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We have developed semi-independent methods for determining CH2O scavenging efficiencies (SEs) during strong midlatitude convection over the western, south-central Great Plains, and southeastern regions of the United States during the 2012 Deep Convective Clouds and Chemistry (DC3) Study. The Weather Research and Forecasting model coupled with chemistry (WRF-Chem) was employed to simulate one DC3 case to provide an independent approach of estimating SEs and the opportunity to study CH2O retention in icewhen liquid drops freeze. Measurements of CH2O instorminflow and outflow were acquired on board the NASA DC-8 and the NSF/National Center for Atmospheric Research Gulfstream V (GV) aircraft employing cross-calibrated infrared absorption spectrometers. This study also relied heavily on the nonreactive tracers i-/n-butane and i-/n-pentane measured on both aircraft in determining lateral entrainment rates during convection as well as their ratios to ensure that inflow and outflow air masses did not have different origins. Of the five storm cases studied, the various tracermeasurements showed that the inflow and outflow from four storms were coherently related. The combined average of the various approaches from these storms yield remarkably consistent CH2O scavenging efficiency percentages of: 54%± 3% for 29 May; 54% ± 6% for 6 June; 58%± 13% for 11 June; and 41 ± 4% for 22 June. The WRF-Chem SE result of 53% for 29 May was achieved only when assuming complete CH2O degassing from ice. Further analysis indicated that proper selection of corresponding inflow and outflow time segments is more important than the particular mixing model employed.

©2015. American Geophysical Union. All Rights Reserved. As part of the Deep Convective Cloud and Chemistry (DC3) experiment, the National Science Foundation/National Center for Atmospheric Research (NCAR) Gulfstream-V (GV) and NASA DC-8 research aircraft probed the chemical composition of the inflow and outflow of two convective storms (north storm, NS, south storm, SS) originating in the Colorado region on 22 June 2012, a time when the High Park wildfire was active in the area. A wide range of trace species were measured on board both aircraft including biomass burning (BB) tracers hydrogen cyanide (HCN) and acetonitrile (ACN). Acrolein, a much shorter lived tracer for BB, was also quantified on the GV. The data demonstrated that the NS had ingested fresh smoke from the High Park fire and as a consequence had a higher VOC OH reactivity than the SS. The SS lofted aged fire tracers along with other boundary layer ozone precursors and was more impacted by lightning NOx (LNOx) than the NS. The NCAR master mechanism box model was initialized with measurements made in the outflow of the two storms. The NS and SS were predicted to produce 11 and 14ppbv of O3, respectively, downwind of the storm over 2days. Sensitivity tests revealed that the ozone production potential of the SS was highly dependent on LNOx. Normalized excess mixing ratios, ΔX/ΔCO, for HCN and ACN were determined in both the fire plume and the storm outflow and found to be 7.0±0.5 and 2.3±0.5pptvppbv-1, respectively, and 1.4±0.3pptvppbv-1 for acrolein in the outflow only.

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-hydro-atmosphere 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 minĝ1, respectively) are consistent with previous observations alluding to unexpectedly intense oxidation within forests. We conclude that a similar mechanism may underlie many such observations. © 2014 Aothor(s).

At the Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) field campaign in the Colorado front range, July-August 2011, measurements of gas- and aerosol-phase organic nitrates enabled a study of the role of NOx (NOx Combining double low line NO + NO2) in oxidation of forest-emitted volatile organic compounds (VOCs) and subsequent aerosol formation. Substantial formation of peroxy- and alkyl-nitrates is observed every morning, with an apparent 2.9% yield of alkyl nitrates from daytime RO2 + NO reactions. Aerosol- phase organic nitrates, however, peak in concentration during the night, with concentrations up to 140 ppt as measured by both optical spectroscopic and mass spectrometric instruments. The diurnal cycle in aerosol fraction of organic nitrates shows an equilibrium-like response to the diurnal temperature cycle, suggesting some reversible absorptive partitioning, but the full dynamic range cannot be reproduced by thermodynamic repartitioning alone. Nighttime aerosol organic nitrate is observed to be positively correlated with [NO2] × [O3] but not with [O3]. These observations support the role of nighttime NO3-initiated oxidation of monoterpenes as a significant source of nighttime aerosol. Nighttime production of organic nitrates is comparable in magnitude to daytime photochemical production at this site, which we postulate to be representative of the Colorado front range forests. © 2013 Author(s).

