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At least 271 records · Page 15

Evaluation of a Gas Chromatograph-Differential Mobility Spectrometer for Potential Water Monitoring on the International Space Station

Environmental monitoring for manned spaceflight has long depended on archival sampling, which was sufficient for short missions. However, the longer mission durations aboard the International Space Station (ISS) have shown that enhanced, real-time monitoring capabilities are necessary in order to protect both the crewmembers and the spacecraft systems. Over the past several years, a number of real-time environmental monitors have been deployed on the ISS. Currently, volatile organic compounds (VOCs) in the station air are monitored by the Air Quality Monitor (AQM), a small, lightweight gas chromatograph-differential mobility spectrometer. For water monitoring, real-time monitors are used for total organic carbon (TOC) and biocide analysis. No information on the actual makeup of the TOC is provided presently, however. An improvement to the current state of environmental monitoring could be realized by modifying a single instrument to analyze both air and water. As the AQM currently provides quantitative, compound-specific information for VOCs in air samples, this instrument provides a logical starting point to evaluate the feasibility of this approach. The major hurdle for this effort lies in the liberation of the target analytes from the water matrix. In this presentation, we will discuss our recent studies, in which an electro-thermal vaporization unit has been interfaced with the AQM to analyze target VOCs at the concentrations at which they are routinely detected in archival water samples from the ISS. We will compare the results of these studies with those obtained from the instrumentation routinely used to analyze archival water samples.

Wallace, William T.↗

Variation in Global Chemical Composition of PM2.5: Emerging Results from SPARTAN

The Surface PARTiculate mAtter Network (SPARTAN) is a long-term project that includes characterization of chemical and physical attributes of aerosols from filter samples collected worldwide. This paper discusses the ongoing efforts of SPARTAN to define and quantify major ions and trace metals found in fine particulate matter (PM (sub 2.5). Our methods infer the spatial and temporal variability of PM (sub 2.5) in a cost-effective manner. Gravimetrically weighed filters represent multi-day averages of PM (sub 2.5), with a collocated nephelometer sampling air continuously. SPARTAN instruments are paired with AErosol RObotic NETwork (AERONET) sun photometers to better understand the relationship between ground-level PM (sub 2.5) and columnar aerosol optical depth (AOD). We have examined the chemical composition of PM (sub 2.5) at 12 globally dispersed, densely populated urban locations and a site at Mammoth Cave (US) National Park used as a background comparison. So far, each SPARTAN location has been active between the years 2013 and 2016 over periods of 2-26 months, with an average period of 12 months per site. These sites have collectively gathered over 10 years of quality aerosol data. The major PM (sub 2.5) constituents across all sites (relative contribution plus or minus Standard Deviation) are ammoniated sulfate (20 percent plus or minus 11 percent), crustal material (13.4 percent plus or minus 9.9 percent), equivalent black carbon (11.9 percent plus or minus 8.4 percent), ammonium nitrate (4.7 percent plus or minus 3.0 percent), sea salt (2.3 percent plus or minus 1.6 percent), trace element oxides (1.0 percent plus or minus 1.1 percent), water (7.2 percent plus or minus 3.3 percent) at 35 percent relative humidity, and residual matter (40 percent plus or minus 24 percent). Analysis of filter samples reveals that several PM (sub 2.5) chemical components varied by more than an order of magnitude between sites. Ammoniated sulfate ranges from 1.1 microns per cubic meter (Buenos Aires, Argentina) to 17 microns per cubic meter (Kanpur, India in the dry season). Ammonium nitrate ranged from 0.2 microns per cubic meter (Mammoth Cave, in summer) to 6.8 microns per cubic meter (Kanpur, dry season). Equivalent black carbon ranged from 0.7 microns per cubic meter (Mammoth Cave) to over 8 microns per cubic meter (Dhaka, Bangladesh and Kanpur, India). Comparison of SPARTAN vs. coincident measurements from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network at Mammoth Cave yielded a high degree of consistency for daily PM (sub 2.5) (r squared equals 0.76, slope equals 1.12), daily sulfate (r squared equals 0.86, slope equals 1.03), and mean fractions of all major PM (sub 2.5) components (within 6 percent). Major ions generally agree well with previous studies at the same urban locations (e.g. sulfate fractions agree within 4 percent for 8 out of 11 collocation comparisons). Enhanced anthropogenic dust fractions in large urban areas (e.g. Singapore, Kanpur, Hanoi, and Dhaka) are apparent from high Zn to Al ratios. The expected water contribution to aerosols is calculated via the hygroscopicity parameter kappa (sub v (volume)) for each filter. Mean aggregate values ranged from 0.15 (Ilorin) to 0.28 (Rehovot). The all-site parameter mean is 0.20 plus or minus 0.04. Chemical composition and water retention in each filter measurement allows inference of hourly PM (sub 2.5) at 35 percent relative humidity by merging with nephelometer measurements. These hourly PM (sub 2.5) estimates compare favourably with a beta attenuation monitor (MetOne) at the nearby US embassy in Beijing, with a coefficient of variation r squared equals 0.67 (number equals 3167), compared to r squared equals 0.62 when v (volume) was not considered. SPARTAN continues to provide an open-access database of PM (sub 2.5) compositional filter information and hourly mass collected from a global federation of instruments.

