Electron tunneling in proteins and water

The subject of this thesis is electronic coupling in donor-bridge-acceptor systems. In Chapter 2, ET properties of cyanide-bridged dinuclear ruthenium complexes were investigated. The strong interaction between the mixed-valent ruthenium centers leads to intense metal-to-metal charge transfer bands (MMCT). Hush analysis of the MMCT absorption bands yields the electronic-coupling strength between the metal centers (H_(AB)) and the total reorganization energy (λ). Comparison of ET kinetics to calculated rates shows that classical ET models fail to account for the observed kinetics and nuclear tunneling must be considered.

In Chapter 3, ET rates were measured in four ruthenium-modified highpotential iron-sulfur proteins (HiPIP), which were modified at position His50, His81, His42 and His18, respectively. ET kinetics for the His50 and His81 mutants are a factor of 300 different, while the donor-acceptor separation is nearly identical. PATHWAY calculations corroborate these measurements and highlight the importance of structural detail of the intervening protein matrix.

In Chapter 4, the distance dependence of ET through water bridges was measured. Photoinduced ET measurements in aqueous glasses at 77 K show that water is a poor medium for ET. Luminescence decay and quantum yield data were analyzed in the context of a quenching model that accounts for the exponential distance dependence of ET, the distance distribution of donors and acceptors embedded in the glass and the excluded volumes generated by the finite sizes of the donors and acceptors.

In Chapter 5, the pH-dependent excited state dynamics of ruthenium-modified amino acids were measured. The [Ru(bpy)_(3)] ^(2+) chromophore was linked to amino acids via an amide linkage. Protonation of the amide oxygen effectively quenches the excited state. In addition. time-resolved and steady-state luminescence data reveal that nonradiative rates are very sensitive to the protonation state and the structure of the amino acid moiety.

Mathematical models for the prediction of temperature distributions resulting from the discharge of heated water into large bodies of water

Mathematical models for heated water outfalls were developed for three flow regions. Near the source, the subsurface discharge into a stratified ambient water issuing from a row of buoyant jets was solved with the jet interference included in the analysis. The analysis of the flow zone close to and at intermediate distances from a surface buoyant jet was developed for the two-dimensional and axisymmetric cases. Far away from the source, a passive dispersion model was solved for a two dimensional situation taking into consideration the effects of shear current and vertical changes in diffusivity. A significant result from the surface buoyant jet analysis is the ability to predict the onset and location of an internal hydraulic jump. Prediction can be made simply from the knowledge of the source Froude number and a dimensionless surface exchange coefficient. Parametric computer programs of the above models are also developed as a part of this study. This report was submitted in fulfillment of Contract No. 14-12-570 under the sponsorship of the Federal Water Quality Administration.

Fish for the poor under a rising global demand and changing fishery regime

In the past, agricultural researchers tended to ignore the fisheries factor in global food and nutritional security. However, the role of fish is becoming critical as a result of changes in fisheries regimes, income distribution, demand and increasing international trade. Fish has become the fastest growing food commodity in international trade and this is raising concern for the supply of fish for poorer people. As a result, the impact of international trade regimes on fish supply and demand, and the consequences on the availability of fish for developing countries need to be studied. Policies aimed at increasing export earnings are in conflict with those aimed at increasing food security in third world countries. Fisheries policy research will need to focus on three primary areas which have an impact on the marginal and poorer communities of developing countries: increased international demand for low-value fish on the supply of poorer countries; improved aquaculture technologies and productivity on poorer and marginal farmers; and land and water allocation policy on productivity, food security and sustainability across farm, fishery and related sectors. The key to local food security is in the integration of agriculture, aquaculture and natural resources but an important focus on fisheries policy research will be to look at the linkages between societal, economic and natural systems in order to develop adequate and flexible solutions to achieve sustainable use of aquatic resources systems.

Effects of water quality in Bassenthwaite Lake on anglers' catches of salmon and sea-trout in the River Derwent

This is the report on the Effects of Water Quality in the Bassenthwaite Lake on Anglers Catches of Salmon and Sea-trout in the River Derwent April 1993 by the Institute of Freshwater Ecology. An analysis of the catch statistics for salmon and sea-trout in the Rivers Derwent and Cocker was undertaken in relation to available information on the algal water quality in Bassenthwaite Lake to test the hypothesis that poor catch returns were associated with a deterioration of water quality within the lake. Analysis of the catch statistics failed to reveal any correlation between water quality and catch returns for either species of fish and it is concluded that any water deterioration in Bassenthwaite Lake has not caused any major damage to the salmon and sea trout fisheries of the Derwent/Cocker system. This conclusion is supported by the analysis of the Windermere/Leven and Crake system, where no correlation could be found between lake water quality and downstream catches of migratory salmonid fish. However, the possibility still exists and such an effect might be detected by further field work on the macroinvertebrates and on the composition of potential salmonid spawning in the area.

