Carbon-13 CP/MAS NMR and DR-FTIR spectroscopic studies of sugarcane distillery waste

Abstract

The application of a sugarcane distillery waste known as vinasse to agricultural land has become a common practice in Brazil. The vinasse samples used in this study were collected from several sugarcane distilleries in Northeastern Brazil. These samples were fractionated into dissolved organic carbon (DOC) and particulate organic carbon (POC) fractions. Unfractionated and fractionated vinasse were studied using 13C cross-polarization and magic-angle spinning nuclear magnetic resonance (CP/MAS NMR) spectroscopy as well as diffuse reflectance Fourier-transform infrared (DR-FTIR) spectroscopy. Approximately 79 to 92% of the total unfractionated vinasse dry matter was in the form of DOC fraction. O-alkyl C (42–53% of the total C) and carboxyl C (12–25% of the total C) comprised a significant portion of the 13C NMR spectra of the DOC fraction. The presence of carbohydrates and COOH/COO− was suggested by the DR-FTIR as well. Both 13C NMR and DR-FTIR spectra of this fraction were generally similar to the spectra of the fulvic acid (FA) fraction of soil and sewage sludge. The spectra of DOC differed from the FA fraction in that they showed smaller amounts of aromatic C and had an absence of amide group (bands at 1650 cm−1 and 1540 cm−1). In the POC fraction, O-alkyl (17–52% of the total C) and alkyl C (15–41% of the total C) were the major contributors. The peaks at 62 ppm, 72 ppm, 84 ppm and 105 ppm in the O-alkyl region indicate the presence of cellulose and/or hemicellulose. The alkyl group was comprised mainly of long-chain structures. The total N content in this fraction is ~3–7 times as much as in the DOC fraction. The presence of amino acids in the POC fraction was suggested by both 13C NMR and DR-FTIR spectra. Key words:13C cross-polarization and magic-angle spinning nuclear magnetic resonance, dissolved organic carbon, Fourier-transform infrared, particulate organic carbon, vinasse