On the use of dioxane as reference for determination of the hydrodynamic radius by NMR spectroscopy.

Measuring the compaction of a protein or complex is key to our understanding of the interactions within and between biomolecules. Experimentally, protein compaction is often probed either by estimating the radius of gyration (Rg) obtained from small-angle X-ray scattering (SAXS) experiments or the hydrodynamic radius (Rh) obtained for example by pulsed field gradient nuclear magnetic resonance (PFG NMR) spectroscopy. PFG NMR experiments generally report on the translational diffusion coefficient, which in turn can be used to estimate Rh using an internal standard to account for sample viscosity and uncertainty about the gradient strength. 1,4-dioxane is one such commonly used internal standard, and the reference value of Rh is therefore important. We have revisited the basis for the commonly used reference value for the Rh of dioxane (2.12 Å) that is used to convert measured diffusion coefficients into a hydrodynamic radius. We followed the same approach that was used to establish the current reference value by measuring SAXS and PFG NMR data for a set of seven different proteins and using these as standards. Our analysis shows that the current Rh reference value for dioxane Rh is underestimated, and we instead suggest a new value of 2.27 Å ± 0.04 Å. Using this updated reference value results in a ∼7% increase in Rh values for proteins whose hydrodynamic radii have been measured by PFG NMR. These results are particularly important when the absolute value of Rh is of interest such as when determining or validating ensemble descriptions of intrinsically disordered proteins.

Tackling Challenges of Long-Term Electrode Stability in Electrochemical Treatment of 1,4-Dioxane in Groundwater.

Electrochemical advanced oxidation is an appealing point-of-use groundwater treatment option for removing pollutants such as 1,4-dioxane, which is difficult to remove by using conventional separation-based techniques. This study addresses a critical challenge in employing electrochemical cells in practical groundwater treatment─electrode stability over long-term operation. This study aims to simulate realistic environmental scenarios by significantly extending the experimental time scale, testing a flow-through cell in addition to a batch reactor, and employing an electrolyte with a conductivity equivalent to that of groundwater. We first constructed a robust titanium suboxide nanotube mesh electrode that is utilized as both anode and cathode. We then implemented a pulsed electrolysis strategy in which reactive oxygen species are generated during the anodic cycle, and the electrode is regenerated during the cathodic cycle. Under optimized conditions, single-pass treatment through the cell (effective area: 2 cm2) achieved a remarkable 65-70% removal efficiency for 1,4-dioxane in the synthetic groundwater for over 100 h continuous operation at a low current density of 5 mA cm-2 and a water flux of 6 L m-2 h-1. The electrochemical cell and pulse treatment scheme developed in this study presents a critical advancement toward practical groundwater treatment technology.

Dichloramine Hydrolysis in Membrane Desalination Permeate: Mechanistic Insights and Implications for Oxidative Capacity in Potable Reuse Applications.

Dichloramine (NHCl2) naturally exists in reverse osmosis (RO) permeate due to its application as an antifouling chemical in membrane-based potable reuse treatment. This study investigated mechanisms of background NHCl2 hydrolysis associated with the generation of oxidative radical species in RO permeate, established a kinetic model to predict the oxidative capacity, and examined its removal efficiency on trace organic contaminants in potable reuse. Results showed that NHCl2 hydrolysis generated transient peroxynitrite (ONOO-) and subsequently dissociated into hydroxyl radical (HO•). The maximal HO• exposure was observed at an RO permeate pH of 8.4, higher than that from typical ultraviolet (UV)-based advanced oxidation processes. The HO• exposure during NHCl2 hydrolysis also peaked at a NH2Cl-to-NHCl2 molar ratio of 1:1. The oxidative capacity rapidly degraded 1,4-dioxane, carbamazepine, atenolol, and sulfamethoxazole in RO permeate. Furthermore, background elevated carbonate in fresh RO permeate can convert HO• to carbonate radical (CO3•-). Aeration of the RO permeate removed total carbonate, significantly increased HO• exposure, and enhanced the degradation kinetics of trace organic contaminants. The kinetic model of NHCl2 hydrolysis predicted well the degradation of contaminants in RO permeate. This study provides new mechanistic insights into NHCl2 hydrolysis that contributes to the oxidative degradation of trace organic contaminants in potable reuse systems.

