2017/4/3 UNINTENTIONAL FORMATION OF PCB FROM CHEMICAL - - PDF document

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2017/4/3 UNINTENTIONAL FORMATION OF PCB FROM CHEMICAL - - PDF document

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2017/4/3 UNINTENTIONAL FORMATION OF PCB FROM CHEMICAL MANUFACTURING PROCESS (POPs) FeCl 3 3,3 -dichlorobenzidine Chlorinated Paraffins Diphenyl Silane diol

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SLIDE 1

2017/4/3 1 非意図的に生成する残留性 有機汚染物質(POPs)

中野 武 （大阪大学 環境安全研究管理センター）

UNINTENTIONAL FORMATION OF PCB FROM CHEMICAL MANUFACTURING PROCESS FeCl3 3,3’-dichlorobenzidine Chlorinated Paraffins Diphenyl Silane diol Organic pigment

  • PCB in silicone-based adhesives and chlorophenylsilanes
  • Congener profiles in adhesives and chlorophenylsilanes : --
  • ------ > quite similar
  • High PCBs were detected in dichlorodiphenylsilane.
  • Similar Congener profiles were come from the chlorobenzene

used for chlorophenylsilanes manufacturing process.

Results

PCB PCB congener profil files s of azo pigme ment

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SLIDE 2

2017/4/3 2

(CuCl2) NaNO2, HCl

Sandme meyer reaction

  • n

Ar-N+≡N + CuX → Ar-X + Cu+ + N2↑

CB-52(25-25) CB CB-101(245-25) CB CB-153(245-245) 2,2’,5,5’- tetrachlo loro benzid idine ine

Compound View JEOL DioK V4.02 2011/05/31 15:04:30 Page 1 DqData: rh (), Injection= P115 (UNK) Original: rh_T-PCB-110420.mfl, InjectionNo= 22, Sample= P115, Date= <Date> 12 14 16 18 20 22 24 26 28 30 Retention Time (min) (341082) 20 40 60 80 100 Intensity D2CB / Average 12 14 16 18 20 22 24 26 28 30 Retention Time (min) (16777200) 20 40 60 80 100 Intensity T4CB / Average 12 14 16 18 20 22 24 26 28 30 Retention Time (min) (225850) 20 40 60 80 100 Intensity P5CB / Average 12 14 16 18 20 22 24 26 28 30 Retention Time (min) (180016) 20 40 60 80 100 Intensity H6CB / Average

#11 (3-3) #52(25-25) #101(245-25) #153(245-245)

PCB cong ngene ners in pigment nt (disazo) permane nent nt yellow w lemon; PY81;

2,2’,5,5 ’- tetrachlo loro benzid idine ine

Results

PC PCB congener profil files s of phthalocyanine pigme ment

phthalocyanine-type pigment phthalic anhydride urea copper chloride raw material pigment green 7 (phthalocyanine green) pigment blue 15 (phthalocyanine blue) chlorination pigment green 7 By By-product

Cl Cl Cl Cl Cl Cl Cl Cl Cl #209 Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl #208 Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl PeCBz

highly chlorinated PCBs D

HCB

PG-7

PCB PCB congener profil files s of diketo-pyrrolo

  • lo-pyr

yrrole pigme ments

PCB-8, PCB-13, PCB-15 >> PCB-4, PCB-6, PCB-11

PR-254

PCB PCB congener profil files s of dio dioxa xazine ne vi violet pigment pigments PV-23

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SLIDE 3

2017/4/3 3

V-70L Δ CB-4 (2-2) CB-6 (2-3) CB-11 (3-3) CB-8 (2-4) CB-13 (3-4) CB-15 (4-4)

CB-6 > CB-8 > CB-11, CB-13 > CB-4 > CB-15 chlorobenzene  DiCB

A B CC AC BC C BB AB AA A B > AC > BB , BC > AA > CC

PCB FORMATION FROM PCBz via different PCBz radicals

V-70L Δ CB-52 (25-25) V-70L Δ CB155 (246-246)

p-dichlorobenzene 1,3,5-trichlorobenzene

  • ne PCB isomer formation

5 3 11 5 2 V-70L Δ CB-56 (23-34) CB-77 (34-34) CB-40 (23-23) CB-5 (23-) CB-12 (34-)

  • -dichlorobenzene

CB-56 > CB-77 > CB-40

A B BB AB AA A B > BB > AA CB128 (234-234) CB-157 (234-345) CB-169 (345-345) V-70L Δ

1,2,3-trichlorobenzene CB-157 > CB-128 > CB-169

A B BB AB AA A > B A B > AA >> BB V-70L Δ CB-4 (2-2) CB-6 (2-3) CB-11 (3-3) CB-8 (2-4) CB-13 (3-4) CB-15 (4-4)

