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.

Post-Miocene tectonics of the Northern Calcareous Alps.

The Late Cretaceous orogeny followed by the Eocene collision of the Adriatic with the European plate dissected the Northern Calcareous Alps (NCA) by a number of well-studied strike-slip fault systems accommodating N-S shortening and E-W stretching. However, the post-Miocene fault activity is poorly constrained due to lack of Neogene faulted sediments, and glacial erosion of geomorphic indicators. Using the protected environment of caves, we fill the knowledge gap in the post-Miocene evolution of the NCA by paleostress analysis of 172 reactivated faults that offset passages in 28 caves near major faults. Constrained maximum age of caves, our results indicate that the NCA have been subjected to N to NE trending compression since Pliocene. Faulted speleothems dated with 230Th/U method, indicate that the recorded present-day stress state did not significantly change during the last 0.5 Ma. In contrast to the previously proposed post-Miocene N-S extension of NCA, but in agreement with what was observed in Vienna and Pannonian basins, we conclude that the eastward extrusion resulting from N-S convergence has continued despite a distinct slowdown of plate tectonic velocities in the late Miocene. The N-S extension affected only the Alpine front during Pliocene Molasse basin inversion, while at the scale of the Alpine orogen the NCA underwent successive N-S shortening and E-W stretching.

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.

Inter-hemispheric synchroneity of Holocene precipitation anomalies controlled by Earth's latitudinal insolation gradients.

Atmospheric circulation is a fundamental component of Earth's climate system, transporting energy poleward to partially offset the latitudinal imbalance in insolation. Changes in the latitudinal distribution of insolation thus force variations in atmospheric circulation, in turn altering regional hydroclimates. Here we demonstrate that regional hydroclimates controlled by the Northern Hemisphere mid-latitude storm tracks and the African and South American Monsoons changed synchronously during the last 10 kyrs. We argue that these regional hydroclimate variations are connected and reflect the adjustment of the atmospheric poleward energy transport to the evolving differential heating of the Northern and Southern Hemispheres. These results indicate that changes in latitudinal insolation gradients and associated variations in latitudinal temperature gradients exert important control on atmospheric circulation and regional hydroclimates. Since the current episode of global warming strongly affects latitudinal temperature gradients through Arctic amplification, our results can inform projections of likely inter-hemispheric precipitation changes in the future.

Dual clumped isotope thermometry resolves kinetic biases in carbonate formation temperatures.

Surface temperature is a fundamental parameter of Earth's climate. Its evolution through time is commonly reconstructed using the oxygen isotope and the clumped isotope compositions of carbonate archives. However, reaction kinetics involved in the precipitation of carbonates can introduce inaccuracies in the derived temperatures. Here, we show that dual clumped isotope analyses, i.e., simultaneous ∆47 and ∆48 measurements on the single carbonate phase, can identify the origin and quantify the extent of these kinetic biases. Our results verify theoretical predictions and evidence that the isotopic disequilibrium commonly observed in speleothems and scleractinian coral skeletons is inherited from the dissolved inorganic carbon pool of their parent solutions. Further, we show that dual clumped isotope thermometry can achieve reliable palaeotemperature reconstructions, devoid of kinetic bias. Analysis of a belemnite rostrum implies that it precipitated near isotopic equilibrium and confirms the warmer-than-present temperatures during the Early Cretaceous at southern high latitudes.

Publisher Correction: Multi-decadal to centennial hydro-climate variability and linkage to solar forcing in the Western Mediterranean during the last 1000 years.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Multi-decadal to centennial hydro-climate variability and linkage to solar forcing in the Western Mediterranean during the last 1000 years.

Here we present a new composite record from two well-dated speleothem records from two caves in Northern Morocco. The high-resolution record covers the last millennium allowing to detect multi-decadal to centennial periodicities. Over the industrial period, δ18O values of our speleothems are shown to be dominated by the main mode of decadal variability in the North Atlantic region: the North Atlantic Oscillation (NAO). Statistical analyses confirm the previously reported multi-decadal variability related to the influence of the Atlantic Multidecadal Oscillation (AMO) in the region. High power and persistent centennial-scale periodicities, similar to the Vries-Suess 200-year solar cycle, are observed as well. Indeed, comparison between solar activity reconstructions and our record confirms the in-phase relationship on centennial time-scales. Low δ18O values, and hence negative phases of NAO that bring precipitation towards the Western Mediterranean, are observed during well-known solar minima periods. The results are consistent with previous models which describe low irradiance as a  trigger for southward shifts of precipitation-bearing westerlies during winter.

