URBAN GEOCHEMISTRY: A STUDY OF ELEMENT DISTRIBUTIONS

IN THE SOILS OF TALLINN (ESTONIA)

L. BITYUKOVA1,∗, A. SHOGENOVA1 and M. BIRKE2

1 Institute of Geology at Tallinn Technical University, Estonia Avenue 7, Tallinn, Estonia;
2 Federal Institute of Geosciences and Natural Resources, Berlin, Germany
(∗ author for correspondence, e-mail: lida@gi.ee)

Received 10 August 1999; accepted 20 May 2000

Abstract. First results are presented from the ‘Urban geochemistry of Tallinn’, a project supported
by the Scientific and Environmental Affairs Division of NATO. The distribution of chemical elements
in 532 samples of the topsoils from the territory of the biggest industrial centre of Estonia (pop.
500,000) is interpreted. Statistical analysis and mapping of major and trace elements at the territory
of the Tallinn region and of the city were performed and background values and local anomalies of
chemical elements on the territory were determined. The investigation focussed on the determination
of zones with anomalously high concentrations of elements and the relationships of soil contamina-
tion with different pollution sources. The increase of the element concentrations has natural as well
as anthropogenic origins. A detailed comparative analysis of the element distributions and the results
of a factor analysis showed that the distribution of the major chemical elements depended mainly on
the composition of the underlying sedimentary rocks.
The territory of Tallinn is characterised by relatively high and widespread concentrations of Ba,
Cr, Ga, Ni, Ti and Zn. Especially intensive local concentrations were determined for As, Cr, Mn,
Ni, Pb, S, V and Zn, which are typical for the local pollution of the soils by industrial sources. The
levels of As, Cr, Mn and V are more than three times. Pb and Zn are more than five times higher in
the geochemical anomalies than for background levels. For the Tallinn region two major associations
of elements connected with industrial pollutions of the soil are typical: the first association includes
Ba, Cr, Mn, Ni and partly Fe and the second one includes As, Pb and Zn. For the city of Tallinn an
increase of Ag, Ba, Be, La, Pb, Sn and Zn concentration in the soil was detected. Ba, Cr, Mn and Ni
occur in high concentrations in the soils around Maardu. Different types of contamination sources
can be identified in Tallinn and its suburbs.

Key words: chemical elements, contamination, environment, geochemistry, soils

1. Introduction

The ecological situation in urban and industrial centres is a decisive factor influen-
cing both the quality of life and the health of people. Poor environmental conditions
have negative influence on human health and can cause serious economic loss. The
impact on the environment is increased by careless intensive industrial develop-
ment and is especially high in the biggest industrial cities. To enable the estimation
of the ecological situation and the impact of the different technologies on the nat-
ural environment it is necessary to carry out complex investigations of the natural
environment. In such cases the geochemical investigation of pollution on industrial

Environmental Geochemistry and Health 22: 173–193, 2000.

© 2000 Kluwer Academic Publishers. Printed in the Netherlands.
174 L. BITYUKOVA ET AL.

centres and the geochemical monitoring of soils is an important contribution to the

characterisation of the state of the environment. Polluted soils are the sources of
increased metal uptake by plants and man. Heavily or extremely polluted soils have
therefore to be excluded from the food plant production to protect human beings,
especially infants and children.
In the oldest and biggest industrial centres the level of environmental pollution
is usually higher than in other regions. The most stressed regions in Estonia are the
north and north-east part of the country, where most of the industrial enterprises
are concentrated. A medical report on the health of the population of Estonia shows
that the incidence of diseases is highest in the industrial towns (Jaakmees, 1992;
Tatar, 1992).
Tallinn is the capital and biggest industrial centre of Estonia. It is located in the
north of the country on the coast of the Baltic sea. Tallinn has a population of about
half a million people, which is a one third of that of the whole of Estonia. More than
100 factories housing textile, food, wood processing, heavy-, energy- and military
industries were based in the city. Tallinn can be subdivided into three types of area:
natural ground (58.9%), industrial ground (33.3%) and reservoirs (8.2%) (Sander,
1986).
During 1987–1990 an initial geochemical programme was carried out in the
Tallinn region. As a result, zones with relatively high concentrations of soil pollut-
ants were defined (Kiipli et al., 1991). Detailed geochemical investigations
included sequential leaching which permitted the intensity of the element migra-
tion and accumulation in different forms to be estimated. The sequential extrac-
tion method (Bityukova, 1994) also made it possible to estimate quantitatively the
different forms of the most harmful elements: Cr, Cu, Mn, Ni, Pb and Zn. The
concentrations of the trace elements in the different parts of the plants (roots,
leaves and flowers) on the industrial territories were also studied (Bityukova,
1996).
The main purpose of the investigation performed within the NATO project was
to monitor soils geochemically within the territory of Tallinn and its suburbs. For
comparative analysis and interpretation the geochemical data were investigated
using univariate and multivariate statistical analysis (correlation and R-mode factor
analysis). The main objectives of the investigation were:
• characterisation of the composition and alteration of natural soils in the terri-
tory of Tallinn;
• estimation of the background concentration of elements;
• detection of soil contaminants and the evaluation of the geochemical ano-
malies;
• establishment of the principal factors controlling pollution of the soils and
identification of pollution sources by using the correlation and factor analysis.
 URBAN GEOCHEMISTRY OF TALLINN 175