Snider, Graydon↗

Measurements of I/SVOCs in biomass-burning smoke using solid-phase extraction disks and two-dimensional gas chromatography

Biomass-burning organic-aerosol (OA) emissions are known to exhibit semi-volatile behavior that impacts OA loading during plume transport. Because such semi-volatile behavior depends in part on OA composition, improved speciation of intermediate and semi-volatile organic compounds (I/SVOCs) emitted during fires is needed to assess the competing effects of primary OA volatilization and secondary OA production. In this study, 18 laboratory fires were sampled in which a range of fuel types were burned. Emitted I/SVOCs were collected onto Teflon filters and solid-phase extraction (SPE) disks to qualitatively characterize particulate and gaseous I/SVOCs, respectively. Derivatized filter extracts were analyzed using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC × GC-TOFMS). Quality control tests were performed using biomass-burning relevant standards and demonstrate the utility of SPEdisks for untargeted analysis of air samples. The observed chromatographic profiles of I/SVOCs in coniferous fuel-derived smoke samples were well correlated with each other, but poorly correlated with other fuel types(e.g., herbaceous and chaparral fuels). Emissions of benzenediol isomers were also shown to be fuel dependent. The combined Teflon and SPE filter data captured differences in gas-particle partitioning of the benzene diolisomers, with hydroquinone having a significantly higher particle-phase fraction than catechol due to its lower volatility. Additionally, the speciated volatility distribution of I/SVOCs in smoke from a rotten-log fire was estimated to evaluate the composition of potentially volatilized primary OA, which was entirely attributed to oxygenated (or other heteroatomic) compounds. The isomer-dependent partitioning and the speciated volatility distributions both suggest the need for better understanding of gas-phase and heterogenous reaction pathways of biomass-burning-derived I/SVOCs in order to represent the atmospheric chemistry of smoke in models.

09 BIOMASS FUELS↗

An operational ASDAR system

The story of the Aircraft to Satellite Data Relay (ASDAR) program began when airline meteorologists realized that B-747's and other commercial jets provided cockpit displays of digital values for outside air temperature and winds. Later, when a few B-747's were used to carry portable air quality monitoring equipment for the Global Air Sampling Program (GASP), scientists at NASA-Lewis explored ways in which these digital values could be used to label data collected during the GASP flights. Digital values of GASP analyses were recorded along with digital values of location and altitude, time, winds, and temperature, obtained by microprocessors from within the host aircraft's avionics. These data suggested a way in which manually recorded in-flight meteorological reports could be replaced by an automatic system, which could record winds and air temperatures as often as desired. NASA's prototype ASDAR showed that automated data relay by meteorological geostationary satellites could be accomplished from an aircraft. Testing of the instruments and analyses of its data are examined.

