Removal of phenol in high salinity media by a hybrid process (activated sludge plus photocatalysis)

The degradation of phenol by a hybrid process (activated sludge + photocatalysis) in a high salinity medium (50 g L-1 of chloride) has been investigated. The sludge used from a municipal wastewater facility was adapted to the high salt concentrations prior to use. The photocatalytic conditions were optimized by means of a factorial experimental design. TiO2 P25 from Degussa was used as the photocatalyst. The initial phenol concentration was approximately 200 mg L-1 and complete removal of phenol and a mineralization degree above 98% were achieved within 25 h of treatment (24 h of biological treatment and I h of photocatalysis). From HPLC analyses, five hydroxylated intermediates formed during oxidation have been identified. The main ones were catechol and hydroquinone, followed by 1,2,4-benzenetriol, 2-hydroxy- 1,4-benzoquinone, and pyrogallol, in this order. No formation of organochlorine compounds was observed. Therefore, the proposed hybrid process showed itself to be suited to treat phenol in the presence of high contents of salt. (c) 2007 Elsevier B.V. All rights reserved.

The Optimal trigger speed of vehicle activated signs

The thesis aims to elaborate on the optimum trigger speed for Vehicle Activated Signs (VAS) and to study the effectiveness of VAS trigger speed on drivers’ behaviour. Vehicle activated signs (VAS) are speed warning signs that are activated by individual vehicle when the driver exceeds a speed threshold. The threshold, which triggers the VAS, is commonly based on a driver speed, and accordingly, is called a trigger speed. At present, the trigger speed activating the VAS is usually set to a constant value and does not consider the fact that an optimal trigger speed might exist. The optimal trigger speed significantly impacts driver behaviour. In order to be able to fulfil the aims of this thesis, systematic vehicle speed data were collected from field experiments that utilized Doppler radar. Further calibration methods for the radar used in the experiment have been developed and evaluated to provide accurate data for the experiment. The calibration method was bidirectional; consisting of data cleaning and data reconstruction. The data cleaning calibration had a superior performance than the calibration based on the reconstructed data. To study the effectiveness of trigger speed on driver behaviour, the collected data were analysed by both descriptive and inferential statistics. Both descriptive and inferential statistics showed that the change in trigger speed had an effect on vehicle mean speed and on vehicle standard deviation of the mean speed. When the trigger speed was set near the speed limit, the standard deviation was high. Therefore, the choice of trigger speed cannot be based solely on the speed limit at the proposed VAS location. The optimal trigger speeds for VAS were not considered in previous studies. As well, the relationship between the trigger value and its consequences under different conditions were not clearly stated. The finding from this thesis is that the optimal trigger speed should be primarily based on lowering the standard deviation rather than lowering the mean speed of vehicles. Furthermore, the optimal trigger speed should be set near the 85th percentile speed, with the goal of lowering the standard deviation.

Speed prediction for triggering vehicle activated signs

Accurate speed prediction is a crucial step in the development of a dynamic vehcile activated sign (VAS). A previous study showed that the optimal trigger speed of such signs will need to be pre-determined according to the nature of the site and to the traffic conditions. The objective of this paper is to find an accurate predictive model based on historical traffic speed data to derive the optimal trigger speed for such signs. Adaptive neuro fuzzy (ANFIS), classification and regression tree (CART) and random forest (RF) were developed to predict one step ahead speed during all times of the day. The developed models were evaluated and compared to the results obtained from artificial neural network (ANN), multiple linear regression (MLR) and naïve prediction using traffic speed data collected at four sites located in Sweden. The data were aggregated into two periods, a short term period (5-min) and a long term period (1-hour). The results of this study showed that using RF is a promising method for predicting mean speed in the two proposed periods.. It is concluded that in terms of performance and computational complexity, a simplistic input features to the predicitive model gave a marked increase in the response time of the model whilse still delivering a low prediction error.

