Rethinking reactive halogen budgets in the midlatitude lower stratosphere

Current stratospheric models have difficulties in fully explaining the observed midlatitude ozone depletion in the lowermost stratosphere, particularly near the tropopause. Such models assume that only long-lived source gases provide significant contributions to the stratospheric halogen budget, while all the short-lived compounds are removed in the troposphere, the products being rained out. Here we show this assumption to be flawed. Using bromine species as an example, we show that in the lowermost stratosphere, where the observed midlatitude ozone trend maximizes, bromoform (CHBr3) alone likely contributes more inorganic bromine than all the conventional long-lived sources (halons and methyl bromide) combined. Copyright 1999 by the American Geophysical Union

Distributions of brominated organic compounds in the troposphere and lower stratosphere

A comprehensive suite of brominated organic compounds was measured from whole air samples collected during the 1996 NASA Stratospheric Tracers of Atmospheric Transport aircraft campaign and the 1996 NASA Global Tropospheric Experiment Pacific Exploratory Mission-Tropics aircraft campaign. Measurements of individual species and total organic bromine were utilized to describe latitudinal and vertical distributions in the troposphere and lower stratosphere, fractional contributions to total organic bromine by individual species, fractional dissociation of the long-lived species relative to CFC-11, and the Ozone Depletion Potential of the halons and CH3Br. Spatial differences in the various organic brominated compounds were related to their respective sources and chemical lifetimes. The difference between tropospheric mixing ratios in the Northern and Southern Hemispheres for halons was approximately equivalent to their annual tropospheric growth rates, while the interhemispheric ratio of CH3Br was 1.18. The shorter-lived brominated organic species showed larger tropospheric mixing ratios in the tropics relative to midlatitudes, which may reflect marine biogenic sources. Significant vertical gradients in the troposphere were observed for the short-lived species with upper troposphere values 40-70% of the lower troposphere values. Much smaller vertical gradients (3-14%) were observed for CH3Br, and no significant vertical gradients were observed for the halons. Above the tropopause, the decrease in organic bromine compounds was found to have some seasonal and latitudinal differences. The combined losses of the individual compounds resulted in a loss of total organic bromine between the tropopause and 20 km of 38-40% in the tropics and 75-85% in midlatitudes. The fractional dissociation of the halons and CH3Br relative to CFC-11 showed latitudinal differences, with larger values in the tropics. Copyright 1999 by the American Geophysical Union

Effects of mixing on evolution of hydrocarbon ratios in the troposphere

Nonmethane hydrocarbon (NMHC) concentration ratios provide useful indicators of tropospheric oxidation and transport processes. However, the influences of both photochemical and mixing processes are inextricably linked in the evolution of these ratios. We present a model for investigating these influences by combining the transport treatment of the Lagrangian particle dispersion model FLEXPART with an ultrasimple (i.e., constant OH concentration) chemical treatment. Required model input includes NMHC emission ratios, but not ad hoc assumed background NMHC concentrations. The model results give NMHC relationships that can be directly compared, in a statistical manner, with measurements. The measured concentration ratios of the longest-lived alkanes show strong deviations from purely kinetic behavior, which the model nicely reproduces. In contrast, some measured aromatic ratio relationships show even stronger deviations that are not well reproduced by the model for reasons that are not understood. The model-measurement comparisons indicate that the interaction of mixing and photochemical processing prevent a simple interpretation of "photochemical age," but that the average age of any particular NMHC can be well defined and can be approximated by a properly chosen and interpreted NMHC ratio. In summary, the relationships of NMHC concentration ratios not only yield useful measures of photochemical processing in the troposphere, but also provide useful test of the treatment of mixing and chemical processing in chemical transport models. Copyright 2007 by the American Geophysical Union

Effect of local and regional sources on the isotopic composition of nitrous oxide in the tropical free troposphere and tropopause layer

Measurements and models of the spatiotemporal variability of surface N 2O mixing ratios and isotopic compositions are increasingly used to constrain the global N2O budget. However, large variability observed on the small spatial scales of soil chambers and shipboard sampling, which appears to be very sensitive to local environmental conditions, has made extrapolation to the global scale difficult. In this study, we present measurements of the isotopic composition of N2O (δ 15Nbulk, δ15N, δ15N, and δ18O) from whole-air samples collected at altitudes of 0.5 to 19km by the NASA DC-8 and WB-57 aircraft during the Costa Rica-Aura Validation Experiment (CR-AVE) and the Tropical Composition, Cloud and Climate Coupling Experiment (TC4) campaigns in January-February 2006 and July-August 2007, respectively. The vertical profiles of isotopic composition showed predictable, repeating patterns consistent with the influence of a surface source at lower altitudes and the influence of stratospheric photochemistry in the lower stratosphere. Their correlations with marine tracers at lower altitudes are consistent with a predominantly oceanic source, although a soil source cannot be ruled out. Measurements in a combustion plume revealed a strong depletion in 15N at the central nitrogen atom (i.e., low δ15N values), providing new information on N2O isotopic compositions from combustion. This new data set demonstrates that a coherent picture of the isotopic composition of tropospheric N2O is possible at currently attainable precisions and that its variations from 0.5 km to the lower stratosphere are a useful tool in investigating the sources and distributions of this important greenhouse gas. Copyright 2010 by the American Geophysical Union

