硅藻土、石英砂和钾离子促进微生物转化酸性矿山废水中亚铁成次生矿物的研究

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。     

粤北大宝山多金属矿酸性矿山废水中氧化亚铁硫杆菌对黄铁矿的生物氧化作用研究

利用从大宝山尾矿库酸性矿山废水培养得到的氧化亚铁硫杆菌(A.f.菌)和废矿石中的黄铁矿进行不同pH值条件下加菌和不加菌氧化实验。通过测定实验过程溶液的阳离子、硫酸根离子含量和pH值,并通过实验固体产物的XRD分析和反应前后黄铁矿表面的扫描电镜(SEM)对比分析,探讨了大宝山酸性矿山废水中的A.f.菌在不同pH值条件下对黄铁矿的氧化作用。认为:大宝山黄铁矿氧化过程中除了产生Fe离子之外,还产生了Cd、As等毒性离子,黄铁矿在pH值为2.00的环境下比pH值为3.00的环境下更容易被氧化;A.f.菌对黄铁矿的氧化有明显的促进作用,在实验条件的30d内使黄铁矿的表观氧化速率提高2～3倍;黄铁矿的生物氧化作用应该包括非接触的间接氧化作用和接触氧化作用。     

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。     

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。     

酸性矿山废水对合山地下水污染的硫氧同位素示踪

以广西合山煤矿为例,应用硫酸盐硫、氧同位素示踪并量化酸性矿山废水对矿区地下水的污染。合山矿井水表现出高浓度SO2-4和低p H值的酸性矿山废水特征,其硫酸盐硫、氧同位素组成显著富集轻同位素,表明煤矸石中黄铁矿的氧化是其产生的主要机制,反应途径为微生物作用下Fe3+对Fe S2的氧化。利用硫酸盐硫、氧同位素组成并应用三元混合模型计算,结果表明矿区地下水基本都受到酸性矿山废水的入渗影响,其对地下水硫酸盐的贡献比例为16%~52%。硫酸盐硫、氧同位素能够示踪酸性矿山废水对地下水的影响,是示踪与评价矿山开采活动对地下水污染的有效手段。     

天然褐铁矿的光电化学响应及对嗜酸性氧化亚铁硫杆菌生长的影响

通过对比实验研究了天然褐铁矿对嗜酸性氧化亚铁硫杆菌(A.f.)生长的影响.利用X射线衍射分析(XRD)确定实验中所用天然褐铁矿样品的主要物相为针铁矿和赤铁矿,紫外-可见漫反射光谱(UV-Vis DRS)和不同光照条件下的时间电流曲线表明天然褐铁矿在可见光下具有良好的光电化学响应.采用H型装置进行双室体系反应,设置了3组对比实验,结果显示A.f.在有光催化电子传入情况下生长较好,在96 h内细胞浓度增加了12倍,3组实验中Fe2+浓度的变化规律与A.f.的生长趋势相对应.由此揭示了天然褐铁矿促进A.f.生长的机制为:在光照作用下天然褐铁矿能产生光生电子-空穴对,光生空穴被电子供体(抗坏血酸)捕获,分离出的光生电子传入阴极室能够将Fe3+还原为Fe2+,实现Fe2+的电化学再生,提供充足的电子能量来源,促进细菌生长.     

矿山酸性废水的环境影响及防治研究进展

矿山酸性废水(AMD)的环境影响是开采矿山或废弃矿山最严重的环境问题之一。介绍了国内外AMD的产生机理、环境危害、控制观点和治理方法。控制观点包括有源头控制和转移控制：源头控制观点就是要在源头防止AMD的形成和转移;转移控制观点就是要中和治理AMD并从中去除金属。治理方法分主动治理和被动治理两种,治理AMD既可以采用非生物路线（化学机制）,也可以采用生物路线（生物机制）。     

