Volume reduction of Cs-contaminated soil using washing

treatment: Basic knowledge of Cs desorption mechanism

from clay minerals of soil

Dr. Herry Wijayanto

Pusat Riset Teknologi Bahan Nuklir dan Limbah Radioaktif

ORTN, BRIN

1
2024.03.28
Contents

• Introduction (Case of Fukushima NPP Accident)

• Decontamination efforts
• Status change of evacuation orders
• Radioactive-contaminated soil
• Waste processing in the Interim Storage Facility (ISF)
• Soil washing by cationic surfactants
• General conclusions

2
Introduction (Case of Fukushima NPP Accident)
Earthquake
• Triggered the emergency stop of
reactors 1-3 of Fukushima Daiichi
Nuclear Power Plant (FDNPP).
• Emergency power supplies were
triggered, starting fuel cooling
operations for reactors 1-6.
Tsunami
• Tsunami causing flooding of the
emergency power supplies,
leading to a loss of power for
reactors 1-5.
Fukushima Daiichi Nuclear Power Plant accident
• Melted in reactors 1-3 and radioactive
substances were released.
• Hydrogen explosions caused damage to reactor
buildings of 1, 3, and 4.
https://www.pref.fukushima.lg.jp/ 3
https://www.ntv.co.jp/
 Cs strongly bound with clay minerals of soil

Soil concentration map as of November 16, 2012

(amount of 137Cs deposited on the ground surface
within 80 km from FDNPP)
Deposition of radioactive
cesium (137Cs)

> 98% of cesium still

remains in the soil within
0-5 cm in depth1
Damaged Fukushima Daiichi
Nuclear Power Plant (FDNPP)
Cs strongly bound with clay
minerals of soil owing to high
affinity and prevent vertical
migration1

Cs was mainly adsorbed to micaceous clay minerals2 and probably also

presented in kaolinite-, and smectite-like clay minerals.3

4
https://radioactivity.nsr.go.jp/
Decontamination efforts
Change in Air Dose Rate

• Soon after the accident, Japanese

government implemented decontamination
work (January 2012) to reduce the amount
of radiation in the living areas.

• It has been 13 years since the FDNPP accident and the radioactive dose level in Fukushima Prefecture has been decreasing substantially due to
natural dispersion and decontamination efforts.

https://www.pref.fukushima.lg.jp/ 5
https://www.reconstruction.go.jp
Status change of evacuation orders
Status on April 22, 2011 Status on Sept 5, 2015 Status on April 1, 2017

First time festival in 7 years

• Accordingly, most of evacuation orders are gradually being lifted, except the Difficult-to-Return Zone (DRZ). The latest data provided
above is the status on April 1, 2017. 7
https://www.pref.fukushima.lg.jp/
METI
Status change of evacuation orders
Status on April 1, 2017
June 12, 2022
• Katsurao village which was considered as “Difficult-to-Return Zone” or DRZ located
within 20 km away from FDNPP has allowed the residents to come back after 11
years.
• However, only 10% of them are coming back due to high level of radiation in some
places in the village.
• Residents are still worried about eating locally grown vegetables even if their safety
is confirmed in testing.
Source: Asahi Shimbun1

August 30, 2022

• Finally for the first time, partial evacuation order was lifted in Futaba town, especially
5.55 km2 of area surrounding Futaba Station.
• Although residents were allowed to return home, however more than 80% of the
town remains designated as “Difficult-to-Return Zone” or DRZ .
• According to survey by Reconstruction Agency in 2021:
• 11.3% wanted to return
• 60.5% decided not to return
• 24.8% not yet reached a decision
• Reasons not to return:
• - Former resident have found jobs and built new lives in other regions in Japan
• - Still lack of facilities such as schools, shops, restaurants, hospitals or public services.
• Survey by the town noted that 66% of households in Futaba said they hoped to
maintain their ties with their hometown. 8
Source: The Japan Times2-4
Radioactive-contaminated soil
Temporary Storage Sites Transfer to ISF Interim Storage Facility [5,6]
(TSS) (ISF)
( ≥ 8,000 Bq kg-1 )
move to final disposal
outside the prefecture or
stored up to other places by 2045
Start: 2015 30 years
Finish (expected): March 2022

Return to the land

Recycled (<8,000 Bq kg-1) Limited use
- Remove foreign materials • Basic structure for
- Classify by concentration farms of flowers &
- Quality control energy crops
• Embankment
materials for roads
• Embankment
materials for coastal
Temporary Storage Sites levees
(TSS)

Temporary Storage Sites

(TSS) 9
 Sept 9th 2022

• Whole area approx. 1,600 ha/16km2 (Shibuya ward).

• The amount of contaminated soil being stored in ISF is approx.
14 million m3

ISF Tour:
https://www.jesconet.co.jp/interim_infocenter/en/observation.html

10
Equivalent to 11 times of Tokyo Dome!
https://www.youtube.com/@easy-radiation
 Soil drying
Sieving of 2 cm
- High pressure water
Sieving of 10 cm to
- Wire
remove big stuff;
- Crushing machine
stones, etc.

To the soil
storage facility

https://www.youtube.com/@easy-radiation
 Leachate Treatment Facility
Soil Storage Facility

Treated water is released to the

environment after monitoring of
materials including Cs-137
Impermeable sheet
Protective mat (preventing leakage into groundwater)
Water shielding sheet
Bentonite mat
Conductive mat
Water shielding sheet
Protective mat

https://www.youtube.com/@easy-radiation
[8]

move to final disposal has not been

outside the prefecture decided yet
• 7 governors opposed the or other places by 2045
reuse of contaminated soil.
• Others decided not to answer.

