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SYNOPSIS
Polycyclic Aromatic Hydrocarbons (PAHs) in Soil a Review
Wolfgang Wilcke1*
1
Institute of Soil Science and Soil Geography, University of Bayreuth, D-95440 Bayreuth, Germany

Accepted 23 March 2000

Summary Zusammenfassung Polyzyklische aromatische Kohlenwasser-


stoffe (PAK) in Bden eine bersicht
PAHs are mainly produced by combustion processes and consist
of a number of toxic compounds. While the concentrations of PAK entstehen vor allem durch Verbrennung; die Stoffklasse
individual PAHs in soil produced by natural processes (e.g., enthlt eine Reihe toxischer Verbindungen. Whrend die durch
vegetation fires, volcanic exhalations) are estimated to be around natrliche Prozesse (z.B. Vegetationsbrnde, Vulkanausbrche)
110 mg kg1, recently measured lowest concentrations are verursachten Hintergrundgehalte von einzelnen PAK in Bden auf
frequently 10 times higher. Organic horizons of forest soils and 110 mg kg1 geschtzt werden, liegen die heute gemessenen
urban soils may even reach individual PAH concentrations of niedrigsten Gehalte oft um den Faktor 10 hher. Organische
several 100 mg kg1. The PAH mixture in temperate soils is often Waldbodenauflagen und urbane Bden knnen sogar mehrere
dominated by benzofluoranthenes, chrysene, and fluoranthene. The 100 mg kg1 an einzelnen PAK enthalten. Das PAK-Spektrum in
few existing studies on tropical soils indicate that the PAH Bden der gemigten Breiten wird oft von den Benzofluoranthe-
concentrations are relatively lower than in temperate soils for most nen, Chrysen und Fluoranthen dominiert. Die wenigen vorliegenden
compounds except for naphthalene, phenanthrene, and perylene Arbeiten zu tropischen Bden deuten an, dass ihre PAK-Gehalte
suggesting the presence of unidentified PAH sources. PAHs im Vergleich zu Bden der gemigten Breiten bis auf die
accumulate in C-rich topsoils, in the stemfoot area, at aggregate Naphthalin-, Phenanthren- und Perylen-Gehalte niedrig sind. Fr
surfaces, and in the fine-textured particle fractions, particularly the Letztere werden bislang unbekannte Quellen in den Tropen
silt fraction. PAHs are mainly associated with soil organic matter vermutet. PAK akkumulieren in C-reichen Oberbden, im Stamm-
(SOM) and soot-like C. Although the water-solubility of PAHs is fubereich, auf Aggregatoberflchen und in den feineren Korn-
low, they are encountered in the subsoil suggesting that they are grenklassen, v.a. im Schluff. PAK sind vor allem mit organischer
transported in association with dissolved organic matter (DOM). Substanz und ruartigem C assoziiert. Obwohl die Wasserlslich-
The uptake of PAHs by plants is small. Most PAHs detected in keit von PAK gering ist, findet man sie im Unterboden, was darauf
plant tissue are from atmospheric deposition. However, earthworms hindeutet, dass PAK in Verbindung mit gelster organischer
bioaccumulate considerable amounts of PAHs in short periods. The Substanz transportiert werden. Die Pflanzenaufnahme von PAK
reviewed work illustrates that there is a paucity of data on the aus dem Boden ist gering. Die meisten PAK, die in Pflanzenge-
global distribution of PAHs, particularly with respect to tropical webe gefunden werden, stammen aus der Atmosphre. Regen-
and southern hemispheric regions. Reliable methods to characterize wrmer sind allerdings in der Lage, in kurzer Zeit erhebliche PAK-
bioavailable PAH pools in soil still need to be developed. Mengen zu akkumulieren. Diese bersichtsarbeit macht deutlich,
Key words: polycyclic aromatic hydrocarbons / PAHs / soil dass es einen Mangel an Information ber die globale PAK-
contamination / global distribution Verteilung gibt. Dies gilt insbesondere fr Bden der Tropen und
der sdlichen Hemisphre. Standardmethoden zur Charakterisierung
bioverfgbarer PAK-Pools mssen noch entwickelt werden.

1 Introduction burden in Great Britain is stored in soil. This estimate


excluded contaminated sites like the gaswork sites, petro-
PAHs are a class of several hundred individual compounds leum refineries, or wood preservation plants.
containing at least two condensed rings. They are produced PAHs have received much attention since they were found
by the incomplete combustion of compounds containing C in soils for the first time by Blumer (1961). The reason is the
and H, and diagenesis (Sims and Overcash, 1983; Baek et al., toxicity to humans and their possible harmful effect on soil
1991). Today, anthropogenic combustion of fossil fuels is organisms and plants (Menzie et al., 1992; Marquardt and
the by far most important source of PAH inputs to the Schfer, 1994). First reviews on the fate of PAH in soil-plant
environment (Baek et al., 1991). Once emitted, they are systems have been presented by Edwards (1983) and Sims
distributed atmospherically and deposited onto terrestrial, and Overcash (1983). In the early eighties some book
lacustrine, and marine surfaces. Wild and Jones (1995) publications dealt with the state-of-the-art in analyzing
estimated that at least 90% of the environmental PAH PAHs and summarized the knowledge of their occurrence
and fate in the environment (Hutzinger, 1980; Lee et al.,
* Correspondence: PD Dr. W. Wilcke; E-mail: wolfgang.wilcke@uni- 1981; Bjrseth, 1983; Grimmer, 1983; Bjrseth and
bayreuth.de Ramdahl, 1985). A review of Venkatesan (1988) informed

J. Plant Nutr. Soil Sci. (2000), 163, 229248 (2000)  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000 1436-8730/00/0306-0229 $17.50+.50/0
230 Wilcke

about sources and fate of perylene in sediments. Reviews of (Sims and Overcash, 1983; Jones et al., 1989c; Reinirkens,
Nikolaou et al. (1984), Baek et al. (1991), and Menichini 1993). PAH concentrations in topsoils increase in the order
(1992) summarized sources and fate of PAHs in the arable soils < mineral soils under forest < permanent
atmosphere; the latter with particular respect to the urban grassland < urban soils < specifically contaminated sites
atmosphere. Cerniglia (1984) gave an overview of the (Reinirkens, 1993, Knoche et al., 1995).
mammalian and microbial metabolism of PAHs.
The objective of this review is to summarize the present
2.2 Deposition from the atmosphere
state of knowledge on the distribution of PAHs in soils and
the processes affecting it on a global scale. Most PAHs reach the soil via deposition from the
atmosphere. Fhr et al. (1986) estimated the PAH emissions
2 Concentrations and distribution of PAHs in soils of the western part of Germany to be in the range of 500 to
1000 t a1 which would correspond to deposition rates of 20
2.1 Concentration levels in soils 40 g ha1 a1. Wild and Jones (1995) estimated emissions of
Individual PAH concentrations in soils produced by natural 11 PAH to the UK atmosphere to total about 700 t a1 and the
processes like vegetation fires and volcanic exhalations have average deposition rate to be 8.4 g ha1 a1. Further estimates
been estimated to be in the range of 110 mg kg1 (Edwards, of deposition rates are given in Tab. 1.
1983). In the most remote areas like the arctic benzo(a)pyr- The flux of PAHs to soil is largely influenced by their
ene concentrations range between 0.8 and 4.3 mg kg1 and concentrations in the atmosphere. In the atmosphere, PAH
thus are still near preindustrial concentration levels (Knoche concentrations vary depending on time of the year, weather
et al., 1995). At present, even the lowest measured PAH conditions, time of the day and properties of the study site. In
concentrations in temperate soils are about 10 times higher winter, PAH concentrations in the atmosphere of the
than the concentrations assumed to have been present prior temperate region are higher because of increased domestic
to industrialization and thus already include an anthropo- heating, reduced thermal and photo-decomposition, and less
genic contribution (Edwards, 1983; Sims and Overcash, atmospheric mixing due to more inversion situations
1983). Generally, PAH concentrations in soils increase with (Masclet et al., 1986; De Raat and Meijere, 1991; Menichini,
increasing impact of industry, traffic, and domestic heating 1992).

Table 1: Deposition rates of PAHs to soil and water surfaces.


Tabelle 1: Depositionsraten von PAK auf Boden und Wasseroberflchen.

