Quantitative and rapid detection of nanoplastics labeled by luminescent metal phenolic networks using surface-enhanced Raman scattering.

The escalating prevalence of nanoplastics contamination in environmental ecosystems has emerged as a significant health hazard. Conventional analytical methods are suboptimal, hindered by their inefficiency in analyzing nanoplastics at low concentrations and their time-intensive processes. In this context, we have developed an innovative approach that employs luminescent metal-phenolic networks (L-MPNs) coupled with surface-enhanced Raman spectroscopy (SERS) to separate and label nanoplastics, enabling rapid, sensitive and quantitative detection. Our strategy utilizes L-MPNs composed of zirconium ions, tannic acid, and rhodamine B to uniformly label nanoplastics across a spectrum of sizes (50-500 nm) and types (e.g., polystyrene, polymethyl methacrylate, polylactic acid). Rhodamine B (RhB) functions as a Raman reporter within these L-MPNs-based SERS tags, providing the requisite sensitivity for trace measurement of nanoplastics. Moreover, the labeling with L-MPNs aids in the efficient separation of nanoplastics from liquid media. Utilizing a portable Raman instrument, our methodology offers cost-effective, swift, and field-deployable detection capabilities, with excellent sensitivity in nanoplastic analysis and a detection threshold as low as 0.1 µg/mL. Overall, this study proposes a highly promising strategy for the robust and sensitive analysis of a broad spectrum of particle analytes, underscored by the effective labeling performance of L-MPNs when coupled with SERS techniques.

Managing PFAS exhausted Ion-exchange resins through effective regeneration/electrochemical process.

This study proposes an integrated approach that combines ion-exchange (IX) and electrochemical technologies to tackle problems associated with PFAS contamination. Our investigation centers on evaluating the recovery and efficiency of IX/electrochemical systems in the presence of five different salts, spanning dosages from 0.1 % to 8 %. The outcomes reveal a slight superiority for NaCl within the regeneration system, with sulfate and bicarbonate also showing comparable efficacy. Notably, the introduction of chloride ion (Cl-) into the electrochemical system results in substantial generation of undesirable chlorate (ClO3-) and perchlorate (ClO4-) by-products, accounting for ∼18 % and ∼81 % of the consumed Cl-, respectively. Several agents, including H2O2, KI, and Na2S2O3, exhibited effective mitigation of ClO3- and ClO4- formation. However, only H2O2 demonstrated a favorable influence on the degradation and defluorination of PFOA. The addition of 0.8 M H2O2 resulted in the near-complete removal of ClO3- and ClO4-, accompanied by 1.3 and 2.2-fold enhancements in the degradation and defluorination of PFOA, respectively. Furthermore, a comparative analysis of different salts in the electrochemical system reveals that Cl- and OH- ions exhibit slower performance, possibly due to competitive interactions with PFOA on the anode's reactive sites. In contrast, sulfate and bicarbonate salts consistently demonstrate robust decomposition efficiencies. Despite the notable enhancement in IX regeneration efficacy facilitated by the presence of methanol, particularly for PFAS-specific resins, this enhancement comes at the cost of reduced electrochemical decomposition of all PFAS. The average decay rate ratio of all PFAS in the presence of 50 % methanol, compared to its absence, falls within the range of 0.11-0.39. In conclusion, the use of 1 % Na2SO4 salt stands out as a favorable option for the integrated IX/electrochemical process. This choice not only eliminates the need to introduce an additional chemical (e.g., H2O2) into the wastewater stream, but also ensures both satisfactory regeneration recovery and efficiency in the decomposition process through electrochemical treatment.

Structural dependence of PFAS oxidation in a boron doped diamond-electrochemical system.

