Superior trichloroethylene removal from water by sulfide-modified nanoscale zero-valent iron/graphene aerogel composite.

Sulfide-modified nanoscale zero-valent iron (S-nZVI) is a promising material for removal of organic pollutants from water, but S-nZVI nanoparticles (NPs) easily agglomerate and have poor contact with organic contaminants. Herein, we propose a new S-nZVI/graphene aerogel (S-nZVI/GA) composite which exhibits superior removal capability for trichloroethylene (TCE) from water. Three-dimensional porous graphene aerogel (GA) can improve the efficiency of electron transport, enhance the adsorption of organic pollutants and restrain the agglomeration of the core-shell S-nZVI NPs. The TCE removal rates of FeS, nZVI, GA and S-nZVI were 27.8%, 42%, 63% and 75% in 2 hr, respectively. Furthermore, TCE was completely removed within 50 min by S-nZVI/GA. The TCE removal rate increased with increasing pH and temperature, and TCE removal followed the pseudo-first-order kinetic model. The results demonstrate the great potential of S-nZVI/GA composite as a low-cost, easily separated and superior monolithic adsorbent for removal of organic pollutants.

Immobilization of cadmium in river sediments by different modified nanoscale zero-valent iron: performance, mechanisms, and Fe dissolution.

Modified nanoscale zero-valent iron (NZVI) exhibited great potential for the remediation of heavy metal contaminated river sediments, but its mechanisms and environmental risks are still unclear. This study systematically discussed the performance and the mechanisms of modified NZVI materials, i.e., sodium alginate-coated NZVI (SNZVI), rhamnolipid-coated NZVI (RNZVI), and graphene oxide-loaded NZVI (GNZVI), for the stabilization of Cd in sediment, with the exploration of their stability to Cd at various pH values and Fe dissolution rate. Compared with the control, the toxicity characteristic leaching procedure (TCLP) leachable Cd decreased by 52.66-96.28%, and the physiologically based extraction test (PBET) extractable Cd decreased by 44.68-70.21% after 56 days of incubation with the immobilization efficiency varying according to GNZVI > RNZVI > SNZVI > NZVI. Besides, the adsorption behavior of Cd on materials was fitted with the Freundlich model and classified as an endothermic, spontaneous, and chemical adsorption process. SEM-EDX, XRD, and FTIR results verified that the stabilization mechanisms of Cd were principally based on the adsorption, complexation of Cd2+ with secondary Fe minerals (including Fe2O3, γ-Fe2O3, and γ-FeOOH) and precipitation (Cd(OH)2). From the risk assessment results, it was observed that the materials were favorable for Cd stabilization at a pH range from 7 to 11, meanwhile, the leaching concentration of Fe in the overlying water was detected below the limit value. These findings pave the way to developing an effective strategy to remediate Cd contaminated river sediments.

Removal of chloramphenicol by sulfide-modified nanoscale zero-valent iron activated persulfate: Performance, salt resistance, and reaction mechanisms.

Herein, sulfide-modified nanoscale zero-valent iron (S-nZVI) was prepared by a liquid-phase reduction route and then applied to activate persulfate (PS) for the degradation of chloramphenicol (CAP). The effects of Fe/S molar ratio, catalyst dosage, PS concentration, initial pH, and co-existing ions (Cl-, SO42-, CO32-) on the catalytic performance of S-nZVI/PS system were investigated. Simultaneously, the fluctuations of solution pH, oxidation-reduction potential, dissolved oxygen, and Fe2+ concentration were also monitored during the reaction. Results shown that 98.8 % of CAP could be removed under the optimum reaction conditions (S-nZVI dosage = 0.1 g/L, PS concentration = 3 mM, initial pH = 6.86). Compared to the pristine nZVI, the sulfidation behavior could critically improve the removal efficiency of CAP, ascribe to the enhancements of hydrophobicity of nZVI, production of hydroxyl radicals, and salt resistance. Furthermore, possible degradation pathways of CAP in S-nZVI/PS system were inferred based on liquid chromatography-mass spectrometry (LC-MS) and density functional theory (DFT) calculations. This study proves that the S-nZVI is a more promising catalyst for activating PS than nZVI, especially in the field of saline pharmaceutical wastewater treatment.

Role of sulfide-modified nanoscale zero-valent iron on carbon nanotubes in nonradical activation of peroxydisulfate.