Ozone and alkyl nitrate formation from the Deepwater Horizon oil spill atmospheric emissions

Ozone (O3), alkyl nitrates (RONO2), and other photochemical products were formed in the atmosphere downwind from the Deepwater Horizon (DWH) oil spill by photochemical reactions of evaporating hydrocarbons with NOx (=NO+NO2) emissions from spill response activities. Reactive nitrogen species and volatile organic compounds (VOCs) were measured from an instrumented aircraft during daytime flights in the marine boundary layer downwind from the area of surfacing oil. A unique VOC mixture, where alkanes dominated the hydroxyl radical (OH) loss rate, was emitted into a clean marine environment, enabling a focused examination of O3 and RONO 2 formation processes. In the atmospheric plume from DWH, the OH loss rate, an indicator of potential O3 formation, was large and dominated by alkanes with between 5 and 10 carbons per molecule (C 5-C10). Observations showed that NOx was oxidized very rapidly with a 0.8h lifetime, producing primarily C6-C10 RONO2 that accounted for 78% of the reactive nitrogen enhancements in the atmospheric plume 2.5h downwind from DWH. Both observations and calculations of RONO2 and O3 production rates show that alkane oxidation dominated O3 formation chemistry in the plume. Rapid and nearly complete oxidation of NOx to RONO2 effectively terminated O3 production, with O3 formation yields of 6.0±0.5 ppbv O3 per ppbv of NOx oxidized. VOC mixing ratios were in large excess of NOx, and additional NOx would have formed additional O3 in this plume. Analysis of measurements of VOCs, O3, and reactive nitrogen species and calculations of O3 and RONO2 production rates demonstrate that NOx-VOC chemistry in the DWH plume is explained by known mechanisms. Copyright 2012 by the American Geophysical Union

Determination of urban volatile organic compound emission ratios and comparison with an emissions database

During the NEAQS-ITCT2k4 campaign in New England, anthropogenic VOCs and CO were measured downwind from New York City and Boston. The emission ratios of VOCs relative to CO and acetylene were calculated using a method in which the ratio of a VOC with acetylene is plotted versus the photochemical age. The intercept at the photochemical age of zero gives the emission ratio. The so determined emission ratios were compared to other measurement sets, including data from the same location in 2002, canister samples collected inside New York City and Boston, aircraft measurements from Los Angeles in 2002, and the average urban composition of 39 U.S. cities. All the measurements generally agree within a factor of two. The measured emission ratios also agree for most compounds within a factor of two with vehicle exhaust data indicating that a major source of VOCs in urban areas is automobiles. A comparison with an anthropogenic emission database shows less agreement. Especially large discrepancies were found for the C2-C4 alkanes and most oxygenated species. As an example, the database overestimated toluene by almost a factor of three, which caused an air quality forecast model (WRF-CHEM) using this database to overpredict the toluene mixing ratio by a factor of 2.5 as well. On the other hand, the overall reactivity of the measured species and the reactivity of the same compounds in the emission database were found to agree within 30%. Copyright 2007 by the American Geophysical Union

Factors controlling tropospheric O3, OH, NOx, and SO2 over the tropical Pacific during PEM-Tropics B

Observations over the tropical Pacific during the Pacific Exploratory Mission (PEM)-Tropics B experiment (March-April 1999) are analyzed. Concentrations of CO and long-lived nonmethane hydrocarbons in the region are significantly enhanced due to transport of pollutants from northern industrial continents. This pollutant import also enhances moderately O3 concentrations but not NOx concentrations. It therefore tends to depress OH concentrations over the tropical Pacific. These effects contrast to the large enhancements of O3 and NOx concentrations and the moderate increase of OH concentrations due to biomass burning outflow during the PEM-Tropics A experiment (September-October 1996). Observed CH3I concentrations, as in PEM-Tropics A, indicate that convective mass outflux in the middle and upper troposphere is largely independent of altitude over the tropical Pacific. Constraining a one-dimensiohal model with CH3I observations yields a 10-day timescale for convective turnover of the free troposphere, a factor of 2 faster than during PEM-Tropics A. Model simulated HO2, CH2O, H2O2, and CH3OOH concentrations are generally in agreement with observations. However, simulated OH concentrations are lower (∼25%) than observations above 6 km. Whereas models tend to overestimate previous field measurements, simulated HNO3 concentrations during PEM-Tropics B are too low (a factor of 2-4 below 6 km) compared to observations. Budget analyses indicate that chemical production of O3 accounts for only 50% of chemical loss; significant transport of O3 into the region appears to take place within the tropics. Convective transport of CH3OOH enhances the production of HOx and O3 in the upper troposphere, but this effect is offset by HOx loss due to the scavenging of H2O2. Convective transport and scavenging of reactive nitrogen species imply a necessary source of 0.4-1 Tg yr-1 of NOx in the free troposphere (above 4 km) over the tropics. A large fraction of the source could be from marine lightning. Oxidation of DMS transported by convection from the boundary layer could explain the observed free tropospheric SO2 concentrations over the tropical Pacific. This source of DMS due to convection, however, would imply in the model free tropospheric concentrations much higher than observed. The model overestimate cannot be reconciled using recent kinetics measurements of the DMS-OH adduct reaction at low pressures and temperatures and may reflect enhanced OH oxidation of DMS during convection. Copyright 2001 by the American Geophysical Union