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施氏矿物是酸性矿山废水中广泛存在的次生矿物,其形成和转化受环境pH值、温度和共存离子等条件影响。文中研究了酸性环境中生物成因施氏矿物和吸附了三价砷的生物成因施氏矿物,在不同温度和钾离子浓度条件下的稳定性。结果表明,老化温度的增加促进施氏矿物相的转变:4℃条件下,在15周的老化时间里,无砷及含砷施氏矿物均未发生相转变;而在40℃条件下,经过15周的老化,则无砷和含砷施氏矿物均发生了部分相转变。此外,钾离子浓度变化可以导致施氏矿物老化产物不同:生物成因施氏矿物在0.01mM钾离子条件下老化15周后的转化产物主要为针铁矿,在100mM钾离子条件下老化产物为黄钾铁矾和针铁矿。含As(Ⅲ)施氏矿物在0.01mM钾离子条件下老化15周后没有发生相转变,在100mM钾离子条件下发生了部分相转变,产物为黄钾铁矾。生物成因施氏矿物中的As(Ⅲ)使得矿物在环境中更加稳定。 相似文献
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《吉林大学学报(地球科学版)》2015,(Z1)
矿山酸性废水(Acid mine drainage,AMD)中,含有大量的溶解性Fe、SO2-4和重金属,因此在AMD这种极端特殊的环境中容易形成含铁硫酸盐次生矿物,比如施氏矿物、水铁矿、黄钾铁矾、针铁矿等。据报道,这些次生矿物对AMD河流中重金属的迁移特性起着至关重要的作用[1,2]。因此对AMD河流沉积物中矿物组成特征的调查研究,有助于了解主要矿物对类重金属迁移转化等地球化学过程的影响,为矿区重金属污染修复提供可靠的理论依据[3]。因此本研究结合差示X射线衍射和连续萃取的方法,建立适合典型金属硫化物矿区受AMD影响河流沉积物的矿物学分析方法,在此基础上研究施氏矿物、水铁矿、黄钾铁矾、针铁矿等次生矿物对类重金属环境特性的影响。本研究以广东省韶关市大宝山矿区(24°34′28″N,113°43′42″E)受AMD污染的横石河流域为研究对象,沿河采集了河床卵石沉积物和河流淤泥两种沉积物样品,共采集了18个点位的沉积物样品,包括3个不受AMD影响的支流对照组。样品经过一系列预处理(冷冻干燥、研磨、过筛等)过程,于4℃下保存备用。本研究利用连续萃取的方法结合扫描电镜、X射线衍射、傅立叶红外光谱、拉曼光谱等手段对沉积物样品进行了萃取和表征。结果表明:p H沿着横石河升高,伴随着矿物的组成出现演替现象并且重金属的含量也随之衰减。沉积物中除了含有硅铝酸盐、石英外,主要成分为铁羟基硫酸盐矿物。其中,横石河上游主要矿物组成为黄钾铁矾和施氏矿物,到中下游时以针铁矿和水铁矿为主。类重金属As、Cd、Cu、Pb、Mo、Cr、Ni、Mn、Zn等以吸附和共沉淀的形式伴随着矿物暂时固定于沉积物中。但是,随着河流环境条件的改变,次生矿物将发生相转化并可能将引起重金属的释放。 相似文献
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粤北大宝山酸性矿山废水(AMD)中形成了呈独特梯田状构造的沉积物,其中的次生矿物可以吸持AMD中的重金属离子,对减少矿山环境的重金属污染有重要意义。本文采集了大宝山AMD中呈梯田状构造中的沉积物,利用多种手段分析了其主要矿物组成以及主要次生矿物的表面形貌特征,探究梯田状沉积物的成因。结果表明,梯田状沉积物的次生矿物以针铁矿、施威特曼石、黄钾铁矾为主,含少量石膏、斜方钙沸石等。针铁矿呈针状、球刺状集合体;施威特曼石呈海胆状、鳞片状,粒度为微米级,海胆状施威特曼石与球刺状针铁矿共生;黄钾铁矾呈不规则的球粒状、片状,与施威特曼石共生。研究表明微生物作用可能是形成铁质梯田状构造的关键因素。 相似文献
