Applied Geochemistry (v.21, #8)

Defects and impurities in jarosite: A computer simulation study by Adrian M.L. Smith; Karen A. Hudson-Edwards; William E. Dubbin; Kate Wright (1251-1258).
Computer modelling techniques involving a rigid ion model have been used to investigate the defect structure and impurity site preferences in end-member K-jarosite. Calculated intrinsic vacancy energies show that the K2SO4 neutral cluster, with an energy per species of 1.34 eV, will be the most common defect in the pure phase. Defect reactions leading to vacancies on the Fe site have high energies, in excess of 4.0 eV per species, and are thus unlikely to occur in great numbers. However, the calculations show that divalent metal cations can be incorporated onto the Fe site via solution reactions with oxides leading to the formation of goethite. Calculated solution reactions are exothermic and thus predicted to be highly favourable. At K sites substitutions occur in the order Cd > Zn > Cu, but will be limited due to endothermic solution energies and structural considerations.

Grains of naturally oxidized arsenopyrite [FeAsS] collected from the oxidation zone in W-mine tailings were investigated, primarily using transmission electron microscopy. The grains are severely pitted and are surrounded by secondary minerals. The pitted nature of the grains is related to mechanisms governing the electrochemical oxidation of sulfide minerals, with prominent cusp-like features occurring at cathodic regions of the surface, and pits occurring at anodic regions. In general, the oxidation of arsenopyrite leads to the formation of an amorphous (or nanocrystalline) Fe–As–O-rich coating that contains small amounts of Si, Ca, Cu, Zn, Pb and Bi; nanoscale variation in the As, Pb, Bi and Zn contents of the coating was noted. Secondary Cu sulfides, thought to be chalcocite [Cu2S] and (or) djurleite [Cu31S16], occur as a layer (generally <500 nm thick) along the arsenopyrite grain boundary, and also within the coating as aggregates, and as layers that parallel the grain boundary. Although the precipitation of secondary Cu minerals along the grain boundary is a nanoscale feature, the process of formation is thought to be analogous to the supergene enrichment that occurs in weathered sulfide deposits. As the oxidation of arsenopyrite proceeds, layers and clusters of secondary Cu sulfides become isolated in the Fe–As–O coating. Secondary wulfenite [PbMoO4] and an unidentified crystalline Bi–Pb–As–O mineral occur in voids within the coating, suggesting that these minerals precipitated from the local pore-water. Small and variable amounts of W, Ca, Bi, As and Zn are associated with the wulfenite, and Zn, Fe and Ca are associated with the Bi–Pb–As–O mineral. Some of the wulfenite is in contact with inclusions of molybdenite [MoS2], suggesting that the oxidation of molybdenite in the presence of aqueous Pb(II) led to the formation of wulfenite. Mineralogical analyses at the nanoscale have improved the understanding of geochemical sources and sinks at this location. The results of this study indicate that the mineralogical controls on aqueous elemental concentrations at this tailings site are complex and are not predicted by thermodynamic calculations.

Manganese removal from mine waters – investigating the occurrence and importance of manganese carbonates by Selina M. Bamforth; David A.C. Manning; Ian Singleton; Paul L. Younger; Karen L. Johnson (1274-1287).
Manganese is a common contaminant of mine water and other waste waters. Due to its high solubility over a wide pH range, it is notoriously difficult to remove from contaminated waters. Previous systems that effectively remove Mn from mine waters have involved oxidising the soluble Mn(II) species at an elevated pH using substrates such as limestone and dolomites. However it is currently unclear what effect the substrate type has upon abiotic Mn removal compared to biotic removal by in situ micro-organisms (biofilms). In order to investigate the relationship between substrate type, Mn precipitation and the biofilm community, net-alkaline Mn-contaminated mine water was treated in reactors containing one of the pure materials: dolomite, limestone, magnesite and quartzite. Mine water chemistry and Mn removal rates were monitored over a 3-month period in continuous-flow reactors. For all substrates except quartzite, Mn was removed from the mine water during this period, and Mn minerals precipitated in all cases. In addition, the plastic from which the reactor was made played a role in Mn removal. Manganese oxyhydroxides were formed in all the reactors; however, Mn carbonates (specifically kutnahorite) were only identified in the reactors containing quartzite and on the reactor plastic. Magnesium-rich calcites were identified in the dolomite and magnesite reactors, suggesting that the Mg from the substrate minerals may have inhibited Mn carbonate formation. Biofilm community development and composition on all the substrates was also monitored over the 3-month period using denaturing gradient gel electrophoresis (DGGE). The DGGE profiles in all reactors showed no change with time and no difference between substrate types, suggesting that any microbiological effects are independent of mineral substrate. The identification of Mn carbonates in these systems has important implications for the design of Mn treatment systems in that the provision of a carbonate-rich substrate may not be necessary for successful Mn precipitation.

