Word to the Wise

JOHN RAKOVAN Department of Geology Miami University Oxford, Ohio 45056 rakovajf@muohio.edu

Environmental Mineralogy

ith all of the news reports of global warming and other environmental troubles facing society today, one might wonder if mineral science has any role to play in solving these problems. It certainly does! Traditionally, the major application of minerals and mineral science has been in the understanding of how rocks form (petrogenesis) and behave. This is essentially the study of the solid part of the earth, or petrology. Mineralogy by its very nature, however, is an interdisciplinary science, as is geology, in which the principles of physics and chemistry are applied to Earth materials. There are numerous other applications of minerals outside the realm of petrology or even geology, and the importance of minerals extends into many areas of scientific and technological pursuit including materials science, environmental science, medicine, biology, and engineering. A series of forthcoming Word to the Wise columns will address modern mineralogy and its application in these diverse disciplines. In this column we explore some of the connections that minerals and mineral science have with our environment and in helping to solve environmental problems facing society today: in other words, environmental mineralogy. So what exactly is environmental mineralogy? To quote the recently established International Mineralogical Association (IMA) Working Group on Environmental Mineralogy and Geochemistry:
Environmental mineralogy [and geochemistry] is an interdisciplinary field dealing with systems at, or near, the surface of the Earth where the geosphere comes into contact with the hydrosphere, atmosphere and biosphere. This is the environment on which plants and animals (including humans) depend for survival and which can be disrupted by human activity, particularly that associated with exploitation and utilization of Earths resources. It deals with those systems containing minerals that constitute key environments (modern sediments, soils, atmospheric aerosols, parts of certain micro and macro organisms including the human body). Both pure systems and those contaminated through human activities

Figure 1. Scanning electron microscopy image of pyromorphite (bright crystals) on ferrihydrite in a Pb-contaminated sediment after the addition of phosphate solution. Growth of pyromorphite sequesters the Pb in a biologically unavailable form. Tomasz Marchlewski photomicrograph. are considered, and with emphasis on a fundamental (predictive) understanding of such systems at scales which can range from molecular to global. Examples of specific topics within the remit of environmental mineralogy and geochemistry include: release, transport and dispersal of toxic wastes from mining and industry (including the nuclear industry) and the safe containment of such wastes; mineral-based atmospheric aerosols; minerals in the human body; geochemistry and human health; preservation of minerals and rocks in culturally important buildings and artifacts.

Dr. John Rakovan, an executive editor of Rocks & Minerals, is a professor of mineralogy and geochemistry at Miami University in Oxford, Ohio.
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Environmental mineralogy is obviously a very diverse subdiscipline of mineralogy, and a comprehensive review of its many aspects is far beyond the scope of this column. To explore the idea to a greater depth, lets look at two

Figure 2. Scanning electron microscopy image of pyromorphite (bright crystals) on smectite in a Pb-contaminated sediment after the addition of phosphate solution. Growth of pyromorphite sequesters the Pb in a biologically unavailable form. Tomasz Marchlewski photomicrograph. Figure 3. Scanning electron microscopy image of asbestos-form chrysotile fibers extracted from an autopsied human lung. The fibers are 530 microns long and are coated with an iron-rich material (cauliflower-like coating) thought to be derived from human proteins. The processes that lead to the development of diseases such as lung cancer are of concern to environmental mineralogy. Image by Lesley S. Smith and Anne F. Sorling, from MSA RIM vol. 28.

