Otimização e validação de metodologia analítica empregando SPE e LC-ESI-MS/MS para determinação de multiclasses de agrotóxicos e metabólitos em água de superfície e de abastecimento público

A aplicação de agrotóxicos nas práticas agrícolas aumentou muito nos últimos anos. Isto vem ocorrendo devido ao crescimento populacional, demandando maior produção de alimentos. O uso de agrotóxicos e seus resíduos tornaram-se um problema devido a possível contaminação das águas de superfície e subterrânea, podendo impactar o meio ambiente e causar danos à saúde pública. Na cidade de Rio Grande, RS, Brasil, o suprimento de água potável é realizado pela CORSAN (Companhia Riograndense de Saneamento), que capta a água do Canal São Gonçalo, o qual estabelece uma ligação entre as duas lagoas: Lagoa dos Patos e Lagoa Mirim. Em suas margens há também a captação de água para irrigação das culturas agrícolas. Esta interação entre o uso da água das lagoas e a agricultura, pode resultar na contaminação das águas que são captadas para abastecimento dos municípios situados na região. Uma metodologia analítica empregando Extração em Fase Sólida (SPE) e Cromatografia Líquida acoplada a uma fonte de ionização por Electrospray tandem Espectrometria de Massas (LCESI-MS/MS) foi desenvolvida e validada para a determinação de dezoito agrotóxicos multiclasses (herbicidas, inseticidas e fungicidas) e dois metabólitos em amostras de água superficial e de abastecimento público. Esta metodologia foi aplicada para monitoramento durante dez meses na água superficial do Canal São Gonçalo e na água de consumo da cidade de Rio Grande, após o tratamento pela CORSAN. Os agrotóxicos selecionados foram: clomazona, bispiribaque-sódio, diurom, atrazina, simazina, imazetapir, imazapique, metsulfuron-metílico, quincloraque, penoxsulam, 2,4-D, pirazosulfuron-etílico, bentazona, propanil, irgarol, tebuconazol, fipronil e carbofurano. Os metabólitos foram: 3,4-DCA e 3-hidroxicarbofurano. Os limites de detecção do método variaram entre 0,4 – 40,0 ng L -1 , enquanto para os limites de quantificação a variação foi de 4,0 – 100,0 ng L -1 . Todos os compostos apresentaram excelente linearidade, com coeficiente de determinação maior do que 0,99. As recuperações empregando SPE com cartuchos contendo 500 mg de C18ec, variaram entre 70 a 120%, para 95% dos compostos, apresentando %RSD 20%. Através do monitoramento de múltiplas reações (MRM), duas transições diferentes (íon precursor – íon produto) foram selecionadas para cada composto, uma para quantificação e outra para confirmação, o que aumentou a seletividade do método. Para as amostras analisadas, foram detectados agrotóxicos nível de ng L -1 . O método desenvolvido é sensível, rápido e apresenta elevada seletividade, permitindo a identificação e a quantificação dos agrotóxicos em águas superficiais e de abastecimento público, atendendo os níveis requeridos pelos órgãos reguladores como da União Européia (98/83/EC) e do Brasil segundo a Portaria Nº. 518 (25/03/2004).

Otimização e validação de métodos empregando DLLME, SPE, HPLC-DAD e LC-ESI-MS/MS para determinação de agrotóxicos em água subterrânea

