Iaea Guide For Iodine PDF

AIRBORNE SPECIES OF IODINE
SOLID SURFACES
PHYSICAL AND CHEMICAL ADSORPTION
TECHNICAL REPORTS SERIES No 148
Control of Iodine
in the Nuclear Industry
J I N T E R N A T I O N A L A T O M I C ENERGY A G E N C Y , V I E N N A , 1 9 7 3
CONTROL OF IODINE
IN THE NUCLEAR INDUSTRY
The following States are Members of the International Atomic Energy Agency:
AFGHANISTAN GUATEMALA PANAMA

ALBANIA HAITI PARAGUAY
ALGERIA HOLY SEE PERU
ARGENTINA HUNGARY PHILIPPINES
AUSTRALIA ICELAND POLAND
AUSTRIA INDIA PORTUGAL
BANGLADESH INDONESIA ROMANIA
BELGIUM IRAN SAUDI ARABIA
BOLIVIA IRAQ SENEGAL
BRAZIL IRELAND SIERRA LEONE
BULGARIA ISRAEL SINGAPORE
BURMA ITALY SOUTH AFRICA
BYELORUSSIAN SOVIET IVORY COAST SPAIN
SOCIALIST REPUBLIC JAMAICA SRI LANKA
CAMEROON JAPAN SUDAN
CANADA JORDAN SWEDEN
CHILE KENYA SWITZERLAND
CHINA KHMER REPUBLIC SYRIAN ARAB REPUBLIC
COLOMBIA KOREA, REPUBLIC OF THAILAND
COSTA RICA KUWAIT TUNISIA
CUBA LEBANON TURKEY
CYPRUS LIBERIA UGANDA
CZECHOSLOVAK SOCIALIST LIBYAN ARAB REPUBLIC UKRAINIAN SOVIET SOCIALIST
REPUBLIC LIECHTENSTEIN REPUBLIC
DENMARK LUXEMBOURG UNION OF SOVIET SOCIALIST
DOMINICAN REPUBLIC MADAGASCAR REPUBLICS
ECUADOR MALAYSIA UNITED KINGDOM OF GREAT
EGYPT, ARAB REPUBLIC OF MALI BRITAIN AND NORTHERN
EL SALVADOR MEXICO IRELAND
ETHIOPIA MONACO UNITED STATES OF AMERICA
FINLAND MOROCCO URUGUAY
FRANCE NETHERLANDS VENEZUELA
GABON NEW ZEALAND VIET-NAM
GERMANY, FEDERAL REPUBLIC OF NIGER YUGOSLAVIA
GHANA NIGERIA ZAIRE, REPUBLIC OF
GREECE NORWAY ZAMBIA
PAKISTAN
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held at United Nations Headquarters, New York; it entered into force on 29 July 1957. The Headquarters of
the Agency are situated in Vienna. Its principal objective is "to accelerate and enlarge the contribution of
atomic energy to peace, health and prosperity throughout the world " .
(£) IAEA, 1973
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writing to the International Atomic Energy Agency, Kârntner Ring 11, P.O. Box 590, A-1011 Vienna, Austria.
Printed by the IAEA in Austria

June 1973
TECHNICAL REPORTS SERIES No. 148
CONTROL OF IODINE
IN THE NUCLEAR INDUSTRY
REPORT OF A PANEL
ON THE CONTROL OF IODINE
AND OTHER CONSTITUENTS
OF AIRBORNE RADIOACTIVE WASTES
HELD IN VIENNA BY THE
INTERNATIONAL ATOMIC ENERGY AGENCY
INTERNATIONAL ATOMIC ENERGY AGENCY

VIENNA, 1973
CONTROL OF IODINE IN THE NUCLEAR INDUSTRY
IAEA, VIENNA, 1973
S T l / D O C / l 0/148
FOREWORD
The protection of man and his environment from harmful concentra-

tions of radioactive materials has been the primary objective of radioactive
waste management activities since the beginning of the nuclear industry.
As the industry grew and its contribution to the welfare of man increased,
a great deal of information became available on the various techniques in
use for safely managing radioactive waste. The Agency periodically con-
venes panels or other meetings to collect and update this information and
publishes Safety Series, Technical Reports Series and Guidebooks to help
disseminate it.
Although several good books are available on air cleaning, a great need
has been expressed by both developed and developing countries for as-
sembling under one cover the up-to-date information on the control of
radioactive iodine from the nuclear industry. This publication results from
a panel on the Control of Iodine and other Constituents of Airborne Radio-
active Wastes, held at the International Atomic Energy Agency's head-
quarters in Vienna from 19 to 23 October 1970, and presents the available
information for the first time in a single volume.
The behaviour of iodine in various types of nuclear reactors and in
fuel reprocessing plants is examined and ways are discussed by which
iodine may enter the off-gases of such facilities. Included are discussions
of the chemical forms in which the iodine may appear and of the influence
that the physical and chemical behaviour of the various forms have on the
development of monitoring and removal system. A brief review is also
made of systems and techniques that have been employed for the removal
of iodine from off-gases and for its monitoring. The radiological aspects
of radioiodine and the procedures for deriving working limits of discharge
to the atmosphere are treated in detail.
The report of the Panel is given as the main part of this publication.
The seven working papers presented and discussed are reproduced as an
Annex.
CONTENTS
REPORT OF THE PANEL
1. Introduction — scope and objectives
2. Radiological aspects of radioiodine discharges to

atmosphere
2. 1. Potential discharges from the nuclear power industry
2.2. Quantities and relative importance of radioiodine
2. 3. Guidelines for control of radioiodine discharges
2.4. Relationships between dose, intake and level of
radioiodine in environmental materials
2.5. Future trends
3. Iodine chemistry related to removal and monitoring

processes
3. 1. Forms of airborne iodine
3.2. Removal mechanisms for airborne iodine
3.3. Precautions for iodine monitoring with respect to
iodine behaviour
4. Systems for iodine removal and monitoring

4. 1. Filter systems
4. 2. Liquid scrubber systems
4. 3. Reactor containment spray systems
4. 4. Pressure suppression pools
4. 5. Ice containments
4. 6. Testing of iodine traps
5. Monitoring devices
5. 1. Charcoal samplers
5.2. Filter packs
5.3. Direct continuous system
5.4. Testing of monitoring systems
6. Behaviour of iodine in reactor systems

6. 1. The reactor as a source term in release calculations
6. 2, Containment of iodine in gas-cooled reactors
6. 3. Behaviour of iodine in a liquid-metal fast breeder
reactor system
7. Control of iodine emissions from reprocessing plants 20
7. 1. Fast reactor fuel reprocessing
8. Conclusions 24
References 25
ANNEX: WORKING PAPERS
Control of radioiodine release from reprocessing plants 29

Pamela M. B r y a n t and B. F. W a r n e r
Inorganic adsorber materials for trapping fission product iodine . . . 47
J.G. W i l h e l m and H. S с hu e 11 e 1 к о p f
Behaviour of iodine isotopes in a high-temperature gas reactor
coolant circuit 57
P. R. R o w l a n d , W . E . B r o w n i n g a n d M. C a r l y l e
Control of airborne radioiodine in the loss-of-fluid test
(LOFT) facility 73
W. P. G am m i 11
К вопросу об анализе радиоактивного йода 79
И.Е. Н а х у т и н , Л.Н. Р а с т у н о в и Н.М. С м и р н о в а
Trapping of radioactive iodine produced by nuclear power
stations: sampling and analysis equipment; on-site checking . . . . 87
J. В r i o n
Experiments and experience with radioiodine at Chalk River
Nuclear Laboratories 95
P.J. B a r r y
LIST OF PARTICIPANTS AND ADVISERS 101

REPORT OF THE PANEL
REPORT OF THE PANEL
1. INTRODUCTION - SCOPE AND OBJECTIVES
Much work has been done in recent years on the safe management of
airborne radioactive wastes. In view of the projected demand for nuclear
reactors to supply the energy requirements for the future and the possibility
of reprocessing short-cooled fast breeder fuel, it is believed that the task
of removing radioactive iodine from the exhaust gases from reactors and
fuel reprocessing plants will increase both in size and in scope. Many
developing countries and some developed countries will in the near future
begin planning and building their first nuclear reactors.
, A Panel of experts from seven Member States and two international
organizations was convened at IAEA Headquarters in Vienna, Austria, from
19 to 23 October 1970 to review the status of monitoring, analysis and
control of iodine emission from nuclear plants. The Panel noted the wide-
spread application of International Commission on Radiological Protection
(ICRP) recommendations for iodine dose limits and also that different
countries use different methods for determining limits of discharge.
The ways in which iodine may enter the reactor or fuel reprocessing
off-gases were examined as were the methods used for sampling, analysis
and control of the radioactive species of iodine. The radiological aspects
of radioiodine and the procedure for deriving working limits of discharge
to the atmosphere were treated in some detail.
The Panel felt that this report will be of value to scientific administra-
tors and those who must make assessments of work to be done to solve their
own particular problems in analysing for or controlling radioactive iodine
and must take a broad interdisciplinary point of view.
Although other volatile fission products appear in the off-gases, they
are not treated in this report since radioactive noble gases were discussed
at an Agency meeting in Paris in October 1969 and a meeting on tritium
was held at IAEA Headquarters in November 1970.
2. RADIOLOGICAL ASPECTS OF RADIOIODINE DISCHARGES TO

ATMOSPHERE
2.1. Potential discharges from the nuclear power industry
A number of isotopes of iodine, notably 131I to 135I and 132I from the
parent 132 Te, are produced in considerable quantities in the fuel of nuclear
reactors. Iodine is a volatile material, but very little escapes from fuel
elements during normal operation due to retention in the fuel matrix and to
effective containment by the fuel cladding. Minor cladding defects during
normal operation lead to limited escape of iodine into the coolant; some
of this might be discharged to atmosphere from reactor types from which
small coolant leaks occur, for example, gas- and water-cooled reactors.
Fuel elements are taken from reactors at the end of their useful life and
subjected to chemical reprocessing to recover valuable materials such as
uranium and plutonium. During reprocessing, removal of the cladding
and dissolution of the fuel lead to release of iodine into gaseous (and liquid)
3
4 REPORT OF THE PANEL
waste streams. When high iodine activity is involved, very strict control
of these processing streams is required to limit iodine discharges to
atmosphere.
Discharges of iodine resulting from reactor fault conditions, for
example overheating of fuel elements and extensive damage to cladding, are
fortunately extremely rare, but the quantity released from fuel could be
considerable. In such potential cases, iodine discharge to atmosphere
would be reduced to the minimum practicable fraction of that which has
escaped from fuel by provision of a containment shell, iodine absorber
systems or other suitable means. Accidental discharges of iodine could
also occur during refuelling of a reactor or transport of fuel elements
between reactor and reprocessing plant.
2.2. Quantities and relative importance of radioiodine
Several isotopes of iodine are present in approximately equal activities

when at equilibrium in reactor fuel, about 10® Ci/t under typical irradiation
conditions in thermal reactors, but the radiological significance of 131I
(8-day half-life) is much greater than that of 132I to 135I and I32r e /i32i which
have shorter half-lives (ranging from approximately 1 hour to 3 days).
It is only in the event of a reactor accident involving iodine discharge during
operation or immediately following shut-down that these other isotopes need
be considered. The very long-lived isotope l 29 I ( 17-million-year half-life)
is present in very small quantities, about 0.02 Ci/t, and would only be of
significance in connection with reprocessing fuel from a large nuclear power
program when the fuel had been cooled for periods long enough for 131I
activity to have decayed to a very low level and where large decontamination
factors for 131I are not required.
2.3. Guidelines for control of radioiodine discharges
The Panel noted that the internationally accepted bases of guidelines for
control of radioiodine discharges during normal operation are the recommend-
ations of the ICRP regarding annual dose limits to thyroid glands of members
of the public and annual maximum permissible doses to thyroids of occupa-
tional workers [1]. National methods of application of these basic standards
have developed along two main lines. The first specifies discharge limits
of wide applicability and the second specifies discharge limits on a case-by-
case basis. The first has sometimes led to application of MPC a values
directly to air which is not available for human use. This is often unneces-
sarily costly in waste management resources. Furthermore, this applica-
tion is occasionally incorrect due to reconcentration in the environmental
pathway back to man, for example via cows' milk. The second method,
which was endorsed by the Panel, leads to derivation of secondary standards
expressed, for example, as limits in environmental materials or limits for
discharge rates from the stack, which take local environmental factors into
account. This is in accord with guidance given by the ICRP regarding
selection of critical groups and exposure pathways [2] . The Panel noted
that considerable published information of generally agreed nature is avail-
able regarding parameters involved in such derivations, and that the numeri-
cal basis of the derivation is the dose limit in some countries and a frac-
tion of the dose limit, e . g . one-third, in others.
Accidental discharges of radioiodine to the atmosphere may evoke the

need to take countermeasures to reduce or prevent radiation doses to human
thyroids. There is no international agreement on dose levels at which such
action might be initiated, although some countries have their own recom-
mendations. Relationships between doses and, forexample, levels of activity
in environmental materials for relatively short discharges have many para-
meters in common with those for controlled, i . e . roughly continuous, dis-
charges; derivations of such relationships have been published. The Panel
endorsed the establishment of relationships of this type as the basis of
emergency pre-planning of countermeasures and assessment of hazards
from accidental releases.
2. 4. Relationships between dose, intake and the level of radioiodine in

environmental materials
Iodine isotopes may be discharged to atmosphere as molecular iodine or

as inorganic or organic iodides, depending upon their origin and the con-
ditions prevailing in the system (see 3.1). Molecular iodine may become
adsorbed on submicron particles during or after discharge to atmosphere.
All forms are subject to dispersion in the atmosphere by natural processes
of turbulence, convection due to solar and other heating, movement by wind,
etc. , and usually do not deposit under the influence of gravity. They are,
however, deposited on the ground and other surfaces such as pasture grass,
at rates which depend upon such variables as the physical and chemical
form of the iodine and weather conditions, including wind speed and rainfall
rates. Following dispersion and deposition, respectively, radioiodine may
be inhaled and ingested by the public. The critical pathway involving in-
gestion may be via cows' milk in milk-producing areas in temperate cli-
mates, or via consumption of vegetables in countries in which little milk
is consumed. The critical pathway involving inhalation may apply in desert
areas and at other sites where farming is not extensively practised. In the
latter case the critical group may well be occupational workers on site; in
milk-producing areas it could well be infants in the first year of life. All
limiting radiation doses in the context of normal operation are expressed as
annual limits; there is no requirement by the ICRP for control of exposure
of the public due to controlled discharges on a shorter time-scale than one
year.
In the case of accidental discharges of radioiodine, intakes and doses
are short-term, compared with the time-scale appropriate to controlled
releases. Control of hazards via inhalation and ingestion depends on the
availability and application of countermeasures; for example, the rapid
passage of a cloud of radioiodine in an accidental discharge may allow only
limited countermeasures to be applied after intake, whereas the time-lag
between deposition and transfer of radioiodine to milk is likely to be sufficient
for effective countermeasures to prevent intake.
In the case of controlled discharges, terms for guidelines used are, for
example, radiation protection guides (RPG* s) in the United States of America
and derived working limits ( D W L ' s ) in the United Kingdom, while in the
case of accidental discharges they are protective action guides (PAG's) and
emergency reference levels (ERL's), respectively. In these guidelines,
references are made to intakes of radioiodine, levels of radioactivity in
environmental materials and often to the radiation doses which may arise.
Detailed assessments of these relationships are available in the open litera-

ture, for example, in Refs [3-6] . Most numerical values are subject to a
wide range of values because of natural variations in metabolic and environ-
mental circumstances and an attempt is made in each derivation to choose
representative values which will not grossly underestimate or overestimate
actual situations. The Panel noted that in many situations 131I would be the
only isotope of radiological significance, but when other isotopes were
involved their contribution to dose should be accounted for, for example, as
shown in Ref. [5] .
2.5. Future trends
The Panel also considered the implications of the increasing use of

nuclear power. For controlled releases from reactors, it is to be expected
that designs of future reactors and their clean-up systems would lead to a
situation very similar to the present one, i . e . discharge rates of 131I would
be well below calculated D W L ' s . For reprocessing plants, the importance
of 129 I in relation to 131I depends upon the cooling time of the fuel. Control
of 131I by a long period of decay would reduce the need for effluent clean-up
systems, and a relatively high proportion of 129I in the throughput might then
be discharged to the environment. Conversely, economic considerations
concerning plutonium stocks might lead to reprocessing of short-cooled fast
reactor fuel which would require very high decontamination factors (about
107 -10 ) to control 131I discharges. Hence, 129I discharges would be reduced
to negligible quantities. The Panel noted that a published assessment of the
relationship between discharges of the very long-lived 129I and doses to
members of the public employed the specific activity method using stable
127 I occurring naturally in the environment and in infant thyroids [7] .
A major problem arising in connection with the projected reprocessing

of short-cooled fast reactor fuel is that of providing safe transport for
irradiated fuel in shipping containers because such a container could contain
in the order of 105 Ci 131I at 30 days' cooling. The consequences of accidental
discharge of even 0. 1% of this at ground level could be serious [8] .
3. IODINE CHEMISTRY RELATED TO REMOVAL AND

MONITORING PROCESSES
3.1. Forms of airborne iodine
Iodine in off-gas systems may appear as elemental iodine or iodine

compounds adsorbed on particles, or in the form of vapour of molecular
iodine, organic iodine compounds such as methyl iodide and as inorganic
compounds like HI and HOI. These various forms present different problems
in clean-up and monitoring systems. Molecular iodine and methyl iodide
today are thought to be the most important forms of iodine with respect to
the design of reactor adsorber devices.
For water-cooled reactors it is currently assumed that the total amount
of methyl iodide in the off-gas stream reaching the iodine filters under
maximum credible accident conditions will not exceed 2 . 5 % of the
amount of iodine in the core. For C0 2 -cooled reactors the amount may be
much higher and filter-systems should be designed for the efficient removal
of methyl iodide amounting to 10% of the iodine in the core. Furthermore,

it should be noted that the amount of methyl iodide in a containment atmos-
phere depends on a number of variables one of which is the amount of
organic compounds available for chemical reaction with iodine. Very low
iodine concentrations (of the order of magnitude of a few jag/m3 or less)
may often exist in the form of a mixture with a relatively large fraction of
methyl iodide and other organic iodine compounds, because the concentra-
tion of iodine is then of the same order of magnitude as that of the organic
impurities. Conditions which favour the existence of methyl iodide in the
containment atmosphere are; high concentration of organic compounds;
reducing atmosphere; large metallic surfaces available for catalytic wall
reactions; extended residence time in the containment; elevated tempera-
ture; irradiation, etc.
3.2. Removal mechanisms for airborne iodine
The removal of iodine from air includes natural removal processes such
as plate-out and adsorption on surfaces, trapping by condensing steam, and
washout by droplets. Far more important is the use of specific clean-up
systems such as filters, scrubbers and spray systems. For filtering iodine
adsorbed on particles, high-efficiency particulate air filters (HEPA filter
units) can be used. Because iodine may desorb from the particles already
trapped, HEPA filter units should be placed upstream of an iodine adsorber.
Preheating of the gas stream may be necessary if the gas moisture content
is high and especially if drops of liquid are present. For more information
on air filtration, see Ref. [9] .
Chemical reaction with an imprégnant on the surface of solid adsorber
material can be used for removing iodine vapours. This reaction can be a
simple isotopic exchange or a chemical reaction to produce an iodine com-
pound of low volatility. Because the imprégnant is fixed to the adsorber
material, the non-volatile reaction product of iodine and imprégnant should
be retained on the adsorber material.
Molecular iodine is easily adsorbed on surfaces. Of special interest
are surfaces of construction materials, particles and adsorbents. If the
material constituting the surface can form stable iodine compounds, the
iodine will become irreversibly bound to the surface. This is particularly
true when pure metal surfaces are exposed to molecular iodine. Protective
layers, such as oxide films, can inhibit the trapping mechanism. Materials
such as glass, which do not react with iodine, are excellent when sorption
must be avoided. Methyl iodide is adsorbed by surfaces to a much lesser
extent than elemental iodine.
Water systems are often used for trapping elemental iodine. To ensure
efficient removal, special chemicals are added to the water. Hydroxides of
the alkali metals ( e . g . NaOH and LiOH) convert the iodine to non-volatile
iodine species ( e . g . alkali iodides). Though the reaction is different, sodium
thiosulphate has the same effect and is preferred over other reagents for
certain applications. Even pure water systems may have a substantial
trapping effect if the iodine concentration is sufficiently low. However,
there is evidence that the systems containing hydroxides or thiosulphates do
not remove methyl iodide efficiently.
For reprocessing plants, data concerning the presence of methyl iodide
and the specific removal efficiency for this species under operational con-
ditions in such liquid systems were not available to the Panel. However, the
figures quoted in Section 7 and in the working paper by P. M. Bryant and
B . F . Warner (see Annex) will include any methyl iodide present in the
system.
3.3. Precautions for iodine monitoring with respect to iodine behaviour
The Panel wishes to draw attention to the importance of adequate iodine

monitoring systems. Erroneous results can arise from the use of long and
narrow-diameter sampling tubes, due to deposition of elemental iodine on the
tube walls, and of large-diameter tubes due to settling out of particulates
containing adsorbed iodine. The use of cartridges filled with an unsuitable
charcoal is inefficient for methyl iodide sampling and can give incorrect
results. The poisoning of charcoal due to a corrosive atmosphere or to use
over too long a period can have the s ame effect. Cartridges filled with a
suitable sorbent and intended for a single determination during a limited
sampling period, therefore, are satisfactory for use in measuring quantities
of both elemental iodine and methyl iodide. Iodine sorbed on particles may
be monitored by means of a particulate filter in front of the adsorber for
gaseous iodine.
Special sampling devices such as the Maypack (see Section 5.2) can be
very useful tools when investigating different iodine forms, but simpler
devices can be used for routine monitoring (see Section 5. 3).
4. SYSTEMS FOR IODINE REMOVAL AND MONITORING
4 . 1 . Filter systems
4.1.1. Activated charcoals
At the moment, the most widely used material for iodine removal is
activated charcoal. The surface areas of activated charcoal run up to
1600 m 2 / g . The adsorption coefficients for molecular iodine on activated
charcoal are very high and it is therefore an extremely effective material
for removing molecular iodine, even at high humidities.
Organic compounds of iodine, such as methyl iodide (CH3I), will be
trapped less efficiently by activated charcoal. In the case of high-capacity
purification plants it is essential to ensure that iodine and its compounds are
trapped in thin layers. For this purpose the charcoals used are impreg-
nated with substances which react chemically with compounds of iodine or
enter into isotopic exchange with gaseous compounds of iodine. At the same
time, adsorption takes place. An example is represented by charcoal
impregnated with potassium iodide (KI), where isotopic exchange occurs
between KI, which contains a stable isotope of iodine, and CH3I, which con-
tains one of its radioactive isotopes.
Another example is charcoal impregnated with triethylenediamine.
Triethylenediamine undergoes a chemical reaction with alkyl halides to
form quaternary ammonium salts. Both types of charcoal are commer-
cially available.
On a laboratory scale many other imprégnants have been tested with
success.
Low volatility of the imprégnant and the final reaction product, good
chemical and radiolytic stability, the price, etc,, are factors in the selection
of an imprégnant.
Important factors affecting the: efficiency of trapping are the relative
humidity and temperature of the off-gas. At low relative humidities both
unimpregnated and impregnated charcoals may be used.
At high relative humidities impregnated charcoals are, as a rule, more
effective. Some imprégnants give good results for the trapping of methyl
iodide at high humidity. Liquid must not be allowed to reach the charcoal.
Flammability and relatively low desorption temperatures limit the use
of impregnated activated charcoal for the removal of fission product iodine.
It is the belief of the Panel that impregnated activated charcoal for the
removal of fission product iodine should not be used above a temperature of
150°C. Activated charcoal will age and can be seriously poisoned by im-
purities such as organic vapours, N0 2 , etc., so that the useful life of the
charcoal may be limited to a few months.
4.1.2. Inorganic adsorbents
For higher temperatures and strongly oxidizing gases, a non-flammable

inorganic adsorber material should be used instead of charcoal. The silver
form of zeolites and AgN0 3 -impregnated catalyst carriers showed good
removal efficiencies for elemental iodine and methyl iodine in a broad range
of temperatures and relative humidities in helium, air, steam, and air-
steam mixtures with and without N0 2 . Iodine and methyl iodide are trapped
in these adsorber materials in the form of silver iodide and possibly other
compounds containing silver and iodine (see working paper by J . G . Wilhelm
and H. Schuettelkopf in the Annex).
4.2. Liquid scrubber systems
In general, liquid scrubber systems for removing radioiodine from

gaseous streams have been studied in relation to a number of possible
applications in the nuclear industry. However, these systems must be
designed for the specific applications to be considered and vary considerably
in character from one application to another. Examples of applications are
found in some sampling studies (see Sections 3.2 and 5), in some reactor
pressure-suppression containment systems (see Sections 4 . 3 - 5 ) and in the
removal of radioiodine from dissolver off-gases (see Section 7 and the
working paper by P . M . Bryant and B . F . Warner in the Annex).
Because of the differences in character of the various scrubber systems,
they will be discussed separately in the appropriate sections.
4. 3. Reactor containment spray systems
Many reactors are provided with containment spray systems. These are
usually designed both to remove heat from the containment atmosphere and
to absorb iodine. To perform the function of removing heat, very high flows
are required; these make the sprays very effective for iodine absorption.
Solutions currently proposed are based on using the borated water in the
refuelling water storage tank. Concentrated NaOH is added to this to neutralize
the boric acid. At present there is no consensus on the optimum concentra-
tion of NaOH. Some systems add enough NaOH to convert the boric acid
to borax (Na 2 B 4 0 7 , pH = 9. 2);others add less, to produce a pH of 7 . 5 to 8.
The higher pH should promote hydrolysis of I 2 ; its disadvantages are that it
is somewhat more corrosive, and some evidence indicates that HOI, one of
the products of I 2 hydrolysis, is volatile.
An alternative approach is to add Na 2 S 2 0 3 in addition to the NaOH. In
this case the iodine is reduced to iodide, and HOI does not form. If N a ^ ^ g
is used, the pH must be kept above 8, otherwise sulphur precipitates when
the solution is irradiated. Under irradiation, the Na 2 S 2 0 3 is gradually
oxidized and the pH of the solution decreases.
Absorption of iodine by solutions with pH in the range of 5 to 8 is much
greater than predicted by simple hydrolysis theory when the dissolved
iodine concentration is 10" 5 M or lower. Evidently the chemistry of dilute
aqueous iodine solutions is not completely understood, even though iodine
distribution between water and organic solvents at similar concentration
levels have also shown much more iodine than expected in the aqueous phase.
Many workers have tried to account for this by suggesting reactions with
unspecified impurities. No really satisfactory explanation has been proposed.
Both experiment and theory indicate that absorption of iodine is gas-
film controlled for most containment spray designs using additives. In
theory, there should be some liquid phase resistance for the NaOH system.
However, the partition coefficient for iodine between the atmosphere and the
solutions increases rapidly with decreasing concentration, and time-
dependent calculations indicate that the resistance to transfer into the liquid
phase is significant only for a very short time. It is unlikely to be observable
experimentally.
For the NaOH solutions, the extent of removal of I 2 is limited by the
equilibrium distribution of iodine between the solution and the atmosphere.
In the case of Na 2 S 2 0 3 solutions, the I2 is expected to be absorbed completely.
However, a small amount of the spray solution will probably be suspended as
very fine droplets for some time after spray shutdown and the limiting
decontamination factor is of the order of a few thousand.
None of the solutions removes methyl iodide at a rate sufficient to give
a significant reduction in the dose resulting from containment during the
first few hours. Over longer periods, significant methyl iodide reduction
will be achieved.
4.4. Pressure-suppression pools
Pressure-suppression containment systems are divided into two compart-

ments. The reactor and most of the primary coolant system are enclosed
in a shell conventionally referred to as the dry well. The pressure-suppression
chamber, which is about half filled with water, is connected to the dry well
by vent pipes that discharge under the surface of the water. The primary
coolant and fission products released from the reactor vessel in the event of
a loss-of-coolant accident (LOCA) enter the surrounding dry well and are
carried into the suppression pool. The steam introduced into the pool would
be condensed, and some of the fission products trapped.
Information on pool-trapping efficiencies for elemental iodine and
methyl iodide is.available for steady-state and rapid blowdown experiments
in both large- and small-scale facilities. The measured decontamination
factors for elemental iodine vary from 10 to 10 4 and, for methyl iodide, from
1 to 5. The factors which can have a significant influence on the pool-

trapping efficiency are the vent air-stream ratio, immersion depth of the
vent in the pool, pool temperature and pool chemical composition.
The major problems encountered in directly applying the available data
to a specific pressure-suppression containment design are:
(1) The post-LOCA containment conditions (temperature, pressure, etc.)

