Publications (12)42.95 Total impact
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Article: Atmospheric observations of Arctic Ocean methane emissions up to 82° north
Nature Geoscience 01/2012; 5:318. · 11.75 Impact Factor -
Article: The NOx−HNO3 System in the Lower Stratosphere: Insights from In Situ Measurements and Implications of the JHNO3−[OH] Relationship
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ABSTRACT: During the 1997 Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission, simultaneous in situ observations of NOx and HOx radicals, their precursors, and the radiation field were obtained in the lower stratosphere. We use these observations to evaluate the primary mechanisms that control NOx−HNO3 exchange and to understand their control over the partitioning between NO2 and HNO3 in regions of continuous sunlight. We calculate NOx production (PNOx) and loss (LNOx) in a manner directly constrained by the in situ measurements and current rate constant recommendations, using approaches for representing albedo, overhead O3 and [OH] that reduce model uncertainty. We find a consistent discrepancy of 18% between modeled rates of NOx production and loss (LNOx = 1.18PNOx) which is within the measurement uncertainty of ±27%. The partitioning between NOx production processes is [HNO3 + OH (41 ± 2)%; HNO3 + hν (59 ± 2)%] and between NOx loss processes is [NO2 + OH, 90% to >97%; BrONO2 + H2O, 10% to <3%]. The steady-state description of NOx−HNO3 exchange reveals the significant influence of the tight correlation between the photolysis rate of HNO3 and [OH] established by in situ measurements throughout the lower stratosphere. Parametrizing this relationship, we find (1) the steady-state value of [NO2]24h-avg/[HNO3] in the continuously sunlit, lower stratosphere is a function only of temperature and number density, and (2) the partitioning of NOx production between HNO3 + OH and HNO3 + hν is nearly constant throughout most of the lower stratosphere. We describe a methodology (functions of latitude, day, temperature, and pressure) for accurately predicting the steady-state value of [NO2]24h-avg/[HNO3] and the partitioning of NOx production within these regions. The results establish a metric to compare observations of [NO2]24h-avg/[HNO3] within the continuously sunlit region and provide a simple diagnostic for evaluating the accuracy of models that attempt to describe the coupled NOx−HOx photochemistry in the lower stratosphere.01/2001; -
Article: Sources, Sinks, and the Distribution of OH in the Lower Stratosphere†
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ABSTRACT: Extensive measurement campaigns by the NASA ER-2 research aircraft have obtained a nearly pole-to-pole database of the species that control HOx (OH + HO2) chemistry. The wide dynamic range of these in situ measurements provides an opportunity to demonstrate empirically the mechanisms that control the HOx system. Measurements in the lower stratosphere show a remarkably tight correlation of OH concentration with the solar zenith angle (SZA). This correlation is nearly invariant over latitudes ranging from 70° S to 90° N and all seasons. An analysis of the production and loss of HOx in terms of the rate determining steps of reaction sequences developed by Johnston and Podolske and Johnston and Kinnison is used to clarify the behavior of the system and to directly test our understanding of the system with observations. Calculations using in situ measurements show that the production rate of HOx is proportional to O3 and ultraviolet radiation flux. The loss rate is proportional to the concentration and the partitioning of NOy (reactive nitrogen) and the concentration of HO2. In the absence of heterogeneous reactions, the partitioning of NOy is controlled by O3 and HOx and the concentration of HO2 is controlled by NOy and O3, so that the removal rate of OH is buffered against changes in the correlation of O3 and NOy. The heterogeneous conversion of NO2 to HNO3 is not an important net source of HOx because production and removal sequences are nearly balanced. Changes in NOy partitioning resulting from heterogeneous chemistry have a large effect on the loss rates of HOx, but little or no impact on the measured abundance of OH. The enhanced loss rates at high NO2/HNO3 are offset in the data set examined here by enhanced production rates resulting from increased photolysis rates resulting from the decreased O3 column above the ER-2.12/2000; -
Article: Troposphere-to-Stratosphere Transport in the Lowermost Stratosphere from Measurements of H2O, CO2, N2O and O3