A preocupação com a poluição das águas por agrotóxicos tem aumentado, visto que aumentou o número de detecções de agrotóxicos em águas. A falta de avaliação da qualidade da água consumida pela população de áreas rurais onde não existe o abastecimento público de água potável, deve ser considerada, pois essas águas se encontram próximo a áreas de cultivo, onde há intensa aplicação de agrotóxicos. Nessas regiões, o abastecimento de água para as residências e para a irrigação é feito geralmente através das águas de poços. Neste trabalho, um método para determinação dos agrotóxicos carbofurano, clomazona, 2,4-D e tebuconazol em água subterrânea foi desenvolvido e validado. O método utilizou a Extração em Fase Sólida (SPE) e determinação por Cromatografia Líquida de Alta eficiência com Detecção por Arranjo de Diodos (HPLC-DAD) e confirmação por Cromatografia Líquida tandem Espectrometria de Massas (LC-MS/MS). Para a SPE utilizou-se cartuchos C18 de 200 mg, e eluição com 1 mL de metanol. Após a otimização dos parâmetros de extração e separação dos compostos, o método foi validado avaliando-se curva analítica, linearidade, limites de detecção e quantificação, precisão (repetitividade e precisão intermediária) e exatidão (recuperação). Todas as curvas analíticas apresentaram valores de r maiores que 0,99. Os LOQs para o método, considerando a etapa de pré-concentração de 250 vezes, foram de 0,2 µg L -1 para todos os agrotóxicos por HPLC-DAD e, por LC-MS/MS, 4,0 ng L -1 para clomazona, carbofurano e tebuconazol e de 40,0 ng L -1 para 2,4-D. As recuperações foram entre 60,3 e 107,7% para a repetitividade e entre 67,5 e 115,3% para a precisão intermediária, com RSD de 0,8 a 20,7% para todos os compostos por HPLC-DAD. Para o LC-MS/MS a precisão em termos de repetitividade, variou entre 0,97 e 20,7%, e as recuperações entre 67,0 e 108,9%. O método foi aplicado na determinação de agrotóxicos em amostras de águas subterrâneas durante um ano. Nas amostras foram detectados agrotóxicos em níveis de µg L -1 . Dentro do contexto atual da Química Analítica, de desenvolver métodos mais rápidos, que utilizem menor quantidade de solvente, de amostra e com altos fatores de enriquecimento, foi otimizado um método de extração para os agrotóxicos carbofurano, clomazona e tebuconazol utilizando a Microextração Líquido-Líquido Dispersiva (DLLME) e determinação por LC-MS/MS. Foram otimizados alguns parâmetros que influenciam no processo de extração, como: tipo e volume dos solventes dispersores e extratores, tempo de extração, força iônica e velocidade de centrifugação. Nas condições otimizadas, as recuperações para os níveis de concentração entre 0,02 e 2,0 g L -1 variaram entre 62,7 e 120,0%, com valores de RSD entre 1,9 e 9,1%. O LOQ do método foi de 0,02 µg L -1 para todos os compostos. Quando comparado com a SPE se demonstrou rápido, simples, de baixo custo, além de necessitar de menores volumes de amostra para determinação de agrotóxicos em águas. O método mostrou-se adequado à análise dos agrotóxicos em água subterrânea e todos os parâmetros de validação obtidos estão dentro dos limites sugeridos para validação de métodos cromatográficos

Otimização e validação de método empregando SPE e LC-APCI-MS/MS para determinação de fármacos em água de supefície e de abastecimento público

O uso mundial dos fármacos classificados como contaminantes emergentes tornouse um novo problema ambiental devido à possível contaminação das águas de superfície e de abastecimento, podendo impactar o meio ambiente e causar danos à saúde pública. Na cidade de Rio Grande, RS, Brasil, o suprimento de água potável é realizado pela CORSAN (Companhia Riograndense de Saneamento), que capta a água do Canal São Gonçalo, o qual estabelece uma ligação entre as lagoas: dos Patos e Mirim. Neste trabalho um método analítico empregando Extração em Fase Sólida (SPE) e Cromatografia Líquida com Fonte de Ionização Química a Pressão Atmosférica acoplada a Espectrometria de Massas (LC-APCI-MS/MS) foi desenvolvido e validado para a determinação dos fármacos atenolol, cafeína, diclofenaco, fluoxetina e sulfametoxazol em amostras de água superficial e de abastecimento público. O método foi validado conforme parâmetros do INMETRO e SANCO. Os limites de detecção do método variaram entre 0,053 – 0,53 µg L -1 , enquanto para os limites de quantificação a variação foi de 0,16 – 1,6 µg L-1 . Todos os compostos apresentaram excelente linearidade, com coeficiente de correlação maior do que 0,99. Os valores de recuperação estiveram na faixa de 70 a 120%, com RSD menores que 20% para todos os compostos. Através do monitoramento de múltiplas reações (MRM), duas transições diferentes (íon precursor – íon produto) foram selecionadas para cada composto, uma para quantificação e outra para confirmação, o que aumentou a seletividade do método. O efeito de matriz foi avaliado, e dois compostos apresentaram supressão de sinal. O efeito de matriz foi compensado com calibração dos padrões na matriz.

