氧瓶燃烧法测定煤中痕量汞的改进

在氧瓶中采用镍铬电炉丝加热燃烧煤样,燃烧过程中形成的汞蒸气被酸性高锰酸钾溶液吸收并氧化成汞离子,经还原后用流动注射-氢化物发生冷原子吸收法测定。方法的相对标准偏差4.8%,相关系数0.999 7,回收率在91.4%~97.3%间,此方法特别适用于批量样品常规分析。     

1953—2005年中国燃煤大气铅排放量估算

采用随时间变化的铅排放因子估算了中国1953—2005年燃煤大气铅排放量。在52年间,中国燃煤累计向大气排放19.1万t铅,平均每年以4.02%的速度增加,其中2001—2005年排铅38 688 t,平均增速达9.55%;工业用煤的铅排量占总量的87%,生活用煤铅排量占8%;2006年的燃煤铅排量超过了10 000 t。这表明,燃煤造成的铅污染已成为当前中国面临的重要环境问题。     

改进的氧瓶燃烧法结合电感耦合等离子体质谱快速测定茶叶样品中的稀土元素含量

建立了电感耦合等离子体质谱法快速测定茶叶中Y~Lu共15种稀土元素的新方法,样品处理基于改进的氧瓶燃烧法,以涂覆甘油的石英布代替滤纸作为引燃和燃烧载体,在500 mL容积燃烧瓶中实现了0.1 g样品量的有氧完全燃烧。系统优化了样品处理关键参数,以5 mL 4％ HNO3+1％ HF(V/V)组合试剂超声提取燃烧残渣1 min,稀土元素回收率大于90％,样品总处理周期小于3 min。6次样品平行测定值的相对标准偏差(RSD)在2.7％~5.5％之间,方法检出限(3σ)在0.001~0.006 mg/kg之间。采用本方法对3种茶叶标准参考物质进行分析,测定结果和标准值吻合良好。     

微波氧燃烧样品前处理法在元素分析中的应用

微波氧燃烧法是近年来兴起的一种微波辅助绿色样品前处理方法。微波氧燃烧反应器结构和应用程序有助于燃烧完全和提高元素回收率。在引燃剂存在的条件下,样品与氧气在微波辐射下迅速发生燃烧反应,反应完毕后待测元素被吸收液回流吸收。吸收液可通过各种元素分析仪器(如AAS,ICP-OES,ICPMS,IC等)很好地检测出元素的种类、含量和价态等。该法适用样品范围广泛、绿色环保、反应时间短、反应后样品残留碳极低且元素的回收率高,可在很大程度上降低挥发性元素的损失。文中介绍了微波氧燃烧的基本原理、反应装置、引燃剂和吸收液、样品制备以及其在食品、生物、聚合物、地质、煤、原油以及碳材料等样品前处理的应用进展及前景,旨在对今后的研究提供更加有效的参考价值和意义。     

Application of the Sulfuric Acid-Halide Salt Reaction to the Analysis of Sulfuric Acid Containing Aerosols

Abstract

A new X-ray fluorescence method for the determination of sulfuric acid in sulfuric acid containing aerosols is presented. The technique makes use of the reaction between sulfuric acid and potassium chloride yielding volatile hydrogen chloride and thus changing the C1/K ratio. Nuclepore^R membrane filters are first loaded with potassium chloride and then used for the collection of the aerosol under study. The chlorine and potassium X-ray signals are measured before and after the sampling of the acid aerosol, and the decrease in the Cl/K intensity ratio is taken as a measure for the amount of sulfuric acid collected.     

A Routine Method for the Quantitative Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Urban Air

Abstract

We have developed a method for the quantitative determination of polycyclic aromatic hydrocarbons (PAHs) present in urban air, which can be performed rather quickly, and which uses a minimal amount of solvents.

Air samples were collected using a home-made low-volume air sampler equipped with glass fibre filter and polyurethane foam plugs. After Soxhlet extraction a liquid-liquid partition was carried out to isolate the PAH fraction. This liquid-liquid partition was performed in micro-scale, enabling us to use small quantities of the solvents and to separate the solution layers very rapidly using a centrifuge. Sample clean-up was accomplished on a high performance liquid chromatograph equipped with two normal phase silica columns. The losses of all investigated PAHs occurring during the various steps of sample clean-up have been determined. The qualitative and quantitative determination of the PAHs was carried out by capillary gas chromatography; the results were confirmed by GC/MS measurements.

