Biological Oxidation of Sulfide Raw Material Using a Culture of Thiobacillus ferrooxidans under Various Conditions of Leaching

Major parameters of the first stage of leaching of a copper–zinc sulfide product (raw material) by a culture of Thiobacillus ferrooxidans have been studied, including the effects of solid-phase concentration, Fe²⁺ and Fe³⁺ ions, pH, and the intensity of mixing. The first stage of leaching of the sulfide raw material is optimum under the following conditions: pH of the original leaching solution equal to 1.6; Fe³⁺ concentration of the order of 10 g/l; and vigorous mixing of the suspension at solid-phase concentrations of 30–35%. A theoretical substantiation of the observed dependences is proposed.     

Chalcopyrite concentrate leaching with biologically produced ferric sulphate

Biological ferric iron production was combined with ferric sulphate leaching of chalcopyrite concentrate and the effects of pH, Fe3+, temperature and solids concentration on the leaching were studied. The copper leaching rates were similar at pH of 1.0-1.8 and in the presence of 7-90 g L-1 Fe3+ despite massive iron precipitation with 90 g L-1 Fe3+. Increase of the leaching temperature from 50 degrees C to 86 degrees C and solids concentration from 1% to 10% increased the copper leaching rate. Increase in solids concentration from 1% to 10% decreased the copper yields from 80% to 40%. Stepwise addition of ferric iron did not improve the copper yields. CuFeS2, Ag and Cu1.96S potentials indicated the formation of a passivating layer, which consisted of jarosite and sulphur precipitates and which was responsible for the decreased leaching rates.     

Microbial leaching of metals from sulfide minerals

Microorganisms are important in metal recovery from ores, particularly sulfide ores. Copper, zinc, gold, etc. can be recovered from sulfide ores by microbial leaching. Mineral solubilization is achieved both by 'direct (contact) leaching' by bacteria and by 'indirect leaching' by ferric iron (Fe(3+)) that is regenerated from ferrous iron (Fe(2+)) by bacterial oxidation. Thiobacillus ferrooxidans is the most studied organism in microbial leaching, but other iron- or sulfide/sulfur-oxidizing bacteria as well as archaea are potential microbial agents for metal leaching at high temperature or low pH environment. Oxidation of iron or sulfur can be selectively controlled leading to solubilization of desired metals leaving undesired metals (e.g., Fe) behind. Microbial contribution is obvious even in electrochemistry of galvanic interactions between minerals.     

Seasonal cycling of Fe in saltmarsh sediments

This study combines an analysis of porewater chemistry with new, solid phase wet chemical extractions to examine the seasonal cycling of Fe in vegetated and unvegetated (cyanobacterial mat) saltmarsh sediments. Saltmarsh sediments are shown to contain more solid phase reactive Fe than other marine sediments studied so far. From the partitioning and speciation of solid Fe, and solid/soluble reduced S analysis in 10 sediment cores, we have observed that a majority of solid Fe in these sediments is cycled rapidly and completely between oxidized reactive Fe and reduced Fe as pyrite. Vegetated porewaters showed a lower pH and much higher Fe(II) concentrations on average than unvegetated porewaters in the top 10 cm, whereas sulfate, alkalinity, and sulfide concentrations were similar in the two environments. The amorphous Fe(III) oxide fraction showed a high negative correlation to solid and soluble reduced S (r ² = –0.86 and –0.71, respectively) in surface vegetated sediments whereas the crystalline Fe(III) oxide fraction showed a high negative correlation (r ² = –0.96) to sulfide only at depth. Though reactive Fe was observed in unvegetated sediments, no seasonal trend was apparent and the speciation of solid Fe revealed that most of it was reduced. Solid phase and porewater chemistry support the dominant role of the biota (Spartina alterniflora and bacteria) in controlling the reactivity of Fe and suggest that the current definition of solid phase, reactive Fe should be expanded to include crystalline Fe(III) minerals which are available for pyrite formation in saltmarsh sediments. In support of previous saltmarsh studies, we present evidence that the redox cycle of solid Fe is controlled by sulfate reduction and sediment oxidation which respond to both annual cycles (light, temperature) and to short-term, episodic effects such as weather and tides.     

