Mercury Waste Management

Universiti Malaya
Mar 4, 2024

Masaki TAKAOKA
Department of Environmental Engineering, Graduate
School of Engineering, Kyoto University

takaoka.masaki.4w@kyoto-u.ac.jp
1
Outline
• General Background of mercury issue
• Minamata Convention on Mercury
• Excess mercury problem
• How can excess mercury be safely disposed of and
managed?
• Conclusions
• Acknowledgements

2
 Ancient and Familiar Element: Mercury
• According to the Nara Period Todaiji Great
Buddha Record, 50 tons of mercury and 9
tons of gold were used for the gilding of
the Great Buddha.
• The name of [丹nyu]・[丹生 nyu] is a
place of mercury production（丹生都比売
神社 Nyutsuhime Jina, Shinto, Shrine）alchemy

出典：フリー素材

• Mercury is the only liquid metal at

room temperature and atmospheric
pressure and has been used in a
variety of products. 3
 Minamata Disease Damages vs. Calculated
Cost of Pollution Prevention Measures
⚫Minamata disease is a mercury poisoning caused by daily intake of fish and
shellfish highly contaminated by methylmercury. Between 1953 and 1960, a
total of 628 patients were recognized, of which 78 had already died.
⚫Calculated Cost of Pollution Prevention Measures
： billion Japanese Yen/year
⚫Damages：12.631 billion Japanese Yen/year
⚫Health damage：7.671 billion Japanese Yen/year
⚫Environmental Pollution damage：4.271 billion Japanese Yen/year
⚫Fishery damage：0.689 billion Japanese Yen/year

Activities that prioritize economic development and neglect the environment can cause
a variety of serious damage that is not easily remedied later, including health damage.
4
Source: Research Group on Global Environmental Economy : Japanese Experience of Environmental pollution, 1991 (in Japanese)
 Post Minamata Disease
• Mercury pollution by Artisanal Small-scale Gold Large-scale epidemiological study of
Mining ingestion exposure to low
• At the 1992 United Nations Conference on concentrations of methylmercury from
Environment and Development in Rio de Janeiro, 1980s
mercury contamination of the Brazilian Amazon
River became known worldwide. Faroe Islands

• Principle 15 in Rio Declaration

• In order to protect the environment, the
precautionary approach shall be widely applied by
States according to their capabilities. Where there
are threats of serious or irreversible damage, lack
of full scientific certainty shall not be used as a
reason for postponing cost-effective measures to Seychelles Island
prevent environmental degradation. 5
 Mercury as a Global Pollutant
• Mercury Study Report to
Congress（US EPA: 1997)
consists of eight volumes.
• U.S. mercury emissions by
source, the health and
environmental impacts of those
emissions, and an assessment
of the availability and cost of
control technologies.
• The UNEP decided to promote
activities related to mercury
pollution on a global scale in
2001 and conducted the Global
Mercury Assessment. 6
 Mercury Atmospheric
Mercury Cycles Emission（2015）
（Total: 2,200 tones）

