The present work aimed at evaluating indicators of hydrocarbon sources to sediments from the Solimões River region, in the central Amazon. The 16PAH, the alkylated homologs and molecular markers were investigated. The entire series of alkylated PAH were present and, in some cases, with a distribution observed when oil residues dominate. Nevertheless, hopanes characterizing immature environments undergoing diagenetic transformation were identified in samples from the Solimões River and in surface as well as in core sediment samples from Preto Lake, in the Coari-Manaus stretch. Investigation suggests early diagenesis of the organic matter confirmed by identifying biogenic markers produced during organic matter transformation. Some of these markers derive from incomplete combustion of biomass and are contained in particulate matter formed during forest burning. In the sediments of an industrial area near the city of Manaus, the entire series of mature hopanes was present indicating anthropogenic source of hydrocarbons. The results so far obtained point out the complexity of PAH source appraisal. region Amazon 16PAH investigated cases dominate Nevertheless Lake CoariManaus Coari Manaus stretch burning hydrocarbons appraisal

Different clean-up methods to determine isotopic composition of n-alkanes were tested. Sources of organic matter in Guanabara Bay were re-examined through the δ13C of individual n-alkanes in surface sediment samples. The n-alkanes were efficiently isolated without significant losses of the compounds of interest. The δ13C of n-alkanes (n-C17 to n-C35) ranged between -34.0 and -26.4‰. More depleted δ13C values associated to higher carbon preference index (CPI > 4) suggest prevalence of biogenic n-alkanes from terrestrial origin in the inner stations influenced by inputs from mangrove areas. Small isotopic differences between odd and even-numbered chains and 13C-enrichment in long-chain homologues indicate a petrogenic hydrocarbons contribution. Higher concentrations of short-chain compounds associated to a more 13C-enriched total organic carbon (TOC) were found near the most intense sewage discharges. Results show that δ13C of n-alkanes can be applied to a highly degraded system as the Guanabara Bay and help improve the characterization of the organic matter.

The goals were to estimate nutrients and carbon flow rates between Guanabara Bay and the adjacent coastal waters, to characterize the provenance of the exported/imported organic matter. Samples were collected from different depths over 25 h in two seasons at the bay entrance. Measurements included physicochemical parameters, nutrients, chlorophylls, dissolved organic carbon (DOC), particulate organic carbon (POC), particulate nitrogen (PN), carbon (δ13C) and nitrogen (δ15N) isotopic composition, sterols in suspended particulate matter (SPM) and bacterioplankton. Most variables showed higher values in ebb tide events. The flow rates calculated on daily basis and estimated on annual basis revealed the exportation to the continental shelf of 1.27 × 104 kmol year-1 dissolved inorganic nitrogen (DIN), 9.52 × 102 kmol year-1 dissolved inorganic phosphorus (DIP), 2.65 × 104 t year-1 DOC, 1.96 × 104 t year-1 POC, and 2.96 × 104 t year-1 PN. The estimates show the bay contributes with 0.01% of the total global carbon influx to the ocean.

Ethanol is a biofuel produced in Brazil through fermentation of sugarcane, requiring vast plantation areas and water availability. The present work aimed at testing isotopic markers as tools for ethanol source appointment or certification of origin. For this, oxygen and hydrogen isotopic patterns were determined in plant-water, soil-water, rainwater, and water from reservoirs and some rivers in four sugarcane crop areas. The isotopic fingerprint of carbon and hydrogen in ethanol produced in the respective mills was also determined. Samples were collected in 2011 and 2012 in crop areas of the state of Amazonas (North), Mato Grosso (Center-West), São Paulo (Southeast) and Rio Grande do Sul (South). The substantial and complex influence of the hydrological cycle on the ethanol δD and the small δ13C variations constrain the use of isotopes for the intended objectives.

O histórico de acumulação em sedimentos de produtos de combustão produzidos na área metropolitana ao redor da Baía de Guanabara foi avaliado através de black carbon (BC) e hidrocarbonetos policíclicos aromáticos (HPA) como indicadores. A concentração de BC variou de 0,23-0,51%, com uma tendência crescente de acúmulo de massa ao longo dos últimos 118 anos, mas a proporção BC/carbono orgânico caiu nos últimos 30 anos, possivelmete reflexo de eutrofização. Observaram-se as maiores concentrações de HPAs pirolíticos nos períodos entre 1925 e 1976, condizendo com o período subsequente de desmatamento, urbanização e industrialização que ocorreu na bacia da Guanabara. Estes HPAs foram melhor caracterizados pelo índice diagnóstico BFl/(BFl+BePy). Os dados obtidos permitiram caracterizar os principais eventos que influenciaram o padrão dos produtos de combustão: queima de biomassa e de derivados de petróleo, a crise econômica nos anos 1970 e 1990 e a entrada de etanol na matriz energética brasileira.

