Geochemical Transactions - Most accessed articles

Formation of H2 and CH4 by weathering of olivine at temperatures between 30 and 70 degrees C

Anna Neubeck — 2011-06-27T00:00:00Z

Hydrocarbons such as CH4 are known to be formed through the Fischer-Tropsch or Sabatier type reactions in hydrothermal systems usually at temperatures above 100°C. Weathering of olivine is sometimes suggested to account for abiotic formation of CH4 through its redox lowering and water splitting properties. Knowledge about the CH4 and H2 formation processes at low temperatures is important for the research about the origin and cause of early Earth and Martian CH4 and for CO2 sequestration. We have conducted a series of low temperature, long-term weathering experiments in which we have tested the CH4 and H2 formation potential of forsteritic olivine.The results show low temperature CH4 production that is probably influenced by chromite and magnetite as catalysts. Extensive analyses of a potential CH4 source trapped in the crystal structure of the olivine showed no signs of incorporated CH4. Also, the available sources of organic carbon were not enough to support the total amount of CH4 detected in our experiments. There was also a linear relationship between silica release into solution and the net CH4 accumulation into the incubation bottle headspaces suggesting that CH4 formation under these conditions could be a qualitative indicator of olivine dissolution.It is likely that minerals such as magnetite, chromite and other metal-rich minerals found on the olivine surface catalyze the formation of CH4, because of the low temperature of the system. This may expand the range of environments plausible for abiotic CH4 formation both on Earth and on other terrestrial bodies.

Geophysical monitoring and reactive transport modeling of ureolytically-driven calcium carbonate precipitation

Yuxin Wu — 2011-09-23T00:00:00Z

Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH4 + production during urea hydrolysis were incorporated in the model and captured critical changes in the major metal species. The electrical phase increases were potentially due to ion exchange processes that modified charge structure at mineral/water interfaces. Our study revealed the potential of geophysical monitoring for geochemical changes during urea hydrolysis and the advantages of combining multiple approaches to understand complex biogeochemical processes in the subsurface.

Acid mine drainage biogeochemistry at Iron Mountain, California

2004-06-30T00:00:00Z

The Richmond Mine at Iron Mountain, Shasta County, California, USA provides an excellent opportunity to study the chemical and biological controls on acid mine drainage (AMD) generation in situ, and to identify key factors controlling solution chemistry. Here we integrate four years of field-based geochemical data with 16S rRNA gene clone libraries and rRNA probe-based studies of microbial population structure, cultivation-based metabolic experiments, arsenopyrite surface colonization experiments, and results of intermediate sulfur species kinetics experiments to describe the Richmond Mine AMD system. Extremely acidic effluent (pH between 0.5 and 0.9) resulting from oxidation of approximately 1 × 105 to 2 × 105 moles pyrite/day contains up to 24 g/1 Fe, several g/1 Zn and hundreds of mg/l Cu. Geochemical conditions change markedly over time, and are reflected in changes in microbial populations. Molecular analyses of 232 small subunit ribosomal RNA (16S rRNA) gene sequences from six sites during a sampling time when lower temperature (<32°C), higher pH (>0.8) conditions predominated show the dominance of Fe-oxidizing prokaryotes such as Ferroplasma and Leptospirillum in the primary drainage communities. Leptospirillum group III accounts for the majority of Leptospirillum sequences, which we attribute to anomalous physical and geochemical regimes at that time. A couple of sites peripheral to the main drainage, "Red Pool" and a pyrite "Slump," were even higher in pH (>1) and the community compositions reflected this change in geochemical conditions. Several novel lineages were identified within the archaeal Thermoplasmatales order associated with the pyrite slump, and the Red Pool (pH 1.4) contained the only population of Acidithiobacillus. Relatively small populations of Sulfobacillus spp. and Acidithiobacillus caldus may metabolize elemental sulfur as an intermediate species in the oxidation of pyritic sulfide to sulfate. Experiments show that elemental sulfur which forms on pyrite surfaces is resistant to most oxidants; its solublization by unattached cells may indicate involvement of a microbially derived electron shuttle. The detachment of thiosulfate (S2O32-) as a leaving group in pyrite oxidation should result in the formation and persistence of tetrathionate in low pH ferric iron-rich AMD solutions. However, tetrathionate is not observed. Although a S2O32--like species may form as a surface-bound intermediate, data suggest that Fe3+ oxidizes the majority of sulfur to sulfate on the surface of pyrite. This may explain why microorganisms that can utilize intermediate sulfur species are scarce compared to Fe-oxidizing taxa at the Richmond Mine site.

