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1.
甲烷渗漏区沉积层中存在的大量自生碳酸盐岩和铁硫化物,是指示天然气水合物存在的标志。但对其形成条件的实验研究还不多见。利用自主研发的模拟装置,首次在富含甲烷氧化菌和硫酸盐还原菌的微生物系统内,通过水化学分析方法,探讨不同温度和压力下水化学组分的变化;通过扫描电镜和能谱分析方法,确定自生碳酸盐和铁硫化物的形态和种类,研究它们在不同温压条件下的形成规律。结果表明:5℃,8℃和10℃实验中,pH保持在6.5~7.4之间,ORP稳定在-100.0 mV附近,HCO3-浓度为202.55~639.93 mg/L。2.5 MPa,5.0 MPa和7.5 MPa实验中,pH在6.1~7.2之间,ORP稳定在-100.0~-50.0 mV之间,HCO3-浓度为324.08~789.95 mg/L。温度和压力通过影响微生物代谢产生S2-和HCO3-、离子结合两个过程,最终控制矿物的形成。碳酸钙、菱铁矿和铁硫化物在各实验中都有生成。温度升高:HCO3-浓度变化范围变小,S2-浓度增加,氧化还原电位减小;碳酸钙形成较少;菱铁矿随温度升高而增加,铁硫化物形成随S2-浓度增加而变广,表明温度升高促进铁硫化物和菱铁矿的形成。压力增加:S2-生成量增加,ORP(氧化还原电位)变得更小;形成的铁硫化物颗粒越大且形态更好;生成的碳酸钙变少,可能受到S2-浓度的影响。这些实验结果对于研究全球海洋中碳和硫的存储及循环、自生矿物的形成机理等都具有重要意义。  相似文献   

2.
Sulfate-reducing bacteria (SRB) are ubiquitous in anoxic environments where they couple the oxidation of organic compounds to the production of hydrogen sulfide. This can be problematic for various industries including oil production where reservoir “souring” (the generation of H2S) requires corrective actions. Nitrate or nitrite injection into sour oil fields can promote SRB control by stimulating organotrophic nitrate- or nitrite-reducing bacteria (O-NRB) that out-compete SRB for electron donors (biocompetitive exclusion), and/or by lithotrophic nitrate- or nitrite-reducing sulfide oxidizing bacteria (NR-SOB) that remove H2S directly. Sulfur and oxygen isotope ratios of sulfide and sulfate were monitored in batch cultures and sulfidic bioreactors to evaluate mitigation of SRB activities by nitrate or nitrite injection. Sulfate reduction in batch cultures of Desulfovibrio sp. strain Lac15 indicated typical Rayleigh-type fractionation of sulfur isotopes during bacterial sulfate reduction (BSR) with lactate, whereas oxygen isotope ratios in unreacted sulfate remained constant. Sulfur isotope fractionation in batch cultures of the NR-SOB Thiomicrospira sp. strain CVO was minimal during the oxidation of sulfide to sulfate, which had δ18OSO4 values similar to that of the water-oxygen. Treating an up-flow bioreactor with increasing doses of nitrate to eliminate sulfide resulted in changes in sulfur isotope ratios of sulfate and sulfide but very little variation in oxygen isotope ratios of sulfate. These observations were similar to results obtained from SRB-only, but different from those of NR-SOB-only pure culture control experiments. This suggests that biocompetitive exclusion of SRB took place in the nitrate-injected bioreactor. In two replicate bioreactors treated with nitrite, less pronounced sulfur isotope fractionation and a slight decrease in δ18OSO4 were observed. This indicated that NR-SOB played a minor role during dosing with low nitrite and that biocompetitive exclusion was the major process. The results demonstrate that stable isotope data can contribute unique information for understanding complex microbial processes in nitrate- and sulfate-reducing systems, and offer important information for the management of H2S problems in oil reservoirs and elsewhere.  相似文献   

