Stabilization of the ionic form of weak acid cation exchange resins

Weak acid cation exchange (WAC) resins are used in the chromatographic separation of betaine from vinasse, a by-product of sugar industry. The ionic form of the resin determines the elution time of betaine. When a WAC-resin is in hydrogen form, the retention time of betaine is the longest and betaine elutes as the last component of vi-nasse from the chromatographic column. If the feed solution contains salts and its pH is not acidic enough to keep the resin undissociated, the ionic form of the hydrogen form resin starts to alter. Vinasse contains salts and its pH is around 5, it also contains weak acids. To keep the metal ion content (Na/H ratio) of the resin low enough to ensure successful separation of betaine, acid has to be added to either eluent (water) or vinasse. The aim of the present work was to examine by laboratory experiments which option requires less acid. Also the retention mechanism of betaine was investigated by measuring retention volumes of acetic acid and choline in different Na/H ratios of the resin. It was found that the resulting ionic form of the resin is the same regardless of whether the regeneration acid is added to the eluent or the feed solution (vinasse). Be-sides the salt concentration and the pH of vinasse, also the concentration of weak acids in the feed affects the resulting ionic form of the resin. The more buffering capacity vinasse has, the more acid is required to keep the ionic form of the resin desired. Vinasse was found to be quite strong buffer solution, which means relatively high amounts of acid are required to prevent the Na/H ratio from increasing too much. It is known that the retention volume of betaine decreases significantly, when the Na/H ratio increases. This is assumed to occur, because the amount of hydrogen bonds between the carboxylic groups of betaine and the resin decreases. Same behavior was not found with acetic acid. Choline has the same molecular structure as betaine, but instead of carboxylic group it has hydroxide group. The retention volume of choline increased as the Na/H ratio of the resin increased, because of the ion exchange reaction between choline cation and dissociated carboxylic group of the resin. Since the retention behavior of choline on the resin is opposite to the behavior of be-taine, the strong affinity of betaine towards hydrogen form WAC-resin has to be based on its carboxylic group. It is probable that the quaternary ammonium groups also affect the behavior of the carboxylic groups of betaine, causing them to form hydrogen bonds with the carboxylic groups of the resin.

Transforming Maritime Safety Culture. Evaluation of the impacts of the ISM Code on maritime safety culture in Finland

The purpose of the METKU Project (Development of Maritime Safety Culture) is to study how the ISM Code has influenced the safety culture in the maritime industry. This literature review is written as a part of the Work Package 2 which is conducted by the University of Turku, Centre for Maritime Studies. The maritime traffic is rapidly growing in the Baltic Sea which leads to a growing risk of maritime accidents. Particularly in the Gulf of Finland, the high volume of traffic causes a high risk of maritime accidents. The growing risks give us good reasons for implementing the research project concerning maritime safety and the effectiveness of the safety measures, such as the safety management systems. In order to reduce maritime safety risks, the safety management systems should be further developed. The METKU Project has been launched to examine the improvements which can be done to the safety management systems. Human errors are considered as the most important reason for maritime accidents. The international safety management code (the ISM Code) has been established to cut down the occurrence of human errors by creating a safety-oriented organizational culture for the maritime industry. The ISM Code requires that a company should provide safe practices in ship operation and a safe working environment and establish safeguards against all identified risk. The fundamental idea of the ISM Code is that companies should continuously improve safety. The commitment of the top management is essential for implementing a safety-oriented culture in a company. The ISM Code has brought a significant contribution to the progress of maritime safety in recent years. Shipping companies and ships’ crews are more environmentally friendly and more safety-oriented than 12 years ago. This has been showed by several studies which have been analysed for this literature research. Nevertheless, the direct effect and influence of the ISM Code on maritime safety could not be isolated very well. No quantitative measurement (statistics/hard data) could be found in order to present the impacts of the ISM Code on maritime safety. In this study it has been discovered that safety culture has emerged and it is developing in the maritime industry. Even though the roots of the safety culture have been established there are still serious barriers to the breakthrough of the safety management. These barriers could be envisaged as cultural factors preventing the safety process. Even though the ISM Code has been effective over a decade, the old-established behaviour which is based on the old day’s maritime culture still occurs. In the next phase of this research project, these cultural factors shall be analysed in regard to the present safety culture of the maritime industry in Finland.

