From "forever chemicals" to fluorine-free alternatives.

Identifying alternatives to PFAS requires weighing trade-offs and uncertainties.

Photo-production of excited triplet-state of dissolved organic matters in inland freshwater and coastal seawater.

The excited triplet-state of dissolved organic matter (3DOM*) is a major reactive intermediate in sunlit waters. Its quantum yield is important in understanding the fate of organic micropollutants. The degradation efficiency of its chemical probe, 2,4,6-trimeythlphenol (fTMP), is generally used as a proxy of the quantum yield. However, fTMP has been described and modelled only for freshwater systems. Therefore, this study quantified fTMP in inland freshwater and coastal seawater sampled in Japan by conducting steady-state photochemical experiments. Optical properties of water were then used to model fTMP. Results indicated that the inland freshwater DOM originated mainly from terrestrial sources, while the coastal seawater DOM were microbial-dominated. On average, inland freshwater exhibited lower fTMP (61.2 M-1) than coastal seawater (79.7 M-1) and the coastal seawater exhibited significant variations in the proportion of high-energy 3DOM* (> 250 kJ/mol). In addition, E2:E3 (ratio of absorbance at 254 to 365 nm) was positively correlated with fTMP of inland freshwater, coastal seawater, and the overall dataset. Catchment conditions such as forest coverage also influenced the production of 3DOM* and high-energy 3DOM* in inland freshwater. Furthermore, the developed models estimated fTMP based on the optical properties of both freshwater and seawater, providing valuable insights about 3DOM* photochemistry in the aquatic environment.

PFAS occurrence and distribution in yard waste compost indicate potential volatile loss, downward migration, and transformation.

We discovered high concentrations of PFAS (18.53 ± 1.5 µg kg-1) in yard waste compost, a compost type widely acceptable to the public. Seventeen out of forty targeted PFAS, belonging to six PFAS classes were detected in yard waste compost, with PFCAs (13.51 ± 0.99 µg kg-1) and PFSAs (4.13 ± 0.19 µg kg-1) being the dominant classes, comprising approximately 72.5% and 22.1% of the total measured PFAS. Both short-chain PFAS, such as PFBA, PFHxA, and PFBS, and long-chain PFAS, such as PFOA and PFOS, were prevalent in all the tested yard waste compost samples. We also discovered the co-occurrence of PFAS with low-density polyethylene (LDPE) and polyethylene terephthalate (PET) plastics. Total PFAS concentrations in LDPE and PET separated from incoming yard waste were 7.41 ± 0.41 µg kg-1 and 1.35 ± 0.1 µg kg-1, which increased to 8.66 ± 0.81 µg kg-1 in LDPE and 5.44 ± 0.56 µg kg-1 in PET separated from compost. An idle mature compost pile revealed a clear vertical distribution of PFAS, with the total PFAS concentrations at the surface level approximately 58.9-63.2% lower than the 2 ft level. This difference might be attributed to the volatile loss of short-chain PFCAs, PFAS's downward movement with moisture, and aerobic transformations of precursor PFAS at the surface.

Sensors for Emerging Water Contaminants: Overcoming Roadblocks to Innovation.

Ensuring water quality and safety requires the effective detection of emerging contaminants, which present significant risks to both human health and the environment. Field deployable low-cost sensors provide solutions to detect contaminants at their source and enable large-scale water quality monitoring and management. Unfortunately, the availability and utilization of such sensors remain limited. This Perspective examines current sensing technologies for detecting emerging contaminants and analyzes critical barriers, such as high costs, lack of reliability, difficulties in implementation in real-world settings, and lack of stakeholder involvement in sensor design. These technical and nontechnical barriers severely hinder progression from proof-of-concepts and negatively impact user experience factors such as ease-of-use and actionability using sensing data, ultimately affecting successful translation and widespread adoption of these technologies. We provide examples of specific sensing systems and explore key strategies to address the remaining scientific challenges that must be overcome to translate these technologies into the field such as improving sensitivity, selectivity, robustness, and performance in real-world water environments. Other critical aspects such as tailoring research to meet end-users' requirements, integrating cost considerations and consumer needs into the early prototype design, establishing standardized evaluation and validation protocols, fostering academia-industry collaborations, maximizing data value by establishing data sharing initiatives, and promoting workforce development are also discussed. The Perspective describes a set of guidelines for the development, translation, and implementation of water quality sensors to swiftly and accurately detect, analyze, track, and manage contamination.

