Acid digestion of carbonates using break seal method for clumped isotope analysis

Rationale Acid digestion of carbonates to release CO2 is a crucial and sensitive step in sample preparation for clumped isotope analysis. In addition to data reduction and instrumental artefacts, many other uncertainties in the clumped isotope analysis of carbonates arise from the method used for the preparation of CO2. We describe here an in-house-designed reaction vessel that circumvents degassing and contamination problems commonly associated with the McCrea-type digestion protocols. Methods We designed a leak-free break seal reaction vessel (made of Pyrex (TM)) suitable for prolonged acid digestion at 25 degrees C. Using this new vessel, several carbonate reference materials widely used in the clumped isotope community and other in-house laboratory standards were acid-digested and analysed for their delta C-13, delta O-18 and Delta(47) values with a dual inlet MAT 253 isotope ratio mass spectrometer following standard gas chromatography purification and data evaluation protocols. Results Long-term reproducibility in Delta(47) determination was established using international references and in-house working standards as follows (mean and SE): Carrara-1 (0.395 +/- 0.002 parts per thousand, n = 43), Carrara-2 (0.441 +/- 0.003 parts per thousand, n = 22), OMC (0.587 +/- 0.004 parts per thousand, n = 16), NBS 19 (0.393 +/- 0.005 parts per thousand, n = 10), NBS 18 (0.473 +/- 0.003 parts per thousand, n = 5), ETH 1 (0.271 +/- 0.005 parts per thousand, n = 7), ETH 3 (0.698 +/- 0.005 parts per thousand, n = 3), MZ (0.715 +/- 0.002 parts per thousand, n = 3) and several others. Conclusions A new method using a break seal tube was found to be efficient for the clumped isotope analysis of carbonates that require longer reaction time at 25 degrees C. This method yields good precision in Delta(47) analysis and was found to be suitable for acid digestions at any desired temperature.