Department of Chemistry, Indiana University, Bloomington, 47405, United States.
Anal Chem. 2013 Jan 2;85(1):50-7. doi: 10.1021/ac302095w. Epub 2012 Dec 11.
Spatially resolved measurements of analyte emission along the cross-sectional axis of an axially viewed inductively coupled plasma (ICP) are utilized to indicate the presence of any of the three major categories of matrix interferences (i.e., plasma-related, sample introduction-related, and spectral interferences). Barium at concentrations of 0.05 or 0.1 M was chosen as a prototype element for plasma-related matrix effects, whereas common mineral acids (nitric, hydrochloric, sulfuric, and phosphoric) at volumetric concentrations from 1% to 20% were used to simulate sample introduction-related matrix effects. Three spectrally interfering line pairs (As and Cd at 228.81 nm, Er and Co at 239.73 nm, and Er and Ce at 302.27 nm) were selected for the study of spectral interferences. Due to dependence on the nature of the interference, the analytical bias at the center of the cross-sectional profile varied between -40% and +50%. In all matrix-interference categories, because plasma characteristics and excitation conditions are heterogeneous along this cross-sectional axis, matrix-induced shifts in analyte emission vary accordingly. As a result, the concentrations determined for an analyte along the cross-sectional plasma axis are not constant but exhibit a position dependence that allows the interference to be flagged. With the exception of spectral interference from emission lines whose total excitation potentials (i.e., the sum of ionization and excitation energies of an ionic emission line) are very close, the spatially resolved concentrations provide an effective indicator for flagging any other matrix interference in axial-viewing ICP-emission spectrometry. The method can be employed under the plasma forward power and carrier-gas flow conditions that are common for robust plasma operation.
轴向观测电感耦合等离子体(ICP)中沿横截面轴向的分析物发射的空间分辨测量用于指示三种主要基质干扰(即等离子体相关、样品引入相关和光谱干扰)中的任何一种的存在。选择浓度为 0.05 或 0.1 M 的钡作为等离子体相关基质效应的原型元素,而常用的矿物酸(硝酸、盐酸、硫酸和磷酸)在体积浓度为 1%至 20%的范围内用于模拟样品引入相关的基质效应。选择三个光谱干扰线对(228.81nm 的 As 和 Cd、239.73nm 的 Er 和 Co 以及 302.27nm 的 Er 和 Ce)来研究光谱干扰。由于分析偏差取决于干扰的性质,因此在横截面轮廓中心的分析偏差在-40%到+50%之间变化。在所有基质干扰类别中,由于等离子体特性和激发条件沿这个横截面轴是不均匀的,因此分析物发射的基质诱导位移也相应变化。结果,沿着横截面等离子体轴确定的分析物浓度不是恒定的,而是表现出位置依赖性,从而可以标记干扰。除了总激发电位(即离子发射线的电离和激发能量之和)非常接近的发射线的光谱干扰之外,空间分辨浓度为轴向观测 ICP 发射光谱中的任何其他基质干扰提供了有效的标记指示。该方法可以在等离子体正向功率和载气流条件下使用,这些条件对于稳健的等离子体操作是常见的。