Adsorption behavior of α-cypermethrin on cork and activated carbon

Studies were undertaken to determine the adsorption behavior of α-cypermethrin [R)-α-cyano-3-phenoxybenzyl(1S)-cis- 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-α-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze α-cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time—24 hours for both cork (1–2 mm and 3–4 mm) and GAC. For the studied α-cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1–2 mm have the maximum amount of adsorbed α-cypermethrin (qm) (303 μg/g); followed by GAC (186 μg/g) and cork 3-4 mm (136 μg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the α-cypermethrin adsorption phenomena on GAC, while α-cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing α-cypermethrin from water.

Effects of early life permethrin exposure on spatial working memory and on monoamine levels in different brain areas of pre-senescent rats

Pesticide exposure during brain development could represent an important risk factor for the onset of neurodegenerative diseases. Previous studies investigated the effect of permethrin (PERM) administered at 34 mg/kg, a dose close to the no observable adverse effect level (NOAEL) from post natal day (PND) 6 to PND 21 in rats. Despite the PERM dose did not elicited overt signs of toxicity (i.e. normal body weight gain curve), it was able to induce striatal neurodegeneration (dopamine and Nurr1 reduction, and lipid peroxidation increase). The present study was designed to characterize the cognitive deficits in the current animal model. When during late adulthood PERM treated rats were tested for spatial working memory performances in a T-maze-rewarded alternation task they took longer to choose for the correct arm in comparison to age matched controls. No differences between groups were found in anxiety-like state, locomotor activity, feeding behavior and spatial orientation task. Our findings showing a selective effect of PERM treatment on the T-maze task point to an involvement of frontal cortico-striatal circuitry rather than to a role for the hippocampus. The predominant disturbances concern the dopamine (DA) depletion in the striatum and, the serotonin (5-HT) and noradrenaline (NE) unbalance together with a hypometabolic state in the medial prefrontal cortex area. In the hippocampus, an increase of NE and a decrease of DA were observed in PERM treated rats as compared to controls. The concentration of the most representative marker for pyrethroid exposure (3-phenoxybenzoic acid) measured in the urine of rodents 12 h after the last treatment was 41.50 µ/L and it was completely eliminated after 96 h.

A study of ternary Cu2SnS3 and Cu3SnS4 thin films prepared by sulfurizing stacked metal precursors

Thin films of Cu2SnS3 and Cu3SnS4 were grown by sulfurization of dc magnetron sputtered Sn–Cu metallic precursors in a S2 atmosphere. Different maximum sulfurization temperatures were tested which allowed the study of the Cu2SnS3 phase changes. For a temperature of 350 ◦C the films were composed of tetragonal (I -42m) Cu2SnS3. The films sulfurized at a maximum temperature of 400 ◦C presented a cubic (F-43m) Cu2SnS3 phase. On increasing the temperature up to 520 ◦C, the Sn content of the layer decreased and orthorhombic (Pmn21) Cu3SnS4 was formed. The phase identification and structural analysis were performed using x-ray diffraction (XRD) and electron backscattered diffraction (EBSD) analysis. Raman scattering analysis was also performed and a comparison with XRD and EBSD data allowed the assignment of peaks at 336 and 351 cm−1 for tetragonal Cu2SnS3, 303 and 355 cm−1 for cubic Cu2SnS3, and 318, 348 and 295 cm−1 for the Cu3SnS4 phase. Compositional analysis was done using energy dispersive spectroscopy and induced coupled plasma analysis. Scanning electron microscopy was used to study the morphology of the layers. Transmittance and reflectance measurements permitted the estimation of absorbance and band gap. These ternary compounds present a high absorbance value close to 104 cm−1. The estimated band gap energy was 1.35 eV for tetragonal (I -42m) Cu2SnS3, 0.96 eV for cubic (F-43m) Cu2SnS3 and 1.60 eV for orthorhombic (Pmn21) Cu3SnS4. A hot point probe was used for the determination of semiconductor conductivity type. The results show that all the samples are p-type semiconductors. A four-point probe was used to obtain the resistivity of these samples. The resistivities for tetragonal Cu2SnS3, cubic Cu2SnS3 and orthorhombic (Pmn21) Cu3SnS4 are 4.59 × 10−2 cm, 1.26 × 10−2 cm, 7.40 × 10−4 cm, respectively.

