Magmatic sulfate‑melt exsolution as a mechanism for excess sulfur in porphyry systems

Sulfur released by magmatic activity strongly impacts the climate and is essential for ore mineralisation. Many porphyry systems contain up to billions of tons of sulfur, far exceeding the sulfur capacity of silicate melt and therefore requiring an additional, efficient S‑transfer mechanism.

We present a unique mafic rock (SiO₂ = 53–59 wt.%, MgO = 5.3–7.3 wt.%) containing ~15–20 vol.% anhydrite, ~30–40 vol.% biotite and ~40–50 vol.% plagioclase from the largest porphyry–epithermal system in China. Magmatic anhydrite, indicated by textural relations and LREE‑rich compositions, yields bulk‑rock S contents of ~2–3 wt.%, far above experimental S solubilities.

Plagioclase shows sharp core–rim decreases from An₅₀–₇₀ to An₂₅–₄₅, recording strong CaO depletion caused by sulfate saturation. Extensive sulfate saturation also suppressed amphibole/orthopyroxene and removed a large proportion of LREEs from the melt, producing flat REE patterns in co-crystallised apatite. Biotite exhibits pronounced Ba depletion from core to rim. Because Ba partitions strongly into sulfate melt, not into anhydrite, this Ba zoning is best explained by the formation of a sulfate melt, rather than by crystallisation of anhydrite from a silicate melt.

Nd isotopic compositions (ԑNd(t) ≈ -1.0) indicate that the magma was derived from partial melting of the mantle wedge. We suggest that ascent of this oxidised, sulfur‑rich mafic magma led to decompression-driven oxidation of S²⁻ to S⁶⁺, sulfate saturation, and exsolution of an immiscible sulfate melt. This discrete sulfate‑melt migrated upward and provided an efficient pathway for long‑distance transfer of large amounts of sulfur to porphyry systems. This sulfate‑melt exsolution process is a previously unrecognised mechanism that relaxes the constraint imposed by the sulfur capacity of silicate melt, and LREE‑depleted apatite associated with abundant magmatic sulfate phases may serve as an indicator of sulfate‑melt exsolution and a proxy for porphyry mineralisation potential in the upper crust.