Fulvic amino acids

NOM is common in sediments, soils, and near ambient (<50 °C) water. The materials result from the partial decomposition of organisms. They contain a wide variety of organic compounds, including carboxylic acids, carbohydrates, phenols, amino acids, and humic substances (Drever, 1997, 107-119 Wang and Mulligan, 2006, 202). Humic substances are especially important in interacting with arsenic. They result from the partial microbial decomposition of aquatic and terrestrial plants. The major components of humic substances are humin, humic acids, and fulvic acids. By definition, humin is insoluble in water. While fulvic acids are water-soluble under all pH conditions, humic acids are only soluble in water at pH >2 (Drever, 1997, 113-114). 

The importance of the interaction of organic compounds with calcium carbonate surfaces has long been recognized. It has been demonstrated that aragonite precipitation is inhibited by uncharacterized dissolved organic matter (Chave and Suess, 1967), and that humic and fulvic acids, and certain aromatic carboxylic acids, inhibit seeded aragonite precipitation from seawater (Berner et al., 1978). The selective adsorption of amino acids on carbonate substrates has received considerable attention. A preferential adsorption of aspartic acid has been shown from humic and fulvic acids and proteinaceous matter (Carter and Mitterer, 1978 Carter, 1978 Mitterer, 1971). 

Figure 10.5 Amino acid photoproduction from Suwannee River fulvic acid (30 mg L ). Chromatograms are of OPA derivatized samples before (A) and after (B) 31 h irradiation in a solar simulator. Labeled peaks increased in size after irradiation are labeled with names of amino acids having the same retention time (Tarr et al., 2001).

Humic and flilvic acids are traditionally extracted from soils and sediment samples as the sodium salts by using sodium hydroxide solution. The material that remains contains the insoluble humin fraction (Figure 3). The alkaline supernatant is acidified to pH 2 with HCl. The humic acid precipitates and the fulvic acid remains in solution with other small molecules such as simple sugars and amino acids. These molecules can be separated by passing the solution through a hydrophobic resin, such as the methacrylate cross-linked polymer, XAD-8. The fulvic acids will sorb to the resin while the more hydrophilic molecules pass through the column. The fulvic acid can be removed with dilute base. 

Despite the current popularity of the polyphenol theory, a completely satisfactory scheme for the occurrence of humic and fulvic acids in diverse geologic environments has yet to be established. In practice, all pathways may be operative, but not to the same extent in all environments or in the same order of importance. A lignin pathway may-predominate in wet sediments, such as peats and swamps. The drastic conditions existing in soils under a harsh continental climate (e.g., some Mollisols) may favor humus synthesis by sugar-amine condensation. The disappearance of amino acids from buried sediments has been attributed to the formation of brown nitrogenous polyelectrolytes by reaction with reducing sugars (Stevenson, 1974). 

The MRTs of individual humus fractions also vary, as can be seen from Table 8. The MRT of the original soil (Melfort silt loam) was 870 years whereas the MRTs of individual fractions ranged from 25 to 1410 years. For both humic and fulvic acids, the acid hydrolyzable fractions (6A HCl for 18 hours) had lower MRTs than the nonhydrolyzable fractions. This result is in accord with expectations, because the hydrolyzable material would include the carbon of readily decomposable substrates (e.g., carbohydrates and amino acids). Stability of the major humus fractions followed the order humin = humic acid > fulvic acid (Campbell et al., 1967a). 

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