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酸性矿山排水（AMD）是硫化矿床矿山环境污染防治的难点，因而持续受到国内外学者的关注。众多的学者对矿区AMD中次生矿物进行了研究。为深入了解AMD中次生矿物的形成和演化，为AMD污染防治提供科学依据，笔者对前人不同环境下AMD中的次生矿物类型、次生矿物形成顺序，以及铝相次生矿物的形成、特征、环境危害及意义进行了简要综述。目前与AMD有关的主要次生矿物存在3种类型，即铁相次生矿物、铝相次生矿物和其他相次生矿物，AMD中的pH、Eh和温度对于次生矿物的形成具有控制性的作用。铁、铝相次生矿物具有吸附金属能力，这一性质有助于在一定程度上实现河流的自净化作用。由于AMD形成条件高，矿物相不稳定，目前有关AMD中铝相次生矿物及“酸性白水”的研究成果有限。因此，加强铝相次生矿物以及“酸性白水”的研究，可以更好地解析蒿坪河流域石煤矿区河流酸性磺水–酸性白水的形成演化机制，以及铝相次生矿物吸附重金属的地球化学过程。 相似文献
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以广东大宝山铁龙酸性矿山废水(AMD)为研究对象,采集了7个采样点的赭色沉积物样品。利用X射线荧光光谱(XRF)、傅里叶变换红外光谱(FTIR)、X射线粉晶衍射(XRD)和场发射扫描电镜/能谱分析(FESEM/EDS),对AMD中赭色沉积物的矿物相及形貌进行鉴定。现场测定采样点水体物理化学参数(pH/Eh),探讨不同物理化学条件对含铁次生矿物相的影响。结果表明,大宝山铁龙AMD中赭色沉积物的含铁次生矿物主要有施威特曼石、黄钾铁矾、针铁矿、水铁矿等,此外沉积物中还含有七水铁矾、叶绿矾、四水白铁矾、针绿矾、纤铁矾、锡铁山石及羟铝矾等可溶性硫酸盐。施威特曼石具有带骨针棒状、海胆状形貌,针铁矿常呈针状及肾状集合体产出,黄钾铁矾呈六方板状,施威特曼石常可与黄钾铁矾或者针铁矿共生。赭色含铁次生矿物能在AMD较大范围的pH条件下存在,但倾向于Eh高的环境。当pH值增大时,施威特曼石有转变为针铁矿的趋势,并且针铁矿能保存施威特曼石的形貌特征。 相似文献
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极端酸性环境下形成的施威特曼石（schwertmannite）及其环境学意义 总被引：5，自引：0，他引：5
施威特曼石(schwertmannite)是近年来发现存在于含SO42-丰富的极端酸性环境下的一种次生羟基硫酸高铁矿物,其结晶度较差,形态特殊,表面基团活性强,对其存在环境中有毒重(类)金属元素的迁移与钝化有重要影响。本文详细地介绍了施威特曼石的形成、组成结构、稳定性能、溶解度及其与重(类)金属元素的相互作用等方面的研究进展,并对其在地下水除砷中的应用前景进行了讨论。 相似文献
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羟基氧化铁(FeOOH)广泛存在于土壤、水体沉积物和矿山废水等环境介质中,通常以针铁矿、四方纤铁矿和纤铁矿等多种同质多像体形式存在.羟基氧化铁因具有稳定的化学性质、较高的比表面积和细微的颗粒结构,在重金属治理中被日益重视.由于矿物的环境功能与所形成矿物的性质如矿相、颗粒形貌及大小和结构界面特性密切相关,而矿物的这些性质又与其合成方法、条件密不可分,故本文介绍了羟基氧化铁的种类、结构组成、矿相稳定性及转化,重点对羟基氧化铁形成、制备方法或途径(水解沉淀、化学氧化、生物氧化与生物矿化和凝胶网格法等)及反应物和反应条件(铁盐种类、沉淀剂、pH值、温度、阴阳离子调节剂和表面活性剂等)对矿物产物性质的影响进行了综述,同时,对不同晶型羟基氧化铁在吸附去除重金属Cr(Ⅵ)上的作用的相关研究进行了概述. 相似文献
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施氏矿物吸附Cu2+及氧化亚铁硫杆菌的实验研究 总被引：8，自引：1，他引：7
在金属硫化物的表生氧化过程中,施氏矿物是最常见的一种次生矿物.施氏矿物具有粒度小、比表面积大、表面吸附能高的特点,能够吸附环境流体中的重金属离子和微生物细胞,从而影响重金属元素及微生物的表生地球化学行为.利用化学合成的施氏矿物,开展了施氏矿物吸附Cu2+及氧化亚铁硫杆菌的实验.结果显示:施氏矿物对金属Cu2+及氧化亚铁硫杆菌均有较强的吸附性;施氏矿物对Cu2+的吸附基本符合Langmuir吸附模型,而对氧化亚铁硫的吸附行为不符合Langmuir模型,可用Freundlich模型描述;施氏矿物的存在对流体中微生物的活动性及其地球化学行为有重要影响,可能会降低氧化菌分解金属硫化物的效率. 相似文献
10.
