Journal of Nuclear Science and Technology

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Boiling and drying accident of high-level liquid

waste in a reprocessing plant: Examination of the
NO2 and NO generation using the simulated waste

Takashi Kodama, Hiroshi Kinuhata, Yuki Shibata, Mikio Kumagai, Kazunori

Suzuki, Shin-Itiro Hayashi & Shingo Matsuoka

To cite this article: Takashi Kodama, Hiroshi Kinuhata, Yuki Shibata, Mikio Kumagai, Kazunori
Suzuki, Shin-Itiro Hayashi & Shingo Matsuoka (2020) Boiling and drying accident of high-
level liquid waste in a reprocessing plant: Examination of the NO2 and NO generation using
the simulated waste, Journal of Nuclear Science and Technology, 57:9, 1101-1110, DOI:
10.1080/00223131.2020.1764405

To link to this article: https://doi.org/10.1080/00223131.2020.1764405

Published online: 09 Jun 2020.

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JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY
2020, VOL. 57, NO. 9, 1101–1110
https://doi.org/10.1080/00223131.2020.1764405

ARTICLE

Boiling and drying accident of high-level liquid waste in a reprocessing plant:

Examination of the NO2 and NO generation using the simulated waste
Takashi Kodamaa, Hiroshi Kinuhataa, Yuki Shibataa, Mikio Kumagaib, Kazunori Suzukib, Shin-Itiro Hayashib
and Shingo Matsuokab
a
Safety and Quality Division, Japan Nuclear Fuel Ltd, Aomori, Japan; bUI Sciences Inc., Tokyo, Japan

ABSTRACT ARTICLE HISTORY

NO2 and NO generated during a boiling and drying accident, which affects the release of volatilized Received 17 January 2020
radioactive Ru into the atmosphere, were examined using various samples including simulated Accepted 30 April 2020
high-level liquid waste and a thermogravimetric analyzer. NO2 and NO in the gas flowing out of the KEYWORDS
analyzer were measured separately using a NOx analyzer equipped with NO2 and NO sensors. The Reprocessing; high-level
samples were heated to 600°C at constant heating rates of mainly 0.2 and 1°C min−1 that was liquid waste; severe accident;
adopted taking into account the decay heat of high-level liquid waste. It was found that under 180° boiling; NO2; NO; RuO4; NOx;
C some nitrates in the liquid waste mainly separated their nitrate groups as HNO3 without O2; drying
generating NOx (a mixture of NO and NO2) and above 300°C the residual HNO3 in the waste
participated in thermal decomposition generating NOx. The generation rates of NO2 and NO were
obtained as a function of time using Arrhenius type equations, and the O2 rate was derived from
these equations using the stoichiometry of the reactions that generate NO2, NO, and O2.

1. Introduction
The boiling accident of high-level liquid waste (HLLW)
has drawn considerable attention among stakeholders
[1,2] because of the potentially high exposure of the
general public to radiation. Accordingly, a Probabilistic
Safety Analysis of this accident, although an internal
event, was conducted for commercial plants in the
United Kingdom, France, and Japan, and the occurrence
frequency and rough radiation dose were reported [3–5].
However, all reports excluded the drying stage probably
because of its extremely low occurrence frequency.
On the other hand, an experiment including an
initial drying stage up to 160°C was carried out in
France using the actual HLLW, and the proportions of
individual radioactive materials released to the gas-
phase were reported [6]. In Japan, the Japan Atomic
Energy Agency, the former Japan Nuclear Energy Safety
Organization and Japan Nuclear Fuel Ltd. examined
jointly the phenomena from boiling to 600°C1 over
a 5-year period from 2009 using mainly the simulated-
HLLW (SHLLW) and partly the actual HLLW [7].
Following this, reflecting on the Fukushima Daiichi
nuclear power plant accident, the evaporation and dry-
ing accident2 and 5 other types of accident were deter-
mined as serious accidents beyond the design-basis
accidents by the Nuclear Regulation Authority, and
the reinforcement not only of preventive but also miti-
gative measures against these accidents was required
[8]. Such reinforcement was required not only for inter-
nal events but also for external events.
It is well known that a large proportion of Ru is
volatilized during the stage from the late period of boiling
to drying [6,7,9–12]. Therefore, in the case that the cool-
ing period of reprocessed spent-fuel is not long, 106Ru
having a 374-day half-life might expose the public to
a large dose.
Since volatilized Ru having the chemical form of
RuO4 [13] shows strong oxidative properties, it is
affected directly or indirectly by coexisting substances
such as H2O, HNO3, HNO2, NO2, NO, and O2 and will
change to nonvolatile Ru. Accordingly, it is important
to know the released rates of these substances from the
beginning of boiling to the end of drying (in this report
600°C). In this report, the generation of NO2 and NO
was examined that are inevitable for the evaluation of
a proportion of the volatilized Ru being released from
the tank to the atmosphere (LPF: Leak path factor [14]).
Although similar reports on the study of NOx3
generation exist [10,11,15], NO2 and NO were not
treated separately. However, the LPF of volatilized
Ru is greatly affected by HNO2 in H2O and HNO3
condensed at the wall [12]. HNO2 is generated from
the NOx absorbed in the condensed liquid and the
NOx absorption rate depends not only on its concen-
tration but also on the proportion of NO2 to NOx.
Further, the amount of O2 generation accompanying
the NOx generation differs from NO2 to NO. O2 plays

