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Chemical Characterization and Reactivity of Fuel-Oxidizer Reaction Product

Fuel-oxidizer reaction product (FORP), the product of incomplete reaction of monomethylhydrazine and nitrogen tetroxide propellants prepared under laboratory conditions and from firings of Shuttle Reaction Control System thrusters, has been characterized by chemical and thermal analysis. The composition of FORP is variable but falls within a limited range of compositions that depend on three factors: the fuel-oxidizer ratio at the time of formation; whether the composition of the post-formation atmosphere is reducing or oxidizing; and the reaction or post-reaction temperature. A typical composition contains methylhydrazinium nitrate, ammonium nitrate, methylammonium nitrate, and trace amounts of hydrazinium nitrate and 1,1-dimethylhydrazinium nitrate. Thermal decomposition reactions of the FORP compositions used in this study were unremarkable. Neither the various compositions of FORP, the pure major components of FORP, nor mixtures of FORP with propellant system corrosion products showed any unusual thermal activity when decomposed under laboratory conditions. Off-limit thruster operations were simulated by rapid mixing of liquid monomethylhydrazine and liquid nitrogen tetroxide in a confined space. These tests demonstrated that monomethylhydrazine, methylhydrazinium nitrate, ammonium nitrate, or Inconel corrosion products can induce a mixture of monomethylhydrazine and nitrogen tetroxide to produce component-damaging energies. Damaging events required FORP or metal salts to be present at the initial mixing of monomethylhydrazine and nitrogen tetroxide.

David, Dennis D.↗

Introduction to the SONEX (Subsonic Assessment Ozone and Nitrogen Oxides Experiment) and POLINAT-2 (Pollution from Aircraft Emissions in the North Atlantic Flight Corridor) Special Issue

Emissions of atmospheric species from the engines of subsonic aircraft at cruise altitude (roughly, above seven kilometers) are of concern to scientists, the aviation industry and policymakers for two reasons. First, water vapor, soot and sulfur oxides, and related heterogeneous processes, may modify clouds and aerosols enough to perturb radiative forcing in the UT/LS (upper troposphere/lower stratosphere). A discussion of these phenomena appears in Chapter 3 of the IPCC Aviation Assessment (1999). An airborne campaign conducted to evaluate aviation effects on contrail, cirrus and cloud formation, is described in Geophysical Research Letters. The second concern arises from subsonic aircraft emissions of nitrogen oxides (NO + NO2 = NO(sub x)), CO, and hydrocarbons. These species may add to the background mixture of photochemically reactive species that form ozone. In the UT/LS, ozone is a highly effective greenhouse gas. The impacts of subsonic aircraft emissions on tropospheric NO(sub x) and ozone budgets have been studied with models that focus on UT chemistry [e.g. see discussions of individual models in Brasseur et al., 1998; Friedl et al., 1997; IPCC, 1999]. Depending on the model used, projected increases in the global subsonic aircraft fleet from 1992 to 2015 will lead to a 50-100 pptv increase in UT/LS NO. at 12 km (compared to 50-150 pptv background) in northern hemisphere midlatitudes. The corresponding 12-km ozone increase is 7-11 ppbv, or 5-10% (Chapter 4 in IPCC, 1999). Two major sources of uncertainties in model estimates of aviation effects are: (1) the often limited degree to which global models - the scale required to evaluate aircraft emissions - realistically simulate atmospheric transport and other physical processes; (2) limited UT/LS observations of trace gases with which to evaluate model performance. In response to the latter deficiency, a number of airborne campaigns aimed at elucidating the effect of aircraft on atmospheric nitrogen oxides and ozone were performed between 1990 and 1996 (see descriptions in Friedl et al., 1997; Brasseur et al., 1998).

Thompson, Anne M.↗

The Influence of Chemical Descriptors on the Reactivity of Potential Hypergolic Fuels With Hydrogen Peroxide

