The carbon isotopic composition of dissolved organic carbon (δ13CDOC) in speleothems, based on high-precision U-Th ages, has great potential to reconstruct past ecology, microbial activity, and carbon cycling. Identifying the reliability of the pretreatment and measurement of speleothem δ13CDOC is therefore essential to putting it into practice. Actually, we have previously verified the reliability of the method for speleothem δ13CDOC measurements. However, it was only based on the final δ13CDOC values of homogeneous speleothem powder and is unable to evaluate the effects of different experimental conditions and the impacts of adding acid on δ13CDOC if using speleothem as the study samples. In this study, we used an organic reagent (potassium sorbate) as the study sample and designed a conditional experiment that simulates the protocols for speleothem δ13CDOC analysis and presented the resulting data to inspect the effects of the experimental processes on the analysis of δ13CDOC. The results show that the standard deviation of duplicate samples is 0.1‰, which is close to that of the previous work for organic reagents and water samples, and the results were not affected by different experimental conditions and operation steps (such as adding orthophosphoric acid, digestion time, and storage duration of resulting CO2 in storage vessels), suggesting that this method is robust to detect the speleothem δ13CDOC. Considering the range and standard deviation of results, we proposed that the δ13CDOC record could be used in various studies when the amplitudes of the δ13CDOC record are larger than 0.1‰, especially greater than 0.4‰.

Speleothems are among the most important archives for past climatic and environmental change. Calcite recrystallization can modify the authigenic structure and geochemical composition of the speleothems and affect the reliability of calcite stalagmites as repositories of authigenic geochemical proxies of past climates and environments. The criteria for distinguishing primary from secondary speleothem calcite, and the conditions (open or semiclosed) of speleothem calcite recrystallization remain poorly understood. Thus, in this study, we investigated the fabric, geochemical composition, and recrystallization dynamics of a partially recrystallized calcite stalagmite (DDH-Z-2) from Didonghe Cave in Shaanxi Province, China, through petrographic observations, fluorescence microscopy, and geochemical analyses (stable isotopes, trace elements, U\\Th isotopes). We found that: (1) in the DDH-Z-2 stalagmite, open elongated columnar calcite recrystallized into compact elongated columnar calcite. Particulate organic matter and fulvic and humic acids were removed during recrystallization, while aromatic compounds were preserved and became incorporated into the secondary calcite; (2) calcite recrystallization was affected by multiple factors, including external fluid chemistry, primary calcite microstructure, and organic matter; (3) calcite recrystallization occurred under open, fluid-buffered conditions for alteration of the stable isotopes (618O and 613C) and trace elements (Mg, Sr, U). The effect of external fluid composition on trace element (Mg, Sr) composition of secondary calcite varied across the stages of calcite recrystallization. Caution should, therefore, be exercised when using geochemical proxies in stalagmites composed of inclusion-free elongated columnar calcite: such calcite is likely to be recrystallized, and thus record the composition of reactive fluids at the time of recrystallization. Regarding the geochemical system of speleothem diagenesis, the contribution of the parent material and the sources of reactive fluids are key factors to consider. (c) 2024 Elsevier B.V. All rights are reserved, including those for text and data mining,

High -precision U-Th age is the key to promoting speleothem as an important archive for paleoclimate study. Notably, obtaining reliable U-Th age primarily relies on the accurate initial 230Th correction. However, correcting the U-Th age of stalagmite with the average 232Th/238U value in the crust is sometimes not enough to eliminate the effect of the initial230Th, using other dating methods (e.g., 14C) and referring to the characteristics of speleothem 818O values are useful to guide its age correction and establish the chronology. This paper presents a comprehensive study of the chronology and isotopic record of a stalagmite XBL-5 from Xiaobailong Cave, Yunnan, China, using a combination of stalagmite U-Th dating, 14C dating, and 818O wiggle match dating. The low uranium content of this stalagmite and the apparent inversion of U-Th dating prevent us from establishing the proxy profiles with reliable chronology. We determined the actual age range based on 14C ages assuming various dead carbon proportion (DCP) and uncorrected U-Th ages, along with the characteristic of stalagmite 818O variations, and then established a credible chronology of this stalagmite through wiggle match of 818O records. Taking the tuned ages as a reference, the initial 230Th/232Th values were reciprocally calculated. The initial 230Th/232Th atomic ratio of the studied samples was back-calculated to be 75.7 +/- 11.4 x 10-6, an order of magnitude higher than the commonly used correction value. The reconstructed XBL-5 818O record spans the Younger Dryas (YD) period, indicating that the precipitation 818O generally increased within the YD chronozone with significant centennial scale oscillations in regions affected by the Indian summer monsoon, in contrast to the speleothem records from East Asian summer monsoon domains which show no or even weakly decreased longterm trend in precipitation 818O. This study highlights the importance of initial thorium correction in stalagmite chronology study and provides a paradigm for sequence reconstruction of similar samples.

