Bacterial dissolution of fluorapatite as a possible source of elevated dissolved phosphate in the environment

In order to understand the contribution of geogenic phosphorus to lake eutrophication, we have investigated the rate and extent of fluorapatite dissolution in the presence of two common soil bacteria (Pantoea agglomerans and Bacillus megaterium) at T = 25 °C for 26 days. The release of calcium (Ca), phosphorus (P), and rare earth elements (REE) under biotic and abiotic conditions was compared to investigate the effect of microorganism on apatite dissolution. The release of Ca and P was enhanced under the influence of bacteria. Apatite dissolution rates obtained from solution Ca concentration in the biotic reactors increased above error compared with abiotic controls. Chemical analysis of biomass showed that bacteria scavenged Ca, P, and REE during their growth, which lowered their fluid concentrations, leading to apparent lower release rates. The temporal evolution of pH in the reactors reflected the balance of apatite weathering, solution reactions, bacterial metabolism, and potentially secondary precipitation, which was implied in the variety of REE patterns in the biotic and abiotic reactors. Light rare earth elements (LREE) were preferentially adsorbed to cell surfaces, whereas heavy rare earth elements (HREE) were retained in the fluid phase. Decoupling of LREE and HREE could possibly be due to preferential release of HREE from apatite or selective secondary precipitation of LREE enriched phosphates, especially in the presence of bacteria. When corrected for intracellular concentrations, both biotic reactors showed high P and REE release compared with the abiotic control. We speculate that lack of this correction explains the conflicting findings about the role of bacteria in mineral weathering rates. The observation that bacteria enhance the release rates of P and REE from apatite could account for some of the phosphorus burden and metal pollution in aquatic environments.     

Cu isotopic fractionation in the supergene environment with and without bacteria

The isotopic composition of dissolved Cu and solid Cu-rich minerals [δ⁶⁵Cu (‰) = (⁶⁵Cu/⁶³Cu_sample/⁶⁵Cu/⁶³Cu_std) - 1)*1000] were monitored in batch oxidative dissolution experiments with and without Thiobacillus ferrooxidans. Aqueous copper in leach fluids released during abiotic oxidation of both chalcocite and chalcopyrite was isotopically heavier (δ⁶⁵Cu = 5.34‰ and δ⁶⁵Cu = 1.90‰, respectively, [±0.16 at 2σ]) than the initial starting material (δ⁶⁵Cu = 2.60 ± 0.16‰ and δ⁶⁵Cu = 0.58 ± 0.16‰, respectively). Isotopic mass balance between the starting material, aqueous copper, and secondary minerals precipitated in these experiments explains the heavier isotopic values of aqueous copper. In contrast, aqueous copper from leached chalcocite and chalcopyrite inoculated with Thiobacillus ferrooxidans was isotopically similar to the starting material. The lack of fractionation of the aqueous copper in the biotic experiments can best be explained by assuming a sink for isotopically heavy copper present in the bacteria cells with δ⁶⁵Cu = 5.59 ± 0.16‰. Consistent with this inference, amorphous Cu-Fe oxide minerals are observed surrounding cell membranes of Thiobacillus grown in the presence of dissolved Cu and Fe.Extrapolating these experiments to natural supergene environments implies that release of isotopically heavy aqueous Cu from oxidative leach caps, especially under abiotic conditions, should result in precipitates in underlying enrichment blankets that are isotopically heavy. Where iron-oxidizing cells are involved, isotopically heavy oxidized Cu entrained in cellular material may become associated with leach caps, causing the released aqueous Cu to be less isotopically enriched in the heavy isotope than predicted for the abiotic system. Rayleigh fractionation trends with fractionation factors calculated from our experiments for both biotic and abiotic conditions are consistent with large numbers of individual abiotic or biotic leaching events, explaining the supergene chalcocites in the Morenci and Silver Bell porphyry copper deposits.     

