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.     

Large earthquakes kill coral reefs at the north-west Gulf of Aqaba

Down‐faulting at the north‐west margins of the Gulf of Aqaba is inferred to have triggered a catastrophic sedimentary event at 2.3 ka that killed the Elat fringing coral reef. Whereas segments of the Holocene reef were perfectly fossilized and preserved beneath a veneer of siliciclastic sediments, other segments were abraded, settled by nomads, and later re‐submerged under 4 m of water. Repeated damage triggered by down‐throwing earthquakes degenerate the fringing reefs of the north‐west end of the gulf. Conversely, on the north‐eastern and southern parts of the gulf, where earthquakes uplift the margins, modern reefs are thriving, attached to uplifted fossil reef terraces. Therefore, coastal subsidence moderates the development of fringing coral reefs during the late Holocene sea‐level stand still.     

Palaeoenvironmental records from fossil corals: The effects of submarine diagenesis on temperature and climate estimates

The geochemistry of coral skeletons may reflect seawater conditions at the time of deposition and the analysis of fossil skeletons offers a method to reconstruct past climate. However the precipitation of cements in the primary coral skeleton during diagenesis may significantly affect bulk skeletal geochemistry. We used secondary ion mass spectrometry (SIMS) to measure Sr, Mg, B, U and Ba concentrations in primary coral aragonite and aragonite and calcite cements in fossil Porites corals from submerged reefs around the Hawaiian Islands. Cement and primary coral geochemistry were significantly different in all corals. We estimate the effects of cement inclusion on climate estimates from drilled coral samples, which combine cements and primary coral aragonite. Secondary 1% calcite or ∼2% aragonite cement contamination significantly affects Sr/Ca SST estimates by +1 °C and −0.4 to −0.9 °C, respectively. Cement inclusion also significantly affects Mg/Ca, B/Ca and U/Ca SST estimates in some corals. X-ray diffraction (XRD) will not detect secondary aragonite cements and significant calcite contamination may be below the limit of detection (∼1%) of the technique. Thorough petrographic examination of fossils is therefore essential to confirm that they are pristine before bulk drilled samples are analysed. To confirm that the geochemistry of the original coral structures is not affected by the precipitation of cements in adjacent pore spaces we analysed the primary coral aragonite in cemented and uncemented areas of the skeleton. Sr/Ca, B/Ca and U/Ca of primary coral aragonite is not affected by the presence of cements in adjacent interskeletal pore spaces i.e. the coral structures maintain their original composition and selective SIMS analysis of these structures offers a route to the reconstruction of accurate SSTs from altered coral skeletons. However, Mg/Ca and Ba/Ca of primary coral aragonite are significantly higher in parts of skeletons infilled with high Mg calcite cement. We hypothesise this reflects cement infilling of intraskeletal pore spaces in the primary coral structure.     

Variability in the uranium isotopic composition of the oceans over glacial-interglacial timescales

Uranium-series mass spectrometric analyses of corals from the uplifted last glacial terraces at Huon Peninsula, Papua New Guinea, that grew from 50,000 years ago to 30,000 years ago show systematically low values of ²³⁴U/²³⁸U, at the time of coral growth, compared with modern corals. When combined with coral data from other studies a systematic trend emerges indicating shifts in the ²³⁴U/²³⁸U ratio at times of major glacial-interglacial transitions that involve large variations in sea-levels. From last glacial to Holocene, the rate of change in δ²³⁴U is approximately 1‰ per thousand years. The variations in the U budget of the oceans appear to be due to accumulation of excess ²³⁴U in near shore areas in anoxic and suboxic sediments, in salt marshes and mangroves, in estuaries, and in continental margins during periods of warm climate and high sea-levels. These near-shore areas are exposed during periods of low sea level resulting in rapid oxidation of U into highly soluble phases. The subsequent release of ²³⁴U-enriched uranium into the oceans occurs over a sustained period, in step with rising sea-levels.     

