater
currents. The variables load on both PCs, i.e. there is
not one analyte, or a set of analytes, mainly influencing
the value of one PC with respect to the other, and vice
versa. There are no anticorrelated variables; anyway,
nearly half have positive loadings, and the other half
negative ones, on PC2; for instance three heavy metals,
namely Cd, Cu, Mn, have positive loadings on PC2,
whereas Fe and Ni have negative ones: therefore, the
influence of heavy metals is in the same direction on
PC1 and has two opposite effects on PC2. No clear
interpretation for this behaviour exists, since it does
not seem to reflect similarities or differences in the
chemical properties or biogeochemical cycles of the
two groups of elements. As it can be seen, there is a
correlation among Ca, Mg, Sr and K, probably because
of dissolution᎐precipitation equilibria involving alka-
line-earth metals. The behaviour of Ba and Li in the
plot is more similar to that of heavy metals. Another
correlation is between the metalloids boron and silicon.
Sodium is not strongly correlated to any other element.
The comparison of loadings and scores shows that all
variables ‘point’ towards the set of samples collected
before pack ice melting, confirming that they have a
higher solute levels.
DA performed on two well-defined classes Ž5᎐14 and
15᎐24 samples, BPM and APM, respectively. yields a
canonical discriminant function and a model; according
to this, all samples were identified as belonging to the
expected classes Ž99.7᎐100% probability. except sample
24. Si, Cd, Fe have the highest discriminating power,
according to their F-ratio values. Table 9 reports uni-
variate F-ratios with 1 and 16 degrees of freedom for
the variables considered.
In the case of 1995᎐96 expedition HCA, PCA ad DA
were unable to discriminate between the two expected
groups of samples, i.e. again, those collected before
and after pack disaggregation, neither could the unsu-
pervised techniques identify other meaningful similari-
ties or differences among specimens. These results are
in part due to the low number of samples involved in
the calculation, but they could also reflect the different
characteristics of the 1994᎐95 and 1995᎐96 sample
sets. In fact samples 31᎐34 ŽAPM. were collected only
a few days after samples 25᎐30 ŽBPM., so that biologi-
cal uptake could have occurred on a limited scale.
4. Conclusions
Major, minor and trace element concentrations in
the Ross Sea show a seasonal variation related to the
melting of pack ice and to the subsequent phytoplank-
ton blooming.
42 O. Abollino et al. r Ad¨ ances in En¨ ironmental Research 6 (2001) 29᎐43
Dissolved levels decrease after thawing because of
water dilution and bioaccumulation. The latter process
particularly, has a relevant influence on heavy metal
concentrations.
Data elaboration by PCA, HCA and DA of the
results obtained in the 1994᎐95 campaign allowed us to
identify sub-groups of samples and to demonstrate the
presence of peculiar ones. Correlations among alka-
line-earth metals and between B and Si were also
found. Heavy metals are divided in two groups. In
general, the distribution of loadings on the two ex-
amined PCs seems to indicate that the behaviour of the
dissolved elements is not only related to chemical equi-
libria but also to biological and physical factors.
The concentrations found in Antarctic seawater are
in agreement with mean typical literature values.
Moreover, no metal pollution was found in coastal
waters close to the Italian Station in Antarctica. Actu-
ally anthropic activities are negligible in this part of the
world, therefore, the study of the composition of sea-
water as well as of other parts of the ecosystem is of
particular interest because element distribution reflects
the extent of natural biogeochemical equilibria. The
Antarctic Ocean is not isolated from the rest of the
planet but is involved in global phenomena such as the
water thermohaline circulation, so it is exposed to the
risk of transport of pollutants from more populated
areas. Therefore, the monitoring of the level of con-
taminants in a clean area such as Antarctica is of aid to
identify trends and changes involving the planet ecosys-
tem.
Acknowledgements
The authors wish to thank all the components of the
group ‘Biogeochemical Cycles of Contaminants’ of the
Italian expeditions to Antarctica in 1993᎐94, 1994᎐95
and 1995᎐96 campaigns for their kind assistance in
collecting the samples and for their cooperation that
made this research possible; the financial support from
C.N.R and E.N.E.A.᎐P.N.R.A. Antarctic Program is
also gratefully acknowledged.
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