Generic Natural Systems Evaluation - Thermodynamic Database Development and Data Management

Thermodynamic data are essential for understanding and evaluating geochemical processes, as by speciation-solubility calculations, reaction-path modeling, or reactive transport simulation. These data are required to evaluate both equilibrium states and the kinetic approach to such states (via the affinity term or its equivalent in commonly used rate laws). These types of calculations and the data needed to carry them out are a central feature of geochemistry in many applications, including water-rock interactions in natural systems at low and high temperatures. Such calculations are also made in engineering studies, for example studies of interactions involving man-made materials such as metal alloys and concrete. They are used in a fairly broad spectrum of repository studies where interactions take place among water, rock, and man-made materials (e.g., usage on YMP and WIPP). Waste form degradation, engineered barrier system performance, and near-field and far-field transport typically incorporate some level of thermodynamic modeling, requiring the relevant supporting data. Typical applications of thermodynamic modeling involve calculations of aqueous speciation (which is of great importance in the case of most radionuclides), solubilities of minerals and related solids, solubilities of gases, and stability relations among the various possible phases that might be present in a chemical system at a given temperature and pressure. If a phase can have a variable chemical composition, then a common calculational task is to determine that composition. Thermodynamic modeling also encompasses ion exchange and surface complexation processes. Any and all of these processes may be important in a geochemical process or reactive transport calculation. Such calculations are generally carried out using computer codes. For geochemical modeling calculations, codes such as EQ3/6 and PHREEQC, are commonly used. These codes typically provide 'full service' geochemistry, meaning that they use a large body of thermodynamic data, generally from a supporting database file, to sort out the various important reactions from a wide spectrum of possibilities, given specified inputs. Usually codes of this kind are used to construct models of initial aqueous solutions that represent initial conditions for some process, although sometimes these calculations also represent a desired end point. Such a calculation might be used to determine the major chemical species of a dissolved component, the solubility of a mineral or mineral-like solid, or to quantify deviation from equilibrium in the form of saturation indices. Reactive transport codes such as TOUGHREACT and NUFT generally require the user to determine which chemical species and reactions are important, and to provide the requisite set of information including thermodynamic data in an input file. Usually this information is abstracted from the output of a geochemical modeling code and its supporting thermodynamic data file. The Yucca Mountain Project (YMP) developed two qualified thermodynamic databases to model geochemical processes, including ones involving repository components such as spent fuel. The first of the two (BSC, 2007a) was for systems containing dilute aqueous solutions only, the other (BSC, 2007b) for systems involving concentrated aqueous solutions and incorporating a model for such based on Pitzer's (1991) equations. A 25 C-only database with similarities to the latter was also developed for the Waste Isolation Pilot Plant (WIPP, cf. Xiong, 2005). The NAGRA/PSI database (Hummel et al., 2002) was developed to support repository studies in Europe. The YMP databases are often used in non-repository studies, including studies of geothermal systems (e.g., Wolery and Carroll, 2010) and CO2 sequestration (e.g., Aines et al., 2011)

A Comparison of Computerized Chemical Models for Equilibrium Calculations in Aqueous Systems

A survey of computer programs which are currently being used to calculate the distribution of species in aqueous solutions, especially natural waters, has been made in order to 1) provide an inventory of available programs with a short description of their uses, 2) compare the consistency of their output for two given test solutions and 3) identify major weaknesses or problems encountered from their use. More than a dozen active programs which can be used for distribution of species and activity calculations for homogeneos equilibria among the major anions and cations of natural waters have been inventoried. Half of these programs can also accept several trace elements including Fe, Al, Mn, Cu, Ni, Zn, Cd, Pb, Ag, Hg, As, Ba, Sr, and B. Consistency between programs was evaluated by comparing the log of the molal concentrations of free ions and complexes for two test solutions: a hypothetical seawater analysis and a hypothetical river water analysis. Comparison of the free major ion concentrations in the river water test case shows excellent agreement for the major species. In the seawater test case there is less agreement and for both test cases the minor species commonly show orders of magnitude differences in concentrations. These differences primarily reflect differences in the thermodynamic data base of each chemical model although other factors such as activity coefficient calculations, redox assumptions, temperature corrections, alkalinity corrections and the number of complexes used all have an affect on the output