2. Material and methods

The territory of the Tallinn region covers approximately 1290 km2 . Soil samples
(532) were collected from the first 10 cm of the upper soil horizon. The study
showed that the granulometrical and geochemical compositions of soils in the ver-
tical section of upper soils horizon (0–10 cm) are very similar (Bityukova, 1994).
The soils were sampled following a 2 × 2 km grid using the topographic maps at the
scale of 1:25,000. The sampling points were digitised and their coordinates were
calculated using the topographic maps at the scale of 1:25,000. These coordinates
were presented in the Projection: Gauss-Krüger, 270 (coordinate system Pulkovo
1942, zone 5) and they were used for processing contour and image geochemical
maps. The locations of sampling sites are shown in Figure 1. Each sample was
collected from a square of about 15 × 15 cm. The square of sampling was larger
if the thickness of soils was less than 10 cm. The total weight of the sample was

Figure 1. Location map of the studied area and sampling points. The territory of Tallinn region – A,
the territory of urban Tallinn – B.
176 L. BITYUKOVA ET AL.

about 1 kg. In central urban Tallinn (covering about 89.6 km2 ) the samples were
collected on denser grid (250 × 250 m). The grid interval varied slightly because
of the problem of sampling in towns (buildings, technical constructions, roads and
so on). In the urban area the sampling was carried out in the open spaces (parks,
public gardens and so on) at a distance of several metres from highways and build-
ings. All samples were air-dried, disaggregated, sieved (<1 mm) and crushed by
a ball mill. The initial geochemical mapping was carried out in 1987–1990. The
fraction <1 mm was used for the analysis according with methodology that was
widely adopted in the Soviet Union. This sampling methodology led to some prob-
lems when comparing our geochemical data with the databases of other countries,
but it permitted the estimation of background concentrations of elements and the
determination of geochemical anomalies in the studied territory.
All samples were analysed by X-ray fluorescence spectrometry in the Institute
of Geology in Tallinn (As, Ba, Cr, Ga, Mn, Ni, Pb, S, Sr, Ti, V, Zn and Zr in all
samples and additionally Si, Al, K, Na, Ca, mg, Fe and P in a subset of 298 samples
from this collection). Twenty two elements were measured in the 198 soil samples
from urban Tallinn by optical emission spectrography in the Chemical laboratory
of the Geological Survey of Estonia. The reliability of the results of both chemical
methods was controlled by the State Certified reference materials of the Former
Soviet Union and by comparative analysis with other methods (bulk chemical ana-
lysis). Quality control was also carried out using the duplicates of samples. The
elements, for which accuracy of the measured values was not in good agreement
with true values, were omitted from the geochemical database. All concentrations
below the detection level were set to one-half of the detection limit as is usual for
geochemical mapping and statistical treatment of the geochemical data (Loukola-
Ruskeeniemi and Heino, 1996; Reimann et al., 1997). Some heavy metals (Co,
Cr, Mn, Ni, Pb, Zn) were studied by sequential extraction, described in detail by
Bityukova (1994).
The geochemical database was subdivided into two discrete sets. The first data
set consisted of 299 topsoils samples from the Tallinn region with concentrations
of 20 major and trace elements. The second data set included the concentrations of
22 trace elements in 198 topsoils samples of urban Tallinn.
It was considered by the authors that the large amount of chemical data, the
very complex character of the relations between the chemical elements and the
numerous sources of pollution required the application of statistical methods for
the interpretation of the obtained data.
During the investigation of soil pollution we usually deal with a complex com-
bination of contamination factors, which is very difficult to identify and study
separately. Very often the interpretation of one of the variables is not clear. In
this case the best method is to investigate all variables together in order to get
the most important factors. The methods of multivariate analysis are very powerful
and permit scientists to analyse together more variables (Davis, 1986).
 URBAN GEOCHEMISTRY OF TALLINN 177

The statistical analysis of the geochemical data, correlation and factor analysis
(R-mode factor analysis) and interpretation of obtained results for every data set
was performed using STATISTICA for WINDOWS software. R-mode factor ana-
lysis is a statistical technique, where the relationship within the set of m variables
is regarded as reflecting the correlations of each of the variables with p mutually
uncorrelated underlying factors. The factors represent linear combinations of the
original variables and hence contain and summarise most or all of the information
(Reyment and Jöreskog, 1993). As a result, a small number of factors may be used
to describe approximately the same amount of information as do the much larger
set of original observations. Factors are determined so as to account for maximum
variance of all the observed variables. The eigenvalue characterise the contribution
of the factor in the total variance of parameters.
The R-mode factor analysis was performed using the following steps:
1. Standardisation of the data, which results in new values for all variables that
not only have zero mean but are measured in units of standard deviations. This
is done by subtracting the mean of the distribution from each observation and
dividing by the standard deviation of the distribution. The new variables have
a standard normal form.
2. Computing of a correlation matrix.
3. Extraction of a factor matrix by the principal component method considering
2–3 dominant significant factors.
4. Rotation of the factor matrix by Varimax-normalised method to achieve a
simple structure for interpretation.
5. Interpretation of dominant factors.
6. Plotting of factor loading on the axes of first two principal factors.
7. Grouping of studied parameters by factor intercorrelations.
8. Interpretation of processes.
The interpretation of dominant factors was made by taking into account the
highest factor loadings on chemical elements. For visualisation of the grouping of
elements on the axes of the first principal factors the plots of factor loadings were
compiled. The maps of the factor scores were computed to observe the spatial
distribution of factors.

