甲醛溶液固定对ICP-MS检测电流损伤皮肤金属化的影响

目的探讨应用电感耦合等离子体质谱（inductively coupled plasma-mass spectrometry ICP-MS）技术检测甲醛溶液固定后电流损伤皮肤中金属元素。方法利用黄铜、铁电极材料以220V交流电电击兔子后肢,电损伤皮肤分别进行甲醛溶液固定1周、6个月后,应用ICP-MS对电流损伤皮肤中金属元素进行测定。结果与对照组皮肤比较,黄铜电击组皮肤中检测出Cr、Ni、Cu、Zn、Pb含量升高（P〈0.05）;固定1周、6个月后仍可检测出Cr、Ni、Cu、Zn、Pb成分,其中Cr、Cu、Zn、Pb含量电击组与固定组差异无统计学意义。与对照组比较,铁电击后皮肤中检测出Fe、Cr、Mn、Ni元素含量升高（P〈0.05）;固定组（1周和6个月）后Fe、Cr、Ni元素含量与电击组差异无统计学意义。结论 ICP-MS可作为检测电流损伤皮肤中金属元素的有效方法,甲醛溶液固定后触电皮肤仍可进行沉积的金属元素检测,且固定对皮肤金属元素的含量影响较小,该方法仍可为电流损伤诊断提供依据。     

微束X射线荧光光谱法检测电流损伤皮肤金属化

目的建立微束X射线荧光光谱（μ-probe X-ray fluorescence,μ-XRF）检测电流损伤皮肤金属化的方法。方法新西兰大白兔32只,随机分为黄铜电击组、紫铜电击组、铁电击组、铝合金电击组,每组8只。电极一极固定于左后腿中部,另一极固定于左前腿,建立电击模型。提取左后腿触电部位皮肤,以及对侧右后腿相应部位皮肤作为对照,应用μ-XRF光谱仪对电流损伤皮肤内金属元素进行测定。结果正常对照组皮肤中检测出磷、氯、钾、钙元素成分;在电击组皮肤中,除正常皮肤检出的元素外,黄铜电击组检测出铜、锌元素,紫铜电击组检出铜元素,铁电击组检出铁元素,铝合金电击组检出铝元素。渗透到电流损伤皮肤内的金属元素呈不均匀分布。结论μ-XRF光谱法检测皮肤金属化可作为诊断电流损伤的特征性指标,并可为触电材料的推断提供依据。     

湖南省人群血液中33种元素的正常值范围

目的调查湖南省一般人群血液中33种元素[锂(Li)、铍(Be)、硼(B)、镁(Mg)、铝(Al)、钙(Ca)、钛(Ti)、钒(V)、铬(Cr)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、镓(Ga)、砷(As)、硒(Se)、铷(Rb)、锶(Sr)、锆(Zr)、钼(Mo)、银(Ag)、镉(Cd)、锑(Sb)、铯(Cs)、钡(Ba)、金(Au)、汞(Hg)、铊(Tl)、铅(Pb)、钍(Th)、铀(U)]的正常值范围。方法采用电感耦合等离子体质谱法(inductively coupled plasma-mass spectrometry,ICP-MS)检测血液中33种元素,测定其正常值范围,并考察区域、性别和年龄对人群血液中元素含量的影响。结果建立了湖南省人群血液中33种元素的正常值范围,其中B、Mg、Ca、Ti、Mn、Fe、Co、Cu、Zn、As、Se、Rb、Sr、Ag、Cd、Cs、Hg和Pb在性别间差异具有统计学意义(P0.05)。女性因年龄不同有差异的元素有Co、Ni、Cs和Hg(P0.05),男性因年龄不同有差异的元素有Cu、Se和Hg(P0.05)。结论不同地区人群血液中元素含量存在差异,建立了湖南省四个市的正常值范围。     

