Near-field solubility constraints on radionuclide mobilization and their influence on waste package design

The paper addresses the physical and chemical processes that can serve to immobilize waste radionuclides within the confines of an underground repository. These processes, which can be made largely independent of the chemical nature of the host rock, depend for their efficacy upon the maintenance of a very low flow rate of groundwater through the repository constituents. The very long-lived waste products, in particular the actinides, are very insoluble in water under conditions of alkalinity and oxygen potential that will exist in a repository when cement is used as a backfill or as a matrix for the waste. The same chemical conditions tend to favour a fairly long life for steel containers. The paper suggests how these factors may be used to immobilize wastes and draws some conclusions on the relative value of the various engineered features of a repository. Some natural geological analogues are explored as a means of assisting the extrapolation of waste behaviour over very long times.

1981 ◽  
Vol 11 ◽  
Author(s):  
David Savage ◽  
Jane E. RObbins

An essential component of any assessment of HLRW geological disposal options is the quantitative prediction of radionuclide release rates from the near-field over time spans of the order of 103-106 years. Fundamental to this assessment is the investigation of the interaction of potential wasteforms with groundwater under repository conditions of temperature, pressure, and groundwater flow-rate. Consequently, many studies world-wide have been initiated to examine the kinetics of wasteform dissolution over a wide range of physical and chemical conditions. Although these studies have provided a considerable amount of invaluable data on wasteform-fluid interactions, they have tended to focus on breakdown of the wasteform itself, and not on the fate of released waste components in the nearfield. For example, effects of saturation of species in solution, precipitation of secondary minerals or amorphous gels, and the effect of host rock chemistry on the products (solid and fluid) of waste-fluid interaction have largely been ignored or even specifically excluded in laboratory experiments. This is despite growing evidence from source term modelling studies which suggest that the above processes may well be the chief factors in governing rates of radionuclide release from the near-field, bearing in mind the limited availability of ground


1992 ◽  
Vol 150 ◽  
pp. 365-370
Author(s):  
J.M.C. Rawlings

Molecular observations and models of the chemical processes in the ejecta of novae and supernovae are reviewed. Although only a few molecular species have been identified, the information that they give has provided great insight into the physical and chemical conditions. We now have quite a detailed understanding of the processes at work in both novae and supernovae.


1997 ◽  
Vol 178 ◽  
pp. 331-340 ◽  
Author(s):  
W.A. Schutte

We review the techniques which are applied to study by means of laboratory simulation the chemical and physical processes taking place in ices in interstellar dense clouds. We summarize the current situation with regard to spectroscopy of interstellar ice analogs and with regard to the simulation of chemical processes such as modification of the ices by UV photons and surface reactions between reactive atoms and molecules. It is discussed how such data can be used to explore the potential of the icy mantles both as a record of the various chemical conditions that occur in dense clouds and as an environment for unique interstellar chemical processes.


2020 ◽  
pp. 823-845
Author(s):  
Stuart F. Simmons ◽  
Benjamin M. Tutolo ◽  
Shaun L.L. Barker ◽  
Richard J. Goldfarb ◽  
François Robert

Abstract Epithermal, Carlin, and orogenic Au deposits form in diverse geologic settings and over a wide range of depths, where Au precipitates from hydrothermal fluids in response to various physical and chemical processes. The compositions of Au-bearing sulfidic hydrothermal solutions across all three deposit types, however, are broadly similar. In most cases, they comprise low-salinity waters, which are reduced, have a near-neutral pH, and CO2 concentrations that range from <4 to >10 wt %. Experimental studies show that the main factor controlling the concentration of Au in hydrothermal solutions is the concentration of reduced S, and in the absence of Fe-bearing minerals, Au solubility is insensitive to temperature. In a solution containing ~300 ppm H2S, the maximum concentration of Au is ~1 ppm, representing a reasonable upper limit for many ore-forming solutions. Where Fe-bearing minerals are being converted to pyrite, Au solubility decreases as temperature cools due to the decreasing concentration of reduced S. High Au concentrations (~500 ppb) can also be achieved in strongly oxidizing and strongly acidic chloride solutions, reflecting chemical conditions that only develop during intense hydrolytic leaching in magmatic-hydrothermal high-sulfidation epithermal environments. Gold is also soluble at low to moderate levels (10–100 ppb) over a relatively wide range of pH values and redox states. The chemical mechanisms which induce Au deposition are divided into two broad groups. One involves achieving states of Au supersaturation through perturbations in solution equilibria caused by physical and chemical processes, involving phase separation (boiling), fluid mixing, and pyrite deposition via sulfidation of Fe-bearing minerals. The second involves the sorption of ionic Au on to the surfaces of growing sulfide crystals, mainly arsenian pyrite. Both groups of mechanisms have capability to produce ore, with distinct mineralogical and geochemical characteristics. Gold transport and deposition processes in the Taupo Volcanic Zone, New Zealand, show how ore-grade concentrations of Au can accumulate by two different mechanisms of precipitation, phase separation and sorption, in three separate hydrothermal environments. Phase separation caused by flashing, induced by depressurization and associated with energetic fluid flow in geothermal wells, produces sulfide precipitates containing up to 6 wt.% Au from a hydrothermal solution containing a few ppb Au. Sorption on to As-Sb-S colloids produces precipitates containing tens to hundreds of ppm Au in the Champagne Pool hot spring. Sorption on to As-rich pyrite also leads to anomalous endowments of Au of up to 1 ppm in hydrothermally altered volcanic rocks occurring in the subsurface. In all of these environments, Au-undersaturated solutions produce anomalous concentrations of Au that match and surpass typical ore-grade concentrations, indicating that near-saturated concentrations of dissolved metal are not a prerequisite for generating economic deposits of Au. The causes of Au deposition in epithermal deposits are related to sharp temperature-pressure gradients that induce phase separation (boiling) and mixing. In Carlin deposits, Au deposition is controlled by surface chemistry and sorption processes on to rims of As-rich pyrite. In orogenic deposits, at least two Au-depositing mechanisms appear to produce ore; one involves phase separation and the other involves sulfidation reactions during water-rock interaction that produces pyrite; a third mechanism involving codeposition of Au-As in sulfides might also be important. Differences in the regimes of hydrothermal fluid flow combined with mechanisms of Au precipitation play an important role in shaping the dimensions and geometries of ore zones. There is also a strong link between Au-depositing mechanisms and metallurgical characteristics of ores.