Effect of 1,4-Dioxane Solvent on ß-Glucuronidation Using Methyl 1,2,3,4-Tetra-O-acetyl-ß-D-glucuronate as the Glycosyl Donor.

A facile and selective ß-D-glucuronidation of alcohols, such as (-)-menthol, cholestanol, (+)- and (-)-borneols, and 2-adamantanol, using commercially available methyl 1,2,3,4-tetra-O-acetyl-ß-D-glucuronate as the glycosyl donor and trimethylsilyl bis(trifluoromethanesulfonyl)imide (Tf2NTMS) (0.5 equivalent) as the activator in 1,4-dioxane at 60 °C gave products in moderate yields. The addition of MS4A increased the ß : α ratios of D-glucuronides when cholestanol, (+)-borneol, and 2-adamantanol were used as the acceptor substrate.

New potent muscarinic receptor ligands bearing the 1,4-dioxane nucleus: Investigation on the nature of the substituent in position 2.

A new series of muscarinic acetylcholine receptor (mAChR) ligands obtained by inserting different substituents in position 2 of the potent 6,6-diphenyl-1,4-dioxane antagonists 4 and 5 was designed and synthesized to investigate the influence of steric bulk on the mAChR affinity. Specifically, the insertion of a 2-methyl group, affording compounds 6 and 9, resulted as the most favorable modification in terms of affinity for all muscarinic subtypes. As supported by computational studies performed on the hM1 receptor, this substituent may contribute to stabilize the ligand within the binding site by favoring the formation of stable interactions between the cationic head of the ligand and the residue D105. The increase of steric bulk, obtained by replacing the methyl group with an ethyl (7 and 10) and especially a phenyl substituent (8 and 11), caused a marked decrease of mAChR affinity, demonstrating the crucial role played by the steric bulk of the 2-substituent in the mAChR interaction. The most intriguing result was obtained with the tertiary amine 9, which, surprisingly, showed two different pKi values for all mAChRs, with preferential subpicomolar affinities for the M1, M3, and M4 subtypes. Interestingly, biphasic curves were also observed with both the eutomer (S)-(-)-9 and the distomer (R)-( + )-9.

Dual phytoremediation and biochar production by Eichhornia crassipes in hydroponic system receiving different 1,4-dioxane dosages.

This study focuses on applying phytoremediation as a low-effective and simple process to treat wastewater laden with 1,4 dioxane (DIOX). A floating macrophyte (Eichhornia crassipes) was cultivated under hydroponic conditions (relative humidity 50-67%, photoperiod cycle 18:6 h light/dark, and 28-33 °C) and subjected to different DIOX loads between 0.0 (control) and 11.5 mg/g fresh mass (FM). The aquatic plant achieved DIOX and chemical oxygen demand (COD) removal efficiencies of 76-96% and 67-94%, respectively, within 15 days. E. crassipes could tolerate elevated DIOX-associated stresses until a dose of 8.2 mg DIOX/g, which highly influenced the oxidative defense system. Malondialdehyde (MDA) content, hydrogen peroxide (H2O2), and total phenolic compounds (TPC) increased by 7.3, 8.4, and 4.5-times, respectively, in response to operating the phytoremediation unit at a DIOX load of 11.5 mg/g. The associated succulent value, proteins, chlorophyll-a, chlorophyll-b, and pigments dropped by 39.6%, 45.8%, 51.5%, 80.8%, and 55.5%, respectively. The suggested removal mechanism of DIOX by E. crassipes could be uptake followed by phytovolatilization, whereas direct photodegradation from sunlight contributed to about 19.36% of the total DIOX removal efficiencies. Recycling the exhausted E. crassipes for biochar production was a cost-efficient strategy, making the payback period of the phytoremediation project equals to 6.96 yr.

Eichhornia crassipes could be used in phytoremediation of 1,4 dioxane (DIOX)-laden water at DIOX load< 8.2 mg/g FM. E. crassipes removed 77­97% DIOX via uptake and phytovolatilization. Recycling exhausted-plant to produce biochar was cost-efficient with 7 yr-payback period.

The electrocatalytic degradation of 1,4-dioxane by Co-Bi/GAC particle electrode.

