施氏矿物吸附Cu2+及氧化亚铁硫杆菌的实验研究

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.     

黄钾铁矾类矿物生成对嗜酸氧化亚铁硫杆菌浸提废旧印刷线路板铜的影响

摘要:研究柱浸条件下黄钾铁矾类矿物生成对嗜酸氧化亚铁硫杆菌浸提废旧印刷线路板金属铜的浸出影响,结果表明:柱浸体系中黄钾铁矾类矿物生成是影响浸铜效率的主要因素;pH值在2.20时可以保持浸出体系中一定的Fe3+量与较高的ORP值;黄钾铁矾类矿物在有细菌作用时生成;加酸维持低pH值(pH2.50)可减少黄钾铁矾类矿物的生成,浸出反应能持续进行。     

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

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。     

Fe(Ⅲ)供应速率对无定型施氏矿物形成的影响

施氏矿物(schwertmannite)已被证实是一种具特异性能的重(类)金属吸附新材料。但在直接由Fe3+或用强氧化剂氧化Fe2+合成该矿物时,常因夹有黄铁矾类物质而降低产品纯度。通过模拟FeSO4-K2SO4-H2O临界成矾体系,发现在嗜酸性氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)作用下存在无定型施氏矿物和晶型黄钾铁矾的合成反应竞争,其中Fe3+供应速率是一个影响铁矿物形成的重要因素,较低的Fe3+供应可以抑制K+的利用,这种变化趋势对无定型施氏矿物合成是有利的。当存在少量K+等成矾导向离子时,可通过合理调低Fe3+供应速率,有利于溶液中Fe3+平缓释放,改善施氏矿物纯度,这为A.ferroxidans菌生物法中直接使用无机盐培养基合成施氏矿物提供了可能。     

广东云浮硫铁矿山氧化亚铁硫杆菌的分离及生长规律研究

从广东云浮硫铁矿坑水中分离得到了氧化亚铁硫杆菌（Acidithiobacillus ferrooxidans）Y1菌株,并对其生长规律进行了初步的研究。发现随着时间的变化,培养基溶液中的Fe^2＋浓度与细菌数量呈明显的负相关,间接证明了A.f菌通过钒化Fe^2＋来获得能量。当溶液中Fe^3＋浓度达到一定程度的时候形成黄钾铁矾沉淀,而溶液的pH值会先变大后变小,维持在2．0～2．5之间。     

酸性矿山废水沉积物中砷形态研究:连续提取法及其条件优化

矿山开采过程中常会将还原条件下稳定的硫化物揭露于地表,在氧气、水和微生物的共同作用下,硫化物发生快速氧化分解,形成酸性矿山排水(AMD),严重污染其流经的水体和土壤。近年的研究发现,当环境条件发生改变时,AMD中会形成多次生矿物如黄钾铁矾、施氏矿、水铁     

不同条件下形成的黄钾铁矾微形貌对比研究

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。     

A.ferrooxidans培养过程中Al/Fe(摩尔比)对铁矿物形成产物的影响

主要研究了磷酸铝(Al PO4)的加入量对氧化亚铁硫杆菌HX3培养液中铁矿物形成的影响,并对相应沉淀产物进行了结构表征分析。结果表明,Al PO4的加入对细菌培养过程中Fe2+的氧化无明显影响,但可促进Fe3+的水解和初始铁矿物相的形成,也可加速黄钾铁矾的转化形成。Al/Fe(摩尔比)为0. 04～1的培养液中主要形成产物为施威特曼石和黄钾铁矾; Al/Fe为0. 4和1时另有磷酸铁矿形成。较高的Al/Fe比值和磷酸根含量有利于磷酸铁矿的形成。     

