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11
Hidetaka Takigami Material and Substance Management Section
Research Center for Material Cycles and Waste Management National Institute for Environmental Studies, Japan
Surveys of hazardous chemicals and their life-cycle stages
Research project :To investigate behavior of chemicals and environmental risks in utilization, disposal and recycling processes of the chemicals for managing hazardous chemicals and promoting recycling of valuable materials.
2
Surveys of hazardous chemicals at each stage throughout their life-cycle: mainly brominated flame retardants(BFRs)
Materials,Substances
Use
Collection,Selection
Resource recovery
Products,Articles
Used products
Raw materials,
Products Import
Reuse
Appropriate treatment, disposal
Pretreatment
Export
Recycled products
Chemicals in articles/products
Supply chain
Recycle chain
Indoor environment at using stage
Compressed packing
Working environment of dismantling process
Waste incineration,
Final disposal site
Granulation of Refused paper and plastic fuel (RPF)
Manufacture of recycled products
Chemicals in used products
Manufacture
Discard
Utilizing chemical substances
Br O
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br O
Br
Br
Br
Br
Br
Br
Br
Br
Br
O
Br
Br
Br
Br
Br
Br
Br
Br
Br
OHHOBr
Br
Br
Br
CH3
CH3
OHHOBr
Br
Br
Br
CH3
CH3
Which stage should we focus to minimize the total risk of chemicals?
BrBr
BrBr BrBr
BrBr
BrBr
BrBr
BrBr
BrBr BrBr
BrBr
BrBr
BrBr
3
0
5,000
10,000
15,000
20,000
25,000
30,000
35,000
amou
nt (t
ons)
yearTBBPA TBBPA polycarbonate oligomerTBBPA epoxy oligomer TBBPA -bis(dibromopropyl ether)HBCD DeBDEDeBDethane TriBph
Brominated flame retardants (BFRs)
The consumption of deca-BDE has increased drastically in rate 1980s.TBBPA and its oligomer have been used for the substitution of deca-BDE in 1990s.
The consumption of triphenylphosphate has increased for the substitution of other halogenated OPEs.The consumption of BDP has drastically increased to replace halogenated FR for PC alloy.
- PFRs has drastically replaced BFRs after 1998. - Chemical bonding type of BFR and condensed type of PFR is gradually increasing.
0
5,000
10,000
15,000
20,000
1996 1998 2000 2002 2004
amou
nt (t
ons)
year
triphenylphosphate tris(2-chloroethyl)phosphate
tris(2-chloroisopropyl)phosphate tris(dichloropropyl)phosphate
RDP (resorcinol bisdiphenylphosphate)
BDP(bisphenol-A bisdiphenylphosphate)
RDXP (resorcinol dixylenylphosphate)
V-6 (2,2-bischolomethyltrimethlenebis(2-choloethyl)phosphate)
CR-504L (polyoxyalkylene bisdichloroalkylphosphate)
OPE typelow m.w.
(classical)
Condensed typehigh m.w.
(newly developed)
Phosphoric flame retardants (PFRs)
Consumption of flame retardants in Japan
DeBDE
TBBPA
TBBPA epoxyoligomer
Triphenylphosphate
BDP
4
Chemicals in products/articlesScreening of Br concentrations in products/articles by a handheld XRF
y = 1.0052x + 1004.5R2 = 0.96
0
20,000
40,000
60,000
80,000
100,000
0 20,000 40,000 60,000 80,000 100,000XRF-Bromine concentrations (mg/kg)
MS-
Brom
ine
conc
entr
atio
ns (m
g/kg
)
Relationship between XRF-measured Br and MS-measured Br in textile samples. Br content in WEEE measured by a handheld XRF
0 50 100 150 200 250
~20%
~10%
~5%
~1%
~0.1%
~0.01%
<5ppm
Br c
onte
nts
Numbers
waste productcommercialized product
14.7%15.7%
3.5%4.7%
7.0%
14.7%39.9%
=> 45.6% of measured products contained Br of over 0.1 wt%.
Products containing Br at high concentration were analyzed accurately by HRGC/HRMS or LC-MS/MS
●HBCDs: LC-MS/MS ○DeBDE : HRGC/HRMS
=> Handheld XRF is a quick and simple method for screening of Br.
PCs, TVs, Printers, Refrigerators, Fan, Washing machines, Electric heaters, Microwaves, etc.
