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Kramer, J. R.; Andren, A. W.; Smith, R. A.; Johnson, A. H.; Alexander, R. B.; Oehlert, G. In Acid Deposition: Long Term Trends; National Research Council; National Academy Press: Washington, DC, 1986; p 231. Biological Survey of the Champlain Watershed, 1929; St. Lawrence Watershed, 1930; Oswegatchie and Black River Systems, 1931; Upper Hudson Watershed, 1932; Raquette Watershed, 1933; Mohawk-Hudson Watershed, 1934; New York State Conservation Department: Albany, NY, 1929-1934. Lake Survey; Adirondack Lake Survey Corp., New York State Department of Environmental Conservation: Albany, NY, 1984-1985; Vol. 1-10. Characteristics of Lakes in the Eastern United States; U.S. Environmental Protection Agency. US.Government Printing Office: Washington, DC, 1986, EPA/600/4-86/007; Vol. 1-3. Colquhoun, J. R.; Kretser, W. A.; Pfeiffer, M. H. Acidity Status of Lakes and Streams in New York State; New York State Department of Environmental Conservation: Albany, NY, 1984. Haines, T. A,; Akielaszek, J. J.; Norton, S. A.; Davis, R. B. Hydrobiologia 1983, 107, 57. Stumm, W.; Morgan, J. J. Aquatic Chemistry, 2nd ed.; Wiley: New York, 1981; pp 184-188. Baker, J.; Harvey, T. Critique of Acid Lakes and Fish Population Status in the Adirondack Region of New York State; draft final report, NAPAP Project E3-25, U S . Environmental Protection Agency. U.S.Government Printing Office: Washington, DC, 1985. Pfeiffer, M. H. Department of Environmental Conservation, Raybrook, NY, personal communication, 1986. Standard Methods, 13th ed.; American Public Health Association: New York, 1971. Standard Methods, 4th ed.; American Public Health Association: New York. 1926.
Standard Methods, 6th ed.; American Public Health Association: New York, 1930. Wetzel, R. G.; Likens, G. E. Limnological Analyses; Saunders: Philadelphia, PA, 1979. Kramer, J. R.; Tessier, A. Environ. Sci. Technol. 1982,16, 606A. Kolthoff, I. M.; Stenger, V. A. Volumetric Analysis; Wiley: New York, 1947; Vol. 11. Esposito, J., Chemist, Hellige Co., New York, personal communication, 1985. Stensland, G. J.; Whelpdale, D. M.; Oehlert, G. In Acid Deposition: Long Term Trends; National Research Council; National Academy Press: Washington, DC, 1986; p 128. Reuss, J. 0.;Johnson, D. W. J. Enuiron. Qual. 1985,140) 26. Kilham, P. Limnol. Oceanogr. 1982,27(5)856. Heimberger, C. C. Forest-Type Studies in the Adirondack Region; Memoir 165; New York State Agricultural Experiment Station, Cornel1 University: Ithaca, NY, 1934. Acid Deposition: Processes of Lake Acidification; National Research Council, National Academy Press: Washington, DC, 1984. Rapp, G., Jr.; Allert, J. D.; Liukkonen, B. W.; Ilse, J. A.; Loucks, 0. L.; Glass, G. E. Environ. Int. 1985, 11, 425. Peters, N. E.; Driscoll, C. T. Biogeochemistry 1987,3, 163. North East Climate Data Center, Cornell University, Ithaca, NY. Unpublished data. Mattson, M. D.; Driscoll, C. T. In preparation. Received for review June 9, 1988. Accepted October 24, 1988. We gratefully acknowledge the financial support of the Mary Flagler Cary Charitable Trust and the Andrew W. Mellon Foundation. A Contribution to the program of the Institute of Ecosystem Studies, The New York Botanical Garden.
Uptake of Airborne Tetrachloroethene by Spruce Needles Hartmut Frank" and Wllfrled Frank Institut fur Toxikologie, Wilhelmstrasse 56, D-7400 Tubingen, Federal Republic of Germany
Tetrachloroethene in spruce needles is quantitatively determined by extraction with hexane, separation by capillary gas chromatography, and detection by chemicalionization mass spectrometry, monitoring the negatively charged chlorine ions. Needle samples from spruces growing in forests and in a city in Southwest Germany and from spruces in exposure chambers have been analyzed; concurrently, the respective air levels have been determined. The concentrations in the needles are correlated to atmospheric levels; below an air concentration of 5 pg/m3, the partition ratio is 520, above it is 50. Introduction
C1 and C2 halocarbons are widely used as solvents in textile and metal industries. During application they escape into the atmosphere, the extent of which is estimated to be -70%. Due to their relatively long atmospheric lifetimes (1) they are transported into rural areas, considered as "clean-air regions" in respect to the air pollutants NO, and SOz. The atmospheric levels of halocarbons in rural areas are 3-5 times lower than over urban centers (2),but sometimes relatively high values may occur in rural air (3). It has been suggested that reactive intermediates of halocarbons generated by photochemical processes may be involved in the phytotoxicological phenomena of forest decline ( 4 ) ,which is most serious in remote areas. 0013-936X/89/0923-0365$01.50/0
An important feature of the less volatile halocarbons is their great lipophilicity (5);as shown in model experiments, they may be enriched in lipids and waxes of cuticles and cellular membranes (6) due to their large partition ratios (Ostwald solubility coefficients), e.g. 2000 (22 "C) for tetrachloroethene. Lipids represent -5% of the weight of a 1-year-old needle, so relative to needle weight partition ratios of 100 are to be expected. The goal of the present study is to ascertain whether this is also true for needles of trees exposed to tetrachloroethene at concentrations in their natural environment, or at levels as they are used in exposure chamber experiments. Tetrachloroethene concentrations have been determined in spruce needles (Picea Abies excelsa) from trees in the Black Forest, from trees growing in the city of Tubingen, and from 8-year-old spruces exposed in chambers to controlled air concentrations of tetrachloroethene. Air samples a t all three locations were taken a t the same time and analyzed for halocarbons. Atmospheric concentrations were determined as described previously (7); for determination of tetrachloroethene in needles, the more selective detection by negative-ion chemical-ionization mass spectrometry was employed.
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Experimental Section Sample Preparation. Culture tubes (8.5 X 100 mm) equipped with screw caps lined with Teflon-laminated rubber seals and disks of polished aluminum foil, thickness
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0.1 mm, are used as sample containers. They are rinsed twice with ultrapure hexane (
