Environ. Sci. Technol. 1986,20,267-274
(29) Baxendale, J. H.; Wilson, J. A. Trans. Faraday SOC.1957, 53, 344-356. (30) Volman, D. H.; Chen, J. C. J. Am. Chem. SOC.1959,81, 4141-4144. (31) Loebl, H.; Stein, G.; Weiss, J. J. Chem. SOC.1949,2074-2076. (32) Walling, C.; Johnson, R. A. J. Am. Chem. SOC.1975, 97, 363-367. (33) Vysotskaya, N. A.; Shevchuk, L. G. Zh. Org. Khim. 1973, 9(10), 2080-2083. (34) Vysotskaya, N. A.; Shevchuk, L. G.: Pokrovskii, V. A. Zh. Org. Khim. 1977, 13(5), 1035-1038. (35) Eberhardt, M. K.; Martinez, G. A,; Rivera, J. I.; FuentesAponte, A. J. Am. Chem. SOC.1982,104, 7069-7073. (36) Fendler, J. H.; Gasowski, G. L. J . Org. Chem. 1968, 33, 1865-1868. (37) Jefcoate, C. R. E.; Lindsay Smith, J. R.; Norman, R. 0. J. Chem. SOC.1969, 1013-1018. (38) Gunter, K.; Filby, W. G.; Eiben, K. Tetrahedron Lett. 1971, 3, 251-254. (39) Gilbert, E. 2.Naturforsch.B Anorg. Chem. Org. 1977,32B, 1308-1313.
Leitis, E. “Investigation into the Chemistry of the UV-Ozone Purifications Process”; Annual Report, Westgate Research Laboratory, Los Angeles, CA, 1979, U.S. Department of Commerce PB-296485. Burlinson, N. E.; Kaplan, L. A.; Adams, C. E. “Photochemistry of TNT”; Naval Ordinance Laboratory, White Oak, Silver Springs, MD, 1972, AD-767670. Kaplan, L. A.; Burlinson, N. E.; Sitzmann, M. E. “Photochemistry of T N T (Part 11)”; Naval Ordinance Laboratory, White Oak, Silver Springs, MD, 1975, ADA020072. Symons, M. C. R. In “Peroxide Reaction Mechanisms”; Edwards, J. O., Ed.; Interscience: New York-London, 1962. Ho, P. C. “Degradation Mechanism of 2,4-Dinitrotoluene in Aqueous Solution (Photooxidation Studies)”; Final Report, Oak Ridge National Laboratory, Oak Ridge, TN, 1984, AMXTH-TE-85001. Diekman, J.; Thomson, J. B.; Djerassi, C. J. Org. Chem. 1968,33, 2271-2284. Draffan, G. H.; Stillwell, R. N.; McCloskey, J. A. Org. Mass Spectrom. 1968, 1, 669-685. Merz, J. H.; Waters, W. A. J. Chem. SOC.1949,2427-2433. Hoigne, J.; Bader, H. Water Res. 1976, 10, 377-386. Hoigne, J.; Bader, H. Science 1975, 190, 782-784. Hunt, J. P.; Taube, H. J. Am. Chem. SOC.1952, 74, 5999-6002. Weeks, J. L.; Matheson, M. S. J. Am. Chem. SOC.1956, 78, 1273-1278. Dainton, F. S. J. Am. Chem. SOC.1956, 78, 1278-1279.
Received for review May 28,1985. Revised manuscript received August 29,1985. Accepted September 23,1985. This research was sponsored by the U.S. Army Toxic and Hazardous Materiak Agency under Interagency Agreement 40-1327-83, Army No. 0-3-78-15. ORNL is operated by Martin Marietta Energy System, Inc., for the US.Department of Energy under Contract DE-AC05-840R21400.
