Arsenic-bearing smectite from the geothermal environment

Arsenic-rich scales are widely associated with geothermal fields and constitute a potential hazard to human health. Such arsenic has hitherto been reported to be almost exclusively hosted by sulphide or oxide phases or occurring as surface species. We report here, however, the occurrence of an arsenic-rich (1500 to 4000 mg kg(-1) As) smectite from geothermal precipitates from a geothermal field in northwestern Japan and present evidence that the arsenic is predominantly hosted within this silicate mineral. Consistently similar to 80% of the total arsenic determined in these geothermal precipitates was found by selective chemical extractions to be associated with an operationally defined clay mineral fraction, with lesser proportions being associated with operationally defined amorphous silica, Fe oxide and sulphide fractions. Analysis by XRD, ATR IR and XRF showed the clay fraction to be dominated by Mg-rich trioctahedral smectite. Arsenic K-edge XAS spectra of the smectite suggested the dominance of AS(III)-O coordinated species with significant contributions from As(V)-O coordinated species. Both XPS and a magnesium chloride chemical extraction indicated minimal adsorption of arsenic on smectite surfaces suggesting that the arsenic was predominantly either dissolved within the smectite or occurred within mineral occlusions. No such occlusions greater than 1 mu m in size were observed in the As-rich smectites. The potential occurrence of arsenic-bearing clays should be considered when determining remediation strategies for geothermal environments or evaluating risks associated with the industrial usage of geothermal precipitates.