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Observations of total peroxy radicals (XO2 = RO2 + HO2) made by the Ethane CHemical AMPlifier (ECHAMP) and concomitant observations of additional trace gases made onboard the Aerodyne Mobile Laboratory (AML) during May 2017 were used to characterize ozone production at three sites in the San Antonio, Texas region. Median daytime [O3] was 48 ppbv at the site downwind of central San Antonio. Higher concentrations of NO and XO2 at the downwind site also led to median daytime ozone production rates (P(O3)) of 4.2 ppbv hr−1, a factor of two higher than at the two upwind sites. The 95th percentile of P(O3) at the upwind site was 15.1 ppbv hr−1, significantly lower than values observed in Houston. In situ observations, as well as satellite retrievals of HCHO and NO3, suggest that the region is NOx limited for times after approximately 09:00 local time, before which ozone production is VOC-limited. Biogenic volatile organic compounds (VOC) comprised 55 % of total OH reactivity at the downwind site, with alkanes and non-biogenic alkenes responsible for less than 10 % of total OH reactivity in the afternoon, when ozone production was highest. To control ozone formation rates at the three study sites effectively, policy efforts should be directed at reducing NOx emissions. Observations in the urban center of San Antonio are needed to determine whether this policy is true for the entire region.

The Aerodyne Mobile Laboratory was deployed to the Houston Ship Channel and surrounding areas during the Benzene and Other Toxics Exposure field study in February 2015. We evaluated atmospheric concentrations of volatile organic hydrocarbons and other hazardous air pollutants of importance to human health, including benzene, 1,3-butadiene, toluene, xylenes, ethylbenzenes, styrene, and NO2. Ambient concentration measurements were focused on the neighborhoods of Manchester, Harrisburg, and Galena Park. The most likely measured concentration of 1,3-butadiene in the Manchester neighborhood (0.17 ppb) exceeds the Environmental Protection Agency's E-5 lifetime cancer risk level of 0.14 ppb. In all the three neighborhoods, the measured benzene concentration falls below or within the E-5 lifetime cancer risk levels of 0.4–1.4 ppb for benzene. Pollution maps as a function of wind direction show the impact of nearby sources.

Limited direct measurements of criteria pollutants emissions and precursors, as well as natural gas constituents, from Marcellus shale gas development activities contribute to uncertainty about their atmospheric impact. Real-time measurements were made with the Aerodyne Research Inc. Mobile Laboratory to characterize emission rates of atmospheric pollutants. Sites investigated include production well pads, a well pad with a drill rig, a well completion, and compressor stations. Tracer release ratio methods were used to estimate emission rates. A first-order correction factor was developed to account for errors introduced by fenceline tracer release. In contrast to observations from other shale plays, elevated volatile organic compounds, other than CH4 and C2H6, were generally not observed at the investigated sites. Elevated submicrometer particle mass concentrations were also generally not observed. Emission rates from compressor stations ranged from 0.006 to 0.162 tons per day (tpd) for NOx, 0.029 to 0.426 tpd for CO, and 67.9 to 371 tpd for CO2. CH4 and C2H6 emission rates from compressor stations ranged from 0.411 to 4.936 tpd and 0.023 to 0.062 tpd, respectively. Although limited in sample size, this study provides emission rate estimates for some processes in a newly developed natural gas resource and contributes valuable comparisons to other shale gas studies.

We statistically analyze the impact of jet fuel properties on aerosols emitted by the NASA Douglas DC-8 (Tail No. N817NA) CFM56-2-C1 engines burning 15 different aviation fuels. Data were collected for this single engine type during four different, comprehensive ground tests conducted over the past decade, which allow us to clearly link changes in aerosol emissions to fuel compositional changes. It is found that the fuel aromatic and sulfur content most affect the volatile aerosol fraction, which dominates the variability (but not necessarily the magnitude) of the number and volume emissions indices (EIs) over all engine powers. Meanwhile, the naphthalenic content of the fuel determines the magnitude of the nonvolatile number and volume EI as well as the black carbon mass EI. Linear regression coefficients are reported for each aerosol EI in terms of these properties, engine fuel flow rate, and ambient temperature and show that reducing both fuel sulfur content and naphthalenes to near-zero levels would r...

