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The employment of chemometric methods is becoming increasingly widespread in several sciences, such as analytical chemistry, engineering and environmental chemistry. Response surface methodology based on statistical design of experiments has several important advantages over univariate analysis for the elucidation of the environmental relevance of photochemical reactions and their contribution to the abiotic transformation of contaminants, including a reduced number of experiments and possibilities to evaluate interactions among variables. The latter is very important considering the complicated indirect photolysis mechanisms that govern the overall fate of organic micro-pollutants. The theoretical background and several critical issues of the discussed chemometric methods are explained, while experimental work with regards to the photolytic transformation of diuron, in natural water as well as in the presence of a variety of photosensitizers, is comprehensively presented.

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