Hollow Plasmonic P-Metal-N S-Scheme Heterojunction Photoreactor with Spatially Separated Dual Cocatalysts toward Artificial Photosynthesis.

Semiconductor-based step-scheme (S-scheme) heterojunctions possess many merits toward mimicking natural photosynthesis. However, their applications for solar-to-chemical energy conversion are hindered by inefficient charge utilization and unsatisfactory surface reactivity. Herein, two synergistic protocols are demonstrated to overcome these limitations based on the construction of a hollow plasmonic p-metal-n S-scheme heterojunction photoreactor with spatially separated dual noble-metal-free cocatalysts. On one side, plasmonic Au, inserted into the heterointerfaces of CuS@ZnIn2 S4 core-shell nanoboxes, not only accelerates the transfer and recombination of useless charges, enabling a more thorough separation of useful ones for CO2 reduction and H2 O oxidation but also generates hot electrons and holes, respectively injects them into ZnIn2 S4 and CuS, further increasing the number of active carriers participating in redox reactions. On the other side, Fe(OH)x and Ti3 C2 cocatalysts, separately located on the CuS and ZnIn2 S4 surface, enrich the redox sites, adjust the reduction potential and pathway for selective CO2 -to-CH4 transformation, and balance the transfer and consumption of photocarriers. As expected, significantly enhanced activity and selectivity in CH4 production are achieved by the smart design along with nearly stoichiometric ratios of reduction and oxidation products. This study paves the way for optimizing artificial photosynthetic systems via rational interfacial channel introduction and surface cocatalyst modification.

Tuning of Persulfate Activation from a Free Radical to a Nonradical Pathway through the Incorporation of Non-Redox Magnesium Oxide.

Nonradical-based advanced oxidation processes for pollutant removal have attracted much attention due to their inherent advantages. Herein we report that magnesium oxides (MgO) in CuOMgO/Fe3O4 not only enhanced the catalytic properties but also switched the free radical peroxymonosulfate (PMS)-activated process into the 1O2 based nonradical process. CuOMgO/Fe3O4 catalyst exhibited consistent performance in a wide pH range from 5.0 to 10.0, and the degradation kinetics were not inhibited by the common free radical scavengers, anions, or natural organic matter. Quantitative structure-activity relationships (QSARs) revealed the relationship between the degradation rate constant of 14 substituted phenols and their conventional descriptor variables (i.e., Hammett constants σ, σ-, σ+), half-wave oxidation potential (E1/2), and pKa values. QSARs together with the kinetic isotopic effect (KIE) recognized the electron transfer as the dominant oxidation process. Characterizations and DFT calculation indicated that the incorporated MgO alters the copper sites to highly oxidized metal centers, offering a more suitable platform for PMS to generate metastable copper intermediates. These highly oxidized metals centers of copper played the key role in producing O2•- after accepting an electron from another PMS molecule, and finally 1O2 as sole reactive species was generated from the direct oxidation of O2•- through thermodynamically feasible reactions.

Comparison study of landfill gas emissions from subtropical landfill with various phases: A case study in Wuhan, China.

The compositions and annual variations of landfill gas (LFG) were studied at two large-scale sites of Chen-Jia-Chong Landfill. Seventy-six wells were built and used for the collection and measurement of LFG. The investigation revealed the similarities and differences of LFG components and variations at two sites with different phases. It was found that ambient temperature and rainfall exhibited strong correlations with LFG components at both sites. Methane (CH4) contents showed excellent correlations with CO2at both sites. Notable correlations between hydrogen sulfide (H2S) and major components (CH4and carbon dioxide [CO2]) were only observed in unstable methane phase. Especially, the CH4/CO2volumetric ratio could act as an excellent indicator for anaerobic reaction stage by judging its phasic variations. The study is beneficial for the efficient operation of LFG collection system and could shed light on gas purification and utilization.

Recycling application of modified waste electrolytic manganese anode slag as efficient catalyst for PMS activation.

