Amperometric hydrogen peroxide biosensor based on immobilization of DNA-Cu(II) in DNA/chitosan polyion complex membrane

DNA/chitosan polyion complex membrane was used as a support for immobilization of electrocatalytic species-copper ions, which specifically bound to dsDNA and catalyzed the hydrogen peroxide reduction. The polyion complex membrane consisted with DNA-Cu(II) complex and chitosan was prepared on a glassy carbon electrode (GCE). Electrochemical measurements of the DNA-Cu(II)/chitosan membrane-modified GCE revealed that the copper ion embedded in the DNA/chitosan layer exhibited good electrochemical behaviors. The DNA-Cu(II)/chitosan/GC electrode showed an excellent electrocatalytic activity for the H₂O₂ reduction. Even in the presence of dissolved oxygen, the sensor exhibited highly sensitive and rapid (response time, about 6 s) response to H₂O₂. The steady-state cathodic current responses of the sensor obtained at ?0.2 V versus Ag/AgCl in air-saturated 100 mmol/L phosphate buffer (pH 5.0) increased linearly up to 10 mmol/L with the detection limit of 3 μmol/L. Effects of applied potential and buffer pH upon the response currents of the sensor were investigated for an optimum analytical performance. Ascorbic acid and glucose almost have no interference to measurement of H₂O₂. In addition, the sensor exhibited good reproducibility.     

Coulometric determination of sulfur speciation in natural waters

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活性炭纤维三维电极电催化降解水中间甲酚——效能及影响因素研究

探讨了以活性炭纤维作为三维粒子电极电氧化降解水中间甲酚的可行性与效果.首先对活性炭纤维的表面形貌,比表面积,孔结构和表面官能团情况进行了表征,发现活性炭纤维（ACFs）以单束纤维的结构交叉排列而成,比表面积较大（>1480m²/g）,另外发现活性炭纤维的表面存在较多官能团种类.结合活性炭纤维表征结果,论文对活性炭纤维三维电极的相关影响因素进行了考察,研究了活性炭纤维种类,活性炭纤维与电极的接触方式以及反应溶液初始pH值对实验结果的影响.结果表明,活性炭纤维表面过多的含氧官能团不利于污染物的快速降解,而三维电极电氧化效果随着pH值的降低而显著增大,不同的电极接触方式对三维电极电氧化效果也有较大影响.     

原水碳源分子量分布及DPB效能对酸化时间的响应

采用超滤-纳滤膜法对污水中碳源分子量(MW)进行切割试验,并测定各区间总有机碳(TOC)浓度以了解污水碳源组成特性;同时采用污水酸化技术,研究在不同酸化时间,碳源分子量分布的变化及对厌氧-膜好氧-反硝化(A2N)工艺中反硝化聚磷菌(DPB)用碳和净污效能的影响.结果表明,试验原水TOC为(58.3±2.83) mg /L,其中颗粒有机碳(POC)为(38.05±1.65)mg /L,占65.27%,剩余溶解有机碳(DOC)在分子量0.5kDa以上区间呈现“W”型分布,其中 MW>100kDa、10k~5kDa、1k~0.5kDa、MW<0.5kDa区间碳源分别占36.20%、12.05%、13.68%和29.83%.在不同酸化时间下,POC含量与DOC分布存在显著差异,在12h内酸化,可以有效将POC转化为DOC,且在14mg/L左右趋于平衡;DOC在大于0.5kDa区间上的分布呈现随时间而整体后移的趋势,在8h时碳源质量最优,其中MW<1kDa的小分子有机物高达17.30mg/L;此时,DPB污泥在厌氧池与缺氧池中的碳源利用率分别为 83.48%、79.59%,比0h时分别提高了23.56%、18.03%;TN、TP去除率分别提高了14.63%、16.98%.     

