[1] A three-dimensional (3-D) cloud-scale chemical transport model that includes a parameterized source of lightning NO x on the basis of observed flash rates has been used to simulate six midlatitude and subtropical thunderstorms observed during four field projects. Production per intracloud (P IC ) and cloud-to-ground (P CG ) flash is estimated by assuming various values of P IC and P CG for each storm and determining which production scenario yields NO x mixing ratios that compare most favorably with in-cloud aircraft observations. We obtain a mean P CG value of 500 moles NO (7 kg N) per flash. The results of this analysis also suggest that on average, P IC may be nearly equal to P CG , which is contrary to the common assumption that intracloud flashes are significantly less productive of NO than are cloud-to-ground flashes. This study also presents vertical profiles of the mass of lightning NO x after convection based on 3-D cloud-scale model simulations. The results suggest that following convection, a large percentage of lightning NO x remains in the middle and upper troposphere where it originated, while only a small percentage is found near the surface. The results of this work differ from profiles calculated from 2-D cloud-scale model simulations with a simpler lightning parameterization that were peaked near the surface and in the upper troposphere (referred to as a ''C-shaped'' profile). The new model results (a backward C-shaped profile) suggest that chemical transport models that assume a C-shaped vertical profile of lightning NO x mass may place too much mass near the surface and too little in the middle troposphere.

Abstract. Understanding lightning NO x (NO + NO2) production on the cloud scale is key for developing better parameterizations of lightning NOx for use in regional and global chemical transport models. This paper attempts to further the understanding of lightning NOx production on the cloud scale using a cloud model simulation of an observed thunderstorm. Objectives are (1) to infer from the model simulations and in situ measurements the relative production rates of NOx by cloud-to-ground (CG) and intracloud (IC) lightning for the storm; (2) to assess the relative contributions in the storm anvil of convective transport of NOx from the boundary layer and NOx production by lightning; and (3) to simulate the effects of the lightning-generated NOx on subsequent photochemical ozone production. We use a two-dimensional cloud model that includes a parameterized source of lightning-generated NOx to study the production and advection of NO x associated with a developing northeast Colorado thunderstorm observed on July 12, 1996, during the Stratosphere-Troposphere Experiment--Radiation, Aerosols, Ozone

[1] Extensive chemical characterization of ozone (O 3 ) depletion events in the Arctic boundary layer during the TOPSE aircraft mission in March-May 2000 enables analysis of the coupled chemical evolution of bromine (BrO x ), chlorine (ClO x ), hydrogen oxide (HO x ) and nitrogen oxide (NO x ) radicals during these events. We project the TOPSE observations onto an O 3 chemical coordinate to construct a chronology of radical chemistry during O 3 depletion events, and we compare this chronology to results from a photochemical model simulation. Comparison of observed trends in ethyne (oxidized by Br) and ethane (oxidized by Cl) indicates that ClO x chemistry is only active during the early stage of O 3 depletion (O 3 > 10 ppbv). We attribute this result to the suppression of BrCl regeneration as O 3 decreases. Formaldehyde and peroxy radical concentrations decline by factors of 4 and 2 respectively during O 3 depletion and we explain both trends on the basis of the reaction of CH 2 O with Br. Observed NO x concentrations decline abruptly in the early stages of O 3 depletion and recover as O 3 drops below 10 ppbv. We attribute the initial decline to BrNO 3 hydrolysis in aerosol, and the subsequent recovery to suppression of BrNO 3 formation as O 3 drops. Under halogen-free conditions we find that HNO 4 heterogeneous chemistry could provide a major NO x sink not included in standard models. Halogen radical chemistry in the model can produce under realistic conditions an oscillatory system with a period of 3 days, which we believe is the fastest oscillation ever reported for a chemical system in the atmosphere.

Measurements of light hydrocarbons, ozone, peroxyacetyl nitrate (PAN), HNO3, NO3−, NOx, NOy, and meteorological parameters were made during a 10‐day period in April and May 1985 at Point Arena, a coastal inflow site on the Pacific Ocean in northern California. The meteorological measurements indicate that during this study the sampled air was usually from the marine boundary layer with little land influence on the meteorological parameters. In this marine air the mixing ratios of the alkanes, ozone, PAN, and HNO3 showed strong correlations coincident with variations in the origins of calculated air parcel trajectories and with variations in the ratios of the light alkanes. This variation in the ratios is attributed to different degrees of photochemical aging of the alkanes that are generally consistent with the calculated trajectories. This behavior indicates that the alkane levels are determined by transport to the marine area from continental sources, most likely Asian, followed by photochemical removal over the Pacific Ocean. Since the concentrations of PAN and ozone correlate well with the alkane ratios, it is concluded that the observed PAN and ozone were dominated by continental sources and removal processes in the marine areas. This and other marine studies have observed a strong correlation of PAN and ozone, and it is suggested that production over the continents, transport to the marine areas, and parallel removal processes account for much of the observed correlation. From the correlation of these two species with the measured alkane ratios, approximate net lifetimes of PAN and ozone in the marine troposphere of ≤2.5 and ≥19 days, respectively, are derived. The primary conclusion is that the alkanes, ozone, and PAN in these air parcels from the Pacific marine troposphere are dominated by transport from continental sources and removal by photochemical processes. Direct emissions of the alkanes and in situ photochemical production of PAN and ozone from precursors emitted into the marine region from the surface or the stratosphere must play less important roles. Similar indications of continental influence in marine areas have been seen in other studies of ozone, the sulfur cycle, oxidized nitrogen, and hydrocarbons. It is suggested that the ratios of the light alkanes provide photochemical “clocks” that are useful for gauging the importance of continental influence in a particular marine measurement.

In situ measurements of the relative humidity with respect to ice (RHi) and of nitric acid (HNO3) were made in both natural and contrail cirrus clouds in the upper troposphere. At temperatures lower than 202 kelvin, RHi values show a sharp increase to average values of over 130% in both cloud types. These enhanced RHi values are attributed to the presence of a new class of HNO3-containing ice particles (Delta-ice). We propose that surface HNO3 molecules prevent the ice/vapor system from reaching equilibrium by a mechanism similar to that of freezing point depression by antifreeze proteins. Delta-ice represents a new link between global climate and natural and anthropogenic nitrogen oxide emissions. Including Delta-ice in climate models will alter simulated cirrus properties and the distribution of upper tropospheric water vapor.