Thermodynamic stability of CoOOH and its coprecipitation with manganese

A precipitate of cobalt oxyhydroxides formed by bubbling oxygen through a dilute solution of Co(NO₃)₂ held at pH 9.0 and 25°C was aged for 23 months in contact with the original solution, with access to atmospheric oxygen. Co₃O₄ and CoOOH were identified in the precipitate by X-ray diffraction. Chemical equilibria involving these solids were evaluated by measurements of solution pH and Co²⁺ activities and by redox potential measurements and gave a $\text{ΔG}{}_{\mathrm{coOOH}}{}^0$ of $\text{?92.3 ± 0.5 kcal/mole}$. This value and other thermodynamic data show relative feasibility of hypothetical reaction steps and changes in reaction paths during automated coprecipitation titrations and subsequent aging of a precipitate that finally contained βMnOOH, MnO₂ (birnessite) and CoOOH.     

pp′-DDT adsorption to suspended particulate matter in sea water

A procedure was devised to study pp′-DDT [2,2-bis($\text{p-}\text{chlorophenyl}$)-1,1,1-trichloroethane] adsorption and desorption to suspended particulates in aqueous solutions. DDT adsorption to a marine sediment, sediment fractions, clay and humic acid suspended in sea water was investigated and the humic fraction was found to have a greater adsorbing capacity than the clay or sediment. Removal of the humic fraction from sediment reduced the adsorption capacity to less than 60 per cent of the original sediment sample. It was concluded that suspended humic particulates may be important agents for transporting chlorinated hydrocarbons through the water column and for concentrating them in sediments and in detritus-feeding organisms.     

Carbon and sulfur in the Swaziland sequence

Sedimentary and igneous rocks of the Swaziland Sequence of South Africa (>3,200 my. old) contain total carbon (0.09–8.28%), organic carbon (0.04–1.95%) and sulfur (9–53,000 ppm). Amounts of organic carbon are generally high in the lower part of the Sequence (based on two samples from the Theespruit Formation). Sulfur content varies widely with no obvious correlations or trends. These rocks may contain clues to the early carbon and sulfur cycles on earth.     

Sulfur in peat-forming systems of the Okefenokee Swamp and Florida Everglades: origins of sulfur in coal

Six sulfur forms were investigated in profiles of freshwater- and marine-derived peat-forming systems of the Okefenokee Swamp, Georgia and Everglades Swamp, Florida. Total sulfur levels of 0.1–10% were found, thus indicating a major incorporation of sulfur in the very early stages of coal formation. The quantities of hydrogen sulfide and elemental sulfur observed appeared to be indicative of whether marine or freshwater conditions prevailed at the site of deposition. Carbon-bonded sulfur accounted for 70% of the total sulfur in the freshwater peat and 50% of the total sulfur in the marine peat. Over 15% of the total sulfur was in pyritic combination in the marine environment, while levels of pyrite in the freshwater peats were an order of magnitude lower. An ester-sulfate fraction represented 25% of the total sulfur in both freshwater and marine peats. The levels of sulfur forms in the peat profiles are compared to those observed in living plants and to various coals; levels of pyrite and organic sulfur in the peat are similar to those found by other investigators in freshwater-derived and marine-derived coals.     

Wetland Loss,Juvenile Salmon Foraging Performance,and Density Dependence in Pacific Northwest Estuaries

During the transition of juveniles from fresh water to estuarine and coastal environments, the survival of Pacific salmon (Oncorhynchus spp.) can be strongly size selective and cohort abundance is partly determined at this stage. Because quantity and quality of food influence juvenile salmon growth, high rates of prey and energy acquisition during estuarine residence are important for survival. Human activities may have affected the foraging performance of juvenile salmon in estuaries by reducing the area of wetlands and by altering the abundance of salmon. To improve our understanding of the effects of wetland loss and salmon density on juvenile salmon foraging performance and diet composition in estuaries, we assembled Chinook salmon (Oncorhynchus tshawytscha) diet and density data from nine US Pacific Northwest estuaries across a gradient of wetland loss. We evaluated the influence of wetland loss and density on juvenile Chinook salmon instantaneous ration and energy ration, two measures of foraging performance, and whether the effect of density varied among estuaries with different levels of wetland loss. We also assessed the influence of wetland loss and other explanatory variables on salmon diet composition. There was no evidence of a direct effect of wetland loss on juvenile salmon foraging performance, but wetland loss appeared to mediate the effect of density on salmon foraging performance and alter salmon diet composition. Specifically, density had no effect on foraging performance in the estuaries with less than 50 % wetland loss but had a negative effect on foraging performance in the estuaries with greater than 50 % wetland loss. These results suggest that habitat loss may interact with density to constrain the foraging performance of juvenile Chinook salmon, and ultimately their growth, during a life history stage when survival can be positively correlated with growth and size.     

Analysis of pressuremeter geometry effects in clay using critical state models

The conventional interpretation methods of pressuremeter testing effectively approximate pressuremeter membranes as infinitely long. As a result, the effects of the two‐dimensional geometry of pressuremeters are ignored, leading to an overestimation of soil shear strength by pressuremeter testing, as demonstrated in several previous studies. This paper presents results of a numerical study of two‐dimensional geometry effects on self‐boring pressuremeter tests in undrained clay. The results are obtained using critical state soil models with an effective stress formulation. This is in contrast to most (if not all) existing studies on pressuremeter geometry effects, which were based on perfectly plastic soil models (e.g. Yu (Cavity expansion theory and its application to the analysis of pressuremeters. DPhil Thesis, The University of Oxford, 1990), Yeung and Carter (Proc. 3rd Int. Symp. on Pressuremeters, 1990), and Houlsby and Carter (Géotechnique, 1993; 43 (4):567–576)). The present study suggests that the overestimation of soil strength due to the neglect of finite pressuremeter length is significantly affected by the soil model used in the calculations. It is found that for clays with a high overconsolidation ratio (OCR) the strength overestimation predicted using critical state soil models could be considerably smaller than that predicted using perfectly plastic soil models. The main conclusion of this numerical study is that care must be exercised before directly applying any numerically determined pressuremeter geometry correction factors in practice. Copyright © 2005 John Wiley & Sons, Ltd.     