• Nihonmatsu residents
also rejected the reuse of
contaminated soil.
[9-11]
Waste processing in the Interim Storage Facility (ISF)

In terms of storage space and

cost, technology for volume
Combustible Soil
(leaves, grass, trees, branches etc) reduction of soil is needed.7

Incineration/ Cannot be
burning burned

Waste storage facility Soil storage facility

15
Soil washing by cationic surfactant

• Soil washing approach has been considered as remediation of 137Cs-contaminated soil concerning its simplicity and cost-
effectiveness.
• This technique is related to the ability of desorption agent (desorbent) to extract contaminants from soil. Therefore, the
suitability of desorbent is needed to be explored.
• The soil washing method by cationic surfactants (R–N(CH3)3+ ; R=long hydrocarbon chain group; N(CH3)3+ = head group)
has been widely used as desorbent to effectively desorb Cs from clay minerals via ion exchange between positively
charged amine groups with Cs ions.
• Moreover, the length of their hydrocarbon chain group plays essential role in enhancing Cs desorption.

• Cationic surfactants are usually applied in hair conditioners,

cleaning enhancers, fabric softener.
Hydrocarbon chain
group
Fig. Cationic surfactant structure
16
Previous studies

• For example, Willms et al (2004)4 studied the effect of hydrocarbon chain lengths of surfactant for Cs desorption from
kaolinite.
C-8 C-12 C-16

OTMAB (8 carbon)
DTAB (12 carbon)
HDTMAB (16 carbon)
Cs desorption increased as the chain length increased due
Kaolinite to stronger affinity for clay surfaces with longer chain
length.

• In the case of Cs desorption from Ca-montmorillonite; the interlayer expansion increased as the alkyl chain length
increased hence Cs desorption efficiency also increased5

• However, the influence of cationic surfactant head group for Cs desorption from clay minerals has not been well
understood.
17
Objectives of study

• To examine the effectiveness of cationic surfactant to desorb Cs from actual 137Cs-contaminated soil from
Fukushima Prefecture.
• To investigate the influence of cationic surfactant head group on the desorption of Cs from specific clays and
clay minerals.

18
Cs desorption from actual contaminated soil of Fukushima Prefecture
MATERIALS & METHODS

1. Samples:
• Actual 137Cs-contaminated soil taken from Fukushima Prefecture
3. Analysis of cesium activity by:
2. Desorption agents (Desorbents):
• Benzyldodecyldimethylammonium Bromide (BDAB)
• Hydrochloric Acid (HCl)

HP-Ge Detector Aloka ARC-380

Gamma counter

4. Characterization by PXRD

Hydrophilic part
(head group)

Hydrophobic part
(chain group)

20
MATERIALS & METHODS
Soil sampling

Sampling Sampling
point
location
Fukushima
Prefecture Approx.
Hiroshima 60 km
Prefecture
Tokyo
FDNPP

Sieving for 4 h
May 18, 2016
Soil with grain size < 75 µm Initial stage before planting
2 mm
Surface soil was taken
(silt & clay) (0-5 cm depth)
850 µm
250 µm
75 µm

< 75 µm Dried at RT and oven

at 105oC for 24 h
21
MATERIALS & METHODS
2500
mm
Fukushima soil < 75 µm
Sample preparation (actual 137Cs-contaminated soil)
1325.48 ch
2000 661.75 keV (137Cs)
Soil (grain size < 75 µm)

Washed 3 times by distilled 1500

Counts
water (1/20; g/mL ratio)

Mixture 1000

Centrifuged at 2400 rpm, 10 min

500

0
0 500 1000 1500 2000 2500 3000 3500
Filtrate Precipitate/Soil
Channel
Dried at 80oC Fig. Gamma-ray spectrum of soil sample taken from Fukushima Pref.
for 24 h

Measured by ALOKA Soil was measured by HP-Ge .......... (Eq 1)

gamma counter detector on August 6, 2020

137Cs was not

detected in the
filtrate

22
MATERIALS & METHODS
Cs desorption experiment

Soil (grain size < 75 µm)

Table. Amount of Cs-adsorbed to actual soil
9 and 50 mM of BDAB and HCl
(1/10; g/mL ratio)
Shaking at 25oC
for 24 h Mixture
Centrifuged at 2400 rpm, 10 min

Filtrate Precipitate/Soil
~equivalent to 0.08x 10-10 mmol Cs/g soil
Washed and dried at 80oC for 24 h

Analyzed by HP-Ge Detector

.......... (Eq 4)

23
RESULTS & DISCUSSION
Cesium desorption efficiency from soil
20
BDAB
(%) (%)

HCl
Table. Amount of Cs-adsorbed to actual soil
efficiency

15 Fukushima soil (grain size < 75 µm)

removal efficiency
desorption

10
Cs

5
Cs
137137

~equivalent to 0.08x 10-10 mmol Cs/g soil

0
HCl 9 mM HCl 50 mM BDAB 9 mM BDAB 50 mM

• In the case of soil, BDAB showed high performance of 137Cs desorption even at very low initial conc. of 137Cs (3.52 Bq/g),
compared to HCl.
• It was due to high sorption of BDAB to soil and clay caused by hydrophobic interaction resulting in strong affinity among
them and leading to contact with cesium which then replace it through ion exchange mechanism.

24
Desorbent Desorption
efficiency (%)

• In general, a great performance of Cs desorption can be

achieved by using high amount of desorbent (solid/liquid
ratio).
• When using acid, hydrothermal treatment should be
implemented to enhance Cs desorption.

• In some studies, initial conc. of 137Cs cannot be related to

desorption efficiency. It depends on characteristic of soil.

