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.     

Characteristics and adaptability of iron- and sulfur-oxidizing microorganisms used for the recovery of metals from minerals and their concentrates

Microorganisms are used in large-scale heap or tank aeration processes for the commercial extraction of a variety of metals from their ores or concentrates. These include copper, cobalt, gold and, in the past, uranium. The metal solubilization processes are considered to be largely chemical with the microorganisms providing the chemicals and the space (exopolysaccharide layer) where the mineral dissolution reactions occur. Temperatures at which these processes are carried out can vary from ambient to 80°C and the types of organisms present depends to a large extent on the process temperature used. Irrespective of the operation temperature, biomining microbes have several characteristics in common. One shared characteristic is their ability to produce the ferric iron and sulfuric acid required to degrade the mineral and facilitate metal recovery. Other characteristics are their ability to grow autotrophically, their acid-tolerance and their inherent metal resistance or ability to acquire metal resistance. Although the microorganisms that drive the process have the above properties in common, biomining microbes usually occur in consortia in which cross-feeding may occur such that a combination of microbes including some with heterotrophic tendencies may contribute to the efficiency of the process. The remarkable adaptability of these organisms is assisted by several of the processes being continuous-flow systems that enable the continual selection of microorganisms that are more efficient at mineral degradation. Adaptability is also assisted by the processes being open and non-sterile thereby permitting new organisms to enter. This openness allows for the possibility of new genes that improve cell fitness to be selected from the horizontal gene pool. Characteristics that biomining microorganisms have in common and examples of their remarkable adaptability are described.     

Formation of water-soluble metal cyanide complexes from solid minerals by Pseudomonas plecoglossicida

A few Pseudomonas species are able to form hydrocyanic acid (HCN), particularly when grown under glycine-rich conditions. In the presence of metals, cyanide can form water-soluble metal complexes of high chemical stability. We studied the possibility to mobilize metals as cyanide complexes from solid minerals using HCN-forming microorganisms. Pseudomonas plecoglossicida was cultivated in the presence of copper- and nickel-containing solid minerals. On powdered elemental nickel, fast HCN generation within the first 12 h of incubation was observed and water-soluble tetracyanaonickelate was formed. Cuprite, tenorite, chrysocolla, malachite, bornite, turquoise, millerite, pentlandite as well as shredded electronic scrap was also subjected to a biological treatment. Maximum concentrations of cyanide-complexed copper corresponded to a solubilization of 42% and 27% when P. plecoglossicida was grown in the presence of cuprite or tenorite, respectively. Crystal system, metal oxidation state and mineral hydrophobicity might have a significant influence on metal mobilization. However, it was not possible to allocate metal mobilization to a single mineral property. Cyanide-complexed gold was detected during growth on manually cut circuit boards. Maximum dicyanoaurate concentration corresponded to a 68.5% dissolution of the total gold added. These findings represent a novel type of microbial mobilization of nickel and copper from solid minerals based on the ability of certain microbes to form HCN.     

Acdidophilic thermophilic archaebacteria: Potential application for metals recovery

Abstract The acidophilic thermophilic archaebacteria Sulfolobus and Acidianus have the potential for applid use in the recovery of metal values from ores through the process of baterial leaching. These microbes readily adapt to the conditions of low pH and high concentrations of metals required for bacterial leaching. In addition, these archaebacteria can exist at high temperatures which can occur during the oxidation of metal sulfides in bioleaching reactors. The acidophilic of copper and molybdenum from chalcopyrite and molybdenite minerals, respectively. The microbes can also enhance the recovery of gold by oxidation of pyrite which occludes gold preventing recovery by standard metallurgical procedures. The ability of this group of microbes to facilitate metals recovery is yet to be developed on a commercial scale.     

