PCB CONGENER PROFILE OF UNINTENTIONAL FORMATION FROM PIGMENT MANUFACTURING PROCESS Takeshi Nakano1 and Katsunori Anezaki2 1Osaka University 2Hokkaido Research Organization PCB CONGENER PROFILE OF UNINTENTIONAL FORMATION FROM PIGMENT MANUFACTURING PROCESS FeCl3 3,3’-dichlorobenzidine Chlorinated Paraffins Diphenyl Silane diol Organic pigment High Volume Air Sampler Noise/Vibration absorption rubber Using chlorinated paraffins containing PCB PCB CONGENER PROFILE OF UNINTENTIONAL FORMATION FROM PIGMENT MANUFACTURING PROCESS FeCl3 Chlorinated Paraffins 3,3’-dichlorobenzidine Diphenyl Silane diol Organic pigment TCPS CTPS DCDPS D Cu,Ag + Si Chlorobenzene Trichlorophenylsilane PCB-1 Dichlorodiphenylsilane Chlorotriphenylsilane PCB-2 PCB-4 PCB-8 PCB-6 PCB-13 PCB-11 PCB-3 MoCBs PCB-15 DiCBs dichlorodiphenylsilane PCBs Sample Diphenylsilanediol (DPSDO) Congener Chlorine Manuf. A G H IUPAC # positions #1 2-MoCB 0.036 1.1 #2 3-MoCB 0.049 11 #3 4-MoCB 0.036 8.7 #4 2,2¢-DiCB 0.16 #6 2,3¢-DiCB 1.6 #7 2,4-DiCB #8 2,4¢-DiCB 0.79 #9 2,5-DiCB 0.0071 #11 3,3¢-DiCB 2.1 #13 3,4¢-DiCB 2.8 #15 4,4¢-DiCB 0.98 #28 2,4,4'-TrCB 0.016 MoCBs 0.12 21 DiCBs 8.4 TrCBs 0.016 S PCBs 0.12 30 Blank spaces indicate that none of that component was detected. 0.89 38 33 2.0 13 4.7 11 11 2.3 71 44 120 PCB congeners in diphenylsilanediol (mg/kg) UNINTENTIONAL FORMATION OF PCB FROM CHEMICAL MANUFACTURING PROCESS FeCl3 3,3’-dichlorobenzidine Chlorinated Paraffins Diphenyl Silane diol Organic pigment Concentrations and Congener Profiles of Polychlorinated Biphenyls, Pentachlorobenzene, and Hexachlorobenzene in Commercial Pigments -A report from the Japan Dyestuff and Industrial Chemicals Association (JDICA) revealed that some organic pigments contained a trace of polychlorinated biphenyl (PCB) unintentionally generated in their manufacturing process. - In response to the report, the Ministry of Economy, Trade and Industry (METI) decided to immediately carry out an investigation into the actual situation and, as an urgent measure for the time being, instruct entrepreneurs to stop manufacture, import or shipment of organic pigments found to contain PCB over the international standard (50ppm). Table 1 List of PCBs, PeCBz and HxCBz standards Congener IUPAC # Recovery Homologue 1) Surrogate standards1) PCBs MoCBs DiCBs TrCBs TeCBs PeCBs HxCBs HpCBs OcCBs NoCBs DeCB #3 #15 #28 #60 #101 #141 #178 #194 #208 #209 #8 #32 #70 #97 #153 #180 #205 #206 Chlorobenzenes PeCBz HxCBz 1) denote 13 #32 #32 C12 labeled standards Results PCB congener profiles of azo pigment NaNO2, HCl 3,3’-dichloro benzidine diazonium N-acetoacetyl aniline diazonium pigment production disazo NaNO2, HCl (CuCl2) CB-52(25-25) CB-101(245-25) 2,2’,5,5’- tetrachloro benzidine Sandmeyer reaction Ar-N+≡N + CuX → Ar-X + Cu+ + N2↑ CB-153(245-245) 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> (341082) D2CB / Average 100 #11 (3-3) Intensity 80 60 40 20 0 12 14 16 18 20 22 Retention Time (min) 24 26 28 30 24 26 28 30 (16777200) T4CB / Average 100 #52(25-25) Intensity 80 60 40 20 0 2,2’,5,5 ’- tetrachloro benzidine 12 14 16 18 (225850) P5CB / Average 100 #101(245-25) 80 Intensity 20 22 Retention Time (min) 60 40 20 0 12 14 16 18 20 22 Retention Time (min) 24 (180016) H6CB / Average 100 28 30 #153(245-245) 80 Intensity 26 60 40 20 0 12 14 16 18 20 22 Retention Time (min) 24 26 28 30 PCB congeners in pigment (disazo) permanent yellow lemon; PY81; azo-type pigment CH3 CO CH3 H 3C CH3 CH HNOC CO Cl N=N N=N CH3 Cl CH3 CONH CH Pigment yellow12 (benzidine yellow) Cl raw material Cl H2 N NH2 #11 Cl Cl 3,3’-dichlorobenzidine Cl Cl Cl Cl Cl Cl #35 Cl #77 azo-type pigment CH3 CH3 H 3C HNOC CH3 CO CH Cl CO Cl N=N N=N Pigment yellow81 (benzidine yellow) raw material Cl H2 N CH3 CONH CH Cl Cl CH3 Cl Cl Cl NH2 Cl Cl #52 Cl Cl 2,2’,5,5’-tetrachlorobenzidine Cl Cl Cl Cl Cl Cl Cl Cl #101 Cl Cl #153 Cl azo-type pigment #11 #52 100 ratio(%) 80 60 40 #35 #77 20 0 A A A A A A A a1 a2 a3 a4 a5 a6 a7 A a8 A A A A A #11 #35 #52 #77 #99 B B a9 a10 a11 a12 a13 a14 a15 PCB congener profiles of azo pigment Results PCB congener profiles of phthalocyanine pigment phthalocyanine-type pigment By-product raw material Cl phthalic anhydride urea copper chloride Cl Cl Cl Cl Cl Cl HCB Cl Cl Cl Cl Cl #209 Cl Cl Cl Cl Cl Cl chlorination D pigment green 7 Cl Cl PeCBz pigment blue 15 (phthalocyanine blue) pigment green 7 (phthalocyanine green) Cl Cl Cl Cl Cl Cl Cl Cl Cl #208 Cl highly chlorinated PCBs phthalocyanine-type pigment pigment green 7 100 ratio(%) 80 pigment blue 15 60 40 #209 #208 #207 #206 #202 #11 20 0 A p1 A p2 A A p3 B p4 p5 PCB congener profiles of phthalocyanine pigment 100 80 60 Pigment yellow81 #52 40 20 #101 0 #153 100 80 60 40 #11 #35 #77 pyrazolone ogange 20 0 #209 100 80 60 40 phthalocyanine green 20 0 10 8 6 4 KC400 2 0 Congener pattern PCB congener profiles of diketo-pyrrolo-pyrrole pigments PCB congener profiles of dioxazine violet pigments PV23 o-DCB + Chloranil o-DCB + 3-amino N-ethyl-carbazole o-DCB only o-DCB + Chloranil + 3-amino Nethylcarbazole trace PCB- 40 PCB- 56 PCB- 77 23- 23 23- 34 34- 34 trace PCB- 40 PCB- 56 PCB- 77 23- 23 23- 34 34- 34 150 C o-DCB + V-70L 40min Radical initiator o-DCB + V-70L 20min Radical initiator V-70L : rac-2,2'-Azobis[(2R*)-2,4-dimethyl-4-methoxypentanenitrile] PCB FORMATION FROM PCBz via different PCBz radicals Only one PCB isomer Formation from one PCBz radical one PCB isomer formation Δ V-70L CB-52 (25-25) p-dichlorobenzene Δ V-70L CB155 (246-246) 1,3,5-trichlorobenzene 3 PCB isomers Formation from 2 PCBz radicals CB-56 > CB-77 > CB-40 11 5 CB-5 (23-) CB-56 (23-34) 5 3 CB-12 (34-) CB-77 (34-34) V-70L 2 Δ CB-40 (23-23) o-dichlorobenzene CB-157 > CB-128 > CB-169 