Geochemical modeling of arsenic sulfide oxidation kinetics in a mining environment     

Maggy F. Lengke  Regina N. Tempel 《Geochimica et cosmochimica acta》2005,69(2):341-356

Arsenic sulfide (AsS (am), As₂S₃ (am), orpiment, and realgar) oxidation rates increase with increasing pH values. The rates of arsenic sulfide oxidation at higher pH values relative to those at pH∼2 are in the range of 26-4478, 3-17, 8-182, and 4-10 times for As₂S₃ (am), orpiment, AsS (am), and realgar, respectively.Numerical simulations of orpiment and realgar oxidation kinetics were conducted using the geochemical reaction path code EQ3/6 to evaluate the effects of variable DO concentrations and mineral reactivity factors on water chemistry evolution during orpiment and realgar oxidation. The results show that total As concentrations increase by ∼1.14 to 13 times and that pH values decrease by ∼0.6 to 4.2 U over a range of mineral reactivity factors from 1% to 50% after 2000 days (5.5 yr). The As release from orpiment and realgar oxidation exceeds the current U.S. National Drinking Water Standard (0.05 ppm) approximately in 200-300 days at the lowest initial dissolved oxygen concentration (3 ppm) and a reactivity factor of 1%. The results of simulations of orpiment oxidation in the presence of albite and calcite show that calcite can act as an effective buffer to the acid water produced from orpiment oxidation within relatively short periods (days/months), but the release of As continues to increase.Pyrite oxidation rates are faster than orpiment and realgar from pH 2.3 to 8; however, pyrite oxidation rates are slower than As₂S₃ (am) and AsS (am) at pH 8. The activation energies of arsenic sulfide oxidation range from 16 to 124 kJ/mol at pH∼8 and temperature 25 to 40°C, and pyrite activation energies are ∼52 to 88 kJ/mol, depending on pH and temperature range. The magnitude of activation energies for both pyrite and arsenic sulfide solids indicates that the oxidation of these minerals is dominated by surface reactions, except for As₂S₃ (am). Low activation energies of As₂S₃ (am) indicate that diffusion may be rate controlling.Limestone is commonly mixed with sulfide minerals in a mining environment to prevent acid water formation. However, the oxidation rates of arsenic sulfides increase as solution pH rises and result in a greater release of As. Furthermore, the lifetimes of carbonate minerals (i.e., calcite, aragonite, and dolomite) are much shorter than those of arsenic sulfide and silicate minerals. Thus, within a geologic frame time, carbonate minerals may not be present to act as a pH buffer for acid mine waters. Additionally, the presence of silicate minerals such as pyroxenes (wollastonite, jadeite, and spodumene) and Ca-feldspars (labradorite, anorthite, and nepheline) may not be important for buffering acid solutions because these minerals dissolve faster than and have shorter lifetimes than sulfide minerals. However, other silicate minerals such as Na and K-feldspars (albite, sanidine, and microcline), quartz, pyroxenes (augite, enstatite, diopsite, and MnSiO₃) that have much longer lifetimes than arsenic sulfide minerals may be present in a system. The results of our modeling of arsenic sulfide mineral oxidation show that these minerals potentially can release significant concentrations of dissolved As to natural waters, and the factors and mechanisms involved in arsenic sulfide oxidation warrant further study.  相似文献   

Book reviews     

Regina Tempel  Jaak Daemen  Donald E. Myers 《Mathematical Geosciences》1996,28(6):819-826

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Assessing streams in Germany with benthic invertebrates: Development of a multimetric invertebrate based assessment system   总被引：3，自引：0，他引：3  

Jürgen Bhmer  Claudia Rawer-Jost  Armin Zenker  Carolin Meier  Christian K. Feld  Regina Biss  Daniel Hering 《Limnologica》2004,34(4):416-432

The main aim of the study was to develop a multimetric assessment system for macroinvertebrate communities of small and mid-sized streams in Germany in accordance with the Water Framework Directive of the European Union. The system should be applicable by water authorities, capable of distinguishing between different impacts, and specifically adapted to all types of small and mid-sized rivers in Germany. An assessment system has been developed consisting of two modules based on the established indices for saprobic degradation and acidity, and a third module covering general degradation. For the third module a new multimetric index (MMI) was developed and tested using preclassifications for stream hydromorphological degradation, land use and general impairment as impact measures. More information on sampling method, season and the type of dominating human impairment allowed to further analyse the index' capabilities and sensitivity. It performed well in all seasons and detected all types of impairment except acidity. The usefulness of the impact measures used in this study is discussed with regard to the development of a multimetric index. The comparison of the new index with other indices showed that it is especially sensitive in detecting macroinvertebrate community responses to hydromorphological degradation and pollution such as the German AQEM index, while IBI 12 and Renkonen's similarity more reflect general community shifts caused by any type of disturbance. The new assessment system will be proposed for future use by state agencies for nationwide monitoring in the context of the Water Framework Directive implementation.  相似文献   

Conceptual study — An improved method to assess acidification in German streams by using benthic macroinvertebrates     

Ulrich Braukmann  Regina Biss 《Limnologica》2004,34(4):433-450

The present study is based mainly upon the authors' hydrochemical and hydrobiological studies of small silicate streams in South-West Germany, principally in the Black Forest and the Odenwald.

