样品厚度对薄膜法X射线荧光光谱测量的影响研究

分别以富集有Cr,Pb和Cd三种元素的尼龙薄膜样品及玻璃纤维滤膜为研究对象,采用滤膜叠加的方式,通过XRF光谱仪测量不同样品厚度下薄膜样品的XRF光谱,根据测得的尼龙薄膜样品中Cr,Pb,Cd元素及玻璃纤维滤膜中Ca,As和Sr元素特征XRF性质的变化,研究样品厚度对薄膜法XRF光谱测量的影响。结果表明：薄膜样品厚度对不同能量区间上元素特征谱线荧光性质的影响并不相同。元素特征谱线能量越大,元素特征X射线荧光穿透滤膜到达探测器的过程中损失越少;但由薄膜样品厚度增加引起的基体效应却越强,相应特征谱线位置处的背景荧光强度就越大,因此样品厚度增加所引起的基体效应对薄膜法XRF光谱测量的灵敏度影响就越大。对于特征谱线能量较低(能量小于7 keV)的元素,以增加薄膜样品厚度的方式来增加待测组分的质量厚度浓度,并不能有效地提高薄膜法XRF光谱测量的灵敏度;对于特征谱线能量较高的元素(能量＞7 keV),可以通过适当增加样品厚度以增加被测组分的质量厚度浓度的方式来提高XRF光谱测量的灵敏度,薄膜样品厚度在0.96～2.24 mm内,更有利于XRF光谱的测量与分析。该研究为大气及水体重金属薄膜法XRF光谱分析中薄样制备及富集技术提供了重要的理论依据。     

青岛海藻重元素富集特性的SR-XRF分析及对海洋环境监测的应用

利用同步辐射X射线荧光 (SR XRF)定性和定量地分析了采自中国青岛海滨的 9种海藻 1 4个样品重元素的富集特性 ,发现不同种海藻重元素的富集特性有很大的差异。海蒿子对As和Sr,鸭毛藻对Br,海带对Ⅰ具有超富集能力。Mn/Fe峰强比的变化 ,是元素间拮抗的结果 ,与海水环境相关。测量了标样植物南极苔藓的检出限。定量地分析和比较了在青岛同一海滨分别于 1 985年和 1 999年采集的 5种海藻样品的XRF谱。1 999年采集的海藻的Fe ,Zn ,As,Br和Pb等元素含量明显上升 ,特别是海蒿子中的As和刺石松中的Pb分别增加了 1 55 %和 1 2 0 % ,结果说明了 1 4年来青岛海洋环境污染加重的趋势。     

ICP-AES测定两种牡丹胚乳中的矿质元素

采用电感耦合等离子体-原子发射光谱法测定了紫斑牡丹和滇牡丹胚乳样品中14种矿质元素（K、Na、Ca、Mg、Fe、Cu、Zn、Mn、Li、Ni、B、Ag、Cd、Pb）含量。结果表明,各测试元素的校准曲线线性良好;两种牡丹胚乳中4种人体必需的常量元素K、Na、Ca、Mg及6种与人体健康和生命有关的必需元素Fe、Cu、Zn、Mn、Ni、B含量丰富,3种对人体有害的微量元素Ag、Cd、Pb中,Ag与Cd均未被检出。表明两种牡丹胚乳矿质营养丰富,值得深入研究和开发利用。     

ICP-AES测定多目标水地球化学普查样品中的14种微量元素

采用IRIS Intrepid Ⅱ SXP ICP光谱仪,对地球化学普查水样中Ba、Be、Cd、Co、Cr、Cu、Fe、Mn、Mo、Ni、P、Pb、Sr和Zn等元素的测量条件进行了探讨,优化了实验条件,进行了大批量实际样品的测定.方法简便,快速.检出限、精密度和准确度均符合质量管理的要求.     

