Avaliação da contaminação humana por hidrocarbonetos policíclicos aromáticos (HPAs) e seus derivados nitrados (NHPAs): uma revisão metodológica

Polycyclic aromatic hydrocabons (PAHs) and their nitroderivatives (NPAHs) are ubiquitous in the environment and they are produced in several industrial and combustion processes. Some of these compounds are potent carcinogens/mutagens and their determination in biological samples is an important step for exposure control. A review of the analytical methodologies used for the determination of PAHs and their metabolites in biological samples is presented.

Persistent organic pollutants in two reservoirs along the Paraíba do Sul-Guandu River system, Rio de Janeiro, Brazil

Sediment contamination is evaluated by determining organic micropollutants (organochlorine compounds - OCs and polycyclic aromatic hydrocarbons - PAHs) in two important Brazilian water reservoirs. Trace levels of OCs were observed in the Santana reservoir (44.8 ng g-1 d.w. of p,p'-DDT), while in the Funil reservoir the levels were below detection level. Forty-eight percent of the found sigmaocs were polychlorinated biphenyls, 29% dichlorodiphenyltrichloroethane (DDT), 18% Drins, and 5% other pesticides (HCB, Heptachlor, Heptachlor-epoxide, gamma-HCH and a-Endosulfan). We observed lower levels of sigmaPAH in the Funil reservoir (1 to 275 ng g-1d.w.) than in the Santana reservoir (2.2 to 26.7 µg g-1 d.w.).

Uso do Blue Rayon para extração/concentração de compostos policíclicos em amostras ambientais

This is a review about the use of Blue rayon in the extraction and concentration of environmental contaminants in the aquatic environment. Blue rayon is an adsorbent composed of fibers covalently linked with copper phthalocyanine trisulphonate that has the ability to selectively adsorb polycyclic compounds. Blue rayon can be used in situ, in columns or in flasks. This method showed to be efficient in the extraction of important classes of environmental contaminants like the polycyclic aromatic hydrocarbons (PAHs), aromatic amines and phenylbenzotriazoles (PBTAs) and can be an important tool in monitoring studies for the evaluation of water quality.

Determinação do coeficiente de distribuição (Kd) de benzo(a)pireno em solo por isotermas de sorção

Leaking of diesel oil from gas stations is frequent in Brazil. The presence of polycyclic aromatic hydrocarbons (PAHs), which are highly toxic is an indication of contamination by heavy hydrocarbons from diesel oil. Here were present the determination of the distribution coefficient (Kd) of benzo(a)pyrene (the most carcinogenic of the PAHs) in tropical soils using the sorption isotherm model. The sorption curves acquired for benzo(a)pyrene were of the S-type, probably due to the water/methanol experimental conditions. The sorption curves allowed calculation of the distribution coefficient (Kd). The experimental Kd values were lower than those calculated from literature Koc values (partition coefficient normalized by organic carbon), due mainly to the cosolvency effect and the percentage of organic matter and clay in soil.

Utilização da extração em fase sólida (SPE) na determinação de hidrocarbonetos policíclicos aromáticos em matrizes aquosas ambientais

Polycyclic aromatic hydrocarbons (PAHs) are a great environmental concern mainly because of their toxic, mutagenic and carcinogenic potential. This paper reports utilization of the solid-phase extraction (SPE) technique to determine PAHs in environmental aqueous matrices. The recovery from environmental aqueous matrices fortified with PAHs varied from 63.7 to 93.1% for atmospheric liquid precipitation, from 38.3 to 95.1% for superficial river water, and from 71.0 to 95.5% for marine water. No negative matrix effect was observed for the recovery of PAHs from atmospheric liquid precipitation and marine water, but was observed for superficial river water, particularly for PAHs possessing 5 and 6 aromatic rings.

