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Fluoxetine (FLX) was shown to be photoreactive in sunlit surface waters. FLX degraded in deionized water when exposed to simulated sunlight with a half-life of 55.2+/-3.6 h(-1). Photodegradation products were identified using high performance liquid chromatography-UV (HPLC-UV) and liquid chromatography tandem mass spectrometry (LC-MS-MS) using electrospray (ES) ionization. Defluorination of the trifluoromethyl group in FLX and in fluometuron and flutalanil,two other compounds containing this functional group, is suggested to be a common direct photolysis pathway for trifluoromethylated compounds. Products resulting from O-dealkylation of FLX were also observed. The rate of degradation was faster in synthetic field water where .OH was the likely dominant oxidant in the system. The bimolecular rate constant for the reaction between FLX and .OH was measured as (8.4+/-0.5) x 10(9) and (9.6 +/-0.8) x 10(9) M(-1) s(-1) using two different methods of competition kinetics. Indirect photodegradation reactions could lead to the production of hydroxylated and O-dealkylated compounds. Although direct photolysis could potentially limitthe persistence of FLX in surface waters, its degradation by indirect photolysis would proceed faster. Thus, this latter process could be important in the elimination of FLX in surface waters.

Pharmaceuticals have been detected in surface waters of the US and Europe, originating largely from two sources, sewage effluent and agricultural runoff. These compounds often occur as mixtures leading to potential combined effects. In order to investigate the effects of a realistic pharmaceutical mixture on an ecosystem, a study utilizing 15 of 12,000 L aquatic microcosms treated with eight common pharmaceuticals (atorvastatin, acetaminophen, caffeine, sulfamethoxazole, carbamazepine, levofloxacin, sertraline, and trimethoprim) at total (summed) molar concentrations of 0, 0.044, 0.608, 2.664, and 24.538 micromol/L (n = 3) was conducted. Phytotoxicity was assessed on a variety of somatic and pigment endpoints in rooted (Myriophyllum sibiricum) and floating (Lemna gibba) macrophytes over a 35-day period. EC10, EC25 and EC50 values were calculated for each endpoint exhibiting a concentration-dependent response. Generally, M. sibiricum and L. gibba displayed similar sensitivity to the pharmaceutical mixture, with phytotoxic injury evident in both species, which was concentration dependent. Through single compound 7-day daily static renewal toxicity tests with L. gibba, the sulfonamide antibiotic sulfamethoxazole, the fluoroquinolone antibiotic levofloxacin and the blood lipid regulator atorvastatin were found to be the only compounds to elicit phytotoxic effects in the concentration range utilized (0-1000 microg/L). Atorvastatin concentration was highly correlated to decreased pigment content in L. gibba, likely inhibiting the known target enzyme HMGR, the rate-limiting enzyme in isoprenoid biosynthesis. Hazard quotients were calculated for both microcosm and laboratory studies; the highest HQ values were 0.235 (L. gibba) and 0.051 (L. gibba), which are below the threshold value of 1 for chronic risks. The microcosm data suggest that at an ecological effect size of >20%, biologically significant risks are low for L. gibba and M. sibiricum exposed to similar mixtures of pharmaceutical compounds. For M. sibiricum and L. gibba, respective minimum differences of 5 and 1%, were detectable, however, these effect sizes are not considered ecologically significant.

The persistence of eight pharmaceuticals from multiple classes was studied in aquatic outdoor field microcosms. A method was developed for the determination of a mixture of acetaminophen, atorvastatin, caffeine, carbamazepine, levofloxacin, sertraline, sulfamethoxazole, and trimethoprim at microg/L levels from surface water of the microcosms using solid phase extraction and high-performance liquid chromatography-ultraviolet (HPLC-UV) and liquid chromatography tandem mass spectrometry (LC-MS-MS). Half-lives in the field ranged from 1.5 to 82 d. Laboratory persistence tests were performed to determine the relative importance of possible loss processes in the microcosms over the course of the study. Results from dark control experiments suggest hydrolysis was not important in the loss of the compounds. No significant differences were observed between measured half-lives of the pharmaceuticals in sunlight-exposed pond water and autoclaved pond water, which suggests photodegradation was important in limiting their persistence, and biodegradation was not an important loss process in surface water over the duration of the study. Observed photoproducts of several of the pharmaceuticals remained photoreactive, which led to further degradation in irradiated surface waters.

A new approach was developed to account for the contribution of indirect photolysis of pesticides and pharmaceuticals in which laboratory test conditions are similar to those prevalent in the aqueous environment. Rates of photolysis as a function of water composition were investigated for several aquatic contaminants. Using the laboratory-based test system, PhotoFate, the dependence of phototransformation rates on concentrations of natural water constituents that are radical producers and scavengers (nitrate, colored dissolved organic matter, bicarbonate) was studied. Mean half-lives of the model compounds in the presence of water constituents were compared to their direct photolysis half-lives to assess the contribution of photosensitized reactions to their fate in surface waters. Reactions mediated by .OH were predominant in waters with high nitrate concentrations. Colored dissolved organic matter (cDOM) acted mainly as a radiation filter and had a more important role in scavenging radicals than in their production. However, in low nitrate waters, the contribution of cDOM-derived reactive intermediates to the degradation of parent compounds became more apparent