Electrocatalytic reduction of nitrate using Pd-Cu modified carbon nanotube membranes

● Pd-Cu modified CNT membranes were prepared successfully by electrodeposition method. ● The deposition voltage and deposition time were optimized for Pd-Cu co-deposition. ● NO₃⁻-N was removed efficiently from water by Pd-Cu modified CNT membranes. ● The presence of dissolved oxygen did not affect the nitrate reduction performance. ● Mass transfer rate was promoted significantly with the increase in membrane flux. Excessive nitrate in water is harmful to the ecological environment and human health. Electrocatalytic reduction is a promising technology for nitrate removal. Herein, a Pd-Cu modified carbon nanotube membrane was fabricated with an electrodeposition method and used to reduce nitrate in a flow-through electrochemical reactor. The optimal potential and duration for codeposition of Pd and Cu were −0.7 V and 5 min, respectively, according to linear scan voltammetry results. The membrane obtained with a Pd:Cu ratio of 1:1 exhibited a relatively high nitrate removal efficiency and N₂ selectivity. Nitrate was almost completely reduced (~99 %) by the membrane at potentials lower than −1.2 V. However, −0.8 V was the optimal potential for nitrate reduction in terms of both nitrate removal efficiency and product selectivity. The nitrate removal efficiency was 56.2 %, and the N₂ selectivity was 23.8 % for the Pd:Cu=1:1 membrane operated at −0.8 V. Nitrate removal was enhanced under acidic conditions, while N₂ selectivity was decreased. The concentrations of Cl⁻ ions and dissolved oxygen showed little effect on nitrate reduction. The mass transfer rate constant was greatly improved by 6.6 times from 1.14 × 10⁻³ m/h at a membrane flux of 1 L/(m²·h) to 8.71 × 10⁻³ m/h at a membrane flux of 15 L/(m²·h), which resulted in a significant increase in the nitrate removal rate from 13.6 to 133.5 mg/(m²·h). These findings show that the Pd-Cu modified CNT membrane is an efficient material for nitrate reduction.     

Biodegradation of 2-methylisoborneol by bacteria enriched from biological activated carbon

One of the most common taste and odour compounds (TOCs) in drinking water is 2-methylisoborneol (2-MIB) which cannot be readily removed by conventional water treatments. Four bacterial strains for degrading 2-MIB were isolated from the surface of a biological activated carbon filter, and were characterized as Micrococcus spp., Flavobacterium spp., Brevibacterium spp. and Pseudomonas spp. based on 16S rRNA analysis. The removal efficiencies of 2-MIB with initial concentrations of 515 ng·L^-1 were 98.4%, 96.3%, 95.0%, and 92.8% for Micrococcus spp., Flavobacterium spp., Brevibacterium spp. and Pseudomonas spp., respectively. These removal efficiencies were slightly higher than those with initial concentration at 4.2 mg·L^-1 (86.1%, 84.4%, 86.7% and 86.0%, respectively). The kinetic model showed that biodegradation of 2-MIB at an initial dose of 4.2 mg·L^-1 was a pseudo-first-order reaction, with rate constants of 0.287, 0.277, 0.281, and 0.294 d^-1, respectively. These degraders decomposed 2-MIB to form 2-methylenebornane and 2-methyl-2-bornane as the products.     

Preparation of a permanent magnetic hypercrosslinked resin and assessment of its ability to remove organic micropollutants from drinking water

