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

17

Thank you for your attention!

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