Congener-Specific Composition of Polychlorinated Naphthalenes

Feb 13, 2004 - Total TEQs roughly estimated from the Japanese production of technical PCNs, 210 kg-TEQ, was about half from technical PCBs, 440 kg-TEQ...
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Environ. Sci. Technol. 2004, 38, 1675-1680

Congener-Specific Composition of Polychlorinated Naphthalenes, Coplanar PCBs, Dibenzo-p-dioxins, and Dibenzofurans in the Halowax Series YUKIO NOMA,* TAKASHI YAMAMOTO, AND SHIN-ICHI SAKAI National Institute for Environmental Studies, 16-2, Onogawa, Tsukuba, Ibaraki 305-8506 Japan

Concentrations and congener compositions of polychlorinated naphthalenes (PCNs), coplanar polychlorinated biphenyls (Co-PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs) were determined in seven Halowax (HW) preparations. In HW 1000 and 1031, lowchlorinated naphthalenes (CNs) and in HW 1051, highly chlorinated naphthalenes were dominant, whereas tri- through penta-CNs were major homologues in other Halowaxes. Concentrations of Co-PCBs were in the range of 2.0-2600 ng/ g. CB 105 and 118 were dominant in all Halowaxes. Concentrations of PCDDs/DFs were in the range of 925900 ng/g. The 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQs) in Halowaxes calculated from the amounts of PCNs, Co-PCBs, and PCDDs/DFs were in the range of 2800220 000 ng-TEQ/g. PCNs accounted for most of the total TEQs in Halowaxes, and the contribution of PCDDs/DFs and Co-PCBs to total TEQs was less than 1/1000 that of PCNs. Congeners that most significantly contributed to TEQs were CN 69, 73, 70, and 63. Total TEQs roughly estimated from the Japanese production of technical PCNs, 210 kgTEQ, was about half from technical PCBs, 440 kg-TEQ on average.

Introduction Polychlorinated naphthalenes (PCNs) are ubiquitous environmental pollutants that are structurally similar to polychlorinated biphenyls (PCBs), polychlorinated dibenzo-pdioxins (PCDDs), and dibenzofurans (PCDFs). There are 75 possible congeners based on the naphthalene ring with one to eight chlorine atoms. PCNs have been used as cable insulation, wood preservatives, engine oil additives, electroplating masking compounds, and in dye production (1). Typical technical PCN formulations were Halowaxes (Koppers Company, U.S.A.), Nibren waxes (Bayer, Germany), Seekay waxes (ICI, UK), Clonacire waxes (Prodelec, France), and Cerifal (Caffaro, Italy). The production and use of PCNs were banned in the U.S. and Europe in the 1980s due to their toxicity and environmental persistence (2). The worldwide production of PCNs is estimated at approximately 150 000 metric tons (3). Numerous studies have been carried out on homologue and congener profiles of technical PCN prepara* Corresponding author phone: +81-29-850-2846; fax: +81-29850-2840; e-mail: [email protected]. 10.1021/es035101m CCC: $27.50 Published on Web 02/13/2004

