ML20128H738
| ML20128H738 | |
| Person / Time | |
|---|---|
| Issue date: | 02/04/1993 |
| From: | Lohaus P NRC OFFICE OF NUCLEAR MATERIAL SAFETY & SAFEGUARDS (NMSS) |
| To: | Miller V NRC OFFICE OF STATE PROGRAMS (OSP) |
| References | |
| REF-WM-105 NUDOCS 9302170145 | |
| Download: ML20128H738 (1) | |
Text
,
FEB - 4 1993 MEMORANDUM FOR:
Vandy L. Miller, Assistant Director for State Agreements Program Office of State Programs FROM:
Paul H. Lohaus, Chief low-Level Waste Management Branch Division of Low-level Waste Management and Decommissioning Of fice of Nuclear Material Safety and Safeguards
SUBJECT:
TECHNICAL EVALVATION REPORT ON THE DIVERSIFIED TECHNOLOGIES, INC., TOPICAL REPORT, "VERl* (VINYL ESTER RESIN IN SITU)
SOLIDIFICATION PROCESS t0R LOW-LEVEL RADI0 ACTIVE WASTE "
REPORT NUMBER DT-VERl-100-NP/P, REVISION 0. DECEMBER 1, 1991, DOCKET NUMBER WM-105 four copies of the subject Technical Evaluation Report (TER) and our letter of transmittal are enclosed.
The TER approves the Diversitied Technologies topical report on the VERI" Solidification Process when tha final revised topical report is submitted.
Please note that final approval is contingent on a revised topical report and satisfactory resolution of the open issues identified in Section 3.0 of the enclosed TER. The revised topical report is due to the Nuclear Regulatory Commission on April 5,1993.
Please transmit the TER's and c a er letters to the Host States, if you have any questions regarding this letter, please contact Jennifer Davis at (301) 504-2697.
Paul 11. Lohaus, Chief low-level Waste Management Branch Division of Low-Level Waste Management r i Decommissioning Office of Nuclear Material Safety and Safeguards
Enclosures:
As stated R111E1DUT10N:
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NAME: JDavis JThoma JCry PL[hNs3 DATE: t/Q/93 H
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ACNW:
YES NO X
Delete file after distribution Yes
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- 8 49 UNITE 3 STATES
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Mr. Charles E. Jensen Vice Pres; dent. Operations Diversified Technologies. Inc.
- 10) Dixon Drive chestertown, MD 21620
Dear Mr. Jensen:
The Nuclear Regulatory Commission has completed its review of topical report.
DT. VERI 100 NP/P, " VERI * (Vinyl Ester Resin In situ) Solidification Process for Lov. Level Radioactive Waste."
The technical review included inforrsation contained in the topical report (TR), and further information that was submitted as a result of the review.
for this review is enclosed.
The Technical Evaluation Report (TER)
Ve have concluded that the topical report supplemented by additional information that was provided in response to staff comments and questions adequately describes low level radioactive vaste forms produced through use of the VERI
- process.
This process applies to the solidification of two waste streams, mixed bed bead resins, and LOH1 resins.
We also conclude that the solidified waste forms described meet the structural stability requirements of 10 CTR 61 for the dicoosal of Class 8 and Class C These conclusions are predicted based on satisfactory completion of a wastes.
final revised topical report which should include all applicable information developed during the technical review, a copy of the enclosed TER, and the t
l following conditions:
1.
The VERI
- waste solidification process shall be used in accordance with the limitations called out in Section 3.1 of this Technical Evaluation Report, and all additional restrictions and requirements specified by the disposal facility operators and governing state agencies.
2.
Diversified Technologies must notify userJ of the VERI" waste
, solidification process that they shall certify that all restrictions and
- requireed procedures have been adhered to, and that the vaste forms do not contain proscribed chemicals or vaste sacerials.
3.
Diversified Technologies must characterize the chemical natwo of the I
resins used in the qualificat! n tests so that users of the process can know what kind of resins can be satisfactorily solidified. This information must be clearly specified in the final revised TR and operating procedures.
4 Diversified Technologies must resolve the outstanding issues specified in Section 3.2 of the enclosed TER.
l l.
h3&ft3trA6-agg.
i cherice Jensen 2
Note that Final Approval is contingent on completion o The revised topical report should be submitted to the NRC within 90 days of this letter, It should be noted that notwithstanding NRC's decisions on the adequacy of the VER1= polymer solidified vastes, the sited States have regulatory authority concerning the conditions of acceptance of vaste forms at their disposal facilities.
It is therefore the licensee's responsibility to contact the State regulatory authorities to deterutne the acceptability of the polymer solidified wastes at their State's facilities.
Copies of the enclosed TER and this letter are being forwarded to the States of Nevada, South Carolina and Vashington for their information and use.
If you have any questions on this matter, please contact me at (301) 504 2697, (301) 504 3450,
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or Jennifer Davis at Sincerely, MMY
\\
l John Thoma, Section Leader Technical and Special Issues Section Lov Laval Vaste Management Branch Division of Low Level Vaste Management and Decommissioning Office of Nuclear Material Safety and Safeguards
Enclosure:
As stated y
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C United'stst:e Nucicer Regulatory Commission Office of Nuelear Motorial safety and Safeguards Washington, DC 20555 TECHNICAL EVALUATION REPORT related to Topical Report DT. VERI.100 NP/P VER15 (Vinyl Ester Resin In' Situ) Solidification Process for Lov Level Radioactive Waste Diversified Technologies Docket No, WN.105
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Prepared by:
law Level Waste Management Branch Division of Low.1mvel Vaste Management and Decommissioning December 1992 1
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i ABSTRACT This Technical Evaluation Report (TER) has been prepared by the Office of Nuclear Katerial Safety and Safeguards of the US Nuclear Regulatory Comm for Diversified Technologies' Topical Report (TR) DT VERI 100 NP/P, "VE11" (Vinyl Ester Rosin In Situ) Solidification Process for Low Level Radioacti Vaste,' (Docket Number VN 105).
ve with the Dow Chemical USA Topical Report DNS RSS 200 NP, "The b Solidification Procese For Low Level Radioactive Vastes* (Docket N 82).
