Kopajtic, Z.

Van Loon, L. R.

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Radiochimica Acta 55, 9 1 - 9 4 (1991) © R. Oldenbourg Verlag, München 1991 - 0033-8230/91 $3.00+0.00 The Adsorption of Radionuclides on Bitumen Part II: Nickel By L. R. Van Loon and Z. Kopajtic Paul Scherrer Institute, Würenlingen and Villigen, CH-S232 Villigen PSI, Switzerland (Received January 16, 1991; revised February 25,1991) Bitumen / Adsorption / Surface complexation / Radionuclides / Nickel / Americium / Uranium Abstract The adsorption of on a pure bitumen (Mexphalt 80/100) was studied as function of pH and ionic strength of the liquid phase. It was found that Ni^ adsorbs on the bitumen surface by an inner sphere surface complexation reaction. The concen-tration ratio increases with increasing pH and ionic strength. At high pH values, the formation of neutral and anionic hydroxocomplexes in Solution competes strongly with the adsorption reaction. In a cementitious environment, the adsorption of Ni^ "^ on bitumen is negligible due to the formation of such hydro-xocomplexes. A theoretical evaluation of the adsorption of A m ' ^ and VOl'*^ on bitumen is given. These elements are expected to behave similarly to Ni^"^, i.e. an increase of R^ as a function of pH in the lower pH ränge, followed by a decrease due to the formation of hydroxocomplexes in the higher pH ränge. Introduction The adsorption of radionuclides on the bitumen matrix could be an important process retarding the release of radionuclides from the near field of a radio-active waste repository. The adsorption of radio-nuclides on bitumen has been studied previously [2— 4] and it appears that the interaction of radionuclides with the bitumen surface is weak. Little information is available on the mechanisms of adsorption on bitumen and knowledge of the relevant parameters controUing the Sorption process(es) is poor. In a previous study [1], the bitumen surface was characterized in terms of the functional group density (A ,^, groups/cm^). The adsorption of Sr^ was measured under a variety of conditions and the results interpreted in terms of the formation of monodendate surface complexes. In this work, the adsorption of Ni^ on bitumen was studied. A mechanistic model was developed to describe the adsorption of Ni^"^ as a function of pH, ionic strength and in the presence of competing ligands. Materials and methods Bitumen emulsions were prepared and characterized as described elsewhere [1]. The emulsions were placed in dialysis membranes (Dialysis Tubing-Visking, Medicell London) and equilibrated with solutions of the desired ionic strength and pH. Between pH 7 and 9, the solutions were buffered with 5 • M TRIS (Tris(hydroxymethyl)-aminomethane). Beyond pH 9, the pH was adjusted to the desired value by NaOH. The ionic strength of the solutions was fixed at 0.001 M with NaC104. In another series of expe-riments, the pH of the solutions was fixed at a value of 8.3 and the ionic strength was varied between 10" ^ M and 10"^ M with NaC104. 20 ml aliquots of the bitu-men emulsion were transferred to 50 ml teflon centri-fuge (Oak Ridge Type) tubes and 5 ml of the equili-brium Solution, spiked with were added. The final concentration of Ni^ "*" was 10"® M. The mixtures were shaken end-over-end for 24 hours and subsequently centrifuged at 11000 g (Heraeus Sepatech, Biofuge 17S) for 30 minutes. 