偏振能量色散X射线荧光光谱法测定地质样品中18种元素

利用偏振能量色散X射线荧光光谱仪分析了硅酸盐基体样品. 选取岩石、土壤、水系沉积物等国家一级标准物质, 采用镶边粉末压片方法, 选择Al2O3偏振靶、 Mo、 Co二级靶, 在真空状态下对K、 Ca、 Ti、 Cr、 Mn、 Fe、 Ni、 Cu、 Zn、 Ga、 As、 Rb、 Sr、 Y、 Zr、 Nb、 Ba、 Pb等18种元素进行选择激发和探测, 所有元素的校正选用扩展的康普顿散射校正模型. 各元素的检出限为0.4～10.9 μg/g;除了As元素外, 均达到了1:25万多目标地球化学调查规范的要求. 根据60个地质调查多目标考核样品的分析结果, 采用Rousseau(2001)所提出的相对不确定度计算方法, 对所建立的方法进行了评估.     

预富集单波长激发能量色散X射线荧光光谱法现场测定地表水中10种重金属

为实现现场快速定量分析地表水中的多种重金属元素,建立了一种树脂预富集-单波长激发能量色散X射线荧光光谱法现场准确快速测定地表水中Cr(Ⅵ)、Mn、Fe、Co、Ni、Cu、Zn、As、Cd、Pb 10种元素的分析方法。对该方法其中的树脂预富集条件进行了优化,结果表明最佳预富集条件为：树脂粒度38μm-75μm;水样体积30mL;水样流速6mL/min;预富集完成后即刻测量;样品pH值为5。在方法学方面考察了该方法的检出限、精密度、正确度,其中Cr(Ⅵ)、Cu、Zn、As、Cd、Pb 元素的检出限低于地表水环境质量标准GB 3838-2002的限值要求;精密度中相对标准偏差范围为2.13%~10.4%;加标回收率为90.0%~114%之间。采用该方法测定实际地表水样品,并与ICP-MS法进行比对,其测定结果基本一致。研究表明该方法检出限可以满足地表水中Cr(Ⅵ)、Mn、Fe、Co、Ni、Cu、Zn、As、Cd、Pb 的检测要求,精密度和准确性较好。该研究对地表水中无机元素分析方法的拓展进行了有益尝试和积累,并为后续相关标准制订提供有益参考。     

Determination of Cr,Fe, Co,Ni, Cu,Zn, As and Pb in liquid chemical waste by energy dispersive X-ray fluorescence

A method for simultaneous determination of Cr, Fe, Co, Ni, Cu, Zn, As e Pb in liquid chemical waste using Energy Dispersive X-Ray Fluorescence (EDXRF) technique was evaluated. A small sample amount (200 μL) was dried on a 6.35 μm thickness Mylar film at 60 °C and the analyses were carried out using an EDXRF spectrometer operated with an X-ray Mo tube (Zr filter) at 30 kV/20 mA. The acquisition time was 300 s and the Ga element was utilized as internal standard at 25 mg/L for quantitative analysis. The method trueness was assessed by spiking and the detection limit for those elements ranged from 0.39 to 1.7 mg/L. This method is notable because it assists the choice of the more appropriated waste treatment procedure, in which inter elemental interference is a matter of importance. In addition, this inexpensive method allows a non-destructive determination of the elements from ₁₉K to ₉₂U simultaneously.     

Simultaneous determination of cobalt, copper and zinc by energy dispersive X-ray fluorescence spectrometry after preconcentration on PAR-loaded ion-exchange resin.

A sensitive method for the preconcentration and determination of trace amounts of Co, Cu and Zn by energy-dispersive X-ray fluorescence spectrometry (EDXRF) has been developed. The method is based on the fact that 4-(2-pyridylazo)-resorcinol (PAR) loaded Dowex anion-exchange resin (PAR-resin) can effectively adsorb Co, Cu and Zn at pH 9.0 to form PAR-metal complexes. The detection limits for Co, Cu and Zn were 1.53, 0.31 and 0.21 ppb, respectively. The precisions for five replicate measurements of the three metals were 3.4, 2.7 and 2.1% RSD, and the calibration curves were linear up to 75 microg with correlation coefficients of 0.9975, 0.9980 and 0.9985, respectively. The method was successfully applied for the simultaneous determination of Co, Cu and Zn in seawater samples at ppb levels.     

