高浓度二氧化氯气体的在线检测研究

在40℃下,高浓度ClO2气体在盘管中迅速溶解于水中达到平衡,使用分光光度法检测平衡溶液的浓度,从而间接测定出ClO2气体的浓度。该方法可检测体积分数大于0.14%的ClO2,响应时间为15~30s,相对标准偏差为0.3%,与连续碘量法相比测定结果没有显著性差异(P<0.01),全过程中未使用化学试剂,操作简便,干扰小,适用于的高浓度ClO2气体在线检测。     

A new sensitive and selective fluorescence method for determination of chlorine dioxide in water using rhodamine S

A new simple, selective and sensitive method for the determination of trace chlorine dioxide in water has been developed, based on the oxidation by chlorine dioxide to reduction the fluorescence of rhodamine dyes in ammonia-ammonium chloride buffer solution. Four rhodamine dyes systems such as rhodamine S, rhodamine G, rhodamine B and butyl-rhodamine B were tested. The rhodamine S system is the best, with a linear range of 0.0060-0.450 μg mL⁻¹ and a detection limit of 0.0030 μg mL⁻¹ ClO₂. It was applied to the determination of chlorine dioxide in synthetic samples and real samples, with satisfactory results. This method has good selectivity, especially, other chlorine species such as chlorine, hypochlorite, chlorite and chlorate do not interfere the determination. The mechanism of fluorescence reduction was also considered.     

纤维染料分析方法的研究进展

纤维染料是使纤维着色的物质,其分析检测对纺织、环保、法庭科学、古文物研究等诸多领域都有重要的意义。然而纤维染料的种类繁多、成分复杂,加之高灵敏度以及原位无损检测的分析需求日益突出,使得纤维染料的分析面临挑战。尽管如此,研究人员一直致力于高效、灵敏、无损的纤维染料分析新方法和新技术的研究,目前已经开发了多种纤维染料的分析方法,这些方法可大致分为3类:光谱法、色谱法及质谱法。该文综述了纤维染料的特点及纤维染料的检测方法及最新研究进展,并对未来纤维染料检测方法的发展进行了展望,为更好地开展纤维染料的分析提供了参考。     

Inorganic by-products in waters disinfected with chlorine dioxide

The continuing diminishing sources of fresh waters has stimulated the search for unconventional water resources, such as effluents from municipal sewage treatment plants, which can be reused for purposes of irrigation in agriculture, cooling water in industry, groundwater aquifer recharge and in the long term even for drinking water. The main problem of using effluents is the presence of pathogenic bacteria and viruses that can affect human and animal health. Therefore, disinfection has been used for many years to control and reduce waterborne diseases.At the moment, most water treatment plants use sodium hypochlorite as their primary biocide. However, the toxicity of chlorinated organic compounds produced during the treatment has led to increased interest in the use of alternative agents. One possible candidate as viable substitute of free chlorine is chlorine dioxide. Before this disinfectant can be recommended for routine use, it is imperative that its safety be assessed.In this research we have investigated the presence of chlorite and chlorate in sewage disinfected with chlorine dioxide. The effect of initial concentration of biocide and contact time was evaluated using a pilot plant fed with the effluent of a municipal treatment plant. Moreover, the influence of ClO₂ generator performance was analyzed and discussed.     

胰岛素样生长因子-I分析方法的新进展

介绍了检测胰岛素样生长因子-I(IGF-I)的各种样品前处理手段、IGF-I的标记方法,以及通过免疫分析、色谱以及色谱-质谱联用技术、表面等离子体共振(SPR)传感器等方法定量检测IGF-I的最新进展。     

Deterioration of polyethylene pipes exposed to water containing chlorine dioxide

Chlorine species used as disinfectants in tap water have a deteriorating effect on many materials including polyethylene. There are only very few scientific reports on the effect on polyethylene pipes of water containing chlorine dioxide. Medium-density polyethylene pipes stabilized with hindered phenol and phosphite antioxidants were pressure tested with water containing 4 ppm chlorine dioxide at 90 °C and pH = 6.8 as internal medium. The stabilizers were rapidly consumed towards the inner pipe wall; the rate of consumption was four times greater than in chlorinated water (4 ppm, pH = 6.8) at the same temperature. The depletion of stabilizer occurred far into the pipe wall. A supplementary study on a polymer analogue (squalane) containing the same stabilizer package showed that the consumption of the phenolic antioxidant was 2.5 times faster when exposed water containing chlorine dioxide than on exposure to chlorinated water. The subsequent polymer degradation was an immediate surface reaction. It was confirmed by differential scanning calorimetry, infrared spectroscopy and size exclusion chromatography that in the surface layer which came into contact with the oxidising medium, the amorphous component of the polymer was heavily oxidized leaving a highly crystalline powder with many carboxylic acid chain ends in extended and once-folded chains. Scanning electron microscopy showed that propagation of cracks through the pipe wall was assisted by polymer degradation.     