CB128 (234-234) Δ V-70L CB-157 (234-345) CB-169 (345-345) 1,2,3-trichlorobenzene CB-157 > CB-128 > CB-169 MCounts 124-TCBz-V70L-40mL-.XMS 360.0>290.0 [-35.0V] Filtered 360.0>290.0 [-35.0V] 15 10 124-TCBz ->HxCB 5 0 MCounts 135-TCBz-V70L-40mL-.XMS 360.0>290.0 [-35.0V] Filtered 360.0>290.0 [-35.0V] 1.25 1.00 135-TCBz ->HxCB 0.75 0.50 CB-157 (234-345) #155 (246-246) 0.25 0.00 kCounts 123-TCBz-V70L-40mL-.XMS 360.0>290.0 [-35.0V] Filtered 360.0>290.0 [-35.0V] 150 123-TCBz ->HxCB 100 CB-169 (345-345) CB128 (234-234) 50 0 MCounts WINDOW-PCB.XMS 360.0>290.0 [-35.0V] Filtered 360.0>290.0 [-35.0V] 200 CB-169 (345-345) CB155 (246-246) 150 Window-PCB 100 50 0 20 25 30 35 trichlorobenzene HxCB 40 45 minutes 6 PCB isomers Formation from 3 PCBz radicals CB-6 > CB-8 > CB-11, CB-13 > CB-4 > CB-15 CB-4 (2-2) CB-6 (2-3) CB-11 (3-3) CB-8 (2-4) CB-15 (4-4) V-70L Δ CB-13 (3-4) chlorobenzene DiCB CB-6 > CB-8 > CB-11, CB-13 > CB-4 > CB-15 MCounts MCBz-V70L-40mL-001.XMS 222.0>152.0 [-30.0V] Filtered 222.0>152.0 [-30.0V] 150 125 #6 (2-3) 100 #13 (3-4) #8 (2-4) #11 (3-3) 75 50 #4 (2-2) #15 (4-4) 25 0 MCounts EC-5433_0.01ppm_611.XMS 222.0>152.0 [-30.0V] Filtered 222.0>152.0 [-30.0V] #10 (26-) 100 75 #4 (2-2) #9 (25-) #8 (2-4) #11 (3-3) #12 (34-) #15 (4-4) 50 25 0 9 10 11 12 13 chlorobenzene DiCB 14 15 minutes CB-68 > CB-47 > CB-73, CB-51 > CB-80 > CB-54 CB-54 (26-26) CB-51 (24-26) CB-73 (26-35) V-70L Δ CB-68 (24-35) CB-80 (35-35) CB-47 (24-24) m-dichlorobenzene #68 #47 kCounts m-DCB-2.74g.xms 292.0>222.0 [-35.0V] Filtered 292.0>222.0 [-35.0V] 80 #51 70 #73 60 50 40 30 20 10 #80 #54 0 kCounts 750 EC-5433_STD_0.01ppm.xms 292.0>222.0 [-35.0V] Filtered 292.0>222.0 [-35.0V] #54 #49 #52 #44 #57 #74 #70 500 #78 #66 #81 250 #77 #79 0 15.0 17.5 20.0 22.5 25.0 m-DCBz TeCB 27.5 30.0 minutes CB-157 > CB-128 > CB-169 CB128 (234-234) Δ V-70L CB-157 (234-345) CB-169 (345-345) 1,2,3-trichlorobenzene CB-157 > CB-128 > CB-169 MCounts 124-TCBz-V70L-40mL-.XMS 360.0>290.0 [-35.0V] Filtered 360.0>290.0 [-35.0V] 15 10 124-TCBz ->HxCB 5 0 MCounts 135-TCBz-V70L-40mL-.XMS 360.0>290.0 [-35.0V] Filtered 360.0>290.0 [-35.0V] 1.25 1.00 135-TCBz ->HxCB 0.75 0.50 CB-157 (234-345) #155 (246-246) 0.25 0.00 kCounts 123-TCBz-V70L-40mL-.XMS 360.0>290.0 [-35.0V] Filtered 360.0>290.0 [-35.0V] 150 123-TCBz ->HxCB 100 CB-169 (345-345) CB128 (234-234) 50 0 MCounts WINDOW-PCB.XMS 360.0>290.0 [-35.0V] Filtered 360.0>290.0 [-35.0V] 200 CB-169 (345-345) CB155 (246-246) 150 Window-PCB 100 50 0 20 25 30 35 trichlorobenzene HxCB 40 45 minutes CB-146, CB-149, CB-135 > CB-153, CB-136, CB-133 CB133 (235-235) CB-135 (235-236) CB-136 (236-236) CB146 (235-245) V-70L Δ CB-149 (236-245) CB-153 (245-245) 1,2,4-trichlorobenzene MCounts 124-TCBz-V70L-40mL-.xms 360.0>290.0 [-35.0V] Filtered 360.0>290.0 [-35.0V] CB-149 (236-245) 15 CB146 (235-245) CB-135 (235-236) 10 CB-136 (236-236) CB133 (235-235) CB-153 (245-245) 5 0 25.0 27.5 30.0 1,2,4-TrCBz HxCB 32.5 minutes - Results - pigment from 3,3’-dichlorobenzidine contain #11, #35, #77 - pigment from 2,2’,5,5’-tetrachlorobenzidine contain #52, #101, #153 - pigment from o-chlorobenzene as solvent contain #40, #56, #77 - phthalocyanine-type pigment contain #209, PeCBz, HCBz - Results Seasonal variations of PCBs, DiCBs, and #11 in ambient air ( Sapporo city, Japan) April 2005 ~ March 2011 50 40 Temp. #11 DiCBs PCBs 1400 1200 1000 800 30 600 20 400 PCBs Conc. (pg/m3) Temperature(oC), DiCBs、#11Conc. (pg/m3) 60 10 200 0 -10 0 -200 Seasonal variations of PCBs, DiCBs, and #11 in ambient air ( Sapporo city : April 2005 ~ March 2011) PCBs: 69-1200 pg/m3, ave:361 pg/m3 #11: 2.4-37 pg/m3, ave:11.4 pg/m3 Jan-11 Oct-10 Jul-10 Apr-10 Jan-10 Oct-09 Jul-09 Apr-09 Jan-09 Oct-08 Jul-08 Apr-08 Jan-08 Oct-07 Jul-07 Apr-07 Jan-07 Oct-06 Jul-06 Apr-06 Jan-06 Oct-05 Jul-05 Apr-05 Ratio (%) Jan-11 Oct-10 Jul-10 Apr-10 Jan-10 Oct-09 Jul-09 Apr-09 Jan-09 Oct-08 Jul-08 Apr-08 Jan-08 Oct-07 Jul-07 Apr-07 Jan-07 Oct-06 Jul-06 Apr-06 Jan-06 Oct-05 Jul-05 Apr-05 Ratio (%) 14 12 Sapporo 10 #11 / ΣPCBs 8 6 4 #52 / ΣPCBs 2 0 20 Muroran 16 12 #11 / ΣPCBs 8 4 #52 / ΣPCBs 0 Anezaki, Nakano :ESPR (2013) Jan-11 Oct-10 Jul-10 Apr-10 Jan-10 Oct-09 Jul-09 Apr-09 Jan-09 Oct-08 Jul-08 Apr-08 Jan-08 Oct-07 Jul-07 Apr-07 Jan-07 Oct-06 Jul-06 Apr-06 Jan-06 Oct-05 Jul-05 Apr-05 Ratio (%) Jan-11 Oct-10 Jul-10 Apr-10 Jan-10 Oct-09 Jul-09 Apr-09 Jan-09 Oct-08 Jul-08 Apr-08 Jan-08 Oct-07 Jul-07 Apr-07 Jan-07 Oct-06 Jul-06 Apr-06 Jan-06 Oct-05 Jul-05 Apr-05 Ratio (%) 100 Sapporo 80 60 #11 / DiCBs 40 20 #52 / TeCBs 0 100 Muroran 80 60 #11 / DiCBs 40 20 0 #52 / TeCBs Anezaki, Nakano :ESPR (2013) - Conclusion use BAT (Best Available Techniques) BEP (Best Environmental Practices) to reduce emissions and human risk. organic pigment product 22,510t (2010) cosmetics - Conclusion organic pigment product 22,510t (2010) use BAT (Best Available Techniques) BEP (Best Environmental Practices) to reduce emissions and human risk. paint ink plastic ICAEC2014 Nov. 24-26, 2014 Chulabhorn Institute Bangkok http://www.j-ec.or.jp/icaec/ http://ee-net.ne.jp/dioxin/ 感谢您的关注 Thank you for your attention Chemical class C.I. name dominant dependent dioxin toxicity dis-azo pyrazolone PY12, PY13, PY14, PY17, PY55, PY83, PY152, PO13, PO16 #11 #35,#77 yes dis-azo phthalocyanine dioxazine diketopyrrolopyrrole naphthol AS naphthol AS PY81 PG7,PG36 PV23,PV37 PR254,PR255 PR9 PR112 #52 #209 #5,#12,#40,#56,#77 #6,#13,#15 #52 #146,#149,#153 #101,#153 #206,#207,#208, etc #1,#16,#20/33, etc #4,#8,#11, etc #18,#31,#101, etc #67,#48,#74,#101,#109,#118 etc no no yes no no yes - Results - pigment from 3,3’-dichlorobenzidine contain #11, #35, #77 - pigment from 2,2’,5,5’-tetrachlorobenzidine contain #52, #101, #153 - pigment from o-chlorobenzene as solvent contain #40, #56, #77 - phthalocyanine-type pigment contain #209, PeCBz, HCBz 3,3’-ジクロロベンジジン (ジアゾニウム塩) 3,3’-ジクロロビフェニル(PCB-11) 3,3’-ジクロロビフェニル(PCB-11) 3,3’,4-トリクロロビフェニル(PCB-35) 3,3’,4,4’-テトラクロロビフェニル(PCB-77) - Conclusion use BAT (Best Available Techniques) BEP (Best Environmental Practices) to reduce POPs emissions. 