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Commission of the European Communities

nuclear science and technology

MANAGEMENT OF
TRITIUM-CONTAMINATED WASTES

A SURVEY OF ALTERNATIVE OPTIONS

Report
EUR 12526 EN

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Commission of the European Communities

nuclear science and technology

MANAGEMENT OF
TRITIUM-CONTAMINATED WASTES
A SURVEY OF ALTERNATIVE OPTIONS

F. MANNONE
Commission of the European Communities
Joint Research Centre
Ispra Establishment
1-21020 Ispra (VA)

Directorate-General Science, Research and Development
Joint Research Centre

1990 EUR 12526 EN

Published by the COMMISSION OF THE EUROPEAN COMMUNITIES Directorate-General Telecommunications.Luxembourg. 1990 . Brussels . Information Industries and Innovation L-2920 LUXEMBOURG LEGAL NOTICE Neither the Commission of the European Communities nor any person acting on behalf of the Commission is responsible for the use which might be made of the following information Catalogue number: CD-NA-12526-EN-C © ECSC — EEC — EAEC.

current strategies and practices to be applied for the routine management of these wastes need also to be defined. For this reason a part of the experimental activities to be performed in ETHEL will be devoted to laboratory research on tritiated waste management. Through an exhaustive literature survey tritiated waste management options till now in- vestigated or currently applied in several countries have been assessed. equipment and containment systems under tritium impact. . A particular importance has been attached to the tritium leach test programmes. which is the intent of this report. since all experimental activities planned for the execution in ETHEL will by itselves generate tritiated wastes. i. To attain this target an adequate background information must be provided. III ABSTRACT The European Tritium Handling Experimental Laboratory (ETHEL) under construction on the site of Ispra Joint Research Centre of the Commission of Euro- pean Communities has been commissioned to experimentally develop operational and environmental safety aspects related to the tritium technology in fusion. However.e. whose results enable to assess the tritium retention efficiency of the various waste immobilization options. dealing with the behaviour and reliability of materials. The conclusions resulting from the overall assessment are presented.

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TRITIUM MONITORING 5 3. Tritium monitoring in solid media 5 3.3. TRITIUM SOURCES AND PRODUCTION RATES 2 2. C O N T E N T S Page 1.2.3. References for Section 5 19 6.2.1. INTRODUCTION 1 2. Tritium monitoring in liquid media 8 3.1. Tritated wastes from heavy water reactors and associated tritium recovery plants 12 4. References for Section 3 11 4.4.2. Required degree of immobilization 23 7. Recovery of tritium losses 18 5.5. References for Section 6 22 7.4.1.4. IMMOBILIZATION AND CONTAINMENT OF TRITIUM FOR WASTE MANAGEMENT PURPOSES 23 7.5. Tritium monitoring in atmospheric air 9 3. References for Section 2 4 < 3.3.3. TRITIATED WASTE MINIMIZATION AT SOURCE 17 5. Tritiated wastes expected from future thermonuclear fusion reactors and associated tritium handling facilities 13 4. General considerations 23 7.1. SORTING AND CLASSIFICATION OF TRITIATED WASTES 21 6. Tritiated wastes from light water reactors 13 4.1. References for Section 4 16 5. Tritiated wastes from fuel reprocessing plants 13 4. ORIGIN AND CHARACTERISTICS OF TRITIUM CONTAMINATED WASTES 12 4. Minimization of suspect solid wastes 19 5. Tritium monitoring on material surfaces 8 3. Potentially applicable methods 24 .2. Tritium confinement 17 5.1.

Absorbers 38 9.3.3. Organic polymers 44 9.1. CONTAINMENT OF TRITIUM IN SOLIDIFIED LIQUID AND ENCAPSULATED SOLID WASTES 68 11.1.2. Packaging of tritiated solid wastes without encapsulation 93 12. Organic polymers 52 9. Hydraulic cements 40 9. TREATMENT AND CONDITIONING OF TRITIATED LIQUID WASTES 32 9.4.1.3.3. References for Section 10 66 11. Factors limiting tritium enrichment 35 9. Solidification of tritiated waste waters 37 9.2. Additional treatments on solidified liquid wastes 68 11.2.4.2. Hydraulic cements 52 9.2. Polymer impregnation 69 11.4. TREATMENT AND CONDITIONING OF TRITIATED SOLID WASTES 58 10.4.3.5.1. Drying agents 37 9. Overpacking of tritiated solid and solidified liquid wastes 95 12.3.3.4. 31 9. References for Section 11 90 12. The multiple physical barrier concept 28 7.3. Tritium separation and enrichment 32 9. Encapsulation 74 11. Criteria for selecting an immobilizing agent 24 7.1. Packaging of tritiated hard waste composites 93 12. DETRITIATION OF GASEOUS WASTES 30 8.4.1. Solidification of tritiated organic liquids 51 9. PACKAGING OF TRITIATED SOLID AND SOLIDIFIED WASTES 93 12. Containerization of solidified liquid wastes 80 11.6.4. References for Section 9 53 10. Absorbers 53 9. Volume reduction of tritiated solid wastes 58 10.1.4.1.1.3.3.4. Containment of encapsulated metallic hard wastes 89 11.2. References for Section 12 100 . References for Section 7 29 8. Detritiation of tritiated metallic hard wastes 60 10. VI 7.2.3.5.5.1. References for Section 8 .1.3 Encapsulation of tritiated metallic hard wastes 65 10. Inorganic salt hydrates and hydroxides 39 9. Surface coating 69 11.

Encapsulation of metallic hard wastes 114 14. Monitoring of tritium outgassing from packaged wastes 118 15.1. Packaging of solid wastes without encapsulation 118 14.1. Containerization of solidified liquid wastes 116 14.2. SUMMARY 107 14. VII 13.3.4.The electrolitic exchange (ELEX) process for isotopie separation & enrichment of tritium from aqueous reprocessing effluents 133 Appendix IV .2.4.3.4.2.3. Waste pretreatment 108 14. Detritiation of gaseous wastes 108 14.Schematic illustrations of tritium removal processes applied at the Darlington and Chalk River plants 135 Appendix V . Overpacking of solid and solidified liquid wastes 118 14.The smear technique 127 Appendix II .Solidification of tritiated waste waters.2. MONITORING OF TRITIUM OUTGASSING FROM PACKAGED WASTES 102 13.1.2. Waste minimization at source 107 14. CONCLUSIONS 120 APPENDICES 125 Appendix I . Containment and packaging of encapsulated metallic hard wastes 117 14.5. Waste immobilization 111 14. Waste containment and packaging 114 14.4.3. References for Section 13 106 14.4.2. Specimen preparation for leach tests at Ontario Hydro 137 .Tritium isotopie separation & enrichment. Schematic flow diagrams illustrating the available process techniques 129 Appendix III .2. Solidification of liquid wastes 111 14.3.4.5. Detritiation of metallic hard wastes 110 14.4. Additional treatments on solidified liquid wastes 115 14.1. Tritium separation and enrichment 109 14.2.1. Volume reduction of solid and liquid wastes 108 14.4.

Specimen preparation for leach tests at Ontario Hydro 151 Appendix X . polymer impregnation and containerization of tritiated waste waters.Solidification. VIII Appendix VI .Burial packaging of solidified tritiated liquid wastes at MLM 153 GLOSSARY 155 ACRONYMES & ABBREVIATIONS 156 .Solidification and encapsulation of tritiated waste waters. Specimen preparation for leach tests at Ontario Hydro 149 Appendix IX . Specimen preparation for leach tests at BNL & MLM 141 Appendix VIII . Specimen preparation for leach tests at KFK. Karlsruhe 139 Appendix VII .Encapsulation of solidified tritiated waste waters.Encapsulation of solidified and containerized tritiated waste waters.

the European Communities Project aimed at the construction of an experimental thermonuclear fusion device of the Tokamak type. . In this frame alternative tritiated waste management options so far inves- tigated or currently applied to this end in Europe. equipments and contain- ment systems under tritium impact. The intent of this report is that of providing this information through an exhaustive litera- ture survey. This was decided by the CEC in the frame of the European Community research programme on Fusion Tech- nology and Safety. To attain this target. current strategies and practices to be applied for the routine management of these wastes need to be defined. in assessing the various waste management alternatives the major at- tention was focused on the presence of tritium rather than on that of gamma-emitters. USA and Canada have been assessed. originated by the neutron activation of structural materials. Since tritiated wastes expected from the ETHEL operation will be contaminated only by tritium. an adequate background information is required. The European Tritium Handling Experimental Laboratory (ETHEL) under con- struction on the site of Ispra Joint Research Centre of the CEC (Commission of the European Communities). A particular importance has been attached to the tritium leach tests in water whose results enable a direct as- sessment of the tritium retention efficiency achievable by the various waste immobi- lization options. The scope of ETHEL is to provide information to design teams and licencing authorities needed for a correct evaluation of operational and environmental safety aspects related to the behaviour and reliability of materials. since all experimental activities planned for the execution in ETHEL will by itselves generate tritiated wastes. The conclusions resulting from this assessment study will also provide a valuable help for defining the subjects and areas of research activities on tritiated waste management to be performed in ETHEL. has been commissioned to experimentally develop various safety aspects related to the tritium technology in fusion. liquid and solid forms. INTRODUCTION The presence of tritium in tritium-burning devices to be built in the frame of large scale research on thermonuclear fusion poses many problems especially in terms of occupational and environmental safety. One of the these problems derives from the production of tritiated wastes under gaseous. For this reason a part of the experimental activities to be performed in ETHEL will be devoted to laboratory research also in the field of tritiated waste management. However.1. All these wastes need to be adequately processed and conditioned to minimize tritium releases to an acceptably low operational and environmental level and consequently to protect workers and populations against the risks of unacceptable tritium dose exposures. In this context ETHEL will contribute to experi- mental research in support of NET.

TRITIUM SOURCES AND PRODUCTION RATES At present tritium arising in the nuclear industry is mainly due to the tritium production in nuclear power reactors..2 taken from ref. (1). . 7 Li.. In heavy water reactors the heavy water of the moderator/coolant is the most large source of tritium generated by neutron reaction on deuterium and this reaction produces two order of magnitude greater activity than it is produced by fission. Furthermore tritium can be accumulated in the coolant because of the tritium fraction that escapes from the fuel in variable percentages depending on cladding types. In Tab. moderators etc. 2. summarizes estimates of the activities (per unit energy generated) emitted to the environment or transferred to a reprocessing plant. . 10B. 6 Li. 8 He usually present as impurities or components in reactor fuels. In such plants tritium is generated by ternary fission of the heavy nuclei occuring in the fuel as well as by neutron reaction on light elements such as 2 H.2. may be emitted to the environment from the reactor site or transferred with fuel to a reprocessing plant. The tritium produced in the nuclear power reactors may be retained in the reactor materials. 2. coolants. In most reactors the major source is the ternary fission occuring in the fuel. Tab. so that variation factors not greater than 2 are observed between the total tritium activi- ties per unit of energy produced by different type reactors (1). In all types of nuclear power reactors tritium is present in the moderator and coolant being directly generated by neutron absorption.1 are summarized typical rates of production of tritium in various power reactors by fission in the fuel as well as by neutron absorption in reactor components.

D.2o) FBR 20-30 25 95 -100 Steel and blanket 3.0(b) <0.a)-1 FRACTION (X) TYPE CLADDING OF TRITIUM ELEMENTS AND MATERIALS PARENT NUCLIDE by Fission by Cumulation RELEASED UNDERGOING NUCLEAR <Nucl. .Sources and Production Rates of Tritium by Neutron Reactions (1).ίη. in H.1X loss of tritium from fuel.9X isotopie purity) for pH control./coolant 6 L1 3 <n.na) mod./coolant AGR 17 >30 Li in graphite moderator. γ ) Zircaloy BUR 15-20 0.4(c) <1 1 Nat.1-0.1X loss of tritium from fuel and for use of Li (>99.TABLE 2.O mod. 'LljCn.e) 1.ρ) HTR 18 -30 impurities in graphite a) Includes estimates of tritium release from fuel. React.and ^■yn. c) Lower limit is for 0.B 5 (n. D.2 Stainless Β and Li impurities in core 10. b) Lower limit is for 0.γ) OJ HUR 20-24 2400 <1 D./cooIant Η. and Li Ήβ^η.0 mod.2 Li impurities in H.1 . nat.2a) 5 Soluble B.) REF. REACTOR PRODUCTION RATE: kCi. in D. γ) PUR 15-20 0.na) 6 Li 3 (n.7-8.5 He in He cool.B (n.(GW(e).55-1. in the fuel into coolant & FROM FUEL TRANSMUTATION moderator (a) Typical M axin 10.O 7 Li 3 (n.

Vienna.TABLE 2. (2) IAEA.4 10-50 90-50 15-20 HWR 24 90 10 20-24 AGR 4.55-1 1 90 15-20 BWR 0.2 . . 2.Tritium emissiona and transfers from various power reactors (1). Technical Reports Series. Handling of Tritium Bearing Wastes.a)" 1 Gaseous phase (%) Liquid phase (%) kCi. IAEA. Vienna. 234. REACTOR EMITTED TO THE ENVIRONMENT TRANSFERRED TO TYPE REPROCESSING PLANT kCi. 5 & 7. low HTR <8.fGWfeJ. IAEA Technical Reports Series.5 -100 a -0 10-17 From helium clean-up system. 1981. p.fGWfeJ.5 10 90 12-IS FBR <1 .a)" 1 PWR 0.1 References for Section 2 (1) IAEA. No.1-0. 3-5. p. 1984. No. . 203. IAEA. Management of Tritium at Nuclear Facilities.

i. . Nevertheless the characterization of tritiated hard wastes in terms of tritium content and release potential is often needed to decide their conditioning and/or pakaging forms.detect in real time and to alarm any increase beyond the authorized limit of tritium concentration in the atmosphere of tertiary containments (i. etc. 3. air locks.e. for comparison with authorized release limits. (1). The major tritium monitoring requiremens are dealing with tritium surface con- tamination of solid materials as well as tritium contamination or content of liquid and gaseous media.1. This is done for radiological protec- tion purposes in order to prevent accidental tritium releases to the working environ- ments. keeping always in mind the low energy and the short range of tritium beta-emissions. More detailed information on them are given in ref. . (2) the determination of tritium released during these treatments will enable to control with a satisfactory degree of approxima- tion the actual tritium concentration as well as the degree of homogeneity of its distribution in the bulk of a hard waste item. glove- boxes. As mentioned in ref. Therefore only the most known tech- niques and instruments currently applied in this measurement field are here briefly outlined. tritium detector must be specifically designed for each of the above mentioned purposes. . 3. TRITIUM MONITORING A deep and exhaustive examination of the problems associated with tritium monitoring is out of the scope of this section. A non-destructive measurement of the total tritium activity in the bulk of a solid waste cannot therefore be sufficiently representative of its effective tritium content.2). . This is done again for radio- logical protection purposes in order to adequately protect the workers and the population against the risk of unacceptable tritium exposures.determine on a time integrated basis the total release of tritium during this time.1 Tritium monitoring in solid media The radioactivity of tritium is known to be due the emission of beta-particles of low energy and short range. To measure tritium activity with the due efficiency.).measure the removable surface contamination and the out gassing rate of tritiated materials and composites for safe handling purposes. The characteristics and application fields of typical tritium detectors are summarized in Tab.determine tritium concentration and/or purity inside the primary containment such as experimental apparatus and storage containers for process control and accoun- tancy purposes. by submitting samples taken from hard waste items to leaching or to thermal treatments (see subsection 10. interspaces. for regulatory purposes. It is well known that tritium monitoring is currently performed in order to: .) as well as in duct or stack exhausts. working environment. i. .3.e. waste stores etc. Such requirements may be met by destructive measurements.g.e.detect in real-time and to alarm any undue increase beyond the admitted level of tritium concentration in the atmosphere of the secondary containments (e. pass-boxes.

TABLE 3.1 - Characteristics and application fields of detectors currently employed for T-monitoring purposes.

TYPE OF MONITORING SENSITIVITY LIMIT COUNTING RESPONSE INTERFERENCES, REQUIREMENTS
Τ-DETECTOR PURPOSE kBq *m microCi *m CHARACTERISTICS TIME ft DRAW BACKS

Ionization Chamber Process monitoring ft accountancy 50 (2) -1.3
(2)
Discontinuous, on gaseous In real time - Radioactive particles ft ambient
(IC) process data, control ft inventory) samples gamma fields
Atmosphere monitoring in sec­ Non-discriminating radio­ - Required a particulate filter,
ondary containments (glove boxes, active particles & ambient an electrostatic precipitator
etc.) gamma emissions and a second compensating IC(3)
Air monitoring in tertiary - Sensitivity to vibrations, to
containments (working environ­ prolonged moisture conditions
ments, waste store, ducts, and to contaminations (memory
stacks) effect)
Emergency monitoring for
σϊ
large T-release

Gas Proportional Air monitoring in tertiary 0.37 10 -2 - Discontinuous on gaseous 1 minute Required a counting gas, (e.g.
Counter (GPC) containments (stacks) samples argon, methane)
Surface contamination mea­ - Direct, on contaminated Too low upper detection limit
surement surfaces (4) ft indirect, (37 MBq-m" 3 )
on filter papers (5) More complex and expensive than
Measurement of tritiated - Indirect, on filter pa­ a IC
particulates in air pers (5)
- Discriminating radioactive
particles & electrons

TABLE 3.1 - Continued

TYPE OF MONITORING SENSITIVITY LIMIT COUNTING RESPONSE INTERFERENCES, REQUIREMENTS
Τ-DETECTOR PURPOSE kBq *m microCi *m CHARACTERISTICS TIME ft DRAW BACKS

Liquid Scinti H a ­ Liquid monitoring -4*10 -10 - Discontinuous on liquid Delayed Chemiluminescent materials
lation Counter samples
(LSC) Air monitoring - Indirect on bubbler Difficulties in providing clean
liquids samples ft proper mixing
Measurement of tritiated particu­ - Indirect on filter papers
lates in air (6)
Surface contamination measurement • Indirect on filter papers
(6)

Plastic Scintilla­ Liquid monitoring -4· 10 -10 - On-line continuous count- In real time Radioactive particles, external
tion Counter (PSC) ing of liquid streams (7) -fields
Surface contamination measurement - Direct on con­ Chemiluminescent ft luminescent
taminated sur­ materials.
faces (8)
Measurement of tritiated particu­ - Indirect (8) on Delayed Required liquid filtration and
lates in air filter papers lead shielding
(9) Memory effect

(1) By installed and portable detectors.
(2) With a 1 dm 3 ion chamber.
(3) Side by side or base to base or concentrically mounted.
(4) By using a counter provided with an open window.
(5) By using a counter provided with a means for introducing samples (e.g., filter papers from smear tests or air filtration) in it.
(6) By counting filter papers from air filtration or smear tests, previously immersed in the liquid scintillation cocktail, inside a standard scintillation vial.
(7) By a scintillation flow cell provided with a solid scintillator of a variable form.
(8) By using a plastic scintillator without a window.
(9) On filter papers from smear tests and air filtration.

3.2 Tritium monitoring on material surfaces

As well illustrated in ref. (1) three different values of tritium activities can be
measured dealing with a tritium contaminated surface, namely:
a) The activity due to the removable tritium surface contamination, i.e. to the frac-
tion of tritium surface contamination which is removable or transferable under
normal working conditions.
b) The activity due to the directly measurable tritium surface contamination i.e. to
the fraction available for a direct "in situ" measurement.
c) The total activity i.e. the sum of the activity fractions due to tritium contamina-
tion sorbed on as well as that sorbed into the surface of the material.
The total tritium surface contamination including the directly measurable as
well as the more deeply absorbed tritium contamination cannot be readily measured
without a destructive method. The direct measurement of detectable tritium surface
contamination is, in principle, feasible using a real time detector such as an open
window proportional counter. A fraction of the removable tritium surface contamina-
tion can be measured by the smear technique, with a removal efficiency being typi-
cally fixed, by convention, to 10 per cent of the removable surface contamination (1).
For safe handling purposes the measurement either of the removable or the
directly detectable tritium surface contaminations appear to be appropriate.
However the latter measurement techniques is sometimes unapplicable, being the
used real time detector often liable to become contaminated because of the high
contamination level and outgassing rate of the material surface.
Furthermore many probes are designed only for being applied to smooth and flat sur-
faces and may require a counting gas (1). Consequently to evaluate a tritium surface
contamination, the smear technique appear to be the most accepted and frequently ap-
plied method. A summary description of the application of this technique taken from
ref. (1) is given in Appendix I.
Finally is worth noting that for the purpose of disposing of tritiated wastes the
measurement of the total tritium surface contamination appears to be, when possible,
the most adequate for making the choice of the most proper disposal route.

3.3 Tritium monitoring in liquid media

To control tritium concentration in liquid waste streams before their processing
or discharge to the environment as well as tritium leakages from tritium handling sys-
tems the measurement of tritium concentration in a liquid medium is to be performed.
The sensitivity and response time required by the measurement are specifically depen-
dent upon the monitoring purpose.
Currently tritium monitoring in liquid media is achieved by means of grab sam-
pling and liquid scintillation counting. Continuous on-line scintillation counting sys-
tems have also been developed and applied (1). The former technique is the most sen-
sitive and reliable for measuring tritium concentration in water. As mentioned in ref.
(1) several automated liquid scintillation/batch sampling systems have been also devel-
oped consisting of a flow system that mixes the liquid scintillation cocktail and the
tritiated liquid sample to be measured and counts the resulting scintillation mixture

consisting of a device containing a small quantity of water. However. 3. absorbent bed colums and diffusion samplers are used to pick up HTO vapor from atmospheric air for tritium measurement purposes. Liquid scintillators.4 Tritium monitoring in atmospheric air HTO Bubblers. due to its low vapor pressure. Bubblers are the most commonly used. being continuously exposed to tritium contami- nated liquid streams. Bubbling a gas sample flow through water or glycol and then purging the circuit by clean air is an effective way to separate HTO vapor from some radioactive gases which may accompany tritium (1). The trapping mechanism is based on a simple isotopie exchange of HTO vapor with water. To prevent any tritium losses several bubblers contain- ing ethylene glycol can be used in series. (1) several type of solid scintil- lators have been applied. This draw-back is caused by the dirt and other radioactive materials which usually are suspended in the liquid streams to be monitored. A diffusion sampler is a simple system used for sampling HTO vapor from atmospheric air. However these systems are unable to give results in real time and therefore appear unadequate if a high sampling rate is needed. the average tritium concentration in the gaseous stream can be calculated. As mentioned in ref. In the case of the ethylene glycol firstly the HTO dissolution and than the isotopie exchange occurs. zeolites and ethylene glycol have been employed as sampling media for diffusion samplers (1). silica gels. For very long bubbling times the ethylene glycol is the most appropriate choice. After a sufficient bubbling time the concentration of the total tritium collected in the water as HTO is determined by liquid scintillation counting. This will consequently require a periodical replacement of the solid scintillator. Silica gel or molecular sieve columns may be also used to remove from atmo- spheric air HTO vapor which is than driven from the absorber bed by heating and collected as a condensate in a cold trap. The continuous on-line scintillation technique involves the use of flow cells containing a solid scintillator. All these suspended materials may of course be reduced by an adequate liquid filtering. through which the air stream to be monitored is bubbled. They usually consist of two simple gas washing bottles containing distilled water or ethylene glycol. No bubbling is necessary since HTO vapor will be picked up from tritiated air by exchange with this water. causing with time an irreversible fouling of the scintillator surface. However it is not excluded that some radioactive particles of very low size may pass through the filter pores. Being the gas flow rate and the bubbling time known. these type of scintillators can build up with time a background activity which is difficult to eliminate.in a standard liquid scintillation counter. A passive diffusion sampler has been developed and applied at Ontary Hydro's Nuclear Generating Stations (1). .

The difference between the first and second measurement will give the HTO concentration. <37 kBq.1). the amount of tritiated air samples that can be added inside a counter must be limited. It is however not specific to tritium since it responds to other airborne radioactive species as well as to ambient gamma fields.m"8 with an overall accuracy of ± 30%. 3. The counting method based on gas proportional counter is applied when the monitoring is required for tritium activities below the sensitivity limit of a ionization chamber (i. (1) measurements of tritium spe- cific activities of 0. they do not discriminate the activities due to HT. argon-methane) and atmospheric air is known to be deleterious to most counting gases. Anyhow the major advantage of such counters is their capability of discriminating external pene- trating radiations (e. HTO and HT The measurement of total tritium activity in atmospheric air may also be per- formed by using a ionization chamber or a gas proportional counter. An alternative method is to pass the air sample through a bubbler system in order to remove HTO and then to convert the residual HT to HTO by catalytic oxida- tion.m"3(0. the air sample is first measured to deter- mine the total tritium activity.g. In some cases a decontamination of HTO from other radioactive gases partially solved in the bubbler water may be needed.e. The measurement by scintillation counting of both the HTO activities (i. after being passed through a bubbler or a molecular sieve or a silica gel column. As reported in ref. . To this end the concentration of these gases in the bubbler water can be very much reduced by purging the water with clean air prior to scintillation counting (1). The counting method based on the ionization chamber gives a response in real time and is the most commonly used. 10 The exchange rate is diffusion limited and reproducible. 3. to determine the activity of HT.g.37 kBq.1). They are also more expensive and complex than ionization chambers. (1) the sensitivity of this sampler is about 500 cpm per 37 kBq-h. Since they require a counting gas (e.m"8)..m"8) are achievable with counting time of about 1 minute.m"8(10 mCi. This is true if no other radioactive gases are present or the used tritium detector has the capability of discriminating the radioactive particles emitted by radioactive gas eventually accompaning the tritium in the air atmosphere.01 micro Ci. They are not species specific tritium monitors i. The upper detection limit of such counters is however limited. typically to 37 MBq. To measure HTO in presence of HT.e. electrons produced by gamma radiations) or radioactive gases accompaning the tritium (see Tab. CHST).g. To reduce these interferences compensating chambers are currently used (see Tab. The resulting HTO is then removed again by flowing the oxidized gas through a second bubbler system. Then another sample is again measured.m"8).e the original one and that obtained by catalytic oxidation) picked up in the bubbler water will respectively give the HTO and HT concentration in the air sample. As pointed our in ref.. HTO or other tritiated gaseous species (e.

et al.. 23-25 Avril.5 Reference for Section 3 (1) Wong K. proposed IAEA Safety Series Procedures and Data Document. (2) Coste G. and Utting R. Dijon. . 11 3. Conditionnement des Déchets Tritiés Issus du Reacteur EL3. Actes des Jounées du Tritium. 1986.. CEN SACLAV (1986). Safe Handling of Tritium.Y.E. December 1987 under publication.

g. in presence of oxygen. hydraulic and/or lubricant oils etc. condensates) depending upon the applied ditritiation procedure. A part from those Tritium Handling Laboratories specifically aimed at perform- ing R&D activities in the field of the Fusion Reactor Technology. Nuclear Powers Reactors as well as Fuel Reprocessing Plants are at present the major sources of triti- um contaminated wastes.e. . The processing of gaseous effluents may in turn generate tritiated solids (e. Advanced nuclear plants such as Tritium Handling Facilities and future Ther- monuclear Fusion Reactors will highly contribute to increase the amounts and the contamination of tritiated wastes because of the much larger tritium activities that will be produced and handled in them. liquid and solids forms. contaminated equipments. HTO). tools. 4. pipings. C0 2 and HTO). A closed-cycle heavy water recovery system.Isotopie exchange reaction with environmental moisture.1 Tritiated wastes from Heavy Water Reactors (HWRs) and associated Tritium Recovery Plants Chronic low-level leakages of tritiated heavy water from HWRs moderator and coolant systems gives rise to tritium contamination in air atmosphere and aqueous effluents.autoradiolyse (i. It may be placed within the reactor containment or even outside in confinement rooms. .g. Liquid and solid tritiated wastes have the particular property of perma- nently generating tritiated gaseous effluents (outgassing) because of the: . Miscellaneous solids and organic liquids from maintenance and repair operation (e. The leakages from both moderator and coolant systems are collected in tanks.g. Distribution values between water and airborne tritium releases may vary depending on various factors (1). Primary wastes can be summarized as follows: 1. associated with the reactor. exhausted absorber beds) or liquids (e. is normally employed to keep tritium concentration in the recovered heavy water to an acceptable occupational level. production of CHST and.e. ORIGIN AND CHARACTERISTICS OF TRITIUM CONTAMINATED WASTES Usually tritium contaminated wastes are generated under gaseous. If the isotopie purity of heavy water from the moderator system is sufficiently high the effluent is fed directly back to the moderator pumping system. ÏZ 4. Different types of tritium-contaminated wastes are produced according to the various tritium handling operations in the reactor and associated tritium recovery plants. Otherwise it is sent to a clean-up system and then to the upgrading by water distillation or other process techniques (see Section 9). Spent reator components contaminated by heavy water.). HT. either purged with air or fitted with air dryer systems (1). . 2.desorption of volatile compounds (i. To ensure the control of airborne contamination the majority of heavy water systems are placed within the reactor containment envelope so that environmental emission and occupational exposure can kept at minimum.

concrete and wood debris.g. Being the reprocessing currently performed according to the standard PUREX flow-sheet. As a result very large volumes of tritiated aqueous effluents (e. temporary floor and wall coverings. Cladding hulls (60% of tritium released from the fuel). 100 m8/t heavy metal) have been produced. exhausted filters and IX resins. contamination control. As before mentioned the processing of gaseous effluents will itself lead to the production of other forms of tritiated wastes such as tritiated solids or condensates. 4.). 4.4 Tritiated wastes expected from future Thermonuclear Fusion Reactors and associated Tritium Handling Facilities Gaseous. These by-products will also be . Tritiated solid wastes generated as a by-product of tritium removal. swabs. gloves. etc.g. 13 3. 6. normal labora- tory and housekeeping operations (e.g. discarded plastic personnel suits. All these wastes will require an adequate processing to minimize any tritium losses to the environment. Miscellaneous solids from decontamination. liquid and solid tritium contaminated wastes will also be generated during the operation and maintenance of future Thermonuclear Fusion Reactors and associated Tritium Handling Facilities. 5. maps. Tritiated wastes currently arising from reprocessing plants include (1): 1. bottles. 2. after the fuel dissolution a considerable fraction of tritium present in the fuel is repeatedly diluted isotopically due to aqueous reagents introduced in the reprocessing cycle. If a modified Purex flow-sheet based on a tritium segregation/recycling concept will be applied in future it can be expected that the volume of tritiated aqueous ef- fluents might significantly decrease. e. Such wastes are managed. 4. con- centrated by distillation).5 m8/t of LWR fuel processed (2). rags. Tritiated aqueous wastes from common acid and water recovery systems where the different raffinâtes of the various Purex extractions cycles are processed (e. paper tissues.3 Tritiated wastes from Fuel Reprocessing Plants (FRPs) At commercial FRPs there have been so far no substantial attemps to confine tritium to as small a volume as possible. vermicu- lite air form respirators.2 Tritiated wastes from Light Water Reactors (LWRs) Because of their low tritium concentration both gaseous and liquid tritiated effluents are currently released to the environment after proper dilution.g. with the major attention being focused on their activation product content rather than tritium contamination level. likewise tritiated solids. Tritiated water concentrates generated as residual effluents from the heavy water clean-up and up-grading (tritium removal) system associated to a HWR. Tritiated liquid wastes generated by decontamination of primary wastes. and secondary wastes: 4. up to 5-0.

the European Communities Project aimed at constructing an experimental thermo- nuclear fusion device of the Tokamak type. and as tritrated liquids: .Miscellaneous combustible and/or compressible solids arising from decontamination operations (e. 4. exhausted filter cartriges. mopheads. shoecovers. 14 introduced into the procedures for processing directly generated liquid and solid tritiated wastes. scintillation cocktails. 4.Miscellaneous combustible and/or compressible solids arising from contamination control operations (e. . contaminated equipment.g. discarded piping and valves. while in Tab. aqueous leakages. solids decontamina- tion.).g. protective clothings.) and normal laboratory operations (e. . Excluding spent reactor components approximately the same type of tritiated wastes are to be expected from Tritium Handling Laboratories which could be design- ed and employed for research and development purposes in the field of the Fusion Reactor Technology (3). In Tab. blanket segments. etc.). hand basin.) as well as from general laboratory cleaning operations (e. tritiated water residues and condensates).2 taken from ref. gloves. contaminated by neutron activation by-products and arising from reactor maintenance operations (e. etc. .g.Tritium permeated hard wastes.Aqueous effluents coming from those areas of the Fusion Reactor and associated Tritium Handling Facilities where the risk of tritium contamination is low (e. swabs. etc.g. bubbler liquid. tritium rework and molecular sieve bed regeneration operations (e.). etc.1 an exemple is given of typical waste arising and sources as tenta- tively anticipated for NET* systems (3). vermiculite from air respirators.g. paper tissues. It is expected that main typical waste arisings from the operation of a Fusion Reactor and associated Tritium Handling Facilities would include (3) as tritiated solids: . etc. tools.g.Aqueous effluents arising from the aqueous leakage collection. discarded plastic personnel suites. .Organic liquids arising from plant maintenance (e. showers. IX resins.g.g. . samples bottles. etc. Next European Torus. hydraulic and lubricant oils.). . temporary floor and wall coverings. solvents. discarded reactor components such as first wall. (4) are shown typical tritiated waste activities and volumes expected for the operation and maintenance of the Darlington Tritium Removal Facility (see subsection 9.).1). rags.Miscellaneous non-compressible solids arising from plant equipment modification and maintenance operations (e.g. cata- lystes and getters etc. detergents. glove boxes and exhausted materials such as molecular sieves. drains). oil sludges) and normal laboratory operations (e.g.

GUT = Gaseous Waste Treatment System. L RED/ΟΧ beds (Cu/CuO) IAP. . E xhausted getters HT Substitution of getters Plasma exhaust purification system AP = Activation Products. IAP ■ Inert Atmosphere Purification System. Tritiated water HTO/AP Leakage collection Drip pans.1 · Typical tritiated wastes expected to arise from NET systems. first wall/ HT/AP Reactor maintenance First wall/blanket blanket segments) 5. GUT) 0 6. HT/AP Maintenance and service areas Decontamination solutions HT/AP Decontamination of equipmen' Decontamination and maintenance areas. TYPE OF WASTE TYPE OF GENERATING OPE RATION GENERATING SYSTE M OR AREA OR E QUIPME NT CONTAMINANT 1. floor sumps and leakage collec­ S spent activated carbon tion systems. E xausted catalysts HT Substitution of catalytic Systems for purification of gaseous wastes (AAP. 8. alkaline aqueous detergents) 4. floor sumps and leakeage collection sys­ HTO Tritium rework tems Tritium rework plant 2. Oil. Air Atmosphere Purification System.g. E xhausted IX­resins. lubricants Combined Maintenance of vacuum pumps Plasma exhaust pumping system. ACU. s IAP.TABLE 4. (acidic. E xhausted molecular sieves HTO Maintenance of: Plasma exhaust pumping system ­ cryopumps Tritium removal system from solid Li­ceramic or en ­ cryoadsorption beds liquid Li/Pb blankets ­ adsorption beds Plasma exhaust purification system System for purification of gaseous waste (AAP. GWT) I 7. AAP . Tritium permeated hard wastes (e. ACU. ACU ■ Air Clean­Up System. HT/AP Decontamination of various aqueous waste System for control and discharge of liquid aris­ D cart r idge f ilters. streams ing from drip pans.

Denver. Tritium Immobilization. et al.5 References for Section 4 (1) IAEA. EUR 6270 en (1979) European Appi. Proc. April 5-10. 193rd ACS Meeting.3 4. Future Trends for Routine Management Practices and Experimental research Activities. of Sym. . (4) Krochmalnek L . 234.S.4 <0.025 (25% KOD) (c) Pump oil 0-1. 1. WASTE ACTIVITY ESTIMATED MAX PRODUCTION TYPE (GBq) (Curies) (m -a ) LIQUID ( -kg" 1 ) (a) Water 37 · 10" β IO' 6 200 (b) Electrolyser Fluid 18-37 0.4-37 · 102 0. IAEA Technical Report Series No. Denver. USA (1987). 3 (1979). Conditioning and Handling of Tritiated Wastes at Canadian Nuclear Power Facilities. 16 TABLE 4.A.2 .2-100 0. Vienna. 3.. Soc. Management of Tritium Contaminated Wastes at the ETHEL Facility.4 (c) High Activity >37 · 10 2 >100 1. 1984.C. on Waste Disposal and Treatment for Fusion Reactor Systems.2 132 (Processible) (b) Medium Activity 7. Annual Meeting. IAEA.075 SOLID ( 'm" 3 ) (a) L ow Activity <7.0 0.Expected tritiated wastes associated with the operation of the Darlington TRF (4).Nucí. (2) McKay H. Management of Tritium at Nuclear Facilities.. No.. . Res. (3) Mannone F.. Sci. and Dworschak H. p. 1987.5-1.8 -10 3 0-50 0. Chem. Vol. Rept. Tech. paper presented at the Am.

such wastes have to be managed following the same procedures used for truly tritium contaminated waste. Since all commercial FRPs are normally operated on the standard Purex flow­ sheet basis very large volumes of tritiated aqueous effluents will consequently be produced (see subsection 4. i. Recycling tritiated aqueous streams in the early part of the plant so that the addi­ tion of a tritium-free solutions (e.e. 3. This is in order to avoid that. Tritium losses must be recovered in the most concentrate form. To this end all process operations which may generate these wastes or increase their volume are to be revised and adapted to the following operational criteria: 1. 17 5. the acidic scrub solution in the 1st extraction contactor) may be kept to a minimum and tritium may thus be concentrated in a smaller volume of effluent. even if they are only suspected of tritium contamination. TRITIATED WASTE MINIMIZATION AT SOURCE The problems posed by the management of trit 'ted waste require at first that all reasonable attemps be made in order to minimize at source tritiated wastes arising from process operations. confinement of tritium into a smaller volume of ef­ fluents may be a mandatory requirement to meet in future for safety reasons. 2. In view of this all reasonable attemps are to be made to avoid any possible isotopie dilutions.g.e. In FRPs tritium confinement may be attained by: 1. Confinement. If a total recycle is applied. 2.1 Tritium confinement In the present scenario based essentially on the existing nuclear plant the tritium confinement concept applies particularly to fuel reprocessing plants where large dilu­ tions are the current rule. the volume of the withdrawal has to be at least as great as that of the tritium-free aqueous scrub. Such effluents may be discharged directly to the sea (dilution effect) or the atmo­ sphere (sun evaporation) depending on sites where plants are located and such proce­ dures feasibles. This implies (1-3) the application of a tritium barrier concept. Some ancillary operations originating non-radioactive solid wastes must be carried out as far as possible outside the controlled areas of the plant. Usually the withdrawal of a certain volume of the tritiated liquid stream from the recycle system is forseen. This in order to reduce to a minimum the tritium "spreading" through any process streams. which is fed to the scrub section of the 1*' contactor. segregation and recycle of tritium must be enhanced in those parts of a plant where tritium is produced and/or processed. 5.3). the scrubbing of the organic phase in the 1st contactor carried out using a tritium-free acid scrub to remove the fraction of tritiated aqueous phase dissolved and entrained in it. Many recycle schemes have been proposed and reviewed (4-10). Segregating tritiated aqueous streams in the early part of a plant where the head­ end treatments and the Γ' extraction cycle are carried out. For inland plants located near closely populated sites where on-site liquid tritium releases are limited. i. because of their origin. .

