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.

Initiation of a stable convective hydroclimatic regime in Central America circa 9000 years BP.

Many Holocene hydroclimate records show rainfall changes that vary with local orbital insolation. However, some tropical regions display rainfall evolution that differs from gradual precessional pacing, suggesting that direct rainfall forcing effects were predominantly driven by sea-surface temperature thresholds or inter-ocean temperature gradients. Here we present a 12,000 yr continuous U/Th-dated precipitation record from a Guatemalan speleothem showing that Central American rainfall increased within a 2000 yr period from a persistently dry state to an active convective regime at 9000 yr BP and has remained strong thereafter. Our data suggest that the Holocene evolution of Central American rainfall was driven by exceeding a temperature threshold in the nearby tropical oceans. The sensitivity of this region to slow changes in radiative forcing is thus strongly mediated by internal dynamics acting on much faster time scales.