Atmospheric chemical loss processes of isocyanic acid (HNCO): a combined theoretical kinetic and global modelling study

Abstract. Isocyanic acid (HNCO) is a chemical constituent suspected to be harmful to humans if ambient concentrations exceed ∼1 ppbv. HNCO is mainly emitted by combustion processes but is also inadvertently released by NOx mitigation measures in flue gas treatments. With increasing biomass burning and more widespread usage of catalytic converters in car engines, good prediction of HNCO atmospheric levels with global models is desirable. Little is known directly about the chemical loss processes of HNCO, which limits the implementation in global Earth system models. This study aims to close this knowledge gap by combining a theoretical kinetic study on the major oxidants reacting with HNCO with a global modelling study. The potential energy surfaces of the reactions of HNCO with OH and NO3 radicals, Cl atoms, and ozone were studied using high-level CCSD(T)/CBS(DTQ)//M06-2X/aug-cc-pVTZ quantum chemical methodologies, followed by transition state theory (TST) theoretical kinetic predictions of the rate coefficients at temperatures of 200–3000 K. It was found that the reactions are all slow in atmospheric conditions, with k(300K)≤7×10-16 cm3molecule-1s-1, and that product formation occurs predominantly by H abstraction; the predictions are in good agreement with earlier experimental work, where available. The reverse reactions of NCO radicals with H2O, HNO3, and HCl, of importance mostly in combustion, were also examined briefly. The findings are implemented into the atmospheric model EMAC (ECHAM/MESSy Atmospheric Chemistry) to estimate the importance of each chemical loss process on a global scale. The EMAC predictions confirm that the gas-phase chemical loss of HNCO is a negligible process, contributing less than 1 % and leaving heterogeneous losses as the major sinks. The removal of HNCO by clouds and precipitation contributes about 10 % of the total loss, while globally dry deposition is the main sink, accounting for ∼90 %. The global simulation also shows that due to its long chemical lifetime in the free troposphere, HNCO can be efficiently transported into the UTLS by deep convection events. Daily-average mixing ratios of ground-level HNCO are found to regularly exceed 1 ppbv in regions dominated by biomass burning events, but rarely exceed levels above 10 ppt in other areas of the troposphere, though locally instantaneous toxic levels are expected.

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Structure-dependence in Initial Decomposition of trans-1,2-Dimethylcyclohexyl Isomers: Kinetic Exploration and Conformational Analysis

10.22541/au.163663301.11280598/v1 ◽

2021 ◽

Author(s):

Huiting Bian ◽

Yongjin Wang ◽

Jing Li ◽

Jun Zhao

Keyword(s):

Conformational Analysis ◽

Alternative Fuels ◽

Kinetic Modelling ◽

Decomposition Reaction ◽

State Theory ◽

Rate Coefficients ◽

Potential Implication ◽

Structure Dependence ◽

Radical Site ◽

Kinetic Predictions

Cyclohexyl radicals are crucial primary intermediates in combustion of fossil and alternative fuels. They would present the inherent conformation feature, i.e. diverse conformers retained in inversion-topomerization pathways, jointly controlled by the varying radical site and specific spatial positions of alkyl side chains on “easy-distortion” cyclic ring. These conformers for one radical have different energies and thermodynamics, and are highly expected to influence their subsequent decomposition reactions in terms of energetics and kinetics. To reveal such impact, all conformational structures and their interconversion mechanisms for trans-1,2-dimethylcyclohexyl isomers were explored by employing quantum chemical calculations coupled with transition state theory. Originated from distinct conformers, all accessible transition states were explicitly identified in different reaction paths for each type of intramolecular H-transfer or β-scission, and then were carefully used in computing rate coefficients. The kinetic predictions demonstrate that the fairly speedy equilibrium among conformers would be established for one isomer via conformation before they proceed the initial decomposition over 300-2500 K. This allows thoroughly evaluating the contribution of various conformers to the kinetics for multiple paths in one reaction regarding to their thermodynamic properties. Moreover, conformational analysis elucidates that H-transfers exhibit strong structure dependence. Note that the most favorable 1,5 H-transfer is only feasible for one twist-boat with radical site in axial side chain accompanied by one isoclinal methyl group. The results for β-scissions are affected by steric energies and substituent effects remained in conformational structures. These findings facilitate to finally suggest the proper kinetic parameters for each decomposition reaction with the aim of their potential implication in kinetic modelling.

