ICP-MS determination of lead isotope ratios in legal and counterfeit cigarette tobacco samples

A method for the determination of Pb isotope ratios (IR) in cigarette tobacco by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) has been developed and applied to tobacco samples from genuine and counterfeit cigarettes obtained in the USA. The IR ²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb were measured using a Q-ICP-MS instrument. Two certified reference materials, grown in the USA and Bulgaria, were also analysed for comparison with the tobacco samples, as were tobacco samples from cigarettes obtained in Pakistan and China. The precision of the results was sufficient to distinguish between the counterfeit and genuine USA cigarettes. All of the genuine cigarettes and both reference materials, grown in different regions, were statistically distinct based on the measured ratios. The counterfeit cigarettes were indistinguishable from the reference material grown in Bulgaria. The technique shows promise as a method for identifying counterfeit cigarettes, possibly determining the source region.     

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.     

Simultaneous qualitative and quantitative analysis of counterfeit and unregistered medicines using Raman spectroscopy

Raman spectroscopy was used to classify a group of seized counterfeit medications associated with erectile dysfunction. Using appropriate data preprocessing, principal component analysis and the classification method soft independent modelling of class analogy (SIMCA), it was possible to classify genuine from unregistered generic and counterfeit Cialis® batches. However, SIMCA did not effectively classify samples on the basis of their active pharmaceutical ingredient (API). Partial least squares discriminant analysis, principal component regression and support vector machines effectively distinguished between the API of the samples but were unable to correctly distinguish all samples as genuine or generic/counterfeit. This study highlights the importance of choosing the correct preprocessing procedures and classification method for the data set. Despite diverse tablet contents in addition to the drug, it was possible to quantify the levels of drug in the medicines as high, medium or low (within ±20 mg g⁻¹ tablet concentration). Overall, the potential for Raman spectroscopy combined with multivariate analysis for qualitative and semiquantitative analysis of counterfeit medicines was demonstrated, and the approach may be used to determine the potential level of harm in counterfeit medicines on the basis of API identity and amount. Copyright © 2013 John Wiley & Sons, Ltd.     

近红外光谱的主成分分析-马氏距离聚类判别用于卷烟的真伪鉴别

为了快速准确的鉴别卷烟真伪,以A牌和假冒A牌卷烟为实验材料,采用近红外光谱法结合主成分分析-马氏距离判别分析方法建立了鉴别模型.首先对经过预处理的光谱数据进行主成分分析,分析结果表明,前4个主成分的累积贡献率已达98.46%,说明这4个变量能够代表原始光谱的主要信息.从120个样品中随机抽取100个用于建立4个主成分变量的定性判别模型,模型的相关系数达到了0.95,对20个未知样品的预测结果准确率为100%.说明近红外光谱结合模式识别方法进行卷烟真伪定性鉴别在技术上是可行的,可以作为卷烟真伪鉴别的一种辅助手段.     

Fast detection and identification of counterfeit antimalarial tablets by Raman spectroscopy

During the last decade there has been an apparent increase in the prevalence of counterfeit medicines in developing as well as developed countries. The pivotal antimalarial artesunate has been counterfeited on a large scale in SE Asia. In this work, the possibilities of Raman spectroscopy are explored as a fast and reliable screening method for the detection of counterfeit artesunate tablets. In this study, 50 ‘artesunate tablets’, purchased in SE Asia, were examined. This spectroscopic method was able to distinguish between genuine and counterfeit artesunate and to identify the composition of the counterfeit tablets. These contained no detectable levels of artesunate, but consisted mostly of starch, calcite (CaCO₃), and paracetamol (4‐acetamidophenol). In one particular case an admixture of rutile (TiO₂) and artesunate was detected. The results of the investigation by Raman spectroscopy were in agreement with those of colorimetric tests and of liquid chromatography‐mass spectrometry on the artesunate. Moreover, principal components analysis (PCA) was combined with hierarchical cluster analysis to establish an automated approach for the discrimination between different groups of counterfeits and genuine artesunate tablets. These results demonstrate that Raman spectroscopy combined with multivariate analysis is a promising and reliable methodology for the fast characterization of genuine and counterfeit artesunate antimalarial tablets. Copyright © 2006 John Wiley & Sons, Ltd.     

