Envlron. Scl. Technol. 1904, 18, 743-748
Susceptibility of Environmentally Important Heterocycles to Chemical Disinfection: Reactions with Aqueous Chlorine, Chlorine Dioxide, and Chloramine Sechoing Lin and Robert M. Carlson" Department of Chemistry, University of Minnesota, Duluth, Minnesota 558 12
Eighteen environmentally significant hetereocycles were subjected to dilute aqueous solutions of chlorine, chlorine dioxide, and chloramine to examine those chemical transformations anticipated during water renovation. The products included those of chlorination and oxygenation, with chlorine dioxide giving oxygenation products. Chloramine was generally quite unreactive except a t low pH where a significant presence of hypochlorous acid may dictate the increase in chlorination products. The concern over the detrimental nature of environmental polynuclear aromatic hydrocarbons (PAH) to health has recently been expanded to include their heterocyclic analogues (1-4). Although the major focus of investigation has been the analysis of these heterocycles from effluents and residuals of energy-generating processes involving fossil fuels (5-15), azaarenes (16-18) and dibenzothiophene (19,20) have been observed in groundwater and surface waters and as constituents of particulates and sediments. The evaluation of the susceptibility of organic materials present in wastewater to chemical transformations during disinfection has included the study of a variety of structural types, including PAH (21). The presence of heterocyclic PAH in environmental settings and the possible toxic nature of these compounds have prompted their inclusion in the reevaluation of the impacts associated with current chemical disinfection practices (Le., the use of chlorine, chlorine dioxide, and chloramines).
Experimental Section Instruments and Apparatus. The Hewlett-Packard 5995C GC-MS was equipped with a split/splitless interface and a cross-linked methylsilicone fused silica column (Hewlett-Packard, 15 m X 0.2 mm i.d.). Some fractions were screened prior to gas chromatography-mass spectroscopy (GC-MS) analysis using a Tracor 550 capillary gas chromatograph fitted with a J & W DB-5 narrow bore column and a flame ionization detector (FID). GC temperature programs were from 40 (or 70 "C) to 290 OC. The HPLC instrumentation consisted of a Waters M6000 pump and U6K injector, a C-18 column (Perkin-Elmer 25 cm X 4.6 mm i.d., Sil-X), Perkin-Elmer LC-75 detector, and a Hewlett-Packard Model 3390A integrator. Chromatographic conditions were varied to achieve adequate retention for the organic components under investigation. The mobile phase was 30%, 45%, or 50% acetonitrile in water with a flow rate of either 0.8 or 1.0 mL/min. Fritted glass columns (24 X 300 mm) containing XAD-2 resin (Amberlite, 16-50 mesh) to a height of approximately 80 mm were used to concentrate the organics. Measurements of pH were carried out on a Graphics Controls Model PHM 7900 pH meter with a Fisher Microprobe combination electrode. Chemicals. Pyridine, 4-picoline, 3-methylindole (7), quinaldine (441, quinoline (391, isoquinoline (51), indole (1),2-phenylindole (131, N-phenylpyrrole (20), carbazole (33), acridine (57), phenanthridine (55), 4-azafluorene (63), 5,6-benzoquinoline (661, 7,8-benzoquinoline (69), benzo00 13-936X/84/09 18-0743$0 1.5010
