Speciation active

Models are often developed to explain certain kinds of data, ignoring other kinds that also might be pertinent. The initial development of Pitzer s equations (33.34) for activity coefficients in concentrated solutions was focused on explaining measurements of vapor pressure equilibrium and of electromotive force (emf). The data could be explained by assuming that the electrolytes examined were, at least in a formal sense, fully dissociated. Later work using these equations to explain solubility data required the formal adoption of a few ion pair species (30). Even so, no speciation/activity coefficient model based on Pitzer s equations is presently consistent with the picture of much more extensive ion-pairing based on other sources, such as Smith and Martell s (35) compilation of association constants. This compilation is a collective attempt to explain other kinds of data, such as electrical conductance, spectrophotometry, and acoustic absorption. 

The relationship between the concentration of a metal in the surrounding water and the concentration in an organism is defined as concentration factor (Baudo 1981). Concentration factors in excess of a thousandfold can be attained (Martincic etal. 1984), and are affected by speciation, active and passive uptake, modalities of uptake, and transformation, transport and distribution between and within tissues, and elimination. 

J. W. Novak, Jr., R. R. Burr, andR. Bednarik, "Mechanisms of Metal Ion Adsorption of Activated Alumina," Vol. 35, Proc. Int. Symp. on Metals Speciation, Separation, and Recorey, Chicago, lU., July 27—Aug. 1, 1986, Industrial Waste Elimination Research Center of the Illinois Institute of Technology, Chicago, lU. 

Sodium-silicate glass, 151 Sol-gel films, 120, 173 Solid electrodes, 110 Solid state devices, 160 Solvents, 102 Speciation, 84 Spectroelectrochenristry, 40 Spherical electrode, 6, 8, 9, 61 Square-wave voltammetry, 72, 92 Staircase voltammetry, 74 Standard potential, 3 Standard rate constant, 12, 18 Stripping analysis, 75, 79, 110 Supporting electrolyte, 102 Surface-active agents, 79... 

The most widely studied interactions between biologically active ligands and organotin(lV) cations relate to the amino acids and their derivatives (N- or S-protected amino acids and peptides), though new data on several of the most commonly occurring amino acids are still being published. This is specially true for aqueous speciation studies. Nice and very detailed reviews were published in this area by Molloy and Nath. ... 

From the beginnings of ecology as a discipline, the mining industry has been at the center of the battle over preservation versus exploitation. As discussed in the introduction to this chapter, human activities such as mining, power production from fossil fuels and discharges of industrial and municipal wastes not only increase the rate at which metals enter the biosphere but may also drastically alter the speciation of metals from what it would be in the undisturbed geologic cycle. 

Mercury provides an excellent example of the importance of metal speciation in understanding biogeochemical cycling and the impact of human activities on these cycles. Mercury exists in solid, aqueous, and gaseous phases, and is transported among reservoirs in all these forms. It undergoes precipitation-dissolution, volatilization, complexation, sorption, and biological reactions, all of which alter its mobility and its effect on exposed populations. The effect of all... 

It must be noted that sometimes calcination is beneficial to create active species. Notable examples are the Sn-beta speciation [176] and generation of extra-framework Al-Lewis sites in beta zeolite for organic transformations... 

Today it has become clear that the effect of trace elements in living systems, in food, and in the environment depends on the chemical form in which the element enters the system and the final form in which it is present. The form, or species, clearly governs its biochemical and geochemical behaviour. lUPAC (the International Union for Pure and Applied Chemistry) has recently set guidelines for terms related to chemical speciation of trace elements (Templeton et al. 2000). Speciation, or the analytical activity of measuring the chemical species, is a relatively new scientific field. The procedures usually consist of two consecutive steps (i) the separation of the species, and (2) their measurement An evident handicap in speciation analysis is that the concentration of the individual species is far lower than the total elemental concentration so that an enrichment step is indispensable in many cases. Such a proliferation of steps in analytical procedure not only increases the danger of losses due to incomplete recovery, chemical instability of the species and adsorption to laboratory ware, but may also enhance the risk of contamination from reagents and equipment. 

Nevertheless, cereal plants can interact with endosymbionts, capable of nitrogen fixation in other species, and be stimulated in their productivity. The odds of soil life are balanced for some bacteria by their interactivity at rhizosphere level, and a realm of exchanged signals dictates entry into hormonally reprogrammed root sites. Specificity for partner plant species is part of a fine speciation process that actively involves the bacterial nodulation genes, and continues to drive their variation dynamics. 

Field and laboratory bioassay of chemosignals from related sympatric and allopatric species (overlapping and discrete distributions) are essential to an understanding of the relatedness or otherwise of functionally active compounds. The semiochemicals involved in speciation surely utilise the main and vomeronasal senses, but their relative contributions cannot be predicted at present. 

Escher, B. I. Snozzi, M. Schwarzenbach, R. P, Uptake, speciation, and uncoupling activity of substituted phenols in energy transducing membranes, Environ. Sci. Technol. 30, 3071-3079 (1996). 

In arid and semi-arid soils with a pH range of 6-9, free calcium is the major Ca speciation form in soil solution. When pH > 9.2-9.5, CaP04 becomes a major calcium species in soil solution of neutral and calcareous soils, especially when the activity of H2P04 is > 10 5 M (Lindsay, 1979), such as after phosphate fertilizers are used. Lindsay (1979) further pointed out that CaS04° contributes significantly to the total calcium in solution when S042- is > 10 M. 

Organic complexed Cd is not important in arid soil solution. Hirsh and Banin (1990) observed 5-10% of Cd bound to organic ligands in Israeli arid soil solution. Emmerich et al. (1982) found that organic-Cd complexes constituted 1-4% of Cd in California arid soil solution. However, Villarroel et al. (1993) reported that in a California sludge-treated soil, Cd was mainly present in both free ion and organic complex forms (each accounted for 32-40% and 30-45% of total Cd in soil solution, respectively), followed by the chloride complexes (8-20%), S04-complex (3-10%), and P04-Cd complex (1.5-7.7%). The nitrate Cd complexes were the lowest. Cadmium activities and speciation is not significantly affected by P and N treatments. 

Trace element speciation in soil solution is affected by total metal concentrations in soils. Free Cu2+ activity increases with total Cu content in soils from Quebec and New York (Sauve et al., 1997). Total free Cu activity in soils could be predicted from total Cu content and soil pH ... 

Candelaria L.M., Chang A.C. Cadmium activities, solution speciation, and solid phase distribution of Cd in cadmium nitrate and sewage sludge-treated soil systems. Soil Sci 1997 162 (10) 722-732. 

Dumestre, A., Sauve, S., McBride, M., Baveye, P. and Berthelin, J. (1999). Copper speciation and microbial activity in long-term contaminated soils , Archives of Environmental Contamination and Toxicology, 36, 124-131. 

A catalytic activity must be present that is linked to the replication process, so that variations in replication affect the catalysed reactions. Under such circumstances, variations will change the fitness of the system and lead to evolution. Compartmentalisation of the replicating catalytic system within a membrane-bound volume allows selection of variations, leading to speciation ... 

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