Ultra-fast green hydrogen production from municipal wastewater by an integrated forward osmosis-alkaline water electrolysis system.

Recent advancements in membrane-assisted seawater electrolysis powered by renewable energy offer a sustainable path to green hydrogen production. However, its large-scale implementation faces challenges due to slow power-to-hydrogen (P2H) conversion rates. Here we report a modular forward osmosis-water splitting (FOWS) system that integrates a thin-film composite FO membrane for water extraction with alkaline water electrolysis (AWE), denoted as FOWSAWE. This system generates high-purity hydrogen directly from wastewater at a rate of 448 Nm3 day-1 m-2 of membrane area, over 14 times faster than the state-of-the-art practice, with specific energy consumption as low as 3.96 kWh Nm-3. The rapid hydrogen production rate results from the utilisation of 1 M potassium hydroxide as a draw solution to extract water from wastewater, and as the electrolyte of AWE to split water and produce hydrogen. The current system enables this through the use of a potassium hydroxide-tolerant and hydrophilic FO membrane. The established water-hydrogen balance model can be applied to design modular FO and AWE units to meet demands at various scales, from households to cities, and from different water sources. The FOWSAWE system is a sustainable and an economical approach for producing hydrogen at a record-high rate directly from wastewater, marking a significant leap in P2H practice.

The Future of Municipal Wastewater Reuse Concentrate Management: Drivers, Challenges, and Opportunities.

Water reuse is rapidly becoming an integral feature of resilient water systems, where municipal wastewater undergoes advanced treatment, typically involving a sequence of ultrafiltration (UF), reverse osmosis (RO), and an advanced oxidation process (AOP). When RO is used, a concentrated waste stream is produced that is elevated in not only total dissolved solids but also metals, nutrients, and micropollutants that have passed through conventional wastewater treatment. Management of this RO concentrate─dubbed municipal wastewater reuse concentrate (MWRC)─will be critical to address, especially as water reuse practices become more widespread. Building on existing brine management practices, this review explores MWRC management options by identifying infrastructural needs and opportunities for multi-beneficial disposal. To safeguard environmental systems from the potential hazards of MWRC, disposal, monitoring, and regulatory techniques are discussed to promote the safety and affordability of implementing MWRC management. Furthermore, opportunities for resource recovery and valorization are differentiated, while economic techniques to revamp cost-benefit analysis for MWRC management are examined. The goal of this critical review is to create a common foundation for researchers, practitioners, and regulators by providing an interdisciplinary set of tools and frameworks to address the impending challenges and emerging opportunities of MWRC management.

Advanced oxidation processes may transform unknown PFAS in groundwater into known products.

Per- and polyfluoroalkyl substances (PFAS) are a group of fluorinated organic contaminants classified as persistent in the aquatic environment. Early studies using targeted analysis approaches to evaluate the degradation of PFAS by advanced oxidation processes (AOP) in real water matrices may have been misinterpreted due to the presence of undetected or unknown PFAS in these matrices. The aims of the present study were to (1) screen selected commercially available AOPs (UV, UV + H2O2, O3/H2O2) and UV photocatalysis in a pilot system using commercially used and novel photocatalysts (TiO2, boron nitride [BN]) for removing PFAS contaminants and (2) evaluate their role on the conversion of non-detected/unknown to known PFAS compounds in real groundwater used as drinking water supplies. Results indicated that, while AOPs have the potential to achieve removal of the EPA method 533 target PFAS compounds (PFDA [100%], PFNA [100%], PFOA [85-94%], PFOS [25-100%], PFHxS [3-100%], PFPeS [100%], PFBS [100%]), AOPs transformed non-detected/unknown longer-chain PFAS compounds to detectable shorter-chain ones under very high-dose AOP operating conditions, leading to an increase in ∑PFAS concentration ranging from 95% to 340%. As emerging PFAS treatment processes transition from lab-scale investigations of target PFAS to pilot testing of real water matrices, studies will need to consider impact of the presence of non-target long-chain PFAS to transform into targeted PFAS compounds. A promising approach to address the potential risks and unforeseen consequences could involve an increased reliance on adsorbable organic fluorine (AOF) analysis before and after advanced oxidation process (AOP) treatment.

Interlaboratory comparison of centrifugal ultrafiltration with ICP-MS detection in a first-step towards methods to screen for nanomaterial release during certification of drinking water contact materials.

