Humic substances solubility

Fulvic acids. Marine sedimentary humic substances soluble in base and acid (fulvic acids) have previously been examined by and NMR (12). The dominant structural components were postulated to be polysaccharide - like substances, probably polyuronic acids. Solid-state NMR spectra of fulvic acids isolated from a number of marine and estuarine sediments are shown in Figure 1. Major peaks at 72 and 106 ppm betray the overwhelming presence of polysaccharide -like substances, and, as shown by Hatcher and others (12.), the moderate peak for carboxyl or amide carbon at 175 ppm suggests that these polysaccharides are more like polyuronides. Aromatic carbons (110 to 160 ppm) are decidedly minor components. Aliphatic carbons (0-50 ppm) are also minor components. H NMR spectra shown by Hatcher and others (12) indicate that these aliphatic structures are highly branched. 

Humic substances, which are biopolymers widely and abundantly present in natural waters and soils, also have a high complexing ability with various heavy metal ions. These compounds are formed by the random condensation of breakdown products of terrestrial and aquatic plants and extracellular metabolites of phytoplankton. Concentrations of metals in marine and fresh waters are often higher than predicted from the solubility products of corresponding hydroxide and carbonate compounds. The complexation of metal ions with dissolved humic substances is responsible for the apparent supersaturation of metals in natural waters [9-21], Water-soluble humic substances are usually divided into two fractions, humic acid (HA) and Mvic acid (FA). HA is defined in operational terms as the fraction of humic substance soluble in alkaline solutions and insoluble in acidic solutions, while FA is the fraction soluble in both alkaline and acidic solutions. A general method for the fractionation of humic substances is illustrated in Fig. 1. HA is easily obtained as a precipitate in acidic solution (pH < 1.5). Although HA appears to be an attractive adsorbent for the recovery of heavy metal ions, there is little information on its practical application as adsorbent. It is difficult to use humic acid as the adsorbent because of its high solubility in water. 

Humic substances in sediments and soils have commonly been, defined as heteropolycondensates of decomposing plant and animal detritus 46. For lack of a better structural definition, these macromolecular substances have been divided into three categories fulvic acids and humic acid and humin. Fulvic acids and humic acids are soluble in dilute alkaline solutions, whereas humin is insoluble. 

Biogeochemical compartment. The biogeochemical compartment consists of the O, A, E, and B horizons of soils, in which substantial organic matter can be an integral component of the soil. The load of the water leaving the soil from the biogeochemical compartment consists mainly of soluble compounds because the matrix of the soil acts as a filter that retains particulate matter. In some cases, however, clay and particulate humic substances are also car-... 

Bone protein was extracted following the method described by Sealy (1986). Bone chips were demineralized in a weak HCl solution, then soaked in 0.1 M NaOH to remove base-soluble humic substances. Remaining material, which is mainly collagen, but includes non-collagenous proteins, was... 

Humic substances can form complexes with metals, including cationic micronutrients (36), thanks to the presence of electron-donor functional groups in these molecules. It therefore appears evident that due to these properties, humic substances can contribute to the regulation of the chemical balances of metals, thus influencing their solubility (5). With regard to plant availability, the molecular dimension and solubility of humic substances are very important. 

A. A. Mohamed, F. Agnolon, S. Ce.sco, Z. Varanini, and R. Pinton, Incidence of lime-induced chlorosis plant re.sponse mechanism and role of water soluble humic substances. Agrochimica 42 255 (1998). 

Extractable concentrations of sediment-bound zinc were positively correlated with zinc concentrations in deposit feeding clams (Luoma and Bryan 1979). Availability of sediment zinc to bivalve molluscs was higher at increased sediment concentrations of amorphous inorganic oxides or humic substances, and lower at increased concentrations of organic carbon and ammonium acetate-soluble manganese. Zinc uptake by euryhaline organisms was enhanced at low water salinity (Luoma and Bryan 1979). 

Florence, T. M., Powell, H. K. J., Stauber, J. L. and Town, R. M. (1992). Toxicity of lipid-soluble copper(II) complexes to the marine diatom Nitzschia Closterium -amelioration by humic substances, Water Res., 26, 1187-1193. 

Partitioning of PCBs into other organic compound mixtures or phases found in the environment alters environmental parameters used to estimate their fate and transport. For example, dissolved phase humic substances (i.e., DPUS) can increase the apparent solubility of organic pollutants [381-390] (see Chap. 2). 

Recall from Chapter 23.2.4 that humic substances are isolated from seawater by adsorption on a hydrophobic resin followed by elution using solvents of varying pH. The desorbed compounds are fractionated into two classes, humic acids fulvic acids based on their solubility behavior. A model structure for a humic acid is illustrated in Figure 23.10a in which fragments of biomolecules, such as sugars, oligosaccharides. 

Fulvic acids Humic substances that are soluble at all pHs. 

Humic substances A series of relatively high-molecular-weight, yellow- to black-colored substances formed by secondary synthesis reactions. The term is used as a generic name to describe the colored material or its fractions obtained on the basis of solubility characteristics. These materials are distinctive to the soil (or sediment) environment in that they are dissimilar to the biopolymers of microorganisms and higher plants (including lignin)... 

Organic matter extracted from earth materials usually is fractionated on the basis of solubility characteristics. The fractions commonly obtained include humic acid (soluble in alkaline solution, insoluble in acidic solution), fulvic acid (soluble in aqueous media at any pH), hymatomelamic acid (alcohol-soluble part of humic acid), and humin (insoluble in alkaline solutions). This operational fractionation is based in part on the classical definition by Aiken et al. (1985). It should be noticed, however, that this fractionation of soil organic matter does not lead to a pure compound each named fraction consists of a very complicated, heterogeneous mixture of organic substances. Hayes and Malcom (2001) emphasize that biomolecules, which are not part of humic substances, also may precipitate at a pH of 1 or 2 with the humic acids. Furthermore, the more polar compounds may precipitate with fulvic acids. 

The enhancement of kerosene dissolution occurs even at low humic acid content in the aqueous solution. In view of the fact that humic substances are relatively high molecular weight species containing nonpolar organic moieties, Chiou et al. (1986) assumed that a partition-like interaction between a solute of very low solubility in aqueous solution and a microscopic organic environment of dissolved humic molecules can explain solute solubility enhancement. 

Phenolic compounds have also been oxidatively polymerized to humic substances by clay minerals (29) and by the mineral fraction of a latasol (66). After a 10-day equilibration period, montmoril-lonite and illite clay minerals yielded 44 to 47% of the total added phenolic acids as humic substances whereas quartz gave only 9%. Samples of a latasol yielded over 63% of the total amount, from mixtures in varied proportion, of mono-, di- and trihydroxy phenolic compounds as humic substances (66). Extractions of the reaction products yielded humic, fulvic, and humin fractions that resembled soil natural fractions in color, in acid-base solubility, and in infrared absorption spectra. Wang and co-workers (67) further showed that the catalytic polymerization of catechol to humic substances was, enhanced by the presence of A1 oxide and increased with pH in the 5.0 to 7.0 range. Thus the normally very reactive products of Itgnin degradation can be linked into very stable humic acid polymers which will maintain a pool of potentially reactive phytotoxins in the soil. 

Preparation of Fulvic and Humic Acids. Waxes, resins, and other substances soluble in organic solvents were removed by successive extractions with petroleum ether (35-60°), chloroform, and ethyl acetate. These extractions removed of the original material. 

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