Use of spatial statistics and isotopic tracers to measure the influence of arsenical pesticide use on stream sediment chemistry in New England, USA

Abstract

Arsenical pesticides and herbicides, principally Pb arsenate, Ca arsenate, and Na arsenate with lesser use of other metal-As pesticides, were widely applied on apple, blueberry, and potato crops in New England during the first half of the twentieth century. Agricultural census data for this time period is used to define an agricultural index that identifies areas that are inferred to have used arsenical pesticides extensively. Factor analysis on metal concentrations in 1597 stream sediment samples collected throughout New England, grouped by agricultural-index categories, indicate a positive association of areas with stream sediment sample populations that contain higher As and Pb concentrations than samples from the region as a whole with sample site settings having high agricultural-index values. Population statistics for As and Pb concentrations and factor scores for an As-Pb factor all increase systematically and significantly with increasing agricultural-index intensity in the region, as tested by Kruskal-Wallis analysis. Lead isotope compositions for 16 stream sediments from a range of agricultural-index settings generally overlap the observed variation in rock sulfides and their weathering products; however, sediments collected from high agricultural-index settings have slightly more radiogenic Pb compositions, consistent with an industrial Pb contribution to these samples. Although weathering products from rocks are likely to be the dominant source of As and metals to most of the stream sediment samples collected in the region, the widespread use of arsenical pesticides and herbicides in New England during the early 1900-1960s appears to be a significant anthropogenic source of As and metals to many sediments in agricultural areas in the region and has raised background levels of As in some regions. Elevated concentrations of As in stream sediments are of concern for two reasons. Stream sediments with elevated As concentrations delineate areas with elevated background concentrations of As from both natural rock and anthropogenic sources that may contribute As to groundwater systems used for drinking water supplies. Conversion of agricultural land contaminated with arsenical pesticide residues to residential development may increase the likelihood that humans will be exposed to As. In addition, many stream sediment sites have As concentrations that exceed sediment quality guidelines established for freshwater ecosystems. Thirteen percent of the New England sediment sample sites exceed 9.79 mg/kg As, the threshold effects concentration (TEC), below which harmful effects are unlikely to be observed. Arsenic concentrations exceed 33 mg/kg, the probable effects concentration (PEC), above which harmful effects on sediment-dwelling organisms are expected to occur frequently, at 1.25% of the sediment sample sites. The sample sites that exceed the PEC value occur predominately in agricultural areas that used arsenical pesticides.