ALBERT

Description: This paper reports results from NASA's Chemical Instrumentation and Test Evaluation (CITE 3) during which airborne measurements of dimethyl sulfide (DMS) from six instruments were intercompared. Represented by the six instruments are three fundamentally different detection principles (flame photometric, mass spectrometric, and electron capture after fluorination); three collection/preconcentration methods (cryogenic, gold wool absorption, and polymer absorbent); and three types of oxidant scrubbers (solid phase alkaline, aqueous reactor, and cotton). The measurements were made over the Atlantic Ocean in August/September 1989 during flights from NASA's Wallops Flight Center, Virginia, and Natal, Brazil. The majority of the intercomparisons are at DMS mixing ratios less than 50 pptv. Results show that instrument agreement is of the order of a few pptv for mixing ratios less than 50 pptv and to within about 15% above 50 pptv. Statistically significant (95% confidence) measurement biases were noted among some of the techniques. However, in all cases, any bias is small and within the accuracy of the measurements and prepared DMS standards. Thus, we conclude that the techniques intercompared during CITE 3 provide equally valid measurements of DMS in the range of a few pptv to 100 pptv (upper range of the intercomparisons).

Description: This paper reports results of NASA's Chemical Instrumentation and Test Evaluation (CITE 3) during which airborne measurements for carbonyl sulfide (COS), hydrogen sulfide (H2S), and carbon disulfide (CS2) were intercompared. Instrumentation included a gas chromatograph using flame photometric detection (COS, H2S, and CS2), a gas chromatograph using mass spectrometric detection (COS) and CS2), a gas chromatograph using fluorination and subsequent SF6 detection via electron capture (COS and CS2), and the Natusch technique (H2S). The measurements were made over the Atlantic Ocean east of North and South America during flights from NASA's Wallops Flight Center, Virginia, and Natal, Brazil, in August/September 1989. Most of the intercomparisons for H2S and CS2 were at mixing ratios less than 25 pptv and less than 10 pptv, respectively, with a maximum mixing ratio of about 100 pptv and 50 pptv, respectively. Carbonyl sulfide intercomparisons were at mixing ratios between 400 and 600 pptv. Measurements were intercompared from data bases constructed from time periods of simultaneous or overlapping measurements. Agreement among the COS techniques averaged about 5%, and individual measurements were generally within 10%. For H2S and at mixing ratio greater than 25 pptv, the instruments agreed on average to about 15%. At mixing ratios less than 25 pptv the agreement was about 5 pptv. For CS2 (mixing ratios less than 50 pptv), two techniques agreed on average to about 4 pptv, and the third exhibited a bias (relative to the other two) that varied in the range of 3-7 pptv. CS2 mixing ratios over the ocean east of Natal as measured by the gas chromatograph-mass spectrometer technique were only a few pptv and were below the detection limits of the other two techniques. The CITE 3 data are used to estimate the current uncertainty associated with aircraft measurements of COS, H2S, and CS2 in the remote troposphere.

Description: As part of the NASA Tropospheric Chemistry Program, a series of field intercomparisons have been conducted to evaluate the state-of-the art for measuring key tropospheric species. One of the objectives of the third intercomparison campaign in this series, Chemical Instrumentation Test and Evaluation 3 (CITE 3), was to evaluate instrumentation for making reliable tropospheric aircraft measurements of sulfur dioxide, dimethyl sulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide. This paper reports the results of the intercomparisons of five sulfur dioxide measurement methods ranging from filter techniques, in which samples collected in flight are returned to the laboratory for analyses (chemiluminescent or ion chromatographic), to near real-time, in-flight measurements via gas chromatographic, mass spectrometric, and chemiluminescent techniques. All techniques showed some tendency to track sizeable changes in ambient SO2 such as those associated with altitude changes. For SO2 mixing ratios in the range of 200 pptv to a few ppbv, agreement among the techniques varies from about 30% to several orders of magnitude, depending upon the pair of measurements intercompared. For SO2 mixing ratios less than 200 pptv, measurements from the techniques are uncorrelated. In general, observed differences in the measurement of standards do not account for the flight results. The CITE 3 results do not unambiguously identify one or more of the measurement techniques as providing valid or invalid SO2 measurements, but identify the range of 'potential' uncertainty in SO2 measurements reported by currently available instrumentation and as measured under realistic aircraft environments.

Description: We predict the present-day rates of change of the lengths of 19 North American baselines due to the glacial isostatic adjustment process. Contrary to previously published research, we find that the three dimensional motion of each of the sites defining a baseline, rather than only the radial motions of these sites, needs to be considered to obtain an accurate estimate of the rate of change of the baseline length. Predictions are generated using a suite of Earth models and late Pleistocene ice histories, these include specific combinations of the two which have been proposed in the literature as satisfying a variety of rebound related geophysical observations from the North American region. A number of these published models are shown to predict rates which differ significantly from the VLBI observations.

Description: Magnetite-wuestite spherules collected from deep-sea sediments are thought to have originally been Fe-Ni metal particles at the top of the atmosphere that were oxidized and melted during entry into the earth's atmosphere. Some likely sources for the metal particles are Fe-Ni interplanetary dust particles (IDP's) and metal or sulfide from stony IDP's that separated after melting. Davis et al. reported that four of these spherules are enriched in the heavy isotopes of iron, with enrichments of 8-23%/amu. We have developed a technique for analysis of both iron and nickel isotopes on the same ion microprobe spot and have applied this technique to a number of deep-sea spherules in order to better understand the processes leading to isotopic mass fractionation. Eight spherules show iron and nickel isotopic mass fractionation, with iron and nickel enriched in the heavy isotopes by 10-19%/amu and 4-32%/amu, respectively. If the mass fractionations are due to Rayleigh fractionation during evaporation, these spherules lost 76-94% of their original mass. We have analyzed the four magnetite-wuestite spherules for which iron isotopic data were reported by Davis et al. as well as four new spherules.

