Can 234U–230Th dating be used to date large semi‐arid tufas? Challenges from a study in the Naukluft Mountains,Namibia

The large, extensive tufa deposits of the semi‐arid Naukluft Mountains, Namibia are potentially important palaeoenvironmental indicators in an area with few proxy records. Tufas are reliable indicators of increased moisture availability, and have been shown to be amenable to ²³⁴U–²³⁰Th dating, although two challenges are detrital contamination and open‐system behaviour. Densely cemented tufa facies are good candidates for dating, minimising these problems. We report attempts to date five densely‐cemented units, which are only found rarely within the Naukluft deposits. We applied a detailed methodology using multiple subsample analysis, measurement of insoluble residues, application of ‘isochron’ mixing lines, and attempted open‐systems modelling, alongside observations of micromorphology and cathodoluminescence in order to assess the validity of any obtained dates. Surprisingly, densely cemented tufas were found not always to be suitable for dating. Two units contained detrital contamination, which could not be corrected for using a single leachate correction or ‘isochron’ methods. Two units contained ‘excess ²³⁰Th’. This could result under a closed‐system if initial (²³⁴U/²³⁸U) was sufficiently high. Alternatively this may be the result of open‐system behaviour, and loss of uranium, or incorporation of initial unsupported ²³⁰Th, which render samples unsuitable for ²³⁴U–²³⁰Th dating. Micromorphological appearance and cathodoluminescence behaviour are used to explore these possibilities. This study exemplifies the need for careful sample selection, and highlights the importance of analysing multiple subsamples from any tufa sample. The detailed methodology applied proves to be a powerful tool for identifying the range of problems that can be encountered when selecting suitable candidate samples for successful dating. It also shows that semi‐arid tufa sequences may contain very little material suitable for dating. A reliable age of c 80 ka was obtained for a banded unit within a large fluvial barrage, with less reliable dates suggesting tufa deposition during times since >350 ka through to the late Holocene. Copyright © 2010 John Wiley & Sons, Ltd.     

A new technique for precise uranium-series dating of travertine micro-samples

Secondary carbonate formations, such as travertine and calcareous tufa deposits, are important archives for quaternary continental climate studies and archaeology. The extremely complex growth mechanisms result in some serious problems for precise mass spectrometric uranium-series dating. Often, detrital and organic particles contaminate the carbonate and large pore volumes yield a great potential for open system behavior. We utilized microscopic, mineralogical and geochemical methods prior to sample selection to determine the abundance of primary calcite, i.e. micrite and spar. Furthermore, the state of alteration was characterized by cathodoluminescence and trace-element analysis. We conclude that travertine and calcareous tufa are appropriate for precise U-series age determination if a) micrite and/or spar are the dominant phases; b) cathodoluminescence of both phases is weak or absent; c) Fe and Al levels are low; and d) Sr concentrations are close to the average of the studied site. We mapped and sampled solely areas of major micrite/spar abundance having minor alteration for accurate U-series dating. When this new method was applied, travertines located in eastern Germany (sites Bad Langensalza, Burgtonna and Weimar-Ehringsdorf) gave single ²³⁰Th/²³⁸U-ages consistent with the lithological growth sequence and greatly improved compared to previously published chronologies. In addition, we determined ²³⁰Th/U isochron ages on bulk samples that confirm our single ages. In contrast to primary calcite, pore cements are homogeneously distributed throughout the travertine fabric and reflect early diagenetic processes and/or weathering.     

Uranium-Series Dating of Carbonate (Tufa) Deposits Associated with Quaternary Fluctuations of Pyramid Lake, Nevada

Uranium-series dating of dense tufa deposited in a small cave, at former lake margins, and in large tufa mounds clarifies the timing of lake-level variation during the past 400,000 yr in the Pyramid Lake basin. A moderate-sized lake occasionally overflowed the Emerson Pass sill at elevation of 1207 m between ca. 400,000 and 170,000 and from ca. 60,000 to 20,000 yr B.P., as shown by²³⁰Th/²³⁴U ages of the cave samples,²³⁰Th-excess ages of tubular tufas, and average isochron-plot ages of shoreline-deposited tufas. (By comparison, modern Pyramid Lake is 50 m below this sill). There is a lack of tufa record during the intervening period from ca. 170,000 to 60,000 yr B.P. After ca. 20,000 yr, Pyramid Lake underwent abrupt changes in level and, based on previous¹⁴C ages, reached its highest elevation (ca 1335 m) at ca. 14,000 yr B.P. The youngest uranium-series ages are comparable with previously reported¹⁴C ages.     

