Otimização e validação de metodologia analítica empregando SPE e LC-ESI-MS/MS para determinação de multiclasses de agrotóxicos e metabólitos em água de superfície e de abastecimento público

A aplicação de agrotóxicos nas práticas agrícolas aumentou muito nos últimos anos. Isto vem ocorrendo devido ao crescimento populacional, demandando maior produção de alimentos. O uso de agrotóxicos e seus resíduos tornaram-se um problema devido a possível contaminação das águas de superfície e subterrânea, podendo impactar o meio ambiente e causar danos à saúde pública. Na cidade de Rio Grande, RS, Brasil, o suprimento de água potável é realizado pela CORSAN (Companhia Riograndense de Saneamento), que capta a água do Canal São Gonçalo, o qual estabelece uma ligação entre as duas lagoas: Lagoa dos Patos e Lagoa Mirim. Em suas margens há também a captação de água para irrigação das culturas agrícolas. Esta interação entre o uso da água das lagoas e a agricultura, pode resultar na contaminação das águas que são captadas para abastecimento dos municípios situados na região. Uma metodologia analítica empregando Extração em Fase Sólida (SPE) e Cromatografia Líquida acoplada a uma fonte de ionização por Electrospray tandem Espectrometria de Massas (LCESI-MS/MS) foi desenvolvida e validada para a determinação de dezoito agrotóxicos multiclasses (herbicidas, inseticidas e fungicidas) e dois metabólitos em amostras de água superficial e de abastecimento público. Esta metodologia foi aplicada para monitoramento durante dez meses na água superficial do Canal São Gonçalo e na água de consumo da cidade de Rio Grande, após o tratamento pela CORSAN. Os agrotóxicos selecionados foram: clomazona, bispiribaque-sódio, diurom, atrazina, simazina, imazetapir, imazapique, metsulfuron-metílico, quincloraque, penoxsulam, 2,4-D, pirazosulfuron-etílico, bentazona, propanil, irgarol, tebuconazol, fipronil e carbofurano. Os metabólitos foram: 3,4-DCA e 3-hidroxicarbofurano. Os limites de detecção do método variaram entre 0,4 – 40,0 ng L -1 , enquanto para os limites de quantificação a variação foi de 4,0 – 100,0 ng L -1 . Todos os compostos apresentaram excelente linearidade, com coeficiente de determinação maior do que 0,99. As recuperações empregando SPE com cartuchos contendo 500 mg de C18ec, variaram entre 70 a 120%, para 95% dos compostos, apresentando %RSD 20%. Através do monitoramento de múltiplas reações (MRM), duas transições diferentes (íon precursor – íon produto) foram selecionadas para cada composto, uma para quantificação e outra para confirmação, o que aumentou a seletividade do método. Para as amostras analisadas, foram detectados agrotóxicos nível de ng L -1 . O método desenvolvido é sensível, rápido e apresenta elevada seletividade, permitindo a identificação e a quantificação dos agrotóxicos em águas superficiais e de abastecimento público, atendendo os níveis requeridos pelos órgãos reguladores como da União Européia (98/83/EC) e do Brasil segundo a Portaria Nº. 518 (25/03/2004).

Learning from the lagoon: Research in development in Solomon Islands

A major challenge for international agricultural research is to find ways to improve the nutrition and incomes of people left behind by the Green Revolution. To better address the needs of the most marginal and vulnerable people, the CGIAR Research Program on Aquatic Agricultural Systems (AAS) developed the research-in-development (RinD) approach. In 2012, WorldFish started to implement RinD in Solomon Islands. By building people’s capacity to analyze and address development problems, actively engaging relevant stakeholders, and linking research to these processes, RinD aims to develop an alternative approach to addressing hunger and poverty. This report describes the key principles and implementation process, and assesses the emergent outcomes of this participatory, systems-oriented and transformative research approach in Solomon Islands.

Desenvolvimento e validação de método voltamétrico para determinação de ferro e sua especiação química em água intersticial no sedimento da Lagoa dos Patos-RS

