CEMENT and CONCRETE RESEARCH. Vol. 22, pp. 465-475, 1992. Printed in the USA. 0008-8846/92 $5.00 + .00.

Copyright 1992 Pergamon Press Ltd.

Thermodynamic modelling of cement degradation: Impact of redox conditions on radionuclide release

U.R.Berner Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland

Abstract
Portland cement, used as a solidification matrix and/or as backfill and construction material will determine the aqueous chemistry of a low- and intermediate level radioactive waste repository for very long periods of time. Based on a recently developed cement degradation model, the present work aims to investigate the influence of Eh on the solubility of actinides during the degradation of cement. Uranium is used as a representative for the actinides. Literature data are used to estimate the solubility of uranium bearing solid phases, which were found to be stable in cement-like systems. Log Kso values of -41 and of -66 are estimated for a solid called x-phase and for uranophane. In a strongly reducing environment (-450 mV) uraninite is the stable solid phase and uranium solubilities in the range 10 -s to 10 -1 M are modelled. Under moderately reducing conditions (-300/-200 mV) the solubility limiting phase depends on the pH of the cement pore solution, and at pH,,~12 a phase transformation is predicted. Modelled solubilities lie between 10 -~ and 10 -1 M. Uranium speciation in solution and the nature of the solubility limiting phase are very sensitive to both Eh and pH, whereas total dissolved uranium is not. It is concluded that the predictability is fair for strongly reducing conditions, but the uranium-cement system is not very well understood at moderately reducing conditions. The study raises a series of still unresolved questions, which clearly indicate the need of further experimental data.

1. I n t r o d u c t i o n
A Swiss repository for low- and intermediate level radioactive wastes will include large quantities of cemented waste matrices, construction elements and backfill materials [1]. The chemistry of hydrated cement will therefore determine the chemical properties of the repository near-field for a long period of time. A model describing the chemical evolution of a cement based repository during degradation in groundwater has recently been published [2,3]. This model is based on the thermodynamic description of the most relevmat hydrated cement phases and on a mixing tank model describing the temporal evolution of the cement degradation. The mixing tank model assumes that intruding groundwater equilibrates with the cement. The equilibrated solution is then replaced by fresh groundwater, whereby the replaced volume corresponds to the total porosity of the hydrated cement. Using a geochemical
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speciation code, the composition of the cement pore solution and of the remaining solid phase inventory is calculated for each replacement of the pore solution. The progress of degradation is therefore expressed in terms of water exchange cycles. The basic assumptions of the mixing tank model include that a) the cement is fully hydrated and all phases are in a state which can be modelled using the concepts of thermodynamic equilibrium, b)the chemical behaviour of cement can be sufficiently well modelled using a small set of model solids, namely CSH-gel, Ca(OH)2, Mg(OH)2, KOH and NaOH, c) the time period to reach equilibrium between cement and groundwater is short compared to transport times. The application of this simple degradation model showed that the hydrated cement phases disappear after 5000 to 10,000 water exchange cycles. Depending on the carbonate level of the groundwater, the hydrated cement phases will either dissolve or be converted into calcite. To predict the solubility/speciation of the radionuclides embedded in the cement matrix, the knowledge of the temporal pH development in the pore solution of the cement is an important prerequisite. During an early stage of cement degradation the pore solution pH is very high (pH 13.5 to 12.5), due to dissolution of Na,KOH. After complete leaching of the alkali hydroxides (typically after 50 to 100 water exchange cycles) the pH drops to 12.5 (saturation w.r. to portlandite) and remains on this level for about 1000 cycles. Due to the incongruent dissolution of calcium silicate hydrate gels (CSH-gels) the pH continuously drops to a value between 10.5 and 10 at ,~5000 cycles. The pH of the pore solution as a function of the cycle number is indicated in Figure 1. The cycle number is not correlated with real time. A guess, based on simple coupled model
-2

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-4

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tm

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et

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-8

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4 CaUO; - 4 5 0
m m m im m im m m im m - m m m m m ~--

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$ $ mmm m m mill

"i
;11

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O

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m m llm im mm m m I ~ LL

.o
I I

-14

1 (0.13 L)

10 (1.32 L)

100

1000

10000

(13.6 L)

(159. L)

Figure 1. Total dissolved uranium in the pore solution of degrading cement at different Eh values. Degradation is expressed in terms of pH vs. cycle numbers. The cycle number indicates how many times the equilibrated pore solution has been replaced by fresh groundwater. For clarification, the cumulative amount of groundwater contacted with 1 kg of hydrated cement is also given.