Johnston and Matzner, 1984b Wickstrm and Jones Sanders et Wild and
Harrison, 1984a Tolonen, et al., al., Jones,
1987c 1989cd 1995e 1995f
Next to Back- Bulk Through-
highway ground fall
g ha1 a1

Naphthalene 0.081.26
Acenaphthylene 1.2
Acenaphthene 0.1 0.091.46g
Fluorene 1.45
Phenanthrene 0.011.00 2.0 0.593.29 2.03
Anthracene 1.2 < 0.001 0.060.97 0.08
Fluoranthene 5.87.9 < 0.001 0.250.69 0.581.00 0.012.8 4.6 0.386.44 1.47
Pyrene 0.011.7 4.0 0.144.48 0.89
Benz(a)anthracene 2.53.0 0.04 0.010.76 2.9 0.112.61h 0.48h
Chrysene 0.012.7i 3.0
Benzo(b)fluoranthene 3.13.8 0.19 6.7 0.095.43 0.68
Benzo(k)fluoranthene 1.11.5 0.08 6.8 0.021.89
Benzo(e)pyrene 0.013.10 3.8
Benzo(a)pyrene 2.32.5 0.05 0.020.11 0.120.21 0.012.60 3.6 0.051.33 0.73
Perylene 0.5
Indeno(1,2,3cd)pyrene 0.070.36 0.270.43 2.5
Dibenz(a, h)anthracene 0.7
Anthanthrene 1.0
Benzo(ghi)perylene 0.100.41 0.360.66 1.6 0.042.65 0.62
Coronene 0.5 ndj0.55
a
UK soils 198283. bGerman forest soils 198081. cNet fluxes to four rural Finnish lakes 17551985. dNet fluxes to a rural UK soil 18811980. eNet fluxes
to a rural UK peat ca. 17801989. fTwo urban UK soils (sampling time unknown). gIncludes fluorene. hIncludes chrysene. iIncludes triphenylene. jNot
detected.
PAHs in soil a review 231

Generally, concentrations of PAHs in soil decrease studies, correlations between organic C and PAH concen-
exponentially with increasing distance from a point source trations in soils have been reported (e.g. Jones et al., 1989d;
(Vogt et al., 1987; Van Brummelen et al., 1996a; Wilcke et Wilcke et al., 1999, b). Pathirana et al. (1994) observed a
al., 1996b). The transport distance of individual PAHs from correlation between PAH and lipid concentrations in soils
the emission sources depends principally on PAH half-lives next to a road near Brisbane (Australia). Correlations
in the atmosphere where PAHs may be degraded by thermal between PAH concentrations and those of other organic
or photo-decomposition and reaction with O3, SO2, SO3, pollutants such as the polychlorinated biphenyls have also
NOx or OH radicals (Butler and Crossley, 1981; Nikolaou et been reported and interpreted as indication of joint sources
al., 1984). The transformation of PAHs in the atmosphere is (Weiss et al., 1994). As traffic exhausts are a source for PAH
reduced when they are sorbed to particles. Depending on the and Pb some authors observed correlations between PAH
nature of the particles, transformation and degradation may and Pb concentrations in soil (Thomas et al., 1984; Boos et
even be completely inhibited. The sorption to soot particles al., 1990; Schulte, 1996). In the vicinity of an industrial area
allows for long-distance transport of unaltered PAHs of Linz (Austria), the PAH concentrations also correlated
(Nikolaou et al., 1984). The extent to which a PAH is with those of other heavy metals such as Cd, Cu, Hg, and Zn
sorbed to atmospheric particles increases with decreasing (Boos et al., 1990; Schulte, 1996).
volatility (Meharg et al., 1998). Yang et al. (1991) and
Meharg et al. (1998) observed that the transport distance
decreased with increasing molecular weight because the
proportion associated with fast settling atmospheric particles
increased. Gaseous PAHs, in contrast, may be distributed
over longer distances.
In forests, the canopy throughfall contains higher PAH
concentrations than the precipitation, because of the washout
of dry depositions. This effect is more pronounced in
coniferous than in deciduous forest (Matzner, 1984;
Blessing, 1996). Additionally, litter fall increases soil PAH
inputs in forests due to sorbed gaseous and particulate PAHs.
Snow and fog seem to have a particularly high scavenging
efficiency for atmospheric PAHs (Hartmann, 1995; Bless-
ing, 1996; Pichler et al., 1996). When PAH depositions
result from long-distance atmospheric transport, concen-
trations increase with increasing altitude (Korff et al., 1980;
Wilcke and Zech, 1997). However, this is not generally true
because Weiss (1998) did not detect a relationship between
altitude and PAH concentrations in organic layers of remote
Alpine forest soils in Austria.

2.3 PAH patterns in soils from temperate zones


Frequently, most individual PAH concentrations in soils
are strongly correlated with each other (e.g., Weiss et al.,
1994, Wilcke et al., 1997, Sauerwein, 1998), because PAH
patterns in soils are similar throughout the temperate zone.
The most abundant individual PAHs include the ben-
zo(b+j+k)fluoranthenes, chrysene, fluoranthene, and pyrene Figure 1: Mean PAH patterns in soils of a) different temperate sites and b)
different tropical sites. The results in a) are from 3 A horizons of forest
(e.g., Jones et al., 1989d; Weiss and Riss, 1992; Berset and soils in Slovakia (Wilcke et al., 1996b), 9 A horizons of forest soils in the
Holzer, 1995; Tab. 2, Fig. 1). Jones et al. (1989a) explained Czech Republic (Wilcke and Zech, 1997), 6 urban topsoils in Stephans-
the similarity in PAH patterns with their weathering, i.e. kirchen (Wilcke et al., 1997), and 25 urban topsoils in Bayreuth
transformation during atmospheric transport. Due to the (Eusterbrock, 1999). The results in b) are from 30 urban topsoils in
Bangkok, 4 rural topsoils in Ghana (Wilcke et al., 1999b), 18 urban topsoils
similarity of the PAH patterns benzo(a)pyrene concentra- in Uberlandia, Brazil, and 3 rural topsoils in the Brazilian savanna (Wilcke
tions may be used to estimate total PAH concentrations (i.e. et al., 1999a). Abbreviations are explained in Table 4.
the sum of the 16 EPA PAHs, e.g., Hellmann, 1982; Tebaay Abbildung 1: Mittlere PAK-Muster in Bden von a) verschiedenen
et al., 1993; Wilcke et al., 1997). The relationship between Standorten der gemigten Breiten und b) verschiedenen tropischen
Standorten. Die Ergebnisse in a) sind von 3 A-Horizonten von Waldbden
benzo(a)pyrene concentrations and those of the sum of the in der Slowakei (Wilcke et al., 1996b), 9 A-Horizonten von Waldbden in
16 EPA PAHs is different for organic and mineral horizons Tschechien (Wilcke and Zech, 1997), 6 urbanen Oberbden in Stephans-
(Figures 2ac). The correlation is weaker for B than for A kirchen (Wilcke et al., 1997) und 25 urbanen Oberbden in Bayreuth
(Eusterbrock, 1999). Die Ergebnisse in b) sind von 30 urbanen Oberbden
horizons because of the chromatographic effect during PAH in Bangkok, 4 lndlichen Oberbden in Ghana (Wilcke et al., 1999b), 18
leaching to greater soil depth (Hartmann, 1995; Guggen- urbanen Oberbden in Uberlandia, Brasilien und 3 lndlichen Oberbden in
berger et al., 1996; Wilcke et al., 1996b). In a range of der brasilianischen Savanne (Wilcke et al., 1999a).
Table 2: Range, arithmetic mean, and median of PAH concentrations in temperate topsoils.

232
Tabelle 2: Spanne, arithmetischer Mittelwert und Median der PAK-Gehalte in Oberbden der gemigten Breiten.

Arablea Grasslandb Forestc Urband


PAH Range Mean Median n Range Mean Median n Range Mean Median n Range Mean Median n
mg kg1

