Transport and chemistry of isoprene and its oxidation products in deep convective clouds

Roman Bardakov; Joel A. Thornton; Ilona Riipinen; Radovan Krejci; Annica M. L. Ekman

doi:10.1080/16000889.2021.1979856

Transport and chemistry of isoprene and its oxidation products in deep convective clouds

Tellus B: Chemical and Physical Meteorology

Volume 73 (2021): Issue 1

By: Roman Bardakov, Joel A. Thornton, Ilona Riipinen, Radovan Krejci and Annica M. L. Ekman

Open Access

|Jan 2021

Figures & Tables

SkewT-logP and wind diagrams for the atmospheric soundings retrieved in Manaus, Brazil on April 8 (a), 2020, April 23, 2020 (b) and April 27, 2020 (c).

Table 1.

Molecular properties for the system compounds used in the simulations.

IDCompound

Δ H, \frac{kJ}{mol}

P_{eff}^{θ},

PaM_g ,

\frac{g}{mol}

0O3 (ozone)23.2

0.5 \times 10^{9}

481NO (nitric oxide)13.2

0.2 \times 10^{10}

302NO2 (nitrogen dioxide)19.9

0.5 \times 10^{9}

463NO3 (nitrate)15.8

1.4 \times 10^{8}

624OH (hydroxyl radical)35.6

0.1 \times 10^{6}

175HO2 (hydroperoxy radical)48.9

0.8 \times 10^{4}

336H2O2 (hydrogen peroxide)48.5

0.6 \times 10^{2}

347CO (carbon monoxide)10.7

0.5 \times 10^{10}

288CH4 (methane)15.7

0.4 \times 10^{10}

169RO2 (organic peroxy radicals)30.7

0.3 \times 10^{6}

4710ROOH (organic hydroperoxide)43.1

0.2 \times 10^{5}

4811CH3OOH (methyl hydroperoxide)43.1

0.2 \times 10^{5}

4812HCHO (formaldehyde)56.4

0.1 \times 10^{4}

3013HNO3 (nitric acid)72.2

0.6 \times 10^{2}

6314HO2NO2 (pernitric acid)69.8

1.4 \times 10^{5}

7915C5H8 (isoprene)36.5

0.4 \times 10^{9}

6816ISOP1O2 (isoprene peroxy radical)52.1

6.1 \times 10^{4}

11717ISOPOOH (first-generation isoprene hydroxy hydroperoxide)84.5

0.5 \times 10^{0}

11818ISOP1Nit (isoprene hydroxy nitrate)79.8

1.0 \times 10^{3}

14719C4CBYL (methyl vinyl ketone (MVK) or methacrolein (MACR) and related analogues)35.6

3.9 \times 10^{5}

7020ISOP1OH (isoprene diol)61.8

5.5 \times 10^{2}

10221IEPOX (isoprene epoxy diol)89.2

0.7 \times 10^{0}

11822ISOP2O2 (second-generation isoprene peroxy radical)110.5

1.5 \times 10^{- 3}

13523DHHPEPOX (isoprene di-hydroxy hydroperoxy epoxide)118.6

2.4 \times 10^{- 4}

13524ISOPDHDHP (di-hydroxy di-hydroperoxides)142.9

1.5 \times 10^{- 7}

13525ISOPDHHPNit (di-hydroxy hydroperoxy nitrates)138.1

2.0 \times 10^{- 5}

19726ISOPTHHP (isoprene tri-hydroxy hydroperoxide)131.3

1.6 \times 10^{- 6}

13527ISOP1NitO2 (isoprene nitrate peroxy radical)105.7

0.2 \times 10^{0}

19628ISOPDiNit (isoprene di-nitrates)133.3

4.7 \times 10^{- 3}

22629C4CBYLNit (nitrates of MVK, MACR and related analogues)82.6

1.2 \times 10^{2}

14930ISOPTHNit (isoprene tri-hydroxy nitrate)126.5

1.9 \times 10^{- 4}

18131C4CBYLO2 (peroxy radicals from MVK, MACR, and related analogues)29.0

1.2 \times 10^{6}

10132PAN (peroxyacetic nitric anhydride)39.4

3.4 \times 10^{5}

121

Table 2.

