Regeneration of exhausted adsorbents after PFAS adsorption: A critical review.

The adsorption process efficiently removes per- and polyfluoroalkyl substances (PFAS) from water, but managing exhausted adsorbents presents notable environmental and economic challenges. Conventional disposal methods, such as incineration, may reintroduce PFAS into the environment. Therefore, advanced regeneration techniques are imperative to prevent leaching during disposal and enhance sustainability and cost-effectiveness. This review critically evaluates thermal and chemical regeneration approaches for PFAS-laden adsorbents, elucidating their operational mechanisms, the influence of water quality parameters, and their inherent advantages and limitations. Thermal regeneration achieves notable desorption efficiencies, reaching up to 99% for activated carbon. However, it requires significant energy input and risks compromising the adsorbent's structural integrity, resulting in considerable mass loss (10-20%). In contrast, chemical regeneration presents a diverse efficiency landscape across different regenerants, including water, acidic/basic, salt, solvent, and multi-component solutions. Multi-component solutions demonstrate superior efficiency (>90%) compared to solvent-based solutions (12.50%), which, in turn, outperform salt (2.34%), acidic/basic (1.17%), and water (0.40%) regenerants. This hierarchical effectiveness underscores the nuanced nature of chemical regeneration, significantly influenced by factors such as regenerant composition, the molecular structure of PFAS, and the presence of organic co-contaminants. Exploring the conditional efficacy of thermal and chemical regeneration methods underscores the imperative of strategic selection based on specific types of PFAS and material properties. By emphasizing the limitations and potential of particular regeneration schemes and advocating for future research directions, such as exploring persulfate activation treatments, this review aims to catalyze the development of more effective regeneration processes. The ultimate goal is to ensure water quality and public health protection through environmentally sound solutions for PFAS remediation efforts.

Mechanochemically sulfidated zero-valent iron as persulfate activation catalyst in permeable reactive barriers for groundwater remediation - A feasibility study.

The technology of permeable reactive barriers is reliable and economically effective to prevent the spread of pollutants in groundwaters. Yet, it is efficacious only with easily reducible chemicals such as heavy metals and halogenated organics. In the present study, sulfidated zero-valent iron solventless synthesized by ball-milling is proposed as a possible barrier filling for activation of persulfate to achieve sound removal of reduction-resistant organic pollutants (the herbicide atrazine was used as a model pollutant). Preliminary batch experiments demonstrated rapid degradation of atrazine. Continuous experiments executed in columns proved the superior efficiency of sulfidated iron as a persulfate activator, compared to zero-valent iron, in terms of removal of both atrazine and byproducts. Optimal atrazine removal in the column was achieved with 10% sulfidated iron packing, and 9 mM persulfate at a hydraulic residence time of 6.02 h. Under such conditions, the estimated bed length of the reactive barrier for 99% atrazine removal was 8.69 cm. The morphology and surface-active species in the column demonstrated that activation of persulfate mainly occurred at the inlet of the column until the complete usage of the active species. Batch experiments with coexisting ions suggested that they have a minor influence on atrazine removal percentage, while Mg2+, Ca2+, CO2- and HCO- had a significant impact on the kinetics of the process. However, analogous column experiments demonstrated that the coexisting ions have a negative influence on both atrazine and its byproducts. The results obtained in this study corroborate the potential application of persulfate-enhanced permeable reactive barriers for in situ removal of atrazine from underground water.

Wastewater surveillance for 168 pharmaceuticals and metabolites in a WWTP: Occurrence, temporal variations and feasibility of metabolic biomarkers for intake estimation.

Wastewater-based epidemiology (WBE) is amply used for mining information about public health such as the estimation of consumption/intake of certain substances. Yet, proper biomarker selection is critical to obtain reliable data. This study measured a broad range of pharmaceuticals and metabolites in a wastewater treatment plant in Beijing, China, and evaluated their suitability as consumption estimation biomarkers. Wastewater sampling was conducted during a normal week and two holiday weeks to assess the impact of the holiday on population normalized daily mass loads (PNDLs). One hundred and forty-nine out of 168 pharmaceuticals were detected, with 94 analytes being quantified in all sampling events. Moreover, digestive drug cimetidine (

Mechanochemical synthesis of catalysts and reagents for water decontamination: Recent advances and perspective.

