Calibration of the dual clumped isotope thermometer for carbonates

Fiebig, Jens; Daëron, Mathieu; Bernecker, Miguel; Guo, Weifu; Schneider, Gerd‐Helge; Boch, Ronny; Bernasconi, Stefano M.; Jautzy, Josué; Dietzel, Martin

doi:10.1016/j.gca.2021.07.012

Cited by 63 publications

(179 citation statements)

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“…Recent modeling predictions from Guo (2020) has aimed to constrain KIEs in the Δ47, Δ48 and ẟ 18 O of the HCO3endmember in hydration and hydroxylation reactions occurring during CO2 absorption, degassing, and DIC-H2O exchange. Bajnai et al (2020) and Fiebig et al (2021) constructed Δ47 and Δ48 slopes relative to an equilibrium regression to remove kinetic biases from warm and cold-water coral, brachiopod, belemnite, stalagmite, and speleothem samples.…”

Section: Disequilibrium Processes In Carbonatesmentioning

confidence: 99%

“…These results lend further support to experimental and field-derived calibration datasets being in near equilibrium. An F test (performed in PRISM 7) was used for a statistical comparison between experimentally determined regressions for Δ47 and Δ48 values for near-equilibrium samples with known precipitation temperatures from Swart et al (2021), Fiebig et al (2021), with results from this study (Table 7). The test determined that the regressions were not statistically different (p = 0.99, Table 8) and a combined regression is represented by equation 15 (Figure 11).…”

Section: Paired Clumped Isotope Data: Near Equilibrium Mineral Compositionsmentioning

confidence: 99%

“…Δ48 CDES 90 = (0.407 ± 0.016) Δ47 CDES 90 + (0.006 ± 0.009); r 2 = 0.98 (15) The data from Fiebig et al (2021) includes lake and cave calcites, inorganic precipitations, and samples equilibrated at high temperatures, with samples having crystallization temperatures from 7.9 o C to 1100 o C. Sample data from Swart et al (2021) includes 7 inorganic calcite precipitations from 5 o C to 65 o C. The experimentally determined regressions from Swart et al (2021), Fiebig et al (2021), and this study are bracketed by regressions from Bajnai et al (2020) and Lucarelli et al (2021) determined using a combination of theory from Hill et al (2014) and Tripati et al (2015) and experimental AFF values. These regressions are statistically indistinguishable from the experimental regressions (p = 0.99).…”

Section: Paired Clumped Isotope Data: Near Equilibrium Mineral Compositionsmentioning

confidence: 99%

“…The use of Δ47 and Δ48 as paleothermometers rely on equilibrium clumped isotope fractionation in the carbonate mineral lattice. However, recent theoretical and experimental work has shown that some biogenic and abiogenic carbonates yield disequilibrium Δ47 (Ghosh et al, 2006;Daëron et al, 2011, Saenger et al, 2012, Tang et al, 2014Tripati et al, 2015;Guo et al, 2019;Daeron et al, 2019) and Δ48 values (Tripati et al, 2015;Guo, 2020;Bajnai et al, 2020;Lucarelli et al, 2021;Fiebig et al, 2021).…”

Section: Introductionmentioning

confidence: 99%

“…The paired measurement of Δ47 and Δ48 has been theoretically (Hill et al, 2014;Tripati et al, 2015;Guo, 2020;Hill et al, 2020) and experimentally (Fiebig et al, 2019;Bajnai et al, 2020;Lucarelli et al, 2021;Fiebig et al, 2021) shown to have a characteristic equilibrium relationship. The equilibrium Δ47-Δ48 relationship along with constrained boundaries of disequilibrium trajectories in dissolved inorganic carbon (DIC) pools and in carbonate minerals may be used to identify the origin of kinetic isotope effects (Tripati et al, 2015;Bajnai et al, 2020;Guo, 2020) and used to correct for such effects and derive expected equilibrium clumped isotope values from samples Guo, 2020).…”

Section: Introductionmentioning

confidence: 99%

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Paired Δ47 and Δ48 analyses and model calculations constrain equilibrium, experimentally-manipulated kinetic isotope effects, and mixing effects in calcite