The aim of the paper is the adaptation of a practically proven four-level biological classification system of different degrees of acidity using benthic maroinvertebrates to a five-level system of acidification of mainly upland streams with low buffer capacity. The main reason for such a five-class system is the Water Framework Directive of the European Union (EU WFD), which lays down a five-level classification system for the assessment of the ecological quality of waters.

The biological method of assessing the state of acidity for evaluation of the degree of anthropogenic acidification under the directive, and principles of the EU WFD, are also described. A list of 278 taxa of the macrozoobenthos has been reclassified from a four-level system to a five-level biological indication system, based upon the authors' scientific expertise and the latest references from literature of different acid sensitive areas in Germany.  相似文献   

FracKfinder: A MATLAB Toolbox for Computing Three-Dimensional Hydraulic Conductivity Tensors for Fractured Porous Media     

Nathan L. Young  Jacqueline E. Reber  William W. Simpkins 《Ground water》2019,57(1):75-80

Fractures in porous media have been documented extensively. However, they are often omitted from groundwater flow and mass transport models due to a lack of data on fracture hydraulic properties and the computational burden of simulating fractures explicitly in large model domains. We present a MATLAB toolbox, FracKfinder, that automates HydroGeoSphere (HGS), a variably saturated, control volume finite-element model, to simulate an ensemble of discrete fracture network (DFN) flow experiments on a single cubic model mesh containing a stochastically generated fracture network. Because DFN simulations in HGS can simulate flow in both a porous media and a fracture domain, this toolbox computes tensors for both the matrix and fractures of a porous medium. Each model in the ensemble represents a different orientation of the hydraulic gradient, thus minimizing the likelihood that a single hydraulic gradient orientation will dominate the tensor computation. Linear regression on matrices containing the computed three-dimensional hydraulic conductivity (K) values from each rotation of the hydraulic gradient is used to compute the K tensors. This approach shows that the hydraulic behavior of fracture networks can be simulated where fracture hydraulic data are limited. Simulation of a bromide tracer experiment using K tensors computed with FracKfinder in HGS demonstrates good agreement with a previous large-column, laboratory study. The toolbox provides a potential pathway to upscale groundwater flow and mass transport processes in fractured media to larger scales.  相似文献   

Does Pumping Volume Affect the Concentration of Micropollutants in Groundwater Samples?          下载免费PDF全文

Inge H. van Driezum  Julia Derx  Ernis Saracevic  Alexander K.T. Kirschner  Regina Sommer  Andreas H. Farnleitner  Alfred Paul Blaschke 《Ground Water Monitoring & Remediation》2017,37(4):82-88

Information on concentrations of micropollutants (such as pharmaceuticals, pesticides, and industrial chemicals) in most highly dynamic riverbank filtration (RBF) systems is lacking, in contrast to data on standard chemical parameters. Sampling protocols have thus far been based on the stabilization of standard chemical parameters in relatively pristine environments. To determine whether groundwater samples for micropollutant analysis can be taken at a similar pumping volume as samples for testing standard chemical parameters in both environments, three groundwater monitoring wells in an RBF system were sampled at two points in time (after pumping of 3 well volumes and after pumping of 15 well volumes). Micropollutant concentrations were not significantly different between the two sampling points; therefore, appropriate samples can be drawn after pumping 3 well volumes. For a specific microbiological parameter (leucin incorporation), a statistically significant difference was found.  相似文献   

NanoSr – A New Carbonate Microanalytical Reference Material for In Situ Strontium Isotope Analysis     

Michael Weber  Federico Lugli  Bodo Hattendorf  Denis Scholz  Regina Mertz‐Kraus  Damien Guinoiseau  Klaus Peter Jochum 《Geostandards and Geoanalytical Research》2020,44(1):69-83

The in situ measurement of Sr isotopes in carbonates by MC‐ICP‐MS is limited by the availability of suitable microanalytical reference materials (RMs), which match the samples of interest. Whereas several well‐characterised carbonate reference materials for Sr mass fractions > 1000 µg g^?1 are available, there is a lack of well‐characterised carbonate microanalytical RMs with lower Sr mass fractions. Here, we present a new synthetic carbonate nanopowder RM with a Sr mass fraction of ca. 500 µg g^?1 suitable for microanalytical Sr isotope research (‘NanoSr’). NanoSr was analysed by both solution‐based and in situ techniques. Element mass fractions were determined using EPMA (Ca mass fraction), as well as laser ablation and solution ICP‐MS in different laboratories. The ⁸⁷Sr/⁸⁶Sr ratio was determined by well‐established bulk methods for Sr isotope measurements and is 0.70756 ± 0.00003 (2s). The Sr isotope microhomogeneity of the material was determined by LA‐MC‐ICP‐MS, which resulted in ⁸⁷Sr/⁸⁶Sr ratios of 0.70753 ± 0.00007 (2s) and 0.70757 ± 0.00006 (2s), respectively, in agreement with the solution data within uncertainties. Thus, this new reference material is well suited to monitor and correct microanalytical Sr isotope measurements of low‐Sr, low‐REE carbonate samples. NanoSr is available from the corresponding author.  相似文献   

