Environ. Sei. Technol. 1987, 21, 96-101
(8) Shafer, K. H.; Hayes, T. L.; Brasch, J. W.; Jakobsen, R. J. Anal. Chem. 1984,56, 237-240. (9) Puskar, M. A.; Levine, S. P. “Characterizationof Bulk Materials on Remedial Action Sites: A Preliminary Comparison of Compatibility Testing, FT-IR/ATR and GC/ MS”;Proceedings of the National Conferenceon Hazardous Waste and Environmental Emergencies, May 1985; HMCRI: Silver Spring, MD, 1985. Shafer, K. H.; Cooke, M.; DeRoos, F.; Jakobsen, R. J.; Rosario, 0.;Mulik, J. D. Appl. Spectrosc. 1981, 35, 469. Erickson, M. D. Appl. Spectrosc. 1981, 35, 181-184. Griffiths, P. R.; Azarraga, L. V.; de Haseth, J.; Hannah, R. W.; Jakobsen, R. J.; Ennis, M. M. Appl. Spectrosc. 1979, 33, 543. Lowry, S. R.; Huppler, D. A. Anal. Chem. 1981,53,889-893. Lowry, S. R.; Huppler, D. A.; Anderson, C. R. J. Chem. Inf. Comput. Sci. 1985,25(3), 253-241. Frankel, D. S. Anal. Chem. 1984,56, 1011. Rasmussen, G. T.; Isenhour, T. L.; Lowry, S. R.; Ritter, G. L. Anal. Chim. Acta 1978,103, 213-221. Antoon, M. K.; D’Esposito, L.; Koenig, J. L. Appl. Spectrosc. 1979, 33, 351-357. Brown, C. W.; Lynch, P. F.; Obremski, R. J.; Lavery, D. S. Anal. Chem. 1982,54, 1472-1479. Maris, M. A.; Brown, C. W.; Lavery, D. S. Anal. Chem. 1983, 55, 1694-1703. Osten, D. W.; Kowalski, B. R. Anal. Chem. 1985, 57, 908-917. Frankel, D. S. Anal. Chem. 1984,56, 1011-1014. Trulson, M. 0.; Munk, M. E. Anal. Chem. 1983, 55, 2137-2142. Puskar, M. A.; Levine, S. P.;Lowry, S. R. Anal. Chem. 1986, 58, 1156-1162. 1
(24) Hallstedt, P. A.; Levine, S. P.; Puskar, M. A. J . Hazard. Waste Hazard. Mater. 1986, 3, 221-232. (25) Eckel, W. P.; Trees, D. P.; Kovell, S. P. “Distribution and Concentration of Chemicals and Toxic Materials Found at Hazardous Waste Dump Sites”;Proceedingsof the National Conference on Hazardous Waste and Environmental Emergencies, May 1985. (26) Puskar, M. A.; Levine, S. P.; Lowry, S. R. Anal. Chem. 1986, 58, 1981-1989. (27) Woodruff, H. B.; Munk, M. E. J. Org. Chem. 1977,42(10), 1761-1767. (28) Woodruff, H. B.; Munk, M. E. Anal. Chim. Acta 1977,95, 13-23. (29) Woodruff, H. B.; Smith, G. M. Anal. Chem. 1980, 52, 2321-2327. (30) Woodruff, H. B.; Smith, G. M. Anal. Chim. Acta 1981,133, 545-553. (31) Tomellini, S. A.; Saperstein, D. D.; Stevenson,J. M.; Smith, G. M.; Woodruff, H. B. Anal. Chem. 1981,53,2367-2369. (32) Tomellini, S. A.; Stevenson, J. M.; Woodruff, H. B. Anal. Chem. 1984,56, 67-70. (33) Tomellini, S. A.; Hartwick, R. A.; Stevenson, J. M.; Woodruff, H. B. Anal. Chim. Acta 1984, 162, 227-240. (34) U S . EPA Test Methods 600; U.S. EPA (EMSL-Cincinnati): Cincinnati, OH, July 1982. (35) Harrick, N. J. Internal Reflection Spectroscopy; 2nd Printing; Harrick Scientific Corp.: Ossining, NY, 1979.
