Catálise eletroquímica da redução do bromato em superfícies modificadas por filmes de molibdênio

In this paper some studies concerning the electroreduction of Mo(VI) in sulphuric acid solutions are described. We have shown that at suitable experimental conditions very stable molybdenum oxide films can be electrochemically deposited at glassy carbon electrodes, the reduction of bromate occurring at less negative potentials on the modified surface. Coulometric experiments have shown that bromide is not the only product of the catalytic bromate reduction by the molybdenum film and species like BrO2 may have part in this process. Based on chronoamperometric curves recorded at -0.60 V, analytical curves have been obtained for the reduction of bromate in the 0.1 - 0.8 mM range, a limit of detection of 20 µM for bromate being determined.

Empirical analysis of solid management waste costs: Some evidence from Galicia, Spain

This paper analyses the factors that determine solid waste service costs. The empirical analysis is based on information derived from a survey conducted in a sample of Galician municipalities. The results reveal economies of scale in municipalities of fewer than 50,000 inhabitants, such that cooperation between these municipalities could lead to cost savings. It also appears that private delivery is not cheaper than public delivery. Finally, designating a larger proportion of the total waste volume to recycling does not imply greater costs.

Climate Change and the Cost of Carbon Sequestration: The Case of Forest Management

The Kyoto protocol allows Annex I countries to deduct carbon sequestered by land use, land-use change and forestry from their national carbon emissions. Thornley and Cannell (2000) demonstrated that the objectives of maximizing timber and carbon sequestration are not complementary. Based on this finding, this paper determines the optimal selective management regime taking into account the underlying biophysical and economic processes. The results show that the net benefits of carbon storage only compensate the decrease in net benefits of timber production once the carbon price has exceeded a certain threshold value. The sequestration costs are significantly lower than previous estimates

Power Consumption in Carbon Capture and Storage Systems (CCS) and Possibilities to Reduce Power Consumption with Variable Speed Drives

The aim of this master´s thesis is to study which processes increase the auxiliary power consumption in carbon capture and storage processes and if it is possible to reduce the auxiliary power consumption with variable speed drives. Also the cost of carbon capture and storage is studied. Data about auxiliary power consumption in carbon capture is gathered from various studies and estimates made by various research centres. Based on these studies a view is presented how the power auxiliary power consumption is divided between different processes in carbon capture processes. In a literary study, the operation of three basic carbon capture systems is described. Also different methods to transport carbon dioxide and carbon dioxide storage options are described in this section. At the end of the thesis processes that consume most of the auxiliary power are defined and possibilities to reduce the auxiliary power consumption are evaluated. Cost of carbon capture, transport and storage are also evaluated at this point and in the case that the carbon capture and storage systems are fully deployed. According to the results, it can be estimated what are the processes are where variable speed drives can be used and what kind of cost and power consumption reduction could be achieved. Results also show how large a project carbon capture and storage is if it is fully deployed.

