Mobilization of metals

Intramolecular mobility of metal complexes of rotaxanes and catenanes with macroheterocyclic fragments 98ACR611. 

Natural mobilization includes chemical, mechanical, and biological weathering and volcanic activity. In chemical weathering, the elements are altered to forms that are more easily transported. For example, when basic rocks are neutralized by acidic fluids (such as rainwater acidified by absorption of CO2), the minerals contained in the rocks can dissolve, releasing metals to aqueous solution. Several examples are listed below of chemical reactions that involve atmospheric gases and that lead to the mobilization of metals ... 

Volcanic activity has a significant effect on the mobilization of metals, particularly the more volatile ones, e.g., Pb, Cd, As, and FFg. Effects of volcanism are qualitatively different from those of the weathering and other near-surface mobilization processes mentioned above, in that volcanism transports materials from much deeper in the crust and may inject elements into the atmospheric reservoir. 

Saitoh, K., Kiyohara, C., and Suzuki, N., Mobilities of metal [i-diketonato complexes in micellar electrokinetic chromatography, ]. High Resolut. Chromatogr., 14, 245, 1991. 

Oxidation-reduction reactions may affect the mobility of metal ions by changing the oxidation state. The environmental factors of pH and Eh (oxidation-reduction potential) strongly affect all the processes discussed above. For example, the type and number of molecular and ionic species of metals change with a change in pH (see Figures 20.5-20.7). A number of metals and nonmetals (As, Be, Cr, Cu, Fe, Ni, Se, V, Zn) are more mobile under anaerobic conditions than aerobic conditions, all other factors being equal.104 Additionally, the high salinity of deep-well injection zones increases the complexity of the equilibrium chemistry of heavy metals.106... 

Kurek E (2002) Microbial mobilization of metals from soil minerals under aerobic conditions. In Huang PM, Bollag J-M, Senesi N (eds) Interactions between soil particles and microorganisms. Impact on the terrestrial ecosystem, vol 8, IUPAC series on analytical and physical chemistry of environmental systems. Wiley, Chichester, UK, pp 189-225... 

Humus can form stable complexes such as chelates with polyvalent cations. SOM is capable of strong polydentate binding to transition metals in a chelate [17,19,45, 65-67]. The complexation of metal ions by SOM is extremely important in affecting the retention and mobility of metal contaminants in solid phases and waters [45]. Several different types of SOM/humus-metal reactions can occur (Fig. 11), and include reactions between DOC-metal ions, complexation reactions between SOM-metal ions, and bottom sediments-metal ions. The functional groups of SOM (Fig. 10) have different affinities for metal ions as shown below ... 

An important consequence of acidification is mobilization of metals from terrestrial watersheds [14]. Particularly important is the release of aluminium because of its toxic effects on freshwater biota especially on fish [15]. Not all A1 forms are toxic. Only cationic species contained within the operational forms termed labile A1 (LAI) or inorganic monomeric A1 (Ali) are gUl-reactive and hence affect fish health [16]. It has been shown that concentrations of soluble aluminium increase with decreasing pH from a pH of ca. 6.3 [17]. 

The mobility of metal atoms in bare metal clusters and small metallic nanoparticles (NPs) is of fundamental importance to cluster science and nanochemistry. Atomic mobility also has significant implications in the reactivity of catalysts in heterogeneous transformation [6]. Surface restmcturing in bimetallic NP and cluster catalysts is particularly relevant because changes in the local environment of a metal atom can alter its chemical activity [7, 8]. 

The mobility of metals in soil solutions is controlled by several processes (1) desorption or dissolution (rate depends on the solubility of metal-mineral form) (2) diffusion (depends on speciation of metal, soil oxidation/reduction potential, and pH) (3) sorption or precipitation (depends on soil solution concentration and rhi-zosphere effects) and (4) translocation in the plants (depends on plant species, soil solution concentration, and competing ions) (McBride... 

