Weathering of chlorite from grain to watershed: The role and distribution of oxidation reactions in the subsurface

Liao, Ruxue; Gu, Xin; Brantley, Susan L.

doi:10.1016/j.gca.2022.07.019

Title: Weathering of chlorite from grain to watershed: The role and distribution of oxidation reactions in the subsurface

Journal Article · 21 July 2022 · Geochimica et Cosmochimica Acta

DOI: https://doi.org/10.1016/j.gca.2022.07.019 · OSTI ID:1977158

Liao, Ruxue ^[1]; Gu, Xin ^[2]; Brantley, Susan L. ^[2]

Pennsylvania State Univ., University Park, PA (United States); Lanzhou Univ. (China); OSTI
Pennsylvania State Univ., University Park, PA (United States)

The reaction mechanism of weathering of chlorite, an important rock-forming phyllosilicate, is not well understood in natural settings. Here, in this work we investigated the weathering of Fe-rich chlorite from deep protolith to saprock to soil across a small shale-underlain watershed in the Appalachian Mountains, USA (Shale Hills). We found that oxidation of Fe(II) in chlorite always occurs prior to dissolution of the interlayers of the mineral. The oxidation of pyrite and chlorite commence near the water table across narrow depth intervals under the upper-catchment ridges, but well below the water table across wide depth intervals under the valley. We hypothesize that these patterns can be explained by hydrological and geochemical differences between the ridge and the valley: oxygenated water descends sub-vertically (1D flow) under the ridge, while under the valley, oxygen-depleted water moves upward to the stream and laterally out of the watershed in the subsurface (3D flow). Geochemical and mineralogical characterization indicates that the transformation of Fe-rich chlorite at Shale Hills is initiated by the oxidation of Fe(II). Next, the interlayer hydroxide sheet dissolves to form hydroxy-interlayered vermiculite and then vermiculite. During the transformation, Mg and Fe are released into solution and Fe is reprecipitated as goethite in pore space. Delivery of oxygen to the deep subsurface by infiltration of meteoric water is thought to control the initial transformation of chlorite at Shale Hills. It is possible that weathering of many Fe(II)-rich minerals is initiated by oxidation as mediated by rates of subsurface oxygen delivery.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Pennsylvania State Univ., University Park, PA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15675

OSTI ID:: 1977158

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Journal Issue: C Vol. 333; ISSN 0016-7037