This paper aims to provide insights on mechanochemistry as a green and versatile tool to synthesize advanced materials for water remediation. In particular, mechanochemical methodologies for preparation of reagents and catalysts for the removal of organic pollutants are reviewed and discussed, focusing on those materials that, directly or indirectly, induce redox reactions in the contaminants (i.e., photo-, persulfate-, ozone-, and Fenton-catalysts, as well as redox reagents). Methods reported in the literature include surface reactivity enhancement for single-component materials, as well as multi-component material design to obtain synergistic effects in catalytic efficiency and/or reactivity. It was also amply demonstrated that mechanochemical surface activation or the incorporation of catalytic/reactive components boost the generation of reactive species in water by accelerating charge transfer, increasing superficial active sites, and developing pollutant absorption. Finally, indications for potential future developments in this field are debated.

Improved fractal kinetic model to predict mechanochemical destruction rate of organic pollutants.

Mechanochemical destruction of organic pollutants by high energy milling with inorganic reagents is considered a promising non-thermal technology to detoxify hazardous waste. However, due to complex nature of the physicochemical phenomena involved, pollutant destruction kinetics heavily depends on the used reagents and operating parameters, thus varying case by case. In the present work, a fractal model was validated as flexible tool to interpolate pollutant mechanochemical destruction data satisfactorily. In addition, such model was expanded to estimate the contributions of the inorganic reagent and the pollutant to the overall reaction rate. Specifically, the kinetic constant associated to mechanical activation of the co-milling reagent and that related to pollutant destruction reaction were calculated. Their values resulted to depend only on the specific compound, hence, the tabulated data could be used to predict the pollutant mechanochemical degradation rate for any kind of mixture.

Occurrence and variations of pharmaceuticals and personal-care products in rural water bodies: A case study of the Taige Canal (2018-2019).

A systematic monitoring campaign of pharmaceuticals and personal-care products (PPCPs) was performed in the Taige Canal basin, which is located in a rural area of the Yangtze River Delta. A total of 55 out of 61 monitored PPCPs were detected, with concentrations up to 647 ng/L. The maximum concentrations of 75% of monitored antibiotics and 80% of non-antibiotics were above the median values of previously reported maximum concentrations in China, indicating that the basin is heavily contaminated. It is estimated that the PPCP mass flow of the Taige Canal (0.06-0.58 kg/day) entering into Lake Taihu is similar to that of the influent of a wastewater treatment plant. Analysis of the seasonal variation shows that, during the wet season, the average total concentration of sulfonamides was 8 and 11 times that of the normal season and dry season, respectively. The concentration of sulfachlorpyridazine accounted for 40.37% of total antibiotics, suggesting heavy pollution from the animal-breeding industry in this area. The PPCP mass flow rates observed in 2019 were lower than those of 2018 in the same season, and this interannual variation is mainly attributable to water pollution controls in the watershed. Combined analysis of ordination and clustering indicates that the distribution of PPCPs in the Taige Canal is affected by the confluence with Yong'an River and human activities such as water pollution control. Water-sediment distribution analysis demonstrates that the sediment-water distribution coefficients of quinolone and macrolide were higher than those of sulfonamide, lincosamide and chloramphenicol.

Role of hydrogenated moiety in redox treatability of 6:2 fluorotelomer sulfonic acid in chrome mist suppressant solution.

