Development of furan oxidation mechanism from OH and NO3 ... Brown...– Furan exposure! – Darker...
Transcript of Development of furan oxidation mechanism from OH and NO3 ... Brown...– Furan exposure! – Darker...
112/18/2018
Development of furan oxidation mechanism from OH and NO3 oxidation within biomass-burning regimes via chamber experiments
Development of furan oxidation mechanism from OH and NO3 oxidation within biomass-burning regimes via chamber experiments
AER:Benjamin Brown-Steiner
Matthew Alvarado
Georgia Tech: Nga Lee (Sally) Ng;
Taekyu Joo
212/18/2018
Development of furan oxidation mechanism from OH and NO3 oxidation within biomass-burning regimes via chamber experiments
Development of furan oxidation mechanism from OH and NO3 oxidation within biomass-burning regimes via chamber experiments
AER:Benjamin Brown-Steiner
Matthew Alvarado
Georgia Tech: Nga Lee (Sally) Ng;
Teakyu Joo
312/18/2018
• Smell your coffee. – Furan exposure!– Darker roasts = more furans
• Furans emitted directly (biomass burning) or form from degradation of VOCs– Rapidly oxidize to form furan derivatives (lifetime ~ hours)– Collectively, these aren’t good to breathe– Are known to produce SOA, which aren’t good to breathe
• Some measurements and laboratory studies exist, but much is still uncertain, unknown, and unconstrained– Branching ratios, SOA formation potential, etc.
• Most mechanisms include furans as lumped form (e.g. MCM)
FuransFurans
Schoenauer and Schieberle (2018)“roasted coffee”: furan‐2‐ylmethanethil
412/18/2018
Furans – Quick ReviewFurans – Quick Review furan
2‐methylfuran
3‐methylfuran
2‐furanaldehyde
3‐furanaldehyde
2,5‐dimethylfuran
5‐methyl‐2‐furanaldehyde
Hatch et al. (2015)
Colmenar et al. (2012)
Black Spruce
Wiregrass
512/18/2018
10% ‐ 15% of Black Spruce and Ponderosa PineUp to 30% ‐ 50% of total SOA in other fuels
612/18/2018
Existing Studies Examining Furan OxidationExisting Studies Examining Furan Oxidation
712/18/2018
Zhao and Wang (2017)
Bierbach et al. (1995)
Furan chemistry is complicatedFuran chemistry is complicated
812/18/2018
Yuan et al. (2017)
Furan chemistry is complicatedFuran chemistry is complicated
912/18/2018
Furan chemistry is complicatedFuran chemistry is complicated
ISOPRENE
Herrmann et al. (2015)
ISOPRENE
Jenkin et al. (2015)
1012/18/2018
So there is a clear need to organize, simplify, and constrain furan chemistry if we are going to
be able to simulate it
So there is a clear need to organize, simplify, and constrain furan chemistry if we are going to
be able to simulate it
1112/18/2018
Furan and Furan Derivative OxidationFuran and Furan Derivative Oxidation
1212/18/2018
• This project:– Identify organic compounds
produced from OH and NO3oxidation of furan compounds and their SOA production potential
– Under different:• VOC:NOx ratios • RH • T conditions (chamber)
– Develop a mechanism for biomass burning plumes (ASP)
– Quantify O3 and PM2.5 (SOA) impacts
Chamber StudiesChamber Studies
RH
T
1312/18/2018
Georgia Tech Environmental Chamber FacilityGeorgia Tech Environmental Chamber FacilityGas‐phase measurements• Gas Chromatograph Flame Ionization Detector (GC‐FID): VOC
measurements• High Resolution Time of Flight Chemical Ionization Mass
Spectrometer (HR‐ToF‐CIMS): oxidized gas‐phase compounds, radicals
• UV absorption O3 analyzer• Chemilumnescence NO/NO2/NOx analyzer• CAPS NO2 monitor
Particle‐phase measurements• High Resolution Time of Flight Aerosol Mass Spectrometer
(HR‐ToF‐AMS): Aerosol composition (organics, sulfate, nitrate, ammonium, chloride), mass loading, aerosol size distribution
• Filter Inlet for Gases and AEROsols High Resolution Time‐of‐Flight Chemical Ionization Mass Spectrometer (FIGAERO‐HR‐ToF‐CIMS): molecular level particle‐phase composition
• Scanning Mobility Particle Sizer (SMPS): aerosol size distribution, volume distribution
• Condensation Particle Counter (CPC): aerosol number concentration
• Offline filter characterization
1412/18/2018
Poster Presentation: Taekyu JooPoster Presentation: Taekyu Joo
Secondary Organic Aerosol Formation and the Oxidation Mechanism of Methylfuran by Nitrate Radical
Oxidation
1512/18/2018
ASP (Aerosol Simulation Program)ASP (Aerosol Simulation Program)
Alvarado and Prinn (2009)
1612/18/2018
OH Oxidation of 2- and 3-methylfuranOH Oxidation of 2- and 3-methylfuran
Aschmann et al. (2013)
1712/18/2018
(next page)
OH Oxidation of 2- and 3-methylfuranOH Oxidation of 2- and 3-methylfuran
Strollo and Ziemann 2013
1812/18/2018
(from previous page)
OH Oxidation of 2- and 3-methylfuranOH Oxidation of 2- and 3-methylfuran
High SOA yields
Strollo and Ziemann 2013
1912/18/2018
OHOxidation
Aschmann et al. (2013)
2012/18/2018
OHOxidation
RO2
RO2
Aschmann et al. (2013)
2112/18/2018
DIALD_A
ALDACID_C HDXYFN_L
ALDEST_G
HDXYFN_K ALDACID_D
DIALD_A
ALDACID_D HDXYFN_K
ALDEST_H
DIALD_B
ALDACID_F HDXYFN_N
ALDEST_J
HDXYFN_M ALDACID_E
DIALD_B
ALDACID_E HDXYFN_M
ALDEST_I
HDXYFN_N ALDACID_F
HDXYFN_L ALDACID_C
25 14potentialproducts
2212/18/2018
aldoesters
hydroxyfuranones
.
”dialdehydes”
.
aldoacids25 14potentialproducts
2312/18/2018
2412/18/2018
2512/18/2018
Furan and Furan Derivative OxidationFuran and Furan Derivative Oxidation
2612/18/2018
Chamber SimulationsChamber Simulations
ICs: MF2, MF3, HONOLights on @ 75 minutes
2712/18/2018
25% each branching ratio
2812/18/2018
100% B Branch
2912/18/2018
50% B Branch, 16.7% to each of the others
3012/18/2018
Gas-PhaseGas-Phase
50% B Branch, 16.7% to each of the others
100% B Branch
25% each branching ratio
30 ppb
42 ppb
35 ppb
OzoneOH
3112/18/2018
• Chamber studies with OH oxidation• Add to ASP:
– NO3 oxidation– NO NO2 chemistry (organic nitrates)– Furfural– Oligomerization parameterizations
• Synthesis and mechanism constraints• 1st year of a 3-year project…so stay tuned!
Next StepsNext Steps
3212/18/2018
Poster Presentation: Taekyu JooPoster Presentation: Taekyu Joo
Secondary Organic Aerosol Formation and the Oxidation Mechanism of Methylfuran by Nitrate Radical
Oxidation
3312/18/2018
Questions?Questions?