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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

X-ray Transient Absorption Studies of Exciton Self-Trapping

Here, we present optical pump/X-ray absorption probe studies to probe changes in electronic distribution and local structure upon formation of a self-trapped exciton. The experiments were carried out on the mixed-valence halide-bridged transition metal linear chain charge density wave material [Pt(en 2 )][Pt(en 2 )Cl 2 ]·(ClO 4 ) 4 . Photoinduced changes in the Pt L III XANES spectrum were measured on a picosecond time scale following generation of excitons via optical excitation of the intervalence charge transfer transition. Ab initio FEFF9 modeling of the spectra and the associated angular momentum projected density of states was used to interpret the response. We find photoinduced changes reflecting electronic redistribution and local lattice distortions that correspond to strong localization of the self-trapped state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

In situ measurements of BrO in the Arctic stratosphere

Mixing ratios of BrO have been measured in the Arctic lower statosphere with an instrument mounted on the NASA ER-2 aircraft. Observations from fourteen flights above the Arctic Circle in January and February of 1989 defined mixing ratios within the vortex of 4 + or - 2 parts per trillion by volume (pptv) at a potential temperature of 400 K, rising to 8 + or - 2 pptv at 470 K. These values are twice as large as values found at equivalent potential temperatures at lower latitudes, and are comparable to the mixing ratios found inside the antarctic polar vortex. Within the statistical uncertainty of the measurements, no BrO was observed in darkness at any time either inside or outside of the vortex, indicating that active bromine was sequestered in long-lived reservoirs, probably BrONO2 and BrCl. These measurements, in conjuction with measurements of ClO, demonstrate that the interaction of bromine and chlorine could represent a major sink for ozone in the presence of sunlight.

Toohey, D. W.↗
NASA NTRS2000

Trajectory Hunting: A Case Study of Rapid Chlorine Activation in December 1992 as Seen by UARS

Trajectory hunting (i.e., a technique to find air parcels sampled at least twice over the course of a few days) is applied to analyze Upper Atmosphere Research Satellite (UARS) measurements in conjunction with the Atmospheric and Environmental Research, Inc. (AER) photochemical box model. As a case study, we investigate rapid chlorine activation in the Arctic lower stratosphere on December 29, 1992 associated with a polar stratospheric cloud (PSC) event. Eleven air parcels that have been sampled several times along 5-day trajectories at the 465 K (approx. 46 hPa), 520 K (approx. 31 hPa), and 585 K (approx. 22 hPa) levels were investigated. For the first time, the latest versions of the Cryogenic Limb Array Etalon Spectrometer (CLAES, version 9) and Microwave Limb Sounder (MLS, version 5) data sets are analyzed, and their consistency is assessed. A detailed sensitivity study with the AER photochemical box model along these trajectories leads to the conclusion that for the December 24-29, 1992 episode (1) the individual CLAES version 9 ClONO2 and MLS version 5 ClO measurements are self-consistent within their uncertainties; and (2) most of the time, UARS measurements of ClO, ClONO2, HNO3, and aerosol extinction at 780 cm (exp -1) agree within the range of their uncertainties with the model calculations. It appears that the HNO3 and aerosol extinction measurements for four parcels at 520 K look more supportive for the nitric acid trihydrate (NAT) scheme. However, the uncertainties in the individual UARS measurements and U.K. Meteorological Office temperature do not allow a definite discrimination between the NAT and supercooled ternary solution (STS) PSC schemes for this chlorine activation episode in December 1992.

Danilin, M. Y.↗
NASA NTRS2000

Trajectory Hunting: A Case Study of Rapid Chlorine Activation in December 1992 as Seen by UARS

