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: Results from an airborne intercomparison of techniques to measure tropospheric levels of sulfur trace gases are presented. The intercomparison was part of the NASA Global Tropospheric Experiment (GTE) and was conducted during the summer of 1989. The intercomparisons were conducted on the Wallops Electra aircraft during flights from Wallops Island, Virginia, and Natal, Brazil. Sulfur measurements intercompared included sulfur dioxide (SO2), dimethylsulfide (DMS), hydrogen sulfide (H2S), carbon disulfide (CS2), and carbonyl sulfide (OCS). Measurement techniques ranged from filter collection systems with post-flight analyses to mass spectrometer and gas chromatograph systems employing various methods for measuring and identifying the sulfur gases during flight. Sampling schedules for the techniques ranged from integrated collections over periods as long as 50 minutes to one- to three-minute samples every ten or fifteen minutes. Several of the techniques provided measurements of more than one sulfur gas. Instruments employing different detection principles were involved in each of the sulfur intercomparisons. Also included in the intercomparison measurement scenario were a host of supporting measurements (i.e., ozone, nitrogen oxides, carbon monoxide, total sulfur, aerosols, etc.) for purposes of: (1) interpreting results (i.e., correlation of any noted instrument disagreement with the chemical composition of the measurement environment); and (2) providing supporting chemical data to meet CITE-3 science objectives of studying ozone/sulfur photochemistry, diurnal cycles, etc. The results of the intercomparison study are briefly discussed.

Description: The flash photolysis-resonance fluorescence system described by Davis et al. (1974) is used to measure the rate constants for the reactions of chlorine nitrate (ClONO2) with stratospheric O(3-P) and OH. Both reactions are examined in a pyrex cell with an internal volume of about 150 cu cm, where the reaction mixture was maintained at 245 K by circulating methanol from a thermostated circulation bath through the outer jacket of the reaction cell. The relative chemical degradation rates as a function of altitude for both reactions are tabulated, which shows that the chemical degradation pathways contribute less than 10% to the total rate of ClONO2 destruction at altitudes less than 30 km. Since the concentration of ClONO2 is calculated to be near its maximum around 25 km and drops off very significantly at higher altitudes, it is concluded that the photochemical decomposition of ClONO2 in the stratosphere is by far the most important degradation path for this molecule.

Description: The White's Point ocean outfall is the method of disposal for approximately 374 million gallons of treated wastewater per day from Los Angeles County. The photosynthetic characteristics and particle distributions have well-defined properties that can be exploited to yield information on transport of the plume, mixing dynamics, and resuspension of bottom sediments during periods of bottom current velocity in excess of ca. 0.1 m/s. This plume of particles serves as a conservative tracer, which was studied using a number of sampling platforms and strategies, including underway sawtooth, or 'tow-yo' sampling, moored arrays of instruments, stationary profiling, and now for the first time with remotely-sensed multispectral color imagery. Research in this area previously focused on examination of the plume as it relates to the local current field and transport of particles, and on the resuspension of bottom sediments during periods of increased currents. In addition, Wu et al elucidated techniques for separating the particle signal into photosynthetic and nonphotosynthetic components, based on the beam attenuation to chlorophyll fluorescence ratio. High-frequency time series measurements of the current field and bio-optical characteristics at a site close to the waste diffusers were also collected. These are being analyzed for the spectral characteristics of the longer-timescale variability, in order to predict particle transport through simple meteorological measurements. With the advent of high spectral and spatial resolution imaging spectrometers such as AVIRIS, it is now possible to construct causal relationships between particle distributions and signature of the upwelled radiance from the surface. The availability of a constant and well-characterized source of material lends itself well to models which predict upwelled radiance from the surface. The availability of a constant and well-characterized source of material lends itself well to models which predict upwelled light as a function of particle distributions, photosynthetic pigments, colored dissolved organic material, and detrital and degradation products of photosynthesis. In addition, the spatial coverage provided by the tow-yo sampling device, combined with the profile measurements of the light field, should facilitate the best inverse modeling attempts possible thus far.

Description: Direct measurements of the OH radical in the vicinity of an isolated power plant plume are reported. These measurements were used to estimate the conversion time of SO2 to H2SO4-sulfate aerosol via the initiating step OH + SO2 + M yields HSO3. Using the near-high-noon measured value of OH (9.5 million per cu cm), resulted in a 1/e conversion time of 1.4 days. The latter lifetime would correspond to a conversion rate of about 2%/hr. When the lifetime calculation was modified to take into consideration the OH diurnal cycle, the 1/e conversion time for SO2 was found to be 4.4 days, giving an apparent overall rate of conversion of about 0.7%/hr. Similar calculations carried out for the conversion of NO2 to NHO3 resulted in 1/e lifetimes for NO2 of 2-3 h for midday time periods.

Description: Two separate techniques were used to obtain important basic data for the adsorption of seven liquid and eight gaseous trace contaminants. A columetric system used in previous HSC studies was modified to determine the HSC capacity of all the contaminants. A second study of six of the liquids was performed in a gas chromatorgraph. The results of these two studies are reported in two parts. First, a brief summary of the chromatographic results are given. Second, a thesis is given which reports in some detail the results of the volumetric studies. Comparison of the data that are common to both studies are also included.