Acidithiobacillus ferrooxidans氧化分解毒砂的次生产物研究

毒砂是常见的含砷硫化物矿物。在金属硫化物矿山环境中,含毒砂矿石和尾矿的风化会导致严重的重金属污染,在其风化过程中,微生物能够显著促进毒砂的氧化分解。本文实验研究了Acidithiobacillus ferrooxidans氧化分解毒砂矿物的现象,利用X射线衍射和扫描电子显微镜,分析了毒砂微生物氧化作用形成的次生矿物类型,发现毒砂表面存在As含量明显不同的2类次生产物,观察到黄钾铁矾、臭葱石、自然硫和施威特曼石等矿物;借助光电子能谱仪重点分析了微生物作用前后毒砂晶面的表面化学组成,基本查明了Fe、As和S三种元素的价态变化,初步探讨了毒砂表面次生矿物成因和As的化学态转化。     

Pyrite oxidation by Acidithiobacillus ferrooxidans at various concentrations of dissolved oxygen

Pyrite oxidation rates were examined at various concentrations of dissolved oxygen (DO) in the presence of the sulfur and iron oxidizer Acidithiobacillus ferrooxidans. Five different batch experiments were performed at room temperature for 75 days under various DO levels (273, 129, 64.8, 13.2, and ≤ 0.006 μM), containing pyrite grains (particle size 63–250 μm) and a modified 9K nutrient medium at pH 3. The reactors were inoculated with A. ferrooxidans. In all experiments, pH decreased with time and sulfur and iron were released to the solution, indicating pyrite oxidation at all DO levels. Pyrite oxidation rates (ca. 5 × 10^− 10 mol m^− 2 s^− 1 at 273 μM DO) from all experiments showed positive correlation with DO, Fe(III), and bacterial concentration. These rates were significantly slower than rates presented in other published studies, but this is probably due to the significantly greater Fe(III) concentration at lower pH in these previous studies. The results obtained in this study suggest that ferric iron reduction at the pyrite surface is the primarily mechanism for microbial pyrite oxidation in the presence of DO. The results from our study support the indirect mechanism of sulfide oxidation, where A. ferrooxidans oxidizes ferrous iron in the presence of DO, which then oxidizes pyrite.     

氧化亚铁硫杆菌与毒砂相互作用的阶段性及其机理研究

设计了毒砂的生物氧化和化学氧化两组对比实验,并对反应35d的溶液化学、固相产物成分和矿物表面元素化合态变化进行了分析,以说明氧化亚铁硫杆菌（A．ferrooxidans）与毒砂的相互作用机理。研究发现,毒砂的生物氧化过程随A．ferrooxidans菌生长规律分为三个阶段：（1）反应前7d,生物氧化作用还很弱,以自然氧化反应为主;（2）反应8～21d,生物氧化反应开始发生,细菌进入迟缓生长期;（3）反应22～35d,细菌处于对数生长期,生物氧化作用强烈。由离子浓度变化规律反映,前两个阶段生物氧化速率低于化学氧化,第三阶段起生物氧化速率高于化学氧化。细菌生长受溶液累积的As抑制,A．ferrooxidans菌能促进As和Fe形成砷酸铁沉淀,以降低As的抑制作用。毒砂表面高价态元素的比例随细菌生长和溶液Fe离子浓度的升高而增大,生物氧化第三阶段毒砂表面高价态元素的比例高于化学氧化。氧化过程中毒砂表面覆盖中间氧化产物S^0和As2S3沉积层,对比化学氧化,Aferrooxidans菌能不断把Fe^2＋氧化成Fe^3＋,促进毒砂表面中间产物氧化,并间接氧化毒砂。     

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (δ¹⁸O_H2O) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O₂ and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ± 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate–water oxygen isotope fractionation, ε¹⁸O_SO4–H2O, of ~ 3.8‰ for the anaerobic experiments. Aerobic oxidation produced apparent ε_SO4–H2O values (6.4‰) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O₂ into sulfate. δ³⁴S_SO4 values are ~ 4‰ lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in δ³⁴S_SO4 of ~? 1.5 ± 0.2‰ was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions.     