Holocene reef sequences and geochemistry, Britomart Reef, central Great Barrier Reef, Australia

Holocene reef development was investigated by coring on Britomart Reef, a mid-shelf reef, 23 km long and 8 km wide situated 120 km north of Townsville in the central Great Barrier Reef (GBR). Two holes were drilled, Britomart 1 on a lagoon patch reef, and Britomart 2 on the windward reef crest. The Holocene reef (25·5 m) is the thickest yet recorded in the GBR and overlies an uneven substrate of weathered Pleistocene limestone. Mineralogical and geochemical analyses show that magnesian calcite and aragonite were converted to low Mg-calcite below the Holocene-Pleistocene disconformity. Corals above the interface have 7500–8500 ppm Sr, but 1650–1500 ppm just below it, decreasing to 400–800 ppm downwards. The intermediate Sr values could be due to partial replacement of aragonite by calcite or higher original Sr content in the corals. Three units are recognized in the Holocene: (1) coral boundstone unit, (2) coral framestone unit, and (3) coral rudstone unit. The coral boundstone unit forms the top 5 m of both cores and is algal-bound coral rubble similar to the present reef top. The coral framestone unit is composed of massive head corals Diploastrea heliopora and Porites sp., and is currently forming in patch reefs situated in the lagoon and along the reef front. The coral rudstone unit comprises coral rudstone and floatstone with unabraded, and unbound, coral clasts in muddy matrix. This matrix may be up to 30% sponge chips. Radiocarbon dating indicates the reef grew more rapidly under the lagoon than under the reef front from 7000 to 5000 yr BP. The rate of reef growth matched existing estimates of sea-level rise, but lagged approximately 1000 years (5–10 m) behind it. Most of the reef mass accumulated between 8500 and 5000 yr BP as a mound of debris, perhaps stabilized by seagrasses or algae. Accretion of the reef top in a windward direction between 5000 and 3000 yr BP created the present, steep reef-front profile.     

Diagenesis and geochemistry of porites corals from Papua New Guinea: Implications for paleoclimate reconstruction

Coral proxy records of sea surface temperature (SST) and hydrological balance have become important tools in the field of tropical paleoclimatology. However, coral aragonite is subject to post-depositional diagenetic alteration in both the marine and vadose environments. To understand the impact of diagenesis on coral climate proxies, two mid-Holocene Porites corals from raised reefs on Muschu Island, Papua New Guinea, were analysed for Sr/Ca, δ¹⁸O, and δ¹³C along transects from 100% aragonite to 100% calcite. Thin-section analysis showed a characteristic vadose zone diagenetic sequence, beginning with leaching of primary aragonite and fine calcite overgrowths, transitional to calcite void filling and neomorphic, fabric selective replacement of the coral skeleton. Average calcite Sr/Ca and δ¹⁸O values were lower than those for coral aragonite, decreasing from 0.0088 to 0.0021 and −5.2 to −8.1‰, respectively. The relatively low Sr/Ca of the secondary calcite reflects the Sr/Ca of dissolving phases and the large difference between aragonite and calcite Sr/Ca partition coefficients. The decrease in δ¹⁸O of calcite relative to coral aragonite is a function of the δ¹⁸O of precipitation. Carbon-isotope ratios in secondary calcite are variable, though generally lower relative to aragonite, ranging from −2.5 to −10.4%. The variability of δ¹³C in secondary calcite reflects the amount of soil CO₂ contributing ¹³C-depleted carbon to the precipitating fluids. Diagenesis has a greater impact on Sr/Ca than on δ¹⁸O; the calcite compositions reported here convert to SST anomalies of 115°C and 14°C, respectively. Based on calcite Sr/Ca compositions in this study and in the literature, the sensitivity of coral Sr/Ca-SST to vadose-zone calcite diagenesis is 1.1 to 1.5°C per percent calcite. In contrast, the rate of change in coral δ¹⁸O-SST is relatively small (−0.2 to 0.2°C per percent calcite). We show that large shifts in δ¹⁸O, reported for mid-Holocene and Last Interglacial corals with warmer than present Sr/Ca-SSTs, cannot be caused by calcite diagenesis. Low-level calcite diagenesis can be detected through X-ray diffraction techniques, thin section analysis, and high spatial resolution sampling of the coral skeleton and thus should not impede the production of accurate coral paleoclimate reconstructions.     

