0000000000046885
AUTHOR
Ulrike Wacker
Clumped isotope analysis of carbonates: comparison of two different acid digestion techniques
RATIONALE The kinetic nature of the phosphoric acid digestion reaction enables clumped isotope analysis of carbonates using gas source isotope ratio mass spectrometry (IRMS). In most laboratories acid digestions are performed at 25°C in sealed vessels or at 90°C in a common acid bath. Here we show that different Δ47 results are obtained depending on the digestion technique employed. METHODS Several replicates of a biogenic aragonite and NBS 19 were reacted with 104% H3PO4 in sealed vessels at 25°C and at 90°C using a common acid bath. The sample size varied between 4 mg and 14 mg. Purification methods that are standard for clumped isotope analyses were applied to the evolved CO2 before meas…
Refining the temperature dependence of the oxygen and clumped isotopic compositions of structurally bound carbonate in apatite
Abstract Clumped isotope data from carbonated apatite from in vivo and in vitro samples are presented to refine the relationship between mineral growth temperature and carbonate clumped isotopic composition (Δ47). Δ47, δ18O and δ13C data were obtained from phosphoric acid digestion (T = 110 °C) of chemically untreated teeth from an African elephant, Greenland sharks, sand tiger sharks and synthetic apatites. These data cover a temperature range between 1 °C and 80 °C and enlarge the calibration dataset presented in Wacker et al. (2016) by a factor of five. Taxon-specific analyses of tooth enamel(oid) and dentine reveal that both tissues show identical Δ47 values even though the content of o…
Empirical calibration of the clumped isotope paleothermometer using calcites of various origins
We present the first universal calibration of the clumped isotope thermometer for calcites of various mineralizing types. These are an eggshell of an ostrich, a tropical bivalve, a brachiopod shell, cold seep carbonate, and three foraminifera samples that grew between 9 and 38 C. CaCO3 was digested at 90 C using a common acid bath. Considering a difference in phosphoric acid fractionation factors between reaction at 25 and 90 C of 0.069& (Guo et al., 2009), the function between growth temperature T and the excess of 13 C– 18 O bonds in the evolved CO2 is expressed by a linear regression between 1/T 2 and absolute D47 (R 2 = 0.9915):
Clumped isotope thermometry of carbonate-bearing apatite: Revised sample pre-treatment, acid digestion, and temperature calibration
Abstract It has recently been shown that the clumped isotopic composition (Δ47) of carbonate-bearing hydroxyapatite (CHAP) from teeth and bones reveals important information about the body temperature of vertebrates (Eagle et al., 2010, 2011). In this study we reinvestigate the temperature dependence of Δ47 in CHAP, extending the temperature range from 2 to 59 °C. In addition, the effects of chemical pre-treatment of CHAP on its bulk and clumped isotopic composition are studied. CHAP is best reacted with phosphoric acid at 90 to 110 °C minimizing the potential of evolved CO2 or reaction intermediates to re-equilibrate with traces of water in the acid environment. Reaction at 110 °C ensures …