X射线荧光光谱法测定橄榄岩主次痕量元素

本文采用熔融玻璃片和粉末压片法制样，用理论ａ系数和散射线内标法校正元素间的效应，     

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.     

An assessment of the impact of construction work on fine particulate matter in the University of Jordan: A PIXE study

Aerosol sampling was carried out prior to and during an active construction work at the University of Jordan in Amman, Jordan. Elemental characterization for 60 PM_2.5 samples was performed by particle-induced X-ray emission (PIXE) technique at the LABEC laboratory of INFN in Florence, Italy. Twenty three elements (Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, Zr, Ba, and Pb) were detected, and their concentrations were assessed during three sampling periods, namely, “No Construction,” “Pouring Concrete,” and “Bleaching.” The results showed higher concentrations of soil-related elements and lower concentrations of anthropogenic-related elements during construction periods compared with their concentrations before construction. Soil-related elements showed very low enrichment factor (EF) and high correlation coefficients during all sampling periods. Anthropogenic-related elements were very much enriched and correlated only during the first sampling period “No Construction.”     

Methodology for the Determination of Stoichiometry and Metal Impurities in New PZT Ceramics by Inductively Coupled Plasma Optical Spectrometry (ICP OES)

ABSTRACT

An inductively coupled plasma optical emission spectrometry (ICP OES) method for Pb, Zr, Ti, Sr, Cr, Fe, Cu, Mn, and Al determination in PZT-ceramics is described. Careful analytical work was carried out in order to evaluate precision, accuracy, and matrix interference. Different procedures were investigated for the ceramics decomposition. Axially viewed plasma operating conditions were evaluated for trace elements (Al, Fe, Cu, Mn, and Cr) in presence of sample matrix. The relative standard deviation (RSD) ranged from 0.7 to 3.9%, whereas the analytes recoveries in the spiked samples ranged from 92 to 119%. The detection limits (LODs) of trace elements ranged from 2.4 to 2.6 µg g^?1. The developed method is useful for evaluating the PZT-ceramics synthesis.     

Trace element composition of common sea buckthorn (Hippophae rhamnoides L.) tissues

Synchrotron radiation X-ray fluorescence analysis is used to determine for the first time the absolute content and biological accumulation coefficients for a set of 21 chemical elements (K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Rb, Sr, Zr, Nb, Y, Mo, and Pb) in the fruits, leaves, bark, roots, and root nodules of the sea buckthorn (Hippophae rhamnoides L. ssp. mongolica Rousi). It is found that all sea buckthorn tissues accumulate Ti, Nb, Cr, and Zr more intensively than the global average for terrestrial phytomass. On the other hand, none of the examined parts of the sea buckthorn plants accumulated the toxic elements Pb and As.     

Energy‐dispersive x‐ray fluorescence analysis of modern coloured glasses from Marinha Grande (Portugal)

The elemental composition (K, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Sr, Ba, Nd and Pb) of modern coloured glasses was obtained by energy‐dispersive x‐ray fluorescence (EDXRF) spectrometry. This non‐destructive technique is frequently used in the analysis of historical glass objects. Two reference glasses were also measured to assess the overall accuracy of the EDXRF method. Reference and unknown glasses were analysed without any preparation. The coloured glass samples studied belong to the Glass Museum of Marinha Grande and were chosen from two distinct collections, which were characterized by the different concentrations of some elements (K, Ti, Cr, Mn, Fe, Ba and Pb). The determined major elements allowed the identification of two raw materials used in glass manufacture, sand and lime. Multivariate statistical analysis, namely principal component extraction, simplified the identification of some of the colouring chemical elements, associating them with the different colours of the glass objects. Copyright © 2003 John Wiley & Sons, Ltd.     

Estimation of trace elements in some medicinal plants used in anti‐cancer drugs by PIXE

A trace elemental analysis was carried out in various parts of 12 anticancer medicinal plants, using the PIXE (particle‐induced X‐ray emission) technique. A 3‐MeV proton beam was used to excite the samples, and spectra were recorded using a Si (Li) detector. Data analysis was done using the GUPIX software. The elements Cl, K, Ca, Ti, V, Mn, Fe, Ni, Cu, Zn, Br and Sr were identified, and their concentrations estimated. The results of the present study provide justification for the usage of these medicinal plants in the development of anticancer drugs. Copyright © 2012 John Wiley & Sons, Ltd.     

