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1.
This study successfully isolates a fraction of intra-crystalline proteins from shells of the marine gastropod Patella vulgata and assesses the suitability of these proteins for IcPD (Intra-crystalline Protein Diagenesis) geochronology. We discuss the mineralogical composition of this gastropod, investigated for the first time by X-ray diffraction mapping, and use the results to inform our sampling strategy. The potential of the calcitic rim and of a bulk sample (containing both apex and rim) of the shell to act as stable repositories for the intra-crystalline proteins during diagenesis is examined. The composition and the diagenetic behaviour of the intra-crystalline proteins isolated from different locations within the shell are compared, highlighting the necessity of targeting consistent sampling positions.We induced artificial diagenesis of both intra-crystalline and whole-shell proteins by conducting high-temperature experiments in hydrous environment; this allowed us to quantify the loss of amino acids by leaching and therefore evaluate the open- or closed-system behaviour of the different fractions of proteins. The results obtained provide further confirmation that patterns of diagenesis vary according to the protein sequence, structure, and location within or outside the intra-crystalline fraction. As Patella is frequently found in the fossil record, both in archaeological and geological contexts, the application of IcPD geochronology to this biomineral opens up the possibility to obtain reliable age information from a range of sites in different areas of the world.  相似文献   

2.
Ostrich eggshell is a favoured substrate for amino acid geochronology, yielding consistent results and thought to approximate a closed system with respect to protein diagenesis. We found that the intra-crystalline fraction in ostrich eggshell is more challenging to isolate than that from mollusc shells, requiring 72 h oxidative treatment with NaOCl, resulting in a loss of up to half of the whole-shell protein. Through high temperature studies we have shown that under continuous leaching conditions approximately 99% of the intra-crystalline amino acids are resistant to leaching. Furthermore, high temperature experiments of the intra-crystalline proteins at pH 5, 7 and 9 have shown that this fraction is unaffected by pH changes over this range. This study confirms that the intra-crystalline protein fraction in OES may approximate a closed system. The intra-crystalline amino acids have been shown to follow predictable patterns of hydrolysis and racemization for all amino acids studied. Most amino acids showed some conformity to pseudo reversible first order reaction kinetics for racemization over limited D/L ranges, but hydrolysis was generally described poorly by first order kinetics. We therefore tried a new scaling method to determine relative reaction rates, estimated by applying scaling factors to overlap the observed rates of racemization (or hydrolysis) at the different temperatures, with the advantage of not forcing a linear relationship with respect to time. Using apparent first order kinetics, constrained power functions and scaling methods, we estimated the Arrhenius parameters (activation energy, EA and frequency factors, A) for both hydrolysis and racemization. The different methods for the estimation of reaction rates can give significantly different, but equally plausible, activation energies. This study reinforces previous work that indicates we need to understand the underlying mechanisms in order to estimate accurate kinetic parameters.  相似文献   

3.
When mollusc shells are analysed conventionally for amino acid geochronology, the entire population of amino acids is included, both inter- and intra-crystalline. This study investigates the utility of removing the amino acids that are most susceptible to environmental effects by isolating the fraction of amino acids encapsulated within mineral crystals of mollusc shells (intra-crystalline fraction). Bleaching, heating and leaching (diffusive loss) experiments were undertaken on modern and fossil Corbicula fluminalis, Margaritifera falcata, Bithynia tentaculata and Valvata piscinalis shells. Exposure of powdered mollusc shells to concentrated NaOCl for 48 h effectively reduced the amino acid content of the four taxa to a residual level, assumed to represent the intra-crystalline fraction. When heated in water at 140 °C for 24 h, only 1% of amino acids were leached from the intra-crystalline fraction of modern shells compared with 40% from whole shell. Free amino acids were more effectively retained in the intra-crystalline fraction, comprising 55% (compared with 18%) of the whole shell after 24 h at 140 °C. For fossil gastropods, the inter-shell variability in D/L values for the intra-crystalline fraction of a single-age population was reduced by 50% compared with conventionally analysed shells. In contrast, analysis of the intra-crystalline fraction of C. fluminalis does not appear to improve the results for this taxon, possibly due to variability in shell ultrastructure. Nonetheless, the intra-crystalline fraction in gastropods approximates a closed system of amino acids and appears to provide a superior subset of amino acids for geochronological applications.  相似文献   

