Abstract Biomarkers of environmental contamination have been frequently used in the assessment of marine ecosystem quality because they provide quantitative measures of biological changes in organisms exposed to pollutants such as hydrocarbons from oil spills. Polychaetes have been tested as sentinel organisms of marine environmental health because they are abundant taxa of benthic assemblages and their sedentary lifestyle ensures chronic exposure to toxins in impacted areas. In this study, we evaluated whether the polychaete Scolelepis goodbodyi can be used as a reliable sentinel species for exposure to polycyclic aromatic hydrocarbons (PAHs) from an experimental diesel spill in a dissipative sand beach in the Southern Atlantic. The design used in this study comprised replicated control and diesel impact sites sampled four times (one, two, four and seven days) before and after the impact. Total PAH levels reached 114.0 ng g -1 in the impact site one day after the diesel spill; however, the pattern of biomarker responses in S. goodbodyi was primarily influenced by spatial variation rather than being attributed to the simulated diesel spill. The apparent absence of a contaminating effect may be linked to the low levels of the toxins retained in the sediment after the spill was simulated to elicit a response or to the presence of an efficient repair system within the organism. Furthermore, the sediments tested in this study, composed of sandy fractions, had a low capacity to concentrate PAHs after the simulated diesel spill, which may have contributed to the low significant changes in their biomarker activities. Based on our results, further studies testing other Polychaeta species and simulating oil spills in sedimentary environments composed of fine sediments such as salt marshes and mangroves may help produce evidence on more effective biomarker responses in these organisms. areas (PAHs Atlantic one, (one two days 1140 114 0 114. 1 - however S organism Furthermore fractions activities results 11

Marine pollution has become relevant for coastal conservation units and ecosystems of great ecological importance. This study validated analytical methods to investigate the occurrence of the emerging contaminants 17β-estradiol (E2), estrone (E1), estriol (E3), and 17α-ethinylestradiol (EE2) in surface waters and suspended particulate matter (SPM) from Guaratuba Bay, South Atlantic, Brazil. The analysis was performed by liquid chromatography coupled to a fluorescence detector (LC-FLD) after pre-concentration of surface water samples by solid phase extraction (SPE) or solid-liquid extraction for SPM samples. The recovery percentages were between 48 and 87%, and the coefficient of variation (CV) between 3 and 24% for SPM and from 64 to 107% (CV of 4 to 42%) for surface water. The method thus proved to be accurate and precise at the concentrations studied (ng g−1 and µg L−1). The concentration ranged from 10 to 177 ng L−1 in surface waters and from 392 to 4108 ng g−1 in SPM. E2, EE2, and E3 were found in SPM under different climatic conditions and population occupation. EE2 was determined in all sampling campaigns, especially in summer, when the number of tourists increases considerably. The presence of EE2 in the SPM of Guaratuba Bay warns for possible implications for the health of coastal environments. importance 17βestradiol βestradiol 17β estradiol β E2 E , (E2) E1, E1 (E1) E3, (E3) 17αethinylestradiol αethinylestradiol 17α ethinylestradiol α EE (EE2 (SPM Atlantic Brazil LCFLD LC FLD (LC-FLD preconcentration pre SPE (SPE solidliquid 87 87% CV 24 6 107 42% 42 g1 g 1 g− L−1. L1 L . L−1) 17 L− 39 410 occupation campaigns summer considerably environments (E2 (E1 (E3 (EE 8 2 41 (E

