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Tropical rivers are the main destinations for tailings from urban, industrial and agricultural activities. The present study aimed to investigate if early stages of zebrafish (Danio rerio) development is a viable biological model to assess the toxicity of surface waters of tropical rivers, and whether that toxicity could be correlated to standard water quality indexes. Embryos were exposed to samples from 55 sites from 10 hydrographic basins of rivers in Pernambuco State, northeastern Brazil. Lethality rates, sublethal toxicity based on the general morphology score (GMS) and frequencies of abnormalities were analyzed. Significant mortality was observed in samples of 7 basins. The GMS indicated significant delay in embryo-larval development in 50% of the samples. Highest toxicity was detected in basins within Recife metropolitan area, where 61% of the samples caused sublethal toxicity. Most frequent developmental abnormalities included non-inflation of the swim bladder, delayed hatching and blood stasis. Highest frequencies of blood stasis were detected in samples with highest NH3 concentrations, corroborated by a positive correlation suggesting the existence of a causal relationship. A significant correlation was detected between water quality indexes and GMS with a greater toxic effect being observed in samples collected in areas of greater urban density and greater contamination by domestic sewage. This study demonstrates that the early stages of the zebrafish is a viable ecotoxicological model to assess the toxicity of surface waters and can contribute to a better understanding between the chemical composition and the adverse effects suffered by fish early life stages in tropical rivers.

The Capibaribe River provides water to a population of 1.7 million people in the Brazilian northeast, while receiving agricultural runoff and industrial and domestic effluents along its 280 km. The present study evaluated the ecotoxicity of surface waters along ten sites in rural and urban areas using zebrafish (Danio rerio) early-life stages and related it to water quality indices and chemical abiotic variables. Lethality rates, delays in embryo-larval development quantified by the general morphology score (GMS), and frequencies of developmental abnormalities were analyzed. A correlation was detected between zebrafish GMS and water quality index (WQI), sensitivity to domestic sewage contamination, and trophic state index, focused on eutrophication. These indices agreed in identifying a spatial pattern of smaller impact in terms of ecotoxicity, domestic sewage contamination, and eutrophication risk at three sites in rural areas (mean GMS 16.9), an intermediate impact at four sites with urban and agricultural influence (mean GMS 16.4), and greatest impacts at three more urbanized sites (mean GMS 14.9). Most frequent developmental abnormalities included noninflation of the swim bladder, delayed hatching, nonprotrusion of the mouth, blood stasis, and nondevelopment of pectoral fins. Toxic NH3 concentrations varied spatially, with higher concentrations in urban sites; and blood stasis correlated positively with NH3 , suggesting a causal relationship. Polycyclic aromatic hydrocarbons were detected in both rural and urbanized sites, contributing to detected toxicity. The present study demonstrates the potential of zebrafish early-life stages as an ecotoxicological model that may contribute to a better understanding of surface water quality and ecotoxicity in tropical river systems. Environ Toxicol Chem 2021;40:3063-3077. © 2021 SETAC.

The oil spill that reached Brazilian Coast in 2019 was one of the most extensive disasters and its effects on distinct species are still under investigation. This study evaluated the effects of the oil spill on the crab Pachygrapsus transversus in four reef areas in Northeast of Brazil that are also under different levels of chronic anthropogenic impacts. Changes in population aspects were investigated including maturity, sex ratio, and relative growth considering periods before and after the oil spill. An acute decrease in the number of females captured in areas most affected by oil spill was evident and may be associated with the closure of burrows used for protection. Crabs from the most touristic area presented a decrease in the medium size of carapace and maturation compared to crabs from other less visited areas, which highlights the importance of studying the effects of impacts on marine fauna.

Water quality on the continental shelf off the eastern Brazilian Northeast region was investigated in two oceanographic campaigns during winter and summer, when vertical profiles of salinity, temperature, turbidity, chlorophyll and dissolved oxygen were recorded. Dissolved / dispersed petroleum hydrocarbons (DDPH) were also analyzed in sub-superficial water samples using fixed wavelength fluorescence spectroscopy methods. Shelf waters are dominated by Tropical Waters, with high salinity (> 36.5 g kg-1) and temperature (> 26 °C) and little continental influence. Turbidity was higher during winter, which may be due to the higher continental contribution and/or higher wave action. Chlorophyll was mostly < 1 µg L-1 and dissolved oxygen saturation was predominantly high (> 90%), but innermost costal stations were influenced by the Capibaribe estuary. Median DDPH concentrations were as low as 0.07 and 0.04 µg L-1 Carmópolis oil equivalents during winter and summer respectively, and 0.02 µg L-1 chrysene equivalent for both periods. An exception was observed off Suape Harbor (0.35 µg L-1 Carmópolis oil equiv. and 0.13 µg L-1 chysene equiv.), suggesting navigation activities as the main local source. The overall DDPH median of 0.06 μg L-1 Carmópolis oil equivalents and 0.02 μg L-1 chrysene equivalents are proposed as the baseline concentration for non-polluted coastal water for the tropical western Atlantic Ocean margin.

