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We analyzed per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foams (AFFFs) used to extinguish a major fire in a petrochemical terminal from the Port of Santos (Brazil). Eight AFFFs from seven known commercial brands and one unknown sample (AFFF-1 to AFFF-8) were evaluated. 17 PFAS were identified and quantified using high performance liquid chromatography (LC/MS). The concentrations of Σ17 PFAS in the AFFFs ranged from 500 to 9000 ng/g, with prevalence of short chain PFAS (~85 %), followed by long chain PFAS. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), included in the global treaty of the Stockholm Convention, were also detected. We estimated that at least 635.96 g of PFAS were introduced in the estuary, representing a massive input of these substances. This investigation reports the PFAS composition of AFFFs used in firefighting in the GRULAC Region (Group of Latin American and Caribbean countries).

Made available in DSpace on 2019-10-06T17:16:00Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-09-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro (FAPERJ) The present study evaluated the ecological risk of metal contamination in sediments of Guanabara Bay (GB) by combining multiple lines of evidence (LOEs). Chemical analysis and a set of whole-sediment toxicity assays were conducted with Tiburonella viscana, Kalliapseudes schubartii, Anomalocardia flexuosa, and Nitocra sp. Results were integrated by multivariate analysis and qualitative methods. Additionally, a whole-sediment Toxicity Identification Evaluation technique (TIE) was applied to identify the chemical groups responsible for the effects. Sediments from harbor and industrial areas exhibited toxicity linked to moderate to high concentrations of Zn, Pb, Cu and Cr. The TIE technique confirmed such effects, but it also indicates the contribution of ammonia and organic compounds to the observed toxicity. Our results demonstrate that the combination of multiple LOEs improves the effectiveness of environmental risk assessment of chemical stressors and management of coastal ecosystems in tropical regions. São Paulo State University (UNESP), Praça Infante Dom Henrique, s/n Fluminense Federal University (UFF) Program of Geochemistry Department of Geochemistry West Pará State Federal University (UFOPA) Engineering and Geosciences Institute Mineral Analysis Coordination Center of Mineral Technology (CETEM), Av. Pedro Calmon, 900, Cidade Universitária Rio de Janeiro Federal University (UFRJ) Health Science Center, Av. Carlos Chagas Filho, 373, Cidade Universitária São Paulo State University (UNESP), Praça Infante Dom Henrique, s/n CAPES: 001 FAPESP: 13/15482-0 FAPESP: 2015/13143-0 CNPq: 308533/2018-6 CNPq: 311609/2014-7 CNPq: 455280/2014-2

Made available in DSpace on 2021-06-25T10:32:42Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-09-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Recent studies have shown that the effectiveness of establishing Marine Protected Areas (MPAs) is threatened by toxic effects of contaminants. São Paulo is the most economically developed state of Brazil, and its coast is protected by a system of MPAs, including the North Shore Marine Protected Area (NSMPA). The present study provides a first assessment of sediment quality in NSMPA and two reference sites. Concentrations of arsenic (As), metals (Al, Fe, Cd, Cr, Cu, Ni, Pb, and Zn) and polycyclic aromatic hydrocarbons (PAHs) and its sources were determined. Comparisons with sediment quality guidelines indicated low contamination, as confirmed by the Geoaccumulation Index, which classified the results as background levels. Whole-sediment exposures of the amphipod Tiburonella viscana were performed to estimate possible acute effects, but samples exhibited no toxicity. The results presented in this study represent a baseline for further monitoring programs of MPAs, supporting conservation actions of management plans. São Paulo State University (UNESP), Praça Infante Dom Henrique, s/n Institute of Marine Sciences (LABOMAR) Federal University of Ceará (UFC), Av. da Abolição, 3207 Oceanographic Institute (IOUSP) University of São Paulo (USP), Praça do Oceanográfico, 191 Department of Chemistry Federal University of Ceará (UFC), Av. Humberto Monte s/n Department of Geochemistry Fluminense Federal University (UFF) São Paulo State University (UNESP), Praça Infante Dom Henrique, s/n CAPES: 001 FAPESP: 2013/15482-0 CNPq: 308533/2018-6 CNPq: 311609/2014-7 CNPq: 455280/2014-2

