Broder J. Merkel

Discrimination of thioarsenites and thioarsenates by X-ray absorption spectroscopy.

Soluble arsenic-sulfur compounds play important roles in the biogeochemistry of arsenic in sulfidic waters but conflicting analytical evidence identifies them as either thioarsenates (= As(V)-sulfur species) or thioarsenites (= As(III)-sulfur species). Here, we present the first characterization of thioarsenates (mono-, di-, and tetrathioarsenate) by X-ray absorption spectroscopy and demonstrate that their spectra are distinctly different from those of As(III)-sulfur species, as well as from arsenite and arsenate. The absorption near edge energy decreases in the order arsenate > thioarsenates > arsenite > As(III)-sulfur species, and individual thioarsenates differ by 1 eV per sulfur atom. Fitted As(V)-S and As(V)-O bond distances in thioarsenates (2.13-2.18 A and 1.70 A, respectively) are significantly shorter than the corresponding As(III)-S and As(III)-O bond distances in As(III)-S species (2.24-2.34 A and 1.78 A, respectively). Finally, we demonstrate that thioarsenates can be identified by principal component analysis in mixtures containing As(III)-sulfur species. This capability is used to study the spontaneous reduction of tetrathioarsenate to As(III)-sulfur species (possibly trithioarsenite) upon acidification from pH 9.5 to 2.8.

Testing the Suitability of Zerovalent Iron Materials for Reactive Walls

Environmental Context. Groundwater remediation is generally a costly, long-term process. In situ remediation using permeable reactive barriers, through which the groundwaters pass, is a potential solution. For redox-sensitive contaminants in groundwater, a metallic iron barrier (zerovalent iron, ZVI) can immobilize or degrade these dissolved pollutants. Scrap iron materials are a low-cost ZVI material but, because of the wide variation of scrap metal compositions, testing methods for characterizing the corrosion behaviour need to be developed. Abstract. Zerovalent iron (ZVI) has been proposed as reactive material in permeable in situ walls for contaminated groundwater. An economically feasible ZVI-based reactive wall requires cheap but efficient iron materials. From an uranium treatability study and results of iron dissolution in 0.002 M EDTA by five selected ZVI materials, it is shown that current research and field implementation is not based on a rational selection of application-specific iron metal sources. An experimental procedure is proposed which could enable a better material characterization. This procedure consists of mixing ZVI materials and reactive additives, including contaminant releasing materials (CRMs), in long-term batch experiments and characterizing the contaminant concentration over the time.

Effect of sulfate, carbonate, and phosphate on the uranium(VI) sorption behavior onto bentonite

Summary Batch experiments were conducted to study the uranium U(VI) sorption onto bentonite as a function of pH (3 to 8), and initial U(VI) concentrations (5 × 10−6 and 5 × 10−5 M) in the presence and absence of sulfate, carbonate, and phosphate. Uranium sorption onto bentonite depended on the initial U(VI) concentration with a stronger sorption at lower concentrations and was high over a wide range of pH in the absence of complexing ligands. In the presence of 0.005 M sulfate, U(VI) sorption was reduced at low pH values due to the competition between SO42− and the uranyl ion for sorption sites on the bentonite surface, or the formation of uranyl-sulfate complexes. In the presence of 0.003 M carbonate, U(VI) sorption decreased sharply at a pH above 7, because of the formation of negatively charged uranyl-carbonate complexes, which are weakly adsorbed onto the bentonite. Uranium sorption onto bentonite was greatly enhanced in the presence of 0.003 M phosphate. Kinetic batch experiments carried out for 5 × 10−5 M U(VI) at pH values of 3, 5, and 8 revealed that the sorption rate was generally rapid over the first 10 min of the experiments, then slowed down appreciably after 1 to 24 h. Sulfate had little effect on the kinetics of U(VI) sorption; both in the absence and presence of sulfate, sorption equilibrium was attained after 4 h. In the presence of carbonate, attainment of sorption equilibrium required more time than in its absence. The presence of 0.003 M phosphate reduced the time required to reach sorption equilibrium across a wide range of pH compared to phosphate-free systems.

Uranium, Mining and Hydrogeology

Since the International Atomic Energy Agency’s foundation in 1957 the IAEA has had an increasing interest in uranium production cycle issues. The recent activities cover tasks including uranium geology & deposits, uranium resources, production, demand, uranium exploration and uranium mining & milling technologies. All the tasks include environmental issues. In addition, many training courses (also on ISL topics) have been organised and are being prepared. In the past 15 years a lot of emphases have been put on the uranium ISL mining technology in consequence with a depressed development of new mining operations and an increased interest in lower cost operations. Several technical meetings and consultancies were organised and led to publishing of an IAEA technical document (TECDOC-1239) Manual on Acid In Situ Leach Uranium Mining Technology.

