Isotopic signature of atmospheric phosphate emitted from coal combustion

Atmospheric deposition of phosphorus (P) serves as an important nutrient input for many terrestrial, marine and freshwater ecosystems, influencing their biogeochemistry and primary production. Fossil fuel combustion, principally coal, is estimated to be a major source of atmospheric-P in industrialized regions. In this research, we aim to find a distinct isotopic signature for fly coal ash, the by-product of coal combustion that is emitted to the atmosphere. This signature could be used to identify coal's contribution to atmospheric-P. For this aim, ten fly coal ash samples from different coal sources, collected by power station filters, were analyzed for P concentrations and stable oxygen isotopic composition (δ18OP). Two inorganic phosphate fractions were analyzed: HCl-extractable and resin-extractable (bioavailable P). High HCl-P concentrations of up to 3500 μg P/g ash were found with a distinct δ18OP range of 17.1-20.5‰. The resin-P concentrations were substantially lower (<8 μg/g) with a wider and significantly lower δ18OP range of 10.6-16.5‰. The ash samples were found to have HCl-P δ18OP higher in ∼0-∼9‰ relative to the source coal. Similar isotopic values were found for ash with the same coal source country, regardless of the power station. Despite the low bioavailable P concentrations, fly ash could still be an important atmospheric P source to the biosphere since these combustion products likely acidify in the atmosphere to become bioavailable. This is also supported by our finding that smaller particles, which are more indicative of the particles actually emitted to the atmosphere, are significantly P-richer. Natural dust sources' δ18OP overlap fly ash's range, complicating the assessment of coal's contribution. Nonetheless, our results provide a new tool for identification of fossil fuel combustion sources in local and global atmospheric P deposition.