PECVD of carbon nanostructures in hydrocarbon-based RF plasmas

Different aspects of the plasma-enhanced chemical vapor deposition of various carbon nanostructures in the ionized gas phase of high-density, low-temperature reactive plasmas of Ar+H2+CH4 gas mixtures are studied. The growth techniques, surface morphologies, densities and fluxes of major reactive species in the discharge, and effects of the transport of the plasma-grown nanoparticles through the near-substrate plasma sheath are examined. Possible growth precursors of the carbon nanostructures are also discussed. In particular, the experimental and numerical results indicate that it is likely that the aligned carbon nanotip structures are predominantly grown by the molecular and radical units, whereas the plasma-grown nanoparticles are crucial components of polymorphous carbon films.

Influence of traffic characteristics on polycyclic aromatic hydrocarbon build-up on urban road surfaces

Traffic is one of the prominent sources of polycyclic aromatic hydrocarbons (PAHs) and road surfaces are the most critical platform for stormwater pollution. Build-up of pollutants on road surfaces was the focus of this research study. The study found that PAHs build-up on road surfaces primarily originate from traffic activities, specifically gasoline powered vehicles. Other sources such as diesel vehicles, industrial oil combustion and incineration were also found to contribute to the PAH build-up. Additionally, the study explored the linkages between concentrations of PAHs and traffic characteristics such as traffic volume, vehicle mix and traffic flow. While traffic congestion was found to be positively correlated with 6- ring and 5- ring PAHs in road build-up, it was negatively correlated with 3-ring and 4 ring PAHs. The absence of positive correlation between 3-ring and 4-ring PAHs and traffic parameters is attributed to the propensity of these relatively volatile PAHs to undergo re-suspension and evaporation. The outcomes of this study are expected to contribute effective transport and land use planning for the prevention of PAH pollution in the urban environment.

Polymorphisms in a desaturase 2 ortholog associate with cuticular hydrocarbon and male mating success variation in a natural population of Drosophila serrata

Elucidating the nature of genetic variation underlying both sexually selected traits and the fitness components of sexual selection is essential to understanding the broader consequences of sexual selection as an evolutionary process. To date, there have been relatively few attempts to connect the genetic variance in sexually selected traits with segregating DNA sequence polymorphisms. We set out to address this in a well-characterized sexual selection system - the cuticular hydrocarbons (CHCs) of Drosophila serrata - using an indirect association study design that allowed simultaneous estimation of the genetic variance in CHCs, sexual fitness and single nucleotide polymorphism (SNP) effects in an outbred population. We cloned and sequenced an ortholog of the D. melanogaster desaturase 2 gene, previously shown to affect CHC biosynthesis in D. melanogaster, and associated 36 SNPs with minor allele frequencies > 0.02 with variance in CHCs and sexual fitness. Three SNPs had significant multivariate associations with CHC phenotype (q-value < 0.05). At these loci, minor alleles had multivariate effects on CHCs that were weakly associated with the multivariate direction of sexual selection operating on these traits. Two of these SNPs had pleiotropic associations with male mating success, suggesting these variants may underlie responses to sexual selection due to this locus. There were 15 significant male mating success associations (q-value < 0.1), and interestingly, we detected a nonrandom pattern in the relationship between allele frequency and direction of effect on male mating success. The minor-frequency allele usually reduced male mating success, suggesting a positive association between male mating success and total fitness at this locus.

Self-assembly of a halogenated molecule on oxide-passivated Cu(110)

The supramolecular self-assembly of brominated molecules was investigated and compared on Cu(110) and Cu(110)[BOND]O(2×1) surfaces under ultrahigh vacuum. By using scanning tunnelling microscopy, we show that brominated molecules form a disordered structure on Cu(110), whereas a well-ordered supramolecular network is observed on the Cu(110)[BOND]O(2×1) surface. The different adsorption behaviors of these two surfaces are described in terms of weakened molecule–substrate interactions on Cu(110)[BOND]O(2×1) as opposed to bare Cu(110). The effect of oxygen-passivation is to suppress debromination and it can be a convenient approach for investigating other self-assembly processes on copper-based substrates.

