Dissolved phosphate decreases the stability of amorphous ferric arsenate and nano-crystalline yukonite.

Extensive research has been conducted on the competitive adsorption of arsenate (AsO43-) and phosphate (PO43-) to mineral surfaces, but the stability of ferric arsenate mineral(oid)s under elevated phosphate levels remains poorly understood. Therefore, we investigated the impact of dissolved phosphate (0, 0.5, 50 mM) on the stability of amorphous ferric arsenate (AFA; FeAsO4·nH2O) and nano-crystalline yukonite [Ca2Fe3(AsO4)3(OH)4·4H2O], both synthetic and contained in natural As-contaminated soil (∼16 g/kg As) and mine-waste material (∼39 g/kg As) for up to one year. Substantial amounts of As (∼45% of total As) were released into solution from AFA and yukonite at high phosphate concentrations due to incongruent dissolution of the solids and substitution of arsenate by phosphate in both mineral(oids). After one year, both solids sequestered ∼8 wt% P with approximately 20-30% accounting for adsorbed and precipitated species. This P increase was also observed in the soil and mine-waste samples, where AFA and yukonite comprised up to 4.3 and 4.9 wt% P, respectively. The high reactivity of ferric arsenates with aqueous phosphate may lead to a substantial overestimation of adsorbed As determined by sequential As extractions of materials containing these phases and requires increased caution when applying phosphate to stabilize polymetallic mine wastes. Furthermore, long-term phosphate additions via fertilization of As-contaminated soil or renaturalized mine tailings containing amorphous or nano-crystalline ferric arsenates should be reduced to limit the export of As(V) into surface streams and groundwater.

Silver isotopes: A tool to trace smelter-derived contamination.

Here, for the first time, we report the concentrations and isotopic data of Ag in a variety of ore and metallurgical samples and forest soils that have been polluted due to Ag-Pb smelter emissions. Similar to the Ag concentrations, we identified a large range of δ109Ag values (from -0.8 to +2.4‰), a ∼3‰ spread, within the primary and secondary materials (i.e., galena, fly ash, slag and matte). This phenomenon, however, is evidently unrelated to Ag isotopic fractionation during the smelting process, but it reflects the starting 109Ag/107Ag signal in ore mineral and/or the specific type of ore genesis. The two studied soil profiles differed in Ag isotopic composition, but on the other hand, they consistently showed significantly lighter Ag (≤+0.8‰) of metallurgical origin in the upper horizons compared to the bottom horizons and bedrocks, with low Ag amounts depleted of 107Ag (≤+2.9‰). This isotopic pattern can be attributed to a ternary mixing relationship involving two major anthropogenic Ag components and a minor contribution from geogenic Ag. Accordingly, we did not observe any post-depositional isotopic fractionation in our soils, since Ag was geochemically stable and it was not subjected to leaching. In summary, the Ag isotopes have a potential to trace variations in anthropogenic phases, to monitor specific geochemical processes, and are clearly applicable as anthropogenic Ag source and Ag load proxies.

Smelter-derived soil contamination in Luanshya, Zambia.

Extensive mining and smelting contributed to the declining quality of Luanshya soils. The local smelter was the epicenter of contamination as shown by a spatial distribution analysis. Closeby soil profiles smelter exhibit extremely high Cu concentrations (up to 46,000 mg kg-1 Cu) relative to deeper layers where only background levels of trace elements were observed. A remote profile did not exhibit significant contamination. Lead isotopic ratios revealed that Pb contamination in the Luanshya soils was not smelter-derived. It was shown in this way that the historical usage of leaded gasoline was the main source of this metal. Although the Luanshya smelter also produced Co, this metal was not an important contaminant. Copper leaching was a concern in Luanshya. Upwards of 52 % of Cu was extractable in the exchangeable step of a sequential extraction procedure (SEP), but only for samples where Cu concentrations were high, suggesting that Cu was released exclusively from anthropogenic particles. This was supported by the SEP results for similar depths at the remote soil, where only a small fraction of Cu was labile (5.6 %). Lead and Co were strongly bound in the soils throughout. The excess of Cu in the topsoils was mostly bound in smelter-derived particles. These appeared as spherical fast-cooled droplets composed mostly of sulfides, oxides, and glass. X-ray diffraction and electron probe microanalysis of those particles allowed for a phase classification. Compositions were regularly not stoichiometric so most particles were classified as intermediate solid solutions. However, molecular proportions often closely resembled those of bornite, chalcanthite, cuprospinel, covellite, delafossite, diginite, or hydrous ferric oxides. Concentrations of Cu were often 100 % near the center of the particles indicating an inefficient smelting process. Weathering to some degree was common, which in conjunction with the susceptibility of Cu leaching was highly alarming.

