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At least 127 records · Page 7

Estimates of total organic and inorganic chlorine in the lower stratosphere from in situ and flask measurements during AASE 2

Aircraft sampling has provided extensive in situ and flask measurements of organic chlorine species in the lower stratosphere. The recent Airborne Arctic Stratospheric Expedition 2 (AASE 2) included two independent measurements of organic chlorine species using whole air sample and real-time techniques. From the whole air sample measurements we derive directly the burden of total organic chlorine (CCl(y)) in the lower stratosphere. From the more limited real-time measurements we estimate the CCl(y) burden using mixing ratios and growth rates of the principal CCl(y) species in the troposphere in conjunction with results from a two-dimensional photochemical model. Since stratospheric chlorine is tropospheric in origin and tropospheric mixing ratios are increasing, it is necessary to establish the average age of a stratospheric air parcel to assess its total chlorine (Cl(sub Total)) abundance. Total inorganic chlorine (Cl(y)) in the parcel is then estimated by the simple difference, Cl(y) = Cl(sub Total) - CCl(y). The consistency of the results from these two quite different techniques suggests that we can determine the CCl(y) and Cl(y) in the lower stratosphere with confidence. Such estimates of organic and inorganic chlorine are crucial in evaluating the photochemistry controlling chlorine partitioning and hence ozone loss processes in the lower stratosphere.

Woodbridge, E. L.↗

Determination of the isotopic composition of atmospheric methane and its application in the Antarctic

A procedure for establishing the C-13/C-12 ratio and the C-14 abundance in the atmospheric methane is discussed. The method involves air sample collection, measurement of the methane mixing ratio by gas chromotography followed by quantitative conversion of the methane in the air samples to CO2 and H2O, and analysis of the resulting CO2 for the C-13/C-12 ratio by stable isotope ratio mass spectrometry and measurement of C-14 content by accelerator mass spectrometry. The carbon isotropic composition of methane in air collected at Baring Head, New Zealand, and in air collected on aircraft flights between New Zealand and Antarctica is determined by the method, and no gradient in the composition between Baring Head and the South Pole station is found. As the technique is refined, and more data is gathered, small seasonal and long-term variations in C-13 are expected to be resolved.

Lowe, David C.↗

Establishing Lagrangian Connections between Observations within Air Masses Crossing the Atlantic during the ICARTT Experiment

The International Consortium for Atmospheric Research on Transport and Transformation (ICARTT)-Lagrangian experiment was conceived with an aim to quantify the effects of photochemistry and mixing on the transformation of air masses in the free troposphere away from emissions. To this end attempts were made to intercept and sample air masses several times during their journey across the North Atlantic using four aircraft based in New Hampshire (USA), Faial (Azores) and Creil (France). This article begins by describing forecasts using two Lagrangian models that were used to direct the aircraft into target air masses. A novel technique is then used to identify Lagrangian matches between flight segments. Two independent searches are conducted: for Lagrangian model matches and for pairs of whole air samples with matching hydrocarbon fingerprints. The information is filtered further by searching for matching hydrocarbon samples that are linked by matching trajectories. The quality of these coincident matches is assessed using temperature, humidity and tracer observations. The technique pulls out five clear Lagrangian cases covering a variety of situations and these are examined in detail. The matching trajectories and hydrocarbon fingerprints are shown and the downwind minus upwind differences in tracers are discussed.

Methven, J.↗

NASA Global Atmospheric Sampling Program (GASP) data report for tape VL0006

The NASA Global Atmospheric Sampling Program (GASP) is obtaining measurements of atmospheric trace constituents in the upper troposphere and lower stratosphere using fully automated air sampling systems on board several commercial B-747 aircraft in routine airline service. Atmospheric ozone, and related flight and meteorological data were obtained during 245 flights of a Qantas Airways of Australia B-747 and two Pan American World Airways B-747s from July 1976 through September 1976. In addition, whole air samples, obtained during three flights, were analyzed for trichlorofluoromethane, and filter samples, obtained during four flights, were analyzed for sulfates, nitrates, fluorides, and chlorides. Flight routes and dates, instrumentation, data processing procedures, data tape specifications, and selected analyses are discussed.