 2004 American Chemical Society

tions (4-16). Wiedmann et al. reported homologue profiles of PCNs in Halowax (HW) 1014 (4). Nakano et al. analyzed equiamount mixtures of the HW series using capillary column gas chromatography with two different stationary phases and reported on the congener profiles of PCNs (5). Imagawa et al. synthesized several congeners of tetra- through hexachloronaphthalenes (CNs) and carried out congenerspecific analysis of PCNs in the HW series (6-8). Congenerspecific analysis using high-resolution gas chromatographyhigh-resolution mass spectrometry (HRGC-HRMS) was also carried out in equiamount mixtures of the HW series (9). Falandysz et al. have recently reported the congener profiles of PCNs in seven HW preparations (10). However, detailed congener profiles of PCNs in HW preparations are not available from those references for the following reasons: (i) equiamount mixtures or only one HW preparation (mainly HW 1014) were analyzed as typical, (ii) only homologue or limited congener (mainly tetra- through hexa-CNs) profiles were determined, and (iii) the detection methods adopted using a flame ionization detector (FID), electron capture detector (ECD), atomic emission detector (AED), and low resolution mass spectrometry (LRMS) were less reliable than HRMS. As Falandysz noted (3), the full congener-specific analysis results of all seven Halowax formulations are not still available. It has been recognized that PCNs show dioxin-like toxicities because of their structural similarity to dioxins. The 2,3,7,8-tetrachlorodibenzo-p-dioxin relative potency factors (RPFs) of individual CN congeners have been estimated using their ethoxyresorufin-O-deethylase (EROD) activity or aryl hydrocarbon receptor (AhR)-mediated activity (17-20). The dioxin-like toxicities of PCNs in environmental samples are estimated using these RPFs (21-23). To estimate the dioxin-like toxicities or to resolve the sources of PCNs found in environmental samples, there is a need for congenerspecific analysis in PCN preparations to be carried out. Furthermore, since technical PCN formulations may contain PCBs, PCDDs, and PCDFs as impurities in the same way as PCB formulations contain PCNs (24-26), there is a need for congener-specific analysis of PCBs, PCDDs, and PCDFs in PCN formulations. To evaluate accurately the dioxin-like toxicities of the Halowax mixtures, the contribution of possible by-side impurities such as PCBs, PCDDs, and PCDFs have to be elucidated also. In this study, concentrations and congener compositions of PCNs, coplanar PCBs (Co-PCBs), and PCDDs/DFs in seven Halowax preparations (1000, 1001, 1013, 1014, 1031, 1051, and 1099) were individually analyzed by isotope dilution using HRGC/HRMS. The 2,3,7,8-tetra-CDD toxic equivalents (TEQs) of specific CN congeners in each Halowax were estimated according to the relative potencies of Ah receptor-mediated responses. The TEQs of PCDDs/DFs and Co-PCBs in each Halowax were calculated using World Health Organization (WHO)-TEFs, and their compositions were also presented. In addition, total TEQs from the production of technical PCNs were estimated and compared to those of technical PCBs in Japan.

Materials and Methods Halowax-Kit RCS-076 for analysis was obtained from Foxboro Co. (MA, U.S.A.). The lot numbers of the Halowaxes tested were J296C (HW 1000), J296D (HW 1001), J296F (HW 1013), J296G (HW 1014), J296B (HW 1031), J296H (HW 1051), and J296E (HW 1099). PCN-MXB for PCNs standard solution was purchased from Wellington Laboratories Inc. (Ontario, Canada). Isotope-labeled PCN standard solution, 1,2,3,4VOL. 38, NO. 6, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