Bioleaching of a Complex Co-Ni-Cu Sulfide Flotation Concentrate by Bacillus megaterium QM B1551 at Neutral pH

Bioleaching of sulfide minerals at neutral pH has been rarely reported. In this study, a bacterium, Bacillus megaterium QM B1551, was isolated from Jinchuan sulfide tailings and used to leach a complex sulfide flotation concentrate for the extraction of Co²⁺, Ni²⁺ and Cu²⁺ at near neutral pH. A total of 38.2% Co, 44.7% Ni and 3.6% Cu were extracted from the sulfide concentrate in 5 days with an initial pH of 6. An enhanced Co²⁺, Ni²⁺ and Cu²⁺ extraction extent was achieved by first bioleaching the concentrate with Bacillus megaterium QM B1551 at 35°C and then followed by chemical leaching with 4 M sulfuric acid at 90°C. As a result, a total of 60.7% Co²⁺, 76.3% Ni²⁺ and 39.8% Cu²⁺ were extracted. On an industrial scale, the profits from the metal recovery by such a combined leaching procedure are optimum if considering the cost-benefit ratio.     

Solid-Phase Products of Bacterial Oxidation of Arsenical Pyrite

Bacterial leaching of an As-containing pyrite concentrate produced acidic (pH < 1) leachates. During the leaching, the bacteria solubilized both As and Fe, and these two elements were distributed in solution-phase and solid-phase products. Jarosite and scorodite were the exclusive crystalline products in precipitate samples from the bacterial leaching of the sulfide concentrate.     

Physicochemical Conditioning of Dredged Heavy Metal‐Polluted Sediment in Suspension

The remediation of heavy metal‐polluted aquatic sediment by solid‐bed bioleaching requires a material well permeable to air and water. Freshly dredged sediment is nearly impermeable and needs previous conditioning to make it suitable for solid‐bed leaching. This conditioning – in practice carried out by planting sediment packages with helophytes – comprises water removal by evapotranspiration, abiotic and microbial oxidation of sediment‐borne reduced compounds, acidification, as well as structural changes improving the sediment permeability. The rate of this process seems to be limited by the transport of oxygen into the sediment bed. For a better understanding of the physicochemical processes occurring during conditioning, sediment oxidation was studied in a stirred suspension to minimize transport limitations. Freshly dredged, silty, anoxic, heavy metal‐polluted sediment from the Weisse Elster River (Germany) was suspended in water and then continuously stirred and aerated at 20 °C. Aerobic conditions appeared within a few hours. The redox potential increased from – 400 to + 220 mV, at first very quickly and later more slowly. Sediment‐borne inorganic sulfur compounds were oxidized to sulfate (S⁰ mainly within two days and sulfide within ten days), which reduced the pH from 7.2 to 5.9. A successive oxidation of FeS to Fe(II) sulfate, the oxidation of Fe(II) to Fe(III) followed by Fe(III) oxyhydrate formation caused the dissolved Fe to sharply increase and thereafter rapidly decrease. Ammonium was completely oxidized in a nitrification process to form nitrate, further decreasing the pH to 5.5. The acidification increased the solubility of Mn, Zn, Mg, Ca, and K. The increase in dissolved Mn rules out any oxidation of Mn(II) to Mn(IV) since Mn(IV) would have been insoluble under the prevailing pH and redox conditions. Sediment oxidation did not proceed in a well‐defined, redox‐potential‐directed order, but individual (partly microbially) oxidation processes superimposed each other. Physicochemical conditioning of suspended sediment was completed after 20 days while conditioning in a solid bed would require months or even years. These different rates result from transport limitations in the solid bed. Sediment conditioning in a solid bed could therefore possibly be accelerated by prior sediment aeration.     

An Integrated System for the Bioremediation of Wastewater Containing Xenobiotics and Toxcic Metals

An integrated system for the biotreatment of acidic wastewaters containing both toxic metals and organics is presented. It consists of two bioprocess stages (i) an anaerobic, SRB stage (containing alkaline‐tolerant s ulfate‐ r educing b acteria) that at pH 8 (chosen to acclimatize the bacteria in the biomedium) produces high concentrations of total sulfide ions (more than 400 mg/L) which are added to the wastewater to precipitate the heavy metals out at pH 2 as metal sulfides, and (ii) an aerobic, acidophilic stage containing heterotrophic bacteria (WJB3) that degrade organic xenobiotics. The anaerobic system was comprised of a 4‐L fluidized bed bioreactor with immobilized SRB, a mixing tank, and a precipitation tank. The effluent from the bioreactor with a high concentration of sulfide ions was fed into a mixing tank where model wastewaters containing toxic metals and phenol at pH 2 were also fed at increasing loading rates until free metal ions could be detected in the precipitation tank outlet. Then the effluent from the precipitation tank outlet was fed into a 2.5‐L aerobic bioreactor in which phenol was degraded. In this research, 100 % removal efficiencies were obtained with wastewaters containing more than 400 mg/L metal ions and 900 mg/L phenol at a 6‐h HRT of the mixing tank.     

