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Ann Arbor, MI, 1979; pp 231-260. (16) Grimmer, G.; Naujack, K.-W.; Schneider, D. Fresenius’ 2. Anal. Chem. 1982,311,475-484. (17) Dunn, B. P.;Armour, R. J. Anal. Chem. 1980,52,2027-2031. (18) Griest, W. H.; Caton, J. E.; Guerin, M. R.; Yeatts, L. B.,
(5) Lee, M. L.; Vassilaros, D. L.; Phillips, L. V.; Hercules, D. M.; Asumaya, H.; Jorgenson, J. W.; Maskarinec, M. P.; Novotny, M. Anal. Lett. 1979, 12 (A2), 191-203. (6) Lao, R. C.; Thomas, R. S.; Oja, H.; Dubois, L. Anal. Chem. 1973,45, 908-915. (7) Lao, R. C.; Thomas, R. S. In “Polynuclear Aromatic Hydrocarbons”; Jones, P. W.; Leber, P., Eds.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 429-452. (8) “Particulate Polycyclic Organic Matter”; National Academy of Sciences: Washington, DC, 1972, Appendix C, p 301. (9) Choudhwy, D. R. In “PolynuclearAromatic Hydrocarbons”;
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Aromatic Hydrocarbons”;Jones, P. W.; Leber, P., Eds.; Ann Arbor Science: Ann Arbor, MI, 1979; pp 217-229. (14) Environmental Protection Agency “GuidelinesEstablishing Test Procedure for the Analysis of Pollutants: Proposed Regulations”. Fed. Regist. 1979, 44, 69464. (15) Snook, M. E.; Severson, R. F.; Higman, H. C.; Arrendale, R. F.; Chortyk, 0. T. In “Polynuclear Aromatic Hydrocarbons”;Jones, P. W.; Leber, P., Eds.; Ann Arbor Science:
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Jr.; Higgins, C. E. In ”Polynuclear Aromatic Hydrocarbons: Chemistry and Biological Effects”; Bjerrseth, A,; Dennis, A. J., Eds.; Battelle Press: Columbus, OH, 1980, pp 819-828. Griest, W. H.; Caton, J. E. In “Polynuclear Aromatic Hydrocarbons: Chemical Analysis and Biological Fate”; Cooke, M.; Dennis, A. J., Eds.; Battelle Press: Columbus, OH, 1981; pp 719-730. Lao, R. C.; Thomas, R. S. In “Polynuclear Aromatic Hydrocarbons: Chemistry and Biological Effects”; Bjerrseth, A.; Dennis, A. J., Eds.; Battelle Press: Columbus, OH, 1980; pp 829-839. Lee, F. S.-C.; Pierson, W. R.; Ezike, J. In “Polynuclear Aromatic Hydrocarbons: Chemistry and Biological Effects”; Bjmseth, A.; Dennis, A. J., Eds.; Battelle Press: Columbus, OH, 1980; pp 543-563. Friedel, R. A.; Orchin, M. “Ultraviolet Spectra of Aromatic Hydrocarbons”; Wiley: New York, 1951.
Received for review August 23,1983. Accepted December 7,1983. This research was supported in part by the U S . Department of Agricu1turelU.S. Department of Energy (Grant 70-59-2181 6-004-1) and in part by the National Science Foundation.
