Elsevier

Science of The Total Environment

Volume 574, 1 January 2017, Pages 724-734
Science of The Total Environment

Risk assessment of airborne pesticides in a Mediterranean region of Spain

https://doi.org/10.1016/j.scitotenv.2016.08.149Get rights and content

Highlights

  • Levels of airborne pesticides ranged from 8 to 30,000 pg m 3.

  • Inhalation exposure was estimated for 40 airborne pesticides.

  • Hazard Quotient was < 1 for all pesticides detected in the three groups of population.

  • Hazard Index was less than 1 for the three groups of population.

Abstract

A risk assessment strategy based on the quantitative target analysis and semi-quantitative retrospective screening determination of pesticides in PM10 has been developed. The proposed methodology was applied to 345 real samples from nine stations of a Mediterranean area in Spain, and the risk was assessed for adult, children and infants. Forty pesticides were detected with average concentrations ranging from 8 to 30,000 pg m 3. Each station showed its specific pesticide profile, which is linked to the different types of crops around each station. For adults, children and infants the estimated chronic inhalation risk, expressed as Hazard Quotient (HQ), was < 1 for all pesticides. The cumulative exposure for organophosphates, neonicotinoids, benzimidazoles, carbamates, micro-organism and triazoles pesticides (HI, Hazard Index) were < 1 for the three groups of populations assessed. For infants, the cancer risk estimated for the detected pesticides classified as possible and potential carcinogens were lower than 1.0 E-06, except for carbendazim and hexythiazox.

Introduction

A wide variety of pesticides can be applied in agriculture and their identity depends on a range of factors including the specific pest and crop of interest. During 2013, about 300,000 t of pesticide active ingredients were used in Europe (EU-15) (Eurostat, 2013, ECPA (European Crop Protection Association), 2010) and around 500 active substances are nowadays authorised by the European Union for their application on various crops according to the Regulation (EC) 1107/2009 (EU Pesticide Database, 2016). The potentially adverse effects of exposure to pesticides on the general population, and specifically on the more susceptible groups such as infants and children, are a public health concern (Marks et al., 2010, London et al., 2012).

Apart from ingestion of food and drinking water, inhalation of ambient air could be a relevant pathway of exposure to pesticides. To perform an inhalation risk assessment of exposures to atmospheric CUPs (currently used pesticides), it is necessary to know the total concentration (gas + particulate phases) of these compounds in the ambient air. This requires that the air samplers collect both the particle phase and the gas phase (using appropriate adsorbents). At present, there is a lack of consistency in sampling methodologies. Standardization of sampling methods for pesticides in the gas phase is the most difficult part, owing to the wide range of physicochemical properties of the active substance currently in use (Yusà et al., 2009). On the contrary, the methods for collection of pesticides bound to the particulate matter seem to be more homogenous, and in general, pesticides are trapped in glass fibre filters (GFF) or quartz fibre filters (QFFs) (Yusà et al., 2009).

The pesticides applied to crops must have no harmful effects on humans. Although international guidelines on pesticide exposure and risk assessment for operators, workers, bystanders and residents have recently been developed (EFSA, 2014), the methodologies focused on the exposure and risk assessment of airborne pesticides on the general population are scarce. Risk assessment to inhalated pesticides have been studied in rural and urban areas worldwide. In Spain, Yusà et al. (2014) proposed a screening approach for inhalation chronic risk assessment of CUPs present in rural ambient air, based on the concentration of these compounds in the inhalable particulate matter (PM10). In that study, total pesticide concentration was estimated applying theoretical partitioning models. In addition, Li et al. (2014) studied the inhalation exposure of organophosphate pesticides in an urban community of South China and Lee et al. (2002) in rural and urban stations in California region (USA).

In this paper, we have assessed the inhalation risk of pesticides in Valencia Region population based on the quantitative (target) and semi-quantitative (retrospective screening) determination of pesticides in PM10. The strategy was applied to six rural stations, two urban stations and one remote station placed in Valencia Region, and the risk was assessed for three populations (adults, children and infants).

