SOA formation from the atmospheric oxidation of 2-methyl-3-buten-2-ol and its implications for PM_2.5

The formation of secondary organic aerosol (SOA) generated by irradiating 2-methyl-3-buten-2-ol (MBO) in the presence and/or absence of NO_x, H₂O₂, and/or SO₂ was examined. Experiments were conducted in smog chambers operated in either dynamic or static mode. A filter/denuder sampling system was used for simultaneously collecting gas- and particle-phase products. The structural characterization of gas and particulate products was investigated using BSTFA, BSTFA + PFBHA, and DNPH derivatization techniques followed by GC-MS and liquid chromatography analysis. This analysis showed the occurrence of more than 68 oxygenated organic compounds in the gas and particle phases, 28 of which were tentatively identified. The major components observed include 2,3-dihydroxyisopentanol (DHIP), 2-hydroxy-2-oxoisopentanol, 2,3-dihydroxy-3-methylbutanal, 2,3-dihydroxy-2-methylsuccinic acid, 2-hydroxy-2-methylpropanedioic acid, acetone, glyoxal, methylglyoxal, glycolaldehyde, and formaldehyde. Most of these oxygenated compounds were detected for the first time in this study. <br><br> While measurements of the gas-phase photooxidation products have been made, the focus of this work has been an examination of the particle phase. SOA from some experiments was analyzed for the organic mass to organic carbon ratio (OM/OC), the effective enthalpy of vaporization (&Delta;H_vap^eff), and the aerosol yield. Additionally, aerosol size, volume, and number concentrations were measured by a Scanning Mobility Particle Sizer coupled to a Condensation Particle Counter system. The OM/OC ratio was 2.1 in the MBO/H₂O₂ system. The ΔH_vap^eff was 41 kJ mol⁻¹, a value similar to that of isoprene SOA. The laboratory SOA yield measured in this study was 0.7% in MBO/H₂O₂ for an aerosol mass of 33 μg m⁻³. Secondary organic aerosol was found to be negligible under conditions with oxides of nitrogen (NO_x) present. Time profiles and proposed reaction schemes are provided for selected compounds. <br><br> The contribution of SOA products from MBO oxidation to ambient PM_2.5 was investigated by analyzing a series of ambient PM_2.5 samples collected in several places around the United States. In addition to the occurrence of several organic compounds in both field and laboratory samples, DHIP was found to originate only from the oxidation of MBO, and therefore this compound could potentially serve as a tracer for MBO SOA. Initial attempts have been made to quantify the concentrations of DHIP and other compounds based on surrogate compound calibrations. The average concentrations of DHIP in ambient PM_2.5 samples from Duke Forest in North Carolina ranged from zero during cold seasons to approximately 1 ng m⁻³ during warm seasons. This appears to be the first time that DHIP has been detected in ambient PM_2.5 samples. The occurrence of several other compounds in both laboratory and field samples suggests that SOA originating from MBO can contribute under selected ambient conditions to the ambient aerosol mainly in areas where MBO emissions are high

The formation of secondary organic aerosol from the isoprene + OH reaction in the absence of NO_x

The reaction of isoprene (C₅H₈) with hydroxyl radicals has been studied in the absence of nitrogen oxides (NO_x) to determine physical and chemical characteristics of the secondary organic aerosol formed. Experiments were conducted using a smog chamber operated in a steady-state mode permitting measurements of moderately low aerosol levels. GC-MS analysis was conducted to measure methyl butenediols in the gas phase and polyols in the aerosol phase. Analyses were made to obtain several bulk aerosol parameters from the reaction including values for the organic mass to organic carbon ratio, the effective enthalpy of vaporization (ΔH_vap^eff), organic peroxide fraction, and the aerosol yield. <br><br> The gas phase analysis showed the presence of methacrolein, methyl vinyl ketone, and four isomers of the methyl butenediols. These gas-phase compounds may serve as precursors for one or more of several compounds detected in the aerosol phase including 2-methylglyceric acid, three 2-methyl alkenetriols, and two 2-methyl tetrols. In contrast to most previous studies, the 2-methyl tetrols (and the 2-methyl alkenetriols) were found to form in the absence of acidic sulfate aerosol. However, reaction conditions did not favor the production of HO₂ radicals, thus allowing RO₂+RO₂ reactions to proceed more readily than if higher HO₂ levels had been generated. <br><br> SOA/SOC (i.e. OM/OC) was found to average 1.9 in the absence of NO_x. The effective enthalpy of vaporization was measured as 38.6 kJ mol^&minus;1, consistent with values used previously in modeling studies. The yields in this work (using an independent technique than used previously) are lower than those of Kroll et al. (2006) for similar aerosol masses. SOC yields reported in this work range from 0.5–1.4% for carbon masses between 17 and 49 μgC m^&minus;3

Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene

The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS)

mRNAs encoding aquaporins are present during murine preimplantation development.

The present study was conducted to investigate the mechanisms underlying fluid movement across the trophectoderm during blastocyst formation by determining whether aquaporins (AQPs) are expressed during early mammalian development. AQPs belong to a family of major intrinsic membrane proteins and function as molecular water channels that allow water to flow rapidly across plasma membranes in the direction of osmotic gradients. Ten different AQPs have been identified to date. Murine preimplantation stage embryos were flushed from the oviducts and uteri of superovulated CD1 mice. Reverse transcription-polymerase chain reaction (RT-PCR) methods employing primer sets designed to amplify conserved sequences of AQPs (1-9) were applied to murine embryo cDNA samples. PCR reactions were conducted for up to 40 cycles involving denaturation of DNA hybrids at 95 degrees C, primer annealing at 52-60 degrees C and extension at 72 degrees C. PCR products were separated on 2% agarose gels and were stained with ethidium bromide. AQP PCR product identity was confirmed by sequence analysis. mRNAs encoding AQPs 1, 3, 5, 6, 7, and 9 were detected in murine embryos from the one-cell stage up to the blastocyst stage. AQP 8 mRNAs were not detected in early cleavage stages but were present in morula and blastocyst stage embryos. The results were confirmed in experimental replicates applied to separate embryo pools of each embryo stage. These results demonstrate that transcripts encoding seven AQP gene products are detectable during murine preimplantation development. These findings predict that AQPs may function as conduits for trophectoderm fluid transport during blastocyst formation