1989 ◽  
Vol 54 (1) ◽  
pp. 117-135
Author(s):  
Oldřich Pytela ◽  
Vítězslav Zima

The method of conjugate deviations based on the regression analysis has been suggested for construction of a new nucleophilicity scale. This method has been applied to a set of 28 nucleophiles participating in 47 physical and chemical processes described in literature. The two-parameter nucleophilicity scale obtained represents-in the parameter denoted as ND-the general tendency to form a bond to an electrophile predominantly on the basis of the orbital interaction and-in the parameter denoted as PD-the ability to interact with a centre similar to the proton (basicity). The linear correlation equation involving the ND, PD parameters and the charge appears to be distinctly better than the most significant relations used. The correlation dependences have the physico-chemical meaning. From the position of individual nucleophiles in the space of the ND and PD parameters, some general conclusions have been derived about the factors governing the reactivity of nucleophiles.


Author(s):  
Andrew Steane

The life of an ordinary tree is described, in terms of the main physical and chemical processes: carbon capture by photosynthesis; entropy and energy; moisture. The information expressed in the tree comes partly from the DNA and partly from the sunlight. The tree does not push upwards from the ground, but solidifies the air.


ACS Photonics ◽  
2019 ◽  
Vol 6 (12) ◽  
pp. 3039-3056 ◽  
Author(s):  
Vanessa N. Peters ◽  
Srujana Prayakarao ◽  
Samantha R. Koutsares ◽  
Carl E. Bonner ◽  
Mikhail A. Noginov

1993 ◽  
Vol 265 (2) ◽  
pp. H543-H552 ◽  
Author(s):  
Y. Yuan ◽  
W. M. Chilian ◽  
H. J. Granger ◽  
D. C. Zawieja

This study reports measurements of albumin permeability in isolated coronary venules. The isolated microvessel technique allows the quantification of transmural exchange of macromolecules under tightly controlled physical and chemical conditions. Transvenular exchange of albumin was studied in isolated coronary venules during alterations in filtration rate caused by changes in intravascular pressure. The apparent permeability coefficient of albumin (Pa) at an intraluminal pressure of 11 cmH2O was 3.92 +/- 0.43 x 10(-6) cm/s. Elevating intraluminal pressure to 16 and 21 cmH2O increased Pa to 5.13 +/- 0.57 x 10(-6) and 6.78 +/- 0.66 x 10(-6) cm/s, respectively. Calculation of the true diffusive permeability coefficient of albumin (Pd) at zero filtration rate was 1.54 x 10(-6) cm/s. The product of hydraulic conductance (Lp) and (1 - sigma), where sigma is the solute reflection coefficient, was 3.25 x 10(-7) cm.s-1 x cmH2O-1. At a net filtration pressure of 4-5 cmH2O, diffusion accounts for > 60% of total albumin transport across the venular wall. Transmural albumin flux is very sensitive to filtration rate, rising 6.7% for each cmH2O elevation of net filtration pressure. At 11 cmH2O net filtration pressure, convection accounts for nearly 70% of net albumin extravasation from the venular lumen. We suggest that the isolated coronary venule is a suitable preparation for the study of solute exchange in the heart.


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