change with time.
(2) The transport mechanisms for the post-blowdown-released fission
products and the driving forces for carrying these fission products
through the dry well to the pool have not been completely defined.
The indications are that a large fraction of the iodine that passes into
the pool of a boiling water reactor pressure-suppression containment
system will be trapped by the pool. However, more information is needed
on the time of fission product release and transport mechanisms to deter-
mine what fraction of the total fission products are trapped.
4.5. Ice containments
Ice-filled compartments have been proposed for nuclear power plants

for use within the containment as a heat sink. When employed in this
manner, the accident blowdown is ducted through these compartments. The
ice is identical in composition to the sodium tetraborate used as a spray
solution.
Some work has been undertaken to study the absorption efficiency of
ice for I 2 and CH3I. Typical experiments consisted of passing an air-stream
containing approximately 5 X 1 0 " 6 mol/1 of I 2 or CH3I through the bed of ice
cubes containing approximately 700 g of ice for about an hour. The iodine
not absorbed by the column was subsequently removed from the air-stream
by the back-up thiosulphate solution and the charcoal filter. This permitted
a determination of the material balance. Immediately afterwards, the ice
column was exposed to a stream of either air or an air-steam mixture at
a flow rate of 1 1/min. This step was performed for various time intervals
up to 10 min.
The efficiency of ice-cubes as absorbents for I2 and CH3I will be in-
fluenced by the weight ratio of these iodine compounds relative to that of
ice. In the test experiments performed, the weight ratios ranged from
5 X10" 3 to 3X10" 1 . These values reflect tests run at iodine concentrations
far in excess of those expected to be encountered in an incident. The tests
were deliberately designed to be conservative, thereby testing the ice
systems' resistance to I2 breakthrough.
The test results for iodine indicated that when frozen distilled water was
used as an absorbent, at least 82% of the iodine was trapped initially. Air-
stripping rapidly reduced the amount of absorbed I 2 as a function of stripping
time. Whenfrozenbase-borate ice cubes were similarly tested, approxi-
mately 60% of the absorbed I2 was trapped irreversibly by the frozen ice.
It has been shown that under comparable test procedures approximately
100% of all the I2 is trapped irreversibly by ice containing 1% by weight of
Na2S£>3 adjusted to a pH of 9.0. The latter results could be significant since
they indicate that the I2 concentration in a containment vessel could be
reduced effectively to zero after the initial blowdown. This rapid reduction
in I2 concentration could also help to minimize the probability of formation

of CH3I other than what is formed in the reactor core.
Once CH3I is formed, however, ice cubes containing additives show
very little affinity for absorbing this compound ( ~ l - 5 % ) . Moreover, even
these efficiencies are rapidly reduced by air-stripping. If an additive for
CH3I is used, it will have to operate in the liquid phase since the frozen
ice form has very little affinity for CH3I.
4.6. Testing of iodine traps
It is necessary to emphasize the need for testing the efficiency of iodine

trapping facilities: (1) at the time of installation, for the detection of con-
struction and assembly defects; (2) at periodic intervals thereafter, es-
pecially in the case of traps operating on a permanent basis, which deter-
iorate relatively rapidly (the logarithm of the decontamination coefficient
may become halved after 6 months permanent use).
In-situ testing of the whole trap assembly is carried out at the time of
installation. Periodic testing can be undertaken advantageously in the labo-
ratory, on small control traps which, during normal operations, are
mounted on the main trap to form a by-pass.
4.6.1. Precautions to be taken
(1) Lack of homogenization of samples taken upstream or downstream

from the trap is often the cause of inaccurate testing. Doubling the number
of samples taken at particular points provides data on the homogeneity of
concentration.
(2) Those parts of the sampling devices in contact with the iodine must
be of a material which is not easily contaminated, e . g . Teflon, glass,
electrolytically polished stainless steel. The surfaces must be completely
clean. Any traces of dirt cause deposition.
(3) The concentration of iodine upstream from the trap should be at
least 0. 1 mg/m 3 in order to obtain efficient decontamination. This concen-
tration is also of the same order of magnitude as the concentration which may
be expected in the event of an accident.
In some cases it is useful to carry out measurements with the aid of
a charcoal column divided into sections with subsequent measurement of the
charcoal activity in each individual section. In this case, absence of iodine
in the successive sections indicates complete iodine trapping.
Even in those cases when liberation of iodine to the gaseous phase occurs
at irregular times, it is advisable to employ continuous sampling throughout
the process in order to determine the mean concentration of liberated iodine
because of slow desorption of iodine from surfaces.
Emphasis should be placed on the need for testing with methyl iodide,
in addition to molecular iodine, for the following reasons:
(a) The removal of methyl iodide is a major function of a charcoal bed,
as elemental iodine plates out relatively easily on the metal surfaces
of duct work, etc.
(b) Use of elemental iodine alone may give an optimistic performance
value for the reason given in (a) above.
(c) The labelled methyl iodide test, particularly for "slug" releasees
very simple.
The tests should be carried out for molecular iodine and then for methyl
iodide; the effects of ageing and poisoning may be different for the two
forms of iodine.
4.6.2. Recapitulation of the principle of iodine testing
Iodine vapour labelled with 131I is injected upstream from the trap being
tested. Activated charcoal is used to take samples of air containing iodine
upstream and downstream from the trap. The efficiency of the trap can be
determined from the radioactive content of the samples.
The on-site testing conditions are generally those of the surrounding
environment (traps placed on the depressurization circuits of gas reactors
are an exception, as the latter must be tested under actual working conditions).
When working conditions are very different (high humidity or temperature)
an attempt should be made to test the control traps under these conditions in
the laboratory.
There are other assay methods, such as the method employing dichloro-
difluorobenzene. The Panel draws attention to the fact'that, while such
methods are permissible for controlling the installation of a new trap, their
usefulness in determining the effects of aging is, to say the least, doubtful.
Components should be checked at the assembly stage, before installa-
tion. In addition to testing their efficiency, their resistance to vibration
should be tested with a view to eliminating components whose design does
not ensure that the adsorbent material remains packed.
The principal characteristics of the adsorbent material should also be
checked, especially when such material is not being manufactured on a
regular basis, as is the case with impregnated materials. In particular, the
friability of the material should be low enough to ensure that the trap will
not disintegrate.
5. MONITORING DEVICES
Devices and systems for monitoring iodine must be designed, tested

and operated in such a way that established requirements of checking stack
off-gases and working areas are met. The general ultimate purpose of the
monitoring is to provide a means of checking the release of iodine. Monitoring
is also necessary for checking filter and process operation. It can some-
times be advantageous to monitor for iodine in the environment of a nuclear
plant as a final check that the releases are within permissible limits. In
milk-producing areas the analysis of milk for radioiodine, for example, by
means of 7-spectrometry is a feasible method for performing this check.
Systems for monitoring iodine in air can be continuous or can rely on
continuous sampling combined with measurements at certain time intervals.
For this, several techniques are used. It is important to make sure that
an appropriate technique is used, as iodine can exist in different physical and
chemical forms (see Section 3.1). Special precautions must be taken to
avoid iodine sorption on surfaces and penetration of organic iodides through
unsuitable adsorbent materials in the samplers. Charcoal samplers for
gaseous iodine are widely used. A particulate filter is placed in front of the
adsorber to collect particles. For certain applications and in research work
special filter packs (Maypacks) are used (see Section 5 . 2 ) . Special gas-
chromatographic techniques have proved valuable in identifying organic

forms of iodine. For laboratory work, small bubblers filled with
0. 1M_ Na 2 S 2 0 3 or NaOH are effective for sampling molecular iodine.
In analysing for radioactive iodine in gases containing nitric oxides,
sampling may be performed by pumping the gas through small columns with
a packing containing AgN0 3 and heated to 190-200°C. The trapped radio-
iodine is monitored for y-radiation. This method, properly implemented,
can ensure high measuring accuracy.
5.1. Charcoal samplers
Sampling of gaseous iodine can be carried out by means of a bed of

charcoal or other suitable adsorbent material. For efficient sampling of
methyl iodide, specially impregnated charcoals are used. As the charcoal
samplers are not effective for particles, it can be advantageous to use a
filter paper in front of the charcoal bed. Precautions must be taken so that
serious poisoning of the charcoal sampler is prevented. Charcoal samplers
therefore cannot be used for too long a time and can be used only to a very
limited extent in poisoning atmospheres. Condensation of water vapour in
the bed must also be avoided. The sampling efficiency depends on the gas
residence time in the bed. For filtering purposes this residence time must
be long enough (0.1 - 1 s) to assure the required removal efficiency but,
for monitoring, a lower efficiency and a shorter residence time (0.01-0.1 s)
can often be tolerated. Thus even charcoal-impregnated filter papers can
be suitable for sampling molecular iodine.
If the gas flow contains large amounts, compared with radioiodine, of
other radioactive volatile substances, these can interfere with the analysis
of iodine collected in an adsorber. If these substances are radioactive
noble gases the interference can be suppressed by elution with an inactive
carrier gas. In some cases, y-ray spectrometry can be used.
5.2. Filter packs
Sometimes it will be necessary to know not only the total amount of

radioiodine but also the composition as to molecular iodine, iodine sorbed
on particles and more penetrating forms, e . g . methyl iodide. The higher
the required efficiency of off-gas cleaning, the more one needs to know about
the iodine forms. Filter packs have been widely used for a rough separation
of the three forms mentioned. One special type consists mainly of a metal
tube into which are inserted metal screens (copper or silver-coated copper)
for removal of molecular iodine, particle filters for separation of iodine
sorbed on particles, charcoal filter papers and a bed for the adsorption of
organic iodine. The units are placed in this order from the inlet side.
This type of filter is called a Maypack after its introduction by
F . G . May at Harwell. Even more elaborate types using other adsorbents
are now in use.
5.3. Direct continuous system
The use of continuous sampling devices for activity measurement

permits accurate recording of releases, but these devices are not always
suitable as instruments for giving direct alarm, e . g . when release limits
are exceeded or when filter banks have to be switched in. To meet demands
for providing immediate alarm, special instruments are sometimes used. These
instruments can be of a type supplied with a moving charcoal paper strip
continuously monitored by a detector and a single-channel analyser.
For some applications a fixed, continuously sampling, cartridge moni-
tored by a detector may be advantageous. It is important that the cartridge
in such a system be replaced before serious poisoning and that interfering
radioactivity is reduced to a proper level.
An alarm device which is not specific for iodine, but which operates
perfectly well if iodine is released accidentally, is a detector consisting of
differentially mounted ionization chambers through only one of which the
gas flow being monitored passes.
5.4. Testing of monitoring systems
As a final check of the reliability of a monitoring system, actual in-situ

tests are often necessary. In this method, known amounts of the relevant
radioactive substance are injected into the gas stream which is to be
monitored. An overall check of correct sampling, suitable adsorbers and
instrument calibration can be obtained by this technique.
6. BEHAVIOUR OF IODINE IN REACTOR SYSTEMS
6.1. The reactor as a source term in release calculations
The ultimate source is clearly the fuel, but from a practical point of
view the immediate source term is likely to arise from the coolant. This
is because, among the large number of fuel cans present in a power reactor,
it is not improbable that at any given time a number will have developed
faults which release iodine and other fission products into the coolant.
All the fission products from a faulty capsule will not escape
immediately — an important fact which enables reactors to be run quite
safely even though there is a small release from the core. The rate of
release will, of course, depend on the type of fuel in a given reactor but, as
an example which may be pertinent to many reactors at present envisaged,
we may consider release from UO2 or UC2. The determining factor then is
the diffusion of fission products out of the crystallites of such fissionable
material. This is a complex process. For example, at low burn-up,
diffusion may be mainly through the lattice but, at higher burn-up, noble
gases may accumulate and aggregate into bubbles. Diffusion of these to the
surface of the crystals may then influence the rate at which fission products
escape.
Factors influencing the effective diffusion coefficient for escape pro-
cesses from crystallites will depend on the size of the crystallite and, in
particular, on fuel temperature. The values of effective diffusion coefficients
are usually sufficiently low for appreciable decay of fission products to
occur during their escape to the crystallite surface and the overall rate of
release of an isotope therefore depends on its decay constant. In order to
take into account the different fission yields of different isotopes, it is usual
to express the rate of leakage of a fission product from the fuel in terms of
an R / B factor (rate of release/rate of birth by fission).
The R / B factor is, in a sense, an inverse decontamination factor and a

low R/B signifies a low release. The theoretical treatment of diffusion from
crystallites is complex but the results of theoretical and experimental studies
can usually be represented well enough for a wide range of isotopes [10] by:
,1/n
(1)
вЧг;
Theoretically the value of the index 1/n should be 1/2 but it may vary in
practice between 1/2 and 1/1 for various fuels, depending on crystal texture,
burn-up, etc.
The effective diffusion constant D is temperature dependent with an acti-
vation energy Q:
-O/RT
D = ke (2)
In general,к and Q and hence D will vary with the chemical nature of the
isotope concerned. Strontium, for example, would not be expected to obey
the same constant as xenon. However, the fuel in most reactors is at a
high enough temperature for iodine to behave as a gas in its diffusion out
of the fuel crystallites, so that it would be expected that the R / B for 8-day
131I into the coolant would, for example, be of the same order as that for
133 Xe which has approximately the same half-life.
The significance of the foregoing is the indication that it is reasonable to

expect a relationship to exist between the R/B 1 s of inert gas and those of
iodines so that by measuring inert gases and then applying a half-life rela-
tionship such as that of E q . ( l ) it should be possible to monitor the iodine
R / B ' s . This is a considerable convenience, since it is appreciably more
difficult to measure the R/B 1 s of iodines than those of noble gases.
However, in order to establish such a relationship for a given reactor
type, it is necessary to carry out measurements of R/B 1 s for noble gases
and for iodines at the same time on a typical reactor at power.
In order to do so, it is necessary to know the total iodine at equilibrium
in the coolant circuit when the reactor is at power; in practice this requires
a measurement of the iodine in the coolant leaving the core and an estimate
of the amount plated out on the steel and other adsorbent surfaces of the
coolant circuit.
Because it is chemically reactive and plates out on the walls of any
pipes used for drawing off coolant samples, special methods must be used
for sampling iodine in the coolant of a reactor. As an illustration, the use
of one such method is described in the working paper by P . R . Rowland,
1 W. E. Browning and M. Carlyle (see Annex). To obtain the total iodine in the
circuit it is also necessary to estimate the amount of iodine plated out on the
steel and other surfaces of the coolant circuit. This requires analysis of
iodines adsorbed on typical coolant surfaces such as those of a heat-exchanger.
Reactors cooled' by organic liquids and molten salt reactors were not
discussed because of the complexity of the chemistry involved. Liquid
sodium coolants are discussed in Section 6. 3 . 1 .
For gas-cooled and water-cooled reactors the expectation is that most
of the iodine which leaks from the core will plate out on the steel of the
coolant circuit, but that a portion in equilibrium with this will circulate in
the coolant. The total of these two sources of iodine will be in decay equili-
brium with the release from the core and will increase as the R / B increases.
Hence, measurement of the ratio in which iodine is apportioned between
the coolant and the steel walls of the circuit (in the plate-out factor), and
monitoring of iodine R/B 1 s by the methods indicated, enables the reactor to
be evaluated as an iodine source term.
6.1.1. Release due to leaks in the coolant circuit
This consideration arises because it is generally accepted that, from a

practical engineering point of view, it is realistic to assume that certain
leakage from flanges, shaft seals, valves, etc., will occur. The maximum
possible release can be calculated from the rate of leakage and the concen-
trations of iodines in the coolant calculated as above. Such calculations can
be used, for example, either to specify maximum allowable design leak
rates (assuming a given percentage of faulty fuel) or the maximum amount of
faulty fuel that can be tolerated in an operating reactor (assuming a normal
leak rate).
6.1.2. Release during maintenance
Knowledge of the amount of iodine in the circuit of a reactor at shut-

down and an estimate of the amount plated out on various components will
enable a calculation to be made of the amount of iodine on a component such
as a heat-exchanger and the time for decay which must be allowed before
the circuit is opened and the component exposed for maintenance.
The Panel notes that only a small fraction of the iodine on the surface of,
say, a heat-exchanger is released on exposure to air, but insufficient data
exist to enable this to be predicted accurately. Such calculations therefore
give maximum possible values rather than expected values. The release
of iodine from heat-exchanger surfaces will depend very much on the surface
temperature.
6.1.3. Loss-of-coolant accident
Knowledge of the concentration of iodines in the coolant will give the

amounts immediately available from the coolant itself. However, the Panel
noted that, in general, insufficient information was available to enable
estimates to be made of the amount of iodine that would be deplated from the
steel surfaces and released either during the loss of coolant or soon after-
wards. Nevertheless, the total iodine in the circuit, i . e . that in the coolant
plus that on the steel (calculated from the plate-out factor), will give an
upper limit to this source.
Hence, knowledge of iodine R/B 1 s and of the distribution of iodine
between the coolant and steel surfaces provides the basic input data on which
to establish control methods, i . e . the specifications of stack adsorption
beds, ventilation rates of operating containments, etc. These data also
provide an estimate of the proportion of iodine which is immediately avail-
able from the coolant circuit in the case of a loss-of-coolant accident.
However, if such an accident is concurrent with or the cause of further
damage to the core, further assumptions must be made concerning the iodine
then released from the damaged fuel. Calculations regarding the l o s s - o f -
coolant accident will therefore be dependent on the type of reactor involved.

In a high-temperature reactor using coated particle fuel, it is likely that
the major source term will simply be the iodine that is present in the coolant
circuit at the time of the incident, since particles do not burst easily under
changes of temperature and pressure. The contribution to release from
fuel damaged by the incident (or at the time of the incident) will be relatively
small and slow. On the other hand, for reactors with metal cans which may
burst at loss of pressure, the contribution of iodine from the burst cans
must be considered. Calculation of filter capacity to deal with this will
follow different lines from those already indicated and will depend on the
assumption made regarding any particular reactor design. The working
paper by W. P. Gammill, in the Annex, includes such an assumption.
The Panel noted that adsorption of iodine by filters, charcoal beds,
molecular sieves, etc., may be affected by the presence of water. This
problem would therefore be expected to be more acute with water-cooled
reactors than with gas-cooled reactors. This will apply to day-to-day leaks
under operating conditions but it should be borne in mind that a burst heat-
exchanger in a gas-cooled reactor may conceivably be associated with a
pressure excursion and a los s-of-coolant incident. The behaviour of adsorber
materials in the presence of water is therefore of general importance.
The magnitude of the adsorption problem may also depend on the
chemistry of the coolant circuit. If, because of the composition of the
coolant, penetrating forms such as methyl iodide are formed, the bed may
need to be thicker and possibly use a different type of adsorber.
No mention has been made of decontamination factors which may be
inherent in such phenomena as plate-out of iodine on the walls of a lead-
path or secondary containment, etc. It is considered that such factors would
have to be established by work directed towards the study of specific reactor
designs.
Finally, mention should be made of the form of iodine which may escape.
This will probably depend on the route of escape. For example, a leak
through an oil-bearing may convert a high percentage of the iodine to vola-
tile organic iodides, i . e . so-called penetrating forms that are more difficult
to adsorb in traps than elemental iodine. Monitoring of the form as well as
the amount of iodine in a release is therefore of value. The working paper
by I . E . Nakhutin et al. in the Annex indicates a method for doing this.
6.2. Containment of iodine in gas-cooled reactors
The integrity of the containment of a water-cooled reactor can usually

be guaranteed to a substantially higher standard than the pressure circuit.
Gas-cooled reactors are designed so that maintenance of adequate cooling
to a shutdown core is guaranteed to a level comparable with that of a con-
tainment. As a result, the containment is not of prime importance to over-
all safety and this is reflected in the requirements of the fission product
trapping plant. For whereas the conditions that would exist in a containment
following melt-out of a core are severe and ill defined, the conditions which
gas-cooled reactor trapping plants must meet are specific.
Melt-out of a fuel channel is one of the more important postulated ac-
cidents in which a trapping plant is an advantage. By allowing the main
circuit to be depressurized to atmospheric pressure through the trapping
plant in a time which is short compared with radioactive decay, the leakage
of activity from the pressure circuit is reduced. The primary heat-exchanger

can be used to control the temperature of the gas fed to the trapping plant.
The gas composition is that of normal coolant. The activity involved, and
hence the fission product heat to be dealt with, is limited to that of a single
channel, while the trap effluent can be sampled and the blowdown rate con-
trolled. Another type of accident which can be controlled by a trapping plant
is a fuel-handling accident in which irradiated fuel overheats within the con-
tainment or the reactor building. Atmospheric air at high relative humidity
must be decontaminated with high efficiency in a ventilation system operating
at ambient pressure and temperature. Trapping plant requirements are not
greatly affected by depressurization accidents since release of activity is
limited by controlling the conditions experienced by the fuel.
Both amine- and iodide-impregnated charcoals offer adequate perform-
ance for the ventilation plant of fuel-handling areas and a mixture may
be used in combination with high-efficiency particulate filters. The main
problem is to protect the filters from damage and the charcoal from expo-
sure to vapours which would poison it by condensing on its surface.
There does not appear to be any compelling need for improved per-
formance or more fundamental data, but added experience is desirable:
(a) in the design of the plant which remains leak-tight and protects its
filter units from damage;
(b) in practical methods of in-situ testing of the plant, particularly
aerosol filters;
(c) in the aging or poisoning of charcoal or zeolites under the con-
ditions met in practice; and
(d) in the use of silver-impregnated zeolites and similar materials
under conditions simulating a reactor blowdown.
6.3. Behaviour of iodine in a liquid-metal fast breeder reactor system
6.3.1. Normal operations
During the normal operation of a liquid-metal fast breeder reactor

(LMFBR), some of the more volatile fission products, including iodine,
enter the primary coolant by means of diffusion through the fuel element
cladding, leakage through cracks resulting from cladding failure, or as a
result of fissioning of uranium contamination (tramp uranium) on the external
surfaces of the fuel elements. Because of its chemical nature, iodine has a
very high affinity for sodium. Thus, it would be expected that essentially
all of the iodine entering the primary coolant would immediately react with
the sodium and would be retained within the primary system. Experience
with operating L M F B R ' s indicates that this is in fact the case.
Iodine concentrations in the sodium coolant have been observed to reach
a steady-state value which is generally dependent upon the integrity of the
fuel cladding. Maximum concentrations can be expected to occur within the
sodium purification cold traps. Although some trace quantities of sodium
iodide may exist in the vapour phase in the inert cover gas, the concentra-
tions are below the detection limits for the analytical procedures generally
used.
Because of the retention of iodine by the sodium, special equipment for
removal or control of iodine is not required for an LMFBR off-gas system.
A high-efficiency particulate filter system for the removal of sodium aerosols
provides adequate control of the radioiodine, even in the event of substantial

cladding failure.
6.3.2. Accident conditions
The Panel noted that the accident situation most likely to arise in a
LMFBR will be a minor sodium spill resulting in a pool fire. The Panel
also recognized the possibility of a sodium spray fire in the event of a leak
in the cooling system. In either event, the concentration of iodine in the
sodium (form of sodium iodide) would be expected to be quite low. Experi-
ments on the behaviour of iodine under the pool fire conditions have been
described (Baurmash, et al. , [11]), which indicate that the sodium iodide will
remain with the sodium oxide.
The Panel would expect this to be true also in the case of spray fire.
Thus, the principal iodine control problem associated with minor, iodine-
contaminated sodium fires will be one of cleaning up the deposited sodium
oxide and replacing particulate filters that might have become loaded with the
airborne sodium oxide.
The Panel recognized that although postulated major accidents and their
consequences will be entirely dependent upon the design of the reactor,
certain general observations can be made. The maximum credible accident
usually involves breaching of the primary system. Under these conditions,
the bulk of the sodium and fission products can be expected to remain within
the reactor vault or cavity. It is difficult to rule out the possibility of some
leakage occurring between the reactor cavity and the secondary containment
structure. As noted above, the iodine can be expected to remain with the
sodium or sodium oxide aerosols. The behaviour of the aerosols will be
dependent upon the concentration, density and size distribution of the aerosol
[12] . However, the iodine control problem will generally be the same as
that described above for minor fires.
The Panel noted that a different type of accident in which iodine is
released from the fuel directly to the containment atmosphere rather than
to the sodium has the potential for presenting a greater iodine control pro-
blem. This type of situation could result from a fuel-handling accident in
which the sodium coolant leaks from the fuel-handling machine with the sub-
sequent melting of a fuel assembly. Under these accident conditions, a
sodium oxide aerosol would be present in the containment atmosphere to act
as a scavenging agent for the iodine. Experiments have been described
(Baurmash, et al. , [11]) in which sodium was allowed to burn in an atmos-
phere containing molecular iodine. The results indicated that the sodium
oxide behaved as an excellent scavenging agent for the molecular iodine,
reducing the concentration of free molecular iodine by a factor of 100 within
a few minutes.
The Panel concluded that, due to iodine's affinity for sodium, radio-
iodine does not appear to present a serious control problem for liquid-
metal fast breeder reactors.
7. CONTROL OF IODINE EMISSIONS FROM REPROCESSING PLANTS
The Panel recognized that, although reprocessing plants serve a large

number of reactors and necessarily produce a number of effluent streams
containing substantial quantities of activity which need ultimately to be con-

tained or dispersed, a long delay between discharge from the reactor and
fuel processing can reduce the 131 I isotope to levels typically only a fraction
of a Ci/t of uranium.
This delay between discharge from the reactor and reprocessing occurs
in the reactor storage pond, in transit and in the reprocessing plant storage
pond. During this period the fuel retains its cladding and is usually free
from cladding defects. It is common practice for defective fuel, identified
as such in the reactor, to be placed in special containers during transport
and storage. For these reasons it has been found that there is no significant
release of iodine from the fuel during the cooling period.
The delay time ("cooling time") allocated to this part of the fuel cycle
does not appear to carry unacceptable economic penalties for thermal
reactor fuels at present, but the Panel noted that it was possible that there
may be some incentive to reduce the delay in certain circumstances even for
thermal reactor fuel cycles.
A reduction from 165 to 100 days "cooling time" increases the 131I by a
factor of 2 50 and to a level at which routinely reliable iodine removal systems
are essential for continuously operated plants.
The Panel noted there was general agreement that for long-cooled fuel
the distribution of iodine in the reprocessing plants results in the main part
of this iodine reaching the -aqueous effluent streams, in particular, the
first cycle solvent wash. The temporary storage of this stream before
further treatment substantially reduces the problem of dealing with iodine
in these systems. It was generally agreed that, for long-cooled fuel, the
residual 131I posed no significant problem in the ultimate disposal of aqueous
wastes.
The residual iodine in long-cooled fuel does, however, pose a minor
problem in the cleaning and disposal of gaseous effluents from the repro-
cessing plants. The radioiodine, released from the matrix of the fuel during
the dissolution stage, partitions the boiling dissolver liquid and the dissolver
atmosphere of nitrous gases, steam and air; most of the iodine can be
expected to be in this gaseous phase. However, the usual technology of
this process is to recover the nitrous gas by oxidation, condensation and
scrubbing with the cold feed of nitric acid to the dissolver.
Where continuous dissolvers are used, the system reaches steady-state
conditions and it is found that under these conditions most of the iodine is in
the dissolver solution while, typically, ~ 5% of the iodine is found in the
residual gases leaving the dissolver acid recovery unit. The proportion of
iodine in the dissolver solution and dissolver off-gas can vary with the
detailed design of the system and with the choice of batch or continuous
dissolution. Batch dissolution of high burn-up thermal fuels does give an
initial burst of iodine to the scrubber system and the latter has tobe designed
to achieve efficient scrubbing of the nitrous gases and thus, inter alia, of
iodine.
Experience available to the Panel from the United Kingdom, the Federal
Republic of Germany and the United States of America shows that the sub-
sequent scrubbing of the dissolver off-gas by means of a cool, counter-
current stream of sodium hydroxide solution gives a further decontamination
of iodine; reduction factors of about 50 are commonly achieved or expected
from tests. Current experience suggests that the scrubbed dissolver gas
stream contains, typically, 0. 1% of the iodine in the fuel fed to the dissolver.
Further data show that similar iodine decontamination factors are obtained
in scrubbers using 5% nitric acid containing O.OOIIV^ mercurous or mercuric
nitrate. The Panel noted that higher removal efficiencies for iodine from
dissolver off-gas are routinely obtained at the Hanford site in the USA. In
this case, greater removal is required because the concentration of iodine
in the fuel is higher as a result of using shorter cooled uranium fuel. The
method of treatment involves the use of silver pellets or of silver nitrate-
impregnated porous ceramic packing at 190°C in an adsorption tower following
liquid scrubbers. The removal efficiency of this unit varies from 99.9% to
99.99%. Final clean-up of the air stream is performed by a 'Fiberglas'
filter unit. The silver reactor can be regenerated by spraying a solution of
silver nitrate on the packing at 67"C followed by a baking period at 110°C.
The gas to the adsorber must be free of ammonia because a serious explo-
sion in the unit was traced to the presence of this compound.
For the removal of iodine the method of isotopic exchange of gaseous
iodine with Agí at 190°-200°C can also be used. A detailed description of this
method is given in Ref. [13].
The Panel drew attention to the contamination of vessel vent-air by
iodine-containing streams, especially if these were disturbed or heated, and
recognized that the iodine content of such air-streams can be minimized by
detailed consideration of liquor transfer and agitation devices. While there
is evidence that dissolver off-gases can be efficiently scrubbed with alkaline
scrubbers, there is little information on the removal efficiency of the
expected alkyl iodides from the solvent extraction cycles.
The discharge of the reprocessing plant air-streams via stacks
120 m high) is common practice and the Panel noted the long experience
of environmental monitoring of 131I, particularly for the critical path in
milk,in the United Kingdom and the United States of America. This has demon-
strated conclusively that the policy of cooling the fuel, coupled with the
scrubbing systems used, maintains the 131I level in milk at or below the
limit of detection for the measuring techniques normally used in monitoring
iodine concentrations in milk, 10-20 pCi/litre. In the United Kingdom
special trials of short duration, when up to 150 Ci 131I were fed to the re-
processing plant daily, substantiated the levels calculated from the disper-
sion deposition model.
The Panel observed that the use of the derived working limit (DWL) for
discharge of l31I requires evaluation for each site and may entail environ-
mental monitoring which is a sensitive and positive assessment of the ade-
quacy of the iodine-measuring devices used to monitor the stack air.
7.1. Fast reactor fuel reprocessing
The fast reactor fuel cycle requires a substantial inventory of plutonium

and, while in the early phases of fast reactor investment supplies of plu-
tonium will be adequate, a large nuclear program based on this reactor
will rapidly lead to the need to reduce to a minimum the plutonium inventory
of the fuel cycle.
The economic advantages of reducing the plutonium inventory in the fuel
cycle seem so substantial that there will be a strong incentive to establish
the technology necessary to achieve this aim. This will demand a rapid
recycle of the fuel which, in turn, requires reprocessing before the 131I has
decayed to levels currently handled in major reprocessing plants.
The Panel, while recognizing that the 131I problem was only one of
many associated with the reprocessing of short-cooled fuel, believed that it
was probably the most difficult one to solve if the requirements of regulatory
authorities are to be met. If a cooling time of 180 days is required before
reprocessing is possible, then the 131I content of 1 t of fast reactor fuel is
about 0 . 5 Ci, while at 50 days'cooling (judged to be a practicable cooling
time for a central plant) the 131I content is about 40 000 Ci/t of fuel. The
allowable discharge of the gaseous effluent from a plant processing 2 t
of fuel per day from a 120-m stack could be, typically, about 100 mCi/d,
requiring an overall decontamination factor
Í 131I in fuel \
v l in stack gas J
131
of 106 for 50-day cooled fuel.

