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. L i t e r a t u r e 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 at 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
a fourth locale, having moderate traffic in addition to petroleum refineries and chemical industry, left coronene and lead as the best indicators of traffic density ( 2 ) .Thus, coronene and lead concentrations were strongly correlated for all four sites. It has been stated that at least 90% of atmospheric lead originates in automotive emissions ( 3 )and, therefore, the strong correlation of this metal’s concentration with traffic is expected in areas where there are no significant nonautomobile lead sources. Coronene concentrations were employed in a later study ( 4 ) to assess the contribution of automotive emissions to airborne PAH levels. However, the generality of the coronene correlation with traffic density (or lead concentration) is less certain. In particular, one wonders whether coronene concentrations could be employed to indicate automobile emission contributions in other areas of the country having different patterns of fuel use. It was duly noted (2) that no coal is burned in Los Angeles and that most heat and power are derived from natural gas. In connection with a program concerned with the monitoring of airborne pollutants a t a variety of New Jersey locations (5-7), it was of interest to examine how well the reported lead-coronene correlation held up in a densely populated, industrial, mid-Atlantic state. Oil fulfills a significant fraction of heating and power requirements in New Jersey while coal plays a fairly minor role. Experimental Section Sample Collection. Twenty-four-hour samples were collected every 6 days at the following four sites (the samples described in this paper were collected from August 1, 1979, through December 29,1979): (1)Newark, NJ-Military Park location in the business district close to avenues of heavy vehicular traffic. (2) Camden, NJ-roof of Rutgers University Camden campus library (ca. 25 ft above ground); there is little vehicular traffic in the immediate vicinity, but the location is less than 0.2 mi from the Benjamin Franklin Bridge to Philadelphia; the area is characterized by nearby chemicalindustry and petroleum-storage facilities. (3) Elizabeth, NJ-adjacent (50 ft) to a trailer a t Exit 13 of the New Jersey Turnpike close to a massive petroleum refinery complex. (4) Rutherford, NJ--yard of a suburban residence on Pierrepont Avenue across from an elementary school which exhibited a cancer cluster in the mid 1970s; the nearest gasoline station is ca. two blocks from the site and there is some chemical industry across the Passaic River. High-volume (blower motor assembly) samplers were used for the collection of airborne particulates at each site. Newark and Camden samples were collected by the New Jersey Department of Environmental Protection (NJDEP) using General Metal Works Hi Vol collectors with 20 X 25 cm rectangular glass-fiber filters (Schleicher and Shull). A 2.5 X 20 cm strip was taken for metal analysis, and a 5 X 20 cm strip was employed for PAH analysis. Rutherford and Elizabeth samples were collected by New Jersey Institute of Technology (NJIT) personnel using General Metal Works GMW 2000 and Staplex TF l a Hi Vol assemblies fitted with a 10.2-cm diameter glass-fiber filter (Gelman Type A/E). Half of each circular filter was employed for metal analysis and half for PAH analysis. The flow measurement of NJDEP-operated samplers was monitored with a pressure transducer which transmitted a signal to a recorder for a continuous log. The exhaust pressure was observed at the beginning and the end of a collection period for the NJIToperated samplers using a 0-2-in. W.C. magnehelic gauge (Dwyer Instruments). In the infrequent circumstance where a flow decrease was observed, the mean flow’was calculated by averaging the initial and final flows. Samples collected by the NJDEP a t Newark and Camden locations were returned to NJIT for analysis during a period of 2-8 weeks following collection. Rutherford and Elizabeth