本文以江西武山吴家山铜矿铁帽为研究对象、以合成针铁矿为对照,研究异化铁还原菌Shewanella oneidensis MR-1还原铁帽过程中的矿物物相变化和重金属的释放。使用邻菲啰呤法、ICP-OES、SEM、TEM、XRD和FTIR等分析方法,系统表征了实验体系中矿物物相和溶液化学组成的变化。Fe的释放趋势表明MR-1菌株还原了铁帽中的高铁矿物,并导致铁帽中重金属元素的释放。由于菌体和次生矿物的影响,不同重金属元素的活动性存在差异,Mn和As多以次生矿物形式再次沉淀,而菌体对Zn和Cu、Pb的吸附能力较强。同时发现死菌组中亦有高铁矿物被还原的现象,可能与有机质的还原有关。 相似文献
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Thomas Genty Bruno Bussière Robin Potvin Mostafa Benzaazoua Gérald J. Zagury 《Environmental Earth Sciences》2012,66(8):2387-2401
Oxidation of sulphide mining waste can generate acid mine drainage (AMD) that has the potential to seriously affect the ecosystems. Acid mine drainage is characterised by a high acidity, high concentrations of sulphates and metals. To reduce the environmental impacts due to AMD, neutralisation using limestone drains is an option proposed in the literature and used around the world. The present study focuses on the influence of the carbonate rock mineralogy and their particle size on the neutralising capacity. The tests were performed in two different anoxic conditions: in batch reactors, and in columns having a hydraulic retention time of 15?h. The results showed that the neutralisation capacity of calcite was more important than for dolomitic rock, and smaller particle size gave higher alkalinity production (fine calcite dissolved faster in contact with AMD). A characterization of metal precipitate in sludge and in limestone coating was performed and demonstrated that gypsum, lepidocrocite and goethite were the predominant secondary minerals to be formed. Finally, this study underlines that anoxic limestone drain cannot be used alone to treat high iron concentrated AMD. 相似文献
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一价阳离子和水溶性有机质对生物沥浸中次生铁矿物形成的影响 总被引：2，自引：0，他引：2
在嗜酸性氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)作用下,污泥生物沥浸体系中常会有次生铁矿物形成,这些矿物对污泥脱水和重金属溶出有重要影响。本研究模拟生物沥浸体系,考察了一价阳离子(K+、NH4+、Na+)和污泥DOM(dissolved organic matter)对次生铁矿物形成的影响。结果表明,一价阳离子生成次生黄铁矾类矿物的能力迥异,其中K+的成矾能力最强,120 mmol/L NH4+和80 mmol/L Na+会抑制体系中黄钾铁矾形成。在1.6 mmol/L K+-120 mmol/L NH4+-40 mmol/L Na+和1.6 mmol/L K+-80 mmol/L NH4+-80 mmol/L Na+两个处理所得矿物的结晶度均低于1.6 mmol/L K+-80 mmol/L NH4+-40 mmol/L Na+处理所得矿物的结晶度。另外,在50 mg/L DOM(以DOC计)存在的生物氧化体系,Fe2+最大氧化速率为4.96 h-1,比没有DOM存在时降低48.1%,矿物结晶度也明显低于后者。可见,过高的一价阳离子和DOM含量会影响A.ferrooxidans菌生理生化活性,降低Fe2+氧化速率,继而影响Fe3+供应,使微环境中的黄铁矾形成动力发生改变,最终在一定程度上影响了次生铁矿物的形成。 相似文献
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Solute transport and chemical neutralization (pH 3 to 7) within a shallow heterogeneous aquifer producing acid mine drainage (AMD) are examined at an abandoned surface coal mine in West Virginia. The aquifer is undergoing partial neutralization by mixing with alkalinity from a leaking sludge disposal pond, extending in preferential zones controlled by aquifer heterogeneity. Hydraulic heads interpolated from wells indicate leakage from a central alkaline (pH 7.1, 0.72 meq/L alkalinity) sludge pond is a principal source of recharge. Chemically-conservative sodium, added to AMD during treatment and leaked into the aquifer with the sludge, develops a dispersion plume over a restricted portion of the aquifer that correlates with pH, hydraulic head, and dissolved metals distributions. Concentrations of aluminum, iron, sulfate and acidity display higher concentrations downgradient from the pond as sludge alkalinity is consumed along flow paths. Before reaching springs, most dissolved iron is oxidized and hydrolyzed, likely precipitating in the aquifer as a ferric hydroxide or hydroxysulfate phase. The spatial pattern of iron and aluminum concentrations suggests accelerated oxidation caused by gas transport along the outer slopes of the spoil. Dissolved aluminum concentrations increase with total acidity, suggesting that dissolution of silicate minerals results from acidity released by iron hydrolysis. Neutralization reactions and higher pH are favored in more highly permeable portions of the spoil, where ferrihydrite and aluminum hydroxysulfate minerals (such as basaluminite) are supersaturated. In acid-producing zones at pH < 4.5, jurbanite is near equilibrium and an aluminum-sulfate phase with similar properties may limit aluminum concentrations, but become undersaturated in zones of advancing neutralization. At this particular site, ferrous iron produced by pyrite oxidation is almost completely oxidized over short transport distances, allowing hydrolysis of iron and aluminum should sufficient alkalinity be added to these acid waters. 相似文献
