Toxic Byproduct Formation during Electrochemical Treatment of Latrine Wastewater

Electrochemical systems are an attractive option for onsite latrine wastewater treatment due to their high efficiency and small footprint. While concerns remain over formation of toxic byproducts during treatment, rigorous studies examining byproduct formation are lacking. Experiments treating authentic latrine wastewater over variable treatment times, current densities, chloride concentrations, and anode materials were conducted to characterize byproducts and identify conditions that minimize their formation. Production of inorganic byproducts (chlorate and perchlorate) and indicator organic byproducts (haloacetic acids and trihalomethanes) during electrolysis dramatically exceeded recommendations for drinking water after one treatment cycle (∼10–30 000 times), raising concerns for contamination of downstream water supplies. Stopping the reaction after ammonium was removed (i.e., the chlorination breakpoint) was a promising method to minimize byproduct formation without compromising disinfection and nutrient removal. Though treatment was accelerated at increased chloride concentrations and current densities, byproduct concentrations remained similar near the breakpoint. On TiO_2/IrO_2 anodes, haloacetic acids (up to ∼50 μM) and chlorate (up to ∼2 μM) were of most concern. Although boron-doped diamond anodes mineralized haloacetic acids after formation, high production rates of chlorate and perchlorate (up to ∼4 and 25 μM) made them inferior to TiO_2/IrO_2 anodes in terms of toxic byproduct formation. Organic byproduct formation was similar during chemical chlorination and electrolysis of wastewater, suggesting that organic byproducts are formed by similar pathways in both cases (i.e., reactions with chloramines and free chlorine)

Multilayer Heterojunction Anodes for Saline Wastewater Treatment: Design Strategies and Reactive Species Generation Mechanisms

Multilayer heterojunction SbSn/CoTi/Ir anodes, which consist of Ir_(0.7)Ta_(0.3)O_2 bottom layers coated onto a titanium base, Co-TiO_2 interlayers, and overcoated discrete Sb-SnO_2 islands, were prepared by spray pyrolysis. The Ir_(0.7)Ta_(0.3)O_2 bottom layer serves as an Ohmic contact to facilitate electron transfer from semiconductor layers to the Ti base. The Co-TiO_2 interlayer and overcoated Sb-SnO_2 islands enhance the evolution of reactive chlorine. The surficial Sb-SnO_2 islands also serve as the reactive sites for free radical generation. Experiments coupled with computational kinetic simulations show that while ·OH and Cl· are initially produced on the SbSn/CoTi/Ir anode surface, the dominant radical formed in solution is the dichlorine radical anion, Cl_2·–. The steady-state concentration of reactive radicals is 10 orders of magnitude lower than that of reactive chlorine. The SbSn/CoTi/Ir anode was applied to electrochemically treat human wastewater. These test results show that COD and NH_4^+ can be removed after 2 h of electrolysis with minimal energy consumption (370 kWh/kg COD and 383 kWh/kg NH_4^+). Although free radical species contribute to COD removal, anodes designed to enhance reactive chlorine production are more effective than those designed to enhance free radical production

Enhancing the activity of oxygen-evolution and chlorine-evolution electrocatalysts by atomic layer deposition of TiO₂

We report that TiO₂ coatings formed via atomic layer deposition (ALD) may tune the activity of IrO₂, RuO₂, and FTO for the oxygen-evolution and chlorine-evolution reactions (OER and CER). Electrocatalysts exposed to ∼3–30 ALD cycles of TiO₂ exhibited overpotentials at 10 mA cm⁻² of geometric current density that were several hundred millivolts lower than uncoated catalysts, with correspondingly higher specific activities. For example, the deposition of TiO₂ onto IrO₂ yielded a 9-fold increase in the OER-specific activity in 1.0 M H₂SO₄ (0.1 to 0.9 mA cm_(ECSA)⁻² at 350 mV overpotential). The oxidation state of titanium and the potential of zero charge were also a function of the number of ALD cycles, indicating a correlation between oxidation state, potential of zero charge, and activity of the tuned electrocatalysts