Cold heavy oil production with sands (CHOPS) is a common oil extraction method in the Canadian provinces of Alberta and Saskatchewan that can result in significant methane emissions due to annular venting. Little is known about the magnitude of these emissions, nor their contributions to the regional methane budget. Here the authors present the results of field measurements of methane emissions from CHOPS wells and compare them with self-reported venting rates. The tracer ratio method was used not only to analyze total site emissions but at one site it was also used to locate primary emission sources and quantify their contributions to the facility-wide emission rate, revealing the annular vent to be a dominant source. Emissions measured from five different CHOPS sites in Alberta showed large discrepancies between the measured and reported rates, with emissions being mainly underreported. These methane emission rates are placed in the context of current reporting procedures and the role that gas-oil ratio (GOR) measurements play in vented volume estimates. In addition to methane, emissions of higher hydrocarbons were also measured; a chemical “fingerprint” associated with CHOPS wells in this region reveals very low emission ratios of ethane, propane, and aromatics versus methane. The results of this study may inform future studies of CHOPS sites and aid in developing policy to mitigate regional methane emissions. Implications: Methane measurements from cold heavy oil production with sand (CHOPS) sites identify annular venting to be a potentially major source of emissions at these facilities. The measured emission rates are generally larger than reported by operators, with uncertainty in the gas-oil ratio (GOR) possibly playing a large role in this discrepancy. These results have potential policy implications for reducing methane emissions in Alberta in order to achieve the Canadian government’s goal of reducing methane emissions by 40–45% below 2012 levels within 8 yr.

A Nodulisporium species (designated Ti-13) was isolated as an endophyte from Cassia fistula. The fungus produces a spectrum of volatile organic compounds (VOCs) that includes ethanol, acetaldehyde and 1,8-cineole as major components. Initial observations of the fungal isolate suggested that reversible attenuation of the organism via removal from the host and successive transfers in pure culture resulted in a 50 % decrease in cineole production unrelated to an overall alteration in fungal growth. A compound (CPM1) was obtained from Betula pendula (silver birch) that increases the production of 1,8-cineole by an attenuated Ti-13 strain to its original level, as measured by a novel bioassay method employing a 1,8-cineole-sensitive fungus (Sclerotinia sclerotiorum). The host plant produces similar compounds possessing this activity. Bioactivity assays with structurally similar compounds such as ferulic acid and gallic acid suggested that the CPM1 does not act as a simple precursor to the biosynthesis of 1,8-cineole. NMR spectroscopy and HPLC-ES-MS indicated that the CPM1 is a para-substituted benzene with alkyl and carboxyl substituents. The VOCs of Ti-13, especially 1,8-cineole, have potential applications in the industrial, fuel and medical fields.

[1] The Aerodyne Research Inc. mobile laboratory performed real-time in-situ measurements of volatile organic compounds, nitrogen oxides, and formaldehyde in Texas City, Texas on 7 May 2009 during the Formaldehyde and olefins from Large Industrial Releases experiment of the 2009 Study of Houston Atmospheric Radical Precursors (SHARP) campaign. Our goal was to identify and quantify emission sources within the largest industrial facility in Texas City most likely responsible for measured concentrations of benzene, an important VOC and hazardous air pollutant. The Houston Advanced Research Center inverse air quality model has been used to infer benzene emission rates from all potential source locations that could account for the benzene concentrations measured by the mobile lab in the vicinity of the facility. A Positive Matrix Factorization receptor model was also applied to the concentrations measured by the mobile lab, the results of which strongly supported the source attribution specified by the inverse model. The two independent source apportionment techniques both implicated flare, storage tank, and ultraformer units in the facility as significant contributors to emission plumes of elevated benzene concentrations observed by the mobile lab. The emissions of some of the flare and tank units were found to be greater than reported in emission inventories by about an order of magnitude.

