GEOLOGIJA 41, 319-338 (1998), Ljubljana 1999 (Ш
Geochemical Soil Survey at Jesenice area, Slovenia
Geokemične raziskave tal na območju Jesenic
Robert Šajn, Milan Bidovec & Mateja Gosar
Geological Survey of Slovenia
Dimičeva 14, 1000 Ljubljana, Slovenia
Simon Pire
University in Ljubljana, Faculty for Natural Sciences and Technology,
Department of Geology
Aškerčeva 12, 1000 Ljubljana
Key words: geochemistry, pollution, soil, household dust, heavy metals, Slovenia
Kjučne besede: geokemija, onesnaženje, tla, bivalni prah, težke kovine, Slovenija
Abstract
The purpose of geochemical investigations in the Jesenice area was to establish
contents and distribution of chemical elements in soils, and to separate the natural
from the man-produced geochemical distributions.
Shown and commented are distributions of 21 elements (Al, Ca, Fe, K, Mg, Ti,
Ва, Cd, Cr, Cu, Hg, La, Mn, Nb, Ni, Pb, Se, Th, V, Zn and Zr). Based on comparison
of distributions of these elements in soils and urban sediments (household and attic
dust) of Slovenia two natural geochemical associations were distinguished in the
Jesenice area (Al-Fe-K-Ti-Ba-La-Nb-Sc-Th-V-Zr and soil pH-Ca-Mg), and two
associations that were influenced by several centuries of mining and iron making
(Cd-Cu-Hg-Mn-Pb-Zn and Fe-Cr-Ni).
Povzetek
Namen geokemičnih raziskav na območju Jesenic je bil ugotoviti vsebnosti in
prostorske porazdelitve kemičnih prvin v tleh ter ločiti naravne geokemične
porazdelitve prvin od antropogeno povzročenih.
Prikazali in komentirali smo porazdelitve 21 kemičnih prvin (Al, Ca, Fe, K, Mg,
Ti, Ba, Cd, Cr, Cu, Hg, La, Mn, Nb, Ni, Pb, Sc, Th, V, Zn in Zr). Na osnovi primerjave
vsebnosti teh prvin v tleh in urbanih sedimentili (stanovanjski in podstrešni prah)
Slovenije smo na območju Jesenic ločili dve naravni geokemični združbi (Al-Fe-K-
Ti-Ba-La-Nb-Sc-Th-V-Zr in talni pH-Ca-Mg) in dve združbi, ki predstavljata
porazdelitev, na katero je vplivala večstoletna železarska dejavnost (Cd-Cu-Hg-Mn-
Pb-Zn in Fe-Cr-Ni).
320_Robert Šajn, Milan Bidovec, Mateja Gosar & Simon Pire
General
Geography and Geology
The Jesenice area is situated in the northwest part of Slovenia (Fig. 1). North of
the town is the N-E trending Karavanke mountain range, in the west the Julian Alps
and in the south the wooded high plateau of Mežakla. In the valley that passes in the
southeast into the Ljubljana basin flows the river Sava. The area is mountainous and
it belongs physiographically to the Southern Alps, and its southeastern part is flat.
The administrative, political and economic centre is the town of Jesenice, a typical
industrial town with ironmaking tradition, inhabited by a population of about 20,000
(http://www.jesenice.si/jeobc.html; R e s m a n, 1990).
The territory is situated at the contact of three geotectonic units: the south Kara-
vanke, the Ljubljana basin and the Julian Alps (Buser&Cajhen, 1980; B u s e r,
1980; Jurkovšek, 1986a and b). The south Karavanke are separated by the NW-
SE trending Sava fault from the Julian Alps and the Ljubljana basin. In the structure
of the southern Karavanke the Košuta nappe and the Southern Karavanke nappe can
be distinguished. The central ridge of Karavanke is built by the Košuta nappe that
consists predominantly of carbonate rocks of Lower to Upper Triassic age. The
southern Karavanke nappe, in the area between the Košuta nappe and the Sava
fault, consists mostly of Paleozoic clastic and carbonate rocks. The Radovljica-Bled
subsided basin in the southeast is filled by Quaternary deposits in the extreme part of
the Ljubljana basin. In the southeast, the Mežakla plateau consists of Lower to
Upper Triassic carbonate rocks (Buser & Cajhen, 1980; Jurkovšek, 1986b).