Trace Organic Contaminant Removal from Municipal Wastewater by Styrenic ß-Cyclodextrin Polymers.

Trace organic contaminants (TrOCs) present major removal challenges for wastewater treatment. TrOCs, such as perfluoroalkyl and polyfluoroalkyl substances (PFAS), are associated with chronic toxicity at ng L-1 exposure levels and should be removed from wastewater to enable safe reuse and release of treated effluents. Established adsorbents, such as granular activated carbon (GAC), exhibit variable TrOC removal and fouling by wastewater constituents. These shortcomings motivate the development of selective novel adsorbents that also maintain robust performance in wastewater. Cross-linked ß-cyclodextrin (ß-CD) polymers are promising adsorbents with demonstrated TrOC removal efficacy. Here, we report a simplified and potentially scalable synthesis of a porous polymer composed of styrene-linked ß-CD and cationic ammonium groups. Batch adsorption experiments demonstrate that the polymer is a selective adsorbent exhibiting complete removal for six out of 13 contaminants with less adsorption inhibition than GAC in wastewater. The polymer also exhibits faster adsorption kinetics than GAC and ion exchange (IX) resin, higher adsorption affinity for PFAS than GAC, and is regenerable by solvent wash. Rapid small-scale column tests show that the polymer exhibits later breakthrough times compared to GAC and IX resin. These results demonstrate the potential for ß-CD polymers to remediate TrOCs from complex water matrices.

Sunrise of PFAS Replacements: A Perspective on Fluorine-Free Foams.

One type of firefighting foam, referred to as aqueous filmforming foams (AFFF), is known to contain per- and polyfluoroalkyl substances (PFAS). The concerns raised with PFAS, and their potential environmental and health impacts, have led to a surge in research on fluorine-free alternatives both in the United States and globally. Particularly, in January 2023, a new military specification (MIL-PRF-32725) for fluorine-free foam was released in accordance with Congressional requirements for the U.S. Department of Defense. This paper provides a critical analysis of the present state of the various fluorine-free options that have been developed to date. A nuanced perspective of the challenges and opportunities of more sustainable replacements is explored by examining the performance, cost, and regulatory considerations associated with these fluorine-free alternatives. Ultimately, this evaluation shows that the transition to fluorine-free replacements is likely to be complex and multifaceted, requiring careful consideration of the trade-offs involved. Yet, the ongoing work will provide valuable insights for future research on alternatives to AFFF and enhancing the safety and sustainability of fire suppression systems.

Total Oxidizable Precursor (TOP) Assay-Best Practices, Capabilities and Limitations for PFAS Site Investigation and Remediation.

The comprehensive characterization of per- and polyfluoroalkyl substances (PFASs) is necessary for the effective assessment and management of risk at contaminated sites. While current analytical methods are capable of quantitatively measuring a number of specific PFASs, they do not provide a complete picture of the thousands of PFASs that are utilized in commercial products and potentially released into the environment. These unmeasured PFASs include many PFAS precursors, which may be converted into related PFAS chemicals through oxidation. The total oxidizable precursor (TOP) assay offers a means of bridging this gap by oxidizing unknown PFAS precursors and intermediates and converting them into stable PFASs with established analytical standards. The application of the TOP assay to samples from PFAS-contaminated sites has generated several new insights, but it has also presented various technical challenges for laboratories. Despite the increased number of literature studies that include the TOP assay, there is a critical and growing gap in the application of this method beyond researchers in academia. This article outlines the benefits and challenges of using the TOP assay with aqueous samples for site assessments and suggests ways to address some of its limitations.

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.