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(transport/chemistry) calculations [4] indicates that the time to complete one cycle falls into a range from 1 to 100 years if the groundwater flow is not restricted by the surrounding host rock. As an application of the cement degradation model, the solubility of uranium in the pore solution was modelled. The results indicated that the solubility of U exclusively depends on pH and on the properties of the solubility limiting phase. The compositions of cement and groundwater had nearly no influence. Depending on the choice of the solubility limiting solid, solubilities ranging from 10 -14 M (CaUOa) to 10 -4 M (UO2) were predicted (at -300 mV). From these results it was concluded that the experimental investigation of the solubility limiting phase is of central importance. Without a better understanding of the stable phases the prediction of uranium solubilities are meaningless if a bandwidth of ten orders of magnitude is considered. Many of the radionuclides relevant for the safety analysis of a repository axe redox sensitive (U, Np, Pu, Tc, Se...). For these elements the redox potential of the pore solution will be an essential parameter if solubility and speciation is concerned. The aim of the present work is therefore to investigate the impact of the redox conditions on the solubility limits. Again, uranium is selected as a representative for the actinides. For uranium a comprehensive collection of high quality thermodynamic data was published recently [5]. In addition, some experimental data concerning the behaviour of uranium in cement-like systems were available [7]. In a Swiss repository the relevant redox condition boundaries are given by the E h of the groundwater (,,~ -200 mV; [6]) and by the redox potential of the anoxic corroding iron (Eh < -450 mV). An Eh range between -450 mV and -200 mV was therefore selected for the present study. Figure 1 shows the solubility of uranium in degrading cement for two distinct solid phases at the upper and lower boundaries of Eh considered (note that for UO2 the -250 mV curve is plotted instead of the -200 mV curve, since very high U concentrations were obtained at -200 mV (cf. Figure 3a). As an indicator the pH of the pore solution is also given. Uraninite and CaUOa show an opposite dependency on the redox potenTable 1. Solubility data for x-phase and uranophane in different solutions as taken from reference [7]. CSH: calcium silicate hydrate gel; C/S: calcium/silicon ratio of CSH. Solid phase x-phase Solution Ca(OH)2(~q) sat. Ca(OH)2(s) sat. CSH(c/S=la) sat. CSH(c/S=la) sat. CSH(c/s=I.7) Total dissolved Total dissolved V (~moles/1) Ca (mmoles/1) 0.0155 11.5 0.0084 18.7 0.0076 0.94 0.0995 0.47 0.301 3.13 11.0 23.2 1.02 3.20 0.069 Measured pH 12.4 12.6 11.6 10.8 12.0 12.4 12.7 11.6 12.1 9.3

uranophane

x-phase: uranophane:

Ca(OH)2(~q) 0.83 sat. Ca(OH)2(s) 0.87 CSH(c/s=I.2) 0.027 CSH(c/s=,.~) 0.322 H20 0.27 Ca2UOs.xH20 Ca(UO2)2(SiO3)2(OH)2.5H20

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tial. The solubility curves indicate that the range of predicted solubilities is reduced at strongly reducing conditions. However, it should be noted that the curves in Figure 1 were modelled without considering, whether the solid phase is thermodynamically stable at the particular conditions or not.

