Factors influencing the oxidation,reduction, methylation and demethylation of mercury species in coastal waters     

Lindsay Whalin  Eun-Hee Kim  Robert Mason 《Marine Chemistry》2007

The objective of this study was to examine the redox reactions and other transformations of mercury (Hg) species in surface waters, and the factors determining the rates of these reactions. For the redox studies completed at the Chesapeake Biological Laboratory (CBL), two isotopes (¹⁹⁹Hg^II and ²⁰²Hg⁰) were added into different types of filtered water (fresh to seawater) to examine the oxidation and reduction reactions. Further studies of both the redox reactions and methylation/demethylation reactions of Hg were conducted with unfiltered water on board research vessels during cruises in May and July 2005 on the Chesapeake Bay and shelf. While CH₃¹⁹⁹Hg^II was added to allow the examination of demethylation, ²⁰¹Hg^II was used to examine both reduction and methylation, and ²⁰²Hg⁰ was used to examine oxidation. Overall, the results showed that both Hg oxidation and reduction were simultaneously occurring and were photochemically mediated in the waters investigated. In contrast to the previously assumed “unreactive” nature of Hg⁰, the studies found that the magnitude of the rate constant for Hg⁰ oxidation was greater than that for reduction, indicating its importance in estuarine and coastal waters. In addition, both experiments at CBL and on board ship showed that Hg^II reduction was similar in magnitude, suggesting that biotic processes were relatively unimportant. While no measurable methylation occurred during the incubation period during the on board studies, concentration of CH₃¹⁹⁹Hg^II decreased over the time during the experiments. It appeared that the demethylation processes were not dominantly photochemically driven, but could be microbially mediated. Further studies are needed in order to help better understand Hg redox and transformations in natural water systems.  相似文献   

大岭子金矿地质特征及选矿浸出率     

赵明统  王华  付冬梅 《云南地质》2008,27(2):149-155

大岭子金矿V1矿体赋存于中元古界高黎贡山群变质岩中,受韧性剪切带控制,矿石类型以氧化矿石为主。提出选矿依据。  相似文献   

Sludge weathering and mobility of contaminants in soil affected by the Aznalcollar tailing dam spill (SW Spain)   总被引：3，自引：0，他引：3  

C. Domnech  C. Ayora  J. de Pablo 《Chemical Geology》2002,190(1-4):355-370

As a result of the collapse of the Aznalcollar mine tailings dam, a large extension of the Guadiamar valley in SW Spain was covered with a layer of pyrite sludge. Although most of the sludge was removed, a small amount remains in the soil, constituting a potential source of water pollution. A column experiment was carried out in order to determine the rate of sludge oxidation in the soil, and the existence of metal retention processes. The column was filled with a mixture of sludge and a sandy soil common in the region. At different time intervals, the column was leached with water and the resulting solution analysed.

The pH of the water dropped to values around 2 after 260 days and then remained constant due to the buffering role of silicate dissolution. The concentration of Zn, Cd and Co in the leachates matched the expected values from flow-through experiments at atmospheric oxygen pressure. This indicates that oxygen diffusion in the pores was complete. Moreover, no efficient processes existed for retaining Zn, Cd and Co, which formed soluble salts and were entirely incorporated into the infiltrating water. During the first 2 months of the experiment, when pH was higher than 4.5, the concentrations of Fe and Al were very low. Saturation indices showed that the solution was in equilibrium with amorphous Fe(OH)₃ and Al(OH)₃. Subsequently, at lower pH values, jarosite [(Na,K)Fe₃(SO₄)₂(OH)₆] formed. This solid phase was identified by X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). Jarosite was also responsible for the depletion of As, Pb, Sb and probably Tl in the water resulting from infiltration.  相似文献   

Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X-ray absorption near-edge structure spectroscopy     

