羧基化碳纳米管载铂催化剂对微生物燃料电池阴极氧还原性能的影响

阴极催化剂是影响微生物燃料电池(microbial fuel cell,MFC)性能的关键要素.为了考察不同羧基化方法改性的碳纳米管(carbon nanotube,CNT)负载Pt的催化氧还原效率,分别在80℃和95℃条件下对CNT进行了羧基化,采用浸渍-沉淀法制备了Pt/CNT催化剂(Pt/CNT-80和Pt/CNT-95),并在空气阴极MFC体系中验证了其催化氧还原效果(MFC-80、MFC-95和MFC-C).结果表明,MFC-95和MFC-80的最大功率密度分别为568.8 mW.m-2和412.8 mW.m-2,内阻分别为204.7Ω和207.7Ω,开路电压分别为0.719 V和0.651 V.而对照MFC-C的最大功率密度仅为5.4 mW.m-2,内阻为826.2Ω.XPS和XRD分析结果显示,Pt/CNT-95催化氧还原效果优于Pt/CNT-80,原因可能是95℃羧基化过程在CNT表面引入了丰富的含氧基团.     

新型生物质活性炭烟气脱硫研究

以农业废弃物核桃壳为原料,天然软锰矿为添加剂共混制备得到的新型生物质柱状活性炭进行烟气脱硫的性能研究.采用固定床反应器进行脱硫实验,装填活性炭质量为16 g,考察了进口SO2含量、空速、床层温度、水蒸气和氧气含量等工艺参数对活性炭脱硫性能的影响.结果表明,进口SO2含量在0.1%～0.3%(体积含量)范围内时,活性炭的穿透硫容和穿透时间随着进口SO2含量的升高而降低;空速越大,活性炭越容易穿透,较佳的空速为600 h-1;最适的床层温度为80℃,过高会降低脱硫效率;水蒸气和氧气的存在大大促进了活性炭对SO2的吸附性能,最佳水蒸气含量为10%,最佳氧气含量为10%～13%.在最佳工艺操作条件下,当进口SO2含量为0.2%时,活性炭穿透硫容为252 mg.g-1,穿透时间可达26 h.     

垦殖对湿地土壤有机碳垂直分布及可溶性有机碳截留的影响

通过测定和计算兴凯湖地区沼泽湿地及由其垦殖而来的旱田和水田土壤剖面有机碳含量和密度及土壤剖面不同深度土壤溶液中可溶性有机碳含量,分析了垦殖对兴凯湖周边沼泽湿地土壤有机碳垂直分布及土壤剖面截留可溶性有机碳的影响.结果表明,垦殖显著影响湿地0～40 cm土壤有机碳含量,大豆田和水稻田0～10、10～20、20～30、30～40 cm土壤有机碳含量与湿地相比分别降低了79.07%和82.01%、79.01%和82.28%、79.86%和92.90%、37.49%和78.05%;40 cm以下土层土壤有机碳含量垦殖前后差异不显著.大豆田和水稻田有机碳密度相比沼泽湿地分别降低了25.50%和47.35%,但三者1 m深土壤中大部分的有机碳均是储存在0～50 cm土层中.垦殖前后土壤有机碳含量与深度之间的关系均可用指数函数来描述,垦殖改变了土壤有机碳含量但并未改变其随土壤深度的变化规律.垦殖为大豆田土壤剖面对可溶性有机碳的截留效果较湿地和水稻田更明显,沼泽湿地和水稻田对可溶性有机碳的截留效果大致相当.     

黄河三角洲碱蓬湿地土壤有机碳及其组分分布特征

应用物理分组方法研究了黄河三角洲典型碱蓬湿地土壤有机碳及其组分分布特征.结果表明,研究区土壤重组有机碳是土壤有机碳的主要组成部分,土壤重组有机碳含量、土壤颗粒有机碳含量与土壤总有机碳含量都显著正相关.研究区土壤轻组组分比例和含量范围分别在0.008%～0.15%和0.10～0.40 g·kg-1,颗粒有机碳分配比例范围为8.83%～30.58%,说明黄河三角洲碱蓬湿地土壤有机碳中非保护性组分较低,碳库相对稳定.     

改良型固定化Pseudomonas oleovorans DT4降解四氢呋喃的研究

成功构建出了新型的海藻酸钠-活性炭纤维复合固定化Pseudomonas oleovorans DT4来去除四氢呋喃,并优化了该复合固定化载体组分的含量,发现在海藻酸钠含量为3%,活性炭纤维含量为1.5%条件下,制备成细胞浓度为6×109g-1的协同固定化细胞在初始THF浓度为360 mg·L-1时的降解速率达到最大为24.0 mg·(L.h)-1,同时其机械强度也得到了显著的提升.此外与游离菌体相比,该固定化细胞在不同温度和pH条件下的降解速率表现得更加稳定,且去除效果均能稳定在80%以上.在改进的反应体系中,协同固定化小球高效降解THF的重复利用次数达到80批以上,显示出该载体良好的可行性.     

Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: Kinetics, isotherms and thermodynamics

The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qm /SSA) and SSA-normalized adsorption coefficient (Kd /SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (△ G0 ) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (△ H0 ), G0 and free energy of adsorption (Ea ), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and K d /SSA or q m /SSA.     