电烧伤皮肤金属元素的测定

本实验系用220V交流电源和直径2.0mm紫铜线为接触电极,在新鲜尸体腹部皮肤上做电烧伤实验。用原子吸收分光光度计对电烧伤皮肤中铜元素含量进行测定。结果表明电烧伤皮肤铜元素含量最高可达137.90μg/g。经10%福尔马林溶液固定40天以上的电烧伤皮肤铜元素含量有昕降低,但仍较正常皮肤含量为高。电烧伤皮肤铜元素含量以电流斑处为最高。本实验为电烧伤皮肤金属元素的定性与定量分析,检材的提取和处理,提供了一个较好的方法,有利于判定案件的性质和确定接触电极的金属种类。     

家兔皮肤低电压电损伤组织病理学研究

目的研究不同数值低电压对家兔皮肤电损伤的组织病理学变化,为皮肤电损伤的法医学鉴定提供一定依据。方法选取家兔35只,随机分为36V、110V、220V生前和死后电击组各3组及正常对照组,共7组,每组5只。应用自制电击装置对家兔进行生前不同数值电压电击和死后不同时间电击,然后对电击处皮肤取材,常规石蜡包埋及HE染色制片并进行组织病理学观察研究。结果 36V生前和死后电击皮肤组织学未见改变;110V、220V生前和死后不同时间予以电击均出现电流斑改变;220V和110V生前与死后电流斑形态无差异;220V较110V电击皮肤电流斑明显。结论电流斑与电压的数值大小存在相关性,电压越高电流斑越明显,36V交流电不能形成电流斑;相同数值电压下电击,生前和死后组电流斑无明显形态学差异,电流斑在36V、110V、220V电压时不能用于区分电击损伤是否为生前或死后所致。     

家兔眼玻璃体液21例元素含量PMI关系的研究

目的寻找一种精确推定PMI的方法。方法应用电感耦合等离子体质谱(ICP-MS),系统研究了家兔死后96h内眼玻璃体液21种元素含量与PMI的相关性。结果眼玻璃体液Co、Mo、Cd、Sb、I、Pb、Bi、Li共8种元素与PMI无关。K、Mg、Fe、P、Na、Al、Ca、Ti、Ni、Cu、Zn、Sr、Ba共13种元素含量与PMI有关。结论眼玻璃体液K、Mg、Fe、P、Na、Al、Ca、Ti、Ni、Cu、Zn、Sr、Ba共13种元素与PMI有关。为研究人尸体眼玻璃体液元素与PMI的关系奠定了选择指标的基础。     

扫描电镜/X射线能谱仪检验电流斑规范化方法探讨

目的探讨电流斑皮肤金属化的机理、检材提取处理和扫描电镜/能谱仪检验规范化方法,对检验结果进行分析和价值判断。方法用扫描电镜/能谱检验,采用低倍大窗口覆盖损伤区域采集平均元素能谱图,并在可能的金属元素富集区域寻找球形金属颗粒。结果扫描电镜下可观察到散在的孔穴、细胞碎屑、龟裂、裂隙等特征,有些电流斑可检出金属元素,其中部分电流斑可发现球形金属颗粒。结论采用规范化的检材提取、处理和检验方法可消除随意性方法造成错检的可能。电流斑皮肤上异常含量的金属附着可支持病理检验符合电流斑表现的结论,同时也为电击导体的推断和金属元素成分比对提供依据。球形金属颗粒的发现揭示存在电弧高温的可能性极大,可强力支持病理检验符合电流斑表现的结论。     

血液中Cr、Cd、As、Tl和Pb的电感耦合等离子体质谱分析

目的 建立血液中Cr、Cd、As、Tl和Pb的电感耦合等离子体质谱(ICP-MS)分析方法. 方法血液采用微波消解仪进行处理,以115In元素作内标,使用ICP-MS方法对血液中Cr、Cd、As、Tl和Pb进行分析.结果 方法检出限为0.00001～0.00249μg/L,准确度为90.1%～110.7%,精密度为4.0%～7.9%. 结论建立的方法准确、快速、线性范围宽、灵敏度高,适用于Cr、Cd、As、Tl和Pb中毒案件的检测.     

