Humic substances are mixtures of macromolecules with varied structures and chemical compositions that are affected by differences in parental biomaterials and environmental conditions. This study used elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and solid-state 13 C nuclear magnetic resonance spectroscopy (NMR) to identify the chemical and structural heterogeneity of 10 humic acids (HAs) and a humin. The HAs were obtained by progressively extracting solution from a soil in western Massachusetts, eight times with 0.1 M Na 4 P 2 O 7 and two times with 0.1 M NaOH. The humin was the residual fraction after 10 base extractions. As indicated by solid state NMR analysis, the aliphatic carbons (0 ϳ 108 ppm) of the HAs increased gradually from 50% in fraction 1 (F-1) to 62% in fraction 9 (F-9) and 70% for the humin, but the aromatic carbons (108 ϳ 162 ppm) were highest in F-1. The band assigned to aliphatic carbon (2930 cm ؊1 ) in the DRIFTS spectra gradually increased with further extractions, and the relative intensity of this peak was the highest in humin. The atomic C/H ratio declined from 1.1 for F-1 to 0.6 for F-10 and the humin, consistent with the spectroscopic analyses. In addition, both elemental and spectroscopic data reveal that the last extracted HA and humin contained relatively lower contents of polar functional groups such as carboxylic and phenolic groups. This study shows significant chemical, structural, and molecular differences among the 10 sequentially extracted HAs and humin, even from a single soil. (Soil Science 2003;Volume 168:880-887)
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