Synthesis of CaCO3 supported nano zero-valent iron-nickel nanocomposite (nZVI-Ni@CaCO3) and its application for trichloroethylene removal in persulfate activated system.

Nano zero-valent (nZVI) based composite have been widely utilized in environmental remediation. However, the rapid agglomeration and quick deactivation of nZVI limited its application on large scale. In this work, CaCO3 supported nZVI-Ni catalyst, namely nZVI-Ni@CaCO3 was prepared and used for the efficient removal of trichloroethylene (TCE) in PS oxidation process. The successful disbursement of nZVI-Ni on CaCO3 support material not only increased the surface area of nZVI-Ni@CaCO3 (69.45 m2/g) with respect to CaCO3 (5.92 m2/g) and bare nZVI (13.29 m2/g) but also improved the catalytic activity. XRD, XPS and FTIR analysis confirmed the successful formation of nZVI-Ni@CaCO3 nanoparticles. The nZVI-Ni@CaCO3 nanoparticles combined with PS had achieved complete removal of TCE (99.8%) with dosage of 36 mg/L and 1.34 mM respectively. These results showed that the use of CaCO3 as support material for nZVI-Ni could have significant influence on contaminant removal process. Scavenging and EPR tests validated the existence of SO4•-, OH• and O2•- radicals in PS/nZVI-Ni@CaCO3 system and highlighted the dominant role of SO4•- radicals in TCE removal process. HCO3- ions and humic acid have shown adverse effect on TCE removal due to radical scavenging and buffering effect. Owing to improved catalytic activity and easy preparation, the nZVI-Ni@CaCO3 nanoparticles could be served as an alternative strategy for environmental remediation.

Innovative strategy for the effective utilization of coal waste slag in the Fenton-like process for the degradation of trichloroethylene.

In response to environmental concerns at the global level, there is considerable momentum in the exploration of materials derived from waste that are both sustainable and eco-friendly. In this study, CS-Fe (carbon, silica, and iron) composite was synthesized from coal gasification slag (CGS) and innovatively applied as a catalyst to activate PS (persulfate) for the degradation of trichloroethylene (TCE) in water. Scanning electron microscope (SEM), fourier transmission infrared spectroscopy (FTIR), energy dispersive x-ray spectroscopy (EDS), brunauer, emmet, and teller (BET) technique, and x-ray diffractometer (XRD) spectra were employed to investigate the surface morphology and physicochemical composition of the CS-Fe composite. CS-Fe catalyst showed a dual nature by adsorption and degradation of TCE simultaneously, displaying 86.1% TCE removal in 3 h. The synthesized CS-Fe had better adsorption (62.1%) than base material CGS (36.4%) due to a larger BET surface area (770.8 m2 g-1), while 24.0% TCE degradation was recorded upon the activation of PS by CS-Fe. FTIR spectra confirmed the adsorption and degradation of TCE by investigating the used and fresh samples of CS-Fe catalyst. Scavengers and Electron paramagnetic resonance (EPR) analysis confirmed the availability of surface radicals and free radicals facilitated the degradation process. The acidic nature of the solution favored the degradation while the presence of bicarbonate ion (HCO3-) hindered this process. In conclusion, these results for real groundwater, surfactant-added solution, and degradation of other TCE-like pollutants propose that the CS-Fe composite offers an economically viable and favorable catalyst in the remediation of organic contaminants within aqueous solutions. Further investigation into the catalytic potential of coal gasification slag-based carbon materials and their application in Fenton reactions is warranted to effectively address a range of environmental challenges.

Ascorbic acid enhanced the circulation between Fe(II) and Fe(III) in peroxymonosulfate system for fluoranthene degradation.

