Degradation of 2,4,6-trichloropenol (TCP) with peroxymonosulfate (PMS) catalyzed by iron porphyrin tetrasulfonate ([FePTS)] was investigated in an 8-to-1 (v/v) CH3OH-H2O mixture. Typical reaction medium contained a 4.00 mL methanol solution of TCP (0.100 mmol), a 0.50 mL aqueous solution of catalyst (5.0 × 10⁻⁴ mmol), and 0.100 mmol PMS (as 0.031 g of Oxone). The reaction was performed at ambient temperature. The conversion of TCP was 74% in 30 min and 80% in 6 h when the catalyst was [FePTS]. Amberlite IRA-900 supported [FePTS] catalyst was also prepared. In the recycling experiments the homogeneous [FePTS] lost its activity after the first cycle, while [FePTS]-Amberlite IRA 900 maintained its activity for the first 2 cycles. After the second cycle, the conversion of TCP dropped to <10% for Amberlite IRA-900 supported [FePTS] catalyst. The degradation of TCP with PMS was also attempted using cobalt, copper, nickel and palladium porphyrin tetrasulfonate catalysts, however, no catalytic activity was observed with these structures.

Using Artemia salina (A. salina) cysts (capsulated and decapsulated) and larvae [instar I (0–24 h), II (24–48 h) and III (48–72 h)] as experimental models, developmental toxicity of oxidized multi-walled carbon nanotubes (O-MWCNTs) was evaluated. Results revealed that hatchability of capsulated and decapsulated cysts was significantly decreased (p < 0.01) following exposure to 600 mg/L for 36 h. Mortality rates were 33.8, 55.7 and 40.7% for instar I, II and III larvae in 600 mg/L. The EC50 values for swimming inhibition of instar I, II and III were 535, 385 and 472 mg/L, respectively. Instar II showed the greatest sensitivity to O-MWCNTs, and followed by instar III, instar I, decapsulated cysts and capsulated cysts. Effects on hatchability, mortality and swimming were accounted for O-MWCNTs rather than metal catalyst impurities. Body length was decreased with the concentrations increased from 0 to 600 mg/L. O-MWCNTs attached onto the cysts, gill and body surface, resulting in irreversible damages. Reactive oxygen species, malondialdehyde content, total antioxidant capacity and antioxidant enzymes (superoxide dismutase, catalase and glutathione peroxidase) activities were increased following exposure, indicating that the effects were related to oxidative stress. O-MWCNTs were ingested and distributed in phagocyte, lipid vesicle and intestine. Most of the accumulated O-MWCNTs were excreted by A. salina at 72 h, but some still remained in the organism. Data of uptake kinetics showed that O-MWCNTs contents in A. salina were gradually increased from 1 to 48 h and followed by rapidly decreased from 48 to 72 h with a range from 5.5 to 28.1 mg/g. These results so far indicate that O-MWCNTs have the potential to affect aquatic organisms when released into the marine ecosystems.

In this study, ZnAlTi layered double hydroxide (ZnAlTi-LDH) combined with fullerene (C60) was fabricated by the urea method, and calcined under vacuum atmosphere to obtain nanocomposites of C60-modified ZnAlTi layered double oxide (ZnAlTi-LDO). The morphology, structure and composition of the nanocomposites were analyzed by Scanning Electron Microscopy, High-resolution transmission electron microscopy, X-ray diffraction patterns, Fourier transform infrared and specific surface area. The UV-vis diffuse reflectance spectra indicated that the incorporation of C60 expanded the absorption of ZnAlTi-LDO to visible-light region. The photo-degradation experiment was conducted by using a series of C60 modified ZnAlTi-LDO with different C60 weight percentage to degrade Bisphenol A (BPA) under simulated visible light irradiation. In this experiment, the degradation rate of C60 modified ZnAlTi-LDO in photo-degradation of BPA under simulated visible light irradiation was over 80%. The intermediates formed in the degradation of BPA process by using LDO/C60-5% were 4-hydroxyphenyl-2-propanol, 4-isopropenylphenol and Phenol. Photogenerated holes, superoxide radical species, ·OH and singlet oxygen were considered to be responsible for the photodegradation process, among which superoxide radical species and ·OH played a predominant role in the photocatalytic reaction system. C60 modified ZnAlTi-LDO catalysts for photocatalytic reduction shows great potential in degradation of organic pollutants and environmental remediation.