Bioleaching review part B:

This review describes the historical development and current state of metals leaching and sulfide mineral biooxidation by the minerals industries. During the past 20 years commercial processes employing microorganisms for mineral recovery have progressed from rather uncontrolled copper dump leaching to mineral oxidation and leaching in designed bioheaps for oxidation of refractory gold ores and for copper recovery. Also during this period of time, stirred tank bioleaching has been commercialized for cobalt recovery and for biooxidation of refractory gold ores. Chalcopyrite bioleaching in stirred tanks is on the verge of commercialization. Commercial applications of biohydrometallurgy have advanced due to favorable process economics and, in some cases, reduced environmental problems compared to conventional metal recovery processes such as smelting. Process development has included recognition of the importance of aeration of bioheaps, and improvements in stirred tank reactor design and operation. Concurrently, knowledge of the key microorganisms involved in these processes has advanced, aided by advances in molecular biology to characterize microbial populations.     

Microbial colonization of metal sulfide minerals at a diffuse‐flow deep‐sea hydrothermal vent at 9°50′N on the East Pacific Rise

Metal sulfide minerals, including mercury sulfides (HgS), are widespread in hydrothermal vent systems where sulfur‐oxidizing microbes are prevalent. Questions remain as to the impact of mineral composition and structure on sulfur‐oxidizing microbial populations at deep‐sea hydrothermal vents, including the possible role of microbial activity in remobilizing elemental Hg from HgS. In the present study, metal sulfides varying in metal composition, structure, and surface area were incubated for 13 days on and near a diffuse‐flow hydrothermal vent at 9°50′N on the East Pacific Rise. Upon retrieval, incubated minerals were examined by scanning electron microscopy with energy‐dispersive X‐ray spectroscopy (SEM‐EDS), X‐ray diffraction (XRD), and epifluorescence microscopy (EFM). DNA was extracted from mineral samples, and the 16S ribosomal RNA gene sequenced to characterize colonizing microbes. Sulfur‐oxidizing genera common to newly exposed surfaces (Sulfurimonas, Sulfurovum, and Arcobacter) were present on all samples. Differences in their relative abundance between and within incubation sites point to constraining effects of the immediate environment and the minerals themselves. Greater variability in colonizing community composition on off‐vent samples suggests that the bioavailability of mineral‐derived sulfide (as influenced by surface area, crystal structure, and reactivity) exerted greater control on microbial colonization in the ambient environment than in the vent environment, where dissolved sulfide is more abundant. The availability of mineral‐derived sulfide as an electron donor may thus be a key control on the activity and proliferation of deep‐sea chemosynthetic communities, and this interpretation supports the potential for microbial dissolution of HgS at hydrothermal vents.     

Getting rid of the unwanted: highlights of developments and challenges of biobeneficiation of iron ore minerals—a review

The quest for quality mineral resources has led to the development of many technologies that can be used to refine minerals. Biohydrometallurgy is becoming an increasingly acceptable technology worldwide because it is cheap and environmentally friendly. This technology has been successfully developed for some sulphidic minerals such as gold and copper. In spite of wide acceptability of this technology, there are limitations to its applications especially in the treatment of non-sulphidic minerals such as iron ore minerals. High levels of elements such as potassium (K) and phosphorus (P) in iron ore minerals are known to reduce the quality and price of these minerals. Hydrometallurgical methods that are non-biological involving the use of chemicals are usually used to deal with this problem. However, recent advances in mining technologies favour green technologies, known as biohydrometallurgy, with minimal impact on the environment. This technology can be divided into two, namely bioleaching and biobeneficiation. This review focuses on Biobeneficiation of iron ore minerals. Biobeneficiation of iron ore is very challenging due to the low price and chemical constitution of the ore. There are substantial interests in the exploration of this technology for improving the quality of iron ore minerals. In this review, current developments in the biobeneficiation of iron ore minerals are considered, and potential solutions to challenges faced in the wider adoption of this technology are proposed.     

Microbial leaching of metals from solid industrial wastes

Biotechnological applications for metal recovery have played a greater role in recovery of valuable metals from low grade sulfide minerals from the beginning of the middle era till the end of the twentieth century. With depletion of ore/minerals and implementation of stricter environmental rules, microbiological applications for metal recovery have been shifted towards solid industrial wastes. Due to certain restrictions in conventional processes, use of microbes has garnered increased attention. The process is environmentally-friendly, economical and cost-effective. The major microorganisms in recovery of heavy metals are acidophiles that thrive at acidic pH ranging from 2.0–4.0. These microbes aid in dissolving metals by secreting inorganic and organic acids into aqueous media. Some of the well-known acidophilic bacteria such as Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans, Leptospirillum ferrooxidans and Sulfolobus spp. are well-studied for bioleaching activity, whereas, fungal species like Penicillium spp. and Aspergillus niger have been thoroughly studied for the same process. This mini-review focuses on the acidophilic microbial diversity and application of those microorganisms toward solid industrial wastes.     

