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Assessment of metal pollution based on multivariate statistical

modeling of hot spot sediments from the Black Sea


V. Simeonov
a,
*
, D.L. Massart
b
, G. Andreev
c
, S. Tsakovski
a
a
Chair of Analytical Chemistry, Faculty of Chemistry, University of Soa ``St. Kl. Okhridski'', J. Bourchier Blvd. 1, Soa 1126,
Bulgaria
b
Vrije Universiteit Brussel, Pharmaceutical Institute, Pharmaceutical and Biomedical Analysis, 1090 Brussels, Laarbeeklaan 103,
Belgium
c
Institute of Oceanology, Bulgarian Academy of Sciences, P.O. Box 152, Varna 9000, Bulgaria
Received 25 August 1999; accepted 24 November 1999
Abstract
The paper deals with application of dierent statistical methods like cluster and principal components analysis
(PCA), partial least squares (PLSs) modeling. These approaches are an ecient tool in achieving better understanding
about the contamination of two gulf regions in Black Sea. As objects of the study, a collection of marine sediment
samples from Varna and Bourgas ``hot spots'' gulf areas are used. In the present case the use of cluster and PCA make it
possible to separate three zones of the marine environment with dierent levels of pollution by interpretation of the
sediment analysis (Bourgas gulf, Varna gulf and lake buer zone). Further, the extraction of four latent factors oers a
specic interpretation of the possible pollution sources and separates natural from anthropogenic factors, the latter
originating from contamination by chemical, oil renery and steel-work enterprises. Finally, the PLSs modeling gives a
better opportunity in predicting contaminant concentration on tracer (or tracers) element as compared to the one-
dimensional approach of the baseline models. The results of the study are important not only in local aspect as they
allow quick response in nding solutions and decision making but also in broader sense as a useful environmetrical
methodology. 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Multivariate statistics; Cluster analysis; Principal component analysis; Partial least squares modeling; Marine sediments;
Heavy metals pollution
1. Introduction
There is growing concern all over the world on the
extent of sediment contamination in coastal regions
(National Research Council, 1989; Environmental Pro-
tection Agency, 1992). The signicance of the sediment
contamination to the overall condition of the aquatic
environment has been recognised since a long time.
Most contaminants discharged into coastal waters rap-
idly become associated with marine particulate matter
and incorporated in sediments. Although diagenetic
processes in the sediments modify and redistribute
contaminants between solid and water phases, immobi-
lization by sedimentation process dominates for most of
the typical pollutants. As already indicated (Martin and
Whiteld, 1983) the contaminant metal accumulation in
coastal sediments provides a record of the spatial and
temporal history of pollution. That is why sediment
monitoring can deliver important information on vari-
ous pollution events.
Chemosphere 41 (2000) 14111417
*
Corresponding author.
E-mail address: VSimeonov@chem.uni-soa.bg (V. Sim-
eonov).
0045-6535/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 9 9 ) 0 0 5 4 0 - 8
Large-scale studies in the USA are dedicated to trace
element contaminants in sediments and carried out by
large organizations like the National Oceanic and At-
mospheric Administration (NOAA) through programs
like National Status & Trends (NS&T) Program for
Marine Environment (Cantillo and O'Connor, 1992;
Hanson et al., 1993; Daskalakis and O'Connor, 1995).
The programs make it possible to compare contaminant
metal levels over large scales of distance and time. But in
this case a method for separating contaminant and
natural components as well as natural and anthropo-
genic contaminant levels is very important. This holds
especially true for evaluation of the pollution in ``hot
spots'', i.e., sampling sites strongly inuenced by human
activity. Usually, these are small zones of higher con-
tamination due to specic anthropogenic point sources
(discharge points, industrial regions). In principle, these
sites are not representative of their natural surroundings
if the scope of a study is to follow a general pattern of
distribution of trace metal in sediments (e.g., world-wide
pattern as indicated by Cantillo and O'Connor, 1992).
But the ``hot spots'' become very interesting to evaluate
or model a local pollution. In this case it is important
even to rank the pollution level for dierent sites in a
larger region in order to get information on the range of
the anthropogenic inuences or to separate them from
the unavoidable natural variability of the sediment
content.
