No abstract

Picloram (4‐amino‐3,5,6‐trichloropicolinic acid) adsorption‐desorption isotherms were derermined on six western USA soils. Adsorption isotherms were determined as a function of temperature, soil/solution ratio, and solution ionic strength. Special attention was given to the effects of pH and organic matter content in the analysis of the result. Adsorption increased with increasing organic matter with soils varying in organic matter content from 0.94% to 4.2%. Variations in adsorption between soils were not correlated with clay content or soil pH in the pH range 5.6 to 7.4, but increased adsorption resulted with decreasing solution pH of any individual soil. Sorption was described by the Freundlich isotherm at equilibrium concentrations less than 20 µg/ml. Temperature had only a slight effect on adsorption by the three soils examined. Increasing temperature from 10 to 20 to 30C generally resulted in decreased adsorption. Increasing the soil/solution ratio from 1:5 to 1:2 increased the Freundlich k value for the five soils tested. Freundlich k values were higher for the desorption isotherms than for the adsorption isotherms for all six soils. Increased adsorption with increasing ionic strength was predictable from associated pH changes and the dissociation constant for picloram.

Dissolved organic matter (DOM) can affect the distribution of solutes between solution and sorbed phases and the availability and environmental fate of the solutes. Batch sorption isotherm techniques were used to evaluate solute-solute and solute-sorbent interactions that control the effects of DOM on the sorption of a nonionic, moderately polar organic solute by solid sorbents. The sorption of napropamide (2-(a-naphthoxy-7V,A'-diethyl propionamide) by NaS Cu 2 *-, and Al^-montmorillonite decreased when dissolved humic acid derived from peat (peat-DHA) was present in the slurry. For Na-montmorillonite, the effect of DOM on sorption was reduced when a dialysis membrane prevented contact between the DOM and the clay. This suggests that competition for sorption sites on the clay between DOM and the pesticide contributed to decreased napropamide sorption. The extent of the DOM effect was also dependent on the concentration and the source of DOM added. In contrast to the montmorillonite system, the effect of DOM on napropamide sorption by soil was observed only when the dialysis membrane was present or when the dissolution of native organic matter from the sorbate surface itself was enhanced by increasing the pH of the slurry system. These results demonstrate that the effect of DOM on the sorption of nonionic pesticides by soils and sediments can be a function of the association of DOM with pesticides in the solution phase, interactive forces of both DOM and the pesticide with the sorbent surface and the nature of the sorbent surface.

No abstract

No abstract

This represents the second phase in our efforts to develop a molecular level understanding of sorption/desorption processes at soil surfaces contributing to prolonged retention of nonpolar organic chemicals. Applying techniques developed with clay minerals, the processes are followed in situ from both kinetic and mechanistic perspectives using controlled environment diffuse reflectance infrared spectroscopy in conjunction with chemicals that exhibit isomerization properties. The rapid accumulation and ease of desorption of the first sorbed species detected as vapor phase chemical flows through humic sorbents is consistent with macroscopic partitioning behavior: its conformer populations are in accord with the nonpolar nature of humic substances. A band for a second species, detected only after several hours of sorption, increases in intensity during the sorption phase of the experiment and continues to increase even after days of desorption. Both of these species appear to be in the vapor state, consistent with structural porosity as a primary factor in controlling the activity of sorbed chemical. Spectral evidence and CO 2determined microporosity support the existence of discrete regions in the macromolecular structures that are more polar, more dense, or more tightly coiled than others. These regions are accessed more slowly but retain sorbed chemical much more strongly.

No abstract

No abstract