Speciation organic complexation

Equilibrium complexation constants for Cu reactions with natural organic matter and the details of Cu speciation are bound to remain somewhat uncertain, since the composition of the complexing molecules varies from site to site. What is not in dispute is that the fraction of dissolved copper present as free aquo Cu is probably very small in any natural water. In extremely pristine waters, hydroxide and carbonate complexes may dominate, but organic complexes usually dominate in waters containing more than a few tenths of a mg/L organic carbon. 

Ra. Exceptions to this are environments where Rn is lost from the system by degassing (e.g., see Condomines et al. 2003), or aqueous systems where the insoluble nature of °Pb leads to its preferential removal. The speciation of Pb in natural waters is rather complex and heavily depends on the availability of organic complexing agents for which Pb has the highest affinity. In the oceans, Pb has a very short residence (30-150 yrs) and is rapidly scavenged by particles. 

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. 

Soil solution to soil ratios also strongly affect distribution of some trace elements such as Zn speciation in arid and semi-arid soils. Fotovat et al. (1997) reported that the proportion of free hydrated Zn2+ to total Zn ranged from 20-65% at field capacity soil water content and decreased with increases in solution to soil ratios, while the proportion of Zn complexed with organic ligands increased dramatically in soils. However, solution to soil ratios do not strongly affect the distribution of Cu speciation in soil solution since Cu primarily occurs as organic complexes in these soil solutions. 

Little is known of the oceanic distribution or speciation of cobalt, because very low concentrations (< 200 pM) make its determination difficult. Laboratory studies indicate that cobalt exists in seawater primarily as the cobalt (II) ion and as the carbonate complex. Organic complexes are not considered important. 

Sunda and Hanson [247] have used ligand competition techniques for the analysis of free copper (II) in seawater. This work demonstrated that only 0.02 -2% of dissolved copper (II) is accounted for by inorganic species. (i.e., Cu2+, CuC03, Cu(OH)+, CuCl+, etc.) the remainder is associated with organic complexes. Clearly, the speciation of copper (II) in seawater is markedly different from that in fresh water. 

In natural waters, dissolved zinc speciates into the toxic aquo ion [Zn(H20)6]2+, other dissolved chemical species, and various inorganic and organic complexes zinc complexes are readily transported. Aquo ions and other toxic species are most harmful to aquatic life under conditions of low pH, low alkalinity, low dissolved oxygen, and elevated temperatures. Most of the zinc introduced into aquatic environments is eventually partitioned into the sediments. Zinc bioavailability from sediments is enhanced under conditions of high dissolved oxygen, low salinity, low pH, and high levels of inorganic oxides and humic substances. 

Xue, H.-B. and Sigg, L. (1998). Cd speciation and complexation by natural organic ligands in freshwater, Anal. Chim. Acta, 363, 249-259. 

For the understanding of the binding of heavy metals on clays one needs to consider - in addition to ion exchange - the surface complex formation on end-standing functional OH-groups. Furthermore, the speciation of the sorbate ion (free hydroxo complex, carbonato- or organic complex) and its pH-dependence has to be known. 

At the pH and ionic strength of seawater, the dominant dissolved species of silicon is orthosilicic acid [H4Si04(aq) or Si(OH)4(aq)]. The speciation of silicic acid is shown in Figure 5.19. At the pH of seawater, a minor amount of dissociation occurs, such that about 5% of the dissolved silicon is in the form of HjSiO faq). Dissolved organic complexes of silicon do not occur naturally. 

The solubility of Hg(II) is controlled by chemical speciation in natural waters, and the availability of ligands for complexation shifts dramatically under varying redox conditions (40). Speciation of dissolved Hg(II) in anoxic environments, such as sediments or the hypolimnion, should be strongly influenced by reactions with reduced sulfur (40, 41), whereas organic complexation is potentially important under oxic conditions (42, 43). 

Lee, J. and Jonasson, I.R. (1983) Contribution of organic complexation to Ni, Co and Cu speciation in surface waters implications for hydrogeochemical surveys. J. Geochem. Explor, 18, 25-48. 

Speciation in solution is considered a major factor in the mobilisation and leaching of metal cations (DeKoninck, 1980 Bloomfield, 1981 Stevenson and Fitch, 1986). Complexation increases the total soluble concentration of a metal and hence increases its potential to be leached. Organic ligands (e.g. humate, ful-vate, citrate, polyphenols) are the major complexers involved in this mechanism, but they are effective only if the soluble organic complex does not become saturated and precipitate (DeKoninck, 1980). 

The seawater chemistries of Mn, Fe, Co, Ni, Cu and Zn are, in many respects, quite diverse. One characteristic that these elements have in common, however, is an accessible +11 oxidation state. Except in the case of iron, which exists dominantly as Fem in seawater, the solution speciation of these elements is dominated by the +11 oxidation state. The aspect of these elements seawater speciation which most distinguishes them from other cations in the Periodic Table is their substantial involvement in organic complexation. 

It is clear from previous comments that radionuclide speciation studies must consider not only oxidation states and specific inorganic forms but also complex species arising through association with natural organic matter and the possibility of different physical states. The relative importance of these various physicochemical forms will, in practice, be dictated by a combination of the basic elemental characteristics of the radionuclide and the type of environment into which it is placed. Thus in seawater, colloidal organic complex species are likely to be far less dominant than for the same radionuclide in a very low ionic strength freshwater. In the case of soil and sediment interstitial waters or groundwaters,... 

Electrochemical methods have been used for determinations of species of elements in natural waters. Of the many electrochemical techniques, only a few have proved to be useful for studies of speciation in complex samples, and to possess the sensitivity required for environmental applications. The greatest concern is the measurement of the toxic fraction of a metal in an aqueous sample. The definition of a toxic fraction of a metal is that fraction of the total dissolved metal concentration that is recognised as toxic by an aquatic organism. Toxicity is measured by means of bioassays. Elowever, a universally applicable bioassay procedure cannot be adopted because the responses of different aquatic species to metal species vary. Nevertheless, bioassays should be used as means of evaluation and validation of speciation methods. A condition is that the test species (of the bioassay) should be very sensitive to the metals being studied so as to simulate a worst case situation (Florence, 1992). 

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