Molecular transformation and composition flow of dissolved organic matter in four typical concentrated leachates from the multi-stage membrane system.

Concentrated leachate (CL), characterized with high content salts and compositional complexity of dissolved organic matter (DOM), is difficult to degrade. Understanding the CL from molecular insight level is the requirement for further disposal based on their components. Here, typical CL samples were collected from the multi-stage membrane separation process in a large-scale leachate plant, including nanofiltration (NF), primary ultrafiltration (PUF), secondary nanofiltration (SNF), and reverse osmosis (RO). More than 95% of DOM was removed from raw CL, of which about 3/4 flowed into PUFCL and 1/5 flowed into SNFCL. DOM with macro-molecular weight (>500 Da, 30.46%) and highly unsaturated compounds (double-bond equivalents >15) were detected in PUFCL. Nearly half of DOM was CHO-only compounds (42.04%) in SNFCL. PUFCL was abundant in heteroatom species with higher-order oxygen (O ≥ 10), which was coincident with the trend of humic substance distribution (humic substance >1/2). Based on these properties results, advanced oxidation processes, such as ozonation, might be the right process for SNFCL rich in heteroatom species with low-order oxygen (O < 10). Abundant disulfides (S2O2-6 classes, 20.19%) and monovalent salts existed in ROCL, which should be removed from the system. These findings might provide basic information for the treatment of CLs from different membranes.

Chemical and olfactive impacts of organic matters on odor emission patterns from the simulated construction and demolition waste landfills.

The explosive increase of construction and demolition waste (CDW) caused the insufficient source separation and emergency disposal at domestic waste landfills in many developing countries. Some organic fractions were introduced to the CDW landfill process and resulted in serious odor pollution. To comprehensively explore the impacts of organic matters on odor emission patterns, five CDW landfills (OIL), with organic matters/ inert CDW components (O/I) from 5% to 30%, and the control group only with inert components (IL) or organics (OL) were simulated at the laboratory. The chemical and olfactive characters of odors were evaluated using the emission rate of 94 odorants content (ERtotal), theory odor concentration (TOCtotal), and e-nose concentration (ERENC), and their correlations with waste properties were also analyzed. It was found that the main contributors to ERtotal (IL: 93.0% NH3; OIL: 41.6% sulfides, 31.0% NH3, 25.9% oxygenated compounds) and TOCtotal (IL: 64.1% CH3SH, 28.2% NH3; OIL: 71.7% CH3SH, 24.8% H2S) changed significantly. With the rise of O/I, ERtotal, TOCtotal, and ERENC increased by 10.9, 20.6, and 2.1 times, respectively. And the organics content in CDW should be less than 10% (i.e., DOC<101.3 mg/L). The good regressions between waste properties (DOC, DN, pH) and ERENC- (r=0.86, 0.86, -0.88, p<0.05), TOCtotal- (r=0.82, 0.79, -0.82, p<0.05) implied that the carbon sources and acidic substances relating to organics degradation might result in that increase. Besides, the correlation analysis results (ERENC-vs.TOCtotal-, r=0.96, p<0.01; vs.ERtotal-, r=0.86, p<0.05) indicated that e-nose perhaps was a reliable odor continuous monitoring tool for CDW landfills.

Advanced treatment of effluents from an industrial park wastewater treatment plant by ferrous ion activated persulfate oxidation process.

The advanced oxidation technology, ferrous ion (Fe(II)) activated persulfate (PS) producing sulfate radicals, was used for the advanced treatment of effluent from an integrated wastewater treatment plant in a papermaking industrial park. Separate and interactive effects of PS dosage, Fe(II)/PS ratio and initial pH on chemical oxygen demand (COD) removal were analyzed by the response surface methodology (RSM). The results showed that Fe(II)-PS system was effective in COD removal from the secondary effluent. PS dosage was the most dominant factor with positive influence on COD removal, followed by initial pH value. The optimum conditions with COD removal of 54.4% were obtained at PS/COD of 2.2, initial pH of 6.47 and Fe(II)/PS of 1.89. UV-visible spectrum analysis showed that after RSM optimization, Fe(II)-PS system effectively degraded large organic molecules into small ones, and decreased humification degree of the effluent. Three-dimensional fluorescence analysis demonstrated that aromatic protein and fulvic substances were fully decomposed by the Fe(II)-PS treatment.