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Chemical loss processes of isocyanic acid, HNCO, in the atmosphere

10.5194/acp-2019-1138 ◽

2020 ◽

Author(s):

Simon Rosanka ◽

Giang H. T. Vu ◽

Hue M. T. Nguyen ◽

Tien V. Pham ◽

Umar Javed ◽

...

Keyword(s):

Potential Energy Surfaces ◽

Deep Convection ◽

Rate Coefficients ◽

Isocyanic Acid ◽

Free Troposphere ◽

Atmospheric Conditions ◽

Kinetic Predictions ◽

High Level ◽

Energy Surfaces ◽

The Impact

Abstract. The impact of chemical loss processes of isocyanic acid was studied by a combined theoretical and modeling study. The potential energy surfaces of the reactions of HNCO with OH and NO3 radicals, Cl atoms, and ozone, were studied using high-level CCSD(T)/CBS(DTQ)//M06-2X/aug-cc-pVTZ quantum chemical methodologies, followed by TST theoretical kinetic predictions of the rate coefficients at temperatures of 200–3000 K. It was found that the reactions are all slow in atmospheric conditions, with k(300 K) ≤ 7 × 10−16 cm3 molecule−1 s−1; the predictions are in good agreement with earlier experimental work, where available. The reverse reactions of NCO radicals, of importance mostly in combustion, were also examined briefly. The global model confirms that gas phase chemical loss of HNCO is a negligible process, contributing less than 1 %. Removal of HNCO by clouds and precipitation is a larger sink, contributing for about 10 % of the total loss, while globally dry deposition is the main sink, accounting for ~ 90 %. The global simulation also shows that due to its long chemical lifetime in the free troposphere, HNCO can be efficiently transported into the UTLS by deep convection events. Average daily concentrations of HNCO are found to rarely exceed levels considered potentially toxic, though locally instantaneous toxic levels are expected.the free troposphere, HNCO can be efficiently transported into the UTLS by deep convection events. Average daily concentrations of HNCO are found to rarely exceed levels considered potentially toxic, though locally instantaneous toxic levels are expected.

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Effect of ammonia and water molecule on OH + CH3OH reaction under tropospheric condition

Scientific Reports ◽

10.1038/s41598-021-90640-6 ◽

2021 ◽

Vol 11 (1) ◽

Author(s):

Mohamad Akbar Ali ◽

M. Balaganesh ◽

Faisal A. Al-Odail ◽

K. C. Lin

Keyword(s):

Water Molecule ◽

Energy Surface ◽

Rate Coefficient ◽

Water Concentration ◽

State Theory ◽

Rate Coefficients ◽

Hydrogen Atoms ◽

Experimental And Theoretical Studies ◽

Effective Reaction ◽

Effective Reaction Rate

AbstractThe rate coefficients for OH + CH3OH and OH + CH3OH (+ X) (X = NH3, H2O) reactions were calculated using microcanonical, and canonical variational transition state theory (CVT) between 200 and 400 K based on potential energy surface constructed using CCSD(T)//M06-2X/6-311++G(3df,3pd). The results show that OH + CH3OH is dominated by the hydrogen atoms abstraction from CH3 position in both free and ammonia/water catalyzed ones. This result is in consistent with previous experimental and theoretical studies. The calculated rate coefficient for the OH + CH3OH (8.8 × 10−13 cm3 molecule−1 s−1), for OH + CH3OH (+ NH3) [1.9 × 10−21 cm3 molecule−1 s−1] and for OH + CH3OH (+ H2O) [8.1 × 10−16 cm3 molecule−1 s−1] at 300 K. The rate coefficient is at least 8 order magnitude [for OH + CH3OH(+ NH3) reaction] and 3 orders magnitude [OH + CH3OH (+ H2O)] are smaller than free OH + CH3OH reaction. Our calculations predict that the catalytic effect of single ammonia and water molecule on OH + CH3OH reaction has no effect under tropospheric conditions because the dominated ammonia and water-assisted reaction depends on ammonia and water concentration, respectively. As a result, the total effective reaction rate coefficients are smaller. The current study provides a comprehensive example of how basic and neutral catalysts effect the most important atmospheric prototype alcohol reactions.

