Erik Charles Richard

Chemical depletion of Arctic ozone in winter 1999/2000

During Arctic winters with a cold, stable stratospheric circulation, reactions on the surface of polar stratospheric clouds (PSCs) lead to elevated abundances of chlorine monoxide (ClO) that, in the presence of sunlight, destroy ozone. Here we show that PSCs were more widespread during the 1999/2000 Arctic winter than for any other Arctic winter in the past two decades. We have used three fundamentally different approaches to derive the degree of chemical ozone loss from ozonesonde, balloon, aircraft, and satellite instruments. We show that the ozone losses derived from these different instruments and approaches agree very well, resulting in a high level of confidence in the results. Chemical processes led to a 70% reduction of ozone for a region ∼1 km thick of the lower stratosphere, the largest degree of local loss ever reported for the Arctic. The Match analysis of ozonesonde data shows that the accumulated chemical loss of ozone inside the Arctic vortex totaled 117 ± 14 Dobson units (DU) by the end of winter. This loss, combined with dynamical redistribution of air parcels, resulted in a 88 ± 13 DU reduction in total column ozone compared to the amount that would have been present in the absence of any chemical loss. The chemical loss of ozone throughout the winter was nearly balanced by dynamical resupply of ozone to the vortex, resulting in a relatively constant value of total ozone of 340 ± 50 DU between early January and late March. This observation of nearly constant total ozone in the Arctic vortex is in contrast to the increase of total column ozone between January and March that is observed during most years.

Evidence of the effect of summertime midlatitude convection on the subtropical lower stratosphere from CRYSTAL‐FACE tracer measurements

[1] Trace gas and particle measurements taken during the CRYSTAL-FACE mission are used to examine mixing in the summer subtropical lower stratosphere. Vigorous convection in the central and eastern United States injected a significant amount of tropospheric air into the lower stratosphere, which was subsequently advected over the region sampled during the CRYSTAL-FACE mission. Aerosols produced by biomass burning were observed over Florida during a time period with a large number of forest fires in the western United States and eastern Canada, providing evidence of convective injection of tropospheric air into the lower stratosphere. The circumstances of the large-scale flow pattern in the upper troposphere and lower stratosphere, vigorous summertime convection, abundant forest fires, and the downstream sampling allow a unique view of mixing in the lower stratosphere. We calculate the fractions of midlatitude tropospheric air in the sampled lower stratosphere and mixing rates on the basis of consistency between a number of tracer-tracer correlations. The tropospheric endpoints to the mixing estimates give an indication of midlatitude continental convective input into the lower stratosphere. We also discuss the possible impact of summertime midlatitude convection on the composition of the stratosphere as a whole.

Large‐scale chemical evolution of the Arctic vortex during the 1999/2000 winter: HALOE/POAM III Lagrangian photochemical modeling for the SAGE III—Ozone Loss and Validation Experiment (SOLVE) campaign

Abstract : The LaRC Lagrangian Chemical Transport Model (LaRC LCTM) is used to simulate the kinematic and chemical evolution of an ensemble of trajectories initialized from Halogen Occultation Experiment (HALOE) and Polar Ozone and Aerosol Measurement (POAM) III atmospheric soundings over the SAGE III-Ozone Loss and Validation Experiment (SOLVE) campaign period. Initial mixing ratios of species which are not measured by HALOE or POAM III are specified using sunrise and sunset constituent CH(4) and constituent PV regressions obtained from the LaRC IMPACT model, a global three dimensional general circulation and photochemical model. Ensemble averaging of the trajectory chemical characteristics provides a vortex-average perspective of the photochemical state of the Arctic vortex. The vortex-averaged evolution of ozone, chlorine, nitrogen species, and ozone photochemical loss rates is presented. Enhanced chlorine catalyzed ozone loss begins in mid-January above 500 K, and the altitude of the peak loss gradually descends during the rest of the simulation. Peak vortex averaged loss rates of over 60 ppbv/day occur in early March at 450 K. Vortex averaged loss rates decline after mid- March. The accumulated photochemical ozone loss during the period from 1 December 1999 to 30 March 2000 peaks at 450 K with net losses of near 2.2 ppmv. The predicted distributions of CH4, O(3), denitrification, and chlorine activation are compared to the distributions obtained from in situ measurements to evaluate the accuracy of the simulations. The comparisons show best agreement when diffusive tendencies are included in the model calculations, highlighting the importance of this process in the Arctic vortex. Sensitivity tests examining the large-scale influence of orographically generated gravity wave temperature anomalies are also presented. Results from this sensitivity study show that mountain-wave temperature perturbations contribute an additional 2-8% O(3) loss during the 1999/2000 winter.