The accumulation history of combustion products from the metropolitan area around Guanabara Bay was evaluated using black carbon and polycyclic aromatic hydrocarbons as indicators. BC concentration varied between 0.23 and 0.51%, with an increasing mass accumulation tendency over the last 118 years, whereas a decrease in the values of the ratio BC/organic carbon was observed in the upper sediment layers, probably reflecting the enhancement of bay's eutrophication process in the last 30 years. Higher concentrations of pyrolytic PAH were observed between 1925 and 1976, being consistent with the subsequent deforestation, urbanization, and industrialization that occurred in the Guanabara basin in the period. These PAHs were best characterized by the BFl/(BFl+BePy) diagnostic ratio. The data obtained allowed the characterization of the main events that influenced the combustion patterns in the region: burning of biomass and fossil fuel, economic crisis of 1970 and 1990 and the introduction of ethanol in the Brazilian energetic matrix.

Um procedimento de microdigestão para a determinação de Cd e Cu em amostras biológicas por espectrometria de absorção atômica em forno de grafite (GF AAS) é descrito. Massas de até 5 mg são pesadas diretamente na cubeta do amostrador automático e 100 µL de solução digestora (HNO3-H2SO4 1:1 v/v ou HNO3 concentrado) são adicionados. As cubetas são fechadas e a digestão é realizada a 60 ºC, por 12 h, em um bloco de digestão especialmente desenhado; seguem-se a adição de 900 µL de água ultrapura, a homogeneização e transferência das cubetas ao amostrador automático. O ambiente fechado e o uso de apenas um único frasco durante todo o processo minimizam os riscos de contaminação e perdas. Curvas analíticas externas, no mesmo meio do branco, mostraram-se adequadas para a calibração. A análise de nove diferentes materiais de referência certificados permitiu a avaliação da exatidão do procedimento. Os limites de quantificação na amostra original (5 mg), calculados a partir de dez sucessivas medições do branco (k = 10) foram 0,07 e 1,7 ou 0,02 e 0,3 µg g-1 para Cd e Cu, respectivamente, usando cada uma das misturas. O procedimento foi utilizado, com sucesso, para a determinação de Cu em amostras de biópsia de fígado humano.

A microdigestion procedure for the determination of Cd and Cu in biological samples by graphite furnace atomic absorption spectrometry (GF AAS) is described. Masses up to 5 mg are directly weighed in the autosampler cup and 100 µL of the digestion solution (1:1 v/v HNO3-H2SO4 or concentrated HNO3) are added. The cups are closed and the digestion is performed, at 60 ºC overnight in a specially designed digestion block. After cooling, 900 µL of ultrapure water is added, the solution is homogenized and the cups are transferred to the autosampler tray. Since the digestion is performed in a sealed environment and the whole procedure uses only one flask, the risks of contamination and losses are minimized. Calibration was performed with external calibration curves, in the same medium as the reagents blank. The analysis of nine different standard reference materials permitted the assessment to the accuracy of the procedure. Considering a 5 mg sample mass, the limits of quantification in the original samples calculated from ten successive measurements of the blank solution (k=10) were 0.07 and 1.7 and 0.02 and 0.3 µg g-1 for Cd and Cu respectively, using the HNO3-H2SO4 mixture or concentrated HNO3 for the digestion. The procedure was used for the determination of Cu in human liver biopsy samples.

As concentrações de black carbon (BC), assim como a contribuição relativa de BC para o total de carbono orgânico sedimentar, foram determinadas pela primeira vez na Baía de Guanabara. A quantificação de BC realizou-se por método térmico (CTO-375) e a de carbono orgânico por método de oxidação a seco. As concentrações de carbono orgânico apresentaram grande variabilidade entre as estações (0,82 a 10,3%), mas foi possível definir regiões distintas na Baía de acordo com parâmetros como granulometria do sedimento, localização e magnitude de fontes autóctonas e alóctonas de matéria orgânica e hidrodinamismo. As concentrações de BC foram inesperadamente baixas (0,03 a 0,31%, com média de 0,19 ± 0,07%, n = 25), levando-se em conta o largo espectro de fontes possíveis, tanto em terra como na água, para essas substâncias. No entanto, em algumas estações o BC estava presente em níveis que podem exercer influência sobre o destino de contaminantes prioritários, tais como HPA e dioxinas. Os resultados mostraram que a distribuição espacial das concentrações de BC na Baía de Guanabara é complexa e não pode ser completamente compreendida no estágio atual de conhecimento, sendo necessárias informações adicionais, tais como fontes de emissão de BC (p.ex., queima de biomassa e consumo de combustíveis) e processos de dispersão de partículas.

The concentration of black carbon (BC), as well as the relative contribution of BC to total organic carbon, was determined for the first time in sediments from Guanabara Bay. BC was quantified by a thermal oxidation method (CTO-375) and total organic carbon by dry oxidation. Sedimentary organic carbon showed a large range in concentrations (0.82 to 10.3%), but it was possible to define distinct regions of the Bay accordingly to variations in sediment grain size, location and magnitude of allochthonous and autochthonous sources of organic matter and hydrodynamic features. Low concentrations of BC were observed (0.03 to 0.31%, with a mean of 0.19 ± 0.07%, n = 25) when considering the large spectrum of possible sources on land and at sea. However, in some stations levels are sufficiently high as to influence the fate of pollutants of concern, such as PAH and dioxins. The space distribution of BC concentrations in Guanabara Bay cannot be fully understood at this stage since further information on contributions from various sources and on natural dispersion processes are required.