3.
崔猛  符晓  郑俊杰  吕苏颖  熊辉辉  曾晨  韩尚宇 《岩土力学》2022,43(11):3027-3035
植物源脲酶诱导碳酸钙沉淀(enzyme induced carbonate precipitation,简称EICP)可以显著改善砂土的工程力学特性,但在具体操作时,参数取值无对应规范,固化效果有待提升。基于黄豆脲酶,研究了温度、脲酶浓度、尿素浓度、钙浓度、pH值、钙源种类等变量对脲酶活性与碳酸钙沉淀的影响,并进行了沉淀物(碳酸钙晶体)的扫描式电子显微镜(scanning electron microscope,简称SEM)与X射线衍射(X-ray diffraction,简称XRD)测试,在此基础上开展了黄豆脲酶固化砂的无侧限抗压强度与固化效果试验研究。结果表明:脲酶活性随脲酶浓度的增加而线性增长,但存在温度阈值,温度超过阈值后,脲酶将完全失活,且阈值随脲酶浓度的增大而降低;尿素浓度与pH值共同影响脲酶活性,二者存在一个最优组合,当尿素浓度在0.1~1.0 mol/L时最优pH值为7,当尿素浓度在1.0~1.5 mol/L时最优pH值为8。脲酶是沉淀反应的催化剂,脲酶浓度越高,反应越完全,碳酸钙沉淀率越高;尿素与钙溶液则主要通过掺入量影响碳酸钙沉淀量,掺量比例宜为1:1,且二者浓度与pH值可通过影响脲酶活性来影响碳酸钙的沉淀情况;不同钙源对碳酸钙沉淀量的影响幅度不大。不同钙源沉淀碳酸钙晶体的成分与密度基本相同,但晶体结构差异较大,氯化钙沉淀碳酸钙晶体以块状为主,表面分布球状、类球状晶体,胶结面大,可作为EICP技术中较为理想的钙源。基于黄豆脲酶和氯化钙钙源固化砂的无侧限抗压强度约为掺粉煤灰砂样的6倍,通过SEM图像可发现,沉淀碳酸钙晶体包裹并黏结砂粒成为整体,固化效果非常理想。  相似文献   

4.
碳酸盐岩红色风化壳中的氧化铁矿物   总被引:6,自引:0,他引:6       下载免费PDF全文
朱立军  李景阳 《地质科学》2001,36(4):395-401
氧化铁矿物是碳酸盐岩红色风化壳的主要矿物成分和重要结构单元。运用X射线衍射、透射电镜、扫描电镜、穆斯堡尔谱和电子探针等方法对碳酸盐岩红色风化壳中的氧化铁矿物进行了系统研究。碳酸盐岩红色风化壳中的氧化铁矿物主要有针铁矿、赤铁矿和磁赤铁矿。氧化铁矿物组合、含量和化学成分随成土环境和风化强度在剖面中呈明显的规律性变化,这为碳酸盐岩风化成土作用、红色风化壳成因与环境问题的深入研究提供了重要的矿物学依据。  相似文献   