Cost-performance analysis of nutrient removal in a full-scale oxidation ditch process based on kinetic modeling

A full-scale oxidation ditch process for treating sewage was simulated with the ASM2d model and optimized for minimal cost with acceptable performance in terms of ammonium and phosphorus removal. A unified index was introduced by integrating operational costs (aeration energy and sludge production) with effluent violations for performance evaluation. Scenario analysis showed that,in comparison with the baseline (all of the 9 aerators activated), the strategy of activating 5 aerators could save aeration energy significantly with an ammonium violation below 10%. Sludge discharge scenario analysis showed that a sludge discharge flow of 250–300 m3/day (solid retention time (SRT), 13–15 days) was appropriate for the enhancement of phosphorus removal without excessive sludge production. The proposed optimal control strategy was: activating 5 rotating disks operated with a mode of "111100100" ( "1"represents activation and "0" represents inactivation) for aeration and sludge discharge flow of 200 m3/day (SRT, 19 days). Compared with the baseline, this strategy could achieve ammonium violation below 10% and TP violation below 30% with substantial reduction of aeration energy cost (46%) and minimal increment of sludge production (< 2%). This study provides a useful approach for the optimization of process operation and control.     

Biodegradation of 2-methylquinoline by Enterobacter aerogenes TJ-D isolated from activated sludge

Bacterial strain Enterobacter aerogenes TJ-D capable of utilizing 2-methylquinoline as the sole carbon and energy source was isolated from acclimated activated sludge under denitrifying conditions. The ability to degrade 2-methylquinoline by E. aerogenes TJ-D was investigated under denitrifying conditions. Under optimal conditions of temperature (35℃) and initial pH 7, 2-methylquinoline of 100 mg/L was degraded within 176 hr. The degradation of 2-methylquinoline by E. aerogenes TJ-D could be well described by the Haldane model (R² > 0.91). During the degradation period of 2-methylquinoline (initial concentration 100 mg/L), nitrate was almost completely consumed (the removal efficiency was 98.5%), while nitrite remained at low concentration (< 0.62 mg/L) during the whole denitrification period. 1,2,3,4-Tetrahydro-2-methylquinoline, 4-ethyl-benzenamine, N-butyl-benzenamine, N-ethyl-benzenamine and 2,6-diethyl-benzenamine were metabolites produced during the degradation. The degradation pathway of 2-methylquinoline by E. aerogenes TJ-D was proposed. 2-Methylquinoline is initially hydroxylated at C-4 to form 2-methyl-4-hydroxy-quinoline, and then forms 2-methyl-4-quinolinol as a result of tautomerism. Hydrogenation of the heterocyclic ring at positions 2 and 3 produces 2,3-dihydro-2-methyl-4-quinolinol. The carbon-carbon bond at position 2 and 3 in the heterocyclic ring may cleave and form 2-ethyl-N-ethyl-benzenamine. Tautomerism may result in the formation of 2,6-diethyl-benzenamine and N-butyl-benzenamine. 4-Ethyl-benzenamine and N-ethyl-benzenamine were produced as a result of losing one ethyl group from the above molecules.     

Influences of perfluorooctanoic acid on the aggregation of multi-walled carbon nanotubes

The aggregation of multi-walled carbon nanotubes (MWCNTs) in the aqueous phase not only inhibits their extensive utilization in various aspects but also dominates their environmental fate and transport.The role of surfactants at low concentration in the aggregation of MWCNTs has been studied,however the effect of perfluorinated surfactants at low concentration is uncertain.To understand this interfacial phenomenon,the influences of perfluorooctanoic acid (PFOA),and sodium dodecyl sulfate (SDS) as a control,on MWCNT aggregation in the aqueous phase were examined by the UV absorbency method.Influences of pH and cationic species on the critical coagulation concentration (CCC) value were evaluated.The CCC values were dependent on the concentration of PFOA,however a pronounced effect of SDS concentration on the CCC values was not observed.The CCC values of the MWCNTs were 51.6 mmol/L in NaCl and 0.28 mmol/L in CaCl 2 solutions,which suggested pronounced differences in the effects of Na+ and Ca2+ ions on the aggregation of the MWCNTs.The presence of both PFOA and SDS significantly decreased the CCC values of the MWCNTs in NaCl solution.The aggregation of the MWCNTs took place under acidic conditions and was not notably altered under neutral and alkaline conditions due to the electrostatic repulsion of deprotonated functional groups on the surface of the MWCNTs.     

Competitive sorption between 17α-ethinyl estradiol and bisphenol A/4-n-nonylphenol by soils

The sorption of 17α-ethinyl estradiol(EE2),bisphenol A(BPA),and 4-n-nonylphenol(NP) in single systems and the sorption of EE2 with different initial aqueous concentrations of BPA or NP were examined using three soils.Results showed that all sorption isotherms were nonlinear and fit the Freundlich model.The degree of nonlinearity was in the order BPA(0.537-0.686) > EE2(0.705-0.858) > NP(0.875-0.0.951) in single systems.The isotherm linearity index of EE2 sorption calculated by the Freundlich model for Loam,Silt Loam and Silt increased from 0.758,0.705 and 0.858,to 0.889,0.910 and 0.969,respectively,when BPA concentration increased from 0 to 1000 μg/L,but the effect of NP was comparably minimal.Additionally,EE2 significantly suppressed the sorption of BPA,but insignificantly suppressed that of NP.These findings can be attributed to the difference of sorption affinity of EE2,NP and BPA on the hard carbon(e.g.,black carbon) of soil organic matter that dominated the sorption in the low equilibrium aqueous concentration range of endocrine-disrupting chemicals(EDCs).Competitive sorption among EDCs presents new challenges for predicting the transport and fate of EDCs under the influence of co-solutes.