Co-occurrence of photochemical and microbiological transformation processes in open-water unit process wetlands

The fate of anthropogenic trace organic contaminants in surface waters can be complex due to the occurrence of multiple parallel and consecutive transformation processes. In this study, the removal of five antiviral drugs (abacavir, acyclovir, emtricitabine, lamivudine and zidovudine) via both bio- and phototransformation processes, was investigated in laboratory microcosm experiments simulating an open-water unit process wetland receiving municipal wastewater effluent. Phototransformation was the main removal mechanism for abacavir, zidovudine, and emtricitabine, with half-lives (t1/2,photo) in wetland water of 1.6, 7.6, and 25 h, respectively. In contrast, removal of acyclovir and lamivudine was mainly attributable to slower microbial processes (t1/2,bio = 74 and 120 h, respectively). Identification of transformation products revealed that bio- and phototransformation reactions took place at different moieties. For abacavir and zidovudine, rapid transformation was attributable to high reactivity of the cyclopropylamine and azido moieties, respectively. Despite substantial differences in kinetics of different antiviral drugs, biotransformation reactions mainly involved oxidation of hydroxyl groups to the corresponding carboxylic acids. Phototransformation rates of parent antiviral drugs and their biotransformation products were similar, indicating that prior exposure to microorganisms (e.g., in a wastewater treatment plant or a vegetated wetland) would not affect the rate of transformation of the part of the molecule susceptible to phototransformation. However, phototransformation strongly affected the rates of biotransformation of the hydroxyl groups, which in some cases resulted in greater persistence of phototransformation products

Enhancing the activity of oxygen-evolution and chlorine-evolution electrocatalysts by atomic layer deposition of TiO₂

We report that TiO₂ coatings formed via atomic layer deposition (ALD) may tune the activity of IrO₂, RuO₂, and FTO for the oxygen-evolution and chlorine-evolution reactions (OER and CER). Electrocatalysts exposed to ∼3–30 ALD cycles of TiO₂ exhibited overpotentials at 10 mA cm⁻² of geometric current density that were several hundred millivolts lower than uncoated catalysts, with correspondingly higher specific activities. For example, the deposition of TiO₂ onto IrO₂ yielded a 9-fold increase in the OER-specific activity in 1.0 M H₂SO₄ (0.1 to 0.9 mA cm_(ECSA)⁻² at 350 mV overpotential). The oxidation state of titanium and the potential of zero charge were also a function of the number of ALD cycles, indicating a correlation between oxidation state, potential of zero charge, and activity of the tuned electrocatalysts

Glucocorticoid signaling enhances expression of glucose-sensing molecules in immature pancreatic beta-like cells derived from murine embryonic stem cells in vitro

Pluripotent stem cells may serve as an alternative source of beta-like cells for replacement therapy of type 1 diabetes; however, the beta-like cells generated in many differentiation protocols are immature. The maturation of endogenous beta cells involves an increase in insulin expression starting in late gestation and a gradual acquisition of the abilities to sense glucose and secrete insulin by week 2 after birth in mice; however, what molecules regulate these maturation processes are incompletely known. Here, we aim to identify small molecules that affect immature beta cells. A cell-based assay, employing pancreatic beta-like cells derived from murine embryonic stem (ES) cells harboring a transgene containing an Insulin 1-promoter driven enhanced green fluorescent protein reporter, was used to screen a compound library (NIH Clinical Collection-003). Cortisone, a glucocorticoid, was among five positive hit compounds. Quantitative RT-PCR analysis revealed that glucocorticoids enhance the gene expression of not only insulin 1 but also glucose transporter-2 (Glut2; Slc2a2) and glucokinase (Gck), two molecules important for glucose sensing. Mifepristone, a pharmacological inhibitor of glucocorticoid receptor (GR) signaling, reduced the effects of glucocorticoids on Glut2 and Gck expression. The effects of glucocorticoids on ES-derived cells were further validated in immature primary islets. Isolated islets from 1-week-old mice had an increased Glut2 and Gck expression in response to a 4-day treatment of exogenous hydrocortisone in vitro. Gene deletion of GR in beta cells using rat insulin 2 promoter-driven Cre crossed with GRflox/flox mice resulted in a reduced gene expression of Glut2, but not Gck, and an abrogation of insulin secretion when islets were incubated in 0.5 mM D-glucose and stimulated by 17 mM D-glucose in vitro. These results demonstrate that glucocorticoids positively regulate glucose sensors in immature murine beta-like cells

