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Rising Importance of Organosulfur Species for Aerosol Properties and Future 2 Air Quality

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Rising Importance of Organosulfur Species for Aerosol Properties and Future 2 Air Quality 1 Rising Importance of Organosulfur Species for Aerosol Properties and Future 2 Air Quality 3 M. Riva1,#,¥,*, Y. Chen1,¥, Y. Zhang1,2, Z. Lei3, N. E. Olson4, H. C. Boyer Chelmo5, S. Narayan5, 4 L. D. Yee6, H. S. Green1,‡, T. Cui1, Z. Zhang1, K. Baumann7, M. Fort7, E. Edgerton7, S. H. 5 Budisulistiorini1,†, C. A. Rose1, I. O. Ribeiro8, R. L. e Oliveira8, E. O. dos Santos9, C. M. D. 6 Machado9, S. Szopa10, Y. Zhao11,§, E. G. Alves12, S. S. de Sá13, W. Hu14, E. M. Knipping15, S. L. 7 Shaw16, S. Duvoisin Junior8, R. A. F. de Souza8, B.B. Palm,14 J. L. Jimenez14, M. Glasius17, A. 8 H. Goldstein6, H. O. T. Pye1,18, A. Gold1, B. J. Turpin1, W. Vizuete1, S. T. Martin13,19, J. A. 10 5 3,4* 1* 9 Thornton , C. S. Dutcher , A. P. Ault , and J. D. Surratt 10 Affiliations: 11 1 Department of Environmental Sciences and Engineering, Gillings School of Global Public 12 Health, The University of North Carolina at Chapel Hill, Chapel Hill, NC, USA. 13 2 Aerodyne Research Inc., Billerica, MA, USA. 14 3 Department of Environmental Health Sciences, University of Michigan, Ann Arbor, MI, USA. 15 4 Department of Chemistry, University of Michigan, Ann Arbor, MI, USA. 16 5 Department of Mechanical Engineering, University of Minnesota-Twin Cities, Minneapolis, 17 MN, USA. 18 6 Department of Environmental Science, Policy, and Management, University of California, 19 Berkeley, CA, USA. 20 7 Atmospheric Research & Analysis, Inc., Cary, NC, USA. 21 8 Escola Superior de Tecnologia, Universidade do Estado do Amazonas, Manaus, Amazonas, 22 Brasil. 23 9 Department of Chemistry, Federal University of Amazonas, Manaus, Amazonas, Brazil. 24 10 Laboratoire des Sciences du Climat et de l'Environnement, CEA-CNRS-UVSQ-IPSL, Gif-sur- 25 Yvette, France. 26 11 Department of Atmospheric Sciences, University of Washington, Seattle, WA, USA. 27 12 Environment Dynamics Department, National Institute of Amazonian Research (INPA), 28 Manaus, Brazil. 29 13 John A. Paulson School of Engineering and Applied Sciences, Harvard University, 30 Cambridge, MA, USA. 31 14 Department of Chemistry and Cooperative Institute for Research in Environmental Sciences, 32 University of Colorado, Boulder, CO, USA. 33 15 Electric Power Research Institute, Washington, D.C, USA. 34 16 Electric Power Research Institute, Palo Alto, CA, USA. 35 17 Aarhus University, Dept. of Chemistry and iNANO, 8000 Aarhus C, Denmark. 1 36 18 National Exposure Research Laboratory, US Environmental Protection Agency, Research 37 Triangle Park, NC, USA. 38 19 Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA, USA. 39 40 # Now at the Univ Lyon, Université Claude Bernard Lyon 1, CNRS, IRCELYON, F-69626, 41 Villeurbanne, France. 42 43 ‡ Now at Department of Food Science and Technology, University of California, Davis, Davis, 44 CA, USA. 45 46 † Now at Earth Observatory of Singapore, Nanyang Technological University, Singapore 47 639798, Singapore. 48 49 § Now at School of Environmental Science and Engineering, Shanghai Jiao Tong University, 50 Shanghai, 200240, China. 51 52 ¥ These authors contributed equally to this work 53 54 *E-mail (M. R.): [email protected] 55 *E-mail (A. P. A): [email protected] 56 *E-mail (J. D. S): [email protected] 2 57 Abstract 58 Acid-driven multiphase chemistry of isoprene epoxydiols (IEPOX), a key isoprene oxidation 59 product, with inorganic sulfate aerosol yields substantial amounts of secondary organic aerosol 60 (SOA) through the formation of organosulfur. The extent and implications of inorganic-to- 61 organic sulfate conversion, however, are unknown. Herein, we reveal that extensive consumption 62 of inorganic sulfate occurs, which increases with the IEPOX-to-inorganic sulfate ratio (IEPOX: 63 Sulfinorg), as determined by laboratory and field measurements. We further demonstrate that 64 organosulfur greatly modifies critical aerosol properties, such as acidity, morphology, viscosity, 65 and phase state. These new mechanistic insights reveal that changes in SO2 emissions, especially 66 in isoprene-dominated environments, will significantly alter biogenic SOA physicochemical 67 properties. Consequently, IEPOX:Sulfinorg will play a central role in understanding historical 68 climate and determining future impacts of biogenic SOA on global climate and air quality. 3 69 Secondary organic aerosol (SOA) formed through the oxidation of volatile organic compounds is 70 a major and globally ubiquitous component of atmospheric fine particulate matter (PM2.5: aerosol 71 particles ≤ 2.5 μm in aerodynamic diameter).1 Aerosol chemical composition and 72 physicochemical properties, such as viscosity and phase state, play a central role in terms of the 73 effects of SOA on air quality and climate.2 Understanding how SOA forms and interacts with 74 other gas- and particle-phase species is crucial to accurately evaluating its importance in the 75 Earth’s climate system and adverse effects on public health. 