Driven by long-term persistence and adverse health impacts of legacy perfluorooctanoic acid (PFOA), production has shifted towards shorter chain analogs (C4, perfluorobutanoic acid (PFBA)) or fluorinated alternatives such as hexafluoropropylene oxide dimer acid (HFPO-DA, known as GenX) and 6:2 fluorotelomer carboxylic acid (6:2 FTCA). Yet, a thorough understanding of treatment processes for these alternatives is limited. Herein, we conducted a comprehensive study using an electrochemical approach with a boron doped diamond anode in Na2SO4 electrolyte for the remediation of PFOA common alternatives, i.e., PFBA, GenX, and 6:2 FTCA. The degradability, fluorine recovery, transformation pathway, and contributions from electro-synthesized radicals were investigated. The results indicated the significance of chain length and structure, with shorter chains being harder to break down (PFBA (65.6 ± 5.0%) < GenX (84.9 ± 3.3%) < PFOA (97.9 ± 0.1%) < 6:2 FTCA (99.4 ± 0.0%) within 120 min of electrolysis). The same by-products were observed during the oxidation of both low and high concentrations of parent PFAS (2 and 20 mg L-1), indicating that the fundamental mechanism of PFAS degradation remained consistent. Nevertheless, the ratio of these by-products to the parent PFAS concentration varied which primarily arises from the more rapid PFAS decomposition at lower dosages. For all experiments, the main mechanism of PFAS oxidation was initiated by direct electron transfer at the anode surface. Sulfate radical (SO4•-) also contributed to the oxidation of all PFAS, while hydroxyl radical (•OH) only played a role in the decomposition of 6:2 FTCA. Total fluorine recovery of PFBA, GenX, and 6:2 FTCA were 96.5%, 94.0%, and 76.4% within 240 min. The more complex transformation pathway of 6:2 FTCA could explain its lower fluorine recovery. Detailed decomposition pathways for each PFAS were also proposed through identifying the generated intermediates and fluorine recovery. The proposed pathways were also assessed using 19F Nuclear Magnetic Resonance (NMR) spectroscopy.

Antimicrobial Activity of Filtered Far-UVC Light (222 nm) against Different Pathogens.

Ultraviolet (UV) light is an effective disinfection technology, able to inactivate a wide range of microorganisms, including bacteria and fungi. A safer UV wavelength of 222 nm, also known as far-UVC, has been proposed to minimize these harmful effects while retaining the light's disinfection capability. This study is aimed at exploring the antimicrobial activity of filtered far-UVC (222 nm) on a panel of pathogens commonly found in nosocomial installations. A panel of Gram-positive and Gram-negative bacteria and yeast pathogens was tested. Microorganisms were deposited on a plastic surface, allowing them to dry before exposure to the far-UVC light at a distance of 50 cm. Results showed that far-UVC light successfully inhibits the growth of the tested pathogens, although at different exposure times. In conclusion, the results of this study provide fundamental information to achieve reliable disinfection performance with far-UVC lamps with potential applications in healthcare facilities like hospitals and long-term care homes.

Design of a new fountain reactor for contamination degradation using advanced oxidation processes with hybrid techniques and modeling evaluation.

Due to the water and energy crises, wastewater treatment systems that are more energy efficient and capable of large volume degradation are a priority. Photochemical decomposition methods have a significant impact on pollutant treatment. The use of these methods in conjunction with a novel designed reactor and hybridization processes can result in considerable treatment results. This research used a fountain system in a UV/H2O2 process to generate a belt-type liquid film with a low thickness and high mixing to remove methyl orange as a model pollutant. The flow rate, H2O2 concentration, temperature, and UV intensity were the parameters evaluated in this series of tests. After 90 minutes under optimum conditions, the maximum degradation of methyl orange was 99.73 percent. The efficiency of the purification process was increased to 99 percent in 75 minutes by using the optimum state of hybridization of UV/US/H2O2 processes. Two deep neural network models and a pseudo-first-order kinetic model were created to fit the experimental data. The results reveal a good fit between the experimental data and the model prediction. The discovered synergistic factor (1.168) and energy yield (2.65 g/kWh) demonstrated the high efficiency of the hybridization process and the outstanding function of the designed system, respectively.

Photolysis of chloramines in vacuum-UV and vacuum-UV/chlorine advanced oxidation processes for removal of 1,4-dioxane: Effect of water matrix, kinetic modeling, and implications for potable reuse.

Advanced oxidation processes (AOPs) are a key step in eliminating persistent micropollutants in potable reuse trains. Under such conditions, chloramines are an inevitable component in the AOP feed water given their application as an antifouling agent for the upstream membrane processes. In cases when other oxidants, such as free chlorine, are to be used in the AOP treatment, the effect of background chloramines and any potential interplays between the oxidants should be considered. In this study, vacuum-UV (VUV) and VUV/Cl2 have been proposed as promising AOP alternatives for potable reuse and the effect of chloramine photolysis has been considered on the removal of 1,4-dioxane. Results indicated that while presence of chloramine reduces the treatment efficiency in the VUV AOP, coexistence of free chlorine and chloramine oxidants significantly improves 1,4-dioxane degradation rates. Experimental data and kinetic modeling both confirmed the roles of OH• and Cl2•- in 1,4-dioxane removal with 62.5% and 32.5% contribution in the VUV/Cl2/chloramines, respectively. Among the other water matrix conditions, Cl- was shown to improve the degradation rates while HCO3- suppressed the reactions by scavenging radical species. Overall, the findings of this research are informative for the design and development of VUV AOPs at small scale potable reuse facilities.

