电化学传感法测定水中亚硝酸盐

借助于简单可控的在线电聚合方法,溴酚蓝被修饰到玻碳电极表面,制备了聚溴酚蓝修饰玻碳电极。实验表明,聚溴酚蓝薄膜对于亚硝酸盐的电化学氧化具有很好的催化作用。经实验优化,聚溴酚蓝膜的最佳厚度为聚合20圈,最佳的检测底液为pH=4.0的0.01 mol/L磷酸盐缓冲溶液。亚硝酸盐在传感器上的电化学氧化是一个双电子双质子参与的过程。在最佳检测条件下,亚硝酸盐的氧化峰电流与其浓度在0.02~109.1μmol/L范围内有良好的线性关系,检测限低至5 nmol/L(S/N=3),所制备的亚硝酸盐传感器线性范围宽、检出限低、稳定性和重现性好、抗干扰能力强,将传感器应用于东湖水样中亚硝酸盐含量的测定,结果令人满意。     

Maize tassel-modified carbon paste electrode for voltammetric determination of Cu(II)

The preparation and application of a practical electrochemical sensor for environmental monitoring and assessment of heavy metal ions in samples is a subject of considerable interest. In this paper, a carbon paste electrode modified with maize tassel for the determination of Cu(II) has been proposed. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were used to study morphology and identify the functional groups on the modified electrode, respectively. First, Cu(II) was adsorbed on the carbon paste electrode surface at open circuit and voltammetric techniques were used to investigate the electrochemical performances of the sensor. The electrochemical sensor showed an excellent electrocatalytic activity towards Cu(II) at pH 5.0 and by increasing the amount of maize tassel biomass, a maximum response at 1:2.5 (maize tassel:carbon paste; w/w) was obtained. The electrocatalytic redox current of Cu(II) showed a linear response in the range (1.23 μM to 0.4 mM) with the correlation coefficient of 0.9980. The limit of detection and current–concentration sensitivity were calculated to be 0.13 (±0.01) μM and 0.012 (±0.001) μA/μM, respectively. The sensor gave good recovery of Cu(II) in the range from 96.0 to 98.0 % when applied to water samples.     

纳米TiO 2 -碳纳米管复合膜修饰电极伏安法测定水中α -萘酚和β -萘酚

摘要：制备了一种新型的纳米TiO2-碳纳米管复合膜修饰电极,在pH值为5.57的NaAc-HAc缓冲溶液中,研究了α-萘酚和β-萘酚在该修饰电极上的电化学行为,据此建立了纳米TiO2-碳纳米管复合膜修饰电极伏安法测定水中α-萘酚和β-萘酚的方法。优化了试验条件,α-萘酚和β-萘酚分别在8.3×10^-7mol／L—1.0×10^-5mol／L和7.8×10^-7mol／L—1.0×10^-5mol／L范围内,浓度与氧化峰电流呈良好的线性关系,开路富集3min,检出限分别为3.5××10^-7mol／L和2.3×10^-7mol／L,模拟水样测定的回收率为97.6％—101％。     

Preparation of a highly sensitive enzyme electrode using gold nanoparticles for measurement of pesticides at the ppt level

A highly sensitive enzyme electrode was prepared based on gold nanoparticles for measurement of pesticides. Gold nanoparticles of 25-30 nm were synthesized on a glassy carbon electrode by double-pulse technique while the coverage was controlled by applied potential and time. The gold nanoparticles were modified to form a self-assembled monolayer, followed by covalent binding of tyrosinase. The TYR-AuNP-GC electrode was compared with bare GC, AuNP-GC, and modified AuNP-GC and TYR-Au (plate type) electrodes in terms of cyclic voltammetry. The voltammograms well represent the sensitivity of enzymatic oxidation of catechol, substrates for the enzyme activity. The prepared electrode integrated into a continuous flow system and was tested to detect pesticides, such as 2,4-D, atrazine, and ziram. Under the optimized conditions of the flow system, the electrode performed reasonably according to the inhibition mechanism in the concentration range of 0.001-0.5 ng mL(-1). The enhanced performance was attributed to the favored microenvironment for the enzyme activity provided by SAM on gold nanoparticles.     

Formation of a Mercury Plated Carbon Paste Electrode by Electroreduction of a Mercury(II) Diethyldithiocarbamate Modified Carbon Paste

A novel approach to formation of a mercury film electrode (MFE) at the surface of a carbon paste electrode is proposed in this paper. This MFE is easy to fabricate, has good reproducibility and avoids the use of a plating mercury solution. In this new type of MFE, mercuric diethyldithiocarbamate (Hg(DDTC)2) was mixed with graphite powder and paraffin oil to form a chemically modified carbon paste electrode. When a -0.95V potential was applied to the electrode, the Hg(II) (in Hg(DDTC)2) was reduced to metallic Hg, thus forming a mercury film at the surface of the carbon paste electrode. The characteristics of this MFE were studied. This modified electrode was used in anodic stripping voltammetry. Conditions for the simultaneous determination of trace amount of Pb(II) and Cd(II) were also investigated.     