The Capibaribe Estuarine System (CES) is a tropical estuary located within a densely populated metropolitan region in the Brazilian Northeast, providing multiple ecosystem services including artisanal fisheries, tourism, and navigation. A significant load of domestic and industrial effluents is causing visible environmental degradation that needs to be characterized. This study evaluated the degree of contamination by domestic sewage and the relative contribution of organic carbon (OC) sources in sediments, measuring carbon-to-nitrogen atomic (C/N)

Organic matter (OM) in aquatic system is originated from autochthonous and allochthonous natural sources as well as anthropogenic inputs, and can be found in dissolved, particulate or colloidal form. According to the type/composition, OM can be divided in non-humic substances (NHS) or humic substances (HS). The present review focuses on the main groups that constitute the NHS (carbohydrates, proteins, lipids, and lignin) and their role as chemical biomarkers, as well as the main characteristics of HS are presented. HS functions, properties and mechanisms are discussed, in addition to their association to the fate, bioavailability, and toxicity of organic microcontaminants in the aquatic systems. Despite the growing diversity and potential impacts of organic microcontaminants to the aquatic environment, limited information is available about their association with OM. A protective effect is, however, normally seen since the presence of OM (HS mainly) may reduce bioavailability and, consequently, the concentration of organic microcontaminants within the organism. It may also affect the toxicity by either absorbing ultraviolet radiation incidence and, then, reducing the formation of phototoxic compounds, or by increasing the oxygen reactive species and, thus, affecting the decomposition of natural and anthropogenic organic compounds. In addition, the outcome data is hard to compare since each study follows unique experimental protocols. The often use of commercial humic acid (Aldrich) as a generic source of OM in studies can also hinder comparisons since differences in composition makes this type of OM not representative of any aquatic environment. Thus, the current challenge is find out how this clear fragmentation can be overcome.

Oil spill events in the marine environment can have a deleterious impact on the affected ecosystems, such as coral reefs, with direct consequences for their socioeconomic value. The mutualistic relationship between tropical corals and their dinoflagellate symbionts (Symbiodiniaceae) provide structural and nutritional basis for a high local biodiversity in oligotrophic waters. Here, we investigated effects of crude oil water-accommodated fraction on the competitive fitness of the model zooxanthellae species Symbiodinium glynnii. Results of laboratory essays demonstrate that crude oil carbon is incorporated into the cellular biomass with a concomitant change of δ13C isotopic value. Carcinogenic/mutagenic polycyclic aromatic hydrocarbons were identified in the culture media and were responsible for a linear reduction in population growth of S. glynnii, presumably related to energy relocation for DNA repair. Additionally, the experiments revealed that physiological effects induced by crude oil compounds are genetically inherited by the following generations under non-contaminated growth conditions, and induce a reduction in the competitive fitness to cope with other environmental parameters, such as low salinity. We suggest that the effects of crude oil contamination represent an imparing factor for S. glynnii coping with anthropogenic drivers (e.g. warming and acidification) and interfere with the delicate symbiont-host relationship of tropical corals. This is especially relevant in the coastal areas of northeastern Brazil where an oil spill event deposited crude oil on shallow water sediments with the potential to be resuspended to the water column by physical and/or biological activity, enhancing the risk of future coral bleaching events.

Products coal tar-based are largely used as concrete structures as protective coatings but some questions about leaching and potential toxic effects remain unclear. A laboratory experiment exposing oysters to miniaturized concrete pillars painted with Lackpoxi N1761 over time was performed and trace elements and 17 PAH were monitored in seawater exposure media, and oyster tissues. The original paint composition was also analyzed, and high concentrations of trace elements and PAH were detected. Sharp increases in PAH concentrations were observed after 6–96 h in exposure media and oyster tissues, suggesting that these compounds were leached from the painted structures. In parallel, the integrity of the hemocytes lysosomal membranes of exposed organisms has been damaged. Based on the response of this biomarker, the use of Lackpoxi N1761 is potentially harmful to the environment and it is required that coal tar-based paints be evaluated according to the environmental risk assessment protocols.

The present study is a literature-based analysis investigating occurrence and the possible consequences of polycyclic aromatic hydrocarbons (PAH) in marine protected areas (MPAs) of Latin America and Caribbean. The approach using overlapping of georeferenced MPA polygons with data compiled from peer-reviewed literature, published during the last 15 years, showed 341 records of PAH in 9 countries. PAH was reported to occur within the boundaries of 36 MPAs located in Argentina, Brazil, Colombia, Mexico, Nicaragua and Uruguay. According to quality guidelines, low to moderate impacts are expected in MPAs categorized in different management classes. Considering sediment samples, 13% of the records presented concentrations enough to cause occasional toxicity. Such level of risk was also seen in Ramsar sites and in Amazonian MPAs. In addition, based on concentrations reported in biota, occasional deleterious effects on organisms from Biosphere Reserves might occur. Diagnostic ratios pointed out petrogenic and pyrolytic processes as PAH predominant sources, and were mainly attributed to the proximity to ports, industries and urban areas. MPAs located in the vicinity of impact-generating areas may be under threat and require government attention and action, mainly through implementation of contamination monitoring programs.

