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Weathering of Almandine Garnet: Influence of Secondary Minerals on the Rate-Determining Step, and Implications for Regolith-Scale Al Mobilization

Published online by Cambridge University Press:  01 January 2024

Jason R. Price ,
Debra S. Bryan-Ricketts ,
Diane Anderson  and
Michael A. Velbel
Jason R. Price*
Affiliation:
Department of Earth Sciences, P.O. Box 1002, Millersville University, Millersville, PA 17551-0302, USA
Debra S. Bryan-Ricketts
Affiliation:
Department of Geological Sciences, 206 Natural Science Building, Michigan State University, East Lansing, Michigan 48824-1115, USA Environmental Protection Division, Los Alamos National Laboratory, Box 1663, Los Alamos, NM 87544, USA
Diane Anderson
Affiliation:
Department of Earth Sciences, P.O. Box 1002, Millersville University, Millersville, PA 17551-0302, USA Celerity, 4720 Gettysburg Rd., Suite 204, Mechanicsburg, PA 17055, USA
Michael A. Velbel
Affiliation:
Department of Geological Sciences, 206 Natural Science Building, Michigan State University, East Lansing, Michigan 48824-1115, USA
*
*E-mail address of corresponding author: Jason.Price@millersville.edu
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Abstract

Secondary surface layers form by replacement of almandine garnet during chemical weathering. This study tested the hypothesis that the kinetic role of almandine’s weathering products, and the consequent relationships of primary-mineral surface texture and specific assemblages of secondary minerals, both vary with the solid-solution-controlled variations in Fe and Al contents of the specific almandine experiencing weathering.

Surface layers are protective (PSL) when the volume of the products formed by replacement is greater than or equal to the volume of the reactants replaced. Under such circumstances, reaction kinetics at the interface between the garnet and the replacing mineral are transport controlled and either transport of solvents or other reactants to, or products from, the dissolving mineral is rate limiting. Beneath PSLs, almandine garnet surfaces are smooth, rounded, and featureless. Surface layers are unprotective (USL) when the volume of the products formed by replacement is less than the volume of the reactants replaced. Under such circumstances, reaction kinetics at the interface between the garnet and the replacing mineral are interface controlled and the detachment of ions or molecules from the mineral surface is rate limiting. Almandine garnet surfaces beneath USLs exhibit crystallographically oriented etch pits. However, contrary to expectations, etch pits occur on almandine garnet grains beneath some layers consisting of mineral assemblages consistent with PSLs.

Based on the Pilling-Bedworth criterion, surface layers are more likely to be protective over a broad range of reactant-mineral compositions when they contain goethite, kaolinite, and pyrolusite. However, this combination requires specific ranges of Fe and Al content of the natural reacting almandine garnet. To form a PSL of goethite and kaolinite, an almandine garnet must have a minimum Al stoichiometric coefficient of ~3.75 a.p.f.u., and a minimum Fe stoichiometric coefficient of ~2.7 a.p.f.u.

Product minerals also influence the mobility of the least-mobile major rock-forming elements. A PSL consisting of goethite, gibbsite, and kaolinite yields excess Al for export during almandine garnet weathering. As the quantity of kaolinite present in the PSL decreases, the amounts of Al available for export increases.

Keywords

Almandine GarnetChemical WeatheringCoweeta Hydrologic LaboratoryGibbsiteGoethiteHematiteKaoliniteProtective Surface LayersSaproliteUnprotective Surface Layers
Type
Research Article
Information
Clays and Clay Minerals , Volume 61 , Issue 1 , February 2013 , pp. 34 - 56
Copyright
Copyright © The Clay Minerals Society 2013

