Approach to Highly Efficient Dechlorination of PCDDs, PCDFs, and

Chemistry, Politehnica University of Bucharest, Spl. Independentei No. 313, Section 6, Bucharest, Romania. HIDEKI TASHIRO AND MASASHI TASHIRO...
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Environ. Sci. Technol. 2004, 38, 1216-1220

Approach to Highly Efficient Dechlorination of PCDDs, PCDFs, and Coplanar PCBs Using Metallic Calcium in Ethanol under Atmospheric Pressure at Room Temperature YOSHIHARU MITOMA, TAIZO UDA, AND NAOYOSHI EGASHIRA* Department of Bioscience Development, School of Bioresources, Hiroshima Prefectural University, 562 Nanatsuka-cho, Shobara City, Hiroshima, 727-0023 Japan CRISTIAN SIMION Department of Organic Chemistry, Faculty of Industrial Chemistry, Politehnica University of Bucharest, Spl. Independentei No. 313, Section 6, Bucharest, Romania HIDEKI TASHIRO AND MASASHI TASHIRO Loker Hydrocarbon Research Institute, University of Southern California, 837 Bloom Walk, LHI, Los Angeles, California 90089-1661 XIAOBO FAN Taihei, Environmental Science Center, 2-2-31, Kanenokuma, Hakata-ku, Fukuoka, 816-0063, Japan

Detoxification of highly toxic polychlorinated aromatic compounds such as polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and dioxin-like compounds such as coplanar polychlorinated biphenyls (co-PCBs) under mild conditions(atmospheric pressure and room temperature) was achieved by a simple stirring operation for 24 h using metallic calcium in ethanol, without any tedious decomposition procedures and harsh conditions such as high temperature and/or high pressure. Metallic calcium can be kept stable under atmospheric conditions for a long period as compared to metallic sodium since the surface is coated with CaCO3, which is formed in the contact with air. Moreover, ethanol, which is one of the safest solvents for humans, acts not only as a solvent but also as an accelerator due to its ablility to remove the carbonated coating. This decomposition method for PCDDs, PCDFs, and co-PCBs therefore is one of the most economical and environmentally friendly detoxification methods with respect to the input energy and safety of reagents used. Concentration for each isomer of PCDDs, PCDFs, and coPCBs was reduced in 98.32-100% conversions by treatment in ethanol at room temperature. The toxicity equivalency quantity (TEQ), which was measured by the HRGC-HRMS analysis, for the total residues of isomers was reduced from 22 000 to 210 pg TEQ/mL of hexane

* Corresponding author phone: +81-8247-4-1748; fax: +81-82474-1748; e-mail: [email protected]. 1216

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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 38, NO. 4, 2004

(conversion: 99.05%) at room temperature. By refluxing over 24 h, the conversion increased up to 99.45%.

Introduction PCDDs and PCDFs, for which the generic term of dioxins is used, and polychlorobiphenyls (PCBs) are known as highly toxic and mutagenic compounds for human beings (1-4). Many methods for the decomposition of PCDDs, PCDFs, and PCBs have been consequently developed. For example, the techniques of decomposition by combustion with or without oxygen gas at high temperature (5, 6), vitrification (7), oxidative treatment using supercritical water (8, 9), and dehalogenation by hydroxide using KOH in DMI (1,3dimethyl-2-imidazolidinone) with heating (10) seemed to present some success for detoxification. However, these methods, which involve high temperature and/or highpressure conditions, have some disadvantages in recovering the vaporized dioxins and PCBs, in driving up operating costs, and in incurring the high risk of de novo synthesis of dioxins. On the other hand, a few methods using mild conditions, such as an alkali metal like metallic sodium in oil (11), bioremediation method (12), and mechanochemical systems by energy emission from collisions between metallic small balls (13) were proposed. However, these methods also present some unfavorable aspects concerning the use of dangerous reducing reagents such as metallic sodium, low decomposition rates, throughput, or efficiency. Thus far, we have been investigating the dehalogenation of organic compounds employing Zn powder/aqueous HCl or NaOH solutions (14, 15) and Ni-Al alloy/10% aqueous alkaline NaOH solution (16). Recently, we revealed that a powerful method for the dechlorination of PCBs was the use of Ni-Al alloy in a 0.5∼1% aqueous alkaline KOH or NaOH solution (17). Moreover, in a series of our research on dehalogenation processes, we discovered that metallic calcium in ethanol was effective for the dechlorination of PCBs to give the dechlorinated compounds in 99.96% yields at ambient temperature (18). Therefore, we applied this method to the dechlorination of dioxins under almost identical conditions. As a result of our investigations, it turned out that this system (metallic calcium in ethanol) as a reducing reagent acts effectively in the decomposition of dioxin. To the best of our knowledge, there is no report regarding a highly efficient dechlorination of dioxins employing metallic calcium under atmospheric pressure and at room temperature. In this paper, we report the first example of highly efficient dechlorination of dioxins using metallic calcium in ethanol under mild conditions. And then, the efficiency of the detoxification is also discussed by means of the evaluation of total TEQ of 7 PCDDs, 10 PCDFs, and 12 co-PCBs.

