The dynamics of fluorescent dissolved organic matter in the Paranaguá estuarine system, Southern Brazil

O objetivo deste estudo foi investigar a dinâmica da matéria orgânica fluorescente (FMOD) no Complexo Estuarino de Paranaguá (CEP) para inferir sobre a contribuição da FMOD alóctone nas águas estuarinas em relação à condição de maré e estações do ano (seca e chuvosa). Empregou-se a técnica de espectroscopia de fluorescência, através da utilização de dois comprimentos de onda de excitação, os quais correspondem a duas classes conhecidas de fluoróforos, λex 350 nm e λex 450 nm, para desta forma determinar o comprimento de onda de máxima emissão (λem) da fluorescência da MOD. Relações entre λem e variáveis ambientais e a relevância das relações nas diferentes condições de maré (sizígia e quadratura) e estações do ano (seca e chuvosa) foram identificadas com o uso de análise de componentes principais. Os resultados demonstraram que a primeira classe de fluoróforos (λex 350 nm) foi alterada durante a transição rio estuário, enquanto a segunda classe (λex 450 nm) apresentou um comportamento mais conservativo. A contribuição da MOD alóctone no estuário foi intensificada durante a estação chuvosa, especialmente durante as marés de sizígia, enquanto na estação seca a MOD autóctone é preponderante na composição da MOD total no CEP. Conclui-se que a variação nos λem da primeira classe de fluoróforos (λex 350 nm) é principalmente relacionada à contribuição alóctone, enquanto as diferenças nos λem da segunda classe (λex 450 nm) estão relacionadas com as flutuações nas contribuições das diferentes fontes de MOD no CEP.The aim of this study was to investigate the dynamics of the fluorescent dissolved organic matter (FDOM) in Paranaguá Estuarine System (PES) as to infer about the contribution of allochthonous FDOM to the estuarine waters in relation to tidal condition and seasons. Fluorescence spectroscopy was used for such purpose and DOM characterization through fluorescence emission was performed using excitation wavelengths of λex 350 nm and λex 450 nm, the two main fluorescence groups known to be present in natural DOM. Relations between emission wavelength (λem) and environmental variables, and the relevance of these variables to the different tides and seasons were identified by principal component analysis. The results showed that the first class of fluorophores (λex 350 nm) changed from the river (freshwater) towards the estuary, whilst the second class (λex 450 nm) has a more conservative nature and does not change as significantly as the first. Allochthonous DOM contribution to the estuarine system is intensified during the rainy season, especially in spring tides, whereas in the dry season the ratio of autochthonous DOM to total DOM in PES waters increased. We concluded that the variation of maximum λem of the first class of fluorophores (λex 350 nm) is mainly related to allochthonous contribution, whilst the maximum of emission for the second class of fluorophores (λex 450 nm) is dependent on the contribution of the different sources of organic matter (freshwater and marine water DOM contribution)

The dynamics of fluorescent dissolved organic matter in the Paranaguá estuarine system, Southern Brazil

The aim of this study was to investigate the dynamics of the fluorescent dissolved organic matter (FDOM) in Paranagua Estuarine System (PES) as to infer about the contribution of allochthonous FDOM to the estuarine waters in relation to tidal condition and seasons. Fluorescence spectroscopy was used for such purpose and DOM characterization through fluorescence emission was performed using excitation wavelengths of lambda ex 350 nm and lambda ex 450 nm, the two main fluorescence groups known to be present in natural DOM. Relations between emission wavelength (lambda em) and environmental variables, and the relevance of these variables to the different tides and seasons were identified by principal component analysis. The results showed that the first class of fluorophores (lambda ex 350 nm) changed from the river (freshwater) towards the estuary, whilst the second class (lambda ex 450 nm) has a more conservative nature and does not change as significantly as the first. Allochthonous DOM contribution to the estuarine system is intensified during the rainy season, especially in spring tides, whereas in the dry season the ratio of autochthonous DOM to total DOM in PES waters increased. We concluded that the variation of maximum lambda em of the first class of fluorophores (lambda ex 350 nm) is mainly related to allochthonous contribution, whilst the maximum of emission for the second class of fluorophores (lambda ex 450 nm) is dependent on the contribution of the different sources of organic matter (freshwater and marine water DOM contribution).Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Univ Fed Parana, Programa Posgrad Ecol & Conservacao, Setor Ciencias Biol, BR-81531980 Curitiba, Parana, BrazilUniv Santa Cecilia, Dept Ecotoxicol, BR-11045907 Santos, SP, BrazilUniv Fed Sao Paulo, BR-11060000 Santos, SP, BrazilUniv Fed Sao Carlos, Dept Bot, BR-13565905 Sao Carlos, SP, BrazilUniv Fed Parana, Ctr Estudos Mar, BR-83255971 Pontal Do Parana, PR, BrazilUniv Fed Sao Paulo, BR-11060000 Santos, SP, BrazilCNPq: 472509/2006-3CNPq: 314361/2009-0Web of Scienc

