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Despite decades of research, the influence of climate on the export of dissolved organic carbon (DOC) from soil remains poorly constrained, adding uncertainty to global carbon models. The limited temporal range of contemporary monitoring data, ongoing climate reorganisation and confounding anthropogenic activities muddy the waters further. Here, we reconstruct DOC leaching over the last ~14,000 years using alpine environmental archives (two speleothems and one lake sediment core) across 4° of latitude from Te Waipounamu/South Island of Aotearoa New Zealand. We selected broadly comparable palaeoenvironmental archives in mountainous catchments, free of anthropogenically-induced landscape changes prior to ~1200 C.E. We show that warmer temperatures resulted in increased allochthonous DOC export through the Holocene, most notably during the Holocene Climatic Optimum (HCO), which was some 1.5-2.5 °C warmer than the late pre-industrial period-then decreased during the cooler mid-Holocene. We propose that temperature exerted the key control on the observed doubling to tripling of soil DOC export during the HCO, presumably via temperature-mediated changes in vegetative soil C inputs and microbial degradation rates. Future warming may accelerate DOC export from mountainous catchments, with implications for the global carbon cycle and water quality., (© 2024. The Author(s).)

The winter and summer monsoons in Southeast Asia are important but highly variable sources of rainfall. Current understanding of the winter monsoon is limited by conflicting proxy observations, resulting from the decoupling of regional atmospheric circulation patterns and local rainfall dynamics. These signals are difficult to decipher in paleoclimate reconstructions. Here, we present a winter monsoon speleothem record from Southeast Asia covering the Holocene and find that winter and summer rainfall changed synchronously, forced by changes in the Pacific and Indian Oceans. In contrast, regional atmospheric circulation shows an inverse relation between winter and summer controlled by seasonal insolation over the Northern Hemisphere. We show that disentangling the local and regional signal in paleoclimate reconstructions is crucial in understanding and projecting winter and summer monsoon variability in Southeast Asia., (© 2023. Springer Nature Limited.)

Fossil and archaeological evidence indicates that hominin dispersals into Southwest Asia occurred throughout the Pleistocene, including the expansion of Homo sapiens populations out of Africa. While there is evidence for hominin occupations in the Pleistocene in Iran, as evidenced by the presence of Lower to Upper Paleolithic archaeological sites, the extent to which humid periods facilitated population expansions into western Asia has remained unclear. To test the role of humid periods on hominin dispersals here we assess Paleolithic site distributions and paleoenvironmental records across Iran. We developed the first spatially comprehensive, high-resolution paleohydrological model for Iran in order to assess water availability and its influence on hominin dispersals. We highlight environmentally mediated routes which likely played a key role in Late Pleistocene hominin dispersals, including the expansion of H. sapiens and Neanderthals eastwards into Asia. Our combined analyses indicate that, during MIS 5, there were opportunities for hominins to traverse a northern route through the Alborz and Kopet Dagh Mountains and the Dasht-I Kavir desert owing to the presence of activated fresh water sources. We recognize a new southern route along the Zagros Mountains and extending eastwards towards Pakistan and Afghanistan. We find evidence for a potential northern route during MIS 3, which would have permitted hominin movements and species interactions in Southwest Asia. Between humid periods, these interconnections would have waned, isolating populations in the Zagros and Alborz Mountains, where hominins may have continued to have had access to water., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2023 Shoaee et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Classic Maya populations living in peri-urban states were highly dependent on seasonally distributed rainfall for reliable surplus crop yields. Despite intense study of the potential impact of decadal to centennial-scale climatic changes on the demise of Classic Maya sociopolitical institutions (750-950 CE), its direct importance remains debated. We provide a detailed analysis of a precisely dated speleothem record from Yok Balum cave, Belize, that reflects local hydroclimatic changes at seasonal scale over the past 1600 years. We find that the initial disintegration of Maya sociopolitical institutions and population decline occurred in the context of a pronounced decrease in the predictability of seasonal rainfall and severe drought between 700 and 800 CE. The failure of Classic Maya societies to successfully adapt to volatile seasonal rainfall dynamics likely contributed to gradual but widespread processes of sociopolitical disintegration. We propose that the complex abandonment of Classic Maya population centres was not solely driven by protracted drought but also aggravated by year-to-year decreases in rainfall predictability, potentially caused by a regional reduction in coherent Intertropical Convergence Zone-driven rainfall., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2023.)

