宁夏决明子中6种无机元素形态分析

用传统煎煮法对宁夏产决明子中钾、钙、锰、铁、铜和锌6种元素进行提取,采用火焰原子吸收光谱法对决明子各种形态中的6种元素进行测定。结果显示,决明子中6种元素在原药、渣和煎汁中总含量特征:K>Ca>Fe>Zn>Mn>Cu。方法的回收率在80.8%—115.1%之间,各元素分析方法的RSD小于3.8%。     

ICP-AES测定云南楚雄糖尿病患者发样微量元素的研究

探讨微量元素与糖尿病间的关联性及临床意义。采用ICP-AES等离子体发射光谱仪测定了楚雄地区糖尿病患者人发中11种元素,采用2,3-二氨基萘荧光法测定发样中的硒元素。选取糖尿病患者120例,对照组35例。糖尿病组发样中常量元素Ca、Mg低于对照组,P高于对照组;除Cd、Cr、Fe外,微量元素Zn、Se、Ni、Mn、Cu等5种元素低于对照组,并有显著差异(P0.01)。糖尿病组间性别比较数据显示男性除发Ni、Mn、P外,其余元素含量均低于女性,其中发锌远低于女性。3个不同年龄段糖尿病人群的微量元素含量变化显示Fe、P2种元素随年龄增加含量增高;Mg、Cd2种元素随年龄增加含量减少;其余各元素变化情况为Fe、P元素在老年组中较高,Cu、Cd、Mg较低;Mn、Cr、Cu元素含量在中年组中较高,而Zn、Se略低;Zn、Se在青年组较高,而Mn、Cr低。城市人群发中Zn、Cd、Cu、Mg、Ca含量比农村人群高;Se元素含量二者间差别也不大,其余元素含量均低于农村人群。楚雄地区糖尿病患者发中Zn、Se、Mg、Mn4种元素水平低,楚雄地区糖尿病患者致病原因可能与地区属低Se水平和患者体内硒水平低有关。     

Trace element categorization of pollution sources in the equator town of Nanyuki,Kenya

An air pollution campaign was carried out in the town of Nanyuki at four different sites during July and August 1999. Nanyuki is situated on the equator on the northwestern slope of Mount Kenya at about 1930 m above sea level. The intention of the project was to characterize aerosol elemental compositions in two size fractions, associated with specific natural and anthropogenic activities. A dichotomous impactor was used for sampling and an energy‐dispersive x‐ray fluorescence spectrometer was used for the analysis. Fourteen elements (Si, S, K, Ca, Ti, Mn, Fe, Cu, Zn, Ga, Br, Rb, Sr and Pb) were analysed in all the samples. The concentration of Pb was highest at a site in the vicinity of open‐air vehicle garages. The four sites recorded high concentrations of fine S, Cl and K. Fine Zn and Br were also measured at all the sites. In the coarse size range, the concentrations of soil‐derived elements (Si, K, Ca and Fe) were dominant. The high concentration of coarse Cl was considered to be due to the contribution of sea salt and that of S to be a contribution of gas to particle conversion of SO₂. The two elements S and Cl signified the influence of long‐distance transported aerosols. The comparatively high concentrations of fine Pb and Br signified the high rate of vehicle repairs, which is a major activity close to one of the sites. Generally, soil dust‐derived particles and those from biomass burning dominated the town aerosols. Copyright © 2004 John Wiley & Sons, Ltd.     

参术汤中8种元素的初级形态分析

对一中药复方参术汤以及组成该复方的4种单味药水煎液中8种元素进行初级形态分析,探讨了复方与单味药中元素含量之间的关系,火焰原子吸收光谱法测定元素含量。测定结果表明:复方中铁、锌、钙的含量分别是单味药中元素含量之和的2.44、2.27、1.26倍;锰为0.84倍;镁、铜、钠、钾相差无几(0.97—1.04倍)。对于可溶态亦具有同样的规律。说明复方水煎液中各成分发生相互作用导致有些元素形态发生改变。     

Multielement analysis in serum of healthy population of the metropolitan region of Rio de Janeiro in Brazil by SRTXRF