Experimental Section General. Distilled water was used in all reactions. Commercially available (Wako Pure Chemicals Industry, Ltd.) ethanol was used. Granular particles of metallic calcium (Kishida Chemical, Co. Ltd.) were directly introduced in the reaction without any pretreatment. 4-Chlorobiphenyl (>99.0%, GC) was purchased from Tokyo Kasei Co., Ltd. PCDDs, PCDFs, and co-PCBs in fly ash were extracted with hexane. Then the extract was condensed to 22 000 pg TEQ/ mL of hexane. In this paper, 7 PCDDs (2,3,7,8-tetraCDD, 1,2,3,7,8pentaCDD, 1,2,3,4,7,8-hexaCDD, 1,2,3,6,7,8-hexaCDD, 1,2,3,10.1021/es034379b CCC: $27.50

 2004 American Chemical Society Published on Web 01/15/2004

7,8,9-hexaCDD, 1,2,3,4,6,7,8-heptaCDD, 1,2,3,4,6,7,8,9-hctaCDD); 10 PCDFs (2,3,7,8-tetraCDF, 1,2,3,7,8-pentaCDF, 2,3,4,7,8-pentaCDF, 1,2,3,4,7,8-hexaCDF, 1,2,3,6,7,8-hexaCDF, 1,2,3,7,8,9-hexaCDF, 2,3,4,6,7,8-hexaCDF, 1,2,3,4,6,7,8-heptaCDF, 1,2,3,4,7,8,9-heptaCDF, 1,2,3,4,6,7,8,9-octaCDF); and 12 co-PCBs (3,4,4′,5-tetraCB, 3,3′,4,4′-tetraCB, 3,3′,4,4′,5pentaCB, 2′,3,4,4′,5-pentaCB, 2,3′,4,4′,5-pentaCB, 2,3,3′,4,4′pentaCB, 2,3,4,4′,5-pentaCB, 3,3′,4,4′,5,5′-hexaCB, 2,3′,4,4′,5,5′hexaCB, 2,3,3′,4,4′,5-hexaCB, 2,3,3′,4, 4′,5′-hexaCB, 2,3,3′,4,4′,5,5′-heptaCB) were measured by the GC-MS method in order to evaluate the total TEQ. co-PCBs usually include diorthosubstituted congeners. However, their TEFs were decided as zero at WHO/IPCS in 1998 (19, 20). Therefore, we omitted the di-substituted compounds. Typical Procedure for the Dechlorination of 4-Chlorobiphenyl (1). A mixture of 4-chlorobiphenyl (1) (0.094 g, 0.50 mmol), metallic calcium (0.80 g, 20 mmol), and ethanol (10 mL) was stirred at room temperature in a round-bottom flask provided with a condenser. After 24 h, the reaction mixture was added to 100 mL of 1 N nitric acid. The solution was extracted with 3 × 20 mL ether. Combined organic layers were washed, dried on MgSO4, and evaporated. The residue (0.075 g) was dried in vacuo. Assignment and Quantitative Determination of Products on the Dechlorination of 4-Chlorobiphenyl (1). The GCMS analyses were carried out on an HP 6890 series gas chromatograph (Hewlett-Packard) equipped with a 30 m DB-1 column (i.d. 0.25 µm) (J&W Scientific) and a JMS-AM II series (JEOL), which is a quadrupole mass spectrometer. Ionization was performed under 70 eV electron-impact (EI) conditions. The GC-17A gas chromatograph (30 m DB-1 and FID detection) (Shimadzu) was also used for routine work and the determination of the yield. Its recorder was a C-R6A Cromatopac (Shimazdu Ltd.). The programs of both GC were the same, as follows: the initial temperature of the column was 60 °C, held for 3 min, then the rate of temperature increase was 25 °C/min up to 250 °C, and the temperature was held for 20 min. Assignment of structures, especially for isomers of cyclohexene and cyclohexadiene with different positions of the double bond in the rings, was obtained by a search of the GC-MS library. Typical Procedure for the Dechlorination of PCDDs, PCDFs, and co-PCBs. A mixture of PCDDs, PCDFs, and coPCBs in 1 mL of hexane solution (its concentration is 22 000 pg TEQ/mL), metallic calcium (0.8 g, 20 mmol), and ethanol (10 mL) was stirred under atmospheric pressure at room temperature in a round-bottom flask provided with a condenser. After 24 h, the reaction mixture was poured into 100 mL of 1 N nitric acid and then was extracted twice with 100 mL of dichloromethane under vigorous shaking. After being separated from the aqueous layer, the combined organic phases were washed with distilled water until the pH of the aqueous layer became 7. The dichloromethane layer was dried by anhydrous MgSO4, then filtered, and concentrated to 10 mL. The method for cleanup of PCDDs, PCDFs, and co-PCBs is already known (21, 22). Assignment and Quantitative Determination of Tetra-, Penta-, and Hexa-Substituted CDDs and CDFs by the HRGC-HRMS Analysis. In the measurement of PCDDs and PCDFs, the conditions of the HRGC-HRMS analysis were as follows: the GC-MS analysis was carried out on an HP 6890 series gas chromatogragh (Hewlett-Packard) equipped with a 60 m SP-2331 (i.d. 0.25 mm, 0.20 µm film thickness) (Supelco) and JMS-700 series (JEOL). The program and pressure of GC was as follows: the initial temperature of the column was 170 °C, held for 1 min (270 kPa), and then the rate of the temperature increase was 20 °C/min (14 kPa/ min) up to 210 °C (298 kPa). The rate was changed to 2 °C/ min (1.4 kPa/min) up to 255 °C (336 kPa), and the temperature was held for 5 min. The temperature of the column was then

