Kristopher McNeill

Photodegradation of pharmaceuticals in the aquatic environment: A review

Abstract.A review with 310 references. Photochemical degradation is likely to be an important loss mechanism for many pharmaceutical pollutants in surface waters. This review summarizes the current knowledge of the photochemical behavior of pharmaceuticals and highlights the use of the fundamental photochemistry and phototoxicity literature to help understand and predict the aquatic fate of pharmaceuticals. Naproxen and diclofenac are shown to exemplify the idea that photochemical behavior obtained from fundamental photochemistry studies can be related to environmental conditions. There are, however, numerous compounds that have been found in environmental matrices for which no photochemistry data relatable to environmental conditions are available. It will be necessary to combine the results available in the large body of fundamental photochemistry and phototoxicity literature with laboratory and field experiments designed to determine direct and indirect photolysis rates and to identify photoproducts. This course will lead to a thorough understanding of the role of photodegradation on the fate and impact of pharmaceutical pollutants.

Photochemical fate of pharmaceuticals in the environment: Naproxen, diclofenac, clofibric acid, and ibuprofen

Abstract.The aqueous photochemistry of four pharmaceutical compounds detected in surface waters (naproxen, diclofenac, ibuprofen, and clofibric acid) was investigating in purified (Milli-Q) water and in Mississippi River water (MRW). Both direct photolysis and hydroxyl radical-mediated indirect photolysis (using a combination of probe and quencher experiments) were studied. Singlet oxygenation was also investigated for naproxen. Second-order rate constants for reaction with hydroxyl radical were determined using Fenton’s reagent. Naproxen was rapidly transformed via direct photolysis in sunlight in both Milli-Q and MRW. The radical quencher isopropyl alcohol (IPA), had a similar effect in both systems, and this effect was interpreted as a reaction of a carboxyl radical intermediate of naproxen. Diclofenac was found to undergo rapid direct photolysis under sunlight, confirming the results of prior studies. Addition of IPA led to more rapid transformation, possibly due to formation of other radical species or photoreduction with IPA serving as the H-source. When irradiated under natural sunlight, slow direct photolysis of clofibric acid is observed in Milli-Q water, and a combination of direct photolysis and radical mediated indirect processes appear responsible for clofibric acid photolysis in MRW. The dominant photochemical loss process for ibuprofen irradiated with a medium pressure Hg-vapor lamp was identified as reaction with photo-generated radicals. These results suggest that photolytic processes are important removal mechanisms for pharmaceutical compounds discharged into sunlit surface waters.

Aqueous photochemistry of triclosan: Formation of 2,4-dichlorophenol, 2,8-dichlorodibenzo-p-dioxin, and oligomerization products

The photochemical fate of the antimicrobial agent triclosan is presented. Experiments performed in both natural and buffered deionized water show that triclosan rapidly photodegrades by direct photolysis (t(1/2) = 5 h, pH 8, noon summer sunlight, 45 degrees N latitude). Both 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) and 2,4-dichlorophenol (2,4-DCP) are produced. The 2,8-DCDD and 2,4-DCP also are photolabile and, thus, are intermediates. The yields for 2,8-DCDD and 2,4-DCP ranged from 3 to 12% depending on the conditions employed. When triclosan is photolyzed in the presence of Suwannee River (GA, USA) fulvic acid, a portion of the initial mass is recovered as insoluble material. Based on experiments in which the formation of insoluble material was monitored with photolysis time, it is postulated that photolysis in natural waters leads to some of the triclosan being coupled to humic matter. Triclosan also reacts rapidly with both singlet oxygen (k(rxn) = 1.07 +/- 0.03 x 10(8) M(-1) s(-1) in water of pH 10) and hydroxyl radical (k(*OH) = 5.4 +/- 0.3 X 10(9) M(-1)(s-1). Indirect photolysis pathways, however, are not expected to be important because of low steady-state concentrations of reactive oxygen species in natural waters and the efficiency of the direct photolysis of triclosan.

