Impact of biogenic secondary organic aerosol (SOA) loading on the molecular composition of wintertime PM2.5 in urban Tianjin: an insight from Fourier transform ion cyclotron resonance mass spectrometry

Abstract. Biomass burning is one of the key sources of urban aerosols in the North China Plain, especially during winter, when the impact of secondary organic aerosols (SOAs) formed from biogenic volatile organic compounds (BVOCs) is generally considered to be minor. However, little is known about the influence of biogenic SOA loading on the molecular composition of wintertime organic aerosols. Here, we investigated the water-soluble organic compounds in fine particulate matter (PM2.5) from urban Tianjin by ultrahigh-resolution Fourier transform ion cyclotron resonanc mass spectrometry (FT-ICR MS). Our results show that most of the CHO and CHON compounds are derived from biomass burning which are poor in oxygen and contain aromatic rings that probably contribute to light-absorbing brown carbon (BrC) chromophores. Under moderate to high SOA-loading conditions, the nocturnal chemistry is more efficient than photooxidation to generate secondary CHO and CHON compounds with high oxygen content. Under low SOA loading, secondary CHO and CHON compounds with low oxygen content are mainly formed by photochemistry. Secondary CHO compounds are mainly derived from oxidation of monoterpenes. However, nocturnal chemistry may be more productive to sesquiterpene-derived CHON compounds. In contrast, the number- and intensity-weight of S-containing groups (CHOS and CHONS) increased significantly with the increase of biogenic SOA loading, which agrees with the fact that a majority of the S-containing groups are identified as organosulfates (OSs) and nitrooxy–organosulfates (nitrooxy–OSs) that are derived from the oxidation of BVOCs. Terpenes may be potential major contributors to organosulfates and nitrooxy–organosulfates. While the nocturnal chemistry is more beneficial to the formation of organosulfates and nitrooxy–organosulfates under low SOA loading. The SOA loading is an important factor that is associated with the oxidation degree, nitrate group content and chemodiversity of nitrooxy-organosulfates. Furthermore, our study suggests that the hydrolysis of nitrooxy-organosulfates is a possible pathway for the formation of organosulfates.

[1]  G. Jiang,et al.  Deciphering dissolved organic matter by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS): from bulk to fractions and individuals , 2022, Carbon Research.

[2]  Zifa Wang,et al.  Measurement report: Optical properties and sources of water-soluble brown carbon in Tianjin, North China – insights from organic molecular compositions , 2022, Atmospheric Chemistry and Physics.

[3]  G. Jiang,et al.  Deciphering 13C and 34S Isotopes of Organosulfates in Urban Aerosols by FT-ICR Mass Spectrometry , 2022, Environmental Science & Technology Letters.

[4]  D. Uhrín,et al.  A New Structural Classification Scheme for Dissolved Organic Sulfur in Urban Snow from North China , 2022, Environmental Science & Technology Letters.

[5]  Hai Guo,et al.  Secondary organic aerosol formed by condensing anthropogenic vapours over China’s megacities , 2022, Nature Geoscience.

[6]  J. Penner,et al.  Brown carbon from biomass burning imposes strong circum-Arctic warming , 2022, One Earth.

[7]  Zhiliang Zhu,et al.  A review of secondary organic aerosols formation focusing on organosulfates and organic nitrates. , 2022, Journal of hazardous materials.

[8]  P. Fu,et al.  Source and formation process impact the chemodiversity of rainwater dissolved organic matter along the Yangtze River Basin in summer. , 2021, Water research.

[9]  P. Fu,et al.  Acidification impacts on the molecular composition of dissolved organic matter revealed by FT-ICR MS. , 2021, The Science of the total environment.

[10]  Gan Zhang,et al.  Molecular Dynamics and Light Absorption Properties of Atmospheric Dissolved Organic Matter. , 2021, Environmental science & technology.

