Fate in the environment and long-range atmospheric transport of the organophosphorus insecticide, chlorpyrifos and its oxon.
The fate and movement of the organophosphorus insecticide chlorpyrifos (CPY;CAS No.2921-88-2) and its metabolite chlorpyrifos-oxon (CPYO; CASNo.5598-15-2) determine exposures in terrestrial and aquatic environments.Detectable concentrations of the organophosphorus insecticide CPY in air, rain,snow and other environmental media have been measured in North America and other locations at considerable distances from likely agricultural sources, which indicates the potential for long range transport (LRT) in the atmosphere. This issue was addressed by first compiling monitoring results for CPY in all relevant environmental media. As a contribution to the risk assessment of CPY in remote regions, a simple mass balance model was developed to quantify likely concentrations at locations ranging from local sites of application to more remote locationsup to hundreds of km distant. Physical-chemical properties of CPY were reviewed and a set of consistent values for those properties that determine partitioning and reactivity were compiled and evaluated for use in the model. The model quantifies transformation and deposition processes and includes a tentative treatment of dispersion to lesser atmospheric concentrations. The model also addressed formation and fate of CPYO, which is the major transformation product of CPY. The Characteristic Travel Distance (CTD) at which 63% of the original mass of volatilized CPY is degraded or deposited-based on a conservative concentration of •OHradicals of 0.7 x 106 molecules cm-3 and a half-life of 3 h, was estimated to be 62 km. At lesser concentrations of •OH radical, such as occurs at night and at lesser temperatures, the CTD is proportionally greater. By including monitoring data from a variety of media, including air, rain, snow and biota, all monitored concentrations can be converted to the equilibrium criterion of fugacity, thus providing asynoptic assessment of concentrations of CPY and CPYO in multiple media. The calculated fugacities of CPY in air and other media decrease proportionally with increasing distance from sources, which can provide an approximate prediction of downwind concentrations and fugacities in media and can contribute to improved risk assessments for CPY and especially CPYO at locations remote from points of application, but still subject to LRT. The model yielded estimated concentrations that are generally consistent with concentrations measured, which suggests that the canonical fate and transport processes were included in the simulation model. The equations included in the model enable both masses and concentrations of CPY and CPYO to be estimated as a function of distance downwind following application.While the analysis provided here is useful and an improvement over previous estimates of LRT of CPY and CPYO, there is still need for improved estimates of the chemical-physical properties of CPYO.Based on the persistence in water, soils, and sediments, its bioconcentration and biomagnification in organisms, and its potential for long-range transport, CPY and CPYO do not trigger the criteria for classification as a POP under the Stockholm convention or a PB chemical under EC 1107/2009. Nonetheless, CPY is toxic at concentrations less than the trigger for classification as T under EC 11 07 /2009; however,this simple trigger needs to be placed in the context of low risks to non-target organisms close to the areas of use. Overall, CPY and CPYO are judged to not trigger the PBT criteria of EC 1107/2009.
Trent University, Peterborough, ON, Canada, dmackay@trentu.ca.
Don
D
Mackay
John P
JP
Giesy
Keith R
KR
Solomon
D000393:Air Pollutants / Q000737:chemistry / Q000633:toxicity*; D000818:Animals; D001272:Atmosphere; D004390:Chlorpyrifos / Q000737:chemistry* / Q000633:toxicity*; D007306:Insecticides / Q000737:chemistry* / Q000633:toxicity*; D014481:United States
D000393:Air Pollutants; D007306:Insecticides; D004390:Chlorpyrifos