Experimental study on weathering of seafloor volcanic glass by bacteria (Pseudomonas fluorescens) – Implications for the contribution of bacteria to the water–rock reaction at the Mid-Oceanic Ridge setting

The biologically mediated weathering of the ocean crust has received increasing attention in recent decades, but the rates and the possible mechanism of elemental release during microbe–basalt interactions occurring below the seafloor have not been studied in detail. In this study, we established an experimental weathering study of seafloor natural basaltic glass comparing the effect of microbial activity (Pseudomonas fluorescens) in P-rich and P-poor media with parallel controls containing either nonviable cells or organic acid. The changes in the chemical parameters, including pH, bacterial densities, and ion concentrations (Ca, Mg, Si, Mn, Al, Fe, and P) in the solution, were examined during the different batch experiments. The results showed that the pH decreased from 7.0 to 3.5 and the bacterial density increased from 10⁵ to 10⁸ cells/ml during the first 120 h, and the cell numbers remained constant at 10⁸ cells/ml and the pH increased from 3.5 to 6 between 120 h and 864 h in the P-bearing reactors containing bacteria. In contrast, during all the experimental time, the pH remained close to neutral condition in the abiotic control systems and the dissolution rates increased markedly with a decrease in pH and became minimal at near-neutral pH in P-bearing reactors containing bacteria, where Ca, Si, and Mg release rates were 2- to 4-fold higher than those obtained in chemical systems and biotic P-limited systems. Furthermore, the surfaces of the natural volcanic glass from the biotic systems were colonized by bacteria. Simultaneously, the etch pits were observed by Scanning Electron Microscope, which further indicate that the bacteria may promote the mineral dissolution for energy gain. Some elements (e.g., Fe, Mn, and Al) releasing from natural volcanic glass are likely an important source of the elemental budget in the ocean, and thus the element release and its possible mechanism conducted in this experimental study have potential implications on the biogeochemical cycling process in the Mid-Oceanic Ridge setting.     

Low-oxygen and chemical kinetic constraints on the geochemical niche of neutrophilic iron(II) oxidizing microorganisms

Neutrophilic iron oxidizing bacteria (FeOB) must actively compete with rapid abiotic processes governing Fe(II) oxidation and as a result have adapted to primarily inhabit low-O₂ environments where they can more successfully compete with abiotic Fe(II) oxidation. The spatial distribution of these microorganisms can be observed through the chemical gradients they affect, as measured using in situ voltammetric analysis for dissolved Fe(II), Fe(III), O₂, and FeS_(aq). Field and laboratory determination of the chemical environments inhabited by the FeOB were coupled with detailed kinetic competition studies for abiotic and biotic oxidation processes using a pure culture of FeOB to quantify the geochemical niche these organisms inhabit. In gradient culture tubes, the maximum oxygen levels, which were associated with growth bands of Sideroxydans lithotrophicus (ES-1, a novel FeOB), were 15-50 μM. Kinetic measurements made on S. lithotrophicus compared biotic/abiotic (killed control) Fe oxidation rates. The biotic rate can be a significant and measurable fraction of the total Fe oxidation rate below O₂ concentrations of approximately 50 μM, but biotic Fe(II) oxidation (via the biotic/abiotic rate comparison) becomes difficult to detect at higher O₂ levels. These results are further supported by observations of conditions supporting FeOB communities in field settings. Variablity in cell densities and cellular activity as well as variations in hydrous ferrous oxide mineral quantities significantly affect the laboratory kinetic rates. The microbial habitat (or geochemical niche) where FeOB are active is thus largely controlled by the competition between abiotic and biotic kinetics, which are dependent on Fe(II) concentration, P_O2, temperature and pH in addition to the surface area of hydrous ferric oxide minerals and the cell density/activity of FeOB. Additional field and lab culture observations suggest a potentially important role for the iron-sulfide aqueous molecular cluster, FeS_(aq), in the overall cycling of iron associated with the environments these microorganisms inhabit.     