The analytical procedure described was applied over a period of one year to measure the concentrations of 21 PAHs in the city of Vienna at a site with high traffic density. The concentrations of the four more volatile PAHs were determined on a semi-quantitative basis. The ratio of two selected PAHs was used to estimate the respective contribution of traffic and domestic heating to the total PAH level at the sampling site.     

CSP分析方法在简化燃烧化学反应系统中的应用

基于计算奇异摄动(CSP)思想, 对甲烷/空气预混燃烧系统进行分析. CSP将反应空间分裂, 消除刚性; 将单点分析和全局分析相结合, 合理选择主要组分和稳态物质, 使用CSP的特征指数简化方程. 构建了针对甲烷/空气预混燃烧系统的总包15步反应机理, 并利用Sandia实验室的PREMIX软件包对该系统进行分析, 验证了简化机理的准确性, 证实了CSP分析方法在燃烧系统中应用的可靠性和优越性, 并为研究简化燃烧系统的分析提供了一种新的思路.     

高频感应炉燃烧–红外吸收法测定银杏及银杏叶中的硫含量

采用高频感应炉燃烧–红外吸收法测定银杏叶、银杏果肉、银杏壳和银杏仁中的硫含量。样品以艾士卡试剂为熔融剂,在800℃马弗炉内熔融1 h,冷却后测定硫含量。硫的质量分数在0.40%~4.00%范围内与吸收峰面积呈良好的线性关系,线性相关系数为0.990 4,检出限为0.000 9%。测定结果的相对标准偏差为4.04%(n=11),平均加标回收率为101.03%。将红外吸收法与电感耦合等离子体原子发射光谱法及硫酸钡重量法进行比对试验,3种方法测定结果相一致。利用该方法测定了不同区域银杏叶中硫的含量,结果表明,风景区和居民区银杏叶干燥基全硫的含量较低,重工业区硫含量较高。对同一地区的银杏果肉、银杏壳、银杏仁中干燥基全硫的含量进行比较,结果表明银杏果肉硫含量最高,银杏壳次之,银杏仁最低。该方法灵敏度高,重现性好,可用于银杏及银杏叶中硫含量的准确测定。     

简易测定发中微量元素铅的方法实验与探讨

通过对简易测定发铅的方法实验，研究与探讨，提出纸色谱法是简易测定发中微量元素铅的较好方法，该法简捷，快速，分析样品量大，成本低，无污染，有推广普及价值。     

无铅汽油中痕量铅的快速测定方法

研究了快速测定无铅汽油中痕量铅的方法。在４９０ｎｍ处,测定经氯化四乙胺的氯仿溶９液和碘溶液处理过的汽油与ＰＡＲ．２Ｎａ反应生成的络合物。线性范围为０－２５．２μｇ／ｍＬ,回归方程为Ａ＝０．０１２３４ｃ＋０．４１８８,相关系数为０．９９９２,检出限为０．２６μｇ／ｍＬ。本方法操作简便,测定一次可在２０ｍｉｎ内完成。     

封闭水浴溶样-载碳泡塑吸附-电感耦合等离子体发射光谱法测定矿石中金含量

采用聚碳酸酯溶样瓶进行封闭水浴溶样,溶液加入NH_4HF_2和酒石酸配合其它干扰金属阳离子,加入载碳泡塑振荡吸附金,使用电感耦合等离子体发射光谱仪(ICP-OES)直接测定.方法检出限为0.005 09μg/g,测定上限为150.0μg/g,相对标准偏差(RSD)低于5.77%,消除了Ag、Sb和Fe等阳离子干扰,通过对不同含量金矿石标准物质的测定,取得了较高的准确度,可满足金矿石分析要求.     