基于近红外光谱特征的三文鱼品质多指标快速检测

三文鱼肉质鲜美、营养丰富，尽管价格昂贵，却深受广大消费者喜爱，2017年我国三文鱼进口额达3.5亿美元。近年来不法商贩为追求高额利润导致三文鱼消费市场“以假乱真”、“以次充好”的问题日益突出，主要表现为：(1)以价格低廉、外观相似的淡水虹鳟、大马哈鱼、太平洋鲑鱼等冒充价格高、消费者认可度高的挪威三文鱼；(2)将低成本、低品质的冰冻三文鱼(-18 ℃储运、保质期长、组织结构被冰晶破坏、口感风味破坏严重)化冻后冒充高成本、高品质的冰鲜三文鱼(0～4 ℃储运、保质期短、无冰晶产生、口感风味最大限度保持)；(3)将次新鲜的三文鱼冒充新鲜三文鱼。针对三文鱼品质感官检测误差大、理化检测耗时费力的不足，拟研究一种基于近红外光谱(NIRs)特征的真品/伪品三文鱼、冰鲜/冻融三文鱼、新鲜/次新鲜三文鱼快速鉴别方法。首先采集真品(挪威三文鱼)/伪品(淡水虹鳟、大马哈鱼和太平洋鲑鱼)三文鱼、冰鲜(冰鲜1，3和5 d)/冻融(冰冻15，30和45 d并化冻)三文鱼和新鲜/次新鲜(冰鲜保藏0，2，4，6和8 d)三文鱼样品的NIRs信息，并将不同储藏天数的冰鲜三文鱼以国标法测定其TVB-N含量。原始光谱经标准正态变量变换(SNV)等方法预处理后，分别使用主成分分析(PCA)和遗传算法(GA)进行光谱数据降维及特征波长筛选。最后，结合K-最近邻法(KNN)和最小二乘支持向量机(LS-SVM)对真品/伪品三文鱼和冰鲜/冻融三文鱼构建识别模型；结合联合区间偏最小二乘法(Si-PLS)对新鲜/次新鲜三文鱼构建TVB-N预测模型。建模结果表明：真品/伪品三文鱼LS-SVM定性识别模型对应的测试集识别率达97.50%，冰鲜/冻融三文鱼LS-SVM定性识别模型对应的测试集识别率达98.89%；TVB-N对应的Si-PLS定量检测模型的预测集相关系数为0.864 1，基于TVB-N预测值建立的三文鱼新鲜度定性鉴别模型对应的测试集准确率为90.00%。研究结果表明，利用近红外光谱特征结合化学计量学方法能够快速、无损检测真品/伪品三文鱼、冰鲜/冻融三文鱼和新鲜/次新鲜三文鱼，实现三文鱼品质多指标快速检测。     

基于元素对研究激光剥蚀-电感耦合等离子体质谱分析硫化物矿物的基体效应

基体效应是影响LA-ICP-MS分析结果准确性的主要因素之一,但目前却没有一种量化基体效应研究的方法。提出了一种以分析元素与内标元素的强度比(I_i/I_is)为纵坐标、浓度比(c_i/c_is)为横坐标绘制I_i/I_is-c_i/c_is图,以元素对I_i/I_is-c_i/c_is图的线性相关系数ｒ量化基体效应的思路。以Fe为内标,考察了13个常用玻璃标准物质与2个硫化物标准及多个硫化物矿物中6个元素对的基体效应,结果显示Cu/Fe和Zn/Fe的线性相关系数r都小于0.99,而痕量元素对Mn/Fe,Co/Fe,Ga/Fe,Pb/Fe的线性相关系数r都大于0.999;以S为内标,考察了2个硫化物标准与多个硫化物矿物中三个主量元素对Fe/S,Cu/S和Zn/S的基体效应,结果显示其线性相关系数r都小于0.999。无论是以Fe为内标结合玻璃标准为外标,还是以S为内标结合硫化物标准为外标分析硫化物矿物,主量元素大多数分析结果的误差大于10%;而以Fe为内标时,绝大多数玻璃标准获得的痕量元素分析结果与MASS-1较为一致,误差小于15%。研究表明,玻璃标准及硫化物矿物标准均与硫化物矿物存在一定的基体效应差异,而采用元素对I_i/I_is-c_i/c_is图的线性相关系数r量化基体效应具有一定的合理性与实用性。研究也表明了以Fe为内标,采用非基体匹配的玻璃标准可用于定量分析硫化物矿物中的痕量元素,尤其是具有较高痕量元素含量的NIST610。     

