乙酰丙酮荧光光度法测定居室空气中微量甲醛

甲醛是日常生活中人们经常接触的一种室内空气污染物,可诱发和发生不良建筑综合症、建筑物关联症、化学物质过敏症,而甲醛是建筑综合症的明确危险因素之一。目前测定甲醛的方法很多,如变色酸法、气相色谱法、AHNT法、酚试剂法。以上方法所用试剂多,操作步骤繁琐。本工作用乙酰丙酮荧光光度法测定居室空气中微量甲醛,方法简单、快速、灵敏度高。     

化妆品及其原料中甲醛含量测定方法的研究

参考相关产品的国家标准和《化妆品卫生规范》（2007年版）,对化妆品及其原料采用水蒸气蒸馏法提取,结合乙酰丙酮比色法测定甲醛。结果表明,该法排除了化妆品及其原料中乳化成分产生的浑浊对样品测定的干扰,为测定化妆品及其原料中的甲醛含量提供多种简便准确的途径。     

液相色谱-柱后衍生法测定化妆品中游离甲醛含量

正甲醛是一种重要的有机物,它作为有机原料使用时,用途非常广泛。当甲醛用于杀菌防腐时,其用量、使用方法和范围有着明确的规定。对于化妆品而言,国际上公认的甲醛安全限量是0.2%。我国的《化妆品安全技术规范》(2015年版)中规定,甲醛属于限制使用的物质,除口腔卫生产品最大允许使用量为0.1%以外,其他化妆品中游离甲醛的最大允许使用量为0.2%(当在化妆品成品中其质量分数超过0.05%时,必须在产品标签中标印"含甲     

臭氧催化氧化脱除低浓度甲醛的新方法

甲醛作为一种典型的室内挥发性有机污染物,对人体健康危害很大.目前,在可用于室内甲醛脱除的诸多方法之中,臭氧催化氧化法因可于室温下使用廉价的金属氧化物催化剂实现对甲醛的高效脱除,从而受到了科研工作者的广泛关注.然而,考虑到室内甲醛的浓度极低,且存在着长期缓慢释放的特点,传统的臭氧催化氧化法应用于实际的室内甲醛脱除不仅会造成能量的浪费,而且还易因未完全分解臭氧的连续释放带来二次污染问题.为了提高臭氧催化氧化脱除甲醛过程的臭氧利用率,降低能耗,并有效缓解未分解臭氧引起的二次污染,本文将一种循环的甲醛存储-臭氧催化氧化新方法应用于室内低浓度甲醛的脱除.该新方法包含甲醛存储与臭氧催化氧化两个过程,在存储阶段低浓度甲醛吸附存储于催化剂表面,而在臭氧催化氧化阶段臭氧将存储的甲醛氧化为CO2与H2O,并重新释放催化剂表面的吸附位.因负载型氧化锰具有优良的臭氧分解能力,本研究以Al2O3负载的MnOx为催化剂,通过研究前驱体及担载量对甲醛脱除反应的影响,筛选出了最优的MnOx/Al2O3催化剂,并对相对湿度的影响规律进行了考察,最后通过低浓度甲醛存储-臭氧催化氧化循环实验验证了该甲醛臭氧催化氧化新过程的可靠性.我们采用传统的等体积浸渍法,基于不同的前驱体制备MnOx/Al2O3催化剂.XRD表征结果表明,乙酸锰为前驱体制得的MA/Al2O3催化剂中MnOx相主要为Mn3O4(粒径约为6.0 nm);而硝酸锰前驱体所得MN/Al2O3催化剂中则含有MnO2与Mn2O3相,且其MnOx颗粒粒径较大,约为9.5 nm.XPS测试结果表明,MA/Al2O3催化剂含有Mn2+,Mn3+及Mn4+,其中Mn3+与Mn4+的含量分别为75%与12%;而MN/Al2O3催化剂则仅含有Mn3+与Mn4+,含量分别为35%与65%.上述XRD与XPS结果相一致,说明以乙酸锰为前驱体所得催化剂的分散度较高且易形成低氧化态的Mn.甲醛存储-臭氧催化氧化实验结果表明,与Al2O3及MN/Al2O3相比,MA/Al2O3催化剂具有更高的甲醛存储与催化氧化脱除性能.基于MA/Al2O3催化剂,不同Mn负载量下的甲醛存储与臭氧催化氧化实验结果表明,Mn负载量为10 wt%时MA/Al2O3的性能最佳.因而,进一步的实验中我们均选用最优的10 wt%MA/Al2O3为催化剂,其在50%相对湿度下的甲醛存储量为26.9μmol/mL,臭氧催化氧化阶段碳平衡为92%,CO2选择性为100%.相对湿度的影响结果(23℃)则表明,由于水分子与甲醛分子间存在着竞争吸附作用,甲醛存储容量随相对湿度的增加而降低;但因相对湿度增加可建立利于甲醛氧化的新途径,故臭氧催化氧化性能随相对湿度增加而增强.综合考虑,10 wt%MA/Al2O3上甲醛存储-臭氧催化氧化的最优相对湿度为50%.为验证所提出新方法的实用性,我们基于10 wt%MA/Al2O3开展了甲醛存储-臭氧催化氧化的4次循环实验.4次循环实验中的甲醛存储以及臭氧催化氧化处理的规律可基本保持一致.50%相对湿度下,低浓度甲醛(15×10-6)在空速为27000 h-1时的穿透时间为110 min,而在臭氧催化氧化阶段(150×10-6臭氧,空速15000 h-1)仅需约50 min即可实现对存储甲醛的氧化脱除(碳平衡大于92%,CO2选择性100%),表明该新方法较传统的臭氧催化氧化方法臭氧用量可节省60%.     