Use of the Optical Cantilever Microphone in Photoacoustic Spectroscopy

A novel cantilever pressure sensor was developed in the Department of Physics at the University of Turku in order to solve the sensitivity problems which are encountered when condenser microphones are used in photoacoustic spectroscopy. The cantilever pressure sensor, combined with a laser interferometer for the measurement of the cantilever movements, proved to be highly sensitive. The original aim of this work was to integrate the sensor in a photoacoustic gas detector working in a differential measurement scheme. The integration was made successfully into three prototypes. In addition, the cantilever was also integrated in the photoacoustic FTIR measurement schemes of gas-, liquid-, and solid-phase samples. A theoretical model for the signal generation in each measurement scheme was created and the optimal celldesign discussed. The sensitivity and selectivity of the differential method were evaluated when a blackbody radiator and a mechanical chopper were used with CO₂, CH4, CO, and C2H4 gases. The detection limits were in the sub-ppm level for all four gases with only a 1.3 second integration time and the cross interference was well below one percent for all gas combinations other than those between hydrocarbons. Sensitivity with other infrared sources was compared using ethylene as an example gas. In the comparison of sensitivity with different infrared sources the electrically modulated blackbody radiator gave a 35 times higher and the CO2-laser a 100 times lower detection limit than the blackbody radiator with a mechanical chopper. As a conclusion, the differential system is well suited to rapid single gas measurements. Gas-phase photoacoustic FTIR spectroscopy gives the best performance, when several components have to be analyzed simultaneously from multicomponent samples. Multicomponent measurements were demonstrated with a sample that contained different concentrations of CO₂, H₂O, CO, and four different hydrocarbons. It required an approximately 10 times longer measurement time to achieve the same detection limit for a single gas as with the differential system. The properties of the photoacoustic FTIR spectroscopy were also compared to conventional transmission FTIR spectroscopy by simulations. Solid- and liquid-phase photoacoustic FTIR spectroscopy has several advantages compared to other techniques and therefore it also has a great variety of applications. A comparison of the signal-to-noise ratio between photoacoustic cells with a cantilever microphone and a condenser microphone was done with standard carbon black, polyethene, and sunflower oil samples. The cell with the cantilever microphone proved to have a 5-10 times higher signal-to-noise ratio than the reference detector, depending on the sample. Cantilever enhanced photoacoustics will be an effective tool for gas detection and analysis of solid- and liquid-phase samples. The preliminary prototypes gave good results in all three measurement schemes that were studied. According to simulations, there are possibilities for further enhancement of the sensitivity, as well as other properties, of each system.

Hidrogenação eletrocatalítica de substratos orgânicos: estudo da eficiência dos metais nobres níquel, paládio e platina usando eletrodos modificados

Nickel, palladium and platinum micro-crystals were dispersed in films covering a vitreous carbon plate electrode by ion exchange followed by electroreduction of their ions. These modified electrodes were used in the electrocatalytic hydrogenation of several substrates of different classes and their efficiency is reported. A comparison among them was performed based on the structural characteristics of the metals. A modified electrode containing platinum showed to be more efficient than a palladium modified electrode and the one of nickel was the less efficient.

Solid phase extraction of iron and lead in environmental matrices on amberlite xad-1180/pv

A solid phase extraction procedure using Amberlite XAD-1180/Pyrocatechol violet (PV) chelating resin for the determination of iron and lead ions in various environmental samples was established. The procedure is based on the sorption of lead(II) and iron(III) ions onto the resin at pH 9, followed by elution with 1 mol/L HNO3 and determination by flame atomic absorption spectrometry. The influence of alkaline, earth alkaline and some transition metals, as interferents, are discussed. The recoveries for the spiked analytes were greater than 95%. The detection limits for lead and iron by FAAS were 0.37 µg/L and 0.20 µg/L, respectively. Validation of the method described here was performed by using three certified reference materials (SRM 1515 Apple Leaves, SRM 2711 Montana Soil and NRCC-SLRS-4 Riverine Water). The procedure was successfully applied to natural waters and human hair.

Estudo da capacidade de complexação e sua relação com algumas variáveis ambientais em cinco represas do Rio Tietê/Brasil

The copper and cadmium complexation properties in natural sediment suspensions of reservoirs of the Tietê River were studied using the solid membrane copper and cadmium ion-selective electrodes. The complexation and the average conditional stability constants were determined under equilibrium conditions at pH=6.00 ± 0.05 in a medium of 1.0 mol L-1 sodium nitrate, using the Scatchard method. The copper and cadmium electrodes presented Nernstian behavior from 1x10-6 to 1x10-3 mol L-1 of total metal concentration. Scatchard graphs suggest two classes of binding sites for both metals. A multivariate study was done to correlate the reservoirs and the variables: complexation properties, size, total organic carbon, volatile acid sulfide, E II and pH.

