230Th/234U dating of Holocene tufas: possibilities and problems

High-resolution chronologies in continental carbonate deposits such as tufas are required for detailed palaeoclimatic and environmental studies. This work set out to establish if high-resolution U-series dating of detritus-rich Holocene tufas is routinely possible. The study centres on a paludal Holocene tufa from southern England that already has an existing Holocene chronology, based on ¹⁴C and supported by biostratigraphy, against which to compare U-series dates. The results show that significant detrital contamination combined with low initial U concentrations, and short time for ingrowth of radiogenic ²³⁰Th make high-resolution U-series dating of Holocene tufa very difficult. Moreover, a single (²³⁰Th/²³²Th)_initial value to correct for the presence of detrital ²³⁰Th is not appropriate at the study site, a finding that may apply to most Holocene tufas. Total sample dissolution of coeval samples demonstrates considerable variability in the isotopic composition of the detritus. The total sample dissolution data are too scattered to constrain chronologies at the required resolution and may indicate the incorporation of a ²³⁰Th-rich component in the detritus.     

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.     

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。     

Travertine formation in Plitvice National Park, Yugoslavia: chemical versus biological control

Hydrochemical studies of the Plitvice Lakes and their tributaries (Croatia/Yugoslavia) were coupled with micromorphological investigations on carbonate lake sediments and recent travertines. Karst springs discharge water from aquifers in Triassic and Jurassic dolomites and limestones and collect in lakes, which are ponded behind accreting travertine dams. Waters at springs have a high CO₂ partial-pressure (greater than 7000 ppm) and are slightly undersaturated with respect to calcite (saturation index less than —0·03). CO₂ partial pressure is quickly reduced in swift running streams, leading to very high supersaturation with carbonate minerals (saturation indices between 0·74 and 0·53). Calcite deposition, however, is restricted to the lake bottoms (formation of lake marl) and to the tufa dams. The annual carbonate precipitating capacity of the system based on water balance and downstream loss of dissolved ions is estimated to be on the order of 10 000 t CaCO₃ as cascade deposits (tufa dams) or as micrite in lakes behind the travertine dams. The initial stages of travertine formation as a result of morphological, biological, and chemical factors are (i) moss settling on small ridges in the creek courses, (ii) epiphytes (diatoms and cyanobacteria) settling on the moss surface, (iii) micrite particles resuspending from lake bottoms and being trapped on mucous excretions from bacteria and diatoms, and (iv) inorganic calcite precipitating as sparite at nucleation sites provided by these crystal seeds. Geochemical studies of the lake marl and tufa dams show that amino acids are dominated by aspartic acid. Carbohydrates come from structural polysaccharides of diatoms. The sticky excretions, rich in aspartic acid, are necessary for the initiation of calcite precipitation. They may be a response of algal and bacterial metabolism to environmental stress by either nutrient depletion or high calcium concentrations in ambient waters. The formation of tufa and micrite (lake marl) appears to be initiated by localized biological factors and is not governed by mere calcite supersaturation of the water. Oligotrophy may be an essential precondition for the formation of fresh water carbonate deposits.     

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.     

Origin of subaerial Holocene calcareous crusts: role of algae, fungi and sparmicritisation

The Pleistocene Miami Limestone that crops out on the lower Florida Keys is overlain by thin (16 cm or less), discontinuous, Holocene calcareous crusts (caliche) that are usually laminated, composed dominantly of calcite micrite and may or may not incorporate part of the underlying limestone. Both allochems and sparry calcite cement in the former unit contain endolithic algae and fungi, borings and unicellular algae. Biogenic structures identical to those in the Miami Limestone also occur in the calcareous crusts but are somewhat less abundant in the latter unit versus the former unit. The calcareous crusts were formed in the vadose diagenetic environment. Some of the CaCO₃ necessary for the micrite that comprises the bulk of the crusts was probably derived from solution of carbonate from a soil cover and some from wind blown salt spray. Most of the micrite, however, was formed by replacement of the uppermost portions of the Miami Limestone. Replacement involved micritisation of allochems and a previously unreported process, sparmicritisation, the degrading recrystallization of sparry calcite to micrite. Minor sparmicritisation was caused by micrite calcification of endolithic fungi or algae within sparry calcite cement or by micrite precipitation in empty borings within such cement. Most sparmicritisation took place by dissolution of sparry calcite and concomitant precipitation of micrite in the space occupied previously by the dissolved spar. Such sparmicritisation is interpreted to be caused by chemical reactions involving the crystals, pore water which is moving slowly but steadily and organic compounds released during bacterial decomposition of fungi, algae or both. It is recognized that sparmicritisation occurs in the marine diagenetic environment and is not, therefore, necessarily indicative of vadose diagenesis. Incomplete sparmicritisation is responsible for some of the clotted textures typically found within calcareous crusts and may explain such textures in many other carbonate rock types. A combination of sparmicritisation and micritisation has probably greatly influenced the porosity of many reefs and, in some cases, led to the formation of ‘micritic reefs’.     