25
XRD analysis of soil

XRD showed that the actual soil contains complex minerals might
affect Cs desorption from the soil.
Influence of head group structure of cationic surfactants on the
desorption of cesium from clays and clay minerals
MATERIALS & METHODS
3. Analysis of cesium activity by:
1. Samples
• Na-bentonite (Na-Bent) (expanding clay) (Kunimine Industries Co., Ltd, Japan)
• Ca-bentonite (Ca-Bent) (expanding clay) (Kunimine Industries Co., Ltd, Japan)
• Kaolinite (Kaol) (non-expanding clay mineral) (Sigma Aldrich)
• Illite (Ilt) (non-expanding clay mineral) (Yongkoong Illite Co., Ltd, Korea)
HPGe-Detector Aloka ARC-380
2. Cationic surfactants:
Gamma counter
• Benzyldodecyldimethylammonium Bromide (BDAB)
• Dodecyltrimethylammonium Bromide (DTAB) 4. Characterization by PXRD and FTIR

Hydrophobic part
(chain group)
Hydrophilic part
(head group)

12 carbon chain length

28
Chemical composition (wt%) and structural formula of clays and clay minerals sample

Na-Bent, (Si4.42)(Al1.03Fe0.08Ti0.01Mg0.17)(Ca0.17Na0.22K0.02) O10(OH)2

Ca-Bent, (Si4.26)(Al1.12Fe0.15Mg0.38)(Ca0.17Na0.04K0.04) O10(OH)2
Kaol, (Si2.19)(Al1.85Fe0.02Ti0.01Mg0.01Mn0.0000197)(Ca0.00044) O5(OH)4
Ilt, (Si4.09)(Al1.30Fe0.21Ti0.03Mg0.11Mn0.003)(Ca0.15Na0.08K0.43) O10(OH)2

The structural formula of samples were calculated based on O10(OH)2 for Bent and
Ilt (2:1 layer structure), and based on O5(OH)4 for Kaol (1:1 layer structure).15
 MATERIALS & METHODS
Adsorption isotherm study Initial concentration of Cs-adsorbed samples
10 gr of clay
• Samples were mixed with CsCl solution (1/10; g/mL ratio) at 25oC, 24 h
• Initial concentration of CsCl was from 3 mM to 100 mM 100 mL of CsCl 100 mM
• 137Cs was added to CsCl with ratio 0.001 mmol/1 Bq (CsCl/ 137Cs) 137Cs was added to CsCl with ratio 0.001 mmol/1 Bq (CsCl/ 137Cs)
• After separation by centrifugation, the liquid was measured by using Shaking at 25oC Mixture
ALOKA gamma counter for 24 h
Centrifuged at 2400 rpm, 10 min
Langmuir equation:

.......... (1)
Filtrate Precipitate

Analyzing by ALOKA - Washing by DW until 137Cs activity in solution

gamma counter is zero (loosely bound 137Cs was removed)
- Dried at 80oC for 24 h
Clay (solid samples) containing cesium
(a) Ca-Bent Kaol (b)
was measured by Hp-Ge Detector
0.7 3.0
Na-Bent Ilt (Determination of RA and C)
Ilt Ca-Bent
0.6 Kaol Na-Bent
2.5

0.5
.......... (Eq 1)
Ce/qe (gml-1)
qe (mmolg-1)

2.0

0.4
1.5
0.3

1.0
0.2

0.5
0.1

0.0 0.0
.......... (Eq 2)
0.00 0.02 0.04 0.06 0.08 0.10 0.00 0.02 0.04 0.06 0.08 0.10

Ce (mmolml-1) Ce (mmolml-1)
30
Fig. (a) Cs adsorption to samples, and (b) Langmuir isotherm plot of Cs adsorption to samples
 Solid sample-based measurement Liquid sample-based measurement
(used for initial concentration)

Cesium was adsorbed 100% of adsorption capacity

of clays and clay minerals

31
MATERIALS & METHODS
Cesium desorption experiment

Cs-adsorbed samples (clays and clay minerals)

BDAB, DTAB, HCl 1-50 mM
Shaking at 25oC, 24 h
(1/10; g/mL ratio)

Mixture .......... (Eq 5)

Centrifuged at 2400 rpm, 10 min

Filtrate Precipitate
Washed and dried at
80oC, 24 h

Analyzed by HP-Ge Detector

32
MATERIALS & METHODS
Influence of pH on Cs desorption by cationic surfactants
pH without adjustment:
• pH of solution BDAB 50 mM = 6.18
Cs-adsorbed samples DTAB 50 mM = 5.25
(Na-Bent/Cs; Ca-Bent/Cs; Kaol/Cs; Ilt/Cs)
HCl or NaOH 1 M

to know the ionization degree

toward surfactants solution

Surfactants solution 50 mM Surfactants solution with Mix up to 24h

pH = 3, 7, 12 adjusted pH

• pH of mixture (adjustment during desorption process)

Cs-adsorbed samples
HCl or NaOH 1 M

to understand the protonation and

deprotonation of Cs-adsorbed
samples in the mixture system

Surfactants solution 50 mM Mixing of

Continue mix up to 24h
surfactants + Cs-adsorbed samples
(pH = 3, 7, 12) 33
RESULTS & DISCUSSION BDAB

Cs desorption from Na-bentonite DTAB

70
0.5 (a)
Amount of Cs desorbed (mmolg-1)

60

Cs desorption efficiency (%)

0.4
50 T
O
T
𝛿- 𝛿- 𝛿- 𝛿- 𝛿-
0.3 40
T

30
O
T
𝛿- 𝛿- 𝛿- 𝛿- 𝛿-
0.2

20
16 Å
BDAB
0.1 DTAB T T 13.6 Å
10
HCl
BDAB extended
DTAB extended
O
T
𝛿- 𝛿- 𝛿- 𝛿- 𝛿- O
T
𝛿- 𝛿- 𝛿- 𝛿- 𝛿-
0.0 0
0 20 40 60 80 100
Desorbent (mM)
20
(b)
(a) (c)
16 Å ¨ Montmorillonite (JCPDS 29-1498)
 Clinoptilolite (39-1383)
§ Quartz (JCPDS 46-1045)
Ñ Feldspars (JCPDS 84-0710)
◼ Calcite (JCPDS 47-1743)
BDAB
DTAB • Cs desorption efficiency from Na-Bent/Cs by BDAB
ª Cristobalite (JCPDS 39-1425)

18
HCl 100 mM was ~44% and was higher than ~29% of
Intensity (a.u.)

16.4 Å BDAB extended

DTAB extended using DTAB 100 mM.
16.9 Å Na-Bent/Cs/BD100

Na-Bent/Cs/BD50 16
• BDAB structure is bulkier than DTAB resulting in
Intensity (a.u.)

