Determination of (Oxy)thioarsenates in Sulfidic Waters
Bibliographic record
Abstract
Although it has long been known that soluble arsenic-sulfur (As-S) compounds exist in sulfidic waters and may play significant roles in several important processes in the biogeochemical arsenic cycle, no suitable analytical methods exist for their determination. We provide evidence that the four homologue (oxy)thioarsenates, mono-, di-, tri-, and tetrathioarsenate (AsO3S3-, AsO2S23-, AsOS33- and AsS43-), can be formed in geochemical model reactions between arsenite and sulfide under anoxic conditions (through currently unknown reaction mechanisms) and that these compounds appear to be major As species in natural sulfidic waters. These As-S species are quantified by anion-exchange chromatography-inductively coupled plasma mass spectrometry (AEC-ICPMS) with instrumental detection limits of approximately 0.1 nmol of As L(-1) in undiluted samples; arsenite, arsenate, and monomethylarsenate are quantified as well, but dimethylarsenate cannot be analyzed by this technique. Sulfur in the eluting peaks can be measured as SO+ with detection limits of approximately 0.1 micromol of S L(-1). The (oxy)thioarsenates were synthesized in solution and characterized by electrospray-tandem mass spectrometry (ES-MS-MS). In geochemical model solutions, we confirmed that both the AEC-ICPMS retention times and the ES-MS-MS spectra of the reaction products of sulfide and arsenite matched the synthesized (oxy)thioarsenate standards; for natural waters, the mass spectrometric confirmation was unsuccessful, due to matrix interferences.
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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 | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 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".