A data driven approach for automating vehicle activated signs

Vehicle activated signs (VAS) display a warning message when drivers exceed a particular threshold. VAS are often installed on local roads to display a warning message depending on the speed of the approaching vehicles. VAS are usually powered by electricity; however, battery and solar powered VAS are also commonplace. This thesis investigated devel-opment of an automatic trigger speed of vehicle activated signs in order to influence driver behaviour, the effect of which has been measured in terms of reduced mean speed and low standard deviation. A comprehen-sive understanding of the effectiveness of the trigger speed of the VAS on driver behaviour was established by systematically collecting data. Specif-ically, data on time of day, speed, length and direction of the vehicle have been collected for the purpose, using Doppler radar installed at the road. A data driven calibration method for the radar used in the experiment has also been developed and evaluated. Results indicate that trigger speed of the VAS had variable effect on driv-ers’ speed at different sites and at different times of the day. It is evident that the optimal trigger speed should be set near the 85th percentile speed, to be able to lower the standard deviation. In the case of battery and solar powered VAS, trigger speeds between the 50th and 85th per-centile offered the best compromise between safety and power consump-tion. Results also indicate that different classes of vehicles report differ-ences in mean speed and standard deviation; on a highway, the mean speed of cars differs slightly from the mean speed of trucks, whereas a significant difference was observed between the classes of vehicles on lo-cal roads. A differential trigger speed was therefore investigated for the sake of completion. A data driven approach using Random forest was found to be appropriate in predicting trigger speeds respective to types of vehicles and traffic conditions. The fact that the predicted trigger speed was found to be consistently around the 85th percentile speed justifies the choice of the automatic model.

Review of the effectiveness of vehicle activated signs

This paper reviews the effectiveness of vehicle activated signs. Vehicle activated signs are being reportedly used in recent years to display dynamic information to road users on an individual basis in order to give a warning or inform about a specific event. Vehicle activated signs are triggered individually by vehicles when a certain criteria is met. An example of such criteria is to trigger a speed limit sign when the driver exceeds a pre-set threshold speed. The preset threshold is usually set to a constant value which is often equal, or relative, to the speed limit on a particular road segment. This review examines in detail the basis for the configuration of the existing sign types in previous studies and explores the relation between the configuration of the sign and their impact on driver behavior and sign efficiency. Most of previous studies showed that these signs have significant impact on driver behavior, traffic safety and traffic efficiency. In most cases the signs deployed have yielded reductions in mean speeds, in speed variation and in longer headways. However most experiments reported within the area were performed with the signs set to a certain static configuration within applicable conditions. Since some of the aforementioned factors are dynamic in nature, it is felt that the configurations of these signs were thus not carefully considered by previous researchers and there is no clear statement in the previous studies describing the relationship between the trigger value and its consequences under different conditions. Bearing in mind that different designs of vehicle activated signs can give a different impact under certain conditions of road, traffic and weather conditions the current work suggests that variable speed thresholds should be considered instead.

Data based Calibration System for Radar used by Vehicle Activated Signs

The accurate measurement of a vehicle’s velocity is an essential feature in adaptive vehicle activated sign systems. Since the velocities of the vehicles are acquired from a continuous wave Doppler radar, the data collection becomes challenging. Data accuracy is sensitive to the calibration of the radar on the road. However, clear methodologies for in-field calibration have not been carefully established. The signs are often installed by subjective judgment which results in measurement errors. This paper develops a calibration method based on mining the data collected and matching individual vehicles travelling between two radars. The data was cleaned and prepared in two ways: cleaning and reconstructing. The results showed that the proposed correction factor derived from the cleaned data corresponded well with the experimental factor done on site. In addition, this proposed factor showed superior performance to the one derived from the reconstructed data.

