RESUMO
Granulometric fractionation as a source of additional information on organic-matter and inorganic matrix components of soils using FTIR-photoacoustic spectroscopy (FTIR-PAS) supported by attenuated-total reflection FTIR spectroscopy (ATR-FTIR) for a wide range of aggregate fractions (10-5000 µm) was used to compare the sensitivity, reproducibility, information contents, and representativity of fractionated samples. For chernozem and sod-podzolic soils and different agricultural-use chernozem samples, differences in the composition were found, manifested in normalized spectra of microaggregate fractions, with the range of 10-100 µm bearing the complete information. Most changes are observed in the soil organic matter range (1900-1340 cm-1), although these changes are slight, and in the soil-matrix region (550-300 cm-1). The latter region increases the intensity of bands corresponding to amorphous silica and clay minerals in fine fractions, while the intensity of bands attributed to quartz lattice vibrations decreases. FTIR-PAS spectra do not differ considerably at high interferometer modulation frequencies as the signal-penetration depth is comparable with particle sizes. The soil fractions below 20 µm result in the maximum sensitivity, reproducibility, and signal-to-noise ratio, showing no changes from coarser fractions by the information content and, thus, providing representative samples for analysis. The fractionation shows more differences in the sod-podzolic and chernozem soil fractions than the whole soil spectra. FTIR-PAS provides better sensitivity and reproducibility in the 4000-2000 cm-1 region and ATR-FTIR in the 2000-100 cm-1 region.
RESUMO
The qualitative analysis of nanodiamonds by FTIR spectrometry as photoacoustic (FTIR-PAS), diffuse-reflectance (DRIFT), and attenuated total reflection (ATR) modalities was evaluated for rapid and nondestructive analysis and comparison of nanodiamonds. The reproducibility and signal-gathering depth of spectra was compared. The assignment of characteristic bands showed that only six groups of bands were present in spectra of all the modalities with appropriate sensitivity: 1760 (C=O stretch, isolated carboxyl groups); 1640-1632 (H-O-H bend, liquid water); 1400-1370 (non-carboxyl C-O-H in-plane bend and CH2 deformation); 1103 (non-carboxyl C-O stretch); 1060 (in-plane C-H bend, non-aromatic hydrocarbons and carbohydrates); 940 cm-1 (out-of-plane carboxyl C-O-H bend). DRIFT provides the maximum number of bands and is capable of measuring hydrogen-bonded bands and CHx groups. ATR provides the good sensitivity for water and C-H/C-C bands in the range 2000-400 cm-1. FTIR-PAS reveals less bands than DRIFT but more intense bands than ATR-FTIR and shows the maximum sensitivity for absorption bands that do not appear in ATR-IR spectra and are expedient for supporting either DRIFT or FTIR-PAS along with depth-profiling. Thus, all three modalities are required for the full characterization of nanodiamonds surface functional groups.
RESUMO
FTIR photoacoustic spectroscopy was used to approach inorganic matrix components and organic-matter constituents of chernozem size fractions (1-5000 µm, by dry sieving) with a different history of use (from intact steppe to permanent bare fallow, a continuous long-term field experiment). The conditions of FTIR photoacoustic measurements in continuous-scan modes were compared with attenuated total reflection measurements, the advantages of photoacoustic measurements resulting from a higher intensity of the incident radiation and signal-generating volume were discussed. Overtone peaks of quartz as a soil matrix component at 2000-1700 cm-1 were selected as a possible internal-standard (guide) bands for the comparison of photoacoustic spectra. For different land-use samples, differences in the composition were found, which are differently manifested in normalized spectra of size fractions, with millimeter-size, 20-100 µm, and silt fraction bearing the maximum information.