葡萄糖与脯氨酸的梅拉德反应物致香成分分析及其在造纸法再造烟叶中的应用

制备了等摩尔的D-葡萄糖和L-脯氨酸在温度95-100℃条件下反应4h的梅拉德反应产物.采用同时蒸馏萃取法对反应产物中的致香成分进行GS/MS分析,并用该产物进行了造纸法再造烟叶加香实验,且将加香后的造纸法再造烟叶样品添加在卷烟配方中进行了评吸.在D-葡萄糖和L-脯氨酸的梅拉德反应产物中一共鉴定出了19个化学物,主要包...     

Determination of Pb,As, Cd and trace elements in polluted soils near a lead–zinc mine using polarized X‐ray fluorescence spectrometry and the characteristics of the elemental distribution in the area

Polarization energy dispersive X‐ray fluorescence spectrometry was used in the determination of Pb, As and Cd, as well as Cr, Cu, Zn, Ni and other minor and trace elements in the soil samples taken from a polluted area by lead mine exploitation. Two difficulties have to be overcome. One is strong overlap of Pb Lα over As Kα and another is lack of suitable certified reference materials. The different excitation conditions and analytical lines were tried to reduce the impact of overlap of Pb Lα over As Kα. When KBr was used as the second target, compared with Zr, the proportion from Pb Lα was reduced about six times. Even so, however, the overlap was not reduced enough to be ignored. The inductively coupled plasma atomic emission spectrometry and mass spectrometry methods were used to analyze parts of soil samples and provide data for compensating lack of reference materials. By this method, the analytical concentration range of Pb, As and Cd were significantly extended. The analytical range of Pb, As and Cd were 1.4 µg/g~4.2%, 0.6 µg/g~9.3% and 0.5 µg/g~1500 µg/g, respectively. The high concentrations of Pb, As and Cd were found in the samples in the vicinity of the Pb‐Zn mine. The concentrations of Pb, As, Cd, Zn and Cu were higher than the Class III in the Chinese environmental quality standard for soils. The highest concentrations of Pb, As, Cd and Zn in the soil samples were 14 960, 2726, 65 and 9439 µg/g, respectively. Copyright © 2012 John Wiley & Sons, Ltd.     

Using Raman Spectroscopy for Determination Methanol Quantity in Illegal Alcoholic Beverages

Illegal production of alcoholic beverages is a common problem in most countries.The consumption of these counterfeit alcoholic products in Turkey has increasingly been one of the major health concerns.In this study,a comparison between GC-MS and Raman spectroscopy techniques was made to determine the amount of methanol in BogmaRaki which is a counterfeit alcoholic beverage produced and consumed in Hatay region. Different ratios of methanol/ethanol concentrations were prepared to obtain a calibration curve.This curve was used to measure the amount of methanol in the actual product samples using both GC-MS and Raman spectros-copy techniques.Results obtained from both techniques were compared using Paired sample t-tests.The Limit of Detection and the Limit of Quantification values were determined as 0.03 (%v/v)and 0.11 (%v/v),re-spectively.Both techniques demonstrated a similar sensitivity in the determination of methanol concentration in these counterfeit products (p>0.05).Raman Spectroscopy,however,has an advantage of being easy to use, inexpensive,rapid and non-destructive analytical technique with little or no sample preparation.     