Epoxidation by sodium chlorite with aldehyde-promoted chlorine dioxide formation

An improved method is described for selective room temperature epoxidation of alkenes by sodium chlorite in a solvent mixture of ethanol, acetonitrile, and water buffered at pH 7. In addition, the use of aldehydes as promoters in chlorite oxidations is described for the first time. The amount of sodium chlorite, the solvent mixture, and the addition of formaldehyde as a practical promoter were optimized. Styrene was used as a test substrate in the optimization studies and the generality of the method was assessed by using a variety of nucleophilic and electrophilic substrates. Yields up to 89% were obtained with styrene and other nucleophilic alkenes are readily converted into epoxides.     

Gas-diffusion flow injection assay for the selective determination of chlorine dioxide based on the fluorescence quenching of chromotropic acid

The present work reports the first spectrofluorimetric gas-diffusion flow injection (GD-FI) assay for the determination of chlorine dioxide in water samples (tap, mineral and soda water). The method is based on the fluorescence quenching of chromotropic acid (CA) (λ_ex. = 347 nm, λ_em. = 371 nm) caused by the analyte. The chemical and instrumental variables of the system were studied in terms of maximum sensitivity. The gas-diffusion cell was thermostated at 40 °C to enhance the vaporization of chlorine dioxide and thus the sensitivity of the method. The quenching effect of chlorine dioxide on CA was linear in the range 0.09-3.41 mg l^− 1, while the precisions either close to the quantitation limit or near to the middle of the linear section of the calibration graph were satisfactory in both cases (s_r = 2.6% and 1.5% (n = 10) at 0.17 and 1.71 mg l^− 1 level, respectively). The developed method proved to be adequately selective and sensitive with 3σ limit of detection equal to c_L = 0.03 mg l^− 1. The application of the assay to spiked tap, mineral and soda water samples yielded accurate results with recovery values in the range 94.1-105.9%.     

Research on the explosion characteristics of chlorine dioxide gas

The explosion characteristics of chlorine dioxide gas have been studied for the first time in a cylindrical exploder with a shell capacity of 201. The experimental results have indicated that the lower concentration limit for the explosive decomposition of chlorine dioxide gas is 9.5% （[ClO2]/[air]）, whereas there is no corresponding upper concentration limit. The maximum pressure of explosion relative to the initial pressure was measured as 0.024 MPa at 10% ClO2 and 0.641 MPa at 90% ClO2. The induction time （the time from the moment of sparking to explosion） at 10% ClO2 was 2195 ms, but at 90% ClO2 the induction time was just 8 ms. The explosion reaction mechanism of ClO2 is of a degenerate chain-branching type involving the formation of a stable intermediate （Cl2O3）, from which the chain branching occurs.     

二氧化氯制备方法及相关产品在我国的研究进展

二氧化氯由于对细菌、病毒有广谱、快速、高效、安全的杀灭特点和优势,正成为水处理取代液氯的最佳换代产品,在饮用水、工业水处理、食品保鲜、纸浆漂白、石油解堵等多种领域获得了越来越广泛的应用,但国外的一些生产方法由于本身存在一些不足并不完全适合于国内使用。因此,我国不少学者开展了二氧化氯新制备方法的研究,并开发了一些稳定性的二氧化氯产品。本文介绍和评述了这些研究成果,并对未来的发展提出了一些建议。     

A review on the electrochemical production of chlorine dioxide from chlorates and hydrogen peroxide

Chlorine dioxide is one of the most interesting oxidants because it combines a strong capacity of oxidation with low formation of hazardous byproducts such as chlorinated organics during its application. Because of that, it is widely used in disinfection of drinking water and, currently, it is aimed to be used in the disinfection of surfaces or buildings. Although it is usually produced by the chemical interaction of chlorite with hypochlorite/chlorine or hydrochloric acid, one interesting alternative for its production is the combination in strongly acidic media of chlorate and hydrogen peroxide. Both compounds are known to be efficiently manufactured with electrochemical technology, opening the possibility of a complete electrochemical process to produce this important oxidant. This review summarizes the recent progress in the electrochemical production of the two raw materials, as well as the complete electrochemical production of chlorine dioxide, not only paying attention to the scientific literature but, most importantly, to recent patents, trying to see in which technology readiness level are each of the technologies and what are the elements of the value chain required for a complete implementation of the technology.     