熔融制样X射线荧光光谱法测定陶瓷、色料和釉等物料中主量及次量元素

采用熔融片制样用X射线荧光光谱法对陶瓷、色料和釉物料中Na、Mg、Al、Si、P、S、K、Ca、Ti、Mn、Fe、Ba、Zr、Zn、Hf等15种元素进行了测定,用理论α系数校正基体效应。方法简便、快速、分析结果的准确度完全能满足上述物料分析的要求。本法还用纯化学试剂和标准样品按一定比例混合制备标准样品,弥补了色料和釉缺少标准或没有标样的困难。又对Zr和Hf元素分析线进行了选择,用ZrLα和HfLB1 作为分析线,而不采用ZrKα,不仅使制备的熔片达到ZrLα线的饱和厚度,使分析结果的准确度和重现性好,而且还消除了ZrKα的谱线对HfL B1分析线的干扰。     

Determination of rare earth elements and thorium in britholite ore by energy dispersive X-ray fluorescence spectrometry

A radioisotope-excited X-ray fluorescence technique is applied for the determination of thorium and rare earth elements in britholite ore from Canada. An annular source of⁵⁷Co is employed for excitation of characteristic K X-rays of thorium and rare earth elements. The peak ratios of lanthanides were used to remove the difficulties because of overlapping lines at the 33–50 keV energy region. Matrix effects are examined also in detail and compensated for infinitely thick powdered ore sample. Results obtained in the analysis agree well with recommended values of Canada.     

Determination of trace elements in Syrian medicinal plants and their infusions by energy dispersive X-ray fluorescence and total reflection X-ray fluorescence spectrometry

X-ray fluorescence (XRF) and total-reflection X-ray fluorescence (TXRF) techniques suited well for a multi-element determination of K, Ca, Mn, Fe, Cu, Zn, Rb, and Sr in some Syrian medicinal plant species. The accuracy and the precision of both techniques were verified by analyzing the Standard Reference Materials (SRM) peach-1547 and apple leaves-1515. A good agreement between the measured concentrations of the previously mentioned elements and the certified values were obtained with errors less than 10.7% for TXRF and 15.8% for XRF. The determination of Br was acceptable only by XRF with an error less than 24%. Furthermore, the XRF method showed a very good applicability for the determination of K, Ca, Mn, Fe, Cu, Zn, Rb, Sr, and Br in infusions of different Syrian medicinal plant species, namely anise (Anisum vulgare), licorice root (Glycyrrhiza glabra), and white wormwood (Artemisia herba-alba).     

熔融制样-X射线荧光光谱法测定锆钛矿中主次成分

为准确测定锆、钛及其共伴生有用有害杂质元素含量,采用稀释比1∶20的四硼酸锂-偏硼酸锂混合熔剂,先将样品700℃预氧化7 min,再1 050℃熔融19 min制样,建立了熔融制样-X射线荧光光谱法测定锆钛矿中SiO₂、Al₂O₃、Fe₂O₃、CaO、MgO、MnO、TiO₂、K₂O、Na₂O、P₂O₅、ZrO₂等11种主次成分的分析方法。采用标准样品加入光谱纯的方式配制锆钛矿的标准系列样品解决锆钛矿石标准样品不足的问题。结果表明,各组分的检出限在0.004%～0.13%,各组分测定结果的相对标准偏差(RSD,n=12)在0.060%～2.6%。对实际样品进行测定,测定值与传统方法测定值一致,并具有操作简便,分析周期短的优点,解决了锆钛矿石前处理过程中锆钛易水解,分析周期长的问题,对综合评价锆钛矿资源具有重要意义。     

便携式X射线荧光光谱法同时测定氧化锌富集物中锌铁氯镉砷

氧化锌富集物的进口能弥补我国锌矿资源的不足,但要求ZnO>50%、Fe<10%、Cl<8%、Cd<0.25%、As<0.6%。目前常采用YS/T 1171.1～10-2017《再生锌原料化学分析方法》检测氧化锌富集物中锌铁氯镉砷含量,该系列检测方法均需要繁琐的湿法样品前处理,测量过程较为冗长,不能满足氧化锌富集物大量进口时快速通关的需求。故实验建立了采用便携式X射线荧光光谱法(PXRF)同时测定氧化锌富集物中锌铁氯镉砷的方法。采用YS/T 1171.3-2017和YS/T 1171.5-2017方法对氧化锌富集物样品进行定值,然后选取21个含量具有梯度的氧化锌富集物样品作为校准样品,建立起各元素X射线荧光强度值与含量的校准曲线。各曲线相关系数在0.8164～0.9999,方法检出限为0.013%～1.95%,各元素的相对标准偏差(RSD,n=11)均小于0.05%。采用本方法和化学方法分别检测氧化锌富集物样品,各元素的本方法检测值与化学分析方法检测值的相对误差均小于20%。本方法能应用到口岸现场进口氧化锌富集物快速筛查,检测一个样品仅需1分钟测量时间,极大地加快了进口氧化锌富集物通关速度。     

电沉积富集制样-X射线荧光光谱法测定痕量Ni、Cd和Pb

提出了电沉积富集制样-X荧光光谱法同时测定水样中痕量Ni、Cd和Pb的方法.方法以平整光滑的高纯铜片为基质,采用电解的方法对待测元素进行电沉积富集,然后用X射线荧光光谱仪进行测定.探讨了沉积电压、溶液pH值、电解质浓度、沉积时间等参数对待测元素电沉积富集的影响.方法精密度(RSD)分 别为Ni 1.6%、Cd 1.2%...     