电流斑的环境扫描电镜X射线能谱分析

目的利用环境扫描电镜-X射线能谱仪(environmental scanning electron microscope and energydispersive X-ray microanalyser,ESEM-EDX)研究电流斑微观形态特征及元素构成,以期为电流斑及电击死的鉴定提供更准确、客观的依据。方法用ESEM-EDX检测5例电流斑的扫描电镜形态、金属颗粒的形态及其元素组成。结果电流斑及周围皮肤可见电穿孔、金属熔珠,熔珠主要由铁、铜、铝等常见金属元素和金、钛、钡等人体少见的金属元素构成。结论 ESEM-EDX检测可为电击死的鉴定提供客观的依据。     

大鼠电流损伤多器官c-Fos表达研究

目的探讨c-fos蛋白能否用于生前电击与死后电击的鉴别。方法建立大鼠生前与死后电流损伤模型。生前电击组大鼠于电击后即刻和1,2,4,8h处死;死后电击组大鼠于死后即刻和15、30min及1h电击大鼠,检测所有实验大鼠心、肝、脾、肺、肾、骨骼肌、皮肤、脑等器官c-fos蛋白的表达情况,其结果经图像分析处理。结果生前电击各组大鼠心、肝、肺、肾、骨骼肌、脑c-fos蛋白呈强阳性表达,脾脏与皮肤呈阴性表达;而于死后电击各组大鼠中,仅死后即刻电击组大鼠心、肝、肺、肾、骨骼肌、脑c-fos蛋白呈很微弱的阳性表达,其余各组各器官均为阴性表达。结论检测各器官c-fos蛋白的表达情况,可以鉴别生前电击与死后电击。     

两种铁铬合金电警棍遗留金属颗粒成分分析

目的检测两种电警棍铁铬合金电极遗留金属颗粒的成分,对同一电警棍电击前后遗留金属颗粒成分特征进行分析,对电警棍遗留金属颗粒成分的稳定性、差异性进行评价。方法使用电警棍分别多次摩擦滤纸和电击猪皮,使用碳导电胶带粘取遗留金属颗粒,应用SEM/EDS技术检测颗粒元素成分,并对数据进行统计学分析。结果两种电警棍电击前遗留铁铬合金颗粒及电击后遗留铁铬合金颗粒成分均稳定,存在差异;实验两种电警棍电击后遗留金属颗粒成分分布发生显著变化,除原成分铁铬颗粒外,实验猪皮表面均检出全新成分的铁铬合金颗粒,且两种电警棍电击后产生的全新铁铬颗粒成分稳定无显著差异。结论通过分析两种电警棍铁铬电极电击前后遗留多金属颗粒成分分布特征,可以实现对两种电警棍电极的识别,为人体电警棍损伤的识别与认定提供技术支持和理论依据。     

Application of atomic absorption spectroscopy for detection of multimetal traces in low-voltage electrical marks

Application of atomic absorption spectroscopy to detect multimetal traces in injured skin is a promising tool for investigation of fatalities caused by electrocution. The present paper is aimed at testing the reliability of this method for metal traces detection in electric current marks and is focused on study of peculiarities of metal penetration into the skin exposed to a current impact. Bare aluminum wire, tin-lead coated copper multistrand wire, and zinc-plated steel rope were used to make electrical marks on pig skin. It is demonstrated that amount of copper, zinc, lead, and iron may serve as statistically reliable indicators for the type of wire, which caused the electrical mark, in spite of the background content of these metals in the skin without injury. Different penetration rates for different metals contained in the wire inflicting an electrical mark were observed.     

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。     

Differentiation of bullet type based on the analysis of gunshot residue using inductively coupled plasma mass spectrometry

Porcine tissue samples shot with two different types of bullets, jacketed and nonjacketed, were collected in the fresh state and throughout moderate decomposition. Wound samples were microwave-digested and analyzed using inductively coupled plasma mass spectrometry (ICP-MS) to detect all elements present at measurable levels in gunshot residue (GSR). Elements detected included antimony (Sb), barium (Ba), and lead (Pb), which are considered characteristic of GSR, as well as iron (Fe) and copper (Cu). These five elements were used to differentiate shot tissue and unshot tissue, as well as tissue shot by the two different bullet types, both in the fresh state and throughout moderate decomposition. The concentrations of Cu, Sb, and Pb were able to distinguish the two bullet types in fresh tissue samples at the 95% confidence level. Cu and Pb were able to differentiate the bullet types throughout moderate decomposition at the 99% confidence level.     

