Richard C. Striebich

Simulations of Flowing Mildly-Cracked Normal Alkanes Incorporating Proportional Product Distributions

Hydrocarbon fuels have been used as a cooling media in aircraft jet engines for many years. However, advanced aircraft engines are reaching a practical heat transfer limit beyond which the sensible heat transfer provided by fuels is no longer adequate. One solution is to use an endothermic fuel that absorbs heat through chemical reactions. A two-dimensional computational model is developed to calculate the heat and mass transport associated with a flowing fuel using a unique global chemical kinetics model. Most past models do not account for changes in the chemical composition of a flowing fuel and also do not adequately predict flow properties in the supercritical regime. The two-dimensional computational model presented calculates the changing flow properties of a supercritical reacting fuel by use of experimentally derived proportional product distributions. The calculations are validated by measured experimental data obtained from a flow reactor in which n-decane and n-dodecane are mildly cracked. It is believed that these simulations will assist the fundamental understanding of high-temperature fuel flow experiments.

Semi-volatile and particulate emissions from the combustion of alternative diesel fuels

Motor vehicle emissions are a major anthropogenic source of air pollution and contribute to the deterioration of urban air quality. In this paper, we report results of a laboratory investigation of particle formation from four different alternative diesel fuels, namely, compressed natural gas (CNG), dimethyl ether (DME), biodiesel, and diesel, under fuel-rich conditions in the temperature range of 800-1200 degrees C at pressures of approximately 24 atm. A single pulse shock tube was used to simulate compression ignition (CI) combustion conditions. Gaseous fuels (CNG and DME) were exposed premixed in air while liquid fuels (diesel and biodiesel) were injected using a high-pressure liquid injector. The results of surface analysis using a scanning electron microscope showed that the particles formed from combustion of all four of the above-mentioned fuels had a mean diameter less than 0.1 microm. From results of gravimetric analysis and fuel injection size it was found that under the test conditions described above the relative particulate yields from CNG, DME, biodiesel, and diesel were 0.30%. 0.026%, 0.52%, and 0.51%, respectively. Chemical analysis of particles showed that DME combustion particles had the highest soluble organic fraction (SOF) at 71%, followed by biodiesel (66%), CNG (38%) and diesel (20%). This illustrates that in case of both gaseous and liquid fuels, oxygenated fuels have a higher SOF than non-oxygenated fuels.

High-temperature degradation of polybrominated flame retardant materials

Abstract This experimental study examined gas-phase oxidative and pyrolytic thermal degradation of three brominated flame retardant materials in a high-temperature flow reactor. Br-benzenes, Br-phenols, PBDDs and PBDFs were formed at intermediate temperatures and subsequently destroyed by 800°C.

Transcriptional profiling suggests that multiple metabolic adaptations are required for effective proliferation of Pseudomonas aeruginosa in jet fuel.

Fuel is a harsh environment for microbial growth. However, some bacteria can grow well due to their adaptive mechanisms. Our goal was to characterize the adaptations required for Pseudomonas aeruginosa proliferation in fuel. We have used DNA-microarrays and RT-PCR to characterize the transcriptional response of P. aeruginosa to fuel. Transcriptomics revealed that genes essential for medium- and long-chain n-alkane degradation including alkB1 and alkB2 were transcriptionally induced. Gas chromatography confirmed that P. aeruginosa possesses pathways to degrade different length n-alkanes, favoring the use of n-C11-18. Furthermore, a gamut of synergistic metabolic pathways, including porins, efflux pumps, biofilm formation, and iron transport, were transcriptionally regulated. Bioassays confirmed that efflux pumps and biofilm formation were required for growth in jet fuel. Furthermore, cell homeostasis appeared to be carefully maintained by the regulation of porins and efflux pumps. The Mex RND efflux pumps were required for fuel tolerance; blockage of these pumps precluded growth in fuel. This study provides a global understanding of the multiple metabolic adaptations required by bacteria for survival and proliferation in fuel-containing environments. This information can be applied to improve the fuel bioremediation properties of bacteria.

