Sorbic acid as a quantitative probe for the formation, scavenging and steady-state concentrations of the triplet-excited state of organic compounds

Sorbic acid (trans,trans-hexadienoic acid) was developed as a probe for the quantification of the formation rate, overall solution scavenging rate and steady-state concentrations of triplet-excited states of organic compounds. The method was validated against literature data for the quenching rate constant of triplet benzophenone by tyrosine obtained by laser flash photolysis and by Stern-Volmer plots of phosphorescence quenching. In contrast to these methods, the probe method does not require knowledge of the optical properties of triplets to monitor their quenching. Moreover, the probe method permits simultaneous quantification of triplet formation, quenching and steady-state concentrations during illumination of complex chromophore mixtures, such as natural organic matter (NOM), with polychromatic light >315 nm. Application of the method to de-aerated Suwannee River NOM illuminated with polychromatic light (315-430 nm) resulted in a triplet quantum yield of 0.062.     

Impact of UV disinfection combined with chlorination/chloramination on the formation of halonitromethanes and haloacetonitriles in drinking water

The application of UV disinfection in water treatment is increasing due to both its effectiveness against protozoan pathogens, and the perception that its lack of chemical inputs would minimize disinfection byproduct formation. However, previous research has indicated that treatment of nitrate-containing drinking waters with polychromatic medium pressure (MP), but not monochromatic (254 nm) low pressure (LP), UV lamps followed by chlorination could promote chloropicrin formation. To better understand this phenomenon, conditions promoting the formation of the full suite of chlorinated halonitromethanes and haloacetonitriles were studied. MP UV/postchlorination of authentic filter effluent waters increased chloropicrin formation up to an order of magnitude above the 0.19 μg/L median level in the U.S. EPA's Information Collection Rule database, even at disinfection-level fluences (<300 mJ/cm(2)) and nitrate/nitrite concentrations (1.0 mg/L-N) relevant to drinking waters. Formation was up to 2.5 times higher for postchlorination than for postchloramination. Experiments indicated that the nitrating agent, NO(2)(?), generated during nitrate photolysis, was primarily responsible for halonitromethane promotion. LP UV treatment up to 1500 mJ/cm(2) did not enhance halonitromethane formation. Although MP UV/postchloramination enhanced dichloroacetonitrile formation with Sigma-Aldrich humic acid, formation was not significant in field waters. Prechlorination/MP UV nearly doubled chloropicrin formation compared to MP UV/postchlorination, but effects on haloacetonitrile formation were not significant.     

Fecal coliform accumulation within a river subject to seasonally-disinfected wastewater discharges

As pathogen contamination is a leading cause of surface water impairment, there has been increasing interest in the implications of seasonal disinfection practices of wastewater effluents for meeting water quality goals. For receiving waters designated for recreational use, disinfection during the winter months is often considered unnecessary due to reduced recreational usage, and assumptions that lower temperatures may reduce pathogen accumulation. For a river subject to seasonal disinfection, we sought to evaluate whether fecal coliforms accumulate during the winter to concentrations that would impair river water quality. Samples were collected from municipal wastewater outfalls along the river, as well as upstream and downstream of each outfall during the winter, when disinfection is not practiced, and during the summer, when disinfection is practiced. During both seasons, fecal coliform concentrations reached 2000–5000 CFU/100 mL, nearly an order of magnitude higher than levels targeted for the river to achieve primary contact recreational uses. During the summer, wastewater effluents were not significant contributors to fecal coliform loadings to the river. During the winter, fecal coliform accumulated along the river predominantly due to loadings from successive wastewater outfalls. In addition to the exceedance of fecal coliform criteria within the river, the accumulation of wastewater-derived fecal coliform along the river during the winter season suggests that wastewater outfalls may contribute elevated loads of pathogens to the commercial shellfish operations occurring at the mouth of the river. Reductions in fecal coliform concentrations between wastewater outfalls were attributed to dilution or overall removal. Combining discharge measurements from gauging stations, tributaries and wastewater outfalls to estimate seepage, dilution between wastewater outfalls was estimated, along with the percentage of the river deriving from wastewater outfalls. After accounting for dilution, the residual reductions in fecal coliform concentrations observed between outfalls were attributed to actual fecal coliform removal. The estimated rate of removal of 1.52 d^?1 was significantly higher than die-off rates determined by previous researchers at similarly low temperatures in laboratory batch experiments, indicating the potential importance of other removal mechanisms, such as predation or sedimentation.     

Separation of methane and nitrogen using ionic liquidic zeolites by pressure vacuum swing adsorption

The separation of methane (CH₄) and nitrogen (N₂) is a significant challenge to the enrichment and utilization of low concentration CH₄ due to the similarity in the physical and chemical properties of the two molecules. In this work, we investigated the separation of CH₄ from N₂ using 100 kg of a new ionic liquidic zeolite (ILZ) material in a 6-bed pilot-scale pressure swing adsorption process. Feed gases with CH₄ concentrations of 5.0% and 16.1% were upgraded to 11.5% and 34.6%, respectively, with CH₄ recoveries higher than 80%. The pilot test results were used to anchor a numerical model that then allowed the efficient investigation of multiple operational parameters including desorption pressure and feed gas flow rates. The numerical model produced CH₄ concentrations for both product streams consistent with those measured in the pilot experiments, with root mean square deviations below 2%. The modeling results revealed that sufficiently low desorption pressures can unexpectedly lead to lower heavy product purities under limited feed gas flow conditions. Furthermore, the optimum feed gas flow rate under which maximum heavy product purity is achieved increases with lower desorption pressure. The maximum CH₄ concentrations increased from 31.8% to 41.5%, as desorption pressures decreased from 22.8 to 12.2 kPa for optimum feed flow rates between 78.2 and 105.5 mol/h. We also demonstrate a method of process optimization based on the bed capacity ratio, ℂ, which provides a scale-independent measure of the degree to which the column is being used effectively. By varying feed flow rate and/or desorption pressure, ℂ values between 0.2 and 0.8 were explored, with maxima in the combined separation performance metric (methane recovery) × (methane purity) occurring for values of ℂ in the range 0.29–0.36. This separation performance optimization by adjusting ℂ provides an effective strategy for integrating and understanding the impact of multiple operating parameters.     

Next Generation Thermal Barrier Coatings for the Gas Turbine Industry

The aim of this study is to develop the next generation of production ready air plasma sprayed thermal barrier coating with a low conductivity and long lifetime. A number of coating architectures were produced using commercially available plasma spray guns. Modifications were made to powder chemistry, including high purity powders, dysprosia stabilized zirconia powders, and powders containing porosity formers. Agglomerated & sintered and homogenized oven spheroidized powder morphologies were used to attain beneficial microstructures. Dual layer coatings were produced using the two powders. Laser flash technique was used to evaluate the thermal conductivity of the coating systems from room temperature to 1200 °C. Tests were performed on as-sprayed samples and samples were heat treated for 100 h at 1150 °C. Thermal conductivity results were correlated to the coating microstructure using image analysis of porosity and cracks. The results show the influence of beneficial porosity on reducing the thermal conductivity of the produced coatings.