A key requirement for evaluating the safety of nano-enabled water treatment devices is measuring concentrations of insoluble nanomaterials released from devices into water that may be ingested by consumers. Therefore, there is a need for simple technique that uses commonly available commercial laboratory techniques to discriminate between nanoparticles and dissolved by-products of the nanomaterial (e.g., ionic metals). Such capabilities would enable screening for particulate or dissolved metals released into water from nanomaterial-containing drinking water contact materials (e.g., paint coatings) or devices (e.g., filters). This multi-laboratory study sought to investigate the use of relatively inexpensive centrifugal ultrafilters to separate nanoparticulate from ionic metal in combination with inductively-coupled plasma mass spectrometry (ICP-MS) detection. The accuracy, precision, and reproducibility for the proposed method were assessed using mixtures of nanoparticulate and ionic gold (Au) in a standard and widely utilized model water matrix (NSF International Standard 53/61). Concentrations for both ionic and nanoparticulate gold based upon measurements of Au mass in the initial solutions and Au permeating the centrifugal ultrafilters. Results across different solution compositions and different participating labs showed that ionic and nanoparticulate Au could be consistently discriminated with ppb concentrations typically resulting in <10 % error. A mass balance was not achieved because nanoparticles were retained on membranes embedded in plastic holders inside the centrifuge tubes, and the entire apparatus could not be acid and/or microwave digested. This was a minor limitation considering the ultrafiltration method is a screening tool, and gold concentration in the permeate indicates the presence of ionic metal rather than nanoforms. With further development, this approach could prove to be an effective tool in screening for nanomaterial release from water-system or device materials as part of third-party certification processes of drinking water compatible products.

The potential of electrodialysis as a cost-effective alternative to reverse osmosis for brackish water desalination.

While electrodialysis (ED) demonstrates lower energy consumption than reverse osmosis (RO) in the desalination of low salinity waters, RO continues to be the predominant technology for brackish water desalination. In this study, we probe this skewed market share and project the potential for future disruption by ED through systematic assessment of the levelized cost of water (LCOW). Using rigorous process- and economic-models, we minimize the LCOW of RO and ED systems, highlighting important tradeoffs between capital and operating expenditure for each technology. With optimized current state-of-the-art systems, we find that ED is more economical than RO for feed salinities ≤ 3 g L-1, albeit to a minor extent. Considering that RO is a highly mature technology, we focus on predicting the future potential of ED by evaluating plausible avenues for capital and operating cost reduction. Specifically, we find that reduction in the price of ion-exchange membranes (i.e., < 60 USD m-2) can ensure competitiveness with RO for feed salinities up to 5 g L-1. For higher feed salinities (≥ 5 g L-1) we reveal that the LCOW of ED may effectively be reduced by decreasing ion-exchange membrane resistance, while preserving high current efficiency. Through extensive assessment of structure-property-performance relationships, we precisely identify target membrane charge densities and diffusion coefficients which optimize the LCOW of ED, thus providing novel guidance for future membrane material development. Overall, we emphasize that with a unified approach - whereby ion-exchange membrane price is reduced and performance is enhanced - ED can become the economically preferable technology compared to RO across the entire brackish water salinity range.

Sous Vide-Inspired Impregnation of Amorphous Titanium (Hydr)Oxide into Carbon Block Point-of-Use Filters for Arsenic Removal from Water.

Carbon block filters, commonly employed as point-of-use (POU) water treatment components, effectively eliminate pathogens and adsorb undesirable tastes, odors, and organic contaminants, all while producing no water waste. However, they lack the capability to remove arsenic. Enabling the carbon block to remove arsenic could reduce its exposure risks in tap water. Inspired by Sous vide cooking techniques, we developed a low-energy, low-chemical method for impregnating commercially available carbon block with titanium (hydr)oxide (THO) in four integrated steps: (1) vacuum removal of air from the carbon block, (2) impregnation with precursors in a flexible pouch, (3) sealing to prevent oxygen intrusion, and (4) heating in a water bath at 80 °C for 20 h to eliminate exposure and reactions with air. This process achieved a uniform 13 wt % Ti loading in the carbon block. Our modified carbon block POU filter efficiently removed both arsenate and arsenite from tap water matrices containing 10 or 100 µg/L arsenic concentrations in batch experiments or continuous flow operations. Surprisingly, the THO-modified carbon block removed arsenite better than arsenate. This innovative method, using 70% fewer chemicals than traditional autoclave techniques, offers a cost-effective solution to reduce exposure to arsenic and lower its overall risk in tap water.

