头发中无机元素分析方法及应用的研究进展

人体无机元素含量在头发中较其它体液或组织中高,易于检出。头发能够存储较长的时间信息,并且能提供其空间信息。通过分析其中的无机元素含量和同位素比例,可以说明元素在体内特定时间的变化以及反映人体的地理位置迁移。综述了头发中无机元素分析的前处理和仪器分析方法,重点介绍头发中无机元素分析在环境、医学及法医学研究中的应用,并对未来的技术发展和应用进行展望。     

癌症病人头发中无机元素含量变化初探

采用ＩＣＰ－ＡＥＳ法测定了肺癌、肝癌、胃癌患者头发中２４种无机元素的含量,与对照组比较,探讨对癌症实验诊断有意义的指标。结果表明：肺癌、肝癌、胃癌患者头发中Ａｌ、Ｃｕ、Ｃｏ、Ｎｉ、Ｓｒ、Ｚｎ、Ｍｎ、Ｍｏ等元素含量与对照组存在显著差异（Ｐ〈０．０５）。因此采用多元素谱作为上述癌症辅助诊断指标相对于采用单元素值或元素比值作为诊断标准更具参考价值。     

百岁老人头发中矿物元素检测分析

应用美国的Ｐｌａｓｍａ－Ｓｐｅｃ光谱仪检测了３１例百岁老人头发中铁、铅、铜、钙、铝、锶、镍、锰、镉１０种元素和含量，并与健康成人组对照比较，发现百岁组发锌、铁增高和发锶、锰、钙、铜减低，与成人组比较有显著差异，另虽发铅、镉、镍增高和发铝减低但与成人组比较，并无统计学意义，文中还对矿物元素分析对健康长寿与疾病的作用进行初步探讨。     

新生儿头发微量及常量元素测定

采用ＪＹ－７０合并型等离子体光谱仪测定了１０４名健康足月新生儿头发中１４种微量元素和２种常量元素含量。结果表明，新生儿发生中Ｆｅ，Ｃｏ，Ｎｉ，Ｍｎ，Ｃｒ，Ｍｏ，Ｓｒ，Ｖ，Ｃａ和Ｍｇ等元素的含量水平较高；新生儿发Ｆｅ男性显著高于女性，发Ｍｇ则女性高于男性，发Ｓｒ女性高于男性，其它各元素性别间无差异或差异不显著。     

头发元素分析的科学意义及医学应用价值

对近100年来头发元素分析发展历史作了简要回顾，并从头发元素水平代表身体元素总体水平、头发元素含量可以准确测定，以及头发元素分析可用于医学诊断等三个方面论述了头发元素分析的生物学基础及临床意义，重点介绍了中国科学工作者在实验研究和临床实践中的探索和发现。科学实践证明，头发元素分析不仅为揭开古代头发神话提供了解释基础，也为头发的现代应用提供了可靠工具和科学依据。     

精神分裂症患者头发5种元素含量变化及临床意义

采用原子吸收光谱法测定了９６例精神分裂症患者和１０１名正常对照组的头发Ｚｎ、Ｃｕ、Ｆｅ、Ｃａ、Ｍｇ元素含量。结果发现，精神分裂症患者头发ｎ和Ｍｇ元素含量明显低于对照组，而Ｃｕ、Ｆｅ和Ｃａ元素含量明显高于对照组。提示精神分裂症的发病，可能与Ｚｎ和Ｍｇ元素含量降低，Ｃｕ、Ｆｅ和Ｃａ元素含量升高有关。     

锦灯笼中无机元素含量测定

采用ＩＣＰ－ＡＥＳ法检测了要笼果实及其干燥宿萼中无机元素含量。结果表明,锦灯笼含有丰富的对人体有益的无机元素,具较高的营养价值。     

13种龟甲的无机元素和氨基酸含量比较

以１３种龟甲为药样，用电感耦合等离子体原子发射光谱法和氨基酸自动分析仪对１３种龟甲的无机元素及９种龟甲的氨基酸含量进行测定，为龟甲的品质评价及资源开发利用提供了科学参考。     

乳腺癌患者头发元素分析

应用装有ＥＰＭ－８１０Ｑ电子探针的扫描分析电镜，对３０例乳腺癌患者作了单根头发中镁、铝、镉、钙、铬、铁、铜、锌、铅、硒、锰１１种元素分析，并与健康组进行比较。结果表明：乳腺癌组缺铝、镁、硒元素明显低于正常人，差异有显著性（Ｐ〈０．０５）。     

等离子体发射光谱法测定茶水中无机元素的含量

采用电感耦合等离子体发射光谱法对茶水中的无机元素进行分析,对其中的Cu、Zn、Mn、P、Fe5种元素进行定量,讨论了等离子体发射光谱法最佳实验条件及影响茶叶中无机元素浸出量的因素。Cu、Zn、Mn、P、Fe的回收率为92．5％～103．5％,测定结果的相对标准偏差为1．34％-4．5％（n=5）。     

