ML20070N336
| ML20070N336 | |
| Person / Time | |
|---|---|
| Site: | Peach Bottom  |
| Issue date: | 03/31/1994 |
| From: | Akers D, Kraft N, Mandler J EG&G IDAHO, INC. |
| To: | NRC OFFICE OF NUCLEAR REGULATORY RESEARCH (RES) |
| References | |
| CON-FIN-A-6359 EGG-2722, NUREG-CR-6164, NUDOCS 9405050409 | |
| Download: ML20070N336 (71) | |
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NUREG/CR-6164 EGG-2722 Release of Racionue:ic.es and ;
C:ae:.ating Agents From Cement- l Solicifiec Decontamination i Low-Level Racioactive Waste ,
Collectec From the Peaca Bot:om Atornic Power Station Unit 3 i
. e ker , N. C. Kraft, J. W. Mandler Idaho National Engineering Laboratory EG&G Idaho, Inc.
Prepared for U.S. Nuclear Regulatory Commission isA"iB88 M888s7e P PDR
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1 DISCLAIMER NOTICE Th:s report was prepared as an account of work sponsored by an agency of the United States Government.
Neither tne United States Government nor any agency thereof, or any of their ernployees, makes ny warranty, expressed or imphe1 or assumes an y ;ega! l,ab.'dy of responsibety for any third part(s use, or the results of such use, of any inf armabon, apparatus. product or prccess dtsclosed in this report or represents that its use by such tMd party wou:d not infnngo pn o e ownm rights 4
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NUREG/CR-6164 EGG-2722 s
Release of Radionuclides and Chelating Agents From Cement-Solidified Decontamination Low-Level Radioactive Waste
. Collected From the Peach Bottom Atomic Power Station Unit 3 l
Manuscript Completed: February 1994 Date Published: March 1994 Prepared by D. W. Akers, N. C. Kraft, J. W. Mandler I
Idaho Engineering Laboratory EG&G Idaho,Inc.
Idaho Falls, ID 83415 w
Prepared for Divisidn of Regulatory Applications Office of Nuclear Regulatory Research i U.S. Nuclear Regulatory Commission Washington, DC 20555-0001 NRC FIN A6359 i
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NUREG/CR-6164 is not a substitute for NRC regulations and compliance is not required. The approaches and/or methods described in this NUREG/CR are pro-l vided for information only. Publication of this report does not necessarily consti-tute NRC approval or agreement with the information contained herein.
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1 ABSTRACT As part of a study being performed for the Nuclear Regulatory Commission (NRC), small-scale waste-form specimens were collected during a low oxidation-state transition-metal ion (LOMI)-nitric permanganate (NP)-LOMI solidification
! performed in October 1989 at the Peach Bottom Atomic Power Station Unit 3. The
! purpose of this program was to evaluate the performance of cement-solidified decontamination waste to meet the low-level waste stability requirements defined l in the NRC's " Technical Position on Waste Form," Revision 1. The samples were l l acquired and tested because little data have been obtained on the physical stability l of actual cement-solidified decontamination ion-exchange resin waste forms and on the teachability of radionuclides and chelating agents from those waste fomis.
The Peach Bottom waste-fomi specimens were subjected to compressive strength, immersion, and teach testing in accordance with the NRC's " Technical Position on
- Waste Form " Revision 1.
t Results of this study indicate that the specimens withstood the compression tests
(>500 psi) before and after immersion testing and leaching, and that the leachabil-ity indexes for all radionuclides, including 14C, 99Tc,and 1291 , are well above the leachability index requirement of 6.0, required by the NRC's " Technical Position on Waste Form," Revision 1.
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FIN No. A6359-Characteristics of Low-Level Radioactive Waste:
! Decontamination Waste iii NUREG/CR-6164 l
l CONTENTS ABSTRACT., , . . .. . . . . iii LIST OF FIGURES . .. ... . . . . ... vi LIST OF TABLES . . .. . ... . . . . viii EXECUTIVE
SUMMARY
. . . ix 1
ACKNOWLEDGMENTS . . . ... . xn l ACRONYMS... . . . xv l 1
INTRODUCTION . . .. . .. . 1 l
l EXPERIMENTAL PROCEDURES . . .. ... .. 5 Sample Collection . . . . .. . 5 ,
1 Leach-Test Method . . . . . . . . 7 Test Procedure ...... . . 8 Data Analysis . . . .. .. 9 Compressive Strength Test Method . . . . I1 Analytical Methods . . . . I1 Radionuclide Analysis . . . . . 12 Elemental Analysis . . . . . . . . . . . 15 Chelating Agent Analysis . . . . . . 15 EXPERIMENTAL RESULTS .. . . . . . .. 16 Waste Form Structural Stability . . . . . . . . .. 16 Leach Test Results . . ... .. .. . . .. . . . 20 Leachate pH and Conductivity . .. . . . . . 20 Concentrations of Radionuclides. Stable Metals, and Chelating Agents in Resin Wastes and the Cemented Waste-Form . . . .. ... . 22 Chelating Agent, Radionuclide, and Stable Metal Releases . . .. . 24 Chelating Agent . . .. ... . . ... . . 25 Decontamination Radionuclide Releases . .. . . . 31 Other Radionuclide Releases . . . . ... . . . .. . 37 Stable Metals . . . . . . ... . . 42 COMPARISON OF PEAC11 BOTTOM-3 RESULTS WITH OT11ER LOMI WASTE FORMS . 48 CONCLUSIONS . . .. . . . . . . .. 54 v NUREG/CR-6164
1 57 REFERENCES . . .. .. ..... .. . . ... . . . . . ., . . ....
Appendix A-LOMI-NP-LOMI Decontamination Process . . . .. . .. . .. . A-1 Appendix B-Summary of Solidification Performed at the Peach Bottom Atomic Power Station Unit 3 . .. . . ... . . . .. . . . . . . .. . . .. B-1 Appendix C-Detailed Procedures for 14C. M e,and 129I Analysis . .. .. . C-1 Appendix D-Leaching Data for Peach Bottom . . . . .. . . . . D-1 Appendix E-Radionuclide, Chelating Agent, and Stable Metal Inventory in Peach Dottom-3 Liner 446828-15 . . ... .. .. . E-1 LIST OF FIGURES
- 1. Peach Bottom leach test specimen .. . . . .. . . 9
- 2. Peach Bottom leach test specimen suspended in leachan. . .. .. . 9
- 3. Compressive strength testing system .. . . . .. 12
- 4. Leachate analysis methods . . . . . . . . . .. . 13
- 5. Peach Bottom waste form specimen after immersion and compression testing . . 19
- 6. Process control program specimen after immersion and compression testing .. . 19
- 7. Leachate pil for all specimens . . . . .. .. . 21
- 8. Leachate conductivity for all specimens . . . . . . .. . 21
- 9. Fractional release rates of picolinic acid , . . . 30
- 10. Cumulative fraction release of picolinic acid . . . . 30
- 11. Fractional release rates of 55Fe . . . .. . . .. 31
- 12. Fractional release rates of 60Co . . . . . 32
- 13. Fractional release rates of 63Ni . . . 32
- 14. Cumulative fraction release of55Fe . .. 35
- 15. Cumulative fraction release of 60Co . . . . . . . 36
- 16. Cumulative fraction release of 63Ni ... . ... . . . . 36
- 17. Fractional release rates of 14C. . . . . . . . .. . 37 l
- 18. Fractional release rates of 94c . . . 38 l NUREG/CR-6164 vi l 1 . - . -- . .__--______!
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- 19. Fractional release rates of t291 ....... . . . . . ........ ... . ....... .. 38
) 20. Cumulative fraction release of 14C ..... 40
- 21. Cumulative fraction release of 99Tc , ... ..... .. . .. . .... .. .... . ... 41 i
' 22. Cumulative fraction release of 129) , ,, , , ,,, , ,, , ,, ,,,,,, ,, 4]
- 23. Fractional release rates of iron . .... .. . . . .... . ... ... . .. 43 i 24. Fractional release mies of nickel . ... .... .. . . .. ..... .. . .. ... 43
! 25. Fractional release rates of chromium ... .. . .... ...... .. ... . .... . .. 44 i J l
] 26. Fractional release rates of cobalt . . .... .. ... ..... .. . . ... .. 44
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- 27. Cumulative fraction release of iron . .. . . . . .. ... .. ... ... 45 ;
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- 28. Cumulative fraction release of nickel . . .. .. .. . . .. .... 46 l
- 29. Cumulative fraction release of chromium . .. . . . .. .. . .... 46
- 30. Cumulative fraction release of cobalt . . .... .. .. . . . . . .. . 47
- 31. Comparison of average fractional release rates of picolinic acid from LOMI waste forms . . . . 48 i 1
- 32. Comparison of cumulative fraction releases of picolinic acid from LOMI waste famis . . . 48
- 33. Comparison of average effective diffusivity of picolinic acid from L OMI waste fonns ... 49
- 34. Comparison ofleachability indexes of picolinic acid from LOMI waste forms .. 49
- 35. Comparison of average fractional releases ofMCo from LOMI waste forms . ... .. 50
- 36. Comparison of average fractional releases of55Fe from LOMI waste forms . . . 50
- 37. Comparison of average fractional releases of 63Ni from LOM1 waste forms . .. .. 50 l
- 38. Cumulative fraction releases of *Co from LOMI waste forms . .. .. ... . 51 I 1
- 39. Cumulative fraction releases of55Fe from LOMI waste forms . . ... . ... .. 51
- 40. Cumulative fraction releases of 63Ni from LOMI waste forms . . . .. 51
- 41. Average effective diffusivity of MCo from LOMI waste forms . . . . 52 5
- 42. Average effective diffusivity of 5Fe from LOMI waste forms . . . .. . . 52
- 43. Average effective diffusivity of 63Ni from LOMI waste forms . . . . . .. . . . 52
- 44. Leachability indexes for 60 Co from LOMI waste forms . . ... . ... ... . .. 53 vii NUREG/CR-6164
- 45. Leachability indexes for 55Fe from LOMI waste forms .. . .. . ..... . . 53
- 46. Leachability indexes for 63Ni from LOMI waste forms . . . . . . . 53 LIST OF TABLES
- 1. Summary of recent cement-solidified resin waste teach studies . .. ... .. . 4
- 2. Compositions of ion-exchange resin wastes in the three liners solidified at Peach Bottom-3 . 5
- 3. Quantities of materials in Peach Bottom-3 liner 446828-15 . ... .. 6
- 4. Physical parameters of ion-exchange resin waste-form specimens collected from Peach Bottom-3 . . .. . . . . . . . .... 8
- 5. Compressive strengths of Peach Bottom-3 waste form samples . . . . . . .. .. . 17
- 6. Summary of Peach Bottom resin and cement waste form characterizations (decay date 10/25/89) . .. . .. . .. . . . . .... . 23
- 7. Leach test results for Peach Bottom solidified resin waste fomi #4, leached in deionized water .. . . . .. . .... ... .. . 26
- 8. Leach test results for Peach Bottom solidified resin waste fonn #12, leached in deionized water . .. . . . .. . . . . . . 27
- 9. Leach test results for Peach Bottom solidified resin waste form #8, leached in deionized water .. . .. . .. . .. . ..... . .. .. . 28
- 10. Weighted average leach test results for Peach Bottom-3 cement-solidified waste forms . . 29 1
NUREG/CR-6164 viii
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EXECUTIVE
SUMMARY
l During light water reactor operation, the in- ion-exchange resin wastes solidified in cement core irradiation of fuel rod cladding and other using the tests from the U.S. Nuclear Regulatory reactor structural surfaces and the subsequent Commission's " Technical Position on Waste corrosion of these components introduces activa- Fomi," Revision 1, for compression testing and tion products such as 54Mn, 55pe,6nCo,63Ni, a nd leachability and to determine the release rates of transuranics into the primary coolant. These radionuclides, chelating agents, and transition activation products are transported by the primary metals from solidified ion-exchange resin wastes
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l coolant throughout the primary system. Some that have been immersed in deionized water.
l fraction of these activation products adheres to j intemal primary system surfaces and, over time, in this study, untreated ion-exchange resin i can result in the buildup of deposited adtivity and wastes and small-scale Portland Type I-P waste-l substantial radiation fields in the vicinity of these form specimens were collected from solidifica-i surfaces. In order te minimize occupational expo. tion vesse!s during a solidification at the Peach sure during primary system maintenance and Bottom Atomic Power Station Unit 3 (Peach inspection activities, chemical decontamination Bottom-3). LOMI-NP-LOMI decontaminations methods are now commonly employed to remove were performed on the primary coolant recircula-activation products from primary system internal tion system and on the reactor water cleanup sys-l surfaces. tem at Peach Bottom-3 during late December 1987 and early January 1988. The ion-exchange The low oxidation-state transition-metal ion _ resins generated as put of this process were soli-nitric pennanganate-low oxidation-state transi. dified in cement in 1989, tion-metal ion (LOMI-NP-LOMI) process is t
among the chemical processes most frequently Two tests were performed to evaluate waste used to decontaminate primary system compo- f rm structural stability and leachability; the nents. A principal reagent used in this process is ASTM C39 compression testing procedure was the chelating agent, picolinic acid. Chelating used to assess structural stability, and the ANSI /
agents are used in reactor system decontamina- ANS 16,1 leach test procedure was used to assess tion formulas because they form strong com- leachability. Compression tests were performed plexes with actinides, lanthanides, heavy metals, both before and after the 7-day immersion testing and transition metals and help them to stay in nd after the 90-day leach test as specified and solution. These chemical decontamination solu- described in Appendix A of the " Technical Posi-tion on Waste Fonn," Revision 1.
tions, once used, are treated with ion-exchange resins to extract soluble metals and chemicals; During the teach test that was performed these resins constitute the final waste to be pro-according to the ANSI /ANS 16.1 standard, mea-cessed sad disposed from the decontamination .
process.
surements were performed for pil and conductiv-
- g7 g g radionuclides, stable metals, and picolinic acid in The resin wastes contain quantities of chelates the waste form; and for the releases of these con-or complexing agents in addition to inventories of stituents from the waste form into the leachant.
radioactive corrosion products. A potential prob-The releases to the leachant are quantified in lem with the chelated decontamination wastes is terms of the absolute and fractional release rates, l the potential for increased solubility of the cumulative fractional release, effective diffusiv-i organo-radionuclide complexes in groundwaters
' ity, and leachability index.
at low-level-waste repositories.
i The primaiy conclusions of this study relate to l The purpose of this research study is to evalu- the structural stability of the Peach Bottom-3 ate the stability of actual low-level radioactive waste form and the releases of radionuclides, l
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stable metals, and the chelating agent (picolinic been added for comparison purposes and because acid) from the waste form. In this study, compari- of the importance of possible releases of 1291 and sons have been made with degraded waste fonns 99Te to the environment.
such as the FitzPatrick waste form from a prior part of this study and with other LOMI waste The summed radionuclide content in the Peach form research.
Bottom-3 waste forms is 7.8 pCi/g of waste form. The primary decontamination radionu-clides present in the resins based on their mea-Key conclusions of the compression tests per- sured concentration are 54Mn, 65Zn, 60Co, 55pe, formed to assess structural integrity are that the 63Ni,and 14C. The summed activity of these Peach Bottom-3 waste forms meet the require.
radionuclides is 7.7 pCi/g waste form or about ments for waste form integrity identified in the 98% of the total activity Carbon-14 makes up
" Technical Position on Waste Form," Revision !
bout 58% of the total activity. The dominant (500 psi or 3.4 x 103 kPa). Post-immersion, decontamination radionuclides,60Co and 55pe, compression-testing results indicate that the com.
make up about 31% and 1.9% of the total activity pressive strengths ranged from 960 to 1,370 psi in the resin waste, respectively. In contrast, the for all leachants with specimens tested in deion.
fissi n products 90Sr,99Tc,129 ,1 and 137Cs collec-ized water and seawater having compressive tively constitute about 0.3% of the total activity.
strengths near 1,350 psi. This is lower than the The concentrations of the transuranic isotopes are compressive strengths oflaboratory specimens of als I w and sum to a total of 14 x 10-3 pCi/g solidified decontamination ion-exchange resin (0.02% of the total activity). Creater than 87(fc of waste fonns solidified using the LOMI process.
the transuranic activity was 2dPu.
In the evaluation of the teach test results, the Among the stable metals whose concentrations primary conclusion was that the Peach Bottom-3 were measured in the resin wastes, the iron con-waste fonn meets the teachability index require- centration was highest at 3,000 pg/ gram resin.
ments specified in the NRC's " Technical Position This was followed by nickel and chromium. In on Waste Form." Revision 1. In addition, pH addition, analyses were performed for sulfate and effects on leachability and the characteristics of phosphate. Neither type of ion was detectable in radionuclide and stable metal releases from the the waste form or the resin samples, waste fomi were also assessed. The pli data sug-gest that the pH of the leachate is affected within A comparison of the leachability characteris-a few hours and probably within a few minutes by tics of picolinic acid from the Peach Bottom-3 the chemistry of the waste form. Other studies and decomposed FitzPatrick samples indicates have indicated that the cement chemistry will that the average absolute and fractional release control the teachate pH unless magnesium, a con- rates of picolinic acid for both waste forms are stituent of seawater, is present in the teachate in similar. The similarity of the release rates of the significant concentrations. It has been further picolinic acid from the two waste fonns (one that suggestea that the ion strength of seawater may remained intact and one that disintegrated) indi-be a more important parameter and have a greater cates that structural integrity is not a factor in effect on radionuclide solubilities in the leachate releases from the waste form. These data suggest than the pH. that chemical mechanisms either in the waste form or in the resin itself control the release rate Primary radionuclides for which measure- from the waste form and that compressive ments were performed were 3 4C, 55Fe, 60Co, strength does not affect retention in the waste 63Ni, 99Tc,1291, and transuranics. Iron-55,6"Co, fonn.
and 63Ni are neutron activation products that are concentrated by the decontamination process and A comparison of the absolute and fractional are:of primary concem in this study. The results release rate data for 55pe,6"Co. and 63Ni, the for 137Cs, 99Tc,and 129, 1 fission products, have three decontamination radionuclides from the NUREG/CR-6164 x
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Peach flottom-3 and FitzPatrick samples, indi- a weighted average fractional release rate 20 l cates that the waste funn structural stability does times faster than 14C.
not appear to affect releases from the waste form.
The average fractional release rate of 63N; from This weighted average fractional release rate of the Peach Bottom-3 samples is higher than that 9*fe is statistically the same as that fw MFe and for the other decontamination radionuclides and PCo and suggests similar chemical and reRase ,
indicates that this radionuclide is released at a rate behavior for 99Tc. This might be expecieu j higher rate than the others. The higher fractional because technetium is a metal and would be j release rates associated with 63 Ni may be due to expected to form complexes with organic com- !
the increased stability of nickel complexes, as the pounds such as chelating agents.
Irving-Williams correlation indicates that the sta-bility of transition metal complexes fall in the The fractional release rates of iodine and order NiU>Co II>Fe ll. These data suggest that the cesium are the highest of all radionuclides present l
stability of the nickel complex with a chelating in the waste fonn and are statistically the same as agent may result in the higher average fractional that for picolinic acid (5.8 x 10~* cnr2. sa y, ,
release rates of 63Ni relative to the other transition which suggests that the maximum diffusional '
metals. fractional release rate from the waste form is between 5x 1040 car2. 3 4 .m d I x 10-9 cm-2 sd, l The best value cumulative fractional release l (CFR) for all radionuclides ranged from 8.8 x Evaluation of the release rate data for the stable 1 0-5 (14C) to 7.7 x 10 2 (1291 ). The best value metals indicates that iron and chromium have i CFR for "Fe was I A2 x 10~3 and is similar to similar release rate characteristics and that the l the CFR for the radionuclide for the degraded release rates (absolute and fractional) of these )
FitzPatrick sample and is similar to that for6 "Co. metals from the intact Peach Hottom-3 waste in contrast to these data, the CFR for 63Ni was fonn are similar to those from the degraJed Fitz-5.9 x 10'3 which is about a factor of three to four Patrick waste form. These data further confirm higher than the other two radionuclides. These the fact that the release of nickel and other ele-data suggest that 55Fe and 6"Co exhibit similar ments are not dependant on waste fonn structural l
cumulatise release behavior : hat is different than stability. In addition, the average fractional the releases of 63Ni, release rate of nickel (9 x 104enr2. sd)is sta-tistically the same as that for picolinic acid. These data suggest that the release of nickel may not be Other radionuclides for which analyses of the controlled by the release of picolinic acid as it is l
waste form and chelating agents were perfonned released at a similar rate to the picolinic acid.
and measurable results were obtained were 14C, i WTc,129g, WSr. and 241Pu. Carbon-14, 9*Fc, and in contrast to nickel, the average fractional 129 1 were detectable in most samples, whereas release rate of iron (6A x 1043 cnr 2. s a) js 90 Sr was detectable in only a few of the teachate about a factor of 100 less than the weighted aver-samples, and 243 Pu was not detectabic m the lea- age fractional release of5 5Fe (6.8 x 104I chates. The weighted average fre.ctional release enr 2. s4) and indicates that 55Fe is released ratis of 14 C are the lowest of any of the radionu- faster than elemental iron from the waste fonn. A clides measured. This !s consistent with the comparison of the average and diffusion-driven results of Krishnamoorthy, who attributes the low fractional release rates indicates that 55Fe release release rate of 14 C measured in his study to the rate is higher during the initial leach oeriods, formation of insoluble hydrates and carbonates, whereas the iron release rates are relaw. i simi-which slow the release of this radionuclide. Fur- lar throughout the teach test. These i n iggest ther, he suggests that the fractional release rate of that 55Fe is in a different chemical ft ian the 6"Co should be slower than 14C. This is inconsis- clemental iron; however, kinetics sugest that tent with our results, in which 6"Co is released ai 55 Fe should be equilibrium with whatever xi NUREG/CR-6164 l
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l chemical form the elemental iron is in. No form does not appear to affect the fractional explanation for this behavior is apparent. release rate. The inventory of picolinic acid in an Indian Point sample was an order of magnitude Absolute release rates for iron, nickel, and less than the other waste fonns and yet the frac-chromium are within a factor of four for all ele- tional release rate was greater than those for FitzPatrick and Peach Bottom-3. However,it ments. These data and the fractional release rate data, which indicate a low fractional release rate should be noted that ahhough all samples were for iron, suggest that the release of these elements solidified using the LOMI process, the formula- j from the waste form is not dependent on the tions used for Indian Point and FitzPatrick were ,
'entory in the waste fonn and that other chemi- considerably different than those used for Peach nechanisms may be controlling factors for Bottom-3. The fact that the CFR of picolinic acid
....ases of stable metals.
for Peach Bottom-3 is considerably lower than that observed for other waste forms suggests that recent changes in the formulation of the LOMI The CFRs f or nickel (2.9 x 10-2) and chro-mium (1.6 x 10-2) are within a factor of two, waste form may have improved the leaching pmperties of the waste form.
whereas the n for iron (4.6 x 10-5) is about 0.1% of the nickel. These data indicate that the irot ined in the waste form to a in summary, the key conclusion from the Peach much greater extent than the other metals, which Bottom-3 study is that the leachability indexes of may be due to the greater complexing capability all radionuclides meet the requirements of the of nickel and the other metals. These data suggest NRC's " Technical Position on Waste Form,"
that a complexing effect is present, which Revision 1, Other primary conclusions are thtt enhances the release of nickel and possibly the release rates of radionuclides, stable metali, chromium. and chelating agents do not appear, in general, to be affected by the structural stability of the waste The coi .uions of radionuclides, chelating form. These data suggest that waste form com-agents, and wable metals in the liner were calcu. pression testing is of limited value in assessing lated as Ci/ liner for radionuclides or kg/ liner of actual waste form stability. Other key points are 63 stable metals or chelates. The summed radionu- that the apparent higher release rate for Ni may ;
clide content of the Peach Bottom-3 liner is 56 Ci. be due to greater stability of complexes formed The primary decontamination radionuclides pres- by this radionuclide and further suggests that ent in the liner, based on their measured con- there are chelant effects on the transition metals.
centrations, are 54Mn,65Zn,*Co 55Fe,63Ni, and These effects are less apparent for 55Fe and MCo, 34G The summed activity of these radionuclides which form complexes that are less stable than .
is S5 Ci or about 98% of the total activity, those formed by 63Ni. Also, the release rate behavior of 99Tc is similar to that of 55Fe and To assess possible radionuclide releases from MCo and suggests similar chemistry for this the liner, the order of the leachability indexes are radionuclide.
summarized below from lowest to highest: 1291 >
137Cs > 90Sr > 63Ni > %1 'c > MCo > 55pe > 14C. Another principal observation is that 14C, As expected, the cations and anions had the low- which had the highest inventory (58%) of any est leachability indexes (8-9), and 14C had the radionuclide in the waste form, had the lowest highest. leahbility index, and indicates that this radionu-clide is strong?y retained in the cement matrix, Comparisons of the releases from the Peach probably as an inwluble hydrate or carbonate. In Bottom-3 LOMI waste forms that have been contrast,129 1, a mot >ile anion, is released at rates leached as part of this study and LOMI waste similar to those for 137Cs and has the lowest fonns leached as part of previous studies indicate teachability index (8.4) or the highest release rate that the inventory of picolinic acid in the waste of all radionuclides measured.
NUREG/CR-6164 xii
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ACKNOWLEDGMENTS The authors are grateful for the support and technical assistance of a number of people in the completion of this pmject. R. M. Neilson, Jr. and C. V. Mctsaac of EG&G Idaho at the Idaho National Engineering Laboratory provided a critical review of the document along with the NRC Program Manager, Phillip R. Reed, l and Mike Dragoo of the staff of the Peach Bottom Atomic Power Station. In addi-tion, Stanley Schuetz assisted in performing the leaching measurements, and others of the INEL staff performed the radiochemical analysis work.
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i xiii NUREG/CR-6164 l
ACRONYMS ANSI /ANS American National Standards INEL Idaho National Engineering Institute /American Nuclear Laboratory Society ISO International Standards AP alkaline permanganate Organization ASTM American Society for Testing LOMI low oxidation-state and Materials transition-metal ion CFR Code of Federal Regulations NP nitric permanganate Cf4R cumulative fractional release NRC U.S. Nuclear Regulatory CNSI Chem Nuclear Systems Commission incorporated PCP process control program HPGe hyperpure germanium Peach Bottom-3 Peach Bottom Atomic Powc ICP-AES inductively coupled Station Unit 3 plasma-atomic emission spectroscopy TSP trisodium phosphate I
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Release of Radionuclides and Chelating Agents from Cement-Solidified Decontamination Low-Level Radioactive Waste Collected from the Peach Bottom Atomic Power Station Unit 3 INTRODUCTION l
During light water reactor operation, the in- complexes in groundwaters at low-level waste core irradiation of fuel rod cladding and other repositories.
reactor structural surfaces, and the subsequent corrosion of these components introduces activa- The U.S. Nuclear Regulatory Commission tion products such as 54Mn, 55pe, mCo, and MNi (NRC) is concerned with the safe disposal of into the primary coolant. These activation prod- these chemical decontamination wastes and has ucts are transported by the primary coolant made provisions for their disposal in " Licensing throughout the primary system. Some fraction of Requirements for Land Disposal of Radioactive these activation products adheres to intemal pri- Waste"(U.S. Code of Federal Regulations Stan-mary system surfaces and over time, can tesult in dard 10, Part 61). Section 61.56 provides the buildup of deposited activity and substantial requirements for the stability of waste fonns that radiation fields in the vicinity of these surfaces. In must be met for the waste form to be acceptable order to minimize occupational exposure during for near-surface disposal. Additional require-primary system maintenance and inspection acti- ments for the disposal of chelated wastes are also vities, chemical decontamination methods are given in burial site regulations. In Section 61.54, now commonly employed to remove activation the wastes are classified as Class A, B, or C, products from primary system intemal surfaces. based on the concentrations of radionuclides in the wastes. Class A wastes have lower concentra-tions and may be disposed of without stabiliza.
The LOMI-NP-LOMI process is among the tion; however, Class A wastes buried with chemical processes most frequently used to Class B and C wastes must be stabilized. Class B decontaminate primary system components. This and C wastes must be structurally stabilized to process is described in Appendix A. A principal ensure that the waste form does not degrade and reagent used in this process is the chelating agent. does not promote slumping, collapse, or failure of picolinic acid. Chelating agents are used in reac- the cap or cover of the near-surface disposal tor system decontamination formulas because trench. In addition, the stability of the waste form they form strong ce;aplexes with actinides, lan- limits exposure to inadvertent intruders. Class B thanides, heavy metals, and transition metals, and and C low-level wastes from light water reactors help them to stay in solution. These chemical (LWRs) may be solidified at LWR sites using decontamination solutions, once used, are treated cement to meet the stability requirements of the with ion-exchange resins to extract soluble metals NRC's " Technical Position on Waste Form,"
and chemicals; these resins constitute the final Revision 1. Solidification of these wastes is waste to be processed and disposed from the intended to provide the structural stability needed decontamination process. The resin wastes con- to ensure that no collapse of the disposal trench tain quantities of chelates or complexing agents in occurs and that the release of radionuclides via addition to inventories of radioactive corrosion leaching is minimized.
products and lesser inventories of fission prod-ucts. A potential problem with the chelated Test procedures to demonstrate waste form sta-decontamination wastes is the potential for bility and to quantify leachability for the low-increased solubility of the organo-radionuclide level wastes from LWRs have been specified by 1 NUREG/CR-6164
7 1
Introduction i
t j the NRC in the Low-Level Waste Management The leachability of decontamination ion-j Branch's " Technical Position on Waste Fonn,"I exchange resin waste forms that contain chelating published in 1983, and in the " Technical Position agents is being evaluated because the leachability i on Waste Form," Revision 1,2 published in of these waste fomis is a function of a number of i f anuary 1991. Both revisions of the Technical factors, including the chemical characteristics of Position specify that small-scale waste-form the radionuclide being leached, resin waste chem-specimens must be prepared and tested to certify istry, solidification agent, chelating agent, and the
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, the stability of the full-scale waste form. A range final solidified matrix. Burial site hydrology and j of tests must be perfonned that include compres- groundwater chemistry also influence leaching
- sion testing and leach testing of small-scale rates, as do cyclic wet and dry conditions. The j waste-form specimens. complexity of the interactions that occur among a
radionuclides, chelating agents, groundwater, and
] soil introduces uncertainties into the models used 1 predict the impact of the decontamination resin The NRC's " Technical Position on Waste wastes on the perfommnce of shallow-land burial l Form," Revision 1, stipulates that the small-scale sites. Therefore, it is important to establish a data l waste-form specimen, after having been j base on the stability and leachability of decon-immersed in deionized water for a minimum of ,
tamination resin waste forms representative of i 90 days, should have a compressive strength of at waste forms commonly generated at operating i least 500 psi (3.4 x 10 3kPa) when tested in accordance with the American Society for Test. commercial power stations in leachants that are ing and Materials ( ASTM) Standard C39,3 expected to be representative or more aggressive i
than the actual disposal site groundwaters. Deion-l " Compressive Strength of Cylindrical Concrete ized water is considered to be an acceptable
) Specimens." In addition, the " Technical Position j on Waste Form," Revision 1, stipulates that the aggressive leachant as discussed in Appendix A 0f the " Technical Position on Waste Form," Revi-i small-scale waste-form specimen should have a ,
leachability index greater than 6 when leach- smn1.
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tested for a minimum of 5 days in accordance l
j with the American National Standards Institute / The results of numerous investigations American Nuclear Society (ANSI /ANS) Stan- reported in the literature indicate that the rate of
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' dard 16.1," Measurement of the Leachability of radionuclide release from a decontamination ion-Solidified Low-Level Radioactive Wastes by a exchange resin waste form is influenced by Short-Term Test Procedure."4 poorly understood interactioes related to the properties of the solid and the Itaching system.
Further, waste forms of this type hue been found The purpose of this research study is to evalu- to not solidify as expected or to praduce poor ate the stability of actuallow-level radioactive waste forms. Among the factors that are known to ion-exchange wastes solidified in cement using influence the teachability of cement-solidified the tests from the " Technical Position on Waste . waste forms are the chemical composition of the Form," Revision 1, for compression testing and cement used, the waste-to-binder ratio, the leachability, and to determine the release rates of amount of water used to set the cement, and the radionuclides, chelating agents, and transition presence of additives that are used to accelerate or metals from solidified ion-exchange resin wastes retard cement hydration. Other factors such as that have been immersed in deionized water. This temperature, leachant composition, pH, volume, work is identified in the NRC's Low-Level and residence time may also influence leachabil-Radioactive Waste Research Program Plan,5 ity. Solidification, which did occur as expected, which defines a strategy for conducting research and the factors affecting solidification were dis-on issues of concern to the NRC in its efforts to cussed in depth at the Workshop on Cement Sta-ensure stability of solidined low-level radioactive bilization of Low-Level Radioactive Waste.6 waste, leading to safe disposal. Specific process details and problem wastes were NUREG/CR-6164 2
l Introduction reviewed. One of the conclusions of this confer- effects of seawater on leach rates of non-resin ence was to revise the solidification formulation wastes by Fuhrman and Colombo28 indicates that 3
to improve the stability of the waste form. As will release rates were a factor of 10 less than those j be discussed, the Peach Bottom Atomic Power observed for deionized water. The slower release l Station Unit 3 (Peach Bottom-3) waste forms rates are thought to occur because of the much leached as part of this study were some of the first higher ionic strength of the seawater leachant and wastes stabilized using improved formulations, cement / waste-leachant reactions. However, stud-and this study was conducted to assess the effec- ies at the Idaho National Engineering Laboratory tiveness of:his improved formulation. (INEL)(Reference 17) indicate that the effect of seawater on radionuclide releases from solidified A number of studies,7-17 as shown in Table 1, decontamination ion-exchange resins varies and have been performed, which address solidified may be similar to groundwaters.
resins or decontamination solutions. Results of these studies are used for comparison purposes or The present study is a continuation of stud-to assist in the interpretation of the results of this iest 2,17.25 previously performed at the INEL for study. Common to these studies is an emphasis on the NRC that measured the compressive strength more realistic leaching situations involving local and leachability of cement-solidified evaporator groundwater,7.10J 2.17 seawater,12J 7 and actual concentrates and decontamination ion-exchange nuclear power plant resin wastes.woJ2a7 In bead resin waste forms leached in deionized these studies, solidified ion-exchange resin speci- water, groundwaters, and seawater. The studies at mens were subjected to leach tests following the INEL are the only continuing studies in which either the ISO 6961 leach-test procedurel8 or the actual commercial nuclear power plant decon-ANSI /ANS 16.1 leach-test procedure. Both of tamination radioactive waste is being evaluated.
these methods are nonequilibrium tests in the respect that the solidified waste-form specimen is in the current study, untreated ion-exchange completely immersed over an extended period of resin wastes and small-scale Portland Type 1-P l time in a large volume of leachate that is periodi- (pozzolonic) waste-form specimens were col- I j cally replaced with new teachant. Other more lected from solidification vessels during a solidi- I recent studies!"23 performed using various fication at Peach Bottom-3. LOMI-NP-LOMI waste types have suggested that leachant effects, decontaminations were performed on the primary
- limited solubility, and breakdown of organo- coolant recirculation system and the reactor water radionuclide complexes may limit the effects of cleanup system at Peach Bottom-3 during late chelating agents on releases from waste fonns. December 1987 and early January 1988. A !
description of these decontaminations is l Differences in leaching behavior have been presented in References 26 and 27, and a sum- I observed in the studies that appear to be a result of mary of the waste solidification and sampling j changes in leachant composition. A study of the process is presented in Appendix B.
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Introduction Table 1. Summary of recent cement-solidified resin waste leach studies.
Solidification Reference number Sample size Leachant Agent (si Resin type Author 2.5 cm x 5.0 cm llanford Portland cement BWR evaporator Cnscenti.L J. 7 Serne, R. J. (diameter x length) groundw ater type III concentrates and ion-exchange resins 8,9 28 mm x 28 mm Demineralized water Portland cement, LOMI ion-exchange resin Howard. C. G.
Jolliffe, C. B. (diameter x length) hlast furnace slag. DOWEX 50X8 6"Co.
Lee, D. J. microsilica 137Cs Small lab-scale Groundwater Cement Spent ion exchange resins lpatti. A. 10 from Losiisa Power Plant liarkonen H. specimens Torstenfelt, B. Not specified Not specified Sulfate resistant Powdered ion <xchange II Portland cement resins with 5 wt.% ecolite liedin G.
5 cm x 10 cm Groundwater and Portland eement Decontamination Mcisaac C. 12 (diameter x length) seawater TypeI-P ion-exchange resms J. W. Mandler IR N-77, IRN-78, C.ltnH.and AMio Imhop, J. V. 13 2 in. x 4 in. Compression test Portland cement lon<xchange resins lonac (diameter x length) only Lime and NaOli A-365 and C-267 with picolmic acid only 14 2m x 4m Demineralved water Portland cement lon-exchange resins Davis. M. S.
(diameter x length) Type I and VES IRN-77, IRN-78, Picuilo P L.
et al. kmac-365 with chelates only Lee.J.O. 15 Not specified Demineralized water Cement, polyester ion exchange resins, Li+ -
llan, K. W. resin and 7eoloin Dil form,*Co, #5Sr, and Buckley, L. P. 9m Na WCs Sm,P 16 5cm x 10 cm Deionized water Portland cement Simulated decontaminated 15 cm x 15 cm Formate and Type I and VES resin waste 30 cm x M) cm pico-linate solutions (diameter x length)
Melsaac et al. 17 5 x 10 cm Deionned water Ponland cement Power plant grounda ater. T)pcl-P decontamination seaw ater ion-exchange resin wastes NUREG/CR-6164 4
EXPERIMENTAL PROCEDURES This section summarizes the experimental pro- faces of the primary coolant recirculation system cedures used in this study. Many are specific to and the reactor water cleanup system were lonae the characterization of commercial reactor waste A-365 weak base anion resin and lonac C-267 streams and cement solidified decontamination strong acid cation resin, w hich are manufactured ion-exchange resin waste forms. Included are the by Sybron Chemicals, Inc., of Birmingham, New methods used to collect the untreated resin waste Jersey. About 160 ft3of anion resin and about 136 ft3 of cation resin were used to process the I and waste-form specimens, procedures used to test the waste-form specimens for compressive LOMI decontamination slurry. During January )
strength and leachability, and the analytical meth- and August 1988, the ion-exchange resins were I ods used to detennine the concentrations of radio- sluiced to three separate liners. A solidification nuclides, metals, and chelating agents in the was attempted in December 1988; however, the untreated resin waste and teachate samples. process control program (PCP) samples failed quality assurance tests, and the solidification was Sample Collection del yed. Infonnation on the decontamination is contained in References 26-28. As will be dis-cussed later, personnel at Chem Nuclear Systems Resin wastes and waste-form specimens were incorporated (CNSI) believe that an enhanced 1 collected at Peach Bottom-3, which is operated exothenn during the initial stages of the solidifi-by the Philadelphia Electric Company, from cation process may result in an improper solidifi-
! October 17 through October 25,1989. The solidi- cation and in poor waste fonn charactenstics.
fication was perfonned on decontamination ion-exchange resins from a LOMI-NP-LOMI Following an attempted solidification in i decontamination performed by Pacific Nuclear December 1988, about 7 ft3 of resin was trans- )
Services tReferences 25 and 26). The Peach ferred from liner 446828-15 to liner 446692-1 in Bottom-3 primary coolant recirculation system order to more evenly distribute the resin among and the reactor w ater cleanup system were decon- the three liners to ensure that the resin loading l
, taminated during late December 1987 and early was more equal for the three liners and thereby January 1988, and the resins were held until reduce the waste-to-cement ratio. All three liners October 1989 for solidification. contained mixtures of anion and cation resins.
i Table 2 presents the types and quantities of ion-l The ion-exchange resins used to process the exchange resins in the three solidification liners l
spent LOMI decontamination reagents and the as of October 1989 when CNSI solidified the i corrosion products removed from internal sur- waste.
