CHEMISTRY MEASURES TO CONTROL ANTIMONY ACTIVITY FOR

MINIMISING RADIATION EXPOSURES DURING LONG SHUTDOWNS

Rajesh Verma, Amit, Sanjay Kumar and Hemant Kumar
Rajasthan Atomic Power Station-3&4, Rawatbhata, Rajasthan-323 303
E-mail: amit@npcilraps.com, hemantkumar@npcilraps.com

ABSTRACT
124
Due to the presence of Sb , a strong gamma-emitting radioisotope, significant increase in
radiation fields on Primary Heat Transport piping and equipments and consequently high man-rem
consumption were observed during the Biennial Shut Down of RAPS-4 in May’2003. As this incidence
was observed for the first time in any Indian PHWR, a systematic study was carried out to establish
the mechanism of release of Sb124 and an innovative and simple chemistry measure was suggested to
prevent its recurrence. Implementation of this measure has helped in minimising man rem
consumption during subsequent long shutdowns. This paper highlights the investigations carried out
at RAPS-3&4 for establishing the source of Sb124 in PHT system and the chemistry measures to avoid
man rem consumption.

Key words: man rem consumption, Sb124, heat transport coolant, long shutdown, source of
antimony, release mechanism, chemistry control measures.

INTRODUCTION
During the Biennial Shut Down (BSD) of RAPS-4 in May’2003, around 33 to 75%
increase in radiation fields on Primary Heat Transport (PHT) equipments were noticed
resulting in high man-rem consumption during various maintenance jobs.

Radiochemical analysis of PHT system heavy water and in-situ gamma spectrometric
survey of PHT components revealed the presence of high level of gamma emitting
radioisotope, antimony-124 (Sb124), with half-life of 60.2 days. This circulating activity was
established to be present in anionic form and hence this activity could be controlled using the
shutdown purification system. Subsequently a detailed investigation was carried out to
establish the source of the antimony, reasons for its release in the PHT system heavy water
and to avoid the recurrence of same phenomenon in future.

OBSERVATIONS
The increase in radiation fields on PHT system was noticed after depressurising PHT in
steps and keeping purification system kept continuously valved in for I131 removal. The PHT
system chemistry was maintained quite well since beginning with low level of trace metallic
impurities.
Initial laboratory investigations with 0.45 µ pore size filter paper and different ion
exchange resins confirmed the Sb124activity to be present in anionic form. It was further
substantiated by the fact that electrolysis of PHT heavy water sample caused Sb124 activity to
be deposited on positive electrode. The anionic nature of Sb124 activity indicated that the
purification system is capable of removing this activity. The circulating Sb124 activity,
observed maximum on 21.05.2003 (160 µCi/l corresponding to approximately 1.8 mg of
natural Sb), could be reduced gradually using the shutdown purification system during
shutdown. After the resumption of normal purification system during subsequent unit
operation, this activity was observed in reducing trend. The radiochemical analysis of spent
resins of ion exchange hoppers, which were in service during this period, revealed presence
of Sb124 activities. It was further observed that the decay pattern of radioactivity was
reconcilable to Sb124 pattern.
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 124
V a ri a t io n o f S b ( µ C i/ l) in P HT s y s t e m o f R A P S - 4 d uring B S D i n M a y '2 0 0 3
1 60

1 40

SD IX taken in service on 21.05.2003

1 20

Unit-4 under BSD from 09.05.2003

Reactor critical on 31.05.2003

1 00
µ

80

60

40
Sb124
<0.50mCi/l from 19.06.2003 onwards
20

Dat e

Figure 1: Variation of Sb124 activity in RAPS-4 PHT during BSD in 2003

It was also noticed that Sb124 was not present in the PHT system of RAPS-4 prior to BSD.
It had appeared in the system after lapse of some days after BSD and there was no further
build up of this activity after its first detection during BSD. Even after isolating purification
system for six hours during subsequent unit operation, no Sb124 activity was observed in the
system indicating that there was no fresh input.

IDENTIFICATION OF SOURCE
After establishing antinomy as the root cause for increase in radiation fields, attempts
were made to find out its source in PHT system. Various possible sources like system
constructional materials (piping, HX, FHS circuits, Primary Circulating Pumps, Shutdown
Cooling Pumps, Primary Pressurising Pumps), gasket materials, anti-seize compounds,
chemical additives, resins, heavy water used for addition and failed fuel were studied in
detail.
After thorough literature survey and discussion with supplier, it was noticed that there
were only three possible components, which could explain the presence of Sb124 activity.
These were carbon steel piping, carbon bearing of PCP (antimony impregnated carbon ring)
and carbon face of Primary Circulating Pumps mechanical seals (antimony impregnated
carbon graphite shrunk fit in SS housing).