TABLE 1. Effect of Volume of Ethanol to Metallic Calcium on Dechlorination ratio of products (%)a entry

ethanol (mL)

1b

2

3

4

5

6

1 2 3

5 10 20

0 1 5

81 88 89

2 0 0

14 10 5

2 1 0

1 1 0

a

The isomers are determined by GC-MS analysis.

b

Recovered.

increased by 40 °C/min (100 kPa/min) up to 260 °C (500 kPa), where it was maintained for 20 min. The injection was performed by a splitless mode. The carrier gas was He (the purity was 99.9999%). The temperature of the injection port and the ion source was 265 and 250 °C, respectively. The ionization energy and current were 45 eV and 600 µA. The resolution was 10 000. The general procedure for the assignment and quantitative determination and the details of cleanup spikes and syringe spike as internal standards for all isomers of PCDDs and PCDFs by HRGC-HRMS are related to relevant regulations (21, 22). Assignment and Quantitative Determination of co-PCBs, Hepta-, and Octa-Substituted CDDs and CDFs by the HRGC-HRMS Analysis. In the measurement of PCBs, the conditions of the GC-MS analysis of chlorinated biphenyls were as follows: the GC-MS analysis was carried out on an HP 6890 series gas chromatogragh (Hewlett-Packard) equipped with a 60 m DB-5 (i.d. 0.25 mm, 0.25 µm film thickness) (J&W Scientific) and JMS-700 series (JEOL). The program of GC was as follows: the initial temperature of the column was 150 °C, held for 1 min, and then the rate of the temperature increase was 20 °C/min up to 185 °C. The temperature of the column was then increased by 2.0 °C/ min up to 245 °C, the temperature was held for 10 min, and then increased by 6 °C/min up to 295 °C, where it was maintained for 15 min. The injection was performed by a splitless mode. The carrier gas was He, and its column flow was 1.7 mL/min. The temperature of the injection port, interface, and ion source was 295, 295, and 250 °C, respectively. The ionization energy and current were 45 eV and 600 µA. The resolution was 10 000. The general procedure for the assignment and quantitative determination and the details of cleanup spikes and syringe spike as internal standards for all isomers of PCDDs and PCDFs by HRGC-HRMS are related to relevant regulations (21, 22).