Article Application of neural network in metal adsorption using biomaterials (BMs): a review.

With growing environmental consciousness, biomaterials (BMs) have garnered attention as sustainable materials for the adsorption of hazardous water contaminants. These BMs are engineered using surface treatments or physical alterations to enhance their adsorptive properties. The lab-scale methods generally employ a One Variable at a Time (OVAT) approach to analyze the impact of biomaterial modifications, their characteristics and other process variables such as pH, temperature, dosage, etc., on the removal of metals via adsorption. Although implementing the adsorption procedure using BMs seems simple, the conjugate effects of adsorbent properties and process attributes implicate complex nonlinear interactions. As a result, artificial neural networks (ANN) have gained traction in the quest to understand the complex metal adsorption processes on biomaterials, with applications in environmental remediation and water reuse. This review discusses recent progress using ANN frameworks for metal adsorption using modified biomaterials. Subsequently, the paper comprehensively evaluates the development of a hybrid-ANN system to estimate isothermal, kinetic and thermodynamic parameters in multicomponent adsorption systems.

Electrochemical degradation of PFOA and its common alternatives: Assessment of key parameters, roles of active species, and transformation pathway.

This study investigates an electrochemical approach for the treatment of water polluted with per- and poly-fluoroalkyl substances (PFAS), looking at the impact of different variables, contributions from generated radicals, and degradability of different structures of PFAS. Results obtained from a central composite design (CCD) showed the importance of mass transfer, related to the stirring speed, and the amount of charge passed through the electrodes, related to the current density on decomposition rate of PFOA. The CCD informed optimized operating conditions which we then used to study the impact of solution conditions. Acidic condition, high temperature, and low initial concentration of PFOA accelerated the degradation kinetic, while DO had a negligible effect. The impact of electrolyte concentration depended on the initial concentration of PFOA. At low initial PFOA dosage (0.2 mg L-1), the rate constant increased considerably from 0.079 ± 0.001 to 0.259 ± 0.019 min-1 when sulfate increased from 0.1% to 10%, likely due to the production of SO4•-. However, at higher initial PFOA dosage (20 mg L-1), the rate constant decreased slightly from 0.019 ± 0.001 to 0.015 ± 0.000 min-1, possibly due to the occupation of active anode sites by excess amount of sulfate. SO4•- and •OH played important roles in decomposition and defluorination of PFOA, respectively. PFOA oxidation was initiated by one electron transfer to the anode or SO4•-, undergoing Kolbe decarboxylation where yielded perfluoroalkyl radical followed three reaction pathways with •OH, O2 and/or H2O. PFAS electrooxidation depended on the chemical structures where the decomposition rate constants (min-1) were in the order of 6:2 FTCA (0.031) > PFOA (0.019) > GenX (0.013) > PFBA (0.008). PFBA with a shorter chain length and GenX with -CF3 branching had slower decomposition than PFOA. While presence of C-H bonds makes 6:2 FTCA susceptible to the attack of •OH accelerating its decomposition kinetic. Conducting experiments in mixed solution of all studied PFAS and in natural water showed that the co-presence of PFAS and other water constituents (organic and inorganic matters) had adverse effects on PFAS decomposition efficiency.

Removal of Zwitterionic PFAS by MXenes: Comparisons with Anionic, Nonionic, and PFAS-Specific Resins.

