Publication: Gas-Phase Oxidation Rates and Products of 1,2-Dihydroxy Isoprene
Publication - Gas-Phase Oxidation Rates and Products of 1,2-Dihydroxy Isoprene
Title:
Gas-Phase Oxidation Rates and Products of 1,2-Dihydroxy Isoprene
DOI:
10.1021/acs.est.1c04177
Publication Year:
2021
Author list:
Kelvin H Bates, James D Cope, Tran B Nguyen
Journal Short Name:
Environ. Sci. Technol.
Publisher:
American Chemical Society
Abstract
1,2-Dihydroxy isoprene (1,2-DHI), a product of isoprene oxidation from multiple chemical pathways, is produced in the atmosphere in large quantities; however, its chemical fate has not been comprehensively studied. Here, we perform chamber experiments to investigate its gas-phase reactions. We find that the reactions of 1,2-DHI with OH radicals and ozone are rapid (kOH = 8.0 (±1.3) × 10–11 cm3 molecule–1 s–1; kO3 = 7.2 (±1.1) × 10–18 cm3 molecule–1 s–1). Reaction with OH, which dominates 1,2-DHI loss, leads primarily to fragmentation and radical recycling; major products under both high- and low-NO conditions include hydroxyacetone, glycolaldehyde, and 2,3-dihydroxy-2-methyl-propanal (DHMP). Radical-terminating hydroperoxide formation from the peroxy radical (RO2) reaction with HO2 and organonitrate formation from RO2 + NO are not observed in the gas phase, possibly due to low volatility; constraints for their branching ratios are instead derived by mass balance. We also measure secondary organic aerosol mass yields from 1,2-DHI (0–23%) and show that oxidation in the presence of aqueous particles leads to formic and acetic acid production. Finally, we incorporate results into GEOS-Chem, a global chemical transport model, to compute the global production (25.3 Tg a–1) and gas-phase loss (20.2 Tg a–1) of 1,2-DHI and show that its oxidation provides non-negligible contributions to the atmospheric budgets of hydroxyacetone, glycolaldehyde, hydroxymethyl hydroperoxide, formic acid, and DHMP.Additional Notes
Experiments (16)
ID | Name | Start date | Experiment Category | Reaction Type | Reactant(s) | Oxidant Name | Temperature | Humidity | Type of Seed | RO2 Main Fate | Data Sets (count) | Actions |
---|---|---|---|---|---|---|---|---|---|---|---|---|
530 | Nguyen Group_20201224_2-methylbut-3-ene-1,2-diol/10028-14-5/hydrogen peroxide_Hydroxyl radical_No Seed | 2020-12-24 | Gas phase chemical reaction | Photooxidation | 2-methylbut-3-ene-1,2-diol, 10028-14-5, hydrogen peroxide | Hydroxyl radical | 22 | 5 | NO | 5 | Download | |
529 | Nguyen Group_20201217_2-methylbut-3-ene-1,2-diol/hydrogen peroxide_Hydroxyl radical_No Seed | 2020-12-17 | Gas phase chemical reaction | Photooxidation | 2-methylbut-3-ene-1,2-diol, hydrogen peroxide | Hydroxyl radical | 22 | 5 | HO2 | 5 | Download | |
531 | Nguyen Group_20201227_2-methylbut-3-ene-1,2-diol/Methyl nitrite/PROPYLENE_Hydroxyl radical_No Seed | 2020-12-27 | Gas phase chemical reaction | Photooxidation | 2-methylbut-3-ene-1,2-diol, Methyl nitrite, PROPYLENE | Hydroxyl radical | 22 | 5 | NO | 6 | Download | |
532 | Nguyen Group_20210107_2-methylbut-3-ene-1,2-diol/hydrogen peroxide/PROPYLENE_Hydroxyl radical_No Seed | 2021-01-07 | Gas phase chemical reaction | Photooxidation | 2-methylbut-3-ene-1,2-diol, hydrogen peroxide, PROPYLENE | Hydroxyl radical | 22 | 5 | HO2 | 6 | Download | |
