电极生物膜自养脱氮系统中的电化学作用

设计构建三维电极生物膜反应器,成功启动后稳定运行,在全自养条件下能较好地处理低碳氮比含氮废水.结果表明,在进水不含有机碳源,电流强度为30 mA,电流密度为0.012 mA·cm-2,运行周期24 h的实验条件下,反应器处理进水氨氮浓度为30 mg·L-1的废水时,氨氮转化率达到了90.3%,总氮去除率为70.0%;处理进水硝态氮浓度为30 mg·L-1的废水时,硝态氮去除率达到了82.7%.在考察电极生物膜反应器脱氮性能的同时,探讨系统中纯电化学作用的脱氮能力.结果显示电极生物膜处理氨氮废水的系统中,纯电化学脱氮作用为系统总脱氮能力的10%左右;而处理硝态氮废水的电极生物膜系统中,无电化学还原去除NO-3-N作用.     

电化学方法检测海水中铁的研究进展

海水中的痕量铁作为限制海洋浮游植物初级生产力的关键因素之一,在海洋生物地球化学循环中起着重要的作用.及时分析海水中铁的不同存在形态及其含量,对于进一步认识铁循环机制和有效预防海洋环境污染具有重要意义.电化学方法较其他分析方法在检测海水中痕量铁的含量,尤其是形态分析方面具有独特的优势.本文总结了运用电化学方法检测海水及其他自然水体中铁的分析方法,以期为发展准确、快速测定海水中痕量铁的形态及其含量的分析技术提供基础性参考.     

电化学方法研究小分子与核酸相互作用的进展(Recent Electrochemical Investigation on the Interaction of Small Molecules with Nucleic Acids)

研究小分子与核酸的相互作用,对了解分子对DNA体内复制和转录的影响、探索疾病的发病机理和寻找新型药物设计等具有重要意义.电化学方法是一种重要的研究小分子与核酸相互作用的方法,而这方面的综述较少.论文首先论述了小分子与核酸相互作用的结合方式,并对采用电化学方法考察无机金属离子、金属配合物、有机药物分子、有机环境污染物与DNA相互作用的研究进展进行了归纳和评述,其中对有机小分子与核酸的相互作用进行了较详细介绍.最后,对该领域研究趋势进行了讨论.     

铂修饰电极催化氧化苯酚的热力学研究

研究苯酚在铂修饰玻碳电极上的电化学氧化.考察了温度、pH值和苯酚浓度对苯酚电化学氧化的影响.结果表明,随着温度的升高,苯酚的氧化峰电位逐渐减小,氧化峰电流逐渐增大;随着pH值的增大,氧化峰电位逐渐减小,峰电流开始逐渐减小,在pH7.5时突然增大,然后又减小;随着苯酚浓度的增大,苯酚的氧化峰电位逐渐减小,峰电流增大.苯酚在铂修饰电极上的电化学氧化反应活化能为14.6 kJ·mol-1.     

噻吩在离子液体中的电化学聚合及其在模拟汽油脱硫中的应用

研究了噻吩在离子液体[HMIM] BF4,[BMIM] BF4和[BMIM] PF6中的电化学聚合,实验证明,噻吩在三种离子液体中均能聚合.将噻吩在离子液体中的电化学聚合应用于模拟汽油脱硫.结果表明:在三种离子液体中都实现了电化学脱除模拟汽油样品中的含硫物质--噻吩.对于不同的离子液体而言,脱硫的最佳电流密度不同,但噻吩的脱除效果均能达到50%-90%.     

Electrocatalytic debromination of BDE-47 at palladized graphene electrode

Graphene electrodes （Ti/Gr） were prepared by depositing Gr sheets on Ti substrate, followed by an annealing process for enhancing the adhesion strength. Electrochemical impedance spectroscopies and X-ray dif- fraction patterns displayed that the electrochemical behavior of Ti/Gr electrodes can be improved due to the generation of TiO2 layer at Ti-Gr interface during the annealing process. The palladized Gr electrodes （Ti/Gr/Pd） were prepared by electrochemical depositing Pd nanoparticles on Gr sheets. The debromination ability of Ti/Gr/Pd electrodes was investigated using BDE-47 as a target pollutant with various bias potentials. The results indicated that the BDE-47 degradation rates on Ti/Gr/Pd electrodes increased with the negative bias potentials from 0V to -0.5 V （vs. SCE）. Almost all of the BDE-47 was removed in the debromination reaction on the Ti/Gr/Pd electrode at - 0.5 V for 3 h, and the main product was diphenyl ethers, meaning it is promising to debrominate completely using the Ti/Gr/Pd electrode. Although the debromination rate was slightly slower at -0.3 V than that under -0.5 V, the current efficiency at -0.3 V was higher, because the electrical current acted mostly on BDE-47 rather than on water.     