Different settings for the simulations.

Simulation ID[Isoprene], ppbAimREF (0)3Base simulation to investigate the system evolution for different parcels and clouds.NULL_CHEM (7)3To quantify the impact of neglecting all the chemical interactions on the system.NULL_ISOP (8)0To understand how OH evolves in the absence of isoprene.LIGHTNING (12)3To investigate how adding NO source of 0.0016 ppb s^–1 from lightning (at 8-12 km) influences the system evolution.LIGHTNING + NULL_COND_ICE (14)3To investigate how adding NO source of 0.0016 ppb s^–1 from lightning (at 8-12 km) along with shutting off the condensation on ice influences the system evolution.

Volatility diagram for the compounds in the modelled system.

Trajectories of the 400 simulated deep convective cloud air parcels for the April 23, 2020 case (grey), parcels averaged by height bins (black), parcel A used for further analysis (red) (a), distribution of parcels according to their final altitude (b), the altitude of parcel A (red line) and the corresponding water vapour concentration (green line) (c), the total water mass of the different types of hydrometeors (d), and the reversed timescale of mixing (e).

Evolution of gas phase concentrations of the 21 selected compounds (see Table 1) along the trajectory A (see Fig. 3) for the REF and NULL_CHEM simulations given in Table 2. The concentrations in ppb are normalised to the corresponding initial values also in ppb. The compound notations are followed by the corresponding volatility acronym in parentheses. Corresponding figures for all the 33 modelled species are provided in SI.

Evolution of OH along the trajectory A (see 3) for the REF (blue solid line), LIGHTNING (black dashed line), LIGHTNING + NULL_COND_ICE (black dotted line), NULL_ISOP (red dotted line) simulations as well as concentration of water vapour (or H₂O, green solid line) as a function of time. Grey shaded area shows lightning period.

Evolution of gas phase concentrations of the 21 studied compounds (see Table 1) along the trajectory A (see Fig. 3) for the simulations REF (blue line), LIGHTNING (dashed black line) and LIGHTNING + NULL_COND_ICE (dotted black line), see Table 2. The grey shaded area denotes period of simulated lightning. The concentrations in ppb are normalised to the corresponding initial values also in ppb. The compound notations are followed by the corresponding volatility acronym in parentheses. Figures for all the 33 modelled species as well as a figure which compares the REF and LIGHTNING cases are provided in SI.

Trajectories from three different simulated deep convective cloud events (a, b and c). All parcels were divided into bins as a function of their arrival altitude and their properties were thereafter averaged (filled circles in a, b and c). Histogram of the final altitudes of the parcels (d) and chemical concentrations (e) in the out-of-cloud background (dashed line) and in the binned parcels after 2 h of simulation for three deep convective cloud cases (colored lines). Simulation settings are according to REF (see Table 2).

Table A1. Coefficients a_ij used for meteorological interactions.

CoefficientExpressiona₁₁

- (a_{1}^{(e v)} - a_{1}^{(rem)} + a_{1}^{(frz)})

a₁₂

a_{2}^{(mlt)}

a₁₃

(a_{3}^{(aut)} + a_{3}^{(acc)})

a₁₄0a₁₅

a_{1}^{(c s)}

a₂₁

a_{1}^{(frz)}

a₂₂

- (a_{2}^{(e v)} - a_{2}^{(rem)} + a_{2}^{(mlt)})

a₂₃0a₂₄

(a_{4}^{(aut)} + a_{4}^{(acc)})

a₂₅

a_{2}^{(c s)}

a₃₁0a₃₂0a₃₃

- (a_{3}^{(e v)} + a_{3}^{(aut)} + a_{3}^{(acc)} + a_{3}^{(frz)})