Arsenic species in weathering mine tailings and biogenic solids at the Lava Cap Mine Superfund Site, CA

Andrea Foster — 2011-01-24T00:00:00Z

Background: A realistic estimation of the health risk of human exposure to solid-phase arsenic (As) derived from historic mining operations is a major challenge to redevelopment of California's famed "Mother Lode" region. Arsenic, a known carcinogen, occurs in multiple solid forms that vary in bioaccessibility. X-ray absorption fine-structure spectroscopy (XAFS) was used to identify and quantify the forms of As in mine wastes and biogenic solids at the Lava Cap Mine Superfund (LCMS) site, a historic "Mother Lode" gold mine. Principal component analysis (PCA) was used to assess variance within water chemistry, solids chemistry, and XAFS spectral datasets. Linear combination, least-squares fits constrained in part by PCA results were then used to quantify arsenic speciation in XAFS spectra of tailings and biogenic solids. Results: The highest dissolved arsenic concentrations were found in Lost Lake porewater and in a groundwater-fed pond in the tailings deposition area. Iron, dissolved oxygen, alkalinity, specific conductivity, and As were the major variables in the water chemistry PCA. Arsenic was, on average, 14 times more concentrated in biologically-produced iron (hydr)oxide than in mine tailings. Phosphorous, manganese, calcium, aluminum, and As were the major variables in the solids chemistry PCA. Linear combination fits to XAFS spectra indicate that arsenopyrite (FeAsS), the dominant form of As in ore material, remains abundant (average: 65%) in minimally-weathered ore samples and water-saturated tailings at the bottom of Lost Lake. However, tailings that underwent drying and wetting cycles contain an average of only 30% arsenopyrite. The predominant products of arsenopyrite weathering were identified by XAFS to be As-bearing Fe (hydr)oxide and arseniosiderite (Ca2Fe(AsO4)3O3•3H2O). Existence of the former species is not in question, but the presence of the latter species was not confirmed by additional measurements, so its identification is less certain. The linear combination, least-squares fits totals of several samples deviate by more than ± 20% from 100%, suggesting that additional phases may be present that were not identified or evaluated in this study. Conclusions: Sub- to anoxic conditions minimize dissolution of arsenopyrite at the LCMS site, but may accelerate the dissolution of As-bearing secondary iron phases such as Fe3+-oxyhydroxides and arseniosiderite, if sufficient organic matter is present to spur anaerobic microbial activity. Oxidizing, dry conditions favor the stabilization of secondary phases, while promoting oxidative breakdown of the primary sulfides. The stability of both primary and secondary As phases is likely to be at a minimum under cyclic wet-dry conditions. Biogenic iron (hydr)oxide flocs can sequester significant amounts of arsenic; this property may be useful for treatment of perpetual sources of As such as mine adit water, but the fate of As associated with natural accumulations of floc material needs to be assessed.

Transport of Pb and Zn by carboxylate complexes in basinal ore fluids and related petroleum-field brines at 100degreesC: the influence of pH and oxygen fugacity

