Electron accepting capacity of dissolved organic matter as determined by reaction with metallic zinc   总被引：2，自引：0，他引：2  

Christian Blodau  Markus Bauer  Simona Regenspurg  Donald Macalady 《Chemical Geology》2009,260(3-4):186-195

Information about the chemical electron accepting capacity (EAC) of dissolved organic matter (DOM) is scarce owing to a lack of applicable methods. We quantified the electron transfer from metallic Zn to natural DOM in batch experiments at DOC concentrations of 10–100 mg-C L^− 1 and related it to spectroscopic information obtained from UV-, synchronous fluorescence, and FTIR- spectroscopy. The electron donating capacity of DOM and pre-reduced DOM was investigated using Fe(CN)₆³⁻ as electron acceptor. Presence of DOM resulted in release of dissolved Zn, consumption of protons, and slower release of hydrogen compared to reaction of metallic Zn with water at pH 6.5. Comparison with reaction stoichiometry confirmed that DOM accepted electrons from metallic Zn. The release of dissolved Zn was dependent on pH, DOC concentration, ionic strength, and organic matter properties. The reaction appeared to be completed within about 24 h and was characterized by pseudo first order kinetics with rate constants of 0.5 to 0.8 h^− 1. EAC per mass unit of carbon ranged from 0.22 mmol g^− 1 C to 12.6 mmol g^− 1 C. Depending on the DOM, a calculated 28–127% of the electrons transferred from metallic Zn to DOM could be subsequently donated to Fe(CN)₆³⁻. EAC decreased with DOC concentration, and increased with aromaticity, carboxyl, and phenolic content of the DOM. The results indicate that an operationally defined EAC of natural DOM can be quantified by reaction with metallic Zn and that DOM properties control the electron transfer. Shortcomings of the method are the coagulation and precipitation of DOM during the experiment and the production of hydrogen and dissolved Zn by reaction of metallic Zn with water, which may influence the determined EAC.  相似文献   

The Skaergaard liquid line of descent revisited   总被引：1，自引：0，他引：1  

Peter Thy  Charles E. Lesher  Christian Tegner 《Contributions to Mineralogy and Petrology》2009,157(6):735-747

There is a fundamental conflict between the suggestion that the iron content of Skaergaard liquids increases during Fe–Ti oxide fractionation and the observation that at the same time oxygen fugacity () drops by two log-units below the fayalite-magnetite-quartz oxygen buffer (FMQ). A new petrographic study of average Skaergaard gabbros shows that the total modal content of Fe–Ti oxides is about 22% in the early LZc and markedly decreases to below 5% in the UZc. Forward modeling based on these modal constraints, as well as experimental results on Skaergaard-related dikes, predicts that fractionation of troctolitic LZa gabbros drives the derivative liquid towards a high-iron content. Strong iron enrichment continues, together with a small decline in silica, during LZb crystallization due to the appearance of augite as a fractionating phase. The fractionation of Fe–Ti oxides in the LZc initially suppresses iron enrichment and reverses the silica trend to one of slight enrichment. However, continued evolution into the UZ produces liquids with maximum UZc FeO* content of 23–25 wt.% and SiO₂ content of 53 wt.% (FeO* is total iron as FeO). The maximum in FeO* is dependent on several factors of which the Fe–Ti oxide mode has the strongest effect. The during crystallization of the LZc is widely thought to have been at, or slightly below, the fayalite-magnetite-quartz oxygen buffer (FMQ). Under closed system evolution, incorporation of ferric iron into augite during formation of the LZb restricts the increase in to about 0.1 log-units above FMQ (=0.1 ΔFMQ). Likewise, crystallization of the LZc through the UZa, involving Fe–Ti oxide minerals, leads to a decline in of less than 0.1 ΔFMQ. Crystallization of the UZb-c gabbros results in oxidation to a maximum of 0.5 ΔFMQ. This behavior can account for the iron-rich character of the UZ gabbros, as well as, the low modal content of Fe–Ti oxides. Thus, evolved Skaergaard liquids are high in iron and contain a modest amount of SiO₂. Our modeling result do not account for a strong drop in through the layered series. Such a drop would require an unacceptably high proportion of Fe–Ti oxides and high-magnetite content in the fractionating assemblage. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.  相似文献   

Diffusion-controlled spherulite growth in obsidian inferred from H<Subscript>2</Subscript>O concentration profiles     

Jim Watkins  Michael Manga  Christian Huber  Michael Martin 《Contributions to Mineralogy and Petrology》2009,157(2):163-172

