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1 Korean Chem. Eng. Res., Vol. 44, No. 2, April, 2006, pp ji (PCP)l z m PCPm k }} mpz l re o o n~ 35-1 (2006 1o 11p r, o 20p }ˆ) Solvent Extraction of Pentachlorophenol(PCP)Gfrom PCP-treated Wood Jong-Chol Lee and Soo Choi Agency for Defense Development, P.O. Box 35-1, Yuseong-gu, Daejeon , Korea (Received 11 January 2006; accepted 20 March 2006) k h mm ˆ (pentachlorophenol : PCP)p } ˆk q qe ˆm, lˆm, k Š p n n l PCP m. e n s, s q e n p n p, e p ˆ, m pž r m. qp PCP 720 ppm plp ˆmp q n m. q e ( 1297 ppm) ˆm ml 2e p l 99Í v r l. se ˆmp n p(v/w)p 10plp p e l e p (chip Š )p m pž np PCP l m p v kk. Abstract Solvent extraction of pentachlorophenol (PCP) from wood chips of the PCP-treated ammunition box has been studied using methanol, ethanol and acetonitrile. Experimental variables were chosen as the composition of solvents, the ratio of solvent per dried wood, size of the substance, extraction temperature and sonication applied to the samples. The average concentration of PCP was 720 ppm and methanol was the most effective for PCP extraction. Above 99Í of PCP were removed from the sample (initial concentration of PCP; 1297 ppm) within 2 h at room temperature by methanol. The minimal ratio of methanol per dried wood chip(v/w) was 10. Type of substances(chip or sawdust), extraction temperature and sonication showed little effects on PCP extraction. Key words: PCP-treated Ammunition Box, Pentachlorophenol(PCP), Solvent Extraction 1. q p q p n q tp p Ž l q sp l n Žopp t, k, fungi l p qnl p. p v qp q n sp o l, r v mm ˆ (pentachlorophenol: PCP) p q } l m. PCP p~m ql l n o k v 1980 v pp k k v r l pl PCP } qp n r p [1]. PCP PCP vp q pme op r pl pl l m ep rr ƒv p [2-4]., p p } ˆk q n m To whom correspondence should be addressed. jcleeadd@hanafos.com p p n pt 80Í PCP } m. p v 2,500 Šp PCP } q l mp } p r l pp PCPp k p k v ~(EPA)p o, s q 1Kg 100 mgp PCP n tp n p rk p. p n p } qp r l p e np v, q(ash) } v k p q vl PCP } q(p PCP } q )p kr } q n l p l m [4-6]. n p r l 1986 p l PCP np v kr q r n p p l ˆk q PCP } l nˆkp n ˆk q v rp pl kr} qp q n p n p. PCP, r f, Žp } r n pp rp kr p~ k ql v 227

2 228 ps~ e m p t., PCP } q mr pme p opp p l e np v p. EPAp en t PCP 1 ppb p p q lq n 0.5 mg/m 3 p [1] f n p rp r n pp o pp PCP } qp q n tp s q 1 Kg 5 mg p r p. p ˆk q k k 1l 3} p rt r l n pp p 20~35 l p. pt 60Í PCP } mp k 250 p. PCP r rp ~, q, Ž l n p. p qp q np o l, r } p p [7, 8]. p rp q chipp r nk p } l creosotem PCP r ˆ vp l l PCPm creosote ql chipp } l 21p l 5 ppm p r p p 98.7Í 21p l r l. PCPm creosote p l l q sp l v q rp v k. PCP km p l qp p l. PCPp n l sp nr pp q l v PCP rrp r p p tn. r PCP } qp } p n o l p s p k PCP p pp q s l v l sq PCPp r np v k. p r l qp l q v. p q p PCP Ž pp } p kl PCP d v } n. d vl 0.04 mg/lp PCP p [5]. o p PCP } ˆk q vll r q p. po kv