Description: The Chemical Instrumentation Test and Evaluation 3 (CITE 3) NO-NO2 database has provided a unique opportunity to examine important aspects of tropospheric photochemistry as related to the rapid cycling between NO and NO2. Our results suggest that when quantitative testing of this photochemical system is based on airborne field data, extra precautions may need to be taken in the analysis. This was particularly true in the CITE 3 data analysis where different regional environments produced quite different results when evaluating the photochemical test ratio (NO2)(sub expt)/(NO2)(sub calc), designated here as R(sub E)/R(sub C). The quantity (NO2)(sub Calc) was evaluated using the following photostationary state expression: (NO2)(sub Calc) = k(sub 1)(O3) + k(sub 4)(HO2) + k(sub 5)(CH3O2) + k(sub 6)(RO2))(NO)(sub Expt)/J(sub 2). The four most prominent regional environmental data sets identified in this analysis were those labeled here as free-tropospheric northern hemisphere (FTNH), free-tropospheric tropical northern hemisphere (FTTNH), free-tropospheric southern hemisphere (FTSH), and tropical-marine boundary layer (plume) (TMBL(P)). The respective R(sub E)/R(sub C) mean and median values for these four data subsets were 1.74, 1.69; 3.00, 2.79; 1.01, 0.97; and 0.99, 0.94. Of the four data subsets listed, the two that were statistically the most robust were FTNH and FTSH; for these the respective R(sub E)/R(sub C) mean and standard deviation of the mean values were 1.74 +/- 0.07 and 1.01 +/- 0.04. The FTSH observations were in good agreement with theory, whereas those from the FTNH data set were in significant disagreement. An examination of the critical photochemical parameters O3, UV(zenith), NO, NO2, and non-methane hydrocarbons (NMHCs) for these two databases indicated that the most likely source of the R(sub E)/R(sub C) bias in the FTNH results was the presence of a systematic error in the observational data rather than a shortening in our understanding of fundamental photochemical processes. Although neither a chemical nor meteorological analyses of these data identified this error with complete certainty, they did point to the three most likely possibilities: (1) an NO2 interference from a yet unidentified NO(y) species: (2) the presence of unmeasured hydrocarbons, the integrated reactivity of which would be equivalent to approximately 2.7 parts per billion by volume (ppbv) of toluene; or (3) some combination of points (1) and (2). Details concerning hypotheses (1) and (2) as well as possible ways to minimize these problems in future airborne missions are discussed.

Description: We predict the present-day rates of change of the lengths of 19 North American baselines due to the glacial isostatic adjustment process. Contrary to previously published research, we find that the three-dimensional motion of each of the sites defining a baseline, rather than only the radial motions of these sites, needs to be considered to obtain an accurate estimate of the rate of change of the baseline length. Predictions are generated using a suite of Earth models and late Pleistocene ice histories; these include specific combinations of the two which have been proposed in the literature as satisfying a variety of rebound related geophysical observations from the North American region. A number of these published models are shown to predict rates which differ significantly from the Very Long Base Interferometry (VLBI) observations.

Description: This project involves obtaining Global Positioning System (GPS) measurements in Scandinavia, and using the measurements to estimate the viscosity profile of the Earth's mantle and to correct tide-gage measurements for the rebound effect. Several aspects of this project are reported.

Description: This project involves obtaining GPS measurements in Scandinavia, and using the measurements to estimate the viscosity profile of the Earth's mantle and to correct tide-gauge measurements for the rebound effect. Below, we report on several aspects of this project. The DSGS was occupied in August 1993. This campaign also inaugurated SWEPOS, the Swedish permanent GPS network. Initial results are presented in Johansson et al., a copy of which is contained in Appendix A. An important technical advance we intend for this project is to use the full three dimensional site velocity information for inferring geophysical parameters. To this end, we have investigated using VLBI determined baseline length rates in North America to constraining proposed combinations of ice history and earth rheology, and presented this work in Mitrovica et al., a copy of which is contained in Appendix B.

Description: This paper reports the overall experimental design and gives a brief overview of results from the third airborne Chemical Instrumentation Test and Evaluation (CITE 3) mission conducted as part of the National Aeronautics and Space Administration's Global Tropospheric Experiment. The primary objective of CITE 3 was to evaluate the capability of instrumentation for airborne measurements of ambient concentrations of SO2, H2S, CS, dimethyl sulfide, and carbonyl sulfide. Ancillary measurements augmented the intercomparison data in order to address the secondary objective of CITE 3 which was to address specific issues related to the budget and photochemistry of tropospheric sulfur species. The CITE 3 mission was conducted on NASA's Wallops Flight Center Electra aircraft and included a ground-based intercomparison of sulfur standards and intercomparison/sulfur science flights conducted from the NASA Wallops Flight Facility, Wallops Island, Virginia, followed by flights from Natal, Brazil. Including the transit flights, CITE 3 included 16 flights encompassing approximately 96 flight hours.