单波长激发-能量色散X射线荧光光谱法检测蔬菜中多种重金属元素

为实现蔬菜中多种元素的快速检测,利用单波长激发-能量色散X射线荧光光谱仪（MW-EDXRF）,建立了蔬菜中As、Pb、Cd、Cr、Ni、Cu、Zn、Rb、Mn等元素的快速检测方法。对XRF的激发时间、载样量、样品压片等条件进行了优化,结果显示当累积激发时间达到600 s、载样量为2 g、样品压片15 Mpa保持60 s时,可以实现XRF最优检测性能。在最优条件下,As、Pb、Cd、Cr、Ni、Cu、Zn、Rb、Mn的检出限（LOD）分别为0.07 mg/kg、0.07 mg/kg、0.07 mg/kg、0.32 mg/kg、0.32mg/kg、1.2 mg/kg、0.4 mg/kg、0.08 mg/kg、0.3 mg/kg;对菠菜、葱、胡萝卜、豆角、番茄、姜、空心菜、莲藕、芹菜、蒜等蔬菜样品测定11次的相对标准偏差（RSD）在3%~10%,表明方法具有良好的精密度;测定5种蔬菜基体标准物质的回收率在93%~119%,与微波消解电感耦合等离子体质谱法（ICP-MS）测定结果对比的线性回归系数（R2）>0.99（Cu的R2=0.9838）,表明方法具有良好的检测准确度。同时,该仪器仅有不到10 kg,不需要样品消解处理,检测时间在10 min左右,非常适合蔬菜多种重金属的现场快速筛查。     

熔融制样-单波长激发能量色散X射线荧光光谱法测定铁矿石中主、次量成分北大核心CSCD

将经1000℃灼烧恒重后的样品0.6000 g、四硼酸锂-偏硼酸锂混合熔剂6.0000 g和碘化铵0.5000 g置于铂-金坩埚中,混匀后在1150℃的自动熔融炉中熔融30 min,待冷却后取出脱模,制备成玻璃样片,采用单波长激发能量色散X射线荧光光谱法测定其中主、次量成分,能有效解决能谱对轻元素的激发效率低和样品散射的连续谱背景过高问题,从而实现对微量轻元素的测定。以理论α影响系数法对基体效应进行校正,建立了各成分的工作曲线。利用铁矿石标准物质或有证化学分析标准样品中低含量成分的3.14倍标准偏差(s)计算检出限(3.14s),SiO_(2)、Al_(2)O_(3)、P、CaO、MgO、Mn的检出限依次为0.022%,0.024%,0.0050%,0.0044%,0.0062%和0.0065%。对不同铁矿石样品测定12次,高于检出限的成分测定值的相对标准偏差均小于8.0%。采用不同方法进行比对试验,除质量分数在0.10%以下的MgO之外,本方法测定其他成分所得结果与对比方法的测定结果吻合。     

单波长X射线荧光光谱法测定加氢催化剂中磷

建立了单波长X射线荧光光谱法测定加氢催化剂中磷含量的方法.将干燥催化剂样品粉末0.2000 g置于银坩埚中,加入10 mL 0.67 g·mL-1氢氧化钠溶液,加热微沸20 min,趁热转移至250 mL烧杯中,加入10 mL 50％(体积分数)硫酸溶液调节体系酸度,加热至样品完全溶解,冷却后,定容至250 mL.取上...     

高精度X射线荧光光谱法快速分析人体血液中6种有毒重金属元素

通过高精度X射线荧光光谱法建立了人体血液中As, Sr, Cd, Hg, Tl, Pb 6种有毒重金属元素的快速定量检测方法。根据每种元素的校准曲线,使用基本参数法对基体效应进行校正,建立了人体血液中有毒重金属的检测模式。6种元素在各自线性范围内呈良好的线性关系,相关系数均大于0.995,检出限在0.037～0.192 mg/L之间,加标回收率为90.1%～114.0%,相对标准偏差（RSD）在0.1%～11%之间。该方法不需前处理即可实现对人体血液中As, Sr, Cd, Hg, Tl, Pb 6种有毒重金属元素的快速测定。     

高能偏振能量色散X射线荧光光谱法分析古陶瓷

以国家地质标准样品制作工作曲线,用粉末压片法制样,高能偏振能量色散X射线荧光光谱法测定古陶瓷中包括15种稀土元素在内的56种元素,通过对6个陶瓷胎标准样品分析,结果表明:钪、钒、锰、铬、锌、镓、锗、铷、锶、钇、锆、铌、镉、锡、铯、钡、镧、铈、镨、钕、钆、钬、铒、铥、镱、镥、钍、铀等28种痕量元素测定值均在参考值的不确定度3～4倍范围,其他痕量元素如镍、铜、钼、锑、钐、铕、铽、铪、铅、铋等10种元素合格率为50%～83%。钠、镁、钾、钙、铁的氧化物和钛等6个项目均在允许误差范围内。氯、硫、磷的合格率均为66.6%。二氧化硅和三氧化二铝测定值和波长色散X射线荧光光谱熔融法测定结果相比,绝对误差分别在0.95%～4.46%和0.60%～1.66%之间。     

