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Atmospheric Environment 41 (2007) 7241–7252
www.elsevier.com/locate/atmosenv
Pesticides analysed in rainwater in Alsace region(Eastern France): Comparison between urban and
rural sites
Anne Scheyer, Stephane Morville, Philippe Mirabel, Maurice Millet�
Laboratoire de Physico-Chimie de l’Atmosphere (UMR 7517), Centre de Geochimie de la Surface et Departement de Chimie de l’Universite
Louis Pasteur, 1, rue Blessig, 67084 Strasbourg cedex, France
Received 23 January 2007; received in revised form 14 May 2007; accepted 15 May 2007
Abstract
Current-used pesticides commonly applied in Alsace region (Eastern France) on diverse crops (maize, vineyard,
vegetables, etc.) were analysed, together with Lindane, in rainwater between January 2002 and June 2003 simultaneously
on two sites situated in a typical rural (Erstein, France) and urban area (Strasbourg, France).
Rainwater samples were collected on a weekly basis by using two automatic wet only collectors associated with an open
collector for the measurement of rainwater height.
Pesticides were analysed by GC-MSMS and extracted from rainwater by SPME. Two runs were performed. The first one
was performed by using a PDMS (100mm) fibre for pesticides where direct injection into GC is possible (alachlor, atrazine,
azinphos-ethyl, azinphos-methyl, captan, chlorfenvinphos, dichlorvos, diflufenican, a- and b-endosulfan, iprodione,
lindane, metolachlor, mevinphos, parathion-methyl, phosalone, phosmet, tebuconazole, triadimefon and trifluralin). The
second run was performed by using PDMS/DVB fibre and this run concerns pesticides where a preliminary derivatisation
step with pentafluorobenzylbromide (PFBBr) is required for very low volatiles (bromoxynil,2,4-MCPA, MCPP and 2,4-D)
or thermo labiles (chlorotoluron, diuron and isoproturon) pesticides.
Results showed that the more concentrated pesticides detected were those used as herbicides in large quantities in
Alsace region for maize crops (alachlor, metolachlor and atrazine). Maximum concentrations for these herbicides
have been measured during intensive applications periods on maize crops following by rapid decrease immediately
after use.
For Alachlor, most important peaks have been observed between 21 and 28 April 2003 (3327 ngL�1 at Erstein and
5590 ngL�1 at Strasbourg). This is also the case for Metolachlor where most important peak was observed during the same
week.
Concentrations of pesticides measured out of application periods were very low for many pesticides and some others
where never detected during this period. This is the case for diflufenican which was detected only during application. Two
important peaks of concentrations were observed; a first one (101 ngL�1) in Erstein in November 2002 (4–11 November)
and a second one (762 ngL�1) also in Erstein (28 April–15 May).
The same behaviour can be seen for chlorfenvinphos and phosalone which have been detected, respectively, 2 and 4
times in Erstein and Strasbourg at high concentrations (28 April 2003–15 May 2003, 187 ngL�1 of phosalone and
157 ngL�1 of chlorfenvinphos in Erstein).
e front matter r 2007 Elsevier Ltd. All rights reserved.
mosenv.2007.05.025
ing author. Tel.: +33390 240 422; fax: +33 390 240 402.
ess: [email protected] (M. Millet).
ARTICLE IN PRESSA. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–72527242
MCPP, 2,4 MCPA and 2,4-D have been detected at high concentrations in rainwater but for the other pesticides very
episodically and mainly during their use in agriculture. Maximal concentrations of MCPP and 2,4 MCPA have been
measured in Erstein between 28 April and 15 May (904 and 746 ngL�1, respectively).
Comparison between rural and urban sites showed that concentrations in rural areas are generally higher except for
pesticides commonly applied in urban areas like Diuron.
No seasonal phenomenon was observed for Diuron. This herbicide has been detected in practically all of the rainwater
samples in Strasbourg (40/41) with a maximum of 1025 ngL�1 (16–23 September 2002) in 38 samples on 41 in Erstein with
a maximum of 317 ngL�1 (15–23 October 2002). The total concentration of Diuron measured between 4 March 2002 and
20 July 2003 is of 4721 ngL�1 in Strasbourg and 5025 ngL�1 in Erstein. This result shows that wet deposition of Diuron in
urban and rural sites was equivalent and can be explained by the ‘‘urban use’’ of this molecule together with its potential
persistence.
r 2007 Elsevier Ltd. All rights reserved.
