Nanoanalytical Identification of Siderite Dissolution-Coupled Pb Removal Mechanisms from Oxic and Anoxic Aqueous Solutions

Lead­(II) is a toxic pollutant often found in metal-contaminated soils and wastewaters. In acidic aqueous environments, Pb­(II) is highly mobile. Chemical treatment strategies of such systems therefore often include neutralization agents and metal sorbents. Since metal solubility and the retention potential of sorbents depend on the redox state of the aqueous system, we tested the efficiency of the naturally occurring redox-sensitive ferrous iron carbonate mineral siderite to remove Pb­(II) from acidic aqueous solutions in batch experiments under oxic and anoxic conditions over a total of 1008 h. Siderite dissolution led to an increase in reactive solution pH from 3 to 5.3 and 6.9, while 90 and 100% of the initial aqueous Pb­(II) (0.48 × 10–3 mol kg–1) were removed from the oxic and anoxic systems, respectively. Scanning and transmission electron microscopy, combined with X-ray absorption and photoelectron spectroscopy, indicated that under oxic conditions, Pb­(II) was consumed by cerussite precipitation and inner-sphere surface complexation to secondary goethite. Under anoxic conditions, Pb­(II) was removed by the rapid precipitation of cerussite. This efficient siderite dissolution-coupled sequestration of Pb­(II) into more stable solid phases demonstrates this potential method for contaminated water treatment regardless of the redox environment.