Elemental Composition of Magnetic Nanoparticles in Wildland-Urban Interface Fire Ashes Revealed by Single Particle-Inductively Coupled Plasma-Time-of-Flight-Mass Spectrometer.

Abstract

This study investigates the elemental composition of magnetic nanoparticles (MNPs) in eleven wildland-urban interface (WUI) fire ashes, including one vegetation, six structural, and four vehicle ashes, along with three fire-impacted soil samples. The WUI fire ash samples were collected following the 2020 North Complex (NC) Fire and Sonoma-Lake-Napa unit (LNU) Lightning Complex Fire in California. Efficiency of magnetic separation was confirmed via Time-Domain Nuclear Magnetic Resonance (TD-NMR); the relaxometry showed that the transverse relaxation rate R₂ decreased from 2.02 s^-1 before separation to 0.29 s^-1 after separation (ΔR₂ = -1.73 s^-1; -86%), due to the removal of magnetic particles. The particle number concentrations, size distributions, and elemental compositions (and ratios) of MNPs were determined using single particle-inductively coupled plasma-time-of-flight-mass spectrometry (SP-ICP-TOF-MS). The major types of nanoparticles (NPs) detected in the magnetically separated MNPs were Fe-, Ti-, Cr-, Pb-, Mn-, and Zn-bearing NPs. The iron-bearing NPs accounted for 3.2 to 83.5% of the magnetically separated MNPs, and decreased following the order vegetation ash (77.4%) > soil (63.2-69.9%) > structural (3.2-83.5%) ash. The titanium-bearing NPs accounted for 3.3 to 66.1% of the magnetically separated MNPs, and decreased following the order vehicle (14.1-66.1%) > structural (3.5-36.4%) > vegetation (3.3%) ash. The majority of the detected NPs in the fire ashes occurred in the form of multi-metal (mm) NPs, attributed to the presence of NPs as heteroaggregates and/or due to the sorption of metals on the surfaces of NPs during combustion. However, a notable fraction (3-91%) of the detected NPs occurred as single-metal (sm) NPs, particularly smFe-bearing NPs, which accounted for 48 to 91% of all the Fe-bearing particles in the magnetically separated MNPs. The elemental ratios (e.g., Al/Fe, Ti/Fe, Cr/Fe, and Zn/Fe) in the magnetically separated MNPs from structural and vehicle ashes were higher than those in the soil samples and vegetation ashes, indicating enrichment of metals in magnetically separated NPs from vehicle and structural ashes compared to vegetation ash. Overall, this study demonstrates that the MNPs generated by WUI fire ash are associated with potentially toxic elements (e.g., Cr and Zn), exacerbating the environmental and human health risks of WUI fires. This study also highlights the need for further research into the properties, environmental fate, transport, and interactions of MNPs with biological systems during and following WUI fires.