Partitioning and isotopic fractionation of Li between mineral phases and alkaline to calc-alkaline melts of explosive and effusive eruptions

Evaluating the lithium (Li) budget of alkaline to calc-alkaline melts and their co-existing mineral phases is crucial to understanding which magmatic or post-eruptive processes can influence the Li contents and isotopic compositions of volcanic deposits. This is also important to be able to better constrain how economically relevant Li deposits form. The lithium contents of many different eruptions from different tectonic settings (intraplate, subduction zone, extensional environment) and cooling environments (quenched, quickly cooled and slowly cooled) were studied by combining new and literature data that were obtained using LA-ICP-MS. We found that the Li concentrations in melt inclusions and re-entrants are independent of tectonic setting (hotspot, subduction zone and rifting) and rarely exceed 100 ppm. When melt inclusions are re-homogenised the Li concentration increases which can lead to the overestimation of the Li budget of a magma.

The highest Li concentrations in the alkaline suite of samples were found in groundmass glass (reaching up to 318 ppm). The Li contents in the co-existing mineral phases decrease in the following order: biotite (0.8–99.3 ppm), plagioclase (0.9–25.1 ppm), clinopyroxene (0.6–31.0 ppm) and sanidine (0.5–38.7 ppm). The highest Li concentrations in the calc-alkaline suite of samples were found in the biotite crystals (10.2–2314 ppm) followed by the groundmass glass (2.1–176 ppm). The Li contents are lower in the other mineral phases, from plagioclase (1.4–35.0 ppm), quartz (3.2–21.1 ppm), olivine (1.0–16.3 ppm), sanidine (0.3–8.1 ppm) to clinopyroxene (0.7–21.8 ppm). The Li concentrations in groundmass glass and co-existing crystal phases are independent of the tectonic setting but appear to be more closely related to their cooling environment. To evaluate the influence of the different cooling environments the Li isotopic compositions (per mil deviation of ⁷Li/⁶Li ratio relative to L-SVEC reference material) of different eruptions were also determined. The Li isotopic compositions of groundmass glass and mineral phases reveal a range in δ⁷Li composition spanning up to 6 ‰ for alkaline samples and >10‰ between bulk sample and mineral phases for calc-alkaline samples. The cooling environment of the samples has a large impact on the Li isotopic compositions of the mineral phases with only quartz seemingly unaffected. Rapidly quenched samples may retain their magmatic δ⁷Li compositions or will only experience small amounts of diffusional overprinting (e.g., by degassing) whereas slowly cooled samples will experience a prolonged diffusional exchange between minerals and matrix overprinting their magmatic δ⁷Li compositions.

The Li inventory in quartz crystals may be influenced by the tectonic setting and water concentration in the crystals. To further assess the influence of tectonic settings on Li behaviour we used a large data set which is based on the 13 alkaline to calc-alkaline eruptions from different tectonic settings and calculated the apparent partition coefficients (Kds) between groundmass glass and co-existing mineral phases. Biotite crystals (alkaline systems) return the highest Kds (subduction-extensional setting: 0.01–0.57, oceanic hotspot: 0.17–2.65) whereas sanidine crystals yield the lowest Kds. Sanidines from the subduction-extensional setting (alkaline trend) have the lowest Kds (0.01–0.07; one outlier ranging from 0.02 to 0.24), followed by the oceanic hotspot setting (alkaline trend, 0.02–0.09) and the extensional setting (calc-alkaline trend; 0.01–0.15). Plagioclase crystals from the subduction-extensional setting (alkaline trend) yield Kds between 0.01 and 0.29, crystals from subduction zone settings (0.06–0.81) and extensional settings (0.09–0.50) have larger ranges in their Kds. The clinopyroxene crystals from the subduction zone settings (calc-alkaline trend) have the largest range in Kds (0.03–0.99), followed by the oceanic hotspot setting (alkaline trend, 0.06–0.48) and subduction-extensional setting (alkaline trend, 0.01–0.22). Quartz crystals (only from the calc-alkaline trend) from subduction zone settings have lower Kds (0.09–0.13) compared to the extensional settings (Bishop Tuff: 0.14–0.28; Caetano Tuff: 0.73–0.94). The wide variety of processes that can affect final Li abundances in melt and crystals (degassing, scavenging into fluids, intra-crystal diffusion, hydration of glasses) makes estimating the partition coefficients particularly difficult and results in the wide ranges observed here. Targeted experimental work would thus help to better constrain the behaviour of Li in alkaline compositions.