The effect of methanogenesis on the geochemistry of low temperature water–Fe0–basalt reactions

Hydrogen gas produced in the subsurface from the hydration of mafic rocks is known to be a major energy source for chemolithotrophic life in extreme environments such as hydrothermal vents. The possibility that in situ anaerobic microorganisms present in the deep subsurface are sustained by low temperature H₂-generating water–rock reactions taking place around them is being investigated. Whether the growth and activity of H₂-utilizing microbes directly influences aqueous geochemistry, rates of mineral dissolution, and the chemical composition of the alteration products is also being quantitatively evaluated.To explore how microorganisms are affected by water–rock reactions, and how their activity may in turn affect reaction progress, laboratory experiments have been conducted to monitor the growth of a methanogenic Archaea in the presence of H_2(g) produced from low temperature water–Fe⁰–basalt reactions. In these systems, the conversion of Fe(II) to Fe(III) and subsequent hydrolysis of water is responsible for the production of H_2(g). To characterize key components of the geochemical system, time series measurements of H₂ and CH₄ gas concentrations, Fe and Si aqueous concentrations, and spatially resolved synchrotron-based analyses of microscale Fe distribution and speciation were conducted. Culture experiments were compared with an abiotic control to document changes in the geochemistry both in the presence and absence of the methanogen.In the control abiotic batch experiment, H₂ was continuously produced, until the headspace became saturated, while in the biotic experiments, microbial consumption of H₂ for methanogenesis draws H₂ down and produces CH₄. Purging the headspace gas reinitiates H₂ and CH₄ production in abiotic and culture experiments, respectively. Mass balance analysis of the amount of CH₄ produced suggests that the total H₂ production in microbial experiments does not exceed the abiotic experiment. Soluble Si concentrations, while buffered to relatively constant values, were higher in culture experiments than the abiotic control.Iron_(aq) concentrations appear to respond to perturbations of H₂ and CH₄ gas concentrations in both culture experiments and the abiotic control. A pulse of Fe preceded the rise in either H₂ or CH₄ production, and as the gas concentrations increased the Fe_(aq) decreased. Iron-bearing mineral assemblages change with increasing reaction time and mineral assemblages vary between culture experiments and the abiotic control. These geochemical trends suggest that there are different reaction paths between the culture experiments and the abiotic control.The hydration of mafic rocks is a common geologic reaction and one that has taken place on Earth for the majority of its history and is postulated to occur on Mars. These reactions are important because of their effect on the rheology and geochemistry of the ocean crust. While most often studied at temperatures of ～250 °C, this work suggests that at lower temperatures microorganisms may have a profound effect on what has long been thought to be solely an abiotic reaction, and may produce diagnostic mineral assemblages that will be preserved in the geological record.     

Characterization of elemental release during microbe-basalt interactions at T = 28 °C

This study used batch reactors to characterize the rates and mechanisms of elemental release during the interaction of a single bacterial species (Burkholderia fungorum) with Columbia River Flood Basalt at T = 28 °C for 36 days. We primarily examined the release of Ca, Mg, P, Si, and Sr under a variety of biotic and abiotic conditions with the aim of evaluating how actively metabolizing bacteria might influence basalt weathering on the continents. Four days after inoculating P-limited reactors (those lacking P in the growth medium), the concentration of viable planktonic cells increased from ∼10⁴ to 10⁸ CFU (Colony Forming Units)/mL, pH decreased from ∼7 to 4, and glucose decreased from ∼1200 to 0 μmol/L. Mass-balance and acid-base equilibria calculations suggest that the lowered pH resulted from either respired CO₂, organic acids released during biomass synthesis, or H⁺ extrusion during uptake. Between days 4 and 36, cell numbers remained constant at ∼10⁸ CFU/mL and pH increased to ∼5. Purely abiotic control reactors as well as control reactors containing inert cells (∼10⁸ CFU/mL) showed constant glucose concentrations, thus confirming the absence of biological activity in these experiments. The pH of all control reactors remained near-neutral, except for one experiment where the pH was initially adjusted to 4 but rapidly rose to 7 within 2 days. Over the entire 36 day period, P-limited reactors containing viable bacteria yielded the highest Ca, Mg, Si, and Sr release rates. Release rates inversely correlate with pH, indicating that proton-promoted dissolution was the dominant reaction mechanism. Both biotic and abiotic P-limited reactors displayed low P concentrations. Chemical analyses of bacteria collected at the end of the experiments, combined with mass-balances between the biological and fluid phases, demonstrate that the absence of dissolved P in the biotic reactors resulted from microbial P uptake. The only P source in the basalt is a small amount of apatite (∼1.2%), which occurs as needles within feldspar grains and glass. We therefore conclude that B. fungorum utilized apatite as a P source for biomass synthesis, which stimulated elemental release from coexisting mineral phases via pH lowering. The results of this study suggest that actively metabolizing bacteria have the potential to influence elemental release from basalt in continental settings.     

