Molecular simulations of metal adsorption to bacterial surfaces     

Kelly J. Johnson  Jeremy B. Fein 《Geochimica et cosmochimica acta》2006,70(20):5075-5088

The atomic-scale interactions that occur between cations and the metal-binding cell wall components common to many gram-positive bacteria were investigated using molecular simulations techniques. We examined the adsorption of Cd and Pb onto peptidoglycan and teichoic acid components of the bacterial cell wall using classical energy force field methods. Within the framework of molecular mechanics and the Cerius² modeling software, we used energy minimization, conformational analysis, and molecular dynamics to examine the different components of the cell wall and to determine relative binding energies and structural configurations of the cell wall components, both with and without the metals present. Electronic structure calculations of representative metal-organic complexes validate the more practical classical methods required in simulating the large number of atoms associated with the cell wall components. The classical force field simulations were conducted in both gas phase and solvated periodic cells. Force field-based simulation techniques can adequately describe the interactions of Cd with the cell wall, defining both metal ion coordinations and binding distances. However, the classical force field approach is inconsistent in describing the observed Pb-cell wall interactions due to possible limitations in the force field parameters, the propensity for Pb to form hydroxides at circumneutral pH, or the dominance of other adsorption mechanisms.  相似文献   

Monazite behaviour and age significance in poly-metamorphic high-grade terrains: A case study from the western Musgrave Block, central Australia     

Nigel M. Kelly  Geoffrey L. Clarke  Simon L. Harley 《Lithos》2006,88(1-4):100-134

Integrated, in situ textural, chemical and electron microprobe age analysis of monazite grains in a migmatitic metapelitic gneiss from the western Musgrave Block, central Australia has identified evidence for multiple events of growth and recrystallisation during poly-metamorphism in the Mesoproterozoic. Garnet + sillimanite-bearing metapelite underwent partial melting and segregation to palaeosome and leucosome during metamorphism between 1330 and 1296 Ma, with monazite grains in leucosome recording crystallisation at 1300 Ma. Monazite breakdown during melting is inferred to have occurred in the palaeosome. During a subsequent granulite facies event at 1200 Ma, deformation and metamorphism of leucosome and palaeosome resulted in partial disturbance of ages and potential minor growth on 1300 Ma monazite in leucosome. Growth of new, high-Y (+HREE) monazite in palaeosome domains occurred during garnet breakdown in the presence of sillimanite to cordierite and spinel, as a result of post-peak isothermal decompression. Diffusive enrichment of resorbed garnet rims in Y + HREE suggests garnet breakdown occurred slower than volume diffusion of REE. Monazite in both palaeosome and leucosome were subsequently partially to penetratively recrystallised during a retrogression event that is suggested to have occurred at 1150–1130 Ma. The intensity of recrystallisation and disturbance of ages appears linked to proximity to retrogressed garnet porphyroblasts and their occurrence in the relatively reactive or ‘fertile’ local environments provided by the palaeosome/mesosome volumes, which caused localised changes in retrogressive fluids towards compositions more aggressive to monazite. Like reaction textures, it is apparent that domainal equilibrium and reaction may control or at least strongly influence monazite REE and U–Th–Pb chemistry and hence ages.  相似文献   

The Role of Organic Matter During Metal Enrichment in Permian Kupferschiefer of the Rudna Mine,Southwest Poland     

孙玉壮  WILHELM PüTTMANN 《中国地球化学学报》2003,22(1):1-10

The bulk composition of organic matter and saturated and aromatic hydrocarbons extracted from 16 samples collected from two Kuperschiefer profiles in the Rudna mine,Southwest Poland has been analyzed to study the role of organic matter during base metal enrichment in the Kupferschiefer shale.The results indicated that the extract yields and saturated hydrocarbon yields decreased with increasing base metal contents.GC and GC/MS analyses indicated that n -alkanes and alkylated aromatic compounds were depleted and may have served as hydrogen donators for thermochemical sulfate reduction.The enrichment of base metal is closely connected with the destruction of hydrocarbons.  相似文献   