Sparkman, James K., Jr.↗

Nonmethane Hydrocarbon Measurements on the North Atlantic Flight Corridor During SONEX

Mixing ratios of nonmethane hydrocarbons (NMHCS) were not enhanced in whole air samples collected within the North Atlantic Flight Corridor (NAFC) during the fall of 1997. The investigation was conducted aboard NASA's DC-8 research aircraft, as part of the Subsonic Assessment-Ozone and Nitrogen Experiment (SONEX). NMHC enhancements were not detected within the general Organized Tracking System (OTS) of the NAFC, nor during two tail-chases of the DC-8's own exhaust. Because positive evidence of aircraft emissions was demonstrated by enhancements in both nitrogen oxides and condensation nuclei during SONEX, the NMHC results suggest that the commercial air traffic fleet operating in the North Atlantic region does not contribute significantly to NMHCs in the NAFC.

Simpson, I. J.↗

Meteorological Conditions and Atmospheric Components Concentration in Urban Sites in Knoxville, USA. 2024

This dataset, which contains five csv files, reports several meteorological conditions such as temperature, wind speed, solar radiation, and net radiation measured in Cumberland Estates Park (CEP) and Socially Equal Energy Efficient Development (SEEED) sites in Knoxville, Tennessee, USA. Also, hourly concentration of particulate matter (PM) with different aerodynamic diameter and inorganic gases such as ozone and nitrogen dioxide measured in the two are included in this dataset. The concentrations of PM and inorganic gases were monitored using the MODULAIR, a low-cost sensor equipped with a solar power module. The measurement of the concentration of biogenic and anthropogenic volatile organic compounds (VOCs) of the two sites was determined using a High-Resolution Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-ToF-MS). The VOCs were collected using miniature canister (400 mL) equipped with female RAVEqc valve to 1/4” male compression fitting and an integrated passive air sampling kit. This work is a part of a larger study which investigates the impact of soil moisture and plant evapotranspiration on ambient temperature and relative humidity in several city parks in Knoxville, Tennessee.

54 ENVIRONMENTAL SCIENCES↗

Measurements of peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN) at selected urban, rural and remote sites

PAN and PPN were measured in a series of eight field studies performed at urban, rural and remote locations in the contiguous U.S. during 1983-1985. Seven of the eight studies were performed in the winter/spring period, a period of sparsely available data. Nearly 2000 air samples were analyzed during these studies. Mean PAN and PPN levels in the range of 45-1600 ppt (max. 7.9 ppb) and 5-230 ppt (max. 0.9 ppb), respectively, were measured. Despite a great deal of observed variability, PAN and PPN showed virtually identical behavior at all sites and in all seasons, supporting the view that these nitrogenous compounds are produced and destroyed by very similar mechanisms. On the average PPN concentrations were about 8 percent (range 3-14 percent) of PAN values. It is inferred that PPN/PAN ratio is highest in urban areas and declines as polluted air masses are transported over long distances.

Singh, Hanwant B.↗

Characterization and assessment of the potential toxicity/pathogenicity of fibrous glaucophane

In California, the metamorphic blueschist occurrences within the Franciscan Complex are commonly composed of glaucophane, which can be found with a fibrous habit. Fibrous glaucophane's potential toxicity/pathogenicity has never been determined and it has not been considered by the International Agency for Research on Cancer (IARC) as a potential carcinogen to date. Notwithstanding, outcrops hosting fibrous glaucophane are being excavated today in California for building/construction purposes (see for example the Calaveras Dam Replacement Project - CDRP). Dust generated by these excavation activities may expose workforces and the general population to this potential natural hazard. In this work, the potential toxicity/pathogenicity of fibrous glaucophane has been determined using the fibre potential toxicity index (FPTI). This model has been applied to a representative glaucophane-rich sample collected at San Anselmo, Marin County (CA, USA), characterized using a suite of experimental techniques to determine morphometric, crystal-chemical parameters, surface reactivity, biodurability and related parameters. Additionally, with respect to the asbestos minerals, the FPTI of fibrous glaucophane is remarkably higher than that of chrysotile, and comparable to that of tremolite, thus supporting the application of the precautionary approach when excavating fibrous glaucophane-rich blueschist rocks. Because fibrous glaucophane can be considered a potential health hazard, just like amphibole asbestos, it should be taken into consideration in the standard procedures for the identification and assessment of minerals fibres in soil and air samples.