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! i Table 2. Compositions of ion-exchange resin wastes in the three liners solidified at Peach Bottom-3. j Anion resin Cation resin Picolinic acid loading ;
3 Liner # 3 (ft ) (m )3 (ft )
3 (m ) (wt%)
446692-1 45.6 1.29 45.6 1.29 1.8 446828-10 59.5 1.68 33.3 0.94 4.5 446828-15 56.0 1.58 57.0 1.61 5.5 t
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1 Experimental Procedures l
By October 1989, personnel at CNSI had was sampled under EG&G Idaho supervision.
developed and tested a revised solidification for- The sampling tool, which was simply a plastic mula that they felt confident would work in solid- tube equipped with a plunger, was inserted into ifying the LOMI decontamination ion-exchange the resin / cement mixture five or six times to a resin wastes being stored at the Peach Bottom depth of about 3 ft below the top surface of the Station. EG&G Idaho personnel requested that mixture. Following each insertion, the material liner 446828-15 be solidified first. Since it con- inside the tube was transferred to a plastic-lined tained the highest concentration of picolinic acid bucket. About 2 gal of resin / cement mixture was and activation metals, for leach testing purposes, collected. The resin / cement mixture was quite it was the best candidate of the three liners for fluid, which made it possible to pour the material sampling. Table 3 lists the contents of liner into the molds that were used to prepare waste-446828-15. form specimens. Between 2:35 and 3:05 p.m. on October 24,19 waste-form samples 2 in. (5 cm) in The initial PCP tests indicated that samples diameter and 4 in. (10 cm) long were prepared.
prepared using smaller quantities of cement than Individual samples had contact exposure rates of the amount used to prepare PCP samples during about 100 mR/ hour. The sample molds were initial tests in December 1987 failed to solidify sealed immediately after they were filled, and at and that in addition, a strong odor of ammonia 6:30 p.m. on October 24, they were all placed in was noticed near the sample that failed to solidify. an oven that was maintained at 145 F to simulate As discussed in Appendix B, additional PCP sam- the hydration exotherm.
ples were prepared with more trisodium phos-phate than those prepared previously. The samples with the revised formulation were hard Three of the waste-form specimens were when examined the following day and, based on removed from the oven the following morning this information,it was determined that the solidi- and were examined. All of the samples that were fication could proceed. removed had some free-standing water on their top surfaces. They felt firm but were certainly not During the solidification of liner 446828-15, yet hard. These samples were then retumed to the after the fill-head was removed from the top of oven, and all 19 specimens were baked at 145 F the liner, the resin / cement mixture inside the liner for a total time of about 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br />.
Table 3. Quantities of materials in Peach Bottom-3 liner 446828-15.
Volume Mass Type of material (ft3) (m3) (Ib) (kg) lonac A-365 anion resin 56.0 1.58 3,749 1,701 lonac C-267 cation resin 57.0 1,61 3,818 1,732 Trisodium phosphate 4.8 0.14 550 249 Flyash 19.8 0.56 2,730 1,238 Portland Type I-P cement 28.78 0.81 4,982 2,260 Total: 166.4 4.7 15,829 7,180 NUREG/CR-6164 6
Experimental Procedures All three liners were solidified during the solid- degrades during the pil adjustment process, ification campaign however, the week after the thereby leaving additional reaction sites for cal-solidification, the liners were visually inspected cium ions. liydration of the calcium would gener-and a bmom handle test was perfonned to assess ate heat that would be localized at the l the strength of the waste form. (A broom handle ion-exchange resin bead and possibly cause gen-l or shaft of a similar diameter is pressed onto the cration of ammonia due to the degradation of the surface of the waste form to assess whether it has resin (a tertiary amine). An industry survey 30 was hardened sufficiently to present penetration into performed to assess the degradation mechanism.
the cement.) Both 446692-1 and 44682810 were Correspondence with Sybron Chemicals,31 the solid; however,446828-15 was caly solidified on manufacturer oflonac A-365, and a review of the l the surface. A thin crust had fonned over the top ion-exchange resin chemistry by this laboratory 32 l surface of the resin / cement mixture, but below indicates that these resins are sensitive to elevated the crust, the material had not yet solidified. temperatures and that they do degrade over their CNSI personnel suggested that ammonia in the service life.
l resin / cement mixture was retarding the setting of the cement. They recommended that the liner be Whether the presence of ammonia would be vented to help remove the ammonia. Plant per. expected to retard solidification has been eva-( sonnel followed the recommendation and began luated,30 31 and this evaluation indicates that low venting the liner the week of October 30. The concentrations of various amine compounds will not retard solidification. Ilowever, other liner was not examined again until December 21, l 1989. On that date, the upper surface of the mono _ reports A32 ndicate that ammoma compounds lith was again probed with a broom handle, and such as ammonium chlorides are strong retarding this time, the broom hardle did not penetrate the agents and will inhibit solidification. In any surface. event, solidification of the vessel containing 5.5 wt% picolinic acid did not occur immediately,
. . and the probable reasons suggested by CNSI are Potential problems w.it h the LOMI decontami-the hydration of calcium released during the pil nation process were evaluated by CNSI person-adjustment period or possibly the presence of nel,28 and they concluded that several factors may .
ammonia caused by degradation of the resins.
be contributing to problems with the solidifica- -
tion of LOMI wastes. They believed that the pres ~
Leach-Test Method ence of calcium ions from the lime used to adjust i the pH of the waste may have caused the exother- The test procedure used to measure the release mic hydration processo to begin earlier than of radionuclides, transition metals, and chelating expected and could have resulted in higher tem- agents from decontamination resin wastes solidi-peratures in the liner when the cement was added, fied in Portland Type I-P cement was ANSI /ANS !
thereby causing a poor solidification. To control 16.1. This standard is intended to provide a means the exothermic process, CNSI proposed that the of quantifying the release of radionuclides from temperature of the liner be monitored during the waste fonns using the results of relatively short-pil adjustment phase and that the liner be allowed term tests performed in a laboratory. It is not to cool before cement was added because the ntended to serve as a representative test for long- !
cement would further increase the temperature term leaching behavior of waste forms under (Reference 28). conditions representing actual burial conditions.
The method specified by the standard for analyz-In addition, CNSI suggested that a possible ing leach test data is based on the assumption that cause of the problems with LOMI solidifications diffusion is the only release mechanism. Other may also be due to the switch to lonac A-365 mechanisms such as dissolution, ion exchange, anion resin (Reference 28), which is reported to corrosion, cracking, etc., are not incorporated into have a greater capacity for picolinic acid and con- the models used to describe releases. Although sequently, more calcium, if the picolinic acid the adequacy of this assumption has been ques-7 NUREG/CR-6164
Experimental Procedures tioned,33 the test procedure is, however, believed were leached in cylindrical polyethylene contain-suitable 2.34 to establish a data base on the release ers having capacities of about 3 L. Figure 2 of radionuclides in the presence of relatively high shows a representative waste-form specimen sus-concer.trations of chelating agents and transition pended in a teach-test vessel. In all cases, the !
metals, waste-form specimen was supported in the leach- l test vessel by coarse mesh plastic netting that was I Test Procedure suspended by a wire from the container lid. The ]
leachant used for this study was deionized water i The three waste-form specimens obtained from having a conductivity of less than 3 pmho/cm at Peach Bottom-3 that were leach tested were right- 298 K (25 C). 4 circular cylindrical solids with nominal dimen- l sions of 1.75 in. (4.4 cm) in diameter by 3.5 in.
(8.9 cm) long. The actual dimensions of each The percentage of dry resin shown in Table 4 i sample and the curing times are shown in was calculated as the ratio of the weight of free Table 4. A photograph of a specimen typical of interstitial water to the weight of cement, triso-the mixed-bed resin waste forms collected from dium phosphate, and flyash used during the solid-Peach Bottom-3 is shown in Figure 1. Figure 1 ification of the full-scale waste form from which shows that the mixed-bed resin waste-form speci- the waste-form specimen was collected. This per-mens prior to being leached were solid right-cir- centage was calculated using the method devel-cular cylinders having smooth surfaces with few oped by Neilson,35 which divides the water surface imperfections and no cracks. All samples content of the resins between the water content of Table 4. Physical parameters of ion-exchange resin waste-form specimens collected from Peach Bottom-3.3 Sample identification Sample characteristic #8 #4 #12 Diameter by height (cm) 4.7 x 9.3 4.4 x 8.9 4.4 x 8.9 Weight (g) 246.3 248.1 244.8 Surface area (cm2 ) 137.2 123.0 123.0 Volume (cm3 ) 161.3 135.2 135.2 Volume-to-surface ratio 1.18 1.10 1.10 Resin loadingb (vol%) 67.9 67.9 67.9 Resin loadingh (wt%) 47.8 47.8 47.8 Dry resin loading (wt%) 14.8 14.8 14.8
- a. Sample #8 was cured for 950 days prior to leach testing, and samples #4 and #12 were cured for 1,304 days prior to leach testing. Compression tests were performed near the earlier time.
- b. leadings determined based on liner composition.
NUREG/CR-6164 8 u_ _ _ _ _ _ _ _ _ _ _ __ _ _ _ _ _ _ _ _ _ _
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- Figure 1. Peach 110ttom leach test specimen. Figure 2. Peach Bottom leach test specimen j suspended in leachant.
{ the 'as-received" and dewatered ion-exchange standard reqllires a minirnum leach period of 5 j resins to determine the amount of.available inter-das s w hich corresponds with the current require-stitial w ater. In addition, there is ty pically a nonu.-
1 .
ment m the " Technical Position on W.aste1.orm.. I l nal I to 2 in. (_3.5 to 5 cm) of tree standing water _
Revision 1. f or a 3-day leach test. During the i above the resin in the hner bed. ~l_his quantity was .
4 period of the 5-day leach testing, the required .
! not included .m the calculation because the actual i ANSI /ANS 16.1 changeout schedule was main-level is not know n. .
tamed w.it hin several minutes and the leachant temperature was maintained at 77 5'F As required by ANSI /ANS 16.1. the ratio of g5 g yg j leachant solume to the geometric surface area ofl the specimen was kept constant at a ratio of at Data Analysis least 10:1. The actual volumes of leach solution 1 used were about 1.7 L. This volume exceeds the I.eaching occurs as the result of mass transport
! 10:1 ratio because ANSI /ANS 16.1 requires that of species both inside and from the surf ace of a I the sample must be surrounded by a leachant waste form. Mass transport processes that have layer exceeding 10 em in thickness or the mini- been identified as occurring in solidified waste j mum specimen dimension. In this case. the mini- forms during leaching include diffusion. dissolu-mum specimen dimension was used to determine lion ion exchange. corrosion, and surf ace effects.
the leachant volume. The pil and conductisity of A considerable amount of data that were obtained the leachates were measured at the end of each from samples that maintained their integrity dur-leaching period. ing leaching indicate that internal bulk diffusion
- is the most likely rate-determining mechanism During leach-testing. the requirements estab. during the later phases of the teaching process lished in ANSI /ANS 16.1 were followed. This (after 1-2 day s).3" The methods used to assess 9 NUREG/CR-6164
. - , ..w .W?v w-
Experimental Procedures i
- leachability (i.e., fractional release, cumulative The cumulative fraction release (CFR) of fractional release, and leachability index) are radionuclides, metals, and chelating agents from based on the premise that internal bulk diffusion the waste-form specimens is the sum of the indi- J is the rate-detennining process and are predicated vidual fractional releases calculated as j q on an intact waste fonn. n s
j (((C )nVn];
t For each waste-fomi specimen that was teach. CFR = (1) tested, the initial inventory of each species in the j waste form was determined by two methods. The wherc
! first method was to multiply the measured con-centration of the species in the untreated wet resin (Ct .)n = the concentration of the species waste, expressed as pCi/g or pg/g, by the mass of in the teachate collected follow-l
- water-saturated resin estimated to be in the waste- ing leaching interval n (pCi/mL form specimen. The quantity of resin estimated to or pg/mL)
I be in the waste fonn is based on the weight frac-tion of water and resin present in the resin / cement Vn = the volume of leachate collected mixture in the solidification liner from which the following leaching interval n
- specimen was obtained. This method is consid. (mL) l cred relatively accurate because the waste-form Cg = the concentration of the species l samples were obtained from the interior of liners that had been well mixed before sample collec_ in the resin waste (pCi/g or pg/g) tion. In addition, to confirm the analysis results Ma = the mass of resin waste estimated for the resin samples, samples of the solidified to be in the waste form (g).
i waste fonn were analyzed to determine the actual radionuclide, metals, and picolinic acid content Uncertainties in the CFRs of selected radionu-per gram of solidified waste. These measure- clides; metals; and citric, oxalic, and picolinie '
- ments indicated that the resin loading was acids were calculated at the one-sigma confi-
! approximately 53 wt% based on the radionuclide dence level using representative data for resin
- content of the resin and waste fonn. This is simi- waste and teachate samples Uncertainties in the lar to the resin loading (48 wt%) determined from absolute counting efficiencies of the hyperpure 4 Table 2. The difference is probably due to small gennanium (HPGe) spectrometers used to deter-irregulanties m the loading of the cement. The mine concentrations of gamma-emitting radionu-53 wt% value is probably more accurate, clides were assumed to be iS%.The uncertainty in the volume of any given leachate sample was j assumed to be 1%, and the uncertainty in the i Upon completion of the leach testing, the mass of resin waste in any given waste-form inventory information and the teach test data are specimen was assumed to be 5%.
used to detennine the average absolute and frac-tional release rates of radionuclides, metals, and The ANSI /ANS 16.1 standard provides for the chelating agents from each waste-fonn specimen. calculation of a leachability index, which is one
, The average absolute release rate is defined as the of the measures used in the NRC's " Technical i quantity released per unit surface area per second Position on Waste Form," Revision 1, to deter-(pCi/cm2. s or pg/cm 2 s), and the fractional mine the acceptability of a waste form for dis-release rate is defined as the fraction of the initial posal at a waste site. The teachability index, L, is inventory released per unit surface area per based on the effective diffusivity of the species second (cm-2 3-1). The surface area used in this being leached from the waste form. When deple-calculation is the external geometrical surface tion of the diffusant is less than 20%, the effective area of the intact waste fonn. diffusivity (Dn) is defined as NUREG/CR-6164 10
Experimental Procedures Dn = x [(an /Ao)/An]2 x (V/S)2 xT (2) k = number ofleaching intervals.
where As shown in Equation (3), the leachability index of a particular diffusing species is the Dn = the effective diffusivity of a spe. summation of the incremental leachability cies during leaching interval n indexes for the all leach intervals.
(cm2fs)
Compressive Strength Test an = the quantity of the species Method leached during leaching interval n (pCi or pg) The test procedure used to measure the com-pressive strength of waste-form specimens was
= the total amount of the species l
Ao ASTM C39," Compressive Strength of Cylindri-originally present in the waste- cal Concrete Specimens,"3 as required by the fonu specimen (pCi or pg) NRC in the " Technical Position on Waste Form."1 The requirement is for a minimum compressive An = the duration of leaching interval strength for waste forms of 50 psi n (s) (3.4 x 102 kPa). This requirement has been modified in Appendix A of the " Technical Posi.
V = the volume of the waste-form tion on Waste Form," Revision 1, to 500 psi specimen (cm3 ) (3.4 x 103 kPa) for cement-solidified waste forms. The revised higher value is deemed neces-S = the external geometric surface sary to ensure that cement-solidified waste forms area of the waste-form specimen maintain integrity and exhibit long-term stability ,
(cm2) as required by 10 CFR 61.34 T =
the leaching time rep' resenting The vice and load gauge used to measure com-the "mean time" of the nth leach- pressive strength are shown in Figure 3. Each ing interval (s). specimen was placed in the vice, and the load on I the specimen was gradually increased until the ;
As shown in Equation (2), effective diffusivity load gauge registered a decrease in load, which !
is proportional to the square of the ratio of speci- occurred when the specimen began to fail. The !
men volume to surface area. maximum load that each waste-form specimen withstood was recorded and was used to compute The leachability index is based on the effective the compressive strength of the specimen based diffusivity of the species of interest, and is also on its cross-sectional area.
dependant on the estimated surface area of the debris. The leachability index L, is defined as Analytical Methods k The data analysis methods of ANSI /ANS 16.1 L =
f (( log (b/D)]n (3) require a knowledge of the initial inventories of n=1 diffusing species in the waste-form sample being tested and a knowledge of their concentrations in where the leachates generated during leach testing. In order to provide a basis for estimating the initial b =
defined constant (1.0 cm2/s) inventories of species of interest, samples of unsolidified resin waste, solidified waste-form D = effective diffusivity of the spe- samples, and leachate samples were analyzed cies (cm2/s) using several different analytical techniques.
Experimental Procedures mg y
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- ammans 7 ,
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- J$ L h h h(N5hpMQ,y.I'
$$$$$gWainkb$b62Nbh$$hM5)$x;LwANN Figure 3. Compressise strength testing sy stem.
Because of the differences in their phy sical char- coupled plasma-atomic emission spectroscopy, acteristics and because the concentrations of and ion chromatography. The detection of chelat-radionuclides and metals in the leachates were ing agents in some leachate solutions required expected to be as much as several orders of mag- that the chelating agent be chemically separated nitude lower in the teachates compared to the res- from other components of the sample prior to ion ins, the methods required to prepare the resin and chromatography analysis teachate samples for analysis were generally different. The following sections provide descriptions of the sample preparation and analysis methods used Prior to analysis, leachate solutions were parti- to analyze the resin waste and leachate samples i tioned into volumetric samples according to the obtained during the course of this study.
analysis scheme shown in Figure 4. The analyti-cal methmis used to determine concentrations of Radionuclide Analysis radionuclides, transition metals, and chelating i agents in leachate samples included high-resolu- Resin waste samples were analyzed for radio-tion gamma ray spectrometry, liquid scintillation nuclides specified in 10 CFR 61 (i.e.,14C, and gas proportional counting, inductisely 6"Co,"3N i, ""S r, ""Tc,129 1, U7Cs, 2 4Pu, 2 WPu, NUREG/CR-6164 12
Experimental Procedures 540 mL HPGe gamma l spectrometry Sd Mn, 6 Co, 65Zn , *37Cs 1 mL Liquid scintillation counting 55 Fe, 63Ni 100 mL Gas proportional counting 8U Sr l
50 mL Lowenergyphgncounting I
Leachate solution 1,25 mL Chemical separation 1-2 L "C , gSTc monitored for pH and conductivity 50 mL ICP-AES (Iron, Nickel, Chromium, Cobalt, Zinc) 10 mL lon chromatography l (Phosphate, Sulfate) 240 mL HPLC l Picolinic acid ARCHIVE Figure 4. Leachate analysis methods.
Experimental Procedures 241Am and 244Cm) and for other radionuclides counter, and the concentration of 90Sr was deter-using standard environmental analysis proce- mined using a gas proportional counter.
dures. Concentrations of gamma-emitting radio-nuclides (e.g.,60co,137Cs. and other measurable The resin and waste-form samples analyzed for gamma emitters) in each resin sample were mea- concentrations of transuranic isotopes were wet-sured by diluting an aliquot of the dissolved resin ashed using nitric, sulfuric, and perchloric acids.
with water and analyzing this volumetric sample This procedure was followed by a pyrosulfate using gamma-spectrometric techniques. When fusion to dissolve any remaining undissolved resin waste-fonn samples were analyzed, a small compounds. The fusion was then dissolved in 2 M sample of the solidified waste was analyzed IICl, and the actinides were precipitated using directly at a distance of 10 cm from the detector. barium sulfate. The barium sulfate precipitate The llPGe spectrometers used to analyze these was then dissolved in alkaline ethylene-diamine-samples were calibrated using reference sources tetra-acetic (EDTA) to precipitate the actinides as traceable to the National Institute of Standards hydroxides. The hydroxide precipitate was then and Technology. dissolved in acid, and then the solution was oxi-dized to adjust the oxidation state of plutonium.
Concentrations of beta emitters (e.g.,55Fe, Americium and curium were precipitated as fluo-63Ni, 90Sr,99Tc,and 24tPu) in the resin wastes rides and, following filtration, this precipitate was were determined using radiochemical separation mounted for analysis using a high-resolution techniques followed by liquid scintillation or gas alpha spectrometer. The filtrate was reduced, and proportional counting. In the case of 14 C, the plutonium was precipitated as plutonium fluo-solid sample is carefully dissolved in an alkaline ride. The plutonium fraction was also analyzed environment, and the dissolved sample aliquot using a high-resolution alpha spectrometer.
undergoes oxidation, separation, collection as carbon dioxide, and analysis via liquid scintilla- .
tion counting 39 in the case of 1291, the sample is """"#"P** "E ' "" # "~
chate samples (e.g.,54Mn,6nCo, and#" h"Cs) 13 were fused with sodium hydroxide and extracted using
""" *ed using gammanay specnomeuy as carbon tetrachloride.40 The 129 1 is quantified .
- "
- E"*
using low-energy photon spectrometry. Specific procedures for these analyses are discussed in Appendix C. Concentrations of 14C, 55Fe, 63Ni, "Tc,1291, and 90 Sr in leachate samples were determined by Stable iron, nickel, iodine, carbon, and stron. first using radiochemical techniques to selec-tium carriers and "5Sr tracer were added to an ali. tively extract and concentrate these radionu-quot of the dissolved resin waste, and the solution elides. Carriers and tracers were added to was then passed through a chloride-form anion volumetric samples of the leachates, and the sam-exchange column. Iron in the solution was left on ples were then evaporated to dryness. The sam-the column while nickel and strontium passed ples were then dissolved in an llCI solution.
through it. Unwanted radionuclides were washed These samples were then processed and analyzed from the column using hcl and HF acids, and the using the same procedures used for the resin-iron was then eluted using 0.5 M hcl. Ammonia waste samples.
and iron were added to the cluent of the column, and this alkaline solution was treated with dime- The procedure used to analyze the teachates for thylglyoxime to selectively extract nickel, and 238Pu, 239Pu,241Am, and 244Cm was the same as sulfate was added to anotF alk luot to precipitate that used for the resins in that a pyrosulfate fusion strontium as strontium sulfate. Concentrations of and the following analysis program were the 55Fe and 63Ni were determined by analyzing the same for both the waste form samples and the lea-separated activities using a liquid scintillation chates.
Experimental Procedures Elemental Analysis only lot-analyzed, trace-metal, analysis-grade reagents were used to prepare standards.
Samples of dissolved resin wastes and leachate solutions were analyzed using inductively Chelating Agent Analysis coupled plasma-atomic emission spectroscopy (ICP-AES). All samples were analyzed for con- The waste-form specimens and Icachates were l centrations of chromium, iron, and nickel. These analyzed for picolinic acid using ion chromatog-elements were selected for analysis because they raphy. A Dionex ion chromatograph equipped are the primary constituents of stainless steel and with an ion-exchange column ( AS-4A) was inconel, the materials used to line the intemal sur- employed using 5 mM sodium hydroxide as an faces of LWR primary coolant systems. In addi- eluent. The detector was set at 254 nm. This tion, the samples were analyzed for zinc, which is method has a sub-parts-per-million detection present in the reactor coolant system due to the limit for picolinic acid. For the Peach Bottom-3 !
presence of Admiralty brass. Potential analytical cemented waste form samples, dilutions of the background interferences introduced by the pres- dissolved samples were analyzed because of the ence of high concentrations of Ca+2 and other high concentration of other waste-form ions were evaluated using prepared standards, constituents present.
I l
l 15 NUREG/CR-6164
_ _ _ . _ _ . -_ . _ _ _ _ _ _ _ _ - _ __ . _ _ . _. ~
EXPERIMENTAL RESULTS Experimental results from the Peach Bottom-3 Form," Revision I, recommends a mean com-waste-form samples can be divided into the pressive strength of 500 psi for waste-form speci-results of two tests that were performed to evalu- mens cured for a minimum of 28 days,it has been ate waste fonn integrity / stability and leachability detennined in previous studies,41 that solidified using the ASTM C39 compression testing proce- ion exchange resins should be able to meet this dure3 and the ANSI /ANS 16.1 leach test proce- criterion.
d ure,4 respectively, Compression tests were perfonned both before and after immersion tests In addition to the initial compression tests, as specified and described in Appendix A of the Appendix A of the " Technical Position on Waste l
" Technical Position on Waste Form " Revision Fonn," Revision 1, requires that a compressive j l
1,2 and discussed in_ Reference 34. The objective strength test be performed after the waste form of the compression tests is to assess the structural has been cured and immersed in water for varying stability of the waste form both before and after periods of time depending on the waste type. In the 7- or 90-day immersion tests speciGed in the the case of decontamination ion-exchange resins regulatory requirement. with chelating agents, the waste form specimen must be cured for at least 180 days, immersed for During the 5-day leach test that was performed a minimum of 7 days, followed by a drying according to the ANSI 16.1 procedure, measure. period of 7 days. After the drying period, the ments were performed for pil and conductivity of waste form compressive strength should exceed the leachate; the concentrations of radionuclides, 500 psi or 75% of the pre-immersion compressive stable metals, and picolinic acid in the waste strength to meet the regulatory requirement. The fonn; and the releases of these constituents from reason for the special requirements for ion-ex-the; waste form into the teachant. The releases to change resins is that several studies have shown the leachant are quantified in tenns of the abso. that cure time and immersion resistance are lute and fractional release rates, cumulative frac. related and that longer cure times improve the ,
tional release, effective diffusivity, and compressive strength of the waste fonn.41,42 In leachability index. addition, in the case of pozzolonic cements (e.g.. ,
Brunswick, FitzPatrick, and Peach Bottom-3),
hydradon of the cement inlower; themfore, uhb Waste Form Structural Stability mate strength may not be obtamed for up to a year.43 44 The Peach Bottom-3 samples were According to 10 CFR 61.56 (b)l,"a structur. cured for 900 days prior to compression testing ally stable waste form will generally maintain its and consequently had reached their maximum physical dimensions and its form under the strength.
expected disposal conditions such as weight of overburden and construction equipment." The in this study, compressive strength measure-i initial criterion for structural stability as identi- ments were performed on specimens both before fied in the NRC " Technical Position on Waste and after immersion testing. The results of the Form"I is that the cement-solidified waste-form structural stability tests can be divided up into the specimen must exhibit a compressive strength of results of the compression testing that was per-50 psi (3.4 x 102 kPa). This was later raised to formed on the specimens before immersion test-60 psi (4.1 x 10 2kPa) to reflect an increase in ing and those performed on ones that retained burial depth to 55 ft at the Hanford site 34 How- their structural stability during immersion testing.
ever, as cement waste fonns are nominally capa- Table 5 summarizes the compressive strength test ble of achieving compressive strengths of 5.000 results for both before and after immersion test-to 6,000 psi (3.4 x 10 to 4. I x 10 kPa),
4 4 ing. Some compression tests were also perfonned Appendix A of the " Technical Position on Waste on the plant PCP samples that are used for the r NUREG/CR-6164 16 y eyy-..y.m, - . - . . w.-e- ,-r--- , - , - - - , . . , , , , -
i !
Experimental Results Table 5. Compressive strengths of Peach Bottom-3 wasle form samples ab Area Yield load Yield strength Sample tin 2/cm?) (th/k g) ips:/kPa) 90-day leach test
- 1. Unicached 2.7/17 4 3,370/I,530 1,240/8,570
- 2. UnleacFcd 2.7/I 7.4 2,620/l,190 970/6,710
- 3. Unleached 2.7/17.4 3,250/I,480 1,210/8,340 Ascrage i o 3,(W N) i 4(X)/( 1,3N) i 180) 1,140 t 150A7,870 i 1,010)
- 1. Deionized water 2,72/17,5 3.240/l.470 1,190/8,210
- 2. Deionized water 2.54/l6.4 3.3W/1,540 1,330/9.200 Average i o 3,320 i 110/(1,500 i 50) 1,260 i l(X)/(8,710 i 700)
I, Sea water 2.7/17.4 2,720/l.230 990/6,840
- 2. Sea water 2.7/17.4 3,81(VI,730 1,370/9,630 Average io - 3,270 i 770/(1,480 i 350) 1,190 i 280/(8,240 i 1,970) 7 tay immersion test Control' -
2.760 i 30/(1,250 i 10) 1,010 i 10A6,9NO i 70)
Deiomied water d -
2,590 1 30/(1,180 i 10) 956 i 10/(6,600 1 70 l
Deionized water' d -
2,750 i 30/(1,250 i 10) 1,010 i 10A6,980 i 70)
Simulated Barnwell' d -
2,750
- 30/(1,250 i 10) 1,020 i 10/(7,060 i 70)
Simulated Barnwelle d -
2NW) i 30/(1,210 1 10) 970 i 10A6,720 i 70)
PCP samples Control (PCP #2) 2.54/16.8 1,780 i 280A810 i 130) 360 i 50A2,490
- 350)
Deinruzed wa:er (PCP #1) 2.69/17.4 5,770 i 270/(2,620 i 122) 1,140 1 50/(7,9(X) i 350) J i
l Simulated Barnwell(PCP #3) 2. 2.250 1 750Al.020
- 340) 385 1 275A 2,670
- 1,9(X))
1 l
, a. The total cure time varied but was approximately 900 days from w hen samples were taken. The water-to<ement ratio is approxi-i mately 0.33 based on the interstitial water content of the samples, and the cross-sectional area for all is nommally 16 cm2 ,
- b. The PCP compression tests identified in the table were performed on conical samples The compression surface area was based on the smaller of the two ends as discussed in 1(cference 48. Nominally, the smaller surface area w as 17 cm2 These samples were leached for 90 days.
- c. Additional measurements were performed to compare compression tests for deioniecd and simulated Barnweit groundwater sam-pies. Ihis compression test study w as performed after the samples had been leached in the listed teachants for a period of 7 days. The data mdicate no significant differences between the effect of the detonized water and simulated Barnwell water on the compiessive strength. Unleached " control" samples were compression tested for quality control purposes and for comparison with the leached samples.
l l d. Compression testing performed after 7 days immersion and 7 days drying All other samples were immersed for 90 days prior to i compression testing.
Experimental Results plant tests and were prepared by the Peach observed in the bottoms of the teaching contain-Bottom staff. They were cast into paper cups and ers. Howes er, all samples maintained their physi-were therefore not true cylinders. After a review cal integrity and remained without cracks during of the compression test procedure," it was deter- the immersion experiment. Figure 5 shows a mined that the yield strength should be calculated Peach Bottom-3 sample after immersion in deion-using the smaller surface area of the two ends, ized water and compression testing, and Figure 6 shows a leached PCP sample after the compres.
sion test. The figures show the difference in the Table 5 lists the compression test results for the configuration of the INEL samples as compared unleached samples. These samples all easily meet '
to the PCP samples prepared by the plant The the regulatory requirement with the exception of crackmg m the waste forms was not present prior one PCP sample, However, their compressive to the beginning of the compression test.
strengths are well below the nominal compressive strength values of 5,000 to 61XX) psi for cement waste forms that don't contain decontamination An assessment of the Peach Bottom-3 post-im-ion-exchange resins. The PCP control sample has metsion compression testing results shown in the lowest compressive strength at 360 psi. The Table 5 indicates that the compressive strengths water-to-cement (w/c) ratio noted in Footnote a of ranged imm 956 to 1,370 psi for all samples Table 5 was calculated as the ratio of the weight except the PCP sample leached in simulated of free interstitial water to the weight of cement Barnwell groundwater. These compressive and other constituents used during the solidifica- strengths are lower than the compressive tion of the full-scale waste fonn from which the strengths of laboratory specimens of solidified waste-form specimen was collected. The w/c decontamination ion-exchange resin." Compres-ratio was calculated using the method developed sion test data from that laboratory study indicated by Neilson,35 which divides the water content of nominal compressive strengths for Citrox waste the resins between the water content of the "as-re- fonns of approximately 3,fXX) psi and of 1,800 psi ceived" and dewatered ion-exchange resins to for LOMI waste fonus. The lower value for the determine the amount of available interstitial LOMI waste form was not explained in Refer-water. It should be noted that the w/c ratio has ence 46. The reduced compressive strength of been identified as the critical parameter affecting the actual waste form samples may be due to the the strength and chemical resistance of a hard- additional constituents found in the waste fonns ened cement mixe and in determining the penne- as compared to the laboratory formulations The ability of a waste form. Studies (Reference 45) low compressive strength of the sample immer-indicate that permeability of the waste form sion tested in simulated Barnwell groundwater increases significantly at w/c ratios greater than may be due to poor sample preparation as the PCP ,
0.5. In this study, the w/e ratio is about 0.3: conse- control sample also had a low compressive quently, the increased permeability due to high strength, w/c ratios would not be expected to influence the results of this study as permeability is similar in The compressive strength data from the deion-the range of w/c ratios f rom 0.3 to 0.5 (Refer- zed water and simulated Barnwell groundwater l ence 5), tests also show no apparent difference in the i effects of the leachants in which the specimens The teachants used for the immersion tests were immersion-tested. Consequently, leachants were deionized water, simulated seawater, and have no apparent effect on compressive strength, simulated groundwater. As indicated in Table 5, Further, there were no apparent differences in the all immersion tests were performed for 90 days compressive strengths of the Peach Bottom-3 with the exception of those identified by Footnote specimens that were immersion-tested for either 7
- d. For the samples that were immersion-tested for or 90 days. In all cases, the waste fonns met the 90 days, after 30 days of immersion, small requirement in the " Technical Position on Waste amounts of resin and cement debris (<lg) were Form," Revision 1, for a 500-psi load, and there NUREG/CR-6164 18
i,- --__ __._ - -__ _ _
i I
(
l Experimental Results l
1
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Figure 5. Peach Bottom waste form specimen after immersion and compression testing.
g s ~ . , - + -
, ?
f 'c:'Q%
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,On.w .-#
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. w.,
En* * - > A YE+W MJs; j Figure 6. Process control program specimen after immersion and compression testing.
i i
! 19 NUREG/CR-6164 i
l Experimental Results l
l were no significant differences between the mechanism and will have slopes that are propor-samples immersed in deionized water and those tional to the corresponding effective diffusivities.
immersed in seawater.
Leachate pH and Conductivity Leach Test Results To assess the effects of pil and conductivity on the leachability of the waste-form specimens, pH Appendix A of the " Technical Position on and conductivity measurements were made on the Waste Form," Revision 1, has made two changes Peach Bottom-3 leach solutions at the end of each to the requirements of the " Technical Position on teaching period. The pH and conductivities for Waste Form" in the area of leach testing. First, the each leaching interval are plotted in Figures 7 leach test period has been reduced from 90 days and 8, respectively, and the numerical results are l to 5 days. Second, the bulk of the teach testing listed in Appendix D. During the first 5 days of may be conducted with only one of two leachants, teaching, leachates were changed out after either deionized water or seawater, whichever is elapsed times of 30 seconds,2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br />,7 hours,24 most aggressive (i.e., whichever has the higher hours,48 hours5.555556e-4 days <br />0.0133 hours <br />7.936508e-5 weeks <br />1.8264e-5 months <br />,72 hours,96 hours0.00111 days <br />0.0267 hours <br />1.587302e-4 weeks <br />3.6528e-5 months <br />, and 120 '
initial release rate). The objective of the 90-day hours. The final pH of the leachates for all three test was to detennine whether the leaching pro- waste-form sampbs reached maxima that ranged l cess was time dependant as has been assumed in between 10.5 and i 1.9 for all leachates except the l
the ANSI /ANS 16.1 leach test procedure. The 30-second prerinse. These data suggest that the changes were reflected in Revision i because it pil is affected within a few hours and probably was assumed that if mechanisms existed other within a few minutes by the chemistry of the than diffusion-controlled leaching (e.g., erosion, waste form.
corrosion, or dissolution), they would be identi-l fied by visual inspection during the immersion Vejmelka19 indicates that the cement chemistry l test and that the primary diffusion-controlled w 11 control the leachate pH unless magnesium, a
! release occurs during the initial 5 days? The pri- constituent of seawater, is present in the leachate mary objective of the leach test is to ensure that in significant concentrations. He indicates that the ,
the leachability index is greater than 6.0, which is solubility of the magnesium hydroxide formed in !
- required to meet the regulatory requirement. solution will set the pH for seawater. The effects of pH on releases of radionuclides and stable met-During the Peach Bottom-3 leach test, lea _ als are not clear because the pH (with the excep-chates were analyzed for the radionuclides, che_ tion of seawater) is controlled by the pH of the lating agents, and stable metals found in the waste form. It has been suggested47 that the ion decontamination resin waste forms. In addition, strength of seawater may be a more important measurements were made on the leachates for pH parameter and have a greater effect on radionu-and conductivity, and to deteimine the leachabil. clide solubilities in the leachate than the pH.
ity of the species released from the decontamina-tion ion-exchange resin waste form. The Conductivity is a measure of the quantity of following sections present results of the pH and ions that are present in a solution and that are conductivity measurements: the concentration capable of transferring an electrical charge. As measurements performed for radionuclides, noted in Reference 47, the conductivity, which is stable metals, and picolinic acid in the waste a measure of ion strength, can affect leachability.
forms; and the leach test results. Leaching data Leachate conductivities shown in Figure 8 are shown graphically as plots of cumulative frac- (expressed as mho/cm at 25 C) were measured tional release versus the square root of elapsed at the same time pH measurements were made at leaching time. This presentation was chosen to the end of each leach period for sample #8. How-facilitate evaluation of the data since the plots ever,in the cases of samples #4 and #12, the con-will be linear if diffusion is the controlling release ductivity measurements were made at a later date NUREG/CR-6164 20
Experimental Results 12
)
11.5 -
" t~~==== = -g x I,/./'
10.5 -
10 O. .
I 9,54 !
I
~
Peach Ilottom #4 m Peach llottom #8
- 8,5 o. Peach Ilottom #12 '
8 O 1 2 3 4 5 6 Time (days)
Figure 7. Leachate pH for all specimens.
1200 1000 -
^
j 800 I
b E6 N --
h 400 %g
-/
200 Peach Ilottom #4 m Peach llottom #8
- Peach Ilottom #12 A on , , , ,
0 1 2 3 4 5 6 Time (days)
Figure 8. Leachate conductivity for all specimens.
Experimental Results because of an instrument failure. Comparison of results for fission products 137Cs, *Fe, and 1291 the results between samples indicates that the have been added for comparison purposes and delay did not effect the conductivities due to the because of the importance of possible releases of similarity between the results for all samples. 1291. Only a brief discussion of the transuranic !
radionuclides is presented as they were measur- !
i For all waste-form samples, the conductivities able in the resin and waste fonn samples, but they were not detected in the leachates. Consequently.
ranged from 255 to 350 pmho/cm after the initial 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br /> of leaching. They then rose to maxima only detection limit values were available for cal-ranging between 560 and 605 pmho/cm between culational purposes.
the first and second day; then they decreased to minima between 341 and 355 pmho/cm for sam- The concentrations of radionuclides, chelating ples #4 and #12. In contrast, the conductivity for agents, and stable metals in the resin wastes and sample #8 went to a maximum of 1,050 pmho/ waste fonns are presented in Table 6 as pCi/g for em at 5 days. This behavior is inconsistent with radionuclides or pg/g of stable metals or chelates the conductivity of the other samples and sug- in the water-saturated resin. Analyses of both gests an instrument or recording error, although resin and solidified waste-fonn samples were per-no discrepancies could be identified. No effect of fonned. The summed radionuclide content is 7.8 this change in conductivity on the pH or leaching pCi/g of waste form based on a combination of results has been identified, the resin and cement results. Resin results for 54Mn,125 Sb,137Cs, 242C m ,14C,and 99Tc were Concentrations of Radionuclides, Stable multiplied by the resin-to-total-material ratio Mete!s, and Chelating Agents in Resin (0.5) for inclusion in the total. The primary Wastes and the Cemented Waste-Form decontamination radionuclides present in the res-ins based on their measured concentration are As noted in Appendix A of the " Technical 54Mn, 65Zn, 60Co, 55 Fe, 63Ni,and 14C. The Position on Waste Fonn," Revision 1, although summed activity of these radionuclides is 7,7 some reactor waste streams are relatively well pCi/g waste fonn or about 98% of the total activ-characterized and free of secondary ingredients, ity. Carbon-14 makes up about 58% of the total some waste streams such as ion-exchange resins activity. The dominant decontamination radionu-may contain chemicals that can retard or acceler- clides,6nCo and 55Fe, make up about 319 and ate the hydration of cement or otherwise 1.9% of the total activity in the resin waste, adversely affect cement waste-fomi perfonnance. respectively, in contrast, the fission products 90S r.