Dissolved silicon in a lake-floodplain system: Dynamics and its role in primary production.

Dissolved silicon (DSi) is essential for aquatic primary production and its limitation relative to nitrogen (N) and phosphorus (P) facilitates cyanobacterial dominance. However, the effects of DSi on phytoplankton growth and community structure have yet to be fully determined in tropical lakes, particularly in relation to N and P. Therefore, this study investigated the role of DSi in Tonlé Sap Lake, Cambodia, a tropical floodplain system well known for its flood-pulse characteristics and high productivity. To that end, seasonal water sampling and in situ water quality measurements were performed around the floating villages of Chhnok Tru region. The concentration of DSi was significantly higher in the dry season than in the wet season at 16.3-22.1 versus 7.2-14.0 mg/L, respectively; however, both sets of measurements were comparable with lakes in other parts of the world. Meanwhile, the average molar ratio of TN:TP:DSi was 69:1:33 in the dry season and 39:1:24 in the wet season, which compared with the Redfield ratio of 16:1:16, suggested limitation of TP and DSi in both seasons. In addition, phytoplankton biomass in terms of chlorophyll-a was found to be a collective function of DSi, TN:TP, dissolved oxygen, and water temperature in both seasons. Taken together, these results suggest that DSi is affected by the annual hydrological cycle in the Tonlé Sap Lake flood-pulse ecosystem, serving as a secondary limiting nutrient of primary production during both the dry and wet seasons.

Emerging investigator series: microplastic-based leachate formation under UV irradiation: the extent, characteristics, and mechanisms.

Microplastics in the aquatic system are among the many inevitable consequences of plastic pollution, which has cascading environmental and public health impacts. Our study aimed at analyzing surface interactions and leachate production of six microplastics under ultraviolet (UV) irradiation. Leachate production was analyzed for the dissolved organic content (DOC), UV254, and fluorescence through excitation emission (EEM) to determine the kinetics and mechanisms involved in the release of organic matter by UV irradiation. The results suggested there was a clear trend of organic matter being released from the surface of the six microplastics caused by UV irradiation based on DOC, UV254 absorbance, and EEM intensity increasing with time. Polystyrene had the greatest and fastest increase in DOC concentrations, followed by the resin coated polystyrene. Experiments conducted at different temperatures indicated the endothermic nature of these leaching mechanisms. The differences in leachate formation for different polymers were attributed to their chemical makeup and their potency to interact with UV. The aged microplastic samples were analyzed by Fourier-transform infrared spectroscopy (FT-IR), Raman, and X-ray photoelectron spectroscopy (XPS), to determine the surface changes with respect to leachate formation. Results indicated that all microplastics had increasing carbonyl indices when aged by UV with polystyrene being the greatest. These findings affirm that the leachate formation is an interfacial interaction and could be a significant source of organic compound influx to natural waters due to the extremely abundant occurrence of microplastics and their large surface areas.

Integrated data-driven cross-disciplinary framework to prevent chemical water pollution.

Access to a clean and healthy environment is a human right and a prerequisite for maintaining a sustainable ecosystem. Experts across domains along the chemical life cycle have traditionally operated in isolation, leading to limited connectivity between upstream chemical innovation to downstream development of water-treatment technologies. This fragmented and historically reactive approach to managing emerging contaminants has resulted in significant externalized societal costs. Herein, we propose an integrated data-driven framework to foster proactive action across domains to effectively address chemical water pollution. By implementing this integrated framework, it will not only enhance the capabilities of experts in their respective fields but also create opportunities for novel approaches that yield co-benefits across multiple domains. To successfully operationalize the integrated framework, several concerted efforts are warranted, including adopting open and FAIR (findable, accessible, interoperable, and reusable) data practices, developing common knowledge bases/platforms, and staying vigilant against new substance "properties" of concern.

Single-Crystalline Imine-Linked Two-Dimensional Covalent Organic Frameworks Separate Benzene and Cyclohexane Efficiently.