Triggering Solar-Powered Vehicle Activated Signs using Self Organising Maps with K-means

Solar-powered vehicle activated signs (VAS) are speed warning signs powered by batteries that are recharged by solar panels. These signs are more desirable than other active warning signs due to the low cost of installation and the minimal maintenance requirements. However, one problem that can affect a solar-powered VAS is the limited power capacity available to keep the sign operational. In order to be able to operate the sign more efficiently, it is proposed that the sign be appropriately triggered by taking into account the prevalent conditions. Triggering the sign depends on many factors such as the prevailing speed limit, road geometry, traffic behaviour, the weather and the number of hours of daylight. The main goal of this paper is therefore to develop an intelligent algorithm that would help optimize the trigger point to achieve the best compromise between speed reduction and power consumption. Data have been systematically collected whereby vehicle speed data were gathered whilst varying the value of the trigger speed threshold. A two stage algorithm is then utilized to extract the trigger speed value. Initially the algorithm employs a Self-Organising Map (SOM), to effectively visualize and explore the properties of the data that is then clustered in the second stage using K-means clustering method. Preliminary results achieved in the study indicate that using a SOM in conjunction with K-means method is found to perform well as opposed to direct clustering of the data by K-means alone. Using a SOM in the current case helped the algorithm determine the number of clusters in the data set, which is a frequent problem in data clustering.

Desenvolvimento de redes de polímeros interpenetrantes (IPN) para a aplicação como eletrólito polimérico

Uma nova rede de polímeros interpenetrantes (IPN) baseada em poliuretana de óleo de mamona e poli(etileno glicol) e poli(metacrilato de metila) foi preparada para ser utilizada como eletrólito polimérico. Os seguintes parâmetros de polimerização foram avaliados: massa molecular do poli(etileno glicol) (PEG), concentração de PEG e concentração de metacrilato de metila. As membranas de IPN foram caracterizadas por calorimetria diferencial de varredura (DSC) e espectroscopia de infravermelho por transformada de Fourier (FT-IR). Os eletrólitos de redes de polímeros interpenetrantes (IPNE) foram preparados a partir da dopagem com sal de lítio através do inchamento numa solução de 10% em massa de LiClO4 na mistura de carbonato de etileno e carbonato de propileno na razão mássica de 50:50. As IPNEs foram caracterizadas por espectroscopia de impedância eletroquímica e Raman. As IPNEs foram testadas como eletrólito polimérico em supercapacitores. As células capacitivas foram preparadas utilizando eletrodos de polipirrol (PPy). Os valores de capacitância e eficiência foram calculados por impedância eletroquímica, voltametria cíclica e ciclos galvonostáticos de carga e descarga. Os valores de capacitância obtidos foram em torno de 90 F.g-1 e eficiência variou no intervalo de 88 a 99%. Os valores de densidade de potência foram superiores a 250 W.kg-1 enquanto que a densidade de energia variou de 10 a 33 W.h.kg-1, dependendo da composição da IPNE. As características eletroquímicas do eletrólito formado pela IPN-LiClO4 (IPNE) foram comparadas aos eletrólitos poliméricos convencionais, tais como poli(difluoreto de vinilideno)-(hexafluorpropileno) ((PVDF-HFP/LiClO4) e poliuretana comercial (Bayer desmopan 385) (PU385/LiClO4). As condutividades na temperatura ambiente foram da ordem de 10-3 S.cm-1. A capacitância da célula utilizando eletrodos de PPy com eletrólito de PVDFHFP foi de 115 F.g-1 (30 mF.cm-2) e 110 F.g-1 (25 mF.cm-2) para a célula com PU385 comparadas a 90 F.g-1 (20 mF.cm-2) para a IPNE. Os capacitores preparados com eletrólito de IPNE apresentaram valores de capacitância inferior aos demais, entretanto provaram ser mais estáveis e mais resistentes aos ciclos de carga/descarga. A interpenetração de duas redes poliméricas, PU e PMMA produziu um eletrólito com boa estabilidade mecânica e elétrica. Um protótipo de supercapacitor de estado sólido foi produzindo utilizando eletrodos impressos de carbono ativado (PCE) e o eletrólito polimérico de IPNE. A técnica de impressão de carbono possui várias vantagens em relação aos outros métodos de manufatura de eletrodos de carbono, pois a área do eletrodo, espessura e composição são variáveis que podem ser controladas experimentalmente. As células apresentaram uma larga janela eletroquímica (4V) e valores da capacitância da ordem de 113 mF.cm-2 (16 F.g-1). Métodos alternativos de preparação do PCE investigados incluem o uso de IPNE como polímero de ligação ao carbono ativado, estes eletrodos apresentaram valores de capacitância similares aos produzidos com PVDF. A influência do número de camadas de carbono usadas na produção do PCE também foi alvo de estudo. Em relação ao eletrólito polimérico, o plastificante e o sal de lítio foram adicionados durante a síntese, formando a IPNGel. As células apresentaram alta capacitância e boa estabilidade após 4000 ciclos de carga e descarga. As membranas de IPN foram testadas também como reservatório de medicamento em sistemas de transporte transdérmico por iontoforese. Os filmes, mecanicamente estáveis, formaram géis quando inchado em soluções saturadas de lidocaina.HCl, anestésico local, em propileno glicol (PG), poli(etileno glicol) (PEG400) e suas misturas. O grau de inchamento em PG foi de 15% e 35% em PEG400. Agentes químicos de penetração foram utilizados para diminuir a resistência da barreira causada pela pele, dentre eles o próprio PG, a 2-pirrolidinona (E1) e a 1-dodecil-2-pirrolidinona (E2). Os géis foram caracterizados por espectroscopia de impedância eletroquímica e transporte passivo e por iontoforese através de uma membrana artificial (celofane). O sistema IPN/ lidocaina.HCl apresentou uma correlação linear entre medicamento liberado e a corrente aplicada. Os melhores resultados de transporte de medicamento foram obtidos utilizando o PG como solvente.