Metal and metalloid multi-elementary ICP-MS validation in whole blood, plasma, urine and hair. Reference values

Four multi-elementary metal and metalloid quantification methods using inductively coupled plasma mass spectrometry (ICP-MS) were developed and validated in human whole blood, plasma, urine and hair by means of a single preparation procedure for each sample. The ICP-MS measurements were performed using a Thermo Elemental X7CCT series and PlasmaLab software without a dynamic reaction cell. With this procedure 27-32 elements can be simultaneously quantified in biological matrices: Li, Be, B, Al, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Mo, Pd, Ag, Cd, Sn, Sb, Te, Ba, W, Pt, Hg, Tl, Pb, Bi, U. Whole blood, plasma and urine samples (0.4 ml each) were diluted with purified water, acid, triton X100 and butanol. Rhodium was used as internal standard. The urine sample results were corrected for enzymatic creatinine determination. Twenty-five milligrams hair samples were acid mineralized after a decontamination procedure and diluted as previously described for biological fluids. To be validated, each element had to show linearity with a correlation coefficient higher than 0.99. The intra-assay and inter-assay inaccuracy, measured as the variation coefficient, were below 5 and 10% respectively. Global performance was assessed by a quality control program. Our laboratory is a registered participant of the Institut National de Santé Publique du Québec (Sainte-Foy, Canada) inter-laboratory comparison program for whole blood, urine, and beard hair of non-occupationally exposed individuals spiked with selected elements. In our study multi-element metal and metalloid analysis was assessed for 27 elements in whole blood, 27 elements in plasma, 30 elements in urine and 32 elements in hair, from 0 to 25, or 250 to 1000 ng/ml, depending on the element. Quantification limits ranged from 0.002 ng/ml (U) to 8.1 ng/ml (Al) for whole blood, from 0.002 ng/ml (U) to 7.7 ng/ml (Al) for plasma, from 0.001 ng/ml (U) to 2.2 ng/ml (Se) for urine, and from 0.2 pg/mg (Tl) to 0.5 ng/mg (B) for hair. Normal values were determined in whole blood (n=100), plasma (n=100), urine (n=100), and hair (n=45) of healthy volunteers, leading to approximately 10,000 analyses. All results are presented and discussed. Clinical toxicology and forensic toxicology applications are also reported. ICP-MS has made significant advances in the field of clinical biology, particularly in toxicological analysis. This is due to the use of extremely effective equipment that permits better clinical and forensic toxicological analysis of metal and metalloid status of each individual patient.     

电警棍致皮肤损伤的实验研究

本研究系用电警棍电击实验动物（猪），观察电击部位的皮肤喷涂金属显色剂后的颜色改变、组织学改变及金属含量的改变。结果表明，电警棍电击机体，不仅可致皮肤产生肉眼可见的损伤，而且可致皮肤细胞产生轻微的极化现象和皮肤金属化，这种金属化可通过金属显色剂喷涂和原子吸收分光光度计检测出来．本实验为电警棍电击伤的定性分析、检材的提取与处理提供了比较好的方法，有利于判定案件的性质和确定电警棍的种类。     

用发射光谱分析测定电流斑中的金属元素

<正> 电流斑由肉眼或组织学观察有时难以确认,尤其是凶杀案件中,在电击死亡后,尸体经伪装或因腐败,从形态学确诊电流斑困难更大。因此,如能在可疑电流斑部位的皮肤组织中,检出接触皮肤导体的金属元素,对确认电击致死具有重要意义。作者结合两起案例,利用原子发射光谱分析法,对人体皮肤电流斑进行检验。现将结果报告于下。