应用XRF与ICP-MS研究陨石样品的元素分布

分别采用X射线荧光光谱无标样全定量分析法(XRF)和微波消解/电感耦合等离子体质谱法(ICP-MS)对铁陨石和石陨石样品进行了元素分析。XRF法检测陨石样品中的常量元素,ICP-MS检测陨石中的微量元素。实验结果表明：XRF法可以检测出陨石样品中含量在10 μg·g-1以上的所有金属和非金属元素,得出两类陨石中共同含有的6种常量元素是Fe,Mg,Si,Na,Al和Ca。不同地区的铁陨石中均含有大量的Fe,石陨石中含有大量的Si。ICP-MS法检测陨石中的24种元素,选出共同存在的9种元素V,Ni,Mo,Ag,Sn,La,Gd,Hg和Pb进行对比分析,得出铁陨石中的重金属元素和稀土元素的含量远高于石陨石。所有的铁陨石样品中Sn元素的含量大约是石陨石的10～25倍,铁陨石中稀土元素La和Gd的含量大约是石陨石的6倍,新疆的5A号和6A号铁陨石中Pb的含量比来自山东的铁陨石(1A, 2A, 3A, 4A)多5～13倍,来自内蒙古的石陨石(9B,10B)比来自新疆的石陨石(7B,8B)多了三种元素La,Mo和Gd。     

兴城地区岩石光谱特征与物性参数、金属元素间响应关系研究

岩石物性参数、元素含量和光谱特征三者之间的相互关系并非独立存在, 研究三者之间的相互关系,对于探索通过遥感信息进行岩石矿物成分、物性参数的定量反演方法奠定基础。采集了兴城地区590块岩样本,分析其物性参数（密度、介电常数、电阻率、磁化率）、金属成分含量（Fe, Ti, V, Mn, Zr, Co, Zn, Nb, Bi, Pb）以及岩石光谱之间的关系。将各物化参数与原始光谱、光谱吸收深度、光谱小波包分解后的高低频做相关性分析,找出各物化参数影响光谱吸收和反射的特征波段,探究关系密切的参数。该研究为岩石岩性分类、某种金属元素和物理特性的反演以及用某种参数来预测关系密切的参数奠定了基础,取得如下结论：（1）获得了火成岩中Fe,Ti,Mn,V,Zn,Bi和Pb等元素的特征谱带,其中Fe元素含量更高,与光谱的相关性更显著。在0.4和0.54 μm波段附近存在Fe的特征反射波段,1.0~1.5 μm波段范围内存在Fe元素的特征吸收波段;在0.4~0.55和0.6~0.65 μm波段范围内,Ti元素与光谱的相关性更显著,在2.28 μm波段附近存在Ti的特征吸收波段;在0.41 μm波段附近存在Mn的特征反射波段;火成岩、沉积岩V元素与光谱相关性差异性较大,在0.76,0.81,0.89,0.95 μm波段附近可能存在火成岩的特征吸收波段和沉积岩的特征反射波段;沉积岩的Zn元素含量与光谱的相关性比火成岩要显著,在0.41,1.36,1.59 μm波段附近可能存在火成岩Zn的特征反射波段,在2.34 μm波段附近可能存在沉积岩Zn的特征波段;2.14 μm波段附近,Bi元素对沉积岩光谱的吸收有一定的作用;Pb的特征谱带可能存在于0.45,0.54,2.29 μm附近;（2）在岩石各物理特性和光谱的关系研究中,在0.57~0.85 μm波段范围内,密度对光谱有很好的吸收反射特征,在0.53 μm波段附近,磁化率使光谱有较强的反射,在1.08 μm波段附近,磁化率使光谱产生较强的吸收;电阻率和光谱的相关关系与密度和光谱的相关关系极为相似;（3）在岩石各物性参数间的关系中发现,密度和电阻率呈显著正相关的关系;（4）在岩石各物性参数与金属元素的关系中研究发现,密度与各金属元素相关性较弱;磁化率与Fe和Ti元素呈显著的正相关关系;电阻率与各金属元素间的相关关系较弱;介电常数与各金属元素含量呈正相关关系,其中与V,Zn,Bi元素的相关关系最显著;（5）在金属元素间,Fe与Ti有较显著的正相关关系,Ti与Fe,V元素间有较强的正相关关系,Zn和Pb存在较强的正相关。     