Simultaneous determination of sixteen major and minor elements in river sediments by energy-dispersive x-ray fluorescence spectrometry after fusion in lithium tetraborate glass

Fluvial sediments, including the NBS SRM-1645 Standard River Sediment, were fused in lithium tetraborate to form glass discs on which determinations of 16 elements (K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr and Pb) were obtained simultaneously at a single set of x-ray conditions by energy-dispersive x-ray fluorescence spectrometry (e.d.x.r.f.). Relatively high sample-to-flux ratios of 1:3 were employed to obtained determinations of several minor as well as major elements on a single disc. Lower sample concentrations 1:6 and 1:10 were also used with the NBS SRM-1645. Inter-element corrections for absorption by iron were significant for detectable elements heavier than iron. In the NBS SRM-1645 samples, corrections were made for the fluorescence of chromium by the Fe K lines as well as the absorption of the Fe K lines by chromium. A background correction was also necessary for manganese in NBS SRM-1645. At the lowest sample-to-flux ratio (1:10) good agreement was obtained between the e.d.x.r.f. determinations and the NBS values for all quantifiable elements except zinc. At higher sample-to-flux ratios, agreement with the NBS values was generally poorer with increasing sample concentration. The relative standard deviation (RSD) of the eight quantifiable major and minor elements (K, Ca, Ti, Mn, Fe, Zn, Sr and Zr) determined under a single set of x-ray conditions ranged from 2 to 9% (RSD) with a mean RSD of 4.4% for a set of replica discs fused with Lake Pueblo/Arkansas River sediment samples.     

X射线荧光光谱法同时测定涂料中的铅、铬、硒和钴

提出了用X射线荧光光谱法同时测定涂料中有害重金属铅、铬、硒和钴的一种新的测试方法. 考察了样品量不同和样品粒度不同对待测元素测试结果的影响. 选用不含待测元素的新鲜涂料作为基体物质制备标准样品, 较好地消除了基体的影响. 各待测元素在50～1000 mg/kg的范围内, 均呈线性关系;Pb、 Cr、 Se、 Co的检出限分别为3.6、 1.2、 0.5及1.5 mg/kg;方法精密度和仪器精密度的相对标准偏差分别低于1.3%和0.50%;用于实际样品测得的结果与电感耦合等离子体原子发射光谱法法测得的结果基本一致.     

Radionuclide X-ray fluorescence determination of Cr, Fe, Cu, Zn and Pb in industrial wastewaters after preconcentration of determined elements

Radionuclide X-ray fluorescence analysis was used for the determination of Cr, Fe, Cu, Zn and Pb in industrial wastewaters (from surface treatment of metals and glasses) after precipitation of determined elements by 8-hydroxyquinoline.     

Assessment of the Lake Gendabi salt for trace elements and toxic heavy metals by energy dispersive X-ray fluorescence spectrometry

This study has analyzed samples of salts from Lake Gendabi, located in the northern part of Tanzania for metal contamination using the EDXRF spectrometry. The aim of the study was to assess the suitability of the salt from Lake Gendabi for human consumption. Seventy-five samples of salt were collected from the Lake Gendabi floor and grouped into five grades (G1, G2, G3, G4 and G5) depending on the position of the salt from the lake shore. In addition to Na and Cl, concentrations of 17 more elements were determined in all five grades of salt. These included seven toxic metals which are Al, Ni, Cr, Cd, Pb as well as Th and U which are both toxic and radioactive. The concentrations of all toxic elements found in the samples were higher than their Maximum tolerable limits set by international organizations. As this salt is used in many parts of Tanzania, it is proposed that the salt should be thoroughly purified before entering the market. Further research to include salt samples from other salt production areas in Tanzania is recommended.     