Database uncertainty as a limiting factor in reactive transport prognosis.

The effect of uncertainties in thermodynamic databases on prediction performances of reactive transport modeling of uranium (VI) is investigated with a Monte Carlo approach using the transport code TReaC. TReaC couples the transport model to the speciation code PHREEQC by a particle tracking method. A speciation example is given to illustrate the effect of uncertainty in thermodynamic data on the predicted solution composition. The transport calculations consequently show the prediction uncertainty resulting from uncertainty in thermodynamic data. A conceptually simple scenario of elution of uranium from a sand column is used as an illustrating example. Two different cases are investigated: a carbonate-enriched drinking water and an acid mine water associated with uranium mine remediation problems. Due to the uncertainty in the relative amount of positively charged and neutral solution species, the uncertainty in the thermodynamic data also infers uncertainty in the retardation behavior. The carbonated water system shows the largest uncertainties in speciation calculation. Therefore, the model predictions of total uranium solubility have a broad range. The effect of data uncertainty in transport prediction is further illustrated by a prediction of the time when eluted uranium from the column exceeds a threshold value. All of these Monte Carlo transport calculations consume large amounts of computing time.

Investigating the Mechanism of Uranium Removal by Zerovalent Iron

Environmental Context.Groundwater is the water that fills the spaces between sand, soil, and rock below the water table. It discharges into ecologically sensitive wetlands and is used as drinking water or in agriculture and industry. Inappropriate waste disposal and poor land management can contaminate groundwater and may minimize its use for decades. The common method for pumping contaminated groundwater to the surface for treatment is costly and labour intensive. Zerovalent iron is a new, more cost-effective method of groundwater remediation. Abstract. Zerovalent iron (ZVI) has been proposed as a reactive material in permeable in situ walls for groundwater contaminated by metal pollutants. For such pollutants that interact with corrosion products, the determination of the actual mechanism of their removal is very important to predict their stability in the long term. From a study of the effects of pyrite (FeS2) and manganese nodules (MnO2) on the uranium removal potential of a selected ZVI material, a test methodology (FeS2–MnO2 method) is suggested to follow the pathway of contaminant removal by ZVI materials. An interpretation of the removal potential of ZVI for uranium in the presence of both additives corroborates coprecipitation with iron corrosion products as the initial removal mechanism for uranium.

ENVIRONMENTAL IMPACT BY SPILL OF GEOTHERMAL FLUIDS AT THE GEOTHERMAL FIELD OF LOS AZUFRES, MICHOACÁN, MEXICO

Monitoring of surface water and shallow aquifers inside and outside of the Los Azufres geothermal fieldduring the period November 1994 to May 1996 led to thedetection of some contamination of surface water andshallow aquifers due to exploitation of the deepbrines. Leaking of evaporation ponds and pipelines,occasionally overflowing of reinjection wells and pondrims as well as outflowing of brines duringrehabilitation or drilling operations, are potentialcontamination sources within the cycle of geothermalproduction.Temporarily and/or permanently increased traceelements concentrations, especially Fe, Mn, F, B, andAs in surface waters within the geothermal field aswell as up to 10 km outside, were observed. Maximumvalues of 125 and 8 mg L-1 were observed for B and As,respectively. The discharge of hypersaline geothermalbrines also causes salinization of surrounding soils.It occasionally happens that cattle drink from thebrines. The use of the river for irrigation anddrinking water supply in the surrounding regions maycause accumulation of toxic elements in the human foodchain or may endanger the public health.The establishment of a closed geothermal productioncycle can be achieved by simple remediationtechniques, such as sealing of the pond walls, removalof overflow channels, direct reinjection without anyreposal time in evaporation ponds, as well as animproved security and control system.