a₃₄

a_{3}^{(mlt)}

a₃₅

a_{3}^{(c s)}

a₄₁0a₄₂0a₄₃

a_{3}^{(frz)}

a₄₄

- (a_{4}^{(e v)} + a_{4}^{(aut)} + a_{4}^{(acc)} + a_{4}^{(frz)})

a₄₅

a_{4}^{(c s)}

a₅₁

a_{1}^{(e v)}

a₅₂

a_{2}^{(e v)}

a₅₃

a_{3}^{(e v)}

a₅₄

a_{4}^{(e v)}

a₅₅

- (\sum_{i = 1}^{5} a_{i}^{(c s)} + a^{(e x)} + a^{(mix)})

a^{(mix)} C^{(B G)}

[i] See Bardakov et al. (2020) for more details about the coefficients.

Table B1. Photolysis reactions.

Photolysis reactionRate, s^–1SourceO3 +

h ν

→ 2OH6.52e-5 k′ [H2O]/(k″[M])TUV model

^{(a, b)}

H2O2 +

h ν

→ 2OH1.18e-6TUV modelCH3OOH +

h ν

→ OH9.9e-6TUV modelHCHO +

h ν

→ 2HO2 + CO9.8e-5TUV modelNO2 +

h ν

→ NO + O31.2e-2TUV modelNO3 +

h ν

→ NO22.8e-4TUV modelISOPOOH +

h ν

→ 2OH + HCHO9.9e-6TUV model

[i] a) [M] = $7.243 \times 10^{16} \frac{P (P a)}{T (K)},$ where P is the air pressure.

[ii] b) $k'$ and $k ″$ are the rates for reactions $O (^{1} D) + H_{2} O \to 2 O H$ and $O (^{1} D) + N_{2} \to O (^{3} P) + M^{*}$ with assumed values of $2.1 \times 10^{- 10}$ and $3.3 \times 10^{- 11}$ respectively (Tan et al., 2019).

[iii] c) all constants in front of the rates are defined for standard TUV calculator simulations.

Table B2. Chemical reactions for the system components and their rates. Part 1.

ReactionRate,

\frac{{cm}^{3}}{molec s}

SourceNO + O3 → NO22.07e-12EXP(-1400/T)IUPACOH + O3 → HO21.7e-12EXP(-940/T)MCMHO2 + O3 → OH2.03e-16(T/300.)

