Objective grading of the anterior eye

Purpose. To convert objective image analysis of anterior ocular surfaces into recognisable clinical grades, in order to provide a more sensitive and reliable equivalent to current subjective grading methods; a prospective, randomized study correlating clinical grading with digital image assessment. Methods. The possible range of clinical presentations Of bulbar and palpebral hyperaemia, palpebral roughness and corneal staining were represented by 4 sets of 10 images. The images were displayed in random order and graded by 50 clinicians using both subjective CCLRU and Efron grading scales. Previously validated objective image analysis was performed 3 times oil each of the 40 images. Digital measures included edge-detection and relative-coloration components. Step-wise regression analysis determined correlations between the average subjective grade and the objective image analysis measures. Results. Average subjective grades Could be predicted by a combination of the objective image analysis components. These digital ``grades'' accounted for between 69%, (for Efron scale-graded palpebral redness) and 98% (for Efron scale-graded bulbar hyperaemia) of the subjective variance. Conclusions. The results indicate that clinicians may use a combination of vessel areas and overall hue in their judgment of clinical severity for certain conditions. Objective grading call take these aspects into account, and be used to predict an average ``objective grade'' to be used by a clinician in describing the anterior eye. These measures are more sensitive and reliable than subjective grading while still utilizing familiar terminology, and can be applied in research or practice to improve the detection, and monitoring of ocular surface changes.

Some aspects of the interaction of humic substances with metal ions

Humic substances are the major organic constituents of soils and sediments. They are heterogeneous, polyfunctional, polydisperse, macromolecular and have no accurately known chemical structure. Their interactions with radionuclides are particularly important since they provide leaching mechanisms from disposal sites. The central theme to this research is the interaction of heavy metal actinide analogues with humic materials. Studies described focus on selected aspects of the characteristics and properties of humic substances. Some novel approaches to experiments and data analysis are pursued. Several humic substances are studied; all but one are humic acids, and those used most extensively were obtained commercially. Some routine characterisation techniques are applied to samples in the first instance. Humic substances are coloured, but their ultra-violet and visible absorption spectra are featureless. Yet, they fluoresce over a wide range of wavelengths. Enhanced fluorescence in the presence of luminescent europium(III) ions is explained by energy transfer from irradiated humic acid to the metal ion in a photophysical model. Nuclear magnetic resonance spectroscopy is applied to the study of humic acids and their complexes with heavy metals. Proton and carbon-13 NMR provides some structural and functionality information; Paramagnetic lanthanide ions affect these spectra. Some heavy metals are studied as NMR nuclei, but measurements are restricted by their sensitivity. A humic acid is fractionated yielding a broad molecular weight distribution. Electrophoretic mobilities and particle radii determined by Laser Doppler Electrophoretic Light Scattering are sensitive to the conditions of the supporting media, and the concentration and particle size distribution of humic substances. In potentiometric titrations of humate dispersions, the organic matter responds slowly and the mineral acid addition is buffered. Proton concentration data is modelled and a mechanism is proposed involving two key stages, both resulting in proton release after some conformational changes.

Technoeconomic modelling of coal conversion processes for liquid fuel production

Since the oil crisis of 1973 considerable interest has been shown in the production of liquid fuels from alternative sources. In particular processes utilizing coal as the feedstock have received considerable interest. These processes can be divided into direct and indirect liquefaction and pyrolysis. This thesis describes the modelling of indirect coal liquefaction processes for the purpose of performing technical and economic assessment of the production of liquid fuels from coal and lignite, using a variety of gasification and synthesis gas liquefaction technologies. The technologies were modeled on a 'step model' basis where a step is defined as a combination of individual unit operations which together perform a significant function on the process streams, such as a methanol synthesis step or a gasification and physical gas cleaning step. Sample results of the modelling, covering a wide range of gasifiers, liquid synthesis processes and products are presented in this thesis. Due to the large number of combinations of gasifier, liquid synthesis processes, products and economic sensitivity cases, a complete set of results is impractical to present in a single publication. The main results show that methanol is the cheapest fuel to produce from coal followed by fuel alcohol, diesel from the Shell Middle Distillate Synthesis process,gasoline from Mobil Methanol to Gasoline (MTG) process, diesel from the Mobil Methanol Olefins Gasoline Diesel (MOGD) process and finally gasoline from the same process. Some variation in production costs of all the products was shown depending on type of gasifier chosen and feedstock.