5.
Tailings generated during processing of sulfide ores represent a substantial risk to water resources. The oxidation of sulfide minerals within tailings deposits can generate low-quality water containing elevated concentrations of SO4, Fe, and associated metal(loid)s. Acid generated during the oxidation of pyrite [FeS2], pyrrhotite [Fe(1−x)S] and other sulfide minerals is neutralized to varying degrees by the dissolution of carbonate, (oxy)hydroxide, and silicate minerals. The extent of acid neutralization and, therefore, pore-water pH is a principal control on the mobility of sulfide-oxidation products within tailings deposits. Metals including Fe(III), Cu, Zn, and Ni often occur at high concentrations and exhibit greater mobility at low pH characteristic of acid mine drainage (AMD). In contrast, (hydr)oxyanion-forming elements including As, Sb, Se, and Mo commonly exhibit greater mobility at circumneutral pH associated with neutral mine drainage (NMD). These differences in mobility largely result from the pH-dependence of mineral precipitation–dissolution and sorption–desorption reactions. Cemented layers of secondary (oxy)hydroxide and (hydroxy)sulfate minerals, referred to as hardpans, may promote attenuation of sulfide-mineral oxidation products within and below the oxidation zone. Hardpans may also limit oxygen ingress and pore-water migration within sulfide tailings deposits. Reduction–oxidation (redox) processes are another important control on metal(loid) mobility within sulfide tailings deposits. Reductive dissolution or transformation of secondary (oxy)hydroxide phases can enhance Fe, Mn, and As mobility within sulfide tailings. Production of H2S via microbial sulfate reduction may promote attenuation of sulfide-oxidation products, including Fe, Zn, Ni, and Tl, via metal-sulfide precipitation. Understanding the dynamics of these interrelated geochemical and mineralogical processes is critical for anticipating and managing water quality associated with sulfide mine tailings.  相似文献   

6.
《Applied Geochemistry》2000,15(2):235-243
Sulfide mineral weathering is a major source of acid generation in mining environments. Oxidation and hydrolysis reactions in soil and geologic material under earth surface conditions causes weathering of reduced sulfide minerals resulting in liberation of weathering products including acid. Pyrite and marcasite are minerals common in mine environments that cause acid generation. Many other sulfide minerals are present in mining environments which may or may not form acid upon weathering. Characterization of complex mineral assemblages containing S compounds is therefore critically important to pre-mine planning and postmine waste characterization. Despite the importance of mineral weathering behavior, little is known about the acid generation characteristics of common sulfide and sulfate minerals. To assess the response of common sulfide and sulfate minerals to oxidizing conditions, 13 minerals were subjected to treatment with 10% H2O2. The resulting leachate was analyzed for pH, electrical conductivity, S and titratable acidity. The sulfide minerals arsenopyrite, pyrite, chalcopyrite, pyrrhotite, marcasite and sphalerite demonstrated significantly elevated levels of titratable acidity and are acid generating in contrast to galena, chalcocite and all the sulfates. The sulfate minerals barite, anhydrite, gypsum, anglesite and jarosite were included in experimentation and were found not to form acid under strongly oxidizing conditions. Remediation strategies for disturbed lands containing reduced S minerals must therefore consider not only the total quantity of sulfide minerals present, but the specific mineralogy of the S compounds.  相似文献   

7.
The aqueous geochemistry of Zn, Cu, Cd, Fe, Mn and As is discussed within the context of an anaerobic treatment wetland in Butte, Montana. The water being treated had a circum-neutral pH with high concentrations of trace metals and sulfate. Reducing conditions in the wetland substrate promoted bacterial sulfate reduction (BSR) and precipitation of dissolved metal as sulfide minerals. ZnS was the most common sulfide phase found, and consisted of framboidal clusters of individual spheres with diameters in the submicron range. Some of the ZnS particles passed through the subsurface flow, anaerobic cells in suspended form. The concentration of "dissolved" trace metals (passing through a 0.45 μm filter) was monitored as a function of H2S concentration, and compared to predicted solubilities based on experimental studies of aqueous metal complexation with dissolved sulfide. Whereas the theoretical predictions produce "U-shaped" solubility curves as a function of H2S, the field data show a flat dependence of metal concentration on H2S. Observed metal concentrations for Zn, Cu and Cd were greater than the predicted values, particularly at low H2S concentration, whereas Mn and As were undersaturated with their respective metal sulfides. Results from this study show that water treatment facilities employing BSR have the potential to mobilize arsenic out of mineral substrates at levels that may exceed regulatory criteria. Dissolved iron was close to equilibrium saturation with amorphous FeS at the higher range of sulfide concentrations observed (>0.1 mmol H2S), but was more likely constrained by goethite at lower H2S levels. Inconsistencies between our field results and theoretical predictions may be due to several problems, including: (i) a lack of understanding of the form, valence, and thermodynamic stability of poorly crystalline metal sulfide precipitates; (ii) the possible influence of metal sulfide colloids imparting an erroneously high "dissolved" metal concentration; (iii) inaccurate or incomplete thermodynamic data for aqueous metal complexes at the conditions of the treatment facility; and (iv) difficulties in accurately measuring low concentrations of dissolved sulfide in the field.  相似文献   