rrp rp } p l p. pp p p Lamarm Scholze[4] (white-rot fungi)p pn l PCP creosote } qp } [5, 9-11]p rk mp } kv., s - r r t n p Šk v o o m r l o p pv l m. Khodadoust [12]p PCP mm Škp lˆm(1:1)p n l 1e l d m pž q l ll. p q } vll mm Š kp PCP r l n rpl. n p s n p rr ˆ l vveˆ p. Meyerm Kleibhner[13] p p pn l tl o PCP r e sp d q l ˆm n, e t v 2pp ne p 3e p m. p q l CO 2 pn ˆmp n n l q chipp PCP p tn e (U.S. toxicity characteristic leaching procedure : TCLP) t 0.1 ppm p v eˆ n p [14]. p l PCP } ˆk qp kr} m } qp q n l Ž o l q chipp Š p PCP r l q np n p pn p ˆv o l m. p e l n nkp v l q n PCP q vp, r } chipp Š p, l, Žrs k p q n p qo } edš l p p m ˆk q k mm ˆn ˆk q 2 l qp,, ~ s - q p, r q v m. qo ˆ ˆ k q l p s ˆk e Ž pp r ˆ k m. q o, l rs mp q k l P p l pl PCP } q qpp p pl. ˆk qp rop Table e e p rs ˆk qp q sp o l q sr n PCP p } l [15]l PCP 5 wtí 1 thinner p o n l } 72e s l r vp k pl k. PCP } q(žq) p kyl l Ž l. r ql q PCP r o l q - q p rn q v m pt 17.5 mmp Žq q /n o l PCP r o l qe 3sp, rs m. v, S-1p 17.5 mmp Žq e e q n p q Ž pn l 5 mm p chipp, e pžqp kyp 3 mm l S-2 m. Grinding 9.5 mmp Žq S-3p l 3s e p PCP r m. qp PCP p vlv ~ e(r92-10 ; )l Š p l d q Table 2m., e v k Žq 2 qo ˆ l PCP 720 ppm pl. Table 1. Characteristics of the PCP-treated ammunition box Category # 1 # 2 Remarks Lot No. LS-61-28A MA-114-6A 81mm HE M374, 3 Ctg., w/fuze PD Total weight of ammunition box 5.88 Kg 7.08 Kg Total weight of lumber 4.32 Kg 5.20 Kg Avg. wt : 4.8 Kg Size of Box 658(L) 348(W) 150(H) mm, thickness of lumber : 17.5 mm Manufactured in April 1971, USA o44 o k

3 PCP } qp n 229 Table 2. PCP concentration of the PCP-treated wood S-1 S-2 S ppm 1,297 ppm 518 ppm Wood samples were prepared by grinding the surface of the wood: S-1; outer surface(thickness, t=5 mm), S-2; inner surface(t=3 mm) and S-3; the remained wood(t=9.5 mm) k }} e p t ql v PCP o l o 3sp e t PCP q S-2 ˆ l chipp pt chipp p Š p rs l chip Š p e e n m. n chipp 10 mm( ) 5 mm( ) 3 mm( ) plp Š p Š rsq (Thomas Scientificp Wiley mill) p 0.5 mmp sieve l rs m n n n HPLCn ˆm, lˆm k Š (Aldrich)p rr v k n m. PCP p qe 2±0.05 g p 3 p p o l n 100 ml tp ml 150 rpmp shakerl m m n p l pre p k 1 mlj l v d lt mr s PCP m. e p s s l PCPp PCP } q q n t v PCP r o l e nn l, r e, se (1 g) n (ml)p n p(v/w), e ˆ(chip Š )l, m pž m p m PCP e p p PCP o ~ e GC/MS-SIMp m. r nkp k 1mlp l v d l p mr s k Š 700 µlm t vp dibenzothiophene(dbz) 100 µlm o ~ v bis(trimethylsilyl), trifluoroacetamide(bstfa) 200 µl 70 o C m l 30 peˆ GC/MS m. p Agilent p 6890N series GCm 5973 Mass Selective Detector v l q l auto injector n m. n p HP-5 MS capillary column (30 m 0.25 mm I.D.,, 0.25 µm) plp m m 2 40 o C ov 10 o Cj m l 280 o Cl 5 ov m. Carrier gas p 1 ml t l injection typep splitless, injector m 250 o C ov m. MS 70 evl positive electron impact n m. tekp PCP(99Í p ) DBZp Aldrich r p, o ~ ekp BSTFA Supelco r p n