Contrast Between 1992 and 1997 High Latitude Spring Haloe Observations of Lower Stratospheric HCl

HCl measurements from HALOE in the northern hemisphere during mid-May 1997 revealed vortex fragments in which the chlorine reservoir partitioning was strongly pushed toward HCl (approx. 90% HCl, approx. 10% ClONO2), similar to partitioning previously observed in the Antarctic vortex region. In contrast, observations of ClONO2 and HCl in the northern polar spring, 1992, and in other years, show these species established the balance typical for gas phase photochemical reactions in this region (approx. 60% HCl, approx. 40% ClONO2). Annually, chlorine reservoirs in the winter lower stratosphere polar vortex are converted to chlorine radicals via heterogeneous reactions on particle surfaces at very cold temperatures (less than about 200 K). As temperatures warm in spring, the heterogeneous processes become insignificant compared with gas phase reactions, and the chlorine reservoirs are reformed. Measurements through the northern winter/spring in 1992 show rapid formation of ClONO2, followed by steady loss of ClONO2 and increasing HCl. Although ClONO2 measurements are not available for 1997, the HCl increase in 1997 is observed to be much more rapid and the eventual HCl mixing ratio is about 50% greater than that of 1992. The observations are examined through comparison with the Goddard three-dimensional chemistry and transport model. This model utilizes winds and temperatures from the Goddard Earth Observing System Data Assimilation System and a complete integration scheme for stratospheric photochemistry. Analysis of the evolution of HCl and ClONO2 shows that the observed difference in the overall rate of HCl formation is explained by the sensitivity of the gas-phase chemistry to the ozone mixing ratio and the temperature. The results show that the model accurately simulates HCl and ClONO2 evolution during these two winters. Model validity is further supported by comparisons with O3 and reactive nitrogen species NO and NO2. This analysis provides a sensitive test of the lower stratospheric chlorine photochemistry, particularly because the analysis considers constituent evolution at a time when the HCl and ClONO2 are far from a photochemical stationary state

The development of new, low-cost perfluoroalkylether fluids with excellent low and high-temperature properties

A series of perfluoroalkylether (PFAE) fluids were synthesized by direct fluorination. Viscosity-temperature properties, oxidation stabilities, oxidation-corrosion properties, and lubricity were determined. The fluids were tested in the presence of common elastomers to check for compatibility. The bulk modulus of each was measured to determine if any could be used as nonflammable aircraft hydraulic fluid. It was determined that as the carbon to oxygen ratio decreases, the viscometric properties improve, the fluids may become poor lubricants, the bulk modulus increases, the surface tension increases, and the fluid density increases. The presence of difluoromethylene oxide units in the polymer does not seriously lower the oxidation and oxidation-corrosion stabilities as long as the difluoromethylene oxide units are separated by other units

The preparation of new perfluoroether fluids exhibiting excellent thermal-oxidative stabilities

A series of low molecular weight perfluoroalkylethers (PFAE) were synthesized by direct fluorination. Viscosity-temperature properties and oxidation stabilities were determined. Viscosity-temperature correlations indicated that increases in branching and increases in the size of the branching substituent caused a deterioration in viscometric properties (i.e., an increase in ASTM slope). In addition, increasing the ratio of carbon to oxygen in these compounds also increased the ASTM slope. Preliminary oxidation stability tests indicated that highly branched PFAE fluids. (i.e., those containing quaternary carbons) may be less stable than either those containing a single trifluoromethyl pendant group or those containing no branching at all

Fall vortex ozone as a predictor of springtime total ozone at high northern latitudes

Understanding the impact of atmospheric dynamical variability on observed changes in stratospheric O₃ is a key to understanding how O₃ will change with future climate dynamics and trace gas abundances. In this paper we examine the linkage between interannual variability in total column O₃ at northern high latitudes in March and lower-to-mid stratospheric vortex O₃ in the prior November. We find that these two quantities are significantly correlated in the years available from TOMS, SBUV, and POAM data (1978-2004). Additionally, we find that the increase in March O₃ variability from the 1980s to years post-1990 is also seen in the November vortex O₃, i.e., interannual variability in both quantities is much larger in the later years. The cause of this correlation is not clear, however. Interannual variations in March total O₃ are known to correspond closely with variations in winter stratospheric wave driving consistent with the effects of varying residual circulation, temperature, and chemical loss. Variation in November vortex O₃ may also depend on dynamical wave activity, but the dynamics in fall are less variable than in winter and spring. We do not find significant correlations of dynamic indicators for November such as temperature, heat flux, or polar average total O₃ with the November vortex O₃, nor with dynamical indicators later in winter and spring that might lead to a connection to March. We discuss several potential hypotheses for the observed correlation but do not find strong evidence for any considered mechanism. We present the observations as a phenomenon whose understanding may improve our ability to predict the dependence of O₃ on changing dynamics and chemistry