Nitrogen flow and the interaction of Boston harbor with Massachusetts Bay     

John R. Kelly 《Estuaries and Coasts》1997,20(2):365-380

This paper summarizes evidence that most of the considerable nitrogen loading (～8, 470 mmol total N m^?2 yr^?1) to Boston Harbor (Massachusetts, USA) is expelled to shallow shelf waters of Massachusetts Bay, where it strongly influences ecological dynamics. Examination of nitrogen concentrations in the harbor, compared with loading, indicated that removal processes are active in the harbor. Comparison to other estuarine systems showed that the harbor’s nitrogen concentrations are consistent with its loading, if they are corrected for tidal flushing effects on the water residence time. Furthermore, extensive measurements of sediment denitrification confirmed that rates of N₂ gas loss are high in an absolute sense (～600–800 mmol N m^?2 yr^?1) but nonetheless remove only a small portion (<10%) of the annual land-derived nitrogen loading. Burial in sediments apparently removes only about 2% of the N input, implying export to offshore environments as the major removal process (～88–90% of N input). Western Massachusetts Bay receiving waters were examined for a signature of export from the harbor. Data consistently show a gradient of decreasing nitrogen concentrations from the harbor to about 10–20 km into the bay. In many cases, plots of nitrogen concentrations versus salinity show nearly conservative mixing character, which implies virtual export. Seasonally, the data suggest most of the export from the harbor in winter is as dissolved inorganic forms (NH₄ ⁺, NO₃ ^?, NO₂ ^?). In summer, export is dominated by the outflow of organic nitrogen forms. Chlorophyll export is evident as well, suggesting that the nutritional coupling of the harbor and bay in summer involves organic fertilization of the bay’s surface water. Finally, high-resolution studies over different stages of the tidal cycle help refine understanding of the advection of chlorophyll and stimulation of in situ chlorophyll growth at the seaward edge of the tidal excursion into the bay.  相似文献   

Dehydration melting of tonalites. Part I. Beginning of melting     

J. Singh  Wilhelm Johannes 《Contributions to Mineralogy and Petrology》1996,125(1):16-25

 The beginning of dehydration melting in the tonalite system (biotite-plagioclase-quartz) is investigated in the pressure range of 2–12 kbar. A special method consisting of surrounding a crystal of natural plagioclase (An₄₅) with a biotite-quartz mixture, and observing reactions at the plagioclase margin was employed for precise determination of the solidus for dehydration melting. The beginning of dehydration melting was worked out at 5 kbar for a range of compositions of biotite varying from iron-free phlogopite to iron-rich Ann₇₀, with and without titanium, fluorine and extra aluminium in the biotite. The dehydration melting of phlogopite + plagioclase (An₄₅) + quartz begins between 750 and 770°C at pressures of 2 and 5 kbar, at approximately 740°C at 8 kbar and between 700 and 730°C at 10 kbar. At 12 kbar, the first melts are observed at temperatures as low as 700°C. The data indicate an almost vertical dehydration melting solidus curve at low pressures which bends backward to lower temperatures at higher pressures (> 5 kbar). The new phases observed at pressures ≤ 10 kbar are melt + enstatite + clinopyroxene + potassium feldspar ± amphibole. In addition to these, zoisite was also observed at 12 kbar. With increasing temperature, phlogopite becomes enriched in aluminium and deficient in potassium. Substitution of octahedral magnesium by aluminium and titanium in the phlogopite, as well as substitution of hydroxyl by fluorine, have little effect on the beginning of dehydration melting temperatures in this system. The dehydration melting of biotite (Ann₅₀) + plagioclase (An₄₅) + quartz begins 50°C below that of phlogopite bearing starting composition. Solid reaction products are orthopyroxene + clinopyroxene + potassium feldspar ± amphibole. Epidote was also observed above 8 kbar, and garnet at 12 kbar (750°C). The experiments on the iron-bearing system performed at ≤ 5 kbar were buffered with NiNiO. The f _{O 2} in high pressure runs lies close to CoCoO. With the substitution of octahedral magnesium and iron by aluminium and titanium, and replacement of hydroxyl by fluorine in biotite, the beginning of dehydration melting temperatures in this system increase up to 780°C at 5 kbar, which is 70°C above the beginning of dehydration melting of the assemblage containing biotite (Ann₅₀) of ideal composition. The dehydration melting at 5 kbar in the more iron-rich Ann₇₀-bearing starting composition begins at 730°C, and in the Ann₂₅-bearing assemblage at 710°C. This indicates that quartz-biotite-plagioclase assemblages with intermediate compositions of biotite (Ann₂₅ and Ann₅₀) melt at lower temperatures as compared to those containing Fe-richer or Mg-richer biotites. This study shows that the dehydration melting of tonalites may begin at considerably lower temperatures than previously thought, especially at high pressures (>5 kbar). Received: 27 December 1995 / Accepted: 7 May 1996  相似文献   