m. q p o l PCP k Šl l 1,000 µg/ml tnkp sr l r (2~10 µg/ml)m (25~125 µg/ml) nkp l p tnk 500 µgl DBZ 100 µg, BSTFA 200 µg, acetone 200 µg 70 o C m l 30 peˆ m. r r p e p e rp t v e GC-MSl tp l lp v t v p r l r l m. Fig. 1. Total ion chromatogram of components in the wood extract by GC-MS analysis: (a) Dibenzothiophene; min, Pentachlorophenol; min, (b) Mass spectrum of derivatives of PCPU Fig. 1p GC-MSp mass spectra (a) qe ˆm np total ion chromatogram(dbz : 17.44, PCP : )p Fig. 1(b) PCPp mass spectrump. nkl Fig. 1(a)m p PCP pnl p k p l pp p ql o vp o PCPp o ~ p Ž e p q PCP tr l mp v p e v kkp p (Wiley 7n.1) n l Š p p tn p m. ˆk q rs e ql } ln PCP rsol 85~98Í p l PCP pnl tri-, tetra- m pme ql p l p p r. e l Fig. 1(a)m p Š p tn PCP pnl ql f kl n arabinose, arabinopyranose p l. p GC, HPLC, GC-MS LC-MS n. GCm HPLC v e l r rp vl p mp n pp r p GC-MS LC-MS p } p. p p p q p p GC-MS ˆ p. Domeo [16]p pe q sp l o PCP ( t 0.15 mg/kg) r o l SPME (solid-phase micro extraction) p rk m., q p PCP r tr s l r n p [17]. n p e p q Korean Chem. Eng. Res., Vol. 44, No. 2, April, 2006

4 230 ps~ rl HPLC pp Hahn [18]p sp ql PCP p r p e l p o ~ p GC-MS pn l 10~20 ppbp v pp PCP t v o ~ p e PCP o ~ p pp t vp p 20 r kp o ~ p e PCP o ~ k Ž o ~ p ltl. 3. y 3-1. h mm PCP m ˆk q Žqp PCP q 720 ppm plp q Žqo l 520~1297 mg/kg kv p kp ql q l pl. pp q l PCP 100 mg/kgp o t pl e p qe p tp 7 p p. PCP } ˆk q n m o p 1991 p p v p m. v, - q o t qo s (RCRA)l vr e l k qq t p plk. ql v. - PCP } q kn e kp o Šk q n n q n pp e, np n v t vl l rq pe qnp np v [5]. PCP l [15]p - k qn r n l 4sp pt s A PCP 5wtÍ n m. n p l PCP } mp 1986 ˆk qn qp p rr l[19] q q p copper- 8-quinoli nolate nkp 1.8Í eˆ r PQ 56p klp 3Í eˆ M-GARD W550(zinc naphthenate) l 1 mr } q p q l 24e k s m. m rq ˆk q( o pr) PCP } l Ž. e l n ˆk q l s p rq, l v p p k lp rs k 30l p v rl ( l p 5wtÍ r)p k 1/70 p q p f PCP ˆkrq r t d v k kpp k p. q Table 2m p qp n k 1.6 kp n p p m S-3(Žqp k p pr q)l p t p 5 p PCP q m. qp k p pr Žqp tk o PCP p q v kk q np p Ž mp e PCP q l p q p lr Žqp rp grindingp p ll PCP q S-2 Žq chipp pt p Š p rs l k m p e l n m kk i }} n s l PCP o l o l q chip 2±0.05 gp p ˆm, lˆm, k Š p 100 mlj mp ov shakerl 4e p o44 o k Fig. 2. Comparison of PCP extractability by 3 solvents (Initial concentration of PCP in the wood chip was 1,297 mg/kg of dry sample). Fig. 2m p ˆm>lˆm>k Š p v m. nkp n r n m. q sp ˆmp 1e p 96Í, 2e l 99Í, 3e l p l ˆm k Š p 3e p, 74Í 40Í l p e p ˆmp n n m. Pal [5]p (k 10,700±180 mg/kg)p PCP } q rtp chip(10 mm 20 mm 2 mm)l p n 42e p, o 3s n p ˆmp (k 7Í o) skp n l p p ll lˆ mp n } m, 2 M nkp 3p l 3Í nl v kk. l p e ˆm lˆmp r p p pp ˆmp 20Í p rpl ˆmp n ˆ m }}k m o o e l ˆmp q r plp e ˆmp r n o l p p o l 2±0.05 gp qe p p ˆmp 10, 20, 40, 60 ml 2e PCP r pp lt e 1g ˆmp (v/w) Fig. 3 p Fig. 3. PCP extraction using various ratios of wood chip and methanol(v/w).

