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1.
考察了不同贮存和制备条件对铜精矿样品铜含量的影响,得出在包装密封不良时铜含量因氧化而产生的变化结果及其趋势;根据X射线衍射所作的矿相分析结果,利用X射线荧光光谱仪观察样品中铜、铁、硫化学态的变化,探讨了铜精矿氧化反应的机理。样品变质主要是低价硫、铜、铁离子与空气中的水和氧发生氧化反应所致,酸度增高会促使氧化反应加速进行。 相似文献
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C-N-S反应体系是地下水系统中氧化还原敏感组分循环和能量流动的关键系统,但它如何与Fe、Mn循环过程、相关功能微生物代谢路径耦合并控制氧化还原敏感组分的迁移转化却并不清楚。本文在对国内外相关文献进行归纳总结的基础上,把地下水中的氧化还原敏感组分分为氧化富集型和还原富集型,较为系统地梳理了地下水系统C、N、S循环驱动的典型氧化还原敏感组分(主要以U、Cr、Fe、As为例)迁移转化过程,指出了该领域的主要研究热点,包括C-N反应体系中典型氧化还原敏感组分的迁移转化、C-S反应体系中还原富集型组分活化和氧化富集型组分固定机理、典型氧化还原敏感组分之间的相互作用、微生物作用下典型氧化还原敏感组分的转化和富集等,并提出基于代谢路径的C-N-S反应体系及其驱动下地下水典型氧化还原敏感组分转化过程和富集机理,将成为本领域的发展趋势。 相似文献
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氧化亚铁硫杆菌与毒砂相互作用的阶段性及其机理研究 总被引：2，自引：0，他引：2
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。 相似文献
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成矿作用过程中赤铁矿—磁铁矿之间非氧化还原转变 总被引：1，自引：0，他引：1
自然界中铁氧化物的主要存在形式为赤铁矿和磁铁矿,两者之间的相互转变一直是人们关注和研究的热点。磁铁矿和赤铁矿之间的相互转变一直被认为是一个氧化还原反应的结果,反应的发生与一定的氧化剂或还原剂密切相关。然而,近年来一个铁氧化物之间的非氧化还原反应机制被提出,这种非氧化还原反应机制对于认识和了解复杂的成矿作用具有重要的意义。本文阐述了自然界中铁氧化物之间的相互交代结构,对BIF研究和实验学两方面的证据进行了综述,认为这种非氧化还原反应可能存在于很多不同类型的成矿作用过程之中。这种赤铁矿和磁铁矿之间的非氧化还原反应机制具有重要的理论和实际意义:一方面,仅靠地质作用过程中出现磁铁矿或赤铁矿现象不一定就能判别其形成流体的氧化还原状态;另一方面,它可以为勘探含后生赤铁矿的铁矿床提供新的找矿思路,进一步指导深埋在古风化面以下铁矿体的寻找。 相似文献
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不同氧化度碱性水钠锰矿氧化As(Ⅲ)和Cr(Ⅲ) 的动力学特性 总被引：1，自引：0，他引：1
用批量法研究了Mn平均氧化度分别为4.02、3.85和3.70的碱性水钠锰矿对As(Ⅲ)和Cr(Ⅲ)氧化的动力学特性。结果表明,碱性水钠锰矿氧化As(Ⅲ)和Cr(Ⅲ)先经历准一级动力学反应阶段,随后表观速率常数(kobs)逐渐减小至趋近零,达到反应平衡,kobs逐渐减小除了逆反应影响外,还与产物在矿物表面不断积累,钝化反应位点有关。初始反应阶段kobs随氧化度增加而增大,氧化As(Ⅲ)的kobs分别为: 0.095 1、0.039 6和0.007 1 min-1;氧化Cr(Ⅲ)的kobs分别为0.034 2、0.017 8和0.014 8 min-1。氧化As(Ⅲ)的初始反应阶段生成的Mn(Ⅱ)基本保留在矿物表面,对反应位点钝化大,使kobs减小速度快。而Cr(Ⅲ) 氧化初始阶段,Mn(Ⅱ)释放明显滞后于Cr(Ⅵ)释放,但随反应进行逐渐增加,与Cr(Ⅵ)释放量比值接近于反应计量比。故Cr(Ⅲ) 氧化生成Mn(Ⅱ)对位点的钝化远小于As(Ⅲ)氧化,其初始反应阶段后kobs减小速度较慢,且氧化度越高,保持一级动力学的初始反应阶段越长,kobs减小越慢。因此,水钠锰矿的Mn氧化度越高,氧化As(Ⅲ)和Cr(Ⅲ)的反应速率越快,As(Ⅲ)和Cr(Ⅲ)在碱性水钠锰矿表面氧化产物的释放行为是影响其反应动力学特性的重要因素。 相似文献
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天然锰氧化物矿物氧化废水中苯酚的动力学研究 总被引：1，自引：0，他引：1
利用天然锰氧化物矿物在酸性条件下的强氧化性,研究其氧化水中苯酚的动力学,模拟锰氧化物矿物氧化苯酚的反应过程。通过测定初始浓度为100~1000 mg/L,pH值为1~2,温度为293~333 K时不同氧化时间锰氧化物矿物对苯酚的氧化结果,比较伪一级和伪二级反应方程的线性拟合情况;结果表明,该反应动力学曲线用伪二级反应模型拟合时相关系数高于用伪一级反应方程线性的拟合,所以这个反应可用来模拟伪二级反应。根据动力学数据得出Arrhenius反应活化能Ea为11.62 kJ/mol,说明温度对该反应影响不显著,且是一个扩散控制反应。 相似文献
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研究烃类的热化学氧化对分析油气保存条件和探讨深部碳循环机制都具有重要意义。本文以轻烃-MnO2-水体系为例，基于熔融石英毛细硅管和拉曼光谱分析技术的在线观测热液实验技术，对油气藏中常见的轻烃热化学氧化反应的发生温度和变化规律进行了研究。结果表明，轻烃热化学氧化温度随烃类碳数的增大而降低，从丁烷到十三烷，其反应发生温度从125℃降到约100℃,与热化学氧化反应的吉布斯自由能变化顺序一致。表明烃类热化学氧化需要的温度条件并不苛刻，在3000 m以下埋深且含有氧化性地层的沉积盆地中即可发生。实验结果与准噶尔盆地地质实例基本相符，油气充注中心区优先氧化高碳数烃类，远离充注中心缺乏液态烃的井区发生甲烷等轻烃氧化，烃类的热氧化过程受烃类氧化顺序和油气充注时空差异性两大因素制约。 相似文献
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为了考察铁锰氧化物对酚类污染物的氧化降解能力,采用天然以及合成的铁锰氧化物对苯酚的氧化降解进行对比实验研究。土壤中铁锰氧化物样品分别为天然针铁矿及氧化锰,合成铁锰氧化物样品分别为合成针铁矿及软锰矿。结果表明：苯酚与铁锰氧化物发生氧化还原作用时,还可能与土壤中杂质发生吸附等作用;铁锰氧化物还原反应强度随着反应介质pH值的升高而迅速下降;可用零级反应动力学方程拟合铁氧化物还原溶解反应,针铁矿溶解反应的强度与介质的pH值呈负相关关系;天然针铁矿对酚类污染物的氧化降解能力明显高于合成针铁矿,pH值对天然针铁矿溶解反应影响较大;可用一级指数衰减方程拟合锰氧化物还原溶解反应,锰氧化物溶解反应的强度与介质的pH值呈指数衰减关系;pH值对软锰矿还原溶解反应的影响大于对土壤中氧化锰的影响,pH值越小,影响越显著;对比pH值对铁和锰还原作用的影响发现,在pH=6.5时,锰氧化物仍有较强的氧化性能。 相似文献
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试样经碱熔,盐酸提取的钛,在以盐酸、硫酸、磷酸组成的强酸性溶液体系中,利用铝片的强还原性,还原四价钛为三价钛。再用三价铁氧化三价钛为四价钛,过量的三价铁离子与硫氢酸根离子生成血红色络合物,根据此原理测定高含量钛。实验证明,溶液在此强酸性体系中,隔绝空气和控制时间的条件下,其含量范围在0.13%～100%内,测定结果准确度高。 相似文献
