Reactivity and speciation of mineral-associated arsenic in seasonal and permanent wetlands of the Mekong Delta

Millions of people in the deltaic regions of S/SE Asia regularly consume As contaminated groundwater. Arsenic persists within these groundwaters despite being flushed by several pore volumes of recharge, indicative of an in situ solid phase source. Despite the importance of this solid phase source, the identity and reactivity of the minerals hosting and releasing As in the deltaic aquifers remain poorly constrained. Here we seek to define the chemistry and reactivity of As and its host minerals in aquifer sediments recharged by both seasonally saturated and permanent wetlands in the Mekong Delta of Cambodia. Sediment cores were retrieved to depths of up to 30 m. Selective extractions on near-surface sediments (to depths of 4-6 m) indicate that more than a third (27-50%) of the Fe in the profile is "reducible" (citrate-bicarbonate-dithionite-extractable) nominally consisting of Fe(III) oxides. The Fe(III) oxide fraction was approximately the same under seasonal wetlands (mean = 39%) compared with sediments from beneath permanent wetlands (mean = 37%). Correspondingly, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectra analysis indicates that the Fe mineral phases are predominantly goethite and hematite (30-50%). Analysis of solid phase As speciation by X-ray absorption near edge structure (XANES) spectroscopy showed arsenate in the shallowest sediments (upper 1 and 4 m of seasonal and permanent wetlands), and arsenite and/or As sulfides as the dominant phases in the deeper sediments. The reducible As fraction ranged from 17% to 42% of the total As at both sites. The exception was found in a peat layer at 6 m beneath the seasonal wetland, in which only 1% of the total As was reducible. Arsenian pyrite was the predominant form of As in the peat. Thus, a pool of As hosted by reducible mineral phases persists in sediments below both the seasonal and permanently saturated wetland sites. (C) 2015 Elsevier Ltd. All rights reserved.