Trace Metals Analysis of Legal and Counterfeit Cigarette Tobacco Samples Using Inductively Coupled Plasma Mass Spectrometry and Cold Vapor Atomic Absorption Spectrometry

ABSTRACT

A closed-vessel microwave-digestion method was developed for the determination of trace amounts of Be, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Mo, Cd, Sb, Ba, Tl, and Pb by inductively coupled plasma mass spectrometry and Hg by cold-vapor atomic absorption spectrometry in cigarette tobacco samples. In order to gauge the effectiveness of the digestion procedure, recovery studies were conducted using solutions prepared from National Institute of Standards and Technology Standard Reference Material 1573a Trace Elements in Tomato Leaves and Polish Certified Reference Material Virginia Tobacco Leaves. Limits of detection were below 1 µg g^?1 for all elements studied. Samples from two genuine-brand and three counterfeit packs were analyzed. The mean amounts of Be, As, Mo, Cd, Sb, Tl, Pb, and Hg were higher in counterfeit cigarettes, while the amounts of V, Cr, Mn, Co, Cu, Zn, Se, and Ba were comparable among legal and counterfeit cigarettes; the amount of Ni was higher in the legal cigarettes. Evaluation of Be, As, Mo, Cd, Sb, Tl, Pb, and Hg with their potential hazards for smokers is briefly discussed.     

天然杂质对黄铁矿的电子结构及催化活性的影响

采用密度泛函理论和平面波赝势方法对含天然杂质黄铁矿的电子结构和光学性质进行了计算,并讨论了二十种天然杂质:钴、镍、砷、硒、碲、铜、金、银、钼、锌、铊、锡、钌、钯、铂、汞、镉、铋、铅和锑,对黄铁矿催化活性的影响.结果表明在过渡金属杂质中,杂质能级主要由它们的d轨道产生,而在主族金属及非金属杂质中,杂质能级主要由它们的s或p轨道产生.含铜、钼、砷、金、银或镍的黄铁矿对氧的还原的电催化能力增强.除锌、钼、钌、砷、锑、硒和碲外,其余杂质能增强黄铁矿表面俘获电子的能力,使光生电子和空穴复合的概率减小.光学性质计算表 关键词： 天然黄铁矿 杂质 电子结构 光学性质     

Ultrasonic Nebulization/UV Photolysis Vapor Generation Sample Introduction System for the Determination of Conventional Hydride (As,Bi, Sb,Se, Sn) and Cold Vapor (Hg,Cd) Generation Elements in Reference Materials in the Presence of Acetic Acid by Microwave-Induced Plasma Spectrometry

ABSTRACT

A novel synergic effect of ultrasonic nebulization (USN) and ultraviolet (UV) radiation (photolysis) when used in combination has been exploited for efficient generation of conventional hydride elements (As, Bi, Sb, Se, Sn), Hg vapor, and volatile molecular Cd species. Several UV-based systems were studied, the most advantageous design being an ultrasonic nebulizer fitted with a 6 W mercury pen lamp supplying a microliter sample to a quartz oscillator, converting liquid into aerosol at the entrance of the UV spray chamber. Optimal conditions utilized a 40% v/v solution of acetic acid as the generation medium. The volatile species are detected by microwave-induced plasma optical emission spectrometry (MIP-OES). The experimental concentration detection limits for simultaneous determination, calculated as the concentration giving a signal equal to three times the standard deviation of the blank (LOD, 3σ_blank criterion, peak height), were 11, 22, 16, 19, 20, 11, and 15 µg L^?1 for As, Bi, Sb, Se, Sn, Cd, and Hg, respectively. The method offers relatively good precision (RSD ranged from 3% to 5%) for liquid analysis and microsampling capability. The methodology was validated through determination of elements in two Certified Reference Materials (NRCC DOLT-2, NIST 1643e) and by the aqueous standard calibration technique.     

Using elemental profiles and stable isotopes to trace the origin of green coffee beans on the global market

A broad elemental profile incorporating 54 elements (Li, Be, B, Na, Mg, Al, P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Mo, Pd, Ag, Cd, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Tm, Yb, Re, Ir, Pt, Au, Hg, Tl, Pb, Bi and U) in combination with δ(2) H, δ(13) C, δ(15) N and δ(18) O was used to characterise the composition of 62 green arabica (Coffea arabica) and robusta (Coffea canephora) coffee beans grown in South and Central America, Africa and Asia, the four most internationally renowned areas of production. The δ(2) H, Mg, Fe, Co and Ni content made it possible to correctly assign 95% of green coffee beans to the appropriate variety. Canonical discriminant analysis, performed using δ(13) C, δ(15) N, δ(18) O, Li, Mg, P, K, Mn, Co, Cu, Se, Y, Mo, Cd, La and Ce correctly traced the origin of 98% of coffee beans. Copyright ? 2012 John Wiley & Sons, Ltd.     