Gauntner, D. J.↗

The active titration method for measuring local hydroxyl radical concentration

We are developing a method for measuring ambient OH by monitoring its rate of reaction with a chemical species. Our technique involves the local, instantaneous release of a mixture of saturated cyclic hydrocarbons (titrants) and perfluorocarbons (dispersants). These species must not normally be present in ambient air above the part per trillion concentration. We then track the mixture downwind using a real-time portable ECD tracer instrument. We collect air samples in canisters every few minutes for roughly one hour. We then return to the laboratory and analyze our air samples to determine the ratios of the titrant to dispersant concentrations. The trends in these ratios give us the ambient OH concentration from the relation: dlnR/dt = -k(OH). A successful measurement of OH requires that the trends in these ratios be measureable. We must not perturb ambient OH concentrations. The titrant to dispersant ratio must be spatially invariant. Finally, heterogeneous reactions of our titrant and dispersant species must be negligible relative to the titrant reaction with OH. We have conducted laboratory studies of our ability to measure the titrant to dispersant ratios as a function of concentration down to the few part per trillion concentration. We have subsequently used these results in a gaussian puff model to estimate our expected uncertainty in a field measurement of OH. Our results indicate that under a range of atmospheric conditions we expect to be able to measure OH with a sensitivity of 3x10(exp 5) cm(exp -3). In our most optimistic scenarios, we obtain a sensitivity of 1x10(exp 5) cm(exp -3). These sensitivity values reflect our anticipated ability to measure the ratio trends. However, because we are also using a rate constant to obtain our (OH) from this ratio trend, our accuracy cannot be better than that of the rate constant, which we expect to be about 20 percent.

Sprengnether, Michele↗

N2O analysis in the atmosphere via electron capture-gas chromatography

The potential of commercially available pulse-modulated electron capture detector (ECD)-equipped gas chromatographs for direct measurement of ambient levels of N2O is assessed. Since the sensitivity of ECD to N2O is directly proportional to the detector operating temperature and detector standing current, it is necessary to use a 'hot' ECD (250-350 C). The method is shown to be very precise with a standard error not exceeding 1% for automated analysis of ambient air samples. The technology is available to permit highly accurate routine direct analysis of N2O in the troposphere and stratosphere. Both captured air samples or direct real-time measurement from research vessels or airborne platforms are possible.

Rasmussen, R. A.↗

Atmospheric Sulfur Cycle Effects of Carbonyl Sulfide (OCS)

Carbonyl Sulfide(OCS) is considered to be one of the major sources of sulfur appearing in the stratosphere due to its relative inertness, about I to 10 yearsl. However, the roles of OCS as well as other reduced sulfur compounds such as carbon disulfide (CS2), hydrogen sulfide (H2S), and dimethyl disulfide(CH3)2S2, are not completely understood in the atmosphenc sulfur cycle. Consequently vely little information is available about the effect of sulfur compounds in the stratosphere. The ability of OCS to penetrate into the stratosphere makes it an excellent tracer for study of the role of the sulfi r cycle in stratospheric chemistry. Previously techniques such as gas chromatography and whole air sampling have been used to measure OCS analytically. Each technique had its drawbacks however, with both being quite slow, and whole air sampling being somewhat unreliable. With molecular spectroscopy, however, it has been found in recent years that the tunable diode laser absorption spectrometer (TDL) provides a very rapid and accurate method of measuring OCS and other trace gases

McBee, Joshua↗

Three field tests of a gas filter correlation radiometer

Test flights to remotely measure nonurban carbon monoxide (CO) concentrations by gas filter correlation radiometry are discussed. The inferred CO concentrations obtained through use of the Gas Filter Correlation Radiometer (GFCR) agreed with independent measurements obtained by gas chromatography air sample bottle analysis to within 20 percent. The equipment flown on board the aircraft, the flight test procedure, the gas chromatograph direct air sampling procedure, and the GFCR data analysis procedure are reported.

