Applied Geochemistry, Vol. 11, pp.

121-127, 1996
Pergamon Copyright Q 1996 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0883-2927/96 $15.00+0.00

0883-2927(95)000763

Polycyclic aromatic hydrocarbons in agricultural soils in Poland:

preliminary proposals for criteria to evaluate the level of soil
contamination

Barbara Maliszewska-Kordybach
Institute of Soil Sciences and Plant Cultivation, 24-100 Puawy, Poland

Abstract-The contamination of agricultural soils in the Upper Silesia region of Poland with polycyclic
aromatic hydrocarbons (PAH) was evaluated on the basis of three criteria: the sum of PAH content; the
number of exceeded reference values for individual PAH (according Dutch regulations); the authors
preliminary proposals for agricultural lands in Poland (the sum of PAH content normalized to average
soil characteristics in the area under investigation). Organic matter content and the < 0.02 mm size fraction
were chosen as the soil properties most adequate for this purpose. The presented results revealed that an
assessment of the level of contamination of agricultural lands with PAH depends on the criteria being
applied. This indicates a need to establish guidelines to allow the proper classification of soils in terms of
their agricultural use and the protection of the environment. Copyright 0 1996 Elsevier Science Ltd

INTRODUCTION was to compare 3 methods of evaluation of the level of

F!olycyclic aromatic hydrocarbons (PAH) represent a
group of highly carcinogenic and mutagenic organic
contaminants included in the priority pollutants
listings produced by the United States Environmental
Agency (US EPA) and by the European Commission.
Soil is the part of the environment which accumulates
most of the hydrophobic organic contaminants such
as PAH. Agricultural soils receive inputs of these
contaminants from atmospheric deposition, sewage
sludges and other organic amendments applied as
fertilizers or accidently, e.g. as a result of spillage
(Jones et al., 1989; Maliszewska-Kordybach, 1993).
Knowledge of soil contamination with PAH is needed
to avoid any food production risk and to restrict the
deleterious effect of these contaminants on the soil
ecosystem. Although food intake is the main route by
which these pollutants enter human organisms (Vaes-
sen et al., 1984; Paterson and McKay, 1989), informa-
tion on the contemporary content of PAH in soils
from agricultural regions is limited (Jones et al., 1989;
Maliszewska-Kordybach, 1993; Tebaay ef al., 1993).
Despite the significance of the problem there is still a
lack of soil quality criteria in many countries,
including Poland. Definitions regarding non-con-
taminated or contaminated soil are open to
various interpretations, especially in the case of
agricultural land. Reference values (A values) from
Dutch regulations (VROM, 1988), sometimes used as
the threshold values for uncontaminated soils, do
not correspond to normal levels of PAH in soils
from unpolluted areas in other countries of Europe
(Maliszewska-Kordybach, 1993; Nemecek et al.,
1994; Tebaay et al., 1993). Intervation values
(C values) from these regulations (VROM, 1988)
refer to very seriously contaminated soils for which
the clean-up action is required. The aim of this work
contamination of soils from agricultural lands with
PAH; one of these methods is the authors preliminary
proposal for agricultural land in Poland. The methods
were based on the following criteria:
(a) sum of the content of 16 PAH (US EPA, 1984);
(b) sum of the content of 16 PAH normalized to
average soil characteristics (authors proposal);
(c) the Dutch List (VROM, 1988) reference
values (A values).
An area in the Upper Silesia region of Poland was
used to compare the 3 methods.
MATERIALS AND METHODS
Soil samples (n = 39) were taken from the &I 5 cm soil
layer of the 4020 ha study area (I sample per 100 ha) in the
southern part of the highly industrialized Upper Silesia
region of Poland (Fig. 1). 60% of the samples were collected
from arable land and 40% from pasture land. The soils were
mainly light textured and acidic with low to medium organic
matter content (Table 1).
PAH content (16 comnounds based on the US EPA list) in
soils was determined (Mgliszewska-Kordybach and Oleszek,
1994). The soil samples (20 g), after drying at room
temperature and sieving through a 2 mm screen, were Soxhlet
extracted with cyclohexane. The extracts were concentrated
to 1 ml at 30C on a rotary evaporator, cleaned-up by the
SPE (Solid Phase Extraction) method on Florisil micro-
columns and analysed for PAH content by HPLC (High
Pressure Liquid Chromatography) using UV detection.
RESULTS AND DISCUSSION
The PAH content (expressed as the geometric
mean) of the soils under investigation is shown in
Table 2. The geometric mean value of 264 pg kg- for
121
122 B. Maliszewska-Kordybach

KRAKdW
0a

Fig. 1. The study area.