CONTACT Takashi Kodama takashi.kodama@jnfl.co.jp Japan Nuclear Fuel Ltd., 4-108, Aza Okitsuke, Oaza Obuchi Rokkasho-mura, Kamikita-gun,
Aomori 039-3212, Japan
*Present address: Japan Nuclear Fuel Chemical Analysis Co., Ltd.
This article has been republished with minor changes. These changes do not impact the academic content of the article.
© 2020 Atomic Energy Society of Japan. All rights reserved.
1102 T. KODAMA ET AL.

the roles of an oxidizer of NO and partly of a carrier 50 ~ 60°C and added to SHLLW. Mo in this solution
gas sending the volatilized Ru to the atmosphere. seems to exist as molybdic acid rather than nitrate
Therefore, in this report, NO2 and NO were measured since a brown colored gas, probably NO2, was evolved
separately, and the amount of O2 accompanying NO2 during the dissolution. Mn nitrate was used as
and NO generation was derived from the stoichiome- a substitute for Tc nitrate [17]. The chemical form of
try of the reactions generating NO2, NO, and O2. Ru nitrate reagent, which was purchased from Tanaka
The reports so far had other issues as follows. The Holdings Co., Ltd., was estimated as Ru(NO)(NO3)3
heating rates used in the experiments [11,15] were ∙1.8H2O from the thermogravimetric analysis shown
more than 10 times faster than that in the realistic in Appendix 1. Concentrations of the nitrates exclud-
accident condition. In the boiling experiments, NOx ing Cs were measured using ICP-AES and that of Cs
was measured after the boiled vapor passed through nitrate using ICP-MS.
a Liebig condenser [10]. In this case, a part of NOx was SHLLW-K contains 10 main nitrates excluding Mn
absorbed in the condensed liquid. With these issues in nitrate. Fe and Ni nitrates were included as the repre-
mind, we carried out experiments simulating the rea- sentatives of corrosion products, although their
listic accident condition. amounts are small. SHLLW-K was mainly used for
the examination of change in chemical forms of
nitrates by the increase in temperature at the drying
2. Experimental stage.
2.1. Preparation of samples
2.1.2. Individual nitrate solutions and their powder
2.1.1. Simulated waste samples
Two types of simulated waste solutions, SHLLW-J and In order to examine the effect of nitric acid in the waste
-K, were prepared. The compositions are shown in solution on the NOx generation, we prepared two types
Table 1. of samples. One is the solutions each containing only one
SHLLW-J simulates HLLW of the Rokkasho major nitrate, that is, Zr, Mn, Ru, Pd, Ce, and Nd in 2 mol
Reprocessing Plant [16]. The nitrates of guaranteed L−1 nitric acid. Concentration of each nitrate was
reagents were dissolved in 2 mol L−1 nitric acid. the same as that in SHLLW-J. The other is the respective
Since Mo nitrate could not be found at a market, Mo powders, ZrO(NO3)2·2H2O, Mn(NO3)2･6H2O,
metal powder was dissolved in 4 mol L−1 nitric acid at RuNO(NO3)3·1.8H2O, Pd(NO3)2･2H2O, Ce(NO3)3
･1.5H2O, and Nd(NO3)3･6H2O.4
Table 1. Compositions of the simulated solutions.
Concentration1) 2.2. Measurement of the NOx generation rate
SHLLW-J SHLLW-K
Element Reagent mol L−1 2.2.1. Method
P H3PO4 0.0035 - The apparatus to measure the NO2 and NO generation
Cr Cr(NO3)3 0.0068 - rate is shown in Figure 1 schematically. The measure-
Fe Fe(NO3)3·9H2O 0.025 0.025
Ni Ni(NO3)2·6H2O 0.003 0.003 ment was performed as follows.
Rb RbNO3 0.015 - SHLLW-J and the individual nitrate solutions were
Sr Sr(NO3)2 0.033 0.034
Y Y(NO3)3·6H2O 0.018 -
concentrated two to three times in advance. Individual
Zr ZrO(NO3)2·2H2O 0.18 0.180 concentrated solutions of 10–100 mg were placed in an
Mo Mo2) 0.117 0.117 alumina or platinum cell and set in the thermogravi-
Mn Mn(NO3)2･6H2O 0.051 -
Ru RuNO(NO3)3·1.8H2O 0.091 0.091 metric analyzer (TG/DTA-50, Shimadzu Corporation)
Rh Rh(NO3)3 0.014 - and the temperature was increased from room tempera-
Pd Pd(NO3)2·2H2O 0.045 0.043
Ag AgNO3 0.0022 - ture to 600°C at constant heating rate of 0.2, 1, and 5°C
Cd Cd(NO3)2·4H2O 0.0035 -
Sn SnO2 0.0024 -
Sb Sb2O3 0.0006 -
Te TeO2 0.016 -
Cs CsNO3 0.068 0.069
Ba Ba(NO3)2 0.040 -
La La(NO3)3·6H2O 0.030 -
Ce Ce(NO3)3·6H2O 0.10 0.099
Pr Pr(NO3)3·6H2O 0.027 -
Nd Nd(NO3)3·6H2O 0.096 0.095
Sm Sm(NO3)3·6H2O 0.017 -
Eu Eu(NO3)3·6H2O 0.0034 -
Gd Gd(NO3)3·6H2O 0.090 0.090
H+ HNO3 2.0 2.0
1) Concentrations were analyzed by ICP-AES or ICP-MS
except oxides and nitric acid. Oxides concentrations were
calculated from the amounts added. Figure 1. Schematic diagram of the apparatus to measure the
2) Metal Mo powder was dissolved in 4mol/L nitric acid. NO2 and NO generation rates.

