Factors Controlling the Fractionation and Seasonal Mobility Variations of Ga and In in Systems Impacted by Acidic Thermal Waters: Effects of Thermodynamics and Bacterial Activity

Yasumasa Ogawa, Daizo Ishiyama, Naotatsu Shikazono, Koichi Suto, Chihiro Inoue, Noriyoshi Tsuchiya, Bernhardt Saini-Eidukat, Scott A. Wood

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)


This work assessed both the fractionation and the seasonal mobility variations of Ga and In in systems impacted by acidic thermal waters. This was accomplished by performing thermodynamic calculations using the PHREEQC algorithm and by assessing the activity of acidophilic iron-oxidizing bacteria. The pH of the Kusatsu thermal waters in Gunma Prefecture, central Japan, is rapidly increased following the addition of a lime suspension. After an abrupt pH increase, under which conditions free ions of Ga and In and their complexes with Cl and SO4 2− exist only in negligible quantities, the majority of dissolved Ga and In is removed by sorption onto suspended hydrous ferric oxides (HFOs). These HFOs are then transported to an artificial lake without significant sedimentation along the river. Subsequently, the suspended HFOs settle out and are added to sediments without significant fractionation between Ga and In. The Tamagawa thermal waters in Akita Prefecture, northeast Japan, are also treated with lime. However, complete neutralization requires mixing with some tributary streams, leading to a gradual downstream increase in pH. Dissolved Ga is, in general, sorbed by HFOs in upstream areas, leading to wide dispersal of Ga across the entire watershed. In comparison, In is transported to the lake inlet predominantly as a Cl complex species without significant removal along the river, with the majority being precipitated in an artificial lake, where Cl concentrations are too low to form stable complex species with In, and thus, dissolved In is sorbed by HFOs. As a result, In is effectively concentrated within downstream lakebed sediments, whereas Ga is dispersed along the river. Seasonal variations in Ga mobility within the Tamagawa field between snowmelt and low-flow seasons are primarily controlled by pH, because hydrolysis reactions of these metals, which are related to sorption reactions, tend to occur in the upstream regions in the snowmelt season. However, under warmer conditions, HFO formation preferably occurs due to the activity of acidophilic iron-oxidizing bacteria. Thus, under similar pH variations, dissolved Ga is more effectively removed by HFOs during warmer seasons. On the contrary, because HFOs are abundantly formed in low-flow season, even under colder conditions, before In hydrolysis reaction starts to occur, In mobility is less affected by water temperature and then bacterial activity.

Original languageEnglish
Pages (from-to)5-25
Number of pages21
JournalAquatic Geochemistry
Issue number1
Publication statusPublished - 2018 Feb 1


  • Acidic river
  • Acidic thermal water
  • Gallium
  • Indium
  • Neutralization

ASJC Scopus subject areas

  • Geophysics
  • Geochemistry and Petrology


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