In this research, ascorbic acid (AA) was used to enhance Fe(II)/Fe(III)-activated permonosulfate (PMS) systems for the degradation of fluoranthene (FLT). AA enhanced the production of ROS in both PMS/Fe(II) and PMS/Fe(III) systems through chelation and reduction and thus improved the degradation performance of FLT. The optimal molar ratio in PMS/Fe(II)/AA/FLT and PMS/Fe(III)/AA/FLT processes were 2/2/4/1 and 5/10/5/1, respectively. In addition, the experimental results on the effect of FLT degradation under different groundwater matrixes indicated that PMS/Fe(III)/AA system was more adaptable to different water quality conditions than the PMS/Fe(II)/AA system. SO4·- was the major reactive oxygen species (ROS) responsible for FLT removal through the probe and scavenging tests in both systems. Furthermore, the degradation intermediates of FLT were analyzed using gas chromatograph-mass spectrometry (GC-MS), and the probable degradation pathways of FLT degradation were proposed. In addition, the removal of FLT was also tested in actual groundwater and the results showed that by increasing the dose and pre-adjusting the solution pH, 88.8 and 100% of the FLT was removed for PMS/Fe(II)/AA and PMS/Fe(III)/AA systems. The above experimental results demonstrated that PMS/Fe(II)/AA and PMS/Fe(III)/AA processes have a great perspective in practice for the rehabilitation of FLT-polluted groundwater.

Estimating the Mass of Pharmaceuticals Harbored in Municipal Solid Waste Landfills by Analyzing Refuse Samples at Various Ages and Depths.

Pharmaceuticals have been detected at high concentrations in municipal solid waste (MSW) landfill leachates, which are recognized as an underestimated source of pharmaceutical residues in the environment. However, limited efforts have been made to characterize pharmaceuticals in MSW landfill refuse, which is also of significant concern given the potential long-term environmental impact. Herein, we excavated landfill refuse from six cells with landfill ages of 7-27 years in the largest MSW landfill in Shanghai (in each cell, landfill refuse was collected from different depths of 2-8 m) and analyzed samples for the presence of 55 pharmaceuticals, including antibiotics and non-antibiotics. The results reveal the presence of 42 pharmaceuticals in landfill refuse, with median concentrations ranging from 0.30 to 116 µg/kg. Antibiotic and non-antibiotic pharmaceuticals exhibited diverse concentration trends with age, related to changes in policy intervention and consumption over time. Different concentration variations of individual pharmaceuticals were observed in refuse samples excavated at different depths and positively correlated to their sorption ability. The mass of pharmaceuticals in the investigated landfill was estimated from the obtained concentrations to be 80-220 tons with 95% probability, based on Monte Carlo analysis. To the best of our knowledge, this study provides the first estimate of pharmaceutical mass in an MSW landfill. The results will be helpful for understanding the potential long-term environmental impact of pharmaceuticals in landfills.

Synergistic enhanced activation of peroxymonosulfate by heterojunction Co3O4-CuO@CN for removal of oxytetracycline: Performance, mechanism, and stability.

Metal-organic frameworks (MOFs) as precursors for catalysts has drawn growing attentions. In this study, heterojunction Co3O4-CuO doped carbon materials (noted as Co3O4-CuO@CN) were prepared by direct carbonization of CuCo-MOF in air. It was found that the Co3O4-CuO@CN-2 exhibited excellent catalytic activity with the highest Oxytetracycline (OTC) degradation rate of 0.0902 min-1 at 50 mg/L of Co3O4-CuO@CN-2 dosage, 2.0 mM of PMS and 20 mg/L of OTC, which was 4.25 and 4.96 times that of CuO@CN and Co3O4@CN, respectively. Furthermore, Co3O4-CuO@CN-2 was efficient over a wide pH range (pH 1.9-8.4), and possessed good stability and reusability without OTC degradation decrease after five consecutive uses at pH 7.0. In a comprehensive analysis, the rapid regeneration of Cu(II) and Co(II) is responsible for their excellent catalytic performance, and the p-p heterojunction structure formed between Co3O4 and CuO acts as an intermediary of electron transfer to accelerate PMS decomposition. Moreover, it was interesting to find that Cu rather than Co species played a vital role in the PMS activation. The quenching experiments and electron paramagnetic resonance demonstrated that .OH, SO4•-, and 1O2 were the reactive species responsible for oxidation of OTC and the non-radical pathway triggered by 1O2 was dominant.

Simultaneous immobilization of heavy metals and nutrient elements in contaminated sediment using a novel composite agent product.