4.
The inter- and intra-crystalline fractions of Patella vulgata limpets recovered from archaeological sites in Northern Spain (covering Neolithic, Mesolithic, Magdalenian, Solutrean, and Aurignacian periods) were examined for amino acid composition and racemisation over time. The calcitic apex and rim areas of the shells were found to probably be composed of similar proteins, as the D/L values and amino acids were comparable and varied in the same way with increasing age; however, the mineral structures present in these areas differed. The aragonitic intermediate part of the shell showed a distinctly different amino acid composition and mineral structure. The main protein leaching from the inter-crystalline fraction occurred within the first 6000 yr after the death of the organism. In contrast, the intra-crystalline fraction — comprised of a different protein composition than the inter-crystalline fraction — appeared to behave as a closed system for at least 34 ka, as reflected by the lack of a significant decrease in the amino acid content; however, changes in the amino acid percentages occurred during this period. The concentration of aspartic acid remained almost constant with age both in inter- and intra-crystalline proteins, and its contribution to the total amino acid content increased with age at the expense of other amino acids such as glutamic acid, serine, glycine and alanine. Temperature is thought to play a key role in the amino acid racemisation of P. vulgata and could explain why in the localities belonging to the Gravettian and Solutrean period, which formed during relatively cold conditions, D/L values were similar to those detected in shells from sites formed during the Magdalenian.  相似文献   

5.
Artificial diagenesis of the intra-crystalline proteins isolated from Patella vulgata was induced by isothermal heating at 140 °C, 110 °C and 80 °C. Protein breakdown was quantified for multiple amino acids, measuring the extent of peptide bond hydrolysis, amino acid racemisation and decomposition. The patterns of diagenesis are complex; therefore the kinetic parameters of the main reactions were estimated by two different methods: 1) a well-established approach based on fitting mathematical expressions to the experimental data, e.g. first-order rate equations for hydrolysis and power-transformed first-order rate equations for racemisation; and 2) an alternative model-free approach, which was developed by estimating a “scaling” factor for the independent variable (time) which produces the best alignment of the experimental data. This method allows the calculation of the relative reaction rates for the different temperatures of isothermal heating.High-temperature data were compared with the extent of degradation detected in sub-fossil Patella specimens of known age, and we evaluated the ability of kinetic experiments to mimic diagenesis at burial temperature. The results highlighted a difference between patterns of degradation at low and high temperature and therefore we recommend caution for the extrapolation of protein breakdown rates to low burial temperatures for geochronological purposes when relying solely on kinetic data.  相似文献   

6.
Radiocarbon dating is the most widely applied and reliable dating technique for providing chronological control during Marine Isotope Stage 3 (MIS3; ∼60–27 cal kyr BP). Past variations in the atmospheric concentration of radiocarbon mean a calibration curve is required. IntCal20 and SHCal20 calibration curves covering MIS3 are presently largely based on non-atmospheric records which, in combination with larger radiocarbon (14C) dating uncertainties, results in significant smoothing and reduced resolution in calibration curve structure. Floating tree ring radiocarbon chronologies that are wiggle-matched to other palaeo records (particularly to Hulu Cave speleothems) have the potential to provide detailed structure to the MIS3 portion of extant calibration curves. New Zealand subfossil kauri (Agathis australis) trees are long-lived and are useful for constructing temporally-floating MIS3 atmospheric radiocarbon datasets. This paper presents extant and emerging data from several important Northland subfossil kauri locations (Omaha, Babylon Coast, Bream Bay, Kai Iwi Lakes, Mangawhai). We show the span of seven floating MIS3 kauri sequences (individual trees and chronologies) from which sequential radiocarbon series covering a total of 7556 years is now in development (representing 23% of the period 60–27 cal kyr BP). We also report radiocarbon dates for an additional 34 ancient kauri from MIS3 that can provide additional coverage. After these floating subfossil wood sequences have been produced, close to 40% of MIS3 (12,420 years) will be covered by contiguous subfossil kauri radiocarbon measurements. Based on our findings, we discuss the prospects and limitations for obtaining a highly resolved and precise atmospheric radiocarbon calibration curve comprehensively covering MIS3 using subfossil kauri.  相似文献   