Experimental evidence for rapid biotic and abiotic reduction of Fe (III) at low temperatures in salt marsh sediments: a possible mechanism for formation of modern sedimentary siderite concretions

Fe (III) reduction is a key component of the global iron cycle, and an important control on carbon mineralization. However, little is known about the relative roles and rates of microbial (biotic) iron reduction, which utilizes organic matter, versus abiotic iron reduction, which occurs without carbon mineralization. This paper reports on the capacity for salt marsh sediments, which typically are rich in iron, to support abiotic reduction of mineral Fe (III) driven by oxidation of sulphide. Sediment was reacted with amorphous FeS under strictly anaerobic conditions at a range of temperatures in biotic and abiotic microcosm experiments. Fe (III) reduction driven by sulphide oxidation occurs abiotically at all temperatures, leading to Fe (II) and elemental sulphur production in all abiotic experiments. In biotic experiments elemental sulphur is also the oxidized sulphur product but higher bicarbonate production leads to FeCO₃ precipitation. Abiotic reduction of Fe (III) occurs at rates that are significant compared with microbial Fe (III) reduction in salt marsh sediments. The solid phases produced by coupled abiotic and biotic reactions, namely elemental sulphur and FeCO₃, are comparable to those seen in nature at Warham, Norfolk, UK. Furthermore, the rates of these processes measured in the microcosm experiments are sufficient to generate siderite concretions on the rapid time scales observed in the field. This work highlights the importance of abiotic Fe (III) reduction alongside heterotrophic reduction, which has implications for iron cycling and carbon mineralization in modern and ancient sediments.     

Effect of bacterial activity on trace metals release from oxidation of sphalerite at low pH (<3) and implications for AMD environment

A series of experiments was conducted to better understand the bacterial influence on the release of trace metals during oxidation of sphalerite mineral and element cycles in acid mine drainage (AMD) systems. Batch experiments were carried out as biotic and abiotic control at pH 3. Acidithiobacillus ferrooxidans, sulfur and Fe(II) oxidizer, was used in the biotic sphalerite experiment. The abiotic control experiment was run without adding the bacteria. The release behavior of six trace metals (As, Cd, Co, Pb, Cu and Mn), Fe and Zn were determined during the period of 54 days. Compared to the abiotic experiments, enhanced oxidation of sphalerite by bacteria produced high sulfate (~2,000 mg/L) and Fe_tot (139 mg/L) along with the low pH (<2.3). Consistent with this, the concentration of trace metals (As, Cd, Co, Pb, Cu and Mn) was significantly higher in the biotic experiments than those in the abiotic experiments. Results indicate that the distributions of Co and Cd in both biotic and abiotic experiments are directly related to the sphalerite dissolution whereas Pb, Cu distribution shows no strong relation to sphalerite dissolution especially in the abiotic experiments. Pb distribution in the solution appears to be controlled by pH-dependent solubility. Approximately 80% of the trace metals were removed from the solution at the end of the biotic experiments along with biologically induced Fe precipitation. Experimental results showed that bacteria play major role not only in the release of trace metal from sphalerite but also in controlling concentration of the metals in the solution by producing Fe-oxyhydroxides. The study suggest that in order to develop an effective rehabilitation strategy for AMD, it is necessary to understand bio/geochemical processes governing mobilization and deposition of trace metals in the environment.     

Roller-coaster atmospheric-terrestrial-oceanic-climatic system during Ordovician-Silurian transition: Consequences of large igneous provinces

