Metal Sorption,Solid Phase Extraction and Preconcentration Properties of Two Silica Gel Phases Chemically Modified with 2-Hydroxy-1-Naphthaldehyde

Active silica gel phase (I) was chemically modified to the corresponding amino- (SiNH₂) and chloro- (SiCl) derivatives via silylation reactions. These were used to synthesize two newly modified silica gel phases (II, III) by direct chemical reaction with 2-hydroxynaphthaldehyde (2-HNA). The surface coverage values are 370, 432µmolg^–1 and 320, 355µmolg^–1 for (II) and (III), on the basis of thermal desorption and metal probe testing method, respectively. The metal sorption properties of silica gel phases (II, III) were studied and compared with active silica gel phase (I). The maximum determined metal capacity values were found to be 10–110, 20–290 and 20–370µmolg^–1 for phases I, II and III, respectively. The distribution coefficient values (K_d) were also determined for a series of metal ions, and the results showed that the two new chemically modified phases (II and III) were highly selective for Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺ and Pb²⁺. The potential applications of silica gel phases (II, III) as solid phase extractors for the same five metal ions spiked in drinking tap water (1.000µgmL^–1) were found to give percentage recovery values in the range of 90.2–96.3±4.1–6.3%, while pre-concentration of the same five metal ions spiked in drinking tap water (50.0ngmL^–1) was successfully accomplished with a percentage recovery range of 92.6–95.8±4.8–5.7%.Received December 16, 2002; accepted May 14, 2003 published online September 1, 2003     

Energy Dispersive X-Ray Fluorescence Analysis and X-Ray Microanalysis of Medieval Silver Coins

 Austrian medieval silver/copper coins were investigated at their surfaces by energy dispersive X-ray fluorescence analysis (EDXRF) and at the cross-sections by X-ray microanalysis in the scanning electron microscope (SEM/EDX) in order to estimate the error occurring when corroded objects of art and archaeology are analyzed on the surface by non-destructive methods. Additionally, Ag/Cu-standards were treated in diluted sulphuric acid and the depletion of copper on the surface was measured by EDXRF. By calculating the ratio of the Ag-K/Ag-L intensity the process of blanching could be studied.     

波长色散X射线荧光光谱无标分析法检测树脂中的铅

建立波长色散X射线荧光光谱检测树脂中重金属元素的无标样分析方法。热塑性塑料在200℃热压成样片;热固性塑料取平面直接测量;涂料研磨成粉末后用硼酸镶边、衬底,经过压样机20 t压力30 s压制成样片。所有样品在真空模式下,以激发电流为50 mA,激发电压为60 kV,分光晶体为LiF(200),准直器为0.23°,测量谱线为Pb Lβ1,峰位(2θ)为28.258的仪器工作条件下测定树脂中铅的含量,通过康普顿比率判断结果的可信度。测定值与标准方法检测值相比,偏差小于10%,测定结果的相对标准偏差小于1%(n=6)。结果表明,波长色散荧光光谱无标分析方法可以快速准确地分析树脂样品中的铅含量。     

波长色散X射线荧光光谱法快速测定纺织面料中的铬、镍、铜

建立波长色散X射线荧光光谱快速检测纺织面料中铬、镍、铜的方法。利用树脂将标准贴衬织物复合到玻璃熔片上,在制备好的织物样片上滴加铬、镍、铜标准溶液,采用波长色散X射线荧光光谱仪检测。根据元素滴加量的变化建立校准曲线,铬、镍、铜3种元素的含量分别在0~853,0~853,0~1 706μg/g范围内与荧光强度呈良好的线性关系,相关系数r2大于0.99。方法回收率为95.0%~98.8%,测定结果的相对标准偏差为3.2%~4.8%(n=6)。利用该方法检测纺织面料中重金属元素含量,方法简便,结果准确,检测成本低。     

Development of an Automated Procedure for the Optimization of Multielement Analysis with Energy Dispersive X-Ray Fluorescence Spectroscopy

Abstract

A system is devised that automatically optimizes energy dispersive x-ray spectrometer settings for multielement determinations under compromise conditions using self-sustained search algorithms. As an objective function, the joint probability of detecting all elements was chosen. The current process is to date limited by the resolution of the commercially available automatic power supply employed. Typical optimization times needed for the entire procedure are on the order of 5 minutes for major constituents, with prolonged times for minor and trace elements as a result of increased counting time to obtain good counting statistics.     