[11]  Yuchen Wang,et al.  Chemical Synthesis of Multifunctional Air Pollutants: Terpene-Derived Nitrooxy Organosulfates. , 2021, Environmental science & technology.

[12]  P. Fu,et al.  Overview of biological ice nucleating particles in the atmosphere. , 2020, Environment international.

[13]  G. Jiang,et al.  Molecular characterization of firework-related urban aerosols using Fourier transform ion cyclotron resonance mass spectrometry , 2020 .

[14]  U. Feudel,et al.  ICBM-OCEAN: Processing ultrahigh-resolution mass spectrometry data of complex molecular mixtures. , 2020, Analytical chemistry.

[15]  L. Poulain,et al.  Organosulfates in Ambient Aerosol: State of Knowledge and Future Research Directions on Formation, Abundance, Fate, and Importance. , 2020, Environmental science & technology.

[16]  Yu Song,et al.  Enhancement in Particulate Organic Nitrogen and Light Absorption of Humic-like Substances over Tibetan Plateau due to Long-Range Transported Biomass Burning Emissions. , 2019, Environmental science & technology.

[17]  Zifa Wang,et al.  Large contributions of biogenic and anthropogenic sources to fine organic aerosols in Tianjin, North China , 2019, Atmospheric Chemistry and Physics.

[18]  G. Jiang,et al.  Molecular characterization of water-soluble organic compounds in PM2.5 using ultrahigh resolution mass spectrometry. , 2019, The Science of the total environment.

[19]  B. Jiang,et al.  Organosulfur Compounds Formed from Heterogeneous Reaction between SO2 and Particulate-Bound Unsaturated Fatty Acids in Ambient Air , 2019, Environmental Science & Technology Letters.

[20]  P. Hopke,et al.  Quantifying primary and secondary humic-like substances in urban aerosol based on emission source characterization and a source-oriented air quality model , 2019, Atmospheric Chemistry and Physics.

[21]  C. N. Hewitt,et al.  Introduction to the special issue “In-depth study of air pollution sources and processes within Beijing and its surrounding region (APHH-Beijing)” , 2018, Atmospheric Chemistry and Physics.

[22]  L. Deguillaume,et al.  Molecular Characterization of Cloud Water Samples Collected at the Puy de Dôme (France) by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. , 2018, Environmental science & technology.

[23]  P. Peng,et al.  Molecular Characterization of Water-Soluble Humic like Substances in Smoke Particles Emitted from Combustion of Biomass Materials and Coal Using Ultrahigh-Resolution Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. , 2018, Environmental science & technology.

[24]  J. Jimenez,et al.  Non-methane organic gas emissions from biomass burning: identification, quantification, and emission factors from PTR-ToF during the FIREX 2016 laboratory experiment , 2017 .

[25]  A. Robinson,et al.  Review of Urban Secondary Organic Aerosol Formation from Gasoline and Diesel Motor Vehicle Emissions. , 2017, Environmental science & technology.

[26]  P. Peng,et al.  Comprehensive characterization of humic-like substances in smoke PM 2.5 emitted from the combustion of biomass materials and fossil fuels , 2016 .

[27]  A. Laskin,et al.  Molecular Characterization of Brown Carbon in Biomass Burning Aerosol Particles. , 2016, Environmental science & technology.

[28]  J. G. Levine,et al.  Molecular composition of organic aerosols in central Amazonia: An ultra-high-resolution mass spectrometry study , 2016 .

[29]  D. Volmer,et al.  Shedding light on the structures of lignin compounds: photo-oxidation under artificial UV light and characterization by high resolution mass spectrometry , 2016, Analytical and Bioanalytical Chemistry.

[30]  A. Gold,et al.  Chemical characterization of organosulfates in secondary organic aerosol derived from the photooxidation of alkanes , 2016 .

[31]  D. Donaldson,et al.  Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Fatty Acids and Long-Chain Alkenes. , 2016, Angewandte Chemie.

[32]  T. Hoffmann,et al.  Real-time detection of highly oxidized organosulfates and BSOA marker compounds during the F-BEACh 2014 field study , 2016 .