Avaliação preliminar da contaminação por BTEX, em água subterrânea de poços tubulares, no município de Natal-RN

Among the different types of pollutants typically attributed to human activities, the petroleum products are one of the most important because of its toxic potential. This toxicity is attributed to the presence of substances such as benzene and its derivatives are very toxic to the central nervous system of man, with chronic toxicity, even in small concentrations. The area chosen for study was the city of Natal, capital of Rio Grande do Norte, where samples were collected in six different areas in the city, comprising 10 wells located in the urban area, being carried out in three distinct periods March/2009, December / June/2010 and 2009, and were evaluated for contamination by volatile hydrocarbons (BTEX - benzene, toluene, ethylbenzene and xylenes), so this work aimed to assess the quality of groundwater wells that supply funding for public supply and trade in the urban area of the city of Natal, in Rio Grande do Norte, contributing to the environmental assessment of the municipality. The analysis of BTEX in water was performed according to EPA Method 8021b. Was used the technique of headspace (TriPlus TP100) coupled to high resolution gas chromatography with selective photoionization detector (PID) and flame ionization (FID) - model Trace GC Ultra, Thermo Electron Corporation brand. The procedure adopted allowed the detection of concentrations of the order of μg.L-1. Data analysis with respect to BTEX in groundwater in the area monitored so far, shows that water quality is still preserved, because it exceeds the limits imposed by the potability Resolution CONAMA Nº. 396, April 2008

Eutrofização do reservatório Engenheiro Armando Ribeiro Gonçalves, no Rio Grande do Norte: implicações para o abastecimento público e para a piscicultura intensiva em tanques-rede

This study aimed to describe the spatial and temporal patterns of variation in trophic state and its relation with the structure and dynamics of planktonic community of a large reservoir located in semi-arid tropical region of Northeast Brazil. The reservoir Armando Ribeiro Gonçalves is the biggest reservoir of the Rio Grande do Norte State and is responsible for about 53% of all surface water accumulated in the State. The samples of water and plankton were taken monthly in 10 points distributed throughout the longitudinal axis of the reservoir and over a full hydrological cycle. The samples were collected to determine concentrations of total phosphorus, total nitrogen, chlorophyll a and suspended solids (fixed and volatile) and for determining the composition and abundance of phytoplanktonic and zooplanktonic species. During the study period, the reservoir was characterized as eutrophic and there was no trend of increasing the trophic state of the reservoir in the period of drought. The concentrations of total phosphorus and suspended fixed solids decreased towards the dam while the N:P ratios increased in the same direction due to the reduction in the phosphorus concentrations and relative constancy in the nitrogen concentrations. The N:P ratios observed were indicative of greater limitation by phosphorus than by nitrogen. However, as concentrations of both nutrients were high and the water transparency was very low, with secchi depth usually lower than one meter, it seems likely that the planktonic primary production of the reservoir is more limited by the availability of light than the availability of nutrients. High nutrient concentrations coupled with low availability of light may explain the continuing dominance of filamentous cyanobacteria such as Cylindrospermopsis raciborskii in the plankton of the reservoir.These cyanobacteria are potentially toxic and pose a serious environmental problem because it compromises the water quality for public supply, recreation and fishing when present in high densities as in this study. The mesozooplankton of the reservoir was dominated by the calanoid Notodiaptomus cearensis and the cladoceran Diaphanosoma spinulosum. In general, the structure of zooplankton community seems to be particularly influenced by the spatial variation of cyanobacteria. The results of the regression analyses show that both the chlorophyll a concentrations and the cyanobacteria biovolume were more strongly correlated with the nitrogen than with phosphorus and that the water transparency was more strongly correlated with algal biomass than with other sources of turbidity. The maximum load of phosphorus to attain the maximum permissible concentration of total P in the reservoir was estimated in 63.2 tonnes P/ year. The current external P load to the reservoir is estimated in 324 tonnes P / year and must be severely reduced to improve the water quality for water supply and allow the implementation of aquaculture projects that could contribute to the socio-economic development of the region

