Adsorption combined with aqueous phase electrochemical regeneration has been shown by researchers at The University of Manchester (UoM) to offer an alternative approach to the removal of organics from waters and wastewater's. The process, based on a regenerable graphite intercalation compound (GIC) adsorbent, produces no secondary waste, is energy efficient and chemical free. A company, Arvia Technology Ltd., was set up in 2007 to commercialise the technology. As part of a growth and development strategy Arvia investigated other possible applications of the technology and found that odour removal from gas streams might be a good fit with technology features. This Engineering Doctorate (EngD) was a direct investigation into both this technology fit and into the market opportunity for technologies treating odours and volatile organic compounds (VOCs) in gas streams. The research conducted demonstrated that the technology in its different applied forms had certain process drawbacks. Where mass transfer, adsorption and regeneration were combined in a single unit, enhanced transfer as a result of higher pollutant Henry's coefficient was offset by lower adsorbate affinity which varied with hydrophobicity. This relation between affinity and hydrophobicity was different for oxygen functionalised aromatic molecules than for the aliphatic molecules studied. Where adsorption occurred in the gaseous phase and regeneration in the aqueous phase, disadvantages such as short adsorbent packed bed lifetimes and lower current efficiencies of oxidation as a result of adsorbate desorption were shown to be an issue. When the above process challenges were set against the challenging market environment and relatively small market opportunity (approx. £52 million in Europe, 2012) it was difficult to recommend further broad research into the technology. However it was concluded that the concept might still be usefully applied to odour and VOC abatement and that further work should focus on a two phase system with a gas phase adsorbent regeneration technique. The relation observed between adsorbate affinity, hydrophobicity and structure allowed the demonstration of the preferential removal of phenol from solutions containing significantly higher concentrations of aliphatic molecules. This finding is considered the most important project output as it highlights an opportunity to develop Arvia's water treatment technology into a targeted water treatment system for the removal of specific, industrially important, organic contaminants.

