Mechanised flow system for on-line microwave digestion of food samples with off-line catalytic spectrophotometric determination of cobalt at ng l-1 levels

A mechanised system for on-line slurry food sample digestion was developed and an off-line cobalt determination was performed. The stabilised slurry sample was introduced into an air carrier stream until reaching the digestion coils located inside a household microwave oven. Software written in Visual Basic 3.0 was developed to permit the transport of the slurry samples and the programming of the microwave oven and also the control of the mineralization valve. The proposed system was optimized for determination of cobalt in certified samples such as mussels, bovine liver and fish and also uncertified fish samples. The digestion parameters were established as 3 mol l-1 HNO3 for mussels, 3 mol l-1 HNO3 plus 0.16% v/v H2O2 for bovine liver and 12 mol l-1 HNO3 for fish employing maximum power for 5 min of microwave actuation. In the subsequent spectrophotometric method for the catalytic determination of cobalt, the Tiron and hydrogen peroxide concentrations were 1.8 x 10(-3) and 3.0 x 10(-4) mol l-1, respectively, and the sample residence time was 300 s as determined by an optimisation process. The proposed method features a linear range from 10 to 200 ng l-1 Co (r > 0.996) with detection and quantification limits of 1.7 and 5.5 ng l-1 Co, respectively. The precision, expressed as RSD, was 2.4% (n = 12) for repeatability and 5.2% (n = 10) for reproducibility and the accuracy of the proposed method was assessed by using certified samples and an alternative technique (ETAAS).     

Determination of lead in plant tissues: a pitfall due to wet digestion procedures in the presence of sulfuric acid.

Two wet digestion procedures for the determination of lead in plant materials by electrothermal atomic absorption spectrometry have been evaluated. The combination of HNO3, H2O2 and HF, though leading to incomplete digestion, yielded values corresponding well with the reference or indicative values of the vegetal tissues used. The mixture of H2SO4, HNO3 and HCIO4 gave results that were too low in some instances, owing to the formation of a mixed precipitate (Pb,Ba)SO4.     

Determination of lead and cadmium in titanium dioxide by differential pulse anodic stripping voltammetry

A procedure for the simultaneous determination of lead and cadmium in TiO(2) by differential pulse anodic stripping voltammetry (ASV) has been developed. The key feature of the method is the use of triethanolamine (TEA) to remove titanium interference: TiO(2) undergoes acidic digestion with HF/H(2)SO(4) at atmospheric pressure, TEA is added to the HCl solution of the residue and the solution is analysed using a standard ASV instrumentation, equipped with a hanging mercury drop electrode. The calibration curves for both lead and cadmium are linear up to 50 mugl(-1) of solution, and the detection limits are 1 mugl(-1), corresponding to 1 mugg(-1) of TiO(2). Method reliability was tested by comparing the results with those given by electrothermal atomic absorption spectroscopy. The method has been successfully applied for determination of both contaminants in powdered titanium dioxide (raw materials) and in titanium dioxide-containing cosmetics (sunscreen products).     

微波消解同时衍生化GC-MS法测定血浆中脂肪酸的研究

研究了利用微波能对样品进行加热, 以Ｈ２ＳＯ４ － 甲苯－ 甲醇体系作衍生化试剂, 在消化的同时对血浆中的脂肪酸进行衍生化, 然后用ＧＣ－ ＭＳ 法测定血浆中脂肪酸。 对微波功率、微波加热时间、消解及衍生化试剂等条件进行了优化, 测定结果较好。该法整个消化及衍生化过程只需２ ｍｉｎ , 与传统方法相比大大缩短了实验操作时间, 特别适用于大量样品的测定。     

Comparison of four microwave digestion methods for the determination of selenium in fish tissue by using hydride generation atomic absorption spectrometry

Four microwave digestion methods of fish tissue for selenium determination by hydride generation atomic absorption spectrometry were compared, in which potassium hexacyanoferrate(III) was chosen as a masking agent for eliminating matrix interferences. The results showed that the methods employing HNO(3)/H(2)O(2), HNO(3)/K(2)S(2)O(8)/H(2)O(2) and HNO(3)/H(3)PO(4)/H(2)O(2) digestion media were unreliable. However, the decomposition using the digestion media of HNO(3)/H(2)SO(4)/H(2)O(2) enabled adequate digestion of fish tissue and retention of selenium in a state amenable for determination. Therefore, the digestion procedures with HNO(3)/H(2)SO(4)/H(2)O(2) media are proposed for the determination of selenium in fish tissue by hydride generation atomic absorption spectrometry. The recoveries of the spiked samples investigated ranged from 90 to 102%. The result obtained from analyzing the NIES CRM No. 6 mussel was in good agreement with the reference value (reference value: 1.5 mug/g; found: 1.45 +/- 0.05 mug/g). The limit of detection for selenium was 0.03 mug/g dry mass for a 100 mg sample. The contents of selenium in local fish species investigated ranged from 0.49 to 2.90 mug/g, and the relative standard deviation for the determination of selenium was less than 8%.     

