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Secondary ion mass spectrometry techniques are used to study trace elements in organic samples where matrix compositions vary spatially. This study was conducted to develop calibrations for lithium content and lithium isotope measurements in kerogen. Known concentrations of Li ions (6Li and 7Li) were implanted into organic polymers, with a range of H/C and O/C ratios similar to kerogen, along with glassy carbon (SPI Glas‐22) and silicate glass (NIST SRM 612). Results show that Li content calibration factors (K*) are similar for carbonaceous samples when analysed using a 5kV secondary ion accelerating voltage. Using a 9 kV secondary ion accelerating voltage, K* factors are negatively correlated with the sample O content, changing ~ 30% between 0 and 15 oxygen atomic %. Thus, to avoid the matrix effect related to O content, using a 5 kV secondary ion accelerating voltage is best for quantification of Li contents based on 7Li+/12C+ ratios. Under these analytical conditions, Li ppm (atomic) = (132 (  8) × 7Li+/12C+) × 12C atom fraction of the sample measured. Lithium isotope ratio measurements of SPI Glas‐22 and NIST SRM 612 are within uncertainty; however, the organic polymer samples as a group show a 10‰ higher δ7Li than NIST SRM 612. 

Lithium isotopes (δ7Li) in coals have been shown to increase with thermal maturity, suggesting preferential release of 6Li from kerogen to porefluids. This has important implications for paleoclimate studies based on δ7Li of buried marine carbonates, which may incorporate Li from porefluids during recrystallization. Here, the Li content and isotopic composition of macerals from two coal seams intruded by dikes, were studied as a function of temperature across a thermal gradient into the unmetamorphosed coal. Samples were collected in Colorado (USA) from a Vermejo Fm. coal seam intruded by a mafic-lamprophyre dike and compared to a Dutch Creek No.2 coal seam intruded by felsic-porphyry dike; a potential source of Li-rich fluids. The Li-content and Li-isotope compositions of coal macerals were measured in situ by Secondary Ion Mass Spectrometry (SIMS). The macerals of the Vermejo coal samples, buried to VRo 0.68% (Tmax = 104 ◦C), contained <1.5 μg/g Li with an average vitrinite δ7Li of −28.4 ± 1.6‰, while liptinite and inertinite were heavier, averaging −15.4 ± 3.6‰ and − 10.5 ± 3.7‰, respectively. The contact metamorphosed vitrinite/coke showed the greatest change with temperature with δ7Li 18 to 37‰ heavier than the unmetamorphosed vitrinite. The Dutch Creek coal, buried to VRo 1.15% (Tmax = 147 ◦C), prior to dike emplacement, may have released Li during burial, as less isotopic change was observed between contact metamorphosed and unmetamorphosed macerals. Overall, Li contents were < 1 μg/g, and the vitrinite in metamorphosed coal had δ7Li values 8 to 21‰ heavier than the unmetamorphosed coal. SIMS measurements on macerals near the dike did not show an increase in Li-content indicative of Li derived from dike fluids, however previous bulk measurements that included silicates showed slightly higher (2-3 μg/g) Li-contents near the dike, suggesting possible Li incorporation from dike fluid into metamorphic silicates. A negative correlation was observed between Li-content and 12C+/30Si+ count ratios, indicating that at metamorphic temperatures Li becomes concentrated in silicates.