GeolCarp_Vol50_No5_409

GEOLOGICA CARPATHICA, 50, 5, BRATISLAVA, OCTOBER 1999

409–412

MINERALOGICAL AND CHEMICAL IMPACT

OF ANTHROPOGENIC EMISSIONS ON SOILS AND ROCKS

OF THE OJCÓW NATIONAL PARK (POLAND)

MARZENA SCHEJBAL-CHWASTEK and MARIOLA MARSZAŁEK

Department of Mineralogy, Petrography and Geochemistry, University of Mining and Metallurgy, al. Mickiewicza 30,

30-059 Kraków, Poland

(Manuscript received February 12, 1998; accepted in revised form December 9, 1998)

Abstract:

Air pollution and its influence on soil contamination and the rate of weathering of Jurassic limestone in the

Ojców National Park (ONP) in Poland were studied. Phase and chemical analyses were carried out for the soils and
rocks. It has been found that the components of anthropogenic origin make up over 90 vol. % of dust particles. The
major phases include sulphates, spherical glass particles, unburned coal fragments and grains of metal oxides. The
analyses of soils have shown elevated amounts of Cd, Pb and Zn, while the total level of hydrocarbons exceeded the
permitted content in soil (samples collected along the road). The limestones are covered with black or white crusts
depending on their degree of shelter from rain water. The components of crusts include aluminosilicate glass spherules,
iron oxides, unburned coal particles and gypsum crystals. The outer layers of limestone are also enriched with heavy
metals. The heavy metals and glass spherules found in the dust fall and in the external parts of Jurassic limestones and
soil, and also the higher level of hydrocarbons in soil samples lead to the conclusion that the anthropogenic pollutants
generated within and outside the ONP play a significant role in contamination of the analysed components of the
environment.

Key words:

Poland, Ojców National Park, air pollution, soil contamination, limestone deterioration.

Introduction

The Ojców National Park (ONP) is situated in the southern
part of the Cracow-Częstochowa Upland, some 30 km north
of Cracow. Its landscape, composed of naturally exposed ele-
ments of the geological structure, mainly Jurassic lime-
stones, is rich in rivers and picturesque monadnocks with
caves, rock-needles and rock-gates. The climate of the park
displays the mountainous features. Soils are developed on
Jurassic and Quaternary rocks. The ruins of Ojców and
Pieskowa Skała castles stand on preserved flat hill-tops.

The ONP is affected by over 200 industrial, air-polluting

emitters (ca. 30 of them situated within the Cracow adminis-
trative province — steel mills, heat-power stations, cement
plants), and their above-norm emissions are degrading the
valuable natural environment of the ONP area. Besides mas-
sive industrial emissions, a significant source of air pollution
is represented by emissions from local boiler-houses as well
as from motor vehicles, the latter associated with dense traf-
fic, mainly of seasonal character (Raport 1996).

Methods

Research on air pollution and its influence on selected

components of the environment within the ONP area was
conducted in 1996/97. Samples of atmospheric precipitation
along with a dust fall were collected by sedimentation at one-
month intervals. Dusts collected together with precipitation
represent a multiphase system, therefore their preparation for
phase and chemical analyses included separation of samples

into fractions easily and hardly soluble in water. The hardly
soluble fraction is composed of dust particles, while the easi-
ly soluble fraction represents a residue after evaporation of
rain water, which also contains very fine (< 1

m) suspended

dust particles. The pH of precipitation was measured, total
dust fall calculated, and phase and chemical compositions
analysed. Soil samples were collected from the immediate
vicinity of sites where dust fall was measured, and also in the
proximity of the major road clossing the ONP area. In addi-
tion to phase and chemical analyses of the soil samples mea-
surements of hydrocarbons were carried out. Samples of Ju-
rassic limestones were also taken, from both natural
exposures and historic buildings situated within the ONP
area (the Ojców and Pieskowa Skała castles). These samples
underwent chemical and phase analyses.

The analyses were carried out by means of a Jenapol (Carl-

Zeiss, Jena) optical microscope in transmitting light, a TUR
M-61 X-ray diffractometer, and a JEOL JMS 5200 scanning
microscope with an EDS EXL attachment for chemical anal-
yses in microareas. Hydrocarbon contents were measured by
the infrared method using a UR-10 spectrometer. Chemical
components, mainly heavy metals, were analysed by the
AAS (Philips PU 9100X) method.

Results and discussion

The average annual dust fall within the ONP area is 50

t/km

(1996/97), exceeds the total suspended particulate stan-

dard for protected areas (Table 1, Fig. 1). Precipitation is acid
and weakly acid (pH values are 3–4.5). Acidification is caused

410 SCHEJBAL-CHWASTEK and MARSZAłEK

Fig. 1.

The annual dust fall in the ONP (t/km

/year).

Table 1:

Mean annual dust fall in the years 1985-93 (Raport

1996) and in 1996/97 (own measurements) in ONP (t/km

/year).