3. Results and discussion

The variability of soil contamination was initially investigated and described by

a comparative analysis of the elements and by geochemical maps. Tables I and
II summarise the range, mean, median and accumulation ratio of the elements in
topsoils of the Tallinn region and urban Tallinn compared with average data from
other parts of the world. The variations in the element concentrations in Tallinn
have both natural and anthropogenic origins. Different types of soils are presented
178 L. BITYUKOVA ET AL.

TABLE I
The range, median, mean (in mg kg−1 , n = 229) and accumulation
ratio of elements in topsoils of Tallinn region

Det. Range Median Mean Clarke Accum.

limit ratio

As 40 20–74 20 23 8.74 2.69

Ba 200 100–1120 370 439 5601 0.78
Cr 34 16–257 63 70 65 1.08
Ga 2 1–92 8 8 282 0.30
Mn 300 26–4260 670 821 545 1.51
Ni 10 2–92 19 23 20 1.15
Pb 30 5–425 51 63 32 1.97
Sr 130 66–4220 350 391 2001 1.96
Ti 100 146–9970 4759 4698 3500 1.34
V 20 7–350 29 35 901 0.39
Zn 50 16–390 110 121 73.51 1.64
Zr 100 74–590 180 s 193 2241 0.86

Mean concentration in the world soils (Clarke) after: 1 Shacklette

and Boerngen, 1984; 2 Wedepohl K., 1978; 3 Erdman et al., 1976,;
4 Shacklette et al., 1974; and other by Kabata-Pendias and Pendias
(1986).

for the studied territory. Sandy and clayey soils occur in the northern part of Tallinn
near the seashore. Sandy shallow soils are also located in the southwestern part of
the studied territory. The underlying rocks in this area are fluvioglacial gravels and
sandy deposits (Karukäpp and Mikalauskas, 1970). Swamp soils occur on the pen-
insulas (seashore areas) and near the lakes. The alvar soils (limestone-rendzinas)
are more than 25% of the eastern part of the studied territory where the bedrocks
are represented by limestones and marls (Rooma and Sepp, 1972). Technogenic
soils are usual on the territory of Maardu. A number of typical lithogenic elements
in the soils depend strongly on the type, and variations in the mineralogical and
granulometrical compositions of subsurface bedrocks.

3.1. ELEMENT CONCENTRATIONS IN THE TOPSOILS OF TALLINN REGION

3.1.1. Typical lithogenic elements distribution

The major element variations in soils from the Tallinn region are determined by the
composition of the underlying rocks, as illustrated in the maps of the major ele-
ments (Birke et al., 1997a). The bedrocks within the territory consist of Cambrian
sandstones, various siltstones and clays and Ordovician carbonate rocks. Locally
(in the quarry Maardu) Upper Ordovician dark argillite (Dictyonema Shale) out-
 URBAN GEOCHEMISTRY OF TALLINN 179
TABLE II
The range, median, mean (in mg kg−1 , n = 198) and accumulation
ratio of elements in topsoils of urban Tallinn

Det. Range Median Mean Clarke Accum.

limit ratio

Ag 0.1 0–3 0.15 0.2 0.71 0.29

B 10 10–100 20 24 9.85 2.44
Ba 100 60–600 250 254 5601 0.45
Be 1 0–2.5 0.6 0.8 1.61 0.50
Co 3 0.8–50 5 5.2 8.5 0.61
Cr 6 5.7–300 33 39.9 65 0.61
Cu 1 7–621 35 45 262 1.73
Ga 3 3–15 8 8 282 0.29
La 10 0–40 20 19 47 0.40
Mn 10 76–1750 320 384 545 0.70
Mo 1 0–30 1.5 1.8 2 0.90
Ni 1 4.3–65 15 16 20 0.80
Pb 3 5.7–602 50 75.3 32 2.35
Sc 1 0.4–13.3 3 3.1 7.13 0.44
Sn 1 0–4 3 4.5 1.1 4.09
Sr 60 30–300 80 94 2001 0.47
Ti 10 190–3500 1735 1734 3500 0.50
V 3 5.7–90 30 31.7 901 0.35
Y 10 10–60 20 23 251 0.92
Yb 1 1–6 2 2 3 0.67
Zn 10 11.4–1560 114 156.1 73.51 2.12
Zr 10 60–400 200 183 2241 0.82

See legend of Table I.

crops. The prevailing subsurface rocks are quaternary deposits. Their genesis and
their composition vary widely. On the basis of the correlation matrix analysis two
associations of the typical lithogenic elements with a high level of the correlation
may clearly be distinguished:
(1) K2 O, Al2 O3 , Fe2 O3 , Ti and Ga;
(2) CaO, MgO, Mn and Fe2 O3 .

