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Pesticides analysed in rainwater in Alsace region (Eastern France): Comparison between urban and rural sites
ARTICLE IN PRESS
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, Ste´phane Morville, Philippe Mirabel, Maurice Millet Laboratoire de Physico-Chimie de l’Atmosphe`re (UMR 7517), Centre de Ge´ochimie de la Surface et De´partement 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 (100 mm) 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 ng L1 at Erstein and 5590 ng L1 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 ng L1) in Erstein in November 2002 (4–11 November) and a second one (762 ng L1) 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 ng L1 of phosalone and 157 ng L1 of chlorfenvinphos in Erstein). Corresponding author. Tel.: +33 390 240 422; fax: +33 390 240 402.
E-mail address: [email protected] (M. Millet). 1352-2310/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.atmosenv.2007.05.025
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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 ng L1, 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 ng L1 (16–23 September 2002) in 38 samples on 41 in Erstein with a maximum of 317 ng L1 (15–23 October 2002). The total concentration of Diuron measured between 4 March 2002 and 20 July 2003 is of 4721 ng L1 in Strasbourg and 5025 ng L1 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 pathway for the transport and dissemination of residues of pesticides. This is firstly observed in the 1960s for organochlorine pesticides when they were intensively used in many countries (Abbott et al., 1965; Wheatley and Hardman 1965; Tarrant and Tatton, 1968). The emissions of current-used pesticide into the atmosphere can be the consequence of ‘‘spray drift’’ followed by volatilisation during application, post-application volatilisation from treated crops and leaves and wind erosion of fine soil particles where pesticides are adsorbed. When in the atmosphere, pesticides can be found in both the gaseous and the particulate phase (Millet et al., 1997) and they can be transported sometimes far from their application site, depending on their potentiality of persistence, and deposited through wet and dry deposition processes. The removal rate of pesticides from the atmosphere by wet deposition depends partly on Henry’s law coefficient, to some extent on their diffusivity in air, and on meteorological conditions (wind speed, atmospheric stability, precipitation) and on the conditions of the surface (for dry deposition only). The atmospheric lifetime of pesticides is not only influenced by their removal rate by dry and wet deposition, but also by photochemical reactions with OH radicals and O3 (Atkinson et al., 1999). The presence of modern pesticides, like 2,4-D, in rainwater were published for the first time in the mid-1960s by Cohen and Pinkerton (Van Dijk and Guicherit, 1999) but until the late 1980s, no special attention was given to this problem. Van Dijk and
Guicherit (1999) and Dubus et al. (2000) published in the beginning of the 2000s reviews on monitoring data of current-use pesticides in rainwater for European countries. Some other measurements were also performed in the US (Mc Connell et al., 1998; Coupe et al., 2000) and in Japan (Haragushi et al., 1995) and more recently in France (Briand et al., 2002), Germany (Epple et al., 2002; de Rossi et al., 2003), Poland (Grybkiewicz et al., 2003), Belgium (Quaghebeur et al., 2004) and Denmark (Asman et al., 2005). Pesticides are generally present in precipitation from few ng L1 to several mg L1 (Van Dijk and Guicherit, 1999) and the highest concentrations were detected during application of pesticides into crops. Generally, a local contamination of rainwater by pesticides was observed but some data show a contamination of rainwater by pesticides in regions where they are not in used (Van Dijk and Guicherit, 1999). These data suggest the potentiality of transport and consequently the potentiality of the contamination of ecosystems far from their application. The actual concentration of a pesticide in rainwater or wet deposition of a pesticide does not only depend on its properties, on the precipitation amount and the meteorological conditions at the observational site, but also on the geographical distribution of the amount of pesticide applied, the type of surface onto which it is applied and the meteorological conditions in the area of which the emissions contribute to the concentration at the measuring site. Actually, little is known about the ecological effects on rainwater deposition of current-used pesticides on aquatic of terrestrial ecosystems.
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The aim of this work was to compare the levels of pesticides in rainwater collected between a rural and an urban site in the north of the Alsace region (Eastern France). This region is densely populated and 41% of its surface is used for agriculture. The main agricultural activity is dominated by cereals and maize (57% of the total agricultural surface) and the number of hectares used for these kinds of cropping have increased by 10% between 1988 and 2000. Others crops type areas remain stable and include vineyards, fruits, vegetables, hop, sugar beet, etc. Intensive agricultural activities and the diversity of crops in the Alsace region are responsible for an important use of synthetic pesticides, including herbicides, fungicides and insecticides. This intensive application of pesticides can induce an important contamination of rainwater. In order to evaluate this contamination and its spatial and temporal variability, rainwater samples were collected for 18 months in a typical rural and urban site situated in Strasbourg (Eastern France) and in its vicinity. 2. Materials and methods 2.1. Chemicals High purity standard pesticides [alachlor (99.7%), atrazine (99.2%), azinphos-ethyl (99.4%), azinphosmethyl (98.6%), bromoxynil (99.3%), captan (99.7%), chlorfenvinphos (98.4%), chlorotoluron (99.6%), 2,4-D (99.6%), dichlorvos (99.0%), diflufenican (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%), phosmet (99.9%), tebuconazole (98.0%), triadimefon (99.9%) and trifluralin (99.3%)] and the internal standards (deuterated naphthalene and tecnazen (99.8%)) were obtained from Promochem (Molsheim, 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 provided from Aldrich and Fluka, respectively. A stock solution (1 g L1) was prepared for each pesticide in methanol. Mixtures of pesticides were prepared in methanol containing 100 mg L1 of each individual pesticide. Ultrapure Milli-Q water
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(Millipore) was used to prepare the different standard solutions. The final percentage of methanol in all standard solution did not exceed 0.1% and did not have an influence on the efficiency of the extraction (Scheyer et al., 2006, 2007a). The solid phase micro-extraction (SPME) holder and fibre assemblies (polydimethylsiloxane (PDMS) and PDMS/DVB (divinylbenzene)) for manual sampling were provided by Supelco (France). 2.2. Sampling location To compare rainwater contamination in different locations, rain samples were collected in two sampling stations (Fig. 1). The first station was chosen in order to represent an urban area and the rainwater collector was placed in the botanical garden of the Strasbourg University situated near the historic centre of Strasbourg (400 000 inhabitants). The particular feature of this city is that intensive agricultural activities (essentially maize) take place at only 15 km of its centre, to the south. The second sampling point was installed in a rural area, situated 25 km southeast of Strasbourg, at 2 km from a small town, Erstein (9000 inhabitants), and 300 m from the nearest treated area. The two collectors were placed on the soil, but far from the treated area in order to avoid the possible direct input of pesticides from treatment into the sampler. 2.3. Sample collection Samples were collected simultaneously on the two sites on a weekly basis between January 2002 and September 2003 by using a wet only rainwater sampler (Pre´cis Me´canique, France) agreed by METEO-France. After sampling, samples were stored in darkness at 18 1C before analysis. In order to eliminate the variations on concentrations inherent to the fluctuation of the precipitation level during a week of sampling, each station was also equipped with a graduated open collector (Pre´cis Me´canique, France). The normalised concentration is calculated according to C i1;norm ¼
C i1 H i , Hm
(1)
where Ci1,norm is the normalised concentration of species 1 in the sample i, Ci1 the concentration of species 1 in the sample i, Hi the precipitation
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Distribution of farming in Alsace Orchards
Crop (maize corn)
wine
Erstein
Pasture and breeding
Vegetable farming and pig breeding area
Forest and breeding area
fish and cow breedind area
Fig. 1. Distribution of agricultural activity in the Alsace region.
height of the sample i (in mm) and Hm the mean precipitation height (in mm). Precipitation heights were determined by using an open graduated rainwater collector. 2.4. SPME extraction of pesticides Alachlor, atrazine, azinphos-ethyl, azinphosmethyl, bromoxynil, captan, chlorfenvinphos, dichlorvos, diflufenican, a- and b-endosulfan, iprodione, lindane, metolachlor, mevinphos, parathionmethyl, phosalone, phosmet, tebuconazole, triadimefon and trifluralin were extracted by using a PDMS (100 mm) SPME fibre for 40 min at 45 1C (pH ¼ 6.0, saturated NaCl). Bromoxynil, chlorotoluron, diuron, isoproturon, 2,4-MCPA, MCPP and 2,4-D were extracted with a PDMS/DVB fibre by direct extraction for 60 min at 68 1C (pH 2 and 75% NaCl). Prior to this extraction procedure, a headspace coating of the fibre with PFBBr for 10 min was performed. Detailed analytical procedures are described elsewhere (Scheyer et al., 2006, 2007a).
