Search

This study details an aluminum‐catalyzed regioselective isomerization of 2,2‐disubstituted oxetanes to yield homoallylic alcohols. The reaction takes place in toluene at 40 °C, employing 1 mol % of Al(C6F5)3 as catalyst. This catalytic system shows a wide substrate scope (12 examples). The optimized conditions are especially useful for electron‐rich aryl oxetanes, completely suppressing the formation of allyl isomers and reducing the amount of the dimer by‐product. The synthetic applicability of the reported methodology is demonstrated by the enantioselective formal synthesis of curcuquinone and the σ1 receptor agonist RC‐33. [ABSTRACT FROM AUTHOR]

Hibernation (i.e., seasonal or multiday torpor) has been described in mammals from five continents and represents an important adaptation for energy economy. However, direct quantifications of energy savings by hibernation are challenging because of the complexities of estimating energy expenditure in the field. Here, we applied quantitative magnetic resonance to determine body fat and body composition in hibernating Dromiciops gliroides (monito del monte). During an experimental period of 31 d in winter, fat was significantly reduced by 5.72 ± 0.45 g, and lean mass was significantly reduced by 2.05 ± 0.14 g. This fat and lean mass consumption is equivalent to a daily energy expenditure of hibernation (DEEH) of 8.89 ± 0.6 kJ d−1, representing 13.4% of basal metabolic rate, with a proportional contribution of fat and lean mass consumption to DEEH of 81% and 18%, respectively. During the deep heterothermic bouts of monitos, body temperature remained 0.41°C ± 0.2°C above ambient temperature, typical of hibernators. Animals shut down metabolism and passively cool down to a critical defended temperature of 5.0°C ± 0.1°C, where they begin thermoregulation in torpor. Using temperature data loggers, we obtained an empirical estimation of minimum thermal conductance of 3.37 ± 0.19 J g−1 h−1 °C−1, which is 107% of the expectation by allometric equations. With this, we parameterized body temperature/ambient temperature time series to calculate torpor parameters and metabolic rates in euthermia and torpor. Whereas the acute metabolic fall in each torpor episode is about 96%, the energy saved by hibernation is 88% (compared with the DEE of active animals), which coincides with values from the literature at similar body mass. Thus, estimating body composition provides a simple method to measure the energy saved by hibernation in mammals. [ABSTRACT FROM AUTHOR]

This study examines the first precisely dated and temporally highly resolved speleothem record from Iberia that reconstructs the Oldest Dryas (OD). The onset of cold conditions in the study area, contemporary with the beginning of Heinrich Stadial 1, is recorded at 18.13 ± 0.08 ka, with a pronounced drop of 6.1‰ in δ13C in 250 years. Henceforth, stadial conditions depict a period of instability in the Atlantic Meridional Overturning Circulation, peaking in freshwater input from iceberg melting during Heinrich Event 1. Anomalies in the δ18O of the stalagmite attributed to such a freshwater event are found from 16.17 to 15.89 ka. Such absolute dates given to the onset of the OD in Iberia and to the main iceberg discharges are reliable anchor points for non-absolute chronologies. Two periods are identified in the OD: OD-a (18.13–16.17 ka) is characterized by wet conditions and a faster growth rate, and OD-b (15.89–14.81 ka) exhibits relative dryness and a slower growth rate. The sudden release of fresh water is considered to be the reason for the disruption of rainfall patterns in eastern Iberia. The present study also highlights the existence of heterogeneous and complex hydrological conditions during the OD in Iberia when both Atlantic and Mediterranean realms are considered. [ABSTRACT FROM AUTHOR]

During the Bronze and Iron Age, Sardinia was home of one of the most technologically advanced Mediterranean societies (the Nuragic culture). Given its key geographical location, the island was also the fulcrum of deep cultural exchanges. Toward the end of the Iron Age, Phoenicians, and especially Carthaginians and Romans, massively frequented Sardinia for different purposes. This marks an important cultural transition for the region, as the ancient Nuragic-related society terminated. At the same time, this impacted the subsistence and land use practices. Together with middle to late Holocene climate changes, the novel anthropic activities had a pivotal role in shaping the landscape around the island. However, high resolution climate and environmental records for these culturally important phases are still lacking in Sardinia. Thus, this paper explores palaeoenvironmental changes from the Bronze Age to post Iron Ages times by using carbonate speleothems from Suttaterra de Sarpis Cave (Urzulei, central east Sardinia), strategically located nearby the Or Murales Nuragic Village. U–Th ages (n = 20) indicate that five stalagmites comprehensively span the last ∼7000 years. Peculiarly, they all show an evident stratigraphic discontinuity. Age models attest that hiatuses can be at times associated with the discontinuities, spanning periods of ∼1200 to ∼200 years. Importantly, the discontinuities occurred from the Late Iron Age to the Roman period. Based on fabric observations, trace elements and δ13C- δ18O analyses, the discontinuities are primarily attributed to a progressive change of land use above the cave. We suppose that deforestation aimed to clearance for agriculture and livestock practices probably was the most impacting factor for infiltration dynamics and soil state, thus affecting the studied speleothems, although archaeological and historical data are absent for the specific study area. Instead, this is in line with the cultural transition occurring in Sardinia toward the end of the Iron Age, with novel agricultural practices imported by the overseas populations. The anthropic disturbance to the millennial-long karst equilibrium possibly overprinted the response of speleothem proxies to climate oscillations, although future higher resolution analyses are necessary to better investigate the evolution of climate during the Holocene as well as its role in the development of ancient civilizations. Indeed, this is the first speleothem-based Holocene palaeoenvironmental reconstruction accomplished in Sardinia. Considering the paucity of natural lakes in this key location, speleothems here demonstrate their potential in exploring human-driven palaeoenvironmental changes during times of cultural transitions within the Mediterranean context. • The first Holocene speleothem paleoenvironmental record from Sardinia (Italy). • Changes in geochemical and physical speleothems' properties point to variation of land use. • Land use variation is connected to cultural shifts during intra- and post-Nuragic period. [ABSTRACT FROM AUTHOR]