Phosphate-induced metal stabilization involving the reactive medium Apatite II™ [Ca10−x Na x (PO4)6−x (CO3) x (OH)2], where x  < 1, was used in a subsurface permeable reactive barrier (PRB) to treat acid mine drainage in a shallow alluvial groundwater containing elevated concentrations of Zn, Pb, Cd, Cu, SO4 and NO3. The groundwater is treated in situ before it enters the East Fork of Ninemile Creek, a tributary to the Coeur d’Alene River, Idaho. Microbially mediated SO4 reduction and the subsequent precipitation of sphalerite [ZnS] is the primary mechanism occurring for immobilization of Zn and Cd. Precipitation of pyromorphite [Pb10(PO4)6(OH,Cl)2] is the most likely mechanism for immobilization of Pb. Precipitation is occurring directly on the original Apatite II. The emplaced PRB has been operating successfully since January of 2001, and has reduced the concentrations of Cd and Pb to below detection (2 μg L−1), has reduced Zn to near background in this region (about 100 μg L−1), and has reduced SO4 by between 100 and 200 mg L−1 and NO3 to below detection (50 μg L−1). The PRB, filled with 90 tonnes of Apatite II, has removed about 4550 kg of Zn, 91 kg of Pb and 45 kg of Cd, but 90% of the immobilization is occurring in the first 20% of the barrier, wherein the reactive media now contain up to 25 wt% Zn. Field observations indicate that about 30% of the Apatite II material is spent (consumed).

Mechanisms controlling acid neutralization and metal mobility within a Ni-rich tailings impoundment by M.R. Gunsinger; C.J. Ptacek; D.W. Blowes; J.L. Jambor; M.C. Moncur (1301-1321).
Low-quality pore waters containing high concentrations of dissolved H+, SO4, and metals have been generated in the East Tailings Management Area at Lynn Lake, Manitoba, as a result of sulfide-mineral oxidation. To assess the abundance, distribution, and solid-phase associations of S, Fe, and trace metals, the tailings pore water was analyzed, and investigations of the geochemical and mineralogical characteristics of the tailings solids were completed. The results were used to delineate the mechanisms that control acid neutralization, metal release, and metal attenuation. Migration of the low-pH conditions through the vadose zone is limited by acid-neutralization reactions, resulting in the development of distinct pore-water pH zones at depth; the neutralization reactions involve carbonate (pH ⩾ 5.7), Al-hydroxide (pH ⩾ 4.0), and aluminosilicate solids. As the zone of low-pH pore water expands, the pH will then be primarily controlled by less soluble solids, such as Fe(III) oxyhydroxides (pH < 3.5) and the relatively more recalcitrant aluminosilicates (pH ⩾ 1.3). Precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxides and hydroxysulfates control the concentrations of dissolved Fe(III). Concentrations of dissolved SO4 are principally controlled by the formation of gypsum and jarosite. Geochemical extractions indicate that the solid-phase concentrations of Ni, Co, and Zn are associated predominantly with reducible and acid-soluble fractions. The concentrations of dissolved trace metals are therefore primarily controlled by adsorption/complexation and (or) co-precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxide and hydroxysulfate minerals. Concentrations of dissolved metals with relatively low mobility, such as Cu, are also controlled by the precipitation of discrete minerals. Because the major proportion of metals is sequestered through adsorption and (or) co-precipitation, the metals are susceptible to remobilization if low-pH or reducing conditions develop within the tailings.