5 1:10 p plp e m o l o l p q l o l e : ˆ mp 1:20 p rn p v Ž l m {m i m }}i e l PCP kk o l p p n l chip Š p 2.0±0.05 g ˆm 100 ml mp shakerl pre p e } l PCP m. Š p p chipp Š rs (Thomas Scientific, Wiley Mill)l p 0.5 mmp sieve l r s m., pž l m p p p pž q m shakerl el v m. e } p e eq 1e p p p p m. Fig. 4 5 pq ˆ pž m l p PCP p p lt. Fig. 4l m p Š p n chip 1e p l 9~17Í v mp 2e p l l 5Í o l d m. er rn e l chipp Š l lp rsp np q n p Ž Fig. 4. Comparison of PCP extractability by two types of substances ( : wood chip, : sawdust). Fig. 5. Effect of sonication and shaking on extraction of PCPG( : shaking, : sonication). PCP } qp n 231 l e n l p Ž. pžl m p shakerl nm l p llp er rn el qlp np p chipp l e m n q p re p m l p pž q lp ql r e p pp p Ž. pž q l n Œe PCP-n p p v eˆ v r v l v p e l m p e : n 1:50p n n pžp m pp n nl p m p p Ž. p e p e en rr pžq (270 w) n mp pžl p m p m p p rtž r pž q n r v p pl m lk p }}j m i m d n v v pp p Ž l p m (50 o C)l m. m p qˆp 250 ml round-bottom flaskl ˆm 100 ml p q ˆm m 50 o C ov r chip 2±0.05 gp 1e k m. ˆmp rp p (65 o C) d l q l l ˆmp v l n v k m. e m p m p r p ll ( m 50 o Cl 1e e 1Í n v ). m e PCP q tar o ( q ) p k p vp n l p np v kk ˆmp q n p eˆ pl m p v v k Ž l }}k m m k m sm z PCP- ˆm nkp v ˆmp np, l q n p. ˆmp rp p PCP( r 310 o C)m r ƒ np k PCP q vp r l n e, p p s} p. l l ˆm v e p ee v kkp ˆmp v q pn l d pp ˆm-PCP nk p p v q l ˆmp r p p l l nk p mr v v v v ˆmp v n q n p Ž. Pal [5]p lˆmp v l q m p v p r o l calcium sulphatep n m., p l PCP k PCPp m pnl q p v, v,, p k vp l p p p r l q vp l p rp Ž PCP z mm m k o pp r p PCP } qp q n tp 5 mg/1 Kg s q r p. qp q n Korean Chem. Eng. Res., Vol. 44, No. 2, April, 2006

6 232 ps~ Table 3. PCP removal from the PCP-treated wood chip depending on the extraction methods(initial concentration was 1,297 mg/kg dried wood chip) No. of extraction Extraction rate of PCP Method 1 * Method 2 ** 1 1,297 ppm 1,297 ppm ** Method 1: PCP was extracted by methanol from the wood chip(v/w : 20) for 2 hr and then the solvent was removed. The sample wood was extracted by the same manner repeatedly for six times. ** Method 2: PCP was extracted as in the Method 1 and then centrifuged. The wood sample was extracted and centrifuged repeatedly. p Š o l e chipp r ˆmp tp l ml PCP o p q n tp s v m. e p 1.0±0.05 gp chipl ˆm 20 ml 150 rpmp shakerl 2e l kp PCP r nkp r p p e l e ˆm 20 ml tp 2e k m. p rp 6 mp qp q n tp s v m. 2 w p p e l ˆm 20 ml 2e kp r q l kp nkp mr r o l 3,500 rpml 5 oe m. e p e l ˆm 20 ml p p oe rp q n tp s v m. e Table 3 p oe rp 4 p PCP qp q n tp pl. nkp r e ˆmp tp p 6 p t v m. po ˆml n l q l v l ˆ kp PCP- ˆmp nkp r v k PCPp mrr l Ž l. p e p p e n l e erp mp ne q q l PCP } qp kr } q n l v n p. 4. Pentachlorophenol(PCP) } ˆk qp q e PCP n p m. qp PCP q o l 520~1300 ppm v k r l. qp q n p Ž o l q l chip Š p l 3sp n n l PCP p r ˆm>lˆm>k Š p v mp ˆmp n l ml 2e 99Í p m. q chip 1 g ˆmp n 10 ml plp Š p n chip v mp e p 2e p p ll. pž m p o44 o k e l l m p tv kkp m(50 o C)l nl m l lp m p v. PCP } q ˆmp 1:20p p 2e oe p 4 p qp q n tp s pl. ˆm-PCP nkp r l p v p ˆmp l q n PCP q vp } p f qop pn qo edš p p. y 1. Environmental Health Criteria 71, Pentachlorophenol, International Programme on Chemical Safety, WHO, Geneva(1987) Lorber, M. N., Barton, R. G., Winters, D. L., Bauer, K. M., Davis, M. and Palausky, J., Investigation of the Potential Release of Polychlorinated Dioxins and Furans from PCP- Treated Utility Poles, The Science of the Total Environment, 290, 15-39(2002). 