Articles | Volume 22, issue 6
01 Apr 2022
Research article | 01 Apr 2022
Formation of organic sulfur compounds through SO2-initiated photochemistry of PAHs and dimethylsulfoxide at the air-water interface
Haoyu Jiang et al.
No articles found.
Xuan Li, Lei Li, Zeming Zhuo, Guohua Zhang, Xubing Du, Xue Li, Zhengxu Huang, Zhen Zhou, and Zhi Cheng
The particle size and chemical composition of bioaerosol were analyzed based on single particle aerosol mass spectrometer. Fungal aerosol of 10 μm was measured for the first time and the characteristic spectrum of bioaerosol was updated. The ion peak ratio method can distinguish bioaerosols from interferers by 97 %. The factors influencing the differentiation of bioaerosols are also discussed. Single particle mass spectrometry can be a new method for real-time identification of bioaerosols.
Chunlin Zou, Tao Cao, Meiju Li, Jianzhong Song, Bin Jiang, Wanglu Jia, Jun Li, Xiang Ding, Zhiqiang Yu, Gan Zhang, and Ping’an Peng
Atmos. Chem. Phys. Discuss.,
Preprint under review for ACPShort summary
In this study, PM2.5 samples were obtained during a winter haze event in Guangzhou, China, and light absorption and molecular composition of HULIS were investigated by UV-vis spectrophotometry and ultrahigh-resolution mass spectrometry. The findings obtained present some differences from the results reported in other regions of China and significantly enhanced our understanding of HULIS evolution during haze bloom-decay process in the subtropic region of South China.
Hongxing Jiang, Jun Li, Jiao Tang, Min Cui, Shizhen Zhao, Yangzhi Mo, Chongguo Tian, Xiangyun Zhang, Bin Jiang, Yuhong Liao, Yingjun Chen, and Gan Zhang
Atmos. Chem. Phys., 22, 6919–6935,Short summary
We conducted field observation employing Fourier transform ion cyclotron resonance mass spectrometry to characterize the molecular composition and major formation pathways or sources of organosulfur compounds in Guangzhou, where is heavily influenced by biogenic–anthropogenic interactions and has high relative humidity and temperature. We suggested that heterogeneous reactions such as SO2 uptake and heterogeneous oxidations are important to the molecular variations of organosulfur compounds.
Beatrix Rosette Go Mabato, Yan Lyu, Yan Ji, Yong Jie Li, Dan Dan Huang, Xue Li, Theodora Nah, Chun Ho Lam, and Chak K. Chan
Atmos. Chem. Phys., 22, 273–293,Short summary
Biomass burning (BB) is a global phenomenon that releases large quantities of pollutants such as phenols and aromatic carbonyls into the atmosphere. These compounds can form secondary organic aerosols (SOAs) which play an important role in the Earth’s energy budget. In this work, we demonstrated that the direct irradiation of vanillin (VL) could generate aqueous SOA (aqSOA) such as oligomers. In the presence of nitrate, VL photo-oxidation can also form nitrated compounds.
Wei Sun, Yuzhen Fu, Guohua Zhang, Yuxiang Yang, Feng Jiang, Xiufeng Lian, Bin Jiang, Yuhong Liao, Xinhui Bi, Duohong Chen, Jianmin Chen, Xinming Wang, Jie Ou, Ping'an Peng, and Guoying Sheng
Atmos. Chem. Phys., 21, 16631–16644,Short summary
We sampled cloud water at a remote mountain site and investigated the molecular characteristics. CHON and CHO are dominant in cloud water. No statistical difference in the oxidation state is observed between cloud water and interstitial PM2.5. Most of the formulas are aliphatic and olefinic species. CHON, with aromatic structures and organosulfates, are abundant, especially in nighttime samples. The in-cloud and multi-phase dark reactions likely contribute significantly.
Johannes Passig, Julian Schade, Robert Irsig, Lei Li, Xue Li, Zhen Zhou, Thomas Adam, and Ralf Zimmermann
Atmos. Meas. Tech., 14, 4171–4185,Short summary
Ships are major sources of air pollution; however, monitoring of ship emissions outside harbours is a challenging task. We optimized single-particle mass spectrometry (SPMS) for the detection of bunker fuel emissions and demonstrate the detection of individual ship plumes from more than 10 km in distance. The approach works independently of background air pollution and also when ships use exhaust-cleaning scrubbers. We discuss the potential and limits of SPMS-based monitoring of ship plumes.
Yibei Wan, Xiangpeng Huang, Bin Jiang, Binyu Kuang, Manfei Lin, Deming Xia, Yuhong Liao, Jingwen Chen, Jian Zhen Yu, and Huan Yu
Atmos. Chem. Phys., 20, 9821–9835,Short summary
Biogenic iodine emission from macroalgae and microalgae could initiate atmospheric new particle formation (NPF). But it is unknown if other species are needed to drive the growth of new iodine particles in the marine boundary layer. Unlike the deeper understanding of organic compounds driving continental NPF, little is known about the organics involved in coastal or open-ocean NPF. This article reveals a new group of important organic compounds involved in this process.
Johannes Passig, Julian Schade, Ellen Iva Rosewig, Robert Irsig, Thomas Kröger-Badge, Hendryk Czech, Martin Sklorz, Thorsten Streibel, Lei Li, Xue Li, Zhen Zhou, Henrik Fallgren, Jana Moldanova, and Ralf Zimmermann
Atmos. Chem. Phys., 20, 7139–7152,Short summary
Particle-bound metals in both natural dusts and polluted air can induce severe health effects. They are also transported by the wind into the oceans; provide micronutrients; and thus modulate biodiversity, fisheries, and climate. We show a way to more efficiently detect metals in individual particles while preserving source information. Our detection scheme is less dependent on the particle type and atmospheric changes and is thus valuable to the study of biogechemical cycles and air pollution.
Jing Cai, Xiangying Zeng, Guorui Zhi, Sasho Gligorovski, Guoying Sheng, Zhiqiang Yu, Xinming Wang, and Ping'an Peng
Atmos. Chem. Phys., 20, 6115–6128,Short summary
The composition and light-induced evolution of a water-soluble organic carbon mixture from fresh biomass burning aerosols was investigated with direct infusion electrospray ionisation high-resolution mass spectrometry (HRMS) and liquid chromatography coupled with HRMS. Our findings indicate that the water-soluble organic fraction of combustion-derived aerosols has the potential to form more oxidised organic matter, contributing to the highly oxygenated nature of atmospheric organic aerosols.
Jiao Tang, Jun Li, Tao Su, Yong Han, Yangzhi Mo, Hongxing Jiang, Min Cui, Bin Jiang, Yingjun Chen, Jianhui Tang, Jianzhong Song, Ping'an Peng, and Gan Zhang
Atmos. Chem. Phys., 20, 2513–2532,Short summary
We investigated the light absorption, fluorescence, and molecular composition of dissolved organic carbon from the simulated combustion of biomass and coal and vehicle emissions with UV–vis spectra, EEM-PARAFAC, and FT-ICR MS. We observed high light absorption capacity from source emissions, and fluorescence spectra and molecular structures varied by source. We concluded that an EEM- and molecular-composition-based methodology could be helpful in the source apportionment of atmospheric aerosols.
Min Cui, Cheng Li, Yingjun Chen, Fan Zhang, Jun Li, Bin Jiang, Yangzhi Mo, Jia Li, Caiqing Yan, Mei Zheng, Zhiyong Xie, Gan Zhang, and Junyu Zheng
Atmos. Chem. Phys., 19, 13945–13956,Short summary
Refined source apportionment is urgently needed but hard to achieve due to a lack of specific biomarkers. Recently, Fourier transform ion cyclotron resonance mass spectrometry has been used to analyse the probable chemical structure of polar organic matter emitted from off-road engines. We found more condensed aromatic rings in S-containing compounds for HFO-fueled vessels, while more abundant aliphatic chains were observed in emissions from diesel equipment.
Yanqing An, Jianzhong Xu, Lin Feng, Xinghua Zhang, Yanmei Liu, Shichang Kang, Bin Jiang, and Yuhong Liao
Atmos. Chem. Phys., 19, 1115–1128,Short summary
Detailed molecular chemical composition of water-soluble organic matter in the Himalayas was characterized by positive electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry for the first time. Many products formed from biogenic volatile organic compounds and biomass-burning-emitted compounds were found in the organic compounds, suggesting the important contribution of these two sources in the Himalayas.
Lin Feng, Yanqing An, Jianzhong Xu, Shichang Kang, Xiaofei Li, Yongqiang Zhou, Yunlin Zhang, Bin Jiang, and Yuhong Liao
Revised manuscript not accepted
Mingjin Tang, Xin Huang, Keding Lu, Maofa Ge, Yongjie Li, Peng Cheng, Tong Zhu, Aijun Ding, Yuanhang Zhang, Sasho Gligorovski, Wei Song, Xiang Ding, Xinhui Bi, and Xinming Wang
Atmos. Chem. Phys., 17, 11727–11777,Short summary
We provide a comprehensive and critical review of laboratory studies of heterogeneous uptake of OH, NO3, O3, and their directly related species by mineral dust particles. The atmospheric importance of heterogeneous uptake as sinks for these species is also assessed. In addition, we have outlined major open questions and challenges in this field and discussed research strategies to address them.
Chunlei Cheng, Mei Li, Chak K. Chan, Haijie Tong, Changhong Chen, Duohong Chen, Dui Wu, Lei Li, Cheng Wu, Peng Cheng, Wei Gao, Zhengxu Huang, Xue Li, Zhijuan Zhang, Zhong Fu, Yanru Bi, and Zhen Zhou
Atmos. Chem. Phys., 17, 9519–9533,Short summary
Oxalic acid is an abundant and ubiquitous constituent in secondary organic aerosol (SOA) and can be an effective tracer for the oxidative processes leading to the formation of SOA. In this work photochemical reactions have a significant contribution to oxalic acid formation in summer, while in winter the formation of oxalic acid is closely associated with the oxidation of organic precursors in the aqueous phase.
Rachel Gemayel, Stig Hellebust, Brice Temime-Roussel, Nathalie Hayeck, Johannes T. Van Elteren, Henri Wortham, and Sasho Gligorovski
Atmos. Meas. Tech., 9, 1947–1959,Short summary
LAAP-ToF-MS has been optimized for particle size and number concentration evolution and characterization of the chemical composition of ambient particles by following specific ions. The advantage of this instrument is that it can analyze the ambient particles online and continuously. It is capable of analyzing inorganic material in ambient particles; in particular the presence of metals can be analyzed. Last but not least, it is a compact and easily transportable tool for field measurements.