13.1 Å
d001 (Å)

Na-Bent/Cs/BD30
16 Å
Na-Bent/Cs/BD10
higher interlayer expansion thereby enhancing Cs
13.6 Å Na-Bent/Cs/DT100 14 desorption.
Na-Bent/Cs/DT50
13.6 Å
Intensity (a.u.)

Na-Bent/Cs/DT30
13.6 Å Na-Bent/Cs/DT10
12
13.5 Å 12.1 Å Na-Bent/Cs
12.2 Å
§ 12.1 Å
(001)

(100)

(105)

12.8 Å Ñ 
¨
¨§ ª
 Na-Bent
12.6 Å
 Ñ ◼ 
Ñ ¨§ §§ §  10
4 6 8 10 12 14 0 10 20 30 40 50 60 70 80 90 100
2q ( ) o 10 20 30 40 50 34
2q (o) Desorbent (mM)
Transmission Electron Microscope (TEM) Measurement

Na-Bent/Cs + BDAB 50 mM

Na-Bent/Cs

Na-Bent/Cs + DTAB 50 mM
 RESULTS & DISCUSSION BDAB DTAB

T
Cs desorption from Ca-bentonite O 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- T

70
T O
T
𝛿- 𝛿- 𝛿- 𝛿- 𝛿-
(a)
(b)
0.5
Amount of Cs desorbed (mmolg-1)

60
15.2 Å

Cs desorption efficiency (%)

T T
14.2 Å
0.4 50 O
T
𝛿- 𝛿- 𝛿- 𝛿- 𝛿- O 𝛿- 𝛿- 𝛿- 𝛿- 𝛿-
T
40
0.3

30
0.2 T - - - - - Divalent cation must associate with negative charge
O
20 T Na+ Na+
on two layers to achieve charge neutrality
0.1
BDAB
DTAB
HCl 10 T - - - - - Infinite T - - - - -
T
O
- - - - -
O separation O T
BDAB extended
DTAB extended
T Na+ Na+ T
Ca2+ Ca2+
0.0 0 Na+ Na+ Ca2+ Ca2+
T Na+ Na+ T T
0 20 40 60 80 100 T
O O O
Desorbent (mM) T - - - - - O
T - - - - - T - - - - - T - - - - -
20
(b)
(b) 15.2 Å ¨ Montmorillonite (JCPDS 29-1498) Ñ Feldspars (JCPDS 84-0710)
(d)
(c) BDAB
 Clinoptilolite (39-1383) ◼ Calcite (JCPDS 47-1743)
§ Quartz (JCPDS 46-1045) ª Cristobalite (JCPDS 39-1425) DTAB
HCl
18
Intensity (a.u.)

14.1 Å Ca-Bent/Cs/BD100 BDAB extended

Ca-Bent/Cs/BD50
DTAB extended • Cs desorption efficiency from Ca-Bent/Cs by 100 mM of
13.6 Å
Ca-Bent/Cs/BD30
16
BDAB and DTAB was not so much different (~62 and
15.2 Å
Intensity (a.u.)

~53%) because increased interlayer distance also had

d001 (Å)

12.6 Å Ca-Bent/Cs/BD10

Ca-Bent/Cs/DT100 small difference between two surfactants.

14.2 Å 14
Ca-Bent/Cs/DT50
14.2 Å
13.6 Å Ca-Bent/Cs/DT30
• Ca-Bent has limitation to be expanded in comparison
Intensity (a.u.)

Ca-Bent/Cs/DT10

13.3 Å
12
12.4 Å to Na-Bent due to different type of exchangeable
12.4 Å Ca-Bent/Cs
12.4 Å cation.
(001)

(100)

§
(105)

12.4 Å ¨ ◼

¨§ ª Ñ ª
14.7 Å ◼
Ñ ª ¨
Ca-Bent 10
4 6 8 10 12 14
0 10 20 30 40 50 60 70 80 90 100 36
o
2q ( ) 10 20 30 40 50
2q ( )o Desorbent (mM)
 Comparison of Cs desorption for Na-Bent and Ca-Bent
70 70
0.5 (a) Na-Bent/Cs (0.77 mmol∙g-1 ) 0.5
(b) Ca-Bent/Cs (0.79 mmol∙g-1 )

Amount of Cs desorbed (mmolg-1)

Amount of Cs desorbed (mmolg-1)

60 60

Cs desorption efficiency (%)

Cs desorption efficiency (%)
0.4 0.4 50
50

40 40
0.3 0.3

30 30
0.2 0.2

20 20
BDAB BDAB
0.1 DTAB 0.1 DTAB
HCl didn’t desorb Cs HCl 10 HCl 10
BDAB extended BDAB extended
DTAB extended DTAB extended
0.0 0 0.0 0
0 20 40 60 80 100 0 20 40 60 80 100

Desorbent (mM) Desorbent (mM)

20 20
(c) (d) BDAB
BDAB
DTAB DTAB
HCl HCl
18 18 BDAB extended
BDAB extended
DTAB extended DTAB extended

16 16
d001 (Å)
d001 (Å)

14 14

12 12

10 10
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

Desorbent (mM) Desorbent (mM)

Layer charge of Na-Bent was more negative (-0.6 molc molfu-1) than Ca-Bent (-0.4 molc molfu-1).
 The degree of change in the clay’s ξ increased with cation
Ca+MMT valency (Na+<Ca2+<Al3+), as predicted by the double layer theory.

