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The budget of reactive nitrogen species, which play a central role in atmospheric chemistry (e.g. in photochemical O3 production), is poorly understood in forested regions. In this study, through observations of NO, NO2 , NOy , and O3 in the Rambouillet Forest near Paris, France, we have examined nighttime processes controlling NOx in an anthropogenically impacted forest environment. The O3 mixing ratios displayed a strong diel profile at the site that was driven by a variable but generally rapid deposition to soil and foliar surfaces. The O3 diel profile was strongly influenced by relative humidity and temperature inversion. Only when the O3 mixing ratio was sufficiently low (and thus the NO lifetime sufficiently long) were sustained NO peaks observed above the instrumental detection limit, enabling the derivation of average NO emission rates of ∼1.4 ppbvh-1 from the soil. Observations of the lack of increase in NO2 at night, despite a significant production rate from the reaction of NO with O3 , enabled an effective lifetime of NO2 of ∼0.5 –3 h to be derived. As the loss of NO2 was not compensated for by the formation of gas- or particle-phase reactive nitrogen species, it was presumably either driven by deposition to soil and foliar surfaces or any products formed were themselves short-lived with respect to deposition. By comparison, the daytime lifetime of NO2 with respect to loss by reaction with OH is about 1 d. Our results indicate that the nighttime deposition of NO2 is a major sink of boundary layer NOx in this temperate forest environment. [ABSTRACT FROM AUTHOR]

We present direct measurements of biogenic volatile organic compound (BVOC)-induced nitrate radical (NO3) reactivity (kVOC) through the diel cycle in the suburban, temperate forest of Rambouillet near Paris (France). The data were obtained in a 6-week summer period in 2022 as part of the Atmospheric ChemistRy Of the Suburban foreSt (ACROSS) campaign. kVOC was measured in a small (700 m2) clearing mainly at a height of 5.5 m above ground level but also at 40 m (for 5 d and nights). At nighttime, mean values (and 25th–75th percentile ranges) of knightVOC(5.5m) = (0.24-0.06+0.32) s-1 and knightVOC(40m) = (0.016-0.007+0.018) s-1 indicate a significant vertical gradient and low NO3 reactivity above the canopy, whereas knightVOC (5.5 m) showed peak values of up to 2 s-1 close to the ground. The strong vertical gradient in NO3 reactivity could be confirmed by measurements between 0 and 24 m on one particular night characterized by a strong temperature inversion and is a result of the decoupling of air masses aloft from the ground- and canopy-level sources of BVOCs (and nitric oxide, NO). No strong vertical gradient was observed in the mean daytime NO3 reactivity, with kdayVOC(5.5m) = (0.12±0.04) s-1 for the entire campaign and kdayVOC(40m) = (0.07±0.02) s-1 during the 5 d period. Within the clearing, the fractional contribution of VOCs to the total NO3 loss rate coefficient (ktot , determined by photolysis, reaction with NO and VOCs) was 80 %–90 % during the night and ∼ 50 % during the day. In terms of chemical losses of α -pinene below canopy height in the clearing, we find that at nighttime hydroxyl radicals (OH) and ozone (O3) dominate, with NO3 contributing "only" 17 %, which decreases further to 8.5 % during the day. Based on measured OH, measured O3 , and calculated NO3 concentrations, the chemical lifetime of BVOCs at noon is about 1 h and is likely to be longer than timescales of transport out of the canopy (typically of the order of minutes), thus significantly reducing the importance of daytime in-canopy processing. Clearly, in forested regions where sufficient nitric oxide and nitrogen dioxide (NOx) is available, the role of NO3 and OH as initiators of BVOC oxidation is not strictly limited to nighttime and daytime, respectively, as often implied in e.g. atmospheric chemistry textbooks. [ABSTRACT FROM AUTHOR]