In this study, solid acid amorphous Fe3O4/SiO2 ceramic coating decorated with sulfur on Q235 carbon steel as Fenton-like catalyst for phenol degradation was successfully prepared by plasma electrolytic oxidation (PEO) in silicate electrolyte containing Na2S2O8 as sulfur source. The surface morphology and phase composition were characterized by SEM, EDS, XRD and XPS analyses. NH3-TPD was used to evaluate surface acidity of PEO coating. The results indicated that sulfur decorated amorphous Fe3O4/SiO2 ceramic coatings with porous structure and higher acid strength had the similar pore size and the surface became more and more uneven with the increase of Na2S2O8 in the silicate electrolyte. The Fenton-like catalytic activity of sulfur decorated PEO coatings was also evaluated. In contrast to negligible catalytic activity of sulfur undecorated PEO coating, catalytic activity of sulfur decorated PEO coating was excellent and PEO coating prepared with 3.0 g Na2S2O8 had the highest catalytic activity which could degrade 99% of phenol within 8 min under circumneutral pH. The outstanding performance of sulfur decorated PEO coating was attributed to strong acidic microenvironment and more Fe²⁺ on the surface. The strong acid sites played a key factor in determining catalytic activity of catalyst. In conclusion, rapid phenol removal under circumneutral pH and easier separation endowed it potential application in wastewater treatment. In addition, this strategy of preparing immobilized solid acid coating could provide guidance for designing Fenton-like catalyst with excellent catalytic activity and easier separation.

Biogenic palladium nanoparticles (bio-Pd NPs) represent a promising catalyst for organohalide remediation in water and sediments. However, the available information regarding their possible impact in case of release into the environment, particularly on the environmental microbiota, is limited. In this study the toxicity of bio-Pd NPs on the model marine bacterium V. fischeri was assessed. The impacts of different concentrations of bio-Pd NPs on the respiratory metabolisms (i.e. organohalide respiration, sulfate reduction and methanogenesis) and the structure of a PCB-dechlorinating microbial community enriched form a marine sediment were also investigated in microcosms mimicking the actual sampling site conditions. Bio-Pd NPs had no toxic effect on V. fischeri. In addition, they had no significant effects on PCB-dehalogenating activity, while showing a partial, dose-dependent inhibitory effect on sulfate reduction as well as on methanogenesis. No toxic effects by bio-Pd NPs could be also observed on the total bacterial community structure, as its biodiversity was increased compared to the not exposed community. In addition, resilience of the microbial community to bio-Pd NPs exposure was observed, being the final community organization (Gini coefficient) of samples exposed to bio-Pd NPs similar to that of the not exposed one. Considering all the factors evaluated, bio-Pd NPs could be deemed as non-toxic to the marine microbiota in the conditions tested. This is the first study in which the impact of bio-Pd NPs is extensively evaluated over a microbial community in relevant environmental conditions, providing important information for the assessment of their environmental safety.

Membrane photocatalytic ozonization coupled with wet absorption offers potential for elemental mercury (Hg0) removal. This study reports on a novel FeTiO2-coated polyvinylidene fluoride (PVDF) wet photocatalytic membrane reactor (WPCMR) for mercury removal in flue gas. Hg0 removal efficiency in the WPCMR reached up to 93.3%. Ozone could enhance mercury oxidation in WPCMR. Wet absorption helps to increases mercury removal efficiency. FeTiO2 catalyst was synthesized by sol-gel method and characterized by XRD, FTIR, UV–Vis, XPS and SEM. XPS analysis confirmed Hg0 oxidation to divalent mercury (Hg (II)). Elemental mercury was oxidized to mercuric oxide followed by wet absorption in the presence of OH free radical and ozone. Wet photocatalytic membrane reactor and photocatalytic membrane reactor (PCMR) of elemental mercury reaction with the FeTiO2/PVDF catalyst all follow Langmuir-Hinshelwood kinetics.

Three-way catalyst (TWC) converter is one of the most important after-treatment device for modern light-duty gasoline vehicles (LDGVs), which can efficiently control exhaust emissions of carbon monoxide (CO), total hydrocarbons (THC) and nitrogen oxides (NOX). Nevertheless, a considerable part of in-use taxis in Beijing would operate with TWC purposely removed, which have been indicated by vehicular on-board diagnostic (OBD) systems. In light of high vehicle-use intensity for taxis, we recruited three China 4 non-TWC taxis and three China 4 normal taxis in a comparative experimental test by using a portable emissions measurement system (PEMS). The results indicated that non-TWC taxis emitted significantly higher emissions of air pollutants than normal taxis with TWC functioning. For example, average emission factors of non-TWC vehicles were comparable to emission levels of China 1 LDGVs measured in previous studies. By contrast, emissions from normal China 4 taxis were all below China 4 emission limits. Furthermore, an operating mode binning method and a micro-trip approach have been employed to link vehicle emissions with driving conditions. For non-TWC taxis, we identified strong correlations of all pollutant categories between emission factors and average speed. However, such correlations for normal taxis were less strong, in particular for CO and THC emissions that were hardly sensitive to speed changes. This phenomenon indicates that the role of traffic conditions in affecting real-world emissions would become weaker when TWC can effectively mitigate emissions. This paper highlights the importance of in-use emission inspection to avoid any “high emitters” that have violated regulation enforcement.