Abstract This study was conducted in Ejulve cave (Spain, southwestern Europe) over a period of four years (2013–2016) to identify the factors affecting the isotopic composition of rainfall, dripwaters, and farmed calcite. The results indicate that δ18O of rainfall in the study area was mainly controlled by the temperature effect (r 2 = 0.82, p -value < 0.001) with source effect and amount effect being secondary controls. Additionally, it exhibited a seasonal pattern with lower values indicated during winter and higher in summer. The use of effective infiltration to evaluate the recharge of the epikarst is extremely important in semi-arid karst climate conditions. This analysis revealed that while the amount effect exerted a moderate control on the annual δ18O in rainfall, it had a lower influence on the isotopic variability of the rainfall potentially infiltrating the karst aquifer. The sampling of 12 drip locations in Ejulve cave indicated that seepage and seasonal drips featured similar δ18O values in dripwaters. The homogenisation process during the infiltration in the epikarst was not complete, therefore, the δ18O seasonality seen in rainfall was also observed in dripwater δ18O, albeit attenuated and lagged. With the seasonal increase in rainfall in autumn, drip rates of seasonal and seepage groups increased within a few weeks. However, the lower δ18O of autumn–winter rain was observed in dripwaters with a lag as long as 21 weeks. The δ18O in farmed calcite showed a small variation of 0.11‰ while the δ13C varied seasonally with a variation of about 0.22‰ and indicated higher values during summer and autumn and lower values in winter and spring. Seasonal and seepage sites exhibited similar δ18O variability. However, δ13C was more positive in seepage sites and was enhanced by degassing kinetics to produce a variability of up to 0.42‰ in contrast to the 0.29‰ observed in the seasonal sites. The δ18O of calcite showed dependence on the δ18O of dripwater with a weak influence of the drip rate. However, δ13C exhibited a higher correlation with the drip rate and high δ13C was explained by enhanced degassing and low water availability while low δ13C values were in concordance with higher microbial activity, vegetation productivity, and greater water availability. The ventilation of the cave during late autumn through spring favoured the higher calcite deposition rates found during that time. [ABSTRACT FROM AUTHOR]

The Late Quaternary glacial-interglacial transitions represent the highest amplitude climate changes over the last million years. Unraveling the sequence of events and feedbacks at Termination III (T-III), including potential abrupt climate reversals similar to those of the last Termination, has been particularly challenging due to the scarcity of well-dated records worldwide. Here, we present speleothem data from southern Europe covering the interval from 262.7 to 217.9 kyBP, including the transition from marine isotope stage (MIS) 8 to MIS 7e. High-resolution δ13C, δ18O, and Mg/Ca profiles reveal major millennial-scale changes in aridity manifested in changing water availability and vegetation productivity. uranium-thorium dates provide a solid chronology for two millennial-scale events (S8.1 and S8.2) which, compared with the last two terminations, has some common features with Heinrich 1 and Heinrich 2 in Termination I (T-I). [ABSTRACT FROM AUTHOR]

New speleothem records from northeastern Iberian caves provide data to explore the climatic patterns during the Holocene. We present δ13C and Mg/Ca from three speleothems from two different caves located in the Iberian Range allowing replication of the climatic signal for several millennia. Through the integration of those stalagmites covering since the Holocene onset to 2 ka, the early Holocene (11.7–8.5 ka) appears as the wettest interval. A marked change towards aridity is observed during the middle Holocene (8.5–4.8 ka) and an increase of humidity afterwards (4.8–2 ka). This three-part pattern, contrasting with other Iberian sequences, seems to be associated with the different role that seasonality has played in the response of different proxies (or records) to changes in water availability. Interpreting our speleothem records as changes in winter-spring precipitation along the Holocene allows reconciling previous data on hydrological variability from the western Mediterranean borderlands. [ABSTRACT FROM PUBLISHER]

