Ácidos húmicos (HA) extraídos de carvões de diferentes ranks, de suas amostras regeneradas e de uma amostra nitrada, foram caracterizados por análise elementar e por espectroscopia de infravermelho (FTIR), de ressonância magnética nuclear de 13 C no estado sólido (NMR) e de ressonância paramagnética eletrônica (EPR). O HA de carvão de baixo rank apresentou maiores valores de teor de C e razão C/N e menores valores de teor de O e razões H/C e O/C do que o de alto rank. Resultados de RMN mostraram que ambas amostras foram mais aromáticas e menos carboxílicas do que HA comuns em solos. Estas características podem limitar o uso de HA de carvão como condicionadores e fertilizantes adequados para solos. A regeneração não provocou alterações relevantes, exceto pelo decréscimo no teor de radicias livres determinados por espectroscopia de EPR. Provavelmente as condições e o tempo de regeneração não foram adequados para oxidar as amostras. Os espectros de FTIR obtidos foram semelhantes, excentuando-se aquele da amostra nitrada, onde a banda de absorção em 1533 cm -1 comprova a presença de grupos nitrogenados. A nitração aumentou o teor de N e reduziu a razão C/N a valores comparáveis aos observados em HA de solos, porém a aromaticidade permaneceu alta e o teor de carboxílicos diminuiu após o processo.Humic acids (HA) extracted from two coals of different ranks, from their regenerated samples and from a nitrated sample, were characterized by elemental analysis and by infra-red (FTIR), solid state 13 C nuclear magnetic resonance (NMR) and eletronic paramagnetic resonance (EPR) spectroscopies. The low rank coal HA presented higher C and lower O contents, higher C/N and lower H/C and O/C ratios than high rank coal HA. NMR results showed that both samples were more aromatic and less carboxylic than common soil HA. Those characteristics may limit the coal HA efficiency as an appropriate soil conditioner and fertilizer. The regeneration process did not produce major alterations in the coal HA, except a decrease of the free radical content as determined by EPR spectroscopy. Probably, the regeneration conditions and time were not adequate to oxidize the samples. The obtained FTIR spectra were much alike, except that from the nitrated sample, where the absorption band at 1533 cm -1 confirms the presence of nitrated groups. The nitration process increased the N content and reduced the C/N ratio to values comparable to those reported for soil HA, but the aromaticity still remained high and the carboxylic content was lowered after the procedure.

a b s t r a c tThe Brazilian oil shale byproducts resulting from the Petrosix pyrolysis (retortage) process were submitted to a set of analytical techniques to evaluate their possible use as agricultural soil conditioners. Liquid dichloromethane extracts from the solid samples were analyzed using capillary column gas chromatography-mass spectrometry. The results showed that of the 16 PAHs designated by the U.S. EPA as priority pollutants, only phenanthrene, fluorene and naphthalene, present in the retorted oil shale sample taken from inside storage piles; benzo[k]fluoranthene, present in the dolomite limestone layer between the two layers of oil shale in the mine structure; and naphthalene, present in powdered raw oil shale, were above the limits established by the EPA. The solid Brazilian oil shale byproduct samples were also analyzed by X-ray diffractometry (XRD), diffuse reflectance ultraviolet-visible spectroscopy (DRUV-VIS), X-ray fluorescence spectroscopy (XRF) and electron paramagnetic resonance (EPR) spectroscopy. The XRD analysis showed that the pyrolysis process produces a "weathering" transformation, for example with the appearance of kaolinite diffraction lines in the retorted samples. The DRUV-VIS and XRF spectroscopy results indicated iron oxide goethite interactions with the PAHs present in the solid samples studied. The EPR spectroscopy showed that the samples row oil shale (g = 2.0044) and the powder oil shale (g = 2.0035), before the dichloromethane extraction, presented organic free radical signals associated with oxygen atoms. The other Brazilian oil shale byproduct samples, before and after the dichloromethane extraction, showed organic free radical signals associated with carbon atoms (g = 2.0022-2.0031).

The present paper describes an interaction study of phenol, o-cresol, and p-cresol with a rich-clay soil sample (clay content of 62.3%). Experiments performed using long contact times, in concentrations of 50.0 mg L(-1) showed practically no signal of phenol, o-cresol, and p-cresol after 48, 72, and 120 h, respectively, suggesting a sorption process. Sorption experiments in the period of 24 h were carried out with the phenolic compounds in concentrations between 5.00 and 500.0 mg L(-1), and negligible interaction between the phenolic species and the soil was observed. Additional experiments were carried out using HgCl(2) or NaN(3) solution as biodegradation inhibitors. After 10 days of contact time in the presence of inhibitors, no alterations in the concentrations of the three compounds studied were observed, and the results suggest no sorption process, with the compounds being almost entirely biodegraded by the soil sample, or possibly the formation of nonextractable residues could occur.

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