Structural Dependence of Reductive Defluorination of Linear PFAS Compounds in a UV/Electrochemical System.

Per and polyfluoroalkyl substances (PFAS), legacy chemicals used in firefighting and the manufacturing of many industrial and consumer goods, are widely found in groundwater resources, along with other regulated compounds, such as chlorinated solvents. Due to their strong C-F bonds, these molecules are extremely recalcitrant, requiring advanced treatment methods for effective remediation, with hydrated electrons shown to be able to defluorinated these compounds. A combined photo/electrochemical method has been demonstrated to dramatically increase defluorination rates, where PFAS molecules sorbed onto appropriately functionalized cathodes charged to low cell potentials (-0.58 V vs Ag/AgCl) undergo a transient electron transfer event from the electrode, which "primes" the molecule by reducing the C-F bond strength and enables the bond's dissociation upon the absorption of a hydrated electron. In this work, we explore the impact of headgroup and chain length on the performance of this two-electron process and extend this technique to chlorinated solvents. We use isotopically labeled PFAS molecules to take advantage of the kinetic isotope effect and demonstrate that indeed PFAS defluorination is likely driven by a two-electron process. We also present density functional theory calculations to illustrate that the externally applied potential resulted in an increased rate of electron transfer, which ultimately increased the measured defluorination rate.

Mineral Scale Prevention on Electrically Conducting Membrane Distillation Membranes Using Induced Electrophoretic Mixing.

The growth of mineral crystals on surfaces is a challenge across multiple industrial processes. Membrane-based desalination processes, in particular, are plagued by crystal growth (known as scaling), which restricts the flow of water through the membrane, can cause membrane wetting in membrane distillation, and can lead to the physical destruction of the membrane material. Scaling occurs when supersaturated conditions develop along the membrane surface due to the passage of water through the membrane, a process known as concentration polarization. To reduce scaling, concentration polarization is minimized by encouraging turbulent conditions and by reducing the amount of water recovered from the saline feed. In addition, antiscaling chemicals can be used to reduce the availability of cations. Here, we report on an energy-efficient electrophoretic mixing method capable of nearly eliminating CaSO4 and silicate scaling on electrically conducting membrane distillation (ECMD) membranes. The ECMD membrane material is composed of a percolating layer of carbon nanotubes deposited on porous polypropylene support and cross-linked by poly(vinyl alcohol). The application of low alternating potentials (2 Vpp,1Hz) had a dramatic impact on scale formation, with the impact highly dependent on the frequency of the applied signal, and in the case of silicate, on the pH of the solution.

BTEX exposures in an area impacted by industrial and mobile sources: Source attribution and impact of averaging time.

UNLABELLED: The impacts of emissions plumes from major industrial sources on black carbon (BC) and BTEX (benzene, toluene, ethyl benzene, xylene isomers) exposures in communities located >10 km from the industrial source areas were identified with a combination of stationary measurements, source identification using positive matrix factorization (PMF), and dispersion modeling. The industrial emissions create multihour plume events of BC and BTEX at the measurement sites. PMF source apportionment, along with wind patterns, indicates that the observed pollutant plumes are the result of transport of industrial emissions under conditions of low boundary layer height. PMF indicates that industrial emissions contribute >50% of outdoor exposures of BC and BTEX species at the receptor sites. Dispersion modeling of BTEX emissions from known industrial sources predicts numerous overnight plumes and overall qualitative agreement with PMF analysis, but predicts industrial impacts at the measurement sites a factor of 10 lower than PMF. Nonetheless, exposures associated with pollutant plumes occur mostly at night, when residents are expected to be home but are perhaps unaware of the elevated exposure. Averaging data samples over long times typical of public health interventions (e.g., weekly or biweekly passive sampling) misapportions the exposure, reducing the impact of industrial plumes at the expense of traffic emissions, because the longer samples cannot resolve subdaily plumes. Suggestions are made for ways for future distributed pollutant mapping or intervention studies to incorporate high time resolution tools to better understand the potential impacts of industrial plumes. IMPLICATIONS: Emissions from industrial or other stationary sources can dominate air toxics exposures in communities both near the source and in downwind areas in the form of multihour plume events. Common measurement strategies that use highly aggregated samples, such as weekly or biweekly averages, are insensitive to such plume events and can lead to significant under apportionment of exposures from these sources.