The Diversified Technologies' TR expanda on the Dow TR in two areas.
First, all of the approved Dow waste forms were limited to a maximum of 50 cubic feet.
The Diversified Technologies' TR was designed to qualify solidification of spent ion exchange resin in a 200 cubic foot liner, using a process similar to the Dow process.
It also contains qualification test results for solidification of spent LOMI (Low Oxidation State Transition Metal lon) ion exchange resin, which was not one of the waste-streams included in the Dew TR.
On the basis of the information presented, the staff concludes that this binder process, when applied to the specified waste streams, should result in vaste forms that meet the structural stability requirements of 10 CFR Part 61 and the guidance provided in the Technical Position on Vaste Form Revision 1 January 1991.
Limiting conditions for use of these waste forms may be specified by the regulating authority for a particular disposal site, i
TABLE OF CONTEWF8 1.0 BACRanc e..,.....................
1.1 Ragulations...
1 1.2 Topical Report submittal 1
1.3 Diversified Technologies Vinyl Ester Resin In. Situ Process 2
3 1
2.0 TECHNICAL EVALUATION
2.1 Vaste Characteristics.
3 2.2 Vaste Streams Considered...................
3 2.3 Minimum Requirements [10 CFR 61.56(a)),,.................
4 2.3.1 Packaging 4
2.3.2 Liquid Waste.
4 4
2.3.3 Free Liquid 4
2.3.4 Reactivity of Product 2.3.5 Toxic Cas Generation..................
5
- 2. 3. 6 - Pyrophoricity..
2.3.7 Caseous Wastes 5
5 2.3.8 Hazardous Vasta 5
5 2.4 Stability Requirements (10 CFR 61.56(b)) and Reconnendations of the Technical Position on Waste Form 2.4.1 6
Structural Stability...........
As. Cured Compressive Strength........-
6 2.4.1.1 7
2.4.1.2 Radiation Resistance 7
2.4.1.3 blodegradation Resistance.
-8 2.4.1.4 Leachability 9
2.4.1.5 Immersion Resistance 10 2.4.1.6 Thermal Cycling.
11 2.4.1.7 Correlation Testing.
12 2.4.1.8 Homogeneity.,............
12 2.4.2 Free Liquid 2.4.3 Void Spaces 13 13 2.5 Process Control Program.
2.6 Reporting of Mishaps 13 14
3.0 CONCLUSION
S 3.1 Limitattorm.
15 3.2 Further Actions.
15 15 REFERENCES 17 LIST OF TABLES Table I. As. Cured Compressive Strengths 7
Table II - Compressive Strengths Following Irradiation 8
Table IIIa = Compressive Strengtha Following 31odegradation Testing l
(Pungal) 9 Table IIIb Compressive Strengths Following Biodegradation Testing L
(Bacterial) 9 Table IV 14achability Indices i-10 Table-V Compressive Strengths Following Immersion 11 Table VI Compressive Strengths following Thermal cycling 12 11 l
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TEC1041 CAL EVALUATION REPORT MR VASTE WRMS PRODUCED 11t0M THE DIVERSIFIED TECHNOLDCIES VERIm PROCESS (VM 1.0 BACKCROUND This report provides the evaluation results of the technical review of information and data submitted by Diversified Technologies in a topical (TR) entitled, "VERIN report Low Level Radioactive Wasts," DT VERI.100.HP/P. December 1, Technical Evaluation Report (TER)
This is a detailed evaluation of the waste form qualification test data provided by Diversified Technologies to confiru that this solidification process will produce a waste form that meets the regulatory requirements of 10 CFR Part 61 with respect to structural stability.
Once a toolcal report review has been completed and the associated product (s) has been approved, the TR process allows a user to reference the report to demonstrate that the subject regulatory review process and is acceptable to the staff. area the report address Thus, the TR process allows the use of a repeated process, action, etc., at several facilities after a single successful review has been completed.
However, in the case of TR'r for waste forms, vaste generators must take additional actions (e.g., plant specific procesu control procedures) to demonstrate that all portions of Part 61 have been met.
1.1 Rerulaciong By Federal Register Notice dated December 27, 1982 (47 FR 57446), the United States Nuclear Regulatory Commission (NRC) amended its regulations to provide specific requirements for licensing of facilities for the land disposal of low level radioactive waste (LLV)
The majority of these requirements are now contained in Part 61 to Title 10 of the Code of Federal Regulations (10 CFR Part 61) entitled " Licensing Requirements for Land Disposal of Radioactive Vaste" (Ref. 1).
These regulations are the culmination of a set of prescribed precedures for LOW disposal that were proposed in the Federal Register on July 24, 1981.
The effective date for the implementation of 10 CFR 20.311/20.2006, (" Standard for Pre'tection Against Radiation') wt'.ch requires vaste generators to meet the vaste cle.ssification and waste form requirements in 10 CFR Part 61, was December 27, 1983.
As set forth in 10 CFR 61.55, Class 8 and Class C waste must meet structural stability requirements that are established under 10 CFR 61,56(b).
As noted in 10 CFR 61.56(b)(1), structural stability could be provided by (a) processing (i.e., solidification of) the waste form, (b) by the waste itself (as with large activated steel components), or (c) by placing the waste in a container or structure which would then provide the required stability (i.e., a high integrity container (HIC)). To the extent practicable, Class B and C waste forms or containers should, according to Section 61.7 of Part 61, maintain structural stability for 300 years.