Na+MMT

• Based on references, zeta potential of Na-MMT was more

negative than Ca-MMT.

• These references supported our layer charge calculation.

Ca-MMT
• Therefore, in our data, Cs was more difficult to be desorbed
from Na-Bent than in Ca-Bent because Cs was tightly bonded in
Na-Bent due to more negatively charged layer.
Na-MMT
 RESULTS & DISCUSSION (a) Far below CMC Cs+
(b) Slightly below CMC
Cs+
Cs+
Cs+
Cs desorption from kaolinite
Cs+ Cs+ Cs+ Cs+ Cs+ Cs+ Cs+ Cs+ Cs+ Cs+

Micelles formation Both surfactants completely formed micelles and reached T

𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿-
T
𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿-
O O

6.3 mM similar % Cs desorption due to similar alkyl chain length

T T
𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- O
𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿-
O

0.030 100
(a)
Amount of Cs desorbed (mmolg-1)

0.025 (c) At/slightly above CMC (d) Far above CMC

Cs desorption efficiency (%)

80
+
Cs+ Cs
Micelles formation Cs+
Cs+ Cs+
0.020 Cs+ Cs
+

15.2 mM Cs+
60 Cs+
Cs+ Cs+ Cs+ Cs+ Cs+

T T
0.015 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- O
𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿-
O

T T
40 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿- 𝛿-
O O
0.010

20 (b)
(a) 7Å

0.005 BDAB No change in basal spacing

DTAB Kaol/Cs/BD50
HCl 7Å

0.000 0

Intensity (a.u.)
0 10 20 30 40 50
Kaol/Cs/DT50

Desorbent (mM) 7Å

• As the surfactant micelle formed earlier, a faster of Cs desorption was achieved (at low
Kaol/Cs
concentration).

(002)
(001)
• As the concentration exceeds the CMC value, bilayer aggregates are completely 7Å

(200, 112)
(201, 130)
formed to be micelles and saturation of Kaol surface coverage is achieved .

(110, 110)
Kaol

(111)

(003)
(1 1 1)

(202)
(020)

(131)
• Therefore, Cs desorption BDAB reached constant ~88% after applying 10 mM
(JCPDS 89-6538)

concentration. 5 10 15 20 25 30 35 40 45 50
• Meanwhile, ~88% desorption of Cs was reached constant after using DTAB 20 mM. 2q ( ) o 39
 2000
(a) (c)
Monomers Monomers Monomers above CMC
1750
y = 26.105x + 350.11
1500 R² = 0.9988

Conductivity (mS/cm)
1250
Water DTAB 1 mM BDAB 1 mM Water DTAB 10 mM BDAB 10 mM

1000

CMC = 6.3 mM
750

500

y = 77.543x + 25.267
250 R² = 0.9924
Monomers near CMC above CMC above CMC
0
0 10 20 30 40 50
Concentration (mM)
2250
Water DTAB 5 mM BDAB 5 mM Water DTAB 20 mM BDAB 20 mM
(b)
2000
y = 23.955x + 988.65
1750 R² = 0.9988
CMC = 15.2 mM
Conductivity (mS/cm)

1500

1250

1000
y = 85.79x + 50.575
DTAB 50 mM
750 R² = 0.9951 Water BDAB 50 mM

500

250

0
0 10 20 30 40 50 DTAB above CMC BDAB above CMC
Concentration (mM)

CMCs of surfactants decreased with increasing their head group sizes Light

while the chain lengths were kept being similar. 8,9

 RESULTS & DISCUSSION
Cs desorption from illite
0.07 100
(a)
(d) (b)
No change in basal spacing
Amount of Cs desorbed (mmolg-1)

0.06 10 Å Ilt/Cs/BD50

Cs desorption efficiency (%)

80

0.05

Intensity (a.u.)
10 Å
60 Ilt/Cs/DT50
0.04

0.03
40 10 Å
Ilt/Cs

(003)
0.02

(001)
20
BDAB

(002)

(021)
0.01 Ilt
10 Å

(110)
DTAB (JCPDS 83-1808)
HCl
0.00 0
0 10 20 30 40 50 5 10 15 20 25 30 35 40 45 50
Desorbent (mM) o
2q ( ) Okumura, et al. J. Environ. Radioact. 189, 135-145 (2018) in [10]

• No significant difference of Cs desorption among desorbent used due to the existence of Cs fixation
Frayed edge sites (FES) in illite clay. Basal surface 𝛿- Exchangeable Cs
• Frayed edge sites (FES) in the illite provokes strong cesium adsorption with high energy T
Hydrated
compared to others (basal surface, edge, and hydrated interlayer).10
Edge O
T
𝛿- 𝛿- 𝛿- interlayer
Interlayer K+ K+ K+ Cs+ Cs+ Cs+
• Ilt is (2:1 layer structure) susceptible upon HCl attack due to the high cations content in the K+ Cs+
T
octahedral sheet. 11,12 O
T
𝛿- 𝛿- 𝛿- 𝛿- Cs+
• The octahedral cations of Ilt for Al substitution consist of Fe, Ti, and Mn (0.21, 0.03, and 0.003 Frayed edge site
per O10OH2, respectively)

41
 RESULTS & DISCUSSION
pH of solution (dashed lines)
Influence of pH on Cs desorption by cationic surfactants

(a)
12
100
(b)
12
100 • Cs desorption from Cs-adsorbed
BDAB, pH of solution BDAB, pH of solution
samples was not significantly influenced
10 10
0.7
0.7
Amount of Cs desorbed (mmolg-1)

Amount of Cs desorbed (mmolg-1)

8 BDAB, pH of mixture 8 BDAB, pH of mixture
Final pH

Final pH
DTAB, pH of solution DTAB, pH of solution
by surfactants pH (pH of solution).