Recent wildfire activity in semi-arid regions like western North America exceeds the range of historical records. High-resolution paleoclimate archives such as stalagmites could illuminate the link between hydroclimate, vegetation change, and fire activity in pre-anthropogenic climate states beyond the timescale of existing tree-ring records. Here we present an analysis of levoglucosan, a combustion-sensitive anhydrosugar, and lignin oxidation products (LOPs) in a stalagmite, reconstructing fire activity and vegetation composition in the California Coast Range across the 8.2 kyr event. Elevated levoglucosan concentrations suggest increased fire activity while altered LOP compositions indicate a shift toward more woody vegetation during the event. These changes are concurrent with increased hydroclimate volatility as shown by carbon and calcium isotope proxies. Together, these records suggest that climate whiplash (oscillations between extreme wetness and aridity) and fire activity in California, both projected to increase with anthropogenic climate change, were tightly coupled during the early Holocene., (© 2022. The Author(s).)

Central Asia is positioned at a crossroads linking several zones important to hominin dispersal during the Middle Pleistocene. However, the scarcity of stratified and dated archaeological material and paleoclimate records makes it difficult to understand dispersal and occupation dynamics during this time period, especially in arid zones. Here we compile and analyze paleoclimatic and archaeological data from Pleistocene Central Asia, including examination of a new layer-counted speleothem-based multiproxy record of hydrological changes in southern Uzbekistan at the end of MIS 11. Our findings indicate that Lower Palaeolithic sites in the steppe, semi-arid, and desert zones of Central Asia may have served as key areas for the dispersal of hominins into Eurasia during the Middle Pleistocene. In agreement with previous studies, we find that bifaces occur across these zones at higher latitudes and in lower altitudes relative to the other Paleolithic assemblages. We argue that arid Central Asia would have been intermittently habitable during the Middle Pleistocene when long warm interglacial phases coincided with periods when the Caspian Sea was experiencing consistently high water levels, resulting in greater moisture availability and more temperate conditions in otherwise arid regions. During periodic intervals in the Middle Pleistocene, the local environment of arid Central Asia was likely a favorable habitat for paleolithic hominins and was frequented by Lower Paleolithic toolmakers producing bifaces., Competing Interests: The authors have decades that no competing interests exist.

Protracted droughts lasting years to decades constitute severe threats to human welfare across the Indian subcontinent. Such events are, however, rare during the instrumental period ( ca . since 1871 CE). In contrast, the historic documentary evidence indicates the repeated occurrences of protracted droughts in the region during the preinstrumental period implying that either the instrumental observations underestimate the full spectrum of monsoon variability or the historic accounts overestimate the severity and duration of the past droughts. Here we present a temporally precise speleothem-based oxygen isotope reconstruction of the Indian summer monsoon precipitation variability from Mawmluh cave located in northeast India. Our data reveal that protracted droughts, embedded within multidecadal intervals of reduced monsoon rainfall, frequently occurred over the past millennium. These extreme events are in striking temporal synchrony with the historically documented droughts, famines, mass mortality events, and geopolitical changes in the Indian subcontinent. Our findings necessitate reconsideration of the region's current water resources, sustainability, and mitigation policies that discount the possibility of protracted droughts in the future.

The influence of climate change on civil conflict and societal instability in the premodern world is a subject of much debate, in part because of the limited temporal or disciplinary scope of case studies. We present a transdisciplinary case study that combines archeological, historical, and paleoclimate datasets to explore the dynamic, shifting relationships among climate change, civil conflict, and political collapse at Mayapan, the largest Postclassic Maya capital of the Yucatán Peninsula in the thirteenth and fourteenth centuries CE. Multiple data sources indicate that civil conflict increased significantly and generalized linear modeling correlates strife in the city with drought conditions between 1400 and 1450 cal. CE. We argue that prolonged drought escalated rival factional tensions, but subsequent adaptations reveal regional-scale resiliency, ensuring that Maya political and economic structures endured until European contact in the early sixteenth century CE., (© 2022. The Author(s).)

Some of the earliest evidence for the presence of modern humans in rainforests has come from the fossil deposits of Lida Ajer in Sumatra. Two human teeth from this cave were estimated to be 73-63 thousand years old, which is significantly older than some estimates of modern human migration out of Africa based on genetic data. The deposits were interpreted as being associated with a rainforest environment based largely on the presence of abundant orangutan fossils. As well as the main fossil-bearing chamber, fossil-bearing passages are present below a sinkhole, although the relationship between the different fossil deposits has only been tenuously established. Here, we provide significant new sedimentological, geochronological and palaeoecological data aimed at reconstructing the speleological and environmental history of the cave and the clastic and fossil deposits therein. Our data suggest that the Lida Ajer fossils were deposited during Marine Isotope Stage 4, with fossils from the lower passages older than the main fossil chamber. Our use of stable carbon and oxygen isotope analyses of mammalian tooth enamel demonstrates that early humans probably occupied a closed-canopy forest very similar to those present in the region today, although the fossil orangutans may have occupied a slightly different niche. This article is part of the theme issue 'Tropical forests in the deep human past'.

