Commission of the European Communities

nuclear science and technology

MANAGEMENT OF
TRITIUM-CONTAMINATED WASTES

A SURVEY OF ALTERNATIVE OPTIONS

Report
EUR 12526 EN

Blow-up from microfiche original

 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, Information Industries and Innovation
L-2920 LUXEMBOURG

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Catalogue number: CD-NA-12526-EN-C

© ECSC — EEC — EAEC. Brussels - Luxembourg, 1990

 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, i.e. dealing
with the behaviour and reliability of materials, equipment and containment systems
under tritium impact.
For this reason a part of the experimental activities to be performed in ETHEL
will be devoted to laboratory research on tritiated waste management. However, since
all experimental activities planned for the execution in ETHEL will by itselves
generate tritiated wastes, current strategies and practices to be applied for the routine
management of these wastes need also to be defined. To attain this target an adequate
background information must be provided, which is the intent of this report. Through
an exhaustive literature survey tritiated waste management options till now in-
vestigated or currently applied in several countries have been assessed. A particular
importance has been attached to the tritium leach test programmes, whose results
enable to assess the tritium retention efficiency of the various waste immobilization
options.
The conclusions resulting from the overall assessment are presented.
 C O N T E N T S

Page

1. INTRODUCTION 1

2. TRITIUM SOURCES AND PRODUCTION RATES 2

2.1. References for Section 2 4

<
3. TRITIUM MONITORING 5

3.1. Tritium monitoring in solid media 5

3.2. Tritium monitoring on material surfaces 8
3.3. Tritium monitoring in liquid media 8
3.4. Tritium monitoring in atmospheric air 9
3.5. References for Section 3 11

4. ORIGIN AND CHARACTERISTICS OF TRITIUM

CONTAMINATED WASTES 12

4.1. Tritated wastes from heavy water reactors and

associated tritium recovery plants 12
4.2. Tritiated wastes from light water reactors 13
4.3. Tritiated wastes from fuel reprocessing plants 13
4.4. Tritiated wastes expected from future thermonuclear
fusion reactors and associated tritium handling
facilities 13
4.5. References for Section 4 16

5. TRITIATED WASTE MINIMIZATION AT SOURCE 17

5.1. Tritium confinement 17

5.2. Recovery of tritium losses 18
5.3. Minimization of suspect solid wastes 19
5.4. References for Section 5 19

6. SORTING AND CLASSIFICATION OF TRITIATED WASTES 21

6.1. References for Section 6 22

7. IMMOBILIZATION AND CONTAINMENT OF TRITIUM FOR

WASTE MANAGEMENT PURPOSES 23

7.1. General considerations 23

7.2. Required degree of immobilization 23
7.3. Potentially applicable methods 24
 VI

7.4. Criteria for selecting an immobilizing agent 24

7.5. The multiple physical barrier concept 28
7.6. References for Section 7 29

8. DETRITIATION OF GASEOUS WASTES 30

8.1. References for Section 8 . 31

9. TREATMENT AND CONDITIONING OF TRITIATED

LIQUID WASTES 32

9.1. Tritium separation and enrichment 32

9.2. Factors limiting tritium enrichment 35
9.3. Solidification of tritiated waste waters 37
9.3.1. Drying agents 37
9.3.2. Absorbers 38
9.3.3. Inorganic salt hydrates and hydroxides 39
9.3.4. Hydraulic cements 40
9.3.5. Organic polymers 44

9.4. Solidification of tritiated organic liquids 51

9.4.1. Hydraulic cements 52
9.4.2. Organic polymers 52
9.4.3. Absorbers 53

9.5. References for Section 9 53

10. TREATMENT AND CONDITIONING OF TRITIATED

SOLID WASTES 58

10.1. Volume reduction of tritiated solid wastes 58

10.2. Detritiation of tritiated metallic hard wastes 60
10.3 Encapsulation of tritiated metallic hard wastes 65
10.4. References for Section 10 66

11. CONTAINMENT OF TRITIUM IN SOLIDIFIED LIQUID AND

ENCAPSULATED SOLID WASTES 68

11.1. Additional treatments on solidified liquid wastes 68

11.1.1. Surface coating 69
11.1.2. Polymer impregnation 69
11.1.3. Encapsulation 74

11.2. Containerization of solidified liquid wastes 80

11.3. Containment of encapsulated metallic hard wastes 89
11.4. References for Section 11 90

12. PACKAGING OF TRITIATED SOLID AND SOLIDIFIED WASTES 93

12.1. Packaging of tritiated solid wastes without

encapsulation 93
12.2. Packaging of tritiated hard waste composites 93
12.3. Overpacking of tritiated solid and solidified
liquid wastes 95
12.4. References for Section 12 100
 VII

13. MONITORING OF TRITIUM OUTGASSING FROM PACKAGED WASTES 102

13.1. References for Section 13 106

14. SUMMARY 107

14.1. Waste minimization at source 107

14.2. Waste pretreatment 108
14.2.1. Detritiation of gaseous wastes 108
14.2.2. Volume reduction of solid and liquid
wastes 108
14.2.3. Tritium separation and enrichment 109
14.2.4. Detritiation of metallic hard wastes 110

14.3. Waste immobilization 111

14.3.1. Solidification of liquid wastes 111
14.3.2. Encapsulation of metallic hard wastes 114

14.4. Waste containment and packaging 114

14.4.1. Additional treatments on solidified
liquid wastes 115
14.4.2. Containerization of solidified liquid
wastes 116
14.4.3. Containment and packaging of encapsulated
metallic hard wastes 117
14.4.4. Packaging of solid wastes without
encapsulation 118
14.4.5. Overpacking of solid and solidified
liquid wastes 118

14.5. Monitoring of tritium outgassing from packaged

wastes 118

15. CONCLUSIONS 120

APPENDICES 125

Appendix I - The smear technique 127

Appendix II - Tritium isotopie separation & enrichment.

Schematic flow diagrams illustrating the
available process techniques 129

Appendix III - The electrolitic exchange (ELEX) process for

isotopie separation & enrichment of tritium
from aqueous reprocessing effluents 133

Appendix IV - Schematic illustrations of tritium removal

processes applied at the Darlington and Chalk
River plants 135

Appendix V - Solidification of tritiated waste waters.

Specimen preparation for leach tests at Ontario
Hydro 137
 VIII

Appendix VI - Solidification and encapsulation of tritiated

waste waters. Specimen preparation for leach
tests at KFK, Karlsruhe 139

Appendix VII - Solidification, polymer impregnation and

containerization of tritiated waste waters.
Specimen preparation for leach tests at
BNL & MLM 141

Appendix VIII - Encapsulation of solidified tritiated waste

waters. Specimen preparation for leach tests
at Ontario Hydro 149

Appendix IX - Encapsulation of solidified and containerized

tritiated waste waters. Specimen preparation for
leach tests at Ontario Hydro 151

Appendix X - Burial packaging of solidified tritiated liquid

wastes at MLM 153

GLOSSARY 155

ACRONYMES & ABBREVIATIONS 156

1. 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, liquid and solid forms. 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.
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), has been commissioned to experimentally develop various
safety aspects related to the tritium technology in fusion. This was decided by the
CEC in the frame of the European Community research programme on Fusion Tech-
nology and Safety.
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, equipments and contain-
ment systems under tritium impact. In this context ETHEL will contribute to experi-
mental research in support of NET, the European Communities Project aimed at the
construction of an experimental thermonuclear fusion device of the Tokamak type.
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, since all experimental activities planned for the execution in ETHEL will
by itselves generate tritiated wastes, current strategies and practices to be applied for
the routine management of these wastes need to be defined.
To attain this target, an adequate background information is required. The
intent of this report is that of providing this information through an exhaustive litera-
ture survey. In this frame alternative tritiated waste management options so far inves-
tigated or currently applied to this end in Europe, USA and Canada have been
assessed.
Since tritiated wastes expected from the ETHEL operation will be contaminated
only by tritium, 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,
originated by the neutron activation of structural materials. 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 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.
2. TRITIUM SOURCES AND PRODUCTION RATES

At present tritium arising in the nuclear industry is mainly due to the tritium
production in nuclear power reactors. 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, 6 Li, 7 Li, 10B, 8 He usually present as impurities or components in
reactor fuels, coolants, moderators etc. ...
In most reactors the major source is the ternary fission occuring in the fuel, 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. 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 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.
In Tab. 2.1 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.
The tritium produced in the nuclear power reactors may be retained in the
reactor materials, may be emitted to the environment from the reactor site or
transferred with fuel to a reprocessing plant. Tab. 2.2 taken from ref. (1), summarizes
estimates of the activities (per unit energy generated) emitted to the environment or
transferred to a reprocessing plant.
TABLE 2.1 - Sources and Production Rates of Tritium by Neutron Reactions (1).

REACTOR PRODUCTION RATE: kCi.(GW(e).a)-1 FRACTION (X)

TYPE CLADDING OF TRITIUM ELEMENTS AND MATERIALS PARENT NUCLIDE
by Fission by Cumulation RELEASED UNDERGOING NUCLEAR <Nucl. React.) REF.
in the fuel into coolant & FROM FUEL TRANSMUTATION
moderator (a) Typical M axin

10,B (n,2a)
5
Soluble B, nat. D- and
^■yn, γ)
PUR 15-20 0.55-1.0(b) <0.2 Li impurities in H.O 7
Li 3 (n,na)
mod./coolant 6
L1 3 <n, γ )
Zircaloy
BUR 15-20 0.1-0.4(c) <1 1 Nat. D, in H,0 mod./cooIant
Η,ίη,γ)
OJ
HUR 20-24 2400 <1 D, in D.O mod./coolant

AGR 17 >30 Li in graphite moderator. 'LljCn.na)

6
Li 3 (n,e)
1,2
Stainless Β and Li impurities in core 10,B 5 (n.2o)
FBR 20-30 25 95 -100
Steel and blanket

3.7-8.5 He in He cool, and Li Ήβ^η,ρ)

HTR 18 -30
impurities in graphite

a) Includes estimates of tritium release from fuel.

b) Lower limit is for 0.1X loss of tritium from fuel and for use of Li (>99.9X isotopie purity) for pH control.
c) Lower limit is for 0.1X loss of tritium from fuel.
TABLE 2.2 - Tritium emissiona and transfers from various power reactors (1).

REACTOR EMITTED TO THE ENVIRONMENT TRANSFERRED TO

TYPE REPROCESSING PLANT

kCi.fGWfeJ.a)" 1 Gaseous phase (%) Liquid phase (%) kCi.fGWfeJ.a)" 1

PWR 0.55-1 1 90 15-20

BWR 0.1-0.4 10-50 90-50 15-20
HWR 24 90 10 20-24
AGR 4.5 10 90 12-IS
FBR <1 - - low
HTR <8.5 -100 a -0 10-17

From helium clean-up system.

2.1 References for Section 2

(1) IAEA, Handling of Tritium Bearing Wastes, IAEA Technical Reports Series,
No. 203, IAEA, Vienna, 1981, p. 5 & 7.

(2) IAEA, Management of Tritium at Nuclear Facilities, Technical Reports Series,

No. 234, IAEA, Vienna, 1984, p. 3-5.
3. TRITIUM MONITORING

A deep and exhaustive examination of the problems associated with tritium

monitoring is out of the scope of this section. Therefore only the most known tech-
niques and instruments currently applied in this measurement field are here briefly
outlined.
It is well known that tritium monitoring is currently performed in order to:
- determine tritium concentration and/or purity inside the primary containment such
as experimental apparatus and storage containers for process control and accoun-
tancy purposes;
- measure the removable surface contamination and the out gassing rate of tritiated
materials and composites for safe handling purposes;
- 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.g. glove-
boxes, pass-boxes, air locks, interspaces, etc.). This is done for radiological protec-
tion purposes in order to prevent accidental tritium releases to the working environ-
ments;
- detect in real time and to alarm any increase beyond the authorized limit of tritium
concentration in the atmosphere of tertiary containments (i.e. working environment,
waste stores etc.) as well as in duct or stack exhausts. 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,
for comparison with authorized release limits, i.e. for regulatory purposes.
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.
To measure tritium activity with the due efficiency, tritium detector must be
specifically designed for each of the above mentioned purposes, keeping always in
mind the low energy and the short range of tritium beta-emissions.
The characteristics and application fields of typical tritium detectors are summarized
in Tab. 3.1. More detailed information on them are given in ref. (1).

3.1 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. 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.
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. Such requirements may be met by destructive measurements, i.e. by
submitting samples taken from hard waste items to leaching or to thermal treatments
(see subsection 10.2). As mentioned 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.
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
Counter (GPC) containments (stacks)
Surface contamination mea­
surement
Measurement of tritiated
particulates in air
0.37 10 -2 - Discontinuous on gaseous 1 minute Required a counting gas, (e.g.
samples argon, methane)
- Direct, on contaminated Too low upper detection limit
surfaces (4) ft indirect, (37 MBq-m" 3 )
on filter papers (5) More complex and expensive than
- Indirect, on filter pa­ a IC
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
in a standard liquid scintillation counter. However these systems are unable to give
results in real time and therefore appear unadequate if a high sampling rate is needed.
The continuous on-line scintillation technique involves the use of flow cells
containing a solid scintillator. As mentioned in ref. (1) several type of solid scintil-
lators have been applied. However, being continuously exposed to tritium contami-
nated liquid streams, these type of scintillators can build up with time a background
activity which is difficult to eliminate. This draw-back is caused by the dirt and other
radioactive materials which usually are suspended in the liquid streams to be
monitored. All these suspended materials may of course be reduced by an adequate
liquid filtering. However it is not excluded that some radioactive particles of very low
size may pass through the filter pores, causing with time an irreversible fouling of the
scintillator surface. This will consequently require a periodical replacement of the
solid scintillator.

3.4 Tritium monitoring in atmospheric air

HTO

Bubblers, absorbent bed colums and diffusion samplers are used to pick up
HTO vapor from atmospheric air for tritium measurement purposes.
Bubblers are the most commonly used. They usually consist of two simple gas washing
bottles containing distilled water or ethylene glycol, through which the air stream to
be monitored is bubbled. After a sufficient bubbling time the concentration of the
total tritium collected in the water as HTO is determined by liquid scintillation
counting. Being the gas flow rate and the bubbling time known, the average tritium
concentration in the gaseous stream can be calculated.
The trapping mechanism is based on a simple isotopie exchange of HTO vapor
with water. In the case of the ethylene glycol firstly the HTO dissolution and than the
isotopie exchange occurs.
For very long bubbling times the ethylene glycol is the most appropriate choice,
due to its low vapor pressure. To prevent any tritium losses several bubblers contain-
ing ethylene glycol can be used in series.
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).
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.
A diffusion sampler is a simple system used for sampling HTO vapor from
atmospheric air. Liquid scintillators, silica gels, zeolites and ethylene glycol have been
employed as sampling media for diffusion samplers (1).
A passive diffusion sampler has been developed and applied at Ontary Hydro's
Nuclear Generating Stations (1), consisting of a device containing a small quantity of
water. No bubbling is necessary since HTO vapor will be picked up from tritiated air
by exchange with this water.
 10

The exchange rate is diffusion limited and reproducible. As reported in ref. (1) the
sensitivity of this sampler is about 500 cpm per 37 kBq-h.m"8 with an overall
accuracy of ± 30%.

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. They are not
species specific tritium monitors i.e. they do not discriminate the activities due to HT,
HTO or other tritiated gaseous species (e.g. CHST).
The counting method based on the ionization chamber gives a response in real
time and is the most commonly used. It is however not specific to tritium since it
responds to other airborne radioactive species as well as to ambient gamma fields. To
reduce these interferences compensating chambers are currently used (see Tab. 3.1).
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.e. <37 kBq.m"8). As pointed our in ref. (1) measurements of tritium spe-
cific activities of 0.37 kBq.m"3(0.01 micro Ci.m"8) are achievable with counting time
of about 1 minute. The upper detection limit of such counters is however limited,
typically to 37 MBq.m"8(10 mCi.m"8). They are also more expensive and complex than
ionization chambers. Since they require a counting gas (e.g., argon-methane) and
atmospheric air is known to be deleterious to most counting gases, the amount of
tritiated air samples that can be added inside a counter must be limited. Anyhow the
major advantage of such counters is their capability of discriminating external pene-
trating radiations (e.g., electrons produced by gamma radiations) or radioactive gases
accompaning the tritium (see Tab. 3.1).
To measure HTO in presence of HT, the air sample is first measured to deter-
mine the total tritium activity. Then another sample is again measured, after being
passed through a bubbler or a molecular sieve or a silica gel column, to determine the
activity of HT. The difference between the first and second measurement will give
the HTO concentration. 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.
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. The resulting HTO is then removed again by flowing the oxidized gas through a
second bubbler system. The measurement by scintillation counting of both the HTO
activities (i.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. In some cases a decontamination of HTO from other radioactive gases partially
solved in the bubbler water may be needed. 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).
 11

3.5 Reference for Section 3

(1) Wong K.Y. and Utting R.E., Safe Handling of Tritium, proposed IAEA Safety
Series Procedures and Data Document, December 1987 under publication.

(2) Coste G. et al., Conditionnement des Déchets Tritiés Issus du Reacteur EL3,
Actes des Jounées du Tritium, Dijon, 23-25 Avril, 1986, CEN SACLAV (1986).
 ÏZ

4. ORIGIN AND CHARACTERISTICS OF TRITIUM CONTAMINATED WASTES

Usually tritium contaminated wastes are generated under gaseous, liquid and
solids forms. Liquid and solid tritiated wastes have the particular property of perma-
nently generating tritiated gaseous effluents (outgassing) because of the:
- desorption of volatile compounds (i.e. HT, HTO),
- autoradiolyse (i.e. production of CHST and, in presence of oxygen, C0 2 and HTO),
- Isotopie exchange reaction with environmental moisture.
The processing of gaseous effluents may in turn generate tritiated solids (e.g.
exhausted absorber beds) or liquids (e.g. 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.
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.

4.1 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. Distribution values between water and airborne tritium releases may vary
depending on various factors (1). 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.
A closed-cycle heavy water recovery system, associated with the reactor, is
normally employed to keep tritium concentration in the recovered heavy water to an
acceptable occupational level. It may be placed within the reactor containment or even
outside in confinement rooms, either purged with air or fitted with air dryer systems
(1).
The leakages from both moderator and coolant systems are collected in tanks. 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. Otherwise it is sent to
a clean-up system and then to the upgrading by water distillation or other process
techniques (see Section 9).
Different types of tritium-contaminated wastes are produced according to the
various tritium handling operations in the reactor and associated tritium recovery
plants. Primary wastes can be summarized as follows:
1. Spent reator components contaminated by heavy water.
2. Miscellaneous solids and organic liquids from maintenance and repair operation
(e.g. contaminated equipments, pipings, tools, hydraulic and/or lubricant oils etc.).
 13

3. Miscellaneous solids from decontamination, contamination control, normal labora-

tory and housekeeping operations (e.g. discarded plastic personnel suits, vermicu-
lite air form respirators, exhausted filters and IX resins, concrete and wood debris,
temporary floor and wall coverings, paper tissues, gloves, bottles, rags, maps,
swabs, etc.).
and secondary wastes:
4. Tritiated water concentrates generated as residual effluents from the heavy water
clean-up and up-grading (tritium removal) system associated to a HWR.
5. Tritiated solid wastes generated as a by-product of tritium removal.
6. Tritiated liquid wastes generated by decontamination of primary wastes.

4.2 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. Such wastes
are managed, likewise tritiated solids, with the major attention being focused on their
activation product content rather than tritium contamination level.

4.3 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. Being the reprocessing currently performed
according to the standard PUREX flow-sheet, 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. As a result very large volumes of
tritiated aqueous effluents (e.g. 100 m8/t heavy metal) have been produced.
Tritiated wastes currently arising from reprocessing plants include (1):
1. Cladding hulls (60% of tritium released from the fuel).
2. Tritiated aqueous wastes from common acid and water recovery systems where the
different raffinâtes of the various Purex extractions cycles are processed (e.g. con-
centrated by distillation).
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.g. up to 5-0.5 m8/t of LWR fuel processed (2).

4.4 Tritiated wastes expected from future Thermonuclear Fusion Reactors and
associated Tritium Handling Facilities

Gaseous, 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. All these wastes will require an adequate
processing to minimize any tritium losses to the environment. 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. These by-products will also be
 14

introduced into the procedures for processing directly generated liquid and solid
tritiated wastes.
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:
- Tritium permeated hard wastes, contaminated by neutron activation by-products
and arising from reactor maintenance operations (e.g. discarded reactor components
such as first wall, blanket segments, etc.).
- Miscellaneous non-compressible solids arising from plant equipment modification
and maintenance operations (e.g. contaminated equipment, discarded piping and
valves, tools, glove boxes and exhausted materials such as molecular sieves, cata-
lystes and getters etc.).
- Miscellaneous combustible and/or compressible solids arising from decontamination
operations (e.g. discarded plastic personnel suites, vermiculite from air respirators,
exhausted filter cartriges, IX resins, etc.) and normal laboratory operations (e.g.
paper tissues, samples bottles, gloves, etc.).
- Miscellaneous combustible and/or compressible solids arising from contamination
control operations (e.g. protective clothings, shoecovers, temporary floor and wall
coverings, etc.) as well as from general laboratory cleaning operations (e.g. rags,
mopheads, swabs, etc.).
and as tritrated liquids:
- Organic liquids arising from plant maintenance (e.g. hydraulic and lubricant oils, oil
sludges) and normal laboratory operations (e.g. bubbler liquid, scintillation cocktails,
solvents, etc.).
- Aqueous effluents arising from the aqueous leakage collection, solids decontamina-
tion, tritium rework and molecular sieve bed regeneration operations (e.g. aqueous
leakages, detergents, tritiated water residues and condensates).
- Aqueous effluents coming from those areas of the Fusion Reactor and associated
Tritium Handling Facilities where the risk of tritium contamination is low (e.g.
showers, hand basin, drains).
In Tab. 4.1 an exemple is given of typical waste arising and sources as tenta-
tively anticipated for NET* systems (3), while in Tab. 4.2 taken from ref. (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).
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).

Next European Torus, the European Communities Project aimed at constructing an experimental thermo-
nuclear fusion device of the Tokamak type.
TABLE 4.1 · Typical tritiated wastes expected to arise from NET systems.

TYPE OF WASTE TYPE OF GENERATING OPE RATION GENERATING SYSTE M OR AREA OR E QUIPME NT
CONTAMINANT

1. Tritiated water
2. Oil, lubricants
Decontamination solutions
(acidic, alkaline aqueous
detergents)
HTO/AP Leakage collection Drip pans, floor sumps and leakeage collection sys­
HTO Tritium rework tems Tritium rework plant
Combined Maintenance of vacuum pumps Plasma exhaust pumping system.
HT/AP Maintenance and service areas
HT/AP Decontamination of equipmen' Decontamination and maintenance areas.

4. Tritium permeated hard

wastes (e.g. first wall/ HT/AP Reactor maintenance First wall/blanket
blanket segments)
5. 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,
s IAP, ACU, GUT)
0 6. E xausted catalysts HT Substitution of catalytic Systems for purification of gaseous wastes (AAP,
L RED/ΟΧ beds (Cu/CuO) IAP, ACU, GWT)
I 7. E xhausted IX­resins, 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, floor sumps and leakage collec­
S spent activated carbon tion systems.
8. E xhausted getters HT Substitution of getters Plasma exhaust purification system

AP = Activation Products.
AAP - Air Atmosphere Purification System.
IAP ■ Inert Atmosphere Purification System.
ACU ■ Air Clean­Up System.
GUT = Gaseous Waste Treatment System.
 16

TABLE 4.2 - Expected tritiated wastes associated with the operation of the Darlington TRF (4).

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 0.5-1.0 0.025
(25% KOD)
(c) Pump oil 0-1.8 -10 3 0-50 0.075

SOLID ( 'm" 3 )

(a) L ow Activity <7.4 <0.2 132

(Processible)
(b) Medium Activity 7.4-37 · 102 0.2-100 0.4
(c) High Activity >37 · 10 2 >100 1.3

4.5 References for Section 4

(1) IAEA, Management of Tritium at Nuclear Facilities, IAEA Technical Report

Series No. 234, IAEA, Vienna, 1984, p. 3.

(2) McKay H.A.C., Tritium Immobilization, EUR 6270 en (1979) European Appi.
Res. Rept. - Nucí. Sci. Tech., Vol. 1, No. 3 (1979).

(3) Mannone F. and Dworschak H., Management of Tritium Contaminated Wastes at

the ETHEL Facility. Future Trends for Routine Management Practices and
Experimental research Activities, Proc. of Sym. on Waste Disposal and Treatment
for Fusion Reactor Systems, 193rd ACS Meeting, Denver, USA (1987).

(4) Krochmalnek L .S. et al., Conditioning and Handling of Tritiated Wastes at

Canadian Nuclear Power Facilities, paper presented at the Am. Chem. Soc.
Annual Meeting, Denver, April 5-10, 1987.
 17

5. 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.
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. Confinement, i.e. segregation and recycle of tritium must be enhanced in those
parts of a plant where tritium is produced and/or processed. This in order to
reduce to a minimum the tritium "spreading" through any process streams.
2. Tritium losses must be recovered in the most concentrate form. In view of this all
reasonable attemps are to be made to avoid any possible isotopie dilutions.
3. Some ancillary operations originating non-radioactive solid wastes must be carried
out as far as possible outside the controlled areas of the plant. This is in order to
avoid that, because of their origin, such wastes have to be managed following the
same procedures used for truly tritium contaminated waste, even if they are only
suspected of tritium contamination.

5.1 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.
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 4.3).
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. For inland plants located near closely populated sites where on-site
liquid tritium releases are limited, confinement of tritium into a smaller volume of ef­
fluents may be a mandatory requirement to meet in future for safety reasons. In FRPs
tritium confinement may be attained by:
1. Segregating tritiated aqueous streams in the early part of a plant where the head­
end treatments and the Γ' extraction cycle are carried out. This implies (1-3) the
application of a tritium barrier concept, i.e. 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.
2. Recycling tritiated aqueous streams in the early part of the plant so that the addi­
tion of a tritium-free solutions (e.g. 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.
Many recycle schemes have been proposed and reviewed (4-10). Usually the
withdrawal of a certain volume of the tritiated liquid stream from the recycle system
is forseen. If a total recycle is applied, the volume of the withdrawal has to be at least
as great as that of the tritium-free aqueous scrub, which is fed to the scrub section of
the 1*' contactor.
 18

Recycling of course will increase the tritium concentration throughout the early
part of the plant. A concentration limit has to be defined based on plant safety con-
siderations. This will hinder to reach too high steady-state tritium concentrations.
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.
In all these operations the volume reduction of tritiated effluents is essential
because their costs would be otherwise prohibitive.
Although its application at FRPs will involve the use of a known and relatively simply
technology, some drawbacks associated with tritium segregation/recycling have been
identified (11) such as:
1. Containment and hazard problems would be complicated due to the increased
steady-state concentration of tritium in the plant.
2. The fraction of tritiated water vapor to be recovered from off-gases and vessel
ventilation streams will increase as the recycle factor increases.
3. The recycle of aqueous streams entraining organic impurities could generated op-
erational problems during the PUREX process operation.
4. An addition of N0 2 to make up nitric acid is required to attain the maximum re-
cycle factor.