Naphthalene* nde20 5.7 4.0 14 nd25 4.0 3.0 33 1.6156 33 20 42 nd269 39 17 47


Acenaphthylene* nd220 17 2.0 14 nd23 2.3 nd 33 nd30 3.4 1.6 43 nd406 16 nd 73
Acenaphthene* nd51 9.6 nd 14 nd54 22 20 33 nd17 2.0 1.2 44 nd1800 57 1.2 73
Fluorene* nd5.0 1.1 nd 10 nd5.0 1.4 1.0 8 nd71 6.9 2.8 54 nd550 23 1.8 63
Phenanthrene* 6.067 26 17 14 7.067 19 14 33 3.2329 60 29 55 nd2809 190 37 108
Anthracene* nd11 2.4 1.6 14 nd4.3 1.6 1.5 33 nd75 8.6 3.4 54 nd1400 58 18 94
Fluoranthene* 3.0230 62 49 20 8.0350 51 34 37 0.1693 118 59 62 nd14200 805 273 138
Pyrene* 5.0134 39 28 15 6.080 25 23 33 0.4453 72 36 54 nd11900 593 155 117
Benz(a)anthracene* 3.0230 39 17 15 3.0100 26 23 33 nd402 43 15 54 nd7734 437 92 118
Chrysenef* 5.082 22 10 10 7.082 21 10 8 nd1123 117 43 54 nd-3556 278 53 106
Benzo(b)fluoranthene* 5.0100 33 30 19 4.0290 34 17 37 nd692 158 80 38 nd9700 456 80 91
Benzo(k)fluoranthene* nd38 10 10 15 2.081 20 11 12 nd2064 186 56 43 nd4224 236 30 81
Benzo(b + j + k)fluorantheneg 6.0100 43 42 20 9.8371 40 18 37 nd2064 243 114 60 1713600 762 190 116
Benzo(e)pyrene 39 39 1 nd775 87 39 42 nd6400 437 140 71
Benzo(a)pyrene* 2.085 18 14 20 3.0170 19 10 37 nd252 39 16 61 nd6461 350 88 138
Perylene 6.97.0 6.9 6.9 2 nd59 8.8 5.1 40 nd2300 93 9.4 59
Indeno(1,2,3-cd)pyrene* 5.035 15 8.0 11 6.035 14 9.0 8 0.4825 82 35 48 nd8000 387 76 90
Dibenz(a, h)anthracene* nd73 11 4.5 14 nd190 10 4.0 33 nd126 15 5.0 44 nd822 55 12 94
Anthanthrene 1.69.2 4.0 3.6 21
Benzo(ghi)perylene* 5.048 19 18 15 nd96 28 23 33 nd523 62 29 48 nd8370 370 91 130
Coronene nd5600 176 50 69
EPA-PAHsh 328 216 284 194 904 410 4420 1103
a
Data from Michels and Siegfried (1985), Jones et al. (1989a, d), Tebaay et al. (1993), Berset and Holzer (1995), Schulz (1995), Wilcke et al. (1997). bData from Jones et al. (1989d), Tebaay et al. (1993), Berset
and Holzer (1995). cData from Matzner (1984), Sullivan and Mix (1985), Fleischmann and Wilke (1991), Weiss and Riss (1992), Mnch (1993), Tebaay et al. (1993), Berset and Holzer (1995), Hartmann (1995),
Pichler (1995), Blessing (1996), Van Brummelen et al. (1996a), Wilcke et al. (1996a, b), Wilcke and Zech (1997), Krau et al. (2000). dData from Butler et al. (1984), Michels and Siegfried (1985), Jones et al.
(1989d), Kasperowski and Frank (1989), Boos et al. (1990), Weiss and Riss (1992), Felix-Henningsen et al. (1993), Joneck and Prinz (1993), Tebaay et al. (1993), Wilcke et al. (1997), Eusterbrock (1999). eNot
detected. fData frequently contains triphenylene. gSum of the benzo(b, j, and k)fluoranthenes. hSum of the means/medians, EPA-PAHs marked with an asterisk.

Wilcke
PAHs in soil a review 233

Arable topsoils typically contain around 200 mg kg1 for the


sum of the 16 EPA PAHs (Hellmann, 1982; Brne, 1986;
Berset and Holzer, 1995; Tab. 2). The low values are
attributable to the location in rural areas and to the dilution
with uncontaminated subsoil material by plowing (Bierl et
al., 1984; Brne, 1986). In permanent grassland soils, the
lack of dilution causes a stronger accumulation near the soil
surface (Brne, 1986; Hembrock-Heger et al., 1992). Soils
of river valleys often exhibit elevated PAH concentrations
following the distribution of fine textured sediment rich in
organic matter (e.g., Tebaay et al., 1993; Schulte, 1996;
Linke et al., 1997).
Concentrations of PAHs in agricultural soils may be
substantially and persistently increased when sewage sludge
(Wild et al., 1990, 1991a, b; Knoche et al., 1995), farmyard
manure (Wild et al., 1990; Schulz, 1995), compost (Brne,
1986) or composted waste-sewage sludge mixtures (Knig et
al., 1987) are applied. Wild et al. (1990, 1991b) detected 30
years after sewage sludge application still 3 times higher
PAH concentrations than in unamended control soils,
particularly of the less biodegradable higher molecular
PAHs. In their review on PAH concentrations in sewage
sludges, Drescher-Kaden et al. (1990) pointed out that PAHs
are present in all sewage sludges often at 10 times or more
higher concentrations than in soil. The application of sewage
sludge also changes soil chemical and biological properties.
The addition of sewage sludge increases the biological
activity, introduces microorganisms adapted to degrade
PAHs, and enhances the leaching of PAHs associated with
DOM, all together resulting in faster disappearance rates. In
contrast, the organic matter additions may cause a stronger
sorption of PAHs and thus inhibit degradation and leaching
(Beck et al., 1996).

2.4.2 Forest soils


Many publications show that PAH concentrations in the
organic layers of forest soils are substantially higher than in
the mineral soil (e.g., Matzner, 1984; Berteigne et al., 1988;
Hartmann, 1995). As the density of the organic layer is
much lower than that of the mineral horizon, the difference
in PAH storage between mineral and organic horizons is
Figure 2: Relationship between the benzo(a)pyrene concentrations and the smaller (Hartmann, 1995).
sum of the concentrations of the 16 EPA PAHs in a) A horizons, b) B In general, PAH concentrations increase in the order Oi <
horizons, and c) Oa horizons (Data from the same sources as in Tab. 2).
Abbildung 2: Beziehung zwischen den Benzo(a)pyren-Gehalten und den
Oe < Oa which is explained by the faster mineralization of
Summengehalten der 16 EPA-PAK in a) A-Horizonten, b) B-Horizonten organic matter than of PAHs and by preferential leaching
und c) Oh-Horizonten (Daten aus den gleichen Quellen wie in Tab. 2). and degradation of the lower molecular PAHs (e.g.,
Berteigne et al., 1988; Hartmann, 1995; Pichler et al.
1996; Fig. 3). Matzner et al. (1981) assumed that the large
2.4 PAH concentrations in differently used soils from surface area of the Oa horizons may increase PAH sorption.
temperate zones
Wilcke et al. (1996b) found highest PAH concentrations in
organic layers heavily polluted by the emissions of an Al
2.4.1 Agricultural soils smelter in the Oe horizon. The authors assumed that either
Besides the deposition from the atmosphere, the type of organic matter mineralization was reduced due to the high
land use influences the PAH concentrations and patterns in pollutant load or PAH inputs from the atmosphere were
soil. Therefore, the specific findings for a given land-use larger than PAH leaching and degradation. However,
type will be discussed in the following. Of course it must be Eschenbach et al. (1991) did not observe a reduction of
considered that distinctions between the various land-use the microbial activity in highly PAH-contaminated soils.
types may sometimes not be sharp because e.g., agricultural The occurrence of maximum PAH concentrations in the Oe
or forest soils may be located in an urban area. horizon in some soils is reflected by the highest arithmetic
234 Wilcke

2.4.3 Urban soils


PAH concentrations in urban soils have received more
attention. Hembrock-Heger et al. (1992) observed increasing
PAH concentrations in soils with increasing population
density. Schulte (1996) found highest PAH concentrations in
urban soils of Leipzig in the inner city center. However, high
PAH concentrations have also been found in a rural village
in southern Germany without industry mainly because of
domestic heating and traffic on a national road (Wilcke et al.,
1997).
Pollutant concentrations in urban soils are highly variable
and strongly depend on the kind and content of technogenic
substrates and on kind and duration of land-use (Blume,
1996). Particularly, technogenic additions may increase
PAH concentrations in urban soils (Meuser, 1996). Typical
for cities which were heavily destroyed during the second
Figure 3: Depth distribution of average benzo(a)pyrene concentrations in world war are soils containing partly burnt rubble which is
organic layers of forest soils. (Data from the same sources as in Table 2). frequently highly PAH-contaminated (Smettan et al., 1993;
Abbildung 3: Tiefenverteilung mittlerer Benzo(a)pyren-Gehalte in der Smettan and Ehrig, 1995; Renger and Mekiffer, 1997).
organischen Auflage von Waldbden (Daten aus den gleichen Quellen wie
in Tabelle 2). In general, PAH concentrations in urban soils decrease
exponentially with increasing depth (Hembrock-Heger et al.,
1992; Schulte, 1996). However, particularly at abandoned
mean of the Oe horizons included in Fig. 3 while the industrial sites, high PAH concentrations may occur in
medians follow the order Oi < Oe < Oa. At sites covered by deeper horizons because of sequential depositions of differ-
mull, PAH concentrations were highest in the A horizon ently contaminated material (Tebaay et al., 1993; Schulte,
probably because of fast biological mixing of degraded litter 1996).
and the mineral soil (Guggenberger et al., 1996). There is a number of studies reporting increased PAH
Some authors assume that the PAH pattern resembles that concentrations in soils next to roads (e.g., Butler et al., 1984;
of the atmospheric deposition in the Oi horizon but is Tebaay et al., 1993; Pathirana et al., 1994). The sources
gradually transformed with increasing soil depth (Hartmann, of these PAHs include tar which may contain up to 1 g
1995; Wilcke and Zech, 1997). Increasing transformation of benzo(a)pyrene kg1 (Borneff and Kunte, 1987), road and
organic matter and PAHs is reflected by decreasing tire abrasion (Tebaay et al., 1993), and street dust which
proportions of lower molecular (and thus more easily often has higher PAH concentrations than soil (Smith et al.,
degradable, more volatile, and more water-soluble) PAHs
in the order Oi > Oe > Oa (Berteigne et al., 1988; Pichler et
al., 1996; Wilcke and Zech, 1997). These differences in PAH
patterns were found to be smaller in heavily polluted organic
layers than in less polluted ones, probably because at high
input rates, PAHs are transported from Oi to Oa horizons
without transformation (Van Brummelen et al., 1996a).
In the mineral soil, the sum of PAH concentrations
decreases and the contribution of lower molecular PAHs to
the sum of PAH concentrations increases with increasing
depth (Guggenberger et al., 1996; Wilcke et al., 1996b;
Cousins et al., 1999). The concentration ratios of individual
PAHs in the B horizon to those in the Oa horizon are related
with the octanol-water partition coefficient (KOW, Fig. 4).
The leaching rate of a PAH increases with increasing water
solubility. The reduced dependence of the B/Oa ratios of
higher molecular PAHs on KOW may be due to the
increasing importance of DOM-associated transport. The
affinity of PAHs to DOM is positively correlated with the Figure 4: Average relationship between the octanol-water partition
KOW (Marschner, 1999). coefficient (KOW) and the ratio of PAH concentrations in the 1520 cm
layer to those in the Oa horizon of 16 north Bavarian Norway spruce (Picea
Deschauer (1995) studied the impact of compost applica- abies (L.) Karst.) sites (Krau et al., 2000). Abbreviations are explained in
tion to nutrient-poor forest soils. He found two years after the footnote of Table 4.
application of up to 100 m3 compost significantly higher Abbildung 4: Mittlerer Zusammenhang zwischen dem Oktanol-Wasser-
Verteilungskoeffizienten (KOW) und dem Verhltnis zwischen den PAK-
PAH concentrations only in the Oi horizons although the Gehalten in der 1520 cm-Schicht des Mineralbodens und im Oh-Horizont
compost contained a 10 times higher PAH concentration auf 16 Fichten-Standorten (Picea abies (L.), Karst.) in Nordbayern (Krau
than the soil. et al., 2000).
PAHs in soil a review 235

