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Aquatic Geochemistry (v.3, #2)


Ionic Strength Dependence of Rare Earth – NTA Stability Constants at 25°C by Biqiong Li; Robert H. Byrne (pp. 99-115).
Observations of competitive complexation of NTA by Cu2+ and rare earth element (REE) ions are used to determine REE-NTA stability constants at ionic strengths between 0.1 and 5.0 molar. Although REE stability constants change markedly with ionic strength, differences in the ionic strength dependence of REE-NTA stability constants across the rare earth element series are small. The ionic strength dependence of logβ1 for Y and REEs with NTA at 25 °C can be described as: logβ1(M) = logβ1(M)0 - 9.198 I1/2/(1+B I1/2)+C I + D I3/2, where β1(M) = [MNTA°][M3+]-1[NTA3-]-1, I is ionic strength, B = 1.732, C = 0.1596, D = 0.0816, and logβ1(M)° is the metal-NTA stability constant at zero ionic strength.

Keywords: rare earth elements; copper; complexation; ionic strength effects; nitrilotriacetic acid; lanthanide; yttrium


Hydrograph Separation of the Amazon River: A Methodological Study by J. Mortatti; J.M. Moraes; R.L. Victoria; L.A. Martinelli (pp. 117-128).
The hydrograph separation of the Amazon river was performed using three different methodologies. Were applied isotopic, filter-separation, and mixing methods to estimate the contributions of the surface runoff (event water) and baseflow (pre-event water) components to the total river flow, during the 1973–1974 hydrological years. The importance of the baseflow contribution, mainly during the peak discharge, suggesting that the groundwater plays a much more active and important role in the storm dynamics, was verified. Similar results were obtained for all the methods used, and the applicability of each one was discussed in detail. For the Amazon river basin, the average contribution of the baseflow was 56% of the total river flow, at peak discharge. The average surface runoff contribution, which represents the water capable of mechanical erosion in drainage basins, expressed in terms of the surface runoff coefficient (Kr), was 31.9%, while the mean contribution of the baseflow, expressed by the baseflow coefficient (Kb), was 68.1%.

Environmental Controls on Groundwater Chemistry in an Offshore Island Aquifer: Fiesta Key, Florida by Donald D. Machusak; Lee R. Kump (pp. 129-167).
A field study was undertaken on the Florida Bay side of Fiesta Key, Florida, to identify the chemical characteristics of a previously unexplored offshore groundwater system and to define the critical parameters affecting groundwater movement and interaction with sediment pore fluids and bedrock. Emphasis was placed on the upper 2 meters of bedrock, where groundwater recharge and discharge potentials are maximized, along a 100 meter transect extending from the island margin. Bedrock cores were used to describe Pleistocene depositional textures, and were sampled at discrete depths to determine the extent of water-rock interaction. Piezometers installed into each core hole were used to monitor surface and ground water tide levels, and for the systematic collection of water samples for a large suite of chemical determinations.Aqueous chemical data indicate that these groundwaters are marine in origin, anoxic, and moderately hypersaline (S = 36–40). Exchange of bedrock pore fluids with overlying Bay waters is restricted by a layer of Holocene sediment and a discontinuous soilstone crust formed at the modern bedrock surface. Groundwater chemistry near the sediment/bedrock interface is marked by elevated concentrations of total alkalinity and Ca2+, and by significant Mg2+ depletion. These waters likely acquired their unusual chemistry by mixing between deeper groundwaters and overlying, early diagenetically altered, sediment porewaters. High alkalinity and calcium concentrations presumably result from the combination of the effects of aerobic metabolism, carbonate dissolution, and sulfate reduction. Mg-depletion most likely resulted from the precipitation of Mg-calcite. These unusual chemistries disappear by 2 m depth in the groundwater system, where Ca2+ and Mg2+ concentrations are similar to those expected for seawater under slightly hypersaline conditions.The Pleistocene bedrock contains low Mg, Sr, F, and P concentrations relative to the overlying unconsolidated Holocene carbonate sediments. This is consistent with the diagenetic recrystallization processes that the bedrock has undergone. Hydraulic conditions favor the net recharge of Florida Bay seawater to the groundwater system, but there are insufficient tide data to identify cyclical water exchange rates or groundwater flow patterns.

A Comparative Study of Molecular Paleosalinity Indicators: Chromans, Tocopherols and C20 Isoprenoid Thiophenes in Miocene Lake Sediments (Nördlinger Ries, Southern Germany) by Assem O. Barakat; Jürgen Rullkötter (pp. 169-190).
Distributions of alkylated chromans and C20 isoprenoid thiophenes were investigated in four organic-matter- and sulfur-rich black shales of Miocene age deposited in the ancient crater lake of the Nördlinger Ries (southern Germany), a meteorite impact crater. Paleosalinity parameters based on these compound classes generally confirm sedimentological evidence of increased salinity over certain periods of the lake's history, but the data from both groups of compounds are not consistent. Diagenetically related molecular constituents were therefore studied to estimate the sensitivity of these parameters. The influence of thiolanes on the isoprenoid thiophene parameter was found to be low, whereas too little is known at present about the origin and diagenetic fate of alkylated chromans to conclude definitely that an alkylated chroman paleosalinity parameter can reliably be applied to a wide range of depositional settings.

Keywords: Chromans; homohopenes; isoprenoid thiolanes; isoprenoid thiophenes; methylated MTTC; Nördlinger Ries; tocopherols

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