Application of an amperometric sensor to in-line monitoring of pulp bleaching with chlorine dioxide

Chlorine dioxide is replacing chlorine as the active compound in pulp bleaching in order to reduce the amount of chlorine used in the process and hence also in the waste waters. In bleaching with chlorine dioxide part of the effective bleaching chemical is usually chlorite. The electrochemistry of chlorine dioxide and chlorite at solid electrodes was studied by cyclic voltammetry at different pH values. The observed voltammograms indicated that reduction of chlorine dioxide gives chlorite and oxidation of chlorite gives chlorine dioxide. Both voltammograms were well developed, indicating a reversible process. Both platinum and glassy carbon were used as the working electrode. The dependence of the limiting current of chlorine dioxide and chlorite on pH was studied at both electrodes. The method was tested in the chlorine dioxide bleaching stage D1 in a typical bleaching process. A good correlation was found between the concentrations of chlorine dioxide and chlorite measured by the in-line amperometric method and a standard titrimetric method.     

二氧化氯催化氧化难降解有机废水在我国的研究进展

难降解有机废水的处理对环境保护有十分重要的意义.在本文中,对用二氧化氯催化氧化技术在不同领域中难降解有机废水的处理和其催化氧化反应机理在我国的研究进展进行了介绍和评述,也指出了该技术未来的发展前景和进一步的研究方向.     

高氯废水化学需氧量分析方法综述

对高氯废水化学需氧量分析方法进行归纳和综述。常用的高氯废水化学需氧量分析方法有氯气校正容量法、降氯密闭消解分光光度法以及高温氧化总有机碳系数换算法等。其中氯气校正容量法操控要求较高,分析耗时较长,不适用于大批量样品同步分析;降氯密闭消解分光光度法灵敏度高,但在降氯过程中增加了重金属盐硫酸汞的用量,分析成本较高,易产生二次污染,且对样品的均质性要求较高;高温氧化总有机碳系数换算法操作便捷、抗干扰能力强,但是换算系数易随不同来源、不同组分的样品发生波动,数据可比性需要通过实验验证。经过梳理归纳,明确各种分析方法的特点和适用范围,为研究人员选择合适的分析方法或进一步开展相关的方法研究提供参考。     

典型全氟有机酸类化合物的样品前处理与分析方法研究进展

全氟辛烷磺酸（PFOS）和全氟辛烷羧酸（PFOA）是两种典型的全氟有机酸类化合物,也是全氟化合物（PFCs）前体物的最终降解产物,具有肝毒性、胚胎毒性、生殖毒性、神经毒性,检出率最高。在各种被污染的介质中,PFOS和PFOA含量往往很低,基体复杂多样,快速高效的样品前处理技术成为测定的关键环节。目前,国际上对PFOS和PFOA的测定无统一标准,而我国关于PFCs的分析研究落后于国际发展水平。该文介绍了PFOS和PFOA的特性,系统总结和评述了前处理技术（液液萃取、固相萃取、固相微萃取、超声萃取和QuEChERS法）及分析方法（色谱-质谱方法、光谱法、酶联免疫法和电化学法）,以期为PFOS和PFOA的分析监测及标准制定提供参考。     

Comparative studies on some analytical methods

This work present comparative results on powder milk storage quality, obtained from analytical methods. Protein content was determined conventional (Kjeldahl) and colorimetric with biuret reagent at 540 nm and integral quality by thermogravimetric and biological methods. A method was developed for the protein separation of powder milk. Powder milk was submitted to degradation processes at 45, 60 and 80°C for 20 days. The results indicated that protein content values were inconsistent if determinations by Kjeldahl and colorimetric methods and biological tests were compared. There is evidence of thermal decomposition of powder milk as detected by biological and thermogravimetric methods.The authors thanks CNP_q/PADCT for financial support.     

