Pyrites in a salt marsh-ria system: quantification, morphology, and mobilization

Abstract

Galician Rias are among the most productive ecosystems in the world. Consequently, the soils of their salt marshes and sediments of the intertidal flats show high organic matter contents, reactive Fe, and sulfate, which promote pyrite synthesis and accumulation, using sulfate for organic matter decomposition. This work studies the morphological variability and concentration of pyrites (individual crystals and framboids) in different geochemical environments found in the Ria de Ortigueira (salt marsh soils and bottom sediments in the inner, middle, and outer section), addressing their dynamics in the marsh-ria system in relation to the hydrodynamic characteristics defined by tides and river discharges. Framboidal pyrites were the dominant morphology in marsh soils and sediments in the middle and inner sections of the Ria, while isolated crystals dominated its outer section. The results showed that lower marsh soils (colonized by Spartina) are the most favorable environment for pyrite synthesis, showing high pyritic Fe concentrations and high degrees of pyritization, largely exceeding the values observed in sediments from Galician Rias and from most sedimentary environments worldwide. However, the amount of framboidal pyrites present in the lower marsh (SPE: 4–5 × 104 framboids) was clearly lower than in bottom sediments of the inner and middle part of the Ria de Ortigueira (∼2–7 × 106 framboids), mainly due to the fact that pyrites were found to form large framboids in lower salt marsh soils. Thus, the amount of framboidal pyrites does not seem to be a good indicator of redox conditions in modern marine sediments. Pyrite crystals found in the sediments of the Ria showed poorly defined vertices and facets, indicating their degradation and suggesting that a significant amount of the pyrites found in the middle and inner sections derive from marsh collapse. Finally, the output of framboidal pyrites towards the outer Ria de Ortigueira reflects the low intensity of residual flows in this Ria. Therefore, the pyrites observed in the outer section consisted only of isolated crystals, presumably formed in situ under low sulfate-reducing activity conditions