W. Berk Knighton

Correlation of secondary organic aerosol with odd oxygen in Mexico City

> 0.9. The dependence of the observed proportionality onthe gas-phase hydrocarbon profile is discussed. Theobservationally-based correlation between oxygenatedorganic aerosol mass and odd oxygen may provide insightinto poorly understood secondary organic aerosolproduction mechanisms by leveraging knowledge of gas-phase ozone production chemistry. These results suggestthat global and regional models may be able to use theobserved proportionality to estimate SOA as a co-product ofmodeled O

Modulation of volatile organic compound formation in the Mycodiesel-producing endophyte Hypoxylon sp. CI-4.

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.

Chemical Speciation of Hydrocarbon Emissions from a Commercial Aircraft Engine

In April 2004, the Aerodyne Mobile Laboratory measured trace gas and particle emissions from a CFM56-2C1 high-bypass-ratio turbofan engine used to power the NASA DC-8 aircraft as part of the Aircraft Particle Emissions Experiment (APEX). This article focuses on the measured hydrocarbon species which include formaldehyde, ethylene, acetaldehyde, benzene, toluene, and several higher aromatic species. Formaldehyde and ethylene were measured by tunable-infrared-laser differential absorption spectroscopy, and the other species were measured by proton-transfer reaction mass spectroscopy. Continuous samples were taken at 1,10, and 30 m downstream of the engine-exit plane of the grounded aircraft and analyzed at a frequency of up to 1 Hz. The engine power was scanned from ground-idle up to takeoff power, and three fuel types (a baseline JP-8, a high-aromatic fuel, and a high-sulfur fuel) were investigated. Fuel type and plume age were shown to have only a minor impact on hydrocarbon emissions within the ranges studied in this experiment. However, ambient temperature was shown to have a substantial effect on these emissions. The sum of these speciated measurements agreed favorably with separate measurements of the total hydrocarbon emissions by flame ionization. The fast time response of the speciated measurements revealed interesting variability and transient behavior on a several-second timescale.

Gas Turbine Engine Emissions—Part I: Volatile Organic Compounds and Nitrogen Oxides

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.

Combustion Products of Petroleum Jet Fuel, a Fischer–Tropsch Synthetic Fuel, and a Biomass Fatty Acid Methyl Ester Fuel for a Gas Turbine Engine

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 organic compound emissions speciation; and (3) particle emissions. Replacing all or part of the petroleum jet fuel with either FAME or FT fuel reduces NOX emissions and may reduce CO emissions. Combustion of FT fuel and fuel blends increases selectivities and in some cases yields of oxygenates and some hydrocarbon volatile organic compound emissions relative to petroleum jet fuel. Combustion of FAME fuel increases propene and butene emissions, but despite its oxygen content does not strongly affect oxygenate emissions. Replacing petroleum jet fuel with zero aromatic alternatives decreases the emissions of aromatic hydrocarbons. The fuel effects become more pronounced as the size of the aromatic molecule increases (e.g., toluene is reduced more strongly than benzene). Particle emissions are decreased in particle size, number density, and total mass when petroleum jet fuel is replaced with the zero aromatic fuels. The effects of fuel composition on particle emissions are most pronounced at lower power conditions, i.e., when combustion temperature and pressure are lower, and less efficient mixing may lead to locally higher fuel/air ratios than are present at higher power.

Determination of the emissions from an aircraft auxiliary power unit (APU) during the Alternative Aviation Fuel Experiment (AAFEX)

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 Administrations (NASAs) 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 × 1015 to 5 × 1015 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 ∼90% for SO2 and particle mass EIs and ∼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 ∼5 as compared with JP-8. Implications: The results of this research show that APUs can be, depending on the level of fuel usage, an important source of air pollutant emissions at major airports in urban areas. Substantial decreases in emissions can also be achieved through the use of Fischer Tropsch (FT) fuel. Based on these results, the use of FT fuel could be a viable future control strategy for both gas- and particle-phase air pollutants. Supplemental Data: Supplemental data is available for this article. Go to the publishers online edition of the Journal of the Air & Waste Management Association for information on the test participants, description of the APU, fuel composition, sampling probes and instrumentation, test matrix, benzene to formaldehyde ratios, and speciated emissions by particle size.

Atmospheric Emission Characterization of Marcellus Shale Natural Gas Development Sites

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.

Resolution of volatile fuel compound profiles from Ascocoryne sarcoides: a comparison by proton transfer reaction-mass spectrometry and solid phase microextraction gas chromatography-mass spectrometry

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.

Multispectral imaging systems on tethered balloons for optical remote sensing education and research

Abstract. 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.

Air Pollutant Mapping with a Mobile Laboratory During the BEE-TEX Field Study

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 Agencys 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.