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: [email protected] (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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