5.2 Recovery of tritium losses

The recovery of tritium losses is aimed at reducing the tritium concentration of

waste arisings. It is mainly performed for safety reasons, 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, local and global ex-
posures.
The recovery of tritium losses applies particularly to tritiated gaseous streams
arising in conventional FRPs (e.g. process off-gases, vessel ventilation streams) and to
the enclosure atmospheres of special Tritium Handling Facilities associated to HWRs
(e.g. 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.g. TSTA at the LASL site, TPL at the JAERI-Tokai site, ETHEL at the
JRC-Ispra 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. These atmospheres are normally purified from
tritium in one-through or alternatively in a recirculatory mode (see Section 8).
It follows that the costs of an overall tritium containment system will highly
depend on the size of the atmosphere detritiation unit, i.e. on the degree of dilution
attained by tritium in that atmosphere.
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 volume of tritium handling enclosure must be kept to a minimum.
2. A double-walled containment must be employed along with intermediate tritium
scavenging by a gas stream.
 19

3. Possibly a closed cycle with a dried gas stream has to be applied for tritium
scavenging.
4. Tritiated gaseous effluents are treated in an atmosphere detritiation system for
tritium removal.
It is worth noting that by limiting tritium dilution in tritiated effluents also the
cost of an isotopie enrichment plant can be reduced.

5.3 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. Conse-
quently, since all wastes generated in a controlled area of a tritium handling labora-
tory or plant, are suspected of tritium contamination, they must be procedurally treat-
ed as tritium-contaminated. Obviously this is done for safety reasons even if pratically
all such wastes are non-radioactive. To reduce the amount of suspect wastes which
after packaging have to be shipped to surface storage or burial grounds, their mini-
mization at source is mandatory. 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.

5.4 References for Section 5

(1) Schenez H. et al., Report Jül-1099-CT (1974), quoted by ref. 10.

(2) Musgrave B.C., Report ICP-1041 (1974), quoted by ref. 10.

(3) Miquel P. et al., Proc. of CEC Seminar on Radioactive Effluents from Nuclear
Fuel Processing Plants, Karlsruhe (1977) 497, quoted by ref. 10.

(4) Burch W.D. et al., Retention of Gaseous Fission Products in Reprocessing

LMFBR Fuels, Advisory Group Meeting on Reprocessing of LMFBR Fuel,
Leningrad, May 1976.

(5) Baetsle L.H., Head-end and Nuclear Gas Purification Research on LMFBR
Fuel Reprocessing in Belgium, Adivisory Group Meeting on Reprocessing of
LMFBR Fuel, Leningrad, May 1976.

(6) Sauteron J. et al., Le Retraitement des Combustibles "Rapides" en France,

Advisory Group Meeting on Reprocessing of LMFBR Fuel, Leningrad, May
1976.

(7) Burger L.L., Trevorrow L.E., Release of Tritium from Fuel and Collection for
Storage, Controlling Airborne Effluents from Fuel Cycle Plants (Proc. ANS-
AIChE meeting, 1976), American Nuclear Society, Hinsdale (1976), BNWL-SA-
5778, CONF-760806-3 (1976).
 20

(8) Henrich E. et al., The Concentration of Tritium in the Aqueous and Solid
Waste of LWR Fuel Reprocessing, Management of Gaseous Wastes from Nuclear
Facilities (Proc. Symp. Vienna, 1980), IAEA, Vienna (1980) 177.

(9) Hartmann K., Brücher H., Die Entsorgung tritumhältiger Abwässer-Technik

und Sicherheit, Kernforschungsanlage Jülich, Interner Bericht KFA-ICT-IB-
468/82.

(10) McKay H.A.C., Tritium Immobilization, EUR 6270 en (1979) European Appi.
Res. Rept. - Nucí. Sci. Tech., Vol. 1, No. 3 (1979).

(11) Bruggeman A. et al., Assessment of Some Methods for the Separation of

Tritium from Aqueous Effluents of a Reprocessing Plant, Centre d'étude de
l'énergie nucléaire, Mol Rep. SCK/CEN.

(12) Dolle L., Production and Treatment of Tritiated Wastes in France, Appendix II
of IAEA Technical Reports Series No. 203, IAEA, Vienna, 1981.
 21

6. 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. These criteria are often dictated by the subse-
quent tritium management routes one intends to apply (e.g. treatment for tritium recy-
cle or tritium immobilization for storage or disposal as a waste).
In principle the classification of tritium contaminated waste materials should
take into account their
- physical state (gaseous, liquid or solid);
- chemical nature (organic, inorganic);
- ability to accept or not a volume reduction treatment (e.g. compressible or uncom-
pressible, combustible or incombustible materials);
- level of tritium contamination (i.e. the specific activity of tritium) so that suspect,
slightly, medium and highly tritium contaminated wastes may be defined. The
boundary between low, medium and high tritium level wastes will depend of course
on standards and regulations applied at the country of the considered plant. One has
to point out, however, that while the determination the specific activity of a tri-
tiated liquid, which is currently done by sampling and scintillation counting do not
meet particular difficulties, for tritiated hardwares and miscellaneous solid, a
specific activity measurement based on such a technique often may result complex
and not sufficiently representative (1). This is due to the massive or miscellaneous
nature of solid wastes as well as to the non-homogeneous distribution of tritium in
them. 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). To assist, other complementary techniques based on the mea-
surement of the surface activity (i.e. smeart tests, see Appendix I) and the outgas-
sing rate may also be employed. This latter technique is normally applied to
drummed tritiated wastes (see Section 13) but, if needed, it may be also to wastes
which are only bagged in bulk.
As illustrated in Section 4 solid and liquid tritiated wastes, which will arise
from the operation and maintenance of future Fusion Reactors and associated Tritium
Handling Plants, are expected to include a large range of material of different origin,
nature and size.

Solid wastes could be classified as:

- Suspect or slightly tritium contaminated wastes including miscellaneous combustible

and/or compactible solids arising from general laboratory cleaning and contamina-
tion control operations.
- Medium or high tritium level wastes, including miscellaneous combustible and/or
compactible solids arising from normal laboratory operations as well as from decon-
tamination, modification and maintenance operations on plant equipments, glove
boxes and fume hoods.
- High tritium level wastes, including tritium permeated hardwares arising from the
repair and maintenance operations in tritium handling plants or reactor systems.

\
 22

Liquid wastes could be classified as:

- Suspect or trace-level effluents, including large volume aqueous streams coming

from some low risk areas of a tritium handling plant or laboratory (e.g. showers,
hand basins drains and sumps).
- Low tritium level effluents, including medium to low volume waters arising from
eventually contaminated drains and sumps as well as from molecular sieve regenera-
tion operations.
- Medium or high tritium level effluents, including:
. low volume waters arising from laboratory experiments, tritium rework, deconta-
mination and cleaning operations, molecular sieve regeneration operations as well
as
. low volume organic liquids arising from plant maintenance and routine laboratory
operations.

6.1 Reference for Section 6

(1) Wong K.Y and Utting R.E., Safe Handling of Tritium, proposed IAEA Safety
Series Procedures and Data Document, December 1987, under publication.

(2) 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 Tech-
nology in Fission, Fusion and Isotopie Application, Toronto, Canada, May 1-6,
1988.
 23

IMMOBILIZATION AND CONTAINMENT OF TRITIUM FOR WASTE

MANAGEMENT PURPOSES

7.1 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.g. transportation, storage or disposal), may be done under the safest condi-
tions. In the event that the outer waste containment package may be breached during
the above operations, 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.
As illustrated below, tritium immobilization may be attained up to a certain ex-
tent by incorporating tritiated wastes into solid matrix materials (e.g. dryers, cements,
polyester or epoxy resins, etc.), 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.
However, as demonstrated by many extensive experimental studies,tritium in-
corporated in such matrices alone cannot be considered sufficiently immobilized, due
to outgassing properties and teachability of final tritiated composites (see subsection
9.3). 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 7.5).

7.2 Required degree of tritium immobilization

It is unanimously recognized that, even if desirable, all causes of tritium re-

leases to the environment occuring during the fission reactor fuel cycle, cannot in
practice be completely eliminated. This means that during the fuel cycle, even if
small, some loss of tritium is normally expected. It is however very difficult to define
to what percentage this loss will amount.
In reference (1) some "initial" tritium loss levels, i.e. 10%, 1% and 0,1%, are
tentatively indicated and assumed for evaluating safety requirements associated with
different storage situations (store failure or constant leakage of store).
In case of a store failure and assuming the above "initial" loss values, the period
for which a safe store of tritium should be guaranted (i.e. the period after which the
tritium accidentally released will at maximum be equal to that "initially" lost) has been
calculated. The period amounts to 41,82 or 123 years if an "initial" tritium loss of
10%, 1% or 0,1% is respectively assumed.
In case of a constant leakage of store and assuming twice the "initial" loss val-
ues, a maximum permissible leakage limit has been calculated. It is intended that
within this limit the total tritium release will never at any time exeed twice the "ini-
tial" 10%, 1% or 0,1% loss value respectively. The calculated tritium leakage limits
amount to 0,009%, 0,007% or 0,00007% per day if "initial" loss values of twice 10%,
1% or 0,1% are assumed respectively. A maximum limit value of 0,001% per day (i.e.
0,36% per years, corresponding to about one tenth of the largest limit value) is finally
 24

suggested (1) as the likely one to be acceptable after a tritium immobilization pro-
cedure.

7.3 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. 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. Drying agents
II. Inorganic hydrates and cements
III. Organic polymers
IV. Metal hydrides.
The application of one or others of these materials primarily depends on the
chemical form of tritium to be immobilized (e.g. tritiated hydrogen or water) which
must be compatible with the selected material.
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 hydrogenated polystyrene) can be properly
utilized only for immobilizing tritiated hydrogen.
Another immobilization technique which is one of the most in use is the simple
packaging of tritium gas in stainless steel cylinders. All the available methods are
compared in Tab. 7.1 where some technical aspects of their application are also sum-
marized.
A proportional order of merit has been proposed by McKay in a CEC sponsored
study on the potential tritium immobilization routes (1). The order of merit derived in
this study was based on the assessment of some properties which are summarized in
Tab. 7.2.
In this study the main topics requiring further R&D work have also been
indicated namely:
- Tritium immobilization techniques and flow-sheets to be extensively developed in
order to attain the highest tritium incorporation yields.
- Tritium retention properties of solid matrices selected for tritium immobilization to
be tested on an experimental basis and over a sufficient long period. This in order
to ensure that all the possible mechanisms of tritium release (e.g. chemical decom-
position, radiolysis, isotopie and chemical exchange, teachability) may be taken into
account.
Among other topics, the isotopie enrichment and the employ of physical barriers
to further contain tritium have been also indicated.

7.4 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.
TABLE 7.1 ­ Potentially applicable methods for tritium immobilization purposes.

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, decay
ZrH.(T) 600°C­900°C 2.2 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 stability Permeation of HT through
HYDROGEN (1 bar)<1> Potential for recover­ the steel container during
(HT) ΥΗ χ (Τ) moderate t"C 2.2 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, 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 . "Burned" gypsum 6.2 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. use of multiple physical
WATER (Si0 2 xH 2 0) Low water retention above barrier systems (i.e. pri­
(HTO) 100­C mary, secondary and ter­
Zeolites (Mol.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.
Commercially available
in pellet and bead forms
TABLE 7.1 - Potentially applicable methods for tritium immobilization purposes (cont.)

Liquid or FORMATION OF INORGA- Strong water retention Utilization of hydroxy-

vapor NIC HYDRATES up to 800°C, 900°C, lapatite on a large plant
. 3 Ca3(P0 4 ) 2 2H 2 0 3.7 275"C and 100°C scale impracticable because Manufacturing routes
. 3 C a j i P O ^ Ca(OH) 2 1.8 respectively of difficult dehydration, still to be established
(Hydroxylapatite) Low equilibrium vapor inhalation hazards (dust
. 3 CaO AljOj 6H 2 0 29 pressure even at high form) or reduced rehydra-
. 3 CaO A1,0, 3CaS0. 46 water loadings, 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) . OPC<2> 25-28 Low costs Mobility of tritiated Most developed
. 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- of development
POLYMERIZATION poration yields
By-product formation
Limited stability to
heating, radiations &
wheather ing

(1) 1 bar = 100 kPa.

(2) Ordinary Portland Cement.
(3) High Alumina Cement.
TABLE 7.2 - The order of merit concerning groups of matrix materials available for tritium immobilization as derived from the McKay study (1).
GROUPS OF MATERIALS IN
MERIT ORDER
(A) Inorganic hydrates, etc.
(B) Metal hydrides
(C) Organic polymers
(D) Hydraulic cement
MERIT ORDER OF MATERIALS WITHIN GROUPS PROPERTIES
(1) Calcium phosphate and hydroxylaptite Insoluble hydrates of very low water vapour pressure are available. Molecular
hydrates sieves can also take up appreciable quantities of water while retaining a very
(2) Molecular sieves low vapour pressure. Tritiated water can be Incorporated in these materials by
(3) Calcium aluminate hydrate a simple heating/dehydration-cooling/rehydration cycle. There are no obvious
disadvantages, but it is still to be demonstrated that the tritium is in fact
sufficiently immobilized. A low water vapour pressure is not a sufficient crite-
rion, since isotopìe exchange processes can still be envisaged that would render
the tritium mobile.
(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. Titanium hydride ap-
pears to be a good alternative, and may even be superior. The main drawback to
these metal hydrides is the necessity to use tritiated hydrogen at high tempera-
tures (~600eC) for their preparation.
(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. In
(3) Polyvinylacetate virtually all cases there would be a necessity to recover, burn and recycle by-
(4) Sili cone/acetylene addition compounds products. Hydrogenated polystyrene may be the best choice since it has good me-
chanical properties, leach resistances and radiation stability, and the tritium
is incorporated in a single reaction stage. All the other indicated polymers
have the disadvantage of requiring a hydrogen or acetylene feed; polymers using
a water feed would generally be expected to give poor immobilization.
Cement is a particular example in the category of inorganic hydrates. As usu-
ally prepared it immobilizes only part of its water content even if the propor-
tion immobilized slowly increases on standing ("curing"). Polymer impregnation
of the cement reduces the tritium leach-rates in water, but the evidence on the
degree of reduction is conflicting; the long-term stability of polymer-impreg-
nated cement, subject to some radiolysis, is also doubtful.
 28

As indicated in ref. (1) the most appropriate matrix should have the following
properties:
- Low chemical and radiological toxicity.
- Low flammability.
- Low exchange rate with environmental water.
- Low costs of matrix production and tritium incorporation.
- High chemical, thermal and radiolytic stability.
- High yield in terms of tritium incorporation.
- High capacity for tritium.
Note that high capacity for tritium becomes less important if the tritium enrich-
ment is carried out before immobilization. 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,
burial or repository) is envisaged for the tritium immobilization product. Storage and
disposal conditions will determine in fact to what extent the material will be subjected
to heating, water leaching, moisture etc. and how much important will be its re-
sistence properties related to these conditions.

7.5 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, 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. The concept essentially relies on
the application of a sequence of successive physical barriers, each of them giving a
contribute to the overall tritium containment.
On the other end if it is true that the overall efficiency of tritium containment
mainly relies on the integrated employ of these barriers, than it can be concluded that
even if insufficient by itself, the use for tritium immobilization purposes of a solid
matrix would become acceptable if integrated in a multi-barrier system. Consequently
even simple and cheap solidification or encapsulating media such as hydraulic cements
can still satisfactorily be employed.
Different multi-barrier containment systems have been assembled by combining
various additional treatment that may be applied on a waste immobilization matrix
(e.g. coating, impregnation, encapsulation) with some containment options such as
simple containerization or simultaneous containerization and container encapsulation.
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 matrix and physical barrier materials as well as the various containers are
usually selected and assembled case by case. This is done not only in compliance with
the chemical form, physical state and concentration of tritium in the waste form but
also depending on what of the available waste storage or disposal routes (e.g. surface
storage, shallow inground burial or deep geological repository) will be subsequently
applied. An exemple of what kind of physical barriers a multibarrier system may
include is given in Fig. 7.1 taken from ref. (5).
 29

Other exemples of multibarrier system are illustrated in Section 12, Figs. 12.1 to 12.3.

Immobilized
V/MMMMM/m tritiated waste

•Primary container

•Encapsuling layer
(optional)
!/ H iii' - ï I 1 -1ιί1.*ίιί^ί4 t * * * * * # f,

WZMZnZMZZM^container
Secondary

FIGURE 7.1 Multiple barrier system conceptually assumed and experimentally investigated at Ontario Hydro
for tritiated waste containment and packaging (S).

7.6 References for Section 7

(1) McKay H.A.C., Tritium Immobilization, EUR 6270 en (1979) Europen Appi.
Res. Rept. - Nucí. Sci. Tech., Vol. 1, No. 3 (1979) 599.

(2) IAEA, Handling of Tritium Bearing Wastes, IAEA Technical Reports Series
No. 203, IAEA, Vienna, 1981.

(3) IAEA, Management of Tritium at Nuclear Facilities, IAEA Technical Reports

Series No. 234, IAEA, Vienna, 1984.

(4) Burger L.L. and Rayan J.L., The Technology of Tritium Tixation and Storage,
BNWL-1807 (1973).

(5) Krasznai J.P., Tritiated Waste Conditioning, Part III - Performance of Con-
tainerized and Encapsulated Waste Forms, Ontario Hydro Research Division
Report No. 85-279-K(1985).
 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.
TABLE 9.2 - Tritium Removal Facilities presently in operation.

TRITIUM ENRICH. FACILITY OWNER OPERATIONAL SERVED Τ-FEED CONC. ANNUAL Τ-EXT. RATE
REF.
PROCESS SITE ORGANIZAT. AVAILABILITY REACTOR GBq -kg" 1
Ci 'kg' 1
PBq(MCi) -a
1

CEN GRENOBLE LAUELANGEVIN INST. High flux Research

VPCE SINCE 10?2 5/
-6 (0.16) 1,4.5
(FRANCE) (1) (F, FRG, UK) Reactor

DARLINGTON G.S. ONTARIO-HYDRO Twelve Pickering &

VPCE 1987-88 Darlington CANDU- 2.6-3.7 7-10 6.3-9.3x10' 3.6,15
(CANADA) TRF (2) (CANADA)
type Reactors xlO' (17-25)

CHALKRIVER NAT. LAB. AECL Research 1.85x10' 5 -18 (0.5)

LPCE AECL (CANADA)
(CANADA), TEP (3) 1987-88 3,13-15
Reactors 9.5x102 25 90 (2.5)
ω
(1) Tritium and Hydrogen Extraction Plant
(2) Tritium Removal Facility
(3) Tritium Extraction Plant
 37

If higher degree of tritium enrichment have to be considered, 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.

9.3 Solidification of tritiated waste waters

As mentioned in subsection 7.3 various matrix materials could be used to

solidify tritiated water, i.e., to incorporate tritiated water in a stable solid matrix, for
tritium immobilization purposes. Incorporation of tritiated water in these materials can
be achieved by:
- mixing tritiated water and the selected solid material in due proportions;
- passing a gaseous stream containing tritiated water vapor through a bed of the
selected material having a particle size (e.g. pellets, beads) suitable for water vapour
removal from the carrier gas stream;
- using tritiated water as a chemical reagent to prepare the incorporating solid mate-
rial itself.
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.
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.
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.g. hydrated
calcium phosphate by precipitation) or alternatively in the chemical preparation of a
tritiated monomer compounds (e.g. tritiated acetylene, acetaldehyde, etc.) which then
has to be polymerized. 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.
Candidate matrix materials specifically applicable for tritiated waste water
solidification are briefly illustrated in this section.
Methods as well as some technical aspects of their application are summarized in
Tab. 7.1.

9.3.1 Drying agents

Silica xero-gel, activated alumina, and molecular sieves are the products usually
taken into consideration as candidate drying agents (1,19). Some others traditional
drying agents (e.g. phosphorus pentoxide and magnesium Perchlorate) have been
excluded because of their high water solubility.
Silica xerogels (xeros - dry) are amorphous dehydrated gels of silica (20,21)
which, due to their highly developed internal surface have a high water capacity,
being capable of loading up to about 40 wt% of water. However at this loading per-
centage the resulting vapor pressure is close to that of pure water. Only at low water
loadings water is strongly held and the lowest values of water vapor pressure can be
attained. It is worth noting that at 10 wt% loading its vapor pressure is still 20% of
 38

that of pure water whereas above 100°C its water retention efficiency become very
low (19).
Activated alumina exhibits a similar unsatisfactory behaviour and a still lower
loading capacity.
Molecular sieves is a commercial name used for a special type of zeolites, i.e. a
class of crystalline compounds (sodium alumino-silicates) which either occur in nature
or may be produced synthetically on a commercial scale.
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.g. Ca0 2 .6H 2 0) (20).
They do not display a stepwise increase of dehydration temperature as it would
be the case if a crystal structure decomposition does occur; their dehydration curves
show in fact inflection points instead of steps (20). 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. A portion of water in most zeolites is
anyhow more firmly bounded than the rest and cannot be expelled without destroying
the crystal lattice.
The LINDE company markets a dried Zeolite A containing 1.5 wt% of water as
type HA molecular sieves.
It is worth noting that zeolite A when fully hydrated (Na 2 O.Al 2 0 3 .2Si0 2 .4.5H 2 0)
contains 22 wt% of water but when water loading diminuishes to 17 wt% (Na2O.Al2Og.
2Si02.3.2H20) its vapor pressure at 25°C amounts to 5x10"4 bar*.
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.
Their peculiar features and their non-negligible cost make them uneconomic for
solidification of waste waters of relatively low tritium concentration.

9.3.2 Absorbers

A variety of mechanical absorbers have so far been used to convert tritiated

water to solid or semisolid materials.
These materials are generally very inexpensive but their efficiency as immobi-
lizing agents is rather limited. 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. 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, diatomaceous earths and other chemically similar products are the most
common materials used as absorbers. They are also used as special material for filling
annular voids between secondary and tertiary waste containment drums.
Vermiculite is a mica-like material (i.e. a hydrated sodium-aluminium silicate)
which exfoliates when heated to 600-900°. It is an excellent liquid absorber and it can

For comparison the vapor pressure of water at 25°C is S· 10 bar.

 39

change its sodium with calcium and magnesium which may help in the uptake of
other nuclides (15,21).
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). This material is notable for its excellent
capacity for absorbing liquids.

9.3.3 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.
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). Hydroxylapatite is a hydrated calcium
phosphate compound that occurs naturally and contains strong bound water. It can be
prepared also synthetically. 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. According to ref. (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:
- Dehydrated form of hydroxylapatite is not easy to prepare (64 hours at 1250'C) and
consequently some problems may arise for its rehydration.
- Although hydroxylapatite is reported (19) to have a very good thermal stability as
compared to most other inorganic hydrates, 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).
- Tritium density reached in the tritiated hydroxylapatite is very low.
- 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. 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.
Calcium aluminate firmly bound water because of its structure corresponding to
the hexahydrate, Ca3[Al(OH)e]2. For tritium immobilization purposes it has to be
dehydrated. At 275°C it evolves 4.5 moles of water and completely the rest of water
only at 1050eC giving anhydrous 3CaO.Al2Os (19).
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.25 H 2 0 (23).
About twenty four of water molecules that are weakly bounded (interstitial position)
are lost at 100-110°C with shrinkage of lattice. The remaining water appears to be
more strongly bounded (hydroxyl position). Therefore to immobilize tritiated water as
 40

more firmly as possible, the direct hydration of an anhydrous mixture of 4 CaO.

AljOj.SO, with CaO and CaS04 of the overall composition 3 CaO.Al2Os.3 CaS04
should preferably be made only to attain the heptahydrate structure (Ca^AKOH)^
(S0 4 ) 5 .H 2 0) instead of the ettringite structure.
Gypsum (CaS04.2H}0) is found widely spread in nature. It loses 75% of its
crystallization water at 128°C to give "burned" gypsum (CaS0 4 .l/2H 2 0), an hem ¡hy-
drate containing 6.2 wt% water that is capable of tacking back the lost water at ordi-
nary temperature (15,20,21). By heating in a oven at 230-240eC anhydrous calcium
sulphate is obtained which is reactive enough for being used as a drying agent. Up to
the hemihydrate composition calcium sulphate binds water strongly giving a dew-point
of -62eC. 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. At MLM (Mound Lab. 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).