Estuaries are considered receptors of various contaminants released into the environment, including Polycyclic Aromatic Hydrocarbons (PAH), a ubiquitous contaminant. In this study, the response of subtidal macrofauna in the polyhaline zone of three tropical estuaries was analyzed using a taxonomic approach, multimetric indices, and functional traits, to three different levels of PAH. The estuaries presented distinct degrees of contamination, with PAH directly correlated with mud percentage and organic matter. The considerable variation in granulometry found in the three studied estuaries may indicate complex hydrodynamics, with very different sedimentary characteristics. The community structure showed typical estuarine characteristics, with low diversity and high dominance. The macrofauna was distinct among estuaries, with no shared dominant species and with several species occurring just in one site, with different compositions, although other parameters of the community structure were similar. The AMBI and functional indices performed better than taxonomic indices in separating the areas with different impacts. In the analyzed communities, the functional traits approach demonstrated consolidated patterns in the estuarine environment, such as the predominance of opportunistic species, generally of smaller size and detritivore/depositivore, under conditions of pollution by the organic load. Local characteristics, such as the predominance of suspensivore organisms and relatively more mobility in areas with higher hydrodynamics, provide insight into the community's behavior on natural and anthropogenic stressors. The multivariate taxonomic and functional analyses were complementary, emphasizing the importance of integrating them in these environments diagnosis. Stressed environments need information from the entire data set for a correct assessment of the community.

Located in Northeastern Brazil, the Capibaribe Estuarine System is an important ecosystem that supplies food and protection for nursery of several species with ecological and economic importance. It is located inside an urbanized area, receives untreated domestic and industrial effluents, and houses some marinas and the Harbor of Recife, which are very important to national and international communities. The distribution and sources of PAHs were investigated in sediments from CES and adjacent shelf. Total PAH concentrations ranged from non-detectable to 497.6 μg g(-1). Pyrolytic sources predominated in most of sites, but petrogenic PAHs were also recorded. The concentration decrease of PAHs toward adjacent shelf suggests that the main source of these compounds is in the upper portion of estuary, where there is an intense discharge of sewage, but atmospheric input also seems to be relevant to the area. The results reinforce the important role of an estuary in contaminant retention.

Large amounts of crude oil were found along Brazil's northeast and southeast seaboard from August 2019 to January 2020. Petroleum companies and oil tankers reported no accidents previously or during this period. The stranded oil on Brazilian beaches looks like tar; it has solid aspect and is denser than seawater. Chemical characterization of this oil showed that light hydrocarbons were still present, increasing the probability of negative effects to coastal organisms and ecosystems upon release in the water column. Diagnostic ratios, chromatogram pattern, and percentage-weathering plots proved that the oil samples share the same oil source. This work provides data for future comparison with oil samples that will likely be found stranded along the Brazilian shoreline in the years to come, helping to understand long term issues associated with the mysterious oil spill that made landfall in late 2019.

The Suape Estuary encompasses the Suape Industrial Port Complex (SIPC), a major industrial development in Brazil's Northeast region, which, in order to be implanted, caused drastic environmental changes in this system. This study presents the first physical characterization of the Suape estuarine system, focusing on the local hydrodynamics, material transport and its influence on some specific properties. Physical properties were also associated to dissolved dispersed petroleum hydrocarbons (DDPHs). A study was undertaken during a complete semi-diurnal tidal cycle (13 hr), during which water level, water flow, current velocity and direction, water properties (salinity, temperature, suspended particulate matter - SPM -, chlorophyll and dissolved oxygen) were recorded using ADCP and CTD systems. The DDPHs were investigated in surface and bottom waters, by spectrofluorescence, using Carmópolis oil and chrysene as analytical standards. Results showed a well-mixed vertical structure, a semi-diurnal tide regime and a diurnal thermal pattern. There was no statistical difference between DDPH concentrations at surface and bottom, due to the tide acting as an important homogenizer. DDPHs were low and the main contribution seems to be that from SIPC, as the residual transport of DDPHs, chlorophyll and dissolved oxygen, was towards the Massangana estuary. An opposite pattern was observed for salinity and SPM, whose residual transport was towards the lagoon. The results pointed local hydrodynamics as an essential tool for understanding material transport and exchanges among the estuarine segments. A longer time series should be studied in order to obtain more robust conclusions. Resumo A instalação do Complexo Industrial Portuário de Suape (CIPS) modificou algumas características físicas, químicas e biológicas do Estuário de Suape. Este estudo apresenta a primeira caracterização física deste sistema, focando na hidrodinâmica local, transporte de materiais e a influência destes sobre algumas propriedades locais. Os parâmetros físicos também foram associados aos hidrocarbonetos de petróleo dissolvidos e/ou dispersos (HPDDs). Durante um ciclo completo de maré (13 h), foram registrados o nível, fluxo e propriedades da água (salinidade, temperatura, material em suspensão - MS -, clorofila e oxigênio dissolvido), além da velocidade e direção das correntes, usando ADCP e CTD. Os HPDDs foram investigados nas águas superficiais e de fundo, através de espectrofluorescência. Os resultados revelaram uma estrutura vertical homogênea, um regime de maré semidiurno e um padrão térmico diurno. As concentrações de HPDDs na superfície e no fundo são baixas e similares, devido à ação da maré. A fonte mais provável é o CIPS, uma vez que o transporte residual dos hidrocarbonetos de petróleo, da clorofila e do oxigênio dissolvido são no sentido do estuário do Massangana. Um padrão oposto foi observado para o transporte residual da salinidade e MS, no sentido da lagoa. Estes resultados indicam que a hidrodinâmica local é essencial para entender o transporte e troca de materiais entre os vários segmentos do estuário. Estudos mais completos são necessários para se obter conclusões mais consistentes.

