Electronic Excitation Characteristics and Spectral Behavior of Phosphate Anions.

Absorption spectra are fundamental bases for the qualitative and quantitative analysis of the target chemical, and the development of an analytical model can be improved by studying its characteristics and rules. In the present study, the electronic excitation characteristics of phosphate anions (H2PO4-, HPO42-, and PO43-) were analyzed based on the charge-transfer spectrum. In addition, the absorption spectra of phosphate anions at the energy level of PBE0/6-311+G (d,p) were recorded based on the time-dependent density functional theory (TD-DFT) method. Different (HPO42-)n·(H2O)10-n molecular clusters were theoretically constructed, and the combined TD-DFT method and independent gradient model revealed that red shift of the maximum absorption wavelength (λmax) with the increase of phosphate anion concentration (0-10 mM) may be caused by the decrease of hydrogen bond interaction. In addition, the prominent dispersion in the short-wave region mainly resulted in the red shift of λmax with the increase in optical path length (1-100 mm). Moreover, with the increase in spectral bandwidth (0.4-3.0 nm), λmax slightly blue-shifted because of the increase in energy through the slit, and repeatability of the corresponding absorbance measurement at λmax gradually improved. As the spectral bandwidth increased, light monochromaticity became poor, resulting in the decrease of the linearly fitted correlation coefficient of the concentration-absorbance curve. Finally, the multivariate analysis of variance results showed that the optical path length was the most significant factor that influenced the absorption spectral characteristics of phosphate anions. This study provides a basis for the qualitative and quantitative analysis of phosphate anions by using absorption spectra and also renders a theoretical reference for absorption spectroscopy of other chemicals.

Comparative Investigation of the Spectroscopic Behavior Based on High-Concentrated Solution in Nitrogen and Air Atmospheres.

In order to accurately obtain photometric information of high concentration SO42- and other substances in the process industry, the spectroscopy behavior of SO42-, S2-, Ni2+ and Cu2+ in air and nitrogen atmosphere was compared based on the UV-visible spectrophotometer with a nitrogen replacing the oxygen. Different from Ni2+ and Cu2+, the accuracy of SO42- and S2- in the ultraviolet region was effectively improved by using a nitrogen atmosphere (P detection results were regressed within the limited standard range, RE < 5%). The nitrogen atmosphere suppressed the additional light attenuation caused by its absorption of ultraviolet rays by isolating oxygen and was also reflected in the decrease in the degree of red shift of the characteristic wavelength for SO42- with increasing concentration. Therefore, the detection results of SO42- showed an effective improvement in sensitivity. Nevertheless, according to the complementary experimental results and theoretical calculations, in addition to oxygen absorption, the low detection accuracy of SO42- high concentration is also attributed to the reduction of the energy required for electronic excitation per unit group caused by the interaction between SO42- groups, resulting in a deviation of the C-A curve from linearity at high concentrations. The influence of this intermolecular force on the detection results is far more important than oxygen absorption. The research can provide reliable theoretical guidance and technical support for the pollution-free direct measurement of high-concentration solutions in the process industry and promote the sustainable development of the process industry.

Differentially Expressed Proteins From the Peritrophic Membrane Related to the Lethal, Synergistic Mechanisms Observed in Hyphantria cunea Larvae Treated With a Mixture of Bt and Chlorbenzuron.

Hyphantria cunea (Drury) (Lepidoptera: Arctiidae) is an important forest insect pest around the world. It attacks a variety of broad-leaf trees. It has caused serious economic and ecological damage to its new habitats. A mixture of Bt and chlorbenzuron has a higher toxicity and faster killed than those of either agent alone to the 4th instar larvae of H. cunea both by the lab and field test results, and the toxic effect of the mixture treatment was significantly enhanced. Using proteomics technology, including SDS-PAGE and MALDI-TOF-TOF MS, we analyzed differentially expressed proteins of the peritrophic membrane (PM) of the 4th instar larvae of H. cunea, which were treated with the mixture. We identified 91 significantly differentially expressed proteins of the PM of the 4th instar larvae of H. cunea and those proteins were found to be involved in different metabolic pathways and processes. The energy-related and structural proteins made up the largest proportion of all of the identified proteins, and the mixture treatment of proteins was the small proportion of the identified structural proteins and energy-related proteins among the Bt, chlorbenzuron, and mixture treatments. Based on the proteomic data, we found that some proteins and their corresponding functions and pathways were related to the lethal mechanisms observed in 4th instar larvae of H. cunea when treated by the mixture.

