Transmission infrared (IR) spectroscopy, either dispersive or Fourier transformed (FTIR), has been used extensively in studies on humic substances. A variety of bands characteristic of molecular structures and functional groups have been identified for these substances. The development of an attachment mounted onto FTIR spectrophotometers has allowed the determination of diffuse reflectance Fourier‐transformed infrared (DRIFT) spectra. The purpose of this work was to study the applicability of DRIFT to soil organic‐matter research and to compare the use of this instrumentation to dispersive and Fourier‐transformed transmission IR spectroscopy. The DRIFT spectra were determined for humic acids, peat samples, and composts. In addition, the possibility of using DRIFT spectra to quantitatively measure sample concentration and measuring the relative concentration of functional groups was assessed. Sample preparation for DRIFT is much simpler than for transmission IR spectroscopy, interferences due to water adsorption are reduced, and resolution is improved. The spectra obtained using DRIFT had a higher degree of resolution as compared with dispersive and Fourier‐transform transmission IR spectroscopy. Bands indicative of aliphatic C‐H, carboxyl and corboxylate functional groups, aromatic C=C, and C‐O stretch of polysaccharides were prominent and very well resolved. The DRIFT spectra obtained can also he used to fingerprint organic matter acquired from various sources. Spectra obtained at various concentrations of humic acid indicated that DRIFT cannot be used to estimate concentrations of organic matter in a given mixture. Relative concentrations of functional groups, however, were found to be fairly constant regardless of sample concentration. Therefore, changes in the relative concentration of functional groups can he measured during the humification process. It is expected that the application of DRIFT to organic‐matter research will prove especially useful for characterizing bulky heterogeneous samples such as peat and composts.
Phenolic compounds undergo several transformation processes in soil and water (i.e., partial degradation, mineralization, and polymerization), many of which have been attributed primarily to biological activity. Results from previous work indicate that naturally occurring Mn oxides are also capable of oxidizing phenolic compounds. In the present study, 14C‐labeled catechol was reacted with birnessite (manganese oxide) in aqueous suspension at pH 4. The mass of catechol‐derived C in solid, solution, and gas phases was quantified as a function of time. Between 5 and 16% of the total catechol C was liberated as CO2 from oxidation and abiotic ring cleavage under various conditions. Most of the 14C (55–83%) was incorporated into the solid phase in the form of stable organic reaction products whereas solution phase 14C concentrations increased from 16 to 39% with a doubling of total catechol added. Polymerization and CO2 evolution appear to be competitive pathways in the transformation of catechol since their relative importance was strongly dependent on initial birnessite–catechol reaction conditions. Solid phase Fourier transform infrared (FTIR) spectra are consistent with the presence of phenolic, quinone, and aromatic ring cleavage products. Carbon dioxide release appears to be limited by availability of reactive birnessite surface sites and it is diminished in the presence of polymerized reaction products.
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