[33]  Seungshik Park,et al.  Chemical and light absorption properties of humic-like substances from biomass burning emissions under controlled combustion experiments , 2016 .

[34]  M. Johnston,et al.  Characterization of Highly Oxidized Molecules in Fresh and Aged Biogenic Secondary Organic Aerosol. , 2016, Analytical chemistry.

[35]  Jianmin Chen,et al.  Molecular characterization of atmospheric particulate organosulfates in three megacities at the middle and lower reaches of the Yangtze River , 2016 .

[36]  M. Shao,et al.  Characteristics of ambient volatile organic compounds and the influence of biomass burning at a rural site in Northern China during summer 2013 , 2016 .

[37]  J. Doussin,et al.  Molecular composition of fresh and aged secondary organic aerosol from a mixture of biogenic volatile compounds: a high-resolution mass spectrometry study , 2015 .

[38]  G. B. Avery,et al.  Characterization of CHOS compounds in rainwater from continental and coastal storms by ultrahigh resolution mass spectrometry , 2015 .

[39]  A. Laskin,et al.  Molecular characterization of organosulfates in organic aerosols from Shanghai and Los Angeles urban areas by nanospray-desorption electrospray ionization high-resolution mass spectrometry. , 2014, Environmental science & technology.

[40]  M. Dubey,et al.  Brownness of organics in aerosols from biomass burning linked to their black carbon content , 2014 .

[41]  A. Hallar,et al.  Atmospheric organic matter in cl ud : exact masses and molecular formula identification using ultrahigh resolution FT-ICR mass spectrometry , 2013 .

[42]  M. Glasius,et al.  Dimers in α-pinene secondary organic aerosol: effect of hydroxyl radical, ozone, relative humidity and aerosol acidity , 2013 .

[43]  Stephen J. Fuller,et al.  Molecular composition of biogenic secondary organic aerosols using ultrahigh resolution mass spectrometry: comparing laboratory and field studies , 2013 .

[44]  J. Collett,et al.  Speciation of “brown” carbon in cloud water impacted by agricultural biomass burning in eastern China , 2013 .

[45]  Yele Sun,et al.  Aerosol composition, sources and processes during wintertime in Beijing, China , 2013 .

[46]  R. Weber,et al.  Sources, composition and absorption Ångström exponent of light-absorbing organic components in aerosol extracts from the Los Angeles Basin. , 2013, Environmental science & technology.

[47]  K. Finster,et al.  Hailstones: A Window into the Microbial and Chemical Inventory of a Storm Cloud , 2013, PloS one.

[48]  Ge Yu,et al.  Evidence and quantitation of aromatic organosulfates in ambient aerosols in Lahore, Pakistan , 2012 .

[49]  J. Yu,et al.  Organosulfates in humic-like substance fraction isolated from aerosols at seven locations in East Asia: a study by ultra-high-resolution mass spectrometry. , 2012, Environmental science & technology.

[50]  H. Tanimoto,et al.  Diurnal variations of organic molecular tracers and stable carbon isotopic composition in atmospheric aerosols over Mt. Tai in the North China Plain: an influence of biomass burning , 2012 .

[51]  R. Zaveri,et al.  Hydrolysis of Organonitrate Functional Groups in Aerosol Particles , 2012 .

[52]  A. Goldstein,et al.  Formation and occurrence of dimer esters of pinene oxidation products in atmospheric aerosols , 2012 .

[53]  J. Seinfeld,et al.  Organosulfates as Tracers for Secondary Organic Aerosol (SOA) Formation from 2-Methyl-3-Buten-2-ol (MBO) in the Atmosphere , 2012, Environmental science & technology.

[54]  J. Neirynck,et al.  Chemical characterisation of atmospheric aerosols during a 2007 summer field campaign at Brasschaat, Belgium: sources and source processes of biogenic secondary organic aerosol , 2012 .

