U.S. Geological Survey |
New Jersey District | U.S. Geological Survey |
New Jersey District | Initial interest in VOCs was related to their presence in the atmosphere. In the 1950s it was discovered that the photooxidation of VOCs in the presence of nitrous oxides resulted in air pollution known as "smog" (Bloemen and Burn, 1993). Later, VOCs in the stratosphere were found to be related to ozone depletion over the Antarctic and to potential global climate change (Bloemen and Burn, 1993). VOCs introduced to the environment by large accidental spills of crude petroleum and fuel products and concentrated in industrial waste also received considerable attention (Schwarzenbach and others, 1993). More recently, however, interest in ambient levels of VOCs in air, soil, and natural waters has increased, partly as a result of unexplained locally elevated cancer rates and other health complaints. The relation between these reports and the presence of VOCs at low concentrations in the environment is an area of active debate and research.
One of the long-term goals of the U. S. Geological Survey's (USGS) National Water Quality Assessment (NAWQA) program is to document the presence and identify possible sources of contaminants in the Nation's water resources. The Long Island-New Jersey (LINJ) coastal drainages study is one of 59 planned investigations that constitute the NAWQA program. Because the LINJ study area is one of the most densely populated and developed areas of the country, VOCs and other toxic chemicals are expected to be present in surface and ground waters. Previous studies of VOCs in surface waters include those by Delzer and others (1996), who reported the frequent detection of VOCs in urban stormwater across the United States, and Terracciano and O'Brien (1997), who examined available data documenting the widespread detection of VOCs in streams on Long Island, New York, and in New Jersey. Sampling for VOCs in the atmosphere and unsaturated zone is also underway as part of a study of toxic compounds in the urban environment in a rapidly developing region of southern New Jersey (A.L. Baehr, U.S. Geological Survey, written commun., 1997).
Samples were collected at the center of flow of each stream with a sampler designed by the USGS for use in the NAWQA program. Shelton (1997) describes the sampler and its use in detail. Samples were acidified with 2 drops of 1:1 HCl and shipped on ice to the USGS National Water Quality Laboratory (NWQL). The samples were analyzed for 86 VOCs by using a recently approved method for the determination of low concentrations of VOCs in water (D. L. Rose, U.S. Geological Survey, written commun., 1997). VOC concentrations were determined by purge-and-trap isolation and concentration and capillary-column gas chromatography/mass spectrometry on the basis of methods described in U.S. Environmental Protection Agency (USEPA) method 524.2, revision 4.0 (U.S. Environmental Protection Agency, 1992), and Rose and Schroeder (1994). The new method includes a larger compound list as a result of minor improvements in instrumental operating conditions, modified quantitation ions, and strategies for reporting data near the method detection levels (D. L. Rose, written commun., 1997). For example, confirmed detections below the non-detect value (NDV) are qualified with an "E" to indicate that accurate quantitation is not guaranteed.
Table 2. Volatile organic compounds analyzed for but not detected in 42 surface-water samples
collected from Long Island and New Jersey streams, January 27-30, 1997.
---------------------------------------------------------------------------------- Compound name (IUPAC/NWQL) Trade name NDV (ug/L) ---------------------------------------------------------------------------------- Vinyl acetate Vinyl acetate 0.05 (1,1-Dimethylethyl)benzene/tert-Butylbenzene N/A 0.05 1,1,1,2,2,2-Hexachloroethane/Hexachloroethane Hexachloroethane 0.05 1,1,1,2-Tetrachloroethane 1,1,1,2-TeCA 0.05 1,1,2,2-Tetrachloroethane 1,1,2,2-TeCA 0.10 1,1,2-Trichloroethane Vinyl trichloride 0.10 1,1-Dichloropropene N/A 0.05 1,2,3-Trichlorobenzene 1,2,3-TCB 0.20 1,2-Dibromo-3-chloropropane DBCP, Nemagon 0.50 1,2-Dibromoethane EDB, Ethylenedichloride 0.10 1,2-Dichloroethane Ethylenedichloride 0.05 1,2-Dichloropropane Propylenedichloride 0.05 1,3-Dichloropropane Trimethylenedichloride 0.05 1-Chloro-4-methylbenzene/4-Chlorotoluene p-Chlorotoluene 0.05 2,2-Dichloropropane N/A 0.05 2-Hexanone 2-hexanone 5.00 2-Propenal/Acrolein Acrolein 2.00 2-Propenenitrile/Acrylonitrile Acrylonitrile 2.00 3-Chloro-1-propene 3-Chloro-1-propene 0.10 Bromobenzene Phenyl bromide 0.05 ----------------------------------------------------------------------------------
The six most frequently detected VOCs were methyl tert-butyl ether (MTBE), acetone, naphthalene, tetrachloroethene (PCE), chloroform, and trichloroethene (TCE) (figure 2). MTBE is a fuel oxygenate added to gasoline to enhance combustion and reduce carbon monoxide emissions and ozone in the atmosphere (Squillace and others, 1997). Acetone is used for cleaning and drying purposes and as a solvent in many industries; it is also a natural biodegradation product prior to the formation of organic acids. Naphthalene is a component of fuel oil; PCE is used extensively in dry cleaning and as a solvent in many industries. Chloroform is used as both a raw material and a solvent in industry and is a byproduct of drinking-water chlorination. TCE is used mainly as a metal degreaser, but is also found in dyes, inks, cleaners, and disinfectants.