2.5. Analysis A Varian Star 3400 CX gas chromatograph equipped with a split–splitless injector and coupled to a Varian Saturn IV mass selective detector was used. A Macherey–Nagel analytical capillary column OPTIMA 5 was chosen (30 m 0.32 mm, film thickness: 0.25 mm). Helium was used as the carrier gas and inlet pressure was 19 psi (corresponding to a flow rate of 2 mL min1). The injector and the transfer line temperatures were kept at 250 1C while the manifold temperature was 200 1C. For SPME analysis of non-derivatised pesticides, the GC temperature program varied between 60 1C (for 2 min) and 163 1C at 25 1C min1, then 163–165 1C at 0.3 1C min1, then 167–210 1C at 301 min1 and finally 210–250 1C (10 min) at 5 1C min1. For the SPME analysis of derivatised pesticides, the GC program varied between 80 1C (2 min) and 150 1C at 15 1C min1, then 150–192 1C at 3.1 1C min1, then 192–193 1C at 0.2 1C min1 and finally 193–250 1C (5 min) at 20 1C min1.
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For the quantification, an internal standard was used: deuterated naphthalene at 10 mg L1 for the non-derivatised runs and tecnazen at 10 mg L1 for the derivatised runs. Detection limits for the non-derivatised pesticides varied between 0.1 and 5 mg L1 while standard deviations varied from 10% to 34% (Scheyer et al., 2006). Detection limits were obtained for all the derivatised compounds that ranged between 10 and 1000 ng L1 with an important uncertainty due to the combination of derivatisation and SPME extraction steps (Scheyer et al., 2007a).
3. Results and discussion Among the 27 pesticides monitored in rainwater between 2002 and 2003 in Erstein and Strasbourg, azinphos-ethyl, azinphos-methyl, dichlorvos, iprodione, mevinphos, bromoxynil, chlorotoluron and
Type of déposition
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isoproturon were never detected. These pesticides were not detected during the sampling periods since:
they were not applied during the sampling period (azinphos-ethyl, azinphos-methyl, dichlorvos and mevinphos), they were applied very episodically at very low amounts (bromoxynil, iprodione), they were very low volatile and detection limits are high (chlorotoluron and isoproturon).
The behaviour of the pesticides detected in rainwater in Erstein and Strasbourg can be ranged in different classes following the classification proposed by Dubus et al. (2000) associating the type of deposition and transport phenomena (Fig. 2). Chlorfenvinphos, diflufenican, parathion-methyl, phosalone, MCPP, MCPA and 2,4-D were detected episodically in some samples while diuron, endosulfan and lindane were detected practically during all the sampling period in Erstein and Strasbourg.
Period of the year
Concentration
Type of Transport
Examples of pesticides
During application
Intermediate to elevated (10-max ng.L-1)
Local transport (< 1 km)
Chlorfenvinphos, phosalone, diflufenican
During season of treatment
Intermediate to elevated (10-max ng.L-1)
Medium to long distance (1 to 1000km)
Atrazine, Alachlore, metolachlor
Global
Lindane
A
B
C During all the year
Low (few ng.L-1to 10 ng.L-1)
D During all the year
Low to intermediate (few ng.L-1 to 1000 ng.L-1)
Local
Diuron, Endosulfan
Eprisodically
Low (few ng.L-1 to 10 ng.L-1)
Local
Trifluraline, parathion-methyl, MCPP, 2,4 MCPA
E
Fig. 2. Classification of pesticides studied following the model proposed by Dubus et al. (2000).
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The other pesticides (trifluralin, alachlor, atrazine and metolachlor) present very important seasonal effects strongly associated with their period of application. 3.1. Pesticides detected episodically Parathion-methyl was detected only two times at concentrations below quantification limits during the sampling period (3–6 June 2002 in Strasbourg; 21–28 April 2003 in Erstein). This insecticide was not detected in air samples collected during the same period of time (Scheyer et al., 2007b). This is not in accordance with results from Coupe et al. (2000) where high levels of methyl-parathion were measured in rainwater (22.9 mg L1) and also in air in the same week in the Mississippi state. The main reason of this difference is certainly the important quantities of methyl-parathion applied in Mississippi during the sampling of rainwater in comparison with the quantities applied in Alsace. Diflufenican was detected in 31% of the samples but in many cases at concentrations below detection limits. However, in contrary to parathion-methyl, it was more frequently detected in the air (Scheyer et al., 2007b). This difference of behaviour between these two pesticides can be explained by their Henry law constant and solubility in water. Indeed, diflufenican presents a high Henry law constant (0.033 Pa m3 mol1) and a poor solubility in water (o0.05 mg L1) which induce a low affinity to the aqueous phase. Parathion-methyl presents a low Henry law constant (9.6.104 Pa m3 mol1) and a good solubility in water (60 mg L1) which permit a good wash out by precipitation. Diflufenican was observed at high concentration in Erstein between 4 November 2002 and 11 November 2002 (101 ng L1) and between 28 April 2003 and 15 May 2003 (762 ng L1) but not in Strasbourg. The first concentration corresponds to a treatment performed in autumn and the second one corresponds to a treatment performed in spring. An important concentration in the air was also observed between 28 April 2003 and 29 April 2003 in Geispolsheim (1534 ng L1), a town in the vicinity of Erstein, but not detected in the same time in Strasbourg (Scheyer et al., 2007b). The concordance of the behaviour of diflufenican between rainwater and air analysis tends to demonstrate a rapid deposition of this fungicide near to the application site and a very limited local transport.
Chlorfevinphos and phosalone were detected, respectively, 2 and 4 times in Erstein and Strasbourg during the sampling period. Between 28 April 2003 and 15 May 2003, 187 ng L1 of phosalone and 157 ng L1 of chlorfevinphos were measured at Erstein while in Strasbourg their concentrations were below the quantification limits. During this period, some insecticide treatments could be performed on vineyard and could explain concentrations measured. This hypothesis is corroborated by their detection in Erstein, which is a site situated directly under the wind of vineyard crops. Aryloxyacids (MCPA, MCPP, 2,4-D) were detected in some rainwater sampled in Erstein and Strasbourg at high concentrations whereas they were practically not detected in air samples (Scheyer et al., 2007b). The main reason is the high detections limits obtained for these pesticides with the analytical method used (Scheyer et al., 2007a). Concentrations and periods of detection are presented in Table 1. They were generally detected in spring at higher concentrations in Erstein than in Strasbourg. These herbicides are applied on cereals crops in spring and their preferential measurements in spring can be explained. The 2,4-D was detected essentially in Strasbourg in spring and summer. No explanation can be, with the current data, advanced for this observation but since these herbicides can be used by local municipalities to control weeds along roadways and other right-of-ways, an urban application of these herbicides can be the most probable reason of their detection in the urban site. 3.2. Pesticides detected seasonally Herbicides commonly and intensively used in maize crops were detected with a pronounced seasonal profile. This is the case for atrazine, alachlor and metolachlor where an increase in concentrations starts in April, reaches a maximum in the beginning of May and decreases at the end of June. This profile was observed during the 2 years of measurements on the two sites and corresponds to the period of application of these herbicides on crops. Alachlor, atrazine and metolachlor present a high water solubility and low Henry’s law constants. These properties are in favour of their enrichment in rainwater since herbicides at low Henry’s law constants are preferentially present in the particle phase and consequently more efficiently deposited by precipitations.
ARTICLE IN PRESS A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–7252 Table 1 Concentrations (in ng L1) of MCPP, MCPA and 2,4-D measured in rainwater samples collected at Erstein and Strasbourg between 2002 and 2003 Period of sampling 4–10/03/02 Strasbourg Erstein 22–29/04/02 Strasbourg Erstein 14–21/05/02 Strasbourg Erstein 15–22/07/02 Strasbourg Erstein 20–26/08/02 Strasbourg Erstein 23–28/10/02 Strasbourg Erstein 09/12/02–04/01/03 Strasbourg Erstein 20–27/01/03 Strasbourg Erstein 27/01–10/02/03 Strasbourg Erstein 01–25/03/03 Strasbourg Erstein 25/03–06/04/03 Strasbourg Erstein 06–14/04/03 Strasbourg Erstein 14–21/04/03 Strasbourg Erstein 21–28/04/03 Strasbourg Erstein 28/04–15/05/03 Strasbourg Erstein
MCPA
MCPP
2,4-D
13
483
50
590
122
527 663 228
79
82 123 145 268
95 70
oQL
oQL
oQL
oQL
oQL oQL
56 59
731 746
oQL 904
237
oQL: below quantification limits.