Khan M. G. Mostofa, Cong-Qiang Liu, WeiDong Zhai, Marco Minella, Davide Vione, Kunshan Gao, Daisuke Minakata, Takemitsu Arakaki, Takahito Yoshioka, Kazuhide Hayakawa, Eiichi Konohira, Eiichiro Tanoue, Anirban Akhand, Abhra Chanda, Baoli Wang, and Hiroshi Sakugawa
Biogeosciences, 13, 1767–1786,
Related subject area
Subject: Gases | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)Impact of cooking style and oil on semi-volatile and intermediate volatility organic compound emissions from Chinese domestic cookingObservations of gas-phase products from the nitrate-radical-initiated oxidation of four monoterpenesInvestigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber)Kinetic study of the atmospheric oxidation of a series of epoxy compounds by OH radicalsAn experimental study of the reactivity of terpinolene and β-caryophyllene with the nitrate radicalOxidation product characterization from ozonolysis of the diterpene ent-kaureneKinetics of OH + SO2 + M: temperature-dependent rate coefficients in the fall-off regime and the influence of water vapourStable carbon isotopic composition of biomass burning emissions – implications for estimating the contribution of C3 and C4 plantsEvaluation of the daytime tropospheric loss of 2-methylbutanalInvestigations into the gas-phase photolysis and OH radical kinetics of nitrocatechols: implications of intramolecular interactions on their atmospheric behaviourReproducing Arctic springtime tropospheric ozone and mercury depletion events in an outdoor mesocosm sea ice facilityN2O5 uptake onto saline mineral dust: a potential missing source of tropospheric ClNO2 in inland ChinaNO3 chemistry of wildfire emissions: a kinetic study of the gas-phase reactions of furans with the NO3 radicalMarine gas-phase sulfur emissions during an induced phytoplankton bloomBiomass burning plume chemistry: OH-radical-initiated oxidation of 3-penten-2-one and its main oxidation product 2-hydroxypropanalAtmospheric photo-oxidation of myrcene: OH reaction rate constant, gas-phase oxidation products and radical budgetsCharacterization of ambient volatile organic compounds, source apportionment, and the ozone–NOx–VOC sensitivities in a heavily polluted megacity of central China: effect of sporting events and emission reductionsAtmospheric oxidation of α,β-unsaturated ketones: kinetics and mechanism of the OH radical reactionReactions of NO3 with aromatic aldehydes: gas-phase kinetics and insights into the mechanism of the reactionAtmospheric photooxidation and ozonolysis of Δ3-carene and 3-caronaldehyde: rate constants and product yieldsMeasurement report: Biogenic volatile organic compound emission profiles of rapeseed leaf litter and its secondary organic aerosol formation potentialHighly oxygenated organic molecules produced by the oxidation of benzene and toluene in a wide range of OH exposure and NOx conditionsMolecular composition and volatility of multi-generation products formed from isoprene oxidation by nitrate radicalHighly oxygenated organic molecule (HOM) formation in the isoprene oxidation by NO3 radicalVolatile organic compound emissions from solvent- and water-borne coatings – compositional differences and tracer compound identificationsEvaluated kinetic and photochemical data for atmospheric chemistry: volume VIII – gas-phase reactions of organic species with four, or more, carbon atoms ( ≥ C4)Chemical characterisation of benzene oxidation products under high- and low-NOx conditions using chemical ionisation mass spectrometryEmissions of non-methane volatile organic compounds from combustion of domestic fuels in Delhi, IndiaA comparative and experimental study of the reactivity with nitrate radical of two terpenes: α-terpinene and γ-terpinenePhotooxidation of pinonaldehyde at ambient conditions investigated in the atmospheric simulation chamber SAPHIRReaction between CH3C(O)OOH (peracetic acid) and OH in the gas phase: a combined experimental and theoretical study of the kinetics and mechanismSnow heterogeneous reactivity of bromide with ozone lost during snow metamorphismEvaluated kinetic and photochemical data for atmospheric chemistry: Volume VII – Criegee intermediatesTechnical Note: Effect of varying the λ = 185 and 254 nm photon flux ratio on radical generation in oxidation flow reactorsKinetics of dimethyl sulfide (DMS) reactions with isoprene-derived Criegee intermediates studied with direct UV absorptionDetermination of the absorption cross sections of higher-order iodine oxides at 355 and 532 nmEvolution of NO3 reactivity during the oxidation of isopreneRate coefficients for reactions of OH with aromatic and aliphatic volatile organic compounds determined by the multivariate relative rate techniqueAtmospheric fate of two relevant unsaturated ketoethers: kinetics, products and mechanisms for the reaction of hydroxyl radicals with (E)-4-methoxy-3-buten-2-one and (1E)-1-methoxy-2-methyl-1-penten-3-oneThe nitrogen budget of laboratory-simulated western US wildfires during the FIREX 2016 Fire Lab studyImportance of isomerization reactions for OH radical regeneration from the photo-oxidation of isoprene investigated in the atmospheric simulation chamber SAPHIRKinetics of the OH + NO2 reaction: effect of water vapour and new parameterization for global modellingKinetic and mechanistic study of the reaction between methane sulfonamide (CH3S(O)2NH2) and OHDimensionality-reduction techniques for complex mass spectrometric datasets: application to laboratory atmospheric organic oxidation experimentsAtmospheric fate of a series of saturated alcohols: kinetic and mechanistic studyMulti-generation OH oxidation as a source for highly oxygenated organic molecules from aromaticsPhotolysis and oxidation by OH radicals of two carbonyl nitrates: 4-nitrooxy-2-butanone and 5-nitrooxy-2-pentanonePotential dual effect of anthropogenic emissions on the formation of biogenic secondary organic aerosol (BSOA)Effect of NOx on 1,3,5-trimethylbenzene (TMB) oxidation product distribution and particle formationMechanistic study of the formation of ring-retaining and ring-opening products from the oxidation of aromatic compounds under urban atmospheric conditions
Kai Song, Song Guo, Yuanzheng Gong, Daqi Lv, Yuan Zhang, Zichao Wan, Tianyu Li, Wenfei Zhu, Hui Wang, Ying Yu, Rui Tan, Ruizhe Shen, Sihua Lu, Shuangde Li, Yunfa Chen, and Min Hu
Atmos. Chem. Phys., 22, 9827–9841,Short summary
Emissions from four typical Chinese domestic cooking and fried chicken using four kinds of oils were investigated to illustrate the impact of cooking style and oil. Of the estimated SOA, 10.2 %–32.0 % could be explained by S/IVOC oxidation. Multiway principal component analysis (MPCA) emphasizes the importance of the unsaturated fatty acid-alkadienal volatile product mechanism (oil autoxidation) accelerated by the cooking and heating procedure.
Michelia Dam, Danielle C. Draper, Andrey Marsavin, Juliane L. Fry, and James N. Smith
Atmos. Chem. Phys., 22, 9017–9031,Short summary
We performed chamber experiments to measure the composition of the gas-phase reaction products of nitrate-radical-initiated oxidation of four monoterpenes. The total organic yield, effective oxygen-to-carbon ratio, and dimer-to-monomer ratio were correlated with the observed particle formation for the monoterpene systems with some exceptions. The Δ-carene system produced the most particles, followed by β-pinene, with the α-pinene and α-thujene systems producing no particles.
Jacky Yat Sing Pang, Anna Novelli, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Philip T. M. Carlsson, Changmin Cho, Hans-Peter Dorn, Andreas Hofzumahaus, Xin Li, Anna Lutz, Sascha Nehr, David Reimer, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 22, 8497–8527,Short summary
This study investigates the radical chemical budget during the limonene oxidation at different atmospheric-relevant NO concentrations in chamber experiments under atmospheric conditions. It is found that the model–measurement discrepancies of HO2 and RO2 are very large at low NO concentrations that are typical for forested environments. Possible additional processes impacting HO2 and RO2 concentrations are discussed.
Carmen Maria Tovar, Ian Barnes, Iustinian Gabriel Bejan, and Peter Wiesen
Atmos. Chem. Phys., 22, 6989–7004,Short summary
This work explores the kinetics and reactivity of epoxides towards the OH radical using two different simulation chambers. Estimation of the rate coefficients has also been made using different structure–activity relationship (SAR) approaches. The results indicate a direct influence of the structural and geometric properties of the epoxides not considered in SAR estimations, influencing the reactivity of these compounds. The outcomes of this work are in very good agreement with previous studies.
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault
Atmos. Chem. Phys., 22, 6411–6434,Short summary
Biogenic volatile organic compounds are intensely emitted by forests and crops and react with the nitrate radical during the nighttime to form functionalized products. The purpose of this study is to furnish kinetic and mechanistic data for terpinolene and β-caryophyllene, using simulation chamber experiments. Rate constants have been measured using both relative and absolute methods, and mechanistic studies have been conducted in order to identify and quantify the main reaction products.
Yuanyuan Luo, Olga Garmash, Haiyan Li, Frans Graeffe, Arnaud P. Praplan, Anssi Liikanen, Yanjun Zhang, Melissa Meder, Otso Peräkylä, Josep Peñuelas, Ana María Yáñez-Serrano, and Mikael Ehn
Atmos. Chem. Phys., 22, 5619–5637,Short summary
Diterpenes were only recently observed in the atmosphere, and little is known of their atmospheric fates. We explored the ozonolysis of the diterpene kaurene in a chamber, and we characterized the oxidation products for the first time using chemical ionization mass spectrometry. Our findings highlight similarities and differences between diterpenes and smaller terpenes during their atmospheric oxidation.
Wenyu Sun, Matias Berasategui, Andrea Pozzer, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 22, 4969–4984,Short summary
The reaction between OH and SO2 is a termolecular process that in the atmosphere results in the formation of H2SO4 and thus aerosols. We present the first temperature- and pressure-dependent measurements of the rate coefficients in N2. This is also the first study to examine the effects of water vapour on the kinetics of this reaction. Our results indicate the rate coefficient is larger than that recommended by evaluation panels, with deviations of up to 30 % in some parts of the atmosphere.
Roland Vernooij, Ulrike Dusek, Maria Elena Popa, Peng Yao, Anupam Shaikat, Chenxi Qiu, Patrik Winiger, Carina van der Veen, Thomas Callum Eames, Natasha Ribeiro, and Guido R. van der Werf
Atmos. Chem. Phys., 22, 2871–2890,Short summary
Landscape fires are a major source of greenhouse gases and aerosols, particularly in sub-tropical savannas. Stable carbon isotopes in emissions can be used to trace the contribution of C3 plants (e.g. trees or shrubs) and C4 plants (e.g. savanna grasses) to greenhouse gases and aerosols if the process is well understood. This helps us to link individual vegetation types to emissions, identify biomass burning emissions in the atmosphere, and improve the reconstruction of historic fire regimes.
