High precision measurements of Mg/Ca and Sr/Ca ratios in carbonates by cold plasma inductively coupled plasma quadrupole mass spectrometry

Chuan Chou Shen*, Han Yi Chiu, Hung Wei Chiang, Mei Fei Chu, Kuo Yen Wei, Stephan Steinke, Min Te Chen, Yu Shih Lin, Li Lo

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Citations (Scopus)


We present a new high precision analytical method for the determination of Mg/Ca and Sr/Ca ratios in carbonates using an inductively coupled plasma quadrupole mass spectrometer (ICP-QMS) with a 650-W cold plasma technique and a desolvation introduction system. Signal intensities are detected in pulse-counting mode and Mg/Ca and Sr/Ca ratios are calculated directly from intensity ratios of 24Mg/43Ca and 86Sr/43Ca using external matrix-matched standards for every 4-5 samples to correct for instrumental mass discrimination and low-frequency ratio drift. Significant matrix effect of Ca content on Mg/Ca determination (- 0.018 Mg/Ca (mmol/mol)/[Ca] (ppm)), can be overcome by diluting [Ca] to 6-8 ppm in the sample solution or using an empirical correction. The Sr/Ca ratio affects the Mg/Ca determination, with a factor of - 0.32% Mg/Ca per mmol/mol. This is mainly caused by the influence of doubly charged 86Sr, which biases the intensity measurement of the 43Ca+ ion beam. This effect results in a trivial offset of less than 0.1% on Mg/Ca measurements for Quaternary foraminiferal and coral samples. The internal precision of our method ranges from 0.1 to 0.2%. Replicate measurements made on standards and samples show long-term external uncertainties (2σ) of Mg/Ca = 0.84% and Sr/Ca = 0.49%. The minimum sample size requirement is only 3.5 μg of carbonate. The application of this newly developed technique on the planktonic foraminifera Globigerinoides ruber from a core recovered in the southern South China Sea yields a glacial-interglacial difference in sea surface temperature (SST) of 3 °C. Three-year coral Sr/Ca data suggest that the seasonal SST ranged from 22.6-23.8 °C in winter to 26.9-27.9 °C in summer in Nanwan, south Taiwan, during 2000-2002. The coral-Sr/Ca inferred SSTs in 2002 match well with instrumental records, which demonstrates the validity of this ICP-QMS method.

Original languageEnglish
Pages (from-to)339-349
Number of pages11
JournalChemical Geology
Issue number3-4
Publication statusPublished - 30 Jan 2007
Externally publishedYes

Bibliographical note

An erratum for this article exists and can be found in Chemical Geology, vol. 240, issue 1-2, pp. 194-195. DOI: 10.1016/j.chemgeo.2007.01.011.


  • Carbonate
  • Cold ICP-QMS
  • Coral
  • Foraminifera
  • Mg/Ca
  • Sr/Ca


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