Isoprene is the most abundant volatile organic compound (VOC) emitted from vegetation, mainly trees. Because it plays an important role in tropospheric chemistry leading to formation of pollutants and enhancing the lifetime of the greenhouse gas methane, concern about the response of isoprene emissions to the rise in atmospheric CO2 concentration and global climate change has been increasing over the last few years. The consequences of predicted climate change will have complex repercussions on global isoprene emission. The increasing atmospheric CO2 per se will have direct effects on terrestrial vegetation since CO2 is the substrate of photosynthesis. Because photosynthesis is limited by CO2 at current ambient concentrations, an increase in CO2 is expected to increase leaf biomass (i.e. isoprene emitting surface). Predicted warmer climate, extended drought periods, the possible shift in plant species in favour of isoprene emitters and the increase in length of growing season, may cause an increase in global isoprene emissions with profound perturbations of air quality and the global carbon cycle. The aim of this thesis was to investigate the effect of environmental variables such as light, temperature, drought and leaf-to-air vapour pressure deficit (VPD), and the short- and long-term effect of atmospheric [CO2] on isoprene emission from temperate and tropical tree species. Both leaf and whole ecosystem level fluxes were studied. At the leaf scale, a short-term experiment with leaves of potted two-year old trees of Quercus virginiana was carried out, exposing plants to two drying-rewatering cycles. Leaf isoprene emission fell, but the process was considerably less sensitive to water stress than photosynthesis and stomatal conductance. In drought conditions, the large reduction in photosynthesis caused the percentage of fixed carbon lost as isoprene to increase as plants became more stressed, reaching peaks of 50% when photosynthesis was almost zero. Isoprene emissions also showed a strong negative linear relationship with pre-dawn leaf water potential (psi-leaf). In another experiment carried out at the large enclosed facility of Biosphere 2 (B2L, Arizona, USA), studying isoprene emission from leaves of three-year-old plants of Populus deltoides grown at three CO2 atmospheric concentrations (430, 800 and 1200 mu mol mol-1 CO2) in non-stressed conditions, instantaneous increases in atmospheric [CO2] always resulted in a reduction of isoprene emission and a stimulation of photosynthesis. Moreover, in the long-term, the CO2 inhibition effect for isoprene emission became a permanent feature for plants growing under elevated [CO2]. Again, isoprene emission was less responsive to drought than photosynthesis. Both water-stress and high VPD strongly stimulated isoprene emission and depressed photosynthetic rate as a result of stomatal closure and the resulting decreases in intercellular [CO2] (Ci). This also led to a dramatic increase in the proportion of assimilated carbon lost as isoprene. The effect of atmospheric elevated [CO2] and its interaction with high VPD and water stress on ecosystem gross isoprene production (GIP) and net ecosystem exchange of CO2 (NEE) in the Populus deltoides plantations was also studied. Although GIP and NEE showed a similar response to light and temperature, NEE was stimulated by elevated CO2 by 72% and depressed by high VPD, while GIP was inhibited by elevated CO2 by 58% and stimulated by high VPD. Similar to what was observed at leaf level, under water stress conditions GIP was stimulated in the short term and declined only when the stress was severe, whereas NEE started to decrease from the beginning of the experiment. This contrasting response led the percentage of assimilated carbon lost by the ecosystem as isoprene to increase as water stress progressed from 2.5% and 0.6% in well-watered conditions to 60% and 40% for the ambient and the elevated CO2 treatments, respectively. Again, we found water limitation and high VPD off-set the inhibitory effect of elevated CO2, leading to increased isoprene emissions. The effect of a mild water stress on GIP and gross primary production (GPP) was also observed in the model tropical rainforest mesocosm of B2L. Although GPP was reduced by 32% during drought, GIP was not affected and correlated very well with both light and temperature. The percentage of fixed C lost as isoprene tended to increase during drought because of the reduction in GPP. Consumption of isoprene by soil was observed in both systems. The isoprene sink capacity of litter-free soil of the agroforest stands showed no significant response to different CO2 treatments, while isoprene production was strongly depressed by elevated atmospheric [CO2]. In both mesocosms, drought suppressed the sink capacity, but the full sink capacity of dry soil was recovered within a few hours upon rewetting. In summary, elevated CO2 increased biomass production and photosynthesis while depressing isoprene production. However, both drought and VPD may off-set the CO2 effect and lead to enhanced isoprene emission. We conclude that the overall effect of global climate change could be of enhancing global isoprene emissions while depressing the soil sink, and that the soil uptake of atmospheric isoprene is likely to be modest but significant and needs to be taken into account for a comprehensive estimate of the global isoprene budget.

This study was to explore the relationships between personal exposure to 10 volatile organic compounds (VOCs) and biochemical liver tests with the application of canonical correlation analysis. Data from a subsample of the 1999-2000 National Health and Nutrition Examination Survey were used. Serum albumin, total bilirubin (TB), alanine aminotransferase (ALT), aspartate aminotransferase (AST), lactate dehydrogenase (LDH), alkaline phosphatase (ALP), and γ-glutamyl transferase (GGT) served as the outcome variables. Personal exposures to benzene, chloroform, ethylbenzene, tetrachloroethene, toluene, trichloroethene, o-xylene, m-,p-xylene, 1,4-dichlorobenzene, and methyl tert-butyl ether (MTBE) were assessed through the use of passive exposure monitors worn by study participants. The first two canonical correlations were 0.3218 and 0.2575, suggesting a positive correlation mainly between the six VOCs (benzene, ethylbenzene, toluene, o-xylene, m-,p-xylene, and MTBE) and the three biochemical liver tests (albumin, ALP, and GGT) and a positive correlation mainly between the two VOCs (1,4-dichlorobenzene and tetrachloroethene) and the two biochemical liver tests (LDH and TB). Subsequent multiple linear regressions show that exposure to benzene, toluene, or MTBE was associated with serum albumin, while exposure to tetrachloroethene was associated with LDH and total bilirubin. In conclusion, exposure to certain VOCs as a group or individually may influence certain biochemical liver test results in the general population.

