History of biohydrometallurgy

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One of the first reports where bioleaching might have been involved in the mobilization of metals is given by the Roman writer Gaius Plinius Secundus (23 - 79 A.D.). In his work naturalis historiae libris XXXVII on natural sciences , Plinius describes how copper minerals are obtained using a leaching process.[1] The translation reads approximately as follows: "Chrysocolla is a liquid in the before mentioned gold mines running from the gold vein. In cold weather during the winter the sludge freezes to the hardness of pumice. It is know from experience that the most wanted [chrysocolla] is formed in copper mines, the following in silver mines. The liquid is also found in lead mines although it is of minor value. In all these mines chrysocolla is also artificially produced by slowly passing water through the mine during the winter until the month of June; subsequently, the water is evaporated in June and July. It is clearly demonstrated that chrysocolla is nothing but a decomposed vein."

The German physician and mineralogist Georgius Agricola (1494 - 1555) mentioned in his work de re metallica also techniques for copper winning based on the leaching of copper-containing ores [2]. A woodcut from his book illustrates the manual transport of metal-containing leachates (resulting from microbial activities) from mines and their evaporation in the warm sunlight:

Image:Agricola.jpg

The Rio Tinto mines in South-Western Spain are usually considered as the cradle of biohydrometallurgy. These mines have been exploited since pre-Roman times for their copper, gold, and silver values. However, with respect to commercial bioleaching operations on an industrial scale, biohydrometallurgical techniques were introduced to the Tharsis mine in Spain earlier [3]. As a consequence of the ban on open air ore roasting and its resulting atmospheric sulfur emissions in 1878 in Portugal, hydrometallurgical metal extraction has been taken into consideration in other countries as well, and more intensely. In addition to the ban, cost savings were an incentive for the development: Heap leaching techniques were assumed to reduce transportation costs and to allow the employment of locomotives and wagons for other services [4]. From 1900 on, no open air roasting of low-grade ore was conducted at Rio Tinto mine.

Efforts to establish bioleaching at the Rio Tinto mines were made in the beginning of the 1890's. Heaps (10 m in height) of low-grade ore (containing 0.75% Cu) were built and left for one to three years for "natural" decomposition [5]. 20% to 25% of the copper left in the heaps was recovered annually. It was calculated that approximately 200'000 tons of rough ore could be treated in 1896. Although industrial leaching operations were conducted at Rio Tinto mines for several decades, the contribution of bacteria to metal solubilization was confirmed only in 1961, when Thiobacillus ferrooxidans (reclassified as Acidithiobacillus) was identified in the leachates.

Although metal leaching from mineral resources has a very long historical record [6] [7] and although the oxidation of reduced sulfur compounds and elemental sulfur resulting in the formation sulfuric acid was demonstrated already in the 1880's [8], the oxidation of metal sulfides was not reported until 1922 when the oxidation of pyrite and the mobilization of zinc from zinc sulfide was investigated [9] [10]. It was found that the transformation of zinc sulfide to zinc sulfate was microbially mediated. Based on these results, the economic recovery of zinc from zinc-containing ores by biological methods was proposed. In 1947, Thiobacillus ferrooxidans was identified as part of the microbial community found in acid mine drainage [11]. A first patent was granted in 1958 [12]. The patent describes a cyclic process where a ferric sulfate sulfuric acid lixiviant solution is used for metal extraction, regenerated by aeration (ferrous iron oxidation by iron oxidizing organisms), and re-used in a next leaching stage.

Fungi are also able to attack solid materials such as minerals or building materials [13]. Early indications are reported in the Old Testament where Chapter 14 of the book of Leviticus describes the growth of red and green organisms [fungi? lichens?] on the walls of houses creating pits and cavities which might be attributed to the excretion of organic acids. It is known that organic acids are formed in situ under conditions of low nutrient availability. Early reports on the action of organic acids on solids describe solubilization of fine powdered glass and a variety of minerals by oxalic acid, which is a fungal metabolite [14] . Phosphates of iron, silver, zinc, and copper, arsenates of iron, silver, and copper, chromates of zinc, bismuth, barium, mercury, and lead are also decomposed by oxalic acid. Slater assumed that the influence of lichens containing oxalic acid was a major factor in effecting the disintegration and decomposition of rocks.

