sufficiently depleted to result in a detectable change in the characteristic curve shown in Figure 3. This was a sufficiently long lifetime for the purposes of our aerosol experiment. The powder retention characteristics of the wall of the stripper were tested by attaching the outlet of the stripper to an aerosol counter, Climet Model 208A, which could measure particles as small as -0.5 pm in diameter. A low-resistance cartridge filter with a 0.3-pm pore size was attached to the stripper inlet. No counts were registered by the counter as long as the stripper was left untouched. However, a fairly strong rapping on the outside of the stripper would produce a sudden burst of counts. From this type of test, we concluded that the retention ability of the PbO2 by the mesh was acceptable as long as reasonable care was taken not to jar or vibrate the stripper or send very high airflow rates through it. Transmission loss of aerosols through the stripper was tested by connecting a Berglund-Liu Model 3050 aerosol generator to the stripper inlet and simultaneously monitoring the input and output ports of the stripper with aerosol counters. At the flow rates required in the aerosol experiment (300-400 cm3/min), almost all of the aerosol particles traversed the stripper. Thus, the fact that the inner surface of the stripper was slightly rough and rippled did not seem to cause a significant loss of aerosol particles. Conclusions
The SO2 stripper reported in this paper had a very high capacity for absorbing SO2 a t ambient levels. The lifetime (defined as the time over which the SO2 output characteristics remained sensibly constant) was estimated to be several
hundred hours a t an input SO2 concentration of 1 ppm. The performance of the stripper agreed well with the GormleyKennedy theory. The main drawbacks in the design of the stripper were that the wall was very delicate, and the replacement of the PbOz in the stripper was somewhat difficult, but the advantages of the high efficiency and absorptive capacity seemed to far outweigh these considerations. Acknowledgment
We thank Dr. James R. Brock for his suggestions and encouragement.
Literature Cited (1) Crider, W. L. Anal. Chem. 1965,37,1770. (2) Durham, J. L.; Wilson, W. E.; Bailey, E. B. Atmos. Enuiron. 1978, 12,883. (3) Fish, B. R.; Durham, J. L. Enuiron. Lett. 1971.2.13. (4) Durham, J. L.; Wagman, J.; Fish, B. R.; Seeley,'F.'G. Anal. Lett. 1972,5,469. (5) Hickey, H. R.: Hendrickson, E. R. J. Air Pollut. Control Assoc. 1965,15,409. (6) Smith, B. M.; Wagman, J.; Fish, B. R. Enuiron. Sci. Tech., 1969, 3, 558. (7) Townsend, J. S. Philos. Trans. R. SOC.London, Ser. A 1900,193, 129. (8) Gormley, P. G.; Kennedy, M. Proc. R. Irish Acad., Sect. A 1949, 52, 163. (9) DeMarcus, W. C.; Thomas, J. W. Oak Ridge, TN, 1952, Oak Ridge National Laboratory Report ORNL-1413. Received for review July 21,1980. Accepted December 18,1980, This work was supported by the Enuironmental Protection Agency under Grant No. R803814.
Identification and Mutagenic Properties of Some Chlorinated Aliphatic Compounds in the Spent Liquor from Kraft Pulp Chlorination Knut P. Kringstad, Pierre 0. Ljungquist, Filipe de Sousa, and Lars M. Stramberg* Swedish Forest Products Research Laboratory, Box 5604, S-114 86 Stockholm, Sweden ~
~
Spent chlorination liquor from the bleaching of softwood kraft pulp responds positively when tested according to the Ames test. This paper describes investigations with the aim of identifying compounds responsible for the mutagenic activity in such liquors. After enrichment by sorption (XAD 4)-and ion exchange (DEAE Sepharose)-analysis by GC-MS showed the presence of a variety of halogenated alkanes, alkenes, esters, cyclic and acyclic ketones, and saturated and unsaturated aldehydes in the spent chlorination liquor. Several of these are known or were found to be mutagenic. Two of the identified compounds appeared to be particularly strong mutagens. These are 1,3-dichloroacetone and 2-chloropropenal. ~