The state-of-the-art for storable hypergolic bipropellant systems is monomethylhydrazine (MMH) and mixed oxides of nitrogen (MON). While MMH and MON provide fast and highly reliable hypergolic ignition with excellent propulsive performance, they suffer from safety concerns impacting their production, cost, and supply to various test and launch facilities. In contrast, identifying and demonstrating low-toxicity fuels hypergolic with rocket grade hydrogen peroxide (H2O2) has been challenging with long ignition delay (IDT) and low propulsive performance affecting their deployment in flight systems. This work describes a preliminary observational study to assess the effects of molecular descriptors suspected to predict the reactivity and hypergolicity of compounds within the same chemical class (i.e., thioamide). The approach centered on evaluating functional groups, electrostatic potential, number of carbons, dipole moment, and adiabatic ionization energy. Thiourea is hypergolic with 89.2 wt.% H2O2 (minimum IDT of 21.9 ms) and was selected as a core fuel to study the reactivity of derived fuels with different functionalities. Additionally, the chemical properties were calculated with the Gaussian16 suite. The results showed that group substitution and generally increased number of carbons on thiourea increases IDT. It was observed that a more positively charged sulfur atom in the thioamide does not increase the reactivity towards H2O2. The dipole moment analysis revealed an overall trend of decreasing IDT due to increasing dipole moment. Finally, a lower adiabatic ionization energy related to increased IDTs for most cases. Additional chemical classes comprising a wider range of functionalities and electrophilic attributes are being investigated in on-going work.

Propellant↗

Florida Thunderstorms: A Faucet of Reactive Nitrogen to the Upper Troposphere

During the NASA Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) enhanced mixing ratios of nitric oxide were measured in the anvils of thunderstorms and in clear air downwind of storm systems on flights of a Wl3-57F high-altitude aircraft. Mixing ratios greater than l0 - 20 times background were readily observed over distances of 25-120 km due to lightning activity. In many of the Florida storms deposition of NO occurred up to near the tropopause but major deposition usually occurred 1 - 2 km below the tropopause, or mostly within the visible anvil volume formed prior to storm decay. Observations from two storms of very different anvil size and electrical activity allowed estimates of the total mass of NO, vented to the middle and upper troposphere. Using the cloud-to ground (CG) flash accumulations from the National Lightning Detection Network, climatological intra-cloud (IC) to CG ratios, and assuming that CG and IC flashes were of equivalent efficiency for NO production, the ranges of production per flash for a moderate-sized and a large storm were (0.51 - 1.0) x l0(exp 26) and (2.3 - 3.1) x 10(exp 26) molecules NO/flash, respectively. Using the recently determined average global flash rate of 44 8, a gross extrapolation of these two storms to represent possible global annual production rates yield 1.6 - 3.2 and 7.3 - 9.9 Tg(N)/yr, respectively. If the more usual assumption is made that IC efficiency is l/l0th that of CG activity, the ranges of production for the moderate-sized and large storm were (1.3 - 2.7) x l0(exp 26) and (6.0 - 8.1) x l0(exp 26) molecules NO/CG flash, respectively. The estimates from the large storm may be high because there is indirect evidence that the IC/CG ratio was larger than would be derived from climatology. These two storms and others studied did not have flash rates that scaled as approx. H(sup 5) where H is the cloud top altitude. The observed CG flash accumulations and NO(x) mass production estimate for the month of July over the Florida area were compared with a representative 3D global Chemistry-Transport Model (CTMJ that uses the Price et al. lightning parameterization. For two land grid points representing the Florida peninsula the model compared well with the observations: CG flash rates were low by only a factor of approx. 2. When the model grid points included the coastal regions of Florida the flash accumulations were lower than observed by a factor of 3.4 - 4.6. It is recommended that models using the Price et al. parameterization allow any global coastal grid point to maintain the land rather than the marine flash rate parameterization. The convection in this CTM underestimated the actual cloud top heights over Florida by 1 - 2 km and thus the total lightning flash rates and the altitude range of reactive nitrogen deposition. Broad scale (20 - 120 km) median mixing ratios of NO within anvils over Florida were significantly larger than in storms previously investigated over Colorado and New Mexico.

Ridley, B.↗

Near Real-time Air Quality Forecasts Using the NASA GEOS Model

NASA's Global Modeling and Assimilation Office (GMAO) produces high-resolution global forecasts for weather, aerosols, and air quality. The NASA Global Earth Observing System (GEOS) model has been expanded to provide global near-real-time 5-day forecasts of atmospheric composition at unprecedented horizontal resolution of 0.25 degrees (~25 km). This composition forecast system (GEOS-CF) combines the operational GEOS weather forecasting model with the state-of-the-science GEOS-Chem chemistry module (version 12) to provide detailed analysis of a wide range of air pollutants such as ozone, carbon monoxide, nitrogen oxides, and fine particulate matter (PM2.5). Future developments for the next GEOS-CF version will be discussed, including the assimilation system is being expanded to include chemically reactive trace gases, specifically using the capabilities of the GEOS Constituent Data Assimilation System (CoDAS).

