Chemical Characterization of Polychlorinated Biphenyls, -Dibenzo-p-Dioxins, and -Dibenzofurans in Technical Kanechlor PCB Formulations in Japan

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1 Arch. Environ. Contam. Toxicol. 49, (2005) DOI: /s Chemical Characterization of Polychlorinated Biphenyls, -Dibenzo-p-Dioxins, and -Dibenzofurans in Technical Kanechlor PCB Formulations in Japan Takumi Takasuga, 1 Kurunthachalam Senthil Kumar, 1 Yukio Noma, 2 Shinichi Sakai 2 1 Shimadzu Techno Research, #1, Nishinokyo-Shimoaicho, Nakagyo-ku, Kyoto , Japan 2 Research Center for Material Cycles and Waste Management, National Institute for Environmental Studies, 16-2 Onogawa, Tsukuba, Ibaraki , Japan Received: 19 October 2004/Accepted: 9 April 2005 Abstract. Technical polychlorinated biphenyl (PCB) formulations Kanechlor KC-200, KC-300, KC-400, KC-500, KC- 600 and KC-1000 produced in Japan were analyzed for the chemical characterization of PCBs, -dibenzo-p-dioxins (PCDDs), and -dibenzofurans (PCDFs) using high-resolution gas chromatography high-resolution mass spectrometry (HRGC-HRMS) by isotope dilution technique. The homologue/congener profiles of Kanechlor formulations resembled those of Clophen, Aroclor, and Delor, respectively, from Germany, the United States, and Czechoslovakia. Twenty-seven major PCB congeners contributed 50% (in KC-200) to 69 71% (in KC-600, 1000, and 500) to total PCBs. Average total PCB concentrations were 510,000, 800,000, 830,000, 840,000, 870,000, and 880,000 lg/g in KC-1000 (51%), KC-200 (80%), KC-500 (83%), KC-400 (84%), KC-300 (87%), and KC-600 (88%), respectively. Kanechlors also contained PCDDs and PCDFs (4.3 to 0.35 lg/g) as impurities which were approximately 1/10,000 to the PCB concentrations. Congener characterization and concentrations of PCBs and PCDFs were considerably varied in between Kanechlor formulations. The potential for the emissions of PCDDs and PCDFs from Kanechlor was estimated to be 1.94 kg and kg, respectively. The average WHO-toxic equivalent (TEQ) was 16 (KC- 500) >12 (KC-400) >10 (KC-1000) >4.1 (KC-600) >3.5 (KC- 300) >1.9 (KC-200) on lgteq/g. Non- and mono-ortho PCBs were the major contributors to the total TEQ in Kanechlor formulations, whereas the PCDD/DF contribution was <2.0%. The environmental input of TEQs from Kanechlors can be estimated to be between 112 and 941 kg. Polychlorinated biphenyls (PCBs) are a class of 209 congeners, manufactured commercially by progressive chlorination of biphenyl in the presence of a suitable catalyst (e.g., iron chloride). Depending on the reaction conditions, the degree of Correspondence to: Kurunthachalam Senthil Kumar; chlorination can vary between 21 and 68% (w/w) (Ahlborg et al. 1992). In particular, PCBs were produced for applications such as flame-resistant oils in transformers and capacitors, as heat transfer medium, and as plasticizers in paint and sealants. Unlike PCBs, polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are formed from municipal solid waste incinerators (MSWI) (Abad et al. 2000), industrial solid waste incinerators (ISWI) (Addink et al. 1998a, 1998b; Kim et al. 2004), impurities from agrochemicals (Harnly et al. 2000; Masunaga et al. 2001) as well as impurities from PCB technical formulations (Takasuga 2001; Takasuga et al. 1996, 2002, 2003, 2005; Kim et al. 2004). PCB congener-specific data are also available for technical PCB mixtures such as Aroclors, Kanechlors, Clophens, Chlorofen, and Sovol (Ballschmiter and Zell 1980; Mullin et al. 1984; Schulz et al. 1989; Ivanov and Sandell 1992; Kannan et al. 1992, 1997; Frame 1997; Taniyasu et al. 2003); nevertheless, these studies report gas chromatography (GC) electron capture detection (ECO) and/or high-resolution gas chromatography low-resolution mass spectrometry (HRGC-LRMS) data. Despite the ban on the production of PCBs in industrialized countries more than years ago, PCBs continue to be detected in environmental as well as biological samples. Temporal trends in environmental concentrations of PCBs tend to be attributed to the patterns of PCB production and usage (Loganathan and Kannan 1991, 1994; Kannan et al. 1992, 2000). PCBs can be degraded by combustion, photolysis, biodegradation (Dietrich et al. 1995; Triska et al. 2004), and chemical decomposition (Takasuga et al. 2002) and lead to the formation of toxic PCDFs. Therefore, production and usage data for PCBs are important to predict future perspectives relating to environmental behaviors. Kanegafuchi Chemical Industry Co., Ltd., Japan produced commercial Kanechlor PCB formulations from 1954to The cumulative Kanechlor production by Kanegafuchi was approximately 56,326 tons and by Mitsubishi, Japan is 2461 tons (Tatsukawa 1976; Tanabe 1988; Breivik et al. 2002). Commercial PCBs were sold on the basis of their physical properties, not their chemical composition. Different batches of commercial formulations may vary somewhat in their composition.