Some chemicals commonly found in nuclear "9Tc,129 1, and 137 Cs collectively constitute about power plants that may affect solidification are 0.3% of the total activity. The concentrations of listed in the proceedings of the Cement Work- the transuranic isotopes are also low and sum to a shop.6 One primary component identified in this total of 1.6 x 10-3 pCi/g (0.02% of the total evaluation was the chelating agent, piccolinic activity). Greater than 87% of the transuranic acid. activity was 241Pu.
In this study. waste stream samples were A review of Table 6 indicates that there are sig-obtained r aetennine the inventories of radionu- nificant differences between the measured resin clides, nable metals, and chelating agents that and waste form concentrations for some radionu-woufd se leached from the waste fonus being clides. In order to compare the resin and waste-leach sted. Table 6 lists the concentrations of form data, the radionuclide concentrations in the radior lides, stable metals, and chelating agents resin are multiplied by the ratio of the weight of preser i in the Peach Bottom-3 wastes solidified resin in the sample to the weight of all compo-as part of this study. In Table 6, the primary nents (0.52) (includes resin, cement, trisodium decontamination-produced radionuclides to be phosphate, and pozzolona) for comparison pur-discussed are 14C, 55 pe, 60Co and 63Ni, The poses. This ratio is approximately 0.5, in contrast NUREG/CR-6164 22
Experimental Results Table 6. Summary of Peach Bottom resin and cement waste form characterizations (decay date 10/25/89).
Peach Hottom cemented waste forms l l
Peach Bottom resin <
l Radionuclide (pCi/g or pg/g) Sample #1 Sample #2 54Mn 4.3E 1
- 2.7E-2 55Fe 1.3E 0 i 5.5E-2 1.5E-1 i 1.6E-2 1.5E-1 i 1.6E 2
- Co 4.6E 0 i 1.2E-2 2.4E0 i 1.5E-2 2.4E0 i 1.5E 2 63Ni 7.5E-2
- 6.8E-3 1.6E-2 i 1.4E-3 3.7E-2 i 3.lE-3
5Zn 6.0E-1 i 1,lE 2 3.9E-1 i 7.8E-2 5.6E1 1 1.6E-1 125Sb 1.7E-2 i 9.8E-4 137Cs 3.6E-3 i 5.lE-4
""Sr 2.2E-5 i 2.3E-6 3.0E-3 i 5.5E-6 5.3E-5 7.6E-6 238Pu 6.6E.5 i 1.6E-6 7.2 E-5 1 4. l E-6 9.5E-5 i 5.2E-6 23*Pu 2.2E-5 i 7.5E-7 2.6E-5 i 1.6E-6 2.4E-5 i 1.5E-6 241Pu 1.8E-2 i 4.3E-4 2.7E-4 + 1.5E-5 2.5E-3 i 1.4E-4 241Am 5.2E 5
- 1.4E-6 1.0E-4 i 6.0E-6 1.3E-4 i 7.0E-6 242Cm 9.2E 6 i 9.2E-7 l
244Cm 1.3E-4 i 1.6E-4 1.5E-4 i 8.0E-6 1.3E-4 i 6.9E-6 !
'4C M.7E+0 i 8.7E 2 3.lE 4 i 2.7E-5 2.5E-4 i 2.l E-5 ,
I
'Mc 3.7E-2 i 8.6E 4 2.7E-4 .i 1.5E 5 1.25E-3 i 6.9E-5 12"I <SE-6 < 5.8E-6 2.4 E-5 -1 3.5E-6 Chromiumd 650 i 20 103 i 6 103 1 6 l Iron
- 3.(KN) i 160 1.73E+4 i 500 1.78E+4 i 600 Zinc' 158 i 12 66 i 3 M3 + 3 Nickel 8 730 i 30 66 i 12 54 1 8 Cobalt 15 12 Boronb , 16 + 2 2113 Phosphate d Sulfateb Picolinic acidc < SE-6 M 1.68 wt% i 0.21 2.02 wt% i 0.08
- a. Analyses performed usmg inductively coupled plasma spectrowopy clernental analysis methaxis.
- b. Analyses performed using ion chromatography.
- c. Analysis performed usmir picohnic acid titration. Due to uncedainities in the solidified waste analysis. the loadmg in the liner will be used.
Experimental Results to the volume ratio (0.68). If this is done, the fol- data again suggest that the waste forms are not lowing radionuclides still have significant differ- homogeneous.
1 ences between the measured resin and waste form concentrations (the factor of the resin divided by The concentration of picolinic acid was mea-the waste form concentration is shown in paren- sured for several waste-form samples. These thesis): 55Fe (4.5), 24 tPu (13),14C (1.6 x 104), results ranged from 1.68 to 2.02 wt%, which is and 99Tc (25). Nominally, these results indicate less than the 5.5 wt% added to the liner. However, significant differences in the radionuclide con. because of concerns about degradation of the centrations in the resi, and the waste-form sam- picolinic acid, the acid teaching technique used ples. However, differences in the concentrations for the waste form measurements may not have in the two waste-form samples that were analyzed provided a quantitative yield. Consequently, the are also indicated in Table 6. Ratios of the radio. liner inventory value will be used for the teaching calculations, nuclide concentrations for the two cemented waste forms analyzed were calculated to assess Chelating Agent, Radionuclide, and significant differences in the waste-form con-centrations. Significant differences are indicated Stable Metal Releases for 63N (2.3),241Pu (9.2h 24iAm (l.3), 244Cm Picaul 46, S 16 and others19 39 48 have (1.2),14C (1.2), and94c (4.6). These data indi-addressed the release of chelating agents, radio-cate that the radionuclide concentrations in the nue s, and/or staW nwtals 1n tM labomtom resin and the waste form are not uniform; there- ,
. These include LOMI decontammation processes fore,the m.ventories are not known withm.a fector . .
with picoh. .me acid as the chelating agent and of between about two and 10 for the identified um waste fonns with other chelating agents.
rad,ionuclides. However, uniformity does not Ilowever, these stud,es used simulated wastes i
ex;ilain the differences observed for 14C and99Tc.
that did not contam all of the constituents found m In both cases, the differences between the res.m .
and waste-form concentrations are large. Discus-
' *"*.al nuclear p wu plant waste stmams;
. - . also, as discussed in Reference 34, other waste sions with laboratory personnel indicates that the
- stream constituents found at commercial nuclear waste-from analyses were difficult and that inter- g ggg ;
ferences or losses due to the presence of the ggg 7 waste-form constituents may have affected the results. Consequently, for calculational purposes, The physical factors that influence mass trans-the higher resin concentrations have been used, fer of chelating agents, radionuclides, and stable These data suggest that differences in leaching metals into the leachant can be divided into three i results that are less than a factor of two are insig- rnechanisms: (a) convection, (b) diffusion
. nificant and that differences of between 5 and 10 through pores within the waste form, and (c) dif.-
are required to make significant conclusions. fusion at the interface of the waste fomi and the surrounding coolant.15 Convection refers to bulk movement through the waste form and is Among the stable metals whose concentrations expected to be insignificant for intact waste were measured in the resin wastes, the iron con- forms. In this study, where a number of the waste centration was highest at 3,000 pg/ gram resin. forms decomposed during teaching, it may This was followed by nickel and chromium, in expected to be significant, but as will be dis.
addition, analyses were performed for sulfate and cussed, there does not appear to be a significant phosphate. Neither type of ion was detectable in difference in the releases from degraded and the waste form or in the resin samples. Differ- intact waste forms. Mechanism 2, pore diffusion, ences between the resin and waste-form con- is induced by concentration gradients within a centrations have also been identified. The ratio of waste matrix and results in diffusion of radionu-the resin to waste-form sample concentrations clides and other constituents to the surface of the differ for chromium (3.2) and nickel (5.5). These waste form. This mechanism has been described NUREG/CR-6164 24
-. -a '- '
Experimental Results as a porous solid with water-filled pores.19A5 The high-rate data from early in the leaching process final mechanism is the diffusion at the interface and low-rate data from later in the process. Aver-between the surface of the waste form and the sur- ages are not typically calcul.a i for phenomena rounding leachant. 'I' sa be considered to be of this type; however, these averages and their the fonnation of a diffusion gradient between the associated uncertainties have been calculated surface of the waste form and the surrounding because they are the comm v method used for leachant. If this diffusion gradient is formed and comparisons with other leac .est studies. Conse-there is little movement of leachant, an equilib- quently, uncenainties assochied with the average rium would be esublished that would be expected rates are expected to be large (typically from to reduce releases from the waste form. Each of 50-100% at one standard deviation). Uncertain-these mechanisms may contribute to releases ties listed for the average absolute release rates, from the intact and degraded waste forms and the average fractional release rates, and the aver-would be expected to be modified by the effects age effective diffusivities are the intemal uncer-of other constituents of the waste form, with che- tainties associated with differences in the rate or
!ating agents possibly having the greatest effect diffusivity results and do not contain uncertain-due to their high concentration in the waste fonn ties associated with counting statistics, waste j (up to 6 wt%). form inventories, or other uncertainties I associated with the leachmg process. These An assessment of the leachability characteris- uncertainties have been excluded because they tics of decontamination ion-exchange resin waste are either small relative to the quoted uncertainty forms is perfonned through comparisons of frac- or are not quantifiable based on the tests per-tional release rates, cumulative fractional formed. Exceptions (e.g. 90Sr) are discussed in releases, effective diffusivities, and leachability the following sections. An uncertainty of one
~
indexes for the species of interest to assess the si ndard deviation is quoted in the tables.
effects of the different chelating agents on releases from the waste forms. Appendix D con. Table 10 contains error-weighted averages tains detailed tables showing the leach test with a one-standard-deviation uncertainty for the results. Raw results with uncertainties are shown results from Tables 7 through 9 for samples #4 in Appendix Table D-5. Appendix Table D-6 has and #12 and for samples #4, #8, and #12. The been included for comparison purposes and con- uncertainties listed in Table 10 are based on the tains the same information for the FitzPatrick uncertainties listed in Tables 7 through 9.
sample (Reference 17), which degraded during teaching. Various forms of data presentation have Chelating Agent oeen used, including cumulative fractional release /cm2 surface area / year, Ci/ year, Ci/ In this study, the release of the chelating agent m 3/ year, cumulative fraction released / year, and picolinic acid was evaluated first because it pro-cum lative fraction released /m /3 year. These data vides a basis for interpreting the radionuclide and are specific to the Peach Bottom-3 waste forms stable-metal results. If the radionuclide or stable-and should not be extrapolated to other waste- metal release is enhanced by chelating effects, the fonn dimensions or compared with releases from release rates of the chelant and the species of other waste forms as the data are decay depen- interest may be comparable and should provide dent- an indication of which radionuclides or stable metals have enhanced release rates. Figures 9 Tables 7 to 9 contain summaries of the CFRs, and 10 show the fractional release rates and the average absolute release rates, the average cumulative fractional releases for picolinic acid.
fractional release rates, the average effective dif- The chelating agent was measured in all the lea-fusivities, and the leachability indexes for the chate samples for waste-form samples #4 and i
Peach Bottom-3 samples. These averages are for #12. The remaining Peach Bottom-3 sample, #8, I nonlinear rate phenomena and, therefore, include was analyzed by a different laboratory, which was l
l 25 NUREG/CR-6164 l
Experimental Results -
Table 7. Leach test results for Peach Bottom solidified resin waste form #4, leached in deionized water.
Release rate Ascrage effective Absolute Fractional diffusivity Leachability i Nuclide CFR (pCi . cm-2 3.l ya (cm-2 . s.t ja (cm2 . 31)a ndex l
Id3C 1.2E-4 6.9 i 13E-9 6.2 i 12E-12 4.3 + 5.0E-14 14.1 I MFe 8.6E-4 1.2 + 2.4E-9 7.6 i 16E-l1 3.8 i 8.2E-12 12.9 i 60Co 1.7E-3 2.4
- 3.l E-8 6.4 i 8.2E-Il 4.4 i 1,9F-12 11.4 63Ni 5.6E-3 1.4 i 1.8E-9 2.1 i 2.7E-10 5.2 S.3E-I l 10.4 8.2 10E-11 10.6 !
"USrb 2.4E-3 4.8 6.4E-12 5.0 6.7 E- 10 Mc 2.1E-3 2.0
- 1.7E-10 4.3 3.6E- 11 9.2
- I7E-12 11.5 12'I 9.6E-2 3.6 i 5.6E-Il 5.9 i 9.3E-9 3.6 i 3.lE-8 7.9 Chelating agent or metal (pg cm-2,31)
Chromium 1.4E-2 1.0 i 1. l E-5 4.1 + 4.2E-10 3.0 t 0.7E-10 9.5 Ironb 1.8E-5 2.2 i 0.5E-6 5.1 i 1.lE-13 2.3 0.7E-15 14.7 l I
l Cobalt 4.3 E-2 5.4 t 6.5E-6 1.7 2.0E-9 3.6 i 3.3E-9 8.6 l l
Nickel 2.3E-2 1.1 i 1.4E-5 7.7 i 9.2E-10 8.5 i. 2.7E-10 9.1 ,
Zinch 4.4E-3 1.1 1.3 E-5 6.1 6.9E- 10 1.4 + 1.0E-10 10.0 )
Boronb 3.0E 2 9.1
- llE-6 2.0 i 2.3E-9 3.1 i 0.9E-9 8.5 Picolinic Acid 2.0E-2 8.2 8.8E-3 6.0 6.5 E- 10 5.4 -i 1.4E-10 9.3
- a. Intemal uncertainty asmciated with cakulated results. Does not include counnng statistics or other untertainties asmciated with the leaching process.
- b. Average values were calculated excludmg teros.
unable to detect picolinic acid in the teachate sam- sample decomposed early in the leaching process ples. The fractional release rates for the Peach Bot. and provides a basis for comparison with the intact tom-3 samples indicate similar behavior for both Peach Bottom-3 samples.
samples with the highest rate for the 2-hour lea-A comparison of the fractional release rates for chate. In addition to the fractional release rates for the Peach Bottom and FitzPatrick samples indi-the Peach Bottom-3 sampi ,the fractional release cates a varying release rate for picolinic acid from rates for the FitzPatrick mixed-bed resin waste- the FitzPatrick sample probably due to convec-form specimen leached in deionized water during tion release during the breakup of the waste form a previous part of this study l7 have been included (significant cracking within 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br />). However, a in Figure 9. As discussed in Reference 17, this comparison of the average fractional release rates NUREG/CR-6164 26
Experimental Results I Table 8. Leach test results for Peach Bottom solidified resin waste form #12, leached in deionized water, i I
Release rate l Average effective l Absolute Fractional diffusivity Leachability Nuclide CFR (pCi . cm.2 31)a (cm.2 . s-1)a (cm 2 s-l)a index lC 5.5E-5 2.7 i 4.3E-9 2.5 t 3.9E-12 5.5 i 4.8E-15 14.4 55Fe 2.0E-3 6.6 6.4 E-10 4.4 4.2E-! ! 1.1 i 1.7E-Il 11.5 60Co 1.7E-3 2.2 i 2.8E-8 6.1 i 7.7E-11 4.4 t 1.5E-12 11.4 63Ni 6.2E-3 1.5 i 2.0E-9 2.4 i 3.2E-10 5.8 2.9E-11 10.3 l
90 Srb 1.4E-3 1.5 i 1.8E-12 1.6 1.9E-10 1.4 i 0.9E-Il 11.2 )
99Tc 3.lE-3 2.0 1.3E-10 4.4 i 2.8E-Il 1.7 1.7E-I l 11.5 1291 5.7E-2 1.6 2.0E-11 2.6 i 3.4E-9 1.9 i 2.8E-8 8.3 Chelating agent or metal (pg . em.2 . s.i)
Chromium 1.9E-2 1.5 i 1.8E-5 6.1 7.3E-10 5.4 1.3E-10 9.3 Ironb 7.4E-5 1.4 i 1.5E-5 3.2 i 3.5E-12 1.1 i 0.6E-14 14.0 Cobalt 4.1E-2 3.7 i 3.9E-6 1.2 i 1.2E.9 3.4 i 2.3E-9 8.7 Nickel 3.5E-2 1.8 i 2.2E-5 1.2
- 1.5E-9 2.0 i 0.6E-9 8.7 Zinc 1.2E-2 8.6 11E-6 4.7 i 6.1E-10 2.6 i 1.5E-10 9.6 Boronb 2.4E-2 6.3 i 4.2E-6 1.4 1 0.9E-9 4.0 i 1.9E-9 8.4 Picolinic 2.0E-2 7.6 7.8E-3 5.6 5.8E-10 5.4 i 1.3E-10 9.3 acid
- a. Internal uncertainty associated with calculated results. Does not include counting statistics or other uncertainties aswciated with the teaching process.
- b. Average values were calculated excluding zeros.
for the Peach Bottom-3 samples with the fractional release rate (2.4 x 10-W cm-2 3 1)
FitzPatrick sample (Tables 7,8, and 9 with the after the initial high rates due to convection is sta-average in Table 10) indicates that the average listically the same as that from the Peach Bottom-3 fractional release rate of picolinic acid for the sample (5.8 4.3 x 10-m em-2 . s-1). These FitzPatrick sample (3 x 10-9 cm-2 s-1)is about data suggest that after an initial high release rate a factor of five higher than that from Peach from the decomposed waste form due to convec-Bottom-3 (5.8 x 10-10 cm-2. s-1). Examinatic- tion, diffusion-driven release is similar for both of the FitzPatrick data indicates that the average intact and decomposed waste forms.
Experimental Results Table 9. Leach test results for Peach Bottom solidified resin waste form #8, leached in deionized water.
l Release rate Average effective Absolute Fractional diffusivity Leachability Nuclide CFR (pCi . cm.2 . 3.na (cm.2 . s.1)a (cm 2 s-l)" index l 1
34C 6.9E-4 2.5 1 3.0E-8 2.2 t 2.8E-Il 9.9 7.2E-13 12.1
, 55Fe 1.9E-2 1.8 i 3.2E-8 1.2 2.lE-9 1.4
- 2.l E-9 9.7 MCo 3.0E-3 3.3 i 4.1E-8 9.0 11E-11 1.8 i 1.6E-11 10.9 j 63 Nib 5.0E-5 2.6 i 3.3E-11 4.0 5.1E-12 1.2 i 1.1E-14 14.3 90 Srb 1.7E-2 1.5 i 2.4E-11 1.6 i 2.5E-9 1.7 1 2.4E-9 9.3 99Tc 2.6E-2 1.9 3.3E-9 4.1 7.0E-10 2.4 i 5.8E-9 10.1 125Sbb 3.7E-3 6.6 i 1.8E-Il 5.5 i 1.5E-Il 4.5 2.7E-I l 10.4 l
l 1291b 2.7E-2 3.4 i 1.6E-12 5.6 2.6E-10 2.4 i 2.lE-9 8.9 l
l j 137Cs 1.8E-2 2.3 i 1.8E-10 4.1 3.3E-10 8.9 i 9.9E-10 9.3 Chelating agent or metal (pg . cm-2 . 3-1)
Iron 4.4 E-4 1.5 i 3.0E-4 3.5 i 7.0E-11 1.1 i 2.1E-12 13.0
- a. Internal uncertainty associated with calculated results. Does not include counting statistics or other uncertain-ties associated with the leaching process.
- b. Average values were calculated excluding zeros.
A comparison of the average absolute release was shown that waste-form chemistry and lea-rates for FitzPatrick (8 x 10-3 pCi/cm . s) and2 chant chemistry (ion strength,leachant chemical Peach Bottom (7.9 x 10-3 pCi/cm2 s) indicates composition, and leachant replacement fre- >
that the release rates are statistically the same for quency) may control teachability. These data tend both waste forms. The absolute and fractional to support that conclusion.
release rate data indicate that the structural stabil-Figure 10 shows the plot of the CFRs of pico-ity of the waste form does not affect the release litac acid from the Peach Bottom-3 and FitzPa-
- rates of picolinic acid from the waste form other trick waste forms. These data show that the CFRs j than an early release due to convection and the for the Peach Bottom-3 waste forms are similar initial increase in the surface area of the decom- and indicate that the release is diffusion-based on posed waste form. The fractional and absolute the slope of the CFR curve.37 38The average CFR release rate data suggests that chemical mecha- of picolinic acid from the Peach Bottom-3 waste nisms either in the waste fonn or in the resin itself fonns (Table 10) is 2.0 x 10 2, whereas for Fitz-control the release rate from the waste form. In a Patrick, the CFR is 0.5 (90-day leach test). A study by D'Angelis 23 and in other studies,49 50 it comparison of the Peach Bottom-3 and NUREG/CR-6164 28
e.
Experimental Results Table 10. Weighted average leach test results for Peach Bottom-3 cement-solidified waste forms.
Release rate Average effective Absolute Fractional diffusivity Leachability Nuclide CFRa (pCi cm'2. s-1)b (cry-2.s-1)b (cm2. 31)b index" 84C 8.8E-5 3.7 i 4.6E-9 3.4 i 4. l E- 12 8.8 t 6.2E-15 14.2 Includes #8C 2.9E-4 5.7 5. l E-9 5.3 i 4.6E-12 1.5 0.7E-14 13.5 55Fe 1.4E-3 7.7 7.1E-10 5.1 i 4.7E-11 6.1 7.8 E- 12 12.2
-c 7.3E-3 1.0 i 0.9E-9 6.8 + 5.7E-11 9.8 i 9.6E-12 11.4 coco 1.7E-3 2.3 2.lE-8 6.2 5.6E-I l 4.4 i 1.2E-12 11.4
-c 2.lE-3 2.6 i 1.9E-8 7.0 i 5.0E-Il 5.2 i 1.6E-12 11.2 63Ni 5.9E-3 1.5 i 1.3E-9 2.2 i 2.lE-10 5.5 i 2.2E-11 10.4
-c 4.0E-3 7.4 i 5.5E-l1 1.5 i 1.0E-11 5.I 1.9E-14 11.7 90Srd 1.9E-3 2.2 i 2.0E-12 2.4 i 2.1E-10 2.0 1.1E-11 10.9
-c 6.9E-3 2.9
- 2.2E-12 3.I i 2.4E-10 2.8 i 1.4E-11 10.4
- Tc 2.6E-3 2.0 1.0E-10 4.4 i 2.2E-11 1.3 1.2E-11 11.5
-c 1.0E-2 2.4 i 1.2E-10 5.2
- 2.7E-11 1.6 i 1.5E-11 11.0 1291 7.7E-2 ~2.1 i 2.lE-11 3.5 i 3.5E-9 2.7 i 2. l E-8 8.1
-c 6.0E-2 5.1 2.1 E-12 8.4 i 4.1E-10 5.5 i 3.2E-9 8.4 j
Chelating agent or metal (pg . cm.2 , 31) j l
Chromium 1.6E-2 1.2 i 1.0E-5 4.8 3.8 E- 10 3.8 0.6E-10 9.4 I Irond 4.6E-5 2.6 i 0.7E-6 5.9 i 1.5E-13 3.2 i 0.9E-15 14.4
--c 1.8E-4 2.8 i 0.8E-6 6.4 1.8E- 13 3.5 1 1. l E-15 13.9 Cobalt 4.2E-2 4.3 i 3.4E-6 1.3 i 1.0E-9 3.5 i 1.9E-9 l
8.6 l Nickel 2.9E-2 1.4 i 1.2C 5 9.3 8.1 E-10 1.2 i 0.3E-9 8.9 Zined 8.2E-3 9.7 i 8.5E-6 a.
- 4.6E-10 1.9 i 0.8E-10 9.8 Borond 2.7E-2 7.1 4.3 E-6 1.6 i 0.9E-9 3.3 0.9E-9 8.4 Picolinic 2.0E-2 7.9 i 5.8E-3 5.8 i 4.3E-10 5.4 i 0.9E-10 9.3 acid
- n. Simple average based on data in Tables 7 through 9.
I
- b. Error weighted average based on data in Tables 7 through 9.
- c. Includes the results from sample #H.
- d. Average values were calculated excluding zeros.
Experimental Results 1E-07 Peach Ilottom #4 "
Peach Ilottom #12 A FitzPatrick DI o T
I T 1E-08 e.
I O
Ei
/
i ,% /
o b IE-09 -
x [jW 5 '\N ' l "N,N . ~ ~ .
e 1 E- 10 0 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 9. Fractional release rates of picolinic acid.
1 E + 00 Pc:ich Ilottom #4 "
Peach llottom #12
- l'iuPatrick Di n 8 a S
g 1E-01 -
g y
s/,
D u'
v
.h~
,s W*
s 1E-02 -
/y' IE-03 O 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 10. Cumulative fraction release of picolinic acid.
Experimental Results FitzPatrick data indicates that the slope of the dif- and M Ni. They are transition metals and form fusional release curves are similar for both waste coordination complexes (i.e., complex hybrid forms. These data confinn the conclusion devel- bonds between metals and anions, cations, or oped from the fractional release rate data that the molecules) with chelating agents that may keep diffusional release (following the high-rate con- these metals in solution and therefore potentially vective release) is similar for both intact and increase their mobility from a waste form. Other decomposed waste forms. radionuclides found in the waste forms *Sr,14C, 99Tc,129 1, and 241 Pu, have varying chemical The average effective diffusivities and leach- characteristics that are discussed below.
ability indexes for picolinic acid are shown in Tables 7 to 10. The teachability indexes for pico-linie acid from the Peach flottom samples as The fractional release rates for 55 Fe, Co N ), and i shown in Appendix D range from 9.1 to 9.5. and M Ni are shown in Figures 11 through 13.
I are above the regulatory requirement of 6.0. The Examination of 55Fe data indicates that there are ;
average leachability index is 9.3. as shown in variations in the fractional release rates for sam-Table 10. pie #4 and that the fractional release rates from i l
sampic #8 are generally higher than those from Decontamination Radionuclide Releases the other two samples. The f ractional release rates from sample #4 at leach times of 2 and 3 days are The releases of radionuclides from the Peach lower than those for samples #8 and #12. Two Bottom-3 cement solidified waste forms is depen- days into the teach test, the release rate from sam-dent not only on the physical and chemical char- ple #4 drops to about 10 43 cm-2 s-l. However, acteristics of the waste fonn but on the chemistry examination of the average fractional release of the radionuclide. The primary radionuclides rates for samples #4 and #12, as shown in from the decontamination process are 55Fe, Co"), Tables 7 and 8, indicates that they are statistically 11! - 07 Peach llottom #4 m Peach llottom #8 +
III-08 - Peach Ilottom #12 ^
liitzPatrick Di o e
- \ ~. s l lII-09 r
a
'N u N's *x E
v III-10 -
,/^\_ \ N'N N g ,
6 11!- 11 - e * 'a a J
's l 3 N y e~. j g 111-12
\ l 113 - 13 -
\\ ,. j l
l
' J ' '
111 - 14 O 0.5 1 1.5 2 2.5 Square root of time (days) l Figure 11. Fractional release rates of55Fe.
Experimental Results 1E-08 Peach Ilottom #4 "
Peach Bottom #8
- Peach Bottom #12 A FitzPatrick DI o 01E-09 -
I
~ .
I sh k 1E-10 -
)
N' .
o
@ % n~=~ ~ . N . '_
1
% 1E-11 - * =4 1 E-12 0 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 12. Fractional release rates of")Co.
1E-07 Peach Bottom #4 =
Peach Bottom #8
- Peach Bottom #12 A 1E -08 -
FitzPatrick DI o 71E-09 -
g
'h
.' w~= a C 1E-10 -
S E .
6
% ' R $ M -I A
o IE-11 -
Z 1E-12 - *N 1 E- 13 -
N.N.
1 E-14 O 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 13. Fractional release rates of63Ni.
4
- j. Experimental Results i
l 4
! the same and have a weighted average value of concentration of the radionuclide in the waste j 5.1 x 1 0-13 cm-2 s-1 as shown in Table 10. form does not affect the absolute re'. ase rate l When the weighted average fractional release rate because the concentration of 55Fe in the for all samples is calculated (including the value FitzPatrick waste form is about a factor of four of 1.2 x 10-9 cm-2 3-1 for sample #8), it is less than that in the Peach Bottom-3 waste form. ;
, 6.8 x 10-Il em-2 3-1, as shown in Table 10. This These absolute release rates indicate that the I i weighted average fractional release rate for all release rate of55 Fe from LOMI waste fonns may j samples is statistically the same as that for sam- be independent of the inventory in the waste form plcs #4 and #8 because of the relatively small and that other factors, besides diffusion, may con-
)
uncertainties associated with the sample #4 and trol the release rate from the waste form.
- 8 results and because of the large uncertainty (2.1 x 10~9 cm-2 3-1) associated with the aver. Figure 12 shows the fractional release rates of ,
W Co from the Peach Bottom-3 samples. These l 3
age fractional release rate of 55Fe from sample 1 #8. This large uncertainty results in the weighted data are similar for all three Peach Bottom-3 j
, average being dominated by the smaller uncer. waste-form samples and suggest that the j 4 tainties associated with samples #4 and #12. Con. observed variations in the leach rates for 55Fe are I not problems associated with the teaching process !
sequently, when large uncertainties are present in the data, the weighted average will be dominated but are indicative of the behavior of 55Fe. A com-
- by the smaller uncertainty. Comparisons in which parison of the *Co fractional release rates for j only the larger uncertainty overlaps the less-cer. Peach Bottom-3 with the FitzPatrick data as
- tain value are not considered to be statistically shown in Figure 12 indicates that the *Co frac-significant in this assessment. No reason for the tional release rate for FitzPatrick is initially lower higher fractional release rates from sample #8 has (first leach period) and then goes above the Peach been identified. Bottom-3 rates for the next 4 days. The weipted
- average of the fractional release rates of *Co foi
~
. all Peach Bottom-3 samples as shown in Table 10 In comparison, the average f.ractional release b7 x 10-H cm-2 s d, which is again statistically rate of 55 Fe from the FitzPatrick sample is the same as that for the FitzPatrick sample 7 x 1043 cmy s .dConsequently, the weighted average fractional release rate Irom the Peach 0 x 10-H cm-2 s d). It should be noted that the M d ng of k feionM Mm e Bottom-3 samples is statistically the same as that for55Fe (Table 10) are the same as those for *Co l l of the FitzPatnck sample. The similarity of these and indicates similar release behavior for both
- data suggests that the fractional release rate of j 55 Fe is not affected by the structural stabih.ty of radionuclides.
- the waste form (remember that the FitzPatrick inspection of Figure 12 suggests that the aver-
, samples fell apart during leaching). A comparison age fractional release rate of *Co for FitzPatrick j of the Peach Bottom-3 data with the weighted should be higher than that for Peach Bottom-3.
average fractional release rate of piccolinic acid However, the high fractional release rates shown (5.8 x 1040 cm-2 . sd) ndicates that the chelat- n Figure 12 for FitzPatrick occur only during the ing agent is being released faster than 55Fe and f rst 5 days of leaching (excludimt the first leach
- that retention mechanisms may hold 55Fe in the period) and after this initial release, the rate drops waste form. to about 1.8 x 1041 cnr2 s d for the duration of the 90-day leach test. As noted above, the average The weighted average of the absolute release fractional release rate of *Co from the FitzPa-rates of 55Fe for the three Peach Bottom-3 waste trick sample over the 90 days is statistically the forms (l.0 x 10-9 pCi/cm 2 s), as shown in same as the weighted average fractional release Table 10, is statistically the same as that measured rate from the Peach Bottom-3 samples as shown for the FitzPatrick waste form (7 x 1040 pCi/ in Table 10. These data again indicate that after an cm2. s) if a similar uncertainty is applied to the initial convective release from the degraded FitzPatrick data. This suggests that the waste form, the fractional release rate from the 33 NUREG/CR-6164
Experimental Results intact waste form .is the same as that from the samples is about a factor of three less than that for degraded waste form. This again suggests that the FitzPatrick sample. This difference is not mechanisms other than structural stability and within the uncertainty listed in Table 10 for the diffusion may be controlling the release process. weighted average fractional release rate and indi-A comparison of the weighted fractional release cates that 63 Ni is being released at a faster frac-rates of 60Co as shown in Table 10 with those of tional release rate from the FitzPatrick waste form picolinic acid again indicates, similar to the 55Fe than from the Peach Bottom-3 waste forms. This data, that the weighted average fractional release is in contrast with the 55Fe and 60Co data, which rates of 60Co are less than those observed for are statistically the same as the FitzPatrick picolinic acid and, similarly, that60Co is being results. No reason for the enhanced fractional released at a lower rate. release rate of 63 Ni from the FitzPatrick sample has been identified, although it may be due to the The average absolute release rates for 60Co different release characteristics of the degraded from the Peach Bottom-3 samples, as shown in waste form.
Table 7 to 9, are statistically the same and have a The weighted average absolute release rate of weighted average value of (2.6 x 10* pCi/ 63 Ni for the Peach Bottom-3 samples (#4 and i em 2 s) as shown in Table 10. This weighted
- 12)is 1.5 x 10* pCi/cm' s, which is approxi- 1 average absolute release rate is statistically higher mately an order of magnitude less than that for the than those for 55Fe and 63Ni and is possibly due to FitzPatrick sample. This rate is statistically the the higher concentration of this radionuclide in same as the weighted average absolute release the Peach Bottom-3 samples. The similarity of rate of 55Fe. However, as indicated in Table 10, the weighted average fractional release rates for ahhough the absolute release rates are statistically the transition metal radionuclides and the differ-the same, the fractional release rate of 63Ni is a ence in the absolute release rates suggests that the factor of three higher, which indicates differences release rate of 60 Co is dependent on the con-centration in the waste form.
in the behavior of the two radionuclides.
A comparison of the absolute and fractional Figure 13 shows the fractic,nal release rates for release rate data for the three decontamination 63Ni and indicates a difference between the sam- radionuclides indicates that the structural stability ples analyzed at one laboratory (#4 and #12) and of the waste form does not appear to significantly a sample analyzed at another laboratory (#8). affect releases from the waste form. For Peach This difference is about two orders of magnitude, Bottom-3. the weighted average fractional release which is well above the statistical differences that rate is 6.8 x 10* cm'2 sd for 55Fe.7 x 10
- might be expected for this type of analysis. These em-2 sd for 60Co. and 2.2 x 1040 enr2 sd for data indicate that the sample #8 63Ni data, which 63 Ni (samples #4 and #12). These data indicate are much lower than that for the other two sam- that release rates are within a factor of four, but ples, are suspect. Discussions with the laboratory that 63Ni probably has a higher release rate than provide no indications as to why this discrepancy the other tiansition metal radionuclides. The frac-should exist. Consequently, only the results for tional release rate of picolinic acid is about samples #4 and #12 will be discussed for this 6 x 10-10 cm-2. sd and is statistically higher radionuclide. than that of 63Ni and the other decontamination radionuclides. The higher fractional release rates The weighted average fractional release rate of associated with 63 Ni may be due to the increased 63 Ni for samples #4 and #12 is about 2.2 x 1040 stability of nickel complexes, as the Irving-Wil-cm-2. s a. A comparison of the sample #4 and #12 liams correlationm2 indicates that the stability data with the average fractional release rate of of transition metal complexes fall in the order 63 Ni from the FitzPatrick sample (6 x 1040 Ni H>Co >Fe".
H These data suggest that the stabil-cm.2 . sa) indicates that the weighted average ity of the nickel complex with a chelating agent l fractional release rate from the Peach Bottom-3 may result in the higher average fractional i
j Experimental Results release rates of 63Ni relative to the other the release rates from a waste form are not depen-transition metals. dent on the structural stability of the waste form.
Figure 16 shows the CFRs for N3Co. The CFRs The CFR plots for the transition metals are for all Peach Bottom-3 samples are similar (i.e.,
shown in Figures 14 through 16. Inspection of from 1.7 x 10-3 to 3 x 10-3) and indicate a j the 55 Fe data in Figure 14 and Tables 7 to 9 indi- higher CFR for sample #8. The average CFR of 60
~
cates that the cumulative fractional release ranges Co for the Peach Bottom-3 samples is from 8.6 >: 10-4 for sample #4 to 1.9 x 10-2 for 2.1 x 10-3, which is less than the CFR of 60Co 1 sample #8. The CFR for sample #8 is about an from the FitzPatrick sampic (5.9 x 10-3 through order of magnitude higher than that for the other 5 days). These data indicate that the CFR from the two samples. This higher CFR is due to high degraded waste fonn is higher. Ilowever, as dis-release rates during the first three leach periods cussed previously, there was an initial high (see Figure 11). Following this initial release, the relea:,e probably due to convection during the j rates are similar to those observed for samples #4 breakup of the waste fonn that was followed by and #12. The aserage CFR for 55Fe from Peach lower release rates. Consequently, it woulo be Bottom-3 samples #4 and #12 is 1.4 x 10-3 and expected that the CFRs of both the Peach Bot-7.3 x 10-3 for all samples (includes #8). No tom-3 and FitzPatrick waste fonns would prob- ;
explanation for the initial high release rates ably be similar at 90 days. These data suggest that i
- associated with sample #8 have been identified. the 90-day teach test is probably more indicative l Figure 14 funher indicates that the CFRs for the of the behavior of the waste fonn than is the 5-day Peach Bottom-3 sa .iples bound the CFR for55Fe test particularly when degrading waste fonns are
! for FitzPatrick. These data further indicate that being tested. l
. 1E + 00 i Peach Bottom #4 m Peach Bottom #8 +
- Peach Bottom #12
- IE-01 -
FitzPatrick DI o o
N U.!
8 . . : : :
j IE-02 -
,/,
U
$ . rd a IE-03 -
n , , , ,
j , _ _ .
E
- s 0
1E-04 -
A lE-05 0 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 14. Cumulative fraction release of 55pe, 35 NUREG/CR-6164
Experimental Results 1E + 00 Peach flottom #4 =
Peach llottom #8
- Peach Bottom #12
- 1E-01 -
FitzPatrick DI "
g to 8
@ 1E-02
'E
{, 1 E -03 -
n X~p/ *-
.-M g [m' pe-6 e n
U a
/
1E-04 -
1E-05 O 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 15. Cumulative fraction release of60Co.
IE+01 Peach Bottom #4 =
Peach flottom #8 +
Peach Bottom #12
- IE + 00 _
FitzPatrick DI o 8
@ IE-01 -
- a. = -c 3 _
a
$ 1E-02 -
y / -,_ __ , n s = = ===s -s -
- IE-03 -
r
.E o
l IE-04 o .__
1E-05 -
' _.a -
1E-06 a.
0 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 16. Cumulative fraction release of 63Ni.
Experimental Results Figure 17 shows the CFRs for63Ni and indi- indexes range from 10.4 to 12.2 with55Fe having cafes a low CFR for sample #8 (5 x 10^)in con- the highest teachability index and61Ni having the trast to the average of samples #4 and #12 lowest. These data again confirm the apparent (5.9 x 10-3). As discussed above, no reason for increased mobility of 63Ni.
the low fractional release rates and low CFR from sample #8 have been identified. The average CFR Other Radionuclide Releases for63Ni(samples #4 and #8)is 5.9 x 10-3 This is higher than those for 55Fe and 60Co.