CoDAS↗

RF sputtered silicon and hafnium nitrides: Properties and adhesion to 440C stainless steel

Silicon nitride and hafnium nitride coatings were deposited by reactive RF sputtering on oxidized and unoxidized 440C stainless steel substrates. Sputtering was done in mixtures of argon and nitrogen gases from pressed powder silicon nitride and from hafnium metal targets. Depositions were at two background pressures, 8 and 20 mtorr, and at two different fractions (f) of nitrogen in argon, 0.25 and 0.60, for hafnium nitride and at f = 0.25 for silicon nitride. The coatings and the interface between the coating and substrates were investigated by X-ray diffractometry, scanning electron microscopy, energy dispersive X-ray analysis and Auger electron spectroscopy. A Knoop microhardness of 1650 + or - 100 kg/sq mm was measured for hafnium nitride and 3900 + or - 500 kg/sq mm for silicon nitride. The friction coefficients between a 440C rider and the coatings were measured under lubricated conditions. Scratch test results demonstrate that the adhesion of hafnium nitride to both oxidized and unoxidized 440C is superior to that of silicon nitride. Oxidized 440C is found to have increased adhesion, to both nitrides, over that of unoxidized 440C.

Grill, A.↗

RF-sputtered silicon and hafnium nitrides - Properties and adhesion to 440C stainless steel

Silicon nitride and hafnium nitride coatings were deposited by reactive RF sputtering on oxidized and unoxidized 440C stainless steel substrates. Sputtering was done in mixtures of argon and nitrogen gases from pressed powder silicon nitride and from hafnium metal targets. Depositions were at two background pressures, 8 and 20 mtorr, and at two different fractions (f) of nitrogen in argon, 0.25 and 0.60, for hafnium nitride and at f = 0.25 for silicon nitride. The coatings and the interface between the coating and substrates were investigated by X-ray diffractometry, scanning electron microscopy, energy dispersive X-ray analysis and Auger electron spectroscopy. A Knoop microhardness of 1650 + or 100 kg/sq mm was measured for hafnium nitride and 3900 + or 500 kg/sq mm for silicon nitride. The friction coefficients between a 440C rider and the coatings were measured under lubricated conditions. Scratch test results demonstrate that the adhesion of hafnium nitride to both oxidized and unoxidized 440C is superior to that of silicon nitride. Oxidized 440C is found to have increased adhesion, to both nitrides, over that of unoxidized 440C.

Grill, A.↗

The enhanced oxidation of SO2 by NO2 on carbon particulates

The oxidation of SO2 on carbon particles in dry air and in air at 65% relative humidity (RH) was found to be greatly enhanced by the presence of gaseous NO2. Exposures of 20-80ppm SO2 + 10ppm NO2 on 1-mg samples of commercial carbon black were found to produce both sorption and desorption coverages (weight retained after desorption into N2) of over one order of magnitude greater than for corresponding SO2 exposures. Significant agglomeration and wetting were observed to occur progressively during exposures at 65% RH, and samples, even after 150-h exposure, rarely reached steady-state weight gain. The wetting may have regenerated fresh reactive carbon surface. Sorptions conducted in nitrogen atmospheres, rather than in air, appeared to produce slightly higher sorptions and weight retentions for equivalent exposure concentrations and times, indicating that NO2 served as the oxidizer and that molecular oxygen, or some trace constitutents in air, may have weakly inhibited the oxidation by NO2. Wet chemical analysis of the desorbed phase indicated that sulfate, presumably H2SO4 accounted for over half of the retained weight. Measurements of pH from water-quenched samples indicated a highly acidic surface phase, and suggested the oxidation process could proceed in an acidic environment.