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Investigation of atmospheric hydrogen cyanide: a modelling perspective

10.5194/egusphere-egu21-8865 ◽

2021 ◽

Author(s):

Antonio G. Bruno ◽

Jeremy J. Harrison ◽

David P. Moore ◽

Martyn P. Chipperfield ◽

Richard J. Pope

Keyword(s):

Biomass Burning ◽

Atmospheric Chemistry ◽

Hydrogen Cyanide ◽

Three Dimensional ◽

Oxidation Reactions ◽

Loss Mechanism ◽

Mixing Ratios ◽

The Individual ◽

Atmospheric Loss ◽

Physical And Chemical

<p>Hydrogen cyanide (HCN) is one of the most abundant cyanides present in the global atmosphere, and is a tracer of biomass burning, especially for peatland fires. The HCN lifetime is 2&#8211;5 months in the troposphere but several years in the stratosphere. Understanding the physical and chemical mechanisms of HCN variability is important due to its non-negligible role in the nitrogen cycle. The main source of tropospheric HCN is biomass burning with minor contributions from industry and transport. The main loss mechanism of atmospheric HCN is the reaction with the hydroxyl radical (OH). Ocean uptake is also important, while in the stratosphere oxidation by reaction with O(<sup>1</sup>D) needs to be considered.</p><p>HCN variability can be investigated using chemical model simulations, such as three-dimensional (3-D) chemical transport models (CTMs). Here we use an adapted version of the TOMCAT 3-D CTM at a 1.2&#176;x1.2&#176; spatial resolution from the surface to ~60 km for 12 idealised HCN tracers which quantify the main loss mechanisms of HCN, including ocean uptake, atmospheric oxidation reactions and their combinations. The TOMCAT output of the HCN distribution in the period 2004-2020 has been compared with HCN profiles measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) over an altitude grid from 6 to 42 km. HCN model data have also been compared with ground-based measurements of HCN columns from NDACC FTIR stations and with in-situ volume mixing ratios (VMRs) from NOAA ground-based measurement sites.</p><p>The model outputs for the HCN tracer with full treatment of the loss processes generally agree well with ACE-FTS measurements, as long as we use recent laboratory values for the atmospheric loss reactions. Diagnosis of the individual loss terms shows that decay of the HCN profile in the upper stratosphere is due mainly to the O(<sup>1</sup>D) sink. In order to test the magnitude of the tropospheric OH sink and the magnitude of the ocean sink, we also show the comparisons of the model tracers with surface-based observations. The implications of our results for understanding HCN and its variability are then discussed.</p>

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Experimental and computational kinetics investigations for the reactions of Cl atoms with series of unsaturated ketones in gas phase

10.5194/acp-2017-163 ◽

2017 ◽

Author(s):

Siripina Vijayakumar ◽

Avinash Kumar ◽

Balla Rajakuma

Keyword(s):

