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Advanced Materials Research Vols. 71-73 (2009) pp 3-10 online at http://www.scientific.

net (2009) Trans Tech Publications, Switzerland Online available since 2009/May/19

Biohydrometallurgy: what is its future? C. L. Brierley


Brierley Consultancy LLC, P.O. Box 630012, Highlands Ranch, Colorado 80163-0012 U.S.A. clbrierley@msn.com Keywords: biohydrometallurgy, bioremediation, bioleaching, minerals biooxidation, heap leaching, models, complex ores, secondary copper sulfide, chalcopyrite

Abstract. Bioleaching/minerals biooxidation and bioremediation have been widely used commercially for heap/dump bioleaching of secondary copper sulfide ores, sulfidic-refractory gold concentrates and treatment of acid rock drainage. Technical and commercial challenges, identified in this paper, remain for bioleaching of primary sulfides and complex ores. New frontiers for the technology exist in processing massive sulfides, silicate-locked minerals and in the more distant future in-situ leaching. Decommissioning of cyanide heap leach operations and stabilizing mine wastes using biotechnology are opportunities requiring intensive and focused research, development and engineering efforts. Introduction The past decade has been particularly dramatic in view of increasing metal prices to unprecedented high levels followed by an unparalleled event of precipitously declining metal prices, rapid increase in production costs, and the global impacts that these factors have had on the mining sector. The mining industry, however, has always been a boom-and-bust business which exhibits cycles of high and low metal prices. These cycles have a substantial effect on the growth and contraction of the industry. When metal prices decline, costs increase, or both, high-cost mines are usually moth-balled, production is often curtailed, mine plans may be changed to target higher metal grades, expenditures including research and development are often severely cut-back, and lay-offs that include research and engineering personnel are implemented. But do boom-and-bust cycles have an effect on innovations relating to metal recovery and the practice of these innovations? Those of us who research, develop, engineer and apply biohydrometallurgical processes for mine production and metals remediation tend to believe that biotechnical processes have lower capital and operating costs than competitive technologies and therefore should perhaps be more economical to implement during mining down-cycles than other processes. Is this really the case? To test this theory, the prices of two metals gold and copper were plotted against time and superimposed on these graphs are biohydrometallurgical processes for mine production and remediation that have been demonstrated or put into practice. This paper discusses these findings, other motivating factors (drivers) for biohydrometallurgical innovation, technical and commercial challenges of implementing biohydrometallurgy in an industry that is prone to the ups and downs of market economics, and concludes with a discussion of the future of biohydrometallurgy which includes both production and metals remediation technologies. Motivating Factors for Biohydrometallurgical Technologies Figures 1 and 2 illustrate the prices of copper and gold [1, 2, 3, 4], respectively, since biotechnology was first implemented for metals extraction and treatment of metal-contaminated water. These two metals were selected, because they represent the focus of most biometallurgical research, development and application. Included on the graphic representations are significant developments in biometallurgy. It is important to highlight that many of these technologies may have been under development for a decade or more before actually being put into commercial practice.
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Fig. 1 and Fig. 2 do suggest that most biohydrometallurgical innovations have been commercially implemented during times of low metal prices, which could be interpreted to mean that the mining industry is more inclined to innovate and apply biohydrometallurgical processes during leaner times. The BioCOP technology was, in fact, demonstrated as the copper price was rapidly increasing. While increasing copper price was unlikely to be the only reason why the technology was not fully commercialized [13], it may have been a contributing factor. Metal prices, of course, are not the only motivating factor for employing biohydrometallurgical processes. Other drivers include: Cost of production. As energy costs have escalated, mining, processing, and environmental costs have substantially increased [14]. Some biohydrometallurgical processes for processing and remediation are less energy intensive than alternative technologies and can potentially reduce costs for the industry. Also, biohydrometallurgical processing methods eliminate Net Smelter Royalties associated with smelting and refining and potential penalty charges associated with smelting feeds with impurities. Sulfuric acid costs can be volatile depending on demand and location [15]; bioleaching/minerals biooxidation can be used in some situations for on-site acid production to eliminate or reduce acid purchases. Exploitation of ore deposits not amenable to conventional processes or otherwise difficult to exploit. One such example is the development of secondary copper sulfide ore deposits, which may be too small or too remote to be economically amenable to making a flotation concentrate either for shipping or onsite smelting. Another example is processing of sulfidic-refractory gold ore properties, located in regions where biooxidation technologies may be more suitable for cost and workforce reasons. A third example is ores deposits with complex mineralogy; such deposits are difficult to treat and biohydrometallurgy may be a viable alternative. Maximizing use of existing capital investment. Many copper operations already have solvent extraction-electrowinning plants that represent a significant investment. Applying bioleaching processes for processing copper sulfides allows for use and expansion of these facilities. Environmental permitting for mining operations can be long and difficult. The use of biohydrometallurgical processes for both mineral processing and treatment of effluents may offer some environmental advantages over more conventional technologies. In some cases bioprocessing is seen as a green technology.