高效液相色谱测定卷烟及其主流烟气中的维生素E

样品用饱和抗坏血酸乙醇溶液萃取,ZORBAX Extend-C18（5μm,4.6×150mm）色谱柱及FLD检测器在激发波长为298nm,发射波长为325nm下检测,流动相为100%甲醇。采用外标法定量,线性相关系数为0.99996,检出限为0.12μg/mL,卷烟及其主流烟气中维生素E平均回收率分别为97.0%和97.4%,RSD分别为0.70%和4.70%。研究表明：烤烟型卷烟烟丝比混合型卷烟烟丝中维生素E含量高,烤烟型卷烟主流烟气比混合型卷烟主流烟气中维生素E含量高,维生素E从卷烟烟丝到主流烟气的迁移率为7%—16%。     

从吸食前后香烟中微量元素含量的变化看吸烟的危害

香烟中的烟丝(吸食前)和其燃烧后的烟灰(吸食后),经过HNO₃+HClO₄消解后,用火焰原子吸收光谱法测定了吸食前后香烟中矿物元素(Cu,Fe,Zn,Mg,Mn,Ca,K,Ni,Cd,Cr,Pb和Co)的含量变化。实验结果表明,香烟中各种矿物元素之间的含量以及吸食前后均有差异, 尤其是对人体有害的铅和镉元素变化较大, 吸食后平均分别降低了26.4%和44.2%。说明香烟中这二种元素吸食以后减少的那部分进入了人体的呼吸系统和空气环境。     

高光谱成像的纸币真伪鉴别研究

人民币是中华人民共和国的法定货币,人民币的真假直接关系到我国社会的和谐与稳定。百元钞票作为我国最大面额钞票,其真假的鉴定显得更为重要。以2005版的百元钞票为例,利用可见/近红外高光谱成像仪获取一张真钞与两张假钞正、背面高光谱影像数据,然后分别在百元钞票的正、背面选取4个特征点,以分析百元真假钞票在正、背面的光谱反射率差异。从真假钞正面四个特征位置的光谱反射率曲线可知,不同特征点处,真钞与假钞之间的有些图案的光谱反射率差异较大,有些图案的光谱反射率则差异并不显著。而不同批次的假钞,其不同位置的光谱反射率也存在较大的差异。对于真假钞背面的分析可知,不同特征点,在不同的波段,真钞与假钞以及假钞之间的光谱反射率同样有一定的差异。根据真钞与假钞正、背面8个特征点的光谱反射率曲线变化特征,选取500,660和870 nm三个波长的灰度图,观察到真钞与假钞在不同特征点的灰度图均表现出明显的差异。真钞在500 nm处的图像轮廓清晰,在660和870 nm两个波长,无论是正面或背面,真钞均有多处特征位置有异于假钞,因此可用660或870 nm区别百元真假钞。为了突出真钞与假钞之间的图像差异,利用基于波段运算得到百元真钞与假钞的灰度图。由图可知,在正、背面上,真钞在多个地方均区别于假钞。由真假钞正面的前12个主成分的灰度图可知,无论从真、假钞正面或是背面,每一主成分均有真钞显著区别于假钞的地方。根据真假钞正背面的纹理特征图可知,真钞的纹理特征显著区别于假钞。研究表明百元真钞与不同版本的假钞在可见/近红外光谱范围内光谱反射率差异显著,近红外特征波段、光谱运算、主成分分析、纹理特征等技术均可探寻到百元真假钞在正、背面存在的位置差异。由此可知,可见/近红外高光谱成像技术可实现不同版本百元真假钞的鉴定,并为假币的溯源提供了可能性和理论支持,此技术在公安实战中具有实际意义。     