Spherulites are spherical clusters of radiating crystals that occur naturally in rhyolitic obsidian. The growth of spherulites requires diffusion and uptake of crystal forming components from the host rhyolite melt or glass, and rejection of non-crystal forming components from the crystallizing region. Water concentration profiles measured by synchrotron-source Fourier transform spectroscopy reveal that water is expelled into the surrounding matrix during spherulite growth, and that it diffuses outward ahead of the advancing crystalline front. We compare these profiles to models of water diffusion in rhyolite to estimate timescales for spherulite growth. Using a diffusion-controlled growth law, we find that spherulites can grow on the order of days to months at temperatures above the glass transition. The diffusion-controlled growth law also accounts for spherulite size distribution, spherulite growth below the glass transition, and why spherulitic glasses are not completely devitrified. An erratum to this article can be found at  相似文献   

Comparative behavior of Sr, Nd and Hf isotopic systems during fluid-related deformation at middle crust levels     

Béatrice Luais  Christian Le Carlier de Veslud  Yves Géraud 《Geochimica et cosmochimica acta》2009,73(10):2961-2977

We have carried out a comparative Rb-Sr, Sm-Nd and Lu-Hf isotopic study of a progressively deformed hercynian leucogranite from the French Massif Central, belonging to the La Marche ductile shear zone, in order to investigate the respective perturbation of these geochronometers with fluid induced deformation. The one-meter wide outcrop presents a strongly deformed and mylonitized zone at the center, and an asymmetric deformation pattern with a higher deformation gradient on the northern side of the zone. Ten samples have been carefully collected every 10 cm North and South away from the strongest deformed mylonitic zone. They have been analyzed for a complete major, trace element data set, oxygen isotopes, Rb-Sr, Sm-Nd and Lu-Hf isotopic systematics.We show that most of major and trace elements except SiO₂, alkaline elements (K₂O, Rb), and some metal transition elements (Cu), are progressively depleted with increasing deformation. This depletion includes REE + Y, but also HFS elements (Ti, Hf, Zr, Nb) which are commonly considered as immobile elements during upper level processes. Variations in elemental ratios with deformation, e.g. decrease in LREE/MREE- HREE, Nd/Hf, Th/Sr, increase in Rb/Sr, U/Th and constant Sr/Nd, lead to propose the following order of element mobility: U ? Th > Sr = Nd ? Hf + HREE. We conclude in agreement with previous tectonic and metallogenic studies that trace element patterns across the shear zone result from circulation of oxidizing F-rich hydrothermal fluids associated with deformation. A temperature of the fluid of 470-480 °C can be deduced from the δ¹⁸O equilibrium between quartz-muscovite pairs.Elemental fractionation induces perturbation of the Rb-Sr geochronometer. The well-defined ⁸⁷Rb/⁸⁶Sr-⁸⁷Sr/⁸⁶Sr correlation gives an apparent age of 294 ± 19 Ma, slightly younger than the 323 ± 4 Ma age of leucogranites in this area. This apparent age is interpreted as dating event of intense deformation and fluid circulation associated with mass transfer, and exhumation of the ductile crust shortly after the leucogranite emplacement. Sm-Nd and Lu-Hf isochron-type diagrams do not define any correlation, because of the low fractionated Sm/Nd and Lu/Hf ratios. Isotopic data demonstrate that only the Lu-Hf geochronometer system is not affected by fluid circulation and gives reliable T_DM age (1.29 ± 0.03 Ga) and ε_Hf signatures. By contrast, the Sm-Nd geochronometer system gives erroneous old T_DM ages of 2.84-4 Ga. There is no positive ε_Nd-ε_Hf correlation, because of decreasing ε_Nd values with deformation at constant ε_Hf values. However, ε_Nd-ε_Hf values remain in the broad ε_Nd-ε_Hf terrestrial array, which strongly indicates that fluid-induced fractionation can contribute to the width of the terrestrial array. The strong ε_Hf negative values of the leucogranite are similar to metasedimentary granulitic xenoliths from the French Massif Central and confirm the generation of the leucogranite by several episodes of reworking of the lower crust.  相似文献   

Mineralisation and structural changes during the initial phase of microbial degradation of pyrogenic plant residues in soil   总被引：1，自引：0，他引：1  

André Hilscher  Katja Heister  Christian Siewert  Heike Knicker 《Organic Geochemistry》2009,40(3):332-342