2. Evaluation of available e x p e r i m e n t a l data

It is obvious that solubility predictions covering more than ten orders of magnitude are not very sensible. Based on experimental data we therefore first try to fix the nature of solubility limiting phases as well as their solubility properties. Atkins et al. [7] investigated the systems CaO-UOa-H20 and CaO-UO3-SiO2-H20. They found a solid with the composition Ca~UOb.l.3-1.7H20 (x-phase) and uranophane (Ca(UO2)2(SiO3)2(OH)2.bH~O) to be the stable phases. The results of the solubility experiments conducted with these two phases are listed in Table 1. From the measured solubility data the solubility products of the solid phases may be calculated by performing a speciation calculation for each measured equilibrium system. Using the data given in Table 1, the calculated solubility products show a large uncertainty range and, therefore, a different method was used for estimating the solubility products. The solubility of the particular phase in degrading cement was modelled using a guessed solubility product. This solubility product was then varied until a reasonable fit with the experimental data was achieved. We obtained Ca2UOb.xH20(~) + (3-x).H20 ~ 2Ca ~+ + UO~+ + 6OH- ; for x-phase and Ca(UO2)2(SiO3)2(OH)~.bH20(,) Ca ~+ + 2UO~ + + 2H~SiO]- + 2 O H - + 3H~O; log K~o ~ -66
~" -2 -4
o

log Kso ~ -41

experlmental data
~ ~O.e'e~ - F ~ uronophane x - phose

-~ -s
o

_c -8 E c -10

j
...

~_ -12 2
13 12 pH o f 11 pore 10 solution

Figure 2. Estimation of the solubility product of x-phase and uranophane. As indicated by the dashed line, the solid lines were obtained by adjusting the solubility product.

for uranophane. The uncertainty is estimated to be in the order of -t- 2 to 3 log K units. A comparison of modelled and experimental data is shown in Figure 2. The model curves are based on cement and on groundwater compositions taken from reference [2]. The dashed line in Figure 2 indicates how the model curve is shifted by varying the solubility product. The model curves are given as a function of the pore solution pH. In order to keep consistency with the thermodynamic laws, a comparison should also be made by giving total U as a function of Ca 2+ (and H2SiO4 in the case 2of uranophane). The comparison using Ca 2+ as the independent variable gives a very poor agreement between

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measured and modelled data and silica was not measured during the experiments. The available data are not complete enough to perfectly characterize the solubility properties of x-phase and uranophane. The solubility products given above should thereforebe considered as semi-quantitative estimates. It is obvious that additional equilibrium data are required to characterize this system. However, the most important result from Atkins' work is the stoichiometric identification of the uranium phases formed in cement-like systems. No thermodynamic modelling can be performed if the composition of the solid phase is not known. Recently, Finch and Ewing [8] reviewed the minerals occurring in the environment of uranium deposits. The phases found by Atkins et al. are compatible with this review. X-phase and also uranophane seem to be common oxidation products of uraninite deposits.

3. M o d e l c a l c u l a t i o n s and results
In this section it is shown how the redox potential of the cementitious environment influences the solubility of selected uranium solids in the pore solution of degrading cement. The modelling of cement degradation in natural groundwaters was summarised in the introduction, a more detailed description is given in [2,3]. The compositions of the cement and of the groundwater are not of key importance concerning the impact of Eh. These data (taken from [2,3]) are therefore not explicitly given in the present work. In addition to x-phase and uranophane, uraninite (UO2) is selected as a solubility determining phase, since uraninite is the most common uranium solid in reducing envi-

-2
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~O n

-10 ,500 -11 13

I

1600
I

,5000
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10

Figure 3a. Modelled solubility of uraninite in the pore solution of degrading cement as a function of pH at different Eh values. For comparison with Figure 1, the number of water exchange cycles is also indicated.

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-2.

-2

o=
E

-3. -4 -5
-6 -7
o

x-phase

-3 -4 -5
-8 -7

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13 12 pH of 11 pore 10 solution

-8 -9
-10 -11

-11

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11 pore

10 solution

Figure 3b. Modelled solubility of xphase in the pore solution of degrading cement as a function of pH at different Eh values.