Efficient degradation of industrial organic wastewater has become a significant environmental concern. Electrochemical oxidation technology is promising due to its high catalytic degradation ability. In this study, Co-Bi/GAC particle electrodes were prepared and characterized for degradation of 1,4-dioxane. The electrochemical process parameters were optimized by response surface methodology (RSM), and the influence of water quality factors on the removal rate of 1,4-dioxane was investigated. The results showed that the main influencing factors were the Co/Bi mass ratio and calcination temperature. The carrier metals, Co and Bi, existed mainly on the GAC surface as Co3O4 and Bi2O3. The removal of 1,4-dioxane was predominantly achieved through the synergistic reaction of electrode adsorption, anodic oxidation, and particle electrode oxidation, with ·OH playing a significant role as the main active free radical. Furthermore, the particle electrode was demonstrated in different acid-base conditions (pH = 3, 5, 7, 9, and 11). However, high concentrations of Cl- and NO3- hindered the degradation process, potentially participating in competitive reactions. Despite this, the particle electrode exhibited good stability after five cycles. The results provide a new perspective for constructing efficient and stable three-dimensional (3D) electrocatalytic particle electrodes to remove complex industrial wastewater.

Isolation and characterization of pure cultures for metabolizing 1,4-dioxane in oligotrophic environments.

1,4-Dioxane concentration in most contaminated water is much less than 1 mg/L, which cannot sustain the growth of most reported 1,4-dioxane-metabolizing pure cultures. These pure cultures were isolated following enrichment of mixed cultures at high concentrations (20 to 1,000 mg/L). This study is based on a different strategy: 1,4-dioxane-metabolizing mixed cultures were enriched by periodically spiking 1,4-dioxane at low concentrations (≤1 mg/L). Five 1,4-dioxane-metabolizing pure strains LCD6B, LCD6D, WC10G, WCD6H, and WD4H were isolated and characterized. The partial 16S rRNA gene sequencing showed that the five bacterial strains were related to Dokdonella sp. (98.3%), Acinetobacter sp. (99.0%), Afipia sp. (99.2%), Nitrobacter sp. (97.9%), and Pseudonocardia sp. (99.4%), respectively. Nitrobacter sp. WCD6H is the first reported 1,4-dioxane-metabolizing bacterium in the genus of Nitrobacter. The net specific growth rates of these five cultures are consistently higher than those reported in the literature at 1,4-dioxane concentrations <0.5 mg/L. Compared to the literature, our newly discovered strains have lower half-maximum-rate concentrations (1.8 to 8.2 mg-dioxane/L), lower maximum specific 1,4-dioxane utilization rates (0.24 to 0.47 mg-dioxane/(mg-protein ⋅ d)), higher biomass yields (0.29 to 0.38 mg-protein/mg-dioxane), and lower decay coefficients (0.01 to 0.02 d-1). These are characteristics of microorganisms living in oligotrophic environments.

Reaction of ß-Ketoester and 1,3-Diol to Access Chemically Recyclable and Mechanically Robust Poly(vinyl alcohol) Thermosets through Incorporation of ß-(1,3-dioxane)ester.

The development of mechanically robust, chemically stable, and yet recyclable polymers represents an essential undertaking in the context of advancing a circular economy for plastics. Here, we introduce a novel cleavable ß-(1,3-dioxane)ester (DXE) linkage, synthesized through the catalyst-free reaction of ß-ketoester and 1,3-diol, to cross-link poly(vinyl alcohol) (PVA) for the formation of high-performance thermosets with inherent chemical recyclability. PVA, modified with ß-ketoester groups through the transesterification reaction with excess tert-butyl acetoacetate, undergoes cross-linking reactions with the unmodified 1,3-diols within PVA itself upon thermal treatment. The cross-linking architecture improves PVA's mechanical properties, with Young's modulus and toughness that can reach up to 656 MPa and 84 MJ cm-3, i.e. approximately 3- and 12-fold those of linear PVA, respectively. Thermal treatment of the cross-linked PVA polymers under acid conditions leads to deconstruction of the networks, enabling the excellent recovery (>90 %) of PVA. In the absence of either thermal or acidic treatment, the cross-linked PVA maintains its dimensional stability. We show that the recovery of PVA is also possible when the treatment is performed in the presence of other plastics commonly found in recycling mixtures. Furthermore, PVA-based composites comprising carbon fibers and activated charcoal cross-linked by the DXE linkages are also shown to be recyclable with recovery of the PVA and the fillers.