Keywords: Pesticides; Rainwater; Urban and rural areas; Temporal and geographical variations of concentrations
1. Introduction
The atmosphere is known to be a good pathwayfor the transport and dissemination of residues ofpesticides. This is firstly observed in the 1960sfor organochlorine pesticides when they wereintensively used in many countries (Abbott et al.,1965; Wheatley and Hardman 1965; Tarrant andTatton, 1968). The emissions of current-usedpesticide into the atmosphere can be the conse-quence of ‘‘spray drift’’ followed by volatilisationduring application, post-application volatilisationfrom treated crops and leaves and wind erosionof fine soil particles where pesticides are adsorbed.When in the atmosphere, pesticides can be foundin both the gaseous and the particulate phase(Millet et al., 1997) and they can be transportedsometimes far from their application site, dependingon their potentiality of persistence, and depositedthrough wet and dry deposition processes. Theremoval rate of pesticides from the atmosphereby wet deposition depends partly on Henry’slaw coefficient, to some extent on their diffusivityin air, and on meteorological conditions (windspeed, atmospheric stability, precipitation) andon the conditions of the surface (for dry deposi-tion only). The atmospheric lifetime of pesticides isnot only influenced by their removal rate by dryand wet deposition, but also by photochemicalreactions with OH radicals and O3 (Atkinson et al.,1999).
The presence of modern pesticides, like 2,4-D, inrainwater were published for the first time in themid-1960s by Cohen and Pinkerton (Van Dijk andGuicherit, 1999) but until the late 1980s, no specialattention was given to this problem. Van Dijk and
Guicherit (1999) and Dubus et al. (2000) publishedin the beginning of the 2000s reviews on monitoringdata of current-use pesticides in rainwater forEuropean countries. Some other measurementswere also performed in the US (Mc Connell et al.,1998; Coupe et al., 2000) and in Japan (Haragushiet al., 1995) and more recently in France (Briandet al., 2002), Germany (Epple et al., 2002; deRossi et al., 2003), Poland (Grybkiewicz et al.,2003), Belgium (Quaghebeur et al., 2004) andDenmark (Asman et al., 2005).
Pesticides are generally present in precipitationfrom few ngL�1 to several mgL�1 (Van Dijk andGuicherit, 1999) and the highest concentrationswere detected during application of pesticides intocrops.
Generally, a local contamination of rainwater bypesticides was observed but some data show acontamination of rainwater by pesticides in regionswhere they are not in used (Van Dijk and Guicherit,1999). These data suggest the potentiality of transportand consequently the potentiality of the contamina-tion of ecosystems far from their application.
The actual concentration of a pesticide in rain-water or wet deposition of a pesticide does not onlydepend on its properties, on the precipitationamount and the meteorological conditions at theobservational site, but also on the geographicaldistribution of the amount of pesticide applied, thetype of surface onto which it is applied andthe meteorological conditions in the area of whichthe emissions contribute to the concentration at themeasuring site.
Actually, little is known about the ecologicaleffects on rainwater deposition of current-usedpesticides on aquatic of terrestrial ecosystems.
ARTICLE IN PRESSA. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–7252 7243
The aim of this work was to compare the levels ofpesticides in rainwater collected between a rural andan urban site in the north of the Alsace region(Eastern France). This region is densely populatedand 41% of its surface is used for agriculture. Themain agricultural activity is dominated by cerealsand maize (57% of the total agricultural surface)and the number of hectares used for these kinds ofcropping have increased by 10% between 1988 and2000. Others crops type areas remain stableand include vineyards, fruits, vegetables, hop, sugarbeet, etc.
Intensive agricultural activities and the diversityof crops in the Alsace region are responsible for animportant use of synthetic pesticides, includingherbicides, fungicides and insecticides. This inten-sive application of pesticides can induce an im-portant contamination of rainwater. In order toevaluate this contamination and its spatial andtemporal variability, rainwater samples were col-lected for 18 months in a typical rural and urban sitesituated in Strasbourg (Eastern France) and in itsvicinity.
2. Materials and methods
2.1. Chemicals
High purity standard pesticides [alachlor (99.7%),atrazine (99.2%), azinphos-ethyl (99.4%), azinphos-methyl (98.6%), bromoxynil (99.3%), captan(99.7%), chlorfenvinphos (98.4%), chlorotoluron(99.6%), 2,4-D (99.6%), dichlorvos (99.0%), diflufe-nican (98.4%), diuron (99.4%), a- and b-endosulfan(99%), iprodione (99.0%), isoproturon (99.0%),lindane (99.0%), MCPA (99.6%), MCPP-P(99.0%), metolachlor (98.0%), mevinphos (91.0%),parathion-methyl (99.6%), phosalone (99.3%), phos-met (99.9%), tebuconazole (98.0%), triadimefon(99.9%) and trifluralin (99.3%)] and the internalstandards (deuterated naphthalene and tecnazen(99.8%)) were obtained from Promochem (Mol-sheim, France), Aldrich and Fluka, respectively.