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The sphalerite oxidative kinetics under hypergene condition was simulated and studied by means of a mixed flow reactor over a pH range of 1.0 7.8,and at dissolution temperatures from 20 to 55℃,ferric ion concentrations from 1.0×10-5 to 1.0×10-2 mol/L,O 2 flux of 0.5 L/min,and oxidants of ferric ion and O 2.It is indicated that with ferric ion as oxidant,the oxidation rate of sphalerite increases with increasing ferric ion concentration,temperature and decreasing pH value,and under the studied conditions,the dissolution rates of Zn and Cd are approximately identical,with the values of activation energy being 41.75 and 42.51 kJ·mol-1,respectively,suggesting that the oxidation rate of sphalerite is controlled by chemical reactions on mineral surface.However,with O 2 as oxidant,the oxidation mechanism of sphalerite varies with pH value.Oxidation rate decreases with increasing pH value when pH is lower than 5.95,whereas the increase of pH value results in an increase in oxidation rate when pH value is higher than 7.The oxidation rate of sphalerite can be expressed as:R Zn =10 1.1663 [Fe3+] 0 0.154 ·[H+] 0.2659 ·e-41.75/RT or R Cd =10 1.7292 [Fe3+] 0 0.170 ·[H+] 0.2637 ·e-42.51/RT 相似文献
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Wang Ende Shenyang Institute of Gold Technology Shenyang Liaoningand Guan Guangyue Northeast U niversity of Technology Shenyang Liaoniny 《《地质学报》英文版》1994,68(1):31-42
The bacteria used in the experiment are Thiobacillus Ferrooxidans separated from acidic mine water in sulphide deposits. The chemoautotrophic bacteria can act directly on sulphides and accelerate the oxidation of sulphides. The experiment shows that the bacteria, as an important microbial factor of gold's supergenous enrichment within the oxidized zones of sulphide deposits, are helpful to dissolve gold and silver in ferric sulphate. In the bacterial oxidation process, the precipitation of goethite is concerned both with the lower activity of ferric ions and with the existence of carbonates in solution. Meanwhile, the acid-resisting and oxidizing ability of the bacteria will certainly lead up to a microbial way of treating the acidic mine water. 相似文献
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Stephen Lehner 《Geochimica et cosmochimica acta》2008,72(7):1788-1800
Pyrite samples synthesized with As, Co, or Ni impurities and without added impurities were oxidized in batch and mixed flow-through reactors in the presence of 1 mM ferric iron, at pH 2. Six samples from each dopant population were used to provide a statistically robust comparison; two natural samples from Leadville, CO (major impurities Pb, As, Bi, Ag, Zn) and Elba, Italy (Co, As) were also included. In each experiment, three reaction progress variables were monitored: ferric iron, ferrous iron, and sulfate. The pyrite samples with impurities have average oxidation rates that are faster than the undoped samples, with As- and Co-doped pyrite having the highest rates. As, Co, and Ni were released to solution in accordance with their concentrations in the solid samples. As concentrations in the batch reactor experiments tended to remain constant, in contrast to Co and Ni, which increased over time. Initial rates, calculated from the batch reactor experiments, were faster than the steady-state rates calculated from the mixed flow-through reactor experiments. Apparent rates calculated using sulfate were