Sludge reduction and performance analysis of a modified sludge reduction process.

A modified sludge process reduction activated sludge (SPRAS) technology was developed by inserting a sludge process reduction (SPR) module, composed of an aeration tank and a settler, before the activated sludge system was proposed in this study. Compared with the anaerobic/anoxic/aerobic (AAO) process, the SPRAS resulted in a remarkable decrease in sludge production by 76.6%; sludge decay owing to lengthy solids retention time (about 121.5 d) could be the major cause. During the 217-day operation, the oxidation-reduction potential (ORP) (from 54 to -198 mV) and pH (from 7.8 to 5.0) at the bottom of the SPR settler gradually decreased, and low ORP and pH were in favor of sludge reduction in the SPRAS system. The insertion of the SPR module improved the removal efficiencies of suspended solids, chemical oxygen demand and ammonium nitrogen, and total nitrogen concentration in the effluent was reduced from 23.89 ± 4.82 to 14.16 ± 3.98 mg/L by 50% influent bypassing the SPR module. These results indicated that the SPRAS process could produce much less excess sludge and guarantee better effluent quality than the AAO process.

Phosphonate removal from discharged circulating cooling water using iron-carbon micro-electrolysis.

Phosphonate is a commonly used corrosion and scale inhibitor for a circulating cooling water (CCW) system. Its discharge could cause eutrophication of receiving waters. The iron-carbon (Fe/C) micro-electrolysis technology was used to degrade and remove phosphonate from discharged CCW. The influences of initial pH, Fe/C ratio (FCR) and temperature on phosphonate removal were investigated in a series of batch tests and optimized by response surface methodology. The quadratic model of phosphonate removal was obtained with satisfactory degrees of fitness. The optimum conditions with total phosphorus removal efficiency of 95% were obtained at pH 7.0, FCR of 1.25, and temperature of 45 °C. The phosphonate removal mechanisms were also studied. Phosphonate removal occurred predominantly via two consecutive reactive phases: the degradation of phosphonate complexes (Ca-phosphonate) and the precipitation of Fe/C micro-electrolysis products (PO4(3-), Ca²âº and Fe³âº).

Carbon sequestration for high-quality sludge-based carbon preparation via K/Na bi-molten salts pyrolysis.

Pyrolysis carbonization of sewage sludge is employed to achieve carbon sequestration and access carbon resources, while the quality of the obtained sludge-based carbon (SBC) is poor due to high ash contents and volatile organic matter. Here, carbonization in KOH/Na2CO3 (K/Na) bi-molten salts was developed for SBC preparation, improvement of carbon exploitation from biomass, and to reduce the contents of ash and volatile organic matter. The results showed that the surface area and pore volume of SBC under optimized conditions reached 1631 m2 g-1 and 1.312 cm3 g-1 at 700 °C, respectively, with a K/Na bi-molten salts/sludge ratio of 2:1 (K:Na = 5:5). Moreover, over fivefold the higher surface area and 43.61% amount of carbon element could be obtained, with a decrease in the mass loss rate for sludge pyrolysis of 25%. The mechanism behind the higher surface area of the SBC was identified and divided into three stages: intense dehydration and dehydrogenation caused by molten salt-enhanced polycondensation of protein and polysaccharide (200-400 °C), strongly reduced carbon-oxygen structure after deoxygenation reactions (400-600 °C), aromatization and cyclization of long-chain fatty acids triggered by deamidation of tar catalyzed by molten salts (600-900 °C). Eventually, 14.63% carbon was sequestered for the high-surface-area SBC prepared by K/Na bi-molten salts system.

Variations of nitrogen-metabolizing enzyme activity and microbial community under typical loading conditions in full-scale leachate anoxic/aerobic system.

