The contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using diamond anodes

In this work, the contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using boron-doped diamond(BDD) anodes was investigated in different electrolytes. A complete mineralization of cyanuric acid was obtained in Na Cl;however lower degrees of mineralization of 70% and 40% were obtained in Na2SO4 and Na Cl O4, respectively. This can be explained by the nature of the oxidants electrogenerated in each electrolyte. It is clear that the contribution of active chlorine(Cl2, HCl O, Cl O-)electrogenerated from oxidation of chlorides on BDD is much more important in the electrolytic degradation of cyanuric acid than the persulfate and hydroxyl radicals produced by electro-oxidation of sulfate and water on BDD anodes. This could be explained by the high affinity of active chlorine towards nitrogen compounds. No organic intermediates were detected during the electrolytic degradation of cyanuric acid in any the electrolytes, which can be explained by their immediate depletion by hydroxyl radicals produced on the BDD surface. Nitrates and ammonium were the final products of electrolytic degradation of cyanuric acid on BDD anodes in all electrolytes. In addition, small amounts of chloramines were formed in the chloride medium. Low current density(≤ 10 m A/cm2) and neutral medium(p H in the range 6–9) should be used for high efficiency electrolytic degradation and negligible formation of hazardous chlorate and perchlorate.     

BDD和PbO2电极电化学氧化苯并三氮唑的对比研究

分别构建了以掺硼金刚石膜电极(BDD)和二氧化铅电极(Pb O2)为阳极的电化学体系,对比考察了两种电极对难降解有机污染物苯并三氮唑(BTA)的降解及体系的矿化效果,并从电极产生羟基自由基(·OH)的数量与形态角度深入探讨了影响电极矿化能力大小的内在因素.结果表明:1BDD和Pb O2电极均对BTA有较好的降解效果,电解12 h后BTA去除率分别为99.48%和98.36%,但BDD电极的矿化能力明显强于Pb O2电极,电解12 h后矿化率分别为87.69%和35.96%;2BDD体系阳极·OH产生速率和阴极H2产生速率均低于Pb O2体系,即表面活性位点数量少于Pb O2电极,因此·OH数量不是决定矿化能力大小的关键;3BDD电极表面吸附氧活性更强,结合能(532.37e V)大于Pb O2(530.74e V),且表面吸附层更薄,产生的·OH形态更自由,是决定其具有更大矿化能力的关键因素.     

电流密度对BDD电极电化学矿化吲哚的影响与机制

掺硼金刚石膜(BDD)电极电化学氧化法是去除难降解有机污染物的有效手段.与总有机碳(TOC)等的测定相比,气态中间产物的逸出量能够更直观有效地反映有机物的矿化程度与去除效果.本研究以吲哚为代表性污染物,通过对比不同电流密度(10、20和30 m A·cm-2)下BDD电极对吲哚的去除率与矿化率,结合降解过程中碳和氮形态的变化与守恒情况,分析吲哚的降解机制.结果表明,BDD电极对吲哚有良好的去除效果,电流密度为10、20、30 m A·cm-2时,吲哚达到100%去除的时间分别为8、5和4 h;TOC去除率、CO_2产生量均随电流密度的增加而增大,证明矿化率与电流密度成正相关;电解产生的CO_2气体与TOC、无机碳(TIC)构成了碳守恒体系.4~5 h时,体系TOC、TON和CO_2产生量均没有变化,表明电解产生的靛红具有较高的稳定性,此时为中间产物积累阶段;XPS表征进一步证实了中间产物靛红、苯醌等在电极表面的吸附,随着电解时间的延长,这些吸附的中间产物可进一步被降解.本研究从气态产物检测及碳氮形态分析与守恒的角度阐释吲哚矿化过程,对于辅助揭示有机物的电解过程有重要意义.     

