A greener and highly sensitive flow-based procedure for carbaryl determination exploiting long pathlength spectrophotometry and photochemical waste degradation

An environmentally friendly analytical procedure with high sensitivity for determination of carbaryl pesticide in natural waters was developed. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. A long pathlength (100 cm) flow cell based on a liquid core waveguide (LCW) was employed to increase the sensitivity in detection of the indophenol formed from the reaction between carbaryl and p-aminophenol (PAP). A clean-up step based on cloud-point extraction was explored to remove the interfering organic matter, avoiding the use of toxic organic solvents. A linear response was observed within the range 5-200 mu g L(-1) and the detection limit, coefficient of variation and sampling rate were estimated as 1.7 mu g L(-1) (99.7% confidence level), 0.7% (n=20) and 55 determinations per hour, respectively. The reagents consumption was 1.9 mu g of PAP and 5.7 mu g of potassium metaperiodate, with volume of 2.6 mL of effluent per determination. The proposed procedure was selective for the determination of carbaryl, without interference from other carbamate pesticides. Recoveries within 84% and 104% were estimated for carbaryl spiked to water samples and the results obtained were also in agreement with those found by a batch spectrophotometric procedure at the 95% confidence level. The waste of the analytical procedure was treated with potassium persulphate and ultraviolet irradiation, yielding a colorless residue and a decrease of 94% of total organic carbon. In addition, the residue after treatment was not toxic for Vibrio fischeri bacteria. (c) 2010 Elsevier B.V. All rights reserved.

A flow-based procedure with solenoid micro-pumps for the spectrophotometric determination of uric acid in urine

The determination of uric acid in urine shows clinical importance, once it can be related to human organism dysfunctions, such as gout. An analytical procedure employing a multicommuted flow system was developed for the determination of uric acid in urine samples. Cu(II) ions are reduced by uric acid to Cu(I) that can be quantified by spectrophotometry in the presence of 2,2`-biquinoline 4,4`-dicarboxylic acid (BCA). The analytical response was linear between 10 and 100 mu mol L(-1) uric acid with a detection limit of 3.0 mu mol L(-1) (99.7% confidence level). Coefficient of variation of 1.2% and sampling rate of 150 determinations per hour were achieved. Per determination, 32 mu g of CuSO(4) and 200 mu g of BCA were consumed, generating 2.0 mL of waste. Recoveries from 91 to 112% were estimated and the results for 7 urine samples agreed with those obtained by the commercially available enzymatic kit for determination of uric acid. The procedure required 100-fold dilution of urine samples, minimizing sample consumption and interfering effects. In order to avoid the manual dilution step, on-line sample dilution was achieved by a simple system reconfiguration attaining a sampling rate of 95 h(-1). (C) 2009 Elsevier B.V. All rights reserved.

Cadmium telluride nanocrystals as luminescent sensitizers in flow analysis

A fully automated multipumping flow system (MPFS) using water-soluble CdTe quantum dots (QD) as sensitizers is proposed for the chemiluminometric determination of the anti-diabetic drugs gliclazide and glipizide in pharmaceutical formulations. The nanocrystals acted as enhancers of the weak CL emission produced upon oxidation of sulphite by Ce(IV) in acidic medium, thus improving sensitivity and expanding the dynamical analytical concentration range. By interacting with the QD, the two analytes prevented their sensitizing effect yielding a chemiluminescence quenching of the Ce(IV)-SO(3)(2-)CdTe QD system. The pulsed flow inherent to MPFS assured a fast and efficient mixing of all solutions inside the flow cell, circumventing the need for a reaction coil and facilitating the monitoring of the short-lived generated chemiluminescent species. QD crystal size, concentration and spectral region for measurement were investigated. (C) 2011 Elsevier B.V. All rights reserved.

An improved procedure for flow-based turbidimetric sulphate determination based on a liquid core waveguide and pulsed flows

An improved flow-based procedure is proposed for turbidimetric sulphate determination in waters. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. Stable baselines were observed in view of the pulsed flow characteristic of the systems designed with solenoid micro-pumps, thus making the use of washing solutions unnecessary. The nucleation process was improved by stopping the flow prior to the measurement, thus avoiding the need of sulphate addition. When a 1-cm optical path flow cell was employed, linear response was achieved within 20-200 mg L(-1), described by the equation S = -0.0767 + 0.00438C (mg L(-1)), r = 0.999. The detection limit was estimated as 3 mg L(-1) at the 99.7% confidence level and the coefficient of variation was 2.4% (n = 20). The sampling rate was estimated as 33 determinations per hour. A long pathlength (100-cm) flow cell based on a liquid core waveguide was exploited to increase sensitivity in turbidimetry. Baseline drifts were avoided by a periodical washing step with EDTA in alkaline medium. Linear response was observed within 7-16 mg L(-1), described by the equation S = -0.865 + 0.132C (mg L(-1)), r = 0.999. The detection limit was estimated as 150 mu g L(-1) at the 99.7% confidence level and the coefficient of variation was 3.0% (n = 20). The sampling rate was estimated as 25 determinations per hour. The results obtained for freshwater and rain water samples were in agreement with those achieved by batch turbidimetry at the 95% confidence level. (C) 2008 Elsevier B.V All rights reserved.