样品处理方法对海洋沉积物有机碳稳定同位素测定的影响

利用元素分析仪-稳定同位素质谱仪（EA-IRMS）联用技术测定海洋沉积物样品有机碳稳定同位素比值,样品的前处理方法会影响测定结果的准确性。本文选取两种常用前处理方法:酸洗法和酸蒸法进行比对。通过对比,酸洗法使用的最佳条件是1 mol/L的HCl,处理8 h,可较好去除沉积物样品中的无机碳;酸蒸法的最佳反应条件是处理12~18 h,且应根据沉积物样品无机碳含量选取相适的处理时间。两种处理方法,在最佳条件下所得测试数据标准偏差均满足测试要求,证明两种方法均适用于沉积物样品的测试。     

Pd/C气体扩散电极用于电化学降解五氯酚钠的研究

采用氢气还原法制备出Pd/C催化剂,利用循环伏安曲线（CV）对氧在Pd/C催化剂上的电化学还原行为进行了分析,并由催化剂制备成Pd/C气体扩散阴极,采用先通H₂后通空气的方式在隔膜电解体系中对五氯酚钠进行降解,比较了不同电极体系下五氯酚钠的去除效果.结果表明,在阴极室,Pd/C气体扩散电极通过外界曝气提供的O₂在阴极还原产生H₂O₂,电解100 min后H₂O₂的稳定浓度达到9.8 mg/L.实验制备的Pd/C气体扩散阴极既对五氯酚钠具有还原脱氯作用（通入H₂时）,又促进O₂还原生成H₂O₂（通入O₂时）,它对五氯酚钠的去除效果要好于不掺杂Pd的气体扩散阴极.反应120 min后,五氯酚钠平均转化率和脱氯率均超过80%,反应200 min后TOC平均去除率分别超过75%.采用高效液相色谱（HPLC）等手段分析出五氯酚钠在阴极室还原脱氯的中间产物主要是苯酚,Pd/C气体扩散阴极利用电化学还原脱氯和阴阳极同时氧化相结合对氯酚类有机物的降解是可行的.     

MnO2@ Graphite电极类电Fenton降解有毒有机污染物

制备了二氧化锰复合石墨(MnO2@graphite)电极,通过XRD,TEM对电极材料进行表征,并通过电化学工作系统(循环伏安法,线性扫描伏安法,计时电量法)对MnO2@graphite电极的电催化机理进行了研究.以有机染料罗丹明B( RhodamineB,RhB)和2,4-二氯苯酚(2,4-DCP)为对象,探讨了 p...     

低碳源条件下BSBR工艺磷酸盐强化吸收影响因素分析

相较于传统强化生物除磷工艺通过测流实现污泥磷酸盐的富集和回收,生物膜法可对废水中的磷酸盐进行高效同步去除和富集,具有应用潜力。针对生物膜法厌氧释磷需要高碳源刺激的问题,通过优化工艺条件强化生物膜好氧吸磷能力提高生物膜蓄磷量,进而减少厌氧释磷时的碳源消耗。采用生物膜法序批式反应器(BSBR),考察了在低碳源投加下,蓄磷量与磷富集罐磷浓度的响应关系,采用正交试验探究溶解氧、搅拌速度以及好氧时间对磷酸盐强化吸收的影响。结果表明:当温度为(25±2)℃、厌氧外加碳源为(180±20) mg/L时,富集罐磷浓度随着生物膜蓄磷量的增加而增加,最高可达到90.62 mg/L。相同蓄磷量下,溶解氧浓度从2 mg/L增加至8 mg/L,磷酸盐最大吸收速率可从2.60 mg/(L·h)上升到8.70 mg/(L·h)。正交实验结果表明:各因素对磷酸盐强化吸收的影响顺序为溶解氧>好氧时间>搅拌速度。当溶解氧浓度为6 mg/L,搅拌速度为200 r/min,好氧时间为5 h时,除磷效率最高可达99.98%。     

