Inter-laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

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 Ca-10(PO4)(6)(F,Cl,OH)(2) solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for Cl-37/Cl-35 homogeneity using SIMS followed by delta Cl-37 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 Cl-37/Cl-35 ratios measured on three oriented apatite fragments. Furthermore, the results of GS-IRMS analyses show small but systematic offset of delta Cl-37(SMOC) values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10(3)delta Cl-37(SMOC) values between +0.09 and +0.42 and in all cases with 1s <= +/- 0.25

Oxygen isotope compositions of conodonts – analytical challenges of in situ SIMS studies

Reliable deep-time environmental and climate reconstructions are needed to understand the drivers of Earthâs system evolution over geological time. Palaeozoic temperature estimates, including reconstructions of the climate change through the Ordovician, are based mainly on oxygen isotope (18O/16O; δ18OVSMOW) thermometry derived from carbonate rocks with fossils such as calcitic brachiopods and phosphatic conodonts that are often the best preserved repositories of environmental conditions. Palaeoenvironmental reconstructions are reliable only if the geochemical data is obtained using well-calibrated analytical tools. Most previous research devoted to oxygen isotope composition of conodonts has been conducted using the bulk method (gas source isotope ratio mass spectrometry (GS-IRMS)) that typically requires pooling several dozens of conodont elements for a single isotope ratio measurement. As such, studies of conodont-poor intervals and assessments of taxon-specific δ18O variability require extensive sample preparation and are challenging using the bulk method. Such challenges can be addressed by in situ secondary ion mass spectrometry (SIMS) analyses using only picogram sampling masses. However, several studies have reported inconsistencies between SIMS and GS-IRMS δ18O data for the same research material. We aim to solve this controversy by establishing a robust analytical protocol for conodont isotope analysis by SIMS. Here we present conodont data on Pterospathodus and Amorphognathus specimens extracted from Ordovician strata in Nurme and Mehikoorma-421 boreholes (Estonia). Oxygen isotope composition of conodonts was analysed by both SIMS and GS-IRMS, where we paid particular attention to four inorganic apatite reference materials in order to understand the offset between these two techniques that have been reported in the literature. While the results of GS-IRMS measurements conducted using high-temperature reduction of Ag3PO4 represent exclusively δ18O of phosphate-bound oxygen, SIMS analyses do not discriminate between different oxygen components (e.g., (PO4)3â, (SiO4)4â, (CO3)2â, and (OH)â) in apatite, inherently providing information on pooled isotope compositions. We conducted quantitative chemical analyses of selected conodont elements by electron probe microanalysis to assess to what extent matrix effects cause the offsets between the two isotope techniques. We also used scanning electron microscopy and white light optical profilometry to evaluate sample topography and porosity, which have a major impact on SIMS data quality. We collected oxygen isotope data using a CAMECA 1280-HR large geometry instrument at the Potsdam SIMS user facility over several months to determine reproducibility of the results and to optimise a routine measurement protocol. Our tests included a variety of instrumental settings, e.g., different raster parameters for both pre-sputtering and data collection, which yielded slightly differing results due to different instrumental mass fractionation. SIMS is a comparative method, and as such relies on reference materials that have been previously characterised by bulk methods, ideally provided by multiple laboratories. We noted that the inconsistent offsets between SIMS and GS-IRMS data obtained for a given conodont specimen (with SIMS δ18O values in most cases being higher) are linked to reference material measurements that are necessary for conodont data calibration and are often biased towards lighter δ18O values. Our tests show that such bias is even more significant when calibration is based on a single reference material characterised by a single GS-IRMS laboratory, which has been a common practice in past conodont studies

Vibrational spectroscopic study of synthetic analogs of schultenite PbHAsO4-"phosphoschultenite" PbHPO4 solid solution series

Lead hydrogen arsenate PbHAsO4 and lead hydrogen phosphate PbHPO4, which can form a continuous solid solution series, have been extensively studied owing to their ferroelectric properties. PbHAsO4 has also been found to occur in weathered As-and Pb-rich outcrops and historically contaminated soils as a schultenite mineral. Although most ferroelectric studies were of substantial interest more than 30 years ago, the contamination of the Earth's surface with toxic Pb and As remains a major concern for environmentalists. In this study, six compounds of PbHAsO4-PbHPO4 solid solution series were synthesized from aqueous solutions at ambient conditions. They were subsequently analyzed using Raman and Fourier transform infrared spectroscopy to describe their vibrational characteristics, which should help identify the series members in natural or synthetic samples in further environmental and mineralogical studies. Additionally, powder X-ray diffraction analyses were conducted to investigate the variations in the unit cell parameters along the series. The results showed linear variations in the band positions in both Raman and infrared spectra, which depend on the extent of the isomorphic substitution of (PO4)(3-) for (AsO4)(3-). However, the bands become broader or split as a result of phosphate substitution, making it difficult to correlate the band positions with the molecular composition of an unknown phase. The X-ray diffraction data revealed linear variations of all lattice constants as a function of P. Moreover, a relevant finding of this study is the systematic deviation in the chemical compositions of the synthetic phases from the composition of aqueous solutions from which they precipitated, caused by the preferential incorporation of (AsO4)(3-) with respect to (PO4)(3-) into the structure

Validity of the Apatite/Merrillite Relationship in Evaluating the Water Content in the Martian Mantle: Implications from Shergottite Northwest Africa (NWA) 2975

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 &gt; 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 &gt; 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

Inter‐laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

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 δ37ClSMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 103δ37ClSMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25.Key Points: Six apatite reference materials having various Cl mass fractions were characterised for chlorine isotope ratios by SIMS and three GS‐IRMS laboratories. A small, but significant, crystal orientation effect was recorded by SIMS analyses. Correlation of instrumental mass fractionation factor with Cl mass fraction is visible along the apatite solid solution series.Narodowe Centrum NaukiDeutscher Akademischer AustauschdienstHelmholtz Recruiting InitiativeInstitute of Geological Sciences, Polish Academy of Science