Others,
285
Waste,
ASGM,
162
Non 838
ferrous,
228

Coal
combusti
Cement, on, 474
233

UNEP Global Mercury Assessment UNEP 7

2018, 2019 homepage
 Mercury concentration in fish
T-Hg
Total mercury
総水銀検 総水銀検 総水銀検 メチル水
Me-Hg Methyl mercury
メチル水 メチル水 メチル水
Provisional total mercury limit：0.4ppm
番号
Fish
魚種
総水銀検
Max Min
Detected 出量最大 Average
出量最小 出量平均 Detected
銀検出検
銀検出量 銀検出量 銀検出量
Max Min Average 漁獲地
species 体数
number （ppm）
(ppm)（ppm） （ppm）
number 最大
体数
(ppm)
最小 平均
（ppm） （ppm） （ppm）
Provisional methyl mercury limit：0.3ppm
3 アオハタ 1 0.32 0.32 0.32 1 0.18 0.18 0.18 鹿児島
6 アカアマダイ 6 0.39 0.15 0.23 1 0.2 0.2 0.2 福井、山口、長崎、宮崎、鹿児島
7 アカカマス 11 0.45 0.04 0.21 2 0.26 0.21 0.23 千葉、東京、三重、大分、長崎、宮崎、鹿児島
23 オニカサゴ 1 1.04 1.04 1.04 1 0.43 0.43 0.43 長崎
32 キダイ 1 0.54 0.54 0.54 1 0.3 0.3 0.3 山口
34 キチジ 2 0.34 0.07 0.21 1 0.24 0.24 0.24 北海道
35 キハダ 1 0.9 0.9 0.9 1 0.54 0.54 0.54 アメリカ
37 キンメダイ 7 1.23 0.37 0.77 7 0.87 0.22 0.55 千葉、東京、神奈川、静岡、長崎
42 クロソイ 3 0.38 0.13 0.29 2 0.25 0.22 0.24 北海道、青森
44 クロマグロ 2 1.32 0.42 0.87 2 0.92 0.35 0.64 長崎、アメリカ
Sword fish
45 クロムツ 25 1.24 0.18 0.39 7 0.81 0.19 0.29 千葉、長崎、鹿児島
49 コショウダイ 1 0.49 0.49 0.49 1 0.31 0.31 0.31 千葉
55 シマアジ 8 0.37 0.14 0.27 4 0.3 0.19 0.26 三重、愛媛、大分、鹿児島
60 スズキ 24 0.28 0.04 0.1 9 0.07 0.03 0.05 宮城、福島、千葉、東京、石川、香川、愛媛
70 ハチジョウアカムツ 1 0.47 0.47 0.47 1 0.37 0.37 0.37 東京
74 ハモ 10 0.39 0.08 0.19 2 0.27 0.19 0.23 愛知、香川、徳島、兵庫、山口、大分、長崎、熊本
80 ホキ 1 0.47 0.47 0.47 1 0.32 0.32 0.32 ニュージーランド
88 マゴチ 4 0.58 0.06 0.24 1 0.2 0.2 0.2 茨城、千葉、愛媛
91 マダイ 10 0.35 0.09 0.21 1 0.28 0.28 0.28 大阪、香川、愛媛、大分、宮崎
Pacific bluefin tuna
97 ミナミマグロ 5 3.91 0.38 1.33 5 2.12 0.26 0.86 オーストラリア、ニュージーランド、南アフリカ
99 ムツ 10 0.48 0.22 0.29 10 0.34 0.18 0.24 静岡 Source：Illustrated Guide to Seafood in the
101 メカジキ 3 2.75 1.24 1.81 3 1.95 0.8 1.3 宮城、中国、太平洋 MarketplaceTokyo Metropolitan Islands
General Center for Agriculture, Forestry and
103 メダイ 2 0.32 0.1 0.21 1 0.21 0.21 0.21 東京、大分 Source: Bureau of Social Welfare and Public
Fisheries
104 メバチ 2 1.57 1.35 1.46 2 1.06 0.84 0.95 千葉、アメリカ Health, Tokyo Metropolitan Government (2019)
108 ユメカサゴ 22 0.95 0.32 0.62 22 0.71 0.22 0.46 長崎 8
淡水魚4 コイ 2 0.52 0.11 0.32 1 0.31 0.31 0.31 群馬、長野
 Methylmercury intake from fish
⚫For a pregnant woman with an average
weight of 50 kg, the amount of
methylmercury she may consume per
week is 0.1 mg (50 kg x 0.002
mg/kg/week)
⚫If the methylmercury concentration in
fish is 0.3 mg/kg, a pregnant woman
may eat 333 g of fish per week. (approx.
less than 50 g/day)
⚫To be on the safe side, she should at
most have a moderate sized fish on the
table once a week.
Cohort Survey in Miyagi Prefecture
By Prof. Nakai in Tohoku University
Source：Journal of Lipid Nutrition 2013 9
Total mercury concentrations (μg/g wet weight) in seafood from fish
complex and wholesale market in West Peninsular Malaysia.