The maximum measured concentrations of these six VOCs were MTBE, 8.7 g/L (micrograms per liter); acetone, 6.6 g/L; naphthalene, 0.68 g/L; PCE, 4.6 g/L; chloroform, 0.1 g/L; and TCE, 1.2 g/L, respectively. These concentrations were measured in samples collected at Sampawams Creek, N.Y. (site 2), Santapogue Creek, N.Y. (site 3), or Elizabeth River, N.J. (site 21) (figure 1). None of the concentrations measured exceeded the USEPA drinking-water maximum contaminant level (MCL) or lifetime health-advisory level (HAL) (table 1). Toxic Release Inventory (TRI) data compiled for the LINJ study area for the six most frequently detected compounds are shown in table 3 (U.S. Environmental Protection Agency, 1994). The TRI is a data base of toxic chemical releases into the environment, that was established under the Emergency Planning and Community Right-to-Know Act of 1986 and expanded under the Pollution Prevention Act of 1990 (described in U.S. Environmental Protection Agency, 1994). The six compounds most frequently detected in this study all ranked within the upper third of VOCs listed in order of total releases to the environment.
Table 3. Toxic Release Inventory Data for the six most frequently detected volatile organic compounds
in samples collected from Long Island and New Jersey streams, (U.S. EPA, 1994)
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Volatile Release to Release to Total Total release
organic water -- water release -- (pounds)
compound Rank (out of (pounds) Rank (out of
24 volatile 111 volatile
organic organic
compounds) compounds)
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Methyl tert-butyl ether 7 212 14 150,007
Acetone 16 49 1 2,852,916
naphthalene 6 261 37 11,707
Chloroform -- 0 35 15,610
Tetrachloroethene -- 0 12 312,286
Trichloroethene 12 94 8 866,175
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The number of VOCs detected at each site was examined with respect to the land-use composition of the basin. The number of VOCs detected at a site ranged from 2 to 30 (figure 3). In general, the number of VOCs detected was highest at sites draining basins with high percentages of urban land use. Relatively high numbers of VOCs were detected in several basins dominated by forested land as well (figure 3), however, indicating the likely presence of a point source in these basins.Because MTBE was the most frequently detected VOC, concentration data for this compound were examined further. With the exception of one site in southern New Jersey, the highest concentrations of MTBE were measured in the most intensively developed parts of the study area (figure 4), in streams draining basins with the highest percentages of urban land use (figure 3). A few high concentrations of MTBE, however, were measured at sites draining primarily forested land.
Evaluation of these data with respect to human and aquatic health is difficult for several reasons. MCLs, HALs, and criteria for aquatic organisms have been established for only a few of the VOCs detected. Futhermore, MCLs and HALs apply to individual compounds; however, most samples contained more than one compound. The potential cumulative or synergistic effects of the presence of multiple compounds is unknown.
Canadian Council of Resource and Environment Ministers, 1991, Canadian water quality guidelines: Ottawa, Ontario, Environment Canada, Inland Waters Directorate, Water Quality Branch (updated May 1996), variously paged.
Delzer, G.C., Zogorski, J.S., Lopes, T.J., and Bosshart, R.L., 1996, Occurrence of the gasoline oxygenate MTBE and BTEX compounds in urban stormwater in the United States, 1991-95: U.S. Geological Survey Water-Resources Investigations Report 96-4145, 6 p.
Rose, D.L., and Schroeder, M.P., 1994, Methods of analyses by the U.S. Geological Survey National Water-Quality Laboratory--Determination of volatile organic compounds in purge and trap capillary gas chromatography/mass spectrometry: U.S. Geological Survey Open-File Report 94-708, 26 p.
Schwarzenbach, R.P., Gschwend, P.M., and Imboden, D.M., 1993, Environmental organic chemistry: New York, John Wiley and Sons, Inc., 681 p.
Shelton, L.R., 1997, Field guide for collecting samples for analysis of volatile organic compounds in stream water for the National Water-Quality Assessment program: U.S. Geological Survey Open-File Report 97-401, 14 p.