Synergistic strategy of solute environment and phase control of Pb-based anodes to solve the activity-stability trade-off.

The contradiction between the activity and stability of metal anodes exists extensively, especially in acid electrooxidation under industrial-level current density. Although the anode modification enhanced the initial activity of anodes, its long-term activity is limited by anode slime accumulation. Herein, a synergistic strategy, coupling the solute environment with the phase control of anodes, is proposed to achieve the trade-off between activity and stability of Pb-based anodes in concentrated sulfuric acid electrolysis. Non-exogenous Mn2+ motivated a series of positive behaviours of reactive-oxygen-species capture, anode reconstruction and corrosion-dependent activity alleviation. The synergistic effects, which are crystal phase-dependent, mainly benefit from the continuous self-healing ability of the specific crystal phase of MnO2 on the anodes by the coexisted Mn2+. Compared with Mn2+/α-MnO2, Mn2+/γ-MnO2 exhibited outperformed activity and stability in boosting oxygen evolution reaction (OER) and reducing hazardous pollutants, which resulted from the energy difference in the rate-determining step of OER and in the selectivity priority of Mn2+/MnO2 oxidation pathway. Interestingly, the pre-coated γ-MnO2 on the anode also presents excellent inheritance, guaranteeing the unchanged crystal phase of MnO2 and the high performance in ultra-low hazardous slime generation in subsequent Mn2+ oxidation. The sustainability of Mn2+/γ-MnO2 was proved in the operating hydrometallurgy conditions on Pb-based anodes. This strategy offers a promising approach for this common issue in electrooxidation-related areas.

Direct determination of high-concentration As(III) by UV high-reference differential absorption spectroscopy for cleaner As(III) removal promotion via sulfurization.

The current methods for determining high-concentration As(III) in the high-acid matrix from the copper smelting industry are complex, time-consuming, and costly. This limits effective modulation of sulfurizing agent dosage for As(III) removal via sulfurization, aggravating hazardous waste generation. Herein, a simple, rapid, and nondestructive UV high-reference differential absorption spectroscopy was developed to directly determine high-concentration As(III) in simulated high-acid wastewater. Time-dependent density functional theory calculations indicated that the spectral curve redshift with As(III) concentration increasing was related to the decrease of electron transition energies and energy gaps. When using high-reference solutions, the least redshift in the maximum absorption wavelength and the highest upper limit of linear fitting concentration could be obtained. Therefore, the piecewise quantitative linear model of differential absorbance and concentration was established under high-reference. The quantitative range of the model within 0.06-20.00 g/L As(III) with a mean relative error of < 5.0 % and standard recovery rates within 98.0 %-104.0 % indicated high accuracy. Additionally, the relative standard deviations of < 1.5 % (n = 5) revealed good precision. All results indicated the high feasibility of the developed method in alleviating linear deviation caused by redshift and absorption saturation. Furthermore, it has potential significance in saving sulfurizing agent dosage and reducing hazardous waste generation from the source, thereby facilitating a cleaner process for removing As(III) via sulfurization.

High-sensitivity detection of low-concentration heavy metal ions in solution by multiple reflection enhanced absorption (MREA) spectroscopy.