applications of environmental mineralogy: (1) remediation of heavy-metal contaminates that are currently in the environment, and (2) the design of solid forms of radioactive waste for stable disposal. Methods for remediation of contaminated sites as well as the disposition of contained waste are two of the most urgent, and potentially costly, environmental problems facing society today (Ewing and Wang 2002; Langmuir 1997). One significant class of environmental pollutants is heavy metals such as Pb, As, Cd, Cr, and Hg, which are toxic, even at low concentrations, and may act as carcinogens. These may be naturally present, but human activity has greatly increased the flux of biologically available forms of heavy metals in the environment. One of the key concepts in planning an effective remediation strategy for sites that are contaminated with heavy metals (e.g., Pb and As in sediments and soils surrounding smelters) is bioavailability. There are several possible forms (speciation) in which metals can be found in a contaminated sediment. They may be dissolved in ground water (aqueous); they may be adsorbed to the surfaces of minerals, organic compounds, or bacteria; or they may be incorporated into the crystal structures of minerals. If the metals are present in a form that cannot get into plants and animals or is nonreactive (i.e., cannot be metabolized), they are not bioavailable and pose a much lower health risk. This leads to one possible strategy for contaminant remediation. Instead of removing the metals from the environment, the idea is to change their speciation to a stable, nonbioavailable form, such as being incorporated into the crystal structure of a mineral with low solubility. One mineral currently being used in this application is apatite. The anthropogenic formation of apatite in contaminated soils and sediments (sometimes called phosphate-induced metal stabilization, PIMS) is a new and promising method for sequestering metals (including radionuclides) and environmental remediation (Chen et al. 1997; Conca et al. 2000; Bostick et al.

2000). PIMS works by precipitation and incorporation of metals into minerals (most importantly apatite) that do not dissolve or leach over very long time periods. After incorporation, the metals are no longer bioavailable, are far less dispersible, and thus pose a substantially reduced health risk. Another example of metal sequestration and stabilization is specific to arsenic contamination in ground waters, a major problem worldwide (Vaughan 2006). PIMS may potentially work in this application because As readily enters the apatite structure (e.g., johnbaumite, Ca5(AsO4)3OH, is isostructural with apatite). However, other minerals, including pyrite and scorodite, are also being used to tie up arsenic in unbioavailable forms. In the case of pyrite, its formation can be induced by stimulating the growth of sulfate-reducing bacteria that naturally exist in many environments or by introducing these bacteria if not naturally present. The reduction of sulfate in the presence of Fe, as part of the biological activity of the bacteria, leads to pyrite formation; if As is present in the ground water, it will also be incorporated (Saunders et al. 2001, 2005). The pyrite will remain stable, with As locked into its structure, as long as conditions remain reducing. Methods in which biological activity is used to help with contaminant immobilization or cleanup, such as this, are known as bioremediation. A related problem is the disposal of industrial waste that is currently contained but in an unfavorable form for disposal (e.g., in aqueous solution). This problem is particularly germane to radioactive waste products from weapons manuVolume 83, March/April 2008 173