A rapid and effective method based on a novel permanent magnetic hypercrosslinked resin W150 was proposed for the removal of organic micropollutants in drinking water. W150 was prepared by suspension and post-crosslinking reaction and found to possess a high specific surface area of 1149.7 m²·g^-1, a small particle size of 50 μm to 100 μm, and a saturation magnetization as high as 8 emu·g^-1. W150 was used to eliminate nitrofurazone (NFZ) and oxytetracycline (OTC) from drinking water compared with commercial adsorbents XAD-4 and F400D. The adsorption kinetics of NFZ and OTC onto the three adsorbents well fitted the pseudo-second-order equation (r>0.972), and the adsorption isotherms were all well described by the Freundlich equation (r>0.851). Results showed that the reduction in adsorbent size and the enlargement in sorbent pores both accelerated adsorption. Moreover, the effect of particle size on adsorption was more significant than that of pore width. Given that the smallest particle size and the highest specific surface area were possessed by W150, it had the fastest adsorption kinetics and largest adsorption capacity for NFZ (180 mg·g^-1) and OTC (200 mg·g^-1). For the adsorbents with dominant micropores, the sorption of large-sized adsorbates decreased because of the inaccessible micropores. The solution pH and ionic strength also influenced adsorption.     

2019年秋季三亚市一次典型臭氧污染个例气象成因解析

三亚市位于海南岛最南端,旅游资源丰富,生态环境良好,是海南建设国际旅游岛和国家生态文明试验区的重要城市之一.2019年秋季三亚市出现的一次臭氧(Ozone,O3)污染过程,为科学认识三亚市此次O3污染特征及气象学成因,也为进一步开展O3污染预警预报和科学治理提供技术支撑,利用2019年11月1—6日三亚市生态环境局对外...     

Influence of aeration intensity on the performance of A/O-type sequencing batch MBR system treating azo dye wastewater

Among the numerous parameters affecting the membrane bioreactor (MBR) performance, the aeration intensity is one of the most important factors. In the present investigation, an anoxic/aerobic-type (A/O-type) sequencing batch MBR system, added anoxic process as a pretreatment to improve the biodegradability of azo dye wastewater, was investigated under different aeration intensities and the impact of the aeration intensity on effluent quantity, sludge properties, extracellular polymeric substances (EPS) amount generated as well as the change of permeation flux were examined. Neither lower nor higher aeration intensities could improve A/O-type sequencing batch MBR performances. The results showed 0.15 m³·h^-1 aeration intensity was promising for treatment of azo dye wastewater under the conditions examined. Under this aeration intensity, chemical oxygen demand (COD), ammonium nitrogen and color removal as well as membrane flux amounted to 97.8%, 96.5%, 98.7% and 6.21 L·m^-2·h^-1, respectively. The effluent quality, with 25.0 mg·L^-1COD, 0.84 mg·L^-1 ammonium nitrogen and 8 chroma, could directly meet the reuse standard in China. In the meantime, the sludge relative hydrophobicity, the bound EPS, soluble EPS and EPS amounts contained in the membrane fouling layer were 70.3%, 52.0 mg·g^-1VSS, 38.8 mg·g^-1VSS and 90.8 mg·g^-1VSS, respectively, which showed close relationships to both pollutant removals and membrane flux.     

多环麝香对蚯蚓的急性和亚急性毒性效应

为探讨多环麝香对土壤动物的毒性效应,以赤子爱胜蚓(Eisenia fetida)为供试生物,采用滤纸接触法与自然土壤法,考察了吐纳麝香(AHTN)和佳乐麝香(HHCB)对蚯蚓的急性和亚急性毒性效应。结果显示,滤纸法测得的AHTN和HHCB对蚯蚓的急性经皮毒性为中等毒性,对蚯蚓的48h-LC_(50)分别为20.76和11.87μg·cm~(-2),而自然土壤法测得的AHTN和HHCB对蚯蚓的14d-LC_(50)分别为436.3和392.4μg·g~(-1),2种多环麝香皆属低毒物质。HHCB对蚯蚓的急性毒性大于AHTN,但2种毒性测定方法中不同的染毒介质和毒性作用途径使AHTN和HHCB的急性毒性等级的界定有所差异。AHTN和HHCB对蚯蚓繁殖率的抑制作用较对生长速率更为明显,2种多环麝香对蚯蚓繁殖率的无可见效应浓度(NOEC)均为30μg·g~(-1),最低可见效应浓度(LOEC)均为50μg·g~(-1)。研究表明,蚯蚓繁殖率可作为一种潜在的生物标志物,用于监测或表征土壤中多环麝香的污染水平及其亚急性毒性效应。     