In this research, an innovative type of sediment resource treatment agent (SRA) was synthesized successfully, which could immobilize ammonia nitrogen (NH3-N), total phosphorus (TP), potassium (K), and simultaneously stabilize cadmium (Cd), lead (Pb), chromium (Cr), copper (Cu), nickel (Ni), and zinc (Zn) in dredged sediment. The effects of SRA dosage on stabilizing the nutrient elements and heavy metals were investigated. The results demonstrated that the increase of SRA dosage significantly enhanced the stabilization of nutrients and heavy metals. The 14-day rainwater infiltration and rainwater scouring experiments were carried out. With the simulation test of rainwater infiltration, the stabilization ratios of Cr, Cu, Ni, Pb, Zn, Cd, NH3-N, TP, and K with 2% SRA addition reached 80.8%, 76.8%, 80.3%, 77.5%, 78.0%, 72.7%, 64.3%, 73.9%, and 73.9%, respectively. Under the action of rainwater scouring, the stabilization ratios of Cr, Cu, Ni, Pb, Zn, Cd, NH3-N, TP, and K with 6.4% SRA addition reached 84.6%, 84.0%, 77.6%, 87.3%, 80.0%, 61.5%, 76.2%, 77.8%, and 91.7%, respectively. Therefore, the results demonstrate that SRA is an excellent composite material in stabilizing heavy metals while reserving the nutrients in dredged sediment, thus showing great potential in the application for dredged sediment resource treatment.

Rainfall Influences Occurrence of Pharmaceutical and Personal Care Products in Landfill Leachates: Evidence from Seasonal Variations and Extreme Rainfall Episodes.

Unused or expired pharmaceutical and personal care products (PPCPs) are usually discharged into municipal solid wastes, then travel to landfills, and eventually percolate into leachates. However, knowledge of their occurrence and temporal dynamics in leachates is limited, making landfill leachate an underappreciated emission source of PPCPs. Furthermore, the differences in PPCP variations in landfill leachates emphasize the necessity for identifying the influencing factors and elucidating the mechanisms for PPCP fluctuations. In this study, successive monthly monitoring of PPCPs in leachates throughout an entire year was performed to determine their seasonal variations and identify their influencing factors. Furthermore, five pairs of additional sampling campaigns were conducted before and after rainfall events during wet seasons to elucidate the influencing mechanisms. The results showed that there was a distinct seasonal variation in PPCPs in landfill leachates-elevated levels during the wet period (from April to September, with a mean concentration of 17.0 µg/L for total monitored PPCPs)-when compared to other months (mean concentration of 3.8 µg/L). Rainfall played a considerable role in mediating PPCP concentrations in leachates. The PPCP responses to five rainfall episodes further verified the influence of rainfall and demonstrated that the tendency to PPCP concentration increase was related to rainfall precipitation. Torrential rain events (i.e., 24 h cumulative precipitation of 50-99.9 mm) led to the most significant increases in PPCP concentrations in landfill leachates. In addition, the hydrophilicity of PPCPs contributed to the different fluctuations during the 1 year investigation and different responses to rainfall. To the best of our knowledge, this study provides the first direct evidence supporting the influence of rainfall on PPCPs in landfill leachates, which can help better understand the occurrence and behavior of emerging contaminants in this underappreciated emission source.

The performance of chlorobenzene degradation in groundwater: comparison of hydrogen peroxide, nanoscale calcium peroxide and sodium percarbonate activated with ferrous iron.

The chlorobenzene (CB) degradation performances by various oxidants, including hydrogen peroxide (H2O2), nanoscale calcium peroxide (nCaO2) and sodium percarbonate (SPC), activated with ferrous iron (Fe(II)) were investigated and thoroughly compared. The results showed that all tested systems had strong abilities to degrade CB. The CB removal rate increased with increasing dosages of oxidants or Fe(II) because the generation of reactive oxygen species could be promoted with the chemical dosages' increase. Response surface and contour plots showed that CB could achieve a better removal performance at the same H2O2 and Fe(II) molar content, but the Fe(II) dosage was higher than that of oxidants in the nCaO2 and SPC systems. The optimal molar ratios of H2O2/Fe(II)/CB, nCaO2/Fe(II)/CB and SPC /Fe(II)/CB were 5.2/7.6/1, 8/8/1, and 4.5/8/1, respectively, in which 98.1%, 98%, and 96.4% CB removals could be obtained in 30 min reaction. The optimal pH condition was around 3, while CB removal rates were less than 20% in all three systems when the initial pH was adjusted to 9. The oxidative hydroxyl radicals (HO•) and singlet oxygen (1O2) had been detected by the electron paramagnetic resonance test. Based upon the results of liquid chromatograph-mass spectrometer analysis, the pathways of CB degradation were proposed, in which 1O2 roles were elaborated innovatively in the CB degradation mechanism. The CB degradation performance was significantly affected in actual groundwater, while increasing the molar ratio of oxidant/Fe(II)/CB was an effective way to overcome the adverse effects caused by the complex of actual groundwater matrix.