There is a variety of approaches for reducing natural
variability and improving the statistical power in data
intercomparison. Metal concentrations are often nor-
malized to a conservative component (very often alu-
minium or iron for sediment samples) whose levels are
unaected by contaminant inputs (DeGroot et al., 1976;
Forstner and Wittmann, 1981; Loring, 1990; Luoma,
1990). The association between Al (or Fe) has a geo-
chemical foundation which can be used as a basis for
development of statistical models. A very interesting
baseline regression model for variety of components on
Al was introduced by Hanson et al. (1993). Based on
observed covariation of elements at 15 estuaries remote
from contaminant inputs, linear regressions of metals on
Al were used to model the metal content in baseline
sediments. A geochemical model for the covariation is
developed, veried and used to guide the statistical
modeling approach. Using these baseline relationships,
sediment metal concentrations can be partitioned into
natural and anthropogenic fractions. Hanson et al.
(1993) believe that this approach works better than the
more complex and more abstract approaches of the
multivariate statistics like principal components analysis
(PCA), principal components regression (PCR) etc.
It has to be mentioned that the baseline model relies
on a substantial amount of data from non-polluted
coastal area which could be easily found for the huge
coastal line of the USA and by the data support of
programs like NS&T. Very often it is necessary to esti-
mate statistically or model ``hot spots'' areas by direct
sampling and analysis of sediments from a limited
number of sites. Quick decisions have to be made with
respect to local pollution events. In this case the multi-
variate statistical approaches seem to deliver more sub-
stantial information on links between sampling sites,
pollutant concentrations, latent factors responsible for
the data set structure and pollutant sources apportion-
ing. As stated by Einax et al. (1997) and Einax and Soldt
(1999), the complexity and the large variance of envi-
ronmental sets limit the use of common statistical
methods for the assessment of the state of pollution, so
the application of geostatistical and multivariate statis-
tical methods is recommendable.
The Bulgarian Black sea coast is known as a recre-
ation area, and this requires a constant environmetrical
control of all marine phases since a large number of
industrial ``hot spots'' are also located near to the shore
(oil renery near to Bourgas gulf, cement and chemical
plants around Varna gulf, steel-works etc.). Usually, the
reaction of the authorities to monitoring data is slow
due to the lack of clear information about the real state
of pollution or to the temporary and local character of
the pollution events. It is the aim of the present study to
perform a chemometric analysis of metal concentrations
in sediments collected at dierent ``hot spots'' sites of the
Bulgarian Black sea coast in order to oer a more in-
formative and rapid assessment of the state of pollution.
2. Experimental
2.1. Sampling and sample analysis
Sediment samples were taken from four dierent
sampling sites: Lake Beloslavsko (10 sites, sample
number 110, close location of glass production facto-
ry), Lake Varnensko (11 sites, sample number 1121,
close location of steel-work), Varna Gulf, close to lake
Varnensko (7 sites, sample number 2228), Varna Gulf
near to coast (7 sites, sample number 2935; close lo-
cation of cement and chemical plants Solvaysoda) and
Bourgas Gulf, near to the waste inlets caused by the
local oil-renery (4 sites, sample number 3639). It is
worth noting that in the conguration of the coastal line,
the two lakes mentioned (Beloslavsko and Varnensko)
serve as a natural buer zone between the industrial
zone and the gulf of Varna. For the gulf of Bourgas no
such zone exists, and there is a direct inlet of contami-
nated waters into the sea.
Sediment samples were obtained with a standard
SmithMcIntyre bottom grab (Hanson et al., 1993) or a
box corer. Three grabs or cores were made at each si-
te(depths between 8 and 50 m). Composite samples were
made from sediments in the cores. Sediment analysis for
1412 V. Simeonov et al. / Chemosphere 41 (2000) 14111417
a site consisted of inorganic (metal components) analy-
sis. In principle the standard procedure suggested by
NOAA (Shigenaka and Lauenstein, 1988) was followed
as closely as possible.
The elements measured throughout this study were
Cu, Pb, Mn, Zn, Co, Cd, Cr, Fe, Ni and As. Digestion in
concentrated hydrouoric acid and subsequent analysis
by atomic absorption were used for quantication.
ETAAS (graphite furnace AAS, Perkin Elmer Z/3030)
was the analytical methods to determine Cu, Pb, Co, Cd,
Cr, Ni, As and ame AAS (Perkin Elmer 603) was used
for Mn, Fe and Zn. Certied reference materials
(MESS-1, BCSS-1 and NBS 1646) were run with each
series of samples. A measured value for the reference
material within the oered tolerance was the criterion
for bias control and check of the data quality. Precision
for Fe, Mn and Zn was 65% (as relative standard de-
viation); for Cu, Cd, Cr, Co, As, Ni and Pb 610% as
RSD.
