Reactivity of liquid and semisolid secondary organic carbon with chloride and nitrate in atmospheric aerosols.
Constituents of secondary organic carbon (SOC) in atmospheric aerosols are often mixed with inorganic components and compose a significant mass fraction of fine particulate matter in the atmosphere. Interactions between SOC and other condensed-phase species are not well understood. Here, we investigate the reactions of liquid-like and semisolid SOC from ozonolysis of limonene (LSOC) and α-pinene (PSOC) with NaCl using a set of complementary microspectroscopic analyses. These reactions result in chloride depletion in the condensed phase, release of gaseous HCl, and formation of organic salts. The reactions attributed to acid displacement by SOC acidic components are driven by the high volatility of HCl. Similar reactions can take place in SOC/NaNO3 particles. The results show that an increase in SOC mass fraction in the internally mixed SOC/NaCl particles leads to higher chloride depletion. Glass transition temperatures and viscosity of PSOC were estimated for atmospherically relevant conditions. Data show that the reaction extent depends on SOC composition, particle phase state and viscosity, mixing state, temperature, relative humidity (RH), and reaction time. LSOC shows slightly higher potential to deplete chloride than PSOC. Higher particle viscosity at low temperatures and RH can hinder these acid displacement reactions. Formation of organic salts from these overlooked reactions can alter particle physiochemical properties and may affect their reactivity and ability to act as cloud condensation and ice nuclei. The release and potential recycling of HCl and HNO3 from reacted aerosol particles may have important implications for atmospheric chemistry.
†Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354 United States.
Bingbing
B
Wang
‡Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.|§Department of Chemistry, University of the Pacific, Stockton, California 95211, United States.
Rachel E
RE
O'Brien
‡Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Stephen T
ST
Kelly
∥Atmospheric Sciences and Global Change Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States.
John E
JE
Shilling
§Department of Chemistry, University of the Pacific, Stockton, California 95211, United States.
Ryan C
RC
Moffet
‡Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Mary K
MK
Gilles
†Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354 United States.
Alexander
A
Laskin
D000336:Aerosols / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry*; D000081008:Bicyclic Monoterpenes; D002244:Carbon / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry*; D053138:Cyclohexenes / Q000737:chemistry; D004058:Diffusion; D005740:Gases / Q000737:chemistry; D005898:Glass / Q000737:chemistry; D006813:Humidity; D000077222:Limonene; D039821:Monoterpenes / Q000737:chemistry; D009566:Nitrates / Q000737:chemistry*; D013729:Terpenes / Q000737:chemistry; D013997:Time Factors; D044366:Transition Temperature; D014783:Viscosity
D000336:Aerosols; D000081008:Bicyclic Monoterpenes; D002712:Chlorides; D053138:Cyclohexenes; D005740:Gases; D039821:Monoterpenes; D009566:Nitrates; D013729:Terpenes; D002244:Carbon; D000077222:Limonene; C005451:alpha-pinene