Chlorite phase compositions

If we look back to the experimental studies on natural expandable minerals at high pressures, it can be recalled that the production of a chlorite-phase occurred when interlayering in the natural dioctahedral mineral had reached about 30% interlayering. It is possible that below this transition only expandable phases are present for most magnesium-iron compositions one is dioctahedral, the other would be trioctahedral. Thus, at temperatures below the transition to an ordered allevardite-type phase, dioctahedral mixed layered minerals will coexist with expandable chlorites or vermiculites as well as kaolinite. The distinction between these two phases is very difficult because both respond in about the same manner when glycollated. There can also be interlayering in both di- and... 

In sediments and the maflc portion of the subducted crust, all of the reactions involving hydrous phases and carbonates involve solid solutions whose compositions depend on the bulk composition, in addition to pressure and temperature. Different bulk compositions cause different phase compositions and thus cause reactions to shift in P-T space, i.e., to start shallower or deeper. In peridotites, amphibole and to some extent chlorite are controlled by continuous and discontinuous reactions however, the other volumetrically important hydrous phases (e.g., brucite, serpentine, talc, and phase A ) in altered harzburgites display a relatively restricted compositional range, at least compared to those present in mafic eclogites. As a result, breakdown reactions of hydrous phases in harzburgites are dominated (in a first approximation) by discontinuous reactions, and take place over a restricted depth range of only a few kilometers. 

Chlorite compositions from areas (Toyoha Pb—Zn vein, Kuroko deposits) deviate significantly from a line of 1 1 slope. This deviation implies that the Fe +/Mg value of chlorite from these areas is controlled not only by the FeO/MgO value of the Ifesh host rocks, but also by factors such as the ratio of Fe " to Mg " " in the fluid phase. 

Lithium isotopes do not fractionate as a result of redox reactions, but Li is preferentially partitioned into the fluid phase, whereas Li prefers sites in alteration minerals such as micas. The Li/ Li ratios of mica and chlorite in alteration zones around uranium deposits are higher and decrease to lower values with distance from the ore relative to background mica in the Athabasca Group sandstones. In barren areas, high ratios are rare and background ratios are dominant. When used together, the isotopic composition of uranium and lithium can be utilized to refine both the genesis of uranium deposits and as exploration tools. 

Figure 1. Representation of the ideal compositions of some major phyllosilicate phases in the MR - 2R - 3R coordinates. M = muscovite, paragonite P - phlogopite Py = pyrophyllite Kaol = kaolinite S serpentine T = talc Chlor = chlorite, 14 8 or aluminous 7 8 polymorphs Ce = celadonite F = feldspar.

Figure 2. Illustration of the possible displacement of a sedimentary bulk composition upon reduction of Fe + to Fe + during diagenesis (after Velde, 1968). I = illite Chi = chlorite Kaol = Kaolinite M03 = expanding trioctahedral phases 1 = initial bulk composition 2 = reduced bulk composition. Upper diagram shows initial assemblage and the lower diagram those after reduction of Fe +.

In zones of hydrothermal alteration it is apparent that the formation of dioctahedral montmorillonites is limited by temperature. They almost never occur in the innermost zone of alteration, typically that of sericitization (hydro-mica or illite), but are the most frequent phase in the argillic-prophylitic zones which succeed one another outward from the zone where the hydrothermal fluid is introduced in the rock. Typically, the fully expandable mineral is preceded by a mixed layered phase (Schoen and White, 1965 Lowell and Guilbert, 1970 Fournier, 1965 Tomita, et al., 1969 Sudo, 1963 Meyer and Hemley, 1959 Bundy and Murray, 1959 Bonorino, 1959). However, temperature is possibly not the only control of expandable clay mineral occurrence, the composition of the solutions and the rock upon which they act might also be important. It is possible that high magnesium concentrations could form chlorite, for example, instead of expandable minerals. 

Considering the compositions of the mixed layered minerals found in sedimentary rocks (Figure 25) it is obvious that magnesian-iron expandable dioctahedral minerals will be in equilibrium not uniquely with kaolinite but also in many instances with a magnesian-iron phase—either chlorite or an expanding trioctahedral mineral. In such a situation the slope in... 

Although the information available from synthetic studies strongly indicates a P-T control of the chlorite polymorph, natural minerals appear to exhibit both polymorph, 7 and 14 8, at low temperature. Most diagenetic chlorites correspond to a 7 8 polymorph. However, there are occurrences especially in deep ocean sediments of a 14 8 phase. The contradiction cannot be resolved with the information available at present. It is probably reasonable to assume that the 7 8 polymorph stable for all chlorite compositions (i.e., various Fe +, Mg, A1 ratios) and that the 14 8 forms are metastable at low temperatures. However, this is certainly not definitive. 