顔料由来の異性体と 環境試料中のPCB 50 KC300-60 40 PCB製品 0 30 20 10 0 60 Sediment 50 40 底質 30 20 10 PCB-11 0 50 Water 40 水質 30 20 10 0 40 35 30 25 20 15 10 5 0 #37 #35 #33/#20 #31/#28 #25 #26 #16/#32 #18/#17 #15 #12/#13 #11 Air (gas phase) #4 大気 Rain #8/#5 雨水 80 70 60 50 40 30 20 10 0 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) 中野武 50才 Simon Litten 50 KC300-60 40 PCB製品 0 30 20 10 0 60 Sediment 50 40 底質 30 20 10 PCB-11 0 50 Water 40 水質 30 20 10 0 40 35 30 25 20 15 10 5 0 #37 #35 #33/#20 #31/#28 #25 #26 #16/#32 #18/#17 #15 #12/#13 #11 Air (gas phase) #4 大気 Rain #8/#5 雨水 80 70 60 50 40 30 20 10 0 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 底質 河川水 河川水 図 底質、表層水中の2塩素化ビフェニールのSIMクロマトグラム #10/(2,6-)#4(2,2'-), #8(2,4-)/#5(2,3-), #11(3,3'-), #12(3,4-)/#13(3,4'), #15(4,4'-) 角谷ら, 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-11 Pigment discharge 4200 3600 WPCF influent 520 490 Trunk1 18 0.07 Trunk2 12 0.4 Trunk3 12 0.6 Trunk4 3 0.08 Trunk5 1 0.2 PCB-35 380 2.3 0 0.02 0.03 0.04 0.02 PCB-77 PCB-126 TEQ(fg/L) 190 1.6 18000 2.5 0.01 150 0 <0.001 15 0.01 <0.0004 13 0.01 <0.001 8 0.05 <0.001 2 0.04 0.001 1 人工水路3 12ng/L 顔料 排出水 4200ng/L 0.06 0.05 0.04 1 0.8 0.6 0.03 0.02 0.01 0 0.4 0.2 0 PCB-11 PCB-35 PCB-77 PCB-11 PCB-126 PCB-35 PCB-77 PCB-126 人工水路4 3ng/L 排水処理場流入水 520ng/L 0.03 0.025 1 0.8 0.6 0.02 0.015 0.01 人口水路1 18ng/L 0.4 0.2 0.005 0 0 PCB-11 PCB-35 PCB-77 PCB-126 PCB-11 PCB-35 PCB-77 PCB-126 人工水路5 1ng/L 人口水路2 12ng/L 0.25 0.035 0.03 0.025 0.02 0.015 0.01 0.005 0 0.2 0.15 0.1 0.05 0 PCB-11 PCB-35 PCB-77 PCB-126 PCB-11 PCB-35 Simon Litten et al, Chemosphere, 46, 1457-1459(2002) PCB-77 PCB-126 安藤良ら, 名古屋市環境科学研究所所報第38号 31-40(2008) 底質中のPCB分析 表 #11の測定値比較 分析方法 #11(μg/kg) 加圧流体抽出法 0.13 ソックスレー抽出法 0.1 加熱アルカリ分解法(乾泥) 0.3 加熱アルカリ分解法(湿泥) 16 松木司ら, 広島市衛生研究所年報第24号 (2005) PCB-11 加圧流体抽出法 ソックスレー抽出法 加熱アルカリ分解法(乾泥) 加熱アルカリ分解法(湿泥) PCB STD 松木司ら, 広島市衛生研究所年報第24号 (2005) Evidence for Unique and Ubiquitous Environmental Sources of 3,3′Dichlorobiphenyl (PCB 11) Lisa A.Rodenburg, Jia Guo, Songyan Du, and Gregory J.Cavallo Environ. Sci. Technol. 2010, 44, 2816–2821 Inadvertent Polychlorinated Biphenyls in Commercial Paint Pigments Dingfei Hu and Keri C. Hornbuckle Environ. Sci. Technol. 2010, 44, 2822–2827 顔料由来の異性体と 環境大気中のPCB Discovery of non-aroclor PCB (3,3'-dichlorobiphenyl) in Chicago air. Hu D, Martinez A, Hornbuckle KC Environ Sci Technol. 2008 Nov 1; 42(21):7873-7. Fig. 3 Seasonal variations of PCBs, DiCBs and #11 congener in Sapporo city Anezaki et al, organohalogen compounds 74,1433-1436 (2012)