Human hair as a marker of pollution by chemical elements emitted by a thermoelectric power plant

A preliminary study was undertaken to assess the risk posed to the environment and health of residents by trace elements released by fuel combustion in the thermoelectric power plant of Pian de’ Gangani (Montalto di Castro, Latium, Italy). In this context, analysis of human hair can be considered as an advantageous approach to monitor the exposure of population to the adverse effects of the power plant, which is now fully operative. To this purpose 92 healthy children (aged 9–10 years) were selected from two primary schools of Montalto di Castro and Pescia Romana. The young age of the donors guarantees that the effects of cosmetic treatment and occupational exposure on the representativeness of data are minimized. Hair samples were collected, washed and digested as prescribed by already well-established procedures. Inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) were employed for the determination of the trace and minor elements of interest (As, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, P, Pb, Sb, Se, Tl, V and Zn). The entire analytical procedure was checked for both measurement precision and accuracy by using the Certified Reference Material BCR No. 397 Human Hair. The mean values obtained were (in μg g⁻¹): As, 0.159±0.044; Ca, 393±187; Cd, 0.047±0.055; Co, 0.040±0.038; Cr, 0.704±0.208; Cu, 12.0±10.3; Fe, 12.1±10.8; Mg, 40.6±27.7; Mn, 0.383±0.296; Ni, 0.868±1.331; P, 141±138; Pb, 1.64±1.63; Sb, 0.041±0.058; Se, 0.430±0.135; Tl, 0.001±0.001; V, 0.185±0.158; and Zn, 177±173. These experimental figures can be assumed to be the baseline values prior to the full operation of the power plant. Within the next 4–5 years it is planned to conduct a similar study with a new group of subjects, comparable for age, sex, style of life and exposure mode, to the present ones so as to detect possible trends in the bioaccumulation of the above elements.     

Quality control in hair analysis: A systematic study on washing procedures for trace element determinations

Trace element analysis of human hair is widely used to provide an indicator of body burden, but there is a major problem associated with preparation. The washing procedure adopted before analysis represents still a critical point which deserves particular attention. This study aimed at comparing the efficiency of the most commonly used washing methods to identify the procedure which allows for satisfactory removal of external contamination alone. As results depend strongly on the element, toxic (Cd and Pb), essential trace (Cr, Cu, Se and Zn) and major (Ca, K and Mg) elements were tested. The comparison was carried out with six different methods which include use of ionic and non-ionic detergents, organic solvents, chelating agents and sonication. Removal efficiency varied according to the element and pretreatment, the highest being observed for EDTA and the lowest for sonication. Unsatisfactory results were found using an acetone/methanol mixture for the potential contamination caused by it. Organic solvents showed the highest removal efficiency for K and toxic elements, and seemed to be effective in removing a limited but significant fraction of element incorporated in the lipid matter of hair. The ionic detergent Na lauryl sulphate, instead, was more effective for essential elements, but also triggered a higher analytic variability. As detergents appear to remove only external contamination, a non-ionic detergent such as Triton X-100 is proposed as a reliable alternative to the acetone method recommended by IAEA. Practical advantages are safe working conditions, rapidity of application and reduction in costs.     

Determination of trace elements in a human serum reference material by inductively coupled plasma mass spectrometry

A method was developed for the determination of Fe, Co, Cu, Zn, Rb, Mo and Cs in human serum by ICP-MS. Sample preparation was kept as limited as possible: Serum samples were diluted with nitric acid and indium was added as internal standard. The results for Fe, Co, Cu, and Zn were corrected for interferences from polyatomic ions using a suitable blank solution. No interferences occur for the considered isotopes of Rb, Mo, and Cs. A second-generation human serum reference material was analyzed, in order to test the accuracy and precision of the analytical procedure. The results obtained are in good agreement with the certified values.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, AustriaResearch Director of the National Fund for Scientific Research (Belgium)     

火焰原子吸收法测定鸡尾木中无机元素的含量

鸡尾木(ExcoecariaVenenataS.LeeetF.N.Wei)属大戟科,海漆属,为民间药用珍贵植物,用于治疗牛皮癣、慢性湿疹等,疗效颇佳[1]。鸡尾木中无机元素,尤其是医学微量元素的测定对其药理效的研究有重要的参考价值。1　实验部分1 1　仪器及试剂TAS 986原子吸收分光光度计(北京普析通用仪器有限责任公司);空心阴极灯:Fe、Cu、Ni、Cr、Cd、Zn、Co、Ba、Ca(北京瑞利普光电器厂);Mg、Pb(北京真空电子技术总公司);Mn(北京市朝阳天宫电器厂);AdventurerTM电子天平(奥豪斯国际贸易〈上海〉有限公司)。标准储备液:配制Zn2+、Mg2+、Fe3+、Mn2…     