We present a detailed analysis of OH observations from the BEACHON (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen)-ROCS (Rocky Mountain Organic Carbon Study) 2010 field campaign at the Manitou Forest Observatory (MFO), which is a 2-methyl-3-butene-2-ol (MBO) and monoterpene (MT) dominated forest environment. A comprehensive suite of measurements was used to constrain primary production of OH via ozone photolysis, OH recycling from HO2, and OH chemical loss rates, in order to estimate the steady-state concentration of OH. In addition, the University of Washington Chemical Model (UWCM) was used to evaluate the performance of a near-explicit chemical mechanism. The diurnal cycle in OH from the steady-state calculations is in good agreement with measurement. A comparison between the photolytic production rates and the recycling rates from the HO2 + NO reaction shows that recycling rates are ~20 times faster than the photolytic OH production rates from ozone. Thus, we find that direct measurement of the recycling rates and the OH loss rates can provide accurate predictions of OH concentrations. More importantly, we also conclude that a conventional OH recycling pathway (HO2 + NO) can explain the observed OH levels in this non-isoprene environment. This is in contrast to observations in isoprene-dominated regions, where investigators have observed significant underestimation of OH and have speculated that unknown sources of OH are responsible. The highly-constrained UWCM calculation under-predicts observed HO2 by as much as a factor of 8. As HO2 maintains oxidation capacity by recycling to OH, UWCM underestimates observed OH by as much as a factor of 4. When the UWCM calculation is constrained by measured HO2, model calculated OH is in better agreement with the observed OH levels. Conversely, constraining the model to observed OH only slightly reduces the model-measurement HO2 discrepancy, implying unknown HO2 sources. These findings demonstrate the importance of constraining the inputs to, and recycling within, the ROx radical pool (OH + HO2 + RO2).

We present simultaneous fast, in-situ measurements of formaldehyde and glyoxal from two rural campaigns, BEARPEX 2009 and BEACHON-ROCS, both located in Pinus Ponderosa forests with emissions dominated by biogenic volatile organic compounds (VOCs). Despite considerable variability in the formaldehyde and glyoxal concentrations, the ratio of glyoxal to formaldehyde, RGF, displayed a very regular diurnal cycle over nearly 2 weeks of measurements. The only deviations in RGF were toward higher values and were the result of a biomass burning event during BEARPEX 2009 and very fresh anthropogenic influence during BEACHON-ROCS. Other rapid changes in glyoxal and formaldehyde concentrations have hardly any affect on RGF and could reflect transitions between low and high NO regimes. The trend of increased RGF from both anthropogenic reactive VOC mixtures and biomass burning compared to biogenic reactive VOC mixtures is robust due to the short timescales over which the observed changes in RGF occurred. Satellite retrievals, which suggest higher RGF for biogenic areas, are in contrast to our observed trends. It remains important to address this discrepancy, especially in view of the importance of satellite retrievals and in situ measurements for model comparison. In addition, we propose that RGF represents a useful metric for biogenic or anthropogenic reactive VOC mixtures and, in combination with absolute concentrations of glyoxal and formaldehyde, furthermore represents a useful metric for the extent of anthropogenic influence on overall reactive VOC processing via NOx. In particular, RGF yields information about not simply the VOCs dominating reactivity in an airmass, but the VOC processing itself that is directly coupled to ozone and secondary organic aerosol production.

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.

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. © 2011 Author(s).

The Sulfur Transport and dEposition Model (STEM) is applied to the analysis of observations obtained during the Intercontinental Chemical Transport Experiment-Phase B (INTEX-B), conducted over the eastern Pacific Ocean during spring 2006. Predicted trace gas and aerosol distributions over the Pacific are presented and discussed in terms of transport and source region contributions. Trace species distributions show a strong west (high) to east (low) gradient, with the bulk of the pollutant transport over the central Pacific occurring between similar to 20 degrees N and 50 degrees N in the 2-6 km altitude range. These distributions are evaluated in the eastern Pacific by comparison with the NASA DC-8 and NSF/NCAR C-130 airborne measurements along with observations from the Mt. Bachelor (MBO) surface site. Thirty different meteorological, trace gas and aerosol parameters are compared. In general the meteorological fields are better predicted than gas phase species, which in turn are better predicted than aerosol quantities. PAN is found to be significantly overpredicted over the eastern Pacific, which is attributed to uncertainties in the chemical reaction mechanisms used in current atmospheric chemistry models in general and to the specifically high PAN production in the SAPRC-99 mechanism used in the regional model. A systematic underprediction of the elevated sulfate layer in the eastern Pacific observed by the C-130 is another issue that is identified and discussed. Results from source region tagged CO simulations are used to estimate how the different source regions around the Pacific contribute to the trace gas species distributions. During this period the largest contributions were from China and from fires in South/Southeast and North Asia. For the C-130 flights, which operated off the coast of the Northwest US, the regional CO contributions range as follows: China (35%), South/Southeast Asia fires (35%), North America anthropogenic (20%), and North Asia fires (10%). The transport of pollution into the western US is studied at MBO and a variety of events with elevated Asian dust, and periods with contributions from China and fires from both Asia and North America are discussed. The role of heterogeneous chemistry on the composition over the eastern Pacific is also studied. The impacts of heterogeneous reactions at specific times can be significant, increasing sulfate and nitrate aerosol production and reducing gas phase nitric acid levels appreciably (similar to 50%).