Dehydration melting of tonalites. Part II. Composition of melts and solids   总被引：6，自引：0，他引：6  

J. Singh  Wilhelm Johannes 《Contributions to Mineralogy and Petrology》1996,125(1):26-44

 Dehydration melting of tonalitic compositions (phlogopite or biotite-plagioclase-quartz assemblages) is investigated within a temperature range of 700–1000°C and pressure range of 2–15 kbar. The solid reaction products in the case of the phlogopite-plagioclase(An₄₅)-quartz starting material are enstatite, clinopyroxene and potassium feldspar, with amphiboles occurring occasionally. At 12 kbar, zoisite is observed below 800°C, and garnet at 900°C. The reaction products of dehydration melting of the biotite (Ann₅₀)-plagioclase (An₄₅)-quartz assemblage are melt, orthopyroxene, clinopyroxene, amphibole and potassium feldspar. At pressures > 8 kbar and temperatures below 800°C, epidote is also formed. Almandine-rich garnet appears above 10 kbar at temperatures ≥ 750°C. The composition of melts is granitic to granodioritic, hence showing the importance of dehydration melting of tonalites for the formation of granitic melts and granulitic restites at pressure-temperature conditions within the continental crust. The melt compositions plot close to the cotectic line dividing the liquidus surfaces between quartz and potassium feldspar in the haplogranite system at 5 kbar and a _{H 2O} = 1. The composition of the melts changes with the composition of the starting material, temperature and pressure. With increasing temperature, the melt becomes enriched in Al₂O₃ and FeO+MgO. Potash in the melt is highest just when biotite disappears. The amount of CaO decreases up to 900°C at 5 kbar whereas at higher temperatures it increases as amphibole, clinopyroxene and more An-component dissolve in the melt. The Na₂O content of the melt increases slightly with increase in temperature. The composition of the melt at temperatures > 900°C approaches that of the starting assemblage. The melt fraction varies with composition and proportion of hydrous phases in the starting composition as well as temperature and pressure. With increasing modal biotite from 20 to 30 wt%, the melt proportion increases from 19.8 to 22.3 vol.% (850°C and 5 kbar). With increasing temperature from 800 to 950°C (at 5 kbar), the increase in melt fraction is from 11 to 25.8 vol.%. The effect of pressure on the melt fraction is observed to be relatively small and the melt proportion in the same assemblage decreases at 850°C from 19.8 vol.% at 5 kbar to 15.3 vol.% at 15 kbar. Selected experiments were reversed at 2 and 5 kbar to demonstrate that near equilibrium compositions were obtained in runs of longer duration. Received: 27 December 1995 / Accepted: 7 May 1996  相似文献   

Geochemical exploration for platinum-group elements in the Bushveld Complex, South Africa   总被引：2，自引：0，他引：2  

H. J. Wilhelm  H. Zhang  F. L. Chen  J. H. Elsenbroek  M. Lombard  D. de Bruin 《Mineralium Deposita》1997,32(4):349-361

Analyses of stream sediment and soil samples from the Bushveld Complex, South Africa have revealed enhanced precious metal concentrations, which can be related both to mining activities and the presence of hidden concentrations of platinum-group elements (PGEs) and gold. The economically important PGE deposits hosted by the Upper Critical Zone of the Rustenburg Layered Suite are revealed by a high PGE and Au content in the overlying soils. A second zone of elevated precious metal concentrations straddles the boundary between the Main and Upper Zones and has to date been traced for more than 100 km. This zone follows the igneous layering of the Rustenburg Layered Suite and is offset by the Brits Graben. It is therefore thought to be the reflection of a magmatic PGE-Au mineralisation. Received: 31 May 1996 / Accepted: 7 January 1997  相似文献   