The analysis of irregularly sampled time series remains a challenging task requiring methods that account for continuous and abrupt changes of sampling resolution without introducing additional biases. The edit distance is an effective metric to quantitatively compare time series segments of unequal length by computing the cost of transforming one segment into the other. We show that transformation costs generally exhibit a nontrivial relationship with local sampling rate. If the sampling resolution undergoes strong variations, this effect impedes unbiased comparison between different time episodes. We study the impact of this effect on recurrence quantification analysis, a framework that is well suited for identifying regime shifts in nonlinear time series. A constrained randomization approach is put forward to correct for the biased recurrence quantification measures. This strategy involves the generation of a type of time series and time axis surrogates which we call sampling-rate-constrained (SRC) surrogates. We demonstrate the effectiveness of the proposed approach with a synthetic example and an irregularly sampled speleothem proxy record from Niue island in the central tropical Pacific. Application of the proposed correction scheme identifies a spurious transition that is solely imposed by an abrupt shift in sampling rate and uncovers periods of reduced seasonal rainfall predictability associated with enhanced El Niño-Southern Oscillation and tropical cyclone activity.

Large changes in hydroclimate in the Neotropics implied by proxy evidence, such as during the Little Ice Age, have been attributed to meridional shifts of the intertropical convergence zone (ITCZ), although alternative modes of ITCZ variability have also been suggested. Here, we use seasonally resolved stalagmite rainfall proxy data from the modern northern limit of the ITCZ in southern Belize, combined with records from across the Neotropics and subtropics, to fingerprint ITCZ variability during the Common Era. Our data are consistent with models that suggest ITCZ expansion and weakening during globally cold climate intervals and contraction and intensification during global warmth. As a result, regions currently in the margins of the ITCZ in both hemispheres are likely transitioning to more arid and highly variable conditions, aggravating current trends of increased social unrest and mass migration., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Tropical rainfall variability is closely linked to meridional shifts of the Intertropical Convergence Zone (ITCZ) and zonal movements of the Walker circulation. The characteristics and mechanisms of tropical rainfall variations on centennial to decadal scales are, however, still unclear. Here, we reconstruct a replicated stalagmite-based 2,700-y-long, continuous record of rainfall for the deeply convective northern central Indo-Pacific (NCIP) region. Our record reveals decreasing rainfall in the NCIP over the past 2,700 y, similar to other records from the northern tropics. Notable centennial- to decadal-scale dry climate episodes occurred in both the NCIP and the southern central Indo-Pacific (SCIP) during the 20th century [Current Warm Period (CWP)] and the Medieval Warm Period (MWP), resembling enhanced El Niñ o -like conditions. Further, we developed a 2,000-y-long ITCZ shift index record that supports an overall southward ITCZ shift in the central Indo-Pacific and indicates southward mean ITCZ positions during the early MWP and the CWP. As a result, the drying trend since the 20 th century in the northern tropics is similar to that observed during the past warm period, suggesting that a possible anthropogenic forcing of rainfall remains indistinguishable from natural variability., Competing Interests: The authors declare no conflict of interest., (Copyright © 2019 the Author(s). Published by PNAS.)

In climates with strongly seasonal rainfall, speleothem-based paleoclimate reconstructions are often thought to reflect wet season conditions, assuming a bias toward the season with greater water supply. This is particularly true in monsoon regions, where speleothem records are interpreted to document monsoon strength changes on multiple timescales. Dry season infiltration variability and rainfall seasonality are not typically considered in these reconstructions, even though cave ventilation could bias speleothem growth toward the cooler season. To investigate the influence of dry season infiltration on speleothem geochemistry, we combine a modern, sub-seasonally resolved trace element record from Mawmluh Cave in Northeast India with forward modeling experiments. We find that variations in the amplitude of seasonal signals in speleothem Mg/Ca, which reflects prior carbonate precipitation, are more sensitive to dry season rather than monsoon season infiltration. This sensitivity may be enhanced by dry season cave ventilation. The Mawmluh speleothem Mg/Ca record is consistent with increased dry season rainfall during the 1976-1998 warm phase of the Pacific Decadal Oscillation relative to 1964-2013. Our work demonstrates the importance of considering non-monsoon season rainfall when interpreting speleothem paleoclimate records and suggests that trace elements could provide insight into periods of enhanced dry season infiltration in monsoonal climates.

