4.8 Article

Real-Time Detection of Aerosol Metals Using Online Extractive Electrospray Ionization Mass Spectrometry

Journal

ANALYTICAL CHEMISTRY
Volume 92, Issue 1, Pages 1316-1325

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.analchem.9b04480

Keywords

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Funding

  1. European Union's Horizon 2020 research and innovation program under Marie Sklodowska-Curie grant [701647]
  2. Division of Energy and Environment Research at PSI (interlaboratory postdoctoral program)
  3. Swiss National Science Foundation [BSSGI0_155846, 200020_172602]
  4. Swiss National Science Foundation (SNF) [200020_172602, BSSGI0_155846] Funding Source: Swiss National Science Foundation (SNF)

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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.

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