We show for the first time quantitative online measurements of five nitrated phenol (NP) compounds in ambient air (nitrophenol C6H5NO3, methylnitrophenol C7H7NO3, nitrocatechol C6H5NO4, methylnitrocatechol C7H7NO4, and dinitrophenol C6H4N2O5) measured with a micro-orifice volatilization impactor (MOVI) high-resolution chemical ionization mass spectrometer in Detling, United Kingdom during January-February, 2012. NPs absorb radiation in the near-ultraviolet (UV) range of the electromagnetic spectrum and thus are potential components of poorly characterized light-absorbing organic matter ("brown carbon") which can affect the climate and air quality. Total NP concentrations varied between less than 1 and 98 ng m(-3), with a mean value of 20 ng m(-3). We conclude that NPs measured in Detling have a significant contribution from biomass burning with an estimated emission factor of 0.2 ng (ppb CO)(-1). Particle light absorption measurements by a seven-wavelength aethalometer in the near-UV (370 nm) and literature values of molecular absorption cross sections are used to estimate the contribution of NP to wood burning brown carbon UV light absorption. We show that these five NPs are potentially important contributors to absorption at 370 nm measured by an aethalometer and account for 4 ± 2% of UV light absorption by brown carbon. They can thus affect atmospheric radiative transfer and photochemistry and with that climate and air quality.

The Marcellus Shale is a rapidly developing unconventional natural gas resource found in part of the Appalachian region. Air quality and climate concerns have been raised regarding development of unconventional natural gas resources. Two ground-based mobile measurement campaigns were conducted to assess the impact of Marcellus Shale natural gas development on local scale atmospheric background concentrations of air pollution and climate relevant pollutants in Pennsylvania. The first campaign took place in Northeastern and Southwestern PA in the summer of 2012. Compounds monitored included methane (CH4), ethane, carbon monoxide (CO), nitrogen dioxide, and Proton Transfer Reaction Mass Spectrometer (PTR-MS) measured volatile organic compounds (VOC) including oxygenated and aromatic VOC. The second campaign took place in Northeastern PA in the summer of 2015. The mobile monitoring data were analyzed using interval percentile smoothing to remove bias from local unmixed emissions to isolate local-scale background concentrations. Comparisons were made to other ambient monitoring in the Marcellus region including a NOAA SENEX flight in 2013. Local background CH4 mole fractions were 140 ppbv greater in Southwestern PA compared to Northeastern PA in 2012 and background CH4 increased 100 ppbv from 2012 to 2015. CH4 local background mole fractions were not found to have a detectable relationship between well density or production rates in either region. In Northeastern PA, CO was observed to decrease 75 ppbv over the three year period. Toluene to benzene ratios in both study regions were found to be most similar to aged rural air masses indicating that the emission of aromatic VOC from Marcellus Shale activity may not be significantly impacting local background concentrations. In addition to understanding local background concentrations the ground-based mobile measurements were useful for investigating the composition of natural gas emissions in the region.

A novel analytical system was developed to rapidly and accurately quantify total volatile organic compound (VOC) production from microbial reactor systems using a platinum catalyst and a sensitive CO2 detector. This system allows nearly instantaneous determination of total VOC production by utilizing a platinum catalyst to completely and quantitatively oxidize headspace VOCs to CO2 in coordination with a CO2 detector. Measurement of respiratory CO2 by bypassing the catalyst allowed the total VOC content to be determined from the difference in the two signals. To the best of our knowledge, this is the first instance of a platinum catalyst and CO2 detector being used to quantify the total VOCs produced by a complex bioreactor system. Continuous recording of these CO2 data provided a record of respiration and total VOC production throughout the experiments. Proton transfer reaction-mass spectrometry (PTR-MS) was used to identify and quantify major VOCs. The sum of the individual compounds measured by PTR-MS can be compared to the total VOCs quantified by the platinum catalyst to identify potential differences in detection, identification and calibration. PTR-MS measurements accounted on average for 94 % of the total VOC carbon detected by the platinum catalyst and CO2 detector. In a model system, a VOC producing endophytic fungus Nodulisporium isolate TI-13 was grown in a solid state reactor utilizing the agricultural byproduct beet pulp as a substrate. Temporal changes in production of major volatile compounds (ethanol, methanol, acetaldehyde, terpenes, and terpenoids) were quantified by PTR-MS and compared to the total VOC measurements taken with the platinum catalyst and CO2 detector. This analytical system provided fast, consistent data for evaluating VOC production in the nonhomogeneous solid state reactor system. Electronic supplementary material The online version of this article (doi:10.1186/s13568-016-0264-2) contains supplementary material, which is available to authorized users.