The first group is a typical natural element association and reflects the influence of
the terrigenous bedrocks and quaternary deposits. The second association is typical
for carbonate rocks. The soils in the studied territory are shallow, therefore, the
influence of composition of underlying rocks on the soils is very high. Such soils
180 L. BITYUKOVA ET AL.

usually contain many minerals and fine fragments derived from the underlying
rocks. The geochemical maps of Al2 O3 , K2 O, Fe2 O3 distributions are very similar
and these elements are strongly positively correlated (Birke et al., 1997a). The
total concentrations of these typical lithogenic elements depend very strongly on
the mineralogical composition and especially on the clay content of the soils. The
high abundance of clay minerals and iron oxides in the soils leads to intensive
adsorption of other elements. Other oxide minerals are subordinate and are there-
fore likely to contribute to a smaller extend to elements adsorption (Yaron et al.,
1996).
The concentrations of Al2 O3 , K2 O, Fe2 O3 are very low in the sandy soils and
high in the soils rich in clay. The SiO2 concentrations are the opposite. The correl-
ation between Al2 O3 and K2 O is very high with a correlation coefficient 0.83. A
significant positive correlation (r = 0.43) was determined for Al2 O3 with Fe2 O3 , a
negative correlation (r = −0.41) was calculated for Al2 O3 with SiO2 . In territories
with glaciogenous and glaciolacustrine parent rocks and boggy deposits, the soils
are characterised by Al2 O3 concentrations between 7–10%, K2 O concentrations
vary from 2.5 to 4% and Fe2 O3 from 4 – 6%. These concentrations are similar to
those observed in clays (Kabata-Pendias and Pendias, 1986). The granulometric
composition of these deposits is represented by loam, sandy loam, loamy sand
and loamy sand with clasts. Usually the boggy deposits have relatively low con-
centrations of Al2 O3 (7–8%) and K2 O (2.5–3%). The concentration of Fe2 O3 in
these types of deposits is constant. The soils which were formed on the different
types of the sandy quaternary marine deposits (sand, gravel and shingle) and on
the glaciofluvial deposits (sand, gravel and pebble) are characterised by lower
contents of major elements: Al2 O3 : 1–4%, K2 O: less than 2%, Fe2 O3 : less than
2%. SiO2 varies between 70–90% in the sandy soils and 60–70% in the loamy
soils.
MgO and CaO have a high positive correlation (0.86) in the soils. The com-
position of the bedrock clearly influences the distribution of these elements. The
average level of CaO in the soils is 4–8% (mean 5.49%), MgO – up to 1.5%
(mean 1.24%). In soils where the thickness of quaternary deposits is lower than
1 m and the underlying Ordovician carbonate rocks outcrop, the concentration of
CaO increases up to 10–16% and MgO up to 2.5%.
All typical lithogenic elements have high loadings on the first factor for the
soils of the Tallinn region. The first factor has the highest total variance (24.82%)
(Table III). For the first factor the positive factor loadings for Al2 O3 , MgO, Fe2 O3 ,
K2 O, Ti, Mn, Ga and V are described in Table IV. SiO2 has a negative factor
loading. The map of the factor scores of the first factor is represented in Figure 2.
The first factor reflects geogenic (pedogenic) influences of natural origin. It has a
high loading in soils of high clay contents (about +1.5) and a lower loading in soils
with a high content of sand (about −1.0). The loading of the first factor decreases
in areas near the seacoast and in the central part of the territory with prevailing
sandy quaternary deposits. In Figure 3 the groups of elements with high loadings
 URBAN GEOCHEMISTRY OF TALLINN 181

TABLE III
Eigenvalues of factors for the Tallinn region

Factor Eigenvalue % of total Cumulative Cumulative

variance eigenvalues percents

1 4.96 24.82 4.96 24.82

2 3.23 16.13 8.19 40.95
3 2.02 10.09 10.21 51.04
4 1.55 7.73 11.75 58.77
5 1.31 6.53 13.06 65.30
6 1.07 5.34 14.13 70.64

TABLE IV
Factor loadings for the Tallinn region

Element Factor 1 Factor 2 Factor 3 Factor 4 Factor 5 Factor 6

CaO −0.03 0.12 0.94 0.11 0.14 −0.01

SiO2 −0.37
0.37 −0.17 −0.82
0.82 −0.13 −0.17 −0.23
Al2 O3 0.81 −0.16 0.24 −0.18 −0.12 −0.00
MgO 0.24 −0.05 0.92 0.07 0.04 −0.05
Fe2 O3 0.63 0.40 0.16 0.03 0.26 0.00
K2 O 0.88 −0.04 0.15 −0.17 −0.09 0.06
P 2 O5 0.00 0.19 0.15 −0.00 0.91 0.06
S −0.07 0.25 0.23 0.22 0.14 0.63
Pb 0.00 −0.03 0.14 0.78 −0.05 0.16
Cr −0.09 0.84 −0.18 0.06 0.12 0.11
Ti 0.57 −0.05 0.35 −0.25 0.03 0.46
Zn 0.07 0.05 0.15 0.60 0.07 0.43
Zr 0.05 0.22 −0.23 −0.04 0.24 0.63
Sr −0.04 0.11 0.10 0.05 0.89 0.26
Mn 0.41 0.64 0.24 0.10 0.21 0.05
Ni 0.09 0.64 0.16 0.06 0.25 0.05
Ga 0.66 −0.23 −0.05 0.33 0.05 −0.10
V 0.56 0.30 −0.03 0.11 −0.02 −0.00
Ba −0.16 0.73 0.08 −0.02 −0.09 0.30
As −0.08 0.15 −0.00 0.66 0.05 −0.22

Expl.Var 3.33 2.62 2.94 1.75 1.97 1.51

Prp.Total 0.17 0.13 0.15 0.09 0.10 0.08

182 L. BITYUKOVA ET AL.

Figure 2. Contour map of the distribution of factor scores for the first factor for topsoils of Tallinn
region.