Solid Phase Extraction and Determination of Lead in Water Samples Using Silica Gel Homogeneously Modified by Thiosalicylic Acid

Abstract

Silica gel was modified by thiosalicylic acid via homogeneous routes to obtain immobilized silica gel sorbent (TSA‐immobilized silica gel). This new sorbent was characterized using variety of physical chemistry techniques including, high resolution solid state ¹³C and ²⁹Si CP/MAS NMR, X‐ray photoelectron spectroscopy (XPS), thermal analysis (TGA and DTA), elemental analysis, and BET surface analysis as well as infrared spectroscopy (FTIR). New support was used for the selective extraction and concentration of lead ions by silica gel modified with thiosalicylic acid, as a highly selective and stable reagent, from aquatic samples and its determination with FAAS. Lead ions can be desorbed with 4 mol dm^?3 HNO₃. The sorption capacity for lead ions are found in the range of 64.40 to 69.90 µmol g^?1 of chelating matrix. Tolerance limits for electrolytes and some trace metals in the sorption of lead is reported. Preconcentration factor was found as 150 for Pb(II). The lead in drinking water, mineral water, tap water, and fruit juice was quantitatively recovered with a relative standard deviation lower than 1.50%. A detection limit of the method for lead ions was found as 3.7 µg l^?1.     

Energy Dispersive X-Ray Spectrometry by Microcalorimetry for the SEM

 Analytical X-ray spectrometry for electron beam instruments has advanced significantly with the development of the microcalorimeter energy dispersive X-ray spectrometer (μcal EDS). The μcal EDS operates by measuring the temperature rise when a single photon is absorbed in a metal target. A cryoelectronic circuit with electrothermal feedback and a superconducting transition edge sensor serves as the thermometer. Spectral resolution approaching 4.5 eV for high energy photons (6000 eV) and 2 eV for low energy photons below 2000 eV has been demonstrated in energy dispersive operation across a photon energy range from 250 eV to 8 keV. Spectra of a variety of materials demonstrate the power of the μcal EDS to solve practical problems while operating on a scanning electron microscope platform.     

Characterization of Modified Silica Gel as a Source of Ethene for Standard Gaseous Mixtures

The application of chemically modified silica gel as a source of gaseous standard mixture containing ethene as a measured component is described. The surface of silica gel was chemically modified, which resulted in the formation of N-oxide of diethylaminopropylsilylated silica gel. This compound undergoes thermal decomposition at 245°C, yielding known amounts of ethene. The process of thermal decomposition of chemically modified silica gel took place in a desorber furnace connected on-line via a four-port valve to the device being calibrated. Such a solution provides convenient calibration of a GC/FID system after direct introduction of a stream of the generated mixture onto the front of a GC. It was found that 480 ± 15 mg of ethene can be generated per 1 g of the modified gel.     

Determination of Metal Ions in Natural Waters by Flame-AAS after Preconcentration on a 5-Amino-1,3,4-Thiadiazole-2-Thiol Modified Silica Gel.

ABSTRACT

5-amino-1,3,4-thiadiazole-2-thiol groups attached on a silica gel surface have been used for adsorption of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II) and Zn(II) from aqueous solutions. The adsorption capacities for each metal ion were (in mmol.g^?1): Cd(II)= 0.35, Co(II)= 0.10, Cu(II)= 0.15, Fe(III)= 0.20, Hg(II)= 0.46, Ni(II)= 0.16, Pb(II)= 0.13 and Zn(II)= 0.15. The modified silica gel was applied in the preconcentration and quantification of trace level metal ions present in water samples (river, and bog water).     

偏振式能量色散X射线荧光光谱仪分析高炉渣

在偏振化能量色散型X射线荧光光谱仪上,使用一个HOPG次级靶,成功地对高炉渣中主要成分进行了分析。总的测量时间为120 s。此方法所得分析结果与标样中有关组分的证书值相符,也与工作标样中组分的已知值(化学法测得)一致。     

Qualitative and Quantitative Analysis of Medieval Silver Coins by Energy Dispersive X-Ray Fluorescence Method

Energy-dispersive X-ray fluorescence spectrometry was applied for the analysis of historical silver coins to determine the elemental composition in a fast and non-destructive way. Ag, Cu and trace elements (V, Cr, Mn, Fe, Co, Ni, Hg, Pd, Zr, Mo, Rh, Ru) were determined in coins of King Mathias (Hungary, 1458–1490). A new data evaluation technique was used to avoid the problems arising from the different sizes, surfaces and geometries. The appropriateness of this method was confirmed by analysing certified silver/copper standard alloys.     