Fate of Hazardous Waste Derived Organic Compounds in Lake Ontario Rudolf Jaffe and Ronald A. Hltes”
School of Public and Environment Affalrs and Department of Chemistry, Indiana University, Bloomington, Indiana 47405
rn Dated sediment cores from Lake Ontario’s four sedimentation basins and sedentary fish from tributaries and embayments were analyzed by gas chromatographic, methane-enhanced, negative ion mass spectrometry for a group of fluorinated aromatic compounds. The historical record of these chemicals in Lake Ontario sediments agrees well with the use of the Hyde Park dump in the city of Niagara Falls, NY. These compounds first appeared in sediments in 1958 and rapidly increased until 1970. These dates coincide with the onset of dumping at Hyde Park and remedial action undertaken when this dump was closed, respectively. Chemicals introduced into Lake Ontario by the Niagara River distribute throughout the lake rapidly and uniformly and accumlate in sedentary fish taken from remote locations in the lake.
Introduction The one environmental problem that has most gripped the nation’s attention in the last few years is the disposal of hazardous wastes. The Love Canal area in western New York State is now famous as a chemical waste dump that went wrong. Almost every state has its equivalent; usually it is a chemical waste dump, and often it is regarded as a severe hazard to both people and the environment. The problem with these dumps is simple: they leak. Migration of chemicals from these dump sites pollutes the surrounding groundwater, surface water, and sometimes, people’s homes. We have previously studied the organic compounds migrating from dump sites in western New York (1,2),an area replete with potentially dangerous dumps. The State of New York has enumerated at least 150 dump sites in this area that are thought to contain hazardous wastes (3). 0013-936X/86/0920-0267$01.50/0
Having so many dumps in this location is particularly unfortunate given its proximity to the Niagara River and Lake Ontario. Our studies of Bloody Run Creek, Bergholtz Creek, and the 102nd Street Bay (see Figure 1)have shown that potentially toxic compounds are migrating out of these dump sites and into the Niagara River (1,2). Once in the river, these compounds are transported to Lake Ontario where they can undergo a variety of fates. For example, they may be accumulated in the sediment of the lake ( 4 , 5) and by the biota (5). Preventing hazardous wastes from entering Lake Ontario is important. Lake Ontario ranks about 10th in the world in size and volume and is a lake of great commercial and recreational importance. About 6.5 X lo6 people live on its shores and even more in its drainage basin; most of these people drink water taken from the lake. The lake’s area is about 19000 km2,and the lake itself occupies 32% of its drainage basin. Its average depth is 86 m, and the deepest spot is about 230 m (6). There are four major zones of sediment deposition, which have been named the Niagara, Mississauga, Rochester, and Kingston basins (7). These zones are outlined in Figure 2; the nearshore zone does not accumulate sediment. The Niagara River has a strong influence on Lake Ontario. The total flow into the lake from the Niagara averages 221 km3/year; this compares to a flow out of the lake (through the St. Lawrence River) of 265 km3/year. Thus, the Niagara River supplies 83% of the water to Lake Ontario (8). Because of the highly industrialized nature of the city of Niagara Falls and other areas along this river, “severe environmental stresses have been noted at the mouth of the Niagara” (6). These stresses include high pesticide concentrations and biological perturbations.
0 1986 American Chemical SockttY
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267
..
NEW YORK STATE
-
\
b
Figure 1. Map of the Nagara River area showing locations of sediment grab and fish samples (circled numbers 1-8) and some of the major hazardous waste dumps.
