Analysis of chromium behaviour and speciation during the electrodialytic process

The interest in chromium (Cr) arises from the widespread use of this heavy metal in various industrial processes that cause its release as liquid, solid and gaseous waste into the environment. The impact of Cr on the environment and living organisms primarily depends on its chemical form, since Cr(III) is an essential micronutrient for humans, other animals and plants, and Cr(VI) is highly toxic and a known human carcinogen. This study aimed to evaluate if the electrodialytic process (ED) is an appropriate treatment for Cr removal, through a critical overview of Cr speciation, before and after the ED experiments, to assess possible Cr(III)-Cr(VI) interconversions during the treatment. ED was the treatment technique applied to two types of matrices containing Cr: chromate copper arsenate (CCA) contaminated soil and municipal solid waste incineration (MSWI) fly ash. In order to study Cr remediation, three EDR set-ups were used: a new set-up, the combined cell (2/3C or 3/2C), with three compartments, alternating current between two anodes and different initial experimental conditions, one set-up with three compartments (3C cell) and the other set-up with two compartments (2C cell). The Cr removal rates obtained in this study were between 10-36% for the soil, and 1-13% for the fly ash. The highest Cr removal rates were achieved in the 26 days experiments: 36% for the soil, 13% for the fly ash. Regarding the 13 days experiments, the highest Cr removal rates were attained with the 2/3C set-up: 24% for the soil, 5% for the fly ash. The analysis of Cr(VI) was performed before and after ED experiments to evaluate eventual changes in Cr speciation during the treatment. This analysis was conducted by two methods: USEPA Method 3060A, for the extraction of Cr(VI); and Hach Company Method 8023, for the detection of Cr(VI). Despite the differences in Cr total concentration, both matrices presented a similar speciation, with Cr(III) being the main species found and Cr(VI) less than 3% of Cr total, before and after the treatment. For fly ash, Cr(VI) was initially below the detection limit of the method and remained that way after the treatment. For soil, Cr(VI) decreased after the treatment. Oxidation of Cr(III) to Cr(VI) did not occur during the ED process since there was no increase in Cr(VI) in the matrices after the treatment. Hence, the results of this study indicate that ED is an appropriate technique to remediate matrices containing Cr because it contributes to Cr removal, without causing Cr(III)-Cr(VI) interconversions.

Removal of organic contaminants from wastewater using the electrodialytic process

Pharmaceuticals and personal care products (PPCPs) are widely used on a daily basis. After their usage they reach the wastewater treatment plants (WWTPs). These compounds have different physico-chemical characteristics, which makes them difficult to completely remove in the WWTPs, througth conventional treatments. Currently, there is no legislation regarding PPCPs thresholds in effluent discharge. But, even at vestigial concentrations, these compounds enclose environmental risks due to, e.g., endocrine disruption potential. There is a need of alternative techniques for their removal in WWTPs. The main goal of this work was to assess the use of electrodialytic (ED) process to remove PPCPs from the effluent to be discharged. A two-compartment ED cell was used testing (i) the effluent position in the cell (anode and cathode compartment); (ii) the use of anion (AEM) and cation exchange membrane (CEM); (iii) the treatment period (6, 12 and 24 hours); (iv) effluent recirculation and current steps; (v) the feasibility of sequential treatments. Phosphorus (P) removal from effluent and energetic costs associated to the process were also evaluated. Five PPCPs were studied – caffeine (CAF), bisphenol A (BPA), 17 β-estradiol (E2), ethinyl estradiol (EE2) and oxybenzone (MBPh). The ED process showed to be effective in the removal when effluent is in the anode compartment. Oxidation is suggested to be the main removal process, which was between 88 and 96%, for all the compounds, in 6 hours. Nevertheless, the presence of intermediates and/or by-products was also observed in some cases. Effluent recirculation should have a retention time in the ED cell big enough to promote removal whereas the current steps (effluent in anode compartment) slightly increased removal efficiencies (higher than 80% for all PPCPs). The sequential set of ED treatment (effluent in anode compartment) showed to be effective during both periods with a removal percentage between 80 and 95% and 73 to 88% in the case of AEM and CEM, respectively. Again, the main removal process is strongly suggested to be oxidation in the anode compartment. However, there was an increase of BOD5 and COD, which might be explained by effluent spiking, these parameters limiting the effluent discharge. From these treatments, the use of AEM, enhanced the P removal from effluent to minimize risk of eutrophication. Energetic costs of the best set-up (6 hours) are approximately 0,8€/m3 of wastewater, a value considered low, attending to the prices of other treatment processes.