Abstract The complexity of processes affecting soil organic carbon (SOC) turnover on spatio‐temporal scales often hinders the extrapolation of results from specific sites to larger scales. This study presents Holocene speleothem U‐Th ages paired with 14C ages of carbonate and dissolved organic carbon (DOC) through three caves located on a north‐south transect through China. The deviations of speleothem 14CDOC ages from the U‐Th ages show clearly spatial variability, and they are positively correlated with mean ages of modern SOC and soil turnover time, suggesting that deviations can be used to infer the SOC turnover. We further demonstrate that slow SOC turnover (large deviation) was associated with weak monsoon (low temperature/less precipitation) on temporal scales. Our findings reveal that climate dominates the speleothem 14CDOC ages and SOC turnover. As global warming likely will intensify, the accelerated turnover of SOC, particularly at higher latitude areas, may partially offset the existing soil carbon stock.

A technique is developed to quantify the ultra-trace 231 Pa (35–3904 ag) concentration in seawater using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The method is a modification of the process developed by Shen et al. (Anal Chem 75(5):1075–1079, 2003. https://doi.org/10.1021/ac026247r ) and extends it to the application of very low levels of actinides, and the 35 ag 231 Pa can be measured with a precision of 15%. The total process blank for the water column was 0.02 ag/g, while the values of the large and small particles were ~ 30 ag/g. The ionization efficiency (ions generated/atom loaded) varies from 0.7 to 2.4%. The measurement time is 2–5 min. The amount of 231 Pa needed to produce 231 Pa data with an uncertainty of ± 0.8–15% is 35–3904 ag (~ 0.9 × 10 5 to 10 × 10 6 atoms). Replicate measurements of known standards and seawater samples demonstrate that the analytical precision approximates that expected from counting statistics, and that based on detection limits of 52 ag, 55 ag, and 28 ag, protactinium can be detected in a minimum seawater sample size of ~ 2.6 L for small suspended particulate matter (> 0.8 μm and < 51 μm), ~ 3.0 L for large suspended particulate matter (> 51 μm), and ~ 56 mL for filtered (< 0.45 μm) seawater. The concentration of 231 Pa (several attograms per liter) can be determined with an uncertainty of ± 2–8% (2 σ ) for suspended particulate matter filtered from ~ 60 L of seawater. For the dissolved fraction, ~ 1 L of seawater yields 231 Pa measurements with a precision of 0.8–10%. The sample size requirements are several orders of magnitude less than traditional decay-counting techniques, and the precision is better than that previously reported for ICP-MS techniques. Our technique can also be applied to other environmental samples, including river, lake, and cave water samples.

The tropical Pacific influences climate patterns across the globe, yet robust constraints on decadal to centennial‐scale climate variations are difficult to extract from sparse instrumental observations in this region. Oxygen isotope (δ 18 O) records from long‐lived corals enable the quantitative reconstruction of tropical Pacific climate variability and trends over the twentieth century and beyond, but such corals are exceedingly rare. Here, we use multiple short coral δ 18 O records to create a coral ‘ensemble’ reconstruction of twentieth century climate in the central tropical Pacific. Ten U/Th‐dated fossil coral δ 18 O records from Kiritimati Island (2°N, 157°W) span 1891 CE to 2006 CE, with the younger samples enabling quantitative comparison to a large ensemble of modern coral records and instrumental sea surface temperature. A composite record constructed of modern and fossil Kiritimati coral δ 18 O records shows a shift toward warmer and fresher conditions from 1970 CE onward, consistent with previously published records in this region.