These figures are given as examples to define the magnitude of the task,
and the Panel felt that the need for a margin of safety in design and the
requirement to use the best practicable means for reducing emissions would
lead to a target decontamination factor of 107 - 108 for the gaseous effluent
streams.
This is about 100-1000 times greater than the highest decontamination
factor recorded for chemical plants (about 105 for the Hanford plant and 10 4
for the RALA process at Idaho) and the Panel identified one of the major
problems in iodine containment to be that of reducing adventitious losses
through minor air leaks, spillages and ventilation upsets in an intensively
worked production plant.
The merits of the removal of iodine from the system at an early stage
of the process were considered and it was agreed that such an approach
offered the best route to a successful design.
The techniques discussed were (a) those relying on heating of the dry
fuel in a gas-stream from which, after cooling, iodine could be scavenged
by a scrubbing system (wet scrubbers followed by silver- or lead-impregnated
beds or dry scrubbers alone) or (b) conventional acid dissolution followed by
removal of iodine from the dissolver solution, e . g . by steam distillation,
and trapping of iodine in the gas from the condenser system by scrubbers and
solid absorbers.
The development of these techniques is at an early stage and the choice
of one or other of the routes will depend not only on the successful outcome
of the iodine removal and trapping development work but also on other factors.
For example, it may be desirable, for reasons other than iodine pre-
treatment, to convert carbide fuels to the oxides by high-temperature
oxidation — a process stage that could simultaneously remove iodine from
the fuel.
The trapped iodine will consist of 127I, 129I and 131I (about 400 g/t fuel)
and it was noted that direct trapping of the iodine present in the fuel by
silver-loaded zeolites or catalyst beds would be expensive, especially if
silver recovery or regeneration is not economically feasible. The life of
such beds under reprocessing plant conditions is not known and a development
program will be required to establish the feasibility of their use. It was
agreed that prior scrubbing with NaOH solution or HNOg-containing mercury
might improve the overall economics of the iodine removal systems. Liquid
scrubbers will lead to large volumes of aqueous effluent which may be eva-
porated and stored while the 131I decays. Although there is some evidence
that iodine does not readily distil from NaOH solutions, the decontamination
factors obtainable are unknown; the target required is estimated as 107 - 108
from iodine in store to that released to atmosphere. There are no data which
the Panel could use to predict the efficiency of liquid scrubbers under all fast-
reactor processing plant conditions. More information is required in cer-
tain areas, such as possible interference by some ions and compounds.
The Panel noted that there were many factors in common with the pro-
blems of scrubbing reactor gases under accident conditions and those ap-
pertaining to the final clean-up of reprocessing plant effluent air. It con-
sidered that exchange of expertise in these two fields would be of the utmost
value, if attention is duly paid to the differences between the two systems.
The Panel did not consider in any depth the problems of 131 I containment
during the transport of short-cooled reactor fuel but noted that the release
of only a small fraction of the total 131I in a flask of 50- day cooled fuel
could give rise to a major incident and that it was therefore essential that
such flasks and their mode of transport must be assessed for the maximum
credible accident conditions.
Finally, on a more optimistic note, there was general agreement among
Panel members that the disposal of 129[ would not pose any severe problems
in the environment.
The Panel concluded that the reprocessing of short-cooled ( e . g . 50 days)
fast reactor fuel in intensively worked commercial reprocessing plants
would pose problems which require the development of new techniques for:
(1) The removal of 131I from the vessel-vent and cell air-streams from
reprocessing and waste treatment plants;
(2) Containment against accidental release; and
(3) Special consideration of short-cooled fuel transport and the study
and testing of designs to remove the associated hazards.
It was agreed that there were several possible approaches to these
problems and that development must be specific to the fuel design and to the
process and plant concept developed by the designer. The testing of such
equipment must ultimately be done on full-scale prototypes and there is
undoubtedly merit in the proposal to equip reprocessing plants with iodine
suppression, storage and control systems at an early stage so that several
years'experience can be gained with longer cooled fuel with typical plant
off-gas compositions (apart from 131 I concentration) before the plant is
intensively worked with short-cooled fuel.
8. CONCLUSIONS
The chemical and physical state of radioiodine has a marked effect on

its behaviour in gaseous environments. It is now well established that in
the gas phase various inorganic and organic compounds may be present. In
particular, molecular iodine, methyl iodide and iodine sorbed on particles
have been found. The presence of these and other forms may require the
use of special techniques or sorption systems to remove radioiodine effi-
ciently from exhaust gas streams. It is also well known that the presence
in the gas stream of other, and for the most part unspecified, substances
may impair the performance of sorption devices which in clean air may be
effective. The Panel noted that while there now exists a large amount of
experience in handling these and related problems, it is still not possible to
give rules of thumb which would be generally valid for the removal of air-
borne iodine.
The Panel noted nevertheless that, on the basis of the evidence available
to it, there did not seem to be any applications in nuclear power reactor
systems or fuel processing plants in common use today for which clean-up
systems for iodine could not be built to meet existing safety standards.
However, the Panel felt that it could not recommend system designs for
general use even for a particular application. Indeed the Panel emphasized
that the selection and detailed design of a clean-up system must be made
after careful examination of the relevant parameters (gas flow-rate, amount
of iodine, forms of iodine, humidity, temperature, impurities, etc.) to
achieve a solution adequate in safety, efficiency and economy.
Noting that clean-up devices for iodine have sometimes given unpredict-
able results, the Panel considers it essential that such clean-up systems be
appropriately tested routinely to prove their continuing ability to meet safety
standards. While the Panel felt that existing technology of iodine clean-up
systems was available for most current applications involving potential
iodine hazards, it noted that this may not be so if fast-breeder reactor sys-
tems come into general use. In this case, a strong economic incentive to
reprocess fuel relatively soon after its removal from the reactor implied a
considerable increase in the amounts of radioiodine available for release
during fuel reprocessing and a correspondingly higher decontamination
factor may be required.
The Panel emphasized that there still remains a need to investigate
quantitatively the chemistry of airborne iodine and to develop better sampling,
analytical and performance-testing techniques. However, the Panel also
emphasized that the amount of investigatory work undertaken for specific
applications would have to be justified by the magnitude of the potential
radiological hazard presented.
The Panel noted that problems or potential problems posed by the
radioiodine in nuclear reactors and fuel processing plants could be handled
by several alternative means, of which sorption or trapping of iodine from
process air systems was but one. Other methods include, for example,
siting of reprocessing plants away from agricultural and residential areas
and changes in the reprocessing conditions. The ultimate choice of method
or combination of methods would depend on local factors and economic con-
siderations. The Panel therefore avoided making specific recommendations.
Finally, while the Panel concerned itself primarily with the potential
sources of airborne iodine associated with nuclear power reactors and fuel
reprocessing plants, it also noted that other potential sources existed.
These include centres for isotope production and handling as well as hospitals
and research institutes in which increasing use is being made of iodine
isotopes.
REFERENCES
[1] Recommendations of the International Commission on Radiological Protection (Adopted 17 September 1965),
ICRP Publication 9, Pergamon Press, Oxford (1966).
[2] principles of Environmental Monitoring Related to the Handling of Radioactive Materials, ICRP Publication 7,
Pergamon Press, Oxford (1965).
[3] Background Material for the Development of Radiation Protection Standards, Federal Radiation Council
Report N o . 2 (1961) ; and Radiation Protection Guidance for Federal Agencies, Federal Register, Federal
Radiation Council, 13 September 1961.
[4] Background Material for the Development of Radiation Protection Standards, Federal Radiation Council
Report N o . 5 (1964) ; and Radiation Protection Guidance for Federal Agencies, Federal Register, Federal
Radiation Council, 22 August 1964.
[5] BRYANT, Pamela M . , Data for assessments concerning controlled and accidental releases of 13I I and
m C s to atmosphere. Health Phys. 17 (1969) 51.
[6] BRYANT, Pamela M . , Derivation of working limits for continuous release rates of m I to atmosphere in a
milk-producing area, Health Phys. ¿ 0 (1964) 249.
[7] BRYANT, Pamela M . , Derivation of working limits for continuous release rates of I29 I to atmosphere,
Health Phys. 19 (1970) 611.
[8] BEATTIE, J . R . , BRYANT, Pamela M . , Assessment of Environmental Hazards from Reactor Fission Product
Releases, UKAEA Rep.AHSB(S)R 135, HMSO (1970).
[9] Air Filters for Use at Nuclear Facilities, IAEA T e c h . R e p . N o . 1 2 2 , IAEA, Vienna (1970).
[10] VANSLAGER, F . E . , BELL, W . E . , SISMAN, О . , MORGAN, M . T . , GA-10073 (1970).
[11] BAURMASH, L . . NELSON, C . , GRANGER, J . , KOONTZ, R . , "Behaviour of iodine in the presence of
sodium oxide aerosols", presented at the 11th AEC Air Cleaning Conference, September 1970.
[12] Aerosol Modelling of Hypothetical LMFBR Accidents, AI-AEC-12977, Atomics International, North
American Rockwell.
[13] NAKHUTIN, I . E . , e t a l . , "Removal of radioactive iodine from gases", 4th I n t . C o n f . P e a c e f u l Uses
At.Energy ( P r o c . C o n f . G e n e v a , 1971), U , UN. New York, and IAEA, Vienna (1972) 399.
ANNEX:
WORKING PAPERS
CONTROL OF RADIOIODINE RELEASE
FROM REPROCESSING PLANTS
Pamela M. BRYANT
National Radiological Protection Board,
Harwell, Didcot, Berks
B.F. WARNER
UKAEA,
Windscale Works,
Sellafield, Cumberland,
United Kingdom
Abstract
CONTROL OF RADIOIODINE RELEASE FROM REPROCESSING PLANTS.

At fuel reprocessing plants the levels of 131 I can be significantly reduced by allowing it to decay before
the decanning and reprocessing of the fuel. Further control is achieved at Windscale by monitoring stack
emission for 1S1I and by monitoring its critical path in the environment, i . e . to milk. A review is given of
the experience gained in reprocessing Magnox fuel through the second Windscale reprocessing plant and
DFR fast reactor fuel through the Dounreay reprocessing plant. The methods used to monitor the discharge
and the environment are discussed and the principles used to calculate the derived working limits for 131I
and 1291 are given. Using this experience, an assessment is made of some of the problems likely to be met in
the processing of short-cooled fast reactor fuel, with particular reference to gaseous and liquid effluents.
1. INTRODUCTION
The problem of iodine release from reprocessing plants would be

severe, were it not possible to allow the radiobiologically significant
isotope 131 I to decay before decanning and reprocessing take place.
Current United Kingdom Government policy [1 ] requires that dis-
charges of radioactive wastes shall be reduced by the best practicable
means so that any resulting radiation doses to members of the public will
be at levels far below the dose limits recommended as maximum exposure
levels by the International Commission on Radiation Protection. Operational
guidance to this end is provided in the UK by derivation of working limits
(DWLs) for discharges which correspond to the recommended dose limits.
It has been the practice in the United Kingdom to allow the 131 I to decay to a
level at which the emission from the reprocessing plant stack is well below
the derived working limit. The cooling time required for a given fuel rating
and throughput is a function of the efficiency of various gas scrubbers. This
policy so reduces the 131I content that its level in aqueous effluents does
not at present pose any significant problems.
This paper reviews the experience gained in reprocessing Magnox fuel
through the second Windscale reprocessing plant and DFR fast reactor fuel
through the Dounreay reprocessing plant. The methods used to monitor
the discharge and the environment are discussed and the principles used to
calculate the derived working limits for 131 I and 129I are given. Using this
29
30 BRYANT and WARNER
experience, an assessment is made of some of the problems likely to be

met in the processing of short-cooled fast reactor fuel, with particular
reference to gaseous and liquid effluents.
2. EXPERIENCE FROM THE SECOND WINDSCALE REPROCESSING

PLANT
2.1. Control of radioiodine
The second separation plant at Windscale was primarily designed to

process 1500 t / y r of the uranium metal arising from Magnox reactors.
The Magnox fuel is natural uranium metal, clad in magnesium metal alloy
and has an average irradiation of 3000 MWd/t at a mean rating of 2. 7 M W / t .
It is cooled in the reactor pondá for at least 90 days before transport.
The 131 I content is a function of the fuel rating and cooling time, whilst
the 129 I and 121 I content is largely governed by the fuel irradiation.
The control of radioiodine release from this plant is achieved by
aging the fuel before treatment, thus limiting the 131 I input to a level
consistent with the lowest practicable discharge from the plant stack.
This philosophy of design thus obviates the need for elaborate and highly
efficient absorbers for 131 I, although some decontamination of the gaseous
effluents is achieved with general-purpose sodium hydroxide scrubbers.
The discharge of radioiodine from the stack is more restrictive than
that to sea. The iodine release to the stack is controlled by authorizations
issued jointly by the Ministries of Housing and Local Government and of
Agriculture, Fisheries and Food, which require the best practicable means
to be used to minimize radioactive emissions to air. The biological environ-
ment is monitored in accordance with a schedule prepared by the Ministry
of Agriculture, Fisheries and Food and agreed by the Ministry of Housing
and Local Government.
To assist in establishing data on the distribution of 131I in the food chain,
a small proportion of short-cooled fuel has been fed to the plant for short
periods by agreement with the controlling authorities. These trials have
yielded information on the behaviour of iodine within the plant as well as
its distribution in the environment.
In brief, the control of radioiodine emission from the plant is achieved
by:
(a) Aging the fuel;
(b) Monitoring stack emissions for 131 I;
(c) Monitoring the critical path (milk) in the environment.
An additional safeguard is provided by the NaOH scrubbers on the

vessel vent air.
2. 2. The iodine content of Magnox fuel
The Magnox reactors have average fuel ratings ranging from 2. 3 to

3 . 3 M W / t U, with peak ratings up to 4. 3 M W / t . The 131 I content and its
variation with cooling time is given in Table I.
41
RADIOIODINE FROM REPROCESSING PLANTS
TABLE I. IODINE-131 CONTENT OF MAGNOX FUEL AND VARIATION

WITH COOLING TIME
Curies of 131I per tonne of fuel

Fuel
with cooling time (days) of:
rating
( M W / t U)
Od 33 d 60 d 100 d 167 d
2.3 60 000 3200 350 12 0.04
2.7 71000 3800 400 14 0.05
3.3 87 000 4700 500 17 0.06
4.3 112 000 6000 650 21 0.07
The daily input of the plant can vary between 5 and 8 t U and the
figures in Table I must be multiplied by these factors to obtain
the daily input of 131 I. Typically, at 7 t/d and 167 days' cooling, even the
highest rated fuel gives an input of only 0. 5 C i / d .
2.3. Outline of the second separation plant
This plant has been described in the literature [2, 3] and, for the
purpose of this paper, it is only necessary to recall its main features.
The Magnox-clad fuel is stored in a cooling pond from which, after
mechanical decanning, it is transported in shielded flasks to the dissolver
charge machine. The individual fuel rods are fed continuously to the
dissolver, from which the nitrous fumes flow counter-currently to an
incoming feed of nitric acid in the fume-oxidizer and absorber unit. This
unit, fitted with an inter-stage cooler, acts as a gas scrubbing unit as
well as a fume absorber. The dissolver off-gases which leave the fume
absorber consist of excess oxygen, air from in-leakage, noble fission
product gases and some N 2 0 . These are further scrubbed by recirculating
NaOH solution before passing to the main ventilation system to join other
ventilation streams (see below).
The solvent extraction plant is separated into highly active and medium
active cells and the ventilation air flows from the operations area to the
access area and thence to the active cells. This air is vented separately
via two heater/filter units to the stack, leaving the latter at the 90 m level.
The vented air from the process vessels, all of which operate at an
air pressure about 5 cmHg below the cell air pressure, is separately
routed through recirculating NaOH scrubbers and thence to a separate pair
of heater/absolute-filter units, one situated at the plant and the other at the
base of the stack. This filtered air is discharged at the 120 m level. The
gas stream from the dissolver system joins the vessel vent air prior to
the primary filter unit. The solvent extraction system is described in [ 2 ] .
Insofar as the fate of iodine is concerned, it is sufficient to note that
the main aqueous effluents can be systematized as in Table II.
TABLE II. MAIN AQUEOUS EFFLUENTS FROM SECOND SEPARATION

PLANT
Highly active raffinate PSI AR - Evaporate and store permanently.
Medium active raffinates PS3 AR and UP1 AR — Evaporate

and delay store.
Highly active solvent Monitor and discharge to sea.

wash wastes
Low active solvent Monitor and discharge to sea.

wash wastes
Nitric acid overheads from Fractionate to recover nitric acid and

raffinate evaporators discharge overheads to sea.
2. 4. The fate of iodine in the separation plant
2.4.1. The dissolver system
There is no significant release of iodine to the cooling pond during the

decanning process. The iodine is released on dissolution and is distributed
between the dissolver liquor and the nitrous fume. The underlying chemistry
of iodine in the dissolver has not been fully explored, largely because the
very low input of radio-iodine to the plant has not led to any difficulties which
would justify expensive, fully active research. However, some investi-
gations have been made and may be of interest.
Reactions of significance to the dissolver conditions, assuming the
iodine in the fuel is present as I 2 and metallic iodides, are:
I2 + 2e - 21" E0 = 0 . 5 4 V
6H + + IOS + 5e - |I2(S) + 3H 2 0 Eo = 1.20 V
8H + + IO¿ + 7e - |I2(S) + 4H 2 0 E 0 = 1. 34 V
Postulated hydrolytic reactions are:
I 2 + H 2 0 ^ HI + HOI
3HOI г* Ю~з+ 3H+ + 21"
The above basic reactions will be affected by the nitrous and nitric acid
concentrations and may be affected by the continuously dissolving uranium
metal, radiolysis products or intermediates and fission products such as
Pd and Ag having insoluble iodides.
Some limited experimental work has been carried out at Windscale in
an attempt to identify the species present in dissolver solution. The free
I 2 content was estimated by the addition of carrier iodine and extraction
41
into CC14, whilst the IO¿ content was determined by the subsequent addition
of carrier IO^to the solution, reduction by KI and a further CC14 extraction.
The results showed that 9 5% of the iodine was present as I 2 and 5% as Ю 3 .
This work also showed no change in the ratio of 1 2 /Ю 3 when the cooled
dissolver solution was aged for 7 days. These results are consistent with
the observation that it is possible to steam-distill 70 - 85% of the iodine in
dissolver solution and that I0 3 is stable to a radiation dose of 10 5 rad [ 4 ] .
The chemical mechanism leading to the small proportion of IC3 in
dissolver solution has not been established; it is well known that I 0 3 i s
produced by the reaction of I2 and strong nitric acid, but the extent of its
formation in dissolver solution continuously purged by nitrous fume cannot
be calculated owing to lack of data. It has been suggested, but not proven,
that the intervention of fission product silver produces iodate ion according
to the reaction:
6Ag + 3I2 + ЗНгО 5Agl + AgI0 3 + 6H+
The absence of iodide ion is consistent with the expected oxidation of I "by
boiling 3N H N 0 3 in the presence of NC^.
Using this background information, one can postulate that the iodine
is present in the dissolver chiefly as which steam-distills with the acid
vapours to the oxidizer-scrubber, where a substantial fraction is refluxed
by the cool H N 0 3 stream returning to the dissolver.
Some small fraction ( e . g . 5%) of the iodine fed leaves the oxidizer-
scrubber to reach the NaOH scrubber, in which the main part (—98%) of the
131 I is removed from the gas stream.
Figure 1 shows the measured behaviour of 131I over the dissolver,

fume-oxidizer and scrubber system and it is to be noted that the release of
131 I to the ventilation system is only 0 . 1 % of that fed to the plant. The
release measured at the stack includes that from the scrubber vessel vent
air, and separate measurements of iodine in this stream are not available.
However, from experience on the first separation plant, the overall
decontamination factor for 131 I of the dissolver-fume-oxidizer-scrubber
system is 30 and if this figure is applied to the mass balance in Fig. 1 we
can infer that most of the 131 I measured in the stack gas is derived from
the dissolver system and that the contribution of the scrubbed vessel vent
gas is small.
In the above discussion it is assumed that the absolute filters do not
significantly contribute to the decontamination of the air stream.
2 . 4 . 2. The solvent extraction system
Measurements of the 131 I distribution in the second separation plant

were made on both the small pilot plant and the main plant itself using a
small proportion of short-cooled fuel in the feed. The two sets of results
are broadly consistent and the distribution found on the plant itself is shown
in Fig. 1. Although this trial was of short duration, the mass balance is
satisfactory; most of the iodine fed to the plant is accounted for by that
leaving in the effluent streams. The level of iodine in the recycled, washed
solvent is to be noted.
ëн ¿¡-
3
2
tí- юOi
41
On reducing the 131 I content of the feed to its normal level, the 131 I
content of the recycled solvent returned to a low level within a few days.
It is possible, but not proven, that the 131 I undergoes a relatively slow
exchange with more persistent compounds of 129 I and 127I already present.
Examination of Fig. 1 shows that the distribution of radioiodine in the
aqueous effluents is largely confined to the first and second cycles and
that 75% of that fed is found in the solvent wash aqueous wastes. At present
these are discharged to sea, the 131 I and 129 I content being well below their
respective derived working limits.
The date of the low levels of 131 I in the evaporation systems used to
concentrate the acidic wastes from the solvent process was not established
during the trial, but laboratory tests suggest that a substantial proportion
will reach the acid fractionation tower and appear in the overhead stream
which is sent to sea.
2. 5. Summary of the behaviour of iodine in the separation plant
Of 100 parts of 131 I fed to the plant, 0 . 1 parts are found in the gaseous
effluent and at least 75 parts are discharged to sea. On average, the 131I
in the long-cooled fuel fed to the plant is about 0. 5 C i / d hence 0. 5 mCi/d
leaves the stack and 0. 4 Ci/d is sent to sea.
3. DERE PLANT EXPERIENCE
The small DERE chemical plant processes enriched uranium fuel from
the DFR fast reactor and has been described in the literature [ 5 ] . Broadly
speaking, thé process consists of batch dissolution followed by three co-
decontamination solvent-extraction cycles in pulsed mixer settlers
employing 20% TBP as the organic phase. Againthe philosophy of control
of 131 I follows that described for Windscale, reliance being placed on
aging the fuel before it is fed to the plant.
Some experience on the behaviour of iodine in the plant has been gained
and it is useful to make such comparisons as are possible with the Windscale
experience. The plant has operated on 90-day cooled fuel with an 131 I feed
of up to 2 - 3 Ci/kg U. A batch dissolver, fitted with an off-gas condenser
system is employed and the nitric acid is fed directly to the dissolver.
Allardice [ 6 ] found that 95% of the iodine would volatilize during dissolution
and that the dissolver off-gas scrubber (a packed tower with water
recirculation) would only give a D F 1 3 1 I = 10, insufficient to reduce the 131 I
to acceptable levels. However, the substitution of 0. 5M H N 0 3 / 0 . 001M HgN0 3
solution for water in the scrubbing tower increased the decontamination
factor to 200.
The residual iodine in the dissolver liquor (5%), when fed to the first
solvent extraction cycle, divided itself between the aqueous raffinate and
the solvent extraction, up to 2 - 3 % of the iodine in the dissolver liquor
being found in the solvent product and this was retained after solvent
washing. Smaller amounts of iodine were found in all streams of the
process following the first cycle but were insufficient to affect the process
or product. Saturation of the solvent with inactive iodine reduced the rate
of build-up of 131 I in the solvent but did not substantially affect the ultimate
level reached.
4. RADIOLOGICAL ASPECTS OF RADIOIODINE DISCHARGES TO