Optimizing Ozone Disinfection in Water Reuse: Controlling Bromate Formation and Enhancing Trace Organic Contaminant Oxidation.

The use of ozone/biofiltration advanced treatment has become more prevalent in recent years, with many utilities seeking an alternative to membrane/RO based treatment for water reuse. Ensuring efficient pathogen reduction while controlling disinfection byproducts and maximizing oxidation of trace organic contaminants remains a major barrier to implementing ozone in reuse applications. Navigating these challenges is imperative in order to allow for the more widespread application of ozonation. Here, we demonstrate the effectiveness of ozone for virus, coliform bacteria, and spore forming bacteria inactivation in unfiltered secondary effluent, all the while controlling the disinfection byproduct bromate. A greater than 6-log reduction of both male specific and somatic coliphages was seen at specific ozone doses as low as 0.75 O3:TOC. This study compared monochloramine and hydrogen peroxide as chemical bromate control measures in high bromide water (Br- = 0.35 ± 0.07 mg/L). On average, monochloramine and hydrogen peroxide resulted in an 80% and 36% decrease of bromate formation, respectively. Neither bromate control method had any appreciable impact on virus or coliform bacteria disinfection by ozone; however, the use of hydrogen peroxide would require a non-Ct disinfection framework. Maintaining ozone residual was shown to be critical for achieving disinfection of more resilient microorganisms, such as spore forming bacteria. While extremely effective at controlling bromate, monochloramine was shown to inhibit TrOC oxidation, whereas hydrogen peroxide enhanced TrOC oxidation.

Characterization of 1,4-dioxane degrading microbial community enriched from uncontaminated soil.

1,4-Dioxane is a contaminant of emerging concern that has been commonly detected in groundwater. In this study, a stable and robust 1,4-dioxane degrading enrichment culture was obtained from uncontaminated soil. The enrichment was capable to metabolically degrade 1,4-dioxane at both high (100 mg L-1) and environmentally relevant concentrations (300 µg L-1), with a maximum specific 1,4-dioxane degradation rate (qmax) of 0.044 ± 0.001 mg dioxane h-1 mg protein-1, and 1,4-dioxane half-velocity constant (Ks) of 25 ± 1.6 mg L-1. The microbial community structure analysis suggested Pseudonocardia species, which utilize the dioxane monooxygenase for metabolic 1,4-dioxane biodegradation, were the main functional species for 1,4-dioxane degradation. The enrichment culture can adapt to both acidic (pH 5.5) and alkaline (pH 8) conditions and can recover degradation from low temperature (10°C) and anoxic (DO < 0.5 mg L-1) conditions. 1,4-Dioxane degradation of the enrichment culture was reversibly inhibited by TCE with concentrations higher than 5 mg L-1 and was completely inhibited by the presence of 1,1-DCE as low as 1 mg L-1. Collectively, these results demonstrated indigenous stable and robust 1,4-dioxane degrading enrichment culture can be obtained from uncontaminated sources and can be a potential candidate for 1,4-dioxane bioaugmentation at environmentally relevant conditions. KEY POINTS: •1,4-Dioxane degrading enrichment was obtained from uncontaminated soil. • The enrichment culture could degrade 1,4-dioxane to below 10 µg L-1. •Low Ks and low cell yield of the enrichment benefit its application in bioremediation.

An integrated assessment of the 1,4-dioxane cancer mode of action and threshold response in rodents.

1,4-Dioxane is an environmental contaminant that has been shown to cause cancer in rodents after chronic high dose exposures. We reviewed and integrated information from recently published studies to update our understanding of the cancer mode of action of 1,4-dioxane. Tumor development in rodents from exposure to high doses of 1,4-dioxane is preceded by pre-neoplastic events including increased hepatic genomic signaling activity related to mitogenesis, elevation of Cyp2E1 activity and oxidative stress leading to genotoxicity and cytotoxicity. These events are followed by regenerative repair and proliferation and eventual development of tumors. Importantly, these events occur at doses that exceed the metabolic clearance of absorbed 1,4-dioxane in rats and mice resulting in elevated systemic levels of parent 1,4-dioxane. Consistent with previous reviews, we found no evidence of direct mutagenicity from exposure to 1,4-dioxane. We also found no evidence of CAR/PXR, AhR or PPARα activation resulting from exposure to 1,4-dioxane. This integrated assessment supports a cancer mode of action that is dependent on exceeding the metabolic clearance of absorbed 1,4-dioxane, direct mitogenesis, elevation of Cyp2E1 activity and oxidative stress leading to genotoxicity and cytotoxicity followed by sustained proliferation driven by regenerative repair and progression of heritable lesions to tumor development.

