自适应平方根卡尔曼滤波法校正ICP－AES光谱干扰的研究

自适应平方根卡尔曼滤波法校正ＩＣＰ－ＡＥＳ光谱干扰的研究李划新，朱明华，邵济才（华东理工大学分析测试中心上海２００２３７）关键词自适应平方根卡尔曼滤波，ＩＣＰ－ＡＥＳ，光谱干扰光谱干扰是ＩＣＰ－ＡＥＳ分析中不可忽视的问题，特别对光谱复杂物测定时更为严...     

ICP－AES中稀土元素Q数据的编辑与Q光谱的模拟

研究了一种将实验数据与计算机模拟相结合的方法，编辑Ｑ数据和模拟Ｑ光谱，从而预测和校正用ＩＣＰ－ＡＥＳ分析稀土元素时的光谱干扰。首先通过实验获得每一稀土元素的原始光谱数据，然后用光谱平均结合Ｋａｌｍａｎ平滑剔除噪声，并校正波长漂移，最后将处理的光谱数据转为Ｑ数据，用于光谱模拟和光谱干扰校正。讨论了光谱模拟和干扰校正中的一些基本问题，结果表明：当光谱干扰不很强时，Ｑ数据用于光谱干扰校正已足够准确；光谱模拟方法在常规分析中是可行的，是稀土分析中处理光谱干扰问题的一个方便、快速的方法。     

ICP—AES中稀土元素Q数据的编辑与Q光谱的模拟

研究了一种将实验数据与计算机模拟相结合的方法，编辑Ｑ数据和模拟Ｑ光谱，从而预测和校正用ＩＣＰ－ＡＥＳ分析稀土元素时的光谱干扰，首先通过实验获得每一稀土元素的原始光谱数据，然后用光谱平均结合Ｋａｌｍａｎ平滑剔除噪声，并校正波长漂移，最后将处理的光谱数据转为Ｑ数据，用于光谱模拟和光谱干扰校正，讨论了光谱模拟和干扰校正中的一些基本问题，结果表明；当光谱干扰不很强时，Ｑ数据用于光谱干扰校正已足够准确，光谱     

电感耦合等离子体发射光谱法测定地质样品中钨时对锌的光谱干扰校正

采用硝酸-氢氟酸-高氯酸消解样品,电感耦合等离子体发射光谱法测定地质样品中的钨.讨论了Zn 207.908对W 207.911的光谱干扰,并应用光谱干扰系数校正法(IEC)校正干扰.结果表明:Zn对W的光谱干扰可以用IEC进行有效的消除,进行光谱校正后的结果明显优于未加校正的试验结果.     

电感耦合等离子体原子发射光谱法分析25种元素对磷的光谱干扰及其校正

利用电感耦合等离子体原子发射光谱法分析了25种元素对磷的光谱干扰及其校正。电感耦合等离子体原子发射光谱法测定样品中磷元素含量时存在光谱干扰,通过干扰系数法,对铍、硼、镁、铝、硅、钙、钪等25种元素对磷元素的光谱干扰情况进行了分析,获得各元素的干扰系数。以国家标准物质GBW 01305为样品,利用该方法对其磷元素含量进行光谱干扰校正分析,测定结果的误差由2.9%降至0.2%。可以该方法为依据对不同材料中磷元素的光谱干扰现象加以校正。     

ICP－AES分析中用Kalman滤波法校正光谱干扰时波长定位误差对结果的影响及消除

本工作以Ｋａｌｍａｎ滤波技术为光谱干扰校正方法，选择典型的光谱干扰为例，系统研究了波长定位误差影响滤波结果准确性的规律性，提出了改善波长定位精度的途径。对于谱线重叠干扰的校正，波长定位精度一般应优于０．１ｐｍ；利用新息序列零均白噪音特性建立指示函数优化扫描光谱峰位，大大提高了波长定位精度，保证了滤波结果的准确性。     