54 ENVIRONMENTAL SCIENCES↗

Model Calculations of the Impact of NO(x) from Air Traffic, Lightning and Surface Emissions, Compared with Measurements

The impact of NO(x) from aircraft emissions, lightning and surface contributions on atmospheric nitrogen oxides and ozone has been investigated with the three-dimensional global chemistry transport model TM3 by partitioning the nitrogen oxides and ozone according to source category. The results have been compared with POLINAT II and SONEX airborne measurements in the North Atlantic flight corridor in 1997. Various cases have been investigated: measurements during a stagnant anti-cyclone and an almost cut-off low, both with expected high aircraft contributions, a southward bound flight with an expected strong flight corridor gradient and lightning contributions in the South, and a transatlantic flight with expected boundary layer pollution near the U.S. coast. The agreement between modeled results and measurements is reasonably good for NO and ozone. Also, the calculated impact of the three defined sources were consistent with the estimated exposure of the sampled air to these sources, obtained by specialized back-trajectory model products.

Meijer, E. W.↗

Measurements of CO and CH4 in the troposphere over Saudi Arabia, India, and the Arabian Sea during the 1979 International Summer Monsoon Experiment /MONEX/

During the 1979 Summer MONEX, 150 air samples collected over Saudi Arabia, India, and the Arabian Sea were analyzed for CO and CH4. Near Dhahran and over the Ganges Valley there were high concentrations of CO, around 300 ppbv, in the boundary layer. Out over the Saudi Arabian desert there was no sharp increase in the boundary layer. It is suggested that these high concentrations originate from pollution sources. Low values of CO, down to 80 ppbv, are found over the Arabian Sea as the monsoon progresses, and these may originate from the Southern Hemisphere. Methane over Saudi Arabia (1.59 ppmv) is a little higher than that over the Arabian Sea (1.54 ppmv) probably because the latter region is influenced by air from the Southern Hemisphere.

Newell, R. E.↗

Evaluating the feasibility of LA-ICP-TOF-MS for the analysis of environmental particle collections

Laser ablation-inductively coupled plasma-time-of-flight-mass spectrometry (LA-ICP-TOF-MS) was employed to rapidly analyze environmental particle samples collected using aerosol contaminate extractors (ACE). The ACE particle collectors were placed at various distances (0.5, 1.3, and 4.5 km) from a source that released Ru-bearing particles. Samples for measurement were then generated (as sub-samples) from the ACE collection plates via particle “lift off” with gunshot residue (GSR) tabs. The LA-ICP-TOF-MS method was employed such that 10+ samples could be analyzed in a single unattended analytical session. A 3 × 1 mm area of individual GSR tab samples were analyzed in less than 30 minutes. This provided spatially resolved elemental and isotopic measurements of the particulate content and confirmed the presence of Ru-bearing particles within the complex background environmental particle loading. As anticipated, measurements showed collectors closest to the source had the highest concentration of the released Ru-bearing particles, while all collectors, regardless of distance, contained similar levels of background particles (e.g., Fe and Sr). Sequential scanning electron microscopy – automated particle analysis (SEM-APA) and LA-ICP-TOF-MS analysis was employed for method validation and a demonstration of the multi-modal approach. The same 2-dimensional region was analyzed by both methods and the particles identified via SEM-APA were also detected using LA-ICP-TOF-MS, with 100% accuracy. Overall, LA-ICP-TOF-MS demonstrated its utility for rapid elemental and isotopic particle analysis from environmental air samples.