Hydroprocessed Renewable Jet Fuel Evaluation, Performance, and Emissions in a T63 Turbine Engine

Due to potential beneficial environmental impacts and increased supply availability, alternative fuels derived from renewable resources are evolving on the forefront as unconventional substitutes for fossil fuel. Focus is being given to the evaluation and certification of Hydroprocessed Renewable Jet (HRJ), a fuel produced from animal fat and/or plant oils (triglycerides) by hydroprocessing, as the next potential synthetic aviation fuel. Extensive efforts have recently been performed at the Air Force Research Laboratory (AFRL) at Wright Patterson Air Force Base (WPAFB) to evaluate the potential of two HRJ fuels produced from camelina and tallow feedstocks. These have included characterization of the fuel chemical, physical fuel characteristics and Fit-for-Purpose properties (FFP). The present effort describes general combustion performance and the emission propensity of a T63-A-700 Allison turbine engine operated on the HRJs and 50/50 (by volume) HRJ/JP-8 fuel blends relative to a specification JP-8. In addition, engine and emission testing with a blend of the tallow-derived HRJ and 16% bio-derived aromatic components was completed. Fundamental engine performance characterization allows for determination of the suitability of potential synthetic fuels while quantitation of gaseous and particulate matter emissions provides an assessment of the potential environmental impact compared to current petroleum-derived fuels. In addition, an extended 150 h endurance test was performed using a 50/50 blend of tallow-derived HRJ with JP-8 to evaluate the long-term operation of the engine with the synthetic fuel blend. This paper discusses the laboratory testing performed to characterize HRJs and results from the basic engine operability and emissions studies of the alternative fuel blends.

Trace-level measurement of complex combustion effluents and residues using multidimensional gas chromatography-mass spectrometry (MDGC-MS)

The identification and quantitation of non-method-specific target analytes have greater importance with respect to EPAs current combustion strategy. The risk associated with combustion process emissions must now be characterized. EPA has recently released draft guidance on procedures for the collection of emissions data to support and augment site-specific risk assessments (SSRAs) as part of the hazardous waste incineration permitting process. This guidance includes methodology for quantifying total organic (TO) emissions as a function of compound volatility. The ultimate intent is to compare the amount of organic material identified and quantified by target analyte-specific methodologies to organic emissions quantified by the TO methodology. The greater the amount accounted for by the target analyte-specific methodologies, the less uncertainty may be associated with the SSRAs. A limitation of this approach is that the target analyte-specific methodologies do not routinely quantify compounds of low toxicological interest; nor do they target products of incomplete combustion (PICs). Thus, the analysis can miss both toxic and non-toxic compounds. As a result, it is unknown whether the uncharacterized fraction of the TO emission possesses toxic properties. The hypothesis that we propose to test is that organic emissions and organics extracted from particulate matter (PM) are more complex than standard GC-MS-based instrumentation can currently measure. This complexity can affect quantitation for toxic compounds, thereby potentially affecting risk assessments. There is a pressing need to better characterize these organic emissions from hazardous waste incinerators and PM extracts from various other combustion sources. We will demonstrate that multidimensional gas chromatography-mass spectrometry (MDGC-MS) procedures significantly improve chromatographic separation for complex environmental samples. Sequential repetitive heart-cutting MDGC, with coupled mass spectrometry will be shown to be a complete analysis technique. The ability of this technique to disengage components from complex mixtures taken from hazardous and municipal waste incinerators will be shown.

Transcriptomic Analyses Elucidate Adaptive Differences of Closely Related Strains of Pseudomonas aeruginosa in Fuel

ABSTRACT Pseudomonas aeruginosa can utilize hydrocarbons, but different strains have various degrees of adaptation despite their highly conserved genome. P. aeruginosa ATCC 33988 is highly adapted to hydrocarbons, while P. aeruginosa strain PAO1, a human pathogen, is less adapted and degrades jet fuel at a lower rate than does ATCC 33988. We investigated fuel-specific transcriptomic differences between these strains in order to ascertain the underlying mechanisms utilized by the adapted strain to proliferate in fuel. During growth in fuel, the genes related to alkane degradation, heat shock response, membrane proteins, efflux pumps, and several novel genes were upregulated in ATCC 33988. Overexpression of alk genes in PAO1 provided some improvement in growth, but it was not as robust as that of ATCC 33988, suggesting the role of other genes in adaptation. Expression of the function unknown gene PA5359 from ATCC 33988 in PAO1 increased the growth in fuel. Bioinformatic analysis revealed that PA5359 is a predicted lipoprotein with a conserved Yx(FWY)xxD motif, which is shared among bacterial adhesins. Overexpression of the putative resistance-nodulation-division (RND) efflux pump PA3521 to PA3523 increased the growth of the ATCC 33988 strain, suggesting a possible role in fuel tolerance. Interestingly, the PAO1 strain cannot utilize n-C8 and n-C10. The expression of green fluorescent protein (GFP) under the control of alkB promoters confirmed that alk gene promoter polymorphism affects the expression of alk genes. Promoter fusion assays further confirmed that the regulation of alk genes was different in the two strains. Protein sequence analysis showed low amino acid differences for many of the upregulated genes, further supporting transcriptional control as the main mechanism for enhanced adaptation. IMPORTANCE These results support that specific signal transduction, gene regulation, and coordination of multiple biological responses are required to improve the survival, growth, and metabolism of fuel in adapted strains. This study provides new insight into the mechanistic differences between strains and helpful information that may be applied in the improvement of bacterial strains for resistance to biotic and abiotic factors encountered during bioremediation and industrial biotechnological processes.

