血、尿中金属毒物的电感耦合等离子发射光谱检测方法

目的建立血和尿中的有毒金属元素快速检测方法。方法通过模拟样品,采用微波消解炉对样品进行预处理,用电感耦合等离子发射光谱仪同时对多种可疑有毒金属元素进行检测。结果血、尿样品经消解或酸稀释处理,镉、钴、铬、铜、镍等元素可检测方法平均回收率范围为75.5%～127.5%,变异系数小于16.4%结论在中毒剂量,对肝脏和肾脏组织中的可疑有毒金属元素,可以采用电感耦合等离子发射光谱仪同时进行检测。     

生物样品中的金属毒物电感耦合等离子发射光谱检验

目的建立有毒金属元素在肝、脾和肾脏组织中的快速检测方法。方法通过模拟样品,采用微波消解炉对样品进行预处理,用电感耦合等离子发射光谱仪同时对多种可疑有毒金属元素进行检测。结果在中毒剂量,对肝脏和肾脏组织中的可疑毒金属元素,可以采用电感耦合等离子发射光谱仪进行检测。     

激光剥蚀电感耦合等离子体质谱技术检测车辆油漆金属元素

目的建立车辆油漆的激光剥蚀电感耦合等离子体质谱（laser ablation inductively coupled plasma mass spectrometry,LA—ICP—MS）分析方法。方法对38种车辆油漆样品采用激光剥蚀,电感耦合等离子体质谱进行测定,通过各油漆样品本含有金属元素种类和金属元素响应相对比值的差异对油漆样品进行区分。结果38种样品中有30种可直接依据所含金属元素种类的差异进行对其进行区分,其余8种依据元素间响应值比值的差异进行区分,方法重现性良好,精密度（RSD）小于10％。结论所建立的LA—ICP—MS方法简便快速、精密度良好、对样品微损,适用于法庭科学对车辆油漆的检测。     

微波消解ICP-MS法测定人发中的汞

目的建立人发中汞的电感耦合等离子体质谱分析方法。方法采用微波消解法处理样品,以铟（115In）作内标,用电感耦合等离子体质谱分析人发中的汞含量。结果方法检出限为0.0032μg/g,准确度通过测定人发标准物质GBW07601、GBW09101b进行验证,检测结果与标准参考值相符。结论该方法快捷、高效,灵敏度、准确度高,适用于人发中汞含量的检测。     

微波消解ICP-MS法测定人头发中24种元素的含量

目的建立人头发中24种无机元素的电感耦合等离子体质谱（inductively coupled plasma-mass spec-trometry,ICP-MS）分析方法。方法采用微波消解法处理样品,以铟（115In）作内标,用ICP-MS分析人头发中的24种元素含量。同时检测56例健康志愿者和10例海洛因滥用者头发中24种元素含量。结果 24种元素的方法检出限范围为0.0003~10.14μg/g,标准物质的测得值与标准值基本相符。海洛因滥用者经戒毒治疗后头发中镁、镓、钡含量下降。结论该方法灵敏度、准确度高,适用于头发中24种元素的测定。     

加热板消解-ICP-MS检测血液中的33种元素

目的 对比微波消解方法,建立加热板消解-电感偶等离子体质谱法（inductively coupled plasma-mass spectrometry,ICP-MS）检测血液中33种元素的方法.方法 以双氧水和浓硝酸为消解试剂,分别采用微波消解和加热板加热的湿法消解方法,对血液进行消解后检测,对两组结果进行t检验.结果 两种前处理方法无显著性差异,所建立的加热板加热消解方法,其33种元素方法检出限为0.0002 ng/mL （Cs） ～ 21.8 ng/mL（Ca）,准确度为91％～112％,日内精密度为0.5％～8.9％,日间精密度为0.4％～10.9％.结论 加热板消解方法简单准确,适用于大量样本的检测.     

应用等离子发射光谱分析技术测定人体组织中的汞含量

汞中毒案件的传统分析是将洁净的铜片或铜丝放入酸性检材试料中煮沸,如表面被一层银灰色沉积物所覆盖,则可以证实检材中含有汞。也可做汞的升华实验来确定汞的存在。用原子吸收光谱仪、原子发射光谱仪、扫描电子显微镜、离子色谱法等分析技术来确定汞的存在与定量,检材需要一定的前处理,有些只能进行半定量分析。本文在改进湿法消化人体生物组织样品(肝、肾)方法的同时,应用等离子体发射光谱分析技术测定人体组织中的汞含量,此法具有可靠、准确、简便、快速、抗干扰性强等特点,同时还可对多种有毒金属元素进行定性、定量。     

微波消解ICP-MS法检测生物检材中汞元素

目的 建立生物检材中汞的电感耦合等离子体质谱分析方法.方法 采用微波消解法处理样品,以铟(115In)作内标,用电感耦合等离子体质谱仪对血液、尿液和头发中的汞含量进行分析.选择金与汞形成金汞齐,对金消除汞记忆效应的能力进行考察.结果 方法检出限为0.01μg/L,准确度为97.0%～107.1%.检测中添加金质量浓度在...     