An improved flow-based procedure for microdetermination of total tannins in beverages with minimized reagent consumption

A flow system designed with solenoid micro-pumps is introduced for spectrophotometric determination of total tannins based on the Folin- Denis reaction. The procedure minimizes the main drawbacks related to the AOAC batch procedure, i.e. interferences from reducing species in the samples, high reagent consumption and waste generation, and low sampling rate. Linear response was observed for tannic acid concentrations in the range 2-100 mg L-1, with a detection limit (99.7% confidence level) of 0.3 mg L-1. The sampling rate and coefficient of variation (n = 10) were estimated as 75 measurements per hour and 1.1%, respectively. Results of determination of total tannin in tea, beer and wine samples were in agreement with those achieved by the batch reference procedure at the 95% confidence level. In comparison to the batch procedure, the reagent consumption and effluent generation were 83 and 60-fold lower, respectively.

Simultaneous flow injection preconcentration of lead and cadmium using cloud point extraction and determination by atomic absorption spectrometry

A flow injection (FI) micelle-mediated separation/preconcentration procedure for the determination of lead and cadmium by flame atomic absorption spectrometry (FAAS) has been proposed. The analytes reacted with 1-(2-thiazolylazo)-2-naphthol (TAN) to form hydrophobic chelates, which were extracted into the micelles of 0.05% (w/v) Triton X-114 in a solution buffered at pH 8.4. In the preconcentration stage, the micellar solution was continuously injected into a flow system with four mini-columns packed with cotton, glass wool. or TNT compresses for phase separation. The analytes-containing micelles were eluted from the mini-columns by a stream of 3 mol L(-1) HCl solution and the analytes were determined by FAAS. Chemical and flow variables affecting the preconcentration of the analytes were studied. For 15 mL. of preconcentrated solution, the enhancement factors varied between 15.1 and 20.3, the limits of detection were approximately 4.5 and 0.75 mu g L(-1) for lead and cadmium, respectively. For a solution containing 100 and 10 mu g L(-1) of lead and cadmium, respectively, the R.S.D. values varied from 1.6 to 3.2% (n = 7). The accuracy of the preconcentration system was evaluated by recovery measurements on spiked water samples. The method was susceptible to matrix effects, but these interferences were minimized by adding barium ions as masking agent in the sample solutions, and recoveries from spiked sample varied in the range of 95.1-107.3%. (C) 2008 Elsevier B.V. All rights reserved.

Zone trapping/merging zones in flow analysis: A novel approach for rapid assays involving relatively slow chemical reactions

A novel strategy for accomplishing zone trapping in flow analysis is proposed. The sample and the reagent solutions are simultaneously inserted into convergent carrier streams and the established zones merge together before reaching the detector, where the most concentrated portion of the entire sample zone is trapped. The main characteristics, potentialities and limitations of the strategy were critically evaluated in relation to an analogous flow system with zone stopping. When applied to the spectrophotometric determination of nitrite in river waters, the main figures of merit were maintained, exception made for the sampling frequency which was calculated as 189h(-1), about 32% higher relatively to the analogous system with zone stopping. The sample inserted volume can be increased up to 1.0 mL without affecting sampling frequency and no problems with pump heating or malfunctions were noted after 8-h operation of the system. In contrast to zone stopping, only a small portion of the sample zone is halted with zone trapping, leading to these beneficial effects. (C) 2011 Elsevier B.V. All rights reserved.

Flow-through peritoneal dialysis in neonatal enema-induced hyperphosphatemia

Fleet enemas are hypertonic solutions with an osmotic action and a high concentration of phosphate. When retained in the human body they have a great toxic potential, causing severe hydro-electrolyte disorders in children, especially in newborns. We report the case of a previously healthy 8-day-old newborn who needed neonatal intensive care treatment after the inadvertent administration of an osmotically active hypertonic phosphate enema. Taking into account that phosphate removal by peritoneal dialysis (PD) strongly depends on total dialysate turnover, we chose continuous flow PD (CFPD) as the treatment option, with a successful outcome. Clinical experience with this dialytic modality is limited to a few case reports in pediatric and adult patients. To the best of our knowledge, we report here the first description of CFPD in the setting of acute phosphate nephropathy in the neonatal period. The modality of PD described here has potential as an alternative management option as it is a highly efficient, methodologically simple, and low-cost method without any need for sophisticated equipment. Physicians and parents should be aware of the adverse effects of a hypertonic phosphate enema and should never use these medications in infants and newborns.

