Sampling methods to determine the spatial gradients and flux of arsenic at a groundwater seepage zone

Sampling techniques with centimeter-scale spatial resolution were applied to investigate biogeochemical processes controlling groundwater arsenic fate across the groundwater-surface water interface at a site characterized by fine sediments (40% sand, 46% silt, 14% clay). Freeze-core sediment collection gave more detailed and depth-accurate arsenic and iron contaminant and microbial distributions than could be obtained with the use of a hand auger. Selective chemical extractions indicated that greater than 90% of the arsenic was strongly sorbed to very amorphous iron oxyhydroxides. These solids accounted for more than 80% of the total iron in the sediments. Microbial enrichments indicated that iron-oxidizing bacteria (IOB) were up to 1% of the total bacterial abundance, whereas iron-reducing bacteria (IRB) were about two orders of magnitude less abundant than IOB. The abundance of IRB mirrored the IOB depth profile. Push-point pore-water sampling captured large amounts of sediment fines, even with controlled (20 ml/min) water withdrawal, thereby necessitating filtration before water quality analysis. Bead columns containing glass media enabled short-term (29 d) characterization of pore water-to-sediment transfer of arsenic and iron. Bead columns indicated quantitative capture of groundwater arsenic and iron during 2003, suggesting that freeze-core inventories corresponded to 2 to 20 years of accumulation, depending on location.