Beruflich Dokumente
Kultur Dokumente
POLLUTION
Abstract
The distribution and accumulation of polycyclic aromatic hydrocarbons (PAH) in soil as well as PAH pro®les have been inves-
tigated in areas with dierent anthropogenic pollution such as the city of Tallinn, the towns of PaÈrnu and Kohtla-JaÈrve and some
rural areas. PAH were identi®ed in 147 soil samples (0±10 cm upper layer) collected in September 1996. The typical PAH level in
Estonian rural soil is about 100 mg/kg dry weight. PAH concentrations in Tallinn, PaÈrnu and Kohtla-JaÈrve soil were quite high (the
mean PAH concentrations were 2240, 7665 and 12 390 mg/kg dry weight, respectively). The dominant PAH in soil samples were
pyrene, triphenylene and ¯uoranthene. 3±4 ring PAH and 5±6 ring PAH ratio altered from 5:1 to 1.7:1. # 1999 Elsevier Science
Ltd. All rights reserved.
Keywords: Polycyclic aromatic hydrocarbons (PAH); Contamination; Pro®les; Soil; Estonia
0269-7491/99/$Ðsee front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S0269 -7 491(98)00207 -3
68 M. Trapido / Environmental Pollution 105 (1999) 67±74
PAH concentration in soil correlates signi®cantly The data from the rural areas were used for the estima-
with the corresponding levels in air (Vogt et al., 1987), tion of the PAH soil background concentrations in
house dust (Chuang et al., 1995), urban street dust Estonia. The sampling areas are shown in Fig. 1 and
(Takada et al., 1990) and plants (Wang and Meresz, characterised in Table 1.
1982), therefore, PAH determination in soil may pro- A total of 133 soil samples (68 rural and 65 urban
vide important information on the environmental pol- areas) were collected and analysed. Soil samples (0±10
lution state. Characteristic ratio of PAH and PAH cm upper layer) were collected in September 1996
pro®les can be used in qualitative and quantitative according to Aamot et al. (1987, 1996). The samples
source estimation (Vogt et al., 1987; Yang et al., 1991). were collected at least 25 m away from roads in the
The concentrations and distribution of PAH in Esto- urban areas and at least 150 m from the roadside in
nia have been studied mainly in water, bottom sedi- the rural ones. Samples were not collected from known
ments, ®sh, etc. (Veldre et al., 1979, 1987; Yegorov et contaminated sites as the territory of power stations and
al., 1989; Trapido and Palm, 1991; Trapido et al., 1992). industrial enterprises, etc.
No studies have been carried out to assess the accumu-
lation and distribution of PAH in soil. The main aims of 2.2. Analysis
the present study were to assess soil contamination by
PAH in Estonia, to relate PAH compound pro®les to The samples were dried at room temperature for 2 days,
dierent types of anthropogenic input and to determine then at 50 C for 2±3 hours, sieved through a 2-mm mesh
the regional background PAH levels in soil. to remove large particles and organic debris, and stored at
5 C prior to analysis. Twenty grams of dry sample were
soaked in 75 ml of hexane (analytical grade, puri®ed
2. Material and methods additionally with activated carbon) overnight. The ultra-
sonic extraction procedure twice during 5 minutes
2.1. Sampling followed (sonicator UZDA-A, Nauchpribor, USSR,
operated at 221.65 kHz; power input was 80 W). The
The concentrations of PAH in soil and PAH pro®les second extraction was conducted with 50 ml of hexane.
were determined in Tallinn, PaÈrnu, Kohtla-JaÈrve, and in The recovery of PAH from soil obtained using ultrasonic
the rural areas: Harjumaa, PaÈrnumaa, and Ida-Virumaa. extraction was comparable to recovery obtained with
Table 1
The sampling sites and the description of the area
Site no. Sampling area Description of area and presupposed PAH sources
(number of samples)
1 Tallinn (34) The capital of Estonia, 420 500a inhabitants, heavy trac, industry and heating
2 Tallinn, centre (7) Extremely heavy trac, domestic heating
3 PaÈrnu (16) Health resort, 51 800a inhabitants, trac, domestic heating
4 Kohtla-JaÈrve (15) Industrial area, 53 500a inhabitants, oil-shale thermal treatment industry (KIVITER), chemical
industry, power station, trac
5 Maardu (16) Rural, 20 000a inhabitants, harbour, phosphorite mining (until 1990), trac
6 Harjumaa (37) Rural, 77 974a inhabitants
7 PaÈrnumaa (38) Rural, 34 800a inhabitants
8 Ida-Virumaa (7) Rural, 22 100a inhabitants, oil-shale mining
a
According to Statistical Yearbook of Estonia, 1997.
