Text

Physical Tests on Solidified Decontamination Wastes from Dresden Unit 1
	ML20083H498
Person / Time
Site:	Dresden
Issue date:	12/31/1983
From:	Adams J, Barletta R, Robert Davis; BROOKHAVEN NATIONAL LABORATORY
To:	; NRC OFFICE OF NUCLEAR MATERIAL SAFETY & SAFEGUARDS (NMSS)
References
	CON-FIN-A-3159 BNL-NUREG-51648, NUREG-CR-3165, NUDOCS 8401130224
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NUREG CR-3165 1

BNL-NUREG-51648 Physical Tests on Solidified Decontamination Wastes from Dresden Unit 1

Prepared by R. E. Barletta, J. W. Adams, R. E. Davis Brookhaven National I.aboratory Nuclear Regulatory Commission t

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NUREG/CR-3165 BNL-NUREG-51648 l

Physical Tests on So idified Decontamination Wastes from Dresden Unit 1 Manuscript Completed: June 1981 Date Published: December 1983 Prepared by R. E. Barletta, J. W. Adams, R. E. Davia l

Department of Nuclear Energy brookhaven National Laboratory Upton, NY 11973 Prcpared for Division of Waste Management Office of Nuclear Material Safety and Safeguards U.S. Nuclear Regulatory Commission Wcshington, D.C. 20555 NRC FIN A3159

i ABSTRACT i

The results of immersion and leach tests of NS-1 concentrate solidified in a vinyl ester-styrene binder are reported.

Immersion tests of waste forms prepared at a solidification demonstration held at the Dresden Nuclear Power i

Station were conducted.

These forms were immersed in toluene, xylene, and water saturated with toluene and xylene. As a result of immersion of samples in the pure organics, large changes in sample volume and weight were observed.

Total weight changes as a result of immersion of 9.6 + 0.3% and 21.6 + 0.7%

were observed after 839 hours0.00971 days 0.233 hours 0.00139 weeks 3.192395e-4 months of immersion in xylene and toluene respectively.

Air drying of the samples led to an overall weight loss of 23.5 + 0.7% for xylene and 35.6 1 0.6% for toluene. Qualitatively, similar changes were ob-served for immersion tests using organic saturated water.' Severe sample deterioration was observed in this case, however.

The behavior of cut and uncut samples from leach tests subjected to immersion in either organic satu-4 rated water or toluene was qualitatively the same as for the sectioned sample.

Severe sample deterioration was noted in both cut and uncut forms immersed in organic saturated water.

1 Leach tests were carried out to measure the iron and nickel and cobalt re-lease from these waste forms in deionized water, groundwater, and seawater, After 64 days, the mean fraction released normalized by V/S for iron was 5.1 +

i 1.9 x 10-3 cm in deionized water, 7.1 + 1.1 x 10-3 cm in groundwater, and 1.0 + 3.2 x 10-3 cm in seawater.

For nickel 64 day release rates observed were 4.6 + 1.6x 10-3 cm, 4.6 + 1.0 x 10-3 cm,, and 5.9 + 0.6 x 10-3 c.m in

~

deionized water, groundwater,~and seawater, respectiveTy$ and 2 8 +

After 50 days, the 59Fe rele 1.0 x 10 gse rates are 5.9 + 0.7 x 10-3, 4.8 + 2.4 x 10 cm in deionized water, groundwater 7 and seawater, respedtively.

For 60Co, the 5 media are 6.0 + 1.7 x 10 g day releases in the three respective leachin cm, 6.8 + 1.0 x 10-3 cm, and 2.3 + 0.2 x 10- cm.

i l

iii

CONTENTS ABSTRACT.................................

iii CONTENTS.................................

v FIGURES.................................

vi TABLES..................................

ix A C KN O WL E D GE ME NTS.............................

xii 1.

INTRODUCTION.

1 2.

IMME RS I ON TE S TS...........................

3 2.1 E x p e r i me n t al..........................

3 2.1.2 Immersion Test of Unleached Samples...........

3 2.1.2 Immersion Test of Samples From Leach Study........

6 2.2 Results and Discussion.....................

10 2.2.1 Immersion Test of Unleached Samples.

10 2.2.2 Immersion Test of Samples From the Leach Study......

19 3.

LEACHING TESTS............................

27 3.1 E x p e r i men t a l..........................

27 3.1.1 Leach Tests of Samples Prepared at Dresden........

27 3.1.2 Leach Tests of 59Fe and 60 o From NS-1/Dow........

C

3. 2 Results and Discussion.....................

30 3.2.1 Leach Tests of Samples Prepared at Dresden........

30 3.2.2 Leach Tests of 59Fe and 60Co From NS-1/Dow........

3.2.3 Comparison of BNL Results With Leach Tests Performed by Dow...........................

63 4.

CONCLUSIONS.............................

65

5. REFERENCES..............................

67 APPENDIX A - RADWASTE SOLIDIFICATION SYSTEM-DRESDEN 1 CHEMICAL CLEANING r

l FACILITY..........................

69 APPENDIX B - COMPUTER PROGRAM USED TO CALCULATE LEACH RATE DATA......

89 APPENDIX C - 00W COMMENT ON LEACH TEST RESULTS..............

98 i

V

FIGURES 2.1 Sampl e 1 P ri o r to Imme rs i o n....................

4 2.2 Apparatus Used to Measure Weight of Disk Suspended in Solution...

5 2.3 Samples Froa Leach Test Prior to the Start of the Immersion Test A, Sample 2; B, Sample 3; C, Sample 4; D, Sample 5; E, Sample 6; F, Sampl e 7 ; G, Sampl e 8 ; H, S ampl e 9...............

7 2.4 Cut Surface of Sample From Leach Test Prior to the Start of the Immersion Test ( Sampl e 9A).................

9 2.5 NS-1/Dow Sample After 14 Days of Immersion in Toluene (Sample 6)..

11 2.6 Plot of N vs Time for NS-1/Dow Sample Disks Immersed in, a, Xylene and, b, Toluene..........................

14 2.7 Plot of E vs Time for NS-1/Dow Sample Disks Drying in Air Af ter Immersion Test in, a, Xylene and, b, Toluene............

15 2.8 Samples of NS-1/Dow After 14 Days of Immersion in Water Saturated With Toluene and Xylene, (a) Sample 7; (b) Sample 8........

17 2.9 Plot of Mean Aw vs time for NS-1/Dow Samples From Leach Tests 1

Immersed in Toluene. o Uncut Samples; o Cut Samples........

22 2.10 Plot of Mean Aw vs Time for NS-1/Dow Samples From Leach Tests Immersed in Organic Saturated Water. O Uncut Sam o Cut Samples..................pl es; 23 2.11 Samples of NS-1/Dow From Leach Test After 14 Days Immersion Test in Organic Saturated Water (Samples 2, 3A, 5, 6A, 8) and Toluene (Samples 3B, 4, 6B, 7, 9B). A-Sample 2; B-Sample 3b; C-Sample 4; D-Sample 5; E-Sample 6a; F-Sample 7; G-Sample 8; H-Sample 9b....

24 i

2.12 Condition of the Cut Surface of Sample 9A Af ter 1 Day Immersion in Organic Saturated Water......................

26 3.1 Cumulative Fraction. Released (C.F.R.) of Fe for NS-1/Dow Leached in Deionized Water. O Sample 2, o Sample 3, A Sample 4 37 3.2 Cumulative Fraction Released (C.F.R.) of Ni for NS-1/Dow Leached in Deionized Water. o Sample 2, o Sample 3, A Sample 4........

37 3.3 Cumulative Fraction Released (C.F.R.) of Fe for NS-1/Dow Leached in Groundwater. O Sampl e 5, o Sampl e 6, A Sample 7..........

38 3.4 Cumulative Fraction Released (C.F.R.) of Ni for NS-1/Dow Leached in Groundwater. O S ampl e 5, o S ampl e 6, A Sampl e 7..........

38 l

vi

, FIGURES, Continued 3.5 Cumulative Fraction Released (C.F.R.) of Fe for NS-1/Dow Leached in Seawater. C Sampl e 8, o Sampl e 9..................

39 3.6 Cumulative Fraction Released (C.F.R.) of Ni for NS-1/Dow Leached in Seawater. O Sampl e 8, o Sampl e 9.................. 39 3.7 Average Cumulative Fraction Released (C.F.R.) of Fe for NS-1/Dow Leached i n Deioni zed Water...................... 40 3.8 Average Cumulative Fraction Released (C.F.R.) of Ni for NS-1/Dow Leached in Deionized Water...................... 40 3.9 Average Cumulative Fraction -Released (C.F.R.) of Fe for NS-1/Dow Leached in Groundwater........................

41 3.10 Average Cumulative Fraction Released (C.F.R.) of Ni for NS-1/Dow Leached i n Groundwa ter........................ 41 3.11 Average Cumulative Fraction Released (C.F.R.) of Fe for NS-1/Dow Leached i n Seawater......................... 42 3.12 Average Cumulative Fraction Released (C.F.R.) of Ni for NS-1/Dow Leached in Seawater......................... 42 3.13 Cumulative Fraction Released (C.F.R.) of Ni for NS-1/Dow Leached in Deionized Water " Worst Case." o Sam Sampl e 4...............pl e 2, o Sampl e 3,

................ 45 3.14 Average Cumulative Fraction Released (C.F.R.) of Ni for NS-1/Dow Leached in Deionized Water " Worst Case."

45 3.15 Cumulative Fracticn Released (C.F.R.) of 59Fe for NS-1/Dow Leached in Deicnized Water. O Sampl e 1, o Sampl e 2............. 56 3.16 Cumulative Fraction Released (C.F.R.) of 60Co for NS-1/Dow Leached in Deionized Water. O Sample 7, o Sample 8, a Sample 9.......

56 3.17 Cumulative Fraction Released (C.F.R.) of 59Fe for NS-1/Dow Leached in Groundwater. o Sampl e 3, o Sampl e 4............... 57 3.18 Cumulative Fraction Released (C.F.R.) of 60Co for NS-1/Dow Leached in Groundwater. o Sampl e 10, o Sampl e 11..............

57 3.19 Cumulative Eraction Released (C.F.R.) of 59 e for NS-1/Dow Leached F

in Seawater. o Sample 5, o Sample 6

................ 58 3.20 Cumulative Fraction Released (C.F.R.) of 60Co for NS-1/Dow Leached in Seawater. O Sampl e 12, o Sampl e 13................

58 vii

i l

l FIGURES, Continued 59 e for NS-1/Dow 3.21 Average Cumulative Fraction Released (C.F.R.) of F

Leached in Deionized Water.....................

E9 60 o for NS-1/Dow 3.22 Average Cumulative Fraction Released (C.F.R.) of C

Leached in Deionized Water.....................

59 4

59 e for NS-1/Dow l

3.23 Average Cumulative Fraction Released (C.F.R.) of F

Leached in Groundwater.......................

60 60Co for NS-1/Dow 3.24 Average Cumulative Fraction Released (C.F.R.) of Leached in Groundwater.......................

60 59 e for HS-1/Dow 3.25 Average Cumulative Fraction Released (C.F.R.) of F

Leached in Seawater........................

61 60Co for NS-1/Dow 3.26 Average Cumulative Fraction Released (C.F.R.) of Leached in Seawater........................

61 I

i i

1 viii

TABLES 1.1 Predominant Radionuclides Expected in the Solidified Waste Resulting From the Decontamination of Dresder-1..........

2 2.1 Initial Dimensions of the Simulated NS-1/Dow Sample Disks Used in Imme rs i o n Te s ti ng.........................

4 2.2 Dimensions of NS-1/Dow Samples From Leach Testing Prior to the Start of Imnersion Testi ng....................

9 2.3 Dimensions of Simulated NS-1/Dow. Sample Disks After Immersion in Tol uen e a nd Xyl e ne........................

10 2.4 Sample Weights With Time of NS-1/Dow Sample Disks Immersed in l

Tol u e n e a n d Xyl e n e........................

12 2.5 Mean Percent Weight Change,17, for NS-1/Dow Samples Immersed in To l u e n e a n d Xy l e n e........................

13 2.6 Weight of NS-1/Dow Sample Disks Drying in Air Af ter Immersion in Toluene and Yylene for 839 Hours.................

14 2.7 Mean Percent Weight Change, ZE, for NS-1/Dow Samples Drying in Air Af ter Immersion in Toluene and Xylene for 839 hrs.......

16 2.8 Sample Weight and Change in Sample Weight, Z7, With Time of NS-1/Dow Sample Disks Immersed in Water Saturated With Toluene a n d Xy l e n e............................

17 2.9 Sample Weights and Change in Weight, ZW, for NS-1/Dow Sample Disks Which are Air Drying Following Immersion in Toluene Sa tur a te d Wa te r..........................

18 2.10 Mean Percent Weight Change, IW, for NS-1/Dow Samples From the 64-Day Leach Test Immersed Cut and Uncut in Toluene and Organic Sa tu ra te d Wa te r..........................

20 2.11 Mean Percent Weight cnunge, 7W, for NS-1/Dow Samples From the 64-Day Leach Test Dryi.g in Air After Immersion in Either Toluene and Organic Saturated Water....................

21 3.1 NS-1/Dow Samples for Leach Test.

27 3.2 Results of Analysis of Groundwater and Seawater Blanks......

28 3.3 NS-1/Dow Deionized Water Leach Results Reported in pg/L (ppb)...

31 3.4 NS-1/Dow Groundwater Leach Results Reported in ug/L (ppb).....

32 ix

TABLES, Continued 1

i 3.5 NS-1/Dow Seawater Leach Results Reported in ug/L (ppb)......

33 i

3.6 Incremental and Cumulative Fraction Released of Fe and Ni for NS-1/Dow Leached in Deionized Water................

34 3.7 Incremental and Cumulative Fraction Released of Fe and Ni for NS-1/Dow Leached in Groundwater..................

35 4

3.8 Incremental and Cumulative Fraction Released of Fe and Ni fo r NS-1/Dow Le a ch ed i n Se a wa t e r...................

36 3.9 Average Cumulative Fraction Release After 50 and 64 Days of Leaching.............................

43 3.10 Average Cumulative Fraction Release x V/S After 50 and 64 Days of Le a c h i n g.............................

43 3.11 Comparison of Prepared Standards Analyzed by Flameless Atomic Absorption Spectroscopy......................

46 3.12 Gross Total Counts and Counts per Minute (cpm) Containing 59pe 60 o in a 10-mL Counting Aliquot for NS-1/Dow Leached in C

or Deionized Water..........................

47 4

3.13 Gross Total Counts and Counts per Minute (cpm) in a 10-mL Counting Aliquot for NS-1/Dow Containing 59Feor 60Co Leached in G r o u n d wa t e r............................

48 3.14 Gross Total Counts and Counts,per Minute { cpm) in a 10-mL Counting 59 e or 6uCo Leached in-Aliquot for NS-1/Dow Containing F

Se a wa t e r.............................

49 59 e for NS-1/Dow 3.15 Incremental and Cumulative Fraction Released of F

Leached in Deionized Water....................

50 59 e for NS-1/Dow 3.16 Incremental and Cumulative Fraction Released of F

Leached in Groundwater......................

51 59 e for NS-1/Dow 3.17 Incremental and Cumulative Fraction Released of F

Leached in Seawater........................

52 3.18 Incremental and Cumulative Fraction Released of 60 o for NS-1/Dow C

Leached in Deionized Water....................

53 60 o for NS-1/Dow 3.19 Incremental and Cumulative Fraction Released of C

Leached in Groundwater....................

54 l

X

TABLES, Continued 60 o for NS-1/Dow 3.20 Incremental and Cumulative Fraction Released of C

Leached in Seawater.........................

55 3.21 Mean Ccmulative Fraction Release After 25 and 50 Days Normalized by 59 e and 60C0 Release for NS-1/Dow in Deionized Water, V/S for F

Groundwater, and Seawater......................

62 l

xi

l ACKNOWLEDGMENTS The authors would like to thank Dr. Nabil Morcos for his help in verify-ing the results of the computer program used in analyzing the leaching data reported herein.

The authors also express thanks to Mr. Allen Weiss for his many helpful comments on the study.

Further, we would like to thank the board of trustees of the Town of Southampton, New York, for allowing us to collect seawater samples for use in these experiments.

Finally, we would like to ac-knowledge the help of Nancy Yerry and Kathy Becker for their preparation of l

the manuscript.

V.i i i

PHYSICAL TESTS ON SOLIDIFIED DECONTAMINATION WASTES FROM i

DRESDEN UNIT 1 1.

INTPODUCTION In an ef fort to decontaminate the pricary cooling system of the Dresden Nuclegr posedil) Power Station Unit No.1, Commonwealth Edison Company has pro-the use of a proprietary solvent containing chelating agents, NS-1, produced by the Dow Chemical Company.

After decontamination, the solvent will be concentrated by evaporaticn and solidified in 55-gallon drums using a vinyl ester-styrene polymer as the binder. The binder, Nuclear Binder-101, is also supplied by Dow.

The waste will then be disposed at a commercial shallow land burial site.

The final environmental impact statement (1) indicates that the decon-tamination of Dresden-1 will generate a liquid waste stream containing dis-solved nonradioactive iron and nickel and a variety of dissolved radioactive corrosion products.

The predominant radionuclides present in the waste are listed in Table 1.1.

It can be seen from this table that two isotopes, 58 o C

and 60Co, will account for over 78% of the activity in the wgste.

The total activity anticipated in the waste is approximately 663.6 Ci.t ll The final waste form is a dispersion of NS-1 concentrate in the vinyl ester-styrene polymer (NS-1/Dow).

The vendor states that the solidification process mechanically entraps rather than chemically fixes the waste stream so that the state of all radionuclides, chelating agents, etc., in the solid product should be unchanged with respect to their form in the concentrate.

Thus, any mechanism for the dissolution of the waste form has as its conse-quence the release of both radioneclides and chelating agents in a mobile (i.e., water soluble) form.

Unbound chelating agents released in this manner have the potential to mobilize other radionuclides which may be present in the soils of the waste disposal site.

One such postulated mechanism for waste form dissolution is contact of the form with organic solvents such as toluene or xylene.

These solvents may be present in the shallow land burial sites as liquid scintillation cocktail wastes or as The final environmental impact statement on Dresden-1(contaminated solvent.1) states that NS-1/Dow be is minimum of 10 feet of soil and will be disposed of in an arid site.U)y)a l

Thus, direct contact of these organics with this waste is unlikely.

Since the behavior of the NS-1 concentrate solidified in vinyl ester-styrene (NS-1/Dow) under these conditions was unknown, it was requested by the Nuclear Materials Safety and Safeguards Division of the Nuclear Regulatory Commission that Brookhaven National Laboratory (BNL) conduct immersion tests of simulated NS-1/Dow waste forms in toluene, xylene, and in water saturated with toluene and xylene.

Further, as a part of this technical assistance ef-fort to conduct confirmatory research, it was requested that BNL conduct leach 1

tests of simulated NS-1/Dow waste forms to determine the release rate of iron, cobalt, and nickel from these forms. These leach tests do not simulate condi-tions at any current shallow land burial site. The leachants - deionized water, groundwater, and seawater - are used to study a broad range of waste form performance. This report is a summary of this two-phase experimental ef fort.

Table 1.1 Predominant Radionuclides Expected in the Solidified Waste Resulting From the Decontamination of Dresden-1(1)'

Estimated Ci/5'S gal Druma I

Nuclide Curies (x10 )

60 o 502.2 4.19 C

55Fe 70.1 0.58 63Ni 26.4 0.22 106Ru 106Rh 22.5 0.19 58 o 18.5 0.15 C

144Ce 144Pr 11.9 0.099 54Mn 6.6 0.055 95Zr 95Nb 4.0 0.033 103 u 0.3 0.025 R

238Pu 0.3 0.025 242 m 243 m 0.3 0.025 C

C 239Pu 240Pu 0.2 0.017 241 m 0.1 0.008 C

244Cm 0.1 0.008 124Sb

<5x10-2

<.004 125Sb

<5x10-2

<.004 57 o

<9x10-3

<7.5x10-5 C

141 e

<9x10-3 (7.5x10-5 C

59 e

<2x10-3

<1.6x10-5 F

154Eu

<1x10-3

<gxio-6 aAssumes that the waste will be uniformly distributed in 1200 drums.

2

2.

IMMERSION TESTS l

The purpose of this experiment was to measure the weight change of simu-lated NS-1/Dow waste forms as a result of immersion in toluene, xylene and in water saturated with toluene and xylene.

The samples used in these studies were obtained by sectioning a waste form prepared by Commonwealth Edison Corporation and Dow Chemical Corporation as a part of a full scale demonstra-tion of the solidification system at the Dresden site on July 9-10, 1980.

Details of this demonstration are given in Appendix A.