Late Palaeolithic cave art and permafrost in the Southern Ural.

Shulgan-Tash (also known as Kapova) cave located on the western slope of the Ural Mountains (Russia) is the easternmost European cave art monument of late Palaeolithic age. Radiocarbon dates from cultural layers in the cave suggest an age of about 16.3 to 19.6 ka (cal BP), but dates directly on the paintings were not obtained. In order to constrain the age of this art using an independent method, we performed detailed 230Th-U dating of calcite flowstone underlying and overgrowing the paintings at 22 sites in three halls of the cave. The youngest age for the underlying calcite (i.e., the maximum age of the cave art) is 36.4 ± 0.1 ka, and the oldest overlying calcite (constraining the minimum age of the cave art) is 14.5 ± 0.04 ka. The ca. 21.9 ka-long hiatus in calcite deposition during which the paintings were made is attributed to regional permafrost conditions and sub-zero temperatures inside the cave during Marine Isotope Stage (MIS) 2. This is supported by samples of cryogenic cave calcite, which document seven episodes of freezing and thawing of permafrost associated with stadials and interstadials of MIS 3, respectively.

Changes to Yucatán Peninsula precipitation associated with salinity and temperature extremes of the Caribbean Sea during the Maya civilization collapse.

Explanations of the Classic Maya civilization demise on the Yucatán Peninsula during the Terminal Classic Period (TCP; ~CE 750-1050) are controversial. Multiyear droughts are one likely cause, but the role of the Caribbean Sea, the dominant moisture source for Mesoamerica, remains largely unknown. Here we present bimonthly-resolved snapshots of reconstructed sea surface temperature (SST) and salinity (SSS) variability in the southern Caribbean from precisely dated fossil corals. The results indicate pronounced interannual to decadal SST and SSS variability during the TCP, which may be temporally coherent to precipitation anomalies on the Yucatán. Our results are best explained by changed Caribbean SST gradients affecting the Caribbean low-level atmospheric jet with consequences for Mesoamerican precipitation, which are possibly linked to changes in Atlantic Meridional Overturning Circulation strength. Our findings provide a new perspective on the anomalous hydrological changes during the TCP that complement the oft-suggested southward displacement of the Intertropical Convergence Zone. We advocate for a strong role of Caribbean SST and SSS condition changes and related ocean-atmosphere interactions that notably influenced the propagation and transport of precipitation to the Yucatán Peninsula during the TCP.

Tides in the Last Interglacial: insights from notch geometry and palaeo tidal models in Bonaire, Netherland Antilles.

The study of past sea levels relies largely on the interpretation of sea-level indicators. Palaeo tidal notches are considered as one of the most precise sea-level indicators as their formation is closely tied to the local tidal range. We present geometric measurements of modern and palaeo (Marine Isotope Stage (MIS) 5e) tidal notches on Bonaire (southern Caribbean Sea) and results from two tidal simulations, using the present-day bathymetry and a palaeo-bathymetry. We use these two tools to investigate changes in the tidal range since MIS 5e. Our models show that the tidal range changes most significantly in shallow areas, whereas both, notch geometry and models results, suggest that steeper continental shelves, such as the ones bordering the island of Bonaire, are less affected to changes in tidal range in conditions of MIS 5e sea levels. We use our data and results to discuss the importance of considering changes in tidal range while reconstructing MIS 5e sea level histories, and we remark that it is possible to use hydrodynamic modelling and notch geometry as first-order proxies to assess whether, in a particular area, tidal range might have been different in MIS 5e with respect to today.

TERMITE: An R script for fast reduction of laser ablation inductively coupled plasma mass spectrometry data and its application to trace element measurements.