Heavy metal ions (Cr6+, Co2+, Ni2+, and Cu2+) in the electroplating and electrolysis industries are significantly related to process parameters and product quality, even at lower concentrations. Absorption spectroscopy is widely used for substance qualitative and quantitative analysis, which is an analytical method with the potential for real-time monitoring of heavy metal ions concentration in industrial processes. In this paper, a low-concentration heavy metal ion analysis method based on multiple reflection enhanced absorption (MREA) is proposed. Compared with traditional absorption, MREA has the advantages of low concentration detection limit and high-sensitivity. First, a reflective film (Al-SiO2) was prepared and a multiple reflection optical structure was designed to realize multiple parallel reflections of light in the solution medium. Then absorption spectra of low-concentration Cr6+, Co2+, Ni2+ and Cu2+ solutions were measured by MREA and traditional absorption methods. Finally, spectral bandwidth and incident light spots were optimized to obtain a superior absorption enhancement effect. The results showed that MREA could effectively increase the substance absorbance compared with traditional absorption. At the same time, with the optimal spectral bandwidth (0.4 nm) and incident light spot (1 mm), the detection limit of Cr6+, Co2+, Ni2+ and Cu2+ was reduced by 81.48%, 82.52%, 80.92% and 82.93%, respectively. The sensitivity was improved by 5-6 times, which was more obvious for low-concentration detection. In addition, the MREA method can achieve ion concentration analysis when Cr6+, Co2+, Ni2+, and Cu2+ coexist, and the linear correlative coefficients of the C-A curves were all greater than 0.999. Moreover, by adjusting reflectivity of the reflective film and the number of reflections in the optical structure, the results of the MREA method can be further optimized for the low-concentration heavy metal ion analysis. The MREA method has the advantages of simplicity, rapidity and versatility, which can provide the technical foundation for real-time monitoring method development of low-concentration heavy metal ions in industrial processes.

TMX2 potentiates cell viability of hepatocellular carcinoma by promoting autophagy and mitophagy.

The dysregulation of membrane protein expression has been implicated in tumorigenesis and progression, including hepatocellular carcinoma (HCC). In this study, we aimed to identify membrane proteins that modulate HCC viability. To achieve this, we performed a CRISPR activation screen targeting human genes encoding membrane-associated proteins, revealing TMX2 as a potential driver of HCC cell viability. Gain- and loss-of-function experiments demonstrated that TMX2 promoted growth and tumorigenesis of HCC. Clinically, TMX2 was an independent prognostic factor for HCC patients. It was significantly upregulated in HCC tissues and associated with poor prognosis of HCC patients. Mechanistically, TMX2 was demonstrated to promote macroautophagy/autophagy by facilitating KPNB1 nuclear export and TFEB nuclear import. In addition, TMX2 interacted with VDAC2 and VADC3, assisting in the recruitment of PRKN to defective mitochondria to promote cytoprotective mitophagy during oxidative stress. Most interestingly, HCC cells responded to oxidative stress by upregulating TMX2 expression and cell autophagy. Knockdown of TMX2 enhanced the anti-tumor effect of lenvatinib. In conclusion, our findings emphasize the pivotal role of TMX2 in driving the HCC cell viability by promoting both autophagy and mitophagy. These results suggest that TMX2 May serve as a prognostic marker and promising therapeutic target for HCC treatment.Abbreviation: CCCP: Carbonyl cyanide 3-chlorophenylhydrazone; Co-IP: co-immunoprecipitation; CRISPR: clustered regularly interspaced short palindromic repeat; ER: endoplasmic reticulum; HCC: hepatocellular carcinoma; KPNB1: karyopherin subunit beta 1; PRKN: parkin RBR E3 ubiquitin protein ligase; ROS: reactive oxygen species; TFEB: transcription factor EB; TMX2: thioredoxin related transmembrane protein 2; VDAC2: voltage dependent anion channel 2; VDAC3: voltage dependent anion channel 3; WB: western blot.

B4GALNT1 promotes hepatocellular carcinoma stemness and progression via integrin α2ß1-mediated FAK and AKT activation.

Background & Aims: ß-1,4-N-Acetyl-galactosaminyltransferase 1 (B4GALNT1) has been reported to contribute to the development of human malignancies. However, its role in hepatocellular carcinoma (HCC) remains uncharacterised. In this study, we aimed to elucidate the role of B4GALNT1 in HCC stemness and progression. Methods: Immunohistochemical staining was used to evaluate B4GALNT1 expression in HCC tissues and adjacent normal liver tissues. Flow cytometry analysis and sphere formation analysis were performed to investigate the role of B4GALNT1 in HCC stemness. Colony formation, Incucyte, wound-healing, Transwell migration, and invasion assays, and an animal model were used to study the role of B4GALNT1 in HCC progression. RNA-sequencing and co-immunoprecipitation were used to investigate the downstream targets of B4GALNT1. Results: B4GALNT1 was upregulated in HCC and associated with poor clinical outcome of patients with the disease. Moreover, B4GALNT1 promoted HCC stemness, migration, invasion, and growth. Mechanistically, B4GALNT1 not only promoted the expression of the integrin α2ß1 ligand THBS4, but also directly interacted with the ß subunit of integrin α2ß1 ITGB1 to inhibit its ubiquitin-independent proteasomal degradation, resulting in activation of FAK and AKT. Ophiopogonin D inhibited HCC stemness and progression by reducing ITGB1 and THBS4 expression and inhibiting FAK and AKT activation. Conclusions: Our study suggests the B4GALNT1/integrin α2ß1/FAK/PI3K/AKT axis as a therapeutic target for the inhibition of HCC stemness and tumour progression. Impact and implications: The role and regulatory mechanism of B4GALNT1 in HCC have not been studied previously. Here, we reveal that B4GALNT1 has a crucial role in HCC stemness and progression by activating the integrin α2ß1/FAK/PI3K/AKT axis, providing a potential target for HCC therapy. In addition, we find Ophiopogonin D as a potential therapeutic drug for patients with HCC.

