Physiological Effects of Five Different Marine Natural Organic Matters (NOMs) and Three Different Metals (Cu, Pb, Zn) on Early Life Stages of the Blue Mussel (Mytilus galloprovincialis)

Metals are present in aquatic environments as a result of natural and anthropogenic inputs, and may induce toxicity to organisms. One of the main factors that influence this toxicity in fresh water is natural organic matter (NOM) but all NOMs are not the same in this regard. In sea water, possible protection by marine NOMs is not well understood. Thus, our study isolated marine NOMs by solid-phase extraction from five different sites and characterized them by excitation-emission fluorescence analysis—one inshore (terrigenous origin), two offshore (autochthonous origin), and two intermediate in composition (indicative of a mixed origin). The physiological effects of these five NOMS alone (at 8 mg/L), of three metals alone (copper, lead and zinc at 6 µg Cu/L, 20 µg Pb/L, and 25 µg Zn/L respectively), and of each metal in combination with each NOM, were evaluated in 48-h exposures of mussel larvae. Endpoints were whole body Ca2++Mg2+-ATPase activity, carbonic anhydrase activity and lipid peroxidation. By themselves, NOMs increased lipid peroxidation, Ca2++Mg2+-ATPase, and/or carbonic anhydrase activities (significant in seven of 15 NOM-endpoint combinations), whereas metals by themselves did not affect the first two endpoints, but Cu and Pb increased carbonic anhydrase activities. In combination, the effects of NOMs predominated, with the metal exerting no additional effect in 33 out of 45 combinations. While NOM effects varied amongst different isolates, there was no clear pattern with respect to optical or chemical properties. When NOMs were treated as a single source by data averaging, NOM had no effect on Ca2++Mg2+-ATPase activity but markedly stimulated carbonic anhydrase activity and lipid peroxidation, and there were no additional effects of any metal. Our results indicate that marine NOMs may have direct effects on this model marine organism, as well as protective effects against metal toxicity, and the quality of marine NOMs may be an important factor in these actions

Physiological effects of five different marine natural organic matters (NOMs) and three different metals (Cu, Pb, Zn) on early life stages of the blue mussel (Mytilus galloprovincialis)

Metals are present in aquatic environments as a result of natural and anthropogenic inputs, and may induce toxicity to organisms. One of the main factors that influence this toxicity in fresh water is natural organic matter (NOM) but all NOMs are not the same in this regard. In sea water, possible protection by marine NOMs is not well understood. Thus, our study isolated marine NOMs by solid-phase extraction from five different sites and characterized them by excitation-emission fluorescence analysis—one inshore (terrigenous origin), two offshore (autochthonous origin), and two intermediate in composition (indicative of a mixed origin). The physiological effects of these five NOMS alone (at 8 mg/L), of three metals alone (copper, lead and zinc at 6 µg Cu/L, 20 µg Pb/L, and 25 µg Zn/L respectively), and of each metal in combination with each NOM, were evaluated in 48-h exposures of mussel larvae. Endpoints were whole body Ca2++Mg2+-ATPase activity, carbonic anhydrase activity and lipid peroxidation. By themselves, NOMs increased lipid peroxidation, Ca2++Mg2+-ATPase, and/or carbonic anhydrase activities (significant in seven of 15 NOM-endpoint combinations), whereas metals by themselves did not affect the first two endpoints, but Cu and Pb increased carbonic anhydrase activities. In combination, the effects of NOMs predominated, with the metal exerting no additional effect in 33 out of 45 combinations. While NOM effects varied amongst different isolates, there was no clear pattern with respect to optical or chemical properties. When NOMs were treated as a single source by data averaging, NOM had no effect on Ca2++Mg2+-ATPase activity but markedly stimulated carbonic anhydrase activity and lipid peroxidation, and there were no additional effects of any metal. Our results indicate that marine NOMs may have direct effects on this model marine organism, as well as protective effects against metal toxicity, and the quality of marine NOMs may be an important factor in these actions

An Extensive Quality Control and Quality Assurance (QC/QA) Program Significantly Improves Inter-Laboratory Concordance Rates of Flow-Cytometric Minimal Residual Disease Assessment in Acute Lymphoblastic Leukemia: An I-BFM-FLOW-Network Report