Made available in DSpace on 2019-10-06T16:45:43Z (GMT). No. of bitstreams: 0 Previous issue date: 2019-01-01 Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação Cearense de Apoio ao Desenvolvimento Científico e Tecnológico In this study, the performance of two native bivalves in responding to sediment resuspension was investigated during dredging operations of a semi-arid bay (Mucuripe, NE Brazil). The clam Anomalocardia flexuosa and the oyster Crassostrea rhizophorae were selected and caged in two sites influenced by the dredging plume. We assessed the bioaccumulation of metals and hydrocarbons in both species as biomarkers of exposure and then, biomarkers’ responses were assessed in gills and digestive glands over a 28 days period, at 7 days intervals: the activities of phase I and II, and antioxidant enzymes, levels of lipid peroxidation and DNA strand breaks. Both transplanted bivalves accumulated Cu, polycyclic aromatic hydrocarbons (PAHs), and linear alkylbenzenes (LABs) in their whole-body tissues, whereas Ni, Pb and Zn accumulation was species-dependent. The exposure time set at day 28 was considered appropriate. Biomarkers exhibited time-related responses in both species, but gills exhibited a more sensitive response, indicating a function of barrier against the uptake of chemicals and also a relevant tissue to be targeted. In clams, Phase I and II enzymes (ethoxyresorufin O-deethylase and glutathione S-transferase) were induced during the period of intense dredging, while in oysters they were activated at the end of operations. Induction of antioxidant enzymes (glutathione peroxidase and glutathione reductase) and elevated levels DNA damage were observed in both exposure surveys. Clams and oysters were sensitive and responded to the exposure of resuspended sediments and the biomarkers of effects were associated with bioaccumulation of contaminants in the integrated analysis. These results indicate that The clam A. flexuosa and the oyster C. rhizophorae are suitable models to be used in monitoring programs or field exposure experiments in tropical regions. Instituto de Ciências do Mar Universidade Federal do Ceará Núcleo de Estudos em Poluição e Ecotoxicologia Aquática UNESP - São Vicente Instituto Oceanográfico Universidade de São Paulo - São Paulo Núcleo de Estudos em Poluição e Ecotoxicologia Aquática UNESP - São Vicente CNPq: 142002/2010-0 Fundação Cearense de Apoio ao Desenvolvimento Científico e Tecnológico: 1571/07 CNPq: 311609/2014-7 CNPq: 552299/2010-3 Fundação Cearense de Apoio ao Desenvolvimento Científico e Tecnológico: BMD-0008-00058.01.18/09

Seasonal distribution of Marine Litter (ML) on Santos beaches was assessed using a citizen science strategy. Plastics and cigarette butts (CB) were the dominant items in all sampling campaigns. Seasonal distribution did not result in significant differences for most items. Plastic and CB amounts were high in summer compared to autumn. For all sampled sites the presence of beach users influenced ML densities. However, results showed that some sites presented an additional influence of local hydrodynamic. Moderate amounts of hazardous items including metal, glass, CB, sanitary waste and plastic tubes used to pack and market illicit drugs represented between 20.8 and 31% of all ML over the seasons. The beaches of Santos were classified as dirty in autumn and spring and as extremely dirty in winter and summer. These findings can serve as a baseline to support mitigating actions by public authorities and start monitoring programs of ML not only in Santos but also in other urbanized beaches.

The presence of legacy contaminants in sediments from three Marine Protected Areas (MPAs) of the coast of São Paulo State was evaluated. Four sampling surveys were conducted between 2013 and 2015 in 10 sites, distributed along the Laje de Santos Marine and Xixova-Japui State Parks (PEMLS and XJSP, respectively) and Central Coast Marine Protection Area (APAMLC). Samples were analyzed for sediment texture, total organic carbon, CaCO3, metals (Al, Fe, Hg, Cd, Co, Cr, Cu, Ni, Pb and Zn), aliphatic and polycyclic aromatic hydrocarbons (AH and PAH). Sediments were generally sandy (excepting muddy samples from APAMLC), with variable amounts of TOC, OM and CaCO3. Most of the sediments exhibited low to moderate concentrations of metals, except APAMLC. Low contamination of sediments by hydrocarbons was found but samples from XLSP and APAMLC exhibited the highest concentrations of biogenic AH and PAH from pyrogenic sources. In APAMLC and PEMLS, the levels of metals can be considered as background levels according to geochemical indices (Igeo and EF). In XJSP and especially in APAMLC data indicated poor sediment quality, probably due to the effect of anthropic activities. Resumo A contaminação dos sedimentos superficiais foi avaliada neste estudo em amostras de áreas marinhas protegidas (AMP) da costa central de São Paulo. Quatro campanhas de amostragem foram feitas entre 2013 e 2015 em 10 sítios localizados nos Parques Estaduais Marinho da Laje de Santos e Xixová-Japuí (PEMLS e PEXJ, respectivamente), e Área de Proteção Ambiental Litoral Centro (APAMLC). As amostras foram analisadas quanto granulometria, carbono orgânico total, CaCO3, metais (Al, Fe, Hg, Cd, Co, Cr, Cu, Ni, Pb e Zn) e hidrocarbonetos alifáticos(AHs) e policíclicos aromáticos (PAHs). Em geral os sedimentos foram arenosos (exceto aqueles de APAMLC, que foram lamosos) e com quantidades variáveis de COT, MO e CaCO3. A maioria das amostras apresentaram baixas concentrações de metais de acordo com índices geoquímicos (Igeo e fatores de enriquecimento - FE). Baixa contaminação por hidrocarbonetos foi encontrada e em APAMLC os sedimentos apresentaram as maiores concentrações de AHs de origem biogênica e PAHs de pirogênicos. Nos sedimentos de APAMLC e PEMLS, os níveis de metais podem ser considerados como valores de referência. Já em PEXJ, os dados indicaram baixa qualidade de sedimentos, possivelmente devido às fontes antrópicas.