High-resolution and precisely dated hydroclimate records in the southeastern Tibetan Plateau (TP) remain sparse beyond the Holocene, which hampers our ability to understand the hydroclimate variability in this important Indian summer monsoon (ISM) fringe area and its global teleconnection. Here we present 3-y resolution δ18O and δ13C records from a laminated stalagmite (RG-3) from Rige Cave in the southeastern TP, spanning the Younger Dryas (YD). The records allow us to precisely characterize the timing, structure, and particularly centennial-scale events within the YD, and probe the control factors of precipitation δ18O (δ18O p) in the ISM fringe area. On centennial–millennial timescales, the Rige δ18O record shows coherent pattern with the East Asian summer monsoon (EASM) counterpart, combined with modeled δ18O p results and spatial analysis, suggesting that δ18O p in this part of the TP is largely controlled by the large-scale atmosphere circulation (or the ISM strength), and the altitude increase in the TP may not potentially result in an opposite δ18O p pattern at least in the monsoonal TP regime. We also found significant δ13C-δ18O covariation on the centennial timescale, suggesting a coincided ISM rainfall and biomass change during the YD. In the Rige records, one weak centennial-scale ISM event (namely the intra-Allerød cold period, IACP) and three strong centennial-scale ISM events within the YD (namely A1′-A2′-A3′) were prominent and occurred between ∼12,470 and 12,310 ± 14, ∼12,210–12,090 ± 12 and ∼12,010–11,920 ± 12 y BP (before present, where present = 1950 CE), respectively. Spectral analyses of Rige records also revealed a significant ∼200-y periodicity, which is nearly in-phase with observed centennial-scale variations of the North Atlantic temperature and mid-latitude westerly-jet during that time. These observations support the hypothesis that the solar de Vries cycle (207-y) triggered the centennial-scale climate variations in high northern latitude, leading to the ISM variations via fast atmospheric processes. • Precipitation δ18O and its millennial-centennial patterns in SE Tibet Plateau are controlled by large monsoon circulations • Centennial δ13C-δ18O covariations in Younger Dryas suggest a link of the local biomass to Indian summer monsoon rainfall • Centennial Indian summer monsoon events in Younger Dryas correlate precisely to the North Atlantic climate variations • Solar de Vries cycle (207-y) triggered centennial Indian summer monsoon variations via North Atlantic climate changes [ABSTRACT FROM AUTHOR]

As a consequence of globalization many processes in human life have changed, which includes how to learn and teach. In this specific scenario ICTs have been positioning themselves in the educational process to become a major facilitator and motivator of learning. In this study we would present the use of virtual portfolio and blog as a space for the development of collaborative learning in the training of social workers at the Catholic University of Maule, and how this tool was perceived by students. [ABSTRACT FROM AUTHOR]

Multiple geochemical proxies (e.g., trace elements, δ18O and δ13C) and precise 230Th ages in speleothems are crucial for conducting robust paleoclimatic reconstructions, but the impact of diagenesis on these proxies and 230Th ages is not well-established. In this study, we investigate the petrography and geochemical composition of six aragonite-calcite stalagmites from Shennong Cave in southeastern China to analyze the transformation from aragonite to calcite (primary versus secondary) and its effects on geochemical proxies and 230Th ages. No aragonite relics are observed in columnar calcite in four aragonite-calcite stalagmites (SN55, SN49, SN104 and SNB1), although traces of aragonite exist between the calcite crystals or grow parallel at the aragonite-calcite borders. This is different from the obvious aragonite relics preserved in secondary mosaic calcite in the other two aragonite-calcite stalagmites (SN3 and SN15). Both mosaic and columnar calcite show various changes in geochemical proxies and 230Th ages compared with primary aragonite. The trend in the geochemical proxies analyzed (trace elements, δ18O and δ13C) of columnar calcite remains consistent with those of aragonite, despite significant differences in their absolute values within the overlapping periods. These differences are due to the different fractionation coefficients of isotopes and trace elements in aragonite and calcite formed under the same solution conditions rather than late diagenesis. The 230Th ages of columnar calcite are similar to those of primary aragonite, and the values of subsamples from the same calcite layer are consistent. In contrast, the trace elements and δ13C values of mosaic calcite are similar to those of primary aragonite, while its 230Th age significantly differs from that of primary aragonite, exhibiting no consistent patterns. Therefore, these geochemical characteristics of columnar calcite are significantly different from secondary mosaic calcite, indicating that the columnar calcite in these four aragonite-calcite stalagmites is primary. A comparison of trace elements and δ13C records between aragonite-calcite and pure aragonite stalagmites during the overlapping period further confirms that these columnar calcites are primary. Their geochemical proxies can be used for paleoclimate reconstruction after careful evaluation, and the transformation from aragonite to columnar calcite is caused by increased precipitation. However, due to age and geochemical proxies change, secondary mosaic calcite is unsuitable for paleoclimate reconstruction, unlike columnar calcite. This study provides competent evidence to identify whether calcite in aragonite-calcite stalagmites is primary versus secondary and whether it can be used for paleoclimatic reconstruction. [ABSTRACT FROM AUTHOR]