Acute Toxicity of Thioarsenates to Vibrio fischeri

Thioarsenic species often are the predominant arsenic species in sulfidic environments, yet little is known about their toxicity. We report to our knowledge the first determination of acute toxicity of mono-, di-, and trithioarsenate to the bioluminescent bacterium Vibrio fischeri, which increases with an increasing number of thio(SH)-groups. Whereas mono- and dithioarsenate are much less toxic (effective analyte concentration causing a 50% decrease in luminescence [EC50], 676 and 158 mg/L, respectively), the toxicity of trithioarsenate (EC50, 14.4 mg/L) is comparable to the toxicities of arsenate and arsenite (EC50, 9.1 and 26.1 mg/L, respectively). The low toxicity of monothioarsenate is remarkable, because it has chemical properties very similar to those of arsenate. In contrast to the toxicities of arsenite and arsenate, the toxicity of thioarsenates increases with exposure time, suggesting a lack of detoxification mechanisms or a conversion of thioarsenic species into arsenic oxyanions after uptake. We determined the acute toxicity of synthetic arsenite solutions with varying sulfide concentration to V. fischeri. Arsenic speciation in these solutions was measured by ion chromatography-inductively coupled plasma-mass spectrometry, and the observed toxicity was related to the different arsenic species present. High inhibition of luminescence was observed at low and high ratios of sulfur to arsenic, in which arsenite or a mixture of di-, tri-, and tetrathioarsenate dominated arsenic speciation. Acute toxicity decreased at sulfur to arsenic ratios of from 1 to 10, with a minimum luminescence inhibition of 30% at a ratio of 3.5, at which concentrations of 55 mg/L of arsenite and 30 mg/L of trithioarsenate were determined. The toxicity observed under these conditions is much lower than that anticipated from the individual dose-response curves that predict each species alone already should cause 70 to 80% inhibition. The low toxicity suggests an antagonistic toxicological interaction between arsenite and trithioarsenate.

The origin of reservoir fluids in the geothermal field of Los Azufres, Mexico — isotopical and hydrological indications

Abstract The calculation of hydrological balance resulted in a potential, average annual infiltration rate of 446±206 mm/m 2 for the Los Azufres geothermal area, which corresponds to a total of 82×10 6 m 3 per a. Due to the highly fractured and faulted structure of the volcanic formations, a considerable potential for the infiltration of recent meteoric water into deeper sections of the volcanic formations can be assumed. Isotopic data indicate the minor importance of recent meteoric water for the recharge of the geothermal reservoir. Very negative δ 13 C values can be explained by the input of organic C from the surface, but the lack of 14 C in the deep fluids reflects a pre-historic age for the infiltration event of fossil meteoric water. The dilution of the meteoric water by 14 C-free CO 2 gas from a shallow magma chamber complicates the exact age determination of the infiltration event, which probably occurred during the Late Pleistocene or Early Holocene glacial period. Strong water–rock interaction processes, such as sericitization/chloritization, caused the primary brine composition to be camouflaged. A preliminary hydrological model of the reservoir can be postulated as follows: the fossil hydrodynamic system was characterized by the infiltration of meteoric water and mixing with andesitic and/or magmatic water. Strong water–rock interaction processes in the main part of the production zone prove the existence of former active fluid circulation systems. Due to changes in pressure and temperature, the rising fluids get separated into liquid and vapour phases at a depth of 1500 m. After cooling, the main portions of both phases remain within the convective reservoir cycle. Isotope analyses of hot spring waters indicate the direct communication of the reservoir with the surface at some local outcrops. A recent reactivation of the hydrodynamic system is caused by the geothermal production, as indicated by the detection of lateral communication between some production and reinjection wells.

Modelling Rainfall Runoff Relations Using HEC-HMS and IHACRES for a Single Rain Event in an Arid Region of Jordan

The HEC-HMS and IHACRES rainfall runoff models were applied to simulate a single streamflow event in Wadi Dhuliel arid catchment that occurred on 30–31/01/2008. Streamflow estimation was performed on the basis of an hourly scale. The aim of this study was to develop a new framework of rainfall-runoff model applications in arid catchments by integrating a re-adjusted satellite-derived rainfall dataset (GSMaP_MVK+) to determine the location of the rainfall storm. The HEC-HMS model was applied using the HEC-GeoHMS extension in ArcView 3.3 while the IHACRES is Java-based version model. The HEC-HMS model input data include soil type, land use/land cover, and slope. By contrast, the lumped model IHACRES was also applied, based on hourly rainfall and temperature data. Both models were calibrated and validated using the observed streamflow data set collected at Al-Za’atari discharge station. The performance of IHACRES showed some weaknesses, while the flow comparison between the calibrated streamflow results fits well with the observed streamflow data in HEC-HMS. The Nash-Sutcliffe efficiency (Ef) for the two models was 0.51 and 0.88 respectively.