6:2 Fluorotelomer sulfonic acid (6:2 FTS) is used as alternative to perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) for different purposes such as chrome mist suppressant (CMS) and active ingredient in fire-fighting foams. In this study, degradability of 6:2 FTS under ultraviolet/persulfate (UV/PS) and ultraviolet/sulfite (UV/SF), which are typical technologies for advanced oxidation and reduction, were investigated respectively. Due to the hydrogenated moiety, 6:2 FTS was decomposed completely by UV/PS within 10 min, forming a mixture of short-chain perfluoroalkyl carboxylic acids with variable chain length (2-7 carbon atoms). Such oxidation products account for > 50% organofluorine of 6:2 FTS unmineralized portion. 6:2 FTS degradability under reductive UV/SF system was dramatically slowed down by the hydrogenated moiety, which lowered electron affinity and, consequently, reactivity with aqueous electron (eaq‾) produced by UV/SF. Fluorine mass balance showed that degradation intermediates were almost negligible: most of decomposed 6:2 FTS fluorine was converted to fluoride. A real 6:2 FTS-based CMS solution prepared from a commercial product was also tested. Both types of treatment were effective and in good agreement with the trends observed for tests with sole 6:2 FTS. Moreover, experimental results highlighted a remarkable amount of identifiable (like 4:2 FTS, 8:2 FTS and other per-/polyfluoroalkyl substances) and unidentifiable components in the CMS mixture. Indeed, fluoride concentration under UV/SF (73.8 mg/L) and UV/PS (44.9 mg/L) treatment were both higher than the estimated total concentration (<23 mg/L, according to 6:2 FTS concentration). Results strongly suggest that an oxidation pretreatment followed by reduction might be a better way to degrade and defluorinate 6:2 FTS and other precursors with non-fluorinated moieties, rather than employing single reduction or oxidation technology.

Characteristics of pharmaceutically active compounds in surface water in Beijing, China: Occurrence, spatial distribution and biennial variation from 2013 to 2017.

Pharmaceutically active compounds (PhACs) are widely found in the environment due to vast human consumption. Lots of work has been devoted to investigating the occurrence and seasonal variations globally. To fully understand characteristics and cross-year variation of PhACs in Beijing, 35 PhACs were analyzed in 46 sites across Beijing from both urban and suburban areas. Concentrations of target PhACs were ranged from levels of ng L-1 to µg L-1. Metoprolol (524 ng L-1), caffeine (390 ng L-1) and acetaminophen (156 ng L-1) were the three most abundant non-antibiotics with the highest median concentration, and nalidixic acid (135 ng L-1), erythromycin (64 ng L-1) and sulfamethoxazole (77 ng L-1) were the most abundant antibiotics. Urban and suburban areas are distinguished by PhAC composition in cluster analysis due to different wastewater collection rate. The ratio of easily removable compound group and hardly removable group was then proposed to reflect the wastewater collection rate. The compositional comparison of PhACs in WWTPs' effluents and their receiving rivers further illustrates the impact of WWTPs in urban area. Higher proportion of antibiotics (>30%) in suburban area reflected the impact of presence of livestock farms, which should be concerned. Further statistical analyses show an improving trend of wastewater collection rate, and excluding metoprolol, an anti-hypertension medicine, the total concentration of 13 target PhACs was reduced by 72% during 2013-2017.

Mechanochemical degradation of perfluorohexane sulfonate: Synergistic effect of ferrate(VI) and zero-valent iron.

Perfluorohexane sulfonate (PFHxS) has been newly recommended to be added into the Stockholm Convention on persistent organic pollutants (POPs). As one of the major perfluoroalkyl pollutants, its long half-time in human serum and neurotoxicity are cause for significant concern. Although mechanochemical degradation has been evaluated as a promising ecofriendly technology to treat pollutants, the extraordinary stability of poly- and perfluoroalkyl substances (PFASs) raises harsh requirements for co-milling reagents. In the present study, zero-valent iron (ZVI) and ferrate(VI) were for the first time used as the co-milling reagents to degrade PFHxS. When ZVI and ferrate(VI) were used alone, both the degradation and defluorination efficiencies were low. However, after milling at the optimum ratio (ferrate(VI):ZVI = 1:2) for 4 h, the synergistic effect of ZVI and ferrate(VI) resulted in almost complete degradation (100%) and defluorination (95%). Two points can account for this excellent performance: (1) the mechanochemical energy input in the system initiates and prominently promotes related reactions; and (2) the active species generated from the reactions among ZVI, ferrate(VI) and other high-valent iron species will accelerate the process of electron transfer. The sulfonate group comprises the favorable attack sites, as corroborated by both the identified intermediates and quantum chemical calculations. The homolysis of the C-S bond is not only the triggering step, but also the rate-limiting step. In summary, the present work confirms the feasibility and underlying mechanism of the ZVI-ferrate(VI) co-milling system to defluorinate PFHxS, which might be a promising technology to treat PFASs in solid wastes.

Effect of high energy ball milling on organic pollutant adsorption properties of chitosan.

