The Martian meteorite ALH84001 contains ∼1% by weight of carbonate formed by secondary processes on the Martian surface or in the shallow subsurface. The major form of this carbonate is chemically and isotopically zoned rosettes which have been well documented elsewhere. This study concentrates upon carbonate regions ∼200 μm across which possess previously unobserved magnesium rich inner cores, interpreted here as rosette fragments, surrounded by a later stage cement containing rare Ca-rich carbonates (up to Ca81Mg07Fe04Mn07) intimately associated with feldspar. High spatial resolution ion probe analyses of Ca-rich carbonate surrounding rosette fragments have δ18OV-SMOW values as low as −10‰. These values are not compatible with deposition from a global Martian atmosphere invoked to explain ALH84001 rosettes. The range of δ18O values are also incompatible with a fluid that has equilibrated with the Martian crust at high temperature or from remobilisation of carbonate of rosette isotopic composition. At Martian atmospheric temperatures, the small CO2(gas)-CO2(ice) fractionation makes meteoric CO2 an unlikely source for −10‰ carbonates. In contrast, closed system Rayleigh fractionation of H2O can generate δ18OH2O −30‰, as observed at high latitudes on Earth. We suggest that atmospheric transport and precipitation of H2O in a similar fashion to that on Earth provides a source of suitably 18O depleted water for generation of carbonate with δ18OV-SMOW = −10‰.