微波消解ICP/AES标准加入法测定尿液中金属毒物

目的建立微波消解ICP/AES标准加入法测定尿液中As、Ba、Pb、Cd、Cr、Zn、Sb金属毒物。方法取1.0mL尿样,加入3mL浓硝酸和0.5mL双氧水,进行微波消解。冷却后,用2%的硝酸定容至10.0mL。采用标准加入ICP/AES法进行定量分析,并优选实验条件及考察方法可靠性。结果尿液中As、Ba、Pb、Cd、Cr、Zn、Sb回收率在98.6%～104%之间;检出限在2.0～5.1ng/mL之间;线性范围Zn为5.0～200.0μg/mL,其余元素为0.5～20.0μg/mL。采用本文方法测定与国家标准物质人发和牛肝数据测定值基本一致。结论该方法回收率高、检测限低、能多元素同时测定,可以用于尿液中金属元素的检测。     

电热板消解电感耦合等离子体质谱法测定人发中33种无机元素的含量

目的建立头发中33种无机元素的电热板消解电感耦合等离子体质谱（inductivelycoupledplas—ma—IllasssDectrometry,ICP—MS）测定方法。方法以锂（6Li）、锗（^72Ge）、钇（^89Y）、铟（^115In）、铽（^159yb）作内标,硝酸和过氧化氢作为消解酸体系．采用电热板消解对头发进行前处理,ICP—MS法分析人发中33种无机元素的含量。结果电热板消解ICP—MS法的检出限为0．0001μg／g（Th）-10．9μg／g（Ca）,定量限为O．0005μg／g（Th）～25μg／g（Ca）,加标回收率为86％～113％,日内及日间精密度≤9.2％,与微波消解法检测结果相比,差异无统计学意义。结论电热板消解ICP—MS法高效、准确度高,适用于对头发中33种无机元素的分析。     

Development and evaluation of a standard method for the quantitative determination of elements in float glass samples by LA-ICP-MS

Forensic analysis of glass samples was performed in different laboratories within the NITE-CRIME (Natural Isotopes and Trace Elements in Criminalistics and Environmental Forensics) European Network, using a variety of Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) systems. The main objective of the interlaboratory tests was to cross-validate the different combinations of laser ablation systems with different ICP-MS instruments. A first study using widely available samples, such as the NIST SRM 610 and NIST SRM 612 reference glasses, led to deviations in the determined concentrations for trace elements amongst the laboratories up to 60%. Extensive discussion among the laboratories and the production of new glass reference standards (FGS 1 and FGS 2) established an improved analytical protocol, which was tested on a well-characterized float glass sample (FG 10-1 from the BKA Wiesbaden collection). Subsequently, interlaboratory tests produced improved results for nearly all elements with a deviation of < 10%, demonstrating that LA-ICP-MS can deliver absolute quantitative measurements on major, minor and trace elements in float glass samples for forensic and other purposes.     

Lower limits of detection of synchrotron radiation high-energy X-ray fluorescence spectrometry and its possibility for the forensic application for discrimination of glass fragments

Synchrotron radiation high-energy X-ray fluorescence (SR-XRF) analysis utilizing 75.5keV X-ray radiation from beam-line BL37XU at Super Photon Ring 8GeV (SPring-8), a third-generation synchrotron facility, was found to have advantages for forensic discrimination of glass samples. The lower limits of detection (LLD) for calibration curves were at the picogram level for Ba, Ce, and Sm and at the 10pg level for Sr, Zr, Sn, and Hf. The spectrum of NIST SRM 612 glass reference material demonstrated K-line peaks of 31 elements including rare-earth elements, and the relative standard deviations (R.S.D.) of all the measured elements except Ca were less than 9.7%. Fragments of collected sheet glass were used as samples for investigating the application of this technique to forensic analysis. Several trace elements such as Pb, Rb, Sr, Zr, La, Ce, and Hf were detected in the spectra of the samples, and these elements could be used as indexes to characterize the glass samples. But the "lower limits of detection (LLD)" of each element were not examined enough. In this report, these limits by synchrotron radiation X-ray spectrometry were clarified. By these results, this technique should provide an effective approach to the nondestructive discrimination of small glass fragments in the field of forensic science.     