7.
We present the results of K-feldspar IRSL dating of the four lower terraces (T3–T6) of the Portuguese Tejo River, in the Arripiado-Chamusca area. Terrace correlation was based upon: a) analysis of aerial photographs, geomorphological mapping and field topographic survey; b) sedimentology of the deposits; and c) luminescence dating. Sediment sampled for luminescence dating gave unusually high dose rates, of between 3.4 and 6.2 Gy/ka and, as a result, quartz OSL was often found to be in saturation. We therefore used the IRSL signal from K-feldspar as the principal luminescence technique. The K-feldspar age results support sometimes complex geomorphic correlations, as fluvial terraces have been vertically displaced by faults (known from previous studies). Integration of these new ages with those obtained previously in the more upstream reaches of the Tejo River in Portugal indicates that the corrected K-feldspar IRSL ages are stratigraphically and geomorphologically consistent over a distance of 120 km along the Tejo valley. However, we are sceptical of the accuracy of the K-feldspar ages of samples from the T3 and T4 terraces (with uncorrected De values >500 Gy). In these cases the Dose Rate Correction (DRC) model puts the natural signals close to luminescence saturation, giving a minimum corrected De of about 1000 Gy, and thus minimum terrace ages; this may even be true for those doses >200 Gy. Luminescence dating results suggest that: T3 is older than 300 ka, probably ca. 420–360 ka (～Marine Isotope Stage [MIS]11); T4 is ca. 340–150 ka (～MIS9-6); T5 is 136–75 ka (～MIS5); T6 is 60–30 ka (MIS3); an aeolian sand unit that blankets T6 and some of the older terraces is 30–≥12 ka. Collectively, the luminescence ages seem to indicate that regional river downcutting events may be coincident with periods of low sea level (associated, respectively, with the MIS10, MIS6, MIS4 and MIS2).  相似文献   

8.
Amino acid racemization (AAR) is a geochronological method that uses the ratio of D- to L-configurations in optically active amino acids from carbonate fossils to determine the time elapsed since the death of an organism. Although AAR techniques have been widely applied to foraminiferal tests, there have been limited dedicated assessments of the potential of isolating a bleach-resistant, intra-crystalline fraction of proteins to improve the reliability of AAR in this biomineral system. In this study, we evaluate the effect of two oxidative pre-treatments (hydrogen peroxide and bleach) on amino acid concentrations and D/L values in sub-modern benthic foraminifers (Ammonia spp. and Haynesina germanica) and well-preserved mid Holocene and mid Pleistocene planktic foraminifers (Pulleniatina obliquiloculata, Globorotalia truncatulinoides, and Globorotalia tumida). The oxidative pre-treatments successfully reduced the amino acid content of the foraminiferal tests to a residual fraction, and with the exception of Ammonia spp., neither pre-treatment substantially affected the relative proportion of individual amino acids. The bleaching pre-treatment does not consistently alter D/L values when compared to peroxide pre-treatment, but it does tend to reduce the subsample variability in D/L values, albeit only to a small degree in an inconsistent fashion. Therefore, we recommend that a relatively weak oxidative pre-treatment with 3% hydrogen peroxide is sufficient for foraminifera-based AAR applications.  相似文献   