Avaliação da influência do manejo agrícola no uso e cobertura das terras através de ferramentas de geoprocessamento e indicadores de qualidade dos solos na bacia hidrográfica do Córrego da Caçada - Paraty/RJ

A avaliação da qualidade dos solos e a redução da Mata Atlântica tem sido alvo de diversas pesquisas no Brasil e no mundo, principalmente quando estes estão atrelados ao recorte espacial de Unidades de Conservação. No entanto, tem sido difícil para os gestores dessas unidades a avaliação dos impactos ambientais gerados ao longo dos anos nas bacias hidrográficas, principalmente pela falta de investimentos. Esta dissertação teve por objetivo geral avaliar o atual estágio de degradação da bacia hidrográfica do Córrego da Caçada pertencente à Área de Proteção Ambiental Federal de Cairuçu, no município de Paraty RJ, analisando quantitativamente e qualitativamente a redução dos fragmentos de Mata Atlântica e estabelecendo relações com a degradação física e química dos solos dentro e fora dos fragmentos florestais. A metodologia utilizada para a redução ou avanço dos fragmentos de Mata Atlântica baseou-se no uso de fotografias aéreas do ano de 1956 e imagens de satélite de 2012, onde possibilitou a avaliação espaço-temporal do uso e cobertura das terras, através da produção de um mapa temático final. Além disso, foram elaborados mapas temáticos de reconhecimento da área de estudo, como o de hipsometria, de declividade, de orientação e forma das encostas, além da geração de perfis topográficos. Para a avaliação da qualidade física, química e biológica dos solos foram determinadas as curvas de distribuição granulométrica, a densidade relativa dos grãos sólidos e a densidade aparente, porosidade total, os limites de liquidez e plasticidade, a estabilidade dos agregados em água, análises morfológicas, a saturação de bases, a capacidade de troca catiônica (CTC), a saturação por alumínio, fósforo, pH e o carbono orgânico. Para tal, foi realizada a abertura de três perfis, sendo um em área de fragmento florestal e dois em áreas de pasto. O resultado das análises permitiu, segundo a Sociedade Brasileira de Ciência do solo, a classificação de dois tipos de solos na bacia, sendo: Cambissolo Háplico Tb Distrófico Típico em área fragmento florestal e em área de pasto, e um Latossolo Amarelo Tb Distrófico Típico em área de pasto. Os resultados de laboratório mostraram que os solos avaliados têm baixa fertilidade e valores variados nos resultados de física do solo. No entanto, além do histórico de uso do solo caracterizado pelas práticas rudimentares do manejo empregado pelos Caiçaras, o clima predominante na região possibilita um regime pluviométrico anual que passa dos 2.000mm de chuva/ano, caracterizando solos muito lixiviados e pobres quimicamente. Portanto, conclui-se que a relação das propriedades físicas e químicas avaliadas junto ao manejo inadequado ao longo dos anos tem apresentado um cenário de grandes dificuldades para a recuperação florestal na bacia hidrográfica do Córrego da Caçada, o que mostra a importância da avaliação dos impactos ambientais não só pelo recorte de bacias hidrográficas, como contextualizar seu posicionamento dentro de Unidades de Conservação, com legislações e objetivos específicos.

Algae and water pollution in Mahi Estuary

Distribution of phytoplankton, chlorophyll A and phaeophytin was studied at different locations in the Mahi Estuary, Gujarat, India during 1982. The water quality at the discharge point was poor while the region away from it was relatively unpolluted. The results indicated a wide range of variation in phytoplankton population (7.68-5010, 96 x 10 super(4) cells/l, chl. a 2.22-58.22 mg/m super(3) and phaeophytin [0.20-10.21 mg/m super(3)]. The ratio of chl. a/phaeophytin were remarkably low at highly polluted stations. Higher abundance of the genera Oscillatoria and Nitzschia were recorded at polluted stations. The diversity of species at the unpolluted station was higher (1.56) as compared to the polluted station (1.07).

Water quality management on the enhancement of shrimp (Penaeus monodon Fab.) production in the traditional and improved-traditional ghers of Bangladesh

On-farm research on enhancement of P. monodon production through water quality management was carried out in five ghers of Paikgacha, Khulna. Based on the prevailing condition of the ghers, lime in the form of CaCO(sub 3), urea and TSP were used as the major inputs to minimize the soil-water acidity and to ensure the availability of natural food particles in the water bodies. Exchange of water at required level also practiced for the qualitative improvement of culture water. Ghers of varying sizes showed that water quality management and fertilization have a positive impact on production performance of P. monodon (61.59% increment) that yielded an average production of 385.43 kg/ha/crop against the present traditional rate of 238.50 kg/ha/year.