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ABSTRACT: The origin of air in the lowermost stratosphere is investigated with measurements from the NASA ER-2 aircraft. Air with high water vapor mixing ratios was observed in the stratosphere at theta = 330-380 K near 40 N in May 1995, indicating the influence of intrusions of tropospheric air. Assuming that observed tracer-tracer relationships reflect mixing lines between tropospheric and stratospheric air masses, we calculate mixing ratios of H2O (12-24 ppmv) and CO2 for the admixed tropospheric air at theta = 352-364 K. Temperatures on the 355 K surface at 20-40 N were low enough to dehydrate air to these values. While most ER-2 CO2 data in both hemispheres are consistent with tropical or subtropical air entering the lowermost stratosphere, measurements from May 1995 for theta < 362 K suggest that entry of air from the midlatitude upper troposphere can occur in conjunction with mixing processes near the tropopause.08/1998; -
Article: Troposphere-to-Stratosphere Transport in the Lowermost Stratosphere from Measurements of H2O, CO2, N2O, and O3
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ABSTRACT: The origin of air in the lowermost stratosphere is investigated with measurements from the NASA ER-2 aircraft. Air with high water vapor mixing ratios was observed in the stratosphere at theta approximately 330-380 K near 40 N in May 1995, indicating the influence of intrusions of tropospheric air. Assuming that observed tracer-tracer relationships reflect mixing lines between tropospheric and stratospheric air masses, we calculate mixing ratios of H2O (12-24 ppmv) and CO2 for the admixed tropospheric air at theta = 352-364 K. Temperatures on the 355 K surface 20-40 N were low enough to dehydrate air to these values. While most ER-2 CO2 data in both hemispheres are consistent with tropical or subtropical air entering the lowermost stratosphere, measurements from May 1995 for theta < 362 K suggest that entry of air from the midlatitude upper troposphere can occur in conjunction with mixing processes near the tropopause.08/1998; -
Article: Observed OH and HO 2 in the upper troposphere suggest a major
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ABSTRACT: ER-2 aircraft observations of OH and HO 2 concentrations in the upper troposphere during the NASA/STRAT campaign are interpreted u sing a photochemical model constrained by local observations of O 3 , H 2 O, NO, CO, hydrocarbons, albedo and overhead ozone column. We find that the reaction O( D) + H 2 O is minor compared to acetone photolysis as a primary source of HO x (= OH + peroxy radicals) in the upper troposphere. Calculations using a diel steady state model agree with ob served HO x concentrations in the lower stratosphere a nd, for some flights, in the upper troposphere. However, for other flights in the upper troposphere, the steady state model underestimates observations by a factor of 2 or more. These model underestimates are found to be related to a recent (< 1 week) convective origin of the air. By conducting time-dependent model calculations along air trajectories determined for the STRAT flights, we show that convective injection o f CH 3 OOH and H 2 O 2 from the boundary layer to the upper troposphere ca n resolve the discrepancy. These injections of HO x reservoirs cause large HO x increases in the tropical upper troposphere for over a week downwind of the convective activity. We propose that this mechanism provides a major source of HO x in the upper troposphere. Simultaneous measurements of peroxides, formaldehyde a nd acetone a long with OH and HO 2 are needed to test our hypothesis.04/1998; -
Article: Dehydration and Denitrification in the Arctic Polar Vortex During the 1995-1996 Winter
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ABSTRACT: Dehydration of more than 0.5 ppmv water was observed between 18 and 19 km (theta approximately 450-465 K) at the edge of the Arctic polar vortex on February 1, 1996. More than half the reactive nitrogen (NO(y)) had also been removed, with layers of enhanced NO(y) at lower altitudes. Back trajectory calculations show that air parcels sampled inside the vortex had experienced temperatures as low as 188 K within the previous 12 days, consistent with a small amount of dehydration. The depth of the dehydrated layer (approximately 1 km) and the fact that trajectories passed through the region of ice saturation in one day imply selective growth of a small fraction of particles to sizes large enough (>10 micrometers) to be irreversibly removed on this timescale. Over 25% of the Arctic vortex in a 20-30 K range Transport of theta is estimated to have been dehydrated in this event.03/1998; -
Article: Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere
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ABSTRACT: The concentrations of the hydrogen radicals OH and HO2in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HOx required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2and NO) is calculated to be about 1 part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more O3 than expected.Science 01/1998; 279(5347):49-53. · 31.20 Impact Factor -
Article: The Effects of Tropical Cirrus Clouds on the Abundance of Lower Stratospheric Ozone