Influent loading determines the performance of leachate treatment plant (LTP) facing the dynamic conditions, but enzyme expression in microbial community is unclear. Here, six nitrogen-metabolizing enzymes were detected during nitrification failures (NF), high loading (HL), low loading (LL), and low carbon/nitrogen (LCN) in a 500 m3/d LTP. Nitrogen removal in LL was 15 ± 5% higher than that in HL. The activity of hydroxylamine oxidoreductase decreased by 90% as the influent total nitrogen increased from 2450 mg/L to 3100 mg/L, which might be a critical enzyme causing the nitrification failure. Denitrifying enzyme abated by 1.3% as the carbon/nitrogen dropped by 1% in LCN. With the influent chemical oxygen demand decreased from 22000 mg/L to 12000 mg/L, the relative abundance of norank_f_Saprospiraceae dropped from 33.66% to 11.94%, and finally disappeared, which seems to be an indicator of the high load operation. These findings provide the basis for improving the efficiency of LTPs.

A variant of TNFR2-Fc fusion protein exhibits improved efficacy in treating experimental rheumatoid arthritis.

Etanercept, a TNF receptor 2-Fc fusion protein, is currently being used for the treatment of rheumatoid arthritis (RA). However, 25% to 38% of patients show no response which is suspected to be partially due to insufficient affinity of this protein to TNFalpha. By using computational protein design, we found that residue W89 and E92 of TNFR2 were critical for ligand binding. Among several mutants tested, W89Y/E92N displayed 1.49-fold higher neutralizing activity to TNFalpha, as compared to that of Etanercept. Surface plasmon resonance (SPR) based binding assay revealed that the equilibrium dissociation constant of W89Y/E92N to TNFalpha was 3.65-fold higher than that of Etanercept. In a rat model of collagen-induced arthritis (CIA), W89Y/E92N showed a significantly better ability than Etanercept in reducing paw swelling and improvement of arthritic joint histopathologically. These data demonstrate that W89Y/E92N is potentially a better candidate with improved efficacy in treating RA and other autoimmune diseases.

Decomposition of oil refinery sludge using E+-Ozonation process for carbon source releasing and TPH removal.

To utilize carbon source and decompose the petroleum hydrocarbon substances simultaneously, adding the electrolysis to ozonation (E+-Ozonation) was employed to deal with hazardous activated petroleum waste sludge (P-sludge). It was found that E+-Ozonation could accelerate the ozone utilization and hydroxyl radical (·OH) generation rate. Soluble chemical oxygen demand (SCOD) increased around 16.3 times than the control one (from 471 to 7700 mg/L). The potential carbon source, such as the short-chain carbon of acetate and propionate, increased from 50 to 1088 mg/L and from 27 to 614 mg/L respectively, and approximately accounted for a quarter of total SCOD. Total petroleum hydrocarbon (TPH) decomposition was observed with a much higher removal rate of 84.3% simultaneously, and the substances with the function group of C=C and C-C bonds decomposed greatly. The long- and medium-chain substances in TPH were converted into the short-chain substances (90% of C28-C40 of hydrocarbons was removed, while C10-C18 increased by 13.8%). E+-Ozonation process could be one of the promising methods for P-sludge decomposition through carbon source releasing and TPH removal.

The typical MSW odorants identification and the spatial odorants distribution in a large-scale transfer station.

Odorants from municipal solid waste (MSW) were complex variable, and the screening of key offensive odorants was the prerequisite for odor control process. In this study, spatial odor emissions and environmental impacts were investigated based on a large-scale working waste transfer station (LSWTS) using waste container system, and a comprehensive odor characterization method was developed and applied in terms of the odor concentration (OC), theory odor concentration (TOC), total chemical concentration (TCC), and electric nose (EN). The detected odor concentration ranged from 14 to 28 (dimensionless), and MSW container showed the highest OC value of 28, EN of 78, and TCC of 35 (ppm) due to the accumulation of leachate and residual MSW. Ninety-two species odorants were identified, and H2S, NH3, benzene, styrene, ethyl acetate, and dichloromethane were the main contributors in the container, while benzene, m,p,x-xylene, butanone, acetone, isopropanol, and ethyl acetate were predominant in the compression surface (CS) and compression plant (CP). Side of roads (SR) and unload hall (UH) showed low odorous impact. Based on this odor list, 20 species of odor substances were screened for the priority control through the synthetic evaluation method, considering the odorants concentrations, toxicity, threshold values, detection frequency, saturated vapor pressure, and appeared frequency. Graphical abstract.