Trajectory hunting (i.e., a technique to find air parcels sampled at least twice over the course of a few days) is applied to analyze Upper Atmosphere Research Satellite (UARS) measurements in conjunction with the Atmospheric and Environmental Research, Inc. (AER) photochemical box model. As a case study, we investigate rapid chlorine activation in the Arctic lower stratosphere on December 29, 1992 associated with a polar stratospheric cloud (PSC) event. Eleven air parcels that have been sampled several times along five-day trajectories at the 465 K (approx. 46 hPa), 520 K (approx. 31 hPa), and 585 K (approx. 22 hPa) levels were investigated. For the first time, the latest versions of the Cryogenic Limb Array Etalon Spectrometer (CLAES, version 9) and Microwave Limb Sounder (MLS, version 5) data sets are analyzed, and their consistency is assessed. A detailed sensitivity study with the AER photochemical box model along these trajectories leads to the conclusion that for the December 24-29, 1992 episode: (1) the individual CLAES ClONO2 and MLS ClO measurements are self-consistent within their uncertainties; and (2) most of the time, UARS measurements of ClO, ClONO2, HNO3, and aerosol extinction at 780 cm(exp -1) agree within the range of their uncertainties with the model calculations. It appears that the HNO3 and aerosol extinction measurements for four parcels at 520 K look more supportive for the nitric acid trihydrate (NAT) scheme, However, the uncertainties in the individual UARS measurements and UK Meteorological Office temperature do not allow a definite discrimination between the NAT and supercooled ternary solution (STS) PSC schemes for this chlorine activation episode in December 1992.

Danilin, M. Y.↗
NASA NTRS2001

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) aboard the Upper Atmosphere Research Satellite (UARS), version 3 Polar Ozone and Aerosol Measurement-III (POAM-111) aboard the French satellite SPOT-IV, version 6.0 Stratospheric Aerosol and Gas Experiment 11 (SAGE-II) aboard the Earth Radiation Budget Satellite, 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 multi-platform satellite measurements made in the polar stratosphere during winter. This intercomparison was performed using a traditional correlative analysis (TCA) and a trajectory hunting technique (THT). 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 110% in the stratosphere up to 1400 K (approximately 35 km). The water vapor measurements from POAM-III and the ER-2 Harvard Lyman-alpha hygrometer and JPL laser hygrometer agree to within 10.5 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 17-20 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 AER box model constrained by the ER-2 measurements for analysis of the ClO and HN03 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 HN03 comparison shows a positive offset of MLS values by approximately 1 and 1-2 ppbv below 400 K and near 450 K, respectively. It is hard to quantify the HN03 offset in the 400-440 K range because of the high sensitivity of nitric acid to the PSC schemes. Our study shows that, with some limitations (like HN03 comparison under PSC conditions), the THT is a more powerful tool for validation studies than the TCA, making conclusions of the comparison statistically more robust.

Danilin, M. Y.↗
NASA NTRS1996

Validation of UARS Microwave Limb Sounder ClO Measurements

Validation of stratospheric ClO measurements by the Microwave Limb Sounder (MLS) on the Upper Atmosphere Research Satellite (UARS) is described. Credibility of the measurements is established by (1) the consistency of the measured ClO spectral emission line with the retrieved ClO profiles and (2) comparisons of ClO from MLS with that from correlative measurements by balloon-based, ground-based, and aircraft-based instruments. Values of "noise" (random), "scaling" (multiplicative), and "bias" (additive) uncertainties are determined for the Version 3 data, in the first version public release of the known artifacts in these data are identified. Comparisons with correlative measurements indicate agreement to within the combined uncertainties expected for MLS and the other measurements being compared. It is concluded that MLS Version 3 ClO data, with proper consideration of the uncertainties and "quality" parameters produced with these data, can be used for scientific analyses at retrieval surfaces between 46 and 1 hPa (approximately 20-50 km in height). Future work is planned to correct known problems in the data and improve their quality.

Waters, J. W.↗
DOE OSTI2020

Correlating Mechanical Sensitivity with Spin Transition in the Explosive Spin Crossover Complex [Fe(Htrz) 3 ] n [ClO 4 ] 2 n

Spin crossover complexes are known to undergo bond length, volume, and enthalpy changes during spin transition. In an explosive spin crossover complex, these changes could affect the mechanical and initiation sensitivity of the explosive and lead to the development of a new class of sensitivity switchable materials. To explore this relationship, the well-known spin crossover compound [Fe(Htrz) 3 ] n [ClO 4 ] 2n (1) was re-evaluated for its explosive properties, and its mechanical impact sensitivity was correlated to spin transition. A variable temperature impact test was developed and used to evaluate the impact sensitivity of 1 in the low spin (LS, S = 0), thermally accessed high spin (HS, S = 2), and mixed LS and HS states. For comparison, the structurally similar Ni compound, [Ni(Htrz) 3 ] n [ClO 4 ] 2n (2), which does not undergo a spin transition at accessible temperatures, was synthesized and characterized, and its explosive properties and variable temperature impact sensitivity measured. These results reveal a correlation between impact sensitivity and spin transition, where 1 exhibits lower impact sensitivity in the LS state and increases in sensitivity upon transition to the HS state. Here, density functional theory was used to predict structural changes that occur upon spin transition that correlate to the change in sensitivity. This demonstrates, for the first time, an explosive spin crossover compound (ExSCO) that exhibits switchable impact sensitivity with a fully reversible internal switching mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1980