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tetrachloro[13C10]naphthalene, 1,2,3,5,7-pentachloro[13C10]naphthalene, 1,2,3,4,5,7- hexachloro[13C10]naphthalene, 1,2,3,4,5,6,7-heptachloro[13C10]naphthalene, and 1,2,3,4,5,6,7,8octachloro[13C10]naphthalene were purchased from Cambridge Isotope Laboratories Inc. (MA, U.S.A.). A set of PCDDs/ DFs calibration solutions (DF-CVS-B10-Set 2), cleanup spike solution (DF-LCS-A200), and syringe spike solution (DF-ISF200) were purchased from Wellington Labs. A set of CoPCBs calibration solutions (PCB-CVS-A10-Set 3), cleanup spike solution (PCB-LCS-A200), and syringe spike solution (PCB-IS-B100) were also purchased from Wellington Labs. All solvents and reagents were of dioxin analysis grade and purchased from Kanto Chemicals (Tokyo, Japan). Chemical Analysis. For PCNs analysis, individual HW preparations (10 mg) were dissolved in 100 mL of hexane and diluted 100 times with hexane. The diluted HW solution was spiked with the isotope-labeled internal standards solution and then measured by HRGC/HRMS. Peaks were identified using information from Nakano et al. (5) and quantified by isotope dilution. For the analysis of tetra- through octa-CDDs/DFs and nonortho PCBs, individual HW preparations (100 mg) were dissolved in 200 mL of hexane. The HW solution was spiked with a cleanup spike solution and then treated with concentrated sulfuric acid, passed through a silica gel column (3 g, eluted with 150 mL of hexane), an alumina column (10 g, washed with 100 mL of 2% dichloromethane/hexane, recovered with 160 mL of 50% dichloromethane/hexane), and a carbon-impregnated silica gel column (1 g, washed with 200 mL of 25% dichloromethane/hexane, recovered with 200 mL of toluene). The sample was concentrated to 100 µL, spiked with syringe spike solution, and quantified by HRGC/ HRMS. For the analysis of mono-ortho PCBs, further applications were necessary due to interference from bulk PCNs. The sample, after being passed through a silica gel column, was fractioned via an alumina column (10 g, washed with 40 mL of hexane, recovered with 100 mL of 5% dichloromethane/ hexane) and subjected to HPLC (Gilson Inc.) fitted with a Hypercarb column (Hypersil, 100 × 4.6 mm i.d., bead size 5 µm). The fraction containing mono-ortho PCBs was recovered with 20 mL of 50% dichloromethane/hexane. This fraction was concentrated and spiked with a syringe spike solution and then measured by HRGC/HRMS. PCN and PCB congeners are represented by their IUPAC numbers throughout this manuscript. HRGC/HRMS measurements were carried out with an Agilent Model 6890 gas chromatograph coupled with a JEOL JMS-700 mass spectrometer. For the measurements of PCNs, an Agilent Ultra 2 capillary column (25 m × 0.2 mm i.d., df ) 0.33 µm) was used. For mono- through tetra-CNs, the column oven temperature was programmed from 70 to 250 °C at a rate of 8 °C/min and then to 320 °C at 20 °C/min, with a final hold time of 2 min. For penta- through octa-CNs, the column oven temperature was programmed from 70 to 310 °C at a rate of 8 °C/min, with a final hold time of 8 min. For the measurements of tetra- through hexa-CDDs/DFs, a Supelco SP-2331 column (60 m × 0.25 mm i.d., df ) 0.2 µm) was used. The column oven temperature was programmed from 100 to 150 °C at a rate of 20 °C/min and then to 261 °C at 3 °C/min and held for 12 min, to 273 °C at 3 °C/min, with a final hold time of 1.5 min. For the measurements of hepta- and octa-CDDs/DFs, a J&W DB-5MS column (30 m × 0.25 mm i.d., df ) 0.25 µm) was used. The column oven temperature was programmed from 100 to 250 °C at a rate of 15 °C/min and then to 290 °C at 5 °C/min, with a final hold time of 6 min. For the measurements of Co-PCBs, a SGE HT-8 column (50 m × 0.22 mm i.d., df ) 0.25 µm) was used, and the column oven temperature was programmed from 130 to 220 °C at a rate of 20 °C/min and then to 320 °C at 1676

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FIGURE 1. Homologue profiles of PCNs in Halowaxes. 5 °C/min, with a final hold time of 4.5 min. The injector temperature was 200 °C (for PCNs) or 270 °C (for PCDDs/ DFs and Co-PCBs). The injection volume was 1 µL. Helium was used as the carrier gas. The mass spectrometer was operated at an electron impact (EI) energy of 38 eV. Mass resolution was over 10 000.

Results and Discussion PCNs. Homologue profiles of PCNs in Halowaxes are shown in Figure 1. The chlorine contents of Halowaxes were 35.0% (HW 1000), 49.0% (HW 1001), 53.9% (HW 1013), 58.7% (HW 1014), 27.5% (HW 1031), 69.7% (HW 1051), and 50.9% (HW 1099). In HW1000, the predominating homologues were di-CNs (76.5%) and mono-CNs (14.9%). The major homologues were tri-CNs (52.0%) and tetra-CNs (41.3%) in HW 1001; tetra-CNs (53.8%) and penta-CNs (26.7%) in HW1013, penta-CNs (51.9%) and hexa-CNs (23.1%) in HW 1014; monoCNs (65.1%) and di-CNs (29.6%) in HW 1031; octa-CNs (81.8%) and hepta-CNs (17.5%) in HW 1051; and tetra-CNs (49.9%) and tri-CNs (38.3%) in HW 1099. The ratio of higher chlorinated homologues rose with increasing chlorine content in HW. There were several differences with Brinkman’s results for the HW series (1); for example, the quantities of