Desalinating a real hyper-saline pre-treated produced water via direct-heat vacuum membrane distillation.

Membrane distillation (MD) is an emerging thermal desalination technology capable of desalinating waters of any salinity. During typical MD processes, the saline feedwater is heated and acts as the thermal energy carrier; however, temperature polarization (as well as thermal energy loss) contributes to low distillate fluxes, low single-pass water recovery and poor thermal efficiency. An alternative approach is to integrate an extra thermal energy carrier as part of the membrane and/or module assembly, which can channel externally provided heat directly to the membrane-feedwater interface and/or along the feed channel length. This direct-heat delivery has been demonstrated to increase single-pass water recovery and enhance the overall thermal efficiency. We developed a bench-scale direct-heated vacuum MD (DHVMD) process to desalinate pre-treated oil and gas "produced water" with an initial total dissolved solids of 115,500 ppm at a feed temperature ranging between 24 and 32 °C. We evaluated both water flux and specific energy consumption (SEC) as a function of water recovery. The system achieved a 50% water recovery without significant scaling, with an average flux >6 kg m-2 hr-1 and a SEC as low as 2,530 kJ kg-1. The major species of mineral scales (i.e., NaCl, CaSO4, and SrSO4) that limited the water recovery to 68% were modeled in terms of thermodynamics and identified by scanning electron microscopy and energy-dispersive X-ray spectroscopy. In addition, we further developed and employed a physics-based process model to estimate temperature, salinity, water transport and energy flows for full-scale vacuum MD and DHVMD modules. Model results show that a direct-heat input rate of 3,600 W can increase single-pass water recovery from 2.1% to 3.1% while lowering the thermal SEC from 7,800 kJ kg-1 to 6,517 kJ kg-1 in an unoptimized module. Finally, the scaling up potential of DHVMD process is briefly discussed.

Potential-Driven Electron Transfer Lowers the Dissociation Energy of the C-F Bond and Facilitates Reductive Defluorination of Perfluorooctane Sulfonate (PFOS).

The widespread environmental occurrence of per- and polyfluoroalkyl substances (PFAS) has attracted significant regulatory, research, and media attention because of their toxicity, recalcitrance, and ability to bioaccumulate. Perfluorooctane sulfonate (PFOS) is a particularly troublesome member of the PFAS family due to its immunity to biological remediation and radical-based oxidation. In the present study, we present a heterogeneous reductive degradation process that couples direct electron transfer (ET) from surface-modified carbon nanotube electrodes (under low potential conditions) to sorbed PFOS molecules using UV-generated hydrated electrons without any further chemical addition. We demonstrate that the ET process dramatically increases the PFOS defluorination rate while yielding shorter chain (C3-C7) perfluorinated acids and present both experimental and ab initio evidence of the synergistic relationship between electron addition to sorbed molecules and their ability to react with reductive hydrated electrons. Because of the low energy consumption associated with the ET process, the use of standard medium-pressure UV lamps and no further chemical addition, this reductive degradation process is a promising method for the destruction of persistent organic pollutants, including PFAS and other recalcitrant halogenated organic compounds.

Coupling hydrothermal liquefaction and membrane distillation to treat anaerobic digestate from food and dairy farm waste.

Increased demand for water, energy and food requires new ways to produce fertilizers, fuels and reusable water. Recovery of resources from wastes could lead to an additional source of energy and nutrients, and also reduce the waste to be disposed. In this work, we used hydrothermal liquefaction to produce a biocrude oil product, followed by membrane distillation of the aqueous effluents to concentrate a nutrient-rich stream that can be used as fertilizer. The motivation for this work is that residual heat from the hydrothermal liquefaction process could be utilized to drive the membrane distillation process, which would improve the efficiency and reduce the cost of the distillation process. The membrane distillation system was demonstrated to be able to recover 75% of the water. The membrane distillation retentate had very high ammonium and phosphate concentrations, making it suitable as a fertilizer. Membrane permeate contained high concentrations of volatile organics.