Compared to most other planetary materials in the Solar System, some lunar rocks display high delta Cl-37 signatures. Loss of Cl in a H << Cl environment has been invoked to explain the heavy signatures observed in lunar samples, either during volcanic eruptions onto the lunar surface or during large scale degassing of the lunar magma ocean. To explore the conditions under which Cl isotope fractionation occurred in lunar basaltic melts, five Apollo 14 crystalline samples were selected (14053,19, 14072,13, 14073,9, 14310,171 along with basaltic clast 14321,1482) for in situ analysis of Cl isotopes using secondary ion mass spectrometry. Cl isotopes were measured within the mineral apatite, with delta Cl-37 values ranging from +14.6 +/- 1.6 parts per thousand to +40.0 +/- 2.9 parts per thousand. These values expand the range previously reported for apatite in lunar rocks, and include some of the heaviest Cl isotope compositions measured in lunar samples to date. The data here do not display a trend between increasing rare earth elements contents and delta Cl-37 values, reported in previous studies. Other processes that can explain the wide inter- and intra-sample variability of delta Cl-37 values are explored. Magmatic degassing is suggested to have potentially played a role in fractionating Cl isotope in these samples. Degassing alone, however, could not create the wide variability in isotopic signatures. Our favored hypothesis, to explain small scale heterogeneity, is late-stage interaction with a volatile-rich gas phase, originating from devolatilization of lunar surface regolith rocks similar to 4 billion years ago. This period coincides with vapor-induced metasomastism recorded in other lunar samples collected at the Apollo 16 and 17 landing sites, pointing to the possibility of widespread volatile-induced metasomatism on the lunar nearside at that time, potentially attributed to the Imbrium formation event. (C) 2018 Elsevier Ltd. All rights reserved.

Earth-like delta D values reported from lunar mare-basalt apatites have typically been interpreted to reflect the intrinsic isotopic composition of lunar mantle water. New data indicates that some of these basalts are also characterized by having experienced a slow cooling history after their emplacement onto the lunar surface. This suggests that these basalts may have experienced metasomatism by fluxes generated during the degassing of the lunar regolith induced by the long-duration, high-temperature residence times of overlying basalts.