Analytical control of silica glass production. Voltammetric determination of titanium and iron in raw materials and silica glass samples

Adsorptive stripping voltammetric (AdSV) methods are presented for the determination of titanium and iron in quartz and silica glass samples obtained after pressure decomposition. Mandelic acid and catechol were used as complexing agents for titanium and iron, respectively. The method for titanium determination is based on the catalytic effect of chlorate ions. An insoluble residue remaining after decomposition of quartz and silica glass samples in HF+H2SO4 mixture was checked by energy-dispersive X-ray analyses. ET-AAS was applied as a reference method to AdSV measurements.     

钛—二溴苯基荧光酮—溴化十六烷基吡啶树脂相光度法测定钢铁中的痕量钛

本文研究了Ｔｉ与二溴苯基荧光酮（ＢＰＦ）及溴化十六溴烷基吡啶（ＣＰＢ）在０．１～１．３ｍｏｌ／Ｌ的硫酸介质中反应生成有色络合物，然后，采用Ｄ１５２Ｈ弱酸性阳离子树脂进行交换，在树脂相下进行光度进行的方法，络合物的最大吸收峰位于６１８ｎｍ处，具有较高的反应灵敏度，在０～２４０μｇ／Ｌ范围内络合物符合比尔定律，此方法用于测定钢铁中痕量钛的含量，结果令人满意。     

Determination of total iodine in foods and dietary supplements using inductively coupled plasma-mass spectrometry

A method was developed and validated for the determination of total iodine in a wide variety of food products and dietary supplements. The method involves a unique sample digestion with a KOH solution in an oven or by using an open-vessel microwave system. After digestion, a stabilizer is added and the solution is taken to volume, then filtered and analyzed either directly or after dilution. The amount of iodine is determined with inductively coupled plasma-mass spectrometry (ICP-MS). The method was validated by experiments to determine its precision, accuracy, linearity, specificity, ruggedness, and robustness. The LOQ of this method is 25-50 microg/kg. The method demonstrated an average RSD of 2.27% during analysis of milk powder and 4.30% during analysis of a dietary supplement tablet reference material. The accuracy of the method as determined with these same reference materials was 100 and 94.2%, respectively. The method has been used successfully on commodity foods, processed foods, dairy products, pet food, infant formula, animal feed, mineral premixes, and a variety of dietary supplements.     

CODCr测量方法优化及其受营养盐胁迫研究

基于CODCr的K2 Cr2O7滴定法和HACH(哈希公司)DR6000,结合design-expert拟合分析,得到CODCr精确测量的最佳方案:消解液加入量为3 mL,K2 Cr2O7与H2 SO4-Ag2 SO4的加入比为1:5(V/V),K2Cr2O7溶液0.046 g/mL、H2SO4-Ag2SO4溶液3 g/L、HgSO40.038 g/支,恒温120℃消解2 h。同时,基于拟定的最佳方案分析了营养盐类对CODCr测定结果的影响,发现氨氮和亚硝态氮对测定结果有明显影响,而磷酸盐和偏磷酸盐对测定结果的影响较小。     

紫外分光光度法测定聚硫密封胶中二氧化钛

基于强酸性溶液中钛氧离子与H2O2发生显色络合反应的原理,建立了浓硫酸–硫酸铵消解–紫外分光光度法测定聚硫密封胶中TiO_2含量的方法。通过对酸液和显色剂用量,以及显色络合物稳定性的系统考察,确定浓硫酸用量为2 mL,双氧水用量为3 mL,检测波长为403 nm。二氧化钛质量浓度在0~130μg/mL范围内与其吸光度呈良好的线性关系,线性方程为A=5.047 8c–0.019 31,r~2=0.999 2,检出限为0.08μg/mL。检测结果的相对标准偏差为0.89%(n=5),3水平加标平均回收率为101.7%。该方法线性范围较宽、检出限低、重复性好,可用于聚硫密封胶中二氧化钛的定量分析。     