María Asensio, María Antiñolo, Sergio Blázquez, José Albaladejo, and Elena Jiménez
Atmos. Chem. Phys., 22, 2689–2701,Short summary
The diurnal atmospheric degradation of 2-methylbutanal, 2 MB, emitted by sources like vegetation or the poultry industry is evaluated in this work. Sunlight and oxidants like hydroxyl (OH) radicals and chlorine (Cl) atoms initiate this degradation. Measurements of how fast 2 MB is degraded and what products are generated are presented. The lifetime of 2 MB is around 1 h at noon, when the OH reaction dominates. Thus, 2 MB will not be transported far, affecting only local air quality.
Claudiu Roman, Cecilia Arsene, Iustinian Gabriel Bejan, and Romeo Iulian Olariu
Atmos. Chem. Phys., 22, 2203–2219,Short summary
Gas-phase reaction rate coefficients of OH radicals with four nitrocatechols have been investigated for the first time by using ESC-Q-UAIC chamber facilities. The reactivity of all investigated nitrocatechols is influenced by the formation of the intramolecular H-bonds that are connected to the deactivating electromeric effect of the NO2 group. For the 3-nitrocatechol compounds, the electromeric effect of the
freeOH group is diminished by the deactivating E-effect of the NO2 group.
Zhiyuan Gao, Nicolas-Xavier Geilfus, Alfonso Saiz-Lopez, and Feiyue Wang
Atmos. Chem. Phys., 22, 1811–1824,Short summary
Every spring in the Arctic, a series of photochemical events occur over the ice-covered ocean, known as bromine explosion events, ozone depletion events, and mercury depletion events. Here we report the re-creation of these events at an outdoor sea ice facility in Winnipeg, Canada, far away from the Arctic. The success provides a new platform with new opportunities to uncover fundamental mechanisms of these Arctic springtime phenomena and how they may change in a changing climate.
Haichao Wang, Chao Peng, Xuan Wang, Shengrong Lou, Keding Lu, Guicheng Gan, Xiaohong Jia, Xiaorui Chen, Jun Chen, Hongli Wang, Shaojia Fan, Xinming Wang, and Mingjin Tang
Atmos. Chem. Phys., 22, 1845–1859,Short summary
Via combining laboratory and modeling work, we found that heterogeneous reaction of N2O5 with saline mineral dust aerosol could be an important source of tropospheric ClNO2 in inland regions.
Mike J. Newland, Yangang Ren, Max R. McGillen, Lisa Michelat, Véronique Daële, and Abdelwahid Mellouki
Atmos. Chem. Phys., 22, 1761–1772,Short summary
Wildfires are increasing in extent and severity, driven by climate change. Such fires emit large amounts of volatile organic compounds (VOCs) to the atmosphere. Many of these, such as the furans studied here, are very reactive and are rapidly converted to other VOCs, which are expected to have negative health effects and to further impact the climate. Here, we establish the importance of the nitrate radical for removing these compounds both during the night and during the day.
Delaney B. Kilgour, Gordon A. Novak, Jon S. Sauer, Alexia N. Moore, Julie Dinasquet, Sarah Amiri, Emily B. Franklin, Kathryn Mayer, Margaux Winter, Clare K. Morris, Tyler Price, Francesca Malfatti, Daniel R. Crocker, Christopher Lee, Christopher D. Cappa, Allen H. Goldstein, Kimberly A. Prather, and Timothy H. Bertram
Atmos. Chem. Phys., 22, 1601–1613,Short summary
We report measurements of gas-phase volatile organosulfur molecules made during a mesocosm phytoplankton bloom experiment. Dimethyl sulfide (DMS), methanethiol (MeSH), and benzothiazole accounted for on average over 90 % of total gas-phase sulfur emissions. This work focuses on factors controlling the production and emission of DMS and MeSH and the role of non-DMS molecules (such as MeSH and benzothiazole) in secondary sulfate formation in coastal marine environments.
Niklas Illmann, Iulia Patroescu-Klotz, and Peter Wiesen
Atmos. Chem. Phys., 21, 18557–18572,Short summary
Understanding the chemistry of biomass burning plumes is of global interest. Within this work we investigated the OH radical reaction of 3-penten-2-one, which has been identified in biomass burning emissions. We observed the primary formation of peroxyacetyl nitrate (PAN), a key NOx reservoir species. Besides, PAN precursors were also identified as main oxidation products. 3-Penten-2-one is shown to be an example explaining rapid PAN formation within young biomass burning plumes.
Zhaofeng Tan, Luisa Hantschke, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Changmin Cho, Hans-Peter Dorn, Xin Li, Anna Novelli, Sascha Nehr, Franz Rohrer, Ralf Tillmann, Robert Wegener, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 16067–16091,Short summary
The photo-oxidation of myrcene, a monoterpene species emitted by plants, was investigated at atmospheric conditions in the outdoor simulation chamber SAPHIR. The chemical structure of myrcene is partly similar to isoprene. Therefore, it can be expected that hydrogen shift reactions could play a role as observed for isoprene. In this work, their potential impact on the regeneration efficiency of hydroxyl radicals is investigated.
Shijie Yu, Fangcheng Su, Shasha Yin, Shenbo Wang, Ruixin Xu, Bing He, Xiangge Fan, Minghao Yuan, and Ruiqin Zhang
Atmos. Chem. Phys., 21, 15239–15257,Short summary
This study measured 106 VOC species using a GC-MS/FID. Meanwhile, the WRF-CMAQ model was used to investigate the nonlinearity of the O3 response to precursor reductions. This study highlights the effectiveness of stringent emission controls in relation to solvent utilization and coal combustion. However, unreasonable emission reduction may aggravate ozone pollution during control periods. It is suggested that emission-reduction ratios of the precursors (VOC : NOx) should be more than 2.
Niklas Illmann, Rodrigo Gastón Gibilisco, Iustinian Gabriel Bejan, Iulia Patroescu-Klotz, and Peter Wiesen
Atmos. Chem. Phys., 21, 13667–13686,Short summary
Within this work we determined the rate coefficients and products of the reaction of unsaturated ketones with OH radicals in an effort to complete the gaps in the knowledge needed for modelling chemistry in the atmosphere. Both substances are potentially emitted by biomass burning, industrial activities or formed in the troposphere by oxidation of terpenes. As products we identified aldehydes and ketones which in turn are known to be responsible for the transportation of NOx species.
Yangang Ren, Li Zhou, Abdelwahid Mellouki, Véronique Daële, Mahmoud Idir, Steven S. Brown, Branko Ruscic, Robert S. Paton, Max R. McGillen, and A. R. Ravishankara
Atmos. Chem. Phys., 21, 13537–13551,Short summary
Aromatic aldehydes are a family of compounds emitted into the atmosphere from both anthropogenic and biogenic sources that are formed from the degradation of aromatic hydrocarbons. Their atmospheric degradation may impact air quality. We report on their atmospheric degradation through reaction with NO3, which is useful to estimate their atmospheric lifetimes. We have also attempted to elucidate the mechanism of these reactions via studies of isotopic substitution and quantum chemistry.
Luisa Hantschke, Anna Novelli, Birger Bohn, Changmin Cho, David Reimer, Franz Rohrer, Ralf Tillmann, Marvin Glowania, Andreas Hofzumahaus, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 21, 12665–12685,Short summary
The reactions of Δ3-carene with ozone and the hydroxyl radical (OH) and the photolysis and OH reaction of caronaldehyde were investigated in the simulation chamber SAPHIR. Reaction rate constants of these reactions were determined. Caronaldehyde yields of the ozonolysis and OH reaction were determined. The organic nitrate yield of the reaction of Δ3-carene and caronaldehyde-derived peroxy radicals with NO was determined. The ROx budget (ROx = OH+HO2+RO2) was also investigated.
Letizia Abis, Carmen Kalalian, Bastien Lunardelli, Tao Wang, Liwu Zhang, Jianmin Chen, Sébastien Perrier, Benjamin Loubet, Raluca Ciuraru, and Christian George
Atmos. Chem. Phys., 21, 12613–12629,Short summary
Biogenic volatile organic compound (BVOC) emissions from rapeseed leaf litter have been investigated by means of a controlled atmospheric simulation chamber. The diversity of emitted VOCs increased also in the presence of UV light irradiation. SOA formation was observed when leaf litter was exposed to both UV light and ozone, indicating a potential contribution to particle formation or growth at local scales.
Xi Cheng, Qi Chen, Yong Jie Li, Yan Zheng, Keren Liao, and Guancong Huang
Atmos. Chem. Phys., 21, 12005–12019,Short summary
In this study, we conducted laboratory studies to investigate the formation of gas-phase highly oxygenated organic molecules (HOMs). We provide a thorough analysis on the importance of multistep auto-oxidation and multigeneration OH reactions. We also give an intensive investigation on the roles of high-NO2 conditions that represent a wide range of anthropogenically influenced environments.
Rongrong Wu, Luc Vereecken, Epameinondas Tsiligiannis, Sungah Kang, Sascha R. Albrecht, Luisa Hantschke, Defeng Zhao, Anna Novelli, Hendrik Fuchs, Ralf Tillmann, Thorsten Hohaus, Philip T. M. Carlsson, Justin Shenolikar, François Bernard, John N. Crowley, Juliane L. Fry, Bellamy Brownwood, Joel A. Thornton, Steven S. Brown, Astrid Kiendler-Scharr, Andreas Wahner, Mattias Hallquist, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 10799–10824,Short summary
Isoprene is the biogenic volatile organic compound with the largest emissions rates. The nighttime reaction of isoprene with the NO3 radical has a large potential to contribute to SOA. We classified isoprene nitrates into generations and proposed formation pathways. Considering the potential functionalization of the isoprene nitrates we propose that mainly isoprene dimers contribute to SOA formation from the isoprene NO3 reactions with at least a 5 % mass yield.
Defeng Zhao, Iida Pullinen, Hendrik Fuchs, Stephanie Schrade, Rongrong Wu, Ismail-Hakki Acir, Ralf Tillmann, Franz Rohrer, Jürgen Wildt, Yindong Guo, Astrid Kiendler-Scharr, Andreas Wahner, Sungah Kang, Luc Vereecken, and Thomas F. Mentel
Atmos. Chem. Phys., 21, 9681–9704,Short summary
The reaction of isoprene, a biogenic volatile organic compound with the globally largest emission rates, with NO3, an nighttime oxidant influenced heavily by anthropogenic emissions, forms a large number of highly oxygenated organic molecules (HOM). These HOM are formed via one or multiple oxidation steps, followed by autoxidation. Their total yield is much higher than that in the daytime oxidation of isoprene. They may play an important role in nighttime organic aerosol formation and growth.
