The effect of 10% HF treatment on the resolution of CPMAS 13C NMR spectra and on the quality of organic matter in Ferralsols

Abstract

The investigation of the chemical composition of soil organic matter (SOM) in Ferralsols by means of solid-state cross-polarization magic angle spinning (CPMAS) 13C nuclear magnetic resonance (NMR) spectroscopy is limited by their high iron oxide concentration and their low organic carbon content. In order to circumvent those limitations, such samples are often treated with hydrofluoric acid (HF) to remove paramagnetic material and to concentrate the amount of SOM. The main objectives of this study were to elucidate the impact of this approach on the resolution of the CPMAS 13C NMR spectra and on the chemical composition of the SOM in the A and B horizons of four Brazilian Ferralsols. Therefore, those soils were subjected to up to eight successive treatments with 10% (w/w) HF. Each of those extractions resulted in an enhancement of the C content of the samples. A relationship between mass loss caused by the treatment and texture and mineralogy was observed. However, high losses of carbon occurred during the HF treatments, particularly in the B horizons, but no consistent alterations in the distribution of carbon functional groups were determined by CPMAS 13C NMR, suggesting that preferential loss of specific carbon groups was not induced. The concentration of total and dithionite extractable Fe increased after two treatments for most of the samples. This may be best explained by the preferential dissolution of silicate leading to a selective enrichment of iron containing minerals. After four treatments, the Fe concentration declined considerably. After the second treatment, the spectral resolution improved. Considering the obtained results, it can be confirmed that the efficiency of the HF treatment is rather controlled by the number than by the duration of the extraction. We suggest that, for A horizons of Ferralsols, four repetitions of HF treatment are sufficient to yield well-defined spectra. For their B horizons, on the other hand, the CPMAS 13C NMR spectra obtained after four HF extractions were of poor quality, indicating that for these soils at least eight HF treatments have to be performed to acquire reasonable spectra.