Gas Phase ◽

State Theory ◽

Rate Coefficients ◽

Gas Phase Reactions ◽

Temperature Dependent ◽

Unsaturated Ketones ◽

Temperature Range ◽

Computational Calculations ◽

Temperature Rate ◽

Cl Atoms

Abstract. Temperature dependent rate coefficients for the gas phase reactions of Cl atoms with 4-hexen-3-one and 5-hexen-2-one were measured over the temperature range of 298–363 K relative to 1-pentene, 1,3-butadiene and isoprene. Gas Chromatography (GC) was used to measure the concentrations of the organics. The derived temperature dependent Arrhenius expressions are k4-hexen-3-one+Cl (298–363 K) = (2.82 ± 1.76)×10−12exp [(1556 ± 438)/T] cm3 molecule−1 s−1 and k5-hexen-2-one+Cl (298–363 K) = (4.6 ± 2.4)×10−11exp[(646 ± 171)/T] cm3 molecule−1 s−1. The corresponding room temperature rate coefficients are (5.54 ± 0.41)×10−10 cm3 molecule−1 s−1 and (4.00 ± 0.37)×10−10 cm3 molecule−1 s−1 for the reactions of Cl atoms with 4-hexen-3-one and 5-hexen-2-one respectively. To understand the mechanism of Cl atom reactions with unsaturated ketones, computational calculations were performed for the reactions of Cl atoms with 4-hexen-3-one, 5-hexen-2-one and 3-penten-2-one over the temperature range of 275–400 K using Canonical Variational Transition state theory (CVT) with Small Curvature Tunneling (SCT) in combination with CCSD(T)/6-31+G(d, p)//MP2/6-311++G(d, p) level of theory. Atmospheric implications, reaction mechanism and feasibility of the title reactions are discussed in this manuscript.

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Estimates of biomass burning emissions in tropical Asia based on satellite-derived data

Atmospheric Chemistry and Physics ◽

10.5194/acp-10-2335-2010 ◽

2010 ◽

Vol 10 (5) ◽

pp. 2335-2351 ◽

Cited By ~ 78

Author(s):

D. Chang ◽

Y. Song

Keyword(s):

Biomass Burning ◽

Atmospheric Chemistry ◽

Crop Residue ◽

Fire Season ◽

Burned Area ◽

Published Data ◽

Tropical Asia ◽

Fire Emissions ◽

Burned Areas ◽

In Fire

Abstract. Biomass burning in tropical Asia emits large amounts of trace gases and particulate matter into the atmosphere, which has significant implications for atmospheric chemistry and climatic change. In this study, emissions from open biomass burning over tropical Asia were evaluated during seven fire years from 2000 to 2006 (1 March 2000–31 February 2007). The size of the burned areas was estimated from newly published 1-km L3JRC and 500-m MODIS burned area products (MCD45A1). Available fuel loads and emission factors were assigned to each vegetation type in a GlobCover characterisation map, and fuel moisture content was taken into account when calculating combustion factors. Over the whole period, both burned areas and fire emissions showed clear spatial and seasonal variations. The size of the L3JRC burned areas ranged from 36 031 km2 in fire year 2005 to 52 303 km2 in 2001, and the MCD45A1 burned areas ranged from 54 790 km2 in fire year 2001 to 148 967 km2 in 2004. Comparisons of L3JRC and MCD45A1 burned areas using ground-based measurements and other satellite data were made in several major burning regions, and the results suggest that MCD45A1 generally performed better than L3JRC, although with a certain degree of underestimation in forest areas. The average annual L3JRC-based emissions were 123 (102–152), 12 (9–15), 1.0 (0.7–1.3), 1.9 (1.4–2.6), 0.11 (0.09–0.12), 0.89 (0.63–1.21), 0.043 (0.036–0.053), 0.021 (0.021–0.023), 0.41 (0.34–0.52), 3.4 (2.6–4.3), and 3.6 (2.8–4.7) Tg yr−1 for CO2, CO, CH4, NMHCs, NOx, NH3, SO2, BC, OC, PM2.5, and PM10, respectively, whereas MCD45A1-based emissions were 122 (108–144), 9.3 (7.7–11.7), 0.63 (0.46–0.86), 1.1 (0.8–1.6), 0.11 (0.10–0.13), 0.54 (0.38–0.76), 0.043 (0.038–0.051), 0.033 (0.032–0.037), 0.39 (0.34–0.47), 3.0 (2.6–3.7), and 3.3 (2.8–4.0) Tg yr−1. Forest burning was identified as the major source of the fire emissions due to its high carbon density. Although agricultural burning was the second highest contributor, it is possible that some crop residue combustion was missed by satellite observations. This possibility is supported by comparisons with previously published data, and this result may be due to the small size of the field crop residue burning. Fire emissions were mainly concentrated in Indonesia, India, Myanmar, and Cambodia. Furthermore, the peak in the size of the burned area was generally found in the early fire season, whereas the maximum fire emissions often occurred in the late fire season.

