Volcanic eruptions release gases and particulates that may adversely affect human health. The Tajogaite eruption on La Palma provided a unique opportunity to evaluate inorganic pollutant exposure in a directly affected population. As part of the ISVOLCAN study, blood samples from 393 adults residing in the island's western region were analyzed for 43 inorganic elements using Inductively Coupled Plasma Mass Spectrometry (ICP-MS), including 20 toxic elements identified by the Agency for Toxic Substances and Disease Registry (ATSDR). The median age of participants was 51 years, and 56.7% were female. Higher levels of Hg and Mn were associated with long-term occupational exposure, while smoking was linked to elevated Cd, Pb, and Sr levels. Participants living within 6.5 km of the volcano had significantly higher concentrations of Al and Ti. Ash cleanup activities were associated with increased levels of Ni and Cu, and those spending over five hours outdoors daily showed elevated Se and Pb. This is the first biomonitoring study to assess blood concentrations of inorganic pollutants in a population exposed to volcanic emissions. The findings highlight key exposure factors and underscore the need for continued research to assess long-term health effects and inform public health measures.