[Advanced Treatment of Effluent from Industrial Park Wastewater Treatment Plant by Ferrous Ion Activated Sodium Persulfate].

Fe(II) activated sodium persulfate (PS) technology was used for advanced treatment of effluent from industrial park wastewater treatment plant. Separate and combined effects of PS/COD, Fe(II)/PS and pH on COD and TOC removal were analyzed by the response surface methodology. Variations of organic substances before and after Fe(II)-PS oxidation were characterized by UV-Vis spectrometry, gel chromatography and three-dimensional fluorescence. PS/COD and Fe(II)/PS had significant effect on COD removal, while all the three factors had significant effect on TOC removal. The combined effect of PS/COD and pH had significant effect on COD removal. COD and TOC removal efficiencies reached 50.7% and 60.6% under optimized conditions of PS/COD 3.47, Fe(II)/PS 3.32 and pH 6.5. Fe(II)-PS oxidation converted macromolecular organic substances to small ones, and reduced contents of protein-, humic- and fulvic-like substances.

Effect of humic substances on phosphorus removal by struvite precipitation.

Humic substances (HS) are a major fraction of dissolved organic matters in wastewater. The effect of HS on phosphorus removal by struvite precipitation was investigated using synthetic wastewater under different initial pH values, Mg/P molar ratios and HS concentrations. The composition, morphology and thermal properties of harvested precipitates were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM) and thermo-gravimetric analysis (TGA), respectively. It showed that inhibition effect of HS reached its maximum value of 48.9% at pH 8.0, and decreased to below 10% at pH>9.0. The increase of Mg/P ratio enhanced phosphorus removal efficiency, and thus reduced the influence of HS on struvite precipitation. At pH 9.0, the inhibitory effect of initial HS concentration matched the modified Monod model with half maximum inhibition concentration of 356mgL(-1), and 29% HS was removed in conjunction with struvite crystallisation. XRD analysis revealed that the crystal form of struvite precipitates was changed in the presence of HS. The morphology of harvested struvite was transformed from prismatic to pyramid owing to the coprecipitation of HS on crystal surface. TGA results revealed that the presence of HS could compromise struvite purity.

Conversion of organic carbon in the decomposable organic wastes in anaerobic lysimeters under different temperatures.

The quantitative fractions of conversion of organic carbon in the decomposable organic wastes with initial moisture of 70% sorted from municipal solid wastes (MSW) in lysimeters into biogas, leachate and solid residue were characterized, under temperatures of 25, 30 and 41 degrees C, respectively, and circulation of leachate generated within the lysimeter. It is found that 27% of organic carbon in the wastes are conversed into gases, 0.8% into leachate, and the other 72% remained in the decomposable solid residues, after 180 days' degradation at 41 degrees C. Higher temperature will lead to more rapid degradation and result to higher conversion of the organic carbon to biogas and lower to both solid residues and leachate, while the pollutant concentrations in leachate will be lower at a higher temperature and the values of COD are quite consistent with TOC.

A micro-aerobic hydrolysis process for sludge in situ reduction: performance and microbial community structure.

A sludge process reduction activated sludge (SPRAS) system by inserting a sludge process reduction (SPR) module, composed of a micro-aerobic tank and a settler, before activated sludge process was operated for sludge in situ reduction. The average removal efficiencies of COD and ammonium nitrogen were 86.6% and 87.9%, respectively. Compared to anoxic/aerobic (AO) process, SPRAS process reduced sludge production by 57.9% with observed sludge yield of 0.076 gVSS/gCOD. Pyrosequencing analyses revealed that the relative abundance and stability of microbial communities in SPRAS system were higher than AO system. Fermentative acidogenic classes Anaerolineae, Actinobacteria, Cytophagia and Caldilineae were enriched in the SPR module and responsible for sludge reduction. Specific comparison down to the genus level identified the enrichment of oxyanion-reducing bacteria (Sulfuritalea; Azospira; Ramlibacter), fermentative acidogenic bacteria (Propionivibrio; Opitutus; Caldilinea), slow growers (Ramlibacter) and predatory bacteria (Myxobacteria) in SPRAS system. Nitrifiers were also more abundant in SPRAS system than AO system.

