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PAHs in Estonia

PAHs in Estonia

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Polycyclic aromatic hydrocarbons in Estonian soil: contamination
and pro\u00aeles
M. Trapido*
Department of Environmental Chemistry and Technology, Institute of Chemistry at Tallinn Technical University; 15, Akadeemia tee,
12618, Tallinn, Estonia
Received 27 April 1998; accepted 12 November 1998

The distribution and accumulation of polycyclic aromatic hydrocarbons (PAH) in soil as well as PAH pro\u00aeles have been inves- tigated in areas with di\u0080erent anthropogenic pollution such as the city of Tallinn, the towns of Pa\u00c8 rnu and Kohtla-Ja\u00c8 rve and some rural areas. PAH were identi\u00aeed in 147 soil samples (0\u00b110 cm upper layer) collected in September 1996. The typical\u00c6 PAH level in Estonian rural soil is about 100mg/kg dry weight. PAH concentrations in Tallinn, Pa\u00c8 rnu and Kohtla-Ja\u00c8 rve soil were quite high (the mean\u00c6 PAH concentrations were 2240, 7665 and 12 390mg/kg dry weight, respectively). The dominant PAH in soil samples were pyrene, triphenylene and \u00afuoranthene. 3\u00b14 ring PAH and 5\u00b16 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\u00aeles; Soil; Estonia
1. Introduction

Polycyclic aromatic hydrocarbons (PAH) released into the environment arise mainly from anthropogenic sources. They are mainly formed as by-products of incomplete combustion of organic materials. PAH have been identi\u00aeed in many emission sources, such as vehicle exhausts, power plants, chemical-, coke- and oil-shale industries, urban sewage. Primary natural sources of PAH are forest \u00aeres and volcanic activity (Suess, 1976; Shabad and Ilnitskii, 1979). United States Environ- mental Protection Agency (US EPA) has identi\u00aeed 16 PAHs as `priority pollutants'. PAH are important environmentally because many individual PAH are genotoxic (White et al., 1998) and may cause mutations and certain types of cancer. PAH compounds convert into carcinogens through metabolic activation in the organism. In many circumstances the environmental occurrence of PAH has been associated with adverse e\u0080ects on public health (Yang et al., 1991).

PAH are quite resistant to degradation. The range of half-lives for PAH in soil estimated by di\u0080erent researchers is quite large. They vary, dependent on the

compound, from 2 month to 2 years (Mackay et al., 1992) and from 8 to 28 years (Wild et al., 1990). When the release of PAH into the environment exceeds their degradation capacity, a signi\u00aecant accumulation of PAH is observed. The existence of permanent pollution sources results in the accumulation of PAH in soil, plants and water bodies.

Soil contamination originates mainly from PAH emissions to the atmosphere, which reach the soil via precipitation. Gaseous and particle-bound PAH can be transported over long distances before deposition (Wania and Mackay, 1996). PAH are accumulated mainly in the humus layer of soil. The further path- ways of PAH dissipation in contaminated soil may be volatilisation, irreversible sorption, leaching, accumu- lation by plants, and biodegradation (Reilley et al., 1996). PAH with three and more rings tend to be strongly adsorbed to the soil. Strong sorption coupled with very low water solubility and very low vapour pressures make leaching and volatilisation insigni\u00aecant pathway of PAH dissipation (Park et al., 1990). Also plants hardly take up any PAH from soil (Shabad and Ilnitskii, 1979; Sims and Overcash, 1983). Soil bacteria are the primary degraders of PAH in soil (Shabad and Ilnitskii, 1979, Gibson and Subramanian, 1984; Boldrin et al., 1993).

0269-7491/99/$\u00d0see front matter# 1999 Elsevier Science Ltd. All rights reserved.
PII: S0269-7491(98)00207-3
Environmental Pollution 105 (1999) 67\u00b174
* Tel.: +372-2536-269; e-mail: trapido@chemnet.ee.