Exchange between the upper tropical troposphere and the lower stratosphere studied with aircraft observations

Exchange between the upper tropical troposphere and the lower stratosphere is considered by examining WB57F and ER-2 aircraft observations of water, ozone, wind, and temperature in the potential temperature range 360 < θ < 420 K. These processes are examined in part by using the technique of unified scale invariance on the airborne data, as has been done previously for the lower stratospheric polar vortex. Scale invariance is found, on scales from a few hundred meters to the maximum flown, 2700 km (25 great circle degrees). The results apply both to vertical exchange at the tropical tropopause and to isentropic exchange at the subtropical jet stream. All scales participate in the maintenance of the mean state, with substantial contributions from relatively infrequent but intense events in the long tails of the probability distributions. Past data are examined and found to fit this general framework. A unique mapping of tropical tropopause temperature to the total hydrogen content of the middleworld and overworld should not be expected; the head of the tape recorder is at 50-60 hPa rather than 90-100 hPa. The tropical tropopause is observed at potential temperatures θ T greater than the maximum moist static surface values θ W , such that θ T - θ W varies between 10 K in fall and up to 40 K in spring. The meridional gradient of θ T is directed from the subtropical jet stream to the inner tropics, with θ T declining by approximately 10 K from near 30°N to near 10°N in the vicinity of 95°W. The maintenance of these θ T values is discussed. Total water (measured as the sum of vapor and vaporized ice) and ozone, major absorbers of solar radiation and emitters/ absorbers of terrestrial infrared radiation, show scale invariance in the upper tropical troposphere. The implications of this result for the notion of a conservative cascade of energy via fluid dynamics from the largest to the smallest scales are discussed. The scaling exponents H z for total water and ozone in the upper tropical troposphere are not the value, 5/9, expected for a passive scalar, probably indicating the presence of sources and/or sinks operating faster than mixing.

Comparison of ER‐2 aircraft and POAM III, MLS, and SAGE II satellite measurements during SOLVE using traditional correlative analysis and trajectory hunting technique

We compared the version 5 Microwave Limb Sounder (MLS), version 3 Polar Ozone and Aerosol Measurement III (POAM III), version 6.0 Stratospheric Aerosol and Gas Experiment II (SAGE II), and NASA ER-2 aircraft measurements made in the Northern Hemisphere in January–February 2000 during the SAGE III Ozone Loss and Validation Experiment (SOLVE). This study addresses one of the key scientific objectives of the SOLVE campaign, namely, to validate multiplatform satellite measurements made in the polar stratosphere during winter. This intercomparison was performed by using a traditional correlative analysis (TCA) and a trajectory hunting technique (THT). TCA compares profiles colocated within a chosen spatial-temporal vicinity. Launching backward and forward trajectories from the points of measurement, the THT identifies air parcels sampled at least twice within a prescribed match criterion during the course of 5 days. We found that the ozone measurements made by these four instruments agree most of the time within ±10% in the stratosphere up to 1400 K (∼35 km). The water vapor measurements from POAM III and the ER-2 Harvard Lyman α hygrometer and Jet Propulsion Laboratory laser hygrometer agree to within ±0.5 ppmv (or about ±10%) in the lower stratosphere above 380 K. The MLS and ER-2 ClO measurements agree within their error bars for the TCA. The MLS and ER-2 nitric acid measurements near 17- to 20-km altitude agree within their uncertainties most of the time with a hint of a positive offset by MLS according to the TCA. We also applied the Atmospheric and Environmental Research, Inc. box model constrained by the ER-2 measurements for analysis of the ClO and HNO3 measurements using the THT. We found that: (1) the model values of ClO are smaller by about 0.3–0.4 (0.2) ppbv below (above) 400 K than those by MLS and (2) the HNO3 comparison shows a positive offset of MLS values by ∼1 and 1–2 ppbv below 400 K and near 450 K, respectively. Our study shows that, with some limitations (like HNO3 comparison under polar stratospheric cloud conditions), the THT is a more powerful tool for validation studies than the TCA, making conclusions of the comparison statistically more robust.