Comparative studies were developed with regard to the criteria emissions of THC - total hydrocarbons, CO - carbon monoxide and NOx - nitrogen oxides, and BTEX (benzene, toluene, ethyl benzene and xylenes). Three four-stroke motorcycles were fuelled with E22 fuel (gasoline with 22% of ethanol). One flex fuel motorcycle was also fuelled with E100, 100% Hydrated Reference Ethanol, and with E61 (61% of ethanol). Criteria emissions were quantified using traditional measurement techniques based on the European Directive 97/24/EC (EURO protocol). To determine the BTEX emissions, gas chromatography coupled with mass spectrometry was employed. All motorcycles were equipped with a catalyst (TWC) used to reduce the amount of toxic emissions in the exhaust gases. To evaluate the performance of the catalyst, one motorcycle was tested with and without the device. One motorcycle was tested according to two different test protocols, namely, the ECE/TRANS/180 WMTC, also known as the Worldwide Motorcycle Test Cycle, and the EURO protocol. The main results were that toluene emissions were more prevalent than other aromatics. The tests with and without the catalyst showed that after the catalyst was employed the conversion efficiencies for benzene, toluene, ethyl benzene and xylene were 52.3%, 84.0%, 85.0%, and 86.0%, respectively. The results regarding the flex fuel motorcycle show that BTEX emissions decrease with an increase of ethanol in the mixture. Comparing the EURO and WMTC protocols, it was observed that the WMTC protocol generates lower emissions compared to the EURO protocol; however, NOx showed the opposite trend of BTEX.

The aim of this study was to evaluate the redox mediating capacity of anthraquinone-2,6-disulfonate (AQDS) immobilized on granular activated carbon (GAC) during the reductive decolorization of direct blue 71 (DB71) under microbial and chemical conditions. The immobilization of AQDS on GAC was conducted by adsorption, and it has obtained an uptake capacity of 0.227 mmol g⁻¹. The anchorage of AQDS on GAC improved its electron transfer capacity (ETC) up to 2.05 times higher than the raw material. Similarly, the addition of GAC-AQDS increased up to 1.75- and 1.16-fold the rate of decolorization (k d) of DB71 under microbial and chemical conditions, respectively, in comparison to the unmodified GAC. Surprisingly, a higher k d value was achieved in incubations without either GAC or GAC-AQDS because of the generation of aromatic amines, from the reduction DB71, taking into account that these species may act as a catalyst in the DB71 reduction process. In contrast, adsorption of aromatic amines on either GAC or GAC-AQDS decreased its redox mediating capacity as evidenced by spectrophotometric screenings of the decolorized solution and the supporting material. The development of materials with enhanced both redox and adsorption properties, as the GAC used in this study, offers a promising way to increase the redox conversion of recalcitrant pollutants commonly found in industrial wastewaters.

Ni, Cu, and Ni-Cu metal oxides supported on granular activated carbon (GAC) were synthesized and used in catalytic ozonation of heavy oil produced water. The effect of preparation conditions on their catalyst composition, catalyst structure, and catalytic activity was investigated. The catalyst structure was characterized by X-ray power diffraction (XRD). The results revealed that the Ni-Cu/GAC has the highest catalytic activity, followed by Cu/GAC and Ni/GAC. Metal oxide loading rate depended on impregnation process, whereas dispersion of metal oxides was controlled by calcination process. The XRD analysis showed that the principal active phase was Cu₂O for Cu/GAC and Ni-Cu/GAC catalyst and NiO for Ni/GAC catalyst. The most active plane was Cu₂O₍₂₀₀₎ and then followed by Cu₂O₍₁₁₀₎ and Cu₂O₍₁₁₁₎ for Cu-supported catalysts. Higher calcination temperature and time favored the generation of Cu₂O but increased the crystalline diameter. It also suggested that promoting the generation of NiO and Cu₂O phase and reducing the crystalline diameter could improve the catalytic activity. During Ni-Cu/GAC preparation, existence of Ni(NO₃)₂ could accelerate the adsorption of Cu(NO₃)₂, promoting the generation of Cu₂O, and improve the dispersion of Cu₂O phase. Graphical Abstract ᅟ