臭氧消毒简介

臭氧是公认的广谱、高效杀菌剂。介绍了臭氧消毒的特点、原理,臭氧的产生方法,臭氧消毒的应用等。     

臭氧催化氧化脱除低浓度甲醛的新方法（英文）

甲醛作为一种典型的室内挥发性有机污染物,对人体健康危害很大.目前,在可用于室内甲醛脱除的诸多方法之中,臭氧催化氧化法因可于室温下使用廉价的金属氧化物催化剂实现对甲醛的高效脱除,从而受到了科研工作者的广泛关注.然而,考虑到室内甲醛的浓度极低,且存在着长期缓慢释放的特点,传统的臭氧催化氧化法应用于实际的室内甲醛脱除不仅会造成能量的浪费,而且还易因未完全分解臭氧的连续释放带来二次污染问题.为了提高臭氧催化氧化脱除甲醛过程的臭氧利用率,降低能耗,并有效缓解未分解臭氧引起的二次污染,本文将一种循环的甲醛存储-臭氧催化氧化新方法应用于室内低浓度甲醛的脱除.该新方法包含甲醛存储与臭氧催化氧化两个过程,在存储阶段低浓度甲醛吸附存储于催化剂表面,而在臭氧催化氧化阶段臭氧将存储的甲醛氧化为CO_2与H_2O,并重新释放催化剂表面的吸附位.因负载型氧化锰具有优良的臭氧分解能力,本研究以Al_2O_3负载的MnO_x为催化剂,通过研究前驱体及担载量对甲醛脱除反应的影响,筛选出了最优的MnO_x/Al_2O_3催化剂,并对相对湿度的影响规律进行了考察,最后通过低浓度甲醛存储-臭氧催化氧化循环实验验证了该甲醛臭氧催化氧化新过程的可靠性.我们采用传统的等体积浸渍法,基于不同的前驱体制备MnO_x/Al_2O_3催化剂.XRD表征结果表明,乙酸锰为前驱体制得的MA/Al_2O_3催化剂中MnO_x相主要为Mn3O4(粒径约为6.0 nm);而硝酸锰前驱体所得MN/Al_2O_3催化剂中则含有MnO2与Mn_2O_3相,且其MnO_x颗粒粒径较大,约为9.5 nm.XPS测试结果表明,MA/Al_2O_3催化剂含有Mn~(2+),Mn~(3+)及Mn~(4+),其中Mn~(3+)与Mn~(4+)的含量分别为75%与12%;而MN/Al_2O_3催化剂则仅含有Mn~(3+)与Mn~(4+),含量分别为35%与65%.上述XRD与XPS结果相一致,说明以乙酸锰为前驱体所得催化剂的分散度较高且易形成低氧化态的Mn.甲醛存储-臭氧催化氧化实验结果表明,与Al_2O_3及MN/Al_2O_3相比,MA/Al_2O_3催化剂具有更高的甲醛存储与催化氧化脱除性能.基于MA/Al_2O_3催化剂,不同Mn负载量下的甲醛存储与臭氧催化氧化实验结果表明,Mn负载量为10 wt%时MA/Al_2O_3的性能最佳.因而,进一步的实验中我们均选用最优的10 wt%MA/Al_2O_3为催化剂,其在50%相对湿度下的甲醛存储量为26.9μmol/mL,臭氧催化氧化阶段碳平衡为92%,CO_2选择性为100%.相对湿度的影响结果(23°C)则表明,由于水分子与甲醛分子间存在着竞争吸附作用,甲醛存储容量随相对湿度的增加而降低;但因相对湿度增加可建立利于甲醛氧化的新途径,故臭氧催化氧化性能随相对湿度增加而增强.综合考虑,10 wt%MA/Al_2O_3上甲醛存储-臭氧催化氧化的最优相对湿度为50%.为验证所提出新方法的实用性,我们基于10 wt%MA/Al_2O_3开展了甲醛存储-臭氧催化氧化的4次循环实验.4次循环实验中的甲醛存储以及臭氧催化氧化处理的规律可基本保持一致.50%相对湿度下,低浓度甲醛(15×10-6)在空速为27000 h-1时的穿透时间为110 min,而在臭氧催化氧化阶段(150×10-6臭氧,空速15000 h-1)仅需约50 min即可实现对存储甲醛的氧化脱除(碳平衡大于92%,CO_2选择性100%),表明该新方法较传统的臭氧催化氧化方法臭氧用量可节省60%.     