CuxSnSx+1 (x = 2, 3) thin films grown by sulfurization of metallic precursors deposited by dc magnetron sputtering

We report the results of the growth of Cu-Sn-S ternary chalcogenide compounds by sulfurization of dc magnetron sputtered metallic precursors. Tetragonal Cu2SnS3 forms for a maximum sulfurization temperature of 350 ºC. Cubic Cu2SnS3 is obtained at sulfurization temperatures above 400 ºC. These results are supported by XRD analysis and Raman spectroscopy measurements. The latter analysis shows peaks at 336 cm-1, 351 cm-1 for tetragonal Cu2SnS3, and 303 cm-1, 355 cm-1 for cubic Cu2SnS3. Optical analysis shows that this phase change lowers the band gap from 1.35 eV to 0.98 eV. At higher sulfurization temperatures increased loss of Sn is expected in the sulphide form. As a consequence, higher Cu content ternary compounds like Cu3SnS4 grow. In these conditions, XRD and Raman analysis only detected orthorhombic (Pmn21) phase (petrukite). This compound has Raman peaks at 318 cm-1, 348 cm-1 and 295 cm-1. For a sulfurization temperature of 450 ºC the samples present a multi-phase structure mainly composed by cubic Cu2SnS3 and orthorhombic (Pmn21) Cu3SnS4. For higher temperatures, the samples are single phase and constituted by orthorhombic (Pmn21) Cu3SnS4. Transmittance and reflectance measurements were used to estimate a band gap of 1.60 eV. For comparison we also include the results for Cu2ZnSnS4 obtained using similar growth conditions.

Self-mated tribological systems based on multilayer micro/nanocrystalline CVD diamond coatings

The tribological response of multilayer micro/nanocrystalline diamond coatings grown by the hot filament CVD technique is investigated. These multigrade systems were tailored to comprise a starting microcrystalline diamond (MCD) layer with high adhesion to a silicon nitride (Si3N4) ceramic substrate, and a top nanocrystalline diamond (NCD) layer with reduced surface roughness. Tribological tests were carried out with a reciprocating sliding configuration without lubrication. Such composite coatings exhibit a superior critical load before delamination (130–200 N), when compared to the mono- (60–100 N) and bilayer coatings (110 N), considering ∼10 µm thick films. Regarding the friction behaviour, a short-lived initial high friction coefficient was followed by low friction regimes (friction coefficients between 0.02 and 0.09) as a result of the polished surfaces tailored by the tribological solicitation. Very mild to mild wear regimes (wear coefficient values between 4.1×10−8 and 7.7×10−7 mm3 N−1 m−1) governed the wear performance of the self-mated multilayer coatings when subjected to high-load short-term tests (60–200 N; 2 h; 86 m) and medium-load endurance tests (60 N; 16 h; 691 m).

Psychometric Properties of the Portuguese Version of the Posttraumatic Growth Inventory Short Form Among Divorced Adults

The aim of this study was to develop and validate a Portuguese version of the Short Form of the Posttraumatic Growth Inventory (PTGI-SF). Using an online convenience sample of Portuguese divorced adults (N = 482), we confirmed the oblique five-factor structure of the PTGI-SF by confirmatory factor analysis. The results demonstrated the measurement invariance across divorce initiator status groups. Total score and factors of PTGI-SF showed good internal consistency, with the exception of the New Possibilities factor, which revealed an acceptable reliability. The Portuguese PTGI-SF showed a satisfactory convergent validity. In terms of discriminant validity, posttraumatic growth assessed by the Portuguese PTGI-SF was a distinct factor from posttraumatic psychological adjustment. These preliminary findings suggest the cultural adaptation and also psychometric properties of the present Portuguese PTGI-SF to measure posttraumatic growth after personal crisis.