Photochemical conversion of triclosan to 2,8-dichlorodibenzo-p-dioxin in aqueous solution

The direct photolysis of triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol), an antimicrobial additive commonly detected in surface waters, is studied. It is found that 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD) is produced in both buffered and natural (Mississippi River) water with yields ranging from 1 to 12% under a variety of conditions. This result indicates that triclosan is likely converted to 2,8-DCDD in sunlight-irradiated surface waters.

Microheterogeneity of Singlet Oxygen Distributions in Irradiated Humic Acid Solutions

Singlet oxygen (1O2) is a highly reactive species formed through solar irradiation of organic matter in environmental waters. Implicated in a range of reactions, it has proven difficult to quantify its spatial distribution in natural waters. We assessed the microheterogeneous distribution of 1O2 in irradiated solutions containing chromophoric dissolved organic matter (CDOM) by using molecular probes of varying hydrophobicity. The apparent 1O2 concentrations ([1O2]app), measured by recently developed hydrophobic trap-and-trigger chemiluminescent probe molecules, were orders of magnitude higher than those measured by the conventional hydrophilic probe molecule furfuryl alcohol. The differential [1O2]app values measured by these probes reflect a steep concentration gradient between the CDOM macromolecules and the aqueous phase. A detailed kinetic model based on the data predicts probabilistic 1O2 distributions under different solvent conditions.

Covariation and photoinactivation of traditional and novel indicator organisms and human viruses at a sewage-impacted marine beach.

Sunlight modulates concentrations of Escherichia coli and enterococci in marine waters. However, the mechanism of photoinactivation is poorly understood. Additionally, little is known about photoinactivation of other fecal indicators and human viruses in recreational waters. We sampled nearshore waters at Avalon Beach, California hourly for 72 h for reactive oxygen species (ROS), traditional indicator bacteria (E. coli and enterococci, and QPCR-based detection of enterococci), F+ (DNA and RNA) and somatic coliphages, the human-specific marker in Bacteroidales (HF marker), human enterovirus, and human adenovirus. E. coli and enterococci (regardless of measurement technique) covaried with each other and the coliphages suggesting similar sources and fates. The occurrence of the HF and enterovirus markers was correlated, but their occurrence was not positively correlated with the other indicators. Lower concentrations or occurrence of all microbes, excluding the HF and enterovirus markers, were observed during sunlit as opposed to dark hours, pointing to the importance of photoinactivation. Empirical-deterministic models for a subset of microbial indicators were created to determine field-relevant sunlight inactivation rates while accounting for time dependent sources and sinks. Photoinactivation rates of enterococci and E. coli, enterococci measured by QPCR, and somatic coliphage were estimated at 7, 6, 3, and 28 d(-1) I(-1), respectively, where I is UVB intensity in W/m(2). Average H(2)O(2) was 183 nM and the maximum singlet oxygen steady state concentration was 6.6 fM. Given the clarity of the water, direct genomic damage of bacteria and coliphage, as well as indirect endogenous damage of bacteria, were likely the most important inactivation mechanisms, but we cannot rule out a contribution by indirect mechanisms involving the H(2)O(2) and singlet oxygen produced exogenously.

Methods for reactive oxygen species (ROS) detection in aqueous environments

This review summarizes direct and indirect analytical methods for the detection and quantification of the reactive oxygen species (ROS): 1O2, O2·−/HOO·, H2O2, HO·, and CO3·− in aqueous solution. Each section briefly describes the chemical properties of a specific ROS followed by a table (organized alphabetically by detection method, i.e., absorbance, chemiluminescence, etc.) summarizing the nature of the observable (associated analytical signal) for each method, limit of detection, application notes, and reaction of the probe molecule with the particular ROS.