Almond shell activated carbon: adsorbent and catalytic support in the phenol degradation

In this work, two technologies are studied for the removal of phenol from aqueous solution: dynamic adsorption onto activated carbon and photocatalysis. Almond shell activated carbon (ASAC) was used as adsorbent and catalytic support in the phenol degradation process. The prepared catalyst by deposition of anatase TiO₂ on the surface of activated carbon was characterized by scanning electron microscopy, sorption of nitrogen, X-ray diffraction, Fourier transform infrared (FT-IR) spectroscopy, and pH_ZPC point of zero charge. In the continuous adsorption experiments, the effects of flow rate, bed height, and solution temperature on the breakthrough curves have been studied. The breakthrough curves were favorably described by the Yoon–Nelson model. The photocatalytic degradation of phenol has been investigated at room temperature using TiO₂-coated activated carbon as photocatalyst (TiO₂/ASAC). The degradation reaction was optimized with respect to the phenol concentration and catalyst amount. The kinetics of disappearance of the organic pollutant followed an apparent first-order rate. The findings demonstrated the applicability of ASAC for the adsorptive and catalytic treatment of phenol.     

Voltammetric trace determination of mercury using plant refuse modified carbon paste electrodes

Citrus limon peel (kitchen waste) and Leucaena leucocephala seeds (agricultural waste) were used as a modifier for fabrication of modified carbon paste electrode for determination of mercury in aqueous sample using differential pulse anodic stripping voltammetry. Mercury was adsorbed on electrode surface at open circuit and anodic stripping voltammetric scan was run from ?0.5 to 0.5 V. Various electrochemical parameters including amount of modifier, supporting electrolyte, accumulating solvent, pH of the accumulating solvent, and accumulation time were investigated. The effect of presence of other metal ions and surfactants was also studied. In comparison C. limon peel proved to be a better modifier than L. leucocephala seed biomass. This was justified by electrode characterization using cyclic voltammetry that indicated decrease in resistance of electrode when C. limon peel was used as modifier and increase when modifier was L. leucocephala seeds. Maximum current response was obtained using 5 % C. limon peel biomass, hydrochloric acid as supporting electrolyte, acetate buffer of pH 6 as an accumulating solvent, 10-min accumulation time, and scan rate of 50 mV/s. Linear calibration curves were obtained in the concentration range 100 to 1,000 μg L^?1 of mercury for accumulation time of 10 min with limit of detection of 57.75 μg L^?1 and limit of quantification of 192.48 μg L^?1. This technique does not use mercury as electrode material and, therefore, has a positive environmental benefit.     

Monitoring of Phenol in Wastewater Bioremediation by HPLC

Bioremediation emphasizes the detoxification and destruction of toxic substances by microorganisms. Wastewater obtained from an industrial concern was solvent extracted with methyl alcohol and dichloromethane and analysed by GC/MS. Besides phenol, a large variety of organic compounds were detected. Under controlled laboratory conditions, the wastewater was innoculated with a mixed culture of microorganisms specially selected for their abilities to degrade phenol. Samples were collected at regular intervals from the stirred tank bioreactor and analysed for phenol by reverse phase HPLC with a C18 column. Results shows that from an initial phenol concentration of 987 ppm, slightly more than 50% was destroyed within 163 hours. The dry weight of the microorganisms and the plate count (CFU/ml) shows a steady increase from 0.5238 gms to 0.5355 gms and from 1.1E+9 to 1.94E+13 respectively over the same period. This suggested that the phenol was consumed by the microorganisms as the sole carbon source.     

用PPO传感器测定水中酚类化合物初探

从马铃薯中提取一种多酚氧化酶，经过固化并与氧电极组装，成为一种可测大部分酚类化合物的ＰＰＯ传感器，其灵敏度、准确度、线性范围、响应速度及抗干扰性等均可基本满足要求，研究证明，该法具有一定的开发价值。     

过氧化聚吡咯/聚乙烯吡咯烷酮修饰碳糊电极测定废水中苯酚

建立了过氧化聚吡咯(OPPy)和聚乙烯吡咯烷酮(PVP)修饰碳糊电极测定废水中苯酚的方法.优化了试验条件,苯酚的氧化峰电流在1.0×10-5 mol/L～1.0×10-3 mol/L之间线性关系良好,检出限为1.0×10-6 mol/L.该电极制作简单,选择性好,测定灵敏度高,精密度与准确度均符合要求.     