Campbell, S. A.↗

Mixing ratios of trace gases in the austral polar atmosphere during August and September of 1987

Mixing ratios are presented for a number of long-lived trace gases in the austral polar atmosphere during August and September of 1987. The recent discovery of a 12-year trend of increasing depletion of ozone over the Antarctic Continent in the spring of each year led to numerous theoretical interpretations and several scientific expeditions to the region. The results herein were obtained as part of a major effort involving penetration of the region of ozone depletion by NASA's multi-instrumented aircraft. One of the 14 instruments on the high-altitude ER-2 aircraft collected pressurized air samples between latitudes of 53 degrees and 72 degrees south at pressure altitudes up to 21 km in a series of 12 flights from Punta Arenas, Chile, over the Palmer Peninsula. The sampling system, located in the nose section of ER-2, has an inlet tube in the free airstream, a metal-bellows air pump, and 14 specially treated 1.6 l stainless-steel canisters for containing the pressurized air at 350 kPa. A typical flight profile consisted of a southbound path on the 428 K potential temperature surface, a descent to a pressure altitude of 13.7 km, a climb to the 460 K surface, and return on this surface. Mixing ratios for the trace gases were obtained from gas chromatographic analyses of the pressurized air samples. Of the species measured, the mixing ratios for CH4, CO, N2O, CF2 Cl2, CFCl3, CH3, CCl3, CCl4, and C2F3Cl3 are reported here.

Vedder, James F.↗

DUS II Soil Gas Sampling and Air Injection Test Results

Soil vapor extraction (SVE) and air injection well testing was performed at the Dynamic Underground Stripping (DUS) site located near the M-Area Settling Basin (referred to as DUS II in this report). The objective of this testing was to determine the effectiveness of continued operation of these systems. Steam injection ended on September 19, 2009 and since this time the extraction operations have utilized residual heat that is present in the subsurface. The well testing campaign began on June 5, 2012 and was completed on June 25, 2012. Thirty-two (32) SVE wells were purged for 24 hours or longer using the active soil vapor extraction (ASVE) system at the DUS II site. During each test five or more soil gas samples were collected from each well and analyzed for target volatile organic compounds (VOCs). The DUS II site is divided into four parcels (see Figure 1) and soil gas sample results show the majority of residual VOC contamination remains in Parcel 1 with lesser amounts in the other three parcels. Several VOCs, including tetrachloroethylene (PCE) and trichloroethylene (TCE), were detected. PCE was the major VOC with lesser amounts of TCE. Most soil gas concentrations of PCE ranged from 0 to 60 ppmv with one well (VEW-22A) as high as 200 ppmv. Air sparging (AS) generally involves the injection of air into the aquifer through either vertical or horizontal wells. AS is coupled with SVE systems when contaminant recovery is necessary. While traditional air sparging (AS) is not a primary component of the DUS process, following the cessation of steam injection, eight (8) of the sixty-three (63) steam injection wells were used to inject air. These wells were previously used for hydrous pyrolysis oxidation (HPO) as part of the DUS process. Air sparging is different from the HPO operations in that the air was injected at a higher rate (20 to 50 scfm) versus HPO (1 to 2 scfm). . At the DUS II site the air injection wells were tested to determine if air sparging affected VOC soil gas concentrations during ASVE. Five (5) SVE wells that were located closest to the air injection wells were used as monitoring points during the air sparging tests. The air sparging tests lasted 48 hours. Soil gas sample results indicate that sparging did not affect VOC concentrations in four of the five sparging wells, while results from one test did show an increase in soil gas concentrations.

54 ENVIRONMENTAL SCIENCES↗

Results from the Space Shuttle STS-95 Electronic Nose Experiment

A miniature electronic nose in which the sensing media are insulating polymers loaded with carbon black as a conductive medium has been designed and built at the Jet Propulsion Laboratory. The ENose has a volume of 1700 cc, weighs 1.4 kg including the operating computer, and uses 1.5 W average power (3 W peak power). This ENose was used in a demonstration experiment aboard STS-95 (October, 1998), in which the ENose was operated continuously for six days and recorded the sensors' response to the air in the middeck. The ENose was designed to detect ten common contaminants in space shuttle crew quarters air. The experiment was controlled by collecting air samples daily and analyzing them using standard analytical techniques after the flight. Changes in humidity were detected and quantified, neither the ENose nor the air samples detected any of the contaminants on the target list. The device is microgravity insensitive.