Measurement of Br concentration in products/articles by X-Ray Fluorescence analyzer
5
Chemicals in products/articles
PBDEs, PBDD/Fs, and Pb in products/articles
Concentration of PBDEs, PBDD/Fs, and Pb in waste home appliances (mg/kg)
Concentration of Pb in plastic shopping bags
0
5
10
15
20
25
30
35
40
45
0~1000
~2000
~3000
~4000
~5000
~6000
~7000
~8000
~9000
~10000
~11000
~12000
~13000
~14000
~15000
~16000
~17000
Pb(ppm)
枚数(枚)
1475
1480
Max 16,000ppm)
n PBDEs PBDD/Fs PbTV Rear cover 5 30,000 0.17 5.2
(0.76-150,000) (0.00041-0.72) (1.0-21)TV Back cover 9 57,000 7.2 0.50
(1.5-130,000) (0.00056-44) (0.30-0.80)TV Printed circuit board 5 4,500 0.76 26000
(2.4-22,000) (0.051-1.4) (1400-86000)Printer 1 100 0.16 naWashing mashine 1 57 0.0036 na
6
Homolog profiles of PBDE in video tapeMoBDEsDiBDEsTrBDEsTeBDEsPeBDEsHxBDEsHpBDEsOcBDEsNoBDEsDeBDE
MoBDEsDiBDEsTrBDEsTeBDEsPeBDEsHxBDEsHpBDEsOcBDEsNoBDEsDeBDE
0%
20%
40%
60%
80%
100%
0%
20%
40%
60%
80%
100%
China JapanKorea ChinaKorea Korea
BFRs and other chemicals in video tape (mg/kg)
- BFRs are usually added by around 10 wt% of plastics for flame resistance.
- These products could be contaminated with BFRs by utilizing plastics recycled from used flame resisting products.
- PBDEs contained in video tape is mainly DeBDE
Country of production PBDEs TBBP-A HBCD DeBDEthane T-Br Sb PbJapan 0.54 0.0030 <0.03 <0.07 <10 <10 <10China 6700 340 15 na 4400 1700 naChina 2400 280 30 190 2500 1100 <10Korea 1600 34 1.1 na 1500 650 naKorea 1300 46 1.6 260 1600 780 53Korea 1000 9.5 0.31 na 610 270 na
Chemicals in products/articlesHazardous chemicals in products/articles using recycled materials
Waste plastics
PBDEs
DeBDEthane, TBBP-A
HBCD
>>
Video tapes
H. Takigami;Organohalogen Compounds, 68, 2190-2193 (2006)
7
Samples: - Liquid crystal display (LCD) TV, Laptop PC, Power supply unit- Wallpaper, Curtain, Heat insulation material
Rear cover
Pulverized samples
Front cover
LCD TV
Chemicals in products/articles
Analysis of chemicals in new products/articles
Analysis method: - Samples were pulverized by frost shattering using liquid N2.- HRGC/HRMS and LC/MS methods.
Target chemicals:- Organobromine compounds (PBPhs, TBBPA, HBCDs, PBDEs)- Phosphoester flame retardants (TMP, TEP, TPrP, TBP, TClPP, TCEP, TBEP, TDCPP, TOP, TPhP, TCP)
New model(2008)
8
Printed circuit board(power supply unit)
Printed circuit board (LCD panel)
Printed circuit board
Pulverized samples
LCD panel
99
- Only 0.1% of total-Br was detected in rear and front cover as MS-measured BFRs.=> Other BFR compounds may be used in this TV. (TBBPA epoxyoligomer and carbonateoligpmer )
- Both BFRs and PFRs were used in liquid crystal and printed circuit board.