Kinetics study of the Cl/2P/ + Cl2O yields Cl2 + ClO reaction at 298 K

The kinetics of the Cl + Cl2O reaction, a possible source of ClO(2 Pi) radicals for atmospheric photochemical studies, are investigated at 298 K. The discharge flow/mass spectrometry and discharge flow/resonance fluorescence techniques were used to monitor the decay of C12O in the presence of excess concentrations of atomic chlorine and chlorine monoxide, respectively. The pseudo-first order rate constants obtained from both experiments are found to be in excellent agreement, averaging 9.8 + or - 0.8 x 10 to the -11th cu cm/molecule per sec. Results are consistent with the lower limit obtained by Edgecombe et al. (1957) but differ by a factor of 150 from those of Basco and Dogra (1971). The present value is also noted to be consistent with a lower value for the rate constant of the reaction of oxygen atoms with Cl2O.

Ray, G. W.↗
NASA NTRS1994

The distribution of hydrogen, nitrogen, and chlorine radicals in the lower stratosphere: Implications for changes in O3 due to emission of NO(y) from supersonic aircraft

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower statosphere during SPADE are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 agree well with measured concentrations of NO and ClO, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for (OH) and (HO2) are reduced if we allow for higher yields of O((1)D) from O2 photolysis and for heterogeneous production of HNO2. The data suggest more efficent catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommendend rates and cross sections. Increased in (O3) in the lower stratosphere may be larger in response to inputs of NO(y) from supersonic aircraft than estimated by current assessment models.

Salawitch, R. J.↗
NASA NTRS1994

The Distribution of Hydrogen, Nitrogen, and Chlorine Radicals in the Lower Stratosphere: Implications for Changes in O3 due to Emission of NO(y) from Supersonic Aircraft

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower stratosphere during the Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE) are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N2O5 agree well with measured concentrations of NO and ClO, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO2 are overestimated by 10 to 30%, and concentrations of HCl are overestimated by a factor of 2. Discrepancies for [OH] and [HO2] are reduced if we allow for higher yields of O(sup 1)D) from 03 photolysis and for heterogeneous production of HNO2. The data suggest more efficient catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommended rates and cross sections. Increases in [O3] in the lower stratosphere may be larger in response to inputs of NO(sub y) from supersonic aircraft than estimated by current assessment models.

Salawitch, R. J.↗
NASA NTRS1996

Bromine-Chlorine Coupling in the Antarctic Ozone Hole

The contribution from the chlorine and bromine species in the formation of the Antarctic ozone hole is evaluated. Since chlorine and bromine compounds are of different industrial origin, it is desirable, from a policy point of view, to be able to attribute chlorine-catalyzed loss of ozone with those reactions directly involving chlorine species, and likewise for bromine-catalyzed loss. In the stratosphere, however, most of the chemical families are highly coupled, and, for example, changes in the chlorine abundance will alter the partitioninig in other families and thus the rate of ozone loss. This modeling study examines formation of the Antarctic ozone hole for a wide range of bromine concentrations (5 - 25 pptv) and for chlorine concentrations typical of the last two decades (1.5, 2.5 and 3.5 ppbv). We follow the photochemical evolution of a single parcel of air, typical of the inner Antarctic vortex (50 mbar, 70 deg. S, NO(sub y) = 2 ppbv, with Polar Stratospheric Clouds(PSC)) from August 1 to November 1. For all of these ranges of chlorine and bromine loading, we would predict a substantial ozone hole (local depletion greater than 90%) within the de-nitrified, PSC- perturbed vortex. The contributions of the different catalytic cycles responsible for ozone loss are tabulated. The deep minimum in ozone is driven primarily by the chlorine abundance. As bromine levels decrease, the magnitude of the chlorine-catalyzed ozone loss increases to take up the slack. This is because bromine suppresses ClO by accelerating the conversion of ClO an Cl2O2 back to HCI. For this range of conditions, the local relative efficiency of ozone destruction per bromine atom to that per chlorine atom (alpha-factor) ranges from 33 to 55, decreasing with increase of bromine.