The chemistry of peroxynitric acid (HO2NO2) and methyl peroxynitrate (CH3O2NO2) is predicted to be particularly important in the upper troposphere where temperatures are frequently low enough that these compounds do not rapidly decompose. At temperatures below 240 K, we calculate that about 20% of NOy in the mid- and high-latitude upper troposphere is HO2NO2. Under these conditions, the reaction of OH with HO2NO2 is estimated to account for as much as one third of the permanent loss of hydrogen radicals. During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) campaign, we used thermal dissociation laser-induced fluorescence (TD-LIF) to measure the sum of peroxynitrates (SigmaPNsequivalent toHO(2)NO(2)+CH3O2NO2+PAN+PPN+...) aboard the NCAR C-130 research aircraft. We infer the sum of HO2NO2 and CH3O2NO2 as the difference between SigmaPN measurements and gas chromatographic measurements of the two major peroxy acyl nitrates, peroxy acetyl nitrate (PAN) and peroxy propionyl nitrate (PPN). Comparison with NOy and other nitrogen oxide measurements confirms the importance of HO2NO2 and CH3O2NO2 to the reactive nitrogen budget and shows that current thinking about the chemistry of these species is approximately correct. During the spring high latitude conditions sampled during the TOPSE experiment, the model predictions of the contribution of (HO2NO2+CH3O2NO2) to NOy are highly temperature dependent: on average 30% of NOy at 230 K, 15% of NOy at 240 K, and

Physical and chemical properties of the atmosphere at 0-8 km were measured during the Tropospheric Ozone Production about the Spring Equinox (TOPSE) experiments from February to May 2000 at mid (40°-60°N) and high latitudes (60°-80°N). The observations were analyzed using a diet steady state box model to examine HOx and O3 photochemistry during the spring transition period. The radical chemistry is driven primarily by photolysis of O3 and the subsequent reaction of O(1D) and H2O, the rate of which increases rapidly during spring. Unlike in other tropospheric experiments, observed H2O2 concentrations are a factor of 2-10 lower than those simulated by the model. The required scavenging timescale to reconcile the model overestimates shows a rapid seasonal decrease down to 0.5-1 day in May, which cannot be explained by known mechanisms. This loss of H2O2 implies a large loss of HOx resulting in decreases in O3 production (10-20%) and OH concentrations (20-30%). Photolysis of CH2O, either transported into the region or produced by unknown chemical pathways, appears to provide a significant HOx source at 6-8 km at high latitudes. The rapid increase of in situ O3 production in spring is fueled by concurrent increases of the primary HOx production and NO concentrations. Long-lived reactive nitrogen species continue to accumulate at mid and high latitudes in spring. There is a net loss of NOx to HNO3 and PAN throughout the spring, suggesting that these long-term NOx reservoirs do not provide a net source for NOx in the region. In Situ O3 chemical loss is dominated by the reaction of O3 and HO2, and not that of O(1D) and H2O. At midlatitudes, there is net in situ chemical production Of O3 from February to May. The lower free troposphere (1-4 km) is a region of significant net O3 production. The net production peaks in April coinciding with the observed peak of column O3 (0-8 km). The net in situ O3 production at midlatitudes can explain much of the observed column O3 increase, although it alone cannot explain the observed April maximum. In contrast, there is a net in situ O3 loss from February to April at high latitudes. Only in May is the in situ O3 production larger than loss. The observed continuous increase of column O3 at high latitudes throughout the spring is due to transport from other tropospheric regions or the stratosphere not in situ photochemistry.