Os sedimentos podem atuar tanto como acumuladores quanto como fontes de poluentes. Em função das atividades portuárias locais estarem em ritmo de crescimento pela ampliação do porto de Rio Grande (RS), estudos que mostrem a situação do local investigado são importantes a fim de prever o aporte do ferro nesse ambiente. Neste trabalho, a especiação química do ferro e a determinação da concentração do metal total e dissolvido em amostras de águas intersticiais no sedimento do Saco do Mendanha (RS) foram avaliadas, utilizando a Voltametria Adsortiva de Redissolução Catódica com o ligante 2,3-Dihidroxinaftaleno. O objetivo principal desse trabalho foi validar a metodologia analítica para realizar a especiação química do ferro em águas intersticiais, o que englobou a faixa linear de trabalho, limites de detecção e de quantificação, a exatidão e precisão. O Limite de Detecção encontrado foi de 0,11 nmol L-1 . Foram determinadas as concentrações de ferro total, dissolvido e lábil em três frações distintas: na interface água/sedimento, entre 0 e -5 cm; e entre -15 e -20 cm de profundidade na coluna sedimentar. Nas amostras analisadas, a concentração de ferro lábil encontrada foi entre 4,64 – 135,37 µmol L-1 ; a concentração do metal dissolvido foi de 6,25 – 322,70 µmol L-1 e de ferro total entre 83,36 – 390,30 µmol L-1 . A concentração do metal lábil em comparação com a fração dissolvida e total indica a presença de complexos estáveis entre o metal e a matéria orgânica natural presente na água intersticial, tornando dessa forma, o metal menos biodisponível para a biota local. Durante os meses de amostragem do sedimento, foi observada variação da concentração do metal, onde no mês de abril ocorreu o maior aporte do metal da coluna d’água para o sedimento. Essa transferência do metal para o sedimento pode estar relacionada pela forte mudança na salinidade no local de amostragem, passando de 16 no mês de fevereiro para 33 no mês de abril e para próximo de zero nos meses de agosto e novembro de 2009.

Especiação química de arsênio inorgânico no estuário da Lagoa dos Patos-RS

A poluição das águas por metais, principalmente os metais pesados, vem chamando a atenção no mundo, pois estes poluentes aquáticos representam um risco em potencial, devido ao seu caráter acumulativo. Entre os metais, o arsênio recebe destaque pelo seu potencial tóxico. O arsênio inorgânico ocorre na natureza em quatro estados de oxidação: As5+, As3+, As0 e As3- . O estado de oxidação do arsênio tem um papel importante no seu comportamento e toxicidade nos sistemas aquáticos. Pelo fato do arsênio ser extremamente perigoso e nocivo para o meio ambiente, novos métodos analíticos de especiação química no meio ambiente têm sido publicados. Neste estudo foi otimizado e validado um método para realizar a especiação química de arsênio inorgânico presente em amostras de água coletadas nos meses de julho e outubro de 2010 no estuário da Lagoa dos Patos (RS, Brasil), como parte das atividades do Programa de Monitoramento Ambiental do Porto do Rio Grande-RS. Foi usada a técnica de espectrometria de absorção atômica com geração de hidretos e injeção em fluxo (FI-HG AAS), podendo ser quantificadas espécies de As3+ e As5+ nas amostras de água estuarina. A concentração do arsênio trivalente inorgânico foi determinada, após adição de solução tampão citrato de sódio (0,4 mol L-1 ; pH = 6,0). A concentração de arsênio inorgânico total foi determinada, após uma etapa de pré-redução da espécie pentavalente para a forma trivalente usando uma mistura de iodeto de potássio, ácido ascórbico em meio ácido clorídrico concentrado. A concentração de arsênio pentavalente foi calculada pela diferença das concentrações de arsênio inorgânico total e trivalente. A interpretação dos resultados gerados pelo método proposto usado ao analisar amostras de águas coletadas no estuário da Lagoa dos Patos foi feita pela análise dos componentes principais. Os dados tratados estatisticamente revelaram uma interação significativa neste estudo entre o arsênio, o material em suspensão (MS) e o NH4 + na superfície da coluna d’água no período da primavera.

Impact of Hypoxia on the Community Structure of Benthic Macroinvertebrates of Lagos Lagoon, Nigeria

Study of the Lagos lagoon was conducted for two years to investigate the impact of hypoxia on the benthic macroinvertebrates. Water and benthic samples were collected monthly along the study stretch and analysed in a standard laboratory. Temporal variation in water physico-chemistry was largely controlled by rainfall pattern while the spatial variation was influenced by proximity to the Harbour as well as the pollution sources and types. A total of 3,159 individuals comprising three phyla, five classes, nineteen families and twenty three species were recorded. Iddo I, Iddo II, Ogudu and Agboyi study stations recorded very low individuals, but relatively high number of polychaetes. Benthic macro- invertebrate community was dominated by the molluscs. Margalef’s index of species richness ranged from 0.79 to 2.57 while Shannon-Wiener index ranged from 0.40 to 2.19. Species evenness index ranged from 0.29 to 0.80. There was generally low biodiversity indicating the stressed nature of the study area.

Processo histórico de criação e expansão do Instituto Federal do Triângulo Mineiro - Campus Patos de Minas

Dissertação (mestrado)—Universidade de Brasília, Faculdade UnB Planaltina, Programa de Pós-Graduação em Gestão Pública, Mestrado Profissional em Gestão Pública, 2016.

