I. Electronic processes in α-sulfur. II. Polaron motion in a D.C. electric field

Part I: The mobilities of photo-generated electrons and holes in orthorhombic sulfur are determined by drift mobility techniques. At room temperature electron mobilities between 0.4 cm²/V-sec and 4.8 cm²/V-sec and hole mobilities of about 5.0 cm²/V-sec are reported. The temperature dependence of the electron mobility is attributed to a level of traps whose effective depth is about 0.12 eV. This value is further supported by both the voltage dependence of the space-charge-limited, D.C. photocurrents and the photocurrent versus photon energy measurements.

As the field is increased from 10 kV/cm to 30 kV/cm a second mechanism for electron transport becomes appreciable and eventually dominates. Evidence that this is due to impurity band conduction at an appreciably lower mobility (4.10^-4 cm²/V-sec) is presented. No low mobility hole current could be detected. When fields exceeding 30 kV/cm for electron transport and 35 kV/cm for hole transport are applied, avalanche phenomena are observed. The results obtained are consistent with recent energy gap studies in sulfur.

The theory of the transport of photo-generated carriers is modified to include the case of appreciable thermos-regeneration from the traps in one transit time.

Part II: An explicit formula for the electric field E necessary to accelerate an electron to a steady-state velocity v in a polarizable crystal at arbitrary temperature is determined via two methods utilizing Feynman Path Integrals. No approximation is made regarding the magnitude of the velocity or the strength of the field. However, the actual electron-lattice Coulombic interaction is approximated by a distribution of harmonic oscillator potentials. One may be able to find the “best possible” distribution of oscillators using a variational principle, but we have not been able to find the expected criterion. However, our result is relatively insensitive to the actual distribution of oscillators used, and our E-v relationship exhibits the physical behavior expected for the polaron. Threshold fields for ejecting the electron for the polaron state are calculated for several substances using numerical results for a simple oscillator distribution.

Bacterial production of nitrate in aquatic systems: progress report. Nitrate-loss processes in raw water

This short interim progress report builds on previous progress reports which have described the quantification of the process both within and between lakes of different degrees of eutrophication. These data indicated that slight changes in methodology, particularly when investigating sediment deposits, could grossly affect the measured activity. The aim of the present research was an attempt to rationalize these differences. If this could be achieved it would enable meaningful interpretation of published data obtained using different methods and therefore enlarge the available database. In addition some observations have been made on the production of nitrite by Grasmere profundal sediment slurries sampled during the circulation period.

The kinetics of calcite precipation and related processes

This review is concerned with the kinetics of calcium carbonate formation and related processes which are important in many hard waters.

Reggeization of some unequal mass processes involving higher spins : the reactions pion-nucleon going to (V,Nucleon), pion-nucleon going to (V,delta-hyperon), and photon-proton going to (positive pion,neutron)

Recent theoretical developments in the reggeization of inelastic processes involving particles with high spin are incorporated into a model of vector meson production. A number of features of experimental differential cross sections and density matrices are interpreted in terms of this model.

The method chosen for reggeization of helicity amplitudes first separates kinematic zeros and singularities from the parity-conserving amplitudes and then applies results of Freedman and Wang on daughter trajectories to the remaining factors. Kinematic constraints on helicity amplitudes at t = 0 and t = (M – M_Δ)² are also considered.

It is found that data for reactions of types πN→VN and πN→VΔ are consistent with a model of this type in which all kinematic constraints at t = 0 are satisfied by evasion (vanishing of residue functions). As a quantitative test of the parametrization, experimental differential cross sections of vector meson production reactions dominated by pion trajectory exchange are compared with the theory. It is found that reduced residue functions are approximately constant, once the kinematic behavior near t = (M – M_Δ)² has been removed.

The alternative possibility of conspiracy between amplitudes is also discussed; and it is shown that unless conspiracy is present, some amplitudes allowed by angular momentum conservation will not contribute with full strength in the forward direction. An example, γp→π⁺n in which the data for dσ/dt indicate conspiracy, is studied in detail.