Table 1. Statistical evaluation of soil characteristics

Geometric Lower Upper

Soil property mean Minimum Maximum quartile quartile

Organic matter (wt%) 2.50 1.45 17.20 2.10 4.08

PH 4.8 3.8 6.3 4.6 5.7
Fraction i 0.02 mm size (%) 15.0 2.0 30.0 10.0 16.0

Table 2. Statistical evaluation of the PAH content of the the sum of PAH is not very high, given the indus-
soils trialization of the region, and is comparable with
typical values for PAH in Welsh surface soils (Jones et
PAH Geometric mean 95% ranp
al., 1989) or with concentration of thesecompounds in
(pg kg-) (pgkg- )
soils from the Czech Republic (NemeEek et al., 1994).
1. Fluorene 7 2-3 I The average contents of individual hydrocarbons were
2. Phenanthrene 16 l-287 all below 30 pg kg-. The highest concentrations for
3. Anthracene 8 242 sums of PAHs did not exceeded 3000 pg kg- and in
4. Fluoranthene 20 l-483
the case of individual compounds were below 500 pg
5. Pyrene 20 l-429
6. Chrysene 19 2-229 kg-.
7. Benzo(a)anthracene 19 l-220 Four classes of soil contamination with PAH were
8. Benzo(b)fluoranthene 28 3-319 proposed (Table 3) for each of the applied methods.
9. Benzo(k)fluoranthene 8 1-59 In the first method the proposed threshold values
10. Benzo(a)pyrene 22 2-248
11. Dibenzo(a,h)anthracene 9 l-90
which were expressed as the absolute sum of the
12. Benzo(ghi)perylene 13 l-167 content of 16 PAH compounds in the soil samples
13. Indeno( 1,2,3-cd)pyrene 29 3-278 (SUM PAH), disregarded PAH composition and soil
Sum of PAH 264 28-2447
characteristics. These values (200, 600 and 1000 pg
kg- ) were derived from the results of determinations
 Polycyclic aromatic hydrocarbons in agricultural soils in Poland 123

Table 3. Proposed classes of soil contamination with PAH

Criterion

Class of soil SUM PAH REL SUM PAH Dutch List

contamination (pg kg-) (pg kg-) (A values exceeded)

Non-contaminated < 200 < 200 0

Weakly contaminated 200-600 200-600 l-3
Contaminated 600-1000 60&1000 4
Heavily contaminated > 1000 > 1000 5%

Table 4. Soil contamination levels as defined by the 3 alternative methods (percent of

soil samples in each soil contamination class)

Dutch List
SUM PAH REL SUM PAH (A values exceeded)
Class of soil
contamination % of soil samples

Non-contaminated 46 48 39
Weakly contaminated 31 26 28
Contaminated 8 13 15
Heavily contaminated 15 13 18