Estimation of Water Circulation in a Mediterranean Salt Marsh and its Relationship with Flooding Causes

Variations in water volume in small depressions in Mediterranean salt marshes in Girona (Spain) are described and the potential causes for these variations analysed. Although the basins appear to be endorrheic, groundwater circulation is intense, as estimated from the difference between water volume observed and that expected from the balance precipitation / evaporation. The rate of variation in volume (VR = AV / VAt) may be used to estimate groundwater supply ('circulation'), since direct measurements of this parameter are impossible. Volume.conductivity figures can also be used to estimate the quantity of circulation, and to investigate the origin of water supplied to the system. The relationships between variations in the volume of water in the basins and the main causes of flooding are also analysed. Sea storms, rainfall levels and strong, dry northerly winds are suggested as the main causes of the variations in the volumes of basins. The relative importance assigned to these factors has changed, following the recent regulation of freshwater flows entering the system

Decolorization and toxicity of municipal waste by horseradish (Cochlearia armoracia)

The Municipal Station of Americana, SP, Brazil, treats a volume of 400 l s-1 of effluent, of domestic and textile origin, and produces about 20 t of sludge per day. The plant horseradish, which contains high amount of peroxidases, was able to decolorize this effluent in 2 h and the solid waste in 2 days, at concentrations of 10 and 50%, respectively. However, there was an increase in the toxicity for the bioassays with Hydra attenuatta, Selenastrum capricornutum and lettuce seeds, indicating formation of more toxic substances. Since horseradish showed the ability to decolorize these residues, it can be used as pre-treatment resulting in a sludge of less complex composition.

Prognosis of after spot volumes at the Scandinavian electricity market

The Thesis is dedicated to development of an operative tool to support decision making in after spot trading on the Nordic electricity market. The basics of the Nordic electricity market, trading mechanisms on the spot and after spot markets are presented in the Thesis. Mathematical equations that describe electricity balance condition in the power system are offered. The main driving factors that impact deviation of actual electricity balance from the scheduled one (object) in the power system have been explored and mathematically defined. The behavioral model of the object and principal trends in change of state of the object under an impact of the driving factors are determined with the help of regression analysis made in Microsoft Office Excel. The behavioral model gives an indication for the total regulation volume (Elbas trades volume, volume of regulation market, balance power) for a certain hour that serves as the base input in estimating prices on the after spot markets. Proposals for development of methodologies of forecasting the after spot electricity prices are offered.

Development of dissolution method for benznidazole tablets

The aim of this work was the development of a dissolution method for benznidazole (BNZ) tablets. Three different types of dissolution media, two stirring speeds and apparatus 2 (paddle) were used. The accomplishment of the drug dissolution profiles was compared through the dissolution efficiency. The assay was performed by spectrophotometry at 324 nm. The better conditions were: sodium chloride\hydrochloride acid buffer pH 1.2 with stirring speed of 75 rpm, volume of 900 mL and paddle as apparatus. Ahead of the results it can be concluded that the method developed consists in an efficient alternative for assays of dissolution for benznidazole tablets.

The history of the rectilinear diameter law

The formulation of the so-called law of rectilinear diameter for the determination of the critical volume of substances in the concluding decades of the nineteenth century became in a very useful and acceptably exact alternative tool for researchers in the field of critical phenomena. Its corresponding original expression, and even those of its early few modifications, were so mathematically simple that their use did not limit to exclusively contribute to remove the by then experimental obstacle for the estimating of this critical parameter, but also extended along several decades in the increasing applications of the principle of corresponding states.

Determination of traces of nitrate in water samples using spectrophotometric method after its preconcentration on microcrystalline naphthalene

Nitrate is quantitatively retained with 2,6-bis(4-methoxyphenyl)-4-phenyl pyrylium perchlorate (PPP) on microcrystalline naphthalene in the pH range of 6.5-9.0 from a large volume of aqueous solutions of various samples. The method was based on the complexation between PPP and nitrate and then, extraction of the resulted complex from aqueous solution by microcrystalline naphthalene. The solid mass consisting of the nitrate complex and naphthalene was then dissolved in dimethyl formamide (DMF) and absorption of the resulted solution was obtained at 328 nm. The linear calibration range for the determination of nitrate was 15-135 μg L-1 with the detection limit of 10 μg L-1.