min−1. For the powder samples, 10–30 mg and the rate
of 5°C min−1 were used. Mass changes of the powder
samples were also measured.
As a carrier gas 100 mL min−1 N2 was introduced to
the thermogravimetric analyzer and the exit gas was
diluted with 1 L min−1 N2. A part of it was introduced
into the NOx analyzer employing a constant potential
electrolysis (HT-2300, Hodaka Co., Ltd.). The analyzer
is equipped with NO2 and NO sensors and NO2 and
NO were measured separately. The amount of NOx
obtained was the sum of NO2 and NO. The accuracy of
the measured value was within ±5% and the minimum
sensitivity was 1 ppm. The analyzer was calibrated
using the standard gas.
In a similar study [15] air was used as the carrier
gas. In the present study, however, N2 was used except
the Nd powder sample. Even if the carrier gas is N2, O2
is generated in the course of nitrate decomposition
which may oxidize NO. However, the estimation of
oxidation rate of NO using the rate constant in the
literature [18] showed no such reaction occurred
owing to the low partial pressure of NO and O2 in
the analyzer.
2.2.2. Setting of the heating rate
In the long-term experiments reported so far [7,10], the
range of the heating rate of 0 ~ 2°C min−1 up to 400°C
was adopted. This range simulated the accident condi-
tion for the HLLW decay heat density of 5 kW m−3.5
Referring to these heating rates, the rates of 0.2 and 1°C
min−1 were mainly adopted in the present experiments.
The rate of 5°C min−1 was used for acceleration experi-
ments to know the general trend. The details of the
change of the heating rate in the realistic accident con-
dition will be discussed in an upcoming paper.
2.3. Experiment for studying the change of
nitrates to oxides
With increasing temperature of the waste solution,
nitrates change to oxides. In order to examine which
nitrate changes to oxide at relatively low temperatures,
the following experiment was carried out.
Two same solutions containing 120 mL SHLLW-K in
500 mL separable flasks were heated up to 180 and 300°
C, respectively. The heating rate was 0.14 ~ 0.17°C min−1
up to 180°C and 0.9°C min−1 between 180 and 300°C.
The dried residues obtained at both temperatures were
used as samples. The residue obtained at 180°C had nitric
acid odor. Although the odor continued after the residue
was dried in a silica gel desiccator for one month, its
treatment became easier since the deliquescency
decreased. 10 ~ 20 mg pulverized samples of the residues
obtained at 180 and 300°C were treated for 10 min under
ultrasonication in 200 mL pure water at room tempera-
ture. The individual solutions were filtrated through
a millipore filter with a pore size of 0.45 μm and the
JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY 1103
concentrations of nitrates dissolved in water were mea-
sured by ICP-AES and ICP-MS for Cs. Comparing the
concentration ratio of a certain metal element to Cs
measured above with that of the initial SHLLW-K,
a proportion of nitrate which changed to oxide was
obtained. The reason why Cs was used as the denomi-
nator of the concentration ratio is that Cs nitrate and its
oxide are both water soluble and so the water soluble
portion is 100% independent of temperature.
3. Results and discussion
3.1. Definition of the NOx Generation Ratio and
its usage
The NOx Generation Ratio GRNOx(θ) [%] is defined as
the ratio of the amount of N in the generated NOx to
the total amount of N in the initial nitrates. GR is
a function of temperature θ [°C]. For example, if the
ratio is 100% when the solution is heated from room
temperature to 600°C and if the NOx consists of 80%
NO2 and 20% NO, GRNOx(RT→600) = 100%, GRNO2
(RT→600) = 80% and GRNO(RT→600) = 20%.
However, even if GRNOx(RT→600) = 100%, it does
not mean that all N in the nitrates is converted to
NOx as is explained in 3.3. and 3.4. Using GRNOx, the
proportion of N in the nitrate converted to NOx was
examined.
3.2. NOx generation from the simulated waste
3.2.1. Generation of NO2 and NO
Figure 2 shows temperature dependence of NO2 and
NO generation rates of SHLLW-J at heating rates of
0.2 and 1°C min−1. Since the NO generation rate is
mostly smaller than that of NO2 in Figure 2(a), the
scale of the longitudinal axis in Figure 2(b) is twice
that of NO2. The unit of the generation rate is % °C−1
which means an increase of GR per 1°C increase. The
temperature increase by 1°C corresponds to 5 min for
the heating rate of 0.2°C min−1 and so on. As the
heating rate is constant in the present case, the tem-
perature dependence curve is easily converted to the
time dependence curve.
We can see 2 to 3 small NO2 peaks in the tempera-
ture range of 110 ~ 130°C and a large peak between
250 and 330°C. In the case of 0.2°C min−1 the NO2
generation ends by 360°C and in the case of 1°C min−1
it is very small above 400°C.
For the NO generation, 3 small peaks appear in the
temperature range of 110 ~ 170°C in the case of 0.2°C
min−1 but its generation in such a low temperature
range is not clear in the case of 1°C min−1. However,
its generation becomes clear above 250°C for the two
heating rates with 2 clear peaks, one around 340°C and
the other 470°C. In the range around 340°C the NO
generation becomes larger than the NO2 and above
1104 T. KODAMA ET AL.