Phenotypic and Transcriptional Responses of Pseudomonas aeruginosa Biofilms to UV-C Irradiation via Side-Emitting Optical Fibers: Implications for Biofouling Control.

Biofilms give rise to a range of issues, spanning from harboring pathogens to accelerating microbial-induced corrosion in pressurized water systems. Introducing germicidal UV-C (200-280 nm) irradiation from light-emitting diodes (LEDs) into flexible side-emitting optical fibers (SEOFs) presents a novel light delivery method to inhibit the accumulation of biofilms on surfaces found in small-diameter tubing or other intricate geometries. This work used surfaces fully submerged in flowing water that contained Pseudomonas aeruginosa, an opportunistic pathogen commonly found in water system biofilms. A SEOF delivered a UV-C gradient to the surface for biofilm inhibition. Biofilm growth over time was monitored in situ using optical conference tomography. Biofilm formation was effectively inhibited when the 275 nm UV-C irradiance was ≥8 µW/cm2. Biofilm samples were collected from several regions on the surface, representing low and high UV-C irradiance. RNA sequencing of these samples revealed that high UV-C irradiance inhibited the expression of functional genes related to energy metabolism, DNA repair, quorum sensing, polysaccharide production, and mobility. However, insufficient sublethal UV-C exposure led to upregulation genes for SOS response and quorum sensing as survival strategies against the UV-C stress. These results underscore the need to maintain minimum UV-C exposure on surfaces to effectively inhibit biofilm formation in water systems.

Per- and polyfluoroalkyl substances and organofluorine in lakes and waterways of the northwestern Great Basin and Sierra Nevada.

Per- and polyfluoroalkyl substances (PFAS) are anthropogenic chemicals that occur ubiquitously in the environment and have been linked to numerous adverse health effects in humans and aquatic organisms. Although numerous environmental monitoring studies have been conducted, only one has evaluated PFAS in surface waters of the northwestern Great Basin, which features unique topography that results in dozens of endorheic basins and terminal lakes with no natural outlet, where PFAS may accumulate. To close this knowledge gap, we evaluated the occurrence of PFAS in grab samples from 15 lakes (headwater and terminal lakes) and 10 rivers in the Great Basin located in Nevada and California of the United States. PFAS and organofluorine were quantified by liquid chromatography tandem mass spectroscopy (LC-MS/MS) and combustion ion chromatography, respectively. The highest concentrations of PFAS occurred in samples taken near sites with known or suspected prior aqueous film forming foam (AFFF) application (~20 to 4754 ng/L). Samples near wastewater treatment plants and in urban areas also tended to have PFAS concentrations greater than those measured in remote, less anthropogenically influenced areas (~2 to 15 ng/L, <3 ng/L respectively). In limited snapshot sampling events PFAS appeared to accumulate in terminal lakes to some extent; in-lake concentrations were two to five times greater than those of their inflows. Fluorotelomer sulfonates were present downstream of a known AFFF application area likely to have had fluorotelomer-based foams applied to it, and the concentrations decayed in a predictable manner, suggesting they may be used as an indicator of PFAS transport away from an AFFF source. In all but two samples, organofluorine concentrations were greater than the sum of targeted PFAS (on a F basis) (median of 0.6 % of organofluorine identified via LC-MS/MS), although there was considerable variability in organofluorine measured in replicate samples.

Mechanistic Study of Arsenate Adsorption onto Different Amorphous Grades of Titanium (Hydr)Oxides Impregnated into a Point-of-Use Activated Carbon Block.