Two-dimensional (2D) covalent organic frameworks (COFs) are composed of structurally precise, permanently porous, layered macromolecular sheets, which are traditionally synthesized as polycrystalline solids with crystalline domain lengths smaller than 100 nm. Here, we polymerize imine-linked 2D COFs as suspensions of faceted single crystals in as little as 5 min at moderate temperature and ambient pressure. Single crystals of two imine-linked 2D COFs were prepared, consisting of a rhombic 2D COF (TAPPy-PDA) and a hexagonal 2D COF (TAPB-DMPDA). The sizes of TAPPy-PDA and TAPB-DMPDA crystals were tuned from 720 nm to 4 µm and 450 nm to 20 µm in width, respectively. High-resolution transmission electron microscopy revealed that the COF crystals consist of layered, 2D polymers comprising single-crystalline domains. Continuous rotation electron diffraction resolved the unit cell and crystal structure of both COFs, which are single-crystalline in the a-b plane but disordered in the stacking c dimension. Single crystals of both COFs were incorporated into gas chromatography separation columns and exhibited unusual selective retention of cyclohexane over benzene, with single-crystalline TAPPy-PDA significantly outperforming single-crystalline TAPB-DMPDA. Polycrystalline TAPPy-PDA exhibited no separation, while polycrystalline TAPB-DMPDA exhibited poor separation and the opposite order of elution, retaining benzene more than cyclohexane, indicating the importance of improved material quality for COFs to exhibit properties that derive from their precise, crystalline structures. This work represents the first example of synthesizing imine-linked 2D COF single crystals at ambient pressure and short reaction times and demonstrates the promise of high-quality COFs for molecular separations.

Low-temperature mineralization of perfluorocarboxylic acids.

Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative pollutants found in water resources at concentrations harmful to human health. Whereas current PFAS destruction strategies use nonselective destruction mechanisms, we found that perfluoroalkyl carboxylic acids (PFCAs) could be mineralized through a sodium hydroxide-mediated defluorination pathway. PFCA decarboxylation in polar aprotic solvents produced reactive perfluoroalkyl ion intermediates that degraded to fluoride ions (78 to ~100%) within 24 hours. The carbon-containing intermediates and products were inconsistent with oft-proposed one-carbon-chain shortening mechanisms, and we instead computationally identified pathways consistent with many experiments. Degradation was also observed for branched perfluoroalkyl ether carboxylic acids and might be extended to degrade other PFAS classes as methods to activate their polar headgroups are identified.

A Tunable Porous ß-Cyclodextrin Polymer Platform to Understand and Improve Anionic PFAS Removal.

Cross-linked polymers containing ß-cyclodextrin (ß-CD) are promising adsorbents with demonstrated removal performances for per- and polyfluoroalkyl substances (PFASs) from contaminated water sources. Despite the promising performance of some ß-CD-based adsorbents for PFAS removal, many of these materials are not amenable for rational performance improvement or addressing fundamental questions about the PFAS adsorption mechanisms. These ambiguities arise from the poorly defined structure of the cross-linked polymers, especially with respect to the random substitution patterns of the cyclodextrins as well as side reactions that modify the structures of some cross-linkers. Here, we report a new ß-CD polymer platform in which styrene groups are covalently attached to ß-CD to form a discrete monomer that is amenable to radical polymerization. This monomer was polymerized with styrene and methacrylate comonomers to provide three ß-CD polymers with high specific surface areas and high isolated yields (all >93%). A ß-CD polymer copolymerized with a methacrylate bearing a cationic functional group achieved nearly 100% removal for eight anionic PFASs (initial concentration of 1 µg/L for each compound) in nanopure water at an exceedingly low adsorbent loading of 1 mg L-1, as compared to previous cyclodextrin polymers that required loadings at least 1 order of magnitude higher to achieve an equivalent degree of PFAS removal. Furthermore, when the adsorbents were studied in a challenging salt matrix, we observed that long-chain PFAS adsorption was controlled by a complementary interplay of hydrophobic and electrostatic interactions, whereas short-chain PFASs primarily relied on electrostatic interactions. This approach demonstrates great promise for anionic PFAS removal, and we anticipate that new compositions will be tailored using the versatility of radical polymerization to simultaneously target PFASs and other classes of micropollutants in the future.