Timeline

  • Old Testament, red and green organisms [fungi? lichens?] on the walls of houses create pits and cavities.
  • 23 - 79 A.D. Roman writer Gaius Plinius Secundus, how copper minerals are obtained using a leaching process. [15] "chrysocolla is also artificially produced by slowly passing water through the mine during the winter until the month of June; subsequently, the water is evaporated in June and July.''
  • 166 A.D. The scientist Galen described "in-situ"-leaching in an old, cypriotic mine. [16]
  • Sometime between 1480-1539. Heap leaching in order to extract FeSO4 was first described in De Pirotechnica by the italian metallurg V. Biringguccio (1480-1539). [17]
  • 1494 - 1555. Georgius Agricola, techniques for copper winning based on the leaching of copper-containing ores. [18] Agricola also described roasting pyrite to prepare for leaching and produce FeSO4.
  • 1572, Industrial heap leaching of copper-sulfides in Rio Tinto, Spain. Roasting of copper- and iron-sulfides, then leaching. [19]
  • 1878, Ban of open air ore roasting to combat its resulting atmospheric sulfur emissions in hydrometallurgical metal extraction has since been taken into consideration in other countries as well.
  • Heap leaching techniques were assumed to reduce transportation costs and to allow the employment of locomotives and wagons for other services [20].
  • Earlier 1890's, efforts to establish bioleaching to the Rio Tinto mines. Heaps of low-grade ore, left for one to three years for "natural" decomposition [21]. The heap leaching in the Rio Tinto mines continued successfully until the 1970's. The reason for the successful process was said to depend on some mystic characteristic of the Rio Tinto ore or on the Spanish climate. [22]
  • 1900, No further open air roasting of low-grade ore was conducted at Rio Tinto mine.
  • 1922, Oxidation of metal sulfides was reported [23] [24].
  • 1940. It was estimated that million of tons of sulfuric acid was discharged into the Ohio river because of the involontary leaching of sulfides in carbon (which was obtained from the carbon mines in Pennsylvania.) Investigations in order to solve the problem. [25]
  • 1947, Thiobacillus ferrooxidans was identified as part of the microbial community found in acid mine drainage [26].
  • 1950's, Leach-dumps (predecessor of leach-heaps) [27]
  • 1958, A first patent was granted [28], cyclic process where a ferric sulfate sulfuric acid lixiviant solution is used for metal extraction, regenerated by aeration (ferrous iron oxidation by iron oxidizing organisms), and re-used in a next leaching stage.
  • 1961, Thiobacillus ferrooxidans (reclassified as Acidithiobacillus) was identified in the leachates.
  • 1965, Discovery of the first iron- and sulfuroxidizing archaea - Acidianus Brierleyi - from an acidic, thermal spring in Yellowstone National Park (USA) [29]
  • 1977, The first international biohydrometallurgy meeting [30]
  • 1995, Bioleaching of chalcopyrite concentrate was developed and evaluated on a commercial scale [31]
  • 2000, Commercial scale applications with archaea [32]
  • 2003, Demonstration of potential commercial applications - the [[BioCopTM]] process by BHP Billiton employed acidophilic, iron-oxidizing archaea for bioleaching of chalcopyrite concentrates in aerated stirred tanks [33]