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Solute transport and chemical neutralization (pH 3 to 7) within a shallow heterogeneous aquifer producing acid mine drainage (AMD) are examined at an abandoned surface coal mine in West Virginia. The aquifer is undergoing partial neutralization by mixing with alkalinity from a leaking sludge disposal pond, extending in preferential zones controlled by aquifer heterogeneity. Hydraulic heads interpolated from wells indicate leakage from a central alkaline (pH 7.1, 0.72 meq/L alkalinity) sludge pond is a principal source of recharge. Chemically-conservative sodium, added to AMD during treatment and leaked into the aquifer with the sludge, develops a dispersion plume over a restricted portion of the aquifer that correlates with pH, hydraulic head, and dissolved metals distributions. Concentrations of aluminum, iron, sulfate and acidity display higher concentrations downgradient from the pond as sludge alkalinity is consumed along flow paths. Before reaching springs, most dissolved iron is oxidized and hydrolyzed, likely precipitating in the aquifer as a ferric hydroxide or hydroxysulfate phase. The spatial pattern of iron and aluminum concentrations suggests accelerated oxidation caused by gas transport along the outer slopes of the spoil. Dissolved aluminum concentrations increase with total acidity, suggesting that dissolution of silicate minerals results from acidity released by iron hydrolysis. Neutralization reactions and higher pH are favored in more highly permeable portions of the spoil, where ferrihydrite and aluminum hydroxysulfate minerals (such as basaluminite) are supersaturated. In acid-producing zones at pH < 4.5, jurbanite is near equilibrium and an aluminum-sulfate phase with similar properties may limit aluminum concentrations, but become undersaturated in zones of advancing neutralization. At this particular site, ferrous iron produced by pyrite oxidation is almost completely oxidized over short transport distances, allowing hydrolysis of iron and aluminum should sufficient alkalinity be added to these acid waters. 相似文献
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The extraction of mineral resources requires access through underground workings, or open pit operations, or through drillholes for solution mining. Additionally, mineral processing can generate large quantities of waste, including mill tailings, waste rock and refinery wastes, heap leach pads, and slag. Thus, through mining and mineral processing activities, large surface areas of sulfide minerals can be exposed to oxygen, water, and microbes, resulting in accelerated oxidation of sulfide and other minerals and the potential for the generation of low-quality drainage. The oxidation of sulfide minerals in mine wastes is accelerated by microbial catalysis of the oxidation of aqueous ferrous iron and sulfide. These reactions, particularly when combined with evaporation, can lead to extremely acidic drainage and very high concentrations of dissolved constituents. Although acid mine drainage is the most prevalent and damaging environmental concern associated with mining activities, generation of saline, basic and neutral drainage containing elevated concentrations of dissolved metals, non-metals, and metalloids has recently been recognized as a potential environmental concern. Acid neutralization reactions through the dissolution of carbonate, hydroxide, and silicate minerals and formation of secondary aluminum and ferric hydroxide phases can moderate the effects of acid generation and enhance the formation of secondary hydrated iron and aluminum minerals which may lessen the concentration of dissolved metals. Numerical models provide powerful tools for assessing impacts of these reactions on water quality. 相似文献