PAH concentration in soil correlates signi\u00aecantly with the corresponding levels in air (Vogt et al., 1987), house dust (Chuang et al., 1995), urban street dust (Takada et al., 1990) and plants (Wang and Meresz, 1982), therefore, PAH determination in soil may pro- vide important information on the environmental pol- lution state. Characteristic ratio of PAH and PAH pro\u00aeles can be used in qualitative and quantitative source estimation (Vogt et al., 1987; Yang et al., 1991).

The concentrations and distribution of PAH in Esto- nia have been studied mainly in water, bottom sedi- ments, \u00aesh, etc. (Veldre et al., 1979, 1987; Yegorov et al., 1989; Trapido and Palm, 1991; Trapido et al., 1992). No studies have been carried out to assess the accumu- lation and distribution of PAH in soil. The main aims of the present study were to assess soil contamination by PAH in Estonia, to relate PAH compound pro\u00aeles to di\u0080erent types of anthropogenic input and to determine the regional background PAH levels in soil.

2. Material and methods
2.1. Sampling

The concentrations of PAH in soil and PAH pro\u00aeles were determined in Tallinn, Pa\u00c8 rnu, Kohtla-Ja\u00c8 rve, and in the rural areas: Harjumaa, Pa\u00c8 rnumaa, and Ida-Virumaa.

The data from the rural areas were used for the estima- tion of the PAH soil background concentrations in Estonia. The sampling areas are shown in Fig. 1 and characterised in Table 1.

A total of 133 soil samples (68 rural and 65 urban areas) were collected and analysed. Soil samples (0\u00b110 cm upper layer) were collected in September 1996 according to Aamot et al. (1987, 1996). The samples were collected at least 25 m away from roads in the urban areas and at least 150 m from the roadside in the rural ones. Samples were not collected from known contaminated sites as the territory of power stations and industrial enterprises, etc.

2.2. Analysis

The samples were dried at roomtemperature for 2 days, then at 50\ue000C for 2\u00b13 hours, sieved through a 2-mm mesh to remove large particles and organic debris, and stored at 5\ue000C prior to analysis. Twenty grams of dry sample were soaked in 75 ml of hexane (analytical grade, puri\u00aeed additionally with activated carbon) overnight. The ultra- sonic extraction procedure twice during 5 minutes followed (sonicator UZDA-A, Nauchpribor, USSR, operated at 22\u008b1.65 kHz; power input was 80 W). The second extraction was conducted with 50 ml of hexane. The recovery of PAH from soil obtained using ultrasonic extraction was comparable to recovery obtained with

Fig. 1. Location of sampling sites for the present study.
M. Trapido / Environmental Pollution 105 (1999) 67\u00b174

Soxhlet extraction (Golden and Sawicki, 1975; Trapido, 1995). Combined hexane extracts were evaporated care- fully to the volume of about 1 ml and then fractionated by the thin-layer chromatography with aluminium oxide (TLC grade, Reanal, Hungary). The mobile phase was hexane\u00b1benzene 4:1 (by volume). PAH fraction was eluted using twice 5 ml of acetone (extra pure grade, Reachim, Russia). Acetone was evaporated dry at room temperature and the residue was dissolved in 0.2\u00c42.0 ml of acetone (dependent to PAH concentration).

Measurement of PAH concentration was carried out with high performance liquid chromatography (HPLC; model 1311, Minsk, Byelorussia). The eluting solvent was a mixture of acetonitrile-water (both HPLC grade) 93:7 (by volume) with \u00afow rate 8ml min\u00c01. Fluores- cence detection with initiation wavelength 254 and 298 nm, the range of registration 330\u00b1600 nm was used. Chromatographic column (0.5\u00c2300 mm) was \u00aelled with Silosorb C18 (Chemapol, Czechoslovakia). The coe\u0081- cient of variation for HPLC method was 1.5%. PAH standards were obtained from Aldrich Chemical Com- pany. Twelve PAH have been quanti\u00aeed in the sam- ples: phenanthrene (Ph), anthracene (A), \u00afuoranthene (Fl), pyrene (P), triphenylene (TPh), benzo(a)anthracene (BaA), chrysene (Chr), benzo(e)pyrene+benzo(b)\u00afuor- anthene (BeP), benzo(k)\u00afuoranthene (BkFl), benzo(a)- pyrene (BaP), and benzo(ghi)perylene (BghiPer).\u00c6 PAH refers to the sum of these 12 compounds. The procedure described earlier has been checked for recovery e\u0081- ciencies by analyzing soil samples spiked with PAH standards. Recovery of PAH was in 86\u00b198% range. Replicate analyses gave an error of$\u008b10%.