Monitoring of minimal residual disease (MRD) by flow cytometry (FCM) is a powerful prognostic tool for predicting outcomes in acute lymphoblastic leukemia (ALL). To apply FCM-MRD in large, collaborative trials, dedicated laboratory staff must be educated to concordantly high levels of expertise and their performance quality should be continuously monitored. We sought to install a unique and comprehensive training and quality control (QC) program involving a large number of reference laboratories within the international Berlin-Frankfurt-Münster (I-BFM) consortium, in order to complement the standardization of the methodology with an educational component and persistent quality control measures. Our QC and quality assurance (QA) program is based on four major cornerstones: (i) a twinning maturation program, (ii) obligatory participation in external QA programs (spiked sample send around, United Kingdom National External Quality Assessment Service (UK NEQAS)), (iii) regular participation in list-mode-data (LMD) file ring trials (FCM data file send arounds), and (iv) surveys of independent data derived from trial results. We demonstrate that the training of laboratories using experienced twinning partners, along with continuous educational feedback significantly improves the performance of laboratories in detecting and quantifying MRD in pediatric ALL patients. Overall, our extensive education and quality control program improved inter-laboratory concordance rates of FCM-MRD assessments and ultimately led to a very high conformity of risk estimates in independent patient cohorts

Efeitos da matéria orgânica dissolvida na acumulação e toxicidade aguda do cobre no marisco Mesodesma mactroides

Dissertação (mestrado)-Universidade Federal do Rio Grande, Programa de Pós-Graduação em Ciências Fisiológicas – Fisiologia Animal Comparada, Instituto de Ciências Biológicas, 2009.No presente estudo foram avaliados os efeitos da matéria orgânica dissolvida (MOD) de duas diferentes fontes naturais sobre a acumulação tecidual e a toxicidade aguda do cobre no marisco Mesodesma mactroides em água do mar. Também foi analisada a especiação e o fracionamento das espécies de cobre nos meios experimentais. Na ausência de cobre, a MOD (até 10.5 mg C/L) não afetou a sobrevivência dos mariscos. A toxicidade do cobre dissolvido (CL50-96h) também não foi alterada pela concentração de MOD na água do mar. Entretanto, as toxicidades baseadas na concentração e atividade do cobre livre foram dependentes da concentração de MOD, sendo menores em baixa concentração (0.60 mg C/L) e maiores em altas concentrações (6.65 e 10.50 mg C/L). O cobre acumulado que induziu um efeito tóxico similar, isto é 50% mortalidade, foi reduzido igualmente na presença de diferentes concentrações de MOD. Não foi observada correlação entre a concentração de MOD e a acumulação ou toxicidade do cobre. As concentrações das frações tóxicas de cobre (Cu2+,CuOH+ and Cu (OH)2(aq)) e suas atividades (Cu2+ and CuOH+) diminuíram com o aumento da concentração de MOD, sendo estas acompanhadas de um aumento na percentagem de cobre ligado aos grupos carboxílicos e fenólicos da MOD. Estes resultados indicam que baixas concentrações de MOD protegem contra a toxicidade aguda do cobre, enquanto altas concentrações aumentam a toxicidade do metal. Esta maior toxicidade parece ser devida a um aumento na concentração de espécies de cobre ligadas à MOD. Por último, os dados sugerem que a concentração de MOD é mais importante que a sua caracteristica, em se tratando da modelagem dos efeitos da MOD na biodisponibildade e toxicidade do cobre em água do mar

Effects of copper exposure on the energy metabolism in juveniles of the marine clam Mesodesma mactroides

In freshwater osmoregulating mollusks, Cu can cause toxicity by inducing ionoregulatory disturbances.In mussels, it inhibits the activity of key enzymes involved in Na+uptake and consequently induces ionicand osmotic disturbances. In snails, Cu induces disruption of the Ca2+homeostasis leading to effects inshell deposition and snail growth. However, the mechanisms involved in Cu toxicity in osmoconformingsweater mollusks remain unclear. Recent findings from our laboratory have suggested that Cu toxicityin marine invertebrates can be associated with both ionic and respiratory disturbances. In the presentstudy, metabolic changes induced by waterborne Cu exposure were evaluated in the osmoconformingclam Mesodesma mactroides, a bivalve species widely distributed along the South American sandy beaches.Juvenile clams were kept under control conditions (no Cu addition in the water) or acutely (96 h) exposedto Cu (96-h LC10= 150 g L−1) in artificial seawater (30 ppt). ATP, protein, lipid, glycogen and glucosecontents were analyzed in gills, digestive gland, pedal muscle and hemolymph. Dinucleotide (NAD+andNADH) content was also analyzed in gills, digestive gland and pedal muscle while pyruvate and lactatecontent was determined in pedal muscle and hemolymph. In all tissues analyzed, Cu exposure did notaffect ATP content and NAD+/NADH ratio, except in the hemolymph, where a decrease in ATP content wasobserved. These findings indicate that clam cells, except those from hemolymph, were able to maintain aconstant level of free energy. A significant increase in total protein content was observed in the digestivegland, which could be a compensatory mechanism to counteract the higher level of protein oxidationpreviously observed in M. mactroides exposed to Cu under the same experimental conditions. Finally,reduced glucose content in the pedal muscle paralleled by increased lactate content in the pedal muscleand hemolymph was observed in Cu-exposed clams. Overall, these findings indicate that Cu exposure isleading to an increased reliance upon the anaerobic energy production to maintain the overall cellularATP production in the clam M. mactroides