9.3.4 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).
The water capacity of commercially available hydraulic cement is in principle
reasonably high, e.g. approximately 25 wt% for portland type cements and up to
50 wt% for high alumina cements. Theoretical values are somewhat higher since they
neglect non-hydrating impurities present in commercial cements. 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):
- the relative amounts of individual cement constituents and the general stoichiome-
try of resulting hydrated and hydroxylated compounds;
- the nature and relative amount of additives eventually added to cement for various
purposes (e.g. increase of the immobilized water loading or workability or resistence
to compression);
- the nature and relative amount of liquid, wet or solid wastes to be incorporated into
cement or concrete (e.g. concentrates, sludges, ion exchange resin, inorganic sorb-
ente, miscellaneous wastes, etc.) which often may act as water carriers or sorbents.
The procedure and technology related to the cement hydration process are sim-
ple and well known. A hydraulic cement mixed with water and aggregates (i.e. sand,
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. Mixing of the
various components can be achieved either by in-drum or in-line techniques, e.g. the
rotary mixing or drum tumbling applied on a batch basis, as well as the screw dynam-
ic mixing applied either on a batch or continuous basis (30).
In the current practice standard types of concrete have been used for several
years to immobilize solid radioactive items and packaged waste. However for medium
and low active liquid wastes and sludges different techniques are required and formu-
 41

lations of neat cement only are replacing the use of concrete (28). Inert materials such
as sand and aggregates have therefore been excluded from the mix. The liquid waste
and sludges can be considered as totally or partially replacing the water normally used
for mixing with the cement.
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. Cement is the cheapest candidate material having a considerably high water sorp-
tion capacity.
II. Cement is an immobilizing agent already accepted and practised in many coun-
tries for incorporating and disposing of various types radioactive wastes.
III. The shielding effect of concrete is particularly useful when gamma-emitter
contaminants such as fission and/or activation products are associated with
tritiated water.
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. This is because an
excess of tritiated water in an unbound state can obviously be more easily leached out
or evaporated.
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. Since the total pore volume is dependent upon the initial w/c
ratio applied to the cement mix, there is, therefore, another incentive to carefully cal-
culate the proportion of water to cement, i.e. to attain a sufficient low porosity along
with a still acceptable consistency of the final cement block.
On the other end the hydration of cement constituents is know to continue in a
cement block over long periods of time. Different periods of time are normally ap-
plied for "curing" (i.e. hydrating) the hardened cement depending on the tipe of ce-
ment used in the mix (35). After these periods however, 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. 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.
2. 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.
3. After hardening the cement block has to be adequately "cured" (i.e. left to stand
under controlled conditions) in order to reach in a reasonable time the maximum
achievable degree of cement hydration.
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, the lat-
ter being dependent on the cement type.
Water to cement ratios near 0.2, allowing to obtain still workable cement mixes,
have thus been applied to prepare tritiated cement specimens tested at the various
laboratory for experimental studies on tritium leaching.
 42

Curing times of 28 days for portland cements (types I, II, 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).
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. However, 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, leading to an increase
of tritium release to the environment.
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. Leach data from experimental tests performed at BNL (Brook-
haven National Lab.) (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 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. A water/adsorber ratio of 0.3 was initially applied, which
represents approximately two-thirds of the water necessary to completely saturate the
silica gel. 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.
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. 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).
As demonstrated at Ontario Hydro (41,42) the addition of Si0 2 to cement in low
proportion (i.e. 5 wt% of "silica fume", see Tab. 9.3) was found:
- 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;
- 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;
- to reduce setting time and improve workability of the cement paste.
- to reduce the teachability of tritiated water from a "neat" cement matrix. As shown
in Tab. 9.3, in comparison with the tritium leach rate of a tritiated portland cement
matrix without additives, the leach rate from the same cement matrix containing
5 wt% of Si0 2 is reduced approximately by a factor 7.
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 II il a modified cement type employed
to yield a lower heat of hydration than type I, slower setting, and a better sulphate resistance. Type III
develops a large fraction of its ultimate strength in very few days and has a larger heat generation rate than
type I. Type IV has a low heat generation rate and amount of heat. Type V is formulated to resist to severe
sulphate attack (SRPC).
 43

should be minimized or eliminated. 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. For this raison an appropriate choice of the cementation procedure and relat-
ed process conditions was needed.
On the light of such consideration available alternatives for the in-drum cement
mixing and casting were consequently evaluated. 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). Rotary mixing appeared
less attractive because, to avoid decontamination and cleaning operation, mixing blades
should be disposed within the solidification container.
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).
The first method entails the end-over-end tumbling of the cement and water in
the containing waste drum (32-36). It is a dynamic in-drum mixing technique produc-
ing a homogeneous mixture. No cleaning of equipment is required but a substantial
volume of cement paste (-90 dm3 inside a 30-gal drum) is to be handled.
When the preparation of smaller size specimens was needed at BNL (37-39), the
required specimens size (-16 dm3 volume) was not compatible with in-drum tumbling
technique developed for large scale PITC composites. 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).
The third method, i.e. the injector technique, is based on a static technique
more compatible with the glove-box or hot cell operations, entailing the handling of
small volumes of highly tritiated aqueous waste (37-40). This method was successfully
applied also at MLM (43-49). 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. 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.
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, the fraction of mobile (evaporable) water held in it and the physical
conditions surrounding the block such as the ambient temperature, moisture and envi-
ronmental water. If not adequately controlled, 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, hence of tritium release
rate to the environment. The probability of keeping tritium release rate as low as pos-
sible will therefore depend on the careful determination of two important process
parameters, i.e. the water to cement ratio originally employed in the cement paste and
the time period applied for "curing" (i.e. hydrating) the cement block.
Many extensive experimental studies have been carried out at BNL (32-40),
MLM (43-49), LASL (Los Alamos Scientific Laboratory) (52) and Ontario Hydro Re-
search Division (41,42,50) in order to investigate the tritium leacheability from
specimens of tritiated cement matrices. Results have been published in several reports
(32-52) and reviewed by various authors (15,19,29,31). Most significant experimental
 44

data from leching tests on tritiated cement specimens published by these laboratories
are reported in Tab. 9.3. The assessment of these data leads to the conclusions already
presented in ref. (31) which can be summarized as follows:
- Hydraulic cements are the simplest and less expensive water solidification media.
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, which may convert to lower
hydrate forms on ageing.
Portland cements appear to be the best cement types utilizable for tritium immobi-
lization purposes. 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.
- Cement additives such as water sorbents (e.g. vermiculite or equivalents) were
found to allow increased tritiated water loading but at the same time higher tritium
release rates. As to the silica gel, although its addition to cement do not involve any
increase of tritium leachability, 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.
Nevertheless the addition to cement of a low proportion of Si0 2 (e.g. 5% of "silica
fume") has been found to be beneficial, especially because of the resulting increased
resistence of the waste composite to tritiated water permeation.
- To minimize the environmental tritium releases (e.g. by leaching or outgassing) to
an acceptably low level the application of other supplementary physical barriers is
anyhow mandatory.

9.3.5 Organic polymers

Organic polymers have been identified (19,53-55) as potentially candidate mate-

rials for tritium immobilization. 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. Other essential advantages as tritium immobilizing media are the chemical
stability, the low volatility and the good mechanical properties.
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. Typical draw-backs especially dealing with some types of polymers are:
- the insufficient yield of tritium incorporation in the polymer;
- the significant yield of tritiated by-product to be retreated;
- the limited stability of tritiated polymer to thermal as well as long-term wheather-
ing effects.
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. Tritiated acetylene is in fact prepared through the reaction of
tritiated water with calcium carbide and then converted to a high molecular weight
polymer. Instead of being directly polymerized, tritiated acetylene may also be con-
verted to a tritiated acetylene-derivative manomer such as ethylene acetaldehyde,
acrylonitrile or vinylacetate, which then is polymerized.
TABLE 9.3 - Comparison of data obtained from tritium leaching tests on untreated tritiated cement specimens at the indicated testing laboratories.

SPECIMEN IDENTIFICATION RESULTS

TESTING REF.
Per Cent Release LABORAT.
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 0.18 -0.2 0.6<1> 3.7 0.1 n.a. 10 65.6 6.56
BNL 34
High Alumina 0.18 n.a. n.a. 3.7 0.1 n.a. 10 35.9 3.59

70 -39.0 0.56
Portland I 0.3 -0.1 -0.83 111 3.0 1-365 140 -47.0 0.34 LASL 52
175 -52.0 0.30 . fe

Portland III n.a n.a 140 2.50 0.018

n.a. n.a. 1.0 MLM 19,29
196 8.00 0.040

Portland 30 -0.28 -0.1 -0.83 60 47.0 0.78

-83.0 2.23 1.0
180 63.0 0.35
High Alumina -0.30 -0.1 -0.83 -93.0 2.51 1.0 180 -77.0 -0.43 Ontario
41,50

Portland 30 (95X) n.a. n.a. -0.83 452.5 12.23 n.a. 60 6.84 Hydro
0.114
Silica Fume<2> (5X)

(1) Estimated values.

(2) It is a 90-95X Si0 2 by-product from the ferrosi licori and silicon metals production.
 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. Tritiated polystyrene can be in fact prepared by reaction of polysty-
rene with tritiated hydrogen at atmospheric pressure and room temperature, in pres-
ence of a catalyst (rhodium on alumina) (55). These process conditions are manda-
tory. 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.
Some organic polymers and related polymerization processes potentially applica-
ble for tritium immobilization purposes are compared in Tab. 9.4, where various types
of polymer instability are also considered.
Static leach test have been performed on tritiated organic polymers, at BNL and
BNWL (Battelle North-West Pacific Laboratory) by immersion of tritiated specimens
in deionized water. Results of tests (19,32,34,54) showed an initial rapid release of
some percents of tritium originally incorporated in the polymer specimen within the
first few leaching days (e.g. 3.8% from tritiated polyacetylene at BNL (34) and 2% and
less than 5% respectively from backelite analogue and polyacrylonitrile polymers at
BNWL) (54). Thereafter very little or negligible tritium releases were detected in both
laboratories over a four to six weeks leaching period. This behaviour was explained as
due to leaching of surface retained by-products (34) as well as unreacted monomer
residues (54). 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.
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:
- Besides the various types of instability (see Tab. 9.4) which are typical of some
polymers, 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.
- 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.
- 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, hence the tritium retention efficiency.
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.
Based on this technique, which is subject of a US patent (56), water extendible poly-
ester (WEP) resins were investigated at Ontario Hydro (57) for solidifying aqueous
radioactive wastes as an alternative to cement hydration. 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.
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.
TABLE 9.4 - Comparison of some organic polymers and related polymerization processes potentially applicable for tritium immobilization.

POLYMERIZATION PROCESS STABILITY

POLYMER TRITIATED TESTING REF.
(9) LABORAT.
TYPE MONOMER Easiness By-products " vield Heatin9 Rad1at
- BSffiSaS ( O wheatheri ng
(5) C O Total gas H20

Difficult C 6 H 6 ; water -30

(3) 325 0.15 ( 1 0 ) Easily oxidised BNL 19,32,34
Polyacetylene TC = C H
(3)

Stable in the dark.

Polyethylene TCH=CH2 Satisfactory -96(6) n.a. 3.1 2.2 Brittle in air & on None 19,54
light

Polyacety- Brittle I friable

(7)
Bakelite type (1) TCH2-CT0 Satisfactory lenes, Croto- -95 (7,8) 0.1 (unless addition of BNWL 19,54.55
naldeyde (4) fibrous fillers)
TCH2-CHO

Polyacrylonitrile TCH»CH Difficult (2) (4) -40(2) 200 0.4 0.1 Good BNWL 19,54
' ¿N 0.8

Fairly good, but it

Polyvinilacetate TCH=CH Satisfactory -99 150 1.4 n.a. absorbs water. Re- None 19
COCH, quires fillers.

Hydrogenated (5) (5) 280 0.03 0.02 Good BNWL 19,54,55

polystyrene 0.08

BNL = Brookhaven National Laboratory, Upton (NY).

BNWL « Battelle Pacific North-West Laboratory, Richland (WA).
n.a. = not available.
TABLE 9.4 - Remarks (Continued).

(1) Phenol or resorci noI-acetaldehyde-formaldehyde type polymer.

(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.

(3) At 280SC and a 50 cm3/min. acetylene flow rate (32).

(4) The condensation product of two molecules of acetaldehyde.

(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.

(6) At about 60°C and in presence of a Ziegler catalyst.

(7) Resorcinol-acetaldehyde-formaldehyde type polymer (CHT-CH = CH-CHO). ^

3
00

(8) Ageing above 130°C, thermal degradation above 230, 50 wtX loss at 390°C.

(9) G value ■ number of molecules formed per 100 ev energy adsorbed.

(10) The G(-C 2 H 2 ) value, measured by irradiation in absence of water is higher than 100 (19,34).
 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 (50,57).
Static leach tests were carried out by immersing each tritiated specimen in 0.2
litres of demineralized water over a leach period of 180 days.
The leachant was not changed and one millilitre sample was periodically taken for the
analysis by liquid scintillation counting after an appropriate dilution (50). For compar­
ison purposes tritiated cement (i.e. portland and high alumina) specimens were also
prepared (see Appendix V) and tested under the same leach conditions. Leaching data
expressed as cumulative per cent tritium releases were plotted vs leach time as shown
Fig. 9.1 taken from ref. (50).

SC. 47

1-

ε
t; 26.27 Portl ond Cement 1 day eure
31,32 Por t lond Cement ¡β day cure
36, 37 High Al umino Cement I doy eure
o.i »t, »2 High Al umino Cement 2t doy eure
St, «7 Water Extendibl e Pol yester I day cure

0.01 ' ' ' ' "III I M I UMI I I I Mill

U 100 1000
Days

FIGURE 9.1 Static leach tests at Ontario Hydro (50). Comparison of solidification matrices. Cumulative per
cent tritium releases in water v s leach time.

Based on these data average daily per cent tritium release (d"1) rates have been
calculated as shown in Tab. 11.5. 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. As shown
 50

in Fig. 9.1 this cannot be applied to all experimental diagrams but nevertheless, as also
pointed out in ref. (50), it enables to compare results on a normalized even if appro­
ximate basis.
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. Anyhow the average values of daily
per cent tritium release rates of all the three solidification matrices were found (see
Tab. 11.5) to vary after 180 days of leaching time from a maximum of 0.42% per day
to a minimum of 0.13% per day. Consequently one has to conclude that the solidifica­
tion of tritiated waste water by a WEP resin, even if appears to be the best option in
terms of tritium retention efficiency, seems to be still not sufficient (like cements) to
attain the maximum tritium release target of 10~*% per day as suggested in ref. (19).
A modified polystyrene resin (Dow­binder 101) has been investigated at KFK­
Karlsruhe (58) as a candidate matrix material for the incorporation of tritiated water.
For this purpose, tritiated polystyrene specimens containing monomer to water ratios
in the range 0,8 to 5 were prepared according to the procedure described in Appendix
VI. Specimens were then submitted to static leach tests by immersion in 0.5 litres of
water over a leaching period of 104 hours (­416 days). Samplings of 1 microlitre were
periodically taken from the leachant. For comparison also tritiated water/portlant
cement specimens (w/c weight ratio = 0.4) were prepared (see Appendix VI) and
tested under the same leach conditions. As it is shown in Fig. 9.2 taken from ref. (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.

0.5
Δι
y
H2O/HTO in cement
Ao 28.6% Η2Ο/ΗΤΟ in specimen
0.4

0.3

0.2

01 H2O/HTO in dow-binder 101

48.9% Η2Ο/ΗΤΟ in specimen

¿­o'0"Ι ­
0.0 " 2
Ο 10 20 30 40 50 60 70 80
,t(h)'

FIGURE 9.2 Static leach tests at KfK (58). Comparison of solidification matrices. Fractional tritium releases
in water vs leach time.

The corresponding average tritium release rate calculated for the polystyrene
specimen (approximately 0.1% per days) is however still far away from the suggested
maximum release target of 10_3% per day (19).
 51

Based on the comparative evaluation of all the above experimental data the fol-
lowing conclusive remarks can be made:
- 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, but not to a sufficient extent. 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.
- This means that even if superior to a neat portland cement, polystyrene and WEP
resins were water solidification media still inadequate to meet alone the suggested
tritium release target of 10"s% per day. As for cement therefore, one or more addi-
tional containment barriers are needed to minimize tritium release rate up to an
acceptably low level.
Furthermore one has to point out that, owing to their rather complex application pro-
cedures, 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.

9.4 Solidification of tritiated organic liquids

Relatively small amounts of tritiated organic liquid wastes (e.g. 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, development
and analytical purposes.
Various alternatives have been foreseen (41,42,59) for the management of such
wastes:
- Rework (i.e., dewatering, filtration and upgrading) for reuse within the originating
facility, provided that their tritium contamination is only at a tracer level or
suspected.
- Incineration, if their recycling is not worthwhile and provided that their radioac-
tivity and tritium concentration do not exceed certain limits.
- Solidification and packaging for storage or disposal, if the above limits are
exceeded.
The rework of radioactive oils is however an operation which may generate in
turn additional (secondary) tritiated organic wastes. At Ontario Hydro (59) the volume
of these additional waste (i.e. 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.
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. This
last option is regarded either as unpractical if, as it would be reasonable, low cost
sorbent material are used with a consequent too high production of residual ashes (e.g.
10 kg/litre of absorbed oil) or uneconomic, if too expensive absorbers (e.g. polyethyl-
ene fibres, polymer beads, etc.) must be used (59) to limit the ash production.
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
 52

storage and/or disposal. As for tritiated waste waters, 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. This requirement can be met if the tritiated organic liquid is incorporated
into or absorbed on a solid matrix. To this end various types of potentially applicable
matrix materials were investigated, namely cements, organic polymers and absorbers
(41,42,59).

9.4.1 Hydraulic cements

Portland and high alumina cements along with the so called Envirostone
Gypsum cement, were investigated at Ontario Hydro (59) as candidate matrices for the
solidification of tritiated organic liquid wastes. They were used in conjunction with
some emulsifiers either commercially available or suitably prepared (i.e. 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,
and mixing at high speed before the addition of the cement powder. 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, portland
type HI cement and water (59).
As reported in ref. (41) a fractional tritium release rate of 1.8xl0"5 cm^d"1 (i.e. an
average daily release of 3.5x10"*%) was measured for specimens of cement solidified
tritiated oil contained inside a 0.1 cm thick polyethylene bottle (v/s=0.476 cm). This
technique therefore appears to be near to meet the 10"*% daily tritium release target
(19). 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. 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. For this reason this technique was deemed to be unsuitable for tritium
immobilization purposes (41).

9.4.2 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.
The final solid composite is then obtained by an intimate mixing with the liquid
organic polymer, by subsequent addition of a suitable catalyst amount and curing.
The application of such a matrix was investigated at Ontario Hydro for the
solidification of polyethylene contained tritiated oils (41). A rather low oil incorpora-
tion yield was attained (i.e. 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, being a polyethylene bottle utilized to contain
the WEP solidified tritiated oils. This was explained as due to the negative effect of
the WEP components on the wall of the polyethylene bottle. For these reasons also the
 53

application of a WEP resin as a solidification matrix for polyethylene contained tri-

tiated oik was deemed to be unsuitable (41).
As pointed out in ref. (59) the use of oil extendible polyurethane resins for in-
corporating tritiated waste oils is, in principle, possible, but sometime difficult
because of the critical dependence of the characteristics (e.g. mechanical strenght and
dryness) of the final solid product from process parameters such as the time and speed
of mixing.
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.
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).
Solidification of waste oils may be attained also by their incorporation into a
urea-formaldehyde resin. However as reported in ref. (59) the resulting wax-like solid
product was not stable. 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.

9.4.3 Absorbers

Another alternative option investigated at Ontario Hydro (41,42,59) for immo-

bilizing tritiated waste oils is based on their absorption on thermally expanded silicates
such as vermiculite, perlite or chemically similar absorbers (41,42,59) provided that oil
loaded absorbers are then contained inside a polyethylene container. Since it was
demonstrated (41,42) that tritium permeability through the polyethylene increases even
if tritiated oil alone is introduced inside the container, the wails of the polyethylene
container must have an adequate thickness to compensate this phenomenon. 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.
As reported in ref. (42) results of leach tests indicated that oil-loaded ver-
miculite or "sorbent-C" (i.e. a perlite-based absorber) inside 1 cm. thick high density
polyethylene container were able to meet a tritium daily release target of 10~3%.
At MLM (59) vermiculite and a chemically similar material were also utilized as
absorbent matrices for immobilizing tritiated waste oils. 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. 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.

9.5 References for Section 9

(1) IAEA, Handling of Tritium Bearing Wastes, IAEA Technical Report Series No.
203, IAEA, Vienna, 1981, p. 15.
 54

(2) Holtslander W.J. et al., Recovery of Tritium from Candu Reactors, Its storage
and Monitoring of Its Migration in the Environment, Appendix I of Ref. 1.

(3) Canadian Tritium Experience Manual, Canadian Fusion Fuel Technology Pro-
ject, Ontario Hydro (1984).

(4) Pautrot Ph., Damiani M., Operating Experience with the Tritium and Hydrogen
Extraction Plant at the Laue-Langevin Institute, Separation of Hydrogen
Isotopes (RAE, H.K., Ed.), ACS Symposium Series No. 68 (1978) 163.

(5) Damiani M., Operating Experience with the Tritium and Hydrogen Extraction
Plant at the Laue-Langevin Institute in Grenoble Appendix V of Ref. (1).

(6) Sood S.K. et al., Removal and Immobilization of Tritium from Ontario Hydro's
Nuclear Generating Stations, Fusion Tech., Vol. 8 (1985) 2478.

(7) Hammerli M. et al., Combined Electrolysis Catalytic Exchange (CECE) Process

for Hydrogen Isotope Separation, Separation of Hydrogen Isotopes (RAE, H.K.,
Ed.), ACS Symposium Series No. 68 (1978) 110.

(8) Butler J.P. et al., Novel Catalyst for Isotopie Exchange between Hydrogen and
Liquid Water, Separation of Hydrogen Isotopes (RAE, H.K., Ed.), ACS
Symposium series No. 68 (1978) 93.

(9) Rogers M.L. et al., Catalytic Detritiation of Water, Separation of Hydrogen

Isotopes, RAE, H.K., Ed., ACS Symposium Series No. 68 (1978) 117.

(10) Mills T.K., Recovery of Tritium from Aqueous Waste Using Combined Elec-
trolysis Catalytic Exchange, Tritium Technology in Fission, Fusion and Isotopie
Application, Proc. ANS Topical Meeting, Dayton, Ohio, 1980, CONF-800427
(1980) 422.

(10) Enright J.T., Chuang K.T., Deuterium Exchange between Hydrogen and Water
in a Trickle Bed Reator, Can. J. Chem. Eng. 56(1978)246.

(11) Morishita T. et al., Tritium Removal by Hydrogen Isotopie Exchange between

Hydrogen Gas and Water on Hydrophobic Catalyst, Tritium Technology in Fis-
sion Fusion and Isotopie Applications, Proc. ANS Topical Meeting, Dayton,
Ohio, 1980, CONF-800427 (1980) 415.

(12) Chuang K.T., Holtslander W.J., Tritium Transfer Process Using the CRNL
Wetproof Catalyst, Tritium Technology in Fission, Fusion and Isotopie Applica-
tion, Proc. ANS Topical Meeting, Dayton, Ohio, 1980, CONF-800427 (1980)
425.

(13) Harrison T.E., Design of a Demonstration Tritium Recovery Plant for Chalk
River, Tritium Technology in Fission, Fusion and Isotopie Application, Proc.
ANS Topical Meeting, Dayton, Ohio, 1980, CONF-800427 (1980) 377.
 55

(14) Holtslander W.J. et al., Recovery and Packaging of Tritium from Canadian
Heavy Water Reactors, Fusion Tech., Vol. 8 (1985) 2473.

(15) IAEA, Management of Tritium at Nuclear Facilities, IAEA Technical Report

Series No. 234, IAEA, Vienna, 1984, pp. 13, 15 & 22.

(16) Bruggeman A. et al., Separation of Tritium from Reprocessing Effluents, Man-

agement of Gaseous Wastes from Nuclear Facilities IAEA-SM-245, Proc. Symp.
Vienna, 1980, IAEA, Vienna (1980) 157.

(17) Bruggeman A. et al., The ELEX Process for Tritium Separation from Aqueous
Effluents, Tritium Technology in Fission, Fusion and Isotopie Applications,
Proc. ANS Topical Meeting, Dayton, Ohio, 1980, CONF-800427 (1980) 411.

(18) Geens L. et al., Separation of tritium from aqueous effluents, EUR 11551EN
(1988).

(19) McKay H.A.C., Tritium Immobilization, EUR 6270 en (1979), European Appi.
Res. Rep. - Nuclear Science and Technology. Vol. 1, No. 3 (1979) 599.

(20) Remy H., Treatise of Inorganic Chemistry, Vol. I, Elsevier Pubi. Co. (1956)
pp. 496, 514, 491, 280.

(21) USERDA, Alternative for Managing Wastes from Research and Post-Fission
Operations in the LWR Fuel Cycle, ERDA-76-43 (1976) Vol. 2, part. 3,
p. 14.10, part 2, p. 12.15, part 3, p. 14.12.

(22) Brldger M.J. and De Freitas C.V., Tritium Immobilization by Incorporation in

Inorganic Solids, Nucl. Sci. and Techn. Vol. 3, No. 6 (1981) 1465, EUR 7653
(1981).

(23) Lea F.M., The Chemistry of Cement and Concrete, 3 rd Ed. (1970), E. Arnold
Pubi. Ltd.

(24) Mershad E.A. et al., Packaging of Tritium-Contaminated Liquid Waste, Nucl.

Tech., Vol.

(25) Burns R.H. et al., Solidification of Low- and Intermediate-Level wastes, Atom.
En. Rev. 2 (1971), 547.

(26) Lokken R.O., A review of Radioactive Waste Immobilization in concrete, PNL-

2654 (1978).

(27) Stone J.A., Evaluation of Concrete as a matrix for Solidification of Savannah

River Plant Waste, DP-1448, SRL, Aiken, SC September 1976.

(28) Palmer J.D., Smith D.L.G., The incorporation of Low and Medium Level
Radioactive Wastes (Solids & Liquids) in cement, EUR 10561 EN (1986).
 56

(29) Williamson A.S., Tritiated Aqueous Waste Immobilization, IAEA Coordinate

Research Meeting on "Handling of Tritium Contaminated Effluents and Wastes",
Juelich, FRG, October 20-24, 1980.

(30) Mannone F., Management and Disposal of Alpha-Contaminated Wastes, EUR

8574 EN (1983).

(31) Mannone F., Immobilization of Tritiated Waste-Water by Hydraulic Cements, A

survey of the State of the Art, Report EUR 11230 EN (1987).

(32) Colombo P. et al., Tritium Storage Development, Prog. Rep. No. 2, BNL-19688
(October-December 1974).

(33) As Ref. 32, PR No. 3, BNL-19981 (January-March 1975).

(34) Colombo P. et al., The Fixation of Aqueous Tritiated Waste in Polymer Im-
pregnation Concrete and in Polyacetilene BNL 20898, Conf.-750989 (1975).

(35) As Ref. 32, PR No. 4, BNL-20421 (April-June 1975).

(36) As Ref. 32, PR No. 5, BNL-20779 (July-September 1975).

(37) As Ref. 32, PR No. 7, BNL-21700 (January-March 1976).

(38) Neilson R.M. et al., Immobilization of Tritiated Aqueous Waste in Polymer

Impregnated Concrete, BNL-22900, Conf.-770611-21 (1977).

(39) As Ref. 32, PR No. 9, BNL-50625 (July-September 1976).

(40) As Ref. 32, PR No. 12, BNL-50733 (April-June 1977).

(41) Krasznai J.P., Conditioning of Tritiated Wastes from a Tritium Removal

Facility, ANS International Topical Meeting on Waste Management and Decon-
tamination, Niagara Falls, N.Y., Sept. 1986.

(42) Krochmalnek L.S. et al., Conditioning and Handling of Tritiated at Canadian

Nuclear Power Facilities, CFFTP-G-87013, paper presented at the Am. Chem.
Soc. Annual Meeting Denver, April 5-10, 1987.

(43) Dauby J.J. et al., Fixation of Aqueous Tritiated Waste in Polymer Impregnated
Concrete, Tritium Waste control Project, MLM-2451 (October 1976 - March
1977).

(44) As Ref. 43, MLM-2484 (April-September 1977).

(45) As Ref. 43, MLM-2502 (October-December 1977).

 57

(46) As Ref. 43, MLM-2519 (January-March 1978).

(47) As Ref. 43, MLM-2542 (July 1978).

(48) As Ref. 43, MLM-2620 (October 1978 - March 1979).

(49) Wleneke R.E. et al., Polymer Impregnated Tritiated Concrete, Final report
MLM-2644 (September 1979).

(50) Hawthorne S.H., Conditioning of Tritiated Wastes, Part II - Solidification and

Encapsulation, Ontario Hydro Research Division Report No 84-6-K (1984).

(51) Sunder Rajan N.S., Proj. Rep. (1.5.1981/30.11.1981), IAEA Research Con-tract
RC 2492/RB quoted by Ref. 7.

(52) Emelity L.A. et al., Tritium Loss From Coated Cement paste Blocks, LA-DC-
12740, Los Alamos Scientific Laboratory, Los Alamos, N.M., August 1971.

(53) Burger L.L. and Rayan J.L., The Technology of Tritium Fixation and Storage,
BNWL - 1807 (1973).

(54) Franz J.A. and Burger L.L., Polymeric Media for Tritium Fixation, BNWL-B-
430 (1975).

(55) Franz J.A. and Burger L.L., BNWL-B-430 SUP I (1976).

(56) Arnold J.L. and Boyle R.M., Eucapsulation of Nuclear Wastes, US Patent 4
0077 901, March 7, 1978.