Nitrates - loss processes in raw water

This project investigated the production of nitrate (nitrification) by bacteria in lakes. The work was undertaken as nitrification is a key process in the nitrogen cycle and previous estimates of rates of nitrification were unreliable. When different methods were used to estimate rates of nitrification within sediment deposits different results were obtained. Investigation' of specific aspects of these methodologies has allowed some rationalization of these observations and also enabled comparisons of previously published data which, beforehand, was not possible. However, it was not clear which methods gave the most reliable rate estimates. Calculation of a nitrate budget for Grasmere lake indicated that the use of methods which involved the mixing of surface sediments (and therefore disrupted preformed nutrient gradients) overestimated the rate of nitrification. The study concludes that slight changes in the method used to prepare sediment slurries can result in large changes, in the measured nitrifying activity. This makes comparisons between studies, using different methods, extremely difficult. Methods to study sediment nitrification processes which do not disrupt preformed substrate gradients within the sediment provide the most reliable rate estimates.

Processes controlling the quantities of biogenic materials in lakes and reservoirs subject to cultural eutrophication

The processes which control the growth, composition, succession and loss from suspension of phytoplankton algae are briefly reviewed, with special reference to function in eutrophic reservoir systems. The ecology of larger algal biomasses supported by high nutrient loading rates are more likely to be subject to physical (wash-out, underwater light penetration, thermal stability and mixing) than to chemical constraints. Sudden changes in the interactions between physical factors temporarily impair the growth of dominant algal species, and advance the succession. Certain algae may be cropped heavily, but selectively, by zooplankton feeding, but they are rarely the species which cause problems in waterworks practice. Grazing, however, does influence succession. A deeper understanding of the operation of loss control mechanism is urgently required. Potentially, manipulation of the physical environment provides an important means of alleviating day-to-day algal problems in eutrophic reservoirs; in terms of cost effectiveness these may prove to be more attractive than reducing nutrient loads at source.

The impact of physical processes on algal growth

Mixing and transport processes in surface waters strongly influence the structure of aquatic ecosystems. The impact of mixing on algal growth is species-dependent, affecting the competition among species and acting as a selective factor for the composition of the biocoenose. Were it not for the ever-changing ”aquatic weather”, the composition of pelagic ecosystems would be relatively simple. Probably just a few optimally adapted algal species would survive in a given water-body. In contrast to terrestrial ecosystems, in which the spatial heterogeneity is primarily responsible for the abundance of niches, in aquatic systems (especially in the pelagic zone) the niches are provided by the temporal structure of physical processes. The latter are discussed in terms of the relative sizes of physical versus biological time-scales. The relevant time-scales of mixing and transport cover the range between seconds and years. Correspondingly, their influence on growth of algae is based on different mechanisms: rapid changes are relevant for the fast biological processes such as nutrient uptake and photosynthesis, and the slower changes are relevant for the less dynamic processes such as growth, respiration, mineralization, and settling of algal cells. Mixing time-scales are combined with a dynamic model of photosynthesis to demonstrate their influence on algal growth.

TRANSFER OF ANALYTICAL METHODS FOR THE CHARACTERISATION OF NATURAL PRODUCTS TO R&D PROCESSES OF IDOKI

IDOKI SCF Technologies S.L. is a technology-based company, set up on September 2006 in Derio (Biscay) with the main scope of developing extraction and purification processes based on the use of supercritical fluid extraction technology (SFE) in food processing, extraction of natural products and the production of personal care products. IDOKI¿s researchers have been working on many different R&D projects so far, most of them using this technology. However, the optimization of a SFE method for the different matrices cannot be performed unless we have an analytical method for the characterisation of the extracts obtained in each experiment. The analytical methods are also essential for the quality control of the raw materials that are going to be used and also for the final product. This PhD thesis was born to tackle this problem and therefore, it is based on the development of different analytical methods for the characterisation of the extracts and products. The projects that we could include in this thesis were the following: the extraction propolis, the recovery of agroindustrial residues (soy and wine) and the dealcoholisation of wine.On the one hand, for the extraction of propolis, several UV-Vis spectroscopic methods were used in order to measure the antioxidant capacity and the total polyphenol and flavonoid content of the extracts. A SFC method was also developed in order to measure more specific phenolic compounds. On the other hand, for the recovery of agroindustrial residues UV-Vis spectroscopy was used to determine the total polyphenol content and two SFC methods were developed to analyse different phenolic compounds. Extraction methods such as MAE, FUSE and rotary agitation were also evaluated for the characterisation of the raw materials.Finally, for the dealcoholisation of wine, the development of a SBSE-TD-GC-MS and DHS-TD-GC-MS methods for the analysis of aromas and a NIR spectroscopic method for the determination of ethanol content with the help of chemometrics was necessary. Most of these methods are typically used in IDOKI¿s lab as routine analyses apart from others not included in this PhD thesis.