In May 1983 the NRC provided additional guidance by means of a Technical Position on Vaste Form (TP) (Ref. 2) that describes test procedures and criteria i
(
th3t een b3 used to demonstrate the required long term, 300 year stability.
to the Technical Position on Vaste Torn, which was issued structural (Ref. 3).
1991 The purpose of this Technical Evaluation Report tuhnical review conducted of the (TER) is to summarize the Technolo6tes (also referred to as the vandor),information submitted by Diversified and to demonstrate that the polymer solidification of 1.1.V by the process described in its topical report
" VERI * (Vinyl Ester Resin In Situ) Solidification Process for Low. level Radioactive Vaste * (Ref. 4), and in associated documents, will meet the Long tern (300 year) the relevant structural stability provisions of 10 CTR 61.56 and Vas te Form.
portions of the January 1991 NRC Staff Technical Position on 1.2 Icoical Pecort SM The NRC staff concluded on June 1.1988 that the Topical Report for the Dow Vaste Solidification Process (Ref. 5),
provides reasonable assurance that subject to certain conditions, of this process meet the structural stability requireannes of 10 Cnt Part 61 ide for the disposal of Class B and C wastes.
This process applies to the vinyl.
ester styrene (VES) solidification of the 7 waste streams that are described in Table A of the applicable NRC Technical Evaluation Report (Ref. 6).
Dow Chemical. USA decided not and the associated topical reportto market the VES process and placed its process in the public domain. This enables waste generators and processors to utilize the VES material to solidify and stabilize low. level wastes subject to the conditions specified in NRC's TER.
One of the 7 waste streaus approved for use with the Dow process was ion-exchange bead resin slurry. On November 14, 1969 Diversified Technologies held a meetina with NRC (Ref. 7), to propose an addendum to the Dow Topical Repoct which would permit solidification of ton exch5nge resin beads in Isrge liners (up to 200 ft ). The original process was qualified only for 3
volumew up to 50 ft.
3 Diversified Technologies submitted their topical report, DTI VMS-100 NP, in August 1990 (Ref. 8).
The "VERIN* process dascribed in the topical report dif fers from the Dow 'VES* process in several ways.
The VER15 process involvep forcing (by pumping) or drawing (by suction) a catalyzed and promoted modified vinyl ester resin through an expended ion exchanger resin container.
The Dow solidificat!on method is a mixing process.
In addition, the binder and promotor specified by Diversified Technologies differ slightly from those used by Dow.
Diversified Technologies also proposed qualification of a waste stream not qualified by Dow; spent IDMI (Low Oxidation State Transition Metal Ion) ion exchange resin. The original Diversified Technologies' topical report also included information on two other Diversified Technologies low-level waste processing methods that were not part of this review.
The NRC concluded that the TR was not an addendum to the approved Dow solidification TR, but was a new TR based on a new process (which results in a polymer vaste form stallar to those from the Dow process). The NRC requested Diversified 2
o.
Technoiteits to submit a revised TR, which they did on December 1 reissued TR and associated documentation.This TER is written tc (Ref, 4).
, 1991 (Ref. 9) and Diversified Technologies
- Response (Re TR, but will be reinstated per RAI (2 and the responses revised material vill be discussed, as it is integral to the TR rtview.
This all future purposes, Note that for Diversified Technologies TR.the December 1991 TR will be considered the " original" 1.3 Diversified Technolonien Vinyl Ester Ramin In Situ Procean The proposed solidification process involves forcing (by pumping, or suction a catalyzed and promoted modified vinyl ester styrene through a disposal liner, demineralizer column, or other expended ion exchange resin container As the bindnr flows through the resin bed.-it fills the void spaces between the resin beads, and forces any free water in the container into the bottom dewataring internals, displacing the excess water, the binder cures to form a liquid. free free standing monolith inside the container.
2.0 TECHNICAL EVALUATION
The information presented in the topical report and Diversified Technologies' letter responses to NRC's comments provide the basis for the technical evaluation presented in the following sections.
conducted by NRC staff members.
The review and evaluation was submitted information is based upon a comparison with the applicableT regulatory requiraments of 10 CFR Part 61 and the guidance on solidified waste forms in the Revised TP (Ref. 3).
2.1 Vaste Characteristics The minimum set of characteristics that all L1H intended for near surface disposal must meet is defined in 10 CFR 61.56(a).
Thaso requirements are intended to provide for ease of waste handling and to provide for the protection of the health and safety of the personne1'at the disposal site.
Class A wastes are only required to meet these minimum requirements if they are segregated and are not solidified waste forms. Class A wastes that arc solidified and disposed of with Class B and Class C wastes shall meet the-stabittty guidance for thesa vastes, in addition to meeting the minimum set of characteristics.
The characteristics the vaste form classified as Class 8 or Class C should exhibit to meet the stability requirements of 10 Crt 61.56(b), are those that will enable the vaste form to maintain its stability and package integrity during vaste handling and emplacement, as well as after disposal. Stability-is intended to ensure that the vaste does not structurally degrade and affect the overall stability of the site through slumping, collapse, or other failure of the disposal unit, and thereby lead to water infiltration._ Stability is 3
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provides a recognizable and nondispersible waste.also a factor in li 2.2 Vaate stram-- considered The TR and subsequent documentation identified the two waste streams listed below.
Ion exchange bead resin.
For the test solidification, this vaste stream consisted of non radioactive ion exchange bead resin obtained from a commercial resin supplier.
The supplied resin consisted of at least eight discrete types of resin beads, inorganic oxides, and water processing media; however, no more explicit information was provided regarding the app oximate quantities or specific types of resin.
should be provided by Diversified Technolostes in their revised This topical report.
