Experimental Characterization of Gas Turbine Emissions at Simulated Flight Altitude Conditions

NASA's Atmospheric Effects of Aviation Project (AEAP) is developing a scientific basis for assessment of the atmospheric impact of subsonic and supersonic aviation. A primary goal is to assist assessments of United Nations scientific organizations and hence, consideration of emissions standards by the International Civil Aviation Organization (ICAO). Engine tests have been conducted at AEDC to fulfill the need of AEAP. The purpose of these tests is to obtain a comprehensive database to be used for supplying critical information to the atmospheric research community. It includes: (1) simulated sea-level-static test data as well as simulated altitude data; and (2) intrusive (extractive probe) data as well as non-intrusive (optical techniques) data. A commercial-type bypass engine with aviation fuel was used in this test series. The test matrix was set by parametrically selecting the temperature, pressure, and flow rate at sea-level-static and different altitudes to obtain a parametric set of data

Evaluation of nitrogen dioxide chemiluminescence monitors in a polluted urban environment

International audienceData from a recent field campaign in Mexico City are used to evaluate the performance of the EPA Federal Reference Method for monitoring the ambient concentrations of NO2. Measurements of NO2 from standard chemiluminescence monitors equipped with molybdenum oxide converters are compared with those from Tunable Infrared Laser Differential Absorption Spectroscopy (TILDAS) and Differential Optical Absorption Spectroscopy (DOAS) instruments. A significant interference in the chemiluminescence measurement is shown to account for up to 50% of ambient NO2 concentration during afternoon hours. As expected, this interference correlates well with non-NOx reactive nitrogen species (NOz) as well as with ambient O3 concentrations, indicating a photochemical source for the interfering species. A combination of ambient gas phase nitric acid and alkyl and multifunctional alkyl nitrates is deduced to be the primary cause of the interference. Observations at four locations at varying proximities to emission sources indicate that the percentage contribution of HNO3 to the interference decreases with time as the air parcel ages. Alkyl and multifunctional alkyl nitrate concentrations are calculated to reach concentrations as high as several ppb inside the city, on par with the highest values previously observed in other urban locations. Averaged over the MCMA-2003 field campaign, the chemiluminescence monitor interference resulted in an average measured NO2 concentration up to 22% greater than that from co-located spectroscopic measurements. Thus, this interference has the potential to initiate regulatory action in areas that are close to non-attainment and may mislead atmospheric photochemical models used to assess control strategies for photochemical oxidants

Engine Gaseous, Aerosol Precursor and Particulated Flight Altitude Conditions

The overall objective of the NASA Atmospheric Effects of Aviation Project (AEAP) is to develop scientific bases for assessing atmospheric impacts of the exhaust emissions by both current and future fleets of subsonic and supersonic aircraft. Among the six primary elements of the AEAP is Emissions Characterization. The objective of the Emission Characterization effort is to determine the exhaust emission constituents and concentrations at the engine exit plane. The specific objective of this engine test is to obtain a database of gaseous and particulate emissions as a function of fuel sulfur and engine operating conditions. The database of the particulate emission properties is to be used as a comparative baseline with subsequent flight measurement. The engine used in this test was a Pratt & Whitney F1OO-200E turbofan engine. Aviation fuel (Jet A) with a range of fuel sulfur was used. Low and high sulfur values are limited by commercially available fuels and by fuel specification limits of O.3% by weight. Test matrix was set by parametrically varying the combustor inlet temperature (T(sub 3) between idle and maximum power setting at simulated SLS and up to five other altitudes for each fuel. Four diagnostic systems, extractive and non-intrusive, were assembled for the gaseous and particulate emissions characterization measurements study. NASA extractive system includes smoke meter and analyzers for measurement of CO, CO2, NO, NOx, O2, total unburnt hydrocarbons (THC), and SO2. Particulate emissions were characterized by University of Missouri-Rolla Mobile Aerosol Sampling System. A chemical ionization mass spectrometer from the Air Force Research Laboratory at Hanscom AFB was used to measure SO2 and HNO3. Aerodyne Research. Inc. used infrared tunable diode laser absorption to measure SO2, SO3, NO, H2O and CO2

Sulindac targets nuclear β-catenin accumulation and Wnt signalling in adenomas of patients with familial adenomatous polyposis and in human colorectal cancer cell lines