TABLE 1. Concentrations of PCN Congeners in Halowaxes mg/ga congener

PCN no.

HW 1000

HW 1001

HW 1013

HW 1014

HW 1031

HW 1051

HW 1099

naphthalene 211,31,4-/1,61,5-/2,72,6-/1,71,22,31,81,3,6-/1,3,51,3,7-/1,4,61,2,41,2,51,2,61,2,71,6,7-/2,3,61,2,31,3,81,4,51,2,81,3,5,71,2,5,7-/1,2,4,6-/1,2,4,71,3,6,71,4,6,71,3,6,8-/1,2,5,61,2,3,5-/1,3,5,81,2,3,61,2,3,4-/1,2,3,71,2,6,71,2,4,52,3,6,7-/1,2,4,81,2,5,8-/1,2,6,81,4,5,81,2,3,81,2,7,81,2,3,5,7-/1,2,4,6,71,2,4,5,71,2,4,6,81,2,3,4,61,2,3,5,61,2,3,6,71,2,4,5,61,2,4,7,81,2,3,5,8-/1,2,3,6,81,2,4,5,81,2,3,4,51,2,3,7,81,2,3,4,6,7-/1,2,3,5,6,71,2,3,4,5,7-/1,2,3,5,6,81,2,3,5,7,81,2,4,5,6,8-/1,2,4,5,7,81,2,3,4,5,61,2,3,4,5,81,2,3,6,7,81,2,3,4,5,6,71,2,3,4,5,6,81,2,3,4,5,6,7,8total

2 1 4 5/7 6/12 11/8 3 10 9 20/19 21/24 14 15 16 17 25/26 13 22 23 18 42 37/33/34 44 47 45/36 28/43 29 27/30 39 32 48/35 38/40 46 31 41 52/60 58 61 50 51 54 57 62 53/55 59 49 56 66/67 64/68 69 71/72 63 65 70 73 74 75

0.017 13 130 16 400 130 100 43 5.0 40 5.1 32 9.5 2.0 1.1 1.7 0.078 0.18 0.044 9.3 0.87 0.67 3.5 ND 0.93 0.17 1.5 ND 0.17 0.12 0.23 1.3 2.8 1.4 0.034 0.13 0.41 0.038 0.46 0.15 0.043 ND 0.55 0.72 0.71 1.1 0.040 0.0062 0.079 0.29 0.65 1.4 0.25 0.50 ND 0.081 0.62 0.14 960

0.00009 0.036 1.2 0.18 28 3.1 2.7 0.71 0.059 0.33 31 280 47 13 6.1 13 0.62 0.79 0.20 110 10 15 80 ND 22 4.1 54 ND 6.1 3.5 8.9 51 97 58 1.5 5.4 3.5 0.61 0.89 2.1 0.67 ND 3.8 6.7 7.5 1.7 1.4 0.31 0.026 0.089 0.17 0.44 0.047 0.15 ND 0.015 0.048 0.068 985

0.00008 0.012 0.29 0.039 3.7 0.54 0.39 0.15 0.010 0.10 3.4 110 13 2.2 1.3 1.5 0.077 0.14 0.024 20 1.3 8.4 120 ND 32 4.5 47 ND 4.6 2.7 6.5 49 150 86 1.2 4.6 14 1.8 35 9.4 3.0 ND 21 35 35 95 6.2 0.77 0.71 2.4 5.2 13 1.6 4.8 ND 0.19 1.0 0.11 960