Electrolytic manganese anode slag (EMAS) is the waste residue produced by electrolytic manganese metal industry. At present, no mature recycling system has been established, which causes a waste of resources and threatens the environment. Therefore, the resource utilization of EMAS has attracted increased attention. In this paper, the in-situ resource utilization of EMAS can be realized by pickling treatment was reported. Specifically, EMAS after pickling treatment (PEMAS) was first used as catalyst to activate PMS to degrade tetrachlorophenol (4-CP). Pickling could remove the inert inorganic components on EMAS and increase the specific surface area, pore volume and Mn distribution of the catalyst, thus improving the catalytic performance of the catalyst. Under the conditions of 4-CP of 40 ppm, PMS of 1 mM and PEMAS of 0.3 g L-1, 85% of 4-CP could be degraded within 50 min. Mechanism studies proved that the main active species were O2- and 1O2. Some O2- contributed to the generation of 1O2 and some O2- directly contributed to the degradation of 4-CP. During the reaction, the valence state of Mn transformed between Mn(III)/Mn(IV) and Mn(II)/Mn(III) and kept the cycle. Moreover, PEMAS/PMS system exhibited excellent independence of the solution pH, resistance to the versatile inorganic ions and background organic matters, and stability of recycling. In a word, this study has achieved the resource utilization of EMAS and the goal of treating waste with waste, which is a win-win strategy of economic and environmental benefits.

Interpret the elimination behaviors of lead and vanadium from the water by employing functionalized biochars in diverse environmental conditions.

Wide-ranging researches have been executed to treat groundwater from different mining areas, although complex behaviors of diverse metal ion species in the groundwater have not been illustrated clearly. This research study explored the mechanisms through which Pb(II) and V(V) are eliminated in single and binary-metal removal processes by oxygen, nitrogen, and sulfur-doped biochars also considering the kinetic and characterization techniques. The adsorption efficiency of V (V) was enhanced by oxygen-doped biochar at pH 4 with an adsorption capacity of ~70 mg/g. However, Pb (II) was rapidly removed at pH 6 with a higher adsorption capacity of ~180 mg/g by the nitrogen and sulfur-doped biochar forming PbCO3 and V(CO)6 crystals along the single-metal removal process. These results could be explained by the Hard Soft Acid Base theory. The hard Lewis acid vanadium was attracted by the hard Lewis base oxygen, and the intermediate Lewis acid lead was attracted by the intermediate and soft Lewis base nitrogen and sulfur. Besides, the removal ability of Pb(II) and V(V) in the binary-metal removal process showed a similar phenomenon for all types of biochars at pH 4 with the adsorption capacity of ~400 mg/g for Pb(II) and 175 mg/g for V(V), but the composition of vanadium species remains unclear on the surface of the biochars. Initially, H3V2O7-, H2VO4-, and HVO42- species were electrostatically attracted by the oxygen-based functionalities, then V(V) species was partially reduced to VO2+ by the oxygen, nitrogen, and sulfur functionalities in different ratios. Finally, H3V2O7-, H2VO4-, and HVO42- species produced Pb5(VO4)3Cl and Pb2V2O7 which co-precipitate with Pb(II), but VO2+ does not generate any form of precipitates. The above-explained technique supports the treatment of vanadium mining groundwater with valuable vanadinite (Pb5(VO4)3Cl) mineral.

Quantitative evaluation of infectious health care wastes from numbers of confirmed, suspected and out-patients during COVID-19 pandemic: A case study of Wuhan.

The fight against coronavirus disease 2019 (COVID-19) is still running its courses. Proper management and disposal of health care wastes (HCWs) are critical to win the fight. To achieve aforementioned tasks, prediction of their production is highly desired. In this study, primary data of production of three kinds of HCWs collected from Wuhan, the first epidemic epicenter worldwide and a mega city with more than 10 million population who has went through a lockdown period of 78 days, were reported for their first time. HCWs were classified into routine HCWs, infectious HCWs (IHCWs) and infectious municipal solid wastes. Among them, infectious HCWs from designated hospitals for COVID-19 were recognized as the most dangerous one. A multiple linear regression (MLR) model was built to predict the production of IHCWs with high significance. Numbers of patients were demonstrated high correlations with the production of IHCWs in an order of confirmed patients ＞ out-patients ＞ suspected patients. By the MLR model, production rates of IHCWs by confirmed, suspected and out patients were determined as 3.2, 1.8 and 0.1 kg/patient, respectively. In addition, constant production of IHCWs during the pandemic period was determined as 13 tons/d. This is the first study on quantitative evaluation of infectious HCWs during COVID-19 pandemic. The achievements in this study have potentials to shed light on global efforts to the prediction, management and disposal of vast HCWs generated in the war against COVID-19.