Electrodialytic remediation of two types of air pollution control residues and their applicability in construction materials

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente Perfil de Engenharia de Sistemas Ambientais

Optimization of the electrodialytic phosphorus recovery from sewage sludge ash

Phosphorus (P) is becoming a scarce element due to the decreasing availability of primary sources. Therefore, recover P from secondary sources, e.g. waste streams, have become extremely important. Sewage sludge ash (SSA) is a reliable secondary source of P. The use of SSAs as a direct fertilizer has very restricted legislation due to the presence of inorganic contaminants. Furthermore, the P present in SSAs is not in a plant-available form. The electrodialytic (ED) process is one of the methods under development to recover P and simultaneously remove heavy metals. The present work aimed to optimize the P recovery through a 2 compartment electrodialytic cell. The research was divided in three independent phases. In the first phase, ED experiments were carried out for two SSAs from different seasons, varying the duration of the ED process (2, 4, 6 and 9 days). During the ED treatment the SSA was suspended in distilled water in the anolyte, which was separated from the catholyte by a cation exchange membrane. From both ashes 90% of P was successfully extracted after 6 days of treatment. Regarding the heavy metals removal, one of the SSAs had a better removal than the other. Therefore, it was possible to conclude that SSAs from different seasons can be submitted to ED process under the same parameters. In the second phase, the two SSAs were exposed to humidity and air prior to ED, in order to carbonate them. Although this procedure was not successful, ED experiments were carried out varying the duration of the treatment (2 and 6 days) and the period of air exposure that SSAs were submitted to (7, 14 and 30 days). After 6 days of treatment and 30 days of air exposure, 90% of phosphorus was successfully extracted from both ashes. No differences were identified between carbonated and non-carbonated SSAs. Thus, SSAs that were exposed to the air and humidity, e.g. SSAs stored for 30 days in an open deposit, can be treated under the same parameters as the SSAs directly collected from the incineration process. In the third phase, ED experiments were carried out during 6 days varying the stirring time (0, 1, 2 and 4 h/day) in order to investigate if energy can be saved on the stirring process. After 6 days of treatment and 4 h/day stirring, 80% and 90% of P was successfully extracted from SSA-A and SSA-B, respectively. This value is very similar to the one obtained for 6 days of treatment stirring 24 h/day.

Electrodialytic recovery of phosphorus and organic contaminants removal from sewage sludge

Phosphorus is a macronutrient essential to life which comes from phosphate rock, a non-renewable resource. Sewage sludge from wastewater treatment plants (WWTP) is a secondary resource rich in phosphorus that can be valorized. However, organic compounds are detected in sewage sludge, due to its non-polar and hydrophobic character, being considered an environmental risk. The present dissertation aims to study the efficiency of the electrodialytic process (ED) when applied to sewage sludge aiming phosphorus recovery and organic contaminants removal. Four organic compounds were analyzed: 17α-ethynylestradiol (EE2), bisphenol A (BPA), caffeine (Caf) and oxybenzone (MBPh). The experiments took place in an ED cell with two compartments and an anion exchange membrane, with the sludge in the cathode compartment. The experiments were carried out for three days with spiked sewage sludge (six assays). One control experiment was done without current, three experiments were carried out applying a constant current of 50, 75, and 100 mA and two experiments were carried out applying sequential currents: 50 mA, 75 mA and 100 mA and the opposite (100-75-50 mA). A qualitative and quantitative analysis of microorganisms existing in the samples was also done. At the end, the pH increased in the sewage sludge favoring phosphorus recovery. In terms of phosphorus, the highest recovery was achieved in the experiment run with 100 mA, where 70.3±2.0% of total phosphorus was recovered in the electrolyte. Generally, compounds degradation was favored by the current. Caf and MBPh achieved degradation percentages of 96.2±0.2% and 84.8±1.3%, respectively, in 100 mA assay. EE2 (83.1±1.7%) and BPA (91.8±4.6%) degradations were favored by 50 mA current. A total of 35 taxa from four different groups were identified, totalizing between 81,600-273,000 individuals per gram of initial sludges. After ED, microbial community population decreased between 47-98%. Arcella gibbosa represented 61% of the total observed organisms and revealed to be more tolerant to medium changes.