samples were returned promptly to the laboratory. Once received, all samples were stored in the dark and analyzed as rapidly as possible. Lead Digestion and Analysis. Particulates on glass-fiber filters were digested in acid solution and analyzed by atomic absorption spectroscopy according to USEPA-approved procedures (8-10). The wavelength employed for lead analysis was 217.0 nm. Calibration curves were prepared each day that samples were analyzed. Digestion and analysis of USEPA lead-impregnated standard filter strips and USNBS-analyzed urban particulate standards consistently showed less than 5% error in the overall procedure. PAH Extraction and Analysis. Particulates on glass-fiber filters were Soxhlet extracted for 8 h with 150 mL of n-hexane (Schleicher and Schull filters) or methylene chloride (Gelman filters). A 1-mL aliquot of a solution containing l-methyltriptycene was added as an internal standard. The extract was rotoevaporated and concentrated to -1 mL, and the PAH fraction isolated by employing thin-layer chromatography (TLC) following a modification of a published procedure (11) (toluene was substituted for benzene). The TLC adsorbent powder containing the PAH fraction was scraped from the plate and rinsed with 3 mL of tetrahydrofuran, and the resulting solution concentrated to -0.1 mL by evaporation under a stream of nitrogen. A 10-pL aliquot was analyzed by employing reverse-phase high-performance liquid chromatography with a polymeric ODS column according to a slight modification of the published procedure (12) (initial 40% aqueous acetonitrile is run linearly to pure acetonitrile over a 15-min period and then maintained a t 100%acetonitrile). Component PAHs are monitored simultaneously a t 280 and 365 nm; fluorescence is also employed to aid in PAH identification (excitation, 360 nm; emission, 2440 nm). Identifications of individual peaks are made by comparison of retention times, “doping” studies, fluorescence properties, and the use of the 280:365-nm absorbance ratios which are characteristic for a given PAH (13). Discussion of Results Table I lists concentrations of total suspended particulate (TSP), lead (Pb), benzo[h]fluoranthene (BkF), benzo[a]pyrene (BaP), benzo[ghi]perylene (BghiP), and coronene (Cor) determined for 20 Newark samples between August 1, 1979, and December 29,1979. The levels of lead (14-16) and PAH (17,18) are similar to those reported in other studies of the New York-New Jersey metropolitan area. Coronene concentrations exhibit the best linear relationship with lead concentrations; the correlation for the Newark site is represented by eq 1and the correlatioil coefficient is 0.909. The next best correlation is between benzo[ghi]perylene and lead concentrations at the Newark location. [coronene (ng/m3)] = 0.932[lead (pg/m3)]
+ 0.033
(1)
Table TI lists a variety of attempted linear correlations between pollutants a t the four locations studied in the present work. The better correlation between P b and T S P a t the Newark site compared to the Camden site clearly indicates that gasoline combustion is a more dominant airborne-particulate contributor at the first location. This is further supported by the observation that the fraction of lead in suspended particulate matter at the Newark site is almost double that a t the Camden site (7). The Rutherford and Elizabeth locations were not sampled by the NJDEP High Vol network, and thus no TSP data are available for these sites. The best PAH-lead correlation is that found for coronene a t the Newark site, an observation consistent with the conclusions of the earlier-cited Los Angeles study. It is quite clear that the other PAH-lead correlations are inferior and are less significant or nonsignificant (see footnotes c-e in Table 11).In Figure Volume 15, Number 5, May 1981
567
Table 1. Concentrations of Total Suspended Particulate (TSP, g/m), Lead (Pb, pg/m3), and Four Selected PAHs a (ng/m3) Including Benzo[klfluoranthene (BkF), Benzo[alpyrene (BaP), Benzo[ghi]perylene (BghiP), and Coronene (Cor) Observed at the Newark, NJ, Site between August 1, 1979, and December 29, 1979 TSP
Pb
BkF
BaP
8/1/79
date
133
1.213
0.15
0.17
0.44
0.74
8/13/79
43
1.185
0.37
0.39
1.55
0.72
8/25/79 9/6/79
70
1.259
0.29
0.32
1.21
0.95
0.873 2.080
0.34
0.45
1.55
0.62
9/12/79
42 96
0.72
0.65
2.78
1.20
9/18/79
79
1.670
0.67
0.74
1.89
1.07
9/24/79
72
2.328
0.91
0.98
3.87
2.29
9 130 179
31
1.123
0.27
0.23
1.66
1.08
10/12/79
89
3.360
2.12
3.65
9.11
4.01
1O /18/79
133
4.003
10/24/79
36
0.867
2.05 0.51
2.98 0.90
8.84 2.88
3.27 1.16
10/30/79
69
1.812
1.19
1.64
4.90
I .98
11/5/79
74
2.187
1.47
2.33
5.43 2.16
2.64 0.58
Cor
BghiP
11111/79
28
0.806
0.58
0.64
1 1117/79
48
1.038
1.19
113
2.794
1.48 2.93
3.29
11/23/79
1.26 2.82
7.08
2.64
11/29/79
31
0.597
12/5/79
86
1.666
0.52 1.60
0.77 2.19
2.29 5.49
1.02 1.87
12/17/79
34
0.702
0.61
0.92
19
0.365
0.40
0.55 0.43
2.67
12/29/79
1.40
0.48
a
Concentrations reported for BkF, BaP, and BghiP are the averages of 280-and 365-nm data; coronene data is based on absorbance at 280 nm.