3.e. The recycle of aqueous streams entraining organic impurities could generated op- erational problems during the PUREX process operation. The recovery of tritium losses applies particularly to tritiated gaseous streams arising in conventional FRPs (e. An addition of N0 2 to make up nitric acid is required to attain the maximum re- cycle factor. 2. 18 Recycling of course will increase the tritium concentration throughout the early part of the plant.g. This will hinder to reach too high steady-state tritium concentrations. ETHEL at the JRC-Ispra site). some drawbacks associated with tritium segregation/recycling have been identified (11) such as: 1. The segregation/recycling is aimed at obtaining a tritium effluent stream suitably con- centrated for subsequent conditioning and disposal or for further concentration by an isotopie enrichment process.g.g. . 5. local and global ex- posures. These atmospheres are normally purified from tritium in one-through or alternatively in a recirculatory mode (see Section 8). To recover tritium losses and to prevent at the same time eccessive dilution of tritium in the atmosphere of tritium enclosures the following critera must be applied in designing Tritium Handling Facilities (12): 1. The fraction of tritiated water vapor to be recovered from off-gases and vessel ventilation streams will increase as the recycle factor increases.2 Recovery of tritium losses The recovery of tritium losses is aimed at reducing the tritium concentration of waste arisings. on the degree of dilution attained by tritium in that atmosphere. The volume of tritium handling enclosure must be kept to a minimum. Although its application at FRPs will involve the use of a known and relatively simply technology. It follows that the costs of an overall tritium containment system will highly depend on the size of the atmosphere detritiation unit. It is mainly performed for safety reasons. In all these operations the volume reduction of tritiated effluents is essential because their costs would be otherwise prohibitive. A concentration limit has to be defined based on plant safety con- siderations. Containment and hazard problems would be complicated due to the increased steady-state concentration of tritium in the plant. 2. vessel ventilation streams) and to the enclosure atmospheres of special Tritium Handling Facilities associated to HWRs (e. i. Tritium Removal Facility at Darlington and Tritium Extraction Plant at Chalk River) or especially designed to perform R&D activities in the field of Fusion Reactor Technology (e. process off-gases. due to the radioecological benefits that can be achieved in such a way by the minimization of tritium releases to the environment and the consequent reduction of operational. 4. TPL at the JAERI-Tokai site. In these facilities the atmospheres of tritium handling or processing enclosures need to be purified from tritium escaped from equipment or intentionally introduced in them for experimental purposes. A double-walled containment must be employed along with intermediate tritium scavenging by a gas stream. TSTA at the LASL site.

they must be procedurally treat- ed as tritium-contaminated. (3) Miquel P. quoted by ref.L. CONF-760806-3 (1976).C.. Retention of Gaseous Fission Products in Reprocessing LMFBR Fuels. . et al. quoted by ref. Conse- quently.. Adivisory Group Meeting on Reprocessing of LMFBR Fuel. Report ICP-1041 (1974). et al. et al. 10. Release of Tritium from Fuel and Collection for Storage. Report Jül-1099-CT (1974). Advisory Group Meeting on Reprocessing of LMFBR Fuel. May 1976.. 5. 1976). Significant achievements in this way can be attained by locating offices outside the controlled areas of tritium handling facilities and un- packaging materials and equipment before entering these areas. (7) Burger L. Leningrad.. Le Retraitement des Combustibles "Rapides" en France. American Nuclear Society.. (4) Burch W.. Leningrad. since all wastes generated in a controlled area of a tritium handling labora- tory or plant. Karlsruhe (1977) 497. of CEC Seminar on Radioactive Effluents from Nuclear Fuel Processing Plants.. 10. Advisory Group Meeting on Reprocessing of LMFBR Fuel.. To reduce the amount of suspect wastes which after packaging have to be shipped to surface storage or burial grounds.E. Head-end and Nuclear Gas Purification Research on LMFBR Fuel Reprocessing in Belgium. (6) Sauteron J. Trevorrow L. et al. (5) Baetsle L. 4. 19 3.3 Minimization of suspect solid wastes At the present time none of the methods currently applied in order to determine the tritium content in tritium-contaminated solid wastes is non-destructive. Obviously this is done for safety reasons even if pratically all such wastes are non-radioactive. BNWL-SA- 5778.4 References for Section 5 (1) Schenez H. ANS- AIChE meeting.H. are suspected of tritium contamination. Controlling Airborne Effluents from Fuel Cycle Plants (Proc. Possibly a closed cycle with a dried gas stream has to be applied for tritium scavenging. May 1976. (2) Musgrave B. their mini- mization at source is mandatory. Tritiated gaseous effluents are treated in an atmosphere detritiation system for tritium removal. Hinsdale (1976). Leningrad. Proc. 5. 10. May 1976.D. quoted by ref. It is worth noting that by limiting tritium dilution in tritiated effluents also the cost of an isotopie enrichment plant can be reduced.

SCK/CEN.. et al. IAEA. 1. Res. et al. Vienna (1980) 177.. Tritium Immobilization. Mol Rep. Die Entsorgung tritumhältiger Abwässer-Technik und Sicherheit. .Nucí. Symp. IAEA. Vienna.. Management of Gaseous Wastes from Nuclear Facilities (Proc. 20 (8) Henrich E.A. Vol. Sci. Interner Bericht KFA-ICT-IB- 468/82.. Rept. (11) Bruggeman A. Kernforschungsanlage Jülich. . (12) Dolle L. Appendix II of IAEA Technical Reports Series No. 203. EUR 6270 en (1979) European Appi. The Concentration of Tritium in the Aqueous and Solid Waste of LWR Fuel Reprocessing. 1980). Centre d'étude de l'énergie nucléaire. Brücher H. 3 (1979).. 1981. (10) McKay H.C.. Tech. No. (9) Hartmann K. Vienna. Assessment of Some Methods for the Separation of Tritium from Aqueous Effluents of a Reprocessing Plant.. Production and Treatment of Tritiated Wastes in France.

smeart tests. combustible or incombustible materials). These criteria are often dictated by the subse- quent tritium management routes one intends to apply (e.e. Their contamination level is thus evaluated through their previous contamina- tion "history" event though this method only offers a rough estimate of their actual tritium content (2). nature and size. a specific activity measurement based on such a technique often may result complex and not sufficiently representative (1). for tritiated hardwares and miscellaneous solid. which will arise from the operation and maintenance of future Fusion Reactors and associated Tritium Handling Plants. inorganic).High tritium level wastes.Medium or high tritium level wastes. . One has to point out. including miscellaneous combustible and/or compactible solids arising from normal laboratory operations as well as from decon- tamination. \ . it may be also to wastes which are only bagged in bulk. compressible or uncom- pressible.level of tritium contamination (i.g. if needed. Solid wastes could be classified as: . including tritium permeated hardwares arising from the repair and maintenance operations in tritium handling plants or reactor systems.physical state (gaseous. . medium and high tritium level wastes will depend of course on standards and regulations applied at the country of the considered plant. To assist.g. This is due to the massive or miscellaneous nature of solid wastes as well as to the non-homogeneous distribution of tritium in them. see Appendix I) and the outgas- sing rate may also be employed. the specific activity of tritium) so that suspect.e. . . which is currently done by sampling and scintillation counting do not meet particular difficulties. that while the determination the specific activity of a tri- tiated liquid. As illustrated in Section 4 solid and liquid tritiated wastes. modification and maintenance operations on plant equipments. medium and highly tritium contaminated wastes may be defined. slightly. The boundary between low. liquid or solid). This latter technique is normally applied to drummed tritiated wastes (see Section 13) but. are expected to include a large range of material of different origin. glove boxes and fume hoods. treatment for tritium recy- cle or tritium immobilization for storage or disposal as a waste). however.Suspect or slightly tritium contaminated wastes including miscellaneous combustible and/or compactible solids arising from general laboratory cleaning and contamina- tion control operations. In principle the classification of tritium contaminated waste materials should take into account their . 21 6. other complementary techniques based on the mea- surement of the surface activity (i.chemical nature (organic. .ability to accept or not a volume reduction treatment (e. SORTING AND CLASSIFICATION OF TRITIATED WASTES Sorting and classification into categories of tritium contaminated wastes are essential operations to be carried out as much as possible at source according to critera which may vary from plant to plant.

6. including large volume aqueous streams coming from some low risk areas of a tritium handling plant or laboratory (e.. under publication. 22 Liquid wastes could be classified as: . Vassallo G. deconta- mination and cleaning operations. 1988.1 Reference for Section 6 (1) Wong K. . Safe Handling of Tritium.. low volume organic liquids arising from plant maintenance and routine laboratory operations. including medium to low volume waters arising from eventually contaminated drains and sumps as well as from molecular sieve regenera- tion operations. including: . low volume waters arising from laboratory experiments. tritium rework. showers. hand basins drains and sumps).g. .Y and Utting R.Suspect or trace-level effluents. Canada. The Routine Handling Processing and Storage of Liquid and Solid Waste at the European Tritium Handling Experi- mental Laboratory. Toronto. paper presented at Third Topical Meeting on Tritium Tech- nology in Fission. (2) Mannone F. and Dworschak H.Low tritium level effluents. molecular sieve regeneration operations as well as . .Medium or high tritium level effluents. December 1987.. proposed IAEA Safety Series Procedures and Data Document.E. Fusion and Isotopie Application. May 1-6.

are tentatively indicated and assumed for evaluating safety requirements associated with different storage situations (store failure or constant leakage of store). In reference (1) some "initial" tritium loss levels.2 Required degree of tritium immobilization It is unanimously recognized that. 0. The calculated tritium leakage limits amount to 0. 0. some loss of tritium is normally expected. A maximum limit value of 0. In the event that the outer waste containment package may be breached during the above operations. even if desirable. i. 23 IMMOBILIZATION AND CONTAINMENT OF TRITIUM FOR WASTE MANAGEMENT PURPOSES 7. 1% and 0. In case of a store failure and assuming the above "initial" loss values. all causes of tritium re- leases to the environment occuring during the fission reactor fuel cycle.82 or 123 years if an "initial" tritium loss of 10%. 1% or 0.1% are assumed respectively. As illustrated below.). However.001% per day (i.009%.36% per years. 1% or 0.5).3). In case of a constant leakage of store and assuming twice the "initial" loss val- ues.1% loss value respectively. The period amounts to 41. This means that during the fuel cycle. corresponding to about one tenth of the largest limit value) is finally . immobilization is also aimed at preventing the spreading of tri- tium in the environment with a consequent exposure to a radiation dose unacceptable for workers and general population. tritium immobilization may be attained up to a certain ex- tent by incorporating tritiated wastes into solid matrix materials (e. cements. polyester or epoxy resins.g. dryers.1% is respectively assumed. due to outgassing properties and teachability of final tritiated composites (see subsection 9. transportation. 7. 1% or 0. as demonstrated by many extensive experimental studies.e. 10%. the period after which the tritium accidentally released will at maximum be equal to that "initially" lost) has been calculated.tritium in- corporated in such matrices alone cannot be considered sufficiently immobilized.g. even if small. It is however very difficult to define to what percentage this loss will amount. To attain an adequate containment of tritium in solid and solidified liquid waste the concept of the multiple physical barrier is currently applied (see subsection 7.007% or 0. storage or disposal).00007% per day if "initial" loss values of twice 10%. cannot in practice be completely eliminated. etc.e. the period for which a safe store of tritium should be guaranted (i. It is intended that within this limit the total tritium release will never at any time exeed twice the "ini- tial" 10%. the attained degree of immobilization being dependent upon the chemical form and the physical state of tritiated wastes as well as on the type of matrix utilized. may be done under the safest condi- tions. a maximum permissible leakage limit has been calculated.e.1%.1 General considerations By tritium immobilization is intended the application of all those processes designed to immobilize tritium in such a chemical form or under such a physical con- dition that after an appropriate packaging the subsequent waste management opera- tions (e.

Among other topics. 7. In this study the main topics requiring further R&D work have also been indicated namely: . 7. 7. isotopie and chemical exchange. Drying agents II.3 Potentially applicable methods As indicated in some preceding literature surveys (1-4) several methods are potentially applicable for implementing the immobilization of tritium in a stable solid form.g. Another immobilization technique which is one of the most in use is the simple packaging of tritium gas in stainless steel cylinders.1 where some technical aspects of their application are also sum- marized.4 Criteria for selecting an immobilizing agent The choice of the most suitable matrix for tritium immobilization is currently governed by some basic criteria that in some cases are conflicting. Materials of first and second group and certain capolymers of third group spe- cially fit for immobilizing tritiated water or water vapour while materials of fourth group and someones of third group (e.g. Inorganic hydrates and cements III. 24 suggested (1) as the likely one to be acceptable after a tritium immobilization pro- cedure. The application of one or others of these materials primarily depends on the chemical form of tritium to be immobilized (e.Tritium immobilization techniques and flow-sheets to be extensively developed in order to attain the highest tritium incorporation yields. Organic polymers IV. This in order to ensure that all the possible mechanisms of tritium release (e. . A proportional order of merit has been proposed by McKay in a CEC sponsored study on the potential tritium immobilization routes (1).Tritium retention properties of solid matrices selected for tritium immobilization to be tested on an experimental basis and over a sufficient long period. chemical decom- position.2. All the available methods are compared in Tab. radiolysis. The order of merit derived in this study was based on the assessment of some properties which are summarized in Tab. In most cases they involve the preparation of a tritiated solid compounds by using special materials acting as immobilizing media. The most known candidate mate- rials are: I. tritiated hydrogen or water) which must be compatible with the selected material. 7. the isotopie enrichment and the employ of physical barriers to further contain tritium have been also indicated. . Metal hydrides. teachability) may be taken into account.g hydrogenated polystyrene) can be properly utilized only for immobilizing tritiated hydrogen.

sieves) 10­20 ­ Stable up to 700°C Possible chemical ex­ tiary containers with sor­ (Na 2 0 Al 2 0 3 2Si0 2 XH 2 0) ­ Drying properties change between firmly tent materials filling in­ at high temperature and loosely bound termediate voids) Low equilibrium vapor water pressure (5x10' bar) at 25 s and 17X water loading. leakage Well established sed or at sub­ SS CYLINDERS Tritium in a easily through valves technology atmospheric available form at rv pressure) any time Liquid or SORPTION BY DRYING AGENTS vapor . secondary and ter­ Zeolites (Mol.TABLE 7.2 stability Permeation of HT through HYDROGEN (1 bar)<1> Potential for recover­ the steel container during (HT) ΥΗ χ (Τ) moderate t"C 2.1 ­ Potentially applicable methods for tritium immobilization purposes. Commercially available in pellet and bead forms .2 ing HT at a later data the MH (T) formation at elevated temperatures High purity needed for both metal and HT reac­ tion components gas (compres­ GAS PACKAGING IN ­ Simple & economic Potential T.2 drogen pressure MHx(T) dusts and HT most advanced without emblittement (1 bar)<1> Well defined thermal handling at 600°C TRITIATED T i H í T ) 400"C­600*C 4.2 Strong water retention Appreciable water solu­ Well established manufac­ Container capable of con­ (2CaS0 4 H20> Low costs bility turing routes taining He or provided Too high vapor pressure with a venting system aimed under 100°C at preventing uncontrolled Low water loadings HTO release to the environ­ Activated Alumina ­20 ­ Large water loading: Low equilibrium vapor ment (AljOj xH 2 0) pressure only at very Containment based on the TRITIATED Silica xerogels ­40 low water loadings. TRITIUM PHYSICAL IMMOBILIZATION H 2 or H 2 0 ADVANTAGES DISADVANTAGES STAGE OF PACKAGE FORM E STAT EM THODS * MATRICE S CAPACITY DEVELOPMENT REQUIREMENTS (wtX) gas CONVERSION TO METAL High capacity for He Relatively high cost Only laboratory scale Cylinders capable of cont­ HYDRIDES (ΜΗχ(Τ)) Low equilibrium hy­ Hazards associated with development but the taining He from T. use of multiple physical WATER (Si0 2 xH 2 0) Low water retention above barrier systems (i.(T) 600°C­900°C 2.e. pri­ (HTO) 100­C mary. decay ZrH. "Burned" gypsum 6.

0. of development POLYMERIZATION poration yields By-product formation Limited stability to heating.7 275"C and 100°C scale impracticable because Manufacturing routes . radiations & wheather ing (1) 1 bar = 100 kPa. HAC (3 > 50-57 High water capacity water held inside pores technology IN) Low water vapor and capillaries of the pressure hydrated cement mass Water and moisture contacts must be prevented to avoid tritium leaching and chemical exchange Liquid CONVERSION TO Very good resistente C-H2 handling hazard Very early stage TRITIATED C 2 H 2 & to water leaching insufficient T-incor. 3 CaO AljOj 6H 2 0 29 pressure even at high form) or reduced rehydra- . still to be established (Hydroxylapatite) Low equilibrium vapor inhalation hazards (dust . OPC<2> 25-28 Low costs Mobility of tritiated Most developed . (3) High Alumina Cement.8 respectively of difficult dehydration. 3CaS0. .Potentially applicable methods for tritium immobilization purposes (cont.1 . (2) Ordinary Portland Cement. Strong water retention Utilization of hydroxy- vapor NIC HYDRATES up to 800°C.) Liquid or FORMATION OF INORGA. no tion kinetics (pellets 31H 2 0 hygroscopic properties form) (ettringite) Hydroxylapatite occurs naturally & shows the highest water retention strenght TRITIATED WATER Liquid HYDRATION OF CEMENTS <HTO) . 3 C a j i P O ^ Ca(OH) 2 1. 46 water loadings. 3 Ca3(P0 4 ) 2 2H 2 0 3. 3 CaO A1. 900°C. lapatite on a large plant .TABLE 7.

The main drawback to these metal hydrides is the necessity to use tritiated hydrogen at high tempera- tures (~600eC) for their preparation. Polymer impregnation of the cement reduces the tritium leach-rates in water. (C) Organic polymers (1) Hydrogenated polystyrene Organic compounds are subject to various types of instability and high tritium (2) Polyethylene incorporation yields are often difficult to achieve owing to side-reactions. polymers using a water feed would generally be expected to give poor immobilization. subject to some radiolysis.2 . Molecular hydrates sieves can also take up appreciable quantities of water while retaining a very (2) Molecular sieves low vapour pressure. and the tritium is incorporated in a single reaction stage. . (B) Metal hydrides (1) Zirconium hydride Zirconium hydride has been shown to fix tritium just sufficiently well in leach- (2) Titanium hydride ing experiments and the best conditions for its preparation for tritium immobi- lization have been extensively studied in the laboratory. A low water vapour pressure is not a sufficient crite- rion. In (3) Polyvinylacetate virtually all cases there would be a necessity to recover. Titanium hydride ap- pears to be a good alternative. (D) Hydraulic cement Cement is a particular example in the category of inorganic hydrates. etc. and may even be superior. but it is still to be demonstrated that the tritium is in fact sufficiently immobilized. leach resistances and radiation stability. but the evidence on the degree of reduction is conflicting. As usu- ally prepared it immobilizes only part of its water content even if the propor- tion immobilized slowly increases on standing ("curing").TABLE 7. since isotopìe exchange processes can still be envisaged that would render the tritium mobile. the long-term stability of polymer-impreg- nated cement. All the other indicated polymers have the disadvantage of requiring a hydrogen or acetylene feed. There are no obvious disadvantages. is also doubtful. Tritiated water can be Incorporated in these materials by (3) Calcium aluminate hydrate a simple heating/dehydration-cooling/rehydration cycle. burn and recycle by- (4) Sili cone/acetylene addition compounds products. GROUPS OF MATERIALS IN MERIT ORDER OF MATERIALS WITHIN GROUPS PROPERTIES MERIT ORDER (A) Inorganic hydrates.The order of merit concerning groups of matrix materials available for tritium immobilization as derived from the McKay study (1). Hydrogenated polystyrene may be the best choice since it has good me- chanical properties. (1) Calcium phosphate and hydroxylaptite Insoluble hydrates of very low water vapour pressure are available.

High yield in terms of tritium incorporation.Low flammability. physical state and concentration of tritium in the waste form but also depending on what of the available waste storage or disposal routes (e.Low costs of matrix production and tritium incorporation.High capacity for tritium.1 taken from ref.High chemical. the containment based on integrated multiple barrier systems has been applied as the only effective mean to reduce the environmental tritium release from a tritiated waste composite to an acceptably low level.5 The multiple physical barrier concept Due to the absence of an adequate tritiated waste immobilization matrix or procedure as well as of container the integrity of which may be guaranted for many tens of years. 28 As indicated in ref. the use for tritium immobilization purposes of a solid matrix would become acceptable if integrated in a multi-barrier system. . encapsulation) with some containment options such as simple containerization or simultaneous containerization and container encapsulation. On the other end if it is true that the overall efficiency of tritium containment mainly relies on the integrated employ of these barriers. (5). .Low exchange rate with environmental water. and how much important will be its re- sistence properties related to these conditions. Costs of matrix production and tritium in- corporation becomes also less important for the same reason. The weight of remaining criteria may be more or less important depending on what kind of final route (storage. Storage and disposal conditions will determine in fact to what extent the material will be subjected to heating.g.g. moisture etc. Consequently even simple and cheap solidification or encapsulating media such as hydraulic cements can still satisfactorily be employed. impregnation. water leaching.Low chemical and radiological toxicity. surface storage. (1) the most appropriate matrix should have the following properties: . thermal and radiolytic stability. This is done not only in compliance with the chemical form. . coating. A still more enhanced barrier effect has been attained by overpacking the waste immobilization matrix into multiwalled containers provided with absorbing materials for filling intermediate annular voids. The concept essentially relies on the application of a sequence of successive physical barriers. The matrix and physical barrier materials as well as the various containers are usually selected and assembled case by case. . Different multi-barrier containment systems have been assembled by combining various additional treatment that may be applied on a waste immobilization matrix (e. . burial or repository) is envisaged for the tritium immobilization product. 7. than it can be concluded that even if insufficient by itself. each of them giving a contribute to the overall tritium containment. Note that high capacity for tritium becomes less important if the tritium enrich- ment is carried out before immobilization. 7. . . An exemple of what kind of physical barriers a multibarrier system may include is given in Fig. shallow inground burial or deep geological repository) will be subsequently applied.

1.P. WZMZnZMZZM^container Secondary FIGURE 7. Tritiated Waste Conditioning. IAEA Technical Reports Series No. (3) IAEA.. (2) IAEA. Vienna.C. Ontario Hydro Research Division Report No. Rept. Tritium Immobilization.1 to 12. 1981. Res.. 203. Immobilized V/MMMMM/m tritiated waste •Primary container •Encapsuling layer (optional) !/ H iii' . IAEA Technical Reports Series No. 12. 29 Other exemples of multibarrier system are illustrated in Section 12. Tech.1 Multiple barrier system conceptually assumed and experimentally investigated at Ontario Hydro for tritiated waste containment and packaging (S). 85-279-K(1985). 1984.6 References for Section 7 (1) McKay H.L. and Rayan J. 7. IAEA. . Figs. 234. The Technology of Tritium Tixation and Storage. Vol..Performance of Con- tainerized and Encapsulated Waste Forms. Vienna.A. No. Management of Tritium at Nuclear Facilities. BNWL-1807 (1973). (4) Burger L. . Part III . (5) Krasznai J.L. Handling of Tritium Bearing Wastes. EUR 6270 en (1979) Europen Appi.*ίιί^ί4 t * * * * * # f.3. Sci. IAEA.. 3 (1979) 599.ï I 1 -1ιί1.Nucí.

30

8. DETRITIATION OF GASEOUS WASTES

As already illustrated in Section 4 tritiated gaseous wastes will arise not only
from conventional plants (e.g. FRPs, HWRs, Candu Reactors, etc.) and special Tritium
Handling Facilities associated to these plants (e.g. TRF at Darlington, TEP at Chalk
River) but also from all those plants or facilities specially designed to perform R&D
activities in the fields of the Fusion Reactor Technology (e.g. TSTA at Los Alamos,
TPL at Tokai, ETHEL at Ispra).
In these facilities the atmospheres of tritium handling or processing enclosures
needs to be continually purified to reduce tritium releases to working areas and exter-
nal environments, i.e. the risks of unacceptable occupational, local and global tritium
exposures.
Any increase beyond the admitted level of tritium concentration of the enclo-
sure atmosphere is monitored and alarmed in real time by means of suitable detectors
(see Section 3).
The presence in these atmospheres of tritium (in elemental or oxide forms or
both) may be due to escaping from equipment or to intentional contamination for
experimental purposes. According to the type of ventilation applied to the enclosure
the atmosphere detritiation may be achieved either in a one-through or a recirculatory
mode.
According to the current practice the atmosphere enclosures containing HT and
HTO are in most cases detritiated by a closed treatment cycle and through a detritia-
tion unit which normally is an essential component of the overall tritium containment
system. HT is removed from the gaseous stream by catalytic oxidation. The resulting
HTO vapor is picked up along with the HTO originally present in the gas mixture by
passing the gaseous stream through a bed of dryer material. To eliminate any needs of
recycling the carrier gas still containing HTO to the detritiation unit, a counter cur-
rent operating mode is applied. A line of several successive bed columns containing
the dryer material in a suitable form (e.g., molecular sieves in pellet form) is currently
used. After saturation and removal from the line Of the first column (for discharge to
waste or regeneration), a new fresh bed column is introduced at the end of the line.
This procedure normally ensures a tritium decontamination of the carrier gas enough
to allow, after monitoring, the recycle to the enclosure or the descharge to the stack.
The detritiation of gaseous waste streams will itself lead to the production of
other forms of tritiated wastes such as exhausted dryer materials or liquid condensates.
These products will be introduced into the procedures for processing liquid and solid
tritiated wastes (1).
An alternative to the catalytic oxidation/sorption on dryers, which uses in a
one-through mode a regenerable chemical getter for a direct tritium scavenging out of
inert {jases, has been experimentally investigated and applied at Ontario Hydro. In
particular the tritium removal properties of the Zr 2 Fe alloy have been tested for this
purpose (2).
Further a process clean-up system based on the use of Zr 3 Fe as tritium removal getter
bed has been constructed at Ontario Hydro research laboratories as an integrated part
of the large scale gas Chromatograph facility which is under development for separat-
ing hydrogen isotopes. The performances of such tritium removal getter have been
determined (3). ! ' ,
«

31

8.1 References for Section 8

(1) Mannone F., Vassallo G. and Dworschak H., The Routine Handling Processing
and Storage of Liquid and Solid Waste at the European Tritium Handling Experi-
mental Laboratory, paper presented at Third Topical Meeting on Tritium
Technology in Fission, Fusion and Isotopie Application, Toronto, Canada, May
1-6, 1988.

(2) Kherani N.P. et al., Tritium Removal from Inert Gases using Zr^Fe, Ontario
Hydro Research Div., paper presented aat the 12th Symposium on Fusion Eng.,
Monterey, California, USA October 1987.

(3) Shmayda et al., Tritium Removal from Noble Gas Streams, Ontario Hydro
Research Div., paper presented at the 34 th AVS National Symposium, Anaheim,
California, USA, November 1987.

32

9. TREATMENT AND CONDITIONING OF TRITIATED LIQUID WASTES

9.1 Tritium separation and enrichment

The isotopie separation of tritium from tritiated aqueous wastes and its subse­
quent enrichment is normally performed in order to obtain:
- a product stream of reduced volume and increased tritium concentration that will
be either stored for later use or disposed of, depending on its purity and concentra­
tion;
- a large volume detritiated waste stream that will be recycled within the generating
system or discharged to the environment.
The tritium separation is essentially aimed at reducing tritium releases and con­
sequently occupational, local and global exposures. Its enrichment is aimed at raising
tritium concentration in the separated product to such a level that tritium storage or
disposal become more economic.
Therefore the isotopie separation and enrichment of tritium appears to be
always beneficai because it enables a reduction of costs of the subsequent tritium
immobilization, transport and storage or disposal as well as the risks of unacceptable
environmental tritium releases. This even beyond the market value of the pure tritium
that may be recovered.
Anyhow one has to point out that the decision on whether to recover and then
to immobilize and store or dispose of tritium is primarily a result of an assessment
involving both radiological health and recovery process costs.
The isotopie separation and enrichment of tritium from tritiated waste waters
may be achieved by implementing a variety of process methods. Single (e.g., water
distillation) repeated (e.g., multistage electrolysis) and combined processes (e.g., cata­
lytic conversion and cryogenic distillation) are in principle available, all of them
already being designed for producing and detritiating a reactor heavy water.
Schematic flow diagrams illustrating these processes are shown in Figs. 1 to 6 of
Appendix II. Advantages and draw backs are summarized in Tab. 9.1.
In general the choice either of these process techniques will be influenced by several
factors (1) the most important being:
- Tritium concentration and impurity content of the initial waste stream.
- Subsequent retrievable storage or disposal option intended for the enriched product
stream.
- Related safety consideration.
- Costs.
Obviously the criteria on which is based the choice of a process technique suit­
able for processing a tritiated light water are different from these used for the heavy
water production and purification purposes. The latter case, where the species to be
separated are Τ and D, is indeed to be distinguished from the former case where Η
and Τ are to be separated. To give an exemple water distillation (on a high efficiency
packing column), which is the most attractive process because of its great simplicity,
appears to be more effective as a Η-T than a D-T separation process, due to its low
D-T separation efficiency.

TABLE 9.1 ­ Process methods applicable for Tritium separation and enrichment purposes.

PROCESS METHOD Τ­SEPARAT ION TEMPERAT. TRITIUM END­
ADVANTAGES DISADVANTAGES REF.
FACTOR <°C> PRODUCT FORM

SF too low, in case of T/D separation, large
Direct Distillation Very simple method. Known tech­ volume columns, high energy consumption. Τ
(DD) ­1.0 60 HTO, DTO, T,0 , „ .. , 1.15.19
' 2 nology. No f ire/explosion in the most radiotoxic form (HTO or DTO) and
hazard concentrated above the feed value (operational
exposure)

Cryogenic Industrial experience existing. Very important cost of refrigeration. Fire/
Distillation CD) 2.0 ­253 HT. DT. T 2 Highly enriched end­products explosion hazard, gaseous feed needed 3.15

High separation factor. High energy and investment costs for a multi­
Direct (multistage)­ HTO
Industrial experience existing stage use. Fire/explosion hazard. Τ end­product
Electrolysis 5­20 DTO, Τ,Ο 15,19
in the most radiotoxic form (HTO or DTO) and T­
(DE)
concentration above the feed value (operational
exposure)

Direct (singlestage)
Highly enriched end­product. Unsuitable when a large plant capacity is ω
Electrolysis n.a. 3,15 ω
High depletion capacity. Indu­ needed. High electricity consuption, fire/
(OE ♦ CD)
dustrial experience existing explosion hazard.
Vapor Phase Well developed on an industrial
Catalytic 5 (1) up to scale. Highly enriched end­product. Low Separation Factor, high process tempera­ 1.3­6.
Exchange 26­36 (2) 200 Low radiation hazard. Preferable ture & multistage system needed. Fire/explo­ 15
(VPCE ♦ CD) for processing slightly tritiated sion hazard
waters

Combined Electrolysis Highly enriched end­product. High Complexity of process, Τ­concentration above
Catalytic Exchange 100 (3) 25 depletion capacity. Advantageous the feed value (operational exposure). Develop­ 1.3.15,
(CECE ♦ CD) for processing slightly tritiated ed on a lab./pilot scale only. Fire/explosion 16­18
waters hazard

Liquid Phase Compared with VPCE, better contain­
Catalytic Exchange ­20 (4) ­50 ment & operability (lower explo­ Developed on a lab./pilot scale only (5) 1.3,12­
(LPCE ♦ CD) sion hazard) & operating costs 14

(1) at the Grenoble (F) plant; (2) at the Darlington (Canada) TRF; (3) at the Mol (B) SCK/CEN pilot plant; (4) at the Chalk River (Canada)
TEP; (5) first full­scale plant experience expected from TEP at Chalk River,
n.a. * not available.

34

However water distillation appear to be, likewise the direct multistage electroly-
sis process, less advantageous from the radiological point of view, since the tritium
enriched product is obtained in the most radiotoxic aqueous form (HTO or DTO).
Furthermore, in spite of the water distillation semplicity, it appears more con-
venient that both recycling and long-term storage of recovered tritium be made in its
elemental form. This because the storage of tritiated water is more complicated than
that of elemental tritium, due to problem of self-radiolysis.
Therefore the most convenient technique for recovering tritium in a concentrat-
ed elemental form results from the combination of two different processes, namely (a)
a transfer process whereby tritium passes from a tritiated heavy or light water form
(DTO or HTO) to a tritiated deuterium or hydrogen form (DT or HT) and (b) an
enrichment process that separes and concentrates tritium in its elemental form from
the concentrated elemental forms of deuterium or hydrogen respectively.
Transfer process options which may used for tritium recovery from reactor
heavy water are the following (2,3):
(a) Vapour-Phase Catalytic Exchange (VPCE) of tritiated D 2 0 vapour with D 2 /DT
mixture (4-6).
(b) Direct Electrolysis (DE) of tritiated D 2 0, producing a D 2 /DT mixture.
(c) Combined Electrolysis-Catalytic Exchange (CECE) (7-11) of tritiated D 2 0 in the
liquid phase with D2/DT producing a D 2 /DT stream enriched in tritium.
(d) Liquid-Phase Catalytic Exchange (LPCE) (12-14) of tritiated DjO with D 2 pro-
ducing a D 2 /DT mixture.
Each of them may be coupled with a subsequent enrichment process. Usually
cryogenic distillation is applied, being the only one developed on a large-scale and
therefore applicable for this purpose. As pointed out in ref. (15) for a given DF to be
attained, the size of the cryogenic distillation unit will depend on the associated trans-
fer process and will increase according to the sequence: CECE, DE, VPCE, LPCE.
Several research, development and demonstration programmes related to the
process methods potentially applicable for removing tritium from heavy and light
water streams have been undertaken (6-14) and are still going on in Canada, USA and
Japan. Most of these techniques (e.g. LPCE, CECE) are dealing with catalytic ex-
change processes using similar hydrophobic catalysts and have been tested under both
laboratory and pilot plant conditions. Furthermore, since 1978 within the CEC shared
cost action programme on management and storage of radwaste, the SCK/CEN of Mol
(Belgium) is developing an ELectrolytic-EXchange (ELEX) process for tritium remov-
al from aqueous reprocessing effluents. As the CECE process, this process (16-18) is a
combination of water electrolysis and tritium exchange between hydrogen and water,
the exchange being promoted by a hydrophobic catalyst. A schematic illustration of
the ELEX process taken from ref. (18) is given in Appendix III.
However, one has to point out that until today the availability of large plants
designed for removing tritium from HWRs and FRPs effluents is rather scarse. Pres-
ently there is only one small operating plant for removing tritium from reactor heavy
water effluents. It is installed at the Laue-Langevin Institute on the CEN-Grenoble
site and it has started to operate with tritiated heavy water in August 1972 (1,4,5,15).
The presently largest two tritium removal facilities have been commissioned in
Canada. The Tritium Removal Facility (TRF) committed by Ontario Hydro is located
at the Darlington Nuclear Generating Station (3,6,15), while the Tritium Extraction

35

Plant (TEP) committed by Atomic Energy of Canada Ltd. (AECL) is situated at the
Chalk River Nuclear Laboratory (CRNL) (3-15). The Ontario Hydro's original intent
was to build two TRFs, one at Pickering G.S. and the other at Darlington G.S. for
tritium removal from reactor heavy waters. However for economic reasons the
Pickering facility was cancelled and the Darlington TRF will serve all twelves
Pickering & Darlington Reators (3). The intent of AECL committing TEP at CRNL
was to built a demonstration plant for tritium removal from the AECL research
reactors in order to reduce operator doses and site emissions. Furthermore, due to its
design, which retains a flexibility for later conversion (3), it will also give the
opportunity of demonstrating eventual new technologies on an industrial scale.
A comparison among the tritium removal facilities in operation and under con-
struction is given in Tab. 9.2. Schematic flow diagrams of process applied at the
Darlington TRF and the Chalk River TEP are shown in Appendix IV, Figs. IV. 1 &
IV.2 respectively.

9.2 Factors limiting tritium enrichment

Radiolysis and helium production (by tritium decay) appear to be most impor-
tant factors limiting the degree of tritium enrichment before immobilization.
A rough calculation (19) of the maximum permissible enrichment degree has
been carried out for some specific tritium immobilization products, on the basis of a
tritium release limit of 0,001% per day. According to the obtained results it appears
that:
- The radiolysis effect causing an increase of tritium release is in general unimportant
below a tritium enrichment (by atoms) of 0,01%.
- For hydraulic cements the radiolysis become important if a tritium enrichment of
0,3% is exceeded.
- For hydrogenated polystyrene the limit value increases to 1%.
- For a lower water content material such as hydroxylapatite, the limit value further
increases to 6%.
Tritium enrichment before immobilization may also be limited because of the
3
He generation by tritium beta-decay (T/2 = 12.3 years).
If tritium is stored as pure gas (T2) at constant volume, the pressure will ulti-
mately reach twice the filling pressure.
If stored as liquid (HTO) 7,5 litres of helium gas at STP would be evolved per
gram of tritium. This would cause a significant pressure build-up in case of tritiated
water stored in sealed tanks.
If tritium is stored after being immobilized in a solid form, the strengh of the
tritium immobilization product could seriously be compromised if the evolved helium
gas is not allowed to diffuse out. Furthermore also the integrity of the sealed package
which normally should be provided to complete the immobilization process, could
seriously be affected if a sufficient portion of the internal package volume is not
made available to compensate the pressure build-up. It is however espected that, as in
the case of radiolysis, such effects might be minimized if tritium enrichment is kept
at 0,01% or less.

