Enhanced refractory organics removal by •OH and 1O2 generated in an electro-oxidation system with cathodic Fenton-like reaction.

Recently, carbon nanotubes coated carbon black and polytetrafluoroethylene (CNTs-C/PTFE) gas diffusion electrode was used as an air-cathode in an electro-oxidation (EO) system for effectively generating hydrogen peroxide (H2O2) through a 2-electron oxygen reduction reaction (ORR). This ORR-EO system not only lowered applied voltage and conserved energy, but the synergistic peroxone (O3/H2O2) reaction could increase hydroxyl radicals (•OH) generation for organics elimination. However, a significant proportion of H2O2 was left in the effluent of ORR-EO, which was a loss of resources and energy. In this study, a Fenton-like reaction for in-situ H2O2 decomposition to generate active oxidation species was inserted by introducing MnO2 into the cathodic catalyst layer, and the sole MnO2/CNTs-C/PTFE air-cathode could accomplish 90% of phenol degradation. When MnO2/CNTs-C/PTFE air-cathode combined with Ti/NATO anode in an ORR-EO system, all anodic oxidation, Fenton-like reaction, and peroxone took place to successfully generate •OH and singlet oxygen (1O2). Over 95% of TOC in phenol and landfill leachate bio-effluent was effectively eliminated, with 20% energy savings compared to the ORR-EO with CNTs-C/PTFE air cathode.

Degradation of triclosan by anodic oxidation/in-situ peroxone process: Kinetics, pathway and reaction mechanism.

Triclosan (TCS) is an emerging contaminant that threatens the environment and human health. This study was conducted to investigate TCS abatement by a novel electro-oxidation (EO) process, which used a Ti-based nickel and antimony doped tin oxide (NATO/Ti) anode and a carbon nanotubes (CNTs) doped carbon/PTFE (CNTs-C/PTFE) gas diffusion electrode (GDE) for oxygen reduction reaction (ORR). A comparative study was also performed for TCS degradation by using a traditional EO with a nickel foam cathode, termed as HER-EO. The optimal initial TCS concentration, current density and solution pH for TCS degradation during the ORR-EO and HER-EO were investigated. Results showed that ORR-EO removed more than 98% of TCS in 10-60 min under the concentration of 5-50 mg/L. The TCS degradation followed pseudo-first-order kinetics and its main intermediates were observed during the ORR-EO and HER-EO using liquid chromatography combined mass (LC-MS). The results of FED analysis and toxicity prediction by ECOSAR software showed that less intermediates accumulated during the ORR-EO and the residues were less harmful. The ORR-EO degradation mechanism for TCS was attacking on the ether bond and the benzene ring by •OH. This novel ORR-EO process exhibits a great merit in the field of emerging contaminants abatement.

Enhanced electro-oxidation/peroxone (in situ) process with a Ti-based nickel-antimony doped tin oxide anode for phenol degradation.

Recently, a novel proof-of-concept oxygen reduction reaction (ORR) based electro-oxidation (EO) process has been developed, which was accomplished by integrating anodic electrochemical oxidation coupled with an in situ electro-peroxone process, by harnessing the anodic by-product O3 reacted with ORR cathode generated H2O2. To further enhance EO coupled in situ electro-peroxone, a nickel and antimony doped tin oxide anodic catalyst layer, namely NATO, was fabricated on Ti mesh to improve anodic oxidation and reinforce the generation of O3, thus promoting in situ Electro-peroxone. As a result, O3 generation rate was enhanced by 12.6%. Complete phenol, as a model organic compound, and 95% of TOC removal were achieved, respectively, during ORR-EO. Through kinetics and instrument analysis, results show that the amount of intermediates accumulated during phenol degradation was much less in this Ti/NATO based ORR-EO system than in a traditional EO system. Moreover, 35.7% of the energy consumption was saved for ORR-EO, owing to its reduced applied voltage and the enhanced in situ electro-peroxone process.

GmWRKY54 improves drought tolerance through activating genes in abscisic acid and Ca2+ signaling pathways in transgenic soybean.

