Desempenho analítico de laboratórios prestadores de serviço na determinação de metais em águas

Analytical laboratories are expected to produce reliable results. Decision makers are guided in their actions (financial, legal and environmental) using analytical data provided by numerous laboratories. This work aimed to evaluate the analytical performance of Brazilian laboratories on producing trustworthy results. Nineteen laboratories, accredited and non-accredited ones, were contracted to analyze a USGS (United States Geological Survey) certified water sample for 17 chemical elements (mostly metals) without knowing the origin of the sample. Considering all the results produced, only 35% of them were valid. Three laboratories present satisfactory performances, whereas the majority showed a very poor overall performance. The outcomes of this work show the need for a more effective analytical quality program to Brazilian laboratories.

Sistema limpo em linha para extração em fase sólida de contaminantes emergentes em águas naturais

A solid-phase in-line extraction system for water samples containing low levels of emerging contaminants is described. The system was specially developed for large volume samples (up to 4 L) using commercial solid-phase extraction (SPE) cartridges. Four sets containing PTFE-made connectors, brass adapters and ball valves were used to fit SPE cartridges and sample bottles to a 4-port manifold attached to a 20 L carboy. A lab-made vacuum device was connected to the manifold cap. The apparatus is robust and less expensive than the typical available system. Its also provides less experimental handling, avoiding cross contamination and sample losses.

Ambientes de cultivo, recipientes e substratos na produção de biomassa foliar e radicular em mudas de maracujazeiro amarelo em Aquidauana - MS

The objective of the work was to evaluate the effects of environment, recipients, and substrate compositions in passion fruit (Passiflora edulis Sims f. flavicarpa Deg.) seedlings biomass production in Pantanal region from September to November of 2006. Experimental trials were conducted in four protected environments, in two types of containers and three different substrate compositions. The environments were: A1 (greenhouse covered with low-density, 150-microns-thick polyethylene film), A2 (monofilament black screened with mesh for 50% of shade), A3 (aluminized screened with mesh for 50% of shade) and A4 (environment covered with straw of native coconut palm); the recipients were: polyethylene bags (R1) (15 x 25 cm) and polystyrene trays (R2) (with 72 cells). There substrates were: S1 (soil + organic compost + vermiculite, 1:1: 1 v/v), S2 (soil + organic compost + sawdust, 1:1: 1 v/v) and S3 (soil + organic compost + vermiculite + sawdust, 1:1: 1/2: 1/2 v/v). The experimental design was completely randomized statistical analysis in split-split-plot, with fifteen replications. The treatments in the plot were environments, in the subplots were pots, and subsubplots were substrates (4 x 2 x 3 = 24 treatments). Fresh and dry mass of aerial and root system parts were evaluated. Environments with screen showed better results for seedlings of yellow passion fruit biomass in polyethylene bags. Polyethylene bags promoted higher biomasses. The substrate with vermiculite showed better results for both types of containers. The substrate with a higher percentage of sawdust showed the worst result.

Avaliação de metais traços e íons majoritários em águas de chuva na cidade de São Paulo

Rainfall samples collected in the downtown area of São Paulo city, during 2003, exhibited average concentrations of cadmium, lead and copper of 1.33, 8.52 and 49.5 nmol L-1, respectively. Among the major ions, NH4+ was the predominant species followed by NO3-, SO4(2-) and Ca2+, with volume weighed mean (VWM) concentrations of 37.1, 20.1, 11.9 and 10.8 µmol L-1, respectively. All the determined species showed high inter-events variability, including free H+ ions whose VWM concentration was 4.03 µmol L-1, corresponding to a pH value of 5.39.

On-line identification of minor flavones from sugarcane juice by LC/UV/MS and post-column derivatization

This work describes the on-line characterization of minor flavones from sugarcane (Saccharum officinarum) juice by high-performance liquid chromatography coupled to diode array UV detection and mass spectrometry (LC/UV/MS) using atmospheric pressure chemical ionization-collision-induced dissociation (APCI-CID-MS/MS) and post-column derivatization using UV shift reagents. HPLC-UV analysis with shift reagents provided information about the substitution pattern in the flavonoid skeleton and, combined with MS data, these techniques allowed for the on-line identification of five "garapa" flavones: luteolin-8-C-glucosyl-7-O-glucuronide; tricin-7-O-neohesperoside-4'-O-rhamnoside; tricin-7-O-methylglucuronate-4'-O-rhamnoside; tricin-7-O-methylglucuronide; swertisin, while four other compounds were partially identified as glycosylflavones. Only swertisin (7-O-methylapigenin-6-C-glucoside) was reported previously in sugarcane molasses.