Uso de bagre amarelo (Cathorops spixii) como modelo biológico de exposição e efeito de contaminantes no complexo estuarino-lagunar Cananéia-Iguape-Peruíbe

Orientador : Prof. Dr. Ciro Alberto de Oliveira RibeiroCo-orientador : Prof. Dr. Denis Moledo de Sousa AbessaTese (doutorado) - Universidade Federal do Paraná, Setor de Ciências Biológicas, Programa de Pós-Graduação em Ecologia e Conservação. Defesa: Curitiba, 27/03/2015Inclui referências : f. 175-187Resumo: Diversas áreas protegidas marinhas e estuarinas (AMP) apresentam níveis moderados de contaminação porém, nestas áreas, as respostas biológicas nem sempre são evidentes. Desta forma, as avaliações de risco ambiental não devem se restringir às analises químicas do sedimento, mas também se faz necessário avaliar parâmetros biológicos que sejam capazes de indicar precocemente os potenciais efeitos de xenobióticos, como os biomarcadores. O primeiro objetivo deste trabalho foi utilizar um conjunto de biomarcadores bioquímicos (GPx, GST, GSH, danos em DNA, LPO, AChE) e somáticos (fator de condição) em diferentes órgãos-alvo (fígado, rim e brânquias) da espécie de peixe Cathorops spixii, e relacionar com os níveis de metais e As bioacumulados nos tecidos e com os hidrocarbonetos policíclicos aromáticos (PAHs) presentes na bile. Assim, foi avaliada a qualidade do ambiente aquático da AMP de Cananéia-Iguape-Peruíbe (APA-CIP) exposta a atividades de mineração pretérita e assentamentos urbanos. O segundo objetivo foi aplicar diferentes ferramentas moleculares e estruturais para investigar possíveis efeitos genotóxicos em C. spixii coletados na APA-CIP. Já o terceiro objetivo foi avaliar as correspondências, complementaridades ou conflitos entre as várias linhas de evidência na qualidade do sedimento da APA-CIP. Nestas análises são incluídos biomarcadores, biacumulação e linhas-de-evidência ?clássicas?, através de uma abordagem de ?peso de evidências?. O quarto objetivo foi estimar o potencial risco de exposição para a saúde humana através do consumo de C. spixii provenientes da APA-CIP. Os resultados confirmaram a utilidade do uso de biomarcadores na avaliação da biota exposta às fontes de poluição localizadas ao longo da APA-CIP. O fígado foi o órgão considerado mais sensível em termos de resposta subcelular, enquanto que as brânquias foram mais sensíveis para avaliar os biomarcadores de efeito. Os resultados indicaram que a APA-CIP é influenciada por duas fontes de contaminação: descargas provenientes do rio Ribeira de Iguape (RIR) e de áreas urbanas da cidade de Cananéia. Os resultados observados apartir do uso de diferentes ferramentas na avaliação da genotoxicidade mostraram que micronúcleos e alterações nucleares estão mais associadas com os níveis de metais bioacumulados nos tecidos do que as análises de danos em DNA. A aplicação dos índices de biomarcadores dentro de uma abordagem de peso-de-evidências mostrou que os índices que incorporam as lesões histopatológicas em C. spixii foram melhor associados com a toxicidade do sedimento, enquanto que os índices de biomarcadores, que incluem apenas as respostas subcelulares e celulares, foram melhor associados com níveis de metais bioacumulados. Os níveis de metais e As no músculo e fígado não se associaram com os níveis de contaminantes nos sedimentos, sugerindo diferentes níveis de biodisponibilidade para C. spixii ou a um mecanismo celular de eliminação destes compostos. As concentrações de Cd, Pb e As encontradas no músculo de C. spixii foram superiores aos níveis máximos permitidos para o consumo humano. Desta forma, o estudo mostra que existe risco de exposição para populações humanas e que mais atenção deve ser dirigida à