There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

The article focuses on adsorption of heavy metal ions on soils and soils constituents such as clay minerals, metal (hydr)oxides, and soil organic matter. Empirical and mechanistic model approaches for heavy metal adsorption and parameter determination in such models have been reviewed. Sorption mechanisms in soils, the influence of surface functional groups and surface complexation as well as parameters influencing adsorption are discussed. The individual adsorption behavior of Cd, Cr, Pb, Cu, Mn, Zn and Co on soils and soil constituents is reviewed.

Adsorption of heavy metal ions on soils and soils constituents

Preface.- Contributors.- List of Abbreviations.- Section 1: Basic Principles: Introduction.-Sources of Heavy Metals and Metalloids in Soils.- Chemistry of Heavy Metals and Metalloids in Soils.- Methods for the Determination of Heavy Metals and Metalloids in Soils.- Effects of Heavy Metals and Metalloids on Soil Organisms.- Soil-Plant Relationships of Heavy Metals and Metalloids.- Heavy Metals and Metalloids as Micronutrients for Plants and Animals.-Critical Loads of Heavy Metals for Soils.- Section 2: Key Heavy Metals And Metalloids: Arsenic.- Cadmium.- Chromium and Nickel.- Cobalt and Manganese.- Copper.-Lead.- Mercury.- Selenium.- Zinc.- Section 3: Other Heavy Metals And Metalloids Of Potential Environmental Significance: Antimony.- Barium.- Gold.- Molybdenum.- Silver.- Thallium.- Tin.- Tungsten.- Uranium.- Vanadium.- Glossary of Specialized Terms.- Index.

Heavy metals in soils : trace metals and metalloids in soils and their bioavailability

http://files.aprendiendoquimica7.webnode.com.co/200000006-1247d13423/Limousin,%20G%20et%20al.%20Sorption%20Isotherms%20A%20review%20on%20Physical%20Bases,%20modeling%20and%20measurement.pdf

Sorption isotherms: A review on physical bases, modeling and measurement

China faces great challenges in protecting its soil from contamination caused by rapid industrialization and urbanization over the last three decades. Recent nationwide surveys show that 16% of the soil samples, 19% for the agricultural soils, are contaminated based on China’s soil environmental quality limits, mainly with heavy metals and metalloids. Comparisons with other regions of the world show that the current status of soil contamination, based on the total contaminant concentrations, is not worse in China. However, the concentrations of some heavy metals in Chinese soils appear to be increasing at much greater rates. Exceedance of the contaminant limits in food crops is widespread in some areas, especially southern China, due to elevated inputs of contaminants, acidic nature of the soil and crop species or cultivars prone to heavy metal accumulation. Minimizing the transfer of contaminants from soil to the food chain is a top priority. A number of options are proposed, including identification of the sources of contaminants to agricultural systems, minimization of contaminant inputs, reduction of heavy metal phytoavailability in soil with liming or other immobilizing materials, selection and breeding of low accumulating crop cultivars, adoption of appropriate water and fertilizer management, bioremediation, and change of land use to grow nonfood crops. Implementation of these strategies requires not only technological advances, but also social-economic evaluation and effective enforcement of environmental protection law.

Soil Contamination in China: Current Status and Mitigation Strategies

Oxides of Fe and Mn in soils are capable of sorbing large amounts of trace metal ions and can therefore be important in controlling trace metal concentrations in soil solution, and hence trace metal bioavailability in soils. There is, however, relatively little information on the rates of desorption of trace metals from oxide materials or on the factors affecting desorption rates. The objective of this study was to examine the kinetics of desorption of Cd and Co from two Fe oxides, goethite and ferrihydrite, and from two Mn oxides, hausmannite and cryptomelane. The concentrations of Cd and Co specifically sorbed by the oxides at pH 6.0 were greater for the Mn oxides than for the Fe oxides. The metals were also much less readily desorbed from the Mn than the Fe oxides and, in general, Cd was more readily desorbed than Co from all four oxides. Increasing the initial sorption period from 1 to 15 wk substantially decreased the proportion of sorbed Cd or Co subsequently desorbed from goethite, with a similar but much smaller effect also observed with the Mn oxides. Desorption kinetics for both Cd and Co were found to be described well by assuming either the occurrence of two simultaneous first-order desorption reactions, or by a continuous distribution of reaction sites, distributed lognormally with respect to desorption first-order rate constant. With increasing initial sorption period, the parameters obtained from fitting either type of kinetic equation to the experimental data could be interpreted as indicating a movement of metal ions to sites with slower desorption reactions.