Municipal Solid Waste Landfills: An Underestimated Source of Pharmaceutical and Personal Care Products in the Water Environment.

Pharmaceutical and personal care products (PPCPs) have been the focus of increasing concern in recent decades due to their ubiquity in the environment and potential risks. Out-of-date PPCPs are usually discharged into municipal solid wastes (MSWs), enter the leachates in MSW landfills, and have serious adverse effects on the surrounding water environment. However, the occurrence and removal of PPCPs from landfill leachates have rarely been examined to date. This lack of knowledge makes the landfill an underestimated source of PPCPs in the environment. In this review, we collected the relevant publications of PPCPs in landfill leachates, systematically summarized the occurrence of PPCPs in landfill leachates globally, evaluated the removal performances for various PPCPs by different types of on-site full-scale leachate treatment processes, and assessed the impacts of landfill leachates on PPCPs in the adjacent groundwater. In particular, influencing factors for PPCPs in landfill leachates, including the physicochemical properties of PPCPs, climate conditions, and characteristics of landfill sites (i.e., landfill ages) as well as sociological factors (i.e., economic development), were extensively discussed to understand their occurrence patterns. Future perspectives were also proposed in light of the identified knowledge gaps. To the best of our knowledge, this is the first review regarding the occurrence and removal of PPCPs from landfill leachates worldwide.

Enhancement of benzene degradation by persulfate oxidation: synergistic effect by nanoscale zero-valent iron (nZVI) and thermal activation.

The feasibility of an advanced oxidation process based upon sodium persulfate (SPS) activated simultaneously by heat (50 °C) and nanoscale zero-valent iron (nZVI) on benzene removal was investigated. The experimental results strongly showed the synergistic effect of thermal and nZVI activation to SPS and benzene removal was enhanced with the increase of SPS/nZVI/benzene molar ratio. Specifically, 94% of benzene could be removed in 1 hr at 50 °C at the SPS/nZVI/benzene molar ratio of 10/5/1. The radical scavenger tests and electron paramagnetic resonance (EPR) analysis confirmed that SO4•- was the predominant species contributing to benzene degradation. Further, the effects of the solution matrix on benzene elimination were investigated. The results indicated that benzene destruction in the thermally activated SPS/nZVI system performed better under acidic conditions, and the high concentration of both Cl- and HCO3 - had adverse effects on benzene elimination. The test for the performance of benzene degradation in the actual groundwater demonstrated that benzene could be degraded entirely at SPS/nZVI/benzene molar ratio of 40/40/1 at 50 °C, indicating that the synergistic catalysis of thermal and nZVI activation to SPS is exploitable and the thermally activated SPS/nZVI system can be applicable to the remediation of benzene contaminated groundwater.

Mechanism of carbon tetrachloride reduction in ferrous ion activated calcium peroxide system in the presence of methanol.

This study investigated the reductive initiation for the depletion of highly oxidized/perhalogenated pollutants, specifically the degradation of carbon tetrachloride (CT) was induced by adding methanol (MeOH) into a ferrous ion (Fe(II)) activated calcium peroxide (CaO2) system. The results indicated that CT could be completely degraded within 20 min at CaO2/Fe(II)/MeOH/CT molar ratio of 30/40/10/1 in this system. Scavenging tests suggested that both superoxide radical anion (O2 •-) and carbon dioxide radical anion (CO2 •-) were predominant reactive species responsible for CT destruction. Hydroxymethyl radicals (•CH2OH), an intermediate in the transformation of MeOH, could also initiate CT degradation by reducing C-Cl bond. GC/MS analysis identified CHCl3, C2Cl4, and C2Cl6 as the intermediates accompanied by CT destruction, and a reduction mechanism for CT degradation was proposed accordingly. In addition, the impact of solution matrix and initial solution pH were evaluated, and the results showed that Cl-, NO3 -, and HCO3 - had adverse effects on CT degradation. Moreover, the alkaline condition was unfavorable to CT depletion. In conclusion, the results obtained in the actual groundwater tests encouragingly demonstrated that the CaO2/Fe(II)/MeOH process is a highly promising technique for the remediation of CT-contaminated groundwater.

