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1.
王红梅  刘烁  刘邓 《地球科学》2015,40(2):305-316
选取酸性矿坑水环境中常见的次生含铁硫酸盐矿物———黄钾铁矾[KFe3(SO4)2(OH)6]为研究对象,用硫酸盐还原菌 Desulfovibriovulgaris 和异化铁还原菌Shewanellaputrefaciens CN32对其进行还原实验,探讨作为重金属治理潜在材料的 黄钾铁矾的微生物稳定性.实验采用非增长型培养基,在中性、厌氧、30℃的条件下进行.采用湿化学方法测量水溶液及还原产 生的总Fe2+ ,利用X射线衍射(X-raydiffraction,简称XRD)来分析反应后残余固体物质的矿物组成,用扫描电镜(scanning electronicmicroscopy,简称SEM)观察固体残余物的形貌特征.结果表明,没有微生物的参与,黄钾铁矾的稳定性较好.异化铁 还原菌S.putrefaciens CN32和硫酸还原菌D .vulgaris 在营养极其匮乏的中性厌氧条件下均能还原黄钾铁矾晶格中的 Fe3+ ,显示出黄钾铁矾被微生物还原的可能性.S.putrefaciens CN32还原黄钾铁矾晶格中Fe3+ 的最大还原速率和最终Fe3+ 还原率分别为0.001mmol·L-1·h-1和0.37%.与S.putrefaciens CN32不同,D .vulgaris 对黄钾铁矾的还原能力较强,不 含有电子穿梭体(Anthraquinone-2,6-disulfonate,简称AQDS)的实验体系中Fe3+ 的最大还原速率和最终Fe3+ 还原率分别为 0.017mmol·L-1·h-1和16.80%,而添加了AQDS的实验体系的则分别达到了0.026mmol·L-1·h-1和24.30%,这可能与 黄钾铁矾中含有SO42- 有关.D .vulgaris 优先还原黄钾铁矾晶格中的SO42- 产生的H2S是强还原剂,也可促进Fe3+ 的还原, 微生物以及H2S的双重作用可能是导致D .vulgaris 体系中Fe3+ 还原率较高的原因.XRD分析表明,黄钾铁矾经过S.putrefaciens CN32的作用,物相没有发生变化;而经过D .vulgaris 作用后,黄钾铁矾的特征峰消失,固相残余物中出现了菱铁 矿(FeCO3)、蓝铁矿[Fe3(PO4)2·8H2O]等次生矿物.由于培养基中没有添加任何的磷酸盐,因此蓝铁矿的出现可能是由于培 养基中添加的少量酵母浸膏降解后产生的磷酸根与D .vulgaris 还原黄钾铁矾产生的Fe2+ 相互作用的结果.这些认识对深入 理解地球表层铁的生物地球化学循环具有重要意义,为矿山环境重金属的污染治理提供了实验依据.   相似文献   
2.
Autoclaves are closed vessels in which liquids can be heated above their ‘normal' boiling points. As a consequence the pressure will rise. This equipment has permitted a variety of processes like the syntheses of organics and the leaching of metal ores. Pressure technologies can be used for accelerating reactions, for specific syntheses or they offer an environmental or economical alternative for existing processes. Wet pressure oxidation of sewage sludge, an organic waste product, has become a proven technology. If less oxygen is added than stoichiometrically required for a complete oxidation, cellulose will break down by a different reaction mechanism, releasing electrons. Under these circumstances reduction of inorganic compounds is possible.  相似文献   
3.
黄钾铁矾是干旱—半干旱地区硫化物矿床氧化带中一种常见表生含钾硫酸盐矿物,对其进行~(40)Ar/~(39)Ar年代学研究,不仅可以直接限定硫化物矿床次生富集的时间,还可以为区域地貌形成演化和古气候演变等重大地质事件提供关键的年代学信息。本文对中国新疆吐哈盆地硫磺山铜多金属矿床氧化带中三个表生黄钾铁矾样品进行了~(40)Ar/~(39)Ar定年,第一次获得了始新世的风化矿物的年龄。结合已发表的年龄数据显示:在吐哈盆地,海拔较高的矿床氧化带剖面(如硫磺山矿床)记录了基岩的持续和较完整的区域风化事件,这些老的风化年龄的存在证明了剥蚀并不是均匀的,即其地貌演化遵循的是斜坡后退模型。对于吐哈盆地的古气候,这些表生硫酸盐的年龄表明:始新世以来吐哈盆地曾多次出现过有利于化学风化和硫化物矿床次生富集的干旱—半干旱气候,且主要集中在以下几个时期:27.7~23.3 Ma、16.4~14.7 Ma、11~7.8 Ma,之后气候开始向极端干旱气候转变,4.1~3.3 Ma之后吐哈盆地可能已经流行大规模的极端干旱气候。  相似文献   
4.
