title: Geochemical weathering increases lead bioaccessibility in semi-arid mine tailings.
abstract: Mine tailings can host elevated concentrations of toxic metal(loid)s that represent a significant hazard to surrounding communities and ecosystems. Eolian transport, capable of translocating small (micrometer-sized) particles, can be the dominant mechanism of toxic metal dispersion in arid or semiarid landscapes. Human exposure to metals can then occur via direct inhalation or ingestion of particulates. The fact that measured doses of total lead (Pb) in geomedia correlate poorly with blood Pb levels highlights a need to better resolve the precise distribution of molecularly speciated metal-bearing phases in the complex particle mixtures. Species distribution controls bioaccessibility, thereby directly impacting health risk. This study seeks to correlate Pb-containing particle size and mineral composition with lability and bioaccessibility in mine tailings subjected to weathering in a semiarid environment. We employed X-ray absorption spectroscopy (XAS) and X-ray fluorescence (XRF), coupled with sequential chemical extractions, to study Pb speciation in tailings from the semiarid Arizona Klondyke State Superfund Site. Representative samples ranging in pH from 2.6 to 5.4 were selected for in-depth study of Pb solid-phase speciation. The principle lead-bearing phase was plumbojarosite (PbFe(6)(SO(4))(4)(OH)(12)), but anglesite (PbSO(4)) and iron oxide-sorbed Pb were also observed. Anglesite, the most bioavailable mineral species of lead identified in this study, was enriched in surficial tailings samples, where Pb concentrations in the clay size fraction were 2-3 times higher by mass relative to bulk. A mobile and bioaccessible Pb phase accumulates in surficial tailings, with a corresponding increase in risk of human exposure to atmospheric particles.
authors.affiliation: Department of Soil, Water and Environmental Science, University of Arizona, Tucson, Arizona 85721, United States.
authors.forename: Sarah M
authors.initials: SM
authors.lastname: Hayes
authors.forename: Sam M
authors.initials: SM
authors.lastname: Webb
authors.forename: John R
authors.initials: JR
authors.lastname: Bargar
authors.forename: Peggy A
authors.initials: PA
authors.lastname: O'Day
authors.forename: Raina M
authors.initials: RM
authors.lastname: Maier
authors.forename: Jon
authors.initials: J
authors.lastname: Chorover
mesh_terms: D001682:Biological Availability; D005591:Chemical Fractionation; D003889:Desert Climate; D055593:Geological Phenomena; D006801:Humans; D007220:Industrial Waste / Q000032:analysis*; D007854:Lead / Q000378:metabolism*; D008906:Mining; D010316:Particle Size; D012015:Reference Standards; D013052:Spectrometry, X-Ray Emission; D014887:Weather; D056928:X-Ray Absorption Spectroscopy
chemical_list: D007220:Industrial Waste; D007854:Lead