The determination of multielemental concentrations in physiological fluids is of considerable interest in clinical chemistry. Since it has been established these levels in human serum can be utilized as indicators for several pathological conditions. The multielement composition determination in human serum is important for the investigation of their role in human physiology and metabolism. From this research, more detailed studies on the health of individuals living in the metropolitan region of the state of Rio de Janeiro can be realized in order to improve the quality of life of these individuals. We studied 180 healthy volunteers (80 males and 100 females) aged 19 to 60 years. All the serum samples had been collected of people who live in the urban area of Rio de Janeiro City/Brazil. The measurements were performed at the X‐Ray Fluorescence Beamline at the Brazilian National Synchrotron Light Laboratory (LNLS), in Campinas, São Paulo. We were able to determine the concentrations of the following 11 elements: Na, P, S, Cl, K, Ca, Fe, Cu, Zn, Br and Rb. In this study, we used statistical analysis for the principal components. We were able to verify the presence of two factors that divided the elements into two groups: group 1 formed by elements: Cl, K, S and Ca and group 2 by elements Cu and Zn. Copyright © 2015 John Wiley & Sons, Ltd.     

Applicability of MiniPal 4 compact EDXRF spectrometer for soil and sediment analysis

Optimum measurement parameters for analysis of soil and sediment samples with the compact MiniPal 4 (MP4)EDXRF spectrometer (PANalytical, Almelo, The Netherlands) were presented. The following elements were considered: K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As and Pb. Since the elements from low Z to medium Z region were covered, three measurement conditions (sequences) were defined. The following parameters were selected for measurement of the elements K, Ti, and V: voltage = 12 kV; current = 750 µA; filter material: Al_thin. Cr, Mn and Fe were measured at 20 kV; 300 µA with Al filter while for measurements of Ni, Cu, Zn, As, Pb, Rb, and Sr an Ag filter was selected and tube voltage and current were 30 kV and 300 µA. Each sequence was measured for 200 s and measurements were done in the air. MP4 spectrometer was characterized with acceptable precision, long‐term stability and satisfactory minimum detection limit for the analyses of soil and sediment materials. For the elements K, Mn, Fe, and Ti the precision of the analysis was better than 0.5% and for all the other elements better than 5%. Detection limits for sediment samples were 20 ppm for K, 6.1 ppm for Ti, 5.2 for Mn, 4 ppm for Fe, 4.2 ppm for As and less than 2 ppm for all the other elements. These values were significantly lower compared to typical concentrations of the same elements found in unpolluted soil and sediments. Copyright © 2008 John Wiley & Sons, Ltd.     

ICP-AES测定肉苁蓉及其提取物中矿质元素含量

采用ICP-AES法测定两种肉苁蓉及其提取物中11种矿质元素,结果表明：肉苁蓉中Mn,K,Ca,Mg,Na含量（μg·g-1）显著高于管花肉苁蓉,分别为17.70,16 278.03,1 947.25,1 662.76,106.79;肉苁蓉50%甲醇提取物中Fe,Cu,P含量为水提物的1.5倍、2.4倍、1.1倍,Mn,Zn,K,P,Mg,Na含量为100%甲醇提取物的3.8倍、1.2倍、1.6倍、2.3倍、2.2倍、1.1倍;管花肉苁蓉50%甲醇提取物中Cu和P含量为水提物的1.6倍和1.2倍,Mn,Zn,K,P,Mg,Na,Al含量为100%甲醇提取物的2.0倍、1.6倍、1.6倍、1.4倍、1.8倍、1.2倍、1.2倍;肉苁蓉和管花肉苁蓉内矿质元素在50%甲醇中的溶出率分别是60.79%～83.10%和44.58%～83.84%,且Mn, Zn, K, P, Ca, Na, Al的溶出率显著高于水和100%甲醇提取。此研究为高效利用肉苁蓉药材中的矿质元素提供了科学依据。     

Levels and sources of heavy metal contamination in road dust in selected major highways of Accra,Ghana

Environmental studies have revealed significant contributions of vehicular exhaust emissions to high pollution levels in urban dwellings. The levels and sources of heavy metal contaminations of some major roads in Accra have been investigated in this work. Street dust samples collected from four major roads in Accra (Mallam Junction‐Weija road, John Teye‐Pokuase road, Tema Motorway and Tetteh Quarshie Interchange in Accra) were analysed for their elemental concentrations using energy‐dispersive X‐ray fluorescence. Twenty elements were identified: K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr and Pb. Significant concentration levels were obtained for K, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, Br, Rb, Sr, Y, Zr and Pb in all the samples and were used for the source identification. Enrichment factors and principal component analysis were used to verify the anthropogenic contribution to road dust. Results obtained for the enrichment factors showed moderate enrichment for V, Cr and Cu, while Zn, Br, Zr and Pb were significantly enriched. Principal component analysis identified four sources and their contributions to the elemental contents in the road dust. Natural crust, brake wear, tyre wear and vehicle exhaust emission were the four sources identified. The contribution of vehicular non‐exhaust emissions to heavy metal contamination in the road dust was found to be greater than that of exhaust emissions. Copyright © 2012 John Wiley & Sons, Ltd.     