In addition to these sectioned samples, immersion tests were performed on both cut and uncut sam-ples which had been subjected to a 64-day leach test.

These samples were also fabricated at the Dresden site.

The immersion tests o' these samples were conducted in toluene and in organic saturated water.

2.1 Experimental 2.1.1 Immersion Test of Unleached Samples The initial waste form used for preparation of samples in this study was a cylindrical specinen with a nominal radius of 2.3 cm and a height of ap-proximately 6.8 cm.

The specimen was solidified and shipped in a polyethylene container.

After solidification, the sample remained capped until used in this study.

The specimen itself was pale yellow in color and the bottom and side walls were almost smooth.

The top surface contained small (<2 mm) craters presumably due to bubble fonnation during solidification.

These craters were less frequent on the bottom surface and the sides of the sample.

To prepare samples for the immersion tests, the specimen was marked into eight equal sections along the height of the sample, and disks cut on a band saw.

The cut surfaces were turned in a lathe to approximately 0.65 cm (approximately 1/4 inch) and finally dry-sanded with 600 grit silicon carbide paper to produce a uniform surface roughness.

A typical disk shaped sample is shown in Figure 2.1.

Dimensions and weights of the individual disks are given in Tabl e 2.1.

Samples 7 and 8 were much thinner than samples 1 through 6.

This was due to material losses in cutting the disks from the initial form.

Sample thickness for sample 7 was 0.475 cm and, for sample 8, 0.556 cm.

Sam-ple 6 contained a saw mark which could not be removed without excessive thin-ning.

Sample 5 contained a dimple impression from the bottom of the polyethy-lene container in which the form was solidified.

A hole (approximately 1.3 mm in diameter) was drilled approximately 1 cm inch from the edge of each disk.

Steel" wire was then bent to form hooks, enabling the samples to be suspended in the solvents during the experiment.

The toluene (J. T. Baker #9460) and xylene (J. T. Baker #5-9490) used during this experiment were both reagent grade materials.

The saturated solu-tion was prepared by vigorous mixing of water with an excess of the toluene and xylene for 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months . After equilibration, the aqueous layer was removed for use. During the immersion tests, a layer of toluene and xylene was kept over this water solution to keep the aqueous layer saturated with organics throughout the immersion test.

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i Figure 2.1 Sample 1 prior to immersion.

Table 2.1 Initial Dimensions of the Simulated NS-1/Dow Sample Disks Used in Immersion Testing Sample lhickness Diameter Volume (V)

Surface V/S Weight 3

Number (cm)

(cm)

(cm )

Area (S)

(cm)

(g) 2 (cm )

la 0.655 4.671 11.2 43.9 0.255 12.1316 2a 0.645 4.597 10.7 42.5 0.252 11.4056 3a 0.660 4.641 11.2 43.5 0.257 12.1634 4b 0.653 4.636 11.2 43.3 0.259 11.9816 Sb 0.645 4.559 10.5 41.9 0.251 11.4238 t

6b 0.648 4.615 10.8 42.9 0.252 11.5022 7c 0.475 4.641 8.04 40.8 0.197 8.2189 8c 0.556 4.656 9.47 42.2 0.224 9.9825 i

l almmersed in xylene.

b mmersed in toluene.

l I

j cImmersed in water saturated with toluene and xylene.

i 4

l The liquid volume used in these experiments was fixed by the sample sur-face area (Table 2.1).

The ratio of solution volume to sample surface area was 10 cm.

This ratio is consistent with that used in the leach testing of these samples (see section 3).

Samples 1, 2, and 3 were placed in xylene, samples 4, 5, and 6 in toluene, and samples 7 and 8 in water saturated with xylene and toluene.

The immersion tests were conducted in 600 mL Pyrex beakers which were loosely capped to prevent large amounts of solvent evapora-tion. The volume of liquid used in these experiments was nelo constant by re-placing any liquid lost through evaporation.

Each sample was suspended in liquid during the course of the immersion test.

The samples were weighed periodically using the apparatus shown in Figure 2.2.

Initially, the samples were only weighed while immersed in the so-lution, the beaker sitting on a bridge over the pan of the balance. Due to errors in buoyancy correction, it was necessary to begin measuring the weight of the soaked samples in air. This was done by dabbing the surface of the sample with a paper towel, taking the reading just as the liquid evaporated (visually) from the surface. This method of weighing in air was started 30 hours3.472222e-4 days 0.00833 hours 4.960317e-5 weeks 1.1415e-5 months after the start of the immersion test.

Weights, soaked and suspended (in liquid), continued to be measured throughout the remainder of the immer-sion phase of the experiment.

N I

\\

- -WIRE LOOP l

STEEL HOOK l

/ LIQUID LEVEL y BEAKER SAMPLE gBRIDGE OVER PAN I

BALANCE PAN Figure 2.2 Apparatus used to measure weight of disk suspended in solution.

5

At the conclusion of the immersion phase of the experiment, the samples were removed, the liquid was poured into stoppered glass flasks, and the thickness and the diameter of each sample were measured.

The samples were returned to their uncapped beaker, and suspended from a wood stick across the too of the beaker. As before, sample weight was recorded as a function of time.

2.1.2 Immersion Test of Samples From Leach Study Upon completion of the 64-day leach test described in section 3, the eight samples which were fabricated during the solidification demonstration at the Dresden site were subjected to an immersion test.

The general form of this test was similar to that for the sectioned samples (see section 2.1.1),

and, consequently, only the dif ferences in procedure will be outlined in this section.

The samples were stored in their respective leachants af ter the conclu-sion of the leach test for 10 weeks. These samples were then removed from the i

liquid and allowed to air dry for 2 days.

Figure 2.3 shows these samples

)

af ter ai r drying.

Three of the samples (samples 3, 6, and 9) were then cut in hal f along the axis of the cylinder.

The cut surfaces were sanded smooth using 400 grit sil4. con caroide paper.

Figure 2.4 shows a typical cut surface after this treatnent.

After sectioning, all samples were measured and initial sample weights taken. These dimensions and weights are given in Table 2.2.

The weights and dimensions of the uncut samples were very close to sample di-mensions prior to the start of leaching experiment (Table 3.1).

The samples were placed in pyrex beakers supported by glass rods to en-able the immersion medium to be in contact with nearly the entire surf ace area of the sample. The immersion medium (toluene or water saturated with toluene and xylene) was placed in the beaker.

The total volume of the immersion lig-uid and sample was 600 mL.

This volume v3s maintained during the immersion test.

Samples were removed periodically from the immersion medium for weighing.

Prior to weighing, surface liquid was removed by dabbing the sur-f ace of the sample with a paper towel.

After weighing, the samples were re-turned to the immersion liquid.

After 14 days, the samples were removed from the innersion liquid and allowed to air dry.

Again, periodic weighings were taken.

6

p y r~-n-w n, m r y : m y]

p~73;m gmr7 y r +i7=9m g-

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q?^;9:.;.yjj)

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ii

' w g,~+f. Q :[

f

~ I' ~:

AAr'

}

~

[

E w ggzqsC;mr-s :s..'.2::&v V,

Figure 2.3a Samples from leach test prior to the start of the immersion test.

A, s, ample 2; B, sanple 3; C, sample 4; D, sample 5.

7

i

'Nbf'-;y...

. s.;(., s N f E

~ '-.

g 1

I l

l

' ~ -'-=:;. (: p 3,

y_,

g.

_:#~.-

G Hi Figure 2.3b Sanples from leach test prior to the start of the immersion test.

E, sample 6; F, sample 7; G, sample 8; H, sample 9.

l l

l 8

w&. cc.

7 z

,/ *>

y

N.

ggw.

_ lp

'V W ; ~,

~

. l\\

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[y $;$ f::$kfX;~

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fr g, w%

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[ ' }[ '.

-p N 3 : QQ 3,

q

n. w

%::$ ft"" ih@$0, Figure 2.4 Cut surface of sample from leach test prior to the start of the immersion test (sample 9A).

Table 2.2 Dimensions of NS-1/Dow Samples From Leach Testing Prior to the Start of Immersion Testing Sample Leach Immersion Thicknesse No.

tiediama tiediumb Top Bottom Height Weight (cm)

(cm)

(g) l 2

DI W

4.745 4.636 7.010 133.13 3A DI W

2.156 6.792 58.46 3B DI T

2.298 6.790 63.18 4

DI T

4.728 4.642 6.968 132.02 5

GW W

4.772 4.626 7.182 136.86 6A GW W

2.368 6.652 63.04 6B GW T

2.170 6.658 56.00 7

GW T

a.740 4.618 6.524 124.57 8

SW W

4.710 4.608 7.052 131.51 9A SW W

2.056 6.620 52,40 9B SW T

2.246 6.622 58.64 aDI = deionized water; GW = groundwater; SW = seawater.

bT = toluene, W = organic saturated water.

cThickness on uncut sample refers to the diameter of the cylin-drical sample, while in the cut sample it is the distance from the edge of the sample to the cut surface.

9

2.2 Results and Discussion 2.2.1 Immersion Test of Unleached Samples 2.2.1.1 Immersion in Xylene and Toluene The surface of the sample disks which were immersed in either toluene or in xylene did not visibly appear to deteriorate as a result of immersion.

Figure 2.5 shows a typical sample after about 14 days (approximately 336 hours0.00389 days 0.0933 hours 5.555556e-4 weeks 1.27848e-4 months ) of immersion. While sample surface deterioration did not occur, color, dimensional, and weight changes were noted in the samples as a result of im-mersion in xylene or in toluene.

All samples darkened to a yellowish green color as a result of immersion in either organic solvent. This darkening was more pronounced for those samples which had been immersed in xylene. The sam-pie dimensions after the 839 hour0.00971 days 0.233 hours 0.00139 weeks 3.192395e-4 months immersion test are given in Table 2.3.

Com-parison of these data with the data in Table 2.1 shows a net volume increase of 12.8 + 1.7% for the samples immersed in xylene and 30.4 + 1.5% for those im-mersed in toluene.

Table 2.3 Dimensions of Simulated NS-1/Dow Sample Disms After Immersion in Toluene and Xylene Sample Thickness Diameter Volume (V) Surface Area (s) V/S No.

(cm)

(cm3)

(cm2)

(cm) la 0.693 4.856 12.8 47.6 0.269 2a 0.660 4.793 11.9 46.0 0.259 3a 0.686 4.836 12.6 47.2 0.267 ab 0.721 5.072 14.6 51.9 0.281 Sb 0.701 4.966 13.6 49.7 0.274 6b 0.706 5.042 14.1 51.1 0.276 almmersed in xylene, blamersed in toluene.

As might be expected the increase in volume is accompanied by an increase in weight. Table 2.4 shows the observed weight with time for sample disks immersed in toluene and in xylene.

In addition to the sample weight in air, the table also shows the sample weight in the organic liquid at each time period. The change in weight, aw, can be calculated from the information in Tables 2.4 and 2.1.

If the data corresponding to immersion in the same liquid are averaged, the mean weight change, Aw, of the NS-1/Dow samples at a given time can be calculated. The results of this calculation are given in Table 2.5 and plotted versus time in Figure 2.6.

10

eq b

7 6

E e

a

$ i

=

4 I

I l

l l

h l

8 l

l U

l I

I e.

s Figure 2.5 NS-1/Dow sample af ter 14 days of immersion in toluene (sample 6).

11

Table 2.4 Sample Weights With Time of NS-1/Dow Sample Disks i

Immersed in Toluer.e and Xylene Time of Immer-Weight in Weight Weight in Weight Weight in Weight sion Liquid in Air Liquid in Air Liquid in Air (hr)

(g)

Sample la Sample 2a Sample 3a 0

3.2750 12.132 3.0524 11.406 3.2051 12.163 30 3.1992 12.448 3.0366 11.676 3.1917 12.456 i

48 3.1887 12.507 3.0265 11.708 3.1808 12.494 106 3.1450 12.611 2.9827 11.787 3.1382 12.592 150 3.1122 12.688 2.9513 11.862 3.1062 12.667 193.5 3.0871 12.745 2.9249 11.918 3.0782 12.723 294.5 3.0301 12.846 2.8766 12.008 3.0273 12.807 343 3.0008 12.856 2.8467 12.015 2.9932 12.819 389 2.9915 12.921 2.8368 12.079 2.9838 12.886 462 2.9668 13.006 2.8100 12.156 2.9567 12.973 624 2.8715 13.135 2.7244 12.283 2.8634 13.073 839 2.7546 13.341 2.6144 12.402 2.7435 13.302

. Sample 4b Sample 5b Sample 6b 0

3.1123 11.982 3.0336 11.424 3.0125 11.502 30 3.0804 12.736 2.9985 12.119 2.9764 12.232 48 3.0623 12.926 2.9110 12.267 2.9542 12.399 106 2.9934 13.247 2.9019 12.628 2.8684 12.760 150 2.9316 13.548 2.8557 12.904 2.8077 13.084 i

193.5 2.8876 13.766 2.8174 13.081 2.7649 13.277 l

294.5 2.8292 14.013 2.7663 13.263 2.6926 13.419 343 2.7867 14.0a2 2.7226 13.288 2.6551 13.517 389 2.7742 14.150 2.7106 13.395 2.6410 13.651 462 2.7286 14.228 2.6700 13.470 2.6012 13.753 624 2.6156 14.279 2.5600 13.526 2.4961 13.778 839 2.4800 14.566 2.4317 13.821 2.3641 14.078 i

aI:1mersed in xylene.

bImmersed in toluene.

12

Air drying of the samples which had been immersed in toluene and xylene resulted in a weight loss in all samples.

The sample weight for each sample at various times during air drying is tabulated in Table 2.6.

In addi-tion to weight loss, all samples warped during air drying.

The surface of tne samples also became uneven ind textured.

Furthennore, the samples appeared noticeably thicker at the edges than in the center in contrast to the uni form sample thickness prior to the immersion test and air drying.

As with the data from the immersion test itself, it is possible to calculate a 5 for the air drying of samples which had been immersed in either toluene or xylene at any time by comparison of the data in Table 2.6 for that time with the initial sample weights given in Table 2.1.

The results of this calculation are given in Table 2.7 and plotted versus time in Figure 2.7.

The times given in Table 2.7 are relative to tt e end of the immersion test.

Thus, the last data point in Table 2.5 at 839 hours0.00971 days 0.233 hours 0.00139 weeks 3.192395e-4 months corresponds to the first data point in Table 2.7 at 0 hours0 days 0 hours 0 weeks 0 months .

Table 2.5 Mean Percent Weight Change, E,a for NS-1/Dow Samples Immersed in Toluene and Xylene Time of Immersion E (%)

(hr)

Samples in Xylene Samples in Toluene 30 2.5 + 0.1 6.2 + 0.1 48 2.8 T 0.2 7.7 7 0.3 106 3.6 T 0.3 10.7 T 0.2 150 4.2 7 0.3 13.3 T 0.4 193.5 4.7 7 0.3 14.9 T 0.5 294.5 5.5 T 0.4 16.6 T 0.4 343 5.6 T 0.4 17.0 T 0.6 389 6.1 T 0.3 18.0 T 0.7 462 6.8 T 0.3 18.7 T 0.8 624 7.8 T 0.4 19.1 T 0.7 l

839 9.6 _T 0.3 21.6 T 0.7 th th 1

weight of i sample - initial weight of i sample 7

x 100 th

" i=1 initial weight of i sample where n is the total number of samples.

b verage of samples 1, 2, 3.

A cAverage of samples 4, 5, 6.

Comparison of the data presented in Figures 2.6 and 2.7 suggests that, when NS-1/Dow forms are immersed in either xylene or toluene, at least two things happen:

13

25 i

i i

i b1 2

20 g

15

-8 m

<3 10 0

5 I

I I

I i

i l

I l

l OO 100 200 300 400 500 600 700 800 TIME (hrs.)

i Figure 2.6 Plot of Tw vs time for NS-1/Dow sample disks immersed in, a, xylene and, b, toluene.

Table 2.6

)

Weight of 'NS-1/00w Sample Disks Drying in Air After Immersion in Toluene and Xylene for 839 Hours Time Since Removal From Weight (g)

Organic Liquid (hrs)

Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 0

13.341 12.482 13.302 14.566 13.821 14.078 5

12.8446 12.0004 12.8119 13.4590 12.7871 12.9994 8.2 12.7123 11.8722 12.6772 13.1317 12.4722 12.6626 24.8 12.2699 11.4399 12.2319 12.0721 11.4444 11.5829 48.2 11.9042 11.0833 11.8656 11.2238 10.6449 10.7293 120.2 11.2303 10.4340 11.2061 9.8559 9.3286 9.3452 193.5 10.7142 9.9402 10.7010 9.0164 8.5129 8.5045 288.5 10.2923 9.5356 10.2845 8.4421 7.9444 7.9332 388.5 9.9118 9.1741 9.9073 8.0927 7.5976 7.6058 l

511 9.6251 8.9059 9.6260 7.9311 7.4433 7.4645 650 9.3410 8.6433 9.3491 7.3081 7.3302 7.3633 l

l aSample from xylene immersion test.

bSample from toluene immersion test.

14 a-

1) The organic liquid is absorbed by the form.

2) The form i s dissolved by the immersion' medium.

Presumably, these ef fects occur simultaneously.

Volume changes after immer-sion indicate that the absorption of the organic liquid is also accompanied by a swelling of the form.

One should also note that there is also the possibility that the dis-solution of the waste form in the organic liquid could be depressed by satura-tion effects as a result of the static test conditions.

Experiments to test this hypothesis have not been conducted.

On the basis of the limited imme -

sion test conducted, extrapolation of these results to a full size waste form under realistic burial conditions is not possible.

30 20 10<

0 d

I<,3

-10 l

l

-20 a

-30 b

g I

1 I

l

-400 100 200 300 400 500 600 700 TIME (hrs)

Figure 2.7 Plot of Ti vs time for NS-1/Dow sample disks drying in air after immersion test in, a, xylene and, b, toluene.

15

)

Table 2.7 a

Mean Percent Weight Change, F, for NS-1/Dow Samples Drying in Air After Immersion in Toluene and Xylene for 839 hrs.

W (%)a Time Since Removal From Samples From Xylene Samples From Toluene Organic Liquid Immersion Testb Immersion Teste (hrs) 0

9. 6 + 0.3 21.6 + 0.7 5

5.5 T 0.3 12.4 T 0.5 8.2 4.4 T 0.4 9.6 T

0. 5 24.8 1.6 T 1.3 0.5 T 0.3 48.2

- 2.4 +

0. 5

- 6.6 + 0.3 1

120.2

- 7.9 + 0.5

-18.3

+ 0.5 193.5

-12.2 7 0.6

-25.4 T

0. 7 388.5

-18.8 T 0.7

-33.3 T 0.7 511.5

-21.1 T 0.7

-34.6 T 0.7 650

-23.5 1 0.7

-35.6 1 0.6 1

th th ap=

l_ f weight of i sample - initial weight of i sample xg i=1 initial weight of i sample where n is the number of samples.

bAverage of samples 1, 2, 3 cAverage of samples 4, 5, 6.

2.2.1.2 Immersion in Organic Saturated Water

~

Immersion tests of the NS-1/Dow samples in water saturated with toluene and xylene produced results which were in marked contrast to those of the immersion tests performed in each of the organics.

During the course of this immersion test, the sample color faded to a paler yellow.

Table 2.8 shows the observed weight of these samples at each measuring interval and the change in sample weight, law, for each sample relative to its initial weight (Table 2.1).

Although the immersion test in organic saturated water was run for the same length of time (839 hrs), as for the immersion tests in toluene and xylene, weight data was not taken after 343 and 193.5 hours5.787037e-5 days 0.00139 hours 8.267196e-6 weeks 1.9025e-6 months for samples 7 l

and 8, respectively since sample deterioration and flaking precluded the i

drying step prior to weighing. Although no further interim weighing of the samples was made, the immersion was continued for a total of 839 hours0.00971 days 0.233 hours 0.00139 weeks 3.192395e-4 months .

As mentioned above, the immersion test of NS-1 Dow samples in water j'

Figure 2.8 shows samples 7 and 8 after 14 days of immersion in the organic saturated with toluene and xylene resulted in severe sample deterioration.

saturated water.

The sample deterioration was accompanied by loss of material due to flaking of the sample. The flaking was more excessive for sample 8 16

Table 2.8 b

Sampic Weighta and Change in Sample Weight, aw,

With Time of NS-1/Dow Sample Disks Immersed in Water Saturated With Toluene and Xylene Time Sample 7 Sample 8 (hrs)

Weight aw Eght E

(g)

(%)

(g)

(%)

30 8.371 1.8 10.144 1.6 48 8.456 2.9 10.221 2.4 l

106 9.651 17.4 11.145 11.7 l

150 9.626 17.1 11.137 11.6 l

193.5c 9.722 18.3 11.212 12.3 1

294.5 9.869 20.1 l

313d 9.858 19.9 aWeight taken in air, b

w,.. At - initial weight

^ * * '

x 100 initial weight cSample 8 interim weighing discontinued after this time.

dSample 7 interim weighing discontinued af ter this time.

i l

l I

l

[e 0

Figure 2.8 Sample disks of NS-1/Dow af ter 14 days of immersion in water saturated with toluene and xylene. (a) sample 7; (h) sample 8.