超临界流体萃取-硅胶柱收集联用提取蓬莪术中有效成分

采用超临界流体CO2萃取和硅胶柱收集在线联用,提取蓬莪术中的挥发油,随后分别用正己烷、乙醇和乙醚对硅胶柱进行选择性洗脱,从而使蓬莪术挥发油中有效成分莪术二酮的相对含量由原来单一萃取的10．7％提高到34．7％。     

金属材料分析国内外标准中波长色散X射线荧光光谱法的应用

对国内外金属材料分析方法标准(包括ASTM、JIS、EN和GB)中应用波长色散X射线荧光光谱法(XRF)的现状,从方法所涵盖的测定元素及其测定的含量范围以及谱线重叠和基体效应的校正等几个方面,并以钢铁分析中的应用为例作了评述。美国材料与试验协会在2012-2016年间先后发布了3个XRF标准方法,分别应用于铸铁、不锈钢、合金钢和低合金钢的分析,测定元素达13项,根据相关钢材的技术规格确定了各元素含量的测定范围。日本工业标准调查会于1997年并于2010年和2013年经修订公布了钢铁XRF分析法JIS标准,可测定各类钢材中主量、次量以及痕量元素达31项,其中镍、铁、钴和测定下限分别延伸至99.5%,50%和60%,从而使此方法有可能扩展应用于镍基、铁镍基和钴基高温合金的分析。我国先后于2007年和2018年由国家标准经主管部门颁布了XRF分析钢铁和高合金钢的两个标准,可测定这2类钢材中的元素为13项和11项,其测定含量范围系根据材料的技术规格确定。关于谱线重叠和基体效应的校正,各标准中在相关部分作了说明,而ASTM有两则独立标准专门论述这两个问题。在此评述对其他金属材料的XRF分析标准也作了介绍(引用文献15篇)。     

用硅烷化处理改性硅胶分离富集痕量元素

将硅胶用二氯二甲基硅烷处理后，能降低硅胶对极性物质的吸附，增加其对非极性物质或弱极性物质如５－Ｂｒ－ＰＡＤＡＰ等大多数螯合剂的吸附，同时使改性硅胶适应的ＰＨ范围扩宽，对金属离子的净化学吸附增大，使用寿命增加。     

血清中碘海醇的X射线荧光光谱测定法

报道以 Br作为内标、滤纸片浸泡制样 ,测定血清中碘海醇的 X射线荧光光谱( XRF)分析方法。方法简便、快速。检出限可达 8.8μg/m L,相对标准偏差为 3.0 9% ,是检测血清中低浓度碘海醇的较为理想的检测方法     

Application of Ionic Liquid Modified Silica for Solid-Phase Extraction of Polysaccharides from Laminaria japonica

Silica-confined ionic liquids were synthesized for solid-phase extraction of polysaccharides, which was determined by high-performance liquid chromatography coupled with RI detection. The sorbent with amino-imidazolium groups was found to be the optimal material by a comparison of the adsorption capacity of fucoidan and laminarin onto different synthetic sorbents. The proper elution solvents for both laminarin and fucoidan were decided from practical tests. The sorbent performed stably and selectively, demonstrating potential applications in the separation of hydrophilic biomacromolecules, such as polysaccharides.     

同步辐射X荧光微探针扫描分析氟碳铈矿物中的稀土元素

北京正负电子对撞机国家实验室的增频光源提供的同步辐射白光，激发ＬＲＥＥＫ－系列，用ＳＲＸＲＦＭ扫描分析氟碳铈矿物中的轻稀土元素的分布。取同一矿区的氟碳铈矿物，粉碎至粒度〈３００目。一部分熔融，沉淀分离，转成稀土氧化物后，用ＸＲＦ法分析稀土分量。另一部分，不加任何粘结物质压在成Φ２６ｎｍ圆片作为ＳＲＸＲＦＭ扫描分析的参比样品，从而可计算样品中稀土的含量。