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First stirred-tank BIOX plant, Fairview, South Africa [5]

GEOCOAT plant commissioned, Fairview, South Africa [8]

RBC for CN- & SCNdegradation & metal sorption, South Dakota, USA [6]

BIOPRO biooxidation heap, Carlin, Nevada [7]

Figure 1. Yearly average gold price (US$/oz) in actual dollars from 1968 through 2008 [1, 2] with significant biohydrometallurgical applications denoted

Constructed anaerobic wetlands used for remediation [10] Bacteriallyassisted dump leaching of Cu implemented [9] Secondary Cu heap bioleaching first applied [11]

THIOPAQ SO42- reduction / metal removal process first implemented [12] BioCOP demonstrated for Cu concentrate tank bioleaching [13]

Figure 2. Yearly average unit copper price (actual US cents/lb) from 1950 through 2008 [3, 4] with significant biohydrometallurgical applications denoted

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Technical and Commercial Challenges of Implementing Biohydrometallurgy Commercial Challenges. Biohydrometallurgical technologies for mineral processing and metals remediation are developed by mining companies, biotechnology companies, government laboratories, university research scientists and engineers, and mining consultants. The path from laboratory research to commercial application of biohydrometallurgical technologies developed by these various entities has many obstacles and challenges: Time - The time required to research, develop, pilot and commercialize the technology can be 10 years to as long as two decades. This calls for long-term commitment of the scientists and engineers developing the technology, by management in the case of industry, and of finances. Site specificity - Bioprocessing and metals bioremediation technologies are usually site specific. Therefore, nearly every process that is developed requires on-site piloting and perhaps even large-scale demonstration. On-site pilot trials and demonstration-scale testing can be very costly and time-consuming. Long-term commitments of time, money, facilities, personnel and management are required not only by the mining company whose property and resources will be used, but also for the company or institution whose technology is being evaluated. Competitiveness - Biohydrometallurgical processes must compete technically and cost-wise with alternative technologies. In the case of bioleaching/minerals biooxidation, the technology must compete with making and selling a concentrate, pressure oxidation, roasting/smelting, and emerging chemical leaching processes. Metals bioremediation must compete with alkaline precipitation a process that has long been used by the industry and other technologies, such as ion exchange and reverse osmosis, which are used by the industry under certain circumstances. There are a number of factors that the mining industry must consider when selecting a processing or remediation technology. Bio-processes may not always meet all of the criteria. Risk - New technologies whether they are bioprocesses or physical/chemical processes have a modest chance of success. The risks involved in commercially exploiting new technologies have been detailed by others [16, 17]. Technology failures are not only financially costly, but can harm the reputations of individuals, institutions which developed the technology, engineering companies involved in final design and commissioning and the mining company itself. Capital investment - New technologies often require a substantial capital investment, since new unit processes may be required on the front-end and the back-end of the actual biohydrometallurgical process. For example, the 20,000 tonne per annum BioCOP demonstration plant at the Chuquicamata Mine in Chile was estimated at US$60 million [18]. A full-scale plant would, of course, have cost substantially more. Intellectual property Patents are usually used to protect intellectual property associated with new technologies. Mining companies often patent bioprocesses to protect their own use of technology they have developed. Entrepreneurial companies patent technologies in order to raise financing and to protect business interests. Some universities and government or quasi-government agencies also patent biohydrometallurgical processes to potentially exploit developments through licensing arrangements. Mining companies, however, often balk at paying licensing fees or royalties for technology. There are several reasons for this: changes in ore type may preclude future need for the technology; newer processes could