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References

Berner, R., 1978 Rate control of mineral dissolution under earth surface conditions American Journal of Science 278 1235–1252.CrossRefGoogle Scholar
Berner, R., Lasaga, A. and Kirkpatrick, R., 1981 Kinetics of weathering and diagenesis Kinetics of geochemical processes Washington, D.C. Mineralogical Society of America 111–134.CrossRefGoogle Scholar
Berner, R.A. and Holdren, G.R., 1977 Mechanism of feldspar weathering: Some observational evidence Geology 5 369–372.2.0.CO;2>CrossRefGoogle Scholar
Berner, R.A. and Holdren, G.R., 1979 Mechanism of feldspar weathering II: Observations of feldspar from soils Geochimica et Cosmochimica Acta 43 1173–7786.CrossRefGoogle Scholar
Berner, R. and Schott, J., 1982 Mechanism of pyroxene and amphibole weathering II. Observations of soil grains American Journal of Science 282 1214–1231.CrossRefGoogle Scholar
Berner, R. Sjoberg, E. Velbel, M. and Krom, M., 1980 Dissolution of pyroxenes and amphiboles during weathering Science 207 1205–1206.CrossRefGoogle ScholarPubMed
Berry, J.L., 1976.Study of chemical weathering in the Coweeta Hydrologic Laboratory, Macon County, North CarolinaGoogle Scholar
Blum, A.E. Lasaga, A.C., Stumm, W., 1987 Monte Carlo simulations of surface reaction rate laws Aquatic Surface Chemistry New York John Wiley & Sons 255–292.Google Scholar
Blum, A.E. Stillings, L.L., White, A.F. and Brantley, S.L., 1995 Feldspar dissolution kinetics Chemical Weathering Rates of Silicate Minerals Washington, D.C. Mineralogical Society of America 291–342.CrossRefGoogle Scholar
Brantley, S.L., Drever, J.I., 2005 Reaction kinetics of primary rock-forming minerals under ambient conditions Surface and Ground Water, Weathering, and Soils Oxford, UK Elsevier-Pergamon 73–117.Google Scholar
Brantley, S.L., Brantley, S.L. Kubicki, J.D. and White, A.F., 2008 Kinetics of mineral dissolution Kinetics of Water-Rock Interaction New York Springer 151–210.CrossRefGoogle Scholar
Brantley, S.L. and Chen, Y., 1995 Chemical weathering rates of pyroxenes and amphiboles Chemical Weathering Rates of Silicate Minerals Washington, D.C. Mineralogical Society of America 119–172.CrossRefGoogle Scholar
Brantley, S.L. Crane, S.R. Crerar, D.A. Hellmann, R. and Stallard, R., 1986 Dissolution at dislocation etch pits in quartz Geochimica et Cosmochimica Acta 50 2349–2361.CrossRefGoogle Scholar
Browning, S. and Thomas, D., 1985.Soil map of Coweeta Hydrologic LaboratoryGoogle Scholar
Bryan, D.S., 1994 Factors controlling the occurrence and distribution of hematite and goethite in soils and saprolites derived from schists and gneisses in western North Carolina Michigan, USA Michigan State University, East Lansing.Google Scholar
Campbell, A. and Schwertmann, U., 1984 Iron oxide mineralogy of placic horizons Journal of Soil Science 35 569–582.CrossRefGoogle Scholar
Ciampone, M.A., 1995 Non-systematic weathering profile on metamorphic rock in the southern Blue Ridge Mountains, North Carolina: Petrography, bulk chemistry, and mineral chemistry of biotite Cincinnati, Ohio, USA University of Cincinnati.Google Scholar
Deer, W.A. Howie, R.A. and Zussman, J., 1997 Rock-Forming Minerals-Orthosilicates London The Geological Society.Google Scholar
Drever, J.I., 1973 The preparation of oriented clay mineral specimens for X-ray diffraction analysis by a filter-membrane peel technique American Mineralogist 58 553–554.Google Scholar
Embrechts, J. and Stoops, G., 1982 Microscopical aspects of garnet weathering in a humid tropical environment Journal of Soil Science 33 535–545.CrossRefGoogle Scholar
Fromhold, A.T. Jr., 1976.Theory of Metal Oxidation. I. FundamentalsGoogle Scholar
Gardner, L.R., 1992 Long-term isovolumetric leaching of aluminum from rocks during weathering: Implications for the genesis of saprolite Catena 19 521–537.CrossRefGoogle Scholar
Ghabru, S. Mermut, A. and St. Arnaud, R., 1989 Characterization of garnets in a typic Cryoboralf (Gray luvisol) from Saskatchewan, Canada Soil Science of America Journal 53 575–582.CrossRefGoogle Scholar