Other radionuclides for which analyses of the waste fonn and chelating agents were performed A comparison of the average CFRs for all and measurable results were obtained were 14 C, decontamination radionuclides indicates that 55Fe 99Te,1291 , 90Sr,and 241Pu. Carbon-14 Wre, and and 60Co are statistically the same if a 100% 129 1 were detectable in most leachate samples, uncertainty is applied. However, both are lower whereas 90 Sr was detectable in only a few of the than the CFR for 63 Ni and again suggests that samples, and 241Pu was not detectable in the lea-63 Ni is being released at a higher rate for the rea- chates. Figures 17 through 19 show the fractional sons discussed previously. release rates for 14C, "Tc,and 1291 . The 14C data shown in Figure 17 indicate that samples #8 and Average effective diffusivities and leachability #12 exhibit nonnal diffusion-driven release char-indexes are listed in Tables 7 through 9 for each acteristics, whereas sample #4 is more variable.
sample and are averaged in Table 10. The average The average fractional release rates of 14C for the effective diffusivities of the transition metals three samples as shown in Tables 7 to 9 range range over an order of magnitude from 6"Co from 2.5 x 1012 to 2.3 x 10-11 cm-2 s-1, an (4.4 x 1012 cm 2 s-1) to 63Ni (5.5 x 10-3 I order of magnitude difference. Sample #8 has the em2. 3-1). In addition, the average leachability highest average fractional release rate. From 1 E -09 l'each Bottom #4 "
Peach Bottom #8
- 1 Peach Hottom #12 a j 1
71E-10 -
~ .
.s I N El N lE-11 -
'N *~~.-
a M
4 't
'm. /. I h NN 6
g /xN.
d IE - 12 'N
\ \'a~-
- , _ *s
.' \
\ / A
', /
IE- 13 l O 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 17. Fractional release rates of 14C.
Experimental Results 1E-08 Peach llottom #4 =
Peach Bottom #8
- Peach Bottom #12 a 71E-09 -
I
?
e.
+
I 9 *
- 71E-10 -
E M
/
/% \
8 N= N c , ~.
=
% 1E-11 -
IE- 12 0 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 18. Fractional release rates of 99Tc.
1E-06 Peach Bottom #4 =
Peach Bottom #8 +
Peach Bottom #12
- 1E-07 -
O e 1
7 IE-08 c.
a I '
5 O a
^
71E-09 -
,__._-+ f"
~ =
\ 'f+ 7-i 6 IE-10 -
i g i d i
1E-11 -
i 1E- 12 i 0 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 19. Fractional release rates of 129g, NUREG/CR-6164 38 f
i i ---_--- -
Experimental Results Table 10, the weighted average fractional release weighted average fractional release rate is also rate of 14 C for all samples is 5.3 x 1042 statistically the same as that for 55Fe and M'Co em-2 3-1 and is statistically the same as that for and suggests similar chemical and release rate samples #4 and #12 alone. Consequently, the behavior for 99 Tc. This might be expected l weighted average fractional release rate for all because technetium is a metal and would be samples will be used for comparison purposes. expected to form complexes with organic com-The weighted average fractional release rates of pounds such as chelating agents.51 I4 C are the lowest of any of the radionuclides measured. This is consistent with the results of The average absolute rele a rates for 99Te Krishnamoorthy,53 who attributes the low release range over an order of magnitude from I rate of 14 C measured in his study to the formation 2.0 x 1040 pCi/cm2s for samples #4 and #12 !
ofinsoluble hydrates and carbonates that slow the to 1.9 x 10-9 pCi/cm 2 s for sample #8. The release of this radionuclide. Further, he suggests weighted average for all samples is 2.4 x 1040 that the fractional release rate of N)Co should be em-2. sa. This is within a factor of three of the 55 slower than 14C. This is inconsistent with our Fe results and suggests some similarity in results in which M)Co is released at a weighted release rate behavior.
average fractional release rate 20 times faster than i 14 C. This enhanced release rate may be due to Figure 19 shows the fractional release rates for ;
chelating agent effects that are increasing the 1291 . As shown in the figure, some teachates did 1 mobility of 8)Co. not have measurable concentrations of 1291 . The average fractional release rates range from in contrast to the fractional release rates, th
. 5.6 x 1040 cm-2 . sa for sample #8 to 5.9 x 10-9 cm-2 . s-1 for sample #4. The 4 absolute release rates of 14C from the Peach Bot-weighted average for all samples is 8.4 x 1040 tom-3 samples are near the highest for any radio-m.2,31. This rate is approximately a factor of nuclide and are only less than those forN'Co.The two greater than the average fractional release weighted average of the '4C absolute release rates rate of 137Cs (4.1 x 1040 cm-2. sa) from sam-as shown m_ Table 10 is 5.7 x 10-9 pCi/cm* s pie #8. Iodine, an anion, would be expected to i for all samples.Th. .is is about 20% of the weighted diffuse similarly to other ionic elements such as average absolute release rate of 60Co, which is cesium and its release would not be expected to released at a faster absolute rate than any other be affected by chelating agent effects.19.54 The radionuclid However, the stable metals are fractional release rates of iodine and cesium are released at faster absolute release rates than any the highest of all radionuclides present in the of the radionuclides. The large difference waste form and are statistically the same as that between the fractional and absolute release rates for picolinic acid (5.8 x 1040 cm-2 sd), which of 34C is due to the relatively large inventory of 14 suggests that the maximum diffusional fractional C m the waste form (approximately 60% of the release rate from the waste form is between total activity) and suggests that the release rate of 5 x 1040 and I x 10-9 cm-2 sa. Krishna-this radionuclide is controlled by waste-form moorthy53observed similar behavior except that chemistry and not diffusion.
he found that cesium was released at a faster rate than the iodine. The observed behavior, as shown The *rc fractional release rate data shown in in Figure 19, suggests that anion release rates Figure 18 are relatively constant, with the excep- may not be affected by other mechanisms besides tion of sample #8, which has a high release rate diffusion and that they are released at higher rates for the first day-long leach period. Further, the than other radionuclides.
release rates at the end of the leach test are similar to those at the heginning. The weighted average The weighted average absolute release rate for fractional release rate of 99Tc is 5.2 x 1041 1291 is 5.1 x1042 pCi/cm 2 s. It s near the lowest em-2 ' sd for all samples and is statistically the for all radionuclides and is only slightly higher same as that for samples #4 and #12 alone. This than that for 90Sr. This low absolute release 39 NUREG/CR-6164
Experimental Results rate is an anifact of the low inventory present in also the highest at 6.0 x 10-2. As discussed pre-the waste form. viously, this high CFR may be expected due to the ionic nature of this radionuclide.
Figures 20 to 22 show the CFRs for 14C,
- Tc, and 129. 1 F gure 20 indicates relatively standard A comparison of the CFRs for 14C, "Tc, and diffusion behavior for 14C for all samples. The 1291 indicates that 14C has the lowest CFR of all average CFR for14 C for all samples (2.9 x 10 ) radionuclides and that 1291 has the highest. Fur-is lower than that for all other radionuclides. This & i oN m N similar to may be due to the fact that, as previously dis- of k sidon mis M as 60Co and cussed,14C may be retained better m the waste 55Fe. This behavior may be expected because form due to the formation of insoluble hydrates wg gg7 g g ;
and carbonates.
complexing agents similar to the transition metals discussed previously.51 Figure 21 shows the CFR of 99Tc from the Peach Bottom-3 waste forms. In this case, the average CFR for all samples is 1.0 x 10-2 and is Average effective diffusivities and leachability (2.3 x 10-3) for samples #4 and #12. These indexes for 14C,99Tc, and 1291 are listed in Tables CFRs are representative of the CFRs of the transi- 7 to 9 for each sample and are averaged in Table i tion metals and suggests similar behavior for this 10. The weighted average effective diffusivities )
radionuclide as discussed previously. for 14C, 99Tc, and i291 are 1.5 x 10-14, '
l.6 x 10-11, and 5.5 x 10 9 cm2, s-1, respec-Figure 22 shows the CFRs of 1291 from the dvely. Kashnamoorthy 53 also measured effective Peach Bottom-3 waste forms. Sample #4 has the diffusivities for cement-solidified waste forms, highest CFR (9.6 x 10-2) of any of the radionu- although his did not contain decontamination ion-14 C, clides measured, and the average CFR for 1291s exchange resins For he measured an 1E-02 Peach llottom #4 m Peach Ilottom #8
- Peach llottom #12 a N
0 3 IE-03 -
E */*
e
.g
.R o "
3 1E-04 -
',7" 5 y a ,, ,_
p .-
,/ *-
a 1 E-05 ' i
_a 0 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 20. Cumulative fraction release of 14C.
Experimental Results I E + 00 i
Peach llottom #4 =
l'each Bottom #8
- Peach Bottom #12 ^
1E-01 -
N 8 .
7 . : . .
@ 1E-02
, *B
-a a*
1E-03 -
a / /.4 u
i 1E-04 -
i i
I 1 1E-05 0 0.5 1 1.5 2 2.5 Square root of time (days) i l Figure 21. Cumulative fraction release of 99Tc. l I
1E+01 l
l'each llottom #4
- Peach llottom #8
- l'esch Bottom #12 A 1 E + 00 -
0 0
mw
$ IE-01 -
/,
.. ^ --a e
e R 1E-02 -
- /, +-
e 1E -03 -
- /
1 E -04 0 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 22. Cumulative fraction release of 129 1, 41 NUREG/CR-6164
Experimental Results effective diffusivity of 3 x 10-13 cm2. s-1, which for comparison with the releases of the decontam-is an order of magnitude higher than the effective ination radionuclides 55pe,63 Ni, and 6"Co. Frac-diffusivity of 14C measured in this study. For 1311, tional release rates for iron, nickel, chromium, Krishnamoorthy measured an effective diffusiv- and cobalt are shown in Figures 23 through 26, ity of 3.4 x 10-7 cm2. s-1, which is several in addition, the fractional release rates for each orders of magnitude higher than the effective dif- element from the FitzPatrick sample leached in fusivity of 129 1 measured in this study. Conse- deionized water are also shown. Inspection of quently, it can be assumed that there are Figures 23 through 25 indicates that the chro-differences between the behavior of the laborato- mium has similar fractional-release-rate charac-ry-prepared specimens and the actual waste-fonn teristics to the nickel and that the fractional specimens used in this study. release rates of nickel from the FitzPatrick sample are similar to that for Peach Bottom-3. The aver-The average leachability indexes of 14C, 99Tc, age fractional release rates for each of the stable metals are shown in Tables 7 to 9, and the and 1291 are 13.5,11.0, and 8.4, respectively. As expected,14C would have a high leachability weighted average fractional release rates are index, and 1291 would have a low one. These data shown in Table 10.
again confirm the increased mobility of 1291.
The weighted average fractional release rate of Other radionuclides for which analyses were nickel (9.3 x 10 40 cm.2 34) and cobalt perfomied as part of this study were 9"Sr,125Sb, (l.3 x 10 9em-2 3-t) are the 'Schest at about a j 137 Cs, and transuranics including 239Pu, 241Pu, factor of two greater than that for chromium. In 242Cm, 244Cm, and 24 tam. Ilowever, the trans- addition, they are statistically the same as that of i uranics were not detectable in any of the leachate picolinic acid. These data suggest that the samples; 125Sb and 137 Cs were measurable only releases of nickel, cobalt, and picolinic acid are in sample #8; and90 Sr was detected in some lea- probably diffusion-driven and are also being chates from each sample. Less-than values were released at the highest rate possible from the not used for calculatii g release rates, effective waste fann (approximately 1 x 10-9 cm.2 3-52),
diffusivities, and leachability indexes for the However, it also suggests that 63 Ni and 6"Co are transuranics because, without any actual results, in a different chemical form than that of the stable these data would be misleading. In contrast, metals because the fractional release rate of 63Ni release rates, effective diffusivities, and leach- is about 25% of the stable-nickel-weighted aver-ability indexes were calculated for 125Sb,137Cs, age fractional release rate and the fractional and90Sr. The average fractional release rates for release rate of 60Co is about 5% of the stable-125S b, 137Cs, and 90Sr are 5.5 x 10-11, cobalt-weighted average fractional rclease rate.
4.1 x 1040, and 3.1 x 1040 cm-2 sa (weighted average). These data indicate that the In contrast to the nickel data, the data in Fig-release rates of 137 Cs and 90Sr are the same. This ure 23 indicate that the fractional releases ofiron behavior is not expected because 90Sr is not ionic from samples #4 and #12 are similar but different and would not be expected to be released at the than that observed for sample #8. The weighted same rate as 137Cs. This observed behavior sug-average fractional release of iron for all samples gests that90 Sr may be enhanced by chelating- s 6.4 x 1043 cm-2. s-1. This compares to an agent effects. average fractional release rate of 6.8 x 1041 cm-2 . sa for 55Fe and indicates that 55pc is Stable Metals released from the waste fonn faster than the ele-mental iron by two orders of magnitude. It should Stable elements for which analyses were per- he noted that comparisons of the fractional formed were iron, nickel, chromium, cobalt, zinc, release rates for iron and 55Fe indicate that 55Fe is and boron. The principal metals of interest are the released faster in the early leach periods, whereas iron, nickel, and cobalt because they can be used the nickel release rate is relatively constant.
Experimental Results 1E-07 Peacn Bottom #4 =
Peach Bottom #8 + i 1E-08 - Peach Hottom #12 A FitzPatrick DI o n ,
I I 1E-09 -
i
. l
'l .
1 s 1E-10 -
a S
- 2 5 1E-11 -
a Nx
$ 1E-12 g
N
---. N . /
- 1 E-13 -
1 1E-14 l 0 0.5 1 1.5 2 2.5 l Square root of time (days)
Figure 23. Fractional release rates of iron.
IE-08 Peach Hottom #4
- Peach Bottom #12 A FitzPatrick DI o A 1 a
1 \
is N U
{1E-09
'y l 8 E o N
8 o i -
N
- y *s -N,
- l N .
n l
l 1E-10 0 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 24. Fractional release rates of nickel.
i 43 NUREG/CR-6164
Experimental Results 111 - 08 Peac lottom #4
- Peach llottom #12 A T
I
?
f4 l
b \
71E-09 -
E w
N 8
m
% 'N N
x .ax ,_ -e % g i
" N ,_ ,
1E-10 '
O 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 25. Fractional release rates of chromium.
1E-07 Peach Ilottom #4 "
Peach Ilottom #12 '
I
(
f 1E-08 f4 1
S 5
'N' ..
8 1E-09 -
N .
Z \ y AN- _,
N N, s *- ,/*-
IE- 10 '
O 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 26. Fractional release rates of cobalt.
i i
Experimental Results l
No reason for this difference in the behavior of #12). If sample #8 is included, the average CFR l 55 '
Fe and iron is apparent because kinetics suggest for all samples is about 1.8 x 10-4. Without sam-that 55 Fe should be in equilibrium with whatever pie #8, which appears to be anomalous, the CFR chemical fami the elemental iron is in. for iron is about 0.1% of the CFR for nickel.
These data indicate that the iron is retained in the The average absolute release rates for iron, waste fomi to a much greater extent than the other nickel, and chromium, as show n in Table 10,indi- metal, which may be due to the greater complex-cate that the rates are within a factor of four for all ing capability of nickel. These data suggest that a elements. These data, when compared with the complexing effect is present that enhances the variable fractional release rate data, suggest that release of nickel, cobalt, and chromium. The high the release of these elements from the waste fonn iron results for sample #8 have not been is not dependant on the inventory in the waste explained.
form.
The CFR curves for iron, nickel, chromium, In addition to the results for the stable metals, and cobalt are shown in Figures 27 through 30. boron and zine were measured in some leachates i in the cases of nickel and cobalt, standard diffu- from samples #4 and #12. Boron was measured in ,
sional release is suggested, and in the case of iron, only three or four samples as shown in Appendix l l
the diffusional release from the intact sample #8 D. As shown in Table 10, the weighted average from Peach Bottom-3 is faster than that for the fractional release rate is 1.6 x 10# cm.2 s-i, degraded FitzPatrick specimen. CFRs for nickel with an average CFR of 2.7 x 10-2 and leach-l (2.9 x 10-2) and chromium (l.6 x 10 2) are ability index of 8.4.These data suggest that boron within a factor of two, whereas the CFR for iron is is relatively mobile and is probably in the form of considerably less at 4.6 x 10-5 (samples #4 and an ion, perhaps a borate. l l
i E-01 Peach Bottom #4 " -
Peach Bottom #8 I l Peach Bottom #12 l l 1E-02 -
FitzPatrick DI o 8
to 8
@ 1E-03 w
jj ,
. -.- 4 . 4 tu b 1E-04 -
E 3
,___-a-' '
/ s-6 l #
o 1 E-05 -
'/, p/ * ,
4 4
1E-06 O 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 27. Cumulative fraction release of iron.
i 4
Experimental Results 1E-01 Peach llottom #4 m Peach llottom #12 a FitzPatrick DI o 8
es /*X' i .
- 7 . ./ "
1E-02 - A o
.8 n .
. / '
3 /-
U 5 /
a IE-03 O 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 28. Cumulative fraction release of nickel.
l IE-01 Peach Ilottom #4
- Peach Ilottom #12 4 8
0 T
M a
o
,, /' .
kg IE -02 -
7 s/y=/*
0
/ /
$ ,/ =
3 /
e / -
,1 E -03 O 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 29. Cumulative fraction release of chromium.
Experimental Results l
1E + 00 Peach Bottom #4 =
Peach Bottom #12 '
M 0 l g IE-01 -
ci e 1 5 . -==t #
,X, 7^
._E
'3 1 E -02 -
.. l I
E
- w U .
i 1 E-03 > >
0 0.5 1 1.5 2 2.5 Square root of time (days)
Figure 30. Cumulative fraction release of cobalt.
Zine was retained to a greater extent in the behavior from the Peach Bottom-3 waste fonns.
waste form than boron and had fractional release The objective of these studies is to assess releases rates similar to chromium and nickel, which sug- from waste sites or liners. Appendix E contains gests that this metal is diffusion-driven and is the inventory of radionuclides in the Peach Bot-released from the waste form relatively quickly. tom-3 liner. The concentrations of radionuclides, chelating agents, and stable metals in the liner is Average effective diffusivities and leachability presented in Table E-1 as Ci/ liner for radionu-indexes for the stable metals are shown in Tables clides or kg/ liner of stable metals or chelates. The 7 through 10. The leachability indexes are all well summed radionuclide content is 56 Ci/ liner. The above the regulatory requirement of 6. The lowest primary decontamination radionuclides present in l is for nickel at 8.9, and the highest, as would be the resins, based on their measured concentra-expected, is for iron at 14.4. tions, are 65Zn, 60Co, 55 pe, 63Ni,and IdC. The summed activity of these radionuclides is 55 Ci or These results suggest that the average frac- about 987e of the total activity. Carbon-14 makes tional releases of the stable metals may be differ- up about 587c of the total activity.
ent than the radionuclides. In addition, the nickel, chromium, and zine are released at a faster rate than other elements and suggests that complexa- To assess possible radionuclide releases from tion of these elements, probably with picolinic the liner, the order of the leachability indexes are acid, may result in enhanced releases of these ele- summarized below from lowest to highest: 129g >
ments. 137Cs > 90Sr > 63Ni > 9T > 60Co > 55pe > 14C.
As expected, the cations and anions had the low-The chelating agent, radionuclide, and stable est teachability indexes (8-9), and IdC had the metal data listed above define the release rate highest (13.5).
47 NUREG/CR-6164 i
i
- COMPARISON OF PEACH BOTTOM-3 RESULTS WITH OTHER LOMI 4 WASTE FORMS 1
l This section compares the release rates of key appear to affect the fractional release rate because constituents of the Peach Bottom-3 waste form the inventory of picoline acid in the Indian Point
) sample is an order of magnitude less than the l with the releases from other LOMI waste fonns
! including those that degraded during leaching. other waste foims and yet the fractional release Inspection of Figure 31 indicates that the LOMI rate is greater than those for FitzPatrick and l
waste fomis have similar fractional release rates Peach Bottom-3.
l for picolinic acid that average about 3 x 10*
I cm"2. s-1. This is interesting because the FitzPa- Figure 32 shows the CFR of picolinic acid for
< trick waste form disintegrated shortly after being the LOMI waste fonns and indicates that 50-60%
l placed in the leach solution and yet the average of the picolinic acid was released from the waste j fractional release rate of picolinic acid (3 x 10 ) forms except for Peach Bottom-3 (3.9%), and that i from the FitzPatrick specimen is similar to the about 80% of the formic was released from the j Indian Point average fractional release rate and Indian Point waste fonn. These data contrast with j only a factor of five greater than the average frac- the laboratory studies performed by Piciulo* in j tional release rate of picolinic acid for Peach which the CFR of picolinic acid for LOMI wastes j Bottom-3. These results are similar, although dif- was between 0.12 and 0.20. Further, the CFR for j ferent LOMI formula.mns were used for all three formic acid in Piciulo's study was ~0.3. These l waste forms. These data suggest that the struc- data indicate that the laboratory cement-solidified l tural stability of the waste form does not affect the decontamination ion-exchange waste fomis may j release rate from the waste form. Also, the inven- not accurately reproduce the waste compositions I
i tory of picolinic acid in the waste form does not found in actual commercial nuclear power plant i
j LOMI Process LOMI Process j Q Pg:ohnic Acid C Picohnic Acid E formic Acid 10, ,
M Formic Acid i
2 10'7,
" $ 9
. ~ 5 9
2 :
" 9m h I fd l 10~, ,
I* j f a 10' -- 2 '
8
! ~E p .;O: ' . . . . -.
' w r . . ,.W+
1 I:dO ,
3::::
. . . . . . . k a)
!h ;;3,,, g3g l ' 2:::p ....
j 5]Ei$,5 -
, 5 j 'igi:
- , 5M, g 10" , * !
- s.i.
, ,, g 3 g.. s v,..... s~
43 fj;;g,.!;%:! ' ~ 92 6 ' ' = ' ' ' ' ' '
f,y g
, :M. 0-
$i4 xi
, '9 .g :R:!:
1040, $'.j!]j Mil , yp$ 104 , ...s
,, ;i:M82 j :;"!833;f' iMR' '
4
- 2:y:+
?.f.: , ,
', ::::gg2:s'
,,;g '
- M$iS' . . j!!81 Mf' , .x
- .; ; ;.
- ig.jj. Ej? JON , ilN] J 10* - 10^3 -
j i Figure 31. Comparison of average fractional Figure 32. Comparison of cumulative fraction
. release rates of picolinic acid from LOMI waste releases of picolinic acid from LOMI waste forms, fonns.
4
! NUREG/CR-6164 48 1
i j
- Comparison Results J
i wastes and that, indeed, the commercial reactor Assessment of the average fractional release wastes may contain constituents that enhance the rates of the transition metals for the LOMI waste
]
- release of picolinic acid from some waste forms forms, as shown in Figures 35 through 37, indi j (up to a factor of three). The fact that the CFR for cates that the N'Co,55Fe, and 63Ni average ft j Peach Bottom-3 is considerably better (i.e., tional releases for Indian Point are similar at i lower) than that observed for other waste forms about 6 x 1012 cm-2. s-1. w hereas for Fit /Pa-f suggests that changes in the formulation of the trick and Peach Bottom-3, M'Co and 55Fe have l waste form may have improved the leaching average fractional releases of about 6.5 x 1011 j pmperties of the waste fonn. cm-2 s-l. In contrast to these data, the 63Ni aver-1 age fractional release rates are approximately Figures 33 and 34 show the average effective 4x 10- W cm.2 . s-t for both FitzPatrick and
] diffusivities and the leachability indexes for pico. Peach Bottom-3. These data indicate a 103 range
- linic acid for the LOMI waste forms. With the of average fractional release rates for the LOMI l
.i exception of Peach Bottom-3, the effective diffu_ waste forms. In contrast, the average fractional
- sivities average 2.5 x 10-7 and suggest that the release for picolinic acid for all three waste fonns l j rates are similar for the intact and decomposed is approximately 3 x 10* cm , s-1. There is no I waste fonns. The teachability indexes are similar evidence why the Indian Point waste form aver-and range from 6.9 to 8.8. In Piciuto's laboratory age fractional release rates are J -ilar for all three I study," his leachability indexes ranged from 8.6 radionuclides and yet there are differences for l
to 9.1, which is reflective of the greater release FitzPatrick and Peach Bottom-3. l l
t rates from the actual waste fonn. In addition, his
- leachability indexes for fonnic acid ranged from The FitzPatrick and Peach Bottom-3 data sug-j 8.0 to 8.6, whereas the leachability index for the gest that M'Co and 55Fe have similar release rates Indian Point waste fonn was 6.7. and therefore may have similar diffusion i
1 l LOMI Process l C Picolinic Acid LOW Process E Formic Acid C Picohnic Acid Formic Acid j 105, 9 j
4 m n
.g j.
14-10% 4 k 12-n i
~
. . . . . 8 I I 9 $
10 7 >:p:
10- Q g j E l :8!:$iji5! .Z. f e j i
- ::;3 sis.j ..,3sf . .,
a y E rg c
-.;, 8 y -y 4
10-a .
_ _e ss;gg$
.y.ki m
e 5
af O
.- --m s2
) MO$$32 g 6- .,,,', ,4,fy
, ;gg <
2
- $3ij:y.; < e
' N265.v 10',
j gs.s .., , f.ii;:ijs u , s8?
'fi!!@ 's s
4 jn i
$hs i sf v '.
3N@E '
l io "-
d 5-x- *# ' ? A d
. . Ji$ i gg;r$.::: d^.
2-
,'S'-
i h"iNy; F s*N ,.
. . , f( '
! 10-" -
0- "-
l
- Figure 33. Comparison of average effective Figure 34. Comparison of leachability 3 diffusivity of picolinic acid from LOMI waste indexes of picolinic acid from LOMI waste 4
forms. forms.
a
! 49 NUREG/CR-6164 1
Comparison Results 1E43 10 %
f (L
1 E O g h._
wwyewyw , , . . #
e se w*nt, M n a
p .
- u. ""?"'" E iSIl'4iiM<
d5E;.9:q2?M 7
"""y 10~ " ' a k [hihb Ik}hi
,e 5
'gj;ggs
%$iR;;8 di,ff(4
~ s2 s
j h(b 4
- .gg;% .3%s
' 3$?
, :^&! StR
- y$ inh 6
$ 15is!Dk .Y . 33. <,v< d :sSik,$. IE8)$
1E 11 - -
, : :g g;p:,; pg.;,:p,:c 10'" , :
vs ! ,(^fg$$ 8{$I,,
yur x. . Od, s$:s i' .,)iSN -
v.s. . .
"J"~".s",
+ . 30@;s.,s;?
.T ,$8sg inyjIg:. - - , ,
(.),, :
-s,35:Zb:.:.P vs ,
i 8' i: gi!$!A8! NO
- , < E8S
.v.
di'y 5::sjhi$is Is3Sh E-121 iEb 'ES M8E! . :si"SE ki:;j:::R E' ^ '
.RjE:
10'u 9
.g ' : jI""m b NUS gg{;s:(
$$s:2i@ SS: ::8:UI Opss8 ^ 8!M !!! ! h5h 'gjg,s[
'Es '.W::$$'
N' '
- MiT ' ' - y:2?:0$$ $Ei:. '" M 5/>jjy'p i ,
'3:ggls8s
%. '$i2 688:269 s
$18)! *%s@f 9W w 525J'" 4: .;it:i .( jigg:gf: lE!@j.?g s![ - - - ::g_ pp i%{i::#s g' ' "
1 E '
10',8 - ~~
l Figure 37. Comparison of average fractional Figure 35. Comparison of average fractional l releases of 60Co from LOMI waste forms. releases of 63Ni from LOMI waste fonns.
1 1
characteristics from the waste fonn. Of primary importance is the fact that the average fractional release rates for these radionucli<ies were similar, although the FitzPatrick waste form decomposed and the Peach Bottom-3 waste form remained 10 intact. The average fractional release rates of 63Ni were also similar for both plants, although the average fractional relense rates are approximately 10 % E an order of magnitude greater than those of the t I other two transition metals. This difference in l
! 1 E
release rate may be due to the relative stability of o E complexes formed by the transition metals. The
' O. , '
jg m ,-
j
_ Irving-Williams correlation 51.52 indicates that the stability of transition metal complexes fall in the j 20s SW u order Ni H>Co ,pe . uThese data suggest that the
'O
,,,,- , :,:p '
c2:g:n::
fs m stability of the nickel complex with a chelating agent may result in the higher average fractional s:id.?!s8-i$ . '..P f release rates of63Ni relative to the other transition metals. Also, the similarity of the picolinic acid 1042- Mk' 9
$@j!: ileh
'* average fractional release rates for all three waste i
"!![e;' ; : ., s_ forms suggests that other factors besides com-jgg ^p"' ijhy h .
plexation with this chelating agent may be affect-
' U'" - "
ing releases from the waste form. In fact, it has Figure 36. Comparison of average fractional been suggested that the pit and ion strength releases of55Fe from LOMI waste forms. associated with the leachant, as affected by the NUREG/CR-6164 50 1
- 4
I Comparison Results chemistry of the waste form, may cause the transition metal chelating agent complex to break down.39 104 9 A comparison of the cumulative fractional releases for the transition metals is shown in Fig- g )
ures 38 through 40. An assessment of the cumu- 4 lative fractional releases indicate that the greatest ,y,. ! g release (9.2%) is for 63Ni from the FitzPatrick _ j waste form. Other cumulative fractional releases . . c&:s 5 range from 0.02 to 1%, with the release of 55pe ssc g ;
~'
and63 Ni from the Indian Point specimen between e s' 17*'
0.02 and 0.03%. In contrast, the CFRs for the che- 5 $$M n..
- ['...
lating agents ranged from 50 to 60% with the $, 5.@
r <- ,s ce. .~9',
exception of Peach Bottom-3 (3.9%). These data 1 M,g.,g@e ;
- xn { 4sn%.s>:
"W suggest that the chelating agent concentration is _
$ ... .li:j@f"-
- i not directly correlatable with the release of radio- 4 30 - js$$p g vgx f C '" I nuclides because the average fractional release 5$32 [ y a rate for the transition metal radionuclides from ]l $jij ]' ' ![ f y' i?
- l{$!S$5 i the Indian Point waste fonn was much less than ""^4: : : s M 5:6
~'
l for the other plants, and yet the average fractional . hsMi: ! i8sd release rate and the CFR (0.6) of the chelating Figure 39. L,umulative fraction releases of agent was the highest for this type of waste form.
55Fe from LOMI waste fonus.
i i
j O
o 10" ' o g
x -
3a r
9; I h 1
..'...... ) $
g
~
t 0^ , --
., o., . ,
N
- s E {; .: R::vi+:. ,
m e j Og;:p::.
f " ' 8P '
g .: :7 ;.. s :@;$ Gb 2 $ 392, '
- n -
f$'l5.la[8
. . . ~
n u2 gg:g3.lq g4.A. .
! 10 - ' j:6..
~
s..,..
))Q.l u- E% ?f: :9); .,
g ....::gg
- y*+g /s..s 30-3, q !2 7*9g
- ik:^q
'f 'i p: 4 s :m ...,..__ i
@@ei:'g:: ;j s 590:?$
f -
( -m mw di'i s i
10a '
' " s%8
, :ss :si;i ; , ,gsp20: ,, s'h ..,
s i 7.,:n yp,s:ls.:.;
- +:. .::, . .s o~.
t
,- . /
10d , i' ijyff' 2'so 56:iij
, Mi: s'gMi3%$5 i ' 0d:s ,s8ssi[
fS 85535 5 s$.'Es cc,.ss? '
~i;ss ?is:$$ s?!F 8;g:x;. s 93$il ;M:~j.;..D
-sy:4:: .'
s:8. s s..,
- 85ffN. W'-. ' Sm 10'8-
"* *' :* is' "- ~ h 10^* -
Figure 38. Cumulative fraction releases of Figure 40. Cumulative fraction releases of N'Co from LOMI waste forms. 63Ni from LOMI waste forms.
Comparison Results Figures 41 through 43 show the average effec-tive diffusivities for the transition metals. These results, as previously discussed, typically follow the results of the fractional release rates. For the 104 ,
LOMI waste forms, there is a broad range with g FitzPatrick having the highest effective diffusiv- {
ity. The average effective diffusivities for 55pe 1040, g j and 63Ni are variable as discussed previously.
Typical ranges are difficult to define due to the
_ j 10'" , j+jis;;.,c..
. m'M A variations in each waste form. ::x::3:43 ,_,.,,,,,,
. x.a
.b e,j}ijf'5bk~ 74
- sula The leachability indexes for the transition met- 10" j [nkOP'hf xS:j..is lifjy als are shown in Figures 44 through 46 are more ta 3 m:n.4.
s.n. s informative. For all transition metals, the teach- 'w g 13s :ic,"
10'u '
2 ., .s-ability indexes are within the requirements of the sx,.gs' g j!iif ilhov
" Technical Position on Waste Form," Revision 1. M. .f.$i.!38 3 s f4:5..!3 s 15 Z ':ssiS
,we This lower leachability index may be due to the ^$:s,yss
. hPs!!s..
PT f E apparent mobility of 63Ni, which appears to be generic for all waste forms.
10-" '
gjg s-
.gs gg [fgsps; ing:g j;s{ii[i- ,
iisssj: y:
'i!:misjsi ij25 fist U 4si?
10d ' -
' ' " ~ ' ' ' ' '
Other radionuclides identified in this study are Figure 42. Average effective diffusivity of NIPu, NC, 99Tc,and 1291 . In the teaching studies 55Fe from LOMI waste forms. t l
9 10-7, 10-71 g E I U '
104, 104 , L' 9 7 E@ , g
- 04 , j f 5
4 10 1 jsj.i:!
4js, j g
g g n:
, !$ss y %
g d '
, g a) A 10"81 10 '1 '
- v. ,
', , . , , , 6 M68 !:!8i:
",( ~ N'pg ' ' ' , :7 $
, ::; p fs;?;'.
f 10-" , (h h j!} eegs 10'" 1 hf$j!h[ji!jfi Mb si, < t*"> , g. ;:
g 30. < jf ,%
10a2, j Mji;gl,g:;, .-j:<j< f:-
, . gg;: 1042q g s,g,
.y. , c *, x4 .y <<
10'" ,
N:@q:q E8 s,M ,.: eg, 10'" ,
f Ek W
, .<o
- $IC' '
- @if+<
... i)[+)@:.M 8.. '
,. ""==,:,
qqy : d8. i$< '
W:iN. .
EkkYjh 10'" 1 ..
< Nii lis :i8i:
I 10'" 1 $21!
.hf
(. Ek '
5/5h'[
':di$is -
10-" - 10^" -
Figure 41. Average effective diffusivity of Figure 43. Average effective diffusivity of 60Co from LOMI waste forms. 63Ni from LOMI waste forms.
l l
Comnarison Results l 20- 20-1 l
l 18- 18- n n y 1
16- g' .
qs.
f c
e .9 j
9 ~12 5 l
14 - E I is j d
g 14 9
[
I --- n. a, g v#' .,, we.
^' 6 12- fii 38s
-33S'fYNh y M
~
'Ikjijn.
f 8e 3
}9'.\9xXS .,,.. s, f s?.h O*
.yy,syk- . . . -
yenn ,y U 10- 3:ps N..n * ' --~~'~
.!:j8E;... . 30 fs? .r:
'25![i$$$$!$$i ' s*3 ~d IS$!k OfE gg y
~
dh5! 8- .,,jiy0 k$h.. :xh..f!.!$...
v ,x4: .. :: 4.
3
- e::.1 x3
~ ~'N is[35.ss:h j:}7.x$$.;q.
.2- ~s -
m:
6- *fs?!( ' s?!.'%':!.O.
~ n .x.,x e
-?.::x
.~ -
IIOSSOs IE:'f::Qb, sx - v.
inoX9n. ,
.,,. : 'f. y(V { ; O- mp/<
,0e '
X.;. . e Y3 ssp.! $$I ^s8f ,
'- , :3%3s3 Wi/" JS->
4- g.:.2 :f :sse
<::SMS XMiw. C'....'
M$p$. i min} 0's s , i:s!5Ei* 4- @$$j$6 $$$E8 . z.
2-($$$ts 's : 2 sin
. ' , .,jy.:. 1inf~ i3M" $50 2- :2s!., p s iO;p:
ii35p;>235 s 37.;S.ff{ ,%.'x.y, 0-
^^-
s
.. .>xg:.;
- ,.3 Figure 44. Leachability indexes forN'Co from Figure 46. Leachability indexes for 63Ni from LOMI waste fonus. I OMI waste forms, performed for 24t Pu, only the inventory in the waste forms was measured. The inventory per 20- gram of resin typically ranged from 10* to 10-4 m pCi/cm 3of resin. Ilowever, no real values were 18 .- I a
measured. Results for 14C,94c,and 1291 were not 3 g comparable with other LOMI waste forms
'8-E j because these radionuclides were not measured in 14- j
- s. previous studies. Consequently, the data devel-m#
Os @' .
2 oped m. this report provide the primary baselinc yssya:;.
12- 85tiis$.~ - for the release of these radionuclides.
bs0.h<a{$,e T
S,.<.,.- .
10- SXmu[4kXQ.f s ><N>D m .g :e ; $.Kl.
+ '$ { ' '-
.'Y .X
'$5'
' ,.g:p:x?
E .v.-
8- -:: !$x
. , g :e:9;s,,,
fidX' Ed, fj?)i'{?).
.:.S((.kh)()',:;
33 :jy:f*$-
^
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- f ;sz pssgr S . Msv..
0-Figure 45. Leachability indexes for 55Fe from LOMI waste forms.
CONCLUSIONS The primary conclusions of this study relate to The summed radionuclide content in the Peach the structural stability of the Peach Bottom-3 Bottom-3 waste forms is 7.8 pCi/g of waste waste form and the releases of radionuclides, form. The primary decontamination radionu-stable metals, and the chelating agent picolinic clides present in the resins based on their mea-acid from the waste form. In this study, compari- sured concentration are 54Mn, 65Zn, 60Co, 55Fe, sons have been made with degraded waste forms 63Ni,and 14 C. The summed activity of these such as the FitzPatrick waste fonn and with other radionuclides is 7.7 pCi/g waste form or about LOMI waste fonns. 98% of the total activity. Carbon-14 makes up about 58% of the total activity. The dominant decontamination radionuclides 60Co and 55Fe The key conclusions of this study are that the make up about 31% and 1.9% of the total activity Peach Bottom-3 waste form meets the stmetural in the resin waste, respectively, In contrast, the stability requirements (compressive strength fiss on products 90S r, 99Tc,129$and 1 137Cs collec-
>500 psi) and leachability requirements (leach' tively constitute about 0.3% of the total activity.
ability index >6.0) identified in the NRC's " Tech-The concentrations of the transuranic isotopes are nical Position on Waste Fom1," Revision 1.
also low and sum to a total of 1.6 x 10~3 pCi/g (0.02% of the total activity). Greater than 87r/c of To assess possible radionuclide releases from the transuranic activity was MPu.
the liner, the order of the leachability indexes are .
summarized below from lowest to highest: 1291>
- " " . Y *" '"
137Cs > "USr > 63Ni > 99Tc > 60Co > 55Fe > 14C. ^ '""?
