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Organic peroxy (RO2) and hydroperoxy (HO2) radicals are key intermediates in the photochemical processes that generate ozone, secondary organic aerosol and reactive nitrogen reservoirs throughout the troposphere. In regions with ample biogenic hydrocarbons, the richness and complexity of peroxy radical chemistry presents a significant challenge to current-generation models, especially given the scarcity of measurements in such environments. We present peroxy radical observations acquired within a ponderosa pine forest during the summer 2010 Bio-hydroatmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen - Rocky Mountain Organic Carbon Study (BEACHON-ROCS). Total peroxy radical mixing ratios reach as high as 180 pptv (parts per trillion by volume) and are among the highest yet recorded. Using the comprehensive measurement suite to constrain a near-explicit 0-D box model, we investigate the sources, sinks and distribution of peroxy radicals below the forest canopy. The base chemical mechanism underestimates total peroxy radicals by as much as a factor of 3. Since primary reaction partners for peroxy radicals are either measured (NO) or underpredicted (HO2 and RO2, i.e., self-reaction), missing sources are the most likely explanation for this result. A close comparison of model output with observations reveals at least two distinct source signatures. The first missing source, characterized by a sharp midday maximum and a strong dependence on solar radiation, is consistent with photolytic production of HO2. The diel profile of the second missing source peaks in the afternoon and suggests a process that generates RO2 independently of sun-driven photochemistry, such as ozonolysis of reactive hydrocarbons. The maximum magnitudes of these missing sources (~120 and 50 pptv min-1, respectively) are consistent with previous observations alluding to unexpectedly intense oxidation within forests. We conclude that a similar mechanism may underlie many such observations. [ABSTRACT FROM AUTHOR]

Volatile organic compound (VOC) mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (Pinus Ponderosa) during the BEACHON-ROCS field study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS), a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS), a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA), a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS) and a Fiber Laser- Induced Fluorescence Instrument (FILIF). The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO) and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK) and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR) is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK+MAC) using PTR-(TOF)-MS at this site. A study-average relative contribution of 85% for MVK+MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20-25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the study, and likely points to an offset in calibration, rather than a difference in the ability to measure the sum of terpenes. The contribution of isoprene relative to MBO inferred from PTR-MS and PTR-TOF-MS was smaller than 12% while GC-MS data suggested an average of 21% of isoprene relative to MBO. This comparison demonstrates that the current capability of VOC measurements to account for OH reactivity associated with the measured VOCs is within 20%. [ABSTRACT FROM AUTHOR]

We report the first observations of formaldehyde (HCHO) flux measured via eddy covariance, as well as HCHO concentrations and gradients, as observed by the Madison Fiber Laser-Induced Fluorescence Instrument during the BEACHON-ROCS 2010 campaign in a rural, Ponderosa Pine forest northwest of Colorado Springs, CO. A median noon upward flux of ~80 µg m-2 h-1 (~24 pptv m s-1) was observed with a noon range of 37 to 131 µg m-2 h-1. Enclosure experiments were performed to determine the HCHO branch (3.5 µg m-2 h-1) and soil (7.3 µg m-2 h-1) direct emission rates in the canopy. A zero-dimensional canopy box model, used to determine the apportionment of HCHO source and sink contributions to the flux, underpredicted the observed HCHO flux by a factor of 6. Simulated increases in concentrations of species similar to monoterpenes resulted in poor agreement with measurements, while simulated increases in direct HCHO emissions and/or concentrations of species similar to 2-methyl-3-buten-2-ol best improved model/measurement agreement. Given the typical diurnal variability of these BVOC emissions and direct HCHO emissions, this suggests that the source of the missing flux is a process with both a strong temperature and radiation dependence. [ABSTRACT FROM AUTHOR]

During the second Texas Air Quality Study 2006 (TexAQS II), a full range of pollutants was measured by aircraft in eastern Texas during successive transects of power plant plumes (PPPs). A regional photochemical model is applied to simulate the physical and chemical evolution of the plumes. The observations reveal that SO2 and NOy were rapidly removed from PPPs on a cloudy day but not on the cloud-free days, indicating efficient aqueous processing of these compounds in clouds. The model reasonably represents observed NOx oxidation and PAN formation in the plumes, but fails to capture the rapid loss of SO2 (0.37 h-1) and NOy (0.24 h-1) in some plumes on the cloudy day. Adjustments to the cloud liquid water content (QC) and the default metal concentrations in the cloud module could explain some of the SO2 loss. However, NOy in the model was insensitive to QC. These findings highlight cloud processing as a major challenge to atmospheric models. Model-based estimates of ozone production efficiency (OPE) in PPPs are 20-50% lower than observation-based estimates. Possible explanations for this discrepancy include the observed rapid NOy loss which biases 15 high some observation-based OPE estimates, and the model\s under-prediction of isoprene emissions. [ABSTRACT FROM AUTHOR]

The article offers information on the 140 intercomparisons of data collected during U.S. National Aeronautics and Space Administration's (NASA) Intercontinental Chemical Transport Experiment-B (INTEX-B) mission. It says that the INTEX-B, part of the NASA-led INTEX-NA mission, was the second major airborne field mission aiming to investigate the transport and transportation of pollution over the North American continent. It notes that it operates in coordination with MILAGRO and IMPEX missions.