Assessing land–ocean connectivity via submarine groundwater discharge (SGD) in the Ria Formosa Lagoon (Portugal): combining radon measurements and stable isotope hydrology

Natural radioactive tracer-based assessments of basin-scale submarine groundwater discharge (SGD) are well developed. However, SGD takes place in different modes and the flow and discharge mechanisms involved occur over a wide range of spatial and temporal scales. Quantifying SGD while discriminating its source functions therefore remains a major challenge. However, correctly identifying both the fluid source and composition is critical. When multiple sources of the tracer of interest are present, failure to adequately discriminate between them leads to inaccurate attribution and the resulting uncertainties will affect the reliability of SGD solute loading estimates. This lack of reliability then extends to the closure of local biogeochemical budgets, confusing measures aiming to mitigate pollution. Here, we report a multi-tracer study to identify the sources of SGD, distinguish its component parts and elucidate the mechanisms of their dispersion throughout the Ria Formosa – a seasonally hypersaline lagoon in Portugal. We combine radon budgets that determine the total SGD (meteoric + recirculated seawater) in the system with stable isotopes in water (δ2H, δ18O), to specifically identify SGD source functions and characterize active hydrological pathways in the catchment. Using this approach, SGD in the Ria Formosa could be separated into two modes, a net meteoric water input and another involving no net water transfer, i.e., originating in lagoon water re-circulated through permeable sediments. The former SGD mode is present occasionally on a multi-annual timescale, while the latter is a dominant feature of the system. In the absence of meteoric SGD inputs, seawater recirculation through beach sediments occurs at a rate of  ∼  1.4  ×  106 m3 day−1. This implies that the entire tidal-averaged volume of the lagoon is filtered through local sandy sediments within 100 days ( ∼  3.5 times a year), driving an estimated nitrogen (N) load of  ∼  350 Ton N yr−1 into the system as NO3−. Land-borne SGD could add a further  ∼  61 Ton N yr−1 to the lagoon. The former source is autochthonous, continuous and responsible for a large fraction (59 %) of the estimated total N inputs into the system via non-point sources, while the latter is an occasional allochthonous source capable of driving new production in the system.

Genetic diversity and connectivity remain high in Holothuria polii (Delle Chiaje 1823) across a coastal lagoon-open sea environmental gradient

Coastal lagoons represent habitats with widely heterogeneous environmental conditions, particularly as regards salinity and temperature,which fluctuate in both space and time. These characteristics suggest that physical and ecological factors could contribute to the genetic divergence among populations occurring in coastal lagoon and opencoast environments. This study investigates the genetic structure of Holothuria polii at a micro-geographic scale across theMar Menor coastal lagoon and nearbymarine areas, estimating the mitochondrial DNA variation in two gene fragments, cytochrome oxidase I (COI) and 16S rRNA (16S). Dataset of mitochondrial sequences was also used to test the influence of environmental differences between coastal lagoon andmarine waters on population genetic structure. All sampled locations exhibited high levels of haplotype diversity and low values of nucleotide diversity. Both genes showed contrasting signals of genetic differentiation (non-significant differences using COI and slight differences using 16S, which could due to different mutation rates or to differential number of exclusive haplotypes. We detected an excess of recent mutations and exclusive haplotypes, which can be generated as a result of population growth. However, selective processes can be also acting on the gene markers used; highly significant generalized additive models have been obtained considering genetic data from16S gene and independent variables such as temperature and salinity.

Feeding habits of the deep-snouted pipefish Syngnathus typhle in a temperate coastal lagoon

Feeding habits of Syngnathus typhle were determined based on monthly sampling during experimental fishing in a coastal lagoon (Ria Formosa, South Portugal) from April 2004 to May 2002. The gut contents of 856 individuals were analysed and quantified with numerical and gravimetric methods, as well as with some complementary indices and measures (vacuity, fullness and relative importance). In this study, this species fed mainly on Copepoda, Mysidacea, small caridean grass shrimps (Hippolytidae and Palaemonidae) and small fishes (Gobiidae) and to a lesser degree on other small invertebrates. No significant differences were found between the diets of males and females. However, significant differences in the fullness indexes of both sexes were observed during the reproductive period. Significant differences in the diet among seasons were also verified but no seasonal trends were discovered. Snout length showed a linear increase with growth while mouth area and total length displayed an allometric relation. Mouth shape varied between an ellipse and an almost perfect circle. The increase in mouth area and snout length as S. typhle grows contributed to the observed ontogenic diet shift with specimens smaller than 10 cm feeding almost exclusively on Copepoda, medium sized specimens feeding mainly on Hippolytidae and Mysidacea, while larger specimens preyed on Hippolytidae, Palaemonidae and Gobiidae. Prey size generally increased with size of S. typhle. (c) 2007 Elsevier Ltd. All rights reserved.