Application of thermal neutron radiography for the mass transport of moisture through freezing soil

This thesis reports on the development of a technique to evaluate hydraulic conductivities in a soil (Snowcal) subject to freezing conditions. The technique draws on three distinctly different disciplines, Nuclear Physics, Soil Physics and Remote Sensing to provide a non-destructive and reliable evaluation of hydraulic conductivity throughout a freezing test. Thermal neutron radiography is used to provide information on local water/ice contents at anytime throughout the test. The experimental test rig is designed so that the soil matrix can be radiated by a neutron beam, from a nuclear reactor, to obtain radiographs. The radiographs can then be interpreted, following a process of remote sensing image enhancement, to yield information on relative water/ice contents. Interpretation of the radiographs is accommodated using image analysis equipment capable of distinguishing between 256 shades of grey. Remote sensing image enhancing techniques are then employed to develop false colour images which show the movement of water and development of ice lenses in the soil. Instrumentation is incorporated in the soil in the form of psychrometer/thermocouples, to record water potential, electrical resistance probes to enable ice and water to be differentiated on the radiographs and thermocouples to record the temperature gradient. Water content determinations are made from the enhanced images and plotted against potential measurements to provide the moisture characteristic for the soil. With relevant mathematical theory pore water distributions are obtained and combined with water content data to give hydraulic conductivities. The values for hydraulic conductivity in the saturated soil and at the frozen fringe are compared with established values for silts and silty-sands. The values are in general agreement and, with refinement, this non-destructive technique could afford useful information on a whole range of soils. The technique is of value over other methods because ice lenses are actually seen forming in the soil, supporting the accepted theories of frost action. There are economic and experimental restraints to the work which are associated with the use of a nuclear facility, however, the technique is versatile and has been applied to the study of moisture transfer in porous building materials and could be further developed into other research areas.

Results of the IEA round Robin on viscosity and aging of fast pyrolysis bio-oils:long-term tests and repeatability

An international round robin study of the viscosity measurements and aging of fast pyrolysis bio-oil has been undertaken recently, and this work is an outgrowth from that effort. Two bio-oil samples were distributed to two laboratories for accelerated aging tests and to three laboratories of long-term aging studies. The accelerated aging test was defined as the change in viscosity of a sealed sample of bio-oil held for 24 h at 80 °C. The test was repeated 10 times over consecutive days to determine the intra-laboratory repeatability of the method. Other bio-oil samples were placed in storage at three temperatures, 21, 5, and -17 °C, for a period of up to 1 year to evaluate the change in viscosity. The variation in the results of the accelerated aging test was shown to be low within a given laboratory. The long-term aging studies showed that storage of a filtered bio-oil under refrigeration can minimize the amount of change in viscosity. The accelerated aging test gave a measure of change similar to that of 6-12 months of storage at room temperature for a filtered bio-oil. Filtration of solids was identified as a key contributor to improving the stability of the bio-oil as expressed by the viscosity based on results of the accelerated aging tests as well as long-term aging studies. Only the filtered bio-oil consistently gave useful results in the accelerated aging and long-term aging studies. The inconsistency suggests that better protocols need to be developed for sampling bio-oils. These results can be helpful in setting standards for use of bio-oil, which is just coming into the marketplace. © 2012 American Chemical Society.