Zwitterionic per- and polyfluoroalkyl substances are increasingly detected in aquatic environments. The magnitude of their concentration and increased frequency of detection worldwide raise questions on their presence in drinking water and associated health risk. Scientific knowledge on the identification of treatment technologies to effectively capture such zwitterionic PFAS from contaminated water sources remains largely unknown. In this study, we investigated the application of anionic organic scavenger ion exchange (IX) resins (A860), nonionic IX resins (XAD 4 and XAD 7), PFAS-specific resins (A694 and A592), and Ti3C2 MXenes (novel two-dimensional metal carbides) for the removal of select fluorotelomer zwitterionic PFAS from natural waters. The cumulative removal of zwitterionic PFAS at pH ∼ 7 follows the order: Ti3C2 MXenes > A694 > A592 > A860 > XAD 4 ∼ XAD 7. Ti3C2 MXenes were able to capture >75% of the total influent zwitterionic PFAS and the performance remained consistent in natural and synthetic water. Ti3C2 MXenes also exhibited efficient regeneration (>90% recovery) with 0.4 M Na2SO3 solution, while the regeneration efficacy of other IX resins generally remained below 20%. Treatment with ∼180 J/cm2 UV dosage in the 0.4 M Na2SO3 regenerant brine solution yielded >99.9% reduction in the zwitterionic PFAS concentration indicating that UV-sulfite systems exhibit promising potential for the treatment of zwitterionic PFAS concentrates.

Total organic fluorine (TOF) analysis by completely converting TOF into fluoride with vacuum ultraviolet.

Quantifying total organic fluorine (TOF) in water is vital in monitoring the occurrence and persistence of all fluorine-containing organic compounds in the environment, while currently most studies focus on analyzing individual fluorine-containing organic compounds. To fill the technology gap, we herein proposed to convert TOF completely into fluoride with vacuum ultraviolet (VUV) photolysis, followed by analysis of fluoride with ion chromatography. Results showed that the tailored VUV photoreactor achieved satisfying recoveries of fluorine from ten model TOF compounds not only in ultrapure water (83.9 ± 2.0% to 109.4 ± 0.8%) but also in real water samples (92.1 ± 1.0%-106.2 ± 15.7%). Unlike other ultraviolet-based processes that favor alkaline conditions, this VUV process preferred either neutral or acidic conditions to defluorinate selected compounds. While the mechanisms remain to be explored in the future, it has been evidenced that the photo-degradation and photo-defluorination rates of these TOF compounds varied significantly among compounds and operation conditions. The method obtained a method detection limit (MDL) of 0.15 µg-F/L, which is lower than the MDLs of many other TOF analytical methods, along with excellent calibration curves for concentrations ranging from 0.01 to 10.0 mg-F/L. Notably, minimizing fluoride in sample prior to photoconversion was necessary to avoid subtraction-induced errors for TOF measurement, especially when the fluoride/TOF ratio was high. The robust VUV is also green for sample pretreatment due to its unreliance of chemicals or additives.

COVID-19 pandemic lesson learned- critical parameters and research needs for UVC inactivation of viral aerosols.

The COVID-19 pandemic highlighted public awareness of airborne disease transmission in indoor settings and emphasized the need for reliable air disinfection technologies. This increased awareness will carry in the post-pandemic era along with the ever-emerging SARS-CoV variants, necessitating effective and well-defined protocols, methods, and devices for air disinfection. Ultraviolet (UV)-based air disinfection demonstrated promising results in inactivating viral bioaerosols. However, the reported data diversity on the required UVC doses has hindered determining the best UVC practices and led to confusion among the public and regulators. This article reviews available information on critical parameters influencing the efficacy of a UVC air disinfection system and, consequently, the required dose including the system's components as well as operational and environmental factors. There is a consensus in the literature that the interrelation of humidity and air temperature has a significant impact on the UVC susceptibility, which translate to changing the UVC efficacy of commercialized devices in indoor settings under varying conditions. Sampling and aerosolization techniques reported to have major influence on the result interpretation and it is recommended to use several sampling methods simultaneously to generate comparable and conclusive data. We also considered the safety concerns and the potential safe alternative of UVC, far-UVC. Finally, the gaps in each critical parameter and the future research needs of the field are represented. This paper is the first step to consolidating literature towards developing a standard validation protocol for UVC air disinfection devices which is determined as the one of the research needs.

Elucidating the removal of organic micropollutants on biological ion exchange resins.