Yu. Mikhlin  Ye. Tomashevich 《Physics and Chemistry of Minerals》2005,32(1):19-27

Fe L-, S L-, and O K-edge X-ray absorption spectra of natural monoclinic and hexagonal pyrrhotites, Fe_1-xS, and arsenopyrite, FeAsS, have been measured and compared with the spectra of minerals oxidized in air and treated in aqueous acidic solutions, as well as with the previous XPS studies. The Fe L-edge X-ray absorption near-edge structure (XANES) of vacuum-cleaved pyrrhotites showed the presence of, aside from high-spin Fe²⁺, small quantity of Fe³⁺, which was higher for a monoclinic mineral. The spectra of the essentially metal-depleted surfaces produced by the non-oxidative and oxidative acidic leaching of pyrrhotites exhibit substantially enhanced contributions of Fe³⁺ and a form of high-spin Fe²⁺ with the energy of the 3d orbitals increased by 0.3–0.8 eV; low-spin Fe²⁺ was not confidently distinguished, owing probably to its rapid oxidation. The changes in the S L-edge spectra reflect the emergence of Fe³⁺ and reduced density of S s–Fe 4s antibonding states. The Fe L-edge XANES of arsenopyrite shows almost unsplit e_g band of singlet Fe²⁺ along with minor contributions attributable to high-spin Fe²⁺ and Fe³⁺. Iron retains the low-spin state in the sulphur-excessive layer formed by the oxidative leaching in 0.4 M ferric chloride and ferric sulphate acidic solutions. The S L-edge XANES of arsenopyrite leached in the ferric chloride, but not ferric sulphate, solution has considerably decreased pre-edge maxima, indicating the lesser admixture of S s states to Fe 3d orbitals in the reacted surface layer. The ferric nitrate treatment produces Fe³⁺ species and sulphur in oxidation state between +2 and +4.  相似文献   

Nonlinear chemical couplings in the tropospheric NO x -HO x gas phase chemistry     

J. Zimmermann  D. Poppe 《Journal of Atmospheric Chemistry》1993,17(2):141-155

A bifurcation phenomenon with relevance to atmospheric chemistry is discussed. The gasphase reactions in the troposphere exhibit two types of temporal evolution which are controlled by the strength of the source,Q, of nitric oxide, NO, via the nonlinear chemical coupling between the hydrogen oxides and nitrogen oxides chemistry. IfQ remains below a threshold value, all short-lived species, including NO, approach steady-state concentrations, while above the threshold bifurcation to another state with increasing (nonstationary) NO concentrations accompanied by a depletion of the OH and HO₂ abundances takes place.  相似文献   

湖南大坊金银矿氧化带特征及工业意义   总被引：1，自引：0，他引：1  

王福山 《湖南地质》1991,10(1):17-24

湖南大坊金银矿位于耒阳—临武南北向构造带中段,控矿层位为石炭系中上统壶天群和下统梓门桥组白云岩。矿体受北西和北东向组扭裂面的控制,产于花岗闪长斑岩内外接触带。氧化带的有用组分为金和银,已圈定矿体7个,其平均品位Au 2.68 g/t,Ag26.20g/t。金的粒度以中—细粒为主,氰化浸出率在91％以上,银经槽浸回收率仅20-30%。鉴于金浸出率高,矿体埋藏浅。开采技术条件简单,交通方便等特点,值得开发利用。  相似文献   

Determination of arsenic(III) for the investigation of the microbial oxidation of arsenic(III) to arsenic(V)     

B. Hambsch  B. Raue  H.-J. Brauch 《洁净——土壤、空气、水》1995,23(4):166-172

Recent evaluations of acute and chronical toxicity of arsenic resulted in a reduction of the standard value for total arsenic from 40 μg/L to 10 μg/L in drinking water which will be valid in Germany after a transition period as from January 1996. Arsenic is well known as substance of deep groundwaters, mainly of geogenic origin and normally found as As(III) or As(V). As(V) is well removable by flocculation and filtration after adding iron salts. As(III), however, has to be oxidized first to As(V). Therefore, it is important for treatment techniques to be able to distinguish between As(III) and As(V). A modified determination of As(III) using flow injection analysis was installed and optimized in order to investigate whether As(III) may be oxidized to As(V) by bacteria in natural waters. The results showed that at 4°C, no As(III)-oxidation was observed within 14 days. At room temperature, however, in the bacteria-containing samples, an As(III)-oxidation was found starting after 3 to 7 days. After 14 days, no As(III) was left over. In contrast, in the sterile samples, no As(III)-oxidation could be observed within 14 days. These results demonstrated that microbial processes influence the oxidation of As(III) to As(V) in natural waters.  相似文献   

淅川石煤钒矿提取技术的研究     

许国镇  陈波珍  韩晓梅  蒋莉 《矿产与地质》1992,(5)

石煤提钒技术关键是钒的氧化和转化。浙川石煤中钒主要有V~(3+)和V~(4+)形式存在,以类质同象取代粘土矿物二八面体中Al~(3+)。钒的价态分布研究表明,低温时有机质和黄铁矿决定了钒的价态,在370℃(风化样)或490℃(原样)V~(3+)全部氧化至V~(4+);高于800℃V~(4+)不再氧化至V~(5+),反应处于动态平衡,此时ηV~(5+)达91％。同时讨论了氯化钠在提钒过程中的氧化和转化作用,石煤钠盐氧化焙烧提钒的最佳条件:矿:盐=100:15,800℃,30分钟,η_培为67.4％。实验表明,焙烧气氛对钒转化有很大影响,氧化—氯化焙烧技术提高η_培6％。  相似文献   