​​​​​​​Volatile organic compounds (VOCs) play a key role in tropospheric chemistry, giving rise to secondary products such as highly oxygenated organic molecules (HOMs) and secondary organic aerosols (SOAs). HOMs, a group of low-volatility gas-phase products, are formed through the autoxidation process of peroxy radicals (RO 2) originating from the oxidation of VOCs. The measurement of HOMs is made by a NO 3- ToFCIMS instrument, which also detects other species like small highly oxygenated VOCs (e.g., dicarboxylic acids) and sulfuric acid (H 2 SO 4). The instrument response to HOMs is typically estimated using H 2 SO 4 , as HOMs are neither commercially available nor easily synthesized in the laboratory. The resulting calibration factor is then applied to quantify all species detected using this technique. In this study, we explore the sensitivity of the instrument to commercially available small organic compounds, primarily dicarboxylic acids, given the limitations associated with producing known amounts of HOMs for calibration. We compare these single-compound calibration factors to the one obtained for H 2 SO 4 under identical operational conditions. The study found that the sensitivity of the NO 3- ToFCIMS varies depending on the specific type of organic compound, illustrating how a single calibration factor derived from sulfuric acid is clearly inadequate for quantifying all detected species using this technique. The results highlighted substantial variability in the calibration factors for the tested organic compounds, with 4-nitrocatechol exhibiting the highest sensitivity and pyruvic acid the lowest. The obtained sulfuric acid calibration factor agreed well with the previous values from the literature. In summary, this research emphasized the need to develop reliable and precise calibration methods for progressively oxygenated reaction products measured with a NO 3- chemical-ionization mass spectrometer (CIMS), for example, HOMs. [ABSTRACT FROM AUTHOR]

We present direct measurements of BVOC-induced nitrate radical (NO3) reactivity (kVOC) through the diel cycle in the suburban, temperate forest of Rambouillet near Paris (France). The data were obtained in a six-week summer period in 2022 as part of the ACROSS campaign (Atmospheric ChemistRy Of the Suburban foreSt). kVOC was measured in a small (700 m²) clearing mainly at a height of 5.5 m above ground level, but also at 40 m (for 5 days/nights). At nighttime, mean values of kVOCnight (5.5 m) = (0.24 ± 0.27) s-1 and kVOCnight (40 m) = (0.016 ± 0.007) s-1 indicate a significant vertical gradient and low NO3 reactivity above the canopy, whereas kVOCnight (5.5 m) showed peak values of up to 2 s-1 close to the ground. The strong vertical gradient in NO3 reactivity could be confirmed by measurements between 0 and 24 m on one particular night characterised by a strong temperature inversion, and is a result of the decoupling of air masses aloft from the ground- and canopy-level sources of BVOCs (and NO). No strong vertical gradient was observed in the mean daytime NO3 reactivity with kVOCnight(5.5 m) = (0.12 ± 0.04) s-1 for the entire campaign and kVOCnight(40 m) = (0.07 ± 0.02) s-1 during the 5-day period. Within the clearing, the fractional contribution of VOCs to the total NO3 loss rate (LNO3, determined by photolysis, reaction with NO and VOCs) was 80-90 % during the night and ~50 % during the day. In terms of chemical losses of α-pinene below canopy height in the clearing, we find that at nighttime OH and O3 dominate with NO3 contributing "only" 17 %, which decreases further to 8.5 % during the day. Based on OH, O3 and NO3 concentrations, the chemical lifetime of BVOCs at noon is about one hour and is likely to be longer than timescales of transport out of the canopy (typically in the order of minutes), thus significantly reducing the importance of daytime, in-canopy processing. Clearly, in forested regions where sufficient NOX is available, the role of NO3 and OH as initiators of BVOC oxidation are not strictly limited to the night and to the day, respectively, as often implied in e.g. atmospheric chemistry text-books. [ABSTRACT FROM AUTHOR]