The climate during the last glacial cycle was characterized by abrupt millennial-scale changes superimposed on long-term orbital control. This study examines this climate variability for northeast Iberia for the time interval 118.9 to 36.9 kyr using a multi-proxy approach (δ18O, δ13C and Mg/Ca) applied to a stalagmite that covers this period continuously. During Marine Isotope Stage (MIS) 5 and 4, δ18O is controlled by orbital pacing, whereby more humid conditions prevailed during minima in boreal summer precession. In contrast, during MIS 3 δ18O lags precession and co-varies with δ13C (ρ = 0.53, p-value < 0.001, n = 500), suggesting a common control of both isotopes by reduced precipitation during dry periods. δ13C shows a positive correlation with Mg/Ca, reflecting water availability, vegetation productivity and microbial activity in the catchment of the cave's drip water. The δ13C values exhibit a response to Heinrich Stadials (HS) and other cold marine events (e.g. C26 to C23), as well as Dansgaard-Oeschger oscillations (D-O). The Last Interglacial ended at 108.6 ± 0.3 kyr at this site. Two periods with a marked "W-shape" pattern in δ13C can be recognized between 70 and 50 kyr (hereafter multi-event). The older multi-event (including HS-6 and D-O 18) is characterized in the North Atlantic by high IRD discharges and cold sea-surface temperatures, while the two phases attending to the hydrology in the study area suggest dry conditions prior to HS-6. A dry climate prevailed during the younger multi-event (including HS-5a and D-O 15), coincident with an increase in productivity-related foraminifera species at lower latitudes, suggesting a reinforcement of the trade winds associated with a stronger Hadley Cell. • First continuous speleothem record from Europe covering MIS 5e to 3. • Precession-paced control of first-order δ18O variability during MIS 5. • Reduced precipitation controlled δ18O and δ13C millennial variability during MIS 4 and 3. • Late demise of the Last Interglacial in NE Iberia. • New insights into the climate variability during HS-6 and 5a, and D-O 15 and 18. [ABSTRACT FROM AUTHOR]

The penultimate deglaciation was characterized by a sub-millennial-scale warm event in the Heinrich Stadial 11(HS11), termed the 134-ka event. However, its precise timing and structure remain poorly constrained due to the lack of high-resolution and precisely dated records. We present an oxygen isotope record of a speleothem with well-developed annual lamina from Zhangjia Cave, located on the north margin of the Sichuan Basin, characterizing Asian summer monsoon (ASM) changes in the 134-ka event, which included an increase excursion of ca. 149 years and decrease excursion of ca. 200 years, inferred from 3.3‰ δ18O variations. This event also divided the weak ASM interval-II (WMI-II), corresponding to HS11, into two stages, the WMI-IIa 132.8–134.1 ka and WMI-IIb 134.4–136.4 ka. With a comparable climatic pattern globally, the 134-ka event is essentially similar to the millennial-scale events in last glacial–deglacial period. Particularly, the observed weak-strong-weak ASM sequence (138.8–132.8 ka) is largely controlled by changes in the Atlantic Meridional Overturning Circulation (AMOC) forced by the meltwater of northern high-latitude ice sheets. Moreover, our results underpin that AMOC, rather than the global ice volume, is more critical to ASM variations during the last two deglaciations. [ABSTRACT FROM AUTHOR]

The marsupial Monito del monte (Dromiciops gliroides) utilizes both daily and seasonal bouts of torpor to preserve energy and prolong survival during periods of cold and unpredictable food availability. Torpor involves changes in cellular metabolism, including specific changes to gene expression that is coordinated in part, by the posttranscriptional gene silencing activity of microRNAs (miRNA). Previously, differential miRNA expression has been identified in D. gliroides liver and skeletal muscle; however, miRNAs in the heart of Monito del monte remained unstudied. In this study, the expression of 82 miRNAs was assessed in the hearts of active and torpid D. gliroides, finding that 14 were significantly differentially expressed during torpor. These 14 miRNAs were then used in bioinformatic analyses to identify Kyoto Encyclopedia of Genes and Genomes (KEGG) pathways that were predicted to be most affected by these differentially expressed miRNAs. Overexpressed miRNAs were predicted to primarily regulate glycosaminoglycan biosynthesis, along with various signaling pathways such as Phosphoinositide‐3‐kinase/protein kinase B and transforming growth factor‐β. Similarly, signaling pathways including phosphatidylinositol and Hippo were predicted to be regulated by the underexpression of miRNAs during torpor. Together, these results suggest potential molecular adaptations that protect against irreversible tissue damage and enable continued cardiac and vascular function despite hypothermia and limited organ perfusion during torpor. [ABSTRACT FROM AUTHOR]