(0.6–0.9) at the first and second factors are shown. Manganese is connected with
the bedrocks as well as with industrial pollution of soils and has significant loadings
for both factors.

3.1.2. Trace elements distribution

Range, median and mean concentrations of elements in the soils of Tallinn re-
gion are described in Table I. A comparison of the mean element concentrations
in the topsoils of the Tallinn region with worldwide average element concentra-
tions of soils (Clarke) from Kabata-Pendias and Pendias (1986) and other authors
(Shacklette et al., 1974; Erdman et al., 1976; Wedepohl K., 1978; Shacklette and
Boerngen, 1984) is presented. The enrichment of trace elements in the topsoil is
considered to be caused mainly by anthropogenic influence. The accumulation
ratio (defined as the mean element concentration of soils divided by the Clarke)
indicates high accumulations in the soils from Tallinn. The mean concentrations
of As, Mn, Pb, Sr, Ti and Zn in the soils from the Tallinn region are higher than
the worldwide average. The mean concentration of Ba, Cr, Ni, and Zr are very
close to the worldwide average value in the noncontaminated soils, as indicated by
Kabata-Pendias and Pendias (1986) and other authors. The concentration of these
elements is tolerable for human health (Yaron et al., 1996). The lower level of
trace elements concentrations in the noncontaminated soils is observed at the areas
where the underlying rocks are presented by sandy and carbonate rocks. The total
level of trace elements is very low in these types of rocks and very small amount
of elements may be extracted from them in the result of dissolution and chemical
weathering. Some amount of underlying rocks is in the soils as an admixture. The
estimation of contribution of the trace elements from the bedrocks is possible only
by special study.
 URBAN GEOCHEMISTRY OF TALLINN 183

Figure 3. Factor loadings for first and second factors for topsoils of Tallinn region. Element
associations with highest values of factor loading are shown inside boxes.

The local geochemical anomalies of Tallinn were plotted in distribution maps

for all measured elements. Especially high local element concentrations were de-
termined for As, Cr, Mn, Ni, Pb, S, V and Zn. The concentrations of As, Cr, Mn
and V are more than three times higher, and Pb and Zn are more than five times
higher than the background levels.
The correlation matrix for the Tallinn region data set shows high correlations
for the following trace element association: As, Ba, Cr, Ni, Pb, S and Zn. The
correlation between the trace elements is usually lower than correlation between
the major elements in the topsoils.
In a factor analysis for the topsoils six dominant factors were chosen for in-
terpretation. In Table III the eigenvalues of the factor scores for these factors are
shown. Six factors account for 70.6% of elements variation for the soils of Tallinn
region. The relations between natural and anthropogenic (technogenic) chemical
parameters in the soils can be recognised. The plot of two dominant factors
(Figure 3) shows that the first factor with the highest values of factor loadings
may reflect the geogenic influence on the topsoils composition (Table IV). Typical
anthropogenic elements have high loadings on the second factor and suggest that
this factor can be associated with intensive anthropogenic contamination. The pos-
itive anomalies on the second factor score map are observed near the main roads
and in Maardu. However, the apparent contamination in Maardu may be connected
with natural leaching processes in Dictyonema Shales and the Maardu phosphorite
deposits and with a secondary concentration of these elements in the soils. In the
Tallinn region two areas of major industrial pollution of soils were revealed. The
first area was characterised by Ba, Cr, Mn, Ni and partly iron whilst the second
group was characterised by As, Pb and Zn.
Soil pollution (enrichment) indices permit a simplified estimation of the intens-
ity of soil contamination by using the multiple element data sets. This index was
184 L. BITYUKOVA ET AL.

Figure 4. Pollution index contour map of topsoils of Tallinn region.

used by Nishida et al. (1982) for the river sediments. Pollution index maps of the
soils also permitted Chon et al. (1996) to classify the soils on the basis of their
geochemistry. The pollution index was calculated by averaging the ratios of the
concentrations of the topsoils divided by the mean concentration of the elements in
worldwide soils:

1X
n
element concentration in topsoili
Pollution index =
n i=1 average element concentration in the worldwide soils

where n is a number of the measured elements.

The maps of the pollution indices for As, Ba, Cr, Ga, Mn, Ni, Pb, Sr, Ti, V,
Zn and Zr of the soils of Tallinn region (Figure 4), show that the highest level
of pollution is concentrated in the northern part of the region. In the south the
pollution index is very close to 1.0 varying between 0.8 to 1.2. The maximum
values of pollution indices are observed in Maardu.
In the large geochemical anomaly at Maardu the level of pollution indices in-
creases to 3.0 and clearly indicates the most intensive contamination of the topsoils
by trace elements. One important source of environmental enrichment in the north-
eastern part of the territory is the Maardu phosphorite deposit (20 km from Tallinn).
Soils from the territory of the phosphorite deposit reach anomalous P2 O5 contents
up to 11%, and because of this, phosphorus was excluded from the calculation of
pollution indices. The exploitation of this deposit is now finished, but the dumps are
still a source of pollution of soils, not only by P2 O5 but also by other elements. The
bedrocks in this area consist of limestone, dark argillite (Dictyonema Shale) with
high concentrations of the toxic elements, terrigenous rocks, quaternary deposits
and also glauconite sandstone and pyrites. Large amounts of polluting elements
are leached from soils and bedrocks and can be found observed in surface water
from the territory of Maardu (Pihlak et al., 1986).
 URBAN GEOCHEMISTRY OF TALLINN 185