Degradation of bisphenol A by microorganisms immobilized on polyvinyl alcohol microspheres

In this study, microorganisms （named B111） were immobilized on polyvinyl alcohol microspheres prepared by the inverse suspension crosslinked method. The biodegradation of bisphenol A （BPA） and 4-hydro- xybenzaldehyde, a degradation product of BPA, by free and immobilized B lll was investigated. The BPA degradation studies were carried out at initial BPA concentrations ranging from 25 to 150 mg·L^-1. The affinity constant Ks and maximum degradation rate Rmax were 98.3 mg·L^-1 and 19.7mg·mg^-1VSS·d^-1 for free B111, as well as 87.2mg·L^-1 and 21.1mg·mg^-1VSS·d^-1 for immobilized B 111, respectively. 16S rDNA gene sequence analyses confirmed that the dominant genera were Pseudomonas and Brevundimonas for BPA biodegradation in microorganisms B 111.     

Using crosslinked polyvinyl alcohol polymer membrane as a separator in the microbial fuel cell

Separator between anode and cathode is an essential part of the microbial fuel cell （MFC） and its property could significantly influence the system perfor- mance. In this study we used polyvinyl alcohol （PVA） polymer membrane crosslinked with sulfosuccinic acid （SSA） as a new separator for the MFC. The highest power density of 7594-4 mW-m-2 was obtained when MFC using the PVA membrane crosslinked with 15% of SSA due to its desirable proton conductivity （5.16 x 10-2 S.cml）. The power density significantly increased to 11064- 30 mW.m-2 with a separator-electrode-assembly config- uration, which was comparable with glass fiber （11704- 46 mW.m-2）. The coulombic efficiencies of the MFCs with crosslinked PVA membranes ranged from 36.3% to 45.7% at a fix external resistance of lO00f2. The crosslinked PVA membrane could be a promising alter- native to separator materials for constructing practical MFC system.     

生物炭对土壤中阿特拉津吸附特征的影响

为探究生物炭对土壤中阿特拉津的吸附特征及影响因素,采用批处理实验研究了灭菌(T1)、5%秸秆生物炭+灭菌(T2)、未灭菌(T3)和5%秸秆生物炭+未灭菌(T4)条件下对土壤中阿特拉津吸附特征及土壤理化性质的影响.结果表明,在最初0—12 h内,不同处理下阿特拉津吸附量均随时间的延长而快速增加,而在12—96 h内增加较为缓慢并逐渐趋于平衡.在96 h时,T2和T4处理下阿特拉津最大吸附量分别达到46.22 mg·kg^-1和46.43 mg·kg^-1,而未添加生物炭的T1和T3处理则有所降低,分别为44.20 mg·kg^-1和43.09 mg·kg^-1.准二级动力学模型更好地拟合不同处理下土壤对阿特拉津吸附特征,T2和T4处理下吸附速率常数K分别为0.257 kg·mg^-1·h^-1和0.339 kg·mg^-1·h^-1,显著高于未添加生物炭处理的T1和T3处理(K分别为-0.083 kg·mg^-1·h^-1和-0.261 kg·mg^-1·h^-1).内扩散模型显示添加生物炭后,土壤对阿特拉津的吸附是一个由边界扩散、内部孔隙扩散等多因素控制的复杂化学过程.添加生物炭可显著提高土壤pH、有机碳、碱解氮、速效磷和速效钾含量,其中土壤有机碳含量与阿特拉津最大吸附量之间存在显著的正相关关系(P<0.05).由此可见,添加生物炭可以提高土壤对阿特拉津的固持能力,减少其淋溶迁移风险,从而达到修复阿特拉津污染土壤的目的.     