Quantification of polycyclic aromatic hydrocarbon (PAH) metabolites in fish bile is widely used to evaluate levels of internal PAH contamination in fish, whereas behavioral effects are deemed important to address potential risks to fish populations. The estuarine guppy Poecilia vivipara was exposed for 96h to waterborne phenanthrene at concentrations of 10, 50, 200 and 500μgL(-1). Phenanthrene and metabolites in bile were analyzed by fixed fluorescence at 260/380nm (excitation/emission) wavelengths. Phenanthrene increased in the bile of exposed fish in a dose-dependent pattern, and log bile bioconcentration factors ranged from 4.3 to 3.9 at 10 and 500μgL(-1) phenanthrene, respectively, values that are similar to predicted bioconcentration factors based on phenanthrene Kow. Swimming resistance index was reduced to 81% of control values at 500μgL(-1). Alteration of swimming speed was non monotonic, with a significant speed increase relative to control fish in treatments 50 and 200μgL(-1) phenanthrene, respectively, followed by a speed decrease in fish exposed to 500μgL(-1). However, swimming trajectories of fish exposed to 50, 200 and 500μgL(-1) was altered by the development of a repetitive circular swimming behavior, in contrast to the controls that explored the entire experimental arena. This change in swimming patterns apparently explains the reduction in prey capture rates at 200μgL(-1) phenanthrene. This study provides important information enabling the use of the estuarine guppy P. vivipara to monitor PAH metabolites in bile and its bioconcentration, linking internal exposure with ecologically relevant behavioral effects in the species.

Goiana estuary is a well preserved marine protected area (MPA) located on the northeastern coast of Brazil. Despite its current state, human activities in the watershed represent a potential threat to long term local preservation. Dissolved/dispersed aromatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) were investigated in water and sediments across the estuarine salt gradient. Concentration of aromatic hydrocarbons was low in all samples. According to results, aromatic hydrocarbons are associated to suspended particulate matter (SPM) carried to the estuary by river waters. An estuarine turbidity maximum (ETM) was identified in the upper estuary, indicating that both sediments and contaminants are trapped prior to an occasional export to the adjacent sea. PAHs distribution in sediments were associated with organic matter and mud content. Diagnostic ratios indicated pyrolytic processes as the main local source of PAHs that are probably associated with sugarcane burning and combustion engines. Low PAH concentrations probably do not cause adverse biological effects to the local biota although their presence indicate anthropogenic contamination and pressure on the Goiana estuary MPA.

Butyltin compounds (BTs) were used worldwide, especially because of their properties as biocides. Due to its high toxicity, the use of tributyltin (TBT) in antifouling paints has been prohibited in most countries. The occurrence and impact of BTs were assessed in surface sediments and in Stramonita rustica populations of two tropical estuaries that host major ports in northeastern Brazil. ΣBT concentrations ranged fromLOQ to 542ngSng

Made available in DSpace on 2018-12-11T16:47:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2017-01-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) During the last years, shell alterations in gastropods have been proposed as tools to be used in monitoring programs. However, no studies were so far performed investigating the relationships among shell parameters and classical biomarkers of damage. The relationship between shell alterations (biometrics, shape and elemental composition) and biomarkers (LPO and DNA strand break) was evaluated in the limpet L. subrugosa sampled along a contamination gradient in a multi-impacted coastal zone from southeastern Brazil. Statistically significant differences were detected among sites under different pollution levels. The occurrence of shell malformations was consistent with environmental levels of several hazardous substances reported for the studied area and related to lipid peroxidation and DNA damage. In addition, considering the low mobility, wide geographic distribution, ease of collection and abundance of limpets in coastal zones, this putative tool may be a cost-effective alternative to traditional biomarkers. Thus, shell alterations in limpets seem to be good proxies for assessing biological adverse effects in multi-impacted coastal zones. Departamento de Ciências do Mar Universidade Federal de São Paulo (UNIFESP) Departamento de Oceanografia Universidade Federal de Pernambuco (UFPE) Museu de Zoologia Universidade de São Paulo (USP) Departamento de Biologia Universidade Católica de Pernambuco Instituto de Biociências Universidade Estadual Paulista (UNESP) Instituto de Biociências Universidade Estadual Paulista (UNESP) CNPq: 166122/2015-7 FAPESP: 2015/25063-0 CNPq: 306486/2015-6 CNPq: 307074/2013-7

