Desenvolvimento de uma unidade laboratorial para quantificação de BTX como poluentes atmosféricos, usando microextração em fase sólida

This dissertation aims the development of an experimental device to determine quantitatively the content of benzene, toluene and xylenes (BTX) in the atmosphere. BTX are extremely volatile solvents, and therefore play an important role in atmospheric chemistry, being precursors in the tropospheric ozone formation. In this work a BTX new standard gas was produced in nitrogen for stagnant systems. The aim of this dissertation is to develop a new method, simple and cheaper, to quantify and monitor BTX in air using solid phase microextraction/ gas chromatography/mass spectrometry (SPME/CG/MS). The features of the calibration method proposed are presented in this dissertation. SPME sampling was carried out under non-equilibrium conditions using a Carboxen/PDMS fiber exposed for 10 min standard gas mixtures. It is observed that the main parameters that affect the extraction process are sampling time and concentration. The results of the BTX multicomponent system studied have shown a linear and a nonlinear range. In the non-linear range, it is remarkable the effect of competition by selective adsorption with the following affinity order p-xylene > toluene > benzene. This behavior represents a limitation of the method, however being in accordance with the literature. Furthermore, this behavior does not prevent the application of the technique out of the non-linear region to quantify the BTX contents in the atmosphere.

Estudos dos aspectos qualitativos e quantitativos da água e do sedimento no baixo curso do Rio Pitimbu (RN)

Urban growth of metropolitan areas has produced impacts of considerable importance on environment and water resources. Such impacts are in general associated with human activities, such as basin area uncontrolled development. In this context, Pitimbu river watershed, located at Natal metropolitan area, has been affected by uncontrolled development caused by urban expansion. Indeed, such effects have been reflected on water quantity and quality, which may produce social consequences. Pitimbu river is an important water supplier for human consumption, actually supplying a 2600 m3/h water discharge. This study aims to analyze the qualitative and quantitative aspects of water and sediment on Pitimbu river lowland portion. For this purpose, physical-chemical water properties were analyzed, and sediment macro invertebrates benthonic were monitored in two cross sections in a period between November 8th, 2007 and October 3rd, 2008. Monitoring methodology consisted of water and sediment sampling for laboratory analysis. Water quality analysis included Dissolved Oxygen, Oxygen Biochemical Demand, Nitrate, pH and Alkalinity, Suspended and Total Solids. The analysis of heavy metals in the sediment included Cadmium, Cobalt, Copper, Chrome, Silver and Nickel. Dry season water discharge data were measured and used to adjust recession function parameters, whose values reveal quick recession and strong river-aquifer unconfined interaction. Water quality analysis revealed the absence of degradation by organic composites. However, DO and BOD levels indicate that more consistent results could be provided if sampling time interval were reduced. Biomonitoring showed signs of aquatic ecosystem degradation by the absence of sensitive and abundance of resistant benthic organisms. Obtained results demonstrate the urgent need of effective management measures to provide environmental protection. The increase of environmental degradation will certainly make impracticable the use of water for human consumption

In vivo CYP2E1 phenotyping as a new potential biomarker of occupational and experimental exposure to benzene