When using small samples to evaluate hydrocarbon reservoirs, proceed with caution

Small-angle neutron scattering (SANS) and ultra-small angle neutron scattering (USANS) with contrast matching techniques (Melnichenko and others, 2012) were used to investigate size distribution and gas accessibility in pores in an approximately 10.6 cm long Mississippian Barnett Shale butt core from the Fort Worth Basin, Texas, USA. SANS and USANS measurements record scattering from all pores, both open and closed, in the size range 10nm - ~10 μ. The techniques can also be used to determine the material that contains pores and the number of pores as a function of size. By injecting deuterated methane gas (CD4) at contrast matching pressure it is possible to distinguish which pores are accessible, or open, to fluids and which ones are not.

Intermolecular interactions in the formation of aromatic hydrocarbon dimers

Both short-range and long-range intermolecular interaction energies between two aromatic hydrocarbon molecules, both in their ground state, separated by a range of interplanar distances of 3 ∼ 4 Aring, are estimated using the standard perturbation theory. The results show that aromatic hydrocarbons can form weak sandwich dimers with larger separation between them than is normally believed in their excimers. The non-sandwich form of dimer in which the long in-plane axes of the monomers are parallel and their short in-plane axes inclined, represents an unstable orientation because this form can pass to the perfect sandwich form without an energy barrier.

Ignition delay studies on hydrocarbon fuel with and without additives

Single pulse shock tube facility has been developed in the High Temperature Chemical Kinetics Lab, Aerospace Engineering Department, to carry out ignition delay studies and spectroscopic investigations of hydrocarbon fuels. Our main emphasis is on measuring ignition delay through pressure rise and by monitoring CH emission for various jet fuels and finding suitable additives for reducing the delay. Initially the shock tube was tested and calibrated by measuring the ignition delay of C2H6-O2 mixture. The results are in good agreement with earlier published works. Ignition times of exo-tetrahdyrodicyclopentadiene (C10H16), which is a leading candidate fuel for scramjet propulsion has been studied in the reflected shock region in the temperature range 1250 - 1750 K with and without adding Triethylamine (TEA). Addition of TEA results in substantial reduction of ignition delay of C10H16.

Functional genes and gene array analysis as tools for monitoring hydrocarbon biodegradation

Bioremediation, which is the exploitation of the intrinsic ability of environmental microbes to degrade and remove harmful compounds from nature, is considered to be an environmentally sustainable and cost-effective means for environmental clean-up. However, a comprehensive understanding of the biodegradation potential of microbial communities and their response to decontamination measures is required for the effective management of bioremediation processes. In this thesis, the potential to use hydrocarbon-degradative genes as indicators of aerobic hydrocarbon biodegradation was investigated. Small-scale functional gene macro- and microarrays targeting aliphatic, monoaromatic and low molecular weight polyaromatic hydrocarbon biodegradation were developed in order to simultaneously monitor the biodegradation of mixtures of hydrocarbons. The validity of the array analysis in monitoring hydrocarbon biodegradation was evaluated in microcosm studies and field-scale bioremediation processes by comparing the hybridization signal intensities to hydrocarbon mineralization, real-time polymerase chain reaction (PCR), dot blot hybridization and both chemical and microbiological monitoring data. The results obtained by real-time PCR, dot blot hybridization and gene array analysis were in good agreement with hydrocarbon biodegradation in laboratory-scale microcosms. Mineralization of several hydrocarbons could be monitored simultaneously using gene array analysis. In the field-scale bioremediation processes, the detection and enumeration of hydrocarbon-degradative genes provided important additional information for process optimization and design. In creosote-contaminated groundwater, gene array analysis demonstrated that the aerobic biodegradation potential that was present at the site, but restrained under the oxygen-limited conditions, could be successfully stimulated with aeration and nutrient infiltration. During ex situ bioremediation of diesel oil- and lubrication oil-contaminated soil, the functional gene array analysis revealed inefficient hydrocarbon biodegradation, caused by poor aeration during composting. The functional gene array specifically detected upper and lower biodegradation pathways required for complete mineralization of hydrocarbons. Bacteria representing 1 % of the microbial community could be detected without prior PCR amplification. Molecular biological monitoring methods based on functional genes provide powerful tools for the development of more efficient remediation processes. The parallel detection of several functional genes using functional gene array analysis is an especially promising tool for monitoring the biodegradation of mixtures of hydrocarbons.