洞穴地点骨化石铀系年龄可信度的讨论*

骨化石是铀不平衡系测年法广泛应用而又颇有争议的研究对象。文章通过对典型铀加入模式的计算,指出以α能谱的精度,二种铀系年龄差异的显著性表明近期内有较大量铀的迁移,但其在误差范围内的一致不能保证样品构成封闭体系。以往积累的数据表明,大多数洞穴地点骨化石给出了二法一致的铀系年龄,但钙板与下伏骨化石铀系年龄大多差异显著且与地层顺序矛盾,即使被次生碳酸盐岩包裹,多半骨化石的铀系年龄仍显著偏低于其包裹体。此外,相当一部分样品的U-Th同位素比难以用简单的铀后期加入或淋失来解释。基于对次生碳酸盐岩铀系年龄可信度的认识,骨化石总体上不构成封闭体系,所载铀系年代信息只具有限的分辨率。     

Pleistocene climatic change in Southern Australia and its effect on speleothem deposition in some Nullarbor caves

Activity ratios of ²³⁴U/²³⁸U, ²³⁰Th/²³⁴U, and ²³⁰Th/²³²Th have been determined for calcite, gypsum and halite speleothems from caves of the Nullarbor Plain, mostly in the area N and NW of Mundrabilla Station, for the purpose of U-series dating. All calcite speleothems contain adequate amounts of uranium for dating, but some show an excess of ²³⁰Th. Stratigraphic relationships indicate that there were at least three phases of calcium carbonate deposition in the Nullarbor caves. The calcite samples, with one possible exception, have ages in excess of ca. 400000 yrs BP. This suggests that no significant amounts of calcium carbonate deposition have taken place during the last 400ka. At present, active deposition of speleothems is restricted almost entirely to gypsum and halite. The only gypsum speleothem dated was found to have a finite age of ca. 185 ka. Six dates on a small halite speleothem containing insect and arachnid remains indicate that it formed rapidly during Holocene time.     

In situ U-series dating by laser-ablation multi-collector ICPMS: new prospects for Quaternary geochronology

The capabilities and potential applications of in situ dating of Quaternary materials using laser ablation-MC-ICPMS are explored. ²³⁴U/²³⁸U and ²³⁰Th/²³⁴U can be measured with precision sufficient for dating at a spatial resolution of 100 μm or better in samples that contain as a little as 1 ppm uranium. Moreover, U and Th concentrations and U-series isotope ratios can be continuously profiled to determine changes in age that occur with sample growth (e.g. in speleothems). These capabilities additionally permit the dating of bones, teeth and possibly molluscs, which are subject to post-mortem open-system behaviour of U-series isotopes, and can be employed to elucidate processes of U-series migration during weathering and diagenesis. A drawback of laser ablation-MC-ICPMS is that it cannot in general provide U-series age estimates with the high precision and accuracy of conventional TIMS or solution MC-ICPMS methods. However, sample preparation is straightforward, the amount of sample consumed negligible, and it can be used to rapidly characterise or screen and select samples from which more precise and accurate dates can be obtained using conventional methods. Given further instrumental developments and the establishment of suitable matrix-matched standards for carbonates and other materials, we foresee that laser ablation-MC-ICPMS will play an increasingly important role in Quaternary dating research.     