Coral microatolls allow for the reconstruction of relative sea level (RSL) and the inference of tectonic deformation along tropical coastlines over the Holocene. Microatolls track RSL with unparalleled vertical precision, and their annual banding allows us to count years precisely over an individual coral’s lifetime; however, RSL histories reconstructed from multiple corals depend on accurate and precise radiocarbon (14C) or uranium-thorium (230Th) ages. We collected coral microatoll slabs from sites in Ilocos Region, northwestern Luzon, Philippines, and dated them with 14C and 230Th techniques. Notably, initial RSL reconstructions for some sites disagreed markedly depending on the dating technique used. Attempts to replicate geochronologic analyses have shown that the coral skeletons are susceptible to diagenesis, complicating efforts to accurately determine coral ages. We are developing a strategy to overcome this limitation. We extracted multiple samples from each microatoll slab for paired 14C and 230Th dating. The number of annual bands separating any dated sample was used to further constrain the age of the coral; by subtracting the number of years from each dated sample, samples taken from different parts of the slab can produce independent estimates of the outermost preserved band. After excluding anomalously young replicate 14C ages and samples flagged as partly calcified by x-ray diffraction, we find that 230Th ages from a single coral disagree at 4σ in 4 of 8 cases, whereas calibrated 14C dates overlap at 2σ in 8 of 9 cases for an arbitrary radiocarbon marine reservoir correction, ∆R = 0 yr. Using OxCal and the Marine20 calibration curve, we apply Bayesian statistics to combine 14C and 230Th ages, to estimate ∆R, and to determine the coral ages using the best available data. We further analyze the ∆R value for each coral, and account for overdispersion and underdispersion, whilst generating a ∆R value per site, and an overall ∆R value (inclusive of all sites). We find no statistically significant difference in ∆R for each site, and we calculate an overall ∆R of -155 ± 117 yr for sites in Ilocos Region since the mid-Holocene, though century-scale variability in ∆R may occur. Additionally, to improve the reliability of our dates, our final dating strategy in OxCal is to apply the previously determined ∆R, to a code that places the corals in sequence (based on precise elevation measurements, morphological similarities, and coral die-down events), along with the 14C dates that are dated to the outermost preserved band.

Dissolved Mn(II) in the hydrothermal plume is known to be microbially oxidized to form Mn(III/IV) oxides, and the Mn oxides scavenge other trace elements in seawater. In the GEOTRACES GP16 cruise, dissolved Mn (dMn) and particulate Mn (pMn) were found to be transported over 4000 km westwards from the Southern Eastern Pacific Rise. Previous studies in this plume showed different removal rates of dMn and pMn as well as pMn size distribution between the near-field (<80 km from the ridge axis) and far-field (>80 km) plumes. In order to understand Mn cycling in these plumes, spatial distribution, oxidation states, and mineral structures of Mn in small size fraction (SSF; 0.8-51 mu m) and large size fraction (LSF; >51 mu m) particles from the near-field and farfield plumes were examined using micro X-ray fluorescence spectrometry (mu-XRF), X-ray absorption near-edge structure spectroscopy (XANES), chemical species mapping, and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the near-field plume, pMn in the SSF is dominated by oxidized Mn with Mn(III) fractions of similar to 30%. They are a mixture of delta-MnO2 and triclinic birnessites that is known to be formed as a result of autocatalytic Mn(II) oxidation at the surface of freshly-formed delta-MnO2, suggesting that both microbial and autocatalytic Mn oxidation occur in the near-field plume. The LSF pMn in the near-field plume is also oxidized and often found in large aggregates several hundreds of mu m in size. These aggregates settle out in the near-field and during transport, and are not found in the far-field plume. In the far-field plume where Mn oxides are not newly formed, pMn in the SSF is oxidized, but their Mn(III) fractions are smaller than in the near-field pMn. Unlike the SSF, the far-field plume LSF pMn is dominated by reduced Mn, implying very slow aggregation of pMn in the far-field plume. The different characteristics of pMn between the near-field and far-field plumes affect its scavenging of other trace elements. In the near-field plume, Co, Mo, Pa-231 are associated with pMn, but not in the far-field plume. Pa-231 is adsorbed to pFe rather than pMn in the far-field plume, and Pb is adsorbed to pFe in the entire plume. The result shows that freshly-formed Mn oxides in the near-field plume have higher scavenging capacity than the far-field plume pMn.

