{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,7]],"date-time":"2026-10-07T04:01:55Z","timestamp":1791345715956,"version":"4.3.1"},"reference-count":31,"publisher":"Wiley","issue":"19","license":[{"start":{"date-parts":[[2020,8,16]],"date-time":"2020-08-16T00:00:00Z","timestamp":1597536000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc\/4.0\/"}],"content-domain":{"domain":["analyticalsciencejournals.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Rapid Comm Mass Spectrometry"],"published-print":{"date-parts":[[2020,10,15]]},"abstract":"\n Rationale<\/jats:title>\n \n Oxygen (\u03b4\n 18<\/jats:sup>\n O) and carbon (\u03b4\n 13<\/jats:sup>\n C) isotope analysis of foraminifera and other CaCO\n 3<\/jats:sub>\n samples has been a key technique for paleoceanographical and paleoclimatological research for more than 60\u2009years. There is ongoing demand for the analysis of ever smaller CaCO\n 3<\/jats:sub>\n samples, driven, for example, by the desire to analyse single specimen planktic foraminifera, or small samples of tooth enamel.\n <\/jats:p>\n <\/jats:sec>\n \n Methods<\/jats:title>\n \n We present a continuous\u2010flow mass spectrometric technique that uses cryo\u2010focusing of sample CO\n 2<\/jats:sub>\n to analyse CaCO\n 3<\/jats:sub>\n samples in a weight range between 10 and 3\u2009\u03bcg. These are considerably lower sample weights than achievable on most currently available standard instrumentation. The technique is automated, so that sample throughput lies at >60 samples per day. The method involves an on\u2010line vial\u2010flushing routine designed to remove machine drift due to blank CO\n 2<\/jats:sub>\n build\u2010up in the sample vials.\n <\/jats:p>\n <\/jats:sec>\n \n Results<\/jats:title>\n \n In a series of experiments the effect of blank CO\n 2<\/jats:sub>\n build\u2010up is quantified, and outgassing from the chlorobutyl septa identified as the source. An improved flushing routine together with the use of a cryo\u2010focusing step in the analysis is demonstrated to provide the analytical stability and sensitivity to analyse CaCO\n 3<\/jats:sub>\n samples in a weight range between 10 and 3\u2009\u03bcg at \u22640.1\u2030 precision (1\u03c3) for both \u03b4\n 18<\/jats:sup>\n O and \u03b4\n 13<\/jats:sup>\n C values. The technique yields similarly precise results for the analysis of the structural carbonate fraction of small tooth enamel samples.\n <\/jats:p>\n <\/jats:sec>\n \n Conclusions<\/jats:title>\n \n This study demonstrates that high\u2010precision oxygen and carbon isotope analysis is possible on CaCO\n 3<\/jats:sub>\n samples smaller than 5\u2009\u03bcg by use of a continuous\u2010flow isotope technique. Of key importance are (1) the application of a cold trap that drastically reduces sample gas loss, and (2) a modified flushing regime that eliminates increasing background CO\n 2<\/jats:sub>\n build\u2010up in sample vials during longer automated sample runs.\n <\/jats:p>\n <\/jats:sec>","DOI":"10.1002\/rcm.8878","type":"journal-article","created":{"date-parts":[[2020,7,7]],"date-time":"2020-07-07T04:20:00Z","timestamp":1594095600000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":36,"title":["High\u2010precision stable isotope analysis of <5 \u03bcg CaCO\n 3<\/sub>\n samples by continuous\u2010flow mass spectrometry"],"prefix":"10.1002","volume":"34","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0897-8244","authenticated-orcid":false,"given":"Hubert B.","family":"Vonhof","sequence":"first","affiliation":[{"name":"Department of Climate Geochemistry Max Planck Institute for Chemistry Hahn\u2010Meitner\u2010Weg 1 Mainz 55128 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1054-1049","authenticated-orcid":false,"given":"Stefan","family":"de Graaf","sequence":"additional","affiliation":[{"name":"Department of Climate Geochemistry Max Planck Institute for Chemistry Hahn\u2010Meitner\u2010Weg 1 Mainz 55128 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5465-8607","authenticated-orcid":false,"given":"Howard J.","family":"Spero","sequence":"additional","affiliation":[{"name":"Department of Earth and Planetary Sciences University California Davis Davis CA 95616 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6252-7647","authenticated-orcid":false,"given":"Ralf","family":"Schiebel","sequence":"additional","affiliation":[{"name":"Department of Climate Geochemistry Max Planck Institute for Chemistry Hahn\u2010Meitner\u2010Weg 1 Mainz 55128 Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Suzan J.A.","family":"Verdegaal","sequence":"additional","affiliation":[{"name":"Department of Earth Sciences, Faculty of Science Vrije Universiteit Amsterdam Amsterdam The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5873-9815","authenticated-orcid":false,"given":"Brett","family":"Metcalfe","sequence":"additional","affiliation":[{"name":"Department of Earth Sciences, Faculty of Science Vrije Universiteit Amsterdam Amsterdam The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gerald H.","family":"Haug","sequence":"additional","affiliation":[{"name":"Department of Climate Geochemistry Max Planck Institute for Chemistry Hahn\u2010Meitner\u2010Weg 1 Mainz 55128 Germany"},{"name":"Department of Earth Sciences, ETH Z\u00fcrich Sonneggstrasse 5 Z\u00fcrich 8092 Switzerland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2020,8,16]]},"reference":[{"key":"e_1_2_6_2_1","doi-asserted-by":"publisher","DOI":"10.1086\/626295"},{"key":"e_1_2_6_3_1","volume-title":"Principles of Stable Isotope Geochemistry","author":"Sharp Z","year":"2017"},{"key":"e_1_2_6_4_1","doi-asserted-by":"publisher","DOI":"10.2113\/gsjfr.25.1.24"},{"key":"e_1_2_6_5_1","doi-asserted-by":"publisher","DOI":"10.1029\/95PA03773"},{"key":"e_1_2_6_6_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF02849675"},{"key":"e_1_2_6_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/0377-8398(93)90045-Y"},{"key":"e_1_2_6_8_1","doi-asserted-by":"publisher","DOI":"10.1017\/pab.2014.7"},{"key":"e_1_2_6_9_1","doi-asserted-by":"publisher","DOI":"10.2517\/2015PR036"},{"key":"e_1_2_6_10_1","doi-asserted-by":"publisher","DOI":"10.5194\/cp-7-1337-2011"},{"key":"e_1_2_6_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/0031-0182(81)90038-9"},{"key":"e_1_2_6_12_1","doi-asserted-by":"publisher","DOI":"10.5194\/bg-12-4781-2015"},{"key":"e_1_2_6_13_1","doi-asserted-by":"publisher","DOI":"10.1017\/S1089332600000383"},{"key":"e_1_2_6_14_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.quascirev.2017.10.007"},{"issue":"6","key":"e_1_2_6_15_1","first-page":"767","article-title":"Problems and prospects for carbon isotope analysis of very small samples of fossil tooth enamel","volume":"168","author":"Lee\u2010Thorp J","year":"1997","journal-title":"Bull Soc Geol Fr"},{"key":"e_1_2_6_16_1","doi-asserted-by":"publisher","DOI":"10.1016\/B978-044451114-0\/50040-5"},{"key":"e_1_2_6_17_1","unstructured":"RadkeJ HauboldP HilckertA.Isotope analysis of 6\u2013130 \u03bcg samples with the KIEL IV carbonate device. 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