The solvents used were HPLC grade n-hexane(n-hex) and dichloromethane (CH2Cl2) (Prolabo,France). Pentaflourobenzylbromide (PFBBr) (99+%) and triethylamine (X99.5%) were providedfrom Aldrich and Fluka, respectively.
A stock solution (1 gL�1) was prepared for eachpesticide in methanol. Mixtures of pesticides wereprepared in methanol containing 100mgL�1 ofeach individual pesticide. Ultrapure Milli-Q water
(Millipore) was used to prepare the differentstandard solutions. The final percentage of metha-nol in all standard solution did not exceed 0.1% anddid not have an influence on the efficiency of theextraction (Scheyer et al., 2006, 2007a).
The solid phase micro-extraction (SPME) holderand fibre assemblies (polydimethylsiloxane (PDMS)and PDMS/DVB (divinylbenzene)) for manualsampling were provided by Supelco (France).
2.2. Sampling location
To compare rainwater contamination in differentlocations, rain samples were collected in two samplingstations (Fig. 1). The first station was chosen inorder to represent an urban area and the rainwatercollector was placed in the botanical garden of theStrasbourg University situated near the historic centreof Strasbourg (400 000 inhabitants).
The particular feature of this city is that intensiveagricultural activities (essentially maize) take placeat only 15 km of its centre, to the south.
The second sampling point was installed in a ruralarea, situated 25 km southeast of Strasbourg, at2 km from a small town, Erstein (9000 inhabitants),and 300m from the nearest treated area. The twocollectors were placed on the soil, but far fromthe treated area in order to avoid the possibledirect input of pesticides from treatment into thesampler.
2.3. Sample collection
Samples were collected simultaneously on the twosites on a weekly basis between January 2002 andSeptember 2003 by using a wet only rainwatersampler (Precis Mecanique, France) agreed byMETEO-France. After sampling, samples werestored in darkness at �18 1C before analysis.
In order to eliminate the variations on concentra-tions inherent to the fluctuation of the precipitationlevel during a week of sampling, each station wasalso equipped with a graduated open collector(Precis Mecanique, France).
The normalised concentration is calculated ac-cording to
Ci1;norm ¼Ci1Hi
Hm, (1)
where Ci1,norm is the normalised concentration ofspecies 1 in the sample i, Ci1 the concentrationof species 1 in the sample i, Hi the precipitation
ARTICLE IN PRESS
Distribution of farming in Alsace
Crop (maize corn)
wine
Vegetable farming
and pig breeding
area
fish and cow
breedind area
Forest and
breeding area
Pasture andbreeding
Orchards
Erstein
Fig. 1. Distribution of agricultural activity in the Alsace region.
A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–72527244
height of the sample i (in mm) and Hm the meanprecipitation height (in mm). Precipitation heightswere determined by using an open graduatedrainwater collector.
2.4. SPME extraction of pesticides
Alachlor, atrazine, azinphos-ethyl, azinphos-methyl, bromoxynil, captan, chlorfenvinphos, di-chlorvos, diflufenican, a- and b-endosulfan, ipro-dione, lindane, metolachlor, mevinphos, parathion-methyl, phosalone, phosmet, tebuconazole, triadi-mefon and trifluralin were extracted by using aPDMS (100 mm) SPME fibre for 40min at 45 1C(pH ¼ 6.0, saturated NaCl).
Bromoxynil, chlorotoluron, diuron, isoproturon,2,4-MCPA, MCPP and 2,4-D were extracted with aPDMS/DVB fibre by direct extraction for 60min at68 1C (pH 2 and 75% NaCl). Prior to this extractionprocedure, a headspace coating of the fibre withPFBBr for 10min was performed.
Detailed analytical procedures are described else-where (Scheyer et al., 2006, 2007a).
2.5. Analysis
A Varian Star 3400 CX gas chromatographequipped with a split–splitless injector and coupledto a Varian Saturn IV mass selective detector wasused. A Macherey–Nagel analytical capillary col-umn OPTIMA 5 was chosen (30m� 0.32mm, filmthickness: 0.25 mm). Helium was used as the carriergas and inlet pressure was 19 psi (corresponding to aflow rate of 2mLmin�1). The injector and thetransfer line temperatures were kept at 250 1C whilethe manifold temperature was 200 1C.