The experimental data for 39 sampling sites each
analyzed for 10 components are presented in Table 1 as
a basic statistical summary of the input set. Single data
are available on request.
2.2. Statistical analysis
Throughout the study various statistical approaches
were used, among them regression analysis (linear and
PCR), cluster analysis, PCA and partial least squares
(PLSs) modeling. All of these methods are well-known
and described in the literature, to mention only a small
part of the huge amount of bibliography (Draper and
Smith, 1981; Massart and Kaufman, 1983; Malinowski,
1991; Einax et al., 1997). Since there are dierent opin-
ions on the use of multivariate statistical methods in
environmental analysis, varying from sceptic accepta-
tion as ``complex and to some extent formal'' (Hanson
et al., 1993) to solid conviction of being ``a useful tool for the
best evaluation and interpretation of environmental
data'' (Einax and Soldt, 1999), it was the aim of this
study to compare in a practical way these two extreme
judgments. Throughout the study the sofware packages
SPSS 8.0, UNSCRAMBLER 5.5 and STATISTICA 5.0
were used.
The possibility to analyze multidimensional data sets
without information about the spatial locations is the
advantage of the multivariate statistics. We consider
that the basic principles and the theoretical fundamen-
tals are known to a substantial part of the readers and
there is no need for a detailed explanation (Einax and
Soldt, 1999). Many studies oer algorithms of dierent
multivariate statistical approaches. For instance, cluster
analysis is carried out to reveal specic linkage between
sampling sites being an indication of similarities or dis-
similarities between their trace metal contamination.
Further, PCA is applied to detect the ``hidden'' structure
of the data set, trying to explain the inuence of latent
factors on the data distribution. The regression analysis
in its classical linear performance or as more sophisti-
cated form of multivariate regression by the use of rst,
X-variables decomposition by PCA and then, regression
of each Y-variables onto the decomposed X-matrix
(Esbensen et al., 1994) makes it possible to create re-
spective trend and prediction models for each contami-
nant. Finally, PLSs modeling allows to nd out a more
detailed connection between, e.g., natural and possible
anthropogenic sources for the sediment diagenesis. It
may be stated that by means of multivariate analysis
that a semiquantitative assessment of the polluted area is
feasible.
In the present chemometric study Wards and single
linkage clustering methods (Euclidean distance as simi-
larity measure), Varimax-rotation for PCA on auto-
scaled data and PLS algorithms for multivariate
regression (Esbensen et al., 1994) were applied.
3. Results and discussion
In order to compare the one-dimensional approach
with the multivariate one, linear regression for the sed-
iment components on iron was performed. The regres-
sion models are summarized in Table 2. Iron was chosen
as tracer since it is a typical natural component for the
Table 1
Descriptive statistics of the input data (concentrations in mg/kg)
Element Mean value Highest value Lowest value S.D. S.E.
Cu 80.00 786.00 3.00 140.76 22.54
Pb 15.96 118.80 1.55 24.76 3.97
Mn 302.92 1710.00 73.67 371.85 59.54
Zn 58.97 265.54 14.77 46.98 7.52
Co 3.69 13.00 0.01 2.50 0.40
Cd 0.81 4.29 0.01 1.12 0.18
Cr 25.59 109.52 3.00 25.54 4.09
Fe 9554.12 98200.00 0.85 26005.57 4164.22
Ni 12.96 28.00 1.00 8.55 1.37
As 29.17 222.72 0.01 52.17 8.35
V. Simeonov et al. / Chemosphere 41 (2000) 14111417 1413
Black sea sediments and its use as regressor in many
sediment studies is acknowledged (Simeonov and
Andreev, 1989).
Acceptable linear regression models are obtained for
Cu, Mn and Co, e.g., for components which are present
in higher natural concentrations in the sediments
(Martens and Naes, 1991). Since no real baseline data
are available for the region of interest, nothing specic
could be concluded about the ecological situation at the
``hot spots'' at the Bulgarian Black sea coast. It seems
also not very reliable to predict the anthropogenically
inuenced concentrations (Pb, Cd, Ni, As) by the iron
tracer.