Abstract The determination of dissolved iron concentrations and speciation was conducted for the first time in surface seawater coastline samples collected during the austral summer of 2020 in Admiralty Bay, King George Island, Antarctica. The technique of competitive ligand exchange/adsorptive cathodic stripping voltammetry with 2,3-dihydroxynaphthalene as the competing ligand was evaluated, showing a sensitivity between 14.25 and 21.05 nA nmol L-1 min-1, with an LOD of 14 pmol L-1 and a mean blank contribution of 0.248 nmol L-1. Physicochemical parameters such as pH (7.85 ± 0.2), salinity (32.7 ± 0.8) and dissolved oxygen (51.3 ± 26.6%) were compatible with those of the literature; however, the average temperature (4.2 ± 0.8 °C) was higher, possibly as a reflection of global warming. The dissolved iron mean value was 18.9 ± 6.1 nmol L-1, with a total ligand concentration of 23.6 ± 12.2 nmol L-1 and a conditional stability complex constant of 12.2 ± 0.2, indicating humic substances as possible ligands. On average, the calculated free iron concentrations were 0.7 ± 0.3 pmol L-1. Relatively high concentrations of iron indicate a possible local source of Fe, likely predominantly from upwelling sediments and secondarily from ice-melting waters, which does not limit the growth of the phytoplankton. 202 Bay Island Antarctica exchangeadsorptive exchange adsorptive 2,3dihydroxynaphthalene 23dihydroxynaphthalene dihydroxynaphthalene 2,3 2 3 evaluated 1425 25 14.2 2105 21 05 21.0 L1 L 1 L- min1, min1 min 1, min-1 0248 0 248 0.24 L1. 1. 7.85 785 7 85 (7.8 02 0.2 , 0.2) 32.7 327 32 (32. 08 8 51.3 513 51 (51. 26.6% 266 26 6 literature however 4.2 42 4 (4. 0. °C C higher warming 189 18 9 18. 61 6. L1, 236 23 23. 122 12 12. ligands 07 03 Fe icemelting ice melting waters phytoplankton 20 3dihydroxynaphthalene 2, 142 14. 210 21. min- 024 24 7.8 78 (7. 32. (32 51. 5 (51 26.6 4. (4 7. (7 (3 (5 26. (

This paper describes the validation of an alternative method for determination of n-alkanes, sterols (OLs) and n-alkanols (ALCs) in marine sediments, through adaptation of clean up. The method reduced the material consumption, the discards produced and working time. The recovery percentages were 60-129% for n-alkanes, 52-67% for OLs and 43-141% for ALCs, acceptable values compared to other studies. The application in Antarctic marine sediments presented satisfactory results indicating contribution of planktonic organisms, higher animals and a little contribution from vegetation.

ResumoA cidade de Montevidéu, com mais de 1,5 milhões de habitantes, circunda a Baía de Montevidéu, onde um dos portos mais ativos e poluídos da América do Sul está localizado. No presente trabalho, foram avaliados esteróis fecais, metais traço, compostos organoclorados e derivados de petróleo nos sedimentos superficiais do Porto de Montevidéu, analisando sua distribuição espacial no interior do porto, bem como em dois dos principais tributários que chegam ao interior da baía. Especificamente para os sítios do porto, foi realizada uma comparação temporal dos metais pesados e hidrocarbonetos, considerando dados pretéritos de 12 anos. Foram observadas alterações significativas nos sítios estudados. Metais, tais como o Pb, Cr e Zn, apresentaram redução nas suas concentrações, enquanto os hidrocarbonetos alifáticos aumentaram seus valores em quase todas as estações. Foram observadas também diferenças entre o verão e o inverno, sugerindo mudanças no padrão de sedimentação, nos ingressos de substâncias e/ou mudanças hidrodinâmicas na área. Os resultados podem vir auxiliar na compreensão do estado atual e para o desenvolvimento de medidas de gestão necessárias para melhorar a qualidade ambiental do porto e da baía.

AbstractSituated opposite the Freshwater Front, Montevideo city with its more than 1.5 million inhabitants encircles Montevideo Bay, where one of the most active and polluted harbors in South America is located. Faecal sterols, trace metals, organochlorine compounds and petroleum derivatives in the sediments of Montevideo Harbor were evaluated and their spatial distribution inside the harbor as well as in the input of two main tributary streams analyzed. Specifically for the harbor sites, a temporal comparison of metal and hydrocarbons was made with previous measurements taken 12 years ago. Clear changes were observed at these sites. The concentration of metals such as Pb, Cr and Zn have diminished, while aliphatic hydrocarbons have increased their values at almost all of the stations studied. Differences were observed between summer and winter suggesting sedimentation, input or hydrodynamic changes in the area. These results help one to understand the present situation and develop the management measures needed to improve the environmental quality of the harbor and bay.