电絮凝法处理地下水的试验研究

利用电絮凝法处理受到污染的高氟地下水,研究了电极间距、原水pH值、电流密度对处理效果的影响。实验结果表明,电絮凝法去除地下水中的氟和TOC时,不需改变原水的pH值。在电极间距为1.0cm,电流密度为32.4A/m2,反应10min后,出水中F-浓度<1.0mg/L,符合国家生活饮用水卫生标准,TOC的去除率达到66%左右,优于传统给水处理工艺对TOC的去除效率。电絮凝对地下水中污染物的去除机理包括电絮凝、电化学氧化和还原以及电气浮等协同作用。     

巢湖夏季水华期间水体中溶解性碳水化合物的研究

在2010年7月巢湖蓝藻水华暴发期间,采集了11个点位的表层水样,分析了叶绿素含量﹑溶解性有机碳﹑不同形态氮磷营养盐以及各种碳水化合物的浓度.研究结果表明,巢湖营养盐浓度呈现西高东低的分布趋势,叶绿素浓度与营养盐浓度分布规律不完全一致,说明影响藻类空间分布的因素很多.硝酸盐浓度是影响溶解性有机碳的重要因素.总溶解性碳水化合物占溶解性有机碳的比例最高为26%,多糖和单糖所占比例分别为21%和6%.叶绿素浓度与溶解性有机碳,各种碳水化合物之间不具有显著相关性,说明在巢湖蓝藻水华暴发期间,除了浮游植物,陆源输入可能也是溶解性有机碳及各种碳水化合物的重要来源.     

A simple and sensitive method for the determination of 4-n-octylphenol based on multi-walled carbon nanotubes modified glassy carbon electrode

A simple and sensitive electroanalytical method was presented for the determination of 4-n-octylphenol (OP) based on multi-walled carbon nanotubes (MWCNTs) modified glassy carbon electrode (GCE). OP was directly oxidized on the MWCNTs/GCE, and the electrochemical oxidation mechanism was demonstrated by a one-electron and one-proton process in the reaction. The oxidation peak current of OP was significantly enhanced by the use of MWCNTs/GCE compared with those of bare glassy carbon electrode, suggesting that the modified electrode can remarkably improve the performance for OP determination. Factors influencing the detection processes were optimized. Under these optimal conditions, a linear relationship between concentration of OP and current response was obtained in the range of 5×10^-8 to 1×10^-5 mol/L with a detection limit of 1.5×10^-8 mol/L and correlation coefficient 0.9986. The modified electrode showed good selectivity, sensitivity, reproducibility and high stability.     

制备工艺对活性炭电极电吸附性能的影响

用活性炭、酚醛树脂和乌洛托品制备了活性炭电极。研究了电极制备过程中黏结剂添加量、活性炭用量以及成型后活性炭的炭化温度和炭化时间对电吸附除盐性能的影响,并利用扫描电子显微镜(SEM)分析了电极的表面形貌。结果表明:当活性炭、酚醛树脂和乌洛托品混合比例为8:1.8:0.2时,电极能够成型,随着黏结剂的比例增加,电极的除盐率降低;随着活性炭用量的增加,吸附平衡的时间增加,除盐率提高,但平衡吸附量降低,当NaCl浓度降低到一定程度时,再增加活性炭用量去除率变化变小,试验选定的活性炭用量为0.45g/片电极;随着炭化温度的升高和炭化时间的增长,活性炭电极电吸附除盐效果明显提高,850℃下炭化2h的电极炭化完全,除盐率是未炭化的电极除盐率的2.08倍。     

微生物电容脱盐燃料电池性能研究

以微生物电容脱盐燃料电池(MCDC)为研究对象,考察了反应时间、盐溶液浓度和电容电极对数对MCDC脱盐效率的影响.试验采用阳离子交换膜分隔阳极室与脱盐室,阴离子交换膜分隔阴极室与脱盐室.试验结果显示在处理5 g·L-1的NaCl溶液试验中,脱盐室溶液盐度先降低后升高,在反应运行30 min时,脱盐室达到最大脱盐率47.83%.同时发现在脱盐过程中,阳极室和阴极室溶液盐度持续降低,运行150 min后分别下降到15.24%和6.12%.随盐溶液浓度的增加,脱盐率降低,单位电极吸附量增加,根据Langmuir方程和Freundlich方程的线性拟合得到,MCDC最大脱盐吸附容量为72.99 mg·g-1,电容吸附为复杂度的双分子层吸附.电极对数从1对增加到4对,MCDC的脱盐效率提高了37.37%.通过电容电极反接,可在1 h内实现电容再生.     