The area is cut by faults of predominantly dinaric (NW-SE) direction. Dominant
among them is the Sava fault. The course of the Sava valley is conditioned by it.
Long dinaric faults were formed in the Upper Pliocene, and the Ljubljana basin
Introduction
Iron making in the Jesenice area is traditional. The development of mines and fur-
naces started end of 14th century as testified by the Ortenburg mining regulations. In
the second half of the 18th century a number of the properties were bought by
Valentin Ruard who started to extend and restore the mining prospects. A number of
prospects were owned also by gross merchant Zois. End of 18th century the Zois fam-
ily ran into financial difficulties owing to obsolete technology and foreign competi-
tion. For these reasons in 1869 the Carniolan industrial society was founded. Two
bloom areas fused into one that was the largest industrial enterprise in the Duchy of
Carniola. From the bloom areas at the banks of the Sava river new modern ironworks
was developed, and the settlement grew into an industrial town that assisted the
development to many other activities (http://www.jesenice.si/jeobc.html; R e s m a n,
1990).
In the Jesenice area a number of investigations of pollution associated chiefly to
emissions of the steelworks were performed. Not known was, however, the "her-
itage"of several centuries of pollution own to ironmaking, and its impact on the geo-
chemical properties of the landscape. In 1994 we started in the frame of a Alps-Adria
project the systematic investigation of soils by sampling them according to pedologie
horizons, and analysing a large number of chemical elements in them.
Geochemical Soil Survey at Jesenice area, Slovenia_321
Fig. 1. Researched area
SI. 1. Lega raziskanega območja
started to sink along them at the start of Pleistocene. The formed basin was filled by
large amounts of mainly carbonate fluvial material (Buser & Cajhen, 1980;
Jurkovšek, 1986b).
The final touch to the physiography v^as given by the glacial age. In spite of heavy
glacial impact, the valley remained relatively narrow. Characteristic of glaciations
are remains of lateral moraines at Mala Mežakla, and front and lateral moraines at
Blejska Dobrava. After retreat of the glacier at Mojstrana a smaller dam lake was
formed.
On the highest steep slopes lithosols occur. Rendzinas are frequent on limestones
and dolomites, carbonate talus and glacial drift. In favourable conditions rendzinas
pass into eutric cambisols or calcareous cambisols on limestones and dolomites. On
silicate (siliceous) clastic rocks largely rankers develop, and to a smaller extent, also
dystric cambisols.
Climatic Characteristics
The Jesenice area is characterized by a predominance of continental properties of
Middle European climate owing to the distance from the sea and the high mountain-
ous barriers in-between. The rainfall regime is of submediterranean type. Apprecia-
ble differences in altitudes result into four climatic belts: the submountainous, moun-
tainous, subalpine and alpine climatic belts (Š i p e c, 1990).
The essential characteristics of climate are cold winters and fresh summers. The
322_Robert Šajn, Milan Bidovec, Mateja Gosar & Simon Pire
mean temperature at Jesenice amounts to -2.5 C tor January, 18 C tor July, and 8 C
for the average year. The rainfall maximums occur in October and in July, and the
minimum in January. The average yearly duration of snow cover is 30 days. The area
is not considerably subject to forming of atmospheric inversion, or to fogs. Only a
yearly average of 10 days are foggy, occurring mainly during the cold part of the year
(Šipec, 1990).
Very important for distributing of pollution are two local winds, the valley wind
and the mountain wind. The first blows mostly during nights when the cooled air
descends towards the Ljubljana basin. The mountain wind blows usually during the
first part of the day. It forms by heating of the air, and is directed up the valley. Next
to local winds also the cyclonic air circulation transversely to the axis of the valley is
present (Šipec, 1990).
Estimate of Pollution
According to earlier data (Šipec, 1990) the daily dust emission from ironworks
prior to 1971 amounted to 48 tons. To this amount also about 270 daily tons of ash
should be added, as a result of production of generator gas and operation of the steel-
works heating plant. Characteristic for the plant was pollution with red dust. Pollu-
tion was disseminated along the valley axis far from the sources, and propelled by
the winds. From 1971 to 1987 the plant undertook a partial remediation and modern-
ization. The energy concept of steelworks was changed, the furnaces reconstructed,
and dust collectors and cleaning devices installed. At that time also regular monitor-
ing of pollution was started. Then followed modernization of Steelworks 1 that fur-
ther reduced the dust emissions. After 1987 follows the final sanitation with aban-
doning of furnaces and Siemens-Martin ovens, and with the start of Steelworks 2
(Osojnik et al., 1988, 1990).
