Oxygen isotope analysis of phosphate: improved precision using TC/EA CF-IRMS
✍ Scribed by D. F. LaPorte; C. Holmden; W. P. Patterson; T. Prokopiuk; B. M. Eglington
- Book ID
- 102378207
- Publisher
- John Wiley and Sons
- Year
- 2009
- Tongue
- English
- Weight
- 186 KB
- Volume
- 44
- Category
- Article
- ISSN
- 1076-5174
- DOI
- 10.1002/jms.1549
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✦ Synopsis
Abstract
Oxygen isotope values of biogenic apatite have long demonstrated considerable promise for paleothermometry potential because of the abundance of material in the fossil record and greater resistance of apatite to diagenesis compared to carbonate. Unfortunately, this promise has not been fully realized because of relatively poor precision of isotopic measurements, and exceedingly small size of some substrates for analysis. Building on previous work, we demonstrate that it is possible to improve precision of δ^18^O~PO4~ measurements using a ‘reverse‐plumbed’ thermal conversion elemental analyzer (TC/EA) coupled to a continuous flow isotope ratio mass spectrometer (CF‐IRMS) via a helium stream [Correction made here after initial online publication]. This modification to the flow of helium through the TC/EA, and careful location of the packing of glassy carbon fragments relative to the hot spot in the reactor, leads to narrower, more symmetrically distributed CO elution peaks with diminished tailing. In addition, we describe our apatite purification chemistry that uses nitric acid and cation exchange resin. Purification chemistry is optimized for processing small samples, minimizing isotopic fractionation of PO~4~^−3^ and permitting Ca, Sr and Nd to be eluted and purified further for the measurement of δ^44^Ca and ^87^Sr/^86^Sr in modern biogenic apatite and ^143^Nd/^144^Nd in fossil apatite. Our methodology yields an external precision of ± 0.15‰ (1σ) for δ^18^O~PO4~. The uncertainty is related to the preparation of the Ag~3~PO~4~ salt, conversion to CO gas in a reversed‐plumbed TC/EA, analysis of oxygen isotopes using a CF‐IRMS, and uncertainty in constructing calibration lines that convert raw δ^18^O data to the VSMOW scale. Matrix matching of samples and standards for the purpose of calibration to the VSMOW scale was determined to be unnecessary. Our method requires only slightly modified equipment that is widely available. This fact, and the demonstrated improvement in precision, should help to make apatite paleothermometry far more accessible to paleoclimate researchers. Copyright © 2009 John Wiley & Sons, Ltd.
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