In the conventional processes for bleaching chemical pulp, treatment of the pulp with an aqueous solution of chlorine is the first of several consecutive steps. Depending upon type, unbleached pulp normally contains between 2% and 6% residual lignin. By the action of chlorine, the lignin is chlorinated, oxidized, and, to some degree, depolymerized, resulting in a partial water solubilization ( 1 , 2 ) . In recent years there has been a growing concern about the possible environmental impact of chlorinated organic compounds. Such compounds are often highly resistant to degradation in nature, which can mean that humans and animals are exposed to the compounds for long periods of time with harmful consequences. Genetic alterations are one such type 562
Environmental Science & Technology
of possible long-term damage which is important since there is a high degree of correlation between genetic-mutagenic effects and the development of cancer ( 3 , 4 ) . When unbleached softwood kraft pulp (kappa number -32) is treated with chlorine under standard bleaching conditions, -20-25 kg of organic material per ton of pulp is dissolved into the chlorination liquor ( 5 ) .A large number of compounds with a broad distribution of relative molecular mass and chemical nature constitute the dissolved organic material. Only a few of these compounds have so far been identified (6-12). Examples include various chlorinated and nonchlorinated aliphatic acids, chlorinated phenolic compounds, and a number of neutral compounds such as various chlorinated alkanes, alkenes, furan, pyrone, thiopene, and cymene derivatives. Recently, it was found that spent chlorination liquors exhibit a significant mutagenic effect when tested according to the Ames test (13, 14). The effect is apparently caused by different compounds with low relative molecular mass which, to a large degree, are soluble in ether. The compounds are formed in reactions between residual lignin and chlorine and are partially unstable under neutral and highly unstable under alkaline conditions ( 1 5 ) . In order to assess risks involved in releasing such liquors from the bleach plants, one needs a knowledge of the nature of the mutagenic compounds. This paper describes studies carried out with the aim of identifying the mutagenic compounds. A number of compounds not previously reported as constituents of spent chlorination liquor, and the mutagenic 0013-936X/81/0915-0562$01.25/0
@ 1981 American Chemical Society
properties of some of these as well as previously identified compounds, are presented.
Experimental Section Mutation Tests. Spent chlorination liquor, ether extracts of the liquor, and single model compounds were tested according to the Ames test as described previously (13).As a test organism, Salmonella typhimurium TA 1535 was used without the addition of liver microsomes (S-9 mix, metabolic activation). The tester strain was obtained from the Wallenberg laboratory (Stockholm) and was originally supplied by Dr. B. N. Ames. All tests were carried out in the direct plating mode. Methyl methanesulfonate (MMS, Eastman Kodak Co., USA) was used as a positive control for the strain. No special tests were conducted to detect mutagenic activity in the vapors of spent chlorination liquor, ether extracts of the liquor, or single model compounds (less hydrophilic compounds), nor were preincubation tests (bacteria plus compound) before incorporation into soft agar carried out. Toxicity of extracts and single model compounds toward the Ames Salmonella typhimurium TA 1535 strain was determined after appropriate dilution of the bacteria and plating onto nutrient broth agar (3 X IO2 cells/plate). The surviving bacteria were estimated by visual comparison of the plates, with 100%representing the same number of bacteria per unit area as the blank with no test solution (no toxicity) and 0 representing death of all bacteria. The spent chlorination liquor was tested by adding 0.4 mL to each plate. The ether extracts of the liquor were tested by adding 20 pL per plate. The final volume of all ether extracts tested was adjusted so that 20 pL corresponded to 0.4 mL of the original chlorination liquor. This means that the number of mutants for each ether extract and spent chlorination liquor are comparable. Model compounds were added in ether solution (20 pL/plate) or aqueous solution (0.4 mL/plate). The amount of single model compound added was varied over a wide range covering a bacterial survival from 0-loo%, including 6-8 different dosage levels. The results presented (Tables I and IV) from the Ames test are mean values of three or more assays (for specific mutagenic compounds, four or more assays). Spent Chlorination Liquor. An industrially