Chapter 1 The Biosphere Chapter 2 The Anthroposphere Introduction Air Pollution Water Pollution Soil Plants Chapter 3 Soils and Soil Processes Introduction Weathering Processes Pedogenic Processes Chapter 4 Soil Constituents Introduction Trace Elements Minerals Organic Matter Organisms in Soils Chapter 5 Trace Elements in Plants Introduction Absorption Translocation Availability Essentiality and Deficiency Toxicity and Tolerance Speciation Interaction Chapter 6 Elements of Group 1 (Previously Group Ia) Introduction Lithium Rubidium Cesium Chapter 7 Elements of Group 2 (Previously Group IIa) Beryllium Strontium Barium Radium Chapter 8 Elements of Group 3 (Previously Group IIIb) Scandium Yttrium Lanthanides Actinides Chapter 9 Elements of Group 4 (Previously Group IVb) Titanium Zirconium Hafnium Chapter 10 Elements of Group 5 (Previously Group Vb) Vanadium Niobium Tantalum Chapter 11 Elements of Group 6 (Previously Group VIb) Chromium Molybdenum Tungsten Chapter 12 Elements of Group 7 (Previously Group VIIb) Manganese Technetium Rhenium Chapter 13 Elements of Group 8 (Previously Part of Group VIII) Iron Ruthenium Osmium Chapter 14 Elements of Group 9 (Previously Part of Group VIII) Cobalt Rhodium Iridium Chapter 15 Elements of Group 10 (Previously Part of Group VIII) Nickel Palladium Platinum Chapter 16 Elements of Group 11 (Previously Group Ib) Copper Silver Gold Chapter 17 Trace Elements of Group 12 (Previously of Group IIb) Zinc Cadmium Mercury Chapter 18 Elements of Group 13 (Previously Group IIIa) Boron Aluminum Gallium Indium Thallium Chapter 19 Elements of Group I4 (Previously Group IVa) Silicon Germanium Tin Lead Chapter 20 Elements of Group 15 (Previously Group Va) Arsenic Antimony Bismuth Chapter 21 Elements of Group 16 (Previously Group VIa) Selenium Tellurium Polonium Chapter 22 Elements of Group 17 (Previously Group VIIa) Fluorine Chlorine Bromine Iodine

Trace elements in soils and plants

https://chemical.eng.usm.my/bassim/PDF/adsorption%20isotherm.pdf

Insights into the modeling of adsorption isotherm systems

Scattered literature is harnessed to critically review the possible sources, chemistry, potential biohazards and best available remedial strategies for a number of heavy metals (lead, chromium, arsenic, zinc, cadmium, copper, mercury and nickel) commonly found in contaminated soils. The principles, advantages and disadvantages of immobilization, soil washing and phytoremediation techniques which are frequently listed among the best demonstrated available technologies for cleaning up heavy metal contaminated sites are presented. Remediation of heavy metal contaminated soils is necessary to reduce the associated risks, make the land resource available for agricultural production, enhance food security and scale down land tenure problems arising from changes in the land use pattern.

/pdf/heavy-metals-in-contaminated-soils-a-review-of-sources-2f0ps3ifym.pdf

Heavy Metals in Contaminated Soils: A Review of Sources, Chemistry, Risks and Best Available Strategies for Remediation

Publisher Summary This chapter discusses the chemistry of submerged soils. The chemical changes in the submerged materials influence: (a) the character of the sediment or soil that forms, (b) the suitability of wet soils for crops, (c) the distribution of plant species around lakes and streams and in estuaries, deltas, and marine flood plains, (d) the quality and quantity of aquatic life, and (e) the capacity of lakes and seas to serve as sinks for terrestrial wastes. The single electrochemical property that serves to distinguish a submerged soil from a well-drained soil is its redox potential. The redox potential of a soil or sediment provides a quick, useful, semiquantitative measure of its oxidation–reduction status. Two recent developments have stimulated interest in the chemistry of submerged soils: the breeding of lowland rice varieties, with a high yield potential, and the pollution of streams, lakes, and seas, by domestic, agricultural, and industrial wastes. The chemistry of submerged soils is valuable: (a) in understanding the soil problems, limiting the performance of high-yielding rice varieties, and (b) in assessing the role of lake, estuarine, and ocean sediments as reservoirs of nutrients for aquatic plants and as sinks for terrestrial wastes.

