Stable carbon isotope fractionation data between H <sub>2</sub> CO <sub>3</sub> <sup>*</sup> and CO <sub>2(g)</sub> extended to 120 °C
Bibliographic record
Abstract
RATIONALE: Literature data on experimentally derived equilibrium stable carbon isotope fractionation (10(3) lnα(13) C) between H2 CO3 (*) (H2 CO3 + CO2(aq) ) and gaseous CO2 (CO2(g) ) are so far only available up to 60 °C and were typically determined at or near atmospheric pressures. Here we experimentally expand this dataset to temperature and pressure conditions close to the supercritical state for CO2 . The objective is to improve the applicability of stable carbon isotopes as a tracer in environments where such conditions prevail. METHODS: Eighteen stable carbon isotope laboratory experiments were conducted in a steel vessel. Deionised water that was acidified with hydrochloric acid (HCl, 1 N) to a pH of 2.4 was equilibrated with CO2(g) at pressures (pCO2 ) of 55 bar for durations between 2 and 188 h. The experiments were conducted at 20, 60, 80, 100 and 120 °C. H2 CO3 (*) and CO2(g) were sampled separately and their carbon isotope ratios were determined by isotope ratio mass spectrometry. RESULTS: At 20 °C, average 10(3) lnα(13) CH2CO3 * -CO2(g) values of -1.0 ± 0.1 ‰ were observed with a preference for (12) C in H2 CO3 (*) consistent with previous research. At elevated temperatures of 120 °C, 10(3) lnα(13) CH2CO3 * -CO2(g) values decreased to an average value of -0.7 ± 0.1 ‰. The resulting temperature dependence for carbon isotope fractionation between H2 CO3 (*) and CO2(g) was 10(3) lnα(13) CH2CO3 * -CO2(g) = (0.0025 ± 0.0004) T(°C) - (1.0 ± 0.03) ‰. Carbon isotope equilibrium between H2 CO3 (*) and CO2(g) was reached within reaction times of 18 h and mostly within 5 h or less. CONCLUSIONS: 10(3) lnα(13) CH2CO3 * -CO2(g) data are now available for temperatures up to 120 °C and for pressures of up to 55 bar. The results suggest that higher pCO2 levels possibly shorten carbon isotope equilibration times. These data are critically important for using δ(13) C values as tracers, for instance at geological CO2 sequestration sites and corresponding natural analogues.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.001 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.001 |
| Science and technology studies | 0.000 | 0.001 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.001 | 0.001 |
| Insufficient payload (model declined to judge) | 0.003 | 0.001 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".