Investigação e gerenciamento de áreas contaminadas por postos revendedores de combustíveis em Natal

Activities that have fuel subterranean storage system are considered potentially polluting fuels by CONAMA Resolution 273, due to the possibility of leak, outpouring and overflow of fuel into the ground. Being even more worrying when contaminate groundwater for public supply, as the case of Natal City. For this reason, the Public Ministry/RN, in partnership with UFRN, developed the project environmental suitability of Gas stations in Natal, of which 36% showed evidence of contamination. This paper describes the four stages of the management of contaminated areas: preliminary assessment of environmental liabilities, detailed confirmatory investigation of the contamination, risk analysis to human health (RBCA), as well as the remediation plan of degraded areas. Therefore it is presented a case study. For the area investigated has been proposed a mathematical method to estimate the volume of LNAPL by a free CAD software (ScketchUp) and compare it with the partition method for grid area. Were also performed 3D graphics designs of feathers contamination. Research results showed that passive benzene contamination in groundwater was 2791.77 μg/L, when the maximum allowed by CONAMA Resolution 420 is 5 μg/L which is the potability standards. The individual and cumulative risks were calculated from 4.4 x10-3, both above the limits of 1.0 x10-5 or by RBCA 1.0 x10-6 by the Public Ministry/RN. Corrective action points that remediation of dissolved phase benzene is expected to reach a concentration of 25 μg/L, based on carcinogenic risk for ingestion of groundwater by residents residential, diverging legislation. According to the proposed model, the volume of LNAPL using the ScketchUp was 17.59 m3, while by the grid partitioning method was 14.02 m3. Because of the low recovery, the expected removal of LNAPL is 11 years, if the multiphase extraction system installed in the enterprise is not optimized

Groundwater from infiltration galleries used for small public water supply systems: contamination with pesticides and endocrine disruptors

Infiltration galleries are among the oldest known means used for small public water fountains. Owing to its ancestral origin they are usually associated with high quality water. Thirty-one compounds, including pesticides and estrogens from different chemical families, were analysed in waters from infiltration galleries collected in Alto Douro Demarcated Wine region (North of Portugal). A total of twelve compounds were detected in the water samples. Nine of these compounds are described as presenting evidence or potential evidence of interfering with the hormone system of humans and wildlife. Although concentrations of the target analytes were relatively low, many of them below their limit of quantification, four compounds were above quantification limit and two of them even above the legal limit of 0.1 lg/L: dimethoate (30.38 ng/L), folpet (64.35 ng/L), terbuthylazine-desethyl (22.28 to 292.36 ng/L) and terbuthylazine (22.49 to 369.33 ng/L).