Graham, R. Weed, S. Bowen, L. and Buol, S., 1989 Weathering of iron-bearing minerals in soils and saprolite on the North Carolina Blue Ridge Front: I. Sand-size primary minerals Clays and Clay Minerals 37 19–28.CrossRefGoogle Scholar
Graham, R. Weed, S. Bowen, L. and Buol, S., 1989 Weathering of iron-bearing minerals in soils and saprolite of the North Carolina Blue Ridge Front: II. Clay Mineralogy Clays and Clay Minerals 37 29–40.CrossRefGoogle Scholar
Graham, R. Daniels, R. and Buol, S., 1990 Soil geomorphic relations on the Blue Ridge Front: I. Regolith types and slope processes Soil Science Society of America Journal 54 1362–1367.CrossRefGoogle Scholar
Graham, R. Daniels, R. and Buol, S., 1990 Soil geomorphic relations on the Blue Ridge Front: II. Soil Characteristics and Pedogenesis Soils Science Society of America Journal 54 1367–1377.CrossRefGoogle Scholar
Hansley, P.L., 1987 Petrologic and experimental evidence for the etching of garnets by organic acids in the Upper Jurassic Morrison Formation, northwestern New Mexico Journal of Sedimentary Petrology 57 666–681.Google Scholar
Hatcher, R.D., 1980.Geologic map of Coweeta Hydrologic Laboratory, Prentiss Quadrangle, North Carolina: State of North Carolina, Department of Natural Resources and Community Development, in Cooperation with the Tennessee Valley Authority, scale 1:14,400, 1 sheetGoogle Scholar
Hatcher, R.D., Swank, W.T. Crossley, D.A. Jr., 1988 Bedrock geology and regional geologic setting of Coweeta Hydrologic Laboratory in the Eastern Blue Ridge Forest Hydrology and Ecology at Coweeta New York Springer-Verlag 81–92.CrossRefGoogle Scholar
Hauffe, K., 1965 Oxidation of Metals New York Plenum.Google Scholar
Kretz, R., 1983 Symbols for rock-forming minerals American Mineralogist 68 277–279.Google Scholar
Klein, C. and Hurlbut, C.S., 1999 Manual of Mineralogy New York John Wiley & Sons, Inc..Google Scholar
Kubaschewski, O. and Hopkins, B.E., 1962 Oxidation of Metals and Alloys 2 London Butterworths.Google Scholar
Lasaga, A. and Blum, A., 1986 Surface chemistry, etch pits and mineral water reactions Geochimica et Cosmochimica Acta 50 2363–2379.CrossRefGoogle Scholar
Lüttge, A. Arvidson, R.S., Brantley, S.L. Kubicki, J.D. and White, A.F., 2008 The mineral-water interface Kinetics of Water-Rock Interaction New York Springer 73–107.CrossRefGoogle Scholar
Miller, C.F. Hatcher, R.D. Jr. Ayers, J.C. Coath, C.D. and Harrison, T.M., 2000 Age and zircon inheritance of eastern Blue Ridge plutons, southwestern North Carolina and northeastern Georgia, with implications for magma history and evolution of the southern Appalachian orogen American Journal of Science 300 142–172.CrossRefGoogle Scholar
Moore, D.M. Reynolds, R.C. Jr., 1997 X-ray Diffraction and the Identification and Analysis of Clay Minerals New York Oxford University Press.Google Scholar
Parisot, J.C. Delvigne, J. Groke, M.T.C., Nahon, D. and Noack, Y., 1983 Petrographical aspects of the supergene weathering of garnet in the Serra dos Carajas (Para, Brazil) International Colloquium CNRS on the Petrology of Weathering and Soils, Abstracts Paris Centre National de la Recherche Scientifique 47.Google Scholar
Price, J.R., 2003 Allanite weathering and rare earth elements in mass balance calculations of clay genesis rates at the Coweeta Hydrologic Laboratory, western North Carolina, USA: The response times of changes in clay mineral assemblages to fluctuations in climate East Lansing, Michigan, USA University.Google Scholar
Price, J.R. Velbel, M.A. and Patino, L.C., 2005 Rates and timescales of clay-mineral formation in the southern Appalachian Mountains from geochemical mass balance Geological Society of America Bulletin 117 783–794.CrossRefGoogle Scholar
Robertson, I.D.M. and Butt, C.R.M., 1997 Atlas of Weathered Rocks Wembley, Western Australia Cooperative Research Centre for Landscape Evolution and Mineral Exploration.Google Scholar
Salvino, J.F. and Velbel, M.A., 1989 Faceted garnets from sandstones of the Munising Formation (Cambrian), northern Michigan: petrographic evidence for origin by intrastratal dissolution Sedimentology 36 371–379.CrossRefGoogle Scholar
Schott, J. and Petit, J.-C., 1987 New evidence for the mechanisms of dissolution of silicate minerals Aquatic Surface Chemistry 255–292.Google Scholar