Insight into CaO2-based Fenton and Fenton-like systems: strategy for CaO2-based oxidation of organic contaminants.

This study conducted a comparison of the CaO2-based Fenton (CaO2/Fe(II)) and Fenton-like (CaO2/Fe(III)) systems on their benzene degradation performance. The H2O2, Fe(II), Fe(III), and HO● variations were investigated during the benzene degradation. Although benzene has been totally removed in the two systems, the variation patterns of the investigated parameters were different, leading to the different benzene degradation patterns. In terms of the Fe(II)/Fe(III) conversion, the CaO2/Fe(II) and CaO2/Fe(III) systems were actually inseparable and had the inherent mechanism relationships. For the CaO2/Fe(III) system, the initial Fe(III) must be converted to Fe(II), and then the consequent Fenton reaction could be later developed with the regenerated Fe(II). Moreover, some benzene degradation intermediates could have the ability to facilitate the transformation of the Fe(III) to Fe(II) without the classic H2O2-associated propagation reactions. By varying the Fe(II) dosing method, an effective degradation strategy has been developed to take advantage of the two CaO2-based oxidation systems. The proposed strategy was further successfully tested in TCE degradation, therefore extending the potential for the application of this technique.

Degradation of trichloroethylene in aqueous solution by nanoscale calcium peroxide in the Fe(II)-based catalytic environments.

In this study, nCaO2 was synthesized successfully and applied in the Fe(II)-based catalytic environments in investigating trichloroethylene (TCE) removal performance. nCaO2 with the particle sizes in the range of 50-200 nm was prepared, and it performed better for TCE removal when compared to the conventional CaO2. Further experimental results showed that 70.4% of TCE could be removed in 180 min at the nCaO2/Fe(II)/TCE molar ratio of 1/2/1, while this data was elevated to 86.1% in the presence of citric acid (CA) at the nCaO2/Fe(II)/CA/TCE molar ratio of 1/2/2/1 in the same test period. Probe compound tests, specifically designed for free radicals confirmation, demonstrated the presence of HO• and O2 -•. Moreover, scavenging tests indicated that HO• was the major radical responsible for TCE degradation but O2 -• promoted the removal of TCE in both nCaO2/Fe(II) and nCaO2/Fe(II)-CA system. In addition, the effects of initial solution pH and anions (Cl-, HCO3 -) were also evaluated. The performance of TCE degradation in actual groundwater demonstrated that both nCaO2/Fe(II) and nCaO2/Fe(II)-CA systems can be applicable for TCE removal in ISCO practice and the nCaO2/Fe(II)-CA system is much promising technique. These fundamental data strongly confirmed the feasibility and potential of nCaO2 based technique in the remediation of TCE contaminated groundwater.

Electrolytic control of hydrogen peroxide release from calcium peroxide in aqueous solution.

The in situ generation of hydrogen peroxide (H2O2) for water treatment is more practical than the use of liquid H2O2, which is costly to store and transport. Calcium peroxide (CaO2), a solid carrier of H2O2, can release H2O2 on dissolution in water. However, the constant H2O2 release rate of CaO2 has been a bottleneck constraining its wider application. In this study, a practical electrochemical method using a divided cell is developed to control the rate of release of H2O2 from CaO2. The results show that the rate of H2O2 release from CaO2 is enhanced in the anolyte. The increase in H2O2 release is positively correlated with the current. Under a current of 100 mA, the H2O2 concentration was 2.5 times higher after 30 min of electrolysis than in the control experiment in which no current was applied. Water electrolysis in the anodic compartment generates protons that not only: (i) en-hance dissolution of CaO2 and release of H2O2, but also (ii) neutralize the alkaline pH resulting from CaO2 dissolution, thus providing new advantages for the use of CaO2. This effective technique may be suitable for the sophisticated control of H2O2 release in environmental applications.

Insight on the generation of reactive oxygen species in the CaO2/Fe(II) Fenton system and the hydroxyl radical advancing strategy.