3.2. ELEMENT CONCENTRATIONS IN TOPSOILS OF URBAN TALLINN

The anthropogenic influence was especially high on the territory of urban Tallinn.
Figure 5 shows the relative changes of the accumulation ratios of elements in the
topsoils of the Tallinn region and of urban Tallinn. The accumulation ratios of Pb
and Zn are higher in the topsoils of urban Tallinn than in the region. The concen-
trations of Ga, V and Zr are relatively low in both areas. A comparison of mean
element concentrations with Clarks (Kabata-Pendias and Pendias, 1986) showed
that the accumulation ratios for B, Cu, Pb, Sn and Zn in the topsoils of the central
part of the city (urban Tallinn) are greater than 1.0. Compared with the data of other
urban regions (Table V) (Lis, 1992; Taraškevicius, 1992; Birke and Rauch, 1994),
it can be shown that the Co, Cu, Pb and Zn mean concentrations in urban Tallinn
are close to mean concentrations in topsoils from Berlin, and that the B, Cr and
V mean concentrations from urban Tallinn are very similar to mean values of the
topsoils in Vilnius. In Warsaw the concentrations of As, Co, Cu and Pb are lower
than in urban Tallinn.
The analysis of the correlation matrix for data from urban Tallinn permits us
to distinguish trace elements associations, caused by different sources of pollu-
tion. The correlation coefficients vary within the range 0.3–0.7. Different element
groups can be clearly distinguished: the first association includes Co, Cr and Ni.
The second includes Be, Ga, La, Sr, Y and Yb. Both groups contain Ba, Mn, Sc, Ti
and V. The third association of elements is represented by Cr, Cu, Pb and Zn. All
these associations reflect the technogenic influence and are controlled by different
contamination sources. Near a furniture plant, the increase of Ba, Be, Cr and Zn
concentrations was established. A high level of Pb was observed close to a railway
station and footwear and radio engineering factories. The contamination of soils
by Co, Cr, Pb, Sn and Zn was connected with metal-working or reworking of
non-ferrous metal factories.
Using R-mode factor analysis for the topsoils of urban Tallinn, seven dom-
inant factors were determined. In Table VI the eigenvalues for these factors are
described. The seven factors account for 65.4% of elements variation in the soils

Figure 5. Accumulation ratios of element concentrations in topsoils of Tallinn region and urban
Tallinn.
186 L. BITYUKOVA ET AL.

TABLE V
The element concentrations (mg kg−1 ) in topsoils of urban Tallinn

Tallinn Berlin Warsaw Vilnius

(Birke & Rauch, 1994) (Lis, 1992) (Taraškevicius, 1992)
n = 198 n = 228 n = 3299 n = 1713 n = 670
Urban Background Mean Background Mean Background Mean

Ag 0.2 0.12
As 22.6 4 2.6 5 2
B 24 14 12 – – 26
Ba 254 363 360
Co 5.2 <5 <5 1.9 1 3.1
Cr 39.9 63.3 27 18 – 34
Cu 45 39 8 10 6 11
Ga 8 8.8 4.3
Mn 384 831.6 640
Mo 1.8 0.89
Pb 75.3 60.7 79 21 20 13 18
Sc 3.1 4.2
Sn 4.5 7.3 2.4
Sr 94 345.6
Ti 1734 4588 2100
V 31.7 34.7 30
Y 2 15
Yb 23 1.5
Zn 156.1 112.5 151 24 54 34 35
Zr 183 186.9 340

TABLE VI
Eigenvalues of factors for urban Tallinn

Factor Eigenvalue % total Cumulative Cumulative

variance eigenvalues percents

1 5.07 23.06 5.07 23.06

2 2.95 13.40 8.02 36.46
3 1.78 8.09 9.80 44.55
4 1.32 6.00 11.12 50.55
5 1.14 5.18 12.26 55.73
6 1.09 4.96 13.35 60.69
7 1.04 4.74 14.39 65.43
 URBAN GEOCHEMISTRY OF TALLINN 187
TABLE VII
Factor loadings for urban Tallinn

Element Factor Factor Factor Factor Factor Factor Factor

1 2 3 4 5 6 7

Sc 0.83 0.14 0.19 −0.03 −0.07 −0.01 0.07

Ti 0.87 0.03 0.02 0.17 0.00 0.07 0.05
V 0.75 0.06 0.24 0.19 0.06 0.04 0.18
Cr 0.14 −0.06 −0.05 −0.07 0.27 −0.10 0.78
Mn 0.50 0.10 0.57 −0.24 0.06 −0.10 0.14
Co 0.12 −0.02 −0.23 −0.30 0.23 −0.05 −0.33
Ni 0.24 0.06 0.02 0.05 0.02 0.15 0.76
Cu 0.00 0.29 0.01 −0.06 0.36 0.66 0.18
Pb −0.17 0.29 −0.05 0.13 0.60 −0.01 0.42
Zn −0.25 0.57 −0.05 0.04 0.33 0.37 0.32
Ga 0.40 0.28 0.27 0.34 0.23 −0.04 0.03
Sn −0.03 −0.08 0.11 0.08 0.73 0.17 0.08
Mo 0.06 −0.15 0.08 0.12 0.03 0.78 −0.04
Zr 0.12 −0.07 0.01 0.79 −0.01 0.10 −0.04
B 0.18 0.12 0.14 0.47 0.37 −0.01 0.13
Y 0.13 0.01 0.86 0.17 0.00 0.03 −0.06
Yb 0.32 0.11 0.73 0.31 0.08 −0.06 −0.01
La 0.20 0.58 0.53 0.07 0.00 −0.01 −0.09
Be 0.37 0.71 0.09 −0.04 −0.11 −0.10 −0.02
Sr 0.03 0.04 0.79 −0.08 0.22 0.18 0.07
Ba 0.12 0.14 0.28 0.36 0.57 −0.06 0.01
Ag 0.03 −0.06 0.03 −0.14 0.76 0.12 0.01