Millions of households still rely on drinking water from private wells or municipal systems with arsenic levels approaching or exceeding regulatory limits. Arsenic is a potent carcinogen, and there is no safe level of it in drinking water. Point-of-use (POU) treatment systems are a promising option to mitigate arsenic exposure. However, the most commonly used POU technology, an activated carbon block filter, is ineffective at removing arsenic. Our study aimed to explore the potential of impregnating carbon blocks with amorphous titanium (hydr)oxide (THO) to improve arsenic removal without introducing titanium (Ti) into the treated water. Four synthesis methods achieved 8-16 wt.% Ti loading within the carbon block with 58-97% amorphous THO content. The THO-modified carbon block could adsorb both oxidation states of arsenic (arsenate and arsenite) in batch or column tests. Modified carbon block with higher Ti and amorphous content always led to better arsenate removal, achieving arsenic loadings up to 31 mg As/mg Ti after 70,000 bed volumes in continuous flow tests. Impregnating carbon block with amorphous THO consistently outperformed impregnation using crystalline TiO2. The best-performing system (TTIP-EtOH carbon block) was an amorphous THO derived using titanium isopropoxide, ethanol, and acetic acid via sol-gel technique, aged at 80° for 18 hours and dried overnight at 60°. Comparable pore size distribution and surface area of the impregnated carbon blocks suggested that chemical properties play a more crucial role than physical and textural properties in removing arsenate via amorphous Ti-impregnated carbon block. Freundlich isotherms indicated energetically favorable adsorption for amorphous chemically synthesized adsorbents. The mass transport coefficients for the amorphous TTIP-EtOH carbon block were fitted using a pore surface diffusion model, resulting in Dsurface = 3.1×10-12 cm2/s and Dpore = 3.2×10-6 cm2/s. Impregnating the carbon block with THO enabled effective arsenic removal from water without adversely affecting the pressure drop across the unit or the carbon block's ability to remove polar organic chemical pollutants efficiently.

Photochemical Transformation of Free Chlorine Induced by Triplet State Dissolved Organic Matter.

Photolysis of free chlorine is an increasingly recognized approach for effectively inactivating microorganisms and eliminating trace organic contaminants. However, the impact of dissolved organic matter (DOM), which is ubiquitous in engineered water systems, on free chlorine photolysis is not yet well understood. In this study, triplet state DOM (3DOM*) was found to cause the decay of free chlorine for the first time. By using laser flash photolysis, the scavenging rate constants of triplet state model photosensitizers by free chlorine at pH 7.0 were determined to be in the range of (0.26-3.33) × 109 M-1 s-1. 3DOM*, acting as a reductant, reacted with free chlorine at an estimated reaction rate constant of 1.22(±0.22) × 109 M-1 s-1 at pH 7.0. This study revealed an overlooked pathway of free chlorine decay during UV irradiation in the presence of DOM. Besides the DOM's light screening ability and scavenging of radicals or free chlorine, 3DOM* played an important role in the decay of free chlorine. This reaction pathway accounted for a significant proportion of the decay of free chlorine, ranging from 23 to 45%, even when DOM concentrations were below 3 mgC L-1 and a free chlorine dose of 70 µM was present during UV irradiation at 254 nm. The generation of HO• and Cl• from the oxidation of 3DOM* by free chlorine was confirmed by electron paramagnetic resonance and quantified by chemical probes. By inputting the newly observed pathway in the kinetics model, the decay of free chlorine in UV254-irradiated DOM solution can be well predicted.

Unraveling mechanisms behind reduced nitrate leaching with graphite nanomaterials addition with fertilizers in soil column experiments.

Overuse or mistimed application of nitrogen fertilizer can cause nitrate contamination in groundwater and surrounding surface waters. Previous greenhouse studies have explored the use of graphene nanomaterials, including graphite nano additive (GNA), to reduce nitrate leaching in an agricultural soil while growing lettuce crops. To investigate the mechanism of GNA addition in suppressing nitrate leaching, we conducted soil column experiments using native agricultural soils under saturated or unsaturated flow conditions to simulate varied irrigation. We investigated the effects of temperature (4 °C compared with 20 °C) on microbial activity and dose effect of GNA was also explored (165 mg/kg soil and 1650 mg/kg soil) for biotic soil column experiments whereas a single temperature condition (20 °C) and GNA dose (165 mg/kg soil) was employed for abiotic (autoclaved) soil column experiments. Results showed GNA addition had minimal effects on nitrate leaching in saturated flow soil columns due to short hydraulic residence times (∼3.5 h). In comparison, longer residence times (∼3 d) in unsaturated soil columns reduced nitrate leaching by 25-31% relative to control soil columns without GNA addition. Furthermore, nitrate retention in the soil column was found to be suppressed at 4 °C compared with 20 °C, suggesting a bio-mediated mechanism for GNA addition to reduce nitrate leaching. In addition, the soil dissolved organic matter was found to be associated with nitrate leaching, where less nitrate leaching occurring when higher dissolved organic carbon (DOC) was measured in leachate water. Following studies of adding soil-derived organic carbon (SOC) resulted in greater nitrogen retention in the unsaturated soil columns only when GNA was present. Overall, the results suggest that GNA-amended soil reduces nitrate loss through increased N immobilization in the microbial biomass or loss of N in gaseous phase through enhanced nitrification and denitrification process.

