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Soil humic acids are the base soluble/acid insoluble organic components of soil organic matter. Most of what we know about humic acids comes from studies of their bulk molecular properties or analysis of individual fractions after extraction from soils. This work attempts to better define humic acids and explain similarities and differences for several soils varying in degrees of humification using advanced molecular level techniques. Our investigation using electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) and nuclear magnetic resonance spectroscopy (NMR) has given new insight into the distinctive molecular characteristics of humic acids which suggest a possible pathway for their formation. Humic acids from various ecosystems, climate regions and soil textural classes are distinguished by the presence of three predominant molecular components: lignin-like molecules, carboxyl-containing aliphatic molecules and condensed aromatic molecules that bear similarity to black carbon. Results show that humification may be linked to the relative abundance of these three types of molecules as well as the relative abundance of carboxyl groups in each molecular type. This work also demonstrates evidence for lignin as the primary source of soil organic matter, particularly condensed aromatic organic molecules often categorized as black carbon and is the first report of the non-pyrogenic source for these compounds in soils. We also suggest that much of the carboxyl-containing aliphatic molecules are sourced from lignin. Abbreviations ESI-FTICR-MS, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry; NMR, Nuclear Magnetic Resonance Spectroscopy; DBE, double bond equivalents; CRAM, carboxyl-rich alicyclic molecules; CCAM: carboxyl containing aliphatic molecules; BC, Black carbon; CPMAS, cross-polarization magic angle spinning; DPMAS, direct polarization magic angle spinning; KMD, Kendrick mass defect; Ai mod , modified aromaticity index

Pu concentrations in wetland surface sediments collected downstream of a former nuclear processing facility in F-Area of the Savannah River Site (SRS), USA, were ∼2.5 times greater than those measured in the associated upland aquifer sediments; similarly, the Pu concentration solid/water ratios were orders of magnitude greater in the wetland than in the low-organic matter content aquifer soils. Sediment Pu concentrations were correlated to total organic carbon and total nitrogen contents and even more strongly to hydroxamate siderophore (HS) concentrations. The HS were detected in the particulate or colloidal phases of the sediments but not in the low molecular weight fractions (<1000 Da). Macromolecules which scavenged the majority of the potentially mobile Pu were further separated from the bulk mobile organic matter fraction ("water extract") via an isoelectric focusing experiment (IEF). An electrospray ionization Fourier-transform ion cyclotron resonance ultrahigh resolution mass spectrometry (ESI FTICR-MS) spectral comparison of the IEF extract and a siderophore standard (desferrioxamine; DFO) suggested the presence of HS functionalities in the IEF extract. This study suggests that while HS are a very minor component in the sediment particulate/colloidal fractions, their concentrations greatly exceed those of ambient Pu, and HS may play an especially important role in Pu immobilization/remobilization in wetland sediments.

To study the effects of natural organic matter (NOM) on Pu sorption, Pu(IV) and (V) were amended at environmentally relevant concentrations (10(-14) M) to two soils of contrasting particulate NOM concentrations collected from the F-Area of the Savannah River Site. More Pu(IV) than (V) was bound to soil colloidal organic matter (COM). A de-ashed humic acid (i.e., metals being removed) scavenged more Pu(IV,V) into its colloidal fraction than the original HA incorporated into its colloidal fraction, and an inverse trend was thus observed for the particulate-fraction-bound Pu for these two types of HAs. However, the overall Pu binding capacity of HA (particulate + colloidal-Pu) decreased after de-ashing. The presence of NOM in the F-Area soil did not enhance Pu fixation to the organic-rich soil when compared to the organic-poor soil or the mineral phase from the same soil source, due to the formation of COM-bound Pu. Most importantly, Pu uptake by organic-rich soil decreased with increasing pH because more NOM in the colloidal size desorbed from the particulate fraction in the elevated pH systems, resulting in greater amounts of Pu associated with the COM fraction. This is in contrast to previous observations with low-NOM sediments or minerals, which showed increased Pu uptake with increasing pH levels. This demonstrates that despite Pu immobilization by NOM, COM can convert Pu into a more mobile form.

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