U-Th dating of Lake Lisan (late Pleistocene dead sea) aragonite and implications for glacial east Mediterranean climate change

U-series dating can be an effective means to obtain accurate and precise ages on Quaternary carbonates. However, most samples require a correction for U and Th in admixed detritus. This complication is often addressed through generation of U-Th isochrons, requiring analyses of several coeval samples. In addition, presence of water-derived (hydrogenous) Th in the carbonate can cause inaccuracies in isochron ages.This study reports a high-resolution U-series chronology of sediments deposited by Lake Lisan, the last glacial precursor of the Dead Sea. The strategy employed combines multiple measurements from a few stratigraphic heights and fewer analyses from many heights in a single described and measured section. The resulting chronology is based on ages at 22 heights in a ∼40-m-thick section covering the interval of ∼70-14 calendar ka BP. The effects of admixed detritus are evaluated using trace elements. Nearly pure aragonite samples, indicated by very low abundances of insoluble elements such as Nb and Zr, were found to contain hydrogenous Th, which causes the uncorrected U-²³⁰Th age of a modern sample to be ∼2.5 ka. Nevertheless, accurate ages have been obtained by correcting for the detrital and aqueous interferences. The resulting ages are in stratigraphic order, and their accuracy is evidenced by consistency of Lisan Formation U-series and ¹⁴C ages with the coral-based calendar-radiocarbon age calibration.The U-Th ages provide a context to unravel the limnological history of Lake Lisan. Boundaries between the Lower, Middle, and Upper stratigraphic units correspond to the MIS 4/3 and 3/2 transitions, respectively. During MIS 2 and 4 the lake generally showed a stable two-layer configuration and a positive fresh-water balance, reflected by deposition of laminated aragonite-detritus. Dry intervals during MIS 2 and 4 are indicated by thick gypsum layers and an inferred depositional hiatus, which are temporally associated with Heinrich events H1 at ∼17 ka and H6 at ∼65 ka, respectively. During MIS 3 the lake level was unstable with intermittent dry periods indicated by abundant clastic layers and a significant hiatus between ∼43-49 ka. Clastic layers are associated with Dansgaard-Oeschger events during MIS 3, and indicate lake level declines during abrupt Northern Hemisphere warmings. Overall, the climate of the Eastern Mediterranean region shows a strong linkage to the Northern Hemisphere climate, with increasing lake size and stability during cold periods, and fluctuations and dessication during warmings and Heinrich events.     

Spatial variability of initial 230Th/232Th in modern Porites from the inshore region of the Great Barrier Reef

The main limiting factor in obtaining precise and accurate uranium-series (U-series) ages of corals that lived during the last few hundred years is the ability to constrain and correct for initial thorium-230 (²³⁰Th₀), which is proportionally much higher in younger samples. This is becoming particularly important in palaeoecological research where accurate chronologies, based on the ²³⁰Th chronometer, are required to pinpoint changes in coral community structure and the timing of mortality events in recent time (e.g. since European settlement of northern Australia in the 1850s). In this study, thermal ionisation mass spectrometry (TIMS) U-series dating of 43 samples of known ages collected from living Porites spp. from the far northern, central and southern inshore regions of the Great Barrier Reef (GBR) was performed to spatially constrain initial ²³⁰Th/²³²Th (²³⁰Th/²³²Th₀) variability. In these living Porites corals, the majority of ²³⁰Th/²³²Th₀ values fell within error of the conservative bulk Earth ²³⁰Th/²³²Th atomic value of 4.3 ± 4.3 × 10^?6 (2σ) generally assumed for ²³⁰Th₀ corrections where the primary source is terrestrially derived. However, the results of this study demonstrate that the accuracy of ²³⁰Th ages can be further improved by using locally determined ²³⁰Th/²³²Th₀ values for correction, supporting the conclusion made by Shen et al. (2008) for the Western Pacific. Despite samples being taken from regions adjacent to contrasting levels of land modification, no significant differences were found in ²³⁰Th/²³²Th₀ between regions exposed to varying levels of sediment during river runoff events. Overall, 39 of the total 43 ²³⁰Th/²³²Th₀ atomic values measured in samples from inshore reefs across the entire region show a normal distribution ranging from 3.5 ± 1.1 to 8.1 ± 1.1 × 10^?6, with a weighted mean of 5.76 ± 0.34 × 10^?6 (2σ, MSWD = 8.1). Considering the scatter of the data, the weighted mean value with a more conservative assigned error of 25% (i.e. 5.8 ± 1.4 × 10^?6) that encompasses the full variation of the 39 ²³⁰Th/²³²Th₀ measurements is recommended as a more appropriate value for initial ²³⁰Th corrections for U-series dating of most Porites samples from inshore regions of the GBR. This will result in significant improvement in both the precision and accuracy of the corrected ²³⁰Th ages related to those based on the assumed bulk Earth ²³⁰Th/²³²Th₀ value of 4.3 ± 4.3 × 10^?6. However, several anomalously high ²³⁰Th/²³²Th₀ values reaching up to 28.0 ± 1.6 × 10^?6 occasionally found in some coral annual bands coinciding with El Niño years imply high ²³⁰Th/²³²Th₀ sources and highlight the complexities of understanding ²³⁰Th/²³²Th₀ variability. For U-series dating of young coral samples from such sites where anomalous ²³⁰Th/²³²Th₀ values occur, we suggest replicate dating of multiple growth bands with known age difference to verify age accuracy.     

