A critical assessment of the photodegradation of pharmaceuticals in aquatic environments: defining our current understanding and identifying knowledge gaps.

This work presents a critical assessment of the state and quality of knowledge around the aquatic photochemistry of human- and veterinary-use pharmaceuticals from laboratory experiments and field observations. A standardized scoring rubric was used to assess relevant studies within four categories: experimental design, laboratory-based direct and indirect photolysis, and field/solar photolysis. Specific metrics for each category are defined to evaluate various aspects of experimental design (e.g., higher scores are given for more appropriate characterization of light source wavelength distribution). This weight of evidence-style approach allowed for identification of knowledge strengths and gaps covering three areas: first, the general extent of photochemical data for specific pharmaceuticals and classes; second, the overall quality of existing data (i.e., strong versus weak); and finally, trends in the photochemistry research around these specific compounds, e.g. the observation of specific and consistent oversights in experimental design. In general, those drugs that were most studied also had relatively good quality data. The four pharmaceuticals studied experimentally at least ten times in the literature had average total scores (lab and field combined) of ≥29, considered decent quality; carbamazepine (13 studies; average score of 31), diclofenac (12 studies; average score of 31), sulfamethoxazole (11 studies; average score of 34), and propranolol (11 studies; average score of 29). Major oversights and errors in data reporting and/or experimental design included: lack of measurement and reporting of incident light source intensity, lack of appropriate controls, use of organic co-solvents in irradiation solutions, and failure to consider solution pH. Consequently, a number of these experimental parameters were likely a cause of inconsistent measurements of direct photolysis rate constants and quantum yields, two photochemical properties that were highly variable in the literature. Overall, the assessment rubric provides an objective and scientifically-defensible set of metrics for assessing the quality of a study. A major recommendation is the development of a method guideline, based on this rubric, for conducting and reporting on photochemical studies that would produce consistent and reliable data for quantitative comparison across studies. Furthermore, an emphasis should be placed on conducting more dual-fate studies involving controlled photolysis experiments in natural sunlight, and whole system fate studies in either natural or artificial systems. This would provide accurate data describing the actual contribution of photolysis to the overall fate of pharmaceuticals in the environment.