Cs desorption efficiency (%)

Cs desorption efficiency (%)

6

0.6 80 6
80
DTAB, pH of mixture 0.6 DTAB, pH of mixture
• BDAB and DTAB were less affected by
4 4

2 2
pHpzc = 8.3 pHpzc = 7.2
0.5 0.5
ionization due to containing permanent
0 0
0 2 4 6 8 10 12
0 2 4 6 8 10 12
Initial pH 60 Initial pH
60
0.4 0.4 positive charge on the nitrogen atom. 13
0.3 40 0.3 40

• Cs desorption from illite was relatively

0.2 0.2
20 20 higher at low pH compared to other
0.1 0.1 samples, supporting that acidic
Na-Bent/Cs Ca-Bent/Cs
0.0 0 0.0 0
conditions are more likely to affect Cs
2 4 6 8 10 12 2 4 6 8 10 12 desorption from Ilt/Cs.
pH pH
0.030 100 0.07 12
100
(c) (d)
10
pH of mixture (solid lines)
Amount of Cs desorbed (mmolg-1)

-1
Amount of Cs desorbed (mmolg )
0.06 8

0.025
Ilt/Cs

Initial pH

Cs desorption efficiency (%)

80 6
80
• Cs desorption from Cs-adsorbed
Desorption efficiency (%)
4

Kaol/Cs 0.05 2 pHpzc = 6

0.020
0 samples still proved constant results
60 0 2 4 6 8 10 12
60
0.04 Initial pH
when pH was adjusted during the
0.015
12 0.03
desorption process (pH of mixture).
40 40
10

0.010 8

0.02
• However, Cs desorption from
Final pH

4
BDAB, pH of solution 20 BDAB, pH of solution 20
0.005 2 pHpzc = 5.7
BDAB, pH of mixture 0.01 BDAB, pH of mixture Ca-Bent/Cs decreased at pH 12.
0
DTAB, pH of solution DTAB, pH of solution
0 2 4 6
Initial pH
8 10 12
DTAB, pH of mixture DTAB, pH of mixture
0.000 0 0.00 0
2 4 6 8 10 12 2 4 6 8 10 12
42
pH pH
RESULTS & DISCUSSION
pH of mixture on the Cs desorption from Ca-Bent/Cs d001 values at pH 12
100
(b)
12
14.4 Å
10 BDAB, pH of solution
0.7

Amount of Cs desorbed (mmolg-1)

8 BDAB, pH of mixture

Final pH
DTAB, pH of solution

Cs desorption efficiency (%)

6
80
0.6 4
DTAB, pH of mixture

It was proposed that the desorbed Cs by

Intensity (a.u)
2 Ca-Bent/Cs/BD50-pH12
pHpzc = 7.2
0.5 0

surfactants was re-adsorbed to Ca-Bent/Cs 0 2 4 6

Initial pH
8 10 12
60
13.4 Å
surface at high pH, resulting in the decrease 0.4 (b) 15.2 Å ¨
of Cs desorption efficiency. 0.3 40

0.2
20 Ca-Bent/Cs/DT50-pH12

Intensity (a.u.)
0.1 14.1 Å
Ca-Bent/Cs 4 6 8 10 12 14
0.0 0 o
2q ( )
2 4 6 8 10 12
pH
(b) 13.6 Å
15.2 Å
pHPZC = 7.2 → neutral surface d001 values without pH adjustment

sity (a.u.) Intensity (a.u.)

12.6 Å

(a.u.)
14.1 Å

(a.u)
pH > PZC 14.2 Å
Ca-Bent/Cs/BD50

Intensity
pH < PZC

Intensity (a.u.)Intensity
13.6 Å
13.6 Å

Positively charge surface Negatively charge surface Ca-Bent/Cs/DT50

12.6 Å

1 2 3 4 5 6 7 8 9 10 11 12 13 14 13.3 Å
7.2 2θ (o) 43
Regarding Ca-Bent has more negative net surface density than Na-Bent

• Sperry and Peirce, 1999 reported that montmorillonite treated by

CaCl2 would have more negative net surface density than treated by
NaNO3 because Ca2+ ions have a stronger electrostatic attraction to
the acid hydroxyl surface site of montmorillonite than Na+ ions.

• For that reason, Ca2+ ions will facilitate the release of more H+ from
montmorillonite surface, becoming more negatively charged.

Sperry, J.M., Peirce, J.J., 1999. Ion exchange and surface charge on montmorillonite clay.
Water Environ. Res. 71, 316–322.
 RESULTS & DISCUSSION
FTIR spectra

Na-bentonite Ca-bentonite Kaolinite Illite

(a) (b) Ca-Bent (c) (d) Ilt
Na-Bent Kaol

836

1630
794
1637
694

1635
912
3631
1637

3448
791
3428

755
3629

3428

520
796

1116
912

700
Ca-Bent/Cs

694
3696
428

3621
3619
520

754
3652
3669
468
468

1035
Ilt/Cs

1035

468
Na-Bent/Cs

912
1032

538

798

476
530
1031
1006
Kaol/Cs

Transmittance (%)
Transmittance (%)

Transmittance (%)
Transmittance (%)

2852
BDAB

725
1473
2923
BDAB

725
BDAB Ca-Bent/Cs/BD50
1473

BDAB
2852
2923

=C-H

2852
asymmetric

2923
symmetric

2852
2923
C-N
C-H
Ilt/Cs/BD50

C-H
Na-Bent/Cs/BD50 Kaol/Cs/BD50
asymmetric

symmetric
symmetric

asymmetric
C-H

=C-H

symmetric
asymmetric

C-H
C-N
C-H

C-H
C-H
C-H
DTAB DTAB
DTAB DTAB

1480
2850
2917
1480

2850
2917
2850

2850
2917

2917
Ca-Bent/Cs/DT50 Kaol/Cs/DT50
Ilt/Cs/DT50

symmetric
symmetric

asymmetric

symmetric
asymmetric

asymmetric
Na-Bent/Cs/DT50

C-N
asymmetric

C-H
symmetric

C-H

C-H

C-H
C-H

C-H
C-H
C-H

C-N

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (cm-1) Wavenumber (cm-1) Wavenumber (cm ) Wavenumber (cm-1)

• New bands appears after surfactant treatment.

