The behaviour of the rare earth elements during estuarine mixing-revisited

Complete rare earth element (except Eu) and Y concentrations from the estuarine mixing zone (salinity =0.2 to 33) of Elimbah Creek, Queensland, Australia, were measured by quadrupole ICP-MS without preconcentration. High sampling density in the low salinity regime along with high quality data allow accurate tracing of the development of the typical marine rare earth element anomalies as well as Y/Ho fractionation. Over the entire estuary, the rare earth elements are strongly removed relative to a freshwater endmember (60-80% removal). This large overall removal occurs despite a strong remineralisation peak (190% for La, 130% for Y relative to the freshwater endmember) in the mid-salinity zone. Removal and remineralisation are accompanied by fractionation of the original (freshwater) rare earth element pattern, resulting in light rare earth element depletion. Estuarine fractionation generates a large positive La anomaly and a superchondritic Y/Ho ratio. Conversely, we observe no evidence to support the generation of the negative Ce anomaly in the estuary. With the exception of Ce, the typical marine rare earth element features can thus be attributed to estuarine mixing processes. The persistence of these features in hydrogenous sediments for at least 3.71 Ga highlights the importance of estuarine processes for marine chemistry on geological timescales. (c) 2005 Elsevier B.V. All rights reserved.

Mean sea-level rise impacts on Santos Bay, Southeastern Brazil - physical modelling study

The greenhouse effect and resulting increase in the Earth`s temperature may accelerate the mean sea-level rise. The natural response of bays and estuaries to this rise, such as this case study of Santos Bay (Brazil), will include change in shoreline position, land flooding and wetlands impacts. The main impacts of this scenario were studied in a physical model built in the Coastal and Harbour Division of Hydraulic Laboratory, University of Sao Paulo, and the main conclusions are presented in this paper. The model reproduces near 1,000 km(2) of the study area, including Santos, Sao Vicente, Praia Grande, Cubatao, Guaruja and Bertioga cities.

Morfologia e distribuição sedimentar em um sistema estuarino tropical : Baía de Vitória, ES

A Baía de Vitória é um sistema estuarino da costa leste do Brasil que apresenta grande importância econômica e características ímpares, já que se desenvolveu entre três unidades geomorfológicas distintas. Apesar disto, este ambiente apresenta poucos estudos relacionados às suas características geológicas e oceanográficas. O presente trabalho se focou no preenchimento desta lacuna através da descrição da morfologia, da distribuição sedimentar e dos padrões sonográficos da Baía de Vitória, buscando relações entre os mesmos e inferindo os processos sedimentares dominantes em cada trecho do estuário. A análise integrada mostrou boa correlação entre os métodos e revelou a grande complexidade deste sistema estuarino. Três diferentes regiões foram identificadas mostrando processos distintos: o estuário superior apresentou input sedimentar fluvial e processos estuarinos; um largo trecho da região central do sistema apresentou características erosivas, relacionadas a adaptações morfológicas e ao aumento das correntes provocadas pelos estreitamentos artificiais da baía, propiciando a formação de formas de fundo; e a boca do estuário se apresentou dominada por processos marinhos. Parte da região central do estuário mostrou características mascaradas pela atividade antrópica através da instalação de pontes, aterros e dragagens.

Geoquímica de fósforo como indicadora da qualidade ambiental e dos processos estuarinos do Rio Jaguaribe - costa nordeste oriental brasileira

Phosphorus geochemistry as a proxy of environmental estuarine processes at the Jaguaribe River, Northeastern Brazil. Sedimentation of different phosphorus geochemical fractions can characterize the natural or anthropogenic processes dominant in the watershed. Selective chemical extraction of different phosphorus geochemical forms in estuarine sediments showed the predominance of inorganic over organic forms suggesting an increase in inorganic phosphorus input from anthropogenic sources. Local hydrochemistry favors the dominance of inorganic ferric and carbonatic phosphorus. Ongoing changes in the estuarine throphy, from mesothrophic to euthrophic, may decrease the immobilization of these forms, increasing dissolved phosphorus and favoring euthrophy. Detritic phosphorus suggests a fluvial origin of this fraction and acts as a tracer of river influence upon the estuary.