0.00006 0.0091 0.24 0.034 3.1 0.50 0.36 0.14 0.0069 0.19 1.9 17 4.3 1.0 0.42 0.73 0.059 0.087 0.022 9.4 1.1 2.2 37 ND 14 1.6 16 ND 1.6 0.73 3.2 14 58 20 0.35 2.4 51 6.6 0.65 21 6.6 ND 72 95 98 140 7.9 1.1 6.3 23 45 98 16 34 ND 5.2 23 1.1 963

0.012 56 560 5.6 170 48 36 13 0.89 6.9 1.9 13 2.6 0.75 0.58 0.93 0.074 0.066 0.0068 4.4 0.44 0.87 4.8 ND 1.2 0.26 2.5 ND 0.33 0.24 0.40 2.3 5.1 2.6 0.056 0.40 0.29 0.038 0.58 0.15 0.058 0.0051 0.31 0.57 0.47 1.0 0.074 0.022 0.015 0.049 0.11 0.23 0.033 0.075 ND 0.04 0.11 0.28 947

0.00013 0.0016 0.015 0.0003 0.0064 0.0027 0.0018 0.0006 ND ND 0.0012 0.0098 0.0031 0.0006 0.0007 0.0010 ND ND ND 0.0030 0.0004 0.0010 0.0058 ND 0.0015 ND 0.0030 ND 0.0009 ND ND 0.0028 0.0057 0.0029 ND 0.0005 0.089 0.0095 0.11 0.033 0.011 ND 0.12 0.17 0.15 0.34 0.023 0.0038 0.91 0.59 1.3 2.9 0.16 0.052 ND 33 140 810 990

0.00009 0.013 0.24 0.031 12 0.75 0.71 0.16 0.012 0.059 22 210 34 9.2 5.3 9.3 0.52 0.55 0.098 81 7.5 16 91 ND 27 5.5 61 ND 7.6 4.1 9.1 60 130 73 1.6 8.0 6.7 1.0 16 3.9 1.7 ND 7.3 13 13 30 2.6 0.69 0.25 0.69 1.4 2.4 0.44 0.71 ND 0.10 0.39 0.13 990

RPFb 1.8 × 10-5 c 1.7 × 10-5 c 2.0 × 10-8 c 1.8 × 10-8 d

2.7 × 10-5

c

2.1 × 10-5 c 8.0 × 10-6 e

6.8 × 10-5 1.7 × 10-4 1.6 × 10-6

c f d

4.6 × 10-5 d 2.5 × 10-3 f 1.0 × 10-3 g 2.0 × 10-3 g 3.5 × 10-6 g 2.0 × 10-3 g 1.1 × 10-3 3.0 × 10-3

d g

a ND; nondetectable, detection limits were 0.00005 (naphthalene), 0.0002 (mono-CNs, di-CNs, tri-CNs), 0.0005 (tetra-CNs, penta-CNs, hexa-CNs), 0.001 mg/g (hepta-CNs, octa-CNs), respectively. b For unresolved peaks, average of RPFs was used. c RPFs were from ref 20. d RPFs were from ref 18. e RPF was from ref 21. f RPFs were from ref 19. g RPFs were from ref 17.

mono-CNs and di-CNs in HW 1000 were reversed. Our results closely matched Imagawa’s results for the HW series using AED (7), with the single exception of the abundance of diCNs and tri-CNs in HW 1000. The profile was quite similar to Harner’s results for HW 1014 using FID (12); but the levels of penta-CNs and hexa-CNs were reversed. The closest matching result was obtained with Wiedmann’s report on HW 1014 using HRMS (4), except for the abundance of octa-

CNs. The homologue profiles of HW 1051 were similar to those reported by Kannan et al. using LRMS (13). Congener-specific analytical results of PCNs in Halowaxes are presented in Table 1 and Figure 2. CN 44, CN 29, and CN 70 were not found in any of the HW preparations. The chief congeners were CN 5/7 (41.7%) and 6/12 (13.5%) in HW 1000; CN 21/24 (28.5%) and 23 (11.6%) in HW 1001; CN 38/40 (15.6%) and 37/33/34 (12.5%) in HW 1013; CN 59 (14.5%) VOL. 38, NO. 6, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

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FIGURE 2. Congener profiles of PCBs in Halowaxes.