CB-6 > CB-8 > CB-11, CB-13 > CB-4 > CB-15 chlorobenzene  DiCB

A B CC AC BC C BB AB AA A B > AC > BB , BC > AA > CC

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SLIDE 4

2017/4/3 4

CB-73 (26-35) CB-68 (24-35) CB-80 (35-35) CB-54 (26-26) CB-51 (24-26) CB-47 (24-24) V-70L Δ

m-dichlorobenzene CB-68 > CB-47 > CB-73, CB-51 > CB-80 > CB-54

A B BC AB BB C CC AC AA BC > CC > A B > AC > BB > AA C > A, B CB146 (235-245) CB-149 (236-245) CB-153 (245-245) CB133 (235-235) CB-135 (235-236) CB-136 (236-236) V-70L Δ

1,2,4-trichlorobenzene

CB-146, CB-149, CB-135 > CB-153, CB-136, CB-133

5 3 11 5 2 V-70L Δ CB-56 (23-34) CB-77 (34-34) CB-40 (23-23) CB-5 (23-) CB-12 (34-)

  • -dichlorobenzene

CB-56 > CB-77 > CB-40

A B BB AB AA A B > BB > AA 原料 顔料 副生PCB PR254

PCB-8 PCB-13 PCB-15 PCB-11 PCB-6 PCB-4

(CuCl2) NaNO2, HCl

サンドマイヤー反応 Ar-N+≡N + CuX → Ar-X + Cu+ + N2↑

芳香族ジアゾニウム塩を塩化銅(存在下に生成させ、加温分解す ると、アミノ基が塩素置換されたアリールが生成 CB-52(25-25) CB CB-101(245-25) CB CB-153(245-245) 2,2’,5,5’-テトラクロロベンジジン

Compound View JEOL DioK V4.02 2011/05/31 15:04:30 Page 1 DqData: rh (), Injection= P115 (UNK) Original: rh_T-PCB-110420.mfl, InjectionNo= 22, Sample= P115, Date= <Date> 12 14 16 18 20 22 24 26 28 30 Retention Time (min) (341082) 20 40 60 80 100 Intensity D2CB / Average 12 14 16 18 20 22 24 26 28 30 Retention Time (min) (16777200) 20 40 60 80 100 Intensity T4CB / Average 12 14 16 18 20 22 24 26 28 30 Retention Time (min) (225850) 20 40 60 80 100 Intensity P5CB / Average 12 14 16 18 20 22 24 26 28 30 Retention Time (min) (180016) 20 40 60 80 100 Intensity H6CB / Average

#11 (3-3) #52(25-25) #101(245-25) #153(245-245) 顔料中のPCB異性体（ジスアゾ系）

permane nent nt yellow w lemon; PY81;

2,2’,5,5’- テトラクロロベンジジン

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SLIDE 5

2017/4/3 5

  • Organic Pigment

Compound View JEOL DioK V4.01 2012/04/10 14:38:21 Page 1 DqData: rh (), Injection= pigment_sample (UNK) Original: rh_T-PCB-110420.mfl, InjectionNo= 18, Sample= PG032, Date= <Date> 12 14 16 18 20 22 24 26 28 Retention Time (min) (1606) (5038) 25 50 75 100 Intensity M1CB / Average 12 14 16 18 20 22 24 26 28 Retention Time (min) (3394356) 25 50 75 100 Intensity D2CB / Average 12 14 16 18 20 22 24 26 28 Retention Time (min) (927733) 25 50 75 100 Intensity T3CB / Average 12 14 16 18 20 22 24 26 28 Retention Time (min) (1169387) 25 50 75 100 Intensity T4CB / Average 12 14 16 18 20 22 24 26 28 Retention Time (min) (911) (3926) 25 50 75 100 Intensity P5CB / Average

D2CB T3CB T4CB #11(3-3) 3) #35(34-3) 3) #77 #77

Pigment-A

M1CB P5CB (N.D.) (N.D.) (34-34) 34)

Compound View JEOL DioK V4.01 2012/04/10 14:48:42 Page 1 DqData: rh (), Injection= P115 (UNK) Original: rh_T-PCB-110420.mfl, InjectionNo= 22, Sample= P115, Date= <Date> 12 14 16 18 20 22 24 26 28 Retention Time (min) (4846) 25 50 75 100 Intensity M1CB / Average 12 14 16 18 20 22 24 26 28 Retention Time (min) (341082) 25 50 75 100 Intensity D2CB / Average 12 14 16 18 20 22 24 26 28 Retention Time (min) (5258927) 25 50 75 100 Intensity T3CB / Average 12 14 16 18 20 22 24 26 28 Retention Time (min) (16777200) 25 50 75 100 Intensity T4CB / Average 12 14 16 18 20 22 24 26 28 Retention Time (min) (225850) 25 50 75 100 Intensity P5CB / Average