Calcium peroxide (CaO2) is a stable hydrogen peroxide (H2O2) carrier, and the CaO2/Fe(II) system has been applied for treatment of various pollutants. It is commonly reported in the literature that hydroxyl radical (HO●) and superoxide radical anions (O2 ●-) are the two main reactive oxygen species (ROSs) generated in the CaO2/Fe(II) system. However, many of the reported results were deduced from degradation performance rather than specific testing of radical generation. Thus, the specific generation of ROSs and the influence of system conditions on ROSs yield is still unclear. To our knowledge, this is the first study specifically focusing on the generation of HO● and O2 ●- in the CaO2/Fe(II) system. Experimental conditions were optimized to investigate the production of HO● and O2 ●-. The results showed the influences of CaO2, Fe(II), and solution pH on HO● and O2 ●- generation, and the HO● generation efficiency was reported for the first time. In addition, the ROSs generation pathways in the CaO2/Fe(II) system were elucidated. A strategy for enhancing HO● yield is developed, based on the continuously dosing Fe(II). This proposed strategy has implications for the effective application of in situ chemical oxidation employing CaO2/Fe(II) for groundwater remediation.

A picture of pharmaceutical pollution in landfill leachates: Occurrence, regional differences and influencing factors.

Municipal solid waste (MSW) landfill sites have been identified as a significant source of pharmaceuticals in the environment because unused or expired pharmaceuticals are discarded into MSW, which eventually percolate into leachates. However, the contamination of pharmaceuticals in landfill leachate in China is not comprehensively understood. Previous research into factors influencing pharmaceutical concentrations focused on a limited number and type of target pollutants or restricted study area. In the present study, 66 pharmaceuticals were analyzed (including 45 antibiotic and 21 non-antibiotic pharmaceuticals, also categorized as 59 prescription and 7 non-prescription pharmaceuticals) in leachate samples from landfill sites with various characteristics in different regions of China. The results indicated that non-antibiotic pollutants were present at significantly higher concentrations than antibiotic pollutants, with median concentrations of 1.74 µg/L and 527 ng/L, respectively. Non-antibiotic pollutants also presented a higher environmental risk than antibiotic pollutants, by 2 to 4 orders of magnitude, highlighting that non-antibiotic pharmaceuticals should not be overlooked during the assessment of landfill leachate. Pharmaceutical concentrations in landfill leachate samples exhibited regional differences; the population size served by the landfills was the dominant factor contributing to the observed differences. In addition, landfill characteristics such as the solid waste composition and MSW loading can also affect pharmaceutical concentrations in landfill leachate. Despite the implementation of the classification and disposal policy of MSW in Shanghai, China since July 2019, specifying that unused or expired pharmaceuticals should be discarded as hazardous waste, high levels of pharmaceutical contaminations were detected in leachate from the main components of classified MSW (i.e., residual and food waste). These findings emphasize the importance of pharmaceutical management in solid waste systems.

Occurrence, behaviors, and fate of per- and polyfluoroalkyl substances (PFASs) in typical municipal solid waste disposal sites.

Per- and polyfluoroalkyl substances (PFASs) have become a crucial environmental concern owing to their exceptional persistence, ability to bioaccumulate within ecosystems, and potential to adversely affect biota. Products and materials containing PFASs are usually discarded into municipal solid waste (MSW) at the end of their life cycle, and the fate of PFASs may differ when different disposal methods of MSWs are employed. To date, limited research has focus on the occurrence, behaviors, and fate of PFASs emitted from various MSW disposal sites. This knowledge gap may lead to an underestimation of the contribution of MSW disposal sites as a source of PFASs in the environment. In this review, we collated publications concerning PFASs from typical MSW disposal sites (i.e., landfills, incineration plants, and composting facilities) and explored the occurrence patterns and behaviors of PFASs across various media (e.g., landfill leachate/ambient air, incineration plant leachate/ash, and compost products) in these typical MSW disposal sites. In particular, this review highlighted ultrashort-chain perfluoroalkyl acids and "unknown"/emerging PFASs. Additionally, it meticulously elucidated the use of non-specific techniques and non-target analysis for screening and identifying these overlooked PFASs. Furthermore, the composition profiles, mass loads, and ecological risks of PFASs were compared across the three typical disposal methods. To the best of our knowledge, this is the first review regarding the occurrence, behaviors, and fate of PFASs in typical MSW disposal sites on a global scale, which can help shed light on the potential environmental impacts of PFASs harbored in MSWs and guide future waste management practices.

Surfactant enhanced persulfate system for the synergistic oxidation and reduction of mixed chlorinated hydrocarbons.