The presence of antimony, in ppm levels, in carbon steel pipes, has been reported in some
literature. If the release of Sb122 and Sb124 is from some other source like carbon steel etc,
then the activation products of other alloying element(s) of the structural material should also
had been observed. However, the gamma spectrometric analysis of PHT heavy water samples
had indicated absence of Fe59, Co60 and Mn54, which are important activated corrosion
products of carbon steel. Theoretical calculation also confirmed that antimony was not
coming from carbon steel and it was substantiated by gamma spectrometric analysis. The fact
that only Sb124 had been observed indicated that source was from a component which
contained only antimony as a metallic component.
The PCP pump shaft is guided by a heavy water lubricated carbon bearing. This carbon
bearing consists a bearing insert of antimony impregnated carbon ring, which is shrunk fit in

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SS housing. Similarly, PCP mechanical seal carbon face is antimony impregnated carbon
graphite shrunk fit in SS housing.
Carbon bearing is manufactured entirely from carbon with high temperature carbonaceous
bonding. It has the strength, hardness and wear resistance of carbon and corrosion resistance
and self lubricating properties of graphite. The inherent porosity of carbon graphite is filled
with antimony impregnant to improve the strength, thermal conductivity, and tribological
characteristics of the material1. The mechanical seal consists of rotating face and stationary
face. While the rotating face of mechanical seal is of carbon graphite impregnated with
antimony, the stationary face is of tungsten carbide.
Based on the RAPS-3&4 observations, experiments and review, the carbon bearing of
PCP (antimony impregnated carbon ring) and carbon face of PCP mechanical seal (antimony
impregnated carbon graphite) were established as the sources of antimony. These facts were
corroborated by independent material testing at Material Science Division, BARC2.
The samples of mechanical seal and carbon bearing were sent to Material Science
Division (MSD), BARC, for characterisation of constituents. Samples were analysed using
Electron Probe Micro Analysis (EPMA), X-ray fluorescence (XRF) and the conventional
Atomic Absorption Spectroscopy (AAS). X-ray diffraction of rotating face of mechanical seal
indicated presence of antimony in the range of 3-5% and silver about 0.1-0.2%. EPMA result
of carbon bearing indicated antimony in the range of around 3-5 %. Samples of carbon
bearing analysed at ARAI, Pune, also confirmed the presence of antimony in the range of
3.38 to 7.33% by weight.
It was further noticed that the Sb124 problem is not unique to RAPS-4. Worldwide the
external dose has been essentially due to activation products like activated cobalt (Co60), but
Zr95, Nb95 and Sb124 have also contributed, and in some stations, antimony has been the
dominant source of external exposure3. Genitlly-2, a Canadian PHWR, has reported
significant antimony fields. In some French PWRs, Sb124 activity has also been reported4. At
both these places (Canada and France), the source of antimony is the PHT pump components
(seal and bearing) containing antimony and Sb124 activities were reported to be reduced after
replacement of pump components containing antimony. In Gentilly-2, after putting back old
seal containing antimony, Sb124 was observed to have increased again5. This conclusively
proved that the source of antimony is the PHT pump components (seal and bearing)
containing antimony

MECHANISM OF ANTIMONY RELEASE

After establishing the source of antimony is the carbon bearing of PCP (antimony
impregnated carbon ring) and carbon face of PCP mechanical seal (antimony impregnated
carbon graphite) efforts were made to understand the reasons for its release in PHT system
during long shutdowns.
While establishing the probable release mechanism, it is to be mentioned that while the
source of antimony has been identified, very little information is available on antimony
transport and activation. There are still many aspects of the mechanism of antimony
deposition in core that are not understood.
The impregnation of antimony can vary from batch to batch and its release in the system is
a random phenomenon. If antimony is coming from manufacturing defects leading to random
slug release, then the probability of release of antimony is more during PCP running
condition i.e. during unit operating condition. Sb122 and Sb124 activities in PHT heavy water,