thiazole (72), benzo[ b]thiophene (741, and dibenzothiophene (77) were all purchased from Aldrich Chemical Co. and checked for purity by high-performance liquid chromatography (HPLC). The mono- and dibasic potassium phosphates, sodium thiosulfate, sodium hypochlorite, and acetonitrile (HPLC grade) were obtained from Fisher Chemical Co. The ammonium hydroxide was purchased from Du Pont. Technical-grade methylene chloride was redistilled and checked for an appropriate low residual before use. The water was purified by passage through a Continental deionizer and a Milli-Q (Millipore Corp.) system. The following reference standards were obtained commercially: isatin (Eastman), anthranilic acid (Matheson Coleman & Bell), N-phenylmaleimide, isotoic anhydride, N-phenylsuccinimide, o-aminoacetophenone, dibenzothiophene S,S-dioxide, S(lOH)-acridone, isocarbostyril, 2-benzothiazolol, oxindole, and N-formylanthranilic acid (Aldrich). A sample of hydroxylactam, 24 (22),was kindly provided by Dr. D. Lightner (University of Nevada, Reno). 3-Methyloxindole (8) (23),3-methyldioxindole (9) (24, 25), 3-chloro-2-phenylindole (14) (26,27),3,3-dichloro-2phenylindole (15) (26),5(6H)-phenanthridone (56) (28), 2-phenyl-3,1-benzoxazin-4(4H)-one (17) (29), 2,5-dichloro-N-phenylpyrrole (26) (30), 2,3,5-trich1oro-Nphenylpyrrole (27) (30), 2,3,4,5-tetrachloro-N-phenylpyrrole (30) (30),and dibenzothiophene oxide (78) (31) were prepared as reference standards by using methods reported in the literature. o-Formamidoacetophenone(10) was synthesized in quantitative yield by heating oaminoacetophenone with excess ethyl formate at 140 OC for 16 h in a stainless-steel reactor. Procedure. The sodium hypochlorite and chlorine dioxide reagent solutions were prepared by dilution from concentrated stock solutions and were titrated (iodometric) prior to use. Sodium hypochlorite (5%;Fisher) was used as a stock solution. The concentrated chlorine dioxide was generated as described in the literature (32). Chloramine solutions were prepared from commercial concentrated ammonium hydroxide stock mixed with hypochlorite to achieve an ammonia to hypochlorite ratio of 3:l. Solutions of the heterocycles were prepared by stirring a carefully weighed amount of the organic (ca. 4 mg) into 4 L of phosphate-buffered water. Each reaction was initiated at 24 f 1 "C by addition, with stirring, of a predetermined volume of the oxidizing reagent to the bottle containing the organic solution. The pH and organic content (HPLC analysis) were monitored throughout the reaction period, and the reaction was quenched with sodium thiosulfate (4 equiv/equiv of hypochlorite). Samples were concentrated either by liquid-liquid extraction (3X, CHzClz)or by adsorption onto XAD-2 resin, followed by elution with CH&N and then by overnight extraction with CHZCl2. In some instances, both techniques were employed. All fractions were concentrated to 1-2.5 mL in vacuo, with additional concentration effected under a stream of nitrogen. All samples were analyzed by GC-MS. Fractions containing acidic componenb were treated with diazomethane
0 1984 American Chemlcal Society
Environ. Sci. Technol., Vol. 18, No. 10, 1984
743
Scheme I
"'"24
1
H
a;H
5
tr
Scheme I1 Scheme IV
n
0
a
'4
,
8
!!
and reanalyzed. The results are described in Tables 1-111 (for Table 111, see paragraph at end of paper regarding supplementary material).