Comparative study on mineral elements in the roots of Rheum tanguticum from Qinghai-Plateau

In the present paper,the authors analysed 10 mineral elements in the roots of Rheum tanguticum collected from 30 different habitats.The mean concentration values of the 10 elements decreased as follows:Ca＞Mg＞K＞Fe＞Mn＞Cr＞Zn＞Ni＞Cu＞Se.Ca,Mg,K and Fe were abundant in this herb.Most elements varied over a wide range depending on the different habitats.The mineral element data were evaluated by principal component analysis to reveal the distribution pattern of elements in tool Four principal components(KCa factor,Cu factor,Mg factor and Zn-Se factor)of plant elements were selected.The authors'study provided a new scientific foundation for further studies and general application of this Chinese herb.     

同步辐射XRF法分析温室油菜中微量元素的分布

蔬菜是补充人体微量元素的重要途径,但是蔬菜不同部位、特别是温室蔬菜不同部位各种元素的分配目前还没有研究清楚。利用同步辐射XRF法测定了温室油菜中各种微量元素中的分配情况。研究结果表明温室油菜中含有许多人体必需的微量元素,特别是Ca,Mn,Fe,Cu和Zn;但是不同的元素在叶片和根系的不同部位含量有所差异,总体上油菜根系中K,Ca和Mg的含量显著高于叶片,叶片中Fe,Zn,Co,Ni和Cu的含量则高于根系,其中侧根中的各种元素含量均很低。K,Ca和Co在叶片中间位置含量较高,由边缘向中部含量逐渐增加;Cu,Mn,Fe和Ni含量由叶片基部到叶尖处含量逐渐增高;Zn总体含量也比较均匀。在主根中各种元素普遍表现为根基部向根尖呈现先上升再降低的规律,根系中间部位各元素含量高,且普遍表现为根基部的含量要高于根尖处的含量。     

Elemental composition of marine sponges from the Berlengas natural park,western Portuguese coast

Analytical studies of sponges have recently become a matter of interest, since these organisms have been reported to accumulate high levels of some elements, including heavy metals, which may have an anthropogenic origin, allowing their application as environmental pollution indicators. In the present work, 35 sponges collected in August 1998 at the Berlengas Natural Park were classified and analysed by secondary target energy‐dispersive x‐ray fluorescence spectrometry (EDXRF). Some major, minor and trace elements could be determined: Al, Si, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, As, Br, Rb, Sr, Zr, I and Pb. To assess some local influences on the sponge composition, two sediment samples were also taken from the area and analysed. Besides these elements, sponges are constituted by fairly high percentages of elements that do not emit characteristic x‐ray lines. Therefore, absorption corrections for quantitative calculations were carried out taking into account the ratio between the inelastic and elastic scattered incident radiation from a silver secondary target to calculate the mean atomic number of the light matrix. Calibration was performed using chemical compounds and standard reference materials. Precision, accuracy and detection limits for the range of elements determined by the method are particularly suitable for the chemical analysis of these organisms. Results for the sediment chemical composition indicated the existence of high Ca and low Si levels and confirmed the absence of any trace metal contamination in the region. The sponge composition showed low Si contents, even in siliceous specimens. Certain high elemental contents determined in some species indicated a clear selective bioaccumulation of particular trace elements, such as Ni, Zn and As, which is not dependent on local influences. Copyright © 2003 John Wiley & Sons, Ltd.     

Effect of radiation therapy on trace elemental concentrations of hair samples of cervical cancer patients—PIXE technique

Trace elemental analysis of hair samples from subjects suffering with cervical cancer before radiation therapy and at successive intervals during radiation therapy was carried out using the PIXE technique. A 2 MeV proton beam was employed. The elements Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn and Pb were identified and their relative concentrations were estimated. The concentrations of Cl, K, Ca, Ti, Cr, Mn, Fe, Ni and Zn were found to be lower in hair samples of cervical cancer patients before radiation therapy than those from controls, whereas the concentration of Cu showed the opposite trend. The concentrations of Cl, K, Ca, Ti, Mn, Fe, Cu, Zn and Pb showed a definite trend of variation with successive intervals of radiation therapy, which indicates that these elements are affected during radiation therapy. The Cu/Zn ratio also decreases with successive radiation therapy. Copyright © 2004 John Wiley & Sons, Ltd.     