Influence of the Matrix on the Atomic Absorption of a Transversely Heated Graphite Atomizer

We have investigated the influence of the sodium chloride and potassium sulfate excess in a sample on the absorption signals of Ag, Al, Au, As, Bi, Cd, Cu, Ga, Ge, In, Mn, Pb, Sb, Se, Sn, and Tl in a transversely heated graphite atomizer (THGA) of the SIMAA 6000 multielement spectrometer with a Zeeman background corrector. The maximum amounts of salts causing no change in the integral atomic absorption and no corrector errors in using the universal Pd-Mg-modifier and varying the internal argon flow have been determined. They range for different elements from a few thousand of micrograms to tens. Comparison, as to this index, with the longitudinally heated atomizer HGA has been made. In many cases, the THGA is much better than the HGA.     

The absolute thermoelectric power of polyvalent liquid metals

Results on the measurement of the absolute thermoelectric power of ten polyvalent liquid metals (Al, Bi, Cd, Ga, Hg, In, Pb, Sn, Tl, Zn) from their melting points to about 750°C are reported. The electrical resistivities and the absolute thermoelectric powers of these metals have been calculated using the latest available data on structure factor and Harrison and Animalu form factors. These are compared with the experimental values. It is seen that whereas the predicted and experimental values of the electrical resistivities are in reasonable agreement, those for the absolute thermoelectric power are not. It is suggested that the experimental data on the absolute thermoelectric powers and the resistivities of liquid metals may be used to find the magnitude of the form factor at K = 2k _F.     

Pressure Dependence of the Transport and Magnetic Properties of Colossal Magnetoresistance Tl 2 Mn 2 O 7 Pyrochlore System

The Tl 2 Mn 2 O 7 pyrochlore system, pure or doped at the Tl position (Cd, Bi, Sc) or at Mn position (Sb, Te, Cr, Pb), present interesting magnetotransport properties characterized by the Colossal Magnetoresistance (CMR) effect. Our data for Tl 2 Mn 2 O 7 and Tl 1.9 Bi 0.1 Mn 2 O 7 indicate a decrease of the ordering temperature, measured from resistivity and magnetic susceptibility up to 70-90 kbars, with a clear increase of T C for higher pressures (up to 120 kbars). By contrast, in the case of Tl 2 Mn 1.8 Sb 0.2 O 7 , T C increases with pressure in the explored pressure range. A recent theory from Nuñez-Regueiro and Lacroix explains this dependence in terms of the existence of a second coupling mechanism between Mn ions, mediated by the conduction band (Tl (6s)). The doping at the Mn position (Sb) strongly increases the charge carrier density, so that this second coupling mediated by the conduction band, is strongly enhanced, in such a way that T C increases with pressure.     

Investigation of surface entropy for liquid less simple metals

We have derived an efficient expression in closed form for the surface entropy of liquid metals from the statistical mechanical theory of zeroth order involving hard sphere model interaction. Using this expression we have investigated the surface entropy for liquid less simple metals namely Zn, Cd, In, Sn, Pb, Sb, Tl and Bi selfconsistently. The effective hard sphere diameters are obtained from the thermodynamic perturbation theory called the LWCA. The prediction of the selfconsistent calculation improves significantly for all concerned systems except for Zn and Cd. The underlying cause of discrepancy for Zn and Cd is also discussed.     

Kinetic Approach to the Interpretation of Analyte Losses During the Preatomization Thermal Treatment in Electrothermal Atomization Atomic Absorption Spectrometry

A method for evaluating E_a(loss), the apparent activation energy of the analyte loss process during the high-temperature thermal pretreatment stage in electrothermal atomization atomic absorption spectrometry (ETA-AAS) has been developed. The method is based on extracting information from the declining portion of thermal pretreatment curves (in this case presented as absorbance vs pyrolysis time at various fixed temperatures). Five volatile analytes (As, Pb, Sb, Se, and Sn) have been studied in the presence of tungsten chemical modifier (20 μg of W in H₂O₂).

The data on E_a (loss) have been utilized together with those obtained from treating the atomization peaks E_a and with literature data on known values of bond energies and enthalpies of certain chemical reactions. Possible mechanisms of analyte losses and atomization are discussed.     

ICP-MS/ICP-AES法快速测定转基因棉花种子中的矿质元素和重金属含量

转基因植物生理生态已成为当前的研究热点,外源基因的导入可能会造成许多无法预料的结果。文章借助ICP-MS/ICP-AES技术对我国自己研制的转基因棉花和对照种子中的矿质元素和重金属进行了研究。结果显示,转基因棉花种子中,所测量的15种矿质元素含量有12种显著低于非转基因对照,说明转基因棉花种子吸收和累积矿质元素的能力下降;而只有镁、铁、铜含量高于对照。在测定的九种重金属(有害元素)中有七种转基因抗虫棉高于对照,特别是铝和砷的含量高出许多甚至上百倍,而铬和汞两种重金属含量明显低于对照。     

Positron annihilation in solid and liquid metals

The angular correlation of the gamma rays resulting from the annihilation of positrons in 15 solid and liquid metals and semiconductors has been studied. Experiments have been done on each material at room temperature and at temperatures above and below the melting point.