Dinâmica de variáveis ambientais e do cobre no Rio Nhundiaquara e complexação do metal com células de Eutetramorus sp

Orientadora: Ana Teresa LombardiCo-orientadora: Eunice da Costa MachadoMonografia (graduação) - Universidade Federal do Paraná, Setor de Ciências da Terra, Centro de Estudos do Mar, Curso de Graduação em OceanografiaEm águas naturais, os metais-traço associam-se a materiais inorgânicos, ligantes orgânicos e superficies de partículas. Isso faz com que ocorram em uma grande variedade de formas químicas, onde os materiais orgânicos dissolvidos naturais (DOM) são capazes de complexá-los. As microalgas também exercem influência na especiação quimica dos elementos metálicos através da produção de ligantes orgânicos extracelulares, adsorção e absorção celular. Portanto, interações envolvendo fons metálicos, microalgas e matéria orgânica dissolvida (MOD) podem resultar em alterações da especiação e biodisponibilidade de metais em ambientes naturais. Ao atravessar o município de Morretes e região o Rio Nhundiaquara, foco deste estudo, recebe esgotos domésticos e pesticidas agrícolas. O objetivo desse estudo constituiu em avaliar os efeitos da atividade antrópica sobre a dinâmica do cobre e de vaiáveis fisico-quimicas nas águas do Rio Nhundiaquara, Paraná. Para tanto, foram determinadas as características fisico-quimicas do ambiente, a concentração de cobre livre, a capacidade de complexação de águas naturais e o poder de complexação dos excretados algais e da superficie de células vivas e mortas da referida microalga. A potenciometria, utilizando-se eletrodo seletivo ao lon (ISE) cobre foi a técnica usada para as titulações. Os resultados demonstraram que o Rio Nhundiaquara apresenta elevado potencial de recuperação da influência exercida pelos efluentes urbanos da cidade de Morretes. As amostras do Rio Nhundiaquara apresentaram concentrações de cobre abaixo do limite estipulado pela legislação, e seus valores estão diretamente relacionados com os parâmetros de complexação, os quais apontam para uma grande capacidade de tamponamento do aporte desse metal. Os experimentos de interações do metal cobre com Eutetramorus sp possibilitaram uma melhor compreensão da dinâmica do metal em relação à sua capacidade de adsorção na superficie celular e de complexação com exudatos algais. Os resultados mostraram um aumento no valor da constante de estabilidade condicional seguindo a ordem: material excretado; células mortas suspensas; e células vivas suspensas, indicando que a Eutetramorus sp., isolada do Rio Nhundiaquara, apresenta potencial contribuição à capacidade de complexação (K'e CL) das águas do sistema lótico estudado. Palavras-chave: Complexação de águas naturais, Complexação algal, Rio Nhundiaquara, alga Eutetramorus sp, Parâmetros físicos - químicos

Dinâmica de variáveis ambientais e do cobre no Rio Nhundiaquara e complexação do metal com células de Eutetramorus sp

Orientadora: Ana Teresa LombardiCo-orientadora: Eunice da Costa MachadoMonografia (graduação) - Universidade Federal do Paraná, Setor de Ciências da Terra, Centro de Estudos do Mar, Curso de Graduação em OceanografiaEm águas naturais, os metais-traço associam-se a materiais inorgânicos, ligantes orgânicos e superficies de partículas. Isso faz com que ocorram em uma grande variedade de formas químicas, onde os materiais orgânicos dissolvidos naturais (DOM) são capazes de complexá-los. As microalgas também exercem influência na especiação quimica dos elementos metálicos através da produção de ligantes orgânicos extracelulares, adsorção e absorção celular. Portanto, interações envolvendo fons metálicos, microalgas e matéria orgânica dissolvida (MOD) podem resultar em alterações da especiação e biodisponibilidade de metais em ambientes naturais. Ao atravessar o município de Morretes e região o Rio Nhundiaquara, foco deste estudo, recebe esgotos domésticos e pesticidas agrícolas. O objetivo desse estudo constituiu em avaliar os efeitos da atividade antrópica sobre a dinâmica do cobre e de vaiáveis fisico-quimicas nas águas do Rio Nhundiaquara, Paraná. Para tanto, foram determinadas as características fisico-quimicas do ambiente, a concentração de cobre livre, a capacidade de complexação de águas naturais e o poder de complexação dos excretados algais e da superficie de células vivas e mortas da referida microalga. A potenciometria, utilizando-se eletrodo seletivo ao lon (ISE) cobre foi a técnica usada para as titulações. Os resultados demonstraram que o Rio Nhundiaquara apresenta elevado potencial de recuperação da influência exercida pelos efluentes urbanos da cidade de Morretes. As amostras do Rio Nhundiaquara apresentaram concentrações de cobre abaixo do limite estipulado pela legislação, e seus valores estão diretamente relacionados com os parâmetros de complexação, os quais apontam para uma grande capacidade de tamponamento do aporte desse metal. Os experimentos de interações do metal cobre com Eutetramorus sp possibilitaram uma melhor compreensão da dinâmica do metal em relação à sua capacidade de adsorção na superficie celular e de complexação com exudatos algais. Os resultados mostraram um aumento no valor da constante de estabilidade condicional seguindo a ordem: material excretado; células mortas suspensas; e células vivas suspensas, indicando que a Eutetramorus sp., isolada do Rio Nhundiaquara, apresenta potencial contribuição à capacidade de complexação (K'e CL) das águas do sistema lótico estudado. Palavras-chave: Complexação de águas naturais, Complexação algal, Rio Nhundiaquara, alga Eutetramorus sp, Parâmetros físicos - químicos