Results and Discussion Investigation of the Most Convenient Ratios of Metallic Calcium to Ethanol. The effect of the type of solvent on the reactivity was reported in a previous paper (18). In this case, ethanol was used as a solvent in this dechlorination process because, beside its reactivity, it presents some other advantages, which are as follows: ethanol is one of the most environmentally friendly solvents, and it is able to dissolve all isomers of PCDDs, PCDFs, and co-PCBs into the solution. Table 1 summarizes the relation of the amount of metallic calcium and the volume of ethanol for the reaction of 4-chlorobiphenyl (0.5 mmol) as a model compound with metallic calcium (Figure 1 and Table 1). In entry 3, the use of a higher amount of ethanol (20 mL) along with metallic calcium consumes most part of the metal. On the other hand, small amounts of ethanol (5 mL) are difficult to stir with a magnetic stir bar due to the formation of a high viscosity slurry in the final reaction mixture (entry 1). We also found that the reduction did not sufficiently proceed when using excess amounts of ethanol because of the smaller surface area of metallic calcium. Therefore, the chosen volume of VOL. 38, NO. 4, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

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FIGURE 1. Dechlorination of 4-chlorobiphenyl with metallic calcium in ethanol.

TABLE 2. Concentration of PCDDs, PCDFs, and co-PCBs with Ca/Alcohol Treatment at Room Temperature final concentration (pg/mL) ethanol at room temp isomers

initial concn (pg/mL)

2,3,7,8-tetraCDD 1,2,3,7,8-pentaCDD 1,2,3,4,7,8-hexaCDD 1,2,3,6,7,8-hexaCDD 1,2,3,7,8,9-hexaCDD 1,2,3,4,6,7,8-heptaCDD 1,2,3,4,6,7,8,9-octaCDD total CDDs

1 300 5 700 4 900 9 600 6 700 47 000 54 000 129 200

2,3,7,8-tetraCDF 1,2,3,7,8-pentaCDF 2,3,4,7,8-pentaCDF 1,2,3,4,7,8-hexaCDF 1,2,3,6,7,8-hexaCDF 1,2,3,7,8,9-hexaCDF 2,3,4,6,7,8-hexaCDF 1,2,3,4,6,7,8-heptaCDF 1,2,3,4,7,8,9-heptaCDF 1,2,3,4,6,7,8,9-octaCDF total CDFs

3 700 8 800 12 000 15 000 13 000 2 200 19 000 3 600 7 700 24 000 109 000

3,4,4′,5-tetraCB 3,3′,4,4′-tetraCB 3,3′,4,4′,5-pentaCB 3,3′,4,4′,5,5′-hexaCB 2′,3,4,4′,5-pentaCB 2,3′,4,4′,5-pentaCB 2,3,3′,4,4′-pentaCB 2,3,4,4′,5-pentaCB 2,3′,4,4′,5,5′-hexaCB 2,3,3′,4,4′,5-hexaCB 2,3,3′,4,4′,5′-hexaCB 2,3,3′,4,4′,5,5′-heptaCB total PCBs

2 500 9 700 7 500 2 800 630 3 700 4 500 1 200 1 400 4 400 2 500 3 800 44 630

9

conversion (%)

concn 21 55 43 96 75 410 400 1 100

ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 38, NO. 4, 2004

concn

conversion (%)

