Experimental calibration of silicon and oxygen isotope fractionations between quartz and water at 250°C by in situ microanalysis of experimental products and application to zoned low δ30Si quartz overgrowths

Anthony D. Pollington; Reinhard Kozdon; Lawrence M. Anovitz; R. Bastian Georg; Michael J. Spicuzza; John W. Valley

doi:10.1016/j.chemgeo.2015.11.011

Experimental calibration of silicon and oxygen isotope fractionations between quartz and water at 250°C by in situ microanalysis of experimental products and application to zoned low δ³⁰Si quartz overgrowths

Anthony D. Pollington
, Reinhard Kozdon
, Lawrence M. Anovitz
, R. Bastian Georg
, Michael J. Spicuzza
, John W. Valley

Geochemistry & Interfacial Science

Research output: Contribution to journal › Article › peer-review

43 Scopus citations

Abstract

The interpretation of silicon isotope data for quartz is hampered by the lack of experimentally determined fractionation factors between quartz and fluid. Further, there is a large spread in published oxygen isotope fractionation factors at low temperatures, primarily due to extrapolation from experimental calibrations at high temperature. We present the first measurements of silicon isotope ratios from experimentally precipitated quartz and estimate the equilibrium fractionation vs. dissolved silica using a novel in situ analysis technique applying secondary ion mass spectrometry to directly analyze experimental products. These experiments also yield a new value for oxygen isotope fractionation. Quartz overgrowths up to 235μm thick were precipitated in silica-H₂O-NaOH-NaCl fluids, at pH12-13 and 250°C. At this temperature, 1000lnα³⁰Si(Qtz-fluid) = 0.55±0.10‰ and 1000lnα¹⁸O(Qtz-fluid) = 10.62±0.13‰, yielding the relations 1000lnα³⁰Si(Qtz-fluid) = (0.15±0.03)*10⁶/T² and 1000lnα¹⁸O(Qtz-fluid) = (2.91±0.04)*10⁶/T² when extended to zero fractionation at infinite temperature. Values of δ³⁰Si(Qtz) from diagenetic cement in sandstones from the basal Cambrian Mt. Simon Formation in central North America range from 0 to -5.4‰. Paired δ¹⁸O and δ³⁰Si values from individual overgrowths preserve a record of Precambrian weathering and fluid transport. The application of the experimental quartz growth results to observations from natural sandstone samples suggests that precipitation of quartz at low temperatures in nature is dominated by kinetic, rather than equilibrium, processes.

Original language	English
Pages (from-to)	127-142
Number of pages	16
Journal	Chemical Geology
Volume	421
DOIs	https://doi.org/10.1016/j.chemgeo.2015.11.011
State	Published - Feb 10 2016

Funding

The WiscSIMS laboratory is supervised by Noriko Kita and maintained by Jim Kern. Brian Hess prepared sample mounts and helped with preparation of quartz chips. Hiromi Konishi and Minglu Liu assisted with XRD analyses. John Fournelle and Phillip Gopon supported SEM work. Ellen Syracuse assisted in drafting figures. Samples from Illinois were provided by the Illinois State Geological Survey, with the assistance of Bob Mumm and Jared Freiburg. Wisconsin sample 07WI-1 was provided by Robert Dott, Jr. who also provided helpful discussions on earlier versions of the manuscript. Hubert King suggested methods to aid the experimental portion of the study. Preliminary analyses of similar Mt. Simon samples were performed by Andrew Trzaskus and Philipp Heck. Funding was provided by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy ( 93ER14389 ) to JWV and Graduate Student Research grants from the Geological Society of America and UW-Madison Department of Geoscience to ADP. LMA was supported by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy . The WiscSIMS laboratory is partially funded by the U.S. National Science Foundation ( EAR-1053466 , 1355590 ). Constructive reviews from Merlin Méheut, an anonymous reviewer, and Editor Michael Böttcher improved the final manuscript.

Keywords

Experimental calibration
Isotope fractionation
Precambrian weathering
SIMS
δO
δSi

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Pollington, A. D., Kozdon, R., Anovitz, L. M., Georg, R. B., Spicuzza, M. J., & Valley, J. W. (2016). Experimental calibration of silicon and oxygen isotope fractionations between quartz and water at 250°C by in situ microanalysis of experimental products and application to zoned low δ³⁰Si quartz overgrowths. Chemical Geology, 421, 127-142. https://doi.org/10.1016/j.chemgeo.2015.11.011

@article{d71611b2b6644684bc7d29fcb090fdbc,

title = "Experimental calibration of silicon and oxygen isotope fractionations between quartz and water at 250°C by in situ microanalysis of experimental products and application to zoned low δ30Si quartz overgrowths",

abstract = "The interpretation of silicon isotope data for quartz is hampered by the lack of experimentally determined fractionation factors between quartz and fluid. Further, there is a large spread in published oxygen isotope fractionation factors at low temperatures, primarily due to extrapolation from experimental calibrations at high temperature. We present the first measurements of silicon isotope ratios from experimentally precipitated quartz and estimate the equilibrium fractionation vs. dissolved silica using a novel in situ analysis technique applying secondary ion mass spectrometry to directly analyze experimental products. These experiments also yield a new value for oxygen isotope fractionation. Quartz overgrowths up to 235μm thick were precipitated in silica-H2O-NaOH-NaCl fluids, at pH12-13 and 250°C. At this temperature, 1000lnα30Si(Qtz-fluid) = 0.55±0.10‰ and 1000lnα18O(Qtz-fluid) = 10.62±0.13‰, yielding the relations 1000lnα30Si(Qtz-fluid) = (0.15±0.03)*106/T2 and 1000lnα18O(Qtz-fluid) = (2.91±0.04)*106/T2 when extended to zero fractionation at infinite temperature. Values of δ30Si(Qtz) from diagenetic cement in sandstones from the basal Cambrian Mt. Simon Formation in central North America range from 0 to -5.4‰. Paired δ18O and δ30Si values from individual overgrowths preserve a record of Precambrian weathering and fluid transport. The application of the experimental quartz growth results to observations from natural sandstone samples suggests that precipitation of quartz at low temperatures in nature is dominated by kinetic, rather than equilibrium, processes.",