2- - 76 Inorganic sulfate species (e.g., SO4 , HSO4 ) are also a significant PM2.5 component with 77 the capacity to impact atmospheric composition and climate, in part, because of its predicted 78 impact on aerosol acidity, hygroscopicity, visibility and cloud nucleation.1,3 The oxidation of 79 sulfur dioxide (SO2) to sulfuric acid (H2SO4) increases aerosol acidity, which enhances SOA 80 formation.4–7 Sulfur (S(VI)) in aerosols was generally assumed to be primarily present as 2- - 81 inorganic sulfate (SO4 and HSO4 ) ions until more recent studies revealed the presence of 8–12 82 organosulfur components in PM2.5. Despite observations that organosulfur compounds are 83 important contributors to SOA mass in a range of environments globally,13–18 estimations of 84 aerosol acidity and liquid water content typically assume that only inorganic sulfate plays a 85 role.19 Correctly identifying the chemical form of sulfate (i.e., inorganic vs. organic), and 86 representing it accurately in atmospheric models is essential as the different forms lead to 87 different aerosol physicochemical properties that will have different predicted impacts on air 88 quality and climate.2 89 Laboratory studies have demonstrated that acid-driven multiphase chemistry (i.e., 90 reactive uptake) of isoprene epoxydiols (IEPOX) is key to explaining the chemical form and 91 extent of SOA formation from photochemical oxidation of isoprene 20–23 and field measurements 4 92 have confirmed this is the predominant pathway.24–29 While chamber studies have shown that 93 organosulfur compounds, specifically organosulfates (OS) 30 formed by the reactive uptake of 94 IEPOX with particulate inorganic sulfate, contribute significantly to IEPOX-SOA,31,32 the extent 95 and implications of sulfate conversion to organic forms have remained unknown. 96 Combined laboratory, field, and modeling studies described herein reveal a hitherto 97 unrecognized impact of the acid-driven multiphase chemistry of IEPOX, specifically substantial 98 conversion of inorganic sulfate to organosulfur compounds. Laboratory experiments show for 99 higher IEPOX:Sulfinorg ratios (e.g., Amazon) increase sulfate conversion versus lower ratios (e.g., 100 southeastern U.S. (SE-U.S.)). Future sulfate reductions in the Northern Hemisphere are expected 101 to greatly increase the fraction of inorganic sulfate converted. This was likely also the case for 102 pre-industrial conditions, when inorganic sulfate was much lower. In sum, these major changes 103 in the SOA chemical composition due to IEPOX reactive uptake govern aerosol physicochemical 104 properties. 105 Uncharted IEPOX conversion of inorganic sulfate to organosulfur. Despite the wealth of 106 studies on the reactive uptake of IEPOX, its reactivity remains poorly constrained.22,23,26,31,33,34 107 We performed controlled chamber experiments in the presence of ammonium bisulfate (ABS) 108 seed particles (pH = 1.5) at ~50 % relative humidity (RH) using atmospherically-relevant ratios 109 of IEPOX:Sulfinorg (Table S1). Fig. 1 shows that immediately following IEPOX addition, rapid 110 conversion of inorganic sulfate is observed under all conditions measured by a particle-into- 111 liquid sampler (PILS) coupled to an ion chromatograph (IC) with 5 minute resolution. This 112 depletion is correlated to IEPOX-OS and oligomeric-OS (quantified by liquid chromatography 113 coupled to electrospray ionization high-resolution mass spectrometry (LC/ESI-HR-MS) from the 114 same PILS samples), which is supported by computational modeling.35 IEPOX-OS accounts for 5 115 most (90-100%) of the converted sulfate within the first 40-60 min under conditions that mimic 116 IEPOX:Sulfinorg ratios relevant to both the SE-U.S. (Fig. 1A) and the Amazon (Fig. 1B). As 117 shown in Fig. 1A and B ~40% of inorganic sulfate injected into the chamber is converted to 118 organosulfur under SE-U.S. conditions, while up to 90% is converted to organosulfur under 119 Amazonian conditions. One hour following IEPOX injection, stabilization of inorganic sulfate 120 commences, indicating that IEPOX uptake is inhibited due to various reasons described further 121 below. One possibility is the presence of organic coating as suggested in recent studies.32,36 122 Meanwhile, the concentrations of IEPOX-OS start to decrease in all experiments. A net 123 reduction (up to 30% in one hour) of the three quantified OS species indicates that IEPOX-OS 124 are not stable and react to yield as yet uncharacterized organosulfur compounds. One potential 125 class of species, sulfur-containing oligomers, were observed below quantifiable levels in the 126 positive ion mode. 127 Interestingly the conversion of inorganic-to-organic sulfate appears to be mainly driven 128 by the IEPOX:Sulfinorg ratio as illustrated in Fig. 1C. Indeed, our results clearly demonstrate that 129 the conversion fraction of inorganic to organosulfur correlate with the initial concentrations of 130 IEPOX and inorganic sulfate. Hence, IEPOX:Sulfinorg ratio is a critical and previously uncharted 131 factor in the conversion of inorganic-to-organic sulfate. High IEPOX:Sulfinorg ratios (>2) are 132 common over large geographic areas globally, as shown in Fig.
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