Browsing by Author "Ye, Connie Z."

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    ItemOpen Access
    A broadband cavity-enhanced spectrometer for atmospheric trace gas measurements and Rayleigh scattering cross sections in the cyan region (470–540 nm)
    (Copernicus, 2019-02-27) Jordan, Nick; Ye, Connie Z.; Ghosh, Satyaki; Washenfelder, Rebecca A.; Brown, Steven S.; Osthoff, Hans D.
    An incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) instrument for quantification of atmospheric trace gases that absorb in the cyan region of the electromagnetic spectrum (470 to 540 nm), including NO2and I2, is described. The instrument uses a light-emitting diode coupled to a 1 m optical cavity consisting of a pair of mirrors in stable resonator configuration. Transmitted light is monitored using a grating spectrometer and charge-coupled device array detector. The average mirror reflectivity was determined from the N2/He and Ar/He ratios of scattering coefficients and was∼99.98 % at its maximum, yielding an effective optical path length of 6.3 km. Cross sections of N2, O2, air, Ar, CO2, and CH4 scattering and of O4 absorption were measured and agree with literature values within the measurement uncertainty. Trace gas mixing ratios were retrieved using the spectral fitting software DOA-SIS (DOAS intelligent system) from 480 to 535 nm. Under laboratory conditions, the 60 s, 1σ measurement precisions were ±124 and ±44 pptv for NO2and I2, respectively. The IBBCEAS instrument sampled ambient air in Ucluelet, BC,Canada, in July 2015. IBBCEAS retrievals agreed with in-dependent measurements of NO2by blue diode laser cavity ring-down spectroscopy (r2=0.975), but ambient I2concentrations were below the detection limit.
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    ItemOpen Access
    A broadband cavity-enhanced spectrometer for atmospheric trace gas measurements and Rayleigh scattering cross sections in the cyan region (470–540 nm)
    (European Geosciences Union, 2019-02-27) Jordan, Nick; Ye, Connie Z.; Ghosh, Satyaki; Washenfelder, Rebecca A.; Brown, Steven S.; Osthoff, Hans D.
    An incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) instrument for quantification of atmospheric trace gases that absorb in the cyan region of the electromagnetic spectrum (470 to 540 nm), including NO2 and I2, is described. The instrument uses a light-emitting diode coupled to a 1 m optical cavity consisting of a pair of mirrors in stable resonator configuration. Transmitted light is monitored using a grating spectrometer and charge-coupled device array detector. The average mirror reflectivity was determined from the N2∕He and Ar∕He ratios of scattering coefficients and was ∼99.98 % at its maximum, yielding an effective optical path length of 6.3 km. Cross sections of N2, O2, air, Ar, CO2, and CH4 scattering and of O4 absorption were measured and agree with literature values within the measurement uncertainty. Trace gas mixing ratios were retrieved using the spectral fitting software DOASIS (DOAS intelligent system) from 480 to 535 nm. Under laboratory conditions, the 60 s, 1σ measurement precisions were ±124 and ±44 pptv for NO2 and I2, respectively. The IBBCEAS instrument sampled ambient air in Ucluelet, BC, Canada, in July 2015. IBBCEAS retrievals agreed with independent measurements of NO2 by blue diode laser cavity ring-down spectroscopy (r2=0.975), but ambient I2 concentrations were below the detection limit.
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    ItemOpen Access
    Emissions of C9 – C16 hydrocarbons from kelp species on Vancouver Island: Alaria marginata (winged kelp) and Nereocystis luetkeana (bull kelp) as an atmospheric source of limonene
    (Elsevier, 2019-01-24) Tokarek, Travis W.; Brownsey, Duncan K.; Jordan, Nick; Garner, Natasha M.; Ye, Connie Z.; Osthoff, Hans D.
    In this paper, measurements of C9 – C16 biogenic volatile organic compounds (BVOCs) in the headspaces above near-shore marine vegetation samples of Fucus gardneri (rock weed), Ulva spp. (sea lettuce), Callophyllis spp. (red sea fans), Alaria marginata (winged kelp), and Nereocystis luetkeana (bull kelp) collected on the west coast of Vancouver Island, British Columbia, Canada, are presented. Numerous BVOCs were observed in the headspace samples, including n-alkanes (e.g., n-dodecane, n-tridecane, n-tetradecane and n-pentadecane) and oxygenated hydrocarbons (e.g., octanal, nonanal, geranyl acetone, and 6-methyl-hepten-2-one), though the majority of VOCs emitted was not identified. The emissions from Ulva spp., Callophyllis spp. and F. gardneri samples contained a similar assortment of n-alkanes and oxygenated BVOCs (e.g., n-aldehydes) as observed at Mace Head, Ireland, whereas the headspaces above N. luetkeana and A. marginata contained monoterpenes, foremost limonene, and toluene. Further studies are needed to constrain emissions of BVOCs from near-coastal vegetation as they have the potential to substantially impact coastal O3 budgets and the organic content of marine derived aerosol.
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    On the photolysis branching ratio of methyl ethyl ketone
    (Elsevier, 2021-06-01) Zborowska, Anna G.; MacInnis, Ceara Y.; Ye, Connie Z.; Osthoff, Hans D.