Comparison of glass fragments using particle-induced X-ray emission (PIXE) spectrometry

A procedure has been developed to analyze the trace element concentrations in glass fragments using particle-induced X-ray emission (PIXE) spectrometry. This method involves using accelerated protons to excite inner-shell electronic transitions of target atoms and recording the resultant X-rays to characterize the trace element concentrations. The protocol was able to identify those glass fragments that originated from different sources based on their elemental analyses. The protocol includes specific approaches to calculating uncertainties and handling measurements below the level of detection. The results indicate that this approach has increased sensitivity for several elements with higher atomic number compared with X-ray fluorescence methods. While not as sensitive as laser-ablation or inductively coupled plasma mass spectrometry methods of dissolved samples, it is entirely nondestructive and entails a much simpler sample preparation process that may be used to presort glass fragments for more comprehensive elemental analysis. As such, the technique described may have a niche role in forensic glass analysis.     

Analysis of glass fragments by laser ablation-inductively coupled plasma-mass spectrometry and principal component analysis

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is used to differentiate glass samples with similar optical and physical properties based on trace elemental composition. Laser ablation increases the number of elements that can be used for differentiation by eliminating problems commonly associated with dissolution and contamination. In this study, standard residential window and tempered glass samples that could not be differentiated by refractive index or density were successfully differentiated by LA-ICP-MS. The primary analysis approach used is Principal Component Analysis (PCA) of the complete mass spectrum. PCA, a multivariate analysis technique, provides rapid analysis of samples without time-consuming pair-wise comparison of calibrated analyses or prior knowledge of the elements present in the samples. Probabilities for positive association of the individual samples are derived from PCA. Utilization of the Q-statistic with PCA allowed us to distinguish all samples within the set to a certainty greater than the 99% confidence interval.     

Lead Theft—A Study of the “Uniqueness” of Lead from Church Roofs

In the United Kingdom, theft of lead is common, particularly from churches and other public buildings with lead roofs. To assess the potential to distinguish lead from different sources, 41 samples of lead from 24 church roofs in Northamptonshire, U.K, have been analyzed for relative abundance of trace elements and isotopes of lead using X‐ray fluorescence (XRF) and inductively coupled plasma mass spectrometry, respectively. XRF revealed the overall presence of 12 trace elements with the four most abundant, calcium, phosphorus, silicon, and sulfur, showing a large weight percentage standard error of the mean of all samples suggesting variation in the weight percentage of these elements between different church roofs. Multiple samples from the same roofs, but different lead sheets, showed much lower weight percentage standard errors of the mean suggesting similar trace element concentrations. Lead isotope ratios were similar for all samples. Factors likely to affect the occurrence of these trace elements are discussed.     

A fast ultrasound-assisted extraction procedure for trace elements determination in hair samples by ICP-MS for forensic analysis

An ultrasound-assisted extraction method is proposed for the determination of trace elements in hair samples by inductively coupled plasma-mass spectrometry (ICP-MS) for forensic investigation. Prior to analysis, 25 mg of hair samples were accurately weighed into (15 mL) conical tubes. Then, 2 mL of 20% HNO₃ is added to the samples, sonicated at 2 min (50 W, 100% amplitude), and then further diluted to 10 mL with Milli-Q water. Resulted diluted slurries are centrifuged and the analytes are directly determined in the supernatant. Calibrations against aqueous solutions were carried out with rhodium as internal standard. The method was successfully applied for the extraction of Al, As, Ba, Be, Cd, Co, Cr, Cu, Mn, Pb, Tl, U, V and Zn with a method detection limit (3 s, n = 20) of 0.1, 0.4, 0.2, 0.09, 0.08, 0.04, 0.1, 2.9, 1.0, 0.9, 0.04, 0.05, 0.1 and 4.2 ng/g, respectively. Method accuracy is traceable to Certified Reference Materials (CRMs) 85 and 86 human hair from the International Atomic Energy Agency (IAEA). Additional validation data are provided based on the analysis of hair samples from the trace elements intercomparison program operated by the Institut National de Sante’ Publique du Quebec, Canada. The proposed method is very simple and can be applied for forensic purposes with the elimination of sample digestion step prior to analysis. Then, a considerable improvement in the sample throughput is archived with the use of the proposed method.     