Danilin, Michael Y.↗
DOE OSTI2021

Origin of the isotopic composition of natural perchlorate: Experimental results for the impact of reaction pathway and initial ClO x reactant

Natural perchlorate (ClO 4 - ) exists in many places on Earth, in lunar regolith, meteorites, and on the surface of Mars. Terrestrial natural ClO 4 - has widely variable Cl and O stable isotopic compositions (δ 37 Cl, δ 18 O, Δ 17 O). The δ 18 O and Δ 17 O values of ClO 4 - from the most hyper-arid locations co-vary. ClO 4 - from less arid areas has relatively little 17 O excess and poor Δ 17 O-δ 18 O correlation. ClO 4 - from the Atacama Desert has unusually low δ 37 Cl (<-10‰) and exhibits a positive correlation between δ 37 Cl and δ 18 O, while the δ 37 Cl of ClO 4 - from all other locations varies between -5 and +7‰ with no δ 37 Cl-δ 18 O covariation. To evaluate the impact of different precursors (ClO x ) and reaction pathways on the isotopic composition of ClO 4 - , we measured the isotopic composition of ClO 4 - produced in the laboratory by UV or O 3 mediated aqueous oxidation of Cl-, OCl-, ClO2-, and ClO2° as well as O 3 mediated oxidation of dry NaCl. ClO x oxidation in aqueous or dry systems enriched in O 3 produced ClO 4 - with Δ 17 O values that generally increased with the number of O atoms required and included evidence that the site-specific 17 O anomaly in O 3 was preferentially transferred to ClO 4 - . Based on the inferred number of O atoms sourced from O 3 , and known Cl and O reaction pathways, it appears that ClO 2 ° and ClO 3 * were required intermediates in the production of ClO 4 - in the O 3 experiments. ClO x aqueous oxidation by UV irradiation produced ClO 4 - with a large range of δ 18 O values and little or no 17 O anomaly. ClO 3 - was produced to a much greater extent than ClO 4 - in all experiments except dry oxidation of NaCl by O 3 . The isotopic composition of ClO 3 - was distinct from that of ClO 4 - produced from the same initial reactants. Combined results of O 3 and UV mediated reactions largely bracketed the range of natural ClO 4 - δ 18 O and Δ 17 O values as well as δ 37 Cl values of non-Atacama natural samples, but no conditions produced the low δ 37 Cl values of Atacama ClO 4 - . Finally, our results indicate that variation in production mechanisms, possibly combined with isotopically variable precursors, could be responsible for much of the observed isotopic variation in natural ClO 4 - and ClO 3 - .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Structural Tuning of Self‐Conductive Polymer as Gas Diffusion Layer for Electrocatalytic Reactions at High Current

Electrocatalytic conversions offer a promising route for sustainable chemical production using renewable energy. Gas diffusion layers (GDLs) enable selective product formation at high current densities but suffer from electrolyte flooding, and polytetrafluoroethylene (PTFE)-based GDLs typically require metal conductive layers, which constrain catalyst development. A recently developed GDL configuration, electropolymerized poly(3,4-ethylenedioxythiophene) (PEDOT)-coated PTFE, demonstrates notable flooding resistance, but suffers from gas diffusion limitations at elevated currents due to limited gas diffusion through the PEDOT layer. Here, different dopants in PEDOT are exploited to modify the physical properties and enhance gas transport. ClO 4 − -doped PEDOT exhibits superior performance due to optimized physical structure, leading to increased gas permeance and faradaic efficiency (FE) for CO production during electrocatalytic CO 2 reduction. Further optimization of coverage and thickness achieved by adjusting charge density led to an optimal configuration at 33 mC cm −2 . This GDL supports various metal electrocatalysts and demonstrates FE CO of > 90% for over 150 h at −200 mA cm −2 using a commercial silver electrocatalyst. This work highlights the importance of GDL engineering in enhancing performance and durability for long-term electrocatalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