Zurahanim Fasha
Anuala et al.,
Microchemical
Journal, 2018
10
 ➢ Aims to protect human
Minamata health and the environment
Convention on from anthropogenic
emissions of mercury and
Mercury mercury compounds
(MCM)
➢ Based on the review of the 2003 Assessment, UNEP formally established the Mercury
Program.
➢ In 2009, an agreement was reached to hold an intergovernmental negotiating committee
in 2010 to establish a treaty on mercury control (negotiations were due at UNEP's 27th
Governing Council Meeting in 2013).
➢ After five rounds of negotiations, the MCM was adopted at a diplomatic conference held in
Kumamoto City in October 2013.
➢ The MCM entered into force in August 2017.
➢ There are 128 signatories to the treaty and 147 parties. 11
 Minamata Convention on Mercury(MCM)
➢ Article1-35.
➢ Article 3 Mercury Supply Sources and Trade
➢ Article 4 Mercury-added products
➢ Article 5 Manufacturing Processes in which mercury or mercury compounds are used
➢ Article 7 Artisanal and Small-scale gold mining
➢ Article 8 Emissions
➢ Article 9 Releases
➢ Article 11 Mercury Waste2
➢ Article 12 Contaminated sites
➢ Article 13 Financial resources and mechanism
➢ Article 14 Capacity-building, technical assistance and technology transfer
➢ Article 22 Effective evaluation
12
Phased out by 2020
Mercury-added products
Batteries, except for button zinc silver oxide batteries with a mercury content < 2% and
button zinc air batteries with a mercury content < 2%
Switches and relays, except very high accuracy capacitance and loss measurement
bridges and high frequency radio frequency switches and relays in monitoring and
control instruments with a maximum mercury content of 20 mg per bridge, switch or
relay
Compact fluorescent lamps (CFLs) for general lighting purposes that are ≤ 30 watts with
a mercury content exceeding 5 mg per lamp burner
Linear fluorescent lamps (LFLs) for general lighting purposes: (a) Triband phosphor < 60
watts with a mercury content exceeding 5 mg per lamp; (b) Halophosphate phosphor ≤
40 watts with a mercury content exceeding 10 mg per lamp
High pressure mercury vapour lamps (HPMV) for general lighting purposes 13
 Phased out by 2020 Dental amalgam

Mercury-added products
Mercury in cold cathode fluorescent lamps and external electrode fluorescent lamps (CCFL
and EEFL) for electronic displays: (a) short length (≤ 500 mm) with mercury content
exceeding 3.5 mg per lamp (b) medium length (> 500 mm and ≤ 1 500 mm) with mercury
content exceeding 5 mg per lamp (c) long length (> 1 500 mm) with mercury content
exceeding 13 mg per lamp
Cosmetics (with mercury content above 1ppm), including skin lightening soaps and creams,
and not including eye area cosmetics where mercury is used as a preservative and no
effective and safe substitute preservatives are available
Pesticides, biocides and topical antiseptics
The following non-electronic measuring devices except non-electronic measuring devices
installed in large-scale equipment or those used for high precision measurement, where no
suitable mercury-free alternative is available: (a) barometers; (b) hygrometers; (c)
manometers; (d) thermometers; (e) sphygmomanometers 14
 Manufacturing process in which mercury or mercury
compounds are used
Manufacturing processes using mercury or
mercury compounds
Chlor-alkali production
Acetaldehyde production in which mercury or
mercury compounds are used as a catalyst
Vinyl chloride monomer production
Sodium or Potassium Methylate or Ethylate
Production of polyurethane using mercury
containing catalysts
Phase-out date
2025
2018
Not decided, but, e.g. Reduce the use of
mercury in terms of per unit production by 50
per cent by the year 2020 against 2010 use;
Not decided, but, Taking measures to reduce
the use of mercury, aiming at the phase out of
this use as fast as possible, within 10 years of
the entry into force of the Convention; 15
 COP-5 Outcome
• The 5th Conference of Parties was held November, 2023 in Geneva, Switzerland.
• Parties decided to amend Annex A to the Convention with new phase-out dates for certain batteries,
switches, relays and fluorescent lamps. Parties agreed on a new requirement to advance the phase-
down of dental amalgam and, as of 2025, no mercury level will be allowed in cosmetics. They also
decided to amend Annex B with a 2025 phase-out date for the production of polyurethane using
mercury catalysts.
• Other technical decisions covered the adoption of guidance for controlling mercury releases to land and
water, and the request for Parties to continue to advance their efforts to control the emissions of
mercury to the atmosphere. After seven years of negotiation, Parties agreed on a 15 mg/kg total
concentration of mercury as the threshold for wastes contaminated with mercury or mercury
compounds.
• The COP established a group to oversee the development of the first report to evaluate the effectiveness
of the Convention, following the agreed indicators, most of them based on national reporting
submissions. Considered a standalone agenda item for the first time, the COP pushed to reduce mercury
supply sources and trade by strengthening capacities at the national level and developing a study on the
global supply, trade, production and use of mercury compounds. 16
Supply and Demand Source: UNEP 2017