Concentrations of atrazine (Fig. 3) on the two sites are on the same order of magnitude, except on the week of 30 April 2002–6 May 2002 (6.25 mg L1 in Erstein) and of 15 May 2003–28 May 2003 (1.5 mg L1 in Erstein). These 2 weeks correspond to the intensive application of atrazine on maize and the Erstein site is
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situated directly near maize crops. Moreover, during the first week (30 April 2002–6 May 2002), wind comes from south and could have induced a short-range transport of atrazine form these areas to the sampling site situated in Erstein. The local drift of atrazine in Erstein in comparison to Strasbourg can be confirmed by the comparison of concentrations obtained in urban rainwater in other studies (Table 2). Concentrations measured in Erstein were the highest ones and confirm an application close to the site. It can also be seen that concentrations of atrazine measured in Strasbourg in 2001 and 2002–2003, period of intensive used of this herbicide, were in the same order of magnitude. Generally, main wind direction in the Rhine upper valley comes from southwest. Concentrations of atrazine were higher in Strasbourg only on the week from 3 June to 10 June. This observation can be explained by a short transport of atrazine applied in the north of Strasbourg. Wind direction during this period, coming from the north, confirms this hypothesis. Concentrations of alachlor and metolachlor present the same profile as concentrations of atrazine. To illustrate this result, the variations of concentrations of alachlor in Strasbourg and Erstein between 2002 and 2003 are presented in Fig. 4. However, the highest concentrations were measured in Strasbourg for alachlor in 2003. It is difficult to explain this phenomenon with the data available. Concentrations measured for alachlor were higher than those measured in the same period for atrazine and this difference can be compared with the quantity of atrazine and alachlor applied by hectare. Indeed, alachlor is applied on maize crop at a concentration of 2.5 more important than atrazine. Since alachlor is more volatile than atrazine, it is possible that this molecule can volatilise more importantly and explain also the elevated concentration measured. For alachlor and metolachlor, some traces were measured out of the normal period of application and this observation could indicate a more persistence of these herbicides in comparison to atrazine. Due to this persistence these compounds could be volatilised from soils of leaves after their application and atmospheric concentrations could be washed out again by precipitation. 3.3. Pesticides detected systematically Among the pesticides monitored, lindane, endosulfan and diuron were detected practically in all
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7248 8000
Strasbourg Erstein
7000
Concentration in ng.L-1
6000
5000 1500 1250 1000 750 500 250
4-10 march 11-18 march 18-24 march 24-1 april 1-8 april 8-15 april 16-22 april 22-29 april 30-06 may 7-13 may 14-21 may 22-29 may 3-10 june 10-17 june 17-24 june 24-1 july 1-7 july 15-22 july 23-30 july 9-16 sept 16-23 sept 23-30 sept 20-27 jan 27-10 feb 10-1 march 1-25 march 25-6 april 6-14 april 14-21 april 21-28 april 28-15 may 16-28 may 28-08 july 8-20 july
0
Period of sampling
Fig. 3. Evolution of the concentrations of atrazine (in ng L1) in the two sites between March 2002 and July 2003. Table 2 Comparison of pesticides concentrations in different parts of the world (in ng L1)
(min/max) Atrazine Trifluralin Lindane Endosulfan Iprodione Metolachlor Diuron Parathion-M Diflufenican
Trevisan et al. (1993) (Italy)
Chevreuil et al. Coupe et al. (1996) (Paris (2000) area) (Mississippi)
Quaghebeur et al. (2004) (Belgium)
Sauret (2002) (Strasbourg)
This study (2002–2003) (Strasbourg)
This study (2002–2003) (Erstein)
150/1990 50/3440 NA NA 111/560 NA NA NA NA
oQL/400 NA 14/350 NA NA NA NA NA NA
/1300 /53 /1700 /285 ND /1100 /6400 /45 NA
oQL/1181 NA NA NA oQL/3249 oQL/1480 NA NA oQL/2894
36/1031 oQL oQL/132 oQL/3667 oQL/5590 oQL/122 oQL/1025 oQL oQL/57
oQL/6248 oQL oQL/174 oQL/1506 oQL/3327 oQL/799 oQL/1317 oQL oQL/762
6/96 o2/10 ND NA ND D NA 24/300 NA
NA, not analysed; oQL: below quantification limit.
anlaysed rainwater samples. For these pesticides, no seasonal trends were observed whatever the sampling site.
Lindane is one of the most studied pesticides in the literature. Dubus et al. (2000) state that this insecticide was generally detected in 90% of the
ARTICLE IN PRESS A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–7252
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6000
5000
Strasbourg
Concentration in ng.L-1
Erstein 4000
3000
1000
4-10 march 11-18 march 18-24 march 24-1 april 1-8 april 8-15 april 16-22 april 22-29 april 30-06 may 7-13 may 14-21 may 22-29 may 3-10 june 10-17 june 17-24 june 24-1 july 1-7 july 15-22 july 23-30 july 9-16 sept 16-23 sept 23-30 sept 20-27 jan 27-10 feb 10-1 march 1-25 march 25-6 april 6-14 april 14-21 april 21-28 april 28-15 may 16-28 may 28-08 july 8-20 july 12-18 nov 9-4 janv 04-20 janv 20-27 janv 27-10 fév 25-6 avril 6-14 avril 14-21 avril 21-28 avril 28-15 mai 16-28 mai 28-08 juil 8-20 juil
0
Period of sampling
Fig. 4. Evolution of the concentrations of alachlor (in ng L1) in the two sites between March 2002 and July 2003.
rainwater samples where it was analysed. In our study, the frequency of detection is lower since it was detected in about 50% of the urban and rural analysed samples (Fig. 5). Lindane presents a low solubility in water and a high volatility and concentrations measured were very low. Highest concentrations were measured between 28 April 2003 and 15 May 2003 (90 and 174 ng L1 in Strasbourg and Erstein, respectively). During this period, an important global radiance was observed by METEOFrance and consequently high temperature favouring volatilisation processes. The increase in the concentrations of lindane measured in rainwater could be the consequence of volatilisation from contaminated soils followed by a local transport. The high levels observed in Strasbourg between 9 December 2002 and 04 January 2003 cannot be explained by volatilisation processes. A global transport phenomenon could explain this concentration. Endosulfan, as for lindane, is an insectricide systematically detected in precipitation when ana-
lysed (Quaghebeur et al., 2004). In this study, it was detected in 85% of the analysed samples. This is not in accordance with the properties of endosulfan which is low soluble in water and has a high Henry’s law constant. Trends of concentrations present the same profile as lindane but concentrations were higher (by a factor of 10). High concentrations were detected in Strasbourg between 9 December 2002 and 4 January 2003. These high concentrations cannot be explained by an application of endosulfan which 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 Arctic region at concentration between 22 and 136 ng L1. This result tends to validate our hypothesis about a long-range transport and also tends to confirm the atmospheric persistence of endosulfan. Endosulfan is characteristic of type of deposition D following the classification of Dubus et al. (2000) while lindane is characteristic of type of deposition C.
ARTICLE IN PRESS A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–7252
7250
250
Strasbourg
Concentration in ng.L-1
200
Erstein
150
100
50
4-10 march 11-18march 18-24 march 24-1 april 1-8 april 8-15 april 16-22 april 22-29 april 30-06 may 7-13 may 14-21 may 22-29 may 3-10 june 10-17 june 17-24 june 24-1 july 1-15 july 15-22 july 23-30 july 30-5 aug 6-13 aug 13-20 aug 20-26 agu 26-2 sept 2-9 sept 9-16 sept 16-23 sept 23-30 sept 30-07 oct 08-15 oct 15-23 oct 23-28 oct 28-4 nov 04-12 nov 12-18 nov 18-26 nov 26-2 dec 2-9 dec 9-4 jan 04-20 jan 20-27 jan 27-10 feb 10-1 march 1-25 march 25-6 april 6-14 april 14-21 april 21-28 april 28-15 may 16-28 may 28-08 july 8-20 juillet
0
Period of sampling Fig. 5. Evolution of the concentrations of lindane (in ng L1) in the two sites between March 2002 and July 2003.