Assessing CYP2E1 phenotype in vivo may be important to predict individual susceptibility to those chemicals, including benzene, which are metabolically activated by this isoenzyme. Chlorzoxazone (CHZ), a specific CYP2E1 substrate, is readily hydroxylated to 6-OH-chlorzoxazone (6-OH-CHZ) by liver CYP2E1 and the metabolic ratio 6-OH-CHZ/CHZ in serum (MR) is a specific and sensitive biomarker of CYP2E1 activity in vivo in humans. We used this MR as a potential biomarker of effect in benzene-treated rats and, also, in humans occupationally exposed to low levels of benzene. Male Sprague-Dawley rats (375-400 g b.w.) were treated i.p. for 3 days with either a 0.5 ml solution of benzene (5 mmol/kg b.w.) in corn oil, or 0.5 ml corn oil alone. Twenty-four hours after the last injection, a polyethylene glycol (PEG) solution of CHZ (20 mg/kg b.w.) was injected i.p. in both treated and control animals. After 2, 5.10,15, 20,30,45, 60, 90, 120, 180, and 240 min from injection, 0.2 ml blood was taken from the tip tail and stored at -20 degrees C until analysis. A modified reverse phase HPLC method using a 5 mu m Ultrasphere C18 column equipped with a direct-connection ODS guard column, was used to measure CHZ and its metabolite 6-OH-CHZ in serum. No statistically significant difference in the MR was observed, at any sampling time, between benzene-treated and control rats. The concentration-versus-time area under the curve (AUC), however, was lower (p < 0.05, Mann-Whitney test), whereas the systemic clearance was higher (p < 0.05) in treated than in control rats. Eleven petrochemical workers occupationally exposed to low levels of airborne benzene (mean +/- SD, 25.0 +/- 24.4 mu g/m(3)) and 13 non-exposed controls from the same factory (mean +/- SD, 6.7 +/- 4.0 mu g/m(3)) signed an informed consent form and were administered 500 mg CHZ p.o. Two hours later a venous blood sample was taken for CHZ and 6-OH-CHZ measurements. Despite exposed subjects showed significantly higher levels of t,t-MA and S-PMA, two biomarkers of exposure to benzene, than non-exposed workers, no difference in the MR mean values +/- SD was found between exposed (0.59 +/- 0.29) and non-exposed (0.57 +/- 0.23) subjects. So, benzene was found to modify CHZ disposition, but not CYP2E1 phenotype in benzene-treated rats, nor in workers exposed to benzene, probably due to the levels of exposure being too low. (C) 2009 Elsevier B.V. All rights reserved.

Effects of adding a spray-dried polyclonal antibody preparation on ruminal fermentation patterns and digestibility of cows fed high concentrate diets

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Temporal patterns of parasitism in Diatraea saccharalis Fabr. (Lep., Crambidae) populations at different spatial scales in sugarcane fields in Brazil

Biological control of Diatraea saccharalis is regarded as one of the best examples of successful classical biological control in Brazil. Since the introduction of the exotic parasitoid, Cotesia flavipes, from Pakistan at the beginning of the 1970s, decrease in D. saccharalis infestation in sugarcane fields has been attributed to the effectiveness of this agent. Recently, the native Tachinidae fly parasitoids (Lydella minense and Paratheresia claripalpis) have also been implicated in this success. However, quantitative data confirming the actual contribution of these agents to the control of D. saccharalis are rather limited. The purpose of this study was to investigate the dynamics of the interactions between D. saccharalis and its parasitoids, emphasizing the temporal patterns of parasitism. To investigate this question, a large data set comprising information collected from two sugarcane mills located in the state of São Paulo, Brazil (Barra and Sao Joao sugarcane mills), was analysed. Basically, the data set contained monthly information about the number of D. saccharalis larvae and their parasitoids in each sample (man-hour per sample), the sugarcane varieties cultivated, the age of the sugarcane plants (only at the Sao Joao sugarcane mill) as well as the sugarcane cut at sampling time. The data were collected from March 1984 to March 1997 and from May 1982 to December 1996 for the Barra and Sao Joao sugarcane mills, respectively. Temporal inverse density-dependent parasitism was predominant for both parasitoid species with respect to all spatial scales. Although the temporal pattern of parasitism was not directly density dependent, it was evident that the tachinids and C. flavipes presented positive numerical responses according to variations in D. saccharalis densities through time.