3. Results and discussion
3.1. PAH concentrations

The mean and standard deviations of PAH con- centrations in soil in di\u0080erent sampling areas are listed in Table 2. The\u00c6 PAH values ranged over 4 orders of

magnitude from 11.2 to 153 000mg/kg. Signi\u00aecant dif- ferences (at least one order of magnitude) were observed in\u00c6 PAH concentrations between rural and urban areas (see Fig. 2).

PAH concentrations in soil in Tallinn also varied to a great extent at di\u0080erent sampling points. The\u00c6 PAH concentration for Tallinn ranged from 35.5 to max- imum 26300mg/kg. PAH concentrations were sig- ni\u00aecantly higher in the central part of the city probably due to intense tra\u0081c (average value 9015\u008b6363mg/kg dry weight) than in the other parts of the city (compare data from Table 2). The investigation of snow cover PAH pollution also indicated enhanced PAH level in the centre of Tallinn compared to the remote sites of the city (Trapido et al., 1992). PAH concentration in soil decreases with increasing distance from the centre of the city. The decrease of\u00c6 PAH in north-east direction is presented in Fig. 3 as a typical example. It declines to the remote level (200mg/kg or less) by the outskirts of the city (8\u00b110 km from the centre).

Transport became the predominant source of envir- onmental pollution in the city of Tallinn during recent 5\u00b16 years contributing up to 90% of air pollution of the city (Statistical Yearbook of Estonia, 1997). The amount of cars has doubled during this period, that is a unique rate all over the world. As the transport system is overloaded, frequent (in some locations close to per- manent) tra\u0081c jams appear in the centre of the city. At the same time air pollution load from stationary sources declined three times due to economical situation (more than 50% falling-o\u0080 of production). Therefore, tra\u0081c 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 high in two other cities \u00d0 Pa\u00c8 rnu and Kohtla-Ja\u00c8 rve. For the latter it has been expected, as Kohtla-Ja\u00c8rve is an industrial town (oil-shale thermal treatment, etc.) and probably the most polluted town in Estonia. High concentrations of PAH in Pa\u00c8rnu (average value 7665 \u008b4306mg/kg dry weight) were unexpected as Pa\u00c8 rnu is a health resort with minor industrial emissions into the

Table 1
The sampling sites and the description of the area
Site no.
Sampling area
(number of samples)
Description of area and presupposed PAH sources
Tallinn (34)
The capital of Estonia, 420 500ainhabitants, heavy tra\u0081c, industry and heating
Tallinn, centre (7)
Extremely heavy tra\u0081c, domestic heating
Pa\u00c8 rnu (16)
Health resort, 51 800ainhabitants, tra\u0081c, domestic heating
Kohtla-Ja\u00c8 rve (15)
Industrial area, 53 500ainhabitants, oil-shale thermal treatment industry (KIVITER), chemical
industry, power station, tra\u0081c
Maardu (16)
Rural, 20 000ainhabitants, harbour, phosphorite mining (until 1990), tra\u0081c
Harjumaa (37)
Rural, 77 974ainhabitants
Pa\u00c8 rnumaa (38)
Rural, 34 800ainhabitants
Ida-Virumaa (7)
Rural, 22 100a inhabitants, oil-shale mining
aAccording to Statistical Yearbook of Estonia, 1997.
M. Trapido / Environmental Pollution 105 (1999) 67\u00b174

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