Dissolved organic matter (DOM) irradiated by sunlight generates photo-oxidants that can accelerate organic contaminant degradation in surface waters. However, the significance of this process to contaminant removal during engineered UV water treatment has not been demonstrated, partly due to a lack of suitable methods in the deep UV range. This work expands methods previously established to detect (1)O2, HO•, H2O2, and DOM triplet states ((3)DOM*) at solar wavelengths to irradiation at 254 nm, typical of UV water treatment. For transient intermediates, the methods include a photostable probe combined with selective scavengers. Quantum yields for (1)O2, (3)DOM* and H2O2 were in the same range as for solar-driven reactions but were an order of magnitude higher for HO•, which other experiments indicate is due to H2O2 reduction. With the quantum yields, the degradation of metoxuron was successfully predicted in a DOM solution irradiated at 254 nm. Further modeling showed that the contribution of DOM sensitization to organic contaminant removal during UV treatment should be significant only at high UV fluence, characteristic of advanced oxidation processes. Of the reactive species studied, (3)DOM* is predicted to have the greatest general influence on UV degradation of contaminants.
Hydraulic fracturing of unconventional gas wells utilizes large volumes of water-based fluid to increase formation permeability and, as a result, generates large amounts of wastewater as flowback. This water requires suitable treatment before being reused or discharged into the environment. A principal ingredient of flowback water is guar gum (a gelling agent), which may adversely affect advanced flowback water treatment such as membrane separation. This study demonstrates the potential of an activated sludge mixed liquor to degrade guar under typical flowback conditions [i.e., high concentrations of total dissolved solids (TDS)]. Guar was efficiently degraded at a TDS concentration of 1500 mg/L, with more than 90% of the dissolved chemical oxygen demand (COD d ) having been removed after 10 h. Increasing the TDS concentration to 45000 mg/L inhibited COD d degradation to 60% removal after 31 h. A high TDS concentration additionally resulted in an increased effluent level of total suspended solids and turbidity; however, these were efficiently reduced using ferric chloride coagulation followed by sedimentation and filtration. Biological reduction of the guar concentration increased the flux of a bench-scale ultrafiltration membrane, demonstrating the potential of the process to treat flowback water prior to membrane separation.
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