Publisher:: Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Understanding watershed hydrogeochemistry: 2. Synchronized hydrological and geochemical processes drive stream chemostatic behavior: CONCENTRATION-DISCHARGE RELATIONSHIP Li, Li; Bao, Chen; Sullivan, Pamela L. Water Resources Research, Vol. 53, Issue 3 https://doi.org/10.1002/2016WR018935	journal	March 2017
Probing deep weathering in the Shale Hills Critical Zone Observatory, Pennsylvania (USA): the hypothesis of nested chemical reaction fronts in the subsurface: NESTED REACTION FRONTS Brantley, Susan L.; Holleran, Molly E.; Jin, Lixin Earth Surface Processes and Landforms, Vol. 38, Issue 11 https://doi.org/10.1002/esp.3415	journal	April 2013
Controls on deep critical zone architecture: a historical review and four testable hypotheses: Four Testable Hypotheses about the Deep Critical Zone Riebe, Clifford S.; Hahm, W. Jesse; Brantley, Susan L. Earth Surface Processes and Landforms, Vol. 42, Issue 1 https://doi.org/10.1002/esp.4052	journal	November 2016
Relating the depth of the water table to the depth of weathering Lebedeva, M. I.; Brantley, S. L. Earth Surface Processes and Landforms, Vol. 45, Issue 9 https://doi.org/10.1002/esp.4873	journal	May 2020
Simulating high-resolution soil moisture patterns in the Shale Hills watershed using a land surface hydrologic model: Simulating High-Resolution Soil Moisture Patterns Shi, Yuning; Baldwin, Douglas C.; Davis, Kenneth J. Hydrological Processes, Vol. 29, Issue 21 https://doi.org/10.1002/hyp.10593	journal	August 2015
Regolith production and transport at the Susquehanna Shale Hills Critical Zone Observatory, Part 2: Insights from meteoric ¹⁰ Be : METEORIC West, Nicole; Kirby, Eric; Bierman, Paul Journal of Geophysical Research: Earth Surface, Vol. 118, Issue 3 https://doi.org/10.1002/jgrf.20121	journal	September 2013
A mechanism of chemical weathering of mudstone in a mountainous area Chigira, Masahiro Engineering Geology, Vol. 29, Issue 2 https://doi.org/10.1016/0013-7952(90)90002-I	journal	July 1990
Chemical weathering mechanisms and their effects on engineering properties of soft sandstone and conglomerate cemented by zeolite in a mountainous area Chigira, Masahiro; Sone, Kenji Engineering Geology, Vol. 30, Issue 2 https://doi.org/10.1016/0013-7952(91)90043-K	journal	April 1991
Constitutive mass balance relations between chemical composition, volume, density, porosity, and strain in metasomatic hydrochemical systems: Results on weathering and pedogenesis Brimhall, George H.; Dietrich, William E. Geochimica et Cosmochimica Acta, Vol. 51, Issue 3 https://doi.org/10.1016/0016-7037(87)90070-6	journal	March 1987
Weathering of chlorite and some associations of trace elements in Permian phyllites in Southeast Queensland Gilkes, R. J.; Little, I. P. Geoderma, Vol. 7, Issue 3-4 https://doi.org/10.1016/0016-7061(72)90008-0	journal	May 1972
Weathering of chlorite in a soil derived from a chloritoschist under humid tropical conditions Herbillon, A. J.; Makumbi, M. N. Geoderma, Vol. 13, Issue 2 https://doi.org/10.1016/0016-7061(75)90059-2	journal	March 1975
Precise determination of ferrous iron in silicate rocks Yokoyama, Tetsuya; Nakamura, Eizo Geochimica et Cosmochimica Acta, Vol. 66, Issue 6 https://doi.org/10.1016/S0016-7037(01)00809-2	journal	March 2002
Chlorite dissolution in the acid ph-range: a combined microscopic and macroscopic approach Brandt, Felix; Bosbach, Dirk; Krawczyk-Bärsch, Evelyn Geochimica et Cosmochimica Acta, Vol. 67, Issue 8 https://doi.org/10.1016/S0016-7037(02)01293-0	journal	April 2003