Schroeder, P.A. Melear, N.D. West, L.T. and Hamilton, D.A., 2000 Meta-gabbro weathering in the Georgia Piedmont, USA: implications for global silicate weathering rates Chemical Geology 163 235–245.CrossRefGoogle Scholar
Schwertmann, U., 1971 Transformations of hematite to goethite in soils Nature 232 624–625.CrossRefGoogle ScholarPubMed
Smyth, J.R. and Bish, D.L., 1988.Crystal Structures and Cation Sites of the Rock-Forming MineralsGoogle Scholar
Swank, W. Crossley, I., Swank, W.T. Crossley, D.A. Jr., 1988 Introduction and site description Forest Hydrology and Ecology at Coweeta New York Springer-Verlag 3–15.CrossRefGoogle Scholar
Velbel, M., 1984 Natural weathering mechanisms of almandine garnet Geology 12 631–634.2.0.CO;2>CrossRefGoogle Scholar
Velbel, M., 1984 Mineral transformations during rock weathering, and geochemical mass-balances in forested watersheds of the Southern Appalachians Connecticut, USA Yale University, New Haven.Google Scholar
Velbel, M., 1985 Geochemical mass balances and weathering rates in forested watersheds of the southern Blue Ridge American Journal of Science 285 904–930.CrossRefGoogle Scholar
Velbel, M.A., Swank, W.T. Crossley, D.A. Jr., 1988 Weathering and soil-forming processes Forest Hydrology and Ecology at Coweeta New York Springer-Verlag 93–102.CrossRefGoogle Scholar
Velbel, M.A., 1989 Weathering of hornblende to ferruginous products by a dissolution-reprecipitation mechanism: petrography and stoichiometry Clays and Clay Minerals 37 515–524.CrossRefGoogle Scholar
Velbel, M.A., 1990 Mechanisms of saprolitization, isovolu-metric weathering, and pseudomorphous replacement during rock weathering-a review Chemical Geology 84 17–18.CrossRefGoogle Scholar
Velbel, M.A., 1993 Formation of protective surface layers during silicate-mineral weathering under well-leached, oxidizing conditions American Mineralogist 78 408–417.Google Scholar
Velbel, M.A., 2004 Laboratory and homework exercises in the geochemical kinetics of mineral-water reaction: rate law, Arrhenius activation energy, and the rate-determining step in the dissolution of halite Journal of Geoscience Education 52 52–59.CrossRefGoogle Scholar
Velbel, M.A., Mange, M.A. and Wright, D.T., 2007 Surface textures and dissolution processes of heavy minerals in the sedimentary cycle: examples from pyroxenes and amphiboles Heavy Minerals in Use New York Elsevier 113–150.CrossRefGoogle Scholar
Velbel, M.A. and Barker, W.W., 2008 Pyroxene weathering to smectite: Conventional and low-voltage cryo-field emission scanning electron microscopy, Koua Bocca ultramafic complex, Ivory Coast Clays and Clay Minerals 56 111–126.CrossRefGoogle Scholar
Velbel, M.A. McGuire, J.T. and Madden, A.S., 2007 Scanning electron microscopy of garnet from southern Michigan soils: Etching rates and inheritance of pre-glacial and pre-pedogenic grain-surface textures Heavy Minerals in Use 58 413–432.CrossRefGoogle Scholar
Velbel, M.A. Donatelle, A.R. and Formolo, M.J., 2009 Reactant-product textures, volume relations, and implication for major-element mobility during natural weathering of hornblende, Tallulah Falls Formation, Georgia Blue Ridge, U.S.A American Journal of Science 309 661–688.CrossRefGoogle Scholar
Wendt, A. D’Arco, P. Goffe, B. and Oberhänsli, R., 1993 Radial cracks around a-quartz inclusions in almandine: Constraints on the metamorphic history of the Oman Mountains Earth and Planetary Science Letters 114 449–461.CrossRefGoogle Scholar
White, A.F. Blum, A.E. Schulz, M.S. Vivit, D.V. Stonestrom, D.A. Larsen, M. Murphy, S.F. and Eberl, D., 1998 Chemical weathering in a tropical watershed, Luquillo Mountains, Puerto Rico: I. Long-term versus short-term weathering fluxes Geochimica et Cosmochimica Acta 62 209–226.CrossRefGoogle Scholar
Wilson, M.J., 1975 Chemical weathering of some primary rock-forming minerals Soil Science 119 349–355.CrossRefGoogle Scholar
Yeakley, J.A. Swank, W.T. Swift, L.W. Hornberger, G.M. and Shugart, H.H., 1998 Soil moisture gradients and controls on a southern Appalachian hillslope from drought through recharge Hydrology and Earth System Sciences 2 41–49.CrossRefGoogle Scholar