Significant multi‐centennial climate oscillations have been documented in a number of well‐dated climate records across the Holocene epoch and left various imprints in human cultural history. In this study, we developed speleothem δ13C, δ18O, trace elements, and lamina thickness records from the Yunnan‐Guizhou Plateau (YGP). Our high‐resolution and precisely dated records show a significant ∼550‐yr cycle as the dominant pattern of regional temperature and vegetation variations between ∼5,870 and ∼3,670 years ago. The phase analyses of the 550‐yr cycles among our speleothem records, other Northern Hemisphere climate records, solar activity index, and Atlantic meridional overturning circulation (AMOC) variations suggest that this climate cycle has a large spatial extent, and may be causally linked to the AMOC changes through coupled oceanic‐atmospheric processes. Additionally, the first cold phase of the ∼550‐yr cycle in our records coincides with the major cultural development on the YGP at ∼5,500–5,000 years ago, suggesting a critical relationship between climate and prehistorical cultural changes in the region. Plain Language Summary: This study presents precisely dated speleothem isotope and lamina thickness records, which shows a ∼550‐yr periodicity of vegetation and temperature changes between ∼5,870 and ∼3,670 years ago in the Yunnan‐Guizhou Plateau (YGP), southwestern China. The phase analyses between our records and other Northern Hemisphere climate records suggest that these climate cycles have a large spatial scale in Northern Hemisphere and may be linked to the Atlantic meridional overturning circulation changes through coupled oceanic‐atmospheric processes. Besides, the records show that a cold phase during ∼5,500–5,000 years ago coincided with the period of development of YGP Neolithic production tools, suggesting a critical role of climate change in the prehistorical cultural evolution in the region. Key Points: A significant multi‐centennial temperature and vegetation oscillation of ∼550‐yr cycles occurred between ∼5,870 and ∼3,670 years ago in the Yunnan‐Guizhou Plateau (YGP)The climate cycles were likely linked to the Atlantic meridional overturning circulation variation through coupled oceanic‐atmospheric processesThe first cold phase of the ∼550‐yr cycles in our records coincided with a change of population and major cultural transform in the YGP at ∼5,500–5,000 years ago, implying a critical role of climate change and resource shortage in the prehistorical cultural evolution in the region [ABSTRACT FROM AUTHOR]

Speleothem oxygen isotope (δ18O) constitutes one of key proxies to reconstruct the Indian and East Asian summer monsoon (ISM and EASM) hydroclimate history on a wide range of timescales. Here, we use three new well-dated speleothem δ18O records from Tianmen cave, in the south-central Tibetan Plateau (TP), together with previous records from the same cave, to reconstruct a composite Tianmen record spanning over the past 414,000 years. The Tianmen δ18O record follows Northern Hemisphere summer insolation (NHSI), broadly coherent with speleothem δ18O records from both ISM and EASM regimes. In comparison with previous model simulations and modern hydroclimate analyses, the Tianmen δ18O was interpreted primarily as a proxy indicating the ISM intensity. The Tianmen δ18O record comprises both high and low NHSI time periods, which reveals an exceptional large amplitude (∼14‰) of δ18O variations at the precession band, possibly resulted from a combination effect of precipitation amount, moisture source, transport pathway, high elevation and rainout. Besides, a broad consistency on orbital-scale variability among Tianmen δ18O, δ13C and trace element records is found, suggesting that the ISM intensity regulates the effective rainfall at the cave site as well. Notably, Tianmen speleothem growth occurred merely during warm-wet interglacial periods, even during low NHSI times near the precession maximum, and in contrast, hiatuses persistently occurred throughout cold-dry glacial periods. This pattern is similar to that found in travertine formations in the region, both suggesting that the interglacial temperature might be a prerequisite for speleothem/travertine formations in the region, while the strong ISM precipitation in turn provides a sufficient condition. Our new Tianmen record, combined with a large set of speleothem records from both Asian Westerlies and Asian monsoon domains, gives further evidence to reinforce a previous hypothesis: a consistent temporal pattern in the δ18O of precipitation on orbital and millennial scales over the vast Asian monsoon and Westerlies regimes. As such, in order to reconcile the precipitation δ18O variations between speleothem and TP ice cores, we argue that the Guliya ice-core chronology may have a basal age of ∼70 ka BP , which is supported by recent dating results from the Guliya ice cap. • Speleothem δ18O records from the south-central Tibetan Plateau primarily indicate the Indian summer monsoon (ISM) intensity. • Combined effect results in a large amplitude (∼14‰) of Tianmen cave δ18O variations at the precession band. • Interglacial temperature and high ISM precipitation are critical factors for the speleothem formations in the region. [ABSTRACT FROM AUTHOR]

The arboreal marsupial monito del monte (genus Dromiciops, with two recognized species) is a paradigmatic mammal. It is the sole living representative of the order Microbiotheria, the ancestor lineage of Australian marsupials. Also, this marsupial is the unique frugivorous mammal in the temperate rainforest, being the main seed disperser of several endemic plants of this ecosystem, thus acting as keystone species. Dromiciops is also one of the few hibernating mammals in South America, spending half of the year in a physiological dormancy where metabolism is reduced to 10% of normal levels. This capacity to reduce energy expenditure in winter contrasts with the enormous energy turnover rate they experience in spring and summer. The unique life history strategies of this living Microbiotheria, characterized by an alternation of life in the slow and fast lanes, putatively represent ancestral traits that permitted these cold‐adapted mammals to survive in this environment. Here, we describe the ecological role of this emblematic marsupial, summarizing the ecophysiology of hibernation and sociality, updated phylogeographic relationships, reproductive cycle, trophic relationships, mutualisms, conservation, and threats. This marsupial shows high densities, despite presenting slow reproductive rates, a paradox explained by the unique characteristics of its three‐dimensional habitat. We finally suggest immediate actions to protect these species that may be threatened in the near future due to habitat destruction and climate change. [ABSTRACT FROM AUTHOR]