RATIONALE: High spatial resolution Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS) determination of trace element concentrations is of great interest for geological and environmental studies. Data reduction is a very important aspect of LA-ICP-MS, and several commercial programs for handling LA-ICPMS trace element data are available. Each of these software packages has its specific advantages and disadvantages. METHODS: Here we present TERMITE, an R script for the reduction of LA-ICPMS data, which can reduce both spot and line scan measurements. Several parameters can be adjusted by the user, who does not necessarily need prior knowledge in R. Currently, ten reference materials with different matrices for calibration of LA-ICPMS data are implemented, and additional reference materials can be added by the user. TERMITE also provides an optional outlier test, and the results are provided graphically (as a pdf file) as well as numerically (as a csv file). RESULTS: As an example, we apply TERMITE to a speleothem sample and compare the results with those obtained using the commercial software GLITTER. The two programs give similar results. TERMITE is particularly useful for samples that are homogeneous with respect to their major element composition (in particular for the element used as an internal standard) and when many measurements are performed using the same analytical parameters. In this case, data evaluation using TERMITE is much faster than with all other available software, and the concentrations of more than 100 single spot measurements can be calculated in less than a minute. CONCLUSIONS: TERMITE is an open-source software for the reduction of LA-ICPMS data, which is particularly useful for the fast, reproducible evaluation of large datasets of samples that are homogeneous with respect to their major element composition. Copyright © 2017 John Wiley & Sons, Ltd.

Climate variations of Central Asia on orbital to millennial timescales.

The extent to which climate variability in Central Asia is causally linked to large-scale changes in the Asian monsoon on varying timescales remains a longstanding question. Here we present precisely dated high-resolution speleothem oxygen-carbon isotope and trace element records of Central Asia's hydroclimate variability from Tonnel'naya cave, Uzbekistan, and Kesang cave, western China. On orbital timescales, the supra-regional climate variance, inferred from our oxygen isotope records, exhibits a precessional rhythm, punctuated by millennial-scale abrupt climate events, suggesting a close coupling with the Asian monsoon. However, the local hydroclimatic variability at both cave sites, inferred from carbon isotope and trace element records, shows climate variations that are distinctly different from their supra-regional modes. Particularly, hydroclimatic changes in both Tonnel'naya and Kesang areas during the Holocene lag behind the supra-regional climate variability by several thousand years. These observations may reconcile the apparent out-of-phase hydroclimatic variability, inferred from the Holocene lake proxy records, between Westerly Central Asia and Monsoon Asia.

Chronology for the Cueva Victoria fossil site (SE Spain): Evidence for Early Pleistocene Afro-Iberian dispersals.

Cueva Victoria has provided remains of more than 90 species of fossil vertebrates, including a hominin phalanx, and the only specimens of the African cercopithecid Theropithecus oswaldi in Europe. To constrain the age of the vertebrate remains we used paleomagnetism, vertebrate biostratigraphy and (230)Th/U dating. Normal polarity was identified in the non-fossiliferous lowest and highest stratigraphic units (red clay and capping flowstones) while reverse polarity was found in the intermediate stratigraphic unit (fossiliferous breccia). A lower polarity change occurred during the deposition of the decalcification clay, when the cave was closed and karstification was active. A second polarity change occurred during the capping flowstone formation, when the upper galleries were filled with breccia. The mammal association indicates a post-Jaramillo age, which allows us to correlate this upper reversal with the Brunhes-Matuyama boundary (0.78 Ma). Consequently, the lower reversal (N-R) is interpreted as the end of the Jaramillo magnetochron (0.99 Ma). These ages bracket the age of the fossiliferous breccia between 0.99 and 0.78 Ma, suggesting that the capping flowstone was formed during the wet Marine Isotopic Stage 19, which includes the Brunhes-Matuyama boundary. Fossil remains of Theropithecus have been only found in situ ∼1 m below the B/M boundary, which allows us to place the arrival of Theropithecus to Cueva Victoria at ∼0.9-0.85 Ma. The fauna of Cueva Victoria lived during a period of important climatic change, known as the Early-Middle Pleistocene Climatic Transition. The occurrence of the oldest European Acheulean tools at the contemporaneous nearby site of Cueva Negra suggest an African dispersal into SE Iberia through the Strait of Gibraltar during MIS 22, when sea-level was ∼100 m below its present position, allowing the passage into Europe of, at least, Theropithecus and Homo bearing Acheulean technology.

Tropical Atlantic temperature seasonality at the end of the last interglacial.

The end of the last interglacial period, ~118 kyr ago, was characterized by substantial ocean circulation and climate perturbations resulting from instabilities of polar ice sheets. These perturbations are crucial for a better understanding of future climate change. The seasonal temperature changes of the tropical ocean, however, which play an important role in seasonal climate extremes such as hurricanes, floods and droughts at the present day, are not well known for this period that led into the last glacial. Here we present a monthly resolved snapshot of reconstructed sea surface temperature in the tropical North Atlantic Ocean for 117.7±0.8 kyr ago, using coral Sr/Ca and δ(18)O records. We find that temperature seasonality was similar to today, which is consistent with the orbital insolation forcing. Our coral and climate model results suggest that temperature seasonality of the tropical surface ocean is controlled mainly by orbital insolation changes during interglacials.