Freshwater calcite precipitates from in vitro mesocosm flume experiments: a case for biomediation of tufas

Freshwater carbonates (tufas) develop today from the Arctic to the tropics, many being localized about springs and upper water courses. Some Quaternary tufas, especially in the Mediterranean region, extend over tens of square kilometres and exceed 30 m in thickness. Radiometric dating of Holocene deposits shows that many have accumulated at an average rate of 1 mm year^?1. However, local precipitation may be much faster and some Holocene deposits may even have outpaced their tropical marine carbonate counterparts. Recently, the study of active sites has attempted to quantify the precipitation mechanisms which lead to tufa deposition. However, field observation and sampling procedures suffer from the inherent disadvantages of uncontrolled fluctuations in environmental conditions during the study programme. These disadvantages compromise any interpretations, particularly where controls on spar versus micrite precipitation are concerned. Many of these problems have been overcome in the current study by the construction and operation of laboratory mesocosm flumes which simulate the natural conditions (e.g. pH, flow rate, ambient temperature and daylight) in which freshwater carbonate (tufa) is deposited. Three mesocosms were supplied with natural river water from tufa precipitating streams and two mesocosms were supplied with UV‐treated (sterile) river water from the same source. One of the untreated flume mesocosms was linked with a calcium reactor, which replaced calcium ions removed during the precipitation process in order to maintain tufa growth over extended experimental runs. Low‐magnesium calcite precipitates (both rhombic sparite grown from long‐crystallite dendrites and short‐crystallite dendrite triad precursors) and micrite peloids (grown from spherulitic precursors) were precipitated in intimate association with biofilm (extracellular polymeric substances) within the four mesocosms supplied with natural river water. Virtually, no tufa‐like precipitate was obtained from the flumes supplied with UV‐treated river water. A second extended run flume experiment was also carried out for comparison purposes using a calcium hydroxide solution in deionized water. Collectively, these experiments provide convincing evidence confirming that the presence of a microbial biofilm strongly influences the precipitation of carbonates in riverine freshwater settings. In particular, experimental results show that micro‐peloidal micrite and short‐crystallite calcite dendrites are only produced in the presence of microbial extracellular polymeric substances.     

The application of cathodoluminescence to interpreting the diagenesis of an ancient calcrete profile

A laterally extensive calcrete profile has been identified in the Late Asbian (Lower Carboniferous) shallow marine shelf limestones of the Llangollen area, North Wales. The upper surface of the profile is defined by a laterally discontinuous palaeokarstic surface and by laminated calcareous crusts which developed within the underlying limestone. The profile contains a unique series of early pore-filling vadose cements which only occur down to 1 m below the palaeokarstic surface. Cathodoluminescence reveals that these cements pre-date the late pore-filling meteoric phreatic cements which occur throughout local Asbian lithologies. A spar cement stratigraphy has been established for the calcrete profile. Subaerial vadose cements comprise two generations of non-luminescent cement, followed by a brightly luminescent generation which occasionally shows an acicular habit. This needle-fibre calcite represents the final stage of vadose cementation. Precipitation of vadose cements was contemporary with subaerial alteration and micritization of the limestone. Textures, visible only with cathodoluminescence, provide evidence of recurrent periods of fabric dissolution. The most extensive phase of dissolution occurred immediately after the precipitation of the non-luminescent subaerial vadose cements. Several different textures have been recorded, each reflecting the morphology of a partially dissolved substrate. Dissolution textures are generally confined to the walls of the larger pores and to early brecciation fractures. These probably acted as fluid pathways in the calcrete during early subaerial diagenesis. Much of the non-marine micrite in the calcrete profile appears as needle-fibre calcite under cathodoluminescence. This acicular calcite was probably formed in response to localized supersaturation of meteoric pore fluids caused by periods of near-surface evaporation. Since needle-fibre luminescence is strongly variable, these ambient conditions are not believed to have directly controlled the activator ion concentrations of cementing pore waters. Needle-fibre calcite is considered to be a cement precipitate which has almost completely recrystallized to micrite, probably during the late stages of subaerial diagenesis. Two generations of subaerial micrite which define a ‘micrite stratigraphy’, have been distinguished under cathodoluminescence. Reconstructing the diagenetic history of this ancient calcrete profile has revealed that subaerial alteration was multistaged, with many diagenetic processes acting simultaneously during a single phase of emergence.     

