Articles | Volume 19, issue 8
https://doi.org/10.5194/amt-19-2715-2026
© Author(s) 2026. This work is distributed under the Creative Commons Attribution 4.0 License.
A novel technique for the humidity dependent calibration of hypoiodous acid (HOI) and iodine (I2)
Download
- Final revised paper (published on 22 Apr 2026)
- Preprint (discussion started on 05 Dec 2025)
Interactive discussion
Status: closed
Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor
| : Report abuse
-
RC1: 'Comment on egusphere-2025-5812', Anonymous Referee #1, 27 Dec 2025
- AC1: 'Reply on RC1', Lewis Marden, 10 Mar 2026
-
RC2: 'Comment on egusphere-2025-5812', Anonymous Referee #2, 01 Jan 2026
- AC1: 'Reply on RC1', Lewis Marden, 10 Mar 2026
Peer review completion
AR – Author's response | RR – Referee report | ED – Editor decision | EF – Editorial file upload
AR by Lewis Marden on behalf of the Authors (27 Mar 2026)
Author's response
Author's tracked changes
Manuscript
ED: Publish as is (30 Mar 2026) by Mingjin Tang
AR by Lewis Marden on behalf of the Authors (05 Apr 2026)
This manuscript presents a novel and well-designed calibration approach for quantifying hypoiodous acid (HOI) based on its conversion to molecular iodine (I2) using a sodium iodide trap, coupled with bromide chemical ionization mass spectrometry (Br-CIMS). The authors systematically investigate the humidity dependence of the instrument’s sensitivity to both HOI and I2, demonstrating that I2 sensitivity becomes essentially independent of humidity above ~50% RH, while HOI exhibits a slight negative dependence. The study also highlights significant inlet-mediated losses and interconversion between HOI and I2, especially in bent or salted inlet configurations mimicking field setups. The manuscript is well written and easy to read. I would recommend it to be published in this journal after the following comments being addressed and revised.
1. The 1:1 conversion of HOI to I2 via the NaI trap is assumed based on analogy with the HOBr–Br2 system. However, small signals of HI and IBr were observed upon trap insertion. Could side reactions or impurities in the NaI trap lead to non‑stoichiometric conversion? Is there additional experimental evidence (e.g., isotopic labeling, independent HOI quantification) to confirm the 1:1 conversion efficiency under varying humidity and concentration conditions?
2. The “water ratio” (H2OBr⁻/Br⁻) is used as a proxy for IMR humidity. While convenient, has this ratio been validated against direct humidity measurements (e.g., using a hygrometer) across the full range of conditions? Could temperature fluctuations in the IMR affect the relationship between the water ratio and actual H2O mixing ratio?
For I2, sensitivity becomes humidity‑independent above a water ratio of ~0.7. The explanation involves a balance between the stabilizing effect of H2O on the adduct and the lower formation enthalpy with H2OBr⁻. Is there quantitative kinetic or quantum‑chemical modeling to support this interpretation? Could the second water cluster Br(H2O)2⁻ play a non‑negligible role at very high humidity?
For HOI, sensitivity decreases with humidity, explained by QRRK theory. Are there computational or experimental data on the binding energies, vibrational frequencies, or number of effective oscillators for HOI·Br⁻ vs. I2·Br⁻ adducts to substantiate this argument?
3. Inlet loss experiments using a T‑piece and a salted PTFE guard show substantial HOI loss (65–75%) with concomitant I2 increase, attributed to reverse hydrolysis. How representative are these laboratory tests of real‑world marine boundary layer conditions, where aerosol composition, surface acidity, and humidity vary continuously? Have you considered performing similar tests with authentic sea‑salt aerosol or under varying RH/T conditions?
The HOI data are presented as an “upper limit” because background subtraction was not performed due to the lack of dry calibration. Could the use of isotope ratio filtering (as done for zeroing checks) or nighttime background estimation provide a way to constrain the background more rigorously? How might this affect the reported diurnal profile and peak mixing ratios?
4. The overall uncertainties for I2 and HOI are given as ~30%, but described as “lower limits” due to unquantified inlet effects. Could repeated loss experiments with different inlet configurations or flow rates help better constrain these uncertainties?
I2 mixing ratios show no clear diurnal cycle, contrary to expectations from photolysis. The authors suggest inlet or background effects, but could there be a daytime source of I2 (e.g., photochemical production or wind‑driven emission) compensating for photolytic loss? Is there corroborative data (e.g., from DOAS, other CIMS, or model simulations during BLEACH) to contextualize this observation?
5. The calibration and inlet loss corrections were developed for marine boundary layer conditions (high RH, sea‑salt influence). How transferable is this method to other environments (e.g., polluted coasts, polar regions, forests) where humidity, aerosol composition, and oxidant levels differ significantly?
For long‑term field deployments, how stable is the Br⁻ reagent ion source and the instrument sensitivity over weeks to months? What quality‑control measures (e.g., regular permeation tube checks, humidity‑adjustment protocols) are recommended for ongoing ambient monitoring of HOI and I2?