NOTES Polynuclear Azaarenes in Wood Preservative Wastewater Jeanette Adamst and Choo-Seng Giam” Department of Chemistry, Texas A&M University, College Station, Texas 77843
Polynuclear azaarenes in a creosote-pentachlorophenol wood preservative wastewater were analyzed. T h e total concentration of azaarenes was determined to be 1300 mg kg-’. Potential adverse effects of these compounds on environmental quality and health suggest a need to develop analytical protocols for measuring azaarenes in hazardous wastes. An evaluation of data in t h e literature indicates t h a t basic polynuclear azaarenes such as quinolines a n d benzoquinolines may be widespread in the environment. They have been identified on air particulate matter from Europe (1, 2),t h e United States (3),a n d t h e southern North Atlantic Ocean ( 4 ) . Moreover, more recent data indicate that these compounds are also present in ambient air in t h e vapor phase and at higher levels than previously reported on particulate matter (5). Polynuclear azaarenes have also been found in lake a n d marine sediments (6-8) a n d *Address correspondence to this author at the Graduate School of Public Health (IEHS), University of Pittsburgh, Pittsburgh, PA 15261. t Present address: Pharmacy and Allied Health Professions, Section of Medicinal Chemistry, Northeastern University, Boston,
MA 02115. 0013-936X/84/0918-0391$01.50/0
groundwater adjacent to a n underground coal gasification site (9). T h e presence of these compounds in t h e environment has been mainly attributed t o the use of fossil fuels (6, 7, 10). T h e occurrence of polynuclear azaarenes in coal tar has been known since the early 1800s (11). They have been identified more recently in both natural a n d synthetic crudes (12-15) a n d subsequently derived distillates and oils (16-19). I n petroleum oils, the total fraction of basic organic nitrogen has been estimated to range from -0.2 to 0.5% (15). For coal-derived liquids, however, this range may approach -10-20% (1419). I n order t o understand some aspects of t h e environmental impact of polynuclear azaarenes, i t is important to determine both sinks and environmental sources (energy and nonenergy related). However, relatively little attention has been given to t h e analysis of these compounds in nonenergy-related hazardous waste streams (20). For example, Lao e t al. (21),in their determination of polynuclear aromatic hydrocarbons in a creosote wood preservative sludge, reported data for only two polynuclear azaarenes, benzoquinoline a n d acridine (7100 and 3500 mg L-I, respectively). Although creosote and benz[ c] acridine have been listed by t h e US.E P A as hazardous pollutants (22),there are no established analytical protocols in t h e U S . EPA
0 1984 American Chemical Society
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organic layers
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polynuclear azaarenes
Figure 2. Flame ionization gas chromatogram of basic fraction of wood preservative wastewater; peak numbers refer to compounds listed In Table I .
I
Flgure 1. Analytical scheme for determlnlng polynuclear azaarenes in wood preservative wastewater.
guidelines (23,24) for specifically determining polynuclear azaarenes. T h e identification and quantitation of polynuclear azaarenes may be particularly relevant since many of these compounds have been reported to be toxic (25, 26), teratogenic (27), mutagenic, and/or carcinogenic (28, 29). We, therefore, wish t o present data from an analysis of these compounds in a creosote-pentachlorophenol wood preservative wastewater. Experimental Section
Reagents. Polynuclear azaarenes were obtained in the highest purity available (>97%) from either Aldrich or Pfaltz & Bauer. Organic solvents were distilled-in-glass from Burdick & Jackson. Control of Blanks. Techniques similar to those described previously were followed to ensure that there was no background contamination (5, 30, 31). For instance, all glassware, NaCl, and NazS04were heated overnight a t 320 OC. Glassware was serially rinsed with methanol, acetone, and twice with petroleum ether (PE). NaCl in water (5% w/v) was prepared with distilled water which had been continuously extracted with PE to remove objectionable organics. Procedure. The wastewater sample collected from an on-site storage pond located a t a Central Texas woodpreserving industry was kindly supplied to us (32). The general procedure (33) is outlined in Figure 1. A sample (44.5 g) was added to a 1-L separatory funnel containing 100 m L of PE and 700 mL of 5% NaCl in water. (The NaCl was used to reduce the aqueous solubility of the organic solutes.) The aqueous layer was made basic (pH >12) with NaOH and extracted. The organic layer was removed, and the aqueous layer was extracted 3 more times with 100-mL portions of PE. The combined PE layers were then extracted with 700 mL of 5% NaCl in water which had been made acidic (pH 12) with NaOH and extracted 3 times with 100-mL portions of PE. The combined organic layers were dried with Na2S04 and concentrated over steam in a Kuderna-Danish evaporative concentrator. The sample concentrate was quantitatively transferred to a 3-dram vial with Teflon-lined cap and diluted as needed. 392