ICP-AES法分析灵芝中的微量元素

采用湿法消解,ICP-AES法分析不同原料的两种灵芝子实体、灵芝子实体根部、灵芝混合物、灵芝破壁与不破壁孢子粉中的20种微量元素,Al,As,Ca,Cd,Co,Cr,Cu,Fe,Ce,Hg,K,Mg,Mn,Na,Ni,P,Pb,S,Se,Zn的含量.结果表明:不同灵芝样品中的矿物元素含量很丰富,其中元素K,Ca,Mg,Fe,Zn,P,S含量较高,主要存在的微量元素有:Cu,CO,Cr,Ni;具有潜在生理毒性的元素为Al,As,Hg,Pb,Cd,抗癌功效元素Se和Ge在所有灵芝样品中并未测得.孢子粉中重金属元素含量相对灵芝原料更低些,灵芝混合物中有添加的功效元素Fe和se,灵芝根部切片样品中的Ca,Cu,Zn含量与其他样品都要高,不同品种的灵芝原料中的微量元素含量存在一定的差异性.     

铅锌矿区居民头发中Pb，As，Cd等有害元素含量、微区分布及元素形态特征研究

头发是人体元素的排泄器官之一,头发中元素含量能反映出一段时间内矿区毒性元素在人体内的吸收和代谢情况。采用电感耦合等离子体质谱(ICP-MS)和电感耦合等离子体原子发射光谱(ICP-OES)对某铅锌矿区居民头发中Pb,As,Cd,Ca,Mg,Fe,Zn,Cu,Mn和Sr进行了定量分析,应用微区X射线荧光(Micro-XRF)和X射线吸收近边结构谱(XANES)测定了头发中的Pb和As等元素微区分布和Pb形态。研究发现(1)当地部分居民已经受到矿区中Pb,Cd,Cu和Mn等重金属污染的危害。(2)不同性别群体的生理特征和生活习惯是决定其分布特征的主要因素,其中女性头发中Pb,Cd,Ca,Mg,Zn,Cu和Sr的平均含量都显著高于男性,男性头发中的Fe显著高于女性;(3)由于各元素性质、来源和吸收机制等原因,矿区居民头发中Ca-Mg-Sr-Zn,Pb-Cd-Cu-Mn,Fe-Mn具有相关性;(4)矿区典型头发样本中Pb和As主要沿头发中轴分布,从发根至发梢含量有逐渐增多的趋势;(5)头发样品中Pb由4.7%Pb₃(PO₄)₂,36.8%Pb-GSH和8.4%PbS组成;(6)头发中不溶性磷酸铅、铅-半胱氨酸巯基结合态是发铅的主要存在形态,揭示了其为人体铅代谢的主要途径之一。     

离子交换树脂-固相萃取富集-电感耦合等离子体光谱法测定水中重金属元素

建立了离子交换树脂-固相萃取富集-电感耦合等离子体光谱(ICP-AES)联用测定水中的重金属元素Zn,Mn,Cu,Co,Ni,Cd,Pb的方法。实验采用Dowex50WX8强酸型阳离子交换树脂,通过优化富集分离条件和排除共存离子的干扰,最终确定最佳的样品pH,样品流速,洗脱液种类和浓度,样品体积分别为3.0~4.0,3.0 mL·min-1,3.0 mol·L-1 HNO₃,200 mL。方法中各元素的检出限和定量限范围分别为0.09~0.45和0.31~1.50 μg·L-1,加标回收率和相对标准偏差RSD(n=6)分别为95.3%～104.2%和1.25%～4.12%。采用该方法测定不同地区的样品,并与直接采用ICP-MS法进行对比,其测定结果基本吻合。实验表明该方法的检出限,定量限可以满足水中重金属元素Zn,Mn,Cu,Co,Ni,Cd,Pb的检测要求,准确性和精密度好,结果可靠,适用于测定水中Zn,Mn,Cu,Co,Ni,Cd,Pb。     