Rapid method for on-site determination of phenolic contaminants in water using a disposable biosensor

A disposable biosensor was fabricated using single-walled carbon nanotubes, gold nanoparticles and tyrosinase (SWCNTs-AuNPs-Tyr) modified screen-printed electrodes. The prepared biosensor was applied to the rapid determination of phenolic contaminants within 15 minutes. The SWCNTs-AuNPs-Tyr bionanocomposite sensing layer was characterized with scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry methods. The characterization results revealed that SWCNTs could lead to a high loading of tyrosinase (Tyr) with the large surface area and the porous morphology, while AuNPs could retain the bioactivity of Tyr and enhance the sensitivity. The detection conditions, including working potential, pH of supporting electrolyte and the amount of Tyr were optimumed. As an example, the biosensor for catechol determination displayed a linear range of 8.0 × 10^-8 to 2.0 × 10^-5 mol·L^-1 with a detection limit of 4.5 × 10^-8 mol·L^-1 (S/N = 3). This method has a rapid response time within 10 s, and shows excellent repeatability and stability. Moreover, the resulting biosensor could be disposable, low-cost, reliable and easy to carry. This kind of new Tyr biosensor provides great potential for rapid, on-site and cost-effective analysis of phenolic contaminants in environmental water samples.     

Gold modified microelectrode for direct tetracycline detection

The residues of tetracycline antibiotics in water have attracted many concerns due to their harmful impact to human health. This paper reports an electrochemical sensor for the determination of tetracycline (TC) by the microelectrode, which was fabricated by electrodeposited gold colloids on tungsten tip. Cyclic voltammerty was used to study the electrochemical behavior of TC on the microelectrode. Well anodic wave was obtained at about 1.5 V in acidic solutions. Electrochemical determination of tetracycline was investigated using microelectrode by cyclic voltammetry. Under optimized conditions, the calibration curves for TC were obtained. The oxidation peak currents were linearly related to TC concentrations in the range of 1–10 mg·L^-1 and 10–100 mg·L^-1, respectively. The detection limit was 0.09 mg·L^-1 (S/N = 3).     

Preparation of hapten-specific monoclonal antibody for cadmium and its ELISA application to aqueous samples

High-affinity and specific monoclonal antibodies against cadmium-ethylene diamine tetraacetic acid (EDTA) complex have been produced using the hybridoma technique. A hapten was synthesized and characterized by Fourier Transform Infrared Spectroscopy (FT-IR) and UV-Vis. Competitive enzyme-linked immunosorbent assay (ELISA) for quantitative detection of cadmium in aqueous sample was developed. The monoclonal antibody with high level of binding affinity for Cd-IEDTA-BSA and high specificity for soluble Cd-EDTA complex showed less than 0.99% cross-reactivity with other 11 metals. The limit of detection was 0.10 μg·L^-1, and the effective linear range was 10^-1–10³ μg·L^-1. The intra- and inter-assay coefficient variations were 1.5%–6.3% and 3.2%–7.4%, respectively. The spike recovery in different water samples were between 98.5% and 110.3%. The detection limit of this assay was well below the allowable concentration of cadmium (3 μg·L^-1), and the working range was wider than that of other methods which showed the range of 2.19–86.38 and 0–10³ μg·L^-1. The competitive ELISA established in this paper was sensitive and accurate in the screening of cadmium in aqueous samples. The results will lay a solid foundation for construction of an immunoassay kit for cadmium.     

球磨零价镁/石墨(ZVMg/C)降解水中三氯乙烯

利用机械球磨法制备了零价镁/石墨(ZVMg/C)材料,并将其用于水溶液中三氯乙烯(TCE)的降解.研究通过SEM、BET和XRD等分析手段解析了ZVMg/C的表面形态结构和成分组成;采用正交实验方法优化了ZVMg/C的制备参数,比较了石墨含量对材料性能的影响;并考察了ZVMg/C投加量、溶液初始pH和地下水中常见阴(C...     