Combined PIXE and X‐ray diffraction analysis of accretionary lapilli from the Cretaceous/Paleogene boundary El Guayal Section,Tabasco, Mexico

By employing the techniques, X‐ray powder diffraction (XRPD) and particle‐induced X‐ray emission (PIXE), it could be obtained in a simply way an overall vision of the structure and chemical composition of a spheroid (lapillus) collected in the K/Pg deposit located at the place called El Guayal in Tabasco, Mexico. The XRPD analysis indicates the presence of an amorphous and four crystalline phases (quartz, calcite, ankerite, and montmorillonite) in the spheroid. None sulfur crystalline phases were detected. PIXE results show the presence of different atoms in a weight percentage that follows the sequence: Si > Al > Ca > Fe > Sr > Cu > Ti > Mn > Y > Rb > Zn > Pb. None of platinum group elements were detected. PIXE analysis by of the lapillus shows the presence of the most abundant atoms in the Earth's crust, but in this case, the relative abundance Fe‐Ca is inverted, and the Sr/Rb proportion is considerably higher than that observed in the crust. Additionally, nor sulfur or any of the platinum group elements was detected in the lapillus. Except for the case of trace elements detected, in general, no characteristic pattern is observed in the distribution of the most abundant elements. Copyright © 2015 John Wiley & Sons, Ltd.     

Studies on the composition of ancient Indian punch‐marked silver coins

Punch‐marked coins are the oldest known numismatic objects used in ancient India. Seven punch‐marked silver coins were analysed by using the non‐destructive multi‐elemental PIXE technique. A 3 MeV proton beam from a pelletron accelerator was used for irradiation of these samples to obtain the spectral data and GUPIX software was employed to derive the elemental concentrations. The results reveals that silver, copper, gold and lead are significant constituents of the punch‐marked silver coins and there are also traces of elements such as Ti, Cr, Mn, Fe, Co, Ni, As and Y, which seems to imply that PIXE can be used effectively for the non‐destructive quantitative analysis of ancient coins. Copyright © 2004 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.     

ICP-AES测定铝-钛-硼合金中的16种元素

电感耦合等离子体-原子发射光谱法(ICP-AES)测定铝-钛-硼合金中钛、硼、铁、硅、镓、铜、锶、锆、锌、镁、锰、镍、铅、钒、镉和铬等16种元素含量.对分析线的选择、铝基体的干扰,样品的预处理过程进行了探讨.经实验,方法的回收率在95%-110%之间,测定结果的相对标准偏差(n=6)在0.4%-3.0%之间.该方法准确...     

Comparison of trace elements analysis of nephrite samples from different deposits by PIXE and ICP‐AES

Comparing values of trace elements determined by external‐beam proton‐induced X‐ray emission (PIXE) and inductively coupled plasma atomic emission spectrometry (ICP‐AES) is important to find the provenience of raw materials of ancient nephrite artifacts, because most previous elemental characterizations of nephrite minerals were obtained by ICP‐AES, but PIXE presents the possibility of nondestructive analysis for largely and integrally ancient nephrite artifacts. In this work based on 12 nephrite minerals, it shows that the distribution of trace elements of nephrite samples both in PIXE and ICP‐AES data are generally consistent, although large differences exist in some elements. According to the trace elements, the two types of nephrite mineralization origins can be distinguished, determined by PIXE and ICP‐AES, respectively. Moreover, depending on the PIXE and ICP‐AES data, Sr can be regarded as fingerprint element of Xiaomeiling nephrite minerals, and the differentiation of Sr content between Xiaomeiling nephrite minerals and ancient nephrite artifacts from Liangzhu culture (3300–2300 bc ) is clear evidence that the raw materials of the artifacts are not from Xiaomeiling deposit. The nephrite minerals from Wenchuan deposit can be distinguished from other samples because of their high values of Mn/Fe. Therefore, the PIXE can be used with ICP‐AES to judge mineralization mechanism and find fingerprint elements of raw materials of ancient nephrite artifacts. Copyright © 2012 John Wiley & Sons, Ltd.     