南海珊瑚礁铀系年龄及其地质意义

珊瑚礁是铀系方法测定年龄相当理想的对象,在国外已获得十分有价值的成果。主要用于讨论更新世以来海平面变化和构造运动上升速率,研究反映环境的珊瑚生长速度。本文珊瑚礁样品选取于海南岛鹿回头、雷州半岛、西沙和中沙群岛等地。成功地测试了铀系年龄,揭示出与¹⁴C 数据的不一致,初步讨论了构造上升速率和南海海面的变化。     

Calcite-filled borings in the most recently deposited skeleton in live-collected Porites (Scleractinia): Implications for trace element archives

Skeletons of the scleractinian coral Porites are widely utilized as archives of geochemical proxies for, among other things, sea surface temperature in paleoclimate studies. Here, we document live-collected Porites lobata specimens wherein as much as 60% of the most recently deposited skeletal aragonite, i.e., the part of the skeleton that projects into the layer of living polyps and thus is still in direct contact with living coral tissue, has been bored and replaced by calcite cement. Calcite and aragonite were identified in situ using Raman microspectroscopy. The boring-filling calcite cement has significantly different trace element ratios (Sr/Ca_(mmol/mol) = 6.3 ± 1.4; Mg/Ca_(mmol/mol) = 12.0 ± 5.1) than the host coral skeletal aragonite (Sr/Ca_(mmol/mol) = 9.9 ± 1.3; Mg/Ca_(mmol/mol) = 4.5 ± 2.3). The borings appear to have been excavated by a coccoid cyanobacterium that dissolved aragonite at one end and induced calcite precipitation at the other end as it migrated through the coral skeleton. Boring activity and cement precipitation occurred concomitantly with coral skeleton growth, thus replacing skeletal aragonite that was only days to weeks old in some cases. Although the cement-filled borings were observed in only ∼20% of sampled corals, their occurrence in some of the most recently produced coral skeleton suggests that any corallum could contain such cements, irrespective of the coral’s subsequent diagenetic history. In other words, pristine skeletal aragonite was not preserved in parts of some corals for even a few weeks. Although not well documented in coral skeletons, microbes that concomitantly excavate carbonate while inducing cement precipitation in their borings may be common in the ubiquitous communities that carry out micritization of carbonate grains in shallow carbonate settings. Thus, such phenomena may be widespread, and failure to recognize even very small quantities of early cement-filled borings in corals used for paleoclimate studies could compromise high resolution paleotemperature reconstructions. The inability to predict the occurrence of cement-filled borings in coralla combined with the difficulty in recognizing them on polished blocks highlights the great care that must be taken in vetting samples both for bulk and microanalysis of geochemistry.     

Effects of diagenesis on paleoclimate reconstructions from modern and young fossil corals

The integrity of coral-based reconstructions of past climate variability depends on a comprehensive knowledge of the effects of post-depositional alteration on coral skeletal geochemistry. Here we combine millimeter-scale and micro-scale coral Sr/Ca data, scanning electron microscopy (SEM) images, and X-ray diffraction with previously published δ¹⁸O records to investigate the effects of submarine and subaerial diagenesis on paleoclimate reconstructions in modern and young sub-fossil corals from the central tropical Pacific. In a 40-year-old modern coral, we find secondary aragonite is associated with relatively high coral δ¹⁸O and Sr/Ca, equivalent to sea-surface temperature (SST) artifacts as large as −3 and −5 °C, respectively. Secondary aragonite observed in a 350-year-old fossil coral is associated with relatively high δ¹⁸O and Sr/Ca, resulting in apparent paleo-SST offsets of up to −2 and −4 °C, respectively. Secondary Ion Mass Spectrometry (SIMS) analyses of secondary aragonite yield Sr/Ca ratios ranging from 10.78 to 12.39 mmol/mol, significantly higher compared to 9.15 ± 0.37 mmol/mol measured in more pristine sections of the same fossil coral. Widespread dissolution and secondary calcite observed in a 750-year-old fossil coral is associated with relatively low δ¹⁸O and Sr/Ca. SIMS Sr/Ca measurements of the secondary calcite (1.96-9.74 mmol/mol) are significantly lower and more variable than Sr/Ca values from more pristine portions of the same fossil coral (8.22 ± 0.13 mmol/mol). Our results indicate that while diagenesis has a much larger impact on Sr/Ca-based paleoclimate reconstructions than δ¹⁸O-based reconstructions at our site, SIMS analyses of relatively pristine skeletal elements in an altered coral may provide robust estimates of Sr/Ca which can be used to derive paleo-SSTs.     