Some of the material used for the test solidification had been stored for up to a year, and other material had been used for sludge filtration after their useful life was expended.
LOMI bead resin.
For the test solidifications, a licensed LON! vendor prepared surrogate LOM1 resin beads by loading LOMI chemicals and non radioactive metals and oxides on cation and anion resins to simulate a typical ion exchange loading for decontamination of sp.ent LOMI decon solution.
2.3 Minimum Reauirements fl0 CFR 61.$6(ail Section 61.56(a) of 10 CFR Part 61 contains the minimum requirements for all classes of vaste.
These requirements are intended to facilitate handling at the disposal site and provide for the protection of health and for the safety of personnel at the disposal site.
The TR was evaluated against each requirement contained in 10 CFR 61.56, as well as the guidance contained in the revised TF on Vasta Form (Refs,1 and 3).
2.3.1 Packarine Section 61.56(a)(1) of 10 CFR Part 61 specifies that vaste must not be packaged for disposal in cardboard or fiberboard boxes. The waste form is contained in steel druma or liners and thus satisfies this requirement.
2.3.2 Liould Vaste y
Section 61.56(a)(2) of 10 CFR Part 61 specifies that liquid waste must be solidified or packaged in sufficient absorbent material to absorb twice the volume of the liquid.
The liquid wastes addressed by the subject topical report and subsequent vendor communications, are solidified and, therefore, fulfill this requirement.
2.3.3 Free Liould Section 61.56(a)(3) of 10 CFR Part 61 specifies that free standing liquid in the solid waste shall not exceed 11 of the volume of the solid wasta.
In the 4
4 TR, th3 v:ndor states that 'the binder cures free standing monolith inside the container *,(emphasis added). forming a licuid fr TR (Ref. 8) stated that 'upon cutting through the sida of the linerThe original amount of water was observed, collected and measured.
{There were, a small approximately 1.5 gallons the small circumferential void between the liner Diversified Technologies' onolith "
discussion of this phenomenon points out 0.10% of the liner volume. amount was less than 0.15% of the waste volume se wel that the Inspection indicated that driven off the monolith by the exothern and volume shrinkage experiencedthe water during the binder curing process.
This is supported by bench scale testing.
han a sample is removed from its mold, a small amount of moisture is evident
=
on its surface.
This surfr-' moisture appears to be independent of the degree of pre dewatering.
Althou6u here may be some free water present following solidification as demonstrated, the volume is well within the maximum, and the waste forms therefore fulfill this requirement.
2.3.4 Peactivity of Product Section 61.56(a)(4) of 10 CFR Part 61 specifies that the waste aust not be readily capable of detonation, explosive decomposition, or reaction, at normal pressures and temperatures, or of explosive reaction with water.
After solidification, the waste forms described in the subject topical report do not contain any substances capable of such reactions and thus satisfy this requirement.
2.3.5 Toxic Cas Generation Section 61.56(a)(5) of 10 CFR Part 61 specifies that the waste must not contain or be capable of generating toxic gases, vapors, or fumes harmful to persons transporting, handling or disposing of the vaste form.
The solidified waste forms emit no such gases, vapors, or fumes and thus satisfy this requirement.
2.3.6 Pyrochoricity A waste must not be pyrophoric, as defined in 10 CPR 61.2 and prohibited in 61.56(a)(6) of the regulations. The solidified wraste forms are not pyrophoric nor do they contain materials which are pyrophoric; therefore, the solidified wastes satisfy this requirement.
2.3,7 +.uassous Vastes This solidification process is not proposed for use on gaseous wastes, so that 10 CPR 61.56(a)(7) of the regulation is not applicable to the Diversified Technologies vaste forms.
2.3.8 liaran)M&MA8 te Under Section 10 CFR 61.56(a)(8), vaste containing hazardcus, biological, pathogenic, or infectious material must be treated to reduce to the maximum extent practicable the potential hazard from the non radiological materials.
5 i
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Neither the VER1* polymer binder material, not th s
s Therefore, the requirements of 10 CFR 61.56(a)(8) have been met.
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It should be noted that the NRC topical report review of the Diversified t
Technologies VERIM solidification process did not address any applicable U.S.
^
Environmental Protection Agency (EPA) requirements relating to hazardous so for which the vendor or waste generator using the Diversified
- waste, t
Technologies VERI
Under RCRA, the EPA has jurisdiction over the management of solid hazardous wastes with the exception of source, byproduct, which NRC regulates under the Atomic Energy Act. and special nuclear material, LLW's contain source, byproduct, or special nuclear materials, but they may also contain chemical constituents which are hazardous under EPA regulations promulgated under Cubtitle C of RCRA.
radioactive and hazardous waste (mixed waste).Such wastes are commonly re Appilcable NRC regulations control the byproduct, source, and special nuclear material components of the mixed LLW (10 cm Parts 30. 40, 61, and 70); EPA regulations control the hazardous component of the mixed LLW (40 cm Parts 260 266, 268 and 270).
Thus, all of the individual constituents of mixed 11R are subject to either NRC or EPA regulations. However, when the components are combined to become mixed LLW, neither agency has excluelve jurisdiction under current Federal law.
wherein NRC regulates the radioactive component and EPA regy,lates t hazardous component. of the same waste.
2.4 Stability Reautrements fl0 CFR 61.56(bil and Reco ndationa of the Technical Position on Vasta Form The requirements of 10 cm 61.56(b) are intended to result in vaste products with structural stability.
Stability is intended to ensure that the waste does not structurally degrade and affect overall stability of the site through slumping,-collapse, or other failure of the disposal unit and thereby lead to water infiltration. Stability is also a factor in limiting exposure to an-inadvertent intruder, since it provides a recognizable and nondispersible The 1991 revised Technical Position on Waste Form elaborates on the waste.
provisions of Section 61.56, 2.4.1 ' Structural Senhility A structurally stable wuce form will generally maintain its physical dimensions and its form under the expected disposal conditions such as weight of overburden and compaction equipment, the presence of moisture and microbial activity, and internal factors such as radiation effects and chemical changes.
