The origin of naturally occurring perchlorate: the role of atmospheric processes

Perchlorate, an iodide uptake inhibitor, is increasingly being detected in new places and new matrices. Perchlorate contamination has been attributed largelyto the manufacture and use of ammonium perchlorate (the oxidizer in solid fuel rockets) and/or the earlier use of Chilean nitrate as fertilizer (approximately 0.1% perchlorate). However, there are regions such as the southern high plains (Texas Panhandle) where there is no clear historical or current evidence of the extensive presence of rocket fuel or Chilean fertilizer sources. The occurrence of easily measurable concentrations of perchlorate in such places is difficult to understand. In the southern high plains groundwater, perchlorate is better correlated with iodate, known to be of atmospheric origin, compared to any other species. We show that perchlorate is readily formed by a variety of simulated atmospheric processes. For example, it is formed from chloride aerosol by electrical discharge and by exposing aqueous chloride to high concentrations of ozone. We report that perchlorate is present in many rain and snow samples. This strongly suggests that some perchlorate is formed in the atmosphere and a natural perchlorate background of atmospheric origin should exist.