Selected Books and Review Volumes on Topics Related to Environmental Mineralogy

Alpers, C. N., J. L. Jambor, and D. K. Nordstrom, eds. 2000. Sulfate mineralsCrystallography, geochemistry, and environmental significance. RIMG* vol. 40. Banfield, J. F., J. Cervini-Silva, and K. M. Nealson, eds. 2005. Molecular geomicrobiology. RIMG vol. 59. Banfield, J. F., and A. Navrotsky, eds. 2001. Nanoparticles and the environment. RIMG vol. 44. Banfield, J. F., and K. H. Nealson, eds. 1998. Geomicrobiology: Interactions between microbes and minerals. RIMG vol. 35. Bish, D., and D. Ming, eds. 2001. Natural zeolites: Occurrence, properties, applications. RIMG vol. 45. Burns, P. C., and R. Finch, eds. 1999. Uranium: Mineralogy, geochemistry and the environment. RIMG vol. 38. Cabri, L. J., and D. J. Vaughan, eds. 1998. Modern approaches to ore and environmental mineralogy. MAC vol. 27. Cotter-Howells, J. D., L. S. Campbell, E. Valsami-Jones, and M. Batchelder, eds. 2000. Environmental mineralogy: Microbial interactions, anthropogenic influences, contaminated land and waste management. MSS. Dove, P. M., J. J. De Yoreo, and S. Weiner, eds. 2003. Biomineralization. RIMG vol. 54. Fenter, P., M. Rivers, N. Sturchio, and S. Sutton, eds. 2002. Applications of synchrotron radiation in low-temperature geochemistry and environmental science. RIMG vol. 49. Fleet, M. E., ed. 1984. Environmental geochemistry. MAC vol. 10. Guthrie, G. D., and B. T. Mossman, eds. 1993. Health effects of mineral dusts. RIMG vol. 28. Henderson, G., and D. Baker, eds. 2002. Synchrotron radiation: Earth, environmental, and material sciences applications. MAC vol. 30. Jambor, J. L., D. W. Blowes, and A. I. M. Ritchie, eds. 2003. Environmental aspects of mine wastes. MAC vol. 31. Kohn, M. L., J. Rakovan, and J. M. Hughes, eds. 2002. PhosphatesGeochemical, geobiological, and materials importance. RIMG vol. 48. Lichtner, P. C., C. I. Steefel, and E. H. Oelkers, eds. 1997. Reactive transport in porous media. RIMG vol. 34. McIntosh, J. M., and L. A. Groat, eds. 1997. Biological-mineralogical interactions. MAC vol. 25. Sahai, N., and M. A. A. Schoonen, eds. 2006. Medical mineralogy and geochemistry. RIMG vol. 64. Vaughan, D. J., and R. A. Wogelius, eds. 2000. Environmental mineralogy. EMU vol. 2.
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Figure 4. False color SEM image of a chain of filamentous bacteria cells (blue; dehydrated because of SEM vacuum) associated with micrometer-scale aggregates of sphalerite. The sphalerite crystals formed as a result of sulfate reduction by the bacteria. From Labrenz et. al. (2000). Reprinted with permission from AAAS.

facture or spent nuclear fuel. Tractable strategies for the disposal of nuclear waste necessitate development and use of highly durable waste forms. Vitrification, the process of converting a material into a glasslike amorphous solid, has been investigated extensively. More recently, there is an increased interest in the potential of locking radioactive elements from nuclear waste into stable mineral structures and then disposing of these minerals in geological repositories such as the Waste Isolation Pilot Plant (WIPP) outside Carlsbad, New Mexico, or Yucca Mountain in southwest Nevada. The idea is that putting radionuclides into stable mineral structures will greatly decrease the potential of their dispersal in the environment after they are buried, for example, through ground-water movement. Examples of minerals that are being investigated for this purpose are zircon, monazite, and apatite. In any mineral waste form, certain characteristics are desired, including (1) a high capacity for the incorporation of the radionuclides (elements) of concern, as well as selected fission products resulting from their decay; (2) a reasonable chemical durability (e.g., low solubility in natural waters) depending on the geochemical environment for disposal; and (3) a propensity for rapid annealing of radiation damage. Ultimately, scientists may find that the best form of radioactive waste for contained disposal is as constituents in mineral structures. Mineralogical solutions to environmental problems sometimes involve the transformation of waste into new, usable materials rather than disposal. One example is the conversion of waste materials created in the recycling of paper. During the manufacture of recycled paper products, paper sludge is generated as an industrial waste. Although not a hazardous material, large quantities of paper sludge are disposed of in landfills, creating an environmental problem because of limited landfill capacities, particularly in countries such as Japan where usable land is at a premium.
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RIMG: Reviews in Mineralogy and Geochemistry published by the Mineralogical Society of America and the Geochemical Society.

MAC: Mineralogical Association of Canada Short-Course volume.

MSS: The Mineralogical Society Series published by the Mineralogical Society of Great Britain and Ireland in association with Kluwer Academic Publishers.

EMU: The European Mineralogical Union Review volumes.

Mineralogists and other scientists (Wajima et al. 2006, 2007) are investigating the potential of converting paper sludge into usable minerals such as zeolites. Once converted, these materials may ultimately find use in other environmental applications such as sorbents for water purification.

