Early Peat Diagenesis Controls on Bromine Accumulation

Peatlands are natural reservoirs of organobromine compounds. Important advances have been made in unraveling the mechanisms involved in bromine (Br) retention in the peat but, to our knowledge, the temporal and spatial variation of the peat organic matter (OM) bromination has not been fully researched. Here, we present the study of 12 short cores (c. 30 cm, c. 150–200 years of peat accumulation) sampled from a small (c. 1 ha) area of an oceanic blanket peatland from northwestern Spain. We combine Br concentrations, spectroscopic analysis (FTIR–ATR), and structural equation statistical modelling (SEM). Our results show that Br is significantly correlated to proxies of peat aerobic decomposition, with concentrations increasing with depth in all cores (×2–10 times). Strong spatial heterogeneity was observed, with some cores showing much higher Br maximum concentrations and larger increases with depth. SEM modelling indicated that various OM functionalities contribute to Br accumulation and that their effects change with depth/age, with aromatics becoming dominant after 20–90 years. Thus, changes in organic matter molecular composition, linked to early peat diagenesis, and the geochemical conditions governing it exerted a strong control on Br accumulation in the studied peatland. Bromine wet deposition was not found to be a limiting factor.