Soil-Air exchange controls on background atmospheric concentrations of organochlorine pesticides

Abstract. Soils are the major terrestrial reservoir of persistent organic pollutants, and thus net volatilization from soil, when it happens, may exert a control on the atmospheric occurrence and variability of organic pollutants. Here, we report and discuss the concentrations of legacy organochlorine pesticides (OCPs) such as hexachlorobenzene (HCB), hexaclorocyclohexanes (HCH) and dichlorodiphenyltrichloroethane (DDT) in the atmosphere and in soils, their measured fugacities in soil, the soil-air partition coefficients (K_SA) and soil-air fugacity ratios (f_s/f_a) in rural background areas of N-NE Spain and N-NW England. Four sampling campaigns were carried out in Spain and UK to assess seasonal variability and differences between sampling sites. K_SA values were significantly dependent on soil temperature and soil organic matter quantity, and to a minor extent on organic matter type. HCH isomers and DDT metabolites in soil are close to equilibrium with the overlying atmosphere at rural background areas of Spain with a tendency to volatilize and deposit during warm and cold periods, respectively. The mixture of HCH and DDT found in the atmosphere is clearly strongly influenced by the mixture of HCH and DDT which escapes from soil, with significant correlations between them (r² ranging between 0.63–0.76 and p-level<0.001 for the Ebro sampling sites), thus suggesting a close coupling of air and soil concentrations, demonstrating that net volatilization from soil control the atmospheric levels of OCPs in the Northern Spain background atmosphere. Conversely, soils at rural UK sites were usually a sink for atmospheric DDT and HCH, but not for HCB. The negative statistically significant relationship found between log K_SA and the log (f_s/f_a) ratio, suggests that high latitude regions, due to the high soil organic matter content and lower temperatures, will act as larger traps and accumulate more atmospheric OCPs. Thus, the extent to which soils are secondary sources to the atmosphere is currently dependent on the reservoir potential of soils for OCPs and shows a marked seasonality in their strength.