Article ID Journal Published Year Pages File Type
4410153 Chemosphere 2012 7 Pages PDF
Abstract

Chlorinated pesticides can contain impurities of dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and their precursors, as a result of various manufacturing processes and conditions. As precursor formation of PCDD/Fs can also be mediated by ultraviolet light (UV), this study investigated whether PCDD/Fs are formed when currently used pesticides are exposed to natural sunlight. Formulations containing pentachloronitrobenzene (PCNB; n = 2) and 2,4-dichlorophenoxyacetic acid (2,4-D; n = 1) were exposed to sunlight in quartz tubes, and the concentration of 93 PCDD/F congeners were monitored over time. Considerable formation of PCDD/Fs was observed in both PCNB formulations (by up to 5600%, to a maximum concentration of 57 000 μg ∑PCDD/F kg−1) as well as the 2,4-D formulation (by 3000%, to 140 μg ∑PCDD/F kg−1). TEQ also increased by up to 980%, to a maximum concentration of 28 μg kg−1 in PCNB, but did not change in the 2,4-D formulation. Assuming similar yields as observed in the present study as a worst case scenario the use of PCNB in Australia may result in the formation of 155 g TEQ annum−1, contributed primarily by OCDD formation. This warrants detailed evaluations on the contemporary release of PCDD/Fs to the environment after the use of pesticides. Changes in congener profiles (including the ratio of PCDDs to PCDFs (DF ratio)) suggest that pesticide sources of PCDD/Fs after sunlight exposure may not be recognized based on matching source fingerprints established from manufacturing impurities. These changes also provide preliminary insights into the possible formation routes and types of precursors involved.

► Exposure to sunlight results in formation of dioxins in PCNB and 2,4-D pesticide formulations. ► TEQ increased by up to 9-fold via photolysis. ► High concentrations of dioxins may thus be formed via this pathway after pesticide use. ► Dioxin fingerprints in pesticides change considerably during sunlight exposure. ► The manufacture of commonly used pesticides can result in dioxin precursor formation.

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Life Sciences Environmental Science Environmental Chemistry
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