Ryan, M. A.↗

Particle phase-state variability in the North Atlantic free troposphere during summertime is determined by atmospheric transport patterns and sources

Abstract. Free tropospheric aerosol particles have important but poorly constrained climate effects due to transformations of their physicochemical properties during long-range transport. In this study, we investigate the chemical composition and provide an overview of the phase states of individual particles that have undergone long-range transport over the North Atlantic Ocean in June and July 2014, 2015, and 2017 to the Observatory of Mount Pico (OMP) in the Azores. The OMP is an ideal site for studying long-range-transported free tropospheric particles because local emissions have a negligible influence and contributions from the boundary layer are rare. We used the FLEXible PARTicle Lagrangian particle dispersion model (FLEXPART) to determine the origins and transport trajectories of sampled air masses and found that most of them originated from North America and recirculated over the North Atlantic Ocean. The FLEXPART analysis showed that the sampled air masses were highly aged (average plume age >10 d). Size-resolved chemical compositions of individual particles were probed using computer-controlled scanning electron microscopy with an energy-dispersive X-ray spectrometer (CCSEM-EDX) and scanning transmission X-ray microscopy with near-edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS). CCSEM-EDX results showed that the most abundant particle types were carbonaceous (∼ 29.9 % to 82.0 %), sea salt (∼ 0.3 % to 31.6 %), and sea salt with sulfate (∼ 2.4 % to 31.5 %). We used a tilted stage interfaced within an environmental scanning electron microscope (ESEM) to determine the phase states of individual submicron particles. We found that most particles (∼ 47 % to 99 %) were in the liquid state at the time of collection due to inorganic inclusions. Moreover, we also observed substantial fractions of solid and semisolid particles (∼ 0 % to 30 % and ∼ 1 % to 42 %, respectively) during different transport patterns and events, reflecting the particles' phase-state variability for different atmospheric transport events and sources. Combining phase state measurements with FLEXPART CO tracer analysis, we found that wildfire-influenced plumes can result in particles with a wide range of viscosities after long-range transport in the free troposphere. We also used temperature and RH values extracted from the Global Forecast System (GFS) along the FLEXPART-simulated path to predict the phase state of the particles during transport and found that neglecting internal mixing with inorganics would lead to an overestimation of the viscosity of free tropospheric particles. Our findings warrant future investigation aiming at the quantitative assessment of the influence of internal mixing on the phase states of the individual particles. This study also provides insights into the chemical composition and phase state of free tropospheric particles, which can help models to reduce uncertainties about the effects of ambient aerosol particles on climate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gas-chromatographic measurements of atmospheric CF2Cl2, CFCl3 and N2O in Antarctica

Stratospheric ozone is produced photochemically and destroyed by reactions with such minor constituents as O, NOx, HOx, and ClOx. Chlorofluoromethanes (CF2Cl2 and CFCl3) and dinitrogen oxide (NwO) are considered as major sources of the stratospheric ClOx and NOx, respectively. It is well known that CF2Cl2 and CFCl3 are released only by man's activities, and are being accumulated in the troposphere. In order to assess the influence of these compounds on the natural ozone balance these gases have been measured over Japan since 1978. Measurements of Antarctic air samples are also indispensable to understanding the global distributions of these gases, because most CF2Cl2 and CFCl3 have been released in the Northern Hemisphere. Antarctic air samples were obtained by the 23rd, 24th and 25th Japanese Antarctic Research Expeditions, and analyzed by a gas-chromatographic method using an electron capture detector. Three experimental results were obtained: (1) latitudinal distribution of these gases from Tokyo to Syowa Station (69.0 deg S, 39.6 deg E), (2) time trends at Syowa Station, and (3) vertical distributions over Syowa Station. Results are reported.

