Selective Dissolution of Manganese Oxides from Soils and Sediments with Acidified Hydroxylamine Hydrochloride

Abstract

AbstractHydrous manganese and iron oxides of soils and sediments are strong scavenging agents for heavy metal ions. Information on heavy metals extracted along with manganese and iron oxides has been used in mineral exploration. But currently used methods do not differentiate metal ions associated with manganese oxides and those associated with iron oxides. Manganese oxides differ from iron oxides in solubility in response to oxidation‐reduction conditions, charge characteristics, and the quantity and kind of metal ions scavenged. This paper reports the development of an extraction method for the selective dissolution of manganese oxides from soils and sediments with minimal attack on the coexisting iron oxides, based on the difference in behavior of manganese oxides and iron oxides toward reduction under various conditions. By dissolving manganese oxides and iron oxides separately and determining respective metal ions which are released in the process, the geochemical significance of interelement relationships may be established.Manganese oxides in soils and sediments are found to be readily dissolved by a hydroxylamine hydrochloride (NH2OH · HCl) solution, leaving the major part of iron oxides in the residue. Although dissolution of manganese oxides is relatively independent of pH (pH 1, 2, and 3) and concentration of the NH2OH · HCl solution (0.025 to 0.25M), and time of equilibration (15 to 60 min), progressively greater amounts of iron oxides are released with lower pH and higher concentration of NH2OH · HCl solution, and with longer time of equilibration. A 0.1M NH2OH · HCl solution prepared in 0.01M HNO3 (pH 2) dissolves, on the average, 85% of manganese oxides and about 5% of iron oxides from various sediments after equilibrating for 30 min. Dissolution of manganese oxides and of iron oxides from four highly weathered soils by this solution amounts, respectively, to 50% and less than 1%. At pH 2, most heavy metal ions released during the dissolution of manganese oxides will be prevented from forming insoluble hydroxides or basic salts through hydrolysis, and then they can be determined in solution by appropriate analytical methods.