Mercury pathways

Balogh S, Liang L. 1995. Mercury pathways in municipal wastewater treatment plants. In Porcella DB, Wheatley B, eds. Mercury as a global pollutant. Proceedings of the Third International Conference Whistler, British Columbia, July 10-14, 1994. Boston, MA Kluwer Academic Publishers, 1181-1190. 

There also exists an acidregioselective condensation of the aldol type, namely the Mannich reaction (B. Reichert, 1959 H. Hellmann, 1960 see also p. 291f.). The condensation of secondary amines with aldehydes yields Immonium salts, which react with ketones to give 3-amino ketones (=Mannich bases). Ketones with two enolizable CHj-groupings may form 1,5-diamino-3-pentanones, but monosubstitution products can always be obtained in high yield. Unsymmetrical ketones react preferentially at the most highly substituted carbon atom. Sterical hindrance can reverse this regioselectivity. Thermal elimination of amines leads to the a,)3-unsaturated ketone. Another efficient pathway to vinyl ketones starts with the addition of terminal alkynes to immonium salts. On mercury(ll) catalyzed hydration the product is converted to the Mannich base (H. Smith, 1964). 

Monoalkylthallium(III) compounds can be prepared easily and rapidly by treatment of olefins with thallium(III) salts, i.e., oxythallation (66). In marked contrast to the analogous oxymercuration reaction (66), however, where treatment of olefins with mercury(II) salts results in formation of stable organomercurials, the monoalkylthallium(III) derivatives obtained from oxythallation are in the vast majority of cases spontaneously unstable, and cannot be isolated under the reaction conditions employed. Oxythallation adducts have been isolated on a number of occasions (61, 71,104,128), but the predominant reaction pathway which has been observed in oxythallation reactions is initial formation of an alkylthallium(III) derivative and subsequent rapid decomposition of this intermediate to give products derived by oxidation of the organic substrate and simultaneous reduction of the thallium from thallium(III) to thallium(I). The ease and rapidity with which these reactions occur have stimulated interest not only in the preparation and properties of monoalkylthallium(III) derivatives, but in the mechanism and stereochemistry of oxythallation, and in the development of specific synthetic organic transformations based on oxidation of unsaturated systems by thallium(III) salts. 

The preference for formation of dihalocarbenes (but not the trihalomethyl radicals) upon thermolysis of trihalomethyl mercury, silicon and germanium derivatives seems to be a result of intermolecular coordination, of type [1], and of a thermodynamic preference for the carbene-forming pathway. The... 

Choi S-C, TT Chase, R Bartha (1994) Metabolic pathways leading to mercury methylation in Desulfovibrio desulfuricans LS. Appl Environ Microbiol 60 4072-4077. 

Ekstrom EB, FM Morel, JM Benoit (2003) Mercury methylation independent of the acetyl-coenzyme A pathway in sulfate-reducing bacteria. Appl Environ Microbiol 69 5414-5422. 

The second pathway is seen distinctly at mercury and graphite electrodes. These electrodes are quite inactive in the catalytic decomposition of H2O2. Moreover, at them the potential where the peroxide is reduced further is more negative than the potential where it is formed from oxygen. Hence, within a certain range of not too negative potentials, the reaction can occur in such a way that the hydrogen peroxide formed accumulates in the solution. 

Fish are often the focal point of interest for methylmercury contamination, representing the main exposure pathway for humans and wildlife. Unfortunately, longterm data sets with records of both mercury deposition and fish mercury concentrations over time are limited. In Sweden, Johansson etal. (2001) estimated that... 

Wildlife toxicologists should be attuned to developments in human health mercury, as assays that have been used successfully on humans may be suitable or adaptable for other vertebrate species. Echeverria and co-workers (Echeverria et al. 2005, 2006 Heyer et al. 2006) have characterized a gene encoding coproporphyrinogen oxidase, a gene in the heme biosynthetic pathway. Polymorphism in this gene predicts differential response to elemental mercury exposure in human subjects. Plans to modify this assay for other mercury species in matrices from wildlife are under way. 

HeyerNJ, Bittner Jr AC, Echeverria D, Woods JS. 2006. A cascade analysis of the interaction of mercury and coproporphyrinogen oxidase (CPOX) polymorphism on the heme biosynthetic pathway and porphyrin production. Toxicol Lett 161 159-166. 

Important link in the pathway between mercury emissions and methyl-mercuiy in biota... 

Nishimura, H. and M. Kumagai. 1983. Mercury pollution of fishes in Minamata Bay and surrounding water analysis of pathway of mercury. Water Air Soil Pollut. 20 401-411. 

As a rule, simulations consider emissions of heavy metals from anthropogenic and natural sources, transport in the atmosphere and deposition to the underlying surface (Figure 6). It is assumed that lead and cadmium are transported in the atmosphere only as a part of aerosol particles. Besides, chemical transformations of these metals do not change removal properties of their particles-carriers. On the contrary, mercury enters the atmosphere in different physical and chemical forms and undergoes numerous transformations during its pathway in the atmosphere (Ilyn et al., 2002 2004 Ilyin and Travnikov, 2003). 

In animal studies [9], up to 8% of isotopically labelled mercuric chloride applied to the skin was absorbed within 5 h. The state of the skin is one factor which determines the rate of absorption [10]. Passive diffusion cannot be the only process involved, since the absolute absorption rate of mercury increases with increasing concentration up to a plateau value. In addition, skin absorption probably occurs transepidermally rather than via the follicular pathway [11]. 

These results have been interpreted in terms of trans addition of mercuric ion and nucleophile where the attack of the mercuric ion takes place from the more hindered side of the diene molecule. A transition state 197, involving an endo attack of mercuric ion with some stabilization by coordination to the 8,9-ethylenic bond to the mercury atom, has been proposed to support the suggested mechanism. Analogously, and in sharp contrast to the results obtained167 in the mercuration of norbomadiene which reacts with mercury salts via the usual scheme of exo-syn addition, the principal pathway in the mercuration of bicyclo[2.2.2]octa-2,5-diene is the formation of endo-syn products (equation 165). 

The classical Hoijtink mechanism and the dianion mechanism have been observed at electrodes with a high hydrogen overvoltage, such as mercury. If mercury is replaced by platinum with its low hydrogen overvoltage, a radical pathway seems to be favored [199], which is closely related to catalytic hydrogenations of hydrocarbons. Spectroelectrochemical experiments provided evidence for an additional hydride mechanism (Eqs. 25-27) [200]. ... 

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