臭氧降解水中邻苯二甲酸二甲酯的动力学及影响因素

利用臭氧(O3)降解含较高浓度邻苯二甲酸二甲酯(DMP)的模拟废水,采用竞争动力学法,以硝基苯为参比有机物,获得了DMP与O3及羟基自由基(·OH)的反应速率常数,研究了·OH抑制剂叔丁醇(TBA)、pH和多种离子对O3降解DMP效果的影响.结果表明,O3降解DMP符合拟一级动力学,DMP与O3的反应速率常数kO3-DMP为(0.064±0.014)L.(mol·s)-1,与·OH的反应速率常数k·OH-DMP为3.59×109L.(mol·s)-1;O3降解DMP过程中,生成的羧酸类中间产物使弱酸或弱碱性反应液的pH下降,但不足以影响强酸或强碱性反应液的pH;降解过程中产生大量中间产物使COD的去除率滞后于DMP的降解率,且部分中间产物不易被矿化;较低浓度的TBA不足以抑制·OH与DMP反应,当TBA的浓度增大到DMP的90.21倍时,DMP的降解率由98.7%降为8.8%,已经基本抑制了·OH与DMP的反应;用磷酸盐缓冲溶液调节反应液pH,DMP的降解效果优于用NaOH/H2SO4调节;水中常见低浓度阴阳离子对DMP的降解效果没有影响,高浓度SO24-、NO3-和HPO24-对DMP降解效果的影响相对较小,高浓度Cl-和HCO3-对DMP的降解有抑制作用,且HCO3-的影响大于Cl-,当Cl-和HCO3-的浓度分别为7 097 mg·L-1和6 093 mg·L-1时,反应40 min,DMP降解率分别为50.5%和26.2%.     

Electro-oxidation of Ni (II)-citrate complexes at BDD electrode and simultaneous recovery of metallic nickel by electrodeposition

The simultaneous electro-oxidation of Ni (II)-citrate and electrodeposition recovery of nickel metal were attempted in a combined electro-oxidation-electrodeposition reactor with a boron-doped diamond (BDD) anode and a polished titanium cathode. Effects of initial nickel citrate concentration, current density, initial pH, electrode spacing, electrolyte type, and initial electrolyte dosage on electrochemical performance were examined. The efficiencies of Ni (II)-citrate removal and nickel metal recovery were determined to be 100% and over 72%, respectively, under the optimized conditions (10 mA/cm², pH 4.09, 80 mmol/L Na₂SO₄, initial Ni (II)-citrate concentration of 75 mg/L, electrode spacing of 1 cm, and 180 min of electrolysis). Energy consumption increased with increased current density, and the energy consumption was 0.032 kWh/L at a current density of 10 mA/cm² (pH 6.58). The deposits at the cathode were characterized by scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). These characterization results indicated that the purity of metallic nickel in cathodic deposition was over 95%. The electrochemical system exhibited a prospective approach to oxidize metal complexes and recover metallic nickel.     

掺硼金刚石电极处理榨菜废水试验研究

掺硼金刚石(BDD)电极在电化学氧化难生物降解性废水时具有电化学性能良好、处理效果好等特点,因而受到广泛关注.本试验采用BDD电极电化学氧化榨菜废水,并考察了稀释比、初始pH值、电流密度、极板间距等参数对COD、氨氮(NH3-N)去除率的影响.试验结果表明:在稀释比为1∶2、电流密度50 mA·cm-2、未调节pH值、极板间距为15 mm的最优工况下,COD、NH3-N去除率分别为96.9%、100%.COD去除率满足线性方程y=0.435t(R2=0.9899),NH3-N去除率满足多项式拟合方程y=0.53+0.936t+0.031t2-3.46×10-4t3(R2=0.9956).研究表明,BDD电极电化学氧化榨菜废水是一种有效的高级氧化工艺.     

邻苯二甲酸二甲酯的紫外光-H2O2降解机制研究

为研究邻苯二甲酸二甲酯(DMP)在紫外光(UV)-H2O2体系下的光降解机制,利用质谱仪鉴定了目标化合物的降解产物,并借此推测其可能的降解途径.结果表明,在UV-H2O2的体系中,10 mg.L-1的DMP在90 min内的降解率达到92.3%,溶液pH值由初始的6.50降至4.98.通过GC/MS、LC/MS分析,DMP在UV-H2O2降解过程中的产物有六类,并且推断出DMP的两条侧链同时发生水解作用,生成的邻苯二甲酸可以异构为更加稳定的对苯二甲酸.此外,DMP还可以发生苯环取代、侧链缩合成环等反应,最后,在.OH的作用下,DMP及其芳香族中间产物发生开环反应,苯环被破坏,生成多种小分子有机酸,并进一步矿化为CO2和水.     