• 2900 and 2850 cm-1 correspond to C-H bond of surfactant alkyl chain
• 1470-1480 cm-1 is related to C-N bond of amine group (bentonites)
• 704-748 cm-1 are attributed to =C-H of aromatic ring (bentonites)
• Intensity at around 3428 and 1637 cm-1 assigned to H2O in the interlayer decreased because the water was replaced by surfactant.
• A band at 1035 cm-1 assigned to Si-O bond increased and sharpened after surfactant treatment. It was expected due to interaction
between silicate layer and surfactant. 45
 RESULTS & DISCUSSION
Cs desorption kinetic

0.5 0.5
Pseudo-first order equation:
Na-Bent/Cs
(a) Ca-Bent/Cs
(b) 60
60
.......... (6)

Cs desorption efficiency (%)

Cs desorption efficiency (%)

0.4 0.4 50
50
qtdes (mmolg-1)

qtdes (mmol.g-1)
40
0.3 40 0.3 Pseudo-second order equation:
30
0.2
30
0.2
.......... (7)
20 20

0.1 0.1
10 10
BDAB BDAB
DTAB DTAB
0.0 0 0.0 0
Initial desorption rate:
0 200 400 600 800 1000 0 200 400 600 800 1000
t (min) t (min) .......... (8)
0.030 100 0.05
Kaol/Cs
(c)
Iltl/Cs
(d)
70

0.025 60
Cs desorption efficiency (%)

Cs desorption efficiency (%)

80 0.04

50
0.020
qtdes (mmolg-1)
qtdes (mmol.g-1)

60 0.03
40
0.015

40 0.02 30

0.010
20

20 0.01
0.005 10
BDAB BDAB
DTAB DTAB

0.000 0 0.00 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120

t (min) t (min)

46
RESULTS & DISCUSSION
Cs desorption kinetic plots

(a) Na-bent/Cs (b) Ca-bent/Cs (c) Kaol/Cs (d) Ilt/Cs

-0.2
Pseudo-first order (PFO)

-2.5 -2.6
(a) -0.2 (b) (c) (d)
BDAB BDAB BDAB BDAB
-0.3 DTAB DTAB -3.0 DTAB DTAB
-0.3
-2.8
-0.4 -3.5
-0.4
ln (qeads - qtdes)

ln (qeads - qtdes)

ln (qeads - qtdes)

ln (qeads - qtdes)
-0.5 -0.5 -4.0 -3.0

-0.6 -0.6 -4.5

-3.2
-0.7 -0.7
-5.0

-0.8 -3.4
-0.8 -5.5
-0.9
-0.9 -6.0
-3.6
-1.0
-1.0 -6.5
0 200 400 600 800 1000 0 200 400 600 800 1000 0 20 40 60 80 100 120 0 20 40 60 80 100 120
t (min) t (min) t (min) t (min)
Pseudo-second order (PSO)

5000
5000
(a) (b) (c) 4000 (d)
2500 4500
3500
4000
4000
t/qtdes (mingmmol-1)

2000
t/qtdes (mingmmol-1)

t/qtdes (mingmmol-1)

t/qtdes (mingmmol-1)
3500 3000

3000 2500
3000 1500
2500
2000

2000 2000
1000 1500
1500
1000
1000 1000
500
BDAB BDAB BDAB 500
500 BDAB
DTAB DTAB
DTAB DTAB
0 0
0 0
0 200 400 600 800 1000 0 20 40 60 80 100 120
0 200 400 600 800 1000 0 20 40 60 80 100 120
t (min) t (min) t (min)
t (min)

47
RESULTS & DISCUSSION
Calculated parameters of Cs desorption kinetics model

• Cs desorption data from all clays and clay minerals used by both surfactant were best fit to pseudo-second order model (R2 and qedes, cal).
• It was suggested that the process was chemical desorption (the reverse process of chemisorption) by involving ion-exchange mechanism.14
• Desorption rate constant (k2) and initial desorption rate (v0) of BDAB is higher than DTAB → desorption was faster.
• However, BDAB and DTAB showed identical rate (v0) values in Na-Bent/Cs → desorption kinetic was similar.
• It was because qedes, cal of BDAB was larger than that of DTAB, hence BDAB took more time to reach desorption equilibrium as DTAB did.

48
Cs desorption from montmorillonite-K10 (addition)

• Tidak mengembang atau membesarnya interlayer MMTK10 disebabkan pengaruh struktur clay itu sendiri.
• MMTK10 merupakan pengembangan produk montmorillonit yang sebelumnya diberi perlakuan aktivasi asam dan perlakuan
suhu.
• Perlakuan aktivasi asam menyebabkan terjadinya pembentukkan poros yang tinggi dengan luas permukaan besar.
• Oleh karena itu dapat mengadsorp Cs dalam jumlah tinggi. Perlakuan suhu menyebabkan hilangnya kemampuan interlayer
untuk mengembang atau membesar.
• Surfaktan menunjukkan desorpsi lebih tinggi dibanding HCl
GENERAL CONCLUSIONS

• Cs desorption from actual 137Cs-contaminated soil of Fukushima using BDAB was more effective than HCl, even with a low BDAB
concentration.
• Cs desorption from Na-bentonite by BDAB was higher than using DTAB because Na-bentonite was more expanded after using BDAB,
thus higher Cs was desorbed.
• Ca-bentonite followed similar mechanism, however Cs desorption by both surfactants was slightly similar since Ca-bentonite has
limitation to be expanded.
• Cs desorption from kaolinite was more governed by surfactant micelles. When the surfactant micelles were formed earlier at low
concentration, considerable desorption of Cs was achieved .
• Cs desorption from illite was more difficult due to the existence of Frayed edge sites (FES) which provokes high retention of Cs.
• The results obtained from this study afford new insights for surfactant selection in the washing remediation technology of Cs-
contaminated clays and clay minerals including soil.