1995). Generally, PAH concentrations decrease with from the average PAH pattern of European soils. Gardens on
increasing distance from the road (e.g., Butler et al., 1984; formerly industrially used land may contain particularly
Yang et al., 1991; Pathirana et al., 1994). high PAH concentrations (Crmann and Wstemann,
The transport distance of PAH from the road ranges 1995).
between 35 m (Mnch, 1992, 1993) and 8 m (Tebaay et al., PAHs are accumulated in soils used to clean waste water by
1993). Near a highway in England, Johnston and Harrison trickling which may be found near some large German cities
(1984) and Harrison and Johnston (1985) found that most (Felix-Henningsen et al., 1993; Bechmann and Grunewald,
PAHs were deposited within the first 3.8 m from the road. 1995). Such soils may contain up to 30 mg PAHs kg1; the
However, they recorded an influence of the road still at a contamination may reach depths > 1 m (Felix-Henningsen et
distance of 70 m. A budget estimate of Hewitt and Rashed al., 1993).
(1990) for PAHs near a major English highway revealed that
PAH accumulation in soils near the road is higher than 2.5 PAHs in soils from arid zones
estimated from deposition measurements. This was due to
the scavenging effect of the vegetation and because the PAH There are few studies on PAH concentrations in soils near
inputs associated with street dusts were more important than oil- and gas-exploitation sites in arid regions. Davani et al.
atmospheric deposition at their study site. They also stated (1986) and Gennadiyev et al. (1990) have shown that oil and
that between 70 and 95% of PAHs in car exhausts are far gas industry has caused significant soil contaminations with
distributed and thus contribute to the diffuse background PAHs. Davani et al. (1986) also demonstrated that PAHs are
concentration. As lower traffic speed and frequent gear mobile in these soils because they were detected several tens
changing result in higher PAH emissions, soils next to roads of meters from a pit used for produced water in New Mexico.
in urban areas often contain higher PAH concentrations than Gennadiyev et al. (1990) found up to 100fold elevated PAH
soils next to roads out of urban areas (Kasperowski and concentrations at a distance of 6 km from a gaswork in
Frank, 1989; Joneck and Prinz, 1993; Wilcke et al., 1997). Astrakhan which significantly inhibited biological activity.
Much work has been addressed to abandoned industrial
sites. Highly contaminated sites include those of coke ovens, 2.6 PAHs in soils from tropical and subtropical zones
gasworks, petroleum refineries, and wood conservation Connell et al. (1999) reported in their review that PAH
plants (Wilson and Jones, 1993). The PAH contamination concentrations in environmental materials of tropical
of soils at gaswork sites results from tar, oil, coal, and ashes regions are lower than in polar regions. Similar observations
remaining as waste (Yu et al., 1990; Wilson and Jones, were made by Smith et al. (1995) who compared PAH
1993). The contamination of industrial sites is characterized concentrations in soils and street dusts of the cities of
by its high spatial variability and often reaches great soil Birmingham/UK and Lahore/Pakistan. The PAH concen-
depths mainly because of the burial of contaminated trations in both materials were lower in Lahore than in
material (Ifland et al., 1993; Tselmann, 1997). Weigand Birmingham. The authors assumed faster microbial degra-
et al. (1997) showed that the distribution of PAH sources and dation and photo-oxidation and enhanced volatilization to be
sorbents in soil may be adequately described with a the reasons. The work of Wilcke et al. (1999a, b, 2000)
stochastic model indicating that there is no systematic in Bangkok/Thailand, Ghana, Uberlandia/Brazil, and the
PAH distribution in such heavily polluted soils. Ifland et al. Amazonas basin also indicates that PAH concentrations in
(1993) assigned typical PAH patterns to specific production tropical soils, on average, are lower than in temperate soils
processes during coal coking and gas production. Partic- under similar land use, although recent PAH emissions by
ularly high PAH concentrations (up to 476 mg kg1) were traffic, industrial activities, and vegetation fires are not
found in Reductosols in the city of Berlin (Germany) derived likely to be lower (Tab. 3).
from municipal waste containing tar paper and from loam of The results of Wilcke et al. (1999a, b) also demonstrate that
coking sites (Renger and Mekiffer, 1997). Frequently, PAH- the PAH pattern is markedly different between tropical and
contaminated industrial substrates were used for land- temperate soils. In the tropical soils under study, naphtha-
scaping. This may be one reason why Gierse (1997) found lene, phenanthrene, and perylene dominate (Fig. 1b). If it is
that more than half of the playgrounds in the city of assumed that, similar to the temperate environment, the PAH
Wuppertal were substantially polluted with PAHs. pattern is weathered in the atmosphere, a typical PAH
Garden soils are often highly contaminated with PAHs (e.g. pattern would be different in tropical than in temperate soils.
Tebaay et al., 1993; Lenz et al., 1997; Eusterbrock, 1999). A The abundance of the volatile and most easily degraded
recent review on the PAH contamination of garden soils has PAHs (naphthalene and phenanthrene), however, is surpris-
been presented by Crmann and Wstemann (1998). The ing and suggests that there are specific sources for these
reasons for high PAH concentrations include additions of compounds in the tropical environment.
composts, garden wastes, ashes, slag, rubble, tar paper, or
the burning of vegetation (Crmann, 1992; Tebaay et al.,
2.7 Pedogenetic influence on PAH distribution in soils
1993; Lenz et al., 1997). Ash from coal combustion for
domestic heating was assumed to be the major source of Hartmann (1995), Guggenberger et al. (1996), and Wilcke
PAHs in garden soils of Bremen as derived from the et al. (1996a) reported that in Podzols the spodic horizon
similarity of the PAH patterns (Lenz et al., 1997). However, serves as subsoil sink of PAHs (Fig. 5a). Blessing (1996) and
the PAH patterns in their study are not distinctly different Pichler (1995) found substantial perylene concentrations in
Table 3: Range, arithmetic mean, and median of PAH concentrations in tropical topsoils.