533 | Nguyen Group_20210108_2-methylbut-3-ene-1,2-diol/hydrogen peroxide_Hydroxyl radical_No Seed | 2021-01-08 | Gas phase chemical reaction | Photooxidation | 2-methylbut-3-ene-1,2-diol, hydrogen peroxide | Hydroxyl radical | 22 | 5 | HO2 | 5 | Download | |
538 | Nguyen Group_20210119_2-methylbut-3-ene-1,2-diol/Methyl nitrite_Hydroxyl radical_N/A | 2021-01-19 | Gas phase chemical reaction | Photooxidation | 2-methylbut-3-ene-1,2-diol, Methyl nitrite | Hydroxyl radical | 22 | 50 | N/A | NO | 5 | Download |
544 | Nguyen Group_20210204_2-methylbut-3-ene-1,2-diol/Methyl nitrite_Hydroxyl radical_Ammonium sulfate | 2021-02-04 | Gas phase chemical reaction | Photooxidation | 2-methylbut-3-ene-1,2-diol, Methyl nitrite | Hydroxyl radical | 35 | 5 | Ammonium sulfate | Autoxidation/Isomerization | 5 | Download |
543 | Nguyen Group_20210123_2-methylbut-3-ene-1,2-diol/Methyl nitrite_Hydroxyl radical_N/A | 2021-01-23 | Gas phase chemical reaction | Photooxidation | 2-methylbut-3-ene-1,2-diol, Methyl nitrite | Hydroxyl radical | 35 | 5 | N/A | Autoxidation/Isomerization | 5 | Download |
542 | Nguyen Group_20210419_2-methylbut-3-ene-1,2-diol/OZONE_Ozone_Ammonium sulfate | 2021-04-19 | Gas phase chemical reaction, Aerosol formation | Dark oxidation | 2-methylbut-3-ene-1,2-diol, OZONE | Ozone | 22 | 56 | Ammonium sulfate | Not Sure | 4 | Download |
541 | Nguyen Group_20210421_2-methylbut-3-ene-1,2-diol/OZONE_Ozone_Ammonium sulfate | 2021-04-21 | Gas phase chemical reaction, Aerosol formation | Dark oxidation | 2-methylbut-3-ene-1,2-diol, OZONE | Ozone | 22 | 5 | Ammonium sulfate | Not Sure | 4 | Download |
540 | Nguyen Group_20210125_2-methylbut-3-ene-1,2-diol/OZONE/CYCLOHEXANE_Ozone_No Seed | 2021-01-25 | Gas phase chemical reaction | Dark oxidation | 2-methylbut-3-ene-1,2-diol, OZONE, CYCLOHEXANE | Ozone | 22 | 5 | Not Sure | 5 | Download | |
539 | Nguyen Group_20210120_2-methylbut-3-ene-1,2-diol/OZONE/CYCLOHEXANE_Ozone_No Seed | 2021-01-20 | Gas phase chemical reaction | Dark oxidation | 2-methylbut-3-ene-1,2-diol, OZONE, CYCLOHEXANE | Ozone | 22 | 50 | Not Sure | 5 | Download | |
534 | Nguyen Group_20210114_2-Methylbut-3-ene-1,2-diol/Hydrogen Peroxide_Hydroxyl radical_Ammonium sulfate | 2021-01-14 | Gas phase chemical reaction, Aerosol formation | Photooxidation | 2-Methylbut-3-ene-1,2-diol, Hydrogen Peroxide | Hydroxyl radical | 22 | 50 | Ammonium sulfate | HO2 | 5 | Download |
535 | Nguyen Group_20210115_2-methylbut-3-ene-1,2-diol/Methyl nitrite_Hydroxyl radical_Ammonium sulfate | 2021-01-15 | Gas phase chemical reaction, Aerosol formation | Photooxidation | 2-methylbut-3-ene-1,2-diol, Methyl nitrite | Hydroxyl radical | 22 | 50 | Ammonium sulfate | NO | 5 | Download |
536 | Nguyen Group_20210117_2-methylbut-3-ene-1,2-diol/hydrogen peroxide_Hydroxyl radical_Ammonium sulfate | 2021-01-17 | Gas phase chemical reaction, Aerosol formation | Photooxidation | 2-methylbut-3-ene-1,2-diol, hydrogen peroxide | Hydroxyl radical | 22 | 5 | Ammonium sulfate | HO2 | 5 | Download |
537 | Nguyen Group_20210118_2-methylbut-3-ene-1,2-diol/hydrogen peroxide/Nitric oxide_Hydroxyl radical_Ammonium sulfate | 2021-01-18 | Gas phase chemical reaction, Aerosol formation | Photooxidation | 2-methylbut-3-ene-1,2-diol, hydrogen peroxide, Nitric oxide | Hydroxyl radical | 22 | 5 | Ammonium sulfate | NO | 5 | Download |