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.

Solid residues generated by the petroleum industry are often classified as hazardous, in part due to the lack of adequate analytical methods for their characterization, given their gluey and highly viscous nature. In this study, an alternative to the method described by the United States Environmental Protection Agency (US EPA) method 1311, replacing the zero headspace extraction (ZHE) approach with solid-phase microextraction followed by analysis via gas chromatography-mass spectrometry was developed, for the determination of aromatic chlorinated and non-chlorinated volatile organic compounds. The method was validated according to national and international regulations, with a working range of 2.00 to 90.00 µg L-1 and limit of detection varying from 0.12 to 0.41 µg L-1. Spiked matrices were analyzed and recovery values ranged from 79.7 to 98.4%. The analysis of real samples revealed levels below limit of quantification for chlorobenzene derivatives (2.00 µg L-1) and for the non-chlorinated aromatic compounds < 19.85 µg L-1, proving to be a viable alternative to overcome the difficulties encountered with filtration techniques.

Microbial volatile organic compounds (MVOCs) are present in several production processes in biotechnology. In this study it is evaluated the viability of use of a method involving solid-phase microextraction (SPME), in vivo SPME, in the extraction of MVOCs, associated with the pigment production process by the Monascus fungus. PDMS/Car/DVB (50/30 µm) fiber in the headspace mode (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) were used to fermentation broth study. Seventeen compounds were found associated with the presence of the fungus, being the main ones ethanol, 2-methyl-propanol, 3-methyl-butanol, 2-methyl-butanol and 2-phenyl-ethanol. These compounds have maximum concentration of 313.87, 5.51, 2.37, 0.95 and 0.70 mg L-1. The values of biomass and red pigment found for fermentation for ten days were 4.03 ± 0.21 g L-1 and 3.96 ± 0.17 (UA480). Regular MVOC productions were observed in this study, which were useful in the prediction and control of fermentation by Monascus fungus.

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.

Application of the headspace solid-phase microextraction and gas chromatography-mass spectrometry (HS-SPME-GC/MS) technique as an analytical tool to monitoring the degradation of phenolic compounds and the formation of by-products in produced water by UV photolysis and UV/peroxide is proposed. All of the experimental conditions for the degradation tests were carried out according to the response of the surface modeling methods developed. The direct photolysis and the UV/H2O2 processes were capable to degrade more than 99% of the initial concentrations of total phenolic components of produced water. The main by-product found was 2,6-di-tert-butylbenzoquinone (DBQ). The presence of DBQ and other hydroxy compounds, constituting the major fraction of by-products identified, demonstrates that the degradations are initiated by the oxidation of the aromatic phenolic ring generating quinones, diphenols, benzoic acids and phenones.

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.

Compostos orgânicos provenientes de cinco amostras de sedimentos e um perfil com 75 cm foram coletados na Lagoa da Conceição, localizada na Ilha de Santa Catarina, com o objetivo de avaliar fontes de matéria orgânica. Os resultados que foram baseados na relação C:N:P, abundância relativa dos esteróis (com predomínio dos C27), álcoois (0,2-1,2 µg g-1) e hidrocarbonetos lineares (0,4-5,0 µg g-1), e no uso do Índice Preferencial de Carbono (CPI), indicaram que a matéria orgânica é preferencialmente de origem terrestre (C/N > 10 e CPI > 2). Em todos os locais observaram-se correlações significativas entre as quantidades de fósforo (TP, média 5,20 µmol g-1) e carbono orgânico total (TOC, média 2,90 mmol g-1) com as frações de silte e argila. No perfil, que foi cronologicamente datado com o radionuclídeo 210Pb, o intervalo de 55 a 75 cm apresentou predomínio de areia (> 50%). Entretanto, outros parâmetros, tais como TOC, TP e hidrocarbonetos também aumentaram nesse intervalo, o que sugere uma mudança na fonte de matéria orgânica.

Lipid compounds from five sediment-water interface samples and a sediment core with 75 cm depth were used to assess sources of organic matter in Conceição Lagoon, located on Santa Catarina Island. The results which were based on the molar C:N:P ratios, relative abundance of sterols (dominated by the C27 sterols), n-alkanols (0.2-1.2 µg g-1), n-alkanes (0.4-5.0 µg g-1) and the Carbon Preference Index (CPI), indicated that the organic matter is predominantly of terrestrial origin (C/N > 10 and CPI > 2). Total phosphorus (TP, average 5.20 µmol g-1) and organic carbon (TOC, average 2.90 mmol g-1) contents were well correlated with the silt and clay fractions at all locations. In the sediment core, chronologically dated with the radionuclide 210Pb, the depth interval from 55 to 75 cm was dominated by the sand fraction (> 50%). However, parameters such as TOC, TP and n-alkane contents increased considerably at this depth suggesting a change in organic matter input sources.

Lipídios provenientes de sete estações sedimentares foram usados para avaliar fontes de matéria orgânica em dois manguezais localizados na Ilha de Santa Catarina, SC. O manguezal de Ratones encontra-se em uma área de preservação permanente, com pouca influência humana. Em contraste, o manguezal do Itacorubi tem sofrido sérios impactos por atividades antrópicas devido à sua proximidade da cidade de Florianópolis. Os maiores níveis de carbono orgânico (2,13 mmol g-1) e fósforo total (14,9 µmol g-1) foram encontrados em Ratones. Entretanto, o percentual de fósforo inorgânico determinado no manguezal de Itacorubi (84%) foi maior do que o de Ratones (58%), possivelmente devido à contaminação urbana. A importância do aporte de esgoto doméstico para o manguezal do Itacorubi foi avaliada a partir da concentração do coprostanol que variou, em média, de 7,7 ng g-1 em Ratones para 1,42 µg g-1 no Itacorubi. Esse nível elevado é compatível com valores encontrados em outros ambientes contaminados.

