Devolatilization history and trace element mobility in deeply subducted sedimentary rocks: Evidence from Western Alps HP/UHP suites

Metapelitic rocks of the Schistes Lustrés in the Cottian Alps, Italy (peak metamorphic conditions of 350–500 °C, 1.2–2.0 GPa) and at the UHP Lago di Cignana locality (Valtournenche, Italy; ~ 550 °C, 2.5–3.0 GPa) preserve records of prograde devolatilization in their mineral modes and chemistry, contents of volatiles and fluid-mobile elements (elements relatively mobile in aqueous fluids), and B and N isotope compositions. This suite allows study of prograde devolatilization history, across a wide range in metamorphic grade, in metasedimentary rocks that experienced high-P/T prograde paths similar to those experienced in most modern subduction zones.Across grade, whole-rock samples are in general uniform in their concentrations of relatively fluid-mobile elements N, B, Li, Cs, Ba, and Rb, normalized to the concentrations of the less mobile K2O and Al2O3, showing only hints of loss in several of the highest-grade samples. With increasing grade, ion microprobe analyses of phengites show subtle decrease in B concentration, uniformity in Ba and Cs concentrations, and increase in Li concentrations, the latter likely due to release from chlorite during its breakdown. In one Cignana sample, phengite inclusions in garnets are enriched in B relative to matrix phengite, consistent with either whole-rock B loss after garnet growth or, more likely, closed-system behavior and partitioning of B into paragonite or tourmaline stabilized after garnet growth. In samples with both paragonite and phengite, paragonite shows relative enrichment in B and Sr, and phengite is enriched in Cs, Ba, and presumably also N and Rb (the latter showing strong whole-rock correlations with K2O).Whole-rock δ15N shows a hint of shift to higher values in the highest grade rocks (Cignana) and, accordingly, calculated prograde dehydration histories for appropriate bulk compositions, using the Perple-X database, indicate that significant (~ 20%) dehydration would for some rocks occur over the temperature interval of 450 to 550 °C, largely related to the breakdown of chlorite (and to a lesser extent carpholite). Small amounts of loss of N into these fluids could have resulted in minor shift in δ15N, with decrease in whole-rock N concentration masked by heterogeneity inherent with the sedimentary protoliths. Partitioning of Cs and Li (possibly also Rb and Ba) from white micas into H2O-rich fluids largely produced by chlorite breakdown could similarly have produced the subtle decreases in the concentrations in these elements noted in several high-grade samples. Neoblastic tourmaline in higher-grade rocks likely sequestered some fraction of the B lost from micas, resulting in a lack of obvious whole-rock B loss to accompany the up-grade trend of decreasing B concentrations in phengite. This tourmaline shows core-to-rim decrease in δ11B consistent with growth during small amounts of progressive B loss from phengites.Taken together, the whole-rock and SIMS data presented here, and the whole-rock dataset of Busigny et al. (2003), demonstrate impressive retention, during prograde forearc devolatilization, of elements thought to be relatively fluid-mobile (particularly H, N, B, Li, Ba, and Cs). Retention of these elements in metasedimentary rocks subducted to depths overlapping those beneath arc volcanic fronts (~ 90 km estimated for subsolidus, peak Cignana metamorphism) implies their availability for transfer into arc source regions, in aqueous fluids or silicate melts, or into the mantle to depths beyond subarc regions.

► Effects of subduction zone metamorphism on sediment compositions were examined.
► Calculated devolatilization history matches history observed in an Italian Alps suite.
► Subducted sediments retain most of their volatiles to depths beneath volcanic fronts.
► Phengite stability largely controls the deep subducton of B, Li, and the LILE.
► Boron subduction cycling is also strongly affected by tourmaline stability.