faster than apparent rates calculated using ferric and ferrous iron, reflecting oxidation of ferrous iron in solution by dissolved oxygen. The results imply that impurities in pyrite do contribute to its reactivity, in agreement with studies using electrochemical methods. Oxidation rate differences among pyrite samples with different impurities are probably too small to warrant explicit consideration in environmental modeling applications, but are important to understanding pyrite oxidation mechanisms and semiconducting properties. 相似文献
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The oxidation of carbonate green rust, GR(CO32−), in NaHCO3 solutions at T = 25°C has been investigated through electrochemical techniques, FTIR, XRD, TEM and SEM. The used GR(CO32−) samples were made of either suspended solid in solution or a thin electrochemically formed layer on the surface of an iron disc. Depending on experimental conditions, oxidation occurs, with or without major modifications of the GR(CO32−) structure, suggesting the existence of two pathways: solid-state oxidation (SSO) leading to a ferric oxyhydroxycarbonate as the end product, and a dissolution-oxidation-precipitation (DOP) mechanism leading to ferric oxihydroxides such as lepidocrocite, goethite, or ferrihydrite. A formula was proposed for this ferric oxyhydroxycarbonate, Fe6IIIO(2+x)(OH)(12-2x)(H2O)x(CO3), assuming that the solid-state oxidation reaction is associated to a deprotonation of the water molecules within the interlayers, or of the hydroxyl groups in the Fe(O,H) octahedra layers. The DOP mechanism involves transformation via solution with the occurrence of soluble ferrous-ferric intermediate species. A discussion about factors influencing the oxidation of carbonate green rust is provided hereafter. The ferric oxyhydroxycarbonate can be reduced back to GR(CO32−) by a reverse solid-state reduction reaction. The potentiality for a solid-state redox cycling of iron to occur may be considered. The stability of the ferric oxyhydroxycarbonate towards thermodynamically stable ferric phases, such as goethite and hematite, was also studied. 相似文献
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黑色页岩水岩化学作用实验研究 总被引：2，自引：0，他引：2
水岩作用是黑色页岩化学风化的重要途径,并与岩体矿物组分、工程性质及地质环境有着密切的联系。利用自制的流通实验装置对取自三江县团结电站附近的寒武系清溪组黑色页岩与富含溶解氧去离子水的化学反应进行试验模拟研究,并利用离子分析仪、电感耦合等离子体质谱仪对反应后溶液离子浓度进行分析,使用扫描电子显微镜观察反应前后岩样微观特征,结合岩样渗透系数的变化监测,对岩样中黄铁矿氧化动力学速率以及受黄铁矿氧化影响形成的酸性环境下硅元素释放速率进行计算分析。结果表明,黄铁矿氧化行为使得岩体渗透率降低约70%,在黑色页岩自身矿物化学组分和岩石物理性质的共同影响下,所含黄铁矿氧化速率与纯黄铁矿颗粒的氧化速率非常接近,同时黄铁矿氧化形成的酸性溶液可溶蚀岩体中石英和伊利石,由于两者含量未能精确测定,因此所测得硅元素释放速率仅表示两者溶解的总反应速率。 相似文献
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Thomas D. Brock Susan Cook Sandra Petersen J.L. Mosser 《Geochimica et cosmochimica acta》1976,40(5):493-500
A survey of hot, acid springs in Yellowstone Park has shown that high concentrations of ferrous and ferric iron are often present. Total ionic iron concentrations in different springs ranged from less than 1 ppm to greater than 200 ppm, and up to 50% of the ionic iron was in the ferrous form. Some of these springs also have high concentrations of reduced sulfur species (S2? and S0). Significant populations of the bacterium Sulfolobus, acidocaldarius, an autotrophic organism able to live and oxidize sulfur compounds at low pH and high temperature, were present in most of these springs. The role of this organism in the oxidation of ferrous iron was