Biomaterial Database

Organosulfate formation in biogenic secondary organic aerosol. 2008

Jason D Surratt, and Yadian Gómez-González, and Arthur W H Chan, and Reinhilde Vermeylen, and Mona Shahgholi, and Tadeusz E Kleindienst, and Edward O Edney, and John H Offenberg, and Michael Lewandowski, and Mohammed Jaoui, and Willy Maenhaut, and Magda Claeys, and Richard C Flagan, and John H Seinfeld

Department of Chemistry, California Institute of Technology, Pasadena, California 91125, USA.

Organosulfates of isoprene, alpha-pinene, and beta-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive series of laboratory photooxidation (i.e., OH-initiated oxidation) and nighttime oxidation (i.e., NO3-initiated oxidation under dark conditions) experiments using nine monoterpenes (alpha-pinene, beta-pinene, d-limonene, l-limonene, alpha-terpinene, gamma-terpinene, terpinolene, Delta(3)-carene, and beta-phellandrene) and three monoterpenes (alpha-pinene, d-limonene, and l-limonene), respectively. Organosulfates were characterized using liquid chromatographic techniques coupled to electrospray ionization combined with both linear ion trap and high-resolution time-of-flight mass spectrometry. Organosulfates are formed only when monoterpenes are oxidized in the presence of acidified sulfate seed aerosol, a result consistent with prior work. Archived laboratory-generated isoprene SOA and ambient filter samples collected from the southeastern U.S. were reexamined for organosulfates. By comparing the tandem mass spectrometric and accurate mass measurements collected for both the laboratory-generated and ambient aerosol, previously uncharacterized ambient organic aerosol components are found to be organosulfates of isoprene, alpha-pinene, beta-pinene, and limonene-like monoterpenes (e.g., myrcene), demonstrating the ubiquity of organosulfate formation in ambient SOA. Several of the organosulfates of isoprene and of the monoterpenes characterized in this study are ambient tracer compounds for the occurrence of biogenic SOA formation under acidic conditions. Furthermore, the nighttime oxidation experiments conducted under highly acidic conditions reveal a viable mechanism for the formation of previously identified nitrooxy organosulfates found in ambient nighttime aerosol samples. We estimate that the organosulfate contribution to the total organic mass fraction of ambient aerosol collected from K-puszta, Hungary, a field site with a similar organosulfate composition as that found in the present study for the southeastern U.S., can be as high as 30%.

UI	MeSH Term	Description	Entries
D010084	Oxidation-Reduction	A chemical reaction in which an electron is transferred from one molecule to another. The electron-donating molecule is the reducing agent or reductant; the electron-accepting molecule is the oxidizing agent or oxidant. Reducing and oxidizing agents function as conjugate reductant-oxidant pairs or redox pairs (Lehninger, Principles of Biochemistry, 1982, p471).	Redox,Oxidation Reduction
D010420	Pentanes	Five-carbon saturated hydrocarbon group of the methane series. Include isomers and derivatives.	Isopentanes
D010777	Photochemistry	A branch of physical chemistry which studies chemical reactions, isomerization and physical behavior that may occur under the influence of visible and/or ultraviolet light.	Photochemistries
D002070	Butadienes	Four carbon unsaturated hydrocarbons containing two double bonds.	Butadiene Derivative,Butadiene Derivatives,Derivative, Butadiene,Derivatives, Butadiene
D002853	Chromatography, Liquid	Chromatographic techniques in which the mobile phase is a liquid.	Liquid Chromatography
D000077222	Limonene	A naturally-occurring class of MONOTERPENES which occur as a clear colorless liquid at room temperature. Limonene is the major component in the oil of oranges which has many uses, including as flavor and fragrance. It is recognized as safe in food by the Food and Drug Administration (FDA).	(+)-(R)-4-isopropenyl-1-methylcyclohexene,(+)-Limonene,(-)-Limonene,(4R)-1-methyl-4-(1-methylethenyl)cyclohexene,(4S)-1-methyl-4-isopropenylcyclohex-1-ene,(D)-Limonene,(R)-(+)-Limonene,(R)-4-isopropenyl-1-methylcyclohexene,1-Methyl-4-(1-methylethenyl)cyclohexene,4-Mentha-1,8-diene,AISA 5203-L (+)Limonene,Cyclohexene, 1-methyl-4-(1-methylethenyl)-, (4R)-,Dipentene,Limonene, (+)-,Limonene, (+-)-,Limonene, (+-)-isomer,Limonene, (R)-isomer,Limonene, (S)-isomer,d-Limonene,4 Mentha 1,8 diene,d Limonene
D000080462	Acyclic Monoterpenes	Linear compounds that contain a single monoterpene unit.	Monoterpenes, Acyclic
D000081008	Bicyclic Monoterpenes	Monoterpenes containing two ring structures that are joined either by bridgehead carbon atoms or fused ring structure.	Camphene Derivatives,Camphenes,Carane Derivatives,Caranes,Pinane Derivatives,Pinanes,Thujane Derivatives,Thujanes,Derivatives, Camphene,Derivatives, Carane,Derivatives, Pinane,Derivatives, Thujane,Monoterpenes, Bicyclic
D000336	Aerosols	Colloids with a gaseous dispersing phase and either liquid (fog) or solid (smoke) dispersed phase; used in fumigation or in inhalation therapy; may contain propellant agents.	Aerosol
D000393	Air Pollutants	Any substance in the air which could, if present in high enough concentration, harm humans, animals, vegetation or materials. Substances include GASES; PARTICULATE MATTER; and volatile ORGANIC CHEMICALS.	Air Pollutant,Air Pollutants, Environmental,Environmental Air Pollutants,Environmental Pollutants, Air,Air Environmental Pollutants,Pollutant, Air,Pollutants, Air,Pollutants, Air Environmental,Pollutants, Environmental Air