Redox-sensitive trace metal hyper-enrichment in Tremadocian Alum Shale (graptolite argillite) in northwestern Estonia, Baltic Palaeobasin

The Alum Shale Formation, a widespread metal-rich black shale in Baltoscandia, was deposited during the Cambrian-Ordovician transition. Given that it straddles a period of alternating extinction/recovery events following the Cambrian Explosion and prior to the Great Ordovician Biodiversification Event, the Alum Shale in Scandinavia has been extensively studied to assess the effect of oceanic redox variations on these biotic events. However, there is an on-going debate about the depositional environment and the prevailing redox state. An Early Ordovician (Tremadocian) equivalent of the Scandinavian Alum Shale, locally known as graptolite argillite, can be found in Estonia and NW Russia, in the easternmost extension of the 'Alum Shale Sea'. In this contribution, we studied the redox-sensitive metal distribution and accumulation mechanisms in graptolite argillite successions in NW Estonia. Our aim was to provide better constraints on redox and depositional environments in the Baltic Palaeobasin. Our findings reveal that despite a consistent mineral and major elemental composition, V, Mo, Re and U contents vary systematically within the stratigraphy of the up to 7-m-thick black shale unit, with element contents reaching up to hyper-enrichment at the base (Mo > 200 mg/kg, U > 100 mg/kg and V > 1000 mg/kg) followed by a declining trend towards the upper part of the succession. This implies that temporal changes in redox conditions or sedimentation rates controlled trace element accumulation in the graptolite argillite. Although the redox-sensitive trace elements are hyper-enriched (particularly Mo), which has previously been interpreted to reflect euxinic depositional conditions, the V/Al vs. U/Al and V/Al vs. Mo/Al ratios indicate a non-euxinic anoxic depositional environment within a perennial oxygen minimum zone for the graptolite argillite. Further evidence of an unrestricted, relatively open marine depositional environment possibly influenced by upwelling is suggested by Cd/Mo and Co x Mn relationships. These results are supported by UEF and MoEF ratios that follow a seawater enrichment trend. The observed redox-sensitive element contents could be explained via diffusion-controlled uptake owing to the low sedimentation rates of the graptolite argillite (3-5 mm/kyr). These results highlight considerable redox variability within the Baltic Palaeobasin underscoring the need for a careful and critical reassessment of global redox interpretations based on Alum Shale data and emphasise the importance of using multiple independent redox and depositional environment proxies to determine palaeoredox conditions.