Eletroforese capilar acoplada à espectrometria de massas (CE-MS): vinte anos de desenvolvimento

CE-MS has been increasingly used for analysis of a vast array of compounds. This article reviews the different electrophoretic modes, interfaces and mass analyzers that are commonly used in the CE-MS coupling, as well as the technique advantages and performance characteristics. A large compilation of CE-MS applications is also presented. Therefore, this review is both a guide for beginners and a collection of key references for people who are familiar to the technique. Furthermore, this is the first CE-MS review published in a Brazilian journal and marks the installation of the first two commercial CE-MS units in Sao Paulo State.

Solid-phase microextraction for determination of 3-chloro-4-(dichloromethyl)-5-hydroxy-2[5H]-furanone in water

Solid-phase microextraction, using on-line bis(trimethylsilyl)trifluoroacetamide derivatisation, gas chromatography, and mass spectrometry, was evaluated in the quantification of 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) in water samples. Fibres encompassing a wide range of polarities were used with headspace and direct immersion sampling. For the immersion procedure, various parameters affecting MX extraction, including pH, salinity, temperature, and extraction time were evaluated. The optimised method (polyacrylate fibre; 20% Na2SO4; pH 2.0; 60 min; 20 °C) was applied for reservoir chlorinated water samples-either natural or spiked with MX (50 ng L-1 and 100 ng L-1). The recovery of MX ranged from 44 to 72%. Quantification of MX in water samples was done using external standard and the selected ion monitoring mode. Correlation coefficient (0.98%), relative standard deviation (5%), limit of detection (30 ng L-1) and limit of quantification (50 ng L-1) were obtained from calibration curve.

Peixes da Estação Ecológica Serra Geral do Tocantins, bacias dos Rios Tocantins e São Francisco, com observações sobre as implicações biogeográficas das "águas emendadas" dos Rios Sapão e Galheiros

Um levantamento preliminar da ictiofauna que ocorre na Estação Ecológica Serra Geral de Tocantins, situada no Sudeste do Estado do Tocantins e Noroeste do Estado da Bahia, é apresentado. A Estação Ecológica Serra Geral de Tocantins situa-se no divisor de águas entre as bacias do Rio São Francisco (Rio Sapão) e Rio Tocantins (bacias dos Rios Novo, Balsas e Manuel Alves). A cabeceira comum ou "água emendada" do Rio Sapão e Rio Galheiros, este um afluente do Rio Novo, situa-se no interior da estação e é considerada na literatura como uma possível área de intercâmbio ictiofaunístico entre a bacia do Rio São Francisco e a bacia do Rio Tocantins. Trinta e cinco espécies de peixes foram registradas dentro da Estação Ecológica Serra Geral de Tocantins e em seu entorno imediato, algumas delas desconhecidas da ciência e possivelmente endêmicas da região. Um total de 111 espécies de peixes foi registrado regionalmente (incluindo espécies de peixes registrados nos trechos do Rio Sapão e do Rio Novo/do Sono abaixo da estação). O acará Cichlasoma sanctifranciscense é aqui registrado pela primeira vez na bacia do Rio Tocantins. A ocorrência desta espécie, bem como do lambari Astyanax novae, no Rio Sapão e no Rio Novo/do Sono, são considerados os únicos exemplos inequívocos de transposição natural de espécies de peixes entre as bacias do Rio São Francisco e Tocantins efetuado pelas águas emendadas dos rios Sapão e Galheiros.