Calcium isotope fractionation in modern scleractinian corals

The ⁴⁴Ca/⁴⁰Ca ratios of cultured (Acropora sp.) and open ocean (Pavona clavus, Porites sp.) tropical reef corals are positively correlated with growth temperature. The slope of the temperature-fractionation relation is similar to inorganic aragonite precipitates. However, δ^44/40Ca of the coral aragonite is offset from inorganic and sclerosponge aragonite by about +0.5‰. This offset can neither be explained by the very fast, biologically controlled calcification of scleractinian corals, nor as a consequence of calcification from a partly closed volume of fluid. As corals actively transport calcium through several cell layers to the site of calcification, the most likely explanation for the offset is a biologically induced fractionation. Our results indicate a limited use of Ca isotopes in scleractinian corals as temperature proxy.     

Heavy metals signature of human activities recorded in coral skeletons along the Jordanian coast of the Gulf of Aqaba, Red Sea

The concentrations of six heavy metals were studied in five living coral species and their fossil counterparts collected along the Jordanian Coast of the Gulf of Aqaba. The study aimed at investigating the validity of using coral skeletons as bioindicators for environmental pollution by heavy metals in the Gulf of Aqaba, Red Sea. The skeletal samples of the collected corals were acid digested and analyzed for Cd, Cu, Fe, Mn, Pb, and Zn content using flame atomic absorption spectrophotometer. The results obtained have shown that higher concentrations of heavy metals were found in coral skeletons from areas hosting intense developments and human activities. The massive Porites sp. coral tended to accumulate the highest metal concentrations among the other species (except for Mn). This was due to interspecific differences or selectivity of heavy metals between different coral species. It was noteworthy that fossil coral species recorded higher average metal concentrations than their living counterparts; this was attributed to surface contamination due to prolonged burial of the fossil corals in sediment over the years. The study concluded that corals (specially the massive Porites species) are vulnerable to the accumulation of high concentrations of heavy metals in their skeletons and therefore can serve as proxies to monitor environmental pollution.     

Relationship between species diversity and reef growth in the Holocene at Ishigaki Island,Pacific Ocean

Coral reefs are influenced by global and local factors, and living corals are currently faced with a potential loss of species diversity. Knowledge of the relationship between species diversity and reef growth during the Holocene is important in terms of accurately reconstructing natural conditions prior to recent disturbances (e.g., human impact, pollution, and over-harvesting) and in predicting future scenarios (e.g., abrupt sea-level rise, coastal change, and economic services). This study seeks to characterize the Holocene and present-day reef at Ishigaki Island in the Ryukyu Islands, focusing on spatial and temporal variations in the relationship between species diversity and reef growth. The analysis is based on a drilling core obtained for the Holocene reefs and quantitative species-diversity data (Shannon and Weaver's diversity index, H′) obtained for the present-day reef. H′ was calculated for four coral communities surveyed at the Ibaruma and Fukido reefs. The Holocene sequence was dominated by the corymbose coral community (e.g., Acropora digitifera, A. hyacinthus, Goniastrea retiformis, and Platygyra ryukyuensis), yielding an H′ value of 1.6. The encrusting coral community (e.g., Echinopora lamellose and Pachyseris rugosa) showed the highest diversity at the reef (H′ = 2.2); however, this community was not one of the main reef builders during the Holocene. The massive coral community (e.g., Porites lutea and Favites chinensis) showed the lowest diversity (H′ = 0.6). It also made a minor contribution to reef building; this community appeared in a shallow lagoon once sea level had stabilized. The arborescent coral community (e.g., A. formosa and A. nobilis) was one of the main reef builders, although yielding an H′ value of much less than 1.0. Species diversity is not a prerequisite in terms of Holocene reef growth. Thus, a few species (e.g., A. digitifera, A. hyacinthus, A. formosa, A. nobilis, G. retiformis, and P. ryukyuensis) from two main reef-building communities are important for reef growth. These corals that act as reefs are characterized by high growth rates, having an upward reef growth rate of 2–12 m kyr^? 1 in the Indo-Pacific during the Holocene.     

