A modified procedure for gas‐source isotope ratio mass spectrometry: the long‐integration dual‐inlet (LIDI) methodology and implications for clumped isotope measurements

Bin, Hu; Radke, Jens; Schlüter, Hans-Jürgen; Heine, Frank Torsten; Zhou, Liping; Bernasconi, Stefano M.

doi:10.1002/rcm.6909

Cited by 61 publications

(74 citation statements)

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“…In the past, slightly reduced Δ 47 external precision specific to the acid drip method was hypothesized to be a result of atmospheric leakage in the reaction vessel, and/or carbonate heterogeneity more pronounced in 0.200 mg subsamples (Schmid and Bernasconi, 2010). However, recent measurement procedure and correction innovations (e.g., Hu et al, 2014;Meckler et al, 2014) have enabled similar Δ 47 external precision to the McCrea-style reaction vessel and common acid bath methods while reducing total carbonate sample size to 1.5-2.0 mg (or less).…”

Section: Acid Drip Methodsmentioning

confidence: 96%

“…This protocol consists of a single sample measurement followed by a single reference measurement of ~600 seconds each (Hu et al, 2014). This process negates the requirement of an initial pressure balancing phase as well as the constant flow of sample CO 2 gas to the exhaust pump, effectively enabling the measurement of the bulk of the available sample CO 2 gas.…”

Section: Alternative δ 47 Measurement Protocolsmentioning

confidence: 99%

“…First, the long-integration dual-inlet (LIDI) protocol which is optimized for micro-volume mode (Hu et al, 2014), and second, the 'multi-collector peak hopping' protocol, in which raw Δ 47 measurements are achieved using only the 3 Faraday cups corresponding to m/z 44, 45, and 46 . Traditionally, dual-inlet measurement protocols waste up to ~70% of sample CO 2 gas through the initial analyte pressure-balancing period, as well as the constant flow of CO 2 sample gas to an exhaust pump during reference measurement (Hu et al, 2014). The LIDI protocol was developed to maximize the efficient usage of available sample CO 2 .…”

Section: Alternative δ 47 Measurement Protocolsmentioning

confidence: 99%

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Carbonate clumped isotope paleothermometry: a review of recent advances in CO2 gas evolution, purification, measurement and standardization techniques

Spencer

Kim

2015

Geosci J

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Carbonate clumped isotope paleothermometry is based upon the principle that the formation temperature of carbonates is proportional to the relative abundance of 13 C 18 O 16 O in CO 2 produced through carbonate acid digestion. Furthermore, the relative abundance of 13 C 18 O 16 O is independent of the δ 18 O value of parent water, providing a viable alternative to the classic oxygen isotope carbonate-water paleothermometer. The temperature resolution of this newly developed paleothermometer primarily relies on the analytical techniques required to determine the clumped isotope composition of a carbonate mineral. These analytical techniques involve: (1) CO 2 gas evolution, in which carbonate is reacted with phosphoric acid, yielding CO 2 with a clumped isotope composition proportional to the carbonate formation temperature; (2) CO 2 purification, in which a rigorous purification of acid-liberated CO 2 is achieved by removing contaminants; (3) clumped isotope measurement, in which a customized gas-source isotope ratio mass spectrometer quantifies the raw clumped isotope composition (Δ 47 ) of the purified CO 2 gas; and (4) inter-laboratory standardization, in which raw Δ 47 values are normalized with respect to a community-accepted reference frame. This review provides an overview and comparison of the analytical techniques currently utilized in stable isotope laboratories for Δ 47 measurements, specifically discussing carbonate pre-treatment techniques, phosphoric acid digestion systems, isotope and temperature effects during carbonate phosphoric acid digestion, CO 2 purification processes, and the challenges associated with the measurement and standardization of the Δ 47 value. Continued refinement of these analytical techniques will aid in reducing sample size, increasing sample throughput, and improving Δ 47 external precision and associated paleotemperature resolution. Furthermore, these advances may assist in elucidating the source of discrepancies in slope between two groups of reported carbonate clumped isotope thermometer calibrations.

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Section: Acid Drip Methodsmentioning

confidence: 96%

Section: Alternative δ 47 Measurement Protocolsmentioning

confidence: 99%

Section: Alternative δ 47 Measurement Protocolsmentioning

confidence: 99%

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Carbonate clumped isotope paleothermometry: a review of recent advances in CO2 gas evolution, purification, measurement and standardization techniques

Spencer

Kim

2015

Geosci J

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“…ETH Zürich), vagy más fejlesztésű minta-előkészítő beren dezéshez csatolva a mé rés automatizál -ható, a mintaszám növelhető, a szük sé -ges anyagmennyiség pedig csökkent -hető (PASSEY et al 2010, SCHMID & BERNASCONI 2010, HU et al 2014. GHOSH et al (2006a) 1-50 °C közötti hőmér sékleti tartományra kidolgozott kalibrációja volt az első publikált ∆ 47 -T összefüggés, ami megmutatta, hogy az elméleti összefüggés a gyakorlatban is érvényes.…”

Section: Műszerekunclassified

“…Kiemelt cél a hatékonyság és a precizitás növelése, illetve a szükséges mintamennyiség csökkentése (pl. HE et al 2012, BERNASCONI et al 2013, ROSENHEIM et al 2013, CUI & WANG 2014, HU et al 2014, RÖCKMANN et al 2016. A kalibrációs munkák célja az alkalmazhatóság kiterjesztése szélesebb hőmérsékleti tartományokra (pl.…”

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Kapcsolt izotópok (clumped isotopes) a földtudományi kutatásokban

Kele

Bajnai

2017

Földt. Közl.