The Effect of Residence Time on the Tensile Properties of Superelastic and Thermal Activated Ni-Ti Orthodontic Wires

Since the 1980s, different devices based on superelastic alloys have been developed to fulfill orthodontic applications. Particularly in the last decades several researches have been carried out to evaluate the mechanical behavior of Ni-Ti alloys, including their tensile, torsion and fatigue properties. However, studies regarding the dependence of elastic properties on residence time of Ni-Ti wires in the oral cavity are scarce. Such approach is essential since metallic alloys are submitted to mechanical stresses during orthodontic treatment as well as pH and temperature fluctuations. The goal of the present contribution is to provide elastic stress-strain results to guide the orthodontic choice between martensitic thermal activated and austenitic superelastic Ni-Ti alloys. From the point of view of an orthodontist, the selection of appropriate materials and the correct maintenance of the orthodontic apparatus are essential needs during clinical treatment. The present work evaluated the elastic behavior of Ni-Ti alloy wires with diameters varying from 0.014 to 0.020 inches, submitted to hysteresis tensile tests with 8% strain. Tensile tests were performed after periods of use of 1, 2 and 3 months in the oral cavity of patients submitted to orthodontic treatment. The results from the hysteresis tests allowed to exam the strain range covered by isostress lines upon loading and unloading, as well as the residual strain after unloading for both superelastic and thermal activated Ni-Ti wires. Superelastic Ni-Ti wires exhibited higher load isostress values compared to thermal activated wires. It was found that such differences in the load isostress values can increase with increasing residence time.

Karyoplast exchange between strontium- and 6-DMAP-parthenogenetically activated zygotes of cattle

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of therapeutic plasma concentrations of non-steroidal anti-inflammatory drugs on the production of reactive oxygen species by activated rat neutrophils