Palaeoenvironmental records in Holocene Spanish tufas: a stable isotope approach in search of reliable climatic archives

Tufa deposits are potential terrestrial archives of palaeoenvironmental and palaeoclimatic information. This study assesses the potential of stable isotopic archives from two closely juxtaposed Holocene tufa sites in SE Spain. The Ruidera site contains deep‐water lacustrine micrites and tufas, whereas the nearby Alcaraz site represents a shallow barrage tufa. Understanding site characteristics is critical to interpreting the stable isotopic variations. These Holocene lacustrine micrites have isotopic compositions consistent with modern European lake shore microbial carbonates, where the isotopic chemistry is strongly influenced by hydrological and residence time effects. All the lacustrine micrite δ¹³C values were influenced by microenvironmental microbial effects to some degree. Because of these effects, stable isotope data from lacustrine microbial micrites and tufas will not normally yield precise information on the isotopic composition of palaeoprecipitation, temperature or vegetation composition of an area. In contrast, Holocene tufas that formed in shallow, fast‐flowing riverine settings may contain valuable palaeoclimatic archives. The tufa deposits must be largely autochthonous, as at Alcaraz, where in situ reed stem encrustations are present. Records of relative change in air temperature and changes in the source of airmasses are potentially resolvable in the δ¹⁸O data. These interpretations can be verified by other independent climatic data where chronology is constrained. Variations in riverine tufa δ¹³C values probably record changes in local vegetation and/or soil respiration. Covariation between δ¹⁸O and δ¹³C values may be intrinsically linked to climatic factors such as aridity. Tentative palaeoclimatic interpretations for the middle Holocene at Alcaraz based on the isotope data suggest warming (or increasing influence of Mediterranean‐sourced precipitation) between approximately 5000–3000 radiocarbon years BP, accompanied by increased aridity. These interpretations are consistent with the sparse independent palaeoclimatic data and climate modelling results for the Holocene of SE Spain. This study supports the growing evidence that well‐chosen tufa sites could yield valuable palaeoclimatic information.     

U—Series Dating of Fossil Bones：Results from Chinese Sites and Discussions on Its Reliability

Calculations,according to some open-system models,point out that while a statistically significant discrepancy between the results of two U-series methods,^230Th/^234U and ^227Th/^220Th(or ^231Pa/^235U),attests a relatively recent and important uranium migration,concordant dates cannot guarantee closes-system behavior of sample.The results of 20 fossil bones from 10 Chinese sites,19 of which are determined by two U-series methods,are given,Judging from independent age controls,8 out of the 11 concordant age sets are unacceptable,The results in this paper suggest that uranium may cycle into or out of fossil bones,such geochemical events may take place at any time and no known preserving condition may securely protect them from being affected.So for the sitew we have studied,the U-series dating of fossil bones is of limited reliability.     

Variation of initial Th/Th and limits of high precision U-Th dating of shallow-water corals