It was estimated that the emission from Steelworks 1, Steelworks 2 and the plants
for regeneration of hydrochloric acid emit daily approximately 2 t dust and 950 kg
SO2 (Šipec, 1990). Traffic and communal emissions contribute during heating sea-
son about 7 t SO2 daily. Iron works are indubitably the principal factor of environ-
mental degradation, followed by dense traffic in the valley, and by households in the
town. The contribution of iron works is gradually diminishing.
Materials and Methods
Sampling
Soil sampling in the Jesenice area was performed at a 1,4 x 1,4 km grid (Figs. 1
and 2). In 44 localities pedologie profiles were dug, and in total 122 samples of soil
horizons collected. Sampled were principally soils on carbonate rocks (30 localities),
followed by sandstone (6 localities) and Quaternary fluvial deposits (8 localities). Soil
types (Š k o r i Ć, 1977) comprised rendzinas in 16 cases, calcareous cambisols in 16
cases, dystric cambisols in 5 cases, ranker in 2, and agricultural soil, fluvisol, luvisol
and eutric cambisol in each one case.
Geochemical Soil Survey at Jesenice area, Slovenia_323
Fig. 2. Digital relief model of Jesenice area with soil profile locations
SI. 2. Digitalni model reliefa območja Jesenic z lokacijami vzorčenja v talnih profilih
Preparation of Samples and Analysis
Preparing of samples for chemical analysis was done along the lines given by
Pire et. al. (1991) that is similar to recommendation s of the UNESCO IGCP 259
project (D a r n 1 e y et al., 1994). The sampled material was first air dried for 15 days,
and then 48 hours in a fan oven at 40°C. The dry soil was gently crushed in a ceramic
mortar. The material was then passed through a stainless steel sieve with 2 mm open-
ings and quartered, and then crushed and milled to the analytical grain size of 0,063
mm.
Analysis in the ACME laboratories in Vancouver, Canada, was performed by plas-
ma emission spectrometry (ICP) after a total 4 acid digestion. The 0,5 g sample was
dissolved at 200 °C in 10 ml mixture of HCIO4, HNO3, HCl and HE In total, 35 ele-
ments were determined by ICP (Al, Ca, Fe, K, Mg, Na, P, Ti, Ag, As, Au, Ba, Be, Bi,
Cd, Co, Cr, Cu, La, Mn, Mo, Nb, Ni, Pb, Sb, Se, Sn, Sr, Th, U, V, W, Y, Zn and Zr). Hg
was determined after aqua regia digestion with atomic absorption spectrometry
(AAS) according to the cool evaporation procedure (ACME, 1994).
Potential acidity was determined by the procedure in which 10 g of sieved soil
sample is left for 24 hours in 25 ml 0,1 N CaCl2, mixed, left for 24 hours, mixed again
and pH measured (R h o a d e s, 1982; Hodnik, 1988).
A number of randomly selected samples was replicated for estimation of precision.
Geologic standard materials GXR-6, SJS-1 and SRM-2711 (Abbey 1983; E p s t e i
n, 1990) were used for estimating accuracy. All soil samples, replicates and geologic
standards were submitted to laboratory in a random succession. This procedure
assured unbiased treatment of samples and random distribution of possible drift of
analytical conditions across all samples.
324_Robert Šajn, Milan Bidovec, Mateja Gosar & Simon Pire
Sensitivity, Accuracy and Precision on Analysis
The sensitivity in the sense of the lower limit of detection was adequate for 28 out
of 36 analysed chemical elements. The elements Ag, Au, Be, Bi, Mo, Sb, Sn and U,
however, were removed from further statistical analysis (M i e s c h, 1976), since their
contents in the majority of analysed samples appeared to be below the lower detec-
tion limit of the analytical method. Excluded were also determinations of W and Co
because of the evidence on contamination of samples from grinding equipment made
out of W-Co steel, as established in former studies (Šajn, 1995).
Accuracy of analytical method for the remaining 26 elements was estimated by
calculation of relative systematic error between the determined and recommended
values of geological standards. Most analysed elements show in the range of the actu-
al soil samples very low deviations. The means of elements in analysed standards
generally differ for less than 15% of the recommended values. Larger negative devia-
tions showed Mg, P, Cd, La, Pb and Th, and larger positive deviations Cr
Precision of determinations was controlled by relative differences between pairs of
analytical determinations of the same samples (B 1 e j e c, 1976). Precision was con-
sidered good, since of the 26 considered elements only Cd, Th and Zr showed less
accurate results.
