skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy

Abstract

The hydrogen and oxygen stable isotope composition (δ2H and δ18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ2H and δ18O values of liquid water samples with precision for δ2H of ± 1.2‰, and for δ18O of ± 0.17‰. For hydration waters in goethite, precision for δ2H ranges from ± 0.3‰ to 1.6‰, and for δ18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ2H and δ18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ2H values that reflect the hydrogen of the OH phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ18O values on goethite reflect the oxygen in OH groups bound to Fe (Fe-OH group), and not themore » oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.« less

Authors:
ORCiD logo [1];  [1];  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1406418
Alternate Identifier(s):
OSTI ID: 1576816
Report Number(s):
LLNL-JRNL-736485
Journal ID: ISSN 0009-2541
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Geology
Additional Journal Information:
Journal Volume: 475; Journal Issue: C; Journal ID: ISSN 0009-2541
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 58 GEOSCIENCES; 07 ISOTOPES AND RADIATION SOURCES; Stable isotope hydrology; Paleoclimatology; Dehydroxylation; Mineral-water fractionation; Hydrous minerals

Citation Formats

Oerter, Erik, Singleton, Michael, and Davisson, Lee. Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy. United States: N. p., 2017. Web. https://doi.org/10.1016/j.chemgeo.2017.10.025.
Oerter, Erik, Singleton, Michael, & Davisson, Lee. Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy. United States. https://doi.org/10.1016/j.chemgeo.2017.10.025
Oerter, Erik, Singleton, Michael, and Davisson, Lee. Sun . "Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy". United States. https://doi.org/10.1016/j.chemgeo.2017.10.025. https://www.osti.gov/servlets/purl/1406418.
@article{osti_1406418,
title = {Hydrogen and oxygen stable isotope signatures of goethite hydration waters by thermogravimetry-enabled laser spectroscopy},
author = {Oerter, Erik and Singleton, Michael and Davisson, Lee},
abstractNote = {The hydrogen and oxygen stable isotope composition (δ2H and δ18O values) of mineral hydration waters can give information on the environment of mineral formation. Here we present and validate an approach for the stable isotope analysis of mineral hydration waters based on coupling a thermogravimetric analyzer with a laser-based isotope ratio infrared spectroscopy instrument (Picarro L-2130i), which we abbreviate as TGA-IRIS. TGA-IRIS generates δ2H and δ18O values of liquid water samples with precision for δ2H of ± 1.2‰, and for δ18O of ± 0.17‰. For hydration waters in goethite, precision for δ2H ranges from ± 0.3‰ to 1.6‰, and for δ18O ranges from ± 0.17‰ to 0.27‰. The ability of TGA-IRIS to generate detailed water yield data and δ2H and δ18O values of water at varying temperatures allows for the differentiation of water in varying states of binding on mineral surfaces and within the mineral matrix. TGA-IRIS analyses of hydrogen isotopes in goethite yields δ2H values that reflect the hydrogen of the OH– phase in the mineral and are comparable to that made by IRMS and found in the literature. In contrast, δ18O values on goethite reflect the oxygen in OH– groups bound to Fe (Fe-OH group), and not the oxygen bound only to Fe (Fe-O group) in the mineral crystal lattice, and may not be comparable to literature δ18O values made by IRMS that reflect the total O in the mineral. TGA-IRIS presents the possibility to isotopically differentiate the various oxygen reservoirs in goethite, which may allow the mineral to be used as a single mineral geothermometer. As a result, TGA-IRIS measurements of hydration waters are likely to open new avenues and possibilities for research on hydrated minerals.},
doi = {10.1016/j.chemgeo.2017.10.025},
journal = {Chemical Geology},
number = C,
volume = 475,
place = {United States},
year = {2017},
month = {10}
}

Journal Article:

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Isotope effects accompanying vacuum extraction of soil water for stable isotope analyses
journal, June 1995


Oxygen isotope fractionation in ferric oxide-water systems: low temperature synthesis
journal, March 1999


Oxygen isotope study of a Precambrian banded iron-formation, Hamersley Range, Western Australia
journal, October 1976


A combined FTIR and TPD study on the bulk and surface dehydroxylation and decarbonation of synthetic goethite
journal, July 2006