Chelsea E. Stockwell, Matthew M. Coggon, Georgios I. Gkatzelis, John Ortega, Brian C. McDonald, Jeff Peischl, Kenneth Aikin, Jessica B. Gilman, Michael Trainer, and Carsten Warneke
Atmos. Chem. Phys., 21, 6005–6022,Short summary
Volatile chemical products are emerging as a large source of petrochemical organics in urban environments. We identify markers for the coatings category by linking ambient observations to laboratory measurements, investigating volatile organic compound (VOC) composition, and quantifying key VOC emissions via controlled evaporation experiments. Ingredients and sales surveys are used to confirm the prevalence and usage trends to support the assignment of water and solvent-borne coating tracers.
Abdelwahid Mellouki, Markus Ammann, R. Anthony Cox, John N. Crowley, Hartmut Herrmann, Michael E. Jenkin, V. Faye McNeill, Jürgen Troe, and Timothy J. Wallington
Atmos. Chem. Phys., 21, 4797–4808,Short summary
Volatile organic compounds play an important role in atmospheric chemistry. This article, the eighth in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers the gas-phase reactions of organic species with four, or more, carbon atoms (≥ C4) including thermal reactions of closed-shell organic species with HO and NO3 radicals and their photolysis. These data are important for atmospheric models.
Michael Priestley, Thomas J. Bannan, Michael Le Breton, Stephen D. Worrall, Sungah Kang, Iida Pullinen, Sebastian Schmitt, Ralf Tillmann, Einhard Kleist, Defeng Zhao, Jürgen Wildt, Olga Garmash, Archit Mehra, Asan Bacak, Dudley E. Shallcross, Astrid Kiendler-Scharr, Åsa M. Hallquist, Mikael Ehn, Hugh Coe, Carl J. Percival, Mattias Hallquist, Thomas F. Mentel, and Gordon McFiggans
Atmos. Chem. Phys., 21, 3473–3490,Short summary
A significant fraction of emissions from human activity consists of aromatic hydrocarbons, e.g. benzene, which oxidise to form new compounds important for particle growth. Characterisation of benzene oxidation products highlights the range of species produced as well as their chemical properties and contextualises them within relevant frameworks, e.g. MCM. Cluster analysis of the oxidation product time series distinguishes behaviours of CHON compounds that could aid in identifying functionality.
Gareth J. Stewart, W. Joe F. Acton, Beth S. Nelson, Adam R. Vaughan, James R. Hopkins, Rahul Arya, Arnab Mondal, Ritu Jangirh, Sakshi Ahlawat, Lokesh Yadav, Sudhir K. Sharma, Rachel E. Dunmore, Siti S. M. Yunus, C. Nicholas Hewitt, Eiko Nemitz, Neil Mullinger, Ranu Gadi, Lokesh K. Sahu, Nidhi Tripathi, Andrew R. Rickard, James D. Lee, Tuhin K. Mandal, and Jacqueline F. Hamilton
Atmos. Chem. Phys., 21, 2383–2406,Short summary
Biomass burning is a major source of trace gases to the troposphere; however, the composition and quantity of emissions vary greatly between different fuel types. This work provided near-total quantitation of non-methane volatile organic compounds from combustion of biofuels from India. Emissions from cow dung cake combustion were significantly larger than conventional fuelwood combustion, potentially indicating that this source has a disproportionately large impact on regional air quality.
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Jean-François Doussin, and Bénédicte Picquet-Varrault
Atmos. Chem. Phys., 20, 15167–15189,
Michael Rolletter, Marion Blocquet, Martin Kaminski, Birger Bohn, Hans-Peter Dorn, Andreas Hofzumahaus, Frank Holland, Xin Li, Franz Rohrer, Ralf Tillmann, Robert Wegener, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 20, 13701–13719,Short summary
The photooxidation of pinonaldehyde is investigated in a chamber study under natural sunlight and low NO conditions with and without an added hydroxyl radical (OH) scavenger. The experimentally determined pinonaldehyde photolysis frequency is faster by a factor of 3.5 than currently used parameterizations in atmospheric models. Yields of degradation products are measured in the presence and absence of OH. Measurements are compared to current atmospheric models and a theory-based mechanism.
Matias Berasategui, Damien Amedro, Luc Vereecken, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 13541–13555,Short summary
Peracetic acid is one of the most abundant organic peroxides in the atmosphere. We combine experiments and theory to show that peracetic acid reacts orders of magnitude more slowly with OH than presently accepted, which results in a significant extension of its atmospheric lifetime.
Jacinta Edebeli, Jürg C. Trachsel, Sven E. Avak, Markus Ammann, Martin Schneebeli, Anja Eichler, and Thorsten Bartels-Rausch
Atmos. Chem. Phys., 20, 13443–13454,Short summary
Earth’s snow cover is very dynamic and can change its physical properties within hours, as is well known by skiers. Snow is also a well-known host of chemical reactions – the products of which impact air composition and quality. Here, we present laboratory experiments that show how the dynamics of snow make snow essentially inert with respect to gas-phase ozone with time despite its content of reactive chemicals. Impacts on polar atmospheric chemistry are discussed.
R. Anthony Cox, Markus Ammann, John N. Crowley, Hartmut Herrmann, Michael E. Jenkin, V. Faye McNeill, Abdelwahid Mellouki, Jürgen Troe, and Timothy J. Wallington
Atmos. Chem. Phys., 20, 13497–13519,Short summary
Criegee intermediates, formed from alkene–ozone reactions, play a potentially important role as tropospheric oxidants. Evaluated kinetic data are provided for reactions governing their formation and removal for use in atmospheric models. These include their formation from reactions of simple and complex alkenes and removal by decomposition and reaction with a number of atmospheric species (e.g. H2O, SO2). An overview of the tropospheric chemistry of Criegee intermediates is also provided.
Jake P. Rowe, Andrew T. Lambe, and William H. Brune
Atmos. Chem. Phys., 20, 13417–13424,Short summary
We conducted a series of experiments in which the 185 to 254 nm photon flux ratio (I185 : I254) emitted by low-pressure mercury lamps installed in an oxidation flow reactor (OFR) was systematically varied using multiple novel lamp configurations. Integrated OH exposure values achieved for each lamp type were obtained as a function of OFR operating conditions. A photochemical box model was used to develop a generalized OH exposure estimation equation as a function of [H2O], [O3], and OH reactivity.
Mei-Tsan Kuo, Isabelle Weber, Christa Fittschen, Luc Vereecken, and Jim Jr-Min Lin
Atmos. Chem. Phys., 20, 12983–12993,Short summary
Dimethyl sulfide (DMS) is the major sulfur-containing species in the troposphere. Previous work by Newland et al. (2015) reported very high reactivity of isoprene-derived Criegee intermediates (CIs) towards DMS. By monitoring CIs with direct UV absorption, we found CI + DMS reactions are very slow, in contrast to the results of Newland et al. (2015), suggesting these CIs would not oxidize atmospheric DMS at any substantial level.
Thomas R. Lewis, Juan Carlos Gómez Martín, Mark A. Blitz, Carlos A. Cuevas, John M. C. Plane, and Alfonso Saiz-Lopez
Atmos. Chem. Phys., 20, 10865–10887,Short summary
Iodine-bearing gasses emitted from the sea surface are chemically processed in the atmosphere, leading to iodine accumulation in aerosol and transport to continental ecosystems. Such processing involves light-induced break-up of large, particle-forming iodine oxides into smaller, ozone-depleting molecules. We combine experiments and theory to report the photolysis efficiency of iodine oxides required to assess the impact of iodine on ozone depletion and particle formation.
Patrick Dewald, Jonathan M. Liebmann, Nils Friedrich, Justin Shenolikar, Jan Schuladen, Franz Rohrer, David Reimer, Ralf Tillmann, Anna Novelli, Changmin Cho, Kangming Xu, Rupert Holzinger, François Bernard, Li Zhou, Wahid Mellouki, Steven S. Brown, Hendrik Fuchs, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 10459–10475,Short summary
We present direct measurements of NO3 reactivity resulting from the oxidation of isoprene by NO3 during an intensive simulation chamber study. Measurements were in excellent agreement with values calculated from measured isoprene amounts and the rate coefficient for the reaction of NO3 with isoprene. Comparison of the measurement with NO3 reactivities from non-steady-state and model calculations suggests that isoprene-derived RO2 and HO2 radicals account to ~ 50 % of overall NO3 losses.
Jacob T. Shaw, Andrew R. Rickard, Mike J. Newland, and Terry J. Dillon
Atmos. Chem. Phys., 20, 9725–9736,Short summary
This work expands upon the recently developed multivariate relative rate technique, presented in Shaw et al. (2019), for the measurement of rates of reaction between aromatic and aliphatic volatile organic compounds (VOCs) and OH. Knowledge of the rates of such reactions are important for understanding air quality in urban environments. This work also provides a key validation of structure–activity relationship models, which provide a theoretical method for estimating OH + VOC kinetics.
Rodrigo Gastón Gibilisco, Ian Barnes, Iustinian Gabriel Bejan, and Peter Wiesen
Atmos. Chem. Phys., 20, 8939–8951,Short summary
Environmental chamber studies were performed to evaluate atmospheric degradation initiated by OH radicals for two unsaturated methoxy ketones. The main gas-phase oxidation products identified and quantified from these reactions are carbonyls and long-lived nitrogen-containing compounds such as peroxyacetyl nitrate and peroxypropionyl nitrate. The kinetic rate constants and atmospheric lifetimes were estimated, degradation mechanisms were developed, and atmospheric implications were assessed.
James M. Roberts, Chelsea E. Stockwell, Robert J. Yokelson, Joost de Gouw, Yong Liu, Vanessa Selimovic, Abigail R. Koss, Kanako Sekimoto, Matthew M. Coggon, Bin Yuan, Kyle J. Zarzana, Steven S. Brown, Cristina Santin, Stefan H. Doerr, and Carsten Warneke
Atmos. Chem. Phys., 20, 8807–8826,Short summary
We measured total reactive nitrogen, Nr, in lab fires from western North American fuels, along with measurements of individual nitrogen compounds. We measured the amount of N that gets converted to inactive compounds (avg. 70 %), and the amount that is accounted for by individual species (85 % of remaining N). We provide guidelines for how the reactive nitrogen is distributed among individual compounds such as NOx and ammonia. This will help estimates and predictions of wildfire emissions.