The cluster analysis results (hierarchical clustering,
Wards method) of the sampling sites as objects are
shown in Fig. 1. Altogether four clusters could be in-
terpreted divided into two bigger subgroups: the rst
contains heavily polluted sites from Varna and Bourgas
gulf (near to the coastal line and the waste inlets, sites
2939 located near a big chemical and cement plant
Varna and an oil renery Bourgas) and several sites
from both coastal lakes located near to industrial
sources (sites 2, 4, 6, 7, 8, 9 from the Lake Beloslavsko
located near to a glass production factory; sites 14, 17,
19 from the Lake Varnensko located near to a steel-
work); the second one indicates a moderately polluted
buer zone consisting of lake and near to the lake Varna
gulf sites. In both big clusters two subgroups could be
found. In the rst one they represent the most severly
polluted gulf areas (sites from Varna gulf 2935 and
from Bourgas gulf 3639) and the less contaminated lake
industrial inlets (sites 2, 4, 69 fom Lake Beloslavsko
and sites 14, 17, 19 from Lake Varnensko). In the second
one they reect the separation between one (Varnensko
lake and non-aected Varna gulf part, sites 1113, 15,
16, 18, 20, 21 and sites 2228, respectively) or another
part (Beloslavsko lake, sites 1, 3, 5, 10) of the buer zone
moderately aected by pollutants.
The next step in the multivariate statistical analysis
was application of PCA in order to group the chemical
components by the loadings plots and the sites by the
scores plots. It is interesting to note that the site score
plot (Fig. 2) reveals a more detailed description of the
region of interest.
Fig. 1. Hierarchical dendrogram (Wards method of linkage) for 39 sampling sites as objects (sites 110 Lake Beloslavsko; sites 1121
Lake Varnensko; sites 2228 Varna Gulf near to lale Varnensko; sites 2935 Varna Gulf near to coast; sites 3639 Bourgas
Gulf).
Table 2
Linear regression models for elements relative to Fe for coastal sediments
Element n Intersept b
0
Slope b
1
S.E. of b
0
S.E. of b
1
r
2
Cu 39 36.67 0.0045 13.30 0.00049 0.71
Pb 39 16.28 )0.00003 4.29 0.00016 0.001
Mn 39 176.16 0.0013 24.00 0.00088 0.87
Zn 39 56.57 0.00025 8.06 0.00029 0.02
Co 39 3.33 0.00004 0.40 0.000015 0.87
Cd 39 0.92 )0.00001 0.19 0.0000068 0.07
Cr 39 27.82 )0.00023 4.30 0.00016 0.06
Ni 39 12.87 0.00001 1.38 0.000054 0.0001
As 39 33.14 )0.00042 8.84 0.00032 0.04
1414 V. Simeonov et al. / Chemosphere 41 (2000) 14111417
The sites in the Bourgas gulf (3639) represent an
independent group (I) of heavily polluted area (oil-re-
nery). They are denitely separated from all other sites
and this is due to the enhanced element concentrations.
The next well-formed group (III) comprises sites from
the moderately contaminated lake buer zone (sites 1
28) which includes sites from the two lakes and Varna
gulf sites located nea to Lake Varnensko. The third
group (II) indicates the intermediate level of pollution
(higher than the buer zone contamination but less than
the Bourgas gulf area) of the sites originating mainly
from the Varna gulf area (sites 2935).
The factor loading matrix is listed in Table 3.
Four factors describe almost 90% of the total vari-
ance of the system. The rst one contains dominantly
copper, manganese and iron and could be conditionally
named ``natural'' since these elements are typical con-
stituents of the Black sea marine sediments. The second
factor includes zinc, cadmium and chromium, the third
lead and arsenic and the fourth nickel and cobalt. The
last three factors reect typical anthropogenic inuences
of heavy metals from various sources such as chemical
and glass producing plants, oil reneris, steel-works and
smelting plants. The detected pollution patterns indi-
cated in a semiquantitative way the emission sources. In
Fig. 3 the 3-D loading plot (PC1 vs. PC2 vs. PC3) is
presented and the relationship between the variables is
readily seen.
It is quite interesting in the next step of the chemo-
metrical analysis to check if it is possible to oer re-
gression models for each contaminant relative to one or
another natural tracer component, e.g., metal f Fe
for linear regression; metal f PC
i
for PCR and
metal f Fe or f (Fe, Mn) for PLSs modeling (PLS1
and PLS2) with one and more than one regressor.
Again, iron was chosen as tracer for PCR and PLS1
modeling variation (only one independent variable). In
both cases an almost complete agreement between the
results of linear regression and these two approaches
was observed. A substantial improvement of the model
signicance was achieved with the PLS2 modeling mode
when two tracer elements (Mn and Fe) were chosen as
independent variables in the multivariate regression. The
results are listed in Table 4.