The Ervedosa Mine, in north-eastern Portugal, has Sn-bearing quartz veins containing cassiterite and sulphides that cut Silurian schists and a Sn-bearing muscovite granite. These veins were mined for Sn and As2O3 until 1969. Cassiterite, the main Sn ore, has alternate lighter and darker growth-zones. The darker zones are richer in Fe, Nb, Ta and Ti, but poorer in Sn than the adjoining lighter zones. Exsolution blebs of ferrocolumbite, manganocolumbite, Ti ixiolite, rutile, ilmenite and rare wolframite were found in the darker zones. Arsenopyrite is the most abundant sulphide and contains inclusions of pyrrhotite, bismuth, bismuthinite and matildite. Other sulphides are pyrite, sphalerite, chalcopyrite and stannite. Secondary solid phases consisting mainly of hydrate sulphate complexes of Al, Fe, Ca and Mg (aluminocopiapite, copiapite, halotrichite, pickeringite, gypsum and alunogen, meta-alunogen) occur at the surface of the Sn-bearing quartz veins and their wall rocks (granite and schist), while oxides, hydroxides, arsenates and residual mineral phases (albite, muscovite and quartz) occur in mining tailings. Toxic acid mine waters (acid mine drainage AMD), which have high conductivity and significant concentrations of As, SO4 and metal (Cu, Zn, Pb, Fe, Mn, Cd, Ni and Co), occur in an area directly affected by the mine. Surface stream waters outside this area have low conductivity and a pH that is almost neutral. Metal and As concentrations are also lower. Stream waters within the impact area have an intermediate composition, falling between that of the AMD and the natural stream waters outside impact area. Waters associated directly with mineralised veins must not be used for human consumption or agriculture.

The chemical speciation of heavy metals (Cd, Cr, Cu, Ni, Pb and Zn) in marine sediments from two coastal regions of Singapore (Kranji in the NW, and Pulau Tekong in the NE) was determined using the latest version of the 3-step sequential extraction procedure, as described by the European Community Bureau of Reference (1999). To obtain a mass balance, a fourth step, i.e., digestion and analysis of the residue was undertaken using a microwave-assisted acid digestion procedure. The total content of all metals except for Pb in sediments was greater in Kranji than in Pulau Tekong. All metals, except Cd were more mobile and bio-available in Kranji, where metals were present at higher percentages in the acid-soluble fractions (the most labile fraction). In sediments from Kranji, the mobility order of the heavy metals studied was Cd > Ni > Zn > Cu > Pb > Cr, whereas sediments from Pulau Tekong showed the same order for Cd, Ni, Pb and Cr, but had a reverse order for Cu and Zn (Cu > Zn). The highest percentages of Cr, Ni and Pb were found in the residual fractions in both Kranji (78.9%, 54.7%, 55.9%, respectively) and Pulau Tekong (82.8%, 77.3%, 62.2%, respectively), meaning that these metals were strongly bound to the sediments. Results are consistent with findings from Barcelona, Spain where similar results for Cr and Ni have also been reported for marine sediments. The sum of the 4 steps (acid-soluble + reducible + oxidizable + residual) was in good agreement with the total content, which implies that the accuracy of the microwave extraction procedure in conjunction with the GFAAS analytical method is assured.

The relationships between factors that control subsurface flow and the timing, duration, and intensity of acidity generation and leaching of metals from waste-rock dumps are investigated. A 12 m high waste-rock pile that had been constructed in 1994 at Key Lake, Saskatchewan, Canada was disassembled, sampled and characterized in 2000. Physical properties that control water flow were characterized by measuring soil–water suction, volumetric water content, and the grain-size distribution at 60 randomized sites within the pile. Grain-size distribution was also measured at an additional 20 grid locations within the pile. Paste pH, pore-water geochemistry, mineralogy, and water-soluble extractions were used to investigate geochemical processes and sulfide oxidation at each of the 20 grid locations. A field-based soil–water characteristic curve could not be developed from the spatially variable and hysteretic field data; consequently, the grain-size distribution was used as a relative measure of subsurface flow and of the tendency to contain water under unsaturated conditions. The geochemical characterization demonstrated that marcasite underwent preferential weathering relative to pyrite and chalcopyrite, that dolomite was the main buffering carbonate mineral, and that gypsum, jarosite, and Fe oxyhydroxides were the main secondary (supergene) minerals. The pore waters contained up to 78,000 mg L−1 SO4, 690 mg L−1 Ni and 1400 mg L−1 U (800, 11.7 and 6 mM, respectively), suggesting that significant weathering had occurred. The pore water chemistry varied considerably between sampling sites. However, neither a correlation of pore-water chemistry with grain-size distribution nor a spatial relationship within the sampled grid was discernible.