Contaminant Binding and Bioaccessibility in the Dust From the Ni-Cu Mining/Smelting District of Selebi-Phikwe (Botswana).

We studied the dust fractions of the smelting slag, mine tailings, and soil from the former Ni-Cu mining and processing district in Selebi-Phikwe (eastern Botswana). Multi-method chemical and mineralogical investigations were combined with oral bioaccessibility testing of the fine dust fractions (<48  and <10 µm) in a simulated gastric fluid to assess the potential risk of the intake of metal(loid)s contaminants. The total concentrations of the major contaminants varied significantly (Cu: 301-9,600 mg/kg, Ni: 850-7,000 mg/kg, Co: 48-791 mg/kg) but were generally higher in the finer dust fractions. The highest bioaccessible concentrations of Co, Cu, and Ni were found in the slag and mine tailing dusts, where these metals were mostly bound in sulfides (pentlandite, pyrrhotite, chalcopyrite). On the contrary, the soil dusts exhibited substantially lower bioaccessible fractions of these metals due to their binding in less soluble spinel-group oxides. The results indicate that slag dusts are assumed to be risk materials, especially when children are considered as a target group. Still, this exposure scenario seems unrealistic due to (a) the fencing of the former mine area and its inaccessibility to the local community and (b) the low proportion of the fine particles in the granulated slag dump and improbability of their transport by wind. The human health risk related to the incidental ingestion of the soil dust, the most accessible to the local population, seems to be quite limited in the Selebi-Phikwe area, even when a higher dust ingestion rate (280 mg/d) is considered.

Effects of a point source of phosphorus on the arsenic mobility and transport in a small fluvial system.

One of the leading causes of As release from streambed sediments into freshwater systems is competition with phosphate. Among important sources of P to the fluvial ecosystems are wastewater treatment plants (WWTP), estimated to account for 25-45% of all P in surface waters. In this paper, long-term effects of discharged phosphorus from a small WWTP on the arsenic mobility were studied in an As-enriched fluvial system (approx. 240 mg/kg) in central Czech Republic. After 7 years of elevated P (≤7.7 mg/L) in the stream water, the total As decreased by 25% and the total P increased by 40% in the sediments downstream (at a distance of 66 m). The results of the chemical extractions and mineralogical analyses indicated that the changes in the concentration were mostly due to the sorption processes in the Fe (oxyhydr)oxides (goethite and hematite). In the downstream samples, the As in these phases decreased two-fold, and P was significantly enriched by 45-140%. Phosphorus was also found precipitated as newly formed Ca phosphates. The stream water monitoring indicated that the discharged P was either sequestered when the levels of dissolved P were high (>2.3 mg/L) or released from the downstream sediments when these levels were low (<∼1.5 mg/L). Meanwhile, As was continuously mobilized from the downstream sediments likely due to (i) the ongoing As desorption from the exterior parts of the Fe (oxyhydr)oxides at high aqueous P levels and (ii) the dissolution of As-bearing Ca phosphates at low dissolved P levels. These findings clearly demonstrate that point sources of P to streams and rivers, such as WWTP, may result in the permanent and long-term release of As from contaminated streambed sediments.

Effect of peat organic matter on sulfide weathering and thallium reactivity: Implications for organic environments.

Weathering of Tl-containing sulfides in a model (12-week) peat pot trial was studied to better understand their geochemical stability, dissolution kinetics, alteration products and the associated release and mobility of anthropogenic Tl in organic environments. We also present the effect of industrial acid rainwater on sulfide degradation and Tl migration in naturally acidic peat. Sphalerite (ZnS) was much less stable in peat than other Tl-containing sulfides (galena and pyrite), and thus acted as a major phase responsible for Tl mobilization. Furthermore, Tl incongruently leached out over Zn from ZnS, and accumulated considerably more in the peat solutions (≤5 µg Tl/L) and the peat samples (≤0.4 mg Tl/kg) that were subjected to acid rain watering compared to a deionized H2O regime. This finding was in good agreement with the absence of secondary Tl-containing phases, which could potentially control the Tl flux into the peat. The behavior of Tl was not as conservative as Pb throughout the trial, since a higher peat mobility and migration potential of Tl was observed compared to Pb. In conclusion, industrial acid precipitations can significantly affect the stability of ZnS even in acidic peat/organic environments, making it susceptible to enhanced weathering and Tl release in the long term.