8.
铁氧化物矿物对苯酚和溶解性有机质表面吸附的初步研究   总被引:2,自引:0,他引:2  
文中以铁氧化物矿物对苯酚和溶解性有机质(DOM)的吸附研究为例开展生态矿物学研究。铁氧化物矿物的吸附作用存在多种机制,这些吸附机制发生作用的条件主要取决于溶液化学性质和吸附质的理化性质。批处理实验研究表明,苯酚吸附在酸性微酸性条件下不强,吸附等温线符合Langmuir方程,属于表面分子吸附模型;DOM的吸附强并发生吸附分异,配体交换、憎水键和范氏力等多种模式并存,在酸性中性条件下对DOM在针铁矿上的吸附起着重要贡献。本文实验条件下DOM吸附等温线近于线性,不能采用Langmuir方程拟合,可能原因是DOM浓度较低。矿物表面荷电性对吸附影响显著,例如,当矿物表面净电荷为零(pH=pHpzc)时,矿物表面水化膜减薄甚至消失,苯酚分子、憎水DOM分子或片断都会倾向于在矿物表面上吸附。由于苯酚吸附机制单一,其受到的影响很明显,所以苯酚在pH值7~8范围内出现吸附最大值;由于配体交换作用主要发生在酸性微酸性条件下,所以在本文pH值约7.5的实验条件下,尽管配体交换仍在发生作用,但它不是主要吸附机制,针铁矿对DOM吸附的主要贡献应是憎水键和范氏力作用,此外,DOM吸附等温方程近于线性还可能与此有关。显然,铁矿物表面作用在对有机质含量低而铁矿物含量高的红壤中污染物和DOM的固定与归宿控制中扮演着重要的角色。  相似文献   

9.
The reaction between dissolved sulfide and synthetic iron (oxyhydr)oxide minerals was studied in artificial seawater and 0.1 M NaCl at pH 7.5 and 25°C. Electron transfer between surface-complexed sulfide and solid-phase Fe(III) results in the oxidation of dissolved sulfide to elemental sulfur, and the subsequent dissolution of the surface-reduced Fe. Sulfide oxidation and Fe(II) dissolution kinetics were evaluated for freshly precipitated hydrous ferric oxide (HFO), lepidocrocite, goethite, magnetite, hematite, and Al-substituted lepidocrocite. Reaction kinetics were expressed in terms of an empirical rate equation of the form:
  相似文献   

10.
 Pore water concentration profiles of sediments at a site on the Amazon Fan were investigated and simulated with the numerical model CoTReM (column transport and reaction model) to reveal the biogeochemical processes involved. The pore water profiles for gravity core GeoB 4417-7 showed a distinct sulfate–methane transition zone in which deep sulfate reduction occurs. Only a small sulfide peak could be observed at the reaction zone. Due to high amounts of iron minerals, the produced sulfide is instantaneously precipitated in form of iron sulfides. We present a simulation which starts from a steady state system with respect to pore water profiles for methane and sulfate. Furthermore, sulfide, iron, pH, pE, calcium and total inorganic carbon (TIC) were included in the simulation. The program calculated mineral equilibria to mackinawite, iron sulfides (more stable than mackinawite), iron hydroxides and calcite via saturation indices (SI) by a module incorporating the program PHREEQC (Parkhurst 1995). The measured sulfide and iron profiles are obtained in the simulation output by using a constant SI (=0) for mackinawite and calcite, while a depth dependent SI distribution is applied for the PHREEQC phases “Pyrite” and “Fe(OH)3(a)”, representing a composition and the kinetics of different iron sulfides and iron hydroxides. These SI distributions control the results of sulfide and iron pore water profiles, especially conserving the sulfide profile at the reaction zone during the simulation. The results suggest that phases of iron hydroxides are dissolved, mackinawite is precipitated within, and other iron sulfides are precipitated below the reaction zone. The chemical reactivity of iron hydroxides corresponds to the rate of sulfide production. The system H2O–CO2–CaCO3 is generally successfully maintained during the simulation. Deviations to the measured pH profile suggest that further processes are active which are not included in the simulation yet. Received: 9 November 1998 / Accepted: 26 October 1999  相似文献   