明胶膜的制备及其交联性能的研究

探讨了溶剂、温度及pH值对明胶膜性能的影响，并以甲醛和戊二醛为交联剂，采用溶液交联和蒸汽交联两种方法对明胶膜进行交联改性。研究结果表明：相对于溶液交联，甲醛蒸汽交联所得膜的拉伸强度从25MPa上升到42MPa，戊二醛交联的膜的拉伸强度从15MPa上升到40MPa，而溶胀率和溶出率均有所下降，蒸汽交联的膜的性能优于溶液交联的膜。     

靛蓝二磺酸钠分光光度法和碘滴定法测定水中臭氧含量适用条件的比较

臭氧是一种微溶于水,具有强烈刺激性气味的气体,氧化性仅次于氟,可以杀菌、消毒[1]、脱色[2]、除臭,氧化废水中的有机、无机污染物,被广泛用于水厂饮用水消毒[3]、城市污水处理、工业废水[4]处理等方面。但是,对于臭氧含量的测定,国家标准中只有针对空气中[5-6]臭氧浓度的测定方法,缺乏对水中臭氧浓度的测定。文献已报道水中臭氧的测定方法有多种[7-11],其中应用较多的是靛蓝二磺酸钠分光     

衍生化处理-气相色谱-质谱法测定生活饮用水中的甲醛

<正>甲醛已经被世界卫生组织确定为致癌和致畸性物质[1],是一种无色,易溶于水、醇、醚的具有强烈刺激性气味的气体[2-3],具有较高毒性,主要用于酚类、三聚氰胺等有机物的生产。在我国有毒化学品优先控制名单上甲醛高居第二位[4]。甲醛对皮肤和黏膜具有刺激作用,进入人体后易对人体的中枢神经系统和视网膜造成损害[5]。长期吸入甲醛可引发鼻咽癌、喉头癌等严重疾病,是公认的变态反应源。生活饮用水及水源水中的甲醛主要来源于二氧化氯、臭氧消毒处理时有机物发生氧化产生的副产物,还有     

液相色谱法测定空气中的甲醛

甲醛可以与湿空气中的离子型氯化物反应,生成双氯甲醚,这是一种强致癌物,可诱发肺癌。 目前测定空气中甲醛的方法主要有,品红亚硫酸法、酚试剂法、乙酰丙酮法等分光光度法及气相色谱法。美国Varian公司色谱应用报告文集中介绍了一种液相色谱法,即将甲醛吸附在涂布了2,4-二硝基苯肼的硅胶上,然后用乙腈将甲醛苯腙衍生物从硅胶上萃取下来,用液相色谱分离测定。     

Specific method for the determination of ozone in the atmosphere

A simple, sensitive and specific method for the determination of ozone in the atmosphere is described. Reactions of ozone with several 1-alkenes were studied at room temperature (25°). Eugenol(4-allyl-2-methoxyphenol), when reacted with ozone, was found to produce relatively large amounts of formaldehyde compared to other 1-alkenes tested. The method described was compared with alkaline iodide method for the determination of various concentrations of ozone in the range 0.05–2.0 p.p.m. Hydrogen peroxide, peracetic acid, sulfur dioxide and various reducing agents commonly present in the air, do not interfere. Formaldehyde when present in the air, must be determined simultaneously and the concentration of formaldehyde subtracted from that of the ozone. Any formaldehyde monitoring equipment can be easily adapted for the determination of ozone.     