High flux Research VPCE SINCE 10?2 5/ -6 (0.4.85x10' 5 -18 (0. ANNUAL Τ-EXT. AECL Research 1.6.3-9. TRITIUM ENRICH.2 . PROCESS SITE ORGANIZAT. UK) Reactor DARLINGTON G. TEP (3) 1987-88 3. ONTARIO-HYDRO Twelve Pickering & VPCE 1987-88 Darlington CANDU.15 (CANADA) TRF (2) (CANADA) type Reactors xlO' (17-25) CHALKRIVER NAT.7 7-10 6.S. FRG.5 (FRANCE) (1) (F. AVAILABILITY REACTOR GBq -kg" 1 Ci 'kg' 1 PBq(MCi) -a 1 CEN GRENOBLE LAUELANGEVIN INST. RATE REF.5) ω (1) Tritium and Hydrogen Extraction Plant (2) Tritium Removal Facility (3) Tritium Extraction Plant .3x10' 3. 2.6-3.5x102 25 90 (2.16) 1.Tritium Removal Facilities presently in operation.13-15 Reactors 9. FACILITY OWNER OPERATIONAL SERVED Τ-FEED CONC.TABLE 9. LAB.5) LPCE AECL (CANADA) (CANADA).

1.passing a gaseous stream containing tritiated water vapor through a bed of the selected material having a particle size (e.21) which.g. beads) suitable for water vapour removal from the carrier gas stream. . Methods as well as some technical aspects of their application are summarized in Tab.g.3 various matrix materials could be used to solidify tritiated water. to incorporate tritiated water in a stable solid matrix. activated alumina.3 Solidification of tritiated waste waters As mentioned in subsection 7. Only at low water loadings water is strongly held and the lowest values of water vapor pressure can be attained. The first technique can be applied efficiently only in the case of calcium alumi- nate and cements where the totality of solid material and tritiated water can be utiliz- ed by simple mixing of the components in the right proportions. It is worth noting that at 10 wt% loading its vapor pressure is still 20% of . pellets. due to their highly developed internal surface have a high water capacity. and molecular sieves are the products usually taken into consideration as candidate drying agents (1.1 Drying agents Silica xero-gel. tritiated acetylene. However in both cases this technique do not appears to be very practical because of the great excess of tritiated water to be recycled or tritiated organic by-products to be further processed for tritium recycle.g.3. for tritium immobilization purposes.19). . With the second technique a countercurrent operating mode (see Section 8) can be applied to eliminate any necessity of recycling the carrier gas stream still con- taining tritiated water vapor. However at this loading per- centage the resulting vapor pressure is close to that of pure water. 9. phosphorus pentoxide and magnesium Perchlorate) have been excluded because of their high water solubility. Some others traditional drying agents (e. experimental tests will become necessary in order to more clearly evaluate the effects of tritium enrich- ment on the safety of tritium storage after immobilization.dry) are amorphous dehydrated gels of silica (20. Silica xerogels (xeros . Incorporation of tritiated water in these materials can be achieved by: .) which then has to be polymerized. The third technique is based on the use of tritiated water as a one of the re- agents required in the chemical preparation of the matrix material itself (e. Candidate matrix materials specifically applicable for tritiated waste water solidification are briefly illustrated in this section. etc.mixing tritiated water and the selected solid material in due proportions.e.. acetaldehyde. i. hydrated calcium phosphate by precipitation) or alternatively in the chemical preparation of a tritiated monomer compounds (e.g. being capable of loading up to about 40 wt% of water. 37 If higher degree of tritium enrichment have to be considered.using tritiated water as a chemical reagent to prepare the incorporating solid mate- rial itself. 9. 7.

38 that of pure water whereas above 100°C its water retention efficiency become very low (19). Molecular sieves is a commercial name used for a special type of zeolites. 2Si02.2H20) its vapor pressure at 25°C amounts to 5x10"4 bar*. The LINDE company markets a dried Zeolite A containing 1. This is due to the fact that in most of these compounds some of water molecules do not occupy fixed positions in the crystal lattice and are able to diffuse out easily. their dehydration curves show in fact inflection points instead of steps (20). It is also a peculiar characteristic of zeolites that they can lose or resorb water contin- uously without involving major changes in their crystal structure as it is the charac- teristic of most crystalline hydrates (e. .e. 9.4. a hydrated sodium-aluminium silicate) which exfoliates when heated to 600-900°. Absorbed liquids can in fact be expressed from them by a simple pressure and can "weep" at the container bottom unless the amount of the liquid absorbed is kept below a certain limit. They do not display a stepwise increase of dehydration temperature as it would be the case if a crystal structure decomposition does occur. These materials are generally very inexpensive but their efficiency as immobi- lizing agents is rather limited.5H 2 0) contains 22 wt% of water but when water loading diminuishes to 17 wt% (Na2O.5 wt% of water as type HA molecular sieves. It is worth noting that zeolite A when fully hydrated (Na 2 O. They are usually used to remove moisture from gaseous streams and will require a passage through successive beads to ensure complete adsorption of tritiated water vapor and to avoid the necessity of recycling the carrier gas stream still tritium con- taminated. Ca0 2 . diatomaceous earths and other chemically similar products are the most common materials used as absorbers.e.6H 2 0) (20). i.g.Al 2 0 3 .3.3.Al2Og. Vermiculite is a mica-like material (i. Activated alumina exhibits a similar unsatisfactory behaviour and a still lower loading capacity. a class of crystalline compounds (sodium alumino-silicates) which either occur in nature or may be produced synthetically on a commercial scale. Their peculiar features and their non-negligible cost make them uneconomic for solidification of waste waters of relatively low tritium concentration.2 Absorbers A variety of mechanical absorbers have so far been used to convert tritiated water to solid or semisolid materials. A portion of water in most zeolites is anyhow more firmly bounded than the rest and cannot be expelled without destroying the crystal lattice. Therefore absorbent materials are to be considered rather than true matrices for tritium retention only a means of minimizing the liquid leakage and dispersion to the environment in the event the container may be breached. Vermiculite.2Si0 2 . It is an excellent liquid absorber and it can For comparison the vapor pressure of water at 25°C is S· 10 bar. They are also used as special material for filling annular voids between secondary and tertiary waste containment drums.

Therefore to immobilize tritiated water as .Al2Os (19).5 moles of water and completely the rest of water only at 1050eC giving anhydrous 3CaO. 9. 39 change its sodium with calcium and magnesium which may help in the uptake of other nuclides (15. According to ref. Ettringite is a hydrated calcium sulphoaluminate that contains a high amount of water (45 wt%) and has a structure corresponding to Cae[Al(OHe]2(S04)s.Tritium density reached in the tritiated hydroxylapatite is very low. Diatomaceous (or infusorial) earth is an amorphous hydrate silicon oxide that occurs in nature in earthy form ("Kieselguhr") and consists of remains of the silica skeleton (20) of former "infusoria" (diatoms).3. Ca3[Al(OH)e]2. Hydroxylapatite is a hydrated calcium phosphate compound that occurs naturally and contains strong bound water. However subsequent experimental results published by the CEC (22) have indicated that the projected use of hydroxylapatite to immobilize tri- tiated aqueous wastes poses some serious practical problems of a chemical engineering nature and do not appear at all promising. in fact it has been found that its ther- mal decomposition begins at 400°C and there is a very wide temperature range over which it looses water (22). . In particular hydrated calcium orthophosphate together with hydroxylapatite was deemed to be the most promising as it results from a study sponsored by CEC on the potential tritium immobilization routes (19).21).3 Inorganic salt hydrates and hydroxides Hydrates and hydroxides of calcium phosphates aluminates and sulphates have been considered to be other potential candidate materials for fixing tritiated waste water. . (22) the design of a safe and at the same time simple chemical engineering plant applying for tritium immobi- lization the reaction of tritiated water vapor with dehydrated hydroxylapatite is hindered principally for the following reasons: .25 H 2 0 (23). . The remaining water appears to be more strongly bounded (hydroxyl position). Calcium aluminate firmly bound water because of its structure corresponding to the hexahydrate. This material is notable for its excellent capacity for absorbing liquids. For tritium immobilization purposes it has to be dehydrated. It can be prepared also synthetically. About twenty four of water molecules that are weakly bounded (interstitial position) are lost at 100-110°C with shrinkage of lattice.Although hydroxylapatite is reported (19) to have a very good thermal stability as compared to most other inorganic hydrates. On the other end a pelletization after rehydration would involve a very toxic and hazardous pressing process to be preferably avoided. Calcium aluminate and ettringite are both formed in hydraulic cements and the latter also occurs naturally. At 275°C it evolves 4.Problems may exist from the view point of inhalation hazard. because of the finely divided nature of the tritiated hydroxylapatite. The production of solid hydroxyla- patite pellets from this powder before rehydration with tritiated water could be applied but this would certainly reduce the rehydration kinetics.Dehydrated form of hydroxylapatite is not easy to prepare (64 hours at 1250'C) and consequently some problems may arise for its rehydration.

At higher water loadings the held water is not firmly fixed (21). However calcium sulphate in both hydrated forms (dihydrate and hemihydrate) exhibits still too high vapor pressure and appreciable solubility in water to be used without additional physical barriers. The water capacity of commercially available hydraulic cement is in principle reasonably high. In the current practice standard types of concrete have been used for several years to immobilize solid radioactive items and packaged waste. concentrates. Theoretical values are somewhat higher since they neglect non-hydrating impurities present in commercial cements.2H}0) is found widely spread in nature.the nature and relative amount of liquid. increase of the immobilized water loading or workability or resistence to compression).) which often may act as water carriers or sorbents.20.Al2Os. sludges. as well as the screw dynam- ic mixing applied either on a batch or continuous basis (30). By heating in a oven at 230-240eC anhydrous calcium sulphate is obtained which is reactive enough for being used as a drying agent. inorganic sorb- ente.2 wt% water that is capable of tacking back the lost water at ordi- nary temperature (15.4 Hydraulic cements Hydraulic cements are the materials most widely investigated ans practised for radwaste conditioning and disposal with the aim of minimizing the risks of radio- nuclide releases from the solidified waste to the environment (26-31).g. Mixing of the various components can be achieved either by in-drum or in-line techniques. It loses 75% of its crystallization water at 128°C to give "burned" gypsum (CaS0 4 .g. .H 2 0) instead of the ettringite structure. ion exchange resin. A hydraulic cement mixed with water and aggregates (i.l/2H 2 0). However the amount of water needed to obtain a waste-cement product that would satisfy storage or dis- posal requirements may vary case by case according to (31): . 40 more firmly as possible. The procedure and technology related to the cement hydration process are sim- ple and well known.21). 9. Up to the hemihydrate composition calcium sulphate binds water strongly giving a dew-point of -62eC. . the rotary mixing or drum tumbling applied on a batch basis. approximately 25 wt% for portland type cements and up to 50 wt% for high alumina cements. e. However for medium and low active liquid wastes and sludges different techniques are required and formu- .3.the relative amounts of individual cement constituents and the general stoichiome- try of resulting hydrated and hydroxylated compounds. with CaO and CaS04 of the overall composition 3 CaO. Gypsum (CaS04.3 CaS04 should preferably be made only to attain the heptahydrate structure (Ca^AKOH)^ (S0 4 ) 5 . miscellaneous wastes. gravel and/or wastes in various forms and sizes) reacts with water to form a paste that sets and hardens to give a final solid product referred to as concrete.e. an hem ¡hy- drate containing 6.g. wet or solid wastes to be incorporated into cement or concrete (e. e. sand.SO. At MLM (Mound Lab.the nature and relative amount of additives eventually added to cement for various purposes (e. AljOj. of Monsanto) (24) a perlited gypsum plaster is mixed with portland cement to give a 3 to 1 dry modified cement mixture which is used to solidify tritiated waste water and is then over-packaged in a triple walled containment system (see Appendix X). etc. the direct hydration of an anhydrous mixture of 4 CaO.g.

III. 3. . to attain a sufficient low porosity along with a still acceptable consistency of the final cement block. II. Inert materials such as sand and aggregates have therefore been excluded from the mix.2. Water to cement ratios near 0. The use of hydraulic cements for the purpose of immobilizing tritiated aqueous wastes has been regarded as an attractive option for the following reasons (31): I. i. The shielding effect of concrete is particularly useful when gamma-emitter contaminants such as fission and/or activation products are associated with tritiated water. After these periods however. The liquid waste and sludges can be considered as totally or partially replacing the water normally used for mixing with the cement. there is. Any excess of tritiated water which might be held in hardened cement as free or unbound water must be avoided in order to prevent an excess of easily removable tritiated water. This is because an excess of tritiated water in an unbound state can obviously be more easily leached out or evaporated. have thus been applied to prepare tritiated cement specimens tested at the various laboratory for experimental studies on tritium leaching. On the other end the hydration of cement constituents is know to continue in a cement block over long periods of time. therefore. left to stand under controlled conditions) in order to reach in a reasonable time the maximum achievable degree of cement hydration. The porosity of the resulting tritiated cement block has to be keept sufficiently low in order to minimize its increasing effect on the rate of tritium release to the environment. Since the total pore volume is dependent upon the initial w/c ratio applied to the cement mix. To solidify tritiated waste-water by cement hydration the initial water to ce- ment weight ratio must be carefully determined mainly with the aim of minimizing the amount of unbound water present in the hardened cement. 2.e.e.e. Different periods of time are normally ap- plied for "curing" (i. Practically these requirements are met by performing an accurate determination and control of process parameters such as the w/c ratio and the "curing" time. Cement is an immobilizing agent already accepted and practised in many coun- tries for incorporating and disposing of various types radioactive wastes. After hardening the cement block has to be adequately "cured" (i. Tritiated water evaporation as well as environmental water and water vapor permeation are well known to occur through capillary and gel pores inside the body of the hardened cement. the lat- ter being dependent on the cement type. the hydration of these ce- ments is never complete as they simply represent the time required for the cement block to obtain a large fraction (~90%) of their ultimate strength. In conclusion to solidify tritiated waste waters by a cement hydration process the following requirements are to be met: 1. hydrating) the hardened cement depending on the tipe of ce- ment used in the mix (35). allowing to obtain still workable cement mixes. another incentive to carefully cal- culate the proportion of water to cement. Cement is the cheapest candidate material having a considerably high water sorp- tion capacity. 41 lations of neat cement only are replacing the use of concrete (28).

e.) (35) demonstrated that the addition of such absorbers to the ce- ment mortar led to an increase of tritiated water loadings but also to an increase of tritium release rate. the leach rate from the same cement matrix containing 5 wt% of Si0 2 is reduced approximately by a factor 7.to reduce setting time and improve workability of the cement paste. 9. and a better sulphate resistance. . 5 wt% of "silica fume". Type III develops a large fraction of its ultimate strength in very few days and has a larger heat generation rate than type I. 9.to effectively reduce the permeability of water through cement by the formation of hydrated forms of silica gel inside the pores of the cement block.3) was found: . slower setting.3 was initially applied. Type II il a modified cement type employed to yield a lower heat of hydration than type I. Leach data from experimental tests performed at BNL (Brook- haven National Lab. leading to an increase of tritium release to the environment. The use of silica gel as a cement additive to allow a larger tritiated water content in a PITC composite was also investigated at BNL (35) always on the basis of leach rate measurements.3. Type IV has a low heat generation rate and amount of heat. The practical application of cement hydration as a tritiated water immobilization procedure requires that secondary low-level tritiated effluents arising from mainte- nance of water-cement mixing equipment and decontamination of operational area Type I portland cement is an ordinary purpose cement (OPC). Type V is formulated to resist to severe sulphate attack (SRPC). However. which represents approximately two-thirds of the water necessary to completely saturate the silica gel. II. It was however found that the benefit of the higher tritiated water amount immo- bilized per volume unit of the composite is offset by the low density of the obtained composite and the high cost of silica relative to the other materials (35). In the current practice of radwaste cementation some materials having a remarkable capability of sorbing water have often been added to the cement mortar with the aim of loading in the hardened cement composite larger water amounts than achievable by cement alone. in comparison with the tritium leach rate of a tritiated portland cement matrix without additives. .to reduce the teachability of tritiated water from a "neat" cement matrix. in applications where tritiated water has to be immobilized any excess of tritiated water loading has to be carefully avoided since it will negatively affect the efficiency of tritium immobilization. The option of adding water absorbent as vermiculite or diatomaceous earth to the cement mortar was experimentally evaluated on the basis of tritium leaching from the various composites. A water/adsorber ratio of 0. 42 Curing times of 28 days for portland cements (types I. As shown in Tab. This because the initial water adsorbed on silica gel is know to be bound more firmely than the water subsequently added and the complete saturation could have had a negative effect on the leach properties of the composite. see Tab. The leach rate data from the preliminary formulations (35) suggested that the use of silica gel as an additive of portland III type cement did not increase tritium teachabil- ity. IV and V*) and 1 day for portland type III and high alumina cements are currently applied as adequate time periods for attaining a sufficient strength in the hardened cement (35). . As demonstrated at Ontario Hydro (41. .42) the addition of Si0 2 to cement in low proportion (i.to rapidly react with alkali and prevent in such a way the formation of products in the cement which can cause cracking and deterioration of the cement block.

e. The most reliable mixing techniques applicable for immobilizing tritiated wastes were found to be the tumbling/rolling for liquid wastes and the gravity mixing for solid wastes (31). entailing the handling of small volumes of highly tritiated aqueous waste (37-40). LASL (Los Alamos Scientific Laboratory) (52) and Ontario Hydro Re- search Division (41. the injector technique. The probability of keeping tritium release rate as low as pos- sible will therefore depend on the careful determination of two important process parameters. hence of tritium release rate to the environment. Rotary mixing appeared less attractive because. i. MLM (43-49). Slow addition of tritiated water is mandatory and cleaning of injector could be avoided if disposable injectors are used or water is allowd to slowly trickle on to the dry cement upper surface. The third method. moisture and envi- ronmental water. mixing blades should be disposed within the solidification container.19. This method was successfully applied also at MLM (43-49). the required specimens size (-16 dm3 volume) was not compatible with in-drum tumbling technique developed for large scale PITC composites. Many extensive experimental studies have been carried out at BNL (32-40).29. When the preparation of smaller size specimens was needed at BNL (37-39). For this raison an appropriate choice of the cementation procedure and relat- ed process conditions was needed. If not adequately controlled. i.e.42. the fraction of mobile (evaporable) water held in it and the physical conditions surrounding the block such as the ambient temperature.50) in order to investigate the tritium leacheability from specimens of tritiated cement matrices. If this requirements is not met uncontrolled clean- ing and maintenance operations could generate additional amounts of tritiated efflu- ents having (even at a low tritium content) larger volumes than the hydration process disposes. to avoid decontamination and cleaning operation. Therefore specimens were pre- pared using a conventional dough type mixer which produced a final product of simi- lar density as that obtained by the in-drum tumbling technique (see Appendix VII). On the light of such consideration available alternatives for the in-drum cement mixing and casting were consequently evaluated. these factors will significantly contrib- ute to increase the mobile fraction of the original tritiated water incorporated into the hardened cement with a simultaneous increase of its mobility. Three blending methods have been applied at BNL (32-40) in the framework of experimental tests on aqueous tritium immobilization based on the PITC process (see Appendix VII). It is a dynamic in-drum mixing technique produc- ing a homogeneous mixture. the water to cement ratio originally employed in the cement paste and the time period applied for "curing" (i. Results have been published in several reports (32-52) and reviewed by various authors (15. is based on a static technique more compatible with the glove-box or hot cell operations. Factors of major influence in determining the degree of tritium retention in hydrated cements have been identified as mainly dealing with the porosity of the cement block. No cleaning of equipment is required but a substantial volume of cement paste (-90 dm3 inside a 30-gal drum) is to be handled.31). Most significant experimental . 43 should be minimized or eliminated. The first method entails the end-over-end tumbling of the cement and water in the containing waste drum (32-36).e. hydrating) the cement block. By such a technique an injector is used to carefully distribute the aqueous tritiated waste into the centre of the dry cement mass inside an appropriate container.

by leaching or outgassing) to an acceptably low level the application of other supplementary physical barriers is anyhow mandatory. vermiculite or equivalents) were found to allow increased tritiated water loading but at the same time higher tritium release rates. . . Typical draw-backs especially dealing with some types of polymers are: . acrylonitrile or vinylacetate.the limited stability of tritiated polymer to thermal as well as long-term wheather- ing effects. (31) which can be summarized as follows: .the significant yield of tritiated by-product to be retreated. which then is polymerized. 9.To minimize the environmental tritium releases (e.Hydraulic cements are the simplest and less expensive water solidification media. Instead of being directly polymerized. As to the silica gel. which may convert to lower hydrate forms on ageing. although its addition to cement do not involve any increase of tritium leachability. . The preparation of a tritiated polymeric organic material may be achieved by incorporating tritium of a tritiated water molecule in a manomer compound which than is polymerized.g. However none of such cements has the capability of retaining the totality of the incorporated water so that none of them can provide by itself an adequate barrier effect against environmental water leaching and water vapour exchange. This is because the hydrogen of these compounds is attached to carbon by a strong covalent bond so that a low probability of tritium ex- change can be expected to occur between tritiated organic polymers and the environ- ment. especially because of the resulting increased resistence of the waste composite to tritiated water permeation.53-55) as potentially candidate mate- rials for tritium immobilization. Nevertheless the addition to cement of a low proportion of Si0 2 (e. The assessment of these data leads to the conclusions already presented in ref. 5% of "silica fume") has been found to be beneficial.the insufficient yield of tritium incorporation in the polymer. 9.g.Cement additives such as water sorbents (e. the low volatility and the good mechanical properties.3.g. Current problems dealing with the application of such a materials for tritium immobilization purposes are represented by the radiolysis effect and the helium pro- duction. 44 data from leching tests on tritiated cement specimens published by these laboratories are reported in Tab. High alumina cements are capable of binding twice as much water as portland type cements but this initial advantage is partially off-set owing to the metastable hydrated compounds produced by HAC hydration. Other essential advantages as tritium immobilizing media are the chemical stability. Portland cements appear to be the best cement types utilizable for tritium immobi- lization purposes. tritiated acetylene may also be con- verted to a tritiated acetylene-derivative manomer such as ethylene acetaldehyde.5 Organic polymers Organic polymers have been identified (19. the benefit of a higher tritiated water loading is off-set by the low density of the final composite and the high cost of the additive. Tritiated acetylene is in fact prepared through the reaction of tritiated water with calcium carbide and then converted to a high molecular weight polymer.3. . .

56 Portland I 0.83 452.018 n.23 n.56 BNL 34 High Alumina 0.30 .TABLE 9. 1.a.78 -83.0 0.30 -0.23 1.3 .50 0.a.a.00 0.6<1> 3.34 LASL 52 175 -52.83 60 47. 60 6.0 0.3 -0.0 2.0 MLM 19. 10 35.040 Portland 30 -0.a.a.0 180 -77.59 70 -39. fe Portland III n.a.51 1.50 Portland 30 (95X) n.5 12. n. n.1 n.1 -0.0 180 63.7 0.1 n. 10 65.35 High Alumina -0.a.18 n.0 0.a 140 2.114 Silica Fume<2> (5X) (1) Estimated values. -0. Type of w/c Volume V/S Trit i um Cure Leach <1) cement ratio (V> (cm) MBq mCuries time (d) time (d) Cumulative Average Daily (d'1) Portland III 0. SPECIMEN IDENTIFICATION RESULTS TESTING REF.84 Hydro 0.7 0.1 -0.83 -93.a n. (2) It is a 90-95X Si0 2 by-product from the ferrosi licori and silicon metals production.83 111 3.43 Ontario 41. 3.a.6 6.1 -0.0 0. Per Cent Release LABORAT.0 -0. .2 0.0 0.Comparison of data obtained from tritium leaching tests on untreated tritiated cement specimens at the indicated testing laboratories.18 -0.a.29 196 8.0 1-365 140 -47. n.0 2.9 3.28 -0.

8% from tritiated polyacetylene at BNL (34) and 2% and less than 5% respectively from backelite analogue and polyacrylonitrile polymers at BNWL) (54). water extendible poly- ester (WEP) resins were investigated at Ontario Hydro (57) for solidifying aqueous radioactive wastes as an alternative to cement hydration. .Even with small volumes of highly tritiated water a significant limitation of tritium concentration in it is represented by the radiation damage affecting the polymer integrity. which is subject of a US patent (56). 9. Static leach test have been performed on tritiated organic polymers. Some organic polymers and related polymerization processes potentially applica- ble for tritium immobilization purposes are compared in Tab.4) which are typical of some polymers. Based on this technique. This behaviour was explained as due to leaching of surface retained by-products (34) as well as unreacted monomer residues (54). hence the tritium retention efficiency. in pres- ence of a catalyst (rhodium on alumina) (55).32.4. A WEP type resin was consi- dered a promising candidate matrix because it can accept up to the 50 wt% of water giving after the curing period of few minutes a hard and dry final product. 3. Results of tests (19. There is another technique which enables to incorporate tritiated water in the mass of a polymeric organic matrix by sealing tritiated water molecules inside the closed cell structure of the final polymeric composite.g. Note that in absence of catalysts (54) temperatures and pressures required to at- tain an acceptable rate of tritiated hydrogen uptake are enough elevated to render tritium containment during the process very difficult. Based on the information available from the literature the conclusions which can be drawn on the convenience of using some organic polymers as a matrix for incorpo- rating tritium in their chemical structure are the followings: . Experimental studies on the solidification of tritiated waste water by such a resin were carried out at Ontario Hydro (50) with the specific aim of determining what degree of tritium immobilization was achievable by this technique under leach conditions. where various types of polymer instability are also considered. 9. . . Tritiated polystyrene can be in fact prepared by reaction of polysty- rene with tritiated hydrogen at atmospheric pressure and room temperature.Tritium incorporation processes requires equipment and operational procedures which are too complex and/or expensive to be justified in dealing with large liquid waste volumes of relatively low tritium concentration. These process conditions are manda- tory. Thereafter very little or negligible tritium releases were detected in both laboratories over a four to six weeks leaching period. Conversely no tritium leaching from tritiated polystyrene was detectable although no mention of results was made concerning tritium release rate after a longer period of leaching. at BNL and BNWL (Battelle North-West Pacific Laboratory) by immersion of tritiated specimens in deionized water. high tritium incorporation yields are in most cases difficult to achieve while very often significant amounts of tritiated organic residues and/or by-prod- ucts need to be reworked for tritium recycle. 46 Another alternative for preparing a tritiated organic polymer is the electrolysis of tritiated water and the subsequent incorporation of the resulting tritiated hydrogen in the polymer.54) showed an initial rapid release of some percents of tritium originally incorporated in the polymer specimen within the first few leaching days (e.34.Besides the various types of instability (see Tab.

8 Fairly good.8) 0. quires fillers.BSffiSaS ( O wheatheri ng (5) C O Total gas H20 Difficult C 6 H 6 .1 (unless addition of BNWL 19.03 0. Polyethylene TCH=CH2 Satisfactory -96(6) n. water -30 (3) 325 0.54.1 2.a.4 n.02 Good BNWL 19. Brittle I friable (7) Bakelite type (1) TCH2-CT0 Satisfactory lenes.Comparison of some organic polymers and related polymerization processes potentially applicable for tritium immobilization. 3. but it Polyvinilacetate TCH=CH Satisfactory -99 150 1.32.15 ( 1 0 ) Easily oxidised BNL 19.4 . = not available. Hydrogenated (5) (5) 280 0. (9) LABORAT.4 0. Upton (NY).1 Good BNWL 19. -95 (7. Richland (WA). Croto. TYPE MONOMER Easiness By-products " vield Heatin9 Rad1at .34 Polyacetylene TC = C H (3) Stable in the dark.a. n.2 Brittle in air & on None 19. BNWL « Battelle Pacific North-West Laboratory.54. POLYMERIZATION PROCESS STABILITY POLYMER TRITIATED TESTING REF. None 19 COCH.55 naldeyde (4) fibrous fillers) TCH2-CHO Polyacrylonitrile TCH»CH Difficult (2) (4) -40(2) 200 0.a.08 BNL = Brookhaven National Laboratory.54 ' ¿N 0. absorbs water.55 polystyrene 0. .TABLE 9.54 light Polyacety. Re.

(1) Phenol or resorci noI-acetaldehyde-formaldehyde type polymer. (6) At about 60°C and in presence of a Ziegler catalyst. measured by irradiation in absence of water is higher than 100 (19. .Remarks (Continued). (10) The G(-C 2 H 2 ) value. acetylene flow rate (32). 50 wtX loss at 390°C. (5) Data not significant for the assessment of the polymer preparation process in terms of tritium fixation in the polymer and losses in the by-products. thermal degradation above 230. (3) At 280SC and a 50 cm3/min.34).4 . ^ 3 00 (8) Ageing above 130°C. (4) The condensation product of two molecules of acetaldehyde.TABLE 9. (2) The divinylacetylene impurity of tritiated acrylonitrile causes a poor tritium incorporation yield (-40X). By purification procedures on an industrial scale the yield can be increased to 70X. (9) G value ■ number of molecules formed per 100 ev energy adsorbed. (7) Resorcinol-acetaldehyde-formaldehyde type polymer (CHT-CH = CH-CHO).

i »t. 11. Leaching data expressed as cumulative per cent tritium releases were plotted vs leach time as shown Fig. »2 High Al umino Cement 2t doy eure St. Based on these data average daily per cent tritium release (d"1) rates have been calculated as shown in Tab. 47 1- ε t. Note that in presenting data on tritium release rate expressed by the above dimension a linear relationship is assumed to exist between leach time and fractional or per cent releases of the original tritium activity. Cumulative per cent tritium releases in water v s leach time. For compar­ ison purposes tritiated cement (i.1 taken from ref.e.5. SC.2 litres of demineralized water over a leach period of 180 days.27 Portl ond Cement 1 day eure 31.1 Static leach tests at Ontario Hydro (50). 26.57). 37 High Al umino Cement I doy eure o. (50). portland and high alumina) specimens were also prepared (see Appendix V) and tested under the same leach conditions. As shown .01 ' ' ' ' "III I M I UMI I I I Mill U 100 1000 Days FIGURE 9. Static leach tests were carried out by immersing each tritiated specimen in 0. Comparison of solidification matrices.32 Por t lond Cement ¡β day cure 36. The leachant was not changed and one millilitre sample was periodically taken for the analysis by liquid scintillation counting after an appropriate dilution (50). 9. «7 Water Extendibl e Pol yester I day cure 0. 49 The preparation of a final tritiated WEP composite as described in Appendix V required the formation of a water­in­oil emulsion between the aqueous waste solution and the organic polymer and the subsequent solidification of this emulsion by addition of a catalyst amount adequately proportioned to the polyester resin mass (50.

. Fractional tritium releases in water vs leach time.2 Static leach tests at KfK (58).6% Η2Ο/ΗΤΟ in specimen 0. seems to be still not sufficient (like cements) to attain the maximum tritium release target of 10~*% per day as suggested in ref. For comparison also tritiated water/portlant cement specimens (w/c weight ratio = 0. 11. Consequently one has to conclude that the solidifica­ tion of tritiated waste water by a WEP resin. As it is shown in Fig. Comparison of solidification matrices.3 0.4 0. tritiated polystyrene specimens containing monomer to water ratios in the range 0. even if appears to be the best option in terms of tritium retention efficiency. 9.1% per days) is however still far away from the suggested maximum release target of 10_3% per day (19).4) were prepared (see Appendix VI) and tested under the same leach conditions.42% per day to a minimum of 0.t(h)' FIGURE 9. 50 in Fig. it enables to compare results on a normalized even if appro­ ximate basis.9% Η2Ο/ΗΤΟ in specimen ¿­o'0"Ι ­ 0. A modified polystyrene resin (Dow­binder 101) has been investigated at KFK­ Karlsruhe (58) as a candidate matrix material for the incorporation of tritiated water.2 taken from ref. Based on the comparison of these leach data it results that the efficiency of a WEP resin in terms of tritium retention is better approximately not more by a factor three than those of portland and alumina cements. 9.1 this cannot be applied to all experimental diagrams but nevertheless. (50).2 01 H2O/HTO in dow-binder 101 48.5) to vary after 180 days of leaching time from a maximum of 0. The corresponding average tritium release rate calculated for the polystyrene specimen (approximately 0. Specimens were then submitted to static leach tests by immersion in 0. Samplings of 1 microlitre were periodically taken from the leachant.8 to 5 were prepared according to the procedure described in Appendix VI.5 Δι y H2O/HTO in cement Ao 28. For this purpose. (19).5 litres of water over a leaching period of 104 hours (­416 days).0 " 2 Ο 10 20 30 40 50 60 70 80 . Anyhow the average values of daily per cent tritium release rates of all the three solidification matrices were found (see Tab. as also pointed out in ref. 0.13% per day. (58) the slope of the tritium leaching curve obtained from the tritiated polystyrene speci­ men containing about 49 w% of H20/HTO is approximately lower by a factor 10 than that obtained from a tritiated cement specimen (29 w% of HjO/HTO) which was leached under the same operating conditions.

polymer beads. Furthermore one has to point out that. if too expensive absorbers (e. filtration and upgrading) for reuse within the originating facility. Various alternatives have been foreseen (41.Incineration.59) for the management of such wastes: . owing to their rather complex application pro- cedures.g. but not to a sufficient extent.This means that even if superior to a neat portland cement.42.Rework (i. Tritiated waste oils and other organic liquid which do not met the contamina- tion limits fixed for recycling or incineration must be immobilized and packaged for . polyethyl- ene fibres. provided that their tritium contamination is only at a tracer level or suspected.) must be used (59) to limit the ash production. if their recycling is not worthwhile and provided that their radioac- tivity and tritium concentration do not exceed certain limits. as it would be reasonable. .Undoubtedly the tritium retention efficiency of a solidified tritiated water is im- proved by using as a solidification matrix a WEP or a polystyrene resin instead of a portland cement. The rework of radioactive oils is however an operation which may generate in turn additional (secondary) tritiated organic wastes. low cost sorbent material are used with a consequent too high production of residual ashes (e. it is very unlikely that these solidification media may be considered more competitive than materials of a much simpler and less expensive application like portland cements. . . 51 Based on the comparative evaluation of all the above experimental data the fol- lowing conclusive remarks can be made: . 10 kg/litre of absorbed oil) or uneconomic. 9. As for cement therefore. At Ontario Hydro (59) the volume of these additional waste (i. This last option is regarded either as unpractical if. dewatering.g. development and analytical purposes.e.4 Solidification of tritiated organic liquids Relatively small amounts of tritiated organic liquid wastes (e. polystyrene and WEP resins were water solidification media still inadequate to meet alone the suggested tritium release target of 10"s% per day. etc. one or more addi- tional containment barriers are needed to minimize tritium release rate up to an acceptably low level. Incineration of tritiated organic liquid waste may be carried out with the liquids being directly burned or after their absorption on an organic sorbent material. if the above limits are exceeded. hydraulic and/or lubricant oils and other mixed organic liquids) are currently produced by the opera- tion of HWRs and associated Tritium Recovery Plants and by the handling of multi- gram quantities of tritium in Tritium Handling Laboratories for research.e.Solidification and packaging for storage or disposal.. oil sludge) arisings were estimated to be within 2-4% of the volume of radioactive waste oils which in future will be produced and reworked for reuse. In comparison with a hydrated ce- ment matrix tritium release rates from a tritiated polystyrene or WEP resin were approximately reduced only by a factor 10 and 3 respectively.g.

e.4.4. an average daily release of 3.59). only 5% of the final product volume against about 25% by volume with cements) and an increase by a factor 10 2 -10 s of tritium permeability through the polyethylene was measured. namely cements. 52 storage and/or disposal.e. To this end various types of potentially applicable matrix materials were investigated. The best combination of flowability of the mixture as well as dryness and compressive strenght of the final solidified product was reached by a mixture of methyl-alcohol. This technique therefore appears to be near to meet the 10"*% daily tritium release target (19).e.2 Organic polymers Water extendible polyester resins must be included like cements into that cate- gory of solidification media the application of which entails that tritiated waste oils has to be emulsified with water before their solidification. 9.1 cm thick polyethylene bottle (v/s=0. and mixing at high speed before the addition of the cement powder. organic polymers and absorbers (41. being a polyethylene bottle utilized to contain the WEP solidified tritiated oils. For this reason this technique was deemed to be unsuitable for tritium immobilization purposes (41). As for tritiated waste waters.8xl0"5 cm^d"1 (i. by subsequent addition of a suitable catalyst amount and curing. (41) a fractional tritium release rate of 1. This was explained as due to the negative effect of the WEP components on the wall of the polyethylene bottle. However its application is precluded by a serious draw back due to the mixing high speed needed to produce the emulsion of the tritiated oil in water to which the cement powder is then added. As reported in ref.1 Hydraulic cements Portland and high alumina cements along with the so called Envirostone Gypsum cement. A rather low oil incorpora- tion yield was attained (i. The application of such a matrix was investigated at Ontario Hydro for the solidification of polyethylene contained tritiated oils (41). gelatin/ methyl alcohol mixture in variable proportions). This technique aimed at achieving a satisfactory solid waste product was based on the previous preparation of an oil-in- water emulsion by adding the tritiated waste oil to a mixture of water and emulsifier.5x10"*%) was measured for specimens of cement solidified tritiated oil contained inside a 0. 9.42. They were used in conjunction with some emulsifiers either commercially available or suitably prepared (i. For these reasons also the .476 cm). this will ensure the safest condi- tions for the subsequent waste management operations and minimize the environ- mental spreading of tritiated liquids in the event that their containment vessel may be breached. It is in fact during such a step of the tritiated oil pro- cessing that a significant fraction of volatile tritiated species initially present in waste oils will be liberated with a consequent partial loss of efficiency in terms of tritium immobilization. portland type HI cement and water (59). The final solid composite is then obtained by an intimate mixing with the liquid organic polymer. were investigated at Ontario Hydro (59) as candidate matrices for the solidification of tritiated organic liquid wastes. This requirement can be met if the tritiated organic liquid is incorporated into or absorbed on a solid matrix.

but sometime difficult because of the critical dependence of the characteristics (e.42. IAEA. Solidification of waste oils may be attained also by their incorporation into a urea-formaldehyde resin.59) provided that oil loaded absorbers are then contained inside a polyethylene container. 9. At MLM (59) vermiculite and a chemically similar material were also utilized as absorbent matrices for immobilizing tritiated waste oils. in principle. Note that the purpose of the absorbent matrix is not only to keep the oil away from the container walls but also to minimize the leakage and dispersion of the content in the event the container may be breached. mechanical strenght and dryness) of the final solid product from process parameters such as the time and speed of mixing. However as reported in ref.4. (59) the resulting wax-like solid product was not stable.42) that tritium permeability through the polyethylene increases even if tritiated oil alone is introduced inside the container. a perlite-based absorber) inside 1 cm. The data obtained from leach tests on the whole package indicated that the amount of tritium released from the package to the ground water each year would not exceed 10"*% of the total tritium contained in the package (59) which is largely below the suggested tritium release target of 10"*% per day. As pointed out in ref. 203. 1981. The loaded-oil absorber was also contained inside a rigid high density polyethylene container which in turn was inserted in a secondary and then in a tertiary containment drum with again vermicu- lite filling the annular void between the two drums. Furthermore the application of such an organic resin is uneconomic for so- lidifying large amounts of tritiated oils because of the high costs of the raw material. possible.5 References for Section 9 (1) IAEA. Since it was demonstrated (41. the wails of the polyethylene container must have an adequate thickness to compensate this phenomenon. In addition this technique would be unpracticable with oils containing tritiated water since tritiated water would be liberated from the final waste composite because of the temperature peak (t*C>150) reached during the exothermic cure step (59).42. 15. Handling of Tritium Bearing Wastes. thick high density polyethylene container were able to meet a tritium daily release target of 10~3%.e.3 Absorbers Another alternative option investigated at Ontario Hydro (41. 53 application of a WEP resin as a solidification matrix for polyethylene contained tri- tiated oik was deemed to be unsuitable (41). As reported in ref. . 9. (59) the use of oil extendible polyurethane resins for in- corporating tritiated waste oils is. IAEA Technical Report Series No. (42) results of leach tests indicated that oil-loaded ver- miculite or "sorbent-C" (i. Vienna. perlite or chemically similar absorbers (41. p. Heated to about 100°C it softened and exuded the most part of oil so that the oil incorporation in such a matrix was not considered applicable for storage or disposal or incineration purposes.59) for immo- bilizing tritiated waste oils is based on their absorption on thermally expanded silicates such as vermiculite.g.