Lipid compounds from seven sedimentary stations were used to assess sources of organic matter in two mangrove ecosystems located on Santa Catarina Island, southern Brazil. Ratones Mangrove forms part of a national preservation area and has suffered only minimal human influence. Itacorubi Mangrove has been seriously impacted by anthropogenic activities due to its proximity to the city of Florianopolis. Higher levels of total organic carbon (2.13 mmol g-1) and total phosphorus (14.9 µmol g-1) were found in Ratones Mangrove sediments. However, sediments from Itacorubi showed a greater percentage of inorganic phosphorus (84%) than those from Ratones (58%), which can be related to urban contamination. The importance of sewage outfalls into the tidal creeks crossing Itacorubi Mangrove was clearly seen as the concentration of coprostanol averaging 7.7 ng g-1 in Ratones sediments was found to be as high as 1.42 µg g-1 in Itacorubi, which is comparable to other sewage contaminated hydrosystems.

No presente trabalho foram desenvolvidos métodos de extração e purificação a fim de determinar e monitorar as concentrações dos pesticidas organofosforados mais utilizados em tomates na grande Florianópolis. A técnica de EFS com carvão ativo foi utilizada para a purificação e recuperação dos pesticidas metamidofós, acefato, malation e paration metílico. Os solventes para a extração e eluição foram escolhidos após diversas análises, sendo que os melhores resultados foram alcançados através da extração dos pesticidas com acetato de etila e eluição com CH2Cl2 - acetato de etila (7:3). A média recuperada dos analitos das matrizes fortificadas com 0,20 - 0,60 mig g-1 variou entre 85,2 e 100 %, com coeficientes de variação entre 1,3 e 6,3 %. Os limites de detecção foram de 0,04 a 0,12 ng g-1. O adsorvente carvão ativo mostrou-se eficiente para a purificação da matriz de tomate e para a recuperação quantitativa dos analitos, especialmente os mais polares.

The present work describes extraction and purification methods that were developed to determine and to monitor the content of organophosphorus pesticides in tomato crops from the agricultural district of Florianópolis, Brazil. SPE technique with activated charcoal was used for purification and recovery of the pesticides methamidophos, acephate, malation and methyl parathion. The solvents used for sample extraction and elution were chosen after several comparative tests. Best results were achieved using ethyl acetate for extraction and dichloromethane - ethyl acetate (7:3) for elution. Average recoveries from the matrices fortified with 0.20 to 0.60 mug g-1 ranged from 85.2 to 100 % with overall coefficients of variation of 1.3 to 6.3 %. The limits of detection of the method varied between 0.04 and 0.12 ng g-1. Activated charcoal demonstrated to be efficient for tomato matrix purification and for quantitative recovery of the analytes.

A variação na abundância de alguns biomarcadores lipídicos derivados de aportes terrestres pode estar relacionada com mudanças climáticas no passado. Apesar dos processos de biodegradação que, na grande maioria, ocorrem na coluna aquática e na interface sedimento-água, esses compostos são encontrados bem preservados em sedimentos oceânicos. Nesse trabalho, a distribuição relativa desses compostos é empregada como uma ferramenta para avaliar mudanças no transporte de material terrestre para o mar em paralelo às variações climáticas durante os intervalos glaciais e interglaciais. As mudanças na distribuição dos biomarcadores foram estimadas em dois testemunhos coletados ao leste do Atlântico Norte e que correspondem aos últimos 210 mil anos. Os resultados mostraram uma boa correlação entre a distribuição dos biomarcadores e outros parâmetros paleoclimáticos previamente avaliados nos perfis, sugerindo que alguns grupos específicos de compostos orgânicos são importantes indicadores de aporte terrestre para ornar.

Variations in the abundance of specific lipid biomarker compounds derived from terrestrial sources are shown to be closely related to past climatic changes. Despite biodegradation processes, which take place mostly at the water column and sediment water interface, these compounds are found well preserved in oceanic sediments. Here, their relative distribution is employed as a tool to assess changes in terrestrial fluxes to the seabed accompanying climatic variations during glacial and interglacial intervals. These changes in biomarker distribution were estimated in two sediment cores taken ttom the eastern North Atlantic, covering the past 210,000 years. Comparisons with other paleoclimate proxies showed good agreement and suggest that some specific groups of biomarkers are important indicators of changes in terrestrial inputs to the sea.

The distribution and abundance of specific lipid biomarkers in marine sediments can play an important rule for the reconstruction of past climatic changes. Here, it is shown the use of a widely known paleo Sea Surface Temperature (SST) proxy based on the unsaturation ratio of a suite of long-chain C37 alkenones: the alkenone unsaturation index, U K37'. These compounds are biosynthesised by only a restricted group of prymnesiophyte algae, mostly notably the coccolithophorid Emiliania huxleyi. To ilustrate the importance of the U K37' index as a molecular tool, the correlation between the SST signal derived from the U K37' and other paleoclimatic records examined in a core from the North Atlantic is discussed.