(57) Williamson A.S., Solidification of Aqueous Decontamination Wastes with Water

Extendible Polymers, Ontario Hydro Research Division Report 81-57-H (1981).

(58) Penzhorn R.D. and Brunner H., Solidification of Tritiated Waste. Fusion
Technology 1986, Vol. 2, p. 1531. Association Euratom/CEA CEN Cadarache,
Pergamon Press.

(59) Hawthorne S.H., Immobilization of Radioactive Waste Oil, Part I - Non Active
Oil Studies, Ontario Hydro Research Division Report 83-350-H (1983).
 58

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.
As illustrated in Section 3 these wastes will include materials which are largely
different in the origin, nature and shape.
They will be classified, sorted and packaged at source. The sorting will be
performed according to classification criteria that may vary from plant to plant (see
Section 6). 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. Suspect, slightly, medium and highly tritium contaminated are the
solid waste categories currently defined for the solid waste classification.
Suspect wastes are non radioactive materials which are assumed to be tritium
contaminated and therefore are procedurally treated as radioactive ones. The bulk of
suspect or slightly and medium contaminated wastes are expected to be combustible or
compressible, while the bulk of highly tritium contaminated ones will consist mainly
of discarded metal components and exhausted materials hence of non-processible
materials.
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.
Pending the conditioning, 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.
Miscellaneous suspect or slightly contaminated wastes are usually considered as
non-outgassing materials so that apart from an eventual volume-reduction treatment
(see subsection 10.1), no immobilization and/or special containment packages have to
be foreseen for tritium containment purposes.
Conversely all the other tritiated solid wastes have different gaseous release
potentials, depending on their nature and contamination level. Consequently tritium
immobilization procedures and special containment barrier systems must be applied in
order to control their outgassing rate.
As illustrated in subsection 10.2 the outgassing potential of tritiated metallic
wastes may be reduced before the conditioning by some surface treatments such as
leaching, isotopie exchange with a moist atmosphere or heating.

10.1 Volume reduction of tritiated solid wastes

The volume reduction of tritiated solid wastes may be attained by different

procedures such as incineration, compaction or vacuum re-packaging according their
nature and tritium contamination level. All these operations are carried out in waste
handling facilities adequately monitored and ventilated.
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
 59

utilized to process all solid reactor wastes, arising from Ontario Hydro CANDU
Nuclear Generating Stations (2-4).
Since 1977 a mechanical compactor has been used at the WVRF to reduce the
volume of tritiated compressible wastes (2-4). The gross volume reduction factor
(VRF) achievable by the compactor was 4.5, while the net stored VRF was only ap-
proximately 2.5 (3). 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,
whereby gross and net VRF values of 7.5-9 and 5-6 were thus attained.
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 (2,3). Ashes were unloaded by gravity descharge
into 2.5 m3 rectangular metal containers which may contain in average ash products of
approximately five incineration batch loads (3). Up to 3x10s m3 of waste per year
have been incinerated (2).
At MLM (5) low specific activity (i.e. < 0.3 mCi/g) tritiated laboratory wastes
are also compacted before to be drummed (see subsection 12.1). A VRF of 4 is
achieved.
If, for any reasons, 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. 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, i.e. the European Tritium Handling Experi-
mental Laboratory of the Commission of European Communities under construction at
Ispra Establishment (6).
During all the above volume-reduction processes the release of tritiated gases is
expected. The containment, detritiation and monitoring of these gaseous waste streams
are operations required to minimize the risks of tritium exposure for operators and
general population. The gaseous discharges from volume reduction operations may be
directed to a detritiation system or directly released through a stack, where exhausts
are monitored for controlling airborne tritium emissions.
At the Ontario Hydro WVRF (2,3) virtually all tritium emitted during the waste
incineration batch operations has been so far discharged to the incineration stack.
Compactor and baler exhausts have been also discharged directly into the
exhaust stack of the building ventilation system for minimizing occupational doses.
Overall releases from the WVRF have been controlled by limiting incineration to
waste with a maximum gross beta-gamma dose rate of 0.6 mSv/h (60 mr/h) (4) and
compaction process to waste with less than 2 mSv/h (200 mr/h) (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.
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). The
aim was to cut large components into pieces acceptable for direct disposal or for melt-
ing. As pointed out in ref. (7), although initially all sizing equipment (i.e. cut-off saw,
 60

pipe cutter, guillotine saw, arc gaugh and plasma torch) have been manually operated
future robotization is foreseen if radiation fields, smoke noise or dust will preclude
manual operations. 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).

10.2 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, non-retrievable metallic components
removed from tritium handling facilities have to be detritiated.
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. In the case of a prominent oxide layer distribution, surface leaching,
with water, isotopie exchange with moisture, as well as surface heating are the most
effective detritiation treatments. In the second case a bulk melting treatment is prefer-
able to achieve an effective detritiation.
Leaching tests for surface decontamination purposes have been performed at
Ontario Hydro (8,9). 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. In Tab. 10.1 taken from ref.
(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. Tritium in
the surface oxide represented about 29% of the total tritium for copper and ranged
from 52% to 80% for stainless steel.
Tritiated metal samples were leached in 50 ml of distilled water for 150 days
(see Fig. 10.1). As to copper samples 26% of the total tritium was removed by the
leachant in the first 7 days, thereafter there was no measurable release. For stainless
steel samples there was a rapid leaching of tritium within the first 7 days which
decreased to 0.1% per day thereafter (9).
Therefore tritium appears to be easily leached off from the surface layers of
both metal samples. As reported in ref. (9) after tritium surface removal the diffusion
rate of tritium from the bulk metal may exceed (e.g. stainless steel) or not exceed (e.g.
copper) the value of 10"3% per day suggested (1) as the maximum admissible tritium
release target. Consequently, depending on the metallic nature of the hard waste, after
the surface layer detritiation, further conditioning may or not be required to minimize
the rate of tritium release to the environment.
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).
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, the whole heating apparatus being installed into a secondary
containment system (i.e. a glove box system). The tritiated gaseous stream coming
 61

TABLE 10.1 - Tritium distribution in metallic specimens (8).

SAMPLE Wt SURFACE TRITIUM BULK TRITIUM TOTAL

MATER. (ï) (MBq) (microCi) (%) (MBq) (microCi) (%) (MBq) (microCi)

1.56 0.33 8.9 29 0.80 21.6 71 1.13 30.4

1.44 - - - - - - 1.22 32.9
Copper 1.47 0.40 10.8 30 0.93 26.1 70 1.33 35.9
1.57 - - - - - 1.40 37.8
1.54 0.34 9.1 29 0.83 22.4 71 1.17 31.5

3.79 0.24 6.6 53 0.21 5.8 47 0.46 12.4

4.41 - - - - - - 0.60 16.0
Stainless 1.12 1.80 48.5 75 0.60 16.2 25 2.40 64.7
Steel 1.81 2.58 69.8 52 2.40 64.9 48 4.98 134.7
1.39 2.18 58.8 80 0.53 14.3 20 2.71 73.1

O.SO

Ό
<υ
ui
ra 0.40
ν
ν Stainless steel
Oí
c
o 0.30 -
υ
ra Copper
0.20
Surface area
12.7cm"
Volume
3
E 0.10
3
(J

0.00 J I I I I I L J I L
20 10 60 80 100 120 IMO 160 160
Days leached

FIGURE 10.1 - Leaching performance of tritiated metallic components (8).

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.
During the year 1983 at the centre of Valduc (CEA-DAM) in France (10,11)
about four tons of tritiated metallic wastes have been submitted to detritiation by a
surface thermal treatment. The campaign required in total 92 individual batch-
operations. 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.
Fairly high tritium decontamination factors (see Figs. 10.2 to 10.4) were measured
after each heating treatment (10,11). This would demonstrate that the most tritium is
permeated in the surface layer of metallic components.
 62

A more drastic thermal treatment to which tritiated metallic components may be

submitted after an adequate size reduction (parcelling) is the melting. Indeed this
technique would in principle allow a more efficient detritiation of the metallic com­
ponent, as a consequence of the complete destruction of the metal crystalline lattice in
which tritium is trapped. 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, hence minimization of the
outgassing surface area;
­ homogeneous distribution of residual tritium concentration, hence reduction of the
number of samples of casting materials which are to be taken to verify the residual
tritium specific activity;
­ considerable reduction of tritium contamination on the ingot surface which enables
in some cases its safe handling even without a secondary containment.

Operating conditions and results of thermal treatment campaigns carried out at

Valduc are summarized in Tab. 10.2.

TABLE 10.2 ­ Results of thermal treatments performed at Valduc on tritiated metallic wastes (10,11).

SAMPLE BATCH TOTAL TREATMENT TRITIUM ACTIVITY Of1) AVERAGE

MATER. TESTS Wt CONDITIONS Initial Residual DECONT.
(No.) (tons) (MBq) (microCi) (kBq) (microCi) FACTOR
(DF)

Steel 92 ­4.41 Heating for 1 at 0.37 10 3.7 0.1 ­20.0

800°C under 1 torr. to to to to to
vacuum 33.3 ­104 180 5.0 ­1.7xl03

Steel 8 ­0.39 Melting for 2 at 0.26 7 11 0.3 ­1.0

1250°C under 1 torr. to to to to to
vacuum 40.7 l.lxlO3 481 13 ­l.SxlO 3

Aluminium 11 ­0.26 Melting for 2 at 0.30 8 3.7 0.1 ­10.0

800°C under to to to to to
reduced pressure 22.2 β.ΟχΙΟ2 74.0 2.0 ­0.7xl03
(0.3­0.5 bar)

As shown in Figs. 10.2 to 10.4 taken from ref. (11), where the decontamination
factor is plotted versus the initial tritium contamination of steel and aluminium
wastes, the decontamination factor increases as the initial activity in metallic wastes
increases.
As explained in ref. (11) the dispersion of the experimental points reported in
Fig. 10.2 may be due either to the possibility of errors in evaluating the initial overall
waste activity (e.g. not sufficiently representative samplings) or to the significantly
different plant operating conditions (e.g. operation time, temperature, pressure, etc.)
 63

10.000

I
c 1.000
o
1E
tn
c
o 100
o
α>
O

10

10.000
Initial Ci.t"

FIGURE 10.2 - Variation of the decontamination factor versus initial activity of the steel hard waste after
heating treatment (2 hours at 800°C and 1 torr. vacuum) (11).

10.000

FIGURE 10.3 - Variation of the decontamination factor versus initial activity of the steel hard waste after
melting treatment (2 hours at 1250°C and 1 torr. vacuum) (11).
 64

1.000
Initial Ci.t-'

FIGURE 10.4 - Variation of the decontamination factor versus initial activity of the aluminium hard waste
after melting treatment (2 hours at 800°C and within 0.3 to 0.5 bar) (11).

under which the metallic item could have been employed in contact with a tritiated
medium. Furthermore in Fig. 10.2 the average slope of the log-log diagram is less
than one. 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, which consequently produces an increasing of the thermal'extraction diffi-
culty for highest tritium contamination levels.
As to Fig. 10.3 and 10.4 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). Nevertheless from
the trend of the few experimental points reported in Fig. 10.3 one could conclude,
even if on an approximate basis, that no substantial differences would be expected in
terms of tritium extraction efficiency between heating and melting treatments on
tritiated steel hard wastes.
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 10.1) for fission waste
volume reduction purposes.
Rooms for waste melting development are located in the basement of the WERF
building. Observation windows, closed circuit television and remote furnace controls
have been installed to allow operation of the furnace from the control room. Metal is
manually charged into the 1500 lb, 1000-Hz coreless induction furnace. 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.
 65

A continuous air monitor constantly samples air entering the facility stack for
airborne radioactivity. In addition, the HEPA filter is routinely replaced and the used
filter is monitored for alpha and beta activity.
Operation of the induction furnace with uncontaminated metals indicated the
importance of preventing slag bridges over the molten metal pool and subsequent pool
overheating. A slag coagulant, perlite ore, was later used which facilitated manual
removal of the slag before metal pouring. In melting operations with contaminated
metal, most of the surface contamination on the piping and tankage was found to be
in the slag and the molten metal was relatively clean. For large-scale and highly
contaminated operations, the removal of slag would have to be done remotely.
After melting, the metal is cast into 680 kg ingots having a 560x1120 mm
surface and a triangular cross section. 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).
The fusion waste issues due to the disposal of fusion reactor components (i.e.
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.
Selection of a suitable slagging agent can remove undesirable elements that oxidize
easily in the melting process.
The employ of low-activation steels (12,13) for fabricating first wall/blanket
components is foreseen to enable their recycling after an adequate detritiation and a
sufficient decay. This recycling is primary aimed at reducing the production rate of
activated hard wastes which otherwise could become eccessive. In fact as reported in
refs. 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.

10.3 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. However water leaching, isotopie exchange with moisture or thermal
surface treatments could be insufficient to reduce their outgassing rates within
acceptably low limits.
In this case, after detritiation, tritiated hard wastes will require further condi-
tioning in order to provide one or more additional barriers against the environmental
tritium release.
The incorporation into a suitable encapsulating medium is the option so far
investigated (9) and applied (14). Water extendible polyester resins and portland
cements were utilized for this purpose.
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. For this reason and to
avoid repetitions such systems will be more extensively illustrated under subsections
11.3 and 12.2 respectively devoted to the containment and packaging of tritiated hard-
waste composites.
 66

10.4 References for Section 10

(1) McKay H.A.C., Tritium Immobilization, EUR 6270 en (1979) European Appi.
Res. Rept. ­ Nucl. Sci. Tech., Vol. 1, No. 3 (1979) 599.

(2) Canadian Tritium Experience Manual, Canadian Fusion Fuel Technology Pro­
ject, Ontario Hydro (1984).

(3) Carter T.J., Radioactive Waste Management Practices at a Large Canadian

Electrical Utility, IAEA­SR­57/1, Proc. of the IAEA Seminar on the Manage­
ment of Radioactive Waste from Nuclear Power Plant, October 5­9, 1981.

(4) Krochmalnek L.S., Tritiated Solid Waste Management, Canadian Fusion Fuel
Technology Project, Tritium Safe Handling Course, August 1984.

(5) Rogers M.L., Treatment and Disposal of Tritium Containing Waste at Mound,
paper presented at the Am. Chem. Soc. Annual Meeting, Denver, April 5­10,
1987.

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

(7) Herring J.S., Application of 10CFR61 to Long Term Fusion Waste Manage­
ment, paper presented at the Am. Chem. Soc. Annual Meeting, Denver, April 5­
10, 1987.

(8) Krasznai J.P., Conditioning of Tritiated Wastes from a Tritium Removal

Facility, ANS International Topical Meeting on Waste Management and
Decontamination, Niagara Falls, N.Y., Sept. 1986.

(9) Krochmalnek L.S., Krasznai J.P., Carney ML, Conditioning and Handling of
Tritiated Waste at Canadian Nuclear Power Facilities, CFFTP­G ­87013, paper
presented at the Am. Chem. Soc. Annual Meeting, Denver, April 5­10, 1987.

(10) Ochem D. and G irou χ P., Traitement des Déchets Métalliques Recyclables,
Actes des Journées du Tritium, Dijon, 23­25 Avril, 1986, CEN­Saclay (1986)
339.

(11) G uetat Ph. and Ochem D., Fusion Management Safety and Environment Stud­
ies, Final Report S.E.P.D. 87/06.

(12) Butterworth G .J. et al., Recycling of Activated Steel First Wall/Blanket

Material from Fusion Reactors, Report of IAEA Tech. Committee Meeting on
Fusion Reactor Safety, Culham, 3­7 November 1986, IAEA­TECDOC­440,
IAEA, Vienna (1987) 257.
 67

(13) Ponti C , Low Activation Elements for Fusion Reactors Materials, ibidem, 229.

(14) Coste G. et al., Conditionnement des Déchets Tritiés Issus du Reacteur EL3,
Actes des Journées du Tritium, Dijon, 23-25 Avril, 1986, CEN-Saclay (1986)
391.
 68

11. 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, the application of integrated multiple barrier systems has been
investigated in order to attain a satisfactory level of tritium containment. The various
options are illustrated in the following subsections.

11.1 Additional treatments on solidified liquid wastes

In subsection 9.3 the performances of several solidification media have been

assessed in terms of tritium retention efficiency. WEP resins and portland cement did
appear the most efficient, although neither tritiated material was capable of retaining
the totality of the incorporated water molecules.
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).
Consequently surface coating, 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.
Thermoplastic and thermosetting organic resins as well as hydraulic cements
were identified as candidate material potentially applicable for the above purposes.
Thermoplastic resins which are solids at normal temperatures need to be heated to
become liquid. 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.
Thermosetting resins (e.g. epoxies, polyesters), which conversely are liquid at
normal temperatures, solidify in presence of a catalyst or a curing agent. During the
thermosetting reaction the temperature in the bulk of the material generally increases
to a maximum and then decreases to the ambient value.
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. To this end a proper choice
of the resin catalyst and cure agent is needed either in the polymer impregnation or
encapsulation options.
Many extensive experimental studies have been carried out in the USA (1,4-19),
Europe (23,24,30) and Canada (25-29) to investigate tritium leachibility from coated,
polymer impregnated and encapsulated tritiated waste composites. Results have been
reviewed by various authors (2,20-22).
As pointed out in these review, even if most laboratory leach tests have been
performed using small volume specimens, which apparently make comparative the
leach test results a comparative evaluation of these results is somewhat difficult. The
difficulty is caused by lack of full experimental details on test specimens (i.e. compo-
sition, preparation, dimensions, surface conditions and porosity, volume to surface
 69

ratio) and by uncomplete reporting of leach test procedures (sample surface to leachate
volume ratio, renewal frequency of leachant). Anyhow some leach test results are pre-
sented in Tabs. 11.1 to 11.5. 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, after decay correction. Average daily per cent
releases are also indicated in each table, although the assumption of a linear relation-
ship between leach time and per cent release is not true for some leaching isotherms.
However this gives a further opportunity of comparing leaching behaviours, even if
on an approximate basis.

11.1.1 Surface coating

Coatings may be applied to cement or concrete blocks by several techniques

such as dipping, painting, or casting around the block. The technique chosen should
minimize handling to reduce the possibility of contamination. With proper process
design, no effluent should be generated. Coating applications should be done in a
closed system to prevent tritium release through evaporation. To minimize evapora-
tion, coating materials and procedures should be selected to avoid applications neces-
sitating high temperature. However, some types of coatings are subject to spelling,
delamination and crackings which would result in a sudden increase in the rate of
tritium release equal to that for an uncoated concrete.
Results of leach test performed at LASL (Los Alamos Scientific Lab.) (1,22) and
BARC (Bhabba Atomic Research Centre) (2,3,22) on surface coated cement specimens
are shown in Tabs. 11.1 and 11.2.
As shown in Tab. 11.1, 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 - 5-9). However as the leach time increased (e.g. after 57 weeks) both
the factors decreased remaining still significant only for beeswax and paraffin
(f ~ 16). If thicker asphalt layers were applied to specimens by successive dippings or
casting techniques still lower cumulative per cent tritium releases were measured.
Commercially available coating paints tested at BARC gave fairly comparable
results. As shown in Tab. 11.2 Shalimastic HD, a cold-applied coal-tar paint appeared
to be the most promising coating material.
After 4.4 weeks of leach testing a reduction factor of 28 was attained with
respect to the uncoated specimen. However, with the increasing of the leach time the
leaching reduction factor decreased as expected, remaining still significant after 35
weeks (f = 10).
It was demonstrated however that, although capable of improving the leach
resistance properties of a tritiated cement composite, such coatings in most cases
cannot keep unchanged their efficiency for long times, since their integrity often
become worse as time goes on. For this reason their application to waste composites
was disregarded.

11.1.2 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
TABLE 11.1 · Results of leach tests performed at LASL on coated tritiated concrete specimens.

SPECIMEN I DENTI FI CATI ON RESULTS

u/c Volume Trit i urn Series Coating Leach Per cent Release Leach Rate Ref.
ratio (dm 3 ) MBq mCi type Time (wk) Reduction
Cumulative Average Factor
Daily (d" 1 )

0.3(1) - 0.1 - 12 -0.32 T6.T16 Uncoated 5 -26.25 7.5x10"1 1 -

-111 3.0 HI Uncoated 5 -32.6 9.3x10"1 1

- 12 0.32 T6.T16 Uncoated 10 -32.0 4.6x10'1

-111 3.0 H1 Uncoated 10 -39.0 5.6x10"1 . _

- 12 0.32 T6.T16 Uncoated 69 -58.0 1.2x1o"1 1

-111 3.0 HI Uncoated 57 -65.0 1.6X10"1 1 1

- 12 0.32 T17 Roofing Asphalt 5 - 3.0 8.5x10" 2 -9<5> -

1 3 (5) 1.22 O
69 -19.0 3.9x10"2

5 (6)
-111 3.0 H7 Asphalt < 2 ) 5 6.3 1.8x1o'1
57 36.0 0.9Χ10"1 -1.8(6)

-111 3.0 H4-H5 Beeswax, Paraffin 5 4.9x10"1 1.4x1o"2 -66< 6 ) - í

57 -4.0 1.0x10'2 16<6>

n.a. n.a. n.a. n.a. n.a. Asphalt ( 3 ) 5 4.8x10"1 -1.4x10" 2 •

n.a. n.a. n.a. n.a. n.a. Asphalt ( 4 ) 4 8.6x10" 3 3.1x10"*

(1) Portland I cement paste prepared by a current laboratory mixer. Curing times variable from 2 days up to a year. Leachant (0.5-1 dm 3 ) changed at
1 and 4 weeks intervals.
(2) Coating obtained by extended dipping in hot asphalt.
(3) Thicker coatings obtained by successive short dipping steps in hot asphalt at 150°C
(4) Thicker coatings (0.75-1 inches thickness) obtained by a casting procedure (5).
(5) Compare with type Τ uncoated samples.
(6) Compare with type Η uncoated samples; n.a. = not available
TABLE 11.2 - Results of tritium leach tests performed at BARC (India) on coated concrete specimens.

SPECIMEN IDENTIFICATION RESULTS

u/c Volume Tritium v/s Coating Leach Per cent Release Leach Rate Ref.
ratio (dm 3 ) MBq curies (cm) Time (wk) Reduction
(mg) Cumulative Average Factor
Daily (d 1 )

0.4 (1) 9.5 2.5x10 H n.a. Uncoated 4.4 14.0 4.5x10

(2.5x10 5 ) 9.6 18.0 2.7x10 -1
-35 20.0 8.0x10'

Epoxy (2) 4.4 3.0 9.6x10 4.7

9.6 6.0 8.9x10" 3.0 2.3,22
-35 16.0 7.0x10" 1.25

(3) 4.4
Sha limasti c HD 0.5 1.6x10 28
9.6 0.8 1.2x10" 22
-35 2.0 0.9x10' 10

Anticor (4) 4.4 0.7 2.2x10 20

9.6 1.0 1.5x10" 18
-35 4.0 1.8x10
-2

(1) 100 g cement + 40 ml tritiated water + 20 g vermiculite; curing time of 28 days. After coating leaching was started at the 4 5 t h day fr
casting.
(2) A two-pack-air drying paint with polyamide as hardener (2).
(3) A cold-applied coal-tar paint CA50 (USA) (2).
(4) CNSL epoxy coal-tar pitch paint (Indian Patent) (2). n.a. « not available
 72

then polymerized "in situ". 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.
The preparation of a polymer impregnated waste composite is described in
Appendix VII.
The resulting composite is essentially impermeable to water and has significantly
improved strength, durability and resistance to chemical attack and wheathering.
Water diffusion inside the concrete block as well as water penetration from outside is
thus minimized.
For these reasons the polymer impregnated tritiated concrete (PITC) has been
regarded as an interesting option for tritium immobilization purposes.
Polymer impegnated tritiated cement (PITC) samples, prepared at BNL (see
Appendix VII) were buried at SRP (Savannah River Plant) (9-12,22) without con-
tainers in individual lysimeters. A PITC specimen of the same dimension and formu-
lation (10-12,22) 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. 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).
Leach data (i.e. cumulative and daily per cent releases) are shown in Tab. 11.3. 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. This was due, as explained in
refs. 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. After 62 weeks in fact the cumulative per cent release
(0.61%, Tab. 11.3) became comparable with the value (0.73%) obtained after about 55
weeks from static tests. This because the former value was obtained by averaging the
leach measurement over a longer time during which the water channeling disappeared,
its effect being compensated.
In Tab. 11.3 have also been reported results obtained from small scale PITC
specimens leached at MLM (see Tab. 5 of ref. 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, the latter showing a tritium retention effi-
ciency from one to two orders of magnitude higher than that of MLM specimens.
Neither laboratory did made any explicative comments on this discrepancy. 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. 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. This could explain the differences in the above results from cement
specimens prepared by a conventional mixer technique (BNL) and gravity injector
technique (MLM).
TABLE 11.3 · Results of tritium leach performed at SRP, BNL and MLM on PITC specimens.

SPECIMEN IDENTIFICATION RESULTS

u/c Volume Tritium v/s Type of Sample Leach Per cent Release Ref.
ratio (dm3) GBq curies (cm) Containment No. Time (wk)
(mg) Cumulative Average
Daily (d ')

0.22 (1) -16 370 10 4.54 PITC/16 (1) 31 0.010 4.80x10

11,12,22
(1) 62 0.61 1.40x10"

0.22
(2) -13 370 10 4.54 PITC/13 -12 0.16 1.98x10
(1) -28 0.39 1.93x10"
11,12,22
-43 0.56 1.88x10'
-55 1.90x10
•3
0.73

0.25
(3) -0.2 14.3 386 1.05 PITC/5 59 13 39.1 4.30x10
x10 3 (38.6) no PB 41 52.0 1.81x10" ω
68 64.0 1.34x10"
13-19,22

0.25 (3) -0.2 14.3 386 1.05 PITC/0.5 72 13 12.1 1.32x10

x10 3 (38.6) no PB 42 24.7 0.84x10"
70 33.0 0.67x10"
100 43.0 0.60x10'

(1) Lysimeter sample tested at SRP without container. Portland type III cement paste prepared at BNL by a conventional dought type mixer. Curing
time of 5 days at 40°C. Release values averaged on four specimens.
(2) Duplicate lysimeter sample prepared at the BNL like samples at point (1) and leach tested at the BNL without container. Leachant (40 dm ) not
changed and sampled (1 ml fractions) periodically for analysis.
(3) Portland type III cement paste prepared at MLM using the injector technique. Polymer impregnation based on the soak technique. No change of
leachant and periodical sampling of 10, 1 and 0.1 microliters fractions.