Selective separation of pyrite from chalcopyrite and arsenopyrite by biomodulation using Acidithiobacillus ferrooxidans

This paper discusses the selective depression of pyrite from chalcopyrite and arsenopyrite by biomodulation using Acidithiobacillus ferrooxidans under natural conditions of pH. The effect of bacteria–mineral interaction on the surface charge of mineral and bacterial cell was studied by microelectrophoresis. Adhesion experiments were conducted to establish the relationship between cell adhesion to specific minerals and the electrokinetic behaviour of the minerals subsequent to interaction with cells. Effect of bacterial interaction on the xanthate-induced flotation of all the minerals was assessed. Adhesion of A. ferrooxidans on pyrite was rapid and tenacious and subsequent to interaction with cells, pyrite remained hydrophilic even in presence of xanthate collector. The collector, on the other hand, was able to render good flotability to chalcopyrite even after interaction with bacterial cells. Copper activated arsenopyrite was able to retain its hydrophobicity in presence of cells due to poor attachment kinetics of cells to the mineral surface. Thus, by suitably conditioning with the cells and collector, it was possible to effectively depress pyrite from chalcopyrite and arsenopyrite.     

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.     

Semiconducting Mineral Photocatalytic Regeneration of Fe2+ Promotes Carbon Dioxide Acquisition by Acidithiobacillus ferrooxidans

Chemoautotrophic organisms have once been excluded from the development of universally applicable CO2 fixation technology due to its low production yields of biomass. In this study, we used Acidithiobacillus ferrooxidans (A.f.) as a model chemoautotrophic microorganism to test the hypothesis that exogenetic photoelectrons from semiconducting mineral photocatalysis can enable the regeneration of Fe2+ that could be then used by A.f. and support its growth. In a simulated electrochemical system, where exogenetic electrons were provided by an electrochemical approach, an accelerated growth rate of A.f. was observed as compared with that in traditional batch cultivation. In a coupled system, where light-irradiated natural rutile provided the primary electron source to feed A.f., the bacterial growth rate as well as the subsequent CO2 fixation rate was demonstrated to be in a light-dependent manner. The sustaining flow of photogenerated electrons from semiconducting mineral to bacteria provided an inexhaustible electron source for chemoautotrophic bacteria growth and CO2 fixation. This finding might contribute to the development of novel effective CO2 fixation technology.     

The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.     

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。     

粤北大宝山多金属矿氧化亚铁硫杆菌对闪锌矿的生物氧化作用初步研究

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)和闪锌矿进行初始pH 2.00和pH 3.00条件下的无菌氧化、含菌含铁氧化和含菌不含铁氧化实验.通过测定实验过程溶液的阳离子、硫酸根离子含量和pH值,实验固体产物的XRD分析和反应前后闪锌矿表面的电镜扫描(SEM)对比分析,获得如下结论:①在不含铁离子的情况下,闪锌矿在pH为2.00的环境下比pH为3.00的环境下更容易被氧化;②氧化亚铁硫杆菌对闪锌矿的氧化有明显的促进作用,其氧化速率比无菌氧化速率要提高10～30倍;③铁离子存在对闪锌矿生物氧化有明显的促进作用,最高可达300倍;④氧化亚铁硫杆菌以及铁离子存在使闪锌矿的生物氧化作用最终溶液pH值明显低于无菌氧化作用的pH值;⑤闪锌矿的微生物氧化的最佳pH条件在2.0～2.4之间.闪锌矿的生物氧化过程中,细菌的直接氧化作用和间接氧化作用可能都是存在的.     

聚铁改性絮凝剂的合成与水处理试验

研究了一种通过用聚铁改性来制备聚硅酸硫酸铁的方法,考察了改性剂中的SiO2质量分数、铁硅比、活化时间、pH值等参数对PFSS(聚硅酸硫酸铁)性能的影响,并进行了水处理实验.结果表明,PFSS制备适宜参数条件为SiO2质量分数为2.0%、铁硅比10:1、活化时间4.Oh,此时其对原水中的浊度和高锰酸盐指数去除率可分别达到98.4%～72.4%,处理后的原水达到饮用水的水质要求.     