We construct a global atmospheric budget for acetaldehyde using a 3-D model of atmospheric chemistry (GEOS-Chem), and use an ensemble of observations to evaluate present understanding of its sources and sinks. Hydrocarbon oxidation provides the largest acetaldehyde source in the model (130 Tg a-1), with alkanes, alkenes, ethanol, and isoprene the main precursors. We use an updated chemical mechanism for GEOS-Chem, and photochemical acetaldehyde yields are consistent with the Master Chemical Mechanism. We apply SeaWiFS satellite observations to define the global distribution of light absorption due to marine dissolved organic matter (DOM), and estimate the corresponding sea-to-air acetaldehyde flux based on measured photoproduction rates from DOM. The resulting net ocean emission is 58 Tg a-1, the second largest global source of acetaldehyde. Quantitative model evaluation over the ocean is complicated by known measurement artifacts in clean air. Simulated concentrations in surface air over the ocean generally agree well with aircraft measurements, though the model tends to overestimate the vertical gradient. PAN:NOx ratios are well-simulated in the marine boundary layer, providing some support for the modeled ocean source. A key uncertainty is the acetaldehyde turnover time in the ocean mixed layer. We introduce the Model of Emissions of Gases and Aerosols from Nature (MEGANv2.1) for acetaldehyde and ethanol and use it to quantify their net flux from living terrestrial plants. Including emissions from decaying plants the total direct acetaldehyde source from the land biosphere is 22 Tg a-1. Other terrestrial acetaldehyde sources include biomass burning (3 Tg a-1) and anthropogenic emissions (2 Tg a-1). Simulated concentrations in the continental boundary layer are generally unbiased and capture the spatial gradients seen in observations over North America, Europe, and tropical South America. However, the model underestimates acetaldehyde levels in urban outflow, suggesting a missing source in polluted air. Ubiquitous high measured concentrations in the free troposphere are not captured by the model, and based on present understanding are not consistent with concurrent measurements of PAN and NOx. We find no compelling evidence for a widespread missing acetaldehyde source in the free troposphere. We estimate the current US source of ethanol and acetaldehyde (primary+secondary) at 1.3 Tg a-1 and 7.0 Tg a-1, approximately 60% and 400% of the corresponding increases expected for a national transition from gasoline to ethanol fuel. [ABSTRACT FROM AUTHOR]

The volatile organic compound (VOC) distribution in the Mexico City Metropolitan Area (MCMA) and its evolution as it is uplifted and transported out of the MCMA basin was studied during the 2006 MILAGRO/MIRAGE-Mex field campaign. The results show that in the morning hours in the city center, the VOC distribution is dominated by nonmethane hydrocarbons (NMHCs) but with a substantial contribution from oxygenated volatile organic compounds (OVOCs), predominantly from primary emissions. Alkanes account for a large part of the NMHC distribution in terms of mixing ratios. In terms of reactivity, NMHCs also dominate overall, especially in the morning hours. However, in the afternoon, as the boundary layer lifts and air is mixed and aged within the basin, the distribution changes as secondary products are formed. The WRF-Chem (Weather Research and Forecasting with Chemistry) model and MOZART (Model for Ozone and Related chemical Tracers) were able to reproduce the general features of the daytime cycle of the VOC OH reactivity distribution showing that NMHCs dominate the distribution except in the afternoon hours and that the VOC OH reactivity peaks in the early morning due to high morning emissions from the city into a shallow boundary layer. The WRF-Chem and MOZART models showed higher reactivity than the experimental data during the nighttime cycle, perhaps indicating problems with the modeled nighttime boundary layer height. In addition, a plume was studied in which air was advected out of the MCMA and intercepted downwind with the DOE G1 on 18 March and the NCAR C130 one day later on 19 March. A number of identical species measured aboard each aircraft gave insight into the chemical evolution of the plume as it aged and was transported as far as 1000km downwind. Ozone and many OVOCs were photochemically produced in the plume. The WRF-Chem and MOZART models were used to examine the spatial and temporal extent of the 19 March plume and to help interpret the OH reactivity in the downwind plume. The model results generally showed good agreement with experimental results for the total VOC OH reactivity downwind and gave insight into the distributions of VOC chemical classes downwind. A box model with detailed gas phase chemistry (NCAR Master Mechanism), initialized with concentrations observed at one of the ground sites in the MCMA, was used to examine the expected evolution of specific VOCs over a 1-2 day period. The models clearly supported the experimental evidence for NMHC oxidation leading to the formation of OVOCs downwind, which then become the primary fuel for ozone production far away from the MCMA. [ABSTRACT FROM AUTHOR]

The NO-NO2 system was analyzed in different chemical regimes/air masses based on observations of reactive nitrogen species and peroxy radicals made during the intensive field campaign MIRAGE-Mex (4 to 29 March 2006). The air masses were categorized into 5 groups based on combinations of macroscopic observations, geographical location, meteorological parameters, models, and observations of trace gases: boundary layer (labeled as "BL"), biomass burning ("BB"), free troposphere (continental, "FTCO" and marine, "FTMA"), and Tula industrial complex ("TIC"). In general, NO2/NO ratios in different air masses are near photostationary state. Analysis of this ratio can be useful for testing current understanding of tropospheric chemistry. The ozone production efficiency (OPE) for the 5 air mass categories ranged from 4.5 (TIC) to 8.5 (FTMA), consistent with photochemical aging of air masses exiting the Mexico City Metropolitan Area. [ABSTRACT FROM AUTHOR]