Abstract

The volatile element Cl can be lost during the formation and evolution of planetary bodies, leading to fractionation of its two stable isotopes 35Cl and 37Cl. Chlorine isotope variations (reported as δ37Cl in parts per thousand (‰) relative to Standard Mean Ocean Chloride, SMOC) are documented to exceed 80‰ between different lunar rock samples and have been variably interpreted as the fingerprint of degassing during accretion, magma ocean, or volcanic portions of lunar history. The large intersample and intrasample variations observed by both bulk isotope ratio mass spectrometry (IRMS) and in-situ secondary ion mass spectrometry (SIMS) methods are difficult to interpret in part because of a paucity of bulk Cl isotope measurements. This lack of high-precision bulk data is due to the relative rarity of IRMS laboratories capable of making these high precision measurements on small samples of precious planetary materials such as those returned by human or robotic exploration. Here we present a new method for performing high precision δ37Cl measurements using the modified Middleton ion source of an existing accelerator mass spectrometer. For samples with as little as 1 μg Cl–the equivalent of 2–4 mm3 of a typical lunar rock sample–the average cathode accuracy is ∼1‰. Cathode reproducibility is typically ∼1‰ (2σ) for samples with at least 10 μg of Cl, increasing to ∼3–6‰ for aliquots with ∼1–2 μg Cl, similar to published SIMS results and sufficient to study astromaterials from the Moon, Mars, or 4 Vesta, which have tens of ‰ observed variations.

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