微波消解–ICP–MS法测定话梅中的二氧化钛

建立了微波消解–电感耦合等离子体质谱仪(ICP–MS)测定话梅中二氧化钛的方法。话梅样品用硝酸及过氧化氢经微波消解仪消解,将消解液除酸定容后用电感耦合等离子体质谱仪测定,以内标法测得钛的含量,并转换成样品中的二氧化钛含量。钛含量在0~500μg/kg范围内与信号强度呈良好的线性,线性相关系数r=0.999 9,检出限为0.04μg/kg。在0.06,0.15,0.30μg/kg的添加水平下,加标回收率为80%~100%,相对标准偏差为3.2%~3.9%(n=6)。该法稳定性好,测定结果准确、可靠。     

Ag2SO4-CuSO4 催化-微波消解快速测定炼油污水中化学需氧量

以Ａｇ２ＳＯ４－ＣｕＳＯ４为催化剂,探讨了微波消解测定炼油污水中化学需氧量（Ｃｈｅｍｉｃａｌ Ｏｘｙｇｅｎ Ｄｅｍａｎｄ,ＣＯＤｃｒ）的方法。确定了微波消解测定炼油污水ＣＯＤｃｒ的最佳条件;消解功率、消解时间、混酸介质Ｈ３ＰＯ４－Ｈ２ＳＯ４用量、催化剂配比等。用该方法测定炼油水各处理装置出水 的ＣＯＤｃｒ,与经典的ＣＯＤｃｒ回流法所得结果一致。方法适用于临控生产过程。     

Formation of TiO2 nanoparticles in water-in-CO2 microemulsions

Titanium dioxide nanoparticles can be produced by the controlled hydrolysis of titanium tetraisopropoxide in water-in-CO2 (w/c) microemulsions stabilized with the surfactants ammonium carboxylate perfluoropolyether (PFPE-NH4) and poly(dimethyl amino ethyl methacrylate-block-1H,1H,2H,2H-perfluorooctyl methacrylate) (PDMAEMA-b-PFOMA); the greater control of hydrolysis and particle growth with PDMAEMA-b-PFOMA is consistent with the differences in the stabilities and interactions for these two microemulsions.     

钛白粉载体对选择性催化还原脱硝催化剂性能的影响

钛白粉(TiO2)是钒钛类选择性催化还原(SCR)脱硝催化剂的载体,TiO2的晶型、比表面积、粒度、孔结构以及SO42-和P2O5含量直接影响所制备的SCR催化剂的性能。一般而言,TiO2的比表面积越大,以其制备的SCR催化剂的比表面积也越大,活性也较高;但对于纳米级TiO2,由于颗粒粒径太小,容易发生烧结,而且形成钒钛化合物,导致催化剂比表面积较载体明显下降,因而活性降低。锐钛型TiO2由于比表面积大和不易被硫化,较金红石型TiO2适合做载体。多孔结构的TiO2使得钒物种在载体表面处于高度分散状态,从而提高催化剂的活性。TiO2中本身含有的少量SO42-和P2O5有助于提高催化剂的性能。     

A simplified modification of the AOAC official method for determination of total dietary fiber using newly developed enzymes

Since 1985, AOAC Method 985.29 has been globally adopted as a standard method for determination of total dietary fiber in foods. Nevertheless, an aspect of AOAC Method 985.29 that needs to be improved is the laborious process to treat 3 enzymes separately at their individual proper pH, which is quite time-consuming. Several examinations have been carried out to resolve this problem. The characteristics of newly developed thermostable alpha-amylase, neutral protease, and amyloglucosidase were evaluated based on the pH-activity profile and the property of starch hydrolysis in comparison with those of the conventional enzyme reagents. These 3 developed enzymes were found to work under the same pH condition and to accomplish sufficient digestion for the typical 3 starches: soluble starch, corn starch, and wheat starch. The experimental results revealed that the dietary fiber determination in foods could be performed without pH adjustment in the enzymatic digestion process. The modified method will be greatly helpful in determining the total dietary fiber contents in food materials with less laborious work and with an accuracy equivalent to that of AOAC Method 985.29.     