The Ordovician-Silurian transition (OST) hosted profound and frequent changes in the atmospheric-terrestrial-oceanic-climatic system (ATOCS). Previous studies have found contrasting stages for such changes, primarily based on hiatus-interrupted sections. However, the dominant driving factors and mechanisms reconciling such frequent changes remain controversial. Mercury isotopes, which undergo both mass-dependent and mass-independent fractionation, can provide critical insights into the deep-time ATOCSs, especially for those impacted by large igneous provinces (LIPs) events. Here, we build a high-resolution multi-proxy record of Hg (concentrations and isotopic compositions) combined with organic carbon isotopes (δ¹³C_org) and whole-rock geochemical data (including trace elements and phosphorus) from continuous cores in the Yangtze Platform, South China. Our data, combined with reported ones, indicate the occurrence of LIP eruptions against localized volcanism, and four successive, yet contrasting stages of ATOCSs during the OST. Moreover, we identified the coupling between two-pulse LIP magmatism and extreme ATOCSs, each with special pCO₂, weathering rate, primary productivity, redox condition, climatic mode, and biotic evolution. For stage I, the first pulse of LIP magmatism triggered global warming, enhanced terrestrial weathering, oceanic acidification, eutrophication, anoxia, P recycling, and thereby widespread deposition of black shales. During stage II, the Hirnantian glaciation and oxygenation arose from the intense chemical weathering and black shale deposition of stage I; slashed terrestrial weathering and oceanic oxygenation facilitated CO₂ accumulation. In stage III, another pulse of LIP magmatism triggered the de-glaciation, and the ATOCS was largely similar to that of stage I. This led to another round of oxygenation and positive δ¹³C_org excursion in stage IV. Compared with the environmental pressure by the peculiar ATOCS of each stage, their transitions might have been more devastating in triggering the prolonged Late Ordovician Mass Extinction (LOME). Moreover, limited biotic recovery was possible in the later portion of stages I and III. The multi-proxy study of continuous strata of the OST provides an excellent framework for better illuminating LIPs’ essential role in driving the “roller-coaster” behavior of the ATOCS and thus biotic crisis during the pivotal period of the OST.     

Dissolution rates of phyllosilicates as a function of bacterial metabolic diversity

Weathering experiments using biotite and phlogopite in the presence of bacteria were conducted to better understand biotic dissolution kinetics and processes (proton- and ligand-promoted dissolution) under aerobic conditions. Miniature batch reactors (300 μl in microplate wells) were used at 24 °C for 3 days with and without bacterial strains. Abiotic experiments were performed with organic and nitric acids in order to calibrate the biotite-phlogopite chemical dissolution. An empirical model was used to fit the pH dependence for iron release rate (r_Fe) considering the influence of both protons and ligands from acidic to neutral conditions (pH ranging from 3 to 7): r_Fe=k_H(a_H+)^m+k_L(a_L)¹ where k is the apparent rate constant, a_H+ and a_L are the activities of protons and ligands, and m and l are the reaction orders. For both minerals in most cases at a given pH, the iron release rates in the presence of bacteria were in good agreement with rates determined by the chemical model and could be explained by a combination of proton- and ligand-promoted processes. Bacteria affect mineral dissolution and iron release rates through the quantities and nature of the organic acids they produce. Three domains were differentiated and proposed as biochemical models of mica dissolution: (1) below pH 3, only proton-promoted dissolution occurred, (2) in weakly acidic solutions both ligand- and proton-promoted mechanisms were involved, and (3) iron immobilization occured, at pH values greater than 4 for biotite and greater than 5 for phlogopite. This model allows us to distinguish the “weathering pattern phenotypes” of strains. Bacteria that are isolated from horizons poor in carbon appear more efficient at weathering micas than bacterial strains isolated from environments rich in carbon. Moreover, our results suggest that the mineral could exert a control on the release of organic acids and the “weathering pattern phenotypes” of bacteria.     

Characterization of elemental release during microbe-granite interactions at T = 28 °C