Hydrocarbon oxidation and three-way catalytic activity on a single step directly coated cordierite monolith: High catalytic activity of Ce0.98Pd0.02O2−δ

Catalytic activity of cordierite honeycomb by a completely new coating method for the oxidation of major hydrocarbons in exhaust gas is reported here. The new coating process consists of (a) dipping and growing γ-Al2O3 on cordierite by combustion of monolith dipped in the aqueous solution of Al(NO3)3 and oxalyldihydrazide (ODH) (or glycine) at 600 °C and active catalyst phase Ce0.98Pd0.02O2−δ on γ-Al2O3-coated cordierite again by combustion of monolith dipped in the aqueous solution of ceric ammonium nitrate, ODH and 1.2 × 10−3 M PdCl2 solution at 500 °C. Weight of active catalyst can be varied from 0.02 wt% to 2 wt% which is sufficient but can be loaded even up to 12 wt% by repeating dip dry combustion. Adhesion of catalyst to cordierite surface is via oxide growth, which is very strong. ‘HC’ oxidation over the monolith catalyst is carried out with a mixture having the composition, 470 ppm of both propene and propane and 870 ppm of both ethylene and acetylene with the varying amount of O2. Three-way catalytic test is done by putting hydrocarbon mixture along with CO (10 000 ppm), NO (2000 ppm) and O2 (15 000 ppm). Below 350 °C full conversion is achieved. In this method, handling of nano-material powder is avoided.

NO reduction, CO and hydrocarbon oxidation over combustion synthesized Ag/CeO2 catalyst

The combustion technique produces ionically dispersed Ag on a nano-crystalline CeO2 surface. The catalysts thus produced were characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Catalytic properties towards NO reduction, CO and hydrocarbon oxidation have been investigated using the temperature programmed reaction technique in a packed bed tubular reactor. These results are compared with alpha-Al2O3 supported finely divided Ag metal particles synthesized by the same method. Both oxidation and reduction reactions over Ag/CeO2 have been observed to occur at lower temperatures compared to Ag/Al2O3. The rate and turnover frequency of the NO+CO reaction over 1% Ag/CeO2 are 56.3 mu mol g(-1) s(-1) and 0.97 s(-1) at 225 degrees C respectively. Activation energy (E-a) values are 71 and 67 kJ mol(-1) for CO+O-2 and NO+CO reactions, respectively, over 1% Ag/CeO2 catalyst.

Estradiol - 17β induces polyaromatic hydrocarbon-inducible cytochrome P-450 in chicken liver

A cDNA clone has been isolated from a chicken liver library prepared against messenger RNA isolated after chronic estradiol-17β treatment. The clone, pP-450 IA - 61, has an insert of 900nt and the sequence shows high homology to CYPIA2 subfamily from four other species. A single injection of estradiol-17β to immature chicken results in a striking induction of mRNA hybridizing to labeled pP-450IA - 61. The probe also hybridizes to mRNA induced by 3 — methylcholanthrene in chicken. These results offer direct proof for the similarity in the mode of action at the transcriptional level of polyaromatic hydrocarbons and estrogenic compounds.

Mechanistic evaluation of mitigation of petroleum hydrocarbon contamination by soil medium