9.
Significant uncertainties remain regarding the temporal evolution of natural vegetation during the Quaternary, and drivers of past vegetation change, on the Chinese Loess Plateau (CLP). This study presents analyses of total organic carbon isotopic composition (TOC) and n-alkane ratios (C31/C27) from the Lingtai loess-palaeosol sequence on the central CLP over the last 450 kyr. The results demonstrate that the vegetation in this region comprised a mix of C3 and C4 plants of herb and woody growth-form. C3 plants dominated for most of the last 450 kyr, but this did not lead to extensive forest. C3 woody plants were more abundant in MIS9 (S3 period) and MIS5 (S1 period) during warm and humid climate conditions. Herbs increased in the region since 130 kyr, possibly as a result of increased aridity. On the orbital timescales, there was a reduction of C3 herbal plants in MIS11 (S4) than in MIS12 (L5), and in Holocene than in the last glacial period. Our isotope and n-alkane proxy records are in agreement with Artemisia pollen changes in the region, which is/was the dominant species in this area and varying due to different heat and water conditions between glacial and interglacial periods. Though the climate in MIS1 (S0) was similar to that in MIS11 (S4), a significant increase in woody plants during the Holocene suggests the impact of human activities and ecological effects of changes in fire activity.  相似文献   

10.
Absolute chronologies in paleoceanographic records are often constructed using the 14C dating of coarse fraction foraminifera (>150 μm). However, due to processes such as changes in sediment sources or abundances, sedimentation rates, bioturbation, reworking, the adsorption of modern carbon, etc., several studies conducted in different environmental settings have shown time-lags between records obtained from various granulometric fractions. In this study, we examined temporal phasing between the coarse foraminifera and fine fractions by studying changes in the abundances of δ18O, the 14C ages of the planktonic foraminifera Globigerinoides ruber (G. ruber, 250–350 μm), and the sediment fine fraction (<63 μm) over the last 45 ka in a core obtained from the northern Caribbean Sea. All of the records were found to be in phase during part of the Holocene (at least for the last ≈6 ka). As determined from δ18O records and 14C ages, the fine fraction was younger than G. ruber during the Last Deglaciation (of 1.89 ka). The coupling between bioturbation and changes in the fine fraction, and G. ruber abundances, as tested using a numerical model of the bioturbation record within a mixed-layer depth of 8 cm, was sufficient to explain the results. 14C age discrepancies increased from 5.64 to 8.5 ka during Marine Isotopic Stages (MIS) 2 and 3, respectively. These chronological discrepancies could not be explained by only one process and seemed to result from the interplay between mechanisms: size-differentiated bioturbation (for 1.5 to 2.5 ka), the adsorption of modern atmospheric CO2 (for 3.04 to 5.92 ka), and variations in sedimentological processes that influenced the fine carbonate fraction. However, even if variations in the mineralogical composition of the fine carbonate fraction were identified using scanning-electron microscopy observations, X-ray diffraction measurements, and geochemical analyses (the mol % MgCO3 of magnesian calcite and the Sr/Ca ratio of the bulk fine fraction), they can not account for the observed age differences. The results presented for core MD03-2628 extend beyond this case study because they illustrate the need for a detailed characterization of the various size fractions prior to paleoclimate signal interpretations, especially for chronological studies.  相似文献   