Electron probe microanalysis of Fe2+/ΣFe ratios in calcic and sodic-calcic amphibole and biotite using the flank method Li, Xiaoyan; Zhang, Chao; Almeev, Renat R. Chemical Geology, Vol. 509 https://doi.org/10.1016/j.chemgeo.2019.01.009	journal	March 2019
The role of iron-bearing minerals for the deep weathering of a hydrothermally altered plutonic rock in semi-arid climate (Chilean Coastal Cordillera) Hampl, Ferdinand J.; Schiperski, Ferry; Byrne, James M. Chemical Geology, Vol. 604 https://doi.org/10.1016/j.chemgeo.2022.120922	journal	August 2022
Particle fluxes in groundwater change subsurface shale rock chemistry over geologic time Kim, Hyojin; Gu, Xin; Brantley, Susan L. Earth and Planetary Science Letters, Vol. 500 https://doi.org/10.1016/j.epsl.2018.07.031	journal	October 2018
Weathering of the Rio Blanco quartz diorite, Luquillo Mountains, Puerto Rico: Coupling oxidation, dissolution, and fracturing Buss, Heather L.; Sak, Peter B.; Webb, Samuel M. Geochimica et Cosmochimica Acta, Vol. 72, Issue 18 https://doi.org/10.1016/j.gca.2008.06.020	journal	September 2008
Mineral weathering and elemental transport during hillslope evolution at the Susquehanna/Shale Hills Critical Zone Observatory Jin, Lixin; Ravella, Ramesh; Ketchum, Blake Geochimica et Cosmochimica Acta, Vol. 74, Issue 13 https://doi.org/10.1016/j.gca.2010.03.036	journal	July 2010
Chemical reactions, porosity, and microfracturing in shale during weathering: The effect of erosion rate Gu, Xin; Rempe, Daniella M.; Dietrich, William E. Geochimica et Cosmochimica Acta, Vol. 269 https://doi.org/10.1016/j.gca.2019.09.044	journal	January 2020
Weathering of rock to regolith: The activity of deep roots in bedrock fractures Hasenmueller, Elizabeth A.; Gu, Xin; Weitzman, Julie N. Geoderma, Vol. 300 https://doi.org/10.1016/j.geoderma.2017.03.020	journal	August 2017
Investigation of Wüstite (FeO) Dissolution: Implications for Reductive Dissolution of Ferric Oxides Jang, Je-Hun; Brantley, Susan L. Environmental Science & Technology, Vol. 43, Issue 4 https://doi.org/10.1021/es8010139	journal	January 2009
Seismic Imaging of a Shale Landscape Under Compression Shows Limited Influence of Topography‐Induced Fracturing Ma, Lisa; Oakley, David; Nyblade, Andrew Geophysical Research Letters, Vol. 48, Issue 17 https://doi.org/10.1029/2021GL093372	journal	August 2021
3D Seismic Anatomy of a Watershed Reveals Climate‐Topography Coupling That Drives Water Flowpaths and Bedrock Weathering Wang, Wei; Nyblade, Andrew; Mount, Greg Journal of Geophysical Research: Earth Surface, Vol. 126, Issue 12 https://doi.org/10.1029/2021JF006281	journal	December 2021
Experimental alteration of chlorites into vermiculites by chemical oxidation Ross, G. J. Nature, Vol. 255, Issue 5504 https://doi.org/10.1038/255133a0	journal	May 1975
Iron-oxidizer hotspots formed by intermittent oxic–anoxic fluid mixing in fractured rocks Bochet, Olivier; Bethencourt, Lorine; Dufresne, Alexis Nature Geoscience, Vol. 13, Issue 2 https://doi.org/10.1038/s41561-019-0509-1	journal	January 2020
Links between physical and chemical weathering inferred from a 65-m-deep borehole through Earth’s critical zone Holbrook, W. Steven; Marcon, Virginia; Bacon, Allan R. Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-019-40819-9	journal	March 2019
Seismic refraction tracks porosity generation and possible CO ₂ production at depth under a headwater catchment Gu, Xin; Mavko, Gary; Ma, Lisa Proceedings of the National Academy of Sciences, Vol. 117, Issue 32 https://doi.org/10.1073/pnas.2003451117	journal	July 2020
Evaluating Aeration Criteria by Simultaneous Measurement of Oxygen Diffusion rate and Soil-Water Regime Feng, G.; Wu, L.; Letey, J. Soil Science, Vol. 167, Issue 8 https://doi.org/10.1097/00010694-200208000-00001	journal	January 2002