Kinetics and corrosion products of aqueous nitrate reduction by iron powder without reaction conditions control

Although considerable research has been conducted on nitrate reduction by zero-valent iron powder (Fe0), these studies were mostly operated under anaerobic conditions with invariable pH that was unsuitable for practical application. Without reaction conditions (dissolved oxygen or reaction pH) control, this work aimed at subjecting the kinetics of denitrification by microscale Fe0 (160–200 mesh) to analysis the factors affecting the denitrification of nitrate and the composition of iron reductive products c...     

Effect of long-term fertilization on C mineralization and production of CH4 and CO2 under anaerobic incubation from bulk samples and particle size fractions of a typical paddy soil

Impacts of nutrient management on C mineralization and greenhouse gas (GHGs) emission from soils have been of much concern in global change. Using laboratory incubation, the production of CH₄ and CO₂ were studied from both bulk samples and the particle size fractions (PSF) of topsoil from a paddy under a long-term different fertilization trial (including non (NF), chemical without (CF) and with manure (CFM) fertilization, respectively) in the Tai Lake Region, China. Four PSFs (2000–200, 200–20, 20–2, <2 μm) were separated from undisturbed samples collected after rice harvest by a low-energy ultrasonic dispersion procedure. Both the bulk samples and PSFs were incubated under submerged condition for 72 days. The concentration of CH₄ and CO₂ evolved during incubation were determined by gas chromatography. C mineralization rates ranged from 0.13 to 0.52 mg C g⁻¹ C day⁻¹, with different fertilizations and size of the PSFs, and were not correlated with C/N ratio. While CO₂ production predominated over CH₄ from C mineralization from both bulk samples and the size fractions, CH₄ production played a predominant role in the total global warming potential (GWP) under all treatments. C mineralization of bulk soil was significantly higher under CF than under CFM and NF. CH₄ production, however, was 3 times as under CFM and 27 times as under NF, indicating a tremendous effect of chemical fertilization alone on the total GWP. CO₂ production from the PSFs differed from CH₄ under a single treatment, which was notably from the coarse PSFs larger than 200 μm. Higher C mineralization and CH₄ production with a higher metabolic quotient under CF implicated a vulnerability of soil functioning of GHGs mitigation in the paddy receiving chemical fertilizers only. Thus, rational organic amendments should be undertaken for mitigating the climate change.     

Bi-PbO2电极电化学氧化去除模拟废水中氨氮的研究

本实验采用钛网作为基体,利用电沉积方法制备了纯PbO2电极和Bi-PbO2电极,通过SEM、XRD、XPS对电极的表面形态进行了表征,利用循环伏安法对Bi-PbO2电极电化学特性进行了研究.同时,以氨氮模拟废水作为研究对象,考察了Bi-PbO2电极的电催化活性,探讨了氨氮电化学氧化降解机理.结果表明,Bi-PbO2电极的形态表征、电催化活性明显高于纯PbO2电极,氨氮的去除效率随电流密度的增加而提高,碱性条件下氨氮的去除效果明显好于酸性条件,适量浓度的Cl-的引入在碱性条件下提高了氨氮的去除效果.当氨氮初始浓度为50 mg·L-1、电流密度为40 mA·cm-2、pH=12、Cl-浓度为600 mg·L-1时,电解120 min后,氨氮100%去除.氨氮的降解机理为:体系中无添加氯离子,酸性条件下氨氮主要是通过间接氧化去除,碱性条件下通过直接电氧化和间接氧化共同完成;体系中添加氯离子,氨氮的去除主要是通过溶液中生成的有效氯间接氧化去除.     