A specific spectrophotometric determination of ozone in air in the presence of sulfur dioxide and nitrogen oxides

A sensitive, specific spectrophotometric method for the determination of ozone in air by the ozonolysis of 1,1-di-phenylethylene (DPE) is described. The yield of formaldehyde from the ozonolysis of several terminal olefins was determined, and DPE was found to give the highest yield, 90%. The method was checked against the EPA iodimetric method, and gives a consistent yield of formaldehyde over the ozone range 0.05–5.00 μg g^-1 of air. As sulfur dioxide is used as a reagent, its presence in air does not interfere. Interference by nitrogen oxides and other free radical oxidants is prevented by the addition of mesitol (2,4,6-trimethylphenol). Formaldehyde in air interferes, but can be determined by using the method with DPE omitted from the sampling train, and so accounted for. In the procedure, formaldehyde is determined by the reverse of the West—Gaeke method for sulfur dioxide.     

Determination of Atmospheric Ozone Using the Centrifugal Photometric Analyzer

Abstract

The production of formaldehyde from the selective cleavage of the double bond of 4-allyl-2-methoxyphenol (eugenol) by ozone permits the specific determination of ozone in air samples. The formaldehyde is determined by a modification of the West-Gaeke procedure for sulfur dioxide. Increased speed, accuracy, and reproducibility is achieved because of the parallel analysis technique of the centrifugal photometric analyzer.     

A diffusive sampling device for simultaneous determination of ozone and carbonyls

A new diffusive sampling method for the simultaneous determination of ozone and carbonyls in air has been developed. In this method, silica gel impregnated with a mixture of trans-1,2-bis(2-pyridyl)ethylene (2BPE) and 2,4-dinitrophenylhydrazine (DNPH) is used as the absorbent; further, a porous sintered polyethylene tube (PSP-diffusion filter), which acts as a diffusive membrane, and a small polypropylene syringe (PP-reservoir) for elution of the analytes from the absorbent are used. The carbonyls present in air react with DNPH in the absorbent to form hydrazone derivatives. Concurrently, ozone in the air reacts with 2BPE to form pyridine-2-aldehyde, which immediately reacts with DNPH to form a pyridine-2-aldehyde hydrazone derivative. All the hydrazones derived from airborne carbonyls, including pyridine-2-aldehyde (formed from ozone), are completely separated and analyzed by high-performance liquid chromatography. The sampling rates of ozone (44.6 mL min(-1)) and formaldehyde (72.0 mL min(-1)) are determined by comparison with the rates obtained in an active sampling method. The sampling rates of other carbonyl compounds are calculated from the respective molecular weights according to a rule based on Graham's law. The calculated sampling rates agree with the experimental values. The DSD-BPE/DNPH method is advantageous because it is simple and allows for the simultaneous analysis of ozone and carbonyls.     

A novel fiber optical device for ultraviolet disinfection of water

Since there are several problems in traditional UV disinfection techniques, a highly efficient, reliable and economical method, using quartz optical fibers to deliver UV light is proposed. The principle of the experimental setup is that ultraviolet rays are gathered by a reflector and converge on a light point, the diameter of approximately 5mm. In this way UV light can be transferred into water to kill the bacteria in the water. This paper presents preliminary results on water disinfection using this new UV disinfection setup. Its suitability for application could be shown in experiments with E. coli (ATCC8099) as test microorganisms. We have optimized the distribution of the optical fibers in the water in bench-scale study. This result can provide guidance for pilot-scale and field-scale study of this new technique. The results show that the new technique had a good performance under different conditions as follows: (a) turbidity level=10.2 NTU, (b) ferric ion concentration=0.3 mg/L, and (c) humic acid concentration=5 mg/L. The new technique provides a promising approach to disinfection treatment of drinking water.     