In the present work, chitosan physicochemical transformations that occur during high energy ball milling are investigated and correlated with adsorption capacity of organic pollutants (using azo-dye reactive red 2 as molecular probe). Experimental results reveal that chitosan ball milled for 1 h shows a 70% increase of adsorption capacity, compared to unmilled one, while longer milling time causes a sensible reduction of such capacity. This trend correlates with specific surface area evolution under milling, thus suggesting the primary role of particle comminution in augmenting chitosan adsorption properties. Amorphization of particle surface was found to be marginally relevant for adsorption capacity enhancement. Maximum adsorption capacity (estimated by isothermal equilibrium study) and adsorption rate are augmented by ball milling, with an optimal value found at 1 h milling. Finally, the milled materials were tested to adsorb perfluorooctane sulfonate, obtaining 1.54 mmol g-1 uptake with 1 h milled chitosan. This suggests that chitosan could be used as a cheap expendable material to remove those pollutants, like perfluorooctane sulfonate and the other perfluoroalkyl substances, that deserves destruction and cannot be removed by conventional degradation technologies.

Ultrasound-Assisted Preparation of Chitosan/Nano-Activated Carbon Composite Beads Aminated with (3-Aminopropyl)Triethoxysilane for Adsorption of Acetaminophen from Aqueous Solutions.

A composite chitosan/nano-activated carbon (CS-NAC) aminated by (3-aminopropyl)triethoxysilane (APTES) was prepared in the form of beads and applied for the removal of acetaminophen from aqueous solutions. NAC and APTES concentrations were optimized to obtain a suitable adsorbent structure for enhanced removal of the pharmaceutical. The aminated adsorbent (CS-NAC-APTES beads) prepared with 40% w/w NAC and 2% v/v APTES showed higher adsorption capacity (407.83 mg/g) than CS-NAC beads (278.4 mg/g). Brunauer-Emmett-Teller (BET) analysis demonstrated that the surface area of the CS-NAC-APTES beads was larger than that of CS-NAC beads (1.16 times). The adsorption process was well fitted by the Freundlich model (R2 > 0.95), suggesting a multilayer adsorption. The kinetic study also substantiated that the pseudo-second-order model (R2 > 0.98) was in better agreement with the experimental data. Finally, it was proved that the prepared beads can be recycled (by washing with NaOH solution) at least 5 times before detectable performance loss.

Cross-linked chitosan/zeolite as a fixed-bed column for organic micropollutants removal from aqueous solution, optimization with RSM and artificial neural network.

Organic micropollutants (MPs) in low concentrations can affect aquatic ecosystems and human health. Adsorption technique is one of the promising methods to remove MPs. Chitosan and zeolites are environmentally friendly and low-cost adsorbents. Thus, removal of organic MPs (such as bisphenol A (BPA), carbamazepine (CBZ), ketoprofen (KTF) and tonalide (TND) from aqueous solution via cross-linked chitosan/zeolite, as a fixed-bed column, was investigated in the current study. Hydraulic retention time was set at 0.8 h pH and concentration of organic MPs ranged from 4 to 8 and 0.50 mg/L to 2.0 mg/L, and they were considered as factors in optimizing the removal of pollutants via response surface methodology (RSM). Approximately 1.4560 mg/L (89.0%) of BPA, 1.4724 mg/L (90.0%) of CBZ, 1.4920 mg/L (91.2%) of KTF and 1.4118 mg/L (86.3%) of TND were removed at 5.1 pH and 1.636 mg/L initial concentration as the optimum removal efficiency on the basis of RSM. Artificial neural network (ANN) was used to optimise removal effectiveness for each MP. The high R2 values and reasonable mean squared errors indicated that ANN optimized MP removal in a logical aspect. Adsorption isotherm studies revealed that organic MP removal through chitosan/zeolite could be explained with Freundlich and Langmuir isotherms.

Removal of F-53B as PFOS alternative in chrome plating wastewater by UV/Sulfite reduction.

