Online gas- and particle-phase measurements of organosulfates, organosulfonates and nitrooxy organosulfates in Beijing utilizing a FIGAERO ToF-CIMS

Abstract

Abstract. A time-of-flight chemical ionization mass spectrometer (CIMS) utilizing the Filter Inlet for Gas and Aerosol (FIGAERO) was deployed at a regional site 40 km north-west of Beijing and successfully identified and measured 17 sulfur-containing organics (SCOs are organo/nitrooxy organosulfates and sulfonates) with biogenic and anthropogenic precursors. The SCOs were quantified using laboratory-synthesized standards of lactic acid sulfate and nitrophenol organosulfate (NP OS). The variation in field observations was confirmed by comparison to offline measurement techniques (orbitrap and high-performance liquid chromatography, HPLC) using daily averages. The mean total (of the 17 identified by CIMS) SCO particle mass concentration was 210 ± 110 ng m−3 and had a maximum of 540 ng m−3, although it contributed to only 2 ± 1 % of the organic aerosol (OA). The CIMS identified a persistent gas-phase presence of SCOs in the ambient air, which was further supported by separate vapour-pressure measurements of NP OS by a Knudsen Effusion Mass Spectrometer (KEMS). An increase in relative humidity (RH) promoted partitioning of SCO to the particle phase, whereas higher temperatures favoured higher gas-phase concentrations. Biogenic emissions contributed to only 19 % of total SCOs measured in this study. Here, C10H16NSO7, a monoterpene-derived SCO, represented the highest fraction (10 %) followed by an isoprene-derived SCO. The anthropogenic SCOs with polycyclic aromatic hydrocarbon (PAH) and aromatic precursors dominated the SCO mass loading (51 %) with C11H11SO7, derived from methyl naphthalene oxidation, contributing to 40 ng m−3 and 0.3 % of the OA mass. Anthropogenic-related SCOs correlated well with benzene, although their abundance depended highly on the photochemical age of the air mass, tracked using the ratio between pinonic acid and its oxidation product, acting as a qualitative photochemical clock. In addition to typical anthropogenic and biogenic precursors the biomass-burning precursor nitrophenol (NP) provided a significant level of NP OS. It must be noted that the contribution analysis here is only representative of the detected SCOs. There are likely to be many more SCOs present which the CIMS has not identified. Gas- and particle-phase measurements of glycolic acid suggest that partitioning towards the particle phase promotes glycolic acid sulfate production, contrary to the current formation mechanism suggested in the literature. Furthermore, the HSO4⋅H2SO4- cluster measured by the CIMS was utilized as a qualitative marker for acidity and indicates that the production of total SCOs is efficient in highly acidic aerosols with high SO42- and organic content. This dependency becomes more complex when observing individual SCOs due to variability of specific VOC precursors.

Chlorine oxidation of VOCs at a semi-rural site in Beijing: significant chlorine liberation from ClNO<sub>2</sub> and subsequent gas- and particle-phase Cl–VOC production

“…The laboratory setup on the Changping University campus of Peking University was situated at a semi-rural site 40 km northwest of Beijing close to Changping (40.2207 • N, 116.2312 • E). The general setup has previously been described by Le Breton et al (2018).…”

“…Gas-and particle-phase ambient species were measured using an iodide ToF-CIMS (resolving power of 3500) coupled to the FIGAERO inlet (Lopez-Hilfiker et al, 2014). The setup for this campaign has previously been described by Le Breton et al (2018). Briefly, the iodide ionisation scheme was utilised to acquire non-fragmented ions of interest by passing ultra-high-purity N 2 over a permeation tube containing liquid CH 3 I (Alfa Aesar, 99 %) and through a Tofwerk X-ray ion source type P (operated at 9.5 kV and 150 µA) to produce the iodide reagent ions.…”

“…Although the mean mixing ratios do not increase significantly during the pollution episodes, the maximum mixing ratios detected overnight increase by up to a factor of 4. Further analysis of N 2 O 5 nighttime chemistry was performed by Wang et al (2018), who calculated an average steady-state lifetime of 310 ± 240 s and mean uptake coefficient of 0.034 ± 0.018.…”

Thermodynamic properties of isoprene and monoterpene derived organosulfates estimated with COSMO<i>therm</i>

“…Recent measurements close to Beijing using a Filter Inlet for Gas and Aerosol (FIGAERO) chemical ionization mass spectrometer (CIMS) have shown that sulfur containing organic compounds, such as organo/nitrooxy organosulfates and sulfonates, can also be present in the gas-phase (Le Breton et al, 2018). Higher temperatures promote the presence of sulfur compounds in the gas phase and furthermore the partitioning to the particle phase was found to be dependent on ambient relative humidity.…”

“…In urban areas, such as Xi'an in northwestern China, organosulfates are primarily of anthropogenic origin (Huang et al, 2018), but already in semi rural locations 40 km northwest of Beijing, up to 19% of the sulfur containing organics have been identified to be of biogenic origin (Le Breton et al, 2018).…”