A self-gating proton-coupled electron transfer reduction of hexavalent chromium by core-shell SBA-Dithiocarbamate chitosan composite.

We have proposed a novel strategy for the reduction plus adsorption process for hexavalent chromium elimination by thiol functional hybrid materials through a self-gating process. Namely, we exploit that coating dithiocarbamate chitosan at the surface of SBA-15 affords a core-shell composite that undergoes reversible shape transformations while thiol functional groups acted as proton-coupled electron donor for [Cr2O7]2-. The reduction of [Cr2O7]2- to Cr3+ was highly efficient and exceptionally rapid, occurred within 5 min with the reduction amount of 899.66 mg of [Cr2O7]2- / 1 g of nanocomposite as a record high value. During the reduction of [Cr2O7]2-, thiol functional groups (-SH) were oxidized into disulfide linkages (SS), and simultaneously chitosan matrix turned into shrunken structure because of the consuming of protons, preventing any release of Cr3+. Disulfides can also be reversely reduced to thiols by thiosulphates (S2O32-), which was attractive for regeneration and recyclability of the nanocomposite. Moreover, the [Cr2O7]2- elimination through self-gating process was highly selective against a huge concentration of background electrolytes. This alternative strategy ensures the outstanding and stable performance in applied fields, and could be conducted in various pollution control techniques like permeable reactive barriers.

Black liquor as biomass feedstock to prepare zero-valent iron embedded biochar with red mud for Cr(VI) removal: Mechanisms insights and engineering practicality.

Black liquor (BL) is an agro-industrial residue with high number of lignocellulosic components which could be recognized as a biomass feedstock. In this work, BL coupled with red mud (RM), were applied to prepare cost-effective zero-valent iron (ZVI) embedded in biochar. The oligomers in BL acted as reductants for RM to generate ZVI, while the organic components could be converted into biochar during pyrolysis. The RM/BL demonstrated excellent performance in the removal of Cr(VI) (349.5 mg/g), as the mechanisms were reduction and adsorption. The fixed-bed column study was conducted and 1.7 L simulated wastewater could be treated by 1.0 g RM/BL. After reaction, 95.5% ± 0.8% and 82.5%±3.2% Cr-loaded adsorbents could be recovered by an external magnet for batch and fixed-bed experiments, respectively. All these results shed light on valorizing these two widespread agro-industrial byproducts, and bridged the knowledge gap between magnetic bio-adsorbent preparation and its industrial practicality on wastewater purification.

Engineered biochar with anisotropic layered double hydroxide nanosheets to simultaneously and efficiently capture Pb2+ and CrO42- from electroplating wastewater.

Cationic and anionic heavy metal contaminants generally co-exist in practical industrial effluent, and simultaneously removal of these species is a bottleneck for most of the bio-adsorbents because of their contrary charge. In this work, pinewood sawdust derived engineered biochar (BC) was fabricated with MgAl layered double hydroxide (MgAl-LDH) nanosheets, which could efficiently and simultaneously capture heavy metal cations and oxyanions from wastewater. The synergetic effect between loaded MgAl-LDH and BC substantially improves its adsorption performance towards both cationic and anionic contaminants, i.e., Pb2+ and CrO42-. The adsorption capacity of MgAl-LDH/BC for Pb2+ reached 591.2 mg/g, which is 263% higher than that of BC, and in the case of CrO42-, the adsorption capacity is 330.8 mg/g, 416% higher than that of BC. The elimination of Pb2+ was mainly attributed to forming complexations with surface functional groups. While for oxyanions removal, CrO42- can be reduced to Cr3+ by functional groups, and then generated Cr3+ could replace Al3+ via morphic substitution, consequently formed an MgCr-LDH structure. Further, in the continuous fixed-bed column study, 225 bed volume of simulating electroplating wastewater co-existed with Pb2+ and CrO42- can be efficiently treated. Hence, this study sheds light on the engineered biochar design to efficiently and simultaneously capture heavy metal cations and oxyanions and its feasibility on real wastewater purification.

