The Identity and Chemistry of C7H7 Radicals Observed during Soot Formation.

We used aerosol mass spectrometry coupled with tunable synchrotron photoionization to measure radical and closed-shell species associated with particle formation in premixed flames and during pyrolysis of butane, ethylene, and methane. We analyzed photoionization (PI) spectra for the C7H7 radical to identify the isomers present during particle formation. For the combustion and pyrolysis of all three fuels, the PI spectra can be fit reasonably well with contributions from four radical isomers: benzyl, tropyl, vinylcyclopentadienyl, and o-tolyl. Although there are significant experimental uncertainties in the isomeric speciation of C7H7, the results clearly demonstrate that the isomeric composition of C7H7 strongly depends on the combustion or pyrolysis conditions and the fuel or precursors. Fits to the PI spectra using reference curves for these isomers suggest that all of these isomers may contribute to m/z 91 in butane and methane flames, but only benzyl and vinylcyclopentadienyl contribute to the C7H7 isomer signal in the ethylene flame. Only tropyl and benzyl appear to play a role during pyrolytic particle formation from ethylene, and only tropyl, vinylcyclopentadienyl, and o-tolyl appear to participate during particle formation from butane pyrolysis. There also seems to be a contribution from an isomer with an ionization energy below 7.5 eV for the flames but not for the pyrolysis conditions. Kinetic models with updated and new reactions and rate coefficients for the C7H7 reaction network predict benzyl, tropyl, vinylcyclopentadienyl, and o-tolyl to be the primary C7H7 isomers and predict negligible contributions from other C7H7 isomers. These updated models provide better agreement with the measurements than the original versions of the models but, nonetheless, underpredict the relative concentrations of tropyl, vinylcyclopentadienyl, and o-tolyl in both flames and pyrolysis and overpredict benzyl in pyrolysis. Our results suggest that there are additional important formation pathways for the vinylcyclopentadienyl, tropyl, and o-tolyl radicals and/or loss pathways for the benzyl radical that are currently unaccounted for in the present models.

Distinguishing Gas-Phase and Nanoparticle Contributions to Small-Angle X-ray Scattering in Reacting Aerosol Flows.

We have developed a strategy for distinguishing between small-angle X-ray scattering (SAXS) from gas-phase species and newly formed nanoparticles in mixed gas- and particle-phase reacting flows. This methodology explicitly accounts for temperature-dependent scattering from gases. We measured SAXS in situ in a sooting linear laminar partially premixed co-flow ethylene/air diffusion flame. The scattering signal demonstrates a downward curvature as a function of the momentum transfer (q) at q values of 0.2-0.57 Å-1. The q-dependent curvature is consistent with the Debye equation and the independent-atom model for gas-phase scattering. This behavior can also be modeled using the Guinier approximation and could be characterized as a Guinier knee for gas-phase scattering. The Guinier functional form can be fit to the scattering signal in this q range without a priori knowledge of the gas-phase composition, enabling estimation of the gas-phase contribution to the scattering signal while accounting for changes in the gas-phase composition and temperature. We coupled the SAXS measurements with in situ temperature measurements using coherent anti-Stokes Raman spectroscopy. This approach to characterizing the gas-phase SAXS signal provides a physical basis for distinguishing among the contributions to the scattering signal from the instrument function, flame gases, and nanoparticles. The results are particularly important for the analysis of the SAXS signal in the q range associated with particles in the size range of 1-6 nm.

Toward verifying fossil fuel CO2 emissions with the CMAQ model: motivation, model description and initial simulation.