Increase of energy recovery from sewage sludge

The use of the pyrolysis process to obtain valuable products from biomass is amongst the technologies being investigated as a source for renewable energy. The pyrolysis process yields products such as biochar, bio-oil and non condensable gases. The main objective of this project is to increase energy recovery from sewage sludge by utilising the intermediate pyrolysis process. The intermediate pyrolysis has a residence time ranging from 5 to 10 minutes. The main product yields from sewage sludge pyrolysis are 50 wt% biochar, 40 wt% bio-oil and 10 wt% non condensable gases. The project was carried out on a pilot plant scale reactor with a load capacity of 20 kg/h. This enabled a high yield of biochar and bio-oil. The characterisation of the products indicated that the organic phase of the bio-oil had good fuel properties such as having high energy content of 39 MJ/kg, low acid number of 21.5, high flash point of 150 and viscosity of 35 cSt. An increase in pyrolysis experiments enabled large quantities of pyrolysis oil production. Co-pyrolysis of sewage sludge was carried out on laboratory scale with mixed wood, rapeseed and straw. It found that there was an increase in bio-oil quantity with rapeseed while co-pyrolysis with wood helped to mask the smell of the sludge pyrolysis oil. Engine test were successfully carried out in an old Lister engine with pyrolysis oil fractions of 30% and 50% blended with biodiesel. This indicates that these pyrolysis oil fractions can be used in similar engine types without any problems however long term effects in ordinary engines are unknown. An economic evaluation was carried out about the implementation of the intermediate pyrolysis process for electricity production in a CHP using the pyrolysis oil. The prices of electricity per kWh were found to be very high.

Geographical variation in carbon dioxide fluxes from soils in agro-ecosystems and its implications for life-cycle assessment

1. Exchange of carbon dioxide (CO2) from soils can contribute significantly to the global warming potential (GWP) of agro-ecosystems. Due to variations in soil type, climatic onditions and land management practices, exchange of CO2 can differ markedly in different geographical locations. The food industry is developing carbon footprints for their products necessitating integration of CO2 exchange from soils with other CO2 emissions along the food chain. It may be advantageous to grow certain crops in different geographical locations to minimize CO2 emissions from the soil, and this may provide potential to offset other emissions in the food chain, such as transport. 2. Values are derived for the C balance of soils growing horticultural crops in the UK, Spain and Uganda. Net ecosystem production (NEP) is firstly calculated from the difference in net primary production (NPP) and heterotrophic soil respiration (Rh). Both NPP and Rh were estimated from intensive direct field measurements. Secondly, net biome production (NBP) is calculated by subtracting the crop biomass from NEP to give an indication of C balance. The importance of soil exchange is discussed in the light of recent discussions on carbon footprints and within the context of food life-cycle assessment (LCA). 3. The amount of crop relative to the biomass and the Rh prevailing in the different countries were the dominant factors influencing the magnitude of NEP and NBP. The majority of the biomass for lettuce Lactuca sativa and vining peas Pisum sativum, was removed from the field as crop; therefore, NEP and NBP were mainly negative. This was amplified for lettuces grown in Uganda (-16·5 and -17 t C ha-1 year-1 compared to UK and Spain -4·8 to 7·4 and -5·1 to 6·3 t C ha-1 year-1 for NEP and NBP, respectively) where the climate elevated Rh. 4. Synthesis and applications. This study demonstrates the importance of soil emissions in the overall life cycle of vegetables. Variability in such emissions suggests that assigning a single value to food carbon footprints may not be adequate, even within a country. Locations with high heterotrophic soil respiration, such as Spain and Uganda (21·9 and 21·6 t C ha-1 year-1, respectively), could mitigate the negative effects of climate on the C costs of crop production by growth of crops with greater returns of residue to the soil. This would minimize net CO2 emissions from these agricultural ecosystems.