小尾寒羊胴体不同部位矿物元素的比较研究

采用火焰原子吸收法对小尾寒羊胴体不同部位的Ca,Fe,K,Cu,Zn和Mg等矿物元素的含量进行了分析测定。该法的加标回收率为96.9%—104.2%,RSD值小于2.0%,具有良好的准确度和精密度。研究结果表明：小尾寒羊肉中Ca,Fe,K,Zn和Mg含量丰富,颈肉中Ca的含量最高,肋肉和腰肉中Mg的含量较高,心和肝中Fe的含量较高,心和颈肉中Zn的含量较高。此测定结果可为探讨羊肉中矿物元素的含量与其代谢调节功效的相关性提供科学依据。     

脉通中金属元素含量的测定

本文采用火焰原子吸收分光光度法测定了中成药脉通中K ,Ca ,Na ,Mg ,Fe,Zn ,Mn ,Cu ,Ni,Cr,Cd和Pb十二种金属元素的含量 ,计算Cu/Zn比值和Ca/Mg比值 ,并对其结果进行了分析。结果显示 ,脉通中含有丰富的宏量元素K ,Ca,Mg和有益的微量元素Cu ,Zn ,Fe等元素 ,有毒元素Cd和Pb的含量较低。金属元素的含量高低顺序为 :K >Ca >Na >Mg >Fe >Zn >Mn >Cu >Ni>Cr>Cd >Pb ,Cu/Zn比值 >Ca/Mg比值。测定结果为探讨中成药中宏量、微量元素与治疗脑血管疾病功效的关系提供了有用的数据。     

荆芥不同器官在不同采收时间的ICP-AES矿质元素分析

各种矿质元素在荆芥各器官间贮藏差异。从矿质元素角度了解荆芥合理的药用部位组成以及收时间。应用ICP-AES技术,测定并分析了在不同采收时间,荆芥的不同器官矿质元素含量、累积量和比例。结果显示, 在不同采收时间,(1)荆芥穗中常量矿质元素K, P和微量矿质元素Cu含量最高,荆芥叶中常量元素Mg, Ca, Na和微量元素Fe, Mn, Zn含量最高。(2)荆芥不同器官所含常量元素中Ca和K含量最高,Na含量最低;所含微量元素中Fe含量最高,Mo含量最低。(3)在荆芥茎中,K∶P最高,而Zn∶Cu则为最低;Ca∶Mg和Fe∶Mn在荆芥穗中最低。(4)随着采收时间的推移,各元素在荆芥不同器官中的含量变化并不显著。荆芥茎中各矿质元素含量均较低; 从矿质元素含量的角度看,在合理的采收时间范围内,荆芥的质量受时间影响不显著。     

FAAS测定提宗龙胆花中的7种矿质元素

采用火焰原子吸收光谱法对藏药提宗龙胆花中Cu、Zn、Fe、Mg、Ca、K、Na 7种矿质元素进行了测定。在选定的测定条件下,提宗龙胆花中各元素间相互干扰小,对测定结果无明显影响。方法的校准曲线线性关系良好(r=0.9944—0.9999),方法的回收率(n=6)在94.5%—107.7%之间。提宗龙胆花中K、Ca、Mg、Fe等元素含量均较高,研究结果为提宗龙胆这一传统藏药的合理开发与利用提供了可靠依据。     

Reference spectra of important adsorbed organic and inorganic phosphate binding forms for soil P speciation using synchrotron‐based K‐edge XANES spectroscopy

