Humic functional groups

In some systems, such as lake and river waters, the suspended inorganic particles may be coated by biological polymers, termed humic substances, which prevent flocculation by either steric or electrostatic mechanisms. These can also interact with added inorganic salts (31) that can neutralize charged functional groups on these polymers. 

Table 1 Range of Di.stribution of Oxygen-Containing Functional Groups in Humic and Fulvic Acids Isolated from Soils of Widely Different Climatic Zones (in mEq/lOO g)...

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. 

This technique is based on the same separation mechanisms as found in liquid chromatography (LC). In LC, the solubility and the functional group interaction of sample, sorbent, and solvent are optimized to effect separation. In SPE, these interactions are optimized to effect retention or elution. Polar stationary phases, such as silica gel, Florisil and alumina, retain compounds with polar functional group (e.g., phenols, humic acids, and amines). A nonpolar organic solvent (e.g. hexane, dichloromethane) is used to remove nonpolar inferences where the target analyte is a polar compound. Conversely, the same nonpolar solvent may be used to elute a nonpolar analyte, leaving polar inferences adsorbed on the column. 

Table 1. Structural carbon distribution (%) of the humic acids extracted from soil horizons, adopted from Xing (2001). The distribution was calculated from solid state 13C Cross-Polarization Magic-Angle-Spinning (CP/MAS) NMR spectra. Chemical shift assignment for carbon functional groups alkyl 0-50 ppm O-alkyl 50-117 ppm aromatic 107-165 ppm.

Much of the Hgt pool was found in the upper part of the soil, which is rich in organic matter. This pattern is likely due to an elevated atmospheric deposition of Hgt over the extended period and immobilization of mercury by organic functional groups and accumulation of organic matter as part of the soil-forming process. The retention of mercury in the mor humus layer was almost complete due to the very strong association between Hgt and humic substances. 

In spite of this variation in molecular weights and solubilities humic acid and fulvic acid have a very similar chemical composition. These acids consist of aromatic moieties such as phenols, benzenepolycarboxylic acids, hydroxybenzenepolycarbo-xylic acids, 1,2-dihydroxybenzene carboxylic acids, together with more complex condensed structures and polycylic compounds. It is conjectured that these various units are joined together by aliphatic chains (45, 54) the distribution of functional groups is presented in Table 5. 

Fig. 10. Functional groups in humic substances from 11 soil samples (mol C/kg) (data were taken from Zelazny and Carlisle [56])...

The concentrations of HS fractions, i. e., fulvic acids, humic acids, and humin expressed as mol Cl kg of SPH s in terms of various functional groups such as carboxyl, phenolic OH, alcoholic OH, and carbonyl are shown in Fig. 10. 

As with the bulk POM and DOM, the operationally defined fractions of UDOM and humic substances are quantified by elemental analysis and via broad molecular-class detection. Other strategies involve measurement of the natural isotopic composition, both stable and radioactive, of the various fractions. Efforts are underway to develop more sophisticated techniques, such as solid-state NMR and high-resolution mass spectrometry, far identification of specific bonds and functional groups. 

Functional groups constitute about 20-30% of the humic molecules About 25% of soil humic acids and about 50-60% of a fulvic acid molecule consist of functional groups... 

The basic structure of humic substances involves a backbone composed of alkyl or aromatic units crosslinked mainly by oxygen and nitrogen groups. Major functional groups attached to the backbone are carboxylic acids, phenolic hydroxyls, alcoholic hydroxyls, ketones, and quinones. The molecular structure is variable as it is dependent on the collection of DOM available in seawater to undergo the various polymerization, condensation, and oxidation reactions and reaction conditions involved in humification, as well as the ambient physicochemical reaction conditions, such as temperature and light availability. 

The capacity of complexing of humic substances is ascribed to their oxygen-based functional group (table 8.19). 

Table 8.19 Oxygen-based functional groups in 1982). Concentrations expressed in mEq/100 g. humic and fulvic acids (from Stevenson, ...

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