2 ml of the clear supernatant were sampled and analyzed for ^^Ni by liquid scintillation counting (Packard, Tricarb 2250 CA) using Instagel (Packard) as the scin-tillation cocktail. The concentration ratio (/?,') was calculated from the difference in concentration before and after equilibrium. Parallel blank tests (without bitumen) were carried out to check the adsorption on the vessel walls. Results and discussion Figure 1 displays the adsorption results cm) as a function of pH. The distribution ratio is defmed as: Ni adsorbed ixmol Ni/cm^ Ni in Solution umol Ni/cm^ (1) As can be seen, the experimental data exhibit a rela-tively large scatter. Despite this, some clear trends can be identified. There is a sharp increase in adsorption with increasing pH in the pH ränge 7 — 8.5. Beyond pH 11, no, or very low, adsorption occurs. The in-crease in adsorption can be explained by an increase in the adsorption capacity (CEC) on the bitumen surface. The low adsorption at pH values > 10.5 can be ex-plained by the hydrolysis of Ni^ . The formation of neutral Ni(OH)5 or anionic Ni(OH)J and N i ( O H ) r species in Solution competes with the adsorption of Ni^ on the solid phase and makes adsorption impos-sible at higher pH values. As Ni^^ forms relatively stable complexes with i.a. carboxyl groups because of 92 L. R. Van Loon and Z. Kopajtic 8 9 10 11 12 13 14 pH Fig. 1. Adsorption of Ni^^ on bitumen as a function of pH at 1 = 0.001 M. »: experimental results; — : calculated from equa-tion (12). its partly unfilled cf-orbitals, the adsorption of Ni^ was assumed to be a surface complexation reaction: Ni^ + + RCOO - ^ RCOONi+. (2) The equilibrium constant is defined by: {RCOONi+} (3) with: (RCOONi""} = adsorbed on the bitu-men (umol/cm^) {RCOO"} = free, deprotonated carboxyl groups (umol/cm^) [Ni^^] = concentrationofNi^""in Solu-tion (timol/cm^) N^i = activity coefficient of Ni^ "" in Solution. In cases where complexation or hydrolysis reactions occur, these reactions have to be combined with the adsorption reaction. The following reactions of Ni^"" occur in Solution: Ni2+ + L^-with -NiL ,2-n [NiL] and Ni2+ + « O H - ^ N i ( O H ) 2 with _ [Ni(OH)^-"] where « = 1, 2, 3, 4. This gives: 4 [Ni],„. = + NiL + X N i ( O H ) r " ] (4) (5) (6) (7) (8) = [Ni^^] 1 + W L ^ - ] + Z • [OH-]" The combination of equations (3) and (8) results in: {RCOONi+} { R C O O - } - [ N i ] . „ . - W ( l + W L ^ " ] + ^ ßnlOH-]") n= 1 (9) Since we are studying the adsorption of Ni^^ at trace levels, the adsorption of Ni^"" on the surface does not change the composition of the surface significantly. Consequently, the activity coefficient of the adsorbed species can be considered to be constant and is in-cluded in the equilibrium constant. The deprotonation of the carboxyl groups is controlled completely by the Na"" concentration in and the pH of the Uquid phase. With {RCOONi+}/[Ni],o, = and {RCOO"} = CEC, equation (9) is transformed in: R\ Ni CEC • )'Ni/(l + K ^ i d l ^ n + Z J?„[OH-]") n = l (10) or • CEC • 1 -h K^idi^n + ^ ßAou-r n=l (11) and with CEC = a • CEC„ R^' = • g • CEC^3x • yNi (1 + K ^ A l ^ n + ^ ßniOB-]") (12) ' = concentration ratio of Ni (cm) = surface complexation constant (cm^/ Ueq) CEC„,ax = maximal CEC (ueq/cm^) ^NiL = stability constant of the NiL complex ( M - ' ) ß„ = hydrolysis constant ofNi(OH)^"" [L^"] = concentration of ligand L in Solution (M) [OH ] = concentration of OH in Solution (M). Equation (12) is the basic equation describing the adsorption of Ni^"" on bitumen as a function of pH and the concentration of competing ligands L and O H " in Solution. ATnil ' [L^~] in equation (12) can be set to zero, since no complex forming organic or inorganic ligands other than O H " were present. The CEC equals the amount of dissociated carboxyl groups on the surface and can be calculated from the lonizable Surface Group Model with pK« = 6.6 and CEC„,„=2.28 ueq/m^ [1]. The solid line in Figure 1 shows a least square fit of the Sorption data derived from equation (12). The Parameter used for the fit are summarized in Table 1. The surface complexation constant was derived from this least square fit and equals 856+122. All other Parameters were fixed. The calculated curve describes The Adsorption of Radionuclides on Bitumen. Part II: Nickel 93 Table 1. Parameter values used in equation (12) to describe the adsorption of Ni^'^ on bitumen Parameter Value pK„** 6.6 856 CFC ** 2.28 [Na^] 0.001 M ßi* 1 0 " " ßz* 10.