Production and Fate of C4 Dihydroxycarbonyl Compounds from Isoprene Oxidation

被引：33

作者：

Bates, Kelvin H. ^{[1
]}

Nguyen, Tran B. ^{[2
]}

Teng, Alex P. ^{[2
]}

Crounse, John D. ^{[2
]}

Kjaergaard, Henrik G. ^{[4
]}

Stoltz, Brian M. ^{[1
]}

Seinfeld, John H. ^{[1
,3
]}

Wennberg, Paul O. ^{[2
,3
]}

机构：

[1] CALTECH, Div Chem & Chem Engn, 1200 East Calif Blvd, Pasadena, CA 91125 USA

[2] CALTECH, Div Geol & Planetary Sci, 1200 East Calif Blvd, Pasadena, CA 91125 USA

[3] CALTECH, Div Engn & Appl Sci, 1200 East Calif Blvd, Pasadena, CA 91125 USA

[4] Univ Copenhagen, Dept Chem, Univ Pk 5, DK-2100 Copenhagen O, Denmark

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2016年 / 120卷 / 01期

基金：

美国国家科学基金会;

关键词：

ORGANIC AEROSOL FORMATION; REACTIVE UPTAKE; RATE CONSTANTS; EPOXYDIOLS; MODEL; PHOTOOXIDATION; DEGRADATION; EMISSIONS; CHEMISTRY; OH;

D O I：

10.1021/acs.jpca.5b10335

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Isoprene epoxydiols (IEPOX) are formed in high yield as second-generation products of atmospheric isoprene oxidation in pristine (low-NO) environments. IEPOX has received significant attention for its ability to form secondary organic aerosol, but the fate of IEPOX in the gas phase, and those of its oxidation products, remains largely unexplored. In this study, three dihydroxycarbonyl compounds with molecular formula of C4H8O3, putative products of IEPOX oxidation, are synthesized to determine their isomer-specific yields from IEPOX. We find that 3,4-dihydroxy-2-butanone (DHBO) comprises 43% and 36% of the products from cis- and trans-beta-IEPOX, respectively, and is by far the most abundant C4H8O3 dihydroxycarbonyl compound produced by this mechanism. OH is found to react with DHBO with a rate coefficient of 1.10 x 10(-11) cm(3) molecule(-1) s(-1) at 297 K, forming two hydroxydicarbonyl compounds that share the molecular formula C4H6O3 with unitary yield. The results of this study are compared with field observations and used to propose a multigenerational mechanism of IEPOX oxidation. Finally, global simulations using GEOS-Chem, a chemical transport model, show that the C4H8O3 dihydroxycarbonyl compounds and their oxidation products are widespread in the atmosphere and estimate annual global production of C4H8O3 dihydroxycarbonyls to be 54 Tg y(-1), primarily as DHBO.

引用

页码：106 / 117

页数：12

共 58 条

[1] Impacts of mechanistic changes on HOx formation and recycling in the oxidation of isoprene [J].

Archibald, A. T. ;

Cooke, M. C. ;

Utembe, S. R. ;

Shallcross, D. E. ;

Derwent, R. G. ;

Jenkin, M. E. .

ATMOSPHERIC CHEMISTRY AND PHYSICS, 2010, 10 (17) :8097-8118

[2] Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II - gas phase reactions of organic species [J].

Atkinson, R. ;

Baulch, D. L. ;

Cox, R. A. ;

Crowley, J. N. ;

Hampson, R. F. ;

Hynes, R. G. ;

Jenkin, M. E. ;

Rossi, M. J. ;

Troe, J. .

ATMOSPHERIC CHEMISTRY AND PHYSICS, 2006, 6 :3625-4055

[3] Atmospheric degradation of volatile organic compounds [J].

Atkinson, R ;

Arey, J .

CHEMICAL REVIEWS, 2003, 103 (12) :4605-4638

[4] ALKYL NITRATE FORMATION FROM THE NOX-AIR PHOTOOXIDATIONS OF C2-C8 N-ALKANES [J].

ATKINSON, R ;

ASCHMANN, SM ;

CARTER, WPL ;

WINER, AM ;

PITTS, JN .

JOURNAL OF PHYSICAL CHEMISTRY, 1982, 86 (23) :4563-4569

[5] Gas Phase Production and Loss of Isoprene Epoxydiols [J].

Bates, Kelvin H. ;

Crounse, John D. ;

St Clair, Jason M. ;

Bennett, Nathan B. ;

Nguyen, Tran B. ;

Seinfeld, John H. ;

Stoltz, Brian M. ;

Wennberg, Paul O. .

JOURNAL OF PHYSICAL CHEMISTRY A, 2014, 118 (07) :1237-1246

[6] Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation [J].

Bey, I ;

Jacob, DJ ;

Yantosca, RM ;

Logan, JA ;

Field, BD ;

Fiore, AM ;

Li, QB ;

Liu, HGY ;

Mickley, LJ ;

Schultz, MG .

JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 2001, 106 (D19) :23073-23095

[7] SYNTHESIS OF ANALOGS OF 1,3-DIHYDROXYACETONE PHOSPHATE AND GLYCERALDEHYDE-3-PHOSPHATE FOR USE IN STUDIES OF FRUCTOSE-1,6-DIPHOSPHATE ALDOLASE [J].

BISCHOFBERGER, N ;

WALDMANN, H ;

SAITO, T ;

SIMON, ES ;

LEES, W ;

BEDNARSKI, MD ;

WHITESIDES, GM .

JOURNAL OF ORGANIC CHEMISTRY, 1988, 53 (15) :3457-3465

[8] Photolysis of 2,3-pentanedione and 2,3-hexanedione: Kinetics, quantum yields, and product study in a simulation chamber [J].

Bouzidi, H. ;

Fittschen, C. ;

Coddeville, P. ;

Tomas, A. .

ATMOSPHERIC ENVIRONMENT, 2014, 82 :250-257

[9] Real-Time Continuous Characterization of Secondary Organic Aerosol Derived from Isoprene Epoxydiols in Downtown Atlanta, Georgia, Using the Aerodyne Aerosol Chemical Speciation Monitor [J].

Budisulistiorini, Sri Hapsari ;

Canagaratna, Manjula R. ;

Croteau, Philip L. ;

Marth, Wendy J. ;

Baumann, Karsten ;

Edgerton, Eric S. ;

Shaw, Stephanie L. ;

Knipping, Eladio M. ;

Worsnop, Douglas R. ;

Jayne, John T. ;

Gold, Avram ;

Surratt, Jason D. .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2013, 47 (11) :5686-5694

[10] Measurement of gas-phase hydroperoxides by chemical ionization mass spectrometry [J].

Crounse, John D. ;

McKinney, Karena A. ;

Kwan, Alan J. ;

Wennberg, Paul O. .

ANALYTICAL CHEMISTRY, 2006, 78 (19) :6726-6732

← 1 2 3 4 5 6 →