Table II. Summary of Attempted Linear Correlations between Pollutants at Four New Jersey Locations slope
intercept
Pb (pglm3) vs. TSPb (pglm3) Newark Camden
correlation, 0 ( y
0.0213 0.00783
0.185 0.150
Cor (ng/m3) vs. Pb (pg/m3) Newark Camden Rutherford Elizabeth
0.932 0.592 1.05 0.593
0.033 0.208 -0.063 0.058
0.909 0.616c 0.757 0.406 d,'
BghiP (ng/m3) vs. Pb (pg/m3) Newark Camden Rutherford Elizabeth
2.27 2.18 1.60 0.483
-0.096 0.109 0.093 0.742
0.865 0.807 0.492c 0.191s
BaP (ng/m3) vs. Pb (pg/m3) Newark Camden Rutherford Elizabeth
0.891 1.472 0.891 0.367
-0.203 -0.027 0.209 0.443
0.815 0.820 0.504c 0.307
0.605 1.45 0.584 0.493
-0.025 -0.096 0.333 0.094
0.791 0.798 0.476d 0.504c
2.43 2.47 2.20 2.07
-0.175 0.064 -0.259 -0.189
0.952 0.879 0.898 0.920
0.990 1.33 1.26 0.974
-0.287 0.145 0.055 0.149
0.929 0.710 0.887 0.889
YS. X )
BkF (ng/m3) vs. Pb (pg/m3) Newark Camden Rutherford Elizabeth BghiP (ng/m3) vs. Cor (ng/m3) Newark Camden Rutherford Elizabeth BaP (ng/m3) vs. Cor (ng/m3) Newark Camden Rutherford Elizabeth
corr coeff
0.768 0.5~11~
Correlations based on following numbers of samples: Newark (20), Camden (13),Rutherford (la),Elizabeth (18). Total suspended particulate (TSP) measured by NJDEP at Newark and Camden only. Cannot reject null hypothesis at 0.01level. Cannot reject null hypothesis at 0.025 level. e Cannot reject null hypothesls at 0.05 level. ' t o 95 value (1.78)barely above test value (1 75).
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Environmental Science & Technology
1a plot is displayed indicating the concentration of coronene vs. the concentration of lead for the Newark location. The graph is fitted by eq 1.