Diagenesis or dire genesis? The origin of columnar spar in tufa stromatolites of central Greece and the role of chironomid larvae

Two Greek Pleistocene tufa stromatolites were examined petrographically and with stable isotope geochemistry to determine whether calcite spar is of primary or diagenetic origin. The younger (ca 100 ka) tufa from Zemeno primarily is micritic, with primary columnar calcite spar restricted to areas immediately above chironomid larval tubes. This relationship suggests that chironomid larval feeding behaviour is responsible for the development of Zemeno tufa columnar calcite, probably involving biological substances smeared onto the tufa surface. Most micritic crystals are not suitably oriented to allow later post‐depositional growth resulting in columnar fabrics. The older (ca 1 Ma) predominantly sparry tufa from Nemea contains some chironomid tubes and organic cyanobacterial filaments preserved in crystal fans but also contains many fabrics found in primary speleothem spar. Columnar spar here is unlikely to be the result of post‐depositional crystal growth. A comparison of stable isotopic trends between the two tufa deposits suggests that both contain interpretable seasonal trends and implies little or minor post‐depositional alteration of either tufa. Consequently, there is no basis for the common assumption that sparry tufa fabrics must be of diagenetic origin.     

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.     

How precise are U-series coral ages?

U-series dating of fossil reef corals is a well established and widely applied technique in paleoclimate research. Many fossil corals, however, show evidence for post-depositional diagenetic alteration, and it is generally accepted that the accuracy of U-series coral ages is more limited due to coral diagenesis than analytical precision. In recent years, three models have been published that try to correct the effects of diagenesis and allow the calculation of model ages [Thompson W. G., Spiegelmann M. W., Goldstein S. L., and Speed R. C. (2003) An open-system model for U-series age determinations of fossil corals. Earth and Planetary Science Letters210, 365-381; Villemant B., and Feuillet N. (2003) Dating open systems by the ²³⁸U-²³⁴U-²³⁰Th method: application to Quaternary reef terraces. Earth and Planetary Science Letters210, 105-118; Scholz D., Mangini A., and Felis T. (2004) U-series dating of diagenetically altered fossil reef corals. Earth and Planetary Science Letters218, 163-178].Here, we assess the age variability of both conventional ²³⁰Th/U-dating and the three models by application to different sub-samples of individual coral specimens. The age variability, estimated as the 2σ-standard deviation on the individual ages, is compared with the errors quoted by the different methods. Our results show that the errors of conventional ²³⁰Th/U-dating as well as those of the method of Thompson et al. (2003) do not account for the true age variability. The age variability of both methods is in the range of the errors given by the models of Villemant and Feuillet (2003) and Scholz et al. (2004).Furthermore, we show that the widely used reliability criteria are not sufficient to identify all diagenetically altered corals. In contrast, analysis of different sub-samples of one coral specimen allows (i) to estimate the real age variability, (ii) to test if the assumptions of the models are fulfilled, and (iii) to investigate the diagenetic processes in more detail. Thus, this method should generally be applied to obtain more reliable U-series coral ages and errors.     

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.     

Calcified microbial mats date prehistoric canals—Radiocarbon assay of organic extracts from travertine

A methodology for radiocarbon dating of calcified microbial mats has been developed and successfully applied in establishing a preliminary chronology for the prehistoric carbonate-encrusted canals of the Tehuacán Valley of Puebla, Mexico. In contrast to traditional carbonate dating techniques, this method focuses on the organic carbon component of the calcareous sediments. This method is based on the assumptions that (1) the carbon being dated is derived from the organisms associated with travertine buildup on canals, (2) these organisms are incorporated into the travertine contemporaneous with calcite precipitation, and (3) this carbon is then sequestered from most subsequent contamination and secondary fractionation. Evidence supporting these assumptions includes δ¹³C values, cultural chronologies, and stratigraphic relationships consistent with expectations. © 1996 John Wiley & Sons, Inc.     

Rates of vadose diagenesis in quaternary dune and shallow marine calcarenites,Warrnambool, Victoria,Australia

Progressively younger cycles of Quaternary dune limestones and shallow marine calcarenites infill a coastal embayment near Warrnambool in southeastern Australia. The formations have been dated using U/Th and C¹⁴ methods or have had their ages estimated by comparison with adjacent deposits. They provide a well-dated framework for the quantification of diagenetic rates in the fresh-water vadose zone.The sequence as a whole shows progressive increase in diagenetic alteration with age, related to increasing duration of subaerial exposure. Diagenesis includes alteration of high-Mg calcite to low-Mg calcite, dissolution of aragonite and precipitation of increasing amounts of void-filling low-Mg calcite spar. These changes are reflected in the progression of bulk-rock isotope values from the youngest to the oldest strata.The rocks at Warrnambool pass through 3 main stages of diagenetic evolution. The end of stage 1 is marked by the disappearance of high-Mg calcite. This occurs in just less than 90,000 years. The end of stage 2 occurs between 400,000 and 700,000 years and is marked by the disappearance of aragonite. The end of stage 3 and the beginning of stage 4 is marked by the complete infilling of all pore space by low-Mg calcite spar. This is not generally seen in this sequence but is restricted to specific diagenetic sites such as immediately below paleosol horizons.     