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H–Abstraction from Dimethyl Sulfide in the Presence of an Excess of Hydroxyl Radicals. A Quantum Chemical Evaluation of Thermochemical and Kinetic Parameters Unveil an Alternative Pathway to Dimethyl Sulfoxide.

10.26434/chemrxiv.11799096.v1 ◽

2020 ◽

Author(s):

Zoi Salta ◽

Jacopo Lupi ◽

Vincenzo Barone ◽

Oscar Ventura

Keyword(s):

Dimethyl Sulfoxide ◽

Hydroxyl Radicals ◽

Quantum Chemical ◽

Dimethyl Sulfide ◽

Computational Study ◽

Alternative Pathway ◽

Oxidation Mechanism ◽

State Theory ◽

Rate Coefficients ◽

Reduced Sulfur Compounds

<div> Elucidation of the oxidation mechanism of naturally emitted reduced sulfur compounds, especially dimethyl sulfide, plays a central role in understanding background acid precipitation in the natural environment. Most frequently, theoretical studies of the addition and H-elimination reactions of dimethyl sulfide with hydroxyl radicals are studied considering the presence of oxygen that further reacts with the radicals formed in the initial steps. Although the reaction of intermediate species with additional hydroxyl radicals has been considered as part of the global mechanism of oxidation, few if any attention has been dedicated to the possibility of reactions of the initial radicals with a second •OH molecule. In this work we performed a computational study using quantum-chemical methods, of the mechanism of H-abstraction from dimethyl sulfide under normal atmospheric conditions and in reaction chambers at different O2 partial pressure, including complete absence of oxygen. Additionally, important rate coefficients were computed using canonical and variational transition state theory. The rate coefficient for abstraction affords a 4.72 x 10-12 cm3 molecule1 s-1 value, very close to the most recent experimental one (4.13 x 10-12 cm3 molecule-1 s-1). According to our best results, the initial methyl thiomethyl radical was obtained at -25.2 kcal/mol (experimentally -22.4 kcal/mol), and four important paths were identified on the potential energy surface. From the interplay of thermochemical and kinetic arguments, it was possible to demonstrate that the preferred product of the reaction of dimethyl sulfide with two hydroxyl radicals, is actually dimethyl sulfoxide. </div><div> </div>

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Modelling the optical properties of fresh biomass burning aerosol produced in a smoke chamber: results from the EFEU campaign

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-7-12657-2007 ◽

2007 ◽

Vol 7 (4) ◽

pp. 12657-12686 ◽

Cited By ~ 2

Author(s):

K. Hungershöfer ◽

K. Zeromskiene ◽

Y. Iinuma ◽

G. Helas ◽

J. Trentmann ◽

...

Keyword(s):

Optical Properties ◽

Biomass Burning ◽

Atmospheric Chemistry ◽

Absorption Efficiency ◽

Max Planck ◽

Fresh Biomass ◽

Biomass Burning Aerosol ◽

Smoke Chamber ◽

The Impact ◽

Mass Absorption Efficiency

Abstract. A better characterisation of the optical properties of biomass burning aerosol as a function of the burning conditions is required in order to quantify their effects on climate and atmospheric chemistry. Controlled laboratory combustion experiments with different fuel types were carried out at the combustion facility of the Max Planck Institute for Chemistry (Mainz, Germany) as part of the 'Impact of Vegetation Fires on the Composition and Circulation of the Atmosphere' (EFEU) project. Using the measured size distributions as well as mass scattering and absorption efficiencies, Mie calculations provided mean effective refractive indices of 1.60−0.010i and 1.56−0.010i (λ=0.55 μm) for smoke particles emitted from the combustion of savanna grass and an African hardwood (musasa), respectively. The relatively low imaginary parts suggest that the light-absorbing carbon of the investigated fresh biomass burning aerosol is only partly graphitized, resulting in strongly scattering and less absorbing particles. While the observed variability in mass scattering efficiencies was consistent with changes in particle size, the changes in the mass absorption efficiency can only be explained, if the chemical composition of the particles varies with combustion conditions.

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