2 386 T. Takasuga et al. Studies on the chemical characterization of PCBs, PCDDs, and PCDFs in individual Kanechlor formulations are not available. Consequently, in the present investigation, homologue and congener-specific characterization of chlorobiphenyls (CB), including non-ortho coplanar PCBs, was carried out in the technical PCB formulations Kanechlor 200, 300, 400, 500, 600, and Kanechlors were also analyzed for occurrence of PCDDs and PCDFs, which are expected to be present as impurities. Therefore, we adopted isotope dilution technique and HRGC-HRMS for target compounds analysis. To our knowledge, this is the first study characterizing PCBs, PCDD/DFs, and their toxic equivalent (TEQ) from different Kanechlor formulations by HRGC-HRMS after rigorous quality assurance/quality control (QA/QC) with ultratrace (<1 ng/g) level. hold for 2 min, 2 C/min to 280 C, hold for 33.5 min (DB-17HT and SP-2331). The temperature programs for PCBs used are as follows: 120 C for 1 min, 40 C/min to 200 C, hold for 2 min, 6 C/min to 320 C, hold for 5 min (for non-ortho PCBs); 70 C for 1 min, 40 C/ min to 190 C, 1 C/min to 240 C, 10 C/min to 310 C, hold for 9 min (for mono-/di-ortho and ortho PCBs). The temperatures of the injector and the ion source were 280 C and 250 C, respectively. The interface temperature was programmed as 5 10 C higher than the maximum value of each temperature program. The carrier gas was helium and the electron impact ionization energy was ev. The selected ion monitoring (SIM) mode was used and the resolution was kept higher than 12,000 (5% valley) in an attempt to reduce the interference of fragment ions from higher chlorinated PCBs with lower chlorinated congeners. Two ions were monitored for each congener group, and isotope ratios were compared to the theoretical values. Individual congeners were identified by comparison to reference standard solutions and published data. Materials and Methods Kanechlor Formulations and Analysis The technical Kanechlor (KC-) PCB formulation (n = 29) was obtained from different laboratories in Japan without opening of the seal or mixing with any solvents due to the strict regulation of PCBs in Japan (Takasuga et al. 2003). Particularly, we selected KC-200 (n = 2), KC-300 (n = 6), KC-400 (n = 7), KC-500 (n = 6), KC-600 (n = 6), and KC-1000 (n = 2) stored in different laboratories. Individual congener and congener group analyses were performed from 1 g of the Kanechlor formulation. Briefly, Kanechlor formulation was initially dissolved in n-hexane containing 10% toluene (Takasuga et al. 2002). The 13 C 12 -labeled internal standards such as 39 major PCBs (including 12 co-planar PCBs), C 12 -labeled 2,3,7,8-chlorine substituted PCDDs/PCDFs, and 13 C 12 -labeled 1,3,6,8-TCDD/ TCDF (Takasuga et al. 2002) were spiked and then subjected into sequence of alumina oxide column cleanup and carbon dispersed silicagel column cleanup. Except for non-ortho PCBs, other PCBs were analyzed prior to alumina oxide cleanup, whereas PCDD/DFs and non-ortho PCBs were analyzed after carbon dispersed silicagel column cleanup. The injection recovery standards for PCBs were 13 C 12 -labeled IUPAC nos. 70, 111, 138, and 170, whereas injection recovery standards for PCDDs and PCDFs were 13 C 12 -labeled 1,2,3,4- TeCDD (Takasuga et al. 2003). The detailed analytical procedure has been described in our earlier studies (Takasuga et al. 1992, 1995, 1996, 2002, 2003, 2005; Yao et al. 2002; Kannan et al. 1987). HRGC/HRMS Analysis For identification and quantification, HRGC (HP6890, Hewlett Packard)/ -HRMS (Autospec Ultima, Micromass) fitted with DB-5MS column (60 m, 0.32 mm i.d. x 0.25-lm film thickness, J&W Scientific) was used for total PCBs and coplanar PCBs quantification. In