The Paleoproterozoic (~1.8 Ga) Penokean Volcanic Belt (PVB) in the Great Lakes Region of North America hosts several polymetallic volcanogenic massive sulfide (VMS) deposits. These deposits were formed by back-arc extensional volcanism during the accretion of island-arc terranes along the southern margin of the Archean Superior Craton. This study reports δ34S values obtained from sulfide minerals collected from eight VMS deposits in the PVB: Back Forty, Bend, Eisenbrey, Flambeau, Horseshoe, Lynne, Reef, and Schoolhouse. The average δ34S values from most of these deposits lie within the mantle-range between −2 and 2‰, relative to Vienna Canyon Diablo Troilite (V-CDT). Average δ34S values from Back Forty and Lynne deposits are slightly higher, at 2.5 and 2.4‰, respectively. No systematic variation in δ34S was observed based on factors such as the kind of sulfide mineral, ore-texture, type of host rock, or the nature of host-rock alteration. The narrow observed range from the PVB offers a clear indication that sulfur in the mineralizing fluid, originated predominantly from a magmatic source. If there was a significant contribution of sulfur from seawater, the δ34S of seawater sulfur must also have been close to the mantle range. Slightly higher values from Back Forty and Lynne indicate minor involvement of oxidized sulfur at shallow water levels, possibly derived from the continental margin.

The total concentrations of rare-earth elements (REE) in the mined kaolin (0.02–0.06 wt.%), kaolin mine tailings (0.03–1.9 wt.%), and the kaolin-associated Marion Member sand lithology (0.03–4.6 wt.%) opened questions regarding the modes of occurrence of the REE and the role(s) of chemical weathering and secondary processes to explain the presence of REE in these materials. The REE were hosted primarily by phosphate minerals (monazite, xenotime) based on mineralogic analyses (scanning electron microscopy, X-ray diffraction). Enrichments in the light rare-earth elements (LREE: La–Gd) and the high correlation coefficient values were noted between P and the total REE concentrations (r2 = 0.99) for the sands and the mine tailings. Lower correlation coefficient values were noted between total REE concentrations and Zr (r2 = 0.31). The coarse fractions of the mined kaolins were enriched in the heavy rare-earth elements (HREE: Y, Tb–Lu) relative to the kaolin-associated sand lithologies. The REE inventory cannot be explained solely by mineral inheritance within the mined kaolins. Lower correlation coefficient values between P and total REE, positive Eu/Eu* anomalies, and the presence of xenotime overgrowths on zircon showed the importance of the role of chemical weathering of the detrital minerals during post-depositional processes (such as diagenesis) leading to redistributed and fractionated REE within the mined kaolin. The possibility of adsorption of the REE to kaolin mineral surfaces in the fine fraction of the mined kaolins remains open and permits further study to characterize fully the multi-modal fractionation of REE possible in the Georgia kaolin deposits.