Ferroplasma and relatives, recently discovered cell wall-lacking archaea making a living in extremely acid, heavy metal-rich environments

For several decades, the bacterium Acidithiobacillus (previously Thiobacillus) has been considered to be the principal acidophilic sulfur- and iron-oxidizing microbe inhabiting acidic environments rich in ores of iron and other heavy metals, responsible for the metal solubilization and leaching from such ores, and has become the paradigm of such microbes. However, during the last few years, new studies of a number of acidic environments, particularly mining waste waters, acidic pools, etc., in diverse geographical locations have revealed the presence of new cell wall-lacking archaea related to the recently described, acidophilic, ferrous-iron oxidizing Ferroplasma acidiphilum. These mesophilic and moderately thermophilic microbes, representing the family Ferroplasmaceae, were numerically significant members of the microbial consortia of the habitats studied, are able to mobilize metals from sulfide ores, e.g. pyrite, arsenopyrite and copper-containing sulfides, and are more acid-resistant than iron and sulfur oxidizing bacteria exhibiting similar eco-physiological properties. Ferroplasma cell membranes contain novel caldarchaetidylglycerol tetraether lipids, which have extremely low proton permeabilities, as a result of the bulky isoprenoid core, and which are probably a major contributor to the extreme acid tolerance of these cell wall-less microbes. Surprisingly, several intracellular enzymes, including an ATP-dependent DNA ligase have pH optima close to that of the external environment rather than of the cytoplasm. Ferroplasma spp. are probably the major players in the biogeochemical cycling of sulfur and sulfide metals in highly acidic environments, and may have considerable potential for biotechnological applications such as biomining and biocatalysis under extreme conditions.     

Fungal biotransformation of zinc silicate and sulfide mineral ores

In this work, several fungi with geoactive properties, including Aspergillus niger, Beauveria caledonica and Serpula himantioides, were used to investigate their potential bioweathering effects on zinc silicate and zinc sulfide ores used in zinc extraction and smelting, to gain understanding of the roles that fungi may play in transformations of such minerals in the soil, and effects on metal mobility. Despite the recalcitrance of these minerals, new biominerals resulted from fungal interactions with both the silicate and the sulfide, largely resulting from organic acid excretion. Zinc oxalate dihydrate was formed through oxalate excretion by the test fungi and the mineral surfaces showed varying patterns of bioweathering and biomineral formation. In addition, calcium oxalate was formed from the calcium present in the mineral ore fractions, as well as calcite. Such metal immobilization may indicate that the significance of fungi in effecting metal mobilization from mineral ores such as zinc silicate and zinc sulfide is rather limited, especially if compared with bacterial sulfide leaching. Nevertheless, important bioweathering activities of fungi are confirmed which could be of local significance in soils polluted by such materials, as well as in the mycorrhizosphere.     

Advances in biotreatment of acid mine drainage and biorecovery of metals: 1. Metal precipitation for recovery and recycle