The reliability of analytical procedures, as shown by the mentioned control of sen-
sitivity, accuracy and precision, was considered adequate for using the determined
elemental contents in further statistical analyses.
Results of Study
In statistical analysis all 122 samples of soil horizons were used. For estimation of
the association between chemical elements multivariate statistical analyses of cluster
and R mode factor analysis were used (Le Maitre, 1982, K o š m e 1 j, 1983,
Davis, 1986, Rodionov et al., 1987). For the measure of similarity between
variables the product-moment correlation coefficient (r) was applied. In the final
multivariate analyses only 21 elements were retained. The elements Na, P, As, Sr and
Y were excluded because of the lack of significant associations with other chemical
elements. These elements formed independent clusters, or they resulted into low
communalities in factor analysis.
For illustration of results of the cluster analysis the dendrogram based on relative
association D/Dmax in percent were used (Fig. 3), and of the factor analysis the
matrix of higher rotated factor loadings (Tab. 2).
The geographic distribution of elemental composition of topsoil and of the lower
soil horizons is illustrated by maps of scores of extracted factors (Figs. 4a to 7b) and
maps of contents of Cd (Figs. 9a and 9b), Pb (Figs. 10a and 10b) and Zn (Figs. 11a and
lib). In the process of construction of geochemical maps the interpolation method of
universal kriging with linear variogram was applied (P e r i š i c, 1983; Davis,
1986). In interpolation of elemental contents 44 samples of topsoil and 78 samples of
lower soil horizons were taken in consideration. The basic cell for interpolation was
of the size of 200 x 200 m.
For class limits the percentile values of distribution of the interpolated values
were taken. Seven classes with the values of the following percentiles were selected:
0-10, 10-25, 25-40, 40-60, 60-75, 75-90, 90-100. The classes around the average are
broader, and the classes at both extremes narrower
Geochemical Soil Survey at Jesenice area, Slovenia__325
Tab. 1. Averages of content of elements in different sample materials (average values of Al, Ca,
Fe, K, Mg, Na, P and Ti are in %, Hg in mg/t, remaining elements in g/t)
Tab. 1. Povprečja vsebnosti prvin v različnih vzorčnih sredstvih (povprečne vrednosti Al, Ca, Fe,
K, Mg, Na, P in Ti so v %, Hg v mg/t, preostalih prvin pa v g/t.)
Clarke   -   Clarke in soil; Svetovno poprečje vsebnosti prvin v tleh (Bowen,1979)
Slo - Slovenian average of elements in soil; Slovensko povprečje vsebnosti prvin v tleh; n
= 817 (Andjelov, 1994); Hg, n = 119 (Pire, 1993)
Jes-ZT - Average of elements in top soil in Jesenice area; Povprečje vsebnosti prvin v zgorn-
jem talnem horizontu na območju Jesenic; n = 44
Jes-ST - Average of elements in bottom soil in Jesenice area; Povprečje vsebnosti prvin v
spodnjih talnih horizontih na območju Jesenic; n = 78
Jes-SP - Average of elements in household dust in Jesenice area; Povprečje vsebnosti prvin v
stanovanjskem prahu na območju Jesenic; n = 3 (Šajn, 1998)
Jes-PP - Average of elements in attic dust in Jesenice area; Povprečje vsebnosti prvin v pod-
strešnem prahu na območju Jesenic; n = 3 (Šajn, 1998)
326_Robert Šajn, Milan Bidovec, Mateja Gosar & Simon Pire
> ! A ! . Tab. 2. Characteristic values of rotated factor loadings; n = 122
Tab. 2. Dominantne vrednosti rotiranih faktorskih obremenitev; n = 122
Fl ... F4 - Factor Loadings; Faktorske obremenitve
Kom      - Communality in %; Komunalnost v %
Var        - Variance in %; Varianca v %
Discussion
With the factor analysis the initial 22 considered variables were reduced to 4 fac-
tors, synthetic variables that represent the geochemical associations of chemical ele-
ments. The four factors explain more than 80% of variability within data (Tab. 2).
The geochemical associations suggested by results of factor analysis are confirmed
also by the outcomes of the cluster analysis (Fig. 3).