Climatic changes have played an important role in societal reorganizations. Particularly, the late 16th and early 17th century coincided with severely cold condition, extremely weak summer monsoon and widespread population decline in China. Here we present new speleothem oxygen isotope records across North and South China, which in concert with historical documents, allow us to characterize the "Late Ming Weak Monsoon Periods" (LMWMP) at an unprecedented annual temporal resolution. Our analysis suggests that as a weak summer monsoon event not seen for nearly 500 years in China, the LMWMP spatiotemporally coincided with the late Ming Dynasty peasant uprising (1627-1658 CE), and thus the transition from Ming to Qing Dynasty. This suggests a plausible role of climate change in shaping the important chapters of the Chinese history. In addition, both speleothem and historical documents reveal that the LMWMP appears to be a north to south time-transgressive event on decadal-timescale. Plain Language Summary This study presents two new speleothem paleoclimate records across northern and southern China, which in concert with the historical documents, allow us to characterize the Late Ming Weak Monsoon Periods (LMWMP) (1580-1660 CE). The records offer that the unprecedented, long-lasting aridity/weakening monsoon period was spatiotemporally synchronized with the late Ming peasantry uprising (1627-1658 CE) and the fall of the Ming Dynasty. The comparisons with many regional paleoclimate records show that the severest drought during the LMWMP was timetransgressive on decadal-timescale: from northern China to the Jiang-Huai region. Mechanistically, solar activity may provide a centennial scale background of precipitation decreases for LMWMP. [ABSTRACT FROM AUTHOR]

Commonly used speleothem-based paleoclimate proxies such as δ18O, δ13C, and trace element ratios are capable of high temporal resolution, but their interpretations are often ambiguous due to the conflated effects of multiple forcings. This complexity motivates the development of targeted proxies that can track specific local hydrological conditions. To this end, the concentration of ferromagnetic Fe-oxide particles in speleothem laminae has been suggested as a potential tracer for local precipitation. Here we use the quantum diamond microscope (QDM) to obtain a sub-annual resolution time series of ferromagnetic content in a Brazilian speleothem from a well-ventilated cave environment covering the period between 1913 and 2016 CE. This high resolution allows us to quantify the correlation between speleothem magnetic properties and an instrumental precipitation record for the first time. We find that ferromagnetic content in the central column displays a modest but significant negative correlation with rainfall ( R 2 = 0.35 ; p = 0.0027) , while magnetism in the speleothem flanks shows a weaker, statistically insignificant relationship. Rock magnetic analyses of the speleothem further reveal ultrafine, pedogenic grains to be the dominant ferromagnetic carriers. Combining QDM and electron microprobe data, we show that these pedogenic grains were likely developed in surface soils and delivered into the cave as part of airborne, 10–200 μm silicate-carbonate soil agglomerates. Our results show that speleothem magnetism holds strong potential as a targeted proxy for paleorainfall and demonstrate a method for identifying the mechanism of magnetic enhancement, which sets the necessary foundation for any paleoclimatic interpretations. • New quantum magnetometer is used obtain a sub-annual magnetic time series of a Brazilian speleothem. • Magnetic signal from speleothem is directly compared to precipitation data. • Cave deposit used to decode paleoclimate precipitation story. • Cave deposit tells story of role of aerosols in stalagmite deposition. [ABSTRACT FROM AUTHOR]

The abrupt climate event Younger Dryas (YD) has been extensively studied; however, its structure is still poorly understood. Climate in northeastern Brazil is very sensitive to the latitudinal position of the intertropical convergence zone (ITCZ) associated with abrupt climate change in the Atlantic. Here, we report changes in the ITCZ position within the YD by using precise speleothem multiproxy records from northeastern Brazil. We provide evidence for a gradual northward migration of the ITCZ preceding poleward shifts of the westerlies and the polar front in northern high latitudes within the YD. This can be attributed to gradual increase in atmospheric CO2 concentration as a consequence of the weakening Atlantic Meridional Overturning Circulation (AMOC). We suggest that a persistent increase in atmospheric CO2 might have triggered a resumption of the AMOC and reorganization of the atmosphere circulation in the Atlantic during the mid‐YD. Plain Language Summary: The Younger Dryas (YD) is the most recent millennial‐scale abrupt climate event in Earth history. Although its origin has been extensively studied, its structure is still poorly understood. Climate in northeastern Brazil is very sensitive to the latitudinal position of the intertropical convergence zone (ITCZ) responds to abrupt climate change in the Atlantic (e.g., YD). By using stable isotope and trace element proxy records of speleothem from Toca da Boa Vista Cave, northeastern Brazil, together with other paleoclimatic records in the Atlantic realm, we provide evidence for a gradual northward migration of the ITCZ preceding poleward shifts of the westerlies and the polar front in northern high latitudes within the YD. This can be attributed to a gradual increase in atmospheric CO2 concentration under the situation of weakening Atlantic Meridional Overturning Circulation (AMOC). A persistent increase in atmospheric CO2 concentration might have triggered a resumption of the AMOC and reorganization of the atmosphere circulation in the Atlantic during the mid‐YD. Key Points: Speleothem and other paleoclimate records confirm a wet climate in tropical South America within the Younger DryasPrecise speleothem multiproxy records reflect a bipartition of the Younger Dryas precipitation in northeastern BrazilGradual South‐North climate transition in the Atlantic responded to a gradual increase in atmospheric CO2 within the YD [ABSTRACT FROM AUTHOR]