Horizontal Grid Size Selection and its Influence on Mesoscale Model Simulations

The use of two-dimensional spectral analysis applied to terrain heights in order to determine characteristic terrain spatial scales and its subsequent use for the objective definition of an adequate grid size required to resolve terrain forcing are presented in this paper. In order to illustrate the influence of grid size, atmospheric flow in a complex terrain area of the Spanish east coast is simulated by the Regional Atmospheric Modeling System (RAMS) mesoscale numerical model using different horizontal grid resolutions. In this area, a grid size of 2 km is required to account for 95% of terrain variance. Comparison among results of the different simulations shows that, although the main wind behavior does not change dramatically, some small-scale features appear when using a resolution of 2 km or finer. Horizontal flow pattern differences are significant both in the nighttime, when terrain forcing is more relevant, and in the daytime, when thermal forcing is dominant. Vertical structures also are investigated, and results show that vertical advection is influenced highly by the horizontal grid size during the daytime period. The turbulent kinetic energy and potential temperature vertical cross sections show substantial differences in the structure of the planetary boundary layer for each model configuration

Substâncias tóxicas persistentes (STP) no Brasil

The present article presents an assessment of PTS in Brazil including polychlorinated biphenyls, polycyclic aromatic hydrocarbons, benzene hexachloride, aldrin, dieldrin, endrin, p,p,-DDT, p,p,DDE, p,p,-DDD, hexachlorocyclohexanes (alpha-HCH, beta-HCH, gamma-HCH and delta-HCH), endossulfan, heptachlor and pentachlorophenol. The data presented here are related to a survey of PTS levels in different environmental matrixes (soil, sediment, water, air, biota) and human tissues (milk, blood, human hair), according to the scope of the UNEP-GEF Regionally Based Assessment of PTSs. Potential sources were evaluated considering national products and imports, since most of the literature does not allow source identification. Finally, Brazilian legislation was updated.

Avaliação do destino e bioacumulação de benzo(a)pireno através de simulação computacional

The objective of this work was to evaluate the environmental distribution of benzo(a)pirene, a polycyclic aromatic hydrocarbon, by the EQC model. The modeling of the contaminant distribution was accomplished by means of the fugacity model applied to a hypothetical scenario constituted by air, water, soil and sediment. The modeling and simulations revealed that the soil is the preferential compartment. We also discuss the implications of the results about fate and ecological risks associated with benzo(a)pirene. We concluded that the emissions of HPAs can not be ignored and bioaccumulation among others risks can be induced.

Técnicas de extrações e procedimentos de clean-up para a determinação de hidrocarbonetos policílicos aromáticos (HPA) em sedimentos da costa do Ceará

Extraction and clean-up are essential points in polycyclic aromatic hydrocarbon (PAHs) analysis in a solid matrix. This work compares extraction techniques and clean-up procedures for PAH analysis. PAH levels, their toxicological significance and source were also evaluated in the waters of the Cocó and Ceará rivers. The efficiency of PAH recovery was higher for the soxhlet and ultrasonic techniques. PAH recovery varied from 69.3 to 99.3%. Total PAH concentration (ΣHPA) varied from 720.73 to 2234.76 µg kg-1 (Cocó river) and 96.4 to 1859.21 µg kg-1 (Ceará river). The main PAH sources are pyrolytic processes and the levels were classified as medium so that adverse effects are possible.

Validation of an analytical methodology for the quantitative analysis of petroleum hydrocarbons in marine sediment samples

This work describes a validation of an analytical procedure for the analysis of petroleum hydrocarbons in marine sediment samples. The proposed protocol is able to measure n-alkanes and polycyclic aromatic hydrocarbons (PAH) in samples at concentrations as low as 30 ng/g, with a precision better than 15% for most of analytes. The extraction efficiency of fortified sediments varied from 65.1 to 105.6% and 59.7 to 97.8%, for n-alkanes and PAH in the ranges: C16 - C32 and fluoranthene - benzo(a)pyrene, respectively. The analytical protocol was applied to determine petroleum hydrocarbons in sediments collected from a marine coastal zone.