^{4.57}

EXP(-693/T)MCMHO2 + NO → OH + NO23.45e-12EXP(270/T)IUPACOH + NO2 → HNO3K1 ^a IUPACOH + HNO3 → NO3KMT11MCMNO + NO3 → 2NO21.8e-11EXP(110/T)MCMHO2 + NO2 → HO2NO2KMT09MCMOH + HO2NO2 → NO23.2e-13*EXP(690/TEMP)MCMOH + HO2 → -4.8e-11*EXP(250/TEMP)MCMOH + HCHO → HO2 + CO4.8e-11*EXP(250/TEMP)MCMHO2 + HO2 → H2O2K2 ^b IUPACOH + CO → HO2KMT05MCMOH + CH4 → RO21.85e-12EXP(-1690/T)IUPAC ^c HO2 + RO2 → ROOHKRO2HO2MCMRO2 + NO → HCHO + NO2KRO2NOMCMIsoprene + OH → ISOP1O22.10e-11 EXP(465/T)IUPACISOP1O2 + HO2 → ISOPOOHKRO2HO2MCMISOP1O2 + NO → 0.104 ISOP1Nit + 0.896 (C4CBYL + NO2 + HCHO + HO2)KRO2NOMCMISOP1O2 + RO2 → 0.3 ISOP1OH + 0.7 C4CBYL + 0.4 HO21e-12assumedISOP1O2 + ISOP1O2 → 2 (C4CBYL + CO + HO2)1e-12assumedISOPOOH + OH → 0.7 IEPOX + 0.7 OH + 0.3 ISOP2O21.54e-10MCMISOP2O2 → DHHPEPOX + OH3.3e12EXP(-8660/T)assumedISOP2O2 + HO2 → ISOPDHDHPKRO2HO2MCMISOP2O2 + NO → 0.13 ISOPDHHPNit + 0.87 (C4CBYL + NO2 + HCHO)KRO2NOMCMISOP2O2 + RO2 → 0.3 ISOPTHHP + 0.7 (C4CBYL + HCHO)e-12assumedISOP1Nit + OH → ISOP1NitO22.17e-11assumedISOP1NitO2 + HO2 → ISOP1NitHPKRO2HO2MCMISOP1NitO2 + NO → 0.16 ISOPDiNit + 0.84 (C4CBYLNit + NO2 + HCHO)KRO2NOMCMISOP1NitO2 + RO2 → 0.3 ISOPTHNit + 0.7 (C4CBYLNit + HCHO)1e-12assumedIEPOX + OH → C4CBYL + HCHO8.4e-12MCMDHHPEPOX + OH → C4CBYL + HCHO + OH8.4e-12MCMC4CBYL + OH → C4CBYLO28.0e-12EXP(380/T)MCMC4CBYLO2 + NO2 → PANKFPANMCMPAN → RO2 + NO2KBPANMCMC4CBYLO2 + NO → 0.07C4CBYLNit + 0.93(2 HCHO + 2 CO + NO2 + HO2)KRO2NOMCMISOPDiNit + OH → C4CBYLNit + HCHO + NO2 + HO21.63e-12assumedISOPDHDHP + OH → C4CBYL + HCHO1.05e-11 EXP(465/T)assumedC4CBYLNit + OH → 2 HCHO + 2 CO + NO2 + HO22.6e-12 EXP(610/T)assumedISOPDHHPNit + OH → C4CBYLNit + HCHO1.05e-11 EXP(465/T)assumedISOPTHHP + OH → C4CBYL + HCHO1.05e-11 EXP(465/T)assumed

[i] a) K1= $\frac{3.2 \times 10^{- 30} {(T / 300)}^{- 4.5} [M] \times 3.0 \times 10^{- 11} F}{3.2 \times 10^{- 30} {(T / 300)}^{- 4.5} [M] + 3.0 \times 10^{- 11}} .$

[ii] b) K2= $2.2 \times 10^{- 13} e^{600 / T} f_{0} + 1.9 \times 10^{- 33} e^{980 / T} [M] f_{0} .$

[iii] $[M] = 7.243 \times 10^{16} \frac{P (P a)}{T (K)},$ where P is the air pressure.

[iv] F is the broadening factor defined from: $l o g_{10} F ≅ \frac{l o g_{10} F_{c}}{1 + [l o g_{10} (k_{0} / k_{\infty}) / (0.75 - 1.25 l o g_{10} F_{c})]},$ with $F_{c} = 0.41 .$

[v] $f_{0} = 1 + 1.4 \times 10^{- 21} [H 2 O] e^{2200 / T} .$

[vi] c) $O H + C H_{4} \to H_{2} O + C H_{3}$ reaction rate used. IUPAC data is available at https://iupac-aeris.ipsl.fr/

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DOI: https://doi.org/10.1080/16000889.2021.1979856 | Journal eISSN: 1600-0889

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Language: English

Page range: 1979856 - 1979856

Published on: Jan 1, 2021

Published by: Stockholm University Press

In partnership with: Paradigm Publishing Services

Keywords:

Convective transport of isoprene,

deep convective cloud trajectories,

photochemical box model

© 2021 Roman Bardakov, Joel A. Thornton, Ilona Riipinen, Radovan Krejci, Annica M. L. Ekman, published by Stockholm University Press
This work is licensed under the Creative Commons Attribution 4.0 License.

Volume 73 (2021): Issue 1

Transport and chemistry of isoprene and its oxidation products in deep convective clouds

Figures & Tables

Fig. 1.

Table 1.

Table 2.

Fig. 2.

Fig. 3.

Fig. 4.

Fig. 5.

Fig. 6.

Fig. 7.

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