In this study, the quality of sediments from three Marine Protected Areas (MPAs) located on the coast of São Paulo (Laje de Santos Marine State Park - PEMLS; Xixova-Japui State Park - XJSP; and Central Coast Marine Protection Area - APAMLC) was assessed. Four sampling surveys were conducted (September/October 2013; January 2014; July 2014; January 2015). Sediment samples were collected at10 sites, distributed along the 3 MPAs. Samples were analyzed for sediment texture, total organic carbon, CaCO3, metals, aliphatic and polycyclic aromatic hydrocarbons, and for whole-sediment and sediment-water interface toxicities. Principal component analysis (PCA) was used to integrate data. Most of the sediments exhibited low concentrations of chemicals, with the exception of those from P2 (APAMLC) where moderate levels of contaminants were detected. Sediments from P7 and P9 (PEMLS) occasionally showed signs of petroleum hydrocarbons. The other sediments showed no relevant contamination but presented variable toxicity, especially those of bioclastic composition. The PCA indicated a contribution of the sediment properties to the toxicities, especially the CaCO3. In bioclastic sediments, toxicity might be due to physical causes by or any indirect factor such as the presence of ammonia. It was concluded that both natural and anthropic factors are causing toxicity in sediments from the MPAs studied. Resumo Este estudo analisou a qualidade dos sedimentos de três Áreas Marinhas Protegidas (AMP) situadas na porção central do litoral paulista (Parque Estadual Marinho da Laje de Santos - PEMLS; Parque Estadual Xixová-Japuí- PEXJ; Área de Proteção Ambiental Marinha do Litoral Centro - APAMLC). Quatro campanhas de coleta foram organizadas (Setembro/Outobro-2013; Janeiro-2014; Julho-2014; Janeiro-2015). Amostras de sedimento foram coletadas em 10 pontos ao longo das 3 AMP. As amostras foram analisadas para granulometria, carbono orgânico total, CaCO3, metais, hidrocarbonetos alifáticos e policíclico aromáticos, e toxicidade de sedimento integral e interface sedimento-água. Análise de Componentes Principais foi utilizada na integração dos dados. A maioria das amostras exibiu baixa contaminação, exceto a amostra de P2 (APAMLC) onde níveis moderados de contaminantes foram detectados. Sedimentos de P7 e P9 (PEMLS) eventualmente apresentaram sinais de hidrocarbonetos de petróleo. As demais amostras não apresentaram contaminação relevante, mas tiveram toxicidades variáveis, especialmente os sedimentos predominantemente bioclásticos. A PCA indicou forte contribuição das propriedades do sedimento, principalmente CaCO3 e amônia, na geração da toxicidade, indicando que fatores naturais e/ou antrópicos podem estar induzindo a toxicidade nas AMP estudadas.

Climate conditions and the movement of water masses are among the main factors that influence the destination of pollutants, acting upon transport and dispersion affecting, thus, the quality of water. Samples from Santos Bay were collected under normal conditions (08/21/2008) and during the entrance of a frontal system (08/22/2008) and tested for chronic ecotoxicity using fertilized eggs of sea urchin Lytechinus variegatus. Samples were toxic for stations near Xixova-Japui State Park, Port of Santos, Submarine Outfall and Moela’s Island, sites related to pollution sources. Differences in climate conditions were observed and its contribution on toxicity seemed to be significant at the entrance of Sao Vicente estuary and Moela’s Island. At the stations in Santos Bay under influence of contamination from multiple sources such as the presence of outfall and sediments disposal from dredging, the continuous release of compounds still plays an important role in environmental quality.