E* *'" '". " . W" #" "*"'
and FitzPatrick samples mdicates that the average As expected. the cations and anions had the low-est leachability indexes (8-9), and 14C had the ute ang awmge fmetmnal dase nney M pic h. ,me acid for both waste forms are s.imilar.
hi @ ' These data indicate that the structural stability has a limited effect on the release rates of picolinic In the evaluation of the leach test results, pri- acid from the waste form and suggest that chemi-mary conclusions were developed in the area of cal mechanisms either in the waste form or in the pil effects on leachability and the characteristics resin itself control the release rate from the waste of radionuclide and stable metal releases from the fonn.
waste form. The pH data indicate that the pil of the leachant is affected within a few hours and A comparison of the absolute and fractional probably within a few minutes by the chemistry mie s mte data for the three decontamination radionuclides,55Fe,60Co, and 63Ni. indicates that of the waste fonn.
the lack of cement-solidified waste form struc-tural integrity (does not hold together) does not In the characterization of the waste stream appear to significantly affect releases from the result.s, concentrations of radionuclides in the res- solidified waste form. The average fractional ins and concrete varied for several radionuclides. release of63 Ni is probably higher than that for the Results of these analyses suggest that there may other decontamination radionuclides and indi-be irregularities in the concentrations of radionu- cates that this rad;onuclide is released at a higher clides in the waste fomt Among the stable metals rate than the others. The nigher fractional release whose concentrations were measured in the resin rates associated with 63 Ni may be due to the wastes, the iron concentration was highest at increased stability of nickel complexes, as the 3,00() pg/ gram resin. This was followed by nickel Irving-Williams correlation indicates that the sta-and chromium. In addition, analyses were per- bility of transition metal complexes fall in the formed for sulfate and phosphate. Neither ion was order Ni H>Co >Fe H
.HThese data suggest that the detected in the waste fom1 or the resin samples. stability of the nickel complex with a chelating NUREG/CR-6164 54
?
l Conclusions i
1 i
l agent may result in the higher average fractional ther confirm the fact that the release of nickel is l- release rates of 63Ni relative to the other transition not dependant m waste-form structural stability.
metals. In addition, the average fractional release rate of nickel (I x 10-9 cm-2. sa) is about a factor of Other radionuclides for which analyses of the two greater than that for picolinic acid.These data waste form and chelating agents were perfomied suggest that the release of nickel and cobalt may and measurable results were obtained were 14C. not be controlled by the release of picolinic acid
" Tc,329 ,1 WSr and 241Pu. Carbon- 14, 99Tc, and because they are released at a statistically faster 1291 were detectable in most samples, whereas rate than the picolinic acid, j 90 j Sr was detectable in only a few of the teachate samples, and 241Pu was not detectable in the lea. In contrast to nickel, the data indicate that 55pe i chates. The weighted average fractional release is released from the waste form faster than the rates of 14C are the lowest of any of the radionu. elemental iron. This suggests that 55Fe is in a dif-clides measured. This is consistent with the ferent chemical form than the bulk of the elemen-results of Krishnamoorthy, who attributes the low tal iron; however, kinetics suggest that 55pe release rate of 14C measured in his study to the should be in equilibrium with whatever chemical formation of insoluble hydrates and carbonates, fomi the elemental iron is in. No explanation for which slow the release of this rad!anuclide. Fur. this behavior is apparent.
ther, he suggests that the fractional release rate of Absolute release rates for iron, nickel, and N)Co should be slower than 14C. This is inconsis-tent with our results in which NICo is released at a chromium indicate that the release rates are within a factor of two for all elements.These data, weighted average fractional release rate 20 times faster than 14C. when compared with the fractional release rate
! data, suggest that the release of these elements .
fr m the waste form is not dependant on the !
This weighted average fractional release rate of 94c is statistically the same as that for 55Fe and '" "#"I 'Y ' " '# * * " " '
M'Go and suggests similar chemical and release The concentrations of radionuclides, chelating rate behavior for 99 Tc. This might be expected agents, and stable metals in the liner were calcu-because technetium is a metal and would be lated as Ci/ liner for radionuclides or kg/ liner of expected to form complexes with orgame com-stal' netals or chelates. The summed radionu-pounds such as chelating agents.
clide content is 56 Ci/ liner. The primary decon-tamination radionuclides present in the liner, Fractional release rates for all radiouclides based on their measured concentration, are 54Mn, range from 3.5 x 10 d em-2 s d (129g) to 65Zn, 6"Co, 55 pe, 63Ni,and 14C. The summed 3.4 x 1042 cm-2 . sa(14C). The fractional release activity of these radionuclides is 55 Ci or about l rates of iodine and cesium are the highest of all 987c of the total activity.
radionuclides present in the waste form and are l statistically the same as that for picolinic acid Cornparisons of the releases from LOMI waste l
(5.8 x 1040 cm-2 sd), which suggests that the forms that have been leached as part of this study maximum diffusional fractional release rate from and as part of previous studies indicate that the l the waste form is hetween 5 x 1040 and inventory of picolinic acid in the waste form does l 1 x 10* cm-2 . sa- not appear to affect the fractional release rates I because the inventory of picoline acid in the Evaluation of the release rate data for the stable Indian Point sample is an order of magnitude less metals indicates that iron, cobalt. and chromium than the other waste forms and yet the fractional have similar release rate characteristics and that release rate is greater than those for FitzPatrick the release of these metals from the intact Peach and Peach Bottom-3. The fact that the CFR for Bottom-3 waste form is similar to that from the Peach Bottom-3 is considerably better (lower) degraded FitzPatrick waste form. These data fur- than that observed for other waste forms suggests l
55 NUREG/CR-6164 l
Conclusions that changes in the formulation of the waste form affects on the transition metals. These effects are may have improved the leaching properties of the less apparent for 55Fe and "Co, which form com-waste form. plexes that are less stable than those formed by 63Ni. Also, the release rate behavior of 99Tcis In summary, key conclusions from the Peach similar to that of55Fe and *Co and suggests sim-Bottom-3 study are that the compression test ilar chemistry for this radionuclide.
results and leachability indexes meet the require-ments of the NRC's " Technical Position on Waste Forms," Revision 1, and that release rates of Another principal observation is that 14C, radionuclides, stable metals, and chelating agents which had the highest inventory (58%) of any do not appear, in general, to be affected by the radionuclide in the waste form, had the lowest structural stability of the waste fomt. These data leachability index, and indicates that this radionu-suggest that waste form compression testing is of clide is strongly retained in the cement matrix, limited value in assessing actual waste-form sta- probably as an insoluble hydrate or carbonate. In bility. Other key points are that the apparent contrast,1291, a mobile anion, is released at rates higher release rate for63Ni may be due to greater similar to those for 137Cs and has the lowest stability of complexes formed by this radionu- leachability index (8.4) or the highest release rate clide and further suggests that there are chelant of all radionuclides measured.
REFERENCES
- 1. " Technical Position on Waste Form," U.S. Nuclear Regulatory Commission, Low-Level Waste Man-agement Branch, Washington, D.C., May 1983.
- 2. " Technical Position on Waste Form," Revision 1. U.S. Nuclear Regulatory Commission, Low-Level Waste Management Branch, Washington, D.C., January 1991.
- 3. " Compressive Strength of Cylindrical Concrete Specimens," ASTM C39, American Society for Test-ing and Materials, October 1984.
- 4. " Measurement of the Leachability of Solidified Low-Level Radioactive Wastes by a Short-Term Test
, Procedure," ANSI /ANS-16.1-1986, American Nuclear Society Standards Committee, April 1986.
- 5. E. O'Donnell and 3. Lamben, Low-Level Radioactive Waste Research Program Plan, NUREG-1380, November 1989.
- 6. Workshop on Cement Stabili:ation of Low-Level Radioactive Waste, Gaithersburg, Maryland, May 3/-June 2,1989, NUREG/CP-0103, October 1989.
- 7. L. Criscenti and R. Seme, Geochemical Analysis of Leachatesfrom Cement / Low-Level Radioactive Waste /SoilSystems, PNL-6544, September 1988.
- 8. C. Howard. C. Jolliffe, and D. Lee,lmmobili:ation in Cement oflon-Exchange Resins Arisingfrom the Purification of Reagents Usedfor the Decontamination of Reactor Circuits, AEEW-M-2536, CPDG-(88)-Pil8, UKAEA Atomic Energy Establishment, Winfrith, England, September 1988.
- 9. C. Howard, C. JolIiffe, and D. Lee,lmmobili:ation in Cement oflon-Exchange Resins Arisingjrom the Purification of Reagents Usedfor the Decontamination of Reactor Circuits, AEEW-M-2558, CPDG-(88)-P208, UK AEA Atomic Energy Establishment, Winfrith, England, February 1989.
- 10. A. Ipatti and H. Harkonen, llaff-Scale Solidification Experiment of Spent lon-Exchange Resins, YJT-89-11, Nuclear Waste Commission of Finnish Power Companies, August 1989.
I1. B. Torstenfelt and G. Hedin," Leaching of Cesium from a Cement Matrix," Materials Research Society Symposium Proceedings, Vol.127, Conference Title 12-International Symposium on the Scientific Basis for Nuclear Waste Management, Berlin, Germany, October 10-13,1988.
- 12. C. Mcisaac and 3. Mandler, TI,e Leachability ofDecontamination lon-Exchange Resins Solidified in Cement at Operating Nuclear Power Plants, NUREG/CR-5224, March 1989.
- 13. 1. V. Bishop, Solidtfication in Cement oflon. Exchange Resinsfrom LOMI Decontamination. EPRI NP-6934, August 1990.
- 14. M. S. Davis, P. L. Piciulo, B. S. Bowerman, et al., The Impact ofLWR Decontamination on Solidifica-tion, Waste Disposal, and Associated Occupational Exposure, Annual Report-Fiscal Year 1984, NUREG/CR-3444, February 1985.
- 15. J. O. Lee, K. W. Han, and L. P. Buckley, "Short-term Leaching Behavior of Co-60, Sr-85, and Cs-137 From Cemented lon-Exchange Resin Waste Forms," Second International Symposium On Stabili:a-tion / Solidification of Ha:ardous, Radioactive, and Mixed Wastes, Williamsburg, Virginia, May 29 through June 1,1990.
References 1 61 P. Soo, L. Milian, and P. Piciulo, The Leachability and AfechanicalIntegrity ofSimulated Decontami-nation Resin IVastes Solidified in Cement and Vinyl Ester-Styrene, NUREGICR-5 l53 May l988.
- 17. .C. V. Mcisaac, D. W. Akers, and J. W. McConnell, Effect ofpH on the Release of Rada nuclides and Chelating Agentsfrom Cement Solidified Decontamination lon-Exchange Resins Collectedfrom Operating Nuclear Power Stations, NUREG/CR-5601, June 1991.
- 18. "Long-Term Leach Testing of Solidified Radioactive Waste Forms," ISO 6961,1982-1015.
l 19. P. Vejmelka and R. Koster," Leach Studies of Chelating Agents and Influence on Radionuclide Leach-ing from Simulated LLW/lLW Cement Waste Forms," Proceedings ofIVaste Afanagement '90,1990.
- 20. R. J. Lemire and E Garisto, "The Effect of lonic Strength, Groundwater Composition, and Tempera-ture on Calculated Radionuclide Solubilities,"Radiochimica Acta,58/59,1992.
- 21. L. W. Jones, M. Bricka, and M. J. Cunnane," Effects of Selected Waste Constituents on Solidified /Sta-bilized Waste Leachability," Proceedings ofSecond International ASTAf Symposium on Stabili:ation!
Solidipcation ofHa:ardous, Radioactive, and Afixed Wastes, Afay 29,1990.
- 22. J. O. Lee, K. W. Han, and L. P. Buckley,"Short-Term Leaching Behavior of Co-60, Sr-85, and Cs-137 from Cemented lon-Exchange Resin Waste Forms," Stabili:ation and Solidification of Ha:ardous, Radioactive, and Afixed Wastes, Vol. 2, ASTM STP 1123,1992.
- 23. G. De Angelis, A. Marchetti, and S. Balzamo," Leach Studies: Influence of Various Parameters on the Leachability of Cesium from Cemented BWR Evaporator Concentrates," Stabilization and Solidifica-tion ofHa:ardous, Radioactive, and Afixed Wastes, Vol. 2, ASTM STP 1123,1992.
- 24. M. Fuhrman and P. Colombo," Radioactive Releases from Cement Waste Fonns in Seawater," Radio-active Waste A1anas ement and the Nuclear Fuel Cycle H, p. 365,1989.
- 25. S. Croney, Leachability ofRadionuclidesfrom Cement Solidified Waste Forms Produced at Operating Nur/ car Power Plants, NUREG/CR-4181, . March 1985.
- 26. M. A. Miller and J. E Remark," Philadelphia Electric Company Peach Bottom Atomic Power Station Unit 3 Decontamination Experience," Proceedings of the Third Seminar on Chemical Decontamina-tion ofBWRs, December 6-8,1988 EPRI 89-wk-52.
- 27. D. Schneidmiller, "Recent Pacific Nuclear Decontamination Experience," Proceedings of the Third Seminar on Chemical Decontamination of BWRs, December 6-8,1988, EPRI 89-wk-52.
- 28. J. Jeffrey " Waste Processing of Resins," Proceedings of the Third Seminar on Chemical Decontami-nation ofBWRs, December 6-3,1988, EPRI 89-wk-52.
- 29. " Improved Cement Solidification of Low and Intermediate Level Radioactive Wastes," Technical Report Series No. 350, International Atomic Energy Agency,1993.
- 30. E P. Glasser et al.," Immobilization of Radwaste in Cement-Based Matrices," Department of the Envi-ronment Radioactive Waste Management Research Programme 1986-7 University of Aberdeen, AB9 2UE, Scotland.
- 31. S. Rakhimbaer and S. M. Bash,"Effect of Organic Substances on the Setting Time of Portland Cement," Zh. Priki. Khim. (Leningrad),41,121. pp. 26118-24,1968.
References
- 32. F. M. Lea, The Chemistry of Cement and Concrete. Arnold Publishing,1970.
- 33. D. R. Douyherty and P. Colombo, Leaching A1cchanisms ofSolidified Lim -Level Waste, The Literature Survey, BNL-51899, June 1985.
i
- 34. B. Siskind and M. G. Cowgill," Technical Justifications for the Tests and Criteria in the Waste Form ;
Technical Position Appendix on Cement Stabilization," Proceedings of Waste Afanagement '92,1992, pp. 1753-1759.
- 35. R. M. Neilsen and P. Colombo, Waste Form Development Program Annual Progress Report, October 1981-September 1982, BNL-51614, September 1982.
- 36. J. E. Mendel et al.. A State-of-the-Art Review of Afaterials Properties of Nuclear Waste Forms, PNL-3802, Battelle Pacific Northwest Laboratory, Richland, WA,1981,
- 37. II. W. Godbee and D. S. 3oy, Assessment of the Loss ofRadioactive isotopesfrom Waste Solids to the Environment, Part 1: Backgrdund and Theory, ORNL-TM-4333,1974.
- 38. O. U. Anders, J. F. Bartel, and S. J. Altschuler," Determination of the Leachability of Solids," Analyti.
cal Chemistry,50,4, pp. 564-569,1978.
- 39. Carbon-14/ Tritium Analysis for 10 CFR 61, TP-691, B&W Nuclear Environmental Services, March 1993.
i l 41. P. L. Piciulo, J. W. Adams, J. II. Clinton, and B. Siskind, The Egert ofCure Conditions on the Stability )
l of Cement Warte Forms After /mmersion in Hitter, WM-3171-4, Brookhaven National Laboratory,
- September 1987.
- 42. B. Siskind, J. W. Adams, J.11. Clinton, and P. L. Piciulo,"The Effect of Cure Conditions on the Stabil-ity of Cement Waste Forms After Immersion in Water," Proceedings of Waste Afanagement '88,1989, pp.613-618.
i
- 43. Intemational Atomic Energy Agency,lmpmved Cement Solidification ofLow andIntermediate Level Radioactive Wastes, Technical Report No. 350, p. 54, January 1993.
- 44. Inte national Atomic Energy Agency, Treatment of Spent lon-Exchange Resinsfor Storage and Dis-posal, Technical Report No. 254, IAEA,1985.
- 45. International Atomic Energy Agency, improved Cement Solidification ofLow andIntermediate Level Radioactive Wastes, Technical Report No. 350, p.15, January 1993.
- 46. P. L. Piciulo, J. W. Adams, M. S. Davis, L. W. Milian, and C.1. Anderson, Release ofOrganic Chelat-ing Agentsfrom Solidified Decontamination Wastes, NUREGICR-4709. July 1986.
- 47. R. J. Lemire and F. Garisto,"The Effect of lonic Strength, Groundwater Composition, and Tempera-ture on Calculated Radionuclide Solubilities," Radiochimica Acta,58/59,1992.
I
- 48. K. . Andersson, B. J. Torstenfeldt, and B. Allard, Sorption and Diffusion Studies of'Cs andIin Concrete, Report 5-412-96, Chalmers University of Technology, Goteburg Sweden,1981.
l I
References
- 49. P. Colombo, et al., Accelerated Leach Test (s) Program Annual Report, BNL-51955, September 1985.
- 50. 11. Nitsche, A. Muller, E. Standifer, R. Deinhammer, K. Becraft, T. Prussin, and R. Gatti," Dependance of Actinide Solubility and Speciation on Carbonate Concentration and lonic Strength in Groundwa-ter," Radiochimica Acta,58/59, pp. 27-32,1992.
- 51. N. N. Greenwood and A. Eamshaw, Chemistry of the Elements, Pergamon Press, New York, NY,1986.
- 52. 11. M. N. H. Irving and R. J. P. Williams, "The Stability of Transition-Metal Complexes," Journal of Chem. Society, pp. 3192-3210,1953.
- 53. T. M. Krishnamoorthy, S. N, Joshi, G. R. Doshi, and R. N. Nair," Desorption Kinetics of Radionuclides Fixed in Cement Matrix," Nuc/ car Technology,104, December 1993.
- 54. G. Rudolph and R. Koester," Source Term Evaluation or Actinide Elements in the System Cemented Waste Form / Salt Brines - Influences of Organic Complexants," Afigration 89, International Confer-ence on Geochemistry and A1igration ofActinides and FP. Aionterey Cahfornia, November 6-10,1989.
l l
I l
i
)
Appendix A LOMI-NP-LOMI Decontamination Process l
4 la A- 1 NUREG/CR-6164
Appendix A Appendix A LOMI-NP-LOMI Decontamination Process In most instances, chemical decontamination ments are used on such films to condition them by process formulas have been developed in a com- rendering the chromium soluble through oxida-petitive environment; therefore, their exact chem- tion from C to +6 valence state.
ical compositions are considered proprietary. The . .
following description of the decontamination The reagents are slurried or dissolved in con-process used at the Peach Bottom Atomic Power centrated form and mjected directly into the pri-Station Unit 3 from which solidified decontami- mary system water and circulated for 1 to 3 days.
nation resin waste forms were collected was During the process, the decontamination solution obtained from the literature and does not include is passed through cation exchange resins to information of a proprietary nature. remove the corrosion and activation products and regenerate the reagents. Following completion of There are two general methods that have been decontamination, mixed-bed resins are nomially developed to perform full system decontamina. used to remove the residual metallic ions and the tions of LWRs: concentrated chemical processes decontamination reagents.
and dilute chemical processes. The concentrated The LOM1 process t.2.3 was developed by the processes use reagent concentrations of between Central Electricity Generating Board in Britain 5 and 25 wt7c, and the dilute processes that are and is now being marketed in the United States by currently employed use reagent concentrations of Vectra Technologies (formerly Pacific Nuclear 1.0 wt7c or less. Based on thee concentrations, Services) and Westinghouse. The basic feature of the quantity of reagents required for a concen-the process is the use of V+2 (as vanadous for-trated process decontamination range from about 3
mate) to reduce the Fe+3 in oxide films to Fe+2 48 to 248 kg of reagent /m of primary system vol-The process involves electron stripping rather ume to be contaminated. A similar estimate for a than attack of the film by acid. It can be a multi-dilute process decontamination is less than step process that nomially employs a chromium 10 kg/m3 During recent years. the dilute chemi-removal step following the initial LOMI process.
cal processes have become the most widely used.
Picolinic acid (as sodium picolinate) is used as a
. complexing agent and is injected into the coolant, The decontamination processes used at the and the coolant is circulated while being main.
LWRs from which samples were obtained were tained at a temperature of between 353 and dilute chemical, multi-step processes. They 368 K (80 and 95 C) under atmospheric pres-employed between 0.1 and 0.6 wt% reagent and were multi-step in the respect that they required sure. Vanadous formate [V(HCOO)2] is then injected to reduce Fe+3 to Fe+2. The reaction des-an initial oxide removal step, a chrome removal tabilizes the oxide film releasing the metal ions to step, and a final oxide-removal step. The the solution. The excess picolinate in the reagent processes were performed at low temperature complexes with the metal ions and keeps them (333 to 368 K (60 to 95 C)] and atmospheric from redepositing on the system surfaces. The pressure. The processes, m general, use a com-LOMI reagents and dissolved radionuclides and bination of organic acids and chelating agents t metal ions are removed from the system through dissolve the oxide film from surfaces and suspend treatment with ion-exchange resin columns. Both the resulting organo-metal complexes in solution.
strong-acid cation and weak-base anion resin col-Corrosion inhibitors are sometimes added t umns are usually employed to process the spent reduce the attack of organic acids on carbon steel LOMI reagent solution.
piping. Some oxide films have significant con-centrations of chromium that adversely affect the The initial LOMI step is followed by the injec-dissolution of the oxide layer. Oxidizing treat- tion of nitric acid potassium permanganate (NP)
A-3 NUREG/CR-6164
Appendix A at a pli of 2.5 or alkaline potassium permanganate products removed during decontamination are (AP), which is currently used at a pH of 10-11.5. processed through ion-exchange resins, and these These solutions render the chromium soluble, resins constitute the decontamination waste leaving behind an iron-rich deposit that can be product.
dissolved using the LOMI reagents. The NP (or AP) reagents are removed on ion-exchange resin The LOMI-NP-LOMI process as described in columns. Residual MnO2 that is formed during References 4,5, and 6 was used for the decontam-the oxidation process is dissolved with oxalic ination at Peach Bottom-3.a The LOMI-NP-acid, which is added directly to the permanganate LOMI decontamination took 4-5 days, and a total solution and removed on a mixed-bed resin col- of 39 Ci was removed.5 Figure A-1 from Refer-umn. Following the oxalic acid rinse, the initial ence 5 shows the release of radioactive material LOMI step can be repeated using a more dilute for each step.
concentration of LOMI reagents. This decontami-nation process is commonly referred to as the LOMI-NP-LOMI (or LOMI-AP-LOMI) process, a. Personal communication, John Remark, Febru.
In,either case, the spent reagents and corrosion ary 17,1994.
{
1 NUREG/CR-6164 A-4
45 -
40 -
npm--w 9 gG u m
35 - r -
J
[
r'L r" 30 -
a E
E r'O a
o_ 25 -
- i?
3o
- 20
> .=
'a $
15 10 -
LOMI- 1 NP OXALIC LOMI - 2 5 -
y OC I I I I I I I I I I I I x 0 4 8 12 16 20 24 m
O >
d Hours y gy, g W E m a E'
5 Figure A-1. Radionuclide release from Peach Bottom-3 LOMI-NP-LOMI decontamination process. >
Appendix A REFERENCES l 1
- 1. R. Soto, Decontamination Waste Management, EPRI NP-4240, September 1985.
- 2. M. Davis, The Impact of LWR Decontaminations on Solidification, Waste Disposal, and Associated Occupationa/ Eiposure, NUREG/CR-3444, August 1983.
- 3. Development of LOMI Chemical Decontamination li chnology, EPRI NP-3177, July 1983.
- 4. M. A. Miller and 3. F. Remark," Philadelphia Electric Company Peach Bottom Atomic Power Station Unit 3 Decontamination Experience," Proceedings of the Third Seminar on Chemical Decontamina-tion of BWR's, December 6-8,1988, EPRI 89-wk-52.
- 5. D. Schneidmiller,"Recent Pacific Nuclear Decontamination Experience," Proceedings of the Third Seminar on Chemical Decontamination ofBWR's, December 6 4,1988, EPRI 89-wk-52.
- 6. 3. Jeffrey, " Waste Processing af Resins," Proceedings of the Third Seminar on Chemical Decontami-nation of BWR's. December 6-8, I988, EPRI 89-wk-52.
NUREG/CR-6164 A-6 l
l
1 j
i i
i i
1 i
Appendix B i Summary of Solidification Performed at the Peach Bottom Atomic Power Station Unit 3
.i a
i i
- 1 i i 1 l
., I i l 1
B-1 NUREG/CR-6164
i Appendix B Appendix B Summary of Solidification Performed at the Peach Bottom Atomic Power Station Unit 3 On October 20,1989, Chem Nuclear Systems The two PCP specimens were removed from Inc. (CNSI) personnel prepared two process con- the oven after they had been baked between 18 trol program (PCP) specimens using 100-mL and 24 hours2.777778e-4 days <br />0.00667 hours <br />3.968254e-5 weeks <br />9.132e-6 months <br /> and were then examined. The sam-samples of wet ion-exchange resin that had been pie that contained 71 g of Portland cement was removed from liner 446828-15 after it had been hard; however, the sample containing 48 g of mixed for about 30 minutes. The PCP specimens Portland cement was somewhat soft. One could were prepared in 250-mL plastic disposable bea- push the tip of a pencil into the surface of the lat-kers that were equipped with air-tight lids. After ter PCP sample. Because the PCP specimen that the resin beads settled in the PCP containers, a contained the smaller quantity of Portland Type thin layer of free-standing water, not more than I-P cement had not set up as hard as the other PCP 1/8-in. thick, covered the beads. The first step in sample, five additional PCP specimens were pre-preparing the PCP samples involved raising the pared on October 23.
pF1 of the resin. This initial pH adjustment was accomplished using a proprietary pli-adjusting The procedure used on October 23 was the agent. The agent was added to each PCP sample same as that previously used, except that the in 2-g increments, and after each addition, the quantity of pil-adjusting agent added to each sample was stirred for 3 minutes, and the pil of sample was increased to 8 g. Two of these PCP the resin was measured. When the pil-adjusting samples were prepared using the same quantities agent was stirred into the resin samples, the free- of Portland cement that had been used on October standing water in each sample turned a burnt- 20; the remaining three PCP samples were pre-orange color. The initial pH of both of the PCP pared using 50,55, and 60 g of Portland cement.
resin samples was about 4, and following the CNSI personnel stated that the quantity of pil-addition of 6 g of the pil-adjusting agent to each adjusting agent added to the PCP specimens was PCP specimen, the pH of both samples was 10.5. increased to help drive off the ammonia. They ;
The pH of the two resin samples was monitored stated that the odor of ammonia was present when 1 for about 20 minutes following the last addition the PCP samples were prepared on October 20 of the pH-adjusting agent and, during this time, and that the smell was particularly strong in the the pH of both samples remained unchanged. In sample that contained the smaller quantity of all,38-l/2 g of flyash was then slowly added to Portland cement. The odor of ammonia was also each PCP sample, and each sample was then quite strong during the preparation of the new stirred for several minutes. Finally, two different PCP samples on October 23. When the final quantities of Portland Type I-P cement were then quantities of Portland cement were stirred into the stirred into the two PCP samples. The quantities five PCP samples, they were sealed, placed in an of Portland Type I-P cement that were added to oven that was maintained at 145 F, and baked the two samples,48 g and 71 g, spanned the ovemight to simulate the hydration exotherm.
range of concentrations that had been certified by CNSI. In each case, the cement was added in 20-g The following morning, the PCP specimens increments every 10 minutes. When the final were removed from the oven and examined. All amounts of cement were stirred into the samples, five of the samples were hard and did not contain they were sealed and placed in an oven that was any free-standing water. Based on the quality of maintained at 145 F, where they were baked these PCP samples, the decision was made to pro-overnight. ceed with the solidification of the three liners B-3 NUREG/CR-6164
Appendix B using the same formula used to prepare the PCP waste-form specimens. Between 2:35 and 3:05 sample containing the largest quantity of cement. p.m. on October 24,19 waste-form samples were EG&G Idaho personnel requested that liner prepared, which were 2 in. in diameter and 4 in.
446828-15 be solidified first. Since it contained long. Individual samples had contact exposure the highest concentrations of picolinic acid and rates of about 100 mR/ hour. The sample molds activation metals, for our leach testing purposes, were sealed immediately after they were filled,
( it was the best candidate of the three liners for and at 6:30 p.m. on October 24, they were all sampling. placed in an oven that was maintained at 145 F.
. Three of the waste-form specimens were The solidification of the ion-exchange resm.sm removed from the oven the following morning liner 446828-15 commenced on October 24, and were examined. All of the samples that were 1989, at 10:46 a.m. when the pH-adjusting agent removed had some free-standing water on their began to be added to the liner. A total of 550 lb of top surfaces. They felt firm but were certainly not TSP was added to the liner over an 8-mmut yet hard. These samples were then retumed to the period. The pH-adjusting agent reduced the vis-oven and all 19 specimens were baked at 145 F cosity of the resin as was evidenced by the drop in
, for a total time of about 72 hours8.333333e-4 days <br />0.02 hours <br />1.190476e-4 weeks <br />2.7396e-5 months <br />. When these the hydrauhc pressure needed to rotate the mixmg samples were examined by Peach Bottom-3 per-blades at 60 rpm. (The hydraulic pressure sonnel during the week of October 30, they were dropped from an mitial value of about 2,000 psig hard, and no free-standing water was visible on to about 1,400 psig after the pH-adjusting agent gg was added.) Following the additmn of the pH-adjusting agent, a total of 2,730 lb of flyash was The waste resins in the remaining two liners, I then added to the liner from i1:10 a.m. to 12:07 which were designated liners 446692-I and )
p.m. When this addition was completed, the 446828-10, were solidified after October 24 using j i material in the liner was stirred for about 20 min- the same solidification formula that had been utes without any new material being added to the used to solidify the ion-exchange resin in liner liner. At 12:27 p.m., the addition of Portland Type 446828-15. During the week of October 30, the I cement began. A total of 4,982 lb of Portland resin / cement mixtures in all three liners were Type I cement was added to the liner between visually examined, and the hardness of the resin /
12:27 p.m. and 1:52 p.m. After the last of the cement monoliths were tested with a broom han-Ponland cement had been added to the liner, the die. The surfaces of the monoliths in liners contents of the liner were mixed for a few minutes 446692-1 and 446828-10 were impenetrable, but before the mixing motor was shut down. The to everyone's surprise, the broom handle pene-quantities of resin and binder materials in the trated the material in liner 446828-15. A thin liner when the solidification operation was com- crust had formed over the top surface of the resin /
pleted are summarized in Table 3. cement mixture, but below the crust, the material had not yet solidified. CNSI personnel suggested After the fill-head was removed from the top of that ammonia in the resin /ccment mixture was the liner, the resin / cement mixture inside the liner retarding the setting of the cement. They recom-was sampled. This sampling tool, which was sim- mended that the liner be vented to help remove ply a plastic tube equipped with a plunger, was the ammonia. The Philadelphia Electric Com-inserted into the resin / cement mixture five or six pany followed the recommendation and began times to a depth of about 3 ft below the top sur- venting the liner the week of October 30. The face of the mixture. Following each insertion, the liner was not examined again until December 21, material inside the tube was transferred to a plas- 1989. On that date, the upper surface of the mono-tic-lined bucket. About 2 gal of resin / cement mix- lith was again probed with a broom handle, and ture was collected. The resin / cement mixture was this time, the broom haadle did not penetrate the quite fluid, which made it possible to pour the surface. During the week of January 15,1990, the material into the molds that were used to prepare wall of liner 446828-15 was drilled at three dif-NUREG/CR-6164 B-4
Appendix 11 ferent heights: about 4 in, from the top, near the employed to remove the plugs so that the surface center, and about 2 in. from the bottom. At the of the resin / cement monolith would not tx dam-lower two locations, a soft, slightly damp material aged during the pmcess of removing the plugs. At adhered to the groves in the drill bit when the bit all three locations where the plugs were removed, was withdrawn from the liner. Personnel from the the surface of the monolith was found to be Philadelphia Electric Company and the NRC w ho smooth and hard. The hardness of the surface of were present when the liner was drilled inter- the monolith was tested by pounding the point of preted the presence of the material on the drill bit a chisel against the surface. The surface was as meaning that the resin / cement mixture had not found to be impenetrable. Following this yet completely solidified
- examination, the CNSI solidification supervisor stated that he felt the liuer had hardened suffi-On February 6,1990, the condition of the ciently to allow it to be shipped to a disposal site. ,
material in liner 446828-15 was reexamined. The lie also suggested that the results of the examina, CNSI solidification supervisor who had super.
vised the solidification of all three liners during tion that had been performed during the week of October 1989 personally conducted the examina_ January 15 might have been misinterpreted. Ifis tion. At a h> cation on the liner wall opposite the point was that solidified ion-exchange resin waste location that had been previously drilled,1.5-in.. forms are not high-density concrete, and there-diameter plugs were removed from the liner wall fore, one would expect to be able to penetrate at three different heights. A hole saw was such waste forms using a high-speed drill.
B-5 NUREG/CR-6164
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i Appendix C
)
Detailed Procedures for 14C,99Tc, and 1291 Analysis i
i i 1 I
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! C-1 NUREG/CR-6164
Appendix C Appendix C Detailed Procedures for 14C,99Tc, and 1291 Analysis Samples of resin wastes and leachates are typi. Attachments 1 through 3 contain summaries of cally analyzed for radionuclides specified in the analytical proceedures used by B&W Nuclear 10 CFR 61 (i.e.,14C, 60Co, 63Ni,90Sr, M c,1291 , Environmental Services to perform the analyses 137Cs, 238 Pu, 239Pu, 241Am, and 244Cm) and for 14C, 99Tc,and 129.1 All procedural steps are other radionuclides using standard environmental included with the exception of laboratory-spe-analysis procudures. Radioanlytical procedures cific information, caluclational methods, and . ;
performed for the analysis of most of these radio- reporting requirements. Further information may l nuclides are specified in References 1 and 2; be obtained from B&W Nuiclear Environmental I however, the procedures for 14C, 99Tc,and 1291 Services at the Lynchburg Technology Center in are not included as only the Peach Bottom-3 sam- Lynchburg, Virginia.
pies have been analyzed for these radionuclides.
l C-3 NUREG/CR-6164
Appendix C REFERENCES
- 1. C. Mclsaac and J. Mandler, The Leachability of Decontamination lon Exchange Resins Solidified in Cement at Operating Nuclear Power Plants, NUREGlCR-5224, March 1989.
- 2. C. V. Mctsaac, D. W. Akers, and J. W. McConnell, Jr., Effect ofp// on the Release of Radionuclides and Chelating Agentsfrom Cement-Solidyicd Decontamination lon-Exchange Resins Collectedfrom Operating Power Stations, NUREG/CR-5601, June 1991.
NUREG/CR-6164 C-4
j Appendix C i
1 Attachment 1 B&W Nuclear Environmental Services, Inc. I j LYNCHBURG TECHNOLOGY CENTER TECHNICAL PROCEDURE i
I i
n j
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NUMBER TP-690 REV. NO. O TITLE TECliNETIUM-99 ANALYSIS d
C-5 NUREG/CR-6164
Appendix C 1.0 APPLICABILITY This procedure applies to all Nuclear Environmental Laboratories personnel who are involved with radioactive waste sample analysis.
2.0 SCOPE This procedure provides the steps necessary to identify and quantify the Technetium-99 in radioactive waste sent to burial sites for disposal. Based on the requirements set forth in the United States Code of Federal Regulations, Title 10 Part 61 (10 CFR 61)," Licensing Requirements for Land Dispos 11 of Low Level Waste, " radwaste samples must be analyzed for radionuclide concentration.
3.0 PROCEDURE
SUMMARY
These samples shall be processed under chain-of-custody requirements. Interlaboratory transfers of samples shall be accompanied by Intemal Chain-of-Custody (ICOC) fonns.
Sample aliquots are obtained from the gamma scan fraction which was prepared in the Gamma Scan Preparation Section of TP-398. The Tc-99 aliquot undergoes an oxidation-reduction process and tributyl phosphate extraction. Care must be taken to prevent volatilization of Tc-99.
All experimental information shall be recorded on Benchsheet 69(bl.
4.0 GLASSWARE Before beginning the separation procedure it is strongly recommended that you gather together and label all of the glassware necessary for the separation of Tc. (All glassware used in this separation procedure shall have been cleaned according to TP-655.)lt is also recommended that colored tape be used to color coordinate the spiked and unspiked samples of the same NEL number in order to reduce the possibility of cross-contamination. ALL LABELS MUST CONTAIN THE COMPLETE LABORATORY WORKING S AMPLE ID NUMBER. THIS NUMBER WILL CONSIST OF THE NEL # AND THE APPROPRIATE TAG NUMBERS (OR LETTERS OR SOME COMBINATION OF THE TWO) USED TO IDENTIFY THE ISOTOPE AND SEPARATION FRACTION.
The glassware listed below is the glassware that is expected to be used for each sample in a batch.
Multiply the amount of glassware by the number of samples (including replicate, QC, and reagent blank) which will be analyzed. This listing does not include miscellaneous glassware used for reagents or chemicals.
4.1 Two beakers and watch glasses of appropriate size (Note: >= 100 mL beakers recommended for soil samples due to the vigorous reaction that occurs)if the hot plate digestion procedure is to be used (Step 9.5).
4.2 Two quartz crucibles if the fumace method of digestion is used (Step 9.5).
4.3 Two funnels for sample filtration (Step 9.5.3).
4.4 Two beakers of appropriate size for the sample filtrate (Step 9.5.3).
4.5 Two 125 mL separatory funnels (larger funnels may be necessary for larger sample sizes)
(Step 9.5.3).
NUREG/CR-6164 C-6
- - -__ _ _ _ _ _ _ _ _ _ _ _ . - _ _ - - - - _ - - - - - - - - - .- .I
Appendix C 4.6 Two 15 mL polypropylene centrifuge tubes with caps (or equivalent)(Step 9.1l).
4.7 Two 4 mL class A pipets (or an appropriate Eppendorf or class A pipet of suitable volume capacity) (Step 9.13).
4.8 Two glass liquid scintillation vials (Step 9.13).
4.9 Two glass liquid scintillation vials for efficiency standard and background (Step 9.15).
5.0 REAGENTS l 5.1 6.0 N Sulfuric Acid (112S0 4)-Carefully add 167 mL of concentrated 11 S04 2 to a one liter volumetric Hask containing 500 mL of reagent grade water and dilute to one liter with reagent I grade water when the solution has cooled. Store in a plastic reagent bottle.
l 5.2 6.0 N II2 SO4-2 % liF(Sulfuric acid and ifydrofluoric acid)- Add 167 mL 11 S04 2 and 20 mL concentrated flF to 500 mL of reagent grade water and dilute one liter with reagent grade water. Cool. Store in a plastic bottle.
5.3 4.0 N IIydrr, chloric '. rid (IICI)- Add 333 mL of concentrated IICI to 500 mL of reagent grade waier and dilutu to one liter with reagent grade water when cool. Store in a plastic ;
bottle.
5.4 9 N (II 2SO 4)- Carefully add 250 mL of concentrated 11 2S04 ot a one liter volumetric flask containing 500 mL of reagent grade water and dilute to one liter with reagent grade water.
5.5 Tributyi Phosphate (TBP) (equilibrated) - Place 100.0 mL of TBP into a 250 mL separatory funnel and add 100.0 mL of 9 N H 2SO4, shake for 5 minutes, allow phases to separate, save TBP (the top layer) in a dark bottle, neutralize and discard the 9N li2 SO4.
5.6 Tc-99 Tracer - NIST traceable or calibrated against a NIST traceable standard.
5.7 Cobalt Carrier (5.0 mg Co/mL)- Dissolve 20 g CoCl 611 3 20 in 500 mL of 0.1 N hcl and dilute to one liter with 0.1 N llCl.
5.8 Cesium Carrier (5.0 mg Cs/mL)- Dissolve 6.3 g CsCl 2in 500 mL of 0.l N hcl and dilute to one liter with 0.1 N hcl.
5.9 Manganese Carrier (5.0 mg Mn/mL)- Dissolve 18.0 g MnCl 4H 2 2O in 500 mL of 0.1 N llCl and dilute to one liter with 0.1 N hcl.
