Isoprene versus Monoterpenes as Gas-Phase Organic Acid Precursors in the Atmosphere

Link, Michael F.; Brophy, Patrick D.; Fulgham, S. Ryan; Murschell, Trey; Farmer, Delphine K.

doi:10.1021/acsearthspacechem.1c00093

Cited by 17 publications

(8 citation statements)

References 78 publications

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“…The MEFO site has been previously used for EC studies of 2‐methyl‐3‐buten‐2‐ol (232‐MBO) and isoprene (Karl et al., 2014), small organic acids (Fulgham et al., 2019), and other oxygenated VOCs (Kaser et al., 2013a; S. Kim et al., 2010). Other detailed atmospheric chemistry studies at MEFO have primarily focused on reactive carbon abundance and chemistry (Karl et al., 2012; Kaser et al., 2013b; Link et al., 2021; Wolfe et al., 2014; Zhou et al., 2015).…”

Section: Methodsmentioning

confidence: 99%

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Closing the Reactive Carbon Flux Budget: Observations From Dual Mass Spectrometers Over a Coniferous Forest

et al. 2023

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We use observations from dual high‐resolution mass spectrometers to characterize ecosystem‐atmosphere fluxes of reactive carbon across an extensive range of volatile organic compounds (VOCs) and test how well that exchange is represented in current chemical transport models. Measurements combined proton‐transfer reaction mass spectrometry (PTRMS) and iodide chemical ionization mass spectrometry (ICIMS) over a Colorado pine forest; together, these techniques have been shown to capture the majority of ambient VOC abundance and reactivity. Total VOC mass and associated OH reactivity fluxes were dominated by emissions of 2‐methyl‐3‐buten‐2‐ol, monoterpenes, and small oxygenated VOCs, with a small number of compounds detected by PTRMS driving the majority of both net and upward exchanges. Most of these dominant species are explicitly included in chemical models, and we find here that GEOS‐Chem accurately simulates the net and upward VOC mass and OH reactivity fluxes under clear sky conditions. However, large upward terpene fluxes occurred during sustained rainfall, and these are not captured by the model. Far more species contributed to the downward fluxes than are explicitly modeled, leading to a major underestimation of this key sink of atmospheric reactive carbon. This model bias mainly reflects missing and underestimated concentrations of depositing species, though inaccurate deposition velocities also contribute. The deposition underestimate is particularly large for assumed isoprene oxidation products, organic acids, and nitrates—species that are primarily detected by ICIMS. Net ecosystem‐atmosphere fluxes of ozone reactivity were dominated by sesquiterpenes and monoterpenes, highlighting the importance of these species for predicting near‐surface ozone, oxidants, and aerosols.

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Section: Methodsmentioning

confidence: 99%

“…Kim et al, 2010). Other detailed atmospheric chemistry studies at MEFO have primarily focused on reactive carbon abundance and chemistry (Karl et al, 2012;Kaser et al, 2013b;Link et al, 2021;Wolfe et al, 2014;Zhou et al, 2015).…”

Section: Measurement Sitementioning

confidence: 99%

Closing the Reactive Carbon Flux Budget: Observations From Dual Mass Spectrometers Over a Coniferous Forest

et al. 2023

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“…The concentrations of non-fossil oxalic acid in the cities in South China were higher in winter than summer. However, biogenic compounds (e.g., isoprene (Bikkina et al, 2014(Bikkina et al, , 2021 and monoterpene (Link et al, 2021)) may contribute a smaller proportion of non-fossil oxalic acid in winter than summer. The high non-fossil oxalic acid concentrations found in winter may therefore have been caused by local and regional biomass burning.…”

Section: Radiocarbon-based Oxalic Acid Source Apportionmentmentioning

confidence: 99%

Fates of secondary organic aerosols in the atmosphere identified from compound-specific dual-carbon isotope analysis of oxalic acid

Tang

et al. 2023

Atmos. Chem. Phys.

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Abstract. Secondary organic aerosols (SOAs) are important components of fine particulates in the atmosphere. However, the sources of SOA precursor and atmospheric processes affecting SOAs are poorly understood. This limits our abilities to improve air quality and model aerosol-mediated climate forcing. Here, we use novel compound-specific dual-carbon isotope fingerprints (Δ14C and δ13C) for individual SOA tracer molecules (i.e., oxalic acid) to investigate the fates of SOAs in the atmosphere at five emission hotspots in China. Coal combustion and vehicle exhaust accounted for ∼ 55 % of the sources of carbon in oxalic acid in Beijing and Shanghai, but biomass burning and biogenic emissions accounted for ∼ 70 % of the sources of carbon in oxalic acid in Chengdu, Guangzhou, and Wuhan during the sampling period. The dual-carbon isotope signatures of oxalic acid and bulk organic carbon pools (e.g., water-soluble organic carbon) were compared to investigate the fates of SOAs in the atmosphere. Photochemical aging and aqueous-phase chemical processes dominate the formation of oxalic acid in summer and in winter, respectively. The results indicated that SOA carbon sources and chemical processes producing SOAs vary spatially and seasonally, and these variations need to be included in Chinese climate projection models and air quality management practices.

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“…However, biogenic compounds (e.g., isoprene (Bikkina et al, 2014;Bikkina et al, 2021) and monoterpene (Link et al, 2021)) may contribute a smaller proportion of non-fossil oxalic acid in winter than summer. The high non-fossil oxalic acid concentrations found in winter may therefore have been caused by local and regional biomass burning.…”

Section: Radiocarbon-based Oxalic Acid Source Apportionmentmentioning

confidence: 99%

Fates of secondary organic aerosols in the atmosphere identified from compound-specific dual-carbon isotope analysis of oxalic acid

Tang

et al. 2022

Preprint

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Abstract. Secondary organic aerosols (SOAs) are important components of fine particulates in the atmosphere. However, the sources of SOA precursor and atmospheric processes affecting SOAs are poorly understood. This limits our abilities to improve air quality and model aerosol-mediated climate forcing. Here, we use novel compound-specific dual-carbon isotope fingerprints (Δ14C and δ13C) for dominant SOA tracer molecules (oxalic acid and related polar compounds) to investigate the fates of SOAs in the atmosphere at five emission hotspots in China. Coal combustion and vehicle exhausts accounted for ~55 % of the sources of carbon in oxalic acid in Beijing and Shanghai, but biomass-burning and biogenic emissions accounted for ~70 % of the sources of carbon in oxalic acid in Chengdu, Guangzhou, and Wuhan. The dual-carbon isotope signatures of SOA molecules and bulk organic carbon pools (e.g., water-soluble organic carbon) were compared to investigate the fates of SOAs in the atmosphere. Photochemical aging of organic aerosols was dominant in summer, but fresh SOA formation from precursor volatile organic compounds was dominant in winter. The results indicated that SOA carbon sources and chemical processes producing SOAs vary spatially and seasonally and these variations need including in Chinese climate projection models and air quality management practices.

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Isoprene versus Monoterpenes as Gas-Phase Organic Acid Precursors in the Atmosphere

Cited by 17 publications

References 78 publications

Closing the Reactive Carbon Flux Budget: Observations From Dual Mass Spectrometers Over a Coniferous Forest

Closing the Reactive Carbon Flux Budget: Observations From Dual Mass Spectrometers Over a Coniferous Forest

Fates of secondary organic aerosols in the atmosphere identified from compound-specific dual-carbon isotope analysis of oxalic acid

Fates of secondary organic aerosols in the atmosphere identified from compound-specific dual-carbon isotope analysis of oxalic acid

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