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This study utilizes speleothem trace elements as climate proxies to reconstruct hydroclimate variability over approximately 350 years in the Southern Cook Islands. Stalagmites Pu17 and Pu4 from Pouatea cave were analyzed using high-resolution LA-ICP-MS for trace elements (Mg, Na, Sr, P, U, Y). By monitoring cave dripwater and conducting regression analysis, we found that Mg, Sr, and Na in Pouatea dripwater mostly originated from marine aerosols, while Sr and Ba were primarily from bedrock, with additional Ba coming from marine aerosols and weathered oceanic basalt leaching. Mg was identified as the most reliable element for hydroclimate reconstruction due to its predominantly marine aerosol origin. Infiltration, via dilution of marine aerosols and bedrock inputs, was identified as the main driver of trace element variations in Pouatea at a seasonal scale. Transfer functions were established between each trace element and effective infiltration was calculated, with Mg showing the strongest correlation. The reconstructed infiltration data were compared with climate indices, showing an overarching role of the SPCZ and ENSO in controlling rainfall in the South Pacific. This research demonstrates the potential of speleothem trace elements for paleohydroclimate reconstructions, improving understanding of rainfall variability in the climatically vulnerable South Pacific Islands over the past millennia. [ABSTRACT FROM AUTHOR]

The 8.2 ka event is the most significant global climate anomaly of the Holocene epoch, but a lack of records from Mainland Southeast Asia (MSEA) currently limits our understanding of the spatial and temporal extent of the climate response. A newly developed speleothem record from Tham Doun Mai Cave, Northern Laos provides the first high‐resolution record of this event in MSEA. Our multiproxy record (δ18O, δ13C, Mg/Ca, Sr/Ca, and petrographic data), anchored in time by 9 U‐Th ages, reveals a significant reduction in local rainfall amount and weakening of the monsoon at the event onset at ∼8.29 ± 0.03 ka BP. This response lasts for a minimum of ∼170 years, similar to event length estimates from other speleothem δ18O monsoon records. Interestingly, however, our δ13C and Mg/Ca data, proxies for local hydrology, show that abrupt changes to local rainfall amounts began decades earlier (∼70 years) than registered in the δ18O. Moreover, the δ13C and Mg/Ca also show that reductions in rainfall continued for at least ∼200 years longer than the weakening of the monsoon inferred from the δ18O. Our interpretations suggest that drier conditions brought on by the 8.2 ka event in MSEA were felt beyond the temporal boundaries defined by δ18O‐inferred monsoon intensity, and an initial wet period (or precursor event) may have preceded the local drying. Most existing Asian Monsoon proxy records of the 8.2 ka event may lack the resolution and/or multiproxy information necessary to establish local and regional hydrological sensitivity to abrupt climate change. Plain Language Summary: The most significant global climate event in the last ∼11,000 years occurred ∼8,200 years ago (the "8.2 ka event"). Many globally distributed records of past climate (paleoclimate) document significant changes during the event, but there are few from Mainland Southeast Asia available to reconstruct the climate impacts in this region. We present a new speleothem (cave sample) record from Tham Doun Mai Cave, Northern Laos that uses multiple geochemical and physical signals (proxies) to document local and regional climate effects of the 8.2 ka event at a high resolution. Using oxygen isotopes, we find that the 8.2 ka event weakened regional monsoon intensity for at least ∼170 years, which resembles findings from other studies. However, other proxies suggest local rainfall changed abruptly decades before the signal of monsoon weakening. Additionally, local drying may have lasted much longer than current estimates of 8.2 ka event responses. Most proxy records of the 8.2 ka event in monsoon regions lack similar multiproxy information and/or do not have high enough resolution to fully capture the climatic response. Additional records like ours from monsoon regions may assist in establishing how sensitive local and regional rainfall is to abrupt climate change. Key Points: High‐resolution speleothem record of the 8.2 ka event in northern Laos shows weakened monsoon intensity and reduced local rainfall amountsMultiproxy data suggest the disruption to local rainfall amounts started decades before the weakened monsoon intensity inferred from δ18OPrevious monsoon records of the event lack the resolution and/or multiproxy dimensions needed to reconstruct local hydrologic changes [ABSTRACT FROM AUTHOR]

In this study, the ‘dead carbon proportion’ (DCP) calculated from combined U-Th and radiocarbon analyses was used to explore the carbon isotope systematics in Corchia Cave (Italy) speleothems, using the example of stalagmite CC26 which grew during the last ∼12 ka. The DCP values in CC26 are among the highest ever recorded in a stalagmite, spanning the range 44.8–68.8%. A combination of almost closed-system conditions and sulphuric acid dissolution (SAD) are proposed as major drivers in producing such a high DCP with minor contribution from old organic matter from the deep vadose zone. The long-term decrease in both DCP and δ 13 C most likely reflects post-glacial soil recovery above the cave, with a progressive increase of soil CO 2 contribution to the total dissolved inorganic carbon (DIC). Pronounced millennial-scale shifts in DCP and relatively small coeval but antipathetic changes in δ 13 C are modulated by the effects of hydrological variability on open and closed-system dissolution, SAD and prior calcite precipitation. Hence, the DCP in Corchia Cave speleothems represents an additional proxy for rainfall amount. [ABSTRACT FROM AUTHOR]