Dating fluvial terraces by Th/U on pedogenic carbonate, Wind River Basin, Wyoming

Reliable and precise ages of Quaternary pedogenic carbonate can be obtained with ²³⁰Th/U dating by thermal ionization mass spectrometry applied to carefully selected milligram-size samples. Datable carbonate can form within a few thousand years of surface stabilization allowing ages of Quaternary deposits and surfaces to be closely estimated. Pedogenic carbonate clast-rinds from gravels of glacio-fluvial terraces in the Wind River Basin have median concentrations of 14 ppm U and 0.07 ppm ²³²Th, with median (²³⁰Th/²³²Th) = 270, making them well suited for ²³⁰Th/U dating. Horizons as thin as 0.5 mm were sampled from polished slabs to reduce averaging of long (≥10⁵ yr), and sometimes visibly discontinuous, depositional histories. Dense, translucent samples with finite ²³⁰Th/U ages preserve within-rind stratigraphic order in all cases. Ages for terraces WR4 (167,000 ± 6,400 yr) and WR2 (55,000 ± 8600 yr) indicate a mean incision rate of 0.26 ± 0.05 m per thousand years for the Wind River over the past glacial cycle, slower than inferred from cosmogenic-nuclide dating. Terrace WR3, which formed penecontemporaneously with the final maximum glacial advance of the penultimate Rocky Mountain (Bull Lake) glaciation, has an age of 150,000 ± 8300 yr indicating that it is broadly synchronous with the penultimate global ice volume maximum.     

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.     

文石-方解石石笋U/Th体系的封闭性判断及意义

湖南省龙山县莲花洞两根大型石笋LLl(文石-方解石型)和LL5(文石型)ICP-MS230Th结果表明,82个年龄数据并不完全符合石笋生长层序律.根据U/Th同位素比值、沉积和矿物学特征,分析了同位素体系开放度对建立石笋正确年代学模式的影响.莲花洞LLl石笋全新世以来234U/238U对230Th/238U的比值具有谐和性特征并且230Th年龄层序正常,说明文石矿物基本接近U/Th同位素封闭系统,实测年龄基本可靠.10～40 ka期间234U/238U与230Th/238U离散度较大和矿物具有溶蚀、风化现象,表明体系发生U加入/流失作用.LL5石笋60～80 ka期间封闭性较好,实测年龄可信.上述结果表明,同一洞穴中文石石笋U/Th同位素体系开放度与时间的关系并不是线性关系,沉积时水文和物理化学性质以及随后的保存状况是决定洞穴文石石笋同位素封闭性的关键因素.     

Physico-chemical environment of pedogenic carbonate formation in Devonian vertic palaeosols, central Appalachians, USA

The morphology and geochemistry of pedogenic carbonate found in vertic claystone palaeosols in the Devonian Catskill Formation in central Pennsylvania preserve a record of the physical and chemical environment of carbonate precipitation. The carbonate is characterized by three distinct petrographic generations. Pedogenic rhizoliths and nodules are the earliest precipitated generation, and typically consist of dull red-brown luminescent micrite. Clear, equant calcite spar cement fills voids in the centres of rhizoliths, as well as circumgranular cracks and septarian voids in nodules. Early spar cements are non-luminescent to dull luminescent, whereas later spar cements exhibit bright yellow-orange luminescence. Late stage pedogenic fractures are always occluded with very bright yellow-orange luminescent spar cements. The incorporation of progressively higher concentrations of Mn (up to 34000 ppm) into successively younger calcite spar cements, without concomitant increases in Fe, suggests carbonate precipitation from an evolving meteoric water in which Mn²⁺ became increasingly mobile over time. The increased mobility is possibly due to decreasing Eh, resulting from oxidation of organic matter after rapid soil burial on the floodplain. The amount of Fe²⁺ available for incorporation into calcite was limited because most iron was immobile, having been earlier oxidized and bound to the palaeosol clay matrix as a poorly crystallized ferric oxide or oxyhydroxide mineral. Carbon isotope compositions of pedogenic carbonate correlate with the inferred depth of carbonate precipitation. Rhizoliths preserved below the lowest stratigraphic occurrences of pedogenic slickensides are consistently depleted in ¹³C relative to nodules, which formed stratigraphically higher, within the zone of active soil shrink and swell processes. Nodular carbonate, precipitated in proximity to deep cracks in the soil, is enriched due to increased gas exchange with isotopically heavy atmospheric CO₂. Accordingly, rhizolith compositions will most accurately estimate palaeoatmospheric levels of CO₂; the use of nodule compositions may result in overestimation of P_CO2 by as much as 30%.     

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.     

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.