addition, HT8-PCB column (60 m x 0.25 mm i.d. SGE), was employed for some PCB congener analysis, whereas the SP-2331 (Supelco) column, DB-17HT (J&W Scientific; 0.25 mm i.d. x 60 m length), and DB-5MS (J&W Scientific; 0.25 mm i.d. x 60 m length) columns were used to separate 17 2,3,7,8-substituted PCDD/DF congeners in which the congeners being interfered in DB-5MS were quantified in DB-17HT and SP An autosampler (GC System Injector, Hewlett Packard) was employed for injection (2 ll, on column). The temperature programs used for PCDD/DF determination are as follows: 160 C for 3 min, 40 C/min to 200 C, hold for 2 min, 2 C/min to 310 C (DB-5MS); 160 C for 3 min, 40 C/min to 220 C, Results and Discussion PCBs in KC-MIX HRGC analysis of Kanechlor formulations revealed a presence of all 39 major PCB congeners including non- and mono-ortho coplanar PCBs with the detection limit of <1 lg/g, representing mono- through deca-cb isomers/congeners (Table 1). For quality assurance, blank (n = 3) samples analyzed do not contain quantifying amounts of any PCBs. Chlorobiphenyl isomers/congeners results in this study identical to Aroclors (technical PCB formulation of United States), Clophen (technical PCB formulation of Germany), Chlorofen (technical PCB formulation of Poland), Sovol (technical PCB formulation of Russia), and Delor (technical PCB formulation of Czechoslovakia) were found in Kanechlor formulations (Mullin et al. 1984; Kannan et al. 1987, 1992; Tanabe et al. 1987; Schulz et al. 1989; Falandysz et al. 1992; Takasuga et al. 2003, 2005; Taniyasu et al. 2003; Kim et al. 2004). The concentrations of major (predominant) PCB congeners, total PCBs (mono- through decachlorobiphenyl homologues), and coplanar PCBs are listed in Table 1. The maximum average total PCBs concentration (880,000 lg/g) was noticed in KC- 600 followed by KC-300 (870,000 lg/g), KC-400 (840,000 lg/g), KC-500 (830,000 lg/g), KC-200 (800,000 lg/g), and KC-1000 (510,000 lg/g). The lower levels in KC-1000 suggest the inclusion of considerable proportions of trichlorobenzenes (TrCBzs) in technical formulation. Major PCBs Among analyzed PCBs, 27 of mono- through decachlorinated biphenyls are considered to be major PCBs due to their average relative abundance of 18% (range: % in each homologue group) to the total PCBs. The major PCBs comprised 50 51% (in KC-200), 54 59% (in KC-300), 55 56% (in KC-400), 68 72% (in KC-500), 69 70% (in KC- 1000), and 68 74% (in KC-600) of the total PCBs (Table 1; Figure 1). A greater contribution by major PCBs in KC- 500, 1000, and 600 was of major concern if they were used at a greater proportion in technical PCB formulations by

3 Table 1. Mean (range) concentrations (lg/g) of mono- through deca-pcbs in Kanechlor formulations Kanechlor formulation IUPAC No. Chlorine positions KC-200 (n = 2) KC-300 (n = 6) KC-400 (n = 7) KC-500 (n = 6) KC-1000 (n = 2) KC-600 (n = 6) Major PCBs #3 4-MoCB 83,000(80,000 86,000) 160 (< ) 84 (< ) 25 (<0.3 47) 12 (11 12) 25 (< ) #8 24 -DiCB 67,000 (65,000 68,000) 66,000 (58,000 80,000) 5300 ( ) 2100 ( ) 1000 ( ) 1400 ( ) # DiCB 17,000 (17,000) 12,000 (< ,000) 1200 (< ) 420 (< ) 270 ( ) 180 (< ) # TrCB 48,000 (47,000 49,000) 93,000 (84,000 96,000) 31,000 (25,000 36,000) 3800 ( ) 2000 ( ) 2000 ( ) #31/ TrCB/244 -TrCB 76,000 (75,000 76,000) 130,000 68,000 (52,000 76,000) 6100 ( ) 3500 ( ) 3100 ( ) (120, ,000) # TrCB 32,000 (31,000 32,000) 56,000 (51,000 65,000) 20,000 (13,000 23,000) 2400 ( ) 1400 ( ) 1200 ( ) # TeCB 17,000 (15,000 18,000) 26,000 (23,000 31,000) 52,000 (45,000 58,000) 13,000 (10,000 15,000) 8200 ( ) 1700 ( ) # TeCB 16,000 (15,000 16,000) 26,000 (21,000 28,000) 59,000 (52,000 70,000) 38,000 (32,000 43,000) 24,000 (24,000) 3300 ( ) # TeCB 15,000 (14,000 15,000) 