Sedimentology and stratigraphy of the Lower Silurian Grimsby formation, in subsurface, Lake Erie and Southwestern Ontario

Since the first offshore Lake Erie well was drilled in 1941, the Grimsby and Thorold formations of the Cataract Group have been economically important to the oil and gas industry of Ontario. The Cataract Group provides a significant amount of Ontario's gas production primarily from wells located on Lake Erie. The Grimsby - Thorold formations are the result of nearshore estuarine processes influenced by tides on a prograding shelf and are composed of subtidal channel complexes, discrete tidal channels, mud flats and non-marine deposits. Deposition was related to a regressive - transgressive cycle associated with eustatic sea level changes caused by the melting and resurgence of continental glaciation centred in Africa in the Late Ordovician/Early Silurian. Grimsby deposition began during a regression with the deposition of subtidal channel complexes incised into the marine deposits of the Cabot Head Formation. The presence of mud drapes and mud couplets suggest that these deposits were influenced by tides. These deposits dominate the lower half of the Grimsby. Deposition continued with a change from these subtidal channel complexes to laterally migrating, discrete, shallow tidal channels and mud flats. These were in turn overlain by the non-marine deposits of the Thorold Formation. Grimsby - Thorold deposition ended with a major transgression replacing siliciclastic deposition with primarily carbonate deposition. Sediment was sourced from the east and southeast and associated with a continuation of the Taconic Orogeny into the Early Silurian. The fluvial head of the estuary prograded from a shoreline that was located in western New York and western Pennsylvania running NNE-SSW and then turning NW-SE and paralleling the present day Lake Erie shoreline. iii The facies attributed to the Grimsby - Thorold formations can be ascribed to the three zones within the tripartite zonation suggested by Dalrymple et ale (1992) for estuaries, that is, a marine-dominated facies, a mixed energy facies, and a facies that is dominated by fluvial processes. Also, sediments within the Grimsby - Thorold are commonly fining upwards sequences which are common in estuarine settings whereas deltaic deposits are normally composed of coarsening upwards sequences in a vertical wedge shape with coarser material near the head. The only coarsening observed was in the Thorold Formation and attributed to non-marine deposition by palynological evidence. The presence of a lag deposit at the base of the sediments of the Grimsby Thorold formations suggests that they were incised into the Cabot Head Formation. Further, the thickness of Early Silurian sediments located between the top of the Queenston Formation, where Early Silurian sedimentation began, to the top of the Reynales - Irondequoit formation are constant whether the Grimsby - Thorold formations are present or not. Also, cross-sections using a sand body located in the Cabot Head Formation for correlation further imply that the Grimsby Formation has been incised into the previous deposits of the Cabot Head.

Nitrogen flows from European watersheds to coastal marine waters

Nitrogen flows from European watersheds to coastal marine waters Executive summary Nature of the problem • Most regional watersheds in Europe constitute managed human territories importing large amounts of new reactive nitrogen. • As a consequence, groundwater, surface freshwater and coastal seawater are undergoing severe nitrogen contamination and/or eutrophication problems. Approaches • A comprehensive evaluation of net anthropogenic inputs of reactive nitrogen (NANI) through atmospheric deposition, crop N fixation,fertiliser use and import of food and feed has been carried out for all European watersheds. A database on N, P and Si fluxes delivered at the basin outlets has been assembled. • A number of modelling approaches based on either statistical regression analysis or mechanistic description of the processes involved in nitrogen transfer and transformations have been developed for relating N inputs to watersheds to outputs into coastal marine ecosystems. Key findings/state of knowledge • Throughout Europe, NANI represents 3700 kgN/km2/yr (range, 0–8400 depending on the watershed), i.e. five times the background rate of natural N2 fixation. • A mean of approximately 78% of NANI does not reach the basin outlet, but instead is stored (in soils, sediments or ground water) or eliminated to the atmosphere as reactive N forms or as N2. • N delivery to the European marine coastal zone totals 810 kgN/km2/yr (range, 200–4000 depending on the watershed), about four times the natural background. In areas of limited availability of silica, these inputs cause harmful algal blooms. Major uncertainties/challenges • The exact dimension of anthropogenic N inputs to watersheds is still imperfectly known and requires pursuing monitoring programmes and data integration at the international level. • The exact nature of ‘retention’ processes, which potentially represent a major management lever for reducing N contamination of water resources, is still poorly understood. • Coastal marine eutrophication depends to a large degree on local morphological and hydrographic conditions as well as on estuarine processes, which are also imperfectly known. Recommendations • Better control and management of the nitrogen cascade at the watershed scale is required to reduce N contamination of ground- and surface water, as well as coastal eutrophication. • In spite of the potential of these management measures, there is no choice at the European scale but to reduce the primary inputs of reactive nitrogen to watersheds, through changes in agriculture, human diet and other N flows related to human activity.