At Brisbane Airport, the construction of a diversion channel for Kedron Brook exposed a former beach, low cliff and sand spit, which, with their associated sediments and acid sulfate soils, demonstrate a postglacial high sea-level 1.3 – 1.4 m above present mean sea-level. The beach appears to date from 4000 to 5000 y BP. It varies in level where it lies above soft ground; these variations, and sag depressions that follow buried streamlines, indicate sediment consolidation since withdrawal of the sea from the former shore. Most of the area consists of former estuarine deposits, mangrove and saline marshes, and stranded tidal flats on which acid sulfate soils are widely developed. The modern landforms mostly reproduce subsurface features, to the extent that the surface relief replicates the landscape transgressed by the sea 7000 years ago. A small rise of sea-level possibly to +0.65 m occurred about 2000 – 3000 years ago. Foredunes near the present shore that are related to a slightly lower level 1000 – 500 years ago (?0.25 m) are currently subject to wave erosion.  相似文献   
5.
A method for the prediction of Gibbs free energies of formation for minerals belonging to the alunite family is proposed, based on an empirical parameter ΔGO= Mz+(c) characterizing the oxygen affinity of the cation Mz+. The Gibbs free energy of formation from constituent oxides is considered as the sum of the products of the molar fraction of an oxygen atom bound to any two cations, multiplied by the difference of oxygen affinity ΔGO= Mz+(c) between any two consecutive cations. The ΔGO= Mz+(c) value, using a weighing scheme involving the electronegativity of a cation in a specific site (12-fold coordination site, octahedral and tetrahedral) is assumed to be constant. It can be calculated by minimizing the difference between experimental Gibbs free energies (determined from solubility measurements) and calculated Gibbs free energies of formation from constituent oxides. Results indicate that this prediction method gives values within 0.5% of the experimentally measured values. The relationships between ΔGO= Mz+(alunite) corresponding to the electronegativity of a cation in either dodecahedral sites, octahedral sites or tetrahedral sites and known as ΔGO= Mz+(aq) were determined, thereby allowing the prediction of the electronegativity of rare earth metal ions and trivalent ions in dodecahedral sites and highly charged ions in tetrahedral sites. This allows the prediction of Gibbs free energies of formation of any minerals of the alunite supergroup (bearing various ions located in the dodecahedral and tetrahedral sites). Examples are given for hydronium jarosite and hindsalite, and the results appear excellent when compared to experimental values.  相似文献   
6.
Abstract. K-Ar age determinations were carried out on vein- and rock-forming minerals from five vein-type tin-polymetallic ore deposits of the Oruro mining district in the central part of the Bolivian tin belt. The sericite from vein selvedges and an altered host rock provides good estimates of the ages of hypogene mineralization, and supergene alunite and jarosite provide ages for erosional and weathering episodes. It is concluded that hypogene mineralization in the Oruro mining district took place during the early to middle Miocene: 15.8±0.8 Ma at San José, 20.1±l.l Ma at Morococala, 20.5±1.0 Ma at Avicaya, and 19.6±1.0 Ma at Llallagua. Fine grained supergene alunite (δ34S = -10.1 960) and jarosite yield K-Ar ages of 6.7±0.7 Ma at Avicaya and 3.9±0.7 Ma at Bolivar, respectively, suggesting that erosion and chemical weathering were active at those times.  相似文献   
7.