a trivalent metal, the above relation does not depend on

the valence number and is also applied to HNO3. The
relation, however, cannot be applied to RuNO(NO3)3,
since it contains NO and furthermore the valence num-
ber of Ru changes during the boiling and drying stage.
However, since the contribution of Ru nitrate compound
to the total amount of NOx is small as shown in 3.3., the
amount of O2 generated as a result of Ru oxidation is not
important for the estimation of the total amount of O2
generation.
Using the relations shown in formulas (1) and (2),
we can estimate the O2 generation rate from the NO2
and NO generation rates.

3.2.3. Change of nitrates to oxides

Figure 2. NO2 and NO generation rates of SHLLW-J heated at
different rates.
400°C NOx consists mostly of NO. The total amount
of NO is 20 ~ 23% that of NOx.
In Table 2, GRs of NO2, NO, and NOx heated from
room temperature to 180 and also to 600°C are given for
the two heating rates of 0.2 and 1°C min−1. GRs of NOx
up to 600°C at which temperature the NOx generation
from the simulated waste ceased were 96 and 104% for
the respective heating rates. Two ratios are almost the
same within the range of error. These values of around
100% mean that the quantity of N contained in the
nitrates is nearly equal to that of N in the NOx generated.
However, it does not mean that nearly all N in nitrates are
converted to NOx. The details are explained in 3.3.
and 3.4.
The results of the water solubility of the major
metal compounds in the residues of SHLLW-K
which were heated up to 180 and 300°C individu-
ally are shown in Figure 3. The soluble portions of
the Zr, Ru, and Pd compounds heated up to 180°C
were 2.6, 2.0, and 0.1%, respectively. The results
show that almost all of these metal nitrates chan-
ged to oxides by 180°C. On the other hand, the
soluble portion of the Ce compound was 100% at
180°C but only 2% at 300°C. This result means
that Ce nitrate changed to oxide between 180 and
300°C. The soluble portions of the Nd and Gd
compounds heated up to 300°C were 70 and
59%, respectively.
Amano et al. [15] estimated the decomposition
temperatures of nitrates using a similar method and
reported that Ce, Nd, and Gd remained as nitrates
up to 270°C and were converted to oxides by 400°
C. Although the heating rate and the temperature
range differ between the present experiment and
that by Amano et al., both results show a similar
trend.