    The methyl ethyl ketone (MEK) photolysis branching ratio (α) was re-evaluated by an end product analysis and box model simulations with the Master Chemical Mechanism (MCM). Using light emitting diodes centered at 285 nm or 315 nm, MEK was irradiated in the presence of nitric oxide and oxygen to produce peroxyacetic and peroxypropanoic nitric anhydride, CH3C(O)O2NO2 (PAN) and C2H5C(O)O2NO2 (PPN), which were quantified by gas chromatography. Box model simulations indicated that PPN is partially produced as a secondary product from chemistry initiated by reaction of the hydroxyl radical (OH) with MEK. Under NOx-limited experimental conditions or in the presence of ethane as an OH quencher, the product distribution observed required α = (7±1)% + (1.1±0.7)×10-4×(T-298) for 250K < T < 300K (2σ uncertainty), independent of pressure (at pressures > 266 hPa) and consistent with current IUPAC recommendations.
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    Quantification of peroxynitric acid and peroxyacyl nitrates using an ethane-based thermal dissociation peroxy radical chemical amplification cavity ring-down spectrometer
    (European Geosciences Union, 2018-07-17) Taha, Youssef M.; Saowapon, Matthew T.; Assad, Faisal V.; Ye, Connie Z.; Chen, Xining; Garner, Natasha M.; Osthoff, Hans D.
    Peroxy and peroxyacyl nitrates (PNs and PANs) are important trace gas constituents of the troposphere which are challenging to quantify by differential thermal dissociation with NO2 detection in polluted (i.e., high-NOx) environments. In this paper, a thermal dissociation peroxy radical chemical amplification cavity ring-down spectrometer (TD-PERCA-CRDS) for sensitive and selective quantification of total peroxynitrates (ΣPN  =  ΣRO2NO2) and of total peroxyacyl nitrates (ΣPAN  =  ΣRC(O)O2NO2) is described. The instrument features multiple detection channels to monitor the NO2 background and the ROx ( =  HO2 + RO2 + ΣRO2) radicals generated by TD of ΣPN and/or ΣPAN. Chemical amplification is achieved through the addition of 0.6 ppm NO and 1.6 % C2H6 to the inlet. The instrument's performance was evaluated using peroxynitric acid (PNA) and peroxyacetic or peroxypropionic nitric anhydride (PAN or PPN) as representative examples of ΣPN and ΣPAN, respectively, whose abundances were verified by iodide chemical ionization mass spectrometry (CIMS). The amplification factor or chain length increases with temperature up to 69 ± 5 and decreases with analyte concentration and relative humidity (RH). At inlet temperatures above 120 and 250 °C, respectively, PNA and ΣPAN fully dissociated, though their TD profiles partially overlap. Furthermore, interference from ozone (O3) was observed at temperatures above 150 °C, rationalized by its partial dissociation to O atoms which react with C2H6 to form C2H5 and OH radicals. Quantification of PNA and ΣPAN in laboratory-generated mixtures containing O3 was achieved by simultaneously monitoring the TD-PERCA responses in multiple parallel CRDS channels set to different temperatures in the 60 to 130 °C range. The (1 s, 2σ) limit of detection (LOD) of TD-PERCA-CRDS is 6.8 pptv for PNA and 2.6 pptv for ΣPAN and significantly lower than TD-CRDS without chemical amplification. The feasibility of TD-PERCA-CRDS for ambient air measurements is discussed.
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    ItemOpen Access
    Quantification of peroxynitric acid and peroxyacyl nitrates using an ethane-based thermal dissociation peroxy radical chemical amplification cavity ring-down spectrometer
    (Copernicus, 2018-07-17) Taha, Youssef M.; Saowapon, Matthew T.; Assad, Faisal V.; Ye, Connie Z.; Chen, Xining; Garner, Natasha M.; Osthoff, Hans D.
    Peroxy and peroxyacyl nitrates (PNs and PANs) are important trace gas constituents of the troposphere which are challenging to quantify by differential thermal dissociation with NO2 detection in polluted (i.e., high-NOx) environments. In this paper, a thermal dissociation peroxy radical chemical amplification cavity ring-down spectrometer (TD-PERCA-CRDS) for sensitive and selective quantification of total peroxynitrates (ΣPN = ΣRO2NO2) and of total peroxyacyl nitrates (ΣPAN = ΣRC(O)O2NO2) is described. The instrument features multiple detection channels to monitor the NO2 background and the ROx ( = HO2+RO2+ΣRO2) radicals generated by TD of ΣPN and/or ΣPAN. Chemical amplification is achieved through the addition of 0.6ppm NO and 1.6% C2H6 to the inlet. The instrument's performance was evaluated using peroxynitric acid (PNA) and peroxyacetic or peroxypropionic nitric anhydride (PAN or PPN) as representative examples of ΣPN and ΣPAN, respectively, whose abundances were verified by iodide chemical ionization mass spectrometry (CIMS). The amplification factor or chain length increases with temperature up to 69±5 and decreases with analyte concentration and relative humidity (RH). At inlet temperatures above 120 and 250°C, respectively, PNA and ΣPAN fully dissociated, though their TD profiles partially overlap. Furthermore, interference from ozone (O3) was observed at temperatures above 150°C, rationalized by its partial dissociation to O atoms which react with C2H6 to form C2H5 and OH radicals. Quantification of PNA and ΣPAN in laboratory-generated mixtures containing O3 was achieved by simultaneously monitoring the TD-PERCA responses in multiple parallel CRDS channels set to different temperatures in the 60 to 130°C range. The (1s, 2σ) limit of detection (LOD) of TD-PERCA-CRDS is 6.8pptv for PNA and 2.6pptv for ΣPAN and significantly lower than TD-CRDS without chemical amplification. The feasibility of TD-PERCA-CRDS for ambient air measurements is discussed.