A bivariate meta-Gaussian density for use in hydrology   总被引：3，自引：0，他引：3  

K. S. Kelly  R. Krzysztofowicz 《Stochastic Environmental Research and Risk Assessment (SERRA)》1997,11(1):17-31

Convenient bivariate densities found in the literature are often unsuitable for modeling hydrologic variates. They either constrain the range of association between variates, or fix the form of the marginal distributions. The bivariate meta-Gaussian density is constructed by embedding the normal quantile transform of each variate into the Gaussian law. The density can represent a full range of association between variates and admits arbitrarily specified marginal distributions. Modeling and estimation can be decomposed into i) independent analyses of the marginal distributions, and ii) investigation of the dependence structure. Both statistical and judgmental estimation procedures are possible. Some comparisons to recent applications of bivariate densities in the hydrologic literature motivate and illustrate the model.  相似文献   

Composition of Kerogen in Kupferschiefer from Southwest Poland     

孙玉壮 《中国地球化学学报》2004,23(2):101-111

Thirty-seven Kupferschiefer samples from southwestern Poland were analyzed by microscopy, Rock-Eval approach and instrumental neutron activation analysis to understand the geochemical and morphological characteristics of kerogen present in the samples. The analytical results indicate that there are two different types of kerogens. One type was only subjected to thermal alteration processes, and the other was further oxidized after deposition of the sediment.In the oxidized samples migrabitumen was transformed into pyrobitumen. Rock-Eval analyses show a significant decrease in HI values in the oxidized samples and an increase in OI values in relation to the samples that were not influenced by oxidation. Variations in S2 versus Corg contents indicate a change in kerogen from Type II to Type III with progressing oxidation. The presence of pyrobitumen and the depletion of hydrogen in the altered kerogen allow one to conclude that the kerogen was used as hydrogen donor for thermochemical sulfate reduction(TSR).  相似文献   

Viruses as potential regulators of regional brown tide blooms caused by the alga,Aureococcus anophagefferens     

Mary Downes Gastrich  Justine A. Leigh-Bell  Christopher J. Gobler  O. Roger Anderson  Steven W. Wilhelm  Martha Bryan 《Estuaries and Coasts》2004,27(1):112-119

Blooms of the brown tide organismAureccoccus anophagefferens have recurred in the coastal bays in New Jersey since 1995 and in the coastal bays of Long Island since 1985. Intracellular viral-like particles (VLPs) were documented during 1999–2000 brown tide blooms in Little Egg Harbor, New Jersey, but it was not determined whether cells were infected during the termination of the bloom. The objective of this study was to determine if VLPs infected and lysed natural populations ofA. anophagefferens in coastal bays of New Jersey and New York in 2002 with the same frequency as in 1999–2000 and especially at the termination of the bloom. Our results confirmed that the highest percentage (37.5%) of VLP-infected cells occurred at the termination of the brown tide bloom in New Jersey in 2002. Intracellular VLPs were present throughout the bloom event. The percentage of visibly infected cells was higher at the beginning of the bloom than during the peak of the bloom. The intracellular VLPs in natural populations ofA. anophagefferens were consistent in size and shape (approximately 140 nm in diameter) and comparable to those in previous studies. Concentrated viral isolates, prepared from waters during brown tide blooms in New York and New Jersey in 2002, infected healthy laboratoryA. anophagefferens cultures in vitro. The viral isolates associated with the highest laboratory viral activity (lysis positive) were concentrated from water samples having the highest viral and bacteria concentrations. The intracellular viruses in these virally infected laboratory cultures ofA. anophagefferens were similar in size and shape to those found in natural populations. The successful isolation of a virus specific toA. anophagefferens from a brown tide bloom in the field, the similarity of ultrastructure of VLPs infecting both natural populations and laboratory infected cultures, and the pattern of VLP infection during bloom activity in combination with the observed high percentage of VLP-infected cells during bloom termination, supports, the hypothesis that viruses may be a major source of mortality for brown tide blooms in regional coastal bays of New Jersey and New York.  相似文献