Many new organic agricultural chemicals have been developed which offer great potential in the production and preservation of food and fiber (Weber 1969). In the process of developing and utilizing these chemicals we must come to understand how they affect the target organisms and what becomes of them after they have done their job. The purpose of this review is to discuss1 the behavior of one family of these organic compounds, the s-triazines, at the molecular level, in systems in which the chemicals are associated with clay minerals. Factors affecting the adsorption and release of s-triazines by clay colloids and the availability of the compounds to plant roots will also be included. The literature citations are limited to those studies in which s-triazines and clays were directly associated and situations in which other compounds behaved in a manner similar to the s-triazines.

Mechanisms of adsorption of s-triazines by clay colloids and factors affecting plant availability.

Current knowledge of clay mineralogy and changing concepts of clay behavior have suggested a re-examination of the experimental data concerning adsorbed water. Data published between 1935 and 1959 have been studied and evaluated. In some instances this requires a reinterpretation of data that may lead to inferences or conclusions not intended by the original author. The intention of the re-evalution of data is to clarify understanding of the nature of adsorbed water and to suggest fruitful avenues for future research. While all literature on the subject has not been included, a concerted effort has been made to include representative data from all viewpoints and experimental methods. Data reviewed come under the following headings: X-ray and electron diffraction, density, dielectric and magnetic, thermodynamic, diffusion and fluid flow, freezing, and rigid water films. Utilizing present knowledge of crystal and surface chemistry of clay leads to the following conclusions: (a) Positions of the oxygen atoms of the adsorbed water molecules have been established by X-ray diffraction of vermiculite. These positions preclude both the ice structure and the Hendricks-Jefferson net structure even after modification to accommodate the exchangeable ions, (b) Density of water sorbed on Na montmorillonite has a minimum value of about 0.97 g/cm3 at a water content of 0.7 g H2O/g clay (approximately the plastic limit). For water contents less than 0.7 the density rapidly rises to about 1.4, and for water contents greater than 0.7 the density gradually rises until at about 6.5 g H2O/g clay the density of the adsorbed water equals that of normal liquid water. (c) The differential entropy of water adsorbed on kaolinite has a minimum value approximately that of ice; however, (1) this minimum occurs at about 0.7 of a monolayer, and (2) the integral entropy is greater than that for normal liquid water up to at least two molecular layers. The apparently contradictory entropy of sorbed water on montmorillonitic clay has not been resolved but is believed to be at least partially associated with clay swelling. (d) Diffusion and fluid flow phenomena are shown to be extremely sensitive to clay fabric; therefore, it is the writer's opinion that diffusion and fluid flow data on loosely compacted clay are of little help in ascertaining the structure of the adsorbed water phase. (e) Adsorbed water is easily supercooled and an appreciable fraction of the adsorbed water remains unfrozen after ice has once formed. The two major hypotheses indicate that the nature of the adsorbed water is: (1) a solidlike substance, or (2) a two-dimensional fluid. In the writer's opinion the only data that cannot be adequately explained by both of the hypotheses are the integral entropy data on kaolinite. The integral entropy data favor the two-dimensional fluid hypothesis; however, the paucity of data requires that this be a very tentative conclusion. The major difficulty encountered in the re-examination of data for this review was that a, rather poorly defined clay surface was employed by various investigators. If progress is to be made in unraveling the water-clay complex, it is deemed absolutely essential that experiments be carried out on very carefully defined and controlled clay surfaces. The nature of adsorbed water as interpreted from physico-chemical data on water-clay systems is no better than the purity of the clay surface regardless of the accuracy and precision of the measurements.

Adsorbed water on clay: a review

Summary

Changes in the strength of remoulded agricultural top soil with ageing are studied for two sandy loam soils from South Australia and a clay soil from Queensland. There is evidence of significant thixotropic behaviour in these soils around the water contents at which tillage is usually performed.



For the Urrbrae soil, in which the dominant clay minerals are illite and kaolinite. the maximum thixotropic strength ratio was obtained at a water content just below the plastic limit. For the Strathalbyn soil, which contains illite and actinolite. and for the Waco soil which contains montmorillonite. the maximum thixotropic strength ratios occurred at water contents between the plastic and liquid limits.



The age hardening for these soils was investigated using probe penetration, tensile strength and compression resistance measurements. The effect was still apparent after sterilization and after removal of organic matter.

Age hardening of agricultural top soils

Sensitive life detection strategies for low-biomass environments: optimizing extraction of nucleic acids adsorbing to terrestrial and Mars analogue minerals.

This review discusses the recent trends in the research over the last 30 years to use clay minerals in natural and modified forms for removing different toxic organic/inorganic pollutants. The natural and modified forms of clay minerals have an exceptional ability to remove different contaminants. However, the modification methods can improve the clay mineral adsorption properties that consequently increase more adsorption sites and functional groups to adsorb different environmental pollutants. This review shows the importance of modification methods and more extension of novel clay preparation based on nanotechnology which could raise the control of pollution. The syntheses of functionalized clays such as pillared clays and porous clay heterostructures introduce the new class of heterostructure materials with high adsorption capacity, capability, and selectivity. Due to the acceptable properties of heterostructure materials including high specific surface area, thermal and mechanical stability, and the existence of multifunctional groups to selective adsorption, this review collects more literature of research related to environmental protection issues. However, it is expected much attention to get a better understanding of the adsorption mechanism, regeneration, and recovery process of these materials.

The advantages of clay mineral modification methods for enhancing adsorption efficiency in wastewater treatment: a review.

H-montmorillonite, -beidellite, and -nontronite were found to change spontaneously into Al-clays. Rates of conversion of H- to Al-clay were slow at 0°C, but at temperatures of around 100°C, moist H-montmorillonite changed to Al-saturated montmorillonite within 24 hours. It appeared that Al-ions moved from lattice positions to exchange positions, with octahedral Al moving more rapidly than tetrahedral Al.

A. C. Mathers

Papers

The Effect of Acid and Heat Treatment on Montmorillonoids