Anna Novelli, Luc Vereecken, Birger Bohn, Hans-Peter Dorn, Georgios I. Gkatzelis, Andreas Hofzumahaus, Frank Holland, David Reimer, Franz Rohrer, Simon Rosanka, Domenico Taraborrelli, Ralf Tillmann, Robert Wegener, Zhujun Yu, Astrid Kiendler-Scharr, Andreas Wahner, and Hendrik Fuchs
Atmos. Chem. Phys., 20, 3333–3355,Short summary
Experimental evidence from a simulation chamber study shows that the regeneration efficiency of the hydroxyl radical is maintained globally at values higher than 0.5 for a wide range of nitrogen oxide concentrations as a result of isomerizations of peroxy radicals originating from the OH oxidation of isoprene. The available models were tested, and suggestions on how to improve their ability to reproduce the measured radical and oxygenated volatile organic compound concentrations are provided.
Damien Amedro, Matias Berasategui, Arne J. C. Bunkan, Andrea Pozzer, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 3091–3105,Short summary
Our laboratory experiments show that the rate coefficient for the termolecular reaction between OH and NO2 is enhanced in the presence of water vapour. Using a chemistry transport model we show that our new parameterization of the temperature, pressure, and bath-gas dependence of this reaction has a significant impact on, for example, NOx and the HNO2 / NO2 ratio when compared to present recommendations.
Matias Berasategui, Damien Amedro, Achim Edtbauer, Jonathan Williams, Jos Lelieveld, and John N. Crowley
Atmos. Chem. Phys., 20, 2695–2707,Short summary
We have determined the rate coefficient and mechanism for the reaction of the OH radical with methane sulphonamide, a trace gas which has recently been found in the atmosphere. The rate coefficient is 1.4 × 10−13 cm3 molec.−1 s−1, which indicates a tropospheric lifetime of > 2 months. The observation of CO, CO2, SO2, HNO3, HCOOH, and N2O products enabled us to derive a detailed reaction mechanism for the reaction, which proceeds predominantly by H abstraction from the CH3 group.
Abigail R. Koss, Manjula R. Canagaratna, Alexander Zaytsev, Jordan E. Krechmer, Martin Breitenlechner, Kevin J. Nihill, Christopher Y. Lim, James C. Rowe, Joseph R. Roscioli, Frank N. Keutsch, and Jesse H. Kroll
Atmos. Chem. Phys., 20, 1021–1041,Short summary
Oxidation chemistry of organic compounds in the atmosphere produces a diverse spectrum of products. This diversity is difficult to represent in air quality and climate models, and in laboratory experiments it results in large and complex datasets. This work evaluates several methods to simplify the chemistry of oxidation systems in environmental chambers, including positive matrix factorization, hierarchical clustering analysis, and gamma kinetics parameterization.
Inmaculada Colmenar, Pilar Martin, Beatriz Cabañas, Sagrario Salgado, Araceli Tapia, and Inmaculada Aranda
Atmos. Chem. Phys., 20, 699–720,Short summary
Saturated alcohols (SAs), such as (E)-4-methylcyclohexanol, 3,3-dimethyl-1-butanol, and 3,3-dimethyl-2-butanol, could be used as biofuels. The atmospheric reactivity of these compounds must be established in order to understand the consequences of the presence of these compounds in the atmosphere. The experimental results obtained in this work reveal that uncontrolled emissions of these saturated alcohols could have important atmospheric implications.
Olga Garmash, Matti P. Rissanen, Iida Pullinen, Sebastian Schmitt, Oskari Kausiala, Ralf Tillmann, Defeng Zhao, Carl Percival, Thomas J. Bannan, Michael Priestley, Åsa M. Hallquist, Einhard Kleist, Astrid Kiendler-Scharr, Mattias Hallquist, Torsten Berndt, Gordon McFiggans, Jürgen Wildt, Thomas F. Mentel, and Mikael Ehn
Atmos. Chem. Phys., 20, 515–537,Short summary
Highly oxygenated organic molecules (HOMs) facilitate aerosol formation in the atmosphere. Using NO3− chemical ionization mass spectrometry we investigated HOM composition and yield in oxidation of aromatic compounds at different reactant concentrations, in the presence of NOx and seed aerosol. Higher OH concentrations increased HOM yield, suggesting multiple oxidation steps, and affected HOM composition, potentially explaining in part discrepancies in published secondary organic aerosol yields.
Bénédicte Picquet-Varrault, Ricardo Suarez-Bertoa, Marius Duncianu, Mathieu Cazaunau, Edouard Pangui, Marc David, and Jean-François Doussin
Atmos. Chem. Phys., 20, 487–498,Short summary
Multifunctional organic nitrates are important atmospheric species that are known to play a key role in the transport of reactive nitrogen and in aerosol composition. However, very little is known about their atmospheric reactivity. Here we provide an experimental study on the photolysis and reaction of two carbonyl nitrates with OH radicals. Atmospheric implications and the influence of the chemical structure on the reactivity are discussed.
Eetu Kari, Liqing Hao, Arttu Ylisirniö, Angela Buchholz, Ari Leskinen, Pasi Yli-Pirilä, Ilpo Nuutinen, Kari Kuuspalo, Jorma Jokiniemi, Celia L. Faiola, Siegfried Schobesberger, and Annele Virtanen
Atmos. Chem. Phys., 19, 15651–15671,Short summary
We present, for the first time, the dual effect of GDI-vehicle exhaust on α-pinene SOA mass yield suppression. The first effect is a well-known NOx effect, but the second effect is more complex. Our results imply that this second effect is related to change of reaction pathways of α-pinene in the presence of GDI exhaust. The presence of vehicle exhaust caused more than 50 % suppression in α-pinene SOA mass yield compared to the α-pinene SOA mass yield measured in the absence of GDI emissions.
Epameinondas Tsiligiannis, Julia Hammes, Christian Mark Salvador, Thomas F. Mentel, and Mattias Hallquist
Atmos. Chem. Phys., 19, 15073–15086,Short summary
The role of anthropogenic VOCs (AVOCs) for SOA formation needs to be scrutinised. The aromatic 1,3,5-trimethylbenzene (TMB) was shown to form highly oxygenated organic molecules (HOMs) in NOx-free environments, possibly contributing to new particle formation (NPF). However, formation of HOMs and particles was suppressed in the presence of NOx, while the formation of organonitrates (ONs) was increased. Thus, aromatic AVOCs may not enhance NPF in urban air masses.
Alexander Zaytsev, Abigail R. Koss, Martin Breitenlechner, Jordan E. Krechmer, Kevin J. Nihill, Christopher Y. Lim, James C. Rowe, Joshua L. Cox, Joshua Moss, Joseph R. Roscioli, Manjula R. Canagaratna, Douglas R. Worsnop, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Chem. Phys., 19, 15117–15129,Short summary
Aromatic hydrocarbons contribute significantly to the production of tropospheric ozone and secondary organic aerosol (SOA). Here later-generation low-volatility oxygenated products from toluene and 1,2,4-TMB oxidation by OH are detected in the gas and particle phases. We show that these products, previously identified as highly oxygenated molecules (HOMs), are formed in more than one pathway with differing numbers of reaction steps with OH. They also make up a significant fraction of SOA.
Allen, H. C., Gragson, D., and Richmond, G.: Molecular structure and adsorption of dimethyl sulfoxide at the surface of aqueous solutions, J. Phys. Chem. B, 103, 660–666, 1999.
Altieri, K. E., Carlton, A. G., Lim, H.-J., Turpin, B. J., and Seitzinger, S. P.: Evidence for oligomer formation in clouds: Reactions of isoprene oxidation products, Environ. Sci. Technol., 40, 4956–4960, https://doi.org/10.1021/es052170n, 2006.
Andreae, M. O. J. L.: Dimethylsulfoxide in marine and freshwaters, Limnol. Oceanogr., 25, 1054–1063, 1980.
Arsene, C., Barnes, I., Becker, K. H., Schneider, W. F., Wallington, T. T., Mihalopoulos, N., and Patroescu-Klotz, I. V. J. E. S.: Formation of methane sulfinic acid in the gas-phase OH-radical initiated oxidation of dimethyl sulfoxide, Environ. Sci. Technol., 36, 5155–5163, 2002.
Asher, E., Dacey, J. W., Ianson, D., Peña, A., and Tortell, P. D.: Concentrations and cycling of DMS, DMSP, and DMSO in coastal and offshore waters of the Subarctic Pacific during summer, 2010–2011, J. Geophys. Res.-Oceans, 122, 3269–3286, 2017.
Barnes, I., Hjorth, J., and Mihalopoulos, N.: Dimethyl sulfide and dimethyl sulfoxide and their oxidation in the atmosphere, Chem. Rev., 106, 940–975, https://doi.org/10.1021/cr020529+, 2006.
Benson, N. U., Essien, J. P., Asuquo, F. E., and Eritobor, A. L.: Occurrence and distribution of polycyclic aromatic hydrocarbons in surface microlayer and subsurface seawater of Lagos Lagoon, Nigeria, Environ. Monit. Assess., 186, 5519–5529, 2014.
Berresheim, H. and Eisele, F.: Sulfur chemistry in the Antarctic Troposphere Experiment: An overview of project SCATE, J. Geophys. Res.-Atmos., 103, 1619–1627, 1998.
Berresheim, H., Eisele, F., Tanner, D., McInnes, L., Ramsey-Bell, D., and Covert, D.: Atmospheric sulfur chemistry and cloud condensation nuclei (CCN) concentrations over the northeastern Pacific coast, J. Geophys. Res.-Atmos., 98, 12701–12711, 1993.
Berresheim, H., Elste, T., Tremmel, H. G., Allen, A. G., Hansson, H. C., Rosman, K., Dal Maso, M., Makela, J. M., Kulmala, M., and O'Dowd, C. D.: Gas-aerosol relationships of H2SO4, MSA, and OH: Observations in the coastal marine boundary layer at Mace Head, Ireland, J. Geophys. Res.-Atmos., 107, PAR 5-1–PAR 5-12,, https://doi.org/10.1029/2000jd000229, 2002.
Binning Jr., R. and Curtiss, L.: Compact contracted basis sets for third-row atoms: Ga–Kr, J. Comput. Chem., 11, 1206–1216, 1990.
