¹²⁹I in sediment cores from the Celtic Sea by AMS through a microwave digestion process

Radiochemical methods before measurement are indispensable to determine Iodine-129 by Accelerator Mass Spectrometry (AMS) in environmental samples. In particular, in sediments, iodine is associated with both inorganic and organic matter, and it presents in several chemical forms. Therefore, the radiochemical procedure must be designed to extract all the different iodine species from the matrix, whilst being as robust and time effective as possible. In this work, different microwave digestion methods, together with the processing of the iodine species to be measured by AMS, were tested and their performances are presented here. Two sediment cores, one with muddy sediment (core A) and one with permeable sandy sediment (core I), collected in the Celtic Sea, were used and the results were evaluated to determine an optimized iodine extraction. The method consisted of a microwave digestion with concentrated nitric acid followed by a double liquid-liquid extraction and the final precipitation of silver iodide (AgI), required to measure iodine by AMS. Back extraction of iodine in a reducing solution during purification was carried out with hydrazine (NH₂-NH₂). Subsequent additional steps were added to optimize all iodine species extraction. First, hydrochloric hydroxylamine (NH₂OH·HCl) and sodium bisulfite (Na₂S₂O₅) were used to homogenize all iodine species before extraction through a redox process. Second, sodium hypochlorite (NaOCl) was added to remove any final organic matter after digestion. The final method incorporated sodium hydroxide (NaOH) combined with NaOCl to facilitate reduction of iodine in solution and enhance the NaOCl effect. The different methods were validated against an internal standard and the last method was chosen, as it showed the most reproducible and accurate results. As practical application, Iodine-129 concentration from both cores were compared, showing concentrations between 0.19 x 10¹² at/kg and 7.16 x 10¹² at/kg for core A and between 0.28 x 10¹² at/kg and 2.40 x 10¹² at/kg for core I. Despite the ¹²⁹I diffusion detected in the deeper layers, depth profiles accurately reproduced Sellafield discharges, which is the nuclear fuel reprocessing plant closest to the cores.