Chemicals in products/articles
BFRs and PFRs in new model LCD TVs
Concentration (ng/g-unit)
Rear cover Front cover LCD panel Printedcircuit board
Printed circuit board(power supply unit)
Printed circuit board(LCD panel)
PBPhs 5,700 4,600 33 730 980 1,200TBBPA 68 92 7 87 90 890HBCDs < 0.5 6 2 < 0.5 130 680PBDEs 14,000 14,000 2 59 15 54DBDPE 130,000 92,000 NA 36 1,100 770T-Br (XRF) 136,000,000 125,000,000 ND 23,900,000 133,000 22,600,000TMP < 0.3 < 0.3 < 0.3 < 0.3 < 0.3 < 0.3TEP 1 3 6 1 4 1TPrP < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5TBP 16 11 3 2 3 2TClPP 10 14 4 23 52 16TCEP 7 4 <4 9 <4 4TBEP <80 <80 <80 <80 <80 <80TDCPP <2 <2 <2 <2 <2 <2TOP 3 17 < 0.9 < 0.9 < 0.9 6TPhP 1,100 2,400 1,200,000 1,600,000 6,700,000 320,000TCP 180 370 54 480 4,500,000 140,000T-P (XRF) ND ND 1,100,000 NA ND ND
BFR
PFR
LCD TV (containing BFRs in its casings)
10
- Most of the units contained approx. 1-1.5 % of TPhP, which may be used as plasticizer and flame retardant. => Other PFR compounds, such as condensed phosphate, may be used in this TV.
- These results show the kinds of flame retardants is exchanging for corresponding some regulations such as RoHS and REACH. However to obtain these information is very difficult now.
Chemicals in products/articles
BFRs and PFRs in new model LCD TVs
Concentration (ng/g-unit)
Rear cover Front cover LCD panel Printedcircuit board
Printed circuit board(power supply unit)
Printed circuit board(LCD panel)
PBPhs 41 65 5 230 270 120TBBPA 15 21 9 770 900 74HBCDs 53 40 < 0.5 550 250 4PBDEs 32 540 5 13 12 45DBDPE NA NA NA 3,500 1,300 380T-Br (XRF) ND ND ND 41,700,000 41,700,000 89,900,000TMP < 0.3 < 0.3 < 0.3 < 0.3 < 0.3 < 0.3TEP 0 0 0 190 190 0TPrP < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5TBP 2 2 2 6 9 2TClPP 4 9 4 2 9 26TCEP <4 <4 <4 6 5 7TBEP <80 <80 <80 <80 <80 <80
TDCPP <2 <2 <2 <2 <2 <2
TOP < 0.9 80 < 0.9 < 0.9 < 0.9 < 0.9TPhP 600,000 940,000 1,200,000 13,000,000 15,000,000 870TCP 47 140 110 85,000 83,000 72T-P (XRF) 527,000 252,000 490,000 ND ND ND
BFR
PFR
LCD TV (containing PFRs in its casings)
11HBCD is highly contained in heat insulating materials.
Chemicals in products/articles
BFRs and PFRs in curtains and heat insulation materials
Concentration (ng/g-material)
Curtain (1) Curtain (2) Heat insulatingmaterial (1)
Heat insulatingmaterial (2)
PBPhs 860 1800 4400 330 TBBPA 21 16 22 22 HBCDs 130000 180000 23000000 18000000 PBDEs 7.4 9.1 63 220 TMP < 0.3 < 0.3 < 0.3 < 0.3TEP < 0.1 < 0.1 11 5.7TPrP < 0.5 < 0.5 < 0.5 < 0.5TBP 1600 1300 8.8 4.8TClPP <3 <3 28 37TCEP 4 6 9 10TBEP <80 <80 890 140TDCPP <2 <2 <2 6TOP < 0.9 < 0.9 < 0.9 6.4TPhP 820000 840000 8700 5300TCP 4900 190000 190 570
BFR
PFR
12
0
20
40
60
80
100
Con
cent
ratio
n (p
g/m3 )
0
20
40
60
80
100
120
Con
cent
ratio
n (n
g/m3 )
020406080
100120140
Con
cent
ratio
n (p
g/m3 )
0
2
4
6
8
Con
cent
ratio
n (p
g/m3 )
0500
100015002000250030003500
Con
cent
ratio
n (p
g/m3 )
0
100
200
300
400
500
600
Con
cent
ratio
n (p
g/m3 )
0
0.5
1
1.5
2
Con
cent
ratio
n (p
g/m3 )
Blank test Test BTest A
PBDEs HBCDs TBBPA TrBPhs
PCBs PBDD/Fs PFRs indoor air
outdoor air
Blank testTest A
Test B
N.D.N.A.