Neutron activation analysis of Mediterranean volcanic rocks – An analytical database for archaeological stratigraphy by Georg Steinhauser; Johannes H. Sterba; Max Bichler; Heinz Huber (1362-1375).
Pumice has been used as a serviceable abrasive or religious artifact since antiquity and has therefore been an object of trade. By analyzing pumice samples from archaeological excavations and comparing the results to an analytical database, it is possible to establish the origin of the sample and thereby get information on the maximum age and the transport route of the pumice sample. In addition, the deposition of primary tephra deposits can be used as time markers, and place constraints on the ages of archaeological materials.Neutron activation analysis (NAA) was applied to determine the concentrations of 25 elements (As, Ba, Ce, Co, Cr, Cs, Eu, Fe, Hf, K, La, Lu, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, U, Yb, Zn and Zr) in pumice samples from the Mediterranean region: Milos, Santorini, Kos, Giali and Nisyros (Greece), Lipari (Italy) and Cappadokia (Turkey). It was found that eruption products like pumice or volcanic ash can be correlated in many cases to their volcanic sources by comparison of the typical main- and trace-elemental concentration patterns (“chemical fingerprint”). Such a distinction is possible if the volcanic rocks are homogenous enough with respect to the concentrations of geochemically relevant elements. Using only the pure glass fraction of tephra, a sample size of 5 mg is sufficient for identification by NAA.

Characterization of arsenic occurrence in the water and sediments of the Okavango Delta, NW Botswana by P. Huntsman-Mapila; T. Mapila; M. Letshwenyo; P. Wolski; C. Hemond (1376-1391).
Detailed chemical analyses were performed on surface water, groundwater and sediment samples collected from the Okavango Delta between February and November 2003 in order to examine the distribution and geochemistry of naturally occurring As in the area. Surface water in the Okavango Delta, which is neutral to slightly acidic and has high dissolved organic C (DOC), was found to be slightly enriched in As when compared to a global value for stream water. Of the 20 new borehole analyses from this project, six were found to have values exceeding 10 μg/L, the current World Health Organization provisional guideline value for As. The results from field speciation indicate that As(III) is slightly more predominant than As(V). There is a positive correlation between As and pH and between As and DOC in the groundwater samples. For the sediment samples, there is a positive correlation between As and Co, As and Fe, As and loss on ignition (LOI) and between As and the percent fines in the sample. Reductive dissolution of oxides and hydroxides in the sediments with organic C as an electron acceptor is the likely mechanism for the release of As from the sediments into the groundwater.

Mineral formation during simulated leaks of Hanford waste tanks by Youjun Deng; James B. Harsh; Markus Flury; James S. Young; Jeffrey S. Boyle (1392-1409).
Highly-alkaline waste solutions have leaked from underground tanks at the US DOE Hanford Site, Washington, causing mineral dissolution and re-precipitation upon contact with subsurface sediments. The main mineral precipitation and transformation pathways were studied in solutions mimicking tank leak conditions at the US DOE Hanford Site. In batch experiments, Si-rich solutions, representing dissolved silicate minerals, were mixed with caustic tank simulants. The tank wastes encompass a large range of chemical compositions. The effect of the following factors on mineral transformations were investigated: temperature (22, 50 and 80 °C), concentration of NaOH (from 0 to 16 M), 6 types of common inorganic anions in the tank supernatant, concentration of NaNO3 (the most abundant electrolyte in the tanks), and the Si/Al ratio in the starting solutions. Precipitates were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FT-IR) spectroscopy. A general mineral transformation pathway was observed: poorly crystalline aluminosilicate → Linde Type A (LTA) zeolite → cancrinite/sodalite. Cancrinite and sodalite were the two stable mineral phases. The concentration of NaOH and the type of anion played the determinative roles in mineral formation and transformation. Increasing NaOH concentration and temperature favored the formation of cancrinite and sodalite. Cancrinite formed in the presence of NO 3 - or SO 4 2 - ; sodalite formed in the presence of Cl or NO 2 - . The experiments indicate that (1) NaOH is a mineralization agent in the mineral transformation and the anions served as templates in the formation of cancrinite and sodalite by forming ion-pairs with Na+ and (2) cancrinite and sodalite with various morphologies and crystallinity should form in the contaminated sediments.