Controle social e gestão participativa em saúde pública em unidades de saúde do município de Campo Grande, MS, 1994-2002

A participação social no Brasil evoluiu de movimento operário e de sindicatos, culminando na institucionalização através de Conselhos. Na área da saúde, foi legalizada pela Lei 8142/90. O objetivo deste estudo é conhecer a prática do controle social exercida em Conselhos de Unidades e sua influência nas políticas de saúde do município de Campo Grande, MS. Foram feitos cinco estudos de caso, tendo como fonte principal as atas de reuniões e como referencial de análise um documento do Ilpes/Claps (1975). Os Conselhos organizam-se em plenário, com coordenador, secretário, composição hoje paritária, representatividade reduzida e periodicidade mensal. O processo decisório contempla principalmente elementos técnico-administrativos e técnico-operacionais. No período 1998-2002, o controle social fortaleceu-se por encaminhamentos mais concretos, mas a capacidade de deliberação precisa ser fortalecida por uma capacitação que inclua elementos técnicos, políticos e administrativos, representatividade, fortalecimento da cidadania, divulgação intensa das atividades dos Conselhos, inclusive na mídia, maior mobilização social e articulação entre os vários Conselhos e instâncias municipais que fazem interface com o setor de saúde.

Caracterização das vítimas de ferimentos por arma de fogo, atendidas pelo Serviço de Atendimento Móvel de Urgência em Campo Grande-MS

A violência, em todas as suas apresentações, tem crescido de forma avassaladora no país, elevando os indicadores de morbidade e mortalidade por causas externas. O uso das armas de fogo, muitas vezes, faz vítimas fatais ou que podem permanecer sequeladas. Tal fato tem aumentado o ônus do estado com internações hospitalares e acréscimo dos anos de vida perdidos da população jovem, que constitui a grande maioria dessas vítimas. Nesse sentido, o presente estudo objetivou fazer um levantamento das vítimas de ferimentos por arma de fogo, atendidas pelo Serviço de Atendimento Móvel de Urgência no município de Campo Grande-MS, no período de abril de 2005 a abril de 2007, nos dois primeiros anos de funcionamento, desde a implantação desse serviço na capital do Estado de Mato Grosso do Sul. Realizou-se estudo descritivo, baseado em análise documental do sistema de informação do SAMU do município de Campo Grande-MS. Foram descritos 233 atendimentos. Os resultados evidenciaram 213 vítimas do sexo masculino, a faixa etária mais acometida foi dos 20 aos 24 anos de idade, a cabeça e o pescoço foram as partes do corpo mais atingidas e a região Sul do município de Campo Grande foi a que concentrou maior número de atendimentos. Conclui-se que a violência por arma de fogo em Campo Grande-MS atinge a camada economicamente ativa da população e provém de regiões de bolsões de pobreza e desigualdade social, justificando a implantação de um serviço como o SAMU.

Situação epidemiológica da brucelose bovina no Estado do Mato Grosso do Sul

Realizou-se um estudo para caracterizar a situação epidemiológica da brucelose bovina no Estado de Mato Grosso do Sul. Foram definidos três estratos (regiões): Pantanal-corte, Planalto-corte e Planalto-leite, este último subdividido em Bolsão, Campo Grande e Dourados. Em cada estrato foram amostradas aleatoriamente propriedades e, dentro dessas, foi escolhido, de forma aleatória, um número pré-estabelecido de animais, dos quais foi obtida uma amostra de sangue. No total, foram amostrados 14.849 animais, provenientes de 1.004 propriedades. Em cada propriedade amostrada foi aplicado um questionário epidemiológico para verificar suas características e também para detectar transtornos reprodutivos que poderiam estar associados à infecção brucélica. O teste utilizado foi o do antígeno acidificado tamponado. O rebanho foi considerado positivo se pelo menos um animal foi reagente à prova sorológica. Para o Estado, a prevalência de focos foi de 41,5% [36,5-44,7%]. As prevalências de focos e de animais infectados por estrato foram, respectivamente, de: 59,0% [52,8-64,9%] e 12,6% [9,1-17,2%] para o estrato Pantanal-corte, e 40,6% [35,8-45,5%] e 4,5% [2,1-9,0%] para Planalto-corte. No estrato Planalto-leite, a prevalência de focos foi de 33,1% [28,4-38,1%]. Os fatores de risco (odds ratios, OR) associados à condição de foco foram: ter ≥500 vacas (OR = 2,46 [1,81-3,34]), ocorrência de bezerros fracos (OR = 1,20 [0,87-1,65]) e uso da inseminação artificial (OR = 0,71 [0,50-1,01]).