Observation of stratospheric ozone depletion associated with Delta II rocket emissions

Ozone, chlorine monoxide, methane, and submicron particulate concentrations were measured in the stratospheric plume wake of a Delta II rocket powered by a combination of solid (NH4ClO4/Al) and liquid (LOX/kerosene) propulsion systems. We apply a simple kinetics model describing the main features of gas-phase chlorine reactions in solid propellant exhaust plumes to derive the abundance of total reactive chlorine in the plume and estimate the associated cumulative ozone loss. Measured ozone loss during two plume encounters (12 and 39 minutes after launch) exceeded the estimate by about a factor of about two. Insofar as only the most significant gas-phase chlorine reactions are included in the calculation, these results suggest that additional plume wake chemical processes or emissions other than reactive chlorine from the Delta II propulsion system affect ozone levels in the plume.

Chlorine activation near the midlatitude tropopause

wave activity, high particulate surface areas (5–20 mm 2 cm �3 ), low ozone, and relatively high humidities (20–25 ppm of H2O, yet undersaturated with respect to ice), consistent with a heterogeneous mechanism on particles formed in recently lofted tropospheric air as it mixed into the lowermost stratosphere. These observations are similar to a previous one of chlorine activation on volcanic aerosol, suggesting a common heterogeneous chemical mechanism involving HCl, ClNO3, and HOCl that even in volcanically quiescent years can impact ozone photochemistry in regions of the lowermost stratosphere influenced by mixing from the tropopause region. Models not incorporating this chlorine activation process may be underestimating the impact on ozone in the midlatitude lowermost stratosphere by decomposition of very short lived halocarbon compounds, including substitutes for ozone-depleting compounds.

Study blazing new trails into effects of aviation and rocket exhaust in the atmosphere

A new study may help resolve uncertainties in the impact of aviation and rocket exhaust on the atmosphere. Results of the project are expected to serve the aviation and rocket communities in their propulsion system choices and fleet operations in the 21st century. The study, known as the Atmospheric Chemistry of Combustion Emissions near the Tropopause (ACCENT) project, follows the lead of two other programs motivated by continuing concern over the impact such emissions are having on upper troposphere and lower stratosphere (UT/LS) ozone and climate. ACCENT in effect combines those two programs, one of which concerns aviation, the other rockets.

Molecular velocity distributions and generalized scale invariance in the turbulent atmosphere

Airborne observations of ozone, temperature and the spectral actinic photon flux for ozone in the Arctic lower stratosphere April-September 1997 and January-March 2000 allow a connection to be made between the rate of production of translationally hot atoms and molecules via ozone photodissociation and the intermittency of temperature. Seen in the context of non-equilibrium statistical mechanics literature results from molecular dynamics simulations, the observed correlation between the molecular scale production of translationally hot atoms and molecules and the macroscopic fluid mechanical intermittency of temperature may imply a departure from Maxwell-Boltzmann distributions of molecular velocities, with consequences for chemistry, radiative line shapes and turbulence in the atmosphere, arising from overpopulated high velocity tails of the probability distribution functions (PDFs).