98.38 99.04 99.12 99.00 98.88 99.13 99.26 99.15

29 100 58 2 200 2 700 9 500 14 000 28 587

97.77 98.25 98.82 77.08 59.70 79.79 74.07 77.87

62 35 150 26 28 nd 110 23 6.2 3.8 444

98.32 99.60 98.75 99.83 99.78 ∼100 99.42 99.36 99.92 99.98 99.59

170 67 180 49 60 41 57 430 47 390 1491

95.41 99.24 98.50 99.67 99.54 98.14 99.70 88.06 99.39 98.38 98.63

17 71 76 28 6.0 32 48 7.4 17 55 32 39 428.4

99.32 99.27 98.99 99.00 99.05 99.14 98.93 99.38 98.79 98.75 98.72 98.97 99.04

5.4 62 26 4.3 71 690 240 12 30 63 16 7.2 1226.9

99.78 99.36 99.65 99.85 88.73 81.35 94.67 99.00 97.86 98.57 99.36 99.81 97.25

ethanol was 10 mL, and the suitable quantity of metallic calcium in 10 mL of ethanol was 20 mmol. Dechlorination of PCDDs, PCDFs, and co-PCBs. Table 2 shows the results of dechlorination of PCDDs, PCDFs, and co-PCBs at room temperature under atmospheric pressure. The initial concentration (total CDDs 129 200; CDFs 109 000; co-PCBs 44 630 pg/mL) of dioxins and co-PCBs is indicated in the second column. The third column presents the measured values after the treatment with Ca/EtOH for 24 h. Concentrations of all isomers suffered drastic decrease, being clearly reduced to dechlorinated compounds by the Ca/EtOH system. For instance, the concentration of 2,3,7,8-tetraCDD, which is one of the most stable isomers in dioxins, decreased to 21 pg/mL in 98.38% conversion. Table 2 presents also the conversion of each chlorinated compound. After treatment with the Ca/EtOH mixture at room temperature, total concentrations of CDDs, CDFs, and co-PCBs of the initial mixture were reduced to 1100 (99.15%), 444 (99.59), and 428.4 (99.04) pg/mL, respectively. Thus, PCDDs, PCDFs, and coPCBs can be easily dechlorinated under mild conditions without any tedious procedures. When performing the dechlorination process in methanol, metallic calcium dis1218

methanol at room temp

solved vigorously along with the formation of a high-viscosity solution and subsequent loss of a large amount of metal. We can assume that the dechlorination process proceeds via an aromatic nucleophilic substitution performed by the first electron from the transformation Ca f Ca+ + e- (first step) f Ca2+ + e- (second step). The aromatic ring is, therefore, transformed into a radical anion that rapidly expels chloride (their presence in the reaction mixture was demonstrated through Mohr’s titration). Due to the relatively powerful electron-withdrawing effect of the chlorine atoms, the first nucleophilic attack should be easier for polychlorinated isomers (a greater number of chlorine atoms present on a nucleus will weaken the C-Cl bond). This assumption was confirmed by the relative dechlorination rates at shorter reaction times when hepta- or octa-chlorinated isomers suffer greater loss of chlorine than tetra- or penta-chlorinated isomers. On the other hand, the effect of the oxygen atom(s) is also very important: results show that dechlorination rates are better for dibenzodioxins than for dibenzofurans. Although in aromatic rings the oxygen atoms present a low electron-withdrawing effect but a powerful electron-donating

TABLE 3. Dechlorination of PCDDs, PCDFs, and co-PCBs with Ca/EtOH Treatment under Reflux Conditions isomers

initial concn (pg/mL)

final concn (pg/mL)

conversion (%)

2,3,7,8-tetraCDD 1,2,3,7,8-pentaCDD 1,2,3,4,7,8-hexaCDD 1,2,3,6,7,8-hexaCDD 1,2,3,7,8,9-hexaCDD 1,2,3,4,6,7,8-heptaCDD 1,2,3,4,6,7,8,9-octaCDD total CDDs 2,3,7,8-tetraCDF 1,2,3,7,8-pentaCDF 2,3,4,7,8-pentaCDF 1,2,3,4,7,8-hexaCDF 1,2,3,6,7,8-hexaCDF 1,2,3,7,8,9-hexaCDF 2,3,4,6,7,8-hexaCDF 1,2,3,4,6,7,8-heptaCDF 1,2,3,4,7,8,9-heptaCDF 1,2,3,46,7,8,9-octaCDF total CDFs 3,4,4′,5-tetraCB 3,3′,4,4′- tetraCB 3,3′,4,4′,5-pentaCB 3,3′,4,4′,5,5′-hexaCB 2′,3,4,4′,5-pentaCB 2,3′,4,4′,5-pentaCB 2,3,3′,4,4′-pentaCB 2,3,4,4′,5- pentaCB 2,3′,4,4′,5,5′-hexaCB 2,3,3′,4,4′,5-hexaCB 2,3,3′,4,4′,5′-hexaCB 2,3,3′,4,4′,5,5′-heptaCB total PCBs

