Emissions of Volatile Organic Compounds Inferred From Airborne Flux Measurements over a Megacity

Toluene and benzene are used for assessing the ability to measure disjunct eddy covariance (DEC) fluxes of Volatile Organic Compounds (VOC) using Proton Transfer Reaction Mass Spectrometry (PTR-MS) on aircraft. Statistically significant correlation between vertical wind speed and mixing ratios suggests that airborne VOC eddy covariance (EC) flux measurements using PTR-MS are feasible. City-median midday toluene and benzene fluxes are calculated to be on the order of 14.1±4.0 mg/m<sup>2</sup>/h and 4.7±2.3 mg/m<sup>2</sup>/h, respectively. For comparison the adjusted CAM2004 emission inventory estimates toluene fluxes of 10 mg/m<sup>2</sup>/h along the footprint of the flight-track. Wavelet analysis of instantaneous toluene and benzene measurements during city overpasses is tested as a tool to assess surface emission heterogeneity. High toluene to benzene flux ratios above an industrial district (e.g. 10–15 g/g) including the International airport (e.g. 3–5 g/g) and a mean flux (concentration) ratio of 3.2±0.5 g/g (3.9±0.3 g/g) across Mexico City indicate that evaporative fuel and industrial emissions play an important role for the prevalence of aromatic compounds. Based on a tracer model, which was constrained by BTEX (BTEX– Benzene/Toluene/Ethylbenzene/m, p, o-Xylenes) compound concentration ratios, the fuel marker methyl-tertiary-butyl-ether (MTBE) and the biomass burning marker acetonitrile (CH<sub>3</sub>CN), we show that a combination of industrial, evaporative fuel, and exhaust emissions account for >87% of all BTEX sources. Our observations suggest that biomass burning emissions play a minor role for the abundance of BTEX compounds in the MCMA (2–13%)

On the Interpretation of the broad-band millimeter-wave flux from Orion

Spectral observations of the core of Orion A at wavelengths around 1.3 mm show a high density of strong, broad emission lines. The combined flux in lines with peak antenna temperatures stronger than 0.2 K accounts for approximately 40 percent of the broad-band millimeter-wave flux from the region. Thus the broad-band flux from Orion A is in large part due to sources other than dust emission

Molecular abundances in OMC-1: The chemical composition of interstellar molecular clouds and the influence of massive star formation

We present here an investigation of the chemical composition of the various regions in the core of the Orion molecular cloud (OMC-1) based on results from the Caltech Owens Valley Radio Observatory (OVRO) millimeter-wave spectral line survey (Sutton et al.; Blake et al.). This survey covered a 55 GHz interval in the 1.3 mm (230 GHz) atmospheric window and contained emission from over 800 resolved spectral features. Of the 29 identified species 14 have a sufficient number of detected transitions to be investigated with an LTE "rotation diagram" technique, in which large numbers of lines are used to estimate both the rotational excitation and the overall abundance. The rotational temperatures and column densities resulting from these fits have then been used to model the emission from those remaining species which either have too few lines or which are too weak to be so analyzed. When different kinematic sources of emission are blended to produce a single feature, Gaussian fits have been used to derive the individual contributions to the total line profile. The uniformly calibrated data in the unique and extensive Caltech spectral line survey lead to accurate estimates of the chemical and physical parameters of the Orion molecular cloud, and place significant constraints on models of interstellar chemistry. A global analysis of the observed abundances shows that the markedly different chemical compositions of the kinematically and spatially distinct Orion subsources may be interpreted in the framework of an evolving, initially quiescent, gas-phase chemistry influenced by the process of massive star formation. The chemical composition of the extended Orion cloud complex is similar to that found in a number of other objects, but the central regions of OMC-1 have had their chemistry selectively altered by the radiation and high-velocity outflow from the young stars embedded deep within the interior of the molecular cloud. Specifically, the extended ridge clouds are inferred to have a low (subsolar) gas-phase oxygen content from the prevalence of reactive carbon-rich species like CN, CCH, and C_3H_2 also found in more truly quiescent objects such as TMC-1. The similar abundances of these and other simple species in clouds like OMC-1, Sgr B2, and TMC-1 lend support to gas-phase ion-molecule models of interstellar chemistry, but grain processes may also play a significant role in maintaining the overall chemical balance in such regions through selective depletion mechanisms and grain mantle processing. In contrast, the chemical compositions of the more turbulent plateau and hot core components of OMC-1 are dominated by high-temperature, shock-induced gas and grain surface neutral-neutral reaction processes. The high silicon/sulfur oxide and water content of the plateau gas is best modeled by fast shock disruption of smaller grain cores to release the more refractory elements followed by a predominantly neutral chemistry in the cooling postshock regions, while a more passive release of grain mantle products driven toward kinetic equilibrium most naturally explains the prominence of fully hydrogenated N-containing species like HCN, NH_3 , CH_3CN, and C_2H_5CN in the hot core. The clumpy nature of the outflow is illustrated by the high-velocity emission observed from easily decomposed molecules such as H_2CO. Areas immediately adjacent to the shocked core in which the cooler, ion-rich gas of the surrounding molecular cloud is mixed with water/oxygen rich gas from the plateau source are proposed to give rise to the enhanced abundances of complex internal rotors such as CH_30H, HCOOCH_3 , and CH_30CH_3 whose line widths are similar to carbon-rich species such as CN and CCH found in the extended ridge, but whose rotational temperatures are somewhat higher and whose spatial extents are much more compact