ICP—AES分析中用Kalman滤波法校正光谱干扰时波长定位误差对结果的…

本工作以Ｋａｌｍａｎ滤波技术为光谱干扰校正方法，选择典型的光谱干扰为例，系统研究了波长定位误差影响滤波结果准确性的规律性，提出了改善波长定位精度的途径。对于谱线重叠干扰的校正，波长定位精度一般应优于０．１ｐｍ；利用新息序列零均白噪音特性建立指示函数优化扫描光谱峰位，大大提高了波长定位精度，保证了滤波结果的准确性。     

高纯氧化镝电感耦合等离子体原子发射光谱法摄谱分析时光谱干扰校正方法的研究

本文建立了高纯氧化镝样品ICP摄谱分析时干扰系数法校正光谱干扰的方法。测定了镝基体对14种稀土杂质元素20条灵敏分析线的干扰系数(KCT)。并有效地校正了镝基体造成的光谱干扰,获得满意的结果。     

ICP-AES中元素间干扰的逐步逼近校正方法

本文基于干扰系数校正法,提出一种新的校正元素间相互干扰的方法——逐步逼近校正法,以及相应的计算机软件系统。对复杂体系中元素间相互光谱干扰和元素“自身”非光谱干扰进行校正,获得了良好的结果。     

ICP-AES法测定不锈钢中高含量镍和铬的光谱干扰和校正

使用HNO3,HF,HCl O4溶解不锈钢样品,以Ni 231.6 nm,Cr 267.7 nm作为分析谱线,以干扰系数法校正Fe对Ni和Cr的光谱干扰,建立了ICP-AES法测定不锈钢中高含量Ni和Cr的方法。通过测定不同铁基体浓度下Ni和Cr的发射强度,考察铁基体对Ni和Cr的光谱干扰。实验结果表明:铁基体对Ni和Cr均存在光谱干扰,将实验方法用于不锈钢标准样品中Ni和Cr的测定,经光谱干扰校正后,结果与参考值吻合,测定结果的绝对误差在0.35%~0.63%间,相对标准偏差(RSD,n=6)在0.68%~1.1%间。     

Interferences of polyatomic and doubly charged ions in the multielement analysis of geological samples by inductively coupled plasma mass spectrometry and their minimization on a high-resolution mass spectrometer

The paper is devoted to various significant polyatomic and doubly charged interferences observed for trace elements determined by inductively coupled plasma mass spectrometry in geological samples. It has been shown that most interferences can be minimized or completely excluded using an ELEMENT 2 high-resolution mass spectrometer. The influence of spectral interferences has been quantitatively estimated. Recommendations are given for the selection of isotopes with minimal spectral interferences and an optimal resolution mode. The detection limits for analytes are evaluated for three resolution modes: 300, 4000 and 10000 together with the interferences related to the errors of rare-earth element determination.     

New method for removal of spectral interferences for beryllium assay using inductively coupled plasma atomic emission spectrometry

Beryllium (Be) has been used widely in specific areas of nuclear technology. Frequent monitoring of air and possible contaminated surfaces in U.S. Department of Energy (DOE) facilities is required to identify potential health risks and to protect U.S. DOE workers from beryllium-contaminated dust. A new method has been developed to rapidly remove spectral interferences prior to beryllium measurement by inductively coupled plasma atomic emission spectrometry (ICP-AES) that allows lower detection limits. The ion exchange separation removes uranium (U), plutonium (Pu), thorium (Th), niobium (Nb), vanadium (V), molybdenum (Mo), zirconium (Zr), tungsten (W), iron (Fe), chromium (Cr), cerium (Ce), erbium (Er) and titanium (Ti). A stacked column consisting of Diphonix Resin and TEVA Resin reduces the levels of the spectral interferences so that low level Be measurements can be performed accurately. If necessary, an additional anion exchange separation can be used for further removal of interferences, particularly chromium. The method has been tested using spiked filters, spiked wipe samples and certified reference material (CRM) standards with high levels of interferences added. The method provides very efficient removal of spectral interferences with very good accuracy and precision for beryllium on filters or wipes. This new method offers improvements over other separation methods that have been used by removing large amounts of all the significant spectral interferences with greater simplicity and effectiveness. The effective removal of spectral interferences allows lower method detection limits (MDL) using inductively coupled atomic emission spectrometry. A vacuum box system is employed to reduce analytical time and reduce labor costs.     