17
Material flow of mercury in Japan (2016)
Import of Export of Import of
Import of raw Export of Import of mercury and mercury add mercury add
materials mercury waste amalgam products products

Domestic demand Domestic

Industrial use Mercury recovery (product:3.5t) consumption

Recycling & Separation &

Recovery Collection Incineration

Total input
Emission and release to To water body
the environment To soil

Emission to Source: MOE

Domestic raw the air
materials Landfill
Total output 18
 Mercury waste
Mercury waste Examples
Reagent, Mercury used as measuring
medium, Mercury recovered from flue gas
Waste
treatment, Mercury recovered from waste
consisting of Hg
contaminated with Hg or waste products,
etc.
Waste contaminated Sludge, Fly ash, etc.
with Hg
Waste Hg added Lamps, Batteries, Measurement equipment,
products (Waste etc.
containing Hg )

19
 New thresholds
15 mg/kg for
prevention of
Sludge from NFMI
Sludge from CRF
atmospheric emission
Other residues from CRF
1000 mg/kg for ban
Fly ash from MSWI of landfilling →
Fly ash from IWI recovery
Slag from NFMI
Residue from NFMI
Fly ash from CC
Gypsum from CC
Sludge from CC NFMI: Non Ferrous Metal Industry
Fly ash from SSI CRF: Crude oil refinement
Fly ash from EF MSW: Municipal Solid waste incinerator
CC: Coal combustion
Fly ash from BF SSI: Sewage Sludge Incinerator
Sludge from BF EF: Electric Furnace
Fly ash from CCB BF: Blast Furnace
CCB: Coal combustion boiler
Fly ash from Crematory
Bottom ash from Crematory

Mercury concentration (ppm)

20
Source: MOE
 Disposal of waste contaminated with Hg

• In Japan, even if mercury wastes are intended for disposal or are

required to be disposed of, these wastes can be landfilled if the
results of leaching tests meet strict regulations.
• Disposal at ordinary, controlled landfill sites is possible as long as
the waste is treated to show a mercury concentration equal to or
below the acceptance criteria

21
 Other wastes
Hg waste Pretreatment Roasting process Refinement

Air separation of mercury- Vacuum-sealed roasting

phosphor powder and tubes process

Crush or cut of lumps

Hg lamps
Separation of each parts

Sewage sludge Dewatering

Separation of only Hg batteries Rotary kiln Condenser/

Hg batteries
Removal of any impurities Multiple hearth process distillation
Hg
Extraction of precipitation/
Liquid Hg products Distillation
Liquid and solid separation

Other Hg waste (ash, slag, etc) Many of these used

products are recycled by a
Recyclable components Recycle specialist recycling
Reusable components Reuse
company (Nomura Mining
Company) in Hokkaido.
Residues Stabilization/
Residues
solidification

22
Final disposal Source: Basel TG D5 2010
Waste Consisting of Hg 1,600
シナリオ1：輸出ゼロ
Source: Sodeno & Takaoka 2017
High scenario: Zero export

mercury (ton)
1,400
●The amount of excess mercury in Japan Medium scenario: 10 ton export
シナリオ２：輸出１０トン