The comparison with the linear regression models
(Table 2) reveals a much better correlation for all an-
thropogenic constituents. It means that their concen-
trations could be more reliably predicted in the ``hot
spot'' areas based on the naturally occurring compo-
nents.
The heavily contaminated Bourgas gulf site forms a
group of outliers. This fact oers an opportunity to
Table 3
Factor loadings (Varimax normalized; marked loadings are
>0.70) for four principal components (PC)
Element PC1 PC2 PC3 PC4
Cu 0.95 0.08 )0.09 0.04
Pb 0.04 )0.04 )0.88 )0.04
Mn 0.96 0.04 0.16 0.17
Zn 0.27 0.90 0.04 0.11
Co 0.31 )0.04 0.17 0.89
Cd )0.15 0.88 )0.26 )0.05
Cr )0.13 0.92 0.05 0.27
Fe 0.95 )0.14 0.07 0.11
Ni )0.01 0.48 )0.04 0.81
As )0.14 0.16 )0.86 )0.06
%Expl.var 29.54 27.07 16.52 15.84
Fig. 3. PCA loading 3-D plot (PC1 vs. PC2 vs. PC3) for 10
chemical components.
Fig. 2. Bivariate PCA scores plot (PC1 vs. PC2) for 39 sam-
pling sites (sites 110 Lake Beloslavsko; sites 1121 Lake
Varnensko; sites 2228 Varna Gulf near to lale Varnensko;
sites 2935 Varna Gulf near to coast; sites 3639 Bourgas
Gulf).
V. Simeonov et al. / Chemosphere 41 (2000) 14111417 1415
check if the model adequateness will be improved by
eliminating the outliers. It should also be mentioned that
in many observations of the sediment diagenesis the
enhanced concentrations of naturally appearing com-
ponents could be the reason for enhanced concentration
of Cd and Pb without additional anthropogenic impact
(Hanson et al., 1993). In this sense the elimination of the
outliers is a good assumption for a more reliable mod-
eling of real contaminants. In Table 5 the results of
PLS2 modeling without the most polluted sites are
presented (metal f(Fe, Mn)).
The choice of two tracers improves substantially the
prediction ability of the models.
4. Conclusion
The high variability of the pollutant concentrations
determined at various sampling sites and various en-
vironmental phases require a very careful evaluation
and interpretation. The application of dierent statis-
tical methods is an ecient tool in achieving better
understanding of the state of the environment. It seems
very recommendable to combine various statistical
approaches instead of relying only on one of them
in order to gain better information of the system of
interest or to try to predict its future trends. In the
present case, the use of cluster and PCA make it
possible to separate three zones of the marine envi-
ronment with dierent levels of pollution by interpre-
tation of the sediment analysis. Further, the extraction
of latent factors (four in the present case) oers an
opportunity of revealing the data structure and of
separating natural from anthropogenic factors. Finally,
the PLSs modeling gives a better opportunity in pre-
dicting contaminant concentration on tracer (or trac-
ers) element as compared to the one-dimensional
approach of the baseline models. The results of the
study are important not only in local aspect as they
allow quick response in nding solutions and decision
making but also in broader sense as a useful environ-
metrical methodology.
Acknowledgements
One of the authors (V. Simeonov) would like to
express his sincere gratitude to the Government of
Brussels-Capital Region for the nancial support (Re-
search in Brussels Grant 1999) which made this study
possible.
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Table 5
PLS modeling using two tracers (Mn and Fe) for sediment data
(except for 4 heavily polluted sites in Bourgas gulf)
a
Element Oset Slope RSMED r
2
Cu 36.38 0.11 31.66 0.27
Pb 14.01 0.13 24.05 0.13
Zn 33.69 0.41 37.46 0.39
Co 2.10 0.38 1.63 0.52
Cd 0.77 0.13 1.06 0.13
Cr 14.58 0.47 18.82 0.48
Ni 8.56 0.33 7.14 0.34
As 27.84 0.14 49.39 0.14
a
For RSMED see note to Table 4.
Table 4
PLS modeling using two tracers (Mn and Fe) for sediment data
(all 39 sites included)
a
Element Oset Slope RSMED r
2
Cu 14.63 0.81 59.42 0.81
Pb 15.14 0.05 23.82 0.05
Zn 43.19 0.27 39.70 0.27
Co 0.15 0.98 1.68 0.98
Cd 0.72 0.11 1.04 0.10
Cr 18.05 0.30 21.17 0.29
Ni 11.30 0.13 7.88 0.13
As 26.63 0.10 49.21 0.09
a
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