Catalysts in production of biodiesel:a review

Biodiesel is a renewable substitute fuel for petroleum diesel fuel which is made from nontoxic, biodegradable, renewable sources such as refined and used vegetable oils and animal fats. Biodiesel is produced by transesterification in which oil or fat is reacted with a monohydric alcohol in the presence of a catalyst. The process of transesterification is affected by the mode of reaction, molar ratio of alcohol to oil, type of alcohol, nature and amount of catalysts, reaction time, and temperature. Various studies have been carried out using different oils as the raw material and different alcohols (methanol, ethanol, butanol), as well as different catalysts, notably homogeneous ones such as sodium hydroxide, potassium hydroxide, sulfuric acid, and supercritical fluids or enzymes such as lipases. Recent research has focused on the application of heterogeneous catalysts to produce biodiesel, because of their environmental and economic advantages. This paper reviews the literature regarding both catalytic and noncatalytic production of biodiesel. Advantages and disadvantages of different methods and catalysts used are discussed. We also discuss the importance of developing a single catalyst for both esterification and transesterification reactions.

Spectral characteristics and thermal evolution of long-period gratings in photonic crystal fibers fabricated with a near-IR radiation femtosecond laser using point-by-point inscription

The spectral properties of long-period gratings (LPGs) fabricated in photonic crystal fibers using femtosecond laser pulses by the point-by-point technique, without oil-immersion of the fiber, are investigated in detail. Postfabrication spectral monitoring at room temperature showed significant long-term instability of the gratings and stable spectra only after 600 h. The stabilized spectral properties of the gratings improved with increasing annealing temperature. The observed changes in resonant wavelength, optical strength, and grating birefringence were correlated to the laser inscription energy and were further used to study the mechanism of femtosecond inscription. Furthermore, the femtosecond-laser inscribed LPGs were compared to electric-arc fabricated LPGs. Comparison of experimental results with theoretical models of LPGs and laser propagation during inscription indicate that the major processes responsible for the index change are permanent compaction and thermally induced strain, the latter can be significantly changed through annealing. © 2011 Optical Society of America.

Factors affecting the nodulation and growth of tropical woody legume seedlings

This study surveys the occurrence of nodulation in woody legume species in Panamá and Costa Rica, describes nodule and root characteristics, and researches host-bacteria specificity, nodulation potential of soils, and the effects of light, added nitrogen, and rhizobia and VA mycorrhizal fungi inoculation on seedling growth. I examined 83 species in 37 genera and found 80% to be nodulated. Percent nodulated species in the Caesalpinioideae, Mimosoideae, and Papilionoideae was 17, 95, and 86, respectively, with no correlation between nodule morphology and tribal classification. Nodules formed mainly at root branch points which supports epidermal breaks as an important rhizobia infection route. More non-nodulated than nodulated species had root hairs. Several species emitted volatile sulfur-containing compounds, including the toxic compound ethylmercaptan, from roots, germinating seeds, and other tissues. These emissions may have an allelopathic action against pathogens, predators, or other plants. In contrast to the general non-specificity of most legumes for rhizobia, Mimosa pigra L. was highly specific and only nodulated in flooded soils. This species' specificity, combined with a limited occurrence of its root nodule bacteria may limit its natural distribution, but its spread as an invasive weed is facilitated when fill material from rivers is deposited in other areas. ^ An experimental light level of 1.5% of full sun completely inhibited seedling nodulation, as do similar naturally low levels in forest understory. In the forest, trees and seedlings were not nodulated. in some soils with suspected high N content. For six experimental species, added N progressively increased seedling growth while decreasing nodule biomass; at the highest level of added N nodulation was completely suppressed. Species and individuals showed variation in nodule biomass at high N applications which may indicate an opportunity for genetic selection for optimal N acquisition. Rhizobia inoculation had a small positive effect on seedling shoot growth, but VA mycorrhiza inoculation overwhelmingly increased seedling size, biomass, and leaf mineral concentration. In lowland tropical forest, VA mycorrhizal colonization appears indispensable for legume nodulation because of the fungus' ability to supply P in deficient soils. This requirement makes the legume-rhizobia-mycorrhiza association obligately tripartite. ^

Sorption characteristics of a nonionic surfactant during remediation of contaminated soil with different organic content