Structural stability can be provided by_ processing the waste to a stable form, such as has been proposed by the Diversified Technologies' polymer solidificction process.
The DiversifiedTechnologiesVERIgroposedwasteformsresultingfromthe process will be packaged in suitable containers, but the containers are given no credit for stability.
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form has been evaluated for use in direct trench burial, but can also be in improved diepeest conditions, such as in a high. integrity container engineered barrier system that mi ht use a concrete vault.
5 or an Additional guidance on meeting the regulatory requirements has been provided in the TP Technologies' polymeric waste forms as described in th The in Section 1.2, above, and evaluate the test results utilizing the crit recommended in the revised TP on Vaste Form.
eria Noth that the Dow samples were tested and approved in accordance with the original TP on Vaste Form (Ref which is very similar to the revised TP with respect to polymer waste forms.
2),
The Diversified Technologies samples were also tested in accordance with the or1 1nal TP, but will be qualified according to the revised TP.
8 2.4.1.1 As Cured ConDressive Strenzth The 1983 TP recommended that the minimum compressive strength for a solidified waste product be at least 50 psi as measured in accordance with the procedure of ASTM C39 (Ref. 11).
The minimum allowable compressive strength was later raised to 60 psi to take into account the increase in buriel depth (and thus burial loading) at Hanford from 45 feet to $5 feet.
The ters
- compressive strength testing" as used in this secticn of the TER is limited to testing of as. cured solidified waste forms.
"As cured" testing refers to testing performed on specimens which have ngg been subjected to environmental influences which have the potential to degrada the specimen (e.g., immersion, thermal cycling, irradiation), hence the equivalent term " pre. environmental."
The compressive strength tests were conducted in accordance with the procedure of ASTM C39 using cylindrical samples machined to a diameter of 1.25" and a length of 2.5".
The tests were conducted by an independent laboratory on three replicates of each type.
The compressive strengths follow:
Table 1. As Cured Compressive Strengths Compressive Mixed Eed Rasin Mixed Bed Rosin Surrog2te Strength (psi)
Data from TR Data from LONI Rosin DNS R$5 200 N7*
200 ft3 Liner Run Data Lab Sample 1919 i 40 2052 1 294 4176 1 232 50 ft8 Sample 5848 i 86 200 ft8 Sample 2633 1 798 Original Dow Topleal Report The compressive strengths of all solidified waste forms tested were well above the 60 psi minimum specified by the Technical Position on Waste Form, and are acceptable.
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2.4.1.2 EAdiation Resistance The Technical Position on Vaste Form recommends that specimens of each proposed waste stream formulation should remain stable after exposure to an absorbed gamma ray dose of 10' rad (or greater if the expected maximum accumulated absorbed dose of the waste is greater).
specimens should have the
- maximum practical compressive strengths"The irradiated wa (i.e. a minimum compressive strer.a h of 60 psi).
(Ref. 3),
c The Diversified Technologies' waste forms were subjected to 10' rads at i'autron Produc ts,
laooratory for compressive strenInc., and after inspection were shipped to an independent sample was also subjected to 10'gth testing. One Dow ton exchan6e bead resin that sample is listed below.
rads, and the compressive strength result for The radiation exposure evaluations were performed on three samples of each Diversified Technologies' formulation.
samples were 1.25< inch diameter by 2.5 inch long cylinders.
Tae the results of compressive strength testing on the irradiated samples:The following are Table II Compressive Strengths Following Irradiation Compressive Mixed Bad Resin Mixed Bed Resin Surrogate Strength (psi)
Data from TR Data from LOMI Rosin DNS RSS 200 NP*
200 ft8 Liner Run Data Lab Sample 1980 4950 508 200 ft8 S ample 2908 i 253 Original Dow Topical Report
~~
All post irradiation compressive strength test values listed are greater than 60 psi, are comparable to the non irradiated compressive strengtha listed in Table I, and are therefore acceptable.
2.4.1.3 Bioderradation Resistaneg The technical position recommends that vaste form specimens for each proposed waste stream formulation be tested for resistance to biodegradation in accord-ance with both ASTM C21 (Ref.12) and ASTM C22 (Ref.13),
which are tests for resistance of synthetic polymeric materials to degradation by fung 1 and by bacteria, respectively.
For polymeric products, some visible cultur's growth from contamination, additives, or biodegradable components on the specimen aarface that do not relate to overall substrate integrity may be If this happens, additional testing should be performed.
Following present.
biodegradation testing, polymeric waste form specimens should have the
" maximum practical compressive strengths" (Ref. 3), (i.e. a minimum compressive strength of 60 pai).
The 1.25 inch diameter by 2.5 inch long cylindrical specimens were evaluated for resistance to fungal and bacterial grovvh. There was no visible fungal or 8
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e bacterial growth on any of the specimens, after the fungal and bacterial testing are as follows:ne compressive strength values i
Table IIIa. Ceepresolve Strengths Following Biodegredation Testing (Fun gal)
Compressive Mixed Red Rosin Mixed led Rosin Surrogate Strength (psi)
Data from til Data from LONI Rosin DNS.RSS.200.NP*
200 ft8 Liner Run Data n.