Nonsteroidal anti-inflammatory drugs (NSAIDs) have chemopreventive potential against colorectal carcinomas (CRCs). Inhibition of cyclooxygenase (COX)-2 underlies part of this effect, although COX-2-independent mechanisms may also exist. Nonsteroidal anti-inflammatory drugs appear to inhibit the initial stages of the adenoma-carcinoma sequence, suggesting a link to the APC/beta-catenin/TCF pathway (Wnt-signalling pathway). Therefore, the effect of the NSAID sulindac on nuclear (nonphosphorylated) beta-catenin and beta-catenin/TCF-mediated transcription was investigated. Nuclear #946;-catenin expression was assessed in pretreatment colorectal adenomas and in adenomas after treatment with sulindac from five patients with familial adenomatous polyposis (FAP). Also, the effect of sulindac sulphide on beta-catenin/TCF-mediated transcription was studied. Adenomas of FAP patients collected after treatment with sulindac for up to 6 months showed less nuclear beta-catenin expression compared to pretreatment adenomas of the same patients. Sulindac sulphide abrogated beta-catenin/TCF-mediated transcription in the CRC cell lines DLD1 and SW480, and decreased the levels of nonphosphorylated beta-catenin. As a result, the protein levels of the positively regulated TCF targets Met and cyclin D1 were downregulated after sulindac treatment. This study provides in vivo and in vitro evidence that nuclear beta-catenin localisation and beta-catenin/TCF-regulated transcription of target genes can be inhibited by sulindac. The inhibition of Wnt-signalling provides an explanation for the COX-2-independent mechanism of chemoprevention by NSAID

Free energies of binding of R- and S-propranolol to wild-type and F483A mutant cytochrome P450 2D6 from molecular dynamics simulations

Detailed molecular dynamics (MD) simulations have been performed to reproduce and rationalize the experimental finding that the F483A mutant of CYP2D6 has lower affinity for R-propranolol than for S-propranolol. Wild-type (WT) CYP2D6 does not show this stereospecificity. Four different approaches to calculate the free energy differences have been investigated and were compared to the experimental binding data. From the differences between calculations based on forward and backward processes and the closure of thermodynamic cycles, it was clear that not all simulations converged sufficiently. The approach that calculates the free energies of exchanging R-propranolol with S-propranolol in the F483A mutant relative to the exchange free energy in WT CYP2D6 accurately reproduced the experimental binding data. Careful inspection of the end-points of the MD simulations involved in this approach, allowed for a molecular interpretation of the observed differences

A cross-sectional study of self-reported chemical-related sensitivity is associated with gene variants of drug-metabolizing enzymes

BACKGROUND: N-acetyltransferases (NAT) and glutathione S-transferases (GST) are involved in the metabolism of several ubiquitous chemical substances leading to the activation and detoxification of carcinogenic heterocyclic and aromatic amines. Since polymorphisms within these genes are described to influence the metabolism of ubiquitous chemicals, we conducted the present study to determine if individuals with self-reported chemical-related sensitivity differed from controls without self-reported chemical-related sensitivity with regard to the distribution of genotype frequencies of NAT2, GSTM1, GSTT1, and GSTP1 polymorphisms. METHODS: Out of 800 subjects who answered a questionnaire of ten items with regard to their severity of chemical sensitivity 521 unrelated individuals agreed to participate in the study. Subsequently, genetic variants of the NAT2, GSTM1, GSTT1, and GSTP1 genes were analyzed. RESULTS: The results show significant differences between individuals with and without self-reported chemical-related sensitivity with regard to the distribution of NAT2, GSTM1, and GSTT1 gene variants. Cases with self-reported chemical-related sensitivity were significantly more frequently NAT2 slow acetylators (controlled OR = 1.81, 95% CI = 1.27–2.59, P = 0.001). GSTM1 and GSTT1 genes were significantly more often homozygously deleted in those individuals reporting sensitivity to chemicals compared to controls (GSTM1: controlled OR 2.08, 95% CI = 1.46–2.96, P = 0.0001; GSTT1: controlled OR = 2.80, 95% CI = 1.65–4.75, P = 0.0001). Effects for GSTP1 gene variants were observed in conjunction with GSTM1, GSTT1 and NAT2 gene. CONCLUSION: The results from our study population show that individuals being slow acetylators and/or harbouring a homozygous GSTM1 and/or GSTT1 deletion reported chemical-related hypersensitivity more frequently