Are models of catalytic removal of O3 by HO(x) accurate? Constraints from in situ measurements of the OH to HO2 ratio

Measurements of the ratio OH/HO2, NO, O3, ClO, and BrO were obtained at altitudes from 15-20 km and latitudes from 15-60 deg N. A method is presented for interpreting the rates of chemical transformations that (1) are responsible for over half the ozone removal rate in the lower stratosphere via reactions of HO2; and (2) control the abundance of HO2 through coupling to nitrogen and halogen radicals. The results show our understanding of the chemical reactions controlling the partitioning of OH and HO2 is complete and accurate and that the potential effects of 'missing chemistry' are strickly constrained in the region of the atmosphere encompassed by the observations. The analysis demonstrates that the sensitivity of the ratio OH/HO2 to changes in NO is described to within 12% by current models. This reduces by more than a factor of 2 the effect of uncertainty in the coupling of hydrogen and nitrogen radicals on the analysis of the potential effects of perturbations to odd notrogen in the lower statosphere.

Cohen, R. C.↗
NASA NTRS2005

Nighttime OClO in the Winter Arctic Vortex

We show that a nighttime profile of OClO in the Arctic vortex during the winter of 2000 is overestimated, by nearly a factor of 2, using an isentropic trajectory model constrained by observed profiles of ClOx (ClO + 2 X ClOOCl) and BrO. Calculated abundances of nighttime OClO are shown to be sensitive to the abundance of BrOx (BrO + BrCl), details of the air parcel history during the most recent sunrise/sunset transitions, and the BrCl yield from the reaction BrO + ClO. Many uncertainties are considered, and the discrepancy between measured and modeled nighttime OClO appears to be robust. This discrepancy suggests that production of OClO occurs more slowly than implied by standard photochemistry. If the yield of BrCl from the reaction of BrO + ClO is increased from 7% (JPL 2002 value) to 11% (near the upper limit of the uncertainty), good agreement is found between measured and modeled nighttime OClO. This study highlights the importance of accurate knowledge of BrO + ClO reaction kinetics as well as air parcel trajectories for proper interpretation of nighttime OClO. These factors have a considerably smaller impact on the interpretation of OClO observations obtained during twilight (90(deg) <=SZA <= 92(deg)), when photolytic processes are still active.

chlorine activation↗
NASA NTRS1993

The Upper Atmosphere Research Satellite microwave limb sounder instrument

The microwave limb sounder (MLS) on the Upper Atmosphere Research Satellite (UARS) is the first satellite experiment using limb sounding techniques at microwave frequencies. Primary measurement objectives are stratospheric ClO, O3, H2O, temperature, and pressure. Measurements are of thermal emission: all are performed simultaneously and continuously and are not degraded by ice clouds or volcanic aerosols. The instrument has a 1.6-m mechanically scanning antenna system and contains heterodyne radiometers in spectral bands centred near 63, 183, and 205 GHz. The radiometers operate at ambient temperature and use Schottky-diode mixers with local oscillators derived from phase-locked Gunn oscillators. Frequency tripling by varactor multipliers generates the 183- and 205-GHz local oscillators, and quasi-optical techniques inject these into the mixers. Six 15-channel filter banks spectrally resolve stratospheric thermal emission lines and produce an output spectrum every 2 s. Thermal stability is sufficient for 'total power' measurements which do not require fast chopping. Radiometric calibration, consisting of measurements of cold space and an internal target, is performed every 65-s limb scan. Instrument in-orbit performance has been excellent, and all objectives are being met.

