Our recent investigations have discovered inward diffusion (in-gassing) of moderately volatile elements (MVEs; e.g., Na, K and Cu) from volcanic gas into volcanic beads/droplets. In this work, we examine the distribution of sulfur in lunar orange glass beads. Our analyses reveal that sulfur exhibits a non-uniform distribution across the beads, forming U or W shaped profiles typical of in-gassing. A model developed to assess sulfur contributions from different sources (original magmatic sulfur versus atmospheric in-gassed sulfur) in the orange beads indicates that atmospheric sulfur in-gassed during eruption contributes approximately 9-24 % to the total sulfur content of an orange bead, averaging around 16 %. This in-gassed sulfur is derived from the eruption plume, where atmospheric sulfur could undergo photochemical reactions induced by UV light, leading to mass independent fractionation and a distinct sulfur isotope signature. Interestingly, a recent study discovered a small mass independent isotope fractionation of sulfur in lunar orange glass beads in drive tube 74002/1 and a lack of such mass independent isotope fractionation in black glass beads in the same lunar sample. This finding contrasts with sulfur in lunar basalts, which typically exhibit mass dependent fractionation. With our work, the observed mass independent fractionation signal in sulfur isotopes of orange beads can be attributed to the in-gassing of photolytic sulfur in the optically thin part of the eruption plume where UV light can penetrate. Using the sulfur isotope data of lunar orange beads, we estimate that the 033S value of atmospheric sulfur is approximately -0.18 %o. Our study provides new insights into the complex dynamics of volatile elements in lunar volcanic processes, highlighting the role of in-gassing in shaping sulfur isotope signatures in volcanic glass beads.

The origin, evolution, and cycling of volatiles on the Moon are established by processes such as the giant moon forming impact, degassing of the lunar magma ocean, degassing during surface eruptions, and lunar surface gardening events. These processes typically induce mass-dependent stable isotope fractionations. Mass-independent fractionation of stable isotopes has yet to be demonstrated during events that release large volumes of gas on the moon and establish transient lunar atmospheres. We present quadruple sulfur isotope compositions of orange and black glass beads from drive tube 74002/1. The sulfur isotope and concentration data collected on the orange and black glasses confirm a role for magmatic sulfur loss during eruption. The Delta S-33 value of the orange glasses is homogenous (Delta S-33 = -0.029 parts per thousand +/- 0.004 parts per thousand, 2SE) and different from the isotopic composition of lunar basalts (Delta S-33 = 0.002 parts per thousand +/- 0.004 parts per thousand, 2SE). We link the negative Delta S-33 composition of the orange glasses to an anomalous sulfur source in the lunar mantle. The nature of this anomalous sulfur source remains unknown and is either linked to (a) an impactor that delivered anomalous sulfur after late accretion, (b) sulfur that was photochemically processed early during lunar evolution and was transported to the lunar mantle, or (c) a primitive sulfur component that survived mantle mixing. The examined black glass preserves a mass-dependent Delta S-33 composition (-0.008 parts per thousand +/- 0.006 parts per thousand, 2SE). The orange and black glasses are considered genetically related, but the discrepancy in Delta S-33 composition among the two samples calls their relationship into question.