THEORETICAL PREDICTION OF FAR WING INFRARED LINESHAPES

$^{1}$ R.W. Davies, R.H. Tipping and S.A. Clough, Phys. Rev. A 26, 3378 (1982). $^{2}$ A. Nauts and R.E. Wyatt, Phys. Rev. A 30, 872 (1984). Work supported by AFOSR under Contract F19628-85-C-0183Author Institution: Center for Chemical and Environmental Physics, Aerodyne ResearchFar wing absorption is important in determining long path atmospheric absorption between strong adsorption bands. Development of a detailed dynamical theory of wing lineshapes for atmospheric molecules is a challenging task. A fully quantum mechanical, time dependent, perturbative $theory^{1}$ has been used to evaluate far wing absorption for the 404-515 self-broadened H2O rotational line. The predicted absorption coefficient increases with temperature, in contrast to experimental observations of a strong negative temperature dependence. Replacement of an Anderson-like ad hoc cutoff by a formal resummation of the perturbation series yielded no improvement. We conclude that perturbative methods using multipole expansions are not adequate for this system. Preliminary calculations for an Ar-HC1 test case using a non-perturbative technique, the Recursive Residue Generation Method,2 will be presented

LASER SPECTROSCOPY OF SiF2SiF_{2} AND CHEMILUMINESCENCE IN REACTIONS WITH FLUORINE ATOMS AND MOLECULES

$^{1}$J.A. Mucha, D.L. Flamm, and V.M. Donnelly, J. Appl. Phys. 53, 4553 (1982). $^{2}$H.F. Winters and F.A. Houle, J. Appl. Phys. 54, 1218 (1983) $^{3}$J.A. Mucha, V.M. Donnelly, and D.L. Flamm, J. Phys. Chem. 85, 3529 (1981)Author Institution: Aerodyne Research, Inc.; Aerodyne Research, Inc.; Aerodyne Research, Inc.; Department of Chemistry, Washington UniversityThe $SiF_{2}$ radical is an important intermediate in the plasma etching of silicon in fluorocarbon plasmas, a widely used semiconductor device fabrication process. We report tunable dye laser fluorescence and tunable diode laser infrared absorption spectra of $SiF_{2}$, taken as part of a program of development of laser diagnostics for such processes. We also used these diagnostics in a fast flow reactor to measure the kinetics of $SiF_{2}$ reactions with F and $F_{2}$. The chemiluminescence observed during plasma etching has been attributed to these $reactions,^{1}$ although some doubt $remains.^{2}$ The similarity in activation engergies for the emission and etching has been used as deciding evidence in a detailed model of the etching process. We will present results on the chemiluminescent spectrum from the reaction of F and $F_{2}$ with $SiF_{2}$ formed from two different sources, $SiF_{4}$ passed over hot Si, and thermal decomposition of $Si_{2} F_{6}$

CAVITY ATTENUATED PHASE SHIFT-BASED MONITORING OF ATMOSPHERIC SPECIES

Author Institution: Aerodyne Research, Inc., Billerica, MA 01821We are developing compact instruments for the monitoring of ambient atmospheric species, specifically nitrogen dioxide and particles, using cavity attenuated phase shift spectroscopy. The sensor, which detects the optical absorption of nitrogen dioxide within a 20 nm bandpass band centered at 440 nm, comprises a blue light emitting diode, an enclosed metal measurement cell (26 cm in length) incorporating a resonant optical cavity of near-confocal design and a vacuum photodiode detector. An analog heterodyne detection scheme is used to measure the phase shift in the waveform of the modulated light transmitted through the cell induced by the presence of nitrogen dioxide and/or particles within the cell. The entire apparatus is encased within a standard 19-inch rack-mounted enclosure. Levels of detection (1 s, 3 $\sigma$) for nitrogen dioxide of ~0.2 ppb and for aerosols of ~3.5 Mm$^{-1}$ have been achieved. Examples of high resolution field measurements and comparisons with other instrumentation will be presented