Acid mine drainage (AMD), an acidic metal-bearingwastewater, poses a severe pollution problem attributedto post mining activities. The metals usuallyencountered in AMD and considered of concern for riskassessment are arsenic, cadmium, iron, lead, manganese,zinc, copper and sulfate. The pollution generated byabandoned mining activities in the area of Butte, Montanahas resulted in the designation of the Silver Bow Creek–ButteArea as the largest Superfund (National Priorities List) sitein the U.S. This paper reports the results of bench-scalestudies conducted to develop a resource recovery basedremediation process for the clean up of the Berkeley Pit.The process utilizes selective, sequential precipitation (SSP)of metals as hydroxides and sulfides, such as copper, zinc,aluminum, iron and manganese, from the Berkeley Pit AMDfor their removal from the water in a form suitable foradditional processing into marketable precipitates and pigments.The metal biorecovery and recycle process is based on completeseparation of the biological sulfate reduction step and themetal precipitation step. Hydrogen sulfide produced in the SRBbioreactor systems is used in the precipitation step to forminsoluble metal sulfides. The average metal recoveries usingthe SSP process were as follows: aluminum (as hydroxide) 99.8%,cadmium (as sulfide) 99.7%, cobalt (as sulfide) 99.1% copper(as sulfide) 99.8%, ferrous iron (sulfide) 97.1%, manganese(as sulfide) 87.4%, nickel (as sulfide) 47.8%, and zinc (as sulfide)100%. The average precipitate purity for metals, copper sulfide,ferric hydroxide, zinc sulfide, aluminum hydroxide and manganesesulfide were: 92.4, 81.5, 97.8, 95.6 , 92.1 and 75.0%, respectively.The final produced water contained only calcium and magnesiumand both sulfate and sulfide concentrations were below usablewater limits. Water quality of this agriculturally usable watermet the EPA's gold standard criterion.     

Application of iron-oxidizing bacteria to hydrometallurgical flue dust treatment and H2S desulfurization

Abstract: Flue dust produced from the Kosaka copper flashsmelting furnace contains metals such as Cu, Pb, Zn, Fc, As, Cd, etc. To recover these metals, the dust is treated in the hydrometallurgical plant. Previous iron oxidation by air blown at pH 5 and at 50°C for removal of iron from the leached solution has been superceded by bacterial iron oxidation and pecipitation processes. The advantages of this bacterial oxidation procedure are (i) low cost; (ii) clear separation of metals; (iii) improvement in settling and dewatering characteristics and smaller, stable of volume precipitate and (iv) possibilities of fixing arsenate to obtain inexpensive ferric ions. A new hydrogen sulfide gas treatment process has been developed to treat the gas from plants producing barium chemicals. Itydrogen sulfide (70% content) is absorbed on ferric iron solution, and is thus oxidized to elemental sulfur. After the sulfur has been separated, the iron- oxidizing bacteria are employed to regenerate the absorbing solution. In this plant, which produces 150 tons sulfur per month, the hydrogen sulfide content of sweet gas is kept under 10 ppm; equivalent to 99.99%,; of the hydrogen sulfide recovery. The advantages of this process are (i) high H 2S gas removal efficiency; (ii) low running cost; (iii) ease of operation and maintenance: (iv) no waste; (v) high H₂S selectivity; and (vi) good flexibility overload fluctuations.     

Genomics, metagenomics and proteomics in biomining microorganisms

The use of acidophilic, chemolithotrophic microorganisms capable of oxidizing iron and sulfur in industrial processes to recover metals from minerals containing copper, gold and uranium is a well established biotechnology with distinctive advantages over traditional mining. A consortium of different microorganisms participates in the oxidative reactions resulting in the extraction of dissolved metal values from ores. Considerable effort has been spent in the last years to understand the biochemistry of iron and sulfur compounds oxidation, bacteria-mineral interactions (chemotaxis, quorum sensing, adhesion, biofilm formation) and several adaptive responses allowing the microorganisms to survive in a bioleaching environment. All of these are considered key phenomena for understanding the process of biomining. The use of genomics, metagenomics and high throughput proteomics to study the global regulatory responses that the biomining community uses to adapt to their changing environment is just beginning to emerge in the last years. These powerful approaches are reviewed here since they offer the possibility of exciting new findings that will allow analyzing the community as a microbial system, determining the extent to which each of the individual participants contributes to the process, how they evolve in time to keep the conglomerate healthy and therefore efficient during the entire process of bioleaching.     

Nicotianamine: mediator of transport of iron and heavy metals in the phloem?