No seasonal trends for diuron were observed as shown in Fig. 6. This herbicide was detected in 40 samples in Strasbourg for a total number of 41 samples. Highest concentrations of 1025 ng L1 were observed in Strasbourg during the week from 16 to 23 September 2002. The frequency of detection was lower in Erstein since diuron was detected on only 38 samples and the maximum concentrations was observed in the week from 15 to 23 October 2002 (1317 ng L1). The high frequency of detection of diuron in rainwater can be explained by its low Henry’s law constant (5.1 105 Pa m3 mol1) which facilitates a more important transfer to rainwater droplets. The sum of the concentration of diuron measured in Strasbourg between 4 March 2002 and 23 July 2003 is 4721 ng L1 and 5025 ng L1 in Strasbourg and Erstein, respectively. The atmospheric deposition of diuron by precipitation is of the same order of magnitude between urban and rural areas explaining the ‘‘urban use’’ of this herbicide. The
same behaviour was observed in air samples collected in the same period (Scheyer et al., 2007b). Quaghebeur et al. (2004) have observed higher concentration of diuron in urban site than in rural site. Their results tend to confirm the hypothesis of the influence of the urban application of diuron. Diuron is characteristic of type of deposition D. 4. Conclusion Rainwater samples were collected simultaneously between 2002 and 2003 on rural and urban sites in Alsace. Results obtained by the SPME analysis of current-used pesticides during this period of sampling show that the contamination of rainwater by pesticides is function of:
the physical and chemical properties of pesticides, the period and the dose of application,
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2000 1800 1600
Strasbourg Erstein
Concentration in ng.L-1
1400 1200 1000 800 600 400 200
18-24 march 24-1 apr 1-8 apr 8-15 apr 16-22 apr 22-29 apr 30-06 apr 7-13 may 14-21 may 22-29 may 3-10 june 10-17 june 17-24 june 24-1 july 1-15 july 15-22 july 23-30 july 30-5 aug 6-13 aug 13-20 aug 20-26 aug 26-2 sept 2-9 sept 9-16 sept 16-23 sept 23-30 sept 30-07 oct 08-15 oct 15-23 oct 23-28 oct 28-4 nov 04-12 nov 12-18 nov 18-26 nov 26-2 dec 2-9 dec 9-4 jan 04-20 jan 20-27 jan 27-10 feb 10-1 march 1-25 march 25-6 apr 6-14 apr 14-21 apr 21-28 apr 28-15 may 16-28 may 28-08 july 8-20 juil
0
Period of sampling Fig. 6. Evolution of the concentrations of diuron (in ng L1) in the two sites between March 2002 and July 2003.
the localisation of the application and the climatic conditions during application, local and long-range transport phenomena.
Rainwater could be a very simple and inexpensive technique for the indirect evaluation of the spatial and temporal evaluation of the atmospheric contamination by pesticides instead of Hi-Vol sampling, generally more complicated to use and analyse. However, the need of regular rain events at moderate intensity is required. Acknowledgements The authors would like to thank the ‘‘Region Alsace’’, the ‘‘DRIRE Alsace’’ and the French Ministry of Ecology and Sustainable Development through the Primequal-2 program for their financial support.
Anne Scheyer particularly thanks ADEME and ‘‘Re´gion Alsace’’ for a PhD grant. The ‘‘Chambre Re´gionale d’Agriculture ‘‘is also gratefully acknowledged, in particular Mr. Jean Richert for his help. References Abbott, D.C., Harrison, R.B., Tatton, J.O’.G., Thomson, J., 1965. Organochlorine pesticides in the atmospheric environment. Nature 208, 1317–1318. Asman, W.A.H., Jørgensen, A., Bossi, R., Vejrup, K.V., Bu¨gel Mogensen, B., Glasius, M., 2005. Wet deposition of pesticides and nitrophenols at two sites in Denmark: measurements and contributions from regional sources. Chemosphere 59, 1023–1031. Atkinson, R., Guicherit, R., Hites, R.A., Palm, W.U., Seiber, J.N., de Voogt, P., 1999. Transformation of pesticides in the atmosphere: a state of the art. Water, Air and Soil Pollution 115, 219–243. Briand, O., Seux, R., Millet, M., Cle´ment, M., 2002. Influence de la pluviome´trie sur la contamination de l’atmosphe`re et des
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eaux de pluie par les pesticides. Revue des Sciences de l’Eau 15, 767–787. Chevreuil, M., Garmouma, M., Teil, M.-J., Chesterikoff, A., 1996. Occurrence of organochlorines (PCBs, pesticides) and herbicides (Triazines, phenylureas) in the atmosphere and in the fallout from urban and rural stations of the Paris area. Science of the Total Environment 182, 25–37. Coupe, R.H., Manning, M.A., Foreman, W.T., Goolsby, D.A., Majewski, M.S., 2000. Occurrence of pesticides in rain and air in urban and agricultural areas of Mississippi, April–September 1995. Science of the Total Environment 248, 227–240. De Rossi, C., Bierl, R., Riefstahl, J., 2003. Organic Pollutants in precipitation: monitoring of pesticides and polycyclic aromatic hydrocarbons in the region of Trier (Germany). Physics and Chemistry Earth 28, 307–314. Dubus, I.G., Hollis, J.M., Brown, C.D., 2000. Pesticides in Rainfall in Europe. Environmental Pollution 110, 331–344. Epple, J., Maguhn, J., Spitzauer, P., Kettrup, A., 2002. Input of pesticides by atmospheric deposition. Geoderma 105, 327–349. Grybkiewicz, M., Polkowska, Z., Go´recki, T., Namies´ nick, J., 2003. Pesticides in precipitation from an urban region in Poland (Gdans´ k-Sopot-Gdynia tricity) between 1998 and 2000. Water, Air and Soil Pollution 149, 3–16. Haragushi, K., Kitamura, E., Yamashita, T., Kido, A., 1995. Simultaneous determination of trace pesticides in urban precipitation. Atmospheric Environment 29, 247–253. Magdic, S., Boyd-Boland, A., Jinno, K., Pawliszyn, J.B., 1996. Analysis of organophosphorus insecticides from environmental samples using solid-phase microextraction. Journal of Chromatography A 776, 219–228. Mc Connell, L.L., LeNoir, J.S., Datta, S., Seiber, J.N., 1998. Wet deposition of current-use pesticides in the Sierra Nevada mountain range, California, USA. Environmental Toxicology and Chemistry 17, 1908–1916.
Millet, M., Wortham, H., Sanusi, A., Mirabel, Ph., 1997. Atmospheric contamination by pesticides: Determination in the liquid, gaseous and particulate phases. Environmental Science and Pollution Research 4, 172–180. Quaghebeur, D., De Smet, B., De Wulf, E., Steurbautb, W., 2004. Pesticides in rainwater in Flanders, Belgium: results from the monitoring program 1997–2001. Journal of Environmental Monitoring 6, 182–190. Sauret, N., 2002. Ph.D. Thesis, University of Strasbourg I, 212pp (in French). Scheyer, A., Morville, S., Mirabel, Ph., Millet, M., 2006a. Analysis of trace levels of pesticides in rainwater using SPME and GC-tandem mass spectrometry. Analytical and Bioanalytical Chemistry 384, 475–487. Scheyer, A., Briand, O., Morville, S., Mirabel, Ph., Millet, M., 2007a. Analysis of trace levels of pesticides in rainwater by SPME and GC-tandem mass spectrometry after derivatisation with PFFBr. Analytical and Bioanalytical Chemistry 387, 359–368. Scheyer, A., Morville, S., Mirabel, Ph., Millet, M., 2007b. Variability of atmospheric pesticide concentrations between urban and rural areas during intensive pesticide application. Atmospheric Environment, in press, doi:10.1016/j.atmosenv. 2006.12.042. Tarrant, K.R., Tatton, J.O’.G., 1968. Organochlorine pesticides in rainwater in the British Isles. Nature 219, 725–727. Trevisan, M., Montepiani, C., Ragozza, L., Bartoletti, C., Ioannilli, E., Del Re, A.A.M., 1993. Pesticides in Rainfall and air in Italy. Environmental Pollution 80, 31–39. Van Dijk, H.F.G., Guicherit, R., 1999. Atmospheric dispersion of current-use pesticides: a review of the evidence from monitoring studies. Water, Air and Soil Pollution 115, 21–70. Wheatley, G., Hardman, J., 1965. Indications of the presence of organochlorine insecticides in rainwater in central England. Nature 207, 486–487.
