Surface enrichment with trace elements

Note finally that, as mentioned in the Introduction, the corrosion of the substrate may also damage irreversibly a microstructured device under the severe conditions of fuel processing reactions. For example, under water vapor pressure, many detrimental effects can occur, such as surface migration of Ni in stainless-steel alloys, surface oxidation of metals (Fe to Fe203), surface enrichment with trace elements able to alloy/react with the coated catalyst (Sn, Pb, Cl ions) and poison it or surface substrate restructuring. 

Figure 13. Overview of contamination processes induced by an ore deposit in a river catchment of a mountainous area. The different places potentially affected by the dispersed chemical elements are indicated with numbers (1) natural outcrop, (2) open pit, (3) mine dump, (4) local vegetation, (5) local surface water, (6) river draining the area of the ore deposit, (7) uncontaminated control area, (8) major river water, possibly carrying trace elements from the ore deposit, (9) river sediment and water plants (e.g. mosses), possibly enriched in trace elements, (10) lake sediments, possibly enriched in trace elements.

In Chapter 4, we saw how conservative chemicals are used to trace the pathway and rates of water motion in the ocean. True conservative behavior is exhibited by a relatively small number of chemicals, such as the major ions and, hence, salinity. In contrast, most of the minor and trace elements display nonconservative behavior because they readily undergo chemical reactions under the environmental conditions found in seawater. The rates of these reactions are enhanced by the involvement of marine organisms, particularly microorganisms, as their enzymes serve as catalysts. Rates are also enhanced at particle interfaces for several reasons. First, microbes tend to have higher growth rates on particle surfaces. Second, the solution in direct contact with the particles tends to be highly enriched in reactants, thereby increasing reaction probabilities. Third, adsorption of solutes onto particle surfaces can create fevorable spatial orientations between reactants that also increases reaction probabilities. 

The influence of river water inputs on trace metal distributions is illustrated in Figure 11.17c, which shows that the surface-water concentration of dissolved Mn in the Pacific Ocean decreases with increasing distance from the California coast. The vertical profile measured in the coastal zone (Figme 11.17b) exhibits a strong surface enrichment characteristic of scavenged trace elements. A similar vertical gradient is seen in the... 

Table 5.1 shows an application of XPS to the study of the promoted iron catalyst used in the Haber synthesis of ammonia. The sizes of the various electron intensity peaks allows a modest level of quantitative analysis. This catalyst is prepared by sintering an iron oxide, such as magnetite (Fe304) with small amounts of potassium nitrate, calcium carbonate, aluminium oxide and other trace elements at about 1900 K. The unreduced solid produced on cooling is a mixture of oxides. On exposure to the nitrogen-hydrogen reactant gas mixture in the Haber process, the catalyst is converted to its operative, reduced form containing metallic iron. As shown in Table 5.1, the elemental components of the catalyst exhibit surface enrichment or depletion, and the extent of this differs between unreduced and reduced forms. 

The contents of some trace elements in the continental crust, shales, soils, bituminous coals and plankton are given in Table 1.1 to provide some perspective when considering other aspects of these elements. In each of these situations, organic matter is associated with the elements to a greater or a lesser degree. This is not usually very marked with crustal rocks except shales, but may be a major factor for some elements in surface soils and coals. The data in Table 1.1 show that, for some elements, e.g. beryllium, cadmium, cobalt and molybdenum, the contents of the various reservoirs are similar, while for others, there may be enrichments relative to the crust, e.g. boron and sulfur in many shales, soils and coals, mercury, nickel and selenium in many shales, and germanium in some coals. 

Thus the surface chemistry of the ocean consists essentially of the chemistry of that part of the uncharacterised and complex part of the DOM in seawater which is surface active. Apart from other effects, this can lead to the entrainment of trace elements in the surface layer by complex formation with the surface active polymers and their enrichment in the microlayer (Barker and Zeitlin, 1972 Duce et al., 1972 Piotrowicz et al., 1972, Hunter, 1977) and possible enrichment of the atmospheric aerosol (Duce et al., 1972,1976), at least near the ocean surface (Chesselet et al., 1976). 

---