.. (12) Chuang K. (4) Pautrot Ph.. Vol.K.T. Removal and Immobilization of Tritium from Ontario Hydro's Nuclear Generating Stations.L.. Canadian Fusion Fuel Technology Pro- ject. 54 (2) Holtslander W. ACS Symposium Series No.K.T. 8 (1985) 2478. Separation of Hydrogen Isotopes. Fusion and Isotopie Application... Operating Experience with the Tritium and Hydrogen Extraction Plant at the Laue-Langevin Institute. Novel Catalyst for Isotopie Exchange between Hydrogen and Liquid Water. 68 (1978) 163. ACS Symposium series No. Proc. Ohio.. (5) Damiani M. Tritium Removal by Hydrogen Isotopie Exchange between Hydrogen Gas and Water on Hydrophobic Catalyst. 68 (1978) 93. Fusion Tech. CONF-800427 (1980) 425. (13) Harrison T. Separation of Hydrogen Isotopes (RAE. 1. ANS Topical Meeting. Holtslander W. H. Deuterium Exchange between Hydrogen and Water in a Trickle Bed Reator. Operating Experience with the Tritium and Hydrogen Extraction Plant at the Laue-Langevin Institute in Grenoble Appendix V of Ref. ANS Topical Meeting. Tritium Technology in Fis- sion Fusion and Isotopie Applications. CONF-800427 (1980) 415. Ohio. et al.). 1980. Ontario Hydro (1984).. Dayton. Its storage and Monitoring of Its Migration in the Environment. ANS Topical Meeting. Recovery of Tritium from Candu Reactors. Catalytic Detritiation of Water.K.J.P. 68 (1978) 117. (9) Rogers M. Damiani M. ACS Symposium Series No. Proc. 68 (1978) 110. ANS Topical Meeting. Ed.K. et al. Ed. Ed. Tritium Transfer Process Using the CRNL Wetproof Catalyst. Dayton..... (3) Canadian Tritium Experience Manual.. CONF-800427 (1980) 422.). Eng. et al. Design of a Demonstration Tritium Recovery Plant for Chalk River. Recovery of Tritium from Aqueous Waste Using Combined Elec- trolysis Catalytic Exchange. CONF-800427 (1980) 377.E.. H.K. Appendix I of Ref. 1980. Dayton.J. Can. . Ohio.. Chuang K. Chem. 1980. Combined Electrolysis Catalytic Exchange (CECE) Process for Hydrogen Isotope Separation. J. Fusion and Isotopie Application.T. 56(1978)246..K. ACS Symposium Series No.. Ed. Fusion and Isotopie Applica- tion. (1). Separation of Hydrogen Isotopes (RAE. Tritium Technology in Fission. RAE. et al. Tritium Technology in Fission. et al. (7) Hammerli M. H. Dayton. (10) Mills T. H. Tritium Technology in Fission. Proc. (6) Sood S. Ohio. (8) Butler J... et al. (11) Morishita T.. Proc. Separation of Hydrogen Isotopes (RAE. (10) Enright J..). 1980.

Separation of Tritium from Reprocessing Effluents. 3. Vienna.15.. (18) Geens L. DP-1448. 234. part 3. EUR 7653 (1981). Atom.A. 3 rd Ed.. (26) Lokken R.J. Fusion Tech. (22) Brldger M. part 2.. pp. PNL- 2654 (1978). et al.. (1970). Tritium Immobilization by Incorporation in Inorganic Solids. 2. et al. Rep.. p. 3 (1979) 599. EUR 11551EN (1988). IAEA Technical Report Series No. et al. 3. Nucl.Nuclear Science and Technology. A review of Radioactive Waste Immobilization in concrete. E. et al..V. Tech. Vol. Smith D.O. The ELEX Process for Tritium Separation from Aqueous Effluents. (20) Remy H.G. (28) Palmer J. Fusion and Isotopie Applications. Recovery and Packaging of Tritium from Canadian Heavy Water Reactors. (15) IAEA. and Techn. Tritium Technology in Fission.. SC September 1976. (17) Bruggeman A. The Chemistry of Cement and Concrete. 14. Sci. Vienna (1980) 157. Vol. Solidification of Low.. Vienna. Aiken.H. EUR 6270 en (1979). Packaging of Tritium-Contaminated Liquid Waste. Proc. p. .M. (24) Mershad E. (21) USERDA. No. Res. (27) Stone J. Alternative for Managing Wastes from Research and Post-Fission Operations in the LWR Fuel Cycle.. (16) Bruggeman A. 491. 15 & 22. 1980. Ltd. 13. Nucl.. and De Freitas C.. Elsevier Pubi. Man- agement of Gaseous Wastes from Nuclear Facilities IAEA-SM-245. 1.. 8 (1985) 2473..J. 496. European Appi. Co. . Vol. 55 (14) Holtslander W. 547. 14. 280. ERDA-76-43 (1976) Vol. 2 (1971).L. Symp. The incorporation of Low and Medium Level Radioactive Wastes (Solids & Liquids) in cement.and Intermediate-Level wastes. IAEA. Dayton. 1980. Management of Tritium at Nuclear Facilities.C. Tritium Immobilization. (1956) pp. En. (23) Lea F. Proc.. Arnold Pubi. ANS Topical Meeting. I. part.A. et al. 1984. Rev. SRL...10. Treatise of Inorganic Chemistry. p. EUR 10561 EN (1986). CONF-800427 (1980) 411. 12.D. Vol. Separation of tritium from aqueous effluents.A. Ohio. No.12. (19) McKay H. et al. Evaluation of Concrete as a matrix for Solidification of Savannah River Plant Waste. IAEA. 6 (1981) 1465. (25) Burns R. 514. Vol.

32. 4. PR No. (43) Dauby J. PR No.J. IAEA Coordinate Research Meeting on "Handling of Tritium Contaminated Effluents and Wastes". Conditioning and Handling of Tritiated at Canadian Nuclear Power Facilities.. Management and Disposal of Alpha-Contaminated Wastes. Tritium Storage Development. Conf. Conditioning of Tritiated Wastes from a Tritium Removal Facility. et al. 2. 32. Chem. Tritium Waste control Project. PR No. (30) Mannone F. (38) Neilson R. April 5-10. (37) As Ref. et al.Y. (40) As Ref. (45) As Ref. BNL-19981 (January-March 1975).-750989 (1975). No. Conf. BNL-20421 (April-June 1975).S. Annual Meeting Denver. PR No. Sept. 1986..P. BNL-20779 (July-September 1975). Niagara Falls. MLM-2502 (October-December 1977). PR No.. (42) Krochmalnek L. Immobilization of Tritiated Waste-Water by Hydraulic Cements. Rep.. MLM-2484 (April-September 1977). BNL-21700 (January-March 1976). ANS International Topical Meeting on Waste Management and Decon- tamination. 5. (39) As Ref. Tritiated Aqueous Waste Immobilization. N. 32. PR No.. FRG. (44) As Ref. 32.M. A survey of the State of the Art. (32) Colombo P.-770611-21 (1977). Fixation of Aqueous Tritiated Waste in Polymer Impregnated Concrete. (35) As Ref. (41) Krasznai J.S. 1987. 9. (33) As Ref. 43. et al. (36) As Ref. MLM-2451 (October 1976 . 32. paper presented at the Am. 12. The Fixation of Aqueous Tritiated Waste in Polymer Im- pregnation Concrete and in Polyacetilene BNL 20898. EUR 8574 EN (1983). October 20-24... 56 (29) Williamson A. et al. (31) Mannone F.March 1977).. BNL-50625 (July-September 1976). 1980. BNL-22900. CFFTP-G-87013. 7.. et al. Juelich. 3. Immobilization of Tritiated Aqueous Waste in Polymer Impregnated Concrete. Soc. BNL-19688 (October-December 1974).. (34) Colombo P. Prog. Report EUR 11230 EN (1987). . BNL-50733 (April-June 1977). 43. 32.

2.S. Immobilization of Radioactive Waste Oil...March 1979). Ontario Hydro Research Division Report No 84-6-K (1984).. Solidification of Tritiated Waste. Rep. BNWL .M. and Burger L. Los Alamos Scientific Laboratory. August 1971.. 7. and Burger L. Conditioning of Tritiated Wastes.1981).Non Active Oil Studies.. et al. US Patent 4 0077 901..S. MLM-2519 (January-March 1978). Final report MLM-2644 (September 1979).5. Polymer Impregnated Tritiated Concrete. (59) Hawthorne S.E. Pergamon Press.1981/30. LA-DC- 12740. 1978.. Fusion Technology 1986. Vol.. BNWL-B-430 SUP I (1976). MLM-2542 (July 1978). (1. 43. et al.Solidification and Encapsulation..L. (49) Wleneke R. N. Solidification of Aqueous Decontamination Wastes with Water Extendible Polymers. (58) Penzhorn R. (54) Franz J. Polymeric Media for Tritium Fixation.M.D. Ontario Hydro Research Division Report 81-57-H (1981).. (55) Franz J. and Boyle R. (56) Arnold J. 57 (46) As Ref. MLM-2620 (October 1978 . and Brunner H. The Technology of Tritium Fixation and Storage.11. Los Alamos.. p.A. (57) Williamson A. BNWL-B- 430 (1975).1807 (1973). Part I . March 7.L. Part II . (52) Emelity L. Proj.L.L. . (48) As Ref. Ontario Hydro Research Division Report 83-350-H (1983). and Rayan J. IAEA Research Con-tract RC 2492/RB quoted by Ref. 43.L. (51) Sunder Rajan N. 43. (47) As Ref. Association Euratom/CEA CEN Cadarache.A.H. (50) Hawthorne S. Tritium Loss From Coated Cement paste Blocks.H.A. Eucapsulation of Nuclear Wastes. (53) Burger L. 1531..

medium and highly tritium contaminated are the solid waste categories currently defined for the solid waste classification. while the bulk of highly tritium contaminated ones will consist mainly of discarded metal components and exhausted materials hence of non-processible materials. All these operations are carried out in waste handling facilities adequately monitored and ventilated. depending on their nature and contamination level. In most cases tritiated solid wastes will be sorted according to their con- tamination history and the capability to accept a volume reduction by compaction (compressible or uncompressible) or incineration (combustible or incombustible). Smear tests and outgassing rate measurements may assist in the evaluation of the waste contamination level. Pending the conditioning. The bulk of suspect or slightly and medium contaminated wastes are expected to be combustible or compressible. Conversely all the other tritiated solid wastes have different gaseous release potentials.1). Consequently tritium immobilization procedures and special containment barrier systems must be applied in order to control their outgassing rate. sorted and packaged at source. As illustrated in Section 3 these wastes will include materials which are largely different in the origin. They will be classified.2 the outgassing potential of tritiated metallic wastes may be reduced before the conditioning by some surface treatments such as leaching. As illustrated in subsection 10. TREATMENT AND CONDITIONING OF TRITIATED SOLID WASTES In addition to the solidified liquid wastes a wide variety of solid wastes will arise from tritium handling facilities and plants as well as from future fusion testing and power reactors. slightly. no immobilization and/or special containment packages have to be foreseen for tritium containment purposes. Suspect. The sorting will be performed according to classification criteria that may vary from plant to plant (see Section 6). Suspect wastes are non radioactive materials which are assumed to be tritium contaminated and therefore are procedurally treated as radioactive ones. 58 10. all the above waste categories are placed and transferred to the waste conditioning plants inside plastic bags or sealed containers in order to minimize tritium releases to the environment.1 Volume reduction of tritiated solid wastes The volume reduction of tritiated solid wastes may be attained by different procedures such as incineration. nature and shape. Miscellaneous suspect or slightly contaminated wastes are usually considered as non-outgassing materials so that apart from an eventual volume-reduction treatment (see subsection 10. In miscellaneous combustible or compressible wastes tritium contaminant will be absorbed mainly as tritiated moisture whereas in hard wastes it will be distributed as tritiated hydrogen in the oxide layer and the bulk of the metal component. compaction or vacuum re-packaging according their nature and tritium contamination level. 10. At the Radioactive waste operation site located at Bruce Nuclear Power Devel- opment and operated by Ontario Hydro a Waste Volume Reduction Facility (WVRF) is . isotopie exchange with a moist atmosphere or heating.

Ashes were unloaded by gravity descharge into 2. . Since 1977 also tritiated combustible wastes have been volume reduced (VRF ~40) in a batch-pyrolysis-prototype starved air incinerator where the wastes were pyrolyzed at 500eC and volatile gases with "particulates" completely burned at 900°C in a propane-fired afterburner chamber (2.5 (3). At the ETHEL waste conditioning plant the gaseous discharges from the vacuum chamber will be directed to a gaseous detritiation system and then released to the stack. where exhausts are monitored for controlling airborne tritium emissions.e. The gaseous discharges from volume reduction operations may be directed to a detritiation system or directly released through a stack. arising from Ontario Hydro CANDU Nuclear Generating Stations (2-4). Up to 3x10s m3 of waste per year have been incinerated (2). whereby gross and net VRF values of 7. Overall releases from the WVRF have been controlled by limiting incineration to waste with a maximum gross beta-gamma dose rate of 0. (7). the European Tritium Handling Experi- mental Laboratory of the Commission of European Communities under construction at Ispra Establishment (6). At the Waste Experimental Reduction Facility (WERF) of INEL (Idaho National Engineering Laboratory) (7) a metallic hard waste sizing facility has been initially developed for volume reduction of internally beta-gamma contaminated piping and tankage removed from the light-water reactor transient test facility (SPERT III). Since 1977 a mechanical compactor has been used at the WVRF to reduce the volume of tritiated compressible wastes (2-4). cut-off saw. i.5 m3 rectangular metal containers which may contain in average ash products of approximately five incineration batch loads (3). If.3 mCi/g) tritiated laboratory wastes are also compacted before to be drummed (see subsection 12. The aim was to cut large components into pieces acceptable for direct disposal or for melt- ing. combustibles and compressible wastes cannot be incinerated or mechanical compacted their volume-reduction may be achieved although to a minor extent by a vacuum re-packaging operation. Compactor and baler exhausts have been also discharged directly into the exhaust stack of the building ventilation system for minimizing occupational doses. 59 utilized to process all solid reactor wastes. detritiation and monitoring of these gaseous waste streams are operations required to minimize the risks of tritium exposure for operators and general population. At MLM (5) low specific activity (i. The containment. At the Ontario Hydro WVRF (2. The gross volume reduction factor (VRF) achievable by the compactor was 4. To improve the storage efficiency of compacted waste a baler provided with a rectangular com párteme n t for waste compaction was installed in 1981.1).5-9 and 5-6 were thus attained. while the net stored VRF was only ap- proximately 2.3) virtually all tritium emitted during the waste incineration batch operations has been so far discharged to the incineration stack. During all the above volume-reduction processes the release of tritiated gases is expected.e.6 mSv/h (60 mr/h) (4) and compaction process to waste with less than 2 mSv/h (200 mr/h) (3).e.5. for any reasons. although initially all sizing equipment (i.3). The application of this procedure is at the present time foreseen for the volume-reduction of bagged tritiated soft wastes in the Waste Conditioning Plant of ETHEL. < 0. A VRF of 4 is achieved. As pointed out in ref.

Another way for achieving the surface decontamination of tritiated metallic components is their heating inside a oven under vacuum or reduced pressure with an inert gaseous stream.1).1% per day thereafter (9). the whole heating apparatus being installed into a secondary containment system (i. In the second case a bulk melting treatment is prefer- able to achieve an effective detritiation. In the present operating conditions the use of this facility is pre- conized to be applicable also for reducing low level hard waste volumes arising from future thermonuclear fusion plants (7). depending on the metallic nature of the hard waste. with water. 10. smoke noise or dust will preclude manual operations. Tritiated metal samples were leached in 50 ml of distilled water for 150 days (see Fig. after the surface layer detritiation. In the case of a prominent oxide layer distribution. The efficiency of this operation depends obviously on whether the distribution of tritium is prominent in the oxide layer or in the bulk of the metallic component to be detritiated. as well as surface heating are the most effective detritiation treatments. For stainless steel samples there was a rapid leaching of tritium within the first 7 days which decreased to 0. guillotine saw. arc gaugh and plasma torch) have been manually operated future robotization is foreseen if radiation fields. As reported in ref.9).1 taken from ref. As to copper samples 26% of the total tritium was removed by the leachant in the first 7 days. a glove box system).2 Detriation of tritiated metallic hard wastes To reduce the outgassing rate of tritiated metallic hard waste and consequently to facilitate their conditioning and safe storage. Leaching tests for surface decontamination purposes have been performed at Ontario Hydro (8.e. In Tab. Tritiated samples of bulk copper and stainless steel tubing removed from a tritium handling loop at AECL-CRNL were used as representative waste samples arising from the Tritium Removal Facility.g. Tritium could be also removed from a tritiated metal surface by isotopie ex- change with a moist inert atmosphere in which the tritiated waste item is allowed to stand (9). Consequently. Therefore tritium appears to be easily leached off from the surface layers of both metal samples. non-retrievable metallic components removed from tritium handling facilities have to be detritiated. surface leaching. 10.g. The tritiated gaseous stream coming . 10. Tritium in the surface oxide represented about 29% of the total tritium for copper and ranged from 52% to 80% for stainless steel. thereafter there was no measurable release. (9) after tritium surface removal the diffusion rate of tritium from the bulk metal may exceed (e. (8) is reported the distribution of tritium in the oxide and bulk metal as determined for both types of samples. The copper samples appeared to have a fairly uniform distribution of tritium activity. whereas in the stainless steel samples it was much more variable. 60 pipe cutter. isotopie exchange with moisture. further conditioning may or not be required to minimize the rate of tritium release to the environment. stainless steel) or not exceed (e. copper) the value of 10"3% per day suggested (1) as the maximum admissible tritium release target.

8 30 0.11) about four tons of tritiated metallic wastes have been submitted to detritiation by a surface thermal treatment. .SO Ό <υ ui ra 0. .60 16.9 Copper 1.1 70 1. .3 20 2.30 - υ ra Copper 0.1 . .1 .7cm" Volume 3 E 0.71 73.60 16. .00 J I I I I I L J I L 20 10 60 80 100 120 IMO 160 160 Days leached FIGURE 10.21 5.81 2. from the oven is directed to an atmosphere detritiation unit whereby released tritium is recovered by catalytic oxidation to tritiated water and subsequently absorbed on a molecular sieve bed.56 0. The campaign required in total 92 individual batch- operations.40 64.Leaching performance of tritiated metallic components (8).41 .6 71 1.5 3.12 1.46 12.7 1.93 26.44 .40 ν ν Stainless steel Oí c o 0.5 75 0.9 29 0. .47 0.11).20 Surface area 12.79 0.8 47 0. .13 30.9 48 4. 1. .8 1.80 21. (ï) (MBq) (microCi) (%) (MBq) (microCi) (%) (MBq) (microCi) 1.4 4. .Tritium distribution in metallic specimens (8).8 52 2.33 35.40 10.4 71 1.9 1. 0. .80 48.0 Stainless 1. Fairly high tritium decontamination factors (see Figs.1 O. .4 1.33 8.24 6. During each treatment pratically the whole tritium fraction achievable by this method was liberated at about 800°C during a time interval of about 1 hour. .98 134.18 58.58 69.6 53 0.2 to 10.22 32.83 22. .57 .2 25 2. SAMPLE Wt SURFACE TRITIUM BULK TRITIUM TOTAL MATER.4) were measured after each heating treatment (10.34 9. 61 TABLE 10. This would demonstrate that the most tritium is permeated in the surface layer of metallic components. 1.40 37.53 14.17 31.7 Steel 1.8 80 0. . During the year 1983 at the centre of Valduc (CEA-DAM) in France (10.54 0. 10. .10 3 (J 0.1 29 0.39 2.40 64.

4 taken from ref. temperature. pressure.2 may be due either to the possibility of errors in evaluating the initial overall waste activity (e.2 ­ Results of thermal treatments performed at Valduc on tritiated metallic wastes (10. as a consequence of the complete destruction of the metal crystalline lattice in which tritium is trapped. Operating conditions and results of thermal treatment campaigns carried out at Valduc are summarized in Tab.3 ­104 180 5. to to to to to vacuum 40. Indeed this technique would in principle allow a more efficient detritiation of the metallic com­ ponent.5 bar) As shown in Figs.30 8 3.SxlO 3 Aluminium 11 ­0. As explained in ref.g. ­ homogeneous distribution of residual tritium concentration.0 ­0.7xl03 (0. hence reduction of the number of samples of casting materials which are to be taken to verify the residual tritium specific activity.41 Heating for 1 at 0.0 1250°C under 1 torr.3 ­1.26 Melting for 2 at 0.1 ­10.11).37 10 3.lxlO3 481 13 ­l. not sufficiently representative samplings) or to the significantly different plant operating conditions (e. SAMPLE BATCH TOTAL TREATMENT TRITIUM ACTIVITY Of1) AVERAGE MATER. etc. Such a process technique appears to be superior to the sur­ face thermal treatment even because the final waste casting offers other non négli­ geable advantages such as: ­ reduction of overall final dimensions of the waste form. ­ considerable reduction of tritium contamination on the ingot surface which enables in some cases its safe handling even without a secondary containment. TESTS Wt CONDITIONS Initial Residual DECONT.0 2. (11). hence minimization of the outgassing surface area. 10. (11) the dispersion of the experimental points reported in Fig.2. (No. operation time.0 ­1.26 7 11 0.0 800°C under 1 torr. the decontamination factor increases as the initial activity in metallic wastes increases.39 Melting for 2 at 0. 10.g.7 0. to to to to to vacuum 33.ΟχΙΟ2 74.7 0.2 β.2 to 10.3­0. TABLE 10.1 ­20.7xl03 Steel 8 ­0. where the decontamination factor is plotted versus the initial tritium contamination of steel and aluminium wastes.7 l.) .0 800°C under to to to to to reduced pressure 22. 62 A more drastic thermal treatment to which tritiated metallic components may be submitted after an adequate size reduction (parcelling) is the melting. 10.) (tons) (MBq) (microCi) (kBq) (microCi) FACTOR (DF) Steel 92 ­4.

Variation of the decontamination factor versus initial activity of the steel hard waste after melting treatment (2 hours at 1250°C and 1 torr. Variation of the decontamination factor versus initial activity of the steel hard waste after heating treatment (2 hours at 800°C and 1 torr. 10.000 I c 1. 63 10.000 FIGURE 10. vacuum) (11). .000 o 1E tn c o 100 o α> O 10 10.t" FIGURE 10.000 Initial Ci.2 . vacuum) (11).3 .

Observation windows. Rooms for waste melting development are located in the basement of the WERF building. Furthermore in Fig. .000 Initial Ci.4 an analysis of the type of correlation existing between the decontamination factor and the initial tritium activity in the metallic waste is rather difficult because of the scarcity of experimental points (11). 10.4 .2 the average slope of the log-log diagram is less than one. 1000-Hz coreless induction furnace.5 bar) (11). Metal is manually charged into the 1500 lb.3 one could conclude. This has been explained (11) as due to a possible tritium diffusion propor- tionally increasing into the bulk of the metallic waste as its contamination level increases.3 and 10. 10. even if on an approximate basis. under which the metallic item could have been employed in contact with a tritiated medium. As to Fig. closed circuit television and remote furnace controls have been installed to allow operation of the furnace from the control room. At Idaho Falls (7) the melting of metallic hard wastes has been initially devel- oped in conjonction with the metal sizing operation carried out in the Waste Experi- mental Reduction Facility (WERF) of INEL (see subsection 10.Variation of the decontamination factor versus initial activity of the aluminium hard waste after melting treatment (2 hours at 800°C and within 0. Nevertheless from the trend of the few experimental points reported in Fig.3 to 0. 10. The furnace is fitted with a close-capture fume hood which carries off-gas to the main facility exhaust for treatment prior to release from the stack. that no substantial differences would be expected in terms of tritium extraction efficiency between heating and melting treatments on tritiated steel hard wastes. which consequently produces an increasing of the thermal'extraction diffi- culty for highest tritium contamination levels. 64 1.t-' FIGURE 10.1) for fission waste volume reduction purposes.

3 Encapsulation of tritiated metallic hard wastes As illustrated in the preceeding subsection the outgassing of a tritiated hard waste may be significantly minimized by removing tritium contamination from its metallic surface. Selection of a suitable slagging agent can remove undesirable elements that oxidize easily in the melting process. isotopie exchange with moisture or thermal surface treatments could be insufficient to reduce their outgassing rates within acceptably low limits. A slag coagulant. In this case.3 and 12. In addition. In melting operations with contaminated metal. Operation of the induction furnace with uncontaminated metals indicated the importance of preventing slag bridges over the molten metal pool and subsequent pool overheating. The employ of low-activation steels (12. The fusion waste issues due to the disposal of fusion reactor components (i.2 respectively devoted to the containment and packaging of tritiated hard- waste composites. For large-scale and highly contaminated operations. However water leaching. The ingot shape was chosen to simplify removal from the mold and so that four could be bundled together for shipment to the INEL Radioactive Waste Management Complex (7). In the current practice these encapsulating materials are usually employed in conjonction either with polyethylene or epoxy resin liners forming with them a double barrier system packaged into metal drum or concrete containers. after detritiation. the metal is cast into 680 kg ingots having a 560x1120 mm surface and a triangular cross section. tritiated hard wastes will require further condi- tioning in order to provide one or more additional barriers against the environmental tritium release. 65 A continuous air monitor constantly samples air entering the facility stack for airborne radioactivity. the HEPA filter is routinely replaced and the used filter is monitored for alpha and beta activity. 7&12 it has been calculated that without recycling the production of structure hard wastes would amount to about 400 tonnes per TW-hr generated. For this reason and to avoid repetitions such systems will be more extensively illustrated under subsections 11. was later used which facilitated manual removal of the slag before metal pouring.13) for fabricating first wall/blanket components is foreseen to enable their recycling after an adequate detritiation and a sufficient decay. most of the surface contamination on the piping and tankage was found to be in the slag and the molten metal was relatively clean. After melting. In fact as reported in refs. The incorporation into a suitable encapsulating medium is the option so far investigated (9) and applied (14). . 10. This recycling is primary aimed at reducing the production rate of activated hard wastes which otherwise could become eccessive. perlite ore. first wall and blanket components) are expected to be fairly similar to those en- countered in the operation of the WERF even if first wall and blanket fusion reactor components will prominently have bulk activation rather than surface contamination. the removal of slag would have to be done remotely. Water extendible polyester resins and portland cements were utilized for this purpose.e.

Treatment and Disposal of Tritium Containing Waste at Mound. Recycling of Activated Steel First Wall/Blanket Material from Fusion Reactors. of the IAEA Seminar on the Manage­ ment of Radioactive Waste from Nuclear Power Plant. 1987. Niagara Falls.J. April 5­10.. Denver. and G irou χ P..P. 1981. Committee Meeting on Fusion Reactor Safety. Dijon. (11) G uetat Ph. Report of IAEA Tech.E.D. and Ochem D. ANS International Topical Meeting on Waste Management and Decontamination. May 1­6. 3 (1979) 599. Res. Proc. Denver.J. (8) Krasznai J. Chem. IAEA. (4) Krochmalnek L. October 5­9. 1987. (9) Krochmalnek L.. Canadian Fusion Fuel Technology Pro­ ject.. (3) Carter T.A. (12) Butterworth G . The Routine Handling.. August 1984. Annual Meeting. (2) Canadian Tritium Experience Manual. Denver. Application of 10CFR61 to Long Term Fusion Waste Manage­ ment. 1986. No. (6) Mannone F. Processing and Storage of Liquid and Solid Waste at the European Tritium Handling Experimental Laboratory. Traitement des Déchets Métalliques Recyclables. Soc. Ontario Hydro (1984).. Carney ML. et al. Sept. April 5­10. 1. (10) Ochem D. 87/06.4 References for Section 10 (1) McKay H. 3­7 November 1986. Annual Meeting. Tritium Safe Handling Course. Chem.S. 1986.S.C. paper presented at the Am.. Tech. Conditioning of Tritiated Wastes from a Tritium Removal Facility. Tritium Immobilization. CEN­Saclay (1986) 339.. IAEA­TECDOC­440.. 66 10.. CFFTP­G ­87013. (5) Rogers M. Vienna (1987) 257.. Fusion and Isotopie Application. N. Canada. Vassallo G . . 1988. Final Report S. Rept.. Soc. Actes des Journées du Tritium.. IAEA­SR­57/1. paper presented at the Am. Canadian Fusion Fuel Technology Project.S. Soc. Chem.P. Fusion Management Safety and Environment Stud­ ies. Radioactive Waste Management Practices at a Large Canadian Electrical Utility. EUR 6270 en (1979) European Appi. (7) Herring J. paper presented at Third Topical Meeting on Tritium Technology in Fission. April 5­ 10.Y. Toronto. Culham. Conditioning and Handling of Tritiated Waste at Canadian Nuclear Power Facilities. Krasznai J.. ­ Nucl. paper presented at the Am. 1987.P. Vol. 23­25 Avril.. and Dworschak H.L. Sci. Annual Meeting. Tritiated Solid Waste Management.

229.. Actes des Journées du Tritium. (14) Coste G. 1986. ibidem. Dijon. Low Activation Elements for Fusion Reactors Materials. CEN-Saclay (1986) 391. 67 (13) Ponti C . 23-25 Avril. . et al. Conditionnement des Déchets Tritiés Issus du Reacteur EL3.

impregnation or encapsulation treatments per- formed on such tritiated waste composites were the options at first investigated to provide an additional physical barrier that might minimize the tritium release from solidified liquid wastes.20-22). 68 11. Europe (23.24. Consequently surface coating. preparation.1 Additional treatments on solidified liquid wastes In subsection 9. To this end a proper choice of the resin catalyst and cure agent is needed either in the polymer impregnation or encapsulation options. although neither tritiated material was capable of retaining the totality of the incorporated water molecules. polymer impregnated and encapsulated tritiated waste composites. compo- sition. epoxies. Many extensive experimental studies have been carried out in the USA (1. surface conditions and porosity. which apparently make comparative the leach test results a comparative evaluation of these results is somewhat difficult. Thermoplastic and thermosetting organic resins as well as hydraulic cements were identified as candidate material potentially applicable for the above purposes. Thermosetting resins (e.e. The difficulty is caused by lack of full experimental details on test specimens (i. The various options are illustrated in the following subsections. It is evident that to minimize the partial evaporation of tritiated water molecules incorporated in a solidification matrix the peak of temperature reached during the thermosetting reaction has to be keep as low as possible. Consequently to minimize the partial evaporation of tritiated water from the solidification matrix during the coating process only relatively low melting material can be applied. the application of integrated multiple barrier systems has been investigated in order to attain a satisfactory level of tritium containment.3 the performances of several solidification media have been assessed in terms of tritium retention efficiency. During the thermosetting reaction the temperature in the bulk of the material generally increases to a maximum and then decreases to the ambient value.g.4-19). polyesters). The obvious conclusion was that the tritium immobilization achieved for a triti- ated liquid incorporated either in a cement or WEP resin cannot be considered suffi- cient to meet the suggested maximum tritium release target of 10 3% per day (20). even if most laboratory leach tests have been performed using small volume specimens. which conversely are liquid at normal temperatures. CONTAINMENT OF TRITIUM IN SOLIDIFIED LIQUID AND ENCAPSULATED SOLID WASTES Since the degree of tritium immobilization achieved by solidification and/or encapsulating media was deemed to be inadequate for reducing tritium releases to an acceptable level. dimensions. Results have been reviewed by various authors (2.30) and Canada (25-29) to investigate tritium leachibility from coated. volume to surface . 11. Thermoplastic resins which are solids at normal temperatures need to be heated to become liquid. solidify in presence of a catalyst or a curing agent. As pointed out in these review. WEP resins and portland cement did appear the most efficient.

However this gives a further opportunity of comparing leaching behaviours. 11.5. It was demonstrated however that. 11. even if on an approximate basis. delamination and crackings which would result in a sudden increase in the rate of tritium release equal to that for an uncoated concrete. with the increasing of the leach time the leaching reduction factor decreased as expected.1.1 Surface coating Coatings may be applied to cement or concrete blocks by several techniques such as dipping.1. or casting around the block. Results of leach test performed at LASL (Los Alamos Scientific Lab. To minimize evapora- tion. For this reason their application to waste composites was disregarded.1. no effluent should be generated. after 57 weeks) both the factors decreased remaining still significant only for beeswax and paraffin (f ~ 16). For harmonization purposes all the reported data have been expressed as cumulative per cent tritium releases referred to the total tritium amount initially present in the package. If thicker asphalt layers were applied to specimens by successive dippings or casting techniques still lower cumulative per cent tritium releases were measured. coating materials and procedures should be selected to avoid applications neces- sitating high temperature. renewal frequency of leachant). 69 ratio) and by uncomplete reporting of leach test procedures (sample surface to leachate volume ratio. since their integrity often become worse as time goes on.22) on surface coated cement specimens are shown in Tabs. The technique chosen should minimize handling to reduce the possibility of contamination.1 to 11. painting. although the assumption of a linear relation- ship between leach time and per cent release is not true for some leaching isotherms. after decay correction.2 Shalimastic HD. 11.2. 11. With proper process design. Average daily per cent releases are also indicated in each table.g. However.4 weeks of leach testing a reduction factor of 28 was attained with respect to the uncoated specimen. Anyhow some leach test results are pre- sented in Tabs.2 Polymer impregnation The polymer impregnation process allows to fill the pores and capillary voids usually present in the body of a cement block with a liquid organic monomer which is .3. However as the leach time increased (e. after 5 weeks of leaching the reduction effect on tritium leach rate was considerably high for beeswax and paraffin (f ~ 66) and still acceptable for asphalt (f . such coatings in most cases cannot keep unchanged their efficiency for long times. After 4. some types of coatings are subject to spelling. However.5-9).1 and 11. although capable of improving the leach resistance properties of a tritiated cement composite. As shown in Tab. 11. 11. As shown in Tab.) (1. a cold-applied coal-tar paint appeared to be the most promising coating material. Coating applications should be done in a closed system to prevent tritium release through evaporation. remaining still significant after 35 weeks (f = 10). Commercially available coating paints tested at BARC gave fairly comparable results.22) and BARC (Bhabba Atomic Research Centre) (2.

9x10"2 5 (6) -111 3. n.8x10"1 -1.0 H1 Uncoated 10 -39.0x10'2 16<6> n.12 -0.a. (3) Thicker coatings obtained by successive short dipping steps in hot asphalt at 150°C (4) Thicker coatings (0.a. = not available .T16 Uncoated 10 -32.22 O 69 -19.6x10" 3 3.0 HI Uncoated 5 -32.0 H4-H5 Beeswax.a.6 9.0. n.32 T17 Roofing Asphalt 5 . Asphalt ( 4 ) 4 8.2x1o"1 1 -111 3.9x10"1 1.6X10"1 1 1 . n. Asphalt ( 3 ) 5 4.25 7. Curing times variable from 2 days up to a year.5-1 dm 3 ) changed at 1 and 4 weeks intervals.1 · Results of leach tests performed at LASL on coated tritiated concrete specimens.0 8.75-1 inches thickness) obtained by a casting procedure (5). Paraffin 5 4.a.0 0.12 0. _ .6x10"1 .12 0. n.a. (2) Coating obtained by extended dipping in hot asphalt.0 1. ratio (dm 3 ) MBq mCi type Time (wk) Reduction Cumulative Average Factor Daily (d" 1 ) 0. SPECIMEN I DENTI FI CATI ON RESULTS u/c Volume Trit i urn Series Coating Leach Per cent Release Leach Rate Ref.32 T6.32 T6.0 4.1 .0 H7 Asphalt < 2 ) 5 6.T16 Uncoated 5 -26.í 57 -4.12 0.TABLE 11.3x10"1 1 .3 1.0 1.T16 Uncoated 69 -58. n.0 HI Uncoated 57 -65.a.4x1o"2 -66< 6 ) .1x10"* (1) Portland I cement paste prepared by a current laboratory mixer.8x1o'1 57 36.a.9Χ10"1 -1.a.0 1.5x10" 2 -9<5> - 1 3 (5) 1.0 5.6x10'1 -111 3.32 T6.a. Leachant (0.3.3(1) . (6) Compare with type Η uncoated samples. n. (5) Compare with type Τ uncoated samples.a.5x10"1 1 - -111 3. n.4x10" 2 • n.0 3.a. n. n.8(6) -111 3.