Mid- to Late-Holocene estuarine infilling processes studied by radiocarbon dates, high resolution seismic and biofacies at Vitoria Bay, Espirito Santo, Southeastern Brazil

A Baía de Vitória é um estuário com 20 km de comprimento, morfologicamente estreito, com um regime de micromaré e, como outros estuários modernos, formado durante a última transgressão pós-glacial. A morfologia de fundo do estrato estuarino é caracterizada por um canal natural principal limitado por planícies de maré com manguezais desenvolvidos. Datações de radiocarbono originais foram obtidas para a área. Cinco idades de radiocarbono estendendo-se de 1.010 a 7.240 anos AP foram obtidas através de dois testemunhos de sedimento, representando uma sequência estratigráfica de 5 m de espessura. Os resultados indicam que até aproximadamente 4.000 anos cal. AP, as condições ambientais da Baía de Vitória eram ainda de uma baía aberta, com uma conexão livre e aberta com águas marinhas. Durante os últimos 4.000 anos a baía experimentou uma fase de regressão importante, tornando-se mais restrita em termos de circulação da água do mar e provavelmente aumentando a energia de marés. Três superfícies estratigráficas principais foram reconhecidas, limitando fácies transgressiva, transgressiva/nível de mar alto e regressiva. A morfologia do canal atual representa um diastema de maré, mostrando fácies regressivas truncadas e erodidas. Biofácies de foraminíferos, passando de ambiente marinho para ambiente salobro e de manguezais em planície de maré confirmam a interpretação sismoestratigráfica. A ausência de biofácies de mangue em um dos dois testemunhos é tambémuma indicação de ravinamento de maré atual.

Synergic Reactions in the Estuarine Environment leading to Modulation of Aluminium metal during Transport Processes (in Cochin Estuary)

The research work which was carried out to Synergic Reactions in the Estuarine Environment leading to Modulation of Aluminium metal during Transport Processes (in Cochin Estuary)Estuaries are considered as sink or source for terrestrial and various anthropogenically generated materials. These include naturally occurring elements Al, Si, Fe or trace inorganics or industrial pollutants of different types. There have been reports on both positive and negative impacts by the introduction of above materials into the ecosystem.This thesis deals with the trace metal Aluminium (Al) whose average concentration (about 8%) in the earths crust is surpassed only by that of Oxygen and Silicon. There can be no doubt that most of the land derived materials reaches the ocean through rivers via estuaries. An important aspect noticed here is that the concentration of dissolved Al is much lower in sea water than in river water.On critically analysing Cochin estuary, for the entire cycles, covering monsoon, postmonsoon and premonsoon, the following salient features are documented as hereunder. Dissolved Al exhibits high and variable trends in Cochin estuary, the influencing parameters being salinity, SPM, pH and dissolved Si. A general profile showed removal in upper/mid estuary followed by regeneration in the mid/lower estuary and further decrease seawards in the southern/northem arms.Distribution appears to be a function of freshwater input, the monsoon season exhibiting very high concentrations throughout the estuary. As the river discharge decreased with the progress of seasons, dissolved Al concentration also decreased, the metal limiting itself to the upper and mid estuary.