ATMOSPHERE
4.1. Principles of the derivation of working limits
Working limits for contamination of environmental materials and for
rates of discharge of radioactivity to atmosphere are derived in the UKAEA
from the upper limits of dose, called dose limits, for members of the public
set out in ICRP Publication 9 [ 7 ] . These dose limits have been endorsed,
as upper limits, for application in the United Kingdom by the Medical
Research Council; that for radioiodine takes the form of an annual dose
limit to thyroid glands of members of the public. It is not feasible to
measure routinely doses received by human thyroids (although the biological
monitoring program includes routine examination of sheep thyroids) and it
is useful to derive a working limit in an appropriate environmental material,
for example milk. Measurements of the 131 I content, if any, of milk samples
can be compared with the DWL in milk to indicate approximate levels of dose,
as a fraction of the dose limit, received by members of the public who
drink the milk.
The critical exposure pathway traversed by radioiodine discharged to
atmosphere is often deposition on pasture grazed by cows and ingestion of
cows' milk by infants during their first year of life. Infants of 6 months
may be taken as representative of the first year and constitute the critical
group because of the predominance of milk in their diet and the small size
of their thyroid glands. It is postulated that all the milk consumed by this
hypothetical group during the year will be from cows grazing contaminated
pastures. This ensures that the estimated dose to the hypothetical group
provides an upper limit to the dose that any real critical group could
receive. The DWL in milk, derived on the above basis, provides an upper
limit of contamination which corresponds to the dose limit and from which
an upper limit for the discharge rate of radioiodine, designated in the
UKAEA the derived working limit for the continuous release rate, can be
derived. The significance of measurements of discharges can be judged
by reference to this DWL. In practice, discharge rates to atmosphere are
usually a small fraction of the DWL due to plant design and management
appropriate to the requirement that the best practicable means shall be
employed to minimize discharges.
Radioiodine, discharged in volatile or sub-micron particulate form, is
dispersed by the normal turbulence of the atmosphere and some will reach
ground level where it may be deposited on pasture. Some of this will be
transferred to the milk of cows grazing the pasture. Numerical values for
the parameters involved in dispersion, deposition and transfer of radio-
iodine to milk are selected with the intention of giving a moderately con-
servative relationship between the DWL in milk and corresponding DWLs
for continuous release rates appropriate to the circumstances of individual
discharges.
Discharges may not be at a steady rate for operational reasons and it
is recommended that the amount of radioiodine discharged in a few hours
should not exceed that permitted for one week. It is considered that this
practice might cause radioiodine levels in milk to r i s e for short periods to
several times the average level, but would not give rise to unacceptable
doses expressed as fractions of the annual dose limit. Thus operational
flexibility is combined into effective control.
RADIOIODINE FROM REPROCESSING PLANTS 37
4. 2. Derived working limits for the Windscale reprocessing plant
The iodine isotope of greatest importance with respect to potential

discharges from the Windscale reprocessing plant is 131 I (8-day half-life).
The DWL in milk corresponding to the current dose limit of 1. 5 rem/year
for children under the age of 16 years [ 7] is 400 p C i / l ; this was derived
from metabolic and dosimetric data [8] approved by the Committee for
Protection against Ionizing Radiations of the United Kingdom Medical
Research Council. This derivation and an earlier one also leading to a
DWL of 400 p C i / l [9] are summarised in [ 1 0 ] .
DWLs for continuous release rates of 131I to atmosphere, corresponding
to the DWL in milk of 400 pCi/l, can be read from Fig. 2 of Ref. [9]
for several chimney heights over a range of distances from the
chimney to pasture land. There are three discharge points at Windscale
connected with chemical reprocessing of fuel; points A and В on the same
stack are at 120 and 90 m above ground and it is calculated that, because of
down draught effects, the effective height of point В is 60 m. These dis-
charge points serve different extract systems of the second separation plant.
Point С (120 metres) serves the head-end plant and the highly active
evaporation and storage plant. DWLs for points A and С are 0. 65 Ci/d
(230 Ci/yr), and for point В is 0. 15 Ci/d (50 Ci/yr), all considered
independently of one another. If actual discharges were required to be
appreciable fractions of the respective DWLs, appropriate control would
be applied to restrict the combined effect of the discharges. The regions
of maximum deposition from the three discharge points overlap within about
1 km of the site.
The above DWLs were derived using simplifying meteorological and
agricultural assumptions. Dispersion in the atmosphere depends upon the
speed of the wind and turbulence of the air caused by solar heating, un-
evenness of the terrain and other factors. Weighted mean concentrations for
unit continuous release rate of windborne material were computed for England
and Wales as a whole by taking the frequency of occurrence of different
classes of weather into account and assuming an even distribution of wind
direction as an average throughout the year [ 9 ] . The situation at Windscale
is not significantly different from this as wind speeds tend to be higher than
average when the wind is from the "prevailing" direction.
Radioiodine is deposited on the ground and on vegetation by diffusion
and impaction processes and wash-out by rain; rates of deposition depend
upon chemical and physical form, particle size, wind speed and rainfall
rate. It is known that a proportion of radioiodine released from the
processing of irradiated fuel elements may appear in organic form,
particularly as methyl iodide [11, 12]. The inorganic portion may be as
elemental iodine or attached to sub-micron particles. The dry deposition
velocity 1 to vegetation of methyl iodide was found to be about 10" 5 m / s
compared with about 10" 2 m / s for elemental iodine [13], while that of sub-
1 Deposition velocity =
rate of deposition of activity per unit area of ground

concentration of activity in air near ground
When the ground carries vegetation, the deposition velocity reflects the higher deposition rate on vegetation
compared with the ground surface itself.
micron particles may be about 10"3 m / s . The methyl iodide portion of a

release, which was found in the case of the Hanford Purex plant to vary
from 10% to 60% [14], contributes a negligible proportion of the conta-
mination of milk compared with the inorganic portion. A safety factor of
up to two in respect of the chemical form is involved in the simplifying
assumption that all the iodine released from the reprocessing plant is
elemental iodine with a deposition velocity of 10"2 m / s . The use of this
value takes no account of the possibility that some or all of the inorganic
iodine may be attached to sub-micron particles (with a lower deposition
velocity) or that the net effect of wash-out by rain may be to enhance
deposition of airborne iodine rather than to remove iodine already deposited
on vegetation. Deposition velocities also vary with weather conditions,
tending to be somewhat lower in inversion conditions with low wind speeds
than in the more usually occurring weather in the United Kingdom with
higher wind speeds. Taking all the relevant factors into account, it is
considered that 10" 2 m / s may be taken as representative of annual average
meteorological and plant conditions at Windscale for the purpose of
calculating the DWL for the continuous release rate.
Values chosen for the parameters involved in transfer of radioiodine
to milk [ 9 ] are based on good grazing conditions in early summer in
Southern England; they may involve a safety factor of two -when applied to
the Windscale area, which is in Northern England where cows are kept
indoors and given supplementary feed for several months in winter. It
must be stressed, however, that all the parameters are subject to
considerable individual variation and any generalization to within a factor
of two in this sphere is difficult.
Working limits for another isotope of iodine, 129I (half-life of 17 million
years), are of interest because increasing use of nuclear power reactors
implies greater production than hitherto of long-lived fission products, which
may become significant from a public health point of view. The grass-cow-
milk pathway used for calculating DWLs for 131 I can also be used, with
appropriate modification, for I29 I. An alternative method involves the
specific activity concept where the term specific activity refers to radio-
activity of 129I relative to mass of stable iodine, e. g. Ci 1 2 9 I/g 121 I in the
medium of interest. Strictly, the specific activity should be expressed in
terms of total iodine mass, but up to permissible levels the effect of the
mass o f 1 2 9 I can be neglected. The specific activity method is valid if there
is no change in the specific activity, produced in air by dispersion of dis-
charged 129 I, along the critical pathway to human thyroids.
In an appraisal of the two methods [15], it was concluded that DWLs
for 129 I calculated by the specific activity method are appropriate for
design purposes. The limiting specific activity in infant thyroids was
calculated to be 6. 2 X 10"6 ^Ci 129I/Mg 127I corresponding to the dose limit of
1. 5 r e m / y r . Combining this with a representative concentration of stable
iodine in air of 0 . 1 jug/m 3 , the limiting concentration in air is
6. 2 X 10"7 ^Ci 1 2 9 I/m 3 . The corresponding DWL for discharge points A
and С is 1. 2 C i / d and for point В is 0 . 2 7 C i / d . These values may well
involve a safety factor of up to ten for the Windscale site as stable iodine
concentrations in air near the sea may be as high as 1 ng/m3. DWLs
calculated for the grass-cow-milk pathway are up to ten times more
restrictive than those given above; as conservative values were used for
agricultural parameters, this is not unexpected. The specific activity
41
method itself probably includes a margin of safety as it is likely that other

sources of stable iodine, e . g . supplementary feed for cows, will reduce
the specific activity along the pathway from air to infants' thyroids. There
is no evidence that enhancement of the specific activity is likely, though
the possibility exists.
4.3. Stack and environmental monitoring program
Control of radioiodine discharges to atmosphere is exercised by

monitoring the effluent stream as it passes up the stack. The instrumentation
and sampling facilities provided for discharges of 131 I from point A (the most
important of the three discharge points) consists of beta-monitoring by a con-
tinuous monitor fitted with a recorder and alarm, and 131 I sampling using a
Maypack. The continuous monitor detects any break-through o f 1 3 1 I but is not
sufficiently sensitive to assess the normal low-level daily discharge; the
131 I sampler is provided for this purpose. The Maypack consists of two
Whatman 90 filter papers to remove particulate fission products and treated,
activated charcoal granules to absorb methyl iodide and elemental iodine.
The granules are supported by glass-fibre paper on a wire-mesh grid.
Normally, the beta monitor and Maypack samplers are changed weekly. The
131 I on the charcoal is assessed using a NE 8421 radioiodine monitor with
a correction factor for radioactive decay during the sampling period. The
discharge rate of 131 I is estimated from information on sampling and stream
flow rates.
Proof of effective control rests with results of the milk monitoring
program. Currently there are ten designated farms from which samples
of milk are collected at fortnightly intervals. Five farms are within two
miles of the Winds cale site and five are between two and four miles away.
Samples are also taken occasionally from bulk supplies at a local Milk
Marketing Board centre. In addition, samples are taken from two reference
farms at about 20 miles from the site. During the few trials with small
amounts of short-cooled fuel, sampling was carried out daily at farms
selected on the basis of wind data.
131 I in milk is determined by the method published in [ 1 6 ] . Aliquots of
milk are first evaporated in the presence of sodium iodide carrier and then
ashed. In a multistage process, the iodine is precipitated as silver iodide
which is mounted on a counting tray for gravimetric determination of
chemical yield prior to the measurement of beta-activity using standard
GM counting equipment calibrated to allow for self-absorption.
4.4. Correlation of stack and environmental monitoring results
Except during the trial periods when small amounts of short-cooled

fuel were added to the main feed, or when fallout levels were high, levels
of 131 I in milk have been below the reporting limit of 20 pCi/1 (based on
the limit of detection of 10 pCi per 500 ml sample portion [16]). This is
to be expected as normal discharge rates of about 0. 5 mCi/d from the
separation plant would produce average levels of about 0. 3 pCi/1, with
peaks of no more than a few pCi/1, on the basis of the relationship used
to calculate the DWL (0. 65 C i / d corresponding to an average of 400 pCi/1
in milk or 1 mCi/d corresponding to an average of 0. 6 pCi/1).
The measured discharge rate during one trial with an 131 I feed rate of
about 150 Ci/d averaged 90 mCi/d, which corresponds theoretically to an
average of 55 p C i / l in milk. However, measured concentrations in milk
at the worst affected farm averaged about 180 pCi/l over the month of the
trial, with a peak value of almost 400 pCi/l. During this restricted period,
the wind blew towards the sector occupied by the farm for 20% of the time,
compared with the theoretical average of 8%, but this was offset by an
average windspeed about three times the typical mean windspeed used in
calculating the DWL. If the radioiodine was discharged wholly in elemental
form, the effective deposition velocity during the trial could have been up
to three times the representative value of 10"2 m / s , but evidence from
other separation plants indicates that elemental radioiodine may constitute
only about half of the iodine discharged. Another uncertainty lies in
measurements of the discharge which, on present techniques, would not be
expected to give an accuracy of better than a factor of about three.
It is concluded that, considering all the variables involved, the measured
average level of 180 pCi/l in milk is not unreasonable compared with the
predicted average of 55 p C i / l .
5. REPROCESSING SHORT-COOLED FAST REACTOR FUELS
5.1. General
Economic assessments of a combined fast reactor and thermal reactor

program show that there will be a substantial benefit in reducing to a
minimum the quantity of plutonium required to operate the program.
Hence there is a strong incentive to reduce the fuel cycle time,
particularly the fuel cooling time, to a practical minimum if a large
program of fast reactors is contemplated.
Such a demand leads to severe problems in the control of 131 I during
transport and reprocessing.
5.2. Iodine content of short-cooled fuel
If one considers a conceptual reprocessing plant, on a central site,

handling only 2 t / d of core plus breeder fuel (at 10% burn-up in the core
fuel, equivalent to about 22 500 MW(e)), the 131 I content of the daily feed
is given in Table III. The size of plant is not likely to be less than 2 t/d
and could well be twice this figure.
The 129 I content of the feed to a 2 t/d fast reactor plant is about
100 mCi/d and, as is demonstrated in Section 4.2, this is less than the DWL
for discharge to atmosphere ( ~ 1 C i / d from a 120-m stack). Similarly,
for aqueous effluent to sea, this amount is within the estimated DWL.
Hence this isotope will not be considered further in this paper as 131 I will
be the major problem.
The fuels principally under consideration are (UPu)0 2 and (UPu)C,
and methods for their reprocessing are being examined prior to
initiation of a major development program, in which assessment and
investigation of the methods available for safe handling of radioiodine will
be an important item.
RADIOIODINE FROM REPROCESSING PLANTS 4 1
TABLE III. IODINE-131 CONTENT OF FAST REACTOR FUEL
Cooling time (days) 10 30 50 90 180
C i / d (2 t / d plant) 2 X 106 4 X 10 5 8 X 104 2 x 103 1
Work on the problem of iodine in carbide fuel reprocessing has yet to

start in the United Kingdom, and the following section, dealing with fast
reactor fuel, will consider only the problem of iodine in oxide fuel r e -
processing through a conventional solvent extraction system.
5.3. Transport of short-cooled fast reactor fuel
Loaded transport flasks have to comply with stringent national and

international requirements prior to and during shipment. Under present
IAEA transport regulations [17] conditions applicable to transport of large
quantities of irradiated fuel include restrictions of the release rate o f 1 3 1 I
prior to shipment to not greater than 3 ;uCi/h,and following an accident,
equivalent to a Type В package test involving a 30 ft drop and an 800°C fire
for 30 minutes, to not greater than 3 Ci/week. It is easy to appreciate the
magnitude of the problem involved in designing a transport flask to meet
such stringent requirements because a flask loaded with fast reactor fuel
cooled for only 30 days could contain 100 000 Ci 131 I, and it is recognized
that extensive and expensive development and testing of the flasks and their
transporters will be required before the transport of short-cooled fuel is
authorized.
The same degree of safety will be required at the fuel loading and un-
loading stations and integration of the latter with the iodine protection
system of the head-end system of the reprocessing plant seems a logical
proposal.
5.4. The gaseous effluent problem
The arguments adduced in Section 4. 2 show that the DWL for the
discharge of 131 I from a single 120-m stack on the Windscale site is
650 mCi/d. If it is assumed that an upper limit for the discharge from
a fast reactor fuel reprocessing plant stack at Windscale could be set at
100 mCi 1 3 1 l/d, the minimum overall decontamination factors (DFs) required
(activity in feed/activity in aerial effluents) for the conceptual plant are
as shown in Table IV.
Now, if a distribution of 131 I in the conceptual fast reactor fuel
reprocessing plant similar to that found in the Magnox plant is assumed,
it can be seen that very considerable quantities of 131 I would enter the
aerial effluents. Thus the scrubbed dissolver off-gas alone, which could
be expected to contain less than 0 , 1 % of the iodine in the fuel, would
contain up to 2 Ci 1 3 1 I/d at 90 days1 cooling and up to 80 Ci 1 3 1 I/d at
50 days' cooling. The off-gas would therefore require an efficient clean-
up system to reduce discharges to the lowest practicable level well within
the derived working limit.
TABLE IV. MINIMUM DECONTAMINATION FACTORS FOR

CONCEPTUAL PLANT
Cooling time (days) 10 30 50 90 180
Overall DFs on gas stream 2 x 10' 4 X 106 S x 10 5 2 X 104 10
Gaseous effluents containing 131 I would also arise from the vessel vents
of the solvent extraction plant. As the 131 I fed to this part of the plant would
be virtually that in the fuel and, in addition, a build-up of 131 I in the
recycled solvent charge could take place, it may be expected that there
would be a significant release of 131 I to gases in the vessel vent system.
This release might be of the order of about 1% of the iodine in the fuel,
i . e . 20 C i / d with 90-day cooled fuel or 800 C i / d with 50-day cooled fuel.
Thus a vessel vent gas iodine removal system would have to achieve
decontamination factors for 131 I of at least 200 for 90-day cooled fuel or
8 X 103 for 50-day cooled fuel even to reduce the release of 131I from this
origin to 100 m C i / d . Higher DFs would, of course, be required to enable
the discharges from greater throughputs to be kept below this discharge
figure.
Use of a recirculating scrubber using dilute aqueous caustic soda or
mercuric nitrate solution to decontaminate the vessel vent gases is un-
likely to give the necessary decontamination at these cooling times,
especially if, as expected, a proportion of the 131 I in the vent gases is in the
form of organic iodides originating from reaction between the iodine and
the solvent.
Thus a primary stage of scrubbing followed by a more sophisticated
system for further decontamination, such as activated charcoal absorbers,
silver nitrate absorbers, etc., would probably be required to reduce the
iodine content of these gases to the lowest practicable level.
The use of continuous dissolution for fast reactor fuel poses many
problems and batch dissolution may have to be adopted. In this context
the DERE results using mercuric nitrate scrubbing are of particular
interest and, directly applied to the conceptual 2 t/d plant, would result
in an aerial effluent from the dissolver off-gas system containing 10 Ci
1 3 1 I/d for 90-day cooled fuel and 400 Ci 1 3 1 I/d for 50-day cooled fuel, again
requiring substantial further decontamination before low levels of dis-

charge could be achieved.
5. 5. Aqueous effluent problems
Because of the negligible amount of 131 I in aqueous effluents discharged

to sea from the Magnox fuel plant at Windscale, no formal separate limit
to the discharge of 131 I has yet been specified, but evaluations suggest that
a discharge the order of 10 C i / d may be acceptable.
Examination of the fate of the very small quantities of iodine in the
Magnox plant shows that 75% of that fed to the solvent extraction cycles
finds its way into effluents which are either directly or ultimately dis-
charged to sea. Obviously if the quantities of iodine contained in the feed
to the conceptual fast reactor plant (Table III) at cooling times less than
41
about 170 days were fed to the solvent extraction system, the arisings in
aqueous effluents would be greatly in excess of the suggested discharge
limit. Thus processing of short-cooled fuel without removal of the iodine
prior to solvent extraction is not an attractive basis for the design of the
plant.
Assuming that a process, such as steam distillation, can be devised
to remove 9 9 . 9 % of the 131 I in the feed, the fate of the residual iodine must
now be considered. For 90-day cooled fuel the 131 I would be 2 C i / d and
at 50 days' cooling 80 C i / d . The distribution of this residual iodine in the
solvent process and its ancillary effluent evaporations is not yet known
but it would appear that about 50% of it is extractable into T B P / O K . How-
ever, it must be recognized that the "inextractable" iodine may well distill
in the effluent evaporators and eventually reach those streams destined for
discharge to sea.
Taking the worst case, i. e. if 100% of the 131 I fed were to reach these
streams, then even 50-day cooled fuel would provide 8 times the estimated
DWL. Thus, the determination of the distribution of the 131 I in a solvent
extraction and effluent recovery systems after steam distillation of the feed
is essential, if minimum fuel cycle times are to be achieved, and it will
be necessary to ascertain methods of reducing the discharge, either by
aging or chemical treatment. Alternatively, the 131I removal process must
achieve at least 99.99% removal of the iodine in the feed.
5.6. Removal of iodine from the feed solution
From the above it will be apparent that it would be advantageous to

prevent the iodine from passing through the plant and especially from
entering the solvent extraction system. This could conveniently be achieved
by removal of virtually all the iodine from the fuel solution at or immediately
after the dissolution stage.
If no special iodine trapping system is installed on the vessel vent air
from the solvent extraction plant, the iodine removal stage must achieve a
DF of at least 10 3 . An obvious method is to vapour-distill the iodine directly
from the dissolver or from a separate distillation vessel following the
dissolver in the plant,and this method is under consideration at Oak Ridge
National Laboratory [18] as well as at Windscale.
Inactive trials at Windscale using simulated fast reactor fuel solution
containing uranium, inactive fission products, and inactive and trace-active
iodine, have shown that it is possible, with the addition of carrier iodide,
to steam-distill 9 9 . 9 % of the radioiodine. However, it is uncertain whether
the radioiodine and other significant fission products such as Pd and Ag
were present in the simulated solution in the same spectrum of species as
that which would result from dissolution of active fuel. The effect that the
intense radiation in short-cooled fuel solutions might have on the species
present is also unknown. Thus fully active trials with solutions produced
by dissolution of short-cooled fuel will have to be carried out before the
feasibility of this method can be substantiated.
The dissolver off-gases from such a system will contain substantial
quantities of short-lived active Xe isotopes in addition to 8 5 Kr and tritium
and it may well prove desirable to compress these gases and delay their
release to atmosphere [ 1 9 ] . Should this be done, the iodine release in
gaseous effluent will certainly be further reduced, thus easing the decon-
tamination requirements.
Alternative methods for removal of radioiodine from simulated fast
reactor fuel solutions have also been examined at Windscale. These include
extraction of the iodine into organic solvents such as carbon tetrachloride,
diethyl benzene, and kerosene, and precipitation of insoluble Pdl^ in some
cases with pretreatment of the aqueous solution. However, these methods
showed less promise than distillation, and would be more difficult to apply
in a fast reactor plant.
Complexing of iodine in the fuel solution by means of added mercuric
and silver ions, in order to suppress its volatilization and solvent extraction,
has also been examined. Neither method suppressed volatilization or
extraction of the iodine to a degree sufficient to enable the technique to be
applied to the fast reactor process as the primary method of iodine control.
5.7. Fate of iodine in the removal system
Containment and disposal of the great bulk of the iodine separated from
short-cooled fuel solution by steam distillation presents its own problems.
The volume of condensate produced in attaining a high degree ( e . g . 99.9%)
of removal of iodine is rather large and it would be desirable to reduce its
bulk. Before this can be done by evaporation, the iodine must be rendered
non-volatile, e . g . by making the solution alkaline, by addition of a complexing
agent or by precipitation as an insoluble compound. Even when this has been
done,a small fraction of the iodine can be expected to be carried over into
the condensate and give rise to an aerial effluent problem. Storage of the
concentrated iodine solution to allow the 131 I to decay to a level at which it
can be discharged to sea will require a considerable investment in shielded
storage tanks. A high degree of integrity and a fool-proof operation control
system would be required for this tank system in view of the very large
quantity of 131 I it would contain. With 50-day cooled fuel the activity held in
one of the tanks when just filled could reach 106 Ci 131 I in the conceptual
plant.
Associated with all the above aqueous iodine-containing effluent and
concentrate streams there will be vessel vent and incondensable gases which
will undoubtedly contain some 131I and probably require decontamination
before discharge to atmosphere.
5.8, General remarks
It should be emphasized that the work in the United Kingdom on the

reprocessing of short-cooled fast reactor fuel is in its early stages and that
the examples quoted above are given to illustrate the magnitude of the
problem and to indicate that possible solutions can be envisaged,but these
can by no means be regarded as definitive.
The development of any chosen route to meet the exacting standards
required by the regulatory authorities will require very considerable effort,
much of it on full-scale prototype equipment. During the development and
design stages the implication of malfunction and failure of all items of
equipment must be considered and provision made for secondary systems
to prevent accidental release of radioiodine. In the case of the high risk
areas of the plant such as the head-end and the iodine storage systems,it
41
is conceivable that this will lead to total enclosure of the plant (in a manner
similar to that employed for reactors) with provision for iodine-absorption
equipment for all the enclosed air.
5.9. Summary of problems in reprocessing short-cooled fast reactor fuels
(a) Radioiodine would be no problem in processing fast reactor fuel

if a cooling time of about 180 days were to be accepted before
reprocessing started.
(b) There is a very considerable financial incentive to reduce this
cooling time to the practicable minimum. To achieve these
financial advantages, it will be necessary to establish new and
very reliable techniques for the containment of radioiodine in
gaseous and aqueous effluents. These techniques must cover
fuel transport, off-loading and head-end process and the solvent
extraction plant. To achieve a minimum cost system, the removal
of the iodine at the head-end stage appears to be desirable.
(c) For oxide fuel, a possible process has been conceived but still
requires proving on active liquors and extensive further develop-
ment. The engineering of such a process to guard against
conceivable malfunction will require a very considerable develop-
ment and design effort.
(d) It is probable that, in view of the magnitude of the problem of
control of radioiodine, a very cautious approach to the intro-
duction of a short-cooled fuel cycle will be adopted and the systems
installed will be tested operationally at low iodine levels for
several years in order to establish their reliability.
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new separation plant, Windscale", 3rd Int. Conf. Peaceful Uses At. Energy (Proc. Conf. Geneva,
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[3] CORNS, H . , CLELLAND, D. W . , HUGHES, T . G . , DE LISLE NICHOLS, J. W . , " T h e new separation
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[7] Recommendations of the International Commission on Radiological Protection (adopted 17 Sep. 1965),
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[11] EGGLETON, A. E.J., ATKINS, D. H . F . , The identification of trace quantities of radioactive iodine
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Fission Product Release and Transport under Accident Conditions (Proc. Int. Symp. Oak Ridge, 1965) 2 ,
USAEC, Div. of T e c h . Inf. (1965) 830.
[13] ATKINS, D . F . , CHADWICK, R . C . , CHAMBERLAIN, A . C . , Deposition of radioactive methyl iodine
to vegetation,Health Phys. 13 (1961) 91.
[14] HALLER, W. A . , PERKINS, R. W . , Organic iodine-131 compounds released from a nuclear fuel c h e m i c a l
processing plant, Health Phys. 13 (1961) 733.
[15] BRYANT, P . M . , Derivation of Working Limits for Continuous Release Rates of 129 I to Atmosphere,
UKAEA Rep. AHSB (RP)R 98 (1969); Health Phys. 19 (1970) 611.
[ 16] Analytical Methods for the Determination of Iodine-131 in Vegetation, Milk, Thyroid Glands and
Natural Waters, UKAEA Production Group Rep. PG 204(W) HMSO, London (1961).
[17] Regulations for the Safe Transport of Radioactive Materials, Safety Series No. 6, IAEA, Vienna (1967).
[18] FERGUSON, D. E., BROWN, K. B., WYMER, R . G . , BLANCO, R. E . , WHATLEY, M . E . , GOELLER, H. E.,
BROOKSBANK, R. E . , C h e m i c a l Technology Division, Annual Progress Report, ORNL-4272 (1968).
[19] DUNSTER, H . J . , WARNER, B . F . , The Disposal of Noble Gas Fission Products from the Reprocessing
of Nuclear Fuel, UKAEA Rep. AHSB(RP)R 101, HMSO, London (1970).
INORGANIC ADSORBER MATERIALS
FOR TRAPPING FISSION PRODUCT IODINE
J . G . WILHELM, H. SCHUETTELKOPF
Radiation Protection and Safety Department,
Karlsruhe Nuclear Research Centre,
Karlsruhe, Federal Republic of Germany
Abstract
INORGANIC ADSORBER MATERIALS FOR TRAPPING FISSION PRODUCT IODINE.

For the removal of fission product iodine at elevated temperatures and in oxidizing gases, inorganic,
non-flammable adsorber materials should be used instead of charcoal. Experimental work was performed
to evaluate the usefulness of inorganic adsorber materials for iodine-filtering devices. Special interest was
concentrated on materials for off-gas cleaning in fuel reprocessing plants and gas cleaning inside the reactor
containment under MCA conditions. In view of the high price of silver and the sensitivity of molecular
sieves for acids, new inorganic adsorber materials were developed with relatively low silver loadings and
high removal efficiencies for methyl iodide and iodine. Experimental data are given for the removal efficien-
cies of new inorganic adsorber materials in wet air and superheated steam. Experiments are reported to
evaluate the effect of nitrogen oxides on the performance of the adsorber materials. The efficiencies and
prices of the new materials are compared with those of silver-impregnated molecular sieves.
1. INTRODUCTION
Relatively low desorption temperatures and flammability limit the use

of impregnated activated carbon for the removal of fission product iodine.
The silver form of zeolites (molecular sieves) showed good removal
efficiencies in dry and wet air up to high relative humidities and high tem-
peratures [1, 2] . In the range of a few milligrams per gram of zeolite AgX
there was no significant influence of loading on the removal efficiency. 1
For higher loadings, an exponential relationship between loading and
removal efficiency could be shown [3] .
For good removal efficiencies of the zeolites, nearly all of the Na + of
the zeolite NaX have to be exchanged with Ag + . The total amount of silver
is then in the range of 50 - 57 g Ag per 100 g zeolite (as delivered). The
price of this material is high. Zeolites do not withstand steam of high
temperature and pressure, nor will they be destroyed by acids.
Search was continued for an inorganic adsorber material with good
removal efficiencies at a low silver content and a high resistance to acids.
Furthermore, the desorption of iodine from the adsorber at elevated tem-
peratures should be very low.
Among the materials tested, different Bayer catalyst carriers im-
pregnated with AgN0 3 in our laboratory showed good CH 3 I removal efficien-
cies. These catalyst carriers are built of amorphous silicic acid, some
with a small amount of aluminium oxide. They have a very broad spectrum
of pores and a porosity above 50%. The specific surface is about 110 m 2 / g
and larger for some of the experimental products. The results of three
different types -of catalyst carriers tested will be reported.
1 These experiments were performed with a sweep gas of lOfy r.h.
47
48 WILHELM and SCHUETTELKOPF
The catalyst carriers KTB, KTC and KTD are experimental products
of the Bayer company. Besides AgNC>3 impregnation, KI was also tested as
an imprégnant on those materials. With KI, removal efficiencies < 1% were
measured for CH 3 I (10 cm bed depth, 0. 4 s stay time and 70% r. h. ). If
not otherwise indicated, the KT material used for the experiments reported
was in the form of beads of diam. between 1 and 2 mm. The pressure drop
of this material is about 60 mm of water for 10 cm bed depth and a super-
ficial air velocity of 25 c m / s (air of 25°C, 1 atm). AgN0 3 impregnation
was made by soaking the KT material with aqueous solutions of A g N 0 3
under vacuum and subsequently boiling for 2 h. Then the material was
dried. The total volume of the AgNO s solution was little more than the bulk
volume of the beads.
2. E X P E R I M E N T A L TECHNIQUE
The method and apparatus used for most of the experiments are r e -
ported in detail elsewhere [4] . T o measure the removal efficiency for
methyl iodide and elementary iodine, they were mixed with 131 I in the form
of tracer amounts of CH 3 131 I and elemental radioiodine, respectively. The
radioactively labelled material was introduced into a sweep gas stream and
sucked through successive test beds of the inorganic adsorber material.
The methyl iodide or elementary iodine which penetrated the test beds was
trapped downstream in 9 successive beds (safety beds). These were made
out of KI-impregnated charcoal in the experiments without nitrogen oxide,
otherwise out of zeolite AgX and/ or AgN0 3 -impregnated KT material. In
some experiments an additional HEPA filter was used between test and
safety beds. Complete removal in the safety beds was assured by a stay
time of 0. 9 s and a decreased r. h. of the sweep gas by heating the safety
beds. After penetration of the safety beds, the wet sweep gas was cooled
to a temperature of 6 - 9°C and the condensate was also measured for
radioactivity.
After the run, the 131 I activity in the test and safety beds was measured
by 7 -spectroscopy. The removal efficiency was calculated from the
1 3 1 I activity in the test beds compared with the total activity in the test and
safety beds. The data calculated by the use of a program are: (a) the
integral removal efficiencies for the successive test beds; (b) the dif-
ferential removal efficiency for each single test bed; (c) the integral
penetrations; (d) the differential penetrations; (e) the integral indices of
performance; and (f) the differential indices of performance. In this
paper it is mainly the integral removal efficiencies which are given for
the successive test beds.
3. E X P E R I M E N T A L RESULTS
Table I shows the standard conditions for the experiments. In Table II,
the removal efficiencies of some zeolites (silver form) and AgN0 3 -
impregnated catalyst carriers are compared. For KTC material some runs
are reported with different silver loadings. As was to be expected, there
is a steep increase in the removal efficiency with an increasing amount of
silver. Compared to types X and Y zeolites, the necessary amount of silver
INORGANIC ADSORBER MATERIALS 49
TABLE I. STANDARD EXPERIMENTAL CONDITIONS FOR TESTING