3.2.2. Generation of O2
The decomposition of nitrate accompanies not only
the NOx generation but also O2. As an example the
decomposition reaction of Nd nitrate is shown below.
4NdðNO3 Þ3 ! 2Nd2 O3 þ12NO2 þ3O2 (1)

4NdðNO3 Þ3 ! 2Nd2 O3 þ12NO þ 9O2 (2)

The number of moles of O2 generation is 1/4 that of NO2
and is 3/4 that of NO. Although this is an example for

Table 2. Generation ratios of NOx from SHLLW-J heated at

different heating rates.
Heating rate/°C min−1 0.2 1
NO2 4 4
GR up to 180°C/% NO 1 1
NOx 6 5
NO2 77 80
GR up to 600°C/% NO 19 24 Figure 3. Water soluble portions of individual major metal com-
NOx 96 104 pounds in the residues of SHLLW-K heated up to 180 and 300°C.

3.3. Quantitative examination of NOx generation
routes from SHLLW
The following 3 routes are considered for the NOx
generation and the fate of nitrate group when the
nitrate solution is heated to 600°C:
(i) thermal decomposition of the nitrate generat-
ing NOx
(ii) release of nitrate group from the nitrate pro-
ducing HNO3 (see below)
(iii) thermal decomposition of HNO3 left in the
residue generating NOx (see below)
We examined the contribution ratio of each route
as follows.
The results shown in Figure 3 mean that almost all the
nitrate groups in Zr, Ru, and Pd nitrates are released by
180°C. If all the released nitrate groups generate NOx, its
amount reaches 680 mol m−3 as the sum of the following.
The unit mol m−3 indicates the number of moles of NOx
generated from 1 m3 of the initial liquid waste.
ZrOðNO3 Þ2 180  2  0:67  0:97 ¼ 230molm3
RuNOðNO3 Þ3 91  4  0:98 ¼ 360molm3
PdðNO3 Þ2 45  2  1:00 ¼ 90molm3
In the above calculation, the concentrations shown in
Table 1 were used. It is known that Zr and Mo pro-
duces ZrMo2O7(OH)2∙2H2O precipitate when the
waste solution is heated to 60 ~ 100°C [19,20]. In
this process all of the Mo compound and one third
of the Zr nitrate are consumed to form the precipitate
and the corresponding nitrate group in Zr nitrate
changes to HNO3. The Mo-Zr precipitation is taken
into account and a factor of 0.67 is multiplied for Zr.
On the other hand, since GRNOx(RT→180) is 5.6%
(see Table 2), the generated amount of NOx up to 180°C
from SHLLW-J is 140 mol m−3. This value is obtained
by multiplying 5.6% by 2,440 mol m−3 which is the total
amount of N in the nitrates in SHLLW-J. The value of
140 mol m−3 is less by 540 mol m−3 than the above
expected value of 680 mol m−3. Such a difference is
explained by some of the nitrates releasing their nitrate
groups as HNO3 or as gases containing N other than
NOx. Candidate gases are N2O and N2. However, since
the concentration of HNO3 in the solution (or in the
residue) becomes higher than 11 mol L−1 [6] and the
temperature is near 180°C, the residue is under a strong
acidic and oxidative atmosphere. Therefore, the possi-
bility of generating these gases is excluded and N in
nitrates of 540 mol m−3 is considered to be released as
HNO3. Further, 120 mol m−3 HNO3 will be released by
the Mo-Zr precipitation and Fe(NO3)3･9(H2O) will
also release 75 mol m−3 HNO3 [21]. Thus, 740 mol m−3
HNO3 will be released from the nitrates in SHLLW-J
JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY 1105
upon heating. This value is 30% of the total amount of
N, that is, 2,440 mol m−3.
Next, we examine the NOx generation above 180°C.
By 180°C, almost all of the Zr, Ru, and Pd nitrates have
been decomposed. The NOx generation source expected
above 180°C is nitrates other than these nitrates. The
total amount of N except Fe, Zr, Ru, and Pd nitrates is
1,540 mol m−3 calculated from Table 1. If all the
N converts to NOx, the amount of NOx generated is
1,540 mol m−3. However, the NOx amount measured
between 180 and 600°C is 2,340 − 140 = 2,200 mol m−3
and it is 660 mol m−3 larger than the above value. The
value of 2,340 is the total amount of NOx measured and
140 is the amount of NOx measured by 180°C at the
heating rate of 0.2°C min−1. This difference of
660 mol m−3 means that NOx is generated from a source
other than the nitrates, that is, from the HNO3 decom-
position. The decomposition of HNO3 in the nitrate
solution is clearly observed as shown in 3.4. below.
The above results lead to Figure 4 as follows. The
amounts in this figure are expressed as relative values to
the total amount of N in the nitrates in SHLLW-J. If A %
is released as HNO3 and B % as NOx, B is equal to
100 − A. A is 30 as stated above. Under such condition,
the relative amount of the NOx generation, C%, by the
decomposition of HNO3 is obtained as C = 96 − B. The
value 96 is that of GRNOx(RT→600) at the heating rate of
0.2°C min−1. However, since the nitrates other than Fe,
Zr, Ru, and Pd nitrates may produce some HNO3,
A might be larger than 30, B less than 70 and C larger
than 26.
3.4. NOx generation from the individual nitrate
solutions and powder samples
The results of the temperature increasing experiments
of the individual nitrate solutions clearly show the
presence of HNO3 decomposition.
GR(RT→600)s of NO2, NO, and NOx obtained
from the individual nitrate solutions containing Zr,
Pd, Ce, Ru, Mn, and Nd and their powder samples
are given in Table 3. The values of GRNOx from the
solutions are 130 ~ 410%, that is, all exceed 100%. On
the other hand, these values from the powders are
Figure 4. Contribution of the three routes for the NOx gen-
eration and the fate of nitrate group in SHLLW-J heated at 0.2°
C min−1 up to 600°C.
1106 T. KODAMA ET AL.