Simultaneous determination of Cu, Cd and Pb in drinking-water using W-Coil AAS

An inexpensive, multi-element, W-coil atomic absorption spectrometer has been developed. Atomization occurs on W-coils extracted from commercially available slide projector bulbs. The system has minimal power requirements, 120 ACV and 15 A. A small, computer controlled CCD spectrometer is used as the detector. A multi-element Cu, Cd and Pb hollow cathode lamp is used as the source. 20 mul volumes are deposited on the coil and atomized at 6.7 A or approximately 2200 degrees C. Cu, Cd and Pb were simultaneously determined in tap water, drinking water and a quality control sample. The instrument detection limits are 0.8, 0.2 and 3.0 mug/l for Cu, Cd and Pb, respectively.     

icp-ms法同时测定卷烟纸中元素铬、镍、铜、砷、硒、镉、铅

电感耦合等离子体质谱(icp-ms);卷烟纸;微波消解     

Trace elements determination by energy dispersive X-ray fluorescence (EDXRF) in human placenta and membrane: a comparative study

This work is an application of energy dispersive X-ray fluorescence (EDXRF) as an analytical technique for trace elemental determination in human membrane and placenta and elemental concentrations correlations in both tissues. Whole samples were collected during the delivery from healthy mothers and full-term pregnancies. The age of the mother was between 25 and 40 years old, and the weight of the infants ranged from 2.56 to 4.05 kg. Samples were lyophilised and analysed without any chemical treatment. No significant differences in elemental content of placenta and membrane samples were observed except for Ca. Very low levels of Se, As and Pb were observed in all the analysed samples. Zn, considered as one of the key elements in newborn health, was not significantly different in the analysed samples, all of which originated from healthy mothers and healthy babies. The obtained values agree with the literature except for Ca, which is much higher in the studied samples.     

X射线荧光光谱仪快捷、准确测定水玻璃主次量元素

本方法介绍了采用X射线荧光光谱仪测定液体水玻璃中的Al2O3、CaO、MgO、Fe2O3、K2O、Na2O、SiO2的含量。研究了适合直接测定液态水玻璃的制样方式、仪器分析参数,建立了工作曲线并录入数据库中。将该方法对未知样品的测定结果与化学法、ICP-AES法对比分析,证实具有良好的准确度,精密度试验显示RSD在0.38%~14.26% 之间。结果显示本方法的准确度、精密度完全可以满足对水玻璃中上述元素的测定要求。     

Preliminary studies of laser-induced breakdown spectrometry for the determination of Ba,Cd, Cr and Pb in toys

The performance of laser-induced breakdown spectrometry (LIBS) for the determination of Ba, Cd, Cr and Pb in toys has been evaluated by using a Nd:YAG laser operating at 1064 nm and an Echelle spectrometer with intensified charge-coupled device detector. Samples were purchased in different cities of São Paulo State market and analyzed directly without sample preparation. Laser-induced breakdown spectrometry experimental conditions (number of pulses, delay time, integration time gate and pulse energy) were optimized by using a Doehlert design. Laser-induced breakdown spectrometry signals correlated reasonably well with inductively coupled plasma optical emission spectrometry (ICP OES) concentrations after microwave-assisted acid digestion of selected samples. Thermal analysis was used for polymer identification and scanning electron microscopy to visualize differences in crater geometry of different polymers employed for toy fabrication. Results indicate that laser-induced breakdown spectrometry can be proposed as a rapid screening method for investigation of potentially toxic elements in toys. The unique application of laser-induced breakdown spectrometry for identification of contaminants in successive layers of ink and polymer is also demonstrated.     

Quantitative analysis of elements (C, N, O, Al, Si and Fe) in polyamide with wavelength dispersive X-ray fluorescence spectrometry

A wavelength dispersive X-ray fluorescence (WD-XRF) spectrometry combined with calibration curve method was established for simultaneously analyzing low-Z elements (C,N,O) and Al,Si,Fe in polyamide.To investigate the origin of plastic material causing deposition and blocking in instrument engines and pipelines,polyamide 6 (PA 6,an engineering plastic) was chosen as the study object on account of its common use in industry.The sample preparation with pressed powder disk has been developed for determination of six elements in PA 6.Pure Cu metal was used as the matrix and PA 6 was regarded as standard sample for C,N,O elements.PA 6 particles were firstly smashed to uniform powder in liquid nitrogen,and then mixed with inorganic standard powders (Fe2O3,Al2O3,SiO2,and Na 2 SiO 3).The mixture was ground to obtain homogeneous calibration materials for WD-XRF analysis.The quantitative property of the calibration curve method for each element was reliable.The limits of detection (S/N≤3) of C,N,O,Al,Si and Fe using WD-XRF were 249,120,101,6.2,3.3,and 1.8 μg/g,respectively.To confirm the accuracy of the proposed WD-XRF calibration curve method,inductively coupled plasma optical emission spectroscopy (ICP-OES) detection for Al,Si,Fe and elemental analyzer (EA) analysis for C,N,O were utilized.A good correlation of the WD-XRF results with the measurements of ICP-OES and EA was observed.