Volatile organic compounds (VOCs) play a key role in tropospheric chemistry, giving rise to secondary products such as highly oxygenated organic molecules (HOMs) and secondary organic aerosols (SOA). HOMs, a group of low-volatility gas-phase products, are formed through the autoxidation process of peroxy radicals (RO2) originating from the oxidation of VOCs. The measurement of HOMs is made by a NO3¯ ToFCIMS instrument, which also detects other species like small highly oxygenated VOCs (e.g. dicarboxylic acids) and sulfuric acid (H2SO4). The instrument response to HOMs is typically estimated using H2SO4, as HOMs are neither commercially available nor easily synthesized in the laboratory. The resulting calibration factor is then applied to quantify all species detected using this technique. In this study, we explore the sensitivity of the instrument to commercially available small organic compounds, primarily dicarboxylic acids, given the limitations associated with producing known amounts of HOMs for calibration. We compare these single compound calibration factors to the one obtained for H2SO4 under identical operational conditions. The study found that the sensitivity of the NO3¯ ToFCIMS varies depending on the specific type of organic compound, illustrating how a single calibration factor derived from sulfuric acid is clearly inadequate for quantifying all detected species using this technique. The results highlighted substantial variability in the calibration factors for the tested organic compounds, with 4-nitrocatechol exhibiting the highest sensitivity, and pyruvic acid the lowest. The obtained sulfuric acid calibration factor agreed well with the previous values from the literature. In summary, this research emphasized the need to develop reliable and precise calibration methods for progressively oxygenated reaction products measure with NO3¯ CIMS, for example, HOMs. [ABSTRACT FROM AUTHOR]

Through observations of NO, NO2, NOY and O3 in the Rambouillet forest near Paris, France, (as part of the ACROSS campaign, 2022) we have gained insight into nighttime processes controlling NOX in an anthropogenically impacted forest environment. O3 mixing ratios displayed a strong diel profile at the site, which was driven by a variable but generally rapid deposition to soil and foliar surfaces. The O3 diel profile was strongly influenced by relative humidity, which impacted the surface resistance to uptake, and temperature inversion, which influenced the rate of entrainment of O3 from above the canopy. Only when the O3 mixing ratio was sufficiently low (and thus the NO lifetime sufficiently long), were sustained NO peaks observed above the instrumental detection limit, enabling derivation of average NO emission rates from the soil of -1.4 ppbv h-1. Observations of the lack of increase in NO2 at night, despite a significant production rate from the reaction of NO with O3, enabled an effective lifetime of NO2 of -0.5-3 h to be derived. As the loss of NO2 was not compensated by the formation of gas- or particle-phase reactive nitrogen species it was presumably driven by deposition to soil and foliar surfaces, or any products formed were themselves short-lived with respect to deposition. By comparison, the daytime lifetime of NO2 with respect to loss by reaction with OH is about 1 day. We conclude that the nighttime deposition of NO2 is a major sink of boundary layer NOX in this temperate forest environment. [ABSTRACT FROM AUTHOR]

Through observations of NO, NO2, NOY and O3 in the Rambouillet forest near Paris, France, (as part of the ACROSS campaign, 2022) we have gained insight into nighttime processes controlling NOX in an anthropogenically impacted forest environment. O3 mixing ratios displayed a strong diel profile at the site, which was driven by a variable but generally rapid deposition to soil and foliar surfaces. The O3 diel profile was strongly influenced by relative humidity, which impacted the surface resistance to uptake, and temperature inversion, which influenced the rate of entrainment of O3 from above the canopy. Only when the O3 mixing ratio was sufficiently low (and thus the NO lifetime sufficiently long), were sustained NO peaks observed above the instrumental detection limit, enabling derivation of average NO emission rates from the soil of ~1.4 ppbv h‑1. Observations of the lack of increase in NO2 at night, despite a significant production rate from the reaction of NO with O3, enabled an effective lifetime of NO2 of ⁓0.5–3 h to be derived. As the loss of NO2 was not compensated by the formation of gas- or particle-phase reactive nitrogen species it was presumably driven by deposition to soil and foliar surfaces, or any products formed were themselves short-lived with respect to deposition. By comparison, the daytime lifetime of NO2 with respect to loss by reaction with OH is about 1 day. We conclude that the nighttime deposition of NO2 is a major sink of boundary layer NOX in this temperate forest environment. [ABSTRACT FROM AUTHOR]