Self-supported polypyrrole flexible electrodes for electrochemical reduction of nitrite.

The efficiency of an electrochemical oxidation/reduction process strongly depends on the working electrode's surface area to volume ratio. By making electrodes flexible and employing different configurations such as roll-to-roll membrane, the surface area to volume ratio can be enhanced, therefore improving the overall efficiency of electrochemical processes. Conductive polymers emerge as a new framework to enable alternative electrochemical water treatment cell configurations. Self-standing polypyrrole flexible electrodes were synthesized by electropolymerization and evaluated on the treatment of an oxyanion pollutant: nitrite. Mechanical characterization through stress-strain curves and bending tests demonstrated high electrode resilience that sustained over 1000 bending cycles without impacting mechanical integrity or electrocatalytic responses. The electrocatalytic response towards nitrite reduction was assessed under linear scan voltammetry (LSV) and removal performance evaluated under potentiostatic conditions reaching 79% abatement of initial concentrations of nitrite of 15 mg/L [NO2--N]. Self-standing flexible electrodes appear as a novel framework to enable modular compact water treatment unit designs that maximize the electrode area/volume ratio and substitute expensive platinum group metal (PGMs) electrocatalysts.

Novel polymer optical fibers with high mass-loading g-C3N4 embedded metamaterial porous structures achieve rapid micropollutant degradation in water.

The performance of conventional photocatalytic reactors suffers from low photocatalyst mass-loading densities affixed to surfaces and light scattering losses or light attenuation in slurry reactors. These limitations are overcome by fabrication of high mass-loading g-C3N4 embedded metamaterial porous structures on flexible polymeric optical fibers (g-C3N4-POFs). In this study, the fabricated g-C3N4-POFs contain g-C3N4 with mass-loading 100-1000x higher than previouly reported, enabling efficient light delivery to g-C3N4 and improved pollutant mass transport within metamaterial porous structures. The key fabrication step involved using acetone, based on its high saturated vapor pressure and low dielectric constant, making roll-to-roll mass production of high mass-loading photocatalyst-embedded metamaterial POFs possible at room-temperature within seconds. Using bundles of 150 individual g-C3N4-POFs in the reactors, we achieved 4x higher degradation rates for micropollutants under visible light irradiation at 420 nm compared with equivalent mass-to-volume ratios of photocatalysts in a slurry suspension reactor. The bundled g-C3N4-POF reactor showed no degradation in the structural integrity or loss of pollutant degradation using deionized or model drinking water under accumulated HO• exposures of ∼4.5 × 10-9 M•s after 20 cycles of treatment. It operates continuously at g-C3N4 dosages equivalent to 100-1000 g/L and a water depth over 40 cm, making it a feasible alternative to conventional photocatalytic reactors.

The Minus Approach Can Redefine the Standard of Practice of Drinking Water Treatment.

Chlorine-based disinfection for drinking water treatment (DWT) was one of the 20th century's great public health achievements, as it substantially reduced the risk of acute microbial waterborne disease. However, today's chlorinated drinking water is not unambiguously safe; trace levels of regulated and unregulated disinfection byproducts (DBPs), and other known, unknown, and emerging contaminants (KUECs), present chronic risks that make them essential removal targets. Because conventional chemical-based DWT processes do little to remove DBPs or KUECs, alternative approaches are needed to minimize risks by removing DBP precursors and KUECs that are ubiquitous in water supplies. We present the "Minus Approach" as a toolbox of practices and technologies to mitigate KUECs and DBPs without compromising microbiological safety. The Minus Approach reduces problem-causing chemical addition treatment (i.e., the conventional "Plus Approach") by producing biologically stable water containing pathogens at levels having negligible human health risk and substantially lower concentrations of KUECs and DBPs. Aside from ozonation, the Minus Approach avoids primary chemical-based coagulants, disinfectants, and advanced oxidation processes. The Minus Approach focuses on bank filtration, biofiltration, adsorption, and membranes to biologically and physically remove DBP precursors, KUECs, and pathogens; consequently, water purveyors can use ultraviolet light at key locations in conjunction with smaller dosages of secondary chemical disinfectants to minimize microbial regrowth in distribution systems. We describe how the Minus Approach contrasts with the conventional Plus Approach, integrates with artificial intelligence, and can ultimately improve the sustainability performance of water treatment. Finally, we consider barriers to adoption of the Minus Approach.