17

than for sample 7.

The sample weights given in Table 2.8 have not been cor-rected for this flaking.

Thus, these data represent the sum of sample weight loss due to flaking and weight gain due to absorption at a given time.

As can be seen in Table 2.8, a overall weight gain of approximately 18% and 11% was observed af ter 193.5 hours5.787037e-5 days 0.00139 hours 8.267196e-6 weeks 1.9025e-6 months of immersior, for samples 7 and 8, respectively.

This weight change is more noticeable at the end cf the experiment.

Table 2.9 gives the measured sample weights and the change in sample weight, aw, relative to the initial sample weights during air drying.

The weight in-creases in the early part of the air dryir.g probably reflect the presence of surface moisture which could not be removed because of the condition of the samples.

In spite of this, data given in Tables 2.8 and 2.9 indicate qualita-tively a gain in sample weight followed by an overall decrease in weight during air drying.

As with the immersion tests in organic liquids, this sug-gests both absorption and dissolution processes are occurring simultaneously.

It should be noted that the weight decreased in Table 2.9.

This represents the sum of sample loss due to dissolution and flaking of the sample. The total weight of filterable solids was 0.26 grams (3.2% of the initial sample weight) for sample 7 and 0.35 grams (3.5% of the initial sample weight) for sample 8.

Table 2.9 Sample Weights and Change in Weight, aw,a for NS-1/Dow Sample Disks Which are Air Drying Following Immercion in Toluene Saturated Water Time Sinc O Samnia 7 Sample 8 Initiation of d Weight tw Weight aw Ai r Dryi ng (g)

(%)

(g)

(%)

(hr) 5 12.6962 54.5 11.2404 12.6

8. 2 9.4927 15.5 10.6549 6.7 24.8 8.8288 7.4 9.1350

-8,5 48.2 8.4556 2.9 8.7902

-11.9 120.2 7.9173

-3.8 8.4086

-15.8 193.5 7.5435

-8.2 8.1142

-18.7 288.5 7.2810

-11.4 7.9230

-20.6 388.5 7.0518

-14.2 7.7711

-22.2 511.5 6.8825

-16.3 7.6271

-23.6 650.0 6.7028

-18.4 7.5295

-24.6 1

a 3w = weight - initial weight x 100 initial weight 18

1 1

l j

The cause of the sample deterioration in the organic saturated water immersion test is unknown.

Samples immersed in the pure organics showed no such deterioration.

Since the solubility of toluene and xylene in water is l

low (0 045 weight percent at 20 C and 0.028 weight percent at 23.5 C, respec-tively(2)), forms which were immersed in water for leach tests (see sec-tion 3) were inspected for deterioration. These samples were immersed as cast, i.e., without the sample preparation of the immersion test specimens.

While similar deterioration could be seen in the leaching samples (see Figure 2.3), it was much less extensive than for the samples used in the im-mersion test.

Further, degradation of the leach specimens was more extensive on the upper flat surf ace of the form.

The upper flat surface of a leaching specimen is somewhat more irregular than the remaining specimen surface. This l

leads to the speculation that the sample preparation for the immersion tests may have sensitized the surface with respect to the degradation process.

2.2.2 Immersion Test of Samples From the Leach Study In order to determine if sample preparation in the immersion tests de-

{

scribed in section 2.2.1 had affected the results, samples from the leach test were immersed in either water saturated with toluene and xylene and in toluene alone.

Both cut and uncut samples were immersed.

The immersion test was quite similar to that of the sectioned sample. The duration of this test, how-ever, was much shorter.

The results of these immersion tests were qualita-tively the same as the results of the immersion test on the sectioned form (disks) described above.

Tables 2.10 and 2.11 list the mean percent weight change Iw during the immersion and air drying phases of the experiment respec-tively.

The mean results c' the immersion portion are plotted in Figure 2.9 for toluene immersion and in Figure 2.10 for organic saturated water.

]

The most significant result of this immersion test is the fact that like the sectioned disk samples, both the uncut and cut samples from the 64-day leach test showed accelerated deterioration upon immersion in organic saturated water. A similar degree of surface deterioration occurred for both I

cut and uncut surfaces. This increased deterioration was not observed upon im-mersion in toluene.

Figure 2,11 shows the samples at the conclusion of the immersion phase.

As with the sectioned samples, weighing of the organic satu-rated water, immersion samples had to be discontinued during the test due to I

sample flaking.

This flaking began quite early in the test. Accelerated sur-face deterioration could be seen after only 1 day of immersion (Figure 2.12).

It is clear from this experiment that the sample degradation which occurs in the immersion of NS-1/Dow in organic saturated water is not the result of sam-ple preparation used in the disk sample immersion tests.

1

(

l 19

I l

Table 2.10 l

Mean Percent Weight Change, EQ',a for NS-1/Dow Samples From the 64-Day Leach Test Immersed Cut and Uncut in l

Toluene and Organic Saturated Water Time ZWi%)

of Samples in j

Immersion Samples in Toluene Uncut Sample 9 Cut Samplese Organic Saturated Water j

(hours)

Uncut Samples" Cut Samples' 1

2 1.15 + 0.28 1.22 + 0.21 0.74 + 0.04 0.61 + 0.05 6

1.48 T 0.19 1.66 T 0.39 0.6170.01 0.84 17 0.10 24 2.03 7 0.001 2.47 7 0.46 1.17 T 0.14 1.85 T 0.22 48 2.33 7 0.15 3.03 T 0.55 1.78 T 0.26 2.95 7 0.28 I

i 75 2.70 T 0.19 3.76 7 0.59 2.37 T 0.30 4.07 7 0.35 149f 3.33 7 0.44 4.77 7 0.65 3.44 T 0.47 6.29 T 1.09 197 3.64 T 0.51 5.33 T 0.75 245 4.42 T 0.48 6.91 7 0.73 312 4.85 T 0.56 7.69 T 0.~/5 333.5 4.99 T 0.59 7.86 T 0.74 358 5.25 T 0.69 8.37 T 0.74 g.,1 n,

th a

th weight of i sample - initial weight of i sample 4,1 initial weight of ith sample n

bAverage of samples 4 and 7.

cAverage of samples 3B, 6B, and 98.

dAverage of samples 2, 5, and 8.

i eAverage of samples 3A, 6A, and 9A.

f eighing of samples in organic saturated water discontinued after this Wtime.

i i.

20

Table 2.11 Mean Percent Weight Change, F,a for NS-1/Dow Samples From the 64-Day Leach Test Drying in Air After Immersion in Either Toluene and Organic Saturated Water al(%)

Drying Samples in Time Samples in Toluene Organic Saturated Water (hours)

Uncut Sampleso Cut Samplesc Uncut Samples Cut Samplest u

1 4.37 + 0.84 7.14 + 0.72 6.53 + 1.11 13.98 + 5.95 4.5 3.49 7 0.87 5.61 T 0.80 4.67 T 0.66 9.85 7 5.51 7.75 2.95 T 0.88 4.77 T 0.80 3.47 7 0.49 7.43 T 3.95 24.25 1.46 T C.89 2.29 7 0.90 1.94 T 0.50 2.82 7 0.83 48 0.33 T 0.70 0.17 T 0.98 1.15 T 0.55 0.98 T 0.45 122

-1.17 7 0.33

-2.68 T 1.07 0.22 7 0.57

-1.26 7 0.41 168.5

-1.77 T 0.32

-3.57 T 1.05

-0.8410.56

-2.21 T 0.40 th th

,1 weight of i sample - initial ight of i sample i=1 initial weight of i sample b verage of samples 4 and 7.

A cAverage of samples 3B, 6B, and 9B.

d verage of samples 2, 5, and 8.

A eAverage of samples 3A, 6A, and 9A.

21

o 9

x o

x-h

-?'

,5 ' '

.L o

e.

~

e 3

..C, y,

~.

G

...-?'

T

{

o 4

6 l

i-, '..

1 a,,.-

1

..,'e:

-1 o

a.

oo a

6 i

i 00 60 0 120 0 180.0 240.0 3$0.0 360.0 Time (hours)

Figure 2.9 Plot of mean aw vs time for NS-1/Dow samples from leach tests immersed in toluene o uncut samples; o cut samples.

l l

22

oo

..C oc-

.&f.

.o p-

., -r -

l I

<3

. -E f.-

a g_

/ '-

,.a._

.x.

o i

i i

i 00 25 0 50 0 75 0 100.0 125.0 150.0 Time (hours)

Figure 2.10 Plot of mean tw vs time for NS-1/Dow samples from leach test immersed in organic saturated water.

O uncut samples; o cut samples.

l 23

= _ - _ - - - - _

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A-'<Qvst i, v' i

A B

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D Figure 2.11a Samples of NS-1/Dow from leach test af ter 14 day immersion test in organic saturated water (samples 2, 3A, 5, 6A, 8) and toluene (samples 3B, 4, 6B, 7, 9B). A-sample 2; B-sample 3B; C-sample 4; D-sample 5.

24

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l Figure 2.11b Samples of NS-1/Dow from leach test af ter 14 day immersion test in organic saturated water (samples 2, 3A, 5, 6A, 8) and 4

toluene (samples 3B, 4, 6B, 7, 9B).

E-sample 6A; F-sample 7; G-sampl e 8; H-sampl e 9B.

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u Figure 2.12 Condition of the cut surface of sample 9A after 1-day immersion in organic saturated water.

i l

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26

3.

LEACHING TESTS The purpose of this experiment was to measure the leachability of iron,

)

nickel, and cobalt from simulated NS-1/Dow waste forms upon immersion in de-ionized water, groundwater, and seawater. This work consisted of two separate leach tasks.

The first task entailed leaching eight samples obtained from Commonwealth Edison Company.

Analysis of nonradioactive iron and nickel leached from the samples was performed.

These results are reported below.

The second task involved preparation and leach testing of 13 additional waste forms, prepared at BNL, coataining nonradioactive iron, nickel, and cobalt, as well as tracer radionuclides of iron and cobalt.

3.1 Experimental 3.1.1 Leach Tests of Samples Prepared at Dresden Specimens were prepared by Dow Chemical Company at the Dresden Nuclear Power Station (see Appendix A).

They consisted of eight cylindrical samples with diameters ranging from 4.67 to 4.72 cm and heights ranging from 6.48 to 7.12 cm.

The dimensions, volume, surface area, and initial weight of each sam-ple are shown in Table 3.1.

The specimens were solidified and shipped in polyethylene containers.

They were identical to the sample sectioned for im-mersion testing (section 2):

pale yellow-green in color, having smooth bottom and side walls and a cratered top surface.

The sample remained capped until initiation of the leach test.

Table 3.1 NS-1/Dow Samples for Leach Test furface Leach Sampl e Diameter Height Volume Area V/S Volume Weight 3

2 No.

(cm)

(cm )

(cm)

(mL)

(g) 2 4.72 6.96 121.99 138.35 0.882 1380 132.43 3

4.72 6.75 118.14 135.10 0.874 1350 130.75 4

4.68 6.91 118.75 135.90 0.874 1360 131.54 5

4.71 7.12 124.25 140.35 0.885 1400 136.11 6

4.68 6.61 113.94 131.76 0.865 1320 125.26 7

4.69 6.48 111.99 130.06

0. 8 61 1300 124.66 8

4.67 7.02 119.95 137.03 0.875 1370 131.39 9

4.70 6.60 114.38 132.07 0.866 1320 125.06 The samples tested had a waste-to-binder ratio of 1.5 to 1.0 by volume, the waste being totally comprised of a concentrated NS-1 solution with a den-si ty of 1. 32 g/mL.

Iron concentration in this solution was 8085 + 75 ppm (9150 + 50 pg/mL).

Nickel concentration was 3490 + 50 ppm (3950 T 50 tg/mL).

27

These values were detemined by Dow. From this infomation and the initial sample volume, the weights of nickel and iron initially present in the samples were detemined. These values ranged from 2.34 x 105 to 2.60 x 105 pg or nickel and 5.43 x 105 to 6.03 x 103 pg of iron.

Sampic 1 was used in the immersion tests described in saction 2.

The remaining samples were used in this leach test. Leaching of samples 2, 3, and 4 was performed using deionized water as the leachant, 5, 6, and 7 using groundwater, and 8 and 9 using seawater. Deionized water was prepared by passing tap water through a Barnstead mixed bed water purification cartridge (D0809). Groundwater was pumped from BNL Well No.1 and stored in 30 gallon drums with polyethylene liners, and seawater was taken from Shinnecock Bay, Long Island, New York, and stored in 20 gallon poiyethylene carboys. The con-ductivity, pH, and ionic constituents, as measured by atomic absorption and flame emission spectroscopy, of these leachants are given in Table 3.2.

Table 3.2 Results of Analysis of Groundwater and Seawater Blanksa Groundwater Seawater (BNL Well No.1)

(Shinnecock Bay)

Co

<0.1 ppm

<0.05 ppm Si 10 ppm 0.05 ppm Al 0.05 ppm 2

ppm Cu 1

ppm 0.05 ppm Na 2

ppm 10500b ppm Mg 10 ppm 1350b ppm Ca 1

ppm 400b ppm pH 6.46 7.82 Conductivity 129 mhos 4.54 x 104 mhos aThe analysis of the leaching media for Fe and Ni are reported in Table 3.3 for deionized water, Table 3.4 for groundwater, and Table 3.5 for seawater.

b verage values taken from R. A. Horne, Marine A

Chemistry, Wiley-Interscience (1969).

After removal of a sample from its original container, it was placed in a volume of leachant ten times its surface area. These leachant volumes, ranging from 1300 to 1400 mL are shown in Table 3.1.

A lucite stand was used to support the sample so that its entire external surface area was exposed to 28

the leachant. Leachate aliquots were taken and the waters changed af ter the folicwing times from initiation of the test: 1,3,4,5,6,7,8,11,12,14,17,25,35, 42,50, and 64 days. Af ter each interval, the sample was removed, the leachate stirred, and the aliquot taken. Fcr the first three sampling periods, as well as the last four, the entire leachate was saved in a collapsible one gallon polyethylene container. For the remaining sampling periods, approximately 150 + 10 mL of the leachate was retained for analysis in a small polyethylene container. The polyethylene lea:h container was then rinsed at least six times with deionized water, the proper volume of fresh leachant poured into it, and the sample returned. All containers were securely capped and stored at room temperature, and the leachants allowed to stand undisturbed between sampling periods.

For analysis, all leachates were poured into identical polyethylene con-tainers (150 + 10 mL) and acidified by addition of 2 mL of ULTREX HNO.

3 Flameless atomic absorption analysis of iron and nickel was performed by Grumman Aerospace Corporation (Analytical Services Group), Bethpage, New York.

Iron and nickel concentrations were reported to 0.01 p g/mL for all leachants except seawater, where nickel concent ation could be detemined to a sensitiv-ity of 0.02 ug/mL.

59 e and 60 o From NS-1/Dow 3.1.2 Leach Tests of F

C Thirteen samples were prepared using NS-1 concentrate from the Dresden test solidification.

This is the same concentrate which was used to fabricate the samples described in section 3.1.1.

However, prior to sample fabrication 2.06 g of CoCl2 per sample were added to simulate the levels of radioactive Co expected in the Dresden-1 decontamination waste concentrate. The concen-trate was divided into two fractions for radioactive tracer addition. To one approximately 20 pCi of ]Fe/ sample was added.60 o/ sample was added, while to fraction, approximately pCi of C

Samples were then fabricated using Nuclear Binder-101, with a waste-to-binder ratio of 1.5 by volume.

Seven cylindrical samples were fabricated from the fraction containing 60Co 59 e.

and six samples from that containing F

Each sample was 3.6 cm in diameter and 3.7 cm high. These dimensions gaveasgmplegeometricsurfaceart of 145.1 cm2 and a volume of 126.6 cm (volume-to-surface area ra io of 0.87 cm). This sample size was chosen to be close to those of sampi fabricated during the Dresden test so-lidification. Af ter mixing in polyetNiene containers, the samples were capped and allowed to stand for 3 days prior to the start of the leach test.

At this time, the samples were hard except for a)1-2 mm layer on the top of each sample which remained a sof t paste. Dow(3a has indicated that this tackiness was most likely due to air inhibition of the polymerization at the surface. This phenomenon has been commonly observed with their process.

Ex-cept for this soft region, the samples were similar in appearance to these fabricated at Dresden. When removed from the container, the sides, as well as top and bottom, were smooth except for markings where the mixer blade had grazed the side walls of the polyethylene container. Upon removal of the form for the container, residual liquid was noticed on the waste form. This 29

l I

" weeping" phenomenon was discussed with Dow.(3a) Such behavior has been l

l observed by Dow when solidification is performed in certain plastic con-tai ne rs.

The container was rinsed with the particular leachant used for the form and that rinse was counted as a part of the first leaching increment (0.125 days).

The leaching experiment itself was carried out in a manner j

similar to that described in section 3.1.1.

The leach volume used in these experiments was approximately ten times the surface area,1450 mL.

Two sam-59 e and three g ntaining 60 o were placed in deionized i

ples containing F

C water.

Two samples containing Fe and likewise two with 6uCo were leached in groundwater (obtained from BNL Well No.1) and two samples of each species were leached in seawater (obtained from Shinnecock Bay, Long Island).

As with samples described in section 3.1.2, the samples were supported by lucite stands.

Leach aliquots were taken and the leachate changed at the fol-l lowing times from the initiation of the test:

0.125, 1, 2, 3, 4, 7, 8, 9, 10, 11,18, 25, 42, and 50 days.

Leaching was carried out using two sets of leach containers. The samples were placed in fresh leachant while the leachate from the previous day was acidified using 25 mL of ULTREX HNO.

The following 2

3 day, approximately 150 mL of this acidified leach. ate was withdrawn and stored in a polyethylene container, the remaining liquid discarded, and the container 1

washed and wiped dry; so that fresh leachant could again be added and the cy-i cle continued.

1 Ten mL aliquots of each leaching sample were analyzed by radioactive (gama) counting using a Nal well detector. The 59Fe and 60C0 were analyzed separately.

In addition to these samples,10 mL aliquots from 60 o or counting standards which contained either approximately 10 pCi of C

approximately 20 pCi of 59Fe dissolved in 1450 mL of water were also counted 1

with the sample. This was done to eliminate any geometry correction for counting the form and to provide a counting standard independent of the waste form.

All samples and backgrounds were counted for 50 minutes.

4 3.2 Results and Discussion 3.2.1 Leach Tests of Samples Prepared at Dresden l

Measured concentrations of nonradioactive iron and nickel in the three leachants are shown in Tables 3.3, 3.4, and 3.5 as a function of leach time.

The fractional release and cumulative fraction release of iron and nickel from the Dow matrix were determined by first correcting background (0.005 ppm for all samples) except for Ni in seawater which was 0.010 ppm) and multiplying by the total volume of the leachant, then dividing by the initial weight of iron or nickel in the sample.

This was done using the computer program listed in l

Appendix B. The calculated incremental and cumulative fractions released (CFR) for each sample are given in Tables 3.6, 3.7, and 3.8 for deionized, ground-l water and seawater leaching, respectively.

Figures 3.1-3.6 show the cumula-l tive fraction release as a function of time.

For each leachate sampling pe-l riod, the mean of the three (or two) points normalized by the volume-to-surface area ratio for the sample was also calculated using the computer pro-gram in Appendix B.

Fiqures 3.7-3.12 show these normalized mean values of the (Continued page 44) 30

i i

Table 3.3 NS-1/Dow Deionized Water Leach Results Reported in ug/L (ppb)

Date Sample 2 Sample 3 Sample 4 Sampleda Iron Nickel Iron Nickel Iron Nickel 10/3 400 240 700 400 1000 560 10/5 70 60 140 80 270 100 10/6 20 10 38 18 40 18 10/7 20

<10 30

<10 40 24 10/8 40 10 65 10 50 22 10/9 36 10 64 16 60 20 10/10 30

<10 40

<10 30

<10 10/13 90 28 170 54 160 34 10/14 20

<10 40 17 60 18 10/16 60 13 86 12 75 29 10/19 100 14 180 46 180 42 10/27 180 40 320 120 380 120 11/6 220 80 300 100 640 220 11/13 130 60 260 110 150 60 11/21 60 60 160 50 100 16 12/5 100 40 230 80 86 22 Leachant Ni Fe Blank No.

