Atmospheric Environment 36 (2002) 5395–5403

Atmospheric bulk deposition of PAHs onto France: trendsfrom urban to remote sites

B. Garbana,*, H. Blanchouda, A. Motelay-Masseib, M. Chevreuila, D. Ollivona

aLaboratoire Hydrologie et Environnement, Ecole Pratique des Hautes Etudes, UMR Sisyphe 7619, Universit!e Pierre et Marie Curie,

4 place Jussieu, case 122, 75252 Paris cedex 05, FrancebLaboratoire de G!eologie Appliqu!ee, UMR Sisyphe 7619, Universit!e Pierre et Marie Curie, 4 place Jussieu, 75252 Paris cedex 05, France

Received 15 March 2002; received in revised form 11 June 2002; accepted 19 June 2002

Abstract

Fifty-eight weekly samples of atmospheric bulk deposition (dry and wet) were collected in France at six specific sites

over a year. Urban, semi-rural, rural and forested sites were chosen on a transverse from West to East at the Paris

latitude. Seasonal variations are described, with winter time concentrations 2–3 times higher than summer ones due to

an increase in fossil fuel consumption in winter. When temperature did not exceed 121C, mean PAH concentrations

varied from 221 ng l�1 in Paris to 25 ng l�1 at a rural site. About 50 km far from Paris, PAH concentrations decreased

by two-thirds. Urban emissions have a local impact on the fallout contamination. Fluxes at the Paris site (from

157–1294 ngm�2 d�1) were from 2.5–6 times higher than in the rural and forested sites. In the latter sites, mean daily

fluxes (50 ngm�2 d�1) were close to those of high European mountains, considered as background levels. In rural sites,

without treatment plant sludge spreading, atmospheric deposition is the major source of PAH inputs to soils.

r 2002 Elsevier Science Ltd. All rights reserved.

Keywords: PAHs; Bulk deposition; Transport; Flux; Seasonal variation

1. Introduction

Polycyclic aromatic hydrocarbons (PAHs) are ubiqui-

tous contaminants of great environmental concern, by-

products from the incomplete combustion of fossil fuels

and wood. Forest fires and volcanoes contribute to the

PAH burden. However, residential heating, coke pro-

duction, incineration and internal combustion engine

are by far major sources of PAHs (Baek et al., 1991;

Harvey, 1997).

Sixteen unsubstituted PAHs, some of which are

considered as being possible or probable human

carcinogens, have been listed by the US Environmental

Protection Agency (EPA) as priority pollutants. Once

they enter the atmosphere, PAHs are redistributed

between gas and particle phases and are subject to

removal mechanisms such as oxidative and photolytic

reactions and wet and dry deposition. During precipita-

tion, PAHs both in gaseous and aerosol forms are

scavenged from the atmosphere by rainwater (Ligocki

et al., 1985a, b; Dickhut and Gustafson, 1995; Hillery

et al., 1998). When deposited, they may be remobilised

and transported by air masses and winds over long

distances to settle again on land and water surfaces.

Thus, PAHs have been found in samples collected in

remote high European mountains (Steinberg et al., 1989;

Carrera et al., 2001) and in Greenland polar ice (Jaffrezo

et al., 1994; Masclet et al., 1995, 2000) or Canadian

arctic (Barrie et al., 1992; Macdonald et al., 2000).

Therefore, atmospheric transport and deposition are

important pathways of PAHs to ecosystems far from

source areas (Barrie et al., 1992) and shown by long-

range transport modelling (Mackay and Wania, 1995;

Di Toro and Hellweger, 1999; Pekar et al., 1999; Beyer

et al., 2000; Halsall et al., 2001).*Corresponding author. Fax: +33-1-44-27-51-25.

E-mail address: Brigitte.Garban@ccr.jussieu.fr (B. Garban).

1352-2310/02/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved.

PII: S 1 3 5 2 - 2 3 1 0 ( 0 2 ) 0 0 4 1 4 - 4

There is a growing concern about pollution by

persistent organic pollutants (POPs) including PAHs.