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嗜酸性氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)能够在低pH值条件下,迅速将Fe2+氧化并产生大量次生羟基硫酸铁沉淀,从而除去水中可溶性Fe2+。这为富含Fe2+的酸性矿山废水(acid mine drainage,AMD)处理提供了新的思路。本文从晶种刺激和阳离子诱导两个方面,分别研究了固定化载体(硅藻土、石英砂)和具有强诱导能力的成矾离子(K+)对微生物转化酸性体系中Fe2+成次生矿物的影响。结果表明,3种材料均有明显促进可溶性Fe2+向次生矿物转化的作用,且总铁(TFe)沉淀率与3种材料的添加量呈正相关关系。在起始Fe2+浓度为160mmol/L,硅藻土、石英砂和钾离子最大添加量分别为10 g、10 g和80 mmol/L时,经过72 h反应后,TFe沉淀率分别比对照增加了8%、24%和20%。矿物中的Fe、K和S元素含量与溶液中的起始K+浓度有非常密切的关系,随着K+浓度的增大,矿物中的K和S含量逐渐增加,而Fe含量则相应减少。 相似文献
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The Mars Global Surveyor, Mars Exploration Rover, and Mars Express missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major recent mission findings are the presence of jarosite (a ferric sulfate salt), which requires formation from an acid-sulfate brine, and the occurrence of hematite and goethite on Mars. Recent ferric iron models have largely focused on 25 °C, which is a major limitation for models exploring the geochemical history of cold bodies such as Mars. Until recently, our work on low-temperature iron-bearing brines involved ferrous but not ferric iron, also obviously a limitation. The objectives of this work were to (1) add ferric iron chemistry to an existing ferrous iron model (FREZCHEM), (2) extend this ferrous/ferric iron geochemical model to lower temperatures (<0 °C), and (3) use the reformulated model to explore ferrous/ferric iron chemistries on Mars.The FREZCHEM model is an equilibrium chemical thermodynamic model parameterized for concentrated electrolyte solutions using the Pitzer approach for the temperature range from <−70 to 25 °C and the pressure range from 1 to 1000 bars. Ferric chloride and sulfate mineral parameterizations were based, in part, on experimental data. Ferric oxide/hydroxide mineral parameterizations were based exclusively on Gibbs free energy and enthalpy data. New iron parameterizations added 23 new ferrous/ferric minerals to the model for this Na-K-Mg-Ca-Fe(II)-Fe(III)-H-Cl-SO4-NO3-OH-HCO3-CO3-CO2-O2-CH4-H2O system.The model was used to develop paragenetic sequences for Rio Tinto waters on Earth and a hypothetical Martian brine derived from acid weathering of basaltic minerals. In general, model simulations were in agreement with field evidence on Earth and Mars in predicting precipitation of stable iron minerals such as jarosites, goethite, and hematite. In addition, paragenetic simulations for Mars suggest that other iron minerals such as lepidocrocite, schwertmannite, ferricopiapite, copiapite, and bilinite may also be present on the surface of Mars. Evaporation or freezing of the Martian brine led to similar mineral precipitates. However, in freezing, compared to evaporation, the following key differences were found: (1) magnesium sulfates had higher hydration states; (2) there was greater total aqueous sulfate (SO4T = SO4 + HSO4) removal; and (3) there was a significantly higher aqueous Cl/SO4T ratio in the residual Na-Mg-Cl brine. Given the similarities of model results to observations, alternating dry/wet and freeze/thaw cycles and brine migration could have played major roles in vug formation, Cl stratification, and hematite concretion formation on Mars. 相似文献
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铁细菌培养过程中低分子有机酸钠盐对含硫酸根铁矿物形成的影响 总被引：1，自引：0，他引：1
普遍存在环境中的低分子有机酸盐对氧化亚铁硫杆菌的矿化产物(施氏矿和黄钾铁矾等铁矿物)会产生影响,从而导致环境中有毒重金属迁移转化发生变化。本文探讨了低分子有机酸钠盐对铁细菌HX3成长过程中代谢产物铁矿物的影响,并利用XRD、FTIR、FESEM和EDS对形成的铁矿物进行了表征与分析。研究结果表明,低浓度低分子有机酸钠盐的加入对细菌氧化Fe~(2+)的影响不明显,但可加速黄钾铁矾的形成;苹果酸钠的加入较柠檬酸钠和草酸钠更利于施氏矿向黄钾铁矾转变。高浓度低分子有机酸钠盐(苹果酸钠、柠檬酸钠和草酸钠依次为20、40和40mmol/L)的加入对细菌培养过程中Fe~(2+)的氧化有抑制作用;抑制影响从大到小的顺序为:苹果酸钠柠檬酸钠草酸钠。该研究结果可为含氧化亚铁硫杆菌等铁细菌的酸性矿山废水中铁矿物的形成转化和生物矿化机理提供理论参考。 相似文献