«° ß3* ß.* 10'^ * Taken from [8], ** Taken from [1], o o: a) K 3 = 1000 b) K s = 5000 c) K s = 10000 d) Ks= 20000 e) Kg = 40000 pKu= 6.6 9 10 pH 1) 11 12 13 14 Fig. 3. Adsorption of UO^'^ on bitumen as a function of pH at 1=0.001 M as calculated from equation (12). 340 320 S 300 280 1 o 260 240 o (E 220 200 180 160 0.005 [Na+]. M 0.01 Fig. 2. Adsorption of Ni^ on bitumen as a function of the Na"^ concentration at pH = 8.3. *: experimental results; — : calculated from equation (12). a) Ks= 1000 b) K s = 5000 c) K s = 10000 d) Ks= 20000 !) K s = 40000 pK^  = 6.6 2) 5 6 7 8 9 10 11 12 13 U pH Fig. 4. Adsorption of Am'^ on bitumen as a function of pH at 1 = 0.001 M as calculated from equation (12). Table 2. Stability constants of complexes between M and acetate [6] Metal log/Ci K, 1.19(1 = 0, 25°C) 15.5 1.43 (1 = 0, 25°C) 26.2 Am' + 2.78 (I = 0,20°C) 602 u o r 3.03 (1 = 0, 20°C) 1071 reasonably the increase of R^' in the pH ränge 7—9, the maximum at a pH of 9.2 and the decrease in ' at pH >9.2. At pH values >11, the adsorption of Ni^ "^ is neghgibly small. Figure 2 shows the adsorption of «^Ni^^ (Ä^') as a function of the Na"^ concentration in the liquid phase at a constant pH of 8.3. The higher the Na"*^  concentration, the higher the adsorption of Ni^^. Ac-cording to the lonizable Surface Group model, the deprotonation of the surface carboxyl groups depends strongly on the ionic strength of the liquid phase in the pH ränge 6 — 11 [1]. The adsorption capacity (CEC) thus increases with increasing ionic strength. When the ionic strength is raised from 0.001 M to O.Ol M at pH 8.3, the value of a increases from 0.15 to 0.29. The CEC (CEC = CEC„3x • a) thus increases by a factor 2 from 0.34 to 0.66 ueq/m^ [1]. Conse-quently, the distribution ratio increases with a factor two by raising the ionic strength from 0.001 M to O.Ol M at a constant pH of 8.3. The solid line in Figure 2 represents the evolution of R^' as a function of the Na^ concentration as calculated by equation (12). The experimental and predicted values are in good agreement. The value of A^' derived from this least Square fit equals 702 + 35 and is similar to the value derived earlier. The surface complexation reaction (interaction of a surface carboxyl groups with Ni^"^) is independent on the Na"^ concentration in Solution. Consequently, this reaction can be assumed to be an inner sphere surface complexation reaction. Inner sphere com-plexes result from the formation of a covalent bond between the coordinating atoms and the metal ions, with partial or total dehydration [5]. The Ni^ "^ ion is thus located in the Stern layer and not in the diffuse part of the double layer. The distribution ratio, how-ever, depends on the ionic strength because the CEC depends on the ionic strength. Equation (12) allows us to evaluate the adsorption of Ni^ "^ on bitumen under the near field conditions of a cement based repository [7], At these high pH values. 94 L. R. Van Loon and Z. Kopajtic Table 3. Parameter values used in equation (12) to calculate adsorption of Am^'^ and UOi"^ on bitumen Parameter Value Species pK„** 6.6 — CECmax** 2.28 -[Na+] 0.001 M -log^,* 6.0 Am(OH)^ + l0g^2* 11.10 Am(OH)+ log^3* 15.50 Am(OH)§ 18.90 Am(OH)^ log^i* 8.20 U02(0H)-' \0gß2* 16.0 UO,(OH)5 logjSj* 18.4 U02(0H)3-logß4* 18.20 U02(0H)^-* Taken from [9]. ** Taken from [1], The same observations can be made as for Ni^ . Adsorption (R^) increases as a function of pH, reaches a maximum and decreases again at higher pH values. The pH at which a maximum occurs depends on the values of the hydrolysis constants. The higher the ten-dency of an ion