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Instrumental Analysis. Polynuclear azaarenes were analyzed by flame ionization gas chromatography (Hewlett-Packard 5830-A) with a 30-m SP-2100 (a dimethyl silicone fluid) glass capillary column. Conditions were as follows: oven temperature 70-280 OC a t 7 deg min-l with 2 min of initial hold; detector 320 "C; injector 250 "C; splitless injection; H 2 carrier gas. For compounds not commercially available, a response factor of 27 area units/ng was employed. This was calculated by averaging the response factors of 12 standard reference compounds, including two- and three-ring azaarenes. Concentrations were not corrected for recoveries. Azaarenes isolated in the basic fraction were characterized by GC-MS (Hewlett-Packard 5992) with a 30-m SP-2100 glass capillary column and capillary interface. Conditions were the same as with the FID-GC analysis except for 5 min of initial hold and injector temperature of 270 "C. MS conditions were as follows: electron impact 70 eV; scan speed 200 amu s-l; electron multiplier 2000 V; scan range 40-450 amu. Results and Discussion The gas chromatogram of the basic fraction isolated from the creosote-PCP wood preservative wastewater indicated that there were numerous compounds present (Figure 2). By use of GC retention time and mass spectral analysis, polynuclear azaarenes such as quinoline, isoquinoline, and alkyl- and benzo-substituted azanaphthalenes were characterized at a total (estimated, minimal) concentration of 1300 mg kg-l (Table I). The presence of polynuclear azaarenes in this wastewater implies t h a t an adverse effect on environmental quality can result from improper disposal of such wastes. For instance, transport of azaarenes through migration in soil (34,35) or by overland flow of contaminated wastewater can deteriorate the quality of potable groundwater (9,35) or aquatic ecosystems. Concentrations of polynuclear azaarenes many times less than those reported here have been shown to have toxic and teratogenic effects on freshwater organisms (27,36). For instance, the 48-h LCm's for Daphnia magna exposed to quinoline, isoquinoline, and acridine are 28.5,4.1, and 2.3 mg L-l, respectively (37). (An analogous LCm for naphthalene is 24.1 mg L-l; anthracene is nontoxic a t aqueous saturation (37).) Besides producing immediate toxic effects, polynuclear azaarenes can also bioaccumulate in aquatic food-chain organisms (38, 39). From results presented here, and the report that azaarenes such as quinoline and isoquinoline resist activated
Table I. Polynuclear Azaarenes in Creosote-PCP Wood Preservative Wastewater mg kg‘’ compoundb no.a 260 quinolineC 1 69 isoquinolineC 2 55 2-methylq~inoline~ 3 11 8-methylq~inoline~ 4 95 C,-azanaphthalened 5 38 7-methylq~inoline~ 6 47 7, 8 C ,-azanaphthalenesd 21 2,6-/2,7-dimethylquinolineC 9 66 10-12 C ,-azanaphthalenesd 14 13, 1 4 methylvinylazanaph thalenesd 12 15 C,-azanaphthalened 16 4-azafluorenec 16 53 7,8-benzoquinolinec 17 55 acridineC 18 5,6-benzoquinoline/phenanthridineC 71 19 350 20-23 C -benzoazanaphthalenesd vinyl benzoazanaph thalened 3.0 24 54 25-27 azafluoranthenes/azapyrenesd 4.4 28, 29 C I -azafluoranthenes/azapyrenesd 5.2 30, 31 dibenzoazanaphthalenesd 1300 total a From Figure 2. C,, C,, and C, = methyl-, dimethylor ethyl-, and trimethyl- or propyl substituents, respectively. Structural assignment from comparison t o GC retention and mass spectral data of authentic standard. Structural assignment from comparison to mass spectral literature data and fragmentation patterns. ~
Table 11. Possible Sources of Polynuclear AzaarenesU industry and EPA hazardous waste no. waste F005 spent solvent and still bottoms from the recovery of pyridine F016 air pollution control scrubber sludges from coke ovens and blast furnaces KO25 still tails from the production of methylethylpyridines KO35 wastewater treatment sludges from the production of creosote K048-KO52 petroleum refining wastes a From ref 22. sludge treatment of wastewaters (40), it may be suggested t h a t the determination of polynuclear azaarenes be included in hazardous waste analytical protocols. Even if organic bases account for a smaller portion of contaminants present in a hazardous waste, their environmental impact may be significantly greater than, for instance, t h a t exhibited by higher concentrations of polynuclear aromatic hydrocarbons (41). Additionally, since polynuclear azaarenes similar to those reported here have been identified in emissions from oil refineries (42) and coke ovens (21, 42), they may be present in a number of other hazardous wastes (Table 11). Registry No. PCP, 87-86-5; quinoline, 91-22-5; isoquinoline, 119-65-3;2-methylquinoline, 91-63-4;8-methylquinoline, 611-32-5; 7-methylquinoline, 612-60-2; 2,6-dimethylquinoline, 877-43-0; 2,7-dimethylquinoline, 93-37-8; 4-azafluorene, 244-99-5; 7,8benzoquinoline, 230-27-3; acridine, 260-94-6; 5,6-benzoquinoline, 85-02-9; phenanthridine, 229-87-8; water, 7732-18-5.
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Pollut. 1965, 9, 291. Received for review July 21, 1983. Accepted December 1, 1983. Partial support for this research was provided by National Science Foundation Projects OCE 80-19601 and OCE 77-12482 and the Robert A. Welch Foundation.