Figure 3c. Modelled solubility of uranophane in the pore solution of degrading cement as a function of pH at different Eh values.

ronments. The solid CaUO4 (shown in Figure 1) is ruled out for several reasons. There is experimental evidence [7] that CaUO4 is not stable in hyperalkaline cement pore solutions. In the comprehensive review of Finch and Ewing [8] CaUO4 is not mentioned. According to [5], there is no doubt about the existence of this solid, but it is questionable, whether it is formed in a cementitious environment or not. The hydrates of U03 (e.g. schoepite) are not considered since these phases would lead to unrealistic high uranium concentrations in alkaline solutions. The mixed valence oxides U409, U30~ and U30s are also neglected: as a first approximation their behaviour may be represented by that of UO2. The solubility of UO2 , x-phase and uranophane in the pore solution of degrading cement at distinct redox potentials is shown in Figures 3a-c. it should be noted that the solubilities are presented as obtained from the model calculation. In particular, the thermodynamic stability of the limiting phase at given redox conditions was not checked. This will be addressed in the subsequent paragraphs. Total uranium is presented as a function of the pore solution pH and not as a function of the water exchange cycles like in Figure 1. With this kind of representation the redox dependency can be demonstrated more clearly (for clarification the number of water exchange cycles is also given in Figure 3a). The solubility of UO2 shows a pronounced dependency on Eh (Figure 3a). At -450 mV the solubility changes from 10 -s M to 10 -1 M in the pH range 13 to 10. The predominant complexes in solution are U(OH)2 and U(OH) . At -200 mV U(VI) is stabilized in the solution and at pH ~13 the solubility increases by six orders of magnitude, compared to -450 mV. The predominant complexes in solution are now UO2(OH)~- and UO2(OH)2. With decreasing pH the U(IV) - hydroxo complexes become stable and the solubility curve approximates the -450 mV curve. The solubility of x-phase is higher in the reducing environment than at -200 mV (300mV; Figure 3b). If compared with UO2 this findings seem to be strange, but the speciation in solution reveals that U(IV) and its hydroxo complexes are stabilized under these conditions. The strong solubility increase at lower pH indicates that x-phase will

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not exist stably below a pH of ~-,10. For uranophane the highest solubility is modelled at -450 mV (Figure 3c), which is due to the stabilization of U(IV) as in the case of x-phase. At -200 mV (-300 mV) a characteristic solubility minimum is obtained between pH 11 and 10. This minimum is

~
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pH of pore solution

pH of pore solution

Figure 4a. Total solubility of U in degrading cement at -450 mV.

Figure 4b. Total solubility of U in degrading cement at -300 mV.

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Figure 4c. Total solubility of U in degrading cement at -200 inV. Experimental data of Atkins et al. [7] are indicated with + (x-phase) and + (uranophane). The phase transformation at pH ~12 requires an oversaturation indicated by the arrow.

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a consequence of the increased silica concentration in this pH region [2,3]. The Figures 3a-c show modelled curves which will not be observed in real systems, since the thermodynamic laws require a minimal solubility for a given equilibrium system. The minimal concentration at any given pH is found by projecting the solubility curves for different solid phases on the same diagram. Depending on the redox potential, the resulting minimal solubility curves presented in Figures 4a-c are obtained. At -450 mV uraninite is the solubility limiting phase and total dissolved uranium varies between 5.10 -9 M and 3.10 -1 M in the pH range 13 to 10 (Figure 4a). At -300 mV and at -200 mV the nature of the solubility limiting phase depends on pH (Figures 4b and c). In the pH range 13 to 12 x-phase becomes stable. A solubility maximum (,-~10-7 M uranium) is predicted near pH 12. Below pH ~12 uraninite or uranophane become stable and total dissolved U decreases to ,,,10 -1 M. At -200 mV uranophane is the solubility limiting phase, whereas at -300 mV it may not be distinguished between uraninite and and uranophane, due to the uncertainty associated with the solubility product of uranophane. For comparison, the experimental data of Atkins et al. [7] are also given in Figure 4c. The speciation of dissolved uranium is not complicated. Due to the high pH only the hydroxo complexes of U(IV) and U(VI) are formed. Complexes with the anionic constituents of the attacking groundwater (CI-, S042-, CO~-, F-, NO3) are not relevant. Table 2 gives the predicted uranium speciation as a function of Eh and pH. In the strongly reducing environment U(IV) is predominant over the entire pH range. Only at pH values around 13 the U(VI) hydroxo complexes contribute significantly to the total dissolved uranium. In the moderately reducing environment U(VI) is predominant above pH ~11, whereas U(IV) hydroxo complexes determine the speciation below pH ~11. Table 2. Predicted uranium speciation in degrading cement as a function of Eh and pH. Complexes whose contribution to the total dissolved U is less than 1 % are not considered. The concentrations indicate total dissolved uranium. pH
13