Suspended solid abatement in a conical fluidized bed flocculator

With the random movement of silica gel beads in a conical fluidized bed, micro-vortices resulting from the fluidization promoted the collision and aggregation of suspended fine kaolin powders. The abatement efficiencies of the suspended fine solids under several hydrodynamic conditions were studied, and a suitable control strategy for operating the conical fluidized bed flocculators was identified. The suspended solids abatement efficiency was found to increase with increasing Camp Number and flocculation time (T), but decreased with the increase of velocity gradient (G) within the range studied in this research (165.1–189.6 s^-1). The abatement efficiencies were all more than 60% at the range of G = 165–180 s^-1 and T = 15–33 s at an initial kaolin solid concentration of 150 mg·L^-1, polymer aluminum chloride dosage of 60 mg·L^-1 and sedimentation time of 20 min. However, the formation of flocs was influenced by the liquid backmixing. Excessive backmixing caused the breakup of flocs and resulted in difficulty for the fine powders to aggregate and sediment to the reactor bottom. The results of the calculated fractal dimension and measured free sedimentation velocity of flocs obtained at different runs showed similar flocs properties, and indicated an easy control strategy for sedimentation of the flocs.     

梵净山不同森林植被生物量、净生产量、碳储量及空间分布特征

为做好梵净山国家级自然保护区森林植被保护,摸清自然保护区森林植被资源家底,采用2016年第四次森林资源规划设计调查数据及变更至2019年的森林资源数据,计算和分析保护区内森林植被生物量、净生产量、碳储量.梵净山8种森林类型的总生物量为443.72×104 t,总碳储量为219.80×104 t,总生长量为29.75×1...     

Ozone kinetics of dimethyl sulfide in the presence of water vapor

The outdoor smog chamber was used to thorough investigate the rate constants of gas-phase reaction between dimethyl sulfide （DMS） and ozone （O3） under conditions of relative humidity 55.0%-67.8% at （296±2）K for the first time. The rate constants were measured, at a total pressure of 1 atm, to be （10.4±0.2） × 10^-19 cm^3·molecule^-1·s^-1 at relative humidity of 67.5%±0.3% at 298K, （10.1±0.1） × 10^-19cm^3·molecule^-1·s^-1 at relative humidity of 66.5%±0.5% at 296K, （7.75±0.39） × 10^-19cm^3·molecule^-1·s^-1 at relative humidity of 64.8%± 0.1% at 294K and （3.42±0.21） × 10^-19cm^3·molecu- le^-1·s^-1at relative humidity of 55.8%±0.8% at 295K. Base on these results, it is possible to see the reaction of O3/ DMS in the presence of water vapor as an important sink for DMS in the earth atmosphere.     

Improvement of the assimilable organic carbon (AOC) analytical method for reclaimed water

Microbial growth is an issue of concern that may cause hygienic and aesthetic problems during the transportation and usage of reclaimed water. Assimilable organic carbon (AOC) is an important parameter which determines the heterotrophic bacterial growth potential of water. Pseudomonas fluorescens P17 and Spirillum sp. NOX are widely used to measure AOC in drinking water. The AOC values of various reclaimed water samples determined by P17 and NOX were compared with those determined by the new strains isolated from reclaimed water in this study. It showed that the conventional test strains were not suitable for AOC measurement of reclaimed water in certain cases. In addition to P17 and NOX, Stenotrophomonas sp. ZJ2, Pseudomonas saponiphila G3 and Enterobacter sp. G6, were selected as test strains for AOC measurement of reclaimed water. Key aspects of the bioassay including inoculum cell density, incubation temperature, incubation time and the pH of samples were evaluated for the newly selected test strains. Higher inoculum density (10⁴ CFU·mL^-1) and higher incubation temperature (25°C) could reduce the time required for the tests. The AOC results of various collected samples showed the advantages of the method proposed based on those five strains in evaluating the biologic stability of reclaimed water.     