Conclusions The best coronene-lead correlation occurred for samples collected at the Military Park location near the Newark business center in a nonresidential area having very concentrated daytime motor-vehicle traffic and no obvious nonautomobile lead sources. The conclusion that automobile traffic was the major PAH source is strengthened by the fact that the least-squares line virtually passes through the origin. The correlation at the residential site in Rutherford is weaker although the least-squares line also virtually passes through the origin. It appears, therefore, that a good correlation between lead and coronene concentrations can be anticipated only where traffic is the predominant particulate contributor. One must recall that significant coronene concentrations also occur in emissions from oil and coal combustion (19).However, the relative concentration of coronene compared to those of other larger (pentacyclic or higher) PAHs is significantly higher in gasoline exhaust than in emissions from oil combustion. Thus, the percentage of coronene in a mixture of selected PAHs also including benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[e]pyrene, perylene, dibenz[ah]anthracene, and benzo[ghi]perylene averages -29% in gasoline emissions (20)and ranges from 2.7% to 7.8% in oil emissions (19). Benzo[a]pyrene, in contrast to the situation for coronene, exhibits similar concentrations in both gasoline (ca. 11%)and oil emissions (ca. 4.0-9.8%) (19,20). Benzo[ghi]perylene, another major PAH in gasoline emissions (average 34%of eight selected PAHs) (20) is also a significant component in oil emissions (19.5-25.6%) (19).Thus, one would expect coronene to be a better indicator of automobile traffic than other PAHs, including benzo(a1pyrene and benzo[ghi]perylene. However,
at sites where oil combustion or some other PAH-producing process is an important source of airborne particulate matter, coronene-lead correlations should break down unless the nonvehicular production of coronene remains fairly constant, in which case it would provide a positive y intercept. The PAH which best reflects automobile emissions appears to be cyclopenta[cd]pyrene (21). Grimmer et al. (21) have demonstrated that levels of this compound collected in automobile emissions and in vehicular tunnels far exceed those of the larger PAHs. Work in our laboratory also supports these findings since it has disclosed that the concentrations of cyclopenta[cd]pyrene found in the airborne particulate matter collected in an underground parking garage is responsible for a considerably larger fraction of the PAH mixture than one finds in ambient air (22).As Grimmer et al. (21) note, cyclopenta[cd]pyrene is significantly more reactive than benzo[a]pyrene, and precautions must be followed in its collection, storage, and workup. Particulate samples immediately refrigerated and placed in the dark following collection had cyclopenta[cd]pyrene fractions as high as 10 times those observed in particulates stored for a few days in the dark a t ambient temperature (7).Blanks (addition of a known amount of PAH in solution to the filter and subsequent workup) of the larger PAHs (pentacyclic or greater) studied in this laboratory indicated recoveries exceeding 90%, with recoveries of benzo[a]pyrene averaging 80%, while cyclopenta[cd]pyrene averaged only 65% (7). Acknowledgment We gratefully acknowledge helpful discussions with Professors Barbara Kebbekus and,Joan Daisey as well as informative correspondence with Professor Gernot Grimmer. Samples of airborne particulate matter obtained at Newark and Camden sites were collected by New Jersey Department of Environmental Protection personnel, under the direction of Les Falkinson, as well as Joanne Held, who supplied TSP data. Literature Cited
1.0
20
30
4.0
Lead (pg/rn3) Figure 1. Plot of the coronene concentration (ng/m3) vs. lead (pg/m3)
for 20 samples collected at the Military Park, Newark, NJ, location from August 1, 1979, through December 29, 1979 (see Table I).