2 380 11 300 9 400 17 400 11 300 83 000 89 000 223 780 6 700 19 700 37 900 29 000 25 700 13 030 44 300 69 000 13 700 57 000 316 030 4 500 15 100 11 300 4 580 990 8 000 6 800 2 190 4 100 7 500 3 720 5 970 74 750

28 90 67 160 130 540 220 1 235 150 58 180 15 22 N.D 42 10 1.2 4.3 482.5 27 110 67 16 7.8 48 41 10 16 37 19 21 419.8

98.82 99.20 99.29 99.08 98.85 99.35 99.75 99.45 97.76 99.71 99.53 99.95 99.91 ∼ 100 99.91 99.99 99.99 99.99 99.85 99.40 99.27 99.41 99.65 99.21 99.40 99.40 99.54 99.61 99.51 99.49 99.65 99.44

one (due to electron lone pairs), only the electron-withdrawing effect is effectively involved in the process (the density of electron lone pairs on the oxygen atom(s) substantially decreased due to the conjugation effects on both polychlorinated aromatic rings). Another experiment shows that when the contribution of the lone pairs is more involved in the conjugation with the aromatic rings (thus the electrondonating effect becomes preponderant), the dechlorination rate decreases drastically. For instance, when performing dechlorination of 4-chlorobiphenyl ether (1.0 mmol) with metallic calcium (20 mmol) in ethanol (10 mL) at room temperature for 24 h, we obtained the biphenyl ether in only 2% yield. On the aromatic rings, chlorine is substituted by hydrogen from the hydroxyl group of the alcohol, the alkoxide ion quenching the Ca2+ cation. During the final workup of the reaction mixture (when pouring into an aqueous acidic solution), this mixture evolved gas and produced a small quantity of heat. This means that metallic calcium in ethanol is still reactive after 24 h. Table 3 indicates the dechlorination of PCDDs, PCDFs, and co-PCBs under reflux conditions. The reactivity increased as compared to the reaction at room temperature. The efficiency for CDDs improved from 99.15% up to 99.45% despite the shorter reaction time (24 h to 2 h). In a similar manner as above, the efficiency for the dechlorination of CDFs and co-PCBs also increased from 99.59% to 99.85% and from 99.04% to 99.44%, respectively. In Tables 2 and 3 are shown the actual concentrations of representative isomers of PCDDs, PCDFs, and co-PCBs. Table 4 represents the TEQ of all isomers. In the TEQ evaluation for the decomposition of PCDDs, PCDFs, and co-PCBs, the initial TEQ of all isomers indicated 22 000 pg TEQ/mL of hexane. After the treatment with Ca/ethanol under mild

TABLE 4. Initial and Final TEQa,b of PCDDs, PCDFs, and co-PCBs with Ca/EtOH or Ca/MeOH Treatment final TEQ at room tempc

final TEQ at refluxd

initial TEQ

ethanol

methanol

initial TEQ

ethanol

22 000

210

920

52 000

280

a

The values of TEF (toxicity equivalency factor) were used according to refs 19 and 20. b pg TEQ/mL of hexane. c The reaction time is 24 h. d The reaction time is 2 h.

conditions, the same system was reduced to a total of 210 pg TEQ/mL of hexane. Under reflux conditions, a mixture with an initial value of 52 000 pg TEQ/mL of hexane was reduced up to 280 pg TEQ/mL of hexane. In conclusion, the use of metallic calcium in ethanol at room temperature under atmospheric conditions is found to be very suitable and environmentally friendly for the dechlorination of PCDDs, PCDFs, and co-PCBs under mild conditions. The efficiency of the dechlorination reached over 99%. This approach may prove useful and convenient with respect to the dechlorination of other harmful chlorinated aromatic compounds.

Acknowledgments We thank Mr. M. Katata and co-workers for their help with the experimental procedure. This work was supported by a grant from Fukuoka Industry, Science & Technology Foundation (Fukuoka IST).