Electrokinetic treatment of environmental matrices. Contaminants removal and phosphorus recovery

There is a need to develop viable techniques for removal and recovery organic and inorganic compounds from environmental matrices, due to their ecotoxicity, regulatory obligations or potential supplies as secondary materials. In this dissertation, electro –removal and –recovery techniques were applied to five different contaminated environmental matrices aiming phosphorus (P) recovery and/or contaminants removal. In a first phase, the electrokinetic process (EK) was carried out in soils for (i) metalloids and (ii) organic contaminants (OCs) removal. In the case of As and Sb mine contaminated soil, the EK process was additionally coupled with phytotechnologies. In a second phase, the electrodialytic process (ED) was applied to wastes aiming P recovery and simultaneous removal of (iii) toxins from membrane concentrate, (iv) heavy metals from sewage sludge ash (SSA), and (v) OCs from sewage sludge (SS). EK enhanced phytoremediation showed to be viable for the remediation of soils contaminated with metalloids, as although remediation was low, it combines advantages of both technologies while allowing site management. EK also proved to be an effective remediation technology for the removal and degradation of emerging OCs from two types of soil. Aiming P recovery and contaminants removal, different ED cell set-ups were tested. For the membrane concentrates, the best P recovery was achieved in a three compartment (3c) cell, but the highest toxin removal was obtained in a two compartment (2c) cell, placing the matrix in the cathode end. In the case of SSA the best approach for simultaneous P recovery and heavy metals removal was to use a 2c-cell placing the matrix in the anode end. However, for simultaneous P recovery and OCs removal, SS should be placed in the cathode end, in a 2c-cell. Overall, the data support that the selection of the cell design should be done case-by-case.

[meanings Of The Sickening Process For Patients With Systemic Lupus Erythematosus: A Review Of The Literature.]

Systemic lupus erythematosus is an autoimmune disease that causes many psychological repercussions that have been studied through qualitative research. These are considered relevant, since they reveal the amplitude experienced by patients. Given this importance, this study aims to map the qualitative production in this theme, derived from studies of experiences of adult patients of both genders and that had used as a tool a semi-structured interview and/or field observations, and had made use of a sampling by a saturation criterion to determine the number of participants in each study. The survey was conducted in Pubmed, Lilacs, Psycinfo e Cochrane databases, searching productions in English and Portuguese idioms published between January 2005 and June 2012. The 19 revised papers that have dealt with patients in the acute phase of the disease showed themes that were categorized into eight topics that contemplated the experienced process at various stages, from the onset of the disease, extending through the knowledge of the diagnosis and the understanding of the manifestations of the disease, drug treatment and general care, evolution and prognosis. The collected papers also point to the difficulty of understanding, of the patients, on what consists the remission phase, revealing also that this is a clinical stage underexplored by psychological studies.

[in Process Citation].

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O aluno com deficiência visual nas aulas de educação física : análise do processo inclusivo = The student with visual impairments : analysis of inclusive process

Universidade Estadual de Campinas . Faculdade de Educação Física

Hegemonia e contra-hegemonia na construção de políticas de esporte e lazer : a experiência do Consórcio Brasília = Hegemony and counter-hegemony in the process of sport and leisure policy-making : the experience of the Consortium Brasilia

Universidade Estadual de Campinas . Faculdade de Educação Física

Effects of the condylar process fracture on facial symmetry in rats submitted to protein undernutrition

PURPOSE: To investigate the facial symmetry of rats submitted to experimental mandibular condyle fracture and with protein undernutrition (8% of protein) by means of cephalometric measurements. METHODS: Forty-five adult Wistar rats were distributed in three groups: fracture group, submitted to condylar fracture with no changes in diet; undernourished fracture group, submitted to hypoproteic diet and condylar fracture; undernourished group, kept until the end of experiment, without condylar fracture. Displaced fractures of the right condyle were induced under general anesthesia. The specimens were submitted to axial radiographic incidence, and cephalometric mensurations were made using a computer system. The values obtained were subjected to statistical analyses among the groups and between the sides in each group. RESULTS: There was significative decrease of the values of serum proteins and albumin in the undernourished fracture group. There was deviation of the median line of the mandible relative to the median line of the maxilla, significative to undernutrition fracture group, as well as asymmetry of the maxilla and mandible, in special in the final period of experiment. CONCLUSION: The mandibular condyle fracture in rats with proteic undernutrition induced an asymmetry of the mandible, also leading to consequences in the maxilla.