Alkene emissions from the petrochemical industry contribute significantly to ozone production in the greater Houston area but are underestimated in emission inventories. It is not well-known which processes (e.g., fugitive emissions, chemical flare emissions, etc.) are responsible for these underreported emissions. We use fast time response and ground-based mobile measurements of numerous trace gas species to characterize alkene plumes from three identified chemical flares in the greater Houston area. We calculate the combustion efficiency and destruction and removal efficiency (DRE) values of these flares using the carbon balance method. All three flares were operating at DRE values lower than required by regulation. An examination of photochemistry in flare exhaust plumes indicates that the impact of direct formaldehyde emissions from flares on ozone formation is small as compared to the impact of alkene emissions.

The destruction and removal efficiency (DRE) computation of target hydrocarbon species in the flaring process is derived using carbon balance methodologies. This analysis approach is applied to data acquired during the Texas Commission on Environmental Quality 2010 Flare Study. Example DRE calculations are described and discussed. Carbon balance is achieved to within 2% for the analysis of flare vent gases. Overall method uncertainty is evaluated and examined together with apparent variability in flare combustion performance. Using fast response direct sampling measurements to characterize flare combustion parameters is sufficiently accurate to produce performance curves on a large-scale industrial flare operating at low vent gas flow rates.

During the 2010 Comprehensive Flare Study a suite of analytical instrumentation was employed to monitor and quantify in real-time the volatile organic compound (VOC) emissions emanating from an industrial chemical process flare burning either propene/natural gas or propane/natural gas. To our knowledge this represents the first time the VOC composition has been directly measured as a function of flare efficiency on an operational full-scale flare. This compositional information was obtained using a suite of proton-transfer-reaction mass spectrometers (PTR-MS) and quantum cascade laser tunable infrared differential absorption spectrometers (QCL-TILDAS) to measure the unburned fuel and associated combustion byproducts. Methane, ethyne, ethene, and formaldehyde were measured using the QC-TILDAS. Propene, acetaldehyde, methanol, benzene, acrolein, and the sum of the C3H6O isomers were measured with the PTR-MS. A second PTR-MS equipped with a gas chromatograph (GC) was operated in parallel and was used to veri...

The petrochemical industry is a major source of 1,3-butadiene and styrene emissions within the Houston-Galveston area. Both compounds are listed as hazardous air pollutants by the Environmental Protection Agency (EPA), and the Texas Commission on Environmental Quality (TCEQ) lists 1,3-butadiene as a highly reactive volatile organic compound. The Aerodyne Mobile Laboratory (AML) was deployed in 2009 as part of the Study of Houston Atmospheric Radical Precursor (SHARP) project to survey the petrochemical complexes in the Houston ship channel area for air toxics releases. This paper describes how the AML, equipped with a modified proton transfer reaction mass spectrometer configured to operate with NO+ as the reagent ion, was used to characterize and quantify fugitive emissions. On April 26, 2009, the AML surveyed the Goodyear Tire and Rubber and Texas Petrochemical (GY-TPC) complex by circumnavigating the facility on public roads while making continuous measurements. The extensive suite of trace gas instrum...