-450 mVolts

-300 mVolts

-200 reVolts

U(OH);/U(OH)~ UO~(OH)~/UO2(OH)~5.10 -9 M

UO2(OH)~/UO2(OH)~10 -s M

UO2(OH)~/UO2(OH)~10 -s M

12

U(OH);/U(OH)
10 - 9 M

UO2(OH)~/UO2(OH)~U(OH);
I0 -r M

UO2(OH)~/UO2(OH)~I0 -7 M

11

U(OH)/U(OH);
5.10 -1 M

U(OH)/U(OH); UO2(OH)~
5.10 -10 M U(OH)/U(OH); 5.10 -1 M

UO2(OH);/U(OH)
2.10 -1 M U(OH)/UO2(OH)~ 10 -1 M

10

U(OH)/U(OH); 5.10 -1 M

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4. S u m m a r y and conclusions
Using a cement degradation model described elsewhere [2,3], the Eh dependency of the uranium solubility in the pore solution of degrading cement was investigated. From experimental data [7] the solubility products of x-phase (Ca2UOs.xH20) and of uranophane (Ca(UO2)2(SiO3)2(OH)2.5H20) were estimated. Based on these solids and on uraninite (UO2) the solubility of uranium was modelled in the Eh range -450 mV to -200 mV. Modelled uranium solubilities range from 10 -T M to 10 -1 M, experimental solubilities measured under oxic conditions cover the range from 10 -6 M to 10 -9 M. Considering the uncertainty of the estimated solubility products of x-phase and uranophane, the total dissolved uranium shows not a very pronounced Eh dependency. In addition, the agreement between measured and modelled solubilities is rather poor, at least below pH ~ 12. The speciation of dissolved uranium is more informative. Here, the results show that the speciation is very sensitive to Eh and pH. According to the thermodynamic data from NEA [5], the hydroxo complexes of uranium are formed exclusively in the high pH environment of cement pore solution. The free ions UO~+ and U 4+ are not important. Therefore, the ratio U(IV)/U(VI) in solution not only depends on Eh but also on the relative stability of the hydroxo complexes formed. The complexes of U(IV) are more stable than those of U(VI) which, for example, leads to the observation that U(OH) is predominant even at -200 mV and pH 10. The question as to the stable, solubility limiting phase is of particular interest. In the strongly reducing environment (-450 mV) the situation is not complicated, since uraninite is the only stable phase. This is in agreement with Np(IV) solubility experiments conducted at high pH and under reducing conditions, reported by Ewart et al. [9]. In the less reducing environment the pH determines which solid phase becomes stable. Above pH ~12, x-phase is stable; below this pH, uraninite or uranophane will limit the solubility. Therefore, the model calculations predict a phase transformation at pH ~12 under moderately reducing conditions. It is questionable whether such phase transformations will occur in a repository environment. A phase transformation requires an oversaturation by 1 to 2 orders of magnitude with respect to precipitation of a new solid phase. Based on the situations presented in the Figures 4b and 4c, the U-solubility will therefore follow the dashed branch of the x-phase curve (Figure 4c) and return to the uraninite/uranophane curve at pH values below 12. In a Swiss repository, the concentration of uranium will be low if compared with the amount of hydrated cement [10]. On a molar scale the averaged ratio U:CSH-gel is lower than 1:1000 and, therefore, the predicted phase transformation is unlikely to occur. It is much more likely that the uranium is sorbed on the cement or is built into the structure of the hydrated cement phases as an "impurity". If this is the case, the thermodynamic approach using well-defined, stoichiometric solids would be an unsuitable tool to predict uranium solubility. X-phase and uranophane were derived from experiments conducted at U:(Ca,Si) ratios in the order of --, 1:1. It would be very interesting to investigate, whether distinct uranium phases are still formed at very low U:CSH-gel ratios or whether the solubility is then determined by other processes (sorption, solid solutions). The following conclusions were drawn from the modelling exercise: In strongly reducing environments (Eh < -450 mV) a fair predictability for the solubility of uranium in degrading cement is expected. Uraninite will be the solubility limiting