Lab sample 201$ i se 4010 t $7 Sample j
200 ft3 i
2059 i 677 Original Dow Topical Report Table Illb Compressive Strengths Following Biodegradation Testing (Bacterial)
Compressive-Mixed led Rosin Mixed Bad Resin Surrogate strength (psi)
Data from 71t Data from IDMI Resin DNS.RSS.200.NP*
200 ft8 Liner Run Data 1.ab Sample 2524 i 291 1806 i 6 f 7 200 it8 Sample 1810 t $67 Original Dow Topical Report All post biodegradation compressive strength test values listed are greater than 60 psi, listed in TableI,. and are therefore acceptable.are comparable to the pre. biodeg 2.4,1.4 Leachability The 1991 TP recoassends that leach testing be performed for a minimum of 90 days in accordance with the procedure described in ANSI /ANS.16.1 (Ref. 14),
in addition to the desineralized water test specified in ANSI /ANS 16.1, the TP recommends that the samples be tested with the synthesized sea water leachant. The TP also recommends that radioactive forms of cobalt, cesium and strontium should be used as tracers. - The leachability index, as calculated in accordance with ANSI /ANS.16.1, should be greater than 6.0.
i The majority of the Dow waste forms were tested before ANS 16.1 was developed and publiebed. The Dow test methods were, however, stallar.to the ANS 16.1<
method, and unach of the Dow data has been verified by other researchers.
The main difference between the ANS 16.1 procedure and the Dow test method -is: in the amount of leachant volume used in the test. The;ANS 16.1 procedute.
specifies that a leachant volume 10-times'the~ external. surface area of the specimen be used.
The leaching in the Dow tests was carried out with smaller amounts of leachant 0.5 to 2 times the specimen surface area in order.that the very low leach rates of the Dow spacimens could be measured-without t
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exceeding the sensitivity et available counting equipment.
testing on vaste solidified using the Dow process indicated thatIndependent leac net. 6 for further information.) amount of lanchant used had no signific the low (see specified by ANS 16.1 for the Diversified Technologias s The a
were 4. 75 cm in diameter X 5.7 cm long, and were immersed in 250 ml of The samples dominera11 red water or synthesized sea water, for a V/S of approximat l either This V/S is deemed appropriate for this type of waste form only because th e y two.
leach indices indicated a correlation for the similar Dow waste formsare relatively h i
The revised TP recommends that *[ flor proposed nuclear power station waste streams cobalt, cesium and strontium should be used as tracers."
or1 81nal TP did not specify tracers.
The using the original TP, The proposed waste forms wr e tested only cobalt was used as a tracer.-nd the method described in the Dow TR (Ref. 5),
and The resulting leach indices in both synthe,1 zed sea water and domineralized water were more than three orders of magnitude greater than the TP criteria of 6.
Because the leach indices for cobalt in these waste forms were so high, and because the available results are similar to the Dow results, which also showed a very low leachability for cesium, testing with centum and strontium tracers is not required at time.
this The results of the Diversified Technologies leach testing are listed in Table IV Table IV Leachability Indices LEACKABILITY INDEX VASTE FORM (Co)
Hixed Bad Resin Mixed Bed R6 sin Surrogate Data from TR Data from LOMI DNS-RSS-200-NP' 200 ft8 Liner Run Rosin Data DEMINERALIZED VATER 16.3 11.9 11.6 SYNTHESIZED SEA VATER 10.1 9.8 9.5 Original Dow Topical Report All of the leach indices are greater than 6.0, and the leachability of these samples is therefore acceptable.
2.4.1.5 langraion Resistance The Technical Position on Waste Form recommands that vasta specimens should maintain the maximum practical compressive strength as tested using ASTM C39 (Ref.11) following immersion for a minimum period of 90 days.
The immersion resistance tests were performed on 1.25 inch diameter by 2.5-inch high cylindrical samples immersed in domineralized water for 90 days.
At the end of the 90 day pe riod compression tests were performed on the samples.
See Table V for the results of the compression tests for each vaste stream.
10
r Tchlo V Comprossivs Strengths P2110 wing Immersion Compressive Mixed 5ed Resin Mixed Bad Resin Surrogate Strength (psi)
Data from TR Data from LOM1 Resin DNS RSS 200 NP*
200 Et3 1.iner Run Data Lab Before Saaple Immersion 1919 i 40 2052 1 294 4176 t 232 Following Immersion 2023 86 2175 421 3801 t 644 50 ft' Before Sample Immersion 5848 66 Following Immersion 4128 1 128 200 ft3 Before Sample immersion 2633 i 798 Following Immersion 2119 i 486 Original Dow Tcpical heport The compressive strengths following immersion are well above the 60 pai required, and are similar to the enspressive strengths prior to immersion.
In addition, the test specimens were visually examined immediately after removal from the water in which they were immersed, and no changes in appearance or physical integrity were evident.
The staff considers that the waste specimens have maintained the maximum practical compressive strengths, and the immersion results for these samples are therefore acceptable.
test 2.4.1.6 Thernal Cvelinz The Technical Position on Waste Form recommends that thermal cycling testing be conducted in heating and cooling chambers conforming to those described in ASTM B553, Section 3 (Ref. 15). A series of 30 thermal cycles between 60*C and -40SJ should be carried out in accordance with ASTM B553.
Following testing, the specimens should have the maximum practical compressive strengths.
The the'rmal cycling test was performed on cylindrical specimens measuring 1.25 inches in diameter by 2.5 inches high.
The vendor ensured that the samples reached charmal equilibrium at each temperature by placing a thermocouple in the center of one of the waste forms.
The sample was placed in the heating chamber, and the time required to reach 60'c was determined.
The sample was allowed to cool to room temperature, then placed in the cooling chamber and the time required to reach 40*C was determined. The qualification test samples were then subjected to thermal cycling for thirty cycles, with the samples held at each temperature ( 40'C, 20*C, and 60*C) for one hour af ter reaching thermal equilibrium. The following are the post thermal cycling compressive strengths:
11
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Table VI. Compressive Strengths Followfng Thermal Cycling Compressive Igized led Resta Mixed led Resin Surrogate Strength (psi)
Data from TR Data iros 14t! Rosin tes.RSS. 200.Np*
200 ft3 1.iner Run Data lab Sample 2492 1 35 5539 i 336
-200 ft3 Sample 2914 1 554
..+
OriginaT~Dow Topical Report Following the thirty cycles, visual examination showed that the samples had maintained their appearance and physical integrity.