PITC/16,13,5,0.5 * Polymer Impregnated Tritiated Concrete with 16,13,5,0.5% catalyst; PB = Polyethylene Bottle Package.
 74

11.1.3 Encapsulation

Extensive experimental studies have been carried out at CEN-Grenoble, Ontario

Hydro and KfK- 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.
At CEN-Grenoble (23,24) 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.e. polyester or epoxy resin). 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 (~ 1.2 mCi). 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. They were
then submitted to leaching tests during 110 days. The initial tritium activity in each
specimen was about 80 and 93 MBq (~ 2.1 and 2.5 mCi) for tritium gas and tritiated
water respectively.
Unfortunately no details are available on commercial types of cement and
polymeric organic resins used for fabricating all these specimens.
Some leach data calculated after comparable leach time and expressed as cumu-
lative and daily per cent release values have been reported in Tab. 11.4 for com-
parison purposes. As shown in Tab. 11.4 after about 1 year the barrier effect of
polyester and epoxy encapsulating media is well evident. The cumulative per cent
releases of tritium from encapsulated specimens decrease from 49% to 7.3x10"*% (f =
7xl0 2 ) in the case of polyesther and from 56% to 2.6x10"2% (f = 2x10s) in the case of
epoxy resin. 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. 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 0.2% (f = 2.5xl0 2 ) measured in the case
of the polyesther. This was explained in ref. (24) as due to the best resistance to the
hydrolyse shown by the epoxy resin in comparison with the polyesther.
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. As shown in Tab. 11.4 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. 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. Furthermore
epoxy encapsulated cement appears to be the most efficient double barrier system for
containing gaseous tritium.
TABLE 11.4 · Results of leach tests performed at CEN­Grenoble.

SPECIMEN IDENTIFICATION RESULTS

i/olume Tritium V/S Solidification Encapsulation Leach Per Cent Release Leach Rate Ref.
(dm3) MBq mcuries (em) or Containment Medium Time Cumulative Average Reduction Factor
Medium (d) Daily (d'1)

97 43 4.4x10 '
­0.1 44.4 1.2<1> 0.833 IX <3> ♦ Polyester None
380 49 1.3x1ο"1 . 23.24
1
97 53 5.5x10"
­0.1 44.4 1.2<1> 0.833 IX <3> ♦ Epoxy None
380 56 1.5x10'1 1
2
97 3.4x10" 3.5x1ο"1 "
­0.1 44.4 1.2<1> 0.833 IX < 3 ) + Polyester Polyester <6)
2 2
380 7.3X10" ­2.0x10'* ­7x10
1) <3> <6> 97 8.3x10'3 8.5x10"5
­0.1 44.4 1.2< 0.833 IX ♦ Epoxy Epoxy
380 2.6x10'2 ­7.0x10"5 ­2x103

(4)
30­70 . ­J
n.a. n.a. n.a. n.a. Cement None 64 0.78
Ol

­0.4 ­93 2.51 1.33 Cement**' Polyester (6) 110 2.0x10"1 Ι.βχΙΟ'3 ­2.5x102 ­ 23,24
<4) (6> 3 5
­0.4 ­93 2.51 1.33 Cement Epoxy 110 1.1X10" I.OxlO" ­5.0x10'*

n.a. n.a. n.a. n.a. Cement <5>

None 64 2­4 ­5.0x10"1 ­ 1

­0.4 ­80 2.16<2> 1.33 Cement <5> Polyester(6> 110 2.0x10'2 1.8x10"* ­2.5x103 23
2 <5) <6) 3 5
­0.4 ­80 2.16< > 1.33 Cement Epoxy 110 ­2.0x10' 1.6x10" ­3.1x10*

(7)
n.a. n.a. n.a. n.a. Polyester Polyester < 8 ) < 1 0 ) 365 10.0 2.7x10'2 ­ ­ 25

n.a. n.a. n.a. n.a. Epoxy <9>

Epoxy (10
> 365 2.0 5.5x10"3 ­ ­ 25

(1) As tritiated water. (7) Hollow polyester cylinder containing tritium gas and I wi th 50wtX
(2) As tritium gas. cement aggregates particles.
(3) Used only as a supporting material for tritiated water. (8) Loaded with sand.
(4) Tritiated cement matrix. (9) Hollow epoxy cylinder loaded as in (7).
(5) Hollow untritiated cement cylinders containing tritium gas. (10) 2 cm thick encapsulating resin.
(6) 1 cm thick encapsulating resin.
 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.
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. 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).
The preparation of WEP and cement specimens incorporating tritiated water and
to be then encapsultated, was carried out as described in Appendix V.
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. Leach tests were performed (26) by immersing each
encapsulated specimen in 0.2 litres of demineralized water. 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). Static
leach data were measured over a maximum leaching period of 150-180 days.
The effect of various encapsulating materials such as cement, 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. 11.1 and 11.2
(taken from ref. 26) where percentage cumulative tritium releases are plotted versus
the leach time. Results of static leach test obtained with non-encapsulated specimens
are also reported for comparison purposes.
In Figs. 11.1 and 11.2 each experimental isotherm corresponds to a composite
specimen resulting from one of the indicated combinations of solidification matrices
with encapsulating media. Most isotherms are linear or pratically linear. The average
daily tritium releases, i.e. the average slopes of these isoterms, have been also calculat-
ed after 60, 150 and 180 days of leaching and reported in Tab. 11.5 along with the
corresponding operating conditions.
From the comparison of leaching isotherms (Figs. 11.1 and 11.2) and their aver-
age slopes (Tab. 11.5) it appears that a WEP resin layer of suitable thickness (i.e.
1 cm) applied over tritiated cement or WEP matrices is the most effective encap-
sulating media for minimizing tritium leaching. After 150 days of leaching it reduces
in both cases the tritium leach rates by a factor 10s. Under the same leach conditions
the efficiency of an identical layer of epoxy resin is comparable in the case of a
tritiated WEP matrix, 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.e. the leach rates) calculated for portland/WEP, WEP/epoxy and WEP/WEP com-
posites (see Tab. 11.5) are approximately one order of magnitude lower than the
suggested (20) maximum tritium release target of 10~3% per day. However one has also
to take note that, as reported in ref. (29), 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 1.7x10"3% per day.
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. Portland cement (PZ 35F type)
and polystyrene (DOW-binder 101) specimens containing respectively about 32 wt% of
 77

,E2*.E2S

2S.27 Portland Ctment/No Encapsulation ƒ * · . " ·

El.El Portland CamtntlEpon IlSISOt j
E3.E« Portland Cernem lipon Slí/LO/LOS
EJ.Et Portland Cernem IWEP ¡
ΕΙ,ΕΙ* Portl ond Cement /Aropol C IOS ·
EM.E» Portl ond Cement /Portland ¡
Cement ;
s.
S
S
£

o.i
Χ' /

ES. ει
s

0.01
/
¿S

O.001 Λ ' ' M ΙΠ£ J ' ι ι uin HI'

io 1000
Oirv un

FIGURE 11.1 ­ Static leach tests at Ontario Hydro (26). Comparison of encapsulation media over a tritiated
portland cement matrix. Cumulative per cent tritium releases in water vs. leach time.

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.
Static leach tests were performed over a leaching period within 50 to 200 days
using as a leachant 0.5 litres of water. Cement and polystyrene specimens directly
loaded with tritiated water were also and tested under the same leaching conditions
(see subsection 9.3.5).
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. 11.3 and 11.4 taken from ref. (30).
From the comparison of the average slopes of tritium leaching isotherms
reported in the above figures and in Fig. 9.2 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;
­ a significant improvement of tritium retention efficiency is achievable only if
tritiated water is directly incorporated into a polystyrene matrix.
 78

«*. ·7 WCP ISo Encaptulation

Ζ E IS . E U WEP/Epon S IS /S OS
- EU.Eli WEP/Epon SI5IL0/10S
- EI1.E2· WEP /Aropol C JOS
E21.E22 WEP/WEP
E27.E2I WtP/Portl ond Cement ..•M.«7

«:
■E1S.E2·
E27.E2S /

/ I
/ I

»
3

0.1

ί
EIS.EI*

■EI7.EII
/
0.01 /
£22

o.ooi ι ι ι ι ι IIII ' Ι Ι Hill Ι Ι Ι Ι Ulli

100 1000
Bays

FIGURE 11.2 - Stati c leach tests at Ontari o Hydro (26). Compari son of encapsulati on medi a over a tri ti ated
WEP matri x. Cumulati ve per cent tri ti um releases i n water vs. leach ti me.

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,,/ΗΤΟ
in spe cime n

10 20 30 40 50 60 70 80
>Γ(η)'"

FIGURE 11.3 - Stati c leach tests at KfK (30). Compari son of encapsulati on medi a over a tri ti ated si li ca gel
matrix. Fracti onal tri ti um releases i n water vs. leach ti me.
TABLE 11.S - Results of leach tests performed at Ontario Hydro.

SPECIMEN IDENTIFICATION RESULTS

W/M < 1 ) Volume < 2 ) Tritium Sample Solidification Encapsulation Leach Per Cent Release Leach Rat· Ref.
ratio (dm ) MBq incuries Code Matrix Medium Time Cumulative Average Reduction Factor
<d) Daily (d 1 )

0.28 -0.1 -83 2.23 26,27 Portland 30 < 4 > None 60 47.0 7.8x10"1 1 -
180 63.0 3.5X10"1 1
0.30 -0.1 -93 2.51 36,37 HAC (5) None 180 76.5 4.2x10"1 - - 26
1.17 -0.1 -99 2.68 46,47 WEP(6> None 60 13.0 2.2x10"1
1
180 24.0 1.3X10"1 -3 1

0.28 -0.1<3> -77 -2.10 E24.25 Portland 30 Portland 30 < 4 ) 60 11.4 1.9x10"1 -4 .
(3
0.28 -0.1 > 85 2.30 E3,4 Portland 30 Epoxy resin 60 1.2x10" 1
1.9x10'3 -
1 3
150 2.1x10' 1.4x10' -300 26
-J
0.28 -0.1 <3> 89 2.18 E29.30 Portland 30 WEP (6) 60 2.0x10"2 3.4x10"* • -
0.28 -0.1<3) -79 2.41 E5.8 Portland 30 WEP<6> 150 4.7x10'2 3.1x10'* -103

1.0 -0.1(3) 100 2.72 £27,28 WEP Portland 30 < 4 > 60 2.9 4.8x102 . -4.5
1.0 -0.1(3) 111 3.00 E17.18 WEP Epoxy resin 60 1.3x10" 2
2.1x10** -
150 3.1x10'2 2.0x10* -770 26
1.0 -0.1(3) 103 2.80 E32.33 WEP WEP<6> 60 2.2x10"3 3.6x10'5 - .
1.0 -0.1(3) 105 2.86 E19.20 WEP WEP<6> 150 2.1x10'2 1.4x10'* . -103

(1) Water to matrix material (cement or WEP) weight ratio.

(2) Volume to geometric surface ratio is 0.833 cm for all specimens.
(3) Including encapsulating material volume.
(4) Portland type 30 Cement.
(5) High Alusina Cement.
(6) Water Extendible unsaturated Polyester, Aropot 661-P, Ashland Chemical.
(7) Epon 815 epoxy resin, Shell Canada Chemical Company. Cure time: 1 and 7 days for solidification and encapsulation media respectively.
 80

K 154 with 21% HjOimO

in Dow-binder 101
13 4% H ? 0/HTO in specimen

in cemenl
6 8% Η,,Ο/ΗΤΟ (trom Κ 154)
in specimen

50 60
> V(h)1

FIGURE 11.4 - Static leach tests at KfK (30). Comparison of encapsulation media over a tritiated seolite
matrix. Fractional tritium releases in water vs. leach time.

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, which appear rather unpractical
for field applications. Furthermore in dealing with tritiated waste materials, coating,
impregnation and encapsulation procedures become still more critical mostly because
of the stringent safety requirements associated with tritium handling.
Conversely the simple "containerization" (i.e. the confinement of tritiated waste
composites inside a suitable primary container) appears to be a more practical and less
expensive option.
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.
High density polyethylene (HDPE) was selected by both laboratories as the best
container material. After polyvinylidene chloride (SARAN), HDPE has the lowest
water permeability and the best thermo-chemical resistence among the common
polymers. Furthermore it is a readily available material (29,31).
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. 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. Their preparation
was done according to the procedure described in Appendix VII. The samples were
than placed in a test apparatus (Fig. 11.5) containing 1.6 litres of distilled water for
leach testing. No change of leachant was made and 10, 1 and 0.1 microlitres fractions
were sampled periodically.
Tritium permeation data (i.e. 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. 11.6 taken from ref. (22).
 81

In this table the corresponding average daily tritium per cent releases have also been
reported for comparison purposes.

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 - Laboratory scale permeation tests at MLM (19). Experimental set up for testing PITC
specimens.

As shown in Tab. 11.6 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. Without
the polyethylene a thin layer of polystyrene was in fact the only barrier between the
cement matrix and the water (18).
The release from sample 72, using 0.5% catalyst (as recommended by the BNL)
was approximately one-half the release from sample 59 using 5% catalyst. The dif-
ference is attributed to a lower rate of polymerization reached with 0.5% catalyst,
yielding consequently a lower internal bulk temperature. 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).
No significant differences were found (see Tab. 11.6) between release data from
the fifth concrete sample group (which did not have styrene added) and those from
first and fourth PITC sample groups. This was attributed to the barrier effect of the
polyethylene bottle which was much thicker than the layer of polystyrene. Such a bar-
TABLE 11.6 ­ Results of tritium permeation tests performed at MLM on tritiated concrete specimens with and without polymer impregnation.

SPECIMEN IDE NTIFICATION RESULTS

u/c Volume Tritium V/S Group Sample Type of Leach Per Cent Release Leach Rate Ref.
ratio (dm 3 ) TBq Ci (cm) No. No. containment Time (wk) Cumulative Average Reduction
(mg) Daily (d' 1 ) Factor

n.a. n.a. n.a. n.a. n.a. ­ TC no PI 20 2.50 ­1.8x10"2 . m .

no PB 28 8.00 ­4.1x10'2 1 ■
­ 20,21,22

0.25(1> ­0.2 14.3 386 1.05 1 57­58 PITC/5 6 0.10 2.4x10"3 .

(38.6) + PB 33 0.50 2.0x10 3 ­
65 0.66 1.4x10'3 ­100

1 59 PITC/5 13 39.1 4.3x10'] . .

no PB 41 (2) 52.0 i.8xio'; ­ ­
68 64.0 1.3x10"' 1 1

4 69­71 PITC/0.5 6 0.11 2.6x10"3 . . CD

IV)
♦ PB 33 0.35 1.5x10 3
13­19,22
64 0.54 1.2x10"3 ­60 ­

4 72 PITC/0.5 13 12.1 13.2x10 2 . .

no PB 42 24.7 8.4x10"2 ­ ­
70(2) 33.0 6.7x10­2 1 2
100 43.0 6.0x10"2 ­ ­

5 73­74 TC ♦ PB 6 0.10 2.5x10'3 . .

no PI 25 0.26 1.5x10"3 ­30 . ­
54 0.43 1.1x10"3 ­ •

(1) Portland type til cement paste preparation based on the injector technique. Polymer impregnation based on the soak technique. No change of
leachant and periodical sampling of 10, 1 and 0.1 microliters fractions.
(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.
n.a. » not available; TC « Tritiated concrete; PB « Polyethylene Bottle Package; PI « Polymer Impregnation; PITC/0.5 or 5 ­ Polymer Impregnated
Tritiated Concrete with 0.5X or 5X catalyst.
 83

rier was in fact so efficient in reducing the tritium leach rate that, when not removed,
it had the capability of masking eventual differences due to a further treatment of the
concrete specimen.
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,
fourth and fifth specimen groups to values which are very near the maximum release
target of 10"*% per day suggested in ref. (20).
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 effect of such a barrier was determined with and without an additional
layer of WEP resin being externally applied to encapsulate the HDPE container.
Commercially available HDPE containers of 25, 125 and 500 millilitres as well
as fabricated HDPE containers of 1, 0.5 and 0.2 cm thickness were utilized in order to
determine the effect of HDPE wall thickness on tritium release rates. A WEP resin
was the matrix material utilized for incorporating tritiated waste water according to
the procedure described in Appendix V. Within 4.3 and 5.8 GBq (116-158 mCi) of
tritium were incorporated in each specimens. 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. The physical characteristics
of specimens are summarized in Tab. 11.7 taken from ref. (29). The effects on tritium
leaching rate due to the containerized WEP matrix (used for tritiated water incorpora­
tion), 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. 11.6, 11.7 and 11.8. Leaching
data, expressed as cumulative fractional tritium releases x(V/S), are plotted versus
leach time. Based on these data, 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) « AVC(C1A.2A)

FIGURE 11.6 - Static leach tests at Ontario Hydro (29). Cumulative fractional releases χ (V/S) versus leach
time for specimens CI,2, W'1,2; CIA, 2A.
TABLE 11.7 - Physical characteristics of specimens utilized at Ontario Hydro for static leach tests.

SAMPLE SAMPLE DIMENSION OF CONTAINER AVG. SURFACE AREA AVG. VOLUME S/V INITIAL TRITIUM Ref.
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 8.8/7.4 0.14 337.4 483.6 0.71 4.83 130.56

W2 500 mL HDPE Container

C1 Solidified HTO/WEP in 8.8/8.0 0.14 354.3 519.4 0.68 4.46 120.57

C2 500 mL HDPE Container 4.64 125.32

C1A Unsolidified HTO/WEP Emulsion 8.8/8.0 0.14 354.3 519.4 0.68 5.61 151.68
C2A in 500 mL HDPE Container 5.85 158.00

PE1 Solidified HTO/WEP in 8.0/8.0 1.00 443.0 722.6 0.61 4.35 117.50
PE2 fabricated HDPE Container 4.52 122.11 27,29

PE3 Solidified HTO/WEP in 8.0/8.0 0.50 395.1 601.2 0.66 4.36 117.80 00
PE4 fabricated HDPE Container 4.28 115.08

PE5 Solidified HTO/WEP in 8.0/8.0 0.20 368.6 539.4 0.68 4.29 116.03
PE6 fabricated HDPE Container 4.36 117.87

E1 Solidified HTO/WEP in 8.0/8.0 0.14 370.9 822.5 0.45 4.41 119.19

E2 500 mL HDPE Container, 4.40 118.94
encapsulated in WEP (1)

46 Solidified HTO/WEP, 5.0/5.0 none 117.7 98.13 1.2 0.100 2.71

47 no contain. & encaps. 0.098 2.66

E19 Solidified HTO/WEP, 5.0/5.0 none 117.7 98.13 1.2 0.104 2.82 26
E20 no container, 0.107 2.90
encapsulated in WEP (2)

HDPE: High Density Polyethylene

(1) 0.85 cm thick encapsulating layer on the HDPE container. (2) 1 cm thick encapsulating layer on the WEP composite
 85

DAYS LEACH EO
O AVG(PE1.2) AVC(PE3.4) » AV
G (PE5.6)

FIGURE 11.7 ­ Static leach tests at Ontario Hydro (29). Cumulative fractional releases χ (V/S) versus leach
time for specimens PEI,2; PEI,2; PE5.6.

80 120 160 200 240

OAYS LEACHED
« (C1.2) (PEI.2) « (W1.2) » (E1.2)

FIGURE 11.8 ­ Static leach tests at Ontario Hydro (29). Cumulative fractional releases χ (V/S) versus leach
time for specimens C1.2; PEI ,2, W 1,2, El ,2.

shown in Tabs. 11.8 and 11.9. Note that data related to the cumulative fractional
release rates have been normalized by introducing the factor V/S, where V is the vol­
ume and S the geometric surface area of the specimen. This enables to make the cor­
relations of data measured for specimens which originally are different in size and
geometry. For comparison purposes leaching data related to specimens of tritiated
WEP composites encapsulated in a layer of WEP resin were also included in Tab. 11.9.
To determine the influence of the matrix material (i.e. WEP or portland cement)
utilized for solidifying the tritiated waste water, ¡each tests were also extended to
specimens of tritiated portland 30 cement, added with 5 wt% of dried silica and con­
fined inside a 0.14 cm thick HDPE container (29). Related leaching data are shown in
TABLE 11.8 ­ Static leach tests performed at Ontario Hydro on containerized tritiated liquid wastes and waste composites. Comparison of results.

SPECIMEN IDE NTIFICATION RESULTS

C0MPOSITE <1> TRITIUM (1> V/S(1> SAMPLE SOLIDIFICATION CONTAINER EL ACH CUMULATIV
E AVG. DAILY CUMUL. FRACT. EL ACH RATE Ref.
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)

473.6 ­4.83 ­130.5 ­1.41 W1,2 (2)

0.14/500 200 3.0x10
­4 ­4 ­6
1.1x10 1.5x10 28 1

519.4 ­5.73 ­155.0 1.47 C1A.2A (3) ­3

0.14/500 200 8.4x10 2.84x10 0.42x10 1 27,29

<4>
519.4 ­4.55 ­123.0 1.47 CI,2 WEP 0.14/500 200 1.86x10 6.3x10­4 0.93x10 4.5 6

539.4 -4.33 -117.0 1.47 PE5.6 WEP<4> 0.2/n.a. 200 1.62x10 5.5x10 0.81x10 1 oo
CD
601.2 -4.31 -116.4 -1.52 PE3.4 WEP<A> 0.5/n.a. 200 0.94x10 3.1x10
­4 0.47x10 ­2 27,29

722.6 -4.43 -120.0 -1.64 PEI,2 WEP (4> 1.0/n.a. 200 1.6x10 0.5x10
­4
0.80x10 ­10

WEP » Water Extendible Polyester Resin

n.a * not available
(1) Average of two samples.
(2) Unsolidified HTO.
(3) Unsolidified UEP/HTO emulsion.
(4) Solidified UEP/HTO emulsion. Water/WEP weight ratio ■ 1.
TABLE 11.9 - Static leach tests performed at Ontario Hydro on containerized and/or encapsulated tritiated waste composites. Comparison of results.

ISPECIMEN 1 DENTIFICATION RESULTS

COMPOSI TE* 1 ) TRITIUM11' V/S(1) SAMPLE SOLIDIFICATION CONTAINER & LEACH CUMULATIVE AV. DAILY CUMUL. FRACT. LEACH RATE Ref.
VOLUME MBq mCi (em) CODE MATRIX ENCAPS. 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, (cm d" 1 )

98.13 -99.3 -2.68 0.833 46,47 WEP<2> no container '

180 0.199 1.33x10'1 1.11x10'3 1 26,27,29
no encapsul.

98.13 -10.5 -2.86 0.833 E19,20 WEP<2> (4)

no container 150 1.75x10"4 1.4x10"4 1.16X10"6 -0.9x10 3 26,27,29
WEP/1 750 1.06x10'2 1.7x10"3 1.4x10"5 -0.8x10 2

519.4 -4.55 -123.0 1.47 CI.2 WEP<2> HDPE/0.14 <5>

200 1.86x10'3 0.63x10"3 0.93X10"5 -10 2 27,29
x10 3 no encapsul.
co
822.5 -4.40 vi
-119.0 2.22 E1.2 WEP<2> HDPE/0.14(6>
x10 3
200 2.8x10' 4
0.6x10" 4
1.4x10" 6
-0.8x10 3
27.29
WEP/0.85

n.a. -4.52 12.23 0.833 n.a. Portland 30 no container

60 0.57X10*1 I.HxIO" 1 0.95x10'3 1 27
Silica Fume (7) no encapsul.

n.a. -5.5 148 1.48 n.a. Portland 30 HDPE/0.14

200 0.92X10'3 3.1x10'* 0.46x10'5 -2.0x10 2 27
x10 3 Silica Fume (7) no encapsul.

WEP * Water Extendible Polyester Resin

HDPE » High Density Polyethylene
(1) Average of two samples.
(2) Water/WEP weight ratio = 1.
(3) HTO solidified by WEP resin only.
(4) HTO solidified by WEP resin and encapsulated in a 1 cm thick layer of WEP resin.
(5) HTO solidified by WEP resin and sealed in a 0.14 cm thick 500 mL HDPE container.
(6) HTO solidified by WEP resfn and sealed in a 0.14 cm thick 500 mL. HDEP container and then encapsulated in a 0.85 cm thick layer of WEP resfn.
(7) 95X Portland 30 cement additioned with 5X Silica Fume, which is a 90-95X Si0 2 by-product from the ferro-silicon ft silicon metal production.
 88

Tab. 11.9 where for comparison purposes data from a non-containerized specimen of
the same tritiated cement composite are also included.
From the comparative assessment of tritium release data reported in Tables 11.8
& 11.9 it follows that
- At present the HDPE appear to be one of the most efficient barrier material against
tritium release from a tritiated waste composite. Leach rate even inferior to the
suggested tritium release target of 10"3% per day are attained by using such a
material.
- The components of the WEP incorporation matrix (i.e. styrene and vinylester and
possibly the methyl-ethyl ketone peroxide) have, even after short contact times, the
capability of permanently increasing the permeability of polyethylene to tritiated
water, i.e. the release of tritium across the HDPE container. This is the conclusion
resulting from the comparison of the leaching data from specimens CIA, 2A with
those from specimens C1.2 and Wl,2, all of them being tested after sealing inside
three identical HDPE containers (Fig. 11.6, Tab. 11.8). In presence of an unsolidi-
fied WEP/HTO emulsion inside the HDPE container (specimens CIA, 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,2) and tritiated water alone (specimens Wl,2). As pointed out in ref.
(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. This makes also evidence that even if the
water permeability through polyethylene is normally expected to be temperature
dependent, it is rather unlikely that thermal conditions such as those ones reached
during the curing step (i.e. exposure to 97eC for seven minutes) may so permanently
affect the polyethylene permeability.

- The altering effect of the WEP components on the polyethylene permeability is also
demonstrated by the fact that tritium leached from specimens C 1,2 (i.e. 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,
confined inside a HDPE container of an identical thickness (Tab. 11.9). 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 46,47) 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, due to the effect of WEP
components.
- The rate of tritiated water release, expressed as cumulative fraction of the original
tritium activity, decreases as the HDPE container thickness increases. This is the
conclusion resulting from the comparison of leaching data related to specimens
PE1.2; PE3.4 and PE5.6 (see Tab. 11.8). However tritium leach rate do not decrease
linearly with the increasing of the container thickness. As pointed out in ref. (29)
there is an approximate hyperbolic relationship between these two parameters,
probably because of the more enhanced effect of the organic components of the
WEP resin on thin polyethylene layers than on thicker ones.
 89

- 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). This is the conclusion resulting from
the comparison of leaching data releated to specimens PEI,2 (Tab. 11.8) and E 19,20
(Tab. 11.9).
- If containerized composite specimens are further encapsulated by a layer of WEP
resin like E 1,2 specimens, the efficiency of the HDPE container is lower than ex-
pected. This clearly results from the comparison of leaching data related to speci-
mens 46,47; E19.20; Cl,2 and E1.2 reported in Tab. 11.9. The effect of encapsulat-
ing a tritiated WEP composite by a WEP resin layer (as it results by comparing
specimens E 19,20 with 46,57) is that of lowering the tritium release rate approxi-
mately by a factor 102-10s. The barrier effect of HDPE container also provides a
reduction factor of approximately 102 (as it results by comparing specimens C 1,2
with 46, 57). Therefore if both these barriers are applied around tritiated WEP
specimens a net reduction factor of at least 10* would be expected. As indicated in
Tab. 11.9 the net reduction factor calculated from the release rate values is however
less than 10s. This make again clear evidence of the altering effect of WEP organic
components on the permeability of the HDPE container, as a consequence, in this
case, of its double exposure to the WEP emulsion during the initial tritiated water
incorporation and final encapsulation processes.
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.