Manard, Benjamin T. [Oak Ridge National Laboratory↗

Analysis of Membrane Lipids of Airborne Micro-Organisms

A method of characterization of airborne micro-organisms in a given location involves (1) large-volume filtration of air onto glass-fiber filters; (2) accelerated extraction of membrane lipids of the collected micro-organisms by use of pressurized hot liquid; and (3) identification and quantitation of the lipids by use of gas chromatography and mass spectrometry. This method is suitable for use in both outdoor and indoor environments; for example, it can be used to measure airborne microbial contamination in buildings ("sick-building syndrome"). The classical approach to analysis of airborne micro-organisms is based on the growth of cultureable micro-organisms and does not provide an account of viable but noncultureable micro-organisms, which typically amount to more than 90 percent of the micro-organisms present. In contrast, the present method provides an account of all micro-organisms, including cultureable, noncultureable, aerobic, and anaerobic ones. The analysis of lipids according to this method makes it possible to estimate the number of viable airborne micro-organisms present in the sampled air and to obtain a quantitative profile of the general types of micro-organisms present along with some information about their physiological statuses.

MacNaughton, Sarah↗

Volatile organic compounds detected in the atmosphere of NASA's Biomass Production Chamber

Atmospheres of enclosed environments in which 20 m2 stands of wheat, potato, and lettuce were grown were characterized and quantified by gas chromatography-mass spectrometry. A large number (in excess of 90) of volatile organic compounds (VOCs) were identified in the chambers. Twenty eight VOC's were assumed to be of biogenic origin for these were not found in the chamber atmosphere when air samples were analyzed in the absence of plants. Some of the compounds found were unique to a single crop. For example, only 35% of the biogenic compounds detected in the wheat atmosphere were unique to wheat, while 36% were unique to potato and 26% were unique to lettuce. The number of compounds detected in the wheat (20 compounds) atmosphere was greater than that of potato (11) and lettuce (15) and concentration levels of biogenic and non-biogenic VOC's were similar.

NASA Discipline Number 61-20↗

Evaluating Precision of Measured Radionuclide Ambient Air Concentrations

According to AIRNET – Quality Assurance Project Plan for the Radiological Air Sampling Network, SOP-5140, Revision 2 (to become EPC-CP-PIP-5140): “The regulation 40 CFR Part 61.93 requires that the system be able to readily detect a dose of 1.0 mrem above background. Following statistical principles and assuming 95% confidence for such a measurement, we require that 95% of all measurements must fall within two standard deviations of the mean. This represents the minimum acceptable precision for decision making.” An independent assessment of the Rad-NESHAP program completed in early 2019 found that no documentation existed proving that the Airnet data meets the precision defined above. Therefore, to address this particular finding, Airnet concentration data was pulled from the Environmental Information Management (EIM), a cloud-based database maintained by Locus Technologies, for analysis.

54 ENVIRONMENTAL SCIENCES↗

Optimization of Ventilation Energy Demands and Indoor Air Quality in the ZEBRAlliance Homes

High-performance homes require that ventilation energy demands and indoor air quality (IAQ) be simultaneously optimized. In this project, Oak Ridge National Laboratory researchers attempted to bridge these two areas by conducting tests in research houses located in Oak Ridge, TN, that were less than 2 years old, energy-efficient (i.e., expected to consume 50% less energy than a house built per the 2006 IRC), tightly-built, unoccupied, and unfurnished. The team identified air pollutants of concern in the test homes that could generally serve as indicators of IAQ, and conduced field experiments and computer simulations to determine the effectiveness and energy required by various techniques that lessened the concentration of these contaminants. Formaldehyde was selected as the main pollutant of concern from initial air sampling surveys. Field data indicate that concentrations were higher during the summer primarily because emissions from sources rise with increases in temperature. Furthermore, supply ventilation and gas-phase filtration were effective means to reduce formaldehyde concentrations; however, exhaust ventilation had minimal influence on this pollutant. Results from simulations suggest that formaldehyde concentrations obtained while ventilating per ASHRAE 62.2-2010 could be decreased by about 20% from May through September through three strategies: 1) increasing ASHRAE supply ventilation by a factor of two, 2) reducing the thermostat setpoint from 76 to 74°F, or 3) running a gas-phase filtration system while decreasing supply ventilation per ASHRAE by half. In the mixed-humid climate of Oak Ridge, these strategies caused minimal to modest increases in electricity cost of ~$5 to ~$15/month depending on outdoor conditions.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Considerable contribution of the Montreal Protocol to declining greenhouse gas emissions from the United States

