Mantle-forming minerals

Figure 2.6 shows P-T stability diagrams for several components exhibiting polymorphism in geology (the Co2Si04 orthosilicate, which is not a major constituent of rock-forming minerals, is nevertheless emblematic of phase transitions observed in the earth s mantle cf section 5.2.3). 

Apatite is a nearly ubiquitous phase in igneous rocks, due in part to the low solubility of P2O5 in silicate (and other) melts, and the limited amount of phosphorus accepted by the major rock-forming minerals. The solubility characteristics have been well characterized and can be used to make estimates of the temperature at which apatite crystallizes in magmatic systems. Apatite is a major repository of the halogens in rocks of the Earth s crust and mantle, and is one of the few phases that can be used to infer information about the composition of crustal and mantle fluids. 

The discussion above has been directed principally to thermally induced spin transitions, but other physical perturbations can either initiate or modify a spin transition. The effect of a change in the external pressure has been widely studied and is treated in detail in Chap. 22. The normal effect of an increase in pressure is to stabilise the low spin state, i.e. to increase the transition temperature. This can be understood in terms of the volume reduction which accompanies the high spin—dow spin change, arising primarily from the shorter metal-donor atom distances in the low spin form. An increase in pressure effectively increases the separation between the zero point energies of the low spin and high spin states by the work term PAV. The application of pressure can in fact induce a transition in a HS system for which a thermal transition does not occur. This applies in complex systems, e.g. in [Fe (phen)2Cl2] [158] and also in the simple binary compounds iron(II) oxide [159] and iron(II) sulfide [160]. Transitions such as those in these simple binary systems can be expected in minerals of iron and other first transition series metals in the deep mantle and core of the earth. 

The sedimentary and metamorphic rocks uplifted onto land have become part of continents or oceanic islands. These rocks are now subject to chemical weathering. The dissolved and particulate weathering products are transported back to the ocean by river runoff. Once in the ocean, the weathering products are available for removal back into a marine sedimentary reservoir. At present, most mass flows on this planet involve transport of the secondary (recycled) materials rather than the chemical reworking of the primary (juvenile) minerals and gases. The natirre of these transport and sediment formation processes has been covered in Chapters 14 through 19 from the perspective of the secondary minerals formed. We now reconsider these processes from the perspective of impacts on elemental segregation between the reservoirs of the crustal-ocean-atmosphere factory and the mantle. 

Chlorine is the major anion in surface- and mantle-derived fluids. It is the most abundant anion in hydrothermal solutions and is the dominant metal complexing agent in ore forming environments (Banks et al. 2000). Despite its variable occurrence, chlorine isotope variations in natural waters conunonly are small and close to the chlorine isotope composition of the ocean. This is also true for chlorine from fluid inclusions in hydrothermal minerals which indicate no significant differences between different types of ore deposits such as Mississippi-Valley and Porphyry Copper type deposits (Eastoe et al. 1989 Eastoe and Guilbert 1992). 

O, H, C, S, and N isotope compositions of mantle-derived rocks are substantially more variable than expected from the small fractionations at high temperatures. The most plausible process that may result in variable isotope ratios in the mantle is the input of subducted oceanic crust, and less frequent of continental crust, into some portions of the mantle. Because different parts of subducted slabs have different isotopic compositions, the released fluids may also differ in the O, H, C, and S isotope composition. In this context, the process of mantle metasomatism is of special significance. Metasomatic fluids rich in Fe +, Ti, K, TREE, P, and other large ion lithophile (LIE) elements tend to react with peridotite mantle and form secondary micas, amphiboles and other accessory minerals. The origin of metasomatic fluids is likely to be either (1) exsolved fluids from an ascending magma or (2) fluids or melts derived from subducted, hydrothermally altered crust and its overlying sediments. 

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