3. Tobia, R. J., Camacho, J. M., Augustin, P., Griffiths, R. A. and Frederick, R. M., Washing Studies for PCP and Creosote-contaminated Soil, J. of Hazardous Materials, 38(1), (2004). 4. Lamar, R. T. and Scholze, R. T., White-rot Fungi Biodegradation of Pcp-treated Ammunition Box, in Proceedings of R&D 92 National Research Development Conference on the Control of Hazardous Materials, U.S.A., 89-94(1992). 5. Pal, N., Korfiatis, G. P. and Patel, V., Sonochemical Extraction and Biological Treatment of Pentachlorophenol Contaminated Wood, J. of Hazardous Materials, 53, (1997). 6. Tennessee Valley Authority, Summary of PCP-treated Wood Waste Management at Army Installations, Prepared for U.S. Army Environment Center(USAEC) APG, MD, U.S.A(1999). 7. Gilbert, R., Benser, A. and Tetreault, P., Method of Extracting Chemical Preservatives from Treated Wood, U.S. Patent No. 5,262,004(1993). 8. Ely, R. L. and Langenberg, M. B., Method of Removing and Restoring Wood, U.S. Patent No. 4,734,138(1988). 9. Illman, B. L., Yang, V. W. and Ferge, L. A., Fungal Degradation and Bioremediation System for Pentachlorophenol-treated Wood, U.S. Patent No. 6,727,087 B2(2004). 10. Choi, I. K., The Method of Bioremediation of Pentachlorophenol Containing Waste by phanerochaete chrysosporium, Korean Patent No (2000). 11. Law, W. M., Lau, W. N., Lo, K. L., Wai, L. M. and Chiu, S. W., Removal of Biocide Pentachlorophenol in Waste System by the Mushroom Compost of pleurotus pulmonarius, Chemosphere, 52, (2003). 12. Khodadoust, A. P., Suidan, M. T., Acheson, C. M. and Brenner R.C., Solvent Extraction of Pentachlorophenol from Contaminated Soils Using a Water-ethanol Mixtures, Chemosphere, 38(11), (1999). 13. Meyer, A. and Kleibhmer, W., Determination of Pentachlorophenol in Leather Using Supercritical Fluids Extraction with in Situ Derivatization, J. Chromatogr. A 718, (1995). 14. Levien, K. L., Morrell, J. J., Lumar, S. and Sahke-Demessie, E., Process for Removing Chemical Preservatives from Wood Using Supercritical Fluid Extraction, U.S. Patent No. 5,364,475(1994).

7 PCP } qp n U.S. Federal Specification, Wood Preservative: Water Repellent, TT-W-572B(1969). 16. Domeo, C., Munizza, G. and Nerin, C., Development of a Solid-phase Microextraction Method for Direct Determination of Pentachlorophenol in Paper and Board Samples: Comparison with Conventional Extraction Methods, J. Chromatogr. A, 1095, 8-15(2005). 17. Becker, R., Buge, H.-G. and Win, T., Determination of Pentachlorophenol(PCP) in Waste Wood-method Comparison by a Collaborative Trial, Chemosphere, 47(9), (2002). 18. Hahn, A., Park, J. H., Choi, H. K., Hong, S. Y., Han, H. C., Jo, B. M. and Oh, J. S., Quantitative Analysis of Pentachlorophenol in Paper Products, J. Korean Ind. Chem., 16(3), (2005). 19. ROK Military Specification, Mil (1988). Korean Chem. Eng. Res., Vol. 44, No. 2, April, 2006

44(3)-16.fm

44(3)-16.fm Korean Chem. Eng. Res., Vol. 44, No. 3, June, 2006, pp. 270-276 지능형헬스케어욕조시스템개발을위한온수온도변화 r ~r l o l l e l 561-756 r rte v v 1 664-14 (2006 3o 9p r, 2006 6o 20p }ˆ) Change of the Warm Water emperature for