Effects of weathering on in situ portable X‐ray fluorescence analyses of geological outcrops: dolerite and rhyolite outcrops from the Preseli Mountains,South Wales

Laboratory experiments were undertaken to investigate the effect of weathering on dolerite and rhyolite samples from the Preseli Mountains, South Wales, an area of archaeological significance for the provenancing of archaeological artefacts. Portable XRF (PXRF) analysis was used to construct a depth profile of elemental concentrations through the weathering layer of suitable rock samples. These measurements were made by sequentially grinding away successive layers, each time measuring the newly exposed surface by PXRF. The elements studied included K, Ca, Ti, Mn, Fe, Ba, Nb, Pb, Sr, Y and Zr. In dolerite samples, Ca, Fe and Y were generally depleted in heavily weathered surface layers, whereas K and Pb were enhanced, the latter element significantly so, probably as a result of anthropogenic activities (emissions from leaded automobile fuel). Element behaviour in rhyolites was less consistent. A correction factor was derived for each element based on the ratio of the weathered surface concentration to the corresponding steady‐state (fresh rock) concentration beneath the altered layer. This correction factor was evaluated as a possible means of compensating for elemental discrepancies when measuring weathered surfaces. Improved data were obtained for a significant number of elements, but further work is required to evaluate this procedure fully. Copyright © 2005 John Wiley & Sons, Ltd.     

Quantitative non‐destructive determination of trace elements in archaeological pottery using a portable beam stability‐controlled XRF spectrometer

A portable beam stability‐controlled XRF spectrometer developed at the LNS/INFN laboratories at Catania (Italy) was used for the non‐destructive determination of some trace elements (Rb, Sr, Y, Zr and Nb) in fine pottery artefacts. The XRF system and the method developed to control the energy and intensity stability of the excitation beam are briefly discussed. Concentrations of Rb, Sr, Y, Zr and Nb were determined in 50 fine potsherds from the votive deposit of San Francesco in Catania by using a multi‐linear regression method. Additionally, in order to test the homogeneity of the material composing the fine pottery samples, a small portion of a few potsherds was powdered and analysed using the XRF system and the multilinear regression method. A comparison between non‐destructive and destructive approaches is presented and discussed. Finally, quantitative XRF data were compared with those obtained by chemical analysis of the powdered samples. The results allowed the testing of a non‐destructive methodology to be used for the identification and grouping of the different typological classes of fine pottery mainly represented in the San Francesco sanctuary. Copyright © 2005 John Wiley & Sons, Ltd.     

X-ray attenuation around <Emphasis Type="Italic">K</Emphasis>-edge of Zr,Nb, Mo and Pd: A comparative study using proton-induced X-ray emission and <Superscript>241</Superscript>Am gamma rays

Mass attenuation coefficients (μ/ρ) for Zr, Nb, Mo and Pd elements around their K-edges are measured at 14 energies in the range 15.744–28.564 keV using secondary excitation from thin Zr, Nb, Mo, Rh, Pd, Cd and Sn foils. The measurements were carried out at the K _α and K _β energy values of the target elements by two techniques: (1) Proton-induced X-ray emission (PIXE) and (2) ²⁴¹Am (300 mCi) source. In PIXE, 2 MeV proton-excited X-rays were detected by a Si(Li) detector. In the second case, X-rays excited by 59.54 keV photons from the targets were counted by an HPGe detector under a narrow beam good geometry set-up with sufficient shielding. The results are consistent with theoretical values derived from the XCOM package and indicate that the PIXE data have better statistical accuracy.     

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.     

Assessing silicon deposits in Zilfi province,Saudi Arabia,using XRF and XRD techniques

The aim of this project is to create a geochemical database of the Nafud Desert in Zilfi Province, which lies 260 km northwest of Riyadh, capital of Saudi Arabia, and assess its potential as a silicon mine. The area of study was surveyed during December 2012 collecting 21 geological samples from 7 places (Alsabla, Almatal, Shlwan, Alaaga, Jaway, Magra and Althuare). Elemental composition was determined using X‐ray fluorescence spectrometry, while mineral content and crystallography analysis was performed using X‐ray diffraction. Analysis results revealed that silicon was abundant in the area, in fairly homogeneous amounts. Silica was found in concentrations of around 93% per sampled mass, and silicon concentrations were around 42%, in the surface layers down to the depth of 40 cm. Other elements (Al, K, Ca, Ti, Cr, Mn, Fe, Sr, Zr and Pd ) were present in very low concentrations, except for aluminium oxide, which was present in three areas (Jaway, Magra and Althuare) at concentrations around 5%, while Alsabla samples showed higher concentrations of CaO. Thus, according to the results, the Nafud Desert is a rich source of silicon that can be exploited very cheaply because of the presence of the raw material on the surface. Copyright © 2016 John Wiley & Sons, Ltd.     