基于丝网印刷电极的电化学传感器在农药残留检测中的应用综述

环境中农药残留具有较强的毒性,其长期残存会对环境生态系统和人类个体产生毒性效应,因而引起科研工作者的关注.目前,传统的色谱分析方法(如气相色谱法、液相色谱-质谱联用法等)是农药残留检测的主要手段,但是存在费时、样本处理复杂、仪器设备昂贵等局限性,因此,迫切需求建立简单、快速、灵敏的农残检测方法.生物传感技术具有诸多优势,特别是其可以简化样本处理/制备过程,实现场地检测,降低检测成本,有望将来取代传统的分析方法.本文主要综述了丝网印刷电极电化学传感器在农残检测中的研究进展.首先,简单介绍了丝网印刷电极及其制备,然后重点介绍了丝网印刷电极电化学传感器在有机磷类、氨基甲酸酯类、除草剂类等三类农药中的应用进展,并分别阐述了以酶、核酸、蛋白、抗体等为分子识别元件的生物传感检测原理,最后对丝网印刷电极的发展进行了展望.     

电化学沉积法制备ZIF-8及其对四环素的吸附

ZIF-8的常用合成方法包括水/溶剂热法、机械研磨法、微波辅助法和超声法等.本实验采用"绿色"、批量、快速的电化学沉积法制备ZIF-8,同时研究导电盐十二烷基三甲基溴化铵(DTAB)质量浓度对ZIF-8形貌及其吸附降解四环素性能的影响.研究结果显示,当2-甲基咪唑(2-MI)与DTAB质量浓度比为10∶3时制得的ZIF-8对四环素吸附效果最好,可达到340.8 mg·g~(-1),其吸附过程符合伪二级动力学模型和Langmuir等温线模型.根据Langmuir等温线模型,计算Gibss自由能变(ΔG~00)、焓变(ΔH~00)和熵变(ΔS~00),说明吸附过程为吸热、趋于无序的自发过程,并且是一个以物理吸附为主的物理化学吸附.本文利用金属有机骨架材料的光催化性能,实现了紫外光照射下ZIF-8对四环素的光催化降解.同时,通过3次循环实验,对ZIF-8的重复利用性进行了探究,其吸附量分别为175.44、165.83、139.19 mg·g~(-1),结果表明ZIF-8具有良好的重复利用性.探讨了不同pH对吸附效果的影响,当4pH8时,其吸附效果最佳,而当pH 4或pH8时都会使其吸附效果变差.通过对ZIF-8进行PXRD、TGA、BET、FTIR、Zeta电位等表征,提出ZIF-8对四环素的吸附机理包括但不限于静电相互作用、氢键作用以及π-π堆积作用. ZIF-8在吸附去除水体中的四环素方面具有很大的应用潜力,同时ZIF-8可利用紫外光照射进行再生,表现出其优越的可持续循环利用性.     

FR-CNTs-PbO2/SnO2-Sb/Ti电极性能及电催化降解罗丹明B

利用碳纳米管(CNTs)的优异性能和氟树脂(FR)的憎水性能,采用电化学共沉积法制备掺杂型FR-CNTs-PbO2/SnO2-Sb/Ti复合电极.运用扫描电子显微镜(SEM)和X射线衍射(XRD)仪对该电极的形貌和组成进行表征,采用接触角仪和阳极极化曲线对电极的电化学性能进行考察.结果表明,该电极比FR-PbO2/SnO2-Sb/Ti和PbO2/SnO2-Sb/Ti电极具有更强的憎水性能和更高的O2析出电位,这将有利于提高电极的电催化性能和电流利用效率.将FR-CNTs-PbO2/SnO2-Sb/Ti电极应用于罗丹明B(RhB)的降解研究,30 mA.cm-2电流密度下,处理10μmol.L-1RhB 15 min,RhB去除率高达90.21%.相同条件下,FR-PbO2/SnO2-Sb/Ti电极对RhB的去除率仅为69.08%.且FR-CNTs-PbO2/SnO2-Sb/Ti电极的反应速率常数为0.2215 min-1,是FR-PbO2/SnO2-Sb/Ti电极(k=0.1191 min-1)的近2倍.由此可见,较强的憎水性和较高的析氧电位,增强了FR-CNTs-PbO2/SnO2-Sb/Ti电极的电化学性质和电催化效果.     