The geochemical distributions in soils of the Jesenice area are compared with the
means for Slovenian soils (Andjelov, 1994), the means for urban sediments from
three localities in the Jesenice area (Šajn, 1998) and with world averages for soils
Geochemical Soil Sui^vey at Jesenice area, Slovenia__327
Fig. 3. Dendrogram of cluster analysis; n = 122
SI. 3. Dendrogram clusterske analize; n = 122
(B o w e n , 1979) (Tab. 1). The samples of all listed studies in Slovenia were analysed
in the same laboratory by using the same procedures of digestion and analysis. The
urban sediments in Š a j n ' s (1998) study are (1) household dust which is closely
associated to rooms where inhabitants live, and (2) attic dust that keeps accumulat-
ing in attics.
Natural Distribution of Chemical Elements
The natural geochemical distributions are suggested by factors 1 and 4 by which
about 45% of total variation within data is accounted for The factor scores of these
factors are the lowest in the topsoil horizons, and they increase in horizons with
depth.
328_Robert Šajn, Milan Bidovec, Mateja Gosar & Simon Pire
Fig. 4a. Distribution of factor 1 (Al, Ва, K, La, Nb, Sc, Ti, Th, V and Zr) in top soil
SI. 4a. Porazdelitev faktorja 1 (Al, Ва, K, La, Nb, Sc, Ti, Th, V in Zr) v zgornjem
talnem horizontu
Fig. 4b. Distribution of factor 1 (Al, Ва, K, La, Nb, Sc, Ti, Th, V and Zr) in bottom soil
SI. 4b. Porazdehtev faktorja 1 (Al, Ва, K, La, Nb, Sc, Ti, Th, V in Zr) v spodnjem
talnem horizontu
Geochemical Soil Survey at Jesenice area, Slovenia_329
Fig. 5a. Distribution of factor 2 (Cd, Cu, Hg, Mn, Pb and Zn) in top soil
SI. 5a. Porazdelitev faktorja 2 (Cd, Cu, Hg, Mn, Pb in Zn) v zgornjem talnem horizontu
Fig. 5b. Distribution of factor 2 (Cd, Cu, Hg, Mn, Pb and Zn) in bottom soil
SI. 5b. Porazdelitev faktorja 2 (Cd, Cu, Hg, Mn, Pb in Zn) v spodnjem talnem horizontu
330_Robert §ajn, Milan Bidovec, Mateja Gosar & Simon Pire
Fig. 6a. Distribution of factor 3 (Cr, Fe and Ni) in top soil
SI. 6a. Porazdelitev faktorja 3 (Cr, Fe in Ni) v zgornjem talnem horizontu
Factors
I    I    I   iM—■
i.     6     6     p     p
кл 1^ f
s    s    Ö    «
Fig. 6b. Distribution of factor 3 (Cr, Fe and Ni) in bottom soil
SI. 6b. Porazdelitev faktorja 3 (Cr, Fe in Ni) v spodnjem talnem horizontu
Geochemical Soil Survey at Jesenice area, Slovenia_331
Fig. 7a. Distribution of factor 4 (Ca, Mg and pH) in top soil
SI. 7a. Porazdelitev faktorja 4 (Ca, Mg in pH) v zgornjem talnem horizontu
Fig. 7b. Distribution of factor 4 (Ca, Mg and pH) in bottom soil
SI. 7b. Porazdelitev faktorja 4 (Ca, Mg in pH) v spodnjem talnem horizontu
332_Robert Šajn, Milan Bidovec, Mateja Gosar & Simon Pire
Fig. 8. Average enrichment ratios of element group with regard sampled material
SI. 8. Povprečni obogatitveni odnosi skupin prvin glede na vzorčeno sredstvo
Geochemical Association Al-K-Ti-Ba-La-Nb-Sc-Th-V-Zr
The factor 1 (Tab. 2; Figs. 4a and 4b) is the strongest, explaining 34% of total varia-
tion. It represents the association of Al, K, Ti, Ba, La, Nb, Sc, Th, V and Zr High values
are typical for lov^er soil horizons, especially in the (Bj.^) horizon of calcareous cambisols.
Chemical comparison with means of soils in Slovenia (Tab.l; Fig. 8) shows that the
mean contents of the chemical elements associated with the first factor are in the
topsoil at Jesenice about 60% of soils in Slovenia, while their contents in the lower
soil horizons are about the same. The contents in household and attic dust in the
Jesenice area are about 40% of the estimated means for Slovenia.
