Hidrocarbonetos policíclicos aromáticos no meio ambiente: diferenciação de fontes em sedimentos e metabólitos em bile de peixes

Many studies on environmental ecosystems quality related to polycyclic aromatic hydrocarbons (PAH) have been carried out routinely due to their ubiquotus presence worldwide and to their potential toxicity after its biotransformation. PAH may be introduced into the environmet by natural and anthropogenic processes from direct runoff and discharges and indirect atmospheric deposition. Sources of naturally occurring PAHs include natural fires, natural oil seepage and recent biological or diagenetic processes. Anthropogenic sources of PAHs, acute or chronic, are combustion of organic matter (petroleum, coal, wood), waste and releases/spills of petroleum and derivatives (river runoff, sewage outfalls, maritime transport, pipelines). Besides the co-existence of multiples sources of PAH in the environmental samples, these compounds are subject to many processes that lead to geochemical fates (physical-chemical transformation, biodegradation and photo-oxidation), which leads to an alteration of their composition. All these facts make the identification of the hydrocarbons sources, if petrogenic, pyrolytic or natural, a challenge. One of the objectives of this study is to establish tools to identify the origin of hydrocarbons in environmental samples. PAH diagnostic ratios and PAH principal component analysis were tested on a critical area: Guanabara Bay sediments. Guanabara Bay is located in a complex urban area of Rio de Janeiro with a high anthropogenic influence, being an endpoint of chronic pollution from the Greater Rio and it was the scenario of an acute event of oil release in January 2000. It were quantified 38 compounds, parental and alkylated PAH, in 21 sediment samples collected in two surveys: 2000 and 2003. The PAH levels varied from 400 to 58439 ng g-1. Both tested techniques for origin identification of hydrocarbons have shown their applicability, being able to discriminate the PAH sources for the majority of the samples analysed. The bay sediments were separated into two big clusters: sediments with a clear pattern of petrogenic introduction of hydrocarbons (from intertidal area) and sediments with combustion characteristics (from subtidal region). Only a minority of the samples could not display a clear contribution of petrogenic or pyrolytic input. The diagnostic ratios that have exhibited high ability to distinguish combustion- and petroleum-derived PAH inputs for Guanabara Bay sediments were Phenanthrene+Anthracene/(Phenanthrene+Anthracene+C1Phenanthrene); Fluorantene/(Fluorantene+Pyrene); Σ (other 3-6 ring PAHs)/ Σ (5 alkylated PAH series). The PCA results prooved to be a useful tool for PAH source identification in the environment, corroborating the diagnostic indexes. In relation to the temporal evaluation carried out in this study, it was not verified significant changes on the class of predominant source of the samples. This result indicates that the hydrocarbons present in the Guanabara Bay sediments are mainly related to the long-term anthropogenic input and not directly related to acute events such as the oil spill of January 2000. This findings were similar to various international estuarine sites. Finally, this work had a complementary objective of evaluating the level of hydrocarbons exposure of the aquatic organisms of Guanabara Bay. It was a preliminary study in which a quantification of 12 individual biliar metabolites of PAH was performed in four demersal fish representing three different families. The analysed metabolites were 1-hydroxynaphtalene, 2-hidroxinaphtalene, 1hydroxyphenanthrene, 9-hydroxyphenanthrene, 2-hydroxyphenanthrene, 1hydroxypyrene, 3-hidroxibiphenil, 3- hydroxyphenanthrene, 1-hydroxychrysene, 9hydroxyfluorene, 4-hydroxyphenanthrene, 3-hydroxybenz(a)pyrene. The metabolites concentrations were found to be high, ranging from 13 to 177 µg g-1, however they were similar to worldwide regions under high anthropogenic input. Besides the metabolites established by the used protocol, it was possible to verified high concentrations of three other compounds not yet reported in the literature. They were related to pyrolytic PAH contribution to Guanabara Bay aquatic biota: 1-hydroxypyrine and 3-hydroxybenz(a)pyrine isomers