活性艳蓝X-BR的电化学行为及机理研究

采用循环伏安法、线性扫描伏安法及微分脉冲伏安法研究了活性艳蓝X BR在0 1mol·l- 1 KCl HCl溶液中的电化学行为 .研究发现 ,在 - 0 45V— 1 0VvsSCE电压范围内的循环过程中出现两对氧化还原电流峰 ,通过考察峰电压随溶液pH值的变化 ,提出了可能的电极反应机理 :阳极区的电极反应是属于失 1质子和 2电子的氧化反应 ,而阴极区的电极反应则是蒽醌基团被还原加氢成为氢醌基团的反应     

Water quality monitoring in a slightly-polluted inland water body through remote sensing — Case study of the Guanting Reservoir in Beijing, China

This study focused on the water quality of the Guanting Reservoir, a possible auxiliary drinking water source for Beijing. Through a remote sensing (RS) approach and using Landsat 5 Thematic Mapper (TM) data, water quality retrieval models were established and analyzed for eight common water quality variables, including algae content, turbidity, and concentrations of chemical oxygen demand, total nitrogen, ammonia nitrogen, nitrate nitrogen, total phosphorus, and dissolved phosphorus. The results show that there exists a statistically significant correlation between each water quality variable and remote sensing data in a slightly-polluted inland water body with fairly weak spectral radiation. With an appropriate method of sampling pixel digital numbers and multiple regression algorithms, retrieval of the algae content, turbidity, and nitrate nitrogen concentration was achieved within 10% mean relative error, concentrations of total nitrogen and dissolved phosphorus within 20%, and concentrations of ammonia nitrogen and total phosphorus within 30%. On the other hand, no effective retrieval method for chemical oxygen demand was found. These accuracies were acceptable for the practical application of routine monitoring and early warning on water quality safety with the support of precise traditional monitoring. The results show that performing the most traditional routine monitoring of water quality by RS in relatively clean inland water bodies is possible and effective.     

Inorganic nitrogen metabolism in marine bacteria: Nitrate uptake and reduction in a marine pseudomonad

Growth experiments in batch cultures indicated that the uptake of nitrate by the marine pseudomonad PL1 was inhibited in the presence of ammonia provided that the ammonia concentration was higher than 1 mM. At ammonia concentrations of less than about 1 mM, however, both nitrate and ammonia were utilised simultaneously. The saturation constants for nitrate and ammonia uptake were both 2.6x10^-4 M, and similar to the Michaelis constants of nitrate reductase for nitrate (2.9x10^-4 M) and glutamine synthetase for ammonia (2x10^-4 M). Nitrate reductase activity linked to NADH was detected in chemostat-grown cultures with nitrate as nitrogen source, and in cultures containing limiting concentrations of nitrate and ammonia, ammonia or glutamate. Enzyme synthesis appeared to be repressed in cultures containing an excess of ammonia or glutamate. Chemostat cultures utilised ammonia or glutamate in preference to nitrate, while there was no marked preference between ammonia and glutamate.     

城市污水厂氨气的来源及排放因子研究

通过对城市污水处理厂进行现场调查和分析,选取广州市猎德污水处理厂的格栅、沉砂池、A-B工艺的曝气池、组合交替式(unitank)生化池、污泥浓缩池及脱水机房采集气样,同时在A-B工艺的曝气池、unitank生化池及A-B工艺的沉淀池采集水样,采用模拟实验测试这些污水处理单元的氨挥发速率,并结合理论计算,研究氨气的来源和排放因子.结果表明,A-B工艺的曝气池和unitank工艺的生化池为城市污水处理厂的主要氨排放源.城市污水处理厂污水的氨气平均挥发速率为21.06μg.m-.2s-1,在此基础上计算出其氨气平均排放因子为0.28 g.m-3,其中A-B工艺曝气池的氨排放因子较高,为0.205 g.m-3;unitank生化池的氨排放因子为0.033 g.m-3;A-B工艺沉淀池的氨排放因子较低,为0.0085 g.m-3.     