Results and Discussion Chlorine, chlorine dioxide, and chloramine are three common disinfectants used in water treatment applications (33,341. Under the pH range as employed in this investigation (pH 5-8) hypochlorous acid and hypochlorite will coexist, with hypochlorite concentration increasing with increasing pH (34). In the presence of ammonia, monochloramine and dichloramine are the predominate species. Higher pH values favor monochloramine over dichloramine (35,36). On the other hand, chlorine dioxide is fairly stable throughout this pH range and was the only oxidative species that was considered (33). The relative reactivities of the hetero-PAH are summarized in Table I. Products, with their relative concentrations, are indicated in Table 11. Mass spectral data (i.e., the eight most abundant ions) are included in Table I11 (supplementary material). Except for a direct probe analysis of an HPLC fraction containing 3,3-dichloro-2phenylindole, GC-MS proved to be a suitable analysis technique. Indole (1). Indole was readily oxidized by hypochlorite/hypochlorous acid, chloramines, and chlorine dioxide to oxindole (3) and isatin (4) (Scheme I). In the case of chloramine the 3-chloroindole (2) (presumably via N-chloroindole) (37) could be detected. The chlorination of indole has been extensively investigated, including recent work which demonstrated the intermediacy of N-chloroindole and 3-chloro-3H-indole (37). Related electrophilic additions and oxidations of indole and its derivatives have been studied in some detail (38). 3-Methylindole (7). With all three oxidizing agents, 3-methyloxindole (8) and o-formamidoacetophenone (10) were the major oxidation products of 3-methylindole (7). Although a pathway involving chlorinated intermediates is shown (Scheme 11) (25,38),a similar product distribution could be envisioned that involves a series of oneelectron transfers. 2-Phenylindole(13). 2-Phenylindole produced 3-chloro products (14, 15) upon reaction with hypochlorite/hypochlorous acid (26) or with chloramine (Scheme 111). 3Chloroindole was the major product generated from low molar ratios of chlorine to 2-phenylindole and from chlo744
Environ. Sci. Technol., Vol. 18, No. 10, 1984
2_4
I
z7
Scheme V 33
-
J
W""
3p, Mono-CI, 2 Isomers 33, Di-CI, 4 Isomers 39 Tri-CI, 2 Isomers 3_7,Tetra-Cl,l Isomer
on 33
ramine. The chloro products were found to parallel those observed when chlorination was carried out in organic solvents. Chlorine dioxide generated oxidation products (16-19) not incorporating chlorine (39). The structures of the products were confirmed by independent synthesis. N-Phenylpyrrole (20). N-Phenylpyrrole and the hypochlorite/hypochlorous acid solution provided a series of oxidation/chlorination products that can be rationalized by sequential chlorination/hydrolysis or by the chlorination of intermediate hydrolysis products (30, 38, 40) (Scheme IV). A similar pattern of oxidation products was observed with chlorine dioxide and with chloramine. Only small amounts of chloro products were observed with either of these latter reagents. Carbazole (33). Carbazole reacted rapidly with chlorine dioxide (1.6 ppm) to give the quinoid compound (Scheme V) as the major product (41,42). At higher concentrations of chlorine dioxide (16 ppm) an orange-brown solution was generated from which no identifiable products could be detected. Moreover, dimerization products commonly observed when oxidation is carried out in organic solvents (43, 44) were also not detected. The reaction of carbazole with hypochlorite/hypochlorous acid occurs more slowly than with chlorine dioxide and gave predominantly chlorinated products (Scheme V). The number of isomers of each type produced suggests that chlorination is occurring only ortho and para to the nitrogen.
