The inversion of aragonite to calcite during the sampling of skeletal archives: Implications for proxy interpretation

Amanda J. Waite, Peter K Swart

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Rationale: Understanding changes in Earth's oceans and climate requires the reliable application of paleo-proxies. However, inconsistencies between individual δ<sup>18</sup>O records within biogenic specimens commonly have significant impacts on environmental reconstructions. This study addresses the stable isotope variability associated with sample milling from aragonitic organisms commonly used for paleoclimate studies. Methods: Aragonite samples were hand-ground and milled from sclerosponge, coral, and mollusc specimens using a computerized micromill. An X-ray diffractometer was used to analyze sample mineralogy prior to measurement of δ<sup>18</sup>O and δ<sup>13</sup>C values via isotope ratio mass spectrometry of CO<inf>2</inf> gases provided from the samples by a Kiel III device. Possible influences on the Sr/Ca ratios were assessed on a sclerosponge through paired elemental analysis by inductively coupled plasma optical emission spectrometry. Results: Analyses revealed up to 36% inversion to calcite in milled samples that correlated with a decrease in the δ<sup>18</sup>O value of 0.02 ‰ per 1% inversion. Replicate sclerosponge transects yielded similar trends in δ<sup>13</sup>C values and Sr/Ca ratios, although the δ<sup>18</sup>O values showed irregular variations consistent with those measured for the inversion of individual organisms during milling. Conclusions: While the δ<sup>13</sup>C values and Sr/Ca ratios of milled samples were largely consistent, the δ<sup>18</sup>O values co-varied with the inversion of aragonite to calcite suggesting significant implications for the resulting temperature and salinity reconstructions from aragonitic archives. The effect appears to be density-driven and, given that the skeletal density tends to vary seasonally in organisms such as corals, would subsequently mask temperature-induced changes in skeletal δ<sup>18</sup>O values.

Original languageEnglish (US)
Pages (from-to)955-964
Number of pages10
JournalRapid Communications in Mass Spectrometry
Volume29
Issue number10
DOIs
StatePublished - May 30 2015

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Calcium Carbonate
Sampling
Isotopes
Molluscs
Mineralogy
Diffractometers
Inductively coupled plasma
Spectrometry
Mass spectrometry
Masks
Gases
Earth (planet)
X rays
Temperature
Chemical analysis

ASJC Scopus subject areas

  • Spectroscopy
  • Analytical Chemistry
  • Organic Chemistry

Cite this

The inversion of aragonite to calcite during the sampling of skeletal archives : Implications for proxy interpretation. / Waite, Amanda J.; Swart, Peter K.

In: Rapid Communications in Mass Spectrometry, Vol. 29, No. 10, 30.05.2015, p. 955-964.

Research output: Contribution to journalArticle

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abstract = "Rationale: Understanding changes in Earth's oceans and climate requires the reliable application of paleo-proxies. However, inconsistencies between individual δ18O records within biogenic specimens commonly have significant impacts on environmental reconstructions. This study addresses the stable isotope variability associated with sample milling from aragonitic organisms commonly used for paleoclimate studies. Methods: Aragonite samples were hand-ground and milled from sclerosponge, coral, and mollusc specimens using a computerized micromill. An X-ray diffractometer was used to analyze sample mineralogy prior to measurement of δ18O and δ13C values via isotope ratio mass spectrometry of CO2 gases provided from the samples by a Kiel III device. Possible influences on the Sr/Ca ratios were assessed on a sclerosponge through paired elemental analysis by inductively coupled plasma optical emission spectrometry. Results: Analyses revealed up to 36{\%} inversion to calcite in milled samples that correlated with a decrease in the δ18O value of 0.02 ‰ per 1{\%} inversion. Replicate sclerosponge transects yielded similar trends in δ13C values and Sr/Ca ratios, although the δ18O values showed irregular variations consistent with those measured for the inversion of individual organisms during milling. Conclusions: While the δ13C values and Sr/Ca ratios of milled samples were largely consistent, the δ18O values co-varied with the inversion of aragonite to calcite suggesting significant implications for the resulting temperature and salinity reconstructions from aragonitic archives. The effect appears to be density-driven and, given that the skeletal density tends to vary seasonally in organisms such as corals, would subsequently mask temperature-induced changes in skeletal δ18O values.",
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N2 - Rationale: Understanding changes in Earth's oceans and climate requires the reliable application of paleo-proxies. However, inconsistencies between individual δ18O records within biogenic specimens commonly have significant impacts on environmental reconstructions. This study addresses the stable isotope variability associated with sample milling from aragonitic organisms commonly used for paleoclimate studies. Methods: Aragonite samples were hand-ground and milled from sclerosponge, coral, and mollusc specimens using a computerized micromill. An X-ray diffractometer was used to analyze sample mineralogy prior to measurement of δ18O and δ13C values via isotope ratio mass spectrometry of CO2 gases provided from the samples by a Kiel III device. Possible influences on the Sr/Ca ratios were assessed on a sclerosponge through paired elemental analysis by inductively coupled plasma optical emission spectrometry. Results: Analyses revealed up to 36% inversion to calcite in milled samples that correlated with a decrease in the δ18O value of 0.02 ‰ per 1% inversion. Replicate sclerosponge transects yielded similar trends in δ13C values and Sr/Ca ratios, although the δ18O values showed irregular variations consistent with those measured for the inversion of individual organisms during milling. Conclusions: While the δ13C values and Sr/Ca ratios of milled samples were largely consistent, the δ18O values co-varied with the inversion of aragonite to calcite suggesting significant implications for the resulting temperature and salinity reconstructions from aragonitic archives. The effect appears to be density-driven and, given that the skeletal density tends to vary seasonally in organisms such as corals, would subsequently mask temperature-induced changes in skeletal δ18O values.

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