About a decade after its introduction, the field of carbonate clumped isotope thermometry is rapidly expanding because of the large number of possible applications and its potential to solve long-standing questions in Earth Sciences. Major factors limiting the application of this method are the very high analytical precision required for meaningful interpretations, the relatively complex sample preparation procedures, and the mass spectrometric corrections needed. In this paper we first briefly review the evolution of the analytical and standardization procedures and discuss the major remaining sources of uncertainty. We propose that the use of carbonate standards to project the results to the carbon dioxide equilibrium scale can improve interlaboratory data comparability and help to solve long-standing discrepancies between laboratories and temperature calibrations. The use of carbonates reduces uncertainties related to gas preparation and cleaning procedures and ensures equal treatment of samples and standards. We present a set of carbonate standards of diverse composition, discuss how they can be used to correct for mass spectrometric biases, and demonstrate that their use significantly improves the comparability among four laboratories. We propose that the use of these standards or of a similar set of carbonate standards will improve the comparability of data across laboratories.

Identifying abrupt transitions is a key question in various disciplines. Existing transition detection methods, however, do not rigorously account for time series uncertainties, often neglecting them altogether or assuming them to be independent and qualitatively similar. Here, we introduce a novel approach suited to handle uncertainties by representing the time series as a time-ordered sequence of probability density functions. We show how to detect abrupt transitions in such a sequence using the community structure of networks representing probabilities of recurrence. Using our approach, we detect transitions in global stock indices related to well-known periods of politico-economic volatility. We further uncover transitions in the El Niño-Southern Oscillation which coincide with periods of phase locking with the Pacific Decadal Oscillation. Finally, we provide for the first time an 'uncertainty-aware' framework which validates the hypothesis that ice-rafting events in the North Atlantic during the Holocene were synchronous with a weakened Asian summer monsoon.

The presence of a low- to mid-latitude interhemispheric hydrologic seesaw is apparent over orbital and glacial-interglacial timescales, but its existence over the most recent past remains unclear. Here we investigate, based on climate proxy reconstructions from both hemispheres, the inter-hemispherical phasing of the Intertropical Convergence Zone (ITCZ) and the low- to mid-latitude teleconnections in the Northern Hemisphere over the past 2000 years. A clear feature is a persistent southward shift of the ITCZ during the Little Ice Age until the beginning of the 19th Century. Strong covariation between our new composite ITCZ-stack and North Atlantic Oscillation (NAO) records reveals a tight coupling between these two synoptic weather and climate phenomena over decadal-to-centennial timescales. This relationship becomes most apparent when comparing two precisely dated, high-resolution paleorainfall records from Belize and Scotland, indicating that the low- to mid-latitude teleconnection was also active over annual-decadal timescales. It is likely a combination of external forcing, i.e., solar and volcanic, and internal feedbacks, that drives the synchronous ITCZ and NAO shifts via energy flux perturbations in the tropics.

Accurately predicting future tropical cyclone risk requires understanding the fundamental controls on tropical cyclone dynamics. Here we present an annually-resolved 450-year reconstruction of western Caribbean tropical cyclone activity developed using a new coupled carbon and oxygen isotope ratio technique in an exceptionally well-dated stalagmite from Belize. Western Caribbean tropical cyclone activity peaked at 1650 A.D., coincident with maximum Little Ice Age cooling, and decreased gradually until the end of the record in 1983. Considered with other reconstructions, the new record suggests that the mean track of Cape Verde tropical cyclones shifted gradually north-eastward from the western Caribbean toward the North American east coast over the last 450 years. Since ~1870 A.D., these shifts were largely driven by anthropogenic greenhouse gas and sulphate aerosol emissions. Our results strongly suggest that future emission scenarios will result in more frequent tropical cyclone impacts on the financial and population centres of the northeastern United States.

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.