In May 2001, a global treaty for the regulation of POPs

was signed: the ‘‘Stockholm Convention’’ which in-

cludes instruments for the total elimination of 12 POPs

on a global scale. Large-scale programs are conducted in

relation to the long-range transboundary atmospheric

pollution (EMEP) or their discharge into the sea

(OSPAR). To these 12 POPs, the United Nations-

European Community added the PAHs of which

benzo(a)pyrene (BaP) is the most toxic. The objective

is to control, reduce or eliminate discharges, emissions

and losses of POPs.

In this context, knowledge on the pollution level and

its dispersion on regional and national scale is essential.

In France, PAH deposition data have been collected in

the Paris area (Ollivon et al., 1999, 2002), but no data

are available for other sites.

This study was part of the PIREN-Seine program

concerning atmospheric loading of POPs on the river

Seine catchment and their comparison with remote sites

(Brittany and Vosges forest). Our purpose was to carry

out measurements in bulk deposition (including wet and

dry deposition) in urban, rural and forested regions in

France and study the progression of the contamination

by PAHs over a West–East transverse, then to assess

daily and annual PAH atmospheric loading.

2. Experimental

2.1. Study area

According to the main wind directions (220–2751)

over France, sampling sites were set up on a transverse

from West to East and close to meteorological stations,

at Ouessant (481280N–51030W), Pleumeur-Bodou

(481460N–31310W), Paris (481490N–21290E), Coulom-

miers (481500N–31000E), Eclaron (481320N–41450E),

Abreschviller (481370N–71O50E) (Fig. 1). Ouessant is a

small island (932 inhabitants) located at a few miles

from the Western point of Brittany. The rain sampler

managed by the Navy was located on the west coast in a

wild moor. The Pleumeur-Bodou rain sampler was

located in a rural area. The nearest city (18 000

inhabitants) is 6 km away. The Paris rain sampler was

located on the roof of a Paris university (Universit!e

Pierre et Marie Curie), 25m above street level (Paris and

suburbs population adds up to 11 millions inhabitants).

The Coulommiers rain sampler was located in a

suburban agricultural (‘‘rurban’’) village close to Cou-

lommiers (14 000 inhabitants), 10 km away. The

Eclaron rain sampler was situated in a rural region;

the nearest city (33 500 inhabitants) is 40 km away to the

Northeast. The collection site in Abreschviller (1300

inhabitants) was in the Donon Massif (Vosges forest).

All the sites were located in open areas, out of vegetation

cover.

Samples were collected weekly from 17 October 1999

to 26 December 1999, and from 20 March 2000 to 10

October 2000 for all sites, except at Eclaron where

sampling began in March 2000. No snowfall occurred

during the overall sampling periods. The bulk atmo-

spheric deposition (wet and dry) were collected using

open pyramidal stainless steel funnels with a 0.36m2

collection area, collecting up to 70mm of rain without

overflow in a 25 l aluminium tank. The collectors receive

both wet and dry deposition. All apparatus and

containers were previously washed with Milli-Q water,

then with HPLC quality grade acetone and hexane.

Samples were mailed by express package within 2 days

to the laboratory. Once in the laboratory, samples are

stored at 41C in darkness and extracted within 48 h, then

the extract was stored at 41C until analysis.

2.2. Meteorological conditions

Precipitation amounts, wind direction, and tempera-

ture were obtained from Meteo France. At Paris, there

were 175 rainy days during the study corresponding to a

precipitation height of 825mm. At Abreschviller, annual

precipitation height from 17 October 1999 to 08 October

2000 was 1590mm (about twice higher than elsewhere:

Ouessant 907mm; Pleumeur-Bodou 979mm; Coulom-

miers 828mm). Considering only the sampling weeks,

mean daily local temperatures ranged from 7.41C to

12.81C at Ouessant, 7.1–13.41C at Pleumeur-Bodou,

8.2–19.71C at Paris, 6.4–171C at Coulommiers, 7.4–

18.91C at Eclaron and 2.2–16.61C at Abreschviller. The

prevailing winds were westerly and southwesterly as

shown in Fig. 1 where annual wind roses are displayed

for three sites.