(ppb)

(ppb) 1

<10

<10 2

<10

<10 3

<10

<10 4

<10 10 aTest started October 2, 1980.

i 31

Table 3.4 NS-1/Dow Groundwater Leach Results Reported in u g/L (ppb)

Date Sample 5 Sam,ple 6 Sample 7 Sampled a Iron Nickel Iron Nickel Iron Nickel 10/3 1310 430 1290 400 1660 530 10/5 200 44 230 50 270 100 10/6 65 16 70 19 85 21 10/7 65 16 65 18 70 19 10/8 55 18 55 17 65 17 10/9 55 17 55 16 45 14 10/10 90 17 45 13 60 10 10/13 260 100 130 32 140 40 10/14 120 20 55 15 45 13 10/16 200 80 70 21 90 24 10/19 340 95 130 19 110 13 10/27 430 130 210 47 220 60 11/6 270 72 270 80 300 80 11/13 130 38 90 25 230 90 11/21 110 50 80 12 200 50 12/5 140 46 90 30 260 60 Leactant Ni Fe Blank No.

(ppb) g(b) 1

<10

<10 2

<10

<10 3

<10

<10 4

<10

<10 aTest started October 2,1980.

l l

l 32 l

Table 3.5 NS-1/Dow Seawater Leach Results Reported in ug/L (ppb)

Date Sample 8 Sample 9 Sampleda Iron Nickel Iron Nickel 10/3 2200 580 1000 1400 10/5 1000 260 1300 72 10/6 180 40 250 66 10/7 120 40 90

<20 10/8 160

<20 22

<20 10/9 22 58 72

<20 10/10 50 26 10

<20 10/13 300

<20 20

<20 10/14 43

<20 16

<20 10/16 54 34

<10

<20 10/19 100 64 10

<20 10/27 440 36 160 32 11/6 320 26 100

<20 11/13 120 40 220 26 11/21 180 58 24

<20 12/5 280 68 46 40 Leachant Ni Fe Blank No.

(ppb) 1(p b) 1

<20

<10 2

<20 10 3

<20

<10 aTest started October 2,1980.

33 l

~_

l.

Table 3.6 Incremental and Eumulative Fraction Released of Fe and Nt for NS-1/Dow Leached in Delontred Water I

l Sample 2 Sample 3 Sample 4 Inc r(mental Lumula tive Incremental Cumulatt we Incremental Cumulative Time Fraction Traction Fraction Fraction Fraction Fraction (Jays)

Released Released Released Released Released Released Iron 1

0.92 E-03 0.92 E-03 0.16 E-02 0.16 E-02 0.23 E-02 0.23 E-02 3

0.15 E-0.7 0.11 E-02 0.32 E-03 0.20 E-02 0.63 E-03 0.30 E-02 4

0.35 E-04 0.11 E-02 0.78 E-04 0.20 E-02 0.83 E-04 0.31 E-02 5

0.35 E-04 0.11 E-02 0.59 E-04 0.21 E-02 0.83 E-04 0.31 E-02 6

0.82 E-04 0.12 E-02 0.14 E-03 0.22 E-02 0.11 E-03 0.32 E-02 7

0.72 E-04 0.13 E-02 0.14 E-03 0.24 E-02 0.13 E-03 0.34 E-02 8

0.58 E-04 0.14 E-02 0.83 E-04 0.25 E-02 C.59 E-04 0.34 E-02 11 0.20 E-03 0.16 E-02 0.39 E-03 0.28 E-02 0.37 E-03 0.38 E-02 12 0.35 E-04 0.16 E-02 0.83 E-04 0.29 E-02 0.13 E-03 0.39 E-32 14 0.13 E-03 0.17 E-02 0.19 E-03 0.32 E-02 0.17 E-03 0.41 E-02 17 0.22 E-03 0.19 E-02 0.41 E-03 0.35"E-02 0.41 E-03 0.45 E-02 25 0.41 E-03 0.24 E-02 0.74 E-03 0.43 E-02 0.88 E-03 0.54 E-02 35 0.50 E-03 0.29 E-02 0.70 E-03 0.50 E-02 0.15 E-G2 0.69 E-02 42 0.29 E-03 0.31 E-02 0.60 E-03 0.56 E-02 0.34 E-03 0.72 E-02 50 0.13 E-03 0.33 E-02 0.37 E-03 0.59 E-02 0.22 E-03 0.75 E-02 64 0.22 E-03 0.35 E-02 0.53 E-03 0.65 E-02 0.19 E-03 0.76 E-02 Nicke' 1

0.13 E-02 0.13 E-02 0.22 E-02 0.22 E-02 0.30 E-02 0.30 E-02 3

0.30 E-03 0.16 E-02 0.41 E-03 0.27 E-02 0.52 E-03 0.36 E-02 4

0.27 E-04 0.16 E-02 0.71 E-04 0.26 E-02 0.71 E-04 0.36 E-02 5

0.0 0.16 E-02 0.0 0.26 E-02 0.10 E-03 0.37 (-02 6

0.27 E-04 0.16 E-02 0.27 E-04 0.27 E-02 0.93 E-04 0.38 E-02 7

0.27 E-04 0.17 E-02 0.60 E-04 0.27 E-02 0.82 E-04 0.39 E-02 8

0.0 0.17 E-02 0.0 0.27 E-02 0.0 0.39 E-02 11 0.12 E-03 0.18 E-02 0.27 E-03 0.30 E-02 0.16 E-03 0.41 E-02 12 0.0 0.18 E-02 0.66 E-04 0.31 E-02 0.71 E-04 0.41 E-02 14 0.43 E-04 0.18 E-02 0.38 E-04 0.31 E-02 0.13 E-03 0.43 E-02 17 0.49 E-04 0.19 E-02 0.22 E-03 0.33 E-02 0.20 E-03 0.45 E-02 25 0.19 E-03 0.21 E-02 0.63 E-03 0.40 E-02 0.63 E-03 0.51 E-02 35 0.41 E-03 0.25 E-07 0.52 E-03 0.45 E-02 0.12 E-02 0.63 E-02 I

42 0.30 E-03 0.28 E-02 0.57 E-03 0.50 E-02 0.30 E-03 0.66 E-02 50 0.30 E-03 0.31 E-02 0.25 E-03 0.53 E-02 0.60 E-04 0.66 E-02 64 0.19 E-03 0.33 E-02 0.41 E-03 0.57 E-02 0.93 E-04 0.67 E-02 c

l 34 i

..m

Table 3.7 Incremental and Cur:ulative Fraction Released of Fe and Ni for NS-1/Dow Leached in Groundwater Sample 5 Sample 6 Sample 7 Increcental Eumala tive Incremental Eumulative Incremental EuGa tive Tine Fraction Fraction Fraction Fraction Fraction Fraction (days)

Released Released Released Released Released Released Iron 1

0.33 E-02 0.30 E-02 0.31 E-02 0.31 E-02 0.40 E-02 0.40 E-02 3

0.45 E-03 0.35 E-02 0.54 E-03 0.36 E-02 0.63 E-03 0.46 E-02 4

0.14 E-03 0.36 E-02 0.16 E ^3 0.37 E-02 0.19 E-03 0.48 E-02 5

0.14 E-03 0.38 E-02 0.14 E-03 0.40 E-02 0.16 E-03 0.49 E-02 6

0.12 E-03 0.39 E-02 0.12 E-03 0.48 E-02 0.14 E-03 0.51 E-02 7

0.12 E-03 0.40 E-02 0.12 E-03 0.41 E-02 0.96 E-04 0.52 E-02 8

0.20 E-03 0.42 E-02 0.95 E-04 0.42 E-02 0.13 E-03 0.53 E-02 11 0.59 E-03 0.48 E-02 0.30 E-03 0.45 E-02 0.32 E-03 0.56 E-02 12 0.27 E-03 0.51 E-02 0.12 E-03 0.47 E-02 0.96 E-04 0.57 E-02 14 0.45 E -03 0.55 E-02 0.16 E-03 0.48 E-02 0.20 E-03 0.59 E-02 17 0.78 E-03 0.63 E-02 0.30 E-03 0.51 E-02 0.25 E-03 0.62 E-02 25 0.99 E-03 0.73 E-02 0.49 E-03 0.56 E-02 0.51 E-03 0.67 E-02 35 0.62 E-03 0.79 E-02 0.63 E-03 0.62 E-02 0.71 E-03 0.74 E-02 42 0.29 E-03 0.82 E-02 0.20 E-03 0.64 E-02 0.54 E-03 0.80 E-02 50 0.24 E-03 0.84 E-02 0.18 E-03 0.66 E-02 0.47 E-03 0.84 E-02 64 0.31 E-03 0.88 E-02 0.20 E-03 0.68 E-02 0.61 E-03 0.90 E-02 Nickel 1

0.23 E-02 0.23 E-02 0.22 E-02 0.22 E-02 0.29 E-02 0.29 E-02 3

0.21 E-03 0.25 E-02 0.25 E-03 0.24 E-02 0.53 E-03 0.34 E-02 4

0.59 E-04 0.26 E-02 0.77 E-04 0.25 E-02 0.89 E-04 0.35 E-02 5

0.59 E-04 0.26 E-02 0.72 E-04 0.26 E-02 0.78 E-04 0.36 E-02 6

0.70 E-04 0.27 E-02 0.66 E-04 0.26 E-02 0.67 E-04 0.37 E-02 7

0.65 E-04 0.28 E-02 0.61 E-04 0.27 E-02 0.50 E-04 0.37 E-02 8

0.65 E-04 0.28 E-02 0.44 E-04 0.28 E-02 0.28 E-04 0.38 E-02 11 0.51 E-03 0.33 E-02 0.15 E-03 0.29 E-02 0.19 E-03 0.39 E-02 12 0.81 E-04 0.34 E-02 0.55 E-04 0.30 E-02 0.44 E-04 0.40 E-02 14 0.40 E-03 0.38 E-02 0.88 E-04 0.30 E-02 0.11 E-03 0.41 E-02 17 0.49 E-03 0.43 E-02 0.77 E-04 0.31 E-02 0.44 E-04 0.41 E-02 25 0.67 E-03 0.50 E-02 0.23 E-03 0.34 E-32 0.31 E-03 0.44 E-02 35 0.35 E-03 0.53 E-02 0.41 E-03 0.38 E-02 0.42 E-03 0.49 E-02 42 0.18 E-03 0.55 E-02 0.11 E-03 0.39 E-02 0.47 E-03 0.53 E-02 50 0.24 E-03 0.58 E-02 0.39 E-04 0.39 E-02 0.25 E-03 0.56 E-02 64 0.22 E-03 0.60 E-02 0.14 E-03 0.41 E-02 0.31 E-03 0.59 E-02 l

l 35 4

Table 3.8 Incremental and Cumulative Fraction Released of Fe and Ni for NS-1/Dow Leached in Seawater Sample 8 Sample 9 Incremental Cumulative Incremental Cumulative Time Fraction Fraction Fraction Fraction (days)

Released Released Released Released i

Iron 1

0.52 E-02 0.52 E-02 0.24 E-02 0.24 E-02 3

0.23 E-02 0.75 E-02 0.31 E-02 0.54 E-02 4

0.41 E-03 0.79 E-02 0.58 E-03 0.60 E-02 5

0.27 E-03 0.82 E-02 0.20 E-03 0.62 E-02 6

0.36 E-03 0.86 E-02 0.40 E-04 0.63 E-02 i

7 0.40 E-04 0.86 E-02 0.16 E-03 0.64 E-02 8

0.11 E-03 0.87 E-02 0.19 E-04 0.64 E-02 11 0.69 E-03 0.94 E-02 0.37 E-04 0.65 E-02 12 0.89 E-04 0.95 E-02 0.26 E-04 0.65 E-02 14 0.12 E-03 0.96 E-02 0.0 0.65 E-02 I

17 0.22 E-03 0.98 E-02 0.12 E-04 0.65 E-02 25 0.10 E-02 0.11 E-01 0.37 E-03 0.69 E-02 35 0.74 E-03 0.16 E-01 0.23 E-03 0.71 E-02 42 0.27 E-03 0.12 E-01 0.51 E-03 0.76 E-02 50 0.41 E-03 0.12 E-01 0.45 E-04 0.77 E-02 64 0.65 E-03 0.13 E-01 0.98 E-04 0.78 E-02 Nickel 1

0.31 E-02 0.31 E-02 0.62 E-02 0.62 E-02 3

0.10 E-02 0.41 E-02 0.34 E-03 0.66 E-02

}

4 0.16 E-03 0.43 E-02 0.31 E-03 0.69 E-02

^

5 0.16 E-03 0.45 E-02 0.0 0.69 E-02 6

0.0 0.45 E-02 0.0 0.69 E-02 7

0.26 E-03 0.47 E-02 0.0 0.69 E-02 I

8 0.87 E-04 0.48 E-02 0.0 0.69 E-02 11 0.0 0.48 E-02 0.0 0.69 E-02 12 0.0 0.48 E-02 0.0 0.69 E-02 14 0.13 E-03 0.50 E-02 0.0 0.69 E-02 17 0.29 E-03 0.53 E-02 0.0 0.69 E-02 25 0.14 E-03 0.54 E-02 0.12 E-03 0.70 E-02 35 0.87 E-04 0.55 E-02 0.0 0.70 E-02 42 0.16 E-03 0.56 E-02 0.88 E-04 0.71 E-02 50 0.26 E-03 0.59 E-02 0.0 0.71~E-02 64 0.32 E-03 0.62 E-02 0.17 E-03 0.73 E-02 36

?

i 9E

'a g

a' O

___m....

oc-a

,, - ',..o- ,,.o-a gj a

q w-a a

y U

3 1

.ab a

0*,W..o ta -

a 4

y c

&Y

.e

/

O O

09 10 0 20 0 30 0 4'00 50 0 soo 70.0 Time (days)

Figure 3.1 Cumulative fraction released (C.F.R.) of Fe for NS-1/Dow leached in deionized water.

o sample 2, o sample 3, a sample 4.

?

S. E a

4 a-

^

- - ~~~

-o -

n O

.. O Ob o

.a^ a

,g.-

c.y w -

gg a

o ab O

a

,eC-C' gn -

g_ d

.f o

O i

a 4

oo 10 0 20 0 30 0 400 50.0 soo

,o o Time (days)

Figure 3.2 Cumulative fraction released (C.F.R.) of Hi for NS-1/Dow leached in def onized water.

o sample 2, o sample 3, a sample 4.

37

o5o a

a j

o a

1 g...

-o a

... o *****,,,___.

y2 $.

a /e

^

C

_o.

a

(

,e.

a a

a,s

- o E-f a

a

. C~

-E N

8o d0 10 0 2'00 3'00 4'00 50 0 6d0 70 0 Time (days)

Figure 3.3 Cumulative fraction released (C.F.R.) of Fe for NS-1/Dow leached in groundwater. o sample 5, o sample 6, A sampl e 7.

Ico rd os-9

. 3..

a do gAAA'"aa

.g-

G-------G-------

-O a

4 + -

y q. O

.. c --

1 g

oo 2'.0 N.0 40.0 5'O.0 6'0.0 70.0 O

0.0 10.0 Time (days)

Figure 3.4 Cumulative fraction released (C.F.R.) of Ni for NS-1/Dow leached in groundwater. o sample 5, o sample 6, A sample 7.

38

io o

/

8,

/

af

/

-4 f.

o' o j

3.......

,,,,,,,.o l

cc..co-o- - c -

....o-g 1,

5.

o E 5 o

00 10 0 20 0 30 0 400 50 0 60 0 70 0 Time (days)

Figure 3.5 Cumulative fraction released (C.F.R.) of Fe for NS-1/Dow leached in seawater. o sample 8, o sample 9.

n'o o T*

m. g y. g..

- o- - - - - -.. - o. - - - O - - - - - - o. - - - - - - - - - O O

o a'

-a c-No

[

%*~

O 1

d oo 0.0 1d.0 20.0 30.0 40.0 50.0 6O.0 70.0 Time (days)

Figure 3.6 Cumulative fraction released (C.F.R.) of Ni for NS-1/D0w leached in seawater. o sample 8, o sample 9.

39

noo 7*

a>

I oe-T l

=

C l

l

__.._ - +-

,3-- -[_

}

z l

--T '

>o_

x

- _r p-3 l

~

j 4-i

L.r '

J.

L r '-, ; '.

t I Jt fN.. '

4' a

Oo E

{

"~

=

+

m' j

a oo 00 lb0 2b 0 3b0 4'00 Sb0 6bo 70 0 Time (days) 1 Figure 3.7 Average cumulative fraction released (C.F.R.) of Fe for NS-1/D0w leached in dei 0nized water.

"o o 7*

I J

_8 -

5 T

-e e r,_

'l Z

l-

.o l

r T

i 4{

t i

<] y! I x

!. :#a.!. 7 r' I

1.

I i

a 7

I j

J*kW,~l E i

i i'

+

Go l

y' lt u lI

[

N~

'l ~

oo 00 lb 0 2b0 3b0 400 5b0 60.0 70 0 Time (days)

Figure 3.8 Average cumulative fraction released (C.F.R.) of Hi for NS-1/D0w leached in dei 0nized water.

40

oo 7*

\\

?

i i

o

_c-l

- m -

l

-y, -+ -

l 7

j 3

1

..y 3

>8

_,z

.,+-hTf'

^

1\\f':

s

?

E bl h" E-o 00 10 0 20 0 30 0 4'00 sbo ebo 700 Time (dztys)

Figure 3.9 Average cumulative fraction released (C.F.R.) of Fe for NS-1/Dow leached in groundwater.

eoo 7*

a C-

=

~-

~

7 v

,9 h;-

I f a..

c r

i t.

i

-,7 ;,;p /

.e _ -

1 y*

l j_

e i

- 7. 7 ~:. 2. r >

L~

do E'

r, 11

n. 3a e

o 2b0 3b0

[00 Sb0 6b0 70 0 00 lb0 Time (daiys)

Figure 3.10 Average cunulative fraction released (C.F.R.) of Ni for NS-1/Dow leached in groundwater.

Al

s c:

O O

1 a

O_

=o

=

S z

u $_

l o

o T Tl T

n,.

. -] g ' "3..___

- + _ _ s,

x Tg' 'c : lm;+

+~*1

,J l

l i-

{ g_

l o

8 O

00 10 0 20 0 300 4'00 50 0 60 0 70 0 Time (days)

Figure 3.11 Average cumulative fraction released (C.F.R.) of Fe for NS-1/Dow leached in seawater.

n OO r*

o_,.,7U 7T r

+

~

.{.

i r !. l ;t '

i

=

u i

I

+3

- _ c,

=

i

' ' -+-M4'h_

i

[

-t t

i g

i v

: .,f ! l l ll i I

I i

l 1

Z p i ;i t [!.i i

i 2

.O 7 :j! i

!l 1 x

Ila_L r

edi OO t

u-O O

00 1h0 eb0 a'0 0 4oo 3'o n ggg

,gg Time (days)

Figure 3.12 Average cumulative fraction released (C.F.R.) of Ni for NS-1/D0w leached in seawater.

42

Table 3.9 Average Cumulative Fraction Release After 50 and 64 Days of Leaching CumulativeFracgion Cumulative Fracgion Released (x10 )a Released (x10 )a Leachant 50 days 64 days Iron Nickel Iron Nickel Deionized Water 5.6 + 2.1 5.0 + 1.8 5.9 + 2.1 5.2 + 1.8 Groundwater 7.8 7 1.1 5.1 T 1.0 8.2 + 1.2 5.3 + 1.1 Seawater 10.0j[3.3 6.5][0.8 10.3}[3.6 6.7}[0.7 aEntries listed in the table are 103 times 5.6 + 2.1 should be read as 5.6 + 2.1 x 10 gheir actual value, e.g.,

Table 3.10 Average Cumulative Fraction Release x V/S After 50 and 64 Days of Leaching Cumulative Fraction Cumulative Fraction Released x V/S Released x V/S 3

3 (cm x 10 )a (cm x 10 )a Leachant 50 days 64 days Iron Nickel Iron Nickel Deionized Water 4.9 + 1.8 4.4 + 1.6 5.1 + 1.9 4.6 + 1.6 Groundwater 6.8 T 1.0 4.4 T 0.9 7.1 T 1.1 4.6 T 1.0 Seawater 8.7][2.9 5.7}[0.7 9.0][3.2 5.9][0.6 aEntries listed in the table are 103 times their actual value, e.g.,

4.9 + 1.8 should be read as 4.9 + 1.8 x 10-3, 4

43

CFR versus time.

In Table 3.9, the leach results (cumulative fraction re-leases) are summarized after 64 days of leaching. To the right of each group is the mean and standard deviation of the three (or two) points. When norma-lized by the appropriate V/S ratio, the values shown in Table 3.10 are ob-tained.

Again, the mean and standard deviation are listed.