电感耦合等离子体原子发射光谱法测定黄铜中主、次量元素

提出了电感耦合等离子体原子发射光谱法同时测定黄铜中铜和锌等主量元素,镍、铅、铝、锡、铁、锰、磷和钴等次量元素的分析方法。选择了各元素的分析谱线,运用干扰元素系数法校正光谱干扰,用内标校正和同步背景校正消除基体影响。各元素的质量分数均在一定的范围内与其信号强度呈线性关系。方法用于分析两个铜合金样品,测定结果与光电直读光谱法、化学法的测定值一致;用于分析3种铜合金标准样品,测定值与标准值相一致。     

Non-linear spectral interferences in an inductively coupled plasma optimized for simultaneous multi-element analysis of plant and soil samples by atomic emission spectrometry

Summary The spectral interferences by Al, Ca, Fe, K, Mg and Na in the direct simultaneous determination of As, Cd, Co, Cu, Hg, Pb and Se in plant and soil samples by ICP-AES are investigated, and a non-linear relationship between the apparent analyte concentration for As, Cd, Co, Hg and Se is observed. A correction method for non-linear spectral interferences is discussed and non-linear spectral correction coefficients are calculated.     

Accurate and rapid estimation on spectral interferences in routine analysis by ICP-AES: use of mutual interference coefficients

A practical method to estimate spectral interferences and to select optimum analytical lines in ICP-AES is suggested. Depending on the matrix composition and the amounts of the analyte, the analytical lines suffering from little interferences and the limit of determination can be determined from calculation using spectral interference coefficients. For this calculation, the spectral interference coefficients, which are defined as apparent mass of the analyte equivalent to the spectral interference from unit mass of the interferent, are obtained experimentally for 639 emission lines of 68 elements. There is a good correlation between the coefficients obtained on two spectrometers having different resolutions.     

Instrumental neutron activation analysis in geochemistry: Emphasis on spectral and uranium fission product interferences

Summary The accuracy of the analytical results may suffer from unsolved interferences both spectral or due to U fission products despite progress performed in electronics and informatics in instrumental neutron activation analysis. This contribution deals with the correction of spectral and U fission product interferences using a multicomponent method based on the resolution of simultaneous equation method and using the Erdtmann isotope-related k_I-factors for the determination of the correction factors of interferences due to U fission products, respectively. These resolution methods were tested on typical phosphate and uraniferous ore samples.     

Influence of methane addition on selenium isotope sensitivity and their spectral interferences

The measurements of stable selenium (Se) isotopic signatures by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) are very challenging, due to the presence of spectral interferences and the low abundance of Se in environmental samples. We systematically investigated the effect of methane addition on the signal of Se isotopes and their interferences. It is the first time that the effect of methane addition has been assessed for all Se isotopes and its potential interferences using hydride generator multi-collector inductively coupled plasma mass spectrometry (HG-MC-ICP-MS). Our results show that a small methane addition increases the sensitivity. However, the response differs between a hydride generator and a standard introduction system, which might be related to differences in the ionization processes. Both argon and hydrogen-based interferences, the most common spectral interferences on selenium isotopes in HG-MC-ICP-MS, decrease with increasing methane addition. Therefore, analyte-interference ratios and precision are improved. Methane addition has thus a high potential for the application to stable Se isotopes ratios by HG-MC-ICP-MS.     

自模型曲线分辨法校正电感耦合等离子体原子发射光谱中严重谱线重叠干扰

对严重重叠的光谱干扰校正,采用较小间隔的光谱扫描测量,并用间隔扫描点的数据计算,可减小计算结果的误差,提高结果的准确性。本方法用于校正Nd359.259nm对Sm359.260nm和V328.939nm对Yb328.937nm谱线重叠干扰,得到了满意的结果。