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The variability of the northern westerlies has been considered as one of the key elements for modern and past climate evolution. Their multiscale behavior and underlying control mechanisms, however, are incompletely understood, owing to the complex dynamics of Atlantic sea-level pressures. Here, we present a multi-annually resolved record of the westerly drift over the past 6,500 years from northern Italy. In combination with more than 20 other westerly-sensitive records, our results depict the non-stationary westerly-affected regions over mainland Europe on multi-decadal to multi-centennial time scales, showing that the direction of the westerlies has changed with respect to the migrations of the North Atlantic centers of action since the middle Holocene. Our findings suggest the crucial role of the migrations of the North Atlantic dipole in modulating the westerly-affected domain over Europe, possibly modulated by Atlantic Ocean variability.

Our understanding of climate dynamics during millennial-scale events is incomplete, partially due to the lack of their precise phase analyses under various boundary conditions. Here we present nine speleothem oxygen-isotope records from mid-to-low-latitude monsoon regimes with sub-centennial age precision and multi-annual resolution, spanning the Heinrich Stadial 2 (HS2) - a millennial-scale event that occurred at the Last Glacial Maximum. Our data suggests that the Greenland and Antarctic ice-core chronologies require +320- and +400-year adjustments, respectively, supported by extant volcanic evidence and radiocarbon ages. Our chronological framework shows a synchronous HS2 onset globally. Our records precisely characterize a centennial-scale abrupt "tropical atmospheric seesaw" superimposed on the conventional "bipolar seesaw" at the beginning of HS2, implying a unique response/feedback from low-latitude hydroclimate. Together with our observation of an early South American monsoon shift at the HS2 termination, we suggest a more active role of low-latitude hydroclimate dynamics underlying millennial events than previously thought.

Characterizing the temporal uncertainty in palaeoclimate records is crucial for analysing past climate change, correlating climate events between records, assessing climate periodicities, identifying potential triggers and evaluating climate model simulations. The first global compilation of speleothem isotope records by the SISAL (Speleothem Isotope Synthesis and Analysis) working group showed that age model uncertainties are not systematically reported in the published literature, and these are only available for a limited number of records (ca. 15 %, n = 107/691). To improve the usefulness of the SISAL database, we have (i) improved the database's spatio-temporal coverage and (ii) created new chronologies using seven different approaches for age- depth modelling. We have applied these alternative chronologies to the records from the first version of the SISAL database (SISALv1) and to new records compiled since the release of SISALv1. This paper documents the necessary changes in the structure of the SISAL database to accommodate the inclusion of the new age models and their uncertainties as well as the expansion of the database to include new records and the qualitycontrol measures applied. This paper also documents the age-depth model approaches used to calculate the new chronologies. The updated version of the SISAL database (SISALv2) contains isotopic data from 691 speleothem records from 294 cave sites and new age-depth models, including age-depth temporal uncertainties for 512 speleothems.

The Younger Dryas (YD), arguably the most widely studied millennial-scale extreme climate event, was characterized by diverse hydroclimate shifts globally and severe cooling at high northern latitudes that abruptly punctuated the warming trend from the last glacial to the present interglacial. To date, a precise understanding of its trigger, propagation, and termination remains elusive. Here, we present speleothem oxygen-isotope data that, in concert with other proxy records, allow us to quantify the timing of the YD onset and termination at an unprecedented subcentennial temporal precision across the North Atlantic, Asian Monsoon-Westerlies, and South American Monsoon regions. Our analysis suggests that the onsets of YD in the North Atlantic (12,870 ± 30 B.P.) and the Asian Monsoon-Westerlies region are essentially synchronous within a few decades and lead the onset in Antarctica, implying a north-to-south climate signal propagation via both atmospheric (decadal-time scale) and oceanic (centennial-time scale) processes, similar to the Dansgaard-Oeschger events during the last glacial period. In contrast, the YD termination may have started first in Antarctica at ∼11,900 B.P., or perhaps even earlier in the western tropical Pacific, followed by the North Atlantic between ∼11,700 ± 40 and 11,610 ± 40 B.P. These observations suggest that the initial YD termination might have originated in the Southern Hemisphere and/or the tropical Pacific, indicating a Southern Hemisphere/tropics to North Atlantic-Asian Monsoon-Westerlies directionality of climatic recovery.

