Comprehensive investigation of chemical generation of volatile species (VSG) of palladium for detection by analytical atomic and mass spectrometry and, specifically, the mechanistic aspects of their formation and tentative identification are presented. VSG was achieved in a flow injection mode using a generator that permitted rapid mixing of acidified sample with NaBH4 reductant. Atomization in a diffusion flame with detection by atomic absorption spectrometry was exclusively used for optimization of generation conditions while inductively coupled plasma mass spectrometry was utilized to investigate overall system efficiency and analytical metrics of the VSG system for potential ultratrace analysis. Sodium diethyldithiocarbamate (DDTC) served as a crucial reaction modifier, enhancing overall system efficiency 9-fold. Combinations of modifiers, Triton X-100 and Antifoam B surfactants provided a synergistic effect to yield a further 2-fold enhancement of VSG. The overall system efficiency was in the range 16-22%, with higher efficiencies correlating with higher Pd concentrations. The contribution of co-generated aerosol to the overall system efficiency, determined by means of concurrent measurement of added Cs, was negligible - less than 0.1%. The nature of the volatile species was investigated using several approaches, but principally by transmission electron microscopy (TEM) after their collection on a grid, and by direct analysis in real time (DART) using high resolution orbitrap mass spectrometry. These experiments suggest a parallel but dual-route mechanism of VSG of Pd, one attributed to generation of a volatile DDTC chelate of Pd and a second to nanoparticle formation.

中文翻译：

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二乙基二硫代氨基甲酸酯增强了挥发性钯物种的化学生成，通过 AAS、ICP-MS、TEM 和 DART-MS 对其进行表征以及提出的作用机制

通过分析原子和质谱法检测钯的挥发性物质 (VSG) 的化学生成的综合研究，特别是它们的形成和初步鉴定的机械方面。VSG 是在流动注射模式下使用发生器实现的，该发生器允许酸化样品与 NaBH4 还原剂快速混合。通过原子吸收光谱法检测的扩散火焰中的雾化专门用于优化生成条件，而电感耦合等离子体质谱法用于研究 VSG 系统的整体系统效率和分析指标，以进行潜在的超痕量分析。二乙基二硫代氨基甲酸钠 (DDTC) 作为一种关键的反应改性剂，将整体系统效率提高了 9 倍。修饰符的组合，Triton X-100 和消泡剂 B 表面活性剂提供协同效应，使 VSG 进一步提高 2 倍。整体系统效率在 16-22% 的范围内，更高的效率与更高的 Pd 浓度相关。通过同时测量添加的 Cs 确定的共生气溶胶对整个系统效率的贡献可以忽略不计 - 小于 0.1%。挥发性物质的性质使用多种方法进行研究，但主要是通过在网格上收集后的透射电子显微镜 (TEM)，以及使用高分辨率轨道阱质谱法进行实时直接分析 (DART)。这些实验表明 Pd 的 VSG 的平行但双途径机制，一个归因于 Pd 的挥发性 DDTC 螯合物的产生，第二个归因于纳米颗粒的形成。