prepared, unbleached softwood kraft pulp with a kappa number of 33 (corresponding to a lignin content of 5.1%) was used. The pulp was extracted in a Soxhlet extractor for 72 h with ethanol and thereafter for an equivalent period of time with dichloromethane to remove extractive materials. After air-drying, the pulp was stored in plastic bags a t 4 "C until used. Chlorination of the pulp was carried out by using 3.6%pulp consistency, a charge of 6% Clz, a temperature of 20 "C, and a reaction time of 60 min. The chlorine used (AGA, Specialgas, Sweden) contained 99.8% Cl2 and 0.2% COz. The spent liquor (pH 1.8) was separated from the pulp by filtration, and any residual chlorine present removed by purging with Nz. The liquor was stored at 4 "C until further use. Fractionation. Fractions containing major proportions of the mutagenic compounds present in the spent chlorination liquor were obtained in two different ways. In one, 3000 mL of the liquor was extracted with 800 mL of ether ((pro analysis) May and Baker Ltd., Dagenham, England) in a percolator for 48 h. After being dried with anhydrous NaZS04, the ether solution was concentrated to a final volume of 5 mL by careful evaporation in an evaporation flask equipped with a Vigreux column. In the other, spent chlorination liquor (2000 mL) was passed through a column (250 X 20 mm i.d.) containing XAD-4 sorption resin (Servachrom, 300-1000 pm, analytical grade, Heidelberg, West Germany). The flow rate used was
1.0 mL/min. Before use, the resin was purified by sequential solvent extractions with methanol, acetonitrile, acetone, and ether in a Soxhlet extractor for 8 h per solvent as recommended previously (16). The mutagenic compounds were eluted from the sorption resin with 150-200 mL of ether. The ether extract, concentrated to 15 mL, was divided into a neutral and an acidic/phenolic fraction by ion exchange using a DEAE-Sepharose CL-6B anion-exchange resin (acetate form (40-160 pm), column size 120 X 12 mm i.d., Pharmacia Fine Chemicals, Uppsala, Sweden). The fraction containing neutral compounds was eluted by passing ether (250 mL) through the column. The fraction containing phenolic and acidic compounds was thereafter obtained by passing CO2-saturated ether (250 mL) through the column ( 1 7 ) . Gas Chromatography and Mass Spectrometry (GCMS). The fraction containing the neutral compounds was evaporated to a final volume of 1-2 mL. For gas-chromatographic (GC) analysis, 1.0 pL of the solution was injected into a Packard-427 gas chromatograph equipped with a flame ionization detector (FID). The columns used were an OV-17 glass WCOT column (49 m X 0.27 mm i.d.1 manufactured by Ultrasep, Abo Akademi, Finland, or an UCON 550 LL glass WCOT column (25 X 0.25 mm i.d.) manufactured by RSL, St. Martens Latem, Belgium. The injector temperature was 120 OC, and the detector temperature 260 "C. Temperature programming for the OV-17 was 30 "C for 10 min followed by an increase in temperature to 235 "C at 2 OC/min. The carrier gas (N2) flow rate was 0.41 mL/min. Temperature programming for the UCON 550 LL was 30 "C for 16 min followed by an increase in temperature to 170 "C at 3 "C/min. The carrier gas (N2) flow rate was 1.82 mL/min. The GC-MS investigations were carried out by using a Carlo Erba (Fraktovap MOD 2900) gas chromatograph-Finnigan mass spectrometer (3200 F) with an on-line computer system (6000). The mass spectra were all run with 70 eV. The injector temperature was 200 "C, the transfer-line temperature 300 OC, and the ion-source temperature -100 "C. Model Compounds. Sources of the tested (Ames test) compounds, most of which were commercially available, are listed in Table IV. The cyclic ketone 2,3-dichlorocyclopentene-1,4-dione and the unsaturated aldehyde 2-chloropropenal were prepared according to methods described in the literature (18,19).2-Chloropropenalshould be handled with great care because of its strong mutagenic effect. The structure of the synthesized compound was confirmed by 13C NMR and MS. 13CNMR (CD3COCD3) 6: 133.45 (C3), 141.26 (C2), 186.29 ((21); spectra recorded with reduction of decoupling effect ("off resonance") showed a doublet (Cl), a singlet (CB), and a triplet (C3); the 13C NMR spectra were run on a Varian CFT-20 spectrometer. Mass spectra: m/e (relative intensity) 90 (loo), 62 (53),61 (52),92 (32), 27 (22), 63 (19), 29 (17).