5.10 1% Potassium Permanganate (KMnO4)(I g/100 mL)- Dissolve 5 g of KMNO4 in 400 mL of reagent water and dilute to 500 mL with reagent grade water.
5.11 0.1 N IICl- Add 8.3 mL of concentrated ilCl to 500 mL of reagent grade water and dilute to one liter with reagent grade water. Store in a plastic reagent bottle.
6.0 TECHNETIUM-99 SAMPLE PREPARATION AND ANALYSIS Sample aliquots shall be removed from the gamma scan fraction (TP 398, Section 9) unless otherwise indicated by the Project Leader. Any deviations from this procedure shall be documented on Benchsheet 690-1.
C-7 NUREG/CR-6164
Appendix C Each sample in a batch is processed in duplicate as a spiked and as an unspiked sample. Each spiked sample contains a known amount of a NIST traceable Tc-99 standard solution of- 100(X)0 dpm.
This separation should be performed in a fume hood as Technetium may be volatile.
6.1 Each batch of 10CFR61 samples processed must contain a QC sample, a reagent blank and a replicate of one sample for each batch of <= 10. If more than 10 but less than 20 samples are processed in a batch then a replicate of two samples must be processed.
6.2 QC Sample - A QC sample is a sample of a matrix similar to that of one of the samples being processed in the batch. Both the spiked and unspiked sample aliquots are spiked with a known amount of a NIST traceable Tc-99 radiotracer (~10,000-50,000 dpm). Whenever possible, use a QC stock sample. If a stock sample is not available, a QC sample may be prepared as follows:
6.2.1 Choose a matrix for the QC sample that will best represent a typical sample of the batch to be processed.
6.2.2 See Section 9.4 regarding recommended sample sizes.
6.2.3 Add a known amount of and NIST traceable Tc-99 standard to the QC sample matrix. Record the standard infomiation, aliquot size, pipet ID and error on Benchsheet 690-1.
6.3 Reagent Blank - A reagent blank is comprised of an aliquot of reagent grade water. NO RADIOTRACER SPIKE IS ADDED TO THE UNSPIKED REAGENT BLANK!
6.3.1 Up to 100 mL of Reagent Grade DI water is used.
6.3.2 Record the sample ID, size (in grams (g) and in milliliters (mL)) and the balance and pipet ids and errors Benchsheet 690-1.
6.4 Sample Aliquot size will vary depending on the sample matrix and the anticipated level of Tc-99 activity. See the Project Leader regarding the recommended sampling sizes. Record all sample ID, size (g or mL), balance or volumetric ID and error information on Benchsheet 690-1.
6.4.1 Single Phase Liquid Sample - typically use approximately 10-20 mL, but up to 100 mL of sample may be used in a 250 mL separatory funnel.
6.4.1.1 Accurately pipet a known volume of sample into a beaker of appropriate size or a quartz crucible (depending upon the digestion method used). Record the sample ID, the sample volume, the pipet ID and the pipet error on Benchsheet 690-1.
6.4.1.2 Prepare a duplicate for each sample adding ~100000 dpm of Tc-99 tracer.
Record the sample ID, volume, pipet ID and error, the Tc-99 standard ID and the volume and pipet ID and error on Benchsheet 690-1.
6.4.2 Two Phase Liquid Sample -Typical sample sizes may be 10-20 mL, however up to 100 mL may be required for samples of low activity.
NUREG/CR-6164 C-8
Appendix C 6.4.2.1 Weigh an empty beaker of appropriate size or a quartz crucible. Record the balance ID and error and the weight of the empty container (Tare Weight) on Benchsheet 6%I.
6.4.2.2 Pipet a known volume into the sample container.
6.4.2.3 Reweigh the container and sample.
6.4.2.4 Record the sample ID, the pipet ID and error, the weight and the volume on Benchsheet 690-1.
6.4.2.5 Prepare a duplicate of each sample adding ~ 100000 dpm of a NIST traceable Tc-99 radiotracer. In addition to the information requested above, record the standard ID, volume added, pipet ID and error on Benchsheet 6%1.
6.4.3 Solid Sample-Typical sample sizes may be 1-3 g, however a larger aliquot (~ 10 g) may be necessary for samples of expected low Tc-99 activity.
6.4.3.1 Typical sizes: mixed Resin (1-3 g), Glter paper (0.5 g) (depending on the amount of sample provided and its anticipated activity) and Soils (1-10 g).
NIST traceable soil-type standards typically use 1-3 grams. Larger sample sizes may be recommended by the Project Leader.
6.4.3.2 Weigh an empty beaker of appropriate size (100-150 mL recommended for soils) or a quartz crucible. Record the balance ID and error and the weight of the empty container (Tare weight) on Benchsheet 6%1.
6.4.3.3 Transfer a sample aliquot to the empty container and reweigh. Record the sample ID and weight on Benchsheet 6%1.
6.4.3.4 . Prepare a duplicate of each sample adding ~100000 dpm of Tc-99 radiotracer. In addition to the information requested above, record the l standard ID, volume added, pipet ID and error on Benchsheet 6W1.
6.5 Sample Digestion - Samples shall be digested using one of the following methods. Record all information on Benchsheet 6%1, including reagent lot numbers, which method of digestion was used and any deviations.
6.5.1 Muffle Furnace Digestion: add 15 mL of concentrated ammonium hydroxide
(.Nif 40ll) to the quartz crucible containing the sample. Slowly evaporate on a hot plate to dryness.
6.5.1.1 Ignite in a muf0e furnace at 400 C for two hours. Allow to cool.
6.5.1.2 Add 15 mL of 6N 11 2S04 and 2 grams of potassium persulfate (K 22 S 0g).
Boil the sample for 20 minutes.
6.5.1.3 Proceed to Step 9.5.3.
i 6.5.2 flot Plate Digestion: for every 3 grams of sample add the following to the sample in j
the 150 mL beaker:
C-9 NUREG/CR-6164 i
Appendix C 6.5.2.1 5 mL of concentrated nitric acid (IINO3 ),5 mL D1 water and ~1. 5 g of K22 S 0s.
CAUTION: These chemicals should be added carefully as a vigorous reaction may occur.
6.5.2.2 Cover the beakers with a watch glass and gently reflux on a hot plate for
> 1 hour1.157407e-5 days <br />2.777778e-4 hours <br />1.653439e-6 weeks <br />3.805e-7 months <br />. (The samples may also be allowed to sit overnight followed by a gentle reflux for ~1 hour.) CAUTION: The addition of heat may initiate a vigorous reaction. Observe the reflux process periodically to ensure samples do not overflow the beakers.
6.5.2.3 Proceed to Step 9.5.3.
6.5.3 Filter the cooled leachate through a Whatman #541 (or equivalent) filter paper into a beaker of an appropriate size.
6.5.3.1 Add 0.5 mL of Cesium and Manganese carriers and 1.0 mL of Cobalt carrier.
6.5.3.2 Wash the residue with sufficient 6 N H2 SO4to give a final volume of 45-50 mL.
6.5.3.3 Quantitatively transfer the sample to a l25 mL separatory funnel (or targer if needed) using 6N li 2SO4 to effect the transfer.
6.5.3.4 Add 10 mL of concentrated ll2SO4 and sufficient 1% KMnO4 solution to maintain a pink color.
6.5.3.5 Proceed to Step 9.6.
6.6 CAUTION
Sample may become hot, wait until sample is cool to the touch before continuing.
6.7 Pipette 5.0 mL of concentrated tributyl phosphate (TBP) that has been previously equilibrated with 9 N H SO4 2 into the separatory funnel (Step 8.5). Record reagent lot numbers, pipet ID and error on Benchsheet 690-1.
6.8 Shake for two minutes, allow phases to separate, drain the aqueous phase (the lower phase) and discard in the appropriate radioactive waste container.
6.9 Wash the TBP with 2.5 mL of 6 N sulfuric acid - 2 % hydrofluoric acid (H2 SO4-ilF), shake for approximately two minutes. Allow the phases to separate and drain the aqueous phase (the lower phase) and discard in the appropriate radioactive waste container.
6.10 Wash the TBP solution with 25 mL of 4 N hydrochloric acid (hcl) and shake for about two minutes. Allow the phases to separate for 10 miautes so that sufficient extract (TBP) will be available for counting.
6.11 Drain and discard the aqueous phase and transfer the extracts (TBP) to a 15 mL centrifuge tube.
NUREG/CR-6164 C-10
Appendix C 6.12 Centrifuge for 2 to 3 minutes to obtain a clear extract 6.13 Accurately pipette 4.0 mL (or an amount reasonably available) of extract into a scintillation vial and add 12.0 mL of scintillation cocktail. Record the volume of TBP recovered (pipet ID and error) and cocktail lot number on Benchsheet 690-1.
6.14 If a prepared c fficiency standard and liquid scintillation background sample are available, proceed to 5:;p 9.17.
6.15 Prepare a counting efficiency standard by placing a known amount of a NIST traceable Tc-99 standard (~100000 dpm), enough TBP to give a 4 mL total volume and 12.0 mL of scintillation cocktail into a scintillation vial. Label the vial with an efficiency ID. Record the sample ID, the standard ID, volume added, reagent lot numbers, pipet ID and error information on Benchsheet 690-1.
6.16 Prepare a background by placing 4.0 mL of TBP and 12.0 mL of scintillation cocktail into a scintillation vial. Label the vial as a sample background. Record the sample ID, the reagent lot numbers, pipet ID and error information on Benchsheet 690-1.
I 6.17 Transfer the samples, efficiency standard and background to the counting room for liquid scintillation analysis with a completed ICOC.
1 C-1I NUREG/CR-6164
Appendix C Attachment 2 B&W Nuclear Environmental Services, Inc.
LYNCHBURG TECHNOLOGY CENTER TECHNICAL PROCEDURE NUMBER TP-493 REV. NO. O TITLE l-129 ANALYSIS NUREG/CR-6164 c-13
Appendix C 1.0 APPLICABILITY .
This procedure applies to all Nuclear Environmental Laboratories personnel who are involved with radiochemical separations.
l 2.0 SCOPE l This procedure provides the steps necessary to identify and quantify the lodine-129 in radioactive l waste sent to burial sites for disposal. Based on the requirements set fonh in the United States Code of Federal Regulations, Title 10 Pan 61 (10 CFR 61)," Licensing Requirements for Land Disposal of i
Low Level Waste," radwaste samples must be analyzed for radionuclide concentration.
3.0
SUMMARY
OF METHOD The sample is fused with sodium hydroxide (NaOH), oxidized with sodium hypochlorite (NaOCl) .
and extracted using either carbon tetrachloride (CCl.3) or chloroform (CHCl 3 ). It is then back-extracted into sodium bisulfite (NallS03) and precipitated using silver nitrate ( AgNO3). The 1-129 is quantitated using a Low Energy Photon Spectrometer (LEPS) detector at 29.7 kev or 39.5 kev. The sample yield is determined chemically with a natural iodine carrier. The sample yield is determined chemically with a natural iodine tracer measured gravimetrically or by ion chromatography.
3.1 Sample aliquots are obtained from the gamma scan fraction which was prepared in TP-393.
The 1-129 aliquot undergoes a solvent extraction separation.
3.2 All experimental information shall be recorded on Benchsheet 693-1 or the appropriate
. Notebook.
4.0 GLASSWARE Before beginning the separation procedure it is strongly recommended that you gather together and label all of the glassware necessary for the separation ofiodine. ( All glassware used in this separation pmcedure shall have been cleaned according to TP-655.) ALL LABELS MUST CONTAIN THE COMPLETE WORKING LABORATORY SAMPLE NUMBER.
The glassware listed below is the glassware that is expected to be used for each sample in a batch. This listing does not include miscellaneous glassware to be used for reagents or chemicals.
SAMPLES 4.1 One nickel crucible.
4.2 One filter funnel.
4.3 One 250 mL beaker.
4.4 Two 250 mL separatory fannels (or appropriate size).
4.5 One 25 mL volumetric flask.
4.6 One 50 mL beaker, c-14 NUREG/CR-6164.
l Appendix C j_
4.7 Two liquid scintillation vials.
l 4.8 One 1 1/4" flat planchet.
4.9 One plastic petri dish.
4.10 One 10 mL volumetric flask.
EFFICIENCY STANDARDS 4.11 Two - Three 50 mL beakers.
4.12 Two - Three 1 1/4" flat planchets.
4.13 Two - Three plastic petri dishes.
CARRIER 4.14 One 25 mL volumetric flask.
4.15 One 10 mL volumetric flask.
5.0 REAGENTS 5.1 lodine Carrier (10 mg I/mL)- Dissolve l 3.0 g potassium iodide (KI) in 500 mL of reagent l grade water and dilute to one liter with reagent grade water.
l 5.2 5% Sodium Hypochlorite (NaOCI)- Purchase a prepared solution from an approved vendor.
5.3 5% Sodium Hydroxide (NaOH)- Dissolve 50 g of NaOH in 400 mL of reagent grade water and dilute to one liter with reagent grade water after allowing the solution to cool.
5.4 20% Sodium Ilisulfite (NaHS03)- PREPARE FRESH JUST PRIOR TO USE-Dissolve 1.04 g NaHS03 in 5 mL of reagent grade water and dilute to 10 mL with reagent grade water.
j 5.5 0.1 N Silver Nitrate Solution (AgNO )- 3 Purchase a prepared solution from an approved vendor.
5.6 I 129 Tracer - NIST traceable or calibrated against a NIST traceable standard.
l
! 5.7 Ethyl Alcohol (ETOH).
5.8 Sodium Hydroxide (NaOH).
6.0 IODINE-129 SAMPLE PREPARATION AND ANALYSIS Sample aliquots shall be removed from the gamma scan fraction unless otherwise indicated by the project leader. Any deviations from this procedure shall be documented on Benchsheet 693-1 or in the appropriate notebook.
6.1 Each sample batch processed must contain a QC sample, a reagent blank, and a replicate of one sample for each batch of s 10. If more than 10 but less than 20 samples are processed in a l
batch then a replicate of two samples must be processed.
NUREG/CR-6164 c-15 l
l Appendix C 6.2 Laboratory Control Sample - A laboratory control sample is a sample comprised of an i approximation of the matrix of one of the samples being processed in the batch. It is spiked l with a known amount of I- 129 radiotracer. Whenever possible, use a laboratory control stock !
sample. If no laboratory control available, the laboratory control sample may be prepared as follows. ,
1 l 6.2.1 Choesc a matrix for trie laboratory control sample that will best represent a typical sample of the batch to be processed.
l 6.2.2 See Section 10.4 regarding recommended sample sizes. !
6.2.3 Add a known amount of a NIST traceable I-129 standard to the laboratory control i sample matrix. Record the laboratory control sample preparation information.
l 6.3 Reagent Blank - A reagent blank is comprised of an aliquot of reagent grade water. NO RADIOTRACER SPIKE IS ADDED!
6.3.1 Up to 250 mL of Reagent Grade DI water is used. Record all sample information.
6.4 Sample Aliquot size will vary depending on the sample matrix and the anticipated level of I 129 activity. See the Project Leader regarding the recommended sampling sizes. Record all sample information.
6.4.1 For a Single Phase Liquid Sample - Shake the sample to homogenize. Liquid samples typically use approximately 1(L20 mL, but up to 250 mL of sample may be used in a 500 mL beaker. Add 1.0 mL iodide carrier (approximately 18 mg) and proceed with Step 10.6 of this procedure. Record the carrier information.
1 i
6.4.2 If the Sample is a Two-Phase Liquid - Shake the sample to homogenize. Pipet a known aliquot of 1(L20 mL or up to 40 mL into a nickel crucible. Record all sample information.
6.4.3 If the Sample is a Solid-accurately weigh an appropriate amount of the sample into a nickel crucible. Typical sample sizes may be 1-3 g, however a larger aliquot
(~10 g) may be necessary for samples of expected low I-129 activity. Record all sample information.
6.4.3.1 Mixed Resin - typically use 1-3 g.
6.4.3.2 Filter paper - typically use 0.5 g, depending on the amount of sample provided and its anticipated activity.
6.4.3.3 Soils- A clean, characterized soil sample typically uses 1-5 grams. NIST traceable soil-type standards typically use ~1 gram. Larger sample sizes may be recommended by the Project Leader.
6.5 Sample Preparation - Record all information on Benchsheet 693-1 or the appropriate Notebook.
6.5.1 Add 1.0 mL of iodide carrier (approximately 18 mg) to the sample.
Q-16 NUREG/CR-6164 l
' Appendix C 6.5.2 Add 4.0 mL of DI water,3.0 mL of ethyl alcohol and 10.0 g of sodium hydroxide (NaOH).
6.5.3 Heat gently on a hot plate or equivalent, until all alcohol has been evaporated.
6.5A Place the crucible in a fumace and slowly raise the temperature to 600 C over a 2-3 hour period. Hold the temperature at 600 C for 2 hours2.314815e-5 days <br />5.555556e-4 hours <br />3.306878e-6 weeks <br />7.61e-7 months <br />.
NOTE: If using a 75 mL nickel crucible, place the crucible on a tray prior to placing it in the muffle furnace. It has been found that when the crucible bottom rests on the bottom of the furnace, the combination of heat and chemicals causes a weakening (possible leaks)in the crucible.
6.5.5 Cool the crucible and add approximately 15 mL of reagent grade water. Boil to .
dissolve the melt.
6.5.6 Filter the dissolved liquid through a Whatman # 41 or equivalent filter paper,into a 250 mL beaker.
6.5.7 Repeat Steps 10.5.5 and 10.5.6 until all of the melt has been dissolved and filtered. If . ,
the sample will not completely dissolve proceed to Step 10.5.8. If complete l dissolution is attained proceed to Step 10.6. ;
i 6.5.8 Return the sample (in the filter paper) to the crucible and add 15 mL of 5% NaOH solution.
6.5.9 Heat the solution in the crucible for about 30 minutes to dissolve the melt, 6.5.10 Filter the solution through a Whatman 41 or equivalent filter paper. Combine the filtrate with that from Step 10.5.6.
6.5.11 Stir the filtered solution for ~20 minutes.
i 6.6 C A UTION: The following step MUST be performed in a hood. While stirring, add 20 mL of 5% sodium hypochlorite (NaOCl or household bleach) solution. Next add concentrated nitric acid (HNO 3) until the pH of the solution is about 1. If the sample was treated with NaOH over i 20 mL of concentrated HNO 3will be required. When proper pH has been reached, all visible reaction will cease and solution will become yellowish to clear in color.
SPECIAL NOTE: This step must be performed in a fume hood because toxic chlorine gas is evolved. This-oxidizes the iodide to iodine so that it may be extracted by the carbon tetrachloride or chloroform. At this time chloride contaminants should be removed by oxidation of the chloride to chlorine gas - which volatilizes. Bromide should remain in its oxidation state to be separated during the extraction to follow.
6.7 Transfer the solution to a 250 mL separatory funnel labeled A.
NOTE: If the sample is a liquid with'a volume greater than 100 mL use a 500 mL separatory funnel. Effect the transfer with D1 H2 0.
6.8 Add 2 grams of hydroxylamine hydrochloride (H2 NOHHCl) and 50.0 mL of carbon tetrachloride (CCl4) or chloroform (CHCl 3) to the separatory funnel. Stopper only after bubbling stops. Gently agitate and release pressure before proceeding to Step 10.8.
NUREG/CR-6164 c-17
Appendix C l
NOTE: Due to new restrictions on the use of CCla, conversion to another extractant is necessary. See the Project Leader to determine when this conversion is to be made and the !
extractant to be used if other than CCl4 .
6.9 Shake the funnel for 2 minutes and drain the organic phase (lower layer) into a 250 mL separatory funnel labeled B. It may take several minutes for complete phase separation to occur.
NOTE: The organic phase will.become pink in the presence of iodine.
6.10 Add I g of hydroxylamine hydrochloride and 50 mL of CCl to 4 the aqueous phase in funnel A l and re-extract by shaking for 2 minutes.
6.11 Allow phase separation to occur. Drain the organic phase (lower phase) into funnel B. ;
Discard the aqueous phase in funnel A into the appropriate radioactive waste container.
6.12 Add 20 mL of DI water and 10 drops of freshly prepared 207c sodium bisulfite (NaHSO3 ) to i the funnel B containing the organic phase and shake for 2 minutes. This will strip the iodine l from the organic phase into the aqueous phase. Drain and discard the organic phase into the l appropriate radioactive waste container. l 6.13 Transfer the aqueous phase into a clean labeled 25 mL volumetric flask. Dilute to the mark with DI water. Transfer the solution into a 50 mL beaker. Remove a 1.0 mL aliquot and transfer to a syringe fitted with an Acrodisc filter (0.45 pm,10 mm). Filter into a labelled scintillation vial for use later in the IC yield analysis. Record all information.
6.14 Add 1 mL of concentrated HNO3 and 2 mL of 0.1 N silver nitrate ( AgNO3) solution to the beaker. Mix well and allow to stand for ~5 minutes.
6.15 Weigh a labelled 1 1/4" planchet with a 0.45 pm glass fiber millipore or equivalent filter along with a piece of two sided tape. Record the weight infonnation. (The sample will be mounted on the BOTTOM of the planchet, therefore label the top side of the planchet.)
6.16 Using a 25 mm filter funnel, filter with suction through the preweighed 0.45 pm glass fiber filter using DI water to effect the transfer. Wash the precipitate with 5 mL of DI water.
6.17 Secure the filter paper on the preweighed planchet with the two sided tape. Weigh ihe planchet to the nearest 0.1 mg. Air dry the sample for ~30 minutes. Record the weight.
6.18 Cover the planchet with x-ray film using tape to hold the film in planchet. Label the tape.
6.19 If no prepared efficiency standards are available, prepare 2--31-129 standard planchets (one for each available LEPS detector) as follows:
6.19.1 Add 25 mL of D1 water,1.0 mL ofiodide carrier (from the same carrier stock solution as used in the analysis of the samples) and an aliquot of an MST traceable 1-129 radiotracer solution of ~40,000 dpm. Record all standard preparation information.
6.19.2 Proceed with Steps 10.13-10.17.
c-18 .NUREG/CR-6164
Appendix C l 7.0 YlELD ANALYSIS .
l 7.1 Remove 0.2 mL of the yield aliquot from Step 10.12 and dilute to 10 mL with D1 water.
Transfer the solution through an Acrodisc / syringe (0A5 pm,10 mm acrodisc) filtration apparatus to a clean labelled scintillation vial for transfer to the analytical laboratory using a completed ICOC form for analysis by ion chromatography. Record all yield information and error information.
7.2 Prepare a 100% iodide carrier solution as follows:
7.2.1 Add 20 mL of DI water and 1.0 mL of the iodide carrier stock solution used for the sample analyses to a 25 mL volumetric flask. Record the volumetric error.
l 7.2.2 Transfer the solution to a 50 mL beaker. Remove 1.0 mL of solution to a labeled scintillation vial.
7.2.3 Place a 0.2 mL of the aliquot from Step i 1.2.1 in a 10 mL volumetric flask and dilute to the mark with DI water. Transfer the solution to a clean, labeled scintillation vial and transfer to the analyticallaboratory with the samples from Step 11.1. Record all carrier information.
7.3 Transfer the samples and standards to the counting room along with a completed ICOC form.
NUREG/CR-6164 C-19
i Appendix C l
)
1 i
I Attachment 3 l B&W Nuclear Environmental Services, Inc. i LYNCHBURG TECHNOLOGY CENTER l TECHNICAL PROCEDURE 1
4 e
i NUMBER TP-691 REV. NO. O TITLE Carbon-14ffritium Analysis for 10 CFR 61 c-20 NUREG/CR-6164
Appendix C 1.0
SUMMARY
OF METHOD Sample aliquots are obtained from the gamma scan fraction which was prepared in TP-398. The C-14/H-3 aliquot undergoes oxidation, separation, and collection as carbon dioxide and water respectively.
All experimental information shall be recorded on Benchsheet 691-1 or in the appropriate notebook.
2.0 EQUIPMENT All reusable glassware used in this separation procedure shall be cleaned according to TP-655.
2.1 One ion-exchange column (at least 0.5X15 cm) with stopcock, per 11-3 sample (including blanks and recovery samples).
2.2 Six liquid scintillation vials per sample (including blanks and recovery samples).
2.3 Four liquid scintillation vials for efficiency and background standards.
2.4 Oxidizer, Packard Instruments, or equivalent.
2.5 Packard "combusto-cones or equivalent.
3.0 REAGENTS 3.1 IRN-150 resin or equivalent. Crack the resin slightly. Condition the resin with reagent grade water. Shake, then allow the resin to settle. Decant and discard the water along with any fine resin particles. Store the resin in reagent grade water as a slurry.
3.2 Packard Permafluor E/Permafluor V or equivalent C-14 cocktail.
3.3 Packard Carbosorb C-14 cocktail or equivalent.
3.4 Instagel scintillation cocktail or equivalent.
3.5 C-14 Standard - NIST traceable or calibrated against a NIST traceable standard.
3.6 11-3 Standard - NIST traceable or calibrated against a NIST traceable standard.
3.7 Methanol 3.8 Industrial grade nitrogen or equivalent.
3.9 Industrial grade oxygen or equivalent.
4.0 C-14/H-3 SAMPLE PREPARATION Sample aliquots shall be removed from the gamma scan fraction prepared in TP-398 unless otherwise indicated by the Project Leader. Any deviations from this procedure shall be documented on Benchsheet 691-1 or in the appropriate Notebook.
NUREG/CR-6164 c-21
Appendix C 4.1 Each sample batch processed must contain a laboratory control sample, a reagent blank, and a replicate of one sample for each batch of s 10. If more than 10 but fewer than 20 samples are processed in a batch, then a replicate of at least two samples must be processed.
4.2 Laboratory Control Sample-This sample is comprised of an approximation of the matrix of one of the samples in the batch. It is spiked with a known amount of C-14/II-3 radiotracer.
Whenever possible, use a QC stock solution. If no QC stock solution is available, a laboratory control sample may be prepared as follows:
4.2.1 Choose a matrix that will best represent a typical sample of the batch to be processed.
4.2.2 See Section 10.4 regarding recommended sample sizes.
4.2.3 Add a known amount of a NIST traceable C-14/H-3 standard to the appropriate matrix. Record all information.
4.3 Reagent Blank - A reagent blank is comprised of a combusto-cone and combust-aid pad or equivalent. NO RADIOTRACER SPIKE IS ADDED!
1 4.4 Sample Preparation - Record all information on Benchsheet 691-1 or the appropriate Notebook.
4.4.1 For a Single Phase Liquid - Shake the sample to homogenize. Pipet up to 0.5 mL into a prepared combusto cone just before analysis. Record all sample information.
4.4.2 For a Two-Phase Liquid - Shake the sample to homogenize. Pipet up 100.5 mL into a prepared, preweighed combusto cone just before analysis. Immediately reweigh the cone containing the sample. Record all sample information.
4.4.3 For a solid sample - Accurately weigh a prepared combusto-cone. Place up to 0.5 g of homogenized sample into the cone and immediately reweigh. Record all sample infonnation.
4.5 Sample Analysis 4.5.1 OX1DIZER START UP: Tum on the Nitrogen and Oxygen gas (at the bottle and at the instrument).
4.5.2 Check the methanol bottle to insure that the level is adequate (~2/3 full) and the tube is submerged.
i CAUTION: IX) NOT OVERFILL THE BOTTLE.
4.5.3 With the power off, remove the overCow trap and replace the glass wool contained therein. Reconnect the trap. CAUTION: TO PREVENT PERSONAL INJURY THE POWER MUST BE OFF BEFORE PERFORMING THIS TASK.
4.5.4 Turn the oxidizer power on and allow ~10 minutes for the instrument to warm up.
During this time check all fluid levels and make additions as necessary. To facilitate cap removal, be sure that the vent / pressure switch is in the vent position and the pumps are off. Each reservoir should be at least half full before operation begins.
c-22 NUREG/CR-6164 l
l .. - . . . _-
. -. . . - . .. - -- = - -- -
Appendix C l 4.5.5' After the warm up period, check the fluid dispensig levels by first switching the
- vent / pressure switch to the on position then toggle each resenoir on/off switch to the on position one at a time to check the volume dispensed. For example, tum on the reagent grade water, leaving the Permalluor and Carbosorb off. Initiate a bum cycle and collect the eluate. Repeat this sequence with the Permafluor and Carbosorb until all liquid levels are producing the desired volume. The optimum volumes are as follows:
REAGENT GRADE WATER = 5 mL PERMAFLUOR = 10 mL CARBOSORB = 5 mL Once all fluids are yielding the desired volume, switch all on/off switches to the on position. The instrument is now ready for operation.
4.6 Preanalysis Blank 4.6.1 PREANALYSIS BLANK ALIQUOT: Remove the caps from two scintillation vials and place the vials into the sample collection slots on the oxidizer. Set the oxidizer bum time for the desired length of time. Place a combusto-cone and pad into the combustion basket and initiate the bum cycle.
4.6.2 Label the caps, removed from the scintillation vials, with the appropriate working lab numbers. When the bum cycle is complete, secure the caps on the appropriate ;
I vials. The C-14 fraction is ready for analysis. The H-3 fraction must be passed through a cation exchange clean-up column before analysis.
4.6.3 PREANALYSIS BLANK #1: Remove the caps from two scintillation vials and place the vials into the sample collection slots on the oxidizer. Set the oxidizer bum time for the desired length of time and initiate the burn cycle.
4.6,4 Label the caps, removed from the scintillation vials, with the appropriate working lab numbers. When the burn cycle is complete, secure the caps on the appropriate vials. The C-14 fraction is ready for analysis. The H-3 fraction must be passed through a cation exchange clean-up column before analysis.
4.6.5 PREANALYSIS BLANK #2: Remove the caps from two scintillation vials and place the vials into the sample collection slots on the oxidizer. Set the oxidizer bum time for the desired length of time and initiate the bum cycle.
4.6.6 Label the caps, removed from the scintillation vials, with the appropriate working lab numbers. When the burn cycle is complete, secure the caps on the appropriate vials. The C-14 fraction is ready for analysis. The H-3 fraction must undergo a cation exchange clean-up column before analysis.
4.7 Sample Aliquot 4.7.1 SAMPLE ALIQUOT: Remove the caps from two scintillation vials and place the vials into the sample collection slots on the oxidizer Set the oxidizer bum time for the desired length of time. Place the combusto-cone containing the sample into the combustion basket and initiate the bum cycle.
NUREG/CR-6164 c-23 k....
Appendix C 4.7.2 Label the caps, removed from the scintillation vials, with the appropriate working lab numbers. When the bum cycle is complete, secure the caps on the appropriate vials. The C-14 fraction is ready for analysis. The 11-3 fraction must be passed through a cation exchange clean-up column before analysis.
4.7.3 S AMPLE BLANK #1: Remove the caps from two scintillation vials and place the vials into the sample collection slots on the oxidizer. Set the oxidizer burn time for the desired length of time.
4.7.4 Label the caps, removed from the scintillation vials, with the appropriate working lab numbers. When the burn cycle is complete, secure the ccps on the appropriate vials. The C-14 fraction is ready for analysis. The 11-3 fraction must be passed through a cation exchange clean-up column before analysis.
4.7.5 S AMPLE BLANK #2: Remove the caps from two scintillation vials and place the vials into the sample collection slots on the oxidizer. Set the oxidizer burn time for the desired length of time.
4.7.6 Label the caps, removed from the scintillation vials, with the appropriate working lab numbers. When the bum cycle is complete, secure the caps on the appropriate vials. The C-14 fraction is ready for analysis. The 11-3 fraction must be passed through a cation exchange clean-up column before analysis.
4.7.7 Repeat Section 10.7 for each sample in the batch then proceed to Step 10.8.
4.8 Carbon 14 Recosery 4.8.1 C-14_ RECOVERY AllQUOT: Remove the caps from two scintillation vials and place the vials into the sample collection slots on the oxidizer. Set the oxidizer bum time for the desired length of time. Place a combusto-cone with pad into the combustion basket. Pipet the appropriate amount of C-14 tracer (~20,000 dpm) into the cone and initiate the burn cycle, 4.8.2 Label the caps, removed from the scintillation vials, with the appropriate working lab numbers. When the burn cycle is complete, secure the caps on the appropriate vials. The C-14 fraction is ready for analysis. The H-3 fraction must be passed through a cation exchange clean-up column before analysis.
4.8.3 C-14 RECOVERY BLANK #1: Remove the caps from two scintillation vials and place the vials into the sample collection slots on the oxidizer. Set the oxidizer bum time for the desired length of time and initiate the bum cycle.
4.8.4 Label the caps, removed from the scintillation vials, with the appropriate working lab numbers. When the bum cycle is complete, secure the caps on the appropriate vials. The C-14 fraction is ready for analysis. The H-3 fraction must be passed through a cation exchange clean-up column before analysis.
4.8.5 C-i4 RECOVERY BLANK #2: Remove the caps from two scintillation vials and placc the vials into the sample collection slots on the oxidizer. Set the oxidizer bum time for the desired length of time and initiate the bum cycle.
C-24 NUREG/CR-6164
_ ~~
Appendix C 4.8.6 Label the caps, removed from tbc scintillation vials, with the appropriate w lab numbers. When the bum cycle is complete, secured the caps on the app vials. The C-14 fraction is ready for analysis. The H-3 fraction must be passe through a cation exchange clean-up column before analysis.
4.9 Tritium Recovery 4.9.1 H-3 RECOVERY ALIQUOT: Remove the caps from two scintillation vi place the vials into the sample collectioni hslots pad intoon the the oxidizer. Set t time for the desired length of time. Place a combusto-cone d w) into t
combustion basket. Pipet the appropriate amount of H-3 tracer (~20,000 pm the cone and initiate the bum cycle.
4.9.2 Label the caps, removed frorn the scintillation vials, with the appropriate lab numbers. When the burn cycle is complete,besecure passed the caps on the a vials. The C-14 fraction is ready for analysis. The H-3 fraction must through a cation exchange clean-up column before analysis.
4.9.3 H-3 RECOVERY BLANK #1: Remove the caps from two scintillation v place the vials into the sample collection slots on the oxidizer. Set t time for the desired length of time and initiate the burn cycle.
4.9.4 Label the caps, removed from the scintillation vials, with the appropriate w lab numbers. When the burn cycle is complete, secure be passed the caps on the a vials. The C-14 fraction is ready for analysis. The 11-3 fraction must through a cation exchange clean-up column before analysis.
4.9.5 H-3 RECOVERY BLANK #2: Remove the caps from two scintillation via place the vials into the sample collection slots on the oxidizer. Set th time for the desired length of time and initiate the burn cycle.
4.9.6 Label the caps, removed from the scintillation vials, with the appropriate lab numbers. When the bum cycle is complete, secured the caps on the a vials. The C-14 fraction is ready for analysis. The H-3 fraction must be passe through a cation exchange clean-up column before analysis.
4.10 Postanalysis Blank 4.10.1 POSTANALYSIS BLANK ALIQUOT: Remove the caps Set the from two scintilla vials and place the vials into the sample collection slots ond the oxidizer.
oxidizer burn time for the desired length of time. Place a combusto-cone w into the combustion basket and initiate the burn cycle.
4.10.2 Label the caps, removed from the scintillation vials, with the appro lab numbers. When the burn cycle is complete, secure dthe caps on the a vials. The C-14 fraction is ready for analysis. The H-3 fraction must be passe through a cation exchange clean-up column before analysis.
4.10.3 POSTAN ALYSIS BLANK #1: Remove the caps from two scinti place the vials into the sample collection slots on the oxidizer. Se time for the desired length of time and initiate the burn cycle. .
- c-25 NUREG/CR-6164 l
r-Appendix C 4.10.4 Label the caps, removed from the scintillation vials, ng with the appropria lab numbers. When the burn cycle is complete, secure the caps on the vials. The C-14 fraction is ready for analysis. The !!-3 fraction must be p through a cation exchange clean-up column before analysis 4.10.5 POSTANALYSIS BLANK #2: Remove the caps from two scintillation vials a place the vials into the sample collection slots on the oxidizer. Set the oxidize time for the desired length of time and initiate the burn cycle.
4.10.6 Label the caps, removed from the scintillation vials, with the appro lab numbers. When the burn cycle is complete, secure the caps on the a vials. The C-14 fraction is ready for analysis. The 11-3 fraction must be pa through a cation exchange clean-up column before analysis.
4.11 Efficiency Standards 4.11.1 if no prepared efficiency standards are available, prepare a C-14 and/or a H 3 standard as follows: For CAR BON- 14, pipet a known amount (~20,000 dpm) appropriate NIST traceable standard into a labeled scintillation vial containin mL of Permafluor and 5 mL of Carbo-sorb (or equivalent). Shake well. For TRITIUM pipet a known amount (~20,000 dpm) of the appropriate NIST trac standard into a labeled scintillation vial containing 10 mL of reagent grade wat Add 10 mL of Instagel or equivalent. Shake well.
4.12 Background Standards 4.12.1 If no prepared background standards are available, prepare a C-14 and/or -
standard as follows: For CARBON-14, pipet 10 mL of Permafluor and 5 mL o Carbo-sorb into a labeled scintillation vial. Shake well. For TRITIUM pipet of reagent vial. Shake well.grade waterand 10 mL of Instagel or equivalent into a labeled sc 4.13 Tritium Purification 4.13.1 For each of the pre and postanalysis blanks, sample aliquots and recov ,
prepare a 10 cm resin bed using prepared IRN-150 resin (see reagents section preparation guidelines). Condition the column with 10 mL of reagent grade wa 4.13.2column Place a clean scintillation vial under the column.
and clute to the top of the resin. quat on Load the the sample ali 4.13.3 Load BLANK #1 on the column and clute to thense .
toptheof the resin Ri scintillation vial (for Blank #1) twice, with ~1 mL of reagent .
e grade water Contin collecting the cluate in the initial scintillation vial until 10 mL has been collecte 4.13.4 When 10 mLof cluate has been collected, replace the collection vial with th e rinsed, BLANK #1, scintillation vial.To the initial collection vial, add 10 mL ofinst equivalent). Place the appropriately labeled cap on the vial and shake well 4.13.5 Elute the rinse solution to the top of the resin.
C-26 NUREG/CR-6164
l Appendix C l l l
- 4.13.6 Continue collecting the eluate into the BLANK #1 vial until 10 mL of elute has been l l collected. Load BLANK #2 on the column and elute to the top of the resin. Rinse the l l scintillation vial (for Blank #2) twice, with ~1 mL of reagent grade water. Continue collecting the eluate in the BLANK #1 scintillation vial until 10 mL has been collected.
l 4.13.7 When 10 mL of eluate has been collected, replace the collection vial with the rinsed, l BLANK #2, scintillation vial. To the BLANK #2 collection vial, add 10 mL of instagel (or equivalent). Place the appropriately labeled cap on the vial and shake well.
- 4.13.8 Rinse the column with reagent water grade until 10 mL of eluate has been collected i l
in the BLANK #2 vial. I 4.13.9 Add 10 mL ofInstagel or equivalent to the vial (BLANK #2). Place the appropriately l labeled cap on the vial and shake well.
4.14 Wipe the exterior of all vials with a lint-free cloth to remove any particles that may interfere with the scintillation analysis.
4.15 Transfer all samples, efficiency and background standards to the Counting Room for Liquid Scintillation beta analysis. All transfers must be accompanied by a completed ICOC form.
c-NUREG/CR-6164 c-27
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Appendix D Leaching Data for Peach Bottom 1
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.I D-1 NUREG/CR-6164 1 -
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Appendix D 1
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Table D-1. Peach Bottom sample #4 cumulative fraction releases, release rates, effective diffusivities, and leachability indexes.
