Matthew F. Campbell

Formation and emission of large furans and oxygenated hydrocarbons from flames

Significance Furans and related large oxygenated organic carbon species (OC) are highly toxic pollutants. Their integration into soot particles may greatly enhance soot’s hygroscopicity, leading to regional and global climate change. We show that furans are the primary oxygenated functional group on soot formed in hydrocarbon combustion and report a reaction scheme that elucidates the interplay between nonoxygenated and oxygenated hydrocarbons. We expect this reaction pathway to be important in many hydrocarbon oxidation systems spanning geosciences, astrophysics, and energy research. We discovered ∼100 oxygenated species previously unaccounted for in hydrocarbon models. This study advances the understanding of the oxidation chemistry of OC, which is critical to many processes, from controlling emissions of toxic combustion by-products to reducing anthropogenic climate change. Many oxygenated hydrocarbon species formed during combustion, such as furans, are highly toxic and detrimental to human health and the environment. These species may also increase the hygroscopicity of soot and strongly influence the effects of soot on regional and global climate. However, large furans and associated oxygenated species have not previously been observed in flames, and their formation mechanism and interplay with polycyclic aromatic hydrocarbons (PAHs) are poorly understood. We report on a synergistic computational and experimental effort that elucidates the formation of oxygen-embedded compounds, such as furans and other oxygenated hydrocarbons, during the combustion of hydrocarbon fuels. We used ab initio and probabilistic computational techniques to identify low-barrier reaction mechanisms for the formation of large furans and other oxygenated hydrocarbons. We used vacuum-UV photoionization aerosol mass spectrometry and X-ray photoelectron spectroscopy to confirm these predictions. We show that furans are produced in the high-temperature regions of hydrocarbon flames, where they remarkably survive and become the main functional group of oxygenates that incorporate into incipient soot. In controlled flame studies, we discovered ∼100 oxygenated species previously unaccounted for. We found that large alcohols and enols act as precursors to furans, leading to incorporation of oxygen into the carbon skeletons of PAHs. Our results depart dramatically from the crude chemistry of carbon- and oxygen-containing molecules previously considered in hydrocarbon formation and oxidation models and spearhead the emerging understanding of the oxidation chemistry that is critical, for example, to control emissions of toxic and carcinogenic combustion by-products, which also greatly affect global warming.

A second-generation constrained reaction volume shock tube.

We have developed a shock tube that features a sliding gate valve in order to mechanically constrain the reactive test gas mixture to an area close to the shock tube endwall, separating it from a specially formulated non-reactive buffer gas mixture. This second-generation Constrained Reaction Volume (CRV) strategy enables near-constant-pressure shock tube test conditions for reactive experiments behind reflected shocks, thereby enabling improved modeling of the reactive flow field. Here we provide details of the design and operation of the new shock tube. In addition, we detail special buffer gas tailoring procedures, analyze the buffer/test gas interactions that occur on gate valve opening, and outline the size range of fuels that can be studied using the CRV technique in this facility. Finally, we present example low-temperature ignition delay time data to illustrate the CRV shock tubes performance.

Evolution of maturity levels of the particle surface and bulk during soot growth and oxidation in a flame

ABSTRACT We performed a study of the evolution of soot composition and fine structure, i.e., maturity level, in an atmospheric ethylene-air diffusion flame. We used laser-induced incandescence (LII) to provide information about maturity level of the bulk primary particle and X-ray photoelectron spectroscopy (XPS) to provide complementary information about particle-surface-maturity level. The results demonstrate that the bulk material and the particle surface evolve separately in the flame. Increased soot-maturity level is associated with increased long-range order of the particle fine structure. This increased order leads to an increase in the absorption cross-section in the visible and near-infrared and a shift of the absorption to longer wavelengths with increasing maturity level of the bulk particle. These trends result in a decrease in the dispersion exponent (?) and increase in the absorption cross-section scaling factor (?), as inferred from LII measurements. LII measurements demonstrate that bulk-maturity level increases with height-above-the-burner (HAB) until it reaches a plateau in the center of the flame at the maximum in the soot volume fraction. Bulk-maturity level only slightly decreases as soot is oxidized at larger HABs. Increased maturity level also leads to an increase in long-range sp2 hybridization. XPS measurements of the sp2/defect ratio demonstrate an increase in soot surface-maturity level with increasing HAB, but the surface-maturity level increases more gradually with HAB than the bulk-maturity level. Whereas the bulk-fine-structure order decreases slightly in the oxidation region, the surface order decreases dramatically, indicating that oxidation occurs preferentially at the surface under these conditions. Copyright

A Second-Generation Aerosol Shock Tube and Its Use in Studying Ignition Delay Times of Large Biodiesel Surrogates

Biodiesel is an oxygenated fuel composed of large fatty acid methyl esters (FAME) and is derived from plant oils and animal fats. Its combustion is associated with significant decreases in pollutant emissions such as hydrocarbons, particulate matter, and carbon monoxide relative to fossil diesel [1]. However, combustion of methyl esters in diesel engines has yielded several troublesome problems, including changes in ignition timing and significant increases in nitrogen oxide emissions [2]. These problems can be overcome by developing and applying detailed chemical kinetic models to the design of diesel engines and fuel blends [3, 4]. Chemical kinetic models are based on experimental combustion data, such as those gathered in jet-stirred reactors, rapid compression machines, flow reactors, laminar flame burners, and shock tube experiments.