能量色散偏振X射线荧光光谱法测定生铁中锰和钛

探讨了应用能量色散偏振X射线荧光光谱仪测定生铁中锰和钛进行炉前快速分析的方法.对测定锰及钛时仪器的工作条件,试样的制备以及工作曲线的制作等因素作了较系统的试验,该方法所得测定结果与化学法测定结果或标样标准值相吻合,相对标准偏差小于1.5%,与化学法相比,锰和钛的测定时间由50 min缩短到2 min.     

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.     

能量色散型X射线荧光光谱法测定聚合物材料中镉和铅含量

提出了能量色散型X射线荧光光谱测定聚合物材料中镉和铅的测试分析方法及制样技巧。按照仪器分析条件测定同时含有镉和铅的6块不同浓度级别的标准物质来建立校准工作曲线,其线性范围分别在250ug·g-1、1100ug·g-1以内。镉和铅的方法检出限依次为4.7ug·g-1、4.1ug·g-1。该方法应用于测定欧洲标准物质ERM-EC680和ERM-EC681k,其镉和铅的实际测定值与标准物质证书的标称值相符,测定实际样品中的镉和铅的回收率介于90~110%。该方法测定标准物质和实际样品中镉和铅的精密度均小于10%。     

Titanium dioxide determination in sunscreen by energy dispersive X-ray fluorescence methodology

Nowadays there are many sun-protection cosmetics incorporating chemical and/or physical UV filters as active ingredients and there are no official methods to determine these kinds of compounds in sunscreen cosmetics. The objective of this work is to estimate TiO₂ concentration, without sample preparation, employing a portable energy dispersive X-ray fluorescence (EDXRF), aiming to estimate the sun protection factor (SPF) due to the physical barrier in sunscreen composition, and also identify the metals present in the samples. A portable EDXRF system was used for the analysis of fifteen commercial samples. It was also prepared three formulations estimated in FPS-30 using TiO₂ at 5%. Quantification was performed using calibration curves with standards from 1 to 30%. The physical barrier contribution in the SPF, associated to Ti concentration, was determined for all samples. The presence of some elements, like K, Zn, Br and Sr was detected in the sunscreen, identifying chemical elements that were not cited in the formulations. Three commercial samples were analyzed for total SPF determination and the result shows that the measured value is 10% lower than the nominal one.     

Evaluation of analytical instrumentation. Part XX Instrumentation for energy dispersive X-ray fluorescence spectrometry

The reports of this series tabulate a number of features of analytical instruments that should be considered when making comparison between various systems. Scoring these features in a rational manner allows a scientific comparison to be made between instruments as an aid to selection. This is the XXth report of the series and deals with instrumentation for energy dispersive X-ray fluorescence spectrometry.     

Direct chlorine determination in crude oils by energy dispersive X-ray fluorescence spectrometry: An improved method based on a proper strategy for sample homogenization and calibration with inorganic standards

Official guidelines to perform chlorine determination in crude oil are (i) American Society for Testing and Materials (ASTM) D6470, which is based on the extraction of water from the oil and subsequent determination of the chloride by potentiometry, (ii) ASTM D3230, that measures the conductivity of a solution of crude oil in a mixture of organic solvents and (iii) US Environmental Protection Agency (EPA) 9075 that uses energy dispersive X-ray fluorescence spectrometry to quantify chlorine and it is applicable for the range from 200 μg g^− 1 to percent levels of the analyte. The goal of this work is to propose method to quantify lower amounts of chlorine in crude oil using energy dispersive X-ray fluorescence spectrometry using a simple calibration strategy. Sample homogenization procedure was carefully studied in order to enable accurate results. The calibration curve was made with standards prepared by diluting aqueous NaCl standard in glycerin. The method presented a linear response that covers the range from 8 to at least 100 μg g^− 1 of chlorine. Chlorine in crude oil samples from Campos Basin - Brazil were quantified by the proposed method and by potentiometry after extraction of chlorine from the oil. Results achieved using both methods were statistically the same at 95% confidence level.     

