Soluble humic substances from in situ precipitated microcrystalline calcium carbonate, internal sediment, and spar cement in a Cretaceous carbonate mud-mound

Abstract

Albian carbonate mud-mound limestones exposed near Iraneta, northern Spain, show a fabric- and particle-specific fluorescence. Intense fluorescence is restricted to in situ precipitated microcrystalline (automicritic) fabrics, calcified demosponges, and coralline sponges. Intermediate intensity derives from micritized bioclasts, pellets, and a rim of marine bladed cement. Most invertebrate skeletons, late-diagenetic equant cement, and crosscutting zones of dolomitization are weakly to nonfluorescent. Internal microcrystalline sediment (allomicrite) and red algae debris have variable fluorescence. Correlation between rock fluorescence and soluble humic substances was evaluated from 3 g of automicrite, allomicrite, and cement. Time-resolved laser-induced fluorescence spectroscopy (TRLFS) with ultra-short pulses on two extracrystalline fractions (NaOH-soluble) and two intracrystalline fractions (HCl-soluble and NaOH-soluble) showed that most of the soluble humic substances of automicrite are within the crystals; but conversely, are significantly enriched on outer surfaces of allomicrite. Spar cement is close to detection limits. Fluorescence lifetimes are in the range of 0.5-2 ns and 3.5-6 ns. We conclude that precipitation of automicrite took place during oxidative organic matter diagenesis, i.e., during condensation reactions of degradation products of marine biopolymers. By contrast, allomicrite formed by skeletal breakdown followed by ingestion, organic coating, and reingestion during deposit feeding. A humic-substance-based model of marine polymer gels represents a new approach for the understanding of ancient polygenetic carbonate muds, so typical of Phanerozoic mud-mounds in deeper water settings.