For SPME analysis of non-derivatised pesticides,the GC temperature program varied between60 1C (for 2min) and 163 1C at 25 1Cmin�1, then163–165 1C at 0.3 1Cmin�1, then 167–210 1Cat 301min�1 and finally 210–250 1C (10min) at5 1Cmin�1.
For the SPME analysis of derivatised pesticides,the GC program varied between 80 1C (2min)and 150 1C at 15 1Cmin�1, then 150–192 1C at3.1 1Cmin�1, then 192–193 1C at 0.2 1Cmin�1 andfinally 193–250 1C (5min) at 20 1Cmin�1.
ARTICLE IN PRESSA. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–7252 7245
For the quantification, an internal standard wasused: deuterated naphthalene at 10mgL�1 for thenon-derivatised runs and tecnazen at 10mgL�1 forthe derivatised runs.
Detection limits for the non-derivatised pesticidesvaried between 0.1 and 5 mgL�1 while standarddeviations varied from 10% to 34% (Scheyer et al.,2006).
Detection limits were obtained for all thederivatised compounds that ranged between 10and 1000 ngL�1 with an important uncertaintydue to the combination of derivatisation and SPMEextraction steps (Scheyer et al., 2007a).
3. Results and discussion
Among the 27 pesticides monitored in rainwaterbetween 2002 and 2003 in Erstein and Strasbourg,azinphos-ethyl, azinphos-methyl, dichlorvos, ipro-dione, mevinphos, bromoxynil, chlorotoluron and
Type of
déposition
Period of the
yearConcen
A
During application
Interme
elev
(10-max
B
During season of
treatment
Interme
elev
(10-max
C
During all the year
L
(few ng
ng
D
During all the year
Low
interm
(few ng
1000 n
E
Eprisodically
Lo
(few ng.
ng.
Fig. 2. Classification of pesticides studied following
isoproturon were never detected. These pesticideswere not detected during the sampling periods since:
�
tra
dia
ate
ng
dia
ate
ng
ow
.L-1
.L-1
to
edi
.L-
g.L
w
L-1
L-1)
th
they were not applied during the sampling period(azinphos-ethyl, azinphos-methyl, dichlorvos andmevinphos),
� they were applied very episodically at very lowamounts (bromoxynil, iprodione),
� they were very low volatile and detection limitsare high (chlorotoluron and isoproturon).
The behaviour of the pesticides detected in rain-water in Erstein and Strasbourg can be ranged indifferent classes following the classification proposedby Dubus et al. (2000) associating the type ofdeposition and transport phenomena (Fig. 2).
Chlorfenvinphos, diflufenican, parathion-methyl,phosalone, MCPP, MCPA and 2,4-D were detectedepisodically in some samples while diuron, endo-sulfan and lindane were detected practically duringall the sampling period in Erstein and Strasbourg.
tionType of
Transport
Examples of
pesticides
te to
d
.L-1)
Local transport
(< 1 km)
Chlorfenvinphos,
phosalone,
diflufenican
te to
d
.L-1)
Atrazine,
Alachlore,
metolachlor
to 10
) Global Lindane
ate1 to-1)
LocalDiuron,
Endosulfan
to 10 Local
Trifluraline,
parathion-methyl,
MCPP, 2,4 MCPA
Medium to
long distance
(1 to 1000km)
e model proposed by Dubus et al. (2000).
ARTICLE IN PRESSA. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–72527246
The other pesticides (trifluralin, alachlor, atrazineand metolachlor) present very important seasonaleffects strongly associated with their period ofapplication.
3.1. Pesticides detected episodically
Parathion-methyl was detected only two times atconcentrations below quantification limits duringthe sampling period (3–6 June 2002 in Strasbourg;21–28 April 2003 in Erstein). This insecticidewas not detected in air samples collected duringthe same period of time (Scheyer et al., 2007b).This is not in accordance with results from Coupeet al. (2000) where high levels of methyl-parathionwere measured in rainwater (22.9 mgL�1) andalso in air in the same week in the Mississippi state.The main reason of this difference is certainlythe important quantities of methyl-parathion ap-plied in Mississippi during the sampling of rain-water in comparison with the quantities applied inAlsace.
Diflufenican was detected in 31% of the samplesbut in many cases at concentrations below detectionlimits. However, in contrary to parathion-methyl, itwas more frequently detected in the air (Scheyeret al., 2007b). This difference of behaviour betweenthese two pesticides can be explained by their Henrylaw constant and solubility in water. Indeed,diflufenican presents a high Henry law constant(0.033 Pam3mol�1) and a poor solubility in water(o0.05mgL�1) which induce a low affinity to theaqueous phase. Parathion-methyl presents a lowHenry law constant (9.6.10�4 Pam3mol�1) and agood solubility in water (60mgL�1) which permit agood wash out by precipitation.