Clearly, the Niagara River is the most important influence on Lake Ontario. Unfortunately, this river is polluted with organic compounds leaching from numerous dump sites along its shores. For example, in our previous work on sediment and fish from the Niagara River and Lake Ontario ( I , 4 , 5 ) ,we have uncovered a series of fluorinated compounds related to the industrial production of 4-(trifluoromethyl)chlorobenzene (see Figure 3). We believe these compounds are the result of the condensation of the precursor, 4-(trichloromethyl)chlorobenzene,in either a head-to-tail reaction (to give a diphenylmethane) or a head-to-head reaction (to give a biphenyl). The former case results in a heptachloro-substituted diphenylmethane that can subsequently be oxidized and fluorinated to form a dichloro(trifluoromethyl)benzophenone,which we will call compound 1. The heptachlor0 intermediate can also be fluorinated directly to form an a,a-difluorodichloro trifluoromethyl diphenylmethane, which we will call compound 2. The head-to-head reaction results in an octachloro-substituted biphenyl, which upon fluorination gives a dichlorobis(trifluoromethy1)biphenyl. This compound was found with homologues containing a total of 1-5 chlorine atoms ( 5 ) ;we will designate this group as compounds 3-1, 3-2, 3-3, 3-4, and 3-5 where the second digit 268
Environ. Sci. Technol., Vol. 20, No. 3, 1986
indicates the total numer of chlorines. Compounds 3-2 and 3-3 are the most abundant members of this series. The source and identification of compounds 1 and 2 have been previously described by Elder et al. ( 1 ) and compounds 3-1 to 3-5 by Jaffe and Hites ( 5 ) . 4-(Trifluoromethy1)chlorobenzene itself has been found in Niagara River fish by Yurawecz (9). Based on analyses of Bloody Run Creek and Lake Ontario sediment samples and various fish samples ( 5 ) ,we have deduced that the Hyde Park dump is the major source of these compounds. This is one of the largest dumps in the city of Niagara Falls; about 80000 tons of chemical wastes are buried there (3),most of it halogenated organics. The goal of this study was to determine the fate of these anthropogenic, organic compounds in Lake Ontario. This was achieved by determining the spatial distribution and depositional history of compounds 1 to 3-5 in Lake Ontario sediment cores and in nearshore sediment and fish samples. The data presented here will tell us where pollutants from a point source on the Niagara River come to rest in the lake and how long it takes for the pollutants to get there.
Experimental Section Sampling. Sediment cores from Lake Ontario were collected by the Canada Centre for Inland Waters in August 1982 and May 1983. Locations are shown in Figure 2. Sampling sites were selected in the sedimentation basins where fine-grained sediments, high in organic carbon, preferentially accumulate. Samples were obtained by subcoring box-core samples in such a way as to maintain the chronological integrity of the sediment. Segments of the subcore were taken in 2-cm intervals and frozen until analysis. Sediment grab samples and fish from several major tributaries to the lake and from Sodus Bay were taken in the summer in 1984. All fish samples, collected by electroshocking, were nonmigratory fish such as carp, goldfish, catfish, and suckers. These samples were taken close to the mouth of the tributaries, except for the Genesee River sample which was taken 2 miles upstream. Extraction and Sample Preparation. The thawed core samples were loaded individually into glass extraction thimbles that had been packed with glass wool. A 24-h Soxhlet extraction with high-purity isopropyl alcohol, to remove water, was followed by a second 24-h extraction with high-purity methylene chloride. Elemental sulfur was removed by passing the combined extracts over an activated copper column. For further cleanup, the sample was eluted from a 1X 30 cm column packed with preextracted (100-200 mesh) silica gel, which had been deactivated with 1%water 24 h prior to use. The sample was eluted with 50 mL each of hexane, 9:l hexane/methylene chloride, methylene chloride, and methanol. The first three fractions were usually combined into one, and their volume was reduced to 0.2 mL for GC/MS analysis. Fish analysis procedures have been described in detail elsewhere (5,lO). GC/MS