In addition, all post.
thermal cycling compressive strength test values listed are greater than 60
- psi, Table I, and are therefore-acceptable.are comparable to the pre thermal cyc 2.4.1.7 Correlation Testine The TP indicates that if-small simulated laboratory. size specimens are used for the qualification testing program, test data from sections or cores of the anticipated full scale products should be obtained to correlate the i
characteristics of actual size products with those of simulated laboratory.
size specimens.
This testing may be performed on non radioactive specimens.
The full scale specimens should be fabricated using actual or comparable solidification equipment.
This correlation should be established by 90 day-immerston tests (including post.ianersion compressive strength tests).
It is also suggested that the correlation testing should be performed on the most conservative waste stream intended for use for the particular solidification medium; that is, the vaste strena that presents the most difficulty in producing stable products should be used.
In essence, this TR is designed for the purposes of correlation testing.
The mixed bed resin waste stream was solidified in a 200 ft 3 liner, with lab scale samples manufactured for correlation, and for the leach tests.
In addition, as a more conservative vaste stress than the surrogate !ANI waste stream, the 200 ft3 liner solidification qualifies the IANI resin beads for large scale.
solidification as well.
The results are summarised in Table V.-
The full scale and lab. scale specimens exceed the 60 pai compressive strength criterfon, and exhibit similar compressive strengths, both before and after 90 day inimersion. In summary, the full. scale specimen results satisfactority -
demonstrate the correlation between full scale and lab scale-samples.
2.4.1.8 Hamnganalty In addition to correlation testing, it is necessary to show that the product is homogeneous to the extent that all regions in the product have compressive strengths analogous to those of the lab-scale specimens.--
12
Eight vortical cores were taken from the solidified 200 ft 8
mixed bed resina.
1.25 inches la diameter by 2.5 inches in length.After coring, I
three samples would be from the top, bottom and m i
c of the The initial compressive test results on the cored samples were t
These results exceed the 60 psi minimum, are similar to the lab scale results!
2633 1 798.
of 2052 1294, and show that the full scale waste form is homogeneous to the extent required, 2.4.2
[rfg Liouid r
Section 10 CFR 61.56(b)(2) requires that vastes processed to a stable form have a liquid content that does not exceed 0.5 percent of the volume of the
- vaste, The revised TP on Vaste Form addresses this requirement.
C.2.g recommends that waste specimens have less than 0.5 percent by volume of Section the waste specimen as free liquids as measured using the method described in ANS 55.1 (Ref. 16)
Free Liquids should have a pH between 4 and 11.
t See section 2.4.3 for a discussion of free liquid found following liner solidification.
The liquid amounted to less than 0.15% of the volume of the waste.
The volume requirement has been satisfied.
not measured when the liquid was discovered, and it The pH of _ the liquid was is no longer possible to make that determination.
Diversified Technologies notsd that the same phenomenon occurs in lab. site samples.
The NRC rev.C.nds that lab. size samples of the LONI and mixed bed resin be manufacear2d, and that the pH be i
determined and reported in the revised Topical Reg ore.
2.4.3 221d_J2A111 Section 61.56(b)(3) of 10 CPR Part 61 states that void spaces within the vaste and between the vaste and its package must be reduced to the extent practicable.
i The polymer binder is forced through the waste, and the waste form solidifies in the con:siner.
A circumferential void usually forms between the liner and the final solidified monolith when the curing binder undergoes shrinkage (approximately 2 51). Otherwise, the solidification reactions are usual polymerization reactions and do not involve-formation of gaseous byproducts which might create gas. filled voids within the solidified waste form.
No voids were noted during visual inspections of the solidified monolith.
The process is effective in minimizing void spaces to the extent practi' cable, however, it is the responsibility of the user to ensure that containers are filled to reduce void spaces.
2.5 Procama control Pronram The introduction to the technical Position on Waste Form recommends that waste generators using an approved topical report: process develop plant specific process control procedures to demonstrate that a stabilized plant specific waste stream satisfies Yart 61 waste form requirements. Diversified Technologies has provided a set of operating procedures as part of the Tcpical Report.
The operating procedures consist of PCP 03.. " Process Control 13
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' General Operating Procedure, Vf. Rim Solidification,' Procedure, Vin The Process control Procedure (PCP) describes the method for developing the quantities of cat and promotor that will achieve the desired optimal solidification formulation.
Once the amounts of catalyst time and quality of the final product have been determined, the General'an operating Procedure lists the steps for final vaste form solidification.
These procedures, with the comments outlined in the RAl's and responses generally acceptable.
, are There is or,e exception, however.
Both documents describe addition of modifiers when necessary.
ion exchange capacity of those resins which have too large a capa the remaining.
This is a reasonable addition; however, the modifiers have not been qualified with the process described in the Diversified Technologies TR.
Diversified Technologies should delete the references to modifiers #1 and #2 in the Process Control Procedure and the General Operating Procedure In order for the modifiers to be qualified, a separate, additional TR should be submitted, which demonstrates that samples manufactured with th3 VERim process, using the modifiers as additives, can be successfully solidified.
2.6 Reoortinr of Mishang As a result of the revision to the TP (Ref. 3), vendors and processors are included in the group who are requested to report mishaps.
For the Diversified Technologies VERIN process, the following types of mishaps are examples of instances that should be reported for solidified Cla.3s B or Class C waste forma exhibiting one of the following characteristics:
Creater than 0.5 percent volume of free liquid.