A fast paced industrial and port development has occurred at Suape Estuary, Northeast Brazil, but no information about hydrocarbon concentrations in water is available to this area. Considering that, the contamination level of Suape was determined by UV-Fluorescence in terms of dissolved and/or dispersed petroleum hydrocarbons (DDPHs), during wet and dry seasons. DDPHs ranged between 0.05 and 4.59 μg L(-1) Carmopolis oil equivalents and 0.01-1.39 μg L(-1) chrysene equivalents, indicating DDPHs close to a baseline contamination level. Some relatively high concentrations (>1 μg L(-1)) were probably associated with shipyard operations (hull paintings and ship docking), pollutants remobilization by dredging operations, occasional industrial discharges and oil derivatives released by vessels. DDPHs concentrations were lower in the wet season suggesting that the increased dilution rates caused by rainfall dominated upon the wet deposition of atmospheric combustion-derived PAHs process. Results in this study may be used as baseline to further studies in this area.

O Sistema Estuarino do Rio Capibaribe (SERC) é um dos sistemas hídricos mais importantes do estado de Pernambuco, e é formado pelo estuário do rio Capibaribe, Bacia do Pina e Bacia Portuária. Infelizmente, a ação das atividades humanas em seu entorno associadas às elevadas cargas de contaminantes provenientes principalmente do lançamento de efluentes domésticos e industriais nos rios que o formam, têm resultado em um elevado nível de poluição ambiental. Com o intuito de avaliar as potenciais fontes de contaminação e grau de degradação deste sistema, foi feito um levantamento das indústrias instaladas nas proximidades do SERC e dos estudos realizados nesta região. Além disto, in situ, foram quantificadas as galerias de águas pluviais ou de lançamento de esgotos localizadas no trecho que compreende o Parque da Jaqueira até a confluência do rio Capibaribe com a Bacia do Pina. Os resultados reportados na literatura indicaram que a qualidade da água deste sistema está altamente comprometida, indicada através dos parâmetros Oxigênio Dissolvido, Demanda Bioquímica de Oxigênio, nutrientes, coliformes termotolerantes, metais, dentre outros, que estiveram em desacordo com os limites estabelecidos pela resolução CONAMA 357/05. Cerca de 57 indústrias de alto e médio potencial de poluição estão localizadas nas imediações do estuário. A presença de 150 pontos de lançamento de águas residuárias foram observadas no trecho estudado. O mau cheiro, lixo e a degradação visual, indicam a possibilidade de lançamentos de esgotos interligados nas saídas de águas pluviais, comprometendo cada vez mais a qualidade das águas, sedimentos e organismos do SERC. Estes resultados são bastante preocupantes, uma vez que essa região é muito importante do ponto de vista econômico, ecológico e social, sendo urgente a tomada de decisões que recuperem e priorizem a conservação desta área. Palavras chave: qualidade da água, galerias de esgotos, águas pluviais, poluição, indústrias.

Admiralty Bay on the King George Island hosts the Brazilian, Polish and Peruvian research stations as well as the American and Ecuadorian field stations. Human activities in this region require the use of fossil fuels as an energy source, thereby placing the region at risk of hydrocarbon contamination. Hydrocarbon monitoring was conducted on water and sediment samples from the bay over 15 years. Fluorescence spectroscopy was used for the analysis of total polycyclic aromatic hydrocarbons (PAHs) in seawater samples and gas chromatography with flame ionization and/or mass spectrometric detection was used to analyse individual n-alkanes and PAHs in sediment samples. The results revealed that most sites contaminated by these compounds are around the Brazilian and Polish research stations due to the intense human activities, mainly during the summer. Moreover, the sediments revealed the presence of hydrocarbons from different sources, suggesting a mixture of the direct input of oil or derivatives and derived from hydrocarbon combustion. A decrease in PAH concentrations occurred following improvement of the sewage treatment facilities at the Brazilian research station, indicating that the contribution from human waste may be significant.

Os sedimentos concentram uma fração considerável dos contaminantes que chegam aos estuários. Estes compostos podem comprometer a sobrevivência, fecundidade e desenvolvimento dos organismos bentônicos. O objetivo deste estudo foi avaliar a toxicidade dos sedimentos superficiais do Sistema Estuarino do Rio Capibaribe (SERC) sobre o copépodo bentônico Tisbe biminiensis. Amostragens de sedimento foram realizadas em cinco estações do SERC. Hidrocarbonetos de petróleo dissolvidos e/ou dispersos na água (HAPDDs) foram analisados em amostras de água de fundo para avaliação do aporte recente destes compostos. Efeitos subletais sobre T. biminiensis foram observados para as amostras coletadas em frente ao Porto do Recife, na desembocadura norte do Rio Capibaribe e na porção superior do estuário. As concentrações de HAPDDs registradas no SERC sugerem que a contaminação ocorre de forma crônica e é proveniente principalmente da descarga de efluentes domésticos e industriais, como também das atividades portuárias. Palavras chave: Fecundidade total, percentual de copepoditos, contaminação, hidrocarbonetos de petróleo.

