The lifetime of nitrogen oxides in an isoprene-dominated forest

The lifetime of nitrogen oxides (NO_x) affects the concentration and distribution of NO_x and the spatial patterns of nitrogen deposition. Despite its importance, the lifetime of NO_x is poorly constrained in rural and remote continental regions. We use measurements from a site in central Alabama during the Southern Oxidant and Aerosol Study (SOAS) in summer 2013 to provide new insights into the chemistry of NO_x and NO_x reservoirs. We find that the lifetime of NO_x during the daytime is controlled primarily by the production and loss of alkyl and multifunctional nitrates (ΣANs). During SOAS, ΣAN production was rapid, averaging 90 ppt h^(−1) during the day, and occurred predominantly during isoprene oxidation. Analysis of the ΣAN and HNO_3 budgets indicate that ΣANs have an average lifetime of under 2 h, and that approximately 45 % of the ΣANs produced at this site are rapidly hydrolyzed to produce nitric acid. We find that ΣAN hydrolysis is the largest source of HNO_3 and the primary pathway to permanent removal of NO_x from the boundary layer in this location. Using these new constraints on the fate of ΣANs, we find that the NO_x lifetime is 11 ± 5 h under typical midday conditions. The lifetime is extended by storage of NO_x in temporary reservoirs, including acyl peroxy nitrates and ΣANs

The lifetime of nitrogen oxides in an isoprene-dominated forest

The lifetime of nitrogen oxides (NOx) affects the concentration and distribution of NOx&nbsp;and the spatial patterns of nitrogen deposition. Despite its importance, the lifetime of NOx&nbsp;is poorly constrained in rural and remote continental regions. We use measurements from a site in central Alabama during the Southern Oxidant and Aerosol Study (SOAS) in summer 2013 to provide new insights into the chemistry of NOx&nbsp;and NOx&nbsp;reservoirs. We find that the lifetime of NOx&nbsp;during the daytime is controlled primarily by the production and loss of alkyl and multifunctional nitrates (&Sigma;ANs). During SOAS, &Sigma;AN production was rapid, averaging 90 ppt h-1 during the day, and occurred predominantly during isoprene oxidation. Analysis of the &Sigma;AN and HNO3 budgets indicate that &Sigma;ANs have an average lifetime of under 2 h, and that approximately 45 % of the &Sigma;ANs produced at this site are rapidly hydrolyzed to produce nitric acid. We find that &Sigma;AN hydrolysis is the largest source of HNO3&nbsp;and the primary pathway to permanent removal of NOx&nbsp;from the boundary layer in this location. Using these new constraints on the fate of &Sigma;ANs, we find that the NOx&nbsp;lifetime is 11&thinsp;&plusmn;&thinsp;5 h under typical midday conditions. The lifetime is extended by storage of NOx&nbsp;in temporary reservoirs, including acyl peroxy nitrates and &Sigma;ANs.</p

The lifetime of nitrogen oxides in an isoprene-dominated forest

The lifetime of nitrogen oxides (NO_x) affects the concentration and distribution of NO_x and the spatial patterns of nitrogen deposition. Despite its importance, the lifetime of NO_x is poorly constrained in rural and remote continental regions. We use measurements from a site in central Alabama during the Southern Oxidant and Aerosol Study (SOAS) in summer 2013 to provide new insights into the chemistry of NO_x and NO_x reservoirs. We find that the lifetime of NO_x during the daytime is controlled primarily by the production and loss of alkyl and multifunctional nitrates (ΣANs). During SOAS, ΣAN production was rapid, averaging 90 ppt h^(−1) during the day, and occurred predominantly during isoprene oxidation. Analysis of the ΣAN and HNO_3 budgets indicate that ΣANs have an average lifetime of under 2 h, and that approximately 45 % of the ΣANs produced at this site are rapidly hydrolyzed to produce nitric acid. We find that ΣAN hydrolysis is the largest source of HNO_3 and the primary pathway to permanent removal of NO_x from the boundary layer in this location. Using these new constraints on the fate of ΣANs, we find that the NO_x lifetime is 11 ± 5 h under typical midday conditions. The lifetime is extended by storage of NO_x in temporary reservoirs, including acyl peroxy nitrates and ΣANs

Evaporation kinetics of aqueous acetic acid droplets: effects of soluble organic aerosol components on the mechanism of water evaporation.

