Arsenic contamination of groundwater associated with mining operations is a widespread problem across the globe. The release of arsenic (As) into the environment occurs naturally by oxidation of exposed sulfide minerals. In the case of gold ores, the mining and beneficiation may also produce As-bearing wastes and this can accelerate the natural mechanisms of As mobilization. The Bakyrchik is the largest gold deposit in Kazakhstan and one of the largest in the world. Gold (Au) is dispersed in pyrite and arsenopyrite in the form of microscopic inclusions. Despite the fact that only 10% of gold ore has been mined to date, it has left behind a dangerous As-containing legacy.

Speciation of As has been determined for samples from Bakyrchik to understand the post-processing environment and the mobility of arsenic in the mining-influenced area. As(III) and As(V) have been detected in water samples using HPLC-ICP-MS. The variability of As species across the narrow pH and Eh range indicates that biogeochemical processes can play a role in the speciation of As in water at the study site. In order to understand processes controlling As mobilization in water, the solid phase speciation of As in Bakyrchik sediments, soil, and metallurgical processing products has been investigated using XRD and EPMA. This revealed arsenopyrite, As-bearing pyrite, and their alteration products containing up to 25% As, iron oxides and oxyhydroxides (with up to 2.5% As), haidingerite, and calcium arsenate in studied samples. Sequential extraction demonstrated that in soil and sediment samples As is associated mainly with Al and amorphous Fe oxyhydroxides. Results suggest that the main mechanisms controlling As mobility in Bakyrchik are dilution with regional waters, adsorption onto iron and aluminium oxyhydroxides, and co-precipitation of dissolved As with alteration products of sulfide minerals. Assessment of As bioaccessibility through inhalation demonstrates its strong dependence on the mineralogy rather than on total As content of the solid samples. Calculated cancer and non-cancer risks of inhalation exposure imply that all samples are highly hazardous for human health.

With the depletion of the oxide lode ore deposits, gold extraction is moving towards the mining of technologically difficult ores, such as those found at Bakyrchik. A new method of Au recovery from double refractory Au-As-bearing concentrates has been developed, allowing recovery of 97% of Au, and the conversion of up to 95% As into iron-arsenic alloy. Fe-As alloy can contain up to 40% As, and do not require further solidification/stabilisation prior to disposal. The method has been published as a patent with the Patent Office of the Republic of Kazakhstan. Quantitative phase composition of the Fe-As alloy, has been determined by EPMA, QEMSCAN, X-ray and neutron diffraction. Toxicity and solubility of Fe-As alloy in aqueous solutions have been characterised. High-temperature structural behaviour of Fe-As alloy and Fe$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$As in inert atmosphere has been determined by $in\; situ$ synchrotron XRD. Results of the study support the development of the new method as an efficient alternative for processing double refractory Au-As-bearing concentrates.