粤北大宝山酸性矿山废水中梯田状沉积物的次生矿物研究

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。     

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。     

江西九瑞矿集区成矿与未成矿中酸性侵入岩年代学、岩石化学、矿物化学特征的异同及地质意义

江西九瑞矿集区主要发育有斑岩型、矽卡岩型及块状硫化物型三种类型的铜多金属矿床,其中斑岩型与矽卡岩型为典型的岩浆热液矿床,块状硫化物型矿床产在五通组砂岩与黄龙组白云岩界面之中,但多数也均位于侵入体附近,通常认为岩浆热液对层状黄铁矿体的叠加作用对其成矿起了重要作用。区内同时发育有大量与成矿岩体岩性相似的未成矿侵入岩,长期以来,一直未能找出成矿侵入岩的判别标志和侵入岩成矿与否的原因。本文对区内岩性为花岗闪长斑岩、石英闪长玢岩的成矿与未成矿侵入岩进行了锆石U-Pb定年、岩石主量元素分析以及造岩矿物电子探针测试工作,结果显示,九瑞地区岩浆活动的时代相对集中,成矿侵入岩的年龄分布于138.2±1.8Ma至148.0±1.0Ma之间,未成矿侵入岩的年龄分布于139.0±1.3Ma至149.6±3.0Ma之间,成矿与未成矿侵入岩的侵位时代基本相同,年龄在误差范围内一致。二者的SiO₂以及其它9种主量元素含量的变化范围都非常接近,或有很大重叠,表明成矿与未成矿侵入岩的主要岩石化学成分基本相同。通过造岩矿物成份计算了岩浆开始固结的温度和侵位压力,成矿侵入岩的平均温度769℃与未成矿侵入岩的平均温度723℃在误差范围内大体一致,但成矿侵入岩的温度变化范围（580~915℃）明显大于未成矿侵入岩（656~796℃）。侵位压力方面,未成矿侵入岩的压力值（平均5.7kbar）显著大于成矿侵入岩（平均1.4kbar）。因此我们认为,成矿与未成矿侵入岩相比,前者经历了更为显著的减压过程,该过程也许对形成岩浆热液矿床非常重要,可能是产生独立热液相的一个主要途径,并且能够在岩体内及围岩中造成大量裂隙,为热液循环提供通道。但是,数据同时显示,并非经历了显著减压过程的侵入岩都能够成矿,最终成矿与否是受到不同阶段多种因素联合控制的,因此显著减压并不是成矿的充要条件,而更可能是前提条件。由已获得的未成矿侵入岩数据来推测,在九瑞地区,侵位压力大于4kbar的中酸性侵入岩,成矿潜力可能较小。由黑云母成份估算的氧逸度显示,成矿侵入岩的氧逸度变化较大并且覆盖了未成矿侵入岩的氧逸度范围,但是未成矿侵入岩的氧逸度均没有超过HM（Fe₃O₄-Fe₂O₃）缓冲线,而成矿侵入岩中有一半左右的数据点高于该缓冲线,表明较高的氧逸度对成矿更为有利,在九瑞地区,氧逸度高于HM（Fe₃O₄-Fe₂O₃）缓冲线的侵入岩,其成矿潜力可能更大。     

Characterization of Kolar gold field mine tailings for cyanide and acid drainage

The gold mining process at Kolar gold field (KGF) mines has generated about 32 million tons of tailings. Gold was extracted from the mined ores using cyanidation technique that involved dissolution of gold in the ore by water soluble alkali metal cyanides (example, sodium cyanide or potassium cyanide). Of the several dumps that received the mine tailings only the Kennedy’s Line dump was active prior to closure of the KGF mines in the year 2000. The Kennedy’s Line dump received sulfide bearing tailings in slurry form that comprised of spent ore and process water bearing soluble alkali metal cyanide. Depending on the pH of the tailing slurry, the free cyanides may exist as aqueous hydrogen cyanide that can escape to the atmosphere as hydrogen cyanide gas or occur as soluble cyanide (CN⁻) ions that can be leached by infiltrating water to the sub-surface environment. Additionally, the presence of pyrite minerals in the Kennedy’s Line dump makes them susceptible to acid drainage. This study examines the potential of gold tailings of Kennedy’s Line dump to release cyanide ions (CN⁻) and acid drainage to the sub-surface environment by performing physico-chemical and leaching tests with tailing samples collected from various depths of the dump, sub-surface soil samples beneath the dump and groundwater samples from vicinity of Kennedy’s Line dump. The chemical mechanisms responsible for the ambient cyanide and pH levels of the tailing dump, sub-surface soil samples and groundwater are also inferred from the laboratory results.     