Cofer, W. R., III↗

Mineral-Catalysed Formation of Marine NO and N 2 O on the Anoxic Early Earth

Microbial denitrification converts fixed nitrogen species into gases in extant oceans. However, it is unclear how such transformations occurred within the early nitrogen cycle of the Archean. Here 5we present experimental anoxic surface-catalyzed reduction of nitrite and nitrate via green rust and magnetite combined with diffusion and photochemical modeling. We find that in a Fe 2+ -rich marine environment, Fe minerals could have catalyzed abiotic denitrification reactions leading to the formation of nitric oxide (NO) and nitrous oxide (N 2 O). Nitrate did not exhibit reactivity in the presence of either mineral or aqueous Fe2+, however, both minerals induced rapid nitrite reduction 10to NO and N 2 O. While N 2 O escaped into the atmosphere (63% of nitrite-nitrogen, with green rust as catalyst), NO remained associated with precipitates (7%) serving as a potential shuttle to the benthic ocean.The modeling suggests that marine N 2 O emissions would have sustained 0.8-6 ppb of atmospheric N 2 O without a protective ozone layer. Our findings add detail to the as yet incompletely documented Archean nitrogen cycle, implying a globally distributed process driven 15by chemical kinetics similar to those of modern enzymatically mediated conversions.

Steffen Buessecker↗

The Icebreaker Mission to Search for Life on Mars

The search for evidence of life on Mars is the ultimate motivation for its scientific exploration. The results from the Phoenix mission indicate that the high N. latitude ice-rich regolith at low elevations is likely to be a recently habitable place on Mars [Stoker et al., 2010]. The near-surface ice likely provided adequate water activity during periods of high obliquity, 3 to 10 Myr ago. Carbon dioxide and nitrogen are present in the atmosphere, and nitrates may be present in the soil. Together with iron in basaltic rocks and perchlorate in the soil they provide carbon and energy sources, and oxidative power to drive metabolism. Furthermore, the presence of organics is possible, as thermally reactive perchlorate would have prevented their detection by Viking and Phoenix. The Mars Icebreaker Life mission [McKay et al., 2013] focuses on the following science goals: (1) Search for biomolecular evidence of life; (2) Search for organic matter from either exogeneous or endogeneous sources using methods that are not effected by the presence of perchlorate; (3) Characterize oxidative species that produced reactivity of soils seen by Viking; and 4) Assess the habitability of the ice bearing soils. The Icebreaker Life payload (Figure 1) includes a 1-m rotary percussive drill that brings cuttings samples to the surface where they are delivered to three instruments (Fig. 1), the Signs of Life Detector (SOLID) [Parro et al., 2011] for biomolecular analysis, Laser Desorption Mass Spectrometer (LDMS) [??? 2015]) for broad spectrum organic analysis, and Wet Chemistry Laboratory (WCL) [Hecht et al., 2009] for detecting soluble species of nutrients and reactive oxidants. The Icebreaker payload fits on the Phoenix spacecraft and can land at the well-characterized Phoe-nix landing site in 2020 in a Discovery-class mission.

Carbon dioxide and nitrogen↗

Dependence of Lightning Cloud-Top Optical Emissions on Channel Characteristics Using Boltzmann Radiative Transfer Modeling

With an estimated global flash rate of 46 lightning per second, a significant amount of lightning nitrogen oxides (LNOx) are produced within the climate system. In turn, LNOx affect the concentrations of ozone (O 3 , an important greenhouse gas) as well as the very reactive hydroxyl radicals (OH, that affect all greenhouse gases). Thus, space-based estimation of LNOx is highly sought [Koshak 2017; Koshak et al. (2015)]. Total lightning channel length, L , is a proxy for the total flash energy (and hence LNOx production). Geostationary lightning mappers provide cloud-top 2D views of the diffuse (i.e., blurry) optical images of lightning, thereby making it difficult to determine L (and other channel features). Transient Boltzmann radiative transfer modeling is applied here to investigate the dependence of the spatio-temporal pattern of cloud-top lightning optical emissions on L and other channel characteristics (e.g., orientation, propagation direction, amplitude, location, ...).

William J Koshak↗

Near real-time air quality forecasts using the NASA GEOS model

NASA's Global Modeling and Assimilation Office (GMAO) produces high-resolution global forecasts for weather, aerosols, and air quality. The NASA Global Earth Observing System (GEOS) model has been expanded to provide global near-real-time5-day forecasts of atmospheric composition at unprecedented horizontal resolution of 0.25 degrees (~25 km). This composition forecast system (GEOS-CF) combines the operational GEOS weather forecasting model with the state-of-the-science GEOS-Chem chemistry module (version 12) to provide detailed analysis of a wide range of air pollutants such as ozone, carbon monoxide, nitrogen oxides, and fine particulate matter (PM2.5). Satellite observations are assimilated into the system for improved representation of weather and smoke. The assimilation system is being expanded to include chemically reactive trace gases. We discuss current capabilities of the GEOS Constituent Data Assimilation System (CoDAS) to improve atmospheric composition modeling and possible future directions, notably incorporating new observations (TROPOMI, geostationary satellites) and machine learning techniques. We show how machine learning techniques can be used to correct for sub-grid-scale variability, which further improves model estimates at a given observation site.