Dissipation of polycyclic aromatic hydrocarbons and microbial activity in a field soil planted with perennial ryegrass

Dissipation and plant uptake of polycyclic aromatic hydrocarbons (PAHs) in contaminated agricultural soil planted with perennial ryegrass were investigated in a field experiment. After two seasons of grass cultivation the mean concentration of 12 PAHs in soil decreased by 23.4% compared with the initial soil. The 3-, 4-, 5-, and 6-ring PAHs were dissipated by 30.9%, 25.5%, 21.2%, and 16.3% from the soil, respectively. Ryegrass shoots accumulated about 280 μg·kg^-1, shoot dry matter biomass reached 2.48 × 10⁴ kg·ha^-1, and plant uptake accounted for about 0.99% of the decrease in PAHs in the soil. Significantly higher soil enzyme activities and microbial community functional diversity were observed in planted soil than that in the unplanted control. The results suggest that planting ryegrass may promote the dissipation of PAHs in long-term contaminated agricultural soil, and plant-promoted microbial degradation may be a main mechanism of phytoremediation.     

Kinetics of oxidation of dimethyl trisulfide by potassium permanganate in drinking water

Metabolites of algae such as geosmin, 2-methylisoborneol etc. are reported to induce pungent odors into drinking water and attract additional scientific attention. Recently, in China, taste and odor outbreaks in drinking water supply have become increasingly common. In source water affected by eutrophication, dimethyl trisulfide, speculated to be produced by decayed algae, was found to be the source of taste and odor issues and can be removed effectively by usual oxidation agents. In this experimental study, batch scale tests were carried out focusing on the removal of dimethyl trisulfide. Reaction kinetics of dimethyl trisulfide oxidized by potassium permanganate in water had been studied; influence factors such as pH, organic substrate, other existed taste, and odor contaminant in equivalent concentration were also discussed. Results showed that dimethyl trisulfide can be removed by potassium permanganate efficiently; the ratio can reach more than 70% with oxidant dosage of 4 mg·L^-1 and contact time prolonged to 120 min. The dimethyl trisulfide decomposition followed a second-order kinetics pattern with a rate constant k = 0.00213 L·(min·mg)^-1. Typically, the degradation rate of dimethyl trisulfide was increased with the increasing KMnO₄ dosage, but dramatically dropped with the increasing levels of humic acid (1.8–4.5 mg·L^-1) and other odor-causing compounds (e.g. β-cyclocitral, 0–1886.0 μg·L^-1). Solution pH (5.2–9.0) and initial dimethyl trisulfide concentration did not significantly affected the degradation. This study demonstrates that KMnO₄ oxidation is an effective option to remove dimethyl trisulfide from water.     

Technical measures to achieve a cleaner production mode for recycled paper mills

China’s paper production reached 79.8 ×10⁶ t in 2008 and ranked number one in the world. Because of its high consumption of water, energy and materials and its serious pollution, the present processes are not likely to be sustainable. An alternative, the closed Water Loop-Papermaking Integration (WLPI) method, is put forward in this paper. The WLPI method can be realized in a recycled paper mill by adding technologies and using recycled water. Many industrial case studies have shown that a large quantity of water, energy and materials can be saved, and the quantity of waste sludge and wastewater discharge was minimized by using the WLPI method. The design of the water reuse system, control of calcium hardness, water recycling and minimal waste sludge are discussed. Anaerobic technology plays an important role in the WLPI method to lower cost, energy use and waste. In the brown paper and coated white board production, zero-effluent discharge can be realized. Fresh water consumption is only 1–2 m³·t^-1. For the paper mills with deinking and bleaching processes, about 10 m³·t^-1 of fresh water and a similar amount of effluent discharge are needed. Power saving using anaerobic technology is 70% when recycled water is used in comparison with the conventional activated sludge process. Waste sludge can be decreased to about 5% of the initial process due to reuse of the waste sludge and the lower bio-sludge production of the anaerobic process.