Expl. Var. 2.97 1.55 2.86 1.52 2.45 1.33 1.72

Prp. Total 0.14 0.07 0.13 0.07 0.11 0.06 0.08

of urban Tallinn. The first factor accounts for 23.06% of the parameter variations.
Be, Ga, Mn, Sc, Ti, V and Yb have a positive loading on this factor (Table VII).
On the map of factor scores for the first factor the local anomalies of factor scores
are clearly observed (Figure 6). The average level of this factor score in the urban
Tallinn area varies between −0.5 and +0.5. Close to industrial sites the factor
scores increase up to +4.0. The maximum factor scores for the first factor in Tallinn
are observed near chemical industries, metal-working, reworking of non-ferrous
metals factories and close to asphalt production factories. They are relatively high
in soils close to the glass factory and machine-building plant.
188 L. BITYUKOVA ET AL.

Figure 6. Contour map of the distribution of factor scores for the first factor for topsoils of urban
Tallinn.

Figure 7. Factor loading for first and second factors for topsoils of urban Tallinn. Element
associations with highest values of factor loading are shown inside boxes.

Factor loadings for the two first factors are shown in Figure 7. The second factor
in urban Tallinn controls the increase in Be, Cu, Ga, La, Pb and Zn. The total
variance of this factor is 13.4%. The map of the factor scores for the second factor
shows anomalies around non-ferrous metals production, processing, machine and
radio engineering factories. The soils near such enterprises show especially high
pollution with Zn, Pb and Cu.
For the soils of urban Tallinn the pollution indices were calculated for the ele-
ments Ag, B, Ba, Be, Co, Cr, Cu, Ga, La, Mn, Mo, Ni, Pb, Sc, Sn, Sr, Ti, Y, Yb,
V, Zn and Zr. The greatest part of urban Tallinn is characterised by low values of
 URBAN GEOCHEMISTRY OF TALLINN 189

Figure 8. Pollution index contour map of topsoils of urban Tallinn.

pollution indices near 1.0. Especially low values of pollution indices (in average
about 0.8) are observed in southern and eastern Tallinn. The most polluted area in
urban Tallinn (Figure 8) is located on the Kopli peninsula and in the central part of
the city. Most factories are located there and some of them are very old and have
been closed for several years. Areas with the highest concentration of industrial
sites have the maximum values of pollution indices (2.0–3.0, locally up to 3.4).
As can be seen in the compiled geochemical maps, in urban Tallinn the level
of element concentrations and the number of local anomalies are generally higher,
depending on the high number of different sources of pollution.
Tallinn is the biggest industrial centre of Estonia and during Soviet times a
great number of enterprises, including textile, food, metal-working, heavy, energy
and military industries, were located on its territory. Some hundred individual in-
dustrial pollution sources can be identified. Transport (public and private, national
and international) is an important additional source. Tallinn is also a railway centre
and an important seaport. The large number of pollution sources and the complex
composition of the emissions make it difficult to identify and estimate the influ-
ence of all sources of pollution. However, the application of correlation and factor
analysis has permitted a more perfect classification of the types of industrial en-
terprises whose production led to contamination with defined groups of pollutants.
In urban Tallinn the contamination of soils by Cr, Cu, Mo, Ni, Pb, Yb and Zn
is connected with metal-working, reworking of non-ferrous metal and machinery
construction factories; increasing of Ag, Co, Cr, Cu, S, Sn and Zn concentrations
was established near plastic article and trade equipment plants; close to the radio
engineering factory the soils are enriched by Cr, Mo, Pb, Sn and Ti. Close to the
railway station and roads a relative increase of Pb and V is observed.
190 L. BITYUKOVA ET AL.

TABLE VIII
Heavy metal distribution in the extracts from upper and lower layers of
topsoils from Tallinn

Elements in % from total amount

Extract Soil layer Pb Cu Mn Ni Cr Zn

1 Upper 0.3 0.3 <0.1 0.2 0.2 0.3

Lower 0.8 0.6 <0.1 0.4 0.3 0.5
2 Upper 1.8 1.1 0.8 0.6 0.3 0.5
Lower 2.0 1.4 0.4 0.6 0.3 0.4
3 Upper 19.6 7.6 31.8 8.6 8.1 43.7
Lower 15.7 6.8 32.8 7.7 7.4 37.2
4 Upper 1.3 47.2 14.9 14.4 16.2 28.1
Lower 5.7 35.4 13.6 12.2 14.2 22.7
5 Upper 56.8 22.9 23.4 17.2 26.1 20.2
Lower 45.6 25.8 23.4 17.2 23.2 27.1
6 Upper 8.5 9.4 7.6 8.5 20.9 7.2
Lower 10.9 12.5 8.7 9.6 20.0 12.1
7 Upper 11.6 11.5 21.4 50.5 28.3 n.m.
Lower 18.5 17.5 20.9 52.3 34.4 n.m.
Extract: 1 – water soluble components; 2 – easily exchanged ions; 3 –
carbonate with some compounds soluble under weakly acid conditions;
4 – organic matter together with some sulphides; 5 – amorphous hydrox-
ides of metals and elements adsorbed on them; 6 – easily decomposed
silicates, and 7 – insoluble residue.