D2CB T3CB T4CB P5CB #11(3-3) 3) #101 #101 (ﾌﾗｸﾞﾒﾝﾄｲｵﾝ) #52 #52

Pigment-B

M1CB (N.D.) (25-25) 25) (245-25) 25)

顔料由来の異性体と 環境試料中のPCB

10 20 30 40 50 KC300-60 5 10 15 20 25 30 35 40 #4 #8/#5 #11 #12/#13 #15 #18/#17 #16/#32 #26 #25 #31/#28 #33/#20 #35 #37 Air (gas phase) 10 20 30 40 50 60 Sediment 10 20 30 40 50 Water 10 20 30 40 50 60 70 80 Rain

図 PCB製品および環境試料中のDi-TrCB異性体分布 #10/(2,6-)#4(2,2'-), #8(2,4-)/#5(2,3-), #11(3,3'-), #12(3,4-)/#13(3,4'), #15(4,4'-), #18(2,2',5-)/#17(2,2',4-), #16(2,2',3-)/#32(2,4',6-), #26(2,3',5-), #25(2,3',4-),#31(2,4',5-)/#28(2,4,4'-),#33(2',3,4-)/#20(2,3,3'-),#35(3,3',4-), #37(3,4,4'-)

中野ら, 環境化学討論会要旨集 P-281 (2001) 底質 水質 PCB製品 雨水 大気 PCB-11

3,3’-DiCB has been associated with 3,3’-dichlorobenzidine salts which are intermediates in the manufacture of diarylide yellow pigments. The pigment factory also discharged two other congeners at high concentrations, 3,3’,4-TriCB and the coplanar 3,3’,4,4’-

  • TeCB. Coplanar 3,3’,4,4’,5- PeCB was also seen in the

discharge at higher than usual proportions. However, the New Jersey effluent was more purely 3,3’-DiCB.

Identification of a novel PCB source through analysis

  • f 209 PCB congeners by US EPA modified method 1668

Simon Litten et al, Chemosphere, 46, 1457-1459(2002)

Identification of a novel PCB source through analysis

  • f 209 PCB congeners by US EPA modified method 1668

Simon Litten et al, Chemosphere, 46, 1457-1459(2002)

Total PCB PCB PCB-11 11 PCB PCB-35 35 PCB PCB-77 77 PCB PCB-12 126 TEQ(fg fg/L /L) Pigment nt dischar arge 4200 4200 3600 3600 380 380 190 190 1.6 1.6 18000 18000 WPCF influen ent 520 520 490 490 2.3 2.3 2.5 2.5 0.01 0.01 150 150 Trunk1 18 18 0.07 0.07 <0.001 01 15 15 Trunk2 12 12 0.4 0.4 0.02 0.02 0.01 0.01 <0.000 004 13 13 Trunk3 12 12 0.6 0.6 0.03 0.03 0.01 0.01 <0.001 01 8 Trunk4 3 0.08 0.08 0.04 0.04 0.05 0.05 <0.001 01 2 Trunk5 1 0.2 0.2 0.02 0.02 0.04 0.04 0.001 0.001 1 PISCES survey, 7/27/00–8/2/00 to locate sources of PCB congeners (ng/l)

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SLIDE 6

2017/4/3 6

5 10 15 20 25 30 35 40 45 50 8-1 8-2 8-3 8-4 8-5 8-6 8-7 8-8 8-9 8-10 8-11 8-12 8-14 8-15 8-16 8-17 8-18 8-20 8-21 8-22 8-23 8-24 8-25 8-26 8-27 8-28 8-30 8-31 concentration (pg/m3 )

PCDF PCDD Low-vol. （PCDD+PCDF) Hi-vol.

Daily Variation of PCDD/PCDF levels in Air (Aug.1-31) Monitoring the air concentrations of POPs

POPs monitoring ③Low (Middle)-Vol ④Passive sampler ①Hi-Vol

PUF

Quartz filter Air PUF×2 Activated carbon filter 大気 PS-Air Air

②PS-Air Cartridge

Sampling period (day) Sampling Volume (m3) ①Hi-Vol 1 1000 ②PS-Air Cartridge 1 – 3 3-9 ③Low (Middle)–Vol 30 (7) 1000 ④Passive sampler 7 – 30 ?

  • Active air sampling（AAS）

Flow meter Pump PS-Air

AAS was performed using a low volume pump and two PS-Air cartridge (Waters)

Passive air sampling(PAS)

Passive air sampler Inside

Polyurethane foam plug (PUF) was set by different size double stainless steel bowl to protect the passive air sampler from direct deposition of particulate matter and to minimize the influence of varying air velocity.