2.3. Analytical procedure

Raw samples including wet and dry deposition were

extracted using a liquid–liquid technique. Samples were

shaken 3 times for 20min in a glass bottle, using 100ml

of a hexane/methylene chloride mixture (v/v 85/15) for

each litre of sample (Ollivon et al., 1999). Extracts were

combined and reduced to 3ml on a rotary evaporator;

after removal of sulphides by adding mercury, no

further purification was performed. As the elution

solvent for HPLC is acetonitrile/water, hexane had to

be exchanged to acetonitrile. For doing so, methylene

chloride and acetonitrile were added to the reduced

extract in a 3/1/1 proportion for hexane/methylene

chloride/acetonitrile, respectively. Then the mixture was

concentrated to about 0.5ml and subjected to liquid

chromatographic analysis.

The identity of each PAH was confirmed by the use of

a standard mixture (PAH-Mix 9 in acetonitrile from

B. Garban et al. / Atmospheric Environment 36 (2002) 5395–54035396

Dr Ehrenstorfer GmbH, Augsburg, Germany) contain-

ing the 16 PAHs recommended by the EPA method No.

610: naphthalene (NAP), acenaphtylene (ACY), ace-

naphtene (ACE), fluorene (FLU), phenanthrene (PHE),

anthracene (ANT), fluoranthene (FTH), pyrene (PYR),

benzo(a)anthracene (BaA), chrysene (CHR), benzo(b)-

fluoranthene (BbF), benzo(k)fluoranthene (BkF), ben-

zo(a)pyrene (BaP), dibenz(a,h)anthracene (DahA),

benzo(g,h,i)perylene (BghiP), and indeno(1,2,3-cd)pyr-

ene (IcdP). When extracted in the same conditions, the

recovery efficiency ranged from 91% to 113% (n ¼ 8).Chromatography of extracts was performed on a

Dionex 4500i chromatograph, equipped with a Vydac

201TP5415 column and two detectors, UV/visible and

fluorimetric. The instrumental conditions are described

in detail elsewhere (Ollivon et al., 1995). Replicate

analyses of standards gave relative standard deviations

(RSD) from74% to78%, and detection limits, in ouranalytical conditions, ranged from 0.06–0.6 ng l�1, both

depending on the PAH analysed. Blanks of ‘‘Albian

aquifer’’ groundwater stored and extracted in the same

conditions were below detection limits and results were

displayed without blank correction. Naphthalene, which

is highly volatile, and acenaphtylene, which is weakly

fluorescent, were not quantified; therefore, ‘‘total

PAHs’’ includes 14 compounds.

3. Results and discussion

3.1. Contamination level

As our purpose was to follow the contamination trend

on the whole transverse, in order to get enough water for

POP analysis, extractions of PAHs were performed

when a minimum of 10mm rainfall occurred at four sites

at least. So during the 39 week sampling period, 58

weekly bulk precipitations were analysed from October

1999 to October 2000. Total PAH concentrations ranged

from 7.6–130 ng l�1 at Ouessant, 1.5–65 ng l�1 at Pleu-

meur-Bodou, 51–323 ng l�1 at Paris, 16–176 ng l�1 at

Coulommiers, 5–28 ng l�1 at Eclaron and 4.8–81 ng l�1

at Abreschviller. Besides, in Paris, monthly sampling

was performed all over the same year and total PAH

concentrations in January reached 995 ng l�1 (Ollivon

et al., 2002).

To display PAH concentration ranges (Fig. 2), two

periods were distinguished according to air temperature.