An endophytic Hypoxylon sp. (strain CI-4) producing a wide spectrum of volatile organic compounds (VOCs), including 1,8-cineole, 1-methyl-1,4-cyclohexadiene and cyclohexane, 1,2,4-tris(methylene), was selected as a candidate for the modulation of VOC production. This was done in order to learn if the production of these and other VOCs can be affected by using agents that may modulate the epigenetics of the fungus. Many of the VOCs made by this organism are of interest because of their high energy densities and thus the potential they might have as Mycodiesel fuels. Strain CI-4 was exposed to the epigenetic modulators suberoylanilide hydroxamic acid (SAHA, a histone deacetylase) and 5-azacytidine (AZA, a DNA methyltransferase inhibitor). After these treatments the organism displayed striking cultural changes, including variations in pigmentation, growth rates and odour, in addition to significant differences in the bioactivities of the VOCs. The resulting variants were designated CI4-B, CI4-AZA and CI4-SAHA. GC/MS analyses of the VOCs produced by the variants showed considerable variation, with the emergence of several compounds not previously observed in the wild-type, particularly an array of tentatively identified terpenes such as α-thujene, sabinene, γ-terpinene, α-terpinolene and β-selinene, in addition to several primary and secondary alkanes, alkenes, organic acids and derivatives of benzene. Proton transfer reaction mass spectroscopic analyses showed a marked increase in the ratio of ethanol (mass 47) to the total mass of all other ionizable VOCs, from ~0.6 in the untreated strain CI-4 to ~0.8 in CI-4 grown in the presence of AZA. Strain CI4-B was created by exposure of the fungus to 100 µM SAHA; upon removal of the epigenetic modulator from the culture medium, it did not revert to the wild-type phenotype. Results of this study have implications for understanding why there may be a wide range of VOCs found in various isolates of this fungus in nature.

We report combustion emissions data for several alternatives to petroleum based Jet A jet fuel, including a natural gas–derived Fischer–Tropsch (FT) synthetic fuel; a 50/50 blend of the FT synthetic fuel with Jet A-1; a 20/80 blend of a fatty acid methyl ester (FAME) with jet fuel; and a 40/60 blend of FAME with jet fuel. The chief distinguishing features of the alternative fuels are reduced (for blends) or negligible (for pure fuels) aromatic content and increased oxygen content (for FAME blends). A CFM International CFM56-7 gas turbine engine was the test engine, and we measured NOX, CO, speciated volatile organic compounds (including oxygenates, olefins, and aromatic compounds), and nonvolatile particle size distribution, number, and mass emissions. We developed several new methods that account for fuel energy content and used the new methods to evaluate potential fuel effects on emissions performance. Our results are categorized as follows: (1) regulated pollutant emissions, CO, and NOX; (2) volatile ...

Volatile organic compounds (VOCs) were measured by proton transfer reaction – mass spectrometry (PTR-MS) on a rooftop in the urban mixed residential and industrial area North Northeast of downtown Mexico City as part of the Megacity Initiative – Local and Global Research Observations (MILAGRO) 2006 field campaign. Thirty eight individual masses were monitored during the campaign and many species were quantified including methanol, acetaldehyde, toluene, the sum of C2 benzenes, the sum of C3 benzenes, acetone, isoprene, benzene, and ethyl acetate. The VOC measurements were analyzed to gain a better understanding of the type of VOCs present in the MCMA, their diurnal patterns, and their origins. Diurnal profiles of weekday and weekend/holiday aromatic VOC concentrations showed the influence of vehicular traffic during the morning rush hours and during the afternoon hours. Plumes including elevated toluene as high as 216 parts per billion (ppb) and ethyl acetate as high as 183 ppb were frequently observed during the late night and early morning hours, indicating the possibility of significant industrial sources of the two compounds in the region. Wind fields during those peak episodes revealed no specific direction for the majority of the toluene plumes but the ethyl acetate plumes arrived at the site when winds were from the Southwest or West. The PTR-MS measurements combined with other VOC measuring techniques at the field site as well as VOC measurements conducted in other areas of the Mexico City Metropolitan Area (MCMA) will help to develop a better understanding of the spatial pattern of VOCs and its variability in the MCMA.

Ethylene glycol (HOCH2CH2OH), used as engine coolant for most on-road vehicles, is an intermediate volatility organic compound (IVOC) with a high Henry's law coefficient. We present measurements of ethylene glycol (EG) vapor in the Caldecott Tunnel near San Francisco, using a proton transfer reaction mass spectrometer (PTR-MS). Ethylene glycol was detected at mass-to-charge ratio 45, usually interpreted as solely coming from acetaldehyde. EG concentrations in bore 1 of the Caldecott Tunnel, which has a 4% uphill grade, were characterized by infrequent (approximately once per day) events with concentrations exceeding 10 times the average concentration, likely from vehicles with malfunctioning engine coolant systems. Limited measurements in tunnels near Houston and Boston are not conclusive regarding the presence of EG in sampled air. Previous PTR-MS measurements in urban areas may have overestimated acetaldehyde concentrations at times due to this interference by ethylene glycol. Estimates of EG emission rates from the Caldecott Tunnel data are unrealistically high, suggesting that the Caldecott data are not representative of emissions on a national or global scale. EG emissions are potentially important because they can lead to the formation of secondary organic aerosol following oxidation in the atmospheric aqueous phase.