11.3 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. As pointed out in subsection
10.2 this may be needed even after a detritiation treatment, especially if the level of
tritium residual contamination is still too high to enable an acceptably low outgassing
rate.
To ensure a sufficient reduction of tritium outgassing rates the encapsulation
(see subsection 10.3) of tritiated metallic hard waste may be applied in conjunction
with a suitable tritium containment barrier. The barrier consists of a layer of organic
polymer lining the inner surface of a metal drum or concrete container.
Water extendible polyester resin (27,28) or portland cement (24,32) have been
utilized as encapsulating media, while polyethylene (28,29) or epoxy resin layers
(24,32) as containment materials to form together with the formers a double barrier
system.
To investigate the individual effect of the encapsulating materials on the overall
efficiency of such a double barrier system, tritium leaching rates from polyethylene
containerized steel specimens with and without a previous WEP encapsulation of the
specimen itself, were experimentally determined and compared at Ontario Hydro (27,
28).
 90

The assessment of experimental results from these leach tests made evidence that
- simple containment of tritiated steel specimens, i.e. containerization in a 1 cm thick
polyethylene container without encapsulation, was found to be ineffective at
minimizing the tritium release rate, since only a reduction factor by two was
achieved in comparison with a non-contained specimen;
- encapsulation of the same specimen in a WEP resin into the same polyethylene con-
tainer, acting as an additional containment barrier, was conversely much effective,
the tritium release rate being in such a way reduced to less than 10~4% per day.
To explain the above different tritium leaching behaviours it was postulated
(27) that:
1. Owing to the large void volume in the specimen container without encapsulating
medium, a high tritium concentration gradient was developed across the container
wall, causing a considerable increase of the polyethylene permeability to tritium.
2. Conversely, due to the presence of an encapsulating medium into the specimen
container, a dilution of tritium released from the specimen in the water fraction of
the WEP solidified emulsion was likely to occur. Under such a condition the at-
tained tritium concentration gradient was significantly lower than developed in
absence of an ecapsulating medium.
3. Consequently the tritium permeability across the polyethylene container and
therefore the tritium release from the overall containment system was also
significantly lowered.

Unexpectedly no comparison was made with a cement encapsulating medium,

nor comments were reported related to the possibility of an altering effect on the
polyethylene permeability, due to the presence of WEP organic components as demon-
strated by other experimental tests at Ontario Hydro (see subsection 11.2). 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.
As reported in subsection 11.1 epoxy resins were extensively investigated at
CEN-Grenoble as potential tritium containment materials (24). Since their containment
efficiency was demonstrated to be superior to that of polyesters (see Tab. 11.4) 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.
However, being such resins normally utilized as an internal liner of final packaging
containers, a more complete and detailed information on the overall containment
system can be found in subsection 12.2.

11.4 References for Section 11

(1) Emelity L.A. et al., Tritium Loss from Coated Cement Paste Blocks, LA-DC-
12740, Los Alamos Scientific Laboratory, Los Alamos, N.M., August 1971.

(2) IAEA, Management of Tritium at Nuclear Facilities, IAEA Technical Report

Series No. 234, IAEA, Vienna, 1984.
 91

(3) Sunder Rajan N.S., Proj. Rep. (1.5.1981/30.11.1981), IAEA Research Contract
RC 2492/RB quoted by ref. 2.

(4) Colombo P. et al., Tritium Storage Development, Prog. Rep. No. 2, BNL-19688
(October-December 1974).

(5) As Ref. 4, PR No. 3, BNL-1998I (January-March 1975).

(6) Colombo P. et al., The Fixation of Aqueous Tritiated Waste in Polymer

Impregnation Concrete and in Polyacetilene BNL 20898, Conf.-750989 (1975).

(7) As Ref. 4, PR No. 4, BNL-20421 (April-June 1975).

(8) As Ref. 4, PR No. 5, BNL-20779 (July-September 1975).

(9) As Ref. 4, PR No. 7, BNL-21700 (January-March 1976).

(10) Neilson R.M. et al., Immobilization of Tritiated Aqueous Waste in Polymer

Impregnated Concrete, BNL-22900, Conf.-770611-21 (1977).

(11) As Ref. 4, PR No. 9, BNL-50625 (July-September 1976).

(12) As Ref. 4, PR No. 12, BNL-50733 (April-June 1977).

(13) Dauby J.J. et al., Fixation of Aqueous Tritiated Waste in Polymer Impregnated
Concrete, Tritium Waste Control Project, MLM-2451 (October 1976 - March
1977).

(14) As Ref. 13 MLM-2484 (April-September 1977).

(15) As Ref. 13 MLM-2502 (October-December 1977).

(16) As Ref. 13 MLM-2519 (January-March 1978).

(17) As Ref. 13 MLM-2542 (July 1978).

(18) As Ref. 13 MLM-2620 (October 1978 - March 1979).

(19) Wieneke R.E. et al., Polymer Impregnated Tritiated Concrete. Final Report
MLM-2644 (September 1979).

(20) McKay H.A.C., Tritium Immobilization, EUR 6270 EN (1979) European Appi.
Res. Rept. - Nucl. Sci. Tech., Vol. 1, No. 3 (1979) 599.

(21) Williamson A.S., Tritiated Aqueous Waste Immobilization, IAEA Coordinate

Research Meeting on "Handling of Tritium Contaminated Effluents and Wastes",
Juelich, FRG, October 20-24,1980.
 92

(22) Mannone F., Immobilization of Tritiated Waste-Water by Hydraulic Cements, A

Survey of the State of the Art, Report EUR 11230 EN (1987).

(23) Aude G. and De Tassigny C, Nuovelle Application des Résines Thermodurcis-

sable dans le Domaine des Déchets Radioactifs,, IAEA SR75/8, Proc.The IAEA
Seminar on the Management of Radioactive Waste from Nuclear Power Plants,
Karlsruhe, October 5-9, 1981, IAEA, Vienna, 1983.

(24) De Tassigny C. and Tardif F., Diffusion de l'Eau Tritiée dans les Résines
Thermodurcissables, Actes des Journées du Tritium, Dijon, 23-25 Avril 1986,
CEN SACLAY (1986), p. 363.

(25) Hawthorne S.H., Conditioning of Tritiated Wastes Part I - Tritiated Water

Immobilization, Ontario Hydro Research Division Report No. 82-531-K, (1982).

(26) Hawthorne S.H., Conditioning of Tritiated Wastes, Part II - Solidification and

Encapsulation, Ontario Hydro Research Division Report No. 84-6-K. (1984).

(27) Krasznai J.P., Conditioning of Tritiated Wastes from a Tritium Removal Facil-
ity, ANS International Topical Meeting on Waste Management and Decontamin-
ation, Niagara Falls, N.Y., Sept. 1986.

(28) Krochmalnek L.S. et al., Conditioning and Handling of Tritiated Wastes at

Canadian Nuclear Power Facilities, CFFTP-G-87013, Paper presented at the
Am. Chem. Soc. Annual Meeting, Denver, April 5-10, 1987.

(29) Krasznai J.P., Tritiated Waste Conditioning, Part III - Performance of Con-
tainerized and Encapsulated Waste Forms, Ontario Hydro Research Division
Report No. 85-279-K (1985).

(30) Penzhorn R.D. and Brunner H., Solidification of Tritiated Waste, Fusion
Technology 1986, Vol. 2, p. 1531, Association Euratom/CEA-CEN Cadarache,
Pergamon Press.

(31) Crank J. and Park G.S., Diffusion in Polymers, Academic Press (1968) quoted
by ref. 29.

(32) Coste G. et al., Conditionnement des Déchets Tritiés Issus du Reacteur EL3,
Actes de Journées du Tritium, Dijon, 23-25 Avril 1986, CEN Saclay (1986), p.
391.
 93

12. PACKAGING OF TRITIATED SOLID AND SOLIDIFIED WASTES

12.1 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.e. drums, sealed special metal containers, playwood or cardboard boxes)
without being submitted to any previous encapsulation treatment.
At Ontario Hydro (1,2) ashes from the incineration of combustible miscellaneous
wastes are placed inside 2.5 m3 sealed metal containers, while plastic bags containing
compactible wastes are directly compacted into 0.4 m s cardboard boxes which are then
secured with steel straps and double plastic bagged.
At TSTA (3,4) compactible and non-compactible wastes of low tritium contami-
nation level (<740 MBq»m"s, <20 mCi-m"8) are bagged and placed in boxes for burial
at LANL Radioactive Disposal Facility. Medium tritium level solid wastes
(740 MBq.m"3 < A < 3.7 TBq-m"3, 20 mCi-m"3 < A > 100-Ci m"3) are packaged in-
side standard drums, internally lined with asphalt, which then are buried in shafts in a
retrievable manner.
At MLM (5) laboratory wastes of low specific activity (i.e. <11 MBq-g"1,
<0.3 mCi'g"1) are compacted and placed into 55-gal. (-210 dm3) steel drums, since
they are considered as non-outgassing wastes. Larger pieces as piping or duct work
from outside the glove boxes are placed into 48x52x82 inches (122x132x82 cm) wooden
boxes.
Also at the Centre of Valduc (CEA-DAM) in France (6), which is presently the
only central deposit for all French non-recyclable solid tritiated wastes, no encapsula-
tion is foreseen before waste packaging into standard 55-gal. drums. The application
of this waste management strategy has been motivated by the insufficient tritium
retention efficiency of cement and modified cement composites, the rather high cost
of thermosetting resins and, not last, the international political constraints presently
hindering the application of the sea dumping option.

12.2 Packaging of tritiated hard waste composites

At CEN-Saclay (7) in France reinforced concrete shells of standard dimensions

(see Fig. 12.1) and 1 m3 internal useful volume are employed for packaging tritiated
hard wastes encapsulated into cement.
Placed inside the concrete shell which is previously lined with a 3-4 mm thick
layer of epoxy resin, tritiated hard waste items are encapsulated by pouring hydrated
cement paste. After cement hardening the continuity of the epoxy resin layer, acting
as the main tritium barrier, 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. 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. 12.1).
Before conditioning the metallic hard wastes are characterized in terms of
tritium contamination level by leaching or thermal treatments on a metallic waste
 94

sample and, if necessary and convenient, previously decontaminated (see subsection

10.2). As pointed out in ref. (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.

Coulis de blocage
Déchets tritiés
01120

Barrière en résine époxy

FIGURE 12.1 - Typical multiple barrier system employed at CEN-Saclay for encapsulating and packaging
tritiated metallic hard wastes from the ELS Reactor (7).

The verification of the resin/concrete thickness and integrity are carried out by
a suitably calibrated ultra-sound machine.
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 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.
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, packaging and
disposing off all radioactive hard wastes generated by dismantling a shielded cell of
the Saclay Hot Laboratory (7).
Note that all mentioned conditioning procedures have necessarily to meet the
specification (see Tab. 13.2) defined for the acceptance of tritiated waste packages by
 95

the French National Agency (ANDRA) that is responsible for the management of long
term waste storage centres (7).
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. In most cases this measurement is based essentially on
water bubbling and scintillation countings (see subsections 3.4 & 13). As indicated in
ref. (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.

12.3 Overpacking of tritiated solid and solidified liquid wastes

At TSTA (3,4) highly tritium contaminated solidified and solid wastes

(>3.7 TBq-m"s, >100 Ci-m"3) (such as sorbed tritiated oils and waste waters, discarded
piping, valves or exhausted uranium storage beds, etc. are packaged into a double
walled container system. As shown in Fig. 12.2 taken from ref. (3) the system consists
of a 30-gal. (-100 dm3) metal drum which is placed into an asphalt-lined 55-gal.
(-210 dm3) drum. An absorber (i.e. vermiculite) is poured into the intermediate void
between the two drums. After sealing the waste package is buried in shafts (4).

55 gal burial
container

Vermiculite
30 gal. primary
container
Hot waste

Asphalt
lined drum

FIGURE 12.2 - Past and present burial container employed at TSTA (3).

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.
(-190 dm3) steel drum liner which is sealed and inserted in a 55-gal. steel drum (DOT
specification 17 H).
If tritiated items are too large to fit into a standard drum they are placed into a
welded steel box. All packaged wastes are checked for outgassing before shipment. If
 96

single drummed laboratory waste is found to be outgassing, also this drum is placed
into a steel box and controlled once again for outgassing.
Facilities and methods have been also developed at MLM (5,8) for the safe
handling and packaging of high specific activity tritiated liquid wastes arising from
tritium decontamination processes on effluent gas streams. Tritiated liquid waste are
also generated by vacuum and transfer pumps (lubricant oils), decontamination opera-
tions (aqueous detergents) and dry box purification processes (tritiated water).
Tritium contaminated aqueous and organic wastes are solidified and packaged at
the Mound Liquid Waste Packaging Facility for burial under total-containment
conditions. The solidification and packaging procedure is described in Appendix X. A
schematic illustration of the overpack employed for containing tritiated waste com-
posites is given in Fig. 12.3 taken from ref. (5).

Type B 30 gal. steel

package TAR drum, sealed
with RTV
25 liter HTO
55 gal. steel unmixed on
17Hdrum 50/50
concrete/ annular space
plaster filled with
absorbent
Organics on
vermiculiti
28 gal.
TAR poly-liner

FIGURE 12.3 - Typical burial package employed at MLM for the containerication and overpacking of
solidified highly tritiated liquid waatea (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). Permeation
tests were performed under static conditions. They consisted of the individual im-
mersion of representative and actual burial packages, containing solidified tritiated
water, oil and octane, in a known volume of leach water. All tests were performed
inside a tight 83-gal. (-318 dm3) drum (see Fig. 12.4). The leach water was periodi-
cally analysed for tritium using a liquid scintillation counter.
Figs. 12.5 to 12.8 taken from ref. (16) show the results obtained after approxi-
mately 580 weeks (-11 years) since the packages were assembled and submitted to
leach tests. Tritium permeation was expressed as total (in millicuries) and fractional
tritium permeation (ratio of total curies permeation to total curies in the package),
both as a function of time. Total actual radioactivity in each package were corrected
for decay time since the package was assembled.
The experimental graphs of Fig. 12.8 show a nearly constant permeation rate
(i.e. slope) for five waste drums. As to the graph related to drum No. 318 the slope
varies significantly with time, since it increases after approximately the 170th week,
 97

-Sample port
Water level ­ Spacer
Spacer -
Asphalt- Λ\\\\\\\\\' ■83-gal
Vermiculite ■ drum
Waste liquid -55-gal
solidified in a . - ι —'
drum
cement-plaster
mixture ï 30-gal
drum
\V\\\\\\\^ 27-gal
Water polyethylene
liner

FIGURE 12.4 ­ Full scale permeation testi at MLM (8). Experimental set up for testing typical burial
packages.

but decreases after the 200 th week and increases again after the 350 th week. Un­
fortunately no explanation was found for this behaviour.
However the experimental data measured during these permeation tests indicate
that even in case of the waste drum N o. 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 (0.36% per year) proposed in ref.
(17) for tritium leakage from packaged wastes.
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). 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.
Last information available from MLM (15) indicates that, after being kept
under permeation test conditions for four years, cumulative tritium releases from these
drums were found to be very low. Tritium activity in both the leach solutions
remained still near the background levels, with pratically no significant difference
between the two drums. 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. 318. N o comments were made to explain these
results.
 98

100.000

10.000
m

ιΧ 1.000
d** ♦*♦♦-♦*
,**♦·* · * ♦

0.100 *a

0.010 * Drum 205 - Water (36,480.0 Ci)

a O Drum 318 · Water (52,128.0 Ci)
a
a

0.001 J- -L
100 200 300 400 500 600
Time since packing, weeks

FIGURE 12.S ­ Full scale permeation tests at MLM (16). Fractional tritium permeation vs. time for two
drums of solidified tritiated water.

100.000

aP m
10.000

Χ' ·♦»♦****
i * * * ' »**

rP , · * *

0.010
e * Drum 217 Oil (1,632.0 Ci)
O Drum 218 · Oil {1.632.0 Ci)

0.001 J_ _l_ _1_ JL

100 200 300 400 500 600
Time since packing, weeks

FIGURE 12.6 ­ Full scale permeation tests at MLM (16). Fractional tritium permeation vs. time for two
drums of solidified tritiated oil.
 99

100.000
I
J^"
10.000

y°
ι
x
i
1.000
o»
*
f
s o*
Fractional pei

E *
8
ρ

0.010
* Drum 113 · Octane (5,892.6 Ci)
O Drum 114· Octane (2,028.6 Ci)

0.001 l i l i l í

100 200 300 400 500 600 700

Tim* since packing, weeks

FIGURE 12.7 ­ Full scale permeation tests at MLM (16). Fractional tritium permeation vs. time for two
drums of solidified tritiated octane.

300
• Drum 113 • Octane (5.892.8 Ci) y
•♦•Drum 114 • Octane (2,028.6 Ci) γ γ
A Drum 217 -Oil (1.832.0Ci) v
τ
«Drum 218 -Oil (1.632.0Ci) VY
250 - X Drum 205 • Water (38.480.0 Ci) Y
Y Drum 318 -Water (52.128.0 Ci) Y

^200 Y

δ
Y
150 _ Y
»v'

3
-

y **
50-
¿xxx* ** +♦

-*IIIBsMVllV
100 200 300 400 500 600 700
Time since packing, weeks

FIGURE 12.8 ­ Full scale permeation tests at MLM (16). Comparison of total tritium permeation for six
typical drums individually containing solidified tritiated water, oil and octane.
 100

12.4 References for Section 12

(1) Krochmalnek L.S. et al., Conditioning and Handling of Tritiated Wastes at

Canadian Nuclear Power Facilities, CFFTP-G-87013, paper presented at the
Am. Chem. Soc. Annual Meeting, Denver, Colorado, April 5-10, 1987.

(2) Krochmalnek O.S., Tritiated Solid Waste Management, Canadian Fusion Fuel
Technology Project, Tritium Safe Handling Course, August 1984.

(3) Nasise J.E., Performance and Improvements of the Tritium Handling Facility at
the LASL, Proc. of ANS Topical Meeting on Tritium Technology on Fission,
Fusion and Isotopie Application, Dayton, Ohio, April 29-May 1, 1980, CONF-
800427 (1980) 347.

(4) Jalbert R.A. and Carlson R.V., Tritium Contaminated Waste Management at the
Tritium System Test Assembly, paper presented at the Am. Chem. Soc. Annual
Meeting, Denver, Colorado, April 5-10, 1987.

(5) Rogers M.L., Treatment and Disposal of Tritium Containing Waste at Mound,
paper presented at the Am. Chem. Soc. Annual Meeting, Denver, April 5-10,
1987.

(6) Mangln D. and Cortella J., La Gestion des Déchets Solide Tritiés Non-Recy-
clable, Actes des Journées du Tritium, Dijon, 23-25 Avril, 1986, CEN-Saclay
(1986) 407.

(7) Coste G. et al., Conditionnement des Déchets Tritiés Issus du Reacteur EL3,
Actes des Journées du Tritium, Dijon, 23-25 Avril, 1986, CEN-Saclay (1986)
339.

(8) Mershad E.A. et al., Packaging of Tritium-Contaminated Liquid Waste, Nucl.

Tech. Vol. 32, (1977) 53.

(9) Gibbs G.E. and Dauby J.J. - Management of High Specific Activity Tritiated
Liquid Wastes, Tritium Waste Control, MLM-2620 (October 1978 - March
1979).

(10) As Ref. 9, MLM-2669 (April-September 1979).

(11) As Ref. 9, MLM-2784 (April-September 1980).

(12) As Ref. 9, MLM-2844 (October 1980-March 1981).

(13) As Ref. 9, MLM-2903 (April-September 1981).

(14) As Ref. 9, MLM-2969 (October 1981-March 1982).

 101

(15) Col vin C.M. and Gibbs G.E. - Management of High Specific Activity Tritiated
Liquid Wastes Tritium Control, MLM-3128 (April-September 1983).

(16) As Ref. 15, MLM-3332 (October 1984-September 1985).

(17) McKay H.A.C. - Tritium Immobilization", EUR 6270 EN (1979), European

Appi. Res. Rept. - Nucl. Sci. Tech., Vol. 1, No. 3 (1979) 599.
 102

13. MONITORING OF TRITIUM OUTGASSING FROM PACKAGED WASTES

An important safety aspect to be considered in handling tritiated solid wastes is

their tritium outgassing property. Due to this property almost all tritiated waste items
have a non-negligible gaseous tritium release potential which may vary depending on
their nature, contamination level, conditioning procedure and package type.
This release potential, which is mainly of concern to waste carriers as well as
surface store and burial ground operators, 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. On such a control measurement is in fact based the
acceptance of packaged wastes for transport, temporary storage and disposal.
The outgassing measurement may be performed on a packaged waste according
to two operational configurations (1), 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.
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.
Along with the selected isolating apparatus a flowmeter, an ionization chamber,
an amplifier and a graphic indicator are currently used to perform the measurement.
Based on the operating parameters and the value of ionization current, 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.
The isolation of drummed wastes during the outgassing measurement may be
done using either a highly ventilated (e.g. 200 m ' - h ' 1 ) fume hoods or a moderately
ventilated (e.g. 0.6 m s -h"1) bell-type apparatus. The choice of one or the other of the
above two options will depend on the sensitivity required by the measurement. As
shown in Tab. 13.1 the current values of the sensitivity limit which may be attained
by the a) configuration are typically 1.85 G B q ' d ' 1 (50 mCi-d" 1 ) in the case of a
fume hood and 5.5 MBq -d"1 (150 microCi -d"1) in the case of a bell-type apparatus.
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. 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. This option is
however rather expensive.
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, specifically designed to receive each waste category. 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. 13.2)

(*) ANDRA ia the French National Agency responsible for the management of national rad waste storage
centres.
 103

outgassing rate values within 100-150 KBq-d' 1 (i.e. 3-4 microCi-d"1) are necessarily
to be measured.
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 5.5 MBq-d' 1 (150 microCi-d'1) to less than
37 kBq -d' 1 (1 microCi 'd' 1 ). Within this range a sensitivity limit up to about
0.1 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. 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.
A sensitivity limit up to than 37 kBq-d"1 (1 microCi-d"1) and lower, referred
to HT or HTO, may be achieved (see Tab. 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. 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. Adequate
samplings from the tritiated water of bubblers and subsequent scintillation countings
will allow to calculate, on the basis of the bubbler water volume and bubbling flow
rate, the permanent tritium outgassing rate of the packaged waste.
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. The most
significant advantage is the low sensitivity limit. Note that the lowest tritium detection
limit which is currently achievable in a bubbler water by means of scintillation
counting technique is 1.85 kBq -dm"8 (-50 nanoCi -dm"3) (1,3).
This method has been applied in France, 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. 13.2) for
accepting tritiated waste packages at the Storage Centre of La Hague.
In Fig. 13.1 taken from ref. (3) is shown the schematic view of the mea-
surement station utilized at Saclay, where four 150 ml distilled water bubblers are
included. With this arrangement the minimum tritium detection limit achievable in the
bubbler water corresponds to a daily total activity release of 1.11 kBq (-30 nanoCi)
(3) per package measurement, which is well below the specification value fixed by
ANDRA (see Tab. 13.2) for the surface storage of tritium bearing waste packages.
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, 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 7.2).
TABLE 13.1 ­ Operational features end sensitivity limits of tritium outgassing measurements performed at some french nuclear centres.

OPERATIONAL SITE GASEOUS WASTE ISOLAT. TRITIUM DETECTION SYSTE M LOWER ME ASURE ME NT DURATION Ref.
CONFIGURATION FLOW RATE APPARATUS TYPE V(dm3) SENSITIVITY SENSITIVITY LIMIT (hours)
(m3­h1) ­3 ­3 Π Τ"
(MBq·«) ^(microCi 'm > (MBq­d > (microCi «d )
Ventilation 1.2 200 Fume­hood IC(4) 10 0.37 10 1.85x103 ­5x10* 1

Ventilation 1 0.6 BelI­type IC(4) 10 0.37 10 5.5 150 1­5 1.2

Confinement 2 2.0 BelI­type IC(5> 10 n.a. n.a. < 0.1 < 3 ­6 1

Bubbling 0.05 Bel I­type Bubblers ft 0.20 (6>

Scintil­ 1.85 (7) 50 <37x10 <1 20(8) 1.3 o
0.18 lation 0.15 (6> ft
Counter 4 (9)

(1) CVA « Centre de Valduc (CE A­DAM), France.

(2) CBIII ■ Cantre de Bruyère­le­Chatel (CE A­DAM), France.
(3) SACLAY ­ Centre Etude Nucleaire de SACLAY (CE A), France.
(4) About 10 dm ionization chamber inserted in a ventilation duct.
(5) About 10 dm ionization chamber inserted in a closed­circuit enclosure.
(6) Water volume in bubblers.
(7) Scintillation counter sensitivity.
(8) Bubbling.
(9) Scintillation analysis,
n.a. = not available.
TABLE 13.2 · Tritium activity limits fixed by ANDRA specifications for the acceptance of tritiated waste packages at the "Centre de Stockage de la
Manche" (La Hague, France).

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,
ACTIVITY <1>
PACKAGE VOLUME INCORP. (t ­m *) (GBq­t') (Ci't') (X d" 1 ) •τ: Τ
(kBq'd' 1 ) (microCi­d"1)
(GBq­t'1)(Ci 't" 1 ) (nf) MATRIX

<7.4 <0.2 drum <2) 0.2 none ­1.5 <7.4 0.2 5x10
­3
111 3.0

7.4 0.2
to to dmn (2 > 0.2 cement ­2.0 <74 2.0 5x10 148 4.0
74.0 2.0 O
en

7.4 0.2
concrete
to to 1.0 cement ­2.0 <74 2.0 5x10 740 20
shell (3,4)
74.0 2.0

(1) Average Initial, per mass unit of radwaste.

(2) Steel or epoxy resin (reinforced by glass fibers) drum lined with a 2 cm thick layer of epoxy resin.
(3) Reinforced concrete shell (C1 type) internally lined with a 2­3 cm thick layer of epoxy resin.
(4) Fractional leach rate by permanent inmersión in water (at a pH within 7­8 and a salt content of 0.5 g*l' 1 ) = 5x10' 2 a"1.
(5) Average Final, per mass unit of radwaste composite.
(6) At t « 20e + 5 e C.
 106

Four · fil de p i a t i n « («.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*·.
Tí
nm—m Λ
Q«rd«

— ­ | Venn« m v i d «

Pompt Sir

Comptawr a 9*1 L.
Typ« Cailut

FIGURE 13.1 ­ Schematic view e/ the assembly employed at CEN­Saclay (S) for tritium outgassing mea­
surements on conditioned and packaged waste·.

13.1 References for section 13

(1) Paillard P., Mesures de Dégazage du Tritium au N iveau des N ormes des Centres
de Stockage de Surface, Actes des Journées du Tritium, Dijon, 23­25 Avril
1986, CEN ­Saclay (1986) 249.

(2) Mangin D. and Cortella J., La Gestion des Déchets Solides Tritiés N on Recy­
clables, ibidem, 407.