西太湖秋季蓝藻水华过后细胞裂解对溶解性有机碳影响

从2009年7月~2010年3月每月采集西太湖表层水样,分析叶绿素含量﹑蓝藻细胞裂解速率﹑磷酸盐浓度的变化,并通过切向流超滤系统分离得到的高分子量(1kDa~0.5μm)溶解性有机物的碳氮比值和高分子量溶解性有机碳浓度的变化.结果表明,西太湖蓝藻细胞裂解速率在11月达到最大值(0.43d-1),而磷酸盐和高分子量溶解性有机碳浓度分别在12月与9月达到最大值.细胞裂解速率与磷酸盐﹑高分子量溶解性有机碳浓度之间没有相关性,说明水华过后影响磷酸盐浓度﹑高分子量溶解性有机碳的因素很多,蓝藻细胞裂解只是其中重要因素之一.藻类水华的出现可能导致水体中其它磷形态(如有机磷)与磷酸盐之间的迁移转化,而大型浅水湖泊扰动导致的沉积物再悬浮和水华过后频繁的细菌活动都可能是影响高分子量溶解性有机碳的因素.秋季水华过后蓝藻细胞裂解释放的有机碳进入微食物网循环,引起细菌活动频繁,而溶解性有机物中含碳化合物比含氮化合物容易降解,所以碳氮比值逐渐减少.此外细菌通过硝酸盐合成溶解性有机氮也可能是碳氮比值减少的一个重要原因.     

碳纳米管电极电还原降解水中头孢他啶

通过SEM、FITR、CV、Tafel等表征,以头孢他啶为目标污染物,研究了自制多壁碳纳米管电极电还原难降解有机物等的特性,并用高效液相色谱检测反应后目标污染物的质量浓度.结果表明,该电极性能稳定,可耐受一定程度的腐蚀,具有较好的性能.循环伏安结果表明,在800 mV左右获得较大的氧化峰,峰值达到-0.2 mA,头孢他啶在该电极上的降解是不可逆的.碳纳米管电极电还原降解头孢他啶的适宜工艺条件为:电极间距1 cm,电压15 V,初始质量浓度1 mg·L-1,离子强度1 g·L-1,pH=6.0.此条件下,反应60 min,头孢他啶的去除效率可达90%以上,该降解过程为二级反应.     

一种基于钴的丝网印刷磷酸盐传感器研究

采用丝网印刷技术制备用于水中磷酸盐检测的传感器,其中,掺有钴粉的碳浆为工作电极,银/氯化银浆为参比电极.在25℃下,对于用pH为4.0邻苯二甲酸氢钾(KHP)缓冲溶液配制的浓度梯度为1×10-5~0.1mol/L的KH2PO4溶液,钴碳比为1:7磷酸盐丝网印刷电极有良好的能斯特响应,响应斜率为-41.63mV/decade,检测限为5×10-6mol/L,响应时间为60s,稳定性较好.丝网印刷电极的重现性很好,测量同一溶液, 同一钴碳比的丝网印刷电极的相对误差小于1%,不同钴碳比的丝网印刷电极的相对误差小于3.5%.     