Regulating the redox centers of Fe through the enrichment of Mo moiety for persulfate activation: A new strategy to achieve maximum persulfate utilization efficiency.

Persulfate Fe-based catalytic oxidation is considered as one of the most attractive strategy for the growing concerns of water pollution. However, the undesirable FeIII/FeII redox cycle restrict them from attending the sustainable activity during practical applications. This study was intended to develop a new strategy to regulate the redox cycles of FeIII/FeII by introducing the second redox center of MoS42- in the interlayers of Fe-based layered double hydroxide (FeMgAl-MoS4 LDH). Based on the first-order kinetic model, the fabricated FeMgAl-MoS4 catalyst was 10-100 fold more reactive than the bench marked peroxymonosulfate (PMS) activators including FeMgAl LDHs and other widely reported nano-catalysts such as Co3O4, Fe3O4, α-MnO2, CuO-Fe3O4 and Fe3O4. The enhanced catalytic activity of FeMgAl-MoS4 LDH was related to the continuous regeneration of active sites (FeII/MoIV), excellent PMS utilization efficiency and generation of abundant free radicals. Moreover, the FeMgAl-MoS4/PMS system shows an effective pH range from 3.0 to 7.0 and the degradation kinetics of parahydroxy benzoic acid (PHB) were not effected in the presence of huge amount of background electrolytes and natural organic matters. Based on the in-situ electron paramagnetic resonance spectroscopy (EPR), chemical scavengers, XPS analysis and gas chromatography couple with mass spectrometer (GC-MS), a degradation pathway based on dominant free radicals (•SO4- and •OH), passing through the redox cycles of FeIII/FeII and MoVI/MoIV was proposed for PMS activation. We believe that this strategy of regulating the redox center through MoS42- not only provides a base to prepare new materials with stable catalytic activity but also broaden the scope of Fe-based material for real application of contaminated water.

Non-radical PMS activation by the nanohybrid material with periodic confinement of reduced graphene oxide (rGO) and Cu hydroxides.

A new strategy was applied by periodic stacking of active sites of Cu and reduced graphene oxide (rGO) in the form of Cu-rGO LDH nanohybrid material. The experimental results revealed that newly prepared Cu-rGO LDH nanohybrid material was extremely reactive in PMS activation as evident from the degradation rate of 0.115 min-1, much higher than Mn-rGO LDH (0.071 min-1), Zn-rGO LDH (0.023 min-1) or other benchmarked material used during the degradation of bisphenol A (BPA). This excellent activity of Cu-rGO LDH nanohybrid was attributed to the better PMS utilization efficiency as compared to the other catalysts. Additionally, the characterization techniques disclosed that the layer by layer arrangement of active sites in the Cu-rGO LDH catalyst promotes interfacial electron mobility owing to the synergistic association between Cu in LDH and interlayered rGO. Based on the in-situ electron paramagnetic resonance spectroscopy (EPR) and chemical scavengers, singlet oxygen (1O2) was unveiled as dominant reactive species for pollutant removal, resulting from the recombination of superoxides (O2-) or reduction of active Cu centers. We believe that this novel Cu-rGO LDH/PMS system will open up a new avenue to design efficient metal-carbon nanohybrid catalysts for the degradation of emerging aquatic pollutants in a real application.

Degradation of Phenol Using Peroxymonosulfate Activated by a High Efficiency and Stable CoMgAl-LDH Catalyst.

In this study, we report on an active and stable CoMgAl layered double hydrotalcite (LDH) catalyst for phenol degradation by heterogeneous activation of peroxymonosulfate (PMS). The CoMgAl-LDH catalyst was synthesized by hydrothermal method. The PMS/CoMgAl-LDH system overcomes the drawbacks of traditional Fenton processes. Various effects, e.g., scavengers, chloride ion, catalyst dosage, PMS concentration, temperature, and pH, were also inspected to evaluate the system. The results indicated that the PMS/CoMgAl-LDH system had extremely high efficiency for phenol degradation; 0.1 mM phenol could be completely degraded by 0.3 g/L catalyst and 3 mM PMS within 60 min at 30 °C. The CoMgAl-LDH catalyst appeared to possess outstanding reusability and stability. After four rounds of recycling, nearly 100% of the phenol was removed within 80 min by the PMS/CoMgAl-LDH system, with only 0.05 mg/L Co2+ leaching. A sulfate radical was the main oxidation species in the PMS/Co-LDH system. The degradation rate of phenol was influenced by temperature, and the activation energy was 65.19 kJ/mol. These advantages proved the PMS/CoMgAl-LDH system is an effective strategy for the treatment of organic contaminants.

