Contribution of Hydroxymethane Sulfonate to Ambient Particulate Matter: A Potential Explanation for High Particulate Sulfur During Severe Winter Haze in Beijing

Moch, Jonathan M.; Dovrou, Eleni; Mickley, Loretta J.; Keutsch, Frank N.; Cheng, Yuan; Jacob, Daniel; Jiang, Jingkun; Li, Meng; Munger, J. William; Qiao, Xiaohui; Zhang, Qiang

doi:10.1029/2018gl079309

Cited by 98 publications

(130 citation statements)

References 87 publications

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“…Similarly, AMS measurements may have identified HMS as sulfate as explained above. This is also consistent with the explanation provided by Moch at al. (2018) and Song at al.…”

Section: Resultssupporting

confidence: 94%

Measurement techniques of identifying and quantifying sulfur compounds in fog and cloud water

Dovrou

Lim

Canagaratna

et al. 2019

Preprint

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Abstract. Oxidation of sulfur dioxide (SO2) in the gas phase and in cloud and fog water leads to the formation of sulfate that contributes to ambient particulate matter (PM). For severe haze events with dim conditions, current models underestimate the levels of sulfate formation which occurs exclusively via the oxidation of sulfur dioxide. We show here that measurement techniques commonly used in the field to analyse PM composition can fail to efficiently separate sulfur-containing species resulting in possible misidentification of compounds. Hydroxymethanesulfonate (HMS), a sulfur(IV) species that can be present in fog and cloud water, has been largely neglected in both chemical models and field measurements of PM composition. As HMS is formed without oxidation it represents a pathway for SO2 to contribute to PM under dim conditions. In this work, we evaluate two techniques for specific quantification of HMS and sulfate in PM, Ion Chromatography (IC) and Aerosol Mass Spectrometry (AMS). In cases where the dominant sulfur-containing species are ammonium sulfate or HMS, differences in AMS fragmentation patterns can be used to identify HMS. However, the AMS quantification of HMS in complex ambient mixtures containing multiple inorganic and organic sulfur species is challenging due to the lack of unique organic fragments and variability of fractional contributions of HxSOy+ ions as a function of matrix. We describe an improved IC method that provides efficient separation of sulfate and HMS and thus allows identification and quantification of both. The results of this work provide a technical description of the efficiency and limitations of these techniques as well as a method that enables further studies of the contribution and role of S(IV) versus S(VI) species to PM under dim atmospheric conditions.

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“…Similarly, AMS measurements may have identified HMS as sulfate as explained above. This is also consistent with the explanation provided by Moch at al. (2018) and Song at al.…”

Section: Resultssupporting

confidence: 94%

Measurement techniques of identifying and quantifying sulfur compounds in fog and cloud water

Dovrou

Lim

Canagaratna

et al. 2019

Preprint

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“…Increasing numbers of observations have revealed that anthropogenic emission-relevant aerosol species, such as sulfate, nitrate and ammonium (denoted as SNA), are the predominant inorganic species in the wintertime PM 2.5 in China (Y. S. Yang et al, 2015). Various reaction paths during haze events have also been proposed (e.g., Zheng et al, 2015;Cheng et al, 2016;Wang et al, 2016;Moch et al, 2018;Wang et al, 2018;Shao et al, 2019). For example, Moch et al (2018) used a 1-D model and revealed the importance of aqueousphase chemistry of HCHO and S(IV) in cloud droplets by forming a S(IV)-HCHO adduct, hydroxymethane sulfonate.…”

mentioning

confidence: 99%

“…Various reaction paths during haze events have also been proposed (e.g., Zheng et al, 2015;Cheng et al, 2016;Wang et al, 2016;Moch et al, 2018;Wang et al, 2018;Shao et al, 2019). For example, Moch et al (2018) used a 1-D model and revealed the importance of aqueousphase chemistry of HCHO and S(IV) in cloud droplets by forming a S(IV)-HCHO adduct, hydroxymethane sulfonate. Shao et al (2019) implemented four heterogeneous sulfate formation mechanisms (via H 2 O 2 , O 3 , NO 2 and transition metal ions on aerosols) into GEOS-Chem model, which partially reduced the modeled low bias in sulfate concentrations.…”

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confidence: 99%

Retrospective analysis of 2015–2017 wintertime PM<sub>2.5</sub> in China: response to emission regulations and the role of meteorology

