Avaliação da qualidade química e microbiológica de tintas didácticas do ensino pré-escolar

As tintas utilizadas nas actividades didácticas possuem na sua composição ingredientes que dada a sua natureza, modo de fabrico e de utilização, podem representar um risco para a saúde das crianças. Neste âmbito, procurou-se com este estudo avaliar a qualidade química e microbiológica das tintas utilizadas pelas crianças no ensino pré-escolar. Vinte e nove amostras de tintas, incluindo guaches, tintas de águas, digitintas e tintas para pinturas faciais foram recolhidas em oito estabelecimentos de ensino, nomeadamente, Jardins de Infância, do conselho de Vila Nova de Gaia. A avaliação microbiológica envolveu não só a determinação da concentração microbiana presente nas amostras, como também, a avaliação da estabilidade microbiana nas tintas das espécies S.aureus e E.coli. Na avaliação química procedeu-se à determinação da concentração dos metais chumbo (Pb), cádmio (Cd), crómio (Cr), cobalto (Co), níquel (Nq), manganês (Mn), cobre (Cu) e zinco (Zn) quer em algumas das amostras recolhidas nos estabelecimentos de ensino, quer em tintas adquiridas em três estabelecimentos comerciais. Os resultados obtidos da avaliação microbiológica revelam uma contaminação estática na generalidade das tintas. Três amostras de tintas apresentaram ainda elevada contaminação por fungos, nomeadamente Aspergillus spp. e Trichophyton spp. Da avaliação da estabilidade microbiana das espécies S.aureus e E.coli observou-se uma sensibilidade das mesmas às tintas, sendo evidenciado, em alguns casos, um decrescimento da concentração ao longo do tempo de exposição, e noutros, uma sensibilidade imediata. A espécie S.aureus revelou, contudo, maior capacidade de resistência que a E.coli. Os resultados obtidos da avaliação química revelaram a presença de Cr em todas as amostras, registando as tintas adquiridas em estabelecimentos comerciais concentrações mais elevadas para este metal. Os metais Cu e Zn foram detectados, em algumas amostras de tintas artísticas, em concentrações acima dos valores limites. Nas tintas para a cara foram encontrados os metais Pb, Cd, Cr e Nq, cuja utilização é interdita nestes produtos. O conhecimento das características químicas e microbiológicas das tintas utilizadas por crianças do ensino pré-escolar revelou-se de grande importância, nomeadamente, para a determinação dos riscos a que este grupo de indivíduos pode estar exposto no seu dia-a-dia quando utilizam estes produtos.

Determination of electricity consumers’ load profiles via weighted evidence accumulation clustering using subsampling

With the electricity market liberalization, the distribution and retail companies are looking for better market strategies based on adequate information upon the consumption patterns of its electricity consumers. A fair insight on the consumers’ behavior will permit the definition of specific contract aspects based on the different consumption patterns. In order to form the different consumers’ classes, and find a set of representative consumption patterns we use electricity consumption data from a utility client’s database and two approaches: Two-step clustering algorithm and the WEACS approach based on evidence accumulation (EAC) for combining partitions in a clustering ensemble. While EAC uses a voting mechanism to produce a co-association matrix based on the pairwise associations obtained from N partitions and where each partition has equal weight in the combination process, the WEACS approach uses subsampling and weights differently the partitions. As a complementary step to the WEACS approach, we combine the partitions obtained in the WEACS approach with the ALL clustering ensemble construction method and we use the Ward Link algorithm to obtain the final data partition. The characterization of the obtained consumers’ clusters was performed using the C5.0 classification algorithm. Experiment results showed that the WEACS approach leads to better results than many other clustering approaches.

Iron oxide/gold core/shell nanomagnetic probes and CdS biolabels for amplified electrochemical immunosensing of Salmonella typhimurium

There is an imminent need for rapid methods to detect and determine pathogenic bacteria in food products as alternatives to the laborious and time-consuming culture procedures. In this work, an electrochemical immunoassay using iron/gold core/shell nanoparticles (Fe@Au) conjugated with anti-Salmonella antibodies was developed. The chemical synthesis and functionalization of magnetic and gold-coated magnetic nanoparticles is reported. Fe@Au nanoparticles were functionalized with different self-assembled monolayers and characterized using ultraviolet-visible spectrometry, transmission electron microscopy, and voltammetric techniques. The determination of Salmonella typhimurium, on screen-printed carbon electrodes, was performed by square-wave anodic stripping voltammetry through the use of CdS nanocrystals. The calibration curve was established between 1×101 and 1×106 cells/mL and the limit of detection was 13 cells/mL. The developed method showed that it is possible to determine the bacteria in milk at low concentrations and is suitable for the rapid (less than 1 h) and sensitive detection of S. typhimurium in real samples. Therefore, the developed methodology could contribute to the improvement of the quality control of food samples.