Sulfamethoxazole (SMX) is highly persistent and difficult to remove, making it urgent to find an efficient method for alleviating the enormous environmental pressure of SMX. In this study, sulfide-modified nanoscale zero-valent iron on carbon nanotubes (S-nZVI@CNTs) was prepared to activate peroxydisulfate (PDS) for the degradation of SMX. The results showed that SMX was completely removed within 40 min (kobs=0.1058 min-1) in the S-nZVI@CNTs/PDS system. By analyzing quenching experiments and electron paramagnetic resonance (EPR), singlet oxygen (1O2) was the main active species of the S-nZVI@CNTs/PDS system. 1O2 might be mediated by the abundant carbonyl groups (CO) on carbon nanotubes through spectroscopic analyses. In addition, sulfur doping transitioned the activation pathway to a nonradical pathway. Spectroscopic analyses and electrochemical experiments confirmed that the formation of CNTs-PDS complexes and S-nZVI could promote electron transfer on the catalyst surface. Furthermore, the main degradation intermediates of SMX were identified, and five possible transformation pathways were proposed. The S-nZVI@CNTs/PDS system possessed advantages including high anti-interference (Cl-, NO3-, HA), a strong applicability, recyclability and a low PDS consumption, offering new insight into the degradation of antibiotic wastewater.

Enhanced degradation of bisphenol S by persulfate activated with sulfide-modified nanoscale zero-valent iron.

Sulfide-modified nanoscale zero-valent iron (S-nZVI) has been considered an efficient material to remove heavy metals and organic contaminants. The experiments of bisphenol S (BPS) degradation by persulfate (PS) activated with S-nZVI (S-nZVI/PS) or nZVI (nZVI/PS) were carried out in this paper. The results show that, compared to the bare nZVI/PS system, the S-nZVI/PS system shows higher activity in BPS degradation, especially at high BPS concentration. The reaction rate constant kobs of BPS removal by the S-nZVI/PS system (0.142 min-1) was much higher than that in nZVI/PS system (0.089 min-1) because more oxidation species were generated in the S-nZVI/PS system. The results of electron paramagnetic resonance (EPR) and radical quenching tests show that both hydroxyl radical (·OH) and sulfate radical (SO4·-) were involved in the degradation of BPS and had a great contribution to BPS removal. Moreover, the effects of S/Fe molar ratio, S-nZVI dosage, initial pH, and initial concentration of PS or BPS on S-nZVI/PS were also studied. The results show that the S/Fe molar ratio has significant influence on the BPS degradation; over 97.7% of the removal efficiency was achieved at 0.035 of S/Fe molar ratio. And the removal efficiency of BPS degradation increased with the increase of the dosage of S-nZVI, PS concentration. Furthermore, BPS could be efficiently removed in solutions with a wide range of initial pH (3.13-9.35). The observed results show that it is promising in the removal of micro-pollutants from water by persulfate activated with S-nZVI.

Inactivation of sulfonamide antibiotic resistant bacteria and control of intracellular antibiotic resistance transmission risk by sulfide-modified nanoscale zero-valent iron.

The inactivation of a gram-negative sulfonamide antibiotic resistant bacteria (ARB) HLS.6 and removal of intracellular antibiotic resistance gene (ARG, sul1) and class I integrase gene (intI1) by nanoscale zero-valent iron (nZVI) and sulfide-modified nZVI (S-nZVI) with different S/Fe molar ratios were investigated in this study. The S-nZVI with high sulfur content (S/Fe = 0.05, 0.1, 0.2) was superior to nZVI and the treatment effect was best when S/Fe was 0.1. The ARB (2 × 107 CFU/mL) could be completely inactivated by 1.12 g/L of S-nZVI (S/Fe = 0.1) within 15 min, and the removal rates of intracellular sul1 and intI1 reached up to 4.39 log and 4.67 log at 60 min, respectively. Quenching experiments and flow cytometry proved that reactive oxygen species and adsorption were involved in the ARB inactivation and target genes removal. Bacterial death and live staining experiments and transmission electron microscopy showed that the ARB cell structure and intracellular DNA were severely damaged after S-nZVI treatment. This study provided a potential alternative method for controlling the antibiotic resistance in aquatic environment.

Elimination of antibiotic resistance genes in waste activated sludge by persulfate treatment during the process of sludge dewatering.