The Chemistry of Submerged Soils

Toxic metal pollution of waters and soils is a major environmental problem, and most conventional remediation approaches do not provide acceptable solutions. The use of specially selected and engineered metal-accumulating plants for environmental clean-up is an emerging technology called phytoremediation. Three subsets of this technology are applicable to toxic metal remediation: (1) Phytoextraction--the use of metal-accumulating plants to remove toxic metals from soil; (2) Rhizofiltration--the use of plant roots to remove toxic metals from polluted waters; and (3) Phytostabilization--the use of plants to eliminate the bioavailability of toxic metals in soils. Biological mechanisms of toxic metal uptake, translocation and resistance as well as strategies for improving phytoremediation are also discussed.

Phytoremediation: A Novel Strategy for the Removal of Toxic Metals from the Environment Using Plants

Lead, copper, nickel, and zinc adsorption by and desorption from pH-adjusted soils has been studied. Surface and subsurface horizon samples of two soils were equilibrated with varying amounts of Ca(OH)/sub 2/ prior to metal addition. The amount of all four metals retained was dependent upon pH of the soil sample, with retention dramatically increasing above pH 7.0 to 7.5. With the exception of Ni, at least 70 to 75% of the retained metal was extractable in 0.01N HCl. Nickel was somewhat less extractable, with that sorbed by the highest pH soils being the least extractable. Based on subsequent extractibility, the soils used appeared to have specific adsorption sites for Pb, Ni, and Cu but little or none for Zn. These studies cast some doubt on the concept of pH management for immobilizing heavy metals placed on the land in that sorbed metals were substantially extractable by 0.01M HCl, which has been used to estimate plant availability of soil ions.

Effect of Soil pH on Adsorption of Lead, Copper, Zinc, and Nickel

Alfisols, Entisols, Inceptisols, Ultisols, Vertisols, and Oxisols are all commonly found in tropical and subtropical regions receiving more than 500 mm mean annual rainfall. Landscapes throughout the tropics and subtropics are, however, dominated by Oxisols and Ultisols occupying extensive areas of potentially highly productive soils. The mineral fractions of these soils consist primarily of low-activity clays having variable surface charge that differs from high activity clays in the origin of that charge. Low activity clays are dominated by iron (Fe) and aluminium (Al) oxyhydroxides and 1:1 layer silicates (kaolin). Much research has been conducted on the effects of pH, organic matter (OM), and cation composition of the soil solution on the surface charge characteristics of variable charge soils from the tropics. In general, net negative surface charge increases with increasing soil pH and OM content. Adsorption of metal ions by variable charge soils and minerals also increases as their pH, clay, and OM contents increase. Although the precise mechanisms for the change in net negative charge of soil and mineral surfaces with increasing pH are not fully understood, the generation of negative charge either through dissociation of H + ions from surfaces or consumption of OH - ions by soils is generally accepted. In soils dominated by permanent charge surfaces, heavy metals are not mobile but in variable charge soils, the low surface charge density creates conditions conducive to increased mobility. Consequently, the adsorption of heavy metals, in particular, cadmium (Cd) by strongly weathered soils in relation to the effects of inorganic and organic ligands and the implications for metal transport are reviewed.

