Humic acids, adsorption

Starek, J., Zukal, A. and Rathousky, J., Comparison of the adsorption of humic acids from aqueous solutions on active carbon and activated charcoal cloths. Carbon, 1994, 32(2), 207 211. 

Phosphorus (P) is one of the major limiting factors for plant growth in many soils. Plant availability of inorganic phosphorus (Pi) can be limited by formation of sparingly soluble Ca phosphates, particularly in alkaline and calcareous soils by adsorption to Fe- and Al-oxide surfaces in acid soils and by formation of Fe/ Al-P complexes with humic acids (94). Phosphorus deficiency can significantly alter the composition of root exudates in a way that is, at least in some plant species, related to an increased ability for mobilization of sparingly soluble P sources (29,31,71). 

Removal to sediments. Removal of surface-reactive trace elements from the oceans readily occurs by adsorption onto settling particles, and this process is most pronounced in the typically high-energy, particle-rich estuarine environment. Particles are supplied by rivers, augmented by additions of organic material generated within the estuary. Also, floes are created in estuaries from such components as humic acids and Fe. The interaction between dissolved and colloidal species is enhanced by the continuous resuspension of sediments in... 

Restricted access phases are another approach to exploiting the differences in characteristics of analytes. Large analytes are excluded from an internal surface on which an adsorptive stationary phase is present. A herbicide analysis for Metsulfuron methyl, Bentazone, Bromoxynil, methylchlorophenoxy acid, and Mecoprop in the presence of humic acid was performed on restricted access reversed phase media.52 The cytostatic compound epirubicin and its metabolites were separated from plasma using a Pinkerton GFF II column.53 Gradient separations of polymers on reversed phase and on normal phase represent an alternative to gel permeation chromatography. Polyesters of noncrystalline materials were separated on a variety of such phases.54... 

Bierkens J, Vangenechten JHD, Van Puymbroeck S, et al. 1986. Effect of Al and humic acids on the 241Am adsorption on the exoskeleton of the crayfish Astacus leptodactylus eschscholtz. Health Phys 50(2) 277-280. 

Wang, L.K., Wang, M.H.S., and Hoagland, F.M., Reduction of color, odor, humic acid and toxic substances by adsorption, flotation and filtration, Water Treatment, 1, 1-16, 1992. 

Figures 1 and 2 show the effect of temperature on the extent of binding of DDT to both Pakim Pond Humic Acid and Boonton Humic Acid. The Y axis in these figures is the amount of DDT bound to the humic acid in nanograms of DDT per gram of humic acid. The X axis is the free, truly dissolved DDT in nanograms per liter. This is similar to the presentation of an adsorption isotherm. If the slope of the lines is multiplied by 1000 it becomes analogous to a weight-weight partition coefficient ([g DDT/g D0C]/[g DDT/g water]). This will be referred to as the binding constant.

Szabo, G., Prosser, S., Bulman, R. A. (1990) Determination of the adsorption coefficient (KoC) of some aromatics for soil by RP-HPLC on two immobilized humic acid phases. Chemosphere 21, 777-788. 

Yoshimura et al. [193] carried out microdeterminations of phosphate by gel-phase colorimetry with molybdenum blue. In this method phosphate reacted with molybdate in acidic conditions to produce 12-phosphomolybdate. The blue species of phosphomolybdate were reduced by ascorbic acid in the presence of antimonyl ions and adsorbed on to Sephadex G-25 gel beads. Attenuation at 836 and 416 nm (adsorption maximum and minimum wavelengths) was measured, and the difference was used to determine trace levels of phosphate. The effect of nitrate, sulfate, silicic acid, arsenate, aluminium, titanium, iron, manganese, copper, and humic acid on the determination were examined. 

Humic acids Adsorption on macroretic-ular resin XAD-2 — — [448-450]... 

Avena, M. J. and Koopal, L. K. (1999). Kinetics of humic acid adsorption at solid-water interfaces, Environ. Sci. Technol., 33, 2739-2744. 

A method [62] has been described for the determination of down to 2.5pg kg-1 alkylmercury compounds and inorganic mercury in river sediments. This method uses steam distillation to separate methylmercury in the distillate and inorganic mercury in the residue. The methylmercury is then determined by flameless atomic absorption spectrophotometry and the inorganic mercury by the same technique after wet digestion with nitric acid and potassium permanganate [63]. The well known adsorptive properties of clays for alkylmercury compounds does not cause a problem in the above method. The presence of humic acid in the sediment did not depress the recovery of alkylmercury compounds by more than 20%. In the presence of metallic sulphides in the sediment sample the recovery of alkylmercury compounds decreased when more than lmg of sulphur was present in the distillate. The addition of 4M hydrochloric acid, instead of 2M hydrochloric acid before distillation completely, eliminated this effect giving a recovery of 90-100%. 

Adsorption isotherm of (Aldrich) humic acid (HM) on 8-AI203 as a function of pH. Extent of adsorption was determined both by measurements of light absorption at 254 and 436 nm, respectively and by measurements of dissolved organic carbon (DOC) of the residual HM in solution (original concentration = 25 mg per liter). 

It is necessary to remind ourselves, that the adsorption of humic acids or fulvic acids correspond to the adsorption of a mixture of adsorbates. Adsorption equations derived for the adsorption of a single adsorbate (Langmuir, Frumkin or Gibbs Equation) cannot be used for mechanistic interpretation of the data even if these data can be fitted to such equations (Tomaic and Zutic, 1988). 

Kinetically, the adsorption of humic acids at a solid-water interface is controlled by convection or diffusion to the surface. Even at concentrations as low as 0.1 mg/e near-adsorption equilibrium is attained within 30 minutes. At high surface densities, a relatively slow rearrangement of the adsorbed molecules may cause a slow attainment of an ultimate equilibrium (Ochs, Cosovic and Stumm, in preparation). The humic acids adsorbed to the particles modify the chemical properties of their surfaces, especially their affinities for metal ions (Grauer, 1989). 

Adsorption isotherms are often plotted for mixtures of adsorbates (humic acid, fatty acids etc.) using collective parameters such as organic carbon. Enumerate the various reasons that make the rational interpretation of such adsorption isotherms difficult. 

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. 

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