LA-ICP-MS imaging technique application on Estonian sedimentary phosphorites: Revealing REE enrichment stages and advanced ore characterisation

The importance of rare earth elements (REEs) in high-tech industries and the growing demand for raw materials have spurred interest in exploring unconventional deposits. Sedimentary phosphorite deposits are among the most prospective, with REE extraction as a P by-product. However, these ores are highly diverse regarding ΣREE content, distribution, and nature of phosphatic materials. This study focuses on the Estonian phosphorites of the Baltic paleobasin, which constitute one of Europe's largest phosphate rock reserves and are characterised by phosphatic shell fragments deposited in nearshore settings.

Geochemical investigations were conducted on carbonate-cemented phosphorites from Toolse and Aseri deposits. The determination of REE distribution and uptake mechanisms within apatites and carbonates was addressed by LA-ICP-MS in situ imaging technique developed by Drost et al. (2018), which allows identification and discrimination of mineral phases by integrating semiquantitative compositional data through the stepwise elemental distribution. Diagenetic enrichment stages were assessed using the following pathfinder elements as pooling channels: Sr and U.

Shelly apatites have homogenous REE-distribution patterns, MREE-enriched up to 15-fold compared to the PAAS, with positive Y and Ce anomalies indicative of an early digenetic overprint traceable by the Sr distribution. The average REE content in studied apatite is 2149ppm. However, the extent of diagenetic overprint and enrichment varies locally. In Toolse, shells show lesser recrystallised textures, and the Sr- and U-depleted stages allow the tracing of pristine signals prior to deposition. In Aseri, U-sorting reveals a second, alteration-driven enrichment in which fragment edges present a ΣREE up to 7020ppm. This alteration stage is less pronounced in Toolse, where REE content reaches only 4150ppm. The distinction between Sr and U-driven enrichment is less evident due to the lower input of hydrogenic or lithogenic REE carriers. The carbonates from both localities were found to be REE depleted compared to PAAS.

Based on these observations, the compositions of the apatite species could be distinguished and modelled to characterise the deposit. The diagenetic enrichment of REE was mainly driven by the upwelling of nutrient-rich waters, Fe and Mn-(oxyhydr)oxide reductive desorption, and secondary phosphatisation and homogenisation of shells. Fluctuations of redox gradients and Fe-Mn cycles led to slight local REE variability. Developing euxinic conditions and lithogenic input endorsed a later alteration-driven uptake, resulting in highly REE-rich edges. Despite differences in enrichment level, the two deposits' REE distribution patterns are similar. Main REEs are Ce (33%), Y (21%), La (12%), Nd (16%) and Dy (3%), and are considered among the most critical elements. On average, U concentrations are 92ppm in Aseri and 31ppm in Toolse, and toxic elements (Cd, Zn, Th) are found in trace amounts.

The study introduces a combined technique based on LA-ICP-MS and empirical distribution function data analyses as a powerful, accurate, cost-effective tool for determining REE distributions. It allows visualisation at different scales, representative measurements and a first approach to semi-quantifying elements. The method could provide insights into factors that control genesis in low-grade sedimentary ores and determine their potential valorisation routes.