One hundred eighty U-Th data, including 23 isochrons on 24 pristine modern and Holocene corals and 33 seawater samples, were analyzed using sector-field mass spectrometry to understand the variability of initial ²³⁰Th/²³²Th (²³⁰Th/²³²Th₀). This dataset allows us to further assess the accuracy and precision of coral ²³⁰Th dating method. By applying quality control, including careful sampling and subsampling protocols and the use of contamination-free storage and workbench spaces, the resulting low procedural blanks give an equivalent uncertainty in age of only ±0.2-0.3 yr for 1-2 g of coral sample. Using site-specific ²³⁰Th/²³²Th₀ values or isochron techniques, our study demonstrates that corals with an age less than 100 yrs can be ²³⁰Th-dated with precisions of ±1 yr. Six living subtidal coral samples were collected from two continental shelf sites, Nanwan off southern Taiwan in the western Pacific and Son Tra off central Vietnam in the South China Sea; one coral core was drilled from an open-ocean site, Santo Island, Vanuatu, in the western tropical Pacific; and modern and fossil intertidal coral slabs, 17 in total, were cut from six sites around the islands of Simeulue, Lago, North Pagai and South Pagai of Sumatra in the eastern Indian Ocean. The results indicate that the main source of thorium is the dissolved phase of seawater, with variation of ²³⁰Th/²³²Th₀ depending on local hydrology. With intense input of terrestrial material, low ²³⁰Th/²³²Th₀ atomic ratios of 4.9 × 10⁻⁶ and 3.2 × 10⁻⁶ with a 10% variation are observed in Nanwan and Son Tra, respectively. At the Santo site, we find a value of 5.6 × 10⁻⁶ at 4 horizons and one high value of 24 × 10⁻⁶ in a sample from AD 1974.6 ± 0.5, likely due to the upwelling of cold water during a La Niña event between AD 1973 and 1976. The natural dynamics of ²³⁰Th/²³²Th₀ recorded in the intertidal corals at sites in the Sumatran islands are complicated so that this value varies significantly from 3.0 to 9.4 × 10⁻⁶. Three of the 141 modern coral ²³⁰Th ages differ from their true ages by −23 to +4, indicating the presence of detrital material with anomalous ²³⁰Th/²³²Th values. Duplicate measurement of coeval subsamples is therefore recommended to verify the age accuracy. This improved high precision coral ²³⁰Th dating method raises the prospects of refining the age models for band-counted and tracer-tuned chronologies and of advancing coral paleoclimate research.     

Climatic significance of seasonal trace element and stable isotope variations in a modern freshwater tufa

We present a continuous ∼14-yr-long (1985 to 1999) high-resolution record of trace element (Mg, Sr, Ba, U) and stable isotope (δ¹³C, δ¹⁸O) variations in a modern freshwater tufa from northwestern Queensland, Australia. By utilizing the temperature dependence of the δ¹⁸O signal, an accurate chronology was developed for the sampled profile, which allowed a comparison of the chemical records with hydrological and meteorological observations. As a consequence, it was possible to constrain the relevant geochemical processes relating climate variables, such as temperature and precipitation, to their chemical proxies in the tufa record. Temperatures calculated from the Mg concentrations of the tufa samples provide close approximations of average annual water temperature variations. Furthermore, we demonstrate that temporal changes in (Mg/Ca)_water can be estimated using an empirically derived equation relating (Mg/Ca)_water to the (Sr/Ba) ratio measured in the tufa samples. By means of this relationship, it is theoretically possible to determine the (Mg/Ca) ratio of paleowaters, and hence to derive reliable estimates of former water temperatures from the Mg concentrations of fossil tufas from the study area. Sympathetic variations in Sr, Ba, and δ¹³C along the sampled profile record changes in water chemistry, which are most probably caused by variable amounts of calcite precipitation within the vadose zone of the karst aquifer. This process is thought to be markedly subdued whenever the amount of wet-season precipitation exceeds a given threshold. Accordingly, distinct minima in Sr, Ba, and δ¹³C are interpreted to reflect years with above-average rainfall. The pronounced seasonal and annual variability of the U concentration along the profile is thought to primarily record changes in the U flux from the soil to the water table. We suggest that during intensive rain events U is transported to the phreatic zone by complexing organic colloids, giving rise to conspicuous U maxima in the tufa after above-average wet seasons. This study demonstrates the potential of freshwater tufas to provide valuable information on seasonal temperature and rainfall variations. If tufa deposits turn out to be reasonably resistant to secondary processes, combined investigation of speleothems and tufas from the same area could become a promising approach in future research. While speleothems offer continuous records of long-term paleoenvironmental changes, tufas could provide high-resolution time windows into selected periods of the past.     