Cosmic Ray Rejection and Readout Efficiency for Large-Area Arrays

We present an algorithm to optimally process uniformly sampled array image data obtained with a nondestructive readout. The algorithm discards full wells, removes cosmic ray (particle) hits and other glitches, and makes a nearly optimum estimate of the signal on each pixel. The algorithm also compresses the data. The computer requirements are modest, and the results are robust. The results are shown and compared to results of Fowler sampled and processed data. Non-ideal detector performance may require some additional code, but this is not expected to cost much processing time. Known types of detector faults are addressed.Comment: This paper has been accepted for publication in the PAS

Validation of Up-the-Ramp Sampling with Cosmic Ray Rejection on IR Detectors

We examine cosmic ray rejection methodology on data collected from InSb and Si:As detectors. The application of an Up-the-Ramp sampling technique with cosmic ray identification and mitigation is the focus of this study. This technique is valuable for space-based observatories which are exposed to high-radiation environments. We validate the Up-the-Ramp approach on radiation-test data sets with InSb and Si:As detectors which were generated for SIRTF. The Up-the-Ramp sampling method studied in this paper is over 99.9% effective at removing cosmic rays and preserves the structure and photometric quality of the image to well within the measurement error.Comment: 30 pages, 13 figures. Accepted for publication in the PASP, 25 October 200

The North Ecliptic Pole Wide survey of AKARI: a near- and mid-infrared source catalog

We present a photometric catalog of infrared (IR) sources based on the North Ecliptic PoleWide field (NEP-Wide) survey of AKARI, which is an infrared space telescope launched by Japan. The NEP-Wide survey covered 5.4 deg2 area, a nearly circular shape centered on the North Ecliptic Pole, using nine photometric filter-bands from 2 - 25 {\mu}m of the Infrared Camera (IRC). Extensive efforts were made to reduce possible false objects due to cosmic ray hits, multiplexer bleeding phenomena around bright sources, and other artifacts. The number of detected sources varied depending on the filter band: with about 109,000 sources being cataloged in the near-IR bands at 2 - 5 {\mu}m, about 20,000 sources in the shorter parts of the mid-IR bands between 7 - 11 {\mu}m, and about 16,000 sources in the longer parts of the mid-IR bands, with \sim 4,000 sources at 24 {\mu}m. The estimated 5? detection limits are approximately 21 magnitude (mag) in the 2 - 5 {\mu}m bands, 19.5 - 19 mag in the 7 - 11 {\mu}m, and 18.8 - 18.5 mag in the 15 - 24 {\mu}m bands in the AB magnitude scale. The completenesses for those bands were evaluated as a function of magnitude: the 50% completeness limits are about 19.8 mag at 3 {\mu}m, 18.6 mag at 9 {\mu}m, and 18 mag at 18 {\mu}m band, respectively. To construct a reliable source catalog, all of the detected sources were examined by matching them with those in other wavelength data, including optical and ground-based near-IR bands. The final band-merged catalog contains about 114,800 sources detected in the IRC filter bands. The properties of the sources are presented in terms of the distributions in various color-color diagrams.Comment: Accepted for publication in A&A, 23 pages, 27 figure

Ultraviolet Signposts of Resonant Dynamics in the Starburst-Ringed Sab Galaxy, M94 (NGC 4736)

M94 (NGC 4736) is investigated using images from the Ultraviolet Imaging Telescope (FUV-band), Hubble Space Telescope (NUV-band), Kitt Peak 0.9-m telescope (H-alpha, R, and I bands), and Palomar 5-m telescope (B-band), along with spectra from the International Ultraviolet Explorer and Lick 1-m telescopes. The wide-field UIT image shows FUV emission from (a) an elongated nucleus, (b) a diffuse inner disk, where H-alpha is observed in absorption, (c) a bright inner ring of H II regions at the perimeter of the inner disk (R = 48 arcsec. = 1.1 kpc), and (d) two 500-pc size knots of hot stars exterior to the ring on diametrically opposite sides of the nucleus (R= 130 arcsec. = 2.9 kpc). The HST/FOC image resolves the NUV emission from the nuclear region into a bright core and a faint 20 arcsec. long ``mini-bar'' at a position angle of 30 deg. Optical and IUE spectroscopy of the nucleus and diffuse inner disk indicates an approximately 10^7 or 10^8 yr-old stellar population from low-level starbirth activity blended with some LINER activity. Analysis of the H-alpha, FUV, NUV, B, R, and I-band emission along with other observed tracers of stars and gas in M94 indicates that most of the star formation is being orchestrated via ring-bar dynamics involving the nuclear mini-bar, inner ring, oval disk, and outer ring. The inner starburst ring and bi-symmetric knots at intermediate radius, in particular, argue for bar-mediated resonances as the primary drivers of evolution in M94 at the present epoch. Similar processes may be governing the evolution of the ``core-dominated'' galaxies that have been observed at high redshift. The gravitationally-lensed ``Pretzel Galaxy'' (0024+1654) at a redshift of approximately 1.5 provides an important precedent in this regard.Comment: revised figure 1 (corrected coordinate labels on declination axis); 19 pages of text + 19 figures (jpg files); accepted for publication in A