Comparing Skill Acquisition Under Varying Onsets of Differential Reinforcement: A Preliminary Analysis

The purpose of the current study was to evaluate the effect of implementing differential reinforcement at different times relative to the onset of teaching new skills to learners with autism spectrum disorder. Specifically, we first determined the most efficient differential reinforcement arrangement for each participant. Using the most efficient arrangement, we evaluated if differential reinforcement from the immediate onset, early onset, or late onset is the most efficient for learners to acquire a new skill. Three children diagnosed with autism spectrum disorder who have a history of receiving intervention based on the principles of applied behavior analysis participated in this study. The immediate onset of differential reinforcement resulted in the most efficient instruction in 6 of 7 comparisons. The results are discussed in light of previous studies and suggestions for future research are provided

Corrosion of the International Simple Glass under acidic to hyperalkaline conditions

Assessment of glass dissolution kinetics, under disposal relevant temperature and pH environments, is required to credibly estimate radionuclide release rates from vitrified radioactive waste. Leaching of the International Simple Glass (ISG) under acidic to hyperalkaline conditions was examined. Forward rate measurements have been obtained using the dynamic leaching SPFT protocol and rate parameters for B, Na and Si in the basic regime; errors in rates predicted using these parameters at high pH and temperature are significant because the fitting uses logarithmic data. Longer term behaviour under hyperalkaline conditions, representative of some disposal environments, was investigated using the PCT and MCC-1 static leaching protocols with Ca(OH)2 solutions for up to 120 days (PCT) and 720 days (MCC-1). In hyperalkaline conditions dissolution was incongruent for all elements and the presence of alternating zirconia-rich and zirconia-poor alteration layers was observed on all leached monoliths, indicating the occurrence of a self-organisation phenomenon during leaching

Ultra-diffuse hydrothermal venting supports Fe-oxidizing bacteria and massive umber deposition at 5000 m off Hawaii

© International Society for Microbial Ecology, 2011. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in The ISME Journal 5 (2011): 1748–1758, doi:10.1038/ismej.2011.48.A novel hydrothermal field has been discovered at the base of Lōihi Seamount, Hawaii, at 5000 mbsl. Geochemical analyses demonstrate that ‘FeMO Deep’, while only 0.2 °C above ambient seawater temperature, derives from a distal, ultra-diffuse hydrothermal source. FeMO Deep is expressed as regional seafloor seepage of gelatinous iron- and silica-rich deposits, pooling between and over basalt pillows, in places over a meter thick. The system is capped by mm to cm thick hydrothermally derived iron-oxyhydroxide- and manganese-oxide-layered crusts. We use molecular analyses (16S rDNA-based) of extant communities combined with fluorescent in situ hybridizations to demonstrate that FeMO Deep deposits contain living iron-oxidizing Zetaproteobacteria related to the recently isolated strain Mariprofundus ferroxydans. Bioenergetic calculations, based on in-situ electrochemical measurements and cell counts, indicate that reactions between iron and oxygen are important in supporting chemosynthesis in the mats, which we infer forms a trophic base of the mat ecosystem. We suggest that the biogenic FeMO Deep hydrothermal deposit represents a modern analog for one class of geological iron deposits known as ‘umbers’ (for example, Troodos ophilolites, Cyprus) because of striking similarities in size, setting and internal structures.Funding has been provided by the NSF Microbial Observatories Program (KJE, DE, BT, HS and CM), by the Gordon and Betty Moore Foundation (KJE), the College of Letters, Arts, and Sciences at the University of Southern California (KJE) and by the NASA Astrobiology Institute (KJE, DE)