Ozone depleting substances (ODSs) controlled by the Montreal Protocol are potent greenhouse gases (GHGs), as are their substitutes, the hydrofluorocarbons (HFCs). Here we provide for the first time a comprehensive estimate of U.S. emissions of ODSs and HFCs based on precise measurements in discrete air samples from across North America and in the remote atmosphere. Derived emissions show spatial and seasonal variations qualitatively consistent with known uses and largely confirm U.S. Environmental Protection Agency (EPA) national emissions inventories for most gases. The measurement-based results further indicate a substantial decline of ODS emissions from 2008 to 2014, equivalent to ~50% of the CO 2 -equivalent decline in combined emissions of CO 2 and all other long-lived GHGs inventoried by the EPA for the same period. Total estimated CO 2 -equivalent emissions of HFCs were comparable to the sum of ODS emissions in 2014, but can be expected to decline in the future in response to recent policy measures.

54 ENVIRONMENTAL SCIENCES↗

Reformulation of dicamba herbicide: Impacts on offsite transport and soybean damage

Abstract The herbicide dicamba (3,6‐dichloro‐2‐methoxybenzoic acid) is commonly used to control broadleaf weeds in soybeans. Dicamba, however, is susceptible to volatilization and drift, thereby causing significant plant damage to nontarget crops downwind. Dicamba was reformulated to reduce volatility and off‐target movement. The effectiveness of the dicamba reformulation was assessed by quantifying dicamba emissions following spray application and investigated how meteorological factors influenced the off‐target movement. The experiments were conducted at the University of Minnesota Agricultural Experiment Station (UMORE Park) during the growing season of 2018, 2019, 2021, and 2022. Multiple high‐flow polyurethane foam air samplers were used to measure dicamba concentrations downwind from a 4‐ha soybean field sprayed with dicamba. Dicamba emissions were estimated using backward Lagrangian modeling constrained by the air sample observations. The results indicate that dicamba emissions and downwind transport were significant for several days following application. Further, non‐traited soybeans located within 15–45 m showed substantial dicamba‐related damage. In warmer, drier seasons, increased dicamba emissions caused more severe damage to downwind soybeans, likely worsened by drought stress preventing recovery. Favorable atmospheric conditions that reduced potential drift can be difficult to achieve in terms of the typical weather experienced over agricultural sites in the Upper Midwest. These results indicate that the dicamba reformulation has not adequately prevented significant post‐spray volatilization losses and downwind transport.

Agriculture↗

Performance Assessment of the CTBTO Noble Gas Network to Detect Nuclear Explosions

Atmospheric radioxenon levels are monitored worldwide by the Comprehensive Nuclear-Test-Ban Treaty Organisation (CTBTO) to detect emissions from nuclear explo-sions. Our paper examines the global network that has been set up to take routine air samples and to determine the atmospheric radioxenon concentrations. It is hypothesised that the monitoring system aims at the detection and localisation of radioxenon relea-ses. Both capabilities are dependent on background levels, explosive yields, leakage rates, transport time, choice of xenon isotope and number and locations of monitoring stations. And for each parameter, the global capabilities to detect and localise emissions from nuclear explosions are analysed. Recommendations for the future of the background sources and the development of the monitoring system are derived.

54 ENVIRONMENTAL SCIENCES↗