Dinâmica complexa no sistema bromato/hipofosfito/acetona/manganês e ferroína

New chemical systems have been recently designed for the study of complex phenomena such as oscillatory dynamics in the temporal domain and spatiotemporal pattern formation. Systems derived from oscillators based on the chemistry of bromate are the most extensively studied, with the celebrated Belousov-Zhabotinsky (BZ) reaction being the most popular example. Problems such as the formation of bubbles (CO2) and solid precipitate in the course of the reaction and the occurrence of simply short-lived oscillations under batch conditions are very common and, in some cases, compromise the use of some of these systems. It is investigated in this paper the dynamic behavior of the bromate/hypophosphite/acetone/dual catalyst system, which has been sugested as an interesting alternative to circumvent those inconvenients. In this work, manganese and ferroin are employed as catalysts and the complete system (BrO3-/H2PO2-/acetone/Mn(II)-ferroin) is studied under batch conditions. Temporal symmetry breaking was studied in a reactor under agitation by means of simultaneous records of the potential changes of platinum and Ag/AgBr electrodes, both measured versus a reversible hydrogen electrode. Additionally, spatio-temporal formation of target patterns and spiral waves were obtained when the oscillating mixture was placed in a quasi two-dimensional reactor.

Nocturnal Transcutaneous Carbon Dioxide and Early Changes in Atherosclerosis in Pre- and Postmenopausal Women

The risk of cardiovascular diseases and sleep-disordered breathing increases after menopause. This cross-sectional study focuses on overnight transcutaneous carbon dioxide (TcCO₂) measurements and their power to predict changes in the early markers of cardiovascular and metabolic diseases. The endothelial function of the brachial artery, the intima-media thickness of the carotid artery, blood pressure, glycosylated hemoglobin A1C and plasma levels of cholesterols and triglycerides were used as markers of cardiovascular and metabolic diseases. The study subjects consisted of healthy premenopausal women of 46 years of age and postmenopausal women of 56 years of age. From wakefulness to sleep, the TcCO₂ levels increased more in postmenopausal women than in premenopausal women. In estrogen-users the increase in TcCO₂ levels was even more pronounced than in other postmenopausal women. From the dynamic behaviour of the nocturnal TcCO₂ signal, several important features were detected. These TcCO₂ features had a remarkable role in the prediction of endothelial dysfunction and thickening of the carotid wall in healthy premenopausal women. In addition, these TcCO₂ features were linked with blood pressure, lipid profile and glucose balance in postmenopausal women. The nocturnal TcCO₂ profile seems to contain significant information, which is associated with early changes in cardiovascular diseases in middle-aged women. TcCO₂ might not only measure the tissue carbon dioxide levels, but the TcCO₂ signal variation may also reflect peripheral vasodynamic events caused by increased sympathetic activity during sleep.

Development of beam and plate finite elements based on the absolute nodal coordinate formulation

The focus of this dissertation is to develop finite elements based on the absolute nodal coordinate formulation. The absolute nodal coordinate formulation is a nonlinear finite element formulation, which is introduced for special requirements in the field of flexible multibody dynamics. In this formulation, a special definition for the rotation of elements is employed to ensure the formulation will not suffer from singularities due to large rotations. The absolute nodal coordinate formulation can be used for analyzing the dynamics of beam, plate and shell type structures. The improvements of the formulation are mainly concentrated towards the description of transverse shear deformation. Additionally, the formulation is verified by using conventional iso-parametric solid finite element and geometrically exact beam theory. Previous claims about especially high eigenfrequencies are studied by introducing beam elements based on the absolute nodal coordinate formulation in the framework of the large rotation vector approach. Additionally, the same high eigenfrequency problem is studied by using constraints for transverse deformation. It was determined that the improvements for shear deformation in the transverse direction lead to clear improvements in computational efficiency. This was especially true when comparative stress must be defined, for example when using elasto-plastic material. Furthermore, the developed plate element can be used to avoid certain numerical problems, such as shear and curvature lockings. In addition, it was shown that when compared to conventional solid elements, or elements based on nonlinear beam theory, elements based on the absolute nodal coordinate formulation do not lead to an especially stiff system for the equations of motion.