Stable isotopes of bulk organic matter to trace carbon and nitrogen dynamics in an estuarine ecosystem in Babitonga Bay (Santa Catarina, Brazil)

The biogeochemical processes affecting the transport and cycling of terrestrial organic carbon in coastal and transition areas are still not fully understood One means of distinguishing between the sources of organic materials contributing to particulate organic matter (POM) in Babitonga Bay waters and sediments is by the direct measurement of delta(13)C of dissolved inorganic carbon (DIC) and delta(13)C and delta(15)N in the organic constituents. An isotopic survey was taken from samples collected in the Bay in late spring of 2004. The results indicate that the delta(13)C and delta(15)N compositions of OM varied from -21.7 parts per thousand to -26 2 parts per thousand. and from + 9 2 parts per thousand. to -0 1 parts per thousand, respectively. delta(13)C from DIC ranges from +0.04 parts per thousand to -12.7 parts per thousand The difference in the isotope compositions enables the determination of three distinct end-members terrestrial, marine and urban Moreover, the evaluation of source contribution to the particulate organic matter (POM) in the Bay, enables assessment of the anthropogenic impact. Comparing the depleted values of delta(13)C(DIC) and delta(13)C(POC) it is possible to further understand the carbon dynamic within Babitonga Bay (C) 2010 Elsevier BV All rights reserved

Air Entrainment Processes in a Full-Scale Rectangular Dropshaft at Large Flows

Rectangular dropshafts, commonly used in sewers and storm water systems, are characterised by significant flow aeration. New detailed air-water flow measurements were conducted in a near-full-scale dropshaft at large discharges. In the shaft pool and outflow channel, the results demonstrated the complexity of different competitive air entrainment mechanisms. Bubble size measurements showed a broad range of entrained bubble sizes. Analysis of streamwise distributions of bubbles suggested further some clustering process in the bubbly flow although, in the outflow channel, bubble chords were in average smaller than in the shaft pool. A robust hydrophone was tested to measure bubble acoustic spectra and to assess its field application potential. The acoustic results characterised accurately the order of magnitude of entrained bubble sizes, but the transformation from acoustic frequencies to bubble radii did not predict correctly the probability distribution functions of bubble sizes.

Transformation processes, pathways, and possible sources of distinctive polychlorinated dibenzo-p-dioxin signatures in sink environments

In recent years, studies on environmental samples with unusual dibenzo-p-dioxin (PCDD) congener profiles were reported from a range of countries. These profiles, characterized by a dominance of octachlorinated dibenzodioxin (OCDD) and relatively low in dibenzofuran (PCDF) concentrations, could not be attributed to known sources or formation processes. In the present study, the processes that result in these unusual profiles were assessed using the concentrations and isomer signatures of PCDDs from dated estuarine sediment cores in Queensland, Australia. Increases in relative concentrations of lower chlorinated PODS and a relative decrease of OCDD were correlated with time of sediment deposition. Preferred lateral, anaerobic dechlorination of OCDD represents a likely pathway for these changes. In Queensland sediments, these transformations result in a distinct dominance of isomers fully chlorinated in the 1,4,6,9-positions (1,4-patterns), and similar 1,4-patterns were observed in sediments from elsewhere. Consequently, these environmental samples may not reflect the signatures of the original source, and a reevaluation of source inputs was undertaken. Natural formation of PCDDs, which has previously been suggested, is discussed; however, based on the present results and literature comparisons, we propose an alternative scenario. This scenario hypothesizes that an anthropogenic PCDD precursor input (e.g. pentachlorophenol) results in the contamination. These results and hypothesis imply further investigations are warrented into possible anthropogenic sources in areas where natural PCDD formation has been suggested.

Functional role of macrobenthos in estuarine sediment dynamics

Thesis submitted to the Universidade Nova de Lisboa,Faculdade de Ciências e Tecnologia for the degree of Doctor of Philosophy in Environmental Engineering

Element speciation and behaviour in metal-rich Boreal river and estuarine systems using ultrafiltration and chemical modelling