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phase and concentrations ranging from 10 -8 to 10-1 M are expected in the pH range 13 to 10. Considering chemical analogies, these predictions agree with experimental data for Np(IV). It is of course a prerequisite that uraninite is really formed under repository conditions. This question still needs to be answered by experimental means. In moderately reducing environments (-300 mV to -200 mV) the predictions are not very reliable. The solubility limiting phase, and also the speciation in solution are very sensitive to both Eh and pH. It should be noted that an additional complication will be concerned with the accurate prediction of a redox state different from "reducing" or "oxidizing". The modelling predicts phase transformations which are thought to be very unrealistic at low uranium/cement ratios, and predicted solubilities do not agree well with the few experimental points. It is not clear, whether thermodynamic data determined under different chemical conditions may be extrapolated to the conditions representative of a real cement system. Therefore, predictions based on a thermodynamic approach remain questionable and further investigations including alternative concepts should be considered. These conclusions may be generalised and transferred to other redox sensitive radionuclides (e.g. Np, Pu, S, Se...) where even less (thermodynamic) data are available. The present model study demonstrates the limitations of the (usually used) thermodynamic approach and raises a series of questions, which finally have to be answered by well-defined and clear experiments. For the safety assessment of cement-based repositories the prediction of radionuclide solubility may be of critical importance. Unfortunately, present model concepts and available data are not in a state where very trustworthy predictions can be obtained.

References
. Project Gewhr 1985, Nuclear Waste Management in Switzerland: Feasibility Studies and Safety Analyses, National Cooperative for the Storage of Radioactive Waste (Nagra), Project Report NGB 85-09, Baden, Switzerland 1985. Berner U., A thermodynamic description of the evolution of pore water chemistry and Uranium speciation during the degradation of cement, PSI Report No. 62, Paul Scherrer Institute, Villigen 1990, Switzerland. Berner U., Evolution of pore water chemistry during degradation of cement in a radioactive waste repository environment, in: Waste Management, Special Issue on Cementitious Materials in Radioactive Waste Management, 1991 (in press). Berner U.R., Jacobsen J., McKinley I.G., The near-field chemistry of a Swiss L/ILW repository, in: Near-Field Assessment of Repositories for Low and Medium Level Radioactive Waste, Proc. NEA Workshop, Baden, Switzerland (1987), Paris 1988. Grenthe I., Fuger J., Lemire J., M/.iller B., Nguyen-Trung C., Wanner H., Chemical Thermodynamics of Uranium, NEA-TDB, OECD, Nuclear Energy Agency Data Bank, final draft 1990, Paris, France. Sedimentstudie - Zwischenbericht 1988, Mhglichkeiten zur Endlagerung radioaktiver Abf~lle in den Sedimenten der Schweiz, National Cooperative for the Storage of Radioactive Waste (Nagra), Technischer Bericht NTB 88-25, Baden, Switzerland 1988.

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10.

Atkins et al., Medium active waste form characterization: the performance of cement-based systems, in: Progress Report of the Third Radioactive Waste Management Programme for the Period May 1985 - March 1990, Commission of the European Communities, contract number F1 IW 0025UK(H), University of Aberdeen, 1990. Finch R., Ewing R., Uraninite alteration in an oxidizing environment and its relevance to the disposal of spent nuclear fuel, SKB Technical Report 91-15, Stockholm, Sweden, 1990. Ewart E.F., Gore S.J.M., Williams S.J., The solubility of Np(IV) at high pH, AERE R 11975, Harwell Laboratory, Oxfordshire, 1985. Projekt Gewhr 1985, Radioaktive Abf/ille: Eigenschaften und Zuteilung auf die Endlagertypen, National Cooperative for the Storage of Radioactive Waste (Nagra), Gew/ihr-Bericht NGB 85-02, Baden, Switzerland, 1985.