PUF: 85mm id x 5omm

＋

大気中PCB同族体分布の変動 (日本)

Daily variation of PCB homologue profiles in air sample

3Cl 3Cl 3Cl 3Cl 2Cl

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SLIDE 7

2017/4/3 7

大気中PCB異性体分布の比較 PassiveとActive sampling (日本)

TrCBs AAS PAS

#19 #18 #17 #31 #32 #16 #26 #33 #22 #28 #37

GC GC-MS/M /MS S Chromato atogram am (TrCB) GC GC-MS/M /MS S Chromato atogram am (TeCB)

AAS PAS

#53 #45 #41 #48,47 #52 #49 #71 #44 #42 #64 #74 #70 #80 #60 #56

TeCBs AAS PAS

#95 #91 #92 #84 #101 #99 #97 #87 #85 #110 #118 #105

GC GC-MS/M /MS S Chromato atogram am (PeCB)

PeCBs AAS PAS

#136 #138 #151 #132 #149 #153

GC GC-MS/M /MS S Chromato atogram am (HxCB)

HxCBs

Sampling Rate の推算 PassiveとActive sampling

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SLIDE 8

2017/4/3 8

Sampling rate e (TrCBs)

(m3/day)

：Sampling rate (Min to Max)

  • ：Sampling rate (average_n=3)

IUPAC No. sampring rate (m3/day) average (m3/day) IUPAC No. sampring rate (m3/day) average (m3/day)

#19 0.1-0.5 0.4 #31 0.7-1.6 1.1 #18 0.5-1.4 0.9 #28 0.6-1.5 1.0 #17 0.4-1.1 0.7 #33 0.5-1.5 1.0 #32 0.2-1.1 0.6 #22 0.5-1.5 0.9 #16 0.4-1.0 0.7 #37 0.5-1.7 0.9 #26 0.8-1.0 0.9

(m3/day)

：Sampling rate (Min to Max)

  • ：Sampling rate (average_n=4)

Sampling rate e (TeCBs)

IUPAC No. sampring rate (m3/day) average (m3/day) IUPAC No. sampring rate (m3/day) average (m3/day) #53 0.4-1.2 0.7 #71 0.4-2.0 0.9 #45 0.3-1.0 0.6 #41 0.3-1.9 0.9 #52 1.0-1.9 1.3 #74 0.5-1.9 1.0 #49 0.6-1.7 1.0 #70 0.8-2.1 1.3 #48,47 0.4-1.4 0.8 #80 0.6-2.0 1.1 #44 0.8-2.2 1.2 #60 0.3-2.3 1.0 #42 0.3-2.1 0.9 #56 0.7-2.4 1.2 #64 0.5-2.4 1.1 (m3/day)

：Sampling rate (Min to Max)

  • ：Sampling rate (average_n=4)

Sampling rate e (PeCBs)

IUPAC No. sampring rate (m3/day) average (m3/day) IUPAC No. sampring rate (m3/day) average (m3/day) #95 1.1-3.2 1.7 #97 0.8-2.1 1.2 #91 0.8-2.9 1.4 #87 0.6-1.7 1.2 #92 0.6-1.9 1.2 #85 0.1-0.9 0.6 #84 0.3-2.5 1.3 #110 0.8-1.8 1.3 #101 0.8-1.9 1.3 #118 0.7-4.0 1.8 #99 0.6-1.1 0.9 #105 0.6-3.1 1.5

(m3/day)

：Sampling rate (Min to Max)

  • ：Sampling rate (average_n=4)

Sampling rate e (HxCBs)

IUPAC No. sampring rate (m3/day) average (m3/day) #136 0.5-1.5 0.9 #151 0.6-0.8 0.7 #149 0.8-1.4 1.1 #132 0.5-1.8 1.2 #153 0.4-2.2 1.3 #138 0.3-2.4 1.4

Average of sampling rate

PCB congeners Average of sampling rate (m3/day) TrCBs 0.4-1.1 TeCBs 0.6-1.3 PeCBs 0.6-1.8 HxCBs 0.7-1.4 R(m3/day) Location Type References 0.57-1.55 indoor UFO Hazrati and Harrad (2007) 1.0-1.1 indoor UFO Nakano et al (2014) 2.0-8.3 indoor UFO Shoeib and Harner (2002) [2] 0.5-6 indoor UFO Building (2014) 0.4-1.1 indoor UFO TrCBs 0.6-1.3 indoor UFO TeCBs 0.6-1.8 indoor UFO PeCBs 0.7-1.4 indoor UFO HxCBs

Comparison