Chemical and physical characterization of clay bodies

Suitable methods for the assessment of the effect of freeze-thaw action upon ceramic tiles have been determined. The results obtained have been shown to be reproducible with some work in this area still warranted. The analysis of Whichford Potteries clays via a variety of analytical techniques has shown them to be a complex mix of both clay and non-clay minerals. 57Fe Mössbauer spectroscopy has highlighted the presence of both small and large particleα-Fe203, removable via acid washing. 19F MAS NMR has demonstrated that the raw Whichford Pottery clays examined have negligible fluorine content. This is unlikely to be detrimental to ceramic wares during the heating process. A unique technique was used for the identification of fluorine in solid-state systems. The exchange of various cations into Wyoming Bentonite clay by microwave methodology did not show the appearance of five co-ordinate aluminium when examined by 27Al MAS NMR. The appearance of Qo silicate was linked to an increase in the amount of tetrahedrally bound aluminium in the silicate framework. This is formed as a result of the heating process. The analysis of two Chinese clays and two Chinese clay raw materials has highlighted a possible link between the two. These have also been shown to be a mix of both clay and non-clay minerals. Layered double hydroxides formed by conventional and microwave methods exhibited interesting characteristics. The main differences between the samples examined were not found to be solely attributable to the differences between microwave and conventional methods but more attributable to different experimental conditions used.

Segregation of Palaemonid Shrimp Along an Everglades Estuarine Gradient: Do Multiple Species Have Similar Trophic Function?

Variation in physical gradients and production along estuaries can alter species compositions. Spatiotemporal variation in abundance and distribution of palaemonid shrimp species was investigated in relation to seasonal freshwater inputs and salinity in the Shark River Estuary, Everglades National Park, Florida, USA. Using trapping techniques, multiple sites were sampled repeatedly extending from the headwaters to the Gulf of Mexico. Stable isotope analyses were also performed on a subset of samples. Five palaemonid species occurred in the samples: Palaemonetes paludosus (Gibbes, 1850), Palaemonetes pugio (Holthuis, 1949), Palaemonetes intermedius (Holthuis, 1949), Palaemon floridanus (Chace, 1942), and Leander paulensis(Ortmann, 1897). Overall, shrimp catches in traps doubled in the dry season. Catches in the upper estuary were dominated by P.paludosus, particularly in the wet season, while catch per unit effort at the most downstream and highest salinity sites were dominated by P. floridanus. At mid-estuary, several species co-occurred. δ15n analyses revealed that most species filled similar roles in the community, with the exception of P. paludosus, which shifted from enrichment in the dry season to depletion in the wet season as it expanded downstream in the estuary. Palaemonid δ13C values varied between sites and seasons, with shrimp in upstream sites being more depleted. These data suggest that changes in salinity regimes resulting from Everglades restoration efforts may result in species replacement, with potential implications for trophic dynamics.

Effects of an extreme temperature event on the behavior and age structure of an estuarine top predator, Carcharhinus leucas

The frequency of extreme environmental events is predicted to increase in the future. Understanding the short- and long-term impacts of these extreme events on large-bodied predators will provide insight into the spatial and temporal scales at which acute environmental disturbances in top-down processes may persist within and across ecosystems. Here, we use long-term studies of movements and age structure of an estuarine top predator—juvenile bull sharks Carcharhinus leucas—to identify the effects of an extreme ‘cold snap’ from 2 to 13 January 2010 over short (weeks) to intermediate (months) time scales. Juvenile bull sharks are typically year-round residents of the Shark River Estuary until they reach 3 to 5 yr of age. However, acoustic telemetry revealed that almost all sharks either permanently left the system or died during the cold snap. For 116 d after the cold snap, no sharks were detected in the system with telemetry or captured during longline sampling. Once sharks returned, both the size structure and abundance of the individuals present in the nursery had changed considerably. During 2010, individual longlines were 70% less likely to capture any sharks, and catch rates on successful longlines were 40% lower than during 2006−2009. Also, all sharks caught after the cold snap were young-of-the-year or neonates, suggesting that the majority of sharks in the estuary were new recruits and several cohorts had been largely lost from the nursery. The longer-term impacts of this change in bull shark abundance to the trophic dynamics of the estuary and the importance of episodic disturbances to bull shark population dynamics will require continued monitoring, but are of considerable interest because of the ecological roles of bull sharks within coastal estuaries and oceans.