The microbial recalcitrance of char accumulated after vegetation fires was studied using pyrogenic organic material (PyOM) with increasing degrees of charring, produced from rye grass (Lolium perenne) and pine wood (Pinus sylvestris) at 350 °C under oxic conditions. Solid state ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy confirmed increasing aromaticity and the formation of heterocyclic N with prolonged charring. After mixing with a mineral soil, the PyOM was aerobically incubated for 48 days at 30 °C. To account for the input of fresh litter after a fire event, unburnt rye grass residue was added as a co-substrate. The grass-derived PyOM showed the greatest extent of C mineralisation. After 48 days incubation, up to 3.2% of the organic C (OC) was converted to CO₂. More severe thermal alteration resulted in a decrease in the total C mineralisation to 2.5% of OC. In the pine-derived PyOM, only 0.7% and 0.5% of the initial C were mineralised. The co-substrate additions did not enhance PyOM mineralisation during initial degradation. ¹³C NMR spectroscopic analysis indicated structural changes during microbial degradation of the PyOM. Concomitant with a decrease in O-alkyl/alkyl-C, carboxyl/carbonyl C content increased, pointing to oxidation. Only the strongly thermally altered pine PyOM showed a reduction in aromaticity. The small C losses during the experiment indicated conversion of aryl C into other C groups. As revealed by the increase in carboxyl/carbonyl C, this conversion must have included the opening and partial oxidation of aromatic ring structures. Our study demonstrates that plant PyOM can be microbially attacked and mineralised at rates comparable to those for soil organic matter (SOM), so its role as a highly refractory SOM constituent may need re-evaluation.  相似文献   

New insights into the genesis of volcanic-hosted massive sulfide deposits on the seafloor from numerical modeling studies   总被引：2，自引：0，他引：2  

Christian Schardt  Ross R. Large 《Ore Geology Reviews》2009,35(3-4):333-351

Numerical computer simulations have been used to gain insight into the evolution of marine hydrothermal systems and the formation conditions of massive sulfide deposits in ancient and modern submarine volcanic terrains. Simulation results have been used to gain a better understanding of the formation of massive sulfide ore deposits, their location, zonation, size, and occurrence in various geotectonic settings.Most hydrothermal fluid discharging at the seafloor exhibits temperatures ranging from 200 °C to about 410 °C and average fluid discharge velocities of 1 to 2 m/s in agreement with seafloor observations. Mass calculations imply that average massive sulfide deposits may form in ~ 5000 years while giant deposits take longer than 5000 years to accumulate; supergiant deposits either need much longer time to form (> 35,000 years) or at least 100 ppm of metal in solution. Results indicate that supergiant deposits may only form in certain geotectonic environments where longevity and preservation potential of the hydrothermal system are high. An additional process (mineral precipitate cap) is proposed here to explain the zinc content of massive sulfide deposits. This cap would prevent the widespread dissolution of anhydrite and the ‘wash-out’ of zinc by subsequent hydrothermal fluid discharge.  相似文献   

Microbial reduction of ferrous arsenate: Biogeochemical implications for arsenic mobilization     

Michael G. Babechuk  Christopher G. Weisener  Brian J. Fryer  Dogan Paktunc  Christian Maunders 《Applied Geochemistry》2009

In reduced aqueous environments, the presence of As in solution is a function of both biotic and abiotic mechanisms. Recent studies have demonstrated a significant release of As(III) through the microbial reduction of dissolved and mineral-bound As(V), which raises health concerns when the greater comparative mobility and toxicity of As(III) is considered. These release mechanisms do not operate in isolation but occur in concert with a number of removal processes, including secondary mineralization and sorption to other natural substrates. Thermodynamic and applied experimental studies have shown that ferrous arsenates, such as symplesite [Fe(II)₃(As(V)O₄)₂·8H₂O], may provide a significant sink for Fe(II) and As(V). In this study, the stability of a representative ferrous arsenate phase in the presence of the arsenate-reducing bacterium Shewanella sp. strain ANA-3 is examined. The reduction of ferrous arsenate by ANA-3 results in the release of aqueous As(III) and, subsequently, the progressive nucleation of a biogenic ferrous arsenite phase proximal to the microbial cells. The valence states of secondary solid-phase products were verified using X-ray absorption spectroscopy (XAS). Electron microscopy reveals that nucleation occurs on cellular exudates which may imply a role of extracellular reduction through c-type cytochromes as investigated in recent literature. These observations provide new insights into the reduction mechanisms of ANA-3 and the biogeochemical cycling of As(III) in natural systems.  相似文献   

