Arsenopyrite (FeAsS) and realgar (As4S4) are two common arsenic minerals that often cause serious environmental issues. Centralised treatment of arsenic-containing tailings can reduce land occupation and save management costs. The current work examined the remediation schemes of tailings from Hunan Province, China, where by different tailings containing arsenopyrite and realgar were blended with exogenous slag zero valence iron (ZVI). Introducing Fe-oxidising bacteria (Acidithiobacillus ferrooxidans) recreates a biologically oxidative environment. All bioleaching experiments were done over three stages, each for 7 days and the solid phase of all tests was characterised by scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy and selective extraction analyses. The results showed that the mixture group reduced arsenic release by 72.9–74.7% compared with the control group. The addition of 0.2 g ZVI clearly decreased arsenic release, and the addition of 4.0 g ZVI led to the lowest arsenic release among all tests. The decrease of arsenic released from the tailings was due to the adsorption and uptake of arsenic by secondary iron-containing minerals and Fe–As(V) secondary mineralisation. The addition of large amounts of ZVI reduced the arsenic detected in the amorphous Fe precipitates. Therefore, a low cost and integrated strategy to reduce arsenic release from tailings is to mix two typical tailings and apply exogenous slag ZVI, which can apply to the in situ remediation of two kinds or more arsenic-containing tailings.

Ambient temperature X-ray diffraction data were collected at different pressures from two crystals of β-As4S4, which were made by heating realgar under vacuum at 295ºC for 24 h. These data were used to calculate the unit-cell parameters at pressures up to 6.86 GPa. Above 2.86 GPa, it was only possible to make an approximate measurement of the unit-cell parameters. As expected for a crystal structure that contains molecular units held together by weak van der Waals interactions, β-As4S4 has an exceptionally high compressibility. The compressibility data were fitted to a third-order Birch–Murnaghan equation of state with a resulting volume V0 = 808.2(2) Å3, bulk modulus K0 = 10.9(2) GPa and K' = 8.9(3). These values are extremely close to those reported for the low-temperature polymorph of As4S4, realgar, which contains the same As4S4 cage-molecule. Structural analysis showed that the unit-cell contraction is due mainly to the reduction in intermolecular distances, which causes a substantial reduction in the unit-cell volume (∼21% at 6.86 GPa). The cage-like As4S4 molecules are only slightly affected. No phase transitions occur in the pressure range investigated.

Micro-Raman spectra, collected across the entire pressure range, show that the peaks associated with As–As stretching have the greatest pressure dependence; the S–As–S bending frequency and the As–S stretching have a much weaker dependence or no variation at all as the pressure increases; this is in excellent agreement with the structural data.