The Temperature, Electron, and Pressure Characteristics of Switchbacks: Parker Solar Probe Observations

Parker Solar Probe (PSP) observes unexpectedly prevalent switchbacks, which are rapid magnetic field reversals that last from seconds to hours, in the inner heliosphere, posing new challenges to understanding their nature, origin, and evolution. In this work, we investigate the thermal states, electron pitch angle distributions, and pressure signatures of both inside and outside switchbacks, separating a switchback into spike, transition region (TR), and quiet period (QP). Based on our analysis, we find that the proton temperature anisotropies in TRs seem to show an intermediate state between spike and QP plasmas. The proton temperatures are more enhanced in spike than in TR and QP, but the alpha temperatures and alpha-to-proton temperature ratios show the opposite trends, implying that the preferential heating mechanisms of protons and alphas are competing in different regions of switchbacks. Moreover, our results suggest that the electron integrated intensities are almost the same across the switchbacks but the electron pitch angle distributions are more isotropic inside than outside switchbacks, implying switchbacks are intact structures but strong scattering of electrons happens inside switchbacks. In addition, the examination of pressures reveals that the total pressures are comparable through a switchback, confirming switchbacks are pressure-balanced structures. These characteristics could further our understanding of ion heating, electron scattering, and the structure of switchbacks.Comment: submitted to Ap

Glucocorticoid signaling enhances expression of glucose-sensing molecules in immature pancreatic beta-like cells derived from murine embryonic stem cells in vitro

Pluripotent stem cells may serve as an alternative source of beta-like cells for replacement therapy of type 1 diabetes; however, the beta-like cells generated in many differentiation protocols are immature. The maturation of endogenous beta cells involves an increase in insulin expression starting in late gestation and a gradual acquisition of the abilities to sense glucose and secrete insulin by week 2 after birth in mice; however, what molecules regulate these maturation processes are incompletely known. Here, we aim to identify small molecules that affect immature beta cells. A cell-based assay, employing pancreatic beta-like cells derived from murine embryonic stem (ES) cells harboring a transgene containing an Insulin 1-promoter driven enhanced green fluorescent protein reporter, was used to screen a compound library (NIH Clinical Collection-003). Cortisone, a glucocorticoid, was among five positive hit compounds. Quantitative RT-PCR analysis revealed that glucocorticoids enhance the gene expression of not only insulin 1 but also glucose transporter-2 (Glut2; Slc2a2) and glucokinase (Gck), two molecules important for glucose sensing. Mifepristone, a pharmacological inhibitor of glucocorticoid receptor (GR) signaling, reduced the effects of glucocorticoids on Glut2 and Gck expression. The effects of glucocorticoids on ES-derived cells were further validated in immature primary islets. Isolated islets from 1-week-old mice had an increased Glut2 and Gck expression in response to a 4-day treatment of exogenous hydrocortisone in vitro. Gene deletion of GR in beta cells using rat insulin 2 promoter-driven Cre crossed with GRflox/flox mice resulted in a reduced gene expression of Glut2, but not Gck, and an abrogation of insulin secretion when islets were incubated in 0.5 mM D-glucose and stimulated by 17 mM D-glucose in vitro. These results demonstrate that glucocorticoids positively regulate glucose sensors in immature murine beta-like cells