Several observations can be drawn from the data in Table 3.9 and 3.10.

The following trend is seen for both iron and nickel leachability: deionized water < groundwater < seawater. At 64 days, 40% more iron is released in groundwater than deionized water, while 76% more iron is released in seawater than in deionized water. For nickel, only 1.7% more leaches in groundwater, while 29% more leaches in seawater.

It is also evident that nearly the same fraction of iron leaches compared to nickel over the same period of time, though this fraction is not constant.

For deionized water, iron leaches 13%

more, for groundwater 54% more, and, for seawater, 53% more than nickel in these leachants.

Finally, the sample-to-sample variation scatter of the data is less for nickel than for iron in all media.

Interestingly, the scatter of

+

nickel data are lowest for seawater samples, followed by groundwater, then deionized water. The scatter of the seawater. data may be explained, however by the fact a large number of the data from sample 9 are at or below the de-tection limit.

For iron data, groundwater samples have the lowest scatter, followed by deionized water and seawater.

J Since there were some samples and all the blanks were reported at or be-low the detection limit of tne analytical technique, it was assumed for the data analysis that a sample reported below the detection limit had a value of one-hal f the detection limit with an error of half the detection limit.

This blank correction was assumed to be one-half the detection limit with a similar error. This had the effect of assuming zero incremental release for those samples below the detection limit.

o A more conservative " worst case" analysis of the data was performed.

Nickel data for deionized leachant was recalculated using a blank correction of 0.000 ppm.

Values of the nickel concentration in the leachate below the detection limit are set equal to the detection limit.

This analysis results in the individual cumulative fraction release versus time curves shown in Figure 3.13.

The mean values normalized by V/S ratio give the curve shown in Fiqure 3.14.

A value of 5.7 + 1.8 x 10-3 for the mean cumulative fraction leaqhed af ter 64 days is obtained.

Compared to the value of 5.2 + 1.8 x 10-J obtained previously, the " worst case" is only 9.6% greater, which is less than the accuracy of the measurement.

Standard solutions included with the leachants to determine precision of the flameless atomic absorption analysis are shc#n in Table 3.11.

The accu-racy of the measured concentration varies widely.

While iron contamination or background interference may account for some of these variaticns, standards made in deionized water (which show the greatest accuracy) deviate up to 30%

from the actual value.

Aside from statistical variations, sources of error arising from both experimental and analytical procedures should be noted.

The possibility of iron contamination was formidable considering the concentration 44

.'o g 7

6

. 4..

.a..

A' S-

.... - o

~ ~.... -o r

.a

..O

a'#

,.O,,.

Mq

,3 aa r4 v-a,6 p.-

3 O

s

,8 4

g_ o' oo oo th0 2b0 3b.0 400 0

70 0 Time (days)

Figure 3.13 Cumulative fraction released (C.F.R.) of Ni for NS-1/Dow leached in deionized water " worst case." osample 2, o sample 3, a sample 4.

eoo r=

o T

T

\\

e-E i

t 2

1 y ~~

T Z

, y A, -

l

[

v.

R, _..

'/

o

/

q i

f x

l i

?

, l l I i l.M, :: ; i' g:

i 1

3 l

y [lilh ^> > j>

'~

v, o r;

i

iJj j

N-l oe 6

70 0

'lir le (day )

Figure 3.14 Average cumulative fraction released (C.F.R.) of Ni for NS-1/Dow leached in defonized water " worst case."

45

= -.

level s measured.

Also, acidi fication of the leach waters was delayed until just before the atomic absorption analysis was performed.

Precipitation of i

the metals may have occurred, especially for those leachates with high iron and nickel concentrations.

Finally, err <.r associated with dilution of the leachate aliquot by acidification was ignored. The approximately 1% error due to dilution was thought to be much less than the statistical error in the atomic absorption analysis. While no steps were made to quantify all possible errors, the largest variations were sure to have been seen in the ir.itial stages of leaching, where metal concentrations were highest and where contami-nation from the leach containers was most likely.

l Table 3.11 Comparison of Prepared Standards Analyzed by Flameless Atomic Absorption Spectroscopya Prepared Concentration Solutionb Measured ConcentrationsC i

Iron Nickel Iron / Nickel Iron / Nickel Iron /Ni_ckel 100 10 DW 65/7 65/5 65/7 50 100 DW 50/65 43/65 45/65 10 50 GW 40/55 15/18 15/37 50 50 SW 41/95 35/d aAll entries in ppb.

bDW = deionized water, GW = groundwe+er, SW = seawater.

l cCorrected for background.

I dBelow detection limit.

1 59 e and 60 o From NS-1/Dow 3.2.2 Leach Tests of F

C

,i 59 e and 60 o, the For the leach tests to detennine the release of F

C gross counts and counts per minute in these leachants are given as a function l

of time in Tables 3.12, 3.13, and 3.14 for deionized water, groundwater, and

{

seawater, respectively.

The gross counts per minute were corrected for back-ground, and the incremental and cumulative fraction released of the particular isotope were calculated using the computer program listed in Appendix B.

All counts were corrected for decay back to the time at which the counting stan-dard was counted.

This is equivalent to decay correction back to sample fab-rication since the counting standard and all samples were fabricated at the same time.

It should be noted that for those calculations when the net count was less than zero, the fraction release was assumed to be zero.

The gross activity in the 10 mL aliquot counting 9 standards was 7370 + 12 cpm (1.8642 +-

0.0019 x 104 for days 42 and 50) for Fe and 1 927 + 0.007 x 10'+ cpm 80 o.

The background was (1.1806 + 0.0015 x 104 for days 42 and 50) for C

22.0 + 077 (44.6 1 0.9 for days 42 and 50) and 19.8 + 0.6 cpm (40.1 + 0.9 for 46

Table 3.12 Gross Total Cgynts and Counts per Minute (cpm) Containing 59 e or ouCo in a 10 mL Counting Aliquot for F

NS-1/Dow Leached in Deionized Water Leach Time Days Counts cpm Counts cpm Counts cpm 59Fe i

Sample 1 Sample 2 0.125 1583+40 31.66+0.80 1925+44 38.50+0.88 1

1262T36 25.24TO.71 1422T38 28.44TO.75 2

1278T36

25. 56TO.72 1255T35 25.10TO.71 3

1166T34 23.3270.68 1143T34 22.86TO.68 4

1218735 24.36TO.70 1236T35 24.7270.70 7

1352T37 27.04T0.74 1396T37 27.92T0.75 8

1024T32 20.48T0.64 1151734 23.02T0.68 9

1148T34 22.96TO.68 1144T34 22.88TO.68 10 1191T35 23.8270.69 1181T34 23.6270.69 11 1186T34 23.72TO.69 1192T35 23.84TO.69 18 1340T37 26.80TO.73 1265T36 25.30T0.71 25 1252T35 25.04T0.71 1256T35 25.12T0.71 42 2708752 54.16T1.04 2597T51 51.94T1.02 50 2285748 45.7010.96 2254T47 45.08TO.95 60Co Sample 7 Sample 8 Sample 9 0.125 2750+52 55.00+1.05 3069+55 61.38+1.11 2557+51 51.14+1.01 1

1225T35 24.50TO.70 1558T39 31.16TO.79 1476T38 29.52TO.77 2

1151T34 23.0270.68 1318T36 26.36T0.73 151 T39 30.3270.78 3

1058T33 21.1670.65 1118T33 22.36TO.67 1191735 23.82TO.70 4

1121T33 22.4270.67 1252T35 25.04TO.71 1229T35 24.58T0.73 7

1136T34 22.7270.67 1639T40 32.78T0.81 1348T37 26.96TO.73 8

1032T32 20.64T0.64 1201T35 24.02T0.69 1105D3 22.10TO.66 9

1029+32 20.58TO.64 1210T35 24.20T0.70 1086T33 21.72TO.66 10 1119T33 72.38T0.67 1306T36 26.12TO.72 1140T34 28.80T0.67 11 1209T35 24.18T0.70 1261T36 25.22T0.71 1117T33 22.34T0.67 4

l 18 1221T35 24.42TO. 70 1854T43 37.08TO.86 1645V41 32.90TO.81 25 1198T35 23.96TO.69 1361737 27.22TO.73 1276T36 25.52TO.71 i

42 3319T58 66.38T1.15 3903T62 78.06T1.25 3211T57 64.22T1.13 l

50 2212147 44.2410.94 2421149 48.4210.98 2189147 43.7810.94 47

j Table 3.13 Gross Total Counts and Counts Per Minute (cpm) in a 10mL Counting Aliquot for NS-1/Dow Containing 59Fe or 00 o Leached in Groundwater C

Leach Time Days Counts cpm Counts cpm i

59 e 4

F Sample 3 Sample 4 0.125 1832 + 43 36.64 + 0.86 1750 + 42 35.00 + 0.84 1

1222 T 35 24.44 T 0.70 1403 T 37 28.06 T 0.75 2

1160 7 34 23.28 T 0.68 1310 T 36 26.20 T 0.72 3

1075 T 33 21.50 T 0.66 1197 T 35 23.94 T 0.69 4

1019 7 32 20.38 T 0.64 1199 T 35 23.98 T 0.69 7

1180 T 34 23.60 T 0.69 1431 T 38 28.62 T 0.76 j

8 1123 T 34 22.46 T 0.67 1151 + 34 23.02 + 0.68 9

1070 T 33 21.40 T 0.65 1208 T 35 24.16 T 0.70 10 1094 T 33 21.88 T 0.66 1115 T 33 22.30 T 0.67 11 1065 T 33 21.30 T 0.65 1189 T 34 23.78 T 0.69 18 1152 T 34 23.04 T 0.68 1336 T 37 26.72 T 0.73 25 1158 T 34 23.16 T 0.68 1197 T 35 23.94 T 0.69 42 2476 7 50 49.52 T 1.00 2736 7 52 54.72 T 1.05 50 2208 47 44.15 T.94 2330 T 48 48.60 T.97 i

60 o C

Sample 10 Sample 11 d

0.125 2303 + 48 46.06 + 0.96 2933 + 54 58.66 + 1.08 I

1 1489 T 39 29.78 T 0.77 1511 7 39 30.22 T 0.78 2

1361 T 37 27.22 T 0.74 1408 T 38 28.16 T 0.75 3

1234 T 35 24.68 T 0.70 1096 T 33 21.92 T 0.66 4

1328 T 36 26.56 T 0.73 1208 T 35 24.16 T 0.70 7

1651 T 40 33.02 T 0.81 1334 T 37 26.68 T 0.73 8

1214 T 35 24.28 T 0.70 1071 T 33 21.42 T 0.65 9

1175 T 34 23.50 T 0.69 1103 7 33 22.06 T 0.66 10 1216 T 35 24.32 T 0.70 1110 T 33 22.20 T 0.67 11 1229 T 35 24.58 T 0.70 1126 7 34 22.52 7 0.67 i

18 1675 T 40 33.50 T 0.82 1501 T 39 30.02 T 0.77 25 1441 T 37 28.82 T 0.76 1282 T 36 25.64 T 0.72 42 4028 T 63 64.22 T 1.13 3242 T 57 80.56 T 1.27 i

50 2704 7 52 43.78 T 0.94 2556 T 51 54.08 T 1.04 t

48

Table 3.14 Gross Total Counts and Counts Per Minute (cpm) in a 10mL Counting Aliquot for NS-1/Dow Containing 59 e or bO o Leached in Seawater F

C Leach Time Days Counts cpm Counts cpm 59Fe Sample 5 Sample 6 0.125 1822 + 43 36.44 + 0.85 1706 + 41 34.12 + 0.83 1

1416 T 38 28.32 T 0.75 1284 T 36 26.68 T 0.72 2

1306 7 36 26.12 T 0.72 1159 7 34 23.18 T 0.68 3

1108 T 33 22.16 T 0.67 1013 T 32 20.26 T 0.64 4

1130 7 34 22.60 T 0.67 1044 7 32 20.88 T 0.65 7

1148 7 34 22.69 T 0.68 1055 T 32 21.10 T 0.75 8

1047 7 34 21.94 7 0.66 1122 T 34 22.44 T 0.67 9

1086 7 33 21.72 T 0.66 1064 T 33 21.28 T 0.65 10 1061 7 33 21.22 T 0.65 1094 T 33 21.88 T 0.66 11 1077 7 33 21.54 T 0.66 1075 T 33 21.50 T 0.66 18 1142 7 34 22.84 T 0.68 1107 T 33 22.14 T 0.77 25 1137 7 34 22.74 T 0.67 1051 T 32 21.02 T 0.65 42 2346 7 48 46.92 T 0.97 2180 7 47 43.60 T 0.93 50 2250147 45.00 1 0.95 2236147 44.72 T 0.95 60Co Sample 12 Sample 13 0.125 2607 + 51 52.14 v 1.02 2571 + 51 51.42 + 1.01 1

1362 7 37 27.24 T 0.74 1611 T 40 32.22 T 0.80 2

1098 T 33 21.96 T 0.66 1162 T 34 23.24 7 0.68 3

970 7 31 19.40 T 0.62 1031 T 32 20.62 T 0.64 4

1010 T 32 20.20 T 0.64 1206 T 35 24.12 T 0.69 7

997 T 32 19.94 7 0.63 1006 T 32 20.12 T 0.63 8

981 T 31 19.62 T 0.63 1001 T 32 20.02 T 0.63 9

997 7 32 19.94 7 0.63 900 T 30 18.00 T 0.60 10 1003 T 32 20.06 T 0.63 991 T 31 19.82 T 0.63 11 979 + 31 19.58 + 0.63 949 + 31 18.98 7 0.62 18 1007 T 32 20.14 T 0.63 950 T 31 19.00 T 0.62 25 958 T 31 19.16 T 0.62 922 T 30 18.44 7 0.61 42 2138 T 46 42.76 T 0.92 1906 T 44 38.12 T 0.87 50 2043[45 40.86[0.90 1872 T 43 37.44 T 0.87 49

= -.

I 4

1 days 42 and 50) for 59Fe and 60Co, respectively for a 10 mL sample.

Tables 3.15, 3.16, and 3.17 list the calculated incremental and cumulative l

f raction releases of 59Fe in the three leachants as a function of time.

It i

i should be noted that the errors given in these tables reflect only that sta-tistical error associated with counting the sample.

The corresponding information for 60Co release are given in Tables 3.18, 3.19, and 3.20.

The cumulative fraction released versus time for 59Fe are shown graphically in Figures 3.15, 3.17, and 3.19 for deionized water, groundwater, and seawater, respectively. The corresponding data for 60Co release are plotted in Figures 3.16, 3.18, and 3.20.

For each sampling period, the mean cumulative fraction release of the two (or three) samples normalized by V/S was also calculated using the computer program in Appendix 59 e and 5.

These data are plotted in Figures 3.21, 3.23, and 3.25 for F

Figures 3.22, 3.24, and 3.26 for 60Co in deionized water, groundwater, and seawater, respectively.

In addition, the mean cumulative fraction release multiplied by V/S for samples in each of the three leachants at the end of 25 and 50 days is given in Table 3.21.

59 e tracer study with F

In comparing the Fe relcase rates from the those measured for nonradioactive Fe, there are some rather strikina similari-ties and differences.

Since it is expected that the 59Fe is in the same

~

l chemical environment, one might expect that within the experimental error the results of the two experiments would be the same.

Based upon the mean values for the iron release rate in Table 3.21, the trend for iron leachability is:

i deionized water > groundwater > seawater.

This is the reverse of the trend observed in the nonradioactive iron release study.

An examination of the i

j errors in the mean values in both Tables 3.10 and 3.21, which is a measure of the sample-to-sample variation of the release rate, indicates that the dis-crepancy between the observed trends can be accounted for by this variation.

i From a comparison of the data in the two tables for a given leachant, it may be seen that given the sample-to-sample variation, the iron release rate of 1

NS-1/Dow in both deionized water and groundwater are the same in both the tracer and " cold" studies. There are large differences between the release rates measured in seawater by the two experiments.

A comparison of l

Figures 3.5 and 3.19 indicates that, although a portion of the difference can be accounted for by the large initial iron release of sample 8 (Figure 3.5),

this difference cannot be totally accounted for by sample to sample variation.

The cause of this difference remains unexplained.

It must also be noted that the analytical errors associated with counting in the tracer experiments (ap-proximately 2%) are much less than those associated with the flameless atomic absorption used in the " cold" leach tests (<30%).

The 6000 leach test results appear to be consistent with the 59pe results.

The mean values of the cumulative fraction release show the fol-lowing trend for 60Co release with leachant:

deionized water i groundwater

> seawater.

If one considers the sample-to-sample variation this trend agrees with the 59Fe data in Table 3.21.

(Continued page 63) 1 50 l

l

-, _. ~.

Table 3.15 59 e for Incremental and Cumulative Fraction Released of F

NS-1/Dow Leached in Deionized Water Time Incremental Cumulative Fraction (days)

Fraction Released Released Sample 1 0.125 0.131 1 0.014 E-02 0.131 f.0.014 E-02 1

0.44310.137 E-03 0.176 j;0.020 E-02 2

0.491 1 0.138 E-03 0.225 1 0.024 E-02 3

0.183 1 0.136 E-03 0.243 1 0.028 E-02 4

0.330 1 0.138 E-03 0.276 1 0.031 E-02 7

0.70910.143 E-03 0.347 1 0.034 E-02 8

0 1 0.134 E-03 0.347 j;0.037 E-02 9

0.13710.139 E-03 0.361 1 0.039 E-02 10 0.262 1 0.141 E-03 0.387 1 0.042 E-02 11 0.249 1 0.142 E-03 0.412 1.0.044 E-02 18 0.670 1 0.148 E-03 0.481 1 0.046 E-02 25 0.446 1 0.146 E-03 0.526 1 0.049 E-02 42 0.811 1 0.117 E-03 0.607 f_0.050 E-02 50 0.094 1 0.112 E-03 0.617 1 0.051 E-02 Sample 2 0.125 0.224 1 0.015 E-02 0.224 1 0.015 E-02 1

0.882 1 0.141 E-03 0.313 1 0.021 E-02 2

0.428 1 0.137 E-03 0.355 1 0.025 E-02 3

0.119 1 0.135 E-03 0.367 1 0.028 E-02 4

0.380 1 0.139 E-03 0.405 1 0.032 E-02 7

0.833 1 0.144 E-03 0.489 1 0.035 E-02 8

0.14510.138 E-03 0.503 1 0.037 E-02 9

0.126 1 0.139 E-03 0.516 1 0.040 E-02 10 0.233 1 0.141 E-03 0.539 1 0.042 E-02 11 0.266 1 0.142 E-03 0.565 1 0.045 E-02 18 0.481 1 0.146 E-03 0.613 1 0.047 E-02 25 0.458 1 0.146 E-03 0.659 1 0.049 E-02 42 0.623 1 0.115 E-03 0.722 1 0.050 E-02 Su 0.041 1 0.112 E-03 0.726 1 0.052 E-02 51

4 Table 3.16 59 e for Incremental and Cumulative Fraction Released of F

NS-1/Dow Leached in Groundwater Time Incremental Cumulative Fraction (days)

Fraction Released Released Sample 3 0.125 0.199 1 0.015 E-02 0.199 1 0.015 E-02 1

0.334 1 0.136 E-03 0.233 1 0.020 E-02 2

0.165 1 0.135 E-03 0.249 1 0.024 E-02 3

0.

1 0.133 E-03 0.249 1 0.028 E-02 f

4 0.

1 0.133 E-03 0.249 1 0.031 E-02 7

0.225 1 0.138 E-03 0.271 1 0.034 E-02 8

0.065 1 0.138 E-03 0.278 1 0.037 E-02 9

0.

10.137 E-03 0.278 1 0.039 E-02 10 0.

1 0.139 E-03 0.278 1 0.041 E-02 11 0.

!_0.139 E-03 0.278 1.0.044 E-02 18 0.152 1 0.142 E-03 0.293 1 0.046 E-02 25 0.170 1 0.142 E-03 0.310 f.0.048 E-02 i

42 0.418 1 0.114 E-03 0.352 1 0.049 E-02 50 0.