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, Ste´phane Morville, Philippe Mirabel, Maurice Millet Laboratoire de Physico-Chimie de l’Atmosphe`re (UMR 7517), Centre de Ge´ochimie de la Surface et De´partement 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 (100 mm) 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 ng L1 at Erstein and 5590 ng L1 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 ng L1) in Erstein in November 2002 (4–11 November) and a second one (762 ng L1) 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 ng L1 of phosalone and 157 ng L1 of chlorfenvinphos in Erstein). Corresponding author. Tel.: +33 390 240 422; fax: +33 390 240 402.
E-mail address: [email protected] (M. Millet). 1352-2310/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.atmosenv.2007.05.025
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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 ng L1, 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 ng L1 (16–23 September 2002) in 38 samples on 41 in Erstein with a maximum of 317 ng L1 (15–23 October 2002). The total concentration of Diuron measured between 4 March 2002 and 20 July 2003 is of 4721 ng L1 in Strasbourg and 5025 ng L1 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 pathway for the transport and dissemination of residues of pesticides. This is firstly observed in the 1960s for organochlorine pesticides when they were intensively used in many countries (Abbott et al., 1965; Wheatley and Hardman 1965; Tarrant and Tatton, 1968). The emissions of current-used pesticide into the atmosphere can be the consequence of ‘‘spray drift’’ followed by volatilisation during application, post-application volatilisation from treated crops and leaves and wind erosion of fine soil particles where pesticides are adsorbed. When in the atmosphere, pesticides can be found in both the gaseous and the particulate phase (Millet et al., 1997) and they can be transported sometimes far from their application site, depending on their potentiality of persistence, and deposited through wet and dry deposition processes. The removal rate of pesticides from the atmosphere by wet deposition depends partly on Henry’s law coefficient, to some extent on their diffusivity in air, and on meteorological conditions (wind speed, atmospheric stability, precipitation) and on the conditions of the surface (for dry deposition only). The atmospheric lifetime of pesticides is not only influenced by their removal rate by dry and wet deposition, but also by photochemical reactions with OH radicals and O3 (Atkinson et al., 1999). The presence of modern pesticides, like 2,4-D, in rainwater were published for the first time in the mid-1960s by Cohen and Pinkerton (Van Dijk and Guicherit, 1999) but until the late 1980s, no special attention was given to this problem. Van Dijk and
Guicherit (1999) and Dubus et al. (2000) published in the beginning of the 2000s reviews on monitoring data of current-use pesticides in rainwater for European countries. Some other measurements were also performed in the US (Mc Connell et al., 1998; Coupe et al., 2000) and in Japan (Haragushi et al., 1995) and more recently in France (Briand et al., 2002), Germany (Epple et al., 2002; de Rossi et al., 2003), Poland (Grybkiewicz et al., 2003), Belgium (Quaghebeur et al., 2004) and Denmark (Asman et al., 2005). Pesticides are generally present in precipitation from few ng L1 to several mg L1 (Van Dijk and Guicherit, 1999) and the highest concentrations were detected during application of pesticides into crops. Generally, a local contamination of rainwater by pesticides was observed but some data show a contamination of rainwater by pesticides in regions where they are not in used (Van Dijk and Guicherit, 1999). These data suggest the potentiality of transport and consequently the potentiality of the contamination of ecosystems far from their application. The actual concentration of a pesticide in rainwater or wet deposition of a pesticide does not only depend on its properties, on the precipitation amount and the meteorological conditions at the observational site, but also on the geographical distribution of the amount of pesticide applied, the type of surface onto which it is applied and the meteorological conditions in the area of which the emissions contribute to the concentration at the measuring site. Actually, little is known about the ecological effects on rainwater deposition of current-used pesticides on aquatic of terrestrial ecosystems.
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The aim of this work was to compare the levels of pesticides in rainwater collected between a rural and an urban site in the north of the Alsace region (Eastern France). This region is densely populated and 41% of its surface is used for agriculture. The main agricultural activity is dominated by cereals and maize (57% of the total agricultural surface) and the number of hectares used for these kinds of cropping have increased by 10% between 1988 and 2000. Others crops type areas remain stable and include vineyards, fruits, vegetables, hop, sugar beet, etc. Intensive agricultural activities and the diversity of crops in the Alsace region are responsible for an important use of synthetic pesticides, including herbicides, fungicides and insecticides. This intensive application of pesticides can induce an important contamination of rainwater. In order to evaluate this contamination and its spatial and temporal variability, rainwater samples were collected for 18 months in a typical rural and urban site situated in Strasbourg (Eastern France) and in its vicinity. 2. Materials and methods 2.1. Chemicals High purity standard pesticides [alachlor (99.7%), atrazine (99.2%), azinphos-ethyl (99.4%), azinphosmethyl (98.6%), bromoxynil (99.3%), captan (99.7%), chlorfenvinphos (98.4%), chlorotoluron (99.6%), 2,4-D (99.6%), dichlorvos (99.0%), diflufenican (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%), phosmet (99.9%), tebuconazole (98.0%), triadimefon (99.9%) and trifluralin (99.3%)] and the internal standards (deuterated naphthalene and tecnazen (99.8%)) were obtained from Promochem (Molsheim, 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 provided from Aldrich and Fluka, respectively. A stock solution (1 g L1) was prepared for each pesticide in methanol. Mixtures of pesticides were prepared in methanol containing 100 mg L1 of each individual pesticide. Ultrapure Milli-Q water
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(Millipore) was used to prepare the different standard solutions. The final percentage of methanol in all standard solution did not exceed 0.1% and did not have an influence on the efficiency of the extraction (Scheyer et al., 2006, 2007a). The solid phase micro-extraction (SPME) holder and fibre assemblies (polydimethylsiloxane (PDMS) and PDMS/DVB (divinylbenzene)) for manual sampling were provided by Supelco (France). 2.2. Sampling location To compare rainwater contamination in different locations, rain samples were collected in two sampling stations (Fig. 1). The first station was chosen in order to represent an urban area and the rainwater collector was placed in the botanical garden of the Strasbourg University situated near the historic centre of Strasbourg (400 000 inhabitants). The particular feature of this city is that intensive agricultural activities (essentially maize) take place at only 15 km of its centre, to the south. The second sampling point was installed in a rural area, situated 25 km southeast of Strasbourg, at 2 km from a small town, Erstein (9000 inhabitants), and 300 m from the nearest treated area. The two collectors were placed on the soil, but far from the treated area in order to avoid the possible direct input of pesticides from treatment into the sampler. 2.3. Sample collection Samples were collected simultaneously on the two sites on a weekly basis between January 2002 and September 2003 by using a wet only rainwater sampler (Pre´cis Me´canique, France) agreed by METEO-France. After sampling, samples were stored in darkness at 18 1C before analysis. In order to eliminate the variations on concentrations inherent to the fluctuation of the precipitation level during a week of sampling, each station was also equipped with a graduated open collector (Pre´cis Me´canique, France). The normalised concentration is calculated according to C i1;norm ¼
C i1 H i , Hm
(1)
where Ci1,norm is the normalised concentration of species 1 in the sample i, Ci1 the concentration of species 1 in the sample i, Hi the precipitation
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Distribution of farming in Alsace Orchards
Crop (maize corn)
wine
Erstein
Pasture and breeding
Vegetable farming and pig breeding area
Forest and breeding area
fish and cow breedind area
Fig. 1. Distribution of agricultural activity in the Alsace region.
height of the sample i (in mm) and Hm the mean precipitation height (in mm). Precipitation heights were determined by using an open graduated rainwater collector. 2.4. SPME extraction of pesticides Alachlor, atrazine, azinphos-ethyl, azinphosmethyl, bromoxynil, captan, chlorfenvinphos, dichlorvos, diflufenican, a- and b-endosulfan, iprodione, lindane, metolachlor, mevinphos, parathionmethyl, phosalone, phosmet, tebuconazole, triadimefon and trifluralin were extracted by using a PDMS (100 mm) SPME fibre for 40 min at 45 1C (pH ¼ 6.0, saturated NaCl). Bromoxynil, chlorotoluron, diuron, isoproturon, 2,4-MCPA, MCPP and 2,4-D were extracted with a PDMS/DVB fibre by direct extraction for 60 min at 68 1C (pH 2 and 75% NaCl). Prior to this extraction procedure, a headspace coating of the fibre with PFBBr for 10 min was performed. Detailed analytical procedures are described elsewhere (Scheyer et al., 2006, 2007a).