Determination of traces of As,Cd, Cr,Hg, Mn,Ni, Sb,Se, Sn and Pb in human hair by triple quadrupole ICP-MS

With the wide range of metallic contaminants discharged in the environment, studying the human health requires a growing number of elements to be monitored in biological samples. Hair analysis has been suggested as a suitable tool for biomonitoring environmental and occupational exposure to toxic elements. This study describes a method for the determination of 10 trace elements in hair samples using ICP-QQQ-MS. Combining the power of the MS/MS high-energy Helium mode with the MS/MS O₂ mass-shift mode, the method offers great analytical performances with detection limits reaching 0.0014 µg g^?1 for As, 0.0016 µg g^?1 for Cd, 0.012 µg g^?1 for Cr, 0.0035 µg g^?1 for Hg, 0.0055 µg g^?1 for Mn, 0.10 µg g^?1 for Ni, 0.0012 µg g^?1 for Sb, 0.0083 µg g^?1 for Sn, 0.011 µg g^?1 for Se and Pb. The accuracy of the method was tested on a human hair ERM® certified reference material. Percent recoveries varied from 91.3% and 106.9% being always in the acceptance range of 90–110%. For all analysed elements, RSD% of repeatability ranged between 0.6% and 9.0% and those of intermediate precision did not exceed the limit of 20% being always lower than 10% (except for As). The proposed method was applied for the determination of trace elements in hair samples from 20 unexposed subjects. The geometric mean levels were as follows: Cr 0.28 µg g^?1, Mn 0.30 µg g^?1, Sn 1.04µg g^?1, Sb 0.07 µg g^?1, Hg 0.42 µg g^?1, As 0.02 µg g^?1, Cd 0.03 µg g^?1, Ni 0.51 µg g^?1, Se 0.45 µg g^?1 and Pb 1.83 µg g^?1. Element concentrations were in the same range with the reported data. The reported results may be useful for environmental exposure assessment or comparisons studies when establishing reference values of trace elements in exposed population.     

广州市孕妇头发微量元素含量测定

测定了286例不同孕周孕妇头发锌、铁、铜、钙、锰、铅含量,并进行了比较分析。结果表明,孕期上述元素的异常率分别为：40．21％、37．76％、15．04％、45．46％、19．58％、27．97％。不同孕周变化各有差异,以孕中期变化最为明显（除铜和锰外,P＜0．01）。提示妊娠期妇女有益微量元素缺乏的现象是很普遍的,妊娠中晚期事理调整膳食结构和营养物质的补充是必要的。     

Concentrations of elements in brain tumours

The aim of our experiments was to investigate the possible elemental concentration changes in brain tumours (glioblastoma multiforme). Our project also incorporated the determination of the regional distribution of elements in normal human brains. 17 elements (Na, K, Ca, Mg, Fe, P, S, Al, B, Ba, Co, Cr, Ni, Mn, Pb, Sr, Zn) have been measured in 21 different regions of 20 normal brains and in clinically and histopathologically selected brain regions of patients with brain tumours. Analyses were carried out by instrumental neutron activation analysis (INAA) and inductively coupled plasma atomic emission spectrometry (ICP-AES). Quality control was ensured by using NBS Bovine Liver 1577a standard reference material. Comparison between the healthy and brain tumour concentration data using statistical evaluation revealed only a few elements (e.g. B, Zn, Sr) which showed significant differences as a consequence of the brain tumour.     

Binding characteristics of ionic surfactants with human hair

Binding isotherms of two types of ionic surfactants, C_mH_{2m +1}SO₄Na (m = 8,10,12) and C_nH_{2n + 1}N⁺(CH₃)₃C1 (n=10, 12), to human hair in aqueous solutions were examined to clarify effects of hydrophobic and electrostatic interaction of ionic surfactants with hair. The binding isotherms of anionic surfactants showed cooperativity with discontinuously increasing shapes, while the binding isotherms of cationic surfactants showed a Langmuir-type, regardless of the difference of a hair condition.The calculated free energy change (— G@#@) for binding, obtained from Klotz' plots, suggests that the binding processes are governed mainly by a hydrophobic interaction, and bound surfactants probably expose their alkyl chains to the aqueous phase, since no-G was observed with the increase of m or n and values of enthalpy change(H) were positive or zero.     

微波消解-超声雾化-ICP-AES测定发样中微量元素

研究了微波消解-超声雾化-ICP-AES测定人发样品中12种常量、微量元素的方法。对样品的测定条件进行了优化，并对20例女性拉祜族长寿老人发样进行了测定。与普通老人比较，女性拉祜族长寿老人发样中Mn、Mo、Ge的含量均明显高于普通老人发样中含量，存在显著性差异。