The elements investigated fall into three categories according to the way the angular correlation distribution changes as the melting point is reached. To within the experimental angular resolution (0.5 milliradians) no change in the angular correlation distribution is observed for Li, Se, Na, and Tl upon heating from room temperature to beyond the melting point. The elements Sb, Bi, Ga, Hg, Sn and Te exhibit changes in their angular correlation distributions only upon being melted, whereas for the metals Al, Cd, In, Pb and Zn changes occur when the specimen is heated from room temperature to temperatures below the melting point.

Changes in the angular correlation distribution upon heating or melting are generally manifested as (a) a narrowing of the central part of the curve, (b) a rounding-off of the parts of the curve near the Fermi cut-off angle and (c) a change in the area of the broad background curve as compared with the area under the central peak.     

Magnetic properties of a higher than second order superconducting phase transition

Based on the measurement of the magnetic characteristics of In−Bi, In−Tl, In−Pb, Sn−Bi and Sn−Sb superconducting alloys it was stated that the phase transition type I→ type II superconductivity is of higher than second order. Comparing the experimental data with the Lifshitz’s theory it is shown that the addition falls between the values of 0.63 and 0.77.

     

ICP-MS检测奶粉中多元素的干扰研究

研究了电感耦合等离子体质谱法(ICP-MS)检测奶粉中Ca、Fe、Zn、Mn、Cu、Ni、Ti、Al、Ba、Pb、As、Cd、Cr、Sn、Sb、Se、Tl等17种元素和15种稀土元素的干扰情况。通过碰撞反应和动能歧视,优化了仪器检测条件,最大程度的减少了多原子干扰和基体效应,采用多内标校正,有效抑制了分析信号的动态飘移。同时探讨了基质中共存元素P对Ti测定的影响。所有元素的加标回收率在87.8%—105.3%之间,相对标准偏差不大于6.3%。方法简便快捷,精密度好,准确性高,可完全满足奶粉中高含量元素和痕量元素同时检测的需要。     

ICP-MS在城市道路尘土中非常规监测微量元素污染评价中的应用

采集了石河子城区32个站点的道路尘土样本,测定了样品中10种非常规监测微量元素(B,Be,Bi,Co,Ga,Li,Sb,Sn,Tl,V)的含量。并采用地积累指数法、元素相关性分析和主成分分析法对尘土中的微量元素污染程度和来源进行了分析。结果表明：道路尘土中微量B,Be,Bi,Co,Ga,Li,Sb,Sn,Tl和V的平均含量分别为41.11,1.68,0.52,13.58,36.26,24.91,3.37,3.64,0.42,72.66 mg·kg-1。其中,Co,Li和Tl的平均含量均低于新疆土壤元素背景值,B,Be和V的平均含量和新疆土壤元素背景值相似,Bi,Ga,Sb和Sn的平均含量高于新疆和世界土壤元素背景值。地积累指数计算结果表明：B,Be,Co,Ga,Li,Tl和V污染级数为0,说明无污染,而Sb,Bi和Sn污染较为严重(污染等级分别为2,1,1)。元素相关性分析和主成分分析多元统计方法计算结果表明,Bi,Co,Sb和Tl主要是人为来源,B,Be,Li和V主要是自然来源,而Ga和Sn可能受自然因素和人为因素的共同影响。     

Diffusion effects in ion implanted germanium

During isochronal anneal sequences the number of Hg, Tl and Bi atoms implanted into Ge has been found to decrease. This decrease occurs for all three species and has been observed for samples implanted at room temperature as well as for hot implants (300—350°C). The decrease starts at anneal temperatures of 350—550°C. Similar results have been obtained for In and Sb implanted Ge. For samples implanted with Hg to doses leading to amorphous layers, the decrease in the number of implanted atoms seems to be related to the reordering of the amorphous layer. The experiments show that no diffusion of the implanted atoms into the bulk material occurs and the decrease observed is attributed to be a diffusion of the atoms to the surface followed by outdiffusion, thermal etching or both.     

