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

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

Organosulfate Formation in Biogenic Secondary Organic Aerosol

Organosulfates of isoprene, α-pinene, and β-pinene have recently been identified in both laboratory-generated and ambient secondary organic aerosol (SOA). In this study, the mechanism and ubiquity of organosulfate formation in biogenic SOA is investigated by a comprehensive series of laboratory photooxidation (i.e., OH-initiated oxidation) and nighttime oxidation (i.e., NO3-initiated oxidation under dark conditions) experiments using nine monoterpenes (α-pinene, β-pinene, d-limonene, l-limonene, α-terpinene, γ-terpinene, terpinolene, Δ3-carene, and β-phellandrene) and three monoterpenes (α-pinene, d-limonene, and l-limonene), respectively. Organosulfates were characterized using liquid chromatographic techniques coupled to electrospray ionization combined with both linear ion trap and high-resolution time-of-flight mass spectrometry. Organosulfates are formed only when monoterpenes are oxidized in the presence of acidified sulfate seed aerosol, a result consistent with prior work. Archived laboratory-generated isoprene SOA and ambient filter samples collected from the southeastern U.S. were reexamined for organosulfates. By comparing the tandem mass spectrometric and accurate mass measurements collected for both the laboratory-generated and ambient aerosol, previously uncharacterized ambient organic aerosol components are found to be organosulfates of isoprene, α-pinene, β-pinene, and limonene-like monoterpenes (e.g., myrcene), demonstrating the ubiquity of organosulfate formation in ambient SOA. Several of the organosulfates of isoprene and of the monoterpenes characterized in this study are ambient tracer compounds for the occurrence of biogenic SOA formation under acidic conditions. Furthermore, the nighttime oxidation experiments conducted under highly acidic conditions reveal a viable mechanism for the formation of previously identified nitrooxy organosulfates found in ambient nighttime aerosol samples. We estimate that the organosulfate contribution to the total organic mass fraction of ambient aerosol collected from K-puszta, Hungary, a field site with a similar organosulfate composition as that found in the present study for the southeastern U.S., can be as high as 30%

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)

The Ultraviolet Imaging Telescope: Instrument and Data Characteristics

The Ultraviolet Imaging Telescope (UIT) was flown as part of the Astro observatory on the Space Shuttle Columbia in December 1990 and again on the Space Shuttle Endeavor in March 1995. Ultraviolet (1200-3300 Angstroms) images of a variety of astronomical objects, with a 40 arcmin field of view and a resolution of about 3 arcsec, were recorded on photographic film. The data recorded during the first flight are available to the astronomical community through the National Space Science Data Center (NSSDC); the data recorded during the second flight will soon be available as well. This paper discusses in detail the design, operation, data reduction, and calibration of UIT, providing the user of the data with information for understanding and using the data. It also provides guidelines for analyzing other astronomical imagery made with image intensifiers and photographic film.Comment: 44 pages, LaTeX, AAS preprint style and EPSF macros, accepted by PAS

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

Boekenspiegel Archeologie.

Prehistory of Nortwestern Europ

The search rate of the African weaver ant in cashew

Oecophylla longinoda is a species of eusocial colony living ants that prey upon other insects to feed their larva. Many of these insects are considered pests. An ecosystem model of the interactions between an O. longinoda colony and its potential prey is under construction by the team behind this article, and it is unknown which functional response equations are useful for eusocial insect colonies. We investigated the search rate of O. longinoda using artificial feeding experiments in a Tanzanian cashew (Anacardium occidentale L.) orchard to determine the search efficiency of the ants, and to assess which functional response equation can be used for eusocial insects. Artificial feeding experiments consisted of providing each of ten colonies 50 pieces of sardine (175 mg dry weight in average) in cashew trees at time 0 and counting the remaining food items at four intervals of 45 minutes during a seven day period. The equations of Gutierrez-Baumgärtner, Lotka-Volterra, and Nicholson-Bailey were assessed and the Nicholson-Bailey equation was found to be most suitable. The Gutierrez-Baumgärtner equation is useful if the demand for storage can be assessed. A large variation in search rates was found between the observed colonies and this problem is discussed in relation to Oecophylla sp. efficacy as a biological control agent