Table I. Approximate Contact Period for the Individual Reaction To Proceed to at Least 95% Completionu“ compd indole 3-methylindole 2-phenylindole N-phenylpyrrole isoquinoline acridine phenanthridine benzothiazole benzo[b] thiophene dibenzothiophene carbazole
reagent At pH 7.0 OCl-/HOC1 OC1-jHOel ClOZ OCl-/NH, OCl-/HOC1 ClOZ OCl-/NH3 OCl-/HOC1 ClOz OCl-/NHa OCl-/HOC1 OCl-/HOC1 ClOz OCl-/HOC1 OCl-/HOC1 OCl-/HOC1 OCl-/HOC1 OCl-/HOC1 c102
At pH 5.3 OCl-/HOC1 indole ClOZ OCl-/NHa OCl-/HOC1 3-methylindole ClOZ’ OCl-/NH3 OCl-/HOC1 2-phenylindole ClOZ OCl-/NH3 OCl-/HOC1 N-phenylpyrrole ClOZ OCl-/NH3 OCl-/HOC1 isoquinoline OCl-/HOC1 acridine ClOz phenanthridine OCl-/HOC1 OCl-/HOC1 benzothiazole OCl-/HOC1 benzo[b]thiophene dibenzothiophene OCl-/HOC1 OCl-/HOC1 quinoline OCl-/HOC1 quinaldine OCl-/HOC1 carbazole clog
Scheme VI
,
contact period, h 0.25 0.25 21.5 0.25 0.25 21.5 0.25
H
43
39
42,
Monochloroquinollne
n=
0
4_3.n= 1
4_1
1.0
3.5 0.25 1.0 50.0
4.0 0.75 46.0 1.0 48.0 1.5
0.25 0.25 0.25
0
--
/
0.25 0.25 1.25 0.25 0.25
5_3
CI
1.25
0.25 0.50 0.50
0.25 0.75
15.25 1.0 0.25 5.3 0.25 24.0 0.25 0.25 6.0
24.0 5.3 0.25
57
60, n=2 Monochloroacridine
6_l,n:3
62
The organic substrates (pyridine, 4-picoline, quinoline, 4-azafluorene, 5,6-benzoquinoline, and 7,8-benzoquinoline) that did not react significantly (Le., less than 95% reacted based upon the disappearance of the organic substrate) over 60 h of contact period under the conditions employed were not listed in the table. *The concentrations of organic substrated in aqueous solution were in to 1.0 X lo4 M. eThe concentration of the range of 1.0 X sodium hypochlorite solution was (2.2-2.5) X lo4 M; the chlorine dioxide solution was 2.4 X lo4 M the chloramine solution was prepared from the same range of sodium hypochlorite concentrations by adding ammonium hydroxide solution to achieve a 3 to 1 mole ratio of ammonia to hypochlorite. dFor those reactions that were extremely fast, 15 min of contact time was allowed before termination. Other reactions were analyzed until 95 h 10% of the organic substrate reacted.
Reaction of Pyridine Derivatives (Quinoline (39) (45), Quinaldine (44), Isoquinoline (51), Acridine (57) ( 4 6 ) , Phenanthridine (55), 4-Azafluorene (63), $6Benzoquinoline (66), and 7,B-Benzoquinoline (69)) with Chlorine. A typical feature of the “disinfection” of mono- and dibenzopyridine derivatives is the generation of products formed by an oxidative combination of oxygenation and chlorine incorporation (Scheme VI). Except for the reaction of phenanthridine and acridine with
chlorine dioxide, products resulted only with the use of hypochlorite/hypochlorousacid. Pyridine and 4-picoline were found to be unreactive under all conditions studied (Table I). Reaction of Benzothiazole (72),Benzo[ blthiophene (74), and Dibenzothiophene (77) with Chlorine, The major oxygen products with hypochlorite/hypochlorous acid with the thiaarenes were those that did not incorpoEnviron. Sci. Technol., VoI. 18, No. 10, 1984 745
Table 11. Product Distribution from the “Disinfection” of Water Containing Heteroarenesa-e compd indole, 1
oxidant (pH)