Corpus Christi among of the largest industrialized coastal urban areas in Texas. The strategic location of the city along the Gulf of Mexico allows for many important industries and an international business to be located. The cluster of industries and businesses in the region contribute to the air pollution from emissions that are harmful to the environment and to the people living in and visiting the area. Volatile organic compounds (VOC) constitute an important class of pollutants measured in the area. The automated gas chromatography (Auto GC) data was collected from Texas Commission of Environmental Quality (TCEQ) and source apportionment analysis was conducted on this data to identify key sources of VOC affecting this study region. EPA PMF 3.0 was employed in this sources apportionment study of measured VOC concentration during 2005 - 2012 in Corpus Christi, Texas. The study identified nine optimal factors (Source) that could explain the concentration of VOC at two urbane monitoring sites in the study region. Natural gas was found to be the largest contributor of VOC in the area, followed by gasoline and vehicular exhaust. Diesel was the third highest contributor with emissions from manufacturing and combustion processes. Refineries gases and evaporative fugitive emissions were other major contributors in the area; Flaring operations, solvents, and petrochemicals also impacted the measured VOC in the urban area. It was noted that he measured VOC concentrations were significantly influenced by the economic downturn in the region and this was highlighted in the annual trends of the apportioned VOC.

There is a need for chemical sensors for monitoring volatile organic compounds (VOCs) in air. Acute and chronic inhalation of toxic VOCs can cause adverse health effects in humans, so monitoring these analytes is important for ensuring that their concentrations are maintained below maximum permissible levels. Chemical sensors using polydimethylsiloxane (PDMS) to extract VOCs with partial selectivity, coupled with label-free optical detection methods based on refractive index, can overcome the limitations of conventional VOC detection methods. A variety of tunable and high refractive index PDMS materials were developed by incorporating a range of titanium and zirconium concentrations (2.5 – 30 mol % and 2.5 – 15 mol %, respectively) using a simple sol-gel synthesis and by incorporating a range of titanium concentrations (2.5 – 10 mol %) into naphthyl-functionalized PDMS. These materials ranged in refractive index from 1.4023 ± 0.0002 to 1.5663 ± 0.0001 at 635 nm and 1.3942 ± 0.0003 to 1.5510 ± 0.0007 at 1550 nm. The ability to use tunable refractive index PDMS films to differentiate between m-xylene and cyclohexane was demonstrated by monitoring changes in refractive index and thickness following absorption of these analytes using a refractometer at 1550 nm. The sensitivity of the refractive index response to an analyte using a particular PDMS film was dependent upon the difference between the refractive index of the analyte and film, as well as the film-air partition coefficient of the analyte. The detection limits for m-xylene and cyclohexane were 81 ppm and 4940 ppm, respectively, using PDMS-titanium-oxo nanocomposites with 5 and 10 mol % Ti, respectively. A simple planar waveguide sensor with an input grating coupler was developed to monitor changes in refractive index of the cladding through shifts in peak resonance wavelength. Using high refractive index PDMS materials as the waveguide core, we monitored changes in refractive index arising from absorption of VOCs into the grating. Here, the sensitivity of the waveguide response was dependent upon the difference in refractive index of the analyte and polymer, as well as the film-air partition coefficient of the analyte. The detection limits for m-xylene and cyclohexane were 1980 ppm and 18000 ppm, respectively. / Thesis (Master, Chemistry) -- Queen's University, 2013-08-24 11:45:57.642

Chemical detection, including analysis of gases and liquids, is a large field in environmental research and industry. It requires sensitive, rapid, and inexpensive chemical sensors. Many industrial materials such as coatings and adhesives readily absorb chemical analytes, which may result in changes of their chemical, mechanical, and optical properties. This uptake of volatile organic compounds either from the gas phase or from an aqueous solution into a thin film is frequently accompanied by a change in material refractive index and film thickness. While the undesired swelling of thin film coatings and their refractive index changes affect their use in harsh environments, the sensitivity of some polymers to solvent vapours can also be exploited for sensing applications. In this project, a method is reported for real-time monitoring of vapour uptake by simultaneous detection of the refractive index, n, and thickness, d, of thin transparent films with a precision of 10-4 for refractive index and 100 nm for thickness. The setup combines a total internal reflection refractometer with an interferometric imaging method. Two setups using 1550 nm and 635 nm measurement wavelengths were developed, with a detection rate of 1 second per measurement. Two processing methods using a fast Fourier transform algorithm to calculate n and d are applied to the experimental results and compared. Both methods could extract n and d simultaneously from each image captured by the refractometer. The results show that the setup is capable of monitoring film RI and thickness change in real-time. The partitioning of volatile organic compound vapours into polydimethylsiloxane (PDMS) and PDMS-polydiphenylsiloxane (PDPS) copolymers is described. The system is also suited for characterization of other solid and liquid films like SU-8 photoresist and crude oil. It shows great potential in commercial applications of thin film characterization. / Thesis (Master, Electrical & Computer Engineering) -- Queen's University, 2013-09-19 22:21:38.836

