17 Feb 2023
 | 17 Feb 2023
Status: this preprint is currently under review for the journal AMT.

Characterisation of the multi-scheme chemical ionisation inlet-2 and the detection of gaseous iodine species

Xu-Cheng He, Jiali Shen, Siddharth Iyer, Paxton Juuti, Jiangyi Zhang, Mrisha Koirala, Mikko M. Kytökari, Douglas R. Worsnop, Matti Rissanen, Markku Kulmala, Norbert M. Maier, Jyri Mikkilä, Mikko Sipilä, and Juha Kangasluoma

Abstract. The multi-scheme chemical ionisation inlet 1 (MION1) allows fast switching between measuring atmospheric ions without chemical ionisation and neutral molecules by multiple chemical ionisation methods. In this study, the upgraded multi-scheme chemical ionisation inlet 2 (MION2) is presented. The new design features improved ion optics that increase the reagent ion concentration, a generally more robust operation and the possibility to run multiple chemical ionisation methods with the same ionisation time.

To simplify the regular calibration of MION2, we developed an open-source flow reactor chemistry model (MARFORCE) to quantify the chemical production of sulfuric acid (H2SO4), hypoiodous acid (HOI) and hydroperoxyl radical (HO2). MARFORCE simulates convection-diffusion-reaction processes inside typical cylindrical flow reactors with uniform inner diameters. The model also provides options to simulate the chemical processes 1) when two flow reactors with different inner diameters are connected together and 2) when two flows are merged into one (connected by a Y-shape tee), but with reduced accuracy. Additionally, the chemical mechanism files in the model are compatible with the widely-used Master Chemical Mechanism, thus allowing future adaptation to simulate other chemical processes in flow reactors.

We further carried out detailed characterisation of the bromide (Br) and nitrate (NO3) chemical ionisation methods with different ionisation times. We calibrated H2SO4, HOI and HO2 by combining gas kinetic experiments with the MARFORCE model. Sulfur dioxide (SO2), water (H2O) and molecular iodine (I2) were evaluated using dilution experiments from a gas cylinder (SO2), dew point mirror measurements (H2O), and a derivatization approach in combination with high-performance liquid chromatography quantification (I2), respectively. We find that the detection limit is negatively correlated with the fragmentation enthalpy of the analyte-reagent ion (Br) cluster, i.e., a stronger binding (larger fragmentation enthalpy) leads to a lower detection limit. Additionally, a moderately longer reaction time enhances the detection sensitivity thus decreasing the detection limit. For example, the detection limit for H2SO4 is estimated to be 2.9 × 104 molec. cm−3 with a 300 ms ionisation time. A direct comparison suggests that this is even better than the widely-used Eisele-type chemical ionisation inlet.

While the NO3 chemical ionisation method is generally more robust, we find that the Br chemical ionisation method (Br-MION2) is significantly affected by air water content. Higher air water content results in lower sensitivity for HO2 and SO2 within the examined conditions. On the other hand, a steep sensitivity drop of H2SO4, HOI and I2 is only observed when the dew point is greater than 0.5–10.5 ℃ (equivalent to 20–40 % RH; calculated at 25 ℃ hereafter). Future studies utilising atmospheric pressure Br chemical ionisation method, including Br-MION2, should carefully address the humidity effect on a molecular basis. By combining methods such as water-insensitive NO3-MION2 with Br-MION2, MION2 should be able to provide greater details of air composition than either of these methods alone.

Combining instrument voltage-scanning, chemical kinetic experiments and quantum chemical calculations, we find that the HIO3 detection is not interfered with by iodine oxides under atmospherically relevant conditions. The IO3, HIO3NO3 and HIO3Br ions measured using the Br and NO3 chemical ionisation methods are primarily, if not exclusively, produced from gaseous HIO3 molecules.

Xu-Cheng He et al.

Status: open (until 28 Mar 2023)

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  • RC1: 'Comment on amt-2023-30', Anonymous Referee #1, 24 Mar 2023 reply

Xu-Cheng He et al.

Xu-Cheng He et al.


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Short summary
In this study, the upgraded multi-scheme chemical ionisation inlet 2 is presented. Sulfuric acid, hypoiodous acid, iodine, sulfur dioxide and hydroperoxyl radical were calibrated and the improved ion optics enable to detect sulfuric acid and iodine-containing molecules at as low as a few parts per quadrillion by volume. Additionally, we confirm in this study that iodic acid is reliably detected by both the nitrate and bromide chemical ionisation methods at atmospherically relevant conditions.