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。     

Elemental distribution and Pb speciation in vegetable and cereal seeds during germination by micro X-ray fluorescence and X-ray absorption near-edge structure

The distribution of the chemical elements in plants is closely correlated with biological functions. Micro X-ray fluorescence (μXRF) and X-ray absorption near-edge structure (XANES) spectrometry can be used to determine uptake, translocation, and accumulation of the elements in plants. In this research, μXRF and XANES were applied in studying distribution of the elements in the vegetable and cereal seeds during germination and the mobilization. It was found that (a) the distribution of the elements in the seeds was element specific; (b) K and Ca were mainly located in the embryo. Fe and Zn, as well as Mn and Cu, concentrated near the radicle and new developed root. Most of Pb was located in the new developing root; (c) the organic-Pb complexes functioned as the main components of translocation of Pb in the seeds during germination, and the formation of Pb₅(PO₄)₃Cl and Pb₃(PO₄)₂ in seed and plant tissues was the mechanism of tolerance and detoxification to Pb in plants.     

Chemical elements and certain risk factors of chronic noncommunicable diseases in the population of Novosibirsk

In a population sample of residents of Novosibirsk between the ages of 45 and 69, the complex of the following chemical components of blood is determined by SR XRF: K, Ca, Fe, Cu, Zn, Ge, Se, Br, Rb, Sr, Zr, and Pb. Risk factors of chronic noncommunicable diseases are determined: obesity, arterial hypertension, dislipidemia, and their associations with chemical elements Ca, Cu, Rb, Y, and Pb.     

等离子体原子发射光谱法(ICP-AES)测定玉米和大豆根系伤流液中无机元素流量

植物根系伤流液组分是根系活力和根冠关系的重要指标,应用高压硝化处理和ICP-AES法分别同时测定了玉米(品种3138)和大豆(品种鲁豆11)根系伤流液中18种无机元素流量。结果表明玉米和大豆根系伤流液中无机元素种类、流量及随生长发育期变化均有差异。玉米根系伤流液中流量较大的为K,Ca,Mg,P,Na, Si,Zn,Mn,Fe等, 范围为1～1 851.5 μg·h-1·plant-1,B,Cu和Mo均低于1 μg·h-1·plant-1,检测不到Co,Cd,Ba,Pb,Sr,As的存在。从拔节期到灌浆期,各无机元素流量有随生育期下降的趋势。大豆根系伤流液中流量较大的为Ca,Mg,K,P,Na,Zn,Mn,Fe,Cu等,范围为1～1 158 μg·h-1·plant-1,B和Mo均低于1 μg·h-1·plant-1,检测不到Si,Co,Cd,Ba,Pb,Sr,As的存在,各元素随大豆生长发育期呈现不同变化。     

Direct determination of mineral nutrients in soybean leaves under vivo conditions by portable X-ray fluorescence spectroscopy

A portable energy dispersive X-ray fluorescence (XRF) spectrometer furnished with an Rh X-ray tube was evaluated for the determination of macronutrients and micronutrients in soybean leaves (Glycine max L.). XRF instrumental parameters were optimized in a univariate way, and emission intensities were measured for 60 s and under vacuum for macronutrients, and during 180 s, under air, and 305 μm Al/25.4 μm Ti filter, for micronutrients. Fresh and dried leaves were irradiated, and it was possible to identify P, K, Ca, S, Mn, Fe, Cu, and Zn Kα emission lines. For comparative purpose, the samples were also microwave assisted, digested and analyzed by inductively coupled plasma optical emission spectrometry. In general, linear correlations between K, Ca, Mn, Fe, Cu, and Zn concentrations in the tested samples and the corresponding portable XRF (pXRF) intensities were obtained. The linear correlation coefficients (R²) ranged from 0.42 to 0.86. In addition, the detection limits were suitable for plant nutrient diagnosis. It is demonstrated that pXRF is a simple and powerful tool for analysis of plant materials.     