Two sludge conditioning modes (nanoscale zero valent iron modified by Ginkgo biloba L. leaf (G-nZVI)/sodium persulfate (PS) conditioning with different ratios (1:0, 1:0.1, 1:1 and 1:10) and G-nZVI/PS conditioning with continuous addition) in reducing the specific resistance of filtration (SRF) and removing antibiotic resistant genes (ARGs) were investigated. After 3 min, the SRF values decreased in following order: 2.45 × 108 m/kg (1:10) > 5.95 × 106 m/kg (1:0.1) > 3.72 × 106 m/kg (1:0) > 4.92 × 105 m/kg (1:1). In the continuous addition (1:1), the SRF value decreased from 1.04 × 108 m/kg to 6.47 × 106 m/kg at 9 min. Removal efficiency of ARGs was 2-6 orders of magnitude and no regeneration of ARGs was observed in sludge and water phase. When treated samples were incubated for 36 h, dominant microflora was negatively correlated with ARGs. This study revealed persulfate treatment could achieve dewatering and remove ARGs, simultaneously.

Interaction between pollutants during the removal of polychlorinated biphenyl-heavy metal combined pollution by modified nanoscale zero-valent iron.

Modified nanoscale zero-valent iron (nZVI) is a promising functional material for the remediation of combined pollutants involving polychlorinated biphenyls (PCBs) and heavy metals. However, the interaction between the two types of pollutants has not been systematically studied for this method of treatment. In this study, 2,2',4,4',5,5'-hexachlorobiphenyl (PCB153), Cu2+, and Ni2+ were selected as the target pollutants. To understand the interaction between pollutants, the efficiencies of nZVI, sulfidated nZVI (S-nZVI), and carboxymethylcellulose stabilized nZVI (CMC-nZVI) were investigated for removal of PCB153, Cu2+/Ni2+, and combined pollution system (PCBs-Cu2+/Ni2+). Results showed that the removal kinetics of the two types of pollutants by the three materials fitted a pseudo-first-order model well and that the reaction mechanisms were similar. Among the three materials, CMC-nZVI showed the highest reactivity to degrade PCB153 (pseudo-first-order kinetic constants (kobs) = 2.7 × 10-4 min-1) and remove Cu2+ (kobs = 2.890 min-1), while S-nZVI showed higher affinity for the removal of Ni2+ (kobs = 0.931 min-1). For the combined pollution system, PCB153 had little effect on the removal of heavy metals by the three materials, while the effect of heavy metals on PCB153 degradation was related to the types of heavy metals and the materials. Cu2+ had no significant effect on PCB153 degradation by the three materials, while the coexistence of Ni2+ promoted PCB153 degradation by nZVI and CMC-nZVI. XPS and electrochemical analysis showed that Cu0 and Ni0 were produced on the surface of the three materials. Ni is a more effective catalyst and promoted the electron transfer efficiency of the materials and had a positive impact on the dechlorination reaction.

Substantially enhanced anaerobic reduction of nitrobenzene by biochar stabilized sulfide-modified nanoscale zero-valent iron: Process and mechanisms.

Nanoscale zero-valent iron (nZVI), although being increasingly used in anaerobic systems for strengthening the removal of various refractory pollutants, is limited by various inherent drawbacks, such as easy precipitation, passivation, poor mass and electron transfer. To address the above issues, biochar stabilized sulfide-modified nZVI (S-nZVI@BC) was added into an up-flow anaerobic sludge blanket (UASB) to investigate the enhancement of anaerobic biodegradation of nitrobenzene (NB) and its impacts on microbial community structure. The results demonstrated that both NB reduction and aniline formation could be substantially facilitated in S-nZVI@BC coupled system compared to other anaerobic ones coupled with nZVI or S-nZVI. The dosage of S-nZVI@BC resulted in the formation of densely packed aggregates, evidently increased the extracellular polymeric substances content, promoted the volatile fatty acids transformation and stimulated the methane yield. Furthermore, species related to fermentation (Bacteroides and Longilinea), methanogenesis (Methanosarcina and Methanomethylovorans), electroactivity (Pelobacter, Thiobacillus and Phaselicystis) as well as reduction (Desulfovibrio) were considerably enriched in S-nZVI@BC coupled system. The activities of electron transport, total adenosine triphosphate, nitroreductase and NAD(P)H, which were closely related to microbial activity and NB transformation, were increased noticeably in S-nZVI@BC coupled anaerobic system. This study demonstrated the promising potential for long-term operation and full-scale application of S-nZVI@BC coupled system for the treatment of NB containing wastewater.