Impact of organic matter on As sulfidation in wetlands: An in situ experiment.

Arsenic incorporation into newly formed As sulfides has recently been identified as an important As sequestration pathway in both laboratory experiments and natural As-wetlands. Here, we used an in situ experimental technique with double nylon experimental bags (10-µm mesh) to study the effect of low-cost organic materials (sawdust, wood cubes and hemp shives) on As sulfidation in three naturally As-enriched wetland soils under water-saturated (~1 m depth) and neutral pH conditions. After 15 months of in situ incubation, all of the organic materials and their corresponding inner bags were covered by yellow-black mineral accumulations, dominantly composed of crystalline As4S4 polymorphs (realgar and bonazziite) and reactive Fe(II) sulfides (probably mackinawite); while the major fraction of As (~80%) was sequestered as AsS minerals. The amount of As accumulation in the experimental bags varied significantly (0.03-4.24 g As kg-1) and corresponded with different levels of As (0.23-9.4 mg As L-1) in the groundwater. Our findings suggest an authigenic formation of AsS minerals in strongly reducing conditions of experimental bags by a combination of reduced exchange of solutes through the pores of the bag and comparatively fast microbial production of dissolved sulfide. Arsenic sulfide formation, as an effective treatment mechanism for natural and human-constructed wetlands, appears to be favored for As(III)-rich waters with a low Fe(II)/As(III) molar ratio. These conditions prevent the consumption of dissolved As and sulfide by their preferential incorporation into natural organic matter, and newly-formed Fe(II) sulfides, respectively.

Arsenic fractionation and mobility in sulfidic wetland soils during experimental drying.

In this study, two Czech wetland soils enriched in authigenic sulfide minerals (especially realgar) were collected from the saturated zone (60-100 cm), flooded with local groundwater and allowed to dry for up to 98 days. The objective was to examine the mobility of As, Fe, S and trace metals using selective chemical extractions, S isotopes and X-ray diffraction through the drying process. During the initial stage of incubation (∼20 days), the re-flooding of the soils triggered a microbially-mediated SO42- reduction, which immobilized the Co, Cu and Ni. The reductive dissolution of As-bearing Fe (oxyhydr)oxides and the release of As were documented only in the Fe-rich/organic-low soil. Over the next stage of incubation (∼75 days), the exposure and drying of the soils led to the oxidation of the Fe and As sulfides. The arsenic and trace metals released via oxidation of the sulfide phases (particularly Fe sulfides) were almost entirely sequestered by the Fe(III) (oxyhydr)oxides, but acidification during the oxidation stage of the incubation resulted in the pH-dependent release of the As and trace metals (Co, Cu, Ni) (especially in the Fe-rich/organic-low soil). These findings suggest that sulfidic soils in wetlands can be considered as long-term sources of As during major drought events.

Slag dusts from Kabwe (Zambia): Contaminant mineralogy and oral bioaccessibility.

The former Pb-Zn mining town of Kabwe in central Zambia is ranked amongst the worst polluted areas both in Africa and in the world. The fine dust particles from the ISF and Waelz slags deposited in Kabwe represent a health risk for the local population. Here, we combined a detailed multi-method mineralogical investigation with oral bioaccessibility testing in simulated gastric fluid (SGF; 0.4 M glycine, pH 1.5, L/S ratio of 100, 1 h, 37 °C) to evaluate the risk related to the incidental dust ingestion. The slag dust fractions contain up to 2610 mg/kg V, 6.3 wt% Pb and 19 wt% Zn. The metals are mainly bound in a slag glass and secondary phases, which formed during the slag weathering or were windblown from nearby tailing stockpiles (carbonates, Fe and Mn oxides, phosphates, vanadates). The bioaccessible fractions (BAFs) are rather high for all the main contaminants, with the BAF values generally higher for the ISF slags than for the Waelz slags: Pb (24-96%), V (21-100%) and Zn (54-81%). The results clearly indicate the potential risks related to the incidental slag dust ingestion. Even when a conservative value of the dust daily intake (100 mg/day) is considered, the daily contaminant intake significantly exceeds the tolerable daily intake limits, especially for Pb â‰« V > Zn. At higher ingestion rates, other minor contaminants (As, Cd) also become a health risk, especially for children. The slag heaps in Kabwe should be fenced to prevent local people entering and should be covered to limit the dust dispersion.