Blair, S. L., MacMillan, A. C., Drozd, G. T., Goldstein, A. H., Chu, R. K., Paša-Tolić, L., Shaw, J. B., Tolić, N., Lin, P., and Laskin, J.: Molecular characterization of organosulfur compounds in biodiesel and diesel fuel secondary organic aerosol, Environ. Sci. Technol., 51, 119–127, 2017.
Bork, N., Elm, J., Olenius, T., and Vehkamäki, H.: Methane sulfonic acid-enhanced formation of molecular clusters of sulfuric acid and dimethyl amine, Atmos. Chem. Phys., 14, 12023–12030, https://doi.org/10.5194/acp-14-12023-2014, 2014.
Brigante, M., Charbouillot, T., Vione, D., and Mailhot, G.: Photochemistry of 1-nitronaphthalene: A potential source of singlet oxygen and radical species in atmospheric waters, J. Phys. Chem. A, 114, 2830–2836, 2010.
Brimblecombe, P. and Shooter, D.: Photo-oxidation of dimethylsulphide in aqueous solution, Mar. Chem., 19, 343–353, 1986.
Brüggemann, M., Hayeck, N., and George, C.: Interfacial photochemistry at the ocean surface is a global source of organic vapors and aerosols, Nat. Commun., 9, 2101, https://doi.org/10.1038/s41467-018-04528-7, 2018.
Bruggemann, M., Xu, R., Tilgner, A., Kwong, K. C., Mutzel, A., Poon, H. Y., Otto, T., Schaefer, T., Poulain, L., Chan, M. N., and Herrmann, H.: Organosulfates in Ambient Aerosol: State of Knowledge and Future Research Directions on Formation, Abundance, Fate, and Importance, Environ. Sci. Technol., 54, 3767–3782, https://doi.org/10.1021/acs.est.9b06751, 2020.
Cai, D., Wang, X., Chen, J., and Li, X.: Molecular Characterization of Organosulfates in Highly Polluted Atmosphere Using Ultra-High-Resolution Mass Spectrometry, J. Geophys. Res.-Atmos., 125, e2019JD032253, https://doi.org/10.1029/2019jd032253, 2020.
Chen, H., Varner, M. E., Gerber, R. B., and Finlayson-Pitts, B. J.: Reactions of Methanesulfonic Acid with Amines and Ammonia as a Source of New Particles in Air, J. Phys. Chem. B, 120, 1526–1536, https://doi.org/10.1021/acs.jpcb.5b07433, 2016.
Chen, J., Ehrenhauser, F. S., Valsaraj, K. T., and Wornat, M. J.: Uptake and UV-photooxidation of gas-phase PAHs on the surface of atmospheric water films. 1. Naphthalene, J. Phys. Chem. A, 110, 9161–9168, 2006.
Chen, Q., Sherwen, T., Evans, M., and Alexander, B.: DMS oxidation and sulfur aerosol formation in the marine troposphere: a focus on reactive halogen and multiphase chemistry, Atmos. Chem. Phys., 18, 13617–13637, https://doi.org/10.5194/acp-18-13617-2018, 2018.
Cincinelli, A., Stortini, A. M., Perugini, M., Checchini, L., and Lepri, L.: Organic pollutants in sea-surface microlayer and aerosol in the coastal environment of Leghorn – (Tyrrhenian Sea), Mar. Chem., 76, 77–98, https://doi.org/10.1016/s0304-4203(01)00049-4, 2001.
Dall'Osto, M., Ceburnis, D., Monahan, C., Worsnop, D. R., Bialek, J., Kulmala, M., Kurten, T., Ehn, M., Wenger, J., Sodeau, J., Healy, R., and O'Dowd, C.: Nitrogenated and aliphatic organic vapors as possible drivers for marine secondary organic aerosol growth, J. Geophys. Res.-Atmos., 117, D12311, https://doi.org/10.1029/2012jd017522, 2012.
Davidovits, P., Kolb, C. E., Williams, L. R., Jayne, J. T., and Worsnop, D. R.: Mass accommodation and chemical reactions at gas-liquid interfaces, Chem. Rev., 106, 1323–1354, 2006.
Dawson, M. L., Varner, M. E., Perraud, V., Ezell, M. J., Gerber, R. B., and Finlayson-Pitts, B. J.: Simplified mechanism for new particle formation from methanesulfonic acid, amines, and water via experiments and ab initio calculations, P. Natl. Acad. Sci. USA, 109, 18719–18724, 2012.
Decesari, S., Finessi, E., Rinaldi, M., Paglione, M., Fuzzi, S., Stephanou, E., Tziaras, T., Spyros, A., Ceburnis, D., and O'Dowd, C.: Primary and secondary marine organic aerosols over the North Atlantic Ocean during the MAP experiment, J. Geophys. Res.-Atmos., 116, D22210, https://doi.org/10.1029/2011JD016204, 2011.
Deng, H., Liu, J., Wang, Y., Song, W., Wang, X., Li, X., Vione, D., and Gligorovski, S.: Effect of Inorganic Salts on N-Containing Organic Compounds Formed by Heterogeneous Reaction of NO2 with Oleic Acid, Environ. Sci. Technol., 55, 7831–7840, https://doi.org/10.1021/acs.est.1c01043, 2021.
Donaldson, D., Kahan, T., Kwamena, N., Handley, S., and Barbier, C.: Atmospheric chemistry of urban surface films, in: Atmospheric Aerosols Characterization, Chemistry, Modeling, and Climate, ACS Publications, 79–89, https://doi.org/10.1021/bk-2009-1005.ch006, 2009.
Falbe-Hansen, H., Sørensen, S., Jensen, N., Pedersen, T., and Hjorth, J.: Atmospheric gas-phase reactions of dimethylsulphoxide and dimethylsulphone with OH and NO3 radicals, Cl atoms and ozone, Atmos. Environ., 34, 1543–1551, 2000.
Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Petersson, G. A., Nakatsuji, H., Li, X., Caricato, M., Marenich, A. V., Bloino, J., Janesko, B. G., Gomperts, R., Mennucci, B., Hratchian, H. P., Ortiz, J. V., Izmaylov, A. F., Sonnenberg, J. L., Williams, Ding, F., Lipparini, F., Egidi, F., Goings, J., Peng, B., Petrone, A., Henderson, T., Ranasinghe, D., Zakrzewski, V. G., Gao, J., Rega, N., Zheng, G., Liang, W., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Throssell, K., Montgomery Jr., J. A., Peralta, J. E., Ogliaro, F., Bearpark, M. J., Heyd, J. J., Brothers, E. N., Kudin, K. N., Staroverov, V. N., Keith, T. A., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A. P., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Millam, J. M., Klene, M., Adamo, C., Cammi, R., Ochterski, J. W., Martin, R. L., Morokuma, K., Farkas, O., Foresman, J. B., and Fox, D. J.: Gaussian 16, Revision. C.01, Gaussian, Inc., Wallingford, CT, USA, 2016.
Gaston, C. J., Pratt, K. A., Qin, X., and Prather, K. A.: Real-time detection and mixing state of methanesulfonate in single particles at an inland urban location during a phytoplankton bloom, Environ. Sci. Technol., 44, 1566–1572, 2010.
González-García, N., González-Lafont, À., and Lluch, J. M.: Variational transition-state theory study of the dimethyl sulfoxide (DMSO) and OH reaction, J. Phys. Chem. A, 110, 798–808, 2006.
González-Gaya, B., Fernández-Pinos, M.-C., Morales, L., Méjanelle, L., Abad, E., Piña, B., Duarte, C. M., Jiménez, B., and Dachs, J.: High atmosphere–ocean exchange of semivolatile aromatic hydrocarbons, Nat. Geosci., 9, 438–442, https://doi.org/10.1038/ngeo2714, 2016.
González-Gaya, B., Martínez-Varela, A., Vila-Costa, M., Casal, P., Cerro-Gálvez, E., Berrojalbiz, N., Lundin, D., Vidal, M., Mompeán, C., and Bode, A.: Biodegradation as an important sink of aromatic hydrocarbons in the oceans, Nat. Geosci., 12, 119–125, 2019.
Grossman, J. N., Stern, A. P., Kirich, M. L., and Kahan, T. F.: Anthracene and pyrene photolysis kinetics in aqueous, organic, and mixed aqueous-organic phases, Atmos. Environ., 128, 158–164, 2016.
Guitart, C., Garcia-Flor, N., Bayona, J. M., and Albaiges, J.: Occurrence and fate of polycyclic aromatic hydrocarbons in the coastal surface microlayer, Mar. Pollut. Bull., 54, 186–194, https://doi.org/10.1016/j.marpolbul.2006.10.008, 2007.
Hardy, J. T., Crecelius, E. A., Antrim, L. D., Kiesser, S. L., Broadhurst, V. L., Boehm, P. D., Steinhauer, W. G., and Coogan, T. H.: Aquatic surface microlayer contamination in chesapeake bay, Mar. Chem., 28, 333–351, 1990.
Harvey, G. R. and Lang, R. F.: Dimethylsulfoxide and dimethylsulfone in the marine atmosphere, Geophys. Res. Lett., 13, 49–51, 1986.
Hatton, A., Malin, G., Turner, S., and Liss, P.: DMSO, A Significant Compound in the Biogeochemical Cycle of DMS., in: Biological and Environmental Chemistry of DMSP and Related Sulfonium Compounds, Springer, 405–412, ISBN 978-1-4613-8024-5, 1996.
Hoffmann, E. H., Tilgner, A., Schrodner, R., Brauer, P., Wolke, R., and Herrmann, H.: An advanced modeling study on the impacts and atmospheric implications of multiphase dimethyl sulfide chemistry, P. Natl. Acad. Sci. USA, 113, 11776–11781, https://doi.org/10.1073/pnas.1606320113, 2016.
Hopkins, R. J., Desyaterik, Y., Tivanski, A. V., Zaveri, R. A., Berkowitz, C. M., Tyliszczak, T., Gilles, M. K., and Laskin, A.: Chemical speciation of sulfur in marine cloud droplets and particles: Analysis of individual particles from the marine boundary layer over the California current, J. Geophys. Res.-Atmos., 113, D04209, https://doi.org/10.1029/2007JD008954, 2008.
Huang, L., Liu, T., and Grassian, V. H.: Radical-Initiated Formation of Aromatic Organosulfates and Sulfonates in the Aqueous Phase, Environ. Sci. Technol., 54, 11857–11864, https://doi.org/10.1021/acs.est.0c05644, 2020.
Jiang, B., Kuang, B. Y., Liang, Y., Zhang, J., Huang, X. H. H., Xu, C., Yu, J. Z., and Shi, Q.: Molecular composition of urban organic aerosols on clear and hazy days in Beijing: a comparative study using FT-ICR MS, Environ. Chem., 13, 888–901, https://doi.org/10.1071/en15230, 2016.