This study used batch reactors to characterize the mechanisms and rates of elemental release (Al, Ca, K, Mg, Na, F, Fe, P, Sr, and Si) during interaction of a single bacterial species (Burkholderia fungorum) with granite at T = 28 °C for 35 days. The objective was to evaluate how actively metabolizing heterotrophic bacteria might influence granite weathering on the continents. We supplied glucose as a C source, either NH₄ or NO₃ as N sources, and either dissolved PO₄ or trace apatite in granite as P sources. Cell growth occurred under all experimental conditions. However, solution pH decreased from ∼7 to 4 in NH₄-bearing reactors, whereas pH remained near-neutral in NO₃-bearing reactors. Measurements of dissolved CO₂ and gluconate together with mass-balances for cell growth suggest that pH lowering in NH₄-bearing reactors resulted from gluconic acid release and H⁺ extrusion during NH₄ uptake. In NO₃-bearing reactors, B. fungormum likely produced gluconic acid and consumed H⁺ simultaneously during NO₃ utilization.Over the entire 35-day period, NH₄-bearing biotic reactors yielded the highest release rates for all elements considered. However, chemical analyses of biomass show that bacteria scavenged Na, P, and Sr during growth. Abiotic control reactors followed different reaction paths and experienced much lower elemental release rates compared to biotic reactors. Because release rates inversely correlate with pH, we conclude that proton-promoted dissolution was the dominant reaction mechanism. Solute speciation modeling indicates that formation of Al-F and Fe-F complexes in biotic reactors may have enhanced mineral solubilities and release rates by lowering Al and Fe activities. Mass-balances further reveal that Ca-bearing trace phases (calcite, fluorite, and fluorapatite) provided most of the dissolved Ca, whereas more abundant phases (plagioclase) contributed negligible amounts. Our findings imply that during the incipient stages of granite weathering, heterotrophic bacteria utilizing glucose and NH₄ only moderately elevate silicate weathering reactions that consume atmospheric CO₂. However, by enhancing the dissolution of non-silicate, Ca-bearing trace minerals, they could contribute to high Ca/Na ratios commonly observed in granitic watersheds.     

中国东部玄武岩风化土壤的粘土矿物及碳 汇地球化学研究

     玄武岩风化是大气CO2 的一个主要碳汇过程,气候条件是影响玄武岩风化和固碳速率的重要因素。该文选择中国东 部不同气候带的新生代玄武岩典型风化剖面,进行了粘土矿物和常量元素分析。结果显示,在内蒙古-海南岛的采样区间内, 随着气候条件由干冷向暖湿转化,风化剖面中粘土矿物组合呈现蒙脱石+ 伊利石+ 高岭石→蒙脱石+ 高岭石→高岭石+ 三水 铝石的转变。剖面中土壤元素得失状况也显示出相应的规律,由于存在粉尘输入与风化淋滤作用的综合影响,在干冷的内 蒙古地区,粉尘对于Ca,K,Na,Si 等元素的输入量大于这些元素的淋失量;在山东地区,Ca,K,Na 元素开始快速淋失, 大于粉尘的输入量;在苏皖地区,Si 元素的淋失量开始小于粉尘输入量;而在湿热的海南地区,风化作用强烈,Si显示出 大量淋失的特点,碱性元素几乎全部流失。根据元素的相对得失率和北方粉尘平均组分的校正,初步估算了研究区内玄武 岩风化对大气CO2 的消耗速率,其数值在5.37~181.00 t（km2·a）之间,与Dessert 等（2003）的研究结果大致相当。     

Impact of nitrogenous fertiliser-induced proton release on cultivated soils with contrasting carbonate contents: A column experiment

An experimental study was carried out in order to evaluate the impact of nitrogen fertiliser-induced acidification in carbonated soils. Undisturbed soil columns containing different carbonate content were sampled in the field. Fertiliser spreading was simulated by NH₄Cl addition on top of the soil column. Soil solution composition (mainly nitrate and base cations) was studied at the soil column’s base. Nitrification occurred to a different extent depending on soil type. Higher nitrification rates were observed in calcareous soils. In all the soil types, strong correlations between leached base cation and nitrate concentrations were observed. Regression coefficients between base cations, nitrate and chloride were used to determine the dominant processes occurring following NH₄Cl spreading. In non-carbonated soils, nitrogen nitrification induced base cation leaching and soil acidification. In carbonated soils, no change of soil pH was observed. However, fertilisers induced a huge cation leaching. Carbonate mineral weathering led to the release of base cations, which replenished the soil exchangeable complex. Carbonated mineral weathering buffered acidification. Since direct weathering might have occurred without atmospheric CO₂ consumption, the use of nitrogen fertiliser on carbonated soil induces a change in the cation and carbon budgets. When the results of these experiments are extrapolated on a global scale to the surface of fertilised areas lying on carbonate, carbonated reactions with N fertilisers would imply an additional flux of 5.7 × 10¹² mol yr⁻¹ of Ca + Mg. The modifications of weathering reactions in cultivated catchments and the ability of nitrogen fertilisers to significantly modify the CO₂ budget should be included in carbon global cycle assessment.     