Reports of the ICSF seminar / workshop on the conditions of fishworkers on distant water vessels, Manila, Philippines, 1-3 February 1991

This ICSF Exchange Programme held in Manila is an offshoot of the Bangkok Conference on “Global Fisheries Trends and Future of Fishworkers” held on January 22–27, 1990. One of the issues raised in that conference was about the operation of Taiwanese fishing vessels outside its territorial waters and the impact of such operations on small fishermen from the countries concerned. The presence of a Taiwanese fishworker as well as an NGO supporter contributed to an enlightening discussion as the former shed light on the sad plight of Taiwanese fishworkers who are the victims of such structural problems. This meaningful exchange between groups of fishermen, particularly Taiwanese and Filipinos, resulted in the plan of the Taiwanese delegation to have some Taiwanese fishermen visit the Philippines and immerse in fishing communities.

Illegal fishing of inland water bodies of Nigeria: Kainji experience

It is a common knowledge that illegal fishing which includes use of wrong gears, explosives, excessive exploitation of choice stocks, enhancement and stocking of water body and pollution has devastating effects on the critical biomass of fish biodiversity and livelihood activities associated with fishing. Efforts worldwide to arrest these menace are significant because it has been found that illegal fishing has made fishing non sustainable, resulted in poor fishermen catches, and exacerbated the use of illegal gears in an effort to a must catch. Conflict between fisher folk and policies has continued to generate different strategies in the control of illegal fishing. Some of these strategies at regional and National levels include creation and implementation of fisheries laws, fishing edicts, code of conduct for responsible fisheries, policing of inland water bodies, capacity building and capability through training of fishermen, creating necessary awareness, arrest and punishment of offenders. There are also other initiative on conservation and management of freshwater ecosystems which have interrelation with illegal fishing. This paper examines efforts in promoting and boosting the fisheries of Lake Kainji, through creating necessary awareness, campaign visits, radio programmes, gear control, reward systems, integration and diversification of livelihood activities, community based management and policing. It further analyses what is working, problems, and prospect of fisheries laws, the need to integrate factors of political policies, other global initiative on water management for people and nature. Recommendations on strategies including protection of fishing grounds, establishment of catch data base, integration of other intervention as alternative source of income to enhance livelihood, reduce fishing pressure, and capacity building of fisher folks, development of rules and regulations that is community based are highlighted.

Nutrient profile of pond water in north-eastern state of Tripura and impact of water acidity on aquaculture productivity

Physicochemical parameters of 31 fish pond water samples of Tripura were studied to ascertain the nutrient profile of acidic soil zone and the impact of water acidity towards aquaculture productivity. The pH was acidic (mean 6.63±0.44) with high Fe (mean1.04±0.40 mglˉ¹) and AI (mean 2.67±2.41 mglˉ¹) contents. These were mostly responsible for pond water acidity and poor productivity with low nitrogen, phosphate and total alkalinity. The study also showed strong negative relationship between water pH and redox potential (R²=0.5251). However, pH was positively significant with electrical conductivity. The roles of redox potential and electrical conductivity in water acidity were found highly important. Available calcium content was also found low (mean 2.91±2.96 mglˉ¹). Elevating level of pH of pond water could be the possible management practices in acidic water so that such unproductive water might be productive enough with higher phosphate and nitrogen levels for better biological production.

Study on regional differences in soil-water characteristics and their relevance to aquaculture productivity and fish disease

A total of 45 ponds used for fish polyculture were investigated in three zones of Bangladesh to identify the differences among the zones in respect to aqua-ecology, culture practices, fish productivity and health management. Four hundred and fifty fish from three zones were clinically examined by naked eye and histopathology. Out of total number of fish examined, 45 fish from Dhaka zones were examined for parasites and bacteria in addition to histopathology. Faded and haemorrhagic gill, skin, fin, scale loss and lesions were observed during fish examination. Aeromonas spp. Pseudomonas spp. and Streptococcus spp. were isolated respectively from 56%, 46% and 39% affected fish. Among the five water quality parameters analyzed, the highest average hardness and alkalinity respectively were recorded in Rajshahi (156 ppm and 142 ppm) followed by Dhaka (146 ppm and 132 ppm) and Chittagong (81 ppm and 90 ppm). The highest average pH was recorded in Mymensingh (7.52) followed by Rajshahi (7.13) and Chittagong (7.05). Water holding capacity of soil in Rajshahi zone was poor compared to other zones and farmers were found to be reluctant to fish farming.