The presence of organic surfactants in atmospheric aerosol may lead to a depression of cloud droplet growth and evaporation rates affecting the radiative properties and lifetime of clouds. Both the magnitude and mechanism of this effect, however, remain poorly constrained. We have used Raman thermometry measurements of freely evaporating micro-droplets to determine evaporation coefficients for several concentrations of acetic acid, which is ubiquitous in atmospheric aerosol and has been shown to adsorb strongly to the air-water interface. We find no suppression of the evaporation kinetics over the concentration range studied (1-5 M). The evaporation coefficient determined for 2 M acetic acid is 0.53 ± 0.12, indistinguishable from that of pure water (0.62 ± 0.09)

Evaporation kinetics of aqueous acetic acid droplets: effects of soluble organic aerosol components on the mechanism of water evaporation.

The presence of organic surfactants in atmospheric aerosol may lead to a depression of cloud droplet growth and evaporation rates affecting the radiative properties and lifetime of clouds. Both the magnitude and mechanism of this effect, however, remain poorly constrained. We have used Raman thermometry measurements of freely evaporating micro-droplets to determine evaporation coefficients for several concentrations of acetic acid, which is ubiquitous in atmospheric aerosol and has been shown to adsorb strongly to the air-water interface. We find no suppression of the evaporation kinetics over the concentration range studied (1-5 M). The evaporation coefficient determined for 2 M acetic acid is 0.53 ± 0.12, indistinguishable from that of pure water (0.62 ± 0.09)

Cation-cation contact pairing in water: guanidinium.

The formation of like-charge guanidinium-guanidinium contact ion pairs in water is evidenced and characterized by X-ray absorption spectroscopy and first-principles spectral simulations based on molecular dynamics sampling. Observed concentration-induced nitrogen K-edge resonance shifts result from π* state mixing and the release of water molecules from each first solvation sphere as two solvated guanidinium ions associate into a stacked pair configuration. Possible biological implications of this counterintuitive cation-cation pairing are discussed

Cation-cation contact pairing in water: guanidinium.

The formation of like-charge guanidinium-guanidinium contact ion pairs in water is evidenced and characterized by X-ray absorption spectroscopy and first-principles spectral simulations based on molecular dynamics sampling. Observed concentration-induced nitrogen K-edge resonance shifts result from π* state mixing and the release of water molecules from each first solvation sphere as two solvated guanidinium ions associate into a stacked pair configuration. Possible biological implications of this counterintuitive cation-cation pairing are discussed

Effects of temperature-dependent NO&lt;sub&gt;&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt; emissions on continental ozone production

Surface ozone concentrations are observed to increase with rising temperatures, but the mechanisms responsible for this effect in rural and remote continental regions remain uncertain. Better understanding of the effects of temperature on ozone is crucial to understanding global air quality and how it may be affected by climate change. We combine measurements from a focused ground campaign in summer 2013 with a long-term record from a forested site in the rural southeastern United States, to examine how daily average temperature affects ozone production. We find that changes to local chemistry are key drivers of increased ozone concentrations on hotter days, with integrated daily ozone production increasing by 2.3 ppb ∘C−1. Nearly half of this increase is attributable to temperature-driven increases in emissions of nitrogen oxides (NOx), most likely by soil microbes. The increase of soil NOx emissions with temperature suggests that ozone will continue to increase with temperature in the future, even as direct anthropogenic NOx emissions decrease dramatically. The links between temperature, soil NOx, and ozone form a positive climate feedback

Organic nitrate contribution to the oxidized nitrogen budget at the 2013 Southern Oxidant and Aerosol Study (SOAS)

Org. nitrates (RONO_2) that are formed from the OH-initiated or NO_3-initiated oxidn. of biogenic alkenes can be important reservoirs and sinks for NO_x (NO + NO_2). Biogenic org. nitrates represent a significant fraction of the total NO_y budget in forested regions. During the 2013 Southern Oxidant and Aerosol Study (SOAS), speciated org. nitrates produced from the oxidn. of isoprene (C_5H_8) and monoterpenes (C_(10)H_(16)) were measured with high temporal resoln. and sensitivity by a time-of-flight chem. ionization mass spectrometer (ToF-CIMS) from a 20 m tower. Both dark and photochem. mechanisms were obsd. to be important for the prodn. of multifunctional org. nitrates at SOAS. The combined vol. mixing ratios of RONO_2 detd. by ToF-CIMS and GC-MS were compared to a thermal-dissocn. laser-induced fluorescence (TD-LIF) measurement of total org. nitrates in the gas and aerosol phase. The mass closure of org. nitrates in the gas-phase and their fractional contributions to the aerosol phase will be presented. The significance of org. nitrates to the overall nitrogen and oxidant budgets at SOAS will be discussed