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ABSTRACT: The distribution of many chemical constituents of the atmosphere (e.g., ozone) is at least partially determined by the distribution of net radiative heating in the atmosphere. In this paper, we demonstrate the significant effect of high cirrus clouds on the net radiative heating of the tropical lower stratosphere. A model of tropical lower stratospheric ozone is then used to demonstrate the sensitivity of calculated ozone to the varying cloud cover used in the model. We conclude that calculated ozone is sensitive to the inclusion of clouds in models and that models of the atmosphere should include a realistic description of tropical cirrus clouds in order to accurately simulate the chemical composition of the atmosphere.02/1996; -
Article: In situ observations in aircraft exhaust plumes in the lower stratosphere at midlatitudes
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ABSTRACT: Instrumentation on the NASA ER-2 high-altitude aircraft has been used to observe engine exhaust from the same aircraft while operating in the lower stratosphere. Encounters with the exhaust plume occurred approximately 10 min after emission with spatial scales near 2 km and durations of up to 10 s. Measurements include total reactive nitrogen, NO(y), the component species NO and NO2, CO2, H2O, CO, N2O, condensation nuclei, and meteorological parameters. The integrated amounts of CO2 and H2O during the encounters are consistent with the stoichiometry of fuel combustion (1:1 molar). Emission indices (EI) for NO(x) (= NO + NO2), CO, and N2O are calculated using simultaneous measurements of CO2. EI values for NO(x) near 4 g/(kg fuel) are in good agreement with values scaled from limited ground-based tests of the ER-2 engine. Non-NO(x) species comprise less than about 20% of emitted reactive nitrogen, consistent with model evaluations. In addition to demonstrating the feasibility of aircraft plume detection, these results increase confidence in the projection of emissions from current and proposed supersonic aircraft fleets and hence in the assessment of potential long-term changes in the atmosphere.03/1995; -
Article: An examination of the total hydrogen budget of the lower stratosphere
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ABSTRACT: We analyze the hydrogen budget of the lower stratosphere using simultaneous in situ measurements of northern hemispheric water vapor (H2O) and methane (CH4) obtained during the spring Stratospheric Photochemistry, Aerosols, and Dynamics Expedition (SPADE), as well as previously published in situ H2 data. Based on this data, we conclude that approximately two H2O molecules are produced for each CH4 molecule destroyed. This implies that H2 production from CH4 oxidation is balanced by H2 oxidation. The uncertainty in this analysis is greatly reduced by the use of multiple data sets. Additionally, we infer that, on an annual and global average, H2O enters the stratosphere with a mixing ratio of 4.2 +/- 0.5 ppmv, and that the quasi-conserved quantity 2 x CH4 + H2O has a value of 7.6 +/- 0.6 ppmv in these northern hemishere air parcels (where xi denotes the mixing ratio of the constituent xi).12/1994; -
Article: Validation of the Harvard Lyman-α in situ water vapor instrument: Implications for the mechanisms that control stratospheric water vapor
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ABSTRACT: Building on previously published details of the laboratory calibrations of the Harvard Lyman-α photofragment fluorescence hygrometer (HWV) on the NASA ER-2 and WB-57 aircraft, we describe here the validation process for HWV, which includes laboratory calibrations and intercomparisons with other Harvard water vapor instruments at water vapor mixing ratios from 0 to 10 ppmv, followed by in-flight intercomparisons with the same Harvard hygrometers. The observed agreement exhibited in the laboratory and during intercomparisons helps corroborate the accuracy of HWV. In light of the validated accuracy of HWV, we present and evaluate a series of intercomparisons with satellite and balloon borne water vapor instruments made from the upper troposphere to the lower stratosphere in the tropics and midlatitudes. Whether on the NASA ER-2 or WB-57 aircraft, HWV has consistently measured about 1–1.5 ppmv higher than the balloon-borne NOAA/ESRL/GMD frost point hygrometer (CMDL), the NOAA Cryogenic Frost point Hygrometer (CFH), and the Microwave Limb Sounder (MLS) on the Aura satellite in regions of the atmosphere where water vapor is <10 ppmv. Comparisons in the tropics with the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite show large variable differences near the tropopause that converge to ~10% above 460 K, with HWV higher. Results we show from the Aqua Validation and Intercomparison Experiment (AquaVIT) at the AIDA chamber in Karlsruhe do not reflect the observed in-flight differences. We illustrate that the interpretation of the results of comparisons between modeled and measured representations of the seasonal cycle of water entering the lower tropical stratosphere is dictated by which data set is used.
