Spectroscopic characterization of humic acid fractions isolated from soil using different extraction procedures

Abstract To extract humic substances from soils, the sequential resin–alkali extraction technique has recently been introduced, providing for milder conditions as compared to the classical isolation procedure. In this study the results of spectroscopic investigations of resin- and alkali-extracted humic acids (HAs) are reported. Five HA fractions were isolated from bog soil (USA) with carboxylate resin (RCOONa) and 0.1 M NaOH by three protocols. They comprised the classical acid–alkali isolation procedure with benzene/methanol pre-treatment of soil (one alkali-extracted fraction), and the sequential resin–alkali extraction both with benzene/methanol pre-treatment of soil and without it (two resin- and two alkali-extracted fractions); then the HA fractions were de-ashed by HCl/HF and freeze-dried. The HA samples were analyzed for elemental composition (C, H, N and O) by Fourier-transformed infrared (FTIR), ultraviolet–visible, and fluorescence spectroscopy in emission and synchronous-scan excitation modes. All the HAs obtained had low ash contents and similar elemental composition. The FTIR evidence suggests that alkali-extracted HAs contain more aliphatics, carbohydrates, aromatics and/or amides as compared to resin-extracted material, which is relatively rich in carboxylic and phenolic groups. Resin-extracted HAs have higher A 254 / A 436 and E 4 / E 6 ratios than the alkali-extracted samples. They also exhibit higher fluorescence emission maximum. The sequential resin–alkali extraction procedure appears to provide isolation of soil HA fractions which vary in nonhumic compounds inclusion and in some photophysical characteristics.

[1]  L. McGown,et al.  Multi-method characterisation of natural organic matter isolated from water: characterisation of reverse osmosis-isolates from water of two semi-identical dystrophic lakes basins in Norway , 1998 .

[2]  G. Sposito,et al.  Flourescence Spectroscopy of Humic Substances , 1988 .

[3]  C. Calmon,et al.  Book reviewHumic substances in soil, sediment and water: by G.R. Aiken, D.M. McKnight, R.L. Wersham and P. McCarthy (Eds.), John Wiley and Sons, New York, 1985, xiii + 692 pages, $59.95 , 1986 .

[4]  M. Ewald,et al.  UV-visible absorption and fluorescence properties of fulvic acids of microbial origin as functions of their molecular weights , 1988 .

[5]  Yona Chen,et al.  Information Provided on Humic Substances by E4/E6 Ratios1 , 1977 .

[6]  M. Hayes,et al.  PROCEDURES FOR THE ISOLATION AND FRACTIONATION OF HUMIC SUBSTANCES , 2000 .

[7]  G. Webster,et al.  Indigenous 13C-NMR structural features of soil humic substances , 1981, Nature.

[8]  M. Ewald,et al.  Characterization by fluorescence of the dissolved organic matter in natural water. application to fractions obtained by tangential ultrafiltration and XAD resin isolation , 1993 .

[9]  M. Schnitzer,et al.  THE EXTRACTION OF SOIL ORGANIC MATTER BY BASE AND CHELATING RESIN , 1967 .

[10]  Hans-Gerd Loehmannsroeben,et al.  Absorption and fluorescence spectroscopic investigations of PAC/humic substance-interactions in water , 1997, Other Conferences.

[11]  Robert L. Tate,et al.  Humic Substances in Soil and Crop Sciences: Selected Readings , 1991 .

[12]  M. Kononova Soil Organic Matter , 1963 .

[13]  Gennaro Brunetti,et al.  Decrease in humification of organic matter with intensified lowland rice cropping: a wet chemical and spectroscopic investigation. , 2000 .

[14]  A. P. Edwards,et al.  Dispersion of Mineral Colloids in Soils using Cation Exchange Resins , 1965, Nature.

[15]  J. A. Rice,et al.  Spectroscopic methods (other than NMR) for determining functionality in humic substances , 1985 .

[16]  D. Sparks Environmental Soil Chemistry , 1995 .

[17]  D. Cheney,et al.  Isolation of humic acid from the brown algaPilayella littoralis , 1994, Journal of Applied Phycology.

[18]  M. Hayes Humic substances II : in search of structure , 1989 .

[19]  G. Abbt-Braun,et al.  Basic characterization of Norwegian NOM samples — Similarities and differences , 1999 .

[20]  Warren A. Dick,et al.  Humic Substances in the Global Environment and Implications on Human Health , 1995 .

[21]  T. Khomutova,et al.  The response of humic substances to soil acidification and freezing , 1994 .

[22]  M. Kononova,et al.  Formation of humic acids during plant residue humification and their nature , 1973 .

[23]  E. A. Ghabbour,et al.  Humic substances : versatile components of plants, soil and water , 2000 .

[24]  T. Miano,et al.  Spectroscopic and compositional comparative characterization of I.H.S.S. reference and standard fulvic and humic acids of various origin , 1989 .

[25]  M. Schnitzer,et al.  EXTRACTION OF HUMIC ACID BY ALKALI AND CHELATING RESIN , 1972 .

[26]  R. Malcolm Variations between humic substances isolated from soils, stream waters, and groundwaters as revealed by 13C-NMR spectroscopy. , 1990 .

[27]  T. Miano,et al.  CHARACTERIZATION, DIFFERENTIATION, AND CLASSIFICATION OF HUMIC SUBSTANCES BY FLUORESCENCE SPECTROSCOPY , 1991 .

[28]  W. Buermann,et al.  Tight metal binding by humic acids and its role in biomineralization , 1997 .