The Asian summer monsoon (ASM) is a vast climate system, whose variability is critical to the livelihoods of billions of people across the Asian continent. During the past half-century, much progress has been made in understanding variations on a wide range of timescales, yet several significant issues remain unresolved. Of note are two long-standing problems concerning orbital-scale variations of the ASM. (1) Chinese loess magnetic susceptibility records show a persistent glacial-interglacial dominated ~100 kyr (thousand years) periodicity, while the cave oxygen-isotope (δ18O) records reveal periodicity in an almost pure precession band (~20 kyr periodicity)—the "Chinese 100 kyr problem". (2) ASM records from the Arabian Sea and other oceans surrounding the Asian continent show a significant lag of 8–10 kyr to Northern Hemisphere summer insolation (NHSI), whereas the Asian cave δ18O records follow NHSI without a significant lag—a discrepancy termed the "sea-land precession-phase paradox". How can we reconcile these differences? Recent and more refined model simulations now provide spatial patterns of rainfall and wind across the precession cycle, revealing distinct regional divergences in the ASM domain, which can well explain a large portion of the disparities between the loess, marine, and cave proxy records. Overall, we also find that the loess, marine, and cave records are indeed complementary rather than incompatible, with each record preferentially describing a certain aspect of ASM dynamics. Our study provides new insight into the understanding of different hydroclimatic proxies and largely reconciles the "Chinese 100 kyr problem" and "sea-land precession-phase paradox". [ABSTRACT FROM AUTHOR]

Mountain glaciers have generally experienced an accelerated retreat over the last 3 decades as a rapid response to current global warming. However, the response to previous warm periods in the Holocene is not well-described for glaciers of the southern Europe mountain ranges, such as the Pyrenees. The situation during the Medieval Climate Anomaly (900–1300 CE) is particularly relevant since it is not certain whether the southern European glaciers just experienced significant ice loss or whether they actually disappeared. We present here the first chronological study of a glacier located in the Central Pyrenees (NE Spain), Monte Perdido Glacier (MPG), carried out by different radiochronological techniques and a comparison with geochemical proxies from neighbouring palaeoclimate records. The chronological model evidences that the glacier persisted during the Roman period and the Medieval Climate Anomaly. The apparent absence of ice in the past ∼ 600 years suggests that any ice accumulated during the Little Ice Age has since ablated. This interpretation is supported by measured concentrations of anthropogenic metals, including Zn, Se, Cd, Hg and Pb, which have concentrations well below those typical of industrial-age ice measured at other glaciers in Europe. This study strengthens the general understanding that warming of the past few decades has been exceptional for the past 2 millennia. [ABSTRACT FROM AUTHOR]

The 8.2 ka abrupt cooling event has been extensively studied, whereas the 7.2 ka event and their comparations rarely mentioned. Here, we present a high resolution (∼4 years) and precisely dated (±25 years) speleothem multi-proxy record from Zhangjia Cave (northern margin of Sichuan basin, China) spanning the 7.2 and 8.2 ka events within the transition of early to middle Holocene. The speleothem δ18O mainly reflects the dynamic facets of the East Asian summer monsoon (EASM) system, while its δ13C and trace elements ratios serve as an indicator of local hydrological conditions. Our results reveal intense dry conditions in southwest China during the 7.2 ka event, despite the 7.2 event was characterized by a relatively stronger monsoon compared to the 8.2 ka event. Furthermore, the hydrological conditions during the 7.2 ka event and the middle Holocene appear to exhibit "north flood and south drought" pattern when compared to different paleoclimate records in EASM domains, while it can be summarized as "spatially consistent drought" in the 8.2 ka event. These different hydrological conditions are a response to the weakening of the EASM, a phenomenon also observed in modern climatic observations and empirical simulations, which underpins our understanding that the speleothem δ18O variations are mainly dynamical manifestations of the EASM system, likely different with its thermodynamical appearances. • In the 7.2 ka event, we observed more intense dryness in southwest China compared to the 8.2 ka event, despite the 7.2 event having a relatively stronger monsoon. • The precipitation patterns differed between the 7.2 ka event, 8.2 ka event, as well as the Early and Middle Holocene. During the 7.2 ka event, hydrological conditions exhibited a "north flood and south drought" pattern, while the 8.2 ka event was characterized by "spatially consistent drought." • The varying precipitation patterns under similar East Asian Summer Monsoon (EASM) intensities enhance our understanding of speleothem δ18O. This suggests that speleothem δ18O primarily reflects the dynamics of the EASM system rather than the thermodynamics. [ABSTRACT FROM AUTHOR]