INORGANIC ADSORBER MATERIALS WITH METHYL IODIDE
Sweep gas: Wet air; filtered by HEPA filter; atmospheric

pressure; temperature: 30°C; r. h. : 70%;
superficial air velocity: 15 m / m i n .
Duration of air flow: prehumidification: s / 2 0 h; CH 3 I

injection: 1 h; air flow continued for
i 20 h. Variations of injection time on
the order of ± a few minutes in some experi-
ments due to correction for loading.
Loading: 1. 5 ± 0. 5 mg CH31271 + 3 to 30 /jCi CH^ 31 1

per g inorganic adsorber material (calculated
for 10-cm bed depth). Within the given
limits, the activity used in a single experi-
ment depends on the expected removal
efficiency.
Concentration: 100 ± 30 mg CH 3 I per m 3 .
for a certain removal efficiency is much lower. For filtering purposes it

should be taken into account that the pressure drop in the KT beds with
beads of 1 - 2 mm diam. is roughly 3 times higher than in the zeolite AgX
beds of the same bed depth, made of pellets of 1. 6 mm diam. With respect
to equal pressure drop, a KT bed ( 1 - 2 mm beads) of 2. 5 cm bed depth
should be compared with a zeolite AgX bed of 7. 5 cm bed depth. With an
impregnation of 18 g Ag/100 g KTC beads (as delivered), for both test beds
of different lengths,the removal efficiency was measured to rj = 98. 6% under
standard conditions (Table II). On this basis (same pressure drop and re-
moval efficiency) the total amount of silver used for the KTC bed is 10 times
lower than for the zeolite AgX bed. The great influence of the bead
diameter on the removal efficiency can be seen by comparison of the results
for KTC 1 - 2 mm beads and KTC 3 - 6 mm beads. Type Y zeolite was tested
because it has a slightly higher resistance to acids (acid degradation below
pH 3) than a type X zeolite (acid degradation below pH 5) and.for the better
hydrolytic and thermal stability of the type Y zeolite.
Table III shows experiments with air of 100% r. h. and 30°C as the sweep
gas. On 100% r.h. the removal efficiency of AgN0 3 -impregnated KT
material for СНз1311 is low. After some hours of prehumidification, the
KT material had a wet appearance. The total amount of adsorbed water
was between 50% and 100% of the impregnated and then dried KT material.
This uptake of water was measured after the experiments were finished.
From the given data, AgNO s -impregnated KT material cannot be used in a
sweep gas of 100% r. h. To avoid these conditions, it will be necessary to
heat off-gases with extremely high relative humidities. In these cases, the
difference between off-gas temperature and the dewpoint temperature should
be at least 10 degC.
Some experiments were performed to test the CH3131I removal
efficiency in superheated steam of 110°C and 150°C. No air was added to
the steam. The removal efficiency in all those experiments was relatively
TABLE II. CH 3 131I REMOVAL EFFICIENCY OF DIFFERENT INORGANIC

ADSORBER MATERIALS UNDER STANDARD CONDITIONS
Material CH 3 1 3 1 I removal e f f i c i e n c y (%)
Adsorber Ag impregnated Bed depth ( c m ) : 2. 5 5. 0 7. 5 10. 0

type (g/100 g ) a Stay time (s): 0.1 0.2 0.3 0.4
Zeolite
54. 0 74.1 94.2 98.7 99. 67
AgXb
Zeolite
45. 0 74. 8 94. 3 98.7 99.69
AgY
KTB 14. 0 96. 8 99. 928 99.9982 99. 9995
KTD 6.8 89.5 98.4 99.86 99. 986
KTC 1. 8 27. 4 47. 5 63. 8 74.4
KTC 3. 2 68.4 91.5 98. 0 99. 32
KTC 7.8 90. 8 99. 45 99. 970 99. 9944
KTC 8. 3 Loading 5 0 p g / g 92.2 99. 62 99.93 99.983
KTC 8. 5 93. 9 99.72 99.975 99. 9938
KTC 8. 5 94.4 99. 76 99. 968 99. 9931
KTC 18. 0 98.6 99. 985 99. 9994 (99. 9997) d
KTC 18. 0 98. 6 99. 985 99. 9996 99. 9997
KTC c 3. 0 18. 7 33. 5 44. 5 54. 5
KTC 0 28. 6 63. 5 85. 8 95. 6 98.7
a g silver per 100 g adsorber material (as delivered),

b pellets, diam. 16. m m , average values of 3 experiments.
c beads, diam. 3 - 6 m m (all other materials in the form of beads, diam, 1 - 2 m m ) .
^ ( ) activity of test bed near background.
TABLE III. CH3131I REMOVAL EFFICIENCY OF DIFFERENT INORGANIC

ADSORBER MATERIALS IN AIR OF 100% r. h.a
Material CH 3 1 3 1 I removal e f f i c i e n c y (fa)
Adsorber Ag impregnated Bed depth ( c m ) : 2.5 5.0 7.5 10.0

type ( g / 1 0 0 g) b Stay time (s): 0.1 0.2 0.3 0.4
Zeolite
54 17.8 34.4 48.8 62. 1
AgXC
KTC 3. 2 1. 6 3. 6 5.7 8.3
KTC 7. 8 2. 9 9.5 18. 0 27. 0
KTB 13. 0 3.3 8.9 17.9 -
a All other conditions are the same as given in Table I.

k g silver per 100 g adsorber material (as delivered).
c pellets, diam. 1. 6 m m .
TABLE IV. CH3131I REMOVAL EFFICIENCY OF DIFFERENT INORGANIC

ADSORBER MATERIALS IN SUPERHEATED STEAM
Material CH 3 1 3 1 I removal e f f i c i e n c y (%)
Adsorber Ag impregnated Bed depth ( c m ) : 2. 5 5. 0 7. 0 10.0

type ( g / 1 0 0 g) a Stay time (s): 0. 1 0.2 0.3 0.4
Superh'd steam temp.
Zeolite
54 150°C 99. 36 99. 944 99. 9985 (99. 9987) c
AgXb
KTC 3. 2 150°C 57. 7 96. 4 99. 88 99. 9986
KTC 7. 8 150°C .75. 6 99.62 99. 9972 99. 9990
KTC 10. 7 110°C 71. 2 99. 84 99. 9982 (99. 9984)°
a g silver per 100 g adsorber material (as delivered).

b pellets, diam. 1 . 6 m m .
c ( ) activity of test bed near background.
TABLE V. CH 3 131 I AND ELEMENTAL RADIOIODINE REMOVAL

EFFICIENCY OF KTC MATERIAL WITH AN A I R - N 0 2 MIXTURE AS THE
SWEEP GAS
Experimental conditions Removal e f f i c i e n c y
Concen-
Ag impregnated NOj Loading Bed depth ( c m ) : 2. 5 5. 0 7.5 10.4
tration
( g / 1 0 0 g) a vol. % (mg/gr ' Stay time (s): 0. 1 0. 2 0.3 0.4
(mg/m3)
8.0 8 1. 6(CH 3 I) 60 89. 8 98. 7 99.66 99. 960
8. 0 10 1.6(CH3I) 60 90.8 98.7 99.43 99. 77

KTC aged
7.8 10 7. 2 (I 2 ) 230 58.4 91. 2 99. 55 99. 87
7.8 10 27. 7 (I 2 ) 440 47. 8 82.1 97. 1 99. 88
8.3 10 26. 2 (I 2 ) 88 46.4 80.9 98.1 99.87
10.4 10 4 . 5 (I 2 ) 150 83. 1 96. 8 98. 9 -
10.4 10 9. 9 (I 2 ) 150 61. 0 92. 8 98.4 99.44
a g silver per 100 g adsorber material (as delivered),

b mg CH 3 I or I z per g of impregnated adsorber material, calculated for 10-cm bed depth.
high (rj > 99. 998%, see Table IV). From the small amount of 131 I activity
on SS screens and springs at the front end of the test beds, it can be con-
cluded that only an unimportant part of the CH 3 I was changed to a more
reactive form like I 2 .
For the steam experiments, loading was 0. 8 - 1. 6 mg CH 3 I per gram
of adsorber material (calculated for 10-cm bed depth). Time of pre-
conditioning with superheated steam was 18 - 24 h and CH 3 I injection time
0. 75 - 1. 5 h; the steam flow was continued for an additional 1 6 - 2 2 h.
TABLE VI. REMOVAL EFFICIENCY OF KTC FOR ELEMENTAL

RADIOIODINE
Experimental conditions 131I removal e f f i c i e n c y (%)
Ag impregnated Loading I2 concentration Bed depth ( c m ) : 2.5 5. 0 7. 5 10.0

(g/100 g (mg/g) (mg/m3) Stay t i m e (s): 0.1 0.2 0. 3 0.4
7.8 1.3 20 r} integral 99.959 99. 984 99. 989 99. 991
J7 diff. 99. 959 61. 6 29.4 17.9
7.8 2. 6 150 Tj integral 99. 83 99. 984 99. 988 99. 990
T) diff. 99.83 90.8 23. 9 18.7
7. 8 9.4 250 r¡ integral 97. 6 99. 975 99. 983 99. 986
i) diff. 97. 6 98.98 30. 1 19.9
8. 5 0. 075 4. 5 T] integral 99. 88 99. 971 99. 987 99. 990

i) diff. 99.88 76. 3 54. 1 29.18
8. 5 1. 0 7. 3 T) integral 99. 953 99.986 99. 992 99. 994

i) diff. 99. 953 68.9 46. 3 20.6
a g silver per 100 g adsorber material (as delivered).

k mg I2 per g of impregnated adsorber material, calculated for 10-cm bed depth.
Because the AgN0 3 -impregnated KT material may be used in iodine

filters for reprocessing plants, further experiments were performed with
sweep gas containing NO2 (mostly 10 vol. %). With a sweep gas of 70% r. h.
and 5 vol. % nitrogen oxides, the adsorbed total amount of nitrogen oxides,
water and acids built up from both was 90 - 140 wt% of the unused KTC
material. The adsorber beds were soaked and practically no removal e f -
ficiency was measured for CH 3 I under otherwise standard conditions. A
series of additional experiments was performed with a temperature of 80°C
in the sweep gas and adsorber bed. The dewpoint of the sweep gas was
30°C. The impregnated KTC material used in one experiment was aged
above fuming HNOs for 1. 5 months and, unfortunately, a small amount was
soaked with HNO3 prior to preconditioning. The total weight gain on aging
and soaking was 63%. Table V shows the results of those experiments.
In the CH3 I experiments the concentration of the CH 3I in the sweep
gas is constant over the injection time. A mixture of gaseous CH 3 I and air
is injected over a flowmeter from a storage tank. The I 2 is injected by a
heated air stream flowing directly through the U-tube with solid elementary
iodine. Temperature and gas flow are controlled, but the evaporation
depends on the surface area of the I2 crystals. The decrease of radio-
activity in the U-tube is measured continuously and the concentration is cal-
culated for the injection time of the main amount of I2.
In the experiments with high I2 loadings (27. 7 m g / g and 26. 2 mg/g)
the first test bed adsorbed 62% and 54%, respectively, of the stoichiometric
amount of iodine with respect to the silver content. The influence of the
I2 concentration on the removal efficiency and loading is obviously low in
the range tested. The concentration was varied between both experiments
by 5 : 1 .
4 5 6 7 8 9 16 18 20
g A g / 1 0 0 g ADSORBENT
FIG. 1. CH 3 131 I penetration of A g-impregnated adsorbents as a function o f the Ag impregnation

Test conditions: Wet air: 3 0 ° C , 70% r . h .
Prehumidification: г 20 h
C H j I loading: 1 - 2 m g / g (calculated for 10 c m bed depth)
CH 3 1 injection: lh
Air flow continued for an additional 20 - 2 4 h.
О = 2. 5 c m bed depth (KTC)

x = 5 c m bed depth (KTC)
• = 7. 5 c m bed depth (KTC)
V = 10 cm bed depth (KTC)
• = 10 c m bed depth ( z e o l i t e ) .
FIG.2. Penetration o f 131I in the form of CH 3 I and I 2 through Ag-impregnated KTC material.
Test conditions: Wet air: 3 0 ° C , 70<í,r.h.
Prehumidification: г 24 h
After « 4 injection, air flow was continued for an additional 20 - 2 4 h.
0 = loading: 2.5mglj/g; concentration: 150mgl2/m3

A= loading: 9mgl2/g; concentration: 250 m g l 2 / m 3
• = loading: 1.2mgCH3I/g; concentration: 60 m g C H , I / i t f .
п
о
о
/^-IMPREGNATED CHARCOAL 1Ю°С

о
/
о
M
/
/
/
/
сх
/
о'
V/
Q J
у(J
a
ce
8
/
С!
!?
?
/о
!
9f
û
II
л-
v—
V
KTC, AgNOj-IMPRECÎNATED 30o ° c
A
//
1CP
/
э
10 15 20 25 30
DESORPTION TIME (days)
FIG.3. Desorption o f i 3 U from different materials.

О , Л = activity desorbed, corrected with respect to injection time (integral)
О , A = actual activity desorbed (integral).
Five experiments are performed with I2 in air of 30°C and 70% r. h.

Prehumidification was ê 20 h. Loading and concentration were changed
within a wide range. After loading, gas flow was continued for an additional
16 -20 h. The conditions and the results are given in Table VI and Fig. 1.
Because the integral removal efficiencies (rj integral) for larger bed depth
are much smaller than expected, the removal efficiency for each single
test bed (differential removal efficiency, r¡ differential) is also given.
From these data it can be concluded that an additional iodine compound is
present. For this compound the KTC material has a very low removal
efficiency, much lower than for CH3131I. Analytical work is in progress
on the chemical nature of this compound. Figure 2 shows the penetra-

tion of the KTC test beds versus bed depth for two I2 experiments. Each
curve represents one of the successive test beds. One run with CH3131I is
also included. As demonstrated, CHa131I is not the penetrating compound
in the 12 runs.
Figure 3 shows the results of two desorption experiments. The 131I
was originally injected in the form of CH3131I, mixed with CH3l27I. One ex-
periment was performed with activated charcoal, type Norit CG 1, 1% KI.
Loading was 80 /ug CH 3 I per gram of charcoal (calculated for 10-cm bed
depth). Sweep gas (dry air) and adsorber temperature was 150°C. The total
amount of iodine desorbed after 20 days amounts to 1. 32% of that originally
removed. Penetration during injection was 0. 00033%. In the second ex-
periment KTC material with an impregnation of 0. 1 g Ag per gram of
catalyst carrier (as delivered) was used. Loading was 250 /ug CH 3 I per
gram of KTC material (calculated for 10-cm bed depth); sweep gas and
adsorber temperature was 300°C. The total amount of iodine desorbed
after 20 days amounts to S 0. 001% on top of a 131I-penetration of 0. 0024%
during injection.
4. CONCLUSIONS
In air of 70% r. h. and in superheated steam of 110°C and 150°C,

AgN0 3 -impregnated KT material showed very high removal efficiencies for
CH3I. Good removal efficiencies could also be measured for CH 3 I and I2
in air-N0 2 mixtures. For I2 in wet air (70% r. h. ) the removal efficiency
is also good, but under these conditions an unknown iodine compound was
detected which is more penetrating than CH 3 I. Under extremely high rela-
tive humidity (100%) , the AgN0 3 -impregnated KT material has low removal
efficiencies and heating of the sweep gas is necessary for good results.
Iodine desorption at elevated temperatures seems to be very low.
So, AgN0 3 -impregnated KT material could be a useful adsorber
material for fission product iodine with special suitability for off-gas
cleaning in reprocessing plants. Because of the small amount of silver
needed for impregnation,the price will be relatively low and is assumed
to be about three times higher than the price of good iodine-impregnated
charcoal.
REFERENCES
[1] MAECK, W . J . , PENCE, D . T . , KELLER, J . H . , "A highly efficient inorganic adsorber for airborne iodine
s p e c i e s " , Proc. 10th AEC Air Cleaning Conference, New York, 1968 (FIRST, M . W . , MORGAN, J . M . , J r . ,
Eds), Harvard U n i v . , Boston (1968) 185.
[2] WILHELM, J . G . , Trapping o f Fission Product Iodine with Silver-Impregnated Molecular Sieves,
Karlsruhe Nuclear Research Centre, KFK 1065 (1969).
[3] SCHUETTELKOPF, H . , WILHELM, J . G . , "Jodfilterprogramm", Annual Report of the Radiation Protection
and Safety Department o f the Karlsruhe Nuclear Research Centre, KFK 1158 (1970) 85.
[4] WILHELM, J . G . , "Testing of iodine filters for nuclear installations", Treatment of Airborne Radioactive
Wastes (Proc. Symp. Vienna, 1968), IAEA, Vienna (1968) 403.
BEHAVIOUR OF IODINE ISOTOPES
IN A HIGH-TEMPERATURE GAS REACTOR
COOLANT CIRCUIT
P.R. ROWLAND, W.E. BROWNING *, M. CARLYLE

OECD Dragon High-Temperature Reactor Project,
AEE Winfrith, United Kingdom
Abstract
BEHAVIOUR OF IODINE ISOTOPES IN A HIGH-TEMPERATURE GAS REACTOR COOLANT CIRCUIT.

The behaviour of iodine in the helium primary coolant circuit of the OECD Dragon High-Temperature
Reactor has been studied by co-ordinating two techniques for measuring its distribution: (a) by using a diffusion
probe technique for estimating the concentration of iodine isotopes at a point in the system between the core gas
exit and a primary heat-exchanger inlet; and(b) by removing a primary heat-exchanger, cutting it up and measuring
the distribution of iodine along the tube bundle. When the results of the two methods are compared, it is found
that about 25% of any given iodine isotope is plated out on the tube bundle (mild steel at about 230°Q for each
pass of the coolant through the heat-exchanger. The shape of the iodine distribution profile along the heat-
exchanger is also in agreement with a plate-out factor of this order. By study of the diffusional behaviour of iodine
isotopes in method (a) it is shown that the iodine is carried by the gas in molecular form rather than by dust. The
results are used to calculate reactor cote release/birth ratios for iodine isotopes, and by comparison with data
obtained for inert gas isotopes it is shown that release of iodine from an HTR core parallels that of xenon of
similar half-life. This is important for safety calculations.
1. INTRODUCTION
In any power-producing reactor there will be a large number of fuel

pins and it is virtually impossible to avoid a certain number of imperfections
that will allow fission products to escape into the coolant. Iodine will clearly
be among the more important of these. In the Dragon High-Temperature
Reactor the fuel is dispersed in small particles enclosed in coatings of
pyrolytic carbon and silicon carbide, which retain the fission products.
However, as with any other system, a small proportion of faulty fuel may
occur and this can give rise to some release of fission products into the
helium coolant. This release is normally low (release/birth ratio - 10 - 6 ,
see later), but clearly the first step in controlling the level of any possible
gasborne or airborne waste from a reactor is to establish firm data and
theories for the behaviour of radioisotopes in the coolant circuit. These can
then be applied either when calculating the way in which radioisotopes may
behave in case of a possible accident, such as a broken coolant duct, or in
calculating the minimum standards of leak-tightness which can be permitted
in a given reactor design. This report therefore describes methods used in
the Dragon High-Temperature Reactor for thp study of the behaviour of
isotopes in the coolant circuit with special reference to iodine. Some of
the methods may be adaptable to systems other than the coolant circuit of
an HTR, especially the diffusion probe, which indicates the form as well as
the concentration of iodine present in a gas.
* Guest Scientist from Oak Ridge National Laboratory, USAEC.
57
58 ROWLAND et a l .
The problems involved in studying iodines in the reactor coolant may be

illustrated by comparing iodine with xenon. Iodine is chemically reactive
(especially with metal surfaces) whereas xenon is not. Hence xenon released
from the reactor core mixes uniformly with the circulating gas and a measure-
ment of the amount of xenon in a sample drawn off through a sampling pipe
will give the concentration and hence (in the case of long-lived or stable
isotopes) the total amount of xenon in the circulating mass of the coolant.
If an attempt is made to use the same technique with iodine, it will plate out
on the walls of the sampling pipe so that the sample that emerges from the
pipe will be depleted and the relationship of the concentration in the sample
to that in the original coolant will be unknown. Special methods (outlined in
the experimental section of the paper) were therefore devised to overcome
these problems when sampling the coolant gas. The work to be described
therefore stems mainly from two sets of experiments:
(a) A method for measuring the iodine burden of the coolant gas at a
point about midway between the core gas exit and a heat-exchanger
entry. In particular, such a measurement was made just prior to
shutting down the reactor and carrying out the second part of the
work.
(b) The second exercise consisted of rapid removal and cutting apart
of a complete primary heat-exchanger soon after shutdown so that the
distribution of 8-day 131 I could be measured before excessive decay.
The measurements were facilitated by the fact that for several weeks
prior to the shutdown and cutting-up of the heat-exchanger the reactor had
contained fuel which had been run to failure for experimental purposes and
the release was therefore higher than that from normal fuel (by about two
orders of magnitude). The concentrations and fractional releases quoted in
this report are therefore for a high-release condition and would have to be
scaled down by about 102 for a normally running power reactor.
The results from (a) and (b) above were co-ordinated with measurements
of krypton and xenon isotope concentrations carried out at the same time as (a).
2. EXPERIMENTAL
2. 1. Coolant circuit
Before describing the experimental techniques, the coolant circuit will

be briefly outlined.
Figure 1 is a much simplified diagram of the reactor and one of the six
helium primary coolant circuits (the other five such circuits, omitted for
simplicity, are arranged symmetrically round the pressure vessel). As
indicated by the arrows, the coolant helium circulates upwards through the
core and thence through a main hot gas duct from which it flows upwards over
the tubes of the heat-exchanger, then through the circulator, and down through
the annular return duct (which is concentric with the main hot gas duct), back
into the main pressure vessel where it flows downwards over the graphite
radial reflector and finally upwards through the core again. Within the heat-
exchanger a small flow (to trim the thermal conditions in the six heat-
exchangers) also passes through the central by-pass duct shown, but this
small "leak" of a few per cent has been neglected in the discussion of the
results.
IODINE ISOTOPES IN HTGR COOLANT 59
FIG.l. Gas sampling probe in Dragon reactor.

60 ROWLAND et al.
FIG.2. Block diagram of coolant circuit.
Figure 2 is the same system further simplified to a block diagram

showing the various components in the order in which the coolant encounters
them. As a reminder that its effect must always be taken into account when
considering isotope concentrations in the coolant, the clean-up plant, which
continuously purifies a small bleed of coolant helium, is included (the make-
up gas system has, however, been omitted).
Iodine in the coolant system has been studied mainly by the methods
outlined in 2. 2 and 2. 3. Inert gas measurements are described in 2 . 4 .
2.2. Totally removable sampling tube (Dragon coolant sampling

module or "Dracule")
To overcome the sampling problems mentioned in the Introduction, a

special sampling tube or probe was designed; this has been described in
previous reports [ 1, 2]. The basic principle is that a sampling tube may be
inserted into its sampling position or removed by means of a gas-lock while
the reactor is running. The tip of the probe tube takes a stream of sample
gas from the centre of the main coolant duct at a point about midway between
the core exit and a heat-exchanger (Fig. 1). The tube is of stainless steel
2 m long with a bore of 7 mm, though in practice this is usually reduced to
about 3 mm by the presence of an insert tube. This is because in the course
of experimental work it has been found advantageous to line the probe with
2 - c m lengths of graphite tube which fit together so that in effect they form a
continuous graphite lining to the probe. Deposition of fission products there-
fore occurs on the inner surfaces of these 2 - c m graphite bobbins, which can
be removed at the end of the experiment and y-counted one at a time to give
FIG.3. and " s i profiles in probe.
a deposition profile along the tube. Apart from its convenience, this
technique enables the fission products to be y-counted in the absence of
background from the activation products which arise in the steel of the probe
because there is a small but appreciable neutron flux in the region of the
probe facility. Measurements have shown that the amounts of fission product
which penetrate the graphite lining and deposit on the steel are negligible.
The downstream (i. e. outlet) end of the probe consists of a Maypack-
type series of filters and charcoal granule beds (for a length of 10 cm)
designed to trap any fission products which have not diffused to the walls of
the main probe. Except for a length of about 15 cm at the inlet end of the
probe tube, the wall temperature is 200°C or less and practically all iodine
molecules striking the walls are deposited. Hence, integration of the quantity
of a fission product deposited on the graphite bobbins and the Maypack gives
the total amount drawn into the probe for a known flow of gas and a known
duration. Probes are normally left running for a period of 2 - 4 weeks so that
62 ROWLAND et a l .
the amount of 8-day 131 I deposited approaches its "equilibrium" or steady-

state value. Sampling rates are normally of the order of 0. 1 - 1 . 0 normal
litres • s" 1 and in tubes of the bores used give flow in the laminar regime.
Figure 3 shows typical tube profiles for 131 1 and 133 1.
The concentration of a given isotope entering the probe is calculated in
the following way.
Let:
с = concentration in atoms of isotope per g of coolant
f = flow along probe (g- s" 1 )
a = total activity of the isotope in probe (curies)
X = decay constant of isotope (s "1)
t = time for which coolant flowed through probe (s)
The number of atoms, n, in the probe is
n = 3. 7 x 1010 - (1)
Л
Also, from the usual build-up equation
n = - J (1 - e - ^ ) (2)
so that, from Eqs (1) and (2)
= â 3. 7 x IP 10 (3)
° f (1 - e'X: )
The size of the particles carrying a given activity may be inferred from
their diffusion coefficient in the coolant and this can be estimated from the
slope of the plate-out profile along the probe tube. It is seen from Fig. 3
that this is a straight line of negative slope on a semi-log plot. The diffusion
coefficient is obtained from the following formula which is derived from the
work of Gormley and Kennedy [ 3] :
D= -0.2004 V A1 °Rx10y (4)
where
D = diffusion coefficient of isotopic species in coolant gas (cm2 - s" 1 )
V = volume flow rate (at pressure) (cm 3 • s" 1 )
y = activity per unit length (/¿Ci - cm" 1 )
x = distance from tube entrance (cm)
A login У
^ ^ — i s , of course, the slope of the profile.
A x
The molecular size of collision cross-section may then be estimated from
formulae and nomographs derived by Othmar and Chen [ 4].
2.3. Plate-out profiles in a heat-exchanger
Because of the short half-life of 131 I (8 days) it was necessary to remove

the heat-exchanger and obtain samples within a period of about 3 weeks from
reactor shut-down. The method of cutting up the heat-exchanger is shown in
FIG.4. Method of cutting up heat-exchanger to obtain fission product plate-out profiles.
Fig. 4. There are 7 concentric rows of tubing; samples of tube, each about
15 cm long, were cut out by means of a slitting disc and removed row by
row. In the photograph, all the samples on the side facing the left-hand
operator have been removed, revealing the by-pass duct. The right-hand
operator is in process of cutting through the final row of samples on his side.
For measurement, samples were trimmed to a standard size and counted
one at a time on a 7-spectrometer. A full report covering several isotopes
will appear elsewhere [ 5] but the relevant data for the study of iodine iso-
topes will be given in Section 3.
64 ROWLAND et a l .
The material of the tube bundle was mild steel and the heat-exchanger
was of nearly isothermal design with nominal surface temperatures in the
region of 233°C. The heat-exchanger which was cut up was not in the same
coolant circuit as that in which the sampling probe is installed, but there is
no reason to believe that its behaviour would differ from any other heat-
exchanger in the reactor.
2.4. Inert gas measurements
Inert gases (kryptons and xenons) in the main coolant circuit of the
Dragon reactor are measured routinely by Operations Group by drawing
samples from a sampling pipe and counting them on a 7-spectrometer. Either
direct counting or counting of daughter activities may be used according to
the isotope concerned.
The probe itself may also be used as a fast response facility for measuring
isotopes of short half-life. For example, 1 4 0 Xe was measured by using the
deposition of its daughter, 140 Ba. The profile of the latter had a slope which
corresponded closely to that which would be observed if deposition were con-
trolled by disintegration of 140 Xe rather than by the (relatively faster) diffusion
of the daughter to the walls. Extrapolation of the 140 Ba value to the tip of the
probe enabled the concentration of 140 Xe in the main coolant to be calculated.
3. RESULTS
3.1. Concentrations of iodine isotopes in the main coolant
Figure 3 shows profiles in the Dracule probe-tube obtained for a period

immediately prior to reactor shutdown and the cutting up of the heat-
exchanger. From these and the relevant flow data, the concentrations of
iodine isotopes in the coolant in the main duct are calculated to have been:
1311 = 3. 97 x 10 8 atom/g He
1331 = 9. 88 x 10 7 atom/g He
These are the concentrations which impinge upon the heat-exchanger.
3.2. Collision cross-sections of iodine carriers
The collision cross-section of 1311 and 1 3 3 I as given by the slopes of the

profiles in Fig. 3 was equivalent to a molecular radius of about 3 A.
3. 3. Plate-out profiles and the 1311 inventory on the heat-exchanger
The 131 1 profile along the tube bundle is shown in Fig. 5 in which the
concentration of isotope in nCi per cm 2 of tube surface is plotted semi-
logarithmically against the area of surface over which the coolant has swept
in reaching any point along the heat-exchanger (this area is practically
proportional to the distance from the bottom of the tube bundle).
The fact that the profile is everywhere either rising or level but never
falling is an important observation which will be discussed later. The
LOWER END UPPER END

A
• -
ROW 1 • •
ROW 2 A
ROW 3 V
ROW i •*
ROW 5 and 7 О
ROW 6 »
10 15 20 25 30
SWEPT SURFACE AREA ( c m 2 «10*)
FIG.5. profile along heat-exchanger.
15 20 25
SWEPT SURFACE AREA (cm!«10')
FIG.6. Caesium profile along heat-exchanger.