The development and optimization of a modified single-drop microextraction method for organochlorine pesticides determination by gas chromatography-tandem mass spectrometry

We have developed a new method for single-drop microextraction (SDME) for the preconcentration of organochlorine pesticides (OCP) from complex matrices. It is based on the use of a silicone ring at the tip of the syringe. A 5 μL drop of n-hexane is applied to an aqueous extract containing the OCP and found to be adequate to preconcentrate the OCPs prior to analysis by GC in combination with tandem mass spectrometry. Fourteen OCP were determined using this technique in combination with programmable temperature vaporization. It is shown to have many advantages over traditional split/splitless injection. The effects of kind of organic solvent, exposure time, agitation and organic drop volume were optimized. Relative recoveries range from 59 to 117 %, with repeatabilities of <15 % (coefficient of variation) were achieved. The limits of detection range from 0.002 to 0.150 μg kg−1. The method was applied to the preconcentration of OCPs in fresh strawberry, strawberry jam, and soil.

Determination of total petroleum hydrocarbons in soil from different locations using infrared spectrophotometry and gas chromatography

Total petroleum hydrocarbons (TPH) are important environmental contaminants which are toxic to human and environmental receptors. Several analytical methods have been used to quantify TPH levels in contaminated soils, specifically through infrared spectrometry (IR) and gas chromatography (GC). Despite being two of the most used techniques, some issues remain that have been inadequately studied: a) applicability of both techniques to soils contaminated with two distinct types of fuel (petrol and diesel), b) influence of the soil natural organic matter content on the results achieved by various analytical methods, and c) evaluation of the performance of both techniques in analyses of soils with different levels of contamination (presumably non-contaminated and potentially contaminated). The main objectives of this work were to answer these questions and to provide more complete information about the potentials and limitations of GC and IR techniques. The results led us to the following conclusions: a) IR analysis of soils contaminated with petrol is not suitable due to volatilisation losses, b) there is a significant influence of organic matter in IR analysis, and c) both techniques demonstrated the capacity to accurately quantify TPH in soils, irrespective of their contamination levels.

Development of polyaniline microarray electrodes for cadmium analysis

Disposable screen-printed electrodes (SPCE) were modified using a cosmetic product to partially block the electrode surface in order to obtain a microelectrode array. The microarrays formed were electropolymerized with aniline. Scanning electron microscopy was used to evaluate the modified and polymerized electrode surface. Electrochemical characteristics of the constructed sensor for cadmium analysis were evaluated by cyclic and square-wave voltammetry. Optimized stripping procedure in which the preconcentration of cadmium was achieved by depositing at –1.20 V (vs. Ag/AgCl) resulted in a well defined anodic peak at approximately –0.7 V at pH 4.6. The achieved limit of detection was 4 × 10−9 mol dm−3. Spray modified and polymerized microarray electrodes were successfully applied to quantify cadmium in fish sample digests.

QuEChERS: a new sample preparation approach for the determination of ibuprofen and its metabolites in soils

Ibuprofen is one of the most used active pharmaceutical ingredients worldwide. A new method for the analysis of ibuprofen and its metabolites, hydroxyibuprofen and carboxyibuprofen, in soils is presented. The extraction of these compounds from the soil matrices was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. The method involves a single extraction of the investigated compounds with purified water (acidified at pH 2.5 with hydrochloric acid), and a slow and continuous addition of the QuEChERS content, followed by the addition of acidified acetonitrile (1% acetic acid), prior to the determination by liquid chromatography coupled with fluorescence detection (LC–FLD). Validation studies were carried out using soil samples with a range of organic carbon contents. Recoveries of the fortified samples ranged from 79.5% to 101%. Relative standard deviations for all matrix–compound combinations did not exceed 3%. The method quantification limits were ≤22.4 μg kg−1 in all cases. The developed method was applied to the analysis of sixteen real samples.