Realizou-se uma investigação nas Baías de Ilha Grande e de Sepetiba sobre a natureza dos hidrocarbonetos não-aromáticos (NAH) em seus sedimentos. A mistura complexa não resolvida (UCM) constituiu de 50 a 90% da concentração dos NAH, que variou entre 2,5 µg g-1 e 193,8 µg g-1. Na maior parte das amostras a distribuição dos n-alcanos foi unimodal com predomínio de compostos de número ímpar de átomos de carbono e máximos em nC29 e nC31. Monolefinas ocorreram em baixas concentrações, enquanto as poliolefinas, incluindo isoprenoides ramificados e esqualeno, variaram entre 0,099 µg g-1 e 1,387 µg g-1, com os baixos valores relativos aos NAH surgindo em áreas de forte influência continental e antrópica. C27 - C33 hopanos foram encontrados em todas as amostras, assim como houve predominância da configuração 17a(H),21b(H), característica de origem petrogênica.

An investigation was conducted in Ilha Grande and Sepetiba Bays aiming at identifying the nature of non-aromatic hydrocarbons (NAH) in surface sediments. NAH concentrations ranged from 2.5 µg g-1 to 193.8 µg g-1 of which the major fraction (53 to 93%) was composed by unresolved complex mixture (UMC). In most samples n-alkane distribution was dominated by compounds of odd carbon number showing maxima in nC29 and nC31. Mono-olefins were at low concentrations and the polyolefins including highly branched isoprenoids and squalene varied from 0.099 µg g-1 to 1.387 µg g-1 with lower values relative to NAH appearing in areas of strong terrestrial and anthropogenic influence. Hopanes between C27 and C33 were observed in all samples with the predominant configuration 17a(H),21b(H), characteristic of a petrogenic origin.

O objetivo deste trabalho foi testar a hipótese de que espécies inorgânicas de cobre poderiam atuar como um fator inibidor da produção primária nas águas de ressurgência de Cabo Frio. Para tal, amostras de água foram coletadas de quatro profundidades diferentes em três estações costeiras ao largo de Cabo Frio, nas quais determinou-se a concentração de espécies macronutrientes, pH, oxigênio dissolvido, alcalinidade, concentração de material particulado, clorofila a, produção primária, especiação de cobre (Cu(II) e Cu(I)) e a capacidade de complexação. Os resultados indicam que a taxa de fotossíntese em águas ricas em nutrientes, mas com mais altas concentrações de cobre e baixas capacidades de complexação, são significantemente reduzidas. Cu(I) constituiu de 2 a 15 % do cobre total, embora não se tenham encontrado evidências de que a sua produção fotoquímica afete a produtividade primária.

The goal of the present work was to test the hypothesis that inorganic species of copper may inhibit primary production in upwelling waters from the Cabo Frio region. Water samples were collected from four different depths up to 50 m at three stations of Cabo Frio and nutrient concentration, pH, dissolved oxygen, alkalinity, seston, chlorophyll a, primary production, NPP, copper speciation, Cu(II) and Cu(I) and complexing capacity were determined. The results indicate that the rate of photosynthesis in nutrient rich waters with higher copper content and lower complexing capacity is significantly reduced. Cu(I) made up 2-15% of the total copper, however, there was no evidence to suggest that the photochemical production of Cu(I) affects NPP.

Realizou-se um estudo ambiental no sistema hidrológico da região do Salobo 3A, localizada no Distrito Mineral de Carajás, com o objetivo de obter dados sobre a química das águas, sobre a distribuição de concentração e especiação do cobre e de avaliar os primeiros impactos derivados de atividades antrópicas. As medições incluíram um número de parâmetros considerados essenciais à caracterização das matrizes. Encontrou-se que a concentração natural de cobre nas águas do Salobo estão próximas de 50-60 nmol L-1, enquanto nas vizinhanças do complexo de mineração os valores encontrados ultrapassam 300 nmol L-1. As concentrações de cobre nos sedimentos encontraram-se na faixa de 61 a 1,744 mig g-1. Além de efeitos sobre a concentração total , as atividades piloto de mineração também alteraram a distribuição do cobre, entre particulado e solução, e a sua especiação nesta fase. De modo geral, as concentrações de solutos principais estão abaixo da média mundial registrada para os rios.

A survey was performed in the hydrological system of the Salobo 3A region, in the Carajás Mining Province, to obtain baseline data on the water chemistry, on the copper concentration and copper speciation, and to evaluate the first environmental impacts derived from anthropogenic activities. Measurements included copper concentration and speciation and a number of essential parameters to characterize water and sediment matrices. The natural background Cu concentration in Salobo waters is around 50-60 nmol L-1 while in the vicinities of the mining complex it reaches more than 300 nmol L-1. In sediments, concentrations ranged between 61 to 1.744 mug g-1. The mining activities at pilot scale resulted in substantial change in the copper distribution between particulate and dissolved phases, as well as in the dissolved copper speciation. Concentration of major water components is low compared to North America and world river average.