et al. 2019

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Abstract. To better characterize anthropogenic emission-relevant aerosol species, the Gridpoint Statistical Interpolation (GSI) and Weather Research and Forecasting with Chemistry (WRF/Chem) data assimilation system was updated from the GOCART aerosol scheme to the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) 4-bin (MOSAIC-4BIN) aerosol scheme. Three years (2015–2017) of wintertime (January) surface PM2.5 (fine particulate matter with an aerodynamic diameter smaller than 2.5 µm) observations from more than 1600 sites were assimilated hourly using the updated three-dimensional variational (3DVAR) system. In the control experiment (without assimilation) using Multi-resolution Emission Inventory for China 2010 (MEIC_2010) emissions, the modeled January averaged PM2.5 concentrations were severely overestimated in the Sichuan Basin, central China, the Yangtze River Delta and the Pearl River Delta by 98–134, 46–101, 32–59 and 19–60 µg m−3, respectively, indicating that the emissions for 2010 are not appropriate for 2015–2017, as strict emission control strategies were implemented in recent years. Meanwhile, underestimations of 11–12, 53–96 and 22–40 µg m−3 were observed in northeastern China, Xinjiang and the Energy Golden Triangle, respectively. The assimilation experiment significantly reduced both high and low biases to within ±5 µg m−3. The observations and the reanalysis data from the assimilation experiment were used to investigate the year-to-year changes and the driving factors. The role of emissions was obtained by subtracting the meteorological impacts (by control experiments) from the total combined differences (by assimilation experiments). The results show a reduction in PM2.5 of approximately 15 µg m−3 for the month of January from 2015 to 2016 in the North China Plain (NCP), but meteorology played the dominant role (contributing a reduction of approximately 12 µg m−3). The change (for January) from 2016 to 2017 in NCP was different; meteorology caused an increase in PM2.5 of approximately 23 µg m−3, while emission control measures caused a decrease of 8 µg m−3, and the combined effects still showed a PM2.5 increase for that region. The analysis confirmed that emission control strategies were indeed implemented and emissions were reduced in both years. Using a data assimilation approach, this study helps identify the reasons why emission control strategies may or may not have an immediately visible impact. There are still large uncertainties in this approach, especially the inaccurate emission inputs, and neglecting aerosol–meteorology feedbacks in the model can generate large uncertainties in the analysis as well.

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“…The oxygen‐containing fragment ions, such as C 2 H 3 O + , C 14 H 7 O 2 + , C 3 H 7 O + , and C 11 H 14 O 5 + , and some oxygen‐containing unsaturated hydrocarbon ions even over m/z 200, such as C 16 H 14 O + , C 17 H 13 O 3 + , and C 22 H 18 O 4 + , may represent alcohols and carbonyl compounds in the atmosphere, which are mainly from automobile exhaust and atmospheric photochemical reactions . The nitrogen‐containing fragment ions and their oxidation derivatives in the atmosphere, such as C 2 H 7 N 3 + , C 2 H 2 N + , C 4 H 12 NO + , C 3 H 8 NO + , and C 5 H 12 N 2 O 3 + , which may be the heterocyclic compounds and the sulfur‐containing fragment ions and their oxidation derivatives, such as C 2 H 4 S 3 + , C 8 H 3 S + , and C 7 H 15 SO + , which may be the thiols and sulfonates are produced mainly by the burning of fossil fuels, biomass, and garbage, as well as vehicle emissions and, even, cooking, with secondary formation produced by landfill fermentation, organic solvent volatility, hydrocarbon oxidation, etc. In Table , unsaturated hydrocarbons ions, including C 16 H 10 + , C 20 H 12 + , and C 22 H 12 + , may be polycyclic aromatic hydrocarbons (PAHs) .…”

Section: Resultsmentioning

confidence: 99%

ToF‐SIMS analysis of chemical composition of atmospheric aerosols in Beijing

Jia

Che

et al. 2019

Surface & Interface Analysis

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Atmospheric aerosols collected from each season in urban Beijing have been studied using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). The chemical composition of atmospheric aerosol particles during various atmospheric pollution levels was analyzed and distinguished by principal component analysis (PCA). The differences and sources of the components of the aerosol particles were explored. The results showed that the fine particulate matter from heavily polluted days mainly consists of inorganic salts and organic compounds, such as hydrocarbons, nitrogen‐ or sulfur‐containing hydrocarbons, and their oxides. Samples collected from clean days in the four seasons were also analyzed. Only the samples collected in spring showed a significant difference from the other three seasons. We concluded that the main source of pollution in the Beijing urban area was fossil fuel combustion from motor vehicles.

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Contribution of Hydroxymethane Sulfonate to Ambient Particulate Matter: A Potential Explanation for High Particulate Sulfur During Severe Winter Haze in Beijing

Cited by 98 publications

References 87 publications

Measurement techniques of identifying and quantifying sulfur compounds in fog and cloud water

Measurement techniques of identifying and quantifying sulfur compounds in fog and cloud water

Retrospective analysis of 2015–2017 wintertime PM<sub>2.5</sub> in China: response to emission regulations and the role of meteorology

ToF‐SIMS analysis of chemical composition of atmospheric aerosols in Beijing

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Contribution of Hydroxymethane Sulfonate to Ambient Particulate Matter: A Potential Explanation for High Particulate Sulfur During Severe Winter Haze in Beijing

Cited by 98 publications

References 87 publications

Measurement techniques of identifying and quantifying sulfur compounds in fog and cloud water

Measurement techniques of identifying and quantifying sulfur compounds in fog and cloud water

Retrospective analysis of 2015–2017 wintertime PM&lt;sub&gt;2.5&lt;/sub&gt; in China: response to emission regulations and the role of meteorology

ToF‐SIMS analysis of chemical composition of atmospheric aerosols in Beijing

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Retrospective analysis of 2015–2017 wintertime PM<sub>2.5</sub> in China: response to emission regulations and the role of meteorology