The large contents of octahedral vacancies in published formulae of chlorite from hydrothermal systems and clastic sequences are shown to be largely caused by inclusion of other minerals. Verification is provided by analytical electron microscope (AEM) analyses of chlorite in pelitic rocks from the Gaspé Peninsula, Quebec and the Gulf Coast, Texas. The Gaspé chlorite occurs as discrete crystals locally coexisting with corrensite, and the Gulf Coast chlorite is free of mixed layers other than local serpentine-like 7-Å layers. Unlike most electron microprobe analyses (EMPA), but like other AEM analyses, the reported chlorite formulae do not have significant octahedral vacancies, are not Si-rich and (Fe + Mg)-poor relative to classic metamorphic chlorite, and have nearly equal amounts of tetrahedral and octahedral Al. The studied chlorites and those in metabasites and clastic rocks that could be positively identified as containing no or minimal mixed layering or submicroscopic intergrowths have little or no Ca or alkalis. In contrast, EMPA of chlorite reported for other clastic sequences show variable amounts of Na + K + 2Ca that exhibit a poorly defined positive correlation with the proportion of octahedral vacancies. The EMPA of chlorite from the Salton Sea and Los Azufres geothermal fields that were suggested to contain temperature-dependent amounts of tetrahedral Al (and thus used as “chlorite geothermometers”) show compositional characteristics similar to those reported for several saponite-chlorite transition series in metabasites.

Continuous increases in octahedral occupancy and tetrahedral Al with increasing metamorphic grade are attributed to decreases in abundance of mixed layers or fine-grained intergrown minerals that commonly occur as a result of increasing crystal size and homogeneity in prograde sequences. Use of “chlorite geothermometry” based on the proportion of apparent octahedral vacancies or tetrahedral Al is therefore unwarranted and leads to inaccurate temperature estimates.

Clay minerals and organic matter occur frequently in fault zones. Their structural characteristics and their textural evolution are driven by several formation processes: (1) reaction by metasomatism from circulating fluids; (2) in situ evolution by diagenesis; and (3) neoformation due to deformation catalysis. Clay-mineral chemistry and precipitated solid organic matter may be used as indicators of fluid circulation in fault zones and to determine the maximum temperatures in these zones. In the present study, clay-mineral and organic-matter analyses of two major fault zones – the Adams-Tinui and Whakataki faults, Wairarapa, North Island, New Zealand – were investigated. The two faults analysed correspond to the soles of large imbricated thrust sheets formed during the onset of subduction beneath the North Island of New Zealand. The mineralogy of both fault zones is composed mainly of quartz, feldspars, calcite, chabazite and clay minerals such as illite-muscovite, kaolinite, chlorite and mixed-layer minerals such as chlorite-smectite and illite-smectite. The diagenesis and very-low-grade metamorphism of the sedimentary rock is determined by gradual changes of clay mineral ‘crystallinity’ (illite, chlorite, kaolinite), the use of a chlorite geothermometer and the reflectance of organic matter. It is concluded here that: (1) the established thermal grade is diagenesis; (2) tectonic strains affect the clay mineral ‘crystallinity’ in the fault zone; (3) there is a strong correlation between temperature determined by chlorite geothermometry and organic-matter reflectance; and (4) the duration and depth of burial as well as the pore-fluid chemistry are important factors affecting clay-mineral formation.

Volcanic rocks in south County Waterford include flow-top hyaloclastite, pillow lavas and peperite, which are formed typically by sub-aqueous eruption or intrusion into unconsolidated sediment. Element mobility in wet sediment during emplacement of volcanic intrusions was reconstructed on a variety of spatial scales using bulk-rock and mineral analysis. Magma-sediment and magma-water interactions enhanced hydrothermal alteration. The chemistry of chlorite was a function of mixing between an Fe-rich magmatic fluid and a Mg-rich meteoric fluid. Chlorite geothermometry yields temperatures of formation between 230 and 388°C compatible with other metamorphic indicators. Fluid inclusion microthermometric data from genetically-related mineralized quartz veins reveal a hydrothermal vein mineralization event that occurred at lower temperatures during the end stage of volcanic activity. A convection driven mixing trend reflects the trapping of co-existing brine with entrained seawater concomitant with, the late stages of emplacement of the Bunmahon Volcano intrusions.