11.
A flight of marine terraces along the Cuban coast records Quaternary sea‐level highstands and a general slowly uplifting trend during the Pleistocene. U/Th dating of these limestone terraces is difficult because fossil reef corals have been affected by open system conditions. Terrace ages are thus often based on geological and geomorphological observations. In contrast, the minimum age of the terraces can be constrained by dating speleothems from coastal mixing (flank margin) caves formed during past sea‐level highstands and carving the marine limestones. Speleothems in Santa Catalina Cave have ages >360 ka and show various cycles of subaerial–subaqueous corrosion and speleothem growth. This suggests that the cave was carved during the MIS 11 sea‐level highstand or earlier. Some stalagmites grew during MIS 11 through MIS 8 and were submerged twice, once at the end of MIS 11 and then during MIS 9. Phreatic overgrowths (POS) covering the speleothems suggest anchialine conditions in the cave during MIS 5e. Their altitude at 16 m above present sea level indicates a late Pleistocene uplift rate of <0.1 mm/ka, but modelling also shows uplift to have been insignificant over a long timespan during the middle Pleistocene since the cave was carved. Our study shows that some flank margin caves in the region of Matanzas are older than commonly believed (i.e. MIS 11 rather than MIS 5). These caves not only can be preserved but are good markers of interglacial sea‐level highstands, more reliable than marine abrasion surfaces. Copyright © 2018 John Wiley & Sons, Ltd.  相似文献   

12.
OSL and IRSL dating are applied to samples from a 152 m-long drill core to constrain the timing of three glaciolacustrine depositional periods within the infill of an overdeepened bedrock trough in the Lower Glatt valley, N Switzerland. The characterisation of the dose-response suggests that the polymineral IRSL50 and pIRIR180/225 signals are close to saturation, while quartz OSL ages are within the range of reliable dating. The demarcation of the upper quartz OSL dating limit, however, remains challenging. Dose-recovery tests performed with long storage periods were used to investigate the reliability of the high region of the dose-response curve. They suggest an upper limit for reliable dating of ∼400 Gy for these samples, which was considerably lower than the commonly used 2D0 criterion. Lifetimes were calculated for the quartz OSL and the thermal stability of the signal is not considered as problematic for the determined ages. Allowing for a contribution from inherited dose due to partial bleaching, places the infill of the overdeepened valley within the penultimate glacial cycle (MIS6).  相似文献   

13.
The taxonomy of the land-snail genus Cerion, and the relevance of hundreds of shell forms to phylogenetic and evolutionary processes has been the subject of much discussion over the past few decades. Fundamental to understanding evolutionary trends is the independent confirmation of the age, biostratigraphic, and chronostratigraphic order of a comprehensive set of fossil forms. Amino acid racemization (AAR) is a geochronological tool applicable to dating living and fossil Cerion shells. The extent of racemization of aspartic acid (Asp D/L) and glutamic acid (Glu D/L) were determined for 507 Cerion shells dating between the early last interglaciation (marine isotope stage (MIS) 5e, c. 125 ka) and the present from the Bahamas. The AAR data based on Cerion support the established morphostratigraphic succession of deposits younger than MIS 5e and provide greater resolution, particularly for biostratigraphic successions of Holocene age. Age models were constructed for Asp and Glu using D/L values paired with 14C ages and historical collection dates from 23 Cerion shells. In addition to the relative-age time series, the Holocene age models developed from D/L Glu and Asp apply to the last 7 ka and geographically within the central Bahamas. In two case studies, large numbers of AAR-generated ages provide insights into the age structure of accretionary soils and rates and age constraints on evolutionary processes related to Cerion land snails.  相似文献   

14.
The concentration ratio of the amino acids alanine and serine in calcite opercula of freshwater gastropods of genus Bithynia has been assessed as an age proxy for British Middle and Late Pleistocene sites. Due to decomposition of peptide-bound serine within intra-crystalline protein molecules, alanine/serine ratios increase with sample age, enabling resolution of the marine oxygen-isotope stage of almost all sites and substage resolution for some sites. However, slight overlaps are evident in alanine/serine ratios between some sites from late in one temperate stage and early in the next; this effect results from the low decomposition rates during cold stages, combined with an evident slight dependence of decomposition rates on site conditions. The technique, which can be extended to the Early Pleistocene without technical refinements, is amenable to quantitative calibration using a first-order rate equation, making it feasible in future to present results as numerical ages, subject to an assumed temperature history. Most Pleistocene sites investigated are shown using this technique to have the same ages as previously deduced using biostratigraphy. However, the serine–alanine ages obtained preclude glaciation of southeast England during MIS 16 or of central England during MIS 10.  相似文献   