The characteristics of ultraviolet absorption and electronic excitation of sulfate at high concentrations.

The variation of spectra and the characteristics of electronic excitation are critical for establishing a model for quantifying sulfate at high concentrations. The absorption characteristics of sulfate are affected by the optical pathlength and sulfate concentration. The absorption coefficient declines by approximately 86.09-96.20% with an increasing concentration (0-130 g/L) at different optical pathlengths (1-100 mm). Moreover, a high sensitivity and accuracy can be achieved at weak absorption wavelengths or at lower optical pathlengths when high concentrations of sulfate are detected. In addition, the maximum absorption wavelength of sulfate redshifts by approximately 0-10 nm with an increasing concentration and optical pathlength, which is significantly affected by the optical pathlength. The (H2SO4)n‧(H2O)4-n models were established at the PBEPBE/6-311++G(d, p) level of theory. There absorption spectra were calculated by the time-dependent density functional theory (TD-DFT) method. As a result, the maximum absorption wavelength redshifted from 180.16 nm to 192.71 nm with an increasing sulfate concentration, and the corresponding absorption coefficient demonstrated a declining trend. Furthermore, the electron-hole and natural bond orbital (NBO) analysis indicate that the type of electronic excitation changes from a n(O) â†’ σ*(S-O) localized excitation to n â†’ σ* charge-transfer excitation as the sulfate concentration increases. This study provides a theoretical foundation for understanding the spectral behavior of sulfates and constructing the quantification models or methods that can also be applied to analyze the spectroscopy of other chemicals.

Highly active and stable Ni-Fe bimetal prepared by ball milling for catalytic hydrodechlorination of 4-chlorophenol.

A novel Ni-Fe bimetal with high dechlorination activity for 4-chlorophenol (4-CP) was prepared by ball milling (BM) in this study. Increasing Ni content and milling time greatly enhanced the dechlorination activity, which was mainly attributed to the homogeneous distribution of Ni nanoparticles (50-100 nm) in bulk Fe visualized by scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDS) with image mapping. In comparison with the Ni-Fe bimetal prepared by a chemical solution deposition (CSD) process, the ball milled Ni-Fe bimetal possessed high dechlorination activity and stability before being used up. Dechlorination kinetics indicated that the dechlorination rates of 4-CP increased with increasing Ni-Fe dose but decreased with increasing solution pH. Solution pH had a significant effect on the dechlorination of 4-CP and the passivation of the Ni-Fe bimetal. The enhanced pH during the dechlorination process significantly accelerated the formation of passivating film on the bimetallic surface. The Ni-Fe bimetal at the dose of 60 g/L was reused 10 times without losing dechlorination activity for 4-CP at initial pH less than 6.0, but the gradual passivation was observed at initial pH above 7.0.

Size effect of γ-MnO2 precoated anode on lead-containing pollutant reduction and its controllable fabrication in industrial-scale for zinc electrowinning.