Comparing methods to deposit Pd-In catalysts on hydrogen-permeable hollow-fiber membranes for nitrate reduction.

Catalytic hydrogenation of nitrate in water has been studied primarily using nanoparticle slurries with constant hydrogen-gas (H2) bubbling. Such slurry reactors are impractical in full-scale water treatment applications because 1) unattached catalysts are difficult to be recycled/reused and 2) gas bubbling is inefficient for delivering H2. Membrane Catalyst-film Reactors (MCfR) resolve these limitations by depositing nanocatalysts on the exterior of gas-permeable hollow-fiber membranes that deliver H2 directly to the catalyst-film. The goal of this study was to compare the technical feasibility and benefits of various methods for attaching bimetallic palladium/indium (Pd/In) nanocatalysts for nitrate reduction in water, and subsequently select the most effective method. Four Pd/In deposition methods were evaluated for effectiveness in achieving durable nanocatalyst immobilization on the membranes and repeatable nitrate-reduction activity: (1) In-Situ MCfR-H2, (2) In-Situ Flask-Synthesis, (3) Ex-Situ Aerosol Impaction-Driven Assembly, and (4) Ex-Situ Electrostatic. Although all four deposition methods achieved catalyst-films that reduced nitrate in solution (≥ 1.1 min-1gPd-1), three deposition methods resulted in significant palladium loss (>29%) and an accompanying decline in nitrate reactivity over time. In contrast, the In-Situ MCfR-H2 deposition method had negligible Pd loss and remained active for nitrate reduction over multiple operational cycles. Therefore, In-Situ MCfR-H2 emerged as the superior deposition method and can be utilized to optimize catalyst attachment, nitrate-reduction, and N2 selectivity in future studies with more complex water matrices, longer treatment cycles, and larger reactors.

Co-Occurrence of Bromine and Iodine Species in US Drinking Water Sources That Can Impact Disinfection Byproduct Formation.

Bromine and iodine species are precursors for forming disinfection byproducts in finished drinking waters. Our study incorporates spatial and temporal data to quantify concentrations of inorganic (bromide (Br-), iodide (I-), and iodate (IO3-)), organic, and total bromine (BrT) and iodine (IT) species from 286 drinking water sources and 7 wastewater effluents across the United States. Br- ranged from <5-7800 µg/L (median of 62 µg/L in surface water (SW) and 95 µg/L in groundwater (GW)). I- was detected in 41% of SW (1-72 µg/L, median = <1 µg/L) and 62% of GW (<1-250 µg/L, median = 3 µg/L) samples. The median Br-/I- ratio in SW and GW was 22 µg/µg and 16 µg/µg, respectively, in paired samples with detect Br- and I-. BrT existed primarily as Br-, while IT was present as I-, IO3-, and/or total organic iodine (TOI). Inorganic iodine species (I- and IO3-) were predominant in GW samples, accounting for 60-100% of IT; however, they contributed to only 20-50% of IT in SW samples. The unknown fraction of IT was attributed to TOI. In lakes, seasonal cycling of I-species was observed and was presumably due to algal productivity. Finally, Spearman Rank Correlation tests revealed a strong correlation between Br- and IT in SW (RBr-,IT = 0.83) following the log10 (Br-, µg/L) = 0.65 × log10 (IT, µg/L) - 0.17 relationship. Br- and I- in treated wastewater effluents (median Br- = 234 µg/L, median I- = 5 µg/L) were higher than drinking water sources.

An autopsy study of hollow fiber and multibore ultrafiltration membranes from a pilot-scale ultra high-recovery filtration system for surface water treatment.