Results and Discussion The spent chlorination liquor investigated in the present work was produced in the laboratory by chlorinating an industrially prepared softwood kraft pulp with a kappa number of 33 corresponding to a content of residual lignin of -5.1%. Before chlorination the pulp was extracted successively with ethanol and dichloromethane to remove any extractives present. When tested according to the Ames test, the numbers of mutants found for the spent chlorination liquor were those shown in Table I. As a first step in the workup of the compounds responsible for the mutagenic effect, the spent chlorination liquor was extracted with ether. As shown in Table I, -75% of the mutagenic activity was found in the ether extract. However, the extraction procedure required the use of a relatively large quantity of ether and a rather long extraction time. FurtherVolume 15, Number 5, May 1981 563
Table 1. Number of Mutants Formed by Testing According to the Ames Test = sample
no. of mutants
survival of test bacterla,
Yo
original C-liquor
-150
100
ether extract of C-liquor ether-extracted C-liquor XAD extract of C-liquor
-120 -50 -1 25 -50 -105
100 100
-20
100
XAD-extracted C-liquor neutral part of ether-extracted or XAD-extracted C-liquor phenolic and acidic part of ether-extracted or XAD-extracted C-liquor ether and NaCl controls a
19
100 100 100
100
Salmonella fyphimurium TA 1535 used as test organism ( 73)
more, it was f o u n d that, even when h i g h l y purified ether was used, small quantities of impurities were introduced which interfered w i t h t h e GC-MS analvsis. F o r these reasons enrichment of the mutagenic compounds was carried o u t instead by sorption on X A D - 4 resin. T h e elution o f the mutagenic compounds f r o m the r e s i n required less ether. As shown in Table I, -7540% o f t h e mutagenic activity could again be isolated f r o m the spent chlorination liquor. With t h e a i m o f obtaining a further concentration of compounds w i t h mutagenic activity, we separated t h e X A D - e x tracted material i n t o a neutral and an acidic/phenolic fraction. The conventional technique o f achieving this, Le., b y adding sodium bicarbonate a n d sodium hydroxide t o t h e ether extract, could n o t be used since t h e mutagenic compounds are unstable under alkaline conditions (15). Instead, t h e m i x t u r e was fractionated o n a DEAE-Sepharose C L - 6 B anion-exchange resin by using ether t o elute n e u t r a l compounds a n d thereafter CO2-saturated ether t o
Table II. Identified Compounds and Their Mutagenic Activity According to the Ames Test identlfied compds
dichloromethane chloroform carbon tetrachloride bromodichloromethane dibromochloromethane trichloroethylene tetrachloroethylene pentachloropropene five isomers of monochlorinated methylbutenes monobrominated methylbutene tetrachloroallene methyl dichloroacetate ethyl chloroacetate ethyl dichloroacetate ethyl trichloroacetate monochloroacetone 1,l-dichloroacetone 1,3-dichIoroacetone
technique of identlficatlon a
A A A B B A A A A
TA 100, pos neg (carcinogen) neg (carcinogen) TA 100, pos TA 100, pos TA 100, pos TA 1535, pos TA 100, pos TA 1535, neg
C C C C B A B A A A B A
TA 100, TA 1535, pos unknown unknown unknown unknown TA 1535, neg unknown TA 1535, neg TA 100, neg TA 1535, neg unknown TA 100, pos TA 1535, pos unknown unknown unknown TA 100, pos TA 1535, neg TA 1535, neg
A
l , l , 1-trichloroacetone 1,1,3-trichloroacetone l,l, 1,3-tetrachIoroacetone 1,1,3,3-tetrachloroacetone pentachloroacetone hexachloroacetone
B B B A
A A A A
trichlorocyclobutenone four chlorinated cyclopentene-l,2-diones monochloroacetaldehyde trichloroacetaldehyde 2-chloropropenal
C C A A A A
ref lo the Ames test
mutagenic activity b
TA 100, pos TA 1535, pos unknown unknown TA 100, TA 1535, pos TA 1535, neg TA 100, pos TA 1535, pos
22 23 24 22 22 22 25 (see Table IV) 25
see Table IV 26
see Table IV see Table IV 27 see Table IV 27 see Table IV
27 see Table IV see Table IV 27 see Table IV
28-3 1 (see Table IV) see Table IV 32 see Table IV
a (A) Complete identification based on mass-spectral interpretation and confirmed by comparison with a reference spectrum of the substance. (8) Complete identification based on mass-spectral interpretationand confirmed by comparison with a reference spectrum from "Eight Peak Index" (33). (C)Tentative structure; identification based on mass-spectral interpretation. Mass spectra (six most abundant mass fragments) of these substances are given in Table Ill. Ames test, Salmonella typhimurlum.