Elemental analysis of glass fragments by ICP-MS as evidence of association: analysis of a case

Inductively coupled plasma mass spectrometry (ICP-MS) was used to analyze glass evidence from a case in which a person broke a window in each of 15 vehicles in a parking lot in order to gain entry into the vehicles. The results of the analysis by traditional methods, which measure the properties of color, thickness, density, and refractive index, are also reported. A total of 15 known samples representing the windows on the cars and 42 questioned glass fragments recovered from the suspect and the police vehicle where the suspect was sitting were submitted for analysis. Density comparisons separated one of the known samples into three samples, increasing the number of known samples from 15 to 17. The concentrations of 16 elements were measured for all but three of the samples using an external calibration ICP-MS method with internal standardization. Color assessment (non-instrumental) separated the 17 known samples into two groups, and refractive index measurements resulted in six groups when the Emmons double variation method was used and ten groups when the Glass Refractive Index Measurement 2 (GRIM2) system was used. Elemental analysis, by itself, differentiated all of the known samples from each other and associated four of the known sample fragments with several of the questioned sample fragments. The informing power of RI, density, and elemental analysis comparisons is evaluated and a summary of the case results is reported.     

Linking ammonium nitrate-aluminum (AN-AL) post-blast residues to pre-blast explosive materials using isotope ratio and trace elemental analysis for source attribution

Forensic science practitioners are often called upon to attribute crimes using trace evidence, such as explosive remnants, with the ultimate goal of associating a crime with a suspect or suspects in order to prevent further attacks. The explosive charge is an attractive component for attribution in crimes involving explosives as there are limited pathways for acquisition. However, there is currently no capability to link an explosive charge to its source via post-blast trace residues using isotope ratios or trace elements. Here, we sought to determine if pre-blast attribution signatures are preserved after detonation and can be subsequently recovered and detected. A field study was conducted to recover samples of post-blast explosives from controlled detonations of ammonium nitrate-aluminum (AN-Al), which were then analyzed via isotope ratio mass spectrometry (IRMS) and inductively coupled plasma-mass spectrometry (ICP-MS) for quantitation and profiling of isotopes ratio and trace element signatures, respectively. Oxygen and nitrogen isotope ratios from AN-Al yielded some of the most promising results with considerable overlap within one standard deviation of the reference between the spreads of pre- and post-blast data. Trace element results from AN-Al support the findings in the isotope ratio data, with 26 elements detected in both pre- and post-blast samples, and several elements including B, Cd, Cr, Ni, Sn, V, and Zn showing considerable overlap. These preliminary results provide a proof-of-concept for the development of forensic examinations that can attribute signatures from post-blast debris to signatures in pre-blast explosive materials for use in future investigations.     

全基因组扩增在微量检材DNA分型中的应用

目的探索全基因组扩增技术对微量检材DNA分型的有效性。方法通过显微操作制备含1~20个细胞的模拟微量检材样本,在常规PCR-STR分型前加入全基因组扩增步骤,从等位基因不平衡、等位基因丢失、基因座丢失、伪等位基因(包含stutter峰)等方面探究PEP和MDA两种全基因组扩增方法对微量检材DNA分型的有效性。结果 MDA扩增效率高于PEP,但等位基因丢失和伪等位基因严重;PEP方法的正确分型率高于MDA,但小片段DNA优势扩增现象较严重。结论 MDA方法并不适合目前以STR分型为主导的法庭科学,当微量检材样本的绝对量相当少时,可以考虑使用PEP方法来扩大样本量,以满足重复检验的要求,但可能面临大片段DNA扩增失败的风险。     

Voltammetric determination of Δ9-THC in glassy carbon electrode: An important contribution to forensic electroanalysis

Teeth are recently drawing attention for their potential as biological modeling investigation samples due to their ability to be collected and their slow substance metabolism. There is no active metabolism of elements after the completion of dentin. Dentin is surrounded by enamel and cementum, and is not affected by the oral environment. Therefore, the amount of trace elements in dentin may change with age, and this is considered to be a reliable biological load index. The objectives in this study are to demonstrate concentrations of elements in the dentin of healthy Japanese subjects by sex and age, and to reveal the relationship between element levels and age. 121 healthy teeth samples were extracted due to periodontal disease or orthodontic treatment. Each tooth was sliced from the crown to the root apex into 0.5-1mm thickness, then enamel, cementum, and the pulp were removed; the dentins were used as samples. The concentration of 10 trace elements (B, Mn, Co, Cu, Zn, Rb, Sr, Mo, Cd, and Pb) in the dentin was measured using inductively coupled plasma mass spectrometer (ICP-MS). The differences Co and Pb in the dentin between men and women were significant (p<0.01). Significant positive correlation was observed between B, Co, Cu, Zn, Sr and Pb concentrations in the dentin and age (p<0.001). The results of the present study suggest that human dentin is an appropriate substance for relativity with sex and age at further future research.