50
Challenge
“The challenge is how to treat secondary wastewater generated from washing soil treatment?”

a) Using small amount of adsorbent

*) S.J. Choi, Y.H. Kim, J.W. Jeon, Y.J. Park, Method for preparing silicotitanate and cs adsorbent, in, US Patent 2015.

• After the soil was washed using K+ as desorption agent, the removed Cs in wastewater was adsorbed using
Silicotitanate with composition of 0.06 g of adsorbent and the 30 mL solution containing Cs+ desorbed from soil.

51
Challenge
“The challenge is how to treat secondary wastewater generated from washing soil treatment?”

b) Precipitation of Cs

Using chemical such as Fe ferrocyanide & BaSO4

https://doi.org/10.1016/j.jece.2023.110306
Using ligand complex for Cs precipitation
https://doi.org/10.1002/chem.201706181

52
Current Project

Enhancing Uranium and Thorium Leaching Efficiency in Tin Slag through Surfactant-Assisted Acid Leaching
(RIIM Research)

• Preliminary results show that surfactant addition to acid solution can significantly enhance U and Th extraction from
Tin Slag, without prior treatment.

The surface tension of the leaching solution in STAC

system was lower than that in the traditional leaching
system, which was beneficial for the entry of the lixiviant
to the internal of the particles

https://doi.org/10.1016/j.jclepro.2019.04.305
REFERENCES

1. Kaneko, M., et al., Front. Energy Res 3, 37, 1-10 (2015).

2. Mukai, H, et al. Environ. Sci. Technol., 48 (22), 13053–13059 (2014).
3. Kozai, N., et al. J. Nucl. Sci. Technol., 49 (5), 473–478 (2012).
4. Willms, C., et al. Appl. Clay Sci., 25 (3–4), 125–133 (2004).
5. B. H. Kim, et al., JNFCWT 15, 1, 27-34 (2017).
6. X. Yin, et al. Chem. Eng. J. 333, 392–401 (2018).
7. H. Iwata, H. Shiotsu, M. Kaneko, and S. Utsunomiya. (2012). "Nuclear accidents in Fukushima, Japan and Exploration of
Effective Decontaminant for the 137Cs-contaminated soils" in Advances in Nuclear Fuel, edited by S. T. Revankar
(InTech, Rijeka, 2012), pp. 123–142.
8. Schnee, V.P., Palmer, C.P., Electrophoresis 29, 767–776 (2008).
9. Mozrzymas, A., J. Solution Chem. 48, 875–890 (2019).
10. Japan Atomic Energy Agency, 2019. JAEA R&D Review 2018-19. JAEA, Ibaraki.
11. Madejová, J., Spectrochim. Acta Part A Mol. Biomol. Spectrosc., 54, 1397–1406 (1998).
12. Pentrák, M., Philos. Mag. 90, 2387–2397 (2010).
13. Kim, B.H., et al. Colloids Surfaces A Physicochem. Eng. Asp., 522, 382–388 (2017).
14. Zou, C., et al. ChemistrySelect 4, 1306–1315 (2019).
15. Deer, W.A., Howie, R.A., Zussman, J. (2013). An Introduction to the Rock-Forming Minerals, 3rd ed. Mineralogical Society
of Great Britain and Ireland, London.
16. R. Watson, "Organoclays: preparation, characterization and use as sorbents and catalysts", Ph.D. thesis, Sheffield Hallam
University.

54
References for news

1. Asahi Shimbun. Nuke evacuees allowed to go home in ‘difficult-to-return’ zone.

https://www.asahi.com/ajw/articles/14643781
2. Asahi Shimbun. Partial lifting of evacuation order fails to bring life back to Futaba.
https://www.asahi.com/ajw/articles/14706619
3. The Japan Times. Fukushima town ready to lift evacuation order but only 10% of residents wish to return.
https://www.japantimes.co.jp/news/2022/07/27/national/fukushima-town-residents-not-returning/
4. The Japan Times. Evacuation order finally lifted for Fukushima nuclear plant town.
https://www.japantimes.co.jp/news/2022/08/30/national/futaba-evacuation-order/
5. http://josen.env.go.jp/en/pdf/environmental_remediation_1910.pdf?ver2
6. http://josen.env.go.jp/en/pdf/progressseet_progress_on_cleanup_efforts.pdf
7. Yamasaki, S. & Utsunomiya, S. A review of efforts for volume reduction of contaminated soil in the ten years after the
accident at the Fukushima Daiichi Nuclear Power Plant. Journal of Nuclear Science and Technology, 59:2, 135-147.
8. http://josen.env.go.jp/en/pdf/initiatives_2304.pdf
9. The Asahi Shimbun, “Survey : Not a single prefecture backs reuse of radioactive soil,” 2022.
https://www.asahi.com/ajw/articles/14311546
10. NHK World Japan, “Disposing of Fukushima’s contaminated soil,” 2019.
https://www3.nhk.or.jp/nhkworld/en/news/backstories/399/
11. The Asahi Shimbun, “Ministry to delay trial on reusing Fukushima soil in Kanto areas,” 2023.
https://www.asahi.com/ajw/articles/14851976 55
Thank you for your kind attention