Simultaneous biodegradation kinetics of 1,4-dioxane and ethane.

Biodegradation of 1,4-Dioxane at environmentally relevant concentrations usually requires the addition of a primary electron-donor substrate to sustain biomass growth. Ethane is a promising substrate, since it is available as a degradation product of 1,4-Dioxane's common co-contaminants. This study reports kinetic parameters for ethane biodegradation and co-oxidations of ethane and 1,4-Dioxane. Based on experiments combined with mathematical modeling, we found that ethane promoted 1,4-Dioxane biodegradation when the initial mass ratio of ethane:1,4-Dioxane was < 9:1 mg COD/mg COD, while it inhibited 1,4-Dioxane degradation when the ratio was > 9:1. A model-independent estimator was used for kinetic-parameter estimation, and all parameter values for 1,4-Dioxane were consistent with literature-reported ranges. Estimated parameters support competitive inhibition between ethane as the primary substrate and 1,4-Dioxane as the secondary substrate. The results also support that bacteria that co-oxidize ethane and 1,4-Dioxane had a competitive advantage over bacteria that can use only one of the two substrates. The minimum concentration of ethane to sustain ethane-oxidizing bacteria and ethane and 1,4-Dioxane-co-oxidizing bacteria was 0.09 mg COD/L, which is approximately 20-fold lower than the minimum concentration reported for propane, another common substrate used to promote 1,4-Dioxane biodegradation. The minimum 1,4-Dioxane concentration required to sustain steady-state biomass with 1,4-Dioxane as the sole primary substrate was 1.3 mg COD/L. As 1,4-Dioxane concentrations at most groundwater sites are less than 0.18 mg COD/L, providing ethane as a primary substrate is vital to support biomass growth and consequently enable 1,4-Dioxane bioremediation.

Biodegradation of 1,4-dioxane by a native digestate microbial community under different electron accepting conditions.

The potential of a native digestate microbial community for 1,4-dioxane (DX) biodegradation was evaluated under low dissolved oxygen (DO) concentrations (1-3 mg/L) under different conditions in terms of electron acceptors, co-substrates, co-contaminants and temperature. Complete DX biodegradation (detection limit of 0.01 mg/L) of initial 25 mg/L was achieved in 119 days under low DO concentrations, while complete biodegradation happened faster at 91 and 77 days, respectively in nitrate-amended and aerated conditions. In addition, conducting biodegradation at 30 ˚C showed that the time required for complete DX biodegradation in unamended flasks reduced from 119 days in ambient condition (20-25 °C) to 84 days. Oxalic acid, which is a common metabolite of DX biodegradation was identified in the flasks under different treatments including unamended, nitrate-amended and aerated conditions. Furthermore, transition of the microbial community was monitored during the DX biodegradation period. While the overall richness and diversity of the microbial community decreased, several families of known DX-degrading bacteria such as Pseudonocardiaceae, Xanthobacteraceae and Chitinophagaceae were able to maintain and grow in different electron-accepting conditions. The results suggested that DX biodegradation under low DO concentrations, where no external aeration was provided, is possible by the digestate microbial community, which can be helpful to the ongoing research for DX bioremediation and natural attenuation.

The industrial solvent 1,4-dioxane causes hyperalgesia by targeting capsaicin receptor TRPV1.

