Oxidation state seawater

Anodic-stripping voltaimnetry (ASV) is used for the analysis of cations in solution, particularly to detemiine trace heavy metals. It involves pre-concentrating the metals at the electrode surface by reducmg the dissolved metal species in the sample to the zero oxidation state, where they tend to fomi amalgams with Hg. Subsequently, the potential is swept anodically resulting in the dissolution of tire metal species back into solution at their respective fomial potential values. The detemiination step often utilizes a square-wave scan (SWASV), since it increases the rapidity of tlie analysis, avoiding interference from oxygen in solution, and improves the sensitivity. This teclmique has been shown to enable the simultaneous detemiination of four to six trace metals at concentrations down to fractional parts per billion and has found widespread use in seawater analysis. 

In oxygenated seawater, uranium is thermodynamically predicted to be present in a hexavalent (-b 6) oxidation state, but it can also exist as the tetravalent U(IV) if conditions are sufficiently reducing. Reduced uranium in the +A oxidation state is highly insoluble or particle reactive. In contrast, U(VI) is readily soluble due to the rapid formation of stable inorganic carbonate complexes. According... 

Sulfur exists naturally in several oxidation states, and its participation in oxidation/reduc-tion reactions has important geochemical consequences. For example, when an extremely insoluble material, FeS2, is precipitated from seawater under conditions of bacterial reduction, Fe and S may be sequestered in sediments for periods of hundreds of millions of years. Sulfur can be liberated biologically or volcanically with the release of H2S or SO2 as gases. 

E. L. Shock (1990) provides a different interpretation of these results he criticizes that the redox state of the reaction mixture was not checked in the Miller/Bada experiments. Shock also states that simple thermodynamic calculations show that the Miller/Bada theory does not stand up. To use terms like instability and decomposition is not correct when chemical compounds (here amino acids) are present in aqueous solution under extreme conditions and are aiming at a metastable equilibrium. Shock considers that oxidized and metastable carbon and nitrogen compounds are of greater importance in hydrothermal systems than are reduced compounds. In the interior of the Earth, CO2 and N2 are in stable redox equilibrium with substances such as amino acids and carboxylic acids, while reduced compounds such as CH4 and NH3 are not. The explanation lies in the oxidation state of the lithosphere. Shock considers the two mineral systems FMQ and PPM discussed above as particularly important for the system seawater/basalt rock. The FMQ system acts as a buffer in the oceanic crust. At depths of around 1.3 km, the PPM system probably becomes active, i.e., N2 and CO2 are the dominant species in stable equilibrium conditions at temperatures above 548 K. When the temperature of hydrothermal solutions falls (below about 548 K), they probably pass through a stability field in which CH4 and NII3 predominate. If kinetic factors block the achievement of equilibrium, metastable compounds such as alkanes, carboxylic acids, alkyl benzenes and amino acids are formed between 423 and 293 K. 

The latter two assumptions are simplistic, considering the number of factors that affect pH and oxidation state in the oceans (e.g., Sillen, 1967 Holland, 1978 McDuff and Morel, 1980). Consumption and production of CO2 and O2 by plant and animal life, reactions among silicate minerals, dissolution and precipitation of carbonate minerals, solute fluxes from rivers, and reaction between convecting seawater and oceanic crust all affect these variables. Nonetheless, it will be interesting to compare the results of this simple calculation to observation. 

Tunicates (ascidians or sea-squirts) are invertebrate marine organisms, which can accumulate vanadium at concentrations approaching 350 mM (the concentration of vanadium in seawater is 10 8 M). This vanadium is taken up as V(V) from seawater (Figure 17.16), reduced to oxidation state III or IV and stored in a soluble form in the blood cells within acidic vacuoles at concentrations a million fold higher than in their external surroundings. 

If ammonium concentrations in seawater are low, phytoplankton will assimilate nitrate and nitrite using chemical-specific permeases. Once inside the cell, these DIN species are transformed into ammonium via redox reactions in which nitrogen is reduced to the -III oxidation state ... 

Sulfur is present in several oxidation states, usually as sulfide and sulfate. Locally native sulfur may occur in significant quantities. Sulfate is present in large concentrations in seawater and is probably the most important oxidizer in the water of anoxic basins such as the Black Sea, Kaoe Bay, and many fjords. 

In the case of chromium it is uncertain, whether the oxidation state (III) or (VI) is predominant in seawater. This is mainly due to the observed very slow oxidation rate of Cr(III) (Elderfield, 1970 Nakayama et al.1981 Gould, 1982 van der Weyden and Reith, 1982). Interesting is the possibility of the existence of Cu(I) in marine surface waters. Reduction of Cu(II) would be initiated by photochemically produced H202- The back oxidation is so slow that Cu(I) species have a sufficiently long lifetime to form complexes,... 

Despite the insights provided by measurements of the concentrations of DOC, DON, and DOP and their molar ratios in bulk seawater, these data alone are insufficient to calculate the mass percentage of carbon in marine DOM, the average oxidation state of carbon in marine DOM, or the degree of unsaturation of marine DOM. All such calculations require that the concentrations of organically bound H and O also be measured. Such measurements cannot be made directly on aqueous samples. 

Although americium (Am) exists in seawater exclusively in the trivalent oxidation state, its profiles in Fig. 12.4 contrast sharply with those of the trivalent lanthanides. Assessments of Nd isotopic ratios in seawater (e.g. Bertram and Elderfield, 1993) indicate that more than 1000 years are required for attainment of steady-state distributions of lanthanides and chemically similar elements in seawater. On such a basis it is expected that, in spite of substantial chemical similarities to the lanthanides, 241Am, a relatively short-lived isotope (half-life 470 years) with variable and recent anthropogenic inputs, will not exhibit profiles similar to those of the lanthanides. 

Thorium (Th), which exists solely in the +IV oxidation state is, like Uff, highly particle reactive. Dissolved Th in seawater should exist principally as Th(OH)4 and Th(OH)3. 

All three Group 5 elements are expected to have +V oxidation states in seawater and are very strongly hydrolysed. The aqueous speciation of Vv in seawater... 

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