TABLE 2. Total TEQs of PCNs, Co-PCBs, and PCDDs/DFs in Halowaxes TEQ (ng/g)

HW 1000

HW 1001

HW 1013

HW 1014

HW 1031

HW 1051

HW 1099

PCNs Co-PCBs PCDDs/DFs total

5700 0.67 4.3 5700

2800 0.00029 1.3 2800

26000 0.050 36 26000

220000 0.13 210 220000

11000 0.23 1.5 11000

100000 0.021 5.1 100000

8700 0.0086 4.7 8700

and 71/72 (10.1%) in HW 1014; CN 1 (59.1%) and CN 5/7 (18.0%) in HW 1031; CN 75 (81.8%) and CN 74 (14.1%) in HW 1051; and CN 21/24 (21.2%) and 38/40 (13.1%) in HW 1099. Among all the HW preparations, alpha (1-,4-,5-,8-) chlorinated congeners were predominant, whereas the beta (2,3-,6-,7-) chlorinated congeners, thought to be of combustion origin, such as CN 10, 16, 17, 45, 39, 51, 54, 66/67 appeared as minor species. Falandysz et al. have presented the charts 1678

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of congener profiles normalized by the most abundant congener in each homologue (10). Compared with their reports, the congener profiles in Halowaxes were similar except in some details: specifically, much lower levels of CN 9 in the 7 HW series and reversed ratios of CN 5/7 to 9 in HW 1000, CN 59 to 53/55 in HW 1001, and CN 37/33/34 to 38/40 in HW 1031. The congener profile in HW1001 and 1014 closely matched the reports (8, 12, 14). The reason that congener

FIGURE 3. TEQs of PCN congeners in Halowaxes. and homologue profiles of PCNs are different between our results and previous studies, for one thing, may be from the analytical procedures. In this study, we quantified PCN congeners by HRMS with an isotope dilution technique. This method can effectively eliminate the interferences from the contaminants in HW and is thought of as more reliable than FID, ECD, and LRMS used in previous studies. Another reason is the variation of PCNs contents in HW among the lots used for analyses. As Kodavanti et al. reported the differences in PCB congener profiles between the different lots of Aroclor 1254 (26), PCN congener profiles are likely different between the different lots of HW. Co-PCBs. The concentrations of Co-PCBs in Halowaxes were 2600 ng/g (HW 1000), 2.0 ng/g (HW 1001), 110 ng/g (HW 1013), 360 ng/g (HW 1014), 1800 ng/g (HW 1031), 99 ng/g (HW 1051), and 40 ng/g (HW 1099), respectively. HW 1000 and 1031 contained the highest levels of Co-PCBs; it was interesting that they showed lower chlorine contents. As for congener profiles of Co-PCBs, CB 105 (2,3,3′,4,4′-) and 118 (2,3′,4,4′,5-) predominated in most HW preparations. Other major congeners were CB 77 (3,3′,4,4′-) in HW 1001, CB 156 (2,3,3′,4,4′,5-) in HW 1051, and CB 123 (2′,3,4,4′,5-) in HW 1099.

