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Cave carbonate minerals are an important terrestrial paleoclimate archive. A few studies have explored the potential for applying carbonate clumped isotope thermometry to speleothems as a tool for constraining past temperatures. To date, most papers utilizing this method have focused on mass-47 clumped isotope values (Δ47) at a single location and reported that cave carbonate minerals rarely achieve isotopic equilibrium, with kinetic isotope effects (KIEs) attributed to CO2 degassing. More recently, studies have shown that mass-47 and mass-48 CO2 from acid digested carbonate minerals (Δ47 and Δ48) can be used together to assess equilibrium and probe KIEs. Here, we examined 44 natural and synthetic modern cave carbonate mineral samples from 13 localities with varying environmental conditions (ventilation, water level, pCO2, temperature) for (dis)equilibrium using Δ47-Δ48 values, in concert with traditional stable carbon (δ13C) and oxygen (δ18O) isotope ratios. Data showed that 19 of 44 samples exhibited Δ47-Δ48 values indistinguishable from isotopic equilibrium, and 18 (95 %) of these samples yield Δ47-predicted temperatures within error of measured modern temperatures. Conversely, 25 samples exhibited isotopic disequilibria, 13 of which yield erroneous temperature estimates. Within some speleothemsamples, we find Δ47-Δ48 values consistent with CO2 degassing effects, however, the majority of sampleswith KIEs are consistent with other processes being dominant. We hypothesize that these values reflect isotopicbuffering effects on clumped isotopes that can be considerable and cannot be overlooked. Using a Raleigh Distillation Model, we examined carbon and oxygen isotope exchange trajectories and their relationships with dual clumped isotope disequilibria. Carbon isotope exchange is associated with depletion of both Δ47 and Δ48 relative to equilibrium, while oxygen isotope exchange is associated with enrichment of both Δ47 and Δ48 relative to equilibrium. Cave rafts collected from proximate locations in Mexico exhibit the largest averagedepartures from equilibrium (ΔΔ47 = − 0.032 ± 0.007, ΔΔ48 = − 0.104 ± 0.035, where ΔΔi is the measured value – the equilibrium value). This study shows how the Δ47-Δ48 dual carbonate clumped isotope framework can be applied to a variety of tcave carbonate mineral samples, enabling identification of isotopic equilibria and therefore quantitative application of clumped isotope thermometry for paleoclimate reconstruction, or alternatively, constraining the mechanisms of kinetic effects. 

Abstract The collapse of the Maya civilization in the late 1st/early 2nd millennium CE has been attributed to multiple internal and external causes including overpopulation, increased warfare, and environmental deterioration. Yet the role hurricanes may have played in the fracturing of Maya socio-political networks, site abandonment, and cultural reconfiguration remains unexplored. Here we present a 2200 yearlong hurricane record developed from sediment recovered from a flooded cenote on the northeastern Yucatan peninsula. The sediment archive contains fine grain autogenic carbonate interspersed with anomalous deposits of coarse carbonate material that we interpret as evidence of local hurricane activity. This interpretation is supported by the correlation between the multi-decadal distribution of recent coarse beds and the temporal distribution of modern regional landfalling storms. In total, this record allows us to reconstruct the variable hurricane conditions impacting the northern lowland Maya during the Late Preclassic, Classic, and Postclassic Periods. Strikingly, persistent above-average hurricane frequency between ~ 700 and 1450 CE encompasses the Maya Terminal Classic Phase, the declines of Chichén Itza, Cobá, and subsequent rise and fall of the Mayapán Confederacy. This suggests that hurricanes may have posed an additional environmental stressor necessary of consideration when examining the Postclassic transformation of northern Maya polities. 

Investigations in the now-submerged cave systems on the Yucatán Peninsula continue to yield evidence for human presence during the Pleistocene-Holocene transition. Skeletal remains are scattered throughout the caves of Quintana Roo, most representing individuals who died in situ. The reasons why they explored these underground environments have remained unclear. Here, we announce the discovery of the first subterranean ochre mine of Paleoindian age found in the Americas, offering compelling evidence for mining in three cave systems on the eastern Yucatán over a ~2000-year period between ~12 and 10 ka. The cave passages exhibit preserved evidence for ochre extraction pits, speleothem digging tools, shattered and piled flowstone debris, cairn navigational markers, and hearths yielding charcoal from highly resinous wood species. The sophistication and extent of the activities demonstrate a readiness to venture into the dark zones of the caves to prospect and collect what was evidently a highly valued mineral resource.