The discussed group of chemical elements represents a most characteristic natural
pattern of behaviour of chemical elements in the Jesenice area. Here, their means in
soils are appreciably higher than in the urban sediments, household and attic dust.
Geochemical Association soil pH-Ca-Mg
The factor 4, loaded with pH, Ca and Mg, explains 12% of total data variation.
Also this geochemical association displays the natural geochemical association of
elements. High factor scores occur in carbonate alluvial spols on the youngest flood
plains of the river Sava. The values increase with depth (Figs. 7a and 7b).
Ca and Mg are typical elements of the carbonate rocks. In comparison with the soil
means for Slovenia (Tab. 1; Fig. 8), for Jesenice somewhat lower values were estab-
lished in topsoils, and up to 50% higher values in the lower soil horizons. The high
Geochemical Soil Survey at Jesenice area, Slovenia_333
Fig. 9a. Distribution of cadmium in top soil
SI. 9a. Porazdelitev kadmija v zgornjem talnem horizontu
Fig. 9b. Distribution of cadmium in bottom soil
SI. 9b. Porazdelitev kadmija v spodnjem talnem horizontu
334_Robert Šajn, Milan Bidovec, Mateja Gosar & Simon Pire
Fig. 10a. Distribution of lead in top soil
SI. 10a. Porazdelitev svinca v zgornjem talnem horizontu
Fig. lOb. Distribution of lead in bottom soil
SI. 10b. Porazdelitev svinca v spodnjem talnem horizontu
Geochemical Soil Survey at Jesenice area, Slovenia_335
Fig. 11a. Distribution of zinc in top soil
SI. 11a. Porazdelitev cinka v zgornjem talnem horizontu
Fig. lib. Distribution of zinc in bottom soil
SI. lib. Porazdelitev cinka v spodnjem talnem horizontu
336_Robert Šajn, Milan Bidovec, Mateja Gosar & Simon Pire
contents of Ca and Mg in household and attic dust, they may be more than 8 times
higher of the Slovenian averages, may be explained by v^eathering of construction
materials and partly by dusting of soils and roads.
Man-made Elemental Distributions *
The man produced distributions of chemical elements are represented by factors 2
and 3 by whom 36% of total variability of the considered 22 chemical elements is
explained. The scores of these factors are the highest in the topsoil horizons, and they
tend to diminish with depth.
Geochemical Association Cd-Cu-Hg-Mn-Pb-Zn
The factor 2 is the second strongest, explaining about 23% of total variability. It is
loaded with Cd, Cu, Hg, Mn, Pb and Zn, with elements, that were introduced to soil
as a result of anthropogenic activities. The factor scores drop with soil depth: they
are several times higher in the topsoil horizons than in the lower soil horizons (Figs.
5a and 5b). These differences are more contrasting on highly polluted localities with
lower soil horizons of brown soils. The differences are less expressed in rendzinas in
which most often only the samples of two horizons (О^А^, AC), were collected.
The impact of the 2 factor elements in the upper soil horizon extends in a 2 to 4 km
wide belt along the entire length of the Sava valley. At Mojstrana, where the valley
widens, the influence is somewhat lower, and it increases again when it narrows
westwards. The shape of the contamination halo is controlled much by the mentioned
two local winds.
Comparisons with world and Slovenian averages suggests strongly increased con-
tents of Pb, Hg, Cd and Zn. The most striking case of man produced impact are dis-
tributions of Cd, Pb and Zn (Figs. 9a to lib). In the upper soil horizons, zinc contents
are on the average 3 times higher than the average of Slovenia, cadmium more than 4
times, and lead 8 to 9 times higher than the Slovenian average. In the lower soil hori-
zons, the increase is appreciable smaller, Cd is on the average 60 percent higher, Pb
30 percent higher, and Zn is about the same as the Slovenian average. The anthro-
pogenic origin of most of Cd, Pb and Zn is especially drastic in the urban sampled
materials. The average contents of Cd in attic dust in the houses at Jesenice is more
than 12 times higher than the average of soils in Slovenia, of Zn 25 times and of Pb
for more than 42 times higher (Tab. 1; Fig. 8).