Application of the background standard method for the determination of Rb,Sr, Y,Zr, and Nb contents in phosphorites by x‐ray fluorescence

The aim of the present work is to demonstrate the application of the x‐ray fluorescence (XRF) technique to the determination of Rb, Sr, Y, Zr, and Nb contents in phosphorites. The effect of a chemical sample composition on fluorescence intensities of analytical lines has been taken into account using the background standard method. A novelty of the work is the detailed study of a background to choose the background position, free from the spectral line overlaps of the elements presented in the sample. The most suitable background position is the position at the angle 2θ = 29° when using the analyzing crystal LiF(200). During our investigation we faced a problem of choice of Certified Reference Materials (CRMs) for the calibration of the phosphorites. To estimate interelement effects and to choose CRMs for the calibration the intensities were theoretically calculated. The statistical processing of analytical results of the technique is carried out. This technique may be applied to the determination of Rb, Sr, Y, Zr, and Nb contents in the phosphorites. Also, the possibility has been demonstrated to use the XRF technique for geochemical investigations of rocks. Phosphorites of Bokson‐Khubsugul Basin were selected as an example. As a result of the investigation the genetic type of phosphorites was established, which corresponded to the present geodynamical depositional environment. The character of the distribution of Rb, Sr, Y, Zr, and Nb contents in the phosphorites was also studied. Copyright © 2008 John Wiley & Sons, Ltd.     

淡水和海水养殖珍珠的微量元素特征

珍珠中的微量元素有其特征规律及作用。前人很早就关注到淡水珍珠和海水珍珠微量元素特征的差异,但限于测试技术及分析方法,测出的微量元素种类相当有限,并且对测试结果也缺乏深入分析。电感耦合等离子体质谱议(ICP-MS)具有检测能力高, 速度快,可同时测试多种痕量及超痕量元素。采用ICP-MS对淡水和海水养殖珍珠的微量元素进行测定,并通过数据处理方法分析, 对比。结果表明：(1) 珍珠中含量较高的微量元素种类(Sr, Zn, Ni, Ba, Mn, Cr, Cu, Pb, Ti, Co, Ce, Zr, La, Rb)大致相同,但淡水养殖珍珠的微量元素总量明显少于海水养殖珍珠;(2) 淡水养殖珍珠的微量元素含量较为规律,具有较为固定的含量序列,即Sr>Mn>Ba>Ni>Cr>Pb;而海水养殖珍珠的微量元素含量差异较大,除了各样品都最富集Sr元素外,没有明显的含量顺序;(3) 珍珠中某些微量元素之间存在显著相关性。结论对养殖珍珠的环境指示, 养殖技术, 鉴定,以及综合开发利用具有一定的指导意义。     

ED‐XRF set‐up for size‐segregated aerosol samples analysis

The knowledge of size‐segregated elemental concentrations in atmospheric particulate matter (PM) gives a useful contribution to the complete chemical characterisation; this information can be obtained by sampling with multi‐stage cascade impactors. In this work, samples were collected using a low‐pressure 12‐stage Small Deposit Impactor and a 13‐stage rotating Micro Orifice Uniform Deposit Impactor^?. Both impactors collect the aerosol in an inhomogeneous geometry, which needs a special set‐up for X‐ray analysis. This work aims at setting up an energy dispersive X‐ray fluorescence (ED‐XRF) spectrometer to analyse quantitatively size‐segregated samples obtained by these impactors. The analysis of cascade impactor samples by ED‐XRF is not customary; therefore, as additional consistency test some samples were analysed also by particle‐induced X‐ray emission (PIXE), which is more frequently applied to size‐segregated samples characterised by small PM quantities. A very good agreement between ED‐XRF and PIXE results was obtained for all the detected elements in samples collected with both impactors. The good inter‐comparability proves that our methodology is reliable for analysing size‐segregated samples by ED‐XRF technique. The advantage of this approach is that ED‐XRF is cheaper, easier to use, and more widespread than PIXE, thus promoting an intensive use of multi‐stage impactors. Copyright © 2011 John Wiley & Sons, Ltd.