Molecular line survey of Sagittarius B2(M) from 330 to 355 GHz and comparison with Sagittarius B2(N)

We have surveyed molecular line emission from Sgr B2 over the range from 330 to 355 GHz at the position designated Sgr B2(M). This position is prominent in millimeter continuum maps of the region and is associated with a compact H II region, a hot NH_3 core, and sources of H_2O and OH maser emission. We have also obtained observations contrasting the submillimeter molecular emission from Sgr B2(M) and Sgr B2(N), an additional center of activity thought to be a dense protostellar core. The picture of the interstellar chemistry of these regions which we derive is substantially different from that determined from previous observations at lower frequencies and with lower spatial resolution. In particular, molecules such as SO_2 and CH_3OH dominate the submillimeter spectrum to a much greater extent than they do the low-frequency observations. Much of this difference is due to the higher spatial resolution of the submillimeter observations, which makes them much more sensitive to emission from compact, dense cores. The millimeter data were most effective at sampling material in the surrounding lower density regions. The chemistry of the core sources in Sgr B2 appears similar to that of other dense cores, such as the core of the Orion molecular cloud. The spectral differences between Sgr B2(M) and Sgr B2(N) primarily relate to differences in excitation and column density. For most molecular species the northern source (N) has a column density significantly higher than that found in the middle source (M), often by a factor of about 5. The principal exceptions are the species SO and SO_2 which seem to be substantially more abundant in the middle source. Generally excitation seems to be higher in the northern source, suggesting a somewhat higher density core, although there are some departures indicating that the excitation situation is more complicated. High optical depths in many of the submillimeter transitions systematically bias the interpretation of both column densities and excitation. Many of the millimeter lines may also have high optical depths, particularly those lines arising from the compact core sources

The rotational emission-line spectrum of Orion A between 247 and 263 GHz

Results are presented from a molecular line survey of the core of the Orion molecular cloud between 247 and 263 GHz. The spectrum contains a total of 243 resolvable lines from 23 different chemical species. When combined with the earlier survey of Orion from 215 to 247 GHz by Sutton et al. (1985), the complete data set includes over 780 emission features from 29 distinct molecules. Of the 23 molecules detected in this survey, only NO, CCH, and HCO^+ were not identified in the lower frequency data. As a result of the supporting laboratory spectroscopy performed to supplement existing millimeter-wave spectral line catalogs, only 33 of the more than 780 lines remain unidentified, of which 16 occur in the upper frequency band. A significant chance remains that a number of these unidentified lines are due to transitions between states of either isotopically substituted or highly excited abundant and complex molecules such as CH_3OH, CH_3OCH_3, and HCOOCH_3, whose rotational spectra are poorly known at present. The very small percentage and weak strength of the unidentified lines implies that the dominant chemical constituents visible at millimeter wavelengths have been identified in the Orion molecular cloud

Observations of pre-stellar cores

Our understanding of the physical and chemical structure of pre-stellar cores, the simplest star-forming sites, has significantly improved since the last IAU Symposium on Astrochemistry (South Korea, 1999). Research done over these years has revealed that major molecular species like CO and CS systematically deplete onto dust grains at the interior of pre-stellar cores, while species like N2H+ and NH3 survive in the gas phase and can usually be detected towards the core centers. Such a selective behaviour of molecular species gives rise to a differentiated (onion-like) chemical composition, and manifests itself in molecular maps as a dichotomy between centrally peaked and ring-shaped distributions. From the point of view of star-formation studies, the identification of molecular inhomogeneities in cores helps to resolve past discrepancies between observations made using different tracers, and brings the possibility of self-consistent modelling of the core internal structure. Here I present recent work on determining the physical and chemical structure of two pre-stellar cores, L1498 and L1517B, using observations in a large number of molecules and Monte Carlo radiative transfer analysis. These two cores are typical examples of the pre-stellar core population, and their chemical composition is characterized by the presence of large freeze out holes in most molecular species. In contrast with these chemically processed objects, a new population of chemically young cores has started to emerge. The characteristics of its most extreme representative, L1521E, are briefly reviewed.Comment: 10 pages, 5 figures. To appear in IAU 231 conf. proc. "Astrochemistry: Recent Successes and Current Challenges," eds. D.C. Lis, G.A. Blake, and E. Herbs