Surfactant enhanced subsurface remediation has gained importance in soil remediation. Since surfactants can be sorbed on soils, the concentration of free surfactant could drop below the critical micelle concentration, CMC, which may reduce the ability of the surfactant to solubilize the contaminants in soils. ^ The main goal of this research was to study the factors affecting the surfactant sorption on soil such as surfactant concentration, soil organic content, and organic contaminants in soil and to determine the organic contaminants removed from soils by surfactant. The results would be served as the basis for the implementation of a future study in the pilot scale and field scale for surfactant enhanced subsurface remediation. ^ This research study investigated the relationship between the organic content of soils and the sorption characteristics of a nonionic surfactant, Triton X-100. The experiments were performed using uncontaminated soils and soil contaminated with naphthalene and decane. The first part of the experiments were conducted in batch mode utilizing surface tension technique to determine the CMC of surfactant Triton X-100 and the effective CMC in the soil/aqueous system. The sorption of Triton X-100 was calculated from the surface tension measurements. The second part of the experiments utilized the SPME/GC/FID technique to determine the concentration of the contaminants solubilized from the soils by the surfactant Triton X-100 at different concentrations. ^ The results indicated that when the concentration of surfactant was lower than the CMC, the amount of surfactant sorbed on soil increased with the increasing surfactant concentration and the surfactant sorption characteristics of the uncontaminated soils could be modeled by the Freundlich isotherm. For the contaminated soils, the amount of surfactant sorbed was higher than those for the uncontaminated soils. The amount of surfactant sorbed on soils also depends on the organic content in the soils. The higher the organic content in the soil, higher is the amount of surfactant sorbed onto the soil. When the concentration of surfactant was higher than the CMC, the amount of surfactant added into the soil/aqueous system will increase the number of micelle and it increase the solubilization of organic contaminant from the soils. The ratio of the moles of organic contaminant solubilized to the moles of surfactant present as micelles is called the molar solubilization ratio (MSR). MSR value for naphthalene was about 0.16 for the soil-water systems. The organic content of soil did not appear to affect MSR for naphthalene. On the other hand, the MSR values for decane were 0.52, 0.39 and 0.38 for soils with 25%, 50% and 75% organic content, respectively. ^

The use of hyphenated spectrometric techniques for the environmental forensic assessment of non-traditional pollutants and degradates in the greater Florida Everglades

A comprehensive investigation of sensitive ecosystems in South Florida with the main goal of determining the identity, spatial distribution, and sources of both organic biocides and trace elements in different environmental compartments is reported. This study presents the development and validation of a fractionation and isolation method of twelve polar acidic herbicides commonly applied in the vicinity of the study areas, including e.g. 2,4-D, MCPA, dichlorprop, mecroprop, picloram in surface water. Solid phase extraction (SPE) was used to isolate the analytes from abiotic matrices containing large amounts of dissolved organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-) in a Quadrupole Ion Trap mass spectrometer was used to perform the characterization of the herbicides of interest. ^ The application of Laser Ablation-ICP-MS methodology in the analysis of soils and sediments is reported in this study. The analytical performance of the method was evaluated on certified standards and real soil and sediment samples. Residential soils were analyzed to evaluate feasibility of using the powerful technique as a routine and rapid method to monitor potential contaminated sites. Forty eight sediments were also collected from semi pristine areas in South Florida to conduct screening of baseline levels of bioavailable elements in support of risk evaluation. The LA-ICP-MS data were used to perform a statistical evaluation of the elemental composition as a tool for environmental forensics. ^ A LA-ICP-MS protocol was also developed and optimized for the elemental analysis of a wide range of elements in polymeric filters containing atmospheric dust. A quantitative strategy based on internal and external standards allowed for a rapid determination of airborne trace elements in filters containing both contemporary African dust and local dust emissions. These distributions were used to qualitative and quantitative assess differences of composition and to establish provenance and fluxes to protected regional ecosystems such as coral reefs and national parks. ^