二维相关红外光谱技术快速鉴别三七及其伪品

采用红外光谱法并结合二维相关红外光谱技术,对三七及其伪品姜黄、白术进行了快速无损的鉴别研究。在一维红外谱图上,三七及其伪品姜黄、白术中的黄酮成分、芳香成分和糖苷类成分的特征吸收峰均存在一定的差异。在1200~700cm~(-1)波数范围内,三七、姜黄均出现淀粉的特征峰,而白术没有显示淀粉的特征峰,根据各药材的红外光谱中淀粉的特征峰的相对强度,可判断三七中淀粉的相对含量要高于姜黄,而白术药材中不含淀粉。在二维红外谱图上,根据三者的自动峰的位置、数量和峰的相对强度的差异,可快速将三者鉴别出来。因此,常规红外光谱法和二维相关红外光谱技术相结合可实现三七的真伪鉴别。     

近化学计量比Ce∶Mn∶LiNbO3晶体光折变性能研究

在LiNbO3中掺进0.015mass%MnCO3和 0.1mass%CeO2,以Czchralski法生长Li/Nb比为1.38的近化学计量比Ce∶Mn∶LiNbO3(Ce∶Mn∶SLN)晶体和Li/Nb比为0.946的同成分Ce∶Mn∶LiNbO3(Ce∶Mn∶CLN)晶体.测试了晶体的红外光谱和紫外可见吸收光谱,讨论了Ce∶Mn∶SLN晶体OH－吸收峰和吸收边移动机理.利用二波耦合光路测试了晶体的指数增益系数,Ce∶Mn∶SLN晶体指数增益系数Γ达到27 cm2－.同时,研究了Ce∶Mn∶SLN指数增益系数提高的机理.     

微型柱现场预富集流动注射火焰原子吸收测定环境水样中的铅和镉

文章以负载8-羟基喹啉(8-HQ, Oxine)、二乙基二硫代氨基甲酸盐(DDTC)和吡咯啶二硫代氨基甲酸铵(APDC)三种螯合剂的活性炭(AC)为微型柱的吸附材料,采用微型柱现场采样 (MFS)分析技术实现了连续现场富集环境水样中的痕量Pb和Cd,并在实验室中采用流动注射(FI) -火焰原子吸收(FAAS)联用技术对吸附柱中富集的Pb和Cd进行测定。该方法用于水中微量元素(GBW—08608)和南湖水样中Pb和Cd的测定均获得了满意的结果。10 mL富集的检出限(3σ)Pb：1.58 μg·L-1;Cd：0.062 μg·L-1 ,相对标准偏差Pb：1.62%;Cd：1.96%。     

鸢尾根致香成分分析及在造纸法再造烟叶中的应用

采用同时蒸馏萃取法,从鸢尾根中提取致香成分,对其主要化学成分进行GC/MS分析,用鸢尾根致香成分进行了造纸法再造烟叶加香试验,并将加香后的造纸法再造烟叶样品添加在卷烟配方中进行评吸。结果表明,鸢尾根致香成分中共鉴定出17个化合物,主要含有癸酸和棕榈酸;鸢尾根致香成分能改善造纸法再造烟叶的烟气品质,并具有降低刺激的作用,加香后的造纸法再造烟叶在卷烟中应用也具有相同的效果。     

UV–visible,infrared absorption spectra of undoped and TiO2-doped lead phosphate glasses and the effect of gamma irradiation

Undoped and TiO₂-doped lead phosphate glasses were prepared. Ultraviolet (UV)–visible and Fourier transform-infrared (IR) absorption spectra of the prepared samples were measured before and after being subjected to doses of 30 and 60 kGy of gamma irradiation. The parent undoped lead phosphate glass reveals charge transfer UV absorption bands which are attributed to the presence of unavoidable iron impurities contaminated within the raw materials used for the preparation of the glasses and the sharing of divalent lead (Pb²⁺) ions. Experimental spectral data indicate that the doped titanium ions are involved in such glasses in two valences, namely the trivalent and tetravalent states. The predominant trivalent titanium (Ti³⁺) ions are characterized by its purple color and exhibiting two visible absorption bands at about 500–550 and 700–720 nm. The lesser tetravalent titanium (Ti⁴⁺) ions belong to the d⁰ configuration and generally exhibit only an UV absorption band. Spectral data show that gamma irradiation causes noticeable changes in the undoped and TiO₂-doped samples in the UV range while the effects are limited in the visible range. The observed changes in the UV region are attributed to photochemical reactions while TiO₂-doped samples show retardation or shielding toward continuous gamma irradiation together with the sharing of heavy Pb²⁺ ions. IR absorption spectra reveal the vibrations of several phosphate groups including the metaphosphate chains as the main structural building units together with the possible Pb?O vibrations.     