15.
Geochemically-fingerprinted tephra beds provide unique chronostratigraphic markers for comparing Quaternary sedimentary records across eastern Beringia (Alaska and Yukon Territory). Establishing reliable numerical age control on these tephra horizons enables them to be placed within firm temporal frameworks and increases their potential as correlative tools for regional palaeoenvironmental reconstructions. To this end we present new single-grain and multi-grain quartz optically stimulated luminescence (OSL) chronologies for loess deposits bracketing three well-documented and regionally significant variants of the Sheep Creek tephra (SCt) at two sites in west-central Yukon Territory (Ash Bend and Quartz Creek). Single-grain OSL ages bracketing the SCt-A and SCt-K reveal that these tephras were deposited during late Marine Isotope Stage (MIS) 5 or early MIS 4. The SCt-C variant and associated organic-rich bed at Ash Bend were likely deposited during late MIS 5, based on a single-grain OSL age of ∼81 ka for the overlying sediments. The single-grain OSL ages obtained for these deposits are in stratigraphic order and in broad agreement with a fission track age estimate of ∼77 ka for the SCt-K. In contrast, comparative chronologies obtained using multi-grain aliquots are stratigraphically inconsistent and unexpectedly young when compared with the independent SCt-K age. Detailed examination of the single-grain OSL datasets reveal a range of unfavourable luminescent properties that could have contributed to the multi-grain aliquot age discrepancies; including, very low yields of luminescent grains, weak OSL signal sensitivities and large populations of aberrant grains (particularly 0 Gy grains and ‘dim’ grains with a tendency to sensitise during the equivalent dose (De) measurement sequence) that have similarly sized OSL signals as grains used for De analysis. Synthetic aliquot De datasets constructed from single-grain OSL measurements reveal that the large proportional light sum contributions of 0 Gy and dim grains could possibly account for multi-grain age underestimations in some of the Ash Bend samples. In light of these potentially problematic averaging effects, we do not consider the multi-grain OSL ages to be reliable and suggest that single-grain approaches may be preferable for dating sediments with similar quartz luminescence behaviours across this region.  相似文献   

16.
We investigated a late Quaternary terrestrial sedimentary sequence (Uwa Formation) in core IC2, from a site adjacent to that of the reported core IC on NW Shikoku Island, SW Japan, and developed its tephra and pollen stratigraphy to refine the age model of the formation. First, we identified 19 horizons with high glass shard concentrations in the IC2 core sediments as possible tephras or cryptotephras, and correlated them with reported tephras on the basis of the major- and trace-element compositions of their glass shards. All correlated widespread tephras and cryptotephras were products of volcanoes in the Kyushu volcanic zone (Aso, Kakuto, Aira, Ata, and Kikai calderas). Second, we confirmed the presence in core IC2 of two pollen zones dominated by Quercus subgen. Cyclobalanopsis, which is an indicator of very warm interglacial vegetation. In the Japanese Islands, these two vegetation zones have usually been considered to characterize marine isotopic stages (MISs) 1 and 11. A previous study of the Uwa Formation correlated the upper pollen zone to MIS 1, but the lower zone was not correlated to MIS 11; rather, it was inferred to be older than MIS 12 because it was stratigraphically below the “Oda” tephra (equivalent to a distal Kasamori 5 [Ks5] tephra [MIS 12]). In this study, however, noting that the Naruohama-IV tephra (Nh-IV; MIS 10d) and Ks5 cannot be distinguished by their shard chemistries, we inferred that the suggested “Oda” tephra actually correlates to Nh-IV, rather than to the Ks5 tephra. By re-assigning the “Oda” tephra to Nh-IV, we could correlate the underlying Quercus subgen. Cyclobalanopsis-abundant zone to MIS 11 and, consequently, a pair of pollen zones indicating cool and warm conditions below the MIS 11 pollen zone to MISs 12 and 13, respectively. The resulting age model whereby tephra and pollen constraints are integrated showed a roughly constant sedimentation rate from MIS 13, without any long-term gaps; further, our MIS 13 horizon in core IC2 corresponds to the reported 1 Ma tephra horizon in core IC. Therefore, these findings represent a dramatic change in the Uwa Formation age model and validate the Uwa Formation as one of the most useful terrestrial archives of Quaternary tephrostratigraphy and paleoclimatic fluctuation in SW Japan.  相似文献   