Current approaches to simulate secondary organic aerosols (SOA) in regional and global numerical models are based on parameterizations of the oxidation of precursor gases in the gas-phase and subsequent partitioning into particles. Recent findings suggest however that formation in the aqueous-phase of aerosols might contribute substantially to ambient SOA load. In this work we investigate the contribution of glyoxal to SOA through chemical processes associated with aerosols. Both a very simple and a more explicit mechanism of SOA formation from glyoxal was included in the regional chemistry transport model WRF/Chem. We simulated the first 2 weeks of June 2010 over the domain of California to make use of the extensive dataset collected during the CARES/CalNex field campaigns to evaluate our simulations. Contributions to total SOA mass were found to range from 1 to 15 % in the LA basin, and

The yearly National Student Solar Spectrograph Competition (NSSSC) is Montana Space Grant Consortium's Education and Public Outreach (EP/O) Program for NASA's Interface Region Imaging Spectrograph (IRIS) mission. The NSSSC is designed to give schools with less aerospace activity such as Minority Serving Institutions and Community Colleges an opportunity for hands on real world research experience. The NSSSC provides students from across the country the opportunity to work as part of an undergraduate interdisciplinary team to design, build and test a ground based solar spectrograph. Over the course of nine months, teams come up with their own science goals and then build an instrument to collect data in support of their goals. Teams then travel to Bozeman, MT to demonstrate their instruments and present their results in a competitive science fair environment. This paper and poster will discuss the 2011-2012 competition along with results as well as provide information on the 2012 -2013 competition opportunities.

The emissions from a Garrett-AiResearch (now Honeywell) Model GTCP85-98CK auxiliary power unit (APU) were determined as part of the National Aeronautics and Space Administration's (NASA's) Alternative Aviation Fuel Experiment (AAFEX) using both JP-8 and a coal-derived Fischer Tropsch fuel (FT-2). Measurements were conducted by multiple research organizations for sulfur dioxide (SO2, total hydrocarbons (THC), carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxides (NOx), speciated gas-phase emissions, particulate matter (PM) mass and number, black carbon, and speciated PM. In addition, particle size distribution (PSD), number-based geometric mean particle diameter (GMD), and smoke number were also determined from the data collected. The results of the research showed PM mass emission indices (EIs) in the range of 20 to 700 mg/kg fuel and PM number EIs ranging from 0.5 x 10(15) to 5 x 10(15) particles/kg fuel depending on engine load and fuel type. In addition, significant reductions in both the SO2 and PM EIs were observed for the use of the FT fuel. These reductions were on the order of approximately 90% for SO2 and particle mass EIs and approximately 60% for the particle number EI, with similar decreases observed for black carbon. Also, the size of the particles generated by JP-8 combustion are noticeably larger than those emitted by the APU burning the FT fuel with the geometric mean diameters ranging from 20 to 50 nm depending on engine load and fuel type. Finally, both particle-bound sulfate and organics were reduced during FT-2 combustion. The PM sulfate was reduced by nearly 100% due to lack of sulfur in the fuel, with the PM organics reduced by a factor of approximately 5 as compared with JP-8.

