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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
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 . 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
.4 5 0 m m m im m im m m im m .6 L) (159. the hydrated cement phases will either dissolve or be converted into calcite. . namely CSH-gel. The cycle number indicates how many times the equilibrated pore solution has been replaced by fresh groundwater. Total dissolved uranium in the pore solution of degrading cement at different Eh values.. . A guess. Depending on the carbonate level of the groundwater. 2/3 speciation code.466 U. Nos. The cycle number is not correlated with real time.32 L) 100 1000 10000 (13..m m m m m ~-- "\ $ $ mmm m m mill "i . After complete leaching of the alkali hydroxides (typically after 50 to 100 water exchange cycles) the pH drops to 12.5 to 12.~5000 cycles.13 L) 10 (1.o I I -14 I 1 (0. To predict the solubility/speciation of the radionuclides embedded in the cement matrix.lml 200 mV m m llm im mm m m I ~ LL .KOH. Degradation is expressed in terms of pH vs.5 (saturation w. 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. L) Figure 1. . to portlandite) and remains on this level for about 1000 cycles. the composition of the cement pore solution and of the remaining solid phase inventory is calculated for each replacement of the pore solution. Due to the incongruent dissolution of calcium silicate hydrate gels (CSH-gels) the pH continuously drops to a value between 10.R. due to dissolution of Na. . During an early stage of cement degradation the pore solution pH is very high (pH 13. . KOH and NaOH. the knowledge of the temporal pH development in the pore solution of the cement is an important prerequisite. 22.11 E O o 03 "0 -10 -12 • OJ mV b~lll= iml m i m im m m i= mmmll~oo N CaU04. The progress of degradation is therefore expressed in terms of water exchange cycles. c) the time period to reach equilibrium between cement and groundwater is short compared to transport times.r. based on simple coupled model -2 t~ 0 -4 uo2. For clarification. the cumulative amount of groundwater contacted with 1 kg of hydrated cement is also given.5 and 10 at . Bemer Vol.000 water exchange cycles.. The application of this simple degradation model showed that the hydrated cement phases disappear after 5000 to 10.5). Ca(OH)2. The pH of the pore solution as a function of the cycle number is indicated in Figure 1. cycle numbers.2 5 o tm my \.'" i: et " "0 0) > -8 mV 4 CaUO. b)the chemical behaviour of cement can be sufficiently well modelled using a small set of model solids. Mg(OH)2.
0 23.~ -200 mV.7) Total dissolved Total dissolved V (~moles/1) Ca (mmoles/1) 0. Figure 3a). Solubility data for x-phase and uranophane in different solutions as taken from reference . Np.2) 0. In a Swiss repository the relevant redox condition boundaries are given by the E h of the groundwater (. the solubility of uranium in the pore solution was modelled. C/S: calcium/silicon ratio of CSH. Ca(OH)2(s) sat..mIG.1 9. CSH(c/S=la) sat. Pu.027 CSH(c/s=. The aim of the present work is therefore to investigate the impact of the redox conditions on the solubility limits.0995 0.6 12. From these results it was concluded that the experimental investigation of the solubility limiting phase is of central importance.2 1. As an application of the cement degradation model. CSH(c/S=la) sat. Uraninite and CaUOa show an opposite dependency on the redox potenTable 1.301 3.94 0.5 0..87 CSH(c/s=I.0076 0. 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.6 11. CSH: calcium silicate hydrate gel.~) 0.13 11. As an indicator the pH of the pore solution is also given. The results indicated that the solubility of U exclusively depends on pH and on the properties of the solubility limiting phase. For uranium a comprehensive collection of high quality thermodynamic data was published recently .83 sat.0 12.7 0. Again.7 11. 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.3 uranophane x-phase: uranophane: Ca(OH)2(~q) 0. since very high U concentrations were obtained at -200 mV (cf. An Eh range between -450 mV and -200 mV was therefore selected for the present study. Se.4 12.8 12. For these elements the redox potential of the pore solution will be an essential parameter if solubility and speciation is concerned. CSH(c/s=I.xH20 Ca(UO2)2(SiO3)2(OH)2. 233 THERMODYNAMIC M O D ~ I J . Tc. Many of the radionuclides relevant for the safety analysis of a repository axe redox sensitive (U. In addition. Depending on the choice of the solubility limiting solid.C E M E N T DEGRADATION. Ca(OH)2(s) 0. The compositions of cement and groundwater had nearly no influence.6 10.02 3.0084 18. solubilities ranging from 10 -14 M (CaUOa) to 10 -4 M (UO2) were predicted (at -300 mV).47 0.20 0.069 Measured pH 12.27 Ca2UOs.).Vol. Nos.. ) and by the redox potential of the anoxic corroding iron (Eh < -450 mV).322 H20 0. some experimental data concerning the behaviour of uranium in cement-like systems were available .0155 11. 22.. uranium is selected as a representative for the actinides. RELEASE 467 (transport/chemistry) calculations  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. Solid phase x-phase Solution Ca(OH)2(~q) sat.4 12.5H20 .