Development of electrochemical based sandwich enzyme linked immunosensor for Cryptosporidium parvum detection in drinking water

Cryptosporidium parvum is one of the most important biological contaminants in drinking water and generates significant risks to public health. Due to low infectious dose of C. parvum, remarkably sensitive detection methods are required for water and food industry analysis. This present study describes a simple, sensitive, enzyme amplified sandwich form of an electrochemical immunosensor using dual labeled gold nanoparticles (alkaline phosphatase and anti-oocysts monoclonal antibody) in indium tin oxide (ITO) as an electrode to detect C. parvum. The biosensor was fabricated by immobilizing the anti-oocysts McAb on a gold nanoparticle functionalized ITO electrode, followed by the corresponding capture of analytes and dual labeled gold nanoparticle probe to detect the C. parvum target. The outcome shows the sensitivity of electrochemical immune sensor enhanced by gold nanoparticles with a limit of detection of 3 oocysts/mL in a minimal processing period. Our results demonstrated the sensitivity of the new approach compared to the customary method and the immunosensors showed acceptable precision, reproducibility, stability, and could be readily applied to multi analyte determination for environmental monitoring.     

线性扫描溶出伏安法同时测定水样中铅镉铜锌

通过多壁碳纳米管-Nafion复合膜修饰电极,建立水样中痕量铅、镉、铜、锌同时测定的线性扫描溶出伏安分析法,优化支持电解质及pH值、修饰剂用量、富集电位及时间等测定条件。实验结果表明,在pH 4.0的NaAc-HAc缓冲液中,-1.20V富集5min后,在电位-1.04V、-0.72V、-0.45V及-0.16V附近分别产生锌、镉、铅、铜的灵敏溶出峰,测定各元素的线性关系良好,相对标准偏差均小于5.4%。该法已成功应用于实际水样中痕量铅、镉、铜、锌的同时测定,加标回收率在93.3%~106.7%之间,结果满意。     

Time dependent influx and efflux of phenol by immobilized microbial consortium

Phenol, like many other organic solvents, is toxic to micro-organisms even at low concentrations. However, some micro-organisms can withstand this toxicity to a certain concentration. To observe the uptake mechanism of phenol, bacteria were isolatedfrom a petroleum refinery effluent and identified. Study was carried out to understand the effect of varying sub-lethal concentrations of phenol, on all the isolated individual bacterial cultures. Out of the bacteria isolated, Serratia liquefaciens was found to tolerate phenol concentration up to 1500 mg l^-1. A microbial consortium of the isolated bacteriawas formulated and immobilized. Individual cultures were also immobilized and uptake of phenol by the immobilized micro-organisms was observed in a nutrient-rich and nutrient-stressed medium containing phenol as a sole source of carbon. A time-dependent uptake of phenol was exhibited by the micro-organismsin nutrient-stressed medium, after which a sudden increase in phenol concentration occurred in the extracellular medium, till it reached back to the initial concentration. This was attributedto an active efflux mechanism adopted by the micro-organisms to withstand the toxic shock.     

库仑滴定法测定一氧化碳

本文就一氧化碳的测定条件和CO氧化过程中氧化剂的选择进行了研究。试验表明:ReAO_4-Ⅱ为氧化CO的活性催化剂,转化率可达100％(在300℃以上),本法简便,可用于空气中一氧化碳的测定和催化剂对CO活性测试。     

Assessment of groundwater quality near the landfill site using the modified water quality index

The purpose of this paper is to assess the groundwater quality near a landfill site using the modified water quality index. A total of 128 groundwater samples were analyzed for pH, electrical conductivity (EC), total organic carbon (TOC), polycyclic aromatic hydrocarbon (PAH), Cd, Pb, Zn, Cu, Cr, and Hg. The analytical results have showed a decreasing trend in concentration for TOC, Cd, Pb, Hg, and Cu and an increasing one for pH, EC, and PAH. The modified water quality index, which was called landfill water pollution index (LWPI), was calculated to quantify the overall water quality near the landfill site. The analysis reveals that groundwater in piezometers close to the landfill is under a strong landfill impact. The LWPI in piezometers ranged from 0.52 to 98.25 with a mean value of 7.99. The LWPI in groundwater from the nearest house wells varied from 0.59 to 0.92. A LWPI value below 1 proves that analyzed water is not affected by the landfill. Results have shown that LWPI is an efficient method for assessing and communicating the information on the groundwater quality near the landfill.     