Development of a flotation-spectrophotometric method for determination of cetylpyridinium chloride in pharmaceutical products

A new simple and sensitive flotation-spectrophotometric method for the determination of cetylpyridinium chloride (CPC) is reported. The method is based on the formation of an ion- associate between CPC and Orange II (OR) which is floated in the interface of aqueous phase and n-hexane by vigorous shaking. The aqueous solution was discarded and the adsorbed ion associate on to the wall of a separating funnel was dissolved in a small volume of methanol solvent and its absorbance was measured at 480 nm. The apparent molar absorptivity (Ε) of the ion associate was determined to be 4.12 x 10(5) L mol-1 cm-1. The calibration graph was linear in the concentration range of 15-800 ng mL-1 of CPC with a correlation coefficient of 0.9988. The limit of detection (LOD) was 10.8 ng mL-1. The relative standard deviation (RSD) for determination of 100 and 800 ng mL-1 of CPC was 3.47 and 2.04% (n=7), respectively. The method was successfully applied to the determination of CPC in a commercial mouth washer product.

Development of Russian Ports in The Gulf of Finland

Russia has been one of the fastest developing economic areas in the world. Based on the GDP, the Russian economy grew evenly since the crisis in 1998 up till 2008. The growth in the gross domestic product has annually been some 5–10%. In 2007, the growth reached 8.1%, which is the highest figure after the 10% growth in 2000. Due to the growth of the economy and wage levels, purchasing power and consumption have been strongly increasing. The growing consumption has especially increased the imports of durables, such as passenger cars, domestic appliances and electronics. The Russian ports and infrastructure have not been able to satisfy the growing needs of exports and imports, which is why quite a large share of Russian foreign trade is going through third countries as transit transports. Finnish ports play a major role in transit transports to and from Russia. About 15% of the total value of Russian imports was transported through Finland in 2008. The economic recession that started in autumn 2008 and continues to date has had an impact on the economic development of Russia. The export income has decreased, mainly due to the reduced world market prices of energy products (oil and gas) and raw minerals. Investments have been postponed, getting credit is more difficult than before, and the ruble has weakened in relation to the euro and the dollar. The imports are decreasing remarkably, and are not forecast to reach the 2008 volumes even in 2012. The economic crisis is reflected in Finland's transit traffic. The volume of goods transported through Finland to and from Russia has decreased almost in the same proportion as the imports of goods to Russia. The biggest risk threatening the development of the Russian economy over long term is its dependence on export income from oil, gas, metals, minerals and forest products, as well as the trends of the world market prices of these products. Nevertheless, it is expected that the GDP of Russia will start to grow again in the forthcoming years due to the increased demand for energy products and raw minerals in the world. At the same time, it is obvious that the world market prices of these products will go up with the increasing demand. The increased income from exports will lead to a growth of imports, especially those of consumer goods, as the living standard of Russian citizens rises. The forecasts produced by the Russian Government concerning the economic development of Russia up till 2030 also indicate a shift in exported goods from raw materials to processed products, which together with energy products will become the main export goods of Russia. As a consequence, Russia may need export routes through third countries, which can be seen as an opportunity for increased transit transports through the ports of Finland. The ports competing with the ports of Finland for Russian foreign trade traffic are the Russian Baltic Sea ports and the ports of the Baltic countries. The strongest competitors are the Baltic Sea ports handling containers. On the Russian Baltic Sea, these ports include Saint Petersburg, Kaliningrad and, in the near future, the ports of Ust-Luga and possibly Vyborg. There are plans to develop Ust-Luga and Vyborg as modern container ports, which would become serious competitors to the Finnish ports. Russia is aiming to redirect as large a share as possible of foreign trade traffic to its own ports. The ports of Russia and the infrastructure associated with them are under constant development. On the other hand, the logistic capacity of Russia is not able to satisfy the continually growing needs of the Russian foreign trade. The capacity problem is emphasized by a structural incompatibility between the exports and imports in the Russian foreign trade. Russian exports can only use a small part of the containers brought in with imports. Problems are also caused by the difficult ice conditions and narrow waterways leading to the ports. It is predicted that Finland will maintain its position as a transit route for the Russian foreign trade, at least in the near future. The Russian foreign trade is increasing, and Russia will not be able to develop its ports in proportion with the increasing foreign trade. With the development of port capacity, cargo flows through the ports of Russia will grow. Structural changes in transit traffic are already visible. Firms are more and more relocating their production to Russia, for example as regards the assembly of cars and warehousing services. Simultaneously, an increasing part of transit cargoes are sent directly to Russia without unloading and reloading in Finland. New product groups have nevertheless been transported through Finland (textile products and tools), replacing the lost cargos. The global recession that started in autumn 2008 has influenced the volume of Russian imports and, consequently, the transit volumes of Finland, but the recession is not expected to be of long duration, and will thus only have a short-term impact on transit volumes. The Finnish infrastructure and services offered by the logistic chain should also be ready to react to the changes in imported product groups as well as to the change in Russian export products in the future. If the development plans of the Russian economy are realized, export products will be more refined, and the share of energy and raw material products will decrease. The other notable factor to be taken into consideration is the extremely fast-changing business environment in Russia. Operators in the logistic chain should be flexible enough to adapt to all kinds of changes to capitalise on business opportunities offered by the Russian foreign trade for the companies and for the transit volumes of Finnish ports, also in the future.