0 2.6 6.0 1.4 14. (2) A two-pack-air drying paint with polyamide as hardener (2).4 3.6 18.0 8.0 2.7 9.7 2.6x10 28 9. curing time of 28 days. « not available . After coating leaching was started at the 4 5 t h day fr casting.0x10' Epoxy (2) 4.a.9x10' 10 Anticor (4) 4.5 2.6 1.Results of tritium leach tests performed at BARC (India) on coated concrete specimens.a. SPECIMEN IDENTIFICATION RESULTS u/c Volume Tritium v/s Coating Leach Per cent Release Leach Rate Ref.0 7.0 9.4 0.2 .4 Sha limasti c HD 0.9x10" 3.6 0.8x10 -2 (1) 100 g cement + 40 ml tritiated water + 20 g vermiculite.0x10" 1.0 4.6x10 4.5x10 H n.7x10 -1 -35 20.25 (3) 4. Uncoated 4.5x10 (2. n.2x10 20 9. ratio (dm 3 ) MBq curies (cm) Time (wk) Reduction (mg) Cumulative Average Factor Daily (d 1 ) 0.3. (4) CNSL epoxy coal-tar pitch paint (Indian Patent) (2).0 8.5x10" 18 -35 4.0 0.5 1.0 1.8 1.TABLE 11. (3) A cold-applied coal-tar paint CA50 (USA) (2).2x10" 22 -35 2.5x10 5 ) 9.22 -35 16.4 (1) 9.

11. A PITC specimen of the same dimension and formu- lation (10-12.3 have also been reported results obtained from small scale PITC specimens leached at MLM (see Tab. From the comparison of SRP and BNL data it appears that the leach rate of tritium unex- pectedly increased with burial time and that after approximately 30 weeks more severe leaching occurred in static than in burial leach tests. Some differences as compared to the lysimeter specimens were due to the higher specimen density prior to impegnation which allowed a lower polymer loading and gives a higher composite density after impegnation (see Appendix VII).22) as those used in lysimeter testing at the SRP was submitted to a static leaching test by distilled water at the BNL in order to make a comparison of results.73%) obtained after about 55 weeks from static tests.3) became comparable with the value (0. The pos- sible negative effect of polymer impregnation on the completeness of cement hydra- tion could in fact be enhanced by the method employed in the production of tritiated cement specimens. Leach data (i. Polymer impegnated tritiated cement (PITC) samples. The resulting composite is essentially impermeable to water and has significantly improved strength. This treatment gives a final composite not subjected to failure like in the case of coating applications and hence it is much more reliable as a mean to achieve a barrier to tritium release.61%. 72 then polymerized "in situ". its effect being compensated. Hawthorne (25) suggested that an eventual interference with the hydration process by the polymer could account for the variability of the results obtained by BNL and MLM. For these reasons the polymer impregnated tritiated concrete (PITC) has been regarded as an interesting option for tritium immobilization purposes.22) without con- tainers in individual lysimeters. durability and resistance to chemical attack and wheathering.e. After 62 weeks in fact the cumulative per cent release (0. 22) after the removal of their polyeth- ylene container. Note that there is a considerable discrepancy in terms of tritium release between the MLM results from PITC specimens 59 & 72 and results of the duplicate lysimeter sample tested at BNL. 11 and 12. to a partial channeling of water down the sides of the lysimeter instead of being homogeneously absorbed in the soil and thus brought in rapid contact with the buried specimen. cumulative and daily per cent releases) are shown in Tab. as explained in refs. the latter showing a tritium retention effi- ciency from one to two orders of magnitude higher than that of MLM specimens. 11. Tab.3. Neither laboratory did made any explicative comments on this discrepancy. The preparation of a polymer impregnated waste composite is described in Appendix VII. . This because the former value was obtained by averaging the leach measurement over a longer time during which the water channeling disappeared. This could explain the differences in the above results from cement specimens prepared by a conventional mixer technique (BNL) and gravity injector technique (MLM). 5 of ref. This was due. prepared at BNL (see Appendix VII) were buried at SRP (Savannah River Plant) (9-12. In Tab. Water diffusion inside the concrete block as well as water penetration from outside is thus minimized. 11.

Release values averaged on four specimens.54 PITC/13 -12 0.1 microliters fractions.05 PITC/0.84x10" 70 33.0.0 1. ratio (dm3) GBq curies (cm) Containment No.1 1.TABLE 11.010 4.6) no PB 42 24.54 PITC/16 (1) 31 0. Polymer impregnation based on the soak technique.5.90x10 •3 0. Time (wk) (mg) Cumulative Average Daily (d ') 0.61 1. SPECIMEN IDENTIFICATION RESULTS u/c Volume Tritium v/s Type of Sample Leach Per cent Release Ref.0 0.5 * Polymer Impregnated Tritiated Concrete with 16. PITC/16.2 14.12.2 14.3 · Results of tritium leach performed at SRP.16 1. 1 and 0.22 (2) -13 370 10 4.34x10" 13-19.22 (1) -16 370 10 4.13.40x10" 0.13.0 1.22 -43 0.05 PITC/5 59 13 39.98x10 (1) -28 0. PB = Polyethylene Bottle Package.22 0.6) no PB 41 52.1 4.30x10 x10 3 (38.80x10 11.73 0.5.56 1.67x10" 100 43. .32x10 x10 3 (38. Portland type III cement paste prepared at BNL by a conventional dought type mixer.3 386 1.5% catalyst.39 1.88x10' -55 1.5 72 13 12.12.0 0.25 (3) -0.25 (3) -0.3 386 1. (3) Portland type III cement paste prepared at MLM using the injector technique.60x10' (1) Lysimeter sample tested at SRP without container.0.81x10" ω 68 64. (2) Duplicate lysimeter sample prepared at the BNL like samples at point (1) and leach tested at the BNL without container.93x10" 11. No change of leachant and periodical sampling of 10. BNL and MLM on PITC specimens. Curing time of 5 days at 40°C.7 0.22 (1) 62 0. Leachant (40 dm ) not changed and sampled (1 ml fractions) periodically for analysis.

5xl0 2 ) measured in the case of the polyesther.6x10"2% (f = 2x10s) in the case of epoxy resin.Karlsruhe to compare the efficiency of encapsulating media such as hydraulic cement and some thermosetting resins with the aim of interposing against tritium release an additional physical barrier between the surface of tritiated waste composite and the primary container. .2% (f = 2.4 after about 1 year the barrier effect of polyester and epoxy encapsulating media is well evident. As shown in Tab. With this encapsulating medium the cumulative per cent release of tritium is reduced after 110 days of leaching up to 10"*% (f » 5xl0 4 ) against only 0. No further experimental details were given on this experiment. Other specimens containing tritiated water solidified by a cement matrix as well as tritium gas confined inside a hollow cylinder of various untritiated barrier materials were encapsulated by 1 to 2 cm thick layers of polyesther or epoxy resin. 11.1.5 mCi) for tritium gas and tritiated water respectively. Leach tests were performed over a leach- ing period of 500 days and with the initial activity of tritium in each specimen being of about 45 MBq (~ 1. The best leach resistance of epoxy resins was confirmed also when encapsulated hollow cement cylinders containing tritium gas were leached over the same leaching period and conditions. Ontario Hydro and KfK. This was explained in ref. When a cement matrix is used for solidifying tritiated water (instead of a IX resin support) and then is encapsulated in a polyester or epoxy resin the best leach resistance effect is largely obtained by the epoxy resin. It is also worth noting that in both cases the average daily per cent release is largely below the suggested (20) maximum release target of 10"3% day.4 the cumulative per cent release of tritium from the epoxy encapsulated specimen after 110 days was of the same order of magnitude of the value measured in the case of tritiated water solidified by a cement matrix. Some leach data calculated after comparable leach time and expressed as cumu- lative and daily per cent release values have been reported in Tab. The cumulative per cent releases of tritium from encapsulated specimens decrease from 49% to 7.4 for com- parison purposes.2 mCi).1 and 2.3 Encapsulation Extensive experimental studies have been carried out at CEN-Grenoble. 11. As shown in Tab. Furthermore epoxy encapsulated cement appears to be the most efficient double barrier system for containing gaseous tritium. polyester or epoxy resin). They were then submitted to leaching tests during 110 days.3x10"*% (f = 7xl0 2 ) in the case of polyesther and from 56% to 2. 74 11. (24) as due to the best resistance to the hydrolyse shown by the epoxy resin in comparison with the polyesther. At CEN-Grenoble (23. The initial tritium activity in each specimen was about 80 and 93 MBq (~ 2. Unfortunately no details are available on commercial types of cement and polymeric organic resins used for fabricating all these specimens.e. 11.24) small scale specimens containing tritiated water absorbed on ion exchange resin and fixed into a matrix of polyester or epoxy resin were fabricated in order to experimentally evaluate and compare the variation of tritium leach rate from specimens with and without a 1 cm thick layer of encapsula- ting material (i.

OxlO" ­5.833 IX ♦ Epoxy Epoxy 380 2.4 1.a.16< > 1. n.5x10"3 ­ ­ 25 (1) As tritiated water.8x10"* ­2. Cement <5> None 64 2­4 ­5. SPECIMEN IDENTIFICATION RESULTS i/olume Tritium V/S Solidification Encapsulation Leach Per Cent Release Leach Rate Ref. n.0 2.2<1> 0.1 44.6x10" ­3. ­J n.4 1. n. . (dm3) MBq mcuries (em) or Containment Medium Time Cumulative Average Reduction Factor Medium (d) Daily (d'1) 97 43 4.a.4 ­93 2.24 1 97 53 5. n.4 1.1 44.33 Cement <5> Polyester(6> 110 2.2<1> 0.33 Cement Epoxy 110 ­2. n.a. n.4 1.78 Ol ­0.51 1.1 44. n.0x10' 1. 23.a.1x10* (7) n. n.0x10'2 1.4 ­80 2.TABLE 11. cement aggregates particles.33 Cement Epoxy 110 1.3X10" ­2. (5) Hollow untritiated cement cylinders containing tritium gas.a.0x10'* n.0 5.5x10"5 ­0.4 · Results of leach tests performed at CEN­Grenoble.5x10" ­0. n.a.4 ­80 2.4x10" 3.24 <4) (6> 3 5 ­0. n. Polyester Polyester < 8 ) < 1 0 ) 365 10. (3) Used only as a supporting material for tritiated water.2<1> 0. n.5x10'1 1 2 97 3.a.5x1ο"1 " ­0.3x1ο"1 .a. (10) 2 cm thick encapsulating resin.a.16<2> 1. (9) Hollow epoxy cylinder loaded as in (7). Cement None 64 0.4x10 ' ­0.1X10" I. n.a.a.a.833 IX <3> ♦ Epoxy None 380 56 1. Epoxy <9> Epoxy (10 > 365 2.4 ­93 2.833 IX < 3 ) + Polyester Polyester <6) 2 2 380 7.a.1 44.833 IX <3> ♦ Polyester None 380 49 1.5x102 ­ 23.0x10'* ­7x10 1) <3> <6> 97 8.7x10'2 ­ ­ 25 n. (8) Loaded with sand. (6) 1 cm thick encapsulating resin. (4) Tritiated cement matrix. (7) Hollow polyester cylinder containing tritium gas and I wi th 50wtX (2) As tritium gas.0x10"1 Ι.3x10'3 8.6x10'2 ­7.33 Cement**' Polyester (6) 110 2.βχΙΟ'3 ­2.a.2< 0.0x10"5 ­2x103 (4) 30­70 .0x10"1 ­ 1 ­0.5x103 23 2 <5) <6) 3 5 ­0.a.a.51 1.

7x10"3% per day. The average daily tritium releases. However one has also to take note that. From the comparison of leaching isotherms (Figs.5 along with the corresponding operating conditions. The preparation of WEP and cement specimens incorporating tritiated water and to be then encapsultated. (29).e.5) it appears that a WEP resin layer of suitable thickness (i. WEP/epoxy and WEP/WEP com- posites (see Tab.2) and their aver- age slopes (Tab. Portland cement (PZ 35F type) and polystyrene (DOW-binder 101) specimens containing respectively about 32 wt% of .5) are approximately one order of magnitude lower than the suggested (20) maximum tritium release target of 10~3% per day.e.2 (taken from ref. Most isotherms are linear or pratically linear. Similar leaching experiments were performed at KfK-Karlsruhe (30) to investi- gate the performance of cement and polystyrene as potential encapsulating media for silica gel and zeolite 5A loaded with tritiated water. 26) where percentage cumulative tritium releases are plotted versus the leach time. 76 A leach test programme was also developed at Ontario Hydro (25-29) to investi- gate the efficiency of polyester and epoxy resins as encapsulating media for tritiated waste composites.2 each experimental isotherm corresponds to a composite specimen resulting from one of the indicated combinations of solidification matrices with encapsulating media. 1 cm) applied over tritiated cement or WEP matrices is the most effective encap- sulating media for minimizing tritium leaching. Leach tests were performed (26) by immersing each encapsulated specimen in 0. The effect of various encapsulating materials such as cement.e. 11. i. 11. 11. was carried out as described in Appendix V. Results of static leach test obtained with non-encapsulated specimens are also reported for comparison purposes. After 150 days of leaching it reduces in both cases the tritium leach rates by a factor 10s. 11. the average slopes of these isoterms. These resins which are listed in Appendix VIII were selected and tested as encapsulating media for water solidification matrices such as Portland Cement type 30 and water extendible polyester (WEP). In Appendix VIII is described the procedure used to apply over both the tritiated WEP and cement specimens a 1 cm thick layer of one or the other of the above encapsulating materials. Static leach data were measured over a maximum leaching period of 150-180 days. whereas is approximately one order of magnitude lower in the case of a tritiated cement matrix. Note that the average daily tritium per cent releases (i. In Figs.2 litres of demineralized water. have been also calculat- ed after 60. 11. Several epoxy and polyester resins with relatively low peak exotherm tempera- tures were identified (23) which did not cause bubbles formation and trapping in the resin just around the cement specimens as occurred with some others resins.1 and 11.1 and 11.1 and 11. an increase by a factor 10 of tritium leach rate from the WEP encapsulated specimen was subsequently observed after 750 days of leaching time corresponding to an average leach rate of 1. as reported in ref. WEP and epoxy resins on the release of tritium from composite specimens (prepared using cement or WEP as tritiated water solidification matrices) are illustrated in Figs. the leach rates) calculated for portland/WEP. Under the same leach conditions the efficiency of an identical layer of epoxy resin is comparable in the case of a tritiated WEP matrix. 11. The leachant was not changed throughout the test and samplings were carried out periodically through a rubber septum by means of a syringe provided with a long needle (150 mm). 150 and 180 days of leaching and reported in Tab.

5). 11. Cement and polystyrene specimens directly loaded with tritiated water were also and tested under the same leaching conditions (see subsection 9. leach time.001 Λ ' ' M ΙΠ£ J ' ι ι uin HI' io 1000 Oirv un FIGURE 11. .E2*.5 litres of water. 9. S S £ o. silica gel (loaded with 26 wt% of H20/HTO) and about 64 wt% of zeolite 5A (loaded with 21 w% of HjO/HTO) were prepared according the procedure described in Ap­ pendix VI. ­ a significant improvement of tritium retention efficiency is achievable only if tritiated water is directly incorporated into a polystyrene matrix.01 / ¿S O. Comparison of encapsulation media over a tritiated portland cement matrix.E» Portl ond Cement /Portland ¡ Cement .4 taken from ref.27 Portland Ctment/No Encapsulation ƒ * · .i Χ' / ES. s.E2S 2S. From the comparison of the average slopes of tritium leaching isotherms reported in the above figures and in Fig.3. Static leach tests were performed over a leaching period within 50 to 200 days using as a leachant 0. ει s 0. (30).Et Portland Cernem IWEP ¡ ΕΙ. 77 .2 of Section 9 it appears evident that: ­ the encapsulation by cement or polystyrene of matrices incorporating tritiated water such as silica gel or zeolite does not significantly increase the efficiency of tritium retention which is normally achievable by the direct solidification of tritiated water by cement.1 ­ Static leach tests at Ontario Hydro (26).E« Portland Cernem lipon Slí/LO/LOS EJ. The effect of cement and polystyrene encapsulating media on the release of tritium from silica gel and zeolite previously loaded with tritiated water is shown in Figs. Cumulative per cent tritium releases in water vs.El Portland CamtntlEpon IlSISOt j E3.3 and 11.ΕΙ* Portl ond Cement /Aropol C IOS · EM. " · El.

3 .ooi ι ι ι ι ι IIII ' Ι Ι Hill Ι Ι Ι Ι Ulli 100 1000 Bays FIGURE 11.Eli WEP/Epon SI5IL0/10S .E2I WtP/Portl ond Cement . Stati c leach tests at KfK (30). Cumulati ve per cent tri ti um releases i n water vs./ΗΤΟ in spe cime n 10 20 30 40 50 60 70 80 >Γ(η)'" FIGURE 11. silicagel with 26% H ? 0/HTO X —— in ce me nt 85% HpO/HTO ifiom silicage l) in spe cime n in [low binde r 101 16 5% Η.E2· E27. 78 «*.. E U WEP/Epon S IS /S OS . Compari son of encapsulati on medi a over a tri ti ated si li ca gel matrix. leach ti me.01 / £22 o. EI1. Compari son of encapsulati on medi a over a tri ti ated WEP matri x..«7 «: ■E1S.E2S / / I / I » 3 0.E2· WEP /Aropol C JOS E21.EI* ■EI7.2 .1 ί EIS. . ·7 WCP ISo Encaptulation Ζ E IS .•M.E22 WEP/WEP E27. EU.EII / 0. leach ti me. Fracti onal tri ti um releases i n water vs. Stati c leach tests at Ontari o Hydro (26).

28 -0.S . (2) Volume to geometric surface ratio is 0.2x10" 1 1. Cure time: 1 and 7 days for solidification and encapsulation media respectively.4x10'* .51 36.28 -0. -4.86 E19.1x10'* -103 1.0 7.20 WEP WEP<6> 150 2. (3 0.1x10'2 2.1(3) 100 2.0 3.3X10"1 -3 1 0. Shell Canada Chemical Company.17 -0.TABLE 11. .68 46.7x10'2 3.25 Portland 30 Portland 30 < 4 ) 60 11. (3) Including encapsulating material volume. ratio (dm ) MBq incuries Code Matrix Medium Time Cumulative Average Reduction Factor <d) Daily (d 1 ) 0.1 -83 2.80 E32.0x10"2 3.8x10"1 1 - 180 63.0 -0.28 WEP Portland 30 < 4 > 60 2.4x10' -300 26 -J 0.30 Portland 30 WEP (6) 60 2. 1.30 E3.1 -99 2.3x10" 2 2.4 Portland 30 Epoxy resin 60 1. -103 (1) Water to matrix material (cement or WEP) weight ratio.1 -93 2.30 -0.28 -0.9 4.00 E17.1x10** - 150 3.23 26.1(3) 103 2. 26 1.2x10"1 .8x102 .0 1.47 WEP(6> None 60 13.0 -0. (5) High Alusina Cement.0 -0.37 HAC (5) None 180 76.2x10"3 3.41 E5.1<3> -77 -2.0x10* -770 26 1.5 1.9x10'3 - 1 3 150 2.18 WEP Epoxy resin 60 1.1(3) 105 2. SPECIMEN IDENTIFICATION RESULTS W/M < 1 ) Volume < 2 ) Tritium Sample Solidification Encapsulation Leach Per Cent Release Leach Rat· Ref.4x10"* • - 0.1 <3> 89 2.1 > 85 2.Results of leach tests performed at Ontario Hydro. (6) Water Extendible unsaturated Polyester.5 4.2x10"1 1 180 24.1x10' 1. (4) Portland type 30 Cement.28 -0. .0 2. Ashland Chemical. .6x10'5 .0 -0.8 Portland 30 WEP<6> 150 4. (7) Epon 815 epoxy resin.18 E29.1x10'2 1.833 cm for all specimens. Aropot 661-P.1(3) 111 3.28 -0.33 WEP WEP<6> 60 2.9x10"1 -4 .5X10"1 1 0.10 E24.1<3) -79 2.27 Portland 30 < 4 > None 60 47.72 £27.4 1.

11.Ο/ΗΤΟ (trom Κ 154) in specimen 50 60 > V(h)1 FIGURE 11.2 Containerization of solidified liquid waste It is undoubt that the above additional treatments of solidified tritiated liquid wastes require the application of complex procedures.e.. 11. 1 and 0. which appear rather unpractical for field applications. Furthermore in dealing with tritiated waste materials. . 11. coating. The samples were than placed in a test apparatus (Fig. impregnation and encapsulation procedures become still more critical mostly because of the stringent safety requirements associated with tritium handling.6 litres of distilled water for leach testing. No change of leachant was made and 10. HDPE has the lowest water permeability and the best thermo-chemical resistence among the common polymers. At MLM (13-19) small-scale specimens were fabricated in the frame of a leaching test programme in order to measure and compare the release of tritium from tritiated concrete with and without polystyrene impregnation.e. Comparison of encapsulation media over a tritiated seolite matrix.6 taken from ref. Static leach tests at KfK (30). 80 K 154 with 21% HjOimO in Dow-binder 101 13 4% H ? 0/HTO in specimen in cemenl 6 8% Η. Furthermore it is a readily available material (29. High density polyethylene (HDPE) was selected by both laboratories as the best container material. Fractional tritium releases in water vs.5) containing 1. After polyvinylidene chloride (SARAN). In this light extensive leach tests programmes have been carried out at MLM (13-19) and Ontario Hydro (27-29) to investigate the efficiency of a primary packag­ ing container acting as an additional physical barrier against tritium release from solidified tritiated liquid wastes.1 microlitres fractions were sampled periodically. Their preparation was done according to the procedure described in Appendix VII. the confinement of tritiated waste composites inside a suitable primary container) appears to be a more practical and less expensive option.4 . leach time. A part from "nude" specimens tested for comparison purposes. all the other specimens were leach tested being contained in 500 ml linear high density polyethylene bottles. (22).31). Tritium permeation data (i. Conversely the simple "containerization" (i. cumulative tritium per cent releases) for the most significant nine test samples prepared using a portland type III cement (13-19) are given in Tab.

6) between release data from the fifth concrete sample group (which did not have styrene added) and those from first and fourth PITC sample groups. As shown in Tab. Without the polyethylene a thin layer of polystyrene was in fact the only barrier between the cement matrix and the water (18). using 0. yielding consequently a lower internal bulk temperature. 11.5 . The release from sample 72. Stopper RTV sealant Coppe spacer Container lid 16 oz RTV sealant polyethylene bottle 1600 cm3 of water 1/2 gal polyethylene bottle Styrene impregnated Copper tritated spacer concrete FIGURE 11.5% catalyst.5% catalyst (as recommended by the BNL) was approximately one-half the release from sample 59 using 5% catalyst.6 the percentage of tritium released into the water bath from samples 59 and 72 after the bottle removal was from 50 to 100 times greater than that diffused through the polyethylene bottle of samples 57 & 58 (first group) and 69 to 71 (fourth group) respectively. The greatly increased tritium releases from these samples was essentially attributed to the removal the polyethylene bottle. Such a bar- . The dif- ference is attributed to a lower rate of polymerization reached with 0. This was attributed to the barrier effect of the polyethylene bottle which was much thicker than the layer of polystyrene. Laboratory scale permeation tests at MLM (19). Experimental set up for testing PITC specimens. 11. 81 In this table the corresponding average daily tritium per cent releases have also been reported for comparison purposes. No significant differences were found (see Tab. The higher polymerization temperature in the 5% catalyst polystyrene was thus deemed as being the most likely responsible for the larger tritium release of sample 59 (18).

7x10­2 1 2 100 43.0 6. n. ratio (dm 3 ) TBq Ci (cm) No. ­ TC no PI 20 2. containment Time (wk) Cumulative Average Reduction (mg) Daily (d' 1 ) Factor n.0 1. no PB 28 8. (38.8xio'.a. ­ 54 0.2x10 2 .4x10'3 ­100 1 59 PITC/5 13 39.0x10"2 ­ ­ 5 73­74 TC ♦ PB 6 0.4x10"3 .1x10"3 ­ • (1) Portland type til cement paste preparation based on the injector technique.a.1 13.11 2.3x10"' 1 1 4 69­71 PITC/0.66 1.2 14.3 386 1.22 64 0.2x10"3 ­60 ­ 4 72 PITC/0.1 4.5 6 0.6 ­ Results of tritium permeation tests performed at MLM on tritiated concrete specimens with and without polymer impregnation.10 2. TC « Tritiated concrete.21.3x10'] . » not available. PI « Polymer Impregnation.1 microliters fractions.0 6.35 1. no PB 41 (2) 52. No change of leachant and periodical sampling of 10. ­ ­ 68 64. (2) E ffective teach times calculated by subtracting 25 and 21 weeks to the permeation time of 1 s t and 4 t h sample groups.5x10'3 .50 ­1.6) + PB 33 0.43 1. .5 13 12.5 or 5 ­ Polymer Impregnated Tritiated Concrete with 0. PITC/0. n. 1 and 0. No.a. n.8x10"2 . .22 0.7 8. CD IV) ♦ PB 33 0.6x10"3 .25(1> ­0.00 ­4.0 i.TABLE 11.a.a.54 1. Polymer impregnation based on the soak technique.5X or 5X catalyst. n. no PB 42 24.1x10'2 1 ■ ­ 20. no PI 25 0.05 1 57­58 PITC/5 6 0.26 1. .50 2.5x10"3 ­30 .4x10"2 ­ ­ 70(2) 33. . PB « Polyethylene Bottle Package. .a. m . n.10 2. SPECIMEN IDE NTIFICATION RESULTS u/c Volume Tritium V/S Group Sample Type of Leach Per Cent Release Leach Rate Ref.0x10 3 ­ 65 0.5x10 3 13­19.

tritium release rates expressed as average daily per cent releases (d"1) and cumulative fractional releases (cm d"1) have been calculated as 1 160 200 240 DAYS LEACHED AVC(W1.2 cm thickness were utilized in order to determine the effect of HDPE wall thickness on tritium release rates. (20).2A) FIGURE 11. 0. 125 and 500 millilitres as well as fabricated HDPE containers of 1. The effect of such a barrier was determined with and without an additional layer of WEP resin being externally applied to encapsulate the HDPE container. fourth and fifth specimen groups to values which are very near the maximum release target of 10"*% per day suggested in ref. Based on these data.7 and 11.7 taken from ref.3 and 5. 11.5 and 0. 83 rier was in fact so efficient in reducing the tritium leach rate that. . Within 4.6 . The effects on tritium leaching rate due to the containerized WEP matrix (used for tritiated water incorpora­ tion).2) « AVC(C1A.6. 2A. when not removed. expressed as cumulative fractional tritium releases x(V/S).8. 11. Leaching data. to the different thickness of the HDPE containers (used for the containerization of tritiated WEP composites) as well as that due to the additional layer of WEP resin applied around the HDPE container are shown in Figs. Commercially available HDPE containers of 25. 11. To encapsulate the HDPE container the procedure described in Appendix VIII was slightly modified (see Appendix IX) in order to prepare replicates which might behave identically. Finally it is worth noting that after approximately a year of leaching time the polyethylene container reduced the average daily tritium per cent release of first.2. A WEP resin was the matrix material utilized for incorporating tritiated waste water according to the procedure described in Appendix V. At Ontario Hydro (27-29) the efficiency of a HDPE container as a barrier against tritium release from waste composites incorporating tritiated water was investi­ gated. The physical characteristics of specimens are summarized in Tab. Static leach tests at Ontario Hydro (29). it had the capability of masking eventual differences due to a further treatment of the concrete specimen. W'1. Cumulative fractional releases χ (V/S) versus leach time for specimens CI.8 GBq (116-158 mCi) of tritium were incorporated in each specimens. (29). CIA. are plotted versus leach time.2.

0 none 117.0 0.3 519.36 117.14 354. VOLUME S/V INITIAL TRITIUM Ref.85 cm thick encapsulating layer on the HDPE container.83 130.29 PE3 Solidified HTO/WEP in 8.7 98.4 0. CODE DESCRIPTION WASTE SPECIMEN THICKNESS OF COMPOSITE OF COMPOSITE ACTIVITY d(cm)/h(cm) (cm) (cm 2 ) (cm 3 ) (cm"1) (GBq) (mCi) U1 Liquid Water in 8.90 encapsulated in WEP (2) HDPE: High Density Polyethylene (1) 0.Physical characteristics of specimens utilized at Ontario Hydro for static leach tests.61 151.0/8.80 00 PE4 fabricated HDPE Container 4.4 483.00 443.TABLE 11.6 0.61 4. & encaps.82 26 E20 no container. 0.3 519.0 0.56 W2 500 mL HDPE Container C1 Solidified HTO/WEP in 8.8/7.66 4.45 4.2 0.14 370.107 2.94 encapsulated in WEP (1) 46 Solidified HTO/WEP.68 5.64 125.13 1.03 PE6 fabricated HDPE Container 4.11 27.100 2. SURFACE AREA AVG.40 118.9 822.32 C1A Unsolidified HTO/WEP Emulsion 8.68 4. 4.13 1.66 E19 Solidified HTO/WEP.29 116.46 120.71 47 no contain.68 C2A in 500 mL HDPE Container 5.7 .0/5.2 0.104 2.14 337. SAMPLE SAMPLE DIMENSION OF CONTAINER AVG.68 4.85 158.19 E2 500 mL HDPE Container.0/5.08 PE5 Solidified HTO/WEP in 8.0 1.4 0. 5.50 PE2 fabricated HDPE Container 4.6 0.2 0.8/8.52 122.0 none 117.098 2.14 354. (2) 1 cm thick encapsulating layer on the WEP composite .0 0.4 0.5 0.28 115.87 E1 Solidified HTO/WEP in 8.0 0.35 117.0/8.50 395. 0.6 539.0 722.20 368.00 PE1 Solidified HTO/WEP in 8.0 0. 5.0/8.71 4.1 601.41 119.57 C2 500 mL HDPE Container 4.36 117.4 0.7 98.8/8.0/8.

PE5. 80 120 160 200 240 OAYS LEACHED « (C1.2. This enables to make the cor­ relations of data measured for specimens which originally are different in size and geometry.8 and 11.2. Cumulative fractional releases χ (V/S) versus leach time for specimens PEI. Cumulative fractional releases χ (V/S) versus leach time for specimens C1.2) FIGURE 11.2.14 cm thick HDPE container (29). where V is the vol­ ume and S the geometric surface area of the specimen.2) AVC(PE3. Related leaching data are shown in .2.2.8 ­ Static leach tests at Ontario Hydro (29).2. Note that data related to the cumulative fractional release rates have been normalized by introducing the factor V/S.4) » AV G (PE5. added with 5 wt% of dried silica and con­ fined inside a 0.9. W 1. PEI. PEI .6. 11. El . ¡each tests were also extended to specimens of tritiated portland 30 cement.6) FIGURE 11. To determine the influence of the matrix material (i. 11.2) » (E1. WEP or portland cement) utilized for solidifying the tritiated waste water.e. For comparison purposes leaching data related to specimens of tritiated WEP composites encapsulated in a layer of WEP resin were also included in Tab.9.7 ­ Static leach tests at Ontario Hydro (29). shown in Tabs. 85 DAYS LEACH EO O AVG(PE1.2) (PEI.2) « (W1.

6 ­4.94x10 3.2 WEP 0.4 WEP<A> 0.a.6 -4.2A (3) ­3 0.14/500 200 8.3x10­4 0.2/n. (3) Unsolidified UEP/HTO emulsion.64 PEI. 200 0.5 ­1.4 ­4.29 <4> 519.0x10 ­4 ­4 ­6 1.47x10 ­2 27. Comparison of results.86x10 6. DAILY CUMUL.31 -116.5 6 539.4 ­5.1x10 1.62x10 5. SPECIMEN IDE NTIFICATION RESULTS C0MPOSITE <1> TRITIUM (1> V/S(1> SAMPLE SOLIDIFICATION CONTAINER EL ACH CUMULATIV E AVG.4 -4.0 1. VOLUME GBq mCi (cm) COD E MATRIX THICKNESS (cm) TIM E FRACTIONAL PER CENT EER LEAS RATE ER DUCTION (cm 3 ) ft VOLUME (cm 3 ) (d) ER EL AS E χ V/S E EREL AS χ V/S FACTOR (cm) (d 1 ) (cm*d'1) 473.47 C1A.42x10 1 27. 200 1.43 -120.a * not available (1) Average of two samples. (4) Solidified UEP/HTO emulsion.55 ­123. FRACT. .80x10 ­10 WEP » Water Extendible Polyester Resin n.47 CI.52 PE3. Water/WEP weight ratio ■ 1.93x10 4.a.TABLE 11.5x10 28 1 519.a.14/500 200 1.14/500 200 3.2 -4.81x10 1 oo CD 601.1x10 ­4 0.83 ­130.0 1.4x10 2.0 -1.47 PE5.4 -1.73 ­155.5x10 0.2 WEP (4> 1.84x10 0.2 (2) 0.5/n.0 1.5x10 ­4 0.6x10 0.29 722. 200 1.6 WEP<4> 0.8 ­ Static leach tests performed at Ontario Hydro on containerized tritiated liquid wastes and waste composites.41 W1. (2) Unsolidified HTO.33 -117.0/n. EL ACH RATE Ref.

0 1. co 822.4x10"5 -0.a.a.2 WEP<2> HDPE/0.6x10" 4 1. Comparison of results.63x10"3 0.29 WEP/1 750 1. -4.06x10'2 1.8x10' 4 0.Static leach tests performed at Ontario Hydro on containerized and/or encapsulated tritiated waste composites. (4) HTO solidified by WEP resin and encapsulated in a 1 cm thick layer of WEP resin.27.16X10"6 -0.5 148 1.3 -2.199 1.5 -4. (5) HTO solidified by WEP resin and sealed in a 0.8x10 2 519.52 12. (6) HTO solidified by WEP resfn and sealed in a 0.27. (cm d" 1 ) 98.14(6> x10 3 200 2.4x10" 6 -0.0 2. Portland 30 no container 60 0.20 WEP<2> (4) no container 150 1.95x10'3 1 27 Silica Fume (7) no encapsul.86x10'3 0. HDEP container and then encapsulated in a 0. (2) Water/WEP weight ratio = 1. LEACH RATE Ref.a. 98.29 WEP/0.1x10'* 0.92X10'3 3.2 WEP<2> HDPE/0. ISPECIMEN 1 DENTIFICATION RESULTS COMPOSI TE* 1 ) TRITIUM11' V/S(1) SAMPLE SOLIDIFICATION CONTAINER & LEACH CUMULATIVE AV.833 E19. DAILY CUMUL.8x10 3 27. . Portland 30 HDPE/0.57X10*1 I. FRACT. LAYER TIME FRACTIONAL PER CENT RELEASE RATE REDUCTION 3 (cm ) THICKNESS (cm) (d) RELEASE χ V/S RELEASE Χ V/S FACTOR (cm) (d'1. -5.4x10"4 1.9x10 3 26.833 n.9 .47 CI.14 cm thick 500 mL. n.55 -123.46x10'5 -2.48 n.0x10 2 27 x10 3 Silica Fume (7) no encapsul. WEP * Water Extendible Polyester Resin HDPE » High Density Polyethylene (1) Average of two samples. (3) HTO solidified by WEP resin only.85 n.86 0. (7) 95X Portland 30 cement additioned with 5X Silica Fume.13 -99.13 -10.29 no encapsul.47 WEP<2> no container ' 180 0.14 <5> 200 1.14 200 0.HxIO" 1 0.33x10'1 1.68 0. which is a 90-95X Si0 2 by-product from the ferro-silicon ft silicon metal production.40 vi -119.75x10"4 1.93X10"5 -10 2 27.11x10'3 1 26.833 46.85 cm thick layer of WEP resfn.22 E1.TABLE 11.14 cm thick 500 mL HDPE container.23 0.29 x10 3 no encapsul.7x10"3 1. VOLUME MBq mCi (em) CODE MATRIX ENCAPS.a.4 -4.5 -2.

even after short contact times.The rate of tritiated water release. all of them being tested after sealing inside three identical HDPE containers (Fig.2. PE3. 11.8).2 (i.The altering effect of the WEP components on the polyethylene permeability is also demonstrated by the fact that tritium leached from specimens C 1. 11. 11. expressed as cumulative fraction of the original tritium activity. (29) this make clear evidence that the increase of HDPE permeability (causing the above increase of tritium release rate) is essentially due to the altering action of the WEP organic components on polyethylene. due to the effect of WEP components. As pointed out in ref. WEP resin specimens incorporating tritiated water and confined inside a HDPE container) is higher by a factor 2 than tritium leached from a tritiated cement-silica matrix.8). .At present the HDPE appear to be one of the most efficient barrier material against tritium release from a tritiated waste composite. This makes also evidence that even if the water permeability through polyethylene is normally expected to be temperature dependent.2) and tritiated water alone (specimens Wl.47) it appear evident that the unexpected increase of tritium release from the WEP/HDPE double barrier system may be explained only by an increased permeability to tritiated water of the HDPE barrier.e. styrene and vinylester and possibly the methyl-ethyl ketone peroxide) have. However tritium leach rate do not decrease linearly with the increasing of the container thickness. decreases as the HDPE container thickness increases. 2A) the cor- responding tritium release rate is approximately higher by a factor 4 and 30 than the values calculated respectively in presence of the solidified WEP/HTO emulsion (specimens CI. This is the conclusion resulting from the comparison of the leaching data from specimens CIA.4 and PE5.6 (see Tab. Tab. the release of tritium across the HDPE container.e. confined inside a HDPE container of an identical thickness (Tab.2 and Wl. .9 where for comparison purposes data from a non-containerized specimen of the same tritiated cement composite are also included. 2A with those from specimens C1. Since without a HDPE container the tritium retention efficiency of a tritiated cement- silica matrix is in the worst case comparable to that of a tritiated WEP matrix (specimens 46. i.9 it follows that . .e. As pointed out in ref.8 & 11. probably because of the more enhanced effect of the organic components of the WEP resin on thin polyethylene layers than on thicker ones. Leach rate even inferior to the suggested tritium release target of 10"3% per day are attained by using such a material. 11. This is the conclusion resulting from the comparison of leaching data related to specimens PE1. In presence of an unsolidi- fied WEP/HTO emulsion inside the HDPE container (specimens CIA. . exposure to 97eC for seven minutes) may so permanently affect the polyethylene permeability.The components of the WEP incorporation matrix (i.e. From the comparative assessment of tritium release data reported in Tables 11.9). 88 Tab. (29) there is an approximate hyperbolic relationship between these two parameters. it is rather unlikely that thermal conditions such as those ones reached during the curing step (i.2. the capability of permanently increasing the permeability of polyethylene to tritiated water.2).6. 11.