Thallium isotopic fractionation in soil: the key controls.

We studied the key geochemical and mineralogical factors that could affect the fractionation of stable thallium (Tl) isotopes in soil. A set of grassland soil samples enriched in geogenic Tl in combination with selected Tl-containing mineral materials from the Czech Republic (Kluky) were investigated for this purpose. The results demonstrate significant incorporation of Tl in pedogenic (specific) Mn-oxide, which led to a large accumulation of the heavy 205Tl isotope (∼+14 ε205Tl units), presumably resulting from oxidative Tl sorption. Consequently, we concluded that the Mn-oxide-controlled Tl uptake is the primary cause of the observed 205Tl enrichment in the middle profile zone, at the A/B soil horizon interface, with up to +4 of ε205Tl. Furthermore, our results displayed a clear relationship between the Tl isotopic fractionation degree and the Mn-oxide soil concentration (R2 = 0.6), as derived from the oxalate-extractable data. A combination of soil and mineralogical considerations suggests that 205Tl enrichment in respective soil samples is also partly due to the Tl present in micaceous clay minerals, mainly illite, which is the predominant pedogenic Tl host phase. In line with our previous results, this Tl behavior can be inferred from systematic Mn-oxide degradation and the associated Tl (enriched in 205Tl) cycling in the studied soils and thus, presumably in the redoximorphic soils in general.

Realgar (As4S4) bioprecipitation in microcosm fed by a natural groundwater and organic matter.

Sequestration of arsenic to biogenic sulfide minerals is known from As-contaminated anoxic environments. Despite numerous successful laboratory experiments, the process remains difficult to predict in moderate arsenic conditions. We performed microcosm experiments using naturally contaminated groundwater (containing ca. 6 mg/L As) and natural organic matter (NOM) particles both collected from wetland soil. Macroscopic realgar precipitates, occasionally accompanied by bonazziite, a FeS phase, elementary S, calcite, and whewellite, appeared after 4 to 18 months. Realgar only precipitated in microcosms moderately poisoned by azide or antibiotics and those in which oxidation of hydrogen sulfide to sulfur took place. The biomineralization process was not affected by the presence of additional carbon sources or the diversity, community structure, and functional composition of the microbial community. Hydrogen sulfide concentration was greater in the realgar-free microcosms, suggesting that arsenic thiolation prevented precipitation of realgar. We compared our data to available microbial community data from soils with different rates of realgar precipitation, and found that the communities from realgar-encrusted NOM particles usually showed limited sulfate reduction and the presence of fermentative metabolisms, whereas communities from realgar-free NOM particles were strongly dominated by sulfate reducers. We argue that the limited sulfate supply and intensive fermentation amplify reducing conditions, which make arsenic sulfide precipitation plausible in high-sulfate, low-arsenic groundwaters.

Oral bioaccessibility of metal(loid)s in dust materials from mining areas of northern Namibia.

