Mid- to late Holocene sea-level rise recorded in Hells Bells 234U/238U ratio and geochemical composition.

Hells Bells are underwater secondary carbonates discovered in sinkholes (cenotes) southeast of Cancun on the north-eastern Yucatán peninsula, Mexico. These authigenic calcite precipitates, reaching a length of up to 4 m, most likely grow in the pelagic redoxcline. Here we report on detailed 230Th/U-dating and in-depth geochemical and stable isotope analyses of specimens from cenotes El Zapote, Maravilla and Tortugas. Hells Bells developed since at least ~ 8000 years ago, with active growth until present day. Initial (234U/238U) activity ratios (δ234U0) in Hells Bells calcite decreas from 55 to 15‰ as sea level converges toward its present state. The temporal evolution of the geochemistry and isotope composition of Hells Bells calcites thus appears to be closely linked to sea-level rise and reflects changing hydrological conditions (desalinization) of the aquifer. We suggest that decelerated leaching of excess 234U from the previously unsaturated bedrock traces Holocene relative sea-level rise. Considering this proxy, the resulting mean sea-level reconstruction contains half as much scatter, i.e. improves by a factor of two, when compared to previously published work for the period between 8 and 4 ky BP.

The impact of seasonal and event-based infiltration on transition metals (Cu, Ni, Co) in tropical cave drip water.

RATIONALE: The first-row transition metals Cu, Ni, and Co show a strong binding affinity to natural organic matter. Compared to dissolved elements and stable water isotopes, they may be transported rapidly through the soil and host rock into caves in response to infiltration events. This study aims to assess the potential of transition metal ratios as indicators for infiltration changes in response to the seasonal and/or event-based rainfall variation. METHODS: We developed a protocol to analyze Cu, Ni, and Co in the cave drip water using collision cell ICP-QMS without extensive sample pretreatment. The high Ca matrix leads to significant isobaric interferences on all isotope masses. Our method includes a correction of these matrix effects and yields results with comparable accuracy and reproducibility to other published methods. We applied this protocol to drip water samples from Larga Cave (Puerto Rico) covering at least two full annual cycles between 2014 and 2019 on a bimonthly scale. RESULTS: The analysis of external reference materials yielded a reproducibility between 4.7% and 9.2% (relative standard deviation), validating the accuracy of the matrix correction method. The limit of detection is <0.04 ppb for Cu, <0.02 ppb for Ni, and <0.008 ppb for Co. The analysis of drip water samples from Larga Cave reveals pronounced changes of several orders of magnitude in all Element (El) to Ca, Cu/Ni, and Cu/Co ratios in response to seasonal infiltration changes. In addition, we observe a partly even stronger response after major tropical storms and heavy precipitation events of the period of record, for example, tropical storm "Bertha" (2014) and the category 5 hurricanes "Irma" and "Maria" (both 2017). CONCLUSIONS: Transition metal ratios can be accurately measured in cave drip waters with high Ca matrix. At our tropical site, these are promising tracers of infiltration changes in response to changes in the amount of rainfall, providing the first step toward tropical cyclone reconstruction using trace elements in speleothems.

Solar forcing of early Holocene droughts on the Yucatán peninsula.

A speleothem record from the north-eastern Yucatán peninsula (Mexico) provides new insights into the tropical hydro-climate of the Americas between 11,040 and 9520 a BP on up to sub-decadal scale. Despite the complex atmospheric reorganization during the end of the last deglaciation, the dominant internal leading modes of precipitation variability during the late Holocene were also active during the time of record. While multi-decadal variations were not persistent, Mesoamerican precipitation was dominated by changes on the decadal- and centennial scale, which may be attributed to ENSO activity driven by solar forcing. Freshwater fluxes from the remnant Laurentide ice sheet into the Gulf of Mexico and the North Atlantic have additionally modulated the regional evaporation/precipitation balance. In particular, this study underlines the importance of solar activity on tropical and subtropical climate variability through forcing of the tropical Pacific, providing a plausible scenario for observed recurrent droughts on the decadal scale throughout the Holocene.