Molybdate oxyanion

Many important soil components are not present as simple cations or anions but as oxyanions that include both important metals and nonmetals. The most common and important metal oxyanion is molybdate (Mo042 ). The most common and important nonmetal oxyanions are those of carbon (e.g., bicarbonate [HC03 ] and carbonate [C032-]), nitrogen (e.g., nitrate [N03 ] and nitrite [NQ2 ]), and phosphorus (e.g., monobasic phosphate [H2P04 ], dibasic... 

The vanadate (1, 2), molybdate (1-5), and tungstate (1-3) systems have been described in previous reviews. Although the focus in this chapter is on more recent developments, earlier well-established knowledge is included where needed for perspective and also to present a coherent picture of the hydrolysis behavior of these oxyanions. Equilibria of mono- and polynuclear species are described and information about known structures are given. Some recent work about mixed polyoxoanions is briefly reviewed. 

Oxyanions also affect the coordination chemistry of the metal center (84). Molybdate and tungstate are tightly bound noncompetitive inhibitors (Ki s of ca. 4 (iM) (85). These anions bind to the reduced form of the enzyme, changing the rhombic EPR spectrum of the native enzyme to axial (Figure 1) and affecting the NMR shifts observed (84,85). Comparisons of the ENDOR spectra of reduced uterofenin and its molybdate complex show that molybdate binding causes the loss of iH features which are also lost when the reduced enzyme is placed in deuterated solvent (86). These observations suggest that molybdate displaces a bound water upon complexation. 

If this conjecture is correct, the intermediate form of MPT would be bound to the synthase protein via thioester linkages. Given the hydrolytic instability of thioesters, the synthase bound MPT derivative should serve as an ideal precursor to metal-containing MPT derivatives that could be generated either by hydrolysis of the thioester followed by complexation or by direct reaction with molybdate, tungstate, or a simple derivative of these oxyanions. 

The final products are simple molybdate or tungstate ions and either an oxyanion or a hydrous metal oxide of the central atom ... 

Fe anchored amino-functionalized MCM-41 effectively adsorbs toxic oxyanions, arsenate, chromate, selenate and molybdate, in the aqueous solution. These adsorbents show ones of the largest adsorption capacities reported in the literature. The molar ratio, oxyanion / Fe, is 2.8, 1.8, 1.5 and 2.3, respectively. They are consistent with the coordination mmibers in the EXAFS structural analysis of adsorption complexes. Cr-Fe adsorption centre is uniform, where 2 1 complex is uniformly generated. On the contraiy, chloride ion remains in As- and Se-Fe complexes and two kinds of coordination with different bonding distances were found in As- and Mo-Fe complexes. 

Molybdenum is primarily in the +6 oxidation state in soils, taking the form of the molybdate anion, MoO . Protonation of this oxyanion, described by the reaction ... 

The molybdate- and tungstate-noseans were much more stable than chromate-nosean under reducing conditions. This is consistent with the properties of the pure salts. Sodium chromate is relatively easily reduced to oxidation state III whereas molybdates and tungstates tend to form polymeric bronzes with oxidation state between V and VI. THe formation of this type of compound is not possible when the oxyanions are separated in cages. The amount of H2(g) adsorbed by molybdate-nosean at 800°C was sufficient to account for less than 14% reduction of the oxyanion to the V oxidation state. 

After synthesis of the dithiolene moiety in MPT (53), the chemical backbone is built for binding and coordination of the molybdenum atom. Molybdenum enters the cell as the soluble oxyanion molybdate for which high-affinity transporters have been described in bacteria " which also exist in higher eukaryotes such as... 

Figure 7.3 plots the ratio of crystal radius versus charge for selected ions. Oxyanions—sulfate, selenate, phosphate, arsenate, borate, molybdate, carbonate, and silicate—are represented by their central cations S6+, Se6+, P5+, As5+, B3+, Mo4+, C4+, and Si4+. The ions fall into three behavioral groups. Ions of high ionic potential, the alkali and alkaline earth cations and the halide anions, large univalent and divalent ions, are highly water soluble, easily weatherable, and leach readily from soils to the sea over geologic time. 

Similarly, molybdate (MoO/) together with other group VI oxyanions are analogues of sulfate and inhibit sulfate reduction competitively. 

As judged from our ecological model compound sea water, the bioavailability of molybdenum (104 nM) is higher than that of chromium (962pM) (see Table 1.1). While chromium is insoluble as Cr(III) in the Earth s crust, the reduction of molybdate is not as easy as chromate reduction, which leads to a factor of 10 000 when the release of chromium and molybdenum from the Earth s crust into sea water is compared. Together with its low toxicity (Nies 1999), this makes molybdate the prime choice for biochemical reactions requiring oxyanion catalysis (Williams and da Silva 2002). 

The phosphate site. The phosphate site is highly regular and can be substituted by vanadate, chromate, arsenate, carbonate, silicate and sulfate, but only vanadate, arsenate and carbonate solid solution is widespread in natural apatites. Charge-coupled substitution schemes to aid incorporation involve the substitution of silicate for phosphate and REE for Ca, and carbonate or sulfate for phosphate and Na for Ca. Numerous oxyanions may act as activators and sensitizers, with the most widespead being molybdate and tungstate, but vanadate and niobate can also activate luminescence (Blasse and Grabmaier 1994). Silicate is a strong absorber of UV radiation and can serve as a... 

Figure 7 Effect of group VIA oxyanion inhibitors on the reduction of arsenate (O) to arsenite ( ) in estuarine sediments slurries incubated (a) without additions, (b) with molybdate, and (c) with tungstate. (From Ref. 39.)...

Its basic form has been used successfully for the collection of Cr(lII) [36], and cadmium [37] fnrni urine. In a detailed study on the behavior of various oxyanions on activated alumina (acidic) Cook et al.[35] have shown that while arsenate, chromate, molybdate, phosphate, selenate, and vanadate were all well retained on the sorbent, only chromate and molybdate could be reasonably well eluted using IM NH4OH, or stronger alkali solutions. About 80% of phosphate and selenate could be eluted using IM KOH, whereas arsenate and vanadates may be de-sorbed only by using stronger eluents such as 5M KOH. 

Identification of the specific species of the adsorbed oxyanion as well as mode of bonding to the oxide surface is often possible using a combination of Fourier Transform Infrared (FTIR) spectroscopy, electrophoretic mobility (EM) and sorption-proton balance data. This information is required for selection of realistic surface species when using surface complexation models and prediction of oxyanion transport. Earlier, limited IR research on surface speciation was conducted under dry conditions, thus results may not correspond to those for natural systems where surface species may be hydrated. In this study we review adsorbed phosphate, carbonate, borate, selenate, selenite, and molybdate species on aluminum and iron oxides using FTIR spectroscopy in both Attenuated Total Reflectance (ATR) and Diffuse Reflectance Infrared Fourier Transform (DRIFT) modes. We present new FTIR, EM, and titration information on adsorbed arsenate and arsenite. Using these techniques we... 

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