Gota suspensa para avaliação de aldeído total no ar interno e externo do ambiente

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A new fluorescence method for determination of ozone in ambient air

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Atividade da urease em latossolos sob influência da cobertura vegetal e da época de amostragem

O presente trabalho teve por objetivo avaliar o efeito do tipo de vegetação e da época de amostragem na atividade da urease em dois diferentes solos tropicais. O experimento foi instalado em Latossolo Vermelho Aluminoférrico típico e Latossolo Vermelho distrófico típico sob cinco diferentes culturas: pinus, eucalipto, citrus, soja e milho. As amostragens de solo foram efetuadas mensalmente, de abril de 1990 a março de 1991, determinando-se a atividade da urease, o N-total e o C-orgânico. A atividade da urease variou de acordo com a época de amostragem, apresentando valores mais elevados nos meses mais quentes e úmidos. A cobertura vegetal influenciou a conversão de N-uréia a N-NH4, observando-se maior atividade da urease nas amostras de solo sob pinus e eucalipto, embora, no início do ciclo das culturas da soja e do milho, a atividade da urease também tenha sido elevada.

Análise de crescimento na cultura da batata submetida a diferentes lâminas de irrigação

Conduziu-se um experimento na Fazenda São Manoel, localizada em São Manuel, SP, pertencente à Faculdade de Ciências Agronômicas da Universidade Estadual Paulista, com o objetivo de avaliar os efeitos de diferentes lâminas de irrigação no crescimento da cultura da batata (Solanum tuberosum ssp. tuberosum), cultivar Aracy. O ensaio foi instalado em um Latossolo Vermelho-Escuro, textura arenosa, sob uma cobertura de plástico. O delineamento experimental utilizado foi o de blocos ao acaso, com cinco tratamentos, cinco coletas de plantas para fins de análise de crescimento, e quatro repetições. Os tratamentos consistiam em irrigar a batata quando a tensão da água no solo atingia 15, 35, 55, 75 e 1.500 kPa. O aumento nas lâminas de irrigação induz incremento no índice de área foliar, na duração da área foliar, na taxa de crescimento relativo e na taxa assimilatória líquida.

Variação sazonal da concentração de macronutrientes em folhas de diferentes genótipos de aceroleira

A aceroleira produz durante o ano inteiro, e seus frutos são ricos em vitaminas e sais minerais. Para a obtenção de produções elevadas e frutos de boa qualidade, é necessário conhecer as necessidades nutricionais e as épocas mais apropriadas para a adubação das plantas. Este trabalho, conduzido em área do Campo Experimental da Empresa Brasileira de Pesquisa Agropecuária (EMBRAPA) Agroindústria Tropical, em Pacajus, Ceará, de dezembro de 1999 a outubro de 2000, teve por objetivo estudar a variação sazonal dos teores de nutrientes (N, P, K, Ca, Mg e S) e determinar a época mais indicada para a análise foliar de seis genótipos (P 52, P 66, P 78, P 91, P 93 e P 97) de aceroleira (Malpighia emarginata D.C.). Adotou-se o delineamento de blocos ao acaso, em esquema de parcelas subdivididas no tempo, com 4 repetições e uma planta por unidade experimental. Existem poucas diferenças no teor de macronutrientes das folhas de distintos genótipos de aceroleiras. O mês de dezembro é a época mais apropriada para diagnosticar os teores de macronutrientes em genótipos de aceroleira no Estado do Ceará, pois é o período menos influenciado pela falta ou excesso de chuva ou pela demanda dos órgãos em formação na planta.

População protozoários ciliados e degradabilidade ruminal em búfalos e bovinos zebuínos sob dieta à base de cana-de-açúcar

Três búfalos e três bovinos zebuínos adultos com cânulas ruminais foram alimentados à vontade com dieta de cana-de-açúcar fresca e picada, suplementada com 3 kg de concentrado/animal, durante 13 semanas. Após duas semanas de adaptação, amostras do conteúdo ruminal foram coletadas semanalmente, em dois tempos de amostragem: antes da alimentação e 40 minutos após para determinação da concentração e composição da fauna ruminal. Na quinta semana do experimento, os conteúdos ruminais foram misturados e reinoculados entre animais de mesma espécie e, na última semana, estimadas as degradabilidades in situ da MS, PB e FDN da cana-de-açúcar e MS e PB do concentrado. A concentração média de protozoários foi maior em bovinos, de 4,85 x 10(5)/mL, que em búfalos, de 3,82 x 10(5)/mL. As composições genéricas para Entodinium e subfamília Diplodiniinae foram 79,2 e 6,2% em bovinos e 32,0 e 54,9% em búfalos, respectivamente. Não houve interação significativa entre espécies animais e tempo de amostragem. Houve aumento da concentração média dos holotricos após 40 minutos da alimentação. As degradabilidades efetivas dos nutrientes estudados foram semelhantes entre as duas espécies animais, observando-se diferenças na cinética da degradação. Concluiu-se que os búfalos apresentaram menor concentração de ciliados no rúmen, maior composição de Diplodiniinae e menor de Entodinium que os bovinos; os holotricos exibiram capacidade de migração e seqüestro no rúmen em ambas as espécies; e as diferenças na fauna ruminal não influenciaram a degradabilidade efetiva dos nutrientes da cana-de-açúcar e do concentrado.