[55]  B. Turpin,et al.  Contribution of organosulfur compounds to organic aerosol mass. , 2009, Environmental science & technology.

[56]  M. Glasius,et al.  Organosulfates and oxidation products from biogenic hydrocarbons in fine aerosols from a forest in North West Europe during spring , 2011 .

[57]  M. J. Elrod,et al.  Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates , 2011 .

[58]  J. Seinfeld,et al.  Mass spectrometric characterization of isomeric terpenoic acids from the oxidation of α-pinene, β-pinene, d-limonene, and Δ3-carene in fine forest aerosol. , 2011, Journal of mass spectrometry : JMS.

[59]  Jared D. Smith,et al.  Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol. , 2011, Nature chemistry.

[60]  J. Seinfeld,et al.  Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene , 2010 .

[61]  J. D. de Gouw,et al.  Contribution of isoprene-derived organosulfates to free tropospheric aerosol mass , 2010, Proceedings of the National Academy of Sciences.

[62]  H. Herrmann,et al.  Methyl-nitrocatechols: atmospheric tracer compounds for biomass burning secondary organic aerosols. , 2010, Environmental science & technology.

[63]  M. Claeys,et al.  Terpenylic acid and related compounds: precursors for dimers in secondary organic aerosol from the ozonolysis of α- and β-pinene , 2010 .

[64]  Stelios Kazadzis,et al.  Inferring absorbing organic carbon content from AERONET data , 2010 .

[65]  J. Yu,et al.  Humic-like substances in fresh emissions of rice straw burning and in ambient aerosols in the Pearl River Delta Region, China , 2010 .

[66]  B. Finlayson‐Pitts,et al.  Identification of organic nitrates in the NO3 radical initiated oxidation of alpha-pinene by atmospheric pressure chemical ionization mass spectrometry. , 2010, Environmental science & technology.

[67]  John H. Seinfeld,et al.  The formation, properties and impact of secondary organic aerosol: current and emerging issues , 2009 .

[68]  Barbara J. Turpin,et al.  Oligomers, organosulfates, and nitrooxy organosulfates in rainwater identified by ultra-high resolution electrospray ionization FT-ICR mass spectrometry , 2008 .

[69]  John H Seinfeld,et al.  Organosulfate formation in biogenic secondary organic aerosol. , 2008, The journal of physical chemistry. A.

[70]  John H. Seinfeld,et al.  Secondary organic aerosol (SOA) formation from reaction of isoprene with nitrate radicals (NO 3 ) , 2008 .

[71]  R. Sleighter,et al.  Molecular characterization of dissolved organic matter (DOM) along a river to ocean transect of the lower Chesapeake Bay by ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry , 2008 .

[72]  T. Sharkey,et al.  Isoprene emission from plants: why and how. , 2007, Annals of botany.

[73]  Edward O. Edney,et al.  Estimates of the contributions of biogenic and anthropogenic hydrocarbons to secondary organic aerosol at a southeastern US location , 2007 .

[74]  T. Hoffmann,et al.  Unambiguous identification of esters as oligomers in secondary organic aerosol formed from cyclohexene and cyclohexene/α-pinene ozonolysis , 2007 .

[75]  Conny Müller,et al.  Evidence for the existence of organosulfates from beta-pinene ozonolysis in ambient secondary organic aerosol. , 2007, Environmental science & technology.

[76]  A. Goldstein,et al.  Known and Unexplored Organic Constituents in the Earth's Atmosphere , 2007 .

[77]  M. Claeys,et al.  Hydroxydicarboxylic acids: markers for secondary organic aerosol from the photooxidation of alpha-pinene. , 2007, Environmental science & technology.

[78]  J. Ortega,et al.  Sesquiterpene emissions from loblolly pine and their potential contribution to biogenic aerosol formation in the Southeastern US , 2006 .

[79]  T. Dittmar,et al.  From mass to structure: an aromaticity index for high‐resolution mass data of natural organic matter , 2006 .