:test without any products:test loaded with homeelectronic products
:test loaded with homeelectronic and textileproducts
:not detected:not analyzed
Blank test Test BTest A
Blank test Test BTest A
Blank test Test BTest A
Blank test Test BTest A
Blank test Test BTest A
Blank test Test BTest A
N.D. N.A. N.A. N.A.
from electronic products from textile products from housing materials
0
20
40
60
80
100
Con
cent
ratio
n (p
g/m3 )
0
20
40
60
80
100
120
Con
cent
ratio
n (n
g/m3 )
020406080
100120140
Con
cent
ratio
n (p
g/m3 )
0
2
4
6
8
Con
cent
ratio
n (p
g/m3 )
0500
100015002000250030003500
Con
cent
ratio
n (p
g/m3 )
0
100
200
300
400
500
600
Con
cent
ratio
n (p
g/m3 )
0
0.5
1
1.5
2
Con
cent
ratio
n (p
g/m3 )
Blank test Test BTest A
PBDEs HBCDs TBBPA TrBPhs
PCBs PBDD/Fs PFRs indoor air
outdoor air
Blank testTest A
Test B
N.D.N.A.
:test without any products:test loaded with homeelectronic products
:test loaded with homeelectronic and textileproducts
:not detected:not analyzed
Blank test Test BTest A
Blank test Test BTest A
Blank test Test BTest A
Blank test Test BTest A
Blank test Test BTest A
Blank test Test BTest A
N.D. N.A. N.A. N.A.
from electronic products from textile products from housing materials
Br 12%
Br 14%
Br 13%
Br 10%
Br 2-8%(cooling fan)
Br 3.5%Br 1.7%
Br 3.5%
T. Kose;Organohalogen Compounds, 70, 2305-2308 (2008)
(Curtain, Blanket, Mattress)
- PBDEs, TBBPA, TrBPhs, PCBs and PBDD/Fs in the indoor air were derived from the electronic products.
- HBCDs in the indoor air were derived from the textile products.
(TV, PC, Copying machine)
Emission from products in use
Chemicals emission from household products in a model room
13
C blank
pg/m3C load
pg/m3EF a
pg/m2・hEF
/year
PBDEs TV sets 14 80 2000 6.7 x 10-8
HBCDs curtains 25 130 850 6.1 x 10-7
EFa (pg/m2・h): Area specific emission rate from productsEF (/year) : Annual emission factors of PBDEs from TV sets and HBCDs from curtains
-3
-2
-1
0
1
TeC
DD
s
PeC
DD
sH
xCD
Ds
HpC
DD
sO
CD
D
ΣPC
DDs
TeC
DFs
PeC
DFs
HxC
DFs
HpC
DFs
OC
DF
ΣPC
DFs
MoC
Bs
DiC
Bs
TrC
Bs
TeC
Bs
PeC
Bs
HxC
Bs
HpC
Bs
OC
Bs
ΣPC
Bs
MoB
DEs
DiB
DEs
TrB
DEs
TeB
DEs
PeD
BEs
HxB
DEs
HpB
DEs
OB
DEs
NoB
DEs
DeB
DE
ΣPB
DEs
TBB
PA
HB
CD
TBPs PC
P
log
(gas
con
c/du
st c
onc)
.
Concentration ratio of air to dust
Adsorption to dust
(Under 0)
Transition to air
(over 0)
=> Most compounds were adsorbed in dust
Emission from products in use
Emission factors from products / Distribution between air and dust
T. Kose;Organohalogen Compounds, 70, 2305-2308 (2008)
Gas-phase emission factors of PBDEs from TV sets and HBCDs from curtains
14
Photodebromination of technical decabromodiphenyl ether (DecaBDE) added to high- impact polystyrene (HIPS) and TV casings under natural sunlight was compared with that of technical decabromodiphenyl ethane (DBDPE).