2002-09-16T00:00:00Z

It is well established through field observations, experiments, and chemical models that oxidation (redox) state and pH exert a strong influence on the speciation of dissolved components and the solubility of minerals in hydrothermal fluids. log –pH diagrams were used to depict the influence of oxygen fugacity and pH on monocarboxylate- and dicarboxylate-transport of Pb and Zn in low-temperature (100°C) hydrothermal ore fluids that are related to diagenetic processes in deep sedimentary basins, and allow a first-order comparison of Pb and Zn transport among proposed model fluids for Mississippi Valley-type (MVT) and red-bed related base metal (RBRBM) deposits in terms of their approximate pH and conditions. To construct these diagrams, total Pb and Zn concentrations and Pb and Zn speciation were calculated as a function of log and pH for a composite ore-brine with concentrations of major elements, total sulfur, and total carbonate that approximate the composition of MVT and RBRBM model ore fluids and modern basinal brines. In addition to acetate and malonate complexation, complexes involving the ligands Cl-, HS-, H2S, and OH- were included in the model of calculated total metal concentration and metal speciation. Also, in the model, Zn and Pb are competing with the common-rock forming metals Ca, Mg, Na, Fe, and Al for the same ligands. Calculated total Pb concentration and calculated total Zn concentration are constrained by galena and sphalerite solubility, respectively. Isopleths, in log –pH space, of the concentration of Pb and concentration of Zn in carboxylate (acetate + malonate) complexes illustrate that the oxidized model fluids of T. H. Giordano (in Organic Acids in Geological Processes, ed. E. D. Pittman and M. D. Lewan, Springer-Verlag, New York, 1994, pp. 319–354) and G. M. Anderson (Econ. Geol., 1975, 70, 937–942) are capable of transporting sufficient amounts of Pb (up to 10 ppm) and Zn (up to 100 ppm) in the form of carboxylate complexes to form economic deposits of these metals. On the other hand, the reduced ore fluid models of D. A. Sverjensky (Econ. Geol., 1984, 79, 23–37) and T. H. Giordano and H. L. Barnes (Econ. Geol., 1981, 76, 2200–2211) can at best transport amounts of Pb and Zn, as carboxylate complexes, that are many orders of magnitude below the 1 to 10 ppm minimum required to form economic deposits. Lead and zinc speciation (mol% of total Pb or Zn) in the model ore fluid was calculated at specific log –pH conditions along the 100, 0.01, and 0.001 ppm total Pb and total Zn isopleths. Along the 100 ppm isopleth conditions are oxidized (∑SO4 >> ∑H2S) with Pb and Zn predominantly in the form of chloride complexes under acid to mildly alkaline conditions (pH from 3 to approximately 7.5), while hydroxide complexes dominate Pb and Zn speciation under more alkaline conditions. Sulfide complexes are insignificant under these oxidized conditions. For more reduced conditions along the 0.01 and 0.001 ppm isopleths chloride complexes dominate Pb and Zn speciation in the SO42- field and near the SO42--reduced sulfur boundary from pH = 4 to approximately 7.5, while hydroxide complexes dominate Pb and Zn speciation under alkaline conditions above pH = 7.5 in the SO42- field. In the most reduced fluids (∑H2S >> ∑SO4) along the 0.01 and 0.001 isopleths, sulfide complexes account for almost 100% of the Pb and Zn in the model fluid. Acetate (monocarboxylate) complexation is significant only under conditions of chloride and hydroxide complex dominance and its effect is maximized in the pH range 5 to 7, where it complexes 2 to 2.6% of the total Pb and 1 to 1.25% of the total Zn. Malonate (dicarboxylate) complexes are insignificant along all isopleths. The speciation results from this study show that deep formation waters characterized by temperatures near 100°C, high oxidation states and ∑H2S < 0.03 mg L-1 ( < 10-6), high chlorinities (~ 100000 mg L-1), and high but reasonable concentrations of carboxylate anions can mobilize up to 3% of the total Pb and up to 1.3% of the total Zn as carboxylate complexes. Furthermore, these percentages, under the most favorable conditions, correspond to approximately 1 to 100 ppm of these metals in solution; concentrations that are adequate to form economic deposits of these metals. However, the field evidence suggests that all of these optimum conditions for carboxylate complexation are rarely met at the same time. A comparison of the composite ore fluid compositions from this study and modern brine data shows that the ore brines, corresponding to log –pH conditions based on the Anderson (1975) and Giordano (1994) model fluids, are similar in many respects to modern, high trace-metal petroleum-field brines. The principal differences between modern high trace-metal brines and the composite ore fluids of Anderson (1975) and Giordano (1994) relate to their carboxylate anion content. The reported concentrations of monocarboxylate anions (∑monocbx) and dicarboxylate anions (Edicbx) in high trace-metal petroleum-field brines (< 1 to 300 mg L-1 and < 1 mg L-1, respectively) are significantly lower than the concentrations assumed in the modelled brines of this study (∑monocbx = 7 700 mg L-1 and ∑dicbx = 300 mg L-1). There are also major differences in the corresponding total chloride to carboxylate ratio (∑mCl/∑mcbx) and monocarboxylate to dicarboxylate ratio (∑mmonocbx/∑mdicbx). Modern high trace-metal brines have much higher ∑mCl/∑mcbx values and, therefore, the contribution of carboxylate complexes to the total Pb and Zn content in these modern brines is likely to be significantly less than the 1 to 3 percent for the composite ore fluids of Anderson (1975) and Giordano (1994). The composite ore-brine based on the Giordano and Barnes (1981) MVT ore fluid is comparable to the high salinity (> 170 000 mg L-1 TDS) subset of modern brines characterized by low trace-metal content and high total reduced sulfur (∑H2S). A comparison of the Sverjensky (1984) composite ore-brine with modern petroleum-field brines in terms of ∑H2S and Zn content, reveals that this ore fluid corresponds to a "border-type" brine, between modern high trace-metal brines and those with low trace-metal content and high ∑H2S. A brine of this type is characterized by values of ∑H2S, ∑Zn, and/or ∑Pb within or near the 1 to 10 mg L-1 range. Based on brine-composition data from numerous references cited in this paper, border-type brines do exist but are rare. The model results and field evidence presented in this study are consistent with other chemical simulation studies of carboxylate complexation in modern petroleum-field brines. Thus, it appears that carboxylate complexation plays a minor, if not insignificant, role as a transport mechanism for Pb and Zn in high salinity Na–Cl and Na–Ca–Cl basinal brines and related ore fluids.