电感耦合等离子体质谱(ICP-MS)法测定农产品地土壤中铅、镉、铬消解方法的改进

采用赶酸电热板消解农产品地土壤中的重金属,电感耦合等离子体质谱(ICP-MS)法同时测定土壤中的铅、镉、铬。研究了酸体系及酸用量、赶酸电热板的升温程序,确定了最佳消解条件。通过统计50个批次土壤样品中加入的质控样,做出质控图,结果表明:各元素测定值均落在中心附近、上下警告线之内,批次内平行样品各元素相对标准偏差均小于5%。方法克服了传统的电热板消解法的缺点,弥补了高压罐消解法和微波消解法的不足,方法快速、准确,适合于大批量样品的分析。     

乳化剂OP存在下微分电位溶出法同时测定铅铜的研究

在乳化剂ＯＰ存在下及０．３ｍｏｌ／Ｌ ＨＣｌ介质中，铅，铜在峰电位－０．５５Ｖ及－０．３４Ｖ处分别有一灵敏的溶出峰。详细探讨了溶出分析的最佳条件。本方法已用于发酵酒，配制酒，蒸馏酒及饮料中铅，铜的直接测定，回收率为９０．６％－１１０％，ＲＳＤ为０．２％－８．２％，检出限为０．０２５－０．００５４μｇ／２０ｍＬ范围。     

Sensitive Simultaneous Determination of Rutin and Folic Acid with the Use of a Solid Lead Electrode by Means of Adsorptive Stripping Voltammetry

In this article a solid lead electrode (PbE) was utilized for the first time for determination of organic substances by means of adsorptive stripping voltammetry. A new procedure of simultaneous determination of rutin and folic acid was developed. Two well shaped and well separated reduction signals of rutin and folic acid were obtained with the use of PbE. The optimization of analytical procedure was presented. The calibration graphs for rutin and folic acid for an accumulation time of 120 s were linear in the ranges from 2×10^?9 to 1×10^?7 mol L^?1 and from 2×10^?9 to 5×10^?8 mol L^?1, respectively. The obtained detection limits for rutin and folic acid determination following accumulation time of 120 s were 7.9×10^?10 and 8.4×10^?10 mol L^?1. Potential interference effects were investigated. The proposed procedure was used for analysis of pharmaceutical preparations with satisfactory results showing practical applications. The analytical parameters of the proposed procedure were compared with other voltammetric procedures of mentioned substances determination.     

Determination of Cd,Pb, and Cu in the Atmospheric Aerosol of Central East Antarctica at Dome C (Concordia Station)

Trace heavy metals Cd, Pb, and Cu were determined (by square wave anodic stripping voltammetry) in aerosol samples collected at Dome C (the Italo-French Station Concordia), a remote site of the Central East Antarctic plateau, for which no data are available until now. During the Austral Summer 2005–2006, three PM10 high-volume impactors were installed in two locations nearby of Concordia station: the first one very close and downwind of the station (about 50 m north), the other two (very close to each other) in a ‘distant’ site, upwind of the station and close to the astrophysics tent (not used in that expedition) at ~800 m south of Station Concordia. For each sample, the availability of the mass of the aerosol collected (obtained by differential weighing carried out on site), in addition to the volume of the filtered air, allowed us to express results both in terms of metal mass fractions in the aerosol and in the usual way of metal atmospheric concentrations. Metal contents increased in the order Cd < Pb < Cu with the following ranges of values: Cd 1.0–8.4 µg g⁻¹ (0.09–3.1 pg m⁻³), Pb 96–470 µg g⁻¹ (12–62 pg m⁻³), and Cu 0.17–20 mg g⁻¹ (0.027–2.4 ng m⁻³). From the metal temporal profiles obtained we estimated the following background values for the area of Dome C, expressed both in mass fractions and in atmospheric concentrations: Cd 1.2 ± 0.2 µg g⁻¹ (0.24 ± 0.13 pg m⁻³), Pb (here fixed as upper limit) 113 ± 13 µg g⁻¹ (21 ± 8 pg m⁻³), and Cu 0.91 ± 0.48 mg g⁻¹ (0.12 ± 0.07 ng m⁻³). The highest values were observed in the first part of the season, and particularly for the site close to the station, possibly related to sample contamination linked to intense activity at the Concordia station connected with the beginning of the expedition, including aircraft arrivals/departures. Increments of up to 10 times (and even 20 times for Cu) were recorded with respect to the background values. The metal excesses of the contaminated over background samples were found approximately, except for Cu, in the same proportion of the metal contents of the special Antarctic blend (SAB) diesel fuel, which is used almost exclusively at Concordia Station. The effect of the wind direction was also observed. Thus in the intermediate period of the campaign, when the wind direction reversed for several days with respect to the prevailing one, Cd and Pb metal contents decreased at the sampling point installed close to the station, now upwind of Concordia station, and increased at the ‘clean’ site astrophysics tent, turned downwind at the main station. No simple and easily interpretable effect of the wind direction was observed for Cu, which suggests that some other extemporaneous and not clearly identified factor may have intervened in this case. These results suggest that the human impact at Dome C influences mainly the zone very close to the station, but also the area in the neighborhood, including the supposed clean site of the astrophysics tent (about 800 m far from the station), when the wind direction reverses with respect to the prevailing one, leaving the site downwind of the station Concordia. Since no other data are reported for the Dome C area, our results are compared with literature data referred to the South Pole Station (the only other plateau site for which data are available) and several other coastal Antarctic sites, observing that our results (excluding Cu) are the lowest ever observed for Antarctic aerosol.     