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elute acidic/phenolic material. This technique has been shown to be an effective way of separating ether-soluble acidic and neutral extractives of pine wood (17). Table I shows that 80%of the mutagenic activity originally present in the XAD-enriched fraction was found in the neutral Table 111. Mass Spectra of Compounds for Which Tentative Structures Are Given in Table II pentachloropropene (Mf 212) fragmentation of the compound: M - 35 (base-peak cluster) m/e (re1 int): 179 (loo), 177 (77), 181 (47), 83 (22), 85 (17), 214 (13) m/e (M): 212 (10) five isomers of monochlorinated methylbutenes (Mr 104; two examples are given) fragmentation of the compound: M - 15, M - 35 m/e (re1 int): 41 (loo), 69 (68), 39 (59), 53 (37), 67 (20), 104 (20) m / s (re1 int): 69 (loo), 41 (69), 104 (35), 53 (33), 39 (29), 67 (27) a monobrominated methylbutene (Mf 148) fragmentation of the compound: M - 15, M 79 m/e (re1 int): 41 (loo), 69 (80), 150 (30), 148 (29), 53 (20), 39 (20)
-
tetrachloroallene (M, 176)
-
fragmentation of the compound: M - 35 - 35 - 35 35 m / e (re1 int): 141 (IOO), 143 (96), 71 (58), 106 (52), 145 (32), 108 (31) m / s (M): 176 (23) trichlorocyclobutenone (Mr 170) fragmentation of the compound: M - 28 - 35, M - 35 - 28 m / e (re1 int): 107 (loo), 109 (62), 142 (48), 144 (48), 72 (35) 135 (23) m / e (M): 170 (21) four chlorinated cycIopentene-l,2diones (2 examples are given): dichlorocyclopentene-1,2-dione (M, 164) fragmentation of the compound: M - 28 - 28 m/e (re1 int): 82 (IOO),54 (87), 136 (82), 73 (70), 164 (69), 110 (60) trichlorocyclopentene-l,2-dione (Mf 198) Fragmentation of the compound: M - 28 - 28 m / e (re1 int): 88 (loo), 60 (go), 107 (62), 198 (52), 200 (48), 110 (48)
fraction obtained in this way. The fraction containing phenolic and acidic material did not show significant mutagenic activity, even after being concentrated 10 times, and therefore was not studied further. The composition of the neutral fraction was investigated by GC-MS, and the compounds so far identified (complete or tentative identification) are listed in Table 11. For those compounds which were identified by mass-spectral interpretation only (tentative identification), the six most abundant fragments of the respective spectra are given in Table 111. As can be seen from Table 11, the identified compounds belong to the following major classes of organics: halogenated alkanes, alkenes, esters, cyclic and acyclic ketones, and saturated and unsaturated aldehydes. Some of the listed alkenes and the cyclic ketones have been found earlier in spent chlorination liquor from the bleaching of softwood kraft pulp (10-12). Monochloroacetaldehyde has been found earlier in the mixture of reaction products resulting from the chlorination of lignosulfonic acid (20). Somewhat surprisingly, there are three bromine-containing compounds among the halogenated alkanes and alkenes (Table 11).It is not clear whether the formation of these is due to the presence of bromine in the chlorine used for bleaching the pulp or to the presence of bromides in the pulp bleached. In the class of halogenated ketones, all possible isomers of chlorinated acetones were found. In the case of the chlorinated cyclopentenediones, it is likely that these are of the 1,2-diketo type, since the mass spectrum of 2,3-dichlorocyclopentene-1,4-dione ( M , 164) did not correspond to the mass spectra obtained from the chlorinated cyclic diketo compounds fou'nd in the liquor. In Table I1 available information on the mutagenic properties of the listed compounds as determined by the Ames test, using Salmonella typhimurium TA 100 and TA 1535, is included. This information was extracted partly from the literature and partly from preliminary tests carried out in this laboratory exclusively using Salmonella typhimurium strain TA 1535 as test organism. The results of the latter are summarized in Table IV. The doses per plate given in the table were about the highest possible which yielded 70-100% bacterial survival for each tested compound, with the exception of the one for monochloroacetaldehyde, which showed 20% bacterial survival at the reported dose.
