Abstract. We describe resonance effects in laser desorption–ionization (LDI) of particles that substantially increase the sensitivity and selectivity to metals in single-particle mass spectrometry (SPMS). Within the proposed scenario, resonant light absorption by ablated metal atoms increases their ionization rate within a single laser pulse. By choosing the appropriate laser wavelength, the key micronutrients Fe, Zn and Mn can be detected on individual aerosol particles with considerably improved efficiency. These ionization enhancements for metals apply to natural dust and anthropogenic aerosols, both important sources of bioavailable metals to marine environments. Transferring the results into applications, we show that the spectrum of our KrF-excimer laser is in resonance with a major absorption line of iron atoms. To estimate the impact of resonant LDI on the metal detection efficiency in SPMS applications, we performed a field experiment on ambient air with two alternately firing excimer lasers of different wavelengths. Herein, resonant LDI with the KrF-excimer laser (248.3 nm) revealed iron signatures for many more particles of the same aerosol ensemble compared to the more common ArF-excimer laser line of 193.3 nm (nonresonant LDI of iron). Many of the particles that showed iron contents upon resonant LDI were mixtures of sea salt and organic carbon. For nonresonant ionization, iron was exclusively detected in particles with a soot contribution. This suggests that resonant LDI allows a more universal and secure metal detection in SPMS. Moreover, our field study indicates relevant atmospheric iron transport by mixed organic particles, a pathway that might be underestimated in SPMS measurements based on nonresonant LDI. Our findings show a way to improve the detection and source attribution capabilities of SPMS for particle-bound metals, a health-relevant aerosol component and an important source of micronutrients to the surface oceans affecting marine primary productivity.
Abstract. We describe resonance effects in laser desorption/ionization (LDI) of particles that substantially increase the sensitivity and selectivity to metals in single particle mass spectrometry (SPMS). Within the proposed scenario, resonant light absorption by ablated metal atoms increases their ionization rate within a single laser pulse. By choosing the appropriate laser wavelength, the key micronutrients Fe, Zn and Mn can be detected on individual aerosol particles with considerably improved efficiency. These ionization enhancements for metals apply to natural dust and anthropogenic aerosols, both important sources of bioavailable metals to marine environments. Transferring the results into applications, we show that the spectrum of our KrF-excimer laser is in resonance with a major absorption line of iron atoms. To estimate the impact of resonant LDI on the metal detection efficiency in SPMS applications, we performed a field experiment on ambient air with two alternately firing excimer lasers of different wavelengths. Herein, resonant LDI with the KrF-excimer laser (248.3 nm) revealed Fe signatures for many more aerosol particles compared to the more common ArF-excimer laser line of 193.3 nm. Moreover, resonant ionization of iron appeared to be less dependent on the particle matrix than conventional non-resonant LDI, allowing a more universal and secure detection of Fe. Our findings show a way to improve the detection and source attribution capabilities of SPMS for particle-bound metals, a health-relevant aerosol component and an important source of micronutrients to the surface oceans affecting marine primary productivity.
Riverbed sediments in agricultural landscapes are loaded with phosphorus (P). They may act as a source or sink for riverine P, possibly causing harmful algae blooms and eutrophication in streams and receiving water bodies, including coastal waters. In this study, we aimed at identifying the labile, moderately labile, and stable P fraction (Hedley fractionation) in sediments of a northeastern German river basin (3000 km2). A non-metrical multidimensional scaling (NMDS) was used to identify the most significant environmental predictors of the P fractionation in sediments. The total P contents of the sediments varied over a wide range (698 ± 701 mg P kg−1 sediment−1), spanning from 98 to 2648 mg P kg−1 sediment−1. Adjacent agricultural reference soils had markedly lower total P contents of 354 ± 132 mg P kg−1 soil−1, ranging from 146 to 483 P kg−1 soil−1. There were almost no differences between the P contents of the top (0–2 cm) and the bottom (2–10 cm) layer. The dominant P fractions were the moderately labile (NaOH-P) and the stable (H2SO4-P) fractions, which accounted for more than 50% of the total P at each sampling point. The NMDS revealed that iron and aluminum contents, as well as land use, are significant predictors for the P fractionation of the sediment. The sediment P-composition reflects the P-status of the agriculturally used mineral soils. However, the size of the contributing catchment as well as the length of the water way have no effects on sediment P. In conclusion, sediment P stocks, though variable, may impede the good ecological status of river waters for decades, especially in lowland basins where hydraulic conditions and a very low stream velocity often create low redox and P dissolution conditions in sediments.
Figure S1: Accumulated mass spectra (n=400) of re-dispersed urban dust particles (Reference Material NIST 1649b), each for non-resonant (blue) and resonant (red) ionization with respect to (a,b) Fe, (c,d) Mn and (e,f) Zn. Some commonly observed ions are indicated.
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