Po and Pb concentration of cigarettes traded in Hungary and their estimated dose contribution due to smoking

It is known that tobacco leaves may contain ²¹⁰Pb and ²¹⁰Po in significant concentrations. The cumulative alpha-radiation dose due to the radioactive content of inhaled cigarette smoke and the increasing number of lung cancer cases explain the importance of the investigation. The present study investigated the activity concentrations of these two radionuclides in 29 Hungarian cigarette samples. The relation between ²¹⁰Po/²¹⁰Pb activity and nicotine/tar content of these cigarettes was also examined. ²¹⁰Po was determined by alpha spectrometry using a PIPS detector after chemical leaching and spontaneous deposition of ²¹⁰Po on a high nickel-content (25%) stainless steel disk. The ²¹⁰Pb activity was calculated from the ²¹⁰Po originated from the decay of ²¹⁰Pb after a waiting period of eight months. The ²¹⁰Po activity concentrations of the measured types of cigarettes ranged from 10.0 to 33.5 mBq/cigarette, and the activity of ²¹⁰Pb varied from 9.6 to 32.5 mBq/cigarette. The average annual committed effective dose is estimated to be $185.6\pm 70.6\mathrm{\mu }\mathrm{Sv}/\mathrm{y}$ and $58.7\pm 22.7\mathrm{\mu }\mathrm{Sv}/\mathrm{y}$ due to cigarette smoking (20 cigarettes/day) for ²¹⁰Po and ²¹⁰Pb, respectively.     

水体中铬、镉和铅的X射线荧光光谱同时快速分析方法研究

以氢氧化钠和硫化钠为沉淀剂采用共沉淀法同时富集水体中的Cr,Cd和Pb,通过对Cr(OH)₃,Cd(OH)₂和PbS沉淀均匀悬浮液抽滤以制成Cr,Cd和Pb均匀分布的薄膜样品并进行能量色散XRF光谱测量,以实现水体中Cr,Cd和Pb的同时快速分析与检测。研究了富集过程中的反应时间和反应物摩尔比对薄膜样品XRF光谱强度的影响,确定了富集过程的最佳反应条件为沉淀反应时间为5 min,OH-与Cr3+的最佳摩尔比为5.0,OH-与Cd2+的最佳摩尔比为5.0,S2-与Pb2+的最佳摩尔比为2;对富集后不同浓度的薄膜样品进行了均匀性检验,富集区域6个不同位置荧光强度的相对标准偏差均小于4.8%,说明富集后的薄膜样品具有较好的均匀性;将不同浓度薄膜样品的理论浓度值与ICP-MS方法测得的浓度值进行对比分析,验证了该富集方法对水样中Cr,Cd和Pb的富集率均能达到90%以上;根据薄膜样品的荧光强度与ICP-MS测得的浓度值,建立了基于该富集方法的水体中Cr,Cd和Pb的X射线荧光光谱定量分析方法,Cr,Cd和Pb校准曲线的线性相关系数分别为0.997 3,0.995 0和0.999 8,当实际采集水样体积为50 mL时,Cr,Cd和Pb的检出限分别为7.4,29.6和8.5 μg·L-1,均低于《污水综合排放标准 GB 8978-1996》中Cr,Cd和Pb的最高允许排放浓度,因此该方法能够实现工业生产及生活排放污水中Cr,Cd和Pb的同时快速分析与检测。该研究为基于X射线荧光光谱法的水体多种重金属同时快速在线监测提供依据。