Assessing the current state of the Gironde Estuary by mapping priority contaminant distribution and risk potential in surface sediment

Based on high spatial resolution monitoring, the first spatial distribution maps for the eight trace elements identified as priority contaminants in aquatic systems (i.e. As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) in surface sediments of the Gironde Estuary (SW France) are presented. This large European fluvial–estuarine system is known for important historical multi-element (mainly Cd, Zn, Cu and Pb) pollution by former mining and mineral processing activation in the Riou-Mort watershed located 350 km upstream the estuary. As a consequence, oyster production in the estuary is prohibited, and Cd concentrations in oysters from the Marennes-Oléron area are close to consumption thresholds. Surface sediment samples were analysed for grain size, particulate organic C and trace element concentrations. Determination of trace elements was carried out by ICP-MS for As, Cd, Cr, Cu, Ni, Pb, Th and Zn, and by CV-AAS for Hg. Total and potentially released trace element stocks in the surface sediment were evaluated by using concentrations in the estuary and in selected sediment core. Assuming that sediment resuspension affects mainly the uppermost sediment layer, the total trace element stocks in the studied 0–10 cm depth range may represent the equivalent of one (Cd) to eight (As, Cr) times the annual fluvial trace element inputs into the estuary. Comparing total trace element concentrations in surface sediment with: (i) data on the regional geochemical baseline to evaluate the potentially remobilised fraction and (ii) the potentially bioavailable fraction aimed at establishing a first spatially resolved risk assessment of the trace element “cocktail” present in these sediments at the estuary scale. After correction for grain size effects by Th normalisation, potentially highly toxic metals such as Cd and Hg showed the highest enrichment factors. From ecotoxicological indices, areas were identified and quantified where trace element levels and mobility may bear a risk to benthic organisms. The GIS-based spatial distribution of ecotoxicological indices for the trace element “cocktail” suggests that ∼95% of the surface sediment are ‘Low–Medium’-priority zones, highlighting the need for further impact studies. The produced maps of trace element distributions and associated risk potentials are likely to be a useful tool to authorities in charge of sustainable estuarine management, e.g. for the optimisation of dredging activities or development of the estuarine infrastructure.     

Has river rehabilitation begun? Social perspectives from the Upper Hunter catchment, New South Wales, Australia

Recognition of the degraded state of rivers across the world has prompted the development of management programmes which promote river repair through rehabilitation practices. Efforts to date have emphasised concerns for biophysical attributes of rivers to the relative exclusion of socio-cultural values. Ultimately, the process of river repair must move beyond this technical focus and incorporate collective societal engagement, participation and ownership. However, the inherent complexities of informing and managing this process limit the prospects that engagement will be translated into an effective and sustained practice. This qualitative case study research analyses the community’s knowledge, views and opinions regarding geomorphic river change and river works projects undertaken in the Upper Hunter catchment, New South Wales, Australia. The responses and views expressed by the participants highlight how ineffective communication and limited understanding of past river work practices has inhibited the connection and ownership between the people and their river. Essentially, historical river management was viewed as a technical process that failed to incorporate social values and aspirations, and which gave inadequate consideration to local knowledge and experience. Participants identified the need to address both diversity and commonality in vision-building and the need for greater confidence and transparency in river science and management. In light of these responses, this paper argues for the adoption of a geo-social, transdisciplinary approach to river rehabilitation.     

Helgoland Roads,North Sea: 45 Years of Change

The Helgoland Roads time series is one of the richest temporal marine data sets available. Running since 1962, it documents changes for phytoplankton, salinity, Secchi disc depths and macronutrients. Uniquely, the data have been carefully quality controlled and linked to relevant meta-data, and the pelagic time series is further augmented by zooplankton, intertidal macroalgae, macro-zoobenthos and bacterioplankton data. Data analyses have shown changes in hydrography and biota around Helgoland. In the late 1970s, water inflows from the south-west to the German Bight increased with a corresponding increase in flushing rates. Salinity and annual mean temperature have also increased since 1962 and the latter by an average of 1.67°C. This has influenced seasonal phytoplankton growth causing significant shifts in diatom densities and the numbers of large diatoms (e. g. Coscinodiscus wailesii). Changes in zooplankton diversity have included the appearance of the ctenophore Mnemiopsis leidyi. The macroalgal community also showed an increase in green algal and a decrease in brown algal species after 1959. Over 30 benthic macrofaunal species have been newly recorded at Helgoland over the last 20 years, with a distinct shift towards southern species. These detailed data provide the basis for long-term analyses of changes on many trophic levels at Helgoland Roads.     

Development of a sharp interface model that simulates coastal aquifer flow with the coupled use of GIS

A simulation program, which works seamlessly with GIS and simulates flows in coastal aquifers, is presented in the present paper. The model is based on the Galerkin finite element discretization scheme and it simulates both steady and transient freshwater and saltwater flow, assuming that the two fluids are separated by a sharp interface. The model has been verified in simple cases where analytical solutions exist. The simulation program works as a tool of the GIS program, which is the main database that stores and manages all the necessary data. The combined use of the simulation and the GIS program forms an integrated management tool offering a simpler way of simulating and studying saline intrusion in coastal aquifers. Application of the model to the Yermasogia aquifer illustrates the coupled use of modeling and GIS techniques for the examination of regional coastal aquifer systems.