The East Asian-Indonesian-Australian summer monsoon (EAIASM) links the Earth's hemispheres and provides a heat source that drives global circulation. At seasonal and inter-seasonal timescales, the summer monsoon of one hemisphere is linked via outflows from the winter monsoon of the opposing hemisphere. Long-term phase relationships between the East Asian summer monsoon (EASM) and the Indonesian-Australian summer monsoon (IASM) are poorly understood, raising questions of long-term adjustments to future greenhouse-triggered climate change and whether these changes could 'lock in' possible IASM and EASM phase relationships in a region dependent on monsoonal rainfall. Here we show that a newly developed nonlinear time series analysis technique allows confident identification of strong versus weak monsoon phases at millennial to sub-centennial timescales. We find a see-saw relationship over the last 9,000 years-with strong and weak monsoons opposingly phased and triggered by solar variations. Our results provide insights into centennial- to millennial-scale relationships within the wider EAIASM regime.

A new instrumental setup, combining laser ablation (LA) with accelerator mass spectrometry (AMS), has been investigated for the online radiocarbon ((14)C) analysis of carbonate records. Samples were placed in an in-house designed LA-cell, and CO2 gas was produced by ablation using a 193 nm ArF excimer laser. The (14)C/(12)C abundance ratio of the gas was then analyzed by gas ion source AMS. This configuration allows flexible and time-resolved acquisition of (14)C profiles in contrast to conventional measurements, where only the bulk composition of discrete samples can be obtained. Three different measurement modes, i.e. discrete layer analysis, survey scans, and precision scans, were investigated and compared using a stalagmite sample and, subsequently, applied to terrestrial and marine carbonates. Depending on the measurement mode, a precision of typically 1-5% combined with a spatial resolution of 100 μm can be obtained. Prominent (14)C features, such as the atomic bomb (14)C peak, can be resolved by scanning several cm of a sample within 1 h. Stalagmite, deep-sea coral, and mollusk shell samples yielded comparable signal intensities, which again were comparable to those of conventional gas measurements. The novel LA-AMS setup allowed rapid scans on a variety of sample materials with high spatial resolution.

The Indian summer monsoon (ISM) monsoon is critical to billions of people living in the region. Yet, significant debates remain on primary ISM drivers on millennial-orbital timescales. Here, we use speleothem oxygen isotope (δ(18)O) data from Bittoo cave, Northern India to reconstruct ISM variability over the past 280,000 years. We find strong coherence between North Indian and Chinese speleothem δ(18)O records from the East Asian monsoon domain, suggesting that both Asian monsoon subsystems exhibit a coupled response to changes in Northern Hemisphere summer insolation (NHSI) without significant temporal lags, supporting the view that the tropical-subtropical monsoon variability is driven directly by precession-induced changes in NHSI. Comparisons of the North Indian record with both Antarctic ice core and sea-surface temperature records from the southern Indian Ocean over the last glacial period do not suggest a dominant role of Southern Hemisphere climate processes in regulating the ISM variability on millennial-orbital timescales.

The collapse of some pre-historical and historical cultures, including Chinese dynasties were presumably linked to widespread droughts, on the basis of synchronicities of societal crises and proxy-based climate events. Here, we present a comparison of ancient inscriptions in Dayu Cave from Qinling Mountains, central China, which described accurate times and detailed impacts of seven drought events during the period of 1520-1920 CE, with high-resolution speleothem records from the same cave. The comparable results provide unique and robust tests on relationships among speleothem δ(18)O changes, drought events, and societal unrest. With direct historical evidences, our results suggest that droughts and even modest events interrupting otherwise wet intervals can cause serious social crises. Modeling results of speleothem δ(18)O series suggest that future precipitation in central China may be below the average of the past 500 years. As Qinling Mountain is the main recharge area of two large water transfer projects and habitats of many endangered species, it is imperative to explore an adaptive strategy for the decline in precipitation and/or drought events.

Approximately half of the world's population lives in the tropics, and future changes in the hydrological cycle will impact not just the freshwater supplies but also energy production in areas dependent upon hydroelectric power. It is vital that we understand the mechanisms/processes that affect tropical precipitation and the eventual surface hydrological response to better assess projected future regional precipitation trends and variability. Paleo-climate proxies are well suited for this purpose as they provide long time series that pre-date and complement the present, often short instrumental observations. Here we present paleo-precipitation data from a speleothem located in Mesoamerica that reveal large multi-decadal declines in regional precipitation, whose onset coincides with clusters of large volcanic eruptions during the nineteenth and twentieth centuries. This reconstruction provides new independent evidence of long-lasting volcanic effects on climate and elucidates key aspects of the causal chain of physical processes determining the tropical climate response to global radiative forcing.