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。     

Structure and reactivity of zinc sulfide precipitates formed in the presence of sulfate-reducing bacteria

The biologically mediated formation of metal sulfide precipitates in anoxic sediments represents a potentially important mechanism for the sequestration of toxic metals. Current knowledge of the structure and reactivity of these biogenic metal sulfides is scarce, limiting the ability to effectively assess contaminant sequestration in, and remobilization from, these solids. In this study, SO₄-reducing bacteria (Desulfovibrio sp.) were grown for 5 days in a high-SO₄, minimal metal media amended with Zn at either 30 or 300 micromolar. Zinc speciation in the reactor solids was determined using X-ray absorption spectroscopy, and the results compared to spectra of known metal sulfide mineral phases and freshly formed metal sulfides synthesized through purely chemical processes. Biogenically mediated Zn sulfides showed significantly more short range crystallographic order than the abiotically prepared amorphous precipitates. The presence of dissolved Fe²⁺ at similar concentrations did not affect the nature of the Zn precipitates formed. The biogenic ZnS solids were also more resistant to re-oxidation than the chemical precipitates but more soluble than sphalerite mineral samples. These results suggest that Zn sulfides formed in anaerobic sediments are likely to be more resistant to re-oxidation than would be expected based on dissolution of Fe sulfides and/or sediment acid volatile sulfides.     

钛白副产绿矾生产聚合硫酸铁的研究

本文以钛白副产品绿矾为原料,氧化后,加入聚合剂生产聚合硫酸铁。     

Surface Mineralogy of Oxidized Pyrite by Acidithiobacillus Ferrooxidans

Sulfide oxidation by microbial activities play an important role in the release of heavy metals. An important source of contamination and formation of AMD is the heavy metals convey to soil, rivulet and groundwater. Pyrite is a commonly sulfide minerals in mine wastes, so it is vitally to prove up the microbial oxidation process.     

Acidithiobacillus ferrooxidans ATCC23270与矿物吸附过程的热量变化及不同条件下代谢热的基础研究

用微量热技术研究了不同条件下Acidithiobacillus ferrooxidans ATCC23270(以下简写为A.ferrooxidans ATCC23270)与硫化矿吸附过程的热量变化以及不同细菌浓度、不同的初始pH值及不同的培养条件下细菌的代谢产热情况.研究发现,矿浆浓度0.03 g/mL,细萧浓度1.7×108个/mL的时候细菌与矿物的吸附放热最大.不同条件培养的细菌胞外多聚物的组成不同,与矿物吸附的反应热也不相同,黄铁矿培养细菌胞外多聚物含量最高,反应热也最高,说明细菌胞外多聚物在吸附过程中起重要作用.用微量热法能够很好地反映出细菌生长代谢过程中每个微观时刻的热量变化.对于A.ferrooxidans ATCC23270,最佳的代谢产热条件为:pH值为2.0和2.3,细菌浓度为3.0×108个/mL.不同培养条件下的细菌的生长代谢热不同,2039+FeSO4培养的代谢热最大、放热最快.     

不同生长阶段氧化亚铁硫杆菌的Cu2+吸附研究

通过不同生长阶段的氧化亚铁硫杆菌对Cu2+的吸附实验研究,发现对数期和稳定期的氧化亚铁硫杆菌的Cu2+吸附容量存在一定差别,对数生长期比稳定期的氧化亚铁硫杆菌吸附量略高.同时,Cu2+的吸附量与溶液的pH值之间存在显著的负相关关系,说明在吸附过程中,Cu2+与氧化亚铁硫杆菌的表面存在的化学基团发生了质子交换反应.对数生长期的氧化亚铁硫杆菌和稳定期的氧化亚铁硫杆菌吸附过程均符合Freundlich吸附模型,表明氧化亚铁硫杆菌细胞的表面化学非均质性较强.不同生长阶段细菌的吸附性能差异可能与细胞表面的化学结构存在差异有关.     

Local structure of ferric iron-bearing garnets deduced by IR-spectroscopy

Powder IR absorption spectroscopy has been used to characterise cation substitutions in three garnet solid solutions: grossular–andradite, skiagite–andradite and skiagite–almandine. The wavenumber shift of the highest energy mode associated with tetrahedral vibrations depends on the type of cation occupying the adjacent sites in the structure. The wavenumber shifts exhibit positive deviations from linearity that correlate closely with the variations of the Si–O bond distances for all three garnet solid solutions. The autocorrelation function has been used to determine an effective line width (Δcorr) of the absorption bands over a given spectral region. Non-linear behaviour of Δcorr was found for all three solid solutions. An empirical calibration between Δcorr excess and calorimetric enthalpy of mixing data gives an estimate for the symmetric Margules parameters W_spec^H of the three solid solutions. Comparison with the systematics of aluminosilicate garnets in terms of W_spec^H vs. ΔV², where ΔV represents the difference in molar volume between the end members in a binary system, reveals that such a relationship is not generally applicable to garnet solid solutions with an octahedral cation other than Al.     

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。