James P. Shine | USGS Science

USGS2022

Germanium redistribution during weathering of Zn mine wastes: Implications for environmental mobility and recovery of a critical mineral

Germanium (Ge) is a metal used in emerging energy technologies, communications, and defense, and has been deemed critical by the United States due to its essential applications and scarce supply. Germanium is recovered as a byproduct of zinc (Zn) sulfides, and mining and processing of these materials lead to waste that could act both as a source of extractable Ge and a source for exposure to humans and ecosystems. Yet the distribution, speciation, and mineral hosts of Ge in mining-impacted areas are poorly understood. The Tar Creek Superfund Site, a former Zn mining area and Ge producer, is a natural laboratory to understand the environmental behavior and economic implications of Ge in mine wastes. We studied the distribution and behavior of Ge in solid wastes at the Tar Creek Superfund Site using bulk and microanalytical techniques. In wastes at this site we find that Ge has been redistributed from its original host, sphalerite (ZnS), to the fine-grained weathering product hemimorphite (Zn4Si2O7(OH)2·H2O), which impacts germanium's mobility, bioaccessibility, and potential for recovery. We provide chemical and mineralogical evidence of this redistribution, along with an evaluation of the oxidation state and molecular-scale substitution of Ge into sphalerite, hemimorphite, and quartz. Geochemical modeling shows that hemimorphite is more stable than sphalerite in waste piles and provides a stable secondary repository for Ge. However, hemimorphite is fine-grained, and if ingested or inhaled is readily soluble, with the potential to release Ge. Lastly, we discuss other sites internationally where similar behavior may be important. This study shows that weathering can have a significant impact on the distribution, speciation, and mineral hosts of Ge in mine wastes; directly influence mobilization from waste piles and subsequent availability to humans and ecosystems; and dictate metallurgical strategies to target Ge for recovery.

Oklahoma↗

USGS2017

The precipitation of indium at elevated pH in a stream influenced by acid mine drainage

Indium is an increasingly important metal in semiconductors and electronics and has uses in important energy technologies such as photovoltaic cells and light-emitting diodes (LEDs). One significant flux of indium to the environment is from lead, zinc, copper, and tin mining and smelting, but little is known about its aqueous behavior after it is mobilized. In this study, we use Mineral Creek, a headwater stream in southwestern Colorado severely affected by heavy metal contamination as a result of acid mine drainage, as a natural laboratory to study the aqueous behavior of indium. At the existing pH of ~ 3, indium concentrations are 6–29 μg/L (10,000 × those found in natural rivers), and are completely filterable through a 0.45 μm filter. During a pH modification experiment, the pH of the system was raised to > 8, and > 99% of the indium became associated with the suspended solid phase (i.e. does not pass through a 0.45 μm filter). To determine the mechanism of removal of indium from the filterable and likely primarily dissolved phase, we conducted laboratory experiments to determine an upper bound for a sorption constant to iron oxides, and used this, along with other published thermodynamic constants, to model the partitioning of indium in Mineral Creek. Modeling results suggest that the removal of indium from the filterable phase is consistent with precipitation of indium hydroxide from a dissolved phase. This work demonstrates that nonferrous mining processes can be a significant source of indium to the environment, and provides critical information about the aqueous behavior of indium.

Colorado↗