Rapid Chemiluminescent Imaging Behind Reflected Shock Waves

Current shock tube combustion experiments generally assume that the test environment behind a reflected shock wave is quiescent and that ignition processes progress uniformly over the entire test volume. However, various past investigations, including those based on schlieren data and sidewall imaging [1, 2], have observed nonuniform ignition in certain test regimes. Here, we use both conventional diagnostics (pressure, emission, and laser absorption) and a high-speed chemiluminescent imaging system to investigate the ignition behavior of n-heptane/oxygen/argon in shock tubes at long test times (greater than 2 ms), in an attempt to map the boundary of uniform and nonuniform ignition behavior in one of our shock tubes.

Critical Assessment of Photoionization Efficiency Measurements for Characterization of Soot-Precursor Species

We present a critical evaluation of photoionization efficiency (PIE) measurements coupled with aerosol mass spectrometry for the identification of condensed soot-precursor species extracted from a premixed atmospheric-pressure ethylene/oxygen/nitrogen flame. Definitive identification of isomers by any means is complicated by the large number of potential isomers at masses likely to comprise particles at flame temperatures. This problem is compounded using PIE measurements by the similarity in ionization energies and PIE-curve shapes among many of these isomers. Nevertheless, PIE analysis can provide important chemical information. For example, our PIE curves show that neither pyrene nor fluoranthene alone can describe the signal from C16H10 isomers and that coronene alone cannot describe the PIE signal from C24H12 species. A linear combination of the reference PIE curves for pyrene and fluoranthene yields good agreement with flame-PIE curves measured at 202 u, which is consistent with pyrene and fluoranthene being the two major C16H10 isomers in the flame samples, but does not provide definite proof. The suggested ratio between fluoranthene and pyrene depends on the sampling conditions. We calculated the values of the adiabatic-ionization energy (AIE) of 24 C16H10 isomers. Despite the small number of isomers considered, the calculations show that the differences in AIEs between several of the isomers can be smaller than the average thermal energy at room temperature. The calculations also show that PIE analysis can sometimes be used to separate hydrocarbon species into those that contain mainly aromatic rings and those that contain significant aliphatic content for species sizes investigated in this study. Our calculations suggest an inverse relationship between AIE and the number of aromatic rings. We have demonstrated that further characterization of precursors can be facilitated by measurements that test species volatility.

Dependence of calculated postshock thermodynamic variables on vibrational equilibrium and input uncertainty

The purpose of this article is to explore the dependence of calculated postshock thermodynamic properties in shock tube experiments upon the vibrational state of the test gas and upon the uncertain...

Photoionization Efficiencies of Five Polycyclic Aromatic Hydrocarbons

We have measured photoionization-efficiency curves for pyrene, fluoranthene, chrysene, perylene, and coronene in the photon energy range of 7.5-10.2 eV and derived their photoionization cross-section curves in this energy range. All measurements were performed using tunable vacuum ultraviolet (VUV) radiation generated at the Advanced Light Source synchrotron at Lawrence Berkeley National Laboratory. The VUV radiation was used for photoionization, and detection was performed using a time-of-flight mass spectrometer. We measured the photoionization efficiency of 2,5-dimethylfuran simultaneously with those of pyrene, fluoranthene, chrysene, perylene, and coronene to obtain references of the photon flux during each measurement from the known photoionization cross-section curve of 2,5-dimethylfuran.

NT security in an open academic environment

Stanford Linear Accelerator Center (SLAC) was faced with the need to secure its PeopleSoft/Oracle business system in an academic environment which only has a minimal firewall. To provide protected access to the database servers for NT-based users all over the site while not hindering the labs open connectivity with the Internet, we implemented a pseudo three-tier architecture for PeopleSoft with Windows Terminal Server and Citrix MetaFrame technology. The client application and Oracle database were placed behind a firewall, and access was granted via an encrypted link to a thin client. Authentication in the future will be through two-factor token cards. NT workstations in the business system unit were further secured through switched network ports and an automated installation process that included SMB signing and disabling LM Authentication in favor of NTLMv2. The hardened workstations then accessed the business system through the Citrix Secure ICA client. How these security measures affected our mixed environment (Windows9x, Samba, Transarc AFS clients, Pathworks, developers, researchers) is discussed.