层状钙华及其地球化学指标的古气候/环境意义

层状钙华作为高分辨率古气候环境重建记录已被国内外许多学者所关注.钙华的微层厚度、氧碳同位素组成和微量元素的含量都呈现出随季节变化的周期性特点.钙华年层的形成与方解石沉积速率或者微生物生长活性的季节变化有关;氧同位素组成的变化主要受温度和沉积水体的δ18O控制,但蒸发作用(尤其是在干旱区)也有重要影响;钙华的稳定碳同位素...     

Comparison of radiocarbon and uranium-series dating methods as applied to marine apatite

A comparison of uranium-series geochronology and radiocarbon dating, the first systematic test of its kind applied to authigenic marine apatite, has been made for nine seafloor phosphate nodules sampled from the Peruvian and Chilean shelves. Radiocarbon ages agree well with the ²³⁰Th ages for all six samples with ²³⁰Th ages younger than the practical dating limit of the ¹⁴C technique for marine samples. Two of three “old” samples contain no significant ¹⁴C activities, as expected. However, one sample with a high concentration of phosphate pellets contains more than 30% of the modern ¹⁴C activity. The discrepancy between the ¹⁴C and U-series age for this sample is thought to be due to post-depositional adsorption of the particle-reactive elements thorium and protactinium onto pellet surfaces.     

山西娘子关泉钙华记录的MIS12/11以来的气候和植被历史

对山西娘子关绵河不同阶地上沉积的泉钙华进行了高精度的230Th定年和碳氧稳定同位素组成测定。结果发现,绵河II级阶地沉积的娘子关泉钙华的最老年龄在407～466ka,远老于早前通过钙华中的石英砂热发光法(TL)获得的年龄,即绵河II级阶地上的娘子关泉钙华是在中更新世MIS12/11阶段形成的,而非原来认为的是晚更新世的产物。由此推测,绵河III级阶地娘子关泉钙华形成的年代更早,可能是中更新世的MIS14/13阶段。230Th测年获得的绵河I级阶地顶部的钙华形成于5ka前,即是在全新世中期以前形成的。结合钙华规模及其碳氧稳定同位素组成分析进一步发现,上述绵河三级阶地上的娘子关泉钙华均主要是湿热气候下的产物。然而,自II级阶地钙华形成至今,气候总体上在向干冷方向发展,泉域植被则呈现退化的趋势。     

Petrography and textural development of inorganic and biogenic lithotypes in a relict barite tufa deposit at Flybye Springs, NT, Canada

A relict mound of Holocene barite (BaSO₄) tufa underlies the Flybye Springs, a small, barium‐rich, cold sulphur spring system in the Northwest Territories of Canada. The tufa is composed of relatively pure barite with ≤0·34 wt% Ca²⁺ and ≤0·77 wt% Sr²⁺. The mound is made up of coated bubble, raft, undulatory sheet, stromatolitic, coated grain and detrital conglomerate barite tufa. Although previously unreported in barite, these lithotypes are akin to facies found in many carbonate spring deposits. Raft and ooid‐coated grain tufa was formed via ‘inorganic’ barite precipitation in spring water ponds and tributaries where rapid oxidation of sulphide to sulphate established barite supersaturation. Undulatory sheet tufa may have formed by the reaction of dissolved barium with sulphate derived from the oxidation of extracellular polysaccharide‐rich colloidal sulphur films floating in oxygenated, barite‐saturated spring water ponds. Coated bubble, oncoid‐coated grain and stromatolitic tufa with filamentous microfossils was formed in close association with sulphur‐tolerant microbes inhabiting dysoxic and oxygenated spring water tributaries and ponds. Adsorption of dissolved barium to microbial extracellular polysaccharide probably facilitated the development of these ‘biogenic’ lithotypes. Detrital conglomerate tufa was formed by barite cementation of microdetrital tufa, allochthonous lithoclasts and organic detritus, including caribou hair. Biogenic textures, organic artefacts and microfossils in the Flybye barite tufa have survived diagenetic aggradational recrystallization and precipitation of secondary cements, indicating the potential for palaeoecological information to be preserved in barite in the geological record. Similarities between the Flybye barite tufa and carbonate spring deposits demonstrate that analogous textures can develop in chemical sedimentary systems with distinct mineralogy, biology and physiochemistry.     