proteção das AMPs, a fim de minimizar os riscos para a biota residente e para população humana. Palavras chave: biomonitoramento, ?peso-de-evidência?; qualidade do sedimento; qualidade de água, biomarcadores; avaliação de risco ambiental; risco a saúde humanaAbstract: Many marine and estuarine protected areas present moderate levels of contamination therefore biological responses are not so evident. Thus, environmental risk assessments should not be restricted to chemical sediment analysis, but it is also necessary to evaluate biological parameters that are able to early indicate the potential effects of xenobiotics, such as biomarkers. The first aim of current work was to investigate the role of a set of biomarkers (GPx, GST, GSH, DNA damage, LPO, AChE and condition index) in different target organs (liver, kidney and gills) of a demersal fish (Cathorops spixii) and its relationship with contaminants (metal body burdens on liver and muscle tissues and PAHs in bile), in order to assess the environmental quality of the Marine Protected Area of Cananéia-Iguape-Peruíbe (APA-CIP), affected by former mining activities and urban settlements. The second goal was to use different structural and molecular tools to detect possible genotoxic effects in C. spixii from the APA-CIP. The third aim was to assess correspondences, complementarity, or conflicts among multiple sediment quality LOEs, including biomarkers analyzes, through a WOE sediment-quality assessment. The fourth aim was to estimate the potential risk of the consumption of C. spixii from APA-CIP for human health. The results confirmed the usefulness of the biomarker approach for the identification of both seasonal and spatial variations in pollution sources around APA-CIP. The liver was found to be more responsive in terms of its antioxidant responses, whereas gills were found to be more responsive to biomarkers of effect. APA-CIP seems to be influenced by two sources of contamination: Ribeira de Iguape River (RIR) mouth and urban areas of Cananéia city. The results of different genotoxicity responses showed that micronucleus and nuclear alterations were more frequently associated with the metal body burdens than the analyses of DNA damage, which suggests that the first analyses are less vulnerable to the effects of confounding factors in mildly contaminated areas. The used of biomarker indices within a WOE approach showed that the biomarker index that incorporates histopathological lesions in resident fish was better associated with sediment toxicity and contamination, whereas the biomarker indices that included only sub-cellular and cellular responses were better associated with metals and As body burdens. Metals and As burdens in muscle or liver tissue, in turn, did not associate with sediment levels of these contaminants, suggesting that C. spixii have a mechanism of internal metal regulation. Cd, Pb, and As were found at concentrations above action levels for human consumption. The study of the risk of C. spixii consumption showed that, depending on the level of exposure of the local population, the levels of metals and As in C. spixii pose risk to human health. Taken altogether, the results of this study showed that more attention should be directed to the protection of MPA in order to minimize risks to the resident biota and sensitive human population. Key words: weight-of-evidence; factor analysis; sediment quality; histopathology; antioxidant responses; genotoxicity; environmental risk assessment, human health ris

Uso de bagre amarelo (Cathorops spixii) como modelo biológico de exposição e efeito de contaminantes no complexo estuarino-lagunar Cananéia-Iguape-Peruíbe