Trace elements in a speleothem have been considered to be effective proxies to characterize hydroclimatic changes. In this study, we present speleothem trace element records of the penultimate glacial‐interglacial transition from 138 to 125.8 ka BP from the Shangxiaofeng cave in northeastern China. We used two analytical methods, namely, inductively coupled plasma optical emission spectrometry (ICP‐OES) and the Avaatech high‐resolution X‐ray fluorescence (XRF) core scanner. Both methods showed good consistency for Sr/Ca but not for Mg/Ca because of the high Mg detection limit of XRF. By comparing the trace element ratios (Sr/Ca and Mg/Ca) with δ 13 C and by analyzing the slope of the regression line of ln(Sr/Ca) versus ln(Mg/Ca), we found that trace element variations were dominated by hydroclimate‐related prior calcite precipitation (PCP) and water‐rock interaction (WRI). A gradually decreasing trend of Sr/Ca, Mg/Ca, and δ 13 C records during the glacial‐interglacial transition indicated that the hydroclimate moved toward a moist condition with an intensified East Asian summer monsoon (EASM) and transgression of the coastline. The transgression shortened the distance between the cave site and the coastline, possibly contributing to persistent rainfall enhancement at the study site.

Trace elements in cave carbonates (both calcite and aragonite) have been considered major proxies in paleo-hydroclimatic research. However, their imprints in authigenic minerals might be altered by neomorphic processes (e.g., aragonite-to-calcite transformation). Therefore, it is crucial to understand the impacts of neomorphism on the trace element compositions of secondary calcite and understand the mechanisms of trace elements redistribution during neomorphic processes. In this study, two aragonite stalagmites (SN3 and SN15) from Shennong Cave, part of which were transformed into calcite, were further inspected and analyzed in terms of petrological observations, trace element geochemistry, and Mg compositional mapping. The results show that (1) the aragonite-to-calcite transformation in SN3 and SN15 occurs by a dissolution-precipitation mechanism and is influenced by several factors, including internal fluid compositions, microstructure (such as porosity and permeability) of the parent material, and crystal defects. (2) The primary aragonite is enriched in Sr but depleted in Mg compared with secondary calcite because of the crystallographic disparity. The non-equilibrium absorption of Mg and slow diffusive element transport may contribute to the extremely high Mg/Ca ratios in secondary calcite near the mineral phase boundary. Incorporation competition among trace elements also plays an important role in affecting the distribution of Sr and Mg in neomorphic calcite. Considering the previous study on the alteration of isotopes (δ18O, δ13C) associated with the aragonite-to-calcite transformation, we propose that intervening fluids play an important role in altering the secondary calcite oxygen isotopic composition and Mg/Ca ratio, while the composition of primary aragonite dictates the secondary calcite carbon isotopic composition and Sr/Ca ratio, provided that the transformation of aragonite to calcite caused by a dissolution–reprecipitation process occurring in trapped pore water. These results highlight the indispensability of petrographic analysis of speleothem specimens before using trace elements and isotopes for paleoclimate research.

Precipitation is the most important factor affecting the formation of speleothems in arid and semi-arid areas; therefore, their growth frequency could be a potential indicator of hydroclimate changes in these areas. Here, we present a cumulative growth frequency record over the past 16 ka B.P. (before 1950), as obtained from 58 Th-230 dates taken from 26 individual stalagmites from Longfeng Cave, Shanxi Province, northern China. The results show that fewer stalagmites formed during 16-12 ka B.P. and that the growth frequency then increased from 12.0-9.5 ka B.P.. The cumulative growth frequency was highest between 9.5 and 5.0 ka B.P., and it then declined significantly after 5 ka B.P.. The pattern is confirmed not only by the similarity of the growth rate record from the same set of stalagmites and the speleothem delta O-18 record from the same region, but also by synchronization with other paleoclimatic records from surrounding areas. These consistencies show that our reconstruction of the local hydroclimate using the cumulative growth frequency of stalagmites is robust.

While Asian monsoon (AM) changes have been clearly captured in Chinese speleothem oxygen isotope (δ18O) records, the lack of glacial-interglacial variability in the records remains puzzling. Here, we report speleothem δ18O records from three locations along the trajectory of the Indian summer monsoon (ISM), a major branch of the AM, and characterize AM rainfall over the past 180,000 years. We have found that the records close to the monsoon moisture source show large glacial-interglacial variability, which then decreases landward. These changes likely reflect a stronger oxygen isotope fractionation associated with progressive rainout of AM moisture during glacial periods, possibly due to a larger temperature gradient and suppressed plant transpiration. We term this effect, which counteracts the forcing of glacial boundary conditions, the moisture transport pathway effect.