Precise two chronometer dating of Pleistocene travertine: The Th/U and Raex/Ra(0) approach

In order to determine the geochemical evolution of a freshwater limestone cave system located in central Switzerland (Hell Grottoes at Baar/Zug,) young postglacial tufaceous limestone and travertine precipitates were investigated using the ²³⁰Th/²³⁴U ingrowth system. Additional analyses of further radionuclides within the ²³⁸U decay chain, i.e. ²²⁶Ra and ²¹⁰Pb, showed that the Th/U chronometer started with insignificant inherited ²³⁰Th over the entire formation period of the travertine setting (i.e. ²³⁰Th(0)=0). A contribution from detrital impurities with ²³⁰Th/²³⁴U in secular equilibrium could be precisely subtracted by applying isochron dating of cogenetic phases and recently formed travertine. The resulting precise ²³⁰Th/²³⁴U formation ages were found to be consistent with the geological stratigraphy and were furthermore used to demonstrate the applicability of the next geologically important chronometer in the ²³⁸U-decay series, based on decay of excess ²²⁶Ra normalized to the initial, i.e.²²⁶Ra_ex/²²⁶Ra(0). This system is suitable for dating phases younger than 7000 yr when the correction of a detritus component increasingly limits the precision of the ²³⁰Th/²³⁴U chronometer. Analytical solutions of the coupled ²³⁴U/²³⁰Th/²²⁶Ra radionuclide system predicted that the ²²⁶Ra_ex/²²⁶Ra(0) chronometer is independent of the actual ²³⁰Th activity build up from decay of ²³⁴U, if the systems starts with zero inherited ²³⁰Th(0). The data set confirmed this hypothesis and showed furthermore that the initially incorporated ²²⁶Ra excess must have remained almost uniform in all limestone over a period of at least 7000 yr, i.e. 4–5 half-lives of ²²⁶Ra. This is concluded because (i) the ²²⁶Ra_ex/²²⁶Ra(0) ages agreed well with those derived from ²³⁰Th/²³⁴U, (ii) all data plot within uncertainty on the ²²⁶Ra_ex/²²⁶Ra(0) decay curve and (iii) the atomic Ba/Ca ratio was found to be constant in the travertine material independent of the sample ages. Provided that such boundary conditions hold, ²²⁶Ra_ex/²²⁶Ra(0) should be applicable to materials which are suitable for ²³⁰Th/²³⁴U dating in sedimentology and oceanography, i.e. travertine, corals, phosphorites, etc., and should strongly support ²³⁰Th/²³⁴U for samples that have been formed a few thousand years ago.     

The timing of sea-level high-stands during Marine Isotope Stages 7.5 and 9: Constraints from the uranium-series dating of fossil corals from Henderson Island

Direct dating of fossil coral reefs using the U-series chronometer provides an important independent test of the Milankovitch orbital forcing theory of climate change. However, well-dated fossil corals pre-dating the last interglacial period (>130 thousand years ago; ka) are scarce due to, (1) a lack of sampling localities, (2) insufficient analytical precision in U-series dating methods, and (3) diagenesis which acts to violate the assumption of closed-system U-series isotopic decay in fossil corals. Here we present 50 new high-precision U-series age determinations for fossil corals from Henderson Island, an emergent coral atoll in the central South Pacific. U-series age determinations associated with the Marine Isotope Stage (MIS) 9 interglacial and MIS 7.5 interstadial periods are reported. The fossil corals show relatively little open-system U-series behaviour in comparison to other localities with fossil coral reefs formed prior to the last glacial cycle, however, open-system U-series behaviour is still evident in most of the dated corals. In particular, percent-level shifts in the [²³⁰Th/²³⁸U]_act composition are observed, leading to conventional U-series ages that are significantly younger or older than the true sample age. This open-system U-series behaviour is not accounted for by any of the open-system U-series models, indicating that new models should be derived. The new U-series ages reported here support and extend earlier findings reported in Stirling et al. (2001), providing evidence of prolific coral reef development on Henderson Island at ∼320 ka, most likely correlated with MIS 9.3, and subsequent reef development at ∼307 ka during MIS 9.1, while relative sea-level was potentially ∼20 m lower than during MIS 9.3. The U-series ages for additional well-preserved fossil corals are suggestive of minor reef development on Henderson Island during MIS 7.5 (245-230 ka) at 240.3 ± 0.8 and 234.7 ± 1.3 ka. All U-series observations are consistent with the Milankovitch theory of climate change, in terms of the timing of onset and termination of the dated interglacial and interstadial periods. The best preserved samples also suggest that the oceanic ²³⁴U/²³⁸U during MIS 9 and MIS 7.5 was within five permil of the modern open ocean composition.     

