The shocking state of apatite and merrillite in shergottite Northwest Africa 5298 and extreme nanoscale chlorine isotope variability revealed by atom probe tomography

The elemental and chlorine isotope compositions of calcium-phosphate minerals are key recorders of the volatile inventory of Mars, as well as the planet's endogenous magmatic and hydrothermal history. Most martian meteorites have clear evidence for exogenous impact-generated deformation and metamorphism, yet the effects of these shock metamorphic processes on chlorine isotopic records contained within calcium phosphates have not been evaluated. Here we test the effects of a single shock metamorphic cycle on chlorine isotope systematics in apatite from the highly shocked, enriched shergottite Northwest Africa (NWA) 5298. Detailed nanostructural (EBSD, Raman and TEM) data reveals a wide range of distributed shock features. These are principally the result of intensive plastic deformation, recrystallization and/or impact melting. These shock features are directly linked with chemical heterogeneities, including crosscutting microscale chlorine-enriched features that are associated with shock melt and iron-rich veins. NanoSIMS chlorine isotope measurements of NWA 5298 apatite reveal a range of delta Cl-37 values (-3 to 1%; 2r uncertainties <0.9%) that is almost as large as all previous measurements of basaltic shergottites, and the measured delta Cl-37 values can be readily linked with different nanostructural states of targeted apatite. High spatial resolution atom probe tomography (APT) data reveal that chlorine-enriched and defect-rich nanoscale boundaries have highly negative delta Cl-37 values (mean of -15 +/- 8%). Our results show that shock metamorphism can have significant effects on chemical and chlorine isotopic records in calcium phosphates, principally as a result of chlorine mobilization during shock melting and recrystallization. Despite this, low-strain apatite domains have been identified by EBSD, and yield a mean delta(37) Cl value of -0.3 +/- 0.6% that is taken as the best estimate of the primary chlorine isotopic composition of NWA 5298. The combined nanostructural, microscale-chemical and nanoscale APT isotopic approach gives the ability to better isolate and identify endogenous volatile-element records of magmatic and near-surface processes as well as exogenous, shock-related effects. (C) 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license.

Automated summary

The chlorine isotopic records in calcium-phosphate minerals of highly shocked shergottite Northwest Africa (NWA) 5298 were evaluated to understand the effects of shock metamorphic processes. The results show significant effects of shock metamorphism on chemical and chlorine isotopic records, with findings suggesting the ability to isolate endogenous volatile-element records from magmatic and near-surface processes as well as exogenous, shock-related effects. High spatial resolution analytical techniques provide detailed insights into the complex nanostructural features associated with shock metamorphism.