Table IV. Mutagenic Activity a for Some Compounds Identified in Spent Chlorination Liquor compd tested
trichloroethylene tetrachloroethylene ethyl chloroacetate ethyl trichloroacetate monochloroacetone 1,3-dichIoroacetone 1,1,3,3-tetrachloroacetone pentachloroacetone hexachloroacetone monochloroacetaldehyde trichloroacetaldehyde 2-chloropropenal NaCl control ether control a
dose/plate
0.1 mg 0.1 mg 0.38 mg 1.26 mg 10 Pg 4.5 PS 16 Pg 50 l.4 1.0 mg 45 Pg 0.5 mg
9.1 PFLQ 0.4 mL
no. of mutants
37 31 14 19 26 248 20 14 38 40 19 368 18 19
added to the bacterial culture in solutlon
ether (20 pL) ether (20 pL) ether (20 pL) ether (20 pL) ether (20 pL) ether (20 pL) ether (20 pL) ether (20 pL) ether (20 pL) water (0.4 mL) water (0.4 mL) ether (20 pL)
source of compd
E. Merck, 99.5% E. Merck, 99.0% Fluka AG, Buchs SG, 99.0% Fluka AG, Buchs SG, 99.0% Ega-Chemie, 97.0 % Fluka AG, Buchs SG, 98.0% Ega-Chemie, 96.0% Ega-Chemie, 97.0% Fluka AG, Buchs SG, 97.0% Ega-Chemie,' 5 0 4 5 % in water Ega-Chemie, 99.0% synthesized ( 79)
20 PL Ames test, Salmone/la typhimurium TA 1535 without metabolic activation.
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565
As shown in Table 11, several of the compounds identified so far in the neutral ether-soluble fraction of spent chlorination liquor from the bleaching of softwood kraft pulp respond positively in the Ames test. A compound was listed positive when the number of revertants exceeded the background level by a factor of 2 or more (21). This is true for some of the halogenated alkanes, alkenes, and acetones as well as for two of the halogenated aldehydes. Of these, 1,3-dichloroacetone and 2-chloropropenal appear to have a particularly high activity, as indicated in Table IV. The compounds show linear doseresponse. However, to what degree each or all of these compounds are responsible for the total mutagenic activity of the spent chlorination liquor cannot yet be decided. This is due to the lack of quantitative data on the occurrence and the activity of the respective mutagens. Also, the number of unidentified compounds in the neutral fraction is still large. Investigations with the aim of extending available knowledge on these questions are presently underway in this laboratory. Although no data are yet available on the concentrations of the described mutagenic compounds in the spent chlorination liquor, studies now in progress indicate that the levels will be low, with an upper limit of -50 pg/L for the most concentrated compounds. Acknowledgment
Thanks are due to Dr. K. Lindstrom and J. Nordin for helpful discussions and criticism of the manuscript. Literature Cited (1) Singh, R. P. “The Bleaching of Pulp”; TAPPI Press Book 0102
B043, Atlanta, GA, 1979. 121 Linderen. B. 0. Suen. Pannerstidn. 1979,82,126. (3) Ramll, C: Ambio 1978, 7; i44. (4) Ames, B. N. Science 1979,204, 587. (5) Hardell, H.-L.; de Sousa, F. Suen. Papperstidn. 1977,80, 110. (6) Das, B. S.;Reid, S. G.; Betts, J. L.; Patrick, K. J . Fish. Res. Board Can. 1969,26,3055. (7) Ota, M.; Durst, W. B.; Dence, C. W. T a p p i 1973,56,139. (8) Rogers, I. H. Pulp Pap. Mag. Can. 1973, 74,111. (9) Lindstrom, K.; Nordin, J. J . Chromatogr. 1976,128,13. (10) Lindstrom, K.; Nordin, J. Suen. Papperstidn. 1978,81,55.
