Kim, H . T., Kline, S. J., Reynolds. W. C., “An Experimental Study of Turbulence Production Near a Smooth Wall in a T u r bulent Boundary Layer with Zero Pressure Gradient,” Report MD-20 Thermosciences Division, Department of Mechanical Engineering, Stanford University, Stanford, Calif., 1968. Kirmse, D. W., “ A Monte Carlo Study of Turbulent Diffusion,” PhD Dissertation, Iowa State University of Science and Technology, Ames, Iowa, 1964. Klebanoff, P . S.. “Characteristics of Turbulence in a Boundary Layer with Zero Pressure Gradient,” National Advisory Committee for Aeronautics, T S 3178, 1954. Kline. S. J., Lisin. A. V.. Waitman, B. A,, “An Experimental Investigation of the Effect of Free Stream Turbulence on the T u r bulent Boundary Layer Growth.” Final Rept for Contract XAW-65OO to the National Advisory Committee for Aeronautics, 1958. Kraichnan. R. H., “Diffusion by a Random Velocity Field,” Phys. Fluids, 13,22, 1970. Lumley, J . L., Panofsky. H . A , , “The Structure of Atmospheric Turbulence.” Interscience, New York, N.Y., 1964. Mickelsen, W . R., “An Experimental Comparison of the Lagrangian and Eulerian Correlation Coefficients in Homogeneous Isotrophic Turbulence,” National Advisory Committee for Aeronautics. Technical S o t e 3570, 1955. Mortensen, R. E.. “Mathematical Problems of Modelling Stochastic Nonlinear Dynamic Systems,” J . S t a t . Physics, 1, 271, 1969.
Panofsky, H . A , , Ileland. R. J.. “One-dimensional Spectra of Atmospheric Turbulence in the Lowest 100 Meters, Atmospheric Diffusion and Air Pollution.” F. N. Frenkiel and P. A . Sheppard, Eds., “Aduances i n Geophysics,” 6, 41, Academic Press. New York, S . Y . , 1959. Papoulis, A . , “Probability, Random Variables and Stochastic Processes.” McGraw-Hill, New York, N.Y., 1965 Pasquill, F., “Atmospheric Diffusion.” D. Van Nostrand, London, 1962.
Patterson. G. S.. Corrsin, S., “Computer Experiments on Random Walks with Both Eulerian and Lagrangian Statistics,” in “Dvnamics of Fluids and Plasmas.” E d Pai. Academic Press. New York, N.Y., 1966. Philliu. J . R.. “Relation Between Eulerian and Lagrangian Statistics,” Phys. Fluids Suppl., 10, S69, 1967. Poreh, M., “Diffusion from a Line Source in a Turbulent Boundary Layer,” PhD Dissertation, Department of Civil Engineering, Colorado State University, Fort Collins, Colo., 1961. Poreh, M., Cermak. J . E., “Study of Diffusion from a Line Source in a Turbulent Boundary Layer,” Int. J . Heat Mass Transfer, 7, 1083, 1964. Priestley, C. H. B., “Turbulent Transfer in the Lower Atmosphere,” University of Chicago Press, Chicago, Ill., 1959. Riley, J., Corrsin, S.. “Simulation and Computation of Dispersion in Turbulent Shear Flow.” Conference on Air Pollution Meteorology, Raleigh, N.C., 1971. Seinfeld. J . H.. “Mathematical Models of Air Qualitv Control Regions.” in ”‘Development of Air Quality Standards.” Chap. 7, Charles Merill Press. Columbus, Ohio, 1970. Slade, D. H . , Ed., “Meteorology and Atomic Energy 1968,” U.S. Atomic Energy Commission, 1968. Snyder. W.H., Lumley. J . L., “Some Measurements of Particle Velocity Autocorrelation Functions in a Turbulent Flow,” J . Fluid Mech., 48,41: 1971. Sutton, 0. G.. “ A Theory of Eddy Diffusion in the Atmosphere,” Proc. Roy. SOC.(London), Series A. 338,143, 1932. Sutton. 0. G.. “Micrometeorology,” McGraw-Hill, New York, X.Y.. 1953. Yeh, F. F., Nickerson, E. C.. “Air Flow Over a Roughness Discontinuity,” Project T H E M I S Rept. KR-062-414. Colorado State University, Fort Collins. Colo., 1970. I
_
Receiued for rec’ieu, April 23, 1973. Accepted October 24, 1973. Support o f t h e National Science Foundation under Grant Y S F GK-31354X is gratefully acknouledged.
Concentration of Heavy Metals in Sediment Cores from Selected Wisconsin Lakes lskandar K. lskandar and Dennis R. Keeneyl D e p a r t m e n t of Soil S c i e n c e , University of Wisconsin, Madison, Wis. 53706
w The concentrations of Cu, Zn, Cd. P b , Cr, and ?Ji in sediment cores from five hard-water and five soft-water lakes in Wisconsin were determined. Based on estimates of sedimentation rates, the sediment samples used for estimation of the early cultural or precultural concentrations were deposited 140 to 400 years ago. The precultural concentrations of Cu.Zn. Cd, and P b were. in nearly all cases, less than those of postcultural and especially of modern (0-10 cm) sediments. In general, there was no significant trend in the vertical distribution of Xi, but four of the 10 lakes had accumulated Cr in recent times. The accumulation of Cu in three of the hard-water lakes investigated was related t o copper sulfate (used as an algalcide) input from 1918 to 1944. Surface enrichment may have been due t o runoff from urban and agricultural lands and from sewage inputs. The noticeable buildup in P b was attributed mainly to atmospheric loading.