余剰水銀量(トン）
1,200
Low scenario:30 ton export
シナリオ３：輸出３０トン
is estimated to be ca. 600 to 1 400 tons 1,000
800
by 2050 . 600

Excess
400
●In Japan, we can’t permanently store 200

mercury wastes in deep geological 0

2029

2047
2015
2016
2017
2018
2019
2020
2021
2022
2023
2024
2025
2026
2027
2028

2030
2031
2032
2033
2034
2035
2036
2037
2038
2039
2040
2041
2042
2043
2044
2045
2046

2048
2049
2050
cavities, e.g., an underground salt mine. 年度
Year

●Treatment & final disposal technologies

toward environmentally sound
management of mercury wastes in a
specially engineered landfill (i.e.,
relatively shallow underground) without
leakage to the environment are
23
essential in Japan. Baart, 2009 DNSC, 2007
 Guideline for the environmentally sound management
of mercury waste in Japan
Waste consisting mercury or mercury compounds
(designated as “industrial waste requiring special management” from 2017)

Collection & Transportation⇒  Purification

Storage⇒ ✓ Purity (Hg) ≧ 99.9%
 Sulfurization to b -HgS
✓ S/Hg molar ratio: 1.05～1.10
Treatment ✓ Purity (S) ≧ 99.9%
✓ Leaching test, JLT-13 (≦ 5 mg/L)
✓ Headspace test (＜ 1 mg/m3)
 Solidification
✓ Modified sulfur (MS50)
Leaching test ✓ HgS ≦ 50wt%
(JLT-13) ✓ Compressive strength (≧ 0.98 MPa)

(＞ 5 mg/L) (≦ 5 mg/L) A defense-in-depth approach

(natural & artificial barriers)

Landfills for hazardous industrial wastes Landfills for industrial wastes

(isolated type) (leachate-controlled type)
(w/ additional measures to avoid contact with rainwater) 24
Source: MOE 2021
 How can excess mercury be safely disposed
of and managed?
A defense-in-
• What are stable mercury compounds?
depth approach
• How to produce stable mercury compounds?
• How can produced mercury compounds be prevented from diffusing
in the environment?
• Are the mercury compounds in the solidified product stable in the
long term?
• Are they stable in a disposal environment close to actual conditions?
• What is the behaviour of mercury in actual landfills?
• How much will be released into the environment in the future?

Establishment of requirements for Long-term safe disposal and management of mercury 25

 What are stable mercury compounds?
(a) (b) (c) (d) (e) (a) (b) (c) (d) (e)
1:Element 元
固体で存在できる (a)-(e)で
元
固体で存在できる (a)-(e)で
Hg組成範囲 貴 希 放 6反 7供 絞込んだ Hg組成範囲 3貴 4希 5放 6反 7供 絞込んだ
2:Hg ratio to form 素1 2 3
金
4
土
5
射 応 給
8 1
素 2
金 土 射 応 給
8
（25℃，1気圧） 保管形態候補 （25℃，1気圧） 保管形態候補
solid(25 C, 1atm) 属 類 性 性 量 属 類 性 性 量
3: Precious metal Ag ≦57mol% × Pb ≦35mol% ○
Au ≦33mol% × Pd ≦80mol% ×
4: Rare earth Ba ≦93mol% × Pr ≦80mol% ×
5: Radioactive Ca ≦88-90mol% × Pt ≦80mol% ×
6: Reactive Cd ≦78mol% ○ Pu ≦74mol% ×
7: Supply Ce ≦80mol% × Rb × ≦91mol%
Cl At 25℃，1atm，45
50-67mol% elements can○ form solid or amalgam
× Rhwith Hg.
≦83mol%
8: Suitable candidate Cs Considering supply, price,
50-80mol% × toxicity etc., solids or amalgam with 12 ○
S ≦50mol%
Cu ≦46mol% ○ Se ≦50mol%
○
Dy elements (Cd，Cl，Cu，Mn，Ni，Pb，S，Se，Sn，Ti，Zn，Zr)
≦75mol% × ×
Sm can be
≦82mol%
Er suitable candidates
≦75mol% × for long-term safe disposal and storage of mercury
Sn ≦12mol%
○
Gd ≦80mol% × Sr ≦92mol% ×
Hf ≦33mol% × Tb ≦80mol% ×
Ho ≦75mol% × Te ≦50mol% ×
In ≦16mol% × Th ≦75mol% ×
K ≦91mol% × Ti ≦75mol% ○
La ≦86mol% × Tl ≦18mol% ×
Li ≦75mol% × U ≦80mol% ×
Mercury is present Mg ≦66mol% × Y ≦80mol% ×
Mn ≦72mol% ○ Yb ≦78mol% ×
as HgS in nature. Na 25-80mol% × Zn ≦28mol% ○
Nd ≦80mol% × Zr ≦75mol% ○
Source: Oguchi 2011 Ni ≦80mol% ○
 How to produce stable mercury compounds?
• To dispose of elemental mercury, sulfidation of
elemental mercury is necessary because mercury
sulfide is a stable chemical form. Mix Pulverization
Hg
• The effect of purity on the leaching concentration of HgS
mercury was checked as a condition for stabilization
of mercury. S Intermediate
• The products from sulfidation treatment at 99.5% Planetary ball mill
purity under optimum conditions exceeded the 100
environmental criteria. 99.9% purity is necessary.