reaction % time, h reacted
3-methylindole, 7
NaOCl (7.0) (5.3) CIOz (7.0)d (5.3)d NaOC1/NH3.(7.0) (5.3) NaOCl (7.0)
0.25 0.25 0.25 0.25 21.5 1.35 0.25
>95 >95 >95 >95 >95 >95 >95
2-phenylindole, 13
(5.3) C102 (7.0) (5.3) NaOCl/NH, (7.0) (5.3) NaOCl (7.0)
0.25 0.25 0.25 21.5 1.25 0.25
>95 >95 >95 >95 >95 >95
(5.3) ClOz (7.0)d
0.25 1.0
>95 >95
0.5
0.25
>95 >95 >95 >95
50.0
80
6.0
>95
NaOCl (7.0)
50.0
32
(5.3)
24.0
>95
oxindoleC(M), 3; isatinc (S), 4; isatonic anhydridec (T), 5 3 (M); 4 (TI 3 (M); 4 (TI; 5 (TI 3 (MI; 4 (M); 5 (T);3-chloroxindole (T), 6 3 (M); 4 (T); 3-chloroindole (S), 2 3 (M); 2 (S) 3-methylo~indole~ (M), 8; o-formamidoacetophenoneC(M), 10; monochloro-o-formamidoacetophenone(TI, 12; 311 methyldioxindolec (T),9; o-aminoacetophenonec (T), 8 (M); 10 (M); 9 (T); 11 (T) 8 (M); 10 (M); 9 (T); 11 (T) 8 (M); 10 (M); 9 (T);11 (T) 8 (M); 10 (S); 9 (T); 11 (T) 8 (M); 9 (SI 3,3-dichloro-2-phenylindoleC (M), 15; 3-chloro-2-phenylindolec (T), 14; 2-phenyl-3,l-benzoxazin-4(4H)-onec (T),17 15 (M); 14 (M); 17 (T); 2-phenylindolenone (S), 16 17 (M); 16 (M); 2-hydroxy-2-phenylindoxyl (T), 18; obenzoylanthranilic acidc (T), 19 17 (M); 16 (M); 18 (T); 19 (T) 14 (M) 14 (M) 2-hydroxy-N-phenylpyrrole (T), 21, 22 (2 isomers); monochloro-2hydroxy-N-phenylpyrrole (T), 23; N-phenylmaleimidec (T), 29; hydroxylactamC(M), 24; N-phenylsuccinimidec (S), 25; monochloro-N-phenylsuccinimide(T), 28; 2,5-dichloro-Nphenylpyrrolee (M), 26; 2,3,5-trichloro-N-phenylpyrr~le~ (M), 27; 2,3,4,5-tetra~hloro-N-phenylpyrrole~ (T),30 21 (S); 23 (T); 29 (S); 24 (M); 25 (T); 27 (T); 30 (T); monohydroxy-N-phenylmaleimide(T),32; monoch1oro-Nphenylmaleimide (T);31 21; 22 (S) (2 isomers); 23 (T); 29 (M); 24 (M); 25 (M); 32 (T) 21; 22 (S) (2 isomers); 29 (S); 24 (M); 25 (M); 32 (T) 21; 22 (M) (2 isomers); 29 (T); 24 (T); 32 (T) 21; 22 (M) (2 isomers); 23 (T);29 (T); 24 (M); 25 (S); 32 (T) monochlorocarbazoles (M), 34 (2 isomers); dichlorocarbazoles (S), 35 (4 isomers); trichlorocarbazoles (T), 36 (2 isomers); tetrachlorocarbazole (T),37 34 (S) (2 isomers); 35 (M) (4 isomers); 36 (S) (2 isomers); 37 (T) 34 (T); azaquinone (M), 38 34 (TI; 38 (M) carbostyril (M), 40; monochloroquinoline (T), 41 40 (M); monochlorocarbostyril (T), 42; 41 (T); dichlorocarbostyril (T), 43 monohydroxyquinaldines (T),45 (2 isomers); monochloroquinaldines (S), 47 (2 ring isomers); monochloroquinaldine (S), 46 (on the methyl group); trichloroquinaldine (T),49; dichloroquinaldines (T),48 (2 isomers) 45 (T); 47 (S) (2 isomers); 46 (S); 48 (S) (2 isomers); 49 (T);
(5.3)
0.25
>95
ClOz (7.0) (5.3) NaOCl/NH, (7.0) (5.3) NaOCl (7.0)
1.0 0.75
>95 >95 >95 >95 >90
NaOCl (7.0)
4.0
>95
monochloroisoquinoline (T),54; isocarbostyril (M), 52;
NaOCl (5.3) NaOCl (7.0) (5.3) ClOz (7.0) (5.3) NaOCl (7.0)
1.0 1.0 0.25 50.0 50.0 0.75
>95 >95 >95 47
54 (M); 52 (M); 53 (T)
(5.3)
0.25
>95
I
N-phenylpyrrole, 20
carbazole, 33
quinoline, 39 quinaldine, 44
productsn*
-
(5.3)d NaOCl/NHQ , ” (7.0) . . (5.3) NaOCl (7.0)
(5.3) ClOz (7.0) (5.3) NaOCl (7.0) (5.3)
3.5 0.5
50.0
15.25 2.0 1.0
0.25 0.25
>95 >95 >95
monochlorohydroxyquinaldine (T), 50
isoquinoline, 51
monochloroisocarbostyril (T), 53
phenanthridine, 55
acridine, 57
58
>95
46.0 2.5
>95 >95
4-azafluorene, 63
ClOz (7.0) (5.3) NaOCl (7.0)
50.0
8
5,6-benzoquinoline, 66
(5.3) NaOCl (7.0)
50.0 50.0
19
7,8-benzoquinoline, 69
(5.3) NaOCl (7.0)
50.0 50.0
33 27
(5.3) NaOCl (7.0) (5.3)
50.0
benzothiazole, 72
48.0 24.0