Assessing the Contribution of Free Hydroxyl Radical in Organic Matter-Sensitized Photohydroxylation Reactions

Photochemical formation of reactive oxygen species from dissolved organic matter (DOM) is incompletely understood, especially in the case of hydroxyl radical (•OH) production. Many studies have used various probes to detect photochemically produced •OH from DOM, but the fundamental reactions of these probes are not necessarily specific for free •OH and may also detect lower-energy hydroxylation agents. In this study, two tests were applied that have previously been used as a diagnostic for the presence of free •OH: methane quenching of •OH and hydroxybenzoic acid (hBZA) product yields. Upon application of these two tests to a set of five DOM isolates, it was found that methane quenching and the hBZA ratio results were not necessarily consistent. Overall, the results provide compelling evidence that all isolates studied photochemically produce free •OH. The hydroxylating acitivity of Elliot Soil Humic Acid and Pony Lake Fulvic Acid, however, also had a significant contribution from a photochemically generated hydroxylating agent that is lower in energy than free •OH. Catalase quenching experiments were conducted to assess whether hydrogen peroxide was the immediate precursor to hydroxyl in these systems. In all cases, catalase addition slowed photohydroxylation of terephthalate, but the contribution of hydrogen peroxide photolysis was determined to be less than 50%.

Direct photochemistry of three fluoroquinolone antibacterials: Norfloxacin, ofloxacin, and enrofloxacin

Fluoroquinolone (FQ) antibacterial compounds are frequently detected in the aquatic environment, and photodegradation is expected to play an important role in FQ fate in some sunlit surface waters. This study investigated the direct aquatic photochemistry of three FQs: norfloxacin, ofloxacin, and enrofloxacin. The direct photolysis rate of each drug exhibited strong pH dependence when exposed to simulated sunlight. For each FQ, direct photolysis rates and total light absorbance were used to calculate quantum yields for each of three environmentally relevant protonation states: a cationic, a zwitterionic, and an anionic form. In each case, quantum yields of the species varied significantly. The quantum yield for the zwitterionic form was 2-3 times higher than that of the anionic form and over an order of magnitude higher than that of the cationic form. Antibacterial activity assays were used to determine whether the loss of parent FQ due to photolysis led to loss of activity. Norfloxacin and ofloxacin photoproducts were found to be inactive, whereas enrofloxacin photoproducts were found to retain significant activity. These results are important for aiding in predictions of the potential impacts of FQs in surface waters.

Dioxin Photoproducts of Triclosan and Its Chlorinated Derivatives in Sediment Cores

Triclosan, a widely used antimicrobial, is known to undergo phototransformation in aqueous solution to form 2,8-dichlorodibenzo-p-dioxin (2,8-DCDD). Two sediment cores from a wastewater-impacted depositional zone of the Mississippi River were analyzed for triclosan by ultra performance liquid chromatography-triple quadrupole mass spectrometry (UPLC-MS-Q(3)) and for a suite of polychlorinated dioxins and furans by high resolution gas chromatography-mass spectrometry (HRGC-MS) to provide evidence of this photoreaction in the environment. 2,8-DCDD was detected at levels that trended with the historical use of triclosan since its introduction in the 1960s. Three other dioxin congeners, 2,3,7-TCDD, 1,2,8-TriCDD, and 1,2,3,8-TCDD, which are known photoproducts of chlorinated derivatives of triclosan, were also detected with similar trend profiles. These four congeners comprised the majority of di- through tetra-chlorinated dioxins. The trend profile of these specific dioxin congeners did not correlate with the trend profile of the higher-chlorinated dioxin homologues or any chlorinated furan homologues, suggesting a unique source. These results are fully consistent with the phototransformation of triclosan and its chlorinated derivatives that form during wastewater chlorine disinfection as the source of 2,8-DCDD, 2,3,7-TriCDD, 1,2,8-TriCDD, and 1,2,3,8-TCDD in this aquatic environment. As the levels of triclosan-derived dioxins increased over time and the total level of chlorinated dioxins decreased, the contribution of triclosan-derived dioxins to the total dioxin pool increased to as high as 31% by mass in recent years, indicating that their contribution to total dioxin toxicity may need consideration.