FIE NAME: C-14 SAWG 0: PEACH BOTTOM #4 I LEACH CUMULATNE ACTMTV RELEASE RELEASE RELEASE INCREMENTALCUMULATWE EFFECT1W LEACH O LEACH TIME LEACHED RATE RATE RATE REEASE RELEASE DIFFUSM1Y IPOEX (days) (uC4) (uCi*cm 8 ') (cm 8
- s ') p*y ') (cm8*s ') 1
. ...... .. .. .....'s----.... - ..... ...... .... . .... - .. 1 I
- 4. (1d) 1.00E +00 t aT-03 1.89E - 10 1.70E - 13 9 30E-07 1.61 E - OS 5.04E-05 8.77E-17 1.61E +01
- 5. pd) 2 0T+00 7.3aE-03 5.49E - 10 4.92E - 13 2.70E-OS 6 61E-(2 5.70E-06 1.81E-15 1.47E + 01 6 pd) 3 00E + 00 6.05E-03 4 51E-10 4.04E- 13 2 21E-OS 5 42E-00 6.24E-05 2.07E-15 1.47E +01 7 (4d) 4 00E+00 3 56E-02 2.65E-09 2.37E-12 1.30C-05 3.19E-05 9.43E-(6 1.0tE-13 1.30E +01
- 8. (5d) 5.00E + CD 2 26E-m 1.68E-09 1.5 t E - 12 827E-05 2.03E-05 1.15E-04 524E-14 1.33E +01 Mean: 6.89E-(D 6.17E - 12 3.39E-05 4.27E- 14 1.41 E +0i Stardard Devistm 1.32E -08 1.18E - t t 6 47E-05 5 0 t E-14 1.07E +00 FILE NAME: Fe-55 8AFLE O. PEACH BOTTOM #4 EACH CUMULATlW ACTMTY RE GASE RELEASE RELEASE INCREMENTAL CUMULATWE EFFECT1W LEACH O LEACH TIME LEACFED RATE RATE RATE REEASE RELEASE DIFFUSMTV IMEX ,
(days) (uCi) (uCi*cm 8*s ')(cm a.g s) (Cleyr 1) (cm'ss ') I 1
I 1.(30s) 3 47E-04 1.74E -CD ---- ---- ---- ---- ---- ---- ----
- 3. (7*v) 2.93E-01 1.8aE-CD 6.73E-10 4 44E-11 3.31E-06 1.24E-04 6 53E-04 1.74E-12 1.t eE +0t 4.(14 1.00E + 00 1.69E-03 1.76E - 10 1 17E-11 6.73E-07 1.11 E -04 7.64E-04 4.18E-13 1.24E +01
- 5. pd) 2 00E+(D 1.04E-05 1.44E-12 9.50E-14 7.00E -09 1.28E -06 7.6cE-04 6 75E-17 1.62E +0!
8.(54 5 00E +00 5 53E-04 4.12E-11 2.71E-12 2.02E-07 3 65E-05 6 59E-04 1.70E- 13 12eE +01 i Mean: 1.15E -(D 7.60E-11 5.66E-06 3.75E - 12 129E +0t Standard Deviatm 2.44E-CD 1.6tE-10 120E-05 8.1oE-12 f .SeE +00 j FILE NAhE: Co-60 SAWLE 0: PEACH BOTTOM #4 LEACH CUMULATWE ACTMTY RELEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECTNE LEACH O LEACH TME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX (days)
(uCQ (uCi*cm 8*s- (cm 8
...... ')......'s..
) ....'., .....- - ..... ........'. .. ...
p*yr- ) (cm8 *s- )
1, pos) 3 47E-04 1.18E-02 ---- ---- ---- --~~ ---- --~~ ----
- 3. (7hr) 2.93E-01 9 53E-02 3 41E-m 9 00E-11 167E-04 2 54E-04 5.42E -04 7.33E - 12 1.1 t E +01 4 (Id) 1.00E + 00 1.41 E - 01 1.48E-08 3 95E-11 7 2BE-05 3 76E-04 9.17E-04 4.77E - 12 1.13E + 01
- 6. pd) 3 00E+00 8 00E-(E 6.00E -CD 1.00E-11 2.95E-05 2.15E -04 1.43E-03 3 27E-12 1.15E +01
- 8. (5d) 5 00E +00 4 84E-CE 3 60E-09 9 61E-12 t .77E -05 1.29E -04 1.73E-03 2.13E-12 1.17E +01 Mean: 2.38E-05 6 30E-11 1.17E-04 4 43E-12 1.14E +01 Standard Deviation: 3.08E -m 8.2 t E- 11 1.51E-04 1.saE-12 1.86E-01 FILE NAME: Ni-63 SAMPLE 0: PEACH OOTTOM #4 LEACH CUMULATNE ACTMTY RELEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECTNE LEACH O LEACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX p*yr ')
(days) (uCi)
. . - ..........-- . . .. ..'s..-')......
(uCi=cm 8 (cm 8 's 5)
(cm8* s- )
- 3. (7hr) 2 93E-01 6 76E-03 2 42E-09 3 6aE-10 1.19E-06 1.03E-03 1.95E-03 1.2T - 10 9 92E+00 4 (14 1.00E + (D 8 30E-CD 8 74E-10 1.33E - 10 4 20E-06 127E-CD 3 22E-CD 5 41E-11 1.03E + 01
- 8. (5d) 5 00E+00 4 21E-CD 313E-10 4 78E-11 1.54E-00 6 42E-04 5 64E-(D 5 20E-11 1.03E +01 Mean: 1.4T -00 214E-10 6 89E-m 5 21E-11 1.04E + 01 Standard Deviatm 1.766-CD 2 e9E-10 S e7E-On 3.34E - i , 2 5E-Oi D-3 NUREG/CR-6164
l l Appendix D 1
Table D-1. (continued).
FILE NAME: St-90 SAMPLE 0: PEACH BOTTOM #4 LEACH CUMULATlW ACTMTY RELEASE RELEASE RELEASE INCREMENTAL CUMLAATNE EFFECT1W LEACH O LEACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX (days) (uCi) (uC1*cm 8's ')(cm 8*s ') (Ci*yr ') (cm8*s ')
1.(30s) 3 47E-04 3 43E-06 ---- --- - -- ---- -- - ----
- 3. (71r) 2.93E-01 N/D NO N!D NO NO 1.64E-(D N!D NO
- 4. lid) 1.00E + 00 NO NO NO N/D NO 164E-(D NO N/D
- 5. (2d) 2.00E +00 3 48E-C6 2 59E-13 2.71 E - 11 127E-09 3 64E-04 2.00E -(G 5.50E-12 1.13E + 01 6 (3d) 3.00E + 00 NO NO NO NO NO 2.00E-CD N/D N/D
- 7. (4d) 4.00E + 00 3.47E-06 2.58E - 13 2.70E - 11 127E-09 163E-04 2.37E-CD 1.31 E - 11 109E+01
- 8. ($d) 5 00E +00 N/D N/D N/D N!D NO 2.3M-(D NO NO Maart 4 80E- t2 5.02E-10 2.36E-08 8 21E-11 1.00E +01 6 91E-01 l Standard Deviatert 6 42E-12 6.72E- to 315E-08 1.03E-10 l
FILE NAME: Tc-99 SAMPLE 0 PEACH BOTTOM #4 LEACH CUMULATNE ACTMTY RELEASE RELEASE RELEASE INCREMENTAL CUMULA7NE EFFECTNE LEACH ID LEACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DiFFUSMTY INDEX (days) (uCs) (uCi*cm 8*s ')(cm 8*s ') (C6
- yr ') (cm8
- s ')
1.(30s) 3 47E-04 N/D ---- ---- - - - --~~ - -- ---- ----
- 7. (4d) 4 00E +00 8.31E-04 619E-11 1.31 E - 11 3 04E-07 1.76E -04 2.00E-(D 3.0aE - 12 1.15E +01 8 (5d) 5.00E +(D 6 28E-04 4 68E-11 9 92E-12 2.30E -07 1.33E-04 2.14E-(0 2 27E-12 1.16E +01 Maart 2.03E - 10 4.31E-11 9.90E- 07 9 23E-12 1.15E +01 Standard Devntert 1.71E-10 3 64E-11 a.42E-07 1.70E-11 4 97E-01 FILE NAME: 1-129 SAMPLE ID: PEACH BOTTOM #4 LEACH CUMULATlW ACTMTY RELEASE RELEASE RELEASE INCREDANTAL CUMULATNE EFFECTIVE LEACH O LEACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX (days) (uCi) (uCiecm 8*s ')(cm 8*s ') (Ci*yr 8) (cm8
- s ')
1.(30s) 3 47E-04 NO ---- ---- ---- ---- ---- ---- ----
- 2. (2hr) 8 44E-CD 1.67E -04 1.48E-10 2 44E-06 7 27E-07 2 76E-02 2.76E-02 6 45E-08 7.10E + 00 3 (7hr) 2.93E-01 NO N/D N/D NO N/D 2.76E-02 N/D N/D
- 5. (2d) 2.00E +00 2.58E-04 1.92E - 11 3.17E-09 9 41E-00 4 25E-02 7 66E-02 7.50E -08 7.12E +00 6 (3d) 3 00E + 00 NO N/D NO N/D NO 7.66E -(2 N/D N/D 7, (4d) 4.00E + 00 1.91E-06 1.42E-12 2.35E-10 6 9eE-09 315E-(D 7.98E -(2 9 85E-10 0 01E+00
- 8. (5d) 5.00E + 00 1.01E-04 7.51E-12 1.24E-09 3 69E-08 167E-CD 9 64E-(2 3 5bE-08 7.45E +00 Meart 3 60E-11 5 95E-(9 1.77E-O'1 3 55E-08 7S2E +00 Standard Deviaten: 5 63E-11 9 30E-00 2 77E-07 3.00E-08 8.28E-01 FILE NAME: Cr SAMPLE 0: PEACH DOTTOM #4 LEACH CUMULATNE ACTMTY RELEASE RELEASE RELEASE INCREMENTALCUMULATNE EFFECTNE LEACH O LEACH TIME LEACHED RATE RATE HATE HELEASE RELEASE DIFFUSMTY INDEX (days) (ug) (ugacm 8's ') (cm 8*s ') (g
- yr ') (cm8.s ') )
1.(30s) 3 47E-04 N/D ---- ---- ---- ---- ---- ---- ~~~-
- 8. (5d) 5 00E +00 4.70E + 01 3 50E-06 1.37E-10 1.72E-Q2 1.84E-03 1,42E -CQ 4 32E-10 9 37E+(D Meart 105E-05 4 09E-10 514E-02 3 03E-10 9 53E+00 Standard Devetsort 1.08E -05 424E-10 5 32E-CE 7.25E-11 104E-01 l
NUREG/CR-6164 D-4
Appendix D Table D-1. (continued). '
l FIG NAME: Fe SAMPLE O. PEACH BOTTOM #4 EACH CUMULATNE ACTMTY REEASE RELEASE RELEASE INCREMENTAL CUMULATNE EFFECTlW LEACH O LEACH TIME LEACTO RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX l (days) (ug) (ugacm 8*s ') (cm 8*s ') (geyr ') (crn8*s ') i 1
1,(30s) 3.47E-On 320E+01 ---- ---- ---- ---- ---- -~~- ----
- 2. (2hr) 8 44E-02 NO NO ND NO N/D ND N/D NO
- 3. (Thr) 2 D3E-01 NO ND ND N/D N/D N/D ND ND
- 5. (2d) 2.00E + 00 N!D NO N/D N/D N/D 6.36E-06 N/D ND
- 8. (5d) 5 00E+ D N/D ND N/D NO N/D 1.79E-05 ND N/D Mean: 2.22E-05 5.10E-13 1.09E-CP 2.33E- 15 1 A7E+01 i Standard Deviation: 4.92E-07 1.13E-13 2 42E-03 7.17E-16 1.5 t E-01 1 1
FILE NAME: Co SAMPLE ID: PEACH BOTTOM #4 LEACH CUMULATNE ACTMTY RELEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECTlW LEACH O LEACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX
.................'.....'s'....').................'........
(days) (ug) (ugacm a.s- ) (cm 8
) (geyr- (cm8* s- )
i 1.(30s) 3 47E-04 1.54E + 01 ---- ---- ---- ---- ---- ---- ---- I
- 3. (7hr) 2.93E-01 320E+ 01 1.14E -m 3 52E-09 5.70E-m 9 86E-(D 1.63E-Q2 1.10E-08 7DSE +(D j
- 7. (4d) 4.00E + 00 1.56E +01 1.16E-06 3 58E-10 5.78E-C0 4 81E-(D 3.71E-G2 2.29E -09 8 64E+00 l
- 8. ($d) 5 00E+00 1 siE +01 1 APE-05 4.38E-10 7 oeE-CD 5.89E-03 4.30E-02 4 42E-CD 8.35E + (D Mean: 5.35E-06 1.65E-00 2.66E-02 3.62E-CD 8.62E + 00 Standard Deviatm 6.47E-OS 1 D9E-09 322E-02 3 2SE-(D 4.22E-01 I
l FILE NAME: Ni SAMPE 0: PEACH BOTTOM #4 1
LEACH CUMULATNE ACTMTY RELEASE RELEASE RELEASE INCREMENTALCUMULATNE EFFECTlW LEACH !
O LEACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX (days) (ug) (ug*cm 8 s ') (cm 8*s 1) (gayr ') (cm8*s ')
1.(30s) 3 47E-04 N/D ---- ---- ---- ---- ---- ---- ----
- 6. (3d) 3 00E +00 5.04E +01 3.76E-06 2.52E - 10 1.85E-m 3.39E-03 1.6aE-m 8.10E - 10 9 09E+00
- 7. (4d) 4 00E SCO 5 03E + 01 3 75E-06 2.52E- ta 1.84E-02 3.38E-(D 2.01E-G2 1.13E-CD 8 95E+00
- 8. (5d) 5.00E + 00 4 35E+01 324E-C6 2.18E- 10 1.59E-m 2 92E-CD 2.31E-02 1.00E-09 8 96E +00 Maart 1.14E-05 7.66E- 10 5 60E-Q2 8 51E-10 9.10E +00 Standard Devataan: 1.37E-05 91GE-10 6.72E-02 2.70E-10 1.62E-01 FILE NAME: 2n SAMPLE 0; PEACH DOTTOM #4 LEACH CUMULATNE ACTMTY FIELEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECTNE LEACH ID LEACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX
......'s' ) (g (ug*cm s.s- ) (cm 8 eyr-(days) (ug) (cm8*s ')
...... ...... ...... ....... .. ......'). ...... . ...... .....--.. .......
1.(30s) 3 47E-04 515E +01 ---- ---- ---- ---- ---- ---- ----
- 2. (2hr) 8 44E-G2 3 31E+01 2 93E-05 1.5aE -(D 144E-01 1.79E-(D 1.79E-CD 2 71E-10 9.57E +00 3 (7hr) 2 93E-01 N/D ND N/D N/D N/D 1.79E-CD N/D N/D 4 (1d) 1.00E + 00 225E + 01 2.37E-00 1.28E-10 1.16E-02 122E-03 3.01 E -(D 5 00E-11 1.03E +01 5 (2d) 2.00E + 00 2.61 E + 01 194E-05 105E-10 9 54E-CD 1 A1E-03 4 42E-03 8 26E-11 1.01 E + 01
- 6. (3d) 3 00E+00 N/D N/D NO ND N/D 4 42E-CD NO ND
- 7. (4d) 4 00E +00 N/D NO NO ND N/D 4 42E-03 N/D N/D
- 8. (5d) 5 00E +00 N/D N/D N/D N/D N/D 4 42E-(D N/D N/D Mearr 1.12E-05 6.06E - 10 5.50E -02 1.35E-10 9 98E+(D Standard Devoteort 128E-05 6 92E-10 6 29E-02 9.74E-11 3.08E-01 D-5 NUREG/CR-6164
Appendix D Table D-1. (continued).
F6 E NAME: B SAMPLE 0: PEACH BOTTOM #4
! EACH CUMULATlW ACTMTY RELEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECTlw LEACH l O LEACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX (days) (ug) (ug*cm a. .') (cm.a .s s) (g*yr ') (cm**e ')
1.(30s) 3 47E-04 3 43E+01 ---- ---- ---- ----
6 82E-03 6 82E-CD 3 94E-00 8 40E +00 j 2 (2hr) 8 44E-02 3.13E + 01 2.77E-05 6 05E-09 1.36E-01 2 93E-01 NO NO N/D NO NO 6 82E-(D NO NO 1 3 (7hr) 1.00E + C0 3 46E+01 3 64E -06 7 93E-10 1.79E-m 7 54E-03 1.44E-02 1.92E-CD 8 72E+(D ,
i 4. (id) 5 (2d) 2.00E + 00 3 48E + 0t 2 59E-06 5 64E-10 127E-02 7 58E-03 219E-(P 2 38E-00 8 62E +00 l 3 00E+00 3 48E+01 2 59E-05 5 64E-10 1.27E-02 7.58E -CD 2 95E-02 4.05E-CD 8 39E+(D
- 6. (3d)
- 8. (5d)
Mean: 914E-06 199E-CD 4 49E-T 3 07E-(D 8 53E+00 Standard Devetgrt 1.08E-05 2.34E -09 5 28E-02 9.30E - 10 1.40E-01 FIE NAME: Pcchne Acid SAWE 0: PEACH BOTTOM #4 LEACH CUMULATlw OUANTITY RELEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECT1W LEACH D LEACH TIME LEACFED RATE RATE RATE REEASE RELEAff DIFFUSMTY INDEX (dnys) (ug) (ug*cm 8*s ') (cm 'as ') (geyr ') (cm8*s 1) 1.(30s) 3 47E-04 NO ---- --~~ ---- ---- ---- ----
- 3. (7hr) 2 93E-01 3 20E + Cd 1.t 6E -02 8 53E-10 $12E + 01 2.39E -(D 4 73E-CD 6 45E-to 919E +00 4 (Id) 1.O(E + 00 6.14E + 04 6 46E-CD 4 74E-10 310E + 01 4 50E-03 9 23C-03 6 84E-10 917E + 00
- 7. (4d) 4.00E + 00 2.85E + D4 2.12E-03 1.55E - 10 104E+ 01 2.09E -03 1.82E -m 4 31E-10 9.37E+00
- 8. (5d) 5.00E + 00 2.21 E + 04 1.64E -CD 1.21 E -10 8 08E+3) 162E-03 199E-02 3.35E - 10 9 48E +00 Maart 8.18E-03 0.00E - 10 4 02E+01 5 45E-10 928E +0)
Stardard Dev.atert 8 84E-CD 6 48E-10 4 34E+01 1.40E - 10 1.10E-01 NUREG/CR-6164 D-6
Appendix D Table D 2. Peach Bottom sample #8 cumulative fraction releases, release rates, effective diffusivities, and leachability indexes.
FILE NAME: C-14 SAMPE 0: Peach Bettcrn #8 LEACH TOTAL ACTMTY RELEASE RELEASE RELEASE INCREMENTAL CUMt.A.ATIVE EFFECTINE LEACH I O TIME LEACFED RATE RATE RATE RELEASE RELEA*iE DIFFUSM TY INDEX '
(days) (uCQ (uCl*cm 8*s ')(cm 8*s ') (Ca*yr ') (cm8*s ')
........................................m............
i 1.(30s) 3 47E-04 122E-m - - - - ---- ---- ---- ---- ---- ---- l l 2. phr) 8 40E-02 1.18E-01 9 40E-08 8.55E-11 5.t oE-04 1.07E-04 107E-04 1.01E - 12 120E + 01
! 3. (7hr) 2 44E-01 9 35E-02 3 91E-08 3 53E-11 213E-04 8.45E -05 1.92E -OL 1.37E - 12 1.19E + 01 1
- 4. (Id) 9 30E-01 120E-01 124E-08 1.12E - 11 018E-05 1.16E-04 3 0HE-04 4 8tE-13 123E +01 l 5. (2d) 1.93E + 00 1.18E -01 8.01 E -(9 723E-12 4 36E-05 1.07E-04 415E-04 5.19E - ?3 123E + 01 1 6. (3d) 2.92E + CD 8 49E-02 5 75E-0D 5.19E-12 313E-05 7.67E -05 4 91E-04 4 02E-13 123E +01 i 7. (4d) 3 91E+00 7.01E-02 4 75E-0D 4 29E-12 2 59E-05 0.33E -05 5.55E-04 4 40E-13 1.34E + 01 l 8. (Sd) 4 00E +00 147E-01 9 98E-09 9 02E-12 5 44E-05 1.33E -04 6 88E-04 2.55E - 12 1.t eE + 01 l Mearr 2 50E-08 22SE-11 1.30E-04 9.88E-13 1.2 tE + 01 Standard Demattart 3 05E-00 2 75E-11 100E-Os 7 20E-13 2.75E-01 l
FitE NAME: Fe-55 i MMPLE 0: Peach Bartorn #8 I i
LEACH TOTAL ACTMTY RELEASE RELEASE RELEASE INCREMENTALCUMULATIVE EFFECTIVE LEACH I ID TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSIVITY INDEX )
(days) (uCi) (uCiacm 8*s ')(cm 8*
') (Ceayr ') (cms .g_i} i i
1.(30s) 3 47E-04 t 91E-01 ---- ---- ---- ---- ---- ---- ----
l
- 2. phr) 8 40E-m 1.f oE-01 9.30E-08 617E-0D 5 07E-04 772E-03 712E-03 570E-0D 8 24E +00 l 3 (7hr) 2.44E-01 6 63E-m 2 77E-m 1.84E-09 1.5 t E -04 4 40E-CD 121E-02 3 71E-09 8.43E + 00 4 (td) 9 30E-Ot 5 27E-02 5 09E-09 3.3BE - 10 2 78E-05 3 50E-m 15cE-m 4 35E- to 9.36E + 00
- 5. (2d) 1.9JE +00 229E-m 1.55E-0D 1.03E - 10 8 43E-00 1.52E -03 t J1E-m 104E-10 9 9aE+00 0 (3d) 2 92E +00 1.04E-m 7.01 E - 10 4 05E-11 3 82E-05 6 87E-04 138E-m 3 70E-11 104E + 01
- 8. (5d) 4 90E+CD 4 80E-03 32eE-10 2.10E-11 177E-00 3.18E -04 185E-02 1 ACE-11 100E+01 Mean- 184E-O'l 122E-03 1.00E -04 1.43E-09 974E + 00 Standard Demotion: 3.18E-m 2.11 E -09 I J3E-04 2.14E-09 1.02E +00 FILE NAME: Co-60 SAMPLE ID: Peach Dcitam #8 LEACH TOTAL ACTMTY RELEASE RELEASE RELEASE INCREMENTALCUMULATIVE EFFECTIVE LEACH O TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX (days) (uCi) (uCi*cm 8*s- )(cm a.s ') (Cl*yr 8) (cm8*s 5) 1.(30s) 3 47E-04 12 t E-(2 ---- ---- --~~ ---- ---- ---- ----
- 2. (2hr) 8 40E-m 1.64E-01 1.31E-07 3 52E-10 7.13E -04 4 41E-04 4 41E-04 1.85E-11 1.07E + 01 3 (7hr) 2.44E-01 9 41E-(2 3 94E-OS 1.00E- 10 2.14E-04 2 53E-04 6 93E-04 123E-11 1. ODE + 0i
- 7. (4d) 3 91E+00 1.00E-01 7 190 - 03 1.93E - 11 3 92F-nS 2 8eE -04 2.32E -CD 9.00E - 12 1.10E + 01
- 8. (5d) 4 90E+00 2.34E-01 1.59E-0B 4 26E-11 8 64L-06 6 2BE-04 2.95E-03 5.00E - 11 1.02E +01 Mean: 3.33E-08 8 95E-11 1.81E -04 1.80E - 11 1.09E + 01 Standard Demation: 4.11E-08 1.10E - 10 2 24E-04 162E-11 212E-01 FILE NAME: Ni-63 SAMPLE 0: Peach Bottom #8 LEACH TOTAL ACTMTY RELEASE Rt" LEASE RELEASE INCREMENTAL CUMULATIVE EFFECTIVE LEACH O TIME LEACFED RATE RATE RATE RELEASE RELEASE DIFFUSM TY INDEX
............-.........')......-............-....................
(days) (uCQ (uCiecm 8*s- (cm 8*s 5) (Ca*yr 8) (cm8*e ')
1.(30s) 3 47E-04 2 57E-05 ~~~~ ---- ---- --~~ ---- ---- ----
- 3. (Thr) 2 44E-01 7 02E-05 2.94E-11 4 50E-12 1.50E-07 1.08E-05 2 78E-05 222E-14 1.37E + 01 4 (Id) 9 39E-01 9 24E-05 8.93E - 12 1.37E - 12 4 57E-08 1 A2E-05 4 20E-05 7.17E - 15 141E + 01 5 pd) 1.03E + 00 377E-05 2.55E - 12 3 91E-13 1.31 E -08 5 78E-Ce 4 78E-m t .51 E - 15 1.48E + 01
- 7. (4d) 391E+00 NO NO NO NO NO 5 02E-05 NO NO
- 8. (5d) 4 90E+00 ND ND ND NS NO $02E-05 NO NO Mean: 2 e?E-11 4 01E-12 1.34E-07 1.18E - 14 1.43E +01 Standard Demation: 3 30E-11 5 OSE~12 1.09E -07 1.12E - 14 6 9tE-01 D-7 NUREG/CR-6164 l
Appendix D Table D-2. (continued).
FILE NAME: Br-90 SAMPE ID: Peach Octtcyn #8 LEACH TOTAL ACTM TY RELEASE RELEASE RELEASE INCnEMENTAL CUMULATIVE EFFECTIVE LEACH 10 TIME LEACHED RATE RATE RATE RELE ASE RELEASE DIFFUSMTY INDEX (days) (uCi) (uCecm 8 s ')(cm 8*s ') (Cryr ') (cm'.s ')
3 47E-04 1.94E-(6 ---- ---- ' ---- ---- ---- ---- ----
1.(30s)
- 5. (2d) 1.93E +00 NO N!D N/D NO No 14eE-02 NO NO 6 (3d) 2.92E +00 NO NO NO NO NO 1.46E-02 NO NO
- 8. (5d) 4 90E +00 6.91E-05 4 09E-13 4 95E-11 2 55E-CD 729E-04 t e5E-T 7 67E-11 1.01E +01 Mean; 1.54E - 11 1.63E-09 8 41E-m 1.70E -09 9 2eE+00 Stardard Deviattart 2.35E-11 2 48E-CD 128E-07 2 38E-09 6 88E-01 FILE NAME: Tc-99 SAMPLE 0; PeachBattom #8 LEACH TOTAL ACTMW RELEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECTlW LEACH O TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX (days) (uCe) (uCiacm 8*s ')(cm 8*sa) (Ci*yr ') (cm8*s ')
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - - = = . . . . . . . - . . . . . . . . . . . . . = = . . . . . . .
1.(30s) 3 47E-04 1.54E-CD ---- ---4 ---- ---- ---- ---- ----
- 8. (5d) 4 00E+00 6.40E-CD 4 39E-10 9.38E-11 2 25E-te i .38E-03 2.55E -02 2.7eE-20 9 5ee+00 Maart 193E-03 413E-10 9 83E-05 2 45E-CD 1.01E +01 Standard Deviatort 3.27E-09 7 00E-10 t 67E-05 5 84E-CD 1.05E +00 FILE NAME: Sb-125 SAMPLE 0: Peach Battcryi #8 LEACH TOTAL ACTMTV RELEASE RELEASE RELEASE INCREMENTAL CUMULATIVE EFFECTIW LEACH 10 TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY lh0EX (days)
(uCl)
(uCiacm a.s 8)(cm 8*s ')
(Cr yr-
.....'). ....... ...... . (cm8* .....'. s- )
1.(30s) 3 47E-04 2.32E-04 ---- ---- ---- ---- ---- ---- ----
- 2. (2hr) 8 40E-02 NO NO NO N/D N/D NO N/D NO
- 3. (Thr) 2 44E-01 NO NO N/D N/D NO N/D NO NO 4, (i d) 9 39E-01 9 72E-04 9.39E - 11 7.91E-11 5.12E-07 819E-04 819E-04 2.39E-11 1.00E + 01
- 8. (5d) 400E+00 9 69E-04 e 5aE-11 5 54E-t t 3.58E-07 8.17E-04 3.71E-03 9 62E-11 1.00E + 01 Mean: 6 53E-11 5.50E-11 4 40E-11 1.04E + 01 Standard Deviatiort 1.80E - 11 1.51E-11 2.68E - 11 223E-01 FILE NAME: 1-120 SAMPLE 0: PeachBottam #8 LEACH TOTAL ACTMTY RELEASE RELEASE RELEASE INCREMENTAL CUMULATIVE EFFECTIVE LEACH ID TitK LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTV INDEX (days) (uCl) (uClacm 8*s ')(cm 8*s ') (Cryr ') (cm8*s ')
1.(30s) 3 47E-04 2.74E-05 ---- ---- ---- ---- ---- ---- ----
- 2. phr) 8 40E-02 5 86E-06 4 eBE-12 7 79E-10 2 55E-08 9 75E-04 9.75E -04 9.00E-11 1.00E +01 3 (Thr) 2 44E-01 147E-05 613E- 12 1.02E-09 3 34E-0B 2 44E-CD 3 41E-(D 1.14E-09 8.94E + 00 4 (1d) 9.39E -01 NO N/D N/D NO NO 3 4 tE-CD N/D N)D
- 8. ($d) 4 90E+00 4.10E-05 2.78E - 12 d o1E-10 1.52E-0B 6 83E-CD 2.00E -02 6 72E-CD 817E +00 Maart 3 37E-12 5 61E-to 1.84E -0B 2 37E-09 8 8eE +CD Stardard Devistort 1.57E-12 2 01E-10 6.54E-00 2.12E-09 5.78E-01 NUREG/CR-6164 D-8
t Appendix D I.
l' l
l Table D-2. (continued). ,
l \
- FIE NAME
- Co-137 SAMPE 0: Peach Bottom #8 j LEACH ~ TOTAL ACTMTV REE ASE REEASE REEASE INCREMENTAL CUMt.AATlW EFFECTlW LEACH O TIME LEACHED RATE RATE RATE REEASE RELEASE DiFFUSMTV INDEX -
(deys) (LO) (uCocm a.s ')(cm 8*s.') (Ceyr ') (cm8*s ')
1.(30s) 3 47E-04 . 3.25E-04 . ---- ---- ---- ---- ---- ---- ----
- 5. (2d) 1.93E + 00 1.12E-CD 7.55E - I t 1.30E-10 4.12E-07 2.05E-G3 7.64E-C0 1.00E-10 9.72E +(D
- 6. (3d) 2.92E +00 1.1 tE-03 7.5 t E - 11 1.38E-10 4.00E-07 2.04E-(D 9 67E-(D 325E-10 9 40E +00
- 8. (Sd) 4.90E+00 - 2.38E-03 1.6tE-10 2.9eE-10 8 79E-07 4 3eE-03 1.84E -02 2.74E-0D 8.5eE+00 Maart 225E-10 413E-10 1.23E-06 8.02E-10 9mE +00 Standard Deviatort 1.82E-10 3.33E - 10 9 90E-07 9 88E-10 4 48E-01 FILE NAME: Fe '
SAMPLE 0: Peach Bortom #8 EACH TOTAL QUANTITY REEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECTlW LEACH ID TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX .
(days) - (ug) (ug*cm e.g 1) (bm 8*s 8) (g a yr- (cm8*s 8)
...... . ... ...... .... . .. ....') .... ...... . . ... .. .
1.(30s) 3.47E-04 2.03E + 03 ---- ---- ---- ---- --~~ ---- ----
- 2. (2hr) 8 40E-02 1.10E +(D 8.81E-04 2.04E-10 4 80E+00 2.55E-04 2.55E -04 6.20E-12 1.12E + 01
- 4. (id) 9.39E-01 1.03E + 02 1.00E-05 2.31E-12 ~ 5 45E-m . 2.39E-05 3.54E-04 2.03E - 14 1.37E +01
- 6. (3d) 2 92E+00 8.62E + 01 5.84E-06 1.35E-12 3.18E-02 1.99E-05 4.08E-04 3.11E-14 1.35E + 01
- 7. (4d) 3.9 tE +00 5.17E + 01 3.50E -08 8 00E-13 1.01E-m 1.19E-05 4.18E-04 1.59E-14 1.38E + 01 8 (5d) 4 90E+00 - 8.62E +01 5 85E-00 1.35E - 12 3.19E-m 1.99E-05 4.38E-04 5.72E-14 1.32E +01 Meart 1.50E-04 3 47E-11 8.20E-01 1.07E-12 1.30E +01 Standard Deviauort 3 02E-04 6.97E-11 1.64E+00 2.13E-12 9.13E-01 l j
I I
l I
i 1
l D-9 NUREG/CR-6164
Appendix D Table D-3. Peach Bottom sample #12 cumulative fraction releases, release rates, effective diffusivities, and leachability indexes.
FILE NAME: C-14 SAMPLE O. PEACH BOTTOM #12 LEACH CUMULATNE ACTMTV RELEASE RELEASE REGASE INCREMENTAL CUMULATlW EFFECTNE LEACH O LEACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTV INDEX (days) (uCl) (uCa*cm 8*s ')(cm 8*s ') (Ci*yr ') (cms .s_i) 1.(30s) 3 47E-04 7.8E-CE ---- ---- ---- ---- - -- - -- ----
3 60E-05 8 94E-m 3.35E - 15 145E +01
5 00E + 00 3.38E-03 2 48E-10 2.25E-13 123E-06 3 00E-m 5 47E-05 1.21E-15 149E+01 )
- 8. (5d)
Maart 2.74E-00 2 49E-12 1.36E-05 5.50E - 15 1 A4E +01 Standard Devaton: 4 27E-09 3 88E-12 2.13E -05 4 83E-15 3 9'E-01 FILE NAME: Fe-55 SAMPLE ID: PEACH BOTTOM #12 LEACH CUMULATlW ACTMTY RELEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECTNE LEACH O LEACH TIME LEAC K D RATE RATE RATE RELEASE RELEASE OtFFUSMTY INDEX l
......................_')......'.....')........_......._...'s8)
(days) (uCl) (uCiecm 8*s- (cm 8*s- ) (Ci*yr- (cm8 l
I 1
1.(30s) 3 47E-04 7.86E-04 ---_ _-__ ____ ___- __-- ___ ----
8.37E-02 8 63E-04 7 61E-10 5.00E-11 3.79E -06 5.76E-05 5 76E-05 2 86E-13 1,25E + 01
- 2. (2hr)
Maart 6 55E-10 4.37E-11 3 26E-06 1.11E-11 1.15E +01 i Standard Decaticrr 6.35E - 10 4 24E -11 3.16E -06 1.70E - 11 7.05E-01 a
l 1
FILE NAME: Co-60 SAMPLE 0: PEACH DOTTOM #12 LEACH CUMULATNE ACTMTY RELEASE RELEASE RELEASE INCREMENTAL CUMULATNE EFFECTNE LEACH O LEACH TIME LEACTO RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX
......................_')......'.....').....................'...'........
(days) (uCl) (uClocm_s*s- (cm 8*s- ) (Ci* yr- (cm es- )
1.(30s) 3 47E-04 3 29E-02 - -- ---- ---- ---- ---- ---- ----
- 2. (2hr) 8.37E -02 1.00E -01 8 85E-0B 2.39E-10 4 40E-04 2 71E-04 2 71E-04 6 36E-12 1.12E +01 3 (7hr) 2.92E-01 911E-C2 3 22E-m 8 70E-11 1.60E-04 2 A7E-04 518E-04 6 92E-12 1.12E +01
- 5. (2d) 2.00E +00 1.11E-01 817E-CD 2 21E-11 4 06E-05 3 01E-04 1.17E -03 3 79E-12 1.14E + 01 6 (3d) 3 00E +CD 8 24E-02 6 06E-03 1.64E - 11 3 01E-05 2 23E-04 1.39E-CD 3 54E-12 1.15E +01
- 7. (4d) 4 00E +00 6.41 E -02 4.71 E -CE 1.27E-11 2.35E-05 1.74E-04 1.56E -00 3 02E-12 1.15E +01
- 8. ($d) 5.00E + 00 5.56E-02 4.00E -CD 1.10E - 11 2.03E-CE 1.50E-04 1.71E-CD 2 9tE-12 1.15E + 01 Mean: 2.24E-m 6.07E-11 1.12E-04 4 38E-12 1.14E + 01 Standard Deviaton: 2 84E-08 7 69E-11 142E-04 149E-12 1.30E-01 FILE NAME: Ni-63 SAMPLE 0: PEACH BOTTOM #12 LEACH CUMULATNE ACTMTV RELEASE RELEASE , RELEASE INCREMENTAL CUMULATNE EFFECTNE LEACH O LEACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSM1Y INDEX
.................._......_')......'_.....')...............___..'...._........
(days) (uCl) (uCecm 8*s- (cm 8*s- ) (Ca e yr- (cm es ')
,. (30s) 3 47E_04 5 59E-m _-_- ____ __-_ ____ ___- ____ _-__
- 2. (2hr) 8 37E-02 7.13E -CD 6 29E-09 9.71 E - 10 3.13E - 05 1.10E - CD 1.10E-CD 1.05E - 10 0 90E+CD 3 (7hr) 2 92E-01 5.97E -00 211E-09 3 25E-10 105E-05 9 22E-04 2 02E-03 9 67E-11 1.00E + 01
- 8. (5d) 5 00E + 00 3.06E-03 2 25E-10 3 47E-11 1.1?E-06 4 73E-04 6 20E-03 2.88E-11 105E + 01 Maart 1.52E-00 2.35E - 10 7.58E -06 5 85E-11 1.03E + 01 Standard Deviaton: 2.04E-CD 3.15E - 10 1.02E-CE 2 93E-11 2.15E-01 NUREG/CR-6164 D-10
f 1
Appendix D 2
Table D-3. (continued).
FILE NAME; Br-90 SAMPLE 0: PEACH BOTTOM #12 LEACH CUMULAffW ACTMTY REEASE REEASE RELEASE INCREMENTAL CUMULATlW EFFECTlW LEACH O EACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DiFFUSMTY IPOEX (days) (uCl) (uClacm hs ')(cm s*s 8) (Clayr ')
...................................'s8) (cm8
} 1.(30s) 3 47E-04 ND ---- -- - ---- ---- ---- ---- ----
t 2. (2hr) 6.37E-m 522E-CD 4.00E 4 88E-10 2 29E-0B 5 54E-04 5.54E-04 2,65E-11 1.00E+01
] 3 (7hr) 2 92E-01 3 47E-CB 122E-12 130E-10 6.09E-09 3 68E-04 9.22E-04 1.54E-f t 1.08E +01
- 5. (2d) 2.00E + C0 N/D N/D ND N/D N/D 1.01E-C0 N/D N/D
- 6. (3d) 3.00E+00 NO N/D N/D N/D ND 1.01E-C0 ND N/D
- 7. (4d) 4.00E + 00 3.deE-05 2.54E-13 2.70E-11 1.27E-09 3.67E-04 - 1.38E-CD 1.35E-11 1.00E + 01
- 8. (5d) 5 00E +00 N/D N/D N/D N/D ND. 1.38E-03 N/D ' N/D Mean: 1.54E - 12 1.64E - 10 7 68E-00 1.30E - 11 1.12E +01 l Standard Dewatiert 1.82E-12 1.93E- 10 0.05E-09 9.30E-12 7.86E -01 i
i FIE NAME: Tc-99 j SAMPLE 0: PEACH BOTTOM #12 LEACH COMULATIW ACTMTY REEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECTNE LEACH O LEACH TIME LEACHED RATE RATE RATE RELEASE DIFFUSMTY INDEX
................').....-..'..................'.......
