Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca₁₀(PO₄)₆(F,Cl,OH)₂ solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for ³⁷Cl/³⁵Cl homogeneity using SIMS followed by δ³⁷Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10‰ (1s) for the five samples with > 0.5 % m/m Cl and ± 0.19‰ (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38‰ between the mean ³⁷Cl/³⁵Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ³⁷Cl_SMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10³δ³⁷Cl_SMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25.

Multiple tools have been used to determine the sensitivity of phosphates from the early Archaean Barberton greenstone belt to transformation. The assessment of the degree of transformation is crucial for verifying data about the parameters of the paleo-environment. From the obtained results, three generations of phosphates can be distinguished. Group A is observed in cherts and banded iron formation BIF early-generation fluor-hydroxyapatite that precipitated from seawater. It is characterized by flat rare earth element (REE) patterns with a positive Eu anomaly and high Y/Ho ratio in the range of 54–70. Apatites in this group lack any visible indicators of secondary alterations at the micro- and nanoscales. Fourier transform infrared spectra indicate that these apatites are relatively rich in water, and, due to cationic substitution, their OH-stretching regions exhibit complex ordering and numerous component bands. The characteristics observed in the cherts and silicified felsic volcaniclastics of group B imply advanced metasomatic alteration. They exhibit light and heavy REE depletion and an absence of water in the halogen site. Nanoscale investigations reveal cracks, pores, nanofluid inclusions and nanochannel-like structures, as well as inclusions. Group C is represented by igneous-derived apatites that partially reflect their igneous origin. The phosphates are predominantly fluorapatite with typical magmatic apatite REE distribution patterns. Imaging at the micro- and nanoscales indicates that they partially preserve the signature of igneous origin. It seems that some of the analyzed apatite partially preserved their primordial features; therefore, they might be used for the reconstruction of Archaean abiotic systems.

Here we report on the oxygen isotope compositions of four proposed apatite reference materials (chlorapatite MGMH#133648 and fluorapatite specimens MGMH#128441A, MZ‐TH and ES‐MM). The samples were initially screened for ¹⁸O/¹⁶O homogeneity using secondary ion mass spectrometry (SIMS) followed by δ¹⁸O determinations in six gas source isotope ratio mass spectrometry laboratories (GS‐IRMS) using a variety of analytical protocols for determining either phosphate‐bonded or “bulk” oxygen compositions. We also report preliminary δ¹⁷O and Δ’¹⁷O data, major and trace element compositions collected using EPMA, as well as CO₃²⁻ and OH⁻ contents in the apatite structure assessed using thermogravimetric analysis and infrared spectroscopy. The repeatability of our SIMS measurements was better than ± 0.25 ‰ (1s) for all four materials that cover a wide range of 10³δ¹⁸O values between +5.8 and +21.7. The GS‐IRMS results show, however, a significant offset of 10³δ¹⁸O values between the “phosphate” and “bulk” analyses that could not be correlated with chemical characteristics of the studied samples. Therefore, we provide two sets of working values specific to these two classes of analytical methodologies as well as current working values for SIMS data calibration.

Phosphates from the Martian shergottite NWA 2975 were used to obtain insights into the source and subsequence differentiation of the melt/melts. The crystallization of two generations of fluorapatite (F > Cl~OH and F-rich), chlorapatite and ferromerrillite-merrillite were reconstructed from TEM (Transmission Electron Microscopy) and geochemical analyses. The research results indicated that the recognized volatiles budget of the two generations of fluorapatite was related to their magmatic origin. The apatite crystals crystallized from an evolved magma during its final differentiation and degassing stage. In turn, chlorapatite replaced ferromerrillite-merrillite and was not related to, mantle-derived shergottite magma. The relationship between merrillite and apatite indicates that apatite is most probably a product of merrillite reacting with fluids. REE (rare earth elements) pattern of Cl-apatite might point to an origin associated with exogenous fluids mixed with fluids exsolved from evolved magma. The study shows that, among the three types of apatite, only the fluorapatite (F > Cl~OH) is a reliable source for assessing the degree of Martian mantle hydration. The occurrence of apatite with merrillite requires detailed recognition of their relationship. Consequently, the automatic use of apatite to assess the water content of the magma source can lead to false assumptions if the origin of the apatite is not precisely determined.

The chemical composition of different rocks as well as volatile-bearing and volatile-free minerals has been used to assess the presence of fluids in the Closepet batholith and to estimate the intensity of the fluid–rock interactions. The data were processed using polytopic vector analysis (PVA). Additional data include measurements of water content in the structure of volatile-free minerals and an examination of growth textures. The composition of mineral domains indicated formation/transformation processes with common fluid–mineral interactions. In general, the results suggested that the processes occurred in a ternary system. Two end-members were likely magmas and the third was enriched in fluids. In contrast, analysis of the apatite domains indicated that they likely formed/transformed in a more complex, four-component system. This system was fluid-rich and included hybrid magma with a large mafic component. PVA implies that the fluids do not appear to come from one source, given their close affinity and partial association with mantle-derived fluids. A dynamic tectonic setting promoting heat influx and redistribution, and interaction of fluids suggests that the formation/transformation processes of minerals and rocks occurred in a hot-spot like environment.