Redox processes, leaching

Some trace metals are transported into the ocean as a component of hydrothermal fluids. This process is discussed further in Chapter 19- To briefly summarize, hydrothermal fluids are produced when seawater penetrates into cracks in the crust near tectonic spreading centers. The seawater is heated as it comes into contact with magma. The hot seawater leaches a number of trace metals from the magma. The resulting hydrothermal fluids are acidic and do not contain O2, so most of the metals are present in reduced form. Because of their high temperatures, the hydrothermal fluids have a lower density than cold seawater. Their increased buoyancy causes them to rise until they are emitted into the deep sea. Admixture with cold, oxic, alkaline seawater causes the hydrothermal metals to undergo various redox and precipitation reactions. 

Oxidation of insoluble mineral sulfides to the usually water-soluble sulfates (PbS04 is an exception) can also be carried out in many cases by microbial leaching, that is, by the use of bacteria such as Thiobacillus fer-rooxidans which can use the sulfide-sulfate redox cycle to drive metabolic processes. The overall reaction still consumes oxygen... 

In the various solvent-extraction circuits employed in this process, use is made of a solution of D2EHPA in kerosene as the extractant. The selective recovery of the various metals is achieved by careful control of the equiUbrium pH value of the aqueous phases in the multistage extraction and stripping operations. After the leach liquor has passed through two separate circuits, each of which comprises five stages of extraction and four of stripping, the europium product is obtained initially as a solution of europium(III) chloride. Further purification of the product is accomplished by reduction with amalgamated zinc to Eu +, which is by far the most stable of the divalent lanthanide ions with respect to the reduction of water cf. the redox potentials of the Eu /Eu and Sm /Sm + couples, which are —0.43 and —1.55 V respectively ). Sulfuric acid is added to the... 

One outcome of the migration of ions fi om one redox region into another should be a zonation of elements in relation to the reduced column. Element zonation is a reported feature of selective leach anomalies (Clark, 1996). Zonation could occur due to a variety of processes, the most important of which would be progressive deposition of redox-active species as they migrate into or out of the reduced column. The migration paths of reduced and oxidised ions are predictable provided the current flow patterns can be inferred and therefore, if the redox behaviour of a particular ion is known, the shape of anomalies can be inferred. 

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