Geochemical Association Cr-Fe-Ni
The geochemical association Cr, Fe and Ni in the Jesenice area is represented by
factor 3 by which 13% of total variability within the data are explained. These ele-
ments were introduced to the topsoil horizons especially through iron melting activ-
ities, especially in the narrow area of Jesenice (Fig. 6a). In the rest of the investigat-
ed territory, the major part of contents of these metals is of geogenie origin; they
tend to accumulate especially in the (B^.^) horizon of the calcareous cambisols (Figs.
6a and 6b).
Geochemical Soil Survey at Jesenice area, Slovenia__337
In comparison to the average contents in the soils of Slovenia area, the average
contents in topsoil and in lov^er soil horizons of the entire Jesenice area are louder
However, in the halo of about 10 km- surrounding the ironworks the averages are
about 40 % higher High contents that surpass the averages of Slovenian for 2 to over
3 times are found in household and even more in the attic dust of the Jesenice town.
Anomalous Cr, Fe and Ni in urban materials are another proof that most of their con-
tents was dispersed into the environment by the metallurgie industry at Jesenice.
Conclusions
Geochemical investigation in the Jesenice area permitted to establish the estimates
of contents and spatial distributions of chemical elements in soils, and to separate
the anthropogenic from the naturally produced geochemical patterns. Distributions
of 21 chemical elements were considered: Al, Ca, Fe, K, Mg, Ti, Ba, Cd, Cr, Cu, Hg,
La, Mn, Nb, Ni, Pb, Se, Th, V, Zn and Zr Two elemental associations, the first Al-Fe-
K-Ti-Ba-La-Nb-Sc-Th-V-Zr, and the second, soil pH-Ca-Mg, are considered of nat-
ural origin, and the associations Cd-Cu-Hg-Mn-Pb-Zn and Cr-Fe-Ni man made,
influenced strongly by the iron metallurgy.
The established estimates of chemical elements and of geochemical trends of single
elements and of their associations in the soils of Jesenice are a good basis for further
research of geochemical distributions in other media, as air, air deposit, stream sedi-
ment and plants. These additional studies should permit to establish the natural and
anthropogenic cycles of chemical elements in the urban environment, and permit to
estimate the hazards for the population.
Alarming is the recognition in the household dust of the Jesenice area of very high
values of Cd, Pb and Zn that are more than 20 times higher than in natural loose
materials. The urban sediments, and especially the household dust, are the sub-
stances to which the people are intensely exposed. These high concentrations are a
potential danger especially to small children who absorb much more dust than
grownups, and are at the same time also more susceptible to the toxicity of the heavy
metals.
Acknowledgements
The study was performed in the frame of the Alps-Adria common research project
with colleagues of the Voest-Alpine, Linz, Austria, Geooeko Vienna, Austria and the
Geological Survey of Croatia, Zagreb. Thanks to the Geological Survey of Slovenia
for enabling the investigation, and to the Ministry for Science and Technology , R.
Slovenia for funding.
References
A b b e y, S. 1983: Studies in „standard samples" of silicate rocks and minerals 1969 - 1982. -
Geological survey of Canada, 109 pp., Ottawa.
Acme Analytical Laboratories Ltd. 1994: Assaying and geochemical analyses. -
Acme analytical laboratories ltd., 10 pp., Vancouver B. C.
338_Robert Šajn, Milan Bidovec, Mateja Gosar & Simon Pire
A n d j e 1 o V, M. 1994: Rezultati radiometričnih in geokemičnih meritev za karto naravne
radioaktivnosti Slovenije. - Geologija 36, 223 - 248, Ljubljana.
B 1 e j e C, M. 1976: Statistične metode za ekonomiste. - Ekonomska fakulteta. Univerza v
Ljubljani, 687 str., Ljubljana
B o w e n, H. J. 1979: Environmental chemistry of the elements. - Academic Press, 318 pp.,
London.
B u s e r, S. & C a j h e n, J. 1980: Osnovna geološka karta SFRJ, list Celovec 1:100.000. -
Zvezni geološki zavod Beograd, Beograd.
B u s e r, B. 1980: Tolmač lista Celovec. Osnovna geološka karta SFRJ 1:100.000. -Zvezni
geološki zavod Beograd, 62 str, Beograd.
D a r n 1 e y, A.G., B j ö r k 1 u n d. A., B o 1 v i k a n, B., G u s t a v s s o n, N., K o v a 1, P.V.,
Plant, J.A., S t e e n f e 11, A., T a u c h i d, M. & X u e j i n g, X. 1994: IGCP Project 259 &
360. -Newsletter 6, JUGS UNESCO, Geological Survey of Canada, 15 pp., Ottawa.