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negate the value of the technology; licensing fees may stifle business deals the mining company may undertake; mining companies may be reluctant to open production logs a move that may be necessary to assess licensing fees; quite often new technology is a singular unit process whose success is largely dependent on upfront unit processes that are part of conventional processing; and there may be a certain amount of not invented here mentality at play. Licensing fees or royalties for biometallurgical processes can be difficult to negotiate particularly for metal production, because there are many factors affecting production that are beyond the control of the technology owner. Process guarantees The mine owner may request process guarantees for mine production and environmental biotechnologies. Guarantees can be very complicated to devise particularly for processes such as heap bioleaching or environmental cleanup, because there are many variables that cant be adequately monitored or controlled. There is also a certain futility in technology guarantees, because the mine owner, in fact, owns the risk. The mining company has invested heavily in the process, controls the quality of the feed to the plant whether it is a mineral processing or environmental technology, and is in command of how the process is operated. Availability of skilled engineers and scientists Dramatic declines in metal prices nearly always result in the mining industry cutting-back on research and development, which means lay-offs of experienced scientists and engineers who may have worked decades on biohydrometallurgical processes. Industry is not the only sector subject to the loss of talent. Declining metal prices and a sluggish economy usually result in less money for R&D at universities and government laboratories. Mining schools may even cut-back curriculum and professors, who have long been involved in biohydrometallurgical research. Such cut-backs in talent and R&D can have a serious impact when the economy recovers and decisions are made to consider biohydrometallurgy as a processing option. Talent is no longer available and corporate memory is lost. It may take years before less experienced scientists and engineers can become acquainted with techniques and historical developments and constructively contribute to the state-of-the-art of the technology.

Technical Challenges. The commercial challenges of implementing biohydrometallurgy should not discourage research and development. Despite the boom-and-bust cycles of mining and metal industries, companies do rely on innovation to remain competitive, decrease production and environmental costs, confidently process complex ores, surmount environmental permitting issues and maximize investment. Some of the technical challenges and opportunities to be addressed by research and development are discussed: Heap leaching of primary sulfide minerals. Progress has been made recently in the heap bioleaching of chalcopyrite [19], but more research and development are necessary to fully understand the conditions under which primary sulfides are leached, how to achieve the conditions necessary for the bioleaching to occur and how to successfully engineer the heaps to maintain the necessary conditions. A more fundamental understanding of the slightly reducing conditions that can occur with the use of thermophiles is needed and particularly in relation to how these conditions correlate with the dissolution of chalcopyrite and other primary copper sulfide minerals. Heap bioleach model development, integration, and validation. There have been mathematical models developed for various heap leaching aspects such as hydrology and heat balance, however, more robust modeling is needed for the microbial aspects of heap leaching. To fully exploit the value of heap modeling, the models must be integrated and validated using data from existing commercial-scale operations. This effort not only

