A simple and efficient method using reduced amounts of solvents for the determination of polycyclic aromatic sulfur heterocycles (PASHs) in aqueous matrices from a lagoon and leachate solid waste from a petrochemical industry is proposed. The target analytes were previously concentrated using the disposable pipette extraction (DPX) technique applying gas chromatography-mass spectrometry (GC-MS) for analysis. In this innovative approach, the DPX was modified with 8-hydroxyquinoline silica gel immobilized with PdII for the pre-concentration of 4-methyldibenzothiophene, 4,6-dimethyldibenzothiophene, 1,2-naphtobenzothiophene, 2-methylbenzothiophene and 3-methylbenzothiophene. To improve the extraction efficiency, parameters such as desorption solvent, ionic strength, extraction and desorption cycles were optimized. The values obtained for the limits of detection (LOD) and quantification (LOQ) are adequate for the determination of PASHs in aqueous and leachate solid waste samples. Precision and accuracy parameters showed satisfactory results, providing relative recoveries of 74.6-131.2% for PASHs from lagoon water samples and 72.7-118.0% for leachate of solid waste samples. In the lagoon samples the relative standard deviation (RSD) values for the five PASHs ranged from 0.3 to 9.2% and 3.8 to 19.4% for the leachate of the solid waste. These results demonstrate that the proposed method represents a promising alternative for the determination of PASHs in aqueous and leachate solid waste samples.

The Itajaí-Açu estuarine system, located in southern Brazil, has great economic importance due to the presence of two ports (Itajaí and Navegantes). This system is affected by industrial and dredging activities, which can cause the remobilization of pollutants accumulated over time in the sediment. In this context, hydrocarbons were assessed in twelve surface sediment samples. n-Alkane and polycyclic aromatic hydrocarbons (PAH) concentrations were determined by gas chromatography and their sources assessed. Total concentrations ranged between 0.50 ± 0.04 and 69.70 ± 3.90 μg g-1 dry weight (d.w.) for n-alkanes and from 63.9 ± 12.1 to 1459.0 ± 43.5 ng g-1 d.w. for PAH. Most of the sediment samples presented carbon preference index (CPI) values close to unity, indicating that the area is submitted to petroleum-related sources, mainly close to Itajaí harbor, where an intense unresolved complex mixture (UCM) was observed. The presence at all stations of αβ-hopane biomarkers also indicated petrogenic input. Based on selected PAH ratios, the sedimentary PAH composition reflects a mixture of both petrogenic and pyrolytic sources. A comparison of the PAH concentrations found in this study with those listed in the sediment quality guidelines (SQGs) indicated that adverse biological effects on the biota are rarely expected.

Este trabalho apresenta um estudo comparativo de diferentes processos de oxidação fotoquímica e uma detalhada caracterização dos subprodutos da degradação de óleo diesel utilizando cromatografia gasosa bidimensional abrangente acoplada à espectrometria de massas por tempo de voo (GC×GC-TOFMS). A degradação de óleo diesel foi realizada em um reator fotolítico usando UV, H2O2, UV/H2O2, O3 ou O3/UV. As melhores condições para cada processo foram otimizadas por análise multivariada e os resultados experimentais indicaram que o processo O3/UV foi o mais viável para o tratamento de efluentes contendo óleo diesel, com uma porcentagem de degradação maior que 90%. A degradação quase completa dos compostos aromáticos foi alcançada. Compostos fenólicos foram identificados como subprodutos das amostras de óleo diesel tratadas com os processos UV, H2O2, O3 e O3/UV. Além desses compostos, outros subprodutos identificados incluem ácidos carboxílicos e éteres no tratamento com UV/peróxido, éteres no tratamento com radiação UV e cetonas no tratamento com ozônio.

This paper provides a comparative study of different photochemical oxidation processes and a detailed characterization of the by-products of diesel oil degradation performed using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS). Diesel degradation was conducted in a photolytic reactor using UV, H2O2, UV/H2O2, O3 or O3/UV. The best conditions for each process were obtained applying multivariate analysis and the experimental results indicated that the O3/UV process was the most feasible for the treatment of wastewater containing diesel fuel, with a degradation percentage of > 90%. Almost complete degradation of the aromatics was achieved. Phenolic compounds were identified as by-products of the diesel samples treated with the UV, H2O2, O3 and O3/UV processes. Besides the phenolic compounds, other by-products identified included carboxylic acids and ethers in the UV/peroxide treatment, ethers in the UV irradiation treatment and ketones in the ozone treatment.

Este trabalho descreve um método simples e rápido para a determinação de BTEX (benzeno, tolueno, etilbenzeno e xileno) em resíduos sólidos e soluções lixiviadas de resíduos sólidos aplicando a Norma Brasileira ABNT NBR 10004/2004. O método proposto possibilita a detecção direta de BTEX usando microextração em fase sólida e cromatografia a gás com detector por ionização em chama (HS-SPME GC/FID). Os limites de quantificação obtidos para BTEX evidenciaram que o método é adequado para a classificação de resíduos sólidos.

This work describes a simple and fast method for the determination of BTEX (benzene, toluene, ethylbenzene and xylene) in solid waste and solutions obtained from leaching applying procedures detailed in the ABNT NBR 10004/2004 Brazilian standard for the classification of solid residues. The proposed method allows the direct detection of BTEX using solid-phase microextraction and gas chromatography with a flame ionization detector (HS-SPME GC/FID). Limits of quantification for BTEX showed that the developed method is suitable for the classification of solid wastes.

Amostras de sedimentos superficiais do Sistema Estuarino de Laguna foram analisadas objetivando a identificação das fontes de matéria orgânica. Razões entre n-alcanos selecionados, elevados teores de hidrocarbonetos alifáticos (HA) (média de 9.168 µg g-1 de carbono orgânico, CO) e policíclicos aromáticos (HPA) (média total de 426.593 ng g-1 CO), e a distribuição de hopanos com estereoquímica αβ detectados nas amostras da Lagoa de Santo Antônio foram evidências de que o aporte de hidrocarbonetos petrogênicos prevalece sobre os de fontes naturais. Nas demais amostras estudadas, a distribuição de HA (de 38 até 2.749 µg g-1 CO), a detecção de hopenos e hopanos-ββ sugerem hidrocarbonetos de fontes mistas. Todavia, o teor de HPA em todas as amostras (de 7.731 até 786.469 ng g-1 CO, sendo que os aromáticos alquilados representaram > 92% do total) revelou contaminação petrogênica crítica. As atividades pesqueira e urbana são fontes potenciais dos hidrocarbonetos petrogênicos detectados nas amostras sedimentares.

Surface sediment samples from the Laguna Estuarine System were analyzed to identify organic matter sources. The ratios between selected n-alkanes, high concentrations of aliphatic hydrocarbons (AH) (average of 9,168 µg g-1 of organic carbon, OC) and polycyclic aromatic hydrocarbons (PAH) (total average of 426,593 ng g-1 OC), and the hopanes distribution with αβ stereochemistry found in the Santo Antônio Lagoon samples were evidence that hydrocarbon inputs from petrogenic sources predominate over natural sources. In the other samples studied, the AH distribution (from 38 to 2,749 µg g-1 OC), and detection of hopenes and hopanes-ββ suggest mixed sources of hydrocarbons. Nevertheless, PAH concentrations in all samples (from 7,731 to 786,469 ng g-1 OC, whereof alkyl naphthalenes accounted for > 92% of the total) indicated critical petrogenic contamination. Fishing and urban activities are potential sources to the petrogenic hydrocarbons detected in these sediment samples.