Soxhlet extraction (Golden and Sawicki, 1975; Trapido, magnitude from 11.2 to 153 000 mg/kg. Signi®cant dif-
1995). Combined hexane extracts were evaporated care- ferences (at least one order of magnitude) were observed
fully to the volume of about 1 ml and then fractionated by in PAH concentrations between rural and urban
the thin-layer chromatography with aluminium oxide areas (see Fig. 2).
(TLC grade, Reanal, Hungary). The mobile phase PAH concentrations in soil in Tallinn also varied to a
was hexane±benzene 4:1 (by volume). PAH fraction was great extent at dierent sampling points. The PAH
eluted using twice 5 ml of acetone (extra pure grade, concentration for Tallinn ranged from 35.5 to max-
Reachim, Russia). Acetone was evaporated dry at room imum 26 300 mg/kg. PAH concentrations were sig-
temperature and the residue was dissolved in 0.22.0 ml ni®cantly higher in the central part of the city probably
of acetone (dependent to PAH concentration). due to intense trac (average value 90156363 mg/kg
Measurement of PAH concentration was carried out dry weight) than in the other parts of the city (compare
with high performance liquid chromatography (HPLC; data from Table 2). The investigation of snow cover
model 1311, Minsk, Byelorussia). The eluting solvent PAH pollution also indicated enhanced PAH level in
was a mixture of acetonitrile-water (both HPLC grade) the centre of Tallinn compared to the remote sites of the
93:7 (by volume) with ¯ow rate 8 ml minÿ1. Fluores- city (Trapido et al., 1992). PAH concentration in soil
cence detection with initiation wavelength 254 and 298 decreases with increasing distance from the centre of the
nm, the range of registration 330±600 nm was used. city. The decrease of PAH in north-east direction is
Chromatographic column (0.5300 mm) was ®lled with presented in Fig. 3 as a typical example. It declines to
Silosorb C18 (Chemapol, Czechoslovakia). The coe- the remote level (200 mg/kg or less) by the outskirts
cient of variation for HPLC method was 1.5%. PAH of the city (8±10 km from the centre).
standards were obtained from Aldrich Chemical Com- Transport became the predominant source of envir-
pany. Twelve PAH have been quanti®ed in the sam- onmental pollution in the city of Tallinn during recent
ples: phenanthrene (Ph), anthracene (A), ¯uoranthene 5±6 years contributing up to 90% of air pollution of
(Fl), pyrene (P), triphenylene (TPh), benzo(a)anthracene the city (Statistical Yearbook of Estonia, 1997). The
(BaA), chrysene (Chr), benzo(e)pyrene+benzo(b)¯uor- amount of cars has doubled during this period, that is a
anthene (BeP), benzo(k)¯uoranthene (BkFl), benzo(a)- unique rate all over the world. As the transport system
pyrene (BaP), and benzo(ghi)perylene (BghiPer). PAH is overloaded, frequent (in some locations close to per-
refers to the sum of these 12 compounds. The procedure manent) trac jams appear in the centre of the city. At
described earlier has been checked for recovery e- the same time air pollution load from stationary sources
ciencies by analyzing soil samples spiked with PAH declined three times due to economical situation (more
standards. Recovery of PAH was in 86±98% range. than 50% falling-o of production). Therefore, trac
Replicate analyses gave an error of 10%. could be one of the main reasons for enhanced PAH
concentrations in soil in the centre of the city.