Avaliação da qualidade do ar e classificação energética de uma piscina coberta e propostas de melhoria

A presente dissertação tem dois objetivos, o primeiro é a realização de uma auditoria energética e avaliação da qualidade do ar às instalações de uma Piscina Municipal, permitindo a sua classificação energética, e o segundo é o estudo de propostas de melhoria que contribuam para uma melhor eficiência energética do edifício. Na análise à qualidade do ar interior os parâmetros avaliados encontravam-se todos dentro dos limites estabelecidos por lei, com exceção dos valores de COVs que em dois pontos de medição (ambos na nave) ultrapassaram os limites estabelecidos por lei. A auditoria ao edifício permitiu verificar que o caudal mínimo de água nova nas piscinas imposto por lei é cumprido pela instalação. No que diz respeito ao caudal de ar novo introduzido, este apenas é respeitado quando a unidade de tratamento de ar está a debitar 100% da sua capacidade. Quando a unidade opera a 50% da sua capacidade apresenta um défice de 5% do valor mínimo estabelecido. Relativamente às perdas energéticas associadas aos tanques de natação, estas apresentam um valor de 95,89 kW, em que 59,09 kW dizem respeito às perdas por evaporação. Foi também possível concluir que as perdas por evaporação representam cerca de 39% da energia calorifica produzida nas caldeiras. O edifício apresenta um consumo anual de eletricidade de 166 482 kWh em que 69% deste valor é provocado pelas unidades de tratamento de ar e a iluminação apresenta apenas um peso de 3%. Em relação ao gás natural consumido pelas caldeiras o seu valor anual é de 1 317 240 kWh. A simulação dinâmica do edifício permitiu concluir que este apresenta um IEE de 1 269,9 kWh/m2.ano. O rácio de classe energética (RIEE) é de 1,24 o que significa que o edifício pertence à classe energética C. As medidas estudadas para a melhoria da eficiência energética, nomeadamente integração energética com uma central de ciclo combinado, aplicação de cobertura isotérmica nas piscinas e substituição do telhado na zona da nave, mostraram-se viáveis. O estudo da possibilidade da realização de uma integração energética permitiu concluir que a poupança anual é de 9 374 € e o investimento é recuperado em menos de 1,5 anos. Relativamente à aplicação de cobertura isotérmica o investimento é de 14 000 € e é recuperado em 2 anos. A substituição do telhado na zona da nave tem um investimento de 20 500 € e a recuperação realiza-se num período de 3,5 anos.

Estudo da redução de consumos energéticos de uma Piscina Municipal

As cada vez mais importantes questões ambientais levam à imprescindibilidade da eficiência energética, sendo que esta tem cada vez mais importância a nível mundial. Deste modo, a eficiência energética, quer por uma obrigação legal (devido aos níveis de consumo) quer por questões de estatuto no mercado (imagem de uma empresa amiga do ambiente), está bem presente no mundo industrial. Portugal apresenta, no que diz respeito à situação energética, uma forte dependência externa, acima dos 70 %. Em 2012, informação disponível pela Direção Geral de Energia e Geologia (DGEG), o consumo total de energia primária era de 21.482 ktep e mais de 55 % desse consumo era proveniente de origem fóssil. Os setores que apresentam maiores consumos de eletricidade por setor de atividade são a Indústria e o setor de Serviços, onde estão presentes os edifícios com consumos perto dos 33 %. De forma a promover a eficiência energética e implementar a utilização racional de energia foram criados programas, estratégias e legislação que permitiram incentivar a diminuição dos consumos de energia nos edifícios de serviço. Uma das metodologias implementadas passa pela gestão de energia, ou seja, para atuar é necessário conhecer os fluxos de energia de um edifício. As auditorias energéticas permitem realizar um levantamento e análise desses mesmos fluxos, com o desígnio de identificar oportunidades de racionalização de consumo de energia. Nesta dissertação foi realizado um estudo da redução de consumos energéticos de uma piscina municipal baseado em dados de uma auditoria energética. Através da auditoria foi possível obter um resultado do exame energético, caracterizar o perfil real de utilização da energia elétrica e caracterizar os equipamentos dos consumidores energéticos instalados. Também permitiu realizar um levantamento térmico, de forma conhecer as temperaturas e a humidade relativa do edifício. Por fim, são apresentadas cinco medidas e algumas recomendações de eficiência energética, que permitem uma redução do consumo anual à instalação de cerca de 20%. Procedeu-se, também, a uma análise dos dados obtidos na auditoria, de forma a identificar algumas oportunidades de racionalização de energia.