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.     

Leaching mechanisms of oxyanionic metalloid and metal species in alkaline solid wastes: A review

An overview is presented on possible mechanisms that control the leaching behaviour of the oxyanion forming elements As, Cr, Mo, Sb, Se, V and W in cementituous systems and alkaline solid wastes, such as municipal solid waste incinerator bottom ash, fly ash and air pollution control residues, coal fly ash and metallurgical slags. Although the leachability of these elements generally depends on their redox state, speciation measurements are not common. Therefore, experimental observations available in the literature are combined with a summary of the thermal behaviour of these elements to assess possible redox states in freshly produced alkaline wastes, given their origin at high temperature. Possible redox reactions occurring at room temperature, on the other hand, are reviewed because these may alter the initial redox state in alkaline wastes and their leachates. In many cases, precipitation of oxyanions as a pure metalate cannot provide a satisfactory explanation for their leaching behaviour. It is therefore highly likely that adsorption and solid solution formation with common minerals in alkaline waste and cement reduce the leachate concentration of oxyanions below pure-phase solubility.     

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.     

Radon transfer from groundwater used in showers to indoor air

Estimation of Rn transfer from water to indoor air based on multi-day measurements may underestimate alpha exposure that occurs at short time scales in confined spaces, such as from showering, in houses with high Rn activities in the water supply. In order to examine one such incremental increase in exposure, variations in Rn in water and indoor air in 18 houses with private wells in western North Carolina (USA) were investigated. Radon in well water ranged from 158 to 811 Bq L⁻¹ (median 239 Bq L⁻¹). After 20-min showers in bathrooms with closed doors, peak Rn in air increases (above background) ranged from 71 to 4420 Bq m⁻³ (median 1170 Bq m⁻³). Calculated transfer coefficients at the scale of a 40-min closed bathroom (20-min shower plus 20 min post-shower) are described by a lognormal distribution whose geometric mean exceeds the widely-used ∼10⁻⁴ whole-house transfer coefficient by about one order of magnitude. As short-lived decay products grow from shower-derived Rn, short-term alpha energy exposure occurs in bathrooms in addition to the exposure caused by Rn mixed throughout the volume of the house. Due to the increasing ratio of Rn decay products to Rn, alpha energy exposure is greatest several minutes after the shower is turned off. For a 7.2-min shower with 10 min of additional exposure before opening the door, a geometric mean 5.6% increase in exposure over the ∼10⁻⁴ whole-house transfer coefficient derived from longer measurement periods was estimated. In addition to Rn activity in water, short-term shower exposure to Rn progeny depends on exposure time, ventilation, attachment and deposition, among other variable factors that characterize individual houses and residents.     

Coupled hydrogeological and reactive transport modelling of the Simpevarp area (Sweden)

The Simpevarp area is one of the alternative sites being considered for the deep geological disposal of high level radioactive waste in Sweden. In this paper, a coupled regional groundwater flow and reactive solute transport model of the Simpevarp area is presented that integrates current hydrogeological and hydrochemical data of the area. The model simulates the current hydrochemical pattern of the groundwater system in the area. To that aim, a conceptual hydrochemical model was developed in order to represent the dominant chemical processes. Groundwater flow conditions were reproduced by taking into account fluid-density-dependent groundwater flow and regional hydrogeologic boundary conditions. Reactive solute transport calculations were performed on the basis of the velocity field so obtained. The model was calibrated and sensitivity analyses were carried out in order to investigate the effects of heterogeneities of hydraulic conductivity in the subsurface medium. Results provided by the reactive transport model are in good agreement with much of the measured hydrochemical data. This paper emphasizes the appropriateness of the use of reactive solute transport models when water-rock interaction reactions are involved, and demonstrates what powerful tools they are for the interpretation of hydrogeological and hydrochemical data from site geological repository characterization programs, by providing a qualitative framework for data analysis and testing of conceptual assumptions in a process-oriented approach.