Fish assemblages of shallow intertidal habitats of the Ria Formosa lagoon (South Portugal): influence of habitat and season

Fish assemblages in seagrass and unvegetated habitats located in shallow intertidal creeks within the saltmarsh area of the Ria Formosa coastal lagoon were sampled with a Riley push net at 3 sites on a monthly basis over a 1 yr period. The objective was to test if both habitats support similar fish assemblages in terms of abundance, diversity, assemblage structure, and size distribution, and to investigate how site and season affect the assemblages. Fish assemblages associated with these habitats were significantly different in terms of diversity, abundance, and assemblage structure. Seagrass supported a larger number of species and greater diversity, while unvegetated habitat supported greater fish numbers but only of a few species. The habitats were dominated by different groups of resident species that were responsible for major differences in fish assemblage structure between habitats. Pomatoschistus microps and young-of-the-year (YOY) Atherina presbyter dominated the unvegetated habitat, while seagrass was dominated by a diverse group of species, in particular syngnathids and small labrids, revealing different habitat preferences. Site and season were determinant factors conditioning the role of habitat in structuring fish assemblages. Distance between habitats, site elevation, and the amount of marsh drained affected fish assemblages in both habitats. Seasonal fluctuations in the presence and abundance of YOY from marine migrant and resident species were responsible for comparable changes in fish assemblage structure in both habitats. Both habitats provide a distinctive nursery area for different species, while common species reveal ontogenic distributional changes between habitats, where smaller fish appear first in unvegetated creeks.

Home range, residency and movements of Diplodus sargus and Diplodus vulgaris in a coastal lagoon: Connectivity between nursery and adult habitats

Acoustic telemetry and standard tag-recapture were used to determine the home range and residency of juveniles and sub-adults of Diplodus sargus and Diplodus vulgaris in the Ria Formosa (Portugal) coastal lagoon. Maximum time between recaptures for the standard tag-recapture method was 128 days for D. sargus and 30 days for D. vulgaris. The majority of the fish were recaptured in the vicinity of the tagging location. Fish tagged with acoustic transmitters had a maximum period of time between first and last detections of 62 days for D. sargus and 260 days for D. vulgaris. Minimum convex polygons areas ranged between 148 024 m(2) and 525 930 m(2) for D. sargus and between 23 786 m(2) and 42134 m(2) for D. vulgaris. Both species presented a high residency index between first and last detections. Two D. sargus tagged with acoustic tags were recaptured by fishermen outside the coastal lagoon at distances of 12 km and 90 km from the tagging position, providing evidence that this species leaves the Ria Formosa during the winter time for the adjacent coastal waters. The results of this study reinforce the importance of Ria Formosa as a nursery for D. sargus and D. vulgaris in the south coast of Portugal. (C) 2009 Elsevier Ltd. All rights reserved.

Long-term changes in fish communities of the Ria Formosa coastal lagoon (southern Portugal) based on two studies made 20 years apart

Fish communities of the Ria Formosa coastal lagoon (south Portugal) were sampled on a monthly basis with a beach seine at 4 sites, during two different time periods: 1980-1986 and 2001-2002. Community indices, species ranking and multivariate analysis were used in order to identify changes in the fish community between the two time periods. A total of 153,511 fish representing 57 taxa were recorded. Although species composition was very similar for both sampling periods, multivariate analysis performed on annual species abundance in number and weight revealed differences in fish community structure between the two periods. Structural changes in fish community were related mostly to a sharp decrease in the abundance of Mugilidae from 1980-1986 to 2001-2002. These changes were probably associated to a decrease in organic matter contents and nutrients concentrations due to improvements in sewage treatment and better water circulation inside the lagoon. The changes in fish community structure are more evident in the inner areas of the lagoon than near the inlet. The association between changes in sewage patterns and changes in the ichthyofaunal community structure reinforces the importance of fish communities as a biological indicator of human induced changes in marine systems. (c) 2007 Elsevier Ltd. All rights reserved.

Seasonal, tidal and diurnal changes in fish assemblages in the Ria Formosa lagoon (Portugal)

Fish fauna were collected in two different subtidal shallow sites, seagrass and sand, using a small beam trawl in the Ria Formosa lagoon (South Portugal). Samples were taken at low and high tides, during day and night, and in each season. Fish assemblages associated with each site were significantly different, with seagrass site supporting greater fish abundance and higher number of species than sand. These site-related differences in fish assemblages were stronger than any other factor studied. Both sites showed seasonal variations in their fish assemblages, mainly because of recruitment of marine juvenile migrants during spring and summer. No significant tidal or diel changes were observed in the fish assemblages of either site, but there was a significant site-tide interaction, with higher fish abundance in seagrass at low tide. In sand, tide effect was evident only for certain species, with resident species more abundant at high tide and marine species more abundant at low tide. Within the Ria Formosa coastal lagoon, ichthyofaunal composition and structure is mainly influenced by site followed by season. (c) 2005 Elsevier Ltd. All rights reserved.