Direct major- and trace-element analyses of rock varnish by high resolution laser ablation inductively-coupled plasma mass spectrometry (LA-ICPMS) by David M. Wayne; Tammy A. Diaz; Robert J. Fairhurst; Richard L. Orndorff; Douglas V. Pete (1410-1431).
Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) was used to determine major and trace element concentrations in rock varnish samples from the Lahontan Range, near Fallon, NV and from a remote wilderness area near the San Juan River, in southeastern Utah. The data indicate that rapid LA-ICPMS analyses provide ample analytical resolution for semi-quantitative compositional determinations of both trace and major elements in the varnish despite the presence of a rock substrate component in most analyses. The overall major element contents of rock varnish from the two localities are grossly similar to rock varnish from other locations analyzed by solution ICPMS, electron microprobe, and energy dispersive scanning electron microscopy (SEM). Differences between microprobe and LA-ICPMS analyses may stem from different sampling scales and different degrees of substrate involvement. It was possible to detect significant variations in trace element contents in the rock varnish samples. The Lahontan Range is situated within a belt of W mineralization, and varnish from that locality contained significantly higher W and Mo contents than varnish from localities outside the W belt. Lead, Tl, Bi, Cd and As contents of varnish-coated pebbles from near the San Juan River in southeastern Utah, varied by an order of magnitude as a function of the position of the sampling site on the pebble. Elevated heavy element contents on the skyward-facing varnish surfaces indicate that heavy elements may be preferentially scavenged at the locations most likely to receive direct inputs of atmospherically-deposited airborne particulates. The source of metal-rich airborne particulates, in this case, is probably any one of several large coal-fired power plants in the Four Corners region, proximal to the San Juan study area. These patterns indicate that rock varnish chemistry is influenced by atmospherically-derived fluxes of both dissolved and particulate constituents, and that rock varnish can be used as a passive environmental indicator for a wide variety of elements, in much the same manner as moss and lichens.

Strontium-, Nd-, and rare-earth-element-isotope data are presented from rock, weathered rock (arene) and saprolite, sediment and soil, shallow and deep groundwater (e.g. mineral-water springs), and surface waters in the Margeride massif, located in the French Massif Central. Granitoid rock and gneiss are the main lithologies encountered in the Margeride, which corresponds to a large and 5-km-deep laccolith. Compared to bedrock, the Sr isotopes in arene, regolith, sediment and soil strongly diverge with a linear increase in the 87Sr/86Sr and Rb/Sr ratios. Neodymium isotopes fluctuate least between bedrock and the weathering products. In order to characterise the theoretical Sr isotopic signature IRf(Sr) of water interacting with granite, a dissolution model was applied, based on the hypothesis that most of the Sr comes from the dissolution of plagioclase, K-feldspar and biotite. Similar to the Sr model, an approach was developed for modelling the theoretical Nd isotopic signature IRf(Nd) of water interacting with a granite, assuming that most Nd originates from dissolution of the same minerals as those that yield Sr, plus apatite. The IRf(Sr) ratio of water after equilibration with the Sr derived from minerals was calculated for the Margeride granite and compared to values measured in surface- and groundwaters. Comparison of the results shows agreement between the calculated IRf(Sr) and the observed 87Sr/86Sr ratios. When calculating the IRf(Nd) ratio of water after equilibration with the Nd derived from minerals of the Margeride granite, the results indicated good agreement with surface-water values, whereas mineralised waters analysed within the Margeride hydrosystem could not be directly linked to weathering of the granite alone. Because the recharge area of deep groundwater is located on the Margeride massif, very deep circulation involving interaction with other rocks (e.g. shales) at depths of >5 km must be considered.