Influence of water chemistry and operating parameters on PFOS/PFOA removal using rGO-nZVI nanohybrid.

Graphene and zero-valent-iron based nanohybrid (rGO-nZVI NH) with oxidant H2O2 can remove perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) through adsorption-degradation in a controlled aquatic environment. In this study, we evaluated how and to what extent different environmental and operational parameters, such as initial PFAS concentration, H2O2 dose, pH, ionic strength, and natural organic matter (NOM), influenced the removal of PFOS and PFOA by rGO-nZVI. With the increase in initial PFAS concentration (from 0.4 to 50 ppm), pH (3 to 9), ionic strength (0 to 100 mM), and NOM (0 to 10 ppm), PFOS removal reduced by 20%, 30%, 2%, and 6%, respectively, while PFOA removal reduced by 54%, 76%, 11%, and 33% respectively. In contrast, PFOS and PFOA removal increased by 10% and 41%, respectively, with the increase in H2O2 (from 0 to 1 mM). Overall, the effect of changes in environmental and operational parameters was more pronounced for PFOA than PFOS. Mechanistically, •OH radical generation and availability showed a profound effect on PFOA removal. Also, the electrostatic interaction between rGO-nZVI NH and deprotonated PFAS compounds was another key factor for removal. Most importantly, our study confirms that rGO-nZVI in the presence of H2O2 can degrade both PFOS and PFOA to some extent by identifying the important by-products such as acetate, formate, and fluoride.

Field evaluation of four denitrifying woodchip bioreactors for nitrogen removal in eastern South Dakota, United States.

Edge-of-field practices such as denitrifying woodchip bioreactors can be used to improve the water quality of agricultural effluents. This study evaluated the effectiveness of four field-scale woodchip bioreactors in removing nitrate­nitrogen (nitrate-N) from subsurface drainage in eastern South Dakota. Four woodchip bioreactors were installed and monitored between 2014 and 2016 near Arlington, Baltic, Hartford, and Montrose, South Dakota. Results showed that reduction in nitrate-N concentration for the four bioreactors ranged from 7 % to 100 %, corresponding to removal rates of 5 to 27 g N/m3/day for the four bioreactors during the study period. Average Nitrate-N load reduction in the four bioreactors studied ranged from 39 % to 89 % during the study period. Reduction of nitrate-N in the four bioreactors decreased, on average, by 30 % when temperature dropped below 12 °C during the study period. Flow rate and hydraulic retention time (HRT) also influenced nitrate-N removal in the bioreactors as samples collected immediately following rainfall events showed high nitrate-N load removal compared to samples collected later after the rainfall events during the study period.

Quantification of pharmaceuticals in the sealant fluids of actively used waterless urinals.

Prior measurements at bench scale revealed that waterless urinal cartridges containing oily sealant fluids are capable of partitioning pharmaceuticals from urine and therefore reducing their concentration in wastewater. We sought to measure pharmaceutical removal from in-use waterless urinals. We developed a method to quantify pharmaceuticals in the sealant phase, which resulted in 79 ± 30% and 71 ± 30% recovery of eight pharmaceuticals from two sealant fluids, respectively. The method was applied to sealant samples collected over three weeks from in-use waterless urinals on a university campus. Six of eight pharmaceuticals were present in the sealant samples from 1.4 µg/L to 241 µg/L. Loads of the six pharmaceuticals detected in the sealants were removed from the receiving wastewater from 0.02 µg/day to 3.4 µg/day across the sampling period. The concentration of the pharmaceuticals were similar over time, indicating rapid saturation and washout of the sealant. We also observed relatively rapid loss of sealant at maintenance intervals consistent with the manufacturer's instructions. These findings indicate that while waterless urinals do remove some pharmaceuticals from the wastewater stream, meaningful changes to wastewater concentrations will only result if the sealant fluid and/or the urinal cartridge are significantly modified. PRACTITIONER POINTS: We developed a quantification method for pharmaceuticals in oily waterless urinal sealants. Pharmaceuticals were present at relatively low concentrations in the sealant phase of two in-use waterless urinals. We identify engineering challenges that must be overcome to meaningfully reduce pharmaceutical loads in wastewater with waterless urinals.

Waterless Urinals Remove Select Pharmaceuticals from Urine by Phase Partitioning.

We investigated the potential for waterless urinal sealants fluids to remove pharmaceuticals from urine. 1H NMR, FTIR, and GC/MS characterization of the fluids indicated that they are mostly composed of aliphatic compounds. Removal of ethinyl estradiol was >40% for two of the three sealant fluids during simulated urination to a urinal cartridge but removal of seven other compounds with greater hydrophilicity was <30%. At equilibrium with Milli-Q water, ≥ 89% partitioning to the sealant phase was observed for three compounds with pH adjusted log Kow (log Dow) > 3.5. At equilibrium with synthetic urine, removal ranged widely from 2% to 100%. Kow was poorly correlated with removal for both matrices at equilibrium, but Dow was correlated with removal from synthetic urine for two of the three sealants, indicating that ionization and hydrophilicity control partitioning between the urine and sealant phases. To improve removal during urination, where equilibrium is not achieved, we increased the hydraulic retention time 100-fold over that of typical male urination. Removal of specific hydrophobic compounds increased, indicating that both hydrophobicity and kinetics control removal. Removal of ethinyl estradiol was ≥90% for all sealants in the increased hydraulic retention time experiment, demonstrating the potential for implementation to female urinals.