Strontium in coral aragonite: 1. Characterization of Sr coordination by extended absorption X-ray fine structure

Aragonite was analyzed from Porites lobata, Pavona gigantea, Pavona clavus, and Montastrea annularis corals by Sr K-edge extended absorption X-ray fine structure (EXAFS) and compared with aragonite, strontianite, and mechanically mixed standards. Bulk analyses were performed and data compared with equivalent micro-EXAFS analyses on small (∼400 μm³) analytical volumes with a microfocused X-ray beam. As a result of the architecture of the coral skeleton, the crystals within the microanalytical volume are not randomly oriented, and the microanalytical X-ray absorption spectra show orientational dependence. However, refinement of bulk and microanalytical data provided indistinguishable interatomic distances and thermal vibration parameters in the third shell (indicative of Sr speciation). The Sr K-edge EXAFS of all the coral samples refine, within error, to an ideally substituted Sr in aragonite, in contrast to previous studies, in which significant strontianite was reported. Some samples from that study were also analyzed here. Strontianite may be less widely distributed in corals than previously thought.     

巴布亚新几内亚合恩半岛晚第四纪上升珊瑚礁造礁珊瑚的成岩历史

更新世以来,剧烈的构造运动已将巴布亚新几内亚合恩半岛东北海岸的晚第四纪珊瑚礁阶地抬升上千米.阶地中造礁珊瑚的成岩变化和成岩产物的组构特征反映了该礁的成岩历史,充分体现该区快速构造上升的影响.海水潜流带和淡水渗流带为上升礁的主要成岩环境.生物钻孔、生物碎屑填隙、珊瑚文石针粗化、珊瑚骨骼的溶解和新生变形转化,以及其不同矿物成分和组构的种种胶结物的胶结作用是造礁珊瑚经历的主要成岩作用.地球化学资料表明其成岩变化发生于开放的化学体系之中.     

Fringing reef growth on a terrigenous mud foundation, Fantome Island, central Great Barrier reef, Australia

The leeward fringing reef at Fantome Island (central Great Barrier Reef province) is a carbonate body which has developed under the influence of terrigenous sedimentation. The reef flat is up to 1000 m wide and is surfaced by mobile sand and gravel, with almost all live corals restricted to the seaward rim. The reef slope has coral columns and heads on the upper part, but below 5 m water depth it is a muddy substrate with scattered mounds of branching corals. Three high recovery cores show the reef is up to 10 m thick and developed over a gently sloping terrace of weathered Pleistocene alluvium. Three post-glacial stratigraphic units are recognised: (1) carbonate reef top unit of coral rudstone and framestone including Sinularia spiculite; (2) lower slope unit of coral floatstone in a terrigenous muddy matrix; and (3) transgressive basal unit of skeletal arkosic sand. The acid insoluble content of matrix and of individual corals increases downwards. Coral growth rates decrease downwards, reflecting slower growth in muddier environments. Radiocarbon dating shows that the reef prograded seaward at almost stable sea level. An average vertical accumulation rate of 6.7 mm yr^-1 is indicated. Two age reversals are interpreted as material transported by storms or by erosion in response to a late Holocene sea-level fall. The carbonate reef top unit has developed adjacent to, and is environmentally compatible with a muddy terrigenous, lower slope unit. Terrigenous influx has not changed during the Holocene, and terrigenous content of sediments is controlled by deposition on the reef slope of fine sediment winnowed from the reef flat and concentration of coarse sediment in the transgressive basal sheet.     