The organic fouling characteristics of hollow fiber ultrafiltration (HFUF) and multibore ultrafiltration (MBUF) membranes from long-term ultrafiltration (UF) membrane systems were systemically investigated in this study. The objective was to obtain insights into the fouling behavior of dissolved organic matter (DOM) in a pilot-scale ultra-high-recovery membrane filtration system (p-UHMS) used for surface water treatment. The pilot system consisted of a series of two different UF membranes (1st stage: polyvinylidene fluoride (PVDF) HFUF and 2nd stage: polyethersulfone (PES) MBUF). It was designed to feed the HFUF concentrate to the MBUF membranes to achieve ≥99.5 % total water recovery for surface water treatment, as these advances might enhance the production efficiencies of drinking water. The experimental results confirmed that hydrophobic DOM controlled the formation of HFUF membrane organic fouling, whereas hydrophilic DOM, including polysaccharide-like and protein-like matter, promoted MBUF membrane fouling. These opposing trends were attributed to the hydrophilic characteristics of the MBUF membrane surfaces (contact angle: PVDF = 90-130° and PES ≤ 80°), which reduced the hydrophobic interactions between the UF membrane surfaces and foulants. The performance declines of the MBUF membrane due to fouling layer formation was considerably severer than those of the HFUF membrane, decreasing total permeate water in the p-UHMS. Moreover, the quantity of the desorbed MBUF membrane foulants via 0.1 N NaOH was roughly 7.2 times larger than that of the desorbed HFUF membrane foulants through 0.1 N NaOH, indicating that alkaline-based cleaning agent could much more efficiently recover the performance of the fouled MBUF membranes. Hence, adequate cleaning strategies using alkaline-based agent for the MBUF membrane appeared to be essential for preventing the performance deterioration of the p-UHMS.

Using radish (Raphanus lativus L.) germination to establish a benchmark dose for the toxicity of ozonated-petroleum byproducts in soil.

The concentration-response relationship between the germination outcome of radish (Raphanus lativus L.) and ozonated petroleum residuals was determined experimentally. The outcomes were used to produce an ecological risk assessment model to predict the extra risk of adverse outcomes based on the concentration of ozonated residuals. A test soil with low organic matter (0.5% w/w) was mixed with raw crude oil, artificially weathered, and treated at three doses of ozone (O3) gas (5 g, 10 g, and 40 g O3 per 600 g of soil). Total petroleum hydrocarbons (TPH) and produced dissolved organic carbon (DOC) were measured. TREATMENT categories (control, petroleum, petroleum + 5 g O3, petroleum + 10 g O3, and petroleum + 40 g O3) were then used to create a dilution series using different proportions of the test soil and a commercially available potting mix (∼75% w/w organic matter) to evaluate the effects of background organic matter (b-ORGANIC) in conjunction with TPH and DOC. Multivariable logistic regression was performed on the adverse germination outcome as a function of TPH, DOC, TREATMENT, and b-ORGANIC. The parameters controlling germination were the continuous variable DOC and the categorical variables TREATMENT and b-ORGANIC. Radish germination was strongly harmed by DOC from ozonation, but DOC's ecotoxicity decreased with increasing O3 dose and the presence of b-ORGANIC beyond 10% (w/w). We used the germination outcome of radish to produce a logistic regression model that computes margins of DOC (± std. error) that create 10%, 25%, and 50% extra risk of adverse germination effects.

One-Electron Oxidant-Induced Transformations of Aromatic Alcohol to Ketone Moieties in Dissolved Organic Matter Increase Trichloromethane Formation.

Radicals in advanced oxidation processes (AOPs) degrade micropollutants during water and wastewater treatment, but the transformation of dissolved organic matter (DOM) may be equally important. Ketone moieties in DOM are known disinfection byproduct precursors, but ketones themselves are intermediates produced during AOPs. We found that aromatic alcohols in DOM underwent transformation to ketones by one-electron oxidants (using SO4•- as a representative), and the formed ketones significantly increased trichloromethane (CHCl3) formation potential (FP) upon subsequent chlorination. CHCl3-FPs from aromatic ketones (Ar-CO-CH3, average of 22 mol/mol) were 6-24 times of CHCl3-FPs from aromatic alcohols (Ar-CH(OH)-CH3, average of 0.85 mol/mol). At a typical SO4•- exposure of 7.0 × 10-12 M·s, CHCl3-FPs from aromatic alcohol transformation increased by 24.8%-112% with an average increase of 53.4%. Notably, SO4•- oxidation of aliphatic alcohols resulted in minute changes in CHCl3-FPs due to their low reactivities with SO4•- (∼107 M-1 s-1). Other one-electron oxidants (Cl2•-, Br2•-,and CO3•-) are present in AOPs and also lead to aromatic alcohol-ketone transformations similar to SO4•-. This study highlights that subtle changes in DOM physicochemical properties due to one-electron oxidants can greatly affect the reactivity with free chlorine and the formation of chlorinated byproducts.