JLT No.46（µg/L）
10 Environmental
HgS produced by planetary ball milling criteria
1 0.5µg/L Rolling ball mill
Hg: >99.9%, S:>99.9%,S/Hg molar ratio:1.05-1.1
0.1
JLT46 0.059μg/L
Property of TCLP 0.26μg/L 0.01
product Mercury concentration 1 1.05 1.05
<1.5μg/m3 S/Hg ratio
in head space Chemicals 27
Hg purity 99.5% 99.9%～ Vapor synthesis
Source: Fukuda et al., 2011
 How to produce stable mercury compounds?
Hg
Small pilot-scale planetary ball mill w/ a Ball S
cooling unit for sulfurization
Volume 2 400 mL
Length to width (L/D) 3.08
Rotation Reverse
Hg 1 152 g
S/Hg (mole) 1.05
Ball diameter 25 mm
Filling ratio 30%
Centrifugal acceleration 30×G
Reaction time 60 min
Reaction vessel
☞ Annual treatment capacity: 1 800 kg-Hg/year (2 400 mL)
Planetary ball mill, BX382
(3 operations/day, 5 days/week, 52 weeks/year) (Kurimoto, Ltd.)
Source: Takaoka et al. ,2017 28
 How can produced mercury compounds be
prevented from diffusing in the environment?
Modified sulfur (MS50)
✓ Japanese standard (MOE guideline)
0分 20分 40分 60分

✓ Dicyclopentadiene (DCPD)-modified sulfur

✓ HgS content: 50wt%
240分 210分 180分 120分
MS50
Epoxy resin (EPR80) Mixer Modification (polymerization) of sulfur

✓ BPA type epoxy resin (jER 828, Mitsubishi Chemical)

✓ Amine curing agent (B-2413, Daito Sangyo)
✓ Curing: 40C, 16 hours
✓ HgS content: 80wt%
Mixing Molding EPR80
Low-alkalinity cement (LAC40)
✓ Conventional solidification material, but low-alkalinity
✓ Haüyne-type HLAC-S (Taiheiyo Consultant)
✓ Water/cement (w/c): 50.0%
✓ Curing: Sealing (20C, 5 days), air (20C, 60%RH)
(in a plastic bottle to prevent rusting) LAC40
✓ HgS content: 40wt% Source: Kusakabe et al. 2022
Mixing Molding & tamping 29
 Development of solidification using polymer
Evaluation items Target values Modified Sulfur (MS) Epoxy Resin(EPR)
HgS blending ratio（wt%） - 50 80
unconfined compression strength（MPa） ≧0.98 30.6 107.0
Japanese Leaching test No.13（mg/L） ≦0.5 0.05±0.01 0.09±0.01
Head space test（mg/m3） ＜1.0 ＜0.1 ＜0.1
Tank leaching test（mg/L） ≦0.5 ＜0.01 ＜0.01
Hg concentration in the working environment
（mg/m3）
25 *1 Max. 5.0 Max. 1.0
Material costs（yen）*2, *3 - 3,494 *4 508 *5
Volume reduction ratio*6 - 1.0 0.5
Gas permeability coefficient
（cm3・cm/(cm2・s・cmHg)）
- 2.70×10-10 3.03×10-11