Biological ion exchange (BIEX) refers to operating ion exchange (IX) filters with infrequent regeneration to favor the microbial growth on resin surface and thereby contribute to the removal of organic matter through biodegradation. However, the extent of biodegradation on BIEX resins is still debatable due to the difficulty in discriminating between biodegradation and IX. The objective of the present study was to evaluate the performance of BIEX resins for the removal of organic micropollutants and thereby validate the occurrence of biodegradation. The removals of biodegradable micropollutants (neutral: caffeine and estradiol; negative: ibuprofen and naproxen) and nonbiodegradable micropollutants with different charges (neutral: atrazine and thiamethoxam; negative: PFOA and PFOS) were respectively monitored during batch tests with biotic and abiotic BIEX resins. Results demonstrated that biodegradation contributed to the removal of caffeine, estradiol, and ibuprofen, confirming that biodegradation occurred on the BIEX resins. Furthermore, biodegradation contributed to a lower extent to the removal of naproxen probably due to the absence of an adapted bacterial community (Biotic: 49% vs Abiotic: 38% after 24 h batch test). The removal of naproxen, PFOS, and PFOA were attributable to ion exchange with previously retained natural organic matter on BIEX resins. Nonbiodegradable and neutral micropollutants (atrazine and thiamethoxam) were minimally (6%-10%) removed during the batch tests. Overall, the present study corroborates that biomass found on BIEX resins contribute to the removal of micropollutants through biodegradation and ion exchange resins can be used as biomass support for biofiltration.

Biological ion exchange as an alternative to biological activated carbon for natural organic matter removal: Impact of temperature and empty bed contact time (EBCT).

Biofiltration is a widely used process in drinking water treatment plants to remove natural organic matter (NOM). A novel biofiltration process using ion exchange resins as supporting media (i.e., biological ion exchange or BIEX) has been demonstrated to provide a superior performance compared to conventional biological activated carbon (BAC). In order to optimize the performance of BIEX filters, the impact of temperature and empty bed contact time (EBCT) on NOM removal was systematically studied. In the present study, bench-scale BIEX filters were set up in parallel with BAC filters and operated at different temperatures (i.e., 4 °C, 10 °C and 20 °C) and EBCTs (i.e., 7.5 min, 15 min and 30 min). Higher average dissolved organic carbon (DOC) removal was achieved in BIEX filters (73 ± 6%) than BAC filters (22 ± 9%) at the steady state with an EBCT of 30 min. Higher temperatures improved NOM removal in both BAC and BIEX filters, with the impact being greater at lower EBCTs (i.e., 7.5 min and 15 min). Higher EBCTs could also improve NOM removal, with the impact being greater at lower temperatures (i.e., 4 °C and 10 °C). DOC removal for BIEX and BAC filters can be modeled with a first-order kinetic model (R2 = 0.93-0.99). BAC had a higher temperature activity coefficient than BIEX (1.0675 vs. 1.0429), indicating that temperature has a greater impact on BAC filtration than BIEX filtration. Overall, temperature and EBCT must be considered simultaneously for biofilters to efficiently remove NOM.

Application of MXenes for water treatment and energy-efficient desalination: A review.

MXenes are a new type of two-dimensional (2D) material which are rapidly gaining traction for a range of environmental, chemical and medical applications. MXenes and MXene-composites exhibit high surface area, superlative chemical stability, thermal conductivity, hydrophilicity and are environmentally compatible. Consequently, MXenes have been successfully employed for hydrogen storage, semiconductor manufacture and lithium ion batteries. In recent years, MXenes have been utilized in numerous environmental applications for treating contaminated surface waters, ground and industrial/ municipal wastewaters and for desalination, often outperforming conventional materials in each field. MXene-composites can adsorb multiple organic and inorganic contaminants, and undergo Faradaic capacitive deionization (CDI) when utilized for electrochemical applications. This approach allows for a significant decrease in the energy demand by overcoming the concentration polarization limitation of conventional CDI electrodes, offering a solution for low-energy desalination of brackish waters. This article presents a state-of-the-art review on water treatment and desalination applications of MXenes and MXene-composites. An investigation into the kinetics and isotherms is presented, as well as the impact of water constituents and operating conditions are also discussed. The applications of MXenes for CDI, pervaporation desalination and solar thermal desalination are also examined based on the reviewed literature. The effects of the water composition and operational protocols on the regeneration efficacy and long-term usage are also highlighted.

Biological ion exchange capable of sulphate-based secondary ion exchange during long-term DOC removal.

