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

2017/4/3 UNINTENTIONAL FORMATION OF PCB FROM CHEMICAL 非意図的に生成する残留性 MANUFACTURING PROCESS 有機汚染物質 (POPs) FeCl 3 3,3’ -dichlorobenzidine Chlorinated Paraffins 中野 武 Diphenyl Silane diol （大阪大学 環境安全研究管理センター） Organic pigment Results PCB PCB congener profil files s of azo pigme ment - 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 . 1

2017/4/3 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> D2CB / Average (341082) 100 #11 (3-3) 80 Intensity 60 40 20 0 12 14 16 18 20 22 24 26 28 30 Retention Time (min) (16777200) T4CB / Average CB-52(25-25) 100 #52(25-25) (CuCl 2 ) 80 NaNO 2 , HCl Intensity 60 40 20 0 2,2’,5,5 ’ - 12 14 16 18 20 22 24 26 28 30 Retention Time (min) tetrachlo loro benzid idine ine P5CB / Average (225850) 100 #101(245-25) 80 Intensity 60 40 20 0 CB-101(245-25) CB 12 14 16 18 20 22 24 26 28 30 Retention Time (min) (180016) H6CB / Average 100 #153(245-245) 2,2’,5,5’ - tetrachlo loro benzid idine ine 80 Intensity 60 40 Sandme meyer reaction on 20 Ar-N + ≡ N + CuX → Ar-X + Cu + + N 2 ↑ 0 12 14 16 18 20 22 24 26 28 30 Retention Time (min) PCB cong ngene ners in pigment nt (disazo) permane nent nt yellow w lemon; PY81; CB CB-153(245-245) Results phthalocyanine-type pigment By-product By raw material Cl phthalic anhydride Cl Cl urea Cl Cl copper chloride PeCBz PCB congener profil PC files s of pigment blue 15 Cl Cl (phthalocyanine blue) Cl Cl phthalocyanine pigme ment Cl Cl chlorination D HCB pigment green 7 pigment green 7 (phthalocyanine green) Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl PG-7 Cl Cl Cl Cl Cl Cl Cl Cl #209 #208 highly chlorinated PCBs PCB PCB congener profil files s of PCB PCB congener profil files s of diketo-pyrrolo olo-pyr yrrole pigme ments dio dioxa xazine ne vi violet pigment pigments PV-23 PR-254 PCB-8, PCB-13, PCB-15 >> PCB-4, PCB-6, PCB-11 2

2017/4/3 CB-6 > CB-8 > CB-11, CB-13 > CB-4 > CB-15 A B > AC > BB , BC > AA > CC AA A AC PCB FORMATION FROM PCBz CB-4 (2-2) CB-8 (2-4) B C AB CC CB-15 (4-4) CB-6 (2-3) via different PCBz radicals Δ V-70L BC BB CB-13 (3-4) CB-11 (3-3) chlorobenzene  DiCB one PCB isomer formation CB-56 > CB-77 > CB-40 A B > BB > AA Δ 11 5 A AB V-70L CB-5 (23-) CB-56 (23-34) CB-52 (25-25) 5 3 BB p -dichlorobenzene B CB-12 (34-) CB-77 (34-34) Δ Δ AA 2 V-70L V-70L CB-40 (23-23) CB155 (246-246) 1,3,5 -trichlorobenzene o -dichlorobenzene CB-157 > CB-128 > CB-169 CB-6 > CB-8 > CB-11, CB-13 > CB-4 > CB-15 A B > AC > BB , BC > AA > CC A B > AA >> BB AA A AA AC CB128 (234-234) CB-4 (2-2) CB-8 (2-4) B C A AB Δ AB CC V-70L CB-157 (234-345) CB-15 (4-4) B CB-6 (2-3) Δ V-70L BB BC BB A > B CB-13 (3-4) CB-169 (345-345) CB-11 (3-3) chlorobenzene  DiCB 1,2,3 -trichlorobenzene 3