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requires a team effort by researchers and engineers, but also the commitment by industry to support the effort by providing information on heaps. Some of the information necessary to validate models will require heap leach data that are currently not collected. Better understanding of secondary copper sulfide heap leaching. Although crushed ore heap leaching of secondary copper sulfides has been widely used for over a decade, there are still some production issues. Some specific technical questions follow: o How long does it take for the microbial population to develop in the heap when the source of the organisms is the raffinate and natural development in the stacked ore? o Would inoculation of the ore be of any benefit? o Is aeration necessary during the entire leach period and what aeration rate is really needed? o Why does the temperature in most secondary copper heap leach operations remain quite cool? Is this a result of slow oxidation of sulfides, the absence of pyrite oxidation, or are there other reasons? o What is occurring at the microbe/mineral interface in terms of ORP, pH, and dissolved metals and how does this relate to what is observed in the bulk solution? Designing heap leaching for complex polymetallic ores, massive sulfide-type ores, and silicate-bound minerals. Heap bioleaching of complex ores can result in conditions considerably different than those observed in secondary copper heap leaching [19, 20]. For example, pyrrhotite, which may be present in complex ores, releases substantial amounts of heat rather quickly and consumes acid, creating operating conditions that must be carefully managed in order to effectively utilize microbial leaching. There has been very limited experience in the bioleaching of massive sulfide deposits. Yet both complex ores and massive sulfide deposits will be exploited in the future and these represent opportunities for bioleaching studies to better prepare us for future use of the technology. Silicate locking of minerals is a significant challenge in many existing mining operations and there are limited options for dealing with the problem. Microorganisms may provide a processing option, but R&D must be closely coupled with economic realities to address this opportunity. In-situ leaching. As the world becomes more urbanized, it is inevitable that more people will live closer to mining operations. Therefore, it is increasingly important that we lessen the footprint of mining. In-situ mining is an approach that could substantially diminish the surface impacts of mining. How to effectively accomplish in-situ mining for many minerals is a huge challenge. Can biological methods somehow be exploited? Can we use microbial technology to contain leach solutions in subsurface deposits? Can we use microbes to increase the permeability of subsurface deposits? Can we use bioleaching? Are there alternative electron acceptors that can be used in the bioleach process? Are there new microbe-based mineral dissolution processes that we should be considering? While in-situ technology for some minerals is far in the future, it is not too soon to begin to develop the fundamentals around such a processing option. Technology for decommissioning cyanide-leached heaps. Rotating biological contactors were developed and used to treat cyanide-, thiocyanate-, and metal-contaminated waters resulting from gold treatment. However, the technology has not been fully developed and evaluated for degrading cyanide and thiocyanate in decommissioned gold heap leaching operations. Biotechnical methods to hasten the decommissioning process could result in substantial cost savings for the industry. Such technology may also be applied

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to decontaminate tailings that contain residual gold values locked in sulfide minerals enabling the biooxidation pretreatment of the tailings for re-processing. Technology for stabilizing sulfide-bearing wastes. Insufficient research has been undertaken on using biotechnology for stabilizing sulfidic waste rock and tailings. New thinking is needed to look at microbial products and processes that will prevent acid rock drainage from ever forming.

Biometallurgys Future Biohydrometallurgy for both mine and production and remediation will continue to play an important role in mining and metal industries. Bioleaching lends itself economically and technically to the processing of small deposits that cant support high capital costs, remote deposits where making and shipping concentrates may not be a viable option, low-grade ores that cant be cost-effectively treated by existing technologies, and complex ores. Bioleaching also offers opportunities as an adjunct process for on-site generation of acid for adjunct operations, such as base metal oxide heap leaching. Bioleaching, in some cases, may be more environmentally acceptable than other technologies resulting in faster permitting of operations. Despite its commercial successes there are technical challenges that need to be addressed even for existing applications. While emphasis has been placed largely on the bioleaching of sulfidic-refractory gold concentrates in stirred-tank reactors and on the dump and heap bioleaching of secondary copper sulfide ores, development is underway on heap leaching of lowgrade chalcopyrite ores [21]. Nevertheless there are new opportunities for bioleaching that have yet to be fully realized. Complex polymetallic deposits, massive sulfide deposits and silicate-bound minerals are new frontiers for bioleaching. Even farther in the future is in-situ leaching using microbial processes. While in-situ leaching is used today for the extraction of certain metals for example, uranium the potential of using microorganisms exists. Substantial research, development and engineering efforts must be mounted to develop viable microbial technologies for these opportunities. The commercial challenges described earlier must also be addressed. Metals bioremediation has been extensively exploited for acid rock drainage treatment using passive methods such as constructive anaerobic wetlands and employing more engineered processes [22, 23]. The degradation of cyanide and thiocyanate complexes and the sorption of metals have seemingly not been commercially exploited to such an extent, despite having been successfully engineered and commercially employed in the early 1990s [6]. There are important opportunities for bioremediation in decommissioning cyanide heap leach operations and for the stabilization and isolation of mine wastes. These opportunities require focused research coupled with aggressive development and engineering. References [1] Information on http://www.kitco.com/charts/livegold.html [2] B. Amey: Gold Metal Prices in the United States through 1998, U.S. Geological Survey, United States Department of the Interior, Information on http://minerals.usgs.gov/minerals/pubs/commodity/gold/300798.pdf [3] Information on http://www.kitcometals.com/charts/copper_historical_large.html#5years [4] D. Edelstein: Copper - Metal Prices in the United States through 1998, U.S. Geological Survey, United States Department of the Interior, Information on http://minerals.usgs.gov/minerals/pubs/commodity/copper/240798.pdf [5] P.C. van Aswegen, J. van Niekerk and W. Olivier, in: Biomining, edited by D.E. Rawlings and B.D. Johnson, pp. 1-33, Springer-Verlag, Berlin Heidelberg (2007) [6] J.L. Whitlock and G.R. Smith, in: Biohydrometallurgy 1989, edited by J. Salley, R.G.L. McCready and P.L. Wichlacz, pp. 613-625, Canada Centre for Mineral and Energy Technology, Ottawa (1989)