Lead (Pb) is the most widely used anode in zinc (Zn) electrowinning and other metallurgical industries. The resource loss and environmental pollution caused by Pb anode corrosion are urgent problems to be solved. A γ-MnO2 precoated anode was prepared successfully to reduce the Pb-containing pollutant. The size effects with its controllable preparation on an industrial scale were studied. Severe nonuniform distribution of γ-MnO2 film was observed with curbing the reduction of anode slime only 68%, when anode size increased from lab to industry. Nonuniform rate (R) and average thickness (d) were found to be the key indicators to determine the film structure distribution and their performance differences, which were random and difficult to be controlled in scale-up size. However, a controllable industrial γ-MnO2 precoated anodes (IMPA) fabricated through optimized current density (J0) and electrodeposition time (t) in our developed film-forming system. Then, the long-term performances of two IMPA with different indicators (IMPA-1: R = 34%, d = 108 µm, IMPA-2: R = 23%, d = 55 µm) were compared with the industrial typical Pb-based anode (ITPA). Of the three different anodes, the optimized IMPA-2 displayed the best performance. Within 24 d of electrowinning cycle, the corrosion inhibition effect and the anode slime reduction rate for IMPA-2 improved by 56% and 30% than IMPA-1, and improved by 100% and 91% than ITPA. Furthermore, the mechanism analysis of size effect change showed that R of IMPA was contributed to the local gas holdup distribution along the anode. Controlled size effect of uniform oxide film will have a future application prospect for the sustainability of industry, which provides an important cleaner production of Zn electrowinning and related hydrometallurgy industries.

Lead release kinetics and film transformation of Pb-MnO2 pre-coated anode in long-term zinc electrowinning.

Lead pollution precaution caused by lead-based anode corrosion is a hot and challenging issue for zinc electrowinning. A novel functional lead-based anode (MnO2 pre-coated anode-MPA) was precisely fabricated and its long-term performances were studied compared with typical Pb-1%Ag anode (TPA). Results indicated that MPA posed excellent effects on synergistic inhibiting lead dissolution and reducing hazardous pollutants generation, and decreasing the lead content of zinc products by 81%. Further, the underlying mechanism of film growth and transformation in structure, composition and crystal phase, the migration and distribution of lead and anode slime during electrolytic, were clarified in-depth. Dynamic material flow analysis confirmed that MPA reduced the entire lead migration amount by over 92% compared with TPA. The compact multilayer structure of the MPA film and self-reparation effects of local structure provided better and persistent protection for the lead matrix, which greatly retarded the high-speed corrosion of lead anode. Compared with α-MnO2 in TPA, the formation and maintenance of γ-MnO2 in MPA accelerated the oxygen evolution reaction and inhibited the anode slime generation. This finding provides new insights in pollution precaution and control by designing and tuning new functional anode in hydrometallurgy process.

Phenol biodegradation and simultaneous nitrogen removal using a carbon fiber felt biofilm reactor.

Phenol biodegradation and its effect on the biological nitrogen removal were studied in a biofilm reactor (15 L) packed with carbon fiber felt carriers. Meanwhile, the effects of the effluent internal recirculation ratios (0, 100% and 200%) and the air flow rates (0.42, 0.83, 1.46, 2.08 and 3.33 L/min) on the performance of system were tested. The system exhibited an excellent capacity for simultaneous phenol biodegradation and biological nitrogen removal without effluent internal recirculation when the influent phenol concentration was as high as 1,000 mg/L (organic loading rate of 9.54 kg COD/(m(3) d)) and the ammonia loading rates of 0.20, 0.32 and 0.40 kg NH(4)(+)-N/(m(3) d) respectively). Nitrification process was inhibited at the influent phenol concentration of 1,200-1,300 mg/L with average ammonia removal efficiency of 26.9%. The nitrifiers activity could be recovered in the perfect performance of system for phenol biodegradation. However, denitrification was not affected by the process of phenol biodegradation. In the air flow rates of 1.46-2.08 L/min, the system manifested stable operation for phenol elimination and nitrogen removal. Dissolved oxygen (DO) distributions in carbon fiber felt biofilm descended gradually from the external to the center of the carrier in all air flow rates.

Preparation of Fe-Cu catalysts and treatment of a wastewater mixture by microwave-assisted UV catalytic oxidation processes.