Emerging investigator series: microplastic sources, fate, toxicity, detection, and interactions with micropollutants in aquatic ecosystems - a review of reviews.

Hundreds of review studies have been published focusing on microplastics (MPs) and their environmental impacts. With the microbiota colonization of MPs being firmly established, MPs became an important carrier for contaminants to step inside the food web all the way up to humans. Thus, the continuous feed of MPs into the ecosystem has sparked a multitude of scientific concerns about their toxicity, characterization, and interactions with microorganisms and other contaminants. The reports of common subthemes have agreed about many findings and research gaps but also showed contradictions about others. To unravel these equivocal conflicts, we herein compile all the major findings and analyze the paramount discrepancies among these review papers. Furthermore, we systematically reviewed all the highlights, research gaps, concerns, and future needs. The covered focus areas of MPs' literature include the sources, occurrence, fate, existence, and removal in wastewater treatment plants (WWTPs), toxicity, interaction with microbiota, sampling, characterization, data quality, and interaction with other co-contaminants. This study reveals that many mechanisms of MPs' behavior in aquatic environments like degradation and interaction with microbiota are yet to be comprehended. Furthermore, we emphasize the critical need to standardize methods and parameters for MP characterization to improve the comparability and reproducibility of the incoming research.

Regrowth of Escherichia coli in environmental waters after chlorine disinfection: shifts in viability and culturability.

Bacterial regrowth after water/wastewater disinfection poses severe risks to public health. However, regrowth studies under realistic water conditions that might critically affect bacterial regrowth are scarce. This study aimed to assess for the first time the regrowth of Escherichia coli (E. coli) in terms of its viability and culturability in environmental waters after chlorine disinfection, which is the most widely used disinfection method. Post-chlorination regrowth tests were conducted in 1) standard 0.85% NaCl solution, 2) river water receiving domestic wastewater effluents, and 3) river water that is fully recharged by domestic wastewater effluents. The multiplex detection of plate count and fluorescence-based viability test was adopted to quantify the culturable and viable E. coli to monitor the regrowth process. The results confirmed that chlorine treatment (0.2, 0.5 and 1.0 mg L-1 initial free chlorine) induced more than 99.95% of E. coli to enter a viable but non-culturable (VBNC) state and the reactivation of VBNC E. coli is presumably the major process of the regrowth. A second-order regrowth model well described the temporal shift of the survival ratio of culturable E. coli after the chlorination (R2: 0.73-1.00). The model application also revealed that the increase in initial chlorine concentration and chlorine dose limited the maximum regrowth rate and the maximum survival ratio, and the regrowth rate and percentage also changed with the water type. This study gives a better understanding of the potential regrowth after chlorine disinfection and highlights the need for investigating the detailed relation of the regrowth to environmental conditions such as major components of water matrices.

Membranes for Oil/Water Separation: A Review.

Recent advancements in separation and membrane technologies have shown a great potential in removing oil from wastewaters effectively. In addition, the capabilities have improved to fabricate membranes with tunable properties in terms of their wettability, permeability, antifouling, and mechanical properties that govern the treatment of oily wastewaters. Herein, authors have critically reviewed the literature on membrane technology for oil/water separation with a specific focus on: 1) membrane properties and characterization, 2) development of various materials (e.g., organic, inorganic, and hybrid membranes, and innovative materials), 3) membranes design (e.g., mixed matrix nanocomposite and multilayers), and 4) membrane fabrication techniques and surface modification techniques. The current challenges and future research directions in materials and fabrication techniques for membrane technology applications in oil/water separation are also highlighted. Thus, this review provides helpful guidance toward finding more effective, practical, and scalable solutions to tackle environmental pollution by oils.

Recent advances on PFAS degradation via thermal and nonthermal methods.

