The reduction of structural Fe in smectite may be mediated either abiotically by reaction with chemical reducing agents or biotically by reaction with various bacterial species. The effects of abiotic reduction on clay surface chemistry are much better known than the effects of biotic reduction, and differences between them are still in need of investigation. The purpose of the present study was to compare the effects of dithionite (abiotic) and bacteria (biotic) reduction of structural Fe in nontronite on the clay structure as observed by variabletemperature Mössbauer spectroscopy. Biotic reduction was accomplished by incubating Na-saturated Garfield nontronite (sample API 33a) with Shewanella oneidensis strain MR-1 (Fe II /total Fe achieved was ~17 %). Partial abiotic reduction (Fe II /total Fe ~23 %) was achieved using pH-buffered sodium dithionite. The nontronite was also reduced abiotically to Fe II /total Fe ~96 %. Parallel samples were reoxidized by bubbling O 2 gas through the reduced suspensions at room temperature prior to Mössbauer analysis at 77 and 4 K. At 77 K, the reduction treatments all gave spectra composed of doublets for structural Fe II and Fe III in the nontronite. The spectra for reoxidized samples were largely restored to that of the unaltered sample, except for the sample reduced to 96 %. At 4 K, the spectrum for the 96 % reduced sample was highly complex and clearly reflected magnetic order in the sample. When partially reduced, the spectrum also exhibited magnetic order, but the features were completely different depending on whether reduced biotically or abiotically. The biotically reduced sample appeared to contain distinctly separate domains of Fe II and Fe III within the structure, whereas partial abiotic reduction produced a spectrum representative of Fe II -Fe III pairs as the dominant domain type. The 4 K spectra of the partially reduced, fully reoxidized samples were virtually the same as at 77 K, whereas reoxidation of the 96 % reduced sample produced a spectrum consisting of a magnetically ordered sextet with a minor contribution from a Fe II doublet, indicating significant structural alterations compared to the unaltered sample.

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SUMMARYThe industrial refining of kaolin involves the removal of iron oxides and hydroxides along with other impurities that cause discoloration of the final product and depreciate its commercial value, particularly undesirable if destined to the paper industry. The chemical leaching in the industrial processing requires treatments with sodium hyposulfite, metallic zinc, or sulfuric and phosphoric acids, in order to reduce, dissolve and remove ferruginous compounds. To mitigate the environmental impact, the acidic effluent from the leaching process must be neutralized, usually with calcium oxide. The resulting solid residue contains phosphorous, zinc, and calcium, among other essential nutrients for plant growth, suggesting its use as a macro and micronutrient source. Samples of such a solid industrial residue were used here to evaluate their potential as soil fertilizer in an incubation greenhouse experiment with two soil samples (clayey and mediumtextured). The small pH shift generated by applying the residue to the soil was not a limiting factor for its use in agriculture. The evolution of the concentrations of exchangeable calcium, and phosphorous and zinc extractability by Mehlich-1 extractant during the incubation period confirms the potential use of this industrial residue as agricultural fertilizer.Index terms: industrial residue, fertilizer, kaolin refining.( O beneficiamento industrial do caulim envolve a remoção de óxidos e hidróxidos de ferro e outras impurezas, que conferem coloração indesejável ao produto final e depreciam seu valor comercial, particularmente se destinado à indústria de papel. A lixiviação química, na linha de processamento industrial, pode ser feita com tratamentos com hipossulfito de sódio, zinco metálico e ácidos sulfúrico e fosfórico, para redução, solubilização e remoção de compostos ferruginosos. A fim de minimizar o impacto ambiental, o efluente ácido, procedente da etapa de lixiviação, deve ser inicialmente neutralizado, usualmente por óxido de cálcio. O resíduo sólido resultante contém fósforo, zinco e cálcio, entre outros nutrientes, o que sugere seu uso como fonte de macro e micronutrientes. O principal objetivo do presente estudo foi avaliar o uso do resíduo sólido como fertilizante agrícola, em experimentos de incubação em casa de vegetação, em amostras de dois solos: um de textura média e outro argiloso. A pequena alteração do pH do solo, em função da aplicação do resíduo, não constitui fator limitante à sua aplicação na agricultura. A evolução das concentrações de cálcio trocável, e fósforo e zinco extraíveis por Mehlich-1, em função do tempo de incubação, confirmam a potencialidade de uso do resíduo industrial como fertilizante agrícola.Termos de indexação: resíduo industrial, fertilizante agrícola, beneficiamento do caulim.