Ore mining and processing in semi-arid areas is responsible for the generation of metal(loid)-containing dust, which is easily transported by wind to the surrounding environment. To assess the human exposure to dust-derived metal(loid)s (As, Cd, Cu, Pb, Sb, Zn), as well as the potential risks related to incidental dust ingestion, we studied mine tailing dust (n = 8), slag dust (n = 5) and smelter dust (n = 4) from old mining and smelting sites in northern Namibia (Kombat, Berg Aukas, Tsumeb). In vitro bioaccessibility testing using extraction in simulated gastric fluid (SGF) was combined with determination of grain-size distributions, chemical and mineralogical characterizations and leaching tests conducted on original dust samples and separated PM10 fractions. The bulk and bioaccessible concentrations of the metal(loid)s were ranked as follows: mine tailing dusts < slag dusts ≪ smelter dusts. Extremely high As and Pb bioaccessibilities in the smelter dusts were caused by the presence of highly soluble phases such as arsenolite (As2O3) and various metal-arsenates unstable under the acidic conditions of SGF. The exposure estimates calculated for an adult person of 70 kg at a dust ingestion rate of 50 mg/day indicated that As, Pb (and also Cd to a lesser extent) grossly exceeded tolerable daily intake limits for these contaminants in the case of slag and smelter dusts. The high risk for smelter dusts has been acknowledged, and the safety measures currently adopted by the smelter operator in Tsumeb are necessary to reduce the staff's exposure to contaminated dust. The exposure risk for the local population is only important at the unfenced disposal sites at Berg Aukas, where the PM10 exhibited high levels of bioaccessible Pb.

Thallium contamination of desert soil in Namibia: Chemical, mineralogical and isotopic insights.

We studied arid desert soils from Namibia (Rosh Pinah) that were contaminated with up to 7 mg kg-1 of thallium (Tl) via dust emitted from a local flotation tailing dam. Chemical extractions of waste and soil materials indicated that most of the Tl is strongly bound, in accordance with X-ray diffraction and X-ray absorption spectroscopy data that point to the predominant association of Tl with metal sulfides and phyllosilicates. The isotope fractionation factor ε205Tl of the soil samples (from -0.4 to +3.8) shows a positive linear relationship (R2 = 0.62) with 1/Tl, indicative for the mixing of two major Tl pools, presumably anthropogenic Tl and geogenic Tl. The ε205Tl value for the topmost soil samples (∼+3) closely matches the ε205Tl value for post-flotation waste particles with a diameter of <0.05 mm, whereas the bulk flotation waste exhibits a significantly larger ε205Tl value (∼+6). These variations are in accordance with predominant atmospheric transfer of Tl from the tailings to the adjacent soils via fine (dust) particles. The identified minimal Tl alteration in soils indicates that only a small part of the Tl could be potentially released and passively enter the vegetation, local population and/or food chain in the long term. From this viewpoint, Tl does not represent such an important environmental concern as other (abundant) contaminants at the locality. Furthermore, there could be a relevance for other alkaline desert soils, including those where Tl pollution plays a major role.

Transformation of arsenic-rich copper smelter flue dust in contrasting soils: A 2-year field experiment.

Dust emissions from copper smelters processing arsenic-bearing ores represent a risk to soil environments due to the high levels of As and other inorganic contaminants. Using an in situ experiment in four different forest and grassland soils (pH 3.2-8.0) we studied the transformation of As-rich (>50 wt% As) copper smelter dust over 24 months. Double polyamide bags with 1 g of flue dust were buried at different depths in soil pits and in 6-month intervals; then those bags, surrounding soil columns, and soil pore waters were collected and analysed. Dust dissolution was relatively fast during the first 6 months (5-34%), and mass losses attained 52% after 24 months. The key driving forces affecting dust dissolution were not only pH, but also the water percolation/retention in individual soils. Primary arsenolite (As2O3) dissolution was responsible for high As release from the dust (to 72%) and substantial increase of As in the soil (to a 56 × increase; to 1500 mg kg-1). Despite high arsenolite solubility, this phase persisted in the dust after 2 years of exposure. Mineralogical investigation indicated that mimetite [Pb5(AsO4)3(Cl,OH)], unidentified complex Ca-Pb-Fe-Zn arsenates, and Fe oxyhydroxides partly controlled the mobility of As and other metal(loid)s. Compared to As, other less abundant contaminants (Bi, Cu, Pb, Sb, Zn) were released into the soil to a lesser extent (8-40% of total). The relatively high mobility of As in the soil can be seen from decreases of bulk As concentrations after spring snowmelt, high water-extractable fractions with up to ∼50% of As(III) in extracts, and high As concentrations in soil pore waters. Results indicate that efficient controls of emissions from copper smelters and flue dust disposal sites are needed to prevent extensive contamination of nearby soils by persistent As.

Characterization and pH-dependent environmental stability of arsenic trioxide-containing copper smelter flue dust.