Inputs from a mercury-contaminated lagoon: impact on the nearshore waters of the Atlantic Ocean

Ria de Aveiro, a Portuguese coastal lagoon that exchanges water with the Atlantic Ocean, received the effluent from a chlor-alkali industry for over 50 years; consequently several tons of mercury had been buried in the sediments of an inner basin. To assess the importance (and seasonal variation) of the lagoon waters as carriers of mercury to the nearby coastal area, we measured total mercury levels in several compartments: in surface sediments, in surface and deep waters (including dissolved and particulate matter!, and in biota. Dissolved (reactive and total) mercury concentrations both in surface and deep waters were low (<1 to 15 ng L '). Mean mercury values in suspended particulate matter varied hetween 0.2 and 0.6 jxg g ' and in sediments between 1 and 9 ng g '. Aquatic organisms displayed levels below regulatory limits but exhibited some bioaccumulation of mercury, with concentrations ranging from 0.05 to 0.8 ^ig g ' Idry weight (dw)|. No seasonal pattern was found in this study for mercury-related determinations. Levels found in the estuary mouth during ebb tide provide evidence for the transport of mercury to the coastal zone. No significant changes in the partition of mercury between dissolved and particulate phases were found in the coastal waters in comparison with the values found in the estuary mouth. In spite of the high levels of mercury found inside some areas of the lagoon, the wide web of islands and channels allows some spreading of contaminants before they reach the coastal waters. Moreover, the low efficiency of local marine sediments in trapping mercury contributes to a dilution of mercury transported in suspended particulate matter over a broader area, reducing the impact in the nearby manne coastal zone.

Desencontros legais e morais na pesca artesanal: a Educação Ambiental política para a transformação socioambiental em Rio Grande/RS e São José do Norte/RS

A dissertação intitulada “Desencontros legais e morais na pesca artesanal: a Educação Ambiental política para a transformação socioambiental em Rio Grande/RS e São José do Norte/RS” busca analisar a compreensão das comunidades de pescadores artesanais do Rio Grande e de São José do Norte acerca de aspectos do desencontro entre as normas legais pesqueiras e as normas morais daqueles atores sociais, e os reflexos na conservação do meio ambiente e no exercício da cidadania ambiental, a fim de colaborar, por intermédio da Educação Ambiental, com o fortalecimento dos pescadores para a reversão do atual quadro de crise social e ambiental vivenciada na pesca artesanal da região, bem como para refletir sobre a ineficiência das regras legais aplicáveis no estuário da Lagoa dos Patos. Para tanto os objetivos foram estruturados de forma a investigar os aspectos do desencontro mencionado; analisar seus reflexos no declínio da conservação dos recursos renováveis e no exercício da cidadania pelos pescadores artesanais; e apresentar alternativas possíveis pela e para a Educação Ambiental, enquanto educação política, visando a proporcionar a transformação socioambiental dos pescadores para a garantia de sua participação cidadã nas esferas de decisão relativas à sua vida social e profissional. A pesquisa teve uma abordagem qualitativa, com enfoque teórico-metodológico nas representações coletivas dos pescadores. O trabalho foi composto de levantamento bibliográfico e documental, que serviu de apoio para a obtenção das representações mediante a realização de grupos focais junto a quatro comunidades de pescadores nas cidades pesquisadas. Esse corpus de pesquisa foi analisado com base na metodologia Análise Textual Discursiva. Os resultados obtidos indicaram que a crise instaurada na pesca ultrapassa a dicotomia existente entre as leis ambientais e as normas morais dos pescadores artesanais, emergindo o aspecto da necessidade financeira e de sobrevivência de pescadores e de suas famílias. Verificou-se, outrossim, que o desencontro pesquisado refletiu negativamente na conservação dos recursos naturais, na medida em que gerou a falta de efetividade de leis relacionadas àquela atividade profissional, repercutindo desfavoravelmente no exercício da cidadania ambiental pelos pescadores. Concluiu-se que a Educação Ambiental política possui um papel fundamental para o empoderamento dos pescadores artesanais em busca de sua participação ativa nos processos de gestão dos recursos pesqueiros estuarinos, numa verdadeira governança participativa, voltada à conservação ambiental e edificação do bem coletivo.

The estuarine geochemical reactivity of Zn isotopes and its relevance for the biomonitoring of anthropogenic Zn and Cd contaminations from metallurgical activities: Example of the Gironde fluvial-estuarine system, France