Davis, J.C. 1986: Statistic and data analysis in geology. - Willey & Sons, 651 pp.. New
York.
E p s t e i n, M. S. 1990: Report of analysis. - U.S. Department of commerce. National insti-
tute of standards and technology, 16 pp., Gaithesburg, Maryland.
H 0 d n i k. A: 1988, Kemične analize talnih vzorcev, rastlinskih vzorcev in odcednih vod. -
Katedra za pedologijo, prehrano rastlin in ekologijo, BTF, Univerza v Ljubljani, 57-58 str.,
Ljubljana.
Jurkovšek, B.1986a: Osnovna geološka karta SFRJ, Beljak in Ponteba 1:100.000. -
Zvezni geološki zavod Beograd, Beograd.
Jurkovšek, B. 1986b: Tolmač lista Beljak in Ponteba. Osnovna geološka karta SFRJ
1:100.000. - Zvezni geološki zavod Beograd, 58 str., Beograd.
K o š m e 1 j, B. 1983: Uvod v multivariatno analizo. - Ekonomska fakulteta. Univerza v
Ljubljani, 272 str, Ljubljana
M i e s C h, A.T. 1976: Geochemical survey of Missouri; methods of sampling, laboratory
analysing, and statistical reduction of data. - Geological survey professional paper, USGS,
9954-a, 39 pp., Washington.
Le Maitre,R. W. 1982: Numerical Petrology; Statistical interpretation of geochemical
data. - Elsevier Scientific Publishing Company, 281 pp., Amsterdam.
ObčinaJesenice 1998: spletna stran (http://wwwjesenice.si/jeobc.html)
O s o j n i k. A., P a v 1 i n. F., B e z 1 a j. D., K r a j n C, I & R a v n i k, A. 1988: Vpliv modern-
izacije jeklarne na ekološke razmere v jeseniški dolini. - Metalurški zavod Ljubljana, 48 str,
Ljubljana.
O s o j n i k. A., P a v 1 i n, F, K r a j n C, L, K u n s t e 1 j, J. & Z a 1 o k a r, M. 1990: Vpliv mod-
ernizacije jeklarne na ekološke razmere v jeseniški dolini, III del. - Metalurški zavod Ljubljana,
14 str, priloge, Ljubljana.
P e r i š i č , M. 1983: Primenjena geostatistika (knjigi 1 in 2). - Rudarski institut Beograd,
534 str, Beograd.
P i r C, S., L e n a r č i č. T., P e h, Z. & S v r k o t a, R. 1987: Geochemical surveys on carbon-
ate terrains in Yugoslavia 1985 - 1987. - Oddelek za geologijo, NTF, Univerza v Ljubljani, 121
pp., Ljubljana.
P i r C, S. 1993: Regional geochemical surveys of carbonate rocks; final report. - Oddelek za
geologijo, NTF, Univerza v Ljubljani, 30 pp., Ljubljana.
R e s m a n, B. 1990: Jesenice. - V: Enciklopedija Slovenije, 4. zvezek. Mladinska knjiga, 294-
296, Ljubljana.
R h o a d e s, J. D. 1982: Soluble salts. -In: P a g e, A. L., ed.. Methods of soil analysis. Part II.
- Soil science society of America, 167 - 208, Madison, Wisconsin.
R o d i o n o V, D. A., K 0 g a n, R. I., G o 1 u b o V a, V. A., S m i r n o v, B. I. &
Sirotinskaja, S. V. 1987: Spravočnik po matematičeskim metodam v geologiji. - Nedra,
332^str, Moskva.
Š a j n, R. 1995: Geokemične lastnosti tal na območju mesta Ljubljane. - Magistrsko delo.
Oddelek za geologijo, NTF, Univerza v Ljubljani, 94 str., Ljubljana
Š a j n, R. 1998: Geokemične lastnosti urbanih sedimentov na ozemlju Slovenije. - Doktorsko
delo. Oddelek za geologijo, NTF, Univerza v Ljubljani, 251 str, Ljubljana.
Š i p e C, S. 1990: Jesenice in njihova ekološko- geografska problematika. - Diplomsko delo.
Oddelek za geografijo. Filozofska fakulteta. Univerza v Ljubljani, 232 str., Ljubljana.
Š k o r i č, A. 1977: Tipovi naših tala. - Sveučilišna naklada Liber, 134 str, Zagreb.