Literature Cited (1) Nicholson, W. J.; Landrigan, P. J. Human Health Effects of Polychlorinated Biphenyls. In Dioxins and Health; Schecter, A., Ed.; Plenum: New York, 1994. (2) Zook, D. R.; Rappe, C. Environmental Sources, Distribution and Fate of Polychlorinated Dibenzodioxins, Dibenzofurans and Related Organochlorines. In Dioxins and Health; Schecter, A., Ed.; Plenum: New York, 1994. (3) Patterson, D. G.; Holler, J. S.; Smith, J. S.; Liddle, J. A.; Sampson, E. J.; Needham, I. L.Chemosphere 1986, 15, 2055. (4) Purchase, I. F. H. Br. J. Cancer 1980, 41, 454. (5) Hagenmaier, H.; Horch, K.; Fahlenkamp, H.; Schetter, G. Chemosphere 1991, 23, 1429. (6) Hirayama, N. Technologies for De-Dioxin; CMC: 1998; p 257. (7) U.S. Congress, Office of Technology Assessment. Dioxin Treatment Technologies-Background Paper; OTA-BP-O-93; U.S. Government Printing Office: Washington, DC, November 1991. (8) Sako, T.; Sato, M.; Sugeta, T.; Otake, K.; Tsugumi, M. (National Institute of Advanced Industrial Science and Technology, AIST). Jpn. Kokai Tokkyo Koho 1997, 327, 678. (9) Weber, R.; Yoshida, S.; Miwa, K. Environ. Sci. Technol. 2002, 36, 1839. (10) Oku, A.; Tomari, K.; Kamada, T.; Yamada, E.; Miyata, H.; Aozasa, O. Chemosphere 1995, 31, 3873. (11) Kawai, T.; Otsuka, T.; Ogura, M.; Konishi, Y.; Kato, O.; Nishimura, H. (Shinko Pantec Co. Ltd.) Jpn. Kokai Tokkyo Koho 2002, P2002121, 155A. (12) Bumpus, J. A.; Tien, M.; Wright, D.; Aust, S. D. Science 1985, 228, 1434. (13) (a) Australian Patent Application PL6474, 1992. (b) Rowlands, S. A.; Hall, A. K.; McCormick, P. G.; Street, R.; Hart, R. J.; Ebell, G. F.; Donecker, P. Nature 1994, 367, 223. (14) Tashiro, M.; Fukata, G. J. Org. Chem. 1977, 42, 835. (15) Tashiro, M.; Iwasaki, A.; Fukata, G. J. Org. Chem. 1978, 43, 196. (16) Liu G. B.; Tsukinoki T.; Kanda T.; Mitoma Y.; Tashiro, M. Tetrahedron Lett. 1998, 39, 5991. (17) Tsukinoki, T.; Kanda, T.; Liu, G. B.; Tsuzuki, H.; Tashiro, M. Tetrahedron Lett. 2000, 41, 5865. (18) Mitoma, Y.; Nagashima, S.; Simion, C.; Simion, A. M.; Yamada, T.; Mimura, K.; Ishimoto, K.; Tashiro, M. Environ. Sci. Technol. 2001, 35, 4145. (19) Ahlborg, U. G.; Becking, G. C.; Birnbaum, L. S.; Brouwer, A.; Derks, H. J. G. M.; Feeley, M.; Golor, G.; Hanberg, A.; Larsen, VOL. 38, NO. 4, 2004 / ENVIRONMENTAL SCIENCE & TECHNOLOGY

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J. C.; Liem, A. K. D.; Safe, S. H.; Schlatter, C.; Waern, F.; Younes, M.; Yrja¨nheikki, E. Chemosphere 1994, 28, 1049. (20) Van den Berg, M.; Birnbaum, L.; Bosveld, A. T. C.; Brunstro¨m, B.; Cook, P.; Feeley, M.; Giesy, J. P.; Hanberg, A.; Hasegawa, R.; Kennedy, S. W.; Kubiak, T.; Larsen, J. C.; van Leeuwen, F. X. R.; Liem, A. K. D.; Nolt, C.; Peterson, R. E.; Poellinger, L.; Safe, S.; Schrenk, D.; Tillitt, D.; Tysklind, M.; Waern, F.; Younes, M.; Zacharewski, T. Environ. Health Perspect. 1998, 106, 775. (21) Measuring method of dioxins and coplanar PCBs in industrial water and industrial liquid waste; JIS K 0312-1999; Japanese Industrial Standards Committee: Tokyo, 1999.

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(22) Japan Ministry of the Environment. http://www.env.go.jp/en/ topic/dioxin/manual.pdf (accessed August 2003). A similar clean-up method for liquid sample is also shown in Manual on Determination of Dioxins in Ambient Air.

Received for review April 22, 2003. Revised manuscript received November 24, 2003. Accepted December 2, 2003. ES034379B