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

Soil Chemical Analysis

Na+ Tolerance and Na+ Transport in Higher Plants

Metal contamination issues are becoming increasingly common in India and elsewhere, with many documented cases of metal toxicity in mining industries, foundries, smelters, coal-burning power plants and agriculture. Heavy metals, such as cadmium, copper, lead, chromium and mercury are major environmental pollutants, particularly in areas with high anthropogenic pressure. Heavy metal accumulation in soils is of concern in agricultural production due to the adverse effects on food safety and marketability, crop growth due to phytotoxicity, and environmental health of soil organisms. The influence of plants and their metabolic activities affects the geological and biological redistribution of heavy metals through pollution of the air, water and soil. This article details the range of heavy metals, their occurrence and toxicity for plants. Metal toxicity has high impact and relevance to plants and consequently it affects the ecosystem, where the plants form an integral component. Plants growing in metal-polluted sites exhibit altered metabolism, growth reduction, lower biomass production and metal accumulation. Various physiological and biochemical processes in plants are affected by metals. The contemporary investigations into toxicity and tolerance in metal-stressed plants are prompted by the growing metal pollution in the environment. A few metals, including copper, manganese, cobalt, zinc and chromium are, however, essential to plant metabolism in trace amounts. It is only when metals are present in bioavailable forms and at excessive levels, they have the potential to become toxic to plants. This review focuses mainly on zinc, cadmium, copper, mercury, chromium, lead, arsenic, cobalt, nickel, manganese and iron.

Heavy metals, occurrence and toxicity for plants: a review

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.

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

Aluminum toxicity is discussed, including general effects (symptoms and physiological effects), differential aluminum tolerance in plants, beneficial effects of aluminum, and the genetic control of aluminum tolerance. Manganese and iron toxicity are discussed in the same framework. The toxicity of other metals (Zn, Cu, Ni, Cd, and Pb) is also discussed, though not as extensively as aluminum, manganese, and iron. 476 references.

The Physiology of Metal Toxicity in Plants

Phytoremediation of soil metals

The contrasting Fe2+ and Fe3+ chelating properties of the synthetic chelators ethylenediaminedi (o-hydroxyphenylacetate) (EDDHA) and 4,7-di(4-phenylsulfonate)-1, 10-phenanthroline (bathophenanthrolinedisulfonate) (BPDS) were used to determine the valence form of Fe absorbed by soybean roots supplied with Fe3+-chelates. EDDHA binds Fe3+ strongly, but Fe2+ weakly; BPDS binds Fe2+ strongly but Fe3+ weakly. Addition of an excess of BPDS to nutrient solutions containing Fe3+-chelates inhibited soybean Fe uptake-translocation by 99+%; [Fe(II) (BPDS)3]4− accumulated in the nutrient solution. The addition of EDDHA caused little or no inhibition. These results were observed with topped and intact soybeans. Thus, separation and absorption of Fe from Fe3+-chelates appear to require reduction of Fe3+-chelate to Fe2+-chelate at the root, with Fe2+ being the principal form of Fe absorbed by soybean.

Obligatory reduction of ferric chelates in iron uptake by soybeans.

Trace element solubility and availability in land-applied residuals is governed by fundamental chemical reactions between metal constituents, soil, and residual components. Iron, aluminum, and manganese oxides; organic matter; and phosphates, carbonates, and sulfides are important sinks for trace elements in soil-residual systems. The pH of the soil-residual system is often the most important chemical property governing trace element sorption, precipitation, solubility, and availability. Trace element phytoavailability in residual-treated soils is often estimated using soil extraction methods. However, spectroscopic studies show that sequential extraction methods may not be accurate in perturbed soil-residual systems. Plant bioassay is the best method to measure the effect of residuals on phytoavailability. Key concepts used to describe phytoavailability are (i) the salt effect, (ii) the plateau effect, and (iii) the soil-plant barrier. Metal availability in soil from metal-salt addition is greater than availability in soil from addition of metal-containing residuals. Plant metal content displays plateaus at high residual loadings corresponding to the residual's metal concentration and sorption capacity. The soil-plant barrier limits transmission of many trace elements through the food chain, although Cd (an important human health concern) can bypass the soil-plant barrier. Results from many studies that support these key concepts provide a basis of our understanding of the relationship between trace element chemistry and phytoavailability in residual-treated soils. Research is needed to (i) determine mechanisms for trace element retention of soil-residual systems, (ii) determine the effect of residuals on ecological receptors and the ability of residuals to reduce ecotoxicity in metal-contaminated soil, and (iii) predict the long-term bioavailability of trace elements in soil-residual systems.

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Trace element chemistry in residual-treated soil: key concepts and metal bioavailability.

Three thousand forty-five surface soil samples from 307 different soil series were analyzed for Pb, Cd, Zn, Cu, Ni, cation exchange capacity (CEC), organic C, and pH in the course of a study of trace element uptake by major agricultural crops. The soil data from this study are summarized here statistically and in map form to show their interactions and generalized geographic distribution patterns. Amounts of all five metal elements are generally low in the Southeast. A regional high of about 15 mg/kg Pb covers the Mississipi, Ohio, and Missouri River valleys. Higher values for other elements are generally concentrated in the West and in the lower Mississippi River Valley. Maximum Cd levels were found in soils of the coast ranges of central and southern California. Copper levels are noticeably higher in organic soil areas of Florida, Oregon, and the Great Lakes. Nickel and Cu concentrations are high in serpentine soil areas of California. Nickel levels are also somewhat higher in the glaciated areas of the northern great plains and in northern Maine. For the entire dataset, the values of the minimum-maximum, 5th, 50th, and 95th percentiles are as follows: (mg/kg dry soil) Cd, <0.005 to 2.0, 0.036, 0.20, 0.78; Pb, 0.5 to 135, 4.0, 11, 23; Zn, 1.5 to 264, 8.0, 53, 126; Cu, 0.3 to 495, 3.8, 18.5, 95; Ni, 0.7 to 269, 4.1, 18.2, 57; pH (pH units) 3.9–8.9, 4.7, 6.1, 8.1; CEC (cmol/kg) 0.6 to 204, 2.4, 14.0, 135; and organic C % 0.09 to 63, 0.36, 1.05, 33.3. Metal levels generally increased with increasing clay concentration. Contribution from the National Soil Survey Lab. Midwest Technical Center, Soil Conservation Service, Lincoln, NE.

Rufus L. Chaney

Papers

The Physiology of Metal Toxicity in Plants

Phytoremediation of soil metals

Obligatory reduction of ferric chelates in iron uptake by soybeans.

Trace element chemistry in residual-treated soil: key concepts and metal bioavailability.

Cadmium, Lead, Zinc, Copper, and Nickel in Agricultural Soils of the United States of America