Mechanisms for the release of halogens from sea salt particles by free radical reaction
Bibliographic record
Abstract
A possible source of gas phase bromine in the Arctic winter and early spring is the sea‐salt aerosol. In this paper, chemical mechanisms for the release of photochemically active bromine from sea‐salt are examined. The first of these is oxidation of bromide to elemental bromine by peroxymonosulfuric acid (Caro's acid) produced by the free radical chain oxidation of S(IV). The chain reaction could be initiated in the dark by NO2 or, following polar sunrise, by the reaction of ozone with Superoxide. Although the yield of Caro's acid at 298 K is small, the yield may increase at the low temperatures encountered in the Arctic. This could result in the conversion of a large fraction of the initial sea‐salt alkalinity to Caro's acid. Caro's acid is known to oxidize bromide to Br2. Since this mechanism requires low temperatures and high SO2 concentrations, it is only effective during the winter and early spring and should not oxidize significant amounts of halides in the global marine boundary layer. A second possible mechanism is the free radical oxidation of aqueous bromide to bromine by OH and HO2. This may be effective at moderate pH and may contribute to Br cycling on a global scale. The evaluation of both mechanisms is highly uncertain because of incomplete physical‐chemical data. In addition to these primary release mechanisms, there are possible autocatalytic cycles for the release of bromine from sea‐salt. These involve the gas phase production of either BrO or HOBr and the return of these species to the sea‐salt particles where they initiate additional oxidation of bromide. The efficiency of these cycles should depend critically on the relative amounts of HOBr and HBr produced by the gas phase chemistry. These mechanisms do not appear to be effective as sources of photochemically active Cl.
Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.
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 | 0.000 |
| Meta-epidemiology (narrow) | 0.001 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.001 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.001 |
| Open science | 0.001 | 0.001 |
| Research integrity | 0.001 | 0.000 |
| 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".