Bi-TiO2纳米管阵列电极对水中硝酸盐的去除

为研究电化学技术对硝酸盐氮的去除作用,本实验以TiO₂纳米管（TiO₂-NT）为基体,利用电沉积法制备了Bi-TiO₂纳米管阵列电极（Bi-TNA）.同时,采用X-射线衍射仪（XRD）、扫描电子显微镜（SEM）对电极涂层表面形貌和晶体结构进行表征,并分析了电流密度、pH、初始浓度对硝态氮去除、亚硝态氮和氨氮转换、总氮去除及氮气选择性的影响.最后分析了Bi-TNA电极对硝态氮去除的动力学模型.结果表明,在单因素水平下,最佳操作条件为：硝态氮浓度为50 mg·L^-1,电流密度为30 mA·cm^-2,pH值为8.5.Bi-TNA电极对硝态氮的还原过程都遵循一级反应动力学.     

纳米Fe3C/炭纤维非均相电芬顿降解二甲基砷的研究

针对结构稳定且难以靠常规方法去除的二甲基砷,制备新型负载Fe_3C纳米粒子的炭纤维催化剂,并对其非均相电芬顿降解二甲基砷进行了研究.结果表明,纳米Fe_3C/CF与阴极产生的H2O2发生电芬顿催化反应产生羟基自由基将二甲基砷降解为一甲基砷和As(V),As(V)可被同步吸附在Fe_3C/CF催化剂表面.通过考察电催化过程中初始p H、反应物初始浓度、电流强度和催化剂投加量等因素对催化氧化DMA效果的影响,表明在初始p H为3,二甲基砷初始浓度为5 mg·L~(-1),Fe_3C/CF投量为500 mg·L~(-1)的最佳条件下,经非均相电芬顿反应360 min后,二甲基砷去除率高达96%.     

钛基改性DSA电极氧化法去除水中全氟化合物

为了提高金属氧化物电极(DSA电极)的稳定性及催化活性,实现全氟化合物(PFCs)的高效降解,分别以溶胶涂覆法和电沉积法制备了改性DSA(Ti/SnO_2-ZnO)电极,并用于全氟辛酸(PFOA)和全氟辛烷磺酸(PFOS)的电化学降解过程研究.实验分别考察了电流密度、溶液初始pH、 PFOA与PFOS初始浓度对PFCs降解效果的影响.结果表明:两种方法制备的改性DSA电极表面均匀负载了SnO_2-ZnO复合涂层.在二维电极体系中,极板面积约为65.0 cm~2,电流密度为20.0 mA·cm~(-2),极板间距为15.0 mm,电解质为1.30 g·L~(-1)次氯酸钠溶液以及电解时间为150 min时,溶胶涂覆法和电沉积法所制备的Ti/SnO_2-ZnO电极对初始浓度为100 mg·L~(-1)的PFOA和PFOS分别在pH为3.50和6.50时去除效果最佳,分别达到了90.6%、94.6%和91.0%、93.7%;循环使用电极3次,其降解过程均符合准一级反应动力学,且电沉积法制备的电极效果优于溶胶涂敷法,表现出对PFCs类污染物稳定、高效的去除能力.     

感应电芬顿降解二甲基砷的效果与机理研究

二甲基砷作为甲基砷的主要种类之一,主要由含砷废水的排放和农药滥用进入环境水体,进而严重威胁着人类的健康.通过改进电芬顿反应中Fe~(2+)的投加方式,构建了以铁棒为感应阳极、RuO_2/Ti网为阳极、2个活性炭纤维为双阴极的感应电芬顿体系.为探究感应电芬顿体系对二甲基砷的降解效果与机理,考察了反应过程中初始pH、电流密度、反应物初始浓度等因素对二甲基砷去除效果的影响.结果表明,在初始pH值为3,电流密度为2 m A·cm~(-2),二甲基砷初始浓度为5 mg·L~(-1)的最佳条件下,经感应电芬顿反应240 min后,二甲基砷去除率高达94.4%.在此体系中,感应铁电极不断释放的Fe~(2+)与阴极产生的H_2O_2发生电芬顿反应产生羟基自由基将二甲基砷降解为一甲基砷、As(Ⅲ)和As(V),同时,铁离子水解生成的铁的羟基络合物将二甲基砷、一甲基砷、As(III)和As(V)吸附在其表面,从而达到二甲基砷的高效去除.     