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[7] T.C. Logan, T. Seal and J.A. Brierley, in: Biomining, edited by D.E. Rawlings and B.D. Johnson, pp. 113-138, Springer-Verlag, Berlin Heidelberg (2007) [8] T.J. Harvey and M. Bath, in: Biomining, edited by D.E. Rawlings and B.D. Johnson, pp. 97-112, Springer-Verlag, Berlin Heidelberg (2007) [9] S.R. Zimmerley, D.G. Wilson and J.D. Prater, U.S. Patent 2,829,964 (1958) [10] R.L.P. Kleinmann, in: Control of Acid Mine Drainage, pp. 48-52, Bureau of Mines Information Circular 9027, United States Department of the Interior (1985) [11] R. Montealegre and S. Bustos, in: Bioleaching from Molecular Biology to Industrial Applications, edited by R. Badilla-Ohlbaum, T. Vargas and L. Herrera, pp. 95-106, Universidad de Santiago de Chile (1990) [12] C. Buisman, R. Post, P. Yspeert, G. Geraats and G. Lettinga: Acta Biotechnol. Vol. 9 (1989), pp. 255 [13] J.D. Batty and G.V. Rorke, in: Proceedings of the 16th International Biohydrometallurgy Symposium, edited by S.T.L. Harrison, D.E. Rawlings and J. Petersen, pp. 153-161, 16th International Biohydrometallurgy Symposium (2005) [14] Information on http://www.zealllc.com/2008/goldmine2.htm [15] P. Moore: Mining Magazine, Vol. 194 (2008), p. 54 [16] T.P. McNulty, in: Managing Innovation in the Minerals Industry, edited by M.C. Kuhn, pp. 114, Society for Mining, Metallurgy, and Exploration, Inc., Littleton, Colorado (1998) [17] J. Canterford, in: Hydrometallurgy 2008, Proceedings of the Sixth International Symposium, edited by C.A. Young, P.R. Taylor, C.G. Anderson and Y. Choi, pp. 14-22, Society for Mining, Metallurgy, and Exploration, Inc., Littleton, Colorado (2008) [18] Information on http://www.min-eng.com/commodities/metallic/copper/news/3.html [19] H.R. Watling: Hydrometallurgy, Vol. 91 (2008), p. 70 [20] P.J. van Staden, M. Gericke and P.M. Craven, in: Hydrometallurgy 2008, Proceedings of the Sixth International Symposium, edited by C.A. Young, P.R. Taylor, C.G. Anderson and Y. Choi, pp. 6-13, Society for Mining, Metallurgy, and Exploration, Inc., Littleton, Colorado (2008) [21] H.R. Watling: Hydrometallurgy, Vol. 84 (2006), p. 81 [22] Information on http://www.bioteq.ca [23] Information on http://www.paques.nl/en/for_water