This make again clear evidence of the altering effect of WEP organic components on the permeability of the HDPE container.9). Cl.57) is that of lowering the tritium release rate approxi- mately by a factor 102-10s.The efficiency of 1 cm thick HDPE container in terms of tritium retention capabi- lity is comparable to that attained by encapsulating the same tritiated water com- posite in a 1 cm thick layer of WEP resin (29).29) or epoxy resin layers (24. while polyethylene (28.9. 11.8) and E 19. were experimentally determined and compared at Ontario Hydro (27. The barrier effect of HDPE container also provides a reduction factor of approximately 102 (as it results by comparing specimens C 1.2 (Tab. Therefore if both these barriers are applied around tritiated WEP specimens a net reduction factor of at least 10* would be expected.If containerized composite specimens are further encapsulated by a layer of WEP resin like E 1. E19. 11.32) have been utilized as encapsulating media. tritium leaching rates from polyethylene containerized steel specimens with and without a previous WEP encapsulation of the specimen itself.20. Therefore one has to conclude that a HDEP container or drum liner used as a barrier to the environmental tritium release from a tritiated waste composite is proven to attain the best efficiency only if it is employed avoiding any previous contact with solidifying or encapsulating organic compounds which may permanently alter the tritium permeability of polyethylene.2 specimens. as a consequence. of its double exposure to the WEP emulsion during the initial tritiated water incorporation and final encapsulation processes.47.9 the net reduction factor calculated from the release rate values is however less than 10s. the efficiency of the HDPE container is lower than ex- pected. The effect of encapsulat- ing a tritiated WEP composite by a WEP resin layer (as it results by comparing specimens E 19. 11. 57).2 reported in Tab.20 with 46.32) as containment materials to form together with the formers a double barrier system. 89 .3 Containment of encapsulated metallic hard wastes Tritiated metallic hard wastes must be conditioned before packaging in order to reduce their outgassing rates within acceptable limits.2 this may be needed even after a detritiation treatment. 11.20 (Tab.2 with 46.28) or portland cement (24. . As pointed out in subsection 10. especially if the level of tritium residual contamination is still too high to enable an acceptably low outgassing rate. 28). This clearly results from the comparison of leaching data related to speci- mens 46. As indicated in Tab.3) of tritiated metallic hard waste may be applied in conjunction with a suitable tritium containment barrier. To ensure a sufficient reduction of tritium outgassing rates the encapsulation (see subsection 10. Water extendible polyester resin (27. The barrier consists of a layer of organic polymer lining the inner surface of a metal drum or concrete container. This is the conclusion resulting from the comparison of leaching data releated to specimens PEI. . To investigate the individual effect of the encapsulating materials on the overall efficiency of such a double barrier system.2 and E1. 11. in this case.

LA-DC- 12740.4 References for Section 11 (1) Emelity L. 11. Note that just because of this effect the employ of a portland cement instead of a WEP resin for encapsulating metallic hard wastes could result a more effective option. was conversely much effective.M.2). since only a reduction factor by two was achieved in comparison with a non-contained specimen. IAEA Technical Report Series No. Conversely. IAEA. nor comments were reported related to the possibility of an altering effect on the polyethylene permeability. 1984. Los Alamos. Unexpectedly no comparison was made with a cement encapsulating medium. et al.e.4) epoxy resins are therefore the material currently employed in France as the barrier material suitable for achieving an adequate containment of cement encapsulated metallic wastes arising from the dismantling of decommissioned nuclear plants and facilities. containerization in a 1 cm thick polyethylene container without encapsulation. . . i. due to the presence of an encapsulating medium into the specimen container. 90 The assessment of experimental results from these leach tests made evidence that . causing a considerable increase of the polyethylene permeability to tritium. acting as an additional containment barrier. Since their containment efficiency was demonstrated to be superior to that of polyesters (see Tab. Owing to the large void volume in the specimen container without encapsulating medium. being such resins normally utilized as an internal liner of final packaging containers. was found to be ineffective at minimizing the tritium release rate. a dilution of tritium released from the specimen in the water fraction of the WEP solidified emulsion was likely to occur. 3..2. the tritium release rate being in such a way reduced to less than 10~4% per day. As reported in subsection 11. a high tritium concentration gradient was developed across the container wall. a more complete and detailed information on the overall containment system can be found in subsection 12.simple containment of tritiated steel specimens.encapsulation of the same specimen in a WEP resin into the same polyethylene con- tainer. Management of Tritium at Nuclear Facilities.A. (2) IAEA. However.. Vienna.1 epoxy resins were extensively investigated at CEN-Grenoble as potential tritium containment materials (24). Los Alamos Scientific Laboratory. due to the presence of WEP organic components as demon- strated by other experimental tests at Ontario Hydro (see subsection 11. Under such a condition the at- tained tritium concentration gradient was significantly lower than developed in absence of an ecapsulating medium. 2. Tritium Loss from Coated Cement Paste Blocks. N. August 1971. 11. Consequently the tritium permeability across the polyethylene container and therefore the tritium release from the overall containment system was also significantly lowered. 234. To explain the above different tritium leaching behaviours it was postulated (27) that: 1.

(6) Colombo P. 2. 4. EUR 6270 EN (1979) European Appi. (14) As Ref. Rep.C. (18) As Ref. Juelich..J. MLM-2451 (October 1976 . 3.. BNL-20779 (July-September 1975). Fixation of Aqueous Tritiated Waste in Polymer Impregnated Concrete. (11) As Ref. (9) As Ref.March 1979). Polymer Impregnated Tritiated Concrete. Immobilization of Tritiated Aqueous Waste in Polymer Impregnated Concrete. PR No. (16) As Ref. (17) As Ref. BNL-1998I (January-March 1975). No. (21) Williamson A. No.-750989 (1975). (10) Neilson R. et al. et al.. Conf. 13 MLM-2519 (January-March 1978). BNL-20421 (April-June 1975).E. 4. Final Report MLM-2644 (September 1979). (19) Wieneke R. BNL-50733 (April-June 1977).M. . Sci. 13 MLM-2542 (July 1978). PR No. Res..1981). Vol. PR No. Tritium Waste Control Project.S. BNL-19688 (October-December 1974). (5) As Ref. (13) Dauby J. 4.. (15) As Ref. BNL-21700 (January-March 1976). (1.1980. (8) As Ref. Proj. October 20-24. 91 (3) Sunder Rajan N. et al. (7) As Ref. 4. PR No. (20) McKay H. Conf. BNL-22900. Rep. 4.-770611-21 (1977). BNL-50625 (July-September 1976). 9. Tritium Storage Development. 1. 13 MLM-2620 (October 1978 . Rept.5. 4. .Nucl. 7. IAEA Coordinate Research Meeting on "Handling of Tritium Contaminated Effluents and Wastes". Prog. FRG. (12) As Ref.March 1977). 13 MLM-2484 (April-September 1977). PR No. 4. (4) Colombo P.11... Tech.S. Tritium Immobilization. 12. IAEA Research Contract RC 2492/RB quoted by ref. 5. The Fixation of Aqueous Tritiated Waste in Polymer Impregnation Concrete and in Polyacetilene BNL 20898. PR No. et al... Tritiated Aqueous Waste Immobilization.A. et al. 3 (1979) 599. 2.1981/30. 13 MLM-2502 (October-December 1977).

(25) Hawthorne S. Niagara Falls. IAEA. Immobilization of Tritiated Waste-Water by Hydraulic Cements. Dijon. Dijon. N. October 5-9..H. . Paper presented at the Am.. (28) Krochmalnek L. Nuovelle Application des Résines Thermodurcis- sable dans le Domaine des Déchets Radioactifs. Conditioning of Tritiated Wastes.H. 92 (22) Mannone F. 391. (1984).P. Vienna.Solidification and Encapsulation. 1983. Part III . Association Euratom/CEA-CEN Cadarache. 1981.Performance of Con- tainerized and Encapsulated Waste Forms. Ontario Hydro Research Division Report No.. Conditioning and Handling of Tritiated Wastes at Canadian Nuclear Power Facilities. Soc. 84-6-K. 2. Conditionnement des Déchets Tritiés Issus du Reacteur EL3.. April 5-10.The IAEA Seminar on the Management of Radioactive Waste from Nuclear Power Plants. 363. 1986. 1987. (30) Penzhorn R. and De Tassigny C. Pergamon Press.. 85-279-K (1985). Diffusion in Polymers. CEN Saclay (1986). Chem. CFFTP-G-87013. 23-25 Avril 1986.D. Conditioning of Tritiated Wastes from a Tritium Removal Facil- ity.. (31) Crank J. IAEA SR75/8..S. Actes de Journées du Tritium. Proc.Tritiated Water Immobilization. CEN SACLAY (1986). Annual Meeting. Denver. (27) Krasznai J. Karlsruhe. (1982). et al. and Tardif F. A Survey of the State of the Art. (24) De Tassigny C. Actes des Journées du Tritium. Solidification of Tritiated Waste. and Park G. ANS International Topical Meeting on Waste Management and Decontamin- ation. 1531. Academic Press (1968) quoted by ref. Report EUR 11230 EN (1987). Vol.. Sept. Conditioning of Tritiated Wastes Part I . Part II . Ontario Hydro Research Division Report No. Ontario Hydro Research Division Report No.. (23) Aude G.S. (29) Krasznai J..P. and Brunner H. p. 29. Diffusion de l'Eau Tritiée dans les Résines Thermodurcissables. 23-25 Avril 1986.Y. (32) Coste G. Tritiated Waste Conditioning. et al. p.. 82-531-K. p. (26) Hawthorne S.. Fusion Technology 1986.

At MLM (5) laboratory wastes of low specific activity (i. Larger pieces as piping or duct work from outside the glove boxes are placed into 48x52x82 inches (122x132x82 cm) wooden boxes. internally lined with asphalt. Placed inside the concrete shell which is previously lined with a 3-4 mm thick layer of epoxy resin. playwood or cardboard boxes) without being submitted to any previous encapsulation treatment. drums. is ensured by depositing on the top of the hardened cement block a resin layer having a thickness identical to that of the epoxy liner. Medium tritium level solid wastes (740 MBq. while plastic bags containing compactible wastes are directly compacted into 0. which is presently the only central deposit for all French non-recyclable solid tritiated wastes.3 mCi'g"1) are compacted and placed into 55-gal. PACKAGING OF TRITIATED SOLID AND SOLIDIFIED WASTES 12. not last.5 m3 sealed metal containers. the international political constraints presently hindering the application of the sea dumping option.7 TBq-m"3.e. (-210 dm3) steel drums. At TSTA (3. no encapsula- tion is foreseen before waste packaging into standard 55-gal.4 m s cardboard boxes which are then secured with steel straps and double plastic bagged. 93 12.1).1) and 1 m3 internal useful volume are employed for packaging tritiated hard wastes encapsulated into cement. sealed special metal containers. which then are buried in shafts in a retrievable manner. tritiated hard waste items are encapsulated by pouring hydrated cement paste. At Ontario Hydro (1. Also at the Centre of Valduc (CEA-DAM) in France (6). <11 MBq-g"1. After cement hardening the continuity of the epoxy resin layer. 12. <0. 12. since they are considered as non-outgassing wastes.2) ashes from the incineration of combustible miscellaneous wastes are placed inside 2.4) compactible and non-compactible wastes of low tritium contami- nation level (<740 MBq»m"s. The application of this waste management strategy has been motivated by the insufficient tritium retention efficiency of cement and modified cement composites. The final package is then completed by covering the resin coating by an adequate layer of cement grout to seal the concrete shell (see Fig.2 Packaging of tritiated hard waste composites At CEN-Saclay (7) in France reinforced concrete shells of standard dimensions (see Fig.m"3 < A < 3.1 Packaging of tritiated solid wastes without encapsulation Suspect and slightly contaminated soft and hard miscellaneous wastes arising from general laboratory operations are currently placed after bagging in appropriate containers (i. acting as the main tritium barrier. 20 mCi-m"3 < A > 100-Ci m"3) are packaged in- side standard drums. 12. Before conditioning the metallic hard wastes are characterized in terms of tritium contamination level by leaching or thermal treatments on a metallic waste .e. the rather high cost of thermosetting resins and. drums. <20 mCi-m"8) are bagged and placed in boxes for burial at LANL Radioactive Disposal Facility.

As pointed out in ref. packaging and disposing off all radioactive hard wastes generated by dismantling a shielded cell of the Saclay Hot Laboratory (7). previously decontaminated (see subsection 10. (7) the measurement of tritium released during these treatments enables to determine with a satisfactory degree of approximation the actual average tritium concentration in the hard waste item and the homogeneity degree of the bulk distribution. The employ with the same conditioning procedure of standard 200 dm3 steel drums instead of reinforced concrete shells is also foreseen when the level of gamma contamination of metallic waste items is acceptably low. Note that all mentioned conditioning procedures have necessarily to meet the specification (see Tab. Coulis de blocage Déchets tritiés 01120 Barrière en résine époxy FIGURE 12. The above procedure was set-up at CEN-Saclay for conditioning about 70 tons of tritiated metallic wastes generated by dismantling the heavy water type EL3 reactor (7). The verification of the resin/concrete thickness and integrity are carried out by a suitably calibrated ultra-sound machine.1 . 13.2). if necessary and convenient.2) defined for the acceptance of tritiated waste packages by .Typical multiple barrier system employed at CEN-Saclay for encapsulating and packaging tritiated metallic hard wastes from the ELS Reactor (7). 94 sample and. Furthermore reinforced concrete shells and 200 dm3 epoxy resin drums (rein- forced by glass fibers and internally lined with a 2 cm thick layer of "neat" epoxy resin) has also been employed again at CEN-Saclay for encapsulating.

vermiculite) is poured into the intermediate void between the two drums. As shown in Fig. To verify that after conditioning and packaging the gaseous release of tritiated wastes was within the ANDRA acceptance limits a measurement of the waste out- gassing rate must be performed. 95 the French National Agency (ANDRA) that is responsible for the management of long term waste storage centres (7). (3) the system consists of a 30-gal.2 taken from ref. valves or exhausted uranium storage beds.4) highly tritium contaminated solidified and solid wastes (>3. >100 Ci-m"3) (such as sorbed tritiated oils and waste waters. 55 gal burial container Vermiculite 30 gal. primary container Hot waste Asphalt lined drum FIGURE 12.e.3 Overpacking of tritiated solid and solidified liquid wastes At TSTA (3.Past and present burial container employed at TSTA (3). (7) outgassing rate values significantly below the suggested maximum tritium re- lease target of 10"*% per day have been measured in the case of the reinforced con- crete shells. etc. discarded piping. (-210 dm3) drum. As indicated in ref.4 & 13). 12.7 TBq-m"s. If tritiated items are too large to fit into a standard drum they are placed into a welded steel box. 12. After sealing the waste package is buried in shafts (4). are packaged into a double walled container system. (-100 dm3) metal drum which is placed into an asphalt-lined 55-gal. All packaged wastes are checked for outgassing before shipment. (-190 dm3) steel drum liner which is sealed and inserted in a 55-gal. At MLM (5) solid wastes coming from the interior of tritium handling glove- boxes and having therefore a great potential for outgassing are placed into a 50-gaI.2 . In most cases this measurement is based essentially on water bubbling and scintillation countings (see subsections 3. An absorber (i. If . steel drum (DOT specification 17 H).

The leach water was periodi- cally analysed for tritium using a liquid scintillation counter. As to the graph related to drum No. 12. decontamination opera- tions (aqueous detergents) and dry box purification processes (tritiated water). The solidification and packaging procedure is described in Appendix X.8 taken from ref. Tritium permeation was expressed as total (in millicuries) and fractional tritium permeation (ratio of total curies permeation to total curies in the package).8 show a nearly constant permeation rate (i.4). since it increases after approximately the 170th week. 12. Permeation tests were performed under static conditions. containing solidified tritiated water. 96 single drummed laboratory waste is found to be outgassing. Facilities and methods have been also developed at MLM (5. oil and octane.e. . Total actual radioactivity in each package were corrected for decay time since the package was assembled. also this drum is placed into a steel box and controlled once again for outgassing.8) for the safe handling and packaging of high specific activity tritiated liquid wastes arising from tritium decontamination processes on effluent gas streams. Type B 30 gal. TAR poly-liner FIGURE 12. All tests were performed inside a tight 83-gal. steel unmixed on 17Hdrum 50/50 concrete/ annular space plaster filled with absorbent Organics on vermiculiti 28 gal.3 . steel package TAR drum. 12. The experimental graphs of Fig. 318 the slope varies significantly with time. (5). In order to determine the leach resistance of their actual burial packages a permeation test programme was initiated at MLM in May 1975 (8-16).3 taken from ref.Typical burial package employed at MLM for the containerication and overpacking of solidified highly tritiated liquid waatea (5). sealed with RTV 25 liter HTO 55 gal.5 to 12. Figs. in a known volume of leach water. A schematic illustration of the overpack employed for containing tritiated waste com- posites is given in Fig. Tritium contaminated aqueous and organic wastes are solidified and packaged at the Mound Liquid Waste Packaging Facility for burial under total-containment conditions. both as a function of time. slope) for five waste drums. They consisted of the individual im- mersion of representative and actual burial packages. (-318 dm3) drum (see Fig. (16) show the results obtained after approxi- mately 580 weeks (-11 years) since the packages were assembled and submitted to leach tests. 12. Tritiated liquid waste are also generated by vacuum and transfer pumps (lubricant oils).

Λ\\\\\\\\\' ■83-gal Vermiculite ■ drum Waste liquid -55-gal solidified in a . N o comments were made to explain these results. 318 the percentage of tritium that would be released in average per year to the ground water from such multi­walled container package is largely below the maximum target value (0. (17) for tritium leakage from packaged wastes. but decreases after the 200 th week and increases again after the 350 th week.4 ­ Full scale permeation testi at MLM (8). . In order to make comparison of permeation rates between burial packages containing PITC samples and tritiated samples of cement­plaster mix. two packages were prepared at MLM in October 1979 and inserted into the permeation test pro­ gramme (11­15). 97 -Sample port Water level ­ Spacer Spacer - Asphalt. Experimental set up for testing typical burial packages. . The comparison of the permeation rates between these two drums should have to indicate any eventual additional benefits in terms of tritium release resulting from the application of the polymer impregnation process. 318. Un­ fortunately no explanation was found for this behaviour.ι —' drum cement-plaster mixture ï 30-gal drum \V\\\\\\\^ 27-gal Water polyethylene liner FIGURE 12. These results were unexpected essentially because the burial package of the tritiated cement­plaster mix was prepared using a procedure identical to that for the above waste drum N o. after being kept under permeation test conditions for four years. Last information available from MLM (15) indicates that. However the experimental data measured during these permeation tests indicate that even in case of the waste drum N o. Tritium activity in both the leach solutions remained still near the background levels.36% per year) proposed in ref. cumulative tritium releases from these drums were found to be very low. with pratically no significant difference between the two drums.

100.000 d** ♦*♦♦-♦* .632. 98 100.S ­ Full scale permeation tests at MLM (16). weeks FIGURE 12. · * * 0.100 *a 0.000 10.0 Ci) a O Drum 318 · Water (52.010 e * Drum 217 Oil (1. time for two drums of solidified tritiated water.0 Ci) a a 0.001 J_ _l_ _1_ JL 100 200 300 400 500 600 Time since packing.**♦·* · * ♦ i 0. -L 100 200 300 400 500 600 Time since packing. .Water (36. Fractional tritium permeation vs.0 Ci) O Drum 218 · Oil {1.010 * Drum 205 .128.000 aP m 10. Fractional tritium permeation vs.000 m ιΧ 1.632.000 Χ' ·♦»♦**** i * * * ' »** rP .480.001 J.6 ­ Full scale permeation tests at MLM (16). weeks FIGURE 12.0 Ci) 0. time for two drums of solidified tritiated oil.

0 Ci) Y ^200 Y δ Y 150 _ Y »v' 3 - y ** 50- ¿xxx* ** +♦ -*IIIBsMVllV 100 200 300 400 500 600 700 Time since packing.7 ­ Full scale permeation tests at MLM (16). Fractional tritium permeation vs.000 o» * f s o* Fractional pei E * 8 ρ • 0.892.000 y° ι x i 1. 99 100.480.028.632.001 l i l i l í 100 200 300 400 500 600 700 Tim* since packing. 300 • Drum 113 • Octane (5.0Ci) VY 250 . weeks FIGURE 12.6 Ci) 0.0 Ci) Y Y Drum 318 -Water (52.000 I J^" 10.832.X Drum 205 • Water (38. weeks FIGURE 12.0Ci) v τ «Drum 218 -Oil (1.028.128. Comparison of total tritium permeation for six typical drums individually containing solidified tritiated water.8 ­ Full scale permeation tests at MLM (16). oil and octane.6 Ci) γ γ A Drum 217 -Oil (1.892. time for two drums of solidified tritiated octane.010 * Drum 113 · Octane (5. .8 Ci) y •♦•Drum 114 • Octane (2.6 Ci) O Drum 114· Octane (2.

9. 32. Vol. and Cortella J. (11) As Ref. 1980. (4) Jalbert R. MLM-2620 (October 1978 .. Treatment and Disposal of Tritium Containing Waste at Mound. April 29-May 1. La Gestion des Déchets Solide Tritiés Non-Recy- clable..J. 9. 100 12. Nucl. and Carlson R. 9. Fusion and Isotopie Application. Dayton.. (13) As Ref.Management of High Specific Activity Tritiated Liquid Wastes. 9. Ohio. Tritium Safe Handling Course. CFFTP-G-87013. . (7) Coste G. CEN-Saclay (1986) 407. 23-25 Avril. 23-25 Avril. MLM-2784 (April-September 1980). Colorado. Annual Meeting. of ANS Topical Meeting on Tritium Technology on Fission. April 5-10. (8) Mershad E. Conditioning and Handling of Tritiated Wastes at Canadian Nuclear Power Facilities. Conditionnement des Déchets Tritiés Issus du Reacteur EL3. and Dauby J. Annual Meeting. Canadian Fusion Fuel Technology Project. (9) Gibbs G.A. Actes des Journées du Tritium. (14) As Ref. et al. (3) Nasise J. Tritium Waste Control.S. (12) As Ref. Denver.March 1979).4 References for Section 12 (1) Krochmalnek L... Denver. 9. Actes des Journées du Tritium.A. 1987. 1986. Tech. August 1984. (6) Mangln D. Colorado. paper presented at the Am. Chem. Tritiated Solid Waste Management. (5) Rogers M. (10) As Ref. MLM-2844 (October 1980-March 1981). paper presented at the Am. Denver. CONF- 800427 (1980) 347. Dijon. et al. Chem.E. MLM-2903 (April-September 1981). (2) Krochmalnek O. Soc. Annual Meeting. .V.E. Chem. paper presented at the Am. Proc. CEN-Saclay (1986) 339. 1987. MLM-2669 (April-September 1979). et al.L... Packaging of Tritium-Contaminated Liquid Waste. 1987. Performance and Improvements of the Tritium Handling Facility at the LASL. Soc.S. April 5-10. Soc. April 5-10. (1977) 53. 1986.. MLM-2969 (October 1981-March 1982). Dijon. Tritium Contaminated Waste Management at the Tritium System Test Assembly.

No. Sci.Nucl. European Appi.M. (17) McKay H. Tech.C. and Gibbs G. . Rept.Tritium Immobilization". EUR 6270 EN (1979). 1.E.A. Res. . MLM-3332 (October 1984-September 1985).. Vol. 15. 101 (15) Col vin C. MLM-3128 (April-September 1983). 3 (1979) 599.Management of High Specific Activity Tritiated Liquid Wastes Tritium Control. (16) As Ref. . .

13. Therefore if the flow rate of the gas carrier cannot be further reduced (1) an improvement of the sensitivity limit of the measurement could indeed be achieved by using an ionization chamber with the largest volume and an highly sophisticated electronics.1 the current values of the sensitivity limit which may be attained by the a) configuration are typically 1. The choice of one or the other of the above two options will depend on the sensitivity required by the measurement. contamination level. Based on the operating parameters and the value of ionization current. an ionization chamber. which is mainly of concern to waste carriers as well as surface store and burial ground operators. This option is however rather expensive. 13.5 MBq -d"1 (150 microCi -d"1) in the case of a bell-type apparatus. an amplifier and a graphic indicator are currently used to perform the measurement. In both cases the waste drum package to be measured is placed inside a suitable isolating apparatus acting as a cap for collecting the gaseous tritium released into the gas-carrier atmosphere flowing through the apparatus or recirculating through the enclosure circuit. namely: a) under (one through) ventilation at a fixed flow rate of a gas-carrier stream or b) under confinement in a closed-circuit enclosure having a pre-fixed volume. 200 m ' . The isolation of drummed wastes during the outgassing measurement may be done using either a highly ventilated (e. specifically designed to receive each waste category. conditioning procedure and package type. . A lower value of the measurement sensitivity limit under ventilation through a bell-type apparatus would be attainable by increasing the ionization chamber sen- sitivity and reducing the ventilation flow rate through the isolating bell. MONITORING OF TRITIUM OUTGASSING FROM PACKAGED WASTES An important safety aspect to be considered in handling tritiated solid wastes is their tritium outgassing property.g. temporary storage and disposal. As shown in Tab.6 m s -h"1) bell-type apparatus. measured at equilibrium by the ionization chamber (which is proportional to tritium activity) the permanent tritium outgassing rate (Bq day' 1 drum' 1 ) can be thus calculated. This release potential.g. However in order to check the lower limit of drum outgassing rate fixed by ANDRA* ' specifications for accepting tritiated waste packages at the Storage Centre of La Hague (see Tab.h ' 1 ) fume hoods or a moderately ventilated (e. makes mandatory all the conditioned and/or packaged wastes be monitored for an outgassing rate control before they are transfer- red to store or ground burial. 102 13.85 G B q ' d ' 1 (50 mCi-d" 1 ) in the case of a fume hood and 5.2) (*) ANDRA ia the French National Agency responsible for the management of national rad waste storage centres. Along with the selected isolating apparatus a flowmeter. Due to this property almost all tritiated waste items have a non-negligible gaseous tritium release potential which may vary depending on their nature. The outgassing measurement may be performed on a packaged waste according to two operational configurations (1). 0. On such a control measurement is in fact based the acceptance of packaged wastes for transport. At the Centre of Valduc (DAM-CEA) in France (2) the (a) measurement con- figuration is currently applied to classify tritiated drummed wastes into various cate- gories and thus to certify their acceptance for storage at the various facilities of the centre.

Adequate samplings from the tritiated water of bubblers and subsequent scintillation countings will allow to calculate.1 MBq -d"1 (~ 3 microCi -d"1) is currently achievable by using the b) configuration with a standard 10 dm3 ionization chamber currently used for controlling nuclear installations. Within this range a sensitivity limit up to about 0.3). (3) is shown the schematic view of the mea- surement station utilized at Saclay. which is well below the specification value fixed by ANDRA (see Tab.2). Note that the lowest tritium detection limit which is currently achievable in a bubbler water by means of scintillation counting technique is 1. at CEN-Saclay (CEA) (3) to verify that after conditioning and packaging tritium release from tritiated metallic hard wastes generated by dismantling the tritium production cell of the Hot Laboratory was sufficiently low to meet the specifications fixed by ANDRA (see Tab. 13.1 taken from ref. In this case the permanent tritium outgassing rate can be calculated by measuring on the diagram paper of the graphic indicator the slope of the graph representing the progressive linear increasing with time of the gaseous tritium concentration in the atmosphere of the confinement enclosure.5 MBq-d' 1 (150 microCi-d'1) to less than 37 kBq -d' 1 (1 microCi 'd' 1 ). where four 150 ml distilled water bubblers are included. the permanent tritium outgassing rate of the packaged waste. Based on such a method out-gassing rates in the order of 10"4% and 10_6% per day have been calculated respectively in the case of tritiated reinforced epoxy drums and concrete shells. referred to HT or HTO. To this purpose a so called "low level installation" (1) has been developed by the Radiation Protection Service at Bruyère-le-Chatel (DAM-CEA) in France to cover the sensitivity measurement range from 5. The most significant advantage is the low sensitivity limit.85 kBq -dm"8 (-50 nanoCi -dm"3) (1. This method has been applied in France. may be achieved (see Tab. In Fig.e. on the basis of the bubbler water volume and bubbling flow rate.2) for accepting tritiated waste packages at the Storage Centre of La Hague. With this arrangement the minimum tritium detection limit achievable in the bubbler water corresponds to a daily total activity release of 1. 13. Both the bubbler systems are designed to pick up in the water the HTO vapor already present in the carrier gas or subsequently produced by catalytic oxidation of HT passed through the first bubbler.11 kBq (-30 nanoCi) (3) per package measurement. 13. .1) by the a) configuration if the ionization chamber is substituted by two water bubbler systems placed before and after a HT catalytic oxidation unit. 3-4 microCi-d"1) are necessarily to be measured. 13. which are significantly lower than the maximum target value (10"3% per day) proposed as a limit acceptable for tritium leakage from conditioned and packaged wastes (see subsection 7. A sensitivity limit up to than 37 kBq-d"1 (1 microCi-d"1) and lower.2) for the surface storage of tritium bearing waste packages. The main desadvantages of this method are due to the fact that operations such as samplings and tritium activity measurements cannot be simultaneously performed and also to the long duration of bubbling times which normally are needed to minimize unacconted tritium remaining inside the bubbling circuit. 103 outgassing rate values within 100-150 KBq-d' 1 (i.

85x103 ­5x10* 1 Ventilation 1 0. (4) About 10 dm ionization chamber inserted in a ventilation duct.1 ­ Operational features end sensitivity limits of tritium outgassing measurements performed at some french nuclear centres. < 0.2 200 Fume­hood IC(4) 10 0.a. = not available.37 10 5. n.20 (6> Scintil­ 1. France.2 Confinement 2 2. (8) Bubbling. France. France. OPERATIONAL SITE GASEOUS WASTE ISOLAT.05 Bel I­type Bubblers ft 0.0 BelI­type IC(5> 10 n.6 BelI­type IC(4) 10 0.TABLE 13. (3) SACLAY ­ Centre Etude Nucleaire de SACLAY (CE A). (5) About 10 dm ionization chamber inserted in a closed­circuit enclosure.15 (6> ft Counter 4 (9) (1) CVA « Centre de Valduc (CE A­DAM). CONFIGURATION FLOW RATE APPARATUS TYPE V(dm3) SENSITIVITY SENSITIVITY LIMIT (hours) (m3­h1) ­3 ­3 Π Τ" (MBq·«) ^(microCi 'm > (MBq­d > (microCi «d ) Ventilation 1. (9) Scintillation analysis.37 10 1.a.18 lation 0.85 (7) 50 <37x10 <1 20(8) 1.a. (7) Scintillation counter sensitivity. TRITIUM DETECTION SYSTE M LOWER ME ASURE ME NT DURATION Ref. .3 o 0. (2) CBIII ■ Cantre de Bruyère­le­Chatel (CE A­DAM).1 < 3 ­6 1 Bubbling 0. n.5 150 1­5 1. (6) Water volume in bubblers.

0 2.0 O en 7.2 concrete to to 1. per mass unit of radwaste composite. (6) At t « 20e + 5 e C.4 0.4) 74.0 2. (4) Fractional leach rate by permanent inmersión in water (at a pH within 7­8 and a salt content of 0. France).0 <74 2.4 0.2 cement ­2. (5) Average Final.5 <7.0 (1) Average Initial.2 · Tritium activity limits fixed by ANDRA specifications for the acceptance of tritiated waste packages at the "Centre de Stockage de la Manche" (La Hague.0 cement ­2.0 5x10 740 20 shell (3.0 7.0 74.2 none ­1.2 5x10 ­3 111 3. (2) Steel or epoxy resin (reinforced by glass fibers) drum lined with a 2 cm thick layer of epoxy resin. RADWASTE & PACKAGE IDENTIF ICATION TRITIUM ACCEPTANCE LIMITS PER PACKAGES SPECIFIC TYPE OF F USE UL TYPE OF DENSITY SPECIFIC ACTIVITY (5) (6) OUTGASSING RATE REFERENCE 1. .0 <74 2.4 0.TABLE 13.2 drum <2) 0.5 g*l' 1 ) = 5x10' 2 a"1.2 to to dmn (2 > 0. (3) Reinforced concrete shell (C1 type) internally lined with a 2­3 cm thick layer of epoxy resin.0 5x10 148 4. ACTIVITY <1> PACKAGE VOLUME INCORP.4 <0. (t ­m *) (GBq­t') (Ci't') (X d" 1 ) •τ: Τ (kBq'd' 1 ) (microCi­d"1) (GBq­t'1)(Ci 't" 1 ) (nf) MATRIX <7. per mass unit of radwaste.

Tí nm—m Λ Q«rd« — ­ | Venn« m v i d « Pompt Sir Comptawr a 9*1 L. and Cortella J. Typ« Cailut FIGURE 13. La Gestion des Déchets Solides Tritiés N on Recy­ clables. (3) Coste G. 407.. Dijon. ibidem. CEN ­Saclay (1986) 249. 13. Conditionnement des Déchets Tritiés Issus du Reacteur EL3. ibidem. Actes des Journées du Tritium.SO "C» Oxydation du Ή gax «η v i p t u r d* naco* d« 9 ard« fSOmt ISO m l lÉCaMtlMlfJ il gard* tSOmt ISO η •araotau*·. Mesures de Dégazage du Tritium au N iveau des N ormes des Centres de Stockage de Surface. 339. (2) Mangin D. 23­25 Avril 1986.. et al. .1 References for section 13 (1) Paillard P.1 ­ Schematic view e/ the assembly employed at CEN­Saclay (S) for tritium outgassing mea­ surements on conditioned and packaged waste·. 106 Four · fil de p i a t i n « («..

Tritium confinement and loss recovery apply particularly to aqueous and venti- lation waste streams of conventional FRPs (subsection S.e. i. even if most or pratically all such wastes are non-radioactive (subsection 5.3). For this reason the minimization at source of "suspect" wastes is mandatory. Containement.2). the confinement of tritium into smaller volumes of effluents as well as the recovery of tritium losses are stringent safety requirements. The ventilation atmospheres of tritium processing enclosures are usually detri- tiated for safety reasons before to be recycled or discharged to stack.l) as well as to ventilation atmospheres of tritium processing enclosures operated in tritium recovery plants and handling laboratories (subsection 5. At present all miscellaneous solid wastes. which otherwise could become prohibitive. Consequently. A substantial reduction of them can be achieved by locating offices outside the controlled areas and unpackaging materials as far as possible before entering these areas. to reduce the proportional amount of exhausted dryers or liquid condensates generated by a detrition unit. Under tritium confinement conditions (i. tritium segregation and recycling) tritium concentration in liquid waste effluents is allowed to increase up to a suitable level. which are generated in a controlled area of a tritium handling facility are procedurally treated as tritium contaminated. re- circulating inside closed ventilation circuits. hazard and operational problems may in fact arise in conse- quence of the increased steady-state concentration of tritium. However the application of this strategy would also entail some non-negligible draw- backs. SUMMARY 14. Their purpose is that of minimizing the risks of unacceptable tritium exposures for operators and general population. . the minimization of the volume of pro- cessing enclosures and their ventilation by means of dried gaseous carrier streams. it is essential that the tritium dilution in the ventilation atmo- sphere of the processing enclosure may be kept as far as possible at minimum.1 Waste minimization at source For inland tritium handling plants located near closely populated sites where tritium releases are strictly limited. For this reason final tritiated liquid effluents are more reduced in volume with a consequent profitable reduction of the costs of subsequent conditioning and disposal or isotopie enrichment and storage. the proportional in- creasing yields to be attained in recovering tritium and the undesired accumulation of impurities in the recycled streams. Therefore some of basis criteria to be applied for de- signing tritium processing facilities have been fixed with the specific aim of minimiz- ing the production of tritiated wastes.e. This requirement can be met by reducing the size and consequently the cost of the overall tritium containment system. 107 14.