Diflufenican was observed at high concentrationin Erstein between 4 November 2002 and 11November 2002 (101 ngL�1) and between 28 April2003 and 15 May 2003 (762 ngL�1) but not inStrasbourg. The first concentration corresponds to atreatment performed in autumn and the second onecorresponds to a treatment performed in spring. Animportant concentration in the air was also ob-served between 28 April 2003 and 29 April 2003 inGeispolsheim (1534 ngL�1), a town in the vicinityof Erstein, but not detected in the same time inStrasbourg (Scheyer et al., 2007b). The concordanceof the behaviour of diflufenican between rainwaterand air analysis tends to demonstrate a rapiddeposition of this fungicide near to the applicationsite and a very limited local transport.
Chlorfevinphos and phosalone were detected,respectively, 2 and 4 times in Erstein and Strasbourgduring the sampling period. Between 28 April 2003and 15 May 2003, 187 ngL�1 of phosalone and157 ngL�1 of chlorfevinphos were measured atErstein while in Strasbourg their concentrationswere below the quantification limits. During thisperiod, some insecticide treatments could be per-formed on vineyard and could explain concentra-tions measured. This hypothesis is corroborated bytheir detection in Erstein, which is a site situateddirectly under the wind of vineyard crops.
Aryloxyacids (MCPA, MCPP, 2,4-D) were de-tected in some rainwater sampled in Erstein andStrasbourg at high concentrations whereas theywere practically not detected in air samples (Scheyeret al., 2007b). The main reason is the high detectionslimits obtained for these pesticides with the analy-tical method used (Scheyer et al., 2007a). Concen-trations and periods of detection are presented inTable 1. They were generally detected in spring athigher concentrations in Erstein than in Strasbourg.These herbicides are applied on cereals crops inspring and their preferential measurements in springcan be explained. The 2,4-D was detected essentiallyin Strasbourg in spring and summer. No explana-tion can be, with the current data, advanced for thisobservation but since these herbicides can be usedby local municipalities to control weeds alongroadways and other right-of-ways, an urban appli-cation of these herbicides can be the most probablereason of their detection in the urban site.
3.2. Pesticides detected seasonally
Herbicides commonly and intensively used inmaize crops were detected with a pronouncedseasonal profile. This is the case for atrazine,alachlor and metolachlor where an increase inconcentrations starts in April, reaches a maximumin the beginning of May and decreases at the end ofJune. This profile was observed during the 2 yearsof measurements on the two sites and correspondsto the period of application of these herbicides oncrops.
Alachlor, atrazine and metolachlor present a highwater solubility and low Henry’s law constants.These properties are in favour of their enrichment inrainwater since herbicides at low Henry’s lawconstants are preferentially present in the particlephase and consequently more efficiently depositedby precipitations.
ARTICLE IN PRESS
Table 1
Concentrations (in ngL�1) of MCPP, MCPA and 2,4-D
measured in rainwater samples collected at Erstein and Stras-
bourg between 2002 and 2003
Period of sampling MCPA MCPP 2,4-D
4–10/03/02
Strasbourg 13
Erstein
22–29/04/02
Strasbourg 483
Erstein
14–21/05/02
Strasbourg 50
Erstein
15–22/07/02
Strasbourg 590
Erstein
20–26/08/02
Strasbourg 122
Erstein
23–28/10/02
Strasbourg
Erstein 527
09/12/02–04/01/03
Strasbourg 663
Erstein 228
20–27/01/03
Strasbourg
Erstein 79
27/01–10/02/03
Strasbourg
Erstein 82
01–25/03/03
Strasbourg 123
Erstein 145
25/03–06/04/03
Strasbourg 268 95
Erstein 70
06–14/04/03
Strasbourg oQL oQL
Erstein
14–21/04/03
Strasbourg
Erstein oQL oQL
21–28/04/03
Strasbourg oQL 56
Erstein oQL 59
28/04–15/05/03
Strasbourg 731 oQL
Erstein 746 904 237
oQL: below quantification limits.