The Weathering of Chloritic Minerals in some Scottish Soils Bain, D. C. Journal of Soil Science, Vol. 28, Issue 1 https://doi.org/10.1111/j.1365-2389.1977.tb02303.x	journal	March 1977
Porosity production in weathered rock: Where volumetric strain dominates over chemical mass loss Hayes, Jorden L.; Riebe, Clifford S.; Holbrook, W. Steven Science Advances, Vol. 5, Issue 9 https://doi.org/10.1126/sciadv.aao0834	journal	September 2019
Acidic Mine Drainage: The Rate-Determining Step Singer, P. C.; Stumm, W. Science, Vol. 167, Issue 3921 https://doi.org/10.1126/science.167.3921.1121	journal	February 1970
Deep abiotic weathering of pyrite Gu, Xin; Heaney, Peter J.; Reis, Fabio D. A. Aarão Science, Vol. 370, Issue 6515 https://doi.org/10.1126/science.abb8092	journal	October 2020
Weathering profiles, mass-balance analysis, and rates of solute loss: Linkages between weathering and erosion in a small, steep catchment Anderson, Suzanne Prestrud; Dietrich, William E.; Brimhall, George H. GSA Bulletin, Vol. 114, Issue 9 https://doi.org/10.1130/0016-7606(2002)114<1143:WPMBAA>2.0.CO;2	journal	September 2002
Development of a Coupled Land Surface Hydrologic Model and Evaluation at a Critical Zone Observatory Shi, Yuning; Davis, Kenneth J.; Duffy, Christopher J. Journal of Hydrometeorology, Vol. 14, Issue 5 https://doi.org/10.1175/JHM-D-12-0145.1	journal	October 2013
Weathering of Chlorite: ii. Reactions and Products in Microsystems Controlled by Solution Avenues Aspandiar, Mehrooz F.; Eggleton, Richard A. Clays and Clay Minerals, Vol. 50, Issue 6 https://doi.org/10.1346/000986002762090100	journal	December 2002
Weathering of Chlorite: i. Reactions and Products in Microsystems Controlled by the Primary Mineral Aspandiar, Mehrooz F.; Eggleton, Richard A. Clays and Clay Minerals, Vol. 50, Issue 6 https://doi.org/10.1346/000986002762090227	journal	December 2002
The Distribution and Identification of Mixed-layer Clays in Sedimentary Rocks1 Weaver, Charles E. Clays and Clay Minerals, Vol. 4, Issue 1 https://doi.org/10.1346/CCMN.1955.0040143	journal	January 1955
Experimental Alteration of a Chlorite into a Regularly Interstratified Chlorite-Vermiculite by Chemical Oxidation Ross, G. J. Clays and Clay Minerals, Vol. 24, Issue 4 https://doi.org/10.1346/CCMN.1976.0240406	journal	January 1976
Oxidation and Reduction of Structural Iron in Chlorite at 480°C Borggaard, Ole K. Clays and Clay Minerals, Vol. 30, Issue 5 https://doi.org/10.1346/CCMN.1982.0300506	journal	January 1982
Supergene Vermiculitization of a Magnesian Chlorite: Iron and Magnesium Removal Processes Proust, Dominique Clays and Clay Minerals, Vol. 34, Issue 5 https://doi.org/10.1346/CCMN.1986.0340511	journal	January 1986
Evidence for Halloysite Formation from Weathering of Ferruginous Chlorite1 Hi, Doo Cho Clays and Clay Minerals, Vol. 40, Issue 5 https://doi.org/10.1346/CCMN.1992.0400516	journal	January 1992
Crossing Disciplines and Scales to Understand the Critical Zone Brantley, S. L.; Goldhaber, M. B.; Ragnarsdottir, K. V. Elements, Vol. 3, Issue 5 https://doi.org/10.2113/gselements.3.5.307	journal	October 2007
Comparison of Iron and Aluminum Hydroxy Interlayers in Montmorillonite and Vermiculite: II. Dissolution Carstea, D. D.; Harward, M. E.; Knox, E. G. Soil Science Society of America Journal, Vol. 34, Issue 3 https://doi.org/10.2136/sssaj1970.03615995003400030044x	journal	May 1970
Transformation of Chlorite to Smectite Through Regularly Interstratified Intermediates Senkayi, A. L.; Dixon, J. B.; Hossner, L. R. Soil Science Society of America Journal, Vol. 45, Issue 3 https://doi.org/10.2136/sssaj1981.03615995004500030043x	journal	May 1981