不同条件下形成的黄钾铁矾微形貌对比研究

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。     

葡聚糖对酸性矿山废水中次生铁矿物形成的影响

采用H2O2氧化Fe2＋并供应4种不同浓度葡聚糖的方法,探讨在H2O2氧化体系中葡聚糖对次生铁矿物形成的影响。结果表明：葡聚糖对次生矿物的形成具有明显的抑制作用;随着葡聚糖浓度的提高,次生矿物内的Fe含量降低,而S含量没有显著变化,且所有处理的K含量均较低;没有葡聚糖处理的次生矿物XRD特征峰与黄钾铁矾吻合,而添加葡聚糖后形成的次生矿物的特征峰与施氏矿物吻合,但是所有处理的次生矿物的结晶度都不高;随着葡聚糖浓度的提高,次生矿物的颗粒尺寸降低,比表面积增加。因此,葡聚糖能够抑制次生矿物的合成,并且阻止次生矿物由施氏矿物向黄钾铁矾的转变。     

Dissolution of jarosite [KFe3(SO4)2(OH)6] at pH 2 and 8: Insights from batch experiments and computational modelling

Jarosite [KFe₃(SO₄)₂(OH)₆] is a mineral that is common in acidic, sulphate-rich environments, such as acid sulphate soils derived from pyrite-bearing sediments, weathering zones of sulphide ore deposits and acid mine or acid rock drainage (ARD/AMD) sites. The structure of jarosite is based on linear tetrahedral-octahedral-tetrahedral (T-O-T) sheets, made up from slightly distorted FeO₆ octahedra and SO₄ tetrahedra. Batch dissolution experiments carried out on synthetic jarosite at pH 2, to mimic environments affected by ARD/AMD, and at pH 8, to simulate ARD/AMD environments recently remediated with slaked lime (Ca(OH)₂), suggest first order dissolution kinetics. Both dissolution reactions are incongruent, as revealed by non-ideal dissolution of the parent solids and, in the case of the pH 8 dissolution, because a secondary goethite precipitate forms on the surface of the dissolving jarosite grains. The pH 2 dissolution yields only aqueous K, Fe, and SO₄. Aqueous, residual solid, and computational modelling of the jarosite structure and surfaces using the GULP and MARVIN codes, respectively, show for the first time that there is selective dissolution of the A- and T-sites, which contain K and SO₄, respectively, relative to Fe, which is located deep within the T-O-T jarosite structure. These results have implications for the chemistry of ARD/AMD waters, and for understanding reaction pathways of ARD/AMD mineral dissolution.     

微生物矿化成因的铁硫酸盐矿物表面特征初探

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。     

酸性矿山废水中生物成因次生高铁矿物的形成及环境工程意义

酸性矿山废水(acid mine drainage,AMD)是一类pH低并含有大量有毒金属元素的废水。AMD及受其影响的环境中次生高铁矿物类型主要包括羟基硫酸高铁矿物(如黄铁矾和施威特曼石等)和一些含水氧化铁矿物(如针铁矿和水铁矿等),而且这些矿物在不同条件下会发生相转变,如施氏矿物向针铁矿或黄铁矾矿物相转化。基于酸性环境中生物成因次生矿物的形成会"自然钝化"或"清除"废水中铁和有毒金属这一现象所获得的启示,提出利用这些矿物作为环境吸附材料去除地下水中砷,不但吸附量大(如施氏矿物对As的吸附可高达120mg/g),而且可直接吸附As(III),还几乎不受地下水中其他元素影响。利用AMD环境中羟基硫酸高铁矿物形成的原理,可将其应用于AMD石灰中和主动处理系统中,构成"强化微生物氧化诱导成矿-石灰中和"的联合主动处理系统,以提高AMD处理效果和降低石灰用量。利用微生物强化氧化与次生矿物晶体不断生长的原理构筑生物渗透性反应墙(PRB)并和石灰石渗透沟渠耦联,形成新型的AMD联合被动处理系统,这将有助于大幅度增加处理系统的寿命和处理效率。此外,文中还探讨了上述生物成因矿物形成在AMD和地下水处理方面应用的优点以及今后需要继续研究的问题。     

Occurrence of jarosite within Quaternary coastal sabkha sediments in Kuwait,Arabian Gulf