A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–7252 7247
Concentrations of atrazine (Fig. 3) on the two sitesare on the same order of magnitude, except on theweek of 30 April 2002–6 May 2002 (6.25mgL�1 inErstein) and of 15 May 2003–28 May 2003 (1.5mgL�1
in Erstein). These 2 weeks correspond to the intensiveapplication of atrazine on maize and the Erstein site is
situated directly near maize crops. Moreover, duringthe first week (30 April 2002–6May 2002), wind comesfrom south and could have induced a short-rangetransport of atrazine form these areas to the samplingsite situated in Erstein. The local drift of atrazine inErstein in comparison to Strasbourg can be confirmedby the comparison of concentrations obtained inurban rainwater in other studies (Table 2). Concentra-tions measured in Erstein were the highest ones andconfirm an application close to the site. It can also beseen that concentrations of atrazine measured inStrasbourg in 2001 and 2002–2003, period of intensiveused of this herbicide, were in the same order ofmagnitude. Generally, main wind direction in theRhine upper valley comes from southwest.
Concentrations of atrazine were higher in Stras-bourg only on the week from 3 June to 10 June. Thisobservation can be explained by a short transport ofatrazine applied in the north of Strasbourg. Winddirection during this period, coming from the north,confirms this hypothesis.
Concentrations of alachlor and metolachlorpresent the same profile as concentrations ofatrazine. To illustrate this result, the variations ofconcentrations of alachlor in Strasbourg andErstein between 2002 and 2003 are presented inFig. 4. However, the highest concentrations weremeasured in Strasbourg for alachlor in 2003. It isdifficult to explain this phenomenon with the dataavailable. Concentrations measured for alachlorwere higher than those measured in the same periodfor atrazine and this difference can be comparedwith the quantity of atrazine and alachlor appliedby hectare. Indeed, alachlor is applied on maizecrop at a concentration of 2.5 more important thanatrazine. Since alachlor is more volatile thanatrazine, it is possible that this molecule canvolatilise more importantly and explain also theelevated concentration measured.
For alachlor and metolachlor, some traces weremeasured out of the normal period of applicationand this observation could indicate a more persis-tence of these herbicides in comparison to atrazine.Due to this persistence these compounds could bevolatilised from soils of leaves after their applicationand atmospheric concentrations could be washedout again by precipitation.
3.3. Pesticides detected systematically
Among the pesticides monitored, lindane, endo-sulfan and diuron were detected practically in all
ARTICLE IN PRESS
Period of sampling
Co
nce
ntr
atio
n in
ng
.L-1
0
250
500
750
1000
1250
1500
5000
6000
7000
8000
Strasbourg
Erstein
4-1
0 m
arc
h
11
-18
ma
rch
18
-24
ma
rch
24
-1 a
pril
1-8
ap
ril
8-1
5 a
pril
16
-22
ap
ril
22
-29
ap
ril
30
-06
ma
y
7-1
3 m
ay
14
-21
ma
y
22
-29
ma
y
3-1
0 ju
ne
10
-17
ju
ne
17
-24
ju
ne
24
-1 ju
ly
1-7
ju
ly
15
-22
ju
ly
23
-30
ju
ly
9-1
6 s
ep
t
16
-23
se
pt
23
-30
se
pt
20
-27
ja
n
27
-10
fe
b
10
-1 m
arc
h
1-2
5 m
arc
h
25
-6 a
pril
6-1
4 a
pril
14
-21
ap
ril
21
-28
ap
ril
28
-15
ma
y
16
-28
ma
y
28
-08
ju
ly
8-2
0 ju
ly
Fig. 3. Evolution of the concentrations of atrazine (in ngL�1) in the two sites between March 2002 and July 2003.
Table 2
Comparison of pesticides concentrations in different parts of the world (in ngL�1)
Trevisan et al.
(1993) (Italy)
Chevreuil et al.
(1996) (Paris
area)
Coupe et al.
(2000)
(Mississippi)
Quaghebeur
et al. (2004)
(Belgium)
Sauret (2002)
(Strasbourg)
This study
(2002–2003)
(Strasbourg)
This study
(2002–2003)
(Erstein)
(min/max)
Atrazine 150/1990 oQL/400 6/96 /1300 oQL/1181 36/1031 oQL/6248
Trifluralin 50/3440 NA o2/10 /53 NA oQL oQL
Lindane NA 14/350 ND /1700 NA oQL/132 oQL/174
Endosulfan NA NA NA /285 NA oQL/3667 oQL/1506
Iprodione 111/560 NA ND ND oQL/3249 oQL/5590 oQL/3327
Metolachlor NA NA D /1100 oQL/1480 oQL/122 oQL/799
Diuron NA NA NA /6400 NA oQL/1025 oQL/1317
Parathion-M NA NA 24/300 /45 NA oQL oQL
Diflufenican NA NA NA NA oQL/2894 oQL/57 oQL/762
NA, not analysed; oQL: below quantification limit.