Orientador : Prof. Dr. Ciro Alberto de Oliveira RibeiroCo-orientador : Prof. Dr. Denis Moledo de Sousa AbessaTese (doutorado) - Universidade Federal do Paraná, Setor de Ciências Biológicas, Programa de Pós-Graduação em Ecologia e Conservação. Defesa: Curitiba, 27/03/2015Inclui referências : f. 175-187Resumo: Diversas áreas protegidas marinhas e estuarinas (AMP) apresentam níveis moderados de contaminação porém, nestas áreas, as respostas biológicas nem sempre são evidentes. Desta forma, as avaliações de risco ambiental não devem se restringir às analises químicas do sedimento, mas também se faz necessário avaliar parâmetros biológicos que sejam capazes de indicar precocemente os potenciais efeitos de xenobióticos, como os biomarcadores. O primeiro objetivo deste trabalho foi utilizar um conjunto de biomarcadores bioquímicos (GPx, GST, GSH, danos em DNA, LPO, AChE) e somáticos (fator de condição) em diferentes órgãos-alvo (fígado, rim e brânquias) da espécie de peixe Cathorops spixii, e relacionar com os níveis de metais e As bioacumulados nos tecidos e com os hidrocarbonetos policíclicos aromáticos (PAHs) presentes na bile. Assim, foi avaliada a qualidade do ambiente aquático da AMP de Cananéia-Iguape-Peruíbe (APA-CIP) exposta a atividades de mineração pretérita e assentamentos urbanos. O segundo objetivo foi aplicar diferentes ferramentas moleculares e estruturais para investigar possíveis efeitos genotóxicos em C. spixii coletados na APA-CIP. Já o terceiro objetivo foi avaliar as correspondências, complementaridades ou conflitos entre as várias linhas de evidência na qualidade do sedimento da APA-CIP. Nestas análises são incluídos biomarcadores, biacumulação e linhas-de-evidência ?clássicas?, através de uma abordagem de ?peso de evidências?. O quarto objetivo foi estimar o potencial risco de exposição para a saúde humana através do consumo de C. spixii provenientes da APA-CIP. Os resultados confirmaram a utilidade do uso de biomarcadores na avaliação da biota exposta às fontes de poluição localizadas ao longo da APA-CIP. O fígado foi o órgão considerado mais sensível em termos de resposta subcelular, enquanto que as brânquias foram mais sensíveis para avaliar os biomarcadores de efeito. Os resultados indicaram que a APA-CIP é influenciada por duas fontes de contaminação: descargas provenientes do rio Ribeira de Iguape (RIR) e de áreas urbanas da cidade de Cananéia. Os resultados observados apartir do uso de diferentes ferramentas na avaliação da genotoxicidade mostraram que micronúcleos e alterações nucleares estão mais associadas com os níveis de metais bioacumulados nos tecidos do que as análises de danos em DNA. A aplicação dos índices de biomarcadores dentro de uma abordagem de peso-de-evidências mostrou que os índices que incorporam as lesões histopatológicas em C. spixii foram melhor associados com a toxicidade do sedimento, enquanto que os índices de biomarcadores, que incluem apenas as respostas subcelulares e celulares, foram melhor associados com níveis de metais bioacumulados. Os níveis de metais e As no músculo e fígado não se associaram com os níveis de contaminantes nos sedimentos, sugerindo diferentes níveis de biodisponibilidade para C. spixii ou a um mecanismo celular de eliminação destes compostos. As concentrações de Cd, Pb e As encontradas no músculo de C. spixii foram superiores aos níveis máximos permitidos para o consumo humano. Desta forma, o estudo mostra que existe risco de exposição para populações humanas e que mais atenção deve ser dirigida à proteção das AMPs, a fim de minimizar os riscos para a biota residente e para população humana. Palavras chave: biomonitoramento, ?peso-de-evidência?; qualidade do sedimento; qualidade de água, biomarcadores; avaliação de risco ambiental; risco a saúde humanaAbstract: Many marine and estuarine protected areas present moderate levels of contamination therefore biological responses are not so evident. Thus, environmental risk assessments should not be restricted to chemical sediment analysis, but it is also necessary to evaluate biological parameters that are able to early indicate the potential effects of xenobiotics, such as biomarkers. The first aim of current work was to investigate the role of a set of biomarkers (GPx, GST, GSH, DNA damage, LPO, AChE and condition index) in different target organs (liver, kidney and gills) of a demersal fish (Cathorops spixii) and its relationship with contaminants (metal body burdens on liver and muscle tissues and PAHs in bile), in order to assess the environmental quality of the Marine Protected Area of Cananéia-Iguape-Peruíbe (APA-CIP), affected by former mining activities and urban settlements. The second goal was to use different structural and molecular tools to detect possible genotoxic effects in C. spixii from the APA-CIP. The third aim was to assess correspondences, complementarity, or conflicts among multiple sediment quality LOEs, including biomarkers analyzes, through a WOE sediment-quality assessment. The fourth aim was to estimate the potential risk of the consumption of C. spixii from APA-CIP for human health. The results confirmed the usefulness of the biomarker approach for the identification of both seasonal and spatial variations in pollution sources around APA-CIP. The liver was found to be more responsive in terms of its antioxidant responses, whereas gills were found to be more responsive to biomarkers of effect. APA-CIP seems to be influenced by two sources of contamination: Ribeira de Iguape River (RIR) mouth and urban areas of Cananéia city. The results of different genotoxicity responses showed that micronucleus and nuclear alterations were more frequently associated with the metal body burdens than the analyses of DNA damage, which suggests that the first analyses are less vulnerable to the effects of confounding factors in mildly contaminated areas. The used of biomarker indices within a WOE approach showed that the biomarker index that incorporates histopathological lesions in resident fish was better associated with sediment toxicity and contamination, whereas the biomarker indices that included only sub-cellular and cellular responses were better associated with metals and As body burdens. Metals and As burdens in muscle or liver tissue, in turn, did not associate with sediment levels of these contaminants, suggesting that C. spixii have a mechanism of internal metal regulation. Cd, Pb, and As were found at concentrations above action levels for human consumption. The study of the risk of C. spixii consumption showed that, depending on the level of exposure of the local population, the levels of metals and As in C. spixii pose risk to human health. Taken altogether, the results of this study showed that more attention should be directed to the protection of MPA in order to minimize risks to the resident biota and sensitive human population. Key words: weight-of-evidence; factor analysis; sediment quality; histopathology; antioxidant responses; genotoxicity; environmental risk assessment, human health ris