236
Tabelle 3: Spanne, arithmetischer Mittelwert und Median der PAK-Gehalte in Oberbden aus den Tropen.

Urban soils in Bangkoka Urban soils in Forest soils in the Rural agricultural and
Uberlandiab Amazonas basinc forest soils in Ghanaa
PAH Range Mean Median n Range Mean Median n Range Mean Median n Range Mean Median n
mg kg1

Naphthalene* 1.7145 17 9.8 30 3.030 13 12 18 3.0356 110 45 6 5.024 16 18 4


Acenaphthylene* 0.14.0 1.0 0.6 30 0.03.1 0.6 0.5 18 0.22.2 0.6 0.2 6 0.11.6 0.8 0.8 4
Acenaphthene* 0.16.1 1.0 0.5 30 0.13.8 0.8 0.5 18 0.22.0 0.8 0.6 6 0.40.8 0.6 0.6 4
Fluorene* 0.24.5 1.2 0.7 30 0.23.9 1.1 0.8 18 0.57.0 3.4 3.3 6 1.32.4 1.7 1.5 4
Phenanthrene* ndd61 10 5.0 30 0.648 11 7.9 18 7.735 22 22 6 7.311 9.0 8.8 4
Anthracene* 0.15.0 1.2 0.7 30 0.06.2 1.0 0.8 18 0.32.6 0.8 0.4 6 1.31.9 1.5 1.4 4
Fluoranthene* nd45 10 6.2 30 0.556 10 8.3 18 0.44.9 2.5 2.1 6 3.54.8 4.3 4.4 4
Pyrene* 0.348 11 5.7 30 0.439 7.6 5.6 18 0.32.3 1.3 1.3 6 3.14.1 3.6 3.5 4
Benz(a)anthracene* 0.135 5.0 2.6 30 0.125 4.2 2.1 18 0.00.2 0.1 0.1 6 0.91.1 1.0 1.0 4
Chrysene/Triphenylene* 0.330 8.5 6.5 30 0.332 7.6 5.4 18 0.00.6 0.4 0.4 6 2.73.5 2.9 2.8 4
Benzo(b+j+k)fluorantheneg 0.850 14 10 30 0.456 16 12 18 0.11.3 0.4 0.3 6 5.76.6 6.1 6.1 4
Benzo(e)pyrene 0.625 8.2 6.5 30 0.222 6.2 4.8 18 0.00.3 0.2 0.1 6 3.03.8 3.4 3.4 4
Benzo(a)pyrene* 0.222 5.5 3.6 30 0.125 5.2 3.6 18 0.01.0 0.3 0.2 6 1.92.2 2.0 1.9 4
Perylene 0.1136 14 3.2 30 0.238 5.4 3.3 18 0.511 2.6 1.0 6 1.619 7.1 3.7 4
Indeno(1,2,3cd)pyrene* 0.428 8.4 5.9 30 0.264 13 8.2 18 0.00.2 0.1 0.1 6 2.22.7 2.4 2.5 4
Dibenz(a, h)anthracene* nd42 1.3 0.9 30 0.114 2.9 1.9 18 0.00.2 0.1 0.1 6 0.20.5 0.4 0.4 4
Benzo(ghi)perylene* 0.759 12 7.5 30 0.460 12 7.9 18 0.00.2 0.1 0.1 6 1.31.9 1.6 1.6 4
EPA-PAHse 11347 107 67 30 6.5361 106 85 18 15397 143 84 6 1518 16 16 4
a
Wilcke et al. (1999b). bWilcke et al., (1999a). cWilcke et al. (2000). dNot detected. eSum of the means/medians, EPA-PAHs marked with an asterisk.

Wilcke
PAHs in soil a review 237

Figure 6: Differences in the sum of 20 PAH concentrations between


aggregate core and surface fractions expressed in % of the cores
concentration along a deposition gradient in central Slovakia. Positive
values indicate enrichment, negative ones depletion in the surface fraction
(Wilcke et al., 1996b).
Abbildung 6: Differenz der Summengehalte von 20 PAK zwischen
Aggregatkern und Aggregatschale ausgedrckt in % der Gehalte im Kern.
Positive Werte bedeuten eine Anreicherung, negative Werte eine
Abreicherung in der Aggregatschale (Wilcke et al., 1996b).

Figure 5: Depth distribution of the sum of the 16 EPA PAHs in a)


a Podzol (Hartmann, 1995) and b) a Gleysol (Blessing, 1996). In b),
additionally the perylene concentration is shown.
Abbildung 5: Tiefenverteilung der Summengehalte der 16 EPA-PAK in a)
einem Podsol (Hartmann, 1995) und b) einem Gley (Blessing, 1996). In b)
sind zustzlich die Perylen-Gehalte dargestellt.

the reduced subsoil horizons of Gleysols hitherto only


reported to occur in marine and lacustrine sediments because
of biological production (Venkatesan, 1988, Fig. 5b).

2.8 Small-scale distribution on PAHs in soils


In general, only a portion of the total PAH concentration is
bioavailable or may be leached (Kelsey et al., 1997). The
size of this reactive PAH pool in soils depends on kind and
location of PAH binding. Recent work demonstrated that Figure 7: Mean enrichment factors of the sum of the concentrations of 20
PAHs are not evenly distributed in soil (Guggenberger et al., PAHs in particle-size separates normalized to the PAH concentrations in
bulk soil. Error bars represent standard deviations, n = 28 (Wilcke et al.,
1996; Wilcke et al., 1996a, b, 1997). 1997 and own unpublished data).
Studies in the northern Czech Republic, in Slovakia, and in Abbildung 7: Mittlerer Anreicherungsfaktor der Summengehalte von 20
urban soils of Rosenheim have shown that, similar to heavy PAK in Korngrenfraktionen normiert auf die PAK-Gehalte im
metals (Koenies, 1985), PAH concentrations are higher in Gesamtboden. Die Fehlerbalken reprsentieren die Standardabweichung,
n = 28 (Wilcke et al., 1997 und eigene unverffentlichte Daten).
soils at the stemfoot of beech trees (Fagus sylvatica L.) than
away from the stems (Wilcke et al., 1996b; Wilcke and Zech,
1997; Wilcke et al., 1997). These results demonstrate that the more pronounced was the accumulation of PAHs at
PAHs in the rain water collected by the canopy are washed aggregate surfaces (Wilcke et al., 1996b; Fig. 6).
down associated with particles without interaction with the In SOM research, theoretically defined reactive soil pools
bark. are approached by physical soil fractions including particle-
PAHs deposited from the atmosphere or leached from size and density separates. These pools are characterized by
overlying horizons are preferentially sorbed to aggregate substantial differences in quantity and quality of organic
surfaces (Wilcke et al., 1996a, b). The higher the PAH load matter (Christensen, 1992; Schulten and Leinweber, 2000).
of soils along a deposition gradient in central Slovakia was, The close association of organic contaminants with soil
238 Wilcke

organic matter consequently results in a heterogeneous PAH


distribution among particle-size fractions (Guggenberger et
al., 1996; Pichler et al., 1996; Wilcke et al., 1996b, 1997).
In organic horizons of forest soils, Pichler et al. (1996)
found increasing PAH concentrations with decreasing
particle size. The concentrations of the less reactive highly
condensed PAHs increased more strongly than those of the
more easily degradable lower molecular PAHs. This
indicates an increasing alteration of the PAH mixture from
coarse to fine particles. At the same time, the C/N ratios
decreased with decreasing particle size. Thus, increasing
alteration of the PAH mixture goes along with increasing
SOM alteration. This conclusion is further supported by the
finding that the increase in PAH concentrations in the fine
fractions from the Oi via the Oe to the Oa horizon is higher
than in the coarse fractions.
In a range of studies, highest PAH concentrations in the Figure 8: Temporal course of estimated deposition rates to subaquatic
limnic sediments (Christensen and Zhang, 1993; Sanders et al., 1993) and
mineral soil have been observed in the silt-sized fraction to peat (Sanders et al., 1995) between the second half of the 18th century
(Guggenberger et al., 1996; Mller et al., 1997; Wilcke et al., and present. Note that the data of Sanders et al. (1993) are magnified
1997). Possible explanations of these results are the high 10fold.
affinity of PAHs for aromatic structures in soil organic Abbildung 8: Zeitlicher Verlauf geschtzter Depositionsraten in subaqua-
tische limnische Sedimente (Christensen und Zhang, 1993; Sanders et al.,
matter (Gauthier et al., 1987; Chiou et al., 1998) which also 1993) und in Moor (Sanders et al., 1995) zwischen der zweiten Hlfte des
show highest concentrations in the silt fraction (Baldock et 18. Jahrhunderts und heute. Die Daten von Sanders et al. (1993) sind
al., 1992) and the deposition of PAHs associated with silt- 10fach berhht.
sized aerosols which persist unchanged in soil. The results of
solution from Alpine Gleysols with stainless-steel tubes. The
Wilcke et al. (1996b) also show that at sites where PAH
soil solution only contained low molecular weight PAHs
deposition rates are high, the fresh particulate organic matter
(naphthalene accounted for 5560%, phenanthrene for 20
of the sand fraction has high PAH concentrations which are
25% of the sum of 20 PAHs (i.e. the 16 EPA PAHs,
correlated with the deposition rate. However, when all
triphenylene, benzo(k)fluoranthene, benzo(e)pyrene, and
available data are pooled, it becomes evident that the
perylene)).
average accumulation of PAH in the silt and clay fractions is
similar and higher than in the sand fractions (Fig. 7). Thus, in
some soils the high surface area and organic matter content 2.10 Temporal trends
of the clay fraction seems to be more important than SOM To determine the temporal trend of PAH depositions,
quality of the silt fraction or particle-size of deposited archived soil samples, dated peat cores, or dated marine and
aerosols. lacustrine sediment cores have been used. Publications on
Similar to the findings for organic horizons, the proportion the retrospective analysis of dated peat cores (Sanders et al.,
of high molecular weight PAHs increases while that of low 1995) and of archived soil material are scarce, the latter up to
molecular weight PAHs decreases with decreasing particle now being restricted to the Rothamsted soil archive (Jones et
size again indicating the advanced state of alteration of the al., 1989a, b, c; Wild et al., 1990). However, there is a range
PAH mixture in the finer fractions (Guggenberger et al., of work on the depth distribution of PAHs in dated sediment
1996; Wilcke et al., 1996a, b, 1997). which may be used to trace back the historical PAH
deposition rates (e.g., Christensen and Zhang, 1993; Sanders
et al., 1993; Simcik et al., 1996). Jones et al. (1989a, b, c,),
2.9 Soil solution Wild and Jones (1990), and Wild et al. (1991a) observed a
Deschauer (1995) found between 3.3 and 736 ng l1 continuous increase in rural topsoil PAH concentrations,
of the sum of 13 PAHs (naphthalene, fluorene, pyrene, particularly of higher molecular PAHs during this century,
phenanthrene, fluoranthene, benzo(a)anthracene, chry- indicating that losses were and still are smaller than the
sene, benzo(b)fluoranthene, benzo(k)fluoranthene, ben- deposition from the atmosphere.
zo(a)pyrene, dibenz(a,h)anthracene, benzo(ghi)perylene, To trace the temporal trend of depositions to sediments no
and indeno(1,2-cd)pyrene) in litter leachates of a forested changes in PAH concentrations may occur after sorption to
Podzol. On average, the most abundant PAHs were the sediment, which has been shown to be the case, and PAH
naphthalene (60% of the sum of 13 PAH concentrations, concentrations have to be corrected for compaction and so-
the concentration ranged from 1.7 to 694 ng l1) > called sediment focussing, i.e. the mixing of sediment
phenanthrene (15%, nd-35 ng l1) > fluorene (5%, nd-20 (Readman et al., 1987; Simcik et al., 1996; Ns and Oug,
ng l1). All other PAHs, on average, accounted for less than 1997).
5% of the 13 PAHs. There were no differences in PAH While with the help of sediment cores taken near industrial
concentrations of soil solutions in control plots and plots activities the history of the emissions caused by these
treated with organic waste. Blessing (1996) extracted soil activities may be traced back, remote lakes without
PAHs in soil a review 239