*1 Concentration under the Occupational Health and Safety Law (Working Environment Assessment Standard); *2 Note that this is an
estimate based on actual purchases at the laboratory and not the actual market price. *3 Cost of solidification material only required
to solidify 1 kg of HgS (not including electricity consumption, etc.). , *4 Powdered sulfur, modifier DCPD only, *5 Main agent &
hardener only, *6 Solidifier volume per kg of mercury sulfide (vs. MS)
(Unpublished data)
 10-L HDPE bottle
Are the mercury compounds in the
solidified product stable in the long term?
• To investigate the influence of various parameters such as pH and redox
conditions on long-term mercury leaching (L/S=100, 500 years) from MS50,
EPR80 & LAC40, serial batch leaching tests and/or percolation test were carried
out under chemically strong conditions.
PTFE rods

Percolation test
Glass column
ガラスカラム
with crushed
（内径15 mm） 主な試験条件
solidified
＋
粉砕試料
product 充填量（g）： 23.0
（0.5～5
(0.5-5 mm）
mm) 温度（℃）： 20.0

Peristaltic Acid 5% H2SO4

送液ポンプ
pump
（約45 mL/d）
Neutral (Neu.) H2O (pure water)
試薬溶液
Solution
00 . 74 Alkaline (Alk.) 5% NaOH
bottle 水封
チューブ
○ I
Oxidizing (Ox.) 0.9 M H2O2
31
Source: Kusakabe et al. 2022 Reducing (Red.) 0.04 M N2H4 w/ N2 purge
 Are the mercury compounds in the solidified
product stable in the long term?
MS50 (Japanese standard method) demonstrated the long-term stability under Acid, Neutral & Reducing
conditions. Even if it is a relatively short-term effect (a few decades?), mixed landfilling with alkaline
wastes such as an incineration fly ash should be avoided.
10000 10000 10000

1000 1000 1000

Leaching value (mg/L)

Leaching value (mg/L)

Leaching value (mg/L)

100 100 100

National
10 effluent 10 10
standard:
5 mg/L Environmental
1 1 1
quality
standard: 0.5

◎ × × mg/L ◎0.1
0.1 ◎ ◎0.1
◎ ◎ 〇 × ◎ 〇 × × 〇
0.01 0.01 0.01
N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2 N=1 N=2
Acid Neu. Alk. Ox. Red. Acid Neu. Alk. Ox. Red. Acid Neu. Alk. Ox. 32 Red.
Source: Kusakabe et al. 2022
 Are they stable in a disposal
environment close to actual
conditions? Controlled waste
Distributor Distributor ➢ Mix（Incineration
Gas sampling Gas sampling ash：Sewage sludge
compost＝8:2）
➢ Incineration ash(IA)
1
0

Gas venting
水銀 pipe
Mercury waste 0.1
Solid waste Solid waste
➢ HgS powder Leachate
浸出水＜Hg＞ Semi-aerobic
準好気性 浸出水＜Hg＞
Leachate MS
改質硫黄
混合廃棄物 改質硫黄
MS 焼却残渣
➢ MS Mix waste EPR
エポキシ IA, Semi-
（準好気性） LAC
セメント
LAC
セメント
➢ EPR Blank aerobic Blank
ブランク
38
45

ブランク
Mercury Waste Mercury Waste 0.01 Anaerobic
➢ LAC Effluent standard
嫌気性
MS
改質硫黄 Effluent standard

Hg [1μ-g/L]
排水基準：0.005mg/L 排水基準：0.005mg/L
Water level
➢ Blank EPR
エポキシ
Blank
ブランク
22