investigated by incubating natural samples of water and assaying for disappearance of ferrous iron. Controls in which bacterial activity was inhibited by addition of 10% NaCl were also run. Bacterial oxidation of ferrous iron occurred in most but not all of the spring waters. The temperature optimum for oxidation varied from spring to spring, but significant oxidation occurred at temperatures of 80–85°C, but not at 90°C. Thus, 85–90°C is the upper temperature at which bacterial iron oxidation occurs; a similar upper limit has previously been reported for sulfur oxidation in the same kinds of springs. The steady-state concentrations of ferrous and ferric iron are determined by the rate at which these ions move into the spring pools with the ground water (flow rate), by the rate at which ferric iron is reduced to the ferrous state by sulfide, and by the rate of bacterial oxidation. The bacterial oxidation rate is faster than the flow rate, so that the rate of reduction of ferric iron is probably the rate-controlling reaction. In several springs, no decrease in ferrous iron occurred, even though high bacterial populations were present. It was shown that in these springs, ferrous iron oxidation occurred but the ferric iron formed was reduced back to the ferrous state again. These springs were all high in suspended sediment and the reductant was shown to be present in the sediment. X-ray diffraction revealed that the sediment contained three major ingredients, elemental sulfur, natroalunite, and quartz. Chemical analyses showed a small amount of sulfide, too little to reduce the ferric iron. Elemental sulfur itself did not reduce ferric iron but when elemental sulfur was removed from the sediment by CS2 extraction, the activity of the sediment was abolished. It is hypothesized that the sulfide present in the sediment (possibly bound to natroalunite) reacts with elemental sulfur to form a reductant for ferric iron. The results show that bacteria can have a profound influence on the ferrous/ferric ratios of geothermal systems, but that temperature and mineral composition of the water may significantly influence the overall result. 相似文献
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Laboratory study of the clogging process and factors affecting clogging in a tailings dam 总被引：2，自引：0，他引：2
Laboratory simulation of clogging in the Lixi tailings dam (Shaanxi Province, China) is urgently required because clogging
is an important factor affecting the dam stability. This work firstly presents the results of ferrous iron oxidation experiments
using buffer solution. The results indicate that the ferrous iron oxidation follows first order kinetics, and the oxidation
process is strongly dependent on pH, a higher pH resulting in a higher oxidation rate. Furthermore, when the pH exceeds 7.0,
the oxidation rate constant increases significantly. Secondly, a column experiment was carried out under the conditions of
the pH ranging from 6.8 to 7.5 and the natural oxygen supply. Ferrous iron oxidation and precipitation were found to reach
equilibrium under these conditions. After 23 days, the column experiment was stopped when the clogging materials blocked the
column outlet. The clogging materials were found to be a mixture of ferric hydroxide and its converted products, and these
existed in amorphous form with a loose cluster microstructure according to the results of XRD and SEM. 相似文献