During the cold period (to121C), concentrations weregenerally higher, reflecting the increase in fossil fuel

consumption in winter. Seasonal variations of PAHs due

to domestic heating have been widely described world-

wide, for atmospheric samples (Baek et al., 1991; Smith

and Harrison, 1996; Coleman et al., 1997; Cortes et al.,

2000; Gigliotti et al., 2000) and precipitation over

Europe (Hart et al., 1993; Halsall et al., 1997; Manoli

et al., 2000; Kiss et al., 2001; Ollivon et al., 2002). The

average PAH concentration in Paris was 221 ng l�1. At

Coulommiers, mean PAH concentration (85 ng l�1)

accounted for the impact of Paris pollution, but the

latter was no longer detected at the eastern sites (25.3

and 29.6 ng l�1 on average at Eclaron and Abreschviller,

respectively). At Ouessant and Pleumeur-Bodou sites,

which we supposed to be background reference sites,

mean PAH concentrations (54.6 and 40.2 ng l�1, respec-

tively) were generally higher than at the other rural and

forest sites. At the Ouessant site, contamination by

intensive boat traffic in the ‘‘rail d’Ouessant’’ might be

considered as a potential source. Moreover, increases of

PAH sorption with salinity in estuaries have been

described (Brunk et al., 1997), and it is therefore

possible that marine aerosols could act the same way

by aggregating PAHs and trapping them.

During the temperate period (t > 121C), the sametrend was observed with lower levels: from Paris to the

eastern sites, mean PAH concentrations decreased from

Fig. 1. Location of the sampling sites. Insets a,b,c, indicate the prevailing winds at the Pleumeur-Bodou, Paris and Abreschviller sites,

respectively. Marne river catchment is figured in gray dotted line.

B. Garban et al. / Atmospheric Environment 36 (2002) 5395–5403 5397

124 to 19.8, 12.3, 14.9 ng l�1, respectively, and levels at

the western sites were 15.1 and 13.4 ng l�1, respectively,

at Ouessant and Pleumeur-Bodou.

Winter concentrations were on average 2–3 times

higher than the summer ones, and can be attributed to:

(a) an increase in consumption of fossil fuel combustible;

(b) an enhancement of the condensation of the PAH

fraction in the gaseous phase as low temperatures lead to

a decrease of the Henry constant. PAH concentrations

were in the same ranges as those reported in the

literature: (i) Kawamura and Kaplan (1983) at Los

Angeles and vicinity described, at urban, semi-rural and

rural sites PAH winter time concentrations of 250, 35,

and 27 ng l�1, respectively; (ii) Leuenberger et al. (1988)

reported in urban rain water in Switzerland PAH

concentrations of 130 ng l�1 in summer, 210 ng l�1 in

spring, and 590 ng l�1 in winter.

Four compounds were generally predominant: phe-

nanthrene, fluoranthene, pyrene and chrysene, that

represented 62–71% of total PAH concentrations. The

six potential carcinogenic PAHs as described by the

International Agency for Research on Cancer (IARC)

(i.e. BaA, BbF, BkF, BaP, DahA, and IcdP) represented

on average 19% of the total PAHs, of which 3% was

benzo(a)pyrene.

3.2. Cross-country dispersion

Nine transverses from West to East were established

when meteorological conditions allowed simultaneous

sampling at 4 sites at least. Concentration trends were as

described previously: Paris is the most urbanised and

industrialised site, and therefore the most polluted one.

PAH concentrations in Paris were from 4 to 20 times

higher than in the coastal, rural or forested sites.

As sampling was performed weekly, it might include

several rain events and, for such a long period, winds

were rarely steady. Therefore, air mass trajectories were

not investigated. However, during the rare weeks when

winds came from West on the transverse, we observed

that the percentage of the heaviest molecular weight

(MW) compounds (C22) decreased from Paris to

Abreschviller, whereas the lightest ones, acenaphtene

and fluorene, increased. Conversely, at the Pleumeur-

Bodou site, C22 compounds were detected mostly with

eastern winds, as displayed in Fig. 3 with PAH patterns.