References

  1. Plinius G. secundus. Naturalis historiae libri XXXVII [on-line access under http://penelope.uchicago.edu/Thayer/E/ Roman/Texts/Pliny_the_Elder/home.html]
  2. Agricola G (1556) De re metallica libri XII. Froben, Basle, Switzerland [on-line access under http://libcoll.mpiwg-berlin.mpg.de/elib/]
  3. Salkield L.U. (1987) A technical history of the Rio Tinto mines: some notes on exploitation from pre-Phoenician times to the 1950s. Institution of Mining and Metallurgy, London, UK
  4. Salkield L.U. (1987) A technical history of the Rio Tinto mines: some notes on exploitation from pre-Phoenician times to the 1950s. Institution of Mining and Metallurgy, London, UK
  5. Salkield L.U. (1987) A technical history of the Rio Tinto mines: some notes on exploitation from pre-Phoenician times to the 1950s. Institution of Mining and Metallurgy, London, UK
  6. Ehrlich H.L. (1999) Past, present and future of biohydrometallurgy. Hydrometallurgy 95:127-134
  7. Rossi G. (1990) Biohydrometallurgy. McGraw-Hill, Hamburg, Germany
  8. Winogradsky S. (1887) Ueber Schwefelbacterien. Botanische Zeitung 45:489-610
  9. Rudolfs W. (1922) Oxidation of iron pyrites by sulfur-oxidizing organisms and their use for making mineral phosphates available. Soil Science 14:135-147
  10. Rudolfs W., Helbronner A. (1922) Oxidation of zinc sulfide by microörganisms. Soil Science 14:459 - 464
  11. Colmer A.R., Hinkle M.E. (1947) The role of microoganisms in acid mine drainage. Science 106:253 - 256
  12. Zimmerley S.R., Wilson D.G., Prater J.D. (1958) US Patent 2,829,964
  13. Sterflinger K. (2000) Fungi as geological agents. Geomicrobiology Journal 17:97-124
  14. Slater J.W. (1856) On some reactions of oxalic acid. Chemical Gazette 14:130-131
  15. Plinius G. Secundus. Naturalis historiae libri XXXVII [on-line access under http://penelope.uchicago.edu/Thayer/E/ Roman/Texts/Pliny_the_Elder/home.html]
  16. Brombacher C., Bachofen R., Brandl H. (1997) Biohydrometallurgical processing of solids: a patent review. Applied Microbiology & Biotechnology 48:577-587
  17. Biometech, Studie avseende Bio & Hydrometallurgiskt center, 2002.
  18. Agricola G (1556) De re metallica libri XII. Froben, Basle, Switzerland [on-line access under http://libcoll.mpiwg-berlin.mpg.de/elib/]
  19. Biometech, Studie avseende Bio & Hydrometallurgiskt center, 2002.
  20. Salkield L.U. (1987) A technical history of the Rio Tinto mines: some notes on exploitation from pre-Phoenician times to the 1950s. Institution of Mining and Metallurgy, London, UK
  21. Salkield L.U. (1987) A technical history of the Rio Tinto mines: some notes on exploitation from pre-Phoenician times to the 1950s. Institution of Mining and Metallurgy, London, UK
  22. Biometech, Studie avseende Bio & Hydrometallurgiskt center, 2002.
  23. Rudolfs W. (1922) Oxidation of iron pyrites by sulfur-oxidizing organisms and their use for making mineral phosphates available. Soil Science 14:135-147
  24. Rudolfs W., Helbronner A. (1922) Oxidation of zinc sulfide by microörganisms. Soil Science 14:459 - 464
  25. Biometech, Studie avseende Bio & Hydrometallurgiskt center, 2002.
  26. Colmer A.R., Hinkle M.E. (1947) The role of microoganisms in acid mine drainage. Science 106:253 - 256
  27. Brierley, J. A., Biohydrometallurgy - This Microbiologist's Perspective, Biohydrometallurgy Symposium 2007
  28. Zimmerley S.R., Wilson D.G., Prater J.D. (1958) US Patent 2,829,964
  29. Brierley, J. A., Biohydrometallurgy - This Microbiologist's Perspective, Biohydrometallurgy Symposium 2007
  30. Brierley, J. A., Biohydrometallurgy - This Microbiologist's Perspective, Biohydrometallurgy Symposium 2007
  31. Brierley, J. A., Biohydrometallurgy - This Microbiologist's Perspective, Biohydrometallurgy Symposium 2007
  32. Brierley, J. A., Biohydrometallurgy - This Microbiologist's Perspective, Biohydrometallurgy Symposium 2007
  33. Brierley, J. A., Biohydrometallurgy - This Microbiologist's Perspective, Biohydrometallurgy Symposium 2007

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