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.

A substantial reservoir (up to 1 kg ha(-1)) of natural perchlorate is present in diverse unsaturated zones of the arid and semi-arid southwestern United States. The perchlorate co-occurs with meteoric chloride that has accumulated in these soils throughout the Holocene [0 to 10-15 ka (thousand years ago)] and possibly longer periods. Previously, natural perchlorate widely believed to be limited to the Atacama Desert, now appears widespread in steppe-to-desert ecoregions. The perchlorate reservoir becomes sufficiently large to affect groundwater when recharge from irrigation or climate change flushes accumulated salts from the unsaturated zone. This new source may help explain increasing reports of perchlorate in dry region agricultural products and should be considered when evaluating overall source contributions.

Natural perchlorate is believed to be of atmospheric origin, yet no systematic study has been conducted to evaluate perchlorate deposition rate and possible seasonal or spatial variations. This study evaluated perchlorate concentrations in weekly composite wet deposition samples acquired through the National Atmospheric Deposition Program from 26 sites across the continental United States, Alaska, and Puerto Rico for a 1−3 year period. Perchlorate concentrations varied from <5 ng/L to a high of 102 ng/L with a mean of 14.1 ± 13.5 ng/L for the 1578 total samples. The annual perchlorate flux by site ranged from a low of 12.5 (TX) to 157 mg/ha-year (NE) and averaged 65 ± 30 mg/ha-year for all sites. Perchlorate concentrations and flux in wet deposition were generally highest in May−August declining to lows in December−February. Average annual perchlorate flux was correlated (r > 0.5; p < 0.001) with Ca2+, K+, NH4 +, NO3 −, Cl−, and SO4 −2. Wet deposition rate of ClO4 − in the conterminous United States (excluding Alaska, Hawaii, and Puerto Rico) while diffuse, represents a potential annual net mass flux of 51 000 kg, a value comparable to the estimated annual environmental releases from other known ClO4 − sources.