Year 1985 1986

1987

1988

1989

1990

1991

1992

1993 1996/97

Dust

fall

Table 2:

Phase composition (XRD, optical microscopy) of rainwater

evaporate from the ONP area (salts and anthropogenic particles).

Fraction

easily soluble in water

Fraction

hardly soluble in water

Gypsum CaSO

2 H

Hematite Fe

Kainite

KM g [Cl/SO

]

3 H

M agnetite

Hexahydrite M gSO

7 H

Anhydrite CaSO

Syngenite K

Ca[SO

]

M ullite aluminosilicate

Langbeinite K

M g

[SO

]

Unburned coal

fragments

Halite NaCl

Silicate glass

M ascagnite (NH

)

Salmiac NH

Sylvite KCl
Burkeite

[CO

(SO

)

]

mainly by anthropogenic emissions of gases with prevailing
SO

. Sulphur dioxide is one of the most hazardous gases,

transported into the area of the ONP (Monitoring 1996).
Amounts reaching up to 2,000

g/m

have been recorded,

while the Polish norm for the areas under protection limits a
temporary concentration to 250

g/m

. In 1985, ten field sta-

tions were established to monitor concentrations of SO

and

particulate matter (Łęcki 1995).

Natural and anthropogenic components (Table 2) have been

distinguished among the polluting compounds. The natural
ones, associated with the secondary deflation of the surface,
include quartz, clay and carbonate minerals, feldspars. The
major anthropogenic components are sulphates with various
degrees of hydration (results of SO

emissions), silicate glass

and unburned coal fragments (high-temperature combustion),
grains of metal oxides (emissions from metallurgical plants —
Fig. 2).

By means of an optical microscope (Table 3) anthropo-

genic particles in dust deposited with rain water have been
quantified conducted. The anthropogenic particles are the
most frequent essential in dust fall. In the case of the ONP
area they form over 90 vol. % of the total dust of particles.
Aggregates with particles of natural origin occur in subordi-
nate quantities.

The granulometric analysis of the dust particles has re-

vealed that 80–90 vol. % of them are contained in the partic-
ularly harmful fraction < 3

m. Such a high amount of this

fraction indicates a significant contribution of grains deposit-
ed from a long transport.

The content of heavy metals (Pb, Zn, Cd, Cr, Ti) is particu-

larly high in rain water (Table 4). These elements enter direct-
ly the biogeochemical cycle of the ONP environment (Fig. 3).

Fig. 2.

Iron oxides particles (mostly spherical) (SEM).

Grain

fraction

0 – 3

3 – 10

> 10

Anthropogenic

particles

Summer period

(no heating)

Winter period

(with heating)

Table 3:

Contents of grain fractions and of anthropogenic parti-

cles in dust fall (wt. % ).

MINERALOGICAL AND CHEMICAL IMPACT OF ANTHROPOGENIC EMISSIONS 411

The soil samples collected include brown and calcareous

(rendzina) soils, and as such should represent rather a good
protection against pollutants (Kabata-Pendias et al. 1993).
Those developed on limestones are composed mainly of
quartz and carbonates: the latter minerals, if they occur in
higher amounts, control the buffer properties of soils. Goethite
and clay minerals are present in minor quantities (< 5 wt. %),
but they are important elements stabilizing heavy metals in
soils. Considering low contents of organic matter (6 wt. % on
average) and a small amount of clay fraction (7 wt. % on the
average), the soils studied reveal a small capacity of their
sorptive complex. An average soil reaction oscillates around
pH = 7, being typical of neutral and alkaline soils. This pH sta-
bilizes heavy metals in soils and thus hinders their migration,
as the metals are bound to inert compounds.

Contamination of soils with petroleum-derived substances

is particularly distinct in the samples collected along the ma-
jor road intersecting the ONP. The total of aliphatic and aro-
matic hydrocarbons is above 300 ppm (the permitted content
in soil is 100 ppm — Fig. 4). Such a high contamination is
caused by very intense traffic of motor vehicles. For compar-
ison purposes, the authors have analysed the amount of hy-
drocarbons in soil samples collected farther (ca. 300 m)
from the main road (Table 5).

Chemical analyses of soil (Table 6) have indicated higher

amounts of Zn, Pb and Cd (the geochemical backgrounds
have been exceeded 5 times for Zn, and 3 times for Pb and
Cd — Fig. 5). High amounts of these elements, particularly
of Pb and Cd, result not only from dust and gas emissions,
but also from motor vehicles, passing a relatively small area
of the ONP. The remaining elements: Cu, Ni, Cr and Mn, oc-
cur in amounts close to their global geochemical back-
grounds, that is their natural content in soils. Mineralogical

F e

T i

M n

Z n

P b

C u

C r

N i

C d

4 6 4 7 7

3 5 3 3

5 5 7

1 8 1 2

5 2 0

2 1 3

1 2 0

1 6 1

3 1

Table 4:

Concentration of trace elements (ppm) in dust fall in the

area of ONP.