Atkins et al.R. They found a solid with the composition Ca~UOb. In order to keep consistency with the thermodynamic laws. o ~_ -12 2 13 12 pH o f 11 pore 10 solution Figure 2. Bemer Vol.+ 3H~O. However. 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.l.2 to 3 log K units. The uncertainty is estimated to be in the order of -t. As indicated by the dashed line.. a different method was used for estimating the solubility products. for uranophane. We obtained Ca2UOb. Estimation of the solubility product of x-phase and uranophane. Nos. 2. This solubility product was then varied until a reasonable fit with the experimental data was achieved. The dashed line in Figure 2 indicates how the model curve is shifted by varying the solubility product.phose -~ -s o • _c -8 E c -10 - j . 2/3 tial.+ 2 O H . 22.bH~O) to be the stable phases.3-1. The model curves are given as a function of the pore solution pH. Based on experimental data we therefore first try to fix the nature of solubility limiting phases as well as their solubility properties.) ¢ Ca ~+ + 2UO~ + + 2H~SiO]. Using the data given in Table 1.H20 ~ 2Ca ~+ + UO~+ + 6OH. whether the solid phase is thermodynamically stable at the particular conditions or not. The comparison using Ca 2+ as the independent variable gives a very poor agreement between . a comparison should also be made by giving total U as a function of Ca 2+ (and H2SiO4 in the case 2of uranophane). log K~o ~ -66 ~" -2 -4 o log Kso ~ -41 experlmental data ~ ~O. therefore. The model curves are based on cement and on groundwater compositions taken from reference . the solid lines were obtained by adjusting the solubility product.xH20(~) + (3-x).468 U.  investigated the systems CaO-UOa-H20 and CaO-UO3-SiO2-H20. for x-phase and Ca(UO2)2(SiO3)2(OH)~. The results of the solubility experiments conducted with these two phases are listed in Table 1... The solubility of the particular phase in degrading cement was modelled using a guessed solubility product. The solubility curves indicate that the range of predicted solubilities is reduced at strongly reducing conditions. 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. it should be noted that the curves in Figure 1 were modelled without considering. A comparison of modelled and experimental data is shown in Figure 2.F ~ ÷ uronophane • x .e'e~ .7H20 (x-phase) and uranophane (Ca(UO2)2(SiO3)2(OH)2.bH20(. the calculated solubility products show a large uncertainty range and.
Recently. the most important result from Atkins' work is the stoichiometric identification of the uranium phases formed in cement-like systems. are compatible with this review. RELEASE 469 measured and modelled data and silica was not measured during the experiments. X-phase and also uranophane seem to be common oxidation products of uraninite deposits. ~ _ -O ~ ~ "..3]. The phases found by Atkins et al. The solubility products given above should thereforebe considered as semi-quantitative estimates.Vol. CEMENT DEGRADATION. . However.. a more detailed description is given in [2. • ~O n -10 . Finch and Ewing  reviewed the minerals occurring in the environment of uranium deposits. 3.L'Lvo/~s . Nos. 22. No thermodynamic modelling can be performed if the composition of the solid phase is not known. -7 .3]) are therefore not explicitly given in the present work. Modelled solubility of uraninite in the pore solution of degrading cement as a function of pH at different Eh values.5000 I o I-- 12 11 pH of pore solution 10 Figure 3a. since uraninite is the most common uranium solid in reducing envi- -2 ~ o -3 uraninife "-.--8 -. For comparison with Figure 1. These data (taken from [2..~ . The available data are not complete enough to perfectly characterize the solubility properties of x-phase and uranophane. the number of water exchange cycles is also indicated. In addition to x-phase and uranophane. %~ ~\~Q -~ -5 C "'-.500 -11 13 I 1600 I . °//v ". 