The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.     

Dissolved metals and associated constituents in abandoned coal-mine discharges,Pennsylvania, USA. Part 1: Constituent quantities and correlations

Complete hydrochemical data are rarely reported for coal-mine discharges (CMD). This report summarizes major and trace-element concentrations and loadings for CMD at 140 abandoned mines in the Anthracite and Bituminous Coalfields of Pennsylvania. Clean-sampling and low-level analytical methods were used in 1999 to collect data that could be useful to determine potential environmental effects, remediation strategies, and quantities of valuable constituents. A subset of 10 sites was resampled in 2003 to analyze both the CMD and associated ochreous precipitates; the hydrochemical data were similar in 2003 and 1999. In 1999, the flow at the 140 CMD sites ranged from 0.028 to 2210 L s⁻¹, with a median of 18.4 L s⁻¹. The pH ranged from 2.7 to 7.3; concentrations (range in mg/L) of dissolved (0.45-μm pore-size filter) SO₄ (34–2000), Fe (0.046–512), Mn (0.019–74), and Al (0.007–108) varied widely. Predominant metalloid elements were Si (2.7–31.3 mg L⁻¹), B (<1–260 μg L⁻¹), Ge (<0.01–0.57 μg L⁻¹), and As (<0.03–64 μg L⁻¹). The most abundant trace metals, in order of median concentrations (range in μg/L), were Zn (0.6–10,000), Ni (2.6–3200), Co (0.27–3100), Ti (0.65–28), Cu (0.4–190), Cr (<0.5–72), Pb (<0.05–11) and Cd (<0.01–16). Gold was detected at concentrations greater than 0.0005 μg L⁻¹ in 97% of the samples, with a maximum of 0.0175 μg L⁻¹. No samples had detectable concentrations of Hg, Os or Pt, and less than half of the samples had detectable Pd, Ag, Ru, Ta, Nb, Re or Sn. Predominant rare-earth elements, in order of median concentrations (range in μg/L), were Y (0.11–530), Ce (0.01–370), Sc (1.0–36), Nd (0.006–260), La (0.005–140), Gd (0.005–110), Dy (0.002–99) and Sm (<0.005–79). Although dissolved Fe was not correlated with pH, concentrations of Al, Mn, most trace metals, and rare earths were negatively correlated with pH, consistent with solubility or sorption controls. In contrast, As was positively correlated with pH.     

The presence of anomalous trace element levels in present day Jamaican soils and the geochemistry of Late-Miocene or Pliocene phosphorites

High levels of Cd and Zn in Jamaican soils observed in geochemical surveys are related to the presence of phosphorites of possible Late-Miocene or Pliocene age. The trace element and REE geochemistry of the phosphorites, together with SEM studies, indicate a guano origin for the phosphorites. No specific host minerals for Cd could be identified in the fossiliferous phosphorite which is characterized by uniquely high levels of Cd, Zn, Ag, Be, U and Y. However, in the soil Cd is present in lithiophorite and a complex history of pedological development is preserved in the aluminous–goethite present in the soil. The unique guano signature is preserved in the soil despite the fact that guanos themselves have either not been observed or have been destroyed by continuing karst and soil development. The phosphorite geochemical signature can be traced in the data of a 1988 island-wide soil geochemical survey, identifying areas where the Palaeo-environment that supported bird ‘rookeries’ existed in the Late-Miocene or Pliocene.     

Geochemical characterization of surface waters and groundwater resources in the Managua area (Nicaragua,Central America)

This paper reports new geochemical data on dissolved major and minor constituents in surface waters and ground waters collected in the Managua region (Nicaragua), and provides a preliminary characterization of the hydrogeochemical processes governing the natural water evolution in this area. The peculiar geological features of the study site, an active tectonic region (Nicaragua Depression) characterized by active volcanism and thermalism, combined with significant anthropogenic pressure, contribute to a complex evolution of water chemistry, which results from the simultaneous action of several geochemical processes such as evaporation, rock leaching, mixing with saline brines of natural or anthropogenic origin. The effect of active thermalism on both surface waters (e.g., saline volcanic lakes) and groundwaters, as a result of mixing with variable proportions of hyper-saline geothermal Na–Cl brines (e.g., Momotombo geothermal plant), accounts for the high salinities and high concentrations of many environmentally-relevant trace elements (As, B, Fe and Mn) in the waters. At the same time the active extensional tectonics of the Managua area favour the interaction with acidic, reduced thermal fluids, followed by extensive leaching of the host rock and the groundwater release of toxic metals (e.g., Ni, Cu). The significant pollution in the area, deriving principally from urban and industrial waste-water, probably also contributes to the aquatic cycling of many trace elements, which attain concentrations above the WHO recommended limits for the elements Ni (∼40 μg/l) and Cu (∼10 μg/l) limiting the potential utilisation of Lake Xolotlan for nearby Managua.     

Rice is a major exposure route for arsenic in Chakdaha block,Nadia district,West Bengal,India: A probabilistic risk assessment

The importance or otherwise of rice as an exposure pathway for As ingestion by people living in Bengal and other areas impacted by hazardous As-bearing groundwaters is currently a matter of some debate. Here this issue is addressed by determining the overall increased cancer risk due to ingestion of rice in an As-impacted district of West Bengal. Human target cancer health risks have been estimated through the intake of As-bearing rice by using combined field, laboratory and computational methods. Monte Carlo simulations were run following fitting of model probability curves to measured distributions of (i) As concentration in rice and drinking water and (ii) inorganic As content of rice and fitting distributions to published data on (i) ingestion rates and (ii) body weight and point estimates on bioconcentration factors, exposure duration and other input variables. The distribution of As in drinking water was found to be substantially lower than that reported by previous authors for As in tube wells in the same area, indicating that the use of tube well water as a proxy for drinking water is likely to result in human health risks being somewhat overestimated. The calculated median increased lifetime cancer risk due to cooked rice intake was 7.62 × 10⁻⁴, higher than the 10⁻⁴–10⁻⁶ range typically used by the USEPA as a threshold to guide determination of regulatory values and similar to the equivalent risk from water intake. The median total risk from combined rice and water intake was 1.48 × 10⁻³. The contributions to this median risk from drinking water, rice and cooking of rice were found to be 48%, 44% and 8%, respectively. Thus, rice is a major potential source of As exposure in the As-affected study areas in West Bengal and the most important exposure pathway for groups exposed to low or no As in drinking water.     

Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

Considerations for conducting incubations to study the mechanisms of As release in reducing groundwater aquifers

Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1× or (4) 10× the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.