Cryptosporidium infection in Brazil: implications for veterinary medicine and public health

O objetivo deste trabalho foi relatar, por meio de revisão de literatura, os resultados de pesquisas sobre a criptosporidiose no Brasil, com ênfase em sua ocorrência em animais e suas implicações em medicina veterinária e em saúde pública. Um número crescente de trabalhos sobre a infecção por Cryptosporidium spp. no Brasil está disponível na literatura nacional e internacional. Nestes trabalhos, são abordados principalmente aspectos relacionados à ocorrência de Cryptosporidium spp. em alimentos, amostras ambientais, no homem e em diversas espécies animais, particularmente em aves, bovinos, cães e gatos. Por meio de técnicas de biologia molecular, a maioria das espécies e alguns genótipos identificados em outros países foram descritos no Brasil. em mamíferos, houve identificação de C. bovis, C. canis, C. felis, C. meleagridis, C. parvum e o genótipo cervídeo; em diversas espécies de aves, foi descrita infecção por C. baileyi, C. galli, C. meleagridis, C. parvum e pelos genótipos I, II e III de aves. Várias espécies foram descritas no homem, como C. parvum e C. hominis, além de algumas espécies adaptadas a hospedeiros animais, como C. canis, C. felis e C. meleagridis.

Molecular detection of Paracoccidioides brasiliensis in soil

The objective of the present study was to evaluate different techniques for the detection of Paracoccidioides brasiliensis in soil, e.g., culture, animal inoculation and specific DNA amplification by Nested PCR. We designed species-specific inner primers derived from rDNA regions (ITS, 5.8S gene) and found their sensitivity to be higher than culture and animal inoculation. In addition, the sensitivity of these primers was higher than p27-gene primers developed for detection of P brasiliensis in soil in a previous study. DNA from P brasiliensis was detected in soil artificially seeded with the fungus (positive soil control) and from environmental samples collected in an armadillo burrow.

Um novo método para quantificar mercúrio orgânico (Hg orgânico) empregando a espectrometria de fluorescência atômica do vapor frio

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

Cobalt phthalocyanine as a biomimetic catalyst in the amperometric quantification of dipyrone using FIA

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

Identification of Mycobacteria by Thin Layer Chromatographic Analysis of Mycolic Acids and Conventional Biochemical Method: Four Years of Experience

Mycolic acids analysis by thin-layer chromatography (TLC) has been employed by several laboratories worldwide as a method for fast identification of mycobacteria. This method was introduced in Brazil by our laboratory in 1992 as a routine identification technique. Up to the present, 861 strains isolated were identified by mycolic acids TLC and by standard biochemical tests; 61% out of these strains came as clinical samples, 4% isolated from frogs and 35% as environmental samples. Mycobacterium tuberculosis strains identified by classical methods were confirmed by their mycolic acids contents (I, III and IV). The method allowed earlier differentiation of M. avium complex - MAC (mycolic acids I, IV and VI) from M. simiae (acids I, II and IV), both with similar biochemical properties. The method also permitted to distinguish M. fortuitum (acids I and V) from M. chelonae (acids I and II) , and to detect mixed mycobacterial infections cases as M. tuberculosis with MAC and M. fortuitum with MAC. Concluding, four years experience shows that mycolic acids TLC is an easy, reliable, fast and inexpensive method, an important tool to put together conventional mycobacteria identification methods.

Solid-phase extraction of sugar cane soot extract for analysis by gas chromatography with flame ionisation and mass spectrometric detection

The incomplete combustion of biomass is one of the most important sources of emissions of organic compounds into the atmosphere, like polycyclic aromatic hydrocarbons (PAHs) which show genotoxic activity. Since environmental samples generally contain interferents and trace amounts of PAHs of interest, concentration and clean-up procedures are usually required prior to the final chromatographic analysis. This paper discusses the performance of Sep-Pak cartridges (silica gel and RP18) on clean-up of sugar cane soot extract. The best results were obtained with a silica Sep-Pak cartridge. The recoveries ranged from 79% (benzo[b]fluoranthene) to 113% (benzo[e]pyrene). (C) 2000 Elsevier B.V. B.V. All rights reserved.

