Seasonal temperature changes obtained from carbonate clumped isotopes of annually laminated tufas from Japan: Discrepancy between natural and synthetic calcites

Hirokazu Kato, Shota Amekawa, Akihiro Kano, Taiki Mori, Yoshihiro Kuwahara, Jay Quade

Research output: Contribution to journalArticle

Abstract

Carbonate clumped isotopes provide a novel paleo-thermometer that does not require knowledge of the isotopic compositions of environmental water. Despite considerable effort, there are substantial inter-laboratory disagreements in empirical calibrations between the abundance anomaly of the clumped isotopes (Δ47) and absolute temperature, and discrepancies in paleo-temperature estimates from natural samples. In this study, clumped isotopes using two types of 17O corrections were analyzed for two sample sets of synthetic calcites and tufas collected monthly from two sites in southwest Japan with known δ18O values and temperatures of parent water. These measurements form the basis for two new temperature calibrations of carbonate clumped isotopes, the first from our Kyushu University laboratory in Japan. The calcites synthesized at four different temperatures (2.9–61.0 °C) yield a temperature-Δ47 relationship of Δ47=0.0354±0.0013×106/T2+0.290±0.015 (R2 = 0.986), which is indistinguishable from the calibrations of other recent studies based on acid digestion experiments at high temperature (70–100 °C). The Δ47 thermometry for the natural tufa samples display the seasonal pattern of water temperature better than the δ18O thermometry. However, the Δ47 values of the tufa samples deposited at temperatures ranging from 5.6 to 16.0 °C were lower than the values expected from the calibration using synthetic calcites, thus providing another temperature calibration of Δ47=0.0336±0.0036×106/T2+0.301±0.048 (R2 = 0.735). Therefore, our results clearly identify a detectable, but fairly uniform, discrepancy in Δ47-temperature calibration between synthetic calcite and natural samples (tufas). The amplitude of Δ47 offset between the tufa and synthetic samples appears to be independent of the seasonal change in water temperature and the chemical properties of water, including pH, pCO2, and precipitation rate of calcite. The lower Δ47 values have been previously reported from other tufas and travertines, and therefore appear to be associated with processes inherent to tufas and travertines, such as CO2 degassing. We also find that our results are insignificantly influenced by types of 17O corrections and almost independent with bulk isotopic composition.

LanguageEnglish
Pages548-564
Number of pages17
JournalGeochimica et Cosmochimica Acta
Volume244
DOIs
Publication statusPublished - Jan 1 2019

Fingerprint

Oxygen Isotopes
tufa
Calcium Carbonate
Carbonates
Isotopes
oxygen isotope
calcite
isotope
carbonate
calibration
temperature
Calibration
Temperature
travertine
Water
isotopic composition
water temperature
acid digestion
degassing
water

All Science Journal Classification (ASJC) codes

  • Geochemistry and Petrology

Cite this

Seasonal temperature changes obtained from carbonate clumped isotopes of annually laminated tufas from Japan : Discrepancy between natural and synthetic calcites. / Kato, Hirokazu; Amekawa, Shota; Kano, Akihiro; Mori, Taiki; Kuwahara, Yoshihiro; Quade, Jay.

In: Geochimica et Cosmochimica Acta, Vol. 244, 01.01.2019, p. 548-564.

Research output: Contribution to journalArticle

@article{c77fc3a3877e43be8e031e5624c14b9e,
title = "Seasonal temperature changes obtained from carbonate clumped isotopes of annually laminated tufas from Japan: Discrepancy between natural and synthetic calcites",
abstract = "Carbonate clumped isotopes provide a novel paleo-thermometer that does not require knowledge of the isotopic compositions of environmental water. Despite considerable effort, there are substantial inter-laboratory disagreements in empirical calibrations between the abundance anomaly of the clumped isotopes (Δ47) and absolute temperature, and discrepancies in paleo-temperature estimates from natural samples. In this study, clumped isotopes using two types of 17O corrections were analyzed for two sample sets of synthetic calcites and tufas collected monthly from two sites in southwest Japan with known δ18O values and temperatures of parent water. These measurements form the basis for two new temperature calibrations of carbonate clumped isotopes, the first from our Kyushu University laboratory in Japan. The calcites synthesized at four different temperatures (2.9–61.0 °C) yield a temperature-Δ47 relationship of Δ47=0.0354±0.0013×106/T2+0.290±0.015 (R2 = 0.986), which is indistinguishable from the calibrations of other recent studies based on acid digestion experiments at high temperature (70–100 °C). The Δ47 thermometry for the natural tufa samples display the seasonal pattern of water temperature better than the δ18O thermometry. However, the Δ47 values of the tufa samples deposited at temperatures ranging from 5.6 to 16.0 °C were lower than the values expected from the calibration using synthetic calcites, thus providing another temperature calibration of Δ47=0.0336±0.0036×106/T2+0.301±0.048 (R2 = 0.735). Therefore, our results clearly identify a detectable, but fairly uniform, discrepancy in Δ47-temperature calibration between synthetic calcite and natural samples (tufas). The amplitude of Δ47 offset between the tufa and synthetic samples appears to be independent of the seasonal change in water temperature and the chemical properties of water, including pH, pCO2, and precipitation rate of calcite. The lower Δ47 values have been previously reported from other tufas and travertines, and therefore appear to be associated with processes inherent to tufas and travertines, such as CO2 degassing. We also find that our results are insignificantly influenced by types of 17O corrections and almost independent with bulk isotopic composition.",
author = "Hirokazu Kato and Shota Amekawa and Akihiro Kano and Taiki Mori and Yoshihiro Kuwahara and Jay Quade",
year = "2019",
month = "1",
day = "1",
doi = "10.1016/j.gca.2018.10.016",
language = "English",
volume = "244",
pages = "548--564",
journal = "Geochmica et Cosmochimica Acta",
issn = "0016-7037",
publisher = "Elsevier Limited",