Effects of soil acidification and subsequent leaching on levels of extractable nutrients in a soil

Summary The effects of soil acidification (pH values from 6.5 to 3.8), and subsequent leaching, on levels of extractable nutrients in a soil were studied in a laboratory experiment. Below pH 5.5, acidification resulted in large increases in the amounts of exchangeable Al in the soil. Simultaneously, exchangeable cations were displayed from exchange sites and Ca, Mg, K and Na in soil solution increased markedly. With increasing soil acidification, increasing amounts of cations were leached; the magnitude of leaching loss was in the same order as the cations were present in the soil: Ca²⁺>Mg²⁺>K⁺>Na⁺. Soil acidification appeared to inhibit nitrification since in the unleached soils, levels of NO ₃ ⁻ clearly declined below pH 5.5 and at the same time levels of NH ₄ ⁺ increased greatly. Significant amounts of NH ₄ ⁺ and larger amounts of NO ₃ ⁻ , were removed from the soil during leaching. Concentrations of NaHCO₃-extractable phosphate remained unchanged between pH 4.3 and 6.0 but were raised at higher and lower pH values. No leaching losses of phosphate were detected. For the unleached soils, levels of EDTA-extractable Mn and Zn increased as the soil was acidified whilst levels of extractable Fe were first decreased and then increased greatly and those for Cu were decreased slightly between pH 6.5 and 6.0 and then unaffected by further acidification. Significant leaching losses of Mn and Zn were observed at pH values below 5.5 but losses of Fe were very small and those of Cu were not detectable.     

Effects of nitrogen fertilization of grapefruit trees on soil acidification and nutrient availability in a Riviera fine sand

Nitrogen (N) fertilizer applied in the NH4+ form results in some degree of soil acidification, which could influence nutrient availability to plants and nutrient losses through leaching. Effects of various N rates (0 – 168 kg N ha-1 yr-1) on soil acidification and nutrient availability were investigated in a Riviera fine sand with 26-year-old white Marsh grapefruit (Citrus paradisi MacFadyen) trees. Soil pH significantly decreased with increasing NH4–N rates. Application of 112 kg N ha-1 yr-1 for four years decreased the pH by 0.7 to 1.7 unit. Soil acidification was greater when the NH4+ form of N fertilizer was applied as dry soluble granular material compared to fertigation or controlled release forms. The marked effect of NH4–N fertilization on the pH of the Riviera fine sand was due to its low buffering capacity. Soil acidification increased the concentration of extractable Fe and P but decreased that of K, Zn and Mn. Soil pH was positively correlated with concentration of Ca, but negatively with concentrations of Fe, Mn and Zn in six-month-old spring flush leaves of the grapefruit trees. Leaf P concentrations, however, were poorly correlated with soil pH. This study also demonstrated an increase in leaching of P and K below the grapefruit trees rootzone with a decrease in soil pH.     

Leaching of copper ore of the Udokanskoe deposit at low temperatures by an association of acidophilic chemolithotrophic microorganisms

Pure cultures of indigenous microorganisms Acidithiobacillus ferrooxidans strain TFUd, Leptospirillum ferrooxidans strain LUd, and Sulfobacillus thermotolerans strain SUd have been isolated from the oxidation zone of sulfide copper ore of the Udokanskoe deposit. Regimes of bacterial-chemical leaching of ore have been studied over a temperature range from −10 to +20°C. Effects of pH, temperature, and the presence of microorganisms on the extraction of copper have been shown. Bacterial leaching has been detected only at positive values of temperature, and has been much more active at +20 than at +4°C. The process of leaching was more active when the ore contained more hydrophilic and oxidized minerals. The possibility of copper ore leaching of the Udokanskoe deposit using sulfuric acid with pH 0.4 at negative values of temperature and applying acidophilic chemolithotrophic microorganisms at positive values of temperature and low pH values was shown.     

