The advantages and limits of empirical, semi-empirical and thermodynamic methods devoted to the estimation of chlorite-formation temperature are discussed briefly. The results of semiempirical and thermodynamic approaches with different assumptions regarding the redox state of iron in chlorite are compared for a large set of natural data covering a range of pressure conditions from a few hundred bars to 18 kbar and temperature from 100 to 500°C. The T-XFe³⁺ evolution estimated using the thermodynamic approach of Vidal et al. (2005) shows a systematic increase in XFe³⁺ with decreasing temperature, which is compatible with the decrease in aO₂ buffered by magnetite- or hematite-chlorite equilibrium. This trend as well as the observed increase in vacancies in chlorite with decreasing temperature is interpreted as the incorporation of Fe³⁺-sudoite. The standard-state properties of this endmember have been derived to reproduce the observed T-aO₂-XFe³⁺ evolutions. It can be used to estimate T-aO₂-XFe³ values with a Chl-Qtz-H₂O multi-equilibrium approach. When combining our results with those of other studies published recently, it appears that thermodynamic approaches and mapping techniques developed for metamorphic rocks can be used to discuss the conditions of formation of very low-grade rocks where kinetics is much more sluggish than in metamorphic rocks. This requires use of appropriate analytical tools and techniques with a spatial resolution of a few hundred nanometres.

Chlorite, a 2:1:1 phyllosilicate, has all the required attributes to form the basis of a geothermometer: this mineral is ubiquitous in metamorphic, diagenetic, and hydrothermal systems with a broad field of stability and a chemical composition partly dependent on temperature (T) and pressure (P) conditions. These properties led to the development of a multitude of chlorite thermometers, ranging from those based on empirical calibrations (linking T to Al^IV content) to thermodynamic or semi-empirical models (linking T to chlorite + quartz + water equilibrium constant). This present study provides an overview of these geothermometers proposed in the literature for low-temperature chlorite (T < 350 °C), specifying the advantages and limitations of each method. Recent analytical developments that allow for circumventing or responding to certain criticisms regarding the low-temperature application of thermometers are also presented. The emphasis is on micrometric and nanometric analysis, highlighting chemical intracrystalline zoning—which can be considered as evidence of a succession of local equilibria justifying a thermometric approach—and mapping ferric iron content. New perspectives in terms of analysis (e.g., Mn redox in Mn-chlorite) and geothermometer (molecular solid-solution model, oxychlorite end-member) are also addressed.