Microwave-assisted UV catalytic oxidation (MW/UV) is a potential method to treat organic pollutants that have non-biological degradability and high toxicity. To achieve high treatment efficiency, it is crucial to prepare heterogeneous photocatalysts with a high activity. Iron-copper catalysts were prepared by four different methods. Synthetic wastewater containing aniline and nitrophenol (TOC = 1000 mg/L) was treated. The key parameters including the proportion of Fe2O3 and CuO and the total content of the active components are discussed. The optimum catalyst dosage and the whole catalytic oxidation process were investigated, and different catalytic oxidation systems were also compared. The catalyst prepared by impregnation was best: the highest TOC removal efficiency reached 78%. The optimum proportion of Fe2O3 and CuO and the content of the total active composition were 4:1 and 30%, respectively. The catalyst preparation method had a greater influence on the MW/UV system than on the microwave (MW) system, and the synergistic effect between MW and UV was verified. The MW/UV system was more susceptible to catalyst dosage than was the MW system, and the optimum catalyst dosage was 5 g/L. The catalyst and H2O2 had a synergistic effect. The presence of a possible non-thermal microwave effect could be expected.

Influence of Mn2+ ions on the corrosion mechanism of lead-based anodes and the generation of heavy metal anode slime in zinc sulfate electrolyte.

The influence of Mn2+ ions on the generation of heavy metal anode slime during zinc electrolysis industry was extensively investigated using several electrochemical methods, electron microscope technologies, and particle size analysis. Results showed that the Mn2+ could obviously promote oxygen evolution reaction (OER) and thereby weaken oxidation efficiency of Mn2+ (ηMnO2) and dissolution of Pb2+. The significant improvement in kinetic parameters for OER was found in electrolytes of 1 and 3 g/L Mn2+, but became unstable as the Mn2+ concentration increased to 10 g/L. This result was correlated with much different properties of oxide layers that its changes of microstructure are involved in, since it confirmed that the positive role of compact oxide layers in contributing to high corrosion resistance and activity for OER, but excessive Mn2+, resulted in its micromorphology of overthickness and instability. Such differences resulted from the effect of the Mn2+ concentration fluctuation on kinetic rates of the nucleation growth process. The formation and adsorption of intermediate MnO2-OHads identified as the controlled step for Mn2+ catalyzing OER was also recommended. The generation mechanism of anode slime was found to be changed in essence due to varying Mn2+ concentrations. In electrolyte of 1 g/L Mn2+, results revealed that the root cause of excessive small suspended anode slime (around 20 µm) was the change of the initial pathway of Mn2+ electro-oxidation, whereas, it showed great improvement in the settling performance as the Mn2+ concentration was increased to 10 g/L. Considering the potential of optimizing Mn2+ concentrations as a cleaner approach to control anode slime, deepening the understanding of the impact mechanism of Mn2+ can provide new insights into intervention in the generation of anode slime.

The oxidative degradation of polystyrene resins on the removal of Cr(VI) from wastewater by anion exchange.

Cr(VI) is a powerful oxidant and is capable of oxidizing most of the organic materials. Therefore, it is possible for Cr(VI) to oxidize the polymeric resins and change the sorption properties of the resins on the removal of Cr(VI) from wastewater by anion exchange. In this study, three polystyrene resins (D201, D202, and D301) with different functional groups (-N(+)(CH3)3, -N(+)(CH3)2(C2H4OH), and N(CH3)2) were assessed on oxidation stability for Cr(VI) removal from wastewater in fixed-bed column experiments. After a 10-cycle operation, due to the oxidation of the resin, the sorption capacity of D201, D202, and D301 resins decreased by 23.5, 29.3, and 17.3%, when approximately 20-34%, 31-50%, and 18-30% of Cr(VI) was reduced to Cr(III) during each cycle respectively. The results of the Fourier transform infrared spectroscopy (FT-IR) showed that both the cleavage of CN and the formation of CO bonds occurred on the polystyrene resins during the Cr(VI) removal process. The resin simulation experiments further validated the oxidation of CC and CN bonds connected with phenethyl groups. Based upon the results from column operations and the resin simulated experiments, the oxidation mechanism of the polystyrene resin was proposed.

Catalytic hydrodechlorination of monochloroacetic acid in wastewater using Ni-Fe bimetal prepared by ball milling.

