Mobility and attenuation of arsenic in sulfide-rich mining wastes from the Czech Republic.

The mineralogical composition of mining wastes deposited in countless dumps around the world is the key factor that controls retention and release of pollutants. Here we report a multi-method data set combining mineralogical (X-ray diffraction, electron microprobe and Raman microspectrometry) and geochemical (sequential extraction and pore water analysis) methods to resolve As mobility in two 50-years-old mining waste dumps. Originally, all of the As in the mining wastes selected for the study was present as arsenopyrite and with time it has been replaced by secondary As phases. At Jedová jáma mining area, the most of As precipitated as X-ray amorphous ferric arsenate (HFA). Arsenic is also accumulated in the scorodite and Fe (hydr)oxide (with up to 3.2wt.% As2O5) that is particularly represented by hematite. Mining wastes at Dlouhá Ves contain only trace amount of scorodite. Arsenic is primarily bound to Pb-jarosite and Fe (hydr)oxides (especially goethite) with up to 1.6 and 1.8wt.% As2O5, respectively. The pore water collected after rainfall events indicated high concentrations of As (~4600µg·L(-1)) at Jedová jáma, whereas aqueous As at Dlouhá Ves was negligible (up to 1.5µg·L(-1)). Highly mobile As at Jedová jáma is attributed to the dissolution of HFA and simultaneous precipitation of Fe (hydr)oxides under mildly acidic conditions (pH~4.4); immobile As at Dlouhá Ves is due to the efficient adsorption on the Fe (hydr)oxides and hydroxosulfates under acidic pH of ~2.8. Taken together, As mobility in the ferric arsenates-containing mining wastes may significantly vary. These wastes must be kept under acidic conditions or with high aqueous Fe(III) concentrations to prevent the release of As from incongruent dissolution of ferric arsenates.

Raman spectroscopic identification of arsenate minerals in situ at outcrops with handheld (532 nm, 785 nm) instruments.

Minerals are traditionally identified under field conditions by experienced mineralogists observing the basic physical properties of the samples. Under laboratory conditions, a plethora of techniques are commonly used for identification of the geological phases based on their structural and spectroscopic parameters. In this area, Raman spectrometry has become a useful tool to complement the more widely applied XRD. Today, however, there is an acute need for a technique for unambiguous in situ identification of minerals, within the geological as well as planetary/exobiology realms. With the potential for miniaturization, Raman spectroscopy can be viewed as a practical technique to achieve these goals. Here, for the first time, the successful application of handheld Raman spectrometers is demonstrated to detect and discriminate arsenic phases in the form of earthy aggregates. The Raman spectroscopic analyses of arsenate minerals were performed in situ using two handheld instruments, using 532 and 785 nm excitation. Bukovskýite, kankite, parascorodite, and scorodite were identified from Kank near Kutná Hora, CZE; kankite, scorodite, and zýkaite were identified at the Lehnschafter gallery in an old silver mine at Mikulov near Teplice, Bohemian Massif, CZE.

Selectivity assessment of an arsenic sequential extraction procedure for evaluating mobility in mine wastes.

An optimized sequential extraction (SE) scheme for mine waste materials has been developed and tested for As partitioning over a range of pure As-bearing mineral phases, their model mixtures, and natural mine waste materials. This optimized SE procedure employs five extraction steps: (1) nitrogen-purged deionized water, 10h; (2) 0.01 M NH4H2PO4, 16 h; (3) 0.2M NH4-oxalate in the dark, pH3, 2 h; (4) 0.2 M NH4-oxalate, pH3/80°C, 4 h; (5) KClO3/HCl/HNO3 digestion. Selectivity and specificity tests on natural mine wastes and major pure As-bearing mineral phases showed that these As fractions appear to be primarily associated with: (1) readily soluble; (2) adsorbed; (3) amorphous and poorly-crystalline arsenates, oxides and hydroxosulfates of Fe; (4) well-crystalline arsenates, oxides, and hydroxosulfates of Fe; as well as (5) sulfides and arsenides. The specificity and selectivity of extractants, and the reproducibility of the optimized SE procedure were further verified by artificial model mineral mixtures and different natural mine waste materials. Partitioning data for extraction steps 3, 4, and 5 showed good agreement with those calculated in the model mineral mixtures (<15% difference), as well as that expected in different natural mine waste materials. The sum of the As recovered in the different extractant pools was not significantly different (89-112%) than the results for acid digestion. This suggests that the optimized SE scheme can reliably be employed for As partitioning in mine waste materials.