Squillace, P.J., Pankow, J.F., Korte, N.E., and Zogorski, J.S., 1997, Review of the environmental behavior and fate of MTBE: Journal of Environmental Toxicology and Chemistry, v. 16, no. 9, p. 1836-1844.
Squillace, P.J., Zogorski, J.S., Wilber, W.G., and Price, C.V., 1996, Preliminary assessment of the occurrence and possible sources of MTBE in groundwater in the United States, 1993-1994: Environmental Science & Technology, v. 30, no. 5, p. 1721-1730.
Terracciano, S.A., and O'Brien, A.K., 1997, Occurrence and distribution of VOCs in streams on Long Island, New York, and in New Jersey--A review of existing and reconnaissance data: U.S. Geological Survey Fact Sheet FS-063-97, 4 p.
U.S. Environmental Protection Agency, 1992, Measurement of purgeable organic compounds in water by capillary-column gas chromatography/mass spectrometry, method 524.2, revision 4.0: Cincinnati, Ohio, Environmental Monitoring Systems Laboratory, August 1992, 50 p.
____ 1994,Toxics release inventory public data release: Washington, D.C., Office of Pollution Prevention and Toxics, EPA 745-R-94-001, 288 p.
____ 1995, Guidance for assessing chemical contaminant data for use in fish advisories: Volume 1, Fish sampling and analysis, 2d ed.: Washington, D.C., Office of Water, EPA 823-R-95-007, 289 p. plus appendixes.
____ 1996, Drinking water regulations and health advisories: Washington, D.C., Office of Water, EPA 822-B-96-002, 16 p.
____ 1996b, Aquatic toxicity information retrieval data base (AQUIRE): Duluth, Minnesota, U.S. Environmental Protection Agency, Environmental Research Laboratory, data retrieved May 1996 (electronic data files).
____ 1996c, Integrated Risk Information System (IRIS): Research Triangle Park, N.C., U.S. Environmental Protection Agency, Office of Health and Environmental Assessment, electronic data files (December 1996 update).
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Compound name Trade name NDV Detection Median Maximum Site of MCL or HAL Freshwater chronic criteria
(IUPAC/NWQL) (µg/L) frequency concentration concentration maximum (µg/L) for aquatic life
in percent of all of all concentration (µg/L)
(number of detections detections (fig. 1)
samples) (µg/L) (µg/L)
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Methyl tert-butyl ether/Methyl-t-butyl ether MTBE 0.10 100 (42) 0.36 8.7 01309100 HAL 20-200 --
Acetone Acetone 5.00 64 (27) E2.6 6.6 01393400 -- --
naphthalene Naphthalene 0.20 55 (23) E0.02 0.68 01393400 HAL 20 USEPA 620
Tetrachloroethene Perchloroethene, PCE 0.05 55 (23) E0.03 4.6 01308200 MCL 5.0 CAN 110
Trichloromethane/Chloroform Chloroform 0.05 55 (23) E0.03 0.10 01393400 MCL 100 CAN 2, USEPA 1,240
Trichloroethene TCE 0.05 50 (21) 0.08 1.2 01309100 MCL 5.0 CAN 20, USEPA 21,900
1,1,1-Trichloroethane Methylchloroform 0.05 43 (18) E0.02 0.92 01309100 MCL 200 --
cis-1,2-Dichloroethene (z)-1,2-Dichloroethene 0.05 41 (17) E0.05 0.90 01309100 MCL 70 --
Methylbenzene/Toluene Toluene 0.05 41 (17) E0.03 0.24 01393400 MCL 1,000 CAN 2
1,3 and 1,4-Dimethylbenzene/m and p-xylene meta and para-Xylene 0.05 26 (11) E0.02 0.20 01393400 MCL 10,000 --
Diethyl ether Diethyl ether 0.10 26 (11) E0.1 0.15 01387041 -- --
tert-Amyl methyl ether TAME 0.10 26 (11) E0.02 0.08 01309100 -- --
Carbon disulfide Carbon disulfide 0.05 24 (10) E0.01 0.02 01309100 -- --