  • Boily, Jean-François; Szanyi, János; Felmy, Andrew R.
  • Geochimica et Cosmochimica Acta, Vol. 70, Issue 14
  • DOI: 10.1016/j.gca.2006.05.013

Isoscapes: Spatial Pattern in Isotopic Biogeochemistry
journal, April 2010


The use of bromine pentafluoride in the extraction of oxygen from oxides and silicates for isotopic analysis
journal, January 1963


Reporting of stable hydrogen, carbon, and oxygen isotopic abundances (Technical Report)
journal, January 1994


Isotopic Variations in Meteoric Waters
journal, May 1961


The influence of memory, sample size effects, and filter paper material on online laser-based plant and soil water isotope measurements: Memory and sample size effect corrections for IM-CRDS
journal, February 2017

  • Cui, Jiangpeng; Tian, Lide; Gerlein-Safdi, Cynthia
  • Rapid Communications in Mass Spectrometry, Vol. 31, Issue 6
  • DOI: 10.1002/rcm.7824

Stable isotopes in precipitation
journal, January 1964


18O/16O and D/H ratios of pedogenic kaolinite in a North American Cenomanian laterite: Paleoclimatic implications
journal, October 2009


The kinetics and reaction mechanism of the goethite to hematite transformation
journal, September 1987


Method of Comparing Solid-State Kinetic Data and Its Application to the Decomposition of Kaolinite, Brucite, and BaCO3
journal, February 1972


Determining the stable isotope composition of pore water from saturated and unsaturated zone core: improvements to the direct vapour equilibration laser spectrometry method
journal, January 2015

  • Hendry, M. J.; Schmeling, E.; Wassenaar, L. I.
  • Hydrology and Earth System Sciences, Vol. 19, Issue 11
  • DOI: 10.5194/hess-19-4427-2015

Advances in laser-based isotope ratio measurements: selected applications
journal, August 2008


Simultaneous Determination of the 2 H/ 1 H, 17 O/ 16 O, and 18 O/ 16 O Isotope Abundance Ratios in Water by Means of Laser Spectrometry
journal, December 1999

  • Kerstel, E. R. Th.; van Trigt, R.; Reuss, J.
  • Analytical Chemistry, Vol. 71, Issue 23
  • DOI: 10.1021/ac990621e

Determination of the Hydrogen Isotopic Compositions of Organic Materials and Hydrous Minerals Using Thermal Combustion Laser Spectroscopy
journal, April 2012

  • Koehler, Geoff; Wassenaar, Leonard I.
  • Analytical Chemistry, Vol. 84, Issue 8
  • DOI: 10.1021/ac3000489

Measurement of stable isotope activities in saline aqueous solutions using optical spectroscopy methods
journal, August 2013

  • Koehler, Geoff; Wassenaar, Leonard I.; Hendry, Jim
  • Isotopes in Environmental and Health Studies, Vol. 49, Issue 3
  • DOI: 10.1080/10256016.2013.815183

Deuterium and oxygen-18 correlation: Clay minerals and hydroxides in Quaternary soils compared to meteoric waters
journal, October 1971


Hydrogen and oxygen isotope systematics in weathering profiles
journal, December 1972


Hydrologic Regulation of Chemical Weathering and the Geologic Carbon Cycle
journal, March 2014


Hydrated silicate minerals on Mars observed by the Mars Reconnaissance Orbiter CRISM instrument
journal, July 2008

  • Mustard, John F.; Murchie, S. L.; Pelkey, S. M.
  • Nature, Vol. 454, Issue 7202
  • DOI: 10.1038/nature07097

Formation and Diagenesis of Weathering Profiles
journal, March 1989

  • Nesbitt, H. W.; Young, G. M.
  • The Journal of Geology, Vol. 97, Issue 2
  • DOI: 10.1086/629290

In situ monitoring of H and O stable isotopes in soil water reveals ecohydrologic dynamics in managed soil systems
journal, April 2017

  • Oerter, Erik J.; Bowen, Gabriel
  • Ecohydrology, Vol. 10, Issue 4
  • DOI: 10.1002/eco.1841

Every apple has a voice: using stable isotopes to teach about food sourcing and the water cycle
journal, January 2017