to undergo hydrolysis, the lower the pH at which an adsorption maximum occurs. The hydrolysis constants of Am^ and U O i f o u n d in the literature exhibit a relatively large uncertainty but this has, however, no influence on the conclusions which can be drawn from the calculations. At pH values typicalofacementitiousenvironment(pH = 12—13), adsorption of both Am^"^ and UOi"^ is expected to be negligible due to complete hydrolysis. For cationic hydrolyzable radionuclides present in the waste matrix, one can conclude, in general, that no or very weak adsorption on bitumen has to be expected in a cementitious environment. is completely hydrolysed (Ni(OH)3: 72%; Ni(OH)4": 28% [8]) and adsorption on bitumen is negligibly small. The i?^' values can be estimated to be <10~®cm. Equation (12) can also be used to evaluate the adsorption of other cationic radionuclides on bitu-men. Let US consider the adsorption of uranium and americium under oxic conditions. Under these con-ditions, U(VI) and Am(III) are predominant. As no information is available on the surface complexation constants K,'" and on bitumen, reasonable esti-mations have to be made. To facilitate this estimation, comparison with sta-bility constants of metal-acetate complexes in Solution were made [6]. Table 2 gives an overview of stability constants of a few 1:1 metal-acetate complexes. The stability constant of Ni^ "^ is about 2 times higher than that for + . The Am^+ and UOi+ constants are 23 and 41 times higher than the Ni^ ^ constants. Taking the surface complexation constant for Ni^ as a refe-rence and assuming a constant ratio between surface COOH and Solution acetate constants, one can calcu-late surface complexation constants of 20000 (Am^"^) and 35000 (UOi^) as reasonable estimates. Figures 3 and 4 display the R^ for UO2 ^  and Am^ ^  as a function of pH. The values of and were varied, for Illustration, between 1000 and 40000. The values of the other parameters used for the calcu-lations are given in Table 3. It is assumed, for sim-plicity, that only the hydrated cation is adsorbed on the bitumen surface. This is probably an over-simplification of the adsorption process but, neverthe-less, enables realistic estimations of the extend of adsorption on the bitumen surface to be made. Acknowledgements The authors like to thank Prof. R. Grauer, Dr. B. Baeyens and Dr. M. Bradbury for the fruitful dis-cussions. This work was supported financially by the Swiss National Cooperative for the Storage of Radioactive Wastes NAGRA. References 1. Van Loon, L. R., Kopajtic, Z.: The adsorption of radio-nuclides on bitumen. Part I: Strontrium. Radiochim. Acta 55, 83-89 (1991). 2. Bumay, S. G.: Sorption effects in the leaching of ^^^Cs from organic matrix waste forms. AERE R 12421 DOE/RW/ 87.083, August 1987. 3. Hietanen, R., Alaluusua, M., Jaakkola, T.: Sorption of Cesium, Strontium, lodine, Nickel and Carbon in mixtures of concrete, crushed rock and bitumen. Report YJT-85-38, 1985. 4. Alaluusua, M., Hakanen, M.: Sorption of Cesium, Stron-tium, Cobalt and Technetium in mixtures of concrete, crushed rock and bitumen. Report YJT-87-10,1987. 5. Büffle, J.: Complexation Reactions in Aquatic Systems: an Analytical Approach, Ist ed., EUis Horwood Limited 1988, p. 692. 6. Sillen, L. G., Martell, A. C.: Stability constants of metal-ion complexes, Special Publication 25, Chemical Society, Bur-lington House, W1 London 1971. 7. Anderson, K.: Transport of radionuclides in Water/Mineral systems. Ph. D. Thesis, ISBN 91-7032-105-1, Chalmers Uni-versity, Goteborg 1983. 8. Baeyens, B., McKinley, I. G.: A PHREEQE Database for Pd, Ni and Se. PSI report 34, Würenlingen and Villigen, Switzerland. 9. PSI/MINEQL Database. 

The Adsorption of Radionuclides on Bitumen: Part II: Nickel

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