1 0.111 E-03 0.352 1 0.051 E-02 Sample 4 0.125 0.177 1 0.015 E-02 0.177 f;0.015 E-02 1

0.831 1 0.141 E-03 0.260 1 0.020 E-02 2

0.580 1 0.139 E-03 0.318 1 0.025 E-02 3

0.270 1 0.137 E-03 0.345 1 0.028 E-02 4

0.277 1 0.138 E-03 0.373 f;0.031 E-02 7

0.933 1 0.145 E-03 0.466 1 0.035 E-02 8

0.14510.138 E-03 0.481 1 0.037 E-02 9

0.308 1 0.141 E-03 0.511 1 0.040 E-02 10 0.043 1 0.139 E-03 0.515 1 0.042 E-02 l

11 0.258 1 0.142 E-03 0.542 1 0.045 E-02 18 0.860 1 0.117 E-03 0.725 1 0.051 E-02 25 0.171 1 0.113 E-03 07429 1 0.052 E-02 l

l 52

l Table 3.17 59 e for Incremental and Cumulative Fraction Released of F

NS-1/Dow Leached in Seawater Time Incremental Cumulative Fraction (days)

Fraction Released Released Sample 5 0.125 0.197 1 0.015 E-02 0.197 1 0.015 E-02 1

0.867 1 0.141 E-03 0.283 1 0.021 E-02 2

0.569 1 0.139 E-03 0.340 1 0.025 E-02 3

0.022 1 0.134 E-03 0.342 1 0.028 E-02 4

0.084 1 0.136 E-03 0.351 1 0.031 E-0^

7 0.135 1 0.137 E-03 0.365 1 0.034 E-02 8

0.

+ 0.137 E-03 0.365 1 0.037 E-02 9

0.

1 0.138 E-03 0.365 1 0.039 E-02 10 0.

1 0.138 E-03 0.365 1 0.042 E-02 11 0.

1 0.139 E-03 0.365 1 0.044 E-02 18 0.123 1 0.142 E-03 0.377 1 0.046 E-02 25 0.109 1 0.143 E-03 0.388 1 0.048 E-02 l

42 0.197 + 0.113 E-03 0.407 + 0.050 E-02 l

50 0.034 + 0.113 E-03 0.410 + 0.051 E-02 Sample 6 0.125 0.165 1 0.015 E-02 0.165 t 0.015 E-02 1

0.505 1 0.138 E-03 0.216 1 0.020 E-02 2

0.163 1 0.135 E-03 0.232 1 0.024 E-02 3

0.

1 0.132 E-03 0.232 1 0.028 E-02 4

0.

1 0.134 E-03 0.232 1 0.031 E-02 7

0.

1 0.135 E-03 0.232 1 0.034 E-02 8

0.063 1 0.138 E-03 0.238 1 0.036 E-02 9

0.

1 0.137 E-03 0.238 1 0.039 E-02 10 0.

1 0.139 E-03 0.238 1 0.041 E-02 11 0.

1 0.139 E-03 0.238 1 0.043 E-02 18 0.020 1 0.141 E-03 0.240 1 0.046 E-02 25 0.

1 0.140 E-03 0.240 t 0.048 E-02 42 0.

+ 0.110 E-03 0.240 + 0.049 E-02 50 0.010 + 0.112 E-03 0.241 + 0.050 E-02 53

. ~.. --

4 i

i i

I Table 3.18 i

6D o for Incremental and Cumulative Fraction Released of C

NS-1/Dow Leached in Deionized Water Time Incremental Cumulative Fraction (days)

Fraction Released Released t

Sample 7 0.125 0.18210.006 E-02 0.182 f.0.006 E-02 1

0.24410.048 E-03 0.207 + 0.008 E-02 l

2 0.167 1 0.047 E-03 0.224 1 0.009 E-02 3

0.706 1 0.046 E-03 0.231 10.010 E-02 4

0.136 1 0.047 E-03 0.245 +. 0.011 E-02 7

0.151 1;0.047 Es03 0.260 f. 0.012 E-02 8

0.436 f. 0.457 E-04 0.2641; 0.013 E-02 9

0.40510.457 E-04 0.268 f 0.014 E-02 10 0.134 f. 0.047 E-03 0'.281 f.0.015 E-02 11 0.228 1 0.048 E-03 0.304 f. 0.015 E-02 18 0.240 1 0.048 E-03 0.328 f.0.016 E-02 25 0.21610.048 E-03 0.350 f 0.017 E-02 42 0.141 + 0.008 E-02 0.491 + 0.019 E-02 1

50 0.222 + 0.070 E-03 0.513 + 0.020 E-02 i

Sample 8 0.125 0.216 1 0.007 E-02 0.216 1 0.007 E-02 1

1 0.590 +. 0.051 E-03 0.274 1 0.008 E-02 2

0.341 2;0.049 E-03 0.309 1 0.010 E-02 3

0.133 f. 0.047 E-03 0.3221. 0.011 E-02 l

4 0.27210.048 E-03 0.349 1 0.012 E-02 7

0.67410.052 E-03 0.417 f 0.013 E-02 8

0.219 1 0.048 E-03 0.43810.014 E-02 l

9 0.22910.048 E-03 0.46110.015 E-02 10 0.329 1. 0.049 E-03 0.494 1 0.015 E-02 11 0.28210.048 E-03 0.52210.016 E-02 18 0.898 1 0.055 E-03 0.61210.017 E-02 25 0.385 f 0.049 E-03 0.651 10.018 E-02 42 0.204 + 0.008 E-02 0.855 + 0,020 E-02 50 0.446 + 0.072 E-03 0.899 + 0.021 E-02 i

Sample 9 0.125 0.163 f. 0.006 E-02 0.163 f.0.006 E-02 1

0.5051. 0.051 E-03 0.213 f. 0.008 E-02 2

0.546 f. 0.051 E-03 0.26810.009 E-02 3

0.20910.047 E-03 0.28910.011 E-02 4

0.248 1 0.048 E-03 0.313 f. 0.012 E-02 7

0.37210.049 E-03 0.351 +.0.013 E-02 8

0.120 1 0.047 E-03 0.362 1 0.013 E-02 9

0.99810.463 E-04 0.37210.014 E-C?

10 0.156 1 0.047 E-03 0.38810.015 E-02 r

11 0.132 f. 0.047 E-03 0.401 1.0.016 E-02 18 0.681 1 0.052 E-03 0.47010.017 E-02 25 0.29810.049 E-03 0.49910.017 E-02 42 0.129 + 0.083 E-02 0.629 + 0.019 E-02 50 0.193 + 0.070 E-03 0.648 + 0.020 E-02 54

i Table 3.19 l

Incremental and Cumulative Fraction Released of 60 o for C

NS-1/Dow Leached in Groundwater Time Incremental Cumulative Fraction (days)

Fraction Released Released Sample 10 0.125 0.136 1 0.006 E-02 0.136 1 0.006 E-02 1

0.518 1 0.051 E-03 0.188 + 0.008 E-02 2

0.38510.049 E-03 0.227 1 0.009 E-02 3

0.253 1 0.048 E-03 0.252 1 0.010 E-02 4

0.351 1 0.049 E-03 0.287 1 0.011 E-02 7

0.686 1 0.052 E-03 0.356 1 0.013 E-02 8

0.233 1 0.048 E-03 0.379 1 0.013 E-02 9

0.192 1 0.047 E-03 0.398 1 0.014 E-02 10 0.235 1 0.048 E-03 0.422 1 0.015 E-02 11 0.249 1 0.048 E-03 0.447 1 0.016 E-02 18 0.712 1 0.053 E-03 0.518 1 0.017 E-02 25 0.469 1 0.050 E-03 0.565 _+ 0.017 E-02 42 0.217 + 0.008 E-02 0.782 + 0.019 E-02 50 0.750 + 0.074 E-03 0.857 + 0.021 E-02 Sample 11 0.125 0.202 1 0.006 E-02 0.202 1 0.006 E-02 1

0.541 1 0.051 E-03 0.256 1 0.008 E-02 2

0.43410.050 E-03 0.299 1 0.010 E-02 3

0.110 1 0.046 E-03 0.310 1 0.011 E-02 4

0.227 1 0.048 E-03 0.333 +_0.012 E-02 7

0.357 1 0.049 E-03 0.369 1 0.013 E-02 8

0.842 1 0.046 E-03 0.377 1 0.013 E-02 9

0.117 1 0.047 E-03 0.388 1 0.014 E-02 10 0.124 1 0.047 E-03 0.401 1 0.015 E-02 11 0.141 1 0.047 E-03 0.415 1 0.016 E-02 18 0.531 10.051 E-03 0.469 1 0.017 E-02 25 0.303 1 0.049 E-03 0.499 1 0.017 E-02 42 0.133 + 0.008 E-02 0.632 + 0.019 E-02 50 0.592 + 0.073 E-03 0.691 + 0.020 E-02

(

55

-. = _.

I Table 3.20 i

i Incremental and Cumulative Fraction Released of60Co for j

NS-1/Dow Leached in Seawater Time Incremental Cumulative Fraction l

(days)

Fraction Released Released f

Sample 12

)

0.125 0.168 1 0.006 E-02 0.168 1 0.006 E-02 i

1 0.386 1 0.049 E-03 0.207 1 0.008 E-02 I.

2 0.112 1 0.046 E-03 0.217 +.0.009 E-02 3

0.

10.045 E-03 0.21710.010 E-02 4

0.208 1 0.454 E-04 0.220 1 0.012 E-02 7

0.07271 0.453 E-04 0.221 1 0.012 E-02 8

0.

1 0.045 E-03 0.221 1 0.013 E-02 4

9 0.07281 0.453 E-04 0.221 1 0.014 E-02 10 0.135 1 0.454 E-04 0.223 1 0.014 E-02 11 0.

10.045 E-03 0.223 1 0.015 E-02 18 0.177 1 0.454 E-04 0.22410.016 E-02 4

25 0.

1 0.045 E-03 0.224 1 0.016 E-02 42 0.143 + 0.069 E-03 0.239 + 0.018 E-02 50 0.041 + 0.068 E-03 0.243 + 0.019 E-02 I

i i

Sample 13 0.125 0.168 1 0.006 E-02 0.164 +_0.006 E-02 l

1 0.645 1 0.052 E-03 0.229 1 0.008 E-02 2

0.17810.047 E-03 0.247 1 0.009 E-02 i

3 0.426 1 0.456 E-04 0.251 1 0.010 E-02 4

0.22410.048 E-03 0.273 1 0.011 E-02 7

0.166 1 0.454 E-04 0.275 1 0.012 E-02 8

0.114 1 0.453 E-04 0.276 1 0.013 E-02 9

0.

1 0.045 E-03 0.276 1 0.014 E-02 10 0.01041 0.452 E-04 0.276 1 0.015 E-02 l

11 0.

1 0.045 E-03 0.276 1 0.015 E-02 i

18 0.

1 0.045 E-03 0.276 1 0.016 E-02 l

25 0.

1 0.044 E-03 0.276 1 0.016 E-02 42 0.

+ 0.067 E-03 0.276 + 0.018 E-02 50 0.

+ 0.067 E-03 0.276 + 0.019 E-02 l

56 l

- ~.. =

obe r*

--9, -

g

~-

y

..... - - o,.. -f.'

T, o.

o 3

.-y J

.,:g. 's.:.

-_/-/

c? d-

...: T 4o y

T N*-..:f.

O

. ev e-4-,.

T en-<_(

8 00 lb0 2b0 3b0 40.0 Sb0 60 0 Time (days) 59 e for Figure 3.15 Cumulative fraction released (C.F.R. ) of F

NS-1/Dow leached in deionzed water. o sample 1, o sample 2.

^6****.

3 "l8 g_

_y...Y s

a.

-d N

^

a o,

x A

a g

d d ag 8

36' 01 00 10 0 2b0 3bo 400 6b0 600 Time (days) 60 o for Figure 3.16 Cumulative fraction released (C.F.R.) of C

l NS-1/Dow leached in deionzed water. a sample 7, o sample 8, A sample 9.

57

i D. a 1

. f,. _ - - -9..

...,..... f.... - T.

o.

i

.,.. 4-r

.L

,o, --

c: o

,.c -

a,-

g

,9

--f--

..a.

0

,3V-T xe

--~

1 oo 00 lb0 2b0 sho 400 Sb0 60 0 Time (days) 59 e for Figure 3.17 Cumulative fraction released (C.F.R.) of F

NS-1/Dow leached in groundwater c sample 3, o sample 4.

@ 8-

- - .E

,, g -

g.

j y

f.,y...

.,, 6. -

u, Y

oe y a

8.

0 lb0 20 0 3'O O 4'O O 5' O 60.0 O

Time (days) i Figure 3.18 Cumulative fraction released (C.F.R.) of 60C0 for l

NS-1/Dow leached in groundwater. o sample 10, o sample 11.

58

,,'c o r=

E-2: o

[

w,.

- II__

s:

,,V Q g

te g, g,...........4.....4...............4......4

.n o

O 00 lbo

$0 3b0 400 Sb0 60 0 Time (days)

Figure 3.19 Cumulative fraction released (C.F.R.) of 59Fe for HS-1/Dow leached in seawater. o sample 5, o sample 6.

'O o 7*

\\

on' g~y....4....4..............4.....4 "s

I

'~

, MD I

j.

do w n-O i

, [

l S.

o o

l 00 lbo 2bo 30 0 400 Sbo 60 0 Time (days)

Figure 3.20 Cumulative fraction released (C.F.R.) of 60 o for C

NS-1/D0w leached ir. seawater. o sample 12, o sample 13.

59

i 8

v

/

o

.-l e-M b.

d Z

__1 -

g:

s 0- Y i t oo

'0 lb0 20 0 30 0 400 5'00 60 0 0

Time (days) l Figure 3.21 Average cumulative fraction release (C.F.R.) of 59Fe for NS-1/Dow leached in deionized water.

?98 o

E g

)

=-

3 en go g

[

^

__.?

y

.gr

[

T 1 _.

g, N-E oo 00 lbo 20 0 300 400 50 0 60 0 Time (days)

Figure 3.22 Average cumulative fraction release (C F.R.) of 60 o for NS-1/Dow leached in deionized water.

C I

60

l "e. :

o c-

.:~

bg_

~

T i

l Uo_

I j

{

r i

4 4

3 00 10 0 20 0 30 0 400 50 0 60 0 Time (days)

Figure 3.23 Average cumulative fraction release (C.F.R.) of 59 e for NS-1/Dow leached in groundwater.

F S, E T-o*-

2 CS cn h$_

2 8-il S

oo 00 10 0 20.0 30 0 400 50 0 60 0 Time (days)

Figure 3.24 Average cumulative fractiort release (C.F.R.) of 60Co for NS-1/Dow leached in groundwater.

61

)

9. $

I oe-m E3 enh-$

x

~~

T e

r l

N w:-

S 00 lbC 2b0 30 0 400

$00 60 0 Time (days)

Figure 3.25 Average cumulative fraction release (C.F.R.) of 59 Fe for NS-1/Dow leached in seawater.

S. $

on-n Eo;

~~ 1TT~

T

~~

go n-N-

1 x

I k ca U o.

t 00 lb0 20 0 3' 0 400 5' 0 60.0 0

0 l

Time (days) l Figure 3.26 Average cumulative fraction release (C.F.R.) of 60Co for NS-1/Dow leached in seawater.

62

Table 3.21 Mean Cumulative Fraction Release After 25 and 50 Days Normalized by 59 e and 60 o Release for NS-1/Dow in V/S for C

F Deionized Water, Groundwater, and Seawater Mean Cumulative Fractgon Released x V/S (x10 cm)a 59pe 60 o 59pe 60 o C

C Deionized Water 5.2 + 0.8 4.4 + 1.3 5.9 + 0.7 6.0 + 1.7 Groundwa ter 4.1 + 2.0 4.6 + 0.4 4.8 + 2.4 6.8 + 1.0 Seawater 2.7 7 0.9 2.2 T 0.3 2.8 T 1.0 2.3 T 0.2 aEntries in this table are 103 times their actual value, e.g.,

5.2 + 0.8 should be read as 5.2 + 0.8 x 10-3, When reviewed as a whole, the leach test results for nonradioactive Fe 59 e and bO o indicate that the fractional release of and Ni release and F

C iron, nickel, and cobalt when leached over long times will be nearly the same.

This conclusion is borne out by comparison of the data in Tables 3.10 and 3.21.

For deionized water, the nonnalized frqctional releases for Fe, Ni, 59Fe and Co are respectively, 5.6 + 2.1 x 10-0 cm, 5.0 + 1.8 x 10-3 cm,

5. 2 + 0. 8 x 10-3 cm, a nd 6. 0 + 1. 7 x 10-3 cm.

A similaF correlation is

~

seen in groundwater.

Seawater as mentioned above remains anomalous.

The de-pendence of the leach rate upon leaching medium appears to be slight (less than a factor of 2), and based on the data as a whole, no clear trend is evi-dent.

Finally, it should be noted that, in all these leach experiments, large sample-to-sample variation is evident.

Some of this variation can be ac-counted for by differences in the initial release, however, an examination of the plotted cumulative fraction release versus time (Figures 3.1 to 3.8 and 3.15 to 3.20) reveals that these differences cannot fully account for the variation.

The cause of this variation is unknown and may only reflect the stochastic nature of the release process.

The relevance of this variation to the long-term release from full-size samples is unknown.

3.2.3 Comparison of BNL Results With Leach Tests Performed by Dow It is difficult to com are he results obtained in this study with l

tive Fe and Ni release, 3b$w. 3b,4 leach tests performed b D In the Dow leach tests on nonradioac-samples of essentially the same size as the l

leach tests reported herein were immersed in 250 mL deionized water.

This gava a leachant volume to sample surface area ratio of approximately 2 cm I

which was about a factor of five less than the BNL leach tests.

Further, the sampling interval was one week for the Dow tests for a total leaching time of 63

i two weeks.

The Fe and Ni release rates in the Dow leach test were approxi-l mately 0.1% for the first seven days and 0.01% for the next seven days.

The data in Table 3.6 indicate an average cumulative release of 0.24 + 0.11% for Fe and 0.27 + 0.11% for Ni after seven days.

Although the Dow results are lower than those found in the BNL experiments, agreement between the two ex-periments is fair considering the experimental errors and the fact that the leach test performed by Dow may have surpressed the observed leach rate due to saturation effects.

60 o release (4) were conducted in a Dow leach tests which measured C

manner similar to their iron and nickel leach studies.

The sampling f requency in the Dow 60Co leach tests was daily for the first two weeks (except week-ends) and at 22, 30, and 70 days. The cumulative fractional release reported was 0.7% at 7 days, 0.8% at 30 days and 0.9% at 70 days.

While no errors are 60 o release measured by Dow appeargO o (see C

to be sig-given for these data, the nificantly higher thgn that measured in this leach study for C

Table 3.21).

Dow's 00Co results are also much higher than the results re-pcrted by Dow for Fe and Ni.

The Dow results appear to contradict their claim that the release rate should not depend on the ion being leached.

Given the sample-to-sample variation observed by BNL, however, resolution of the differ-ences in the Dow studies and the differences between the Dow results and those reported herein must await some estimate by Dow of the uncertainty in their

)

consistent with Dow's claim than data presented by Dow.(3b,4)be much more reported release rates.

The data presented herein appear to 1

The results of these tests have been discussed with Dow. Given the differences between Dow and the authors regarding the interpretation of the results, we have included Dow's comments in Appendix C.

l l

l 64 l

4.

CONCLUSIONS i

The results of the immersion tests of NS-1 concentrate solidified in Dow vinyl ester-styrene indicate that toluene and xylene interact strongly with t

the waste form.

Swelling of the waste and absorption of these organics found in the immersion tests conducted in the pure organic, as well as the weight losses observed on drying the forms af ter immersion, indicate that waste solidified in this binder should be separated from sources of these organics upon disposal in shallow land burial.

NS-1/Dow also interacts strongly with organic saturated water.

The behavior of the waste form in water saturated with organics is not well understood, however.

The leaching behavior of the NS-1/Dow waste forms observed appears to cor-relate with that reported by Dow for Fe and Ni.

The Co release rate is much l ower than that reported by Dow.

However, this rate itself appears much higher than that reported by Dow from Fe and Ni.

The Fe, Ni, and Co frac-tional release rates appear to be nearly the same witi'in the experimental Also, within the error, the release rate appeacs to be only weakly error.

dependent upon the leaching medium. A large sample-to-sample variation was noted in the leach experiment.

The cause of this variation is not known.

t l

65

5.

REFERENCES 1.

U.S. Nuclear Regulatory Canmission, " Final Environmental Statement Related to Primary Cooling System Chemical Decontamination at Dresden Nuclear Power Station, Unit No.1," USNRC Report, NUREG-0686, October 1980.

2.

H. Stephen and T. Stephen, Eds., Solubilities of Inorganic and Organic Compounds, Volume 1, Binary Systems, Part 1, Pergamon Press, Oxford, 1963.

3.

(a) H. Filter, Dow Chemical Corp., Midland, MI, private canmunication to R. E. Barletta (June 3, 1981) (see also Appendix C). (b) H. Filter, Dow Chemical Corp., Midland, MI, private conmunication to A. J. Weiss (June 29, 1980).

4.