Determination of chlorpheniramine in human plasma by HPLC-ESI-MS/MS: application to a dexchlorpheniramine comparative bioavailability study

In the present study a fast, sensitive and robust validated method to quantify chlorpheniramine in human plasma using brompheniramine as internal standard (IS) is described. The analyte and the IS were extracted from plasma by LLE (diethyl ether-dichloromethane, 80:20, v/v) and analyzed by HPLC-ESI-MS/MS. Chromatographic separation was performed using a gradient of methanol from 35 to 90% with 2.5 mm NH(4)OH on a Gemini Phenomenex C(8) 5 mu m column (50 x 4.6 mm i.d.) in 5.0 min/run. The method fitted to a linear calibration curve (0.05-10 ng/mL, R > 0.9991). The precision (%CV) and accuracy ranged, respectively: intra-batch from 1.5 to 6.8% and 99.1 to 106.6%, and inter-batch from 2.4 to 9.0%, and 99.9 to 103.1%. The validated bioanalytical procedure was used to assess the comparative bioavailability in healthy volunteers of two dexchlorpheniramine 2.0 mg tablet formulations (test dexchlorpheniramine, Eurofarma, and reference Celestamine (R), Schering-Plough). The study was conducted using an open, randomized, two-period crossover design with a 2 week washout interval. Since the 90% confidence interval for C(max) and AUC ratios were all within the 80-125% interval proposed by ANVISA and FDA, it was concluded that test and reference formulations are bioequivalent concerning the rate and the extent of absorption. Copyright (C) 2009 John Wiley & Sons, Ltd.

Enantioselective determination of chloroquine and its n-dealkylated metabolites in plasma using liquid-phase microextraction and LC-MS

A selective method using three-phase liquid-phase microextraction (LPME) in conjunction with LC-MS-MS was devised for the enantioselective determination of chloroquine and its n-dealkylated metabolites in plasma samples. After alkalinization of the samples, the analytes were extracted into n-octanol immobilized in the pores of a polypropylene hollow fiber membrane and back extracted into the acidic acceptor phase (0.1 M TFA) filled into the lumen of the hollow fiber. Following LPME, the analytes were resolved on a Chirobiotic V column using methanol/ACN/glacial aceti acid/diethylamine (90:10:0.5:0.5 by volume) as the mobile phase. The MS detection was carried out using multiple reaction monitoring with ESI in the positive ion mode. The optimized LPME method yielded extraction recoveries ranging from 28 to 66%. The method was linear over 5 - 500 ng/mL and precision (RSD) and accuracy (relative error) values were below 15% for all analytes. The developed method was applied to the determination of the analytes in rat plasma samples after oral administration of the racemic drug.

Online identification of chlorogenic acids, sesquiterpene lactones, and flavonoids in the Brazilian arnica Lychnophora ericoides Mart. (Asteraceae) leaves by HPLC-DAD-MS and HPLC-DAD-MS/MS and a validated HPLC-DAD method for their simultaneous analysis

Lychnophora ericoides Mart. (Asteraceae, Vernonieae) is a plant, endemic to Brazil, with occurrence restricted to the ""cerrado"" biome. Traditional medicine employs alcoholic and aqueous-alcoholic preparations of leaves from this species for the treatment of wounds, inflammation, and pain. Furthermore, leaves of L. ericoides are also widely used as flavorings for the Brazilian traditional spirit ""cachaca"". A method has been developed for the extraction and HPLC-DAD analysis of the secondary metabolites of L. ericoides leaves. This analytical method was validated with 11 secondary metabolites chosen to represent the different classes and polarities of secondary metabolites occurring in L. ericoides leaves, and good responses were obtained for each validation parameter analyzed. The same HPLC analytical method was also employed for online secondary metabolite identification by HPLC-DAD-MS and HPLC-DAD-MS/MS, leading to the identification of di-C-glucosylflavones, coumaroylglucosylflavonols, flavone, flavanones, flavonols, chalcones, goyazensolide, and eremantholide-type sesquiterpene lactones and positional isomeric series of chlorogenic acids possessing caffeic and/or ferulic moieties. Among the 52 chromatographic peaks observed, 36 were fully identified and 8 were attributed to compounds belonging to series of caffeoylferuloylquinic and diferuloylquinic acids that could not be individualized from each other.