Temporal Stability of Soil Moisture Spatial Pattern and Subsurface Preferential Flow Pathways in the Shale Hills Catchment Lin, Henry Vadose Zone Journal, Vol. 5, Issue 1 https://doi.org/10.2136/vzj2005.0058	journal	January 2006
Opening the “Black Box”: Water Chemistry Reveals Hydrological Controls on Weathering in the Susquehanna Shale Hills Critical Zone Observatory Jin, Lixin; Andrews, Danielle M.; Holmes, George H. Vadose Zone Journal, Vol. 10, Issue 3 https://doi.org/10.2136/vzj2010.0133	journal	January 2011
Susquehanna Shale Hills Critical Zone Observatory: Shale Hills in the Context of Shaver's Creek Watershed Brantley, Susan L.; White, Tim; West, Nicole Vadose Zone Journal, Vol. 17, Issue 1 https://doi.org/10.2136/vzj2018.04.0092	journal	January 2018
Atomic-resolution transmission electron microscope evidence for the mechanism by which chlorite weathers to 1:1 semi-regular chlorite-vermiculite Banfield, Jillian F.; Murakami, Takashi American Mineralogist, Vol. 83, Issue 3-4 https://doi.org/10.2138/am-1998-3-419	journal	April 1998
The iron oxidation state of garnet by electron microprobe: Its determination with the flank method combined with major-element analysis Hofer, H. E.; Brey, G. P. American Mineralogist, Vol. 92, Issue 5-6 https://doi.org/10.2138/am.2007.2390	journal	May 2007
Chlorite and biotite weathering, Fe2+-rich corrensite formation, and Fe behavior under low PO2 conditions and their implication for Precambrian weathering Sugimori, H.; Iwatsuki, T.; Murakami, T. American Mineralogist, Vol. 93, Issue 7 https://doi.org/10.2138/am.2008.2663	journal	July 2008
Characterization of deep weathering and nanoporosity development in shale--A neutron study Jin, L.; Rother, G.; Cole, D. R. American Mineralogist, Vol. 96, Issue 4 https://doi.org/10.2138/am.2011.3598	journal	March 2011
Chlorite topography and dissolution of the interlayer studied with atomic force microscopy Gazze, S. A.; Stack, A. G.; Ragnarsdottir, K. V. American Mineralogist, Vol. 99, Issue 1 https://doi.org/10.2138/am.2014.4478	journal	January 2014
Approaches to Modeling Weathered Regolith Brantley, S. L.; White, A. F. Reviews in Mineralogy and Geochemistry, Vol. 70, Issue 1 https://doi.org/10.2138/rmg.2009.70.10	journal	January 2009
Oxidative dissolution under the channel leads geomorphological evolution at the Shale Hills catchment Sullivan, Pamela L.; Hynek, Scott A.; Gu, Xin American Journal of Science, Vol. 316, Issue 10 https://doi.org/10.2475/10.2016.02	journal	December 2016

Similar Records

3D Seismic Anatomy of a Watershed Reveals Climate–Topography Coupling That Drives Water Flowpaths and Bedrock Weathering

Journal Article · 2021 · Journal of Geophysical Research. Earth Surface · OSTI ID:1864535

Wang, Wei; Nyblade, Andrew; Mount, Greg; +6 more

Seismic Imaging of a Shale Landscape Under Compression Shows Limited Influence of Topography–Induced Fracturing

Journal Article · 2021 · Geophysical Research Letters · OSTI ID:1864537

Ma, Lisa; Oakley, David; Nyblade, Andrew; +9 more

Comparative study of inorganic and organic components of soil formation in two watersheds of Alabama

Conference · 1993 · Geological Society of America, Abstracts with Programs; (United States) · OSTI ID:6078503

Kornegay, C; Donahoe, R

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
58 GEOSCIENCES
Chlorite weathering
Flow path
Geochemistry & Geophysics
Pyrite oxidation
Vermiculitization

Title: Weathering of chlorite from grain to watershed: The role and distribution of oxidation reactions in the subsurface

Citation Formats

References (54)

Similar Records

Related Subjects