Poor fish farmers' accessibility to credits: A review

Fisheries sector contributes about 5.3% to GDP and about 6% of the export earnings of Bangladesh. There are about 4.1 million ha of inland water bodies in Bangladesh. However, over last two decades the catch from inland capture fishery has decreased due to filling of wet lands and other anthropogenic reasons. Accordingly, the production of inland fish has decreased not only for the decrease of water bodies but also due to irrational catch of fish fries, brood fishes and use of current nets for fishing. Significant responses from the fisheries entrepreneurs have not been received for the small loan scheme of the Bangladesh Bank. The bank could not disburse more than Tk. 500 million under the scheme. The total revolving credit under the scheme was Tk. 1,000 million with the assistance from the World Bank. The business houses having fixed assets of value not more than Tk. 10 million will be eligible to borrow from this fund. About Tk. 0.2-5.0 million can be borrowed as term loan and working capital from Bangladesh Bank through commercial banks. The loan was given to the commercial banks at 5% interest (bank rate) and the commercial banks shall also bridge finance to the entrepreneurs at a lower rate of interest. Working capital time limit is for a maximum of 1 year with half yearly rest, mid-term loan maximum of 3 years in 5 installments and with 6 months grace period and long-term loan maximum of 5 years in 9 installments with 6 months grace period.

QM/MM simulation of liquid water with an adaptive quantum region.

The simulation of complex chemical systems often requires a multi-level description, in which a region of special interest is treated using a computationally expensive quantum mechanical (QM) model while its environment is described by a faster, simpler molecular mechanical (MM) model. Furthermore, studying dynamic effects in solvated systems or bio-molecules requires a variable definition of the two regions, so that atoms or molecules can be dynamically re-assigned between the QM and MM descriptions during the course of the simulation. Such reassignments pose a problem for traditional QM/MM schemes by exacerbating the errors that stem from switching the model at the boundary. Here we show that stable, long adaptive simulations can be carried out using density functional theory with the BLYP exchange-correlation functional for the QM model and a flexible TIP3P force field for the MM model without requiring adjustments of either. Using a primary benchmark system of pure water, we investigate the convergence of the liquid structure with the size of the QM region, and demonstrate that by using a sufficiently large QM region (with radius 6 Å) it is possible to obtain radial and angular distributions that, in the QM region, match the results of fully quantum mechanical calculations with periodic boundary conditions, and, after a smooth transition, also agree with fully MM calculations in the MM region. The key ingredient is the accurate evaluation of forces in the QM subsystem which we achieve by including an extended buffer region in the QM calculations. We also show that our buffered-force QM/MM scheme is transferable by simulating the solvated Cl(-) ion.

Calculation of point defects in rutile TiO 2 by the screened-exchange hybrid functional

The formation energies of the oxygen vacancy and titanium interstitial in rutile TiO 2 were calculated by the screened-exchange (sX) hybrid density functional method, which gives a band gap of 3.1 eV, close to the experimental value. The oxygen vacancy gives rise to a gap state lying 0.7 eV below the conduction band edge, whose charge density is localized around the two of three Ti atoms next to the vacancy. The Ti interstitial (Ti int) generates four defect states in the gap, whose unpaired electrons lie on the interstitial and the adjacent Ti 3d orbitals. The formation energy for the neutral oxygen vacancy is 1.9 eV for the O-poor chemical potential. The neutral Ti interstitial has a lower formation energy than the O vacancy under O-poor conditions. This indicates that both the O vacancy and Ti int are relevant for oxygen deficiency in rutile TiO 2 but the O vacancy will dominate under O-rich conditions. This resolves questions about defect localization and defect predominance in the literature. © 2012 American Physical Society.

Finite element modelling of the sismic behaviour of water front structures

Water front structures have suffered significant damage in many of the recent earthquakes. These include gravity type quay walls, vertically composite walls, cantilever retaining walls, anchored bulkheads and similar structures. One of the primary causes for the poor performance of these classes of structures is the liquefaction of the foundation soil and in some instances liquefaction of the backfill soil. The liquefaction of the soil in-front of the quay wall tends to cause large lateral displacements and rotation of the wall. Often such gravity walls are placed on rubble mound deposited onto the sea bed.This paper presents finite element analyses of such a problem in which strength degradation of the foundation soil and the backfill material will be modelled using PZ mark III constitutive model. The performance of the wall in terms of its lateral displacement, vertical settlement and/or the rotation suffered by the wall will be presented. In addition, the contours of the horizontal and vertical effective stresses and the excess pore pressure ratio will be presented at different time instants together with hyrdraulic gradients. Immediately after the earthquake, the hydraulic gradients indicate migration of pore water into the region below the wall, suggesting further softening of the foundation soil below the wall.