Jiang, H., Carena, L., He, Y., Wang, Y., Zhou, W., Yang, L., Luan, T., Li, X., Brigante, M., Vione, D., and Gligorovski, S.: Photosensitized Degradation of DMSO Initiated by PAHs at the Air-Water Interface, as an Alternative Source of Organic Sulfur Compounds to the Atmosphere, J. Geophys. Res.-Atmos., 126, e2021JD035346, https://doi.org/10.1029/2021JD035346, 2021.
Kamens, R. M., Zhang, H., Chen, E. H., Zhou, Y., Parikh, H. M., Wilson, R. L., Galloway, K. E., and Rosen, E. P.: Secondary organic aerosol formation from toluene in an atmospheric hydrocarbon mixture: Water and particle seed effects, Atmos. Environ., 45, 2324–2334, https://doi.org/10.1016/j.atmosenv.2010.11.007, 2011.
Karl, M., Gross, A., Leck, C., and Pirjola, L.: Intercomparison of dimethylsulfide oxidation mechanisms for the marine boundary layer: Gaseous and particulate sulfur constituents, J. Geophys. Res.-Atmos., 112, D15304, https://doi.org/10.1029/2006jd007914, 2007.
Kourtchev, I., O'Connor, I. P., Giorio, C., Fuller, S. J., Kristensen, K., Maenhaut, W., Wenger, J. C., Sodeau, J. R., Glasius, M., and Kalberer, M.: Effects of anthropogenic emissions on the molecular composition of urban organic aerosols: An ultrahigh resolution mass spectrometry study, Atmos. Environ., 89, 525–532, https://doi.org/10.1016/j.atmosenv.2014.02.051, 2014.
Kroll, J. A., Frandsen, B. N., Kjaergaard, H. G., and Vaida, V.: Atmospheric hydroxyl radical source: Reaction of triplet SO2 and water, J. Phys. Chem. A, 122, 4465–4469, 2018.
Kukui, A., Borissenko, D., Laverdet, G., and Le Bras, G.: Gas-phase reactions of OH radicals with dimethyl sulfoxide and methane sulfinic acid using turbulent flow reactor and chemical ionization mass spectrometry, J. Phys. Chem. A, 107, 5732–5742, 2003.
Kundu, S., Quraishi, T. A., Yu, G., Suarez, C., Keutsch, F. N., and Stone, E. A.: Evidence and quantitation of aromatic organosulfates in ambient aerosols in Lahore, Pakistan, Atmos. Chem. Phys., 13, 4865–4875, https://doi.org/10.5194/acp-13-4865-2013, 2013.
Lammel, G.: Polycyclic aromatic compounds in the atmosphere – a review identifying research needs, Polycycl. Aromat. Comp., 35, 316–329, 2015.
Lee, P. and De Mora, S.: DMSP, DMS and DMSO concentrations and temporal trends in marine surface waters at Leigh, New Zealand, in: Biological and Environmental Chemistry of DMSP and Related Sulfonium Compounds, Springer, 391–404, ISBN 978-0-306-45306-9, 1996.
Lee, P. A., de Mora, S. J., and Levasseur, M.: A review of dimethylsulfoxide in aquatic environments, Atmos.-Ocean, 37, 439–456, https://doi.org/10.1080/07055900.1999.9649635, 1999.
Legrand, M., Sciare, J., Jourdain, B., and Genthon, C.: Subdaily variations of atmospheric dimethylsulfide, dimethylsulfoxide, methanesulfonate, and non-sea-salt sulfate aerosols in the atmospheric boundary layer at Dumont d'Urville (coastal Antarctica) during summer, J. Geophys. Res.-Atmos., 106, 14409–14422, 2001.
Li, G., Bei, N., Cao, J., Huang, R., Wu, J., Feng, T., Wang, Y., Liu, S., Zhang, Q., Tie, X., and Molina, L. T.: A possible pathway for rapid growth of sulfate during haze days in China, Atmos. Chem. Phys., 17, 3301–3316, https://doi.org/10.5194/acp-17-3301-2017, 2017.
Li, J., Li, F., and Liu, Q.: PAHs behavior in surface water and groundwater of the Yellow River estuary: evidence from isotopes and hydrochemistry, Chemosphere, 178, 143–153, 2017.
Librando, V., Tringali, G., Hjorth, J., and Coluccia, S.: OH-initiated oxidation of DMS/DMSO: reaction products at high NOx levels, Environ. Pollut., 127, 403–410, 2004.
Librando, V., Bracchitta, G., de Guidi, G., Minniti, Z., Perrini, G., and Catalfo, A.: Photodegradation of anthracene and benzo [a] anthracene in polar and apolar media: new pathways of photodegradation, Polycycl. Aromat. Comp., 34, 263–279, 2014.
Lin, P., Rincon, A. G., Kalberer, M., and Yu, J. Z.: Elemental composition of HULIS in the Pearl River Delta Region, China: results inferred from positive and negative electrospray high resolution mass spectrometric data, Environ. Sci. Technol., 46, 7454–7462, https://doi.org/10.1021/es300285d, 2012.
Lohmann, R., Gioia, R., Jones, K. C., Nizzetto, L., Temme, C., Xie, Z., Schulz-Bull, D., Hand, I., Morgan, E., and Jantunen, L. J. E. S.: Organochlorine pesticides and PAHs in the surface water and atmosphere of the North Atlantic and Arctic Ocean, Environ. Sci. Technol., 43, 5633–5639, 2009.
Ma, Y., Xie, Z., Yang, H., Möller, A., Halsall, C., Cai, M., Sturm, R., and Ebinghaus, R.: Deposition of polycyclic aromatic hydrocarbons in the North Pacific and the Arctic, J. Geophys. Res.-Atmos., 118, 5822–5829, 2013.
Ma, Y., Xu, X., Song, W., Geng, F., and Wang, L.: Seasonal and diurnal variations of particulate organosulfates in urban Shanghai, China, Atmos. Environ., 85, 152–160, https://doi.org/10.1016/j.atmosenv.2013.12.017, 2014.
Martins-Costa, M. T., Anglada, J. M., Francisco, J. S., and Ruiz-Loìpez, M. F.: Photochemistry of SO2 at the air–water interface: a source of OH and HOSO radicals, J. Am. Chem. Soc., 140, 12341–12344, 2018.
McLean, A. and Chandler, G.: Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18, J. Chem. Phys., 72, 5639–5648, 1980.
Mekic, M., Zeng, J., Jiang, B., Li, X., Lazarou, Y. G., Brigante, M., Herrmann, H., and Gligorovski, S.: Formation of Toxic Unsaturated Multifunctional and Organosulfur Compounds From the Photosensitized Processing of Fluorene and DMSO at the Air-Water Interface, J. Geophys. Res.-Atmos., 125, https://doi.org/10.1029/2019jd031839, 2020a.
Mekic, M., Zeng, J., Zhou, W., Loisel, G., Jin, B., Li, X., Vione, D., and Gligorovski, S.: Ionic Strength Effect on Photochemistry of Fluorene and Dimethylsulfoxide at the Air–Sea Interface: Alternative Formation Pathway of Organic Sulfur Compounds in a Marine Atmosphere ACS Earth Space Chem., 4, 1029–1038, https://doi.org/10.1021/acsearthspacechem.0c00059, 2020b.
Monge, M. E., George, C., D'Anna, B., Doussin, J.-F., Jammoul, A., Wang, J., Eyglunent, G., Solignac, G., Daele, V., and Mellouki, A.: Ozone formation from illuminated titanium dioxide surfaces, J. Am. Chem. Soc., 132, 8234–8235, 2010.
Ning, A., Zhang, H., Zhang, X., Li, Z., Zhang, Y., Xu, Y., and Ge, M.: A molecular-scale study on the role of methanesulfinic acid in marine new particle formation, Atmos. Environ., 227, 117378, https://doi.org/10.1016/j.atmosenv.2020.117378, 2020.
Nizkorodov, S. A., Laskin, J., and Laskin, A.: Molecular chemistry of organic aerosols through the application of high resolution mass spectrometry, Phys. Chem. Chem. Phys., 13, 3612–3629, 2011.
Oppenheimer, C., Francis, P., Burton, M., Maciejewski, A., and Boardman, L.: Remote measurement of volcanic gases by Fourier transform infrared spectroscopy, Appl. Phys. B-Lasers O., 67, 505–515, https://doi.org/10.1007/s003400050536, 1998.
Otto, S., Streibel, T., Erdmann, S., Klingbeil, S., Schulz-Bull, D., and Zimmermann, R.: Pyrolysis–gas chromatography–mass spectrometry with electron-ionization or resonance-enhanced-multi-photon-ionization for characterization of polycyclic aromatic hydrocarbons in the Baltic Sea, Mar. Pollut. Bull., 99, 35–42, 2015.
Passananti, M., Kong, L., Shang, J., Dupart, Y., Perrier, S., Chen, J., Donaldson, D. J., and George, C.: Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Fatty Acids and Long-Chain Alkenes, Angew. Chem. Int. Ed., 55, 10336–10339, 2016.
Pérez-Carrera, E., León, V. M. L., Parra, A. G., and González-Mazo, E.: Simultaneous determination of pesticides, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in seawater and interstitial marine water samples, using stir bar sorptive extraction–thermal desorption–gas chromatography–mass spectrometry, J. Chromatogr. A, 1170, 82–90, 2007.
Perraud, V., Horne, J. R., Martinez, A. S., Kalinowski, J., Meinardi, S., Dawson, M. L., Wingen, L. M., Dabdub, D., Blake, D. R., Gerber, R. B., and Finlayson-Pitts, B. J.: The future of airborne sulfur-containing particles in the absence of fossil fuel sulfur dioxide emissions, P. Natl. Acad. Sci. USA, 112, 13514–13519, https://doi.org/10.1073/pnas.1510743112, 2015.
Richards, S., Rudd, J., and Kelly, C.: Organic volatile sulfur in lakes ranging in sulfate and dissolved salt concentration over five orders of magnitude, Limnol. Oceanogr., 39, 562–572, 1994.
Richards-Henderson, N. K., Goldstein, A. H., and Wilson, K. R.: Sulfur dioxide accelerates the heterogeneous oxidation rate of organic aerosol by hydroxyl radicals, Environ. Sci. Technol. Lett., 50, 3554–3561, 2016.