}

TY - JOUR

T1 - Seasonal temperature changes obtained from carbonate clumped isotopes of annually laminated tufas from Japan

T2 - Geochmica et Cosmochimica Acta

AU - Kato, Hirokazu

AU - Amekawa, Shota

AU - Kano, Akihiro

AU - Mori, Taiki

AU - Kuwahara, Yoshihiro

AU - Quade, Jay

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Carbonate clumped isotopes provide a novel paleo-thermometer that does not require knowledge of the isotopic compositions of environmental water. Despite considerable effort, there are substantial inter-laboratory disagreements in empirical calibrations between the abundance anomaly of the clumped isotopes (Δ47) and absolute temperature, and discrepancies in paleo-temperature estimates from natural samples. In this study, clumped isotopes using two types of 17O corrections were analyzed for two sample sets of synthetic calcites and tufas collected monthly from two sites in southwest Japan with known δ18O values and temperatures of parent water. These measurements form the basis for two new temperature calibrations of carbonate clumped isotopes, the first from our Kyushu University laboratory in Japan. The calcites synthesized at four different temperatures (2.9–61.0 °C) yield a temperature-Δ47 relationship of Δ47=0.0354±0.0013×106/T2+0.290±0.015 (R2 = 0.986), which is indistinguishable from the calibrations of other recent studies based on acid digestion experiments at high temperature (70–100 °C). The Δ47 thermometry for the natural tufa samples display the seasonal pattern of water temperature better than the δ18O thermometry. However, the Δ47 values of the tufa samples deposited at temperatures ranging from 5.6 to 16.0 °C were lower than the values expected from the calibration using synthetic calcites, thus providing another temperature calibration of Δ47=0.0336±0.0036×106/T2+0.301±0.048 (R2 = 0.735). Therefore, our results clearly identify a detectable, but fairly uniform, discrepancy in Δ47-temperature calibration between synthetic calcite and natural samples (tufas). The amplitude of Δ47 offset between the tufa and synthetic samples appears to be independent of the seasonal change in water temperature and the chemical properties of water, including pH, pCO2, and precipitation rate of calcite. The lower Δ47 values have been previously reported from other tufas and travertines, and therefore appear to be associated with processes inherent to tufas and travertines, such as CO2 degassing. We also find that our results are insignificantly influenced by types of 17O corrections and almost independent with bulk isotopic composition.

AB - Carbonate clumped isotopes provide a novel paleo-thermometer that does not require knowledge of the isotopic compositions of environmental water. Despite considerable effort, there are substantial inter-laboratory disagreements in empirical calibrations between the abundance anomaly of the clumped isotopes (Δ47) and absolute temperature, and discrepancies in paleo-temperature estimates from natural samples. In this study, clumped isotopes using two types of 17O corrections were analyzed for two sample sets of synthetic calcites and tufas collected monthly from two sites in southwest Japan with known δ18O values and temperatures of parent water. These measurements form the basis for two new temperature calibrations of carbonate clumped isotopes, the first from our Kyushu University laboratory in Japan. The calcites synthesized at four different temperatures (2.9–61.0 °C) yield a temperature-Δ47 relationship of Δ47=0.0354±0.0013×106/T2+0.290±0.015 (R2 = 0.986), which is indistinguishable from the calibrations of other recent studies based on acid digestion experiments at high temperature (70–100 °C). The Δ47 thermometry for the natural tufa samples display the seasonal pattern of water temperature better than the δ18O thermometry. However, the Δ47 values of the tufa samples deposited at temperatures ranging from 5.6 to 16.0 °C were lower than the values expected from the calibration using synthetic calcites, thus providing another temperature calibration of Δ47=0.0336±0.0036×106/T2+0.301±0.048 (R2 = 0.735). Therefore, our results clearly identify a detectable, but fairly uniform, discrepancy in Δ47-temperature calibration between synthetic calcite and natural samples (tufas). The amplitude of Δ47 offset between the tufa and synthetic samples appears to be independent of the seasonal change in water temperature and the chemical properties of water, including pH, pCO2, and precipitation rate of calcite. The lower Δ47 values have been previously reported from other tufas and travertines, and therefore appear to be associated with processes inherent to tufas and travertines, such as CO2 degassing. We also find that our results are insignificantly influenced by types of 17O corrections and almost independent with bulk isotopic composition.

UR - http://www.scopus.com/inward/record.url?scp=85055915197&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85055915197&partnerID=8YFLogxK

U2 - 10.1016/j.gca.2018.10.016

DO - 10.1016/j.gca.2018.10.016

M3 - Article

VL - 244

SP - 548

EP - 564

JO - Geochmica et Cosmochimica Acta

JF - Geochmica et Cosmochimica Acta

SN - 0016-7037

ER -