负载多壁碳纳米管的多孔Ti/SnO2-Sb-Ni电极电催化氧化双酚A

为发展废水中双酚A（BPA）的处理技术和保护水环境安全,采用“电沉积-热分解”法制备负载多壁碳纳米管（MWCNTs）的多孔Ti/SnO₂-Sb-Ni电极,研究了电极对BPA的去除能力、动力学特征和矿化效率,初步分析了BPA的降解途径.结果表明,当浸渍液中n（Sn）∶n（Sb）∶n（Ni）为100∶10∶1、ρ（MWCNTs）为0.8g·L^-1时,制备的电极对BPA的去除效果最好;负载MWCNTs使得电极表面的晶体尺寸更小,可增大电极的比表面积,为电催化反应提供更多的活性位点,进而提高电极的电催化效率.当c（Na₂SO₄）为10mmol·L^-1、反应液初始pH为5和电流密度为50 mA·cm^-2时,对50 mg·L^-1的BPA降解60 min时去除效率达到99.76%;去除过程符合一级反应动力学方程,速率常数为0.096 min^-1;电解120 min时,TOC去除率达到67.01%.采用液相色谱-串联质谱分析法（...     

水中腐殖酸对高级氧化联用技术去除内分泌干扰物（DMP）的影响

使用腐殖酸模拟本底天然有机物进行试验,采用UV-H₂O₂、O₃、UV-O₃3种高级氧化工艺,研究了水中腐殖酸对3种高级氧化联用技术去除饮用水中内分泌干扰物(DMP)的影响.结果表明,UV-H₂O₂联用工艺氧化DMP的过程符合伪一级反应动力学,水中腐殖酸的存在对UV-H₂O₂联用工艺氧化DMP的影响非常大,伪一级反应的速率常数与本底TOC值的关系式为K=0.162 0[TOC]₀^{-0.817 1};同时水中腐殖酸对UV-O₃联用工艺氧化DMP的效果影响比较大,而总体上腐殖酸对O₃氧化DMP的去除影响不大.从效果分析知,在一定浓度腐殖酸本底条件下单独O₃氧化和UV-O₃联用工艺对DMP的氧化均以O₃分子对DMP的氧化起主导作用,当腐殖酸浓度变小,UV-O₃联用工艺体系中.OH自由基氧化DMP的重要性增大.水中腐殖酸对3种高级氧化工艺的影响程度顺序依次为:UV-H₂O₂>UV-O₃>O₃.     

阴极原位产H2O2强化光电催化降解水中EDTA的研究

本研究构建了以活性碳纤维(Activated Carbon Fiber,ACF)为阴极,TiO_2/Ti与Ru O_2/Ti为双阳极的光电催化体系.该体系中,Ru O_2/Ti电阳极和TiO_2/Ti光阳极均有氧化作用,可同时氧化降解污染物;且电阳极具有较强析氧作用,能产生大量O_2;ACF阴极具有还原作用,可将体系中产生的O_2原位还原为H_2O_2;H_2O_2在紫外光下产生·OH,进而强化光电催化与电催化氧化过程,实现对水中乙二胺四乙酸二钠(EDTA)的高效去除.本论文详细考察了电流密度、pH、曝气等因素对EDTA降解效果的影响.结果表明,在EDTA初始浓度为300 mg·L~(-1)、溶液初始pH=4.84、电流密度为12 m A·cm~(-2)和光电流密度为0.012 m A·cm~(-2)的条件下,反应90 min后,EDTA降解率高于90%.该催化体系实现了EDTA的高效降解.     

Cation exchange capacities of soil organic matter fractions in a Ferric Lixisol with different organic matter inputs