Environmental mineralogy is by no means new, but it is certainly seeing an impressive rise in scope and activity. One indication of this is the number of recent books and monographs that review the immense literature and diverse applications of environmental mineralogy. The sidebar lists numerous examples of such review volumes. Recently, both the American Mineralogist and Mineralogical Magazine published special green issues that focus on environmental mineralogy. The important role of minerals in many interesting environmental problems makes today a very exciting time for mineralogy.
ACKNOWLEDGMENTS I thank Bob Cook and Olaf Borkiewicz for their reviews of this manuscript and their helpful suggestions. I also thank Tomasz Marchlewski, Lesley Smith, and Anne Sorling for the use of their images. REFERENCES Bostick, W. D., R. J. Jarabek, D. A. Bostick, and J. L. Conca. 2000. Phosphate induced metal stabilization: Use of apatite and bone char for the removal of soluble radionuclides in authentic and simulated DOE groundwaters. Advances in Environmental Research 3:48898. Chen, X., J. Wright, J. L. Conca, and L. M. Peurrung. 1997. Evaluation of heavy metal remediation using the mineral apatite. Water, Air and Soil Pollution 98:5778. Conca, J. L., N. Lu, G. Parker, B. Moore, A. Adams, J. V. Wright, and P. Heller. 2000. PIMS remediation of metal contaminated waters and soils. In Remediation of chlorinated and recalcitrant compounds, ed. Wickramanayake, Gavaskar, Gibbs, and Means, vol. 7, 31926. Columbus, Ohio: Battelle Memorial Institute. Ewing, R. C., and L. Wang. 2002. Phosphates as nuclear waste forms. In Phosphates: Geochemical, geobiological and materials importance, ed. M. Kohn, J. Rakovan, and J. M. Hughes, 67399. Reviews in mineralogy and geochemistry, vol. 48. Washington, DC: Mineralogical Society of America. Labrenz, M., G. K. Druschel, T. Thomsen-Ebert, B. Gilbert, S. A. Welch, K. M. Kemner, G. A. Logan, R. E. Summons, G. De Stasio, P. L. Bond, B. Lai, S. D. Kelly, and J. F. Banfeld. 2000. Formation of sphalerite (ZnS) deposits in natural biofilms of sulfate-reducing bacteria. Science 290:174447. Langmuir, D. 1997. Aqueous environmental chemistry. Upper Saddle River, NJ: Prentice Hall. Saunders, J. A., M.-K. Lee, J. M. Whitmer, and R. C. Thomas. 2001. In-situ bioremediation of metalsContaminated groundwater using sulfate-reducing bacteria: A case study. Proceedings 6th International Symposium on In-Situ and On-Site Bioremediation 6 (9):10512. Saunders, J. A., S. Mohammad, N. E. Korte, M. -K. Lee, D. Castle, M. O. Barnett, M. Fayek, and L. Riciputi. 2005. Groundwater geochemistry, microbiology and mineralogy in two arsenic-bearing Holocene alluvial aquifers from the USA. In Advances in arsenic research: Integration of experimental and observational studies and implications for mitigation, 191205. American Chemical Society symposium series, vol. 915. Vaughan, D. J., guest ed. 2006. Arsenic. Elements 2 (2): 65128. Wajima, T., M. Haga, K. Kuzawa, H. Ishimoto, O. Tamada, K. Ito, T. Nishiyama, R. Downs, and J. Rakovan. 2006. Zeolite synthesis from paper-sludge ash at low temperature (90C): Addition of diatomite for SiO2. Journal of Hazardous Materials B132:24452. Wajima, T., H. Ishimoto, K. Kuzawa, K. Ito, O. Tamada, M. E. Gunter, and J. Rakovan. 2007. Material conversion from paper-sludge ash in NaOH, KOH, and LiOH solutions. American Mineralogist 92:110511.

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