Determination of low-aliphatic aldehydes indoors by micellar electrokinetic chromatography using sample dissolution manipulation for signal enhancement

This work describes a novel approach for the analysis of selected aldehydes (formaldehyde, acetaldehyde, propionaldehyde, and acrolein) and acetone in environmental samples using micellar electrokinetic chromatography (MEKC). The method is based on the reaction of carbonyl compounds with 3-methyl-2-benzothiazoline hydrazone (MBTH) that gives an azine intermediate with maximum absorbance at 216 nm. A systematic evaluation of sample dissolution medium was conducted as a means to enhancing sensitivity. In the best condition, samples were dissolved in 0.030 mol.L-1 tetraborate solution. This condition presented enhancement factors in the range of 35-54 for the aldehydes under investigation, computed as the improvement of the concentration limits of detection (LODs) with reference to the sample dissolved in pure water. The running buffer was 0.020 mol.L-1 tetraborate, pH 9.3, containing 0.050 mol-L-1 sodium dodecyly sulfate (SIDS). The overall methodology presented several advantages over established methods for aldehydes. Worthy mentioning that MBTH is available in high purity degree, dispensing laborious reagent purification procedures. A few method validation parameters were determined revealing good migration time repeatability (< 2.5% coefficient of variation, CV) and area repeatability (< 4% CV), excellent linearity (20-120 mug/L, r > 0.995) and adequate sensitivity for environmental applications. The LODs with respect to each single aldehyde were in the range of 0.54-4.0 mug.L-1 and 11 mug.L-1 for acetone. The methodology was applied to the determination of aldehydes indoors. Samples were collected in an impinger flask containing 0.05% MBTH solution, at a flow rate of 0.80 L.min(-1), during 2.5 h, at different times during the day. The most abundant carbonyls in the samples were acetone, followed by formaldehyde and acetaldehyde, with estimate peak concentrations of 452, 5.2 and 2.2 ppbv, respectively.

Microcystin-producing genotypes from cyanobacteria in Brazilian reservoirs

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

Sensor for diuron quantitation based on the P450 biomimetic catalyst nickel(II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine

A biomimetic sensor based on a carbon paste electrode modified with the nickel(II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine complex was developed as a reliable alternative technique for the sensitive and selective analysis of the herbicide diuron in environmental media. The sensor was evaluated using cyclic voltammetry and amperometric techniques. The best amperometric responses were obtained at 750 mV vs. Ag/AgCl (KClsat), using 0.1 mol L-1 phosphate buffer solution at pH 8.0. Under these conditions, the sensor showed a linear response for diuron concentrations between 9.9 × 10-6 and 1.5 × 10-4 mol L -1, a sensitivity of 22817 (±261) μA L mol-1, and detection and quantification limits of 6.14 × 10-6 and 2 × 10-5 mol L-1, respectively. The presence of the nickel complex in the carbon paste improved selectivity, stability, and sensitivity (which increased 700%), compared to unmodified paste. The applicability of the sensor was demonstrated using enriched environmental samples (river water and soil). © 2012 Elsevier B.V. All rights reserved.

Study of adsorption and preconcentration by using a new silica organomodified with [3-(2,2′-dipyridylamine)propyl] groups