industrial sewage additions and without commercial or combustion of organic material. This occurs naturally in
leasure motorboat activity may be used to analyze the vegetation fires, volcanic activity, and diagenetic processes.
background temporal trend. Most studies on PAH However, it is believed that by far most PAHs in temperate
concentrations in sediment cores of both industrially or regions are released into the environment by anthropogenic
traffic-influenced and remote lakes show that PAH concen- combustion of wood and fossil fuels. The way and extent of
trations in sediments increased in the second half of the 19th PAH formation during combustion of organic matter
century (e.g. Wickstrm and Tolonen, 1987; Cranwell and depends on local temperature and mixing conditions in the
Koul, 1989; Simcik et al., 1996; Fig. 8). Cranwell and Koul flame. Therefore, the PAH pattern in emissions of the same
(1989), Sanders et al. (1993), and Simcik et al. (1996) source may be highly variable (Ramdahl et al., 1982;
reported decreasing deposition rates since the mid seventies Colmsj et al., 1986; Masclet et al., 1987). Generally, the
because of a change in fuel consumption from coal to oil and lower combustion temperatures are the more PAHs will be
gas. This coincides with the decrease in PAH concentrations released. At high temperatures more highly condensed PAHs
of urban air after 1970 (Menichini, 1992; Jacob et al., 1993). are produced than at low temperatures; low temperatures
The data indicate that recent PAH deposition rates are still favor the formation of alkyl homologues (Masclet et al.,
markedly higher compared to the beginning of industriali- 1987; Gonzales-Vila et al., 1991).
zation. Wickstrm and Tolonen (1987) found that PAH In addition to combustion processes, there is some evidence
concentrations continuously increased since about 1850 in for biological PAH formation. Perylene is believed to be
the sediments of three remote lakes in Finland. Readman et produced biologically from pigments of fungi, insects, and
al. (1987) also reported continuously increasing PAH marine organisms which e.g., contain 4,9-dihydroxipery-
concentrations in sediments of the Tamar Estuary (UK) lene-3,10-quinone as possible perylene precursor under
since 1940 correlating with the increase in traffic. anaerobic conditions in subaquatic sediments (Venkatesan,
Like in soils, the PAH pattern is similar in all sediment 1988), in soils (Blessing, 1996; Guggenberger et al., 1996;
cores of the temperate region. All studies show that PAH Wilcke et al., 1999b), and in termite nests (Wilcke et al.,
patterns changed from being dominated by perylene of 2000). From the occurrence of phenanthrene, methyl-
biological origin in deep sediment layers (Venkatesan, 1988) phenanthrene and methyl-anthracene in preindustrial lake
to other PAHs in more recent sediment layers. sediments, Wickstrm and Tolonen (1987) suspected that
these compounds may be produced biologically. Similar
conclusions had already been drawn by Laflamme and Hites
2.11 Source identification
(1978) who detected the phenanthrene homologues retene
The sources of PAHs are discussed in a range of reviews (1-methyl-7-iso-propylphenanthrene) and pimanthrene (1,7-
(e.g. Sims and Overcash, 1983; Nikolaou et al., 1984; Baek dimethyl-phenanthrene) in noncontaminated remote soils
et al., 1991). Briefly, the major PAH source is incomplete and sediments and assumed that these compounds result

Table 4: Ratios of individual PAHs in emissions of specific fuels and aerosols affected by specific fuels (Freeman and Cattell, 1990; Jacob et al., 1993;
Aboul-Kassim and Simoneit, 1995; Khalili et al., 1995).
Tabelle 4: Verhltnisse einzelner PAK in Emissionen spezifischer Brennstoffe bzw. in Aerosolen, die von spezifischen Emissionen betroffen sind
(Freeman and Cattell, 1990; Jacob et al., 1993; Aboul-Kassim and Simoneit, 1995; Khalili et al., 1995).

FLUA PYR CHRY B(BJK) B(A)P FLUA PYR B(A)A CHRY B(A)P DIBE B(GHI) PHEN/ B(A)A/ B(E)P/ IND/
/B(E)P /IND (ANTH+PHEN) (B(A)A+ (B(E)P+ (IND+
CHRY+TRI) B(A)P) B(GHI))

Lignite 8 5 3 4 1.7
Hard coal 7 6.5 2.2 3 1
Diesel 7 8 1 2 0.5
Petrol 20 35 3 1 1
Oil 80 25 30 4 0.2 0.98 0.16 0.87
Used motor 0.78 0.50 0.64 0.25
oil
Car 0.3 0.9 0.1 1.0 0.77 0.53 0.18
emissions,
gasoline
Coal soot 0.30 0.56
Coke oven 0.67 0.43 0.23
emission
Vegetation 2.2 2.0 0.9 2.0 0.6 0.1 0.3
fire 13.3 19.5 3.9 10.0 10.0 0.7 0.8

Abbreviations: ACEN = acenaphthene, ACENY = acenaphthylene, ANTH = anthracene, B(A)A = benz(a)anthracene, B(A)P = benzo(a)pyrene, B(BJK) =
benzo(b+j+k)fluoranthenes, B(E)P = benzo(e)pyrene, B(GHI) = benzo(ghi)perylene, CHRY = chrysene, DIBE = dibenz(a,h)anthracene, FLUA =
fluoranthene, FLUO = fluorene, IND = indeno(1,2,3-cd)pyrene, NAPH = naphthalene, PERY = perylene, PHEN = phenanthrene, PYR = pyrene, TRI =
triphenylene.
240 Wilcke