Spatial variation of redox and trace metal geochemistry in a minerotrophic fen

Pore water and solid phase samples were collected from the upper 50 cm of a peat profile at four sites within a 10 m² area in Kleinstuck Marsh, a minerotropic fen located in Kalamazoo, MI. Although the chosen sites are in close proximity to each other, they differ with respect to vegetation species and density. Pore water analyses for a suite of redox sensitive species (pH, alkalinity, dissolved Mn(II), Fe(II), Fe(III), sulfide, sulfate), together with Fe and Mn distributions inferred from operationally-defined sequential extractions, demonstrate that Fe(III) and Mn(IV) reduction occurs in the shallow peat at three of the four sites. At the fourth site, the only site containing the invasive purple loosestrife (Lythrum salicaria), accumulation of dissolved sulfide in the pore waters and increased levels of oxidizable phases in the shallow peat point to increased net sulfate reduction relative to the other three sites. Speciation calculations indicate that pore water concentrations of phosphate, especially below ∼10 cm depth, are largely controlled by the solubility of phases such as strengite or hydroxylapatite, and that at all but the loosestrife site, dissolved Ca and Mg are likely determined by carbonate solubility. Fe and Mn distribution among operationally defined solid phase fractions are consistent with reductive dissolution of FMO in the uppermost peat, leading to precipitation of Fe sulfides and Mn carbonates deeper in the peat profile. Zn, Co, Cr and Ni distributions are consistent with release from FMO to form sulfides or organic associations deeper in the peat. Pb and Cu may also be released by reductive dissolution of FMO, or more likely, shift from primary association with organic matter to increased association with sulfides under more sulfidic conditions. This study highlights the existence of extreme lateral variations in peat pore water and solid phase geochemical profiles, even over quite small areas.     

嗜酸氧化亚铁硫杆菌的高效培养及浸出黄铜矿初探

采用向硫化矿培养基中补加FeSO4的方式以维持Fe2+ 浓度为4～8 g/L,可使嗜酸氧化亚铁硫杆菌菌浓在培养39 h时达到6.25×108 cells/mL,并在比生长速率几乎不降低的前提下提高了转化率和生产强度.然后对低氧化还原电位下低品位黄铜矿的浸出进行初步研究,结果表明经过30 d浸出,铜的浸出率可达28.5%...     

Kinetics and mechanism of the reaction between 1,2-diaminopropanetetra-acetatoferrate(III) and cyanide ion

The present study examines the kinetics and mechanism of the system [FePDTA(OH)]²⁻ + 5CN⁻ ⇌ [Fe(CN)₅OH]³⁻ + PDTA⁴⁻ at pH= 11.0±0.02, I= 0.25 M and temperature = 25 ± 0.1 °C. The reaction has been studied spectrophotometrically at 395 nm (λ_max of [Fe(CN)₅OH]³⁻). The data show that the reaction has three distinguishable stages; the first stage is formation of [Fe(CN)₅OH]³⁻, the second is conversion of [Fe(CN)₅OH)]³⁻ to [Fe(CN)₆]³⁻ and last is reduction of [Fe(CN)₆]³⁻ to [Fe(CN)₆]³⁻ by the released ligand, viz., PDTA. The first reaction shows variable order dependence on cyanide concentration, one at high cyanide concentration and two at low cyanide concentration. The second reaction exhibits first order dependence on the concentration of [Fe(CN)₅OH]³⁻ as well as cyanide. The reverse reaction between [Fe(CN)₅OH]³⁻ and PDTA is first order in [Fe(CN)₅OH]³⁻ and PDTA, and inverse first order in cyanide. On the basis of forward and reverse rate studies, a five-step mechanism has been proposed for the first reaction.     

韶山针阔叶混交林凋落物层的淋溶及缓冲作用

在韶山森林设立4个10m×10m的标准样地,分别收集凋落物、凋落物层淋滤液和冠层穿透水,研究了韶山森林凋落量季节动态,凋落物淋滤液和冠层穿透水特征以及凋落物层对酸沉降的缓冲作用.结果表明:(1)韶山森林凋落高峰出现在秋季,凋落量随着海拔增加而增加;(2)凋落物淋滤液中盐基阳离子浓度除夏季K ＞Ca2 外,其余季节均为:Ca2 ＞K ＞NH 4 ＞Mg2 ＞Na ,与冠层穿透水中阳离子浓度分布基本是一致的;(3)除Ca2 外,凋落物淋滤液和穿冠水中各阳离子浓度相关性显著,K 达到了极显著相关水平,证实了韶山森林通过凋落物养分归还的K 主要来自森林冠层的滤出;(4)除个别点外,凋落物淋滤液中各阳离子总浓度较冠层穿透水均有不同程度的增加,秋季增幅最大,冬季次之,这与凋落物量变化一致;(5)韶山森林冠层穿透水pH值变动范围为4.58～7.13,最低值出现在冬季,最高值出现在夏季,凋落物淋滤液pH值变动范围为5.02～6.69,均高于韶山表层土壤pH平均值5.0,且最低值出现在春季,最高值出现在秋季;(6)冬季凋落物淋滤液pH值较冠层穿透水均增加,增幅范围在0.06～1.35之间,而其他季节(除样地C的秋季外)pH值均有所下降,这表明韶山森林凋落物层冬季具有较强的酸缓冲作用,而其他季节由于盐基阳离子的滤出不足以抵消凋落物本身分解产生的有机酸类物质的酸化作用,而使凋落物淋滤液pH值降低.     