One of the most important natural sunlight absorbing substances in water is the chromophoric dissolved organic material (CDOM). Its influence on optical properties has been studied for many years, but questions of how its structural and optical characteristics change in the environment still remain. CDOM water samples were collected from coastal waters of southwest Florida during three cruises in the year 2001: one in the dry season (June) and two in the rainy season (September and November). Analyses of molecular mass (MM) distribution and optical characteristics were done using the flow field-flow fractionation (FlFFF) separation technique with absorbance and fluorescence detectors. On the basis of the results, mixing, source variability, degradation, and excited state quenching processes are important determinants of CDOM composition and optical properties in this region. During the dry season, the MM distribution did not change significantly spatially. In September and November, higher MM compounds and an increase of CDOM fluorescence were observed, found inside the rivers and in near-coastal samples, consistent with the rivers being a significant CDOM source. Results suggest that chromophores were broken down to smaller MM compounds faster than fluorophores, indicating that the fluorescent moieties are more resistant to degrading/removal processes than the non-fluorescing compounds, even though the fluorophores were always centered at lower MM. On the other hand, the fluorescence quantum yield decreased faster than absorbance coefficients, suggesting that fluorophores were quenched by complexing with some metals. For all months, the chromophores' MM for offshore samples remained the same. The carbon concentration ratio between chromophores and fluorophores changed from lower to higher salinities, suggesting that the composition of the waters changed toward offshore. The differences in the optical characteristics, MM distributions, and carbon concentration observed suggest that the CDOM sources, physical, and photochemical degradation processes change seasonally.

Seawater from 8 stations in Admiralty Bay was systematically sampled during the summer of 1994, 1995, 1996 and 1997 and analyzed by spectrofluorimetry to measure dissolved/dispersed petroleum hydrocarbons (DDPHs). The purpose of this study was to detect some temporal and spatial changes in terms of oil contamination of the region. The results indicate low levels of oil pollution with relatively high concentrations near the research stations located in the study area. During the summers of 1995 and 1996 the average concentrations for individual stations were low and below of 0.50 ¼g.L-1. Summers of 1994 and 1997 had relatively higher average concentrations (up to 1.57 ¼g.L-1), mainly in front of Arctowski and Ferraz Research Stations.Amostras de água na Baía do Almirantado, Península Antártica, foram sistematicamente coletadas em 8 estações durante os verões de 1994 a 1997 onde foram analisados hidrocarbonetos do petróleo dispersos e dissolvidos por espectrofluorescência. O objetivo foi avaliar variações temporais e espaciais em termos de contaminação por óleo na região. Os resultados em geral indicam baixos níveis de poluição embora tenham sido verificadas algumas concentrações relativamente maiores nas proximidades das estações de pesquisa fixadas na região de estudo. Durante os anos de 1995 e 1996 a média das concentrações foram baixas e menores que 0,50 ¼g.L-1 para os pontos individuais. Os verões de 1994 e 1997 tiveram concentrações médias mais elevadas (até 1,57 ¼g.L-1), e os maiores valores foram nas proximidades das estações brasileira e polonesa.

Colored dissolved organic material (CDOM) is an important sunlight absorbing substance affecting the optical properties of natural waters. However, little is known about its structural and optical properties mainly due to its complex matrix and the limitation of the techniques available. A comparison of two southwestern Florida rivers [the Caloosahatchee River (CR) and the Shark River (SR)] was done in terms of molecular mass (MM) and diffusion coefficients (D). The novel technique Frit inlet/frit outlet-flow field-flow fractionation (FIFO-FIFFF) with absorbance and fluorescence detectors was used to determine these properties. The SR receives organic material from the Everglades. By contrast, the CR arises from Lake Okeechobee in central Florida, receiving anthropogenic inputs, farming runoff, and natural organics. Both rivers discharge to the Gulf of Mexico. Fluorescence identified, for both rivers, two different MM distributions in low salinity water samples: the first was centered at approximately 1.7 kDa (CR) and approximately 2 kDa (SR); the second centered at approximately 13 kDa for both rivers, which disappeared gradually in the river plumes to below detection limit in coastal waters. Absorbance detected only one MM distribution centered at approximately 2 kDa (CR) and 2.2-2.4 kDa (SR). Fluorescence in general peaked at a lower MM than absorbance, suggesting a different size distribution for fluorophores vs chromophores. A photochemical study showed that, after sunlight, irradiated freshwater samples have similar characteristics to more marine waters, including a shift in MM distribution of chromophores. The differences observed between the rivers in the optical characteristics, MM distributions, and D values suggest that the CDOM sources, physical, and photochemical degradation processes are different for these two rivers.