延缓燃烧法应用于直接燃烧-气体容量法测定不锈钢中低含量碳

随着冶金工业质量控制实验室的不断发展,测定不锈钢中低碳燃烧气体分析仪的水平不断提高,如应用容量半自动定碳仪测定不锈钢中低碳。本工作用瓷舟上加燃烧延缓盖的延缓燃烧法及双金属助熔剂（芯为夹层铜）,利用双金属助熔剂的层间引起弱的范德华力的夹层方法,解决了不锈钢中低碳测定结果不稳定和重现性差的问题。     

原子荧光法测定食品中铅的介质酸度控制数学模型

构建了采用原子荧光法测定食品中铅含量时控制反应介质酸度的数学模型,根据该数学模型可以协调样品及载流中盐酸的体积分数、硼氢化钾的质量浓度、还原剂中氢氧化钾的质量浓度等反应介质的重要参数,保证铅烷发生的效率。采用该数学模型对2010年度国际弗帕斯（FAPAS）考核样品（辣椒粉）和国家标准物质（茶叶GBWl0016和灌木枝叶GBW07602）中的铅含量进行了测试,测定值的回收率介于98．9％～109．4％之间,取得满意结果,表明该模型可以指导实际应用。     

Simultaneous Determination of Nitrite and Hydrogen Peroxide Using Hemoglobin Modified Pencil Lead Electrode as a Novel Biosensor: Application to the Analysis of Mother’s Milk

In the present paper simultaneous determination of nitrite and hydrogen peroxide using hemoglobin modified pencil lead electrode (Hb/PLE) prepared by a simple and rapid electroless method was described. In the first part of the work the reduction of NO₂ and H₂O₂ at the modified electrode was investigated by cyclic voltammetry. Then under optimal conditions using differential pulse voltammetry, the biosensor could be used for the determination of H₂O₂ at concentration ranging from 5 to 240 M and NO₂ at concentration ranging from 10 to 240 M. The detection limits were 3×10^?6 and 5×10^?6 M, for NO₂ and H₂O₂ respectively. Differential pulse voltammetry also used for the simultaneous determination of NO₂ and H₂O₂. This modified electrode successfully used for the determination of NO₂ and H₂O₂ in tap water and mother’s milk samples.     

Development and Validation of a Liquid Chromatographic Method for the Determination of Leflunomide: Application to in vitro Drug Metal Interactions

Leflunomide is a leading drug for the treatment of rheumatoid arthritis. The principle aim of this study was to develop and validate an RP‐HPLC method for the determination of leflunomide in bulk and pharmaceutical dosage form using diclofenac sodium as an internal standard. For this purpose, chromatography was accomplished on a Purospher Start, C₁₈ (5 (m, 12.5 cm×0.46 cm) column at ambient temperature. Methanol:water (80:20, V/V) solvent system was selected as mobile phase, the pH of which was adjusted to 3.4 by ortho‐phosphoric acid and delivered at a flow rate of 1.2 mL·min⁻¹. Seperation of leflunomide and diclofenac sodium was carried out on a Purospher Start, C₁₈ equipped with a UV‐visible detector at 248 nm. The suitability of the method for the quantitative determination of the drugs is proven by validation in accordance with the requirements laid down by the International Conference on Harmonization (ICH) guidelines. The method was accurate (99.55%–100.03%), specific, linear (R²>0.999) and precise (intra‐day precision 0.023%–0.93% and inter‐day precision 0.26%–0.944%) in the range of 0.5–20 (g·mL⁻¹. The minimum limit of detection and quantification in pharmaceutical formulation were 0.05 and 0.15 (g·mL⁻¹, respectively. Thus the proposed method is simple, accurate, reproducible and suitable for the routine analysis of leflunomide in pharmaceutical formulations and was applied to study in vitro drug‐metal interactions.