黄钾铁矾的形成条件研究及其环境意义   总被引:14,自引:0,他引:14  
黄钾铁矾的化学合成实验表明,调整合适的pH值及介质浓度,常温常压下可以实现黄钾铁矾的快速形成。影响黄钾铁矾形成的主要因素包括pH值、温度及硫酸铁介质的浓度。常温下,当pH值在2.60~3.10时,24h内即有黄钾铁矾沉淀出现,2d内则有大量黄钾铁矾生成;在90℃左右时,形成黄钾铁矾的溶液pH值范围增大至1.20~3.10,而且在该范围内,pH值越大越利于黄钾铁矾的形成。高硫酸铁浓度有利于黄钾铁矾的形成,硫酸铁浓度较高(大于0.05M)时,形成较纯的黄钾铁矾矿物;而低浓度时,生成的黄钾铁矾常常含有水绿矾及胶体状的红色无定形羟基硫酸铁杂质。黄钾铁矾的沉淀过程可以用来治理矿山及工业废水,去除其中的S、Fe及As、Cr、Hg、Pb等有毒有害元素。常温常压下黄钾铁矾快速形成的实现为在产生酸性废水的矿山废石堆上形成黄钾铁矾类矿物胶体隔离防渗层提供了良好的潜在应用前景。  相似文献   
8.
微生物矿化成因的铁硫酸盐矿物表面特征初探   总被引:12,自引:1,他引:12  
研究表明,生物一矿物相互作用是地球表层系统演化的重要地质营力之一。微生物与矿物岩石之间进行着活跃的物质交换,微生物通过营造微观地球化学环境和提供吸附、成核中心影响着矿物的溶解和结晶,其中生物一矿物界面是物质交换和化学反应最为活跃的场所,矿物表界面记录着丰富的微生物作用信息。在综述前人微生物一矿物相互作用界面研究的基础上,利用气体吸附技术,对比分析了微生物矿化成因和无机合成含水铁硫酸盐矿物的表面积、表面分形和表面吸附能特征,初步讨论了微生物矿化成因铁硫酸盐矿物的表面特征和控制机理。  相似文献   
9.
黄钾铁矾是酸性矿山废水(AMD) 中常见的次生矿物,能有效吸附AMD中Cu、Pb、Zn、Gd、As等重金属元素。不 同条件下形成的黄钾铁矾微形貌不同,其吸附能力也不同。文章通过化学法和微生物法合成了黄钾铁矾,并在粤北大宝山 矿酸性矿山废水中采集了含黄钾铁矾的泥样。利用扫描电镜-能谱分析(SEM) 和X光衍射(XRD),对三种不同条件下形 成的黄钾铁矾进行鉴定和微形貌特征观察,并分析黄钾铁矾的形成条件。结果表明,常温条件下,pH值2.0~2.5时能够化 学合成黄钾铁矾,其晶体粒径约2~10 μm,且晶形呈板状;而在65℃时,可在pH2.0~3.0之间化学合成黄钾铁矾,但晶形 差。微生物法合成黄钾铁矾pH范围是2.0~5.0,其晶形完好,呈菱面体且晶体大小比较均匀,而约为2~4 μm。酸性矿山废 水中的黄钾铁矾形成的pH值为2.5~3.5,晶形为菱面体形,单个晶体大小多为1~2 μm。根据其形成条件和微形貌特征,文 章推测酸性矿山废水中形成的黄钾铁矾可能是微生物成因。  相似文献   
10.
Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO4 solutions. Single-crystal XRD refinement with R1=0.0232 for the unique observed reflections (|Fo| > 4F) and wR2=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, Vo=160.11(4) cm3, and fractional positions for all atoms except the H in the H3O groups. The chemical composition of this sample is described by the formula (H3O)0.91Fe2.91(SO4)2[(OH)5.64(H2O)0.18]. The enthalpy of formation (Hof) is –3694.5 ± 4.6 kJ mol–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H2O, and -MgSO4. The entropy at standard temperature and pressure (So) is 438.9±0.7 J mol–1 K–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (Cp) data between 273 and 400 K were fitted to a Maier-Kelley polynomial Cp(T in K)=280.6 + 0.6149T–3199700T–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol–1. Speciation and activity calculations for Fe(III)–SO4 solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the Cp data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in Cp, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H3O)Fe3(SO4)2(OH)6 was estimated: Gof= –3226.4 ± 4.6 kJ mol–1, Hof=–3770.2 ± 4.6 kJ mol–1, So=448.2 ± 0.7 J mol–1 K–1, Cp (T in K)=287.2 + 0.6281T–3286000T–2 (between 273 and 400 K).  相似文献   
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