2/3 THERMODYNAMIC MODE1JJNG. The compositions of the cement and of the groundwater are not of key importance concerning the impact of Eh.. It is obvious that additional equilibrium data are required to characterize this system. The modelling of cement degradation in natural groundwaters was summarised in the introduction. uraninite (UO2) is selected as a solubility determining phase. 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 solubility of UO2 shows a pronounced dependency on Eh (Figure 3a). compared to -450 mV. -2 o= E -3. there is no doubt about the existence of this solid. ronments. The predominant complexes in solution are now UO2(OH)~. At -200 mV U(VI) is stabilized in the solution and at pH ~13 the solubility increases by six orders of magnitude. schoepite) are not considered since these phases would lead to unrealistic high uranium concentrations in alkaline solutions. Figure 3c.hydroxo complexes become stable and the solubility curve approximates the -450 mV curve. According to . 2[3 -2. whether it is formed in a cementitious environment or not.470 U.and UO2(OH)2. The hydrates of U03 (e. -4 -5 -6 -7 o x-phase -3 -4 -5 -8 -7 -4~0 revolt= urenophane g E -8 -9 -10 :2Z 13 12 pH of 11 pore 10 solution -8 -9 -10 -11 2 -11 13 12 pH of 11 pore 10 solution Figure 3b. In the comprehensive review of Finch and Ewing  CaUO4 is not mentioned. At -450 mV the solubility changes from 10 -s M to 10 -1° M in the pH range 13 to 10. Nos. The solid CaUO4 (shown in Figure 1) is ruled out for several reasons. If compared with UO2 this findings seem to be strange.g. The predominant complexes in solution are U(OH)2 and U(OH) °. x-phase and uranophane in the pore solution of degrading cement at distinct redox potentials is shown in Figures 3a-c. but the speciation in solution reveals that U(IV) and its hydroxo complexes are stabilized under these conditions. In particular. The solubility of UO2 . 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). U30~ and U30s are also neglected: as a first approximation their behaviour may be represented by that of UO2. 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. There is experimental evidence  that CaUO4 is not stable in hyperalkaline cement pore solutions.R. This will be addressed in the subsequent paragraphs. but it is questionable. The strong solubility increase at lower pH indicates that x-phase will . the thermodynamic stability of the limiting phase at given redox conditions was not checked. Bemer Vol. Figure 3b). The mixed valence oxides U409. With decreasing pH the U(IV) . Modelled solubility of xphase in the pore solution of degrading cement as a function of pH at different Eh values. The solubility of x-phase is higher in the reducing environment than at -200 mV (300mV. Modelled solubility of uranophane in the pore solution of degrading cement as a function of pH at different Eh values. it should be noted that the solubilities are presented as obtained from the model calculation. 22.
-12 ~ o10 o 13 12 11 10 13 12 11 10 pH of pore solution pH of pore solution Figure 4a. .o . E M E N T DEGRADATION.4 5 0 mVolts -2" -4" ~Q. 2/3 T H E R M O D Y N A M I C MODF. c o w ÷.. Nos. Figure 4b.. 22." -4 -8 °o .~.10.!/biG.Vol." " -4" c "-. • + e= -8 _ -.3 0 0 mVolts ~e • ooO uronOP b°n° • . Experimental data of Atkins et al.I . The phase transformation at pH ~12 requires an oversaturation indicated by the arrow.. •~ -10 uranophane -12 13 I I I 12 pH of 11 pore solution 10 Figure 4c. -2 - 200 mVolts ~- -4 -6 -. "-~m "" 4. For uranophane the highest solubility is modelled at -450 mV (Figure 3c). At -200 mV (-300 mV) a characteristic solubility minimum is obtained between pH 11 and 10. Total solubility of U in degrading cement at -450 mV. % ~ . + .~. Total solubility of U in degrading cement at -300 mV.- 4¢~ "@" -6" E c -8 uronlnlt° i 1 1 ~ r o n l n l t e -10. ". which is due to the stabilization of U(IV) as in the case of x-phase. This minimum is ~ o -2 ... ° / .~<. Total solubility of U in degrading cement at -200 inV.%. RELEASE C 471 not exist stably below a pH of ~-.  are indicated with + (x-phase) and + (uranophane). .
