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McCarthy, P. L. In Environmental Biotechnology: Reducing Risks from Environmental Chemicals through Biotechnology; Omenn, G. S., Ed.; Plenum Press: New York, 1988;pp 143-162. Bouwer, E. J.; McCarthy, P.L. Biotechnol. Bioeng. 1985, 27, 1564-1571. Gantzer,C. J.; Kollig, H. P.; Rittmann, B. E.; Lewis, D. L. Water Res. 1988,22,191-200. Zehnder, A. J. B.; Schraa, G. GWF, Gas- Wasserfach: WasserlAbwasser 1988,129,79-83. Matson, J. V.; Characlis, W. G. Water Res. 1976, 10, 877-885. Williamson, K.; McCarty, P. L. J.-Water Pollut. Control. Fed. 1976,48,9-24. Siegrist, H.; Guyer, W. Water Res. 1985,19,1369-1378. Suidan, M. T.; Rittmann, B. E.; Traegner, U. K. Water Res. 1987,21,491-498. Chen, Y.S.;Bungay, H. R. Biotechnol. Bioeng. 1981,23, 781-792. Opperhuizen,A.; Gobas, F. A. P. C.; Van der Steen, J. M. D.; Hutzinger, 0. Environ. Sci. Technol. 1988,22,638-646. Focht, D. D.;Brunner, W. Appl. Environ. Microbiol. 1985, 50,1058-1063. Moody, G. J.; Thomas,J. D. R. In Chromatographic Separation and Extraction with Foamed Plastics and Rubbers; Moody, G. J., Thomas, J. D. R., Eds.; Marcel Dekker Inc.: New York, 1982;pp 79-103. Gomez-Belinchon,J. I.; Grimalt, J. 0.;Albaiges, J. Environ. Sci. Technol. 1988,22,677-685.
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Atrazine and Other s-Triazine Herbicides in Lakes and in Rain in Switzerland Hans-Rudolf Buser
Swiss Federal Research Station, 8820 Wadenswil, Switzerland All of the 18 Swiss lakes analyzed contained detectable quantities of some s-triazine herbicides. Atrazine was the major herbicide present, accompanied by smaller amounts of simazine, terbuthylazine, and occasionally (methylthio)-s-triazines, The concentration of atrazine was lowest (1ng/L or less) in mountain lakes (altitude >800 msl) and highest (up to 460 ng/L) in lakes situated in areas with intensive use of atrazine. Seasonal trends were observed, with a concentration increase in the epiliinia around June, apparently resulting from previous spring applications of the herbicides. Vertical concentration profiles of the herbicides in Lake Zurich were consistent with stratification of the lake during the warmer season and mixing in the colder one. The data suggest atrazine to be rather stable and its removal from the lakes is mainly by export via outflowing waters and less by degradation. Atrazine and other s-triazines were also detected in rainwater during the warmer season. Volatilization and wind erosion of soil particles from areas treated with these herbicides are likely the cause for the presence of these compounds in rain and aerial transport and subsequent deposition the reasons that we find these compounds in mountain lakes. However, major input of these herbicides in most other lakes stems from agricultural practices and nonagricultural uses along roads and railroads. Introduction
Natural waters may become contaminated with pesticides and other chemicals. Herbicides are especially prone 0013-936X/90/0924-1049$02.50/0
to contaminating waters because they are directly applied to soil and may then leach into groundwater, streams, rivers, and lakes. Among the herbicides, the s-triazines are an important group consisting of chloro-, (methy1thio)-, methoxy-, and some other s-triazines. Considering the amounts sold, the chloro-s-triazinesand especially atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine] are most important. The latter is one of the most heavily used herbicides worldwide. In Switzerland, its estimated use in 1986 reached 120 tons (105 tons in agriculture, predominantly cultivation of corn; 15 tons on railroads) ( 1 ) . The global release in 1980 for atrazine was estimated at 90 x IO3tons (2). In Switzerland the following s-triazines are currently registered for agricultural use: atrazine, aziprotryn, simazine, terbuthylazine, terbutryn, and terbumeton (3). The cultivation of corn, the main crop for atrazine, has greatly increased (20-fold) during the last three decades, and similarly, the use of atrazine has increased. Additionally, s-triazines were used for weed control along roads and railroads, e.g., atrazine in combination with prometryn, and terbuthylazine in combination with phenoxy acid herbicides. s-Triazines are somewhat hydrophilic (water solubilities in the mg/L range; atrazine, log P = 2.75; P, n-octanoll water partition coefficient; see ref 4) and thus to some degree mobile in the environment. Not surprisingly, traces of atrazine and some other s-triazines were detected in groundwater, rivers, and lakes (5-12). Atrazine was also detected in drinking water supplies and in rainwater
0 1990 American Chemical Society
Envlron. Sci. Technol., Vol. 24, No. 7,
1990
1049
Table I: Data on Lakes Analyzed and Sampling Locations' lake and rain (snow) (sampling location)
latitude, longitude
L. Zurich, Limmat central basin, Thalwil central basin, Stiifa L. Zurich, upper basin, Lachen L. Walen, Quinten L. Baldegg L. Sempach L. Biel, Ligerz L. Neuenburg, Neuenburg L. Murten, Murten L. Geneva, Lausanne L. Lungern, Lungern L. Sarnen, Sarnen L. Alpnach, Lopper L. Lucerne, Lucerne L. Klontal L. Obersee/Nafels L. Murg L. Glattalp L. Limmern L. Mutt Wadenswil (rain, snow, pond) Zurich (rain) Bachtel (rain) Lagern (rain)
47'21.8', 8'32.8' 47'17.3', 8'35.5' 47'13.6', 8'43.0' 47'12.4', 8'49.8' 47' 7.6', 9'13.6' 47'11.9', 8'15.8' 47' 8.5', 8' 9.7' 47' 5.0', 7' 9.7' 46'59.0', 6'57.9' 46'56.2', 7' 6.2' 46'27.3', 6'35.4' 46'47.5', 8' 9.3' 46'52.6', 8'13.8' 46'58.3', 8'18.9' 47' 3.2', 8'18.7' 47' 2.0', 8'59.6' 47' 5.2', 9' 1.0' 47' 2.5', 9' 9.3' 46'55.1', 8'54.4' 46'50.6', 9' 1.5' 46'51.7', 9' 1.8' 47'13.7', 8'40.0' 47'23.9', 8'33.0' 47O18.1', 8'53.7' 47'28.5', 8'21.9'
elev, mslb
volume theor. residence ( ~ 1 m3) 0 ~ time, yearsc
largest/ av depth, m
depths sampled, m
surface area, km2
1
406
3370
1.2 (0.23)
136150
406 419 463 504 429 429 429 372 689 469 434 434 848 983 1820 1852 1857 2446 470 510 950 690
500 2520 173 639 1240 1400 610 89000 62 244 100 11800 48 0.5
0.18 1.2 (0.11) 5.5 (1.5) 17 (3.6) 0.16 (0.05) 8.2 (1.1) 1.3 (0.42) 12 0.5 0.8 0.25 3.4
49/24 151/104 66/33 87/44 74/31 153164 49/26 3101153 68/31 52/32 33/20 2141104 49 3-5 30 25/10 120 70