A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–72527248
anlaysed rainwater samples. For these pesticides, noseasonal trends were observed whatever the sam-pling site.
Lindane is one of the most studied pesticides inthe literature. Dubus et al. (2000) state that thisinsecticide was generally detected in 90% of the
ARTICLE IN PRESS
Period of sampling
Co
nce
ntr
atio
n in
ng
.L-1
0
1000
3000
4000
5000
6000
Strasbourg
Erstein
4-1
0 m
arc
h
11
-18
ma
rch
18
-24
ma
rch
24
-1 a
pril
1-8
ap
ril
8-1
5 a
pril
16
-22
ap
ril
22
-29
ap
ril
30
-06
ma
y
7-1
3 m
ay
14
-21
ma
y
22
-29
ma
y
3-1
0 ju
ne
10
-17
ju
ne
17
-24
ju
ne
24
-1 ju
ly
1-7
ju
ly
15
-22
ju
ly
23
-30
ju
ly
9-1
6 s
ep
t
16
-23
se
pt
23
-30
se
pt
20
-27
ja
n
27
-10
fe
b
10
-1 m
arc
h
1-2
5 m
arc
h
25
-6 a
pril
6-1
4 a
pril
14
-21
ap
ril
21
-28
ap
ril
28
-15
ma
y
16
-28
ma
y
28
-08
ju
ly
8-2
0 ju
ly
12
-18
no
v
9-4
ja
nv
04
-20
ja
nv
20
-27
ja
nv
27
-10
fé
v
25
-6 a
vril
6-1
4 a
vril
14
-21
avril
21
-28
avril
28
-15
ma
i
16
-28
ma
i
28
-08
ju
il
8-2
0 ju
il
Fig. 4. Evolution of the concentrations of alachlor (in ngL�1) in the two sites between March 2002 and July 2003.
A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–7252 7249
rainwater samples where it was analysed. In ourstudy, the frequency of detection is lower since it wasdetected in about 50% of the urban and ruralanalysed samples (Fig. 5). Lindane presents a lowsolubility in water and a high volatility andconcentrations measured were very low. Highestconcentrations were measured between 28 April 2003and 15 May 2003 (90 and 174 ngL�1 in Strasbourgand Erstein, respectively). During this period, animportant global radiance was observed by METEO-France and consequently high temperature favouringvolatilisation processes. The increase in the concen-trations of lindane measured in rainwater could bethe consequence of volatilisation from contaminatedsoils followed by a local transport. The high levelsobserved in Strasbourg between 9 December 2002and 04 January 2003 cannot be explained byvolatilisation processes. A global transport phenom-enon could explain this concentration.
Endosulfan, as for lindane, is an insectricidesystematically detected in precipitation when ana-
lysed (Quaghebeur et al., 2004). In this study, it wasdetected in 85% of the analysed samples. This is notin accordance with the properties of endosulfanwhich is low soluble in water and has a high Henry’slaw constant. Trends of concentrations present thesame profile as lindane but concentrations werehigher (by a factor of 10). High concentrations weredetected in Strasbourg between 9 December 2002and 4 January 2003. These high concentrationscannot be explained by an application of endosulfanwhich is not used in Alsace during this period.A long-range transport phenomenon, as for lindane,could explain this concentration. Magdic et al. (1996)have detected endosulfan in snow and ice from Arcticregion at concentration between 22 and 136ngL�1.This result tends to validate our hypothesis about along-range transport and also tends to confirm theatmospheric persistence of endosulfan.
Endosulfan is characteristic of type of depositionD following the classification of Dubus et al. (2000)while lindane is characteristic of type of deposition C.
ARTICLE IN PRESS
Period of sampling
Concentr
ation in n
g.L
-1
0
50
100
150
200
250
Strasbourg
Erstein
4-1
0 m
arc
h11-1
8m
arc
h18-2
4 m
arc
h24-1
april
1-8
april
8-1
5 a
pril
16-2
2 a
pril
22-2
9 a
pril
30-0
6 m
ay
7-1
3 m
ay
14-2
1 m
ay
22-2
9 m
ay
3-1
0 june
10-1
7 june
17-2
4 june
24-1
july
1-1
5 july
15-2
2 july
23-3
0 july
30-5
aug
6-1
3 a
ug
13
-20
au
g20-2
6 a
gu
26
-2 s
ep
t2-9
sept
9-1
6 s
ep
t16-2
3 s
ept
23-3
0 s
ept
30-0
7 o
ct
08-1
5 o
ct
15
-23
oct
23-2
8 o
ct
28-4
nov
04-1
2 n
ov
12
-18
no
v18-2
6 n
ov
26-2
dec
2-9
de
c9-4
jan
04-2
0 jan
20-2
7 jan
27-1
0 f
eb
10-1
marc
h1-2
5 m
arc
h25-6
april
6-1
4 a
pril
14-2
1 a
pril
21-2
8 a
pril
28
-15
ma
y16-2
8 m
ay
28-0
8 july
8-2
0 juill
et
Fig. 5. Evolution of the concentrations of lindane (in ngL�1) in the two sites between March 2002 and July 2003.