/pdf/kinetics-of-cadmium-and-cobalt-desorption-from-iron-and-zitagocrwq.pdf

Kinetics of cadmium and cobalt desorption from iron and manganese oxides

Soil solution metal concentrations and hence metal bioavailability are controlled by sorption-desorption reactions at the surfaces of soil colloids. Compared with the numerous studies on sorption of metals by soils, there are relatively few that examine desorption, and even fewer that have measured desorption kinetics. The objective of this study was, using techniques and models developed previously for studies with synthetic oxides, to examine the effect of sorption period on the subsequent desorption kinetics of Cd and Co from two natural soil clay fractions. Cobalt was less readily desorbed from the clay fractions than Cd, but with both metals and clay fractions, increases in sorption period were accompanied by substantial decreases in the proportions of sorbed metal desorbed. As with the oxides studied previously, desorption kinetics for Cd and Co sorbed onto clay fractions were found to be described well by both a two-site first-order model and a model involving a lognormal distribution of first-order rate constants. Reaction half-lives derived from the models suggested a movement of Cd and Co to slower desorption reactions with increasing sorption period. However, some caution should be used in interpreting such parameters.

/pdf/cadmium-and-cobalt-desorption-kinetics-from-soil-clays-zgnl7ijvvk.pdf

Cadmium and cobalt desorption kinetics from soil clays: effect of sorption period

[1] Defining background concentrations for heavy metals in soils is essential for recognizing and managing soil pollution. However, background concentrations of metals in soils can vary naturally by several orders of magnitude. Moreover, many soils have also been subject to unquantifiable anthropogenic inputs of metals, in some cases, for centuries. Hence determination of heavy metal background concentrations in soils has to date been fraught with difficulty. Here we demonstrate that there are associations between the background heavy metal and Fe or Mn contents in soils which appear to be consistent for seven important heavy metals of environmental concern. The relationships are remarkably independent of both soil type and climatic setting. These observations provide the basis for a series of general equations from which it is proposed Southeast Asian including Australian, and possibly worldwide background concentrations for As, Cr, Co, Cu, Ni, Pb, and Zn in soils can be derived.

/pdf/geochemical-indices-allow-estimation-of-heavy-metal-2fn44bhsgc.pdf

Geochemical indices allow estimation of heavy metal background concentrations in soils

Adsorption of Au(I, III) complexes on Fe, Mn oxides and humic acid

Phosphatic fertilizers contain appreciable concentrations of cadmium (Cd) which may elevate the Cd concentrations of soils and crops, yet the impact of Cd on poorly buffered Western Australian soils is not known. We measured soil Cd, P and Zn concentrations at different depths and with total (mixed acid) and partial extractants (CaCl2, EDTA and HCl) at sites with a known phosphate fertilizer history. Accumulation of Cd in soils where P fertilizers had been applied varied greatly, with the Cd content of fertilized soils generally having significantly higher Cd contents than for unfertilized soils. In a ferruginous sandy loam, the highest concentrations of Cd were in the top 2 cm and these concentrations increased with increasing amounts of fertilizer application. A gravelly lateritic soil in an orchard contained 3.6 mg Cd kg-1, which was 20-fold higher than the equivalent unfertilized soil. Very sandy horticultural soils which are characteristic of Western Australia did not have higher exchangeable Cd, and showed small increases in total Cd, despite the high amounts of phosphatic fertilizers applied. The largest proportional increases in soil Cd were generally for analyses using partial extractants rather than for total Cd.

Andrew W. Rate

Papers

Kinetics of cadmium and cobalt desorption from iron and manganese oxides

Cadmium and cobalt desorption kinetics from soil clays: effect of sorption period

Geochemical indices allow estimation of heavy metal background concentrations in soils

Adsorption of Au(I, III) complexes on Fe, Mn oxides and humic acid

Cadmium accumulation in agricultural soils in Western Australia