Sensitivity of whole wood stable carbon and oxygen isotope values to milling procedures.

RATIONALE: Milling of wood samples is a widely applied preparation method for pooling tree-rings from different trees or periods of several years for determination of δ(13)C and δ(18)O values. In this study, whole wood samples were milled using different procedures in order to evaluate potential effects of this preparation method on δ(13)C and δ(18)O values. METHODS: Subsamples of a 5 cm(3) wood piece of a single tree-ring from a lowland white fir were used. The samples were milled with different setups: (i) two and three stainless-steel balls, (ii) 3, 5 and 8 min milling time, and (iii) discontinuous and continuous milling. The δ(13)C values were measured using an elemental analyser connected to an IsoPrime mass spectrometer and δ(18)O values using a Thermo Scientific MAT 253 mass spectrometer and a TC/EA connected by a ConFlo IV. RESULTS: The results show that varying the milling procedure does not alter the δ(13)C and δ(18)O values in comparison to non-milled blank samples. For shorter milling times, an increased variance of δ(18)O values is recorded, probably caused by isotopic gradient between early- and latewood portions of the tree-ring and thereby biasing the insufficiently homogenised samples. No overheating effects on the δ(13)C and δ(18)O values were detected. CONCLUSIONS: Milling of wood samples for carbon and oxygen isotope analyses is an appropriate preparation method.

Quantification of low molecular weight fatty acids in cave drip water and speleothems using HPLC-ESI-IT/MS -- development and validation of a selective method.

This study presents a novel method for the analysis of low molecular weight (LMW) fatty acids in cave drip water and speleothems. The method development included optimization of sample preparation procedures, e.g., blank reduction, solid phase extraction, concentration of extracts as well as liquid chromatography coupled to electrospray ion-trap mass spectrometry (HPLC-ESI-IT/MS) measurement parameters. Retention times for five analytes (lauric acid, myristic acid, palmitic acid, stearic acid and arachidic acid) were between 5 and 13.5 min. Spiking experiments were performed to accomplish external calibrations which ranged from 12.5 to 75 ng per spiked water sample. The correlation coefficient ranged from 0.9558 to 0.9989. Inter-batch precision, expressed as the relative standard deviation of three replicates, was <7 %. Limits of detection ranged from 0.77 to 55.97 ng for the diverse analytes; obtained recoveries varied from 30 to 103 %. For a first application, cave drip water and stalagmite samples from Herbstlabyrinth-Adventhöhle cave system were analyzed. Concentrations ranged from 38.37 to 9,982.54 ng L(-1) for water samples and 2.52 to 1,344.96 ng g(-1) for the stalagmite. Thereby, the different fatty acids showed a distinctive variation. Whereas shorter-chained fatty acids exhibited similarities, arachidic acid showed opposite trends. Diverse correlations were found, which could improve the understanding of different organic sources of the lipids transported by drip water and preserved in speleothems. This new method provides a more selective extraction process, particularly adjusted to LMW fatty acids and therefore reduces the required sample size. Furthermore, it is applicable to stalagmite as well as cave drip water samples.

Increased seasonality in Middle East temperatures during the last interglacial period.

The last interglacial period (about 125,000 years ago) is thought to have been at least as warm as the present climate. Owing to changes in the Earth's orbit around the Sun, it is thought that insolation in the Northern Hemisphere varied more strongly than today on seasonal timescales, which would have led to corresponding changes in the seasonal temperature cycle. Here we present seasonally resolved proxy records using corals from the northernmost Red Sea, which record climate during the last interglacial period, the late Holocene epoch and the present. We find an increased seasonality in the temperature recorded in the last interglacial coral. Today, climate in the northern Red Sea is sensitive to the North Atlantic Oscillation, a climate oscillation that strongly influences winter temperatures and precipitation in the North Atlantic region. From our coral records and simulations with a coupled atmosphere-ocean circulation model, we conclude that a tendency towards the high-index state of the North Atlantic Oscillation during the last interglacial period, which is consistent with European proxy records, contributed to the larger amplitude of the seasonal cycle in the Middle East.