SAMPLESHIPS (high impact polystyrene)HIPS + technical DecaBDE (ca. 0.1%)HIPS + technical DBDPE (ca. 0.1%)Used TV casing
Sept. 2006 ~ May 2007
HIPS +DecaBDE +DBDPE TV casing
BDE209 nd 1,300+89 nd 96,000+7,400PBDEs - 1,500+67 - 110,000+7,100DBDPE nd nd 930+15 140+5.7PBDDs nd nd nd 0.095+0.014PBDFs nd 0.24+0.023 nd 23+0.36
PBDD/Fs - 0.24+0.023 - 23+0.38
HIPS: No target compounds were detectedHIPS+DecaBDE: BDE209 contents was about 0.13%HIPS+DBDPE: DBDPE contents was about 0.1%TV casing: BDE209 contents was about 10%
HIPS: No target compounds were detectedHIPS+DecaBDE: BDE209 contents was about 0.13%HIPS+DBDPE: DBDPE contents was about 0.1%TV casing: BDE209 contents was about 10%
N. Kajiwara, Environ. Sci. Technol. 2008, 42, 4404-4409
Behavior at use stage of products/articlesPhotolysis of DecaBDE & DeBDEthane in plastic under natural sunlight
BrBr
CC CCHH HH
HH HH
BrBr BrBr
BrBr
BrBrBrBr
BrBr
BrBr
BrBrBrBr
DBDPEDecaBDE
Br
Br Br
BrBr
OBr
Br Br
BrBr
BDE-209
Temperature-controlled glass room (22 °C)
15
0
500
1000
1500
0 50 100 150 200 250
Sunlight exposure (day)
Con
cent
ratio
n (m
g/kg
)
HIPS+DBDPE
TV casing
0
5
10
15
20
25
30
0 50 100 150 200 250
M1BDFs
D2BDFs
T3BDFs
T4BDFs
P5BDFs
H6BDFs
H7BDFs
O8BDF
PBDFs
Total PBDFs
HIPS+DecaBDE
0
500
1000
1500
0 50 100 150 200 250Sunlight exposure (day)
Con
cent
ratio
n (m
g/kg
)
BDE209 BDE209 (unexposed)BDE209
Rapid photodegradation.Concentration decreased to less than 20% of the initial level after the 224 day exposure.
Half-life of BDE209 in HIPS: 51 days
DBDPE:No significant loss during the 224 day exposure
More resistant to UV irradiation compared to BDE209
BDE209Rapid photodegradation.Concentration decreased to less than 20% of the initial level after the 224 day exposure.
Half-life of BDE209 in HIPS: 51 days
DBDPE:No significant loss during the 224 day exposure
More resistant to UV irradiation compared to BDE209
HIPS+DecaBDE:PBDF concentration increased by approximately 40 times after one week exposure to sunlight, and then decreased gradually (same pattern as BDE209).
PBDF originated from BDE209 were also photodegraded
TV casing:PBDF concentration increased continuously during the experiment (over 20 times after 224 day exposure).
HIPS+DecaBDE:PBDF concentration increased by approximately 40 times after one week exposure to sunlight, and then decreased gradually (same pattern as BDE209).
PBDF originated from BDE209 were also photodegraded
TV casing:PBDF concentration increased continuously during the experiment (over 20 times after 224 day exposure).0
5
10
15
20
25
30
35
40
45
50
0 50 100 150 200 250
HIPS+DecaBDEFormation of PBDFs (polybrominated dibenzofurans)
Photodegradation of DecaBDE and DBDPE
BDE209 in flame resisting plastics photodegraded under natural sunlight exposure, and contributed to the synthesis of PBDFs (not PBDDs) . Formation of PBDFs was clearly apparent in the flame resisting plastics. Although the concentrations of PBDFs found in the plastic matrices tested were 1-4 orders of magnitude lower than those of
PBDEs, more attention should be paid to the fact that PBDFs are formed by sunlight exposure during normal use of flame resisting consumer products.
Total PBDFs
[BD
F]/[t
otal
PB
DF]
0
Sunlight exposure (day)
m + n = 1~8OBrm Brn
m + n = 1~8OBrmBrm Brn
O
mm + + nn = 1~10= 1~10BrBrmm BrBrnn
O
mm + + nn = 1~10= 1~10BrBrmm BrBrnn
16
Materials,Substances
Use
Collection,Selection
Resource recovery
Products,Articles
Used products
Raw materials,
Products Import
Reuse
Appropriate treatment, disposal
Pretreatment
Export
Recycled products
Chemicals in articles/products
Supply chain
Recycle chain
Indoor environment at using stage
Compressed packing
Working environment of dismantling process
Waste incineration,
Final disposal site
Granulation of Refused paper and plastic fuel (RPF)
Manufacture of recycled products
Chemicals in used products
Manufacture
Discard
Utilizing chemical substances
Br O
Br
Br
Br
Br
Br
Br
Br
Br
Br
Br O
Br
Br
Br
Br
Br
Br
Br
Br
Br
O
Br
Br
Br
Br
Br
Br
Br
Br
Br
OHHOBr
Br
Br
Br
CH3
CH3
OHHOBr
Br
Br
Br
CH3
CH3
- The information from supply chain is not enough (hardly available in many cases).=> We have to utilize analytical method to obtain such information.- Products/articles containing hazardous substances should all be accompanied by relevant information
for users, workplaces and disposal sites in order to reduce risks to users and environment.