Zinc stable isotopes measurements by MC-ICP-MS, validated by laboratory intercalibrations, were performed on wild oysters, suspended particles and filtered river/estuarine water samples to provide new constraints for the use of Zn isotopes as environmental tracers. The samples selected were representative of the long range (400 km) transport of metal (Zn, Cd, etc.) contamination from former Zn-refining activities at Decazeville (i.e. δ66Zn > 1 ‰) and its phasing out, recorded during 30 years in wild oysters from the Gironde Estuary mouth (RNO/ROCCH sample bank). The study also addresses additional anthropogenic sources (urban and viticulture) and focuses on geochemical reactivity of Zn in the turbidity gradient and the maximum turbidity zone (MTZ) of the fluvial Gironde Estuary. In this area, dissolved Zn showed a strong removal onto suspended particulate matter (SPM) and progressive enrichment in heavy isotopes with increasing SPM concentrations varying from δ66Zn = -0.02 ‰ at 2 mg/L to +0.90 ‰ at 1310 mg/L. These signatures were attributed to kinetically driven adsorption due to strongly increasing sorption sites in the turbidity gradient and MTZ of the estuary. Oysters from the estuary mouth, contaminated sediments from the Lot River and SPM entering the estuary showed parallel historical evolutions (1979-2010) for Zn/Cd ratios but not for δ66Zn values. Oysters had signatures varying from δ66Zn = 1.43 ‰ in 1983 to 1.18 ‰ in 2010 and were offset by δ66Zn = 0.6 - 0.7 ‰ compared to past (1988) and present SPM from the salinity gradient. Isotopic signatures in river-borne particles entering the Gironde Estuary under contrasting freshwater discharge regimes during 2003-2011 showed similar values (δ66Zn ≈ 0.35 ± 0.03 ‰; 1SD, n=15), i.e. they were neither related to former metal refining activities at least for the past decade nor clearly affected by other anthropogenic sources. Therefore, the Zn isotopic signatures in Gironde oysters reflect the geochemical reactivity of Zn in the estuary rather than signatures of past metallurgical contaminations in the watershed as recorded in contaminated river sediments. The study also shows that the isotopic composition of Zn is strongly fractionated by its geochemical reactivity in the Gironde Estuary, representative of meso-macrotidal estuarine systems.

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.

Hidrocarbonetos policíclicos aromáticos em sedimentos de fundo do estuário do rio Potengi, região da grande Natal (RN): implicações ambientais

Estuaries are environments prone to the input of chemical pollutants of various kinds and origins, including polycyclic aromatic hydrocarbons (PAHs). Anthropogenic PAHs may have two possible sources: pyrolytic (with four or more aromatic rings and low degree of alkylation) and petrogenic (with two and three aromatic rings and high degree of alkylation). This study aimed to evaluate the levels, distribution and possible sources of polycyclic aromatic hydrocarbons in the estuary of the Potengi river, Natal, Brazil. Samples of bottom sediments were collected in the final 12 km of the estuary until its mouth to the sea, where the urbanization of the Great Natal is more concentrated. Sampling was performed on 12 cross sections, with three stations each, totaling 36 samples, identified as T1 to T36. The non alkylated and alkylated PAHs were analyzed by gas chromatography coupled to mass spectrometry (GC / MS). PAHs were detected in all 36 stations with total concentration on each varying 174-109407 ng g-1. These values are comparable to those of several estuarine regions worldwide with high anthropogenic influence, suggesting the record of diffuse contamination installed in the estuary. PAHs profiles were similar for most stations. In 32 of the 36 stations, low molecular weight PAHs (with 2 and 3 ring: naphthalene, phenanthrene and their alkylated homologues) prevailed, which ranged from 54% to 100% of the total PAH, indicating that leaks, spills and combustion fuels are the dominant source of PAH pollution in the estuary. The level of contamination by PAHs in most stations suggests that there is potential risk of occasional adverse biological effects, but in some stations adverse impacts on the biota may occur frequently. The diagnostic ratios could differentiate sources of PAHs in sediments of the estuary, which were divided into three groups: petrogenic, pyrolytic and mixing of sources. The urban concentration of the Great Natal and the various industrial activities associated with it can be blamed as potential sources of PAHs in bottom sediments of the estuary studied. The data presented highlight the need to control the causes of existing pollution in the estuary

Hidrocarbonetos alifáticos em sedimentos de fundo do estuário do Rio Potengi, grande Natal (RN): implicações ambientais

The Potengi river estuary is located in the region of Natal (RN, Brazil), comprising a population of approximately 1,000,000 inhabitants. Besides the dominant urban presence, the estuary has fragments of mangrove forest. The objective of this study is to determine the aliphatic hydrocarbons found in the bottom sediments of this estuary, identifying their levels, distribution and their possible origins through the diagnostic rates, indexes and results comparisons with the local anthropic and natural characteristics. The samples were obtained according to a plan that allowed sampling of the estuary up to 12 km upstream from it as mounth. 36 stations were selected, grouped into 12 cross sections through the course of the river and spaced on average by 1 km. Each section consisted of three stations: the right margin, the deepest point and the left margin. The hydrocarbon n-alkanes from C10 to C36, the isoprenoids pristane and phytane, the unresolved complex mixture (UCM) and the total resolved hydrocarbons were analyzed by gas chromatography. N-alkanes, pristane, phytane and UCM were detected only at some stations. In the other, the concentration was below the detection limit defined by the analytical method (0.1 mg / kg), preventing them from being analyzed to determine the origin of the material found. By using different parameters, the results show that the estuary receives both the input of petrogenic hydrocarbons, but also of biogenic hydrocarbons, featuring a mixture of sources and relatively impacted portions. Based on the characteristics and activities found in the region, it is possible to affirm that petrogenic sources related to oil products enter the estuary via urban runoff or boats traffic, boat washing and fueling. Turning to the biogenic source, the predominant origin was terrestrial, characterized by vascular plants, indicating contribution of mangrove vegetation. It was evident the presence of, at specific points in the estuary, hydrocarbon pollution, and, therefore is recommended the adoption of actions aimed at interrupting or, at least, mitigating the sources potentially capable of damp petrogenic hydrocarbons in the estuary studied.