Mass spectrometry parameters optimization for the 46 multiclass pesticides determination in strawberries with gas chromatography ion-trap tandem mass spectrometry

Multiclass analysis method was optimized in order to analyze pesticides traces by gas chromatography with ion-trap and tandem mass spectrometry (GC-MS/MS). The influence of some analytical parameters on pesticide signal response was explored. Five ion trap mass spectrometry (IT-MS) operating parameters, including isolation time (IT), excitation voltage (EV), excitation time (ET),maximum excitation energy or “q” value (q), and isolationmass window (IMW) were numerically tested in order to maximize the instrument analytical signal response. For this, multiple linear regression was used in data analysis to evaluate the influence of the five parameters on the analytical response in the ion trap mass spectrometer and to predict its response. The assessment of the five parameters based on the regression equations substantially increased the sensitivity of IT-MS/MS in the MS/MS mode. The results obtained show that for most of the pesticides, these parameters have a strong influence on both signal response and detection limit.Using the optimized method, a multiclass pesticide analysis was performed for 46 pesticides in a strawberry matrix. Levels higher than the limit established for strawberries by the European Union were found in some samples.

Determination of the radiochemical purity of 99mTc-Tetrofosmin: comparision between five methods

GOAL: The manufacturing and distribution of strips of instant thin - layer chromatography with silica gel (ITLC - SG) (reference method) is currently discontinued so there is a need for an alternative method f or the determination of radiochemical purity (RCP) of 99m Tc - tetrofosmin. This study aims to compare five alternative methods proposed by the producer to determine the RCP of 99m Tc - tetrofosmin. METHODS: Nineteen vials of tetrofosmin were radiolabelled with 99m Tc and the percentages of the RCP were determined. Five different methods were compared with the standard RCP testing method (ITLC - SG, 2x20 cm): Whatman 3MM (1x10 cm) with acetone and dichloro - methane (method 1); Whatman 3MM (1x1 0 cm) with ethyl acetate (method 2); aluminum oxide - coated plastic thin - layer chromatography (TLC) plate (1x10 cm) and ethanol (method 3); Whatman 3MM (2x20 cm) with acetone and dichloro - methane (method 4); solid - phase extraction method C18 cartridge (meth od 5). RESULTS: The average values of RCP were 95,30% ± 1,28% (method 1), 93,95 ± 0,61% (method 2), 96,85% ± 0,93% (method 3), 92,94% ± 0,99% (method 4) and 96,25% ± 2,57% (method 5) (n=12 each), and 93,15% ± 1,13% for the standard method (n=19). There we re statistical significant differences in the values obtained for methods 1 (P=0,001), 3 (P=0,000) and 5 (P=0,004), and there were no statistical significant differences in the values obtained for methods 2 (P=0,113) and 4 (P=0,327). CONCLUSION: From the results obtained, methods 2 and 4 showed a higher correlation with the standard method. Unlike method 4, method 2 is less time - consuming than the reference method and can overcome the problems associated with the solvent toxicity. The remaining methods (1, 3 and 5) tended to overestimate RCP value compared to the standard method.

Enzymatic determination of choline in milk using a FIA system with potentiometric detection

The development of a FIA system for the determination of total choline content in several types of milk is described. The samples were submitted to hydrochloric acid digestion before injection into the system and passed through an enzymatic reactor containing choline oxidase immobilised on glass beads. This enzymatic reaction releases hydrogen peroxide which then reacts with a solution of iodide. The decrease in the concentration of iodide ion is quantified using an iodide ion selective tubular electrode based on a homogeneous crystalline membrane. Validation of the results obtained with this system was performed by comparison with results from a method described in the literature and applied to the determination of total choline in milks. The relative deviation was always < 5%. The repeatability of the method developed was assessed by calculation of the relative standard deviation (RSD) for 12 consecutive injections of one sample. The RSD obtained was < 0.6%.

Flow amperometric determination of carbofuran and fenobucarb

A simple, rapid, and precise amperometric method for quantification of N-methylcarbamate pesticides in water samples and phytopharmaceuticals is presented. Carbofuran and fenobucarb are the target analytes. The method is developed in flow conditions providing the anodic oxidation of phenolic-based compounds formed after alkaline hydrolysis. Optimization of instrumental and chemical variables is presented. Under the optimal conditions, the amperometric signal is linear for carbofuran and fenobucarb concentrations over the range of 1.0*10-7 to 1.0*10-5 molL-1, with a detection limit of about 2 ngmL-1. The amperometric method is successfully applied to the analysis of spiked environmental waters and commercial formulations. The proposed method allows 90 samples to be analysed per hour, using 500 mL of sample, and producing wastewaters of low toxicity. The proposed method permits determinations at the mgL 1 level and offers advantages of simplicity, accuracy, precision, and applicability to coloured and turbid samples, and automation feasibility.

