Real-Time Detection of Aerosol Metals Using Online Extractive Electrospray Ionization Mass Spectrometry
Real-Time Detection of Aerosol Metals Using Online Extractive Electrospray Ionization Mass Spectrometry
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DOI：
10.1021/acs.analchem.9b04480
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发表时间：
2020-01-07
影响因子：
7.4
通讯作者：
Slowik, Jay
中科院分区：
文献类型：
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作者：
Giannoukos, Stamatios;Lee, Chuan Ping;Slowik, Jay
金属排放因其对人类健康和生态系统的剧毒影响而成为主要的环境和实际问题。目前市场上可用的检测技术通常受到 1 小时或更长的时间分辨率的限制（例如，通过半连续 X 射线荧光测量），或者是非定量的（例如，激光烧蚀质谱法）。在这项工作中，我们报告了一种新技术的开发，该技术使用提取电喷雾电离（EESI）源与高分辨率飞行时间质谱仪（TOF-MS）相结合，实时检测和监测金属颗粒。实验在负电离模式下进行，使用乙二胺四乙酸二钠（EDTA）二水合物与金属螯合并形成稳定的金属配合物。获得了水溶性金属化合物的结果。检查了以下代表性金属离子：Pb、Cd、Zn、Ce (III)、Ba、Ni、Fe(II)、Fe(III)、Cu(II)、Cr、Mo、Co(II)、Mg、Nd、Li、Ti、Ca、Cs、Ag、Tm、Er(III)、La(III)、Yb(III)、Eu(III)、Pr(III)、Gd(III)、Lu(III)、Dy(III)、 Tb(III)、Ho 和 Ru(III)。结果显示出非常好的线性质量响应 (R-2 = 0.9983)、低 ng/m(3) 检测限 (LoD) 和快速响应时间 (1 s)。所开发的 EESI-TOF-MS 的稳定性和重复性在复杂的动态和周期性实验条件下进行了测试，并且对内部和外部混合的金属颗粒测量了可忽略不计的基体效应。还进行了针对电感耦合等离子体质谱 (ICP-MS) 的基准测试，突出了 LoD 低于 ICP-MS 的气溶胶金属的在线测量能力。在印度新德里进行了概念验证环境测量，并获得了非常有希望的结果，从而可以在其他地方进一步利用。
Metal emissions are of major environmental and practical concern because of their highly toxic effects on human health and ecosystems. Current technologies available in the market for their detection are typically limited by a time resolution of 1 h or longer (e.g., via semicontinuous X-ray fluorescence measurements) or are nonquantitative (e.g., laser ablation mass spectrometry). In this work, we report the development of a novel technique for the real-time detection and monitoring of metal particles in situ using an extractive electrospray ionization (EESI) source coupled to a high -resolution time -of-flight mass spectrometer (TOF-MS). The experiments were conducted in negative ionization mode using disodium ethylenediamine tetraacetic acid (EDTA) dihydrate to chelate with metals and form stable metal complexes. Results for water-soluble metal compounds were obtained. The following representative metal ions were examined: Pb, Cd, Zn, Ce (III), Ba, Ni, Fe(II), Fe(III), Cu(II), Cr, Mo, Co(II), Mg, Nd, Li, Ti, Ca, Cs, Ag, Tm, Er(III), La(III), Yb(III), Eu(III), Pr(III), Gd(III), Lu(III), Dy(III), Tb(III), Ho, and Ru(III). The results showed a very good linear mass response (R-2 = 0.9983), low ng/m(3) limits of detection (LoD), and a fast response time (1 s). The stability and repeatability of the developed EESI-TOF-MS were tested under complex dynamic and periodic experimental conditions, and negligible matrix effects were measured for internally and externally mixed metal particles. Benchmark testing against inductively coupled plasma-mass spectrometry (ICP-MS) was also performed, highlighting the online measurement capabilities of aerosol metals with a LoD lower than those of ICP-MS. Proof-of-concept ambient measurements were performed in New Delhi, India, and very promising results were obtained, allowing further exploitation elsewhere.