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Resumen Se ha desarrollado un modelo casi tridimensional de elementos finitos para simular el flujo de agua dulce y salada, tanto en régimen estacionario como en transitorio, en sistemas acuíferos costeros, bajo la hipótesis de separación por medio de una interfaz abrupta. Las ecuaciones del modelo han sido discretizadas mediante un esquema de Galerkin de discretización en elementos finitos. El modelo ha sido verificado en casos sencillos para los que existe solución analítica. Todos los datos necesarios se introducen y gestionan con un Sistema de Información Geográfica [SIG] por ordenador. El programa de simulación forma parte del programa de SIG, constituyendo una herramienta integrada de gestión para estudiar la intrusión salina en acuíferos costeros. La aplicación del modelo al acuífero de Yermasogia ilustra el uso acoplado de las técnicas de modelación y de SIG con el fin de examinar sistemas acuíferos costeros a escala regional.

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Résumé Pour étudier un système aquifère côtier, nous avons développé un modèle aux éléments finis en quasi 3-D qui simule les écoulements deau douce et deau salée en régime aussi bien permanent que transitoire. Les équations qui les régissent sont discrétisées par un schéma de discrétisation de Garlekin aux éléments finis. Le modèle a été vérifié dans des cas simples où il existe des solutions analytiques. Toutes les données nécessaires sont introduites et gérées grâce à un logiciel de gestion de SIG. Le programme de simulation est utilisé comme un outil du logiciel de SIG, constituant ainsi un outil de gestion intégrée dont le but est de simuler et détudier lintrusion saline dans les aquifères côtiers. Lapplication du modèle à laquifère de Yermasogia illustre lutilisation couplée de la modélisation et des techniques de SIG pour létude des systèmes aquifères côtiers régionaux.

     

Influence of localised igneous activity on cleat dawsonite formation in Late Permian coal measures, Upper Hunter Valley, Australia

Stable (δ¹³C and δ¹⁸O) and radiogenic ⁸⁷Sr/⁸⁶Sr isotopic data have been used to investigate the origin of cleat dawsonite (NaAlCO₃(OH)₂) in the Late Permian Wittingham Coal Measures of the Upper Hunter region in the Sydney Basin, New South Wales. The δ¹³C_PDB values have a narrow range (− 1.7‰ to + 2.4‰), with an average of + 0.3‰, suggesting a magmatic source for the carbon. In contrast, δ¹⁸O_SMOW values have a wide range (+ 13.6‰ to + 19.8‰), and decrease systematically with decreasing distance from a major intrusion. This systematic variation reflects establishment of localised hydrothermal cells. Water–rock interaction between fluids associated with these hydrothermal cells, and Rb-poor volcaniclastic detritus in the coal measures, produced mantle-like ⁸⁷Sr/⁸⁶Sr (0.705032 to 0.706464) in the dawsonite.     

Biodiversität und Ökologie aquatischer Oomycetes‐Arten im Auesee und in der Fulda in Kassel (Hessen)

Biodiversity and Ecology of Species of Aquatic Oomycetes in the Aue Lake and the River Fulda in Kassel (Hessen) In this study, we record diversity and ecology of aquatic Oomycetes in the Aue Lake and the river Fulda in Kassel (Hesse, Germany). We monthly collected water samples of both water bodies from July 2003 to June 2004. The baiting method was used to gain an insight into the occurrence of aquatic Oomycetes. A total of 14 species of aquatic Oomycetes belonging to the orders Saprolegniales, Leptomitales and Olpidiopsidales could be isolated of both water bodies. Numerous saprophytic isolates of Rhizophydium Schenk (Chytridiomycetes), Rhizophydium carpophilum (Zopf) Fischer, parasitic on Oomycetes, and additionally one species of Plasmodiophoromycetes, Woronina polycystis Cornu could be isolated. Many isolates of Saprolegniales attributable to the genera Achlya Nees, Dictyuchus Leitgeb, Saprolegnia Nees and Pythium Pringsheim (Pythiales), which could only be identified on generic level, could be isolated as well. The species were examined and discussed with respect to their occurrence in the stagnant water Aue Lake and/or in the running water of the river Fulda. Half of the isolated species only occurred in one of the water bodies. In this study the occurrence of Achlya proliferoides Coker could be documented for Germany for the first time. The trophic status of the Aue Lake and of the classification of water quality of the river Fulda were determined by limnological‐chemical parameters obtained by simultaneous investigations of both water bodies.     