Response of reef coral communities to sea-level rise: a Holocene model from Mauritius (Western Indian Ocean)

The fringing reef at Pointe-au-Sable (Mauritius, Indian Ocean) was used to examine the effects of Holocene sea-level rise on coral growth. This reef is about 1000 m wide and comprises a forereef slope (30 m maximum depth), a narrow reef crest and a very shallow backreef (1·5 m maximum depth). Four major coral communities were recognized, which developed within relatively narrow depth ranges: a Pachyseris/Oulophyllia community (deeper than 20 m), an Acropora‘tabulate’Faviid community (20–6 m); a robust branching Acropora community (less than 6 m) and a Pavona community (less than 10m). Three high-recovery cores show the Holocene reef sequence is a maximum of 19·3 m thick and comprises four coral biofacies which are similar to counterparts identified in modern communities: robust branching, tabular-branching, robust branching-domal and foliaceous coral facies. A minimum sea-level curve for the past 7500 years was constructed. Using distribution patterns of coral biofacies and radiocarbon dates from corals, reconstruction of reef growth history indicates that both offshore and onshore reef zones were developing coevally, aggrading at rates of 4·3 mm year^?1 from 6900 years B.P. The reef caught up with sea-level only after sea-level stabilized. Changes in coral community and reef growth rates were driven principally by increasing water agitation due to the decrease in accommodation space. Based on the composition of the successive coral assemblages, the reef appears to have grown through successive equilibrium stages.     

Th/U/U and Pa/U ages from a single fossil coral fragment by multi-collector magnetic-sector inductively coupled plasma mass spectrometry

The ²³⁰Th/²³⁴U/²³⁸U age dating of corals via alpha counting or mass spectrometry has significantly contributed to our understanding of sea level, radiocarbon calibration, rates of ocean and climate change, and timing of El Nino, among many applications. Age dating of corals by mass spectrometry is remarkably precise, but many samples exposed to freshwater yield inaccurate ages. The first indication of open-system ²³⁰Th/²³⁴U/²³⁸U ages is elevated ²³⁴U/²³⁸U_initial values, very common in samples older than 100,000 yr. For samples younger than 100,000 yr that have ²³⁴U/²³⁸U_initial values close to seawater, there is a need for age validation. Redundant ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in a single fossil coral fragment are possible by Multi-Collector Magnetic Sector Inductively Coupled Plasma Mass Spectrometry (MC-MS-ICPMS) and standard anion exchange column chemistry, modified to permit the separation of uranium, thorium, and protactinium isotopes from a single solution. A high-efficiency nebulizer employed for sample introduction permits the determination of both ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in fragments as small as 500 mg. We have obtained excellent agreement between ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in Barbados corals (30 ka) and suggest that the methods described in this paper can be used to test the ²³⁰Th/²³⁴U/²³⁸U age accuracy.Separate fractions of U, Th, and Pa are measured by employing a multi-dynamic procedure, whereby ²³⁸U is measured on a Faraday cup simultaneously with all minor isotopes measured with a Daly ion counting detector. The multi-dynamic procedure also permits correcting for both the Daly to Faraday gain and for mass discrimination during sample analyses. The analytical precision of ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U dates is generally better than ±0.3% and ±1.5%, respectively (2 Relative Standard deviation [RSD]). Additional errors resulting from uncertainties in the decay constant for ²³¹Pa and from undetermined sources currently limit the ²³¹Pa/²³⁵U age uncertainty to about ±2.5%. U isotope data and ²³⁰Th/²³⁴U/²³⁸U ages agree with National Institute of Standards and Technology (NIST) reference materials and with measurements made by Thermal Ionization Mass Spectrometry (TIMS) in our laboratory.     