Inducing mineral precipitation in groundwater by addition of phosphate

Karen Wright — 2011-10-26T00:00:00Z

Background: Induced precipitation of phosphate minerals to scavenge trace elements from groundwater is a potential remediation approach for contaminated aquifers. The success of engineered precipitation schemes depends on the particular phases generated, their rates of formation, and their long term stability. The purpose of this study was to examine the precipitation of calcium phosphate minerals under conditions representative of a natural groundwater. Because microorganisms are present in groundwater, and because some proposed schemes for phosphate mineral precipitation rely on stimulation of native microbial populations, we also tested the effect of bacterial cells (initial densities of 105 and 107 mL-1) added to the precipitation medium. In addition, we tested the effect of a trace mixture of propionic, isovaleric, formic and butyric acids (total concentration 0.035 mM). Results: The general progression of mineral precipitation was similar under all of the study conditions, with initial formation of amorphous calcium phosphate, and transformation to poorly crystalline hydroxylapatite (HAP) within one week. The presence of the bacterial cells appeared to delay precipitation, although by the end of the experiments the overall extent of precipitation was similar for all treatments. The stoichiometry of the final precipitates as well as Rietveld structure refinement using x-ray diffraction data indicated that the presence of organic acids and bacterial cells resulted in an increasing a and decreasing c lattice parameter, with the higher concentration of cells resulting in the greatest distortion. Uptake of Sr into the solids was decreased in the treatments with cells and organic acids, compared to the control. Conclusions: Our results suggest that the minerals formed initially during an engineered precipitation application for trace element sequestration may not be the ones that control long-term immobilization of the contaminants. In addition, the presence of bacterial cells appears to be associated with delayed HAP precipitation, changes in the lattice parameters, and reduced incorporation of trace elements as compared to cell-free systems. Schemes to remediate groundwater contaminated with trace metals that are based on enhanced phosphate mineral precipitation may need to account for these phenomena, particularly if the remediation approach relies on enhancement of in situ microbial populations.

A 50-year record of NOx and SO2 sources in precipitation in the Northern Rocky Mountains, USA

David Naftz — 2011-03-07T00:00:00Z

Ice-core samples from Upper Fremont Glacier (UFG), Wyoming, were used as proxy records for the chemical composition of atmospheric deposition. Results of analysis of the ice-core samples for stable isotopes of nitrogen (δ15N, ) and sulfur (δ34S, ), as well as and deposition rates from the late-1940s thru the early-1990s, were used to enhance and extend existing National Atmospheric Deposition Program/National Trends Network (NADP/NTN) data in western Wyoming. The most enriched δ34S value in the UFG ice-core samples coincided with snow deposited during the 1980 eruption of Mt. St. Helens, Washington. The remaining δ34S values were similar to the isotopic composition of coal from southern Wyoming. The δ15N values in ice-core samples representing a similar period of snow deposition were negative, ranging from -5.9 to -3.2 ‰ and all fall within the δ15N values expected from vehicle emissions. Ice-core nitrate and sulfate deposition data reflect the sharply increasing U.S. emissions data from 1950 to the mid-1970s.