Soil organic matter (SOM) has an important effect on the physicochemical status of highly weathered soils in the tropics. This work was conducted to determine the contribution of different SOM fractions to the cation exchange capacity (CEC) of a tropical soil and to study the effect of organic matter inputs of different biochemical composition on the CEC of SOM. Soil samples were collected from a 20-year-old arboretum established on a Ferric Lixisol, under seven multipurpose tree species: Afzelia africana, Dactyladenia barteri, Gliricidia sepium, Gmelina arborea, Leucaena leucocephala, Pterocarpus santalinoides, and Treculia africana. Fractions were obtained by wet sieving and sedimentation after ultrasonic dispersion. Relationships between CEC and pH were determined using the silver thiourea-method and were described by linear regression. The CEC of the fractions smaller than 0.053 mm was inversely related to their particle size: clay (<0.002 mm)>fine silt (0.002–0.02 mm)>coarse silt (0.02–0.053 mm), except for the soils under T. africana, D. barteri, and L. leucocephala, where the CEC of the fine silt fraction was highest or comparable to the CEC of the clay fraction. The clay and fine silt fractions were responsible for 76–90% of the soil CEC at pH 5.8. The contribution of the fine silt fraction to the CEC at pH 5.8 ranged from 35 to 50%, which stressed the importance of the fine silt fraction for the physicochemical properties of the soil. Differences in CEC between treatments for the whole soil and the fractions could be explained by the differences in carbon content. Except for the intercept for the clay fraction, SOM had a significant (P<0.001) contribution to both the intercepts (=estimated CEC at pH 0) and slopes (=pH-dependent charge) of the CEC–pH relationships for the whole soil and the fractions. The CEC of SOM at pH 5.8 varied between 283 cmol_c kg⁻¹ C for particulate organic matter, and 563 cmol_c kg⁻¹ C for the fine silt fraction. The biochemical composition of the organic inputs did not have an important effect on the CEC of SOM. In total, SOM was responsible for 75–85% of the CEC of these soils.     

Effect of background electrolytes on the adsorption of nitroaromatic compounds onto bentonite

To further elucidate interaction of nitroaromatic compounds with mineral surface, the sorption of m-dinitrobenzene (m-DNB) and nitrobenzene to original bentonite in aqueous solution containing di erent electrolytes (i.e., KCl, NH4Cl, CaCl2 and Tetramethylammonium bromide (TMAB)) was studied. The sorption of m-DNB was greatly enhanced with the presence of KCl and NH4Cl, while little influence was observed with CaCl2 and TMAB, following the order of KCl > NH4Cl TMAB, CaCl2, or DI water. For nitrobenzene, sorption enhancement only occurred at high nitrobenzene concentrations in the presence of KCl, and the solute equilibrium concentration at inflexion point was lowered with increasing KCl concentration. These sorption enhancements were significantly promoted with the increase of electrolyte concentration. The salting-out e ect is insu cient to account for the sorption enhancement by original bentonite with increasing KCl or NH4Cl concentration. X-ray di raction patterns of bentonite suspensions indicated that the sorption enhancement of m-DNB was attributed to the intercalation of K+ or NH4 + into bentonite interlayer and then dehydration with m-DNB to form inner-sphere complexes, which caused previously expanded bentonite interlayers to collapse in aqueous suspension, thus further enhanced the interaction of phenyl with siloxane surface. In comparison, the sorption enhancement of NB is attributed to the formation of outer-sphere complexes with K+ at high solute-loadings (> 200–400 mg/kg). The sorption of m-DNB to initially modified TMA+-bentonite and K+-bentonite was almost the same as respective sorption to original bentonite in solution containing TMA+ and K+.     

藻源性黑水团环境效应:对水-沉积物界面氮磷变化的驱动作用

利用自制的静态模拟实验装置,通过连续抽取间隙水来研究藻细胞沉降在沉积物表面后对水-沉积物界面处的N、P变化的驱动作用及影响效果.结果表明,藻细胞沉降后,在50 min内就完全消耗掉水-沉积物界面处的溶解氧,同时水体出现严重的发黑、发臭现象;形成的厌氧、强还原环境,使得死亡的藻细胞在界面处发生强烈的厌氧矿化作用,界面处的水溶性PO34--P、NH 4+-N在实验的第2 d开始向上覆水中扩散,含量不断增加.至实验结束时(实验第8 d),界面处PO34--P、NH 4+-N的含量分别达到4.00 mg/L、39.45 mg/L,分别为同期对照实验样柱中的10倍和241倍(对照样柱中的PO43--P、NH 4+-N的含量分别为0.42 mg/L、0.16 mg/L).藻细胞的厌氧矿化加剧了氮磷营养盐向上覆水的扩散,在加重水体营养盐含量的同时,也为藻华的再次发生提供了物质基础.