The quality of climate proxy data from speleothem archives depends to varying degrees on crystallization processes, which result in diverse fabrics. Here, we document shifts in calcite growth mechanisms, from ion-by-ion to nanoparticle/nanocrystal attachment, in stalagmites from the tropical island of Atiu (South Pacific). Changes in solution stoichiometry and organic matter content result in the development of two columnar fabrics that are common elsewhere in settings characterized by seasonal contrast. A porous columnar fabric, characterized by intracrystalline micro and nanoporosity grows via a non-classical pathway through amorphous calcium carbonate (ACC) nanoparticles (∼2–4 nm in diameter) and calcite nanocrystal attachment. Despite subsequent transformation of nanoparticles/crystals into a large calcite crystal, the porous columnar fabric appears to preserve a δ18O signal that faithfully reflects that of the parent fluid via quasi-equilibrium fractionation. Furthermore, the porous fabric shows random and fuzzy lateral distributions of Sr, another hydrological proxy, yet this element's incorporation follows equilibrium partitioning. The chemical properties of compact columnar fabrics, which appear to grow by classical ion-by-ion attachment, may not directly reflect those of the original depositional environment because of degassing, the presence of growth inhibitors (such as Na) and very early diagenetic modifications. Columnar porous calcite fabrics that formed through non-classical pathways in other settings may faithfully record the original properties of the parent drip water, whereas compact fabrics that formed through classical pathways elsewhere may not. It is concluded that the study of fabrics at the nano-scale is a necessary complement to speleothem research to identify the influence of crystallization pathways on the accuracy of proxy data. • Stalagmite calcite forms through complex crystallization pathways. • Both classical and non-classical processes are involved. • Particle and nanocrystal attachment operate to yield a porous fabric. • Columnar porous calcite may faithfully record the original properties of the parent drip water. • Oxygen isotopes and trace element concentration correlate with fabrics through crystallization. [ABSTRACT FROM AUTHOR]

Carbonate-associated sulphate (CAS) is a useful carrier of palaeoenvironmental information throughout the geologic record, particularly through its stable isotope composition. However, a paucity of experimental data restricts quantitative understanding of sulphate incorporation into carbonates, and consequently CAS concentrations and their diagenetic modifications are rarely interpreted. However, in the case of calcite speleothems, the remarkably high-resolution CAS records which are obtainable via modern microanalytical techniques represent a potentially invaluable source of palaeoenvironmental information. Here, we describe the results of controlled experiments of sulphate co-precipitation with calcite in freshwater solutions where pH, saturation state, and sulphate concentration were varied independently of each other. Solution pH is confirmed as the principal control on sulphate incorporation into calcite. The relative efficiency of incorporation was calculated as a partition coefficient D SO 4  = (mSO 4 /mCO 3 ) solid /(mSO 4 /mCO 3 ) solution . High crystal growth rates (driven by either pH or saturation state) encouraged higher values of D SO 4 because of an increasing concentration of defect sites on crystal surfaces. At low growth rates, D SO 4 was reduced due to an inferred competition between sulphate and bicarbonate at the calcite surface. These experimental results are applied to understand the incorporation of sulphate into speleothem calcite. The experimentally determined pH-dependence suggests that strong seasonal variations in cave air PCO 2 could account for annual cycles in sulphate concentration observed in stalagmites. Our new experimentally determined values of D SO 4 were compared with D SO 4 values calculated from speleothem-drip water monitoring from two caves within the Austrian and Italian Alps. At Obir cave, Austria, D SO 4 (×10 5 ) varies between 11.1 (winter) and 9.0 (summer) and the corresponding figures for Ernesto cave, Italy, are 15.4 (winter) and 14.9 (summer). These values approximate predicted D SO 4 values based on our chamber experiments containing both low (2 ppm) and high (20 ppm) sulphate concentrations. Our experimental values of D SO 4 obtained at crystal growth rates typical of stalagmites, closely match those observed in other cave sites from around the world. This validates the universality of the controls behind D SO 4 and will enhance the use of speleothem CAS as a palaeoenvironmental proxy. [ABSTRACT FROM AUTHOR]