Performance of small wind turbines: simulation of electricity supply to loads connected to the public or isolated grid

ABSTRACT The successful in the implementation of wind turbines depends on several factors, including: the wind resource at the installation site, the equipment used, project acquisition and operational costs. In this paper, the production of electricity from two small wind turbines was compared through simulation using the computer software HOMER - a national model of 6kW and an imported one of 5kW. The wind resources in three different cities were considered: Campinas (SP/BR), Cubatão (São Paulo/BR) and Roscoe (Texas/ USA). A wind power system connected to the grid and a wind isolated system - batteries were evaluated. The results showed that the energy cost ($/kWh) is strongly dependent on the windmill characteristics and local wind resource. Regarding the isolated wind system – batteries, the full supply guarantee to the simulated electrical load is only achieved with a battery bank with many units and high number of wind turbines, due to the intermittency of wind power.

External control of the public water supply in 29 Brazilian cities

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Use of the HDS system (hydric depuration with soils) associated to other constructed wetlands techniques for public water supply

Two projects of water treatment for public water supply were developed and operated by using combined systems of constructed wetlands. One of the projects was carried out in the town of Analandia, Sao Paulo, Brazil and wetlands with floating aquatic plants associated to the HDS system were used. Nearly 6480 inhabitants were supplied. The other conducted project was an experimental station in partnership with SABESP (Sao Paulo State Sanitation Agency/Brazil), for the pretreatment of 1700 l.s-1 of waters from the Cotia River, which is used for the population's supply after conventional treatment at the Lower Cotia Water Treatment Station. For this pilot project, wetlands with emergents and floating plants associated to the HDS system were used. The proposed objectives were achieved in both projects.

Performance of constructed wetland system for public water supply

The project is being conducted in the town of Analândia, São Paulo, Brazil. The constructed wetlands system for water supply consists of a channel with floating aquatic macrophytes, HDS system (Water Decontamination with Soil - Patent PI 850.3030), chlorinating system, filtering system and distribution. The project objectives include investigating the process variables to further optimize design and operation factors, evaluating the relation of nutrients and plants development, biomass production, shoot development, nutrient cycling and total and fecal coliforms removal, comparing the treatment efficiency among the seasons of the year; and moreover to compare the average values obtained between February and June 1998 (Salati et al., 1998) with the average obtained for the same parameters between March and June 2000. Studies have been developed in order to verify during one year the drinking quality of the water for the following parameters: turbidity, color, pH, dissolved oxygen, total of dissolved solids, COD, chloride, among others, according to the Ministry of Health's Regulation 36. This system of water supply projected to treat 15 L s-1 has been in continuous operation for 2 years, it was implemented with support of the National Environment Fund (FNMA), administered by the Center of Environmental Studies (CEA-UNESP), while the technical supervision and design were performed by the Institute of Applied Ecology. The actual research project is being supported by FAPESP.

Fluoridation of the public water supply and prevalence of dental fluorosis in a peripheral district of the municipality of Bauru, SP

Objectives: The objectives of this study were to assess the fluoride concentration in the public water supply and the prevalence of dental fluorosis in schoolchildren between 7 and 15 years old, living in a peripheral district of the municipality of Bauru. Material and Methods: For this, fifty two water samples were collected on three different days of one week. These samples were analyzed for fluoride by means of the ion-sensitive electrode method (Orion 9609) coupled to a potentiometer (Procyon, model 720). In this method, 1.0 mL of TISAB II (Orion) was added to 1.0 mL of the sample. For the epidemiological survey of fluorosis, 52 schoolchildren of both genders, aged between 7 and 15 were assessed, with prior authorization from their caretakers. Only one person examined the children, after supervised toothbrushing and drying with cotton wool rolls. The TF index was used. Results: The fluoride concentrations in the water samples ranged from 0.62 to 1.20 mg/L, with a mean of 0.9 mg/L. The prevalence of dental fluorosis was 33%, with severity ranging from TF1 to TF4 (Kappa of 0.73 and concordance of 83.33%). Conclusions: The results from the analysis of water samples indicated a fluoride concentration greater than recommended for Bauru. The fluorosis levels found were higher than expected for a peripheral district, in which water is one of the few sources of fluoride.