2.5. Analysis A Varian Star 3400 CX gas chromatograph equipped with a split–splitless injector and coupled to a Varian Saturn IV mass selective detector was used. A Macherey–Nagel analytical capillary column OPTIMA 5 was chosen (30 m 0.32 mm, film thickness: 0.25 mm). Helium was used as the carrier gas and inlet pressure was 19 psi (corresponding to a flow rate of 2 mL min1). The injector and the transfer line temperatures were kept at 250 1C while the manifold temperature was 200 1C. For SPME analysis of non-derivatised pesticides, the GC temperature program varied between 60 1C (for 2 min) and 163 1C at 25 1C min1, then 163–165 1C at 0.3 1C min1, then 167–210 1C at 301 min1 and finally 210–250 1C (10 min) at 5 1C min1. For the SPME analysis of derivatised pesticides, the GC program varied between 80 1C (2 min) and 150 1C at 15 1C min1, then 150–192 1C at 3.1 1C min1, then 192–193 1C at 0.2 1C min1 and finally 193–250 1C (5 min) at 20 1C min1.
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For the quantification, an internal standard was used: deuterated naphthalene at 10 mg L1 for the non-derivatised runs and tecnazen at 10 mg L1 for the derivatised runs. Detection limits for the non-derivatised pesticides varied between 0.1 and 5 mg L1 while standard deviations varied from 10% to 34% (Scheyer et al., 2006). Detection limits were obtained for all the derivatised compounds that ranged between 10 and 1000 ng L1 with an important uncertainty due to the combination of derivatisation and SPME extraction steps (Scheyer et al., 2007a).
3. Results and discussion Among the 27 pesticides monitored in rainwater between 2002 and 2003 in Erstein and Strasbourg, azinphos-ethyl, azinphos-methyl, dichlorvos, iprodione, mevinphos, bromoxynil, chlorotoluron and
Type of déposition
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isoproturon were never detected. These pesticides were not detected during the sampling periods since:
they were not applied during the sampling period (azinphos-ethyl, azinphos-methyl, dichlorvos and mevinphos), they were applied very episodically at very low amounts (bromoxynil, iprodione), they were very low volatile and detection limits are high (chlorotoluron and isoproturon).
The behaviour of the pesticides detected in rainwater in Erstein and Strasbourg can be ranged in different classes following the classification proposed by Dubus et al. (2000) associating the type of deposition and transport phenomena (Fig. 2). Chlorfenvinphos, diflufenican, parathion-methyl, phosalone, MCPP, MCPA and 2,4-D were detected episodically in some samples while diuron, endosulfan and lindane were detected practically during all the sampling period in Erstein and Strasbourg.
Period of the year
Concentration
Type of Transport
Examples of pesticides
During application
Intermediate to elevated (10-max ng.L-1)
Local transport (< 1 km)
Chlorfenvinphos, phosalone, diflufenican
During season of treatment
Intermediate to elevated (10-max ng.L-1)
Medium to long distance (1 to 1000km)
Atrazine, Alachlore, metolachlor
Global
Lindane
A
B
C During all the year
Low (few ng.L-1to 10 ng.L-1)
D During all the year
Low to intermediate (few ng.L-1 to 1000 ng.L-1)
Local
Diuron, Endosulfan
Eprisodically
Low (few ng.L-1 to 10 ng.L-1)
Local
Trifluraline, parathion-methyl, MCPP, 2,4 MCPA
E
Fig. 2. Classification of pesticides studied following the model proposed by Dubus et al. (2000).
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The other pesticides (trifluralin, alachlor, atrazine and metolachlor) present very important seasonal effects strongly associated with their period of application. 3.1. Pesticides detected episodically Parathion-methyl was detected only two times at concentrations below quantification limits during the sampling period (3–6 June 2002 in Strasbourg; 21–28 April 2003 in Erstein). This insecticide was not detected in air samples collected during the same period of time (Scheyer et al., 2007b). This is not in accordance with results from Coupe et al. (2000) where high levels of methyl-parathion were measured in rainwater (22.9 mg L1) and also in air in the same week in the Mississippi state. The main reason of this difference is certainly the important quantities of methyl-parathion applied in Mississippi during the sampling of rainwater in comparison with the quantities applied in Alsace. Diflufenican was detected in 31% of the samples but in many cases at concentrations below detection limits. However, in contrary to parathion-methyl, it was more frequently detected in the air (Scheyer et al., 2007b). This difference of behaviour between these two pesticides can be explained by their Henry law constant and solubility in water. Indeed, diflufenican presents a high Henry law constant (0.033 Pa m3 mol1) and a poor solubility in water (o0.05 mg L1) which induce a low affinity to the aqueous phase. Parathion-methyl presents a low Henry law constant (9.6.104 Pa m3 mol1) and a good solubility in water (60 mg L1) which permit a good wash out by precipitation. Diflufenican was observed at high concentration in Erstein between 4 November 2002 and 11 November 2002 (101 ng L1) and between 28 April 2003 and 15 May 2003 (762 ng L1) but not in Strasbourg. The first concentration corresponds to a treatment performed in autumn and the second one corresponds to a treatment performed in spring. An important concentration in the air was also observed between 28 April 2003 and 29 April 2003 in Geispolsheim (1534 ng L1), a town in the vicinity of Erstein, but not detected in the same time in Strasbourg (Scheyer et al., 2007b). The concordance of the behaviour of diflufenican between rainwater and air analysis tends to demonstrate a rapid deposition of this fungicide near to the application site and a very limited local transport.
Chlorfevinphos and phosalone were detected, respectively, 2 and 4 times in Erstein and Strasbourg during the sampling period. Between 28 April 2003 and 15 May 2003, 187 ng L1 of phosalone and 157 ng L1 of chlorfevinphos were measured at Erstein while in Strasbourg their concentrations were below the quantification limits. During this period, some insecticide treatments could be performed on vineyard and could explain concentrations measured. This hypothesis is corroborated by their detection in Erstein, which is a site situated directly under the wind of vineyard crops. Aryloxyacids (MCPA, MCPP, 2,4-D) were detected in some rainwater sampled in Erstein and Strasbourg at high concentrations whereas they were practically not detected in air samples (Scheyer et al., 2007b). The main reason is the high detections limits obtained for these pesticides with the analytical method used (Scheyer et al., 2007a). Concentrations and periods of detection are presented in Table 1. They were generally detected in spring at higher concentrations in Erstein than in Strasbourg. These herbicides are applied on cereals crops in spring and their preferential measurements in spring can be explained. The 2,4-D was detected essentially in Strasbourg in spring and summer. No explanation can be, with the current data, advanced for this observation but since these herbicides can be used by local municipalities to control weeds along roadways and other right-of-ways, an urban application of these herbicides can be the most probable reason of their detection in the urban site. 3.2. Pesticides detected seasonally Herbicides commonly and intensively used in maize crops were detected with a pronounced seasonal profile. This is the case for atrazine, alachlor and metolachlor where an increase in concentrations starts in April, reaches a maximum in the beginning of May and decreases at the end of June. This profile was observed during the 2 years of measurements on the two sites and corresponds to the period of application of these herbicides on crops. Alachlor, atrazine and metolachlor present a high water solubility and low Henry’s law constants. These properties are in favour of their enrichment in rainwater since herbicides at low Henry’s law constants are preferentially present in the particle phase and consequently more efficiently deposited by precipitations.
ARTICLE IN PRESS A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–7252 Table 1 Concentrations (in ng L1) of MCPP, MCPA and 2,4-D measured in rainwater samples collected at Erstein and Strasbourg between 2002 and 2003 Period of sampling 4–10/03/02 Strasbourg Erstein 22–29/04/02 Strasbourg Erstein 14–21/05/02 Strasbourg Erstein 15–22/07/02 Strasbourg Erstein 20–26/08/02 Strasbourg Erstein 23–28/10/02 Strasbourg Erstein 09/12/02–04/01/03 Strasbourg Erstein 20–27/01/03 Strasbourg Erstein 27/01–10/02/03 Strasbourg Erstein 01–25/03/03 Strasbourg Erstein 25/03–06/04/03 Strasbourg Erstein 06–14/04/03 Strasbourg Erstein 14–21/04/03 Strasbourg Erstein 21–28/04/03 Strasbourg Erstein 28/04–15/05/03 Strasbourg Erstein
MCPA
MCPP
2,4-D
13
483
50
590
122
527 663 228
79
82 123 145 268
95 70
oQL
oQL
oQL
oQL
oQL oQL
56 59
731 746
oQL 904
237
oQL: below quantification limits.