(3) Coste G. et al., Conditionnement des Déchets Tritiés Issus du Reacteur EL3,
ibidem, 339.
 107

14. SUMMARY

14.1 Waste minimization at source

For inland tritium handling plants located near closely populated sites where
tritium releases are strictly limited, the confinement of tritium into smaller volumes of
effluents as well as the recovery of tritium losses are stringent safety requirements.
Their purpose is that of minimizing the risks of unacceptable tritium exposures for
operators and general population.
Tritium confinement and loss recovery apply particularly to aqueous and venti-
lation waste streams of conventional FRPs (subsection S.l) as well as to ventilation
atmospheres of tritium processing enclosures operated in tritium recovery plants and
handling laboratories (subsection 5.2).
Under tritium confinement conditions (i.e. tritium segregation and recycling)
tritium concentration in liquid waste effluents is allowed to increase up to a suitable
level. 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, which otherwise could become prohibitive.
However the application of this strategy would also entail some non-negligible draw-
backs. Containement, hazard and operational problems may in fact arise in conse-
quence of the increased steady-state concentration of tritium, the proportional in-
creasing yields to be attained in recovering tritium and the undesired accumulation of
impurities in the recycled streams.
The ventilation atmospheres of tritium processing enclosures are usually detri-
tiated for safety reasons before to be recycled or discharged to stack. Consequently, to
reduce the proportional amount of exhausted dryers or liquid condensates generated
by a detrition unit, 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. This
requirement can be met by reducing the size and consequently the cost of the overall
tritium containment system. 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, i.e. the minimization of the volume of pro-
cessing enclosures and their ventilation by means of dried gaseous carrier streams, re-
circulating inside closed ventilation circuits.
At present all miscellaneous solid wastes, which are generated in a controlled
area of a tritium handling facility are procedurally treated as tritium contaminated,
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. 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.
 108

14.2 Waste pretreatment

14.2.1 Detritiation of gaseous wastes

Tritiated gaseous wastes arise 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) 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.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 environment, i.e. the risks of unacceptable occupational, local and global tritium
exposures.
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 each enclosure,
the atmosphere detritiation may be achieved either in a one-through or a recirculatory
mode through an adeguate detritiation unit.
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).
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, which normally is an essential component of the overall tritium con-
tainment 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
the need of recycling the carrier gas still containing HTO to the detritiation unit, a
counter current operating mode is applied. 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.
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 gases, has been experimentally investigated and applied at Ontario Hydro. In
particular the tritium removal properties of the Zr}Fe alloy have been tested for this
purpose.
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.

14.2.2 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.
 109

In the case of tritiated solid wastes it may be attained by different procedures

(e.g. compaction, incineration, etc.) that are selected according to the characteristics
and tritium contamination level of original wastes. The volume reduction of bagged
tritiated solid wastes may be achieved also by vacuum repackaging, especially if they
cannot be incinerated or compacted (subsection 10.1). As to the uncompressible and
incombustible tritiated wastes, e.g. metallic hard wastes, a reduction of their overall
dimensions may be attained simultaneously when they are submitted to the detritiation
treatment by melting (see subsection 14.2.4).
Tritiated liquid organic wastes may be significantly volume-reduced by an
incineration process (subsection 9.4). This is performed if their recycling is not worth
and provided that their radioactivity and tritium concentration do not exceed certain
limits, which may vary from site to site.
A significant volume reduction is also attained in the case of tritiated aqueous
waste streams if they are processed for tritium removal purposes. 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.
One has to point out that the containment, 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. Depending on their tritium contamination level these gaseous discharges
may be directed to an adequate detritiation unit or directly released through a stack,
where exhausts are continuously monitored for controlling airborne tritium emissions.

14.2.3 Tritium separation and enrichment

Beyond the market value of the pure tritium that may be recovered from triti-
ated waste water, the tritium isotopie separation is normally performed in order to
reduce the risk or unacceptable environmental tritium releases. Its enrichment is aimed
at minimizing the costs of the subsequent management steps (e.g. immobilization,
pakaging and storage or disposal). 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 9.1).
Tritium enrichment is limited to a significant extent by radiolysis and helium
production by tritium beta-decay. The effect of radiolysis, which normally causes an
increasing of tritium releases, is negligible below a tritium enrichment (by atoms) of
0.01%. For hydraulic cements, hydrogenated polystyrene and lower hydrated material
(e.g. hydroxylapatite) the radiolysis effect become important if tritium enrichment
levels of respectively 0.3%, 1% and 6% are exceeded (subsection 9.2).
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. 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. Consequently a sufficient
portion of the internal package volume is currently designed to compensate the effect
of this phenomenon.
 110

A variety of methods are applicable to attain the isotopie separation and enrich-
ment of tritium. Besides the radiological risks and the process costs, other factors will
influence the choice of either of these techniques, 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.
Among the available methods the most widely investigated and tested in Europe,
USA, Canada and Japan at laboratory and pilot plant scales are dealing with catalytic
exchange process (e.g. LPCE, CECE, ELEX processes) using similar hydrophobic
catalyst (subsection 9.1). 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, where a vapor phase catalytic exchange (VPCE)
process is applied for removing tritium from reactor heavy water effluents. Two much
larger tritium separation plants have recently been built in Canada, namely the Triti-
um Removal Facility at the Darlington Nuclear Generating Station and the Tritium
Extraction Plant at the Chalk River Nuclear Laboratory. 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, whose
operational availability has been attained in 1988 (subsection 9.1).

14.2.4 Detritiation of tritiated metallic hard wastes

In order to facilitate the conditioning and the safe storage or disposal of tritiat-
ed metallic hard wastes, i.e. to reduce their outgassing rate, metallic components dis-
carded from tritium handling facilities must be detritiated. The detritiation efficiency
obviously depends on tritium distribution into the tritium permeated metallic compo-
nent. In the case of a prominent oxide layer distribution, surface leaching with water,
isotopie exchange with moisture as well as surface heating have been demonstrated to
be the most effective detritiation treatments (subsection 10.1). A more drastic thermal
treatment such as melting is required if the bulk distribution of tritium is prominent.
It is currently applied to tritiated metallic hard wastes after an adequate reduction of
their dimensions. Besides the reduction of the waste a outgassing rate, the additional
advantages which may be attained by melting are a more homogeneous distribution of
the residual tritium concentration, a minimization of the surface outgassing area and a
significant reduction of tritium contamination on the ingot surface, allowing a safe
handling of final wastes even without a secondary containment.
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, at the
centre of Valduc (DAM-CEA).
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. 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. 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. For this purpose the employ of low-activation steels as fabrication
material for first wall/blanket components is mandatory (subsection 10.2).
 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.g. transportation, storage or disposal), may be done under the safest condi-
tions. In the event that the outer waste containment package may be breached during
the above operations, 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.
For waste management purposes tritium immobilization may be attained up to a
certain degree by incorporating tritiated wastes into solid matrix materials (e.g. water
solidification, metal encapsulation etc.). 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.

14.3.1 Solidification of liquid wastes

Various matrix materials such as:

- silica, alumina and molecular sieves,
- vermiculite and other chemically similar products,
- hydrated calcium orthophosphate, hydroxylapatite, calcium aluminate and sulphate,
- portland and high alumina cements,
- polyacetylene, bakelite type polymers, polyacrylonitrile, polystyrene and water ex-
tendible polyesters,
potentially applicable for immobilizing (i.e. for solidifying) tritiated waste waters
under liquid and vapor forms in a stable solid form, have been extensively investi-
gated in Europe, USA and Canada.
Furthermore some of them, namely portland cements, water extendible resins
and vermiculite or equivalent, were also tested as solidifying media potentially ap-
plicable for immobilizing tritiated waste oils and other organic liquids.
Results from the experimental tests carried out to determine the tritium reten-
tion efficiency of such matrix materials have been published. A comparative assess-
ment of these results leads to conclude that tritium incorporated in such solidification
matrices cannot be considered sufficiently immobilized, due to outgassing and leach-
ability properties of the final tritiated composites. Consequently to attain an adequate
tritium containment all such materials incorporating tritiated liquid wastes must be
integrated in a multiple barrier system, i.e. used in conjunction with one or more
additional physical barriers.
Based on information available from the literature, conclusions are drawn on the
specific properties and applicability of the various candidate materials for tritium
immobilization purposes. 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, semplicity and cost of related procedures, equipment
and raw-materials.
 112

Drying agents

Although the high nominal water capacity (~ 40 wt%) of dehydrated silica gel,
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.
In the case of gypsum even with a low water loading (i.e. CaS0 4 .l/2 H 2 0) a too
high water vapor pressure is attained. At 25°C molecular sieves may strongly held wa-
ter up to 17 wt% with a vapor pressure of 5xl0"4 bar, but the rather high cost make
their use preferable only for immobilizing highly tritiated waters (subsection 9.3.1).

Absorbers

Vermiculite and other chemically similar products cannot be considered as true

matrices, i.e. comparable in terms of tritium immobilization with other inorganic
materials used for this purpose. 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.
For this reason vermiculite and chemically similar products find their best
application as materials for supporting mechanically sorbed tritiated oils inside poly-
ethylene containers. 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 9.3.2).

Inorganic salt hydrates and hydroxides

Although their excellent properties (e.g. insolubility and very low water vapor
pressure) many problems have been found to interfere with the plant-scale application
of hydroxylapatite, which is among the candidate inorganic salt hydrates and hydrox-
ides the most promising in terms of tritium immobilization.
Such problems are dealing with the difficult preparation of the dehydrated pro-
duct, 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.
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 9.3.3).

Hydraulic cements

Hydraulic cements are the simplest and less expensive water solidication media.
High alumina cements are capable of binding twice as much water as portland type
cements, but this advantage is partially off-set owing to the metastable hydrated com-
pounds produced by HAC hydration, which may convert to lower hydrate-forms on
ageing. Portland cements appear to be the best cement types applicable for tritium im-
mobilization purposes. 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.
 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. As to
the silica gel, although its addition to cement do not ¡ ι volve any increase of tritium
teachability, 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. Nevertheless the addition
to cement of a low proportion of Si0 2 (e.g. 5% of "silica fume") has been found to be
beneficial, especially because of the resulting increased resistence of the waste com­
posite to tritiated water permeation.
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, the application of other supplementary physical barriers is
anyhow mandatory (subsection 9.3.4).
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, to which the cement powder is then added.
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. For this
reason this technique wast deemed to be unsuitable for immobilizing tritiated organic
liquid wastes (subsection 9.4.1).

Organic polymers

Based on the information available from the literature, polymeric organic mate­
rials such as polyacetylene, bakelite type polymers and polyacrylonitrile do not appear
well suitable for incorporating tritium in their chemical structure.
This mainly is due to:
­ a limited stability of tritiated polymers to heating, radiation damage and long­term
wheatering.
­ the difficulty of achieving high tritium incorporation yields.
­ the considerable amounts of tritiated organic residues or by­products to be rework­
ed for tritium recycle.
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.
Apart from this latter draw­back, 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 9.3.5).
However, 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 does not occur to a sufficient extent. 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 9.3.4 & 9.3.5). This means that, even if superior to a neat portland cement,
polystyrene and WEP resins are water solidification media still inadequate to meet the
 114

suggested maximum tritium release target of 10"3% per day. As for cements there-
fore, one or more additional containment barriers are needed to minimize tritium
release from them up to an acceptably low level.
WEP resins could be utilized also for solidifying tritiated organic liquids. How-
ever also in this case complex procedures are required. Tritiated oils must previously
be emulsified with water. Then the resulting emulsion must be intimately mixed with
the liquid organic polymer and solidified by adding the catalyst. However, 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 9.4.2). 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.
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.g. dryness, mechanical strenght, stability etc.), strongly de-
pendent on their preparatory conditions.

14.3.2 Encapsulation of metallic hard wastes

Experimentally it has been found that even if submitted to a surface detritiation

treatment (e.g. water leaching, moisture isotopie exchange or surface thermal treat-
ments) the outgassing rate of a tritiated hard waste could results still too high (subsec-
tion 10.3). 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. Water extendible polyester resins and portland cements have been cur-
rently employed for this purpose.
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. For this reason the conclusions
which can be drawn from the comparative assessment of these systems are presented
under subsection 14.4.3.

14.4 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, the application of integrated multiple barrier systems was the option
applied to attain a satisfactory level of tritium containment. This option essentially
relies on the application of successive physical barriers, each of them giving a con-
tribute to the overall tritium containment.
Different multi-barrier containment systems have been assembled by combining
various additional treatment that may be applied on a waste immobilization matrix
(e.g. coating, impregnation, encapsulation) with some containment options such as
simple containerization or simultaneous containerization and container encapsulation.
A still more enhanced barrier effect has been attained by overpacking the waste im-
 115

mobilization matrix inside multiwalled containers provided with containment barrier

materials (i.e. absorbers) for filling intermediate annular voids.
The matrix and barrier materiate as well as the various containers are usually
selected and assembled case by case. This is done not only in compliance with the
chemical form, physical state and concentration of tritium in the waste form but also
depending on what of the available waste storage or disposal routes (e.g. surface
storage, shallow inground burial or deep geological repository) will be subsequently
applied.

14.4.1 Additional treatments on solidified liquid wastes

Surface coating

Surface coatings could be applied to cement or concrete blocks by dipping,

painting or casting around each block. Results of static leach tests performed in a
water bath for differently coated cement specimens (i.e. beeswax, paraffin, asphalt,
coal-tar and epoxy/coal-tar paints) demonstrated that such coatings are capable of
improving the leach resistance properties of a tritiated cement composite. However it
also appears difficult that their efficiency may remain unchanged for long time. Their
integrity often may become worse as time goes, owing to spalling, delamination or
cracking of the coating layer.

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, durability and resistance to chemical attack and long-term
wheathering. Water diffusion from inside and penetration from outside of the compos-
ite is thus minimized.
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. However contradictory results have been
reported by some USA laboratories concerning the extent of this reduction, and un-
fortunately no attempts were made to explain this discrepancy. An eventual
interference with the hydration process by the polymer, accounting for the variability
of the results, was suggested (subsection 11.1.2). However besides the uncertainty of
results, 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.

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. Portland cements, polyester and epoxy resins as well as polystyrene were
investigated as the media potentially applicable for this purpose. In order to produce
 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. In addition to cement and WEP resins, silica gel, zeolites were
used as matrices to solidify tritiated waste waters (subsection 11.1.3).
Static leach tests were performed in a water bath to investigate the efficiency of
the above encapsulating media as additional barriers against tritium release. Results of
these tests (subsection 11.1.3) demonstrated that:
- WEP, 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, while epoxy and
polyester resins particularly for encapsulating tritiated IX resins incorporated into
epoxy or polyester matrices, tritiated cements as well as untritiated cement hallow
cylinders containing tritiated hydrogen under gaseous form.
- 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. 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 7.2).
- 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.
However, although these promising results, 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.
Furthermore one has to point out that in dealing with tritiated wastes the complexity
of these procedures will significantly increase, mainly owing to the stringent safety
requirements associated with tritium handling operations.

14.4.2 Containerization of solidified liquid wastes

The containerization, i.e. the confinement of a tritiated waste composite inside a

suitable primary container, appear to be the most simple, practical and less expensive
option for providing an efficient additional barrier against tritium release.
Extensive water permeation tests programmes have been developed at some USA
and Canada laboratories to investigate the efficiency of a polyethylene primary
container. High density polyethylene (HDPE) was selected because of its excellent
resistance to water vapor permeation, the best thermochemical resistence and, not last,
the prompt availability on the market. The cement and WEP resins were the two types
of matrices selected for incorporating tritiated water, i.e. for preparing the tritiated
waste composites to be sealed inside the polyethylene container and then submitted to
leach test.
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 11.2) that:
- 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
 117

against tritium release. Leach rates even inferior to the suggested maximum release
target of 10'*% per day (subsection 7.2) are attained by using such a material. In
terms of tritium retention efficiency 1 cm of HDPE is pratically equivalent to 1 cm
of WEP resin.
- In the case of a WEP solidified tritiated water, the basic WEP components (i.e.
styrene and vinylester and possibly the methy-ethyl ketone peroxide) have, even
after short contact times, the capability of permanently increasing the permeability
of polyethylene to tritiated water, i.e. the release of tritium across the HDPE
container. 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.
- With a further external layer of WEP resin being applied around the HDPE con-
tainer, the overall tritium retention efficiency of the resulting triple barrier system
(i.e. 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. WEP/WEP and WEP/HDPE respectively) in which the above
triple barrier system could be subdivided.

14.4.3 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. This could be necessary even
after a detritiation treatment, if the level of tritium residual contamination is still too
high to enable an acceptably low outgassing rate.
Leaching data from experimental tests, performed at Ontario Hydro and CEN-
Grenoble on containerized and matrix incorporated tritiated metallic hard wastes, have
shown that (subsection 11.3):
- 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. 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. Unfortunately no comments were reported concerning the possibility of an
altering effect of the WEP components on the permeability of HDPE, like that
observed during the experimental studies on WEP solidification and HDPE
containerization of tritiated waters (see subsection 14.4.2).
- Epoxy resins appear to be superior to polyester resins as a barrier material applied
to attain an additional tritium containment in a cement matrix, incorporating tri-
tiated metallic hard wastes. 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. Such wastes were mainly
produced by dismantling some nuclear plant and facilities (e.g. the EL3 heavy water
reactor and tritium production hot cell at Saclay, the ELAN 2B installation at La
Hague).
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
12.2). The tritium containment degree achieved using such waste packages has been
 118

controlled by tritium outgassing measurements. Considerably low outgassing rate

have been measured, which proves the efficiency and reliability of the conditioning
and packaging procedure (see subsection 14.5).

14.4.4 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. internally lined drums, sealed special metal containers, playwood or
cardboard boxes) without encapsulation. At some nuclear sites (e.g. MLM, TSTA,
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 10.1 & 12.1).

14.4.5 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. This option essentially relies on
the successive application of different physical barriers such as, for instance, an
immobilization matrix incorporating solid or solidified liquid waste items, a multi-
walled container system in which the above tritiated composite is confined, a sorbent
material which is introduced between secondary and tertiary container walls for filling
intermediate annular voids. The various components of such an overpacking system
normally are selected and assembled case by case, according to the chemical form, the
physical state and concentration of tritium in the waste form. Another important
criterion governing the choice is based on what waste storage or disposal route (e.g.
surface storage, shallow inground burial or deep geological repository) subsequently
one intends to apply.
Extensive water permeation test programmes have been undertaken at MLM on
highly tritiated solidified liquid wastes under total containment conditions, i.e. under
an adequate confinement of tritium immobilizing waste composites inside a burial
package assembly like one of those above mentioned. After many years since the
starting of water permeation tests, permeation data indicated that the percentage of
tritium released in average per year to the ground water was largely below the
maximum target value (0.36% per year) proposed as an acceptable limit for tritium
leakage from conditioned and packaged wastes (subsection 7.2).

14.5 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.
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, storage or disposal of such packages. One of the waste acceptance
criteria for the above management operations is in fact based on the compliance with
a fixed outgassing limit.
This safety requirement, which is mainly of concern to waste carriers as well as
surface store and burial ground operators, makes mandatory all tritiated waste pack-
 119

ages be monitored for a control measurement of their outgassing rate before they are
transferred to store or ground burial.
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.
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). The choice of one or the other of the above two options
will depend on the sensitivity required by the measurement. The current lowest sensi-
tivity limit easily achievable by the a) configuration is typically 5.5 MBq -d"1
(150 micro Ci-d' 1 ). By using a higher sensitivity ionization chamber and a lower
ventilation flow rate the limit value may be lowered up to about 2.6 MBq -d"1
(-70 micro Ci-d' 1 ).
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,
specifically designed to receive each waste category.
A so called "low level installation" has been developed at the Centre of Bruyère
le Chatel (DAM-CEA), in France, to cover the sensitivity range from 5.5 MBq 'd"1 to
less than 37 kBq -d"1 (1 micro Ci 'd' 1 ). The current lowest sensitivity limit achievable
by the b) configuration is typically 0.2 MBq -d"1 (~6 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. 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. Adequate
samplings from the tritiated water of bubblers and subsequent scintillation countings
will allow to calculate, on the basis of the bubbler water volume and bubbling flow
rate, the permanent tritium outgassing rate of the packaged waste.
This method has been applied at CEN-Saclay (CEA, France) to verify that,
after conditioning and packaging, 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, (Section 13, Tab. 13.2) the French
National Agency responsible for the management of the national radwaste storage
centres. The acceptance of tritium bearing packaged wastes in such centres is in fact
strictly dependent on the compliance with the above specifications. The minimum tri-
tium detection limit achievable in the bubbler water by such a method corresponds to
a daily total activity release of 1.11 kBq (-30 nanoCi) per package measurement,
which is well below the maximum release limit imposed by the ANDRA specifications
for the surface storage.
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).
 120

15. 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. Beside the operational and environmental safety
implications of methods, system and materials presently applicable or applied for con-
ditioning tritiated wastes, 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.

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:
- Minimization of the volume of tritiated atmospheres of tritium handling enclosures,
that currently are detritiated before to be recycled or discharged to stack. 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.
- Confinement of tritium into small volumes of liquid effluents. This is a stringent
safety requirement especially for inland tritium handling plants located near closely
populated sites. Under confinement conditions tritium concentration in the liquid
effluent stream is allowed to increase up to a suitably fixed level. This is beneficial
both for reducing the final volume of tritiated liquid waste and the cost of the sub-
sequent management operations (e.g. conditioning, disposal or isotopie enrichment).
However, the application of this criterion raises a number of non-negligible design
and operational problèmes dealing with tritium containment and exposure hazard.
- 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. 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.

Waste pretreatment

The reduction of the tritiated waste volume can be attained by incinerating

combustible wastes (e.g. soft materials and organic liquids) as well as by compacting
compressible wastes. The incineration of combustible wastes is authorized only within
certain tritium concentration limits which may vary from site to site.
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 either for safety reasons, i.e. if tritium content of wastes is low but still unac-
ceptable for being released to the environment or for economic reasons, i.e. if tritium
content is appreciably high to justify tritium recovery.
 121

The volume reduction of bagged tritiated solid wastes may be achieved also by
vacuum repackaging, especially if their incineration or compaction is not possible or
allowed.
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.
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. As a results of CECE and ELEX processes tritium can be separated and con-
centrated in a reduced volume of highly tritiated water.
The gaseous atmospheres of tritium handling or processing enclosures needs to
be continually purified to reduce tritium releases to working areas and external
environment.
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.
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). 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.
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.
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.
Tritium can be isotopically separated from highly tritiated waters and then
suitably enriched in order to minimize its environmental release and management
costs. A variety of methods based on catalytic exchange processes (e.g. LPCE, VPCE,
CECE, ELEX) and using similar hydrophobic catalysts are available to this purpose.
To complete the isotopie enrichment of tritium a cryogenic distillation process is nor-
mally applied in conjunction with processes. 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.
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 choice of the detritiation
method is dependent on the distribution of tritium into the permeated metallic com-
ponent. Isotopie exchange with moisture or surface leaching with water as well as sur-
face heating are the most effective treatments, if the oxide layer distribution is
prominent. 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.
 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, organic polymers, absorbers and driers. 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.
Hydraulic cements are the waste immobilization media of simplest and cheapest
application. Portland cements appear the most adequate cement types for tritiated
water solidification and solid incapsulation. 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. To reach the maximum
achievable degree of cement hydration after hardening the cement block has to be
adequately "cured", i.e. left to stand under controlled conditions. No individual cement
type or combination of them is however capable of retaining the totality of the
incorporated 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.
Among the organic polymers water extendible polyesters and modified poly-
styrene resins are the most suitable media for solidifying tritiated water. However,
even if superior to portland cements, they are still inadequate to meet the target tri-
tium release value of 10"*% per day. Furthermore water solidification procedures
required by such materials are too complex and expensive.
Therefore, in spite of their superior leach resistance properties, polystyrene and WEP
resins presently appear less competitive than portland cements which have the ad-
vantage of a much simpler and less expensive application.
The same draw-back hinders the practical application of such media for solidi-
fying tritiated organic liquids, while also the encapsulation of tritiated solid wastes is
limited by a considerable price difference in favour of cements.
Inorganic materials such as hydrates and hydroxides of calcium phosphates,
aluminates and sulphates, potentially applicable for immobilizing tritiated waste
waters, cannot be competitive with cements because of the rather difficult applica-
bility, limited water loading and the poor mechanical and thermal properties of the
final waste composites.
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.
Silica xero-gel is a drying agent able to attain acceptably low water vapor pres-
sures, but only at rather low water loadings. Its tritium retention efficiency becomes
however very low above 100*C. Activated alumina ex i bits similar unsatisfactory pro-
perties associated with even a lower loading capacity.
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. They are capable of firmly
binding water. At a water loading of 17 wt%, which is not far from the fully hydra-
tion (22 wt%), their vapor pressure at 25°C is approximately two order of magnitude
lower than the vapor pressure of free water. However a low water vapor pressure is
not a sufficient judgement criterion since a tritium isotopie exchange may also occur.
 123

Molecular sieves loaded with tritiated water vapors can be regenerated to recover
tritiated water or discharged and conditioned as a disposable tritiated waste.
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.

Waste containment and packaging

Additional treatments of primary solid waste composites by surface coatings (i.e.

beeswax, paraffin, asphalt, coal-tars and epoxy paints) are able to give an improve-
ment of the tritium leach resistance. However the coating integrity, hence their con-
tainment efficiency, is likely to decrease with time due to spalling, delamination and
cracking.
The resin impregnation of tritiated cement blocks was found to improve their
strength, durability and resistance to a chemical attack and long-term weathering.
Polystyrene impregnated cement blocks exibited a non-negligible reduction effect on
tritium teachability but contradictory results were found concerning the extent of this
effect.
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.
A layer of a tritium-free solidifying or encapsulating material either of the
same nature as the primary matrix (e.g. Portland cement or WEP) or a different
material (e.g. epoxy or polyesther resins) is another useful way for protecting the pri-
mary solid waste composite with an additional containment barrier. High density poly-
ethylene is proven to be one of the most effective barrier material against tritium
release. Among the common polymers it has one of the lowest water permeability and
the best thermochemical resistance. 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. The integrity of the
primary HDPE container during the time is normally ensured by leaving in it an
empty espace. 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.
In order to attain its highest efficiency as a tritium containment material, HDPE
should therefore avoid any contact with components of solidifying/encapsulating
organic media which may permanently alter its resistance to tritium permeability.
Also epoxy resin layers formed around a cement block encapsulating tritiated
metallic wastes were demonstrated to act as an efficient containment barrier. Various
containers (e.g. reinforced concrete shells, 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.
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.e. overpacking) is mandatory.
 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.
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. This clearly demonstrated the high efficiency of such a containment
barrier assembly against tritium and water permeation, but also the excellent leak
tightness of the containers forming the overpack.