A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–72527250
No seasonal trends for diuron were observed asshown in Fig. 6. This herbicide was detected in 40samples in Strasbourg for a total number of 41samples. Highest concentrations of 1025 ngL�1
were observed in Strasbourg during the week from16 to 23 September 2002. The frequency ofdetection was lower in Erstein since diuron wasdetected on only 38 samples and the maximumconcentrations was observed in the week from 15 to23 October 2002 (1317 ngL�1).
The high frequency of detection of diuron inrainwater can be explained by its low Henry’s lawconstant (5.1� 10�5 Pam3mol�1) which facilitates amore important transfer to rainwater droplets.
The sum of the concentration of diuron measuredin Strasbourg between 4 March 2002 and 23 July2003 is 4721 ngL�1 and 5025 ngL�1 in Strasbourgand Erstein, respectively. The atmospheric deposi-tion of diuron by precipitation is of the same orderof magnitude between urban and rural areasexplaining the ‘‘urban use’’ of this herbicide. The
same behaviour was observed in air samplescollected in the same period (Scheyer et al.,2007b). Quaghebeur et al. (2004) have observedhigher concentration of diuron in urban site than inrural site. Their results tend to confirm thehypothesis of the influence of the urban applicationof diuron. Diuron is characteristic of type ofdeposition D.
4. Conclusion
Rainwater samples were collected simultaneouslybetween 2002 and 2003 on rural and urban sites inAlsace. Results obtained by the SPME analysis ofcurrent-used pesticides during this period of sam-pling show that the contamination of rainwater bypesticides is function of:
�
the physical and chemical properties of pesti-cides, � the period and the dose of application,
ARTICLE IN PRESS
Period of sampling
Concentr
ation in n
g.L
-1
0
200
400
600
800
1000
1200
1400
1600
1800
2000
Strasbourg
Erstein
18-2
4 m
arc
h24-1
apr
1-8
apr
8-1
5 a
pr
16-2
2 a
pr
22-2
9 a
pr
7-1
3 m
ay
8-2
0 juil
14-2
1 m
ay
22-2
9 m
ay
3-1
0 june
10-1
7 june
17-2
4 june
24-1
july
1-1
5 july
15-2
2 july
23-3
0 july
30-5
aug
6-1
3 a
ug
13-2
0 a
ug
20-2
6 a
ug
26-2
sept
2-9
sept
9-1
6 s
ept
16-2
3 s
ept
23-3
0 s
ept
30-0
7 o
ct
08-1
5 o
ct
15-2
3 o
ct
23-2
8 o
ct
28-4
nov
04-1
2 n
ov
12-1
8 n
ov
18-2
6 n
ov
26-2
dec
2-9
dec
9-4
jan
04-2
0 jan
20-2
7 jan
27-1
0 f
eb
10-1
marc
h1-2
5 m
arc
h25-6
apr
6-1
4 a
pr
14-2
1 a
pr
21-2
8 a
pr
28-1
5 m
ay
16-2
8 m
ay
28-0
8 july
30-0
6 a
pr
Fig. 6. Evolution of the concentrations of diuron (in ngL�1) in the two sites between March 2002 and July 2003.
A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–7252 7251
�
the localisation of the application and theclimatic conditions during application, � local and long-range transport phenomena.Rainwater could be a very simple and inexpensivetechnique for the indirect evaluation of the spatialand temporal evaluation of the atmospheric con-tamination by pesticides instead of Hi-Vol sam-pling, generally more complicated to use andanalyse.
However, the need of regular rain events atmoderate intensity is required.
Acknowledgements
The authors would like to thank the ‘‘RegionAlsace’’, the ‘‘DRIRE Alsace’’ and the FrenchMinistry of Ecology and Sustainable Developmentthrough the Primequal-2 program for their financialsupport.
Anne Scheyer particularly thanks ADEME and‘‘Region Alsace’’ for a PhD grant.
The ‘‘Chambre Regionale d’Agriculture ‘‘is alsogratefully acknowledged, in particular Mr. JeanRichert for his help.
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