Platinums sensitize human epithelial tumor cells to lymphotoxin alpha by inhibiting NFkappaB-dependent transcription.

Lymphotoxin alpha (LTalpha) was first identified as a direct anti-tumor factor, whereas increasing evidence has recently shown that in most cases the growth inhibition mediated by LTalpha requires the synergistic action of other factors, such as RNA transcription or protein synthesis inhibitor. In this study, we evaluated the combined effects of LTalpha and ten chemotherapeutic drugs on cell growth in a panel of human epithelial tumor cells, and explored the molecular mechanism of their mutual action. The results showed that platinums (cisplatin, carboplatin, oxaliplatin) are more universally effective than other chemotherapeutic drugs (doxorubicin, epi-doxorubicin, 5-flourouracil, mitomycin, cyclophosphamide, vincristine and vinorelbine) to enhance the response of six human epithelial tumor cell lines (A375, Bcap37, NCI-H157, SW480, BGC-823 and HeLa) to LTalpha. A systemic treatment with a combination of LTalpha and cisplatin in a human Bcap37 breast cancer xenograft nude mice model dramatically improved the therapeutic efficacy of LTalpha. Further analysis revealed that the sensitization of platinums was associated with platinums-induced suppression of nuclear factor-kappaB (NFkappaB) and subsequent downregulation of X-linked inhibitor of apoptosis protein (XIAP), which rescued caspase-3 from inhibition. Our results suggested that a proper combination of bio-agents such as LTalpha and conventional chemotherapeutic drugs such as platinums may be an efficient treatment strategy for human epithelial cancers.

Indomethacin enhances the cytotoxicity of recombinant human lymphotoxin alpha on tumor cells by suppressing NFkappaB signaling.

Indomethacin is widely used to treat inflammatory and prevent adverse events which frequently accrue in biotherapy. In phase I clinical trial of recombinant human lymphotoxin alpha (rhLTalpha), indomethacin was premedicated to alleviate chill and fever. However, it is unknown whether indomethacin influences the therapeutic efficacy of rhLTalpha. In this study we found that pre-treatment with low dose of indomethacin enhanced the cytotoxicity of rhLTalpha and/or cisplatin/adriamycin on human tumor cells. Further investigation demonstrated that indomethacin dose-dependently suppressed the activation of nuclear factor kappa B (NFkappaB) by inhibiting phosphorylation and degradation of IkappaBalpha. In addition, indomethacin decreased the expression of NFkappaB-regulated gene products involved in rhLTalpha-induced anti-apoptosis (XIAP, cFLIP and cIAP-1), which may explain its sensitization of tumor cells to rhLTalpha and/or cisplatin/adriamycin.

[Construction of combined site-directed random mutation libraries of recombinant human lymphotoxin].

To construct the combined site-directed random mutation library of recombinant human Lymphotoxin (rhLT) for in vitro molecular evolution study, and to study the structure and function relationship. The random point mutations at the sites of 46,106 and 130 were individually generated by overlap PCR amplification with the random nucleotide primers. The three point mutations were combined and cloned into pMD-18T vector to construct the combined mutation library. DNA sequencing was used to evaluate the diversity and randomness of the mutation sites. The combined mutation library was re-engineered, inserted in prokaryotic expression vector pBV220, transformed and expressed in Escherichia coli strain DH5alpha. The biological activity of some of the mutants was tested in 1929 mouse fibroblast cells. As much as 1.5 x 10(5) clones were obtained, which represents 4.5 times of the complete mutation libraries at 99% confidence. Sequencing 50 clones revealed no obvious bias in the nucleotide and amino acid mutations at the sites. Among the 30 expressed samples underwent for the bioassay, 70% (21 samples) were inactive, 23.3% (7 samples) had lower activity than rhLT, the remaining 6.7% (2 samples) had higher activity than rhLT. The combined site-directed random mutation library of rhLT has been constructed successfully. In combination with phase display, the library is ready for in vitro molecular evolution study.