Influence of specimens' design and manufacturing process on microtensile bond strength to enamel: laboratory and FEA comparison

This study evaluated the effect of specimens' design and manufacturing process on microtensile bond strength, internal stress distributions (Finite Element Analysis - FEA) and specimens' integrity by means of Scanning Electron Microscopy (SEM) and Laser Scanning Confocal Microscopy (LCM). Excite was applied to flat enamel surface and a resin composite build-ups were made incrementally with 1-mm increments of Tetric Ceram. Teeth were cut using a diamond disc or a diamond wire, obtaining 0.8 mm² stick-shaped specimens, or were shaped with a Micro Specimen Former, obtaining dumbbell-shaped specimens (n = 10). Samples were randomly selected for SEM and LCM analysis. Remaining samples underwent microtensile test, and results were analyzed with ANOVA and Tukey test. FEA dumbbell-shaped model resulted in a more homogeneous stress distribution. Nonetheless, they failed under lower bond strengths (21.83 ± 5.44 MPa)c than stick-shaped specimens (sectioned with wire: 42.93 ± 4.77 MPaª; sectioned with disc: 36.62 ± 3.63 MPa b), due to geometric irregularities related to manufacturing process, as noted in microscopic analyzes. It could be concluded that stick-shaped, nontrimmed specimens, sectioned with diamond wire, are preferred for enamel specimens as they can be prepared in a less destructive, easier, and more precise way.

Effect of nitric oxide inhibitor and donor substances on the infammatory process caused by endodontic irrigants

Nitric oxide (NO) has been considered a key molecule in infammation. OBJECTIVE: The aim of this study was to evaluate the effect of treatment with L-NAME and sodium nitroprussiate, substances that inhibit and release NO, respectively, on tissue tolerance to endodontic irrigants. MATERIAL AND METHODS: The vital dye exudation method was used in a rat subcutaneous tissue model. Injections of 2% Evans blue were administered intravenously into the dorsal penial vein of 14 male rats (200-300 g). The NO inhibitor and donor substances were injected into the subcutaneous tissue in the dorsal region, forming two groups of animals: G1 was inoculated with L-NAME and G2 with sodium nitroprussiate. Both groups received injections of the test endodontic irrigants: acetic acid, 15% citric acid, 17% EDTA-T and saline (control). After 30 min, analysis of the extravasated dye was performed by light absorption spectrophotometry (620 nm). RESULTS: There was statistically signifcant difference (p<0.05) between groups 1 and 2 for all irrigants. L-NAME produced a less intense infammatory reaction and nitroprussiate intensifed this process. CONCLUSIONS: Independently of the administration of NO inhibitors and donors, EDTA-T produced the highest irritating potential in vital tissue among the tested irrigating solutions.

Dependence of the crossover exponent with the diffusion rate in the generalized contact process model

We study how the crossover exponent, phi, between the directed percolation (DP) and compact directed percolation (CDP) behaves as a function of the diffusion rate in a model that generalizes the contact process. Our conclusions are based in results pointed by perturbative series expansions and numerical simulations, and are consistent with a value phi = 2 for finite diffusion rates and phi = 1 in the limit of infinite diffusion rate.

Screening process for activity determination of conductive oxide electrodes for organic oxidation

A modified method for the calculation of the normalized faradaic charge (q fN) is proposed. The method involves the simulation of an oxidation process, by cyclic voltammetry, by employing potentials in the oxygen evolution reaction region. The method is applicable to organic species whose oxidation is not manifested by a defined oxidation peak at conductive oxide electrodes. The variation of q fN for electrodes of nominal composition Ti/RuX Sn1-X O2 (x = 0.3, 0.2 and 0.1), Ti/Ir0.3Ti0.7O2 and Ti/Ru0.3Ti0.7O2 in the presence of various concentrations of formaldehyde was analyzed. It was observed that electrodes containing SnO2 are the most active for formaldehyde oxidation. Subsequently, in order to test the validity of the proposed model, galvanostatic electrolyses (40 mA cm-2) of two different formaldehyde concentrations (0.10 and 0.01 mol dm-3) were performed. The results are in agreement with the proposed model and indicate that this new method can be used to determine the relative activity of conductive oxide electrodes. In agreement with previous studies, it can be concluded that not only the nature of the electrode material, but also the organic species in solution and its concentration are important factors to be considered in the oxidation of organic compounds.