from the reduction of abietic and pimaric acid which occur sorbing PAHs strongly. Sorption of PAHs has been shown to
e.g., in Pinus species. Wilcke et al. (1999a, b, 2000) found resemble the partitioning of PAHs among water and an
substantial phenanthrene concentrations in tropical soils and organic solvent. The most important observations from PAH
also assumed biological phenanthrene sources. Furthermore, sorption experiments include that there is no curvature of the
naphthalene was detected in Magnolia flowers (Azuma et al., sorption isotherms up to 50% saturation of the sorbent, PAH
1996), forehead hair of deer (Gasset et al., 1997), and termite sorption is rapid and endogenous indicating that it is an
nests (Chen et al., 1998a, b; Wilcke et al., 2000) which also entropy-driven process (Chiou et al., 1979; Means et al.,
points at biological production. Initial results of Wilcke et al. 1980; Chiou et al., 1983, 1998). While early work on PAH
(2000) indicate that in tropical regions the naphthalene sorption indicated that there were no competitive effects in
production in termite nests and woody plants may be the sorption of certain aromatic compounds to soil (Chiou et
considerable. al., 1983) recent experiments have shown strong interactions
Although transformation processes during atmospheric e.g., between phenanthrene and pyrene (White and Pigna-
transport, deposition, and in soils result in similar PAH tello, 1999). Two phases of PAH sorption take place. The
patterns in temperate soils, diffences in the mixture of the first is a rapid one probably corresponding to the sorption to
more persistent highly condensed PAHs may give hints at sites near the surface of organic macromolecules. The
possible sources of PAHs in soils (Wilcke et al., 1997, 1999a, second process is slow (aging) and may be explained by the
b). Methods to trace PAH sources include the comparison of diffusion of PAHs to internal binding sites (Weissenfels et
ratios among individual PAHs with those of specific sources. al., 1992).
Statistical methods such as cluster and principal component While early work did not consider the influence of organic
analyses have been used to identify the sources of PAHs matter quality on PAH sorption (Means et al., 1980; Sullivan
sorbed to aerosols (Aceves and Grimalt, 1993; Aboul-Kassim and Mix, 1985), in recent work there are indications that soil
and Simoneit, 1995) and in soils (Wilcke et al., 1997, 1999a, organic matter (SOM) quality influences PAH sorption.
b). To distinguish between PAHs from traffic exhausts and Schoone et al. (1997) observed an increasingly stronger
other sources the benzo(ghi)perylene to indeno(1,2,3- sorption of pyrene the less polar SOM is. In their study,
cd)pyrene ratio is most suitable as benzo(ghi)perylene is polarity was measured as the ratio of carboxyl-C+O-alkyl-C
considered as particular marker for traffic exhausts (Kasper- to aryl-C+alkyl-C. However, in the same work no relation-
owski and Frank, 1989; Freeman and Cattell, 1990; ship between the sorption of phenanthrene and any SOM
Menichini, 1992). Lee et al. (1990) used the PAH/Pb ratio property was observed. Chiou et al. (1998) found a more
to distinguish between domestic fire and traffic emissions. pronounced sorption of PAHs to sediments than to soils and
However, with increasing use of unleaded gasoline the assumed that sediment organic matter is less polar.
correlation between PAHs and Pb from traffic exhausts will Raber and Kgel-Knabner (1995) determined desorption
disappear. Statistical methods have been used to separate isotherms and found a rapid linear desorption. The PAH
soils contaminated by a specific emitter, e.g., an Al smelter concentrations in the water used for the desorption experi-
from uncontaminated soils (Soft Independent Modeling of ment reached 90% of the equilibrium concentrations after
Class Analogy SIMCA, Vogt et al., 1987) or to elucidate 14 hours and 100% after 24 hours. Desorption may be
the impact of Al and Mn smelters on the PAH composition in enhanced by dissolution of organic matter serving as PAH
marine sediments (Ns and Oug, 1997). Khalili et al. (1995) carrier or by the presence of organic solvents like anthracene
proposed the Chemical Mass Balance Receptor Model oil which is found at many industrially contaminated sites
which allows for the calculation of the contributions of (Tebaay et al., 1991; 1992).
various known sources to the PAH pattern found in aerosols. Simmleit and Herrmann (1987b) found that the sorption of
As the model does not take into account possible trans- PAHs to the residual silicate material of limestone weath-
formations of the PAH pattern between the emitter and the ering was ten times lower than to an A horizon; the sorption
receptor its use for soils is limited. Tab. 4 summarizes some of PAHs to dolomite powder was 10100 times lower.
source-related ratios of individual PAHs. Leichtle and Totsche (1997) reported that PAHs were sorbed
to all of almost C-free sea sand, goethite-covered sand, and
3 Processes in soil montmorillonite. Sorption to these materials depends on the
specific surface area and increases in the order sand <
3.1 Sorption goethite-covered sand < montmorillonite. The sorption
Sorption and desorption are crucial processes for PAH isotherms are not linear, sand and montmorillonite show a
bioavailability and PAH transport in soil. The literature saturation curve, goethite exhibits cooperative sorption. The
about sorption of PAHs to soil has been reviewed by sorption to all materials is completely reversible.
Dzombak and Luthy (1984) and recently by Marschner Sorption of PAHs has been described by the partition
(1999). Therefore, only the most important results on PAH coefficient (K) normalized to the organic carbon fraction
sorption are briefly presented. (fOC, Equation 1):
SOM is the most important sorbent of PAHs (Means et al., KOC = K/fOC (1)
1980; Sims and Overcash, 1983; Dzombak and Luthy, 1984).
However, Gustafsson et al. (1997) have shown that soot- The KOC may be estimated from the octanol-water partition
like C or black C in soil resulting from vegetation fires and coefficient KOW and from the water solubility of the liquid or
soot deposition from the atmosphere is also capable of subcooled liquid compounds (SW). In the literature a range
PAHs in soil a review 241

of equations have been proposed to estimate KOC from KOW Several authors observed a mobility-increasing effect of
or SW (Equations 27). PAHs by a synthetic polysaccharide (Bengtsson et al., 1987)
log KOC = log KOW 0.317 (Means et al., 1980) (2) and complex natural organic macromolecules (Enfield et al.,
log KOC = 0.989 log KOW 0.346 (Karickhoff, 1984) (3) 1989; Kan and Tomson, 1990; Magee et al., 1991) in water-
log KOC = 0.54 log SW + 0.44 (Karickhoff et al., 1979) (4) saturated soil columns containing < 2 g kg1 organic C. The
log KOC = 0.686 log SW + 4.273 (Means et al., 1980) (5) effect is more pronounced for high molecular weight PAHs
log KOC = 0.729 log SW + 0.001 (Chiou et al., 1983) (6) (e.g., pyrene, benzo(a)pyrene) than for low molecular weight
log KOC = 0.57 log SW + 5.19 (Nielsen et al., 1997) (7) PAHs (e.g., anthracene, Enfield et al., 1989; Johnson and
SW is in mol l-1 except for equations (6) and (7) (mg l-1). Amy, 1995). However, in soil columns containing either C-
Miller et al. (1985) have shown that the log-log plot of KOW poor or C-rich material which was not water-saturated, the
versus SW of PAHs is linear with a slope of 0.8. However, presence of DOM may also reduce PAH mobility because of
the authors doubt that octanol is a suitable SOM surrogate. the sorption of the carrier to soil solid phase (cosorption of
Dzombak and Luthy (1984) summarize possibilities to PAHs, Totsche et al., 1997). Subsoil horizons rich in Fe
estimate the KOW from molecular properties. oxides, like spodic horizons, may act as barrier for PAH
transport because DOM is strongly retained (Guggenberger
et al., 1996; Wilcke et al., 1996a; Totsche et al., 1997). In a
3.2 Transport column experiment, Marschner (1995) studied the effect of
Although PAHs are strongly sorbed in soil they are found at varying pH on the transport of benzo(a)pyrene in a trickle-
greater soil depth indicating leaching (Wild and Jones, 1995; field soil leached with distilled water. It was found that
Wilcke et al., 1996b; Krau et al., 2000). Based on the acidification from pH 5.7 to 3.3 resulted in increased DOM
analysis of archived soil samples, Jones et al. (1989b) but in reduced benzo(a)pyrene leaching, probably because
estimated PAH leaching rates of 0.0090.14 mg m1 a1. In the released DOM mainly consisted of hydrophilic acids
their study, the leaching rate did not decrease with increasing having low affinity for PAHs.
molecular weight to the extent one would expect from water Furthermore, the partitioning of PAHs among soil solid
solubilities of the individual compounds. This indicated phase, soil water, and DOM is crucial for PAH leaching. The
DOM-mediated or particle-associated PAH transport of the sorption of PAHs to DOM may be studied with various
high molecular weight PAHs. Deschauer (1995) calculated methods. Among the most frequently used are solubility
field KOC values for the Oa horizon using PAH concen- enhancement (Gauthier et al., 1987; Chin et al., 1997),
trations in soil solution. The KOC values of the low molecular fluorescence quenching (Gauthier et al., 1986), dialysis
weight PAHs (up to four fused rings) were higher than KOC
(McCarthy and Jimenez, 1985), and solid phase extraction
values determined in the laboratory, those of the high
(C18 columns, reverse phase HPLC, Landrum et al., 1984;
molecular weight PAHs were lower or equal. Possible
reasons for lower field KOC than laboratory KOC include Maxin and Kgel-Knabner, 1995). The results have been
nonequilibrium conditions, lateral flow, and desorption summarized by Marschner (1999). Methodological prob-
hysteresis. Enhanced solubility of the higher molecular lems of the various methods are discussed in Gauthier et al.
PAHs may be caused by association with DOM (Gauthier (1986) and in Maxin (1992). Briefly, the sorption process to
et al., 1987; Maxin and Kgel-Knabner, 1995; Chin et al., DOM is similar to that of solid phase organic matter, it is a
1997). linear, fast, and reversible partitioning process which may be
Simmleit and Herrmann (1987a, b) detected substantial described with the partition coefficient normalized to
PAH concentrations in a Karst source following snow dissolved organic C (KDOC). The partition coefficient KDOC
melting. Their results indicated that almost no PAHs were is related with KOC according to Equation 8.
transported as truly dissolved solute but associated with KOCeff = KOC (1+CDOC x KDOC)1 (8)
particulate matter. Comparison of the PAH output with the where KOCeff is the apparent partition coefficient between
source water and PAH input data suggested that 99% of the soil organic C and soil solution and CDOC is the concen-
input is retained in the uppermost 2 m of soil. In contrast, tration of dissolved organic C in soil solution.
Blessing (1996) reported that about 50% of the input left a There is evidence that the quality of DOM and solution
small Alpine catchment with surface flow after having properties such as pH and ionic composition are much more
passed through the soils. The similarity of the PAH mixtures important for PAH-DOM than for PAH-solid organic matter
in the rainwater and in the surface water suggested that association. The association of PAHs with DOM depends on
PAHs were transported along preferential flow paths without the polarity, molecular size, configuration, and chemical
much interaction with soil solid phase. composition of the carrier molecule. It has been shown that
To describe the transport of PAHs, a model which large molecules containing nonpolar domains such as humic
considers the solid, the dissolved, and the particle-/colloid- acids have a higher capacity to bind organic contaminants
associated phase is widely used (McCarthy and Zachara, than the more polar fulvic acids (Chiou et al., 1983, 1986).
1989; Johnson and Amy, 1995; Totsche, 1995). Particularly Gauthier et al. (1986, 1987) and McCarthy et al. (1989) have
DOM may act as PAH carrier thus increasing PAH mobility. shown that increasing aromaticity increases KDOC of PAHs.
DOM interacts with the soil solid phase and may be While Gauthier et al. (1986) for pyrene and Nielsen et al.
microbially altered, produced or consumed resulting in (1997) for a range of PAHs found increasing KDOC with
changing DOM quality over time and space (Kaiser, 1996; decreasing pH, Jones and Tiller (1999) reported increasing
Totsche et al., 1997). KDOC for phenanthrene with increasing pH at low ionic
242 Wilcke