Analysis of Pesticides Using a Polyppyrole Modified Electrode

Electrochemical methods can provide fast, sensitive and sometimes real time detection of pesticides. In the course of this work, a dispersed mercury electrode has been used to detect pesticides electrochemically. The electrode was prepared by depositing a thin mercury film on a glassy carbon disc and then coating a layer of polypyrrole on the disc. The effect of coating thickness on detection sensitivity was studied. A thin mercury film of 0.34 µm dispersed by one cycle polymerization of pyrrole was preferred. The influence of electrolyte, pH and organic solvent content on pesticide response was also investigated. The polypyrrole dispersed mercury electrode (Hg-PPy/GC) was not suitable for a pH above 6 but it can tolerate acetonitrile up to 10% at which concentration the mercury film coated glassy carbon electrode (Hg/GC) failed to response. Methyl parathion, methyl azinphos, parathion and fenitrothion were detected. The sensitivity of the dispersed mercury electrode was similar to a normal thin mercury film electrode in this case. A good response can be obtained for 1 ppm pesticides using fast linear sweeping voltammetry.     

活性炭负载催化剂去除燃煤烟气中单质汞的研究

以贵州凯里褐煤进行燃烧实验,研究采用CoCl2(负载量20%)改性的活性炭去除烟气中的单质汞。颗粒态汞占烟气总汞的87%,而单质汞占气态汞的80.4%。改性活性炭吸附了气态汞中97%的单质汞,而吸收液只吸收了3%的单质汞。可见改性活性炭也能有效地吸附煤燃烧实验中的烟气汞。实验结果表明,煤中汞的释放率为59.5%,1kg的改性活性炭可以吸附208t煤所产生的烟气中的气态单质汞。     

Dechlorination of pentachlorophenol in supercritical carbon dioxide with zero-valent palladium-magnesium bimetallic mixture

A stream of substrate pentachlorophenol [PCP, 5 mg min(-1) in water-methanol (1 + 4, v/v)] was merged with 1.5 ml min(-1) of supercritical carbon dioxide (scCO2) and delivered to a reactor column (25 cm x 1 cm) of zero-valent palladium-magnesium mixture. The resulting dechlorinations, although very efficient, were not quantitative. For continuous operation at 400 degrees C for 6 h, phenol was the principal product, with lesser quantities of methylated products and only traces of chlorinated products (principally monochlorinated species). PCP deoxygenation was not observed and ring methylation was decreased relative to analogous reactions in hydroxylic organic solvent. With time, the reactor column slowly lost dechlorination activity. Reducing the loading of Pd0 on Mg0 from 2% to 1% (w/w) apparently did not change the course of the reaction; however, the dechlorination capacity was decreased correspondingly. None the less, over 6 h or 5 h of continued operation, the dechlorination efficiency was 0.995 for the 2% (w/w) loading of Pd0 on Mg0 and 0.984 for the 1% (w/w) loading.     

Clear and present danger? The use of a yeast biosensor to monitor changes in the toxicity of industrial effluents subjected to oxidative colour removal treatments

Discharges of coloured effluents into surface waters provide conspicuous evidence of the impact of industry on the environment. The textile industry is an obvious candidate for sources of such discharges. Conventional treatment methods appear to alleviate this situation by removing colour, however the affect on toxicity is less obvious. The objective of this study was to examine the changes in effluent toxicity during the course of two alternative wastewater treatment methods, ozonation and electrochemical oxidation, using a novel toxicity biosensor, GreenScreen EM. The biosensor is capable of measuring both general acute toxicity (cytotoxicity), and more specifically genotoxicity, that is damage to a cell's DNA structure, replication or distribution, caused by substances that may be mutagenic and/or carcinogenic. The biosensor utilises a modified strain of the brewers yeast Saccharomyces cerevisiae, incorporating a gene encoding green fluorescent protein (GFP) linked to the inducible promoter of the DNA damage responsive RAD54 gene. Upon exposure to a genotoxin, the production of GFP is up-regulated in parallel with RAD54, and the resulting cellular fluorescence provides a measure of genotoxicity. Acute toxicity is simultaneously determined by monitoring relative total growth of the cell culture during incubation. The results presented in this paper show that a reduction in colouration does not necessarily correspond to a reduction in effluent toxicity.     

无人监测船在城市内河水质监测中的应用

采用无人船监测技术结合镇江市内河水质状况普查工作,大于120 h的航行试验,总航行里程约为90 km,对建成区水体中的氨氮(NH3-N)、溶解氧(DO)、氧化还原电位(ORP)和浊度进行原位监测,结果表明,通过合理选择搭载相应的测量电极,无人监测船能够满足地表水测量数据准确度的要求,同时可实现研究区域的监测全覆盖,提升了地表水环境监测的工作效率。