Adsorptive purification of heavy metal contaminated wastewater with sewage sludge derived carbon-supported Mg(II) composite.

A rod-like SDBC-Mg(II) composite was synthesized and optimized in the conditions of 25% Mg(II) loading and 500 °C calcination temperature. As-prepared SDBC-25%Mg(II)-500 adsorbent attained equilibrium in 30 min, with an extraordinary capacity of 2931.76 mg g-1 (Pb(II)) and 861.11 mg g-1 (Cd(II)), revealing a promising adsorbent for the removal of such metals so far. The adsorption kinetics was well described by the pseudo-second-order model while the adsorption isotherm could be fitted by Redlich-Peterson model. Furthermore, SDBC-25%Mg(II)-500 has a high anti-interference and selectivity in the presence of competing ions/other environmental factors and, also effectively eliminates >99% of Pb2+, Cd2+, Ag+ and Cu2+ ions from pond water, lake water and tap water. The adsorption process demonstrated a synergetic adsorption mechanism comprised of ion exchange with Mg(II), coordination with surface and inner carboxylic or carbonyl functional groups and co-precipitations as metal silicates, which is responsible for its superb adsorption performance. Besides, surface carvings of Mg(II) and tunnels on the rods resulting from the sludge carbonization provided a high surface area (91.57 m2 g-1), extra sorption sites and room for easy pollutant diffusion which contributed to surface physical adsorption. Furthermore, this technique demonstrate an alternative pathway that will relieve the burdens of sewage sludge treatment process and turn this solid waste into highly efficient adsorbent for eliminating heavy metal ions from wastewater. This can be considered as a feasible waste resource utilization to meet with the requirement from both ecology and economy for auspicious applications in industries.

Towards a better understanding on mercury adsorption by magnetic bio-adsorbents with γ-Fe2O3 from pinewood sawdust derived hydrochar: Influence of atmosphere in heat treatment.

Pyrolysis under protective atmosphere was regarded as an indispensable process for the preparation of biomass-based adsorbents to achieve higher surface areas. In this paper, magnetic carbon composites (MCC) that fabricated under air atmosphere showed an adsorption capacity of 167.22 mg/g in 200 ppm Hg(II), which was significantly higher than magnetic biochar (MBC, 31.80 mg/g) that fabricated under traditional nitrogen protection, and this remarkable performance of MCC was consistent in a wide range of pHs. Based on BET, XRD, FTIR, SEM and Boehm titration, MCC was demonstrated with limited surface area (43.29 m2/g) but large amount of surface functional groups comparing with MBC. Additionally, γ-Fe2O3 with a high degree of crystallization was generated in MCC, which led to a better magnetic property and recyclability. Moreover, characterizations, Langmuir isotherm and pseudo-second-order kinetics demonstrated the chemisorption was dominant for MCC in mercury capture, and surface complexation co-precipitate of Hg4Fe8O16C56H40 were also formed.

Pd based in situ AOPs with heterogeneous catalyst of FeMgAl layered double hydrotalcite for the degradation of bisphenol A and landfill leachate through multiple pathways.

In situ degradation of organic contaminants by Pd and electro-generated H2 and O2 overcomes the drawbacks to traditional Fenton process, and conducting heterogeneous catalyst of FeMgAl layered double hydrotalcite (LDH) further improved the efficiency and stability. Using bisphenol A (BPA) as the model contaminants, 90% removal can be achieved with 1200 mg/L Pd/Al2O3 and FeMgAl-2. The reusability was satisfying due to the very limited leaching of Fe ions at 0.1 ppm level. FeMgAl also amplified the window of pH for Pd-catalyzed in situ advanced oxidation processes (AOPs) from 3 by homogenous Fe(II) to 3-7 by FeMgAl LDH. The COD of landfill leachate effluent of the MBR system removed by about 52.3% by this system by the initial pH was 5. Characterizations revealed the distinguishing features associated with LDH structure such as large surface area, good stability, basic character, and strong linage among active sites were accounted for the remarkable performances over a wide pH window. Five reactive intermediates were observed and multiple degradation pathways were proposed in Pd-catalyzed in situ AOP for the first time. Interestingly, because of the unique role of Pd catalyst, these degradation pathways were clearly distinguished from traditional Fenton or Fenton-like AOPs and may provide a new approach of in situ heterogeneous AOPs for refractory contaminants in future.