Volatile organic compounds (VOCs) are organic chemicals typically characterized as having low molecular weight, low solubility in water, and high vapor pressure. Consequently, they readily evaporate from liquid to the gaseous phase at standard temperature and pressure. VOCs are produced by many microorganisms as a result of both uninduced and induced metabolic pathways. Volatile-based microbial inhibition in environments such as soil is well founded, with numerous antimicrobial VOCs and formulations having been identified. Inhibitory VOCs are of particular interest as microbial control agents, as low concentrations of gaseous VOCs have been observed to elicit significant antimicrobial effects. It is believed that this contact-independent antagonism may present unique advantages over traditional microbial control methods, particularly where contact-dependent treatment methods are either impractical or inconvenient. This method may be of particular benefit for managing infections where disease may become pervasive in the population, such as with white-nose syndrome (WNS) among bats. A list of potential antifungal compounds and formulations was compiled by referencing the scientific literature. Screening of compounds and formulations was conducted through toxicity analyses and antimicrobial susceptibility testing for the in vitro ability of VOCs and formulations to inhibit growth of select pathogenic fungi. A dispersal system was developed that entailed electrical circuit and software engineering as well as quantitative analysis to validate consistent and accurate dispersal of potential treatment compounds and formulations. Successful completion of these goals culminated in exposure trials involving live bats to determine any significant toxicological effects. Ex and in situ treatment trials were conducted to determine efficacy of promoting the reduction of disease severity and increasing survivorship of infected bat populations. The identification of volatile-based inhibitory compounds, in conjunction with a novel method for accurate and automated delivery, could prove a promising treatment and prophylactic in combatting microbial pathogenesis and contamination.

This study aimed at providing a thorough understanding of temporal and spatial variations of VOCs and underlying factors in different microenvironments in two different urban atmospheres, with different degrees of regulatory enforcement. The VOC data were collected in field campaigns conducted in Ankara, Turkey, and Ottawa, Canada over the years 2000-2004. Insight into the sources of VOCs in different urban atmospheres was sought by using three commonly used receptor models namely / Positive Matrix Factorization (PMF), Chemical Mass Balance (CMB) Model and Conventional Factor Analysis (CFA). Motor vehicle related source profiles were developed to use in receptor modeling. Motor vehicles are the most abundant VOC sources with about 60% and 95% contributions to ambient levels in Ankara and Ottawa, respectively. Residential heating (31%) during winter season, biogenic (9%) and architectural coating (12%) emissions during summer season and solvent use (about 12%) emissions are the next abundant VOC sources in Ankara. In addition, a new method to estimate the contribution of sources from wind sectors in urban atmosphere was developed and implemented in this study. The comparison of the results of these two cities demonstrated the influence of control measures on ambient levels and sources of VOCs observed in different urban atmospheres. VOC levels in Ankara exceed EU levels and they are about factor of two higher than that are measured in Ottawa owing to lack of implementation of emission control regulations for VOCs in Ankara compared to well adopted regulations in Ottawa.

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京都大学 / 新制・課程博士 / 博士(農学) / 甲第23522号 / 農博第2469号 / 新制||農||1087(附属図書館) / 学位論文||R3||N5353(農学部図書室) / 京都大学大学院農学研究科地域環境科学専攻 / (主査)教授 小杉 緑子, 教授 北山 兼弘, 教授 柴田 昌三 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM