The OH radical is the most important tropospheric oxidant. An important question surrounds missing OH sink terms observed in biogenically influenced regions, which have been proposed to be caused by unmeasured biogenic volatile organic compounds (BVOCs). Formaldehyde (HCHO) is formed during oxidation of virtually all BVOCs. Observation of the HCHO efflux from the forest provides a direct measure of HCHO sources and serves as constraint on the in-canopy oxidation of unmeasured, reactive BVOCs. We present the first reported measurements of HCHO flux via eddy covariance observed with the Madison Fiber Laser-Induced Fluorescence instrument in a rural forest northwest of Colorado Springs, CO. Upward HCHO fluxes up to 200 μg m -2 hr -1 were observed. We investigate the contribution of fast VOC oxidation chemistry and other HCHO emission sources, such as soil, leaf litter and plants, to assess whether the observed fluxes can be explained with known in-canopy sources and sinks of HCHO.

Airborne measurements of formaldehyde (CH2O) were acquired employing tunable diode laser absorption spectroscopy (TDLAS) during the 2000 Tropospheric Ozone Production About the Spring Equinox (TOPSE) study. This study consisted of seven deployments spanning the time period from 4 February to 23 May 2000 and covered a wide latitudinal band from 40°N to 85°N. The median measured CH2O concentrations, with a few exceptions, did not show any clear temporal trends from February to May in each of five altitude and three latitude bins examined. Detailed measurement-model comparisons were carried out using a variety of approaches employing two different steady state models. Because recent emissions of CH2O and/or its precursors often result in model underpredictions, background conditions were identified using a number of chemical tracers. For background conditions at temperatures warmer than -45°C, the measurement-model agreement on average ranged between -13% and +5% (measurement- model/measurement), which corresponded to mean and median (measurement- model) differences of 3 ± 69 and -6 parts per trillion by volume (pptv), respectively. At very low temperatures starting at around -45°C, significant and persistent (measurement-model) differences were observed from February to early April from southern Canada to the Arctic Ocean in the 6-8 km altitude range. In such cases, measured CH2O was as much as 392 pptv higher than modeled, and the median difference was 132 pptv (83%). Low light conditions as well as cold temperatures may be important in this effect. A number of possible mechanisms involving the reaction of CH3O2 with HO2 to produce CH2O directly were investigated, but in each case the discrepancy was only minimally reduced. Other possibilities were also considered but in each case there was no compelling evidence to support any of the hypotheses. Whatever the cause, the elevated CH2O concentrations significantly impact upper tropospheric HOx levels at high latitudes (>57°N ) in the February-April time frame.

Abstract. Evolution of organic aerosol (OA) and their precursors in the boundary layer of Colorado Front Range during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ, July–August 2014) was analyzed by in-situ measurements and chemical transport modeling. Measurements indicated significant production of secondary OA (SOA), with enhancement ratio of OA with respect to carbon monoxide (CO) reaching 0.068 ± 0.004 μg m−3 ppbv−1. At background mixing ratios of CO, up to ~ 2 μg m−3 background OA was observed, suggesting significant non-combustion contribution to OA in the Front Range. The mean concentration of OA in plumes with a high influence of oil and natural gas (O&G) emissions was ~ 40 % higher than in urban-influenced plumes. Positive matrix factorization confirmed a dominant contribution of secondary, oxygenated OA (OOA) in the boundary layer instead of fresh, hydrocarbon-like OA (HOA). Combinations of primary OA (POA) volatility assumptions, aging of semi-volatile species, and different emission estimates from the O&G sector were used in the Weather Research and Forecasting model, coupled with Chemistry (WRF-Chem) simulation scenarios. The assumption of semi-volatile POA resulted in greater than a factor of 10 lower POA concentrations compared to PMF-resolved HOA. Including a top-down modified O&G emissions resulted in substantially better agreements in modeled ethane, toluene, hydroxyl radical, and ozone compared to measurements in the high O&G-influenced plumes. By including emissions from the O&G sector using the top-down approach, it was estimated that the O&G sector contributed to

The evolution of organic aerosols (OAs) and their precursors in the boundary layer (BL) of the Colorado Front Range during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ, July-August 2014) was analyzed by in situ measurements and chemical transport modeling. Measurements indicated significant production of secondary OA (SOA), with enhancement ratio of OA with respect to carbon monoxide (CO) reaching 0.085±0.003ĝ€μgĝ€mĝ'3 ppbvĝ'1. At background mixing ratios of CO, up to ĝ1/4 ĝ€1.8ĝ€μgĝ€mĝ'3 background OA was observed, suggesting significant non-combustion contribution to OA in the Front Range. The mean concentration of OA in plumes with a high influence of oil and natural gas (O&G) emissions was ĝ1/4 ĝ€40ĝ€% higher than in urban-influenced plumes. Positive matrix factorization (PMF) confirmed a dominant contribution of secondary, oxygenated OA (OOA) in the boundary layer instead of fresh, hydrocarbon-like OA (HOA). Combinations of primary OA (POA) volatility assumptions, aging of semi-volatile species, and different emission estimates from the O&G sector were used in the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) simulation scenarios. The assumption of semi-volatile POA resulted in greater than a factor of 10 lower POA concentrations compared to PMF-resolved HOA. Including top-down modified O&G emissions resulted in substantially better agreements in modeled ethane, toluene, hydroxyl radical, and ozone compared to measurements in the high-O&G-influenced plumes. By including emissions from the O&G sector using the top-down approach, it was estimated that the O&G sector contributed to < ĝ€5ĝ€% of total OA, but up to 38ĝ€% of anthropogenic SOA (aSOA) in the region. The best agreement between the measured and simulated median OA was achieved by limiting the extent of biogenic hydrocarbon aging and consequently biogenic SOA (bSOA) production. Despite a lower production of bSOA in this scenario, contribution of bSOA to total SOA remained high at 40-54ĝ€%. Future studies aiming at a better emissions characterization of POA and intermediate-volatility organic compounds (IVOCs) from the O&G sector are valuable.