WRKY transcription factors play important roles in response to various abiotic stresses. Previous study have proved that soybean GmWRKY54 can improve stress tolerance in transgenic Arabidopsis. Here, we generated soybean transgenic plants and further investigated roles and biological mechanisms of GmWRKY54 in response to drought stress. We demonstrated that expression of GmWRKY54, driven by either a constitutive promoter (pCm) or a drought-induced promoter (RD29a), confers drought tolerance. GmWRKY54 is a transcriptional activator and affects a large number of stress-related genes as revealed by RNA sequencing. Gene ontology (GO) enrichment and co-expression network analysis, together with measurement of physiological parameters, supported the idea that GmWRKY54 enhances stomatal closure to reduce water loss, and therefore confers drought tolerance in soybean. GmWRKY54 directly binds to the promoter regions of genes including PYL8, SRK2A, CIPK11 and CPK3 and activates them. Therefore GmWRKY54 achieves its function through abscisic acid (ABA) and Ca2+ signaling pathways. It is valuable that GmWRKY54 activates an ABA receptor and an SnRK2 kinase in the upstream position, unlike other WRKY proteins that regulate downstream genes in the ABA pathway. Our study revealed the role of GmWRKY54 in drought tolerance and further manipulation of this gene should improve growth and production in soybean and other legumes/crops under unfavorable conditions.

Metal trabecular bone reconstruction system better improves clinical efficacy and biomechanical repair of osteonecrosis of the femoral head than free vascularized fibular graft: A case-control study.

In this study, we aim to compare and analyze the biomechanical repair and clinical efficacy of osteonecrosis of the femoral head (ONFH) with the use of metal trabecular bone reconstruction system and free vascularized fibular graft. The study enrolled 66 adult patients from medical records of nontraumatic ARCO 2A-3B stage ONFH. A simple ONFH model without surgical treatment was established in 13 cases, 29 cases were treated with metal trabecular bone reconstruction system, and 24 cases were treated with free vascularized fibular graft. Computer-recognized and extracted femur outlines were imported, and three-dimensional reconstructions were performed. The stress concentration and stress peak value were analyzed, and the Harris score, visual analog scale pain score, and operation status of the above patients were compared. Finally, quality of life assessment was performed using SF-36 scale. Metal trabecular bone reconstruction system provided less operation time, blood loss, and the total length of postoperative hospital stay than free vascularized fibular graft. Metal trabecular bone reconstruction system promoted bone reconstruction, increased bone mineral density and Harris score. The total clinical effective rate of young patients (20-40 years) was higher than that of older patients (41-60 years). Metal trabecular bone reconstruction system provided higher physical component summary, mental component summary, and role/social component summary than free vascularized fibular graft. This study demonstrates that both metal trabecular bone reconstruction system and free vascularized fibular graft can prevent or delay the progression of ONFH, while metal trabecular bone reconstruction system is a better choice because of better short-term clinical efficacy.

A robust and cost-effective integrated process for nitrogen and bio-refractory organics removal from landfill leachate via short-cut nitrification, anaerobic ammonium oxidation in tandem with electrochemical oxidation.

A cost-effective process, consisting of a denitrifying upflow anaerobic sludge blanket (UASB), an oxygen-limited anoxic/aerobic (A/O) process for short-cut nitrification, and an anaerobic reactor (ANR) for anaerobic ammonia oxidation (anammox), followed by an electrochemical oxidation process with a Ti-based SnO2-Sb2O5 anode, was developed to remove organics and nitrogen in a sewage diluted leachate. The final chemical oxygen demand (COD), ammonia nitrogen (NH4(+)-N) and total nitrogen (TN) of 70, 11.3 and 39 (all in mg/L), respectively, were obtained. TN removal in UASB, A/O and ANR were 24.6%, 49.6% and 16.1%, respectively. According to the water quality and molecular biology analysis, a high degree of anammox besides short-cut nitrification and denitrification occurred in A/O. Counting for 16.1% of TN removal in ANR, at least 43.2-49% of TN was removed via anammox. The anammox bacteria in A/O and ANR, were in respective titers of (2.5-5.9)×10(9) and 2.01×10(10)copy numbers/(gSS).

Nonionic surfactant greatly enhances the reductive debromination of polybrominated diphenyl ethers by nanoscale zero-valent iron: mechanism and kinetics.

Nanoscale zero-valent iron (nZVI) has been considered as an effective agent for reductive debromination of polybrominated diphenyl ethers (PBDEs). But the high lipophilicity of PBDEs will hinder their debromination owing to the inefficient contact of PBDEs with nZVI. In this study, different ionic forms of surfactants were investigated aiming to promote PBDE debromination, and the beneficial effects of surfactant were found to be: nonionic polyethylene glycol octylphenol ether (Triton X-100, TX)>cationic cetylpyridinium chloride (CPC)>anionic sodium dodecyl benzenesulfonate (SDDBS). Except for with SDDBS, the promotion effect for PBDE debromination was positively related to the surfactant concentrations until a critical micelle concentration (CMC). The debromination process of octa-BDE and its intermediates could be described as a consecutive reaction. The corresponding rate constants (k) for the debromination of parent octa-BDE (including nona- to hepta-BDEs), the intermediates hexa-, penta-, and tetra-BDEs are 1.24 × 10(-1) h(-1), 8.97 × 10(-2) h(-1), 6.50 × 10(-2) h(-1) and 2.37 × 10(-3) h(-1), respectively.