Measurements of ambient ozone using indigo blue-coated filters

Ozone monitoring techniques utilize expensive instruments that are often large and heavy. These instruments are not easy to handle in the field, and their size also limits some sampling schemes, principally for indoor ozone determination. We have developed a lightweight, inexpensive, and sensitive method that offers flexibility to undertake measurements of ambient ozone in many environments, both indoor and outdoor. The method is based on the reaction of ozone with indigo blue dye. The indigo molecule contains 1 carbon double bond (C = C) that reacts with ozone and results in nearly colorless reaction products. During sample collection, 2 cellulose filters coated with 40 mu L of 1.0 x 10(-3) M indigo blue were used. The determinations were done spectrophotometrically at 250 and 600 nm. The analytical parameters studied were sampling time and flow rate. Analytical curves were constructed with concentrations ranging from 37 to 123 parts per billion by volume (ppbv) of standard ozone, at 0.4 L/min and 15 min sampling time. The detection limits achieved were 6 and 9 ppbv, respectively, at 250 and 600 nm. Considering interferences, measurements made at 250 nm gave more reliable and specific values for ozone.

Colorimetric determination of ammonia in air using a hanging drop

A simple and sensitive method for determining atmospheric ammonia (NH3), using a hanging drop, is described. A colorimetric sensor is composed of two optical fibers and the source of monochromatic light implemented was a red light emitting diode (LED) (635 nm). Preliminary experiments were carried out in order to optimize the geometry of the sensor. These tests showed that the best signal absorbance was obtained using a 22 muL deionized water drop for sampling the gas and as addition of 4 muL of each of the reactants to form the blue dye (indophenol). Some important analytical parameters were also studied, including sampling time and flow rate. The analytical curve was constructed with a concentration range of 3-20 ppbv of gaseous NH3 standard. The detection limit reached was of ca 0.5 ppbv. It was observed that formaldehyde and diethylamine did not interfere. However, studies showed that hydrogen sulfide caused a negative interference of 20%, when present in the atmosphere in a concentration equal to that of NE3. The method considered here was shown to be easy to apply, making it possible to make a determination every 17 min.

Construction and performance of a drop cell for the nephelometric determination of sulfur dioxide

A nephelometric technique based on a liquid drop is described for the measurement of atmospheric sulfur dioxide. A 40-mul drop of barium chloride and hydrogen peroxide solution is suspended in a flowing-air sampling stream. The sulfur (IV) collected is oxidized to sulfur (VI) and finally precipitated as barium sulfate. Nephelometric detection of drop is achieved by an appropriate arrangement consisting of an optical fiber contacting the drop and a photodiode placed at 90degrees relative to the fiber. The design and characteristics of this drop-based gas sensor system are described. The analytical response, as photocurrent, is proportional to the product of the sampling period and the sulfur dioxide concentration. The detection limit is ca. 1.1 mg m(-3) for a 10-min sampling time. The present technique is fairly rapid and simple, uses a small amount of reagent and is set up with low-cost equipment, making this system economically viable. (C) 2002 Elsevier B.V. B.V. All rights reserved.

A Method for Determination of Ammonia in Air using Oxalic Acid-Impregnated Cellulose Filters and Fluorimetric Detection

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)