2-Butanone/Methylethyl ketone Methylethyl ketone 5.00 21 (9) E0.5 2.0 01391500 -- --
1,2,4-Trimethylbenzene Psudocumene 0.05 17 (7) E0.02 0.42 01393400 -- --
1,4-Dichlorobenzene p-dichlorobenzene, 1,4-DCB 0.05 17 (7) E0.01 0.09 01309100 MCL 75 CAN 4.0
1,1-Dichloroethane Ethylidene dichloride 0.05 14 (6) 0.14 0.81 01308200 -- --
Benzene Benzene 0.05 14 (6) E0.04 0.10 01393400 MCL 5.0 CAN 300
1,2-Dichlorobenzene o-Dichlorobenzene, 1,2-DCB 0.05 12 (5) 0.09 0.18 01308200 MCL 600 CAN 2.5, USEPA 763
1,2-Dimethylbenzene/o-Xylene o-Xylene 0.05 12 (5) E0.03 0.10 01393400 MCL 10,000 --
Chlorobenzene Monochlorobenzene 0.05 12 (5) 0.1 0.10 01403900 MCL 100 CAN 15, USEPA 50
1,1-Dichloroethene Vinylidene chloride 0.10 10 (4) 0.15 0.32 01309100 MCL7.0 --
4-Methyl-2-pentanone/Methyl isobutyl ketone Methyl isobutyl ketone 5.00 10 (4) E0.1 0.4 01308200 -- --
Ethylbenzene Phenylethane 0.05 12 (5) E0.01 0.06 01393400 MCL 700 CAN 90
1,3-Dichlorobenzene m-Dichlorobenzene 0.05 7 (3) E0.02 0.03 01309100 HAL 600 CAN 25, USEPA 763
1,1,2-Trichloro-1,2,2-trifluoroethane/Freon 113 Freon 113, CFC 113 0.05 5 (2) N/A 0.07 01309100 -- --
1,2,3,4-Tetramethylbenzene/Prer-nitene Prer-nitene 0.05 5 (2) N/A 0.36 01393400 -- --
1-Chloro-2-methylbenzene/2-Chlorotoluene o-Chlorotoluene 0.05 5 (2) N/A E0.01 01308200 HAL 100 --
01309100
1-Ethyl-2-methyl-benzene/2-Ethyltoluene 2-Ethyl toluene 0.05 5 (2) N/A 0.09 01393400 -- --
Chloroethane Ethyl chloride 0.10 5 (2) N/A E0.04 01367770 -- USEPA 230,000
Chloroethene/Vinyl chloride Vinyl chloride 0.10 5 (2) N/A E0.07 01367770 MCL 2 --
Chloromethane/Methyl chloride Methyl chloride 0.20 5 (2) N/A E0.08 01464515 HAL 3.0 --
01475000
Dichloromethane/Methylene chloride Methylene chloride 0.10 5 (2) N/A E0.08 01309100 MCL 5.0 CAN 98
1,4-EpoxybutaneTetrahydrofuran Tetrahydrofuran 5.00 5 (2) N/A E2.8 01467329 -- --
trans-1,2-Dichloroethene (E)-1,2-Dichloroethene 0.05 5 (2) N/A E0.02 01309100 MCL 100 --
Trichlorofluoromethane CFC-11, Freon 11 0.10 5 (2) N/A 0.53 01393400 HAL 2,000 --
(1-Methylethyl)benzene/Isopropylbenzene Cumene 0.20 2 (1) N/A E0.01 01393400 -- --
(1-Methylpropyl)benzene/sec-Butylbenzene N/A 0.05 2 (1) N/A E0.03 01393400 -- --
1,2,3,5-Tetramethylbenzene/Isodurence Isodurence 0.05 2 (1) N/A 0.22 01393400 -- --
1,2,3-Trichloropropane Allyl trichloride 0.20 2 (1) N/A E0.11 01309100 HAL 40 --
1,2,3-Trimethylbenzene 1,2,3-Trimethylbenzene 0.05 2 (1) N/A 0.1 01393400 -- --
1,3,5-Trimethylbenzene Mesitylene 0.05 2 (1) N/A 0.09 01393400 -- --
1-Isopropyl-4-methylbenzene/p-Isopropyltoluene p-Cymen 0.05 2 (1) N/A E0.04 01393400 -- --
Bromodichloromethane Dichlorobromomethane 0.10 2 (1) N/A E0.02 01382000 MCL 100 --
Dichlorodifluoromethane CFC-12, Freon-12 0.20 2 (1) N/A 0.24 01308200 HAL 1,000 --
Ethenylbenzene/Styrene Styrene 0.05 2 (1) N/A E0.009 01393400 MCL 100 --
Ethyl tert-butyl ether/Ethyl-t-butyl ether ETBE 0.10 2 (1) N/A E0.02 01411110 -- --
Iodomethane/Methyl iodide Methyl iodide 0.05 2 (1) N/A E0.02 01475000 -- --
n-Propylbenzene Isocumene 0.05 2 (1) 0.04 E0.04 01393400 -- --
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Information related to NAWQA can be obtained from:
NAWQA Project Chief, USGS
810 Bear Tavern Road, Suite 206
West Trenton, New Jersey 08628
phone 609-771-3943