Impacts of acid mine drainage on a stream in subtropical China during a major flood event

Field and laboratory work was carded out to investigate the chemistry and ecotoxicity of stream water affected by acid mine drainage in a tributary catchment of the Pearl River in subtropical China during a major flood event that corresponded to a return period of 100 years occurred in the study area. The results indicate that stream water was affected by acid mine drainage from the Dabaoshan Mine at least to a distance of 25 km downstream of the mine water discharge point. It appears that sulfide-H^＋ from the waste rock dumps was readily available for discharging and the amount of H^＋ being transported outwards depended on the volume of out-flowing waters. However, there was a lag time for the discharge of the metals. This may be attributed to the slower release of metals, relative to H^＋, because it might take more time for the dissolution of heavy metal-bearing compounds. Fe, Zn and Al were the major metals of potential toxicity contained in the AMD-affected stream water, followed by Mn, Cu, Pb, As, Cd and Ni. Acute toxicity tests show that the AMD-affected stream water at 3.5 km downstream of the discharge point was highly toxic to the test organisms.     

Ephemeral acid mine drainage at the Montalbion silver mine,north Queensland

Sulfide‐rich materials comprising the waste at the abandoned Montalbion silver mine have undergone extensive oxidation prior to and after mining. Weathering has led to the development of an abundant and varied secondary mineral assemblage throughout the waste material. Post‐mining minerals are dominantly metal and/or alkali (hydrous) sulfates, and generally occur as earthy encrustations or floury dustings on the surface of other mineral grains. The variable solubility of these efflorescences combined with the irregular rainfall controls the chemistry of seepage waters emanating from the waste dumps. Irregular rainfall events dissolve the soluble efflorescences that have built up during dry periods, resulting in ‘first‐flush’ acid (pH 2.6–3.8) waters with elevated sulfate, Fe, Cu and Zn contents. Less‐soluble efflorescences, such as anglesite and plumbojarosite, retain Pb in the waste dump. Metal‐rich (Al, Cd, Co, Cu, Fe, Mn, Ni, Zn) acid mine drainage waters enter the local creek system. Oxygenation and hydrolysis of Fe lead to the formation of Fe‐rich precipitates (schwertmannite, goethite, amorphous Fe compounds) that, through adsorption and coprecipitation, preferentially incorporate As, Sb and In. Furthermore, during dry periods, evaporative precipitation of hydrous alkali and metal sulfate efflorescences occurs on the perimeter of stagnant pools. Flushing of the streambed by neutral pH waters during heavy rainfall events dissolves the efflorescences resulting in remobilisation and transport of sulfate and metals (particularly Cd, Zn) downstream. Thus, in areas of seasonal or irregular rainfall, secondary efflorescent minerals present in waste materials or drainage channels have an important influence on the chemistry of surface waters.     

Field assessment of acid mine drainage contamination in surface and ground water

Both sulfate and conductivity are useful indicators of acid mine drainage (AMD) contamination. Unlike pH, they are both extremely sensitive to AMD even where large dilutions have occurred. The advantage of using sulfate to trace AMD is that unlike other ions it is not removed to any great extent by sorption or precipitation processes, being unaffected by fluctuations in pH. These two parameters are also closely associated as would be expected, as conductivity is especially sensitive to sulfate ions. Therefore, as sulfate analysis is difficult in the field, conductivity can be used to predict sulfate concentration in both AMD and contaminated surface waters using regression analysis. Most accurate predictions are achieved by using equations given for specific conductivity ranges or AMD sources. There is also potential to use conductivity to predict approximate concentrations of key metals when the pH of the water is within their respective solubility ranges.     