The bioavailability of metals and their potential for environmental pollution depends not simply on total concentrations, but is to a great extent determined by their chemical form. Consequently, knowledge of aqueous metal species is essential in investigating potential metal toxicity and mobility. The overall aim of this thesis is, thus, to determine the species of major and trace elements and the size distribution among the different forms (e.g. ions, molecules and mineral particles) in selected metal-enriched Boreal river and estuarine systems by utilising filtration techniques and geochemical modelling. On the basis of the spatial physicochemical patterns found, the fractionation and complexation processes of elements (mainly related to input of humic matter and pH-change) were examined. Dissolved (<1 kDa), colloidal (1 kDa-0.45 μm) and particulate (>0.45 μm) size fractions of sulfate, organic carbon (OC) and 44 metals/metalloids were investigated in the extremely acidic Vörå River system and its estuary in W Finland, and in four river systems in SW Finland (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), largely affected by soil erosion and acid sulfate (AS) soils. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these investigated waters. One of the most important findings of this study is that the very large amounts of metals known to be released from AS soils (including Al, Ca, Cd, Co, Cu, Mg, Mn, Na, Ni, Si, U and the lanthanoids) occur and can prevail mainly in toxic forms throughout acidic river systems; as free ions and/or sulfate-complexes. This has serious effects on the biota and especially dissolved Al is expected to have acute effects on fish and other organisms, but also other potentially toxic dissolved elements (e.g. Cd, Cu, Mn and Ni) can have fatal effects on the biota in these environments. In upstream areas that are generally relatively forested (higher pH and contents of OC) fewer bioavailable elements (including Al, Cu, Ni and U) may be found due to complexation with the more abundantly occurring colloidal OC. In the rivers in SW Finland total metal concentrations were relatively high, but most of the elements occurred largely in a colloidal or particulate form and even elements expected to be very soluble (Ca, K, Mg, Na and Sr) occurred to a large extent in colloidal form. According to geochemical modelling, these patterns may only to a limited extent be explained by in-stream metal complexation/adsorption. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of AS soils, known to exist in the catchment, could be clearly distinguished in the Sirppujoki River as it had very high concentrations of a metal sequence typical of AS soils in a dissolved form (Ba, Br, Ca, Cd, Co, K, Mg, Mn, Na, Ni, Rb and Sr). In the Paimionjoki River, metal concentrations (including Ba, Cs, Fe, Hf, Pb, Rb, Si, Th, Ti, Tl and V; not typical of AS soils in the area) were high, but it was found that the main cause of this was erosion of metal bearing phyllosilicates and thus these metals occurred dominantly in less toxic colloidal and particulate fractions. In the two nearby rivers (Laajoki and Mynäjoki) there was influence of AS soils, but it was largely masked by eroded phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high background metal concentrations due to erosion. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring, or geochemical modelling based on such data, can lead to a great overestimation of the water toxicity in this environment. The potentially toxic elements that are of concern in AS soil areas will ultimately be precipitated in the recipient estuary or sea, where the acidic metalrich river water will gradually be diluted/neutralised with brackish seawater. Along such a rising pH gradient Al, Cu and U will precipitate first together with organic matter closest to the river mouth. Manganese is relatively persistent in solution and, thus, precipitates further down the estuary as Mn oxides together with elements such as Ba, Cd, Co, Cu and Ni. Iron oxides, on the contrary, are not important scavengers of metals in the estuary, they are predicted to be associated only with As and PO4.

Unraveling a Benchmark for Sulphur Akin in the Cochin Estuarine System

The thesis deals with a benchmark study of dissolved and sedimentary sulphur compounds which play prominent roles in the prevailing redox conditions in the selected sites of Cochin estuarine system. Sulphur and its analogues play prominent roles in estuarine biochemical processes. A complete knowledge on the sulphur involvement in these processes is restricted due to the lacking of data on the organic sulphur compounds. Sulphate and sulphide in surface and bottom water and Sulphate, acid volatile sulphide and total sulphur in sediments were studied and correlated to know their interrelations in determining the redox condition of the environment. It also characterises the sediments of the sites on the basis of total organic carbon: total sulphur ratio. The study had attempted to decrease the concentration levels of sulphur in the sedimentary environment by the application of a remedial measure. Knowledge of sulphur uptake by plants from prior literatures has prompted to use phytoremediation for decreasing the sulphur concentration. Phytoremediation is an emerging technology that uses plants to clean up or remediate contaminated soil, sludges, sediments, and ground water through contaminant removal, degradation or containment. The plant selected was wheat grass since earlier studies have shown that wheat grass is effective in remediating pollutants particularly trace metals. So reduction in the concentration of selected trace metals was also focussed.