11.
The adsorption of pentachlorophenol (PCP) onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH = 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation, meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmnir equation with the correlation coefficient R〉0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order: hematite 〉 lepidocrocite 〉 goethite 〉 kaolinite 〉 quartz 〉 montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China.  相似文献   

12.
A section through the late Archean Mt. McRae Shale comprising, in ascending order, a lower shale interval (LSI), a banded iron formation (BIF), an upper shale (USI) and a carbonate (C1) has been analyzed for total Fe and Al contents and authigenic Fe present as carbonate, oxide, sulfide and silicate phases. The authigenic mineralogy is controlled by the episodic addition of Fe from hydrothermal activity and removal of Fe by sulfide, relative to rates of clastic sedimentation. The LSI and BIF have mean FeT/Al values of 2 and 5, respectively, that record iron enrichment from hydrothermal sources. Iron was precipitated primarily as siderite accompanied by Fe-rich chlorite from anoxic bottom waters rich in dissolved Fe. Pyrite formation was probably limited by the availability of sulfate, which was present at low concentrations and became rapidly depleted. The USI has generally lower FeT/Al values (0.6-1.3), similar to those found in Paleozoic shales, with the exception of one interval where enrichment may reflect either a weak hydrothermal source or the operation of an iron shuttle. This interval contains authigenic Fe predominantly as pyrite, where high values for DOP (>0.8) indicate the existence of a water column that became rich in dissolved sulfide (euxinic) when sulfate concentrations increased due to a transient or secular increase in ocean/atmosphere oxygenation. High concentrations of dissolved sulfide maintained low concentrations of dissolved Fe, which allowed only minor amounts of Fe to be precipitated as carbonates and silicates. The USI also has elevated concentrations of organic matter that most probably reflect increased productivity and likely limited euxinia to midportions of the water column on the basin margin. The carbonate C1 represents a basinal chemistry where sulfide has been removed and FeT/Al values are ∼1 indicating that hydrothermal activity again produced dissolved Fe-rich bottom waters. Detailed iron speciation of the Mt. McRae Shale can be used to recognize spatial and temporal variations in iron and sulfur inputs to the late Archean Hamersley Basin, just prior to the Paleoproterozoic rise in atmospheric oxygenation, and our refined methods have relevance to all Fe-rich deposits.  相似文献   

13.
The sediment from an acid mine drainage affected reservoir of Guizhou province of China has the iron and arsenic concentration of about 400 and 2.6 g/kg, respectively. Sediment cores were collected, and were used to study the arsenic behavior in the seriously acidified reservoir from the viewpoint of chemical thermodynamics. The limestone neutralization and ferric iron hydrolysis regulated the porewater pH from about 2.9–5.8. The reductive dissolution of As–Fe-rich (hydr)oxides under the mild acidic conditions was the main mechanism for the release of absorbed arsenic into porewater. The maximum concentrations of iron, sulfate and arsenic reached to about 2,800, 9,000 and 1 mg/l, respectively. Arsenic speciation transformation and hydrous ferric oxide (HFO) crystallization enhanced the arsenic mobility in sediment. In addition, the iron sulfide minerals diagenesis could play a role in removing the dissolved arsenic from porewater. The actual distribution of arsenic concentration in porewater was well simulated using the model of surface complexation of arsenic to HFO. Although arsenic concentration in porewater could be above 100 times higher than that of reservoir water, it was not easy to release into the reservoir water through diffusion, because the shallow sediment had relatively strong arsenic adsorption capacity, and new HFO could be generated continuously at the sediment water interface.  相似文献   