34 >90 >90
746
Envlron. Scl. Technol., Vol. 18, No. 10, 1984
8
5(6H)-phenanthrid~ne~ (M), 56 56 (M) 56 (MI 56 (M)
9(10H)-acridonec (S), 58; monochloro-9(10H)-acridone (M), 59; dichloro-9(10H)-acridones (S), 60 (2 isomers); trichloro-9(10H)acridone (T), 61 monochloroacridine (T), 61; 58 (S), 59 (MI, 60 (S) (2 isomers); 61 (T) 58 (M) 58 (M) monochloro-4-azafluorene (T),64 (2 is0 mers); monohydroxy-4azafluorene (TI, 65 64
(T); 65 (T)
monohydroxy-5,6-benzoquinoline(S), 67; monochloro-5,6benzoquinoline (T),68 (2 isomers) 67 (S); 68 (T) monohydroxy-7,8-benzoquinoline(T),70; monochloro-73benzoquinoline (T), 71 (2 isomers) 70 (T); 71 (T)
2-benzothiazoloF (M), 73 73 (M)
Table I1 (Continued)
compd
oxidant (pH)
reaction time, h
reacted
productsa"
benzo[b]thiophene, 74
NaOCl (7.0)
1.5
>95
benzo[b]thiophene S-oxide (TI, 75; benzo[b]thiophene S,Sdioxide (M), 76
dibenzothiophene, 77
NaOCl (7.0)
0.25 0.25
>95 >95
(5.3)
0.25
>95
75 (T); 76 (M) dibenzothiophene &oxidec (T), 78; dibenzothiophene S,SdioxideC(M), 79 78 (T); 79 (M)
(5.3)
%
'M, major; S, minor; T, trace, bThe presence of the isomers was confirmed by resolved GC peaks and mass spectra. "he product identification is based upon the comparison of the unknown with GC and/or HPLC retention times and mass spectra of authentic compounds. 1.6 ppm of chlorine dioxide was employed for the reaction. e GC-MS identification was made via the comparison with a mixture reported to contain all of the chloro products. Scheme VI1
72
73
L7
7!3
79
rate chlorine (47) (Scheme VII). In the reaction of aqueous chlorine with benzo[ b]thiophene, the sulfone predominates, while the sulfoxide is present in only trace amounts (48). In contrast, dibenzothiophene gave a greater amount of the sulfoxide relative to the sulfone. The sulfoxides are presumed to be reaction intermediates in sulfone formation. No reaction was observed with chlorine dioxide or with chloramine. Effects of pH Change (5.3-7.0). The results indicate that although there was a substantial effect upon the rate of reaction of those agents where equilibria is influenced by PH OC1-
HOCl
"a
HOCl e NHzCl
NHCl2
there were only minimal changes in the distribution of the major products. A particularly dramatic rate enhancement was observed for chloramines at lower pH. This phenomenon may be interpreted as the regeneration of hypochlorous acid when such solutions are acidified (49). Implications to Health. All of the compounds that were investigated have been shown to be present in environmental settings. In addition, several examples of azaor thiaheterocyclic PAH included in this study have exhibited mutagenic activity (2,13-15,50-54). Among the products observed in this investigation, only phenanthridone (55,56)has been determined to be directly mutagenic, although B(~-quinolinone (e.g., carbostyril) (57), S(lOH)-acridone (58),and o-aminoacetophenonehave been described as cocarcinogens (59). However, because only limited studies of product toxicity have been performed, the actual impact to health of disinfection practices involving the aqueous chemistry of chlorine, chloramines, or chlorine dioxide with hetero-PAH remains an open question. Conclusions. (1) Reactions with hypochlorous acid/ hypochlorite generate products that incorporate chlorine
