Samples of Marshall Sandstone, a major source of groundwater with elevated arsenic levels in southeast Michigan, were exposed to bicarbonate ion under controlled chemical conditions. In particular, effects of pH and redox conditions on arsenic release were evaluated. The release of arsenic from the aquifer rock was strongly related to the bicarbonate concentration in the leaching solution. The results obtained suggest that the carbonation of arsenic sulfide minerals, including orpiment (As2S3) and realgar (As2S2), is an important process in leaching arsenic into groundwater under anaerobic conditions. The arseno-carbonate complexes formed, believed to be As(CO3)2-, As(CO3)(OH)2-, and AsCO3+, are stable in groundwater. The reaction of ferrous ion with the thioarsenite from carbonation process can result in the formation of arsenopyrite which is a common mineral in arsenic-rich aquifers.Samples of Marshall Sandstone, a major source of groundwater with elevated arsenic levels in southeast Michigan, were exposed to bicarbonate ion under controlled chemical conditions. In particular, effects of pH and redox conditions on arsenic release were evaluated. The release of arsenic from the aquifer rock was strongly related to the bicarbonate concentration in the leaching solution. The results obtained suggest that the carbonation of arsenic sulfide minerals, including orpiment (As2S3) and realgar (As2S2), is an important process in leaching arsenic into groundwater under anaerobic conditions. The arseno-carbonate complexes formed, believed to be As(CO3)2-, As(CO3)(OH)2-, and AsCO3+, are stable in groundwater. The reaction of ferrous ion with the thioarsenite from carbonation process can result in the formation of arsenopyrite which is a common mineral in arsenic-rich aquifers.The role of bicarbonate in leaching arsenic into groundwater was investigated by conducting batch experiments using core samples of Marshall Sandstone from southeast Michigan and different bicarbonate solutions. The effects of pH and redox conditions on As dissolution were examined. Results showed that As was not leached significantly out of the Marshall Sandstone samples after 3 d using either deionized water or groundwater, but As was leached efficiently by sodium bicarbonate, potassium bicarbonate, and ferric chloride solutions. The leaching rate with sodium bicarbonate was about 25% higher than that with potassium bicarbonate. The data indicated that bicarbonate ion was involved primarily in As dissolution and that hydroxyl radical ion did not affect As dissolution to any significant degree. The amount of As leached was dependent upon the sodium bicarbonate concentration, increasing with reaction time for each concentration. Significant As leaching was found in the extreme pH ranges of <1.9 and 8.0-10.4. The resulting arseno-carbonate complexes formed were stable in groundwater.