Hirota, H.↗

Monitoring space shuttle air quality using the Jet Propulsion Laboratory electronic nose

A miniature electronic nose (ENose) has been designed and built at the Jet Propulsion Laboratory (JPL), Pasadena, CA, and was designed to detect, identify, and quantify ten common contaminants and relative humidity changes. The sensing array includes 32 sensing films made from polymer carbon-black composites. Event identification and quantification were done using the Levenberg-Marquart nonlinear least squares method. After successful ground training, this ENose was used in a demonstration experiment aboard STS-95 (October-November, 1998), in which the ENose was operated continuously for six days and recorded the sensors' response to the air in the mid-deck. Air samples were collected daily and analyzed independently after the flight. Changes in shuttle-cabin humidity were detected and quantified by the JPL ENose; neither the ENose nor the air samples detected any of the contaminants on the target list. The device is microgravity insensitive.

manned↗

Atmospheric CO Concentrations from the CSIRO GASLAB Flask Sampling Network

Individual measurements have been obtained from flask air samples returned to the CSIRO GASLAB. Typical sample storage times range from days to weeks for some sites (e.g. Cape Grim) to as much as 1 year for Macquarie Island and the Antarctic sites. Experiments carried out to test for changes in sample CO mixing ratio during storage have shown significant drifts in some flask types over test periods of several months to years (Cooper et al., 1999). Corrections derived from the test results are applied to network data according to flask type. (Data from the S160 flasks have been rejected due to large and variable drift.)An annual cycle of CO is evident, largely due to an increase in its destruction by the OH radical during the summer months. Additional influences include spatial and seasonal differences in source strength associated with varying trajectories of arriving air at different times of the year. Annual average CO mixing ratios at Alert in 2001 had decreased by about 13 percent of their 1993 value. A string of abnormally high monthly mixing ratios during the winter of 1998-1999, coupled with higher than normal mixing ratios during the previous summer, led to an anomalously high annual average for 1998. Elevated CO mixing ratios were observed on a global scale during 1998 (see Langenfelds et al., 2002).

54 ENVIRONMENTAL SCIENCES↗

Background Concentrations of Argon-39 in Shallow Soil Gas

While radioisotopes of noble gases are known to be indicators of underground nuclear explosions (UNE), McIntyre et al. (2017) was the first to report the presence of 39Ar in shallow soil gas in association with a decades old UNE. While this finding hinted at the potential application of 39Ar to be used as an indicator of an UNE, doing so would also require an understanding of the natural concentrations of 39Ar present in soil gas. Without knowing the expected range and variability of naturally occurring concentrations of 39Ar, it is difficult to determine what measured concentrations would be indicative of an elevated concentration. This paper presents results from 16 soil gas samples and three atmospheric air samples collected from various locations across the western United States. Shallow soil gas samples were collected into self-contained underwater breathing apparatus (SCUBA) tanks using a custom-built soil gas sampling system and then processed and analyzed for 39Ar. The measured concentrations of 39Ar varied from atmospheric air concentrations to about 3.5 times atmospheric air concentrations. The variation in concentration was primarily attributed to the latitude the sample was collected at, which was consistent with previous work (Johnson et al. 2015). The results presented here represent the first measurements of natural background 39Ar concentrations in shallow soil gas. This data will be necessary if 39Ar is to be used as an indicator of UNE.

Fritz, Brad G.↗

Aircraft instrumentation system for the remote sensing of carbon monoxide

A light twin-engine aircraft has been instrumented with a carbon monoxide remote gas sensor system and test flown over the Southern Lake Michigan basin during August, 1976. The remote sensor is based on the gas filter correlation technique. The radiance levels from the sensor along with the data on the surface temperature, air temperature, dewpoint, and altitude were digitized and recorded on seven-track magnetic tape. Air samples were collected at various altitudes over selected sites for later analysis of carbon monoxide concentration and comparison with the inferred concentration from the remote sensor. The values of carbon monoxide obtained from the air samples and the values inferred from the remote sensor for data collected over water are in good agreement.

Beck, S. M.↗