Ridgeway, R. G., Thornton, D. C., and Bandy, A. R.: Determination of trace aqueous dimethylsulfoxide concentrations by isotope dilution gas chromatography/mass spectrometry: Application to rain and sea water, J. Atmos. Chem., 14, 53–60, 1992.
Riva, M., Tomaz, S., Cui, T., Lin, Y. H., Perraudin, E., Gold, A., Stone, E. A., Villenave, E., and Surratt, J. D.: Evidence for an unrecognized secondary anthropogenic source of organosulfates and sulfonates: gas-phase oxidation of polycyclic aromatic hydrocarbons in the presence of sulfate aerosol, Environ. Sci. Technol., 49, 6654–6664, https://doi.org/10.1021/acs.est.5b00836, 2015.
Riva, M., Da Silva Barbosa, T., Lin, Y.-H., Stone, E. A., Gold, A., and Surratt, J. D.: Chemical characterization of organosulfates in secondary organic aerosol derived from the photooxidation of alkanes, Atmos. Chem. Phys., 16, 11001–11018, https://doi.org/10.5194/acp-16-11001-2016, 2016.
Rosati, B., Christiansen, S., de Jonge, R. W., Roldin, P., Jensen, M. M., Wang, K., Moosakutty, S. P., Thomsen, D., Salomonsen, C., Hyttinen, N., Elm, J., Feilberg, A., Glasius, M., and Bilde, M.: New Particle Formation and Growth from Dimethyl Sulfide Oxidation by Hydroxyl Radicals, ACS Earth Space Chem., 5, 801–811, https://doi.org/10.1021/acsearthspacechem.0c00333, 2021.
Schobesberger, S., Junninen, H., Bianchi, F., Lonn, G., Ehn, M., Lehtipalo, K., Dommen, J., Ehrhart, S., Ortega, I. K., Franchin, A., Nieminen, T., Riccobono, F., Hutterli, M., Duplissy, J., Almeida, J., Amorim, A., Breitenlechner, M., Downard, A. J., Dunne, E. M., Flagan, R. C., Kajos, M., Keskinen, H., Kirkby, J., Kupc, A., Kurten, A., Kurten, T., Laaksonen, A., Mathot, S., Onnela, A., Praplan, A. P., Rondo, L., Santos, F. D., Schallhart, S., Schnitzhofer, R., Sipila, M., Tome, A., Tsagkogeorgas, G., Vehkamaki, H., Wimmer, D., Baltensperger, U., Carslaw, K. S., Curtius, J., Hansel, A., Petaja, T., Kulmala, M., Donahue, N. M., and Worsnop, D. R.: Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules, P. Natl. Acad. Sci. USA, 110, 17223–17228, https://doi.org/10.1073/pnas.1306973110, 2013.
Seidel, M., Manecki, M., Herlemann, D. P., Deutsch, B., Schulz-Bull, D., Jürgens, K., and Dittmar, T.: Composition and transformation of dissolved organic matter in the Baltic Sea, Front. Earth Sci., 5, 31, https://doi.org/10.3389/feart.2017.00031, 2017.
Shang, J., Passananti, M., Dupart, Y., Ciuraru, R., Tinel, L., Rossignol, S. p., Perrier, S. B., Zhu, T., and George, C.: SO2 Uptake on oleic acid: A new formation pathway of organosulfur compounds in the atmosphere, Environ. Sci. Technol. Lett., 3, 67–72, 2016.
Smith, S. J., Pitcher, H., and Wigley, T. M. L.: Global and regional anthropogenic sulfur dioxide emissions, Global Planet. Change, 29, 99–119, https://doi.org/10.1016/s0921-8181(00)00057-6, 2001.
Staudt, S., Kundu, S., Lehmler, H.-J., He, X., Cui, T., Lin, Y.-H., Kristensen, K., Glasius, M., Zhang, X., Weber, R. J., Surratt, J. D., and Stone, E. A.: Aromatic organosulfates in atmospheric aerosols: Synthesis, characterization, and abundance, Atmos. Environ., 94, 366–373, https://doi.org/10.1016/j.atmosenv.2014.05.049, 2014.
Stortini, A., Martellini, T., Del Bubba, M., Lepri, L., Capodaglio, G., and Cincinelli, A.: n-Alkanes, PAHs and surfactants in the sea surface microlayer and sea water samples of the Gerlache Inlet sea (Antarctica), Microchem. J., 92, 37–43, 2009.
Styler, S. A., Loiseaux, M.-E., and Donaldson, D. J.: Substrate effects in the photoenhanced ozonation of pyrene, Atmos. Chem. Phys., 11, 1243–1253, https://doi.org/10.5194/acp-11-1243-2011, 2011.
Tao, S., Lu, X., Levac, N., Bateman, A. P., Nguyen, T. B., Bones, D. L., Nizkorodov, S. A., Laskin, J., Laskin, A., and Yang, X.: Molecular characterization of organosulfates in organic aerosols from Shanghai and Los Angeles urban areas by nanospray-desorption electrospray ionization high-resolution mass spectrometry, Environ. Sci. Technol., 48, 10993–11001, 2014.
Urbanski, S., Stickel, R., and Wine, P.: Mechanistic and kinetic study of the gas-phase reaction of hydroxyl radical with dimethyl sulfoxide, J. Phys. Chem. A, 102, 10522–10529, 1998.
Vácha, R., Jungwirth, P., Chen, J., and Valsaraj, K.: Adsorption of polycyclic aromatic hydrocarbons at the air–water interface: Molecular dynamics simulations and experimental atmospheric observations, Phys. Chem. Chem. Phys., 8, 4461–4467, 2006.
Valavanidis, A., Vlachogianni, T., Triantafillaki, S., Dassenakis, M., Androutsos, F., and Scoullos, M.: Polycyclic aromatic hydrocarbons in surface seawater and in indigenous mussels (Mytilus galloprovincialis) from coastal areas of the Saronikos Gulf (Greece), Estuar. Coast. Shelf Sci., 79, 733–739, 2008.
von Sonntag, C., Dowideit, P., Fang, X., Mertens, R., Pan, X., Schuchmann, M. N., and Schuchmann, H.-P.: The fate of peroxyl radicals in aqueous solution, Water Sci. Technol., 35, 9–15, 1997.
Wang, Y., Zhang, Q., Jiang, J., Zhou, W., Wang, B., He, K., Duan, F., Zhang, Q., Philip, S., and Xie, Y.: Enhanced sulfate formation during China's severe winter haze episode in January 2013 missing from current models, J. Geophys. Res.-Atmos., 119, 10425–10440, https://doi.org/10.1002/2013jd021426, 2014.
Wang, Y., Mekic, M., Li, P., Deng, H., Liu, S., Jiang, B., Jin, B., Vione, D., and Gligorovski, S.: Ionic Strength Effect Triggers Brown Carbon Formation through Heterogeneous Ozone Processing of Ortho-Vanillin, Environ. Sci. Technol., 55, 4553–4564, https://doi.org/10.1021/acs.est.1c00874, 2021.
Weigend, F.: Accurate Coulomb-fitting basis sets for H to Rn, Phys. Chem. Chem. Phys., 8, 1057–1065, 2006.
Weigend, F. and Ahlrichs, R.: Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy, Phys. Chem. Chem. Phys., 7, 3297–3305, 2005.
Wilkinson, F., Helman, W. P., and Ross, A. B.: Rate constants for the decay and reactions of the lowest electronically excited singlet state of molecular oxygen in solution. An expanded and revised compilation, J. Phys. Chem. Ref. Data, 24, 663–677, 1995.
Yassine, M. M., Harir, M., Dabek-Zlotorzynska, E., and Schmitt-Kopplin, P.: Structural characterization of organic aerosol using Fourier transform ion cyclotron resonance mass spectrometry: aromaticity equivalent approach, Rapid Commun. Mass Spectrom., 28, 2445–2454, 2014.
Zhang, L., Kuniyoshi, I., Hirai, M., and Shoda, M.: Oxidation of dimethyl sulfide byPseudomonas acidovorans DMR-11 isolated from peat biofilter, Biotechnol. Lett, 13, 223–228, 1991.
Zhang, M., Gao, W., Yan, J., Wu, Y., Marandino, C. A., Park, K., Chen, L., Lin, Q., Tan, G., and Pan, M.: An integrated sampler for shipboard underway measurement of dimethyl sulfide in surface seawater and air, Atmos. Environ., 209, 86–91, 2019.
Zhang, S. H., Yang, G. P., Zhang, H. H., and Yang, J.: Spatial variation of biogenic sulfur in the south Yellow Sea and the East China Sea during summer and its contribution to atmospheric sulfate aerosol, Sci. Total Environ., 488–489, 157–167, https://doi.org/10.1016/j.scitotenv.2014.04.074, 2014.
Zhang, Y., Wang, Y., Gray, B. A., Gu, D., Mauldin, L., Cantrell, C., and Bandy, A.: Surface and free tropospheric sources of methanesulfonic acid over the tropical Pacific Ocean, Geophys. Res. Lett., 41, 5239–5245, https://doi.org/10.1002/2014gl060934, 2014.
Zhao, H., Jiang, X., and Du, L.: Contribution of methane sulfonic acid to new particle formation in the atmosphere, Chemosphere, 174, 689–699, https://doi.org/10.1016/j.chemosphere.2017.02.040, 2017.
Zhao, Y. and Truhlar, D. G.: The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals, Theor. Chem. Acc., 120, 215–241, 2008.
Zhou, S., Hwang, B. C. H., Lakey, P. S. J., Zuend, A., Abbatt, J. P. D., and Shiraiwa, M.: Multiphase reactivity of polycyclic aromatic hydrocarbons is driven by phase separation and diffusion limitations, P. Natl. Acad. Sci. USA, 116, 11658–11663, https://doi.org/10.1073/pnas.1902517116, 2019.
Zhu, M., Jiang, B., Li, S., Yu, Q., Yu, X., Zhang, Y., Bi, X., Yu, J., George, C., and Yu, Z.: Organosulfur Compounds Formed from Heterogeneous Reaction between SO2 and Particulate-Bound Unsaturated Fatty Acids in Ambient Air, Environ. Sci. Technol. Lett., 6, 318–322, 2019.
Heterogeneous oxidation of SO2 is suggested to be one of the most important pathways for sulfate formation during extreme haze events in China, yet the exact mechanism remains highly uncertain. Our study reveals that ubiquitous compounds at the sea surface PAHS and DMSO, when exposed to SO2 under simulated sunlight irradiation, generate abundant organic sulfur compounds, providing implications for air-sea interaction and secondary organic aerosols formation processes.
Heterogeneous oxidation of SO2 is suggested to be one of the most important pathways for sulfate...