These figures were established for the cold period,

using mean values of 2 weeks when rain was predomi-

nantly with westerly winds and 3 weeks with easterly

winds. C20 and C22 compounds increased together

0

100

200

300

400

Σ14 PAHTemperature < 12˚C

Ouessant Pleumeur-B Paris Coulommiers Eclaron Abreschviller0

100

200

300

Σ14 PAHTemperature > 12˚C

(a)

(b)

PA

H c

once

ntra

tion

(ng

L-1)

PA

H c

once

ntra

tion

(ng

L-1)

Fig. 2. Statistics of weekly PAH concentrations at the six sites

during (a) cold period (to121C) and (b) temperate period(t > 121C). Boxes show the range between the 25th and 75thpercentiles. The whiskers extend from the edge of the box to the

5th and 95th percentile of the data. The horizontal line inside

indicates the median value.

Fig. 3. Mean relative PAH distribution at the Pleumeur-Bodou

site according to the wind direction. Values in brackets were not

quantified.

B. Garban et al. / Atmospheric Environment 36 (2002) 5395–54035398

from 4% to 16%, respectively, according to wind

direction. PAH finger prints were very different: by

eastern winds, the occurrence of the heaviest MW

PAHs, typical of anthropogenic pollution, indicates that

they are mainly transported from continental, distant

and urbanised areas, since by oceanic winds they are

negligible.

On the one hand, we tried to correlate the deposition

with local sources and on the other hand, we tried to

correlate the deposition with the transport from Paris

area. As PAH sources are mainly anthropogenic, the

local emissions were highlighted by the correlation

between PAH concentrations in bulk deposition and

population density at each area (Fig. 4). Determination

coefficients were high but we missed intermediate values

of population density to certify the correlation.

PAH concentrations decreased proportionally from

the distance from the main pollutant source, e.g. Paris.

Concentration data (Cx) fit the following relationship

Cx ¼ C0e�kx where C0 is the concentration measured in

Paris, k a dilution/loss coefficient function of physico-

chemical properties of each compound and meteorolo-

gical conditions and x the distance from Paris. The

linear regression curves for the four predominant PAHs

plus benzo(a)pyrene are displayed in Fig. 5. On the

whole, the higher the vapour pressure, the smaller the

coefficient k (kPHE ¼ 0:0027 and kBAP ¼ 0:0048).Obviously, both, distance from pollution sources and

population density, are factors which influence the

atmospheric pollution. The longer the distance from

main source, the more important the relative contribu-

tion of local input.

3.3. Deposition fluxes

Daily bulk deposition of total PAHs were calculated

and compared to other PAH fluxes worldwide in similar

environmental areas (Table 1).

At the Paris site, bulk deposition was from 2.5 to 6

times higher than those in the rural and forested sites,

but daily fluxes (157–1294 ngm�2 d�1) were lower than

those reported by Halsall et al. (1997) in 1991–1992 at

Manchester and Cardiff (UK), that are highly indus-

trialised cities. At the Ouessant site, daily fluxes were in

agreement with those calculated by Brorstr .om-Lunden

(1996) for the Swedish west coast, and by Lipiatou et al.

(1997) for sites over Mediterranean sea. Generally, bulk

deposition is in good agreement with those reported by

the PAH pilot study built up by the OSPAR commission

(2001). This commission studied typical areas similar to

ours: Belgium urban, German coastal, Swedish rural,

and Danish forested sites. The lowest PAH deposition

fluxes were found for temperate periods in rural and

forested sites, at about 50 ngm�2 d�1. These values are

close to those determined in remote sites, and considered

as background deposition: from 11 to 100 ngm�2 d�1

onto European high mountains (Carrera et al., 2001),

and from 14 to 46 ngm�2 d�1 (S7 PAHs includingnaphthalene) onto the Agassiz Ice Cap (Canada) (Peters

et al., 1995).

We attempted to assess annual fluxes from respective

mean daily fluxes in cold and temperate periods, each

0

50

100

150

200

250

0 200 400 600 800 1000

Population density (inhabitants.Km-2)

Co

nce

ntr

atio

n (

ng

.L-1

)

t <12˚CR2 = 0.99

t >12˚CR2 = 0.98

(P)

(PB)

(C)

(E)(A)

Fig. 4. Correlation between PAH concentrations in bulk

deposition and population density during cold (to121C) andtemperate (t > 121C) periods at Pleumeur-Bodou (PB), Paris(P), Coulommiers (C), Eclaron (E), and Abreschviller (A).