Barath, F. T.↗
NASA NTRS1992

Venus lower thermosphere studies

Studies undertaken in this project have sought to understand lower thermospheric structure and dynamics (less than or equal to 145 km), particularly the processes responsible. This is a region just below the reach of in-situ instruments onboard PVO (Pioneer Venus Orbiter) during the first few diurnal cycles. PVO remote airglow observations (nitric oxide, O2, visible, O 1304A) have been coupled with ground-based observations (CO densities, winds, temperatures, O2 IR nightglow) to address the behavior of lower thermospheric winds and chemistry over 95 to 150 km. This interpretation of PVO and related data is accomplished by using the NCAR Venus thermospheric general circulation model (VTGCM) (Bougher et al., 1988; 1990). This model has been modified over the last two years to improve its ability to calculate O, CO, and O2 densities, temperatures, nightglow, and subsolar-to-antisolar and zonal winds over 95 to 150 km (Bougher and Borucki, 1992). Our VTGCM studies show that: (1) O2 visible and IR nightglow distributions can be used to trace lower thermosphere / upper mesosphere winds over 100-130 km. Typically, weak zonal winds (less than or equal to 25 m/sec) and nightglow maximum patches near 0100 LT prevail. Occasionally, strong zonal winds (30-60 m/sec) and airglow patches peaking near 0300 LT characterize the Venus lower thermosphere. (2) It is clear that the dynamics of the Venus 90-130 km region is highly variable on time scales as short as an hour. This is most likely due to the time variable nature of upward propagating gravity waves, which grow in amplitude and eventually break. The resulting turbulence gives rise to local time variable eddy diffusion and momentum drag, both of which strongly impact global density and nightglow distributions. (3) The oxygen chemistry (O, O2, etc.) over 90-120 km is strongly dependent on HO(x) and CLO(x) tracer species that must be properly included in any coupled chemical dynamical model. (4) The density profiles of light species (O, CO, N, He) are strongly affected by large-scale transport by the winds. Strong eddy diffusion is not a suitable model parameterization for approximating these light species, especially for extrapolation into the region below 140 km where PVO in-situ data is lacking. Instead, the fully coupled chemical dynamical VTGCM model should be used to improve estimates of densities within the VTS3 empirical model (Hedin et al., 1983) below 140 km.

Bougher, Stephen W.↗
NASA NTRS2006

Long-term Evolution of Upper Stratospheric Ozone at Selected Stations of the Network for the Detection of Stratospheric Change (NDSC)

The long-term evolution of upper stratospheric ozone has been recorded by lidars and microwave radiometers within the ground-based Network for the Detection of Stratospheric Change (NDSC), and by the space-borne Solar Backscatter Ultra-Violet instruments (SBUV), Stratospheric Aerosol and Gas Experiment (SAGE), and Halogen Occultation Experiment (HALOE). Climatological mean differences between these instruments are typically smaller than 5% between 25 and 50 km. Ozone anomaly time series from all instruments, averaged from 35 to 45 km altitude, track each other very well and typically agree within 3 to 5%. SBUV seems to have a slight positive drift against the other instruments. The corresponding 1979 to 1999 period from a transient simulation by the fully coupled MAECHAM4-CHEM chemistry climate model reproduces many features of the observed anomalies. However, in the upper stratosphere the model shows too low ozone values and too negative ozone trends, probably due to an underestimation of methane and a consequent overestimation of ClO. The combination of all observational data sets provides a very consistent picture, with a long-term stability of 2% or better. Upper stratospheric ozone shows three main features: (1) a decline by 10 to 15% since 1980, due to chemical destruction by chlorine; (2) two to three year fluctuations by 5 to 10%, due to the Quasi-Biennial Oscillation (QBO); (3) an 11-year oscillation by about 5%, due to the 11-year solar cycle. The 1979 to 1997 ozone trends are larger at the southern mid-latitude station Lauder (45 S), reaching 8%/decade, compared to only about 6%/decade at Table Mountain (35 N), Haute Provence/Bordeaux (approximately equal to 45 N), and Hohenpeissenberg/Bern(approximately equal to 47 N). At Lauder, Hawaii (20 N), Table Mountain, and Haute Provence, ozone residuals after subtraction of QBO- and solar cycle effects have levelled off in recent years, or are even increasing. Assuming a turning point in January 1997, the change of trend is largest at southern mid-latitude Lauder, +11%/decade, compared to +7%/decade at northern mid-latitudes. This points to a beginning recovery of upper stratospheric ozone. However, chlorine levels are still very high and ozone will remain vulnerable. At this point the most northerly mid-latitude station, Hohenpeissenberg/Bern differs from the other stations, and shows much less clear evidence for a beginning recovery, with a change of trend in 1997 by only +3%/decade. In fact, record low upper stratospheric ozone values were observed at Hohenpeissenberg/Bern, and to a lesser degree at Table Mountain and Haute Provence, in the winters 2003/2004 and 2004/2005.

Steinbrecht, W.↗