Observations show that summer rainfall over large parts of South Asia has declined over the past five to six decades. It remains unclear, however, whether this trend is due to natural variability or increased anthropogenic aerosol loading over South Asia. Here we use stable oxygen isotopes in speleothems from northern India to reconstruct variations in Indian monsoon rainfall over the last two millennia. We find that within the long-term context of our record, the current drying trend is not outside the envelope of monsoon's oscillatory variability, albeit at the lower edge of this variance. Furthermore, the magnitude of multi-decadal oscillatory variability in monsoon rainfall inferred from our proxy record is comparable to model estimates of anthropogenic-forced trends of mean monsoon rainfall in the 21st century under various emission scenarios. Our results suggest that anthropogenic-forced changes in monsoon rainfall will remain difficult to detect against a backdrop of large natural variability.

Rationale: Carbonate clumped isotope thermometry is a powerful new technique increasingly used in many fields in earth science. Recently, it has been shown that clumped isotope measurements can be performed with a Kiel carbonate preparation device and micro-volume analyses, allowing measurements of small (1.5-2 mg) carbonate samples. However, common data correction schemes rely on measurements of gases prepared offline, potentially leading to unrecognized biases in the results., Methods: We propose a new correction scheme for the Kiel device method including: (1) A pressure-sensitive baseline correction (PBL) of the raw beam signals; (2) Transfer of data to the absolute reference frame; (3) Correction for acid fractionation; (4) Correction for average standard offsets; (5) When necessary, correction for Δ47 scale compression based on offsets among standards with different ordering state. The long-term performance of the new scheme was tested with a large set of standard measurements (N = 432) obtained over the course of 15 months., Results: The PBL correction reliably removes composition-dependent artifacts, which are commonly corrected for with gas measurements, and offsets observed in micro-volume measurements when ion beams are imbalanced. We show that the shape of the PBL can vary strongly and needs to be properly characterized. Combined PBL and standard correction resulted in long-term stability with standard deviations in Δ47 of 0.012-0.016 ‰ for the five standards over the whole period, close to the average error of 0.011 ‰ observed for individual measurements consisting of 10 replicate analyses., Conclusions: Our correction scheme eliminates the need for routine gas measurements, allowing for equal treatment of samples and standards with the Kiel device setup. While the PBL and standard data obtained over 15 months reveal variable mass spectrometer behavior, they provide a robust means of correction, yielding reproducible results from small carbonate samples in the long term., (Copyright © 2014 John Wiley & Sons, Ltd.)

Rationale: The measurement of the abundances of minor isotopologues by mass spectrometry requires correction of subtle non-linearities in the mass spectrometer that cause deviations in the relationship between actual and measured isotope ratios. Here we show that negative backgrounds on the Faraday cups recording the minor ion beams are the cause of the observed non-linearities in the measurement of CO(2) isotopologues, and propose a new correction procedure for clumped isotope measurements., Methods: We carefully investigated the cause of non-linearity effects in the measurement of the abundance of (13)C(18)O(16)O, a minor isotopologue of CO(2) with m/z 47, on two different mass spectrometers. By using gases of different composition with close to stochastic and with non-random distribution of isotopes we demonstrate that the apparent dependence of the excess abundance of the isotopologue of m/z 47 on the bulk isotopic composition of CO(2) is due to a background interference that is linearly dependent on the partial pressure of the gas in the source of the mass spectrometer., Conclusions: Background determination with gas flowing into the source of the mass spectrometer is necessary for accurate clumped isotope measurements of CO(2). Background corrections can be performed accurately if the slit width of the m/z 44 Faraday cup significantly exceeds that of the one for m/z 47, using a correlation between m/z 44 signal intensity and the corresponding minimum in m/z 47 background. We propose two new correction schemes that reduce the time-consuming measurement of gases of different bulk isotopic compositions. These findings may also be relevant for the measurement of other rare isotopologues by mass spectrometry., (Copyright © 2013 John Wiley & Sons, Ltd.)

The role of climate change in the development and demise of Classic Maya civilization (300 to 1000 C.E.) remains controversial because of the absence of well-dated climate and archaeological sequences. We present a precisely dated subannual climate record for the past 2000 years from Yok Balum Cave, Belize. From comparison of this record with historical events compiled from well-dated stone monuments, we propose that anomalously high rainfall favored unprecedented population expansion and the proliferation of political centers between 440 and 660 C.E. This was followed by a drying trend between 660 and 1000 C.E. that triggered the balkanization of polities, increased warfare, and the asynchronous disintegration of polities, followed by population collapse in the context of an extended drought between 1020 and 1100 C.E.