The role of hydrous ferric oxide precipitation in the fractionation of arsenic, gallium, and indium during the neutralization of acidic hot spring water by river water in the Tama River watershed, Japan

Abstract

The Obuki spring is the largest and most acidic of the Tamagawa hot springs (Akita Prefecture, northern Japan), and it discharges ca. 9000L/min of chloride-rich acidic water (pH 1.2) that contains high concentrations of both As and rare metals such as Ga and In. This paper aims to quantify seasonal variations in the mobility of these elements in the Shibukuro and Tama rivers, which are fed by the thermal waters of the Obuki spring, caused by sorption onto hydrous ferric oxide (HFO).Seasonal observations revealed the following relationships with respect to As removal by HFO: (a) the oxidation of Fe2+ is predominantly controlled by both pH and water temperature, and progresses more quickly in less acidic and warmer conditions; (b) HFO formation was predominantly controlled by pH; and (c) the removal of dissolved arsenate is directly related to the amount of HFO present. Consequently, the oxidation to Fe3+ was slower during periods of cold and lower pH, and the amount of HFO was too small to remove the dissolved arsenate effectively. Consequently, considerable amounts of dissolved arsenate and Fe2+ remained in river water. In contrast, when HFO production from Fe3+ increased, and dissolved arsenate was removed during warmer and less acidic periods, only small amounts of dissolved arsenite and Fe2+ remained in the river water. The geochemical behavior of Ga and In was essentially controlled by pH; however, when HFO production was limited by a pH of less than 3.5, Ga behavior was controlled mainly by the amount of HFO. Gallium tended to be sorbed under more acidic conditions than was In.Due to differences in sorption behavior, Ga, As, and In were fractionated during sedimentation. In the upstream reaches, arsenate and dissolved Ga sorbed onto HFO, and were widely distributed across the watershed. Conversely, dissolved In was removed by HFO downstream. As a result, In is relatively concentrated on the downstream lakebed, unlike As and Ga, and In-rich mineral deposits are accumulating at present.