Biological ion exchange (BIEX) offers removal of dissolved organic carbon (DOC) with greatly reduced regeneration frequency. In the present work, a strong base anionic exchange resin was operated without regeneration and using inlet water with either Low (12 mg L-1) or High (60 mg L-1) sulphate and DOC of 2.75 or 5.0 mg L-1. Filters operated continuously for 226 days (16,500 bed volumes) and achieved DOC removal varying from 32% to 50%. Initially, sulphate and DOC were retained by the resin with chloride being released. During this period, DOC removal occurred due to traditional mechanisms, referred to as primary ion exchange. Following this initial period, DOC removal continued even though the conventionally defined resin capacity was exhausted (based on chloride loading). During the later period, no chloride release was observed, but instead sulphate was released. Although suggested by others, the present study is the first to confirm the direct exchange in charge equivalence of anions removed (DOC and nitrate) to released (sulphate) during the secondary ion exchange mechanism. Further, increasing inlet sulphate from 12 to 60 mg L-1 resulted in a 19% decrease in DOC removal. Finally, percent DOC removal was affected only by an increase of inlet DOC but not changes to the counter ion or after DOC loading on the resin increased to 1/3 of total capacity. This work promotes BIEX as a viable alternative to biological activated carbon and a leading solution for low-maintenance DOC removal.

PFAS removal by ion exchange resins: A review.

Per- and poly-fluoroalkyl substances (PFAS) represent a large family of anthropogenic organic compounds with a wide range of industrial and commercial applications. PFAS have become a global concern due to their toxicity and bio-accumulative properties. PFAS species have been ubiquitously detected in natural waters, wastewaters, sludge, and aquatic and terrestrial species which are anionic, zwitterionic and neutral. The ion exchange (IX) process for PFAS removal is an efficient technology for the remediation of PFAS-laden surface, ground and effluent wastewaters. This approach is more effective towards eliminating emerging short-chain PFAS which are not removed by carbon-based adsorption processes. This article presents a state-of-the-art review of PFAS removal from water via IX process. The evaluation and comparison of various IX resins in terms of kinetics and isotherms is presented. Literature data indicates that IX isotherm uptake capacity for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) can range up to 5 mmol/g on commercially available IX resins such as IRA 958 and IRA 67. The mechanism involved in the PFAS uptake process, such as diffusion, electrostatic interactions and hydrophobic effects are discussed. The effects of the eluent variability on the regeneration efficacy are also highlighted and the effect of single-use vs reuse for newly developed PFAS-specific IX resins are also examined based on the reviewed literature.

PFAS and DOM removal using an organic scavenger and PFAS-specific resin: Trade-off between regeneration and faster kinetics.

Treatment technologies such as ion exchange (IX) process exhibit promising potentials for the removal of toxic per- and poly-fluoroalkyl substances (PFAS) from natural waters. In recent years, industries have started manufacturing PFAS-specific resins which are typically operated in a single use-and-dispose mode until exhaustion. However, this increases the resin demand and the consequent operational cost and environmental burden of the IX process. In this study, the performance of a PFAS-specific resin (A592) was compared with that of a regenerative organic scavenger resin (A860) which is traditionally employed for dissolved organic matter (DOM) and micorpollutant removal. Comparative studies were performed to examine the removal of multiple long- and short-chain carboxylic, sulfonic, precursor and emerging PFAS (including GenX) from synthetic and natural waters. The A592 resin exhibited faster uptake kinetics for PFAS while simultaneously removing 10-15% of DOM. The A860 resin removed ~60-70% of DOM; however, it required approximately 3-fold higher contact times for achieving the same degree of PFAS removal when compared to the PFAS-specific resin. The resin breakthrough (Ctreated (PFAS) > 70 ng/L) was observed around 125,000 ± 5000 bed volumes (BVs) for the PFAS-specific resin (via multiple loading tests), while it ranged between 15,000-27,000 BVs for the organic scavenger. Yet, a mass balance on PFAS and DOM removal indicated ~90-98% site saturation (in milli-equivalents (meqs)) on both IX resins before exhaustion. More importantly, the regenerated organic scavenger resin (A860) exhibited PFAS and DOM removal capabilities for longer operational BVs when compared to A592 operated in a single-use-mode in natural waters.

The impact of chloride and chlorine radical on nitrite formation during vacuum UV photolysis of water.