Enhancement on the ammonia oxidation capacity of ammonia-oxidizing archaeon originated from wastewater: Utilizing low-density static magnetic field

• AOA’s ammonia oxidizing capacity was enhanced under moderate magnetic field. • AOA possessed a certain magnetotaxis under uneven magnetic field. • Enhanced ammonia oxidizing capacity was lost once magnetic field was removed. Ammonia-oxidizing archaeon (AOA) could play important roles for nitrogen removal in the bioreactors under conditions such as low pH and low dissolved oxygen. Therefore, enhancing ammonia oxidation capability of AOA has great significance for water and wastewater treatment, especially under conditions like low dissolved oxygen concentration. Utilizing a novel AOA strain SAT1, which was enriched from a wastewater treatment plant by our group, the effect of magnetic field on AOA’s ammonia oxidation capability, its magnetotaxis and heredity were investigated in this study. Compared with control experiment, AOA’s maximum nitrite-N formation rate during the cultivation increased by 56.8% (0.65 mgN/(L·d)) with 20 mT magnetic field. Also, it was testified that AOA possessed a certain magnetotaxis. However, results manifested that the enhancement of AOA’s ammonia oxidation capability was not heritable, that is, lost once the magnetic field was removed. Additionally, the possible mechanism of improving AOA’s ammonia oxidation capability by magnetic field was owing to the promotion of AOA single cells’ growth and fission, rather than the enhancement of their ammonia oxidation rates. The results shed light on the application of AOA and methods to enhance AOA’s ammonia oxidation capability, especially in wastewater treatment processes under certain conditions.     

Impact of total organic carbon and chlorine to ammonia ratio on nitrification in a bench-scale drinking water distribution system

Nitrification occurs in chloraminated drinking water systems and is affected by water quality parameters. The aim of this study was to investigate the impact of total organic carbon and chlorine to ammonia ratio on nitrification potential in a simulated drinking water distribution system as during chloramination. The occurrence of nitrification and activity of nitrifying bacteria was primarily monitored using four rotating annular bioreactors (RAB) with different chlorine to ammonia ratios and total organic carbon (TOC) levels. The results indicated that nitrification occurred despite at a low influent concentration of ammonia, and a high concentration of nitrite nitrogen was detected in the effluent. The study illustrated that reactors 1(R1) and 3 (R3), with higher TOC levels, produced more nitrite nitrogen, which was consistent with the ammonia-oxidizing bacteria (AOB) counts, and was linked to a relatively more rapid decay of chloramines in comparison to their counterparts (R2 and R4). The AOB and HPC counts were correlated during the biofilm formation with the establishment of nitrification. Biofilm AOB abundance was also higher in the high TOC reactors compared with the low TOC reactors. The chlorine to ammonia ratio did not have a significant impact on the occurrence of nitrification. Bulk water with a high TOC level supported the occurrence of nitrification, and AOB development occurred at all examined chlorine to ammonia dose ratios (3:1 or 5:1).     

新疆盐渍化土壤氮肥氨挥发损失特征初步研究

在室温下应用“静态吸收法”,研究不同盐渍化程度的盐化土壤和碱化土壤上氮肥氨挥发损失特征。结果表明:(1)除碱土外碱化土壤上氮肥氨挥发量随时间延长呈现下降趋势,在盐化土壤上氨挥发量随时间呈现先上升后下降趋势。(2)供试9个典型盐渍化土壤样品上氮肥氨挥发量(Y)与时间(t)关系均符合Y=at2 bt c动力学方程,相关性呈极显著水平。(3)氨挥发总量(Y)、氨挥发速率(Yi)与土壤含盐量(x)呈极显著正相关;氨挥发持续时间随着盐渍化程度的增加而延长。(4)氨挥发总量、挥发速率与盐渍土pH相关性未达到显著水平;盐渍土上pH值对氨挥发的影响需要进一步研究。以上结果表明,盐渍化耕作土壤上氮肥氨挥发的控制要依据盐渍化类型的不同而制定相应的措施。     

Ammonia and phosphorus removal from agricultural runoff using cash crop waste-derived biochars