Because the compositions are basic, the expanding minerals are trioctahedral and they are apparently associated in all facies with chlorite. The occurrence of a regularly interstratified montmorillonite (saponite) -chlorite mineral, corrensite, is typified by an association with calcic zeolites and albite. Temperature measurement in the "hydrothermal" sequences at several hundred meters depth indicate that the ordered, mixed layered mineral succeeds a fully expandable phase between 150-200 C and this ordered phase remains present to about 280°C. In this interval calcium zeolites disappear, being apparently replaced by prehnite. The higher temperature assemblage above corrensite stability typically contains chlorite and epidote. 

Figure 41. Phase diagram for the extensive variables R -R -Si combining the data for synthetic magnesian chlorites and the compositional series of natural sepiolites and palygorskites. Numbers represent the major three-phase assemblages related to sepiolite-palygorskite occurrence in sediments. Chi = chlorite M03 = trioctahedral montmorillonites M02 = dioctahedral montmorillonite Sep = sepiolite Pa = palygorskite Kaol = kaolinite T = talc.

If we consider three components, the phases will be arranged as in Figure 48a at conditions of initial burial. The solid solution series are somewhat abbreviated for simplicity. The phase relations are dominated by fully expanding and mixed layered minerals which cover a large portion of the compositional surface. Notably two dioctahedral expandable minerals exist as does a large undefined series of trioctahedral phases designated as expanding chlorite, vermiculite and trioctahedral montmorillonite. 

The second facies is marked by the instability of the fully expanding dioctahedral phases and the existence of a kaolinite-illite tie-line (Figure 48b). In this facies the siliceous alkali zeolites (other than analcite) become unstable, the compositional range of the trioctahedral expanding phases is reduced and aluminous 14 8 chlorite-"allevardite"... 

Figure 2. Projection on planes Na—K—Mg and Ca—K—Mg of the composition of possible equilibrium phases and of marine sediment minus carbonate. CH = chlorite, IL — illite (hydromica), = montmorillonite, PH = phillipsite, SED = sediments [according to Goldschmidt (7)], CA = average calcareous, SI = average siliceous, AR = average argillaceous sediments (from Ref. 22), OW = ocean water, GL = glauconite,...

From the same compositions, but at lower temperatures (below 400—500°C), a 7 A structure of the kaolinite-type is developed. Nelson and Roy (1958) called these materials septechlorites. It was not established whether the 7 A phase was metastable or not, but able to persist for long periods as a stable low-temperature polymorphic form of chlorite. They did not synthesize any ferroan chlorites but believed that similar polymorphic relations should exist in the iron chlorites. Tumock and Eugster (1958) synthesized a 7 A chlorite, daphnite, at a temperature of 400°C with a composition of (Fes AlXSi3 A1)0, o(OH)8 but were not able to convert it completely to the 14 A polymorph. 

The hydrothermal dioctahedral chlorites have considerably less tetrahedral substitution than those formed in sediments. The former would appear to be a stable phase and the latter a metastable phase. The tetrahedral composition of the hydro-thermal specimens is similar to that for the other dioctahedral clays and represents a reasonable fit between the tetrahedral and octahedral sheets. 

There have been tremendous strides made recently towards understanding how volatiles in general and water in particular is transported and stored in the mantle. This progress is based on research on a number of fronts studies of mantle-derived samples have provided insight into the nature and occurrence of hydrous phases such as amphibole, mica, and chlorite, and have provided constraints on the capacity of nominally anhydrous minerals (NAMs) such as olivine, pyroxenes, and garnet to contain water by a variety of substimtion mechanisms. Experimental studies on mantle-derived magmas have provided constraints on volatile contents in their source regions. Other studies have constrained the pressure, temperature, and composition conditions over which hydrous phases are stable in the mantle. 

The definition of the verdine facies is largely due to the work of Odin (1988). Bailey (1988) defined the mineral odinite. Verdines and odinite span much of the range of octahedral site occupation from 2.5 to 2.0 ions, containing much ferric iron and alumina. Assuming that all of the minerals are 7 A structures, the difference in observed composition of the different phases can be illustrated by their octahedral cation occupancy AI2 kaolinite (dioctahedral) (Mg, Al)3 2.5 7 A trioctahedral chlorite and (Mg, Al)2 2.5 odinite (di-, trioctahedral). 

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