BACKGROUND: The synthetic chemical 1,4-dioxane is used as industrial solvent, food, and care product additive. 1,4-Dioxane has been noted to influence the nervous system in long-term animal experiments and in humans, but the molecular mechanisms underlying its effects on animals were not previously known. RESULTS: Here, we report that 1,4-dioxane potentiates the capsaicin-sensitive transient receptor potential (TRP) channel TRPV1, thereby causing hyperalgesia in mouse model. This effect was abolished by CRISPR/Cas9-mediated genetic deletion of TRPV1 in sensory neurons, but enhanced under inflammatory conditions. 1,4-Dioxane lowered the temperature threshold for TRPV1 thermal activation and potentiated the channel sensitivity to agonistic stimuli. 1,3-dioxane and tetrahydrofuran which are structurally related to 1,4-dioxane also potentiated TRPV1 activation. The residue M572 in the S4-S5 linker region of TRPV1 was found to be crucial for direct activation of the channel by 1,4-dioxane and its analogs. A single residue mutation M572V abrogated the 1,4-dioxane-evoked currents while largely preserving the capsaicin responses. Our results further demonstrate that this residue exerts a gating effect through hydrophobic interactions and support the existence of discrete domains for multimodal gating of TRPV1 channel. CONCLUSIONS: Our results suggest TRPV1 is a co-receptor for 1,4-dioxane and that this accounts for its ability to dysregulate body nociceptive sensation.

Effect of the Temperature on the Process of Preferential Solvation of 1,4-Dioxane, 12-Crown-4, 15-Crown-5 and 18-Crown-6 Ethers in the Mixture of N-Methylformamide with Water: Composition of the Solvation Shell of the Cyclic Ethers.

The aim of the work was to analyze the preferential solvation process, and determine the composition of the solvation shell of cyclic ethers using the calorimetric method. The heat of solution of 1,4-dioxane, 12-crown-4, 15-crown-5 and 18-crown-6 ethers in the mixture of N-methylformamide with water was measured at four temperatures, 293.15 K, 298.15 K, 303.15 K, and 308.15 K, and the standard partial molar heat capacity of cyclic ethers has been discussed. 18-crown-6 (18C6) molecules can form complexes with NMF molecules through the hydrogen bonds between -CH3 group of NMF and the oxygen atoms of 18C6. Using the model of preferential solvation, the cyclic ethers were observed to be preferentially solvated by NMF molecules. It has been proved that the molar fraction of NMF in the solvation shell of cyclic ethers is higher than that in the mixed solvent. The exothermic, enthalpic effect of preferential solvation of cyclic ethers increases with increasing ring size and temperature. The increase in the negative effect of the structural properties of the mixed solvent with increase in the ring size in the process of preferential solvation of the cyclic ethers indicates an increasing disturbance of the mixed solvent structure, which is reflected in the influence of the energetic properties of the mixed solvent.

Environmental Potential for Microbial 1,4-Dioxane Degradation Is Sparse despite Mobile Elements Playing a Role in Trait Distribution.

1,4-Dioxane (dioxane) is an emerging contaminant of concern for which bioremediation is seen as a promising solution. To date, eight distinct gene families have been implicated in dioxane degradation, though only dioxane monooxygenase (DXMO) from Pseudonocardia dioxanivorans is routinely used as a biomarker in environmental surveys. In order to assess the functional and taxonomic diversity of bacteria capable of dioxane degradation, we collated existing, poorly-organized information on known biodegraders to create a curated suite of biomarkers with confidence levels for assessing 1,4-dioxane degradation potential. The characterized enzyme systems for dioxane degradation are frequently found on mobile elements, and we identified that many of the curated biomarkers are associated with other hallmarks of genomic rearrangements, indicating lateral gene transfer plays a role in dissemination of this trait. This is contrasted by the extremely limited phylogenetic distribution of known dioxane degraders, where all representatives belong to four classes within three bacterial phyla. Based on the curated set of expanded biomarkers, a search of more than 11,000 publicly available metagenomes identified a sparse and taxonomically limited distribution of potential dioxane degradation proteins. Our work provides an important and necessary structure to the current knowledge base for dioxane degradation and clarifies the potential for natural attenuation of dioxane across different environments. It further highlights a disconnect between the apparent mobility of these gene families and their limited distributions, indicating dioxane degradation may be difficult to integrate into a microorganism's metabolism. IMPORTANCE New regulatory limits for 1,4-dioxane in groundwater have been proposed or adopted in many countries, including the United States and Canada, generating a direct need for remediation options as well as better tools for assessing the fate of dioxane in an environment. A comprehensive suite of biomarkers associated with dioxane degradation was identified and then leveraged to examine the global potential for dioxane degradation in natural and engineered environments. We identified consistent differences in the dioxane-degrading gene families associated with terrestrial, aquatic, and wetland environments, indicating reliance on a single biomarker for assessing natural attenuation of dioxane is likely to miss key players. Most environments do not currently host the capacity for dioxane degradation-the sparse distribution of dioxane degradation potential highlights the need for bioaugmentation approaches over biostimulation of naturally occurring microbial communities.