Construction and performance of a drop cell for the nephelometric determination of sulfur dioxide

A nephelometric technique based on a liquid drop is described for the measurement of atmospheric sulfur dioxide. A 40-μl drop of barium chloride and hydrogen peroxide solution is suspended in a flowing-air sampling stream. The sulfur (IV) collected is oxidized to sulfur (VI) and finally precipitated as barium sulfate. Nephelometric detection of drop is achieved by an appropriate arrangement consisting of an optical fiber contacting the drop and a photodiode placed at 90° relative to the fiber. The design and characteristics of this drop-based gas sensor system are described. The analytical response, as photocurrent, is proportional to the product of the sampling period and the sulfur dioxide concentration. The detection limit is ca. 1.1 mg m⁻³ for a 10-min sampling time. The present technique is fairly rapid and simple, uses a small amount of reagent and is set up with low-cost equipment, making this system economically viable.     

干果类食品的样品前处理与分析检测方法研究进展

坚果、果脯等干果类食品含有丰富的营养成分,深受国内外广大消费者的喜爱.但这些食品在果实生产、加工、储运时会使用农药或产生霉变等,造成干果中农药、重金属、霉菌毒素或添加剂等有害成分残留,甚至超过国家限量要求,带来严重的食品安全问题.因此,加强干果类食品的质量监督具有重要的经济和社会意义.但干果类食品基质复杂,有害物质种类...     

六氯丁二烯分析方法研究进展

六氯丁二烯是一种持久性有机污染物,于2015年和2017年分别被列入《斯德哥尔摩公约》附件A和附件C的受控污染物名单中。六氯丁二烯的来源、环境赋存和影响等研究对控制该新增受控持久性有机污染物污染具有重要意义,而灵敏可靠的六氯丁二烯分析方法是开展相关研究的前提和基础。近年来已有不少学者将六氯丁二烯作为分析目标物之一进行了检测或方法学研究。基于这些研究成果,该文综述了六氯丁二烯分析方法的研究进展,其中重点介绍了空气、水体、土壤、污泥、生物组织等多种介质中六氯丁二烯的样品前处理方法,并比较了各方法的优缺点,以期为该领域的进一步研究提供参考。空气中六氯丁二烯主要由泵抽气通过吸附管而采集,再经热脱附后进行仪器分析,检出限在ng/m³水平。也有研究应用聚氨酯泡沫被动采样器和吸附剂填充聚氨酯泡沫被动采样器采集大气中六氯丁二烯及其他污染物。基于吸附剂填充聚氨酯泡沫被动采样器的分析方法灵敏度较高,其对六氯丁二烯的检出限低至0.03 pg/m³。然而目前被动采样体积仅根据六氯丁二烯的log K_OA系数估算,未来仍需进一步实验校正。水体样品前处理通常也较简单,通过吹扫捕集、液-液萃取或固相萃取目标物后进行仪器分析。固相萃取法能够同步实现目标物的提取、净化和浓缩,在水样中六氯丁二烯分析方面具有明显优势。固相萃取柱类型以及干燥步骤中柱中残留水分去除率均会影响六氯丁二烯的回收率。灰尘、土壤、沉积物、污泥和生物组织等固体介质样品基质最为复杂,需联合多种方法进行前处理。固体样品中六氯丁二烯提取方法包括索氏提取,加速溶剂萃取和超声萃取,其中超声萃取法应用最为广泛。固体基质净化方面主要采用层析柱色谱法,多根净化柱联用或多层复合柱能够提升净化效果。仪器分析方面,六氯丁二烯主要采用气相色谱和质谱联用检测,高性能质谱检测器如串联质谱能够大大提高六氯丁二烯的检测灵敏度,具有较大的应用潜力。     

油脂性食品中脂肪酸氯丙醇酯检测方法的研究进展

脂肪酸氯丙醇酯污染是近年来国际上新出现的热点食品安全问题之一,尤其是3-氯-1,2-丙二醇脂肪酸酯(3-MCPD酯)污染问题更为突出。3-MCPD酯在食用油、婴幼儿奶粉等多种食品中的含量较高,以3-MCPD的最大耐受剂量(TDI)评估时所引起的健康风险较高。国外已对3-MCPD酯等氯丙醇酯的检测方法、污染调查和形成机制等开展了不少的研究,国内开展的研究较少。本文主要对油脂食品中3-MCPD酯的检测方法(包括前处理过程,如3-MCPD酯的提取、水解和衍生)、3-MCPD酯总量以及3-MCPD单酯和双酯的检测方法进行了综述。