Polymer product engineering utilising oscillatory baffled reactors

The Oscillatory baffled reactor (OBR) can be used to produce particles with controlled size and morphology, in batch or continuous flow. This is due to the effect of the superimposed oscillations that radially mixes fluid but still allows plug-flow (or close to plug flow) behaviour in a continuous system. This mixing, combined with a close to a constant level of turbulence intensity in the reactor, leads to tight droplet and subsequent product particle size distributions. By applying population balance equations together with experimental droplet size distributions, breakage rates of droplets can be determined and this is a useful tool for understanding the product engineering in OBRs. (C) 2002 Elsevier Science B.V All rights reserved.

Field hydraulic properties of an Alfisol under various fallow systems in southwestern Nigeria

The effects of various fallow management systems and cropping intensities on water infiltration were measured on an Alfisol at Ibadan in southwestern Nigeria. The objective was to determine the influence of the land use systems (a combination of crop-fallow sequences and intercropping types) on soil hydraulic properties obtained by disc permeameter and double-ring infiltration measurements. The experiment was established in 1989 as a split-plot design with four replications. The main plots were natural fallow, planted Pueraria phaseoloides and planted Leucaena leucocephala. The subplots were 1 year of maize/cassava intercrop followed by 3-year fallow (25% cropping intensity), or 2-year fallow (33% cropping intensity), or 1-year fallow (50% cropping intensity), or no fallow period (100% cropping intensity). Water infiltration rates and sorptivities were measured under saturated and unsaturated flow. Irrespective of land use, infiltration rates at the soil surface (121-324 cm h(-1)) were greater than those measured at 30 cm depth (55-144 cm h(-1)). This indicated that fewer large pores were present below 30 cm depth compared with 0-30 cm, depth. Despite some temporal variation, sorptivities with the highest mean value of 93.5 cm h(-1/2) increased as the cropping intensity decreased, suggesting a more continuous macropore system under less intensive land use systems. This was most likely due to continuous biopores created by perennial vegetation under long fallow systems. Intercropped maize and cassava yields also increased as cropping intensity decreased. The weak relationship between crop yields and hydraulic conductivity/infiltration rates suggests that the rates were not limiting.

Avaliação técnica e econômica de um biodigestor de fluxo tubular: estudo de caso do modelo implantado na etec "orlando quagliato" em Santa Cruz do Rio Pardo, SP

Pós-graduação em Agronomia (Energia na Agricultura) - FCA

Aplicação de metodologias Lean ao fabrico de elevadores

Num mercado cada vez mais competitivo, torna-se fundamental para as empresas produzirem mais com menos recursos, aumentando a eficiência interna, através da otimização dos seus processos. Neste contexto aparece o Lean Manufacturing, metodologia que tem como objetivo criar valor para os stakeholders, através da eliminação de desperdício na cadeia de valor. Este projeto descreve a análise e a formulação de soluções do processo de produção de um Módulo de Serviço, produto que faz parte do sistema elétrico de um elevador. Para análise do problema utilizamos técnicas e ferramentas lean, tais como, o value stream mapping (VSM), o diagrama de processo e o diagrama de spaghetti. Para formulação do problema usamos o value stream design (VSD), a metodologia 5S, o sistema Kanban e a criação de fluxo contínuo, através do conceito takt time, do sistema Pull, da definição do processo pacemaker, da programação nivelada (Heijunka), do conceito pitch time e da caixa de nivelamento (Heijunka Box). Com este projeto pretendemos demonstrar que a implementação de um fluxo unitário de peças através da filosofia Lean Manufacturing, acrescenta qualidade ao produto, cria flexibilidade, aumenta a produtividade, liberta áreas de produção, aumenta a segurança, reduz o custo com o stock e aumenta a motivação organizacional.

Estudo e desenvolvimento de sistema de cobrança de portagens baseado em NFC

Tese para obter o grau de Mestre em Engenharia Electrónica e Telecomunicações

Virtual Communities of Practice: Design and Development of Support Platforms and Participation Fostering

Mestrado em Engenharia Informática - Área de Especialização em Sistemas Gráficos e Multimédia

Characterization of an in vitro fed-batch model to obtain cells released from S. epidermidis biofilms

Both dynamic and fed-batch systems have been used for the study of biofilms. Dynamic systems, whose hallmark is the presence of continuous flow, have been considered the most appropriate for the study of the last stage of the biofilm lifecycle: biofilm disassembly. However, fed-batch is still the most used system in the biofilm research field. Hence, we have used a fed-batch system to collect cells released from Staphylococcus epidermidis biofilms, one of the most important etiological agents of medical device-associated biofilm infections. Herein, we showed that using this model it was possible to collect cells released from biofilms formed by 12 different S. epidermidis clinical and commensal isolates. In addition, our data indicated that biofilm disassembly occurred by both passive and active mechanisms, although the last occurred to a lesser extent. Moreover, it was observed that S. epidermidis biofilm-released cells presented higher tolerance to vancomycin and tetracycline, as well as a particular gene expression phenotype when compared with either biofilm or planktonic cells. Using this model, biofilm-released cells phenotype and their interaction with the host immune system could be studied in more detail, which could help providing significant insights into the pathophysiology of biofilm-related infections.