Sediment toxicity identification evaluation (TIE phases I and II) based on microscale bioassays for diagnosing causes of toxicity in coastal areas affected by domestic sewage

Domestic sewage is a major problem in highly urbanized coastal areas worldwide. In the present study, toxicity identification evaluation (TIE) phases I and II were applied to sediment interstitial water from 2 locations along the Sao Paulo coast in southeastern Brazil: the sewage outfalls from the city of Santos, a densely urbanized area, and the city of Bertioga, a less urbanized area. An adapted microscale sea urchin embryo-larval development bioassay was employed. Phase TIE-I manipulations were 1) ethylenediamine tetraacetic acid (EDTA) addition, 2) aeration at modified pH, 3) C18 solid-phase extraction (SPE), and 4) addition of Na2S2O3. The results of the Santos TIE-I indicated toxicity by sulfides and substances with affinity to C18 resin. In Bertioga, toxicity was the result of NH3, metals, and arsenic, as well as substances with affinity to C18 resin. Phase TIE-II aimed to specify the causes of toxicity by testing the toxicity of eluates of the sublation and C18 SPE manipulation. The results reinforced the role of both surfactants and nonpolar compounds as causative agents of toxicity in both Santos and Bertioga. Chemical analyses of sediment interstitial water or whole sediment ruled out the influence of polycyclic aromatic hydrocarbons (PAHs) or polychlorinated biphenyls (PCBs) in the toxicity of both sampling sites. Other hydrophobic substances may play a role in the toxicity of Santos and Bertioga effluents. Efforts to remove such substances from sanitary effluents must be prioritized. (C) 2017 SETACConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Univ Santa Cecilia, Dept Ecotoxicol, Sao Paulo, BrazilFed Univ Sao Paulo UNIFESP, Grad Program Integrated Environm Anal, Sao Paulo, BrazilFed Univ Parana UFPR, Dept Cellular Biol, Cellular Toxicol Lab, Curitiba, Parana, BrazilSao Paulo State Univ, Lab Study Aquat Pollut & Ecotoxicol NEPEA, Sao Vicente Campus UNESP,Campus Litoral Paulista, Sao Paulo, BrazilFed Univ Sao Paulo UNIFESP, Dept Marine Sci, Campus Baixada Santista, Sao Paulo, BrazilFed Univ Sao Paulo UNIFESP, Grad Program Integrated Environm Anal, Sao Paulo, BrazilFed Univ Sao Paulo UNIFESP, Dept Marine Sci, Campus Baixada Santista, Sao Paulo, BrazilCNPq: 486350/2013-4CNPq: 308079/2015-9FAPESP: 2015/00030-2Web of Scienc