Waste package monitoring

One of the acceptance criteria allowing the transportation, storage or disposal of

tritiated waste packages is dealing with a limit value of their outgassing rate that
cannot be exceeded.
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. Therefore one can
conclude that the monitoring of gaseous tritium release from each individual package
containing tritiated wastes is an essential control measurement, to be strictly per-
formed before any transportation, storage or disposal in order to carry out such waste
management operations under the safest operational and environmental conditions.
 125

APPENDICES
 127

Appendix I - THE SMEAR TECHNIQUE

As described in ref. (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.g. filter or blotter paper). The total area swiped must be
known or estimated. A few tens of cm2 is appropriate but 100 cm2 is typical. The
swipe is then introduced into a standard liquid scintillation vial that has been pre-
viously filled with the liquid scintillation cocktail. The vial is allowed to stand 10-20
minutes before counting in a liquid scintillation counter. A typical removal efficiency
is 10% but large variations are possible. The counting efficiency will have to be
determined for every particular combination of liquid scintillation cocktail and swipe
material used. If a small paper piece is used, the counting efficiency is not signifi-
cantly affected by its presence. The choice of the scintillation cocktail does not appear
to be particularly critical. The use of wet swipes is sometimes proposed for higher
sensitivity. 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.
As an alternative to liquid scintillation counting, swipes are sometimes measured
in proportional flow counters or plastic scintillation counters. This has the advantage
that the swipe activity measurement may be done directly on the field.

Reference

(1) Wong K.Y., Utting R.E., Safe Handling of Tritium, proposed IAEA Safety
Series Procedures and Data Document, December 1987, under publication.
 129

Appendix II - TRITIUM ISOTOPIC SEPARATION ft ENRICHMENT.

SCHEMATIC FLOW DIAGRAMS ILLUSTRATING THE
AVAILABLE PROCESS TECHNIQUES (1)

( 0 . 5 XF)

" ^ U T O , H,O

HTO. H,0

(Xc)

HTO. H,0
'(200-1000 X F )

FIGURE II.1 - Direct Water Distillation. C - Condenser; D - Distillation column; V - Evaporator; XF

Mole fraction of HTO in the feed (1).

(0.1 x F )
HTO. H,0

(X F )

Hfö. H,0

HTO, M;0
-► ( l o o xF)

FIGURE II.2 - Direct Multistage Electrolysis. E - Electrolysis cell; R - Recombiner; XF - Mole fraction of
HTO in the feed (l).
 130

c
ε
o
ιέ
oc

o. Oetntiated
Heavy ' '
Water

j _ Q 5
Electru'y/ei Puntier n /DT
Π,/ΟΤ 2

Tntiated
'—Heavy
Wat«
Tritium Fixation
and Storage »

FIGURE II.3 - Tritium Extraction by Direct Singlestage Electrolysis and Cryogenic Distillation (2).

D2
1, , ^-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
' ! ^.._|»_
3,/DT
σ»
O and Storage
♦■ 1
>
ò
£;lectro'v'e f

FIGURE II.4 ­ Tritium Extraction by CECE and Cryogenic Distillation (2).

 131

Oxygen ot
Tritiated Supply Recombiner To Reactor
B>—Τ
Heavy Water D}0
Cndr
Irom —s> Evap* caf
Reactor Units •·· n°'
3Ü fo,o Oj
1
;NDR Cat Evap 1

1
\ι <

Cryogenic Distillation System

—ι
—1
1
J
~fiïo T°>
Evap Cat Cndr

Tower

Tower
Gas
fc-io D,/DT Purifier Dj/OT
uO,

-
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.5 ­ Tritium Extraction by VPCE and Cryogenic Distillation (2).

Tritiated Heavy Water

from Reactor Units
Dj/DT

Γ -ι
ι Τ
I I

a
l°i

I
ι
Detonated I Tritium
Heavy Water I Fixation
J "♦" ano-
to Reactor Storage
Units

FIGURE II.6 ­ Tritium Extraction by LPCE and Cryogenic Distillation (2).

Reference

(1) IAEA, Handling of Tritium Bearing Wastes, IAEA Technical Report Series No.
203, Vienna (1985) pp. 16­19.

(2) Canadian Tritium Experience Manual, Canadian Fusion Fuel Technology,

Ontario Hydro (1984).
 133

Appendix III - THE ELECTROLITIC EXCHANGE (ELEX) PROCESS FOR

SEPARATION OF TRITIUM FROM AQU EOU S REPROCESSING
EFFLUENTS

0.33 F,0
Effluent: 1.32 F. 0.01 XF
Tritium free
water
~u Decontaminated hydrogen

c
E
D
Feed: F, Xp 8 catal.
Tritium contam. - O) HT + Η2Ο i=zz^ Η 2 + HTO
water c
CO Keq = 5 (60 'C)
χ:
υ
χ
111

■H 2 (HT)

Eel
Electrol. -z_^ H2O (HTO) — * H2 (HT) +1/2 O2
a Un = 5-15

Concentrate: 0.01 F, 100 XF

Tritium enriched water

FIGURE IIII - A schematic illustration of the ELEX process (6).

The ELEX process (1-6), which has been devel oped for the separation of
tritium from aqueous reprocessing effl uents, combines water el ectrol ysis and tritium
exchange between hydrogen gas and water. The exchange reaction is promoted by a
hydrophobic catal yst, devel oped and manufactured at SCK./CEN of the Mol (Bel gium).
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. As the tritium-free l iquid water trickl es down the
column it becomes more and more enriched in tritium. The hydrogen gas, which is
already tritium depl eted in comparison with the el ectrol yte from which it evol ves,
becomes more and more depl eted when it fl ows from bottom to top. 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. Tritium free
water is added at the top of the col umn. 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. Al ternatives are possibl e, e.g. if
reliable fuel cell s become avail abl e, the decontaminated hydrogen can be oxidized
instead of being vented and the el ectricity can be del ivered to the el ectrol yser.
 134

References

(1) Bruggeman A. et al., Separation of Tritium from Aqueous Effluents, European

Appi. Res. Rept. - Nucl. Sci. Technol., 4, 1 S1982, 63.

(2) Bruggeman A. et al., "Separation of Tritium from Reprocessing Effluents",

IAEA-SM-245/52 (1980).

(3) Bruggeman A. et al., "The ELEX Process for Tritium Separation from Aqueous
Effluents", Tritium Technology in Fission, Fusion and Isotopie Applications,
American Nuclear Society (1980), (Proc. ANS National Topical Meeting,
Dayton, Ohio, 1980).

(4) Bruggeman A. et al., "Separation of Tritium from Aqueous Effluents", EUR

9107 (1984).

(5) Bruggeman A. et al., European Patent No. 4S.5S2; United States Patent No.
4.376.066; Canadian Patent No. 1.171.059.

(6) Geens L. et al, Separation of Tritium from Aqueous Effluents, Final Report
EUR 11551 EN (1988).
 135

Appendix IV - SCHEMATIC ILLUSTRATIONS OF TRITIUM REMOVAL

PROCESSES APPLIED AT THE DARLINGTON AND CHALK
RIVER PLANTS

Deu let, urn „ 0

r Hecombuier
Mskf Up
0, Svitem . HOO/OjO
System D
,i ' Cold Bos
Caïinq
I

I
JL
Expawon \ I
Γ
T
I
r""1 - ) — 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.itanon
I „ »Vt»
iL
fied
Treatment Deuterium
System Loop

0,0 D;O/0T0 ■A _ V
Cold B o .
c»»« I

FIGURE IV.l ­ The tritium removal process at the Darlington TRF (1).

Helium
Relnoerelor

Oetntiated

FIGURE IV.2 ­ The tritium removal process at the Chalk River TEP (1).
 136

Reference

(1) Canadian Tritium Experience Manual, Canadian Fusion Fuel Technology Pro-
ject, Ontario Hydro (1984).
 137

Appendix V - SOLIDIFICATION OF TRITIATED WASTE WATERS.

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. A known mass of cement powder was added slowly while stirring into a known
volume of tritiated water.
A super plasticizer Mighty 150 (sulphonated napthalene formaldehyde, manufactured
by KAO, Japan, and distributed by Atkemix, Brantford) was added to the portland
type 30 up to a concentration of 20 g per kg of dry cement.
A "Jiffy" mixing blade was used at approximately 100 rpm. Once the mixture was
completed as made evident from the consistency of the cement paste, 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. A batch of cement
paste composed of 1000 g of cement, 300 g of water (water/cement ratio * 0.3),
enough to produce 5 specimens was prepared in a 1.3 litre container. A tritium activi­
ty of approximately 80 to 100 MBq (2.2 to 3 mCi) was fixed in each specimens by
means of a known volume of tritiated water (- 2 MBq ml"1, ~ 50 microCi ml"1) added
to the initial batch. All specimens and containers were weighed and a theoretical ac­
tivity was calculated. As a control, one specimen was placed into 1000 ml of deminer-
alized water before it cured and thoroughly agitated. This was allowed to stand 24 h
before a 1.0 ml sample was withdrawn for analysis.
After 1 or 28 days cure, the specimens were stripped from the molds. All
operations were completed in a fume hood.

Water Extendible Polyester - Aropol WEP 661-P, 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. 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. The specimen container, size and
activity was similar to those of cement samples.
To determine the activity in each specimen, 1 ml of uncatalyzed emulsion was
dissolved in 100 ml of methylethylketone and the activity of the solution measured.

Reference

(1) Hawthorne S.H., Conditioning of Tritiated Wastes, Part II - Solidification and

Encapsulation, Ontario Hydro Research Division Report No. 84-6-K (1984).
 139

Appendix VI - SOLIDIFICATION AND ENCAPSULATION OF TRITIATED WASTE

WATERS. SPECIMEN PREPARATION FOR LEACH TESTS AT
KFK, KARLSRUHE (1)

All specimens were of nearly cylindrical shape, with a volume of approx.

143 ml and an activity in the order of 1.7 MBq (46 microCi) per specimen. The curing
time of polystyrene and cement specimens was 3 and 28 days respectively.

Water/polystyrene
-Water=monomer (DQWzbJnder 101) mixtures containing monomer to water
ratios in the range 0.8 to 5.0 were first emulsified with a powerful mixer at 2000 rpm.
Occasionally an extender was added to the mixture to stabilize the emulsion. Polymer-
ization was initiated with a catalyst (di-benzoil-peroxide) in conjunction with an ac-
celerator (dimethyl-p-toluidin or dimethyl-aniline). During the initial stages of the
polymerization a center-line temperature increase up to 65°C was observed in the
specimens. The max. temperature increased with decreasing water content in the
sample.

Waier/cement
Specimens were prepared from Portland PZ 35 F type cement. 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 0.4.

Zeolite/polystyrene
For the preparation of zeolite with a known HjO (HTO) content samples of
zeolite 5A (K 154, Bayer Leverkusen) were first slowly dehydrated by heating up to
400°C over a period of 30 hours (water content approx. 0.8% by weight). The samples
were then rehydrated in a dessicator with known amounts of HjO (HTO) up to the
desired concentration, i.e.: 5, 15 or 20% by weight. The zeolites were then immobi-
lized following the method described above. Main parameters were the amount of
catalyst and the type and amount of accelerator. Gelation occured after a few min-
utes, solidification after a hour. Specimens prepared with zeolite having low water
content attained the highest center-line temperature, i.e. < 80°C, and solidified poorly.

Silica gel/polystyrene
The procedure employed for the dehydration and loading of silica gel (SG 127,
Grace) with up to 25% by weight of H 2 0 (HTO) was similar to that described previ-
ously for zeolites. Solid blocks were obtained with a DOW binder/silica gel weight
ratio of 0.55. After about 30 minutes the center-line temperature of the block reached
a max. of 65°C.
 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, containing 21 or 25% by weight of
H 2 0 (HTO) respectively, with 156 g of PZ 35 F cement and 50 g of H 2 0.

Reference

(1) Penzhorn R.D. and Brunner H., Solidification of Tritiated Waste, Fusion Tech-
nology 1986, Vol. 2, p. 1531, Association Euratom/CEA-CEN Cadarache,
Pergamon Press.
 141

Appendix VII - SOLIDIFICATION, POLYMER IMPREGNATION AND CON-

TAINERIZATION OF TRITIATED WASTE WATERS. 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).
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, were developed for blending tritiated aqueous waste with cement.

1. End-over-end tumbling technique

In this process (2-5, 7, 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. Monitoring of this drum filling step was done on a
weight rather than volumetric basis to ensure a proper formulation. If necessary, a
mixing weight could also be added to the drum at that time to assure an adequate
mixing.

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 - Conceptual fixation of tritiated aqueous waste in polymer impregnated concrete (PITC) by
in-drum tumbling and soak impregnation techniques (3).
 142

The mixing and casting operations simply consisted of adding the required
amount of tritiated aqueous waste to the drum, closing the bung-hole, transferring the
drum to the tumbler and tumbling the mix. 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).
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 dimensions of such a drum are approximately 46 cm I.D.
by 69.5 cm high. A composite occupying 80% of the nominal volume of this container
will have a volume of about 90 litres. 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.
Portland type III and high alumina cements were selected because of their rapid
curing properties.
Both types of cements were mixed with tritiated water to give a w/c weight
ratio of about 0.2 (3). HAC can, of course, hydrate considerably more water
(~ 50 wt%) than does portland cements (~ 25 wt.%), but a significant increase of the
w/c value above that used would result in too dense cement blocks, not easily
permeable by styrene monomer (4).
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. Since the drum also serves as the casting container the need
of a transfert operation is eliminated.
After mixing the cement paste was cured at 40°C. For portland type III or HA
cements the curing required about 24 hours to induce complete hydration. The con-
crete, equilibrated to room temperature, was then impregnated by a soak technique.
Styrene monomer, catalyzed with 5 g per kg of 2.2-[Azobis-2-methylpropionitrile]
(AIBN cathalyst) or benzoyl-peroxide (used as a low temperature catalyst) (1-9, 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. Approximately 4-5 hours
soaking was allowed. Note that the time required for a complete impregnation
depending on the concrete volume, density and composition, is available, but typically
requiries a few hours. 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).
Catalyst-promoter systems which cure at room temperature were not applied to
PITC since the viscosity changes, which may occur during impregnation due to the
initiation of polymerization, may impede the complete permeation of the matrix by
the monomer (4,5).

2. Conventional mixer technique

Smaller size but similar density specimens (6-9) were also produced at BNL for
lysimeter tests at SRP (see subsection 10.3.1) using a conventional dough type mixer
and a w/c weight ratio of 0.22, i.e. the same value applied with the end-over-end
tumbling technique, hence well representative of this type of composite. The water
necessary to give a w/c ratio of 0.22, added along with a suitable amount of tritiated
 143

water to provide a total activity of 370 GBq (10 Ci) for each specimen, was mixed
until a uniforme consistency was obtained.
The portlant type HI cement mix was transferred to a 5-gal (~ 19 dm3) poly­
ethylene carboy, the latter being vibrated to provide proper packing of the mix. The
carboy was then sealed and placed in a oven for five days at 40eC to ensure the
complete curing of the cement.
After removal from the oven the casting was allowed to equilibrate at room
temperature before polymer impregnation. The same soak impregnation techniques was
applied as described for the above tumbling method. 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 , a volume to surface ratio of 4.545 and a density
before impregnation of 1.465 gfcm"3 (8,9).
In the case of lysimeter test at SRP impregnation produced PITC specimens
with a density of 1.707 g*cm"3 and a polymer loading of 16.5% and in the case of
duplicate lysimeter tests at BNL PITC specimens with a density of 1.725 g-cm"3 and a
polymer loading of 12.9% (8,9).

3. Injector technique

In this process (6-14, Figs. VH.2,3,4) 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, was inserted into the dry cement. Tritiated
aqueous waste was then introduced into the cement through the injector. Aqueous
waste was added to the cement until the waste reached the external surfaces of the
cement as evidenced by dampness. The injector was withdrawn and the cement casting
was allowed to cure. After the casting had cured, catalyzed styrene monomer was
introduced into the casting container and allowed to soak through the composite. After
the casting had been completely permeated by the monomer, the monomer was
thermally polymerized. Subsequent to the waste injection, the process was the same as
the previously developed end-over-end drum tumbling method (9).
Injector and soak impregnation techniques applied at BNL (9) produced "hot"
PITC specimens with an average density of 1.783 g.cm"3, an average polymer loading
of 23.15% and a total activity of 170 GBq (4.6 Ci) for each specimen. The specimen
geometry was cylindrical with approximate dimensions of 28 cm diameter χ 26.3 cm
height, representing a volume of about 16 dm 3 and a V/S ratio of about 4.6. Unfortu­
nately no data are available on the results of static leach tests which were foreseen for
these samples.
The same injector technique was applied at MLM in order to produce tritiated
concrete specimens for small- and full-scale leaching tests on packaged PITC com­
posites (10-14).

3.1 Small-scale PITC specimens

The specimens were prepared (14) by filling a 500 ml linear high-density-poly­

ethylene bottles (6.67 cm diam.) with 250 g of portland type III cement to a height of
 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.2 - Conceptual fixation of tritiated aqueous waste in polymer impregnated concrete (PITC) by
the injector and soak impregnation techniques (6,9).

CATALYST
AOOITION
MIXER AQUEOUS
WASTE
MONOMER RESERVOIR
RESERVOIR VALVE
SHUT-
OFF
VALVE

-INJECTOR

FIGURE VII.3 - Injector technique for the fixation of aqueous wastes in polymer impregnated concrete (9).

5.79 cm, then vibrating the bottles to compact the cement. An injector was used to in­
troduce 64 g of tritiated water containing 14.3 TBq (386 Ci) of tritium into the center
of the cement mass at a rate of 2 ml-min"1. After this mixture was cured at room
temperature for 5 days, 62.5 g of styrene monomer containing 0.5% 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. The specimens were then placed in an oven at 40°C
(5% catalyst) or 55°C (0.5% catalyst) for 18 hours to obtain styrene polymerization
(11).
 145

I. CONTAINER FILLED WITH 2. INJECTION BEGUN.AQUEOUS

DRY CEMENT; WASTE I N ­ WASTE DIFFUSES INTO DRY
JECTOR INSERTED. CEMENT THROUGH INJECTOR
PORTS.

. AQUEOUS WASTE OIFFUSES 4. AFTER IMPREGNATION, THE

THROUGH THE CEMENT.
THE WASTE CONTENT IN
THE CEMENT DECREASES
AS THE CASTING SURFACES
ARE APPROACHED.
POLYMER LOAOING OF THE
COMPOSITE IS HIGHEST AT
THE CASTING SURFACES.
EFFECTIVELY ENCAPSULATING
THE WASTE. POLYMER IS
PRESENT THROUGHOUT THE
COMPOSITE.

FIGURE VII.4 - Fixation of aqueous waate in polymer impregnated concrete by the injector techniques (9).

3.2 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. Place a 27-gal high-density-polyethylene drum liner into a 30-gal (~ 115 dm3)
steel drum. Note that cross-linked high-density polyethylene is more desirable
because of its superior resistance to styrene and heat damage.
2. Fill the liner with 112 kg of portland type III cement and vibrate the drum to
settle cement.
3. Place the injector vertically in the axis of the drum, so that the end of the rod is
in the center of the cement mass. The injection rod is 1/2 in. copper tubing with
one end capped. Holes (1/8 in. diameter) are drilled: one in the cap and four
groups of four holes arranged radially, which start at the end and are spaced at 2-
1/2 in. intervals.
4. Insert three thermocouples for monitoring and process control at the:
- center of cement block,
- circumference of the cement block, and at the
- outside surface of the steel 30-gal drum under the heaters (locations: I, 3, and 4
or 5 on Fig. VII.5).
 146

Inject 27 dm 3 of water at 0.23 dm 3 per minute, then remove the injector rod,
filling the hole with cement.
6. Replace bungs on the liner and allow the cement to cure from 3-5 days at ambient
temperature.
7. Install band heaters and insulation on the 30-gal drum and heat the package to
45°C. When the correct temperature has been established, add 24.3 kg of styrene
monomer containing 0.75 wt.% of catalyst (2.2'-azobis [2-methyl-propionitrile] to
the void above the cement block and allow it so soak into the cement.
Increase the heat when the package reaches ~ 45"C again (~ 2 hours), being
careful not to exceed 110°C at the liner. Heat until 70°C is attained at the circum-
ference of the cement block (~ 5 hours), then turn off the heaters. Polymerization
should occur within approximately 7 hours.

30 gal steel
drum
27 gal polyethylene
drum linear

Wraparound
: TC 6
band heater
Thermocouples
Insulation

Styrene polymer

"Concrete

FIGURE VII.5 - Schematic view of the assembly used at MLM (14) for fabricating full scale PITC waste
packages.

References

(1) Colombo P. et al. - Tritium Storage Development, Prog. Rep. No. 2, BNL-
19688 (October-December 1974).

(2) As Ref. 1, PR n° 3, BNL-19981 (January-March 1975).

(3) Colombo P. et al. - The Fixation of Aqueous Tritiated Waste in Polymer

Impregnated Concrete and in Polyacetylene, BNL 20898, Conf. 750989 (1975).

(4) As Ref. 1, PR n° 4, BNL-20421 (April-June 1975).

 147

(5) As Ref. 1, PR n° 5, BNL-20779 (July-September 1975).

(6) As Ref. 1, PR n" 7, BNL-2I700 (January-March 1976).

(7) Neilson R.M. et al. - Immobilization of Tritiated Aqueous Waste in Polymer

Impregnated Concrete, BNL-22900, Conf. 770611-21 (1977).

(8) As Ref. 1, PR n° 9, BNL-50625 (July-September 1976).

(9) As Ref. 1, PR n" 12, BNL-50733 (April-June 1977).

(10) Dauby J.J. et al. - Tritium Waste Control Project, MLM-2451 (October 1976 -
March 1977).

(11) As Ref. 10, MLM-2484 (April-September 1977).

(12) As Ref. 10, MLM-2519 (January-March 1978).

(13) As Ref. 10, MLM-2542 (July 1978).

(14) Wieneke R.E. et al. - Polymer Impregnated Tritiated Concrete. Final Report
MLM-2644 (September 1979).
 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).
 151

Appendix IX - ENCAPSULATION OF SOLIDIFIED AND CONTAINERIZED TRI-

TIATED WASTE WATERS. 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. 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.
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. The WEP resin encapsulating material was then poured
over the waste form and allowed to set for 4-5 hours. The suspending wire was then
cut flush with the top of the solidified specimen and a 0.5 cm cap of WEP resin was
poured on top of this to minimize the possibility of leakage at the wire/WEP interface
(Fig. IX. 1).
The dimensions of containerized and encapsulated specimens of solidified
tritiated water are reported in Tab. 11.7 of Section 11.
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.1 - Cross section of an encapsulated and containerised specimen of solidified tritiated water (1).

Reference

(1) Krasznai J.P., Tritiated Waste Condioning. Part III - Performance of Con-
tainerized and Encapsulated Waste Forms, Ontario Hydro Research Division
Report No. 85-279-K, (1985).
 153

Appendix Χ - 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.l, taken
from ref. (1).

TABLE X.l - Recommended burial package for tritiated liquid wastes.

CONTAINMENT

Primary: rigid polyethylene, polypropylene, or equivalent corrosion

and impact resistant Material, with leak-tight closure; must
fit inside 30-gal (115 on ) secondary.

Secondary: asphalt coated 30-gal (115 dm ) 17H steel drum.

Tertiary: 55-gal (210 dm ) 17H steel drum.

SOLIDIFICATION

Water: maximum weight ratio of one part water to three parts dry cement-
plaster mixture.

Oil and organica: maximum weight ratio of two parte oil or organice to one part
vermiculite or three parts "Absorbai".

TRITIUM CONTENT

Maximum of 70.000 Ci (2.59 PBq) (- 7 g tritium) per 30-gal (115 drri ) drum.

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 . 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 9.5 kg (~ 90
dm 8 ) of vermiculite for organic (pump oil) wastes; 32 kg (~ 90 dm 8 ) of "Absorbai"
may be substituted for packaging organic wastes. The steel drum is then connected to
the bottom of an inert handling enclosure (e.g. a glove-box) for total containment
during transfer of the liquid.
After analysis by calorimetry, the liquid waste is transferred via a calibrated
metering pump into the polyethylene drum; the volume transferred is verified using
calibrated sight glasses on the holding tanks. A maximum of 27 dm 8 of water (within

a DOT Specification 2S, polyethylene, 0.0625-in. minimum wall thickness, 27-gal capacity, closures to be two
2-in. Buttress threaded fittings (1).
b DOT Specification 17H, 18-gauge body and head, 18 25-in. i.d., 12-gauge bolted ring, drop forged lugs, all
external and internal surfaces coated with 10- to 15 mil Cabot's FLEXIBLAC #3230 (1).
 154

37-74 TBq of tritium per dm8) or 25 dm8 of pump oil (about 1.75 TBq of tritium per
dm8) is transferred into the polyethylene drum. 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, with less than 0.5% of the oil separating from the absorber after one year. As
illustrated in ref. (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. No mechanical mixing is necessary. When the transfer is
completed, the polyethylene drum is sealed with a silicon rubber adhesive and the
inert enclosure is flushed with argon to remove residual tritium. The polyethylene
drum is checked for leakage, then the steel drum is removed from the bottom of the
enclosure. The void volume above the polyethylene drum is filled with asphalt0, and
the steel drum lid is sealed in place using a sealant and a bolted clamp ring. The steel
drum is then checked for leakage.
The sealed, 30-gal (115 dm8) drum is then centered in a 55-gal (210 dm8) steel
drum containing ~ 4 gal (15 dm8) of asphalt. Vermiculite or "Absorbai" is then poured
between the two drums to a level ~ 2 in. (50 mm) below the top of the 30-gal drum
lid. The remaining void volume is filled with more asphalt, and the 55-gal drum lid is
sealed with a sealant and a bolted clamp ring.

Reference

(1) Mershad E.A. et al., Packaging of Tritium-Contaminated Liquid Wastes, Nucl.

Tech. 32 (1977) 53.

(2) Rogers M.L., Treatment and Diposa! of Tritium Containing Waste at Mound,
paper presented at the Am. Chem. Soc. Annual Meeting, Denver, April 5-10,
1987.

c Bituminous coating, formulation to conform to specification MIL-C- 102A-Type I (1).

 155

GLOSSARY

Tritium (Τ) Isotope of hydrogen, jH

Pure tritium gas
HT Tritiated hydrogen, no defined percentage of tritium
τ2ο Pure tritium water
HTO Tritiated water, no defined percentage of tritium
Deuterium (D) Isotope of hydrogen, H
D
2 Pure deuterium gas
DT, HD Mixture of hydrogen gas, no defined percentages of tritium,
deuterium and protium
D20 Pure deuterated water
DTO, HDO Tritiated and deuterated water, no defined percentages of tritium,
deuterium and protium
Protium (H) Isotope of hydrogen, χΗ
H Hydrogen as name for the isotope in any chemical form
H
2
Pure hydrgen gas
Η,Ο Normal water
CH3t Tritiated methane
TC CH Tritiated acetylene
TCH = CH2 Tritiated ethylene
TCH - CTO Di-Tritiated acetaldehyde
TCH - CH Tritiated acrylonitrile
CN
TCH «CH Tritiated vinylacetate
OCOCH
 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, Ispra
Site, 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, 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, Ohio, USA)
NET Next European Torus
 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.)
TPL Tritium Processing Laboratory (Tokai-Mura, Japan)
TRF Tritium Recovery Facility (Chalk River, Ca.)
TSTA Tritium System Test Assembly (Los Alamos, NM, USA)
USERDA United States Energy Research & Development Agency
VPCE Vapor Phase Catalytic Exchange
VRF Volume Reduction Factor
WERF Waste Experimental Reduction Facility (Idaho, USA)
WEP Water Extendible Polymer
WVRF Waste Volume Reduction Facility (Ontario Hydro, Ca.)