Made available in DSpace on 2018-11-26T17:12:16Z (GMT). No. of bitstreams: 0 Previous issue date: 2016-12-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Government of Andalusia, Spain European Regional Development Fund (ERDF) The marine amphipod Ampelisca brevicornis was used as model organism of benthic macrofauna to assess the possible adverse effects of pharmaceuticals bound to sediments. Organisms were exposed to sediment spiked with novobiocin (NOV) and methotrexate (MTX) for 10 days in order to estimate the acute toxicity (lethal effects) produced by the two compounds. The surviving organisms were pooled and analyzed to determine their sublethal responses associated with different phases of metabolism (enzyme activities in phases I and II), oxidative stress (antioxidant enzyme activities and lipid peroxidation), and genotoxicity (DNA damage in the form of strand breaks). No lethal or sublethal effects were observed in the amphipods exposed to NOV. For organisms exposed to sediments spiked with MTX the results were found to calculate the concentration that was lethal to 50% of the organisms exposed in the toxicity tests (LC50 of 30.36 ng/g). MTX also induced the metabolism of enzyme detoxification activities in phases I and II. Oxidative stress and DNA damage in particular were also observed, indicating responses associated with MTX's mechanism of action. Both mortality and the set of applied biomarkers allowed for the assessment of bioavailability, oxidative stress, and genotoxicity of NOV and MTX. The information obtained in this investigation can assist in ecological risk assessment of marine sediments contaminated by pharmaceuticals. (C) 2016 Elsevier Ltd. All rights reserved. Sao Paulo State Univ Julio de Mesquita Filho, Biosci Inst, Pca Infante D Henrique, BR-11330900 Sao Vicente, Brazil Univ Fed Ceara, Inst Marine Sci, BR-60165081 Fortaleza, Ceara, Brazil Univ Cadiz, Dept Phys Chem, Fac Marine & Environm Sci, Cadiz 11510, Spain Sao Paulo State Univ Julio de Mesquita Filho, Biosci Inst, Pca Infante D Henrique, BR-11330900 Sao Vicente, Brazil CAPES: 5133/11-4 CAPES: BEX 0362/10-7 Government of Andalusia, Spain: P09-RNM-5136

This study aimed to evaluate the environmental quality of the marine portion of Xixova-Japui State Park (XJSP), an urban marine protected area, which is influenced by multiple contamination sources, by using ecotoxicological and geochemical analyses. Sediments were predominantly sandy, with low CaCO3 and organic matter contents, and presented contamination by metals (Cd, Cu, Zn). Acute toxicity was detected in three tested samples, and copepod exposed to sediments from four stations exhibited lower fecundities, despite the absence of significant effects. Contamination and toxicity seemed to be associated, suggesting that the environment is degraded and presents risks to the biota. Whole sediment TIE indicated ammonia as a main responsible for toxicity, suggesting sewage is a main contributor to sediment degradation. As external contamination sources seem to be negatively influencing the sediment quality, the park conservation objectives are not being fully reached, demanding actions to mitigate impacts.

