Goullé Jean-Pierre, Mahieu Loïc, Castermant Julien, Neveu Nicolas, Bonneau Laurent, Lainé Gilbert, Bouige Daniel, Lacroix Christian
Laboratoire de Pharmacocinétique et de Toxicologie Cliniques, Groupe Hospitalier, BP 24, 76083 Le Havre, France.
Forensic Sci Int. 2005 Oct 4;153(1):39-44. doi: 10.1016/j.forsciint.2005.04.020.
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.
通过对每个样本采用单一制备程序,开发并验证了四种使用电感耦合等离子体质谱法(ICP-MS)对人体全血、血浆、尿液和毛发中的多种元素及类金属进行定量的方法。使用Thermo Elemental X7CCT系列和PlasmaLab软件在无动态反应池的情况下进行ICP-MS测量。通过该程序可同时对生物基质中的27 - 32种元素进行定量:锂(Li)、铍(Be)、硼(B)、铝(Al)、钒(V)、铬(Cr)、锰(Mn)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、镓(Ga)、锗(Ge)、砷(As)、硒(Se)、铷(Rb)、锶(Sr)、钼(Mo)、钯(Pd)、银(Ag)、镉(Cd)、锡(Sn)、锑(Sb)、碲(Te)、钡(Ba)、钨(W)、铂(Pt)、汞(Hg)、铊(Tl)、铅(Pb)、铋(Bi)、铀(U)。全血、血浆和尿液样本(各0.4 ml)用纯净水、酸、曲拉通X100和丁醇稀释。铑用作内标。尿液样本结果通过酶法测定肌酐进行校正。25毫克毛发样本在去污程序后进行酸矿化,并按先前描述生物体液的方法进行稀释。为进行验证,每种元素的线性相关系数须高于0.99。以变异系数衡量的批内和批间不精密度分别低于5%和10%。通过质量控制程序评估整体性能。我们的实验室是加拿大魁北克国家公共卫生研究所(魁北克省圣福瓦)针对非职业暴露个体全血、尿液和胡须毛发添加选定元素的实验室间比对计划的注册参与者。在我们的研究中,对全血中的27种元素、血浆中的27种元素、尿液中的30种元素和毛发中的32种元素进行了多元素金属和类金属分析,浓度范围为0至25或250至1000 ng/ml,具体取决于元素。全血的定量限范围为0.002 ng/ml(U)至8.1 ng/ml(Al),血浆为0.002 ng/ml(U)至7.7 ng/ml(Al),尿液为0.001 ng/ml(U)至2.2 ng/ml(Se),毛发为0.2 pg/mg(Tl)至0.5 ng/mg(B)。在100名健康志愿者的全血(n = 100)、血浆(n = 100)、尿液(n = 100)和毛发(n = 45)中测定了正常值,共进行了约10,000次分析。所有结果均已呈现并讨论。还报告了临床毒理学和法医毒理学应用。ICP-MS在临床生物学领域取得了重大进展,特别是在毒理学分析方面。这得益于使用了极其有效的设备,能够对每位患者的金属和类金属状态进行更好的临床和法医毒理学分析。