An evaluation of acid deposition on cation leaching and weathering rates of an Andosol and a Cambisol

An evaluation of the response of an Andosol and a Cambisol to acid deposition and weathering rates was studied by using a controlled laboratory leaching experiment. Both soils where derived from mafic parent material, a Histic Andosol from Western Iceland and a Cambisol from North East Scotland. De-ionized water and water acidified with H₂SO₄ (pH 3) was leached through reconstructed soil columns to simulate 34 years of precipitation.Acidic input increased cation leaching and weathering rates in both soil types and reduced pH levels. The Andosol proved generally to have higher weathering rates, leaching potential, ion exchange and acid-buffering capacity as well as maintaining a relatively steady pH despite intense acidic input. This was due to differences in parent material and mineral composition. The Andosol was developed from basaltic volcanic tephra, which had higher dissolution rates due to its amorphous mineral structures. The Cambisol was developed from gabbro with more stable mineral structures.     

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ⁶⁶Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ⁶⁶Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ⁶⁶Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe₂O₄)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ⁶⁶Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ⁶⁶Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ⁶⁶Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.     

Plant and mycorrhizal driven silicate weathering: Quantifying carbon flux and mineral weathering processes at the laboratory mesocosm scale

The rise of vascular land plants in the Paleozoic is hypothesized to have driven lower atmospheric CO₂ levels through enhanced weathering of Ca and Mg bearing silicate minerals and rocks. However, this view overlooks the co-evolution of roots and mycorrhizal fungi, with many of the weathering processes ascribed to plants potentially being driven by the combined activities of roots and fungi. Here mesocosm scale controlled laboratory experiments quantifying the effects of plant and fungal evolution on silicate rock weathering under ambient and elevated CO₂ concentrations are described. A snapshot is presented of C allocation through roots and mycorrhizal fungi and biological activity associated with geochemical changes in weathered mineral substrates via transfer of elements from solid phases into solution.     

Geochemical characteristics of stream sediments,sediment fractions,soils, and basement rocks from the Mahaweli River and its catchment,Sri Lanka

Geochemical variations in stream sediments (n = 54) from the Mahaweli River of Sri Lanka have been evaluated from the viewpoints of lithological control, sorting, heavy mineral concentration, influence of climatic zonation (wet, intermediate, and dry zones), weathering, and downstream transport. Compositions of soils (n = 22) and basement rocks (n = 38) of the catchment and those of <180 μm and 180–2000 μm fractions of the stream sediments were also examined. The sediments, fractions, soils and basement rocks were analyzed by X-ray fluorescence to determine their As, Pb, Zn, Cu, Ni, Cr, V, Sr, Y, Nb, Zr, Th, Sc, Fe₂O₃, TiO₂, MnO, CaO, P₂O₅ and total sulfur contents. Abundances of high field strength and ferromagnesian elements in the sediments indicate concentration of durable heavy minerals including zircon, tourmaline, rutile, monazite, garnet, pyriboles, and titanite, especially in <180 μm fractions. The sediments show strong correlation between Ti and Fe, further suggesting presence of heavy mineral phases containing both elements, such as ilmenite and magnetite. The basement rocks range from mafic through to felsic compositions, as do the soils. The river sediments lack ultrabasic components, and overall have intermediate to felsic compositions. Elemental spikes in the confluences of tributary rivers and high values in the <180 μm fractions indicate sporadic inputs of mafic detritus and/or heavy minerals to the main channel. Al₂O₃/(K₂O + Na₂O) and K₂O/Na₂O ratios of the sediments and LOI values of the soils correlate well with the climatic zones, suggesting intense weathering in the wet zone, lesser weathering in the intermediate zone, and least weathering in the dry zone. Low Sr and CaO contents and Cr/V ratios in stream sediments in the wet zone also suggest climatic influence. Fe-normalized enrichment factors (EFs) for As, Pb, Zn, Cu, Ni and Cr in stream sediments in the main channel are nearly all <1.5, indicating there is no significant environmental contamination. The chemistry of the sediments, rocks and the soils in the Mahaweli River are thus mainly controlled by source lithotype, weathering, sorting, and heavy mineral accumulation.     