Concentrations of atrazine (Fig. 3) on the two sites are on the same order of magnitude, except on the week of 30 April 2002–6 May 2002 (6.25 mg L1 in Erstein) and of 15 May 2003–28 May 2003 (1.5 mg L1 in Erstein). These 2 weeks correspond to the intensive application of atrazine on maize and the Erstein site is
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situated directly near maize crops. Moreover, during the first week (30 April 2002–6 May 2002), wind comes from south and could have induced a short-range transport of atrazine form these areas to the sampling site situated in Erstein. The local drift of atrazine in Erstein in comparison to Strasbourg can be confirmed by the comparison of concentrations obtained in urban rainwater in other studies (Table 2). Concentrations measured in Erstein were the highest ones and confirm an application close to the site. It can also be seen that concentrations of atrazine measured in Strasbourg in 2001 and 2002–2003, period of intensive used of this herbicide, were in the same order of magnitude. Generally, main wind direction in the Rhine upper valley comes from southwest. Concentrations of atrazine were higher in Strasbourg only on the week from 3 June to 10 June. This observation can be explained by a short transport of atrazine applied in the north of Strasbourg. Wind direction during this period, coming from the north, confirms this hypothesis. Concentrations of alachlor and metolachlor present the same profile as concentrations of atrazine. To illustrate this result, the variations of concentrations of alachlor in Strasbourg and Erstein between 2002 and 2003 are presented in Fig. 4. However, the highest concentrations were measured in Strasbourg for alachlor in 2003. It is difficult to explain this phenomenon with the data available. Concentrations measured for alachlor were higher than those measured in the same period for atrazine and this difference can be compared with the quantity of atrazine and alachlor applied by hectare. Indeed, alachlor is applied on maize crop at a concentration of 2.5 more important than atrazine. Since alachlor is more volatile than atrazine, it is possible that this molecule can volatilise more importantly and explain also the elevated concentration measured. For alachlor and metolachlor, some traces were measured out of the normal period of application and this observation could indicate a more persistence of these herbicides in comparison to atrazine. Due to this persistence these compounds could be volatilised from soils of leaves after their application and atmospheric concentrations could be washed out again by precipitation. 3.3. Pesticides detected systematically Among the pesticides monitored, lindane, endosulfan and diuron were detected practically in all
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7248 8000
Strasbourg Erstein
7000
Concentration in ng.L-1
6000
5000 1500 1250 1000 750 500 250
4-10 march 11-18 march 18-24 march 24-1 april 1-8 april 8-15 april 16-22 april 22-29 april 30-06 may 7-13 may 14-21 may 22-29 may 3-10 june 10-17 june 17-24 june 24-1 july 1-7 july 15-22 july 23-30 july 9-16 sept 16-23 sept 23-30 sept 20-27 jan 27-10 feb 10-1 march 1-25 march 25-6 april 6-14 april 14-21 april 21-28 april 28-15 may 16-28 may 28-08 july 8-20 july
0
Period of sampling
Fig. 3. Evolution of the concentrations of atrazine (in ng L1) in the two sites between March 2002 and July 2003. Table 2 Comparison of pesticides concentrations in different parts of the world (in ng L1)
(min/max) Atrazine Trifluralin Lindane Endosulfan Iprodione Metolachlor Diuron Parathion-M Diflufenican
Trevisan et al. (1993) (Italy)
Chevreuil et al. Coupe et al. (1996) (Paris (2000) area) (Mississippi)
Quaghebeur et al. (2004) (Belgium)
Sauret (2002) (Strasbourg)
This study (2002–2003) (Strasbourg)
This study (2002–2003) (Erstein)
150/1990 50/3440 NA NA 111/560 NA NA NA NA
oQL/400 NA 14/350 NA NA NA NA NA NA
/1300 /53 /1700 /285 ND /1100 /6400 /45 NA
oQL/1181 NA NA NA oQL/3249 oQL/1480 NA NA oQL/2894
36/1031 oQL oQL/132 oQL/3667 oQL/5590 oQL/122 oQL/1025 oQL oQL/57
oQL/6248 oQL oQL/174 oQL/1506 oQL/3327 oQL/799 oQL/1317 oQL oQL/762
6/96 o2/10 ND NA ND D NA 24/300 NA
NA, not analysed; oQL: below quantification limit.
anlaysed rainwater samples. For these pesticides, no seasonal trends were observed whatever the sampling site.
Lindane is one of the most studied pesticides in the literature. Dubus et al. (2000) state that this insecticide was generally detected in 90% of the
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6000
5000
Strasbourg
Concentration in ng.L-1
Erstein 4000
3000
1000
4-10 march 11-18 march 18-24 march 24-1 april 1-8 april 8-15 april 16-22 april 22-29 april 30-06 may 7-13 may 14-21 may 22-29 may 3-10 june 10-17 june 17-24 june 24-1 july 1-7 july 15-22 july 23-30 july 9-16 sept 16-23 sept 23-30 sept 20-27 jan 27-10 feb 10-1 march 1-25 march 25-6 april 6-14 april 14-21 april 21-28 april 28-15 may 16-28 may 28-08 july 8-20 july 12-18 nov 9-4 janv 04-20 janv 20-27 janv 27-10 fév 25-6 avril 6-14 avril 14-21 avril 21-28 avril 28-15 mai 16-28 mai 28-08 juil 8-20 juil
0
Period of sampling
Fig. 4. Evolution of the concentrations of alachlor (in ng L1) in the two sites between March 2002 and July 2003.
rainwater samples where it was analysed. In our study, the frequency of detection is lower since it was detected in about 50% of the urban and rural analysed samples (Fig. 5). Lindane presents a low solubility in water and a high volatility and concentrations measured were very low. Highest concentrations were measured between 28 April 2003 and 15 May 2003 (90 and 174 ng L1 in Strasbourg and Erstein, respectively). During this period, an important global radiance was observed by METEOFrance and consequently high temperature favouring volatilisation processes. The increase in the concentrations of lindane measured in rainwater could be the consequence of volatilisation from contaminated soils followed by a local transport. The high levels observed in Strasbourg between 9 December 2002 and 04 January 2003 cannot be explained by volatilisation processes. A global transport phenomenon could explain this concentration. Endosulfan, as for lindane, is an insectricide systematically detected in precipitation when ana-
lysed (Quaghebeur et al., 2004). In this study, it was detected in 85% of the analysed samples. This is not in accordance with the properties of endosulfan which is low soluble in water and has a high Henry’s law constant. Trends of concentrations present the same profile as lindane but concentrations were higher (by a factor of 10). High concentrations were detected in Strasbourg between 9 December 2002 and 4 January 2003. These high concentrations cannot be explained by an application of endosulfan which 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 Arctic region at concentration between 22 and 136 ng L1. This result tends to validate our hypothesis about a long-range transport and also tends to confirm the atmospheric persistence of endosulfan. Endosulfan is characteristic of type of deposition D following the classification of Dubus et al. (2000) while lindane is characteristic of type of deposition C.
ARTICLE IN PRESS A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–7252
7250
250
Strasbourg
Concentration in ng.L-1
200
Erstein
150
100
50
4-10 march 11-18march 18-24 march 24-1 april 1-8 april 8-15 april 16-22 april 22-29 april 30-06 may 7-13 may 14-21 may 22-29 may 3-10 june 10-17 june 17-24 june 24-1 july 1-15 july 15-22 july 23-30 july 30-5 aug 6-13 aug 13-20 aug 20-26 agu 26-2 sept 2-9 sept 9-16 sept 16-23 sept 23-30 sept 30-07 oct 08-15 oct 15-23 oct 23-28 oct 28-4 nov 04-12 nov 12-18 nov 18-26 nov 26-2 dec 2-9 dec 9-4 jan 04-20 jan 20-27 jan 27-10 feb 10-1 march 1-25 march 25-6 april 6-14 april 14-21 april 21-28 april 28-15 may 16-28 may 28-08 july 8-20 juillet
0
Period of sampling Fig. 5. Evolution of the concentrations of lindane (in ng L1) in the two sites between March 2002 and July 2003.