14.
利用厌氧微生物分离技术,对深度为1.2 m 的海南红树林湿地沉积物钻孔样品进行了分离培养,共获得11 株 厌氧sulfate-reducing bacteria(SRB) 菌株。经显微观察和16S rDNA序列分析,可归纳为6个属,其中已经报道有芽孢杆菌 属(Bacillus)、弧菌属(Vibrio) 和梭状芽胞杆菌属(Clostridium),另外3个属分别为伯克霍尔德菌属(Burkholderia)、希瓦氏菌属(Shewanella) 和海杆菌属(Marinobacterium)。不同属的细菌对硫酸盐还原的速率最低为14.71%,最高可达 56.78%,并且以上6属11株菌都能将+6价的硫还原生成-2价硫,并与培养基中的Fe2+结合生成黑色FeS沉淀,而这些无定 形FeS沉淀是生成黄铁矿的前体。红树林湿地SRB种群数量随沉积物深度的增加而降低,结合沉积物的地球化学分析测试 结果表明,表层(0 cm) 水界面的沉积物由于处于氧化-还原界面,氧气的周期性输入在一定程度上抑制了SRB的生长;随着 深度增加(10~40 cm),充足的有机质、偏中性的pH值以及厌氧环境的增强,使得SRB种类和数量明显增加;而60 cm以下 沉积物中因TOC含量降低,减少了微生物可利用的碳源,pH值明显降低,Na+和Ca2+离子浓度明显增加,这些因素都抑制了 SRB的生长,使得深部沉积物中SRB的种类和数量显著减少。  相似文献   

15.
石膏在有机物厌氧分解中的固碳效应   总被引:2,自引:0,他引:2  
本文以牛肉膏蛋白胨为厌氧微生物的营养源,研究了石膏对厌氧微生物生化系统中甲烷释放量和有机物矿化的影响.根据溶液中总有机碳(TOC)、总无机碳(TIC)、硫酸根、硫化物、pH值以及气体中CO2,CH4和H2S的释放量的观测,以及固体产物的扫描电镜(SEM)、能谱(EDS)、X-射线衍射(XRD)分析结果,探讨了石膏对抑制...  相似文献   

16.
Four cores of anoxic sediments were collected from the Seine estuary to assess the early diagenesis pathways leading to the formation of previously reactive phase. Pore waters were analyzed for dissolved iron (Fe) and manganese (Mn) and different ligands (e.g., sulfate, chloride, total inorganic carbon). The anoxic zone is present up to the first centimeter depth, in these conditions the reduction of Mn and Fe oxides and SO4 2− was verified. The sulfate reduction was well established with a subsequent carbon mineralization in the NORMAI94 core. The chemical speciation of Mn and Fe in the dissolved and solid phases was determined. For the dissolved phase, thermodynamic calculations were used to characterize and illustrate the importance of carbonate and phosphate phases as sinks for Fe and Mn. The ion activity product (IAP) of Fe and Mn species was compared to the solubility products (Ks) of these species. In the solid phase, the presence of higher concentration of calcium carbonate in the Seine sediments is an important factor controlling Mn cycle. The carbonate-bound Mn can reach more than 75% of the total concentration. This result is confirmed by the use of electron spin resonance (ESR) spectroscopy. The reduction of Fe is closely coupled to the sulfate reduction by the formation of new solid phases such as FeS and FeS2, which can be regarded as temporal sinks for sulfides. These forms were quantified in all cores as acid volatile sulfide (AVS: FeS+ free sulfide) and chromium reducible sulfide (CRS: FeS2+elemental sulfur S0).  相似文献   