Fig. 5. Relationship between LogC/C0 (see text) and distance

from Paris during the 2–10 October 2000 week for PHE, FTH,

PYR, CHR, and BaP.

B. Garban et al. / Atmospheric Environment 36 (2002) 5395–5403 5399

accounting for six months. It is likely that the fluxes

were underestimated due to the lack of values during the

coldest months (January and February), when the

highest PAH concentrations are usually observed. So,

we attempted to estimate total annual deposition fluxes

from monthly deposition calculated from mean weekly

concentrations and monthly rainfall. Missing data were

extrapolated and added to obtain the annual deposition.

It yields at Pleumeur-Bodou 52 mgm�2 yr�1, Paris

227mgm�2 yr�1, Coulommiers 91mgm�2 yr�1, Eclaron

59mgm�2 yr�1, Abreschviller 68 mgm�2 yr�1. The dis-

crepancy between the two calculations were 19%; 11%;

35%; 40%, and 44%, respectively, increasing as a

function of median winter temperature. At the Paris

site, we can compare this flux estimation

(227mgm�2 yr�1) from sequential weekly concentrations

to the total deposition calculated from a continuous

bimonthly sampling (234mgm�2 yr�1 for S14 PAHS) forthe same period (Ollivon et al., 2002). The excellent

agreement, with only 3% discrepancy validates the

calculation. In the same way, benzo(a)pyrene deposition

for Paris was estimated at 8.5 mgm�2 yr�1 and about

1.5mgm�2 yr�1 at the other sites. According to the site,

winter deposition ranged from 70% to 87% of total

annual flux.

Using the estimations of atmospheric bulk deposition

in typical areas, i.e. urban, rurban and rural, it was

therefore possible to assess the annual PAH atmospheric

deposition onto a wider region made up of a number of

typical areas. Then, we estimated the PAH deposition

from the atmosphere onto the Marne river basin. This

catchment (12 640 km2) can be split up into three distinct

zones according to population density: 10% urban, 14%

rurban and 76% rural (Meybeck et al., 1998), to which

were assigned annual fluxes of Paris, Coulommiers and

Eclaron, respectively. In this way the PAH loading to

the Marne river basin was estimated at 1010 kg yr�1.

For the whole country (551 602 km2), where urban

areas represent 18.4% (Chavouet and Fanouillet, 2000),

total PAH atmospheric deposition was estimated at

about 48 t yr�1 including 1.5 t yr�1 of benzo(a)pyrene.

Using models based on emission estimates, Shatalov

et al. (2000) calculated a total benzo(a)pyrene deposition

of 5.74 t yr�1. More recently, Ollivon et al. (2002)

assumed the maximal annual benzo(a)pyrene deposition

to be 2.9 t yr�1 for the same area.

The atmospheric deposition of PAHs is known to be

one of the major sources of PAHs in soil (KEMI, 1995).

We can compare inputs to soil, first via atmospheric

deposition, second via spreading of sludges from an

urban waste water treatment plant. Concerning the

sludge, European legislation takes into account only 3

PAHs: fluoranthene, benzo(b)fluoranthene and ben-

zo(a)pyrene. As estimated above at Coulommiers, which

Table 1

Comparison of daily bulk PAH deposition (ngm�2 d�1) at various environmental sites in France with other similar sites worldwide

PAHs (ngm�2 d�1) Coastal Coastal-rural Urban Rurban Rural Forest

France (this study)a

Oct. 1999–2000

(O) n ¼ 8 (PB) n ¼ 9 (P) n ¼ 13 (C) n ¼ 10 (E) n ¼ 5 (A) n ¼ 13

to121C 104–620 (291) 49–274 (179) 355–1294

(794)

2–631 (285) 110–149 (130) 27–493 (161)

t > 121C 54–213 (128) 10–102 (53) 157–655 (333) 19–93 (42) 20–94 (70) 12–92 (50)