基于钴的磷酸盐离子选择性电极研究

文章以金属钴为基体,在其表面形成对磷酸二氢盐有良好电化学响应的氧化钴敏感膜,成功的制备了磷酸盐离子选择性电极。详细讨论了不同活化时间和不同活化溶液对磷酸盐检测的线性响应范围、响应斜率及检测限的影响。实验结果表明:该基于钴的磷酸盐离子选择性电极在0.025 mol/L邻苯二甲酸氢钾的底液中,对磷酸二氢盐在10-4~10-1mol/L浓度范围内呈线性响应,其响应斜率为-48.27 mV/dec,检测限为2.27×10-5mol/L,相关系数R2为0.99。该电极具有良好的稳定性和重现性。已成功用于实际自来水样中磷酸二氢盐的检测,结果满意。     

Electrochemical decolorization of dye wastewater by surface-activated boron-doped nanocrystalline diamond electrode

Complex organics contained in dye wastewater are difficult to degrade and often require electrochemical advanced oxidation processes (EAOPs) to treat it. Surface activation of the electrode used in such treatment is an important factor determining the success of the process. The performance of boron-doped nanocrystalline diamond (BD-NCD) film electrode for decolorization of Acid Yellow (AY-36) azo dye with respect to the surface activation by electrochemical polarization was studied. Anodic polarization found to be more suitable as electrode pretreatment compared to cathodic one. After anodic polarization, the originally H-terminated surface of BD-NCD was changed into O-terminated, making it more hydrophilic. Due to the oxidation of surface functional groups and some portion of sp² carbon in the BD-NCD film during anodic polarization, the electrode was successfully being activated showing lower background current, wider potential window and considerably less surface activity compared to the non-polarized one. Consequently, electrooxidation (EO) capability of the anodically-polarized BD-NCD to degrade AY-36 dye was significantly enhanced, capable of nearly total decolorization and chemical oxygen demand (COD) removal even after several times of re-using. The BD-NCD film electrode favored acidic condition for the dye degradation; and the presence of chloride ion in the solution was found to be more advantageous than sulfate active species.     

Effect of denitrifying bacteria on the electrochemical reaction of activated carbon fiber in electrochemical biofilm system

An electrochemical-activated denitrifying biofilm system consisting of activated carbon fiber electrodes immobilized with denitrifying bacteria film as cathode was studied. A revised model for an electrochemical-activated denitrifying biofilm was developed and validated by electrochemical analysis of cathodal polarization curves and nitrate consumption rate. The cathodal polarization curve and nitrate consumption rate were introduced to verify the rate of electrochemical reaction and the activity of denitrifying bacteria, respectively. It was shown that the denitrification process effectively strengthened the electrochemical reaction while the electron also intensified denitrification activity. Electron was transferred between electrochemical process and biological process not only by hydrogen molecule but also by new produced active hydrogen atom. Additionally, a parameter of apparent exchange current density was deprived from the cathodal polarization curve with high overpotential, and a new bio-effect current density was defined through statistical analysis, which was linearly dependent to the activity of denitrification bacteria. Activated carbon fiber (ACF) electrode was also found to be more suitable to the electrochemical denitrifying system compared with graphite and platinum. Translated from Environmental Pollution & Control, 2005, 27(7): 501–504 [译自: 环境污染与防治]     

东平湖DOM荧光特征及与氢氧同位素指标的相关性

本研究在运用三维荧光光谱示踪平水期东平湖DOM荧光特征的基础上,进一步分析其与氢氧同位素指标的相关性,并在此基础上尝试对大气降水的DOC贡献进行估算,以期为东平湖的污染控制及治理提供依据.结果表明,东平湖平水期DOM主要由类蛋白组分（C1和C4）和类腐殖质组分（C2和C3）构成,以类酪氨酸组分C1为主,C1所占比重将近50%.平水期东平湖DOM同时受陆源、内源及大气降水的影响,但以内源输入为主;外源输入中大气降水补给与大汶河输入所占比例相当;大气降水中的溶解性有机碳输入可能会对东平湖DOM产生不可忽视的影响,需进一步系统研究.氢氧稳定同位素与溶解态有机碳以及类腐殖质荧光之间呈显著相关关系,可以在一定程度上指示DOM的变化趋势.