Atmospheric Environment 77 (2013) 394e403
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LC-MS characterization of contemporary pesticides in PM10 of Valencia Region, Spain Clara Coscollà a, Elizabeth Hart a, Agustín Pastor b, Vicent Yusà a, b, * a b
Centre for Public Health Research (CSISP-FISABIO), 21, Avenida Catalunya, 46020 Valencia, Spain Analytical Chemistry Department, Universidad de Valencia, Edifici Jeroni Muñoz, 50, Dr. Moliner, 46100 Burjassot, Valencia, Spain
h i g h l i g h t s 40 current-used pesticides were monitored in PM10 in Valencia Region (Spain). 17 current-used pesticides were detected at frequencies from 1 to 75%. Average pesticide concentrations ranged from 7 to 141 pg m3. Pesticide profiles were linked to the agricultural practices in the surroundings. Pesticides levels were greater in spring and early summer, the application period.
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Article history: Received 3 December 2012 Received in revised form 30 April 2013 Accepted 13 May 2013
Pesticides in the inhalable fraction of particulate matter (PM10) should be well tracked in order to contribute information to future exposure assessment in individuals of the general public. A total of 40 current-used pesticides and metabolites were searched for in ambient air samples collected from January through December 2010. The samples were taken from one remote, one urban and three rural sites in Valencia Region (Spain) and analyzed using liquid chromatography coupled to mass spectrometry in tandem (LC-MS/MS). In the PM10 fraction 17 pesticides and metabolites were detected overall, two of them currently banned (carbofuran and omethoate, although the latter is a metabolite of the permitted pesticide dimethoate). The detected pesticides appeared at frequencies ranging from 1 to 75%, with omethoate, terbuthylazine and its metabolites, and carbendazim presenting the highest frequencies. The concentrations detected ranged from few pg m3 to thousands of pg m3, with omethoate having the highest average concentration (141.15 pg m3) in the 5 sites overall. Each station showed its own specific pesticide profile, which is linked to the different types of crops around each site. In the rural stations pesticide levels were greater in spring and early summer, which correlates with their application in agricultural practices. These findings suggest that more efforts are required to implement an extensive air monitoring network in Europe for pesticide control and to develop regulations or recommendations regarding safer pesticide levels in ambient air. Ó 2013 Elsevier Ltd. All rights reserved.
Keywords: Pesticides Monitoring Air PM10 LC-MS/MS
1. Introduction Spain is one of the biggest pesticide users in the EU. In 2010, pesticide active ingredient consumption in the EU 15 was about 208,000 tonnes, with Spain using a total of 19% of these pesticides (about 39,000 tonnes) (ECPA, 2010). The second largest agricultural
* Corresponding author. Public Health Laboratory of Valencia (CSISP-FISABIO), 21, Avenida Catalunya, 46020 Valencia, Spain. Tel.: þ34 961925865; fax: þ34 961925888. . E-mail address:
[email protected] (V. Yusà). 1352-2310/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.atmosenv.2013.05.022
area in Spain is Valencia Region, the focus of this paper. This region, situated on the East coast, made up 12.1% of the total national consumption in 2009 (AEPLA, 2010). The main irrigated crops are citrus fruit, other fruit trees (mainly peach, apricot and plum trees) rice and garden produce (primarily watermelon, cabbage, artichoke, lettuce, cauliflower, tomatoes, potatoes and onion). The main dry crops are vineyards, olive trees and almonds (CAPA, 2010). Currently used pesticides (CUPs) include those that are used at present, as well as those that are currently prohibited but have been used in recent years (EU Pesticides Database, 2012). Up to 90% of pesticides are applied by spraying (NASDA, 2008), during which a fraction of the dosage applied to the target area is deposited onto
C. Coscollà et al. / Atmospheric Environment 77 (2013) 394e403
the adjacent non-target areas (spray drift) and another fraction is lost to the atmosphere. After application, wind erosion of soil particles containing sorbed pesticides and volatilization from soil and plants may represent further significant pesticide input into the troposphere for several days or even weeks after application (Bedos et al., 2002; Voutsas et al., 2005). In the air, pesticides can be distributed between the gas and particulate phases depending on some specific physicalechemical properties and environmental factors (Sauret et al., 2008). Total suspended particulate matter (TSP) is usually bypassed in studies in order to focus on PM10 and PM2.5 as indicators of air pollution. This selection is based on health considerations, since the fine fraction of PM can enter the lungs and is therefore the most dangerous for human health. Pesticides can easily adhere to atmospheric particulate matter (PM) and can produce adverse health effects (Arya, 2005). Several monitoring studies have detected pesticide concentrations in remote, rural and urban zones of different countries. Yusà et al. (2009) reported approximately 100 pesticides that have been determined in ambient air in studies during the last several years, with concentrations ranging from a few pg m3 to many ng m3. The majority of these pesticides are now prohibited. In general, the reported values are the sum of the pesticides present in both the gas and particulate phases, although some studies show the distribution between gas and particles. In a recent study, by Borrás et al. (2011), 4 sampling sites were analyzed in Spain for 16 atmospheric CUPs. Twelve pesticides were detected at values ranging from 0.08 to 5.83 ng m3 in the particulate phase and from 19.97 to 1428.28 ng m3 in the gas phase. Chlorpyrifos was mostly present in the gas phase while propachlor, chlorpyrifos-m and malathion were mostly detected in the particulate phase. In another study, Schummer et al. (2010) detected 38 CUPs in the atmosphere of Strasbourg, France, in air concentrations ranging from 0.09 to 110.42 ng m3. Some pesticides, like trifluralin, myclobutanil and clomazone, were mostly present in the gas phase (66.5%; 71.9%; 83.4%), whilst others, like alachlor, metolachlor or penconazole, were mostly detected in the particulate phase (83.5%; 75.4%; 88.5%). Scheyer et al. (2008) present the G/P partitioning of six current-use pesticides collected in Alsace region, France. These pesticides were present mainly in the particulate phase (from 50 to 100%) in concentrations from sub to a few ng m3 Coscollà et al. (2009) focused their study on 30 airborne CUPs in PM2.5 in Spain. They found 19 pesticides with concentrations ranging from 6.5 to 1208 pg m3. We recently published a monitoring article (Hart et al., 2012) covering the same time period and stations as this current article, but with pesticide analysis focused on 42 GCeMS/MS amenable pesticides. Of these, 24 pesticides were detected in the PM10 fraction, in frequencies ranging from