This study provides dissolved and particulate 230Th and 232Th results as well as particulate 234Th data collected during expeditions to the central Arctic Ocean (GEOTRACES, an international project to identify processes and quantify fluxes that control the distributions of trace elements; sections GN04 and GIPY11). Constructing a time series of dissolved 230Th from 1991 to 2015 enables the identification of processes that control the temporal development of 230Th distributions in the Amundsen Basin. After 2007, 230Th concentrations decreased significantly over the entire water column, particularly between 300 and 1500 m. This decrease is accompanied by a circulation change, evidenced by a concomitant increase in salinity. A potentially increased inflow of water of Atlantic origin with low dissolved 230Th concentrations leads to the observed depletion in dissolved 230Th in the central Arctic. Because atmospherically derived tracers (chlorofluorocarbon (CFC), sulfur hexafluoride (SF6)) do not reveal an increase in ventilation rate, it is suggested that these interior waters have undergone enhanced scavenging of Th during transit from Fram Strait and the Barents Sea to the central Amundsen Basin. The 230Th depletion propagates downward in the water column by settling particles and reversible scavenging.

The El Nino-Southern Oscillation (ENSO) represents the largest source of year-to-year global climate variability. While Earth system models suggest a range of possible shifts in ENSO properties under continued greenhouse gas forcing, many centuries of preindustrial climate data are required to detect a potential shift in the properties of recent ENSO extremes. Here we reconstruct the strength of ENSO variations over the last 7,000 years with a new ensemble of fossil coral oxygen isotope records from the Line Islands, located in the central equatorial Pacific. The corals document a significant decrease in ENSO variance of similar to 20% from 3,000 to 5,000 years ago, coinciding with changes in spring/fall precessional insolation. We find that ENSO variability over the last five decades is similar to 25% stronger than during the preindustrial. Our results provide empirical support for recent climate model projections showing an intensification of ENSO extremes under greenhouse forcing. Plain Language Summary Recent modeling studies suggest that El Nino will intensify due to greenhouse warming. Here new coral reconstructions of the El Nino-Southern Oscillation (ENSO) record sustained, significant changes in ENSO variability over the last 7,000 years and imply that ENSO extremes of the last 50 years are significantly stronger than those of the preindustrial era in the central tropical Pacific. These records suggest that El Nino events already may be intensifying due to anthropogenic climate change.

Significance Plankton in the sunlit surface ocean photosynthesize, fixing dissolved CO 2 into particulate organic carbon (POC). This POC sinks and is respired, releasing CO 2 into subsurface waters that are sequestered from the atmosphere. The depth scale over which this regeneration happens strongly affects atmospheric CO 2 , but estimates to date have been sparse and challenging to interpret. We use a new geochemical method to determine POC regeneration depth scales at unprecedented resolution in the South Pacific Ocean, finding shallow regeneration in both oxygen-deficient zone and oligotrophic gyre settings. Our results imply decreased future ocean carbon storage due to gyre expansion and two opposing feedbacks to expanding oxygen-deficient zones, the net effects of which on ocean carbon storage require future research.

Since the 1980-1990s, international research efforts have augmented our knowledge of the physical and chemical properties of the Arctic Ocean water masses, and recent studies have documented changes. Understanding the processes responsible for these changes is necessary to be able to forecast the local and global consequences of these property evolutions on climate. The present work investigates the distributions of geochemical tracers of particle fluxes and circulation in the Amerasian Basin and their temporal evolution over the last three decades (from stations visited between 1983 and 2015). Profiles of 230-thorium (230Th) and 231-protactinium (231Pa) concentrations and neodymium isotopes (expressed as εNd) measured in the Amerasian Basin prior to 2000 are compared to a new, post-2000s data set. The comparison shows a large scale decrease in dissolved 230Th and 231Pa concentrations, suggesting intensification of scavenging by particle flux, especially in coastal areas. Higher productivity and sediment resuspension from the shelves appear responsible for the concentration decrease along the margins. In the basin interior, increased lateral exchanges with the boundary circulation also contribute to the decrease in concentration. This study illustrates how dissolved 230Th and 231Pa, with εNd support, can provide unique insights not only into changes in particle flux but also into the evolution of ocean circulation and mixing.