The potential human health and environmental impacts of aircraft gas turbine engine emissions during normal airport operation are issues of growing concern. During the JETS/Aircraft Particle Emissions eXperiment(APEX)-2 and APEX-3 field campaigns, we performed an extensive series of gas phase and particulate emissions measurements of on-wing gas turbine engines. In all, nine different CFM56 style engines (including both CFM56-3B1 and -7B22 models) and seven additional engines (two RB211-535E4-B engines, three AE3007 engines, one PW4158, and one CJ6108A) were studied to evaluate engine-to-engine variability. Specific gas-phase measurements include NO2, NO, and total NOx, HCHO, C2H4, CO, and a range of volatile organic compounds (e.g., benzene, styrene, toluene, naphthalene). A number of broad conclusions can be made based on the gas-phase data set: (1) field measurements of gas-phase emission indices (EIs) are generally consistent with ICAO certification values; (2) speciation of gas phase NOx between NO and NO2 is reproducible for different engine types and favors NO2 at low power (and low fuel flow rate) and NO at high power (high fuel flow rate); (3) emission indices of gas-phase organic compounds and CO decrease rapidly with increasing fuel flow rate; (4) plotting EI-CO or volatile organic compound EIs against fuel flow rate collapses much of the variability between the different engines, with one exception (AE3007); (5) HCHO, ethylene, acetaldehyde, and propene are the most abundant volatile organic compounds present in the exhaust gases that we can detect, independent of engine technology differences. Empirical correlations accurate to within 30% and based on the publicly available engine parameters are presented for estimating EI-NOx and EI-NO2. Engine-to-engine variability, unavailability of combustor input conditions, changing ambient temperatures, and complex reaction dynamics limit the accuracy of global correlations for CO or volatile organic compound EIs.

To help airports improve emission inventory data, speciated hydrocarbon emission indices have been measured from in-use commercial, airfreight, and general aviation aircraft at Oakland International Airport. The compounds reported here include formaldehyde, acetaldehyde, ethene, propene, and benzene. At idle, the magnitude of hydrocarbon emission indices was variable and reflected differences in engine technology, actual throttle setting, and ambient temperature. Scaling the measured emission indices to the simultaneously measured formaldehyde (HCHO) emission index eliminated most of the observed variability. This result supports a uniform hydrocarbon emissions profile across engine types when the engine is operating near idle, which can greatly simplify how speciated hydrocarbons are handled in emission inventories. The magnitude of the measured hydrocarbon emission index observed in these measurements (ambient temperature range 12-22 degrees C) is a factor of 1.5-2.2 times larger than the certification benchmarks. Using estimates of operational fuel flow rates at idle, this analysis suggests that current emission inventories at the temperatures encountered at this airport underestimate hydrocarbon emissions from the idle phase of operation by 16-45%.

An endophytic fungus, Gliocladium roseum (NRRL 50072), produced a series of volatile hydrocarbons and hydrocarbon derivatives on an oatmeal-based agar under microaerophilic conditions as analysed by solid-phase micro-extraction (SPME)-GC/MS. As an example, this organism produced an extensive series of the acetic acid esters of straight-chained alkanes including those of pentyl, hexyl, heptyl, octyl, sec-octyl and decyl alcohols. Other hydrocarbons were also produced by this organism, including undecane, 2,6-dimethyl; decane, 3,3,5-trimethyl; cyclohexene, 4-methyl; decane, 3,3,6-trimethyl; and undecane, 4,4-dimethyl. Volatile hydrocarbons were also produced on a cellulose-based medium, including heptane, octane, benzene, and some branched hydrocarbons. An extract of the host plant, Eucryphia cordifolia (ulmo), supported the growth and hydrocarbon production of this fungus. Quantification of volatile organic compounds, as measured by proton transfer mass spectrometry (PTR-MS), indicated a level of organic substances in the order of 80 p.p.m.v. (parts per million by volume) in the air space above the oatmeal agar medium in an 18 day old culture. Scaling the PTR-MS profile the acetic acid heptyl ester was quantified (at 500 p.p.b.v.) and subsequently the amount of each compound in the GC/MS profile could be estimated; all yielded a total value of about 4.0 p.p.m.v. The hydrocarbon profile of G. roseum contains a number of compounds normally associated with diesel fuel and so the volatiles of this fungus have been dubbed ‘myco-diesel’. Extraction of liquid cultures of the fungus revealed the presence of numerous fatty acids and other lipids. All of these findings have implications in energy production and utilization.