Section snippets

Reagents and chemicals

Certified commercial standards were of high purity and purchase from Dr. Ehrenstorfer (Augsburg, Germany) and Sigma Aldrich (Barcelona, Spain). Individual stock standards were prepared weighing 10 mg of pure standard using a 5 decimal analytical balance and dissolving each compound in 50 mL of acetone. They were stored in capped amber vials at − 21 °C (SANCO, 2007). Mix working solutions at 10 and 1 mg L 1 were prepared with methanol. Calibration solutions were prepared by adding variable volumes of

Overall pesticide concentrations (PM10)

Spain was the European country with the highest consumption of pesticides (19.5%) in 2013 (Eurostat, 2015). Valencia region is a Mediterranean area located at the East coast of Spain. In this region the use of pesticides is very intensive in agricultural practices. In the present study, 345 real samples were analyzed for airborne pesticides. Overall, 40 pesticides were detected in the atmosphere in PM10, mainly of them were insecticides (37%) and fungicides (33%) (see Table 2).

Regarding to

Conclusions

A total of 40 pesticides (mainly insecticides and fungicides) were detected in the ambient air of rural, remote and urban stations placed in Valencia Region (Spain). Only two pesticides were detected in all stations (buprofezin and carbendazim). Rural and urban stations presented different profiles depending mainly on the agricultural practices around the sampling site (agricultural practices, seasonal application and climate).

Overall, inhalation exposure to studied pesticides in the different

Acknowledgements

This study was financed by the Generalitat Valenciana through the DIPA project (GV/2014/005) from the Conselleria d'Educació, the Spanish Ministerio de Economia y Competitividad for IMPLACAVELES project (CGL2013-49093-C2-1-R) and the FISABIO for AIRPEST project (UGP-15-250). The authors wish to acknowledge also Generalitat Valenciana – Spain, for the DESETRES-Prometeo II project. CEAM – is partly supported by Generalitat Valenciana.

References (59)

  • A. López et al.

    Retrospective screening of pesticide metabolites in ambient air using liquid chromatography coupled to high-resolution mass spectrometry

    Talanta

    (2016)
  • Y. Luo et al.

    Multimedia transport and risk assessment of organophosphate pesticides and a case study in the northern San Joaquin Valley of California

    Chemosphere

    (2009)
  • A. Muñoz et al.

    Studies on atmospheric degradation of diazinon in the EUPHORE simulation chamber

    Chemosphere

    (2011)
  • A. Muñoz et al.

    The gas-phase degradation of chlorpyrifos and chlorpyrifos-oxon towards OH radical under atmospheric conditions

    Chemosphere

    (2014)
  • A. Sanusi et al.

    Comparison of atmospheric pesticide concentrations measured at three sampling sites: local, regional and long-range transport

    Sci. Total Environ.

    (2000)
  • C. Schummer et al.

    Temporal variations of concentrations of currently used pesticides in the atmosphere of Strasbourg, France

    Environ. Pollut.

    (2010)
  • V. Yusà et al.

    Sampling and analysis of pesticides in ambient air

    J. Chromatogr. A

    (2009)
  • V. Yusà et al.

    New screening approach for risk assessment of pesticides in ambient air

    Atmos. Environ.

    (2014)
  • AEPLA (Asociación Empresarial para la Protección de las Plantas)

    Memoria AEPLA 2014

  • F. Aulagnier et al.

    Pesticides measured in air and precipitation in the Yamaska Basin (Québec): occurrence and concentrations in 2004

    Sci. Total Environ.

    (2008)
  • P. Avino et al.

    Investigation on the behaviour of pesticides in the atmosphere

    Aerosol Air Qual. Res.

    (2011)
  • L. Baraud et al.

    A multi-residue method for characterization and determination of atmospheric pesticides measured at two French urban and rural sampling sites

    Anal. Bioanal. Chem.

    (2003)
  • CAPA (Conselleria de Agricultura, Pesca y Alimentación de la Generalitat Valenciana)

    Informe del sector agrario 2012

  • CEPA, California Environmental Protection Agency

    Environmental Monitoring Branco, Air Monitoring Network Results for 2013–2014

    (2014)
  • Department of Pesticide Regulation, California

    Air Monitoring Network Study: Long-term Ambient Air Monitoring for Pesticides in Multiple California Communities

    (2011)
  • ECPA (European Crop Protection Association)

    Industry statistics 2001–2010

  • EFSA (European Food Safety Authority)

    Scientific opinion on preparation of a guidance document on pesticide exposure assessment for workers, operators, bystanders and residents

    EFSA J.

    (2014)
  • EFSA (European Food Safety Autority)

    Guidance of the scientific committee on a request from EFSA related to uncertainties in dietary exposure assessment

    EFSA J.

    (2006)
  • EFSA (European Food Safety Autority)

    International Frameworks Dealing with Human Risk Assessment of Combined Exposure to Multiple Chemicals

    (2013)
  • Cited by (46)

    View all citing articles on Scopus
    View full text