Enhanced degradation of isoproturon in soil through persulfate activation by Fe-based layered double hydroxide: different reactive species comparing with activation by homogenous Fe(II).

Phenylurea herbicide residuals in soil may continuously contaminate surface water and groundwater due to unregulated and improper use. Herein, we reported a stable and active oxidation system including heterogeneous Fe-based layered double hydroxide materials as persulfate (PS) activators. Under mild conditions, 1% LDH in weight and 70 mM PS can completely degrade 500 mg/kg isoproturon in soil within 10 h, during which less than 0.1 ppm heavy metal leaching was detected. This remarkable performance was consistent in a broad pH range (3~11) and was resistant to various inorganic anions (Cl-, Br-, NO3-, HCO3-) and humic acid. Mechanism studies from scavenging tests, EPR, and fluorescence spectra collectively proved that besides •OH and •SO4-, singlet oxygen (1O2) and superoxide (•O2-) were also generated and were accounted for the oxidative degradation. This unique mechanism of generating diverse radicals was clearly distinguished from classic Fe(II)/PS system, significantly reduced the influence of varying parameters in water and soil matrix, and was suggestive to chemical oxidation system in soil remediation to avoid scavenging effects by background electrolytes or other components in water/soil matrix. Graphical abstract ᅟ.

Monitoring bioaccumulation and toxic effects of hexachlorobenzene using the polyurethane foam unit method in the microbial communities of the Fuhe River, Wuhan.

Hexachlorobenzene (HCB) is a chlorinated aromatic hydrocarbon that was widely used for seed dressing in prevention of fungal growth on crops, and also as a component of fireworks, ammunition, and synthetic rubbers. Because of its resistance to degradation and mobility, HCB is widely distributed throughout the environment and is accumulated through food chains in different ecosystems. In this study, a preliminary investigation was carried out on the bioaccumulation and the toxic effects of HCB in the microbial (protozoan in particular) communities in the Fuhe River, Wuhan, a water body receiving industrial wastewaters containing HCB and other pollutants, using the standardized polyurethane foam units (PFU) method. Field samples were taken from eight stations established along the Fuhe River in January and August 2006. The concentration ratios of HCB in microbial communities and in water were 9.66-18.64, and the microbial communities accumulated 13.29-56.88 [ig/L of HCB in January and 0.82-10.25 microg/L HCB in August. Correlation analysis showed a negative correlation between the HCB contents in the microbial assemblage, and the number of species and the diversity index of the protozoan communities. This study demonstrated the applicability of the PFU method in monitoring the effects of HCB on the level of microbial communities.

Fe-MoS4: An Effective and Stable LDH-Based Adsorbent for Selective Removal of Heavy Metals.

It has always been a serious challenge to design efficient, selective, and stable absorbents for heavy-metal removal. Herein, we design layered double hydroxide (LDH)-based Fe-MoS4, a highly efficient adsorbent, for selective removal of heavy metals. We initially synthesized FeMgAl-LDH and then enriched its protective layers with MoS42- anions as efficient binding sites for heavy metals. Various characterization tools, such as X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray, X-ray photoelectron spectroscopy (XPS), CHN analysis, and inductively coupled plasma analysis, were applied to confirm structural and compositional changes during the synthesis of Fe-MoS4 as final product. The prepared Fe-MoS4 offered excellent attraction for heavy metals, such as Hg2+, Ag+, Pb2+, and Cu2+, and displayed selectivity in the order Hg2+ ∼ Ag+ > Pb2+ > Cu2+ > Cr6+ > As3+ > Ni2+ ∼ Zn2+ ∼ Co2+. The immense capacities of Hg2+, Ag+, and Pb2+ (583, 565, and 346 mg/g, respectively), high distribution coefficient (Kd ∼ 107-108), and fast kinetics place Fe-MoS4 on the top of materials list known for removal of such metals. The sorption kinetics and isothermal studies conducted on Hg2+, Ag+, Pb2+, and Cu2+ suit well pseudo-second-order kinetics and Langmuir model, suggesting monolayer chemisorption mechanism through M-S linkages. XRD and FTIR studies suggested that adsorbed metals could result as coordinated complexes in LDH interlayer region. More interestingly, LDH structure offers protective space for MoS42- anions to avoid oxidation under ambient environments, as confirmed by XPS studies. These features provide Fe-MoS4 with enormous capacity, good reusability, and excellent selectivity even in the presence of huge concentration of common cations.