A Rapid Method for the Determination of Trace Element Impurities in Silicons Oils by ICP-MS After Microwave-Assisted Digestion

Abstract

A microwave-assisted digestion procedure has been developed for the treatment of silicone oil samples. Inductively coupled plasma mass spectrometry (ICP-MS) was used to determine the concentration level of 40 trace element impurities, like Li, Na, Mg, Al, P, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Sr, Rb, Zr, Nb, Mo, Ag, Cd, Sn, Sb, Ba, La, Ce, Nd, Hf, W, Au, Pb, Hg, Th, Bi and U in these samples, having obtained average relative standard deviation values of 9.6%. The methodology developed has been tested by recovery studies on different natural samples spiked with known amounts of Mg, Cr, Mn, Fe, Zn and Pb at concentration levels of 10, 0.5, 5, 5, 10 and 1 μg g^?1 and recovery percentage values varies from 97 to 105 %.     

钯盐作为改进剂在微波消化-石墨炉原子吸收法测量食品中微量元素的应用

本文研究了钯盐作为改进剂在微波消化-石墨炉原子吸收法测量食品中微量元素As、Cd、Cr、Ni、Pb、Sb、Se、Sn的作用。实验发现钯盐的改进剂作用远好于其他情况。氯化钯加抗坏血酸对上述元素测量具有较好的改进作用,但受硝酸浓度影响很大。硝酸钯加硝酸镁在测量铬、镉、锡时效果较好,且受硝酸影响小。     

Dimers of heavy <Emphasis Type="Italic">p</Emphasis>-elements of groups IV–VI: Electronic,vibrational, and magnetic properties

Equilibrium lengths and binding energies, vibrational frequencies, width of the HOMO–LUMO gap, and the magnetic anisotropy energies for one- and two-component dimers of heavy p elements of Groups IV (Sn, Pb), V (Sb, Bi), and VI (Se, Te) with a pronounced relativistic effect have been calculated with the use of the formalism of the density functional theory. It has been shown that it is necessary to take into account the spin–orbit coupling, which significantly affects the energy parameters of clusters. The analysis of the data obtained has revealed that the Pb–Te, Pb–Se, Sn–Te, and Sn–Se dimers have the widest gap at the Fermi level and the lowest reactivity. The magnetic anisotropy energy has been calculated for all single- and doublecomponent dimers and the direction of the easy magnetization axis has been determined.     

Bi,Sn and Sb valence states in highT c (Bi,Pb/Sn,Sb)2Sr2Ca2Cu3Oy

The valence of Bi and its substituents Sn and Sb are investigated in the high temperature superconductor (Bi_0.8X_0.15Sb_0.05)₂Sr₂Ca₂Cu₃O_y (often denoted 2223) where X=Pb or Sn. Pb and Sn are isoelectronic with the valence states 2+ and 4+; Bi and Sb are as well with valence states 3+ and 5+. The valence state of Sn and Sb has been obtained from Mössbauer spectroscopy: they exist in the high charge states 4+ and 5+ respectively. Sn, Sb, and presumably Pb, take on the high valence state, and so furnish electrons to the conduction band. This is probably the reason why, although the (Pb, Sb)-doping aids in stabilizing the 2223 crystal structure, it is detremental to the electronic properties which lead to the superconducting phase. The valence state of Bi has been studied using X-ray photoelectron spectroscopy (XPS). These results show clearly that the Bi-based superconductor has a metal-like density of states at the Fermi level, and that the valence in the (Pb, Sb)-doped compounds is less than 3. This very surprising change in valence will have a profound effect on the superconducting properties, and is probably associated with the high valent states of Pb, Sn and Sb.     

ICP-MS法测定采血管中的20种微量元素

采用ICP-MS法对国内市场常用的13种采血管中铝、钒、铬、锰、铁、钴、镍、铜、锌、砷、硒、钼、镉、锡、锑、钡、钨、汞、铊和铅元素进行测定。通过对采血管的纯水浸出液和10%硝酸浸出液进行20种微量元素含量分析,得到了13种采血管中20种微量元素的含量。根据近年发表的文献中有关人体血清、血浆和全血微量元素含量参考范围,详细分析了各种采血管适用的微量元素检测种类。分析结果表明：最适用于血清分析的为采血管1,该采血管适用于18种血清微量元素的分析;最适用于血浆分析的为采血管6,该采血管适用于15种血浆微量元素的分析;最适用于全血分析的为采血管13,该采血管适用于17种全血微量元素的分析。但是,值得注意的是,采血管1中的锑和钨元素,采血管6中的钒、铬、镍和锑元素,以及采血管13中的铝,锑和钨元素,其纯水浸出液中这几种微量元素的含量与正常人血液(血清、血浆、全血)中微量元素含量处于同一数量级,可能会对血液微量元素的测量结果造成影响。该研究也对比了采血管1和采血管3对实际血清样本检测结果的影响,结果表明,采血管1的检测结果中几乎所有微量元素含量都低于采血管3的检测结果,尤其是铝,钒,铬,锰,砷,锡,锑等几种元素,说明在实际采血过程中,采血管的选择对微量元素检测结果影响很大。