[1] Photochemically processed urban emissions were characterized at a mountain top location, free from local sources, within the Mexico City Metropolitan Area. Analysis of the Mexico City emission plume demonstrates a strong correlation between secondary organic aerosol and odd oxygen (O3 + NO2). The measured oxygenated-organic aerosol correlates with odd oxygen measurements with an apparent slope of (104–180) μg m−3 ppmv−1 (STP) and r2 > 0.9. The dependence of the observed proportionality on the gas-phase hydrocarbon profile is discussed. The observationally-based correlation between oxygenated organic aerosol mass and odd oxygen may provide insight into poorly understood secondary organic aerosol production mechanisms by leveraging knowledge of gas-phase ozone production chemistry. These results suggest that global and regional models may be able to use the observed proportionality to estimate SOA as a co-product of modeled O3 production until more complete models of SOA formation become available.

We demonstrate the use of an aldehyde scrubber system to resolve isobaric aldehyde/alkene interferences in a proton transfer reaction mass spectrometer (PTR-MS) by selectively removing the aldehydes from the gas mixture without loss of quantitative information for the alkene components. The aldehyde scrubber system uses a bisulfite solution, which scrubs carbonyl compounds from the gas stream by forming water-soluble carbonyl bisulfite addition products, and has been evaluated using a synthetic mixture of acrolein and isoprene. Trapping efficiencies of acrolein exceeded 97%, whereas the transmission efficiency of isoprene was better than 92%. Quantification of the PTR-MS response to acrolein was validated through an intercomparison study that included two derivatization methods, dinitrophenylhydrazine (DNPH) and O-(4-cyano-2-ethoxybenzyl)hydroxylamine (CNET), and a spectroscopic method using a quantum cascade laser infrared absorption spectroscopy (QCL) instrument. Finally, using cigarette smoke as a complex matrix, the acrolein content was assessed using the scrubber and compared with direct QCL-based detection.

A set of low-cost, compact multispectral imaging systems have been developed for deployment on tethered balloons for education and outreach based on basic principles of optical remote sensing. They have proven to be sufficiently capable, and they are now being used in research as well. The imagers use tiny complementary metal-oxide semiconductor cameras with low-cost optical filters to obtain images in red and near-infrared bands, and a more recent version includes a blue band. The red and near-infrared bands are used primarily for identifying and monitoring vegetation through the normalized difference vegetation index (NDVI), while the blue band can be used for studying water turbidity and so forth. The imagers are designed to be carried by tethered balloons to altitudes currently up to approximately 50 m. These undergraduate-student-built imaging systems are being used by university and college students for a broad range of applications in multispectral imaging, remote sensing, and environmental science.

Engaging students actively is essential for an effective outreach program. Our program engages students by appointing them as chief detectives in a mystery. Their goal is to determine the identify of the thief. The program is designed for middle school students with little or no laboratory experience and is structured so that these students can solve the mystery themselves with minimal assistance from laboratory supervisors. Students are presented with a synopsis of the mystery, small samples of evidence collected at the scene and information about the suspects. Through a series of chemical experiments students identify the evidence collected. Using this information together with the information provided about the suspects and the crime scene, students determine the identify of the thief. Students involved in this program learn about experimental design, careful observation, analytical reasoning and have fun in the process. The program is designed to spark interest in science and to build student self-con...

Volatile hydrocarbon production by Ascocoryne sacroides was studied over its growth cycle. Gas-phase compounds were measured continuously with a proton transfer reaction-mass spectrometry (PTR-MS) and at distinct time points with gas chromatography-mass spectrometry (GC-MS) using head space solid phase microextraction (SPME). The PTR-MS ion signal permitted temporal resolution of the volatile production while the SPME results revealed distinct compound identities. The quantitative PTR-MS results showed the volatile production was dominated by ethanol and acetaldehyde, while the concentration of the remainder of volatiles consistently reached 2,000 ppbv. The measurement of alcohols from the fungal culture by the two techniques correlated well. Notable compounds of fuel interest included nonanal, 1-octen-3-ol, 1-butanol, 3-methyl- and benzaldehyde. Abiotic comparison of the two techniques demonstrated SPME fiber bias toward higher molecular weight compounds, making quantitative efforts with SPME impractical. Together, PTR-MS and SPME GC-MS were shown as valuable tools for characterizing volatile fuel compound production from microbiological sources.