Evaluation of metal release from battery and electronic components in soil using SR‐TXRF and EDXRF

Potentially toxic elements may be leached contaminating the soil, surface, and ground water due to the improper disposal of batteries and electronic devices. The objective of this study was to evaluate metal release from batteries and electronic components deposited in specific receptacles filled with soil in which acid rain was simulated. The leachate solution and the soil were analyzed by synchrotron radiation total reflection x‐ray fluorescence and benchtop energy dispersive x‐ray fluorescence, respectively. Results indicate that batteries released K, Mn, Fe, Cu, Zn, and Pb and electronic component released Ti, Mn, Fe, Cu, Zn, and Pb. For batteries' leachate test samples, higher amounts of Fe, Cu, Mn, Zn, and Pb have been released compared with electronic component ones under same the experimental conditions. The Fe, Cu, and Pb concentrations in battery leachate test samples were above their National Environment Council maximum permitted values (MPV) and in the electronic waste leachate ones, only the Pb concentrations was above MPV. For soil sample containing batteries K, Mn and Zn presented higher concentrations, mainly at the 10‐cm topsoil, ranging from 0.16 to 0.50, 0.27 to 8.67, and 0.03 to 1.26, in % (% w/w), respectively. The Zn–C battery soil samples present similar behavior to the alkaline ones. The impact due to the Pb release was higher in the soil test samples with electronic components, in which their concentrations ranged from 51 to 394 mg/kg, above its MPV up to 28‐cm soil layer. The X‐ray fluorescence techniques employed were suitable for water and soil environmental evaluation.     

波长与能量色散复合式X射线荧光光谱仪特性研究及矿区土壤分析

波长与能量色散(WD-ED)复合式X射线荧光(XRF)光谱仪是一型国际上新近研发的XRF光谱仪。该研究比较了此型光谱仪的特性,建立了联用分析方法,并用不确定度对所建方法进行了评估,证明WD-EDXRF复合型光谱仪及其所建分析方法可用于土壤样品中主、次、痕量元素定量测定,并兼具了WD和ED各自的优点。研究表明：(1)对土壤质量和生态环境评价中具有重要意义的Mg,Al,P和K等元素,因WDXRF对轻元素具有更高灵敏度,故采用该型光谱仪和所建方法,可弥补单一采用ED方法的不足,从而为土壤质量和生态环境评价提供了更为灵敏和准确可靠的分析技术手段;(2)在本方法实验条件下,采用WDXRF测定,主元素Na₂O,MgO,Al₂O₃,P₂O₅,K₂O的检出限优于EDXRF,而SiO₂, SO₃, CaO, MnO, Fe₂O₃则是由EDXRF测定的检出限更优。对于谱线重叠较严重的微量元素,多数情况下WDXRF的检出限更低;(3)对主元素而言,总体上K及其原子序数之前的轻元素WDXRF准确度更好,Ca及其之后的元素EDXRF准确度更好。然而,由WDXRF和EDXRF获得的准确度也与样品相关,在某些情况下,EDXRF测定K的准确度会更好。微量元素和重叠干扰比较大的元素,采用分辨率好的WDXRF可获得更好的准确度;对于受其他元素谱线重叠影响较小的元素,EDXRF给出的结果准确度更好;(4)选用添加石蜡粘结剂的粉末压片法,利用该方法制成的地质样品粉末压片结实、无脱落,未观察到掉渣、掉粉现象,且分析准确度和精密度良好;(5)利用所建立的WD-EDXRF方法测定了采自集中开采矿区和附近河流及河漫滩沉积物,揭示矿区表层土含有较高浓度的Cu,Pb和Zn,可为找矿提供指示信息;(6)进行了矿区周边农田土壤分析,获得了元素分布趋势图,揭示矿集区附近农田土壤Pb和As等浓度较高,需要采取必要的生态与环境保护措施,以减小和避免对于人类健康的潜在影响。     