Changes in geochemistry and mineralogy of thermally altered coal, Upper Hunter Valley, Australia

Igneous intrusions thermally and geochemically alter coal, commonly causing economic and safety problems for many coal mines. The effects of two dykes on the inorganic content of the Late Permian bituminous Upper Wynn seam were determined from analyses of 44 samples that were collected along transects approaching the intrusions. Petrographic and XRD data were used to determine sample mineralogy, and INAA and XRF spectrometry were utilised to determine the contents of 57 elements. The mineralogy of the unaltered coal, altered coal and dyke is dominated by carbonates, particularly dawsonite, which formed by epigenetic precipitation at a late stage, after thermal alteration. Ankerite and siderite are the products of thermal alteration and are restricted to the altered coal and dykes.Principal component analysis, correlations and compositional trends approaching the intrusions were used to subdivide the elements into groups and to identify the mineralogical affinity of each group. Geochemical data are more sensitive than mineralogy for defining the size of the alteration halo, and three zones ranging from unaltered coal, through altered coal to highly coked coal are recognised as each intrusion is approached.The alteration halos differ in extent (9.5 and 56 m wide), but their size is not a multiple of the size of the causative intrusion. At the contact between coal and intrusion, concentrations of elements with affinities to some aluminosilicates, oxides, carbonates, sulphides and organic components are enriched, while other aluminosilicate-related elements are depleted. In the altered coal towards the edge of the alteration halo, some aluminosilicate elements are enriched and oxide elements are depleted.     

Heat capacities of Fe2O3-bearing silicate liquids

Direct measurements of liquid heat capacity, using a Setaram HT1500 calorimeter in step-scanning mode, have been made in air on six compositions in the Na₂O-FeO-Fe₂O₃-SiO₂ system, two in the CaO-FeO-Fe₂O₃-SiO₂ system and four of natural composition (basanite, andesite, dacite, and peralkaline rhyolite). The fitted standard deviations on our heat capacity measurements range from 0.6 to 3.6%. Step-scanning calorimetry is particularly useful when applied to iron-bearing silicate liquids because: (1) measurements are made over a small temperature interval (10K) through which the ferric-ferrous ratio of the liquid remains essentially constant during a single measurement; (2) the sample is held in equilibrium with an atmosphere that can be controlled; (3) heat capacity is measured directly and not derived from the slope of enthalpy measurements with temperature. Liquid compositions in the sodic and calcic systems were chosen because they contain large concentrations of Fe₂O₃ (up to 19 mol%), and their equilibrium ferric-ferrous ratios were known at every temperature of measurement. These measurement have been combined with heat capacity (Cp) data in the literature on iron-free silicate liquids to fit Cp as a function of composition. A model assuming no excess heat capacity (linear combination of partial molar heat capacities of oxide components) reproduces the liquid data within error (±2.2% on average). The derived partial molar heat capacity of the Fe₂O₃ component is 240.9 ±7.9 J/g.f.w.-K, with a standard error reduced by more than a factor of two from that in earlier studies. The model equation, based primarily on simple, synthetic compositions, predicts the heat capacity of the four magmatic liquids within 1.8% on average.     

A transferable interatomic potential for crystalline phases in the system MgO—SiO2

A central interatomic potential model is presented for compounds in the binary system MgO-SiO₂. The potential, of a simple form which consists of a Coulombic term, a Born repulsive term, and a Van der Walls term for oxygen-oxygen interactions, is designed to predict the properties of magnesium silicates containing Si in octahedral and tetrahedral coordination. This is achieved by fitting simultaneously to forsterite and MgSiO₃ ilmenite crystal structure data, and fixing the partial ionic charges using elastic data for forsterite. The potential is found to transfer successfully to γ-Mg₂SiO₄ and MgSiO₃ perovskite. The potential results in local structural errors around the bridging oxygen ions in clinoenstatite and β-Mg₂SiO₄. The predicted structure for MgSiO₃ garnet is similar to the experimentally measured structure of the MnSiO₃ analogue. Calculated elastic constants average to K=2.41 Mbar and μ=1.44 Mbar for the bulk and shear moduli of MgSiO₃ perovskite, and K=1.87 Mbar and μ=1.10 Mbar for the bulk and shear moduli of MgSiO₃ garnet.     

Thermochemistry of phases in the system MgGa2O4-Mg2GeO4

The enthalpies of solution in molten 2PbO · B₂O₃ of phases synthesized at one atmosphere in the system MgGa₂O₄-Mg₂GeO₄ have been measured. A spinel solid solution, which is stable at 1400 °C from the MgGa₂O₄ end-member to 27 mole percent Mg₂GeO₄, shows endothermic heats of mixing of up to 10 kJ/mole at the solubility limit. The spinelloid phase, Mg₃Ga₂GeO₈, is energetically less stable than a mixture of terminal spinel solid solutions (0.73 MgGa₂O₄·0.27 Mg₂GeO₄(sp)+Mg₂GeO₄(sp)), by 3.63±3.64 kJ/mole. This indicates that the spinelloid is a high-entropy phase.The volume of the spinel solid solution, MgGa₂O₄-Mg₂GeO₄, shows a positive deviation from Vegard's Law. Modeling of the cation distribution in the solid solution indicates that this V is due to a change in the spinel type from inverse towards normal as the Mg₂GeO₄ content increases.