The impact of chloride ion and chlorine radical on the formation of nitrite was investigated under Vacuum-UV (VUV) photolysis of nitrate contaminating water. An increase in chloride concentration reduced nitrite formation in part due to the relatively high VUV absorption of chloride. The use of various radical scavengers, such as acetate and acetone, helped delineate the specific roles of hydroxyl radical (HO) and chlorine radical (Cl) in oxidation and VUV photolysis of nitrate, and the subsequent formation of nitrite. HO reduced nitrite formation due to its high reaction rate constant with nitrite. Nitrite formation in both chloride and dissolved organic carbon (DOC) containing solution depended primarily on their relative concentrations. Carbamazepine (CBZ) was also used to analyze the effect of Cl on both the degradation of CBZ and the formation of nitrite. Cl showed to significantly increase the degradation of CBZ, but it had little impact on the formation of nitrite. This paper, utilizing detailed experimental data combined with kinetic modeling and mechanistic analysis of VUV photolysis in the presence of chloride and nitrate, provides the necessary scientific guidance towards more effective and optimized applications of VUV technology for drinking water treatment.

Removal of legacy PFAS and other fluorotelomers: Optimized regeneration strategies in DOM-rich waters.

We present the first study investigating optimized regeneration strategies for anionic ion exchange (IX) resins during the removal of persistent per- and poly-fluoroalkyl substances (PFAS, including GenX) from surface and treated wastewater effluents. IX regeneration studies are of critical importance from environmental perspectives. Specifically, the knowledge is essential for water utilities who presently operate IX (for PFAS removal) in a single use-and-dispose mode. In this study, legacy PFAS such as PFOA/PFOS were tested along with other harmful short-chained PFAS (PFBA/PFBS) and other toxic perfluorinated substitutes (GenX). Studies were performed on synthetic water (spiked with Suwannee River Natural Organic Matter (SRNOM), Fulvic Acid (SRFA) and Humic Acid (SRHA)), surface water, and wastewater effluents, and the regeneration was performed in batch stirred reactors. The resin service life with and without regeneration was investigated in the presence of background organic matter. In ultra-pure waters, all PFAS (C0 ∼10 µg/L, concentrations similar to that of natural waters) were effectively removed for >100,000 Bed Volume (BV) of operation. This was reduced to ∼23,500 BV in the presence of SRNOM (C0 = 5 mg C/L), 20,500 BV in SRFA and 8500 BV in SRHA, after which the saturated resins required regeneration. More importantly, all resin breakthrough (PFAS> 70 ng/L) corresponded to > 90% resin site saturation (in meqs), an essential information for optimizing IX loading. The competitive dissolved organic matter (DOM) fractions were estimated to be approximately 5-9% of the initial DOC, as estimated by the IAST-EBC model. Finally, it was identified that IX regeneration efficiency improved with increasing brine contact time but effectiveness plateaued for brine concentrations above 10% (W/V). Nonetheless, a regeneration with 10% NaCl solution with a contact time of 2 h was found to be optimal for IX operations in synthetic and natural waters. Therefore, this study provides key knowledge essential for the scientific community and the water industry on optimizing IX operational parameters for DOM and PFAS removal and would be highly valuable for systems which presently operate IX in a use-and-dispose mode.

Degradation of cyanotoxin microcystin-LR in synthetic and natural waters by chemical-free UV/VUV radiation.

This study investigated the capability of ultraviolet radiation at 254 nm and 185 nm (UV/VUV) to degrade cyanotoxin microcystin-LR (MC-LR). Results showed 70% toxin reduction solely by 254 nm direct photolysis (ε254 = 13,225 ±â€¯814 M-1cm-1; Φ254 = 0.29 ±â€¯0.03 mol/Einstein). The addition of 185 nm increased MC-LR degradation through advanced oxidation by •OH (k•OH,MC-LR = 2.25 ±â€¯0.39 × 1010 M-1s-1). Alkalinity and organics (DOC) reduced MC-LR degradation by scavenging •OH (kobs,MilliQ = 0.117 cm2/mJ; kobs,50ppmAlk. = 0.0497 cm2/mJ; kobs,6ppmDOC = 0.019 cm2/mJ). Chloride absorbed 185 nm, impacting •OH formation and generating Cl•, while also scavenging •OH. However, Cl• is reactive and •OH scavenging is reversible, resulting in relatively low impact on MC-LR degradation (kobs,50ppmCl = 0.0939 cm2/mJ). In natural water, MC-LR could be degraded from a typical concentration (˜15 µg/L) to below detection (<0.5 µg/L) with a UV254 fluence of 200 mJ/cm2 using UV/VUV. The presence of cyanobacterial cells impeded MC-LR degradation; however, 90% MC-LR degradation could still be achieved. UV/VUV is a promising chemical-free technology capable of MC-LR degradation in a variety of water conditions, and a potentially suitable treatment option for small, remote communities.