1021
during steady unit operation or during shutdown of short period, were consistently observed
below their minimum detection limit (0.50µCi/l). The fact that Sb122 and Sb124 activities are
mostly observed below their minimum detection limit during unit operating condition, ruled
out the probable mechanism of random slug release.
Release from excessive wear is possible when bearing is in service but this is expected to
increase vibration. The performances of the PCP pumps were monitored on regular basis by
taking vibration and pump seal cavity pressure data and these were observed well within the
limit indicating satisfactory performance of PCP’s. Hence only natural wear can be expected
in the rotating parts and it is believed that antimony is released from this natural wear.
However the natural antimony released during this process is too small to be detected by
either visual examination of components or by normal chemistry analytical techniques. The
visual observation of removed old carbon bearing and mechanical seal of PCP-2 also did not
indicate any apparent abrasion or wear. This may be because of the fact that the amount of
natural antimony released (~1.8mg) from sixteen components of all the four PCPs is too
small for detection.
During normal operating condition, The PHT system chemistry is highly reducing and
under these conditions antimony is not present in soluble form and hence not detected by
conventional chemical analysis. During long shutdown, maintenance jobs are taken on PHT
system equipments and this creates an opportunity for atmospheric air (containing nitrogen,
oxygen and carbon dioxide) to ingress into the system. The effect of carbon dioxide is to
convert the hydroxides into bicarbonates thereby reducing the system pH gradually. The
oxygen present in the atmospheric air dissolves in PHT coolant and interacts with the
deposits on the structural material. The dissolved oxygen seems to be primarily responsible
for converting the deposited antimony into the soluble antimonate (SbO3-) form. The
dissolution process seems to be slow, as Sb122 and Sb124 are not observed immediately after
shutdown. This soluble and circulating antimonate (consisting of Sb122 and Sb124) increases
the radiation field in the PHT circuit.

CHEMISTRY ASPECTS
Natural antimony consists of Sb121 (abundance 57.36%, neutron absorption cross section
5.9 barns) and Sb123 (abundance 42.64%, neutron absorption cross section 4.1 barns), which
under the influence of neutronic field form Sb122 (half life 2.70 days, gamma energies 546
KeV, 693 KeV) and Sb124 (half life 60.20 days, gamma energies 603 KeV, 1691 KeV)
respectively.
Due to the complex chemistry of antimony, existence of multiple oxidation status and
sensitivity to varying pH and dissolved condition, different species (oxo and hydrous) of
antimony get stabilised and also get distributed among coolant, crud and surface deposits.
The antimony released during the process is transported to the core, gets activated and
absorbed into iron oxide lattice of system structural materials at some inaccessible locations.
The deposition is irreversible due to growth of oxide film during operation. The deposition of
activity is used as a generic term and it includes adsorption, ion exchange, electrodeposition,
precipitation and particle deposition6. The incorporation of antimony in the iron oxide lattice
is supported by the fact that Sb122 and Sb124 are observed in PHT crud samples although their
levels are very small.
Under oxidizing conditions, Sb (V) is formed. At alkaline pH and low and moderate
temperatures, Sb (V) exists in solution in anionic form which can be removed on an anion

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exchange resin. Under reducing conditions Sb (III) species are formed. Under highly
reducing conditions, antimony metal is expected.

Under normal operating condition, Sb is present During shutdown and oxygenated condition, Sb
as Sb (III) or metallic Sb, which is not soluble. is present as soluble SbO3- form.

Simplified Pourbaix diagram for Sb at 300oC Simplified Pourbaix diagram for Sb at 80oC

Figure 2: Simplified Pourbaix diagram for antimony at 80oC and 300oC.

It is reported that standard decontamination process, used in India and aboard, such as
CANDECON or AP (Alkaline Permanganate) do not effectively remove antimony. Antimony
is mobilised from out of the core surfaces during the decontamination process by the
dissolution of deposited oxides. Antimony, released during the decontamination process,
tends to redeposit on to the carbon steel feeders and pipes. The surface charge of magnetite is
positive in reducing and low pH conditions during the decontamination process. This favours
the adsorption of anionic or neutral antimony species. With reference to above, any
decontamination process will result in mobilisation of antimony from one location and its
redeposition on system piping at other locations. Hence the decontamination processes,
presently in vogue, will not be useful for getting rid of Sb124 activity problem.

CORRECTIVE AND PREVENTIVE MEASURES

It was felt imperative to replace the components containing antimony with antimony free
materials. Accordingly antimony free carbon bearing and mechanical seals were procured by
site. However before putting these antimony free bearings and seals in the PHT system, these
were sent to MSD, BARC, for characterisation of constituents.
EPMA report of antimony free carbon bearing showed the absence of antimony and
presence of silver particles distributed within the matrix. X-ray analysis also showed presence
of silver (about 0.10%) and the absence of antimony. AAS analysis showed presence of 78
ppm antimony and only 4 ppm silver. The above results were reviewed and discussed in
COSWAC and it was noted that both the new bearings and seal contain insignificant
quantity of Ag and Sb as compared to the seals and bearings employed earlier. As the
activity due to Ag110M, Sb122 and Sb124 would be very less with new seals and bearing. After
the approval from COSWAC for their use in the system, the carbon bearing and mechanical
seal of PCP-2 were replaced with antimony free material in BSD in 2003. It was planned to
change the carbon bearing and mechanical seal with antimony free carbon bearing and
mechanical seal in remaining PCPs after assessing the performance of new bearing and seal.