BrBr
BrBr BrBr
BrBr
BrBr
BrBr
BrBr
BrBr BrBr
BrBr
BrBr
BrBr
18
The following slides are reference work.
• Behavior of chemicals in recycling process of waste products and plastics
• Behavior of chemicals in combustion of waste printed circuit boards
• Behavior of chemicals in treatment process of landfill leachate
19H. Takigami;Organohalogen Compounds, 68, 2190-2193 (2006)
Investigated facility:
- Dismantling and shredding of waste TVs.- Dismantling approximately 600 TVs/day.- New dust collection apparatuses were introduced during investigation.
Schematic diagram of the investigated TV dismantling process
Survey:
- Sampled air in working place before and after introduction of the apparatus.- Difference of BFRs and PBDD/Fs concentrations and patterns in air samples was evaluated.
Behavior and emission control at recycling/waste treatment stage
BFRs and PBDD/Fs in recycling plant of waste home appliances
( : introduced apparatus for dust collection)
20
The differences in concentration of PBDD/Fs and BFRs in for two dust samples and two related plastic samples
0.1
1
10
100
1000
10000
100000
1000000
ΣTeB
DD
s
ΣHpB
DD
s
OB
DD
ΣPB
DD
s
2378
-TeB
DF
ΣTeB
DFs
ΣPeB
DFs
1234
78-H
xBD
F
ΣHxB
DFs
1234
678-
HpB
DF
ΣHpB
DFs
OB
DF
ΣPB
DFs
ΣPB
DD
s/D
Fs
MoB
DEs
DiB
DEs
TrB
DEs
TeB
DEs
PeB
DEs
HxB
DEs
HpB
DEs
OB
DEs
NB
DEs
DB
DE
ΣPB
DEs
TBB
P-A
HB
CD
Con
cent
ratio
n (p
g/m
3 ) Before improvement After improvement
PBDD/DFs PBDEsOther BFRs
Air concentrations of PBDD/Fs and BFRs in the TV dismantling process before and after introducing dust collection apparatuses Before improvement
PBDEs:510,000pg/m3PBDD/Fs: 2,400pg/m3
- The patterns and concentrations of PBDEs in the airbone dust were quite similar to those of the TV inside dust.=> The airbone dust derived from the TV inside dust.
- Emission control of dust is effective for reducing the concentration of BFRs and PBDD/Fs.
Behavior and emission control at recycling/waste treatment stage
BFRs and PBDD/Fs in recycling plant of waste home appliances
After improvementOne order magnitude lower
21
Behavior and emission control at recycling/waste treatment stageFlame retardants and VOCs in recycling process of waste plastics
0
200000
400000
600000
800000
1000000
1200000
1400000
1600000
FY20
02
FY20
03
FY20
04
FY20
05
FY20
06
FY20
07
FY20
08
FY20
09
RPF
dem
and
(ton/
year
)
Refused Paper & Plastic Fuel (RPF)
RPF demands in JapanRPF Granulation
Compressed Packing Alternate of fossil fuels, such as coalsMade from plastics with papers/woodsIncrease in demand and number of
factories
Many local government are operating the plants in Japan.For easy transportation of waste plastics and pretreatment for next recycling processes