• Orange tree residuals biochar had a better ability to adsorb ammonia. • Modified tea tree residuals biochar had a stronger ability to remove phosphorus. • Partially-modified biochar could remove ammonia and phosphorus at the same time. • The real runoff experiment showed an ammonia nitrogen removal rate of about 80%. • The removal rate of total phosphorus in real runoff experiment was about 95%. Adsorption of biochars (BC) produced from cash crop residuals is an economical and practical technology for removing nutrients from agricultural runoff. In this study, BC made of orange tree trunks and tea tree twigs from the Laoguanhe Basin were produced and modified by aluminum chloride (Al-modified) and ferric sulfate solutions (Fe-modified) under various pyrolysis temperatures (200°C–600°C) and residence times (2–5 h). All produced and modified BC were further analyzed for their abilities to adsorb ammonia and phosphorus with initial concentrations of 10–40 mg/L and 4–12 mg/L, respectively. Fe-modified Tea Tree BC 2h/400°C showed the highest phosphorus adsorption capacity of 0.56 mg/g. Al-modified Orange Tree BC 3h/500°C showed the best performance for ammonia removal with an adsorption capacity of 1.72 mg/g. FTIR characterization showed that P = O bonds were formed after the adsorption of phosphorus by modified BC, N-H bonds were formed after ammonia adsorption. XPS analysis revealed that the key process of ammonia adsorption was the ion exchange between K⁺ and NH₄⁺. Phosphorus adsorption was related to oxidation and interaction between PO₄^3– and Fe³⁺. According to XRD results, ammonia was found in the form of potassium amide, while phosphorus was found in the form of iron hydrogen phosphates. The sorption isotherms showed that the Freundlich equation fits better for phosphorus adsorption, while the Langmuir equation fits better for ammonia adsorption. The simulated runoff infiltration experiment showed that 97.3% of ammonia was removed by Al-modified Orange tree BC 3h/500°C, and 92.9% of phosphorus was removed by Fe-modified Tea tree BC 2h/400°C.     

饮用原水中微量NH_3-N的生物膜脱除

针对NH3-N浓度为1mg.l-1的饮用原水,分别以硅锰砂石和聚胺脂海绵作为硝化生物膜载体,考察了自制固定床生物膜反应器的脱氨效果.30d的连续运行结果表明,砂石载体系统达到95%—100%的NH3-N去除率,出水NH3-N浓度接近0,出水NO2--N浓度在0—0.02mg.l-1之间;而海绵载体系统虽然挂膜快,但运行阶段NH3-N去除率仅为10%—35%,出水NH3-N不能达标,且具有生物可降解性,反硝化过程优先导致NO2--N的积累.进一步考察了硅锰砂石生物膜系统稳定运行的最优参数,得出试验条件下,水力停留时间为6min,气水比为1:1,反冲洗周期为6d.硅锰砂石因其良好的孔隙率、粒径分布和密度等物理特性,以及化学稳定性和生物安全性,是含低浓度NH3-N原水生物膜净化的良好载体选择.     

Electricity-driven ammonia oxidation and acetate production in microbial electrosynthesis systems

• MES was constructed for simultaneous ammonia removal and acetate production. • Energy consumption was different for total nitrogen and ammonia nitrogen removal. • Energy consumption for acetate production was about 0.04 kWh/g. • Nitrate accumulation explained the difference of energy consumption. • Transport of ammonia and acetate across the membrane deteriorated the performance. Microbial electrosynthesis (MES) is an emerging technology for producing chemicals, and coupling MES to anodic waste oxidation can simultaneously increase the competitiveness and allow additional functions to be explored. In this study, MES was used for the simultaneous removal of ammonia from synthetic urine and production of acetate from CO₂. Using graphite anode, 83.2%±5.3% ammonia removal and 28.4%±9.9% total nitrogen removal was achieved, with an energy consumption of 1.32 kWh/g N for total nitrogen removal, 0.45 kWh/g N for ammonia nitrogen removal, and 0.044 kWh/g for acetate production. Using boron-doped diamond (BDD) anode, 70.9%±12.1% ammonia removal and 51.5%±11.8% total nitrogen removal was obtained, with an energy consumption of 0.84 kWh/g N for total nitrogen removal, 0.61 kWh/g N for ammonia nitrogen removal, and 0.043 kWh/g for acetate production. A difference in nitrate accumulation explained the difference of total nitrogen removal efficiencies. Transport of ammonia and acetate across the membrane deteriorated the performance of MES. These results are important for the development of novel electricity-driven technologies for chemical production and pollution removal.     

沉水植物对水-沉积物界面各形态氮含量的影响

在室内模拟条件下研究沉水植物对水-沉积物界面的上覆水、不同层次的间隙水和沉积物中不同形态氮含量的影响.结果表明:总体上,上覆水和间隙水中不同形态氮含量的顺序为有机氮＞氨氮＞硝态氮;沉积物中可交换态无机氮以氨氮为主,沉水植物的存在并没有改变这一格局.不同处理不同层次的间隙水中,各形态氮含量均为下层＞中层＞上层,但沉积物中氨氮和硝态氮含量变化规律不明显.水-沉积物界面氨氮和硝态氮含量呈现明显季节性变化.总之,水-沉积物界面氨氮是沉积物向上覆水扩散的主要氮组分,沉水植物降低了氨氮和硝态氮的扩散通量.