Per- and polyfluoroalkyl substances (PFAS) are a set of synthetic chemicals which contain several carbon-fluorine (C-F) bonds and have been in production for the past eight decades. PFAS have been used in several industrial and consumer products including nonstick pans, food packaging, firefighting foams, and carpeting. PFAS require proper investigations worldwide due to their omnipresence in the biotic environment and the resulting pollution to drinking water sources. These harmful chemicals have been associated with adverse health effects such as liver damage, cancer, low fertility, hormone subjugation, and thyroid illness. In addition, these fluorinated compounds show high chemical, thermal, biological, hydrolytic, photochemical, and oxidative stability. Therefore, effective treatment processes are required for the removal and degradation of PFAS from wastewater, drinking water, and groundwater. Previous review papers have provided excellent summaries on PFAS treatment technologies, but the focus has been on the elimination efficiency without providing mechanistic understanding of removal/degradation pathways. The present review summarizes a comprehensive examination of various thermal and non-thermal PFAS destruction technologies. It includes sonochemical/ultrasound degradation, microwave hydrothermal treatment, subcritical or supercritical treatment, electrical discharge plasma technology, thermal destruction methods/incinerations, low/high-temperature thermal desorption process, vapor energy generator (VEG) technology and mechanochemical destruction. The background, degradation mechanisms/pathways, and advances of each remediation process are discussed in detail in this review.

Ecological and human health risks of manure-borne steroid estrogens: A 20-year global synthesis study.

Estrone (E1), 17α-estradiol (17α-E2), 17ß-estradiol (17ß-E2), and estriol (E3) are persistent in livestock manure and present serious pollution concerns because they can trigger endocrine disruption at part-per-trillion levels. This study conducted a global analysis of estrogen occurrence in manure using all literature data over the past 20 years. Besides, predicted environmental concentration (PEC) in soil and water was estimated using fate models, and risk/harm quotient (RQ/HQ) methods were applied to screen risks on children as well as on sensitive aquatic and soil species. The estradiol equivalent values ranged from 6.6 to 4.78 × 104 ng/g and 12.4 to 9.46 × 104 ng/L in the solid and liquid fraction. The estrogenic potency ranking in both fractions were 17ß-E2> E1>17α-E2>E3. RQs of measured environmental concentration in the liquid fraction pose medium (E3) to high risk (E1, 17α-E2 & 17ß-E2) to fish but are lower than risks posed by xenoestrogens. However, the RQ of PECs on both soil organisms and aquatic species were insignificant (RQ < 0.01), and HQs of contaminated water and soil ingestion were within acceptable limits. Nevertheless, meticulous toxicity studies are still required to confirm (or deny) the findings because endocrine disruption potency from mixtures of these classes of compounds cannot be ignored.

Novel fluorescence-based method for rapid quantification of live bacteria in river water and treated wastewater.

Monitoring bacteria is essential for ensuring microbial safety of water sources, including river water and treated wastewater. The plate count method is common for monitoring bacterial abundance, although it cannot detect all live bacteria such as viable but non-culturable bacteria, causing underestimation of microbial risks. Live/Dead BacLight kit, involving fluorochromes SYTO 9 and propidium iodide (PI), provides an alternative to assess bacterial viability using flow cytometry or microscopy. However, its application is limited due to the high cost of flow cytometry and the inapplicability of microscopy to most environmental waters. Thus, this study introduces the combination of BacLight kit and fluorescence spectroscopy for quantifying live bacteria in river water and treated wastewater. Mixtures of live and dead Escherichia coli (E. coli) with various ratios and total cell concentrations were stained with SYTO 9 and PI and measured by fluorescence spectroscopy. The fluorescence emission peak area of SYTO 9 in the range of 500-510 nm at the excitation wavelength of 470 nm correlates linearly with the viable cell counts (R 2 > 0.99, p < 0.0001) with only slight variations in the complex water matrix. The tested method can quantify the live E. coli from 3.67 × 104 to 2.70 × 107 cells per mL. This method is simple, sensitive and reliable for quantifying live bacteria in environmental water, which can be later integrated into real-time monitoring systems.