17.
High-temperature isothermal heating of biominerals has commonly been used to artificially accelerate protein degradation in order to extrapolate kinetic parameters to the lower temperatures experienced in vivo and in the burial environment. It is not easy to test the accuracy of these simulations due to the difficulty of finding samples of known age held at a known temperature. We compare protein degradation in the intra-crystalline organic matrix of heated (80 °C, 110 °C, and 140 °C) massive Porites sp. coral to that directly measured in the skeleton of colonies growing at ∼26 °C and deposited over the last five centuries. This provides the opportunity to critically evaluate the underlying assumption that high-temperature experiments accurately mimic degradation processes and kinetics occurring in a ‘naturally aged’ biomineral. In all samples the intra-crystalline protein fraction was isolated and the L- and D- concentration of multiple amino acids measured using reverse-phase high-performance liquid chromatography (RP-HPLC). There was no evidence of a failure of the closed system in the high-temperature experiments (assessed by X-ray diffraction, thermogravimetric analyses and determination of leached amino acid concentration). We compared conventional methods for estimation of kinetic parameters with a new ‘model-free’ approach that makes no assumptions regarding the underlying kinetics of the system and uses numerical optimisation to estimate relative rate differences. The ‘model-free’ approach generally produced more reliable estimates of the observed rates of racemization in ‘naturally aged’ coral, although rates of hydrolysis (as estimated from the release of free amino acids) were usually over-estimated. In the amino acids for which we were able to examine both racemization and hydrolysis (aspartic acid/asparagine, glutamic acid/glutamine and alanine), it was clear that hydrolysis was less temperature sensitive than racemization, which may account for the differences in degradation patterns observed between the ‘naturally aged’ coral and high-temperature data. It is clearly important to estimate the individual temperature dependence of each of the parallel reactions.  相似文献   

18.
Reliable chronology is critical for reconstructing estuarine delta process. In this study, detailed chronological framework has been performed on a core HPQK01 (52 m in depth) from the central Pearl River delta (PRD) of China. Both quartz OSL and feldspar post-IR IRSL (pIRIR) methods for late Pleistocene sediments, as well as radiocarbon dating for Holocene sediments, were applied to date the core. Results show that quartz OSL ages range from 125 ± 18 ka to 58 ± 6 ka, and that all of them were minimum ages due to the OSL signal saturation. Feldspar pIR200IR290 protocol shows some overestimation in dose recovery test, with the recovered to the given ratio of 1.2, while a ratio of around 1 was obtained for feldspar pIR50IR250 signals. Robust ages have been obtained from feldspar fading corrected pIR50IR250 dating with ages ranging from 150 ± 17 ka to 98 ± 12 ka. AMS 14C results suggest that subtidal-intertidal zone was deposited during the middle Holocene from 8.21 ± 0.19 cal ka BP to 4.99 ± 0.25 cal ka BP. The sedimentology of core HPQK01 record two marine transgressive-regressive cycles. Based on the dating results, the lower fluvial sediment unit (T2) could be correlated to marine isotope stage (MIS) 6, and the lower marine unit (M2) was deposited during MIS 5. A sedimentary hiatus occurred with age range of from MIS 4 to MIS 2. Since middle Holocene, another marine stratum (M1) has been accumulated. Overall, our findings suggest that feldspar pIRIR dating method has the potential to establish the Quaternary chronostratigraphic framework of the PRD for samples with ages within 150 ka.  相似文献   