X射线荧光光谱理论强度计算中激发因子的选择

激发因子是X射线荧光强度理论计算中的重要参数。对目前常用的四种激发因子算法进行了较为详细的比较,并设计了一种评价激发因子算法的实验方法,即用人工合成试样测定了八对能量接近的X射线特征谱线的强度比,然后根据不同的激发因子算法用理论方法计算出这些谱线对的强度比值,以两者的接近程度来判断这四种激发因子算法的适用性。结果表明,使用NRLXRF程序修改版中的激发因子算法计算出来的理论强度比与实测值之间的相对偏差最小。     

Chemometric methods in energy dispersive X-ray fluorescence

Chemometric methods like principal component regression (PCR) are an excellent tool for the determination of matrix parameters from scattered radiation. PCR is used for the determination of carbon, hydrogen and oxygen from water and oil-based samples. This information is used in combination with fundamental parameters to determine zink in liquid samples. The method allows an accurate prediction of element concentrations in strong varying matrices.     

Direct rapid analysis of trace bioavailable soil macronutrients by chemometrics-assisted energy dispersive X-ray fluorescence and scattering spectrometry

Precision agriculture depends on the knowledge and management of soil quality (SQ), which calls for affordable, simple and rapid but accurate analysis of bioavailable soil nutrients. Conventional SQ analysis methods are tedious and expensive. We demonstrate the utility of a new chemometrics-assisted energy dispersive X-ray fluorescence and scattering (EDXRFS) spectroscopy method we have developed for direct rapid analysis of trace ‘bioavailable’ macronutrients (i.e. C, N, Na, Mg, P) in soils. The method exploits, in addition to X-ray fluorescence, the scatter peaks detected from soil pellets to develop a model for SQ analysis. Spectra were acquired from soil samples held in a Teflon holder analyzed using ¹⁰⁹Cd isotope source EDXRF spectrometer for 200 s. Chemometric techniques namely principal component analysis (PCA), partial least squares (PLS) and artificial neural networks (ANNs) were utilized for pattern recognition based on fluorescence and Compton scatter peaks regions, and to develop multivariate quantitative calibration models based on Compton scatter peak respectively. SQ analyses were realized with high CMD (R² > 0.9) and low SEP (0.01% for N and Na, 0.05% for C, 0.08% for Mg and 1.98 μg g⁻¹ for P). Comparison of predicted macronutrients with reference standards using a one-way ANOVA test showed no statistical difference at 95% confidence level. To the best of the authors’ knowledge, this is the first time that an XRF method has demonstrated utility in trace analysis of macronutrients in soil or related matrices.     

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).     

Determination of wear metals in engine oil by mild acid digestion and energy dispersive X-ray fluorescence spectrometry using solid phase extraction disks

A simple, particle size-independent spectrometric method has been developed for the multi-element determination of wear metals in used engine oil. A small aliquot (0.5 ml) of an acid-digested oil sample is spotted onto a C-18 solid phase extraction disk to form a uniform thin film. The dried disk is then analyzed directly by energy dispersive X-ray fluorescence spectrometry. This technique provides a homogeneous and reproducible sample surface to the instrument, thus overcoming the typical problems associated with uneven particle size distribution and sedimentation. As a result, the method provides higher precision and accuracy than conventional methods. Furthermore, the disk sample may be stored and re-analyzed or extracted at a later date. The signals arising from the spotted disks, and the calibration curves constructed from them, are stable for at least 2 months. The limits of detection for Fe, Cu, Zn, Pb, and Cr are 5, 1, 4, 2, and 4 μg g⁻¹, respectively. Recoveries of these elements from spiked oil samples range from 92 to 110%. The analysis of two standard reference materials and a used oil sample produced results comparable to those found by inductively coupled plasma atomic emission spectrometry.     

Application of energy dispersive X-ray fluorescence spectrometry as multielemental analysis to determine the elemental composition of crumb rubber samples

The elemental content of different rubber samples was analyzed using different analytical methods (inductively coupled atomic emission spectroscopy and non-polarized energy dispersive X-ray fluorescent spectroscopy). A new application of energy dispersive X-ray spectrometry as an analytical method for the determination of elemental content of rubber samples was investigated. Control analyses were also carried out to compare the results by ICP-AES. In one hand four samples contained same quality of elements (Mg, Si, P, S, Ca, Fe, Zn), while another four samples were without phosphorous. On the other hand there were significant differences in the ratio of C/H in the case of each sample. Based on the results, it was concluded that the X-ray spectrometry as an analytical method is well-applicable to determine the elemental composition of rubber samples, but the calibration is a key part of the analysis. A good correlation was observed between the different methods, but the correlation was the function of characteristic of matrices. Significant matrix effect from the presence of phosphor was observed in the case of some samples, while the change of C/H ratio could not result notable matrix effect.