Lucarelli¹,

Purgstaller²,

Parven³

et al. 2022

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The high-precision analysis of the abundance of the dominant m/z 47 CO2 isotopologue derived from acid digestion of carbonate minerals (13C18O16O; denoted by Δ47) forms the basis for carbonate clumped isotope thermometry. Since the first measurements were published 16 years ago, considerable effort has gone into characterizing the relationship between Δ47 and carbonate precipitation temperature, and in identifying carbonates that do not achieve isotopic equilibrium. Mass spectrometry is now capable of the paired measurement of the primary m/z 47 and m/z 48-isotopologues (Δ47 and Δ48; 12C18O2 is denoted by Δ48), which has the potential to place additional constraints on kinetic isotope effects in carbonate minerals and trace distinct reaction pathways. Here, we explored factors that contribute to calcite mineral equilibrium and disequilibrium in Δ47 and Δ48 using a combination of experiments and theoretical calculations with three types of models. We precipitated calcite at pH 8.3 with carbonic anhydrase (CA) to approach quasi-isotopic equilibrium in the dissolved inorganic carbon pool and report values for Δ47, Δ48, and oxygen isotopes (δ18O) for calcite grown over a temperature range from 5 to 25 oC and compare our findings to predictions from an ion-by-ion model that support equilibrium precipitation. We also compare results to the Devils Hole slow-growing cave calcite, and other published temperature calibration data. We report the following combined equilibrium calibration relationships: Δ48 CDES 90 = (0.429 ± 0.010) Δ47 CDES 90 - (0.006 ± 0.006); r2 = 0.98; Δ47 I-CDES = (0.037 ± 0.001) × 106T-2 + (0.178 ± 0.009); r2 = 0.99; Δ48 CDES 90 = (0.015 ± 0.0005) × 106T-2 + (0.078 ± 0.006); r2 = 0.98. We used paired measurements of Δ47 and Δ48 to constrain kinetic isotope effects in calcite precipitated at pH ranging from 8.3-11 and temperatures from 5 to 25 oC, with and without CA present, and observe kinetic enrichments in Δ47, negative (hyperstochastic) values for Δ48, and depleted values of δ18O, compared to equilibrium values. Experimentally constrained kinetic trajectories, when compared with an ion-by-ion model and IsoDIC theoretical predictions, are consistent with CO2 hydration/hydroxylation. Mixing drives elevated Δ47 and Δ48 values and was assessed using mixing experiments with endmembers of varying isotopic compositions and compared to a Δ47 and Δ48 mixing model that constrains nonlinear mixing trajectories for calcite. While mixing may induce artifacts in two-component mixtures when endmember bulk compositions differ by more than 7 ‰, or if endmember Δ47 and Δ48 differ by more than 0.03 ‰, this should be detectable and potentially correctible using paired clumped isotope measurements and is unlikely to be important for some materials.

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Section: Disequilibrium Processes In Carbonatesmentioning

confidence: 99%

Section: Paired Clumped Isotope Data: Near Equilibrium Mineral Compositionsmentioning

confidence: 99%

Section: Paired Clumped Isotope Data: Near Equilibrium Mineral Compositionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Paired Δ47 and Δ48 analyses and model calculations constrain equilibrium, experimentally-manipulated kinetic isotope effects, and mixing effects in calcite

Lucarelli¹,

Purgstaller²,

Parven³

et al. 2022

Preprint

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Temperature dependence of clumped isotopes (∆47) in aragonite

Winter

Witbaard

Kocken

et al. 2022

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Wang et al., 2004), carbonate clumped isotope analysis has developed into a valuable tool for paleothermometry in the geosciences. Clumped isotope analysis is based on the thermodynamic principle that molecules with multiple heavy isotopes (so-called "multiply-substituted isotopologues") have lower vibrational energies than molecules containing lighter isotopes (Urey, 1947). Consequently, the increase in system entropy at higher temperatures causes a decrease in the occurrence of multiply-substituted isotopologues, and "clumping" of heavy isotopes within the same molecule is favored in low-energy systems (Eiler, 2007). In carbonates, this principle causes heavy carbonate ions (e.g., 13 C 18 O 16 O 2 ; mass 63 or 12 C 18 O 2 16 O; mass 64) to become more abundant with decreasing calcification temperatures (Ghosh et al., 2006). The distribution of these isotopologues is proportional in the CO 2 gas after reaction of carbonates with acid (e.g., 13 C 18 O 16 O; mass 47 and 12 C 18 O 2 , mass 48 respectively) and is measured with reference to the distribution of isotopologues in a fully scrambled heated CO 2 gas with the same isotopic composition:

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Paired dual carbonate clumped isotopes (Δ47-Δ48) constrains kinetic effects and timescales in peridotite-associated springs at The Cedars, Northern California

Parvez

Matamoros

Rubi

et al. 2022

Preprint

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Eagle-Tripati LaboratoriesGuide for clumped isotope data quality assessment, including measurement flagging December 2022 J. Lucarelli and A. Tripati • Definitions:○ Data quality assessment: the process of assessing if data are reproducible, including identifying if there were statistical outliers that may arise due to incomplete sample digestion, voltage fluctuations, exchange with water, carousel not advancing properly, or other processes relating to sample reaction, purification, and measurement, etc., resulting in an erroneous measurement or non-representative value ○ Flagging: identifying a statistical outlier that you hypothesize is due to an erroneous measurement or is not representative of the sample, that you think should not be included in calculations.■ You need ≥3 replicates to begin flagging. ○ Outlier: an observation that statistically lies an abnormal distance from other values in a random sample from a population. ○ Exclusion: removal of an analysis from the population.■ Before excluding a replicate, talk to Aradhna/Rob and Ben about why it's being excluded -there may be a solution to the issue. ■ You must include detailed notes on the justification in both the run log and in Easotope, after discussion with Aradhna/Rob and Ben ○ Standard deviation: a measure of the amount of variation or dispersion of a set of values.A low standard deviation indicates that the values tend to be close to the mean (also called the expected value) of the set, while a high standard deviation indicates that the values are spread out over a wider range.

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Calibration of the dual clumped isotope thermometer for carbonates

Cited by 63 publications

References 63 publications

Paired Δ47 and Δ48 analyses and model calculations constrain equilibrium, experimentally-manipulated kinetic isotope effects, and mixing effects in calcite

Paired Δ47 and Δ48 analyses and model calculations constrain equilibrium, experimentally-manipulated kinetic isotope effects, and mixing effects in calcite

Temperature dependence of clumped isotopes (∆47) in aragonite

Paired dual carbonate clumped isotopes (Δ47-Δ48) constrains kinetic effects and timescales in peridotite-associated springs at The Cedars, Northern California

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