[Reductive debromination of polybrominated diphenyl ethers in aquifier by nano zero-valent iron: debromination kinetics and pathway].

Nano-zerovalent iron (nZVI) approach is effective in the debromination of polybrominated biphenyl ethers (PBDEs). The kinetics and degradation pathway are the key issues to understand the PBDEs degradation mechanisms. In this study, nZVI, synthesized through liquid phase reduction method, coupled with Triton X-100, could completely debrominate the highly brominated congeners of a commercial octa-BDEs mixture within 46 h. The debromination of octa-BDEs could be described by means of pseudo-first-order kinetics with the reaction constant (k) of 0.106 h(-1). In case of lacking the PBDE standards, an effective approach has been developed to determine the unknown PBDE congeners using the quantitative-structure retention relationship (QSRR) model. The retention time of all 39 PBDE congeners in a standard mixture was firstly analyzed with gas chromatography coupled with an electron capture detector (GC-ECD), and the relative retention time (RRT) for each standard was obtained after normalizing the RT by the average RT of BDE47 and BDE183. Then a QSRR model was developed by fitting the RRT of each PBDE congener and its specific RRT index. The debromination products of octa-BDEs were identified using this QSRR model and the degradation pathway of octa-BDEs was elucidated. The results showed that in the stepwise reductive debromination process of PBDEs by nZVI, meta-debromin was facile to be degraded.

Nernst-ping-pong model for evaluating the effects of the substrate concentration and anode potential on the kinetic characteristics of bioanode.

Understanding the electron-transfer mechanism and kinetic characteristics of bioanodes is greatly significant to enhance the electron-generating efficiencies in bioelectrochemical systems (BESs). A Nernst-ping-pong model is proposed here to investigate the kinetics and biochemical processes of bioanodes in a microbial electrolysis cell. This model can accurately describe the effects of the substrate (including substrate inhibition) and the anode potential on the current of bioanodes. Results show that the half-wave potential positively shifts as the substrate concentration increases, indicating that the rate-determining steps of anodic processes change from substrate oxidation to intracellular electron transport reaction. The anode potential has negligible effects on the enzymatic catalysis of anodic microbes in the range of -0.25 V to +0.1 V vs. a saturated calomel electrode. It turns out that to reduce the anodic energy loss caused by overpotential, higher substrate concentrations are preferred, if the substrate do not significantly and adversely affect the output current.

Characterization of a butanol-acetone-producing Clostridium strain and identification of its solventogenic genes.

A unique Clostridium species strain G117 was obtained in this study to be capable of producing dominant butanol from glucose. Butanol of 13.50 g/L was produced when culture G117 was fed with 60 g/L glucose, which is ~20% higher than previously reported butanol production by wild-type Clostridium acetobutylicum ATCC 824 under similar conditions. Strain G117 also distinguishes itself by generating negligible amount of ethanol, but producing butanol and acetone as biosolvent end-products. A butanol dehydrogenase gene (bdh gene) was identified in strain G117, which demonstrated a ~200-fold increase in transcription level measured by quantitative real-time PCR after 10h of culture growth. The high transcription suggests that this bdh gene could be a putative gene involved in butanol production. In all, Clostridium sp. strain G117 serves as a potential candidate for industrial biobutanol production while the absence of ethanol ensures an economic-efficient separation and purification of butanol.

Quantification and characterization of ß-lactam resistance genes in 15 sewage treatment plants from East Asia and North America.

The emerging antibiotic resistance genes in the aquatic environment have aroused public concern. As ß-lactam is the most widely used group of antibiotics, ß-lactam resistance genes were selected to investigate their distribution and diversity in the activated sludge from 15 geographically different sewage treatment plants (STPs) of China, Singapore, USA, and Canada. Specific PCR and quantitative real-time PCR (q-PCR) were used to investigate the occurrence and abundance of nine ß-lactam resistance genes. Five genes (OXA-1, OXA-2, OXA-10, ampC, and TEM-1) were detected in most of the sludge collected, while three genes (mecA, CTX-M-1, and SME) were not found in any sludge sample. The total abundances of the six detected ß-lactam resistance genes in the 15 STPs varied from 5.34 × 10(1) copies/ng DNA (ampC) to 5.49 × 10(4) copies/ng DNA (OXA-1). Overall, OXA-1 had the highest total concentration, followed by IMP and OXA-10. Noticeably, the abundances of TEM-1 in Chinese STPs were generally higher than those in the STPs of other countries, while the abundances of OXA-2 and IMP in the STPs of North America were much greater than those of East Asia. A total of 78 clones carrying ß-lactam resistance genes were randomly selected from six clone libraries for phylogenetic diversity analysis; the similarity of these cloned genes to known ß-lactam resistance genes with sequence identities ranged from 96% to 100%. Furthermore, OXA-1, ampC, and IMP were found to be more diverse than the other ß-lactam resistance genes.