酸性矿山废水中石灰岩包壳作用研究

研究石灰岩包壳作用有助于深入了解酸性矿山废水(AMD)在富含石灰岩的金属硫化物尾矿中的释放机制。采用AMD滞留浸泡石灰岩颗粒试料的实验方法,研究在酸水饱和条件下石灰岩次生包壳的形成作用。研究表明,AMD的Fe含量是影响石灰岩包壳作用的主因之一。在高Fe浓度(如1 029~1 033 mg/L)的AMD中,石灰岩颗粒表面可依次沉淀富Al相、石膏、纤铁矿(吸附Zn、Cu及As等),发生石灰岩包壳/钝化作用,使溶液维持酸性;而在低Fe浓度(6.71~74.8 mg/L)的AMD中,次生包壳难以生成,石灰岩得以大量溶解释碱并充分中和溶液中的H~+,使溶液达到中性。因此,Fe硫化物含量较高(如Fe含量10.62%、S含量5.70%)的石灰岩尾矿,由于其氧化后可生成高Fe浓度的酸性水而导致石灰岩包壳作用,具有释放AMD(及重金属)的危险,应注意防控。     

Chemistry of acid production in black coal mine washery wastes

Column leaching tests on black coal mine washery wastes were performed, to determine the chemistry of acid generation. Coal mine coarse rejects and tailings were subjected to wet and dry cycle dissolution and subsequently column leached. The rates of iron sulphide oxidation and carbonate mineral dissolution were determined based on the drainage chemistry. The kinetic data from column leach experiments are used to predict the time required to deplete the acid producing and acid consuming minerals in the mine wastes. The acid production in the mine rejects was found to depend upon iron chemistry, carbonate chemistry, diffusion of oxygen, and permeability. The chemistry of the drainage from two different coal mines is compared.     

安徽铜陵狮子山硫化物矿山酸矿水中微生物功能群的研究

从安徽铜陵狮子山硫化物矿山酸矿水溪流获得样品,采用YE、Feo、FeSo、FeTo 4种选择性培养基,利用overlay分离技术,获得7株细菌菌株.利用16S rRNA基因序列同源性分析,与目前已分离得到的酸矿水微生物进行了比较.利用分离菌株16S rRNA基因序列构建系统进化树,结果表明获得的菌株可分为3个功能群:嗜酸性异养菌、嗜酸性自养菌、中度嗜酸性铁氧化细菌.嗜酸性异养菌主要与酸矿水中三价铁的异化还原和寡营养状态的维持有关;嗜酸性自养菌与酸矿水中铁、硫元素的氧化有关,是酸水中的生产者;中度嗜酸性铁氧化细菌能将二价铁氧化成三价铁,并产生难溶性的矿物,可实现酸矿水与酸矿水底泥之间铁元素的动态平衡.     

Geochemical characteristics of acid mine drainage and sediments from coal mines, Shanxi Province, China

In this study, geochemical characteristics of acid mine drainage （AMD） and its sediments from the Malan and Sitai coalmines, Shanxi Province, China, were investigated. Many analytical approaches such as IC, ICP-MS, XRD, XRF, and modeling calculation of hydrogeochemistry using PHREEQCI software were employed. The AMD is characterized by higher concentrations of iron and sulfate, a low pH, and elevated concentrations of a wide variety of heavy metals. The results of modeling calculation by PHREEQCI software demonstrate the metals in AMD are present mainly as Me^n＋ and MeSO4^n-2 species. The sediments of AMD are composed mainly of iron-beating minerals such as goethite and schwertmannite, which are controlled by pH, Fe and SO4^2- concentrations. The schwertmannite mineral has been found for the first time in China.