Development of molecular approaches to assess the diversity and abundance of marine nematodes assemblages for assessment of Good Environmental Status of the estuarine and marine ecosystems

In Europe, the concerns with the status of marine ecosystems have increased, and the Marine Directive has as main goal the achievement of Good Environmental Status (GES) of EU marine waters by 2020. Molecular tools are seen as promising and emerging approaches to improve ecosystem monitoring, and have led ecology into a new era, representing perhaps the most source of innovation in marine monitoring techniques. Benthic nematodes are considered ideal organisms to be used as biological indicator of natural and anthropogenic disturbances in aquatic ecosystems underpinning monitoring programmes on the ecological quality of marine ecosystems, very useful to assess the GES of the marine environment. dT-RFLP (directed Terminal-Restriction Fragment Length Polymorphism) allows to assess the diversity of nematode communities, but also allows studying the functioning of the ecosystem, and combined with relative real-time PCR (qPCR), provides a high-throughput semi-quantitative characterization of nematode communities. These characteristics make the two molecular tools good descriptors for the good environmental status assessment. The main aim of this study is to develop and optimize the dT-RFLP and qPCR in Mira estuary (SW coast, Portugal). A molecular phylogenetic analysis of marine and estuarine nematodes is being performed combining morphological and molecular analysis to evaluate the diversity of free-living marine nematodes in Mira estuary. After morphological identification, barcoding of 18S rDNA and COI genes are being determined for each nematode species morphologically identified. So far we generated 40 new sequences belonging to 32 different genus and 17 families, and the study has shown a good degree of concordance between traditional morphology-based identification and DNA sequences. These results will improve the assessment of marine nematode diversity and contribute to a more robust nematode taxonomy. The DNA sequences are being used to develop the dT-RFLP with the ability to easily process large sample numbers (hundreds and thousands), rather than typical of classical taxonomic or low throughput molecular analyses. A preliminary study showed that the digest enzymes used in dT-RFLP for terrestrial assemblages separated poorly the marine nematodes at taxonomic level for functional group analysis. A new digest combination was designed using the software tool DRAT (Directed Terminal Restriction Analysis Tool) to distinguished marine nematode taxa. Several solutions were provided by DRAT and tested empirically to select the solution that cuts most efficiently. A combination of three enzymes and a single digest showed to be the best solution to separate the different clusters. Parallel to this, another tool is being developed to estimate the population size (qPCR). An improvement in qPCR estimation of gene copy number using an artificial reference is being performed for marine nematodes communities to quantify the abundance. Once developed, it is proposed to validate both methodologies by determining the spatial and temporal variability of benthic nematodes assemblages across different environments. The application of these high-throughput molecular approaches for benthic nematodes will improve sample throughput and their implementation more efficient and faster as indicator of ecological status of marine ecosystems.

Salinity Intrusion and Seasonal Water Quality Variations in the Tidal Canals of Cochin

The study conducted on the salinity intrusion and seasonal water quality variations in the tidal canals of cochin. The main objectives are, salinity intrusion profile, water quality variation of the surface water of the canals,hierarchical utility of the water bodies and to understand the non-conservative components in the water body. The parameters monitored werepH,temperature,alkalinity,conductivity,DO(dissolvedoxygen),COD(chemical oxygen demand),BOD(biochemical oxygen demand0,chloride, total hardness, calcium hardness, dissolved phosphate, nitrate, total iron, sulphate, turbidity, total coliform and SUVA at 254nm. The tidal canals of GCDA were found to be creeks extending to the interior, canals inter connecting parts of the estuary or canals with seasonally broken segments. Based on utility the canals could be classified as: canals heavely polluted and very saline,canals polluted by urban waste , canals having fresh water for most part of the year and not much polluted, fresh water bodies heavily polluted. During the rainy months carbon fixation by plankton is nonexistent,and during the dry months Chitrapuzha becomes a sink of phosphate. The study indicated abiotic subrouts for dissolved phosphate and revealed the potential pitfalls in LOICZ modeling exercise on sewage ladentidal canals. It was also found that all canals except for the canals of West cochin and chittoorpuzha have fresh water for some part of the year. The water quality index in the durable fresh water stretches was found to be of below average category.