H. Filter, " Leach Test Data on Solidified Radioactive Decontamination Solvent," Dow Chemical Corporation Report, B 600-138-79, Midland, MI, 1980.

l l

67

APPENDIX A RADWASTE SOLIDIFICATION SYSTEM CRESDEN 1 CHEMICAL CLEANING FACILITY PREPARED FOR:

UNITED.STA RS NUCLEAR REGULATORY COMMISSION INSPECTION TEAM July 9, 1980 l

l 69

I TABLE OF CONTENTS Pages 71 1.

AGENDA 72 II. SYSTEM DESCRIPTION 72 i

A.

Feed Control 72 B.

Filling and Mixing (Level Control)

--Simplified Flow Diagram - Figt!re 1 74 C.

Curing 74 D.

Quality Monitoring 74 i

E.

Capping and Radiation Monitoring 75 F.

Positioning and Drive 75 G.

Instrument and Controls 75 H.

Interlocks and Alarms 75 I.

Design and Operating Conditions 75 III. PROCESS PARAMETERS 75 A.

pH of the Liquid Waste 76 B.

Waste Temperature 76 C.

Binder Temperature D.

Waste to Binder Ratio 76 78 E.

Sequence of Addition of Catalyst and Promoter F.

Promoter and Catalyst Quantities 78 78 G.

Mixer Speed 79 IV. RESULTS 79 A.

Hardness 80 B.

Temperature Rise 80 i

C.

Free Liquid 81 i

V.

SOLIDIFICATION AGENT / CLASSIFICATION 82 REFERENCES 83 APPENDIX I l

i 70 l

(

AGENDA For Solidification Demonstration Commonwealth Edison - Dresden Station Wednesday, July 9, 1980 1:00 PM Introduction and Overview - (handout)

(Administration Building) 1:30 PM Security Clearance 2:00 PM Beginning of Demonstration 1.

Nake verification sample.

(sample sink) 2.

Add binder to test barrels.

1 3.

Move drum to mixer.

4.

Mix; add catalyst, promoter, and simulated waste.

5.

Move to holding section of conveyor for curing / hardening.

6.

Repeat steps 3,4,5 for second barrel.

7.

During hardening period, prepare additional verification samples.

8.

Test barrels with Quality check devices.

9.

Cap barrels with double seamer.

10.

Wipe exterior of barrel, i

11.

Transfer to storage area using Whiting crane.

12.

Label and initial test barrels Thursday, July 10, 1980 9:00 AM Meeting at Administration Building and proceed through security 1.

Retrieve one test barrel.

2.

Cut steel away with metal s a w'.

3.

Chain-saw solidified waste.

4.

Present samples to NRC representatives.

11: 30 AM Leave Site fML/ji 71 7-8-80 4890A

i 1

l II. SYSTEM DESCRIPTION (Reference 1)

The radioactive waste solidification system is based on a Dow Chemical Company (Dow) proprietary process which forms stable mixtures that are then chemically cured to form hard, solid monoliths.

Liquid or slurry waste is stirred with a commercially available modified vinyl ester resin until a stable mixture is formed.

The mixture then is cured by the addition of a i

catalyst and a promoter.

The final result is a homogeneous solid which contains no free liquid.

A detailed version of this section classified as Dow Procrietary has been filed with the Nuclear Regulatory Commission (NRC) f in Report DNS-RSS-001-P-A.

l 1

A simplified ficw diagram, Figure 1, shows the major components used in the l

radwaste solidification system at Dresden Station.

A.

Feed Control 4

Waste is tranferred frcm the collection and storage tanks to a tank

)

where it is thoroughly mixed. A representative sample is withdrawn.

This sample is solidified - the verification step - to determine that t

the solidification process will operate properly. This sample solidification step also establishes the operating parameters for the specific waste to be processed.

B.

Filling and Mixing (Level Control)

The volume of waste for solidification is controlled by batch processing through the metering tank.

The radwaste metering tank is filled to its predetermined volume by pumping waste frcm the evaporator bottoms tank with gravity overflow return to the evaporator botters tank.

72

I CONTR01. LED AREA l

OUTSIDli 0F SOLIDIFICATION l

AREA FROM UNCONTROLLED AREA I

RADWASTE STORAGE g

+ -c4 BOUNDARY I

RESIN OR l

RADWASTE GRAVITY N METEllING l

RETURN EVAPORATOR T-ll8 TANK g

isOTTOMS OR ION

?"$2s \\/

excuAuGE uATen I

BINDER TANKS l

T-115 (A,B,c,t.0)

CATALYST l

l U

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l SAMPLE a

l PROMOTER l-------

l CONTROLLED AREA g

l SOLIDIFICATION AREA l

QUALITY d,",,

y 1

MONITOR SMEAR 6 l

HIXER CONTAINER RADIATION l

IIOLDING ZONE SEAL MONITORING

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- CONVEYOR TO STORAGE l

SIMPLIFIED FLOW DIAGRAM FIGURE 1

The solidification container is loaded with a predetermined quantity of binder at the prep station and transferred to the mixing station by ccnveyor.

At the mixing station, the waste and binder are combined in their measured proportions. A drum will centain 20 gallons of binder.

30 gallons of liquid waste will be added, followed by promoter; and finally, the catalyst will be added to in'tiate the curing process.

r C.

Curing i

The mixture is allowed to cure (solidify) while remaining on the conveyor.

The curing will result in solidification in about one hour, and temperature of the mixture will not exceed 212*F.

D.

Quality Monitoring At the quality monitoring station, the solidified contents of the container are tested to assure proper product quality. This monitoring consists of measuring two separate properties which are unique characteristics of the solid produced by the solidification l

process:

(1) the solidification is an exothermic reaction and the resulting temperature rise is ceasured for comparison with the representative sample test, the verification step, 'and (2) resistance to penetration (hardness) is measured to assure i

that the reaction is completed and that a solid block has been obtained.

E.

Caccing and Radiation Monitoring The container of solidified and quality monitored waste is sealed.

It is then subjected to the radiation surveys and smear testing required for storage and shipment.

74

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F.

Positioning and Drive A roller conveyor is used for transfer of the container from the prep station through the solidification process.

Stops and clamps are used for positioning and holding the container at the various stations where operations are performed.

G.

Instrument and Controll The system is operated remotely froin control panels (CP-401 and CP-402).

Visual inspection of the operations is by remote TV and lead glass windows.

1 H.

Intericc b and Alarms, Interlocks and alarms are providea to maintain proper operating sequence and prevent mechanical damage.

I.

Design and Operating Conditions The system is designed to solidify wastes at a rate of six 55 gallon drums / hour.

III. PROCESS PARAMETERS The following is a list of the significant variables that must be controlled during the operation of the sclidification process.

A.

CH of the Licuid Waste Evaporator bottoms or the ion exchange slurry must be in the pH range of 2.5 to 11.

If eitner fall outside of the range, caustic soda must 75

be added to raise the pH or sulfuric acid must be added to lower the pH.

These additions should be added directly to the evaporator bottoms tanks,115A, B, or C, or to the ion exchange tank,1150. The tanks must be agitated until a consistent pH reading is obtained.

This procedure is continued until a consistent pH reading is obtained in the range of 2.5 to 11.

B.

Waste Temcerature Evaporator bottoms er ion exchange resin slurries (wastes) must have a temperature below 140*F.

If an evaporator bottoms tank does have a temperature that exceeds this limit, it will be allowed to cool by natural convection until the waste temperature is below 140*F.

Providing that the waste and binder can be pumpad, there is no lower temperature limit for the solidification of the waste.

C.

Binder Temcerature The binder, which is stored in a 5,800 gallon tank inside the chemical cleaning building, will approach the room temperature of 70 to 95'F.

In this range, the temperature of the binder is acceptable and does not need additional control.

D.

Waste to Binder Ratio The waste to binder ratio is dependent upon the type of radwaste to be solidified. For solidification of evaporator bottoms, the waste to binder volumetric ratia can vary between 1.35/1.0 and 1.65/1.0. For solidification of ion exchange slurries, the waste to binder volumetric ratio may vary between 1.8/1.0 and 2.2/1.0. For 76

1 solidification of the evaporator bottoms at Dresden, the waste to binder volumetric ratio will be 1.5/1.0.

For the ion exchange slurries the ratio will be 2.0/1.0.

The proper ratio is assured by controlling the weight of binder added to each drum. A conveyor drum stop prevents advancement of any drum containing an improper amount of binder.

The 115-Evaporator Bottoms Tank is recirculated through the 118-Radwaste Metering Tank to the overflow level and back to the Evaporator Bottoms Tank. The overflow level on the metering tank is set at 30 gallons.

To assure that there are 30 gallons of waste in the metering tank, the dump valve allowing the waste to flow into the drum containing the binder will not be opened until the following conditions have been met:

(1) The overflow switch at the 30 gallon level has been activated indicating flow.

(2) The flow switch at the 30 gallon level has been deactivated indicating no flow and that all waste in the metering tank above the 30 gallon overflow has drained.

In a similar manner, the ion exchange slurries are metered in the 125-Radwaste Metering Tank to give a volume of 33.3 gallons of waste.

This is added to a drum to which 16.7 gallons of binder have been added which will yield the desired 2.0/1.0 waste to binder ratio.

In addition to the above, CP-401 has tank level indication and a high level alarm for the 118 and 125-Radwaste Metering Tanks.

77

E.

Secuence of Addition of Catalyst and Promoter The folicwing sequence of addition of catalyst and promoter will be used and will be set by the PROM / CAT switch on CP-402.

(1) For evaporator bottoms - promoter first.

(2) For ion exchange slurries - catalyst first.

F.

Promoter and Catalyst Quantities The quantities of the promoter and catalyst will be determined by a verification step where the amount of these two ingredients are aojustad until an acceptable procuct is produced.

This is a small scale laceratory test tnat is performed on a sample from each new tank of waste or new batch of binder, catalyst, or promoter.

The tank contaf ning the waste is isolated and beccmes a batch for which a recipe remains constant until it is all solidified.

Based on the quantities of catalyst and promoter used in the verification procedure, a graph in the operating procedure will be used to determine the amounts to be used during the solidification. These quantities are set on the catalyst and promoter injection accumulators and a position indicator light indicates that they are full and ready for injection into the drum.

G.

Mixer Soeed Since the wastes to be solidified are all water based and the binder l

used is insoluble in water, it is essential that the two are mixed j

thoroughly to farm a good emulsion. This is done by vigorous 78

- - - - --.__--- _ -. - - -_-=____ -

1 1

l mechanical mixing. A 12.4 inch (dia.) and a 15-inch (dia.) marine j

type impeller counted on a shaft are lowered into the 22.5 inch (dia.)

drum.

The shaft is then rotated at more than 300 rpm in order to emulsify the mixture. An air motor is used to drive the impellers.

The operator controls the speed of the impellers by adjusting the 1

motor air pressure at the control panel (CP-402). Mixer rpm is displayed on the control panel.

1 f

IV. RESUI.TS Tile following observations are made to ' determine that the liquid waste has been properly solidified:

'l A.

Hardnes_s_

After the waste and the binder are mixed and the promoter and catalyst added, the drum is allowed to sit on the conveyor line for 60 minutes to allow the polymerization reaction to be completed. At the end of this time, the drum is moved to a quality monitoring statien where the hardness of the solidified product is determined.

This is done by i

applying pressure to the solidified material with a metal probe and t

measuring the amount of back pressure created by resistance to penetration. Sufficient hardness is indicated by a red light on the control panel.

The back pressure is measured by an air piston on the l

upper end of the metal probe.

Back pressure limits corresponding to acceptable hardness have been determined experimentally.

79

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B.

Temeerature Rise 1

During the 60 minutes following the mixing of the ingredients for the I

solidified waste, an exothermic chemical reaction (polymerization) occurs which gives off a certain amount of heat.

For a given mixture of solidifying agents this heat will result in a temperature rise in the solidified drums that is consistently the same. Therefore, the measurement of this temperature rise is an indication that the proper polymerization has occurred to produce a solidified product.

During the verification step, the maximum temperature rise is noted and recorded. A thermoccuple elemer.t is located in the end of the metal probe of the hardness tester. The prebe is maintained in f

contact with the solidified waste until the temperature readout on the centrol panel stabilizes.

This temperature is r.oted and recorded.

For the temperature to be acceptable, the measured temperature must be within a preset limit. The proper temperature (+10*F) is the sum of the verification maximum temperature rise plus the waste temperature.

A red pilot light on the control panel indicates when the temperature i

is in the acceptable range.

l C.

Free Licuid At the time the drum is being quality monitored for hardness, a TV camera with a zocm lens will be used to visually inspect the top of the solidified product to determine whether there is free liquid present.

80 l

V.

SOLIDIFICATION AGENT / CLASSIFICATION (Reference 1) i I

A.

The binder is a commercial vinyl ester resin which has six months' shelf life when stored at temperatures below 80*F.

8.

The catalyst is a commercial product and storage temperatures below 80*F are recommended for maximum shelf life.

l i

C.

The promoter is a ccmmercial non-regulated product and can be stored 4

at room temperature with no shelf life or storage problems.

(

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)

References:

" Topical Report, The Dow System for Solidification of low-Level Radioactive l

Waste from Nuclear Power Plants", -- Report submitted to:

U.S. Nuclear Regulatory Commission by Dow Nuclear Services -- March, 1978. --

i DNS-RSS-001-NP-A.

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l TEST PROCEDURES FOR flS-1 SOLIDIFIED WASTE Commonwealth Edison, Dresden Station I.

Initial Conditions for Corrosion Test.

A.

Visually inspect and confirm barrel wall thickness as required 1

per specification.

II.

Specifications for Corrosion Test Specimens.

A.

1-1/2" - 2" diameter coupons to be removed f rom test b arrel.

(16 samples + 8 control samples) 8.

Samples to be taken at the top, middle and bottom of the barrel (Figure 1).

These locations will be stencilled and initialled as a means of identification.

C.

Samples te be cut out using a hole saw.

O.

Coupons to be removed at four time intervals:

1.

t = 0 days (control sample) 2.

t s 30 days 3.

t E 60 days 4.

t ~ 90 days E.

Barrel to be resealed using a silicate rubber material to insure barrel / solidified waste integrity.

I'II.. Acceptance criteria 50% of barrel specification wall thickness at 30 days.

IV.

Do c um ?.n t results (i.e. data including photographs).

l IML/dg 4944A l

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' hohnt.hm W4padrents 1o be sampleda.f 2 ate: Tran+ ' View denotes 1 o t

Die appropriate inferwl of Swe.

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"Eccaliaucs) of barret Coe-rosion %f Specimen (s)"

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l Coeroobn$ % &am ohs hderva1 Locatim Sample 2 oo Tp I

oo Tp 2

00 Cr 1

oo Cr 2

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%w 1

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30 Tp 30 Tp-2 30 Cr 1

30 Cr 2

30

@w f

30 hw 2

6O Ty 1

60

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60 Cr 1

60 Cr Z

60 8m 1

60 bm' 2

90 h

1 90 Tp 2

9o C.r 1

9o Cr 2

90

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85

WATER IP!iER SIO!! TEST PURPOSE:

To determine the eff ect of water upon the structural integrity of the solid simulated radwaste matrix.

I.

Initial Condition A.

Select verification sample of solidified simulated radwaste to be used for testing.

B.

Confirm its weight.

C.

Photograph sample (along with an appropriata scale) to record its initial state.

II.

Test Specifications A.

Place the samcle in a beaker of demineralized water.

B.

Maintain sample under water for the duration of the experiment.

C.

Ramove and examine.

ZII.

Consequent Analysis / Documentation A.

Photograph the sample to show final condition of the soldified waste following extended exposure to water.

B.

Reweigh Sample and compare to original weight.

C.

Document and submit results.

CRITERIA: No visible disintegration of the solid matrix structure, i

fML/ji 4951A July 8, 1980 l

I 86

i LEACH RATE TEST PURPOSE: To determine the iron (Fe) and nickel (NI) content of field prepared simulated radwaste samples (see " Attachment"), when exposed to simulated groundwater conditions in a laboratory situation.

1.

Prepare 9 verification samples per Dow Procedure 441-1.

(Each sample to be approximately 150 mi in volume.)

11.

Distribute chemical analysis of the simulated radwaste.

(Attachment to be submitted to the NRC at a later date.)

lit.

Present samples to NRC Representatives.

CRITERIA:

To be developed by NRC.

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APPENDIX B COMPUTER PROGRAM USED TO CALCULATE LEACH RATE DATA i

The following program was used to calculate incremental and cumulative re-leases from leach data. The program was written for interactive use in INTERCOM subsystem of the CDC 6600-15 computer at Brookhaven National Laboratory.

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PROGRAM LCH(INPUT,00TPUT, TAPE 4, TAPE 5)

DIMENSION C(10,100),P(10,10),

1N2(10),N3(100),YFSt100),YSS(100) 2,SFN(10,100),AR(10,100)

COMMON SV(10),A(10,100),SF(10,100),F(10,100) 2 WRITE 3 3 FORMAT (/,1X,'D0 YOU WISH TO CONTINUE 7')

READ 5,R1 5 FORMAT (A3)

IF(R1.NE.'YES") GO TO 3000 WRITE 10 10 FORMAT (1X,' ENTER TYPE OF LEACH DATA, <AA> OR < COUNT >:")

READ 15,R2 15 FORMAT (A5)

IF(R2.EQ." COUNT *)

GO TO 20 CALL AA(C,N1,N2,P,AR,CFN)

GO TO 30 20 CALL COUNT (C,N1,N2,P,AR,SFN) 30 CONTINUE WRITE 70 70 FORMAT (1X,'D0 YOU WISH TO AVERAGE THE DATA?")

READ 5,R3 IF ( R3. NE. "t ES " ) GO TO 1000 J=N2(1)

S=SV(1)

DO 90 I=1,J N3(I)=1 YFS(I)=F(1.I)/S YSS(I)=SF(1,I)/S 90 CONTINUE DO 150 K=2,N1 S=SV(K)

JJ=N2(K)

DD 150,N=1,J DO 150 L=1,JJ IF(A(1,N).NE.A(K,L)) GO TO 150 IF(YFS(N).LT.O.0) N3(N)=0 1

YFS(N)=YFS(N) + (F(K,L)/S)

YSS(N)=YSS(N) + (SF(K,L)/S)

N3(N)=N3(N)+1 150 CONTINUE DO 155 M=1,J YFS(M)=YFS(M)/N3(M)

YSS(M)=YSS(M)/N3(M) 155 CONTINUE C

OUTPUT AVERAGE VALUES OF FRACT. AND CUM FRACT. RELEASE WRITE 160 J

160 FORMAT (1X,3X," TIME",5X,"AV. FRACT. REL X V/S(CM)",5X, 1

1 i

90 d

3 L_

1'AV. CUM. FRACT. REL. X V/S(CM)",/)

DO 180 MM=1,J WRITE 175,A(1,MM),YFS(MM),YSS(MM) 175 FORMAT (1X,G10.4,13X,G10.4,23X,G10.4) 180 CONTINUE 1000 CONTINUE C

PLOTTING OPTION 4

WRITE 1001 1001 FORMAT (1X,'D0 YOU WISH TO PREPARE A PLOT FILE FOR DATA?"

1,1X)

READ 5,R4 1

IF(R4.NE.*YES') GO TO 2999 NG=1 IF(R3.EO.*YES") NG=2 CALL GPRP(NG,N1,N2,A,YSS) 2999 CONTINUE GO TO 2 3000 CONTINUE STOP ENU SOBROUTINE AA(CrN1,N2,P,AR,SFN)

DIMENSION B(10,100)sC(10,100),P(10,10) 1,BL(100),N2(10) 2,AR(10,100),SFN(10,100)

COMMON SV(10),A(10,100),SF(10,100),F(10,1.00)

C ENTER TIME DATA IN

'A' AND CONCENTRATION DATA IN

B' URITE 1 1 FORMAT (1X,* ENTER NUMBER OF DATA SETS (I2): ")

l READ 2,N1 2 FORMAT (I2)

WRITE 5 5 FORMAT (1X,'IS THE DATA IN < TAPES >?")