Climatic change recorded by stable isotopes and trace elements in a British Holocene tufa

Combined stable isotope (δ¹⁸O and δ¹³C) and trace element (Mg, Sr) geochemistry from bulk tufa calcite and ostracod shell calcite from an early Holocene British tufa reveal clear records of Holocene palaeoclimatic change. Variation in δ¹⁸O is caused principally by change in the isotopic composition of Holocene rainfall (recharge), itself caused mainly by change in air temperature. The δ¹³C variability through much of the deposit reflects increasing influence of soil‐zone CO₂, owing to progressive woodland soil development. Bulk tufa Mg/Ca and Sr/Ca are controlled by their concentrations in the spring water. Importantly, Mg/Ca ratios are not related to δ¹⁸O values and thus show no temperature dependence. First‐order sympathetic relationships between δ¹³C values and Mg/Ca and Sr/Ca are controlled by aquifer processes (residence times, CO₂ degassing and calcite dissolution/reprecipitation) and probably record intensity of palaeorainfall (recharge) effects. Stable isotope records from ostracod shells show evidence of vital effects relative to bulk tufa data. The ostracod isotopic records are markedly ‘spiky’ because the ostracods record ‘snapshots’ of relatively short duration (years), whereas the bulk tufa samples record averages of longer time periods, probably decades. The δ¹⁸O record appears to show early Holocene warming, a thermal maximum at ca. 8900 cal. yr BP and the global 8200 yr BP cold event. Combined δ¹³C, Mg/Ca and Sr/Ca data suggest that early Holocene warming was accompanied by decreasing rainfall intensity. The Mg/Ca data suggest that the 8200 yr BP cold event was also dry. Warmer and wetter conditions were re‐established after the 8200 yr BP cold event until the top of the preserved tufa sequence at ca. 7100 cal. yr BP. Copyright © 2004 John Wiley & Sons, Ltd.     

Recurrent spring‐fed rivers in a Middle to Late Pleistocene semi‐arid grassland: Implications for environments of early humans in the Lake Victoria Basin,Kenya

The effect of changing palaeoclimate and palaeoenvironment on human evolution during the Pleistocene is debated, but hampered by few East African records directly associated with archaeological sites prior to the Last Glacial Maximum. Middle to Late Pleistocene deposits on the shoreline of eastern Lake Victoria preserve abundant vertebrate fossils and Middle Stone Age arte‐facts associated with riverine tufas at the base of the deposits, which are ideal for palaeoenvironmental reconstructions. New data from tufas identified on Rusinga Island and on the mainland near Karungu, Kenya are provided from outcrop, thin sections, mineralogical, stable isotopic and U‐series dating analyses. Tufa is identified in four sites: Nyamita (94·0 ± 3·3 and 111·4 ± 4·2 ka); Kisaaka, Aringo (455 ± 45 ka); and Obware. The age ranges of these tufa deposits demonstrate that spring‐fed rivers were a recurrent, variably preserved feature on the Pleistocene landscape for ca 360 kyr. Poor sorting of clastic facies from all sites indicates flashy, ephemeral discharge, but these facies are commonly associated with barrage tufas, paludal environments with δ¹³C values of ca 10‰ indicative of C₃ plants and fossil Hippopotamus, all of which indicate a perennial water source. Other tufa deposits from Nyamita, Obware and Aringo have a mixed C₃/C₄ signature consistent with a semi‐arid C₄ grassland surrounding these spring‐fed rivers. The δ¹⁸O values of tufa from Nyamita are on average ca 1‰ more negative than calcite precipitated from modern rainfall in the region, suggesting greater contribution of depleted monsoonal input, similar to the Last Glacial Maximum. Microdebitage and surface‐collected artefacts indicate that early modern humans were utilizing these spring‐fed rivers. The presence of spring?fed rivers would have afforded animals a reliable water source, sustaining a diverse plant and animal community in an otherwise arid environment.