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Aquatic Geochemistry (v.5, #4)
Comparison of the Complexation of Cu and Cd by Humic or Fulvic Acids and by Ligands Observed in Lake Waters by Hanbin Xue; Laura Sigg (pp. 313-335).
The complexation of Cu and Cd by ligands observed in filtered unfractionated lakewaters is compared to the complexation by humic and fulvic acids. Complexation parameters (conditional stability constants and ligand concentrations) of Suwannee River fulvic acids (FA), purified peat humic acids (HA) and of ligands in lakewater samples have been determined using the same methods (ligand-exchange and CSV (cathodic stripping voltammetry) or ASV (anodic stripping voltammetry)), and the same titration ranges of Cu, Cd and organic carbon concentrations. The performance of the used techniques is first evaluated in FA and HA suspensions, and gives comparable results with the literature values for the same materials, according to published models (5-site model, NICA model) and parameters. Model calculations using the WHAM model for FA and HA (Tipping, 1994) are also presented. The comparison of titrations of FA and HA with Cu and Cd with those of lakewater samples indicates that stronger ligands than FA and HA are present at low concentrations in the lakewaters. Specific strong ligands occur in particular in eutrophic lake waters, whereas in a lake with higher metal concentrations and low biological productivity the ligands more closely match the fulvic acid characteristics.
Keywords: Cd complexation; Cu complexation; humic-metal complexation; humic substances; lake water; natural ligands
Estimation of Pore Water Concentrations from DGT Profiles: A Modelling Approach by Michael P. Harper; William Davison; Wlodek Tych (pp. 337-355).
The technique of Diffusional Gradients in Thin-films (DGT) can be used in situ to obtain high resolution profiles of trace-metals in sediment pore waters. Substances sampled by DGT continuously diffuse through a ‘diffusion layer’ comprising a hydrogel prior to being immobilized by binding to a resin layer. DGT therefore measures a time averaged flux from the pore water to the resin. Interpretation of this flux as pore water concentration is problematic for two reasons. Firstly, the pore water concentration adjacent to the sampler may become depleted by the DGT induced flux. Secondly, if there are steep vertical chemical gradients in the pore waters, they may relax by diffusion along the gradient within the gel layer. The extent of relaxation depends on the diffusion coefficient, gradient steepness, and diffusion layer thickness. Two dimensional (2D) numerical models of DGT deployments in horizontally uniform sediments were used to investigate to what extent DGT measured profiles accurately reproduced (a) the shape of pore water concentration profiles, and (b) the magnitude of pore water concentrations. A method is developed which translates high resolution DGT measured flux profiles into reliable estimates of pore water concentrations. Linear relationships are given which estimate the minimum DGT measured peak width (as a function of diffusion layer thickness) that ensures accurate reproduction of the shape and the magnitude of peaks in pore water concentrations. Peaks in DGT profiles obtained from assemblies with diffusion layer thicknesses of 0.3 mm (0.5 mm) should be at least 1.2 mm (1.8 mm) wide for their shape to reflect accurately their true shape in the pore water, and at least 1.7 mm (2.7 mm) wide to ensure the peak concentration is accurately estimated.
Keywords: concentration-depth profiles; DGT; modelling; pore water; sediments
Weathering and Geochemical Processes Controlling Solute Acquisition in Ganga Headwater–Bhagirathi River, Garhwal Himalaya, India by Shiv Kumar Pandey; Abhay Kumar Singh; S. I. Hasnain (pp. 357-379).
Water and suspended sediment samples were collected along a longitudinal transect of the Bhagirathi – a headwater stream of the river Ganga, during the premonsoon and postmonsoon seasons, in order to assess the solute acquisition processes and sediment transfer in a high elevation river basin. Study results show that surface waters were dominated by HCO3 and SO4 in anionic abundance and Ca in cationic concentrations. A high concentration of sulphate in the source region indicates oxidative weathering of sulphide bearing minerals in the drainage basin. The combination of high concentrations of calcium, bicarbonate and sulphate in river water suggests that coupled reaction involving sulphide oxidation and carbonate dissolution are mainly controlling the solute acquisition processes in the drainage basin. The sediment transfer reveals that glacial weathering and erosion is the major influence on sediment production and transfer. The seasonal and spatial variation in ionic concentration, in general, is related to discharge and lithology. The sediment mineralogy and water mineral equilibrium indicate that water composition is in equilibrium with kaolinite. The river Bhagirathi annually delivers 0.74 M.tons of dissolved and 7.88 M.tons of suspended load to the river Ganga at Devprayag. The chemical and physical denudation rate of the Bhagirathi is 95 and 1010 tons/km2/yr, higher than the Indian and global average.
Keywords: Bhagirathi river; Ganga headwater; solute acquisition; suspended sediments; weathering
The Speciation of (CH3)2Sn2+ in Electrolyte Solution Containing the Major Components of Natural Waters by Claudia Foti; Antonio Gianguzza; Frank J. Millero; Silvio Sammartano (pp. 381-398).
Hydrolysis constants of dimethyltin(IV) cation, in different salt solutions (CaCl2: 0.15 ≤ I ≤ 0.90; MgCl2: 0.30 ≤ I ≤ 0.60; NaCl-–NaClO4, NaCl-–NaNO3 mixtures: I = 3; NaCl-–Na2SO4 mixtures: I = 1 mol dm-3) were determined by potentiometric ([H+]-glass electrode) measurements. These data, together with previous data (De Stefano et al., 1996b) were interpreted in terms of DHT (Debye–Hückel type) and Pitzer equations. The mixed electrolyte solution results also allowed us to obtain Θ and Ψ parameters for the Pitzer equation. Calorimetric measurements were made at different ionic strengths in order to find the temperature dependence of hydrolysis constants and of the relative interaction parameters. The body of results allows us to determine the speciation of natural waters in a wide range of ionic strengths and temperatures.
Keywords: dependence on medium of hydrolysis constants; ΔH° for the hydrolysis of (CH3)2Sn2+ ; hydrolysis of (CH3)2Sn2+ ; Pitzer interaction parameters; speciation of (CH3)2Sn2+ in natural waters