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Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is known to undergo reduction mediated by ferrous iron in the presence of minerals, including magnetite. Idealized laboratory conditions may not provide representative reaction kinetics or pathways compared to field conditions. The effects of magnetite mineral morphology, the aquifer material matrix, the presence of aqueous Fe(II), and the buffer identity on RDX reduction kinetics and intermediate formation are investigated in this work. Reactions in bicarbonate buffer were substantially slower than those performed in 3-(N-morpholino)propanesulfonic acid (MOPS) buffer, and the presence of quartz and clays in magnetite-containing aquifer material resulted in slower reaction kinetics and production of additional iron oxide phases. Buffer identity also changed the rate controlling step and reaction product distribution. Conditions as close to those expected in field systems are necessary to evaluate the reaction rates and pathways of RDX in reduced groundwater systems., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The hydrology and water chemistry of prairie pothole wetlands vary spatially and temporally, on annual and decadal timescales. Pesticide contamination of wetlands arising from agricultural activities is a foremost concern. Photochemical reactions are important in the natural attenuation of pesticides and may be important in limiting ecological and human exposure. Little is known, however, about the variable influence of wetland water chemistry on indirect photochemistry. In this study, seasonal water samples were collected from seven sites throughout the prairie pothole region over three years to understand the spatiotemporal dynamics of reactive intermediate photoproduction. Samples were classified by the season in which they were collected (spring, summer, or fall) and the typical hydroperiod of the wetland surface water (temporary or semi-permanent). Under photostable conditions, steady-state concentrations and apparent quantum yields or quantum yield coefficients were measured for triplet excited states of dissolved organic matter, singlet oxygen, hydroxyl radical, and carbonate radical under simulated sunlight. Steady-state concentrations and quantum yields increased on average by 15% and 40% from spring to fall, respectively. Temporary wetlands had 40% higher steady-state concentrations of reactive intermediates than semi-permanent wetlands, but 50% lower quantum yields. Computed quantum yields for reactive intermediate formation were used to predict the indirect photochemical half-lives of seven pesticides in average temporary and semi-permanent prairie pothole wetlands. As a first approximation, the predictions agree to within two orders of magnitude of previously reported half-lives., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Triclosan, a common antimicrobial agent, may react during the disinfection of wastewater with free chlorine to form three chlorinated triclosan derivatives (CTDs). This is of concern because the CTDs may be photochemically transformed to tri- and tetra-chlorinated dibenzo-p-dioxins when discharged into natural waters. In this study, wastewater influent, secondary (pre-disinfection) effluent, and final (post-disinfection) effluent samples were collected on two occasions each from two activated sludge wastewater treatment plants, one using chlorine disinfection and one using UV disinfection. Concentrations of triclosan and three CTDs were determined using ultra performance liquid chromatography-triple quadrupole mass spectrometry with isotope dilution methodology. Triclosan and the CTDs were detected in every influent sample at levels ranging from 453 to 4530 and 2 to 98 ng L(-1), respectively, though both were efficiently removed from the liquid phase during activated sludge treatment. Triclosan concentrations in the pre-disinfection effluent ranged from 36 to 212 ng L(-1), while CTD concentrations were below the limit of quantification (1 ng L(-1)) for most samples. In the treatment plant that used chlorine disinfection, triclosan concentrations decreased while CTDs were formed during chlorination, as evidenced by CTD levels as high as 22 ng L(-1) in the final effluent. No CTDs were detected in the final effluent of the treatment plant that used UV disinfection. The total CTD concentration in the final effluent of the chlorinating treatment plant reached nearly one third of the triclosan concentration, demonstrating that the chlorine disinfection step played a substantial role in the fate of triclosan in this system., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Triclosan, a common antimicrobial agent, may react during the disinfection of wastewater with free chlorine to form three chlorinated triclosan derivatives (CTDs). This is of concern because