Background error covariance estimation for atmospheric CO 2 data assimilation

In any data assimilation framework, the background error covariance statistics play the critical role of filtering the observed information and determining the quality of the analysis. For atmospheric CO 2 data assimilation, however, the background errors cannot be prescribed via traditional forecast or ensemble‐based techniques as these fail to account for the uncertainties in the carbon emissions and uptake, or for the errors associated with the CO 2 transport model. We propose an approach where the differences between two modeled CO 2 concentration fields, based on different but plausible CO 2 flux distributions and atmospheric transport models, are used as a proxy for the statistics of the background errors. The resulting error statistics: (1) vary regionally and seasonally to better capture the uncertainty in the background CO 2 field, and (2) have a positive impact on the analysis estimates by allowing observations to adjust predictions over large areas. A state‐of‐the‐art four‐dimensional variational (4D‐VAR) system developed at the European Centre for Medium‐Range Weather Forecasts (ECMWF) is used to illustrate the impact of the proposed approach for characterizing background error statistics on atmospheric CO 2 concentration estimates. Observations from the Greenhouse gases Observing SATellite “IBUKI” (GOSAT) are assimilated into the ECMWF 4D‐VAR system along with meteorological variables, using both the new error statistics and those based on a traditional forecast‐based technique. Evaluation of the four‐dimensional CO 2 fields against independent CO 2 observations confirms that the performance of the data assimilation system improves substantially in the summer, when significant variability and uncertainty in the fluxes are present. Key Points Difference in modeled CO2 fields is used to define background errors in CO2‐DA Both atmospheric transport & flux pattern differences impact background errors Evaluation using independent data shows positive impact on analysis estimatesPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/100305/1/jgrd50654.pd

Using CO 2 spatial variability to quantify representation errors of satellite CO 2 retrievals

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95625/1/grl24793.pd

Physical and chemical properties of some new perfluoropolyalkylether lubricants prepared by direct fluorination

A series of perfluoropolyalkylether (PFPAE) fluids was synthesized by direct fluorination. Viscosity-temperature properties, oxidation stabilities, oxidation-corrosion properties, bulk modulus, lubricity, surface tension and density were measured. It was shown that as the carbon to oxygen ratio in the polymer repeating unit decreases, the viscometric properties improve, the fluids may become poorer boundary lubricants, the bulk modulus increases, the surface tension increases and the fluid density increases. The presence of difluoromethylene oxide units in the polymer does not significantly lower the oxidation and oxidation-corrosion stabilities as long as the difluoromethylene oxide units are separated by other units

Development of Optical Parametric Amplifier for Lidar Measurements of Trace Gases on Earth and Mars

Trace gases in planetary atmospheres offer important clues as to the origins of the planet's hydrology, geology. atmosphere. and potential for biology. Wc report on the development effort of a nanosecond-pulsed optical parametric amplifier (OPA) for remote trace gas measurements for Mars and Earth. The OP A output light is single frequency with high spectral purity and is widely tunable both at 1600 nm and 3300 nm with an optical-optical conversion efficiency of approximately 40%. We demonstrated open-path atmospheric measurements ofCH4 (3291 nm and 1651 nm). CO2 (1573 nm), H20 (1652 nm) with this laser source

When Will the Antarctic Ozone Hole Recover?

The Antarctic ozone hole demonstrates large-scale, man-made affects on our atmosphere. Surface observations now show that human produced ozone depleting substances (ODSs) are declining. The ozone hole should soon start to diminish because of this decline. Herein we demonstrate an ozone hole parametric model. This model is based upon: 1) a new algorithm for estimating C1 and Br levels over Antarctica and 2) late-spring Antarctic stratospheric temperatures. This parametric model explains 95% of the ozone hole area s variance. We use future ODS levels to predict ozone hole recovery. Full recovery to 1980 levels will occur in approximately 2068. The ozone hole area will very slowly decline over the next 2 decades. Detection of a statistically significant decrease of area will not occur until approximately 2024. We further show that nominal Antarctic stratospheric greenhouse gas forced temperature change should have a small impact on the ozone hole

The Ability of GeoCarb to Constrain the Interannual Variability of Carbon Gases over the Amazon

We perform a number of idealized assimilation experiments with the GEOS constituent data assimilation system to test the ability of GeoCarb retrievals of CO, CO2, and CH4 to constrain the interannual variability of these gases over the Amazon. Retrievals for instruments on other satellites which observe in similar channels (e.g. MOPITT, GOSAT, and OCO-2) are limited due to persistent cloud coverage. Given its ability to sample the same location multiple times in one day, the expectation is that GeoCarb retrievals will return more soundings than those from previous missions. The goal of the assimilation experiments is to understand which scanning strategies lead to the best sounding densities and thus have the best chance of constraining interannual variability in the carbon species. The experiments each begin by picking a given year at random from a nature run (i.e., a model simulation meant to represent the truth). The model fields are sampled according to a given strategy and then screened to account for cloud coverage. Next, we pick another year at random and assimilate the synthetic GeoCarb samples into the GEOS model for that year. The output of the assimilation, 6-hourly, 3D fields of each constituent, is then directly comparable to the nature run. This comparison allows us to evaluate the ability of GeoCarb measurements to constrain the interannual variability of each gas