Waste plastics after compressed packing
Compression
2222
Flam
e re
tard
ants
0.01
0.1
1
10
100
1000
10000
100000PB
DEs
Dec
aBD
E
Oct
aBD
Es
Tetra
BD
Es
HB
CD
s
TBB
PA
DB
DPE
PBB
zs
Hex
aBB
z
PBPh
s
2,4,
6-Tr
iBPh
PFR
s
Con
cent
ratio
n (n
g/m
3 )
DetectionLimits
Working Environment Emission Gas
0.01
0.1
1
10
100
1000
10000
100000
PBD
Es
Dec
aBD
E
Oct
aBD
Es
Tetra
BD
Es
HB
CD
s
TBB
PA
DB
DPE
PBB
zs
Hex
aBB
z
PBPh
s
2,4,
6-Tr
iBPh
PFR
s
DetectionLimits
VOC
sC
once
ntra
tion
( mg
mg/
m3 )
0.0001
0.001
0.01
0.1
1
10
Tolu
ene
m,p
-Xyl
ene
o-X
ylen
e
Ethy
lben
zene
Styr
ene
Trim
ethy
lben
zene
Ben
zene
Dic
hlor
omet
hane
Form
alde
hyde
Ace
tald
ehyd
e
Trim
ethy
lam
ine
Am
mon
ia
DetectionLimits
0.0001
0.001
0.01
0.1
1
10
Tolu
ene
m,p
-Xyl
ene
o-X
ylen
e
Ethy
lben
zene
Styr
ene
Trim
ethy
lben
zene
Ben
zene
Dic
hlor
omet
hane
Form
alde
hyde
Ace
tald
ehyd
e
Trim
ethy
lam
ine
Am
mon
ia
DetectionLimits
Behavior and emission control at recycling/waste treatment stage
Concentration in compressed packing plant of waste plastics
2323
Flam
e re
tard
ants
Con
cent
ratio
n (n
g/m
3 )
DetectionLimits
0.01
0.1
1
10
100
1000
10000
100000PB
DEs
Dec
aBD
E
Oct
aBD
Es
Tetra
BD
Es
HB
CD
s
TBB
PA
DB
DPE
PBB
zs
Hex
aBB
z
PBPh
s
2,4,
6-Tr
iBPh
PFR
s
0.01
0.1
1
10
100
1000
10000
100000
PBD
Es
Dec
aBD
E
Oct
aBD
Es
Tetra
BD
Es
HB
CD
s
TBB
PA
DB
DPE
PBB
zs
Hex
aBB
z
PBPh
s
2,4,
6-Tr
iBPh
PFR
s
DetectionLimits
Working Environment Emission Gas
VOC
sC
once
ntra
tion
( mg
mg/
m3 )
0.0001
0.001
0.01
0.1
1
10
Tolu
ene
m,p
-Xyl
ene
o-X
ylen
e
Ethy
lben
zene
Styr
ene
Trim
ethy
lben
zene
Ben
zene
Dic
hlor
omet
hane
Form
alde
hyde
Ace
tald
ehyd
e
Trim
ethy
lam
ine
Am
mon
ia
DetectionLimits
0.0001
0.001
0.01
0.1
1
10
Tolu
ene
m,p
-Xyl
ene
o-X
ylen
e
Ethy
lben
zene
Styr
ene
Trim
ethy
lben
zene
Ben
zene
Dic
hlor
omet
hane
Form
alde
hyde
Ace
tald
ehyd
e
Trim
ethy
lam
ine
Am
mon
ia
DetectionLimits
Behavior and emission control at recycling/waste treatment stage
Concentration in granulation of refused paper & plastic fuel (RPF)
24M. Watanabe; Organohalogen Compounds, 70, 78-81 (2008)
Air
Fixed speed feeder
Rotary kiln primary combustion chamber(Electrical heating)
Ver
tical
sec
onda
ry
com
bust
ion
cham
ber
(Ele
ctric
al h
eatin
g)
Gas
coo
ling
zone
Bag
Filte
r
Act
ivat
ed c
arbo
n ad
sorp
tion
tow
er
Wet
scr
ubbe
r
Bottom ash Fly ash
Kiln exit gas
Input (wP-CBs)
Bag filter entry gas Bag filter exit gas Final exit gas
NaHCO3
900˚C3 sec.
840˚C
150˚C
Printed circuit boards (P-CBs) usedMainly from waste personal computers (PCs).Manufactured mostly within a decade.Approximately 20 kg of P-CBs used for the study.