71

65

6C 1000 ppb

55 200 ppb

5u

Fig. 2. Soils contamination with PAH using the SUM PAH method.
124 B. Maliszewska-Kordybach
70
60
50
Fig. 3. Soils contamination with PAH using the REL SUM PAH method.
of PAH content of soils in Europe (Jones et al., 1989;
Maliszewska-Kordybach, 1993; Maliszewska-Kordy-
bath et al., 1995; Maliszewska-Kordybach and
Smreczak, 1995; Nemecek et al., 1994; Tebaay et al.,
1993), as well as from an estimation of the risk of
human exposure (the possibility of PAH transfer into
the food chain) (Paterson and McKay, 1989) and the
average intake rates (Dennis et al., 1983; Vaessen et
al., 1984). As can be seen from Table 4, in 46% of soil
samples the content of the sum of PAH was below 200
pg kg - i; i.e. corresponding to natural concentrations
of these compounds in most Polish soils from
agricultural regions (Maliszewska-Kordybach and
Smreczak, 1995). These soils were considered to be
non-contaminated. In 15% of soils the content of
PAH was over 1000 pg kg- (heavy contamination).
The spatial distribution (Fig. 2) of the 4 defined (Table
3) classes of soils corresponded roughly to local
sources of pollution (urban agglomerations, roads,
etc.). It should be emphasised that this method does
not take into account soil properties which may
1000 ppb
600 ppb
200 ppb
significantly affect PAH sorption and degradation
(Maliszewska-Kordybach, 1993; Park et al., 1990;
Scott-Fordsman and Pedersen, 1994; Wild and
Jones, 1992).
In the second method (authors preliminary propo-
sals for agricultural lands) the same threshold values
were applied (Table 3), but there they referred to the
sum of 16 PAH contents normalized to 2 average
soil properties; organic matter content and the
content of the fraction co.02 mm size. Organic
matter content of the soil is the most important
factor influencing sorption of non-polar, hydrophobic
organic pollutants (Chiou, 1989; Dzombak and
Luthy, 1984; Harmsen, 1993). However, under certain
conditions PAH may be sorbed on the inorganic
compounds of the soil (Chiou, 1989). Soil texture
and structure is crucial to many processes in agricul-
tural systems and disregarding this characteristic may
result in misleading soil quality assessments. In the
proposed criterion the co.02 mm soil-size fraction
was used because it is correlated with the content oft
 Polycyclic aromatic hydrocarbons in agricultural soils in Poland
soil colloids (Pondel et al., 1985) exhibiting strongest
sorption tendencies towards organic pollutants
(Dzombak and Luthy, 1984; Chiou, 1989) and it is
one of the most important properties used to classify
agricultural soils in Poland. The related sum of PAH
content (REL SUM PAH) in soil samples was
calculated as follows:
REL SUM PAH (gg kg-i)
= SUMPAH(pgkg-) x 2.5(%) x 15(%)
OM (%) x fr. < 0.02 mm (%)
where OM = the soil organic matter content,
fr. x0.02 mm - the co.02 mm soil-size fraction
content. The value 2.5 corresponded to mean soil OM
content in the area under investigation and the value
15 to mean content of the soil fraction < 0.02 mm size
(Table 1). For wails with organic matter content
~2.0% the OM value was taken as 2.0 since other
work (Maliszewska-Kordybach, 1993; VROM, 1988)
has not indicated a correlation between OM and PAH
concentrations in these soils. Although the percentage
of soil samples in each of the 4 pollution classes (Table
4) was similar to those in the first method, their spatial
distribution (Fig. 3) was different. According to
method 2 (Fig. 3) the southern part of the area,
where low-organic matter light soils predominate, was
most contaminated. The proposed method is rather
simple but important in that it takes into considera-
tion soil characteristics. Further development of this
method is envisaged in the future.
In method 3 the threshold values did not refer
directly to concentrations of PAH in the soil but to the
Fen
Ant
Flllt
Plr
Chr
Fig. 4. Percent of soil samples with exceeded PAH reference values (A values -
regulations).
125
number of exceeded Dutch A values for individual
hydrocarbons. This method takes into consideration
soil properties (organic matter content), as well as the
composition of PAH. Reference values (A values)
for each PAH from the Dutch List (given the soil
with 10% OM) (VROM, 1988) were recalculated for
the content of OM in each soil sample and compared
with the determined PAH concentrations. The results
of these evaluations depended strongly on the PAH
compound being taken into consideration (Fig. 4). If
the assessment was based on the sum of PAH, 85% of
soil samples could be considered as unpolluted. If
fluoranthene or pyrene were taken into account, A
values were not exceeded in 59% of soils. However, if
the estimation was based on the content of chrysene,
only 37% of all soil samples could be described as
uncontaminated. This method of evaluation of soil
contamination is unclear and very difficult to apply.
The division of soils into 4 classes (Table 3) simplified
the problem; the threshold values for these classes
were chosen in such a way that the classes of soil
contamination would correspond most closely to the 2
previous methods. According to these criteria the first
group (non-contaminated soils) comprised 39% of
soil samples, whereas the last group (A values
exceeded for at least 5 hydrocarbons; heavily con-
taminated soils) comprised 18% of the samples (Table
4). The spatial distribution of soils is presented in Fig.
5. For practical purposes, however, this way of
calculation seems unnecessarily complicated.
The results presented show that an assessment of
the level of pollution of agricultural lands with PAH
depends on the criteria being applied. There is a need
50 60 70
according to Dutch
126 B. Maliszewska-Kordybach

70

60

50

45 sb 55

Fig. 5. Soils contamination with PAH based on values exceeding the Dutch List A values,

to establish guidelines to enable the proper classifica-
tion of the soils in terms of their agricultural use and
for the protection of the terrestrial ecosystems.
Acknowledgements-The work was partly sponsored by
Polish State Committee for Scientific Research (Project No.
5 S302 05.505).
Editorial board: Mike Billett.
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