Origin,age, and significance of deep‐seated granulite‐facies migmatites in the Barrow zones of Scotland,Cairn Leuchan,Glen Muick area          下载免费PDF全文

Richard M. Palin  Abdul B. Sayed  Richard W. White  Regina Mertz‐Kraus 《Journal of Metamorphic Geology》2018,36(8):1071-1096

Petrological modelling of granulite‐facies mafic and semipelitic migmatites from Cairn Leuchan, northeast Scotland, has provided new constraints on the pressure (P) and temperature (T) conditions of high‐grade metamorphism in the type‐locality Barrow zones. Phase diagrams constructed in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O₂ system have constrained the P?T conditions of peak metamorphism in the Glen Muick region of the upper sillimanite zone (Sill+Kfs) to have been at least ～840°C at ～9 kbar (high‐P granulite facies). These conditions are ～120°C and ～3 kbar higher than those recorded by lower sillimanite zone (Sill+Ms) units located only a few kilometres away to the southeast at Glen Girnock, indicating the presence of a significant thermal and barometric high exposed within the Scottish Dalradian, and supporting previous suppositions of a potential tectonic break between the two regions. U–Pb zircon geochronology performed on these mafic migmatites produced ages of c. 540–470 Ma from grains with both igneous and metamorphic morphological characteristics. Their basaltic protoliths likely formed during a period of volcanism dated at c. 570 Ma, associated with passive‐margin extension prior to the onset of Iapetus Ocean closure, and high‐grade metamorphism and partial melting is interpreted to have taken place at c. 470 Ma, synchronous with sillimanite‐grade metamorphism recorded elsewhere in the Dalradian. These high‐grade Cairn Leuchan lithologies are interpreted as representing a fragment of Grampian Terrane lower crust that was exhumed via displacement along a steeply dipping tectonic discontinuity related to the Portsoy–Duchray Hill Lineament, and are not pre‐Caledonian Mesoproterozoic basement, as suggested by some previous studies. Veins within some mafic migmatites in the Cairn Leuchan area, composed almost entirely (>80%) of garnet, with minor quartz, plagioclase, amphibole, and clinopyroxene, are interconnected with leucosomes and are interpreted to represent former garnet‐bearing melt segregations that have been locally drained of almost all melt. Thus, mafic components of the lower crust, currently underlying relatively lower grade metasediments exposed to the southeast, may represent a potential source rock for widely documented, post‐orogenic felsic plutons, sills, and dykes that occur throughout the Grampian Terrane.  相似文献   

Geostandards and Geoanalytical Research Bibliographic Review 2009     

Klaus P. Jochum  Xiaohong Wang  Regina Mertz-Kraus  Uwe Nohl  Steffen Schmidt  Beate Schwager  Brigitte Stoll  Qichao Yang  Ulrike Weis 《Geostandards and Geoanalytical Research》2010,34(4):407-410

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Characterisation of Apatites as Potential Uranium Reference Materials for Fission‐track Dating by LA‐ICP‐MS          下载免费PDF全文

Cleber J. Soares  Regina Mertz‐Kraus  Sandro Guedes  Daniel F. Stockli  Thomas Zack 《Geostandards and Geoanalytical Research》2015,39(3):305-313

We report homogeneity tests on large natural apatite crystals to evaluate their potential as U reference materials for apatite fission‐track (AFT) thermochronology by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS). The homogeneity tests include the measurements of major element concentrations by electron probe microanalysis (EPMA), whereas for U concentration, isotope dilution (ID) ICP‐MS and laser ablation (LA) ICP‐MS were employed. Two apatite crystals are potential reference materials for LA‐ICP‐MS analysis: a 1 cm³ fraction of a Durango crystal (7.5 μg g^?1 U) and a 1 cm³ Mud Tank crystal (6.9 μg g^?1 U). The relative standard deviation (1 RSD) of the U concentration determined by ID‐ICP‐MS of both apatite crystals was ≤ 1.5%, whereas 1 RSD for the LA‐ICP‐MS results was better than 4%, providing sufficient homogeneity for fission‐track dating. The results on the U homogeneity for two different apatite samples are an important step towards establishing in situ dating routines for AFT analysis by LA‐ICP‐MS.  相似文献