Continuous culture of Thiobacillus ferrooxidans on a zinc sulfide concentrate

A zinc sulfide concentrate was leached microbiologically by Thiobacillus ferrooxidans in a continuous stirred tank reactor. A model was developed to predict, the leaching kinetics when the bacterial growth rate was not limited by any substrate other than the zinc concentrate, and it was modified to explain the observed results. Stable steady sates were obtained over a range of dilution rates from 0.0171 to 0.1038 hr^?1. Because a solid substrate was used, the specific growth rate of the bacaeria was not a unique function of the subastrate concentration, and conventional contnuous culture theory based on the Monod equation did not apply to this system. The leaching rates and bacterial growth rates were first order in mineral surface area cocentration.     

Migration of arsenic(III) during bacterial oxidation of arsenopyrite in chalcopyrite concentrate by Thiobacillus ferrooxidans

During bacterial oxidation of the arsenopyrite that contaminated a chalcopyrite concentrate, the bioextraction of arsenic from the concentrate was examined. A long-term constant As(III) concentration, representing a large portion of the total arsenic, occurred in the leaching medium. As(III) was not further oxidized, either under bioextraction conditions or by Fe(III) in the presence of the mesophilic bacterium Thiobacillus ferooxidans. These results are discussed in relation to the influence of leaching microorganisms on the form of arsenic in the solution. Dissolved As(III) could be reversed into a solid phase by adsorption of As(III) by forming an iron precipitate. Correspondence to: M. Mandl     

Chemical and biological leaching of enargite

Enargite (Cu 3 AsS 4 ) was leached faster by bacteria in sulfuric acid medium (pH 1.6) with added ferric sulfate than by chemical leaching at the same or higher iron concentration. During chemical leaching with ferric iron, the copper dissolution rate decreased from an initial value of 0.03% per hour to a value of 0.002% per hour. Enargite is oxidized to elemental sulfur and dissolved arsenic (As 3+ and As 5+ ). Less than 10% of sulfur is oxidized to sulfate. The arsenic and copper dissolutions observed in bacterial leaching experiments suggest the existence of a specific bacterial action on the leaching of enargite, demonstrated by the ability of bacteria to oxidize enargite at very low concentration of dissolved iron and by the higher dissolution rate obtained in bacterial leaching compared to chemical ferric leaching.     

Ferriprotoporphyrin IX mediated oxygen activation/insertion reactions: the anerobic reduction of the aniline-Fe3+-microperoxidase-8 complex by NADH

A spectrophotometric study of the reduction of the Fe3+ microperoxidase-8-aniline (Fe3+-MP-8-An) complex has been carried out. Addition of NADH to a solution of Fe3+-MP-8-An under strictly anerobic conditions results in the formation of a species with lambda max = 414 nm (Fe3+-MP-8-An lambda max 407 nm). The kinetics of formation of this species show an induction period (tau) which follows saturation kinetics with respect to [aniline] with Km(app) = 2.2 x 10(-3) mol dm-3, i.e., close to that obtained in the preceding paper from O2 consumption kinetics mediated by MP-8. Addition of an anerobic solution of the NADH reduced MP-8-An complex, to a saturated O2 solution at pH 12 in the presence of 0.5 mM NADH and aniline 10 mM results in the virtual elimination of the induction phase, which has previously characterized O2 consumption kinetics in ferriprotoporphyrin IX oxygen activation systems. The Arrhenius activation energy for the reduction of the Fe3+-MP-8-An complex is close to that observed for the first reductive step in the cyt P-450 O2 activation cycle. Anerobic reduction of Fe3+-MP-8 by sodium dithionite in 20% MeOH/Aq at pH 8 followed by anerobic titration of the Fe2+-MP-8 (lambda max 420.5 nm) with aniline at pH 12 gives rise to a species lambda max 415 with KD for the process = 4.4 x 10(-3) mol dm-3 (+/- 1.2 x 10(-3) mol dm-3).     

Microbiological leaching of a zinc sulfide concentrate

The microbiological extraction of zinc from a high-grade zinc sulfide concentrate has been investigated, using a pure strain of Thiobacillus ferrooxidans. Conditions such as temperature, pH, pulp density, nutrient, concentration, and specific surface of solids have been studied in terms of their effects on zinc extraction rate and in some instances on final zinc concentration in solution. Where appropriate, optimum conditions for leaching have been specified.