66 ROWLAND et al.
profiles for caesium are shown for comparison in Fig. 6 and it is seen that,
in contrast to iodine, they are continuously falling curves.
The total amount of 131 1 on the heat-exchanger was found by graphical
integration of Fig. 6 to be 4. 95 Ci.
3. 4. Relationship of inert gas R / B to X
From the measured values of krypton and xenon isotopes in the coolant,
their release rate/birth rate ratios were calculated. Those for krypton were
then lowered by a factor of 4 [ 6] to bring them into line with xenons because
kryptons, having lighter and smaller atoms, are released more rapidly from
damaged fuel. When the xenon values and normalized krypton values were
plotted against respective decay constants on a logarithmic graph (Fig. 7) it
was found that the points tended to follow the relationship:
(5)
The reasons for this are dealt with in the next section.
FIG. 7. Plot of log R/B against log A. for inert gases and iodines.
4. DISCUSSION
The fact that the 131 I profile along the heat-exchanger is not a falling
curve has important implications. It suggests that the coolant gas still
contains ample reserves of iodine and is far from depleted by the time it
reaches the downstream end of the tube bundle. This theory can be tested
by comparing the rate of arrival of iodine at the heat-exchanger with the
amount actually trapped on its surface.
From the results obtained with the Dracule probe, the concentration of
131 I arriving at the heat-exchanger is 3. 97 x 10 8 atom - g " 1 . The flow into
a single heat-exchanger is F = 1. 68 x 10 3 g. s" 1 so that the rate of arrival of
1311 atoms, r, is:
r = FC = 6. 67 x 10 1 1 atom • g" 1 (6)
It is reasonable to assume that the 8-day 131 I on the heat-exchanger had

reached a steady state because the reactor had been running for several weeks
prior to shutdown. Take the fraction plated out on the heat-exchanger at one
pass of the coolant through it as h, so that the rate of arrival of 131 I atoms
on the surface is hr. Then the steady-state number of atoms on the surface
is rh/Л. The corresponding activity will be r h / 3 . 7 x 10 1 0 Ci. Equating this
with the 4. 95 Ci actually found:
rh = 4. 95 x 3. 7 x 10 1 0 (7)
and using the value of r calculated in Eq. (6):
h = 0. 27 (8)
Although it decayed too quickly to be measured on the heat-exchanger,

it is assumed that 133 I behaved in a similar manner. Hence only about a
quarter of the iodine is plated out in the heat-exchanger at one pass and the
plate-out profile would not be expected to fall by more than 25% along its
length. If the surface were saturated, a completely horizontal profile would
be expected. However, a rising profile, such as that seen at the upstream
end in Fig. 5, is difficult to explain without invoking variations in mass
transfer conditions or in surface temperature along the length of the tube
bundle. The former explanation would require that the turbulence region
at the upstream end differed from that at the downstream end in such a way
as to make the mass-transfer rate smaller. However, this argument is
contradicted by the caesium profiles (Fig. 6). These conform fairly well to
an exponential fall-off along the heat-exchanger (i. e. a straight line on a
semi-log plot) except at the upstream end where, contrary to 131 1, plate-out
is enhanced. Hence it is not possible to explain both the iodine and caesium
profiles on the basis of different boundary layer effects in the initial position
of the heat-exchanger from the main portion.
It is considered more likely that the effect may be due to higher surface
temperatures on the gas side of the tubes at the upstream end, where, apart
from the steady-state conditions, temperature excursions have been observed
due to instabilities in the two-phase water/stream flow within the cooling
tubes. It is estimated that the tube surface temperature at the downstream
end could possibly be 50°C above the 233° nominal value. This would result
68 ROWLAND et a l .
in lower plate-out of iodine or volatile compounds such as Ре1г or possibly

surface migration of plated-out iodine downstream on to the cooler portions.
Another possible explanation is that helium atoms which have been
excited into high electronic energy states in the core may, on first striking
the tube bundle, transmit energy to bound iodine and release it. so that it
migrates further along the tube bundle. The excited states would decay as the
helium passed along the tube bundle so that comparatively little iodine would
be removed from the downstream end. Either of the foregoing hypotheses
regarding iodine profiles would not be incompatible with the caesium profile
since the latter is more strongly adsorbed (90% plate-out at one pass) and
its deposition would be less influenced by temperature variations or excited
atoms.
Integration of the 131 1 on the heat-exchangers gives 5 Ci on each,
i . e . 30 Ci for all six. This corresponds to 10 18 atoms and the total number
of atoms plated out in the circuit must be greater than or equal to this value.
If the average concentration in the gas throughout the circuit is taken as that
sampled by the probe, the number of atoms in the 60 kg of circulating gas is
about 2. 4 x 10 1 3 . If the plate-out factor is taken as the ratio of the foregoing
numbers it is 4 x 10 4 . It would seem reasonable, therefore, to assume a
plate-out factor of the order of 10 4 based on the situation in the heat-
exchanger branches. (If plate-out in other parts of the circuit is assumed
on the basis of an average value in the gas lower than that measured at the
probe, the plate-out factor will be higher. )
With regard to the concentrations of iodine adsorbed, the maximum sur-
face concentration of ca. 50 ^Ci • cm" 2 shown in Fig. 5 is equivalent to about
2 x 10 12 atom of 13 4 • cm" 2 , which is about 10" 3 of a monolayer, assuming
the surface of the steel to be smooth. Application of a roughness factor would
not be expected to alter this greatly [ 7] . The contribution of 133 I, if the
same as that in the vapour, would be about 2 5% of the 131 I value, i, е. a
marginal increase. The flattening of the profile at the downstream end of
the heat-exchanger, and the fact that only 27% of the 131I is trapped, suggest
an equilibrium between adsorbed atoms and the vapour. If this is so, there
should be exchange between adsorbed iodine atoms and those in the vapour
phase, in which case the stable ( 127 I) and long-lived (1. 6 x 107 y r I29j)
isotopes will come to equilibrium (via the coolant) with the clean-up plant,
the clean-up constant for which i s a (= 1. 5 x 1 0 - 4 s _ 1 ) . It is interesting to
calculate roughly the ratio of stable and long-lived iodine in the coolant
circuit to 131 I and 133 1. In order to calculate the concentration of stable
and long-lived types it is necessary to know their effective R / B . For such
atoms, decay rate is negligible and virtually every atom produced in a
damaged particle eventually diffuses into the coolant, so that the R / B ratio
is practically equal to the fraction of damaged particles in the fuel, 0. The
number of atoms in the circuit is thus;
0FY s (1 - e'a'l)/a (9)
where a* is the effective clean-up constant = л/plate-out factor

(= 1. 5 x 10" 8 s" 1 ), F is the fission rate, Y s is the total yield of "stable" iso-
topes and t is the build-up time. The rate of release, R 1 , for relatively
rapidly decaying species is given by the usual formula [ 8] :
R' = 3 F Y ' / A (10)

where A = •j a 2 X / D , a is the effective microparticle radius within the

kernel, D the diffusion constant and Y' the yield of active isotopes. Hence,
if it is assumed that most of the radioactive atoms are adsorbed and reach
effective decay equilibrium within a few half-lives, their number is 3 F Y ' / A X .
The ratio of "stable" to active isotopes is thus:
N s / N ' = Y 0 A (1 - е^'МЗУ'о 1 (11)
Typical values of the components of A are D = 6. 5 x 10" 16 (at 1500°K) and

a = 3 ц т [ 9]. Using these values and taking the build-up time, t, for "stable"
isotopes at about 100 days, gives N s / N ' = 10. This gives a total iodine
concentration in the gas of about 4 x 10 9 atom/g He (5 x 10" 13 atm for coolant
at 20 atm) and a surface coverage of about 10" 2 monolayers at the time of
the experiment. Unfortunately there are insufficient literature data [ 7, 10]
in the appropriate temperature and pressure ranges (230°C and 10" 13 atm)
with which to compare these values, although they would not appear to be
incompatible with the fact that Neill [ 7] found a ratio of adsorbed atoms to
partial pressure of about 1/ 10 of the above value at a higher temperature
and partial pressure (400°C and 5 x 10" 10 atm). The ratio deduced above
will therefore be regarded as plausible but tentative.
It is unlikely that all of the iodine which escapes from the heat-
exchanger without being trapped will recirculate through the core, since
before doing so it passes over the graphite radial reflector which, being
porous, will have a very large internal surface, part of which will be at
only about 400°C and would adsorb iodine and Fel2 arriving from the heat-
exchanger. For the purpose of calculation it will be assumed that the fraction
of iodine removed at each pass by the heat-exchanger and by adsorption in the
graphite reflector, etc., is y. Then for a steady-state system the rate of
removal equals the rate of release from the core, R, so that for all six
coolant circuits:
R = 6 y FC = 6 y r (12)
where r has the value calculated in Eq. (6), i. e. 6. 67 x 10 1 1 ; since

F = 1. 68 x 10 3 g - s" 1 and y = 0 . 2 7 or greater, the effect of the clean-up
plant with a flow of only 10. 5 g - s " 1 can be neglected.
At 20 MW the rate of birth of 131I is 1. 89 x 1016 atom - s " 1 , which gives
an effective core release of:
I = 2. 12 x 10" 4 y (13)
Without more detailed knowledge of plate-out in the reflector it is not

possible to say more than that y is between 0. 27 and 1. 0. The latter figure
will therefore be taken since it gives a more pessimistic (i. e. larger) value
for the effective R / B :
I = 2 . 1 2 x 10" 4 (14)
a
It is interesting to compare the R / B values obtained for iodines with
those for inert gases, since the comparison should throw light upon the
mechanism by which iodine escapes from the kernels Of damaged particles.
70 ROWLAND et a l .
It would be expected that at the temperatures of the fuel in an HTR

(about 1200°C) iodine would be highly mobile since most chemical compounds
formed by it are weakly bonded and dissociate at relatively low temperatures.
Hence, at the temperatures concerned, iodine would be expected to behave
like an inert gas of comparable molecular weight and size, i . e . xenon.
It is well known [ 8] that diffusion of inert gases from the UO2 or UC2
grains of the kernels of damaged particles is dependent on half-life (because
of decay while diffusing) and should obey Eq. (5), i. e. R / B oc
to a good approximation over a wide range of half-lives. Plotting R / B against
X for iodines and inert gases on the same graph should therefore give an indi-
cation whether iodine behaves similarly to inert gases.
Hence, for a series of six different probes, the R / B s for 131 1 and 133 1
as calculated above were plotted together with those for kryptons (normalized)
and xenons obtained at the same times. Although scatter in the results was
somewhat high, the points in each case tended to lie along a line of the ex-
pected slope, i. e. (~i). In Fig. 7 six such graphs have been summarized by
normalizing each to give the same R / B for 1 3 3 Xe, which is the gas most
frequently measured in the reactor and which, having a half-life of similar
magnitude to that of 131 1, would be expected to be most readily comparable
in R / B .
It is seen that the general trend is along a line of ( - } ) , with the possible
exception of 16-s 1 4 0 Xe, which is rather low. As indicated by the dotted line,
this low value may be a real effect because the time for a gas molecule to
diffuse through the graphite sleeve in which the fuel is held is of the order of
10-100 s and gases of short half-life may therefore suffer an extra attenuation
due to decay during transit through the sleeve.
The main observation, however, is that within the general scatter, the
131 I and 133 1 lie on a common line with the kryptons and xenons. This is a
significant result since it shows that iodine release from the core can be
treated in the same way as xenon release, i. e. an iodine isotope has the
same R / B as a xenon isotope of the same half-life would have.
These values may err slightly in the direction of pessimism since the
values calculated for Fig. 7 are based upon the assumption that У in Eq.(10)
equals 1. 0, but a more optimistic assumption such as that iodine only
plates out in the heat-exchanger would be unjustified and the factor gained
w'ould lower the values by less than the order of experimental scatter.
With regard to the form of the iodine as measured in the Dracule
probe, the 3 A collision radius found is about twice that expected for an iodine
atom. A possible explanation is that if the atoms were ionized, e. g. by
reaction with excited helium atoms, interaction between them and surrounding
molecules may take place over a relatively long distance and give rise to a
high effective radius. However, the main point is that the value found is
definitely in the molecular range and far below dust particles in size. Other
probes gave similar or smaller values. This was supported by the fact that
when a probe was run with a fast flow of coolant so that iodine reached the
Maypack at the downstream end in measurable amounts, the iodine was found
on the charcoal packing rather than on the glass-fibre dust filters which
preceded it.
A special probe was designed [ 11] in which the gas entering it suffered a
sharp change in direction, which would tend to deposit dust on the outside
circumference of the turn. However, no evidence that 1 3 1 I was carried by
dust was found.
Thus the iodine measured in the Dracule probes was in molecular form
and not carried by dust.
5. CONCLUSIONS
Putting the conclusions in order of importance, they are

(1) The R / B of an iodine isotope from damaged particles in a high-
temperature reactor is computed as equal to that which a xenon iso-
tope of the same half-life would have.
(2) In a heat-exchanger of the type studied the amount of iodine trapped
per pass is of the order of 2 5% of that in the gas which enters.
(3) The plate-out factor in the Dragon reactor is 10 4 .
(4) The iodine measured in the probe technique described was in mole-
cular form and not carried by dust.
ACKNOWLEDGEMENTS
We wish to thank Dragon Operations Group for operation of the Dracule

probe and for values of R / B for the inert gases. Our thanks are also due to
Chemistry Group at Harwell and especially to Mr. P. E. Brown for the
radiochemical measurements on samples. We are also grateful to
Mr. R. Hewitson for computational assistance and to Mr. D. Barnes for
assistance in organizing the cutting-up of the heat-exchanger.
REFERENCES
[1] ROWLAND, P . R . , PITCHFORD, В . , BROWNING, W. E., CARLYLE, M . , D . P . (British) Rep.660 (1970).

[2] ROWLAND, P . R . , CARLYLE, M . , SOUBELET, G. C . , D . P . (British) Rep. 702 (1969).
[3] GORMLEY and KENNEDY, Proc. Roy. Irish Acad. A52 (1949) 163.
[4] OTHMER, D . F . , CHEN, H . T . , Ind. Eng. C h e m . , Process Des. Dev. 1 (1962) 249.
[5] ROWLAND, P . R . , BROWN, P. E., D . P . (British) Rep. (to be published)
[6] Approximate estimate from values given by F. P. O. ASHWORTH (private c o m m u n i c a t i o n ) .
[7] NEILL, F . H . , ORNL-TM-2763 (1970).
[S] FLOWERS, R . H . , D . P . (British) Rep.719, Part 7 (1970).
[9] HOINKIS, E. , ORNL-TM-2916 (1970).
[10] VANSLAGER, F. E., BELL, W. E., SISMAN, О . , MORGAN, M . T . , Gulf General Atomic Rep. GA 10073
(1970).
[11] BROWNING, W . E . , ROWLAND, P. R . , D . P . (British) Rep. (unpublished)
CONTROL OF AIRBORNE RADIOIODINE IN
THE LOSS-OF-FLUID TEST (LOFT) FACILITY
W.P. GAMMILL
Division of Reactor Development and Technology,
United States Atomic Energy Commission,
Washington, D.C. , United States of America
Abstract
C O N T R O L O F AIRBORNE RADIOIODINE IN THE LOSS-OF-FLUID TEST (LOFT) FACILITY.

A description is given of the o b j e c t i v e s of the l o s s - o f - f l u i d test (LOFT) program, which is one of the
USAEC's m a j o r nuclear safety research and d e v e l o p m e n t programs, and of the facilities used in this
program, A h a l o g e n and particulate removal system is an integral part o f the heating, ventilating and air-
conditioning system o f the containment building. T h e filter train consists o f an entrained moisture
separator, an e l e c t r i c duct heater, a filter assembly containing both roughing filters and HEPA filters,
and i o d i n e - i m p r e g n a t e d c h a r c o a l adsorbers. T h e basic o b j e c t i v e of the filter system is to reduce the
turn-round t i m e between experiments or to permit earlier access to the test c h a m b e r following a nuclear
experiment. T h e design e f f i c i e n c y of the filter system is considered to be m u c h greater than would
normally b e required for a recirculating filter system, but the possibility of operating the system in a single
pass m o d e justifies the higher design e f f i c i e n c y .
1. INTRODUCTION
The l o s s - o f - f l u i d test ( L O F T ) p r o g r a m is one of the United States

A t o m i c E n e r g y C o m m i s s i o n ' s m a j o r nuclear safety r e s e a r c h and d e v e l o p -
ment p r o g r a m s . The L O F T f a c i l i t y will be one in which integral safety
tests can be conducted on a m a j o r l o s s - o f - c o o l a n t accident experiment
to study accident initiation, r e s p o n s e and consequence phenomena in a
single test with engineered safety s y s t e m s in operation.
The original o b j e c t i v e s of the L O F T p r o g r a m w e r e :
(a) T o conduct tests which would demonstrate the behaviour of a typical

p r e s s u r i z e d water r e a c t o r system and plant equipment with r e s p e c t
to safety under simulated accident conditions, and
(b) T o provide quantitative information on the behaviour of f i s s i o n products
following a l o s s - o f - c o o l a n t accident in such a system.
O v e r the past few y e a r s , there has been an i n c r e a s e d emphasis on

the c i r c u m s t a n c e s leading to the l o s s - o f - c o o l a n t accident and the analysis
a s s o c i a t e d with preventing a c o r e ' m e l t d o w n . Thus in 1967 it was decided
that L O F T would be of m o r e value as a f a c i l i t y in which e m e r g e n c y c o r e
c o o l i n g s y s t e m s could be tested under r e a l i s t i c r e a c t o r accident conditions.
The experimental o b j e c t i v e s of the r e o r i e n t e d L O F T p r o g r a m a r e as
follows:
(a) T e s t the adequacy of analytical methods used to predict:

(i) the l o s s - o f - c o o l a n t phenomena affecting c o r e thermal r e s p o n s e ;
(ii) the capability of the e m e r g e n c y c o r e cooling s y s t e m to fulfil
the intended function;
73
74 GAMMILL
(iii) the m a r g i n s of safety inherent in the capability of the e m e r g e n c y

core cooling system;
(iv) the thermal and m e c h a n i c a l r e s p o n s e of the c o r e and p r i m a r y
system components;
(v) the p r e s s u r e - t e m p e r a t u r e r e s p o n s e of the containment a t m o s p h e r e ;
and
(vi) the magnitude, c o m p o s i t i o n and distribution with r e s p e c t to time
of the f i s s i o n products in the containment building.
(b) V e r i f y the design r e q u i r e m e n t s which determine the capability of the

e m e r g e n c y c o r e c o o l i n g system and the p r e s s u r e reduction system to
f u l f i l their intended functions.
(c) R e v e a l thresholds o r unexpected phenomena which m a y a f f e c t the
validity of the analytical methods used to predict the e f f e c t s of a l o s s - o f -
coolant accident as listed above.
The r e d i r e c t i o n of the LOFT p r o g r a m has necessitated many changes

in the design of the f a c i l i t y as well as in the experimental p r o g r a m which,
in turn, have caused construction delays. The facility, which is being
constructed at the National R e a c t o r Testing Station (NRTS) in Idaho, is
about 55% completed (as of late 1970). Initial cold blowdown tests are
scheduled f o r 1973 with the f i r s t hot r e a c t o r tests to be conducted in 1974.
Although no c o r e meltdown tests are now planned, the f a c i l i t y is still
designed to tolerate such a condition without creating an undue hazard to
operating p e r s o n n e l o r p e r s o n s living near the NRTS.
2. DESCRIPTION OF F A C I L I T Y
The LOFT f a c i l i t y is c o m p o s e d of three main structures: the contain-

ment building, the c o n t r o l and equipment building and the containment
s e r v i c e s building.
The containment building is designed to house the experiment and to
contain the radioactive m a t e r i a l s r e l e a s e d as a result of the experiment.
The containment shell is a steel cylinder with a h e m i s p h e r i c a l top and
ellipsoidal bottom. The shell is 70 ft in d i a m e t e r , 129 ft high, and
97 ft above ground. The f r e e volume of the building is 302 000 ft 3 . The
underground portion of the structure is isolated f r o m the main test c h a m b e r .
A condensation sump 17. 5 ft deep and 8. 5 ft in diameter is located in the
centre of the test c h a m b e r f l o o r . The basement is divided into r o o m s
round the central sump. Adequate c o n c r e t e shielding is provided to allow
a c c e s s to the equipment r o o m in the basement at all times. The shell is
designed to maintain its leak-tightness when subjected to an internal
p r e s s u r e of 40 l b / i n 2 gauge and temperature of 260°F. The design leak
rate is 0. 2% by weight of the f r e e volume in 24 hours. The l a r g e s t opening
in the containment building is the 2 2 - f t wide by 33-ft high d o o r which will
allow passage of the r e a c t o r s y s t e m and r a i l r o a d dolly on which the
r e a c t o r is mounted.
The c o n t r o l and equipment building is an underground r e i n f o r c e d c o n -
c r e t e structure c o v e r e d with 8 ft of earth. The building has two l e v e l s
and m e a s u r e s approximately 105 ft X 94 ft. It contains the main control
r o o m , data handling r o o m s , l a b o r a t o r i e s , counting r o o m , o f f i c e s ,
RADIOIODINE IN THE LOFT FACILITY 75
e m e r g e n c y p o w e r g e n e r a t o r , e l e c t r i c a l equipment r o o m , shower and

c h a n g i n g - r o o m , etc.
The containment s e r v i c e s building is a s i n g l e - l e v e l underground
structure, with the exception of a tower structure which is adjacent to
the containment building. This building connects the control and equip-
ment building to the containment building. It houses the f i l t e r s y s t e m ,
the equipment r o o m s f o r the e m e r g e n c y c o r e cooling and hot waste s y s t e m s ,
e l e c t r i c a l equipment r o o m and a c c e s s to the tower structure. The tower
structure houses an a i r l o c k a c c e s s r o o m , cable and pipe shielding
labyrinths, stairway and equipment a c c e s s shaft.
The r e a c t o r and p r i m a r y cooling system will be typical of current
p r e s s u r i z e d light-water r e a c t o r s except f o r s i z e . The initial c o r e will
be a U 0 2 pin type about 66 inches long. The r e a c t o r and p r i m a r y c o o l i n g
system design will a c c o m m o d a t e later c o r e s up to 12 feet long. The
power level will be 55 MW(th) with a m a x i m u m power density of 19 k W / f t
to provide a uniform thermal behaviour region that will have a hot spot
behaviour equivalent to that of a typical P W R .
3. HALOGEN AND P A R T I C U L A T E R E M O V A L SYSTEM
The L O F T halogen and particulate r e m o v a l system is an integral

part of the containment building heating, ventilating and air-conditioning
s y s t e m . The s y s t e m will be housed in a vault designed to a c c o m m o d a t e
two parallel f i l t e r and a d s o r b e r trains. H o w e v e r , the initial system will
c o n s i s t of only one of the f i l t e r trains, the other being d e f e r r e d until a
need is demonstrated.
The f i l t e r train c o n s i s t s of an entrained m o i s t u r e s e p a r a t o r , an
e l e c t r i c duct heater, a f i l t e r a s s e m b l y containing both roughing f i l t e r s
and HEPA f i l t e r s , and i o d i n e - i m p r e g n a t e d c h a r c o a l a d s o r b e r s .
The entrained m o i s t u r e s e p a r a t o r is a d e m i s t e r designed to r e m o v e ,
f r o m an a i r f l o w of 4000 ft 3 /min, not l e s s than 99% of entrained water in
the droplet s i z e range of 1 - 5 ц т and 100% of droplets l a r g e r than 5 ц т .
The d e m i s t e r m e d i a will be a l-in.-thick m u l t i l a y e r mat fabricated f r o m
0. 0008 T F F T e f l o n yarn and 0.006 type 304 stainless steel wire with type 304
stainless steel casing and retaining s c r e e n s on both f a c e s . The d e m i s t e r
m e d i a will be installed and attached to the housing in 24 in. banks with a
drain c o l l e c t i o n through and down spout to prevent spillage a c r o s s the f a c e
of a l o w e r bank.
The purpose of the e l e c t r i c duct heater is to l o w e r the relative
humidity of the air going to the f i l t e r s to prevent plugging of the f i l t e r s
with condensation. The heater is sized to r a i s e the 4000 ft 3 /min, air flow
a minimum of 20 degF above its dewpoint temperature.
The f i l t e r a s s e m b l y housing p r o v i d e s r e c e p t a c l e s f o r the roughing
f i l t e r s and the HEPA f i l t e r s . The f i l t e r bank will contain f o u r
24-in. X 24-in. X l l | - i n . f i l t e r s in a v e r t i c a l arrangement. F i l t e r e f -
f i c i e n c y will be 85% NBS. The HEPA f i l t e r s will be the same s i z e as the
roughing f i l t e r and will have an e f f i c i e n c y of 99.97% with 0.3 д т DOP p a r t i c l e s .
The halogen r e m o v a l a d s o r b e r s will be located downstream of the
HEPA f i l t e r s and will be made up of three a d s o r b e r a s s e m b l i e s in s e r i e s .
Each a s s e m b l y will c o n s i s t of f o u r a c c o r d i o n - t y p e carbon a d s o r b e r c e l l s
in parallel. Each cell will be nominally 24 in. X 24 in. X l l | in. The
76 GAMMILL
adsorption m e d i a will be i o d i n e - i m p r e g n a t e d , activated c h a r c o a l . The

thickness of the a d s o r b e r bed will be approximately one inch. The
e f f i c i e n c y f o r the r e m o v a l of elemental iodine will be at least 99. 99%. The
f i r s t bank of c h a r c o a l a d s o r b e r s is provided with a separate c o o l i n g system
to be used to r e m o v e decay heat generated by a d s o r b e d radioactive halogens.
T h i s system will only be used when it is n e c e s s a r y to interrupt the main
f i l t e r flow o r if the r e c i r c u l a t i n g fan fails. If this system is unable to
c o n t r o l the temperature r i s e , the vault will be isolated and an inert gas
r e l e a s e d to smother the f i r s t a d s o r b e r bank. Enough nitrogen will be
available to s u b m e r g e the isolated a r e a c o m p l e t e l y .
The s y s t e m will be capable of operation in a single pass m o d e with
the exhaust going to the stack, o r in a r e c i r c u l a t i n g m o d e with the a i r
being returned to the test c h a m b e r . Under n o r m a l operating conditions,
the f i l t e r system will be bypassed and the ventilation outlet will be direct
to the stack. The f i l t e r system is located outside the containment building
and is not designed to withstand the p r e s s u r e s that will be e x p e r i e n c e d
within the containment. T h e r e f o r e , following an accident o r simulated
accident, when the test c h a m b e r p r e s s u r e builds up toward its m a x i m u m ,
the containment vess'el isolation valves will be automatically c l o s e d .
A f t e r the p r e s s u r e has been reduced in the test c h a m b e r , the c l e a n - u p
system will be actuated and the containment atmosphere will be circulated
through the f i l t e r system and returned to the test c h a m b e r .
4. PRESSURE REDUCTION SPRAY SYSTEM
The p r e s s u r e reduction spray system will be an experimental system

designed to evaluate the e f f e c t s of sprays on the p r e s s u r e - t e m p e r a t u r e
r e s p o n s e of the test c h a m b e r atmosphere and on the r e m o v a l of a i r b o r n e
f i s s i o n products. Although no f i r m d e c i s i o n has yet been made (as of
late 1970), the s y s t e m is not at present c l a s s i f i e d as a plant protection
s y s t e m . Current plans a r e f o r the system to be designed so as to facilitate
the addition of the redundancy required in a safety system if such a system
should be r e q u i r e d by future p r o g r a m s .
The principal components of this system will c o n s i s t of a pump, spray
ring, header with n o z z l e s , n e c e s s a r y piping, v a l v e s , instrumentation,
c o n t r o l s and a sump f o r storing solutions. A l l active components of the
system will be located in the containment basement. Only the n o z z l e s and
piping located in the test c h a m b e r will be subjected to the s t e a m - a i r
environment.
The spray solution chosen f o r the p r e s s u r e reduction system will
c o n s i s t of d e m i n e r a l i z e d water containing b o r i c acid at a concentration of
about 2000 ppm. In addition, other c h e m i c a l additives typical of those
used in c o m m e r c i a l nuclear p o w e r plants, such as sodium hydroxide, m a y
be added to the solution. About 12 000 gal of the solution will be m i x e d
immediately b e f o r e the start of any nuclear operation and stored in a
p r e s s u r e reduction and decontamination sump adjacent to the condensate
sump.
The spray n o z z l e s a r e attached to two c o n c e n t r i c header rings mounted
horizontally near the top of the containment v e s s e l . The outer ring will
contain twenty n o z z l e s and the inner ring will contain eight. Solid cone
f o g n o z z l e s w e r e s e l e c t e d as m o s t suitable because of the need f o r relative
RADIOIODINE IN THE LOFT FACILITY 77
u n i f o r m c o v e r a g e in the spray pattern. T h e s e n o z z l e s will provide spray

droplets having a mean diameter of 700-800 Mm.
A 50-hp e l e c t r i c pump will transport the spray solution to the n o z z l e s
at a rate of 500 g a l / m i n . The spray droplets, on reaching the f l o o r ,
will be c o l l e c t e d in a peripheral trench and flow to a f i l t e r sump. The
f i l t e r sump contains a strainer that will r e m o v e p a r t i c l e s of diameter
l a r g e r than about 3/32 in. The n o z z l e s will be capable of passing p a r t i c l e s
up to 1 / 8 in. d i a m e t e r . F r o m the f i l t e r sump the solution will be returned
to the p r e s s u r e reduction and decontamination sump. Upon c o m p l e t i o n
of each experiment the spray solution will either be discharged to the
liquid waste tank o r stored in the sump f o r use in the next experiment.
5. CONCLUSION
Although no f i r m d e c i s i o n s have been m a d e , neither of the two s y s t e m s

d e s c r i b e d in this paper is at p r e s e n t designed to m e e t the United States
standards f o r an engineering safety feature. Both s y s t e m s a r e provided
to fulfil p r o g r a m m a t i c needs.
The b a s i c objective of providing a f i l t e r system f o r the LOFT f a c i l i t y
is to reduce turn-round time between e x p e r i m e n t s or to p e r m i t e a r l i e r
a c c e s s to the test c h a m b e r following a nuclear experiment. The design
f l o w rate of 4000 f t 3 / m i n will provide one change of building a i r e v e r y
o n e - a n d - a - q u a r t e r hours. T h i s is obviously too low to have any significant
e f f e c t on leakage of f i s s i o n products f r o m the containment building. T h i s
is e s p e c i a l l y true since the s y s t e m is not designed to operate while the
test c h a m b e r is p r e s s u r i z e d — the p e r i o d during which m a x i m u m leakage
would be expected to o c c u r . However, the system should be e f f e c t i v e in
reducing the a i r b o r n e concentration of persistent s p e c i e s of iodine, such
as methyl iodide, which will probably exist after the p r e s s u r e reduction
s p r a y s have been turned off. T h i s should allow personnel a c c e s s to the
test c h a m b e r within a reasonably short time. The system could a l s o be
of value in the event of m i n o r leaks in the r e a c t o r system during n o r m a l
operations.
The design e f f i c i e n c y of the f i l t e r system is c o n s i d e r e d to be much
g r e a t e r than would n o r m a l l y be r e q u i r e d f o r a r e c i r c u l a t i n g f i l t e r system.
However, the p o s s i b i l i t y of operating the system in the single pass m o d e
j u s t i f i e s the higher design e f f i c i e n c y .
The need f o r duplicating the spray conditions in a typical p r e s s u r i z e d
light-water r e a c t o r , i. e. droplet size and flow p e r unit of containment
c r o s s - s e c t i o n a l a r e a , was c h o s e n as the design b a s i s f o r the p r e s s u r e
reduction spray system. While the spray solution selected f o r the initial
tests is typical of what would be used in m o s t nuclear power plant spray
s y s t e m s , the requirement f o r multiple or repeated use of the L O F T
facility m a y eliminate the p o s s i b i l i t y of using m o r e effective but m o r e
c o r r o s i v e solutions, such as sodium thiosulphate.
К ВОПРОСУ ОБ АНАЛИЗЕ РАДИОАКТИВНОГО
ЙОДА
И . Е . Н А Х У Т И Н , JI. H. P A C T У НОВ,
Н.М.СМИРНОВА
Государственный комитет
по использованию атомной энергии С С С Р ,
Москва,
Союз С о в е т с к и х Социалистических Республик
Abstract-Аннотация
ANALYSIS OF RADIOIODINE.
T h e authors consider the problem o f analysing radioiodine in the atmosphere. An all-purpose
m e t h o d providing a general analysis is the adsorption of radioiodine on activated c h a r c o a l or on a bundle
of filters containing activated c h a r c o a l . T h e i o d i n e compounds can be d e t e c t e d , and their contribution
to the overall activity determined, from the iodine distribution in the analytical c o l u m n and the slope
angles o f curves plotted on the c o - o r d i n a t e s lg C ( x ) .
Individual c o m p o u n d s can be identified by means o f g a s - l i q u i d chromatography. Columns containing
c i t r i c a c i d tri-isopropyl ether or triphenylphosphate show separation o f a m i x t u r e o f 7 - c o m p o n e n t i o d o -
hydrocarbons, including the unsaturated type, but the triphenylphosphate c o l u m n is less e f f i c i e n t .
К ВОПРОСУ ОБ АНАЛИЗЕ РАДИОАКТИВНОГО ЙОДА.