Analytical procedure for the simultaneous voltammetric determination of trace metals in food and environmental matrices. Critical comparison with atomic absorption spectroscopic measurements

An analytical procedure fit for the simultaneous determination of copper (II), chromium(VI), thallium(I), lead(II), tin(II), antimony(III), and zinc(II) by square wave anodic stripping voltammetry (SWASV) in three interdependent environmental matrices involved in foods and food chain as meals, cereal plants and soils is described. The digestion of each matrix was carried out using a concentrated HCl-HNO3-H2SO4 (meals and cereal plants) and HCl-HNO3 (soils) acidic attack mixtures. 0.1 mol/L dibasic ammonium citrate pH 8.5 was employed as the supporting electrolyte. The voltammetric measurements were carried out using, as working electrode, a stationary hanging mercury drop electrode (HMDE) and a platinum electrode and an Ag/AgCl/KClsat electrode as auxiliary and reference electrodes, respectively. The analytical procedure was verified by the analyses of the standard reference materials: Wholemeal BCR-CRM 189, Tomato Leaves NIST-SRM 1573a and Montana Soil Moderately Elevated Traces NIST-SRM 2711. For all the elements in the certified matrix, the precision as repeatability, expressed as relative standard deviation (Sr %) was lower than 5%. The accuracy, expressed as percentage relative error (e %) was of the order of 3-7%, while the detection limits were in the range 0.015-0.103 microg/g. Once set up on the standard reference materials, the analytical procedure was transferred and applied to commercial meal samples, cereal plants and soils samples drawn in sites devoted to agricultural practice. A critical comparison with spectroscopic measurements is also discussed.     

食品中维生素D与25-羟基维生素D检测技术及含量分布研究进展

维生素D是一种对于维持人体健康具有重要作用的脂溶性维生素,25-羟基维生素D是其在人体内循环和存储的主要形式。食品中维生素D和25-羟基维生素D前处理的通常采用碱皂化、有机溶剂提取、固相萃取或者半制备色谱净化;其测定方法多为放射免疫法和液相色谱法。液相色谱串联质谱凭借高灵敏度和高准确度,目前在食品中维生素D和25-羟基维生素D测定中发挥重要作用。近年来二维液相色谱和超高效超临界流体色谱由于其强大的分离能力,在食品中维生素D和25-羟基维生素D的分析中表现出强大的潜力。该文综述了近年来食品中维生素D和25-羟基维生素D的检测方法及二者在动物食品和植物食品中的含量分布研究,以期为建立适合不同食物样品的测定方法,指导居民合理膳食,进行膳食摄入量评估等研究工作提供参考。     

Physicochemical and electrorheological properties of titanium dioxide modified with metal oxides

The properties of electrorheological fluids containing dispersed phase of titanium dioxide nanoparticles prepared via the sol-gel method and modified with metal oxides have been studied. Titanium dioxide has the anatase structure with crystallite sizes of 8–10 nm and a specific surface area of 90–140 m²/g. It has been found that the magnitude of the electrorheological response of the filler is determined by the specific surface area and the content of a modifying component. The strongest electrorheological response has been revealed for titanium dioxide modified with aluminum oxide at an Al content of 6.5–7.0 mol % relative to TiO₂.     

预处理方法对钛硅沸石催化性能的影响

 采用不同的介质（HCl－H2O2,NH4F－H2O2,HNO3－H2O2,H2SO4－H2O2）对钛硅沸石TS－1进行预处理,并用IR,XRD,UV－Vis,XRF和27AlMASNMR对样品进行了表征;以丙烯环氧化为探针反应,考察了样品的催化性能．结果表明,经预处理后,TS－1中的TiO2均被脱除约20％,而Al几乎未被脱除;所脱除的TiO2为非骨架钛;环氧丙烷的选择性降低,但H2O2的有效利用率明显升高．特别是采用NH4F－H2O2预处理时,H2O2的转化率和有效利用率均提高10％．     

Heavy metal determination in aquatic species for food purposes

New analytical procedures and sample mineralizations are proposed regarding the determination of arsenic, selenium, copper, lead, cadmium, zinc and mercury in matrices involved in food chain as mussel, clams and fishes. As regard As, Se, Cu, Pb, Cd and Zn determinations, H2SO4-HNO3 acidic mixture is used for the digestion of each matrix. In the case of Hg the sample digestion is performed using a concentrated suprapure H2SO4-K2Cr2O7 mixture and the results are compared with those from other conventional methods. Differential pulse cathodic (DPCSV) and anodic stripping voltammetry (DPASV) are employed for determining simultaneously selenium, arsenic and copper, lead, cadmium, zinc, respectively, while mercury determination is carried out by the cold vapour atomic absorption spectrometry (CV-AAS) with reduction with SnCl2. The voltammetric measurements were performed using a conventional three-electrode cell and the ammonia-ammonium chloride buffer (pH 9.3) as supporting electrolyte. For all the elements, in addition to the detection limits, precision and accuracy data are also reported: the former, expressed as relative standard deviation (Sr), and the latter, expressed as relative error (e), are in all cases between 3 to 6%.