Excitation of methyl cyanide in the hot core of Orion

The excitation of CH_3CN in the hot core of Orion is examined using high-sensitivity observational data at 1.3 mm. Observed line fluxes are analyzed by means of multilevel statistical equilibrium (SE) calculations which incorporate current theoretical values of the collisional excitation rates. The analysis is applied to both optically thin models of the hot core region and models with significant optical depths. Trapping is found to play a critical role in the excitation of CH_3CN. An optically thin analysis yields a kinetic temperature of 275 K and a cloud density of 2 x 10^6 cm^(-3). Unequal column densities are deduced in this case for the two symmetry species: N_A = 1.4 x 10^(14) cm^(-2) and N_E = 2.0 x 10^(14) cm^(-2). The deduced cloud density and temperature are lowered to 1.5 x 10^6 cm^(-3) and 240 K. The model with trapping is favored because of the agreement with measured sizes of the hot core source and the more plausible N_A/N_E ratio. Analysis of radiative excitation in the hot core indicates it is unlikely to significantly affect the ground vibrational state populations of CH_3CN. It most likely is significant for excitation of the V_8 band

Cost analysis of advanced turbine blade manufacturing processes

A rigorous analysis was conducted to estimate relative manufacturing costs for high technology gas turbine blades prepared by three candidate materials process systems. The manufacturing costs for the same turbine blade configuration of directionally solidified eutectic alloy, an oxide dispersion strengthened superalloy, and a fiber reinforced superalloy were compared on a relative basis to the costs of the same blade currently in production utilizing the directional solidification process. An analytical process cost model was developed to quantitatively perform the cost comparisons. The impact of individual process yield factors on costs was also assessed as well as effects of process parameters, raw materials, labor rates and consumable items

Viral proteins expressed in the protozoan parasite Eimeria tenella are detected by the chicken immune system

BACKGROUND: Eimeria species are parasitic protozoa that cause coccidiosis, an intestinal disease commonly characterised by malabsorption, diarrhoea and haemorrhage that is particularly important in chickens. Vaccination against chicken coccidiosis is effective using wild-type or attenuated live parasite lines. The development of protocols to express foreign proteins in Eimeria species has opened up the possibility of using Eimeria live vaccines to deliver heterologous antigens and function as multivalent vaccine vectors that could protect chickens against a range of pathogens. RESULTS: In this study, genetic complementation was used to express immunoprotective virus antigens in Eimeria tenella. Infectious bursal disease virus (IBDV) causes Gumboro, an immunosuppressive disease that affects productivity and can interfere with the efficacy of poultry vaccination programmes. Infectious laryngotracheitis virus (ILTV) causes a highly transmissible respiratory disease for which strong cellular immunity and antibody responses are required for effective vaccination. Genes encoding the VP2 protein from a very virulent strain of IBDV (vvVP2) and glycoprotein I from ILTV (gI) were cloned downstream of 5’Et-Actin or 5’Et-TIF promoter regions in plasmids that also contained a mCitrine fluorescent reporter cassette under control of the 5’Et-MIC1 promoter. The plasmids were introduced by nucleofection into E. tenella sporozoites, which were then used to infect chickens. Progeny oocysts were sorted by FACS and passaged several times in vivo until the proportion of fluorescent parasites in each transgenic population reached ~20 % and the number of transgene copies per parasite genome decreased to < 10. All populations were found to transcribe and express the transgene and induced the generation of low titre, transgene-specific antibodies when used to immunise chickens. CONCLUSIONS: E. tenella can express antigens of other poultry pathogens that are successfully recognised by the chicken immune system. Nonetheless, further work has to be done in order to improve the levels of expression for its future use as a multivalent vaccine vector. ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (doi:10.1186/s13071-016-1756-2) contains supplementary material, which is available to authorized users

Eimeria tenella protein trafficking: differential regulation of secretion versus surface tethering during the life cycle

Eimeria spp. are intracellular parasites that have a major impact on poultry. Effective live vaccines are available and the development of reverse genetic technologies has raised the prospect of using Eimeria spp. as recombinant vectors to express additional immunoprotective antigens. To study the ability of Eimeria to secrete foreign antigens or display them on the surface of the sporozoite, transiently transfected populations of E. tenella expressing the fluorescent protein mCherry, linked to endogenous signal peptide (SP) and glycophosphatidylinositol-anchor (GPI) sequences, were examined. The SP from microneme protein EtMIC2 (SP2) allowed efficient trafficking of mCherry to cytoplasmic vesicles and following the C-terminal addition of a GPI-anchor (from surface antigen EtSAG1) mCherry was expressed on the sporozoite surface. In stable transgenic populations, mCherry fused to SP2 was secreted into the sporocyst cavity of the oocysts and after excystation, secretion was detected in culture supernatants but not into the parasitophorous vacuole after invasion. When the GPI was incorporated, mCherry was observed on the sporozites surface and in the supernatant of invading sporozoites. The proven secretion and surface exposure of mCherry suggests that antigen fusions with SP2 and GPI of EtSAG1 may be promising candidates to examine induction of protective immunity against heterologous pathogens