Investigation of waste incineration of fluorotelomer-based polymers as a potential source of PFOA in the environment.

In light of the widespread presence of perfluorooctanoic acid (PFOA) in the environment, a comprehensive laboratory-scale study has developed data requested by the U.S. Environmental Protection Agency (EPA) to determine whether municipal and/or medical waste incineration of commercial fluorotelomer-based polymers (FTBPs) at end of life is a potential source of PFOA that may contribute to environmental and human exposures. The study was divided into two phases (I and II) and conducted in accordance with EPA Good Laboratory Practices (GLPs) as described in the quality assurance project plan (QAPP) for each phase. Phase I testing determined that the PFOA transport efficiency across the thermal reactor system to be used in Phase II was greater than 90%. Operating at 1000°C over 2s residence time with 3.2-6.6mgdscm(-1) hydrogen fluoride (HF), corrected to 7% oxygen (O2), and continuously monitored exhaust oxygen of 13%, Phase II testing of the FTBP composites in this thermal reactor system yielded results demonstrating that waste incineration of fluorotelomer-based polymers does not result in the formation of detectable levels of PFOA under conditions representative of typical municipal waste combustor (MWC) and medical waste incinerator (MWI) operations in the U.S. Therefore, waste incineration of these polymers is not expected to be a source of PFOA in the environment.

A comprehensive multi-omics approach uncovers adaptations for growth and survival of Pseudomonas aeruginosa on n-alkanes.

BackgroundExamination of complex biological systems has long been achieved through methodical investigation of the system’s individual components. While informative, this strategy often leads to inappropriate conclusions about the system as a whole. With the advent of high-throughput “omic” technologies, however, researchers can now simultaneously analyze an entire system at the level of molecule (DNA, RNA, protein, metabolite) and process (transcription, translation, enzyme catalysis). This strategy reduces the likelihood of improper conclusions, provides a framework for elucidation of genotype-phenotype relationships, and brings finer resolution to comparative genomic experiments. Here, we apply a multi-omic approach to analyze the gene expression profiles of two closely related Pseudomonas aeruginosa strains grown in n-alkanes or glycerol.ResultsThe environmental P. aeruginosa isolate ATCC 33988 consumed medium-length (C10–C16) n-alkanes more rapidly than the laboratory strain PAO1, despite high genome sequence identity (average nucleotide identity >99%). Our data shows that ATCC 33988 induces a characteristic set of genes at the transcriptional, translational and post-translational levels during growth on alkanes, many of which differ from those expressed by PAO1. Of particular interest was the lack of expression from the rhl operon of the quorum sensing (QS) system, resulting in no measurable rhamnolipid production by ATCC 33988. Further examination showed that ATCC 33988 lacked the entire lasI/lasR arm of the QS response. Instead of promoting expression of QS genes, ATCC 33988 up-regulates a small subset of its genome, including operons responsible for specific alkaline proteases and sphingosine metabolism.ConclusionThis work represents the first time results from RNA-seq, microarray, ribosome footprinting, proteomics, and small molecule LC-MS experiments have been integrated to compare gene expression in bacteria. Together, these data provide insights as to why strain ATCC 33988 is better adapted for growth and survival on n-alkanes.

Draft Genome Sequence of Pseudomonas frederiksbergensis SI8, a Psychrotrophic Aromatic-Degrading Bacterium

ABSTRACT Pseudomonas frederiksbergensis strain SI8 is a psychrotrophic bacterium capable of efficient aerobic degradation of aromatic hydrocarbons. The draft genome of P. frederiksbergensis SI8 is 6.57 Mb in size, with 5,904 coding sequences and 60.5% G+C content. The isopropylbenzene (cumene) degradation pathway is predicted to be present in P. frederiksbergensis SI8.