Abstract
Perchlorate (ClO4-) has been detected over an expansive area in groundwater and soils in the southwestern United States. Because of its wide distribution, much of the ClO4- is presumed to be from natural sources, primarily atmospheric deposition and accumulation. The objective of this study was to evaluate the range of the isotopic composition of natural ClO4- indigenous to the southwestern U.S. Stable isotope ratios of Cl and O were determined for ClO4- collected from numerous sources, including: groundwater from several locations in the southern high plains (SHP) of Texas and New Mexico and the middle Rio Grande Basin in New Mexico, vadose zone soil from the SHP, and surface NO3--rich caliches from four locations in Death Valley, CA. The data suggest that natural ClO4- in the southwestern U.S. has at least two distinctive isotope signatures that differ both from each other and from those previously reported for natural ClO4- from the Atacama Desert of Chile and all anthropogenic ClO4- sources tested to date. The ClO4- in four caliche samples collected in Death Valley has high Δ17O values (8.6 to 18.4 ‰), similar to those described for ClO4- from the Atacama, and suggesting atmospheric formation via reaction with ozone (O3). However, the Death Valley samples have δ37Cl values (-3.1 to -0.8 ‰) and δ18O values (+2.9 to +26.1‰), that are appreciably higher than Atacama perchlorate (δ37Cl; -14.3 to -10.2‰ and δ18O; (-10.5 to -2.2 ‰, respectively). In contrast, samples from 8 locations in West Texas and New Mexico were characterized by only a slight elevation in Δ17O (0.3 to 1.3‰), suggesting either that this material is not primarily generated with O3 as a reactant or that the ClO4- has been consistently altered post-deposition by one or more processes that caused isotopic exchange of O. The δ37Cl values in the SHP perchlorate (+ 3.4 to + 5.1 ‰) were consistently higher than for the Atacama or Death Valley salts, while the δ18O values (+ 0.5 to + 4.8 ‰) overlapped significantly with those from Death Valley. Additional studies are necessary to better understand the various origins and potential exchange reactions of natural perchlorate, however, the data presented herein provide constraints on natural isotope signatures important for interpretation of isotope values at locations in which ClO4- sources in groundwater or drinking water are unknown.