Concentrations of radionuclides greater than the concentrations demonstrated to be stable in the waste forls in qualification testing accepted by the regulatory agency.
Creater or lasser amounts of solidification media than were used in qualification testing accepted by the regulatory agency.
Presence of chanical ingredients not present or accounted for in qualification testing accepted by the regulatory agency.
Instability evidanced by crumbling, cracking, spalling, voids, softening, disintegration, non homogeneity, or change in dimensions.
Evidence of processing phenomena that exceed the limiting processing conditions identified in the applicable TR's or operating procedures, sich as foaming, excessive temperature, premature or slow hardening, production of volatile material, etc.
Vaste form mishaps should be reported to the NRC's Director of the Division of Low Level Vaste Management and Decommissioning and the dasignated State 14 I
disposal site regulatory authority within 30 days of knowledge of the incident.
should not be shipped off. site until approval is obt site regulatory authority generators and processors.
The reason for this is that the low level waste that are required by 10 CFR 20.311/20.2006 waste forms that are subjecttheir waste forms meet all applicable requirem to certify
. and required long term structural stability.to the types of mishaps m possess the When mishaps of the nature described above occur, it is expected that, before the vaste form is shipped to a disposal facility, either adequate sitigation of the potential effects on the vaste form or an acceptable justification concerning the lack of any potential significant effects of the affected waste form on the overall performance of the disposal facility would be provided.
3.0 CONCLUSION
S The Diversified Technologies Topical Report. with the Diversified Technologies responses to NRC comments and questions, for licensing the waste form produced by the VERIis acceptable as a reference document S process, subject to the certain limitations and further actions by Diversified Technologies.
3.1 Limitations a)
The vaste forms produced are limited to those made from the reactants specifically identified in the TR as those used to prepare the test specimens on which the data were obtained.
Subject to the above limitation, and after completing the further actions listed below, the Diversified Technologies waste forms should be capable of meeting the stability requirements of 10 CFR Part 61 when produced using the process described in the Topical Report (Ref. 4).
3.2 Further Actions a)
Information to be added to the revised Topical Report:
1.
Diversified Technologies must characterize the chemical nature of the resina used in the qualification tests so that users of the process can know what kind of resins can be satisfactorily solidified. Diversified Technologies should also state what actual nuclear power plant resins are represented by the simulated mixed bed resin vaste stream.
2.
Diversified Technologies stated that *each media type was separately tested and shown to successfully solidify."
The results of these tests should be provided in the revised Topical Report, as they provido vital bounding information.
3.
Diversified Technologies should determine the approximate pH of any free liquid resulting from the solidification process, and include the figure or range in the revised Topical Report.
(See Section 2.4.2 of this TER for more details).
15
Q t
i Diveratfied Technologies should revise the Process Control Procedure b) j to inslude any 1Latts on the types of resina that can be solidttt d using this process, e
c)
Diversified Technologies should delete the references to modifiers #1 arW1 #2 in the Process Control Procedure and the General Operating Procedure.
16
G REFERENCES 1.
Code of Federal Regulations, Title 10, Part 61, ' Licensing Requireme for land Disposal of Radioactive V3ste," Nuclear Regulatory Commiss Vashington, D.C., January 1, 1991.
2.
U.S. Nuclear Regulatory Commission, ' Technical Position on Vaste Form
- Rev. O. May 1983.
3.
U.S. Nuclear Re6ulatory Commission, " Technical Position on Vaste Fori
- Rev. 1, January 1991.
4.
Diversified Technolostee. Inc., Topical Report, " VERI" (Vinyl Ester Resin In Situ)
DT. VERI 100 NP/P, December 1,1991. Solidification Process for Low. Leve 5.
Dow Chemical Company, Topical Report, "The Dow Vaste Solidification Process for Low. Level Radioactive Vastes.. Generic Vaste Form certification Results," DOV RSS 200 NP.A June 1984.
6.
Technical Evaluation Report, "TER Related to the TR DNS RSS 200 NJ, Covering the Dow Polymer (Vinyl Ester Styrene (VES)) Process for Solidification of Low Level Vaste Form," April 1988.
7.
Memo from E. Wick, through M. Tokar, to J. Surmeier, dated December 4, 1989 " Summary of November 14, 1989 Meeting with Diversified Technologies, Group, Inc."
8.
Diversified Technologies, Inc., Topical Report, "A Vaste Management System Utilizing VPS", NVV", and VER1* Process Systems and Technology,"
DTI VMS.100 NP, August 1990, 9.
Memo from J. Kane (NRC) to C. Jensen (Diversified Technologies), dated April 14, 1992.
10.
Memo from C. Jensen (Diversified Technologies) to J. Kane (NRC),
" Response to Request for Additional Information (RAI) #2...,' dated June 12, 1992.
11.
ASTM C39, " Standard Test Method for Compressive Strength of Cylindrical C.oncrete Specimens," American Society for Testing and Katerials,1980.
12.
ASTM C21, ' Standard Practice for Determining Resistance of Synthetic Polymeric Materials to Fungi," American Society for Testing and Materials, 1970.
13.
ASTM G22, " Standard Practice for Determining Resistance of Plastics to l
Bacteria," American Society for Testing and Materials,1976, 14 ANS/ ANSI 16.1, " Measurement of the Leachability of Solidified Low Laval Radioactive Vastes by a Short Ters Test Procedure," American Nuclear Society, 1986, 17 L
1 15.
A5138 4513. " Standard Test Method for Nrmal Cycling of Rioctroplat Plastias,' Aastiaan Society for Testing and Materials, 1979 c
16.
ANS SS.I. 'American National Standard for Solid Radioactive V Procesalag System for Li ht Water Cooled Reactor Plants.' American l
Nuclear Society, 1979.
t 4
18
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