RELEASE (days) (uCl) (uClocm 8*s- (cm 8*s ') (Clayr- ) (cm8*s- )
1.(30s) 3 47E-04 N/D . ---- ---- ---- ---- ---- ---- ' ----
(
- 3. (7hr) 2.92E-01 7.05E-04 2.70E-10 5.80E- 11 1.34E-05 1.64E-04 1.79E-04 3.09E-12 1.15E +01
)
1
- 5. (2d) 2.00E + 00 ' 5 0eE-(D 3.72E-10 ' 8.00E-11 1.85E-06 1.09E -(D 2.02E-CD . 4 96E-11 1.03E + 01 1
- 0. (3d) 3.00E + CD 2.97E-CD 2.19E-10 4.70E-11 1.09E-ce 6.39E-04 2.66E-CD 2.91E-11 1.0SE + 01
- 7. (4d) 4.00E + 00 1.80E-04 1.32E- 11 2.84E-12 0 58E-08 3.87E-C6 2.7CE-03 1.50E-13 1.28E+01
- 8. ($d) 5 00E+CD 1.67E-03 1.22E-10 2 63E-11 6.10E-07 3.58E-04 3.0eE-CD -.1.06E-11 1.08E +01 Mean: 2.03E - 10 4.36E-11 1.01E-06 1.30E-11 1.15E+01 Standard Dewatlert 1.32E-10 2.84E-11 0 59E-07 1.08E-11 121E+00 FILE NAME: 1-129 SAMPLE ID: PEACH BOTTOM #12 LEACH CUMULATNE ACTMTY RELEASE RELEASE RELEASE INCREMENTALCUMULATlw EFFECTlW LEACH O LEACH TIME LEACHED RALE RATE RATE RELEASE RELEASE DIFFUSMTY lbOEX
....-..............--....'..................(cm'....)....
(days) (uCl) (uClacm 8*s ')(cm-8*s-- ) (Ci*yr 5) se 5 1.(30s) 3 47E-04 1.0eE-05 .---- ~~~- ---- ---- ~~~- ---- ----
- 3. (7hr) 2.92E-01 )
N!D N/D ND N/D ND 1.08E-m ND N/D
- 5. (2d) 2.00E + 0D 9.40E-OS 6 00E-13 1.10E-10 3.43E-00 1.57E -03 2.35E-CG 1.04E-10 9.98E + 00
- 0. (3d) 3.00E + 00 5.84E-05 4.30E-12 7.19E-10 2.14E-m 9.70E-(D 3 33E-02 0.82E-09 8.17E+00
- 7. (4d) 4.00E +CD ND NO N/D NO ND 3.33E-CE ND ND
- 8. (5d) 5.00E + CD 1.44E-04 1.06E-11 1.78E-09 5.28E-OS 2.42E-02 5.74E-Ce 7,54E -08 7.12E +00 Mean: 1.58E-11 2.64E-09 7.84E-08 1.93E-08 8.33E+00 Standard Demahort 2.05E-11 3.44E-09 1.02E-07 2.82E-0B 9.31E-01 FILE NAME: Cr SAMPLE 0: PEACH BOTTOM #12 LEACH CUMULAT1W QUANTITY RELEASE RELEASE O RELEASE INCREMENTALCUMULATlw EFFECT!W EACH LEACH TIME EACED RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDFX (days) (ug) (ug*cm 8*ss) (t:m-hs ') (gayr ') s
....-.........-...........--................(cm.ss} . . . . . . . .
- 1. f30s) 3 47E-(M 4.56E + 01 ---- ---- ---- ---- ---- ---- ----
- 2. (2rv) 8 37E-02 0.01E+01 5 83E-05 2.3 t E -CD - 2 00E-01 2.62E-CD 2.62E-03 2.92E-01 5.03E-10 9.23E +00
- 5. (2d) 2.00E + 00 3 47E-10 9 40E+00 7.60E + 01 5 63E-05 2.23E-10 2.80E-CE 3 04E-CD 1.13E-02 3 87E-10 9.41E+00
- 8. (5d) 5,00E +00 6.11 E- 10 9 21E+00 5.92E + 01 4.34E-06 1.72E - 10 2.16E-02 2.35E-CD 1.87E-02 7.00E - 10 9.15E + 00 Maart 1.54E-05 0 00E- 10 7.64E-m 5.43E-10 928E+00 Standard Dewatiert 1.84E-05 7.30E - 10 91eE-02 128E-10 1.10E-01 D-11 NUREG/CR-6164 g ( wg.w-w w w -> + v-R*'9e-F*.*,.r4.e t- t e e-.m t. ,M e.wa.m-w -'. mew *- PN1-**-*N"* *" " - - ^ - - -
Appendix D Table D-3. (continued).
FILE NAME: Fe SAWLE 0: PEACH BOTTOM #12 LEACH CUMULATNE QUANTITY RELEASE RELEASE RELEASE INCREMENTALCUMULATNE EFFECTlW LEACH O LEACH TIME LEACKD RATE RATE. RATE RELEASE RELEASE DIFFUSMTV IPOEX (days) (ug) (ugacm 8*ss) (cm 8*ss) (g.yr ') (cm8 *ss)
- 1. (30s) - 3 47E-04 KO ---- ---- ---- ---- ---- ---- ----
2 (2hr) 8 37E-m 5 04E+01 4 45E-05 1.04E - I t 2 21E-01 1.17E-05 1.17E-05 1.10E-14 1.39E + 01
- 6. (3d) 3.00E + 00 417E +01 3.07E-06 7.14E-13 1.53E-02 ' 012E-06 6A1E-05 6 73E-15 1.4?E +01 7, (4d) 4.00E +(D 4.33E +01 S taE-m FA0E-13 1.5aE-02 1.01E -05 7A2E-05 1.02G-14 1 A0E+01
- 8. (5d) 5.00E + 00 N/D NO ND NO -ND 7 A2E -05 . ND ND Montt 1.30E-05 323E-12 6 91E-02 1.11E-14 1 A0E+0t Standard Devietm 1.5 t E -05 3 52E-12 7.5?E-02 5 58E-15 1.91E-01 =
FILE NAME: Co SAWLE 0: PEACH BOTTOM #12 LEACH CUMULATlW QUANTITY RELEASE RELEASE ' RELEASE INCREMENTALCUMULATlW EFFECTlW LEACH O LEACH TIME LEACHED RATE RATE RATE RELEASE RELEASE DIFFUSMTY lh0EX (deys) (ug) (ug*cm 8+ss) (cm 8*ss) (g*yr 8) (cm8*s 8) 6 1,(30s) 3 47E-04 1.69E +00 ---- ---- ---- ---- ---- ---- ----
- 0. (3d) 3.00E + 00 2J8E +01 2.05E-C6 6.36E-10 1.02E-02 8 68E-(D 2.00E-02 5.3eE-09 8 27E+00 7 (4d) 4.00E +00 2 A2E +01 t J8E-05 5 55E-10 8 8eE-03 7.55E-CD 3.35E-m . SJ2E-CD 824E +00
- 8. ($d) 5.00E + 00 22eE+01 1.6eE-05 5.18E-10 8 2eE-03 7.05E-(D 4.0eE-m 6 4 tE-09 819E +(D
........~....... . ... .... . ...... .. .. ~ .
Mean: 37(E-05 1.15E-09 1.84E-m 3.38E-CD 800E+00 Standard Dewhatiart 3 8eE-06 120E-09 1.92E-02 2.30E-09 4.81E-01 FILE NAW: NI SAWLE 0: PEACH BOTTOM #12 LEACH CUMULATNE QUANTITY RELEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECTlW LEACH O LEACH TIME LEACKD RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX (days) (ug) (ugacm a.s- ) (cm 8*s 8) (ga yr- (cm8 *s- )
...............'..........')............'...
1,(30s) 3 47E-04 ND ---- ---- ---- ---- ---- ---- ----
- 4. (t d) 1.00E +00 9 2eE+01 0 00E-06 6.54E-10 4 78E-(E 6.30E-03 1.64E-02 1.35E-09 8 87E+0D
- 8. ($d) 5.00E + 00 6 9eE+01 51 t E-Os 3 4aE-10 2 54E-02 414E-CD 3.53E-02 ' 2.89E-09 8.54E +0 Meert 1.7eE-05 120E-(n 878E-CE 1.90E-09 873E+00 Standard Devinhart 2.20E-OL 1.50E-09 1.00E-01 6 ACE-10 1.59E-Ot I,
FILE NAME: Zn SAWLE 0: PEACH OOTTOM #12 LEACH CUMULATNE QUANTITY RELEASE RELEASE RELEASE INCREMENTAL CUMULATlW EFFECTlw LEACH O LEACH TIME LEACKD RALE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX
.......................'.....'.....')..............'s'.......
(deys) (uG) (ugacm 8*s- ) km 8*e- ) (g *yr- (cma
)
1.(30s) 3 47E-04 2 37E +0i ---- -__- -_-- ---- ---- ---- ----
- 6. (3d) 3 00E +00 2 26E +01 f .coE-05 9 t tE-it 8 27E-(D 124E-CD 9 50E-03 1.0GE- 10 9 0eE+00 7, (4d) 4.00E +00 2 00E+01 1.9f E-OS 10SE-10 9 49E-03 l A2E-(D 1.00E-m 2.03E-10 9 00E+CD 8 (5d) 5.00E + 00 27BE+01 2 04E-OS 1.12E - 10 1.02E-CE 1.53E-CD 124E-02 3 00E-10 9 52E+00 Maart 8 58E-05 4 70E-10 427E-02 2 62E-10 9 65E+00 Standard Devnshort 1.1 tE-05 0.07E- 10 5.5 tE-02 1 A7E-10 2 A4E-01 l NUREG/CR-6164 D-12 l
Appendix D Table D-3. (continued).
FILE NAME: B SAMPE D. PEACH BOTTOM F12 LEACH CUMULATNE QUANTITY REEASE RELEASE REEASE INCRENENTALCUMULATlW EFFECTIVE EACH O LEACH TIME LEACKD RATE RATE RATE RELEASE RELEASE DIFFUSMTY INDEX
................'s'......'.....')..........................
(days) (ug) (ugacm.s
) (cm 8*s- ) (gayr- (cma .s ')
1.(30s) 3 47E-04 NO ---- ---- ---- ---- ---- ---- ----
- 2. (2tv) 8 37E-m N/D ND NO NO NO N/D N/D N/D
- 5. (2d) 2.00E + C0 3 83E+01 2.81E-OS 6.21 E- 10 1.4E-02 8.45E-(D 2.44E-m 3.00E -09 8.52E +00
- 0. (3d) 3 00E +00 N/D N/D NO NO ND 2.44E-m NO N/D
- 7. (4d) 4.00E + 00 N/D N/D N/D N/D ND 2 44E-02 ND ND
- 8. (5d) 5 00E + 00 N/D ND ND N/D NO 2.44E-m NjD ND Maart e.32E-OS 1.4E -CD 31E-Ce 4.01E-09 8 44E+00 Standard Deviatm 42 tE-C8 9 29E-10 2.00E-02 1.91E-09 1.93E-01 FIE NAnAE: Poohruc Acid SAMPE 0: PEACH DOTTOM #12 LEACH CUMULATNE QUANTITY RELIASE RELEASE RELEASE INCREMENTAL CUMULATPE EFFECTIVE EACH D LEACH YlME LEACHED RATE RATE RATE RELEASE P.ELEASE OtFFLKiM TY INDEX
...........................'....').......................
(days) (ug) (ugacm **s ') (cm 8*s- ) (g eyr- (cm8*s 1)
- 1. (36n) 3 47E-04 ND ---- ---- ---- ---- ---- ---- -~~~
- 2. (2tv) 8.37E -CE 2.89E + 04 2 55E-m 1.89E-09 1.27E +02 2.14E-03 2.14E-CD 3.97E - 10 9 40E+00
- 3. (7tv) 2 02E-01 3.02E + 04 1.DeE-02 7.91E-10 5 30E + 01 2 24E-03 4.39E-03 5.72E -10 9 24E +00 4 (10) 1.00E + 00 6 04E +04 0 20E-(n 4 65E-10 3.12E + 01 4 4ttE-00 8 87E-03 6.83E - 10 9.17E +00
- 5. (2d) 2.00E+(D 5 67E+04 4.17E -C0 3.10E-10 2.07E + 01 4 21E-(n 1.31E-T 7.45E- 10 9.13E + 00
- 7. (4d) 4.0E +0C 2 84E+04 2.00E-m 1.55E-10 1.04E +01 2.11 E - 03 1.80E -02 4.45E - 10 9.35E +(D
- 8. (5d) 5.00E +00 2.31 E + 04 1.70E-00 12eE-10 8 45E +00 1.72E -(D 1.97E-CE 3 81E-10 9 42E+00 Meert 7.59E-03 S e3E-10 3 7BE+01 5.41 E - 10 92eE+00 8tarderd Deviatm 7.84E-C0 5.82E-10 3 90E+01 1.30E-10 1.05E-01 i
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D-13 NUREG/CR-6164 l
\
Appendix D Table D-4. Radionuclide concentrations ir leachates (decay corrected to May 19,1993).
Analyte Units PB #4 PB#8 PD#12 Prerinse (30s)
C-14 (uCi/ml) 4.03E-06
- 3.70E-07 7.07E-06
- 1.90E-06 4.67F 43
- 4.20E-06 Fe-55 (uCi/ml) 1.01E-06
- 1.06E-08 1.11E-04
- 2.01 E-06 4.6D-07
- 8.4BE-09 Co-60 (uCi/ml) 6.90E-06
- 6.18E-07 7.04 E-06 1.95E-J5
- 1.44E-06 Ni-63 (uCi/ml) 3.80E-07
- 2.00E-08 1.49E-08
- 2.98E-09 3.31 E-06
- 1.80E-07 Sr-90 (uCi/ml) 2.00E-09
- 2.00E-09 1.12E-08
- 2.93E-09 -2.00E-09
- 2.00E-09 Tc-99 (uCi/ml) -8.60E-08
- 8.60E-09 8.92E-07 i 4.90E 08 -2.48E-08
- 2.40E-09 I-129 (uCi/ml) <1.47E-07 1.59E-08
- 2.00E-09 6.30E-09
- 3.40E-09 Cs-137 wCi/ml) N/D 1.93E-07 1.00E-06
- 2.00E-07 Total alphs* (uCi/mt) 2.00E-09
- 2.00E-09 8.00E-10
- 1,50E-09 Cr (ug'ml) e N/D <0.03 2.70E#7
- 4.00E-03 Fe (ug'ml) 1.90E-02
- 4.00E-03 1.18E+ 00 N/D Co (ug'mt) 9.00E-03
- 8.00E-03 N/D 1.00E-03
- 5.00E-03 Zn (ug/ml) 3.00E-02
- 5.00E-03 5.00E-02 1.40E-02
- 3.00E-03 H (ug/mt) 2.00E-02
- 5.00E-03 1.00E-02 N/D Ni (ug/ml) N/D <0.03 N/D PO4 (ug'mt) 8.00E-02
- 1.00E-02 6.71 E
- 02 as P (total) <0.50 sol (ug'ml) 8.60E-01
- 4.00E-02 <l .00 3.68E+ 00
- 1.80E-01 Picolinic Acid (ug/ml) N/D <6.16E4 01 N/D 2 Ilours C-14 (uCi'ml) 2.53E-05
- 2.20E 06 6.87E-05
- 3.60E-06 8.49E-06
- 7.90E-07 Fe-55 (uci/ml) 4.61 E-06
- 8.48E-08 6.75 E-05
- 1.58E-06 4.96E-07
- 1.90E-07 5.45E-08
- 1.59E-08 4.10E-06
- 2.00E-09 Tc-99 (uci/m!) 3.42E-07
- 2.90E-08 1.47E-06 + 4.50E-08 3.93E.08 * .s.60E-09 l-129 (uCi/ml) 9.10E-07
- 2.40E-08 3.40E-09 i 1.80E 09 3.70E-08
- 2.00E-07 Total alpha * (uCi/ml) 2.00E-09
- 2.00E-09 1.00E-09
- 2.00E-09 Cr (ug/ml) 2.30E-02
- 4.00E-03 <0.03 3.80E-02
- 3.00E-03 Fe (ug/ml) N/D 6.40E-01 2.90E-02
- 4.00F,03 l
Co (ug/ml) 1.20E-02
- 7.00E-03 N/D 8.00E-03
- 5.00E 03 Zn (ug'ml) 1.90E-02
- 4.00E-03 <0.03 2.20E-02
- 4.00E-03 B (ug/ml) 1.80E-02
- 4.00E-03 <0.01 N/D Ni (ug'ml) 2.80E-02
- 5.00E-03 <0.03 4.50E-02
- 5.00E-03 PO4 (ug/ml) 6.00E-02
- 1.00E-02 <0.50 as P (total) <0.50 SO4 (ug'ml) 1.60E+00
- 8.00E-02 <l .00 6.20E400
- 3.00E-01 Picolinic Acid (ug/ml) 1.84E+01 <6.16E+01 1.66E+0!
NUREG/CR-6164 D-14
Appendix D Table D-4. (continued).
Analyte Units PB #4 PB#8 PB#12 l
7 Ilours C-14 (uCi/ml) 5.87E-06
- 5.30E-02 5A2E-05
- 3.37E 06 5.54 E-06
- 5.20E-07 Fe-55 (uCi/ml) 1.06E-06
- 1.80E-08 3.84E-05 i 1.59E46 3.35E-06
- 6.36E-08 Co-60 (uCi/ml) 5.36E-05
- 4.12E-06 5.46E-05 5.25E-05
- 4.12E-06 Ni-63 (uCi/ml) 3.80E-06
- 2.00E-07 4.07E-08
- 9.93E-09 3.44E-06
- 1.90E-07 Sr-90 (uCi/mt) -2.00FA9
- 1.00E-09 1.50E-08
- 2.93E-09 2.00E-09
- 1.00E-09 Tc-99 (uCi/ml) 3.04E-07
- 2.60E-08 1.13E-06 i 4.00E4 4AIE-07
- 3.80E-08 I-129 (uCUml) <4.02E-08 8.50E-09
- 1.80E-09 <l .08E-08 Cs-137 (uCi/ml) N/D 4.8 t E 07 N/D Total alpha * (uCi/ml) 1.00E-09
- 2.00E-09 8.00E-10
- 1.90E-09 Cr (ug/ml) 2.30E-02
- 4.00E-03 <0.03 3.50E-02
- 4.00E-03 Fe (ug'ml) N/D 1.90E-01 3.50E-02
- 5.00E-03 Co (ug/ml) 1.80E-02
- 9.00E-03 N/D 1.00E-02
- 7.00E-03 Zn (ug'mt) N/D (0.03 2.30E-02
- 4.00E-03 D (ug'ml) N/D <0.01 2.00E-02
- 4.00E-03 Ni (og/mt) 2.60E-02
- 5.00E-03 <0.03 4.00E-02
- 7.00E 03 PO4 (ug/ml) <0.50 <0.50 as P (total) <0.50 SO4 (ug'ml) 7.00E+01
- 3.00E+00 <l .00 8.30E+00
- 4.00FAI Picolinic Acid (ug'ml) 1.83E+01 <6.16E
- 01 1.74E+01 1 Day C-14 (uCi/ml) 3.04 E-06
- 2.80E-07 7A6E-05
- 3.70E-06 4.48E-06
- 4.20E-07 Fe-55 (uCi/ml) 9.76E-07
- 1.70E-08 3.05E-05
- 1.77E-06 I A2E-06
- 2.12E 08 Co-60 (uCi/ml) 8.14 E-05
- 6.18E 06 1.18E44 7.52E-05
- 5.15E-06 Ni-63 (uCi/ml) 4.80E-06
- 3.00FA7 5.36E-08
- 1.39E 08 5.30E-06
- 3.00FA7 Sr-90 (uCi/ml) -9.00E 10
- 1.00E-09 2.03E-08
- 2.93E-09 5.00E-10
- 1.00E-09 Tc-99 NCi/ml) 7.16E-07
- 6.00E 08 5.88E-05
- 1.60E-06 2.05E-06
- 1.40E 07 1-129 (uCi/ml) 2.27E-08
- 6.30FA9 <l E-09 3.88E-08
- 9.20E-09 Cs-137 (uCi/mi) N/D 1.26E-06 8.00E-07
- 2.00E-07 Total alpha * (uCi/ml) 2.00E-09
- 2.00E-09 3.00E-09
- 2.00E-09 Cr (ug/ml) 3.80E-02
- 6.00E-03 <0.03 4.70E 02
- 3.00E-03 Fe (ug/ml) 1.60E-02
- 4.00E-03 6.00E-02 4.20E-02
- 4.00E-03 Co (ug'ml) 1.70E-02
- 8.00E-03 N/D 5.00E-03
- 6.00E43 Zn (ug/ml) 1.30E 02
- 4.00E-03 <0.03 2.50E-02
- 4.00E 03 D (ug/ml) 2.00E-02
- 5.00FA3 <0.01 2.20E-02
- 4.00E-03 Ni (ug/ml) 3.00E-02
- 8.00E-03 <0.03 5.40E-02
- 5.00E-03 PO4 (ug/ml) <0.50 <0.50 as P (total) <0.50 SO4 (ug/ml) 1.13E+0i
- 6.00E 01 9.33E+00 1.06E+ 01
- 5.00E-01 Picolinic Acid (ug'ml) 3.55E+01 <6.16E+ 01 3.52E+01 D-15 NUREG/CR-6164
Appendix D Table D-4. (continued).
Analyte Units PB #4 PB#8 PH#12 2 Days C-14 (uCi/ml) 4.24E-06
- 4.00E-07 6.86E-05
- 3.57E-06 5.66E-06
- 5.30E-07 Fe-55 (uCi/ml) 1.l lE-08
- 2.12E-10 1.32E-05
- 7.95E-07 1.65E-06
- 3.18E-08 Co-60 (uCi/ml) 6.49E-05
- 5.15E-06 1.03E-04 6.39E-05 i 5.15E-06 ;
Ni-63 (uCi'ml) 3.07E-06
- 1.70E-07 2.18E-08 i 4.97E-09 3.90E-06
- 2.00E-07 St-90 (uCi'ml) 2.00E-09 i 1.00E-09 <l.0E-09 -5.00E-10
- I .50E-09 )
Tc-99 (uci/ml) 3.00E-06
- 2.30E-07 1.54 E-06
- 4.60E-08 2.91 E-06
- 2.10E-07 l-129 (uCi/ml) 1.48E-07
- 3.10E-08 2.41E-08
- 2.60E-09 5.40E-09
- 7.50E-09 Cs-137 (uCi/ml) N/D 8.65 E-07 N.D Total alpha' (uCi/ml) 1.10E-09
- 2.00E-09 1.00E-09
- 3.00E-09 Cr (ug/ml) 3.80E-02
- 6.00E-03 <0.03 4.40E-02
- 3.00E-03 Fe (ug/ml) N/D 8.00E-02 2.90E-02
- 3.00E-03 Co (ug/m!) 6.00E-03
- 6.00E-03 N/D 9 00E-03
- 6.00E-03 Zn (ug/ml) 1.50E-02
- 4.00E 03 <0.03 1.70E-02
- 5.00E-03 II (ug/ml) 2.00E-02
- 5.00E-03 <0.01 2.20E-02
- 4.00E-03 l Ni (ug'ml) 3.00E-02
- 5.00E-03 <0.03 4.00E-02
- 6.00E-03 4 I PO4 (ug/ml) <0.50 <0.50 as P (total) <0.50 SO4 (ug'mt) 1.04E401
- 5.00E-01 7.97E4 00 1.18E+ 01
- 6.00E-01 Picolinic Acid (ug'ml) 3.34 E+ 01 <6.16E401 3.26E+ 01 1 i
, 3 Days l l
C-14 (uC./ml) 3.48E-06
- 3.30E-07 4.93 E-05
- 3.13 E-06 6.13E-06
- 5.80E-07 Fe-55 (uCi'ml) 8.10E-08
- 1.38E-09 6 00E-06
- 5.29E-07 7.26E-06
- 1.27E-07 Co-60 (uCi/ml) 4.64 E-05
- 3.09E-06 6.86E-05 4.74 E-05
- 3.09E-06 Ni-63 (uCi/ml) 2.14 E-06
- 1.20E-07 8.94 E-09
- 3.97E-09 2.54E 06
- 1.40E-07 Sr-90 (uCUml) -2.00E-09
- 2.00E-09 <l E-09 -5.00E-09
- 1.00E-09 Tc-99 (uci/ml) 5.81 E-07
- 5.00E-08 1.59E-06
- 5.90E-08 1.71E-06
- 1.20E-07 l129 (uCi/ml) <7.96E-09 2.07E-08
- 3.80E-09 3.36E-08
- 3.00E-09 2.00E-09
- 2.00E-09 Cr (ug'ml) 3.20E-02
- 3.00E-03 <0.03 3.80E-02
- 3.00E-03 Fe (ug'ml) 1.50E-02
- 4.00E43 5.00E-02 2.40E-02
- 4.00E 03 Co (ug'ml) 7.00E-03
- 5.00E-03 N,D 1.60E-02
- 8.00E-03 Zn (ug/ml) N/D <0.03 1.30E-02
- 4.00E-03 Il (ug'mi) 2.00E-02
- 5.00E-03 <0.01 N.D Ni (ug'mt) 2.90E-02
- 5.00E-03 <0.03 4.30E-02 i 6.00E-03 PO4 (ug'ml) <0.50 <0.50 as P (total) <0.50 SCM (ug'ml) 8.10E+00
- 4.00E-01 6 69E+00 8.20E 4 00 1 4 00E-01 Picolinic Acid (ug'ml) 2.09E401 <6.16 E + 01 2.18E +01 NUREG/CR-6164 D-16
Appendix D Table D-4. (continued').
Analyte Units PB #4 PD#8 PB#12 4 Days C 14 (uCUmi) 2.05E-05
- 1.90E-06 4.07E-05
- 1.37E-06 2.48F-06
- 2.40E-07 Fe-55 (uCi/ml) 4.17E-07
- 7.42E-09 2.86E-06
- 6.70E-07 1.52E-06
- 3.18E-08 Co-60 (uCi/ml) 3.61E-05
- 3.09E-06 6.16E-05 3.71 E-05 i 3.09E-06 Ni-63 (uCi/ml) 1.51 E-06
- 8 00E-08 <5 E-09 2.14E-06
- 1.20E-07 Sr-90 (uCUml) 2.00E-09
- 1.00E-09 6.35E-09
- 3.32E-09 2.00E-09
- 1.00E-09 Tc-99 (uci/ml) 4.79E-07
- 4.20E-08 7.31E-07 4 4.60E-08 1.04 E-07
- 8.20E-08 I-129 (uCi'ml) 1.10E-08
- 1.00E-08 1.2 t E-08
- 2.60E-09 <l .90E-07 Cs-137 (uCi/ml) N/D 6.58E-07 N/D Total alpha' (uCi/ml) 1.00E-09
- 2.00E-09 2.00E49
- 2.00E-09 Cr (q/ml) 2.20E-02 4.00E-03 <0.03 3.60E 02
- 3.00E-03 Fe (ug'ml) 1.40E-02
- 4.00E-03 3.00E-02 2.50E-02
- 4.00E-03 Co (ug/ml) 9.00E-03
- 7.00E-03 N/D 1.40E-02 i 7.00E 03 Zn (ug/ml) N/D 3.00E-02 1.50E-02
- 4.00E-03 D (ug/ml) N/D 2.00E-01 N/D Ni (ug'ml) 2.90E-02
- 5.00E-03 <0.03 3.70E-02 i 6.00E-03 PO4 (ug'mi) <0.50 3.00E-02 as P (total) < 0.50 SO4 (ug'ml) 6.80E+00
- 3.00E-01 8.00E+00 6.20E+00
- 3.00E-01 Picolinic Acid (ug'ml) 1.64E+01 <6.16E4 01 1.64 E401 5 Days C-14 (uCUm!) 1.30E-05 i 1.20E-06 8.53E-05 1.71 E-06
- i 1.94E-06 1.80E-07 Fe-55 (uci,ml) 3.18E-07
- 5.30E-09 2.78E-06
- 9.74 F.-07 1,48E-06
- 3.18E-08 Co-60 (uCi/ml) 2.78E-05
- 2.06E-06 ! .36E-04 3.19E-05
- 2.06E-06 Ni-63 (uCi/ml) 2.42E-06
- 1.30E-07 <5 E-09 1.76E-06
- 9.00E-08 Sr-90 (uCi/ml) -4.00E-09
- 2.00E-09 4.0! E-09
- 1.95E-09 2.00E-09
- 2.00E-09 Tc-99 (uCi/m!) 3.61 E-07
- 3.20E-08 3.75E-06
- 1.32E-07 9.58E-07
- 6.90E-08 1-129 (uCi/mi) 5.80E-08
- 1.50E-08 2.38E-08 i 2.90E-09 8.30E-08
- 3.10E-08 Cs-137 (uci/mi) N/D 1.41 E-06 N/D Total alpha * (uCi/ml) 1.30E-09
- 1.70E-09 1.00E-09
- 2.00E-09 Cr (ug/ml) 2.70E-02
- 4.00E-03 <0.03 3.40E-02
- 4.00E-03 Fe (ug'm!) N'D 5.00E-02 N/D Co (ug/ml) 1.10E-02 i 6 00E-03 N/D 1.30E-02
- 7.00E-03 Zn (ug'ml) N/D 7.00E-02 1.60E-02
- 3.00E-03 D (ug'ml) N/D 6.00E-02 N/D Ni (ug'ml) 2.50E-02
- 6 00E-03 <0.03 4.00E-02
- 8.00E-03 PO4 (ug'ml) <0.50 6.00E-02 <0.50 as P (total) sot (ug'ml) 5.30E+00
- 3.00E-01 1.llE+01 5.30E+00
- 3.00E-Ol Picolinic Acid (ug/ml) 1.27E+ 0! <.6.16 E + 01 1.33E+01
- The activity of the nuclides was at or below the detection limit o(atmut 0.004 pCi/mL. The value reported is the sum of all actinide activity, except protactinium, found in the sample.
D-17 NUREG/CR-6164
Appendix D Table D-5. Leach test results for James A. FitzPatrick mixed-bed resin waste-form specimen leached in deionized water.a Release rate Average effective diffusivity Leachability Nuclide CFR (LCi . em.2 . 3-1) (cm.2 . 3-1)b (cm2. s-1) index 54Mn 5.6 (-4) 1.0 i 0.5 (-9) 6 i 3(-12) 3 i I (-13) 13.3 0.3 55Fe 6.1 (-3)c 7 i 5 (-10) 7 i 5 (-11) 3 2 (-l1) I1.6 i 0.8 58Co 1.2 (-2) 9 i 2 (-9) 5 i I (-11) 2.6 i 0.7 (-11) 10.8 i 0.2 60Co 1.7 (-2) 5 i 1 (-8) 7 2 (-l1) 5 i I (-l1) 10.5 0.2 63Ni 9.2 (-2)c 1.3 i 0.4 (-8) 6 i 1 (-10) 4 1 (-9) 8.9 i 0.3 65Zn 2.3 (-3) 4 2 (-10) 1.0 0.5 (- 1 I ) 1.2 i 0.4 (-12) 12.3 i 0.2 90Sr --d --d -d -d .-d 125Sb <7.7 (-3) <7.9 (-l 1) <5.1 (-l 1) <3.6 (-l 1) > l 1.0 134Cs 7.3 (-1) 8 i 3 (-9) 6 i 2 (-9) 3.6
- 0.7 (-7) 6.6 i 0.2 137Cs 6.4 (-1) 1.5 i 0.5 (-8) 512(-9) 1.5 i 0.5 (-7) 7.1 i 0.2 241Pu -c 6.7 (-12) 6.9 (-13) 2.2 (-15) 14.7 Acid or metal (pg/cm2 s)
Picolinic acid 5.4 (-1) 8 i 3 (-3) 3 i I (-9) 1.4 i 0.8 (-7) 7.5 i 0.3 Chromium <6.6 (-3)c <l .6 (-6) <5.7 (- 11) <2.4 (-11) > l 1.2 Iron <3.3 (-3)c <l.0 (-5) <2.6 (-l I ) <5.4 (-12) > l 2.0 Cobalt <2.5(-2)c <8.0 (-6) <# 10) <3.5 (-10) > 10.0 Nickel 5.0 (-2)c 5 t 2 (-6) 3 1 (-10) 1.1 i 0.5 (-9) 9.4 i 0.4
- a. Results are for only the first 90 days of leaching.
- b. Fraction of initial inventory released per square centimeter of specimen surface area per second.
- c. Not all leachate samples were analyzed for this radionuclide or metal. CFR value was estimated by interpolating measured incremental release rates.
- d. Concentrations of radionuclide in teachate samples were not determined.
- c. Only the leachate corresponding to teaching interval number three was analyzed for 241Pu. Leaching results are tbase determined for leaching interval number three.
NUREG/CR-6164 D-18
4 5
l i
. 1 i
i i
Appendix E l
Radionuclide, Chelating Agent, and Stable Metal Inventory in Peach Bottom-3 Liner 446828-15 l
1 E-1 NUREG/CR-6164
sh+44--se.--*=--4 A DA4 --LS
_ __. 4 Ae-awr, emaaaw-M.n.4y-"sha.,We--4**,. A4 -J p - .4 s.ma m A.ha enwee- 4ps, ses.w - a. as *>-s-ema--.me-a3ah-ma a- - - - . . -> -ayw--
9 e
J t
e h
i 0
h f
1 I
[
't
$ YTT FT'Vs.TNFP M41'y MMMW 9 ggg wyg' M g , , a-W,, ,,w wpg;*We 3m 9.gemyty .ggme ygygwwesp we wagoevow
Appendix E Appendix E Radionuclide, Chelating Agent, and Stable Metal inventory in Peach Bottom-3 Liner 446828-15 Table E-1 surnmarizes the radionuclide, chelat. 54Mn,125Sb,137Cs, 242Cm,14C,and99Tc were ing agent, and stable metal inventories in Peach multiplied by the resin-to-total-material ratio Bottom-3 lir.er #446828. All inventories are (0.5) for inclusion in the total. The primary based on the measured radionuclide content in the decontamination radionuclides present in the res-cemented waste form with the exception of those ins based on their measured concentration are listed below. These radionuclide concentrations 54M n, 65Zn, 60Co, 55pe, 63Ni,and 14C. The were taken from the resin samples due to apparent summed activity of these radionuclides is 55 Ci or problems with the analysis of the waste-form about 98% of the total activity. Carbon-14 makes samples. The total mass of material in the liner up about 58% of the total activity. The dominant was 7,180 kg and the radionuclide concentra-decontamination radionuclides 60Co and 55pe tions have been extrapolated to this mass based on make up about 31% and 1.9% of the total activity.
the data summarized m Table 6. The liner was a L14-170 liner with a capacity of 4.79m3. In c ntrast, the fiss. ion products 90S r, 99Tc,1291, and 137Cs collectively constitute about 0.3% of The concentrations of radionuclides, chelating the total activity. The concentrations of the trans-agents, and stable metals in the liner is presented uranic isotopes are also low and sum to a total of in Table E-1 as Ci/ liner for radionuclides or kg of 1.I x 10-2 Ci (0.02% of the total activity).
stable metals or chelates. The summed radionu- Greater than 87% of the transuranic activity was clide content is 56 Ci/ liner. Resin results for 241Pu.
E-3 NUREG/CR-6164
Appendix E Table E-1. Radionuclide, stable metal, and chelating agent inventory in Peach Bottom-3 liner
- 446828-15 (Ll4-170 with a capacity of 4.79mh (Decay date 10/25/89).
Peach Bottom-3 liner inventory Radionuclide (Ci or g) 54Mn 1.5E-0 0.2E- 1 55Fe 1.0E O 3.9E- 1 60Co 1.7 E+ 1 8.6E-3 s
63Ni 1.9E- 1 2.2E-2 65Zn 3.4E O 1.1 E O 125Sb 6.lE-2 3.5E-3 137Cs 1.3E-2 1.8E-3 WSr 3.0E-4 5.4E-5 238Pu 5.9E-4 i 3.7E-5 239Pu 1.8E-4 1. l E-5 241Pu 9.9E-3 t 1.0E-3 24iAm 7.2 E-4 5.0E-5 242Cm 2.9E-5 i 3.3E-6 244Cm 1.3 E-4 1.6E-4 14C 3. l E+ 1 3.lE-l Mc 1.3E-1 i 3.0E-3 1291 1.7E-4 i 2.5E-5 Chromiuma 7.4E+2 1.4E+ 1 frona 2. l E+1 t 1. lE O Zinca 1. l EO 8.6E-1 Nickel 8 5.2E0 2.lE-1 Cobalt 1. l E- 1 Boronb 1.3 E- 1 Picolinic acide 3.9E- 1
- a. Analyses performed using inductively coupled plasma spectroscopy elemental analysis methods,
- b. Analyses performed using ion chromatography.
- c. Analysis performed using picolinic acid titration. Due to uncertainties in the solidified waste analysis, the kmding m the liner will be used.
NUREG/CR- E-4
NIC PomM 335 U.S. NUCL E AR REGUL ATORY COMMil$lON 1. REPORT NUMBER C e 102.
- .m2 BIBUOGRAPHIC OATA SHEET b M"[MYf, *""*
is,,,meroom en en. n , NUREG/CR-6164
- 2. TITLE AND SUBTITLE EGG-2722 Release of Radionuclides and Chelating Agents from Cement-Solidified Decontamination Low-Level Radioactive Waste Collected from the Peach 3. DATE REPORT PUGLISHED Bottom Atomic Power Station Unit 3 "o
- u*a l
h ret 1994
- 4. F 6N OR GR ANT NUM6E R A6359 L AUTHOR (5)
- 6. TYPE OF REPORT D. W. Akers, N. C. Kraft, L W. Mandler Technical
- 1. PE R JOD COV E R k O nwuseer Osten
- 8. negee PE R sed F0R uiMG MG ANSI ATLON - NAM E ANO AOORlSS uso Nnc. s.,evoer oneonoon. Orroce or nepron, u5 Nucmar norusorary commeas on and masne een eso, or sentracter. orevoar M,fedJne SWO8Wst/
Idaho National Engineering Laboratory EG&G Idaho ine P.O. Box 1625 Idaho Falls, Idaho 83415 i O R R G Ak6Z A TION - N AM E Ako AODR EbS too Nnc. troe some as aae,e". er coorrocror orav.or Nnc o, .s on. oro,co or neeen. v1 Noewer noruietare ce,amowee.
Division of Regulatory Applications Office of Nuclear Regulatory Research U.S. Nuclear Regulatory Commission Washington, D.C. 20555-00',1 10 SUPPLEMENTARY NCTES
- 11. A857 R AcT ttoo . ores or mm As part of a study being perfonned for the Nuclear Regulatory Commission (NRC), small-scale waste-fonn specimens were collected during a low oxidation-state transition-metal ion (LOMI)-nitric permanganate (NP)-LOMI solidification performed in October 1989 at the Peach Bottom Atomic Power Station Unit 3. The purpose of this program was to evaluate the performance of cement-solidined decontamination waste to meet the low-level waste stability requirements defined in the NRC's " Technical Position on Waste Form," Revision 1. The samples were acquired and tested because little data have been obtained on the physical stability of actual cement-solidified decontamination ion-exchange resin waste forms and on the leachability of radionuclides and chelating agents from those waste forms. The Peach Bottom waste-form specimens were subjected to compressive strength, immersion, and leach testing in accordance with the NRC's " Technical Position on Waste Form,"
Revision 1.
Results of this study indicate that the specimens withstood the compression tests (>500 psi) before and after immersion testing and leaching, and that the leachability indexes for all radionuclides, including 14C, Me, and 129g, are well above the leachability index requirement of 6.0, required by the NRC's " Technical Position on Waste Form," Revision 1.
2 K E Y WOR DS/DE sca tPTOR S roar .oros er aarws en,# mu mor ,wenm o. soc,,o e en ,e,on.s is. Ava.Lasiutv sTarsueNT Waste Form Stability, Leachability, Decontamination Process, Radionuclide Behavior Unlimited
- 14. 6t Cuni t V CLA SSJ 6 CAT.QN IThos 9eper Unclassified ITne nooorro Unclassified
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