2. 14. The resulting HTO vapor is picked up along with the HTO originally present in the gas mixture by passing the gaseous stream through a bed of dryer material. In particular the tritium removal properties of the Zr}Fe alloy have been tested for this purpose. According to the type of ventilation applied to each enclosure. has been experimentally investigated and applied at Ontario Hydro. . To eliminate the need of recycling the carrier gas still containing HTO to the detritiation unit.e. ETHEL at Ispra). i.1 Detritiation of gaseous wastes Tritiated gaseous wastes arise from conventional plants (e. the risks of unacceptable occupational. HWRs. TRF at Darlington. which uses in a one-through mode a regenerable chemical getter for a direct tritium scavenging out of inert gases. According to the current practice the atmosphere of a processing enclosure con- taining HT and HTO is in most cases detritiated by a closed treatment cycle through a detritiation unit.2 Waste pretreatment 14. a counter current operating mode is applied.2 Volume reduction of solid and liquid wastes To minimize the volume of packaged waste composites to be shipped to surface stores or burial grounds the reduction of the original tritiated waste volume is manda- tory. Candu Reactors. TPL at Tokai.g. Any increase beyond the admitted level of tritium concentration in the enclo- sure atmosphere is monitored and alarmed in real time by means of suitable detectors (Section 3). etc. In these facilities the atmospheres of tritium handling or processing enclosures needs to be continually purified to reduce tritium releases to working areas and exter- nal environment. which normally is an essential component of the overall tritium con- tainment system. These products will be introduced into the procedures for processing liquid and solid tritiated wastes. after monitoring. This procedure normally ensures a tritium decontamination of the carrier gas enough to allow. the atmosphere detritiation may be achieved either in a one-through or a recirculatory mode through an adeguate detritiation unit. TEP at Chalk River) as well as from all those plants or facilities specially designed to perform R&D activities in the fields of the Fusion Reactor Technology (e. the recycle to the enclosure or the descharge to the stack. An alternative to the catalytic oxidation/sorption on dryers. The detritiation of gaseous waste streams will itself lead to the production of other forms of tritiated wastes such as exhausted dryer materials or liquid condensates.TSTA at Los Alamos.g. HT is removed from the gaseous stream by catalytic oxidation.g. The presence in these atmospheres of tritium (in elemental or oxide forms or both) may be due to escaping from equipment or to intentional contamination for experimental purposes. FRPs.2. local and global tritium exposures. 108 14.) and special Tritium Handling Facilities associated to these plants (e.

hydrogenated polystyrene and lower hydrated material (e. a reduction of their overall dimensions may be attained simultaneously when they are submitted to the detritiation treatment by melting (see subsection 14. As a result of CECE and ELEX processes (see next subsection) tritium originally diluted in heavy or light water streams is separated and concentrated in a reduced volume of highly tritiated water. 14. the tritium isotopie separation is normally performed in order to reduce the risk or unacceptable environmental tritium releases. e. is negligible below a tritium enrichment (by atoms) of 0. Tritiated liquid organic wastes may be significantly volume-reduced by an incineration process (subsection 9. 1% and 6% are exceeded (subsection 9. hydroxylapatite) the radiolysis effect become important if tritium enrichment levels of respectively 0. Tritium enrichment is limited to a significant extent by radiolysis and helium production by tritium beta-decay. monitoring and detritiation of all the gaseous atmosphere discharges from the above volume-reduction processes are manda- tory to minimize the risks of unacceptable tritium exposure for operators and general population.g. metallic hard wastes. which may vary from site to site.2. where exhausts are continuously monitored for controlling airborne tritium emissions. which normally causes an increasing of tritium releases. 109 In the case of tritiated solid wastes it may be attained by different procedures (e.g. One has to point out that the containment.g.2. If tritium is stored as pure gas or as liquid (HTO) in sealed tanks the helium production by tritium decay has to be seriously taken into account since it will cause a significant pressure build-up. .1).3%.2). pakaging and storage or disposal).g. The decision on whether and how to recover and then to immobilize tritium for storage or disposal is therefore a result of an assessment which involves both radiological risk and process cost considerations (subsection 9. immobilization.4). This is performed if their recycling is not worth and provided that their radioactivity and tritium concentration do not exceed certain limits. Its enrichment is aimed at minimizing the costs of the subsequent management steps (e. The volume reduction of bagged tritiated solid wastes may be achieved also by vacuum repackaging. As to the uncompressible and incombustible tritiated wastes. incineration. The effect of radiolysis.) that are selected according to the characteristics and tritium contamination level of original wastes.1). For hydraulic cements. A significant volume reduction is also attained in the case of tritiated aqueous waste streams if they are processed for tritium removal purposes. especially if they cannot be incinerated or compacted (subsection 10. For the same reason if tritium is stored after being immobilized in a solid form the strenght of the incorporation matrix as well as the integrity of the sealed package could seriously be affected. Depending on their tritium contamination level these gaseous discharges may be directed to an adequate detritiation unit or directly released through a stack. etc.01%. Consequently a sufficient portion of the internal package volume is currently designed to compensate the effect of this phenomenon.3 Tritium separation and enrichment Beyond the market value of the pure tritium that may be recovered from triti- ated waste water. compaction.4).

allowing a safe handling of final wastes even without a secondary containment. Besides the reduction of the waste a outgassing rate. Besides the radiological risks and the process costs.g. Untili now the only available plant-scale experience in the field of tritium isotopie separation and enrichment is that achieved in France at the Laue-Langevin Institute of Grenoble. the additional advantages which may be attained by melting are a more homogeneous distribution of the residual tritium concentration. The detritiation efficiency obviously depends on tritium distribution into the tritium permeated metallic compo- nent. 14. whose operational availability has been attained in 1988 (subsection 9.2). at the centre of Valduc (DAM-CEA). to reduce their outgassing rate. other factors will influence the choice of either of these techniques. LPCE. To reduce the rate of production of activated hard wastes the recycle of low-activated structural material is foreseen after suitable detritiation and decay steeps.1).2. namely the Triti- um Removal Facility at the Darlington Nuclear Generating Station and the Tritium Extraction Plant at the Chalk River Nuclear Laboratory.e. isotopie exchange with moisture as well as surface heating have been demonstrated to be the most effective detritiation treatments (subsection 10. It is currently applied to tritiated metallic hard wastes after an adequate reduction of their dimensions. In the case of a prominent oxide layer distribution. a minimization of the surface outgassing area and a significant reduction of tritium contamination on the ingot surface. USA. A more drastic thermal treatment such as melting is required if the bulk distribution of tritium is prominent. CECE. metallic components dis- carded from tritium handling facilities must be detritiated. where a vapor phase catalytic exchange (VPCE) process is applied for removing tritium from reactor heavy water effluents.1). . The fusion waste issues asso- ciated with the disposal of tritiated and activated first wall/blanket components of future fusion reactors are expected to be fairly similar to those encountered in the operation of the WERF. ELEX processes) using similar hydrophobic catalyst (subsection 9. i. namely the tritium content and the impurities concentration in the waste stream as well as the kind of management option which one intends to apply to the final tritium enriched product.4 Detritiation of tritiated metallic hard wastes In order to facilitate the conditioning and the safe storage or disposal of tritiat- ed metallic hard wastes.1). Two much larger tritium separation plants have recently been built in Canada. For this purpose the employ of low-activation steels as fabrication material for first wall/blanket components is mandatory (subsection 10. surface leaching with water. A large laboratory scale experience in the field of the detritiation of metallic hard wastes by heating and melting treatments has been achieved in France. Among the available methods the most widely investigated and tested in Europe. At the waste Experimental Reduction Facility of INEL at Idaho Falls a melting treatment of metallic hard wastes has been developed in conjection with a metal sizing operation for fission waste volume reduction purposes. Canada and Japan at laboratory and pilot plant scales are dealing with catalytic exchange process (e. 110 A variety of methods are applicable to attain the isotopie separation and enrich- ment of tritium. To remove tritium from heavy water the vapor phase catalytic exchange (VPCE) and the liquid phase catalytic exchange (LPCE) are applied respectively at Darlington and Chalck River.

Consequently to attain an adequate tritium containment all such materials incorporating tritiated liquid wastes must be integrated in a multiple barrier system.vermiculite and other chemically similar products. This will enable to orientate case by case the choice of the most adequate matrix material by making a balance between the achievable degree of tritium retention and the safety.silica. water extendible resins and vermiculite or equivalent. metal encapsulation etc. A comparative assess- ment of these results leads to conclude that tritium incorporated in such solidification matrices cannot be considered sufficiently immobilized.1 Solidification of liquid wastes Various matrix materials such as: . Furthermore some of them. water solidification. due to outgassing and leach- ability properties of the final tritiated composites.g. namely portland cements. immobilization is also aimed at preventing the spreading of tri- tium in the environment with the consequent exposure of workers and general population to unacceptable radiation doses. alumina and molecular sieves. potentially applicable for immobilizing (i. conclusions are drawn on the specific properties and applicability of the various candidate materials for tritium immobilization purposes. USA and Canada.e. Ill 14.3 Waste immobilization By tritium immobilization is intended the application of all those processes designed to immobilize tritium in such a chemical form or under such a physical con- dition that after an appropriate packaging the subsequent waste management opera- tions (e. polystyrene and water ex- tendible polyesters. transportation. calcium aluminate and sulphate. were also tested as solidifying media potentially ap- plicable for immobilizing tritiated waste oils and other organic liquids. equipment and raw-materials. 14. In the event that the outer waste containment package may be breached during the above operations.). Results from the experimental tests carried out to determine the tritium reten- tion efficiency of such matrix materials have been published. . . have been extensively investi- gated in Europe. semplicity and cost of related procedures. may be done under the safest condi- tions.3. i. Based on information available from the literature. .portland and high alumina cements. storage or disposal). .polyacetylene.e. The attainable immobilization degree is de- pendent upon the chemical form and the physical state of tritiated wastes as well as on the type of matrix utilized. hydroxylapatite. polyacrylonitrile. bakelite type polymers. For waste management purposes tritium immobilization may be attained up to a certain degree by incorporating tritiated wastes into solid matrix materials (e.g. .hydrated calcium orthophosphate. used in conjunction with one or more additional physical barriers. for solidifying) tritiated waste waters under liquid and vapor forms in a stable solid form.

They may be also used as barrier materials for filling intermediate annular voids between secondary and tertiary containers in multiwalled pakage systems for tritiated waste composites (subsection 9. the inhalation hazard related to the tritiated product in a dust form as well as the reduced rehydration kinetic shown by the product under a pellet form.3. In the case of gypsum even with a low water loading (i.e. High alumina cements are capable of binding twice as much water as portland type cements. At 25°C molecular sieves may strongly held wa- ter up to 17 wt% with a vapor pressure of 5xl0"4 bar. However none of such cements has the capability of retaining the totality of the incorporated water so that none can provide by itself an adequate barrier effect against environmental water leaching and water vapor exchange. it is only at a much lower loading percentage (~ 10 wt%) that the sorbed water is strongly held and the lowest water vapor pressure can be attained. but this advantage is partially off-set owing to the metastable hydrated com- pounds produced by HAC hydration.3. They are generally deemed to be well effective for minimizing possible leakages and dispersion to the environment of tritiated liquids in the event that their outer container may be breached. Therefore as indicated by experimental results published in 1981 by the CEC it can be concluded that the use of hydroxylapatite to immobilize tritiated aqueous wastes poses some serious practical problems of chemical engineering nature and do not appear promising at all (subsection 9. i. insolubility and very low water vapor pressure) many problems have been found to interfere with the plant-scale application of hydroxylapatite.3). 112 Drying agents Although the high nominal water capacity (~ 40 wt%) of dehydrated silica gel.3. Such problems are dealing with the difficult preparation of the dehydrated pro- duct. For this reason vermiculite and chemically similar products find their best application as materials for supporting mechanically sorbed tritiated oils inside poly- ethylene containers. which may convert to lower hydrate-forms on ageing. Hydraulic cements Hydraulic cements are the simplest and less expensive water solidication media. but the rather high cost make their use preferable only for immobilizing highly tritiated waters (subsection 9.g.e.2). CaS0 4 .1). Inorganic salt hydrates and hydroxides Although their excellent properties (e. which is among the candidate inorganic salt hydrates and hydrox- ides the most promising in terms of tritium immobilization. . Absorbers Vermiculite and other chemically similar products cannot be considered as true matrices.l/2 H 2 0) a too high water vapor pressure is attained. Portland cements appear to be the best cement types applicable for tritium im- mobilization purposes. comparable in terms of tritium immobilization with other inorganic materials used for this purpose.

5). the benefit of a higher tritiated water loading is off­set by the low den­ sity of the final composite and the high cost of the additive. In comparison with a hydrated cement matrix the tritium release rate from a tritiated polystyrene or a WEP resin were approximately reduced only by a factor 10 and 3 respectively (sub­ section 9.3.g. especially because of the resulting increased resistence of the waste com­ posite to tritiated water permeation. As to the silica gel.1). bakelite type polymers and polyacrylonitrile do not appear well suitable for incorporating tritium in their chemical structure. even if some improvement of tritium immobilization degree can be achieved by using as a water solidification matrix a WEP or a polystyrene resin instead of a portlant cement. This mainly is due to: ­ a limited stability of tritiated polymers to heating.4. this does not occur to a sufficient extent. even if superior to a neat portland cement. 5% of "silica fume") has been found to be beneficial.3. 113 Cement additives such as vermiculite or equivalent were found to allow in­ creased tritiated water loading but at the same time higher tritium release rates. although its addition to cement do not ¡ ι volve any increase of tritium teachability. to which the cement powder is then added. radiation damage and long­term wheatering.4). However. This means that. ­ the considerable amounts of tritiated organic residues or by­products to be rework­ ed for tritium recycle. polymeric organic mate­ rials such as polyacetylene.3.5). polystyrene and WEP resins are water solidification media still inadequate to meet the .3. Furthermore tritium immobilization by such polymers requires equipment and procedures that are too complex and expensive to be justified in dealing with large liquid waste volumes of relatively low tritium concentration. tritiated polystyrene and water extendible polyester (WEP) appear to be the best available options for tritium immobilization purposes since these polymers show the highest tritium retention efficiency under water leaching conditions (subsection 9. the application of other supplementary physical barriers is anyhow mandatory (subsection 9. In conclusion to minimize to an acceptably low level the environmental tritium releases attained by the leaching or the outgassing of hydrated cement matrices in­ corporating tritiated water. For this reason this technique wast deemed to be unsuitable for immobilizing tritiated organic liquid wastes (subsection 9. Organic polymers Based on the information available from the literature. Nevertheless the addition to cement of a low proportion of Si0 2 (e.4 & 9. ­ the difficulty of achieving high tritium incorporation yields. As to the immobilization of tritiated organic liquids the application of cements is precluded by a serious draw back due to the mixing high speed needed to produce the emulsion of the tritiated oil in water. Apart from this latter draw­back. It's in fact during such a step of the tritiated oil processing that a significant fraction of volatile tritiated species initially present in waste oils will be liberated with a consequent partial loss of efficiency in terms of tritium immobilization.

one or more additional containment barriers are needed to minimize tritium release from them up to an acceptably low level. 14.3. the mixing high speed needed to produce the oil-in-water emulsion will liberate the volatile tritiated species initially present in the waste oil (subsection 9. dryness. Water extendible polyester resins and portland cements have been cur- rently employed for this purpose. Then the resulting emulsion must be intimately mixed with the liquid organic polymer and solidified by adding the catalyst. However.g.4.).2 Encapsulation of metallic hard wastes Experimentally it has been found that even if submitted to a surface detritiation treatment (e. A still more enhanced barrier effect has been attained by overpacking the waste im- .2). Tritiated oils must previously be emulsified with water. To reduce the outgassing rate to an acceptably low level the metallic waste incorporation into a suitable encapsulating medium is the option mostly investigated and applied.g. coating. mechanical strenght.3).3. WEP resins could be utilized also for solidifying tritiated organic liquids.4 Waste containment and packaging Since the degree of tritium immobilization achieved by solidification or encap- sulating media was deemed to be inadequate for reducing tritium releases to an ac- ceptable level. For this reason the conclusions which can be drawn from the comparative assessment of these systems are presented under subsection 14. stability etc. 114 suggested maximum tritium release target of 10"3% per day.4. water leaching. the application of integrated multiple barrier systems was the option applied to attain a satisfactory level of tritium containment. In the current practice these encapsulating media are employed in conjunction with polyethylene or epoxy resin liners forming with them a double barrier system packaged into a metal drum or a concrete container. moisture isotopie exchange or surface thermal treat- ments) the outgassing rate of a tritiated hard waste could results still too high (subsec- tion 10. Furthermore the application of a WEP resin appears unpracticable also because of the altering effect of the WEP constituents on the permeability of the polyethylene linear usually employed as primary container. each of them giving a con- tribute to the overall tritium containment. The use of other polymers such as oil extendible polyurethane or urea-formal- dehyde resins does not appear practicable because of the variability of the final com- posite characteristics (e. 14. As for cements there- fore. How- ever also in this case complex procedures are required. encapsulation) with some containment options such as simple containerization or simultaneous containerization and container encapsulation.g. impregnation. Different multi-barrier containment systems have been assembled by combining various additional treatment that may be applied on a waste immobilization matrix (e. strongly de- pendent on their preparatory conditions. This option essentially relies on the application of successive physical barriers.

e. absorbers) for filling intermediate annular voids. Results of static leach tests performed in a water bath for differently coated cement specimens (i. However contradictory results have been reported by some USA laboratories concerning the extent of this reduction. was suggested (subsection 11. An eventual interference with the hydration process by the polymer. polyester and epoxy resins as well as polystyrene were investigated as the media potentially applicable for this purpose. one has also to point out that the application of the polymer impregnation process on a full plant-scale is expected to become a rather complex process owing to the complicated system needed for its monitoring and control. However it also appears difficult that their efficiency may remain unchanged for long time. Result of static leach tests performed in a water bath demonstrated that if polystyrene is used to impregnate a tritiated cement block a non-negligible reduction of tritium leaching from it may be achieved. 14. physical state and concentration of tritium in the waste form but also depending on what of the available waste storage or disposal routes (e.4. Encapsulation Another physical barrier which may be interposed between the surface of a tri- tiated waste composite and its primary container is a layer of untritiated encapsulating material. The matrix and barrier materiate as well as the various containers are usually selected and assembled case by case.e.g. painting or casting around each block. durability and resistance to chemical attack and long-term wheathering. and un- fortunately no attempts were made to explain this discrepancy. paraffin. Water diffusion from inside and penetration from outside of the compos- ite is thus minimized. Portland cements. Their integrity often may become worse as time goes. shallow inground burial or deep geological repository) will be subsequently applied. asphalt. owing to spalling. accounting for the variability of the results. This is done not only in compliance with the chemical form. delamination or cracking of the coating layer. However besides the uncertainty of results. Polymer impregnation The polymer impregnation of a tritiated cement block has been found to pro- duce a final tritiated waste composite which is impermeable to water and has signifi- cantly improved strenght.1. beeswax. coal-tar and epoxy/coal-tar paints) demonstrated that such coatings are capable of improving the leach resistance properties of a tritiated cement composite. In order to produce .2).1 Additional treatments on solidified liquid wastes Surface coating Surface coatings could be applied to cement or concrete blocks by dipping. 115 mobilization matrix inside multiwalled containers provided with containment barrier materials (i. surface storage.

WEP. High density polyethylene (HDPE) was selected because of its excellent resistance to water vapor permeation.The excellent leach resistance properties of all such encapsulating media have been proven by the values of tritium leach rate which may be calculated from leach data resulting from experimental tests. i. the prompt availability on the market. silica gel. practical and less expensive option for providing an efficient additional barrier against tritium release. appear to be the most simple.At present the high density polyethylene used for the primary containment of tri- tiated waste composites appear to be one of the most efficient barrier materials .1. Static leach tests were performed in a water bath to investigate the efficiency of the above encapsulating media as additional barriers against tritium release. 14. In addition to cement and WEP resins. mainly owing to the stringent safety requirements associated with tritium handling operations. the best thermochemical resistence and. for preparing the tritiated waste composites to be sealed inside the polyethylene container and then submitted to leach test. . zeolites were used as matrices to solidify tritiated waste waters (subsection 11. epoxy and polyester resins appear the best encapsulating media which could be used to form with tritiated waste composites a double barrier system against tritium leaching. WEP and epoxy resins have been found to be particularly suitable for encapsulating matrices of tritiated WEP and portland cement. i. Extensive water permeation tests programmes have been developed at some USA and Canada laboratories to investigate the efficiency of a polyethylene primary container. .2) that: . the confinement of a tritiated waste composite inside a suitable primary container.2).2 Containerization of solidified liquid wastes The containerization. tritiated cements as well as untritiated cement hallow cylinders containing tritiated hydrogen under gaseous form. The cement and WEP resins were the two types of matrices selected for incorporating tritiated water. However. Furthermore one has to point out that in dealing with tritiated wastes the complexity of these procedures will significantly increase.e. not last. although these promising results.4.Conversely the encapsulation by cement or polystyrene of tritiated silica gel or zeolite matrices does not significantly increase the degree of tritium retention of tritiated water by cement alone.3) demonstrated that: .e.1. These values were within one and two order of magnitude lower than the maximum target value (10"*% per day) proposed as an acceptable limit for tritium release after immobilization (subsection 7. Results of static permeation tests performed in a water bath on tritiated waste composites provided with polyethylene containers of variable wall thickness de- monstrated (subsection 11. the encapsulation of tritiated waste composites requires the employ of procedures which are too complex and consequently of a difficult application on a full plant-scale. 116 initiated composite specimens epoxy and polyester resins were used as matrices to incorporate tritiated IX resins while cement and polyester resins as container materials to confine tritium gas.3). while epoxy and polyester resins particularly for encapsulating tritiated IX resins incorporated into epoxy or polyester matrices. Results of these tests (subsection 11.

the release of tritium across the HDPE container. 117 against tritium release. 14. Unfortunately no comments were reported concerning the possibility of an altering effect of the WEP components on the permeability of HDPE. the overall tritium retention efficiency of the resulting triple barrier system (i. Such wastes were mainly produced by dismantling some nuclear plant and facilities (e.e. i. Steel or reinforced epoxy resin drums as well as reinforced concrete shells were used as containers for the ultimate packaging of the tritiated composites (subsection 12. performed at Ontario Hydro and CEN- Grenoble on containerized and matrix incorporated tritiated metallic hard wastes. incorporating tri- tiated metallic hard wastes. In terms of tritium retention efficiency 1 cm of HDPE is pratically equivalent to 1 cm of WEP resin. WEP/WEP and WEP/HDPE respectively) in which the above triple barrier system could be subdivided.In the case of a WEP solidified tritiated water.3): .3 Containment and packaging of encapsulated metallic hard wastes Tritiated metallic hard wastes must be conditioned before packaging in order to reduce their outgassing rates within acceptable limits. WEP/HDPE/WEP) was found to be significantly below the value expected by cumulating the barrier effects resulting from the separate application of the two barriers systems (i.e.2).4. the ELAN 2B installation at La Hague). the EL3 heavy water reactor and tritium production hot cell at Saclay. have shown that (subsection 11.With a further external layer of WEP resin being applied around the HDPE con- tainer. Inside the HDPE container the WEP encapsulation of tritiated steel specimens enables to reduce the tritium leach rate to less than 10~4% per day. . Leaching data from experimental tests. Leach rates even inferior to the suggested maximum release target of 10'*% per day (subsection 7. styrene and vinylester and possibly the methy-ethyl ketone peroxide) have. .2). the capability of permanently increasing the permeability of polyethylene to tritiated water. the basic WEP components (i. like that observed during the experimental studies on WEP solidification and HDPE containerization of tritiated waters (see subsection 14.e. This could be necessary even after a detritiation treatment. The tritium containment degree achieved using such waste packages has been . Consequently such resins have widely been utilized in France in conjunction with a cement matrix to implement an adequate double containment barrier for tritiated metallic hard wastes. As a proof of this negative effect the results of static leach tests have demonstrated that a WEP solidified tritiated water confined in a HDPE container did loss tritium in the water leachant twice as fast as a cement solidified tritiated water in an identical container. .4.e.A WEP resin matrix incorporating tritiated steel specimens inside a HDPE container was found to reduce the tritium release more efficiently than it was attained by us- ing the HDPE container alone.Epoxy resins appear to be superior to polyester resins as a barrier material applied to attain an additional tritium containment in a cement matrix.g. even after short contact times. if the level of tritium residual contamination is still too high to enable an acceptably low outgassing rate.2) are attained by using such a material.

an immobilization matrix incorporating solid or solidified liquid waste items. Another important criterion governing the choice is based on what waste storage or disposal route (e.4 Packaging of tritiated solid wastes without encapsulation Suspect and slightly contaminated soft and hard miscellaneous wastes arising from general laboratory operations are currently placed after bagging in appropriate containers (i.e. playwood or cardboard boxes) without encapsulation.e.2).36% per year) proposed as an acceptable limit for tritium leakage from conditioned and packaged wastes (subsection 7. One of the waste acceptance criteria for the above management operations is in fact based on the compliance with a fixed outgassing limit. The various components of such an overpacking system normally are selected and assembled case by case.1). This safety requirement. makes mandatory all tritiated waste pack- .4. the physical state and concentration of tritium in the waste form. for instance. MLM.5 Overpacking of tritiated solid and solidified liquid wastes A considerably improved tritium containment efficiency has been achieved by overpacking tritiated solid and solidified liquid wastes. a sorbent material which is introduced between secondary and tertiary container walls for filling intermediate annular voids.4. TSTA. under an adequate confinement of tritium immobilizing waste composites inside a burial package assembly like one of those above mentioned. storage or disposal of such packages. according to the chemical form. internally lined drums. 118 controlled by tritium outgassing measurements. 14. a multi- walled container system in which the above tritiated composite is confined. which is mainly of concern to waste carriers as well as surface store and burial ground operators. Considerably low outgassing rate have been measured.g. surface storage.5). sealed special metal containers. 14. i.5 Monitoring of tritium outgassing from packaged wastes Due to their outgassing property most of tritiated waste items have a non- negligible potential of releasing tritium even after their conditioning and packaging. 14. At some nuclear sites (e. After many years since the starting of water permeation tests. This option essentially relies on the successive application of different physical barriers such as. Extensive water permeation test programmes have been undertaken at MLM on highly tritiated solidified liquid wastes under total containment conditions. Ontario Hydro) laboratory solid wastes which are suspect or tritium contaminated only within certain low limits are compacted or incinerated before to be containerized (subsections 10. which proves the efficiency and reliability of the conditioning and packaging procedure (see subsection 14. shallow inground burial or deep geological repository) subsequently one intends to apply.g. permeation data indicated that the percentage of tritium released in average per year to the ground water was largely below the maximum target value (0. Consequently a stringent limitation of tritium outgassing from waste packages is imposed to minimize the risk of unacceptable tritium doses eventually associated with the transportation.1 & 12.

In both cases the waste drum package to be measured is placed inside a suitable isolating apparatus acting as a cap for collecting the gaseous tritium released into the gas-carrier atmosphere flowing through the apparatus or recirculating through the en- closure circuit (Section 13). on the basis of the bubbler water volume and bubbling flow rate. The current lowest sensi- tivity limit easily achievable by the a) configuration is typically 5. Both the bubbler systems are designed to pick up in the water the HTO vapor already present in the gas carrier or subsequently produced in it by the catalytic oxidation of HT. This method has been applied at CEN-Saclay (CEA. the permanent tritium outgassing rate of the packaged waste.6 MBq -d"1 (-70 micro Ci-d' 1 ). A sensitivity limit lower than 37 kBq-d"1 (1 micro Ci d"1) referred to HT or HTO may be achieved by substituting the ionization chamber with two water bubbler systems placed respectively before and after a HT catalytic oxidation unit. (Section 13.5 MBq 'd"1 to less than 37 kBq -d"1 (1 micro Ci 'd' 1 ).2) the French National Agency responsible for the management of the national radwaste storage centres. The outgassing measurement may be performed on a packaged waste according to two operational configurations namely: a) under (one through) ventilation at a fixed flow rate of a gas-carrier stream or b) after confinement in a closed-circuit enclosure having a pre-fixed volume and subsequent release.11 kBq (-30 nanoCi) per package measurement. A so called "low level installation" has been developed at the Centre of Bruyère le Chatel (DAM-CEA). to cover the sensitivity range from 5.2 MBq -d"1 (~6 micro Ci 'd' 1 ). The choice of one or the other of the above two options will depend on the sensitivity required by the measurement. The acceptance of tritium bearing packaged wastes in such centres is in fact strictly dependent on the compliance with the above specifications. the tritium release from tritiated wastes generated by dismantling the tritium production cell of the Hot Laboratory was sufficiently low to meet the specification limits fixed by ANDRA. France) to verify that. in France. specifically designed to receive each waste category. At the Centre of Valduc (DAM-CEA) in France the (a) measurement configu- ration is currently applied to classify tritiated drummed wastes into various categories and thus to certify their acceptance for storage at the various facilities of the centre. . 119 ages be monitored for a control measurement of their outgassing rate before they are transferred to store or ground burial. Based on such a method outgassing rates in the order of 10 4% and 10"6% per day have been determined respectively in the case of tritiated reinforced epoxy drums and concrete shells which are significantly below the maximum target value (10_3% per day) proposed for tritium leakage from conditioned and packaged wastes (subsec- tion 7.2). after conditioning and packaging. Tab. Adequate samplings from the tritiated water of bubblers and subsequent scintillation countings will allow to calculate. 13. The minimum tri- tium detection limit achievable in the bubbler water by such a method corresponds to a daily total activity release of 1. By using a higher sensitivity ionization chamber and a lower ventilation flow rate the limit value may be lowered up to about 2.5 MBq -d"1 (150 micro Ci-d' 1 ). which is well below the maximum release limit imposed by the ANDRA specifications for the surface storage. The current lowest sensitivity limit achievable by the b) configuration is typically 0.

if tritium content of wastes is low but still unac- ceptable for being released to the environment or for economic reasons. Additional process steps such as the water vapor trapping from the combustion gases and the previous detritiation of solid waste items before compaction may be necessary. This is beneficial both for reducing the final volume of tritiated liquid waste and the cost of the sub- sequent management operations (e.g. Under confinement conditions tritium concentration in the liquid effluent stream is allowed to increase up to a suitably fixed level. However.Confinement of tritium into small volumes of liquid effluents. conditioning.g. This is a stringent safety requirement especially for inland tritium handling plants located near closely populated sites.Minimization of the volume of tritiated atmospheres of tritium handling enclosures. that currently are detritiated before to be recycled or discharged to stack. i. .Minimization of the amount of so called "suspect" miscellaneous solid wastes that must procedurally be treated as tritium contaminated wastes even if most or pratically non-radioactive.e. The incineration of combustible wastes is authorized only within certain tritium concentration limits which may vary from site to site. Offices normally located outside controlled areas and un- packaging operations performed strictly outside these areas are the design and operational criteria to be applied to attain this purpose. This is either for safety reasons. these conclusions also allow to identify some criteria which are essential for designing and operating tritium processing facilities with the intent of minimizing their tritiated waste arisings. i. the application of this criterion raises a number of non-negligible design and operational problèmes dealing with tritium containment and exposure hazard. . .e. disposal or isotopie enrichment). This volume reduction will allow to proportionally reduce the tritium dilution in the atmosphere to be detritiated and consequently the proportional amount of exhausted driers or liquid condensates generated by the detrition unit. if tritium content is appreciably high to justify tritium recovery. Beside the operational and environmental safety implications of methods. CONCLUSIONS Based on the comparative evaluation of alternative procedures and materials till now investigated or currently applied for managing tritium bearing wastes a number of conclusions can finally be drawn. system and materials presently applicable or applied for con- ditioning tritiated wastes. Waste minimization at source To minimize tritiated waste arisings from tritium handling and/or processing facilities some basic design and operational criteria need to be applied such as: . 120 15. Waste pretreatment The reduction of the tritiated waste volume can be attained by incinerating combustible wastes (e. soft materials and organic liquids) as well as by compacting compressible wastes.

As a results of CECE and ELEX processes tritium can be separated and con- centrated in a reduced volume of highly tritiated water. Beside the radiological risks and the pro- cess costs other factors governing the process choice are the content of tritium and impurities of the waste water effluent as well as the management route envisaged for the final tritium enriched product. An alternative to the catalytic oxidation/sorption on MS uses in a one-through mode a regenerable chemical getter for a direct tritium scavenging out of inert gases. This procedure normally ensures a tritium decontamination of the carrier gas enough to allow. especially if their incineration or compaction is not possible or allowed. To complete the isotopie enrichment of tritium a cryogenic distillation process is nor- mally applied in conjunction with processes. if the oxide layer distribution is prominent. . LPCE. CECE. The detritiation of metallic hard wastes discarded from tritium handling facili- ties is necessary to reduce their tritium outgassing rates and consequently to later facilitate the safe storage or disposal of waste packages. The detritiation of gaseous waste streams will itself lead to the production of other forms of tritiated wastes such as exhausted MS or liquid condensates which will be induced into the procedures for processing tritiated liquid and solid. According to the current practice the atmosphere of a processing enclosure con- taining HT and HTO is in most cases detritiated by a gas-solid treatment through a detritiation unit where HT is removed from the gaseous stream by catalytic oxidation. ELEX) and using similar hydrophobic catalysts are available to this purpose. The resulting HTO vapor is picked up along with the HTO originally present in the gas mixture by passing the gaseous stream through a bed of adsorbent materials such as molecular sieves (MS). Isotopie exchange with moisture or surface leaching with water as well as sur- face heating are the most effective treatments. Conversely in case of a prominent bulk distribution a melting treatment is necessary which also results in a homogenization of residual tritium distribution and very often in a safe handling of final waste without need of a secondary containment. 121 The volume reduction of bagged tritiated solid wastes may be achieved also by vacuum repackaging. the recycle to the enclosure or the descharge to the stack. A variety of methods based on catalytic exchange processes (e.g. With uncompressible and incombustible wastes such as tritiated metallic hard wastes an overall reduction of their dimensions may simultaneously be reached when they are submitted to a detritiation treatment by melting. The gaseous atmospheres of tritium handling or processing enclosures needs to be continually purified to reduce tritium releases to working areas and external environment. Tritium can be isotopically separated from highly tritiated waters and then suitably enriched in order to minimize its environmental release and management costs. after monitoring. A direct volume reduction of tritiated aqueous effluents can also be achieved if a combined electrolysis-catalytic exchange process is applied for tritium removal pur- poses. The choice of the detritiation method is dependent on the distribution of tritium into the permeated metallic com- ponent. VPCE.

Furthermore water solidification procedures required by such materials are too complex and expensive. The achievable tritium immobilization degree is dependent on the chemical form and physical state of the waste as well as on the nature and quality of the material selected as an immobilization matrix. . aluminates and sulphates. No individual cement type or combination of them is however capable of retaining the totality of the incorporated water. However a low water vapor pressure is not a sufficient judgement criterion since a tritium isotopie exchange may also occur. while also the encapsulation of tritiated solid wastes is limited by a considerable price difference in favour of cements. their vapor pressure at 25°C is approximately two order of magnitude lower than the vapor pressure of free water. which is not far from the fully hydra- tion (22 wt%). potentially applicable for immobilizing tritiated waste waters. Vermiculite and other chemically similar absorbers are more suitably applied as absorbers for supporting oils and as back filling materials into annular voids of waste overpacks. To solidify tritiated water the initial water to cement weight ratio must be carefully determined mainly to avoid excessive unbound water and porosity of the final cement block. 122 Waste immobilization The immobilization of tritium present in the various tritiated waste forms may be achieved by incorporating such wastes into a solid matrix such as hydraulic ce- ments. At a water loading of 17 wt%. To reach the maximum achievable degree of cement hydration after hardening the cement block has to be adequately "cured". organic polymers. However. Molecular sieves are the water adsorbent materials currently used for detritiating on an industrial scale gas-carrier streams used for one-through or close-circuit ventilation of tritium handling and processing enclosures. Hydraulic cements are the waste immobilization media of simplest and cheapest application. Inorganic materials such as hydrates and hydroxides of calcium phosphates. They are capable of firmly binding water. As a consequence tritium leach and outgassing rates achievable by such an immobilization matrix are far away from the release target value of 10_3% per day. Portland cements appear the most adequate cement types for tritiated water solidification and solid incapsulation. they are still inadequate to meet the target tri- tium release value of 10"*% per day. cannot be competitive with cements because of the rather difficult applica- bility. The same draw-back hinders the practical application of such media for solidi- fying tritiated organic liquids. but only at rather low water loadings. Therefore. limited water loading and the poor mechanical and thermal properties of the final waste composites. even if superior to portland cements. in spite of their superior leach resistance properties.e. left to stand under controlled conditions. absorbers and driers. Silica xero-gel is a drying agent able to attain acceptably low water vapor pres- sures. Its tritium retention efficiency becomes however very low above 100*C. i. Activated alumina ex i bits similar unsatisfactory pro- perties associated with even a lower loading capacity. Among the organic polymers water extendible polyesters and modified poly- styrene resins are the most suitable media for solidifying tritiated water. polystyrene and WEP resins presently appear less competitive than portland cements which have the ad- vantage of a much simpler and less expensive application.

steel or reinforced epoxy resin drums) have been currently used for the ultimate packaging of waste composites with acceptably low outgassing rate being measured from them.e. However the coating integrity. The full scale application of both coating and impregnation techniques in a waste conditioning plant is however unpractical due to the complexity of the required procedures. They can also be used as a supporting matrix for temporary immobilization and stor- age of retrievable highly tritiated waters pending their rework for tritium recovery. Various containers (e. High density poly- ethylene is proven to be one of the most effective barrier material against tritium release. The tritium leach rate of a tritiated cement composite is known to become even lower than the target value of 10-8% -d"1 if the cement composite is sealed into a HDPE primary container. If tritium content of the waste composite sealed in its primary container is high enough to produce unacceptable tritium outgassing rates the further packaging of this container by one or more additional containers (i. A layer of a tritium-free solidifying or encapsulating material either of the same nature as the primary matrix (e. durability and resistance to a chemical attack and long-term weathering. Waste containment and packaging Additional treatments of primary solid waste composites by surface coatings (i. epoxy or polyesther resins) is another useful way for protecting the pri- mary solid waste composite with an additional containment barrier.g. delamination and cracking. Also epoxy resin layers formed around a cement block encapsulating tritiated metallic wastes were demonstrated to act as an efficient containment barrier. This enables to compensate the pressure build-up in the container due to the gas production by radiolysis and the helium formation by tritium decay. Conversely HDPE is not fully compatible with a tritiated WEP composite as demon- strated by the measured leach rates values unexpectedly higher than those from a cement composite into a HDPE container. coal-tars and epoxy paints) are able to give an improve- ment of the tritium leach resistance. The resin impregnation of tritiated cement blocks was found to improve their strength. Portland cement or WEP) or a different material (e. . HDPE should therefore avoid any contact with components of solidifying/encapsulating organic media which may permanently alter its resistance to tritium permeability. reinforced concrete shells. beeswax. paraffin. 123 Molecular sieves loaded with tritiated water vapors can be regenerated to recover tritiated water or discharged and conditioned as a disposable tritiated waste. The integrity of the primary HDPE container during the time is normally ensured by leaving in it an empty espace. is likely to decrease with time due to spalling. asphalt. hence their con- tainment efficiency.e. Polystyrene impregnated cement blocks exibited a non-negligible reduction effect on tritium teachability but contradictory results were found concerning the extent of this effect. In order to attain its highest efficiency as a tritium containment material.g. overpacking) is mandatory. Among the common polymers it has one of the lowest water permeability and the best thermochemical resistance.g.

storage or disposal of tritiated waste packages is dealing with a limit value of their outgassing rate that cannot be exceeded. storage or disposal in order to carry out such waste management operations under the safest operational and environmental conditions. This clearly demonstrated the high efficiency of such a containment barrier assembly against tritium and water permeation. Waste package monitoring One of the acceptance criteria allowing the transportation. to be strictly per- formed before any transportation. This limit is aimed at minimizing the risk of unacceptable tritium doses to waste carriers as well as to operators of surface stores and burial grounds. Full scale permeation tests on such overpacks containing solidified tritiated water and oils did not show any significant leach of tritium over about ten years of permeation time. . 124 A type of multi-barrier overpack widely employed in USA is a combination of asphalt lined secondary and tertiary containment drums usually provided with ab- sorbing materials filling the interspaces between them. Therefore one can conclude that the monitoring of gaseous tritium release from each individual package containing tritiated wastes is an essential control measurement. but also the excellent leak tightness of the containers forming the overpack.