Air Quality Forecast↗

Sensitivity of Tropospheric Ozone Over the Southeast USA to Dry Deposition

Dry deposition (DD) is a major loss process for tropospheric ozone and some reactive nitrogen and carbon precursors. We investigate the response of summertime ozone and its production chemistry over the Southeast United States (USA) to variability in this sink. Turning off DD of oxidized nitrogen, ozone, or all species over the United States in the Geophysical Fluid Dynamics Laboratory AM3 model increases regional mean surface ozone by 5, 18, or 25 ppb, respectively. Additional sensitivity simulations demonstrate that, assuming linearity, surface ozone has a similar sensitivity to ozone DD as to NOx emissions. Trends in ozone production efficiency derived from observed relationships between ozone and precursor oxidation products may not solely reflect precursor emission changes if ozone DD varies (e.g., with meteorology). We conclude that DD variability merits consideration when interpreting observed ozone trends. Quantifying the impact of changes in sinks versus sources will require long‐term DD measurements across the region of interest.

dry deposition↗

NASA's High-Resolution GEOS Forecasting and Reanalysis Products: A Unified Tool from Local to Global Scales

NASA's GMAO produces high-resolution global forecasts for weather, aerosols, and air quality. The NASA Global Earth Observing System (GEOS) model has been expanded to provide global near-real-time 5-day forecasts of atmospheric chemical composition at unprecedented horizontal resolution of 0.25 degrees (~25 km), freely available to the public. This composition forecast system (GEOS-CF) combines the operational GEOS weather forecasting model with the state-of-the-science GEOS-Chem chemistry module to provide detailed analysis of a wide range of air pollutants such as ozone, carbon monoxide, nitrogen oxides, and fine particulate matter (PM2.5). GEOS-CF also assimilated satellite observations into the system for improved representation of weather and smoke. The assimilation system is currently being expanded to include chemically reactive trace gases. While the main focus of this new product is on tropospheric air quality information, the GEOS-Chem chemistry model used in this system includes the unified tropospheric stratospheric chemistry mechanism for improved forecasts of total column ozone during anomalous dynamical and chemical events. I will discuss current capabilities of the GEOS Constituent Data Assimilation System (CoDAS) to improve atmospheric composition modeling and possible future directions for GEOS-CF and reanalysis products. In addition, I will show how machine learning techniques can be used to correct for sub-grid-scale variability, which further improves model estimates at a given observation site.

Co-DAS↗

GOES-16 GLM Observations for National Climate Assessments

The heating of air by a lightning discharge, followed by rapid cooling, leads to the production of lightning nitrogen oxides (“LNO x ” for brevity, where NO x = NO + NO 2 ). The LNO x are important trace gases because they control the concentration of the greenhouse gas ozone (O 3 ) and the highly reactive hydroxyl radicals (OH). In fact, LNO x are the most important source of NO x in the upper troposphere at tropical and subtropical latitudes, and climate is most sensitive to O 3 in the upper troposphere. Since lightning indirectly influences the Earth's climate, it is a key variable to monitor in National Climate Assessment (NCA) studies. In this work, GOES-16 Geostationary Lightning Mapper (GLM) flash counts and flash optical properties (i.e., optical energy, optical area, …) that are linked to LNO x production are examined in detail for the continental United States analysis region, and are compared with ground-based National Lightning Detection Network (NLDN) observations.