Increase of ambient formaldehyde in Beijing and its implication for VOC reactivity

Influencing atmospheric OH radical budget and tropospheric ozone production,ambient formaldehyde(HCHO) is one of the key oxygenated volatile organic compounds(OVOCs).We present the variations on formaldehyde column densities in summertime in Beijing retrieved from ozone monitoring instrument(OMI) between 2005 and 2011.Satellite columns of HCHO correlated well with available ground-based measurements despite some noticeable differences.The orthogonal distance regression(ODR) method was used to estimate the ratio between satellite columns and ground-level concentrations,whereas ordinary least squares(OLS) method was used to fit the trend of ambient formaldehyde.The formaldehyde concentrations derived from HCHO columns were in the range of 7-12 ppbv and steadily increased at an approximate rate of 0.64 ppbv/yr(7.8%at 2005 level) with an uncertainty of 51%.VOC reactivity quantified by means of OH loss rates showed increasing contribution from formaldehyde and acetaldehyde, rising from 35%in 2005 to 40%in 2010,and decreasing contribution from anthropogenic VOCs,dropping from 49%in 2005 to 40%in 2010.More attention should be paid to understanding the net feedback of increasing formaldehyde to ozone formation potential.     

Concentration measurements of ozone in the 1200-300ppbv range: an intercomparison between the BNM ultraviolet standard and infrared methods

Simultaneous ultraviolet (UV) and infrared (IR) measurements of ozone concentration in air in the 1200-300 ppbv range have been performed using the ultraviolet absorption in the Hartley band at 0.2537 microm and the infrared absorption of a doublet at 9.507 microm in the nu(3) vibration-rotation band. Infrared concentration measurements were achieved using the tunable diode laser spectrometer of LPMA in Paris with interferometric control of the emitted wavelength while the UV concentration measurements were performed with the 49PS Megatec ozone generator of the Bureau National de Metrologie (BNM). The simultaneous recording of spectra of a reference cell filled with pure distilled ozone and of a low concentration mixture inside a long absorbing path Herriott cell allows to carry out infrared concentration measurements with an accuracy of the same order as the ultraviolet ones and provides the instrumental parameters of the spectrometer corresponding to each concentration measurement, which reduces systematic errors. Within the respective absolute uncertainties proper to the two techniques, no systematic discrepancy was evidenced between the IR and the UV measurements. The ozone ultraviolet absorption coefficient value determined by Hearn (308.3 +/- 4 cm(-1)atm(-1)) and used by the BNM and the National Institute of Standards and Technology (NIST) is confirmed by the present work.     

Application of Dielectric Barrier Discharge Reactor Immersed in Wastewater to the Oxidative Degradation of Organic Contaminant

Dielectric barrier discharge (DBD) is an effective method available for the production of ozone and ultraviolet light. The wastewater treatment system of this study was designed to utilize both ozone and ultraviolet light produced in the DBD reactor for the degradation of organic contaminant. The DBD reactor consisted of a quartz cylinder and a coaxial ceramic tube inside of which a steel rod was placed. The DBD reactor was immersed in the wastewater that was grounded. In this case, the wastewater acted not only as an electrode but also as the cooling medium for the DBD reactor. An azo dye, Acid Red 27, was used as the organic contaminant. In this system, the organic contaminant was degraded by two oxidation pathways induced by ozone and ultraviolet light. The concentration of ozone, the ultraviolet radiation intensity and the degradation efficiency of the organic contaminant were measured by varying the discharge. The results showed that the present system was very effective for the degradation of the organic contaminant. The energy requirement for the degradation was found to be 0.654 kJ/mg, which is much smaller value than those obtained with an ultraviolet/photocatalytic process.     

A new fluorescence method for determination of ozone in ambient air

A new simple method for determination of ozone in ambient air is presented. The reaction employed is based on the known ozonolysis of indigo dye. The indigotrisulfonate molecule contains one carbon–carbon double bond (C═C), which reacts with ozone and generates isatinsulfonates and sulfoanthranilate. The quantitatively formed sulfoanthranilate presents fluorescence (λ_ex 245 nm, λ_em 400 nm). Ozone was collected using two cellulose filters coated with 40 μL of 1.0 × 10^{− 3} mol L^{− 1} of indigotrisulfonate. The analytical response was linear in the range 0–150 ppbv ozone, and a detection limit of 7 ppbv was achieved using a sampling time of 15 min and an optimum sampling air flow rate of 0.4 L min^{− 1}. There was no interference from sulfur dioxide, formaldehyde or nitrogen dioxide. The ozonolysis mechanism and the reaction products are discussed.