Analysis. Quantitative analyses were carried out by using methane-enhanced, negative ion mass spectrometry. A Hewlett-Packard 5985B GC/MS system, fitted with a J & W fused silica, 30-m, DB-5 column was used. The GC oven was programmed from 40 "C for 4 min to 280 "C for 20 min at 6 OC/min. Helium was used as the carrier gas at a velocity of about 40 cm/s. Injector, transfer line, and ion source temperatures were 280, 285, and 100 "C, respectively. Quantitation of the sediments was done in the selected ion monitoring mode and was based on the internal standard, 2-chloro-5-trifluoromethylbenzophenone, which was purchased from PCR, Inc. (Gainesville, FL). Response factors for compounds
Flgure 2. Map of Lake Ontario and Nlagara River showing locations of sediment cores (uncircled numbers) and flsh and sediment grab samples (circled numbers 6-15). ~
~~
Table 1. Sedimentation Rates of Lake Ontario Sediment Cores, Determined by '%" Datinga
sample site
sedimentation rate, cm/year
sample site
Niagara Basin
I"'
J
YUllAWECZ ,1979
CI CI
CI
13 15 20 23 25 297 287
0.33 0.18 0.29 0.45 0.37 0.35 0.24
sedimentation rate, cm/year
Rochester Basin 64 69 596 597 599
0.42 0.33 0.35 0.35 0.25
Kingston Basin 79
0.38
Mississauga Basin
2 JAFFE I HITES, 1 9 8 5
36 39 529 593 595
0.17 0.41 0.24 0.23 0.25
For locations of the sample sites, see Figure 2. C
O
C
O
61'
C
I
O
F
&
) CF3
2
A ELDER et al,,1981
Figure 3. Structures of the fluorinated compounds discussed in the text and scheme showing their relationship to each other and to the production of 4-(trifluoromethyl)chlorobenzene.
1 and 2 were determined by use of authentic standards synthesized by PCR, Inc. Since no such standards were available for the polychlorinated bis(trifluoromethy1)biphenyls, the response factors were assumed to be the same as the internal standard. Identifications were based on comparison of mass spectra and retention times. Blanks were run through the procedure. Based on these data, the limit of reliable detection was found to be 0.004 pg/g. Sediment Core Dating. Sedimentation rates were determined by using 137Csdating, utilizing the 1963 subsurface maximum and/or the 1952 horizon. The dried
sediment samples were weighed into scintillation vials and counted for approximately 12 h. Background levels were determined every 36 h, and the Li/Ge detector response was calibrated with a 13'Cs standard. The sedimentation rates for our sediment cores are listed in Table I. For the calculation of these sedimentation rates, we have assumed that effects of sediment mixing due to benthic organisms are negligible. Our core profiles show that no extensive mixing has occurred at the locations discussed here. The sedimentation rates measured in this way agreed with those in the literature. Kemp et al. (11)reported modern sedimentation rates ranging from 0.10 to 0.54 cm/year for five locations in Lake Ontario. Robbins et al. (12) and Durham and Oliver (13) reported sedimentation rates of about 0.30 and 0.47 cm/year, respectively, for sites in the Niagara Basin. Additional support for our sedimentation rates was obtained from one sediment core that was analyzed for DDT and its metabolites. It showed a maximum concentration around 1962; this was in good Environ. Sci. Technol., Vol. 20, No. 3, 1986
269
I
uui;iiriaJlaJlaJ 1971
j
80 60 40 80 60 40 80 60 40 80 60 40 80 60 40 80 60 40
80 60 40 80 60 40 80 60 40 80 60 40
597
I1
599
I
Flgure 4. Concentration profiles (ng/g dry weight) of compound 1 vs. year of deposition in Lake Ontario sediment cores. Gaussian curves were fitted to the data. The four numbers given in each panel indlcate (from top to bottom) site number, maximum concentration as read from Gaussian curve, year of maximum concentration, and year of advent (given by mean minus 2 standard deviations). The dotted line is the average maximum concentration in the whole lake.
Figure 8. Concentration profiles (ng/g dry weight) of compound 3-2 vs. year of depositlon in Lake Ontario sediment cores. Gaussian curves were fitted to the data. The four numbers given in each panel indicate (from top to bottom) site number, maximum concentration as read from Gaussian curve, year of maximum concentration, and year of advent (given by mean minus 2 standard deviations). The dotted line is the average maximum concentration in the whole lake.