Time-resolved and steady-state fluorescence measurements were used to characterize dissolved organic matter (DOM) in bulk water samples from a fresh to marine transition zone. The region studied was the Shark River and Florida Bay in Everglades National Park in Southwestern Florida. Samples were taken from the fresh waters at the head of the Shark River, the mouth of the river, and in the fresh-water river plume as it mixed into the saline waters of Florida Bay. The salinity varied from 0.47 at the head of the river to 36.0 for this series of 11 samples. Steady-state fluorescence intensity decreased with increasing salinity from the head of the Shark River into Florida Bay. This is due to dilution by mixing, as changes in the fluorescence intensity also correlated with changes in the levels of total organic carbon (TOC). Fluorescence lifetime measurements were performed on the five most concentrated samples (salinity from 0.47 to 30.5). The decay of the time-resolved fluorescence could be reasonably fit to a multi-exponential function, with three lifetime components on the order of 0.5–0.8, 2–3, and 6–9 ns. These ranges are in agreement with previous literature results for humic acids, fulvic acids, and marine CDOM concentrated by ultrafiltration. This is the first study of CDOM fluorescence lifetimes in coastal waters in a fresh to marine transition zone. Although photochemical and biological transformations of CDOM occur in these zones, no statistically significant difference in lifetimes was observed with increasing salinity. However, irradiating fresh water samples from the head of the Shark River at 280 and 334 nm resulted in a significant decrease in the two shorter lifetime components (by a factor of ∼4), but only a slight decrease in the longest lifetime component.

Results from the first application FIFO–FlFFF (1 frit inlet/frit outlet–flow field-flow fractionation) to the characterization of colored dissolved organic material (CDOM) in river and coastal waters are described. FlFFF separates compounds based on their diffusional characteristics. The frit inlet/frit outlet (FIFO) feature was recently developed to concentrate samples inside the FlFFF channel for improved stability, reproducibility and sensitivity. Our results show that FIFO increases sensitivity by an order of magnitude and the system has a linear response to molecular weight and concentration over a wide dynamic range. Errors for replicate analyses with a Caloosahatchee River sample from southwest Florida were

An oil pipeline ruptured in May 1994 and 2 700 tons of crude oil leaked into the São Sebastião Channel, affecting several neighboring areas. A program for the monitoring of hydrocarbons in sediments, using the gas chromatography / flame ionization detector methodology, was being undertaken in the area at the time. The data obtained were compared to those of samples collected after the accident to determine the fate of the oil spilled and ascertain its contribution to the environment. The earlier results showed that hydrocarbons were introduced from two different sources: biogenic, mainly from terrestrial plants, and anthropogenic, as oil, in sewage and from shipping. The later data indicated that the site closest to the pipeline rupture had been the most affected. Following that, two stations located at the north entrance of the channel presented the highest n-alkane concentrations, suggesting that the northeasterly wind-driven currents had carried the oil northward. Seven months later, one of these stations, a high-energy site, showed some signs of recovery, but this process was not observed at the other, which seemed to be a low-energy site. In conclusion, the data showed that the aliphatic hydrocarbon analyses were powerful tools for the assessment of the fate of the oil spill and that the northern part of the São Sebastião Channel is more subject to the effects of oil spills. A ruptura de um oleoduto em maio de 1994 introduziu 2.700 tons de óleo cru no Canal de São Sebastião, contaminando algumas áreas. Na ocasião um monitoramento de hidrocarbonetos em sedimentos estava sendo realizado na região, utilizando o método de cromatografia em fase gasosa/ detecção por ionização de chama. Os dados obtidos nesse monitoramento foram comparados aos resultados das amostras coletadas logo após o acidente, com o objetivo de verificar a extensão da contaminação por óleo e os lugares mais atingidos. Os dados prévios mostraram duas fontes de introdução de hidrocarbonetos: biogênica, com predomínio de plantas superiores, e antrópica, causada por atividades náuticas e esgotos. Os dados posteriores mostraram que a estação de coleta mais próxima ao oleoduto foi a mais atingida. Na sequencia, as duas estações localizadas na entrada norte do canal apresentaram as maiores concentrações de n-alcanos, sugerindo que as correntes NE, impulsionadas pelo vento, transportaram o óleo no sentido norte do canal. Sete meses depois uma destas estações, aquela situada em local de alta energia, mostrou sinais de recuperação, o que, contudo, não foi observado na outra, considerada de ambiente deposicional. Em conclusão, pode-se afirmar que análises de hidrocarbonetos são ferramentas poderosas para avaliar o destino de um óleo e que a parte norte do Canal de São Sebastião tem maior probabilidade de ser afetada na ocasião de um derrame de óleo.