PCDDs and PCDFs. The concentrations of PCDDs/DFs in Halowaxes were 240 ng/g (HW 1000), 92 ng/g (HW 1001), 1200 ng/g (HW 1013), 5900 ng/g (HW 1014), 180 ng/g (HW 1031), 430 ng/g (HW 1051), and 250 ng/g (HW 1099), respectively. HW 1014 and 1013 contained higher levels of PCDDs/DFs than others. The concentrations of 2,3,7,8substituted congeners were 110 ng/g (HW 1000), 16 ng/g (HW 1001), 290 ng/g (HW 1013), 1600 ng/g (HW 1014), 110 ng/g (HW 1031), 300 ng/g (HW 1051), and 55 ng/g (HW 1099), respectively. In HW 1000 and 1031, octa-CDD was dominant. 2,3,7,8-tetra-CDF was the major congener in HW 1001, 1099, 1013 and 1014. In Halowax 1051, octa-CDF was the most abundant congener. Toxic Potential. The 2,3,7,8-tetra-CDD toxic equivalents in HW preparations were calculated from the amounts of PCNs, Co-PCBs, and PCDDs/DFs present. When calculating TEQs from specific CN congeners, RPFs were used from the refs 17-21. WHO-TEFs were used for the calculation of TEQs of Co-PCBs and PCDDs/DFs. TEQs of PCNs were 2800220 000 ng-TEQ/g (Table 2). HW 1014 gave the highest TEQ, followed by HW 1051 and 1013. Congeners that contributed significantly to TEQs were CN 69, 73, 70, and 63 (Figure 3). TEQs of Co-PCBs were in the range of 0.00029-0.67 ngTEQ/g (Table 2). HW 1000 gave the highest TEQs, followed by HW 1031 and 1014. CB 126, 118, 105, and 156 accounted for the large proportions of TEQs. TEQs of PCDDs/DFs were in the range of 1.3-210 ng-TEQ/g (Table 2). HW 1014, followed by HW 1013, gave the highest TEQs values. 2,3,7,8tetra-CDF, 1,2,3,7,8-penta-CDF, and 2,3,4,7,8-penta-CDF were major contributors to TEQs. Total TEQs of dioxin-like compounds in Halowaxes were 2800-220 000 ng-TEQ/g. PCN congeners accounted for almost the entire TEQs value. The contribution of PCDDs/DFs and Co-PCBs to total TEQs was less than 1/1000 that of PCNs. From these results and the Japanese production (4000 metric tons) of technical PCNs preparations (27), the total TEQs in PCNs preparations were estimated as 11-880 kg-TEQ (average; 210 kg-TEQ). As for the TEQ values of technical PCBs preparations, we analyzed PCDDs/DFs and Co-PCBs accurately in different lots of Kanechlor preparations (Kanegafuchi Chemicals Industry Co. Ltd., Japan) and estimated their TEQs values (28). The TEQs in the Kanechlors were 1900-16 000 ng-TEQ/ g. From these results and the Japanese production rate (59 000 metric tons) of technical PCBs preparations (29), total TEQs in PCBs preparations are estimated to be 110-940 kg-TEQ (average; 440 kg-TEQ). The roughly estimated total TEQs from PCNs are about half from PCBs on average, although the production of PCBs is about 10 times that of PCNs. In the environmental samples, on the other hand, it was reported that contribution of PCBs and PCNs to sum TEQs in fishes collected from Michigan waters were 86% and 14%, respectively (21). This shows the contribution of PCNs is six times less than that of PCBs. The estimated TEQs from the production might be different from those of the environmental emissions. Further studies are necessary in order to clear the detailed contribution of the environmental emissions. In many countries, PCBs wastes are now scheduled to be stored and destructed; however, PCNs wastes are still not effectively managed. Therefore, it is necessary to know the state of use of PCNs and to investigate and eliminate the routes of PCNs into the environment.

Literature Cited (1) Brinkman, U. A. Th.; Reymer, H. G. M. J. Chromatogr. 1976, 127, 203-243. (2) Hayward, D. Environ. Res. 1998, 76, 1-18. (3) Falandysz, J. Environ. Pollut. 1998, 101, 77-90. (4) Wiedmann, T.; Ballschmiter, K. Fres. J. Anal. Chem. 1993, 346, 800-804. (5) Nakano, T.; Fujimori, K.; Takaishi, Y.; Umeda, H. Report Hyogo Prefectural Institute Environ. Sci. 1993, 25, 34-41 (in Japanese). VOL. 38, NO. 6, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

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Received for review October 5, 2003. Revised manuscript received January 9, 2004. Accepted January 12, 2004. ES035101M