Lightning↗

Effective radiative forcing from emissions of reactive gases and aerosols - a multi-model comparison

This paper quantifies the pre-industrial (1850) to present-day (2014) effective radiative forcing (ERF) of anthropogenic emissions of NOX, volatile organic compounds (VOCs; including CO), SO2, NH3, black carbon, organic carbon, and concentrations of methane, N2O and ozone-depleting halocarbons, using CMIP6 models. Concentration and emission changes of reactive species can cause multiple changes in the composition of radiatively active species: tropospheric ozone, stratospheric ozone, stratospheric water vapour, secondary inorganic and organic aerosol, and methane. Where possible we break down the ERFs from each emitted species into the contributions from the composition changes. The ERFs are calculated for each of the models that participated in the AerChemMIP experiments as part of the CMIP6 project, where the relevant model output was available. The 1850 to 2014 multi-model mean ERFs (± standard deviations) are −1.03 ± 0.37 W/sq.m for SO2 emissions, −0.25 ± 0.09 W/sq.m for organic carbon (OC), 0.15 ± 0.17 W/sq.m for black carbon (BC) and −0.07 ± 0.01 W/sq.m for NH3. For the combined aerosols (in the piClim-aer experiment) it is −1.01 ± 0.25 W/sq.m. The multi-model means for the reactive well-mixed greenhouse gases (including any effects on ozone and aerosol chemistry) are 0.67 ± 0.17 W/sq.m for methane (CH4), 0.26 ± 0.07 W/sq.m for nitrous oxide (N2O) and 0.12 ± 0.2 W/sq.m for ozone-depleting halocarbons (HC). Emissions of the ozone precursors nitrogen oxides (NOx), volatile organic compounds and both together (O3) lead to ERFs of 0.14 ± 0.13, 0.09 ± 0.14 and 0.20 ± 0.07 W/sq.m respectively. The differences in ERFs calculated for the different models reflect differences in the complexity of their aerosol and chemistry schemes, especially in the case of methane where tropospheric chemistry captures increased forcing from ozone production.

radiative forcing↗

Correction to "Asian chemical Outflow to the Pacific in Spring: Origins, Pathways, and Budgets" by Isabelle Bey et al.

We analyze the Asian outflow of CO, ozone, and nitrogen oxides (NOx) to the Pacific in spring by using the GEOS-CHEM global three-dimensional model of tropospheric chemistry and simulating the Pacific Exploratory Mission-West (PEM-West B) aircraft mission in February-March 1994. The GEOS-CHEM model uses assimilated meteorological fields from the NASA Goddard Earth Observing System (GEOS). It reproduces relatively well the main features of tropospheric ozone, CO, and reactive nitrogen species observed in PEM-West B, including latitudinal and vertical gradients of the Asian pollution outflow over the western Pacific although simulated concentrations of CO tend to be too low (possibly because biogenic sources are underestimated). We use CO as a long-lived tracer to diagnose the processes contributing to the outflow. The highest concentrations in the outflow are in the boundary layer (0-2 km), but the strongest outflow fluxes are in the lower free troposphere (2-5 km) and reflect episodic lifting of pollution over central and eastern China ahead of eastward moving cold fronts. This frontal lifting, followed by westerly transport in the lower free troposphere, is the principal process responsible for export of both anthropogenic and biomass burning pollution from Asia. Anthropogenic emissions from Europe and biomass burning emissions from Africa make also major contributions to the Asian outflow over the western Pacific; European sources dominate in the lower troposphere north of 40 degrees N, while African sources are important in the upper troposphere at low latitudes. For the period of PEM-West B (February-March) we estimate that fossil fuel combustion and biomass burning make comparable contributions to the budgets of CO, ozone, and NO, in the Asian outflow. We find that 13% of NO, emitted in Asia is exported as NO, or PAN, a smaller fraction than for the United States because of higher aerosol concentrations that promote heterogeneous conversion of NOx to HNO3. Production and export of ozone from Asia in spring is much greater than from the United States because of the higher photochemical activity.

Bey, Isabelle↗

A one-dimensional photochemical model of the troposphere with planetary boundary-layer parameterization

A time-dependent, one-dimensional photochemical model of the troposphere is used to describe the vertical distribution of atmospheric trace constituents for summer-time conditions at midlatitudes in the Northern Hemisphere. The model incorporates a planetary boundary layer (PBL) parametrization and a detailed chemical mechanism that includes the photochemistry of important nonmethane hydrocarbon species formed during the oxidation process. One result of the parametrized PBL is that the concentrations of some trace species in the free troposphere are 20-30 percent higher than when mixing processes are described by a vertical eddy diffusion coefficient which is held constant with respect to height and time. The lifetime of the oxides of nitrogen against photochemical conversion to nitric acid during summertime conditions is on the order of six hours. This lifetime is short enough to deplete most of the NO(x) in the PBL so that other reactive nitrogen species are more abundant than NO(x) throughout the free troposphere.

Fishman, J.↗