m 4 4
0.09 1963 1945
0. 13 1973 1963
0.33 1967 1957
0. 31 1972 1961
0.25 1972 1959
t
1.11
-
0 80 60 40 80 60 40 80 60 40 80 60 40 80 60 40
80 60 40 BO 60 40 80 60 40 80 60 40
U
K
3
a Z
1
0. 19 1970 1960
0. 28 1969 1956
0.28 1969 1956
0.26
0. 22 1973
0.63
1974 1964
0.31 1972 1961
0.37 1968 1956
19671
80 60 40 80 60 40 80 60 40 80 60 40 80 60 40 80 60 40
Flgure 5. Concentration profiles (ng/g dry weight) of compound 2 vs. year of deposition in Lake Ontario sediment cores. Gaussian curves were fitted to the data. The four numbers given in each panel indicate (from top to bottom) site number, maximum concentration as read from Gaussian curve, year of maximum concentration, and year of advent (given by mean minus 2 standard deviations). The dotted line is the average maximum concentration in the whole lake.
agreement with the 1960 maximum observed for these compounds in Lake Ontario by other workers (14).
Results and Discussion The concentrations of compounds 1, 2, and 3-2 to 3-4 vs. date of deposition are given in Figures 4-8. The data 270
Environ. Sci. Technoi., Vol. 20, No. 3, 1986
Flgure 7. Concentration profiles (ng/g dry weight) of compound 3-3 vs. year of depositlon in Lake Ontarlo sediment cores. Gaussian curves were fitted to the data. The four numbers given in each panel indicate (from top to bottom) site number, maximum concentration, as read from Gaussian curve, year of maximum concentration, and year of advent (given by mean minus 2 standard deviations). The dotted line is the average maximum concentration in the whole lake.
have been fitted by a Gaussian curve. We selected this curve to smooth the data and to establish the year of maximum deposition, the corresponding concentration maximum, and the year of advent. The Gaussian curve, however, does not imply a model for an input function. The core profiles corresponding to sites 15,34,36, and 591 showed a maximum in the top 2-cm segment of the core.
Table 11. Average Maximum Concentration (ng/g Dry Sediment), Average Year of Maximum Deposition, and Average Year of Advent of Compounds 1,2, and 3-2 to 3-4 in the Three Major Sedimentation Basins of Lake Ontario, As Determined from Gaussian CurvesR-
parameter
1
2
compd 3-2
3-3
3-4
concn max year max year advent concn max year max year advent concn max year max year advent
0.61 (0.17) 1971 (2) 1960 (2)
1.09 (0.85) 1970 (2) 1957 (2)
0.23 (0.17) 1971 (2) 1960( (1)
0.20 (0.14) 1971 (3) 1960 (2)
0.05 (0.05) 1972 (3) 1963 (3)
0.55 (0.36) 1968 (4) 1958 (2)
1.48 (0.58) 1970 (2) 1956 (4)
0.21 (0.06) 1969 (2) 1957 (3)
0.27 (0.06) 1969 (1) 1957 (2)
0.06 (0.02) 1971 (1) 1960 (3)
0.36 (0.26) 1971 (0) 1958 (1)
1.59 (0.74) 1970 (1) 1957 (2)
0.36 (0.14) 1970 (1) 1958 (3)
0.38 (0.18) 1970 (2) 1959 (2)
0.08 (0.09) 1972 (2) 1960 (3)
depositional basin Niagara
Mississagua
Rochester
See Figures 4-8. The values in parentheses are standard deviations. Cores 13 and 64 have been omitted from these calculations because of excessive scatter, However, cores 25 and 69, where some of these compounds were not detected, were included in the calculations of
average basin concentrations.