Dispersive liquid-liquid microextraction for the simultaneous separation of trace amounts of zinc and cadmium ions in water samples prior to flame atomic absorption spectrometry determination

In the proposed method, carbon tetrachloride and ethanol were used as extraction and dispersive solvents. Several factors that may be affected on the extraction process, such as extraction solvent, disperser solvent, the volume of extraction and disperser solvent, pH of the aqueous solution and extraction time were optimized. Under the optimal conditions, linearity was maintained between 1.0 ng mL-1 to 1.5 mg mL-1 for zinc and 1.0 ng mL-1 to 0.4 mg mL-1 for cadmium. The proposed method has been applied for determination of trace amount of zinc and cadmium in standard and water samples with satisfactory results.

Treatment for purification water of biodiesel using electrofloculation

Biodiesel was created as a solution for a great economic and enviromental problem of petroleum, a resource with sustainable characteristics. But its production still needs optimization, because it uses a lot of water and generates a large volume of this residue, which appears improper to disposal without correct treatment. This work propose an economic, viable and efficient way to treat the Biodiesel purification water, not only aiming at a proper disposal, but the reuse as input in the process, generating a large industrial economy, and greater environmental progress. For both treatment uses the electrofloculation technique.

Dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous separation/preconcentration of nickel, cobalt and copper prior to determination by electrothermal atomic absorption spectrometry

A dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous extraction of trace amounts of nickel, cobalt and copper followed by their determination with electrothermal atomic absorption spectrometry was developed. 300 µL of acetone and 1-undecanol was injected into an aqueous sample containing diethyldithiocarbamate complexes of metal ions. For a sample volume of 10 mL, enrichment factors of 277, 270 and 300 and detection limits of 1.2, 1.1 and 1 ng L-1 for nickel, cobalt and copper were obtained, respectively. The method was applied to the extraction and determination of these metals in different water samples.

Equipamento de baixo custo para extração em fase sólida em amostras aquosas de grande volume utilizando pressão positiva de N

Extraction/concentration is a crucial step for the analysis of organic compounds at trace level concentrations and dispersed in complex matrices. Solid-phase extraction (SPE) is one of the techniques used for this purpose. In this work, a low cost apparatus for SPE was developed that uses nitrogen under positive pressure and ensures the maintenance of the sample flow, while also allows the simultaneous extraction of different samples without cross-contamination and sample contact with plastic materials. For the system set up, easily accessible materials were used such as hypodermic needles, stainless steel tubes, rubber stoppers, and 3-way valves from serum delivery apparatus.

Spectrophotometric determination of Sudan Blue II in environmental samples after dispersive liquid-liquid microextraction

A dispersive liquid-liquid microextraction procedure coupled to spectrophotometry is described for the determination of the trace levels of Sudan Blue II. Analytical parameters, such as pH, volume of extraction solvent (carbon tetrachloride), volume of dispersant (ethanol), volume of sample, and extraction time, were optimized. Matrix effects were also investigated. Preconcentration factor was found to be 200. Detection limit and relative standard deviation (RSD) were 0.55 µg L-1 and 3.9%, respectively. The procedure was successfully used for the determination of trace levels of Sudan Blue II in food, ink, antifreeze, and industrial waste-water samples.