XRF applications in archaeometry: analysis of Marajoara pubic covers and pigments from the sarcophagus cartonage of an Egyptian mummy

This work presents two applications of XRF in archaeometry. The first case involved a female mummy from the Roman period, which is considered one of the most important pieces of the National Museum (Rio de Janeiro), because of its unconventional embalming with legs and arms swathed separately. The objective was to characterize the elemental composition of the pigments found in the sarcophagus cartonage and to verify whether they were in accordance with those used by Egyptian craftsmen in the cited period. The elements identified were Si, S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Sr, Hg, and Pb. In the second case, the composition of decorated pottery pubic covers (tangas) from the Marajoara culture was evaluated using EDXRF. Ceramics from the Marajó Island (at the mouth of Amazon River, Brazil) represent one of the most beautiful and sophisticated styles of the pre‐Columbian art. Decorated tangas were used by Marajoara girls probably as part of puberty rites. The analyzed samples were two tangas and four fragments from the National Museum's collection. One fragment (sample 22245) presented a different design pattern that seemed to indicate a different provenance. The elements identified were K, Ca, Ti, Mn, Fe, Cu, Zn, Ga, Rb, Sr, Y, Zr, and Pb. Multivariate statistical analysis was applied to the results. Copyright © 2007 John Wiley & Sons, Ltd.     

ICP－AES法测定富锗酵母中微量元素

本文采用美国ＬｅｅｍａｎＬａｂｓ公司中阶梯光栅光谱仪测定了人工培养的富锗酵母中高含量锗及镁、铜、锌、铁、钾、钠等微量元素，研究了富锗样品的前处理方法，样品加标回收率在９０％－１０３％之间，测量相对标准偏差：锗１０％，镁、铜、锌、铁、钾、钠等元素小于７％。     

Measurement of K,Fe, Cu and Zn levels in secondary colorectal liver cancer and surrounding normal liver tissue,and their potential as a tissue classifier

An x‐ray fluorescence (XRF) system utilising a synchrotron radiation source was used to quantify the levels of Fe, Cu, Zn and K in colorectal liver metastases and surrounding normal liver tissue as a possible mechanism for detecting cancer in a tissue biopsy. Sixty samples were measured and a lower level of all four elements was found in the cancer samples compared with that of the normal liver. The difference in levels of Zn, Fe, Cu and K between cancer and normal tissue was significant with p values of < 0.01 for Zn, Fe and K, and 0.033 for Cu. The precision was estimated by repeated measurements yielding a precision of 96, 91, 95 and 86% for Zn, Cu, Fe and K, respectively. The homogeneity of the distribution of elemental concentrations was assessed by measuring eight normal liver and eight cancer samples from the same patient. The variation of Zn, Cu, Fe and K levels between normal liver samples was 10.4, 15.4, 15.85 and 29.1%, respectively, and in the colorectal metastases was 10.18, 15.92, 8.44 and 22.35%, respectively. Receiver operator characteristic (ROC) analysis was performed for all elements and showed that Zn could be a reliable indicator of tissue classification with an ROC area under the curve of 0.998 and a resulting sensitivity and specificity of 100 and 96.67%, respectively. Fe had an ROC area under the curve of 0.856 and sensitivity and specificity of 83.3 and 76.67%, respectively. Cu and K did not perform as well with areas under the curve of 0.75 and 0.706, respectively. Copyright © 2008 John Wiley & Sons, Ltd.