The release of reactive oxygen specie (ROS) by activated neutrophil is involved in both the antimicrobial and deleterious effects in chronic inflammation. The objective of the present investigation was to determine the effect of therapeutic plasma concentrations of non-steroidal anti-inflammatory drugs (NSAIDs) on the production of ROS by stimulated rat neutrophils. Diclofenac (3.6 µM), indomethacin (12 µM), naproxen (160 µM), piroxicam (13 µM), and tenoxicam (30 µM) were incubated at 37ºC in PBS (10 mM), pH 7.4, for 30 min with rat neutrophils (1 x 10(6) cells/ml) stimulated by phorbol-12-myristate-13-acetate (100 nM). The ROS production was measured by luminol and lucigenin-dependent chemiluminescence. Except for naproxen, NSAIDs reduced ROS production: 58 ± 2% diclofenac, 90 ± 2% indomethacin, 33 ± 3% piroxicam, and 45 ± 6% tenoxicam (N = 6). For the lucigenin assay, naproxen, piroxicam and tenoxicam were ineffective. For indomethacin the inhibition was 52 ± 5% and diclofenac showed amplification in the light emission of 181 ± 60% (N = 6). Using the myeloperoxidase (MPO)/H2O2/luminol system, the effects of NSAIDs on MPO activity were also screened. We found that NSAIDs inhibited both the peroxidation and chlorinating activity of MPO as follows: diclofenac (36 ± 10, 45 ± 3%), indomethacin (97 ± 2, 100 ± 1%), naproxen (56 ± 8, 76 ± 3%), piroxicam (77 ± 5, 99 ± 1%), and tenoxicam (90 ± 2, 100 ± 1%), respectively (N = 3). These results show that therapeutic levels of NSAIDs are able to suppress the oxygen-dependent antimicrobial or oxidative functions of neutrophils by inhibiting the generation of hypochlorous acid.

Oxidation of melatonin and its catabolites, N-1-acetyl-N (2)-formyl-5-methoxykynuramine and N-1-acetyl-5-methoxykynuramine, by activated leukocytes

N-1-acetyl-N-2-formyl-5-methoxykynuramine (AFMK) and N-1-acetyl-5-methoxykynuramine (AMK), two melatonin catabolites, have been described as potent antioxidants. We aimed to follow the kinetics of AFMK and AMK formation when melatonin is oxidized by phorbol myristate acetate (PMA) and lipopolysaccharide (LPS)-activated leukocytes. An HPLC-based method was used for AFMK and AMK determination in neutrophil and peripheral blood mononuclear cell cultures supernatants. Samples were separated isocratically on a C18 reverse-phase column using acetonitrile/H2O (25:75) as the mobile phase. AFMK was detected by fluorescence (excitation 340 nm and emission 460 nm) and AMK by UV-VIS absorbance (254 nm). Activation of neutrophils and mononuclear cells with PMA produces larger amounts of AFMK than activation with LPS, probably due to the lower levels of reactive oxygen species formation and myeloperoxidase (MPO) degranulation that occurs when cells are stimulated with LPS. The concentration of AMK found in the supernatant was about 5-10% (from 18-hr cultures) compared with AFMK. This result may reflect its reactivity. Indeed AMK, but not AFMK, is easily oxidized by activated neutrophils in a MPO and hydrogen peroxide-dependent reaction. In conclusion, we defined a simple procedure for the determination of AFMK and AMK in biological samples and demonstrated the capacity of leukocytes to oxidize melatonin and AMK.

Effectiveness of Photogem (R) activated by LED on the decontamination of artificial carious bovine dentin

The aim of this study was the evaluation of the effectiveness of photodynamic therapy on the decontamination of artificially induced carious bovine dentin, using Photoge(R) as the photosensitizer agent and an LED device as a light source. Dentin samples obtained from bovine incisors were immersed in sterile broth supplemented by Lactobacillus acidophillus 10(8) colony formation units (CFU) and Streptococcus mutans 10 8 CFU. Different concentrations of photosensitizer, PA = 1 mg/ml, PB = 2 mg/ml, and PC = 3 mg/ml, and two fluences, D = 24 J/cm(2) and D = 48 J/cm(2), were investigated. After CFU counting per milligram of carious dentin and statistical analysis, we observed that the photodynamic therapy (PDT) parameters used were effective for bacterial reduction in the in vitro model under study. The best result was achieved with the application of Photoge(R) at 2 mg/ml and photoactivated under 24 J/cm(2) showing a survival factor of 0.14. At higher photosensitizer concentrations, a higher dark toxicity was observed. We propose a simple mathematical expression for the determination of PDT parameters of photosensitizer concentration and light fluence for different survival factor values. Since LED devices are simpler and cheaper compared to laser systems, it would be interesting to verify their efficacy as a light source in photodynamic therapy for the decontamination of carious dentin.