0.02 1964 1947
m 4
a
. a
0.03 1975 1966
0. 12 1968 1959
0.04 1974 1966
0.05 1973 1962
80 60 40 80 60 40 80 60 40 80 60 40 80 60 40
E
4
eo
0.03 1972 1964
0.06
0. 06
1973 1962
1971 1957
0. 07 1970 1960
0. oe 1976 1968
0.03 1973 1961
0.21 1970 1959
0.04 1974 1966
60 40
eo
60 40 80 60 40
eo
60 40
0.02 1975 1967
eo
60 40
Figure 8. Concentration profiles (ng/g dry weight) of compound 3-4 vs. year of deposition in Lake Ontario sediment cores. Gaussian curves were fitted to the data. The four numbers given In each panel Indicate (from top to bottom) slte number maximum concentrationas read from Gaussian curve, year of maximum concentration,and year of advent (given by mean minus 2 standard deviations). The dotted line is the average maximum concentration in the whole lake.
This anomaly with respect to the data shown in Figures 4-8 is due to the very low sedimentation rates at these locations. Note that sites 34 and 591 are in the nondepositional zone between the Niagara and Mississauga Basins. Because of the very low sedimentation rates, the profile maximum is not resolved in the top segments of cores 15,34,36, and 591. For this reason, data from these sites are not shown or discussed further. Compound 3-1 was found only in isolated segments of 12 cores, and compound 3-5 was found in only one segment of core 23. Because data for those compounds were so sparse, they will not be discussed further. Each panel of Figures 4-8 represents the concentration measurements of the appropriate compound in each core section plotted against the average year when that core section was deposited. Four numbers are given in each panel: the top is the site number (see Figure 2); the second is the maximum concentration (ng/g) as read from the fitted curve; the third is the year in which the concentration reached this maximum; and the bottom is the year in which the compound started to appear in the Lake. The
cores have been grouped by basin. The dotted lines indicate the overall average maximum concentration for a particular compound in the entire lake. Averages are reported for each compound in each basin in Table 11. In each case, the standard deviations are given in parenthesis after the average. The following paragraphs discuss the conclusions that we draw from these data. Distribution of Fluorinated Compounds in Lake Ontario Sedimentation Basins. Concentrations of each individual compound in sediments from the Niagara, Mississauga, and Rochester basins were compared by using a one-way analysis of variance; this showed that there were no significant differences among the basins. The F values were 0.57,0.86, 1.58, 1.64, and 0.29 for compounds 1 to 3-4, respectively; a significant F value was 4.0 at 2 and 11 degrees of freedom and P < 5%. This uniformity of concentrations throughout the lake is also visually apparent by comparing each core maximum to the dotted lines drawn in Figures 4-8. There are few substantial deviations from this average except for the Kingston Basin. Clearly, chemicals entering Lake Ontario from the Niagara River are distributed uniformly throughout the lake. Frank et al. (15) suggested that the Rochester basin would preferentially accumulate pollutants entering from the Niagara River. Our data contradict this suggestion. In general, no change in concentration was observed from the western to the eastern end of the lake, with the exception of concentrations in the Kingston Basin, which were significantly lower (however, only one sample was analyzed). We also observed (see Table 11) that the concentrations maximize at roughly the same time in the three major basins: within 2 years of 1970. This observation agrees with a particle-associated pollutant transport mechanism, which occurs in a time frame much shorter than the lake’s mean water residence time (approximately 50 years). We conclude that pollutants leaving the Hyde Park dump are quickly and uniformly distributed throughout the lake. This rapid and uniform distribution can be explained by the following mechanism: Suspended sediment with its load of organic compounds enters the lake from the Niagara River and is swept along the southern nearshore zone by water currents. Sediment deposits temporarily all along this zone in a rather uniform distribution and, because water flow in this zone is rapid, this distribution takes place within a few months. From this point, mixing takes place in two ways. First, the sediment from the nearshore zone is mixed into the deep zones of the lake, Environ. Scl. Technol., Vol. 20, No. 3, 1986
271
Table 111. Concentrations (ng/g Dry Sediment) of Compounds 1 to 3-4 in Grab Sediment Samples from Sodus Bay and the Salmon River”
sample
1
2
SodusBay Salmon River
NDb ND
0.13 0.02
See Figure 2 for locations.
compd 3-1 3-2
3-3
3-4
ND ND
0.03 0.01
ND ND
0.03 0.005
Not detected (