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 In order to avoid inadvertent man-rem exposure due to Sb124 following unit shutdown, the
practice of analysing PHT samples for Sb124, along with other isotopes, on daily basis, was
instituted. It was emphasised that whenever any Sb124 activity is observed in the system
during shutdown, no maintenance work in the system shall be taken up until Sb124 activity is
brought down to an acceptable level.

CONTROL OF ANTIMONY ACTIVITY DURING SHUTDOWN

Experiences at RAPS-3&4 and at other NPPs indicated that the Sb122 and Sb124 are
released only during long shutdown. In Gentilly-2, a Canadian PHWR had reported release of
Sb122 and Sb124 during shutdown leading to large increase in radiation fields. The ingressed
air increases the dissolved oxygen content in PHT system heavy water and converts the
deposited antimony into the soluble antimonate form.
As the antimony activity in PHT system was established in the form of an anionic species
- antimonate (SbO3-), it was thought that by controlling the dissolved oxygen in the PHT
system heavy water during long shutdown, the probability of formation of soluble antimonate
anion could be avoided.
It was thought that hydrazine hydrate, added in PHT system during shutdown, would react
with any oxygen entered in the PHT system. Hydrogen formed by the radiloytic
decomposition of hydrazine will also help in maintaining reducing atmosphere for longer
time during shutdown and will also radiolytically recombine with any oxygen that enters
PHT system under shutdown radiation field.
Accordingly permission was sought from COSWAC for addition of hydrazine hydrate in
PHT system heavy water during BSD for dissolved oxygen control. The proposal was
reviewed by COSWAC and approval was given for maintaining 5.0 ppm hydrazine
concentration in PHT system heavy water during shutdown and to maintain low oxygen in
PHT storage tank cover gas system7.
During the BSD of RAPS-3 in August’2004, hydrazine hydrate was added in the PHT
system. After a lapse of four days, both the isotopes of Sb122 and Sb124 were observed in the
PHT coolant water, their values being 34.0 and 20.5µCi/l respectively. These Sb122 and Sb124
activities were very less as compared to the activities levels observed in RAPS-4 PHT system
during May’2003. No increase in radiation fields in PHT system equipments and piping were
noticed as reported by Health Physics Unit. The trend in Sb124 activity observed in RAPS-3
PHT system heavy water, during August’2004, is shown in figure-3.

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 Va ria tio n o f S b 1 2 2 a nd S b 1 2 4 ( µ Ci/ l) in P HT s ys te m o f RAP S -3 during B S D in 2 00 4

160

SD IX valved in at 1830

Reactor critical on 14.09.2004

140

Hydrazine hydrate added on

hrs of 19.08.2004
Unit BSD from 16.08.2004
120
100
µ

80
16.08.2004 Sb122
60 Maximum value 34.0 µCi/l on 19.08.2004
40 Sb124
20 Maximum value 20.5 µCi/l on 19.08.2004

Da te
124
Figure 3: Variation of Sb activity in RAPS-3 PHT during BSD in 2004
The experience of hydrazine hydrate addition in RAPS-3 PHT system was discussed and
reviewed in the 116th meeting of COSWAC. Based on the encouraging results achieved after
hydrazine hydrate addition and the experiences gained, it was recommended to maintain
5.0ppm hydrazine concentration in RAPS-4 PHT system heavy water during the ensuing
BSD.
During the BSD of RAPS-4 in April’2005, the exercise for controlling release of Sb124
activity was repeated again. In order to take care of hydrazine depletion by thermal and
radiloytic decomposition and removal by ion exchange system, a slight excess of hydrazine
hydrate was added in the PHT heavy water. After a lapse of four days, 4.71µCi/l Sb122
activity was observed in the PHT coolant heavy water but subsequent sampling and analysis
showed it to be in decreasing trend. Sb124 activity was not observed any time in the primary
coolant heavy water during the period of shutdown and after subsequent unit operation. The
trend in Sb122 and Sb124 (BDL) activity observed in RAPS-4 PHT system heavy water, during
April’2005, is shown in figure-4.