Р а с с м а т р и в а е т с я в о п р о с о б а н а л и з е р а д и о а к т и в н о г о й о д а в в о з д у х е . Для о б щ е г о
а н а л и з а у н и в е р с а л ь н ы м м е т о д о м я в л я е т с я а д с о р б ц и я на а к т и в н о м у г л е или на п а к е т е ф и л ь -
т р о в , содержащих активный у г о л ь . Обнаружение соединений йода и определение их вклада
в о б щ у ю а к т и в н о с т ь м о ж е т быть п р о и з в е д е н о по распределению йода в аналитической к о -
лонке и у г л а м наклона кривых в координатах I g C ( X ) .
Идентификация о т д е л ь н ы х соединений м о ж е т быть произведена с помощью г а з о -
жидкостной хроматографии. На к о л о н к а х с т р и - и з о п р о п и л о в ы м э ф и р о м л и м о н н о й к и с л о т ы ,
а также с трифенилфосфатом разделена с м е с ь йодистых у г л е в о д о р о д о в из 7-ми компонен-
т о в , в т о м числе непредельных у г л е в о д о р о д о в , однако колонка с трифенилфосфатом я в л я е т -
ся менее эффективной.
Анализ общего содержания радиоактивного йода в воздухе и других

г а з а х не представляет о с о б ы х трудностей и может быть осуществлен
многими способами . Наиболее универсальным м е т о д о м в о т с у т с т в и и
агрессивных г а з о в является адсорбция йода на активном угле с п о с л е -
дующей регистрацией е г о излучения. Универсальность э т о г о м е т о д а
связана с т е м , что на активном угле адсорбируется не только м о л е к у -
лярный йод, но и г а з о о б р а з н ы е соединения йода.
При очень длительном пропускании воздуха через слой угольной
шихты в ы с о т о й 30-40 см можно уловить микропримеси, содержащиеся
в чрезвычайно малых количествах [ 1 ] . Если слой угольной шихты р а з -
делить по в ы с о т е на секции, т о такая секционированная колонка п о з в о -
ляет обнаруживать г а з о о б р а з н ы е соединения йода и оценить их вклад в
общую активность . Это производится по измерению углов наклона о т -
резков прямых на графике l g C = f (X), где С - концентрация радиоактив-
ного йода в у г л е , а X - расстояние от входа в колонку [1].
79
80 НАХУТИН и др.
При анализах общего содержания йода в ы с о т а слоя шихты зависит

от точности, которую необходимо получить. При не очень точных ана-
лизах в ы с о т а слоя может быть небольшой. Кроме т о г о , в ы с о т а слоя
шихты существенно зависит от грануляции угля . При анализе общего
содержания возможно также предварительное каталитическое сжигание
йодистых углеводородов [1]. Установка аналитического аэрозольного
фильтра перед углем позволяет регистрировать йод также и в а э р о з о л ь -
ной ф а з е . Модификацией э т о г о метода является применение пакета
фильтров из фильтрматериала, содержащего активный у г о л ь .
Удовлетворяя потребности в м а с с о в ы х анализах, эти м е т о д ы , однако,
не позволяют производить идентификацию соединений йода, находящихся
в газовой ф а з е . Между т е м , как правило, именно газообразные плохо
адсорбируемые соединения йода ограничивают коэффициенты очистки.
П о э т о м у при выборе с р е д с т в очистки существенно знать не только общее
содержание радиоактивного йода в г а з а х , но и с о с т а в соединений, в к о -
т о р ы х он п р и с у т с т в у е т . Чем выше коэффициент очистки, который мы
хотим получить, тем подробнее необходимо знать химический с о с т а в
соединений йода.
Работами Эглтона и Аткинса [2], а также Смита и В е с т а [3], было
показано, что в воздухе присутствуют йодистый метил и некоторые д р у -
гие алкилйодиды . Однако, с о с т а в йодистых углеводородов в настоящее
время изучен н е д о с т а т о ч н о . Кроме т о г о , э т о т с о с т а в может резко и з -
меняться в зависимости от происхождения анализируемых г а з о в . В с в я -
зи с этим мы исследовали возможности разделения и идентификации
различных йодистых углеводородов (в том числе и непредельных) при
помощи с о о т в е т с т в у ю щ е г о подбора неподвижной фазы в х р о м а т о г р а ф и -
ческом анализе.
ИССЛЕДОВАНИЯ ВОЗМОЖНОСТЕЙ Х Р О М А Т О Г Р А Ф И Ч Е С К О Г О
АНАЛИЗА РАЗЛИЧНЫХ ЙОДИРОВАННЫХ УГЛЕВОДОРОДОВ
Вначале исследования проводились с нерадиоактивными йодистыми

углеводородами на г а з о в о м хроматографе " Х р о м - 2 " . Затем аналогичные
опыты были проведены с йодистыми соединениями, меченными й о д о м - 1 3 1 ,
на хроматографической установке с анализатором по радиоактивности.
Метка вводилась в йодсодержащее соединение м е т о д о м изотопного
обмена.
U - о б р а з н ы е колонки с внутренним диаметром 6 мм заполнялись
насадками с различными неподвижными фазами ( Н . Ф . ) . В качестве
Н . Ф . испытывались: с к в а л а н , динонилфталат, дибутилфталат, с м е с ь
дибутилфталата и дифенилформамида, трифенилфосфат и три-изопропи-
ловый эфир лимонной кислоты . Эффективная длина колонок во в с е х
опытах составляла 85 с м . Носитель " С ф е р о х р о м - I " (фракция 0,315-0,4 мм)
перед нанесением Н . Ф . прокаливался при t = 900°С в течение 4 - х часов .
Содержание Н . Ф . на носителе и в колонке приведено в т а б л . 1 .
Сложная неподвижная фаза готовилась из расчета 75% в е с . дибутил-
фталата и 2 5% в е с . дифенилформамида от общего содержания Н . Ф . на
носителе. В к а ч е с т в е г а з а - н о с и т е л я во в с е х опытах использовался а з о т .
С к о р о с т ь потока г а з а - н о с и т е л я в разных опытах поддерживалась в п р е д е -
лах 59-61 м л / м и н . Колонки термостатировались при t = 50 ± 0,5°С.
Анализ радиоактивного йода 81
ТАБЛИЦА I. СОДЕРЖАНИЕ Н . Ф . НА НОСИТЕЛЕ И В КОЛОНКЕ
Концентра- В е с насадки Количество

ция H . ф . в в колонке, H.ф . в ко-
Неподвижная фаза
насадке, г лонке,
% вес. г
Сквалан 10,4 14,97 1,56
Динонилфталат 10,6 1 5 , 1* 1,6
Дибутилфталат 10,23 13,3 1,36
Дибутилфталат + Дифенил- 9,78 13,86 1,36

формамид
Три-изопропиловый эфир 9,5 14,14 1,34

лимонной кислоты
Трифенилфосфат 9,5 14,56 1,38
Проба, составленная из паров й о д и с т о г о метила (0,1 мл), й о д и с т о г о

этила (0,1 мл), й о д и с т о г о изопропила (0,1 мл), йодистого пропила (0,15 мл),
й о д и с т о г о аллила (0,15 мл), й о д и с т о г о изобутила (0,2 мл) и йодистого
бутила (0,2 мл), в з я т ы х при комнатной температуре, вводилась в х р о м а -
тограф с помощью шприца. Хроматографическая установка, в которой
разделялись соединения, содержащие 1 3 1 J , была снабжена детектором
по радиоактивности. Выход пиков регистрировался по /3-активности с
помощью счетчика )3-частиц С И - 2 Б .
В с е испытанные Н.Ф. хорошо делят пики как нормальных йодистых
алкилов, составляющих гомологический ряд, так и нормальных алкилов
с их и з о м е р а м и . Однако лишь только три-изопропиловый эфир лимонной
кислоты, трифенилфосфат и Н . Ф . , состоящая из дибутилфталата и д и -
фенилформамида, позволяют частично разделить пики йодистого пропила
и й о д и с т о г о аллила. На колонках с дибутилфталатом и динонилфталатом
эти компоненты вообще не делятся (рис.1 и 2), а на колонке с о скваланом
пик й о д и с т о г о пропила в отличие от других Н . Ф . выходит за пиком
йодистого аллила в виде ступеньки ( р и с . 3 ) .
В т а б л . I I представлены значения коэффициентов селективности ( К с ) ,
рассчитанные по формуле:
v = о V*
—S- V'-Я-
К с ¿ vs + W '
где Vg и Vg — абсолютные удерживаемые объемы соседних пиков,

К с — коэффициент селективности, зависящий только от природы
Н . Ф . (так как Vg пропорционален коэффициенту р а с п р е д е -
ления) и характеризующий селективность самой Н . Ф . по
отношению к йодистым углеводородам различных к л а с с о в .
Рис.1. Х р о м а т о г р а м м а й о д и с т ы х у г л е в о д о р о д о в на к о л о н к е с " д и б у т и л ф т а л а т о м " .

Пики 1 - 3 не и д е н т и ф и ц и р о в а н ы , 4 — й о д и с т ы й м е т и л , 5 — й о д и с т ы й э т и л , 6 - й о д и с т ы й
изопропил, 7 - й о д и с т ы й пропил + й о д и с т ы й аллил, 8 - й о д и с т ы й и з о б у т и л , 9 - й о д и с т ы й
бутил.
4 3
Рис.2. Х р о м а т о г р а м м а й о д и с т ы х у г л е в о д о р о д о в на к о л о н к е с " д и н о н и л ф т а л а т о м " .

П и к и 1 - 2 не и д е н т и ф и ц и р о в а н ы , 3 - й о д и с т ы й м е т и л , 4 - й о д и с т ы й э т и л , 5 - й о д и с т ы й и з о -
пропил, 6 - й о д и с т ы й пропил + й о д и с т ы й аллил, 7 - й о д и с т ы й и з о б у т и л , 8 - й о д и с т ы й б у т и л .
Рис.3. Х р о м а т о г р а м м а й о д и с т ы х у г л е в о д о р о д о в на к о л о н к е с о " с к в а л а н о м " .

Пики 1 - 2 н е и д е н т и ф и ц и р о в а н ы , 3 — й о д и с т ы й м е т и л , 4 — й о д и с т ы й э т и л , 5 - й о д и с т ы й и з о -
пропил, 6 - й о д и с т ы й аллил, 7 - й о д и с т ы й пропил, 8 - й о д и с т ы й и з о б у т и л , 9 - й о д и с т ы й
бутил.
ТАБЛИЦА II. КОЭФФИЦИЕНТЫ СЕЛЕКТИВНОСТИ
Разделяемые компоненты
Неподвижная CHqJ C2H5J и-С3 H7J H-C3H7J СН2 = C H - C H 2 J И - С 4 Н9 J

фаза Q> H 5 J И-С3 H7J н - С 3 Н7 J CH2 = CH-CH2J и-C4H9J Н - С 4 Hg J
Сквалан 0,87 0,55 0,33
Динонилфталат 0,83 0,52 0 0,37
Дибутилфталат 0,82 0,50 0,44 0,06 0,44 0,34
Дибутилфталат + 0,86 0,47 0,44 0,16 0,38 0,34

+ дифенилформа-
мид
Три-изопропило- 0,57 0,44 0,4 0,2 0,32 0,3

вый эфир лимон-
ной кислоты
Трифенил фосфат 0,77 0,40 0,45 0,2 0,25 0,37
Из данных таблицы видно, что Н . Ф . обладают наибольшим коэффици-

ентом селективности для йодистых алкилов, причем коэффициент с е л е к -
тивности падает при переходе к изомерам йодистых алкилов (например,
н - С 3 Н 7 - н - С 3 H 7 ) , а также к непредельным соединениям с одинаковым
числом углеродных атомов (йодистый пропил - йодистый аллил). Кроме
т о г о , полученные коэффициенты селективности для динонилфталата и
дибутилфтолата показывают, что данные Н . Ф . не пригодны для анализа
соединений с близкими точками кипения, таких как йодистый пропил и
йодистый аллил.
С добавлением к дибутилфталату т а к о г о сильно полярного вещества
как дифенилформамид, обладающего высокой селективностью по о т н о ш е -
нию к непредельным углеводородам, в о з р о с коэффициент селективности
Н . Ф . для с и с т е м ы йодистый пропил - йодистый аллил. Эта сложная Н . Ф .
позволила разделить пики этих компонентов со степенью разделения
<Р= 0,19 ( р и с . 4 ) . Приблизительно вдвое большей степени разделения пиков
й о д и с т о г о пропила и йодистого аллила удалось достигнуть на колонках с
три-изопропиловым эфиром лимонной кислоты и трифенилфосфатом
(рис . 5 и 6). Однако, если на трифенилфосфате пики йодистого аллила и
йодистого изобутила разделились неполностью (степень разделения
<р = 0,46), то на три-изопропиловом эфире лимонной кислоты эти к о м п о -
ненты разделены полностью (К р = 1,01) при равных степенях разделения
йодистого пропила и йодистого аллила ( т а б л . Ш ) .
Средние значения В Э Т Т , вычисленные по хроматографическим пикам
для каждого компонента, показывают, что колонка с три-изопропиловым
эфиром лимонной кислоты имеет несколько большую эффективность по
сравнению с колонкой с трифенилфосфатом .
Проведенные исследования с нерадиоактивными йодистыми соединени-
ями позволили найти неподвижную фазу, на которой в с е компоненты э т а -
лонной с м е с и делятся удовлетворительно, а также условия проведения
х р о м а т о г р а ф и ч е с к о г о анализа. На р и с . 7 представлена хроматограмма

йодистых у г л е в о д о р о д о в , меченных й о д о м - 1 3 1 , полученная на х р о м а т о - .
графической у с т а н о в к е , собранной нами.
Для х р о м а т о г р а ф и ч е с к о г о анализа использовалась спиральная с т е к -
лянная колонка длиною в 1 м, заполненная насадкой с три-изопропиловым
эфиром лимонной кислоты в качестве неподвижной фазы. Остальные
условия проведения хроматографического анализа остались прежними.
Несколько худшее разделение пиков й о д и с т о г о пропила и йодистого
аллила можно объяснить несовершенством детектора по радиоактивности.
Рис.4. Х р о м а т о г р а м м а й о д и с т ы х у г л е в о д о р о д о в на к о л о н к е с " д и б у т и л ф т а л а т о м " + " д и -

фенилформамидом". Пики 1 - 4 н е и д е н т и ф и ц и р о в а н ы , 5 — й о д и с т ы й м е т и л , 6 - н е и д е н т и -
ф и ц и р о в а н , 7 - й о д и с т ы й э т и л , 8 - й о д и с т ы й и з о п р о п и л , 9 — й о д и с т ы й п р о п и л , 10 — й о д и с -
т ы й а л л и л , 11 - й о д и с т ы й и з о б у т и л , 12 - й о д и с т ы й б у т и л .
Рис.5. Х р о м а т о г р а м м а й о д и с т ы х у г л е в о д о р о д о в на к о л о н к е с " т р и - и з о п р о п и л о в ы м э ф и р о м
л и м о н н о й к и с л о т ы " . Пики 1 - 5 не и д е н т и ф и ц и р о в а н ы , 6 - й о д и с т ы й м е т и л , 7 - не и д е н т и ф и -
ц и р о в а н , 8 - й о д и с т ы й э т и л , 9 - й о д и с т ы й и з о п р о п и л , 10 - й о д и с т ы й п р о п и л , 11 - й о д и с т ы й
а л л и л , 12 - й о д и с т ы й и з о б у т и л , 1 3 — й о д и с т ы й б у т и л .
Рис.6. Х р о м а т о г р а м м а й о д и с т ы х у г л е в о д о р о д о в на к о л о н к е с "трифенилфосфатом".
П и к и 1 - 5 не и д е н т и ф и ц и р о в а н ы , 6 - йодистый метил, 7 - не и д е н т и ф и ц и р о в а н , 8 - йодистый
э т и л , 9 — й о д и с т ы й и з о п р о п и л , 10 - й о д и с т ы й п р о п и л , 11 - й о д и с т ы й а л л и л , 12 — й о д и с т ы й
изобутил, 13 — йодистый бутил.
ТАБЛИЦА III. КРИТЕРИИ (К р ) И СТЕПЕНИ (<р) РАЗДЕЛЕНИЯ

КОМПОНЕНТОВ НА РАЗНЫХ НЕПОДВИЖНЫХ ФАЗАХ
Разделяемые компоненты
Неподвижная CH3J С , Hñ J и - С , H7J н-С, H,J CH2 = CH-CH2J И - С 4 Hg J

фаза C2H5J н-С3 H7J н-С3 H7J CH2 = CH-CH2J H-C4H9J H - C 4 Hg J
К Р
К
Р К Р
<P Kp ip Kp
Сквалан 2,21 1,5 0 1,09
Динонилфталат 2,13 1,32 0 1Д
Дибутилфталат 2,44 1,48 0 1,28
Дибутилфталат + 2,24 1,48 1,41 0,19 1,28

+ Дифенилформа-
мид
Три-изопропило- 2,16 1,28 1,19 0,43 1,01 1,04

вый эфир лимон-
ной к и с л о т ы
Трифенил фосфат 2,03 1,15 1,29 0,42 0,46 1,15

Рис . 7. Х р о м а т о г р а м м а й о д и с т ы х у г л е в о д о р о д о в , м е ч е н н ы х й о д о м - 1 3 1 , на к о л о н к е с "три-
изопропиловым эфиром лимонной кислоты".
Однако, несмотря на указанный н е д о с т а т о к , устранить который не пред-

ставляет о с о б о й трудности, данная колонка позволяет установить при-
с у т с т в и е й о д и с т о г о пропила и й о д и с т о г о аллила в анализируемой п р о б е .
Учитывая также, что в с е компоненты эталонной с м е с и выходят из х р о -
матографической колонки в порядке возрастания температур кипения,
можно считать, ч т о йодистый этил и йодистый этилен, для которых р а з -
ница в температурах кипения равна 16,2°С, также разделятся на этой
колонке, позволившей разделить пики йодистого аллила и йодистого п р о -
пила, для которых разница в температурах кипения с о с т а в л я е т в с е г о
0,7°С.
В большинстве случаев перед анализом т р е б у е т с я проводить кон-
центрирование анализируемых йодистых у г л е в о д о р о д о в , поскольку п о -
следние присутствуют в воздухе в крайне малых количествах.
ЛИТЕР АТУ P А
[1] НАХУТИН, И.Е. и д р . , "Атомная энергия" 26 4 (1969) 390-391.

[2] EGGLETON, A.E.I.', ATKINS, D.H.F., " R a d i o c h i m . a c t a " 3 3 ( 1 9 6 4 ) 151 - 5 8 .
[3] SMITH, S. R . , WEST, D.L., "Nucl.Appl." 3 1 (1967) 43-45.
TRAPPING OF RADIOACTIVE IODINE
PRODUCED BY NUCLEAR POWER STATIONS:
SAMPLING AND ANALYSIS EQUIPMENT;
ON-SITE CHECKING
J. BRION
Service Technique d'Etudes de Protection,
Centre d' Etudes Nucléaires de Fontenay-aux-Roses, France
Abstract
TRAPPING OF RADIOACTIVE IODINE PRODUCED BY NUCLEAR POWER STATIONS: SAMPLING AND

ANALYSIS EQUIPMENT; ON-SITE CHECKING.
Particulate i o d i n e and e l e m e n t a l gaseous iodine can be trapped by aerosol and activated c o c o n u t
c h a r c o a l filters, but organic iodides are not e f f e c t i v e l y r e m o v e d by such filters and are not dissolved in
aqueous solutions. In humid air at temperatures from 25°C to 100°C the e f f i c i e n c y of iodine r e m o v a l by
c h a r c o a l can be increased by impregnation with triethylenediamine or potassium i o d i d e . A l l adsorbents
are subject to loss of e f f i c i e n c y upon aging and must be c h e c k e d p e r i o d i c a l l y .
1. INTRODUCTION
The realization of the danger p o s e d by r a d i o a c t i v e iodines in the event

of a r e a c t o r accident led to studies being undertaken in F r a n c e and e l s e -
where to develop efficient trapping equipment [ 1 ] . Activated c h a r c o a l was
found to p r o d u c e good r e s u l t s , and it was t h e r e f o r e decided to p r o c e e d
i m m e d i a t e l y to equip the ventilation s y s t e m s of French r e a c t o r containment
s t r u c t u r e s with activated coconut c h a r c o a l , p r e c e d e d by a e r o s o l f i l t e r s
(Figs l a and l b ) . It was v e r y s o o n d i s c o v e r e d , h o w e v e r , that,in addition
to the particular iodine and elementary gaseous iodine which until then had
been the s o l e object of attention,there w e r e unknown f o r m s which p a s s e d
through the f i l t e r s and which w e r e not p r o p e r l y adsorbed by the c h a r c o a l and
other adsorbents, and w e r e not soluble in the aqueous solutions; these
w e r e t e r m e d penetrating f o r m s and, on the b a s i s of the work of Collins
and Eggleton [ 2 ] , a hypothesis was formulated regarding their organic
nature.
2. SAMPLING AND ANALYSIS
The sampling equipment used, consisting of Maypack type traps c o m p o s e d

b a s i c a l l y of a f i l t e r with a e r o s o l s and of one o r m o r e l a y e r s of filter
m a t e r i a l s , was a l s o used f o r analysis, to the extent that the adsorbents w e r e
s e l e c t e d with r e f e r e n c e to the iodine f o r m s expected. The equipment of
this type which we u s e , namely, a l a b o r a t o r y tube ( F i g . 2) whose c o n -
struction is d e s c r i b e d in F i g . 3, is made of glass and stainless steel for
l a b o r a t o r y experiments and entirely of stainless steel f o r o n - s i t e t e s t s .
87
TRAPPING RADIOACTIVE IODINE 89
FIG. 2 . Laboratory tube.
The number of filter l a y e r s can be varied at will by superposing s e v e r a l

trapping units between the two end parts A and B; the m o s t frequent
embodiment c o m p r i s e s - in this o r d e r - a c o p p e r plug, a filter paper, and
one o r m o r e l a y e r s of activated c h a r c o a l . The a s s e m b l y as a whole is
designed to retain iodine in m o l e c u l a r f o r m , in a e r o s o l f o r m and in the
penetrating f o r m s . The interpretation of the distribution of iodine on the
v a r i o u s components of the l a b o r a t o r y tube is in fact inconclusive [ 3 - 6 ] .
None of the components is c o m p l e t e l y s e l e c t i v e and retention rates f o r the
v a r i o u s f o r m s v a r y with t e m p e r a t u r e , humidity and the nature of the
c a r r i e r g a s . The Maypack is a c o m p a r a t i v e l y s i m p l e and robust sampling
and analysis d e v i c e and is e a s y to u s e ; it can show the variations in the
c o m p o s i t i o n of a gaseous mixture when the p r e c i s i o n r e q u i r e d is not too
great.
T o m e a s u r e a i r b o r n e r a d i o a c t i v e wastes in the event of malfunction
o r accident, a s i m p l e g a s - m a s k c a r t r i d g e of n o r m a l manufacture can be
u s e d . The radioactivity of the sampled iodine can be m e a s u r e d and no
dismantling of the d e v i c e is required [ 7 ] . F o r r e a s o n s given below, this
type of trap is r e l i a b l e only f o r sampling at ambient temperature and o v e r
a limited p e r i o d ( l e s s than 24 h o u r s ) .
BRION
FIG.3. Construction of a laboratory tube.