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Biohydrometallurgy 2009 doi:10.4028/www.scientific.net/AMR.71-73 Biohydrometallurgy: What is its Future? doi:10.4028/www.scientific.net/AMR.71-73.3 References [1] Information on http://www.kitco.com/charts/livegold.html [2] B. Amey: Gold Metal Prices in the United States through 1998, U.S. Geological Survey, United States Department of the Interior, Information on http://minerals.usgs.gov/minerals/pubs/commodity/gold/300798.pdf [3] Information on http://www.kitcometals.com/charts/copper_historical_large.html#5years [4] D. Edelstein: Copper - Metal Prices in the United States through 1998, U.S. Geological Survey, United States Department of the Interior, Information on http://minerals.usgs.gov/minerals/pubs/commodity/copper/240798.pdf [5] P.C. van Aswegen, J. van Niekerk and W. Olivier, in: Biomining, edited by D.E. Rawlings and B.D. Johnson, pp. 1-33, Springer-Verlag, Berlin Heidelberg (2007) doi:10.1007/978-3-540-34911-2_1 [6] J.L. Whitlock and G.R. Smith, in: Biohydrometallurgy 1989, edited by J. Salley, R.G.L. McCready and P.L. Wichlacz, pp. 613-625, Canada Centre for Mineral and Energy Technology, Ottawa (1989) [7] T.C. Logan, T. Seal and J.A. Brierley, in: Biomining, edited by D.E. Rawlings and B.D. Johnson, pp. 113-138, Springer-Verlag, Berlin Heidelberg (2007) doi:10.1007/978-3-540-34911-2_6 [8] T.J. Harvey and M. Bath, in: Biomining, edited by D.E. Rawlings and B.D. Johnson, pp. 97-112, Springer-Verlag, Berlin Heidelberg (2007) doi:10.1007/978-3-540-34911-2_5 PMid:17165141 [9] S.R. Zimmerley, D.G. Wilson and J.D. Prater, U.S. Patent 2,829,964 (1958) [10] R.L.P. Kleinmann, in: Control of Acid Mine Drainage, pp. 48-52, Bureau of Mines Information Circular 9027, United States Department of the Interior (1985) [11] R. Montealegre and S. Bustos, in: Bioleaching from Molecular Biology to Industrial Applications, edited by R. Badilla-Ohlbaum, T. Vargas and L. Herrera, pp. 95-106, Universidad de Santiago de Chile (1990) [12] C. Buisman, R. Post, P. Yspeert, G. Geraats and G. Lettinga: Acta Biotechnol. Vol. 9

(1989), pp. 255 doi:10.1002/abio.370090313 [13] J.D. Batty and G.V. Rorke, in: Proceedings of the 16th International Biohydrometallurgy Symposium, edited by S.T.L. Harrison, D.E. Rawlings and J. Petersen, pp. 153-161, 16th International Biohydrometallurgy Symposium (2005) [14] Information on http://www.zealllc.com/2008/goldmine2.htm [15] P. Moore: Mining Magazine, Vol. 194 (2008), p. 54 [16] T.P. McNulty, in: Managing Innovation in the Minerals Industry, edited by M.C. Kuhn, pp. 1- 14, Society for Mining, Metallurgy, and Exploration, Inc., Littleton, Colorado (1998) [17] J. Canterford, in: Hydrometallurgy 2008, Proceedings of the Sixth International Symposium, edited by C.A. Young, P.R. Taylor, C.G. Anderson and Y. Choi, pp. 14-22, Society for Mining, Metallurgy, and Exploration, Inc., Littleton, Colorado (2008) [18] Information on http://www.min-eng.com/commodities/metallic/copper/news/3.html [19] H.R. Watling: Hydrometallurgy, Vol. 91 (2008), p. 70 [20] P.J. van Staden, M. Gericke and P.M. Craven, in: Hydrometallurgy 2008, Proceedings of the Sixth International Symposium, edited by C.A. Young, P.R. Taylor, C.G. Anderson and Y. Choi, pp. 6-13, Society for Mining, Metallurgy, and Exploration, Inc., Littleton, Colorado (2008) [21] H.R. Watling: Hydrometallurgy, Vol. 84 (2006), p. 81 doi:10.1016/j.hydromet.2006.05.001 [22] Information on http://www.bioteq.ca [23] Information on http://www.paques.nl/en/for_water