Selective associations of organic matter components with ferrihydrite: Implications for Fe-organic matter preservation in tidal flat wetlands

Abstract

The association of organic matter (OM) with iron (Fe) is a critical mechanism to preserve OM in intertidal coastal ecosystems such as salt marshes and mangroves. The present study aimed to investigate the influence of the organic carbon to Fe molar ratio (OC/Fe), ionic strength, and OM composition on Fe-OM association. Fe-OM was prepared using humic acids extracted from salt marsh and mangrove sediments by the adsorption process in the OC/Fe molar ratios of 0.01–1.0 and by the coprecipitation process in the OC/Fe molar ratios of 0.1–9.9. Sample properties were studied by X-ray diffraction, scanning electron microscopy, ultraviolet–visible spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, three-dimensional fluorescence excitation emission matrix spectroscopy, and pyrolysis–gas chromatography/mass spectrometry. The results showed that selective associations of OM components with ferrihydrite were affected by the association mode (e.g., adsorption and coprecipitation), OC/Fe molar ratio, OM composition and ionic strength. Abundant aliphatic compounds could be adsorbed on ferrihydrite. Moreover, ferrihydrite was prone to preserve humic-like fluorescent components through the adsorption process. The protein-like fluorescent components and aliphatic compounds had high affinity for ferrihydrite during coprecipitation with low OC/Fe molar ratios. An increase in the OC/Fe molar ratio resulted in coprecipitation of aromatic compounds with ferrihydrite. Salinity-induced flocculation caused more amount of aromatic and polycyclic aromatic compounds to associate with ferrihydrite during the coprecipitation process. Compared to the salt marsh OM, more N-compounds and less aliphatic compounds in the mangrove OM were coprecipitated with ferrihydrite. This study provided important insights into the mechanisms of OM preservation with ferrihydrite in tidal wetland ecosystems.