Mineralogical and geochemical behavior of mill tailing material produced from lead-zinc skarn mineralization,Hanover, Grant County,New Mexico,USA   总被引：3，自引：0，他引：3  

I. F. Walder  W. X. Chavez Jr. 《Environmental Geology》1995,26(1):1-18

Mineral extraction and processing, especially metal mining, produces crushed and milled waste; such material, exposed to weathering, poses the potential threat of environmental contamination. In this study, mill tailings from inactive Pb-Zn mines in New Mexico, southwest USA, have been examined for their potential environmental impacts by means of detailed mineralogical and geochemical characterization. The principal ore minerals remaining in the tailings material are sphalerite, chalcopyrite, and very minor galena, smithsonite, and cerrusite, accompanied by the gangue minerals pyrite, pyrrhotite, magnetite, hematite, garnet, pyroxene, quartz, and calcite. White precipitate occurring on tailings surfaces is composed of gypsum and hydrated magnesium sulfates. Pyrite is mostly unaltered or shows only micron-scale rims of oxidation (goethite/hematite) in some surface samples. This iron oxide rim on pyrite is the only indication of weathering-derived minerals found by microscopy. There are variations in element concentrations with depth that reflect primary variations through time as the tailings ponds were filled. Cadmium and Zn concentrations increase with depth and Ag and Pb are low for the uppermost core samples, while Cu, Ni, and Co concentrations are generally high for the uppermost core samples. These elemental distributions indicate that little or no leaching has taken place since emplacement of the tailings because no accumulation or enrichment of these metals is observed in Hanover tailings, even in reducing portions of tailings piles. Element concentrations of surface samples surrounding the tailings reflect underlying mineralized zones rather than tailings-derived soil contamination. We observed no successive decreasing metal concentrations in prevalent wind directions away from the tailings. Stream sediment samples from Hanover Creek have somewhat elevated Zn, Cd, and Pb concentrations in areas that receive sediments from erosion of the tailings. However, input from tributaries downstream of the ponds appears to be principal source of heavy metals in Hanover Creek. The results of this study indicate that there is low risk for groundwater heavy-metal contamination from Hanover tailings. Tailings material do not show significant geochemical oxidation/alteration or metal leaching with depth. Our studies indicate that neutralizing minerals present in the tailings are sufficient to keep the tailings material chemically stable. Geochemically, however, tailings materials are being eroded and may pose a threat to Hanover Creek via siltation.  相似文献   

Mobility of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric O2: an experimental study   总被引：1，自引：0，他引：1  

Mats Åström 《Environmental Geology》1998,36(3-4):219-226

 The major aim was to increase our knowledge on the behaviour of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric oxygen. Samples of this type of sediment collected in a previous investigation at eight sites in western Finland were digested in HClO₄-HNO₃-HCl-HF at 200  °C and in HCl:HNO₃:H₂O at 95  °C (aqua regia), and subjected to extractions with ammonium acetate and hydrogen peroxide. Metals and S in the leachates were determined with ICP-AES. The results of the chemical analyses are compared with previously reported experimental data. The concentrations of Al and Fe in the sulphide-bearing fine-grained sediments are about 7% and 5%, respectively. Of the trace metals studied, Mn is most abundant followed in decreasing order by V>Cr>Ni>Cu>Co. On oxidation of the sediments, high proportions of Co, Mn and Ni, intermediate proportions of Cu but low proportions of Fe, Al, Cr and V are released. The extent of the release of a metal on oxidation is controlled either by (1) the level to which the pH of the sediments drops on oxidation (Al, Cu, Cr, V), (2) the amount of the metal associated with easily reduced phases (metal sulphides) in the sediments (Ni, Co) or (3) the sum of the amount associated with reduced phases and adsorbed on soil compounds (Mn). No control of the release of Fe on oxidation of the sediments was identified. Based on the results of the study it is argued that artificial drainage and the subsequent oxidation of sulphide-bearing sediments will result in extensive leaching of Co, Mn and Ni, moderate leaching of Cu and limited leaching of Cr and V into drainages. The major elements, Fe and Al, have the potential to be mobilised and leached in large amounts, though the proportions mobilised/leached will remain low. It is suggested that the identification of sulphide-bearing sediments with a high potential of metal release should be based on determination of metals in easily mobilised reduced compounds (dissolved e.g. in H₂O₂) and of the level to which the pH of the sediments drops on oxidation. Received: 16 October 1997 · Accepted: 9 March 1998  相似文献