17.
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   

18.
The iron mineralization is hosted in carbonate beds of the Garagu Formation (Early Cretaceous) at Gara Mountain, Duhok Governorate, Kurdistan Region, NE Iraq. The Garagu Formation is composed of a series of limestone and siltstone beds with iron-rich beds in the middle part. The iron-rich limestones are iron-rich oolitic grainstone and bioclastic wackestone with hematite and goethite minerals. Geochemical results drawn from this study indicate that the percentage of iron in these beds reaches 19.73 %. Moreover, petrographical investigation of thin and polished sections reveals the presence of different types of fossils, indicating an open marine interior platform depositional environment. Different iron minerals, including hematite, goethite, siderite, pyrite and magnetite, were identified in the sections, and their geneses were related to syngenetic and diagenetic processes. The geochemical distribution of major and trace elements, as well as the V/Ni, V/(V+Ni), V/Cr and Sr/Ba ratios, indicates a reducing environment during the precipitation of carbonate sediments and a subsequent oxidizing condition during the concentration of iron minerals via diagenesis.  相似文献   

19.
Quartz and iron (hydr)oxide are reactive surface phases that are often associated with one another in soils and sediments. Despite the several studies on the coating of quartz with iron oxides, the reactivity of dissolved species (Si) leached from quartz with iron (hydr)oxides has received limited attention. In this study, goethite synthesized on quartz substrates were characterized using field emission scanning electron microscopy, X-ray diffraction (XRD), transmission electron microscopy, and Fourier-transform infrared (FT-IR) spectroscopy. The SEM characterization revealed that bundles of thin parallel aligned goethite rods were formed at pH?>?10, while large pseudohexagonal crystals of twinned goethite needles were synthesized at pH?≤?10 after dehydration and hydration in the alkaline media. TEM analysis showed expanded and distorted lattice spacing of the crystal structure of iron (hydr)oxide due to silica incorporation. The characterization showed that silica increased the crystallite size of the goethite and transformed its acicular texture to a larger, twinned needle structure. FT-IR and XRD analyses revealed band shifts in crystal bonds as well as new bond formations, which indicate the presence of changes in the chemical environment of Fe–O and Si–O bonds. Thus, the presence of sorbed silicates modifies the crystal and lattice structure of goethite.  相似文献   

20.
Acid mine drainage (AMD) is a common pollution in mining areas due to the oxidation of pyrite and associated sulfide minerals at mines, tailings and mine dumps. Elevated metals (Fe, Mn, Al) and metalloids (As, Hg) in AMD would deteriorate the local aquatic environment and influence the water supply. A carbonate basin with deposits of high-arsenic coal in Xingren County, southwestern China, was chosen to study the behavior of As and other chemical constituents along a river receiving AMD. Heavy metals (Fe, Mn) and major ions such as (Ca2+, Mg2+, Cl, SO4 2−) in surface water, and As in sediment and surface water were analyzed. It was found that high concentrations of SO4 2− (1,324–7,560 mg/L) and Fe (369–1,472 mg/L) in surface water were mainly controlled by the interactions between water and rocks such as the oxidation of pyrite in the local coal seams, precipitation and adsorption of iron minerals. Although ubiquitous carbonate minerals in the bedrock and the riverbeds, low pH (<3) water was maintained until 2 km downstream from the AMD source due to the Fe(hydro)oxide minerals coating on the surface of carbonate minerals to restrain the neutralization of acidic water. Moreover, the formation of Fe(hydro)oxide precipitations absorbed As was dominated the attenuation of As from water to sediment. Whereas, the dilution also played an important role in decrease of As in river water.  相似文献   

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