An experimental model approach of biologically-assisted silicate dissolution with olivine and Escherichia coli – Impact on chemical weathering of mafic rocks and atmospheric CO2 drawdown

Chemical weathering of Mg, Ca-silicates and alumino-silicates contributes significantly to the drawdown of atmospheric CO₂ over long time scales. The present work focuses on how this mode of weathering may change in the presence of free-living bacteria in oligotrophic waters, which compose most of the surface freshwaters of the Earth. Forsterite (Fo90) was reacted for 1 week with a stable Escherichia coli population in water maintained at 37 °C and neutral pH in a batch reactor. Control samples with suspensions of pure olivine powders and E. coli cells in pure water were also used for reference. Olivine controls reproduce the Mg, Si and Fe release in solutions predicted from rates published in the literature with pH shifts of less than 0.5 unit. After 1 week, under abiotic conditions, weathered surfaces are enriched in Fe and Fe³⁺ relative to the initial composition of the mineral. Bacterial controls (without minerals) show decreasing Eh with increasing cell concentrations (−50 mV with 7 × 10⁷ cells/mL and −160 mV with 8 × 10⁸ cells/mL). Magnesium concentrations in bacterial control solutions are in the μg/L range and can be accounted for by the release of Mg from dead cells. More than 80% of the cells were still alive after 1 week. The solutions obtained in the experiments in which olivine reacts in the presence of cells show Mg and Si concentrations a few tens of percent lower than in the mineral control samples, with a prominent depletion of Fe(III) content of the mineral surfaces. Magnesium mass balance discounts both significant bacterial uptake and inhibition of the Mg dissolution rates as a consequence of changing pH and Eh. Coating by bacterial cell layers is also negligible. E. coli reduces the chemical weathering of olivine. This study infers that the presence of free-living Proteobacteria, a prevalent group of subsurface bacteria, should decrease the amount of riverine Mg released by chemical weathering of mafic rocks.     

火山岩风化过程中难熔元素的活动性研究——以广西凭祥英安岩风化剖面为例

对广西凭祥叫弄英安岩风化剖面中6个难熔元素的活动性进行了研究。结果表明，Ti,Nb和Ta 3种元素在整个风化成土过程中基本上保持了它们的不活动性。Zr,Hf和Th在风化的初期阶段基本上保持不活动，而在风化中期表现出一定的富集，风化高级阶段则有明显的富集。Th的富集可能与风化壳表层（已剥蚀）淋溶出来的Th向下迁移过程中被氧化铁吸附和形成磷酸盐矿物有关，而Zr的富集则可能与淋溶出来的Zr与SiO2或磷酸盐结合形成某种硅酸盐矿物和磷酸盐矿物有关，具体富集原因还需作进一步的研究。     

Copper isotope fractionation in acid mine drainage

We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The δ⁶⁵Cu values (based on ⁶⁵Cu/⁶³Cu) of enargite (δ⁶⁵Cu = −0.01 ± 0.10‰; 2σ) and chalcopyrite (δ⁶⁵Cu = 0.16 ± 0.10‰) are within the range of reported values for terrestrial primary Cu sulfides (−1‰ < δ⁶⁵Cu < 1‰). These mineral samples show lower δ⁶⁵Cu values than stream waters (1.38‰ ? δ⁶⁵Cu ? 1.69‰). The average isotopic fractionation (Δ_aq-min = δ⁶⁵Cu_aq − δ⁶⁵Cu_min, where the latter is measured on mineral samples from the field system), equals 1.43 ± 0.14‰ and 1.60 ± 0.14‰ for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in ⁶⁵Cu relative to chalcopyrite (1.37 ± 0.14‰) and enargite (0.98 ± 0.14‰) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (Δ_aq-min^o=-0.57±0.14‰, where min^o refers to the starting mineral) and no apparent fractionation for enargite (Δ_aq-min^o=0.14±0.14‰). Abiotic fractionation is attributed to preferential oxidation of ⁶⁵Cu⁺ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of ⁶⁵Cu_aq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of δ⁶⁵Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage remediation and ore prospecting purposes.