keywords = "Experimental calibration, Isotope fractionation, Precambrian weathering, SIMS, δO, δSi",

author = "Pollington, \{Anthony D.\} and Reinhard Kozdon and Anovitz, \{Lawrence M.\} and Georg, \{R. Bastian\} and Spicuzza, \{Michael J.\} and Valley, \{John W.\}",

note = "Publisher Copyright: {\textcopyright} 2015 Elsevier B.V.",

year = "2016",

month = feb,

day = "10",

doi = "10.1016/j.chemgeo.2015.11.011",

language = "English",

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Pollington, AD, Kozdon, R, Anovitz, LM, Georg, RB, Spicuzza, MJ & Valley, JW 2016, 'Experimental calibration of silicon and oxygen isotope fractionations between quartz and water at 250°C by in situ microanalysis of experimental products and application to zoned low δ³⁰Si quartz overgrowths', Chemical Geology, vol. 421, pp. 127-142. https://doi.org/10.1016/j.chemgeo.2015.11.011

Experimental calibration of silicon and oxygen isotope fractionations between quartz and water at 250°C by in situ microanalysis of experimental products and application to zoned low δ³⁰Si quartz overgrowths. / Pollington, Anthony D.; Kozdon, Reinhard; Anovitz, Lawrence M. et al.
In: Chemical Geology, Vol. 421, 10.02.2016, p. 127-142.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Experimental calibration of silicon and oxygen isotope fractionations between quartz and water at 250°C by in situ microanalysis of experimental products and application to zoned low δ30Si quartz overgrowths

AU - Pollington, Anthony D.

AU - Kozdon, Reinhard

AU - Anovitz, Lawrence M.

AU - Georg, R. Bastian

AU - Spicuzza, Michael J.

AU - Valley, John W.

PY - 2016/2/10

Y1 - 2016/2/10

N2 - The interpretation of silicon isotope data for quartz is hampered by the lack of experimentally determined fractionation factors between quartz and fluid. Further, there is a large spread in published oxygen isotope fractionation factors at low temperatures, primarily due to extrapolation from experimental calibrations at high temperature. We present the first measurements of silicon isotope ratios from experimentally precipitated quartz and estimate the equilibrium fractionation vs. dissolved silica using a novel in situ analysis technique applying secondary ion mass spectrometry to directly analyze experimental products. These experiments also yield a new value for oxygen isotope fractionation. Quartz overgrowths up to 235μm thick were precipitated in silica-H2O-NaOH-NaCl fluids, at pH12-13 and 250°C. At this temperature, 1000lnα30Si(Qtz-fluid) = 0.55±0.10‰ and 1000lnα18O(Qtz-fluid) = 10.62±0.13‰, yielding the relations 1000lnα30Si(Qtz-fluid) = (0.15±0.03)*106/T2 and 1000lnα18O(Qtz-fluid) = (2.91±0.04)*106/T2 when extended to zero fractionation at infinite temperature. Values of δ30Si(Qtz) from diagenetic cement in sandstones from the basal Cambrian Mt. Simon Formation in central North America range from 0 to -5.4‰. Paired δ18O and δ30Si values from individual overgrowths preserve a record of Precambrian weathering and fluid transport. The application of the experimental quartz growth results to observations from natural sandstone samples suggests that precipitation of quartz at low temperatures in nature is dominated by kinetic, rather than equilibrium, processes.

AB - The interpretation of silicon isotope data for quartz is hampered by the lack of experimentally determined fractionation factors between quartz and fluid. Further, there is a large spread in published oxygen isotope fractionation factors at low temperatures, primarily due to extrapolation from experimental calibrations at high temperature. We present the first measurements of silicon isotope ratios from experimentally precipitated quartz and estimate the equilibrium fractionation vs. dissolved silica using a novel in situ analysis technique applying secondary ion mass spectrometry to directly analyze experimental products. These experiments also yield a new value for oxygen isotope fractionation. Quartz overgrowths up to 235μm thick were precipitated in silica-H2O-NaOH-NaCl fluids, at pH12-13 and 250°C. At this temperature, 1000lnα30Si(Qtz-fluid) = 0.55±0.10‰ and 1000lnα18O(Qtz-fluid) = 10.62±0.13‰, yielding the relations 1000lnα30Si(Qtz-fluid) = (0.15±0.03)*106/T2 and 1000lnα18O(Qtz-fluid) = (2.91±0.04)*106/T2 when extended to zero fractionation at infinite temperature. Values of δ30Si(Qtz) from diagenetic cement in sandstones from the basal Cambrian Mt. Simon Formation in central North America range from 0 to -5.4‰. Paired δ18O and δ30Si values from individual overgrowths preserve a record of Precambrian weathering and fluid transport. The application of the experimental quartz growth results to observations from natural sandstone samples suggests that precipitation of quartz at low temperatures in nature is dominated by kinetic, rather than equilibrium, processes.

KW - Experimental calibration

KW - Isotope fractionation

KW - Precambrian weathering

KW - SIMS

KW - δO

KW - δSi

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U2 - 10.1016/j.chemgeo.2015.11.011

DO - 10.1016/j.chemgeo.2015.11.011

M3 - Article

AN - SCOPUS:84953351218

SN - 0009-2541

VL - 421

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EP - 142

JO - Chemical Geology

JF - Chemical Geology

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