Chrome mist suppressants are key chemicals used in the chrome plating industry to reduce exposure of workers by inhalation to airborne chromic acid pollution. Perfluoroalkyl sulfonated compounds are excellent mist suppressants, thanks to their chemical stability and surface activity. Therefore, despite mounting evidence for their persistence, bioaccumulation and toxicity, it is likely that such chemicals will continue to be used for the foreseeable future because of their importance and lack of alternatives. The present study is aimed at assessing the feasibility of advanced reduction as an effective technology to treat chrome plating industry wastewater. In particular, wastewater containing a chlorinated polyfluorinated ether sulfonate (i.e. F-53B), an alternative to perfluorooctanesulfonate (PFOS) used to prepare chrome mist suppressant in China, was treated by UV-activated sulfite. Results demonstrates that in ultrapure water F-53B can be easily degraded within 1 min-much faster than PFOS. Stoichiometric fluoride recovery was also achieved, confirming significant defluorination of the pollutant. Such superior reducibility was due to the presence of chlorine atoms, as corroborated by quantum chemical calculations. F-53B degradation was also achieved in chrome plating industrial wastewater, which yielded results were slower than those achieved in the laboratory nonetheless obtained complete abatement within 60 min. These results suggest that the proposed advanced reduction process is one of the safest options to control PFAS discharge in the environment and reduce the related risks to ecosystems.

Synthesis and Regeneration of A MXene-Based Pollutant Adsorbent by Mechanochemical Methods.

In the present study, an adsorbent material for removal of organic contaminants in wastewater is synthetized by a green and facile mechanochemical method. It is composed of Ti3C2Tx MXene layers (obtained by mechanochemical etching of MAX phase with concentrated HF) pillared with terephthalate by rapid direct reaction. Such material shows high specific surface area (135.7 m2 g-1) and excellent adsorption capability of methylene blue (209 mg g-1) because of the larger interlayer space among MXene sheets and free carboxylate groups of terephthalate. The spent adsorbent is reutilized (with addition of sole aluminum) to synthetize the MAX phase by mechanochemical procedure, where the terephthalate and the pollutant are carbonized into the carbide. In this way, new MXene-based adsorbent can be re-synthetized for further use.

Wastewater-based epidemiology in Beijing, China: Prevalence of antibiotic use in flu season and association of pharmaceuticals and personal care products with socioeconomic characteristics.

Wastewater-based epidemiology is an emerging field that has mostly been applied to investigate consumption of illicit drugs. In this study, the wastewater-based epidemiology approach was employed to study consumption of pharmaceuticals and personal care products (PPCPs) and measure their prevalence of use in eight densely populated, urban areas of Beijing, China. Ammonium loads were used to estimate the population equivalents of each sewershed. These estimates were applied to calculate population-normalized antibiotic consumption and prevalence of use during flu season, when antibiotics are frequently misused as a medical treatment. Results indicated that 21.9 g d-1 (104 people)-1 of ten popular antibiotics were consumed across the eight sewersheds, indicating that 1.98‰ of the 12.5 million population equivalents used these antibiotics during the sampling period. A comparison of these results to calculations made using previously reported data from 2013 suggest that recent Chinese antibiotic control policies have been effective. Uncertainty analyses were conducted to identify the 95% confidence range for antibiotic prevalence of use as 1.44-3.61‰. Human excretion factors were identified as the most sensitive variable. The wastewater-based epidemiology methods were also applied to a wider range of PPCPs, and the results indicated positive relationships between consumption and socioeconomic factors, such as housing price and population density. Overall, this work provides important public health information on antibiotic use and elucidates relationships between PPCP consumption and socioeconomic characteristics.

Degradation of Ofloxacin by Perylene Diimide Supramolecular Nanofiber Sunlight-Driven Photocatalysis.

This study describes a promising sunlight-driven photocatalyst for the treatment of ofloxacin and other fluoroquinolone antibiotics in water and wastewater. Perylene diimide (PDI) supramolecular nanofibers, which absorb a broad spectrum of sunlight, were prepared via a facile acidification polymerization protocol. Under natural sunlight, the PDI photocatalysts achieved rapid treatment of fluoroquinolone antibiotics, including ciprofloxacin, enrofloxacin, norfloxacin, and ofloxacin. The fastest degradation was observed for ofloxacin, which had a half-life of 2.08 min for the investigated conditions. Various light sources emitting in the UV-vis spectrum were tested, and blue light was found to exhibit the fastest ofloxacin transformation kinetics due to the strong absorption by the PDI catalyst. Reactive species, namely, h+, 1O2, and O2•-, comprised the primary photocatalytic mechanisms for ofloxacin degradation. Frontier electron density calculations and mass spectrometry were used to verify the major degradation pathways of ofloxacin by the PDI-sunlight photocatalytic system and identify the transformation products of ofloxacin, respectively. Degradation mainly occurred through demethylation at the piperazine ring, ketone formation at the morpholine moiety, and aldehyde reaction at the piperazinyl group. An overall mechanism was proposed for ofloxacin degradation in the PDI-sunlight photocatalytic system, and the effects of water quality constituents were examined to determine performance in real water/wastewater systems. Ultimately, the aggregate results from this study highlight the suitability of the PDI-sunlight photocatalytic system to treat antibiotics in real water and wastewater systems.

