The role of sub-continental mantle as both "sink" and "source" in deep Earth volatile cycles

The extent to which Earth's sub-continental lithospheric mantle modulates the flux of volatile elements from our planet's deep interior to its atmosphere (via volcanism) is poorly constrained. Here, we focus on "off-craton" sub-continental lithospheric mantle because this long-lived reservoir potentially acts as both a volatile "sink" and "source" during major heating and rifting events. The sub-continental lithospheric mantle is primarily formed of peridotites with subordinate amounts of pyroxenites. While both lithologies are dominated by nominally-volatile-free mantle minerals, some of these phases have been shown to contain non-negligible amounts of H2O (e.g. 100's of ppmw in clinopyroxene). Data for volatile elements other than Li are, however, limited. We present new, high-precision, in-situ Secondary Ion Mass Spectrometry analyses of H, F, Cl, Li and B in olivine and pyroxenes from well-characterised garnet- and spinel-bearing peridotites and pyroxenites (from southern Patagonia and the Antarctic Peninsula). Our study confirms that clinopyroxene is the main host of H2O and F. The maximum F contents we report (up to 154 ppmw) are higher than those in previous studies and occur in Ti-Cr diopsides in highly-metasomatised peridotites and Ti-Al augites from clinopyroxenite veins. Water contents of clinopyroxenes (up to 615 ppmw) are within the range previously published for continental mantle. Lithium concentrations are low (<5 ppmw) in all analysed phases and both Cl and B are below detection levels (14 ppmw and 0.03 ppmw, respectively). Unique to our study is the large variation in major- and trace-element concentrations of the clinopyroxenes, which allows us to place quantitative constraints on how volatiles are stored in the mantle. We demonstrate that: (i) F contents of clinopyroxenes closely correlate with Ti and (ii) D-H(Cpx-Opx) and D-F(Cpx-Opx) is systematic and inversely correlated with temperature. Despite the redistribution of volatiles during sub-solidus re-equilibration, we show that the first order control on the concentration of volatiles in clinopyroxene is the style of metasomatism, i.e. channellised flow versus reactive percolation. The mean bulk volatile contents of peridotites from Pali Aike and the Antarctic Peninsula (H2O = 89 +/- 31 ppmw, F = 16 +/- 11.2 ppmw and Li = 2 +/- 0.7 ppmw) are within the range previously published for continental "off-craton" mantle. The pyroxenites have significantly higher mean bulk concentrations of H2O (260 +/- 59 ppmw), F (86 +/- 43 ppmw) and Li (1.0 +/- 0.35 ppmw). While the greater capacity of mantle pyroxenites to host H2O relative to the associated peridotites has previously been observed in global "off-craton" mantle xenolith suites (e.g. Oahu, Hawaii; eastern China and the Rio Grande Rift, SW USA), here we show for the first time that pyroxenites are also major hosts of F (but not Cl, Li or B). Because of their relatively low solidus temperatures, pyroxenites in "off-craton" settings will be readily re-mobilised during lithospheric extension (and heating). We suggest these pyroxene-rich mantle lithologies may be responsible for the elevated concentrations of H2O and F observed in basalts and volcanic gasses from major continental rift zones and flood basalt provinces, and hence an important consideration in models of global volatile cycles. (C) 2020 Elsevier Ltd. All rights reserved.