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Calculating Photoabsorption Cross-Sections for Atmospheric Volatile Organic Compounds.

ABSTRACT: Characterizing the photochemical reactivity of transient volatile organic compounds (VOCs) in our atmosphere begins with a proper understanding of their abilities to absorb sunlight. Unfortunately, the photoabsorption cross-sections for a large number of transient VOCs remain unavailable experimentally due to their short lifetime or high reactivity. While structure-activity relationships (SARs) have been successfully employed to estimate the unknown photoabsorption cross-sections of VOCs, computational photochemistry offers another promising strategy to predict not only the vertical electronic transitions of a given molecule but also the width and shape of the bands forming its absorption spectrum. In this work, we focus on the use of the nuclear ensemble approach (NEA) to determine the photoabsorption cross-section of four exemplary VOCs, namely, acrolein, methylhydroperoxide, 2-hydroperoxy-propanal, and (microsolvated) pyruvic acid. More specifically, we analyze the influence that different strategies for sampling the ground-state nuclear density-Wigner sampling and ab initio molecular dynamics with a quantum thermostat-can have on the simulated absorption spectra. We highlight the potential shortcomings of using uncoupled harmonic modes within Wigner sampling of nuclear density to describe flexible or microsolvated VOCs and some limitations of SARs for multichromophoric VOCs. Our results suggest that the NEA could constitute a powerful tool for the atmospheric community to predict the photoabsorption cross-section for transient VOCs.

SUBMITTER: Prlj A

PROVIDER: S-EPMC8785186 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The Arctic is a climatically sensitive region that has experienced warming at almost 3 times the global average rate in recent decades, leading to an increase in Arctic greenness and a greater abundance of plants that emit biogenic volatile organic compounds (BVOCs). These changes in atmospheric emissions are expected to significantly modify the overall oxidative chemistry of the region and lead to changes in VOC composition and abundance, with implications for atmospheric processes. Nonetheless, observations needed to constrain our current understanding of these issues in this critical environment are sparse. This work presents novel atmospheric in situ proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS) measurements of VOCs at Toolik Field Station (TFS; 68°38' N, 149°36' W), in the Alaskan Arctic tundra during May-June 2019. We employ a custom nested grid version of the GEOS-Chem chemical transport model (CTM), driven with MEGANv2.1 (Model of Emissions of Gases and Aerosols from Nature version 2.1) biogenic emissions for Alaska at 0.25° × 0.3125° resolution, to interpret the observations in terms of their constraints on BVOC emissions, total reactive organic carbon (ROC) composition, and calculated OH reactivity (OHr) in this environment. We find total ambient mole fraction of 78 identified VOCs to be 6.3 ± 0.4 ppbv (10.8 ± 0.5 ppbC), with overwhelming (> 80 %) contributions are from short-chain oxygenated VOCs (OVOCs) including methanol, acetone and formaldehyde. Isoprene was the most abundant terpene identified. GEOS-Chem captures the observed isoprene (and its oxidation products), acetone and acetaldehyde abundances within the combined model and observation uncertainties (±25 %), but underestimates other OVOCs including methanol, formaldehyde, formic acid and acetic acid by a factor of 3 to 12. The negative model bias for methanol is attributed to underestimated biogenic methanol emissions for the Alaskan tundra in MEGANv2.1. Observed formaldehyde mole fractions increase exponentially with air temperature, likely reflecting its biogenic precursors and pointing to a systematic model underprediction of its secondary production. The median campaign-calculated OHr from VOCs measured at TFS was 0.7 s-1, roughly 5 % of the values typically reported in lower-latitude forested ecosystems. Ten species account for over 80 % of the calculated VOC OHr, with formaldehyde, isoprene and acetaldehyde together accounting for nearly half of the total. Simulated OHr based on median-modeled VOCs included in GEOS-Chem averages 0.5 s-1 and is dominated by isoprene (30 %) and monoterpenes (17 %). The data presented here serve as a critical evaluation of our knowledge of BVOCs and ROC budgets in high-latitude environments and represent a foundation for investigating and interpreting future warming-driven changes in VOC emissions in the Alaskan Arctic tundra.

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Calculating Photoabsorption Cross-Sections for Atmospheric Volatile Organic Compounds.

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