Received for review January 9,1986. Revised manuscript received July 14,1986. Accepted August 29,1986. This work was supported by Grant 1-R01-OH02066-01 from the National Institute for Occupational Safety and Health, Centers for Disease Control.
Contamination of Soil around Wood-Preserving Facilities by Polychlorinated Aromatic Compounds Veikko H. Kltunen, Risto J. Valo, and Mirja S. Saikinoja-Salonen” Department of General Microbiology, University of Helslnki, 00280 Helsinki, Finland
The fate of the different constituents of wood-preserving chlorophenol formulation in soil near the preserving facilities at four different sawmills was studied. The sawmills were in normal operation during the examination period. Penetration and stability of chlorophenols and the dimeric impurities of the contaminating formulation polychlorinated phenoxyphenols and polychlorinated dibenzofurans in soil were followed. The concentrations of all compounds were very high in soil, 500-3500 ppm for chlorophenols, 1-50 ppm for polychlorinated phenoxyphenols, and 0.2-5 ppm for polychlorinated dibenzofurans (dry weight of soil), showing that soil was heavily contaminated near the preserving facilities. No clear decrease of soil concentrations of these compounds was seen within 1 year after one mill stopped using technical chlorophenol. Chlorophenols were found to be metabolizable and mobile in soil whereas polychlorinated phenoxyphenols and polychlorinated dibenzofurans were persistent and immobilized in the top layer of the soil.
Introduction Technical chlorophenol (CP, Figure 1)formulations have been widely used as preservatives against rot and bluestaining of wood by fungi in the sawmilling industry both in Europe and in the U.S.A. CPs are toxic for terrestial and aquatic life. The use of technical CPs has led to serious pollution of the environment and hazardous situ96
Environ. Sci. Technol., Vol. 21, No. 1, 1987
ations a t the work place (1-8). Commerical C P formulations are usually synthesized by direct chlorination of phenol yielding a mixture of CPs, the main components being pentachlorophenol (PCP), 2,3,4,6-tetrachlorophenol (TeCP), and 2,4,6-trichlorophenol (TCP), and the byproducts polychlorinated phenoxyphenols (PCPPs, Figure 1) (9-11), polychlorinated diphenyl ethers (PCDPEs) (11,12), polychlorinated dibenzofurans (FCDFs, Figure 1) (11,12), and polychlorinated dibenzodioxins (PCDDs) (11-13). It was for reasons of the toxicity of the active ingredients and these impurities that Sweden banned the use of CPs for wood preservation in 1978, and the US.EPA has recently issued a ban, effective since 1984 (14), on consumer market use of PCP. In Finland, the manufacture of CPs-containing wood preservative for sawmill use was discontinued in 1984. There are many reports on the wide-spread contamination of the environment caused by leaching of CPs from dumping sites (15,16) or following accidental spill of CPs from industries using these chemicals (1,3,17). We have earlier shown that normal operation of a CP dip-treatment facility for timber and lumber in the sawmill industry has lead to serious local contamination of soil and groundwater (18,19) by CPs and the minor constituents of technical C P formulations, PCPPs (10, 11, 19) and PCDFs (11). This work was done to measure the leachability, vertical migration, and persistence of these compounds in soil.
0013-936X/87/0921-0096$01.50/0
0 1986 American Chemical Society
4
4
4
3
0
3
6
B
A
2
C
E
Figure 1. Numbering of CPs (A), PCDFs (B),PCPPs (C), 2-phenoxyphenols, (D) 3-phenoxyphenols, and (E) 4-phenoxyphenols.
Such information is needed for the estimation of future hazards formed to groundwater and redevelopment of such contaminated soils. To our knowledge, this paper is the first report on the migration of PCPP and PCDF compounds in soil.