19.
Zafarraya Cave is considered a reference site for the last presence of Homo neanderthalensis presence in the south of the Iberian Peninsula. In this paper, accelerator mass spectrometry (AMS) radiocarbon dates were carried out on charcoals and faunal remains, U–Th dating using either alpha spectrometry or Thermal-Ionization Mass Spectrometry (TIMS) and ESR dating were performed on faunal remains. These analyses were carried out on samples from the Mousterian levels of the site (archaeostratigraphic units UC, UD, UE, UF, UG). The 14C AMS dates of charcoal samples (n = 11) were scattered and displayed no coherence with the stratigraphy suggesting possible alteration. The delicate charcoal and faunal samples underwent the gentle RR, ZR (ABA) or AG (ABA) pretreatment procedures at ORAU. The RR protocol is currently considered too gentle and the results are considered with caution. Four ZR charcoal pretreatments failed due to the fact that the charcoal samples were altered. Only two charcoals samples subjected to the ZR pretreatment yielded a reliable % C (>60%) (OxA-9001 and OxA-9002, 40,294–42,761 and 38,763–40,604 cal BP). Their ages are consistent with the stratigraphy and are considered to provide the best age estimate for the level bearing the Z2 Neandertal mandible (Unit UE). For the dentine and the bone samples, the 14C AMS were less dispersed. 14C analyses failed for four bone samples due to insufficient collagen content. Moreover, the %C is very low for two samples, suggesting alteration of the fossil remains at Zafarraya. Only two other samples with enough %C (>30%) were retained: OxA-8024 and OxA-8999 (Unit UE). The respective 14C ages range from ∼34 to 39 ka cal BP. The U/Th (TIMS) analyses of enamel samples displayed an extremely low uranium content (< ∼ 0.02–0.04 ppm). Moreover, the U/Th age range of faunal remains is large, thus providing no conclusive results. ESR dating was chosen for this exercise as, in combination with U-series, it can be used to assess U-uptake in open systems. The combined ESR and U/Th (TIMS) age estimates on tooth enamel yielded US-ESR ages between 33 (+3/−4) ka to 43 ± 3 ka (MIS3) for two Equus teeth and one Capra tooth in unit UE, overlapping with the oldest charcoal and bone 14C dates. The age of the Zafarraya fossil remains was derived from the US-ESR time range of 30–46 ka (MIS 3). We consider this age range to be more representative of the Neandertal occupations at the site than the hitherto widely cited uncalibrated 14C age of around 30 ka.  相似文献   

20.
The Bohai Sea is a semi-enclosed continental shelf sea in northern China. Three transgression layers have been identified from the Late Quaternary strata in the western Bohai Sea and the coastal regions, which provide critical information on Late Quaternary sea-level fluctuations and landscape development. The three transgression layers were previously assigned to Marine Isotope Stage (MIS) 1 (transgression 1, T1), MIS 3 (T2) and MIS 5 (T3), respectively, mainly based on 14C dating. However, this chronological framework aroused an enigma that the regional sea level in MIS 3 was even higher than that of MIS 5, conflicting with the context of global sea-level pattern. In order to clarify this issue, here quartz optically stimulated luminescence (OSL) dating (four samples) was used to constrain the T2 chronology of borehole TJC-1 from the western Bohai Sea. Radiocarbon samples (eight) of peaty sediments were also measured for reference and comparison. All the four OSL samples showed saturation ages of >80 ka, suggesting that the T2 layer should have formed at least in MIS 5, instead of in MIS 3. Radiocarbon ages in T2 should have been severely underestimated, with a saturation age range of 22–30 cal ka BP, similar to all the previous published radiocarbon ages. The renewed OSL chronological framework for Late Quaternary transgressions in the western Bohai Sea is in better compliance with the history of global sea-level change.  相似文献   

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