125 APPENDICES .

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THE SMEAR TECHNIQUE As described in ref. The total area swiped must be known or estimated. This has the advantage that the swipe activity measurement may be done directly on the field.E. under publication.. December 1987. the counting efficiency is not signifi- cantly affected by its presence. Reference (1) Wong K. filter or blotter paper).g. (1) the smear (swipe) technique can be applied according to the following procedure: The surface to be measured must be uniformly scrubbed with a dry or moist piece of swipe material (e. The vial is allowed to stand 10-20 minutes before counting in a liquid scintillation counter.Y. swipes are sometimes measured in proportional flow counters or plastic scintillation counters. A typical removal efficiency is 10% but large variations are possible. A few tens of cm2 is appropriate but 100 cm2 is typical. proposed IAEA Safety Series Procedures and Data Document. Safe Handling of Tritium. As an alternative to liquid scintillation counting. The swipe is then introduced into a standard liquid scintillation vial that has been pre- viously filled with the liquid scintillation cocktail. Note that an adequate sensitivity is available with dry swipes but signifi- cant losses may occur if the paper is not quickly inserted into the liquid of the counting vial. . The use of wet swipes is sometimes proposed for higher sensitivity. The counting efficiency will have to be determined for every particular combination of liquid scintillation cocktail and swipe material used. 127 Appendix I .. Utting R. The choice of the scintillation cocktail does not appear to be particularly critical. If a small paper piece is used.

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1 x F ) HTO. Direct Water Distillation. 129 Appendix II .2 . XF Mole fraction of HTO in the feed (1). H. .Distillation column.Evaporator.Mole fraction of HTO in the feed (l). D . V . R .0 HTO. 5 XF) " ^ U T O . H.1 . (0.0 '(200-1000 X F ) FIGURE II.0 -► ( l o o xF) FIGURE II. E .O HTO.0 (X F ) Hfö.Condenser.TRITIUM ISOTOPIC SEPARATION ft ENRICHMENT. M.Direct Multistage Electrolysis.Recombiner.0 (Xc) HTO.Electrolysis cell. H. SCHEMATIC FLOW DIAGRAMS ILLUSTRATING THE AVAILABLE PROCESS TECHNIQUES (1) ( 0 . H. C . XF . H.

4 ­ Tritium Extraction by CECE and Cryogenic Distillation (2)._|»_ 3. ^-r Recombiner Reflux. DjT Oetntiated 11 1 Tritiated 1 Heavy Catalytic Water Heavy Water Bed l°5 g to Reactor 4 41 trom ~" _ T > Units Reactor Units -t 1[0^1 O JS IM O c Tritium F ixation OTO/Dj 0 I ' ! ^.lectro'v'e f FIGURE II.Tritium Extraction by Direct Singlestage Electrolysis and Cryogenic Distillation (2)../DT σ» O and Storage ♦■ 1 > ò £./ΟΤ 2 Tntiated '—Heavy Wat« Tritium Fixation and Storage » FIGURE II. .3 . 130 c ε o ιέ oc o. . D2 1. Oetntiated Heavy ' ' Water j _ Q 5 Electru'y/ei Puntier n /DT Π.

131 Oxygen ot Tritiated Supply Recombiner To Reactor B>—Τ Heavy Water D}0 Cndr Irom —s> Evap* caf Reactor Units •·· n°' 3Ü fo. Vienna (1985) pp.NDR Cat Evap 1 1 \ι < Cryogenic Distillation System —ι —1 1 J ~fiïo T°> Evap Cat Cndr Tower Tower Gas fc-io D. - Detritiated Heavy Water Γ — Cndr Cat Evap Tritium to "· Tj Fixation ι 1 1 Reactor Units L_ and Storage 1 * Evaporator Plus Superheater ' · Catalytic Exchanger · * · Condenser FIGURE II. Handling of Tritium Bearing Wastes. (2) Canadian Tritium Experience Manual. 16­19. . Ontario Hydro (1984).6 ­ Tritium Extraction by LPCE and Cryogenic Distillation (2). 203. Tritiated Heavy Water from Reactor Units Dj/DT Γ -ι ι Τ I I E a l°i I ι Detonated I Tritium Heavy Water I Fixation J "♦" ano- to Reactor Storage Units FIGURE II./DT Purifier Dj/OT uO. Canadian Fusion Fuel Technology. IAEA Technical Report Series No. Reference (1) IAEA.o Oj 1 .5 ­ Tritium Extraction by VPCE and Cryogenic Distillation (2).

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combines water el ectrol ysis and tritium exchange between hydrogen gas and water. 133 Appendix III . The hydrogen gas. -z_^ H2O (HTO) — * H2 (HT) +1/2 O2 a Un = 5-15 Concentrate: 0.01 F. 100 XF Tritium enriched water FIGURE IIII .32 F.g. Tritium free water is added at the top of the col umn. Tritium contam. . the decontaminated hydrogen can be oxidized instead of being vented and the el ectricity can be del ivered to the el ectrol yser. Xp 8 catal. devel oped and manufactured at SCK. The tritium depl eted hydrogen stream at the top of the col umn can be vented and a smal l tritium enriched water fraction removed from the el ectrol yser for immobil ization and storage. The exchange reaction is promoted by a hydrophobic catal yst. The ELEX process (1-6). if reliable fuel cell s become avail abl e. 0.0 Effluent: 1. becomes more and more depl eted when it fl ows from bottom to top.THE ELECTROLITIC EXCHANGE (ELEX) PROCESS FOR SEPARATION OF TRITIUM FROM AQU EOU S REPROCESSING EFFLUENTS 0.33 F.01 XF Tritium free water ~u Decontaminated hydrogen c E D Feed: F. Al ternatives are possibl e. O) HT + Η2Ο i=zz^ Η 2 + HTO water c CO Keq = 5 (60 'C) χ: υ χ 111 ■H 2 (HT) Eel Electrol. The tritium contaminated water is fed into the exchange col umn at the point where its tritium content corresponds to the l ocal tritium content of the l iquid phase. which has been devel oped for the separation of tritium from aqueous reprocessing effl uents.A schematic illustration of the ELEX process (6). which is already tritium depl eted in comparison with the el ectrol yte from which it evol ves./CEN of the Mol (Bel gium). e. . As the tritium-free l iquid water trickl es down the column it becomes more and more enriched in tritium. Its appl ication is essentially based on the empl oy of an el ectrol yser for the production of hydrogen and a countercurrent packed-bed reactor for tritium exchange between hydrogen gas and l iquid water.

Tritium Technology in Fission. et al.059. Ohio. (Proc. 4. 1 S1982. et al. "Separation of Tritium from Reprocessing Effluents".171. (2) Bruggeman A. et al. 4S. Res. Rept. 4. Dayton... (4) Bruggeman A. EUR 9107 (1984). (6) Geens L.Nucl. Separation of Tritium from Aqueous Effluents. et al.5S2. Technol. European Patent No. 134 References (1) Bruggeman A. IAEA-SM-245/52 (1980). Canadian Patent No. 1980).. 63. . et al. . "Separation of Tritium from Aqueous Effluents". European Appi.066. ANS National Topical Meeting.. Sci. "The ELEX Process for Tritium Separation from Aqueous Effluents". American Nuclear Society (1980). 1.376. Fusion and Isotopie Applications... United States Patent No. et al. Final Report EUR 11551 EN (1988). Separation of Tritium from Aqueous Effluents. (3) Bruggeman A. (5) Bruggeman A.

SCHEMATIC ILLUSTRATIONS OF TRITIUM REMOVAL PROCESSES APPLIED AT THE DARLINGTON AND CHALK RIVER PLANTS Deu let.) — Ί Li Low Tritium I I Adsorber Distillation I Unit Heavy Wale· I D2/DT| * Loop l_ l°î (— Cryogenic Vapour Pha*e Gatd'yt't ι L UT: Ret π ger at o r System Exchange High TrilHim D'lt.i ' Cold Bos Caïinq I I JL Expawon \ I Γ T I r""1 .2 ­ The tritium removal process at the Chalk River TEP (1). Svitem . urn „ 0 r Hecombuier Mskf Up 0. . c»»« I FIGURE IV.0 D. HOO/OjO System D .l ­ The tritium removal process at the Darlington TRF (1).O/0T0 ■A _ V Cold B o . 135 Appendix IV . Helium Relnoerelor Oetntiated FIGURE IV.itanon I „ »Vt» iL fied Treatment Deuterium System Loop 0.

Canadian Fusion Fuel Technology Pro- ject. Ontario Hydro (1984). . 136 Reference (1) Canadian Tritium Experience Manual.

A batch of cement paste composed of 1000 g of cement. the specimens were stripped from the molds. and distributed by Atkemix. A known mass of cement powder was added slowly while stirring into a known volume of tritiated water.Solidification and Encapsulation.3). manufactured by KAO. A "Jiffy" mixing blade was used at approximately 100 rpm. . 137 Appendix V . The specimen container.H. Conditioning of Tritiated Wastes. A super plasticizer Mighty 150 (sulphonated napthalene formaldehyde. one specimen was placed into 1000 ml of deminer- alized water before it cured and thoroughly agitated. The emulsion was formed by pouring the water slowly into the polyester resin while stirring and was then solidified by adding the methylethylketone peroxide catalyst at a concentration of 20 g per kg of polyester resin and allowed to cure for 1 day. size and activity was similar to those of cement samples.2 to 3 mCi) was fixed in each specimens by means of a known volume of tritiated water (. After 1 or 28 days cure. All specimens and containers were weighed and a theoretical ac­ tivity was calculated. Ashland Chemicals An emulsion consisting of 50:50 by volume of tritiated water and Ashland Aropol WEP 661 -P water extendible polyester resin was produced using a high speed mixer and a simple three bladed stirrer at 3000 rpm. All operations were completed in a fume hood. enough to produce 5 specimens was prepared in a 1. Part II . A tritium activi­ ty of approximately 80 to 100 MBq (2. Brantford) was added to the portland type 30 up to a concentration of 20 g per kg of dry cement. Reference (1) Hawthorne S.2 MBq ml"1. 84-6-K (1984). Japan.3 litre container. To determine the activity in each specimen.. Once the mixture was completed as made evident from the consistency of the cement paste. 1 ml of uncatalyzed emulsion was dissolved in 100 ml of methylethylketone and the activity of the solution measured. SPECIMEN PREPARATION FOR LEACH TESTS AT ONTARIO HYDRO (1) Portland Type 30 and High Alumina Cements The same method was applied for preparing the specimens of these two cement types. As a control. 300 g of water (water/cement ratio * 0.Aropol WEP 661-P.0 ml sample was withdrawn for analysis. This was allowed to stand 24 h before a 1. ~ 50 microCi ml"1) added to the initial batch. SOLIDIFICATION OF TRITIATED WASTE WATERS. samples were poured into 120 ml high density polyethylene jars (dimensions 50 mm diameter χ 65 mm high) to a height of 50 mm and sealed with screw caps. Ontario Hydro Research Division Report No. Water Extendible Polyester .

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4. SPECIMEN PREPARATION FOR LEACH TESTS AT KFK. i. 139 Appendix VI . During the initial stages of the polymerization a center-line temperature increase up to 65°C was observed in the specimens.7 MBq (46 microCi) per specimen. Bayer Leverkusen) were first slowly dehydrated by heating up to 400°C over a period of 30 hours (water content approx.SOLIDIFICATION AND ENCAPSULATION OF TRITIATED WASTE WATERS. Waier/cement Specimens were prepared from Portland PZ 35 F type cement. 0. The max. with a volume of approx. and solidified poorly. The zeolites were then immobi- lized following the method described above. < 80°C. 143 ml and an activity in the order of 1.8% by weight). Grace) with up to 25% by weight of H 2 0 (HTO) was similar to that described previ- ously for zeolites. . Occasionally an extender was added to the mixture to stabilize the emulsion. of 65°C. solidification after a hour.e.: 5. Polymer- ization was initiated with a catalyst (di-benzoil-peroxide) in conjunction with an ac- celerator (dimethyl-p-toluidin or dimethyl-aniline).55.e. The samples were then rehydrated in a dessicator with known amounts of HjO (HTO) up to the desired concentration. Water/polystyrene -Water=monomer (DQWzbJnder 101) mixtures containing monomer to water ratios in the range 0. i. temperature increased with decreasing water content in the sample. Gelation occured after a few min- utes.0 were first emulsified with a powerful mixer at 2000 rpm. Main parameters were the amount of catalyst and the type and amount of accelerator. Silica gel/polystyrene The procedure employed for the dehydration and loading of silica gel (SG 127. KARLSRUHE (1) All specimens were of nearly cylindrical shape. Zeolite/polystyrene For the preparation of zeolite with a known HjO (HTO) content samples of zeolite 5A (K 154. Solid blocks were obtained with a DOW binder/silica gel weight ratio of 0. A known mass of such a cement was added slowly while stirring to a known volume of tritiated water to produce a cement grout with a water/cement weight ratio of 0. The curing time of polystyrene and cement specimens was 3 and 28 days respectively.8 to 5. After about 30 minutes the center-line temperature of the block reached a max. 15 or 20% by weight. Specimens prepared with zeolite having low water content attained the highest center-line temperature.

with 156 g of PZ 35 F cement and 50 g of H 2 0. 1531. 140 Zeolite or silica gel/cement The preparation of cement blocks was carried out by mixing either 100 g of zeolite 5A K 154 or 100 g of silica gel SG 127. . Solidification of Tritiated Waste. Reference (1) Penzhorn R.. 2. and Brunner H. Fusion Tech- nology 1986.D. Pergamon Press. p. Vol. containing 21 or 25% by weight of H 2 0 (HTO) respectively. Association Euratom/CEA-CEN Cadarache.

Conceptual fixation of tritiated aqueous waste in polymer impregnated concrete (PITC) by in-drum tumbling and soak impregnation techniques (3). Fig. VILI) the cement was added to the mixing drum (which also becames the casting and storage container) in a "cold" area of the disposal facility and stored until needed. 141 Appendix VII . a mixing weight could also be added to the drum at that time to assure an adequate mixing. . 7. If necessary. were developed for blending tritiated aqueous waste with cement. CEMENT MUrfOMfcK DRUM STORAGE TUMBLING OPERATION TRITIATED AQUEOUS MIXER MIXER CATALYST WASTE CAST ANO CURED FORM ADSORBER OPTIONAL) MONOMER SOAK IMPREGNATION MONOMER CURE PITC TO STORAGE FIGURE VIM . SPECIMEN PREPARATION FOR LEACH TESTS AT BNL & MLM In the USA the immobilization of tritiated water has been investigated since seventies at BNL and MLM with particular emphasis being given to the polymer impregnation of tritiated concretes (1-14). Monitoring of this drum filling step was done on a weight rather than volumetric basis to ensure a proper formulation. POLYMER IMPREGNATION AND CON- TAINERIZATION OF TRITIATED WASTE WATERS. End-over-end tumbling technique In this process (2-5. 1.SOLIDIFICATION. In the frame of the PITC process developed at BNL and MLM conventional as well as special mixing techniques such as end-over-end tumbling and injector tech- niques.

closing the bung-hole. hydrate considerably more water (~ 50 wt%) than does portland cements (~ 25 wt. For portland type III or HA cements the curing required about 24 hours to induce complete hydration. The water necessary to give a w/c ratio of 0.2-[Azobis-2-methylpropionitrile] (AIBN cathalyst) or benzoyl-peroxide (used as a low temperature catalyst) (1-9. Mixing by the drum tumbling technique eliminates the need of equipment cleaning operations and also minimizes the possibility of contamination as mixing occurs in a closed drum. Experiments demonstrated that a casting in excess of 2/3 of the volume of a 30-gal (-115 dm8) drum can be thoroughly mixed by tumbling at 20 rpm for 10 minutes without a mixing weight (3). density and composition.5).2 (3). Catalyst-promoter systems which cure at room temperature were not applied to PITC since the viscosity changes. hence well representative of this type of composite. 14) was added to the waste container through an opening in the drum cover in the pro- portion of 150-200 g of styrene per kg of cement paste. transferring the drum to the tumbler and tumbling the mix. After the soak impregnation was completed the casting was heated to 50-70°C (depending on the catalyst used) to induce polymerization which was completed in 24 hours (7). but typically requiries a few hours. which may occur during impregnation due to the initiation of polymerization. by 69. Approximately 4-5 hours soaking was allowed. may impede the complete permeation of the matrix by the monomer (4.1) using a conventional dough type mixer and a w/c weight ratio of 0.%). is available. not easily permeable by styrene monomer (4). was then impregnated by a soak technique. Both types of cements were mixed with tritiated water to give a w/c weight ratio of about 0.3. Note that the time required for a complete impregnation depending on the concrete volume. Standard 30-gal DOT 17C mild steel drum were selected as casting containers based on consideration of exotherm temperature resulting from the heat of hydration of a water-cement mix. The con- crete. 2.e. the same value applied with the end-over-end tumbling technique. Portland type III and high alumina cements were selected because of their rapid curing properties. Conventional mixer technique Smaller size but similar density specimens (6-9) were also produced at BNL for lysimeter tests at SRP (see subsection 10. equilibrated to room temperature. Styrene monomer. A composite occupying 80% of the nominal volume of this container will have a volume of about 90 litres. but a significant increase of the w/c value above that used would result in too dense cement blocks. 142 The mixing and casting operations simply consisted of adding the required amount of tritiated aqueous waste to the drum. After mixing the cement paste was cured at 40°C.22.22. added along with a suitable amount of tritiated .D. Since the drum also serves as the casting container the need of a transfert operation is eliminated. The dimensions of such a drum are approximately 46 cm I. Such a 30-gal drum may also be inserted into a standard 55-gal (~ 210 dm3) drum in the event of a contamination or leakage and therefore in order to provide an additional containment barrier. catalyzed with 5 g per kg of 2.5 cm high. of course. i. HAC can.

707 g*cm"3 and a polymer loading of 16.15% and a total activity of 170 GBq (4.5% and in the case of duplicate lysimeter tests at BNL PITC specimens with a density of 1. an average polymer loading of 23. In the case of lysimeter test at SRP impregnation produced PITC specimens with a density of 1. Unfortu­ nately no data are available on the results of static leach tests which were foreseen for these samples.783 g.3 cm height. After the casting had been completely permeated by the monomer.9% (8.4) the 5-gal cement casting container was filled with dry portland type III cement and compacted by vibration. The injector which is simply a hollow tube containing several orifices along its lenght through which the aqueous waste is dispersed. Tritiated aqueous waste was then introduced into the cement through the injector. VH. the process was the same as the previously developed end-over-end drum tumbling method (9). The same injector technique was applied at MLM in order to produce tritiated concrete specimens for small.3. Subsequent to the waste injection. After the casting had cured. the latter being vibrated to provide proper packing of the mix. was mixed until a uniforme consistency was obtained. Aqueous waste was added to the cement until the waste reached the external surfaces of the cement as evidenced by dampness. was inserted into the dry cement. 143 water to provide a total activity of 370 GBq (10 Ci) for each specimen.725 g-cm"3 and a polymer loading of 12.545 and a density before impregnation of 1.cm"3. The specimen geometry was cylindrical with approximate dimensions of 27 cm diameter χ 28 cm heigh for a com­ posite volume of about 16 dm 3 .465 gfcm"3 (8.9).67 cm diam. Injector technique In this process (6-14. representing a volume of about 16 dm 3 and a V/S ratio of about 4.2. catalyzed styrene monomer was introduced into the casting container and allowed to soak through the composite.6 Ci) for each specimen. 3. The specimen geometry was cylindrical with approximate dimensions of 28 cm diameter χ 26. After removal from the oven the casting was allowed to equilibrate at room temperature before polymer impregnation. The portlant type HI cement mix was transferred to a 5-gal (~ 19 dm3) poly­ ethylene carboy. The same soak impregnation techniques was applied as described for the above tumbling method.1 Small-scale PITC specimens The specimens were prepared (14) by filling a 500 ml linear high-density-poly­ ethylene bottles (6. Injector and soak impregnation techniques applied at BNL (9) produced "hot" PITC specimens with an average density of 1. The carboy was then sealed and placed in a oven for five days at 40eC to ensure the complete curing of the cement.9). 3.) with 250 g of portland type III cement to a height of . Figs. a volume to surface ratio of 4. the monomer was thermally polymerized.and full-scale leaching tests on packaged PITC com­ posites (10-14).6. The injector was withdrawn and the cement casting was allowed to cure.

5.9).3 TBq (386 Ci) of tritium into the center of the cement mass at a rate of 2 ml-min"1.2 . . Conceptual fixation of tritiated aqueous waste in polymer impregnated concrete (PITC) by the injector and soak impregnation techniques (6.3 .5% and 5% of AIBN catalyst (see above) was added to the void space above the concrete and allowed to soak into the block for 5 hours.5% catalyst) for 18 hours to obtain styrene polymerization (11).Injector technique for the fixation of aqueous wastes in polymer impregnated concrete (9). 62. The specimens were then placed in an oven at 40°C (5% catalyst) or 55°C (0. then vibrating the bottles to compact the cement. After this mixture was cured at room temperature for 5 days. CATALYST AOOITION MIXER AQUEOUS WASTE MONOMER RESERVOIR RESERVOIR VALVE SHUT- OFF VALVE -INJECTOR FIGURE VII. An injector was used to in­ troduce 64 g of tritiated water containing 14. 144 Aqueous Co t o l y r e d Dry Cement Waste Monomer i Container Injector I Waste Cement 1 Soak The r mol » Impregnation Polymer- Filling Insertion ln|tctlon Cure liatlon τ Container 1 ' Disposal Vibration FIGURE VII.79 cm.5 g of styrene monomer containing 0.

AQUEOUS WASTE OIFFUSES 4. copper tubing with one end capped.4 . CONTAINER FILLED WITH 2.AQUEOUS DRY CEMENT. 3. Insert three thermocouples for monitoring and process control at the: . VII. 2. Note that cross-linked high-density polyethylene is more desirable because of its superior resistance to styrene and heat damage.Fixation of aqueous waate in polymer impregnated concrete by the injector techniques (9). FIGURE VII.center of cement block. and at the . AS THE CASTING SURFACES EFFECTIVELY ENCAPSULATING ARE APPROACHED. AFTER IMPREGNATION. 145 I.5).outside surface of the steel 30-gal drum under the heaters (locations: I. CEMENT THROUGH INJECTOR PORTS. THE THROUGH THE CEMENT. POLYMER LOAOING OF THE THE WASTE CONTENT IN COMPOSITE IS HIGHEST AT THE CEMENT DECREASES THE CASTING SURFACES. INJECTION BEGUN. Fill the liner with 112 kg of portland type III cement and vibrate the drum to settle cement. The injection rod is 1/2 in. WASTE I N ­ WASTE DIFFUSES INTO DRY JECTOR INSERTED. . POLYMER IS PRESENT THROUGHOUT THE COMPOSITE. and 4 or 5 on Fig. THE WASTE. Place a 27-gal high-density-polyethylene drum liner into a 30-gal (~ 115 dm3) steel drum. diameter) are drilled: one in the cap and four groups of four holes arranged radially. . Holes (1/8 in.2 Full-scale PITC waste packages The following procedure was applied at MLM (14) for successfully fabricating PITC waste packages utilized for full-scale tests: 1. intervals. 4. which start at the end and are spaced at 2- 1/2 in. 3. . so that the end of the rod is in the center of the cement mass. 3.circumference of the cement block. Place the injector vertically in the axis of the drum.

Increase the heat when the package reaches ~ 45"C again (~ 2 hours). No. 1.23 dm 3 per minute. PR n° 3. .5 .% of catalyst (2.Tritium Storage Development. Rep. Conf. et al. Schematic view of the assembly used at MLM (14) for fabricating full scale PITC waste packages. Prog. Polymerization should occur within approximately 7 hours. (2) As Ref. When the correct temperature has been established. 2. then turn off the heaters.2'-azobis [2-methyl-propionitrile] to the void above the cement block and allow it so soak into the cement. 146 Inject 27 dm 3 of water at 0. PR n° 4. BNL- 19688 (October-December 1974).75 wt. then remove the injector rod. 1. filling the hole with cement. being careful not to exceed 110°C at the liner. et al. (3) Colombo P. Heat until 70°C is attained at the circum- ference of the cement block (~ 5 hours). 7.3 kg of styrene monomer containing 0. . Install band heaters and insulation on the 30-gal drum and heat the package to 45°C. (4) As Ref. BNL-20421 (April-June 1975). BNL 20898. 750989 (1975). . Replace bungs on the liner and allow the cement to cure from 3-5 days at ambient temperature. 6. 30 gal steel drum 27 gal polyethylene drum linear Wraparound : TC 6 band heater Thermocouples Insulation Styrene polymer "Concrete FIGURE VII. References (1) Colombo P. BNL-19981 (January-March 1975).The Fixation of Aqueous Tritiated Waste in Polymer Impregnated Concrete and in Polyacetylene. add 24.

MLM-2519 (January-March 1978).Tritium Waste Control Project. . (9) As Ref. (7) Neilson R. PR n° 5. 1. et al. 1. 10.E. Final Report MLM-2644 (September 1979).Immobilization of Tritiated Aqueous Waste in Polymer Impregnated Concrete. BNL-2I700 (January-March 1976). 770611-21 (1977). PR n" 12. et al. 1. PR n" 7. et al. (14) Wieneke R. BNL-20779 (July-September 1975). PR n° 9. Conf. 10. 147 (5) As Ref. 1. MLM-2542 (July 1978). BNL-22900. MLM-2484 (April-September 1977). . (10) Dauby J. (11) As Ref.Polymer Impregnated Tritiated Concrete. . (12) As Ref. MLM-2451 (October 1976 - March 1977). (13) As Ref. (8) As Ref.J. BNL-50625 (July-September 1976). 10.M. BNL-50733 (April-June 1977). (6) As Ref. .

149

Appendix VIII ENCAPSULATION OF SOLIDIFIED TRITIATED WASTE
WATERS. SPECIMEN PREPARATION FOR LEACH TESTS
AT ONTARIO HYDRO (1)

Tritiated water was previously solidified as described in Appendix V using WEP
resin or Portland type 30 cement to produce specimens 30 mm diameter by 30 mm
high, containing a tritium activity of approximately 80 to 100 MBq (~ 2.2 to 3.0 mCi)
per specimen. After curing for 1 day in sealed polyethylene containers, the specimens
were placed into 120 ml polyethylene containers, 50 mm diameter by 65 mm high.
The solidified specimens were centered by using a wire basket and the encapsulation
materials poured around the smaller specimens to produce a 10 mm thickness of en­
capsulation material around the entire specimen as detailed in Fig. VIII. 1. After a 7
days cure all specimens were removed from molds and placed into appropriate tests.
Types and manufacturers of the used encapsulating materials are listed below
(0:

Encapsulating Material Manufacturer
Epon 815 epoxy resin cured with Ancamine 506 Shell Canada
amido­amine Chemical Company
Epon 815 epoxy resin cured with a 50:50 Shell Canada
mass ratio of Ancamine Lo/Los aromatic amine Chemical Company
Water Extendible Polyester ­ Aropol WEP 661­P,
50/50 water/WEP volume ratio Ashland Chemical
Polyester resin Aropol C­308 combined with
1.5 volumes of No. 2 sandblasting sand and Ashland Chemical
0.75 volumes of bentonite clay
(Black Hills Bentonite Clay Co.)
Encapsulation
material
10 mm thick

Solidified
specimen
30 χ 30 mm

■■■■ .■■■■.·■■·■■■:■·>:■·.·.:·■■.·■·■■.;

\ ! /
V
Wire basket
1 mm diameter wire
FIGURE V i l l i ­ Cross section of an encapsulated and containerised specimen of solidified tritiated water (1).

150

Reference

(1) Hawthorne S.H., Conditioning of Tritiated Wastes. Part II - Solidification and
Encapsulation, Ontario Hydro Research Division Report No. 84-6-K, (1984).

The dimensions of containerized and encapsulated specimens of solidified tritiated water are reported in Tab. (1985). IX.P. 11.1 . 85-279-K. Part III . 151 Appendix IX . The suspending wire was then cut flush with the top of the solidified specimen and a 0. Layer of WEP to cover suspending Copper wire glued to wire / ' c o n t a i n e r lid Tritiated water solidified 'in WEP Encapsulating layer of WEP" Polyethylene container FIGURE IX.Performance of Con- tainerized and Encapsulated Waste Forms. Ontario Hydro Research Division Report No.Cross section of an encapsulated and containerised specimen of solidified tritiated water (1). SPECIMEN PREPARATION FOR LEACH TESTS AT ONTARIO HYDRO (1) The procedure used to encapsulate solidified waste water specimens in WEP resin described in Appendix VIII was modified. . To avoid this problem a single piece of copper wire was fixed with epoxy glue to the polyethylene container cap which was used to suspend the waste form in the encapsulating material mold. Reference (1) Krasznai J. This was necessary because the preparation of replicates behaving identically was a problem due to the difficulty of obtaining a leak tight joint between the wire basket holding the waste and the encapsulating material..5 cm cap of WEP resin was poured on top of this to minimize the possibility of leakage at the wire/WEP interface (Fig.ENCAPSULATION OF SOLIDIFIED AND CONTAINERIZED TRI- TIATED WASTE WATERS. 1).7 of Section 11. The WEP resin encapsulating material was then poured over the waste form and allowed to set for 4-5 hours. Tritiated Waste Condioning.

.

or equivalent corrosion and impact resistant Material. Secondary: asphalt coated 30-gal (115 dm ) 17H steel drum. minimum wall thickness. 18-gauge body and head. drop forged lugs.to 15 mil Cabot's FLEXIBLAC #3230 (1). polypropylene. TABLE X.Recommended burial package for tritiated liquid wastes. 0. a glove-box) for total containment during transfer of the liquid. polyethylene. BURIAL PACKAGING SOLIDIFIED TRITIATED LIQUID WASTES AT MLM The description of the burial package applied at MLM for the multibarrier containment of solidified tritiated liquid wastes is summarized in Table X. closures to be two 2-in.g.7 g tritium) per 30-gal (115 drri ) drum.d.5 kg (~ 90 dm 8 ) of vermiculite for organic (pump oil) wastes. The polyethylene drum is filled with either 81 kg (~ 90 dm 8 ) of a 3-to-l dry mixture of perlited gypsum plaster and portland cement for water or 9. Tertiary: 55-gal (210 dm ) 17H steel drum. 12-gauge bolted ring. After analysis by calorimetry.. 32 kg (~ 90 dm 8 ) of "Absorbai" may be substituted for packaging organic wastes. 18 25-in. A maximum of 27 dm 8 of water (within a DOT Specification 2S. Oil and organica: maximum weight ratio of two parte oil or organice to one part vermiculite or three parts "Absorbai". must fit inside 30-gal (115 on ) secondary. 153 Appendix Χ .000 Ci (2. (1).59 PBq) (.l . Buttress threaded fittings (1). CONTAINMENT Primary: rigid polyethylene. with leak-tight closure. The standard primary/secondary burial package is prepared by inserting a 27- gal (100 dm3) polyethylene drum* into an asphalt-coated 30-gal (115 dm8) steel drum b . i. taken from ref. .0625-in. the volume transferred is verified using calibrated sight glasses on the holding tanks. The steel drum is then connected to the bottom of an inert handling enclosure (e. TRITIUM CONTENT Maximum of 70. SOLIDIFICATION Water: maximum weight ratio of one part water to three parts dry cement- plaster mixture. the liquid waste is transferred via a calibrated metering pump into the polyethylene drum. all external and internal surfaces coated with 10.l. b DOT Specification 17H. 27-gal capacity.

.

then the steel drum is removed from the bottom of the enclosure. A more recent information (2) indicates that a maximum of 25 dm8 of highly tritiated waste water and 28 dm8 of oil are incorporated in 24-gal (~ 95 dm8) of cement-plaster mix and vermiculite respec- tively.A. with less than 0. The sealed. paper presented at the Am. 30-gal (115 dm8) drum is then centered in a 55-gal (210 dm8) steel drum containing ~ 4 gal (15 dm8) of asphalt. Denver. the polyethylene drum is sealed with a silicon rubber adhesive and the inert enclosure is flushed with argon to remove residual tritium. As illustrated in ref.. The polyethylene drum is checked for leakage. and the steel drum lid is sealed in place using a sealant and a bolted clamp ring. et al.. Treatment and Diposa! of Tritium Containing Waste at Mound. Packaging of Tritium-Contaminated Liquid Wastes. Nucl. Chem. No mechanical mixing is necessary. 154 37-74 TBq of tritium per dm8) or 25 dm8 of pump oil (about 1.L. . (2) the liquid transfer process consists of slowly adding tritiated waste water or oil into the polyethylene drum containing 24-gal of the cement-plaster mix or oil absorber. Vermiculite or "Absorbai" is then poured between the two drums to a level ~ 2 in. Soc. The remaining void volume is filled with more asphalt. April 5-10.75 TBq of tritium per dm8) is transferred into the polyethylene drum. Reference (1) Mershad E. The steel drum is then checked for leakage. (2) Rogers M. and the 55-gal drum lid is sealed with a sealant and a bolted clamp ring. c Bituminous coating.5% of the oil separating from the absorber after one year. Tech. When the transfer is completed. 1987. 32 (1977) 53. formulation to conform to specification MIL-C. Annual Meeting. The void volume above the polyethylene drum is filled with asphalt0. (50 mm) below the top of the 30-gal drum lid.102A-Type I (1).

deuterium and protium D20 Pure deuterated water DTO. 155 GLOSSARY Tritium (Τ) Isotope of hydrogen. no defined percentages of tritium. χΗ H Hydrogen as name for the isotope in any chemical form H 2 Pure hydrgen gas Η. no defined percentage of tritium Deuterium (D) Isotope of hydrogen. jH Pure tritium gas HT Tritiated hydrogen. HD Mixture of hydrogen gas.Ο Normal water CH3t Tritiated methane TC CH Tritiated acetylene TCH = CH2 Tritiated ethylene TCH .CTO Di-Tritiated acetaldehyde TCH . no defined percentages of tritium. deuterium and protium Protium (H) Isotope of hydrogen. H D 2 Pure deuterium gas DT.CH Tritiated acrylonitrile CN TCH «CH Tritiated vinylacetate OCOCH . no defined percentage of tritium τ2ο Pure tritium water HTO Tritiated water. HDO Tritiated and deuterated water.

Ispra Site. 156 ACRONYMES & ABBREVIATIONS AAP Air Atmosphere Purification ACU Air Clean-Up AECL Atomic Energy Canada Limited AGR Advanced Gas-cooled Reactor ANDRA Agence National pour la gestion des Déchets RAdioactifs (France) AP Activation Product BARC Bhabba Atomic Research Centre (India) BNL Brookhaven National Laboratory (USA) BNWL Battelle Pacific North-West Laboratory (USA) BWR Boiling Water Reactor CANDU Canadian Depleted Uranium CA Cryogenic Distillation CEA Commissariat Energie Atomique (France) CEC Commission of European Communities CECE Combined Electrolysis Catalytic Exchange CEN Centre d'Etudes Nucléaires (France) CRNL Chalk River National Laboratory (Ca) DAM Division Applications Militaires (France) DD Direct Distillation ELEX ELectroiitic Exchange ETHEL European Tritium Handling Experimental Laboratory (CEC. Ohio. USA) NET Next European Torus . LANL Los Alamos Scientific (now National) Laboratory (USA) LPCE Liquid Phase Catalytic Exchange LSC Liquid Scintillation Counter LWR Light Water Cooled Reactor MLM Mound Laboratory of Monsanto (Miamisbury. Italy) FBR Fast Breeder Reactor FRP Fuel Reprocessing Plant GPC Gas Proportional Counter GS Generating Station GWT Gaseous Waste Treatment HAC High Alumina Cement HDPE High Density PolyEthylene HEPA High Efficiency PArticulate HTR (helium cooled) High Temperature Reactor HWR Heavy Water-Reactor IAEA International Atomic Energy Agency IAP Inert Air Atmosphere IC Ionization Chamber INEL Idaho Falls Engineering Laboratory (USA) IX Ion exchange JAERI Japan Atomic Energy Research Institute KfK KernForschungszentrum. Karlsruhe LASL.

Japan) TRF Tritium Recovery Facility (Chalk River. NM. Ca.) . USA) USERDA United States Energy Research & Development Agency VPCE Vapor Phase Catalytic Exchange VRF Volume Reduction Factor WERF Waste Experimental Reduction Facility (Idaho. 157 OPC Ordinary Portland Cement PITC Polymer Impregnated Tritiated Cement PSC Proportional Scintillation Counter PUREX Plutonium-URanium Extraction PWR Pressurized Water Reactor SRP Savannah River Plant (USA) SCK/CEN Centre d'Etude Nucléaires (Belgium) TEP Tritium Extraction Plant (Ontario Hydro. Ca. Ca.) TPL Tritium Processing Laboratory (Tokai-Mura.) TSTA Tritium System Test Assembly (Los Alamos. USA) WEP Water Extendible Polymer WVRF Waste Volume Reduction Facility (Ontario Hydro.