strength (0.001 M) and no effect of pH on KDOC of PAHs were spiked to a sandy soil, amended with a mineral
phenanthrene at ionic strengths between 0.001 and 0.01 M. medium, and continuously stirred in a bioreactor. Mackay
Jones and Tiller (1999) also demonstrated that KDOC for and Leinonen (1975) found surprisingly high volatilization
phenanthrene increases with decreasing ionic strength rates from open water bodies even for higher molecular
probably because of a more open configuration of the PAHs. Wilcke et al. (1999b) suspected that low PAH
DOM molecules and less cation bridging. The latter concentrations in urban soils of Bangkok may partly be
assumption is further supported by the finding that KDOC explained with volatilization possibly enhanced by frequent
for phenanthrene decreases with increasing valence of the soil water saturation, high temperatures, and frequent
cation in soil solution at constant ionic strength. After drying-rewetting cycles. However, this hypothesis needs
sorption of the humic acids used as DOM surrogate to clay further substantiation. Up to now, nothing is known about
minerals KOC for phenanthrene is reduced compared with volatilization rates of field-aged PAHs. In all published
the dissolved state. The remaining dissolved fraction of the research work on volatilization rates, PAHs were spiked to
humic acids has a lower capacity to sorb phenanthrene. The the studied soil prior to the measurement of volatilization
valence of the cations in soil solution at constant ionic rates.
strength affects phenanthrene sorption to clay mineral-
sorbed humic acids in the same way as sorption to the 3.4 Transfer soil biosphere
dissolved humic acids, i.e. KOC decreases with increasing
valence. Soil PAHs may be transferred to plants and to animals and
humans directly by soil ingestion or indirectly via plants
(Knoche et al., 1995). The bioavailability of PAHs, i.e. the
3.3 Volatilization potential to be transferred from soil to living organisms
depends on their hydrophilicity and on their binding in soil
Volatilization may be an important pathway of PAH loss,
(Alexander, 1995; Beck et al., 1996). The more water-
particularly for low molecular weight compounds. However,
soluble a PAH is, the higher is the uptake by plants
volatilization of PAHs is still poorly understood and
(Crmann, 1992) while the reverse is true for the uptake by
warrants further research (Wild and Jones, 1995). This
earthworms (Van Brummelen et al., 1996b) or in the
includes the development of methods which allow for
gastrointestinal tract of cows (Beck et al., 1996). With
distinguishing appropriately between the various abiotic
increasing residence time of PAHs in soils their extract-
disappearence rates (Park et al., 1990a). The volatilization
ability, degradability, and toxicity decrease due to aging
rate is presumed to depend on the Henry coefficient, wind
(Alexander, 1995; Hatzinger and Alexander, 1995; Beck
speed, atmospheric turbulence, and temperature (Sims and
et al., 1996). The solubility enhancement of PAHs by
Overcash, 1983). Ophoff et al. (1996) assumed that soil
association with DOM may not result in increased bioavail-
moisture had an indirect influence on volatilization rates of
ability (McCarthy et al., 1989).
fluoranthene via soil water evaporation. These authors
furthermore found a diurnal fluctuation of the volatilization Transfer (or bioconcentration) factors (TFs or BCFs) are
rates of fluoranthene and concluded that air temperature had calculated as a measure for the extent of PAH transfer from
a major influence on volatilization rates. soil to plants or animals (Equation 9).
Park et al. (1990b) reported 30% volatilization loss of the TF = cbiomass/csoil (9)
naphthalene spiked to two C-poor soils which were held at a where cbiomass is the PAH concentration in plants or animals
moisture content of about 60% of the field capacity within and csoil that in the soil. TF is unitless.
2 days. In contrast, only < 0.1% of three-ring PAHs Transfer factors for plants are small and range between
(anthracene and phenanthrene) are volatilized in the same 0.001 and 0.4 with the majority being lower than 0.01
time period. Goodin and Webber (1995) found about 0.2% (Edwards, 1983; Crmann, 1992; Goodin and Webber,
volatilization loss of anthracene spiked to soil grown with 1995). The determination of the TFs is complicated by the
rye grass, soybean, and cabbage after 14 weeks and no fact that PAHs enter plants not only from soil but also from
detectable volatilization loss of benzo(a)pyrene. Ophoff et the atmosphere (Beck et al., 1996) and from soil particles
al. (1996) observed a loss of 12.433.6% of the radioactivity adhering to the plant tissue as a consequence of splash due to
of surface-applied 14C-labeled fluoranthene within 14 d in a rain drop impact (Delschen et al., 1999). In animals and
wind tunnel experiment. They found that 8990% of the plants, PAH metabolism may also affect the determination
volatilized radioactivity was the original fluoranthene; only of TFs (Edwards, 1983; Pathirana et al., 1994; Van
minor amounts of metabolites were detected. When the Brummelen et al., 1996b). This may explain the weak
fluoranthene was incorporated into the soils only between correlations between soil and plant/animal PAH concen-
1.4 and 1.8% of the applied radioactivity were lost by trations (e.g. Hembrock-Heger et al., 1992; Pathirana et al.,
volatilization. The volatilization rates were highest during 1994; Van Brummelen et al., 1996b). Nevertheless, the
the first days after application. After about 4 days lower uptake of PAHs by plants from soil has been shown to be
constant rates were observed. The volatilization of PAHs likely using 14C-marked compounds (Knoche et al., 1995;
may also depend on soil redox potential. Volatilization Schnder, 1995). However, with this approach it may not be
losses of acenaphthene, acenaphthylene, fluorene, and ruled out completely that the 14C activity in plants is related
anthracene under denitrifying conditions are considerably with degradation products but not the originally spiked
lower than under aerobic conditions (Leduc et al., 1992). The PAHs. Furthermore, these experiments have been conducted
PAHs in soil a review 243

with spiked soil where PAHs will be more bioavailable than However, up to now little is known about the climatic effect
in soils with aged PAH contamination. Crmann (1992) on the PAH patterns on a global scale.
found increasing PAH concentrations in plants with The bioavailability and mobility of PAHs depend on PAH
increasing concentrations in soil. sorption and sequestration in soils. Although much research
The most important source of PAHs for plants is the has been addressed to the partitioning of organic contam-
atmosphere from where PAHs may enter plants via the inants between soil solution and soil solid phase, still little is
gaseous phase or deposit bound to particles on plant surfaces known about the binding types and mechanisms and about
(Sims and Overcash, 1983; Hembrock-Heger et al., 1992; the influence of SOM quality and soil solution composition
Knoche et al., 1995). This is reflected by higher PAH on PAH sorption.
concentrations in plants with large surface areas and by It is well known that only part of the total PAH
similar PAH patterns in different plant compartments (Jones concentrations in soil is available to organisms and leaching.
et al., 1989a; Hembrock-Heger et al., 1992; Wild et al., However, there are still no reliable methods to characterize
1992). Wild et al. (1992) also reported a higher similarity PAH pools differing with respect to their bioavailability.
between PAH patterns of airborne particles and gaseous Furthermore, it has been shown that PAHs are unevenly
PAHs in the atmosphere and plant compartments than distributed among various soil pools. Further research is
between soil PAH patterns and those in plants. However, necessary to address the influence of the heterogeneous
airborne PAH patterns were not identical to those in the distribution of PAHs in soil on PAH bioavailability and
plants which may indicate that PAHs in plants result from reactivity.
both atmospheric and to a smaller extent soil uptake,
although the air samples in the study of Wild et al. (1992)
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