27,000 (20,000 33,000) 51,000 (44,000 57,000) 6500 ( ) 4500 ( ) 2000 ( ) # TeCB 16,000 (16,000) 28,000 (21,000 33,000) 63,000 (58,000 69,000) 22,000 (18,000 25,000) 14,000 (13,000 14,000) 2800 ( ) # PeCB 2700 ( ) 4500 ( ) 20,000 (17,000 22,000) 61,000 (53,000 66,000) 39,000 (38,000 40,000) 18,000 (16,000 20,000) # PeCB 3100 ( ) 5300 ( ) 22,000 (20,000 24,000) 77,000 (70,000 80,000) 48,000 (46,000 50,000) 22,000 (19,000 23,000) # PeCB 1600 ( ) 2900 ( ) 12,000 (6,400 15,000) 21,000 (19,000 23,000) 14,000 (13,000 14,000) 2100 ( ) # PeCB 3300 (3300) 5800 ( ) 26,000 (20,000 29,000) 77,000 (72,000 83,000) 48,000 (45,000 51,000) 9,000 ( ,000) # PeCB 2400 ( ) 4300 ( ) 17,000 (10,000 20,000) 54,000 (49,000 57,000) 33,000 (30,000 35,000) 4600 ( ) # HxCB 1400 ( ) 2600 ( ) 5300 ( ) 66,000 (57,000 75,000) 39,000 (35,000 42,000) 44,000 (41,000 47,000) # HxCB 890 ( ) 1600 ( ) 3900 ( ) 48,000 (40,000 52,000) 30,000 (28,000 31,000) 80,000 (72,000 90,000) # HxCB 940 ( ) 1800 ( ) 3900 ( ) 49,000 (43,000 52,000) 30,000 (26,000 33,000) 83,000 (75,000 88,000) # HpCB 270 ( ) 680 ( ) 1200 ( ) 8400 ( ) 5300 ( ) 44,000 (40,000 46,000) # HpCB 140 ( ) 290 (37 440) 650 ( ) 4800 ( ) 3200 ( ) 48,000 (43,000 50,000) # HpCB 360 ( ) 760 ( ) 1700 ( ) 10,000 ( ,000) 6500 ( ) 110,000 (90, ,000) # HpCB 130 ( ) 240 (41 360) 670 ( ) 3800 ( ) 2500 ( ) 56,000 (46,000 64,000) # OcCB 65 (43 87) 180 ( ) 400 (94 730) 980 ( ) 680 ( ) 21,000 (19,000 23,000) # OcCB 46 (37 54) 100 ( ) 310 ( ) 720 ( ) 530 ( ) 26,000 (22,000 29,000) # OcCB 59 (46 71) 130 ( ) 360 ( ) 940 ( ) 680 ( ) 28,000 (24,000 34,000) # NoCB 21 (15 27) 60 ( ) 120 (19 240) 230 (38 400) 160 (95 220) 5100 ( ) # DeCB 6.0 ( ) 3.1 ( ) 6.1 (1.6 10) 9.4 (4.2 15) 5.5 ( ) 64 (49 77) Sum major PCBs 400,000 (400,000) 500,000 (480, ,000) 470,000 (420, ,000) 580,000 (530, ,000) 360,000 (340, ,000) 610,000 (550, ,000) Monochlorobiphenyls 250,000 (240, ,000) 650 ( ) 270 ( ) 75(45 130) 34(25 43) 85 (34 210) Dichlorobiphenyls 130,000 (130,000) 110,000 (97, ,000) 9300 ( ,000) 3700 ( ) 1800 ( ) 2,000 ( ) Trichlorobiphenyls 250,000 (250,000) 460,000 (430, ,000) 170,000 20,000 (15,000 28,000) 11,000 (10,000 12,000) 10,000 ( ,000) (130, ,000) Tetrachlorobiphenyls 140,000 (140,000) 250,000 (200, ,000) 470, ,000 (90, ,000) 64,000 (64,000) 18,000 ( ,000) (430, ,000) Pebtachlorobiphenyls 19,000 (19,000) 35,000 (17,000 44,000) 160,000 (130, ,000) Hexachlorobiphenyls 5300 ( ) 10,000 ( ,000) 24,000 (14,000 31,000) 390,000 (360, ,000) 270,000 (250, ,000) 240,000 (220, ,000) 170,000 (160, ,000) 61,000 (50,000 77,000) 320,000 (290, ,000) Heptachlorobiphenyls 1200 ( ) 2600 ( ) 5600 ( ) 39,000 (33,000 45,000) 25,000 (24,000 26,000) 360,000 (320, ,000) Octachlorobiphenyls 230 ( ) 540 (36 980) 1400 ( ) 3500 ( ) 2500 ( ) 100,000 (90, ,000) Nonachlorobiphenyls 26 (15 36) 70 ( ) 170 (33 310) 300 (41 500) 210 ( ) 7400 ( )

4 Table 1. Continued Kanechlor formulation IUPAC No. Chlorine positions KC-200 (n = 2) KC-300 (n = 6) KC-400 (n = 7) KC-500 (n = 6) KC-1000 (n = 2) KC-600 (n = 6) Decachlorobiphenyl 6 ( ) 3.12 ( ) 6.1 (1.6 10) 9.4 (4.2 15) 5.5 ( ) 64 (49 77) Sum total PCBs 800, ,000 (820, ,000)840,000 (770, ,000)830,000 (760, ,000)510,000 (480, ,000)880,000 (790,000 1,000,000) (790, ,000) Coplanar PCBs # TeCB 2000 ( ) 3900 ( ) 5800 ( ) 750 ( ) 450 ( ) 270 ( ) # TeCB 100 (93 110) 170 ( ) 260 ( ) 24 (11 41) 38 (27 48) 13 (4.1 28) # PeCB 10 (8.7 12) 19 (8.5 24) 72 (30 86) 22 (18 28) 18 (17 19) 12 (2.5 43) # HxCB ( )0.05 ( ) 0.22 ( ) 0.45 ( ) 0.28 ( ) 0.11 ( ) # PeCB 1600 ( ) 2900 ( ) 12,000 ( ,000) 21,000 (19,000 23,000) 14,000 (13,000 14,000) 2100 ( ) # PeCB 120 ( ) 230 (98 290) 1000 ( ) 1200 ( ) 750 ( ) 130 (67 320) # PeCB 2400 ( ) 4300 ( ) 17,000 (10,000 20,000) 54,000 (49,000 57,000) 33,000 (30,000 35,000) 4600 ( ) # PeCB 100 (89 110) 160 (58 190) 690 ( ) 1000 ( ) 880 ( ) 540 ( ) # HxCB 220 (220) 530 (43 810) 970 ( ) 8800 ( ,000) 5200 ( ) 3300 ( ) # HxCB 49 (48 50) 120 ( ) 230 (54 380) 1900 ( ) 1100 ( ) 260 ( ) # HxCB 73 (71 74) 150 (16 230) 290 (93 460) 3,000 ( ) 1800 ( ) 1100 ( ) # HpCB 13 (13) 32 (1.2 56) 45 (11 78) 310 ( ) 180 (180) 910 ( ) Sum coplanar PCBs 6600 ( ) 12,000 ( ,000) 39,000 (21,000 47,000) 93,000 (85,000 98,000) 56,000 (53,000 60,000) 13,000 ( ,000) The values are founded. Kanegafuchi Chemical Industry, Co., Ltd. Based on the available reports (Y. Noma, unpublished data), the production of KC-300 and KC-500 was comparatively higher than other formulations. The major PCBs and indicator PCBs estimation has also been established by European nations in 1987 and was updated in 2001 (Deutsches Institut fur Normung e. V. 1987). Based on this method, the estimation of total PCBs from the major PCBs is possible but not qualitative. Nevertheless, based on the major PCBs data, the estimation of total PCBs was found to be impossible. If this is the case, analysis of total PCBs can be estimated based on the major PCB congener concentrations that were determined in the present study. Among major PCBs, IUPAC-3, IUPAC-31/28, IUPAC-8, and 2IUPAC-18 were predominant in KC-200. IUPAC-31/28, IUPAC-18, IUPAC-8, and IUPAC-33 were predominant in KC-300. IUPAC-31/28, IUPAC-66, IUPAC-52, IUPAC-43 were predominant in KC-400. In KC-500 and 1000, IUPAC- 110, IUPAC-101, IUPAC-138, and IUPAC-95 were prevalent. However, in KC-600, IUPAC-180, IUPAC-153, IUPAC-149, IUPAC-187, and IUPAC-174were prevalent (Table 1 and Figure 1). A similar congener pattern has been noticed in Aroclor, Clophen, and Delors (Ballschmiter and Zell 1980; Mullin et al. 1984; Schulz et al. 1989; Ivanov and Sandell 1992; Takasuga et al. 2002; Taniyasu et al. 2003). Homologue Profiles of PCBs The homologue profiles of major (predominant) PCBs in Kanechlor formulations were about 88% (Table 1). The remaining 12% of PCBs might be lost during dilutions of the Kanechlor formulations during analysis. In addition, uncertain analytical errors such as standard dilution, sample weight measurement, standard solution purity, varied sensitivity of PCB congeners, standard deviation of calibration mixture, and HRGC-HRMS conditions should not be ignored. Based on homologue composition, the approximate chlorine contents of Kanechlor 200, 300, 400, 500, 1000, and 600 were estimated to be 34.5%, 43.1%, 48.5%, 55.3%, 55.4%, and 60.8%, respectively. Mono-/tri-CB homologues ( 30% each) were prevalent in KC-200, whereas tri-/tetra- ( 70%), tetra- (>50%), penta- ( 40%), hexa-/hepta- ( 60%), and penta-/ hexa- ( 70%) were prevalent homologues in KC-300, 400, 500, 600, and 1000, respectively (Figure 2). It is noteworthy that homologue profiles of Kanechlor (KC-300, KC-400, KC- 500, and KC-600) resembled those of Clophen (A-30, A-40, A-50, and A-60), Aroclor (1016, 1248, 1254, and 1260), Delors (103, 104, 105, and 106), respectively (Takasuga et al. 2002; Mullin et al. 1984; Schulz et al. 1989). Coplanar PCBs The concentrations of coplanar PCBs (the sum of four nonortho and eight mono-ortho PCBs that contain WHO-TEFs that were established in 1998 [Van den Berg et al. 1998]) contributed from 0.84% to 11.19% to the total PCBs (Table 1, Figure 3). The average concentrations of coplanar PCBs were 6600, 12,000, 39,000, 93,000, 56,000, and 13,000 lg/g, for