Can leachates of environmentally relevant concentrations of microplastics in marine sediments affect the reproduction of an epibenthic copepod?

Most studies on the effects of microplastics on marine biota are carried out using unrealistically high concentrations. Moreover, although microplastics are capable of carrying toxic substances and thus can cause adverse effects even without coming into direct contact with organisms, little is known about the effects of not accessible for ingestion microplastics on benthic biota. Considering that the presence of microplastic particles can itself cause effects to the biota due to toxic substances leached, the present study evaluated the ecotoxicological effects of microplastic leachates of virgin and beach stranded in marine sediments (whole sediments and elutriates) on the epibenthic copepod Nitokra sp. (size 3 ± 1 mm). Effects on reproduction were evaluated using clean sediment enriched with environmentally relevant concentrations [1 pellet: 46.67g sediment (Low) and 1 pellet: 1.67g sediment (High)] of two types of plastic pellets (size 4 ± 1 mm) (i) virgin (obtained from the manufacturer) or (ii) stranded (collected from Santos beach, São Paulo, Brazil, a highly urbanized beach). The results of the present study showed that microplastics leachate (virgin or from the environment) did not cause an inhibiting effect on reproduction in Nitokra sp. in any of the scenarios tested. These results contribute to further risk assessments of plastic particles for marine biota.Most studies on the effects of microplastics on marine biota are carried out using unrealistically high concentrations. Moreover, although microplastics are capable of carrying toxic substances and thus can cause adverse effects even without coming into direct contact with organisms, little is known about the effects of not accessible for ingestion microplastics on benthic biota. Considering that the presence of microplastic particles can itself cause effects to the biota due to toxic substances leached, the present study evaluated the ecotoxicological effects of microplastic leachates of virgin and beach stranded in marine sediments (whole sediments and elutriates) on the epibenthic copepod Nitokra sp. (size 3 ± 1 mm). Effects on reproduction were evaluated using clean sediment enriched with environmentally relevant concentrations [1 pellet: 46.67g sediment (Low) and 1 pellet: 1.67g sediment (High)] of two types of plastic pellets (size 4 ± 1 mm) (i) virgin (obtained from the manufacturer) or (ii) stranded (collected from Santos beach, São Paulo, Brazil, a highly urbanized beach). The results of the present study showed that microplastics leachate (virgin or from the environment) did not cause an inhibiting effect on reproduction in Nitokra sp. in any of the scenarios tested. These results contribute to further risk assessments of plastic particles for marine biota

A reply to -Reviewing the effects of contamination on the biota of Brazilian coastal ecosystems: Scientific challenges for a developing country in a changing world

A reply to “Reviewing the effects of contamination on the biota of Brazilian coastal ecosystems: Scientific challenges for a developing country in a changing world”Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)FAPESP: 2020/00068-8FAPESP: 2021/08471-