Recent work has demonstrated that minerals in plants are circulated between root and shoot. This occurs during the whole life time and renders possible response to changing environmental conditions. This mineral circulation occurs through intensive solute exchange between xylem and phloem in roots, stems, and leaves. The transport form of heavy metals such as iron, manganes, zinc and copper in the phloem, whether ionic or chelated, is unclear in most cases.
The unusual amino acid nicotianamine (NA) is ubiquitous throughout the plant kingdom. It is a chelator of several divalent transition metals. Its physiological role was investigated with the tomato mutant chloronerva, the only known NA-free multicellular plant. The mutant also exhibits disturbances of its iron metabolism and that of other heavy metals. This leads, among others, to a typical intercostal chlorosis and progressive iron accumulation in the leaves. From the heavy metal chelating properties of NA and from the phenotype of the mutant chloronerva it is concluded that NA is needed for normal distribution of heavy metals in young growing tissues fed via the phloem. This function could be fulfilled by mediating phloem loading or unloading of heavy metals as well as by preventing their precipitation in the alkaline phloem sap. An attempt is made to explain the chloronerva phenotype in the light of the phloem transport hypothesis of chelated iron.     

Burning question: Are there sustainable strategies to prevent microbial metal corrosion?

The global economic burden of microbial corrosion of metals is enormous. Microbial corrosion of iron-containing metals is most extensive under anaerobic conditions. Microbes form biofilms on metal surfaces and can directly extract electrons derived from the oxidation of Fe⁰ to Fe²⁺ to support anaerobic respiration. H₂ generated from abiotic Fe⁰ oxidation also serves as an electron donor for anaerobic respiratory microbes. Microbial metabolites accelerate this abiotic Fe⁰ oxidation. Traditional strategies for curbing microbial metal corrosion include cathodic protection, scrapping, a diversity of biocides, alloys that form protective layers or release toxic metal ions, and polymer coatings. However, these approaches are typically expensive and/or of limited applicability and not environmentally friendly. Biotechnology may provide more effective and sustainable solutions. Biocides produced with microbes can be less toxic to eukaryotes, expanding the environments for potential application. Microbially produced surfactants can diminish biofilm formation by corrosive microbes, as can quorum-sensing inhibitors. Amendments of phages or predatory bacteria have been successful in attacking corrosive microbes in laboratory studies. Poorly corrosive microbes can form biofilms and/or deposit extracellular polysaccharides and minerals that protect the metal surface from corrosive microbes and their metabolites. Nitrate amendments permit nitrate reducers to outcompete highly corrosive sulphate-reducing microbes, reducing corrosion. Investigation of all these more sustainable corrosion mitigation strategies is in its infancy. More study, especially under environmentally relevant conditions, including diverse microbial communities, is warranted.     

Biogeochemical phenomena induced by bacteria within sulfidic mine tailings

Summary Mill tailings resulting from mining and metallurgical processes are usually disposed of into open-air impoundments, where they become subjected to chemical or microbial leaching. At the surface of the tailings, where oxic conditions prevail, acidophilic bacteria, such as thiobacilli, can oxidize sulfidic minerals (e.g. pyrite and pyrrhotite) and generate acidic metal-rich leachates as by-products of their metabolism. This, combined with chemical oxidation, leads to acid mine drainage (AMD). Biomineralization, whereby a proportion of the metal leachate is precipitated, can also occur in the oxidized tailings, often as a result of a close metal-bacteria interaction. Iron-rich precipitates are usually found on bacterial cell walls, and are thought to serve as nucleation sites for further mineralization within the tailings impoundments. As depth increases in mine tailings, oxygen depletion and the presence of water-saturated pores usually lead to anoxic conditions. Under such redox and chemical conditions, populations of sulfate-reducing bacteria (SRBs) can colonize the tailings. As a result of their metabolic activity, sulfate is reduced to hydrogen sulfide, which in turn can react with dissolved metals to form metal sulfide precipitates. Microbial sulfate reduction also generates alkalinity, although chemical dissolution of carbonate and oxide minerals probably also play an important role in the generation of alkaline conditions in mine tailings.     