Degradation of PFOA Substitute: GenX (HFPO-DA Ammonium Salt): Oxidation with UV/Persulfate or Reduction with UV/Sulfite?

Hexafluoropropylene oxide dimer acid (HFPO-DA, ammonium salt with trade name: GenX) has been recently detected in river water worldwide. There are significant concerns about its persistence, and potential adverse effects to the biota. In this study, the degradability of GenX by typical advanced redox technologies (UV/persulfate and UV/sulfate) is investigated. Results demonstrate that <5% GenX is oxidized after 3 h in UV/persulfate system, which is much lower than ∼27% for PFOA. In comparison, GenX can be readily degraded and defluorinated by hydrated electron (eaq-) generated by UV/sulfite system. Specifically, GenX is not detectable after 2 h, and >90% of fluoride ion is recovered 6 h later. This is attributed to the accumulation and subsequent degradation of CF3CF2COOH and CF3COOH, which are stable intermediates of GenX degradation. Mechanistic investigations suggest that the etheric bond in the molecule is a favorable attack point for the eaq-. Such finding is corroborated by quantum chemical calculations. The side CF3- at the α-carbon probably acts as an effective barrier that prevents GenX from being cleaved by SO4-• or OH• at its most sensible point (i.e. the carboxyl group). This study illustrates that reduction by UV/sulfite might be a promising technology to remove GenX from contaminated water.

Mechanochemical enhancement of the natural attenuation capacity of soils using two organophosphate biocides as models.

Mechanochemical treatment by high energy ball milling is a promising technology to safely destroy organic pollutants in contaminated soil and allow its possible beneficial reuse. The present study investigates the mechanochemical activation of four major soil components, which induces generation of electrons on particle surfaces. Such phenomenon is demonstrated to occur on oxides by formation of trapped electrons in oxygen vacancies (following a zeroth-order kinetics), as well as on quartz and clayey materials to form fresh electron-rich surfaces by homolytic bond rapture (according to a first-order kinetics). Two toxic organophosphate biocides (i.e. chlorpyrifos and glyphosate) are used as model pollutants. Results show that the aromatic structure of chlorpyrifos determines a faster degradation rate, compared to the aliphatic one of glyphosate, because of the higher stability of generated radical intermediates. Moreover, the aromatic moiety facilitates adsorption on clays, thus temporarily sequestering the molecule and delaying its degradation. The many heteroatoms in both organophosphates have analogous fate: mineralization to inorganic form.

Typical pharmaceuticals in major WWTPs in Beijing, China: Occurrence, load pattern and calculation reliability.

Pharmaceutically active compounds (PhACs) are recognized as one of the most serious emerging micropollutants. Wastewater treatment plants are the major way through which such contaminants enter the environment. Therefore, an appropriate management of PhACs in these facilities can reduce their release into the environment. In particular, a proper sampling methodology is necessary to identify and quantify micropollutants in wastewater. In this study, 37 pharmaceuticals (including 23 antibiotics) are investigated in eight major wastewater treatment plants in Beijing. An optimized sampling methodology is successfully implemented to monitor bihourly variation of the contaminants, thus averting uncertainties derived from conventional sampling methods. In this way, more accurate pharmaceutical load patterns are determined and discussed. Thanks to the synchronous data on pharmaceutical concentration and wastewater flow, we also compare performances of various treatment processes and optimize different calculation methods for removal efficiency.

Correction to: Formation of brominated and chlorinated dioxins and its prevention during a pilot test of mechanochemical treatment of PCB and PBDE contaminated soil.

The destruction of persistent organic pollutants(POPs) is a large challenge in particular in developing and emerging economies.