Heterogeneous formation of nitryl chloride and its role as a nocturnal NO<i><sub>x</sub></i> reservoir species during CalNex‐LA 2010
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Bibliographic record
Abstract
Abstract The nocturnal conversion of dinitrogen pentoxide (N 2 O 5 ) to nitryl chloride (ClNO 2 ) on chloride‐containing aerosol can be a regionally important NO x (= NO + NO 2 ) recycling and halogen activation pathway that affects oxidant photochemistry the following day. Here we present a comprehensive measurement data set acquired at Pasadena, California, during the CalNex‐LA campaign 2010 that included measurements of odd nitrogen and its major components (NO y = NO x + NO 3 + 2N 2 O 5 + ClNO 2 + HNO 3 + HONO + peroxyacyl, alkyl, and aerosol nitrates) and aerosol size distribution and composition. Nitryl chloride was present during every night of the study (median mixing ratio at sunrise 800 pptv) and was usually a more significant nocturnal NO x and odd oxygen (O x = O 3 + NO 2 + 3N 2 O 5 + ClNO 2 ) reservoir species than N 2 O 5 (whose concentrations were calculated from its equilibrium with NO 2 and NO 3 ). At sunrise, ClNO 2 accounted for 21% of NO z (=NO y − NO x ), 4% of NO y , and 2.5% of O x , respectively (median values). Kinetic parameters for the N 2 O 5 to ClNO 2 conversion were estimated by relating ClNO 2 concentrations to their time‐integrated heterogeneous production from N 2 O 5 and were highly variable between nights. Production of ClNO 2 required conversion of N 2 O 5 on submicron aerosol with average yield (φ) and N 2 O 5 reactive uptake probability (γ) of γφ = 0.008 (maximum 0.04), scaled with submicron aerosol chloride content, and was suppressed by aerosol organic matter and liquid water content. Not all of the observed variability of ClNO 2 production efficiency could be rationalized using current literature parameterizations.
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Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.001 | 0.001 |
| 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 | 0.001 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| 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 it