Increasing amounts of impurities (especially As) in Cu ores have aggravated the problem of flue dust generation in recent years. As an example from a smelter processing As-rich Cu ores, we characterized a flue dust particularly rich in As (>50 wt%) to understand its mineralogy and pH-dependent leaching behavior, with special emphasis on binding, release and solubility controls of inorganic contaminants (As, Bi, Cd, Cu, Pb, Sb, Zn). Whereas arsenolite (As2O3) was the major host for As and Sb, other contaminants were bound in sulfides, arsenates, alloys and slag-like particles. The EU regulatory leaching test (EN 12457-2) indicated that leached As, Cd, Sb and Zn significantly exceeded the limit values for landfills accepting hazardous waste. The pH-dependent leaching test (CEN/TS 14997) revealed that As, Sb and Pb exhibited the greatest leaching at pH 11-12, whereas Cd, Cu and Zn were leached most under acidic condition (pH 3) and Bi leaching was pH-independent. Mineralogical investigation of leached residue coupled with geochemical modeling confirmed that newly formed Ca, Pb and Ca-Pb arsenates (mimetite, Pb5(AsO4)3Cl) partly control the release of As and other contaminants under circumneutral and alkaline conditions and will be of key importance for the fate of smelter-derived contamination in soils or when stabilization technology is employed.

Bioaccessibility of As, Cu, Pb, and Zn in mine waste, urban soil, and road dust in the historical mining village of Kank, Czech Republic.

Historical mining activities in the village of Kank (in the northern part of the Kutná Hora ore district, Czech Republic) produced large amounts of mine wastes which contain significant amounts of metal(loid) contaminants such as As, Cu, Pb, and Zn. Given the proximity of residential communities to these mining residues, we investigated samples of mine waste (n = 5), urban soil (n = 6), and road dust (n = 5) with a special focus on the solid speciation of As, Cu, Pb, and Zn using a combination of methods (XRD, SEM/EDS, oxalate extractions), as well as on in vitro bioaccessibility in simulated gastric and lung fluids to assess the potential exposure risks for humans. Bulk chemical analyses indicated that As is the most important contaminant in the mine wastes (~1.15 wt%), urban soils (~2900 mg/kg) and road dusts (~440 mg/kg). Bioaccessible fractions of As were quite low (4-13%) in both the simulated gastric and lung fluids, while the bioaccessibility of metals ranged between <0.01% (Pb) and 68% (Zn). The bioaccessibilities of the metal(loid)s were dependent on the mineralogy and different adsorption properties of the metal(loid)s. Based on our results, a potential health risk, especially for children, was recognized from the ingestion of mine waste materials and highly contaminated urban soil. Based on the risk assessment, arsenic was found to be the element posing the greatest risk.

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.

Arsenic mineralogy and mobility in the arsenic-rich historical mine waste dump.

A more than 250 year-old mine dump was studied to document the products of long-term arsenopyrite oxidation under natural conditions in a coarse-grained mine waste dump and to evaluate the environmental hazards associated with this material. Using complementary mineralogical and chemical approaches (SEM/EDS/WDS, XRD, micro-Raman spectroscopy, pore water analysis, chemical extraction techniques and thermodynamic PHREEQC-2 modeling), we documented the mineralogical/geochemical characteristics of the dumped arsenopyrite-rich material and environmental stability of the newly formed secondary minerals. A distinct mineralogical zonation was found (listed based on the distance from the decomposed arsenopyrite): scorodite (locally associated with native sulfur pseudomorphs) plus amorphous ferric arsenate (AFA/pitticite), kankite, As-bearing ferric (hydr)oxides and jarosite. Ferric arsenates and ferric (hydr)oxides were found to dissolve and again precipitate from downward migrating As-rich solutions cementing rock fragments. Acidic pore water (pH3.8) has elevated concentrations of As with an average value of about 2.9 mg L(-1). Aqueous As is highly correlated with pH (R2=0.97, p<0.001) indicating that incongruent dissolution of ferric arsenates controls dissolved As well as the pH of the percolating waste solution. Arsenic released from the dissolution of ferric arsenates into the pore water is, however, trapped by latter and lower-down precipitating jarosite and especially ferric (hydr)oxides. The efficiency of As sequestration by ferric (hydr)oxides in the waste dump and underlying soil has been found to be very effective, suggesting limited environmental impact of the mine waste dump on the surrounding soil ecosystems.