Thallium diagenesis in lacustrine sediments

Dated sediment cores and porewaters from two Canadian Shield lakes, located 40 km from Québec City (L. Tantaré) and 25 km downwind from an important smelter in northwestern Québec (L. Vose), were analyzed for thallium and other geochemical variables. Atmospheric deposition is the only source of anthropogenic Tl to these lakes. The porewater Tl concentration profiles in L. Tantaré display a peak below the sediment-water interface that suggests post-depositional Tl remobilization and transport to the overlying water and deeper sediments; such a dissolved Tl peak occurs just above the sediment-water interface in L. Vose. Modeling the porewater Tl profiles with a diagenetic reaction-transport equation reveals a zone of dissolved Tl production lying above a zone of Tl consumption in L. Tantaré sediments. In contrast, in L. Vose, Tl diffuses across the sediment-water interface from the anoxic hypolimnion and is fixed to the surficial sediments. The localization of the consumption zones, the shape of the dissolved Tl, sulfide and iron profiles, as well as calculations of saturation states are all consistent with the removal of Tl from porewater by co-precipitation with and/or adsorption to Fe sulfides. The concentrations of Tl removed from or added to sediments after their deposition (i.e., diagenetic Tl) amount to up to 36% of measured sediment Tl concentrations. Comparison of the reconstructed historical Tl records with those of polycyclic aromatic hydrocarbons (PAHs) and of Pb originating from coal burning or from smelting activities indicate that coal combustion is the major source of atmospheric Tl to L. Tantaré and that an additional important Tl source to L. Vose is the nearby smelter.     

Détermination expérimentale des paramètres équivalents d'un milieu poreux hétérogène en écoulements uniforme ou radial

Tracer tests are carried out in a heterogeneous porous medium that has a 3D correlated random distribution of the permeabilities. The fitting of numerical models provides the values of equivalent permeability and macrodispersivity characterizing a 2D homogeneous horizontal medium. Different flow configurations are studied: uniform, radial and pump and treat (doublet). The fitted parameter sets are independent of the flow type, except for the doublet. They are greater than the values predicted by stochastic theories, due to the small number of correlation lengths explored by the tracer and the limited extension of the experimental set-up. To cite this article: C. Danquigny, P. Ackerer, C. R. Geoscience 337 (2005).     

Effects of nonlinear model response on allocation of streamflow depletion: exemplified by the case of Beaver Creek,USA

Anomalies found when apportioning responsibility for streamflow depletion are examined. The anomalies arise when responsibility is assigned to the two states that contribute to depletion of Beaver Creek in the Republican River Basin in the United States. The apportioning procedure for this basin presumes that the sum of streamflow depletions, computed by comparing simulation model runs with and without groundwater pumping from individual states, approximates the streamflow depletion when both states are pumping. In the case study presented here, this presumed superposition fails dramatically. The stream drying and aquifer-storage depletion, as represented in the simulation model used for allocation, are examined in detail to understand the hydrologic and numerical basis for the severe nonlinear response. Users of apportioning procedures that rely on superposition should be aware of the presence and likely magnitude of nonlinear responses in modeling tools.     

Heat-producing elements in the lunar mantle: Insights from ion microprobe analyses of lunar pyroclastic glasses

We provide new estimates for the abundance of heat-producing elements in the lunar mantle by using SIMS techniques to measure the concentrations of thorium and samarium in lunar pyroclastic glasses. Lunar pyroclastic glasses are utilized in this study because they represent quenched products of near-primary melts from the lunar mantle and as such, they provide compositional information about the mantle itself. Thorium and samarium were measured because: (1) Th is not significantly fractionated from Sm during partial melting of the pyroclastic glass source regions, which are dominated by olivine and pyroxene. Therefore, the Th/Sm ratios that we measure in the pyroclastic glasses reflect the Th/Sm ratio of the pyroclastic glass source regions. (2) Strong correlations between Th, U, and K on the Moon allow us to use measured Th concentrations to estimate the concentrations of U and K in the pyroclastic glasses. (3) Th, Sm, U, and K are radioactive elements and as such, their concentrations can be used to investigate heat production in the lunar mantle.The results from this study show that the lunar mantle is heterogeneous with respect to heat-producing elements and that there is evidence for mixing of a KREEP component into the source regions of some of the pyroclastic glasses. Because the source regions for many of the glasses are deep (?400 km), we propose that a KREEP component was transported to the deep lunar mantle. KREEP enriched sources produce 138% more heat than sources that do not contain KREEP and therefore, could have provided a source of heat for extended periods of nearside basaltic magmatism. Data from this study, in conjunction with models for the fractional crystallization of a lunar magma ocean, are used to show that the average lunar mantle contains 0.15 ppm Th, 0.54 ppm Sm, 0.039 ppm U, and 212 ppm K. This is a greater enrichment in radiogenic elements than some earlier estimates, suggesting a more prolonged impact of radiogenic heat on nearside basaltic volcanism.