9 M UO2(OH)~/UO2(OH)~U(OH). Bemer Vol.10 -1° M U(OH)°/U(OH). whereas at -300 mV it may not be distinguished between uraninite and and uranophane.R. Table 2./U(OH)~ UO~(OH)~/UO2(OH)~5.3]. Due to the high pH only the hydroxo complexes of U(IV) and U(VI) are formed. the experimental data of Atkins et al. The minimal concentration at any given pH is found by projecting the solubility curves for different solid phases on the same diagram. 2/3 a consequence of the increased silica concentration in this pH region [2.10 -9 M UO2(OH)~/UO2(OH)~10 -s M UO2(OH)~/UO2(OH)~10 -s M 12 U(OH).10 -1° M. The Figures 3a-c show modelled curves which will not be observed in real systems. The speciation of dissolved uranium is not complicated. In the strongly reducing environment U(IV) is predominant over the entire pH range. the resulting minimal solubility curves presented in Figures 4a-c are obtained.10 -9 M and 3. Depending on the redox potential.10 -1° M UO2(OH). S042-. 5. F-.. Table 2 gives the predicted uranium speciation as a function of Eh and pH.10 -1° M ./U(OH) ° 2. due to the uncertainty associated with the solubility product of uranophane.10 -1° M U(OH)°/UO2(OH)~ 10 -1° M 10 U(OH)°/U(OH).-~10-7 M uranium) is predicted near pH 12. The concentrations indicate total dissolved uranium. Below pH ~12 uraninite or uranophane become stable and total dissolved U decreases to .10 -10 M U(OH)°/U(OH). A solubility maximum (. At -450 mV uraninite is the solubility limiting phase and total dissolved uranium varies between 5. whereas U(IV) hydroxo complexes determine the speciation below pH ~11.10 -1° M in the pH range 13 to 10 (Figure 4a)./U(OH) ° 10 . CO~-. Only at pH values around 13 the U(VI) hydroxo complexes contribute significantly to the total dissolved uranium. 22. At -200 mV uranophane is the solubility limiting phase. For comparison. Complexes whose contribution to the total dissolved U is less than 1 % are not considered. In the pH range 13 to 12 x-phase becomes stable. since the thermodynamic laws require a minimal solubility for a given equilibrium system. Nos. I0 -r M UO2(OH)~/UO2(OH)~I0 -7 M 11 U(OH)°/U(OH). Predicted uranium speciation in degrading cement as a function of Eh and pH. 5. UO2(OH)~ 5. NO3) are not relevant. 5. pH 13 -450 mVolts -300 mVolts -200 reVolts U(OH).  are also given in Figure 4c. At -300 mV and at -200 mV the nature of the solubility limiting phase depends on pH (Figures 4b and c).472 U.. Complexes with the anionic constituents of the attacking groundwater (CI-. In the moderately reducing environment U(VI) is predominant above pH ~11.
According to the thermodynamic data from NEA . The free ions UO~+ and U 4+ are not important. 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.3]. the total dissolved uranium shows not a very pronounced Eh dependency. RELEASE 473 4. Therefore. the agreement between measured and modelled solubilities is rather poor. On a molar scale the averaged ratio U:CSH-gel is lower than 1:1000 and. In the strongly reducing environment (-450 mV) the situation is not complicated.xH20) and of uranophane (Ca(UO2)2(SiO3)2(OH)2. This is in agreement with Np(IV) solubility experiments conducted at high pH and under reducing conditions. The speciation of dissolved uranium is more informative. 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". Modelled uranium solubilities range from 10 -T M to 10 -1° M. If this is the case. It would be very interesting to investigate. 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. Therefore. the model calculations predict a phase transformation at pH ~12 under moderately reducing conditions. 22. stoichiometric solids would be an unsuitable tool to predict uranium solubility. X-phase and uranophane were derived from experiments conducted at U:(Ca. since uraninite is the only stable phase. It is questionable whether such phase transformations will occur in a repository environment. x-phase is stable. experimental solubilities measured under oxic conditions cover the range from 10 -6 M to 10 -9 M. Based on the situations presented in the Figures 4b and 4c. Uraninite will be the solubility limiting . the results show that the speciation is very sensitive to Eh and pH. The question as to the stable. In a Swiss repository. 1:1. S u m m a r y and conclusions Using a cement degradation model described elsewhere [2. solid solutions). below this pH. CEMENTDEGRADATION. A phase transformation requires an oversaturation by 1 to 2 orders of magnitude with respect to precipitation of a new solid phase. for example. Considering the uncertainty of the estimated solubility products of x-phase and uranophane. Based on these solids and on uraninite (UO2) the solubility of uranium was modelled in the Eh range -450 mV to -200 mV.Si) ratios in the order of --. the thermodynamic approach using well-defined. at least below pH ~ 12. The complexes of U(IV) are more stable than those of U(VI) which. 2]3 THERMODYNAMIC MOI~H B4G. In addition. the ratio U(IV)/U(VI) in solution not only depends on Eh but also on the relative stability of the hydroxo complexes formed. uraninite or uranophane will limit the solubility.5H20) were estimated. In the less reducing environment the pH determines which solid phase becomes stable. the concentration of uranium will be low if compared with the amount of hydrated cement . therefore.Vol. Above pH ~12. Here. leads to the observation that U(OH) ° is predominant even at -200 mV and pH 10. the hydroxo complexes of uranium are formed exclusively in the high pH environment of cement pore solution. solubility limiting phase is of particular interest. . From experimental data  the solubility products of x-phase (Ca2UOs. 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. the predicted phase transformation is unlikely to occur. Nos. reported by Ewart et al. the Eh dependency of the uranium solubility in the pore solution of degrading cement was investigated.
