Environmental control on concretion-forming processes: Examples from Paleozoic terrigenous sediments of the North Gondwana margin, Armorican Massif (Middle Ordovician and Middle Devonian) and SW Sardinia (Late Ordovician)

Concretions of various compositions are common in the Paleozoic terrigenous successions of the north Gondwana margin. This study focuses on phosphatic (P) and siliceous (Si) concretions present in some successions of the Armorican Massif (NW France) and SW Sardinia (W Italy). It shows that they consist of mudstones, fine- to very fine-grained sandstones or shellbeds with a more or less abundant P-cement and form a continuum between a phosphatic end-member and a siliceous biogenic end-member. The P2O5 contents are ranging from 0.26% to 21.5% and are related to apatite. The SiO2 contents vary from 25% to 82% and are linked both to a terrigenous phase and to a biogenic silica phase. Concretions showing the lower P-contents (P2O5<1.5%) are often enriched in biogenic silica (SiO2/Al2O3>5). Comparison with the surrounding sediments shows that all the concretions are enriched in chlorite and in Middle Rare Earth Elements (La-s/Gd-s: 0.12-0.72) and some of them in Y (up to 974 ppm), Rare Earth Elements (more than 300 ppm) and Sr (260-880 ppm). The concretions with highest biogenic silica concentrations are contained in the outer shelf sediments whereas the other concretions are present from the proximal part of the inner shelf to the outer shelf. A genetic model in two stages is proposed. During early diagenesis, the dissolution of shells and degradation of organic matter progressively enrich the pore water in dissolved Si, Ca and P. When the suboxic zone is reached, P-precipitation begins, leading to the formation of protoconcretions. In shallow environments, the relative permeability of sediments and the winnowing or reworking of the upper few centimetres by bottom currents allow for suboxic conditions to be maintained, leading to P-rich concretion formation. In deeper environments, the anoxic zone is reached more rapidly, thereby preventing extensive phosphogenesis. Nevertheless in the protoconcretions the early P-cement preserves pore spaces from compaction. In the presence of biogenic siliceous particles, the fluids are enriched in dissolved silica and diffuse towards the protoconcretions. Silica precipitation can thus occur later in the intergranular spaces. (C) 2012 Elsevier B.V. All rights reserved.