Experimental Section Sampling. The soil was sampled in 1983 and 1984 at four sawmills (A, B, C, and R) in tightly closed tin-plated jars. Samples were taken at a distance of 5-30 m from the preserving facilities. All samples were stored in the dark a t 4 "C until analyzed. The mills had been in operation for 3 years (A), over 20 years (B), 25 years (C), and -40 years (R). The recent annual production volumes of the mills were as follows (CP-treated portion given in parentheses): mill A, 25 000 m3 (5000 m3);mill B, 42000 m3 (15000 m3);mill C, 330000 m3 (250 000 m3); mill R, 100 000 m3 (35 000 m3). Mills A-C used dip treatment for wood preservation; mill R had an impregnation ditch. All mills used a preservative marketed under the name Ky-5 (Kymi-Kymmene OY, Finland), which contained 60 wt. % of CPs (for further information, see ref 9,11, and 18-21). Mill A discontinued the use of Ky-5 in 1983. Mill B had operated the dipping facility a t the present place for 4 years. The approximate annual use of Ky-5 a t the mills in the recent past was as follows: 1000 (A), 3000 (B), 20000 (C), and 5000 kg (R). Chemicals. HPLC-grade solvents were used (Rathburn). Silica gel (Kieselgel 60, 70-230 mesh, Merck Darmstadt) was washed 3 times with CH,C12, heated overnight at 600 "C, and moistened to 10% (w/w) with water before use. Basic alumina (Woelm) was conditioned at 140 "C for 12 h. All other chemicals were analytical-grade and obtained from commercial sources (Fluka, EGA-Chemie, Merck, and Bayer) except for the model compounds, which were synthesized by T. Humppi (Department of Chemistry, Jyvaskyla University) as described in ref 9,20, and 21. A reagent blank was run with all samples to monitor for laboratory background contamination. Extraction and Analysis of Samples. CPs and PCPPs were extracted and analyzed as described previously (11,18,21). PCDFs were extracted for 48 h with a Soxhlet apparatus of 50-150-g samples of overnight airdried soil with acetone/hexane (1/1v/v) solution. Solvent was then evaporated in a mild air stream and the residue redissolved in 20 mL of pentane and transferred to a Teflon-lined glass tube. A 10-mL aliquot of concentrated HzS04 was added, and the mixture was shaken for 5 min. The HzS04phase was washed twice with 20 mL of pentane, and the combined pentane extracts were evaporated to 5 mL and pipeted on a chromatography column (10 X 300 mm) containing 10 mm of silica gel (upper layer), 50 mm of concentrated H,S04/silica gel (2/3 w/w), and 30 mm of basic alumina. The columns were first eluted with 20 mL of dichloromethane/hexane (1/49 v/v) and then
with 20 mL of dichloromethane/hexane (1/1v/v) solution. The latter fraction contained the PCDFs (22). The CPs and PCPPs were quantitated by a HewlettPackard 5790A gas chromatograph (GC) equipped with a 63Nielectron-capture detector (ECD), and SE-30 silica capillary column (i.d. 0.32 mm, 50 m, Orion Analytica), and a Hewlett-Packard 3390A integrator, after identification of the peaks by gas chromatography-mass spectrometry (GC-MS, Dani 3800 HR and Jeol DX 300 with JMA 2000 H computer) with 2,6-dibromophenol (Fluka) and 5chloro-2-(2,4-dichlorophenoxy)phenol(Irgasan DP-300, Bayer AG, Hamburg) as internal references spiked to samples before extraction. In GC-ECD analysis, the carrier gas was Hz and the makeup gas argon/methane (95/5). All the PCPPs were identified and quantitated with the response factor of the respective compounds except for 5 and 8 as indicated in the table where the response factors of isomers were used because the model compounds were not available. The recovery of the CPs and PCPPs from soil was calculated from the ratio of internal to external reference. If it was