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BevezetésA geokémiai vizsgálatok mára a geológia minden terü -letén -az őslénytantól a rétegtanon át, a paleoklíma kutatásig -megkerülhetetlenné váltak. Az izotóp-geokémia tör té nete a XX. század első felére nyúlik vissza. Az első tömegspektrométer megalkotása 1947-ben Alfred NIER nevé hez fűződik. Ebben az időben publikálta UREY (1947), valamint BIGELEISEN & MAYER (1947 O egy többszörösen helyettesített CO 2 izotopológ). Mivel az ilyen izotopológok rendkívül alacsony előfordulási aránya a mérésüket korábban lehetetlenné tette, a többszörösen helyettesített izotopológok egészen az 1980-as évek végéig érintetlen kutatási területnek számítottak. Az első, kifejezetten erre a témára irányuló kutatás az atmoszféra metán -jának izotópos összetételét vizsgálta (MROZ et al. 1989 O isotopes within one molecule. Using the clumped isotope thermometer, the temperature of the carbonate precipitating fluids can be determined with high precision, based solely on the clumped isotope value (∆ 47 ) of carbonates. Besides palaeoclimatology, the method can be used in several research fields in geology, including palaeoceanography, atmospheric research, reservoir geology, geomorphology, structural geology, diagenesis, biogeochemistry, low temperature metamorphic processes, and meteorite research. Due to continuous developments, the number of applications is still significantly increasing. This paper briefly introduces the reader to the principles of clumped isotope geochemistry, reviewing its theoretical basis, and possible applications, and also looks at available calibrations. Furthermore, it provides an overview of the current state-of-the-art.Keywords: stable isotopes, clumped isotopes, geochemistry, thermometry, climate reconstruction, methodology Összefoglalás A kapcsoltizotóp-geokémia (clumped isotope geochemistry), egy olyan új, dinamikusan fejlődő kutatási módszer, amely a 13 C és a 18 O izotópok egy molekulán belüli kapcsolódásának hőmérsékletfüggésén alapszik. Segítségével a karbonátok kiválási hőmérséklete nagy pontossággal meghatározható, kizárólag a karbonát fázis kapcsoltizotóp-értéke (∆ 47 ) alapján. A paleoklimatológiai alkalmazások mellett a módszer a geológiai kutatások számos területén (pl. paleooceanográfia, atmoszféra-kutatás, rezervoár-geológia, geomorfológia, tektonika, diagenezis, biogeokémia, alacsony hőmérsékletű metamorf folyamatok, meteorit-kutatás, stb.) alkalmazható, és a műszerfejlesztések révén az alkal mazá -sok köre folyamatosan bővül. A cikk röviden áttekinti a kapcsolt izotópos módszert, bemutatva annak alapjait, a rendelkezésre álló kalibrációkat, a lehetséges alkalmazási területeket és a témában eddig megjelent publikációkat.

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A Reassessment of the Precision of Carbonate Clumped Isotope Measurements: Implications for Calibrations and Paleoclimate Reconstructions

Fernández

Müller

Rodríguez‐Sanz

et al. 2017

Geochem Geophys Geosyst

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Carbonate clumped isotopes offer a potentially transformational tool to interpret Earth's history, but the proxy is still limited by poor interlaboratory reproducibility. Here, we focus on the uncertainties that result from the analysis of only a few replicate measurements to understand the extent to which unconstrained errors affect calibration relationships and paleoclimate reconstructions. We find that highly precise data can be routinely obtained with multiple replicate analyses, but this is not always done in many laboratories. For instance, using published estimates of external reproducibilities we find that typical clumped isotope measurements (three replicate analyses) have margins of error at the 95% confidence level (CL) that are too large for many applications. These errors, however, can be systematically reduced with more replicate measurements. Second, using a Monte Carlo‐type simulation we demonstrate that the degree of disagreement on published calibration slopes is about what we should expect considering the precision of Δ47 data, the number of samples and replicate analyses, and the temperature range covered in published calibrations. Finally, we show that the way errors are typically reported in clumped isotope data can be problematic and lead to the impression that data are more precise than warranted. We recommend that uncertainties in Δ47 data should no longer be reported as the standard error of a few replicate measurements. Instead, uncertainties should be reported as margins of error at a specified confidence level (e.g., 68% or 95% CL). These error bars are a more realistic indication of the reliability of a measurement.

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A modified procedure for gas‐source isotope ratio mass spectrometry: the long‐integration dual‐inlet (LIDI) methodology and implications for clumped isotope measurements

Cited by 61 publications

References 32 publications

Carbonate clumped isotope paleothermometry: a review of recent advances in CO2 gas evolution, purification, measurement and standardization techniques

Carbonate clumped isotope paleothermometry: a review of recent advances in CO2 gas evolution, purification, measurement and standardization techniques

Kapcsolt izotópok (clumped isotopes) a földtudományi kutatásokban

A Reassessment of the Precision of Carbonate Clumped Isotope Measurements: Implications for Calibrations and Paleoclimate Reconstructions

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