X-ray diffractometer analysis and SEM investigation confirmed the occurrence of jarosite and alunogen minerals in the Quaternary siliciclastic sabkha sediments of northern Kuwait within the Bahrah oilfield area, Arabian Gulf. Jarosite is relatively abundant in a near-surface whitish sticky tidal muddy sand layer about 60 cm thick that overlies the ferruginous sandstone of the Oligo-Miocene Ghar Formation. Jarosite occurs as clusters of euhedral pseudo-cubes of about 1 μm in size and as agglomerated nanoglobules of 250 nm in size. A hypogenetic origin related to the reaction of sulfuric acid produced by the oxidation of H₂S associated with hydrocarbon gas seepages with K and Fe leachates is suggested. The restricted occurrence of jarosite within near-surface sabkha sediments may be attributed to limited tidal inundation and prevalence of arid climatic conditions.     

The mechanisms of forming iron-base metal gossan minerals

Laboratory studies of the weathering of sulphide ores have centred around using samples of ore as electrodes and accelerating the weathering processes by passing an electric current. The results of reacting 19 different ore types under varying conditions are compared with data from co-precipitating, Fe and Cu, Fe and Ni, Fe and Zn, Fe and Co, and Fe and Pb, over a pH range from 2 to 11. An electrochemical cell specially designed to fit onto an optical microscope has allowed direct observation of the changes in sulphide mineral grains as they are anodically weathered.These experiments are used to demonstrate that the pH of the environment during the weathering of sulphides to sulphates is the most important parameter in determining the initial gossan minerals that form. Factors that will cause the pH to be high are buffering from gangue and wallrock minerals, low iron content in the sulphide and a high metal to sulphur ratio in the sulphide. A low pH is favoured by the converse, namely a sulphide sufficiently massive to override the buffering effects of the wallrocks and any gangue minerals present, a high iron content in the sulphide and a low metal to sulphur ratio in the sulphide.Two mechanisms of iron hydrolysis dominate the weathering processes where iron is a major metal being released from a sulphide.

1. (1) The high pH process. Where there is sufficient buffering for the pH to remain at or above 7, most of the base metals including ferrous iron will be hydrolysed and pyroaurite type of minerals form for Ni, Zn and Co, while mixed Fe-Cu hydroxycarbonates and hydroxysulphates form for Cu, and mixed iron lead hydrocarbonates form for Pb. The iron is located in these initial compounds as a green rust where it is effectively bound as ferrous hydroxide. Subsequent oxidation of this hydroxide produces no further acid. 4Fe(OH)₂ + O₂ + 2H₂0 → 4Fe(OH)₃

2. (2) The low pH process. Where the buffering is insufficient and the pH is below 7, even though some of the ferrous iron will have precipitated as an equivalent to Fe(OH)₂, the solubility is such that sufficient Fe²⁺ will remain in solution so that further oxidation will produce acid. 4Fe²⁺ + O₂ + 1OH₂O → Fe(OH)₃ + 8H⁺ This acid will bring more of the Fe²⁺ into solution to create more acid and the pH will gradually fall even further, so that the gossan forming environment will be at a pH less than 5 and may be as low as 3. At these low pH values, the base metals are soluble and not prone to co-precipitation or adsorption with the gossan minerals. Only elements present in solution as anions, such as Se, As, Mo and Sb, are likely to be bound into gossans forming at low pH.

The results from weathering tests carried out on gossan minerals formed at higher pH show that these minerals are reasonably stable if treated with solutions that have a pH above 7, but they can break down if treated with a solution of pH 5. Thus they could be expected to be leached by rain water saturated with CO₂.When investigating a likely gossan, all aspects — the iron oxides, the silicates, the carbonates and penetrations into the footwall and hanging wall — should be examined carefully, being ever mindful of the effect that pH would have had during the formation and reworking of the minerals. The composition of gossan minerals, their adsorption properties, the solubilities of metal ions, the mechanisms of Fe precipitation, the co-precipitation of other metals with Fe, the stability of carbonates and the binding of humic materials are all pH dependent in the same way. At high pH, metals are immobilized; at low pH, they tend to be in solution.