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]

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]

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]

The Chinese Loess Plateau (CLP) is located in northern China, a region climatically dominated by the East Asian monsoon. Speleothem records from this region are crucial to fully understand the variability of the East Asian summer monsoon (EASM) and reconcile the disparity seen between loess records and speleothem δ18O records for the EASM. Here, we present an absolutely dated stalagmite isotope record spanning most of Marine Isotope Stage (MIS) 5 to MIS 3 from Xiaotian Cave, southeast CLP. The Xiaotian speleothem δ18O record is dominated by precessional variations and punctuated by notable millennial‐scale oscillations; in particular, the δ18O values in MIS 5e, 5c and 5a were in the same range, consistent with other speleothem δ18O records from the EASM region within quoted errors, verifying the difference between speleothem δ18O and loess records (e.g. magnetic susceptibility) and the proposition that those two archives may record different aspects of the EASM changes. The similar values in MIS 5e, 5c and 5a observed from the speleothem δ18O records in EASM regions, incompatible with the relatively higher North Hemisphere Summer Insolation (NHSI) during MIS 5e, were probably caused by an equivalent or even increased contribution of 18O‐enriched moisture from the South China Sea and North Pacific, implying that an El Niño‐like state existed during MIS 5e. The Xiaotian δ18O values increased abruptly at ~121.7 thousand years (kyr) before the present (bp, present refers to ad 1950), consistent with the trend seen in previously reported Chinese speleothem δ18O records, indicating an abrupt regime shift in atmospheric circulations or hydroclimate conditions in the Asian monsoon systems. It cannot be definitely ruled out that an increase in sea ice extent in the northern North Atlantic, responding to a decrease of NHSI, reached a threshold to have led to abrupt changes in the Asian summer monsoon (ASM) through rapid shifts in the position of circulation of the westerlies and/or in the position of Intertropical Convergence Zone (ITCZ). Here, we hypothesized that sea surface cooling in the tropical Indian and Pacific Ocean caused by the decreased summer insolation reached a threshold that eventually resulted in an abrupt shift to more positive precipitation δ18O, either through weakened convection over the tropical ocean, or through abrupt shifts in moisture transport and cycling of tropical moisture sources for the ASM. The Xiaotian speleothem δ18O record also shows centennial‐scale variability with amplitude up to 3‰ within MIS 5e. These changes are similar to variations recorded by the speleothem δ18O record from Tianmen Cave on the south‐central Tibetan Plateau and Shangxiaofeng Cave in Shandong Province, northern China, suggesting a heightened sensitivity of precipitation δ18O to climate changes at the marginal zone of the ASM even during the warm and humid MIS 5e interglacial. Climatic oscillations during MIS 5e appear to be comparable to those typical of the Holocene, implying rather unstable climate conditions during the Last Interglacial. [ABSTRACT FROM AUTHOR]

The carbon isotopic signature inherited from soil/epikarst processes may be modified by degassing and prior calcite precipitation (PCP) before its imprint on speleothem calcite. Despite laboratory demonstration of PCP effects on carbon isotopes and increasingly sophisticated models of the governing processes, to date, there has been limited effort to deconvolve the dual PCP and soil/epikarst components in measured speleothem isotopic time series. In this contribution, we explore the feasibility, advantages, and disadvantages of using trace element ratios and δ44Ca to remove the overprinting effect of PCP on measured δ13C to infer the temporal variations in the initial δ13C of dripwater. In 8 examined stalagmites, the most widely utilized PCP indicators Mg/Ca and δ44Ca covary as expected. However, Sr/Ca does not show consistent relationships with δ44Ca so PCP is not universally the dominant control on Sr/Ca. From δ44Ca and Mg/Ca, our calculation of PCP as fCa, fraction of initial Ca remaining at the deposition of the stalagmite layer, yields multiple viable solutions depending on the assumed δ44Ca fractionation factor and inferred variation in DMg. Uncertainty in the effective fractionation of δ13C during degassing and precipitation contributes to uncertainty in the absolute value of estimated initial δ13C. Nonetheless, the trends in initial δ13C are less sensitive to these uncertainties. In coeval stalagmites from the same cave spanning 94 to 82 ka interval, trends in calculated initial δ13C are more similar than those in measured δ13C, and reveal a common positive anomaly initial δ13C during a stadial cooling event. During deglaciations, the trend of greater respiration rates and higher soil CO2 is captured in the calculated initial δ13C, despite the tendency of higher interglacial dripwater situation to favor more extensive PCP. [ABSTRACT FROM AUTHOR]