5 Technical Kanechlor PCBs in Japan 389 Fig.1. Percentage contributions of major PCBs to the total PCBs in Kanechlor formulations Kanechlor 200, 300, 400, 500, 1000, and 600, respectively (Table 1). Percent contribution of coplanar PCBs was 0.84 ( in KC-200), 1.42 ( in KC-300), 4.65 ( in KC-400), ( in KC-500), ( in KC-1000), and 1.50 ( in KC-600) to the total PCBs. It is prominent that IUPAC-118, IUPAC-105, IUPAC-156, and IUPAC-77 were prevalent coplanar PCBs in all Kanechlor formulations (Figure 3). The congener pattern of coplanar PCBs was dominated by IUPAC-118, IUPAC-77, and IUPAC-105 in KC-200, KC-300, and KC-400. In KC-500, 600, and 1000 but more so IUPAC-156, the congener pattern is similar to other formulations, but IUPAC-77 contributed less. In general, coplanar PCBs pattern has been similar to or less than those measured in Delor, Aroclor, Clophen, and/or Kanechlor (Takasuga et al. 2002; Taniyasu et al. 2003). The formulation-dependent concentration was also noticed for coplanar PCBs, with similar reasons discussed for major PCBs. PCDD/DFs in KC-MIX The concentrations and homologue profiles of PCDDs and PCDFs in Kanechlor samples are shown in Table 2 and Figure 4, respectively. For quality assurance, blank (n = 3) samples analyzed do not contain quantifying amounts of PCDDs and PCDFs. When compared to the PCB concentrations, the levels of PCDDs and PCDFs were several magnitudes less (1/ 10,000). The maximum concentrations were noticed in KC- 400 (15 lg/g) followed by KC-600 (8.7 lg/g), KC-500 (7.8 lg/ g), KC-1000 (7.1 lg/g), KC-300 (5.6 lg/g), and KC-200 (3.2 lg/g). Occurrence of PCDFs at ppm levels in Aroclors, Kanechlors, and Delor has been reported (Wakimoto et al. 1988; Taniyasu et al. 2003). When total PCDDs (including non 2,3,7,8-congeners) were considered, KC-500 contained 0.10 lg/g concentrations followed by KC-600 (0.074 lg/g), KC-1000 (0.02 lg/g), KC-400 (0.016 lg/g), KC-200 (0.006 lg/g), and KC-300 (0.002 lg/g). Only KC-400, 500, and 600 contained all PCDD homologues, whereas OCDD was less than the detection limit in KC-200, 300, and For total PCDFs (including non 2,3,7,8- congeners), average concentrations were noticed in KC-400 (15 lg/g) followed by KC-600 (8.6 lg/g), KC-500 (7.7 lg/g), KC-1000 (7.1 lg/g), KC-300 (5.6 lg/g), and KC-200 (3.2 lg/ g). TeCDFs and PeCDF homologues were abundant in KC- 200, KC-300, and KC-400 (Figure 4). HxCDF followed by PeCDF and HpCDF was abundant in KC-500 and KC-1000, whereas OCDF followed HxCDF and PeCDF was prevalent in

6 390 T. Takasuga et al. Fig.2. Contribution (%) of PCB homologues in Kanechlor formulations Fig.3. Concentrations (lg/g) and congener patterns of coplanar PCBs in Kanechlor formulations KC-600 (Figure 4). On the basis of median concentrations of PCDDs (0.033 lg/g) and PCDFs (7.9 lg/g) and the approximate cumulative production estimates of Kanechlor (58,787 tons), the total PCDD and PCDFs formation from the use of Kanechlor can be estimated to be 1.94 and kg, respectively. PCDF homologues (only 2,3,7,8-congeners) were the predominant impurities rather than PCDD (only 2,3,7,8-congeners). Only HpCDDs and OCDDs were noticed in KC-400, 500, 1000, and 600 formulations at trace levels when the seven 2,3,7,8-PCDDs congener is concerned. 2,3,7,8-PeCDFs and TeCDFs contributed more than 60% in KC-200, 300, and 400, whereas PeCDFs and TeCDFs were equivalently contributed (>75%) in KC ,3,7,8-HxCDFs, HpCDFs, OCDF were the prevalent (>50%) PCDF congeners in KC-500 and 600. Taniyasu et al. (2003) reported PCDFs in Delor-104, Delor- 105, and Delor-106. According to their observation, PeCDFs were the predominant homologue group rather than TeCDF, HxCDF, and HpCDF. Congener, specifically, 2,3,4,7,8-PeC- DF, was prevalent in KC-200, KC-300, and KC-400. The 1,2,3,4,7,8-HxCDF was the abundant congener in KC-500 and KC-1000, whereas OCDF was the predominant in KC-600, and 1,2,3,7,8,9-HxCDF was the least contaminant in all PCB formulations. Other predominant PCDF congeners are 1,2,3,4,6,7,8-HpCDF, 1,2,3,4,7,8,9-HpCDF, 2,3,7,8-TCDF, and 2,3,4,6,7,8-HxCDF.