2017/4/3 CB-68 > CB-47 > CB-73, CB-51 > CB-80 > CB-54 CB-146, CB-149, CB-135 > CB-153, CB-136, CB-133 BC > CC > A B > AC > BB > AA AA A AB CB133 (235-235) CB146 (235-245) B CB-54 (26-26) CB-73 (26-35) C AC BC CB-149 (236-245) CB-135 (235-236) Δ CB-68 (24-35) V-70L CB-51 (24-26) Δ V-70L CC BB CB-153 (245-245) CB-80 (35-35) CB-136 (236-236) CB-47 (24-24) C > A, B m -dichlorobenzene 1,2,4 -trichlorobenzene CB-56 > CB-77 > CB-40 原料 PR254 顔料 A B > BB > AA 11 5 A AB CB-5 (23-) CB-56 (23-34) 5 3 BB B CB-12 (34-) CB-77 (34-34) Δ AA 2 V-70L 副生 PCB PCB-8 PCB-15 PCB-13 CB-40 (23-23) PCB-6 PCB-4 PCB-11 o -dichlorobenzene 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> D2CB / Average (341082) 100 #11 (3-3) 80 Intensity 60 40 20 0 12 14 16 18 20 22 24 26 28 30 Retention Time (min) T4CB / Average (16777200) CB-52(25-25) 100 #52(25-25) 80 (CuCl 2 ) NaNO 2 , HCl Intensity 60 40 20 0 2,2’,5,5’ - 12 14 16 18 20 22 24 26 28 30 Retention Time (min) テトラクロロベンジジン (225850) P5CB / Average 100 #101(245-25) 80 Intensity 60 40 20 CB CB-101(245-25) 0 12 14 16 18 20 22 24 26 28 30 Retention Time (min) H6CB / Average (180016) 100 #153(245-245) 2,2’,5,5’ - テトラクロロベンジジン 80 Intensity 60 40 サンドマイヤー反応 20 Ar-N + ≡ N + CuX → Ar-X + Cu + + N 2 ↑ 0 12 14 16 18 20 22 24 26 28 30 Retention Time (min) 顔料中 の PCB 異性体（ジスアゾ系） 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 permane nent nt yellow w lemon; PY81; CB CB-153(245-245) 4

2017/4/3 - Organic Pigment Pigment-A Compound View Pigment-B Compound View JEOL DioK V4.01 2012/04/10 14:38:21 Page 1 JEOL DioK V4.01 2012/04/10 14:48:42 Page 1 DqData: rh (), Injection= P115 (UNK) DqData: rh (), Injection= pigment_sample (UNK) Original: rh_T-PCB-110420.mfl, InjectionNo= 22, Sample= P115, Date= <Date> Original: rh_T-PCB-110420.mfl, InjectionNo= 18, Sample= PG032, Date= <Date> M1CB / Average M1CB / Average (N.D.) M1CB (N.D.) M1CB Intensity Intensity (5038) (4846) 100 100 75 (1606) 75 50 25 50 25 0 0 12 14 16 18 20 22 24 26 28 12 14 16 18 20 22 24 26 28 Retention Time (min) Retention Time (min) D2CB / Average (3394356) D2CB / Average (341082) 100 100 顔料由来の異性体と #11(3-3) 3) D2CB #11(3-3) 3) D2CB 75 75 Intensity Intensity 50 50 25 25 0 0 環境試料中の PCB 12 14 16 18 20 22 24 26 28 12 14 16 18 20 22 24 26 28 Retention Time (min) Retention Time (min) T3CB / Average (5258927) T3CB / Average (927733) 100 100 T3CB #35(34-3) 3) T3CB ( ﾌﾗｸﾞﾒﾝﾄｲｵﾝ ) 75 75 Intensity Intensity 50 50 25 25 0 0 12 14 16 18 20 22 24 26 28 12 14 16 18 20 22 24 26 28 Retention Time (min) Retention Time (min) (1169387) T4CB / Average #77 #77 (16777200) T4CB / Average 100 #52 #52 100 T4CB 75 T4CB 75 Intensity (34-34) 34) Intensity (25-25) 25) 50 50 25 25 0 0 12 14 16 18 20 22 24 26 28 12 14 16 18 20 22 24 26 28 Retention Time (min) Retention Time (min) P5CB / Average P5CB / Average (225850) #101 #101 100 (N.D.) P5CB 75 P5CB Intensity Intensity (245-25) 25) 50 25 (3926) 100 (911) 25 50 75 0 0 12 14 16 18 20 22 24 26 28 12 14 16 18 20 22 24 26 28 Retention Time (min) Retention Time (min) 50 KC300-60 0 40 3,3’ - DiCB has been associated with 3,3’ -dichlorobenzidine salts 30 PCB 製品 20 which are intermediates in the manufacture of diarylide yellow 10 0 pigments. 60 Sediment 50 40 底質 30 20 The pigment factory also discharged two other congeners at 10 PCB-11 0 high concentrations, 3,3’,4 - TriCB and the coplanar 3,3’,4,4’ - 50 Water 40 TeCB . Coplanar 3,3’,4,4’,5 - PeCB was also seen in the 30 水質 20 discharge at higher than usual proportions. 10 0 However, the New Jersey effluent was more purely 3,3’ -DiCB . 80 70 Rain 60 50 雨水 40 Identification of a novel PCB source through analysis 30 20 of 209 PCB congeners by US EPA modified method 1668 10 0 40 Simon Litten et al, Chemosphere, 46, 1457-1459(2002) Air (gas phase) 35 30 25 大気 20 15 10 5 0 #4 #8/#5 #11 #15 #26 #25 #35 #37 #12/#13 #18/#17 #16/#32 #31/#28 #33/#20 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) Identification of a novel PCB source through analysis of 209 PCB congeners by US EPA modified method 1668 Simon Litten et al, Chemosphere, 46, 1457-1459(2002) PISCES survey, 7/27/00 – 8/2/00 to locate sources of PCB congeners (ng/l) 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 0 <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 5