PNNL

Abstract

Sediment-associated natural organic matter (NOM) is a complex assemblage of organic molecules with a wide range of sizes, functional groups, and structures, which is intricately associated with mineral particles. Organic carbon (OC) concentrations in subsurface sediments are typically 10 to 200 times lower than in surface soils, posing a distinct challenge for characterization. A range of chemical extractions were evaluated for extraction of NOM, and a NOM extraction scheme was developed using a combination of sequential extraction with water (MQ) and sodium pyrophosphate at pH 10 (PP), and purification by dialysis and solid phase extraction in order to isolate different fractions of sediment-associated NOM. Analysis of these different NOM fractions was then carried out by Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible (UV-Vis) spectroscopy, and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS). The OC extraction efficiency of the tested extractions followed the order PP>NaOH>HCl=hydroxylamine hydrochloride>dithionite. Greater concentrations of OC in PP vs NaOH extracts suggest that metal complexation and/or ligand exchange plays an important role in OC stabilization. Characterization of different pools of extraction NOM by FITR shows that the water soluble fraction has a higher fraction of aliphatic and carboxylic groups, while the PP fractions have higher C=C groups. This trend from aliphatic to more aromatic is also supported by the UV-Vis and ESI-FTICR-MS data.