Experimental Study of Cement-Sandstone/Shale-Brine-CO2 Interactions

Susan Carroll — 2011-11-11T00:00:00Z

Background: Reactive-transport simulation is a tool that is being used to estimate long-term trapping of CO2, and wellbore and cap rock integrity for geologic CO2 storage. We reacted end member components of a heterolithic sandstone and shale unit that forms the upper section of the In Salah Gas Project carbon storage reservoir in Krechba, Algeria with supercritical CO2, brine, and with/without cement at reservoir conditions to develop experimentally constrained geochemical models for use in reactive transport simulations. Results: We observe marked changes in solution composition when CO2 reacted with cement, sandstone, and shale components at reservoir conditions. The geochemical model for the reaction of sandstone and shale with CO2 and brine is a simple one in which albite, chlorite, illite and carbonate minerals partially dissolve and boehmite, smectite, and amorphous silica precipitate. The geochemical model for the wellbore environment is also fairly simple, in which alkaline cements and rock react with CO2-rich brines to form an Fe containing calcite, amorphous silica, smectite and boehmite or amorphous Al(OH)3. Conclusions: Our research shows that relatively simple geochemical models can describe the dominant reactions that are likely to occur when CO2 is stored in deep saline aquifers sealed with overlying shale cap rocks, as well as the dominant reactions for cement carbonation at the wellbore interface.

Isolation and purification of Cu-free methanobactin from Methylosinus trichosporium OB3b

Marie-Laure Pesch — 2011-02-07T00:00:00Z

Background: The isolation of highly pure copper-free methanobactin is a prerequisite for the investigation of the biogeochemical functions of this chalkophore molecule produced by methane oxidizing bacteria. Here, we report a purification method for methanobactin from Methylosinus trichosporium OB3b cultures based on reversed-phase HPLC fractionation used in combination with a previously reported resin extraction. HPLC eluent fractions of the resin extracted product were collected and characterized with UV-vis, FT-IR, and C-1s NEXAFS spectroscopy, as well as with elemental analysis and ESI-MS. Results: The results showed that numerous compounds other than methanobactin were present in the isolate obtained with resin extraction. Molar C/N ratios, mass spectrometry measurements, and UV-vis spectra indicated that methanobactin was only present in one of the HPLC fractions. On a mass basis, methanobactin carbon contributed only 32% to the total organic carbon isolated with resin extraction. Our spectroscopic results implied that besides methanobactin, the organic compounds in the resin extract comprised breakdown products of methanobactin as well as polysaccharide-like substances. Conclusion: Our results demonstrate that a purification step is indispensable in addition to resin extraction in order to obtain pure methanobactin. The proposed HPLC purification procedure is suitable for semi-preparative work and provides copper-free methanobactin.

Quantifying hydrogen peroxide in iron-containing solutions using leuco crystal violet

2005-06-14T00:00:00Z

Hydrogen peroxide is present in many natural waters and wastewaters. In the presence of Fe(II), this species decomposes to form hydroxyl radicals, that are extremely reactive. Hence, in the presence of Fe(II), hydrogen peroxide is difficult to detect because of its short lifetime. Here, we show an expanded use of a hydrogen peroxide quantification technique using leuco crystal violet (LCV) for solutions of varying pH and iron concentration. In the presence of the biocatalyst peroxidase, LCV is oxidized by hydrogen peroxide, forming a colored crystal violet ion (CV+), which is stable for days. The LCV method uses standard equipment and allows for detection at the low microM concentration level. Results show strong pH dependence with maximum LCV oxidation at pH 4.23. By chelating dissolved Fe(II) with EDTA, hydrogen peroxide can be stabilized for analysis. Results are presented for hydrogen peroxide quantification in pyrite–water slurries. Pyrite–water slurries show surface area dependent generation of hydrogen peroxide only in the presence of EDTA, which chelates dissolved Fe(II). Given the stability of CV+, this method is particularly useful for field work that involves the detection of hydrogen peroxide.