Os marcadores orgânicos moleculares (hidrocarbonetos alifáticos, esteróis e álcoois) em amostras de sedimentos superficiais e de testemunhos curtos coletados em diápiros e pockmarks localizados no talude sul do Brasil, foram utilizados para identificar as possíveis contribuições biogênicas (autóctones / alóctones). De modo geral, tanto nas amostras superficiais como ao longo dos testemunhos, o maior acúmulo de carbono orgânico total nos pockmarks foi observado, indicando o possível aprisionamento de sedimentos e de matéria orgânica no interior das concavidades. A presença de β-sitosterol, campesterol, álcoois e n-alcanos pesados, indicaram contribuições terrígenas para a área de estudo, que pode ser advinda da descarga continental do Rio da Prata, uma vez que a predominância terrígena é proveniente das pradarias, típica vegetação do Uruguai e do sul do Rio Grande do Sul. O transporte de sedimentos terrígenos ocorre em direção ao norte, ao longo da plataforma continental sul brasileira, pela Corrente Costeira do Brasil. A presença de detritos de fitoplâncton e zooplâncton também ocorre devido à influência dos nutrientes do Rio da Prata. As possíveis liberações de gás/fluido, que sustentaram ecossistemas quimiossintéticos em diferentes intervalos de dois testemunhos em pockmark e diápiro foram constatadas através da presença relativamente maior de n-alcanos leves com número par de carbonos. Organic molecular markers (aliphatic hydrocarbons, sterols and alcohols) in superficial and short cores sediment samples collected in diapirs and pockmarks located in the southern slope of Brazil were used in order to identify the possible biogenic contributions (autochthonous / allochthonous). In general, in surface samples and throughout the cores samples, the greatest accumulation of total organic carbon in the pockmarks was observed, indicating the possible entrapment of sediments and organic matter inside the concavities. The presence of β-sitosterol, campesterol, alcohols and heavy n-alkanes indicated terrigenous contributions to the study area, which may be due to the continental discharge of Río de la Plata, since the terrigenous predominance is due to the prairies, a typical vegetation of Uruguay and the south of Rio Grande do Sul. The terrigenous sediments transport is carried through the North, along the Brazilian continental shelf, by the Coastal Stream of Brazil. The presence of phytoplankton and zooplankton debris is also due to the influence of the nutrients contribution from Río de la Plata. Possible gas / fluid releases, which sustained chemosynthetic ecosystems at different intervals of two pockmark and diaper cores, were verified by the relative predominance of even-numbered carbon n-alkanes.

Este estudo teve como objetivo avaliar a toxicidade do sedimento da Enseada de Ubatuba através de testes de toxicidade, utilizando-se fase aquosa e sedimento total antes e depois do aumento da população de veraneio e a contaminação por esgoto urbano. Realizaram-se testes de toxicidade com a água intersticial e interface água/sedimento e larvas de L. variegatus. No testes com sedimento total utilizou-se anfípodo T. viscana. Utilizaram-se as análises de esteróis fecais para verificar a contaminação por esgoto. Foram coletadas em 17 estações. Uma estação do canto direito da Praia do Itaguá foi a única que obteve toxicidade nos três testes na campanha após o aumento da população de veraneio. Para os testes com a fase aquosa, uma estação próxima ao Instituto de Pesca e duas na Praia do Perequê-Açú foram tóxicas nas duas campanhas. Apresentaram contaminação por esgoto e toxicidade para os testes de fase aquosa três estações do canto direito da Praia do Itaguá, uma próxima ao Rio Acaraú, outra em frente ao Rio Grande e também uma na Praia do Perequê-Açú. Uma estação próxima a saída do Rio Grande apresentou indício de contaminação por esgoto, mas não obteve toxicidade na fase aquosa. O aumento da população de veraneio mostrou uma maior toxicidade para os testes com a fase aquosa e uma diminuição do número de sobreviventes de anfípodos. A Enseada de Ubatuba apresentou toxicidade nos testes com fase aquosa em quase todas as estações após o aumento da população, assim deve ser monitorada com freqüência e melhorar a infra-estrutura de saneamento. The goal of this study was to evaluate the toxicity of the sediment in Ubatuba small Bay through toxicity tests using liquid phase and the total sediment before and after the increase of the floating population and the sewage contamination. The liquid phase was evaluated through toxicity test with interstitial water and water/sediment interface, both with embryos of L. variegatus. The tests with total sediment were utilized amphipod T. viscana. The analyses with chemical faecal steroids marks was utilized for the sewage contamination in the sediment. It was realized samples in 17 stations. One station localized in the right corner of Itaguá beach, was the only one that showed toxicity in the three of the tests in the campaign after the increase of the floating population, two tests with de liquid phase in one station, localized near to Pesca Institute, two stations, localized in the Perequê-Açu beach, was toxic in both campaigns. Contamination by urban sewage and toxicity tests of liquid phase was observed in three stations localized in the right corner of Itaguá beach, other near the mouth of the Acaraú river, and another in front of Grande river and as well one station in the Perequê-Açu beach. One station near the mouth of Grande river had showed indication of contamination by urban sewage, but the liquid phase showed no sign of toxicity. The increase of the floating population showed a high toxicity for the test with liquid phase and a decrease in the number of survives in the amphipods tests. The small bay of Ubatuba showed toxicity in the liquid phase tests in almost of all stations after the increase in the floating population, then the region must be monitored with frequency and it is necessary to improve the structure of the sanitation in the area.