Submitted by Guilherme Lemeszenski (guilherme@nead.unesp.br) on 2013-08-22T18:43:46Z No. of bitstreams: 1 S1679-87592010000700011.pdf: 61956 bytes, checksum: fcdc6ce87c2e044a8a8af744be8588d9 (MD5) Made available in DSpace on 2013-08-22T18:43:46Z (GMT). No. of bitstreams: 1 S1679-87592010000700011.pdf: 61956 bytes, checksum: fcdc6ce87c2e044a8a8af744be8588d9 (MD5) Previous issue date: 2010-06-01 Made available in DSpace on 2013-09-30T17:41:33Z (GMT). No. of bitstreams: 2 S1679-87592010000700011.pdf: 61956 bytes, checksum: fcdc6ce87c2e044a8a8af744be8588d9 (MD5) S1679-87592010000700011.pdf.txt: 27786 bytes, checksum: 16c167b2d5e3ce2a437e4dd048347001 (MD5) Previous issue date: 2010-06-01 Submitted by Vitor Silverio Rodrigues (vitorsrodrigues@reitoria.unesp.br) on 2014-05-20T13:12:25Z No. of bitstreams: 2 S1679-87592010000700011.pdf: 61956 bytes, checksum: fcdc6ce87c2e044a8a8af744be8588d9 (MD5) S1679-87592010000700011.pdf.txt: 27786 bytes, checksum: 16c167b2d5e3ce2a437e4dd048347001 (MD5) Made available in DSpace on 2014-05-20T13:12:25Z (GMT). No. of bitstreams: 2 S1679-87592010000700011.pdf: 61956 bytes, checksum: fcdc6ce87c2e044a8a8af744be8588d9 (MD5) S1679-87592010000700011.pdf.txt: 27786 bytes, checksum: 16c167b2d5e3ce2a437e4dd048347001 (MD5) Previous issue date: 2010-06-01 Alterações hematológicas em peixes são consideradas uma importante ferramenta para avaliar processos patológicos decorrentes da exposição a poluentes ambientais. Micropogonias furnieri (Desmarest, 1823) (corvina) é comumente encontrada em regiões estuarinas e eventualmente está exposta a inúmeros contaminantes. No presente estudo foi avaliado o quadro hematológico de indivíduos de M. furnieri coletados na Baixada Santista: o Sistema Estuarino de Santos, considerado poluído, e o estuário do Rio Itanhaém (controle). Foram avaliados o número de Eritrócitos (Er), o Hematócrito (Ht), a taxa de Hemoglobina (Hb), o Volume Corpuscular Médio (VCM) e a Concentração de Hemoglobina Corpuscular Média (CHCM). Nos peixes coletados no Sistema Estuarino de Santos, os níveis de Ht foram significativamente menores, enquanto os níveis de CHCM e Hb foram significativamente mais altos, indicando que os prováveis efeitos estejam atribuídos aos diferentes níveis de contaminação encontrados nos estuários. Hematological alterations in fish are considered a useful tool to evaluate pathological processes resulting from the exposure to environmental pollutants. The whitemouth croaker Micropogonias furnieri is a common species in estuarine areas and potentially exposed to many contaminants. In the present study, the hematological characteristics of fish collected at two sites in Baixada Santista (Santos Estuarine System - SES, a polluted site; and the Estuary of Itanhaém River - EIR, unpolluted site) del was analysed. The following blood descriptors were analyzed: number of Erythrocytes (Er), Hematocrit (Ht), Hemoglobin (Hb), Mean Corpuscular Volume (MCV) and Mean Corpuscular Hemoglobin concentration (MCHC). Fish from SES exhibited significant lower levels of Ht and increase on MCHC and Hb. Such differences are likely related to the different contamination levels found in these estuaries. Universidade Estadual Paulista Júlio de Mesquita Filho Campus Experimental do Litoral Paulista Universidade Federal do Ceará (UFC) Instituto de Ciências do Mar Universidade Santa Cecília Universidade de São Paulo Instituto Oceanográfico Instituto de Pesca Laboratório de Patologia de Organismos Aquáticos Universidade Estadual Paulista Júlio de Mesquita Filho Campus Experimental do Litoral Paulista

The present study aimed to assess the sediment quality in a tropical estuary located in the northeast of Brazil under semi-arid conditions and multiple sources of contamination, using both toxicity bioassays and metal distribution. The metal distribution followed a concentration gradient decreasing one order of magnitude from the inner station toward the outer estuary, with amounts in the following order: Fe > Al > Zn > Cr > Pb > Cu. The index of geoaccumulation indicated a metal enrichment in the Ceara river sediment, mainly at inner sites, considered from moderately to strongly contaminated by Al, Cu, Cr and Zn. Sediment samples were considered toxic by means of whole sediment tests with copepods (reproduction) and amphipods (survival), and also elutriate fraction and sediment-water interface with sea urchin embryos (development). Acute and chronic toxicity did not exhibit a significant correlation with metals, emphasizing the influence of other contaminants mainly related to the pollution sources installed in the mid-estuary.

The present study reports the use of biomarkers analyzes in mangrove root crab Goniopsis cruentata tissues to assess the environmental quality of two tropical estuarine areas. Animals from Ceara River estuary presented inhibition of ChE and GST enzymatic activities and higher rates of DNA damage with respect to those sampled in a pristine environment. G. cruentata appears to represent a proper species to monitor the quality of tropical estuaries. Since Ceara River is a legally protected area, this survey highlight the needs to implement actions to control pollution loads and improve the protection of natural ecosystems and resources.