Replication Data for: Addressing matrix effects for 193 nm excimer LA-ICP-MS analyses of Fe-rich sulfides and a new predictive model.

Abstract: Laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is one of the most popular techniques for determining trace element concentrations in sulfides. Due to the lack of matrix-matched standards, standardization of sulfide analyses are usually based on silicate glass calibrant materials. Matrix effects during ns-LA-ICP-MS analyses of Fe-rich sulfides were quantified for many trace elements by comparison of elemental concentrations obtained by LA-ICP-MS and electron microprobe (EPMA) for many synthetic sulfides. The data was used to obtain the fractionation indices (Fi, the ratio between the EPMA- and LA-ICP-MS-determined concentrations of element i) for many elements while considering Fe, Cu and Ni as internal standards. The results show that significant (>15% RD) matrix effects arise during ns-LA-ICP-MS analyses of Ti, Zn, Ge, Se, Mo, Cd, In, Sb, Te, Pb, Bi in sulfides when using Fe as the internal standard. The use of Ni as an internal standard yields on average higher Fi values for most elements, resulting in more pronounced matrix effects for refractory elements and less so for volatile elements, relative to Fe. The use of Cu as an internal standard yields overall more significant matrix effects for volatile elements (i.e., lower Fi values). The Fi values for most elements remain constant with increasing concentrations, and matrix correction factors for these elements can therefore be applied across the ppm to wt% range. In agreement with previous observations for Fe-rich metals and silicate glasses, the magnitudes of the matrix effects for the various elements are strongly correlated with elemental volatility. This correlation was used to obtain a predictive model for describing Fi for Fe-rich sulfides. The results were used to assess the effects of matrix effects on calculated sulfide liquid–silicate melt partition coefficients derived from experiments. Matrix effects arising through the use of non-matrix-matched standards will result in significant discrepancies between measured and true partition coefficients, the extent mainly depending of the volatility of the element considered. Corrections on ns-LA-ICP-MS derived element concentrations therefore need to be performed to obtain true abundances in the absence of matrix-matched standards. TRR 170 no. 90摘要：激光剥蚀电感耦合等离子体质谱法（LA-ICP-MS）是测定硫化物中微量元素含量的主流技术之一。由于缺乏基体匹配标准物质，硫化物分析的标准化通常以硅酸盐玻璃校准材料为依据。本研究针对富铁硫化物的纳秒级LA-ICP-MS（ns-LA-ICP-MS）分析过程中的多种微量元素基体效应，通过对比多组合成硫化物的LA-ICP-MS与电子探针微区分析（EPMA）测得的元素浓度，实现了定量表征。研究以铁、铜、镍作为内标，计算得到多种元素的分馏指数（Fi，即EPMA与LA-ICP-MS测得的元素i的浓度比值）。结果显示，当以铁作为内标时，针对硫化物中钛（Ti）、锌（Zn）、锗（Ge）、硒（Se）、钼（Mo）、镉（Cd）、铟（In）、锑（Sb）、碲（Te）、铅（Pb）、铋（Bi）的纳秒级LA-ICP-MS分析会产生相对偏差大于15%的显著基体效应。相较于以铁作为内标，采用镍作为内标时，多数元素的Fi值平均更高，导致难熔元素的基体效应更为显著，而挥发性元素的基体效应则相对减弱。采用铜作为内标时，挥发性元素的基体效应整体更为显著（即Fi值更低）。多数元素的Fi值随浓度升高保持稳定，因此针对这些元素的基体校正因子可应用于百万分之一（ppm）至质量百分比（wt%）的浓度区间。与此前针对富铁金属及硅酸盐玻璃的研究结论一致，各类元素的基体效应强度与元素挥发性显著相关。基于该相关性，本研究构建了适用于富铁硫化物的Fi值预测模型。本研究结果被用于评估基体效应对实验测得的硫化物熔体-硅酸盐熔体分配系数的影响。采用非基体匹配标准物质所引入的基体效应，会导致测得的分配系数与真实值间出现显著偏差，其偏差程度主要取决于目标元素的挥发性。因此，在缺乏基体匹配标准物质的情况下，需对纳秒级LA-ICP-MS测得的元素浓度进行基体校正，以获取真实的元素丰度。TRR 170 no. 90