Enhancement of hydrogen production in a single chamber microbial electrolysis cell through anode arrangement optimization.

Reducing the inner resistances is crucial for the enhancement of hydrogen generation in microbial electrolysis cells (MECs). This study demonstrates that the optimization of the anode arrangement is an effective strategy to reduce the system resistances. By changing the normal MEC configuration into a stacking mode, namely separately placing the contacted anodes from one side to both sides of cathode in parallel, the solution, biofilm and polarization resistances of MECs were greatly reduced, which was also confirmed with electrochemical impedance spectroscopy analysis. After the anode arrangement optimization, the current and hydrogen production rate (HPR) of MEC could be enhanced by 72% and 118%, reaching 621.3±20.6 A/m3 and 5.56 m3/m3 d respectively, under 0.8 V applied voltage. A maximum current density of 1355 A/m3 with a HPR of 10.88 m3/m3 d can be achieved with 1.5 V applied voltage.

Phthalates biodegradation in the environment.

Phthalates are synthesized in massive amounts to produce various plastics and have become widespread in environments following their release as a result of extensive usage and production. This has been of an environmental concern because phthalates are hepatotoxic, teratogenic, and carcinogenic by nature. Numerous studies indicated that phthalates can be degraded by bacteria and fungi under aerobic, anoxic, and anaerobic conditions. This paper gives a review on the biodegradation of phthalates and includes the following aspects: (1) the relationship between the chemical structure of phthalates and their biodegradability, (2) the biodegradation of phthalates by pure/mixed cultures, (3) the biodegradation of phthalates under various environments, and (4) the biodegradation pathways of phthalates.

Anaerobic degradation of dimethyl phthalate in wastewater in a UASB reactor.

Over 99% of dimethyl phthalate (DMP) and 93% of chemical oxygen demand (COD) were effectively removed in a continuous upflow anaerobic sludge blanket (UASB) reactor from a wastewater containing 600 mg/L DMP at 8h of hydraulic retention time (HRT), corresponding to a loading rate of 3g-COD/(Ld). Each gram of sludge, expressed as volatile suspended solids (VSS), had a maximum specific methanogenic activity (SMA) of 24 mg-CH(4)/(g-VSSd) using DMP as the sole carbon source. The sludge yield was estimated as 0.08 g-VSS/g-COD. During anaerobic degradation, DMP was de-esterified, first to mono-methyl phthalate (MMP) and then to phthalate, before being de-aromatized and subsequently converted to CH(4) and CO(2). The maximum specific degradation rates of DMP, MMP and phthalate were 415, 88 and 36 mg/(g-VSSd), respectively. Analysis based on polymerase chain reaction (PCR) and denaturing gradient gel electrophoresis (DGGE) showed a gradual shift of microbial population with the increase of DMP loading.

Denitrifying degradation of dimethyl phthalate.

Results of batch experiments on the denitrifying degradation of dimethyl phthalate (DMP) was most favorable at pH 7-9 and 30-35 degrees C. DMP was first degraded to monomethyl phthalate (MMP), which was in turn degraded to phthalate before complete mineralization. There was no fatty acid residue in the mixed liquor throughout the experiments. The maximum specific degradation rates were 0.32 mM/(gVSS x h) for DMP, 0.19 mM/(gVSS x h) for MMP, and 0.14 mM/(gVSS x h) for phthalate. About 86% of available electron in DMP was utilized for denitrification; the remaining 14% was presumable conserved in the new biomass with an estimated yield of 0.17 mg/mg DMP. Based on 16S rDNA analysis, the denitrifying sludge was mainly composed of beta-subdivision and alpha-subdivision of Proteobacteria (33 and 5 clones out of a total of 43 clones, respectively), plus some Acidobacteria. Using a primer set specifically designed to amplify the denitrification nirK gene, 10 operational taxonomy units (OTUs) were recovered from the clone library. They clustered into a group in the alpha-subdivision of Proteobacteria most closely related to denitrifier Bradyrhizobium japonicum USDA110 and several environmental clones.