Reported here are tropical/subtropical Pacific basin OH observational data presented in a latitude/altitude geographical grid. They cover two seasons of the year (spring and fall) that reflect the timing of NASA's PEM-Tropics A (1996) and B (1999) field programs. Two different OH sensors were used to collect these data, and each instrument was mounted on a different aircraft platform (i.e., NASA's P-3B and DC-8). Collectively, these chemical snapshots of the central Pacific have revealed several interesting trends. Only modest decreases (factors of 2 to 3) were found in the levels of OH with increasing altitude (0-12 km). Similarly, only modest variations were found (factors of 1.5 to 3.5) when the data were examined as a function of latitude (30° N to 30° S). Using simultaneously recorded data for CO, O3, H2O, NO, and NMHCs, comparisons with current models were also carried out. For three out of four data subsets, the results revealed a high level of correspondence. On average, the box model results agreed with the observations within a factor of 1.5. The comparison with the three-dimensional model results was found to be only slightly worse. Overall, these results suggest that current model mechanisms capture the major photochemical processes controlling OH quite well and thus provide a reasonably good representation of OH levels for tropical marine environments. They also indicate that the two OH sensors employed during the PEM-Tropics B study generally saw similar OH levels when sampling a similar tropical marine environment. However, a modest altitude bias appears to exist between these instruments. More rigorous instrument intercomparison activity would therefore seem to be justified. Further comparisons of model predictions with observations are also recommended for nontropical marine environments as well as those involving highly elevated levels of reactive non-methane hydrocarbons. Copyright 2001 by the American Geophysical Union.

Coral reef symbioses are well-established models for studying multi-level networks of species interactions that provide nutritional benefits to partners. While the contributions of endosymbionts to cnidarian hosts have been extensively documented, relatively little is known about how exosymbionts contribute to nutrient cycling in coral reef cnidarians. We investigated exosymbiotic sources of ammonia and their contributions to physiological processes in Caribbean corkscrew sea anemones Bartholomea annulata. In laboratory experiments, anemones absorbed ammonia from seawater, which significantly enhanced the mitotic index of their endosymbiotic microalgae Symbiodinium, while anemone shrimp presence alone had no effect. Anemone shrimps excreted ammonia at much slower rates than anemones were able to absorb it, indicating that shrimp alone were not able to meet host nitrogen demand. Client fishes excreted ammonia ~10x more rapidly than did associated shrimps. On Caribbean coral reefs, anemone shrimps attract diverse client fishes through their parasite-cleaning behavior; these fishes excrete substantial ammonia near anemones while being cleaned. Exosymbiotic anemone shrimps thus may provide nutritional benefits to host anemones and microalgae indirectly, through their attraction of nitrogen-excreting fishes. This multi-level mutualistic network facilitates tight nutrient cycling among diverse species belonging to several phyla on coral reefs. While we assessed the rates and benefits of nutrient transfer under laboratory conditions, further research is needed to quantify the contributions of ammonia and other nutrients from client fishes through cleaner shrimps to host sea anemones in the field., Author(s): C. E. Cantrell [sup.1] , R. P. Henry [sup.1] , N. E. Chadwick [sup.1] Author Affiliations: (Aff1) grid.252546.2, 0000000122978753, Department of Biological Sciences, Auburn University, , 101 Rouse Life [...]

The equilibrium constant for N2 O5 ⇄NO2 +NO3 [reaction (1)], has been determined through direct concentration measurements of N2 O5, NO2, and NO3 in a temperature controlled long path cell, using absorption spectroscopy in the infrared and visible regions from 243 to 397 K. The results give K1C =1.30×1026 exp(-21 490/RT) molecules cm-3 with an estimated overall uncertainty of 30% at the 95% confidence level. This results in an equilibrium constant near room temperature approximately one-half that of previously accepted values. Using the temperature dependence of the equilibrium constant and new data for the enthalpy of formation of gaseous N2 O5 yields an enthalpy of formation for NO3 of 15.39±0.72 kcal mol-1. In additional experiments the temperature dependent first order decay rates of N2 O5 were determined from which a value for the product of the equilibrium constant (K1C ) and the rate constant for reaction (2): NO2 +NO3 →NO+NO2 +O2 was obtained for temperatures from 298 to 396 K: K1 k2 =1.23×1013 exp(-24 300/RT) s.-1 When this is combined with the equilibrium constant of the present study the following expression is obtained for k2 : 9.5×10-14 exp(-2810/RT) cm3 molecule-1 s.-1 [ABSTRACT FROM AUTHOR]