Table 3. NOx generation ratios of each metal nitrate solution initial mass. Since the mass decrease from the powder
and powder heated at 5°C min−1 up to 600°C. is significantly larger than that after the release of
Generation ratio(%) crystal water, some nitrate group should be released
Compound Form1) NO2 NO NOx2) from the powder. However, NOx generation is not
ZrO(NO3)2 · 2H2O Solution 120 9 130
Powder 55 5 61
observed below 150°C. Accordingly, it is concluded
Mn(NO3)2 · 6H2O Solution 290 28 320 that the nitrate group is released as HNO3 from the
Powder 100 3 100 powder. HNO3 may be produced after reacting with
RuNO(NO3)3 · 1.8H2O Solution 140 49 180
Powder 64 27 91 the crystal water. Above 300°C the mass of the powder
Pd(NO3)2 · 2H2O Solution 370 44 410 is 44 ~ 46%. Since the mass of PdO is 46% that of the
Powder 23 5 28
Ce(NO3)3 · 1.5H2O Solution 140 27 160 initial powder, the powder is converted to the oxide.
Powder 90 10 100 Figure 6 shows the results of the Ce nitrate solution
Nd(NO3)3 · 6H2O Solution 140 36 180
Powder 83 12 95 and the powder. GRNOx(RT→600) of the solution is
1) Solution: 2 mol L−1 nitric acid solution containing the nitrate of the 160%, suggesting significant amounts of NOx are gen-
same concentration as in SHLLW-J; Powder: Powder sample erated from the decomposition of HNO3, but that of the
2) NOx is the sum of NO2 and NO, but the values may seem to have some
discrepancies among them. These discrepancies are due to significant powder is 100%. The NOx generation begins above 220°
digits, rounding, and loss of decimal places. C for the both samples and the curves resemble each
other up to 300°C. However, above 300°C the NOx
28 ~ 100% and do not exceed 100%. GRNOx exceeding generation from the solution is remarkably larger than
100% means that NOx has been generated from the that of the powder. The mass of the powder decreases to
decomposition of HNO3. On the other hand, GRNOx 92% by 220°C and to 46% by 600°C. If the release of
less than 100% means that some nitrate released crystal water occurs, the mass will decrease to 92%.
nitrate group as HNO3 out of the sample. We exam- Further, if the release of nitrate group occurs in succes-
ined the NOx and NO generation curves as a function sion resulting in Ce2O3, the mass will decrease to 46%.
of temperature as follows. Both masses accord with the measured values.
Figure 5 shows the results of the Pd nitrate solution Figure 7 shows the results of the Nd nitrate solution
and the powder. GRNOx(RT→600) of the solution is and the powder. GRNOx(RT→600) of the solution is
410% but that of the powder is 28%. The NOx gen- 180% and that of the powder 95%. The NOx generation
eration rate curve of the solution consists of two peaks, curves from the solution and the powder have similar
one appears below 250°C and the other above two large sharp peaks at high temperature range over
250°C. GRNOx below 250°C is 53% and that above 360°C. From the solution the NOx broad generation
250°C is 361%. Accordingly, the large amount of over 300°C was also observed under the sharp peaks.
NOx in the second peak is produced from the decom- For all the solution samples, the broad NOx gen-
position of HNO3. On the other hand, the NOx gen- eration curves over 300°C were observed and the NO
eration from the powder begins from 150°C. At this generation begins over 350°C (dotted lines in Figure
temperature, the mass of the powder decreases to 66%. 5–7). This should be attributed to the residual HNO3
If the crystal water is released, that is, Pd(NO3)2∙2H2 decomposition and will explain the cause of GRNOx
O→Pd(NO3)2 + 2H2O, the mass will be 86% of the