Cadmium Sorption and Transport in Variable Charge Soils: A Review

When studying metal sorption by soils, the potential influence of environmental and solution parameters on the experimental systems cannot be ignored. Characteristics of the soil mineral surfaces are the final determinative factors in whether a metal ion will be sorbed, but soil-solution composition affects both mineral surface properties and whether the metal ions will be in forms that can react with the surfaces. Examples of factors affecting sorption of metals by soil surfaces include ionic strength, cations, anions, and/or organic ligands present in solution, solution pH, and solution metal concentration. In addition, sorption will be affected by external factors such as pressure, temperature, soil/solution ratio, and the manner in which soils to be studied are sampled and stored before investigation. To date, there has been little attempt to standardize experimental protocol, so results obtained using varied systems in different laboratories cannot be readily compared. An initial suggestion that all sorption studies include at least one treatment meeting minimal standards of ionic strength (0.01), background electrolyte (NaNO 3 ), pH (between 5.5 and 6.0), and temperature (25 ± 3°C) is presented as a first step toward enabling improved ability to make interlaboratory comparisons.

An assessment of environmental and solution parameter impact on trace-metal sorption by soils

Publisher Summary This chapter focuses on the nature of interaction among trace metals in soil solution, dissolved organics in soil solution, and solid surfaces. The interaction between metal cations and dissolved polyfunctional organic compounds of low molecular weight is important because of its role in mineral-weathering and soil-forming processes and its potential role in heavy metal contamination of soil and groundwater. The chapter presents the organics and metals in the soil solution. Dissolved organics that interact with soil constituents and trace metal ions are of two major kinds: a range of low-molecular-weight organic acids—including polyphenols, simple aliphatic acids, amino acids, sugar acids, and hydroxamate siderophores; and a series of soluble humic/fulvic acids. Numerous environmental issues arise in relation to the interaction of metal ions with soluble organics. Some of these include the phytoavailability of metals, plant nutrient availability, toxicological effects of coordinated metal ions on aquatic and marine organisms, and transport of contaminants, particularly in relation to implications for surface and groundwater quality and soil genesis. All of these issues are highly dependent on the nature and concentration of the contaminant in the soil solution phase. Extant research indicates that low-molecular-weight ligands in soil solution may either enhance or retard reactions with solid surfaces—depending on the functional groups on the organic molecule, soil surface properties, and soil solution conditions. It is imperative that increased research efforts be devoted to evaluating the effects of these organics on metal reactions in the soil.

Role of Metal-Organic complexation in metal sorption by Soils

Soil solutions contain a variety of low molecular weight dissolved organics from breakdown of plant residues and exudation from plant roots, and complexation of metals by these organic ligands can play an important role in controlling metal solubility. The effect of the organic ligands acetate, citrate, fumate, malonate, maleate, salycylate, succinate, and tartrate on the extractability and sorption of Cd was investigated in a range of Cd-treated soils varying widely in soil chemical characteristics. Experimental parameters were adjusted to investigate the effect of pH and organic ligand concentration on Cd extractability. The soils were also extracted with NaNO 3 of equivalent pH and concentration. The organic ligands always extracted more Cd than did NaNO 3 , indicating that organic complexation increased the extractability of Cd from soil, Extractable Cd ranged from fumarate = succinate > tartrate > malonate > oxalate > salicyclate when the pH of the extract was between 3.1 and 3.4; in this pH range competition for complexation between the metal ion and ligand anion is greater than the affinity of the metal ion for the soil surface. For all soils and organics, extractable Cd decreased with increasing pH of the ligand solutions. The amount of NaNO 3 -extractable Cd also decreased with increasing pH, and the amount desorbed was not detectable at pH values exceeding 5.5, suggesting that at high pH values, Cd is released into soil solution only as metal-organic complexes.

Robert D. Harter

Papers

Effect of Soil pH on Adsorption of Lead, Copper, Zinc, and Nickel

Cadmium Sorption and Transport in Variable Charge Soils: A Review

An assessment of environmental and solution parameter impact on trace-metal sorption by soils

Role of Metal-Organic complexation in metal sorption by Soils

Effect of Different Organic Ligands on Cadmium Sorption by and Extractability from Soils