The Clean Air Act of 1990 has made trace metal content in fuels and wastes the final ash-related compositional characteristic of significance. Considerable attention is paid (ca 1993) to emissions of such metals as arsenic, cadmium, chromium, lead, mercury, silver, and zinc. The concentration of these metals in both grate ash and flyash is of significance as a result of federal and state requirements of particular importance is the mobility of metals. This mobility, and the consequent toxicity of the ash product, is determined by the Toxic Characteristic Leaching Procedure (tclp) test. Tables 8—10 present trace metal contents for wood wastes and agricultural wastes, municipal waste, and refuse-derived fuel, respectively. In Table 8, the specific concentration of various components in the RDF governs the expected average concentration of trace metals. 

The flux of DOC from terrestrial landscapes to surface runoff has wide-ranging consequences for aquatic chemistry and biology. DOC affects the complexation, solubility, and mobility of metals (Perdue et al., 1976 Driscoll et al., 1988 Martell et al., 1988 see Chapter 8) as well as the adsorption of pesticides to soils (Senesi, 1992 Worrall et al., 1997). Formation of trihalomethanes when drinking water is disinfected with chlorine, a worldwide threat to water supplies, is also linked to DOC concentrations (Siddiqui et al., 1997). DOC attenuates ultraviolet-B (UV-B) radiation and thus provides some protection to aquatic biota from exposure to harmful UV radiation (e.g., Williamson and Zagarese, 1994). Finally, DOC affects the heat balance and thus stratification in lakes, which is an important constraint for aquatic organisms with limited habitats (Schindler et al., 1996, 1997). 

Inorganic speciation in solution can also affect the mobility of metal ions (Doner, 1978). The formation of an ion-pair with Cl can more than double the mobility of Cd in the presence of 200molm 3NaCl. At the same chloride concentration, however, the mobilities of Cu2+ and Ni2+ are only increased slightly (5-10%), presumably because of very weak complexation with Cl. This mechanism could increase the leaching of Cd from saline soils but it may not be effective in non-saline soils because the ratio of the total concentrations of Cd Cl must be >1 106 before >50% of total Cd is complexed by Cl (estimated using the computer model TITRATOR (Cabaniss, 1987), which considered the chloro and hydroxy complexes of Cd at pH 5.0 and a total Cd concentration of 0.1 mmolm-3 equilibrium constants were taken from Lindsay (1979)). 

By binding with metallothionein, the mobility of metals by diffusion is greatly reduced and the metals are prevented from binding to enzymes or other proteins essential to normal metabolic function. 

Redox reactions control the mobility of metal ions in solution by changing the valence state, which in turn changes the solubility of metals causing them to dissolve into or precipitate out of solution a common example is the reduction/ oxidation of iron ... 

Species such as, Cl, or F that increase the mobility of metal atoms may cause either redispersion or increased sintering rates. The role of Cl in redispersion has been discussed elsewhere [16]. There is evidence that S and F poisons increase rates of sintering. For example, Erekson and Bartholomew [57] found that an unsupported Ni powder with particles having diameters of 2-6 pm was relatively stable during reduction in H2 at 725-775 K over a period of 18 h. However, after exposure for just 6 h to 0.2 ppm H2S/H2 at either 725 or 775 K, (but not below 725 K) most of the small particles had agglomerated to large (100-250 pm)... 

Forstner, U. and Salomons, W. 1991. Mobilization of metals from sediments. In E. Merian, Ed. Metals and Their Compounds in the Environment Occurrence, Analysis, and Biological Relevance. VCH Publishers, New York, pp. 379-398. 

Partitioning and mobility of metal ions, metal complexes, and ligands in soils or sediments are affected by their adsorption onto a variety of substrates. As mentioned earlier (see Section 6.3.1), natural oxides offer suitable adsorption sites for some of these species and may even undergo dissolution as a result. Here, an understanding of the bonding phenomena is crucial. For example, the adsorption of [Co(III)EDTA] (here written as [ML]-) on hydrated aluminum oxide surfaces (written as =A10H) can be represented as ... 

Organic acid complexes with metal ions significantly affect the mobility of metal ions in plants and soils. Toxic... 

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