Regional review: the hydrology of the Okavango Delta, Botswana—processes, data and modelling     

Christian Milzow  Lesego Kgotlhang  Peter Bauer-Gottwein  Philipp Meier  Wolfgang Kinzelbach 《Hydrogeology Journal》2009,17(6):1297-1328

The wetlands of the Okavango Delta accommodate a multitude of ecosystems with a large diversity in fauna and flora. They not only provide the traditional livelihood of the local communities but are also the basis of a tourism industry that generates substantial revenue for the whole of Botswana. For the global community, the wetlands retain a tremendous pool of biodiversity. As the upstream states Angola and Namibia are developing, however, changes in the use of the water of the Okavango River and in the ecological status of the wetlands are to be expected. To predict these impacts, the hydrology of the Delta has to be understood. This article reviews scientific work done for that purpose, focussing on the hydrological modelling of surface water and groundwater. Research providing input data to hydrological models is also presented. It relies heavily on all types of remote sensing. The history of hydrologic models of the Delta is retraced from the early box models to state-of-the-art distributed hydrological models. The knowledge gained from hydrological models and its relevance for the management of the Delta are discussed.  相似文献   

Roadheader performance prediction using genetic programming (GP) and gene expression programming (GEP) techniques     

Roohollah Shirani Faradonbeh  Alireza Salimi  Masoud Monjezi  Arash Ebrahimabadi  Christian Moormann 《Environmental Earth Sciences》2017,76(16):584

Roadheading machines play a vital role in excavation operation in tunneling and mining industries notably when selective mining is required. Roadheaders are more effective in soft to medium rock formations due to a higher cutting rate in such strata. A precise prediction of machine’s performance is a crucial issue, as it has considerable effects on excavation planning, project’s cost estimation, machine specification selection as well as safety of the project. In this research, a database of machine performance and some geomechanical parameters of rock formations from Tabas coal mine project, the largest and fully mechanized coal mine in Iran, has been established, including instantaneous cutting rate (ICR), uniaxial compressive strength, Brazilian tensile strength, rock quality designation, influence of discontinuity orientation (Alpha angle) and specific energy. Afterward, the parameters were analyzed through genetic programming (GP) and gene expression programming (GEP) approaches to yield more accurate models to predict the performance of roadheaders. As statistical indices, coefficient of determination, root mean square error and variance account were used to evaluate the efficiency of the developed models. According to the obtained results, it was observed that developed models can effectively be implemented for prediction of roadheader performance. Moreover, it was concluded that performance of the GEP model is better than the GP model. A high conformity was observed between predicted and measured roadheader ICR for GEP model.  相似文献   

Effect of Fenton process on treatment of simulated textile wastewater: optimization using response surface methodology     

S. Sharma  S. Kapoor  R. A. Christian 《International Journal of Environmental Science and Technology》2017,14(8):1665-1678

A large portion of water is consumed during various textile operations thereby discharging wastewaters with pollutants of huge environmental concern. The treatment of such wastewaters has promising impact in the field of environmental engineering. In this work, Fenton oxidation treatment was engaged to treat simulated textile wastewater. Box–Behnken design and response surface methodology were employed to optimize the efficiency of Fenton process. Iron dose, peroxide dose and pH were considered as input variables while the responses were taken as chemical oxygen demand and color removal. A total of 17 experiments were conducted and analyzed using second-order quadratic model. The quadratic models generated for chemical oxygen demand and color removal efficiencies were validated using analysis of variances, and it was found that the experimental data fitted the second-order model quite effectively. Analysis of variances demonstrated high values of coefficient of determination (R ²) for chemical oxygen demand and color removal efficiencies with values of 0.9904 and 0.9963 showing high conformation of predicted values to the experimental ones. Perturbation plots suggested that the iron dosage produced the maximum effect on both chemical oxygen demand and color removal efficiencies. The optimum parameters were determined as Fe²⁺ dose—550 mg/L, H₂O₂ dose—5538 mg/L, pH—3.3 with corresponding chemical oxygen demand and color removal efficiencies of 73.86 and 81.35%. Fenton process was found efficient in treatment of simulated textile wastewater, and optimization using response surface methodology was found satisfactory as well as relevant. From the present study, it can also be concluded that if this method is used as pretreatment integrated with biological treatment, it can lead to eco-friendly solution for treatment of textile wastewaters.  相似文献