Monochloroacetic acid (MCA) is a chemically stable and biologically toxic pollutant. It is often generated during the production of the pesticide dimethoate. Conventional wastewater treatment processes have difficulty degrading it. In this work, the dechlorination effects of Ni-Fe bimetal prepared using ball milling (BM) technology for the high concentrations of MCA in wastewater were examined. The MCA in aqueous solution was found to be degraded efficiently by the Ni-Fe bimetal. However, S-(methoxycarbonyl) methyl O, O-dimethyl phosphorodithioate (SMOPD) in wastewater, a by-product of the dimethoate production process, significantly inhibited the reductive dechlorination activity of Ni-Fe bimetal. Increasing the reaction temperature in the MCA wastewater enhanced the reduction activity of the Ni-Fe bimetal effectively. Oxygen was found to be unfavorable to dechlorination. Sealing the reaction to prevent oxidation was found to render the degradation process more efficient. The process retained over 88% efficiency after 10 treatment cycles with 50 g/L of Ni-Fe bimetal under field conditions.

Mutually beneficial host exploitation and ultra-biased sex ratios in quasisocial parasitoids.

Selfish interests usually preclude resource sharing, but under some conditions collective actions enhance per capita gains. Such Allee effects underlay early explanations of social evolution but current understanding focusses on kin selection (inclusive fitness). We find an Allee effect that explains unusual quasisociality (cooperative brood care) among parasitoid wasps without invoking or precluding kin selection effects. In Sclerodermus harmandi, individual females produce most offspring when exploiting small hosts alone. However, larger hosts are more successfully exploited by larger groups of females, with the per-female benefits outweighing the costs of host sharing. Further, the extremely biased sex ratios (97% female) are better explained by mutually beneficial female-female interactions that increase the reproductive value of daughters (local resource enhancement), rather than by the usually invoked local mate competition between males. Thus, atypical quasisocial behaviour in a parasitoid wasp directly enhances reproductive success and selects for very extremely female-biased sex ratios.

Mechanochemical destruction of pentachloronitrobenzene with reactive iron powder.

Pentachloronitrobenzene (PCNB) has been identified as a potential persistent organic pollutant, and received concerns from many countries for regulation due to its impurities such as dioxins and furans. Considering the need for its disposal, the mechanochemical destruction approach was investigated for the applicability. PCNB was co-ground with reactive iron powder in a high energy planetary ball mill at room temperature. PCNB was found to be destructed finally, and the Dioxins and coplanar-PCBs concentrations in PCNB had been degraded from 1146 ng-TEQ/kg to 0.04 ng-TEQ/kg finally. Pentachloroaniline (PCA), 2,3,5,6-tetrachloroaniline (2,3,5,6-TeCBA) and 3,4,5,6-tetrachloroaniline (3,4,5,6-TeCBA) were detected as intermediates during the ball milling process and were destructed completely after 8h milling. The amount of water soluble chlorides (Cl(-)) reached 95.8% of the theoretical amount of chlorine in original PCNB sample after 12h ball milling. The solvent acetone might play a role as the main hydrogen donor, which gives rise to the amination reaction of nitro-group. Metastable structures with high molecular were proposed to be formed during the ball milling process as intermediates. Carbonization was confirmed by Raman spectrum as the final degradation product of PCNB.

[Influences of inorganic anions on oxidation of phenol by CuO-H2O2].

Phenol was selected as a model pollution substrate. The influences and mechanism of inorganic anions on its oxidation were investigated in neutral solution at low temperature and atmospheric pressure. Results showed that phenol could be removed efficiently by CuO and H2O2 with 94.7% removal rate in 10 min, which followed hydroxyl radical oxidation mechanism. Inorganic anions influenced the oxidation with different mechanisms. Higher concentration would lead to more significant influences. HCO3(-) accelerated the inefficient decomposing of H2O2. The decomposing rate constants increased from 0.3738 min(-1) at concentration of 0 mmol x L(-1) to 0.5347 min(-1) at concentration of 20 mmol x L(-1). The TOC removal rate constants decreased from 0.267 min(-1) to 0.0194 min(-1) correspondingly. HPO4(2-) retarded the H2O2 decomposing and inhibited the phenol oxidation. The decomposing rate constants of H2O2 and the removal rate constants of TOC decreased from 0.3738 min(-1), 0.267 min(-1) to 0.0338 min(-1), 0.0338 min(-1) respectively. Cl(-) was good at H2O2 decomposing and phenol removal with simultaneously increasing the H2O2 decomposing rate constants and the TOC removal rate constants from 0.3738 min(-1), 0.267 min(-1) to 0.6040 min(-1), 0.3879 min(-1) respectively. NO3(-) and SO4(2-) had few influences on H2O2 decomposing and phenol removal.