Direct speciation of soil phosphorus (P) by linear combination fitting (LCF) of P K‐edge XANES spectra requires a standard set of spectra representing all major P species supposed to be present in the investigated soil. Here, available spectra of free‐ and cation‐bound inositol hexakisphosphate (IHP), representing organic P, and of Fe, Al and Ca phosphate minerals are supplemented with spectra of adsorbed P binding forms. First, various soil constituents assumed to be potentially relevant for P sorption were compared with respect to their retention efficiency for orthophosphate and IHP at P levels typical for soils. Then, P K‐edge XANES spectra for orthophosphate and IHP retained by the most relevant constituents were acquired. The spectra were compared with each other as well as with spectra of Ca, Al or Fe orthophosphate and IHP precipitates. Orthophosphate and IHP were retained particularly efficiently by ferrihydrite, boehmite, Al‐saturated montmorillonite and Al‐saturated soil organic matter (SOM), but far less efficiently by hematite, Ca‐saturated montmorillonite and Ca‐saturated SOM. P retention by dolomite was negligible. Calcite retained a large portion of the applied IHP, but no orthophosphate. The respective P K‐edge XANES spectra of orthophosphate and IHP adsorbed to ferrihydrite, boehmite, Al‐saturated montmorillonite and Al‐saturated SOM differ from each other. They also are different from the spectra of amorphous FePO₄, amorphous or crystalline AlPO₄, Ca phosphates and free IHP. Inclusion of reference spectra of orthophosphate as well as IHP adsorbed to P‐retaining soil minerals in addition to spectra of free or cation‐bound IHP, AlPO₄, FePO₄ and Ca phosphate minerals in linear combination fitting exercises results in improved fit quality and a more realistic soil P speciation. A standard set of P K‐edge XANES spectra of the most relevant adsorbed P binding forms in soils is presented.     

Characterization of essential and toxic elements in cephalopod tissues by EDXRF and AAS

Concentrations of K, Ca, Cr, Fe, Ni, Cu, Zn, Se, Rb, Sr, Cd, Hg and Pb were measured in the muscle, digestive glands and gonads of Octopus vulgaris, Lolligo vulgaris and Sepia officinalis captured in the west and south coast of Portugal. Essential elements (K, Ca, Fe, Cu, Zn, Se, Rb and Sr) were obtained by energy dispersive x‐ray fluorescence spectrometry, while toxic elements (Cr, Ni, Cd, Hg and Pb) were obtained by atomic absorption spectrometry. The latter technique was used owing to its higher sensitivity, since these elements were not detected by the first technique. The tissues of the three species present a similar pattern for essential elements. Potassium and Ca are present at the highest concentration in all the studied samples. The highest levels for toxic elements were found in the digestive glands, exceeding the maximum allowed values in the case of Se and Cd. However, in the muscle tissue these values were never reached. Comparing both coasts, we can say that the west coast presents higher levels of Pb while the south coast presents enhanced levels of Hg. Copyright © 2007 John Wiley & Sons, Ltd.     

绿松石成分的EDXRF方法研究

利用激光剥蚀电感耦合等离子体质谱仪(LA-ICP-MS)测试方法对来自湖北的26块表面相对干净、颜色均匀的绿松石样品进行定值,每个样品表面按照“田字格”的方式逐一测试9个点,用于评价绿松石成分的均匀性。数据结果显示,绿松石样品中Al,P,K,Cu,Fe,V,Cr和Zn的平均变异系数在5.4%以下,而CaO和SiO₂的平均变异系数分别为34.8%和16.2%,说明绿松石中Si和Ca元素存在明显的不均匀性。选取其中的21个样品作为参考标准样品,5个作为未知样品,采用能量色散型X射线荧光光谱仪(EDXRF)建立绿松石的工作曲线,用于测定绿松石的成分。研究结果显示主量元素Al,P和Cu工作曲线的相关系数在92.3%~94.3%之间,平均相对误差在4.6%~9.7%;微量元素Fe,Cr和Zn的相关系数达到0.990以上,K和V元素工作曲线的相关系数分别为0.939和0.972,这五种元素平均相对误差范围在7.2%~13.9%;而Si和Ca元素工作曲线的相关系数分别为0.958和0.866,且在5个未知样品中,Si和Ca元素的平均相对误差分别为348%和27.8%,这与绿松石中Si和Ca元素的含量低和不均匀性,以及仪器方法的检出限等影响因素有关。重复性实验显示Al,P,Cu,Fe和Zn元素的相对标准偏差(RSD)均在1%以内,精密度较高;V,Cr,K,Ca和Si元素的RSD在1.34%~10.17%之间。该研究为快速、准确、无损地定量测定绿松石中Al,P,Cu,Fe,Cr,Zn,V和K等元素的含量提供了一种新思路和新方法,可运用于实验室的绿松石检测鉴定。     

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.