Figure 5. NOx and NO generation rates of Pd nitrate solution, Figure 6. NOx and NO generation rates of Ce nitrate solution,
and their generation rates and residual mass percentage of Pd and their generation rates and residual mass percentage of Ce
nitrate powder sample heated at 5°C min−1. nitrate powder sample heated at 5°C min−1.
 JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY 1107

in Figure 2(a). For the NO generation rate, two group

equations were used to approximate the curve in
Figure 2(b).
We assume that the time change of the amount of
the source material of NOx [mol] contained in the ith
group per 1 m3 of the initial waste solution is
expressed as M i(t) [mol m−3] and its derivative is
equal to the NOx (NO2 or NO) generation rate. We
assume that the NOx generation is a first-order reac-
tion with the rate constant given by the Arrhenius type
equation. Therefore M i(t) is described by:


dMi ðtÞ Ei
¼ Ai Mi ðtÞ exp  (3)
dt R½θðtÞ þ 273:15

θðt Þ ¼ rt þ θð0Þ (4)

Figure 7. NOx and NO generation rates of Nd nitrate solution, In the above equations, Ai [min−1] is the frequency
and their generation rates and residual mass percentage of Nd factor, Ei [kJ mol−1] the activation energy,
nitrate powder sample heated at 5°C min−1. (For only this
R = 0.00831 kJ mol−1 K−1 the gas constant, θ(t) [°C]
powder sample, air was used as a carrier gas.)
the temperature of the SHLLW at time t [min] and r [°
C min−1] the constant heating rate. The solution of
Equation (3) is given as:
(RT→600) over 100%. However, such generation does
not seem to occur for the powder samples. For Zr, Ru,  ðt
 
Ei
and Mn nitrates, the similar trend was observed as can Mi ðtÞ ¼ Mi ð0Þ exp Ai exp  dt0
0 R½θðt0 Þ þ 273:15
be seen in Table 3.
Thus, the NOx generation rate curve differs from The total generation rate RT(t) is expressed as:
nitrate to nitrate. Further, the curve from SHLLW is X dMi ðtÞ
quite different from the sum of the curves from the RT ðtÞ ¼ 
dt
individual nitrate solutions. Such phenomenon was X
i  ðt
 