O Estuário de Paranaguá é um dos ambientes mais importantes da costa Sul-Americana. A ocupação urbana, a pesca, o turismo, as indústrias, a introdução de esgoto e o principal porto de exportação de grãos do Brasil são fontes de impactos ambientais. As fontes de matéria orgânica sedimentar foram avaliadas através das concentrações de esteróis, obtidas por cromatografia gasosa acoplada à espectrometria de massas (GC-MS). Os níveis de coprostanol foram comparativamente baixos, exceto próximo da cidade de Paranaguá, onde as altas concentrações indicaram contaminação de esgotos. A análise de componentes principais mostrou a distinção entre os esteróis de origem marinha (colesterol, colestanol, estigmasterol e campesterol), fecal (coprostanol e epicoprostanol) e aportes terrígenos (β-sitosterol). A composição dos esteróis nos sedimentos indicou predomínio de matéria orgânica marinha associada ao fitoplâncton. Contribuições terrígenas foram verificadas próximas a manguezais, rios e pequenas baías não contaminadas. Contribuição de esgotos é restrita ao entorno da cidade de Paranaguá.

The Paranaguá Estuarine System is one of the most important environments of the South American coast. Fishing, urban and tourist activities, industries, sewage and the main shipping port for the export of grains in Brazil are sources of environmental impacts. The sources of sedimentary organic matter were evaluated by sterol concentrations which were obtained by gas chromatography with a mass spectrometer (GC-MS). The coprostanol levels were comparatively low, except at sites close to Paranaguá City, where high concentrations have shown sewage contamination. The principal component analysis showed the distinction between sterols from marine (cholesterol, cholestanol, stigmasterol and campesterol), fecal (coprostanol and epicoprostanol) and terrigenous inputs (β-sitosterol). The sterol composition of the sediments indicated that the estuary system is an embayment dominated by inputs of marine organic matter associated with phytoplankton. Terrestrial inputs were detected only at sites close to mangroves, uncontaminated rivers and semi-closed inlets. Fecal input is restricted around Paranaguá City.

Com o intuito de determinar as características sedimentológicas e físico-químicas do ambiente bentônico e também o nível, distribuição e prováveis fontes dos hidrocarbonetos alifáticos e policíclicos aromáticos, foram coletadas amostras de sedimento em 28 estações localizadas na porção nordeste da Baía de Todos os Santos. A região central e leste da área de estudo apresentaram características de ambientes deposicionais com predomínio de silte e argila e com maiores teores de carbono orgânico total, nitrogênio e enxofre. As razões C/N variaram entre 8,8 e 27,6 indicando uma origem mista da matéria orgânica com contribuições marinha e continental relativamente variáveis. As concentrações de hidrocarbonetos alifáticos totais variaram entre 1,56 e 246,91 µg.g-1 de sedimento seco, correspondendo as maiores concentrações às estações localizadas na região central e leste da área de estudo. A Mistura Complexa não Resolvida (UCM) representou entre 60 e 90% dos hidrocarbonetos alifáticos totais, indicando um alto grau de contribuição antrópica e a presença de resíduos de petróleo degradado. As concentrações de hidrocarbonetos policíclicos aromáticos totais variaram de 8 a 4163 ng.g-1 de sedimento seco. A maior concentração de hidrocarbonetos policíclicos aromáticos foi registrada na estação 5 situada na área adjacente à refinaria de petróleo.

In order to determine the sedimentological and physico-chemical characteristics of the benthic environment and also the level, distribution and probable sources of aliphatic and polycyclic aromatic hydrocarbons, sediment samples were collected at 28 stations in the northeast portion of Todos os Santos Bay. The centre and the east region of the study area showed characteristics of depositional environments with the predominance of silt and clay and high percentages of TOC, nitrogen and sulphur. The molar C/N ratios varied between 8.8 and 27.6 indicating a mixed origin of organic matter with variable marine and continental contributions. Total aliphatic hydrocarbon concentrations ranged between 1.56 and 246.91 µg.g-1 dry weight, corresponding the high concentrations to the stations situated in the centre and in the east region of the study area. The UCM represented between 60 and 96% of the total aliphatic hydrocarbons, indicating a high degree of anthropogenic contribution and the presence of petroleum degraded residues. Total PAH concentrations varied from 8 to 4163 ng.g-1 dry weight. The highest total PAH concentration was recorded at station 5 situated adjacent to the oil refinery.