Speleothem records from NE Asia are essential to understand the spatial patterns of the Asian Summer Monsoon (ASM) variability. In this paper, we present a new high-resolution and chronologically well-resolved speleothem record from Liu-li (LL) cave, NE China, through δ18O, δ13C and Sr/Ca ratio characterizing a dynamic ASM history over the past 6680 years. The LL δ18O record shows a long-term trend to higher values, following the North Hemisphere summer insolation (NHSI), with the exception of the last 2 kyr characterized by a negative δ18O excursion. The '2-kyr shift' is evident in NE Asia over the past 2 kyr, originally inferred from the speleothem δ18O negative excursion in South China, as well as in many other proxy records from East China, but it merely manifests a flat trend in most of the western East Asian Summer Monsoon (EASM) and Indian Summer Monsoon (ISM) regions, rather than a negative excursion. On multi-centennial to millennial timescales, the intensification of the Tsushima Warm Current (TWC) can amplify rainfall on both sides of the Japan Sea. A close comparison between the monsoon reconstruction and the cultural changes in NE Asia suggests contemporary climatic and cultural regime-shifts, implying an important role of the ASM weakening in the collapse of Neolithic and Early Bronze cultures in this region. • The records we present and the comparison with many regional paleoclimate records offers new evidences of the distribution of the '2-kyr shift'. • On multi-centennial to millennial timescales, the covariation of different records in NE Asia suggests that the intensification of the Tsushima Warm Current can amplify rainfall on both sides of the Japan Sea. • The contemporary climatic and cultural regime-shifts suggest that the monsoon weakening might play an important role in the collapse of the Neolithic and Early Bronze cultures from this region. [ABSTRACT FROM AUTHOR]

In glaciated areas, the environmental evolution before MIS 2 is usually poorly constrained mainly due to the later glacial erosion during the global Last Glacial Maximum (LGM). However, in carbonate areas, karst caves can preserve records of pre-LGM paleoenvironment. We studied a cave (1350 m altitude) to establish the paleoenvironmental evolution of a glaciated karst area in Picos de Europa (SW Europe). For this objective, a glacial reconstruction, cave sedimentology analyses, and macro- and micromammal remains are com bined with ten U–Th, OSL and AMS 14C ages. The paleo-glacial reconstruction indicates glaciers descended down to 810–1040 m of altitude covering an area of 36.18 km2 in the surroundings of Covadonga Lakes during the glacial local maximum, with the equilibrium line altitude located at 1524 ± 36 m. The geomorphological study of the cave and the U–Th and OSL dates reveal the presence of three allochthonous alluvial sediment sequences at 132–135, 98–60 and ca. 36 ka. These last two sequences would come from the erosion of fluvioglacial sediments including teeth fragments of Pliomys coronensis (= P. lenki), an unusual species in high areas of NW Spain during the Upper Pleistocene. In addition, remains of chamois (Rupicapra pyrenaica) dated in 37–33 cal ka BP constitutes the oldest evidence of chamois above 800 m asl in the region. All the presented data indicate the development of alpine glacier-free areas covered by fluvioglacial sediments at ca. 1450 m altitude at 98–60 and 37–33 ka, corresponding to glacial retreat stages. • Paleoenvironmental evolution based on glacial, cave, fossils, U–Th, OSL and 14C data. • Cave and mammal fossils data constrain the timing of reconstructed glaciers. • Pliomys coronensis lived up to 1400 m in NW Spain during MIS 4. • The oldest evidence of Rupicapra pyrenaica above 1000 m asl of NW Spain. • Fossil remains indicate ice-free conditions around 98–60 and 37–33 ka at 1400 asl [ABSTRACT FROM AUTHOR]

Speleothems (secondary cave carbonates) are a widely used archive for the palaeoclimatereconstruction, particularly for high-resolution climate variability, due to their exceptionalchronological control. The first version of the SISAL database contains 376 speleothemrecords from across the globe; about a quarter of these records are from Western Europe,making it the region with the highest density of published speleothem datasets. WesternEurope also possesses the highest density of Global Network of Isotopes in Precipitation(GNIP) stations, some of the longest meteorological records, and global modelling andreanalysis datasets, as well as a large number of continuous, high-resolution multiannual cavemonitoring time-series. This is a great advantage for the interpretation of δ18O value inspeleothems, which is driven by a complex interplay of regional and site-specificfactors. This study is the first assessment of the Western European data from the SISAL database,which reviews the SISAL records within the wider (palaeo-)climatic context of WesternEurope, with the objective to investigate the suitability of large compilations of speleothemrecords to reveal the existence of regional trends in time, as well as to identify and promotethe potential of cave sites in the region for future palaeoclimate studies. We find that i)present-day spatial trends in δ18O from Western European speleothems generally mirror thetrends in precipitation δ18O. ii) Over the late Quaternary, site-specific noise in speleothemsδ18O presents the main issue for the extraction of a regional climate signal, especially overthe Holocene. iii) Results are improved through the use of statistical methods, allowing theextraction of regional climate modes. Use of other types of data and more information aboutcave monitoring as well as an updated age modelling technique intercomparison study,can significantly enhance the potential of these records for regional palaeoclimatestudies. SISAL is a new valuable tool for intercomparison of speleothem δ18O in a regional andglobal context. Inclusion of missing records in the future of versions of SISAL canconsiderably improve temporal and spatial coverage of the dataset. Furthermore, updating theage-models to include age-model uncertainties for all records would reduce the overalluncertainty of δ18O time-series, and thus improve the level of accuracy in subsequentanalyses. [ABSTRACT FROM AUTHOR]