Photocatalytic Degradation for Treating Multipesticide Residues Using [Ru(bipy)3] Cl2-Doped TiO2/SiO2 Based on Surface Response Methodology

This study aimed to develop and optimize an efficient photocatalytic process employing ruthenium [Ru(bipy)3]2+ doped TiO2-SiO2 for degrading synthetic wastewater containing six classes of pesticides (bentazone, carbofuran, clomazone, diuron, tebuconazole and pyraclostrobin). To optimize the degradation conditions for the six pesticides and assess the effect of two variables (reaction time and adsorption equilibrium time) on the heterogeneous photocatalytic process, a 22 experimental design with a central composite rotatable design (CCRD) was used. The CCRD was suitable for optimizing the heterogeneous photocatalysis, and the generated surface responses indicated that the best removal conditions were 15 min adsorption equilibrium time and 110 min reaction time. Under these conditions, a pesticide removal between 71.00 and 99.98% was obtained. Furthermore, the system yielded an excellent degree of synthetic wastewater mineralization, with 97.60% total organic carbon (TOC) removal after 110 min

Negative metal bioaccumulation impacts on systemic shark health and homeostatic balance

Contamination by metals is among the most pervasive anthropogenic threats to the environment. Despite the ecological importance of marine apex predators, the potential negative impacts of metal bioaccumulation and biomagnification on the health of higher trophic level species remains unclear. To date, most toxicology studies in sharks have focused on measuring metal concentrations in muscle tissues associating human consumption and food safety, without further investigating potential impacts on shark health. To help address this knowledge gap, the present study evaluated metal concentrations in the gills, muscle, liver and rectal gland of coastal sharks opportunistically sampled from Brazilian waters and tested for potential relationships between metal bioaccumulation and general shark health and homeostatic balance metrics. Results revealed high metal concentrations in all four tissue types, with levels varying in relation to size, sex, and life-stage. Metal concentrations were also associated with serum biomarkers (urea, lactate, ALT, triglycerides, alkaline phosphatase, and phosphorus) and body condition, suggesting potential negative impacts on organismal health. [Display omitted] •Alterations in hepatic markers with the bioaccumulation of Co, Fe, and Hg in the liver of sharks were observed.•Alterations in urea and lactate with the bioaccumulation of Fe and Hg in the gills of sharks were detected.•Alteration in phosphorus with the bioaccumulation of Co, Mn, and Hg in the rectal gland of sharks was also observed.•Body condition was influenced by metals, differing between males and females.•Energy mobilization was influenced by metals, differing between adults and juveniles

Photocatalytic Degradation for Treating Multipesticide Residues Using [Ru(bipy)3] Cl2-Doped TiO2/SiO2 Based on Surface Response Methodology

This study aimed to develop and optimize an efficient photocatalytic process employing ruthenium [Ru(bipy)3]2+ doped TiO2-SiO2 for degrading synthetic wastewater containing six classes of pesticides (bentazone, carbofuran, clomazone, diuron, tebuconazole and pyraclostrobin). To optimize the degradation conditions for the six pesticides and assess the effect of two variables (reaction time and adsorption equilibrium time) on the heterogeneous photocatalytic process, a 22 experimental design with a central composite rotatable design (CCRD) was used. The CCRD was suitable for optimizing the heterogeneous photocatalysis, and the generated surface responses indicated that the best removal conditions were 15 min adsorption equilibrium time and 110 min reaction time. Under these conditions, a pesticide removal between 71.00 and 99.98% was obtained. Furthermore, the system yielded an excellent degree of synthetic wastewater mineralization, with 97.60% total organic carbon (TOC) removal after 110 min