Surfactant-enhanced in-situ chemical oxidation (S-ISCO) is widely applied in soil and groundwater remediation. However, the role of surfactants in the reactive species (RSs) transformation remains inadequately explored. This work introduced nonionic surfactant Tween-80 (TW-80) into a nano zero-valent iron (nZVI) activated persulfate (PS) system. The findings indicate that PS/nZVI/TW-80 system can realize the concurrent removal of trichloroethylene (TCE), tetrachloroethene (PCE), and carbon tetrachloride (CT), whereas CT cannot be eliminated without TW-80 presence. Further analysis unveiled that hydroxyl (HO•) and sulfate radicals (SO4－•) were the primary species for TCE and PCE degradation, while CT was reductively eliminated by surfactant radicals generated from TW-80. Moreover, the surfactant radicals were found to accelerate Fe(III)/Fe(II) cycle, reduce the production of iron sludge, and increase PS decomposition. The possible degradation routes of mixed chlorinated hydrocarbons (CHCs) and the decomposition pathways of TW-80 were proposed through the density function theory (DFT) calculation and intermediates analysis. Additionally, the effects of other nonionic surfactants on the simultaneous removal of TCE, PCE, and CT, and the practical applications using the actual contaminated groundwater were also evaluated. This study provides theoretical support for the simultaneous removal of CHCs, particularly those containing perchlorinated contaminants, using the S-ISCO techniques.

Insights into enhanced removal of fluoranthene by sulfidated nanoscale zero-valent iron: In aqueous solution and soil slurry.

In this study, 90.9% fluoranthene (FLT) was degraded in sodium percarbonate (2Na2CO3·3H2O2, SPC) oxidation system by Fe(II) combined with sulfidated nano zero valent iron (S-nZVI) activation within 60 min in aqueous solution. Scavenging experiments and electron paramagnetic resonance detection suggested that HO•, O2-•, and 1O2 contributed to the removal of FLT in SPC/Fe(II)/S-nZVI system. Based on the FLT degradation intermediates that were analyzed by GC-MS in SPC/Fe(II)/S-nZVI process, three potential FLT degradation pathways were speculated. The removal efficiency of FLT was inhibited with the presence of humic acid (HA) unless the concentration of HA was controlled at 1.0 mg L-1, and the presence of 1.0 mg L-1 HA favored the generation of HO•. The excellent removal performance of FLT (88.6%) could be achieved in actual groundwater by increasing the chemical dosages and adjusting the initial solution pH to acid environment. In soil slurry tests, the optimal reaction time and soil/water ratio were obtained as 24 h and 2/10, respectively, and the desired FLT degradation performances were obtained at pH 3 and 5 with the soil/water ratio of 2/10. This work effectively demonstrates the application potential of SPC/Fe(II)/S-nZVI system for the remediation of PAHs contamination in actual industrial sites.

Efficient degradation of trichloroethene with the existence of surfactants by peroxymonosulfate activated by nano-zero-valent iron: performance and mechanism investigation.

In this study, the degradation of trichloroethylene (TCE) with the existence of tween-80 (TW-80) or sodium dodecyl sulfate (SDS) using peroxymonosulfate (PMS) activated by nano-zero-valent iron (nZVI) was investigated. Over 87.6% TCE (with 1.3 g L-1 TW-80 presence) was degraded by 0.9 mM PMS and 0.12 g L-1 nZVI, while 89.7% TCE (with 2.3 g L-1 SDS presence) was degraded by 1.2 mM PMS and 0.20 g L-1 nZVI, in which more than 71.9% TCE with TW-80 existence and 87.5% TCE with SDS existence were dechlorinated. Besides, the effects of some factors (i.e., PMS and nZVI dosages, initial solution pH, and inorganic anions) on TCE removal were evaluated. The degradation of TCE was restrained continuously with increasing surfactant concentration, and TW-80 was more easily decomposed than SDS in PMS/nZVI system. Furthermore, sulfate radical (SO4-•) and hydroxyl radical (HO•) were demonstrated the main reactive oxygen species (ROS) contributing to TCE degradation and SO4-• played a dominant role through EPR tests and ROS scavenging experiments. Finally, the results of TCE degradation in actual groundwater confirmed that PMS/nZVI process has great advantages and potential in remediation of actual TCE-contaminated groundwater with TW-80 or SDS existence.