7 Technical Kanechlor PCBs in Japan 391 Table 2. Concentrations ((lg/g) of PCDDs and PCDFs in Kanechlor formulations Kanechlor formulations PCDD/DFs KC-200 (n = 2) KC-300 (n = 6) KC-400 (n = 7) KC-500 (n = 6) KC-1000 (n = 2) KC-600 (n = 6) 2,3,7,8-TeCDD <0.001 <0.001 <0.001 <0.001 <0.001 < ,2,3,7,8-PeCDD <0.001 <0.001 < (0.001) <0.001 < ,2,3,4,7,8-HxCDD <0.001 <0.001 <0.001 <0.001 <0.001 < ,2,3,6,7,8-HxCDD <0.001 <0.001 < (0.003) <0.001 < ,2,3,7,8,9-HxCDD <0.001 <0.001 < (0.003) < (0.003) 1,2,3,4,6,7,8-HpCDD <0.001 < (0.005) ( ) (0.002) ( ) OCDD <0.001 < ( ) ( ) < ( ) 2,3,7,8-TeCDF ( ) 0.07 ( ) 0.24 ( ) ( ) ( ) ( ) 1,2,3,7,8-PeCDF ( ) 0.03 ( ) 0.12 ( ) ( ) ( ) ( ) 2,3,4,7,8-PeCDF 0.11 ( ) 0.15 ( ) 0.54 ( ) 0.21 ( ) 0.23 ( ) 0.27 ( ) 1,2,3,4,7,8-HxCDF ( ) 0.14 ( ) 0.31 ( ) 0.80 ( ) 0.68 ( ) 0.42 ( ) 1,2,3,6,7,8-HxCDF ( ) 0.04( ) 0.09 ( ) 0.20 ( ) 0.19 ( ) 0.11 ( ) 1,2,3,7,8,9-HxCDF < ( ) 0.01 ( ) 0.02 ( ) ( ) ( ) 2,3,4,6,7,8-HxCDF ( ) ( ) 0.04 ( ) ( ) ( ) 0.1 ( ) 1,2,3,4,6,7,8-HpCDF ( ) 0.089( ) 0.09 ( ) 0.30 ( ) 0.26 ( ) 0.38 ( ) 1,2,3,4,7,8,9-HpCDF ( ) 0.09 ( ) ( ) 0.34 ( ) 0.27 ( ) 0.32 ( ) OCDF ( ) 0.16 ( ) 0.16 ( ) 0.23 ( ) 0.25 ( ) 2.5 ( ) TeCDDs ( ) ( ) 0.004( ) 0.01 ( ) (0.006) ( ) PeCDDs (0.002) ( ) ( ) 0.05 ( ) 0.011(0.011) ( ) HxCDDs (0.0032) < ( ) ( ) (0.012) ( ) HpCDDs (0.0029) < ( ) ( ) 0.004(0.004) ( ) OCDD <0.001 < ( ) ( ) < ( ) Sum PCDDs ( ) (< ) ( ) 0.10 ( ) 0.02 (< ) ( ) TeCDFs 2.1 (2.1) 3.5 (2 5) 9.1 (2.5 22) 1.4( ) 1.2 ( ) 0.92 ( ) PeCDFs 0.72 ( ) 1.1 ( ) 4.3 ( ) 1.7 ( ) 1.8 ( ) 1.5 (1 2.4) HxCDFs 0.23 ( ) 0.54 ( ) 1.2 ( ) 3.1 ( ) 2.9 ( ) 1.8 ( ) HpCDFs 0.10 ( ) 0.29 ( ) 0.36 ( ) 1.2 ( ) 0.99 ( ) 1.9 ( ) OCDF ( ) 0.16 ( ) 0.16 ( ) 0.23 ( ) 0.25 ( ) 2.5 ( ) Sum PCDFs 3.2 (3.2) 5.6 ( ) 15 (4.5 31) 7.7 (3.8 12) 7.1 ( ) 8.6 (6.9 10) Sum PCDD/DFs 3.21 ( ) 5.6 ( ) 15 (4.5 31) 7.8 (3.8 12) 7.12 ( ) 8.7 (7.0 10)

8 392 T. Takasuga et al. Fig.4. Contribution (%) of PCDD and PCDF homologues in Kanechlor formulations Laboratory-specific (Kanechlor obtained from different laboratories) differences of PCDFs were noticed, which is in contrast to total PCBs. Furthermore, the composition of PCDD/PCDFs in between the same KC formulations was considerably varied. Although there exist quantitative differences in the composition of minor constituents, there was a qualitative similarity between Kanechlors and correspondingly similar technical PCB formulations. The differences in the composition of minor compounds could arise from differences in the boiling point fractionations of PCB mixtures during manufacturing. Furthermore, these results indicate that formation of PCDFs during Kanechlor production may be related to the presence of impurities of PCDFs in raw materials, rather than to the processing conditions. In addition, the varied congener pattern in Kanechlor formulations can also be explained as the temperature and reaction difference of PCB formulations. Toxic Equivalency The 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) of coplanar PCBs (non- and mono-ortho PCB congeners) and 2,3,7,8-chlorine-substituted PCDD/DFs were calculated using the World Health Organization's (WHO) mammalian toxic equivalency factors (TEFs) that were established in 1998 (Van den Berg et al. 1998). TEQ concentrations and the congener contribution to the total TEQ were shown in Table 3 and Figure 5. The maximum TEQ was noticed for KC- 500 (16 lg/g), followed by KC-400 (12 lg/g), KC-1000 (10 lg/g), KC-600 (4.1 lg/g), KC-300 (3.5 lg/g), and KC-200 (1.9 lg/g). These results suggest that exposure to Kanechlor 500, 400, and 1000 may result in higher toxic impacts, due to the greater concentrations of coplanar PCBs found in these formulations. Based on the total TEQ concentrations in Kanechlors and their cumulative production, the potential for the emission of TEQs from Kanechlors can be estimated to be between 112 and 941 kg (mean: 473 kg; median: 423 kg). The WHO-TEQ concentrations in Delors formulations were reported with a range of 781 to 4190 ng/g (Taniyasu et al. 2003) in which PCDFTEQ contribution was similar to PCBs TEQ (e.g., Delor 104) and much less (e.g., Delors 105 and 106). Non-ortho PCBs were prevalent (60 70% to the total TEQ) in KC-200, 300, and 400 (Figure 5). In particular, PeCB-126 contributed more than 50% of the TEQ followed by HxCB- 156, PeCB-118, and PeCB-105. Mono-ortho PCBs were major accumulants (85%) in KC-500, 600, and KC-1000 (Figure 5). Especially, PeCB-118 and HxCB-156 contributed more than 60% in these formulations. The TEQ contribution by PCDDs and PCDFs was very low, with less than 2% in all the samples (Figure 5). In particular, PCDDs were never noticed in any of the Kanechlor samples as TEQ contributors, and their influence in this regard could be negligible. Apart from the PCB isomers, 2,3,7,8-TeCDF, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8- HxCDF, and 2,3,4,6,7,8-HxCDF also contributed to the TEQ with less than 2% (Figure 5). In conclusion, quantitative characterization of Kanechlors KC-300, 400, 500, and 600 suggests their resemblance to Aroclor 1016, 1248, 1254, and 1260, Clophen A-30, A-40, A- 50, and A-60, and Delors 103, 104, 105, and 106, respectively, in terms of homologue composition and chlorination levels. In addition, concentrations and profiles of PCDDs and PCDFs in Kanechlors were presented. Such an analysis will be useful to estimate emission inventories on a per-congener basis and to track sources of exposures by fingerprinting of the congener profiles.

