High-precision triple oxygen isotope analysis of Archean and Proterozoic carbonates
Bibliographic record
Abstract
Oxygen isotopes are a widely used tracer in the field of paleoceanography and provide unique information on mineral formation and environmental conditions. Carbonate sediments record a shift in δ18O of 10 to 15‰ from the Archean towards higher values in the Phanerozoic. Three different scenarios are suggested to explain this observation: (I) hot Archean oceans, (II) depletion of 18O in Archean oceans compared to present day and (III) diagenetic alteration of the primary isotopic signature [1]. Recent advances in high-resolution gas source isotope ratio mass spectrometry provide a new tool that may allow to decipher the origin of this isotopic shift observed in the early rock record. We performed high-precision 18O/16O and 17O/16O measurements on oxygen ion fragments (16O+, 17O+, 18O+) generated in the ion source from CO2 gas [2]. Isobaric interferences on m/z=17 (16OH+) and m/z=18 (H216O+) are separated by means of high mass resolution. The CO2 gas is first liberated from carbonate samples by orthophosphoric acid digestion and then analyzed on a Thermo Scientific Ultra dual-inlet gas source isotope ratio mass spectrometer [3]. By adding the dimension of 17O/16O to the classical 18O/16O system, equilibrium trajectories of carbonates that are defined by the equilibrium fractionation factor (18aeq) and the triple isotope fractionation exponent (θ) can be predicted as a function of temperature. Minerals that were altered by or formed in meteoric water can be distinguished from those that precipitated in equilibrium with ambient sea water. Therefore, triple oxygen isotope analysis of carbonates does not only hold the potential for a new single-phase paleothermometer, but may also be used to trace the origin of carbonates. Here, we present high-precision triple oxygen isotope data for carbonates from the Pilbara and the Kaapvaal cratons that cover nearly one billion years from the Paleoarchean to the Paleoproterozoic. Marine carbonates from the Phanerozoic complement the dataset. The carbonates were formed in different marine settings, from shallow marine stromatolites to carbonates grown in the interstitial space of basaltic pillows. Phanerozoic carbonates record equilibrium conditions with modern sea water at moderate temperatures. The majority of Precambrian carbonates plot below the predicted equilibrium curve in the δ’18O-Δ‘17O space and do not reflect equilibrium conditions with modern sea water at elevated temperatures that were proposed for the Archean oceans. Modeling the triple oxygen isotope composition of carbonates in equilibrium with sea water, that is depleted in 18O also cannot explain the observed isotopic shift. Further modeling of post-depositional alteration suggests that most carbonates interacted and re-equilibrated with meteoric waters at variable water-rock ratios and temperatures. [1] Shields and Veizer, 2002, Geochem., Geophy., Geosyst., 10.1029/2001GC000266 [2] Getachew et al., 2019, Rapid Commun. Mass. Spectrom., 10.1002/rcm.847 [3] Eiler et al., 2013, Int. J. Mass. Spectrom., 335, 45-56.
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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 | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.000 |
| Scholarly communication | 0.001 | 0.000 |
| Open science | 0.000 | 0.001 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.001 | 0.000 |
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".