The fate of organic pollutants in frozen waters: sunlight photodecomposition of uracil herbicides in frozen aqueous solutions

A study of the sunlight irradiation effects, during the winter, on two herbicides present in sensitized, frozen, aqueous solutions is reported. These solutions of bromacil (3-sec-butyl-5-bromo-6-methyluracil) and of terbacil (3- t-butyl-5-chloro-6-methyluracil) were exposed directly to sunlight or covered by different layers of ice. Both herbicides were rapidly decomposed by sunlight in the presence of sensitizers like methylene blue (1.0 ppm), rose bengal (2.0 ppm), and riboflavin (4.0 ppm), at different pH (6.8, 8.2 and 9.1) of the solutions. The best results were obtained in the alkaline range of pH. At least 70 or 75% (at pH 9.1) and 25 or 60% (at pH 8.2) of the initial amounts of bromacil or terbacil, respectively, were decomposed in the first 2 h of irradiation, using the above sensitizers. At pH 6.8, a practical rate of photodecomposition reaction was observed only in the terbacil experiments. When the frozen samples were covered by ice blocks, up to 11 cm thick, the amount of incident light reaching them was usually attenuated, but the photodecomposition reaction rates remained high enough to be of practical value. The extract residues of the irradiated solutions (6 h, pH 8.2) of bromacil (1.0 ppm MB) and terbacil (2.0 ppm RF), analyzed by TLC and by GC-MS, were found herbicide free. Only minute amounts of one and four decomposition products were present in the concentrated solutions of these residues of bromacil and terbacil, respectively.