The spatiotemporal variability of the Asian Monsoon (AM) over the last two millennia has been attributed to a combination of external solar and volcanic forcing and/or internal coupled atmosphere-ocean dynamics, but the relative importance of these mechanisms remains unresolved. The present knowledge of multidecadal to centennial-scale AM variability over Mainland Southeast Asia is not well-constrained, despite substantial progress in understanding seasonal to decadal variability from tree ring records. Here we present the first high-resolution stable isotope (δ 13 C and δ 18 O) speleothem record from northern Laos spanning the Common Era (∼50 BCE to 1880 CE). The δ 13 C record reveals substantial centennial-scale fluctuations primarily driven by local water balance. Notably, the driest period at our site occurred from ∼1280 to 1430 CE, during the time of the Angkor droughts, supporting previous findings that this megadrought likely impacted much of Mainland Southeast Asia. In contrast, variations in stalagmite δ 18 O reflect changes in rainfall upstream from our study site. Interestingly, the δ 18 O record exhibits a positive correlation with solar activity that persists after 1200 CE, contrary to the findings in previous studies. Solar-forced climate model simulations reveal that these δ 18 O variations may be driven by solar-forced changes in upstream rainout over the tropical Indian Ocean, which modify the δ 18 O of moisture transported to our study site without necessarily affecting local rainfall amount. We conclude that future rainfall changes in Mainland Southeast Asia are likely to be superimposed on multidecadal to centennial-scale variations in background climate driven primarily by internal climate variability, whereas solar forcing may impact upstream rainout over the Indian Ocean. • New high-resolution speleothem record from northern Laos spanning ∼50 BCE to 1880 CE. • δ 13 C reflects local water balance and records centennial-length dry periods during the Little Ice Age. • δ 18 O reflects upstream rainout over the Indian Ocean and may be influenced by solar forcing. [ABSTRACT FROM AUTHOR]

Organic phosphorus incorporated in calcite during laboratory precipitation experiments and in natural cave deposits was investigated by solid-state NMR spectroscopy. For calcite precipitated in the presence of organic phosphoesters of varying size and functionality, solid-state 31 P{ 1 H} CP/MAS NMR shows that the phosphoesters were incorporated intact into the solid. Systematic changes in the 31 P NMR chemical shift of the phosphate group were observed between the solid phosphoester and that incorporated in the solid precipitate, yielding 31 P NMR chemical shifts of the coprecipitates in the range of +1.8 to −2.2 ppm. These chemical shifts are distinct from that of similarly prepared calcite coprecipitated with inorganic phosphate, 3.5 ppm. Only minor changes were noted in the phosphoester 31 P chemical shift anisotropy (CSA) which suggests no significant change in the local structure of the phosphate group, which is dominated by C–O–P bonding. Close spatial proximity of the organic phosphate group to calcite structural components was revealed by 31 P/ 13 C rotational echo double resonance (REDOR) experiments for coprecipitates prepared with 13 C-labeled carbonate. All coprecipitates showed significant 31 P dephasing effects upon 13 C-irradiation, signaling atomic-scale proximity to carbonate carbon. The dephasing rate for smaller organophosphate molecules is similar to that observed for inorganic phosphate, whereas much slower dephasing was observed for larger molecules having long and/or bulky side-chains. This result suggests that small organic molecules can be tightly enclosed within the calcite structure, whereas significant structural disruption required to accommodate the larger organic molecules leads to longer phosphate–carbonate distances. Comparison of 31 P NMR spectroscopic data from the synthetic coprecipitates with those from calcite moonmilk speleothems indicates that phosphorus occurs mainly as inorganic orthophosphate in the natural deposits, although small signals occur with characteristics consistent with phosphate monoesters. The results of this study indicate that trace- to minor concentrations of dissolved organic molecules can be effectively taken up during calcite precipitation and incorporated in the structure, leaving a resilient record of materials present during crystallization. [ABSTRACT FROM AUTHOR]

Abstract: Sulphur emitted into the atmosphere from industrial activity is regarded as a key mechanism in forcing recent climate and has impacts upon the environment and human health at both local and regional scales. Trace amounts of sulphate present within speleothem carbonate can be used to provide an emissions inventory for regional sulphur loading to the atmosphere where sulphur isotopes can be extracted and used as a tool for provenance. However, speleothem sulphur concentrations are low and manual techniques for sulphur isotope analysis allow only low sampling resolution. SIMS (Secondary Ionisation Mass Spectrometry) is used here to develop records of sulphur isotopic change in speleothems from the Italian and Austrian Alps, where annual laminae are less than 100µm thick. Analysis at annual resolution over the past 100years demonstrates an excursion in sulphur isotopic composition from values close to the carbonate bedrock end-member composition in the pre-industrial era, to values isotopically depleted in 34 S. This trend is mirrored by increasing concentrations of sulphate and is suggested to reflect the increase in SO2 emissions with industrial activity. Subsequent decline in speleothem sulphate concentrations in one of the stalagmites reflects the recent European decline in industrial atmospheric SO2 content and is matched by a rebound in sulphur isotopic composition to values more enriched in 34 S. Superimposed on this general secular trend are smaller (annual) variations in concentration reflecting cave environmental conditions. High magnitude events of short duration, potentially reflect volcanic inputs of SO2 or the incorporation of dust particulates into the speleothem carbonate. This is the first micro-analysis of carbonate-associated sulphate (CAS) sulphur isotopes by SIMS. SIMS analysis of δ 34S–SO4 in speleothem carbonate reveals a high resolution archive depicting a regional sulphur emissions inventory for SO2 loading to the atmosphere. [Copyright &y& Elsevier]