(11) Lindstrom, K.; Nordin, J.; Osterberg, F., submitted for publication in the Proceedings of the National Meeting of the American Chemical Society, Las Vegas, Aug 24-28,1980, (12) Bjqh-Seth, A.; Carlberg, G. E.; M$ller, M. Sci. Total Enuiron. 1979,11,197. (13) Ander, P.; Eriksson, K.-E.; Kolar, M.-C.; Kringstad, K.; Rannug, U.; Ramel, C. Suen Papperstidn. 1977,80,454. (14) Eriksson, K.-E.; Kolar, M.-C.; Kringstad, K. Suen. Papperstidn. 1979,82,95. (15) Stockman, L.; Stromberg, L.; de Sousa, F. Cellul. Chem. Technol. 1980,14,517. (16) Junk, G. A,; Richard, 3. J.; Grieser, M. D.; Witiak, D.; Witiak, J. L.: Areuello. M. D.: Vick. R.: Svec. H. J.: Fritz. J. S.: Calder. G. V. J . ChFomatogr. 1974,99,745. (17) Zinkel, D. F.; Rowe, J. W. Anal. Chem. 1964.36. 1160. (18) Roedig, A.; Hornig, L. Chem. Ber. 1955,88,2003. (19) Shostakovskii, M. F.; Annenkova, V. Z.; Ivanova, L. T.; Ugryumova, G. S. I z u . Sib. O t d . Akad. Nauk. S S S R , Ser. Khim. Nauk 1967,6, 104. (20) Schwabe, K. Monatsh. Chem. 1950,81,609. (21) Seiler, J. P.; Mattern, I. E.; Green, M. H. L.; Anderson, D. Meeting Report, Second EuroDean Workshop on Bacterial in vitro Mutagenicity Test Systems (Ames Test Meeting, 1979); Mutat. Res. 1980, 74, 71. (22) Simmon. V. F.: Kauhanen., K.:, Tardiff. R. G. Dev. Toxicol. Enuiron. sci. i977,2,249. (23) National Cancer Institute. USA “Reaort on Carcinoeenesis Bioassay of Chloroform”; 1976. (24) McCann, J.; Choi, E.; Yamasaki, E.; Ames, B. N. Proc. Natl. Acad. Sci. U.S.A. 1975,72,5135. (25) Cernl, M.; K y p h o v i , H. Mutat. Res. 1977,47,217. (26) Nestmann, E. R.; Lee, E. G.-H.; Matula, T . I.; Douglas, G. R.; Mueller, J. C., submitted for publication in Mutat. Res. (27) Rapson, W. H.; Nazar, M. A.; Butsky, V. V. Bull. Enuiron. Contam. Toxicol. 1980,24,590. (28) Malaveille, C.; Bartsch, H.; Barbin, A.; Camus, A. M.; Montesana, R.; Croisy, A.; Jacquignon. P. Biochem. Biophys. Res. Commun. 1975,63, 363. (29) McCann. H.: Simmon. V.: Streitwieser., D.:, Ames. B. N. Proc. fiatl. Acad’Sci’. U.S.A. 1975, 72, 3190. (30) Rannue, U.; Gothe, R.: Wachtmeister, C. A. Chem.-Biol. Interact. 1976,12, 251. (31) Rosenkranz, H. S. Enuiron. Health Perspect. 1977,21,79. (32) Rosen, I. D.; Segall, Y.; Casida, J. E. Mutat. Res. 1980, 78, 113. (33) “Eight Peak Index of Mass Spectra”; Mass Spectrometry Data Center, Atomic Weapons Research Establishment: Aldermaston, England, 1970; Vols. 1and 2. Y
Received for reuieu; July 28,1980. Accepted December 9, I980
Correlations between Lead and Coronene Concentrations at Urban, Suburban, and Industrial Sites in New Jersey Arthur Greenberg,” Joseph W. Bozzelli,” Frank Cannova, Eric Forstner, Philip Giorgio, Douglas Stout, and Rina Yokoyama Department of Chemical Engineering and Chemistry, New Jersey institute of Technology, Newark, New Jersey 07 102 Concentrations of lead and selected polycyclic aromatic hydrocarbons have been monitored a t four New Jersey sites which can be characterized as urban, suburban, or industrial. A correlation between lead and coronene concentrations reported for sites in Los Angeles has been investigated for the New Jersey locations. The lead-coronene correlation is verified only for a location a t which motor-vehicle traffic is the overwhelming contributor to the airborne particulate load. One reason for the dichotomy between the published Los Angeles study and the present study is the significant dependence upon oil combustion for space heating in the Northeast in contrast to primary dependence on natural gas in Los Angeles.
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Introduction
The use of concentrations of the polycyclic aromatic hydrocarbon (PAH) coronene (more specifically, low benzo[a]pyrene/coronene ratios) as possible indicators of automobile emissions was suggested in 1962 by Sawicki and co-workers (1).A later California study ( 2 ) of airborne particulate matter implied that coronene is, like lead, a strong indicator of traffic density in the Los Angeles area. The study found that concentrations of total suspended particulates (TSP),lead, and various PAH, including benzo[a]pyrene, benzo[k]fluoranthene, benzo[ghi]perylene, and coronene were directly proportional to traffic density at three locations where traffic was the dominant airborne-particulate contributor. Inclusion of 0013-936X/81/0915-0566$01.25/0
@ 1981 American Chemical Society