Fig. 3.

Concentration of trace elements in dust fall (ppm).

Fig. 4.

Contamination of soil with hydrocarbons (ppm). A — soil

samples distant from the main road, B — soil samples close to the
major trunk road.

Hydrocarbons

Aliphatic

2.63

263.75

Aromatic

5.56

45.68

Total

8.19

309.43

1 — soil samples distant from the main road,
2 — soil samples along the major road.

Table 5:

Contamination of soils with hydrocarbons (ppm).

E lem ent

M n

Z n

P b

C u

C r

N i

C d

Fractio n > 10

5 7 4

5 0 0

1 3 2

3 6

3 5

2 4

Fractio n < 10

6 0 1

9 5 0

2 0 8

4 8

3 4

3 7

T o tal

1 1 7 5

1 4 5 0

3 4 0

8 4

6 9

6 1

1 5

Table 6:

Concentration of trace elements (ppm) in soil in ONP.

Fig. 5.

Concentration of trace elements in soil (ppm).

and chemical investigations have shown that the soils of the
ONP actually possess rather weak protective properties and
not too high resistance to contaminations.

This resistance is, however, partly enhanced by acid-basic

equilibrium of the soils in question (due to the presence of
carbonate minerals), and this slightly lowers the mobility and
harmful effects of toxic forms of heavy metals.

The outer surfaces of Jurassic limestones are covered most

often by strongly coherent, black crusts 0.3 mm thick. Some-
times, mainly where there is shelter from rain water, it is pos-
sible to find white crusts (on stone elements exposed to rain-
falls) and black dendritic ones (along the borders between
the stone areas exposed to and sheltered from running rain
water). The components of crusts include aluminosilicate
glass spherules, iron oxides (hematite, magnetite), unburned
or coked coal particles, and gypsum crystals (Figs. 6, 7). The
outer layers are enriched in heavy metals (Table 7), and
among others Pb, Cd, Fe, Zn contents exceed the clark val-
ues for calcareous rocks (Fig. 8).

412 SCHEJBAL-CHWASTEK and MARSZAłEK

Sample

O-2

8.03

14. 60

6.50

3.80

O-4

3.05

1.53

6.25

0.27

O-5

8.38

8.47

10.25

3.91

O-6

3.03

0.90

9.50

0.35

Z-1

4.95

2.69

7.75

0.47

Z-2

5.88

3.42

3.00

0.66

Z-3

6.93

2.99

6.25

–

Z-4

3.78

1.57

7.75

0.61

Z-5

4.33

7.12

6.75

0.45

Z-7

7.38

5.46

9.50

1.14

O — Ojców; Z — Pieskowa Skala

Table 7:

Coefficients of enrichment of trace elements in the Juras-

sic limestones studied (calculated against a „clean Jurassic lime-
stone”, i.e. the limestone unexposed to dust fall).

Fig. 7.

SEM-EDS analysis of Jurassic limestone — the image

shows concentration of S at the rock surface.

Fig. 8.

Concentration of trace elements in Jurassic limestones from

ONP (calculated against a „clean Jurassic limestone” unexposed to
dust fall).

Conclusions

High contents of heavy metals have been found in the dust

fall, in soils and in coating crusts on Jurassic limestones
(Manecki et al. 1996). Higher levels of hydrocarbons have
also been observed in soil samples collected along the major
road. These facts point to the significant adverse effects of
the urban and industrial agglomerations, bordering the ONP.
The biggest emitters in southern Poland are the power and
metallurgical industries (iron, steel and of base metals). An-
other source of pollution is road traffic, which is too inten-
sive for the small area of the ONP.

Acknowledgements:

The study was supported by the Uni-

versity of Mining and Metallurgy, Grant No. 10.140.562.

References

Kabata-Pendias A. & Pendias H., 1993: Biogeochemia pierwiast-

ków śladowych, PWN Warszawa.

Łęcki E., 1995: Monitoring SO

w powietrzu atmosferycznym na

terenie Ojcowskiego Parku Narodowego, Ojców.

Manecki A., Marszałek M., Schejbal-Chwastek M. & Skowroński

A., 1997: Stone decay in some historic buildings of Cracow
(Poland) and its reasons. Folia Fac. Sci. Nat. Univ. Masaryki-
anae

Brunesis, Geologia, 39, 149–156.

Monitoring ekologiczny w woj. krakowskim w latach 1986–92,

WIOŚ - Kraków, 1993.

Monitoring ekologiczny w woj. krakowskim w latach 1993–95,

WIOŚ - Kraków, 1996.

Raport o stanie środowiska w woj. krakowskim, WIOŚ - Kraków,

1996.

Note:

This paper was presented at the Conference of the IGCP Project #405 — “ENVIVEATH”, held in Bratislava from 24th to 26th November, 1997

Fig. 6.

The surface layer of Jurassic limestone with gypsum crys-

tals (SEM).