Assessment of Non-Occupational 1,4-Dioxane Exposure Pathways from Drinking Water and Product Use.

1,4-Dioxane is a persistent and mobile organic chemical that has been found by the United States Environmental Protection Agency (USEPA) to be an unreasonable risk to human health in some occupational contexts. 1,4-Dioxane is released into the environment as industrial waste and occurs in some personal-care products as an unintended byproduct. However, limited exposure assessments have been conducted outside of an occupational context. In this study, the USEPA simulation modeling tool, Stochastic Human Exposure and Dose Simulator-High Throughput (SHEDS-HT), was adapted to estimate the exposure and chemical mass released down the drain (DTD) from drinking water consumption and product use. 1,4-Dioxane concentrations measured in drinking water and consumer products were used by SHEDS-HT to evaluate and compare the contributions of these sources to exposure and mass released DTD. Modeling results showed that compared to people whose daily per capita exposure came from only products (2.29 × 10-7 to 2.92 × 10-7 mg/kg/day), people exposed to both contaminated water and product use had higher per capita median exposures (1.90 × 10-6 to 4.27 × 10-6 mg/kg/day), with exposure mass primarily attributable to water consumption (75-91%). Last, we demonstrate through simulation that while a potential regulatory action could broadly reduce DTD release, the proportional reduction in exposure would be most significant for people with no or low water contamination.

Single-Atom Cobalt Incorporated in a 2D Graphene Oxide Membrane for Catalytic Pollutant Degradation.

We introduce a new graphene oxide (GO)-based membrane architecture that hosts cobalt catalysts within its nanoscale pore walls. Such an architecture would not be possible with catalysts in nanoscale, the current benchmark, since they would block the pores or alter the pore structure. Therefore, we developed a new synthesis procedure to load cobalt in an atomically dispersed fashion, the theoretical limit in material downsizing. The use of vitamin C as a mild reducing agent was critical to load Co as dispersed atoms (Co1), preserving the well-stacked 2D structure of GO layers. With the addition of peroxymonosulfate (PMS), the Co1-GO membrane efficiently degraded 1,4-dioxane, a small, neutral pollutant that passes through nanopores in single-pass treatment. The observed 1,4-dioxane degradation kinetics were much faster (>640 times) than the kinetics in suspension and the highest among reported persulfate-based 1,4-dioxane destruction. The capability of the membrane to reject large organic molecules alleviated their effects on radical scavenging. Furthermore, the advanced oxidation also mitigated membrane fouling. The findings of this study present a critical advance toward developing catalytic membranes with which two distinctive and complementary processes, membrane filtration and advanced oxidation, can be combined into a single-step treatment.

Occurrence, Distribution, and Environmental Behavior of Persistent, Mobile, and Toxic (PMT) and Very Persistent and Very Mobile (vPvM) Substances in the Sources of German Drinking Water.

Persistent, mobile, and toxic (PMT) and very persistent and very mobile (vPvM) substances have been recognized as a threat to both the aquatic environment and to drinking water resources. These substances are currently prioritized for regulatory action by the European Commission, whereby a proposal for the inclusion of hazard classes for PMT and vPvM substances has been put forward. Comprehensive monitoring data for many PMT/vPvM substances in drinking water sources are scarce. Herein, we analyze 34 PMT/vPvM substances in 46 surface water, groundwater, bank filtrate, and raw water samples taken throughout Germany. Results of the sampling campaign demonstrated that known PMT/vPvM substances such as 1H-benzotriazole, melamine, cyanuric acid, and 1,4-dioxane are responsible for substantial contamination in the sources of German drinking water. In addition, the results revealed the widespread presence of the emerging substances 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and diphenylguanidine (DPG). A correlation analysis showed a pronounced co-occurrence of PMT/vPvM substances associated predominantly with consumer or professional uses and also demonstrated an inhomogeneous co-occurrence for substances associated mainly with industrial use. These data were used to test the hypothesis that most PMT/vPvM substances pass bank filtration without significant concentration reduction, which is one of the main reasons for introducing PMT/vPvM as a hazard class within Europe.