Survey of trace elements (Al, As, Cd, Cr, Co, Hg, Mn, Ni, Pb, Se, and Si) in retail samples of flavoured and bottled waters

Concentrations of eleven trace elements (Al, As, Cd, Cr, Co, Hg, Mn, Ni, Pb, Se, and Si) were measured in 39 (natural and flavoured) water samples. Determinations were performed using graphite furnace electrothermetry for almost all elements (Al, As, Cd, Cr, Co, Mn, Ni, Pb, and Si). For Se determination hydride generation was used, and cold vapour generation for Hg. These techniques were coupled to atomic absorption spectrophotometry. The trace element content of still or sparkling natural waters changed from brand to brand. Significant differences between natural still and natural sparkling waters (p<0.001) were only apparent for Mn. The Mann–Whitney U-test was used to search for significant differences between flavoured and natural waters. The concentration of each element was compared with the presence of flavours, preservatives, acidifying agents, fruit juice and/or sweeteners, according to the labelled composition. It was shown that flavoured waters generally increase the trace element content. The addition of preservatives and acidifying regulators had a significant influence on Mn, Co, As and Si contents (p<0.05). Fruit juice can also be correlated to the increase of Co and As. Sweeteners did not provide any significant difference in Mn, Co, Se and Si content.

New biomimetic sensors for the determination of tetracycline in biological samples: batch and flow mode operations

New potentiometric membrane sensors with cylindrical configuration for tetracycline (TC) are described based on the use of a newly designed molecularly imprinted polymer (MIP) material consisting of 2-vinylpyridine as a functional monomer in a plasticized PVC membrane. The sensor exhibited significantly enhanced response towards TC over the concentration range 1.59 10 5–1.0 10 3 mol L 1 at pH 3–5 with a lower detection limit of 1.29 10 5 mol L 1. The response was near-Nernstian, with average slopes of 63.9 mV decade 1. The effect of lipophilic salts and various foreign common ions were tested and were found to be negligible. The possibility of applying the proposed sensor to TC determination in spiked biological fluid samples was demonstrated.

Electroanalytical determination of oxadiazon and characterization of its base-catalyzed ring-opening products

The electrochemical behavior of the hydrolysis products of oxadiazon was studied by cyclic and square-wave voltammetry using a glassy carbon electrode. Maximum currents were obtained at pH 12.8 in an aqueous electrolyte solution containing 30% ethanol and the current did not decrease with time showing that there was little adsorption of the reaction products on the electrode surface. The hydrolysis products of oxadiazon were identi®ed, after isolation and puri®cation, as 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl)-2-ethoxycarbonylhydrazine (Oxa1) and 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl) hydrazine (Oxa2) with redox potentials 0.6Vand 70.1V (vs. Ag=AgCl), respectively. Based on the electrochemical behavior of 1-trimethylacetyl-2-(2,4-dichloro-5-isopropoxyphenyl) hydrazine (Oxa2) a simple electroanalytical procedure was developed for the determination of oxadiazon in commercial products used in the treatment of rice crops in Portugal that contain oxadiazon as the active ingredient. The detection limit was 161074 M, the mean content and relative standard deviation obtained for seven samples of two different commercial products by the electrochemical method were 28.4 0.8% (Ronstar) and 1.9 0.2% (Ronstar GR), and the recoveries were 100.3 5.4% and 101.1 5.3 %, respectively.

Determination of tartaric acid in wines by FIA with tubular tartrate-selective electrodes

A flow injection analysis (FIA) system comprising a tartrate- (TAT) selective electrode has been developed for determination of tartaric acid in wines. Several electrodes constructed for this purpose had a PVC membrane with a complex of quaternary ammonium and TAT as anion exchanger, a phenol derivative as additive, and a more or less polar mediator solvent. Characterization of the electrodes showed behavior was best for membranes with o-nitrophenyl octyl ether as solvent. On injection of 500 μL into a phosphate buffer carrier (pH = 3.1; ionic strength 10–2 mol/L) flowing at 3 mL/min, the slope was 58.06 ± 0.6 with a lower limit of linear range of 5.0 × 10–4 mol/L TAT and R2 = 0.9989. The interference of several species, e.g. chloride, bromide, iodide, nitrate, gallic acid, tannin, sucrose, glucose, fructose, acetate, and citrate, was evaluated in terms of potentiometric selectivity coefficients. The Hofmeister series was followed for inorganic species and the most interfering organic ion was citrate. When red and white wines were analyzed and the results compared with those from an independent method they were found to be accurate, with relative standard deviations below 5.0%.