Calculation of the carbon footprint of Finnish barley products - methodology and possible applications

The purpose of this thesis was to define how product carbon footprint analysis and its results can be used in company's internal development as well as in customer and interest group guidance, and how these factors are related to corporate social responsibility. From-cradle-to-gate carbon footprint was calculated for three products; Torino Whole grain barley, Torino Pearl barley, and Elovena Barley grit & oat bran, all of them made of Finnish barley. The carbon footprint of the Elovena product was used to determine carbon footprints for industrial kitchen cooked porridge portions. The basic calculation data was collected from several sources. Most of the data originated from Raisio Group's contractual farmers and Raisio Group's cultivation, processing and packaging specialists. Data from national and European literature and database sources was also used. The electricity consumption for porridge portions' carbon footprint calculations was determined with practical measurements. The carbon footprint calculations were conducted according to the ISO 14044 standard, and the PAS 2050 guide was also applied. A consequential functional unit was applied in porridge portions' carbon footprint calculations. Most of the emissions from barley products' life cycle originate from primary production. The nitrous oxide emissions from cultivated soil and the use and production of nitrogenous fertilisers contribute over 50% of products' carbon footprint. Torino Pearl barley has the highest carbon footprint due to the lowest processing output. The reductions in products' carbon footprint can be achieved with developments in cultivation and grain processing. The carbon footprint of porridge portion can be reduced by using domestically produced plant-based ingredients and by making the best possible use of the kettle. Carbon footprint calculation can be used to determine possible improvement points related to corporate environmental responsibility. Several improvement actions are related to economical and social responsibility through better raw material utilization and expense reductions.

Population-based multicase-control study in common tumors in Spain (MCC-Spain): rationale and study design

INTRODUCTION: We present the protocol of a large population-based case-control study of 5 common tumors in Spain (MCC-Spain) that evaluates environmental exposures and genetic factors. METHODS: Between 2008-2013, 10,183 persons aged 20-85 years were enrolled in 23 hospitals and primary care centres in 12 Spanish provinces including 1,115 cases of a new diagnosis of prostate cancer, 1,750 of breast cancer, 2,171 of colorectal cancer, 492 of gastro-oesophageal cancer, 554 cases of chronic lymphocytic leukaemia (CLL) and 4,101 population-based controls matched by frequency to cases by age, sex and region of residence. Participation rates ranged from 57% (stomach cancer) to 87% (CLL cases) and from 30% to 77% in controls. Participants completed a face-to-face computerized interview on sociodemographic factors, environmental exposures, occupation, medication, lifestyle, and personal and family medical history. In addition, participants completed a self-administered food-frequency questionnaire and telephone interviews. Blood samples were collected from 76% of participants while saliva samples were collected in CLL cases and participants refusing blood extractions. Clinical information was recorded for cases and paraffin blocks and/or fresh tumor samples are available in most collaborating hospitals. Genotyping was done through an exome array enriched with genetic markers in specific pathways. Multiple analyses are planned to assess the association of environmental, personal and genetic risk factors for each tumor and to identify pleiotropic effects. DISCUSSION: This study, conducted within the Spanish Consortium for Biomedical Research in Epidemiology & Public Health (CIBERESP), is a unique initiative to evaluate etiological factors for common cancers and will promote cancer research and prevention in Spain.

Produção de biossurfactante por Aspergillus fumigatus utilizando resíduos agroindustriais como substrato

The objective of this study was to investigate biosurfactant production in solid state by Aspergillus fumigatus in fixed-bed column bioreactors using substrate based on agricultural residues. Without a supplementary carbon source the highest emulsifying activity (EA) was 11.17 emulsifying units (EU) g-1 of substrate at an aeration rate of 148 mL h-1g-1 but in the presence of diesel oil the highest EA value was 9.99 EU g-1 at an aeration rate of 119 mL h-1g-1 of substrate while supplementation with soya oil resulted in only 8.47 EU g-1 of substrate at an aeration rate of 119 mL h-1g-1.

Recovery of manganese and zinc from spent Zn-C and alkaline batteries in acidic medium

The anode and the internal paste of spent Zn-C and alkaline batteries were leached with 2 mol L-1 H2SO4 at 80 ºC for 2 h. Solid/liquid ratio was 1/10 (g mL-1). The leachate was treated with Na2S in order to precipitate Hg, Cd and Pb. Zn was quantitatively isolated at pH 1,5-2 by adding Na2S. Mn can be precipitated at pH close to 7. Na2S may be replaced by oxalic acid. Zn precipitated at pH around 0, whereas Mn was quantitatively recovered at pH > 4. Acidity control is a critical parameter. Na2SO4 and carbon are the end products.