UNLABELLED: Motivated by the question of whether and how a state-of-the-art regional chemical transport model (CTM) can facilitate characterization of CO2 spatiotemporal variability and verify CO2 fossil-fuel emissions, we for the first time applied the Community Multiscale Air Quality (CMAQ) model to simulate CO2. This paper presents methods, input data, and initial results for CO2 simulation using CMAQ over the contiguous United States in October 2007. Modeling experiments have been performed to understand the roles of fossil-fuel emissions, biosphere-atmosphere exchange, and meteorology in regulating the spatial distribution of CO2 near the surface over the contiguous United States. Three sets of net ecosystem exchange (NEE) fluxes were used as input to assess the impact of uncertainty of NEE on CO2 concentrations simulated by CMAQ. Observational data from six tall tower sites across the country were used to evaluate model performance. In particular, at the Boulder Atmospheric Observatory (BAO), a tall tower site that receives urban emissions from Denver CO, the CMAQ model using hourly varying, high-resolution CO2 fossil-fuel emissions from the Vulcan inventory and Carbon Tracker optimized NEE reproduced the observed diurnal profile of CO2 reasonably well but with a low bias in the early morning. The spatial distribution of CO2 was found to correlate with NO(x), SO2, and CO, because of their similar fossil-fuel emission sources and common transport processes. These initial results from CMAQ demonstrate the potential of using a regional CTM to help interpret CO2 observations and understand CO2 variability in space and time. The ability to simulate a full suite of air pollutants in CMAQ will also facilitate investigations of their use as tracers for CO2 source attribution. This work serves as a proof of concept and the foundation for more comprehensive examinations of CO2 spatiotemporal variability and various uncertainties in the future. IMPLICATIONS: Atmospheric CO2 has long been modeled and studied on continental to global scales to understand the global carbon cycle. This work demonstrates the potential of modeling and studying CO2 variability at fine spatiotemporal scales with CMAQ, which has been applied extensively, to study traditionally regulated air pollutants. The abundant observational records of these air pollutants and successful experience in studying and reducing their emissions may be useful for verifying CO2 emissions. Although there remains much more to further investigate, this work opens up a discussion on whether and how to study CO2 as an air pollutant.

Integrated fiber optic incoherent broadband cavity enhanced absorption spectroscopy detector for near-IR absorption measurements of nanoliter samples.

An integrated fiber-optic sensor is described that uses incoherent broadband cavity enhanced absorption spectroscopy for sensitive detection of aqueous samples in nanoliter volumes. Absorption was measured in a 100 µm gap between the ends of two short segments of multimode graded-index fiber that were integrated into a capillary using a precision machined V-grooved fixture that allowed for passive fiber alignment. The other ends of the fibers were coated with dielectric mirrors to form a 9.5 cm optical resonator. Light from a fiber-coupled superluminescent diode was directly coupled into one end of the cavity, and transmission was measured using a fiber-coupled silicon photodiode. Dilute aqueous solutions of near infrared dye were used to determine the minimum detectable absorption change of 2.4×10(-4) under experimental conditions in which pressure fluctuations limited performance. We also determined that the absolute minimum detectable absorption change would be 1.6×10(-5) for conditions of constant pressure in which absorption measurement is limited by electronic and optical noise. Tolerance requirements for alignment are also presented.

Application of laser photofragmentation-resonance enhanced multiphoton ionization to ion mobility spectrometry.

We demonstrate detection of nitro-containing compounds with laser photofragmentation (PF) coupled with resonance enhanced multiphoton ionization (REMPI) and ion mobility spectrometry (IMS). In PF-REMPI, a laser dissociates the parent molecules, producing fragments that can then be ionized by absorption of additional laser photons. The production of these ions strongly depends on the wavelength of laser light, with ion yields corresponding to the absorption spectrum of the fragments [nitric oxide (NO) in the present case]. Combining IMS with PF-REMPI provides further specificity, separating ions according to their mobilities through an atmospheric-pressure drift tube. In this work, we use a pulsed UV laser to examine the characteristics of atmospheric-pressure PF-REMPI, the chemistry occurring in the ionization region and drift tube, and the viability of detecting ions created by both resonance-enhanced and nonresonant ionization. Probing NO in a helium-nitrogen bath, we demonstrate that the detection of ions displays single-shot response to changes in ion generation, with an ion extraction-to-collection efficiency of approximately 12%. We then evaluate the sensitivity and specificity of PF-REMPI/IMS as applied to the detection of both the explosive surrogate 2, 4-dinitrotoluene and the nuisance compound nitrobenzene.

Frequency-locked, injection-seeded, pulsed narrowband optical parametric generator.

A frequency-locked, injection-seeded, pulsed optical parametric generator (OPG) has been developed for short-range infrared differential absorption lidar (DIAL) applications. The periodically poled lithium niobate OPG is pumped by a passively Q-switched Nd:YAG microlaser and is seeded by a distributed feedback (DFB) diode laser. The OPG is designed for DIAL measurement of a narrow R-branch transition of methane at 3.2704 microm. The output of the OPG is a two-pulse sequence with a 100-micros temporal separation between the pulses, where the first pulse is absorbed by methane and the second pulse is not absorbed. The first pulse is actively locked to the methane absorption feature by use of the derivative of the transmission spectrum through a reference cell. Although the device was not optimized for output power, the 3.27-microm OPG output energies of the first and second pulses are 5.5 and 5.9 microJ, respectively, producing 21 mW when operated at 1818 Hz.