READ 6,RO 6 FORMAT (A3)

DO 1000 I=1,N1 WRITE 100,I 100 FORMAT (1X,* ENTER NUMBER OF SAMPLE POINTS IN DATA SET ",I2,/

i 1,10X,'C J',/)

READ 101,N2(I) 101 FORMAT (I3)

WRITE 110 110 FORMAT (1X,' ENTER SAMPLE TIME AND CONCENTRATION IN SAMPLE',/

1,10X,"E TIME JE PPM 3',/)

N22=N2(I)

DD 150 J=1,N22 l

IF(RO.NE.'YES') GO TO 140 READ (5,120) A(I,J),B(I,J) 120 FORMAT (2G10.4)

GO TO 150 140 WRITE 143 143 FORMAT (1X,/)

91

READ 120,A(I,J),B(I,J) 150 CONTINUE WRITE 160 160 FORMAT (1X,"ARE THE BLANK CORRECTIDNS CONSTANT FOR THIS DATA' 1,*

SET 7*)

READ 161,R1 161 FORMAT (A3)

IF(R1.NE.*YES*) GO TO 180 WRITE 165 165 FORMAT (1Xt' ENTER BLANK CORRECTION',/,10X,'E PPM 3",/)

READ 167.BLA 167 FORMAT (G10.4)

GO TO 190 180 CONTINUE WRITE 181 181 FORMAT (1X,' ENTER BLANK CORRECTION FOR EACH SAMPLE',/,10X, 1*C PPM J',/)

190 CONTINUE DO 195 K=1,N22 IF(R1.EO.'YES') BL(K)=BLA IF(R1.EO.*YES') GO TO 194 WRITE 193 193 FORMAT (1X)

READ 167,BL(K) 194 C(I,K)=B(I,K)-BL(K) 19S CONTINUE C

CALCULATE FRACTION RELEASEsF*AND CUMMULATIVE FRACTION C

RELEASE, SF WRITE 200 200 FORMAT (1X,* ENTER SAMPLE VOLUME, LEACH VOLUME, SAMPLE SURFACE",

l' AREA.',/,1X,"AND CONCENTRATION IN SAMPLE',/,10X, 2'E CM**3 JE ML JE CM**2 3E PPM 3'

3,/)

READ 210,P(I,1),P(I,2),P(I,3),P(I,4) 210 FORMAT (4G10.4)

SV(I)=P(I,3)/P(I,1)

DO 250 L=1,N22 SF(I,L)=0.0 250 CONTINUE DO 300 M=1,N22 F(I,M)=(C(I,M)*P(I,2))/(P(I,4)*P(I,1))

IF(M.EO.1) SF(I,M)=F(I,M)

IF(M.EO.1) GO TO 300 MM=M-1 SF(I,M)=SF(I,MM)+F(I,M) 300 CONTINUE 1000 CONTINUE C PRINT FRACTION RELEASE AND CUMMULATIVE FRACTION RELEASE DO 2000 II=1,N1 WRITE 1001,II,SV(II) 1001 FORMAT (1X,' DATA SET :

",I2,/,1X,' SURFACE / VOLUME = ",

92

1G10.4,* CH-1*,/,1X,3X,* TIME *,8X,* FRACTION RELEASE *,5X, 2"CUMMULATIVE FRACTION RELEASED *,/)

N23=N2(II)

DO 1100 IK=1,N23 AR(II,IK)=A(II,IK)**0.5 SFN(II,IK)=SF(II,IK)/SV(II)

WRITE 1050,A(II,IK),F(II,IK),SF(II,IK) 1050 FORMAT (1X,G10.4,8X,G10.4,18X,G10.4,/)

1100 CONTINUE WRITE 1110 1110 FORMAT (1X,"SQ. ROOT OF TIME",5X,' CUM. FRACT. X V/S(CH)",/)

DO 1120 IL=1,N23 WRITE 1115,AR(II,IL),SFN(II,IL) 1115 FORMAT (1X,4X,G10.4,14X,G10.4) 1120 CONTINUE 2000 CONTINUE RETURN END SUBROUTINE COUNT (C,N1,N2,P,AR,SFN)

DIMENSION B(10,100),C(10,100),P(10,10) 1,BL(100),N2(10) 2,T(10,100),UC(4),AR(10,100),SFN(10,100) 3,El(10,100)eE2(100),E3(10,100),E4(100),ES(100),E6(10,100) 4,E7(10,100),E8(10,100)

COMMON SV(10),A(10,100),SF(10,100),F(10,100)

C ENTER TIME DATA IN

'A' AND ACTIVITY DATA IN

'B' WRITE 1 1 FORMAT (1X,"CNTER NUMBER OF DATA SETS (I2)!")

READ 2,N1 2 FORMAT (I2)

URITE 3 3 FORMAT (1X,* ENTER NUCLIDE AND HALF LIFE',/,10X, 1*XXXXXXC DAYS J',/>

4 FORMAT (A6,G10.4)

READ 4,UC(1),UC(2)

UC(3)=(ALOG(2.0))/UC(2)

WRITE 5 5 FORMAT (1X,"IS THE DATA IN < TAPES >7')

READ 6,RO 6 FORMAT (A3)

DO 1000 I=1,N1 WRITE 100,I 100 FORMAT (1X,' ENTER NUMBER OF SAMPLE POINTS IN DATA SET *,I2,/

1,10X,'E J',/)

READ 101,N2(I) 101 FORMAT (I3)

WRITE 110 l

110 FORMAT (1X,' ENTER SAMPLE TIME AND ACTIVITY IN SAMPLE",/

1,1X,' ENTER TIME FROM EXPERIMENT START THAT SAMPLE WAS

2," COUNTED",/

3,10X,*C TIME JE CPM /ML JE ERROR JE DAYS J",/)

t 93

N22=N2(I)

DD 150 J=1,N22 IF(RO.NE.'YES*) GO TO 140 READ (5,120) A(IrJ),B(I,J),El(I,J),T(IrJ) 120 FORMAT (4G10.4)

GO TO 150 d

140 WRITE 143 143 FORMAT (1Xe/)

READ 120, A(I r J),B(I,J),t 1(I,J),T(I,J) 150 CONTINUE C

BACKGROUND CORRECTION WRITE 160 160 FORMAT (1X,"ARE THE BACKGROUND CTS CONSTANT FOR THIS DATA' 1,"

SET?")

READ 161,R1 161 FORMAT (A3)

IF(R1.NE.*YES') GO TO 180 WRITE 165 165 FORMAT (1X,* ENTER BACKGROUND CTS",/,10X,*E CPM /HL 3C ERROR 3'r/)

READ 167,BLArER 167 FORMAT (2G10.4)

GO TO 190 180 CONTINUE WRITE 181 181 FORMAT (1X,' ENTER BACKGROUND CTS FOR EACH SAMPLE'r/,10X, l'E CPM /HL 3E ERROR J',/)

190 CONTINUE DO 195 K=1,N22 IF(R1.EO.*YES') BL(K)=DLA IF(R2.EG.'YES") E2(K)=ER IF(R1.EO.'YES") GO TO 194 WRITE 193 193 FORMAT (1X)

READ 167,DL(K),E2(K) 194 C(I,K)=B(I,K)-BL(K)

E3(I,K)=((El(irk)**2.0)+(E2(K)**2.0))**0.5 C

DECAY CORRECTION C(I,K)=C(irk)*EXP(UC(3)*T(I,K))

E3(irk)=E3(irk)*EXP(UC(3)*T(I,K))

195 CONTINUE C

CALCULATE FRACTION RELEASE,FrAND CUMMULATIVE FRACTION C

RELEASE, SF WRITE 200 200 FORMAT (1X," ENTER FORM VOLUME, LEACH VOLUMErFORM SURFACE",

1* AREA.",/,10X,'E CM**3 3E ML JE CM**2 3"r/)

READ 204,P(I,1),P(Ir2),P(I,3).

l 204 FORMAT (3G10.4)

WRITE 206 206 FORMAT (1X,* ENTER ACTIVITY IN FORMrERRORr*

1' BACKGROUND COUN'TS,ERRORrAND TIME IT WAS COUNTED",/r10X 2,'E CMP /ML 3C ERROR JE CPN/ML 3E ERROR 3C DAYS 3"r/)

94

READ 208,P(Ir4),E4(I),P(Ir5),E5(I),P(Ir6) 208 FORMAT (5G10.4)

SV(I)=P(Ir3)/P(Iri)

DO 250 L=1rN22 SF(IrL)=0.0 250 CONTINUE DO 300 M=1rN22 F(I,M)=(C(IrM)*P(Ir2))/(((P(Ir4)-P(Ir5))*EXP 1(UC(3)*P(Ir6)))*P(Iri))

ERN=E3(IrH)*P(Ir2)

ERS=((E4(1)**2.0)+(ES(I)**2.0))**0.5 ERS=ERS*P(I.1)*EXP(UC(3)*P(Ir6))

FTN=C(IrM)*P(Ir2)

FTD=(P(Ir4)-P(Ir5))*P(Iri)*EXP(UC(3)*P(Ir6))

E6(IrM)=((ERN*ERN)+(CERS*F(I.M))**2.0))/(FTD*FTD)

E6(IrM)=E6(IrM)**0.5 IF(F(IrM).LT.O.0) F(IrM)=0.0 IF(M.EO.1) SF(I,M)=F(IrH)

IF(M.EG.1) E7(IrM)=E6(IrM)

IF(M.EG.1) GO TO 300 MM=M-1 SF(IrH)=SF(IrMM)fF(IrM) l E7(IrM)=((E7(IrMM)**2.0)+(E6(IrM)**2.0))**0.5 300 CONTINUE 1000 CONTINUE C PRINT FRACTION RELEASE AND CUMMULATIVE FRACTION RELEASE URITE 1001,UC(1) 1001 FORMAT (1X.A6," RELEASE RATE DATA'r/)

DO 2000 II=1rN1 WRITE 1002rIIrSV(II) 1002 FORMAT (1X,' DATA SET : ",I2r/r1Xr* SURFACE / VOLUME = ",

1G10.4," CM-1"r/r 21X,3X," TIME"r10X,' FRACTION'r8X,' ERROR"r7Xe* CUMULATIVE"r8X, 3* ERROR *,/r1X,16X,' RELEASED",22X,' FRACTION"r16X,/r1X,46X, 4' RELEASED *,/r1X,5("__________'r5X),/)

N23=N2(II)

DD 1100 IK=1rN23 AR(II,IK)=A(IIrIK)**0.5 SFN(II,IK)=SF(IIrIK)/SV(II)

EG(IIrIK)=E7(IIrIK)/SV(II)

WRITE 1050rA(IIrIK),F(II,IK),E6(IIrIK)rSF(II,IK),E7(II,IK) 1050 FORMAT (1X,5(G10.4,5X))

1100 CONTINUE WRITE 1110 1110 FORMAT (1Xr*SG. ROOT OF TIME"r5Xr* CUM. FRACT. X V/S(CM)'r8X, l' ERROR"r/>

DD 1120 IL=1rN23 WRITE 1115,AR(IIrIL),SFN(II,IL),E8(IIrIL) 1115 FORMAT (1X,4X,G10.4,14X,G10 4r9X,G10.4) 1120 CONTINUE 2000 CONTINUE 95

(

i RETURN END SUBROUTINE GPRP(NG,N1,N2,AR,YSS)

DIMENSION DEL (10),NP(10,4),X(100),

1ITI(20),IXTI(20),IYTI(20),

4N2(10),AR(10,100),YSS(100)

COMMON SV(10),A(10,100),SF(10,100),F(10,100) 1 FORMAT (2I3,2A6) 2 FORMAT (I3,2A6) 3 FORMAT (I2) 4 FORMAT (2G10.4) 5 FORMAT (6A10) 7 FORMAT (A6,4G10.4) 8 FORMAT (F6.3)

C ENTER DATA WRITE (4,3) NG DO 1000 I=leNG IF(I.EG.1) NC=N1 IF(I.EG.2) NC=1 WRITE (4,3) NC NPO=0 DO 100 II=1,NC IF(I.EG.1) NP(II,1)=N2(II)

IF(I.EQ.2) NP(II,1)=N2(1) 1 WRITE 1003 READ 2, NP(II,2),NP(II,3),NP(II,4)

WRITE (4,1) NP(II,1),NP(II,2),NP(II,3),NP(II,4)

IF(NP(II,4).NE.'SM00TH') GO TO 9 WRITE 1005 READ 8, DEL (II)

WRITE (4,8) DEL (II) 9 CONTINUE LE=NP(IIri)

DO 10 III=1,LE IF(I.EG.1) WRITE (4,4) AR(II,III),SF(II,III)

IF(I.EO.2) WRITE (4,4) AR(1,III),YSS(III) 10 CONTINUE 12 FORMAT (A6,2I3,2G10.4) 13 FORMAT (8010.4)

WRITE (4,25) 25 FORMAT ("NO

')

100 CONTINUE C

ENTER PLOTTING INFORMATION C

READ IN PLOT AND AXIS TITLES WRITE 101 101 FORMAT (1X,* ENTER PLOT TITLE",/,

110X,"E 3'

2,/)

READ 5, (ITI(K),K=1,6)

WRITE (4,5) (ITI(K),K=1,6)

WRITE 102 96

102 FORMAT (1X,* ENTER AXIS TITLESrX THEN Ye ONE PER LINE'r/r 110X'E J",

2/)

READ 5, (IXTI(K),K=1,6)

WRITE 103 103 FORMAT (1X,"

'r/,10X, l'c J'r/)

WRITE (4,5) (JXTI(K),K=1,6)

READ Sr (IYTI(K),K=1,6)

WRITE (4,5) (IYTI(K),K=1,6)

C READ IN PLOT SIZE WRITE 104 104 FORMAT (1X,* ENTER PLOT SIZE IN INCHES, X THEN Y'r/r 110X,'E JE

]*,/)

READ 14, XLENrYLEN WRITE (4,14) XLENrYLEN 14 FORMAT (2F6.3)

XPG=XLENt2.0 YPG=YLEN+3.0 C

ENTER GRAPH TYPE AND PARAMETERS WRITE 107 107 FORMAT (1X,' ENTER TYPE OF GRAPHrX ORIGINeX SCALER"r/r 11X,"Y ORIGIN,Y SCALE"r/r10X,'E JC JC J",

2'E JC J'r/)

READ 7,TY,XOrXCS,YO,YCS WRITE (4,7) TYeX0rXCSrY0rYCS 1002 FORMAT (1X,' ENTER NUMBER OF CURVES ON THIS GRAPH (I2)",

1/)

1003 FORMAT (1Xe' ENTER DATA SPOTTING, TYPE OF"r/r 11X,'LINE, AND TYPE OF FITTING'r/r10Xe'E JC JE J'r 2/)

1005 FORMAT (1X," ENTER DELTA Y IN INCHES" /r10X,*E 3",

1/)

1008 FORMAT (11X,'D0 YOU WISH TO FIT WITH A POWER SERIES?(A3)")

300 CONTINUE 400 CONTINUE 1000 CONTINUE 1001 FORMAT (1X,* ENTER NUMBER OF GRAPHS'r/r10Xr*CJ"r/)

2000 CONTINUE RETURN END

)

97

I APPENDIX C DOW COMMENT ON LEACH TEST RESULTS The following comment has been received from Dow Chemical Corporation regarding the results of the leach tests discussed in the interim report of this work (BNL-NUREG-29273).

1 99

1 DOW CHEMICAL U.S.A.

June 12, 1981 LARKIN LABORATORY 1691 N SWEDE RD.

MIDLAND. MICHIGAN 48640 Mr. Allen J.

Weiss Nuclear Vaste Management Group Department of Nuclear Energy Building 830 Brookhaven National Laboratory Upton, New York 11973

Dear Allen:

This letter will confirm my telephone conversation with Bob Barletta on June 8, 1981.

The subject of this discussion was the BNL Interim Report entitled, "Phsycial Tests on Solidified Decontamination wastes from Dresden Unit 1."

Bob indicated that BNL had been requested to write a final report on this work and we discussed clarification of several points for this report.

I will cover these points in the order of discussion during our conversation.

1)

The weeping or residual liquid noted on the surface of samples prepared in polyethylene at BNL when they were removed from the container.

We have found that solidification of samples in certain types of plastic containers will result in an extremely thin layer of water on the sample surface.

This phenomenon was discussed with Bob Neilson during his initial visit in Midland in July 1977.

It is assumed to be related to con-tainer size, surface tension and mold release and not to the process.

A statement in the final report that this behavior has been observed by Dow when solidification is performed in some types of plastic containers would not be proprietary.

2)

The surface tackiness of the top 1-2 mm layer of the samples.

This tackiness is due to air inhibition and is a known phe-nomenon with any styrene type polymerization.

The tackiness of the top surface disappears within 24 hours2.777778e-4 days 0.00667 hours 3.968254e-5 weeks 9.132e-6 months .

3)

The interpretation of the final two sentences of Section 3.2.3 - Comparison of BNL Results With Leach Tests Performed by Dow.

Dow agrees that BNL data supports the hypothesiF that the release rate should not depend on the ion leached.

Dow l

100 AN OPERATING UNIT OF THE DOW CHEMIC AL COMPANY l

1

Mr. Allen J. Weiss June 12, 1981 objects to the statement, "No attempt was made to account for this difference in spite of the fact that it contradicts their claim that release rates should not depend on the ion leached," on both a technical and interpretation basis.

On a technical basis the Dow data cited in the report comes from two separate experiments with different forms of waste.

Therefore, one would expect some differences in the values without their contradicting the claim cited.

Additional Dow data agrees with the BNR results.

More importantly if this statement is lifted from the report and quoted as it stands it leaves the impression that Dow is reporting false information.

We are certain that this is not the intent of the authors of the report.

4)

The effect of immersion of samples in water saturated with toluene and xylene.

We have confirmed the type of deterioration you have reported.

However, leach tests on the samples indicate the impact is not as severe as the appearance of the samples indicate.

Leach results after 14 days indicate approxi-mately 0.9% of the iron has leached from the samples immersed in the organic saturated water compared to 0.5% leached with tap water.

If you have any questions or need further information, please contact me.

Very truly yours, Harold E.

Filter Research Associate Nuclear & Solidification Services 517-636-3468 fo cc:

Robert E.

Barletta Richard E.

Davis 101

SER M N W DOCJ U.S. NUCLEA2 REGULATORY COMMtBSION m*8 NUREG/CR-316 BIBUOGRAPHIC DATA SHEET BNL-NUREG-48

4. T AND SUETsTLE Mdd vaknae Nn. tf eparapnen) 2.LeeeWok)l Phys al Teste on Solidified Decontamination Wastes

/

^#'"'""

from D sden Unit I

7. AUTHOR 15

5. D[ REPORT COMPLETED

. E. Barletta, J.W. Adams, and R.E. Davis foNTH Lya 4R June 1981 F

9. PERFORMtNG O NIZATION N AME AND MAILING ADDRESS # ache E, coel DATE REPORT ISSUED Brookhaven Nati 1 Laboratory Ye*cember IM Department of lear Energy

, g,, y,,,,

Upton, Long Islan New York 11973

s. n,= wmki

12. SPONSORING ORGANIZATI NAME AND MAILING ADDRESS # ache Ep dwirl Division of Waste Mana ment Office of Nuclear Mater is Safety and Safeguards

11. CONTRACT NO.

U. S. Nuclear Regulatory mmission A3159 Washington, D.C. 20555

(

13. TYPE OF REPORT PE RIOD Cove RED #acAnsa, slees)

Technical Report

15. SUPPLEMENTARY NOTES

14. neee Wmkl

16. A8STRACT ODO wents or dras/ The resul ts o ersion and le5ch tests of NS-1 concentrate soli-dified in a vinyl ester-styrene binde re reported.

Immersion tests of waste forms prepared at a solidification demonst n held at the' Dresden Nuclear Power Station were conducted. These forms were i 'ers in toluene, xylene, and water saturated with toluene and xylene. As a resul t 'of.immer n of samples in the pure organics, large changes in sample volume and weig. were o rved.

Total weight changes as a result of immersion of 9.6 + 0.3% and 21.6 0.7% were%bserved after 839 hours0.00971 days 0.233 hours 0.00139 weeks 3.192395e-4 months of imaersion in xylene and toluene respectively. = Air drying 4(flor toluene.the samples led to an ov,erall loss of 23.5 + 0.7% for xylene d 35.6 + 0.6%

Qualitatively, similar changes were observed for imme ion tests using ot Severe sample his case, however ;ganic saturated water.

deterioration was observed in yhe behavior of cut and uncut samples ft:om leach tests subjected t immersion in either organic saturated water or toluene was qualitat' ively the same as f the sectioned sample. ~ vere sample deterioration was not ed in both cut 'and uncut form < immersed in organic satura d water.

17. KEY WoRDs AND DOCUME AN ALYSIS<

17as DESCRIPTOR$

1) Preparation of D ontamination Low-Level Wastes for Disposal

2) Dresden Unit 1 econ Wastes

3) Disposal of lating Agent Wastes 171 IDENTIFIE RS/

4NDE D TERMS

18. AVAf LAstLITY STATEMENT

19. ECURITY CLASS (24 suport/

21.h0. OF PAGES Unclassified

\\

unlimited 2a sECuR TY CLASS (mh papf

22. PRfCE s

CRC FORM 335 (7 77)

I UNITED STATES f ou1TM CLL51; All NUCLEAR REEULATOhY COMMISSl!N post Act a riss e: o

. usmac WASHINGTON, D.C. 20556 WASH 0 C Ptamt m. m OFFICIAL BU$lNESS PENALTY FOR PRIVATE USE. 4330 s

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ML20083H498

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