Present in situ chemical treatment technologies for mitigation of petroleum hydrocarbon contamination are in the developmental stage or being tested. To devise efficient strategies for restricting the movement of petroleum hydrocarbon (PHC) molecules in the contaminated soil, it is proposed to utilize the sorption–interaction relationships between the petroleum contaminants and the soil substrate. The basic questions addressed in this paper are as follows (i) What are the prominent chemical constituents of the various petroleum fractions that interact with the soil substrate? (ii) What are the functional groups of a soil that interact with the contaminants? (iii) What are the bonding mechanisms possible between the soil functional groups and the PHC contaminants? (iv) What are the consequent changes brought about the soil physical properties on interaction with PHC's? (v) What are the factors influencing the interactions between PHC molecules and clay particles of the soil substrate? (vi) What is the possibility of improving the soil's attenuation ability for PHC's? The development of answers to the basic questions reveal that petroleum hydrocarbons comprise a mixture of nonpolar alkanes and aromatic and polycyclic hydrocarbons, that have limited solubility in water. The bonding mechanism between the nonpolar PHC's and the clay surface is by way of van der Waals attraction. The adsorption of the nonpolar hydrocarbons by the clay surface occurs only when their (i.e., the hydrocarbon molecules) solubility in water is exceeded and the hydrocarbons exist in the micellar form. Dilute solutions of hydrocarbons in water, i.e., concentrations of hydrocarbons at or below the solubility limit, have no effect on the hydraulic conductivity of clay soils. Permeation with pure hydrocarbons invariably influences the clay hydraulic conductivity. To improve the attenuation ability of soils towards PHC's, it is proposed to coat the soil surface with "ultra" heavy organic polymers. Adsorption of organic polymers by the clay surface may change the surface properties of the soil from highly hydrophilic (having affinity for water molecules) to organophilic (having affinity for organic molecules). The organic polymers attached to the clay surface are expected to attenuate the PHC molecules by van der Waals attraction, by hydrogen bonding, and also by adsorption into interlayer space in the case of soils containing swelling clays.

V2o5-Based Hydrocarbon Sensors

V2O5 supported on ZrO2 is found to be an excellent sensor for n-propane-butane mixtures at 625 K; in-situ X-ray diffraction studies show that V2O5 is reduced to VO2 with a metastable monoclinic structure on contact with the hydrocarbons and is oxidised back to the parent oxide on exposure to air.

The potential of microbial ecological indicators to guide ecosophisticated management of hydrocarbon-contaminated soils

Soil is an unrenewable natural resource under increasing anthropogenic pressure. One of the main threats to soils, compromising their ability to provide us with the goods and ecosystem services we expect, is pollution. Oil hydrocarbons are the most common soil contaminants, and they disturb not just the biota but also the physicochemical properties of soils. Indigenous soil micro-organisms respond rapidly to changes in the soil ecosystem, and are chronically in direct contact with the hydrophobic pollutants on the soil surfaces. Soil microbial variables could thus serve as an intrinsically relevant indicator of soil quality, to be used in the ecological risk assessment of contaminated and remediated soils. Two contrasting studies were designed to investigate soil microbial ecological responses to hydrocarbons, together with parallel changes in soil physicochemical and ecotoxicological properties. The aim was to identify quantitative or qualitative microbiological variables that would be practicable and broadly applicable for the assessment of the quality and restoration of oil-polluted soil. Soil bacteria commonly react on hydrocarbons as a beneficial substrate, which lead to a positive response in the classical microbiological soil quality indicators; negative impacts were accurately reflected only after severe contamination. Hydrocarbon contaminants become less bioavailable due to weathering processes, and their potentially toxic effects decrease faster than the total concentration. Indigenous hydrocarbon degrader bacteria, naturally present in any terrestrial environment, use specific mechanisms to improve access to the hydrocarbon molecules adsorbed on soil surfaces. Thus when contaminants are unavailable even to the specialised degraders, they should pose no hazard to other biota either. Change in the ratio of hydrocarbon degrader numbers to total microbes was detected to predictably indicate pollutant effects and bioavailability. Also bacterial diversity, a qualitative community characteristic, decreased as a response to hydrocarbons. Stabilisation of community evenness, and community structure that reflected clean reference soil, indicated community recovery. If long-term temporal monitoring is difficult and appropriate clean reference soil unavailable, such comparison could possibly be based on DNA-based community analysis, reflecting past+present, and RNA-based community analysis, showing exclusively present conditions. Microbial ecological indicators cannot replace chemical oil analyses, but they are theoretically relevant and operationally practicable additional tools for ecological risk assessment. As such, they can guide ecologically informed and sustainable ecosophisticated management of oil-contaminated lands.