References . . final draft 1990. National Cooperative for the Storage of Radioactive Waste (Nagra). . Sedimentstudie . Baden.... Considering chemical analogies.Zwischenbericht 1988. which finally have to be answered by well-defined and clear experiments.. . predictions based on a thermodynamic approach remain questionable and further investigations including alternative concepts should be considered. 62. Technischer Bericht NTB 88-25. 2/3 phase and concentrations ranging from 10 -8 to 10-1° M are expected in the pH range 13 to 10.. Se.. PSI Report No. Villigen 1990. Pu. The solubility limiting phase. Paris 1988.. Berner Vol. Chemical Thermodynamics of Uranium.G. present model concepts and available data are not in a state where very trustworthy predictions can be obtained. Mhglichkeiten zur Endlagerung radioaktiver Abf~lle in den Sedimenten der Schweiz. The present model study demonstrates the limitations of the (usually used) thermodynamic approach and raises a series of questions. For the safety assessment of cement-based repositories the prediction of radionuclide solubility may be of critical importance. Therefore.iller B. France. National Cooperative for the Storage of Radioactive Waste (Nagra).. In moderately reducing environments (-300 mV to -200 mV) the predictions are not very reliable..R. Baden. Switzerland (1987). This question still needs to be answered by experimental means. Wanner H. Switzerland 1988. NEA-TDB. Nos. Switzerland 1985. Proc. Special Issue on Cementitious Materials in Radioactive Waste Management. and also the speciation in solution are very sensitive to both Eh and pH. S. 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. Nuclear Energy Agency Data Bank. Lemire J. These conclusions may be generalised and transferred to other redox sensitive radionuclides (e. Grenthe I. and predicted solubilities do not agree well with the few experimental points... Berner U. M/. . 22. McKinley I. Evolution of pore water chemistry during degradation of cement in a radioactive waste repository environment. Jacobsen J. in: Near-Field Assessment of Repositories for Low and Medium Level Radioactive Waste. these predictions agree with experimental data for Np(IV). Paris. .R. whether thermodynamic data determined under different chemical conditions may be extrapolated to the conditions representative of a real cement system..g. NEA Workshop. Project Report NGB 85-09.474 U. Berner U. Switzerland. Unfortunately. Berner U. A thermodynamic description of the evolution of pore water chemistry and Uranium speciation during the degradation of cement. Nguyen-Trung C. Nuclear Waste Management in Switzerland: Feasibility Studies and Safety Analyses. OECD. Np. It is not clear. It is of course a prerequisite that uraninite is really formed under repository conditions. Fuger J. Baden. in: Waste Management. Paul Scherrer Institute. . 1991 (in press).. The near-field chemistry of a Swiss L/ILW repository. Project Gew£hr 1985.) where even less (thermodynamic) data are available.
University of Aberdeen.J. AERE R 11975. Williams S.F.. Medium active waste form characterization: the performance of cement-based systems. contract number F1 IW 0025UK(H). Nos..Vol. Baden. The solubility of Np(IV) at high pH..M. 1985. Oxfordshire.. Switzerland. 22. . 2/3 THERMODYNAMIC MODELLING. Gore S. Sweden. 1990..J. Uraninite alteration in an oxidizing environment and its relevance to the disposal of spent nuclear fuel. Radioaktive Abf/ille: Eigenschaften und Zuteilung auf die Endlagertypen. 10. in: Progress Report of the Third Radioactive Waste Management Programme for the Period May 1985 . Gew/ihr-Bericht NGB 85-02. 1990.CEMENTDEGRADATION. National Cooperative for the Storage of Radioactive Waste (Nagra). Projekt Gew£hr 1985. Ewing R. Atkins et al.March 1990. . 1985. SKB Technical Report 91-15. Commission of the European Communities. Stockholm. Harwell Laboratory. Ewart E.RELEASE 475 . Finch R.. .