Φ5.5

Stone Φ1.3 Stone 0.001

Environmental criteria Environmental criteria
環境基準：0.0005mg/L
環境基準：0.0005mg/L
5

Unit:cm
Leachate
25×25 collection pipe
Semi-aerobic lysimeter Anaerobic lysimeter 0.0001
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24
Source: Hirata et al. 2021 and 2023 Time(経過月数
months) 経過月数
Time( months)
 Are they stable in a disposal environment close
to actual conditions? ✓ No leakage of mercury in the
solidified product.
✓ little or no vaporization of mercury in
solidified material from the upper
layers
✓ Little or no methylmercury formation
Upper from solidified products

Middle

Lower

Upper Middle Lower

Source: Hirata et al. 2021; Takaoka et al, 2023
 What is the behaviour of mercury in real landfills?
⚫ Assuming long-term disposal of mercury waste in the future, it is
necessary to assess the stability of mercury waste past landfilled and
the real landfilled environment.
⚫ To determine the depth profile of mercury, the levels of methyl mercury
(MeHg), and the factors controlling methylation in an old landfill site
that received waste for over 30 years were examined. Boring Core samples
T-Hg: 19-975 ng/g Me-Hg: 0.2-19.6% of T-Hg

hgcA: Methylation
merA: Reduction
merB:Demethylation

35
Source: Yang et al., 2018
 How much will be released into the environment in the
future?
➢ Computer simulation for a landfill ➢ With upper isolation layer (UIL) + ➢ Simulation of potential mercury
environment to calculate future releases adsorption layer(AL), after 2900 years, run-off from disposal sites and
into the environment from solidified mercury concentration in leachate factors affecting it, based on
products (Ishigaki et al., 2018) peaks at 0.03 µg/L (environmental groundwater and leachate
Rainfall infiltration criteria 0.5 µg/L). (Ishigaki et al., 2018). studies for waste disposal sites
Upper isolation with poor hydrological conditions

Cumulative Mercury Release (mg/m)

layer(cover soil) (Takemura et al., 2017).
Waste layer No UIL &
Soil adsorption No AL
layer Only AL ➢ Even in the most hazardous cases,
Mercury runoff from the impermeable
solidified product Only UIL layer can take more than 1000
UIL+AL
years to occur.
Soil adsorption
➢ Observation wells need to be
layer
placed at certain intervals in
Waste layer order to detect mercury
Time (year)
concentration in ground water.
Changes over time in cumulative
Leachate collection pipe emissions from MS solidified products
 • Landfill the waste in a specific area and record the
Controlled landfill site information. Do not disperse the waste.
• Do not mix with other wastes.
with special • Take necessary measures to prevent mercury release
• Take necessary measures to prevent rainwater
requirements infiltration to the waste

37
Source: Toyohara, 2023
 Conclusions
• Activities that prioritize economic development and neglect the environment can
cause a variety of serious damage that is not easily remedied later.
• The long-term storage or disposal of wastes consisting of mercury is an inevitable
issue after the Minamata Convention on Mercury.
• A defense-in-depth approach is important to minimize the mercury release to the
environment.
• High purity, stabilization methods and solidification methods are key elements for
the production of long-term stable mercury waste.
• The solidified material has to be confirmed for long-term environmental safety by
various methods.
• Mercury can be safely sequestered for long periods without waste rock salt mines.

38
Acknowledgements
• Environment Research and Technology Development Fund
• SII-6-1(FY2020-2022)
• 3-1701(FY2017-2019)
• 3K143002(FY2014-2016)
• K113001(FY2011-2013)
• K22062(FY2010)
• K2147(FY2009)
• K2006(FY2008)
• Many collaborators: Fumitake Takahashi (TIT), Taketoshi Kusakabe (OIT), Ryuji
Yanase (FU), Osamu Hirata (FU), Takefumi Hayashi(NIES), Akira Sano(KU, FU),
Akito Matsuyama(NMD), Jiro Takemura (TIT), Hiroshi Moritomi (GU), Masahiro
Oguchi (NIES), Hiroshi Miura (Nomura Kohsan), Satoshi Mizutani (OMU), Misuzu
Asari (KU), Akiko Kida(NIES) , Reiko Sodeno (SIT), Habuer (OU)
• Supporters, students, staffs
39