  • Oerter, Erik; Malone, Molly; Putman, Annie
  • Hydrology and Earth System Sciences, Vol. 21, Issue 7
  • DOI: 10.5194/hess-21-3799-2017

Memory effect in deuterium analysis by continuous flow isotope ratio measurement
journal, July 2006

  • Olsen, Jesper; Seierstad, Inger; Vinther, Bo
  • International Journal of Mass Spectrometry, Vol. 254, Issue 1-2
  • DOI: 10.1016/j.ijms.2006.05.004

Intercomparison of soil pore water extraction methods for stable isotope analysis: Intercomparison of Soil Pore Water Extraction Methods
journal, June 2016

  • Orlowski, Natalie; Pratt, Dyan L.; McDonnell, Jeffrey J.
  • Hydrological Processes, Vol. 30, Issue 19
  • DOI: 10.1002/hyp.10870

Method for Simultaneous Oxygen and Hydrogen Isotope Analysis of Water of Crystallization in Hydrated Minerals
journal, August 2008

  • Rohrssen, Megan; Brunner, Benjamin; Mielke, Randall E.
  • Analytical Chemistry, Vol. 80, Issue 18
  • DOI: 10.1021/ac800618p

The oxygen and hydrogen isotope geochemistry of clay minerals
journal, January 1970


The hydrogen and oxygen isotope geochemistry of pedogenic clay minerals: principles and theoretical background
journal, February 1998


The double dehydroxylation peak of goethite
journal, July 1984


A rapid method for determination of hydrogen and oxygen isotope ratios from water and hydrous minerals
journal, August 2001


Surface and Bulk Thermal Dehydroxylation of FeOOH Polymorphs
journal, August 2016

  • Song, Xiaowei; Boily, Jean-François
  • The Journal of Physical Chemistry A, Vol. 120, Issue 31
  • DOI: 10.1021/acs.jpca.6b04294

Precise oxygen and hydrogen isotope determination in nanoliter quantities of speleothem inclusion water by cavity ring-down spectroscopic techniques
journal, January 2016


Continual in situ monitoring of pore water stable isotopes in the subsurface
journal, January 2014


High Resolution Pore Water δ 2 H and δ 18 O Measurements by H 2 O (liquid) −H 2 O (vapor) Equilibration Laser Spectroscopy
journal, December 2008

  • Wassenaar, L. I.; Hendry, M. J.; Chostner, V. L.
  • Environmental Science & Technology, Vol. 42, Issue 24
  • DOI: 10.1021/es802065s

Discrepancies between isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters
journal, June 2010

  • West, Adam G.; Goldsmith, Gregory R.; Brooks, Paul D.
  • Rapid Communications in Mass Spectrometry, Vol. 24, Issue 14
  • DOI: 10.1002/rcm.4597

Stable hydrogen and oxygen isotopes in mineral-bound water and the indication for chemical weathering intensity
journal, November 2016


Oxygen and hydrogen isotope variations among goethites (α-FeOOH) and the determination of paleotemperatures
journal, February 1987


Oxygen isotope effects associated with the solid-state α-FeOOH to α-Fe2O3 phase transformation
journal, January 1990


Rusty Relics of Earth History: Iron(III) Oxides, Isotopes, and Surficial Environments
journal, May 2001


Stable hydrogen isotopes in iron oxides—II. variations among natural goethites
journal, February 1985


Stable hydrogen isotopes in iron oxides: 111. Nonstoichiometric hydrogen in goethite
journal, August 1995


Environmental memory and a possible seasonal bias in the stable isotope composition of (U–Th)/He-dated goethite from the Canadian Arctic
journal, August 2011


    Works referencing / citing this record:

    Isotope Drift Characteristics in Ordovician Limestone Karst Water Caused by Coal Mining in Northern China
    journal, March 2019


    Environmental behaviors of PAHs in Ordovician limestone water of Fengfeng coal mining area in China
    journal, November 2018

    • Hao, Chunming; Huang, Yue; Ma, Dengjun
    • Environmental Monitoring and Assessment, Vol. 190, Issue 12
    • DOI: 10.1007/s10661-018-7074-8