Hidrocarbonetos policíclicos aromáticos (HPAS) em cachaça, rum, uísque e álcool combustível

The concentration of 15 polycyclic aromatic hydrocarbons (PAHs) in 57 samples of distillates (cachaça, rum, whiskey, and alcohol fuel) has been determined by HPLC-Fluorescence detection. The quantitative analytical profile of PAHs treated by Partial Least Square - Discriminant Analysis (PLS-DA) provided a good classification of the studied spirits based on their PAHs content. Additionally, the classification of the sugar cane derivatives according to the harvest practice was obtained treating the analytical data by Linear Discriminant Analysis (LDA), using naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, benz[b]fluoranthene, and benz[g,h,i]perylene, as a chemical descriptors.

Avaliação de solventes de extração por ultrassom usando-se cromatografia líquida de alta eficiência para a determinação de hidrocarbonetos policíclicos aromáticos em solos contaminados

A method using ultrasonication extraction for the determination of 17 polycyclic aromatic hydrocarbons (PAHs), selected by the USEPA and NIOSH as "consent decree" priority pollutants, in soil by High Performance Liquid Chromatography (HPLC) was studied. Separation and detection were completed in 20 min with a C18 columm, acetonitrile-water gradient elution and ultraviolet absorption and fluorescence detections. The detection limits, for a 10 µL of solution injection, were less than 9,917 ng/g in UV detection and less than 1,866 ng/g in fluorescence detection. Several organic solvents were tested for extraction of the 17 PAHs from soils. Acetone was the best solvent among the three solvents tested, and the order of the extraction efficiencies was: acetone>methanol>acetonitrile. Ultrasonication using acetone as solvent extraction was used to evaluate the biodegradation of those compounds in contaminated soil during a vermicomposting process.

Synchronous scanning phosphorimetry for the selective determination of chrysene: a metrological study

Room-temperature phosphorimetry was used to quantify trace levels of chrysene in sugar-cane spirits and in fish bile. A selective phosphorescence enhancer (AgNO3) and synchronous scanning allowed the detection of ng amounts of chrysene. Accuracy (113 ± 17%) and selectivity was evaluated using the CRM-NIST-1647d - Priority Pollutant Polycyclic Aromatic Hydrocarbons in acetonitrile. Analysis of sugar-cane spirit samples enabled recovery of 108 ± 18% which agreed with the one achieved using HPLC. Method's uncertainty was equivalent to 3.4 ng of the analyte, however, the analyte pre-concentration (SPE) improved sensibility and minimized the relative uncertainty. Characterization and homogeneity studies in fish bile were also performed.

Contenido, distribución y origen de hidrocarburos en sedimentos de tres lagunas urbanas de Concepción - Chile

Aliphatic hydrocarbon content, distribution and origin in superficial and deep sediments of three interconnected urban lagoons located in Concepción-Chile were studied. In all lagoons, the analysis showed that aliphatic hydrocarbons present were of biogenic and anthropogenic origin, and n-alkanes were predominantly from odd carbon, confirmed by a relatively high Pristane/Phytane ratio. The most abundant Polycyclic Aromatic Hydrocarbons (PAHs) were two high-molecular weight species (Fluoranthene and Pyrene) whose presence may be related with the regular activities of the area as well as with combustion processes.

Efeitos energético-estruturais em compostos heteropolicíclicos com oxigénio ou enxofre

The present article involves a comparative study of the influence of oxygen or sulfur heteroatoms present in the central ring of polycyclic compounds, in order to clarify the correlation between the respective thermophysical or thermochemical properties and structural characteristics. Considering the importance of these types of compounds for their broad spectrum of application in diverse fields, from pharmacology to the development of new materials, the critical interpretation of such properties for their crucial role in the reactivity of these substances is of great interest. Knowledge on these thermodynamic data for key compounds is also relevant to the prediction and understanding of the properties and behavior of other parent compounds.