Variation of Sb122 and Sb124 (µCi/l) in PHT system of RAPS-4 during BSD in April'2005

160
SD IX taken in service at 1605 hrs

140
Reactor critical on 21.05.2005

120
(µCi/l)

Unit SD on 01.04.2005

100
124

80
& Sb

60
Sb122
122

40 Sb124
Sb

Maximum value observed 4.71 µCi/l Observed <0.50mCi/l

20
0
31.04.05
01.05.05
02.05.05
03.05.05
04.05.05
05.05.05
06.05.05
07.05.05
08.05.05
09.05.05
10.05.05
11.05.05
12.05.05
13.05.05
14.05.05
15.05.05
16.05.05
17.05.05
18.05.05
19.05.05
20.05.05
21.05.05
22.05.05
23.05.05
24.05.05
25.05.05

Date & Time (hrs)

Figure 4: Variation of Sb124 activity in RAPS-4 PHT during BSD in 2005

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CONSEQUENCES OF HYDRAZINE ADDITION
Before hydrazine hydrate addition, it must be ensured that there are no copper bearing
alloys or components in the PHT system because the ammonia formed by decomposition of
hydrazine react with copper and will dissolve it by complexation. Consequent to hydrazine
hydrate addition the pH, specific conductivity and dissolved hydrogen concentration in PHT
system heavy water are expected to increase. If a mixed bed ion exchange column (IX)
having Li+ & OH- as exchangeable ions is used during hydrazine addition, hydarzinium ion
replaces Li+ , increasing the concentration of Li+ in the system. It is better to use pure anion
based IX columns during hydrazine addition as it would not remove the added hydrazine and
will also help in removing Sb124 activity should they appear subsequently in the system.
During header level control ingress of air from atmosphere to PHT system will take place.
Due to presence of CO2 of air, lithium hydroxide is converted into lithium carbonate and
hence causing drop in coolant pH. In absence of availability of main purification system
during long shutdown, the low pH condition may continue to prolong and may lead to
corrosion. A precise amount of lithium hydroxide can be added in the system during header
level control to maintain the pH in the specified range.
The presence of dissolved deuterium can be attributed by radiolytic decomposition of
ammonia present in the system to nitrogen and hydrogen. The generated hydrogen helps in
suppressing radiolysis and in maintaining reducing atmosphere. The same method is used in
VVER for maintaining reducing atmosphere.
After normalisation of main purification system, the extra lithium ions, residual hydrazine
and ammonia should be removed by using deuterated hydrogen based mixed bed IX column.
The system pH should be restored back by converting carbonates into hydroxides. This can
be accomplished by valving in lithium based mixed bed or anion based IX columns of main
purification system.

CONCLUSION
The carbon bearing of PCP (antimony impregnated carbon ring) and carbon face of PCP
mechanical seal (antimony impregnated carbon graphite) are established as the sources of
antimony based on the investigations carried out. These facts were corroborated by
independent material testing at Material Science Division, BARC. The antimony activities
are observed only when maintenance jobs are taken in PHT system equipments during long
shutdown, which creates an opportunity for atmospheric air to ingress into the system. The
ingressed air increases the dissolved oxygen content in PHT system heavy water, which aids
in releasing the deposited antimony into coolant in antimonate form.
As a long-term solution it is better to eliminate the source term i.e. to replace the
components containing antimony with antimony free materials. However it is possible to
control the release of antimony activities during long shutdown by use of purification system
and by scavenging the dissolved oxygen ingressed into the coolant.

ACKNOWLEDGEMENT
Authors are thankful to Sh. Subhash Mittal, Director (Operations) for his consistent support, valuable
guidance and encouragement in carrying out this work. The technical assistance rendered by COSWAC is
greatly acknowledged. We deeply appreciate and record our thanks for the meritorious support extended by Sh.
Manish Kumar,K.G.Dashora, and other staff members of RAPS-3&4 Chemistry Control Section.

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REFERENCES:

1. “Carbon-graphite materials” downloaded from Internet.

2. “Report on analysis of antimony in carbon bearing and mechanical seal of Primary
coolant Pumps of RAPS-3” by Dr. P.K.De, MSD, BARC, issued vide letter no
MSD/PKD/2004/329 dated 18.03.20054.
3. “Environmental considerations” downloaded from candu.canteach.org web site.
4. “Impact of main radiological pollutants on contamination risks (ALARA)- Optimisation
of physico chemical environment and retention techniques during operation and
shutdown.” by A. Rocher, Electricité de France / GPr- J.L. Bretelle, Electricité de
France / GDL M.Berger, Electricité de France/SETTEN.
5. “ISOE 1999 Report-submission for Canada” downloaded from Internet.
6. “Antimony Transport and Removal” by D.A. Guzons, H.A. Allsopand and D.G.Webb,
AECL, Chalk River Laboratories, Chalk River, Ontario.
7. Minutes of 112th, 113th, 114th, 115th and 116th meeting of COSWAC.

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