In this work, a silica surface chemically modified with [3-(2,2′-dipyridylamine)propyl] groups, named [3-(2,2′- dipyridylamine)propyl]silica (Si-Pr-DPA) was prepared, characterized, and evaluated for its heavy metal adsorption characteristics from aqueous solution. To our knowledge, we are the first authors who have reported the present modification. The material was characterized using infrared spectroscopy, SEM, and NMR 29Si and 13C solid state. Batch and column experiments were conducted to investigate for heavy metal removal from dilute aqueous solution by sorption onto Si-Pr-DPA. From a number of studies the affinity of various metal ions for the Si-Pr-DPA sorbent was determined to follow the order Fe(III) > Cr(III) >> Cu(II) > Cd(II) > Pb(II) > Ni(II). Two standard reference materials were used for checking the accuracy and precision of the method. The proposed method was successfully applied to the analysis of environmental samples. This ligand material has great advantage for adsorption of transition-metal ions from aqueous medium due to its high degree of organofunctionalization associated with the large adsorption capacity, reutilization possibility, and rapidity in reaching the equilibrium. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of heavy metal ions and epoxidation catalysis using a new polyhedral oligomeric silsesquioxane

The objective of this research was the preparation of a silsesquioxane functionalized with eight chloropropyl chains (T8-PrCl) and of a new derivative functionalized with a pendant linear chain (2-amino-1,3,4-thiadiazole - ATD; T8-Pr-ATD). The two nanostructured materials were characterized by 13C and 29Si NMR, FTIR and elemental analysis. The new nanostructured material, octakis[3-(2-amino-1,3,4-thiadiazole)propyl] octasilsesquioxane (T8-Pr-ATD), was tested as a ligand for transition-metal ions with a special attention to adsorption isotherms. The adsorption was performed using a batchwise process and the organofunctionalized surface showed the ability to adsorb the metal ions Cu (II), Co (II), and Ni (II) from water and ethanol. The adsorption isotherms were fitted by Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R) model. The kinetics of adsorption of metals were performed using three models such as pseudo-first order, pseudo-second order and Elovich. The Langmuir and Elovich models were the most appropriate to describe the adsorption and kinetic data, respectively. Furthermore, the T8-Pr-ATD was successfully applied to the analysis of environmental samples (river and sea water). Subsequently, a new nanomaterial was prepared by functionalization of the T8-Pr-ATD with a Mo (II) organometallic complex (T8-Pr-ATD-Mo). Only a few works in the literature have reported this type of substitution, and none dealt with ATD and Mo (II) complexes. The new Mo-silsesquioxane organometallic nanomaterial was tested as precursor in the epoxidation of cyclooctene and styrene. © 2012 Elsevier B.V.

Simple procedure for nutrient analysis of coffee plant with energy dispersive X-ray fluorescence spectrometry (EDXRF)

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

Ocorrência de Listeria spp. e de Listeria monocytogenes, em um matadouro-frigorífico de bovinos do estado de São Paulo

We evaluated the presence of Listeria spp. and Listeria monocytogenes in environmental samples by means of swabs collected the bovine slaughter plant enabled to export, located in the state of Sao Paulo, Brazil. After the pre-enrichment at 30±1°C for 22 to 26h the samples were analyzed using the BAX System Listeria. Those positive for Listeria spp. were submitted a second PCR reaction to confirm the presence of Listeria monocytogenes. From 411 environmental samples analyzed, 62 (15.1%) were positive for Listeria spp. and 21 (5.1%) for Listeria monocytogenes, which showed their persistence in the slaughter plant. There were no statistical differences between the rainy and dry periods and between areas sampled, although it has been found between sectors. The floor surface and the sector cuts have higher rates of positivity.

Development and application of an electronic tongue for detection and monitoring of nitrate, nitrite and ammonium levels in waters

This work presents the first study and development of an electronic tongue analysis system for the monitoring of nitrogen stable species: nitrate, nitrite and ammonium in water. The electronic tongue was composed of an array of 15 potentiometric poly(vinyl chloride) membrane sensors sensitive to cations and anions plus an artificial neural network (ANN) response model. The building of the ANN model was performed in a medium containing sodium, potassium, and chloride as interfering ions, thus simulating real environmental samples. The correlation coefficient in the cross-validation of nitrate, nitrite and ammonium was satisfactory in the three cases with values higher than 0.92. Finally, the utility of the proposed system is shown in the monitoring of the photoelectrocatalytic treatment of nitrate. © 2013 Elsevier B.V.