The average PAH concentrations in soil were quite
3. Results and discussion high in two other cities Ð PaÈrnu and Kohtla-JaÈrve. For
the latter it has been expected, as Kohtla-JaÈrve is an
3.1. PAH concentrations industrial town (oil-shale thermal treatment, etc.) and
probably the most polluted town in Estonia. High
The mean and standard deviations of PAH con- concentrations of PAH in PaÈrnu (average value 7665
centrations in soil in dierent sampling areas are listed 4306 mg/kg dry weight) were unexpected as PaÈrnu is a
in Table 2. The PAH values ranged over 4 orders of health resort with minor industrial emissions into the
70 M. Trapido / Environmental Pollution 105 (1999) 67±74
Table 2
The mean concentrations and standard deviations of PAH in soil, mg/kg dry weight
PAH, polycyclic aromatic hydrocarbons; phenanthrene, Ph; anthracene, A; ¯uoranthene, Fl; pyrene, P; triphenylene, TPh; benzo(a)anthracene,
BaA; chrysene, Chr; benzo(e)pyrene+benzo(b)¯uoranthene, BeP; benzo(k)¯uoranthene, BkFl; benzo(a)pyrene, BaP; and benzo(ghi)perylene,
BghiPer.
than those reported for the areas contaminated by alu- PAH pattern. The mean PAH concentrations were
minium plant (Vogt et al., 1987), by blast furnace plant higher in PaÈrnumaa and Ida-Virumaa than in Harjumaa.
(Van Brummelen et al., 1996) and in soil samples col- Typical soil PAH concentration derived from
lected 0.5 m from the roadway (Yang et al., 1991). In samples from rural areas is estimated at about 100 mg/
23.4% of soils sampled in the urban areas (see Fig. 4) kg dry weight. This concentration is typical in the areas
PAH exceeded 4000 mg/kg. The data in Table 2 indi- where no anthropogenic pollution sources occur. In
cates that the average PAH concentration in the cities this study 40.3% of soils sampled in the rural areas
was at least one order of magnitude higher than in rural have PAH concentration less than 100 mg/kg (see
areas. Fig. 4). As it has been suggested (Shabad and Ilnitskii,
PAH concentrations in three rural areas (PaÈrnumaa, 1979; Edwards, 1983) that the typical endogenous
Harjumaa and Ida-Virumaa) varied from 11.2 to 2240 PAH in soil, resulting from plant synthesis and natural
mg/kg. The lowest value was determined in Harjumaa ®res, is in the range of 1±10 mg/kg. It can be concluded
and the highest in Ida-Virumaa. The latter demonstrates that typical Estonian soils from rural areas are con-
that PAH pollution level is enhanced not only in the taminated with PAH above the natural level. This may
town of Kohtla-JaÈrve, but also in the surrounding be due to long-range atmospheric transport of PAH
rural area of Ida-Virumaa. The data for soil PAH from source regions to these remote sites. Taking into
from Maardu were treated separately from the data from account that the climate conditions in Estonia are
the rest Harjumaa, as there are some dierences in the unfavourable for PAH degradation in soil during sub-
human activities in Maardu and the rest of Harjumaa stantial part of the year due to low bacterial activity, it
(see Table 1), and therefore some dierences in soil PAH can be assumed that typical soil PAH level is dierent
could be expected. The analysis of the data showed that when compared with soils in other climates. Therefore,
there were no dierences in concentrations or in the the typical soil PAH typical level in Estonia can only
be compared with the data from other northern coun-
tries. PAH from Estonian rural areas is signi®cantly
lower than in south Norway, similar to rural areas in
Wales and twice that in central Norway (Jones et al.,
1989; Aamot et al., 1996). The typical PAH levels in
Estonia were higher than the target value set by Dutch
government for unpolluted soil (20±50 mg/kg dry
weight; Van Brummelen et al., 1996). This target value
was reached in less than 10% of all samples from
Estonian rural areas.
Fig. 5. Bar diagram of normalised average polycyclic aromatic hydrocarbons (PAH) concentrations in soil in dierent sampling areas. Normal-
isation has been done by dividing the average concentration for each PAH by the concentration pyrene (P) in each separate sampling site. PAH:
1, phenanthrene; 2, anthracene; 3, ¯uoranthene; 4, pyrene; 5, triphenylene; 6, benzo(a)anthracene; 7, chrysene; 8, benzo(e)pyrene+benzo(b)¯uor-
anthene; 9, benzo(k)¯uoranthene; 10, benzo(a)pyrene; 11, benzo(ghi) perylene.
has enhanced amount of phenanthrene. PAH pro®le in The important characteristic feature of PAH pro®le in
Kohtla-JaÈrve is dierent from that in Tallinn and Kohtla-JaÈrve is relatively high concentration of benzo
PaÈrnu, and similar to soil PAH pro®le in rural areas. (ghi)perylene.
M. Trapido / Environmental Pollution 105 (1999) 67±74 73
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