3. ADSORBENTS
The use of Maypack o r l a b o r a t o r y tube type equipment afforded a

means of studying the e f f i c i e n c y in trapping iodine and methyl iodide (the
o r g a n i c compound type) exhibited by v a r i o u s adsorbents (activated coconut
c h a r c o a l and c h a r c o a l produced f r o m coal, whether impregnated o r not
with p o t a s s i u m iodide o r triethylenediamine, and s i l v e r - e x c h a n g e d
m o l e c u l a r sieve) in a t m o s p h e r i c a i r , f o r the p r o b a b l e concentrations in the
event of an accident (10" 3 g / m 3 ) , with humidity ranging f r o m 0 to 90%,
t e m p e r a t u r e ranging f r o m ambient to 200°C,and scavenging time varying
f r o m four hours to s e v e r a l days [8 - 1 1 ] . The following conclusions w e r e
drawn f r o m this study:
(a) In d r y air and at ambient t e m p e r a t u r e , coconut c h a r c o a l is the

m o s t efficient adsorbent;
(b) In humid air and at t e m p e r a t u r e s ranging f r o m 25°C to 100°C,
c h a r c o a l produced f r o m coal and coconut c h a r c o a l impregnated
with triethylenediamine o r p o t a s s i u m iodide a r e m o r e efficient
than other adsorbents (E > 104 after six d a y s ' scavenging).
At t e m p e r a t u r e s ranging f r o m 130°C to 150°C, the iodine compounds

passing through the impregnated c h a r c o a l show marked d e s o r p t i o n (through
l o s s of imprégnant). T h e only efficient adsorbent at t e m p e r a t u r e s above
150°C is the s i l v e r - e x c h a n g e m o l e c u l a r s i e v e (E > 10 4 after six days'
scavenging).
4. CHECKS
The application of these results to the c h o i c e of iodine traps to be

installed in the ventilation c i r c u i t s o r r e a c t o r containment structures is
not e a s y ; since there is no single " a l l - p u r p o s e " adsorbent, each type of
r e a c t o r accident has to be studied individually. M o r e o v e r , all these
adsorbents a r e subject to an aging e f f e c t when air is p a s s e d through them
constantly [12 - 1 4 ] . This e f f e c t j e o p a r d i z e s the e f f i c i e n c y of the traps
and, ultimately, the safety of the installation. The traps must t h e r e f o r e
be checked p e r i o d i c a l l y . We p r o p o s e that the following p r o c e d u r e be adopted:
one o r two control traps containing a l a y e r of adsorbent of the s a m e type as
the adsorbent in the main trap and functioning under the s a m e conditions a r e
mounted on to the main trap to f o r m a b y - p a s s . The reduced load in the
main trap e n s u r e s circulation in the pilot t r a p s . F r o m time to time one of
these traps is dismantled and tested for m o l e c u l a r iodine and methyl i o d i d e .
On c o m p l e t i o n of the test the control trap is remounted on to the main trap
to f o r m a b y - p a s s . When tests show that e f f i c i e n c y has d e c r e a s e d
significantly, an o n - s i t e check is c a r r i e d out and the results thus obtained
indicate whether the main iodine trap and the control traps should be
retained o r r e p l a c e d .
O n - s i t e checking of traps for m o l e c u l a r iodine is now a fully developed
and tested p r o c e d u r e [ 1 2 , 1 5 ] ; the s a m e technique can easily be adapted to
checking for methyl i o d i d e . F o r the p r e s e n t tests (with a ventilation rate of
up to 100 000 m 3 / h ) , a prototype portable generator is being used ( F i g . 4);
this generator can contain up to 30 m C i of 1 3 1 I. A s i m p l e calculation shows
92 BRION
FIG. 4 . Portable iodine source.
that f o r a ventilation rate of 100 000 m 3 / h and a sampling rate of 3 m 3 / h

we can obtain a t r a p - s c r u b b i n g c o e f f i c i e n t of the o r d e r of 10 000 (with 30 m C i
131 I radioactivity and a general detection sensitivity of 10" 10 C i ) . In s o m e
exceptional c a s e s use is made of a portable s o u r c e which may contain up to
3 Ci of 1 3 1 I. T h e s e s o u r c e s a r e , of c o u r s e , s o designed that the m a x i m u m
p e r m i s s i b l e radiation dose is not reached in the conditions under which they
are used.
REFERENCES
[1] PRADEL, J . , CHEVALIER, C . , BILLARD, F . , Etude de l'arrêt de l ' i o d e par les charbons actifs
(Study on iodine capture by activated c h a r c o a l ) , Rapport C E A - R - 2 2 3 1 (1962) (in French).
[2] COLLINS, R . D . , EGGLETON, A . E . J . , " C o n t r o l of gas-borne activity arising from reactor faults",
P e a c e f u l Uses of A t o m i c Energy (Proc. 3rd Int. C o n f . Geneva, 1964) 1 3 , UN, New York (1965) 6 9 .
[3] COLLINS, D . A . , TAYLOR, R . , YUILLE, W . D . , " S a m p l i n g and characterization techniques used
in the study of iodine release from irradiated fuel e l e m e n t s " , Fission Product Release and Transport
under A c c i d e n t Conditions (Proc. Symp. Oak Ridge, 1965), 1096.
[4] COLLINS, D . A . , McINTOSH, A. E . , TAYLOR, R . , YUILLE, W . D . , Experiments relating to the
control of fission-product release from advanced g a s - c o o l e d reactor, J. N u c l . Energy 20 (1966) 9 1 .
[5] ADAMS, R . E . , BENNETT, R . , COMBS, Z . , Distinguishing Iodine Forms at High Temperatures and
Humidities, ORNL-4076 (1961) 163.
[6] HOWES, J . E . , RITZMAN, R . L . , MORRISON, A. L . , TOWNLEY, C . W . , Investigation of Techniques

fot Sampling and Analysis of Iodine under Simulated Reactor A c c i d e n t Conditions, BMI-1814 (1961).
[7] BILLARD, F . , CHEVALIER, G . , GAILLARD, P . , PRADEL, J., Quelques méthodes de détection de
contaminations atmosphériques par l ' i o d e 131 ( S o m e methods of detecting atmospheric c o n t a m i n a t i o n
by i o d i n e - 1 3 1 ) , Note C E A - N - 4 8 0 (1964) (in French).
[8] BILLARD, F . , CHEVALIER, G . , CARON, J., VANDERMEERSCH, J . , Influence de l ' h u m i d i t é et de
la concentration en iode sur 1'adsorption de l ' i o d e 131 par les charbons actifs ( I n f l u e n c e of humidity
and iodine concentration on the adsorption o f i o d i n e - 1 3 1 by activated c h a r c o a l ) , Rapport C E A - R - 2 9 0 8
(1966) (in French).
[9] Etat d ' a v a n c e m e n t des principales études au 1 e r janvier 1968 (Progress report on main studies as at
1 January 1968), DPSR/STEP/Groupe Aérosols et Mines, C E A - N - 9 9 9 (1968) (in French).
[10] Etat d ' a v a n c e m e n t des principales études au 1 e r janvier 1969 (Progress report on main studies as at
1 January 1969), DPSR/STEP/Groupe Aérosols et Mines, C E A - N - 1 2 4 6 (1970) (in French).
[ 11] Etat d ' a v a n c e m e n t des principales études au 1 e r janvier 1970 (Progress report on main studies as at
1 January 1970), DPSR/STEP/Groupe Aérosols et Mines, C E A - N - 1 3 6 4 (in French).
[12] BILLARD, F . , " S o l u t i o n adoptée en France pour l'épuration des radioiodes" (Method for the r e m o v a l
of radioactive iodides adopted in France), Containment and Siting of Nuclear Power Plants (Proc.
Symp. Vienna, 1967), IAEA, Vienna (1967) 681.
[13] BILLARD, F . , Vieillissement des pièges à i o d e , nécessité des contrôles, modalités prévues (Aging in
iodine traps; need for c h e c k i n g ; methods planned), C E A - N - 6 3 7 (1967) (in French).
[14] Etude du vieillissement des tamis m o l é c u l a i r e s échangés à l'argent (Study of aging in s i l v e r - e x c h a n g e d
m o l e c u l a r sieves), DPSR/STEP/Groupe Aérosols et Mines (unpublished results) (in French).
[15] BILLARD, F . , BRION, J . , C o n t r ô l e des installations d'épuration de Vair - Essais de c o n f o r m i t é des
éléments - Tests in situ ( C h e c k i n g of air-purification installations - C o m p o n e n t c o n f o r m i t y tests -
On-site tests), C E A - R - 3 2 2 7 (1967) (in French).
EXPERIMENTS AND EXPERIENCE WITH
RADIOIODINE AT CHALK RIVER NUCLEAR
LABORATORIES
P.J. BARRY
Atomic Energy of Canada Ltd,
Biology and Health Physics Division,
Chalk River Nuclear Laboratories,
Chalk River, Ontario, Canada
Abstract
EXPERIMENTS AND :EXPERIENCE WITH RADIOIODINE A T CHALK RIVER NUCLEAR LABORATORIES.

From the b i o l o g i c a l point of v i e w , the various c h e m i c a l forms of radioiodine are nearly equivalent, but
they may behave quite differently toward m e d i a used to measure or control the levels of i o d i n e c o n t a m i n a t i o n in
air. M a y p a c k s a r e useful for application in research to distinguish the c h e m i c a l forms of i o d i n e , and results are
presented on studies of the absorption of i o d i n e by c o p p e r screens used in the M a y p a c k . However, practical
monitoring for i o d i n e requires a quicker and simpler sampling d e v i c e . Chalk River Nuclear Laboratories (CRNL)
h a v e d e v e l o p e d an automatic monitor sensitive to all forms of airborne i o d i n e using c h a r c o a l - i m p r e g n a t e d paper
filters pretreated with e l e m e n t a l b r o m i n e ; in such filters the e f f i c i e n c y for absorption of methyl i o d i n e is
greater than 99%.
Radioiodine releases are controlled at CRNL by ventilating the reactor stack and c e l l s through ducts equipped
with c o m m e r c i a l l y manufactured activated c h a r c o a l filters in addition to filters to r e m o v e particles. The average
l i f e of the c h a r c o a l filters is about nine months.
1. INTRODUCTION
T h e r e a r e no s e r i o u s o r p r e s s i n g p r o b l e m s due to radioiodine at Chalk

R i v e r Nuclear L a b o r a t o r i e s (CRNL). Nevertheless we apply established
radiation protection p r a c t i c e s and endeavour w h e r e v e r p o s s i b l e to r e d u c e
even further the a l r e a d y low l e v e l s of radioiodine contamination that s o m e -
t i m e s o c c u r . Although we are not c o m p l a c e n t , we do not maintain a team
of w o r k e r s continuously studying the behaviour and the c o n t r o l of r a d i o -
iodine. Instead, individuals f r o m time to time work on an isolated p r o b l e m ,
usually to find an answer to a s p e c i f i c question but o c c a s i o n a l l y to s a t i s f y
a p e r s o n a l interest in s o m e particular a s p e c t . In this short r e v i e w I shall
mention s o m e recent experiments as well as s o m e routine operating p r a c t i c e s
that we have evolved as a result of our own e x p e r i e n c e .
2. REVIEW O F PROBLEMS ASSOCIATED WITH RADIOIODINE
The main p r o b l e m s with radioiodine a r i s e b e c a u s e the element, in the

vapour phase, o c c u r s in s e v e r a l c h e m i c a l f o r m s depending on, but apparently
not e a s i l y predictable f r o m , the environmental conditions. It s e e m s that,
f r o m the b i o l o g i c a l point of view, the v a r i o u s c h e m i c a l f o r m s a r e f o r the
m o s t part equivalent. T h e y may, h o w e v e r , behave quite differently toward
media used to control o r m e a s u r e the l e v e l s of iodine contamination in a i r .
95
96 BARRY
This means that d e v i c e s suitable f o r detecting o r r e m o v i n g one c h e m i c a l

s p e c i e s m a y be inadequate f o r others. I think, t h e r e f o r e , that it is m o s t
important when testing o r experimenting to define the c h e m i c a l f o r m s with
which one is working. Similarly, one has a l s o to know what c h e m i c a l f o r m s
m a y o c c u r in the s p e c i f i c operating conditions f o r which the tests o r e x p e r i -
ments a r e c a r r i e d out.
T o distinguish and a s s a y separately the c h e m i c a l f o r m s present we use,
w h e r e v e r p o s s i b l e , the Maypack. While this has s o m e s h o r t c o m i n g s which
I will d i s c u s s later, I r e g a r d it as one of the most important single d e v i c e s
we have f o r c a r r y i n g out experiments on radioiodine.
Perhaps one of the m o s t s e r i o u s drawbacks to this device is that while
an apparatus of this name has been used by many people, the Maypack has
never been standardized. I find that different investigators mean different
things when they use the t e r m and this is a s o u r c e of confusion when results
f r o m one l a b o r a t o r y are c o m p a r e d with those f r o m another.
In our p r a c t i c e , the Maypack c o n s i s t s of the following f i l t e r components
listed in o r d e r :
(a) Facing the incident air s t r e a m are at least three and, depending on
the sampling conditions, p r e f e r a b l y m o r e , c o p p e r o r s i l v e r - p l a t e d
copper screens;
(b) A single h i g h - e f f i c i e n c y l o w - r e s i s t a n c e particulate f i l t e r .
(c) At least one c h a r c o a l - i m p r e g n a t e d paper filter; and finally,
(d) A bed of activated c h a r c o a l .
I think it would be v e r y much worth while to standardize the Maypack

s o that we all know what we a r e talking about when the t e r m is used.
Another drawback with the Maypack, at least in the f o r m which I have
just d e s c r i b e d , is that while the multiple f i l t e r arrangement does give a
nice clean separation of three f r a c t i o n s (four if we count the particulate one)
we cannot unequivocally identify any given f r a c t i o n with a s p e c i f i c c h e m i c a l
entity. F o r example, it is generally a g r e e d that if methyl iodide (or its
h o m o l o g u e s ) is present in the mixture it would appear in the c h a r c o a l bed and
not e l s e w h e r e in the pack. We cannot, however, be certain that any r a d i o -
iodine we pick up on the bed is only methyl iodide.
E l s e w h e r e [ 1 ] , I have shown that iodine picked up on the metal s c r e e n s
is a r e a c t i v e c h e m i c a l f o r m having a m o l e c u l a r diffusivity which is consistent
with its being m o l e c u l a r iodine. Nevertheless, the equation (see Eq. (4) later)
d e s c r i b i n g the absorption kinetics shows that the rate'of absorption v a r i e s
only as the quarter p o w e r of the diffusivity. I think that a s i m i l a r l y r e a c t i v e
s p e c i e s like hydrogen iodide could v e r y well be absorbed at a l m o s t the s a m e
rate. Thus the m o l e c u l a r weights of I2 and HI d i f f e r by a f a c t o r of v e r y n e a r l y
two, so that the diffusivities will differ by a f a c t o r of about 1. 4 (i. e.4~2). The
rates of absorption will only d i f f e r by a f a c t o r of l e s s than 10% and this is not
n o r m a l l y detectable.
Of c o u r s e , these m o r e p r e c i s e distinctions may, in p r a c t i c e , turn out to
be relatively unimportant and I b e l i e v e this is the c a s e . M o r e refined t e c h -
niques a r e available to identify at least s o m e s p e c i f i c c h e m i c a l f o r m s and the
positive identification of methyl iodide by gas chromatography is an example,
but such techniques r e q u i r e s p e c i a l i z e d apparatus and trained o p e r a t o r s .
What we s o often want to find out is the c o m p o s i t i o n of iodine compounds
arising unintentionally in operating p r a c t i c e . We do not, however, always
EXPERIENCE A T CHALK RIVER 97
have time to set up such an apparatus and we must often r e l y on people with'
out s p e c i a l training who have other j o b s to do during such incidents than to
c o l l e c t s a m p l e s f o r us.
3. REVIEW OF EXPERIMENTS CARRIED OUT ON

RADIOIODINE A T CRNL
3.1. A b s o r p t i o n of iodine by c o p p e r s c r e e n s
This work [ 1] was p e r f o r m e d to find out how the sampling conditions

a f f e c t e d the p e r f o r m a n c e of the c o p p e r s c r e e n s in the Maypack. The s c r e e n
e f f i c i e n c y , a, was defined as the ratio of the iodine a b s o r b e d by the s c r e e n
to the iodine reaching the f i l t e r .
If each s c r e e n in the pack r e m o v e s a constant f r a c t i o n of the iodine
presented to it, then if A 0 is the amount presented to the f i r s t s c r e e n , an
amount aA0 is deposited. The n th s c r e e n in a s e r i e s a b s o r b s an amount
A0a (l-a)"'1, s o that the ratio of the amount of the t r a c e r on the n t h s c r e e n
to that on the f i r s t is (l-a) 1 1 " 1 . Thus, plotting the logarithm of this ratio
against n gives a straight line having a slope l o g ( l - a ) . This was the method
we used to estimate a . It has the advantage that neither the amount of m o l e -
cular iodine issuing f r o m the generator n o r the amount l o s t to the walls of
the apparatus b e f o r e the s c r e e n s need be known.
It was shown in the paper that, by definition:
f 0 . 79 М Л
) -Id ...
(1)
where M is the m e s h s i z e in w i r e s per inch

d is the w i r e diameter (cm)
u is the average v e l o c i t y of the air passing the s c r e e n ( c m . s " 1 )
с is the average concentration of m o l e c u l a r iodine in the air s t r e a m
(g- c m " 3 )
I is the rate of deposition of iodine on the w i r e (g • cm" 2 • s" 1 ).
Dividing (1) through by D, the m o l e c u l a r diffusivity of iodine vapour, and

rearranging, gives:
i l B 1 - ^ = S h (2)
cD 0. 797Г MD ЙП [¿ >
where Sh is the Sherwood number, i. e. the d i m e n s i o n l e s s number relevant

to m a s s t r a n s f e r and c o m p a r a b l e to the Nusselt number of heat t r a n s f e r .
Experimental v a r i a b l e s included m e s h s i z e of the s c r e e n (and hence
also the w i r e diameter), the f a c e v e l o c i t y , the c a r r i e r gas (air o r helium),
the depositing entity (I2 o r t h o r i u m - B ions) and the s u r f a c e m a t e r i a l (copper
or silver-plated copper screens).
It was found that the experimental results could be e x p r e s s e d in the f o r m :
= 0. 74 R e 0 - 7 8 S c 0 - 7 5 (3)
where Re is the R e y n o l d ' s number equal to ud/v, v being the kinematic

v i s c o s i t y of the c a r r i e r gas, and Sc is the Schmidt number equal to v / D .
98 BARRY
Equation (3) can be r e d u c e d to the f o r m
a = 0. 74 MD 0 - 2 5 v 0 - 0 3 d 0 - 78 u" 0 - 22 (4)
showing that the e f f i c i e n c y a d e c r e a s e s as the f a c e v e l o c i t y i n c r e a s e s . F o r

example, with a v e l o c i t y of 4 c m - s " 1 (a = 0. 7) two s c r e e n s s u f f i c e to c o l l e c t
o v e r 90% of the m o l e c u l a r iodine in the incident air, whereas with a v e l o c i t y
of 26 c m * s " 1 (a = 0. 4) five s c r e e n s a r e needed to c o l l e c t 90% of the incoming
iodine.
I think it is a good idea to plot against n logarithm of the ratio of the
activity on the n t h f i l t e r to that on the f i r s t , to check the e f f i c i e n c y of the
s c r e e n s which m a y not have been p r o p e r l y p r e p a r e d - o r may subsequently
have b e c o m e contaminated by other substances in the a i r . Copper s c r e e n s had
to be etched b e f o r e use with a strong solution of hydrogen iodide, o t h e r -
w i s e the e f f i c i e n c y was v e r y v a r i a b l e and l o w e r than t h e o r e t i c a l . I found
that the s c r e e n s had to be etched l e s s than 24 h o u r s v b e f o r e use, otherwise
the e f f e c t w o r e off and their e f f i c i e n c y d e c r e a s e d s e r i o u s l y . On the other
hand, c o p p e r s c r e e n s electroplated with s i l v e r retained theoretical e f f i c i e n c y
even after two y e a r s ' s t o r a g e . S o m e t i m e s there is not enough time to p r e p a r e
c o p p e r s c r e e n s p r o p e r l y and we have found it useful to keep on hand, f o r
e m e r g e n c y use, a supply of s i l v e r - p l a t e d s c r e e n s .
3.2. Sampling f o r radioiodine in operational conditions
Useful as the Maypack is f o r r e s e a r c h , f o r sampling under operating

conditions something s i m p l e r and quicker is needed. In the CRNL r e a c t o r
buildings, radioiodine s o m e t i m e s e s c a p e s to the air b e c a u s e of leaks in
the w a t e r - c o o l a n t piping of single experimental channels containing d e l i b e r -
ately defected fuel. A f t e r examining s e v e r a l such incidents using a s i m p l e
pack consisting of a c h a r c o a l - i m p r e g n a t e d f i l t e r paper f o l l o w e d by an activated
c h a r c o a l bed, we found that l e s s than 50% of the total iodine was r a r e l y found
on the paper f i l t e r . Since the c h a r c o a l bed was inconvenient b e c a u s e of the
l a r g e flow r e s i s t a n c e we now use a single c h a r c o a l - i m p r e g n a t e d f i l t e r in
conjunction with a h i g h - v o l u m e suction pump. The apparent concentration
obtained by this method is then multiplied by two. The method is used to
decide whether o r not the operating staff should wear r e s p i r a t o r s and f o r
this it is d e s i r a b l e to have a v e r y quick means of checking f o r iodine and
estimating its concentration.
H o w e v e r , the p r o c e d u r e m a y not always be s a t i s f a c t o r y ; conditions m a y
a r i s e in which the a r b i t r a r y f a c t o r of two is inappropriate and the magnitude
of the potential hazard m a y be s e r i o u s l y underestimated. F u r t h e r m o r e ,
unless s a m p l e s a r e c o l l e c t e d continuously, which is usually not p o s s i b l e ,
there must be s o m e d e v i c e f o r warning the staff that radioiodine m a y be
p r e s e n t . Fortunately, in the c a s e just mentioned, radioactive noble gases
a r e invariably p r e s e n t with the iodine in amounts sufficient to set off l o w -
l e v e l a l a r m s . In other c i r c u m s t a n c e s this may not be s o , and f o r such c a s e s
R. M. H o l f o r d of the Health P h y s i c s Branch at CRNL has developed an auto-
matic m o n i t o r sensitive to all f o r m s of airborne radioiodine [ 2 ] .
The operation of this m o n i t o r depends on the fact that if c h a r c o a l -
impregnated paper f i l t e r s are p r e t r e a t e d with elemental b r o m i n e the e f f i -
c i e n c y f o r absorption of methyl iodide i n c r e a s e s f r o m nearly z e r o to o v e r
99%. The d e v i c e u s e s the c h a r c o a l - i m p r e g n a t e d f i l t e r paper in r o l l f o r m .
EXPERIENCE A T CHALK RIVER 99
The i n c o m i n g a i r p a s s e s through a c o i l of T e f l o n tubing i m m e r s e d in liquid

b r o m i n e . Sufficient b r o m i n e diffuses through the tube wall to sensitize the
c h a r c o a l - i m p r e g n a t e d paper. This arrangement is a c o n s i d e r a b l e i m p r o v e -
ment o v e r that d e s c r i b e d in the original paper which used a c o m p l e x s y s t e m
of v a l v e s activated by e l e c t r o n i c a l l y c o n t r o l l e d s o l e n o i d s . The portion of
the paper r o l l in use is held between a cup-shaped c l a m p and f i x e d b a s e .
The a i r sample flows through the top clamp, p a s s e s through the paper to the
base c l a m p f r o m which it is sucked with a suitable pump. The base c l a m p
fits o v e r an activated sodium iodide c r y s t a l and photo multiplier a s s e m b l y
in standard f o r m a t . The c r y s t a l a s s e m b l y i s shielded with lead to r e d u c e
i n t e r f e r e n c e f r o m background radiation,and energy discrimination of the out-
put pulses p r o v i d e s additional selectivity. During the sampling interval the
r e c o r d e r r e g i s t e r s the accumulated radioactivity due to the build-up of iodine
on the f i l t e r . A range switch is provided so that the instrument c o v e r s a
wide range of concentrations without losing sensitivity at the low l e v e l s . At
the end of a p r e d e t e r m i n e d sampling interval, the paper is advanced and the
range switch r e s e t in r e a d i n e s s f o r the next sample.
3. 3. Controlling radioiodine inhalation hazards
On a v e r a g e , l e s s than 1 mCi per day of 1 3 1 I is r e l e a s e d to the a t m o s p h e r e

at CRNL through the r e a c t o r ventilating stack which, f u r t h e r m o r e , is p a r t i -
c u l a r l y favourably placed s o that the effluent is well d i s p e r s e d . The other
main s o u r c e s of 1 3 i I at CRNL a r e the fuel examination c e l l s where test fuel
s p e c i m e n s a r e cut up and p r e p a r e d f o r examination while still containing
s o m e f i s s i o n product 131 I.
The c e l l s a r e ventilated through r o o f vents and a r e situated among other
buildings. The exhaust duct is equipped with c o m m e r c i a l l y manufactured
activated c h a r c o a l f i l t e r s in addition to f i l t e r s to r e m o v e p a r t i c l e s . New
c h a r c o a l f i l t e r s a r e tested a f t e r they have been installed and p e r i o d i c a l l y
t h e r e a f t e r . We found this testing to be important b e c a u s e of a gradual l o s s
of e f f i c i e n c y during s e r v i c e which ultimately r e q u i r e s a change of f i l t e r s .
The a v e r a g e life of the f i l t e r s in our application is about nine months.
4. CONCLUSIONS
The operating r e c o r d at CRNL f o r internally deposited radioiodine has

been v e r y good. This is b e c a u s e r e l e a s e s of radioiodine to the working
environment have been s m a l l and infrequent and because, as we have found
f r o m analysing a l a r g e number of s a m p l e s c o l l e c t e d with a Maypack, methyl
iodide is not present in those r e l e a s e s that have o c c u r r e d . F o r the remaining
c h e m i c a l f o r m s of radioiodine, adequate methods of detecting and controlling
inhalation hazards a r e available and are in standard use.
REFERENCES
[1] BARRY, P . J . , Health Phys. 15 (1968) 243.

[2] HOLFORD, R . M . , " A n a u t o m a t i c monitor f o t all forms of airborne r a d i o i o d i n e " , Treatment of A i t b o m e
R a d i o a c t i v e Wastes ( P r o c . S y m p . New York, 1968), IAEA, Vienna (1968) 7 .
LIST OF PARTICIPANTS AND ADVISERS
PARTICIPANTS
P.J. Barry (Chairman) A t o m i c Energy of Canada Ltd,

Chalk River Nuclear Laboratories,
Chalk River, Ontario, Canada
J. Brion Service technique d ' é t u d e s de p r o t e c t i o n ,

Centre d ' é t u d e s nucléaires
de Fontenay-aux-Roses, France
W.P. Gammill Division of Reactor D e v e l o p m e n t and T e c h n o l o g y ,

USAEC,
Washington, D . C . , United States of A m e r i c a
A . C . Poliakov Kurchatov Institute of A t o m i c Energy,

M o s c o w , USSR
B.F. Warner UKAEA,

Windscale Works,
S e l l a f i e l d , C u m b e r l a n d , United Kingdom
I . G . Wilhelm Radiation Safety and Protection Department,

Karlsruhe Nuclear Research Centre,
Karlsruhe, Federal Republic of Germany
ADVISERS
P a m e l a M . Bryant National R a d i o l o g i c a l Protection Board,

Harwell, D i d c o t , Berks, United Kingdom
L. D e v e l l Aktiebolaget Atomenergi,
Studsvik, Nykoping, Sweden
W. Knoch Gesellschaft zur Wiederaufarbeitung von Kembrennstoffen m b H ,

Leopoldshafen, Federal Republic o f Germany
P. Rowland OECD Dragon H i g h - T e m p e r a t u r e Reactor P r o j e c t ,

AEE Winfrith,
Dorchester, Dorset, United K i n g d o m

G . Meilland
WHO Liaison O f f i c e , IAEA
C . M . Slansky
Division of Nuclear Safety and Environmental Protection, IAEA
SCIENTIFIC SECRETARY
E . W . Wiederhold Division o f Nuclear Safety and Environmental Protection, IAEA
101
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AIRBORNE SPECIES OF IODINE

TECHNICAL REPORTS SERIES No 148

AFGHANISTAN GUATEMALA PANAMA

(£) IAEA, 1973

Printed by the IAEA in Austria

INTERNATIONAL ATOMIC ENERGY AGENCY

The protection of man and his environment from harmful concentra-

REPORT OF THE PANEL

1. Introduction — scope and objectives

2. Radiological aspects of radioiodine discharges to

3. Iodine chemistry related to removal and monitoring

4. Systems for iodine removal and monitoring

6. Behaviour of iodine in reactor systems

7. 1. Fast reactor fuel reprocessing

ANNEX: WORKING PAPERS

Control of radioiodine release from reprocessing plants 29

LIST OF PARTICIPANTS AND ADVISERS 101

1. INTRODUCTION - SCOPE AND OBJECTIVES

2. RADIOLOGICAL ASPECTS OF RADIOIODINE DISCHARGES TO

2.1. Potential discharges from the nuclear power industry

2.2. Quantities and relative importance of radioiodine

Several isotopes of iodine are present in approximately equal activities

2.3. Guidelines for control of radioiodine discharges

Accidental discharges of radioiodine to the atmosphere may evoke the

2. 4. Relationships between dose, intake and the level of radioiodine in

Iodine isotopes may be discharged to atmosphere as molecular iodine or

Detailed assessments of these relationships are available in the open litera-

2.5. Future trends

The Panel also considered the implications of the increasing use of

A major problem arising in connection with the projected reprocessing

3. IODINE CHEMISTRY RELATED TO REMOVAL AND

3.1. Forms of airborne iodine

Iodine in off-gas systems may appear as elemental iodine or iodine

of methyl iodide amounting to 10% of the iodine in the core. Furthermore,

3.2. Removal mechanisms for airborne iodine

3.3. Precautions for iodine monitoring with respect to iodine behaviour

The Panel wishes to draw attention to the importance of adequate iodine

4. SYSTEMS FOR IODINE REMOVAL AND MONITORING

4.1.1. Activated charcoals

4.1.2. Inorganic adsorbents

For higher temperatures and strongly oxidizing gases, a non-flammable

4.2. Liquid scrubber systems

In general, liquid scrubber systems for removing radioiodine from

4. 3. Reactor containment spray systems

4.4. Pressure-suppression pools

Pressure-suppression containment systems are divided into two compart-

1 to 5. The factors which can have a significant influence on the pool-

(1) The post-LOCA containment conditions (temperature, pressure, etc.)

4.5. Ice containments

Ice-filled compartments have been proposed for nuclear power plants

in I2 concentration could also help to minimize the probability of formation

4.6. Testing of iodine traps

It is necessary to emphasize the need for testing the efficiency of iodine

4.6.1. Precautions to be taken

(1) Lack of homogenization of samples taken upstream or downstream

4.6.2. Recapitulation of the principle of iodine testing

Devices and systems for monitoring iodine must be designed, tested

chromatographic techniques have proved valuable in identifying organic

5.1. Charcoal samplers

Sampling of gaseous iodine can be carried out by means of a bed of

5.2. Filter packs

Sometimes it will be necessary to know not only the total amount of

5.3. Direct continuous system