9 Technical Kanechlor PCBs in Japan 393 Table 3. WHO TEQ concentrationw ((lg/g) by PCDDs, PCDFs, and coplanar PCBs in Kanechlor formulations Kanechlor formulations PCDD/DFs KC-200 (n = 2) KC-300 (n = 6) KC-400 (n = 7) KC-500 (n = 6) KC-1000 (n = 2) KC-600 (n = 6) PCDD/DFs 2378-TeCDD PeCDD HxCDD HxCDD HxCDD HpCDD OCDD TeCDF 0.004( ) ( ) 0.024( ) ( ) ( ) ( ) PeCDF ( ) ( ) ( ) ( ) ( ) ( ) PeCDF ( ) 0.08 ( ) 0.27 ( ) 0.11 ( ) 0.12 ( ) 0.14 ( ) HxCDF ( ) ( ) ( ) 0.08 ( ) 0.07 ( ) 0.04 ( ) HxCDF (0.002) 0.004( ) ( ) 0.02 ( ) 0.02 (0.02) 0.01 ( ) HxCDF ( ) ( ) ( ) ( ) ( ) HxCDF (0.001) ( ) ( ) 0.006( ) ( ) 0.01 ( ) HpCDF ( ) ( ) ( ) ( ) ( ) ( ) HpCDF ( ) ( ) ( ) ( ) ( ) ( ) OCDF ( ) CoplanarPCBs TeCB # ( ) 0.39 ( ) 0.58 ( ) 0.08 ( ) ( ) 0.03 ( ) TeCB # ( ) 0.02 ( ) 0.03 ( ) ( ) ( ) ( ) PeCB # ( ) 1.9 ( ) 7.2 ( ) 2.2 ( ) 1.8 ( ) 1.2 ( ) HxCB# ( ) ( ) ( ) ( ) (0.003) ( ) PeCB # ( ) 0.29 ( ) 1.2 ( ) 2.1 ( ) 1.4 ( ) 0.21 ( ) PeCB # ( ) 0.11 ( ) 0.50 ( ) 0.61 ( ) 0.38 ( ) 0.07 ( ) PeCB # ( ) 0.43 ( ) 1.7 ( ) 5.4 ( ) 3.3 ( ) 0.46 ( ) PeCB # ( ) 0.02 ( ) ( ) 0.10 ( ) 0.09 ( ) ( ) HxCB# (0.11) 0.27 ( ) 0.48 ( ) 4.4 ( ) 2.6 ( ) 1.6 ( ) HxCB# ( ) 0.06 ( ) 0.11 ( ) 0.94 ( ) 0.55 ( ) 0.13 ( ) HxCB # (0.001) ( ) ( ) 0.03 ( ) 0.02 (0.02) ( ) HpCB # (0.001) ( ) ( ) 0.03 ( ) (0.018) ( ) PCDD TEQ ( ) ( ) PCDF TEQ 0.07 (0.07) 0.11 ( ) 0.35 ( ) 0.23 ( ) 0.22 ( ) 0.22 ( ) NO 1 PCBs TEQ 1.25 ( ) 2.3 ( ) 7.8 ( ) 2.3 ( ) 1.9 ( ) 1.2 ( ) MO 2 PCBs TEQ 0.60 ( ) 1.2 ( ) 4.1 ( ) 14 (12 15) 8.3 ( ) 2.7 ( ) Total TEQ 1.91 ( ) 3.5 ( ) 12 (5.5 15) 16 (14 17) 10 (9.6 11) 4.1 ( ) TEQ with below detection limit are considered as zero; 1 Indicates non-ortho PCBs and 2 denotes mono-ortho PCBs.

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