the CTDs may be photochemically transformed to tri- and tetra-chlorinated dibenzo-p-dioxins when discharged into natural waters. In this study, wastewater influent, secondary (pre-disinfection) effluent, and final (post-disinfection) effluent samples were collected on two occasions each from two activated sludge wastewater treatment plants, one using chlorine disinfection and one using UV disinfection. Concentrations of triclosan and three CTDs were determined using ultra performance liquid chromatography-triple quadrupole mass spectrometry with isotope dilution methodology. Triclosan and the CTDs were detected in every influent sample at levels ranging from 453 to 4530 and 2 to 98 ng L(-1), respectively, though both were efficiently removed from the liquid phase during activated sludge treatment. Triclosan concentrations in the pre-disinfection effluent ranged from 36 to 212 ng L(-1), while CTD concentrations were below the limit of quantification (1 ng L(-1)) for most samples. In the treatment plant that used chlorine disinfection, triclosan concentrations decreased while CTDs were formed during chlorination, as evidenced by CTD levels as high as 22 ng L(-1) in the final effluent. No CTDs were detected in the final effluent of the treatment plant that used UV disinfection. The total CTD concentration in the final effluent of the chlorinating treatment plant reached nearly one third of the triclosan concentration, demonstrating that the chlorine disinfection step played a substantial role in the fate of triclosan in this system., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Iron metal (Fe(0)) is a potent reductant capable of reducing a wide variety of halogenated organic compounds including disinfection byproducts (DBPs). These reduction reactions may play a role in DBP fate in iron water mains and potentially could be exploited to remove DBPs from drinking water or wastewater in a packed-bed configuration. Oxidants (i.e., dissolved oxygen (DO) and chlorine) present in the water, however, may decrease the DBP degradation rate by competing for reactive sites and rapidly aging or corroding the iron surface. Thus, batch experiments were performed to investigate the effect of DO on the degradation rates of selected DBPs by Fe(0). Experiments were performed under anaerobic conditions, in initially oxygen saturated buffer without DO control, and under controlled DO (approximately 4.0 or 8.0 mg l(-1)) conditions. The effect of short-term (25-105 min) iron aging in DO-containing buffer on DBP degradation rate also was investigated in separate experiments. For fresh Fe(0), the degradation rates of trichloronitromethane (TCNM) and trichloroacetonitrile (TCAN) in initially oxygen saturated buffer were similar to their respective rates under anaerobic conditions. The degradation rate of 1,1,1-trichloropropanone (1,1,1-TCP), however, decreased significantly in the presence of DO and the effect was proportional to DO concentration in the controlled DO experiments. For a DO concentration of 4 mg l(-1), the degradation rate of the three DBPs was greater for longer aging times as compared to their respective rates after 25 min, suggesting the formation of a mineral phase that increased reactivity. For a DO concentration of 8 mg l(-1), the effects of increasing aging time were mixed. TCNM degradation rates were stable for all aging times and comparable to that under anaerobic conditions. The TCAN and 1,1,1-TCP degradation rates, however, tended to decrease with increasing aging time. These results suggest that the reduction of highly reactive DBPs by Fe(0) will not be affected by the presence of DO but that the reaction rates will be slowed by DO for DBPs with slower degradation kinetics.

Pharmaceuticals and personal care products are an emerging class of environmental pollutants. Photolysis is expected to be a major loss process for many of these compounds in surface waters, including the common non-steroidal anti-inflammatory drug mefenamic acid. The direct photolysis solar quantum yield of mefenamic acid was observed to be 1.5+/-0.3x10(-4). Significant photosensitization was observed in solutions of Suwanee River fulvic acid and Mississippi River water, as well as for the model photosensitization compounds 3'-methoxyacetophenone, 2-acetonaphthone and perinaphthenone. Quenching, sparging and light-filtering experiments suggested a direct reaction of mefenamic acid with excited triplet-state dissolved organic matter as the major photosensitization process. The persistence of the model photosensitizer suggests that the photosensitization by perinaphthenone occurs either by triplet-energy transfer or an electron transfer followed by rapid regeneration of the sensitizer. Due to its low quantum yield, the loss of mefenamic acid in sunlit natural waters is expected to depend on both direct and indirect photodegradation processes.