(1) Sawicki, E.; Hauser, T. R.; Elbert, W. C.; Fox, F. T.; Meeker, J. E. Am. Ind. Hyg Assoc. J. 1962, 7,137. (2) Gordon, R. J.; Bryan, R. J. Enuiron. Sci. Technol. 1973, 7, 1050. (3) Faoro, R. B.; McMullen, T. B. Washington, DC, USEPA Report EPA-450/1-77-003. (4) Gordon, R. J. Enuiron. Sci. Technol. 1976,10, 370. ( 5 ) Bozzelli, J. W.; Kebbekus, B. B. “Analysis of Selected Volatile Organic Substances in Ambient Air”; New Jersey Department of Environmental Protection, Oct 1979. (6) Bozzelli, J. W.; Kebbekus, B. B. “Lead and Toxic Metals in Airborne Particulates”; New Jersey Department of Environmental Protection, Oct 1979. (7) Bozzelli, J. W.; Kebbekus, B. B.; Greenberg, A. “Analysis of Selected Toxic and Carcinogenic Substances in Ambient Air”; New Jersey Department of Environmental Protection, Sept. 1980. ( 8 ) USEPA “National Ambient Air Quality Standard For Lead”; Federal Register 43, No. 194, 1978, p 46 246. (9) Mitchel, W. J.; Midgett, M. R. J. Air Pollut. Control Assoc. 1979, 29,959. (10) American Society for Testing and Materials “Tentative Method of Analysis for Lead Content of Atmospheric Particulate Matter Using Atomic Absorption Spectroscopy”; ASTM Method No. 315, Standard Methods of Analysis, ASTM 1978. (11) Zoccolillo, L.; Liberti, A.; Brocco, D. Atmos. Enuiron. 1972,6, 715. (12) Ogan, K.; Katz, E.; Slavin, W. Anal. Chem. 1979,51, 1315. (13) Greenberg, A.; Yokoyama, R.; Giorgio, P.; Cannova, F. “Polynuclear Aromatic Hydrocarbons: Chemistry and Biological Effects”; Bjdrseth, A,, Dennis, A. J., Eds.; Battelle Press: Columbus, OH, 1980; pp 193-8. (14) USEPA Report No. EPA-600/4-76-041, National Aerometric Sampling Network, 1976. (15) Stevens, R. K.; Dzubey, T. G.; Russwurm, G.; Rickel, D. Atmos. Enuiron. 1978,12,55. (16) Kneip, T. J.;Lioy, P. J.;Wolff, G. T. J. Air Pollut. Control Assoc. 1978,28,510. Volume 15, Number 5, May 1981
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(17) Dong, M.; Locke, D. C.; Ferrand, E. Anal. Chem. 1976, 48, 368. (18) Daisey, J. M.; Leyko, M. A. Anal. Chem. 1979,51,24. (19) Brockhaus, A.; Tomingas, R., Staub-Reinhalt. L u f t 1976,36, 96. (20) Grimmer, G.; Bohnke, H.; Glaser, A. Zbl. Baht. Hyg., I. Abt. Orig. B 1977,164,218. (21) Grimmer, G.; Naujack, K.-W.; Schneider,D. "Polynuclear Aromatic Hydrocarbons: Chemistry and Biological Effects"; Bjorseth,
A., Dennis, A. J., Eds.; Battelle Press: Columbus, OH, 1980; pp 107-25. (22) Greenberg, A.; Giorgio, P., unpublished observations.
Received for review July 30,1980. Accepted December 17,1980. This work was supported by the New Jersey Department of Enuironmental Protection and t h e New Jersey Institute o f Technology Research Foundation.
Analysis of Organic Substances in Highly Polluted River Water by Mass Spectrometry Akio Yasuhara,* Hiroaki Shiraishi, Masahiko Tsuji,? and Toshihide Okunot Division of Chemistry and Physics, National Institute for Environmental Studies, Yatabe, Tsukuba-gun, lbaraki 305, Japan
atile compounds or thermally unstable compounds. This paper also describes the environmental application of FD-MS to the analysis of trace amounts of nonvolatile organics in river water. Volatile and nonvolatile compounds were separated by vacuum distillation and were identified by GC/MS and FD-MS, respectively.
