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

Abstract This research study sought to evaluate aimed at evaluating the possible advantages of using Fuzzy Logic as opposed to Boolean Logic to assess environmental contamination and source appraisal for polycyclic aromatic hydrocarbons (PAH). Results obtained through traditional assessment tools for two different tropical coastal areas through using traditional clustering and principal components analysis were compared with those derived from the Fuzzy Logic, using the by Fuzzy C-means algorithm. The feedings achieved through Fuzzy Logic showed a greater qualitative detail than those derived from traditional tools. The abrupt and unnatural changes obtained from the usual classification methods were avoided by having membership values varying continuously in space, providing a more accurate picture of environmental contamination in complex and multiple sources environments. Furthermore, by not depending on statistic suppositions distribution of data like other methods, becomes more suitable for environmental data. Although Fuzzy Logic does not produce quantitative interpretations, its application generates adequate the data needed to avoid environmental management bias in the inference of contamination sources.

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.

The Marine and Environmental Studies Laboratory at PUC-Rio, in partnership with the PETROBRAS R&D Center (Brazil), conducted an interlaboratory comparison of aliphatic and aromatic hydrocarbons and trace element determinations. The goal of this study was to produce a homogeneous and stable material and obtain consensus concentration values for its use as a reference material (RM) for sediments from tropical regions. The prepared material is adequate for use as a reference material because it has remained stable (Test F, ANOVA, p < 0.05) since its preparation in 2007. In this study, several alkylated polycyclic aromatic hydrocarbon (PAH) compounds were included, and the resulting dispersion was the same order of magnitude as the parental PAH (16 PAH USEPA).

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.

Três testemunhos sedimentares foram coletados na Baía de Guanabara. Dois deles apresentaram perfis de concentração de 210Pb que poderiam ser utilizados para fins de datação. Taxas de sedimentação de aproximadamente 1 cm ano-1 (cinco vezes superior aos valores de linha de base) foram observadas para os dois testemunhos, coerentes com os dados existentes na literatura relacionada à datação de sedimentos da Baía de Guanabara, empregando-se 210Pb. A validação da datação foi realizada com base nos perfis de cobre, cromo e chumbo, no fluxo de 210Pb e no registro histórico das principais intervenções físicas ocorridas no século passado, tais como aterro, a canalização de rios principais e a construção de vias rápidas. No final deste processo, apenas a datação de um único testemunho pôde ser adequadamente validada.

Three sediment cores were taken from Guanabara Bay. Two of them yielded 210Pb profiles that could be applied for dating purposes. Actual sedimentation rates of approximately 1 cm year-1 (five times higher than the baseline values) were observed for both sediment cores, which agree with the reviewed existing data in the literature related to Guanabara Bay sedimentation rates based on 210Pb. Dating validation was carried out based on the chromium, copper and lead profiles, on the 210Pb flux and on the historical record of the main physical interventions occurring in the last century, such as embankment, the channeling of main rivers and the construction of express roads. At the end of this process, only one sediment core dating could be adequately validated.

Butyltin compounds were investigated in surface sediments from 17 stations in Todos os Santos Bay. Analytical conditions for organotin determination in marine sediments were optimized for GC with pulsed flame photometric detection. Detection limits were: 5.4 µg kg-1 for TBT; 0.2 µg kg-1 for DBT; and 2.1 µg kg-1 for MBT, using a 610-nm filter. In general, TBT concentrations were low and in the range of <DL to 15.9 µg kg-1. Only in one of the investigated stations DBT and MBT were above detection limit despite the oxic to slightly anoxic conditions in the sediments. The presence of paint particles in the sediments and degradation in the water column during resuspension events followed by removal of the more soluble DBT and MBT may explain these observations.

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.

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.

A Baía de Guanabara no Rio de Janeiro tem sofrido profundas alterações ambientais. O aumento da concentração de metais-traço em seus sedimentos está entre as alterações mais relevantes. O objetivo deste trabalho foi verificar a contaminação por metais-traço e avaliar a disponibilidade em sedimentos de áreas de manguezais (Surui, Nova Orleans e Piedade). Concentrações de Cd, Zn, Pb, Ni, Cu e Al foram determinadas em segmentos de testemunhos após tratamento com 1 mol L-1 de HCl e com HNO3. Fe e Mn foram determinados na lixívia de HNO3 concentrado. As concentrações foram baixas em comparação com aquelas reportadas para a Baía de Guanabara e o Cd mostrou a mais alta recuperação em 1 mol L-1 HCl (90%). Apesar de oxidados ou subóxicos os sedimentos mostraram SAV na faixa de 0,07 to 18,79 mmol g-1 sugerindo heterogeneidade e desequilíbrio aparente. Óxidos de Fe, Mn, carbonatos e matéria orgânica são as fases que mais provavelmente controlam a biodisponibilidade dos metais.

The Guanabara Bay in Rio de Janeiro has undergone profound alterations of its natural environmental conditions. Metal concentration increase in sediments has been reported to be among these alterations. Trace-metal contamination and availability were studied in sediments of 3 mangrove areas of the bay. Cd, Zn, Pb, Ni, Cu and Al concentrations were determined in segments of sediment cores, after treatment with 1 mol L-1 HCl and with concentrated HNO3. Fe and Mn were determined in the leach with HNO3. Concentrations were low in comparison to those reported for Guanabara Bay and Cd showed up to 90% recovery in the HCl extract. Sediments found to be oxic to suboxic showed AVS concentrations in range of 0.07 (bottom) to 18.79 mmol g-1(sub-surface) indicating heterogeneity and apparent disequilibrium. Fe and Mn oxides, carbonates and organic matter may be the most important phases controlling metal availability and distribution.

O presente texto trata das limitações, impostas pela escassez de informação científica confiável, à implementação de programas eficazes e sustentáveis de gestão costeira em paises em desenvolvimento. São sugeridas alternativas às abordagens correntes de monitoramento, as quais visam aprimorar o nível de conhecimento sobre o estado do meio ambiente e decrescer a carência de dados sobre suas condições pretéritas. As discussões apresentadas pretendem encorajar o redesenho das práticas de monitoramento em países em desenvolvimento de forma que passem a se fundamentar no melhor conhecimento científico atual.

This paper addresses the limitations the scarcity of reliable scientific information poses to the implementation of effective and sustainable coastal management programmes in developing countries. Alternatives to the current monitoring approaches are suggested as to improve information level on the state of the environment and to decrease data gap on past conditions. The paper aims at encouraging the redesign of monitoring practices in developing countries as to be ground on the best actual scientific knowledge.

Foram coletados espécimes de mexilhões Perna perna de diversas estações ao longo da costa do Rio de Janeiro e analisados os conteúdos de cobre, zinco, cádmio e cromo. Apesar da grande variabilidade nos organismos pertencentes à mesma população, a avaliação estatística permitiu a diferenciação através de níveis de metal traço entre regiões e estações de coleta assim como entre machos e fêmeas. Diferenças nos conteúdos de metais não confirmam as espectativas baseadas em fontes de contaminação e dados existentes da concentração nas águas.

Perna perna was collected from several sites along the coast of Rio de Janeiro and analysed for the content of copper, zinc, cadmium and chromium. In spite of the observed concentration variability in organisms pertaining to the same population, statistical evaluation allowed metal level differentiation among regions and sites as well as between males and females. Differences in metal contents did not confirm expectations based on source strength and existing data on water concentration.

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.