Accumulation of heavy metals in the environment. particularly surface waters is currently receiving considerable attention. Verylittle is known about the fate and distribution of heavy metals in aquatic ecosystems, but it is probable that a considerable proportion of the elements which reach surface waters eventually are deposited in the sedi‘To whom correspondence should be addressed.
ments. Precultural levels of heavy metals in natural systems are needed to evaluate the rate and extent of accumulation of these elements due to man’s activities. In lakes, sediment cores have been used to evaluate accumulation of N, C, P, Ca, Mg, Al, Fe, Mn? Cu. As, and Hg (Keeney et al., 1970; Konrad et al., 1970; Ruch et al.. 1970; Kennedy et al., 1971; Sanchez, 1971: Bortleson and Lee, 1972; Shukla et al., 1972; Frye and Shimp. 1973; Syers et al., 1973). The results of several studies (Shimp et al., 1970; Collinson and Shimp, 1972) and recent reports of on-going research (Edginton and Thommes, 1972: Robbins et al., 1972; Skoch and Turk, 1972; Smith and Moore, 1972; Wahlgren et al., 1972) suggest that the distribution of heavy metals in sediment cores varies appreciably among lakes but in most recent sediment studies the tendency is toward an accumulation. The purpose of this paper is to report on a survey of the vertical distribution and precultural concentrations of Cu. Zn, Cd, Pb, Cr, and Ni in sediment cores from widely divergent Wisconsin lakes and to evaluate the relationship between concentration of these elements and some sediment components thought to be of potential importance in retaining heavy metals. The work is an extension of a recent survey (Syers et al.. 1973) on Hg in sediment cores of a number of Wisconsin lakes. Lakes Sediment cores were taken from a number of Wisconsin lakes differing in sediment properties and in degree of Volume 8, Number 2, February 1974
165
Table I. Lakes Investigated Possible sources of heavy metals
Lake
1. Mendota 2. Monona
5. Wingra
Dane Dane Dane Dane Dane
6. Mary 7. Tomahawk 8. Minocqua 9. Butternut 10. Phillips
Vilas Oneida Oneida Price Price
3. Waubesa 4. Kegonsa
Area, ha
County
Maximum depth, m
Sedimentation rate, mm/yr Runoff
Sewage effluent Added
Period
Chemical treatment Period
No Yes Yes Yes
1919-1944 1939-1944 1939-1944
...
High Very high Low Low Medium
.*. ... ... ... ...
Very low Low Medium Low Medium
Southern Wisconsin Lakes (Calcareous Sediments) 25 4.2. R, U 5 Yes Until 1898 20 5.3~ R, U Yes Until 1950 10 ... R Yes Until 1959 860 1100 10 ... R Indirect ... 140 3 ... R, U No ...
3940 1350
Northern Wisconsin Lakes (Noncalcareous Sediments) No ... 20 ... R 1 24 18 7 16
1470 520 340 170
a Average value of Bortleson a n d Lee, 1972.
5
...
R R, U R R
2a
... ...
R = Rural: U = Urban.
Table II. Analytical Wave Lengths, Linear Range, and Reproducibility of Atomic Absorption Methods Metal
Wave length, nm
Slit, mm
Copper Zinc Cad mi um Lead Chromium Nickel
325 214 229 283 358 232
4 4 4 4 4 3
Linear range, ppm
5 1 2 20 5 5
Coefficient of variation,"
%
4.9 3.9 7.7 4.6 14.5 6.9
Determined b y analyzlng (in duplicate) a dredge s a m p l e f r o m Phillips Lake on 10 different days ( n = 20 for each metal).
urban and industrial influence. The cores were taken from the deep water areas of Lakes Mendota, Monona, Waubesa, Kegonsa, and Wingra in southern Wisconsin, and from Tomahawk, Mary, Minocqua, Butternut, and Phillips lakes in northern Wisconsin (Figure 1 and Table I). Further information on these lakes is given in Lawton (1961), Frey (1963), Keeney et al. (1970), and Syers et al. (1973). Butternut, Phillips, and Tomahawk were sampled in the summer of 1972, while the other lakes were sampled in the winter of 1970.
e
No
...
Yes Yes Yes
Until 1959 Unknown Unknown
Traffic density
Added
No No No
No No No
...
Average value of Bortleson, 1970.
scribed by Christian and Feldman (1972). Cu, Zn, Cd, Pb, Cr, and Ni were determined on aliquots of the digest by a Perkin-Elmer 306 Atomic Absorption Spectrophotometer (air and acetylene as the oxidant and fuel). Reagent blanks were carried throughout the procedure. High-purity salts of the metals dissolved in dilute H N 0 3 were used as standards. The calibration curve for each metal was prepared in the presence of the other metals a t concentrations encountered in the sediments to compensate for possible interferences between different metals. The analytical conditions and reproducibility are given in Table 11. Organic C (Bremner and Jenkinson, 1960), calcium carbonate (Leo, 1963), and free iron oxides (short-range-order hydrated iron oxides), extractable with citrate-dithionitebicarbonate (Jackson, 1956) were determined in selected samples. All results are averages of closely agreeing duplicate samples, and the results are expressed on the basis of oven-dry weight of sediment.
Results and Discussion The lakes investigated (Table I and Figure 1) were selected to provide a range in size, depth, and cultural influence. Lakes Mendota. Monona, Waubesa and Minocqua are subject to considerable cultural influence; all have
Sample Collection and Analysis
The cores were collected by a piston corer having an 8.9-cm i.d. clear plastic barrel and a weighted steel head (Wentz, 1967). The cores were extruded, sliced into 5-cm intervals (or as indicated) and placed in glass bottles. Each sediment sample was mixed thoroughly, and a subsample was dried at 105°C in a forced-air oven. The dried sample was ground (