m Volatile and nonvolatile organics in Hayashida River water which contained effluents from the leather industry were separated and analyzed by mass spectrometry. Volatile components were concentrated by steam distillation using a Nickerson-Likens apparatus or by vacuum distillation. The extracts were analyzed with a computerized gas chromatography/mass spectrometry system using a glass-packed column with high resolution. The results of the analyses indicated particularly the presence of large amounts of ethanediol monoalkyl ethers. The nonvolatile organics in the residue from vacuum distillation were extracted and analyzed by field desorption-mass spectrometry. The results showed the presence of polyethylene glycols, many kinds of poly( oxyethylene) alkylphenyl ethers, and some free fatty acids. Introduction I t is very important to determine various kinds of organic substances in river water from the viewpoint of water pollution. Many techniques have been developed for extraction and identification of organic compounds present in river water. For separation of very volatile compounds the head-space gas has been used (1-9). Adsorption methods with resin such as XAD-2 have also given good results ( 1 0 , l l ) .Recently several hundreds of compounds have been detected in the retained entities of reverse osmosis (12).Although direct extraction with organic solvents is very popular for the analysis of organics, direct extraction of organic substances from highly polluted water is very difficult because emulsions form by mixing with organic solvents and because hydrophilic compounds are only slightly transferred to the organic layer. From the point of view of gas-chromatographic analysis, the inclusion of nonvolatile organics is very undesirable because of a decrease in column resolution. Steam distillation or vacuum distillation is suitable for the separation of volatile and nonvolatile compounds. The usual technique for steam distillation is unfavorable because the volume of distillate is large and because extraction efficiency is bad. In this study the Nickerson-Likens apparatus (13),which provides a combination of cyclic steam distillation and continuous extraction, was used for improved extraction efficiency and to avoid the contamination potential from steam and solvent. Identification was carried out by gas chromatography/mass spectrometry (GC/MS). Recently field desorption-mass spectrometry (FD-MS) has shown great success for the analysis of nonvol-
t The Environmental Science Institute of Hyogo Prefecture, Suma-ku,Kobe, Hyogo 654, Japan. 570
EnvironmentalScience & Technology
Experimental Section Sampling and Separation Procedure. Water was sampled from the Hayashida River a t the Matsubara area in Tatsuno City, Hyogo Prefecture, on April 2,1980. The water was divided into two parts. One part (1.7 L) was steam-distilled with a Nickerson-Likens apparatus with diethyl ether (100 mL) for 3 days. The ether solution was dried on anhydrous sodium sulfate and then concentrated with a Kuderna-Danish concentrator under atmospheric pressure. The concentrated solution was analyzed by GC/MS. The other part (2 L) of the water was vacuum-distilled a t Torr after freezing, and the receiver was cooled a t -80 "C. From the trapped water in the receiver, organic substances were extracted with ether (300 mL) for 24 h with a continuous liquid-liquid extractor. The extracted solution was concentrated with a Kuderna-Danish concentrator under atmospheric pressure. The concentrated solution was analyzed by GC/MS. Nonvolatile organics in the residue after vacuum distillation were extracted with ethyl acetate (400 mL) a few times. The solution was concentrated by a rotary evaporator under reduced pressure. The concentrated solution was analyzed by FD-MS. Analytical Procedure. Gas chromatograms and mass spectra were measured with a JEOL Model JMS-D 100 mass spectrometer connected with a JEOL JGC-BOK gas chromatograph and a JEOL JMA-2000 mass data analysis system. The glass column (3 m X 2 mm i.d.) was packed with Thermon-1500, which is a packing material coated with 5% polyester plus 5% starch plus 0.3% phenolic resin on 80-100-mesh, acid-washed, DMCS-treated Chromosorb-W and was obtained from Shinwa Kako Co., Ltd. (Japan). The column temperature was set at 50 "C for 2 min, followed by an increase to 210 "C at a rate of 4 "C/min, and then held at 210 "C until completion of analysis. The injector temperature was 240 "C, and the helium carrier gas flow rate was 40 mL/min. The separator temperature for GC/MS was 240 "C. The gaschromatographic conditions for the analysis of fatty acids were as follows: column, glass column (2 m X 2 mm i.d.) packed with 5% FFAP on Uniport S (60-80 mesh); column temperature, 240 "C; injector temperature, 300 "C; helium carrier gas rate, 40 mL/min. The mass-spectrometric conditions were as follows: ionizing current, 3 X lo-* A; ionizing energy, 25 eV; accelerating voltage, 3 kV; scan range, m/z 10-400; scan speed, 2.6 s/scan; scan interval, 5 s. FD-MS was performed on a
0013-936X/81/0915-0570$01.25/0 @ 1981 American Chemical Society
