Dissolved Organic Matter Sorption and Molecular Fractionation by Naturally Occurring Bacteriogenic Iron (Oxyhydr)oxides

• Published in: Environmental science & technology Vol. 53; no. 8; pp. 4295 - 4304
• Main Authors: Sowers, Tyler D, Holden, Kathryn L, Coward, Elizabeth K, Sparks, Donald L
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 16-04-2019
• Subjects: Affinity; Aliphatic compounds; Arsenates; BIOS; Carbon compounds; Carboxylic acids; Chromate; Chromates; Contaminants; Cyclotron resonance; Desorption; Dissolved organic matter; Environmental impact; Fourier transforms; Fractionation; Infrared spectroscopy; Ionic strength; Ions; Iron; Leaf litter; Mass spectrometry; Mass spectroscopy; Nutrient cycles; Nutrient transport; Organic carbon; Oxides; Rivers; Soil contamination; Sorbents; Sorption; Terrestrial environments; Water analysis; Waterways
• ISSN: 0013-936X; 1520-5851
• DOI: 10.1021/acs.est.9b00540

Iron (oxyhydr)­oxides are highly reactive, environmentally ubiquitous organic matter (OM) sorbents that act as mediators of terrestrial and aqueous OM cycling. However, current understanding of environmental iron (oxyhydr)­oxide affinity for OM is limited primarily to abiogenic oxides. Bacteriogenic iron (oxyhydr)­oxides (BIOs), common to quiescent waterways and soil redox transitions, possess a high affinity for oxyanions (i.e., arsenate and chromate) and suggests that BIOs may be similarly reactive for OM. Using adsorption and desorption batch reactions, paired with Fourier transform infrared spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry, this work demonstrates that BIOs are capable of sorbing leaf litter-extracted DOM and Suwannee River Humic/Fulvic Acid (SRHA/SRFA) and have sorptive preference for distinct organic carbon compound classes at the biomineral interface. BIOs were found to sorb DOM and SRFA to half the extent of 2-line ferrihydrite per mass of sorbent and was resilient to desorption at high ionic strength and in the presence of a competitive ligand. We observed the preferential sorption of aromatic and carboxylic-containing species and concurrent solution enrichment of aliphatic groups unassociated with carboxylic acids. These findings suggest that DOM cycling may be significantly affected by BIOs, which may impact nutrient and contaminant transport in circumneutral environments.