The decoding of the complex character of soil contaminations by industrial

sources and the typifying of the sources of pollutions was carried out by Birke and
Rauch (1997b) in Berlin. According to these results the most intensive pollution
by Be, Cu, Ni, Ti and Zn is connected with mechanical engineering; detergent
production led to soil contamination by B, Ba, Be, Co, Ge, Sb, Se, Sn, Sr, Zn and
Zr; pollution by Cd, Cr, Fe, Pb, Sn and Zn was established close to factories of
metal-working and ferrous metal building industry. In the soils near petrol pumps
and industrial railway stations high levels of Fe, Mn, Pb and Zn concentrations
were determined. According to Taraškevicius (1992) the general sources of soil
contamination in Vilnius for Ag, Cd, Cr, Cu, Mn, Mo, Ni, Pb, Sc, Sn, V and
Zn are the heating plants. Pollution by Ag, Cr, Cu, Sn and Zn is connected with
printing plants. The increase of Cd, Cr, Cu, Mo, Ni, Pb, Sn and Zn concentra-
tions is observed close to metal-working and instrument-making industry factories.
Around these industries are also high levels of Ni, Pb, V and Zn. Summing up, it
can be said, that in urban areas the anthropogenic influence is very strong and
the special features are formed by the location type and intensity of the industrial
production.
 URBAN GEOCHEMISTRY OF TALLINN 191

The geochemical maps of urban areas illustrate that strong geochemical anom-
alies are resulting from emission from very nearby industrial enterprises (Birke
et al., 1997a). Considering the mobility of some elements (Cr, Cu, Mn, Ni, Pb and
Zn) with high concentrations in the soils of Tallinn it is evident that only a limited
part of the total contents of these elements in the soils can easily by mobilised
(Bityukova, 1994). In Table VIII the distributions of the element concentrations
in the different extracts are represented. As we can see, the distribution and the
concentration of the elements in the extracts from the upper (0–5 cm) and the lower
(5–10 cm) soil horizons are very similar. About 30% of the total content of Cu, Mn
and Pb are concentrated in the studied topsoils in the water-soluble form, freely
interchangeable ions and compounds, soluble in weakly acid condition. Extraction
of Cr, Mn and Ni is still more difficult (about 10%). Taking into account the amount
of elements connected with organic matter in the soils it can be said, that by the
extraction only about 50% from the total content of these elements are freely avail-
able for plants. These results permitted to estimate the real danger of soil pollutions
for human health, agriculture and growing of plants.

4. Conclusions

The regional geochemical sampling of urban Tallinn and the Tallinn region permit-
ted us to determine the background level of the major and trace element concentra-
tions in the topsoils of the biggest industrial centre of Estonia and its suburbs. The
major element concentrations are generally of natural origin and correlate with the
composition of the underlying rocks. The soils of the Tallinn region are character-
ised by higher mean concentrations of As, Mn, Pb, Sr, Ti and Zn in comparison
to average concentrations in the worldwide soils. Urban soils show significant
increases in the mean concentrations of B, Cu, Pb, Sn and Zn.
Comparative analysis of the obtained data, interpretation of geochemical maps
and the calculation of pollution indices permitted to reveal the geochemical anom-
alies in the studied area. Elevated concentrations of Ba, Cr, Mn and Ni were found
in soils around the Maardu phosphate mine and its dumps. The local anomalies in
urban Tallinn are characterised by significant increased concentrations of As, Cr,
Mn and V (more than three times) and of Pb and Zn (more than five times) over
background levels. To comment on the use of the soils for agricultural purposes it
is necessary to take into account the possible mechanism of element migration and
plant uptake. This is especially necessary for Cu, Mn and Pb which are elements
with higher mobility in acidic soils.
The application of multivariate statistical analysis for the assessment of the
geochemical data permitted the determination and classification of the different
sources of contaminants. In urban Tallinn the influence of different types of con-
tamination is complex. The most intensive soil contaminations are caused by metal-
working, reworking of non-ferrous metal and machinery construction industry.
192 L. BITYUKOVA ET AL.

As a result of this initial stage of the geochemical investigations the further

monitoring of the soils in the Tallinn area can be planned.

Acknowledgements

The authors wish to thank our former colleagues from the Institute of Geology
(Tallinn) Dr. K. Tibar, Dr. K. Vares, Dr. B. Naumov and Dr. A. Smirnov for their
assistance in the field and laboratory. We are very grateful to the Federal Institute of
Geosciences and Natural Resources, Germany (BGR) staff and personally to Uwe
Rauch for the help and discussions about data processing and mapping. We are
thankful to the Scientific and Environmental Affairs Division NATO that supported
this work. The authors are grateful to Mr. B. Smith and anonymous reviewer for
the constructive comments, which significantly improved this paper.

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