Treatment of refractory contaminants by sludge-derived biochar/persulfate system via both adsorption and advanced oxidation process.

A novel strategy for the removal of refractory organic contaminants was realized through sludge-derived biochar (SDBC)/persulfate (PS) system via both adsorption and advanced oxidation process under ambient conditions. SDBC was prepared by one single step of slow pyrolysis of municipal sewage sludge, appeared a porous structure, and contained abundant oxygen-containing functional groups as well as amorphous Fe species. Large surface area and porous structure of SDBC benefitted the adsorption and enrichment of contaminants, while oxygen-containing functional groups and Fe species on the surface were considered as reactive components for the activation of PS. Under conditions of [PS]0 = 1.85 mM, [4-chlorophenol]0 = 0.039 mM, [SDBC]0 = 1 g L-1, pH0 = 6.30 and temperature = 25 °C, the removal of model compound of 4-chlorophenol achieved 92.3%, and this significant performance of SDBC/PS system was consistent in a broad pH window. Radical scavengers and electron paramagnetic resonance (EPR) studies suggested that SDBC successfully activated PS to produce various oxidative radicals. Meanwhile, recycle experiments and Fe3+ leaching tests further demonstrated the stability of SDBC during the activation of PS. Municipal landfill leachate effluent through a membrane bio-reactor was testified as the refractory real wastewater, in which both the removal of total organic carbon and ammonia was significant. Thus, SDBC showed certain advantages in PS activation such as feasible preparation method, remarkable efficiency and stability. These advantages proved SDBC/PS system as an effective strategy of controlling waste by waste, and implicated its potential application in full-scale for the treatment of refractory organic contaminants.

[16S rDNA-RFLP analysis of structure and diversity of an aerobic microbial community degrading hexachlorobenzene].

Hexachlorobenzene is a chlorinated aromatic hydrocarbon that was widely used as a seed dressing for prevention of fungal growth on crops, and is also a component of fireworks, ammunition, and synthetic rubbers. Because of the bioaccumulation and persistence of hexachlorobenzene as well as its potential toxicity, hexachlorobenzene must be removed from environment. The potential for aerobic dechlorination of hexachlorobenzene by a hexachlorobenzene-adapted mixed culture was investigated. An aerobic microbial community which was able to grow at the presence of hexachlorobenzene was enriched from sediment from contaminated site after incubating about 2 months. During the growth of the mixed microorganisms on hexachlorobenzene, the accumulating consumption of oxygen, the microbial population curve and the release of Cl- were investigated. The data suggest the rapid degradation of hexachlorobenzene to support microbial growth and the aerobic decholrination of hexachlorobenzene was observed. The result showed that the mixed microorganisms were able to utilize hexachlorobenzene as sole carbon and energy source. It was shown that up to 55% of HCB could be degraded during 18 days incubation at 30 degrees C in mineral salts medium (pH 7.0) with 4.5mg/L HCB. The calculated rate of hexachlorobenzene biodegradation was 137.5 microg/ (L x d). The 16S rDNA genes were amplified from community DNA by using primers specific to bacteria and were subsequently cloned. The cloned 16S rDNA fragments were reamplified, and restriction analysis was performed following separate digestion with enzymes Hae III and Rsa I. Application of restriction fragment length polymorphism screening approach revealed 9 clusters, and 3 major clusters were sequenced. Nearly complete 16S rDNA sequence analysis show that the microbial community was dominated by Alcaligenes and Azospirillum groups. This is the first report describing aerobic dechlorination of hexachlorobenzene via dehalorespiration by a microbial community which was enriched from contaminated site. The microbial community can be used to degrade highly recalcitrant chlorinated pollutants.