as well as introduced oxygen into the molecule. Chlorine dioxide gave predominantly oxygenation products. (2) The reactions involving chloramines (NH2Cl/NHCl,) proceed at such a very slow rate relative to chlorine dioxide or hypochlorous acid/hypochlorite that significant amounts of reaction products from hetero-PAH should not be observed during normal water disinfection processes. However, where the pH may be lowered to about 5 , a significant increase in product formation should be anticipated. (3) An aqueous reaction medium has a significant impact upon the nature of the products. For example, dimerization products often seen in the oxidation of indole (60), 2-phenylindole (29),and N-phenylpyrrole (61) in organic solvents were not detected in this study. (4) Some of the products of chemical disinfection of hetero-PAH have adverse biological activity. This observation may offset the positive effect of "eliminating" some of the hetero-PAH which themselves are reported to possess possible mutagenic properties. Acknowledgments
Excellent technical assistance in preparing the manuscript was provided by R. Liukkonen, M. Lukasewycz, J. Bastian, and R. Thom. Supplementary Material Available Table I11 giving mass spectral data for products obtained from the disinfection of water containing heteroarenes (7 pages) will appear following these pages in the microfilm edition of this volume of the journal. Photocopies of the supplementary material from this paper or microfiche (105 X 148 mm, 24X reduction, negatives) may be obtained from Microforms Office, American Chemical Society, 1155 16th St., N.W., Washington, DC 20036. Full bibliographic citation (journal, title of article, author, page number) and prepayment, check or money order for $12.00 for photocopy ($14.00 foreign) or $6.00 for microfiche ($7.00 foreign), are required. Registry No. 1,120-72-9; 2,16863-96-0; 3,59-48-3; 4,91456-5; 5, 118-48-9; 6,68235-96-1; 7,83-34-1; 8, 1504-06-9; 9,3040-34-4; 10, 5257-06-7; 11, 551-93-9; 12, 91311-32-9; 13, 948-65-2; 14, 76794-16-6; 15, 76794-18-8; 16, 2989-63-1; 17, 1022-46-4; 18, 19282-62-3; 19, 579-93-1; 20, 635-90-5; 21, 91311-34-1; 22, 55609-32-0; 23, 91311-36-3; 24, 26709-62-6; 25, 83-25-0; 26, 3006846-5; 27, 77124-13-1; 28, 36342-11-7; 29, 941-69-5; 30, 77124-14-2; 31, 42595-16-4; 32, 91311-33-0; 33, 86-74-8; 34, 54886-36-1; 35, 28804-85-5; 36, 91327-54-7; 37, 28804-84-4; 38, 54049-15-9; 39,91-22-5; 40,59-31-4; 41,91311-37-4; 42,1810-67-9; 43, 91311-38-5; 44, 91-63-4; 45, 1333-48-8; 46, 4377-41-7; 47, 91311-39-6; 48, 91311-41-0; 49, 91311-40-9; 50, 91311-42-1; 51, 119-65-3; 52,491-30-5; 53,91311-44-3; 54,91311-43-2; 55,229-87-8; 56, 14548-01-7; 57, 260-94-6; 58, 578-95-0; 59, 91311-45-4; 60, 91311-46-5; 61, 91311-47-6; 62, 91311-48-7; 63, 244-99-5; 64, 91311-49-8; 66, 91311-50-1; 66, 85-02-9; 67, 91311-51-2; 68, 91311-52-3; 69,230-27-3; 70,91311-53-4; 71,91311-54-5; 72,95-16-9; Environ. Sci. Technol., Vol. 18, No. 10, 1984 747
73,934-34-9;74,95-15-8; 75,51500-42-6;76,825-44-5;77,132-65-0; 78,1013-23-6; 79, 1016-05-3; HOCl, 7790-92-3; ClOz, 10049-04-4.
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Receiwed September 2,1983. Revised manuscript received March 19, 1984. Accepted April 6, 1984. Financial support for this project was provided by the U.S. Environmental Protection Agency (Grants R807455 and R809695). The contents of this paper do not necessarily reflect the views and policies of the U.S. EPA, and the mention of trade names and commercial products does not constitute their endorsement.