Chesapeake Bay 1991

(a)

420–540

Manchester 1991–

1992 (b)

Cardiff 1991–1992 1000–24 200

800–19 600

Swedish West coast

(c)

April 1991–June 1994 100–650

Northern Greece (d)

Sept. 1996–May 1997 200–1100

Europe (e) 260 1100 460 430

Mediterranean sea (f) 112–225

aS14 PAHs including: acenaphtene (ACE), fluorene (FLU), phenanthrene (PHE), anthracene (ANT), fluoranthene (FTH), pyrene(PYR), benzo(a)anthracene (BaA), chrysene (CHR), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP),

dibenz(a,h)anthracene (DahA), benzo(g,h,i)perylene (BghiP), indeno(1,2,3-cd)pyrene (IcdP).

(O) Ouessant; (PB) Pleumeur-Bodou; (P) Paris-Jussieu; (C) Coulommiers; (E) Eclaron; (A) Abreschviller.

(a) Dickhut and Gustafson (1995) S14 PAHs; (b) Halsall et al. (1997) S13 PAHs; (c) Br .orstrom-Lunden (1996) S11 PAHs; (d) Manoliet al. (2000) S15 PAHs; (e) OSPAR Oct.–Nov.–Dec. 1998 S12 PAHs; (f) Lipiatou et al. (1997) S11 PAHs.

B. Garban et al. / Atmospheric Environment 36 (2002) 5395–54035400

is located in the ‘‘Seine et Marne’’ district (591 500 ha),

atmospheric deposition in this rurban area was

0.91 g ha�1 yr�1, that represents 0.2 g ha�1 yr�1 for the

S3 PAHs (Garban et al., 2002), and gives an annualatmospheric input of 125 kg on the whole district. In this

district for the year 2000, 2336 t of dehydrated sludges,

containing on average 1.5mgkg�1 of the S3 PAHs werespread on 324.5 ha, corresponding to 10.8 g ha�1 yr�1

locally. Regardless of the local spreading, the global

input of the S3 PAHs by sludges onto the district was3.5 kg. As a function of the spreading surface, at the field

scale, spreading is the major input, however, at the

district scale, atmospheric deposition is the major one

(97% of total input). If agricultural spreading of sludge

is banned in France in the near future, atmospheric

deposition will become the major source of PAH input

to agricultural soils.

4. Conclusion

For the first time, simultaneous PAH bulk deposition

onto six various areas in France were studied. PAH

concentrations were within the range of concentrations

reported from other European studies, with the highest

values recorded in winter. More than 70% of the

annual loading took place during this period. The

present study clearly indicates the seasonal variations

and the impact of anthropogenic activities. Additional

research will be required to estimate repartition of wet

and dry deposition. On the transverse, PAH pollution

decreases proportionally from the distance of the main

PAH sources, e.g. Paris. PAH fluxes in the Paris urban

area were five times higher than in the coastal and rural

ones (227 and 55 mgm�2 yr�1, respectively). The lowest

PAH depositions were calculated for the temperate

period in rural and forested sites with about

50 ngm�2 d�1, values close to those determined in

remote sites such as European mountains. Western

coast sites, locally less polluted under oceanic influence,

are submitted, by eastern winds, to a more distant

continental pollution. Atmospheric deposition was the

main source of PAHs to terrestrial ecosystems and

especially to soils. As some of the PAHs studied are

potentially carcinogenic, the international community

recently declared the necessity of reducing emissions.

Further studies will be needed to observe real declines of

PAH levels in air and atmospheric deposition concen-

trations.

Acknowledgements

This study was supported by the programme PIREN-

Seine initiated by the CNRS. We would like to thank,

F. Mouchot (Office National des For#ets), P. Ansart

(CEMAGREF), Mrs. Valac and M. Beaudouin

(Institution Interd!epartementale des Barrages-

R!eservoirs du Bassin de la Seine), Ist-Ma#ıtres Berthel!e

and Le Gall (Marine Nationale) and P. Le Guillou

(volunteer) who collected and mailed so carefully our

rain samples.

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