Metal resistance and accumulation in bacteria

Recent research on the ecology, physiology and genetics of metal resistance and accumulation in bacteria has significantly increased the basic understanding of microbiology in these areas. Research has clearly demonstrated the versatility of bacteria to cope with toxic metal ions. For example, certain strains of bacteria can efficiently efflux toxic ions such as cadmium, that normally exert an inhibitory effect on bacteria. Some bacteria such as Escherichia coli and Staphylococcus sp. can volatilize mercury via enzymatic transformations. It is also noteworthy that many of these resistance mechanisms are encoded on plasmids or transposons. By expanding the knowledge on metal-resistance and accumulation mechanisms in bacteria, it may be possible to utilize certain strains to recover precious metals such as gold and silver, or alternatively remove toxic metal ions from environments or products where their presence is undesirable.     

Extraction of copper from an oxidized (lateritic) ore using bacterially catalysed reductive dissolution

An oxidized lateritic ore which contained 0.8 % (by weight) copper was bioleached in pH- and temperature-controlled stirred reactors under acidic reducing conditions using pure and mixed cultures of the acidophilic chemolithotrophic bacterium Acidithiobacillus ferrooxidans. Sulfur was provided as the electron donor for the bacteria, and ferric iron present in goethite (the major ferric iron mineral present in the ore) acted as electron acceptor. Significantly more copper was leached by bacterially catalysed reductive dissolution of the laterite than in aerobic cultures or in sterile anoxic reactors, with up to 78 % of the copper present in the ore being extracted. This included copper that was leached from acid-labile minerals (chiefly copper silicates) and that which was associated with ferric iron minerals in the lateritic ore. In the anaerobic bioreactors, soluble iron in the leach liquors was present as iron (II) and copper as copper (I), but both metals were rapidly oxidized (to iron (III) and copper (II)) when the reactors were aerated. The number of bacteria added to the reactors had a critical role in dictating the rate and yield of copper solubilised from the ore. This work has provided further evidence that reductive bioprocessing, a recently described approach for extracting base metals from oxidized deposits, has the potential to greatly extend the range of metal ores that can be biomined.     

A novel mineral flotation process using Thiobacillus ferrooxidans.

Oxidative leaching of metals by Thiobacillus ferrooxidans has proven useful in mineral processing. Here, we report on a new use for T. ferrooxidans, in which bacterial adhesion is used to remove pyrite from mixtures of sulfide minerals during flotation. Under control conditions, the floatabilities of five sulfide minerals tested (pyrite, chalcocite, molybdenite, millerite, and galena) ranged from 90 to 99%. Upon addition of T. ferrooxidans, the floatability of pyrite was significantly suppressed to less than 20%. In contrast, addition of the bacterium had little effect on the floatabilities of the other minerals, even when they were present in relatively large quantities: their floatabilities remained in the range of 81 to 98%. T. ferrooxidans thus appears to selectively suppress pyrite floatability. As a consequence, 77 to 95% of pyrite was removed from mineral mixtures while 72 to 100% of nonpyrite sulfide minerals was recovered. The suppression of pyrite floatability was caused by bacterial adhesion to pyrite surfaces. When normalized to the mineral surface area, the number of cells adhering to pyrite was significantly larger than the number adhering to other minerals. These results suggest that flotation with T. ferrooxidans may provide a novel approach to mineral processing in which the biological functions involved in cell adhesion play a key role in the separation of minerals.     

Progress in bioleaching: part B: applications of microbial processes by the minerals industries

This review presents developments and applications in bioleaching and mineral biooxidation since publication of a previous mini review in 2003 (Olson et al. Appl Microbiol Biotechnol 63:249–257, 2003). There have been discoveries of newly identified acidophilic microorganisms that have unique characteristics for effective bioleaching of sulfidic ores and concentrates. Progress has been made in understanding and developing bioleaching of copper from primary copper sulfide minerals, chalcopyrite, covellite, and enargite. These developments point to low oxidation–reduction potential in concert with thermophilic bacteria and archaea as a potential key to the leaching of these minerals. On the commercial front, heap bioleaching of nickel has been commissioned, and the mineral biooxidation pretreatment of sulfidic-refractory gold concentrates is increasingly used on a global scale to enhance precious metal recovery. New and larger stirred-tank reactors have been constructed since the 2003 review article. One biooxidation–heap process for pretreatment of sulfidic-refractory gold ores was also commercialized. A novel reductive approach to bioleaching nickel laterite minerals has been proposed.