Sample preparationRemoved large metal parts, such as radiatorsCrushed into small pieces (< 5 mm) and then crushed under low temperature condition (< room temp.) using Liquid N2
Behavior and emission control at recycling/waste treatment stageBehavior of BFRs, PFRs and PXCD/Fs in combustion of printed circuit board
Thermal treatment plant equipment at our center
25
0300060009000
12000
This study 1987-1995
PBDEs
0
200
400
600
This study 1987-1995
TBBPA
0
50
100
150
This study 1987-1995
PBDD/Fs
050
100150200
This study 1987-1995
PBPhs
0300060009000
12000
This study 1987-1995
PBDEs
0
200
400
600
This study 1987-1995
TBBPA
0
50
100
150
This study 1987-1995
PBDD/Fs
050
100150200
This study 1987-1995
PBPhs
PBDEs
0
200
400
600
This study 1987-1995
TBBPA
0
200
400
600
This study 1987-1995
TBBPA
0
50
100
150
This study 1987-1995
PBDD/Fs
0
50
100
150
This study 1987-1995
PBDD/Fs
050
100150200
This study 1987-1995
PBPhs
050
100150200
This study 1987-1995
PBPhs0
100
200
300
400
500PB
DE
s
DB
DPE
PBPh
s
TB
BPA
PBB
zs
HB
CD
s
PFR
s
PBD
D/F
s
PXD
D/F
s
PCD
D/F
s
<0.7 <0.00002
Con
cent
ratio
n (m
g/kg
)
Brominated organic compounds measured by HRGC/HRMS and LC/MS720 mg-Br/kg = Only 2.6% of total Br (28,000 mg-Br/kg)
=> Other types of BFRs:97.4%
Volatile matter C H N Br Cl O29.6 20.6 2.0 0.4 2.8 0.13 3.7
Elemental Composition (wt %) of crushed waste P-CBs using in this study
Con
cent
ratio
n (m
g/kg)
Comparison with old waste P-CBsConcentrations in present waste P-CBs
Behavior and emission control at recycling/waste treatment stageChemicals contents of waste printed circuit boards used for the study
2626
1.E-2
1.E-1
1.E+0
1.E+1
1.E+2
1.E+3
1.E+4
1.E+5
1.E+6In
put
Kiln
exi
t
BF
entry
BF
exit
Fina
l exi
t
DeBDE DBDPE TBBPA
Con
cent
ratio
n (m
g/to
n on
inpu
t bas
is)
1.E-3
1.E-2
1.E-1
1.E+0
1.E+1
1.E+2
1.E+3
1.E+4
1.E+5
1.E+6
Inpu
t
Kiln
exi
t
BF
entry
BF
exit
Fina
l exi
t
OctaBDEs TrBPhs HxBBz
1.E-4
1.E-3
1.E-2
1.E-1
1.E+0
1.E+1
1.E+2
1.E+3
1.E+4
Inpu
t
Kiln
exi
t
BF
entry
BF
exit
Fina
l exi
t
PBDD/Ds PXDD/Fs PCDD/Fs
1.E-4
1.E-3
1.E-2
1.E-1
1.E+0
1.E+1
1.E+2
1.E+3
1.E+4
Inpu
t
Kiln
exi
t
BF
entry
BF
exit
Fina
l exi
tDiBDEs MoBPhs DiBBzs
Behavior and emission control at recycling/waste treatment stage
Results of combustion experiment
27
Raw LeachatePBDE:0.23ng/LHBCD:1.3ng/LPBB, PBDD/Fs, TBBPA, DeBDethane: ND
Leachate Regulatingtank
Chemicaltreatment
Biologicaltreatment
Advanced water treatment effluent
Coagulation with aluminum sulfatetype coagulant
(1) (2) (3) (4)
Activated sludge and nitrogen removal treatment
Sand filtration andactivated carbontreatment
B
0
0.5
1
1.5
2
(1) (2) (3) (4)
Con
cent
ratio
n (n
g/L)
α-HBCDPBDEs
0
100
200
300
400
500
(1) (2) (3) (4)
Con
cent
ratio
n (n
g/L)
Tris(2-chloroisoporopyl)phosphate bTris(2-chloroisoporopyl)phosphate a
TriethylphosphateTributylphosphate
Tris(2-chloroethyl)phosphateTris(butoxyethyl)phosphateTris(1,3-dichloro-2-propyl)phosphatePBDEs
TBBPA
Leachate from landfill site in Japan (reference data)PBDEs: 30~18000 pg/L, TBBPA: <1000~620000 pg/L (Osako
et al. (2004) Chemosphere, 57, 1571-1579)
Behavior and emission control at recycling/waste treatment stageConcentration of BFRs and OPEs in landfill leachate
(3) Process water after biological treatment(4) Effluent
(1) Raw leachate after regulation(2) Process water after chemical treatment