d Ei
¼ Mi ð0Þ exp Ai exp  dt0
reported first by Amano et al. [15]. As a typical exam- i
dt 0 R½θðt 0 Þ þ 273:15
ple, we take Pd nitrate. Most of Pd nitrate in SHLLW- (5)
K converts to the oxide by 180°C (see 3.2.3) with
generating a small amount of NOx. On the other The constants used in Equation (5) are given in Table 4.
hand, the Pd nitrate solution generated NOx between The frequency factor and the activation energy were
120 and 600°C and GRNOx was 410%. However, the obtained to simulate the experimental results shown in
decomposition of HNO3 that generates NOx was Figure 2 at 0.2 and 1°C min−1. The sum of M i(0) was set
observed both in SHLLW-J and the solution contain- to 2440 mol m−3, which is a total amount of N of the
ing one nitrate. nitrates in SHLLW-J. If a better match between the
measured and predicted curves is necessary, GR
shown in Table 2 may be used for the sum of M i(0).
3.5. Prediction of the NOx generation rate The generation rates of NO2 and NO as a function of
temperature with the heating rates of 0.2 and 1°C min−1
We tried to predict the generation rates of NO2 and NO are shown in Figure 8. A comparison of the accumulated
as a function of time using Arrhenius type equation. amounts of NOx as a function of temperature between
Since a constant temperature increasing rate is adopted the predicted and the observed results is given in Figure 9.
in the present experiment, temperature is easily con-
verted to time as shown in Equation (4) below The
reverse is also the same. A similar trial was reported Table 4. List of constants used in the Arrhenius type
equations.
before [7]. There, they treated NOx without separating
Initial amount Frequency factor A Activation energy E
NO2 and NO and attempted to correlate the predicted
Group mol m−3 min−1 kJ mol−1
curve with the experimental one at a heating rate of 5°C NO2 1 83 5.0E+17 150
min−1. In that case larger deviation between them was 2 116 2.0E+13 140
observed at 2°C min−1 which is even higher than the 3
4
349
1,246
2.0E+10
2.0E+12
120
150
heating rate of HLLW in the realistic accident condition. 5 233 3.0E+10 140
In the present study, five group equations were used NO 6 266 2.0E+06 100
to approximate the NO2 generation rate curve shown 7 150 1.0E+12 200
1108 T. KODAMA ET AL.
Figure 8. NO2 and NO generation rates of SHLLW-J predicted
using Arrhenius type equations.
Figure 9. Comparison of the accumulated amounts of NOx
between the predicted and the observed results.
In these figures the results from Equation (5) were con-
verted to those of function of temperature using Equation
(4) and the correction factors of 0.96 and 1.04 were used.
Comparing the predicted curves shown in Figure 8
with the corresponding observed ones shown in
Figure 2, good correlations are observed. The accumu-
lated amounts of NOx also agree well each other
especially in the case of 0.2°C min−1 as can be seen
in Figure 9. If the number of groups of Arrhenius type
equations is increased, much better correlation will be
obtained. However, we consider the present correla-
tion is sufficient for the purpose to evaluate the LPF.
Although the composition of SHLLW-J shown in
Table 1 is based on the ORIGEN-2 results, in the
actual liquid waste the insoluble residues containing
Ru, etc. are produced [22] and they would not gener-
ate nitrates. If we assume that 60% of Ru is contained
in the insoluble residue, the amount of N in the Ru
nitrate decreases from 360 to 150 mol m−3. Only 20%
of the total N atoms in the Zr, Ru, and Pd nitrates
generates NOx as was explained in 3.3. Assuming that
this average ratio of 20% is applicable to the Ru nitrate,
the decreased amount of the NOx generation due to
the insoluble residue becomes (360 − 150) ×
0.2 = 42 mol m−3. This value is only 2% of the total
amount of NOx generation shown in Table 2. Thus,
the effect of the insoluble residue is insignificant.
4. Conclusion
If the long-term cooling function loss occurs, HLLW in
a tank begins to boil and eventually dries. In this course,
the waste temperature increases and various radioactive
and non-radioactive materials will be released from the
tank. Our final purpose of the work is to predict the
release rate of these materials to the atmosphere as
a function of time. Such information can be used effec-
tively not only for the evaluation of the radiation dose to
the general public but also for the implementation of the
accident management and also the disaster prevention.
In the present work, Arrhenius type equations were
used to predict the NO2 and NO generation rates as
a function of time for the heating rate between 0.2 and
1°C min−1. The generation rate of O2 was derived from
those of NO2 and NO. Further we found that some
nitrates separated their nitrate groups as HNO3 with-
out generating NOx and above 300°C the residual
HNO3 in the waste participated in the thermal decom-
position generating NOx. The NOx generation affects
the LPF of volatilized Ru and the accompanying O2
may partially act as a carrier gas at the waste tempera-
ture above 200°C that sends Ru to the atmosphere.
In an upcoming paper, we will treat the waste
temperature increase and the release of H2O and
HNO3 vapors accompanying the accident.
Notes
1. The generation of carrier gases such as vaporized H2
O and HNO3 and NO2, NO, and O2 gases which play
the role of sending the radioactive materials from the
tank into the atmosphere will cease by 600°C.
2. In the regulation [8] the term ʻevaporationʼ is used
instead of ʻboilingʼ. Since the accident occurs above the
boiling point of HLLW, ʻboilingʼ is used in this report.
3. In this report, NOx means a mixture of NO and NO2.
4. Numbers of crystal water were used as were described in
labels of reagents without Ru (see Appendix 1.) and Ce.

Ce(NO3)3∙6H2O purchased was dried at 110°C for
24 hours. From the weight decrease, we estimated a num-
ber of 1.5.
5. Assuming the following parameters for reprocessed
PWR spent fuel, the decay heat density of HLLW is
about 5 kW m−3: specific power of 38 MW t−1, burn-
up of 45,000 MWd t−1, cooling time of the fuel 6 y,
and generation of 0.4 m3 HLLW per 1 t fuel.
Disclosure statement
No potential conflict of interest was reported by the authors.
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1110 T. KODAMA ET AL.

Appendix
The powder sample of the Ru nitrate, a guaranteed reagent, of 16.3 mg was heated at 1°C min−1 up to 500°C in the
thermogravimetric analyzer. The residual mass percentage and the generation rates of NOx and NO were measured as functions
of temperature. By 120°C the crystal water was vaporized and the mass decreased to 91%. Afterwards, the mass decreased rapidly
by the thermal decomposition of the nitrate. By 350°C the decomposition and dehydration finished and the mass decreased to an
asymptotic value of 38%. If the initial chemical form is assumed to be Ru(NO)(NO3)2∙1.8H2O, the residual mass after the release
of water is 91% and that after the decomposition of the nitrate is 38%, in accordance with the measured values. Thus, we
estimated the chemical form of the Ru nitrate as Ru(NO)(NO3)2∙1.8H2O.