No seasonal trends for diuron were observed as shown in Fig. 6. This herbicide was detected in 40 samples in Strasbourg for a total number of 41 samples. Highest concentrations of 1025 ng L1 were observed in Strasbourg during the week from 16 to 23 September 2002. The frequency of detection was lower in Erstein since diuron was detected on only 38 samples and the maximum concentrations was observed in the week from 15 to 23 October 2002 (1317 ng L1). The high frequency of detection of diuron in rainwater can be explained by its low Henry’s law constant (5.1 105 Pa m3 mol1) which facilitates a more important transfer to rainwater droplets. The sum of the concentration of diuron measured in Strasbourg between 4 March 2002 and 23 July 2003 is 4721 ng L1 and 5025 ng L1 in Strasbourg and Erstein, respectively. The atmospheric deposition of diuron by precipitation is of the same order of magnitude between urban and rural areas explaining the ‘‘urban use’’ of this herbicide. The
same behaviour was observed in air samples collected in the same period (Scheyer et al., 2007b). Quaghebeur et al. (2004) have observed higher concentration of diuron in urban site than in rural site. Their results tend to confirm the hypothesis of the influence of the urban application of diuron. Diuron is characteristic of type of deposition D. 4. Conclusion Rainwater samples were collected simultaneously between 2002 and 2003 on rural and urban sites in Alsace. Results obtained by the SPME analysis of current-used pesticides during this period of sampling show that the contamination of rainwater by pesticides is function of:
the physical and chemical properties of pesticides, the period and the dose of application,
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2000 1800 1600
Strasbourg Erstein
Concentration in ng.L-1
1400 1200 1000 800 600 400 200
18-24 march 24-1 apr 1-8 apr 8-15 apr 16-22 apr 22-29 apr 30-06 apr 7-13 may 14-21 may 22-29 may 3-10 june 10-17 june 17-24 june 24-1 july 1-15 july 15-22 july 23-30 july 30-5 aug 6-13 aug 13-20 aug 20-26 aug 26-2 sept 2-9 sept 9-16 sept 16-23 sept 23-30 sept 30-07 oct 08-15 oct 15-23 oct 23-28 oct 28-4 nov 04-12 nov 12-18 nov 18-26 nov 26-2 dec 2-9 dec 9-4 jan 04-20 jan 20-27 jan 27-10 feb 10-1 march 1-25 march 25-6 apr 6-14 apr 14-21 apr 21-28 apr 28-15 may 16-28 may 28-08 july 8-20 juil
0
Period of sampling Fig. 6. Evolution of the concentrations of diuron (in ng L1) in the two sites between March 2002 and July 2003.
the localisation of the application and the climatic conditions during application, local and long-range transport phenomena.
Rainwater could be a very simple and inexpensive technique for the indirect evaluation of the spatial and temporal evaluation of the atmospheric contamination by pesticides instead of Hi-Vol sampling, generally more complicated to use and analyse. However, the need of regular rain events at moderate intensity is required. Acknowledgements The authors would like to thank the ‘‘Region Alsace’’, the ‘‘DRIRE Alsace’’ and the French Ministry of Ecology and Sustainable Development through the Primequal-2 program for their financial support.
Anne Scheyer particularly thanks ADEME and ‘‘Re´gion Alsace’’ for a PhD grant. The ‘‘Chambre Re´gionale d’Agriculture ‘‘is also gratefully acknowledged, in particular Mr. Jean Richert for his help. References Abbott, D.C., Harrison, R.B., Tatton, J.O’.G., Thomson, J., 1965. Organochlorine pesticides in the atmospheric environment. Nature 208, 1317–1318. Asman, W.A.H., Jørgensen, A., Bossi, R., Vejrup, K.V., Bu¨gel Mogensen, B., Glasius, M., 2005. Wet deposition of pesticides and nitrophenols at two sites in Denmark: measurements and contributions from regional sources. Chemosphere 59, 1023–1031. Atkinson, R., Guicherit, R., Hites, R.A., Palm, W.U., Seiber, J.N., de Voogt, P., 1999. Transformation of pesticides in the atmosphere: a state of the art. Water, Air and Soil Pollution 115, 219–243. Briand, O., Seux, R., Millet, M., Cle´ment, M., 2002. Influence de la pluviome´trie sur la contamination de l’atmosphe`re et des
ARTICLE IN PRESS 7252
A. Scheyer et al. / Atmospheric Environment 41 (2007) 7241–7252
eaux de pluie par les pesticides. Revue des Sciences de l’Eau 15, 767–787. Chevreuil, M., Garmouma, M., Teil, M.-J., Chesterikoff, A., 1996. Occurrence of organochlorines (PCBs, pesticides) and herbicides (Triazines, phenylureas) in the atmosphere and in the fallout from urban and rural stations of the Paris area. Science of the Total Environment 182, 25–37. Coupe, R.H., Manning, M.A., Foreman, W.T., Goolsby, D.A., Majewski, M.S., 2000. Occurrence of pesticides in rain and air in urban and agricultural areas of Mississippi, April–September 1995. Science of the Total Environment 248, 227–240. De Rossi, C., Bierl, R., Riefstahl, J., 2003. Organic Pollutants in precipitation: monitoring of pesticides and polycyclic aromatic hydrocarbons in the region of Trier (Germany). Physics and Chemistry Earth 28, 307–314. Dubus, I.G., Hollis, J.M., Brown, C.D., 2000. Pesticides in Rainfall in Europe. Environmental Pollution 110, 331–344. Epple, J., Maguhn, J., Spitzauer, P., Kettrup, A., 2002. Input of pesticides by atmospheric deposition. Geoderma 105, 327–349. Grybkiewicz, M., Polkowska, Z., Go´recki, T., Namies´ nick, J., 2003. Pesticides in precipitation from an urban region in Poland (Gdans´ k-Sopot-Gdynia tricity) between 1998 and 2000. Water, Air and Soil Pollution 149, 3–16. Haragushi, K., Kitamura, E., Yamashita, T., Kido, A., 1995. Simultaneous determination of trace pesticides in urban precipitation. Atmospheric Environment 29, 247–253. Magdic, S., Boyd-Boland, A., Jinno, K., Pawliszyn, J.B., 1996. Analysis of organophosphorus insecticides from environmental samples using solid-phase microextraction. Journal of Chromatography A 776, 219–228. Mc Connell, L.L., LeNoir, J.S., Datta, S., Seiber, J.N., 1998. Wet deposition of current-use pesticides in the Sierra Nevada mountain range, California, USA. Environmental Toxicology and Chemistry 17, 1908–1916.
Millet, M., Wortham, H., Sanusi, A., Mirabel, Ph., 1997. Atmospheric contamination by pesticides: Determination in the liquid, gaseous and particulate phases. Environmental Science and Pollution Research 4, 172–180. Quaghebeur, D., De Smet, B., De Wulf, E., Steurbautb, W., 2004. Pesticides in rainwater in Flanders, Belgium: results from the monitoring program 1997–2001. Journal of Environmental Monitoring 6, 182–190. Sauret, N., 2002. Ph.D. Thesis, University of Strasbourg I, 212pp (in French). Scheyer, A., Morville, S., Mirabel, Ph., Millet, M., 2006a. Analysis of trace levels of pesticides in rainwater using SPME and GC-tandem mass spectrometry. Analytical and Bioanalytical Chemistry 384, 475–487. Scheyer, A., Briand, O., Morville, S., Mirabel, Ph., Millet, M., 2007a. Analysis of trace levels of pesticides in rainwater by SPME and GC-tandem mass spectrometry after derivatisation with PFFBr. Analytical and Bioanalytical Chemistry 387, 359–368. Scheyer, A., Morville, S., Mirabel, Ph., Millet, M., 2007b. Variability of atmospheric pesticide concentrations between urban and rural areas during intensive pesticide application. Atmospheric Environment, in press, doi:10.1016/j.atmosenv. 2006.12.042. Tarrant, K.R., Tatton, J.O’.G., 1968. Organochlorine pesticides in rainwater in the British Isles. Nature 219, 725–727. Trevisan, M., Montepiani, C., Ragozza, L., Bartoletti, C., Ioannilli, E., Del Re, A.A.M., 1993. Pesticides in Rainfall and air in Italy. Environmental Pollution 80, 31–39. Van Dijk, H.F.G., Guicherit, R., 1999. Atmospheric dispersion of current-use pesticides: a review of the evidence from monitoring studies. Water, Air and Soil Pollution 115, 21–70. Wheatley, G., Hardman, J., 1965. Indications of the presence of organochlorine insecticides in rainwater in central England. Nature 207, 486–487.