U-series and oxygen isotope chronology of the mid-Pleistocene Lake Amora (Dead Sea basin)

This study establishes for the first time the chronology and limnological history of Lake Amora (Dead Sea basin, Israel), whose deposits (the Amora Formation) comprise one of the longest exposed lacustrine records of the Pleistocene time. The Amora Formation consists of sequences of laminated primary aragonite and silty-detritus, Ca-sulfate minerals, halite and clastic units. This sedimentary sequence was uplifted and tilted by the rising Sedom salt diapir, exposing ∼320 m of sediments on the eastern flanks of Mt. Sedom (the Arubotaim Cave (AC) section).The chronology of the AC section is based on U-disequilibrium dating (²³⁰Th-²³⁴U and ²³⁴U-²³⁸U ages) combined with floating δ¹⁸O stratigraphy and paleomagnetic constraints. The determination of the ²³⁰Th-²³⁴U ages required significant corrections to account for detrital Th and U. These corrections were performed on individual samples and on suites of samples from several stratigraphic horizons. The most reliable corrected ages were used to construct an age-elevation model that was further tuned to the oxygen isotope record of east Mediterranean foraminifers (based on the long-term similarity between the sea and lake oxygen isotope archives).The combined U-series-δ¹⁸O age-elevation model indicates that the (exposed) Amora sequence was deposited between ∼740 and 70 ka, covering seven glacial-interglacial cycles (Marine Isotope Stages (MIS) 18 to 5).Taking the last glacial Lake Lisan and the Holocene Dead Sea lacustrine systems as analogs of the depositional-limnological environment of Lake Amora, the latter oscillated between wet (glacial) and more arid (interglacial) conditions, represented by sequences of primary evaporites (aragonite and gypsum that require enhanced supply of freshwater to the lakes) and clastic sediments, respectively. The lake evolved from a stage of rapid shifts between high and low-stand conditions during ∼740 to 550 ka to a sabkha-like environment that existed (at the AC site) between 550 and 420 ka. This stage was terminated by a dry spell represented by massive halite deposition at 420 ka (MIS12-11). During MIS10-6 the lake fluctuated between lower and higher stands reaching its highest stand conditions at the late glacial MIS6, after which a significant lake level decline corresponds to the transition to the last interglacial (MIS5) low-stand lake, represented by the uppermost part of the Formation.δ¹⁸O values in the primary aragonite range between 6.0 and −1.3‰, shifting cyclically between glacial and interglacial intervals. The lowest δ¹⁸O values are observed during interglacial stages and may reflect short and intense humid episodes that intermittently interrupted the overall arid conditions. These humid episodes, expressed also by enhanced deposition of travertines and speleothems, seem to characterize the Negev Desert, and in contrast to the overall dominance of the Atlantic-Mediterranean system of rain patterns in the Dead Sea basin, some humid episodes during interglacials may be traced to southern sources.     

Coupled uranium isotope and sea-level variations in the oceans

Globally, rivers supply uranium to the oceans with excess ²³⁴U relative to secular equilibrium and ²³⁴U taken-up by corals can be used for dating. In addition, the ²³⁴U abundance in sea water, at the time the coral was growing, can be measured independently. The veracity of U-series ages used in determining past sea-level variations is dependent on selecting pristine corals free from diagenetic alteration. A quantitative test for alteration assumes invariant ²³⁴U abundances in the oceans for at least the past half a million years and results from samples outside of a narrow range in modern ocean ²³⁴U abundance are excluded from data sets. Here, we have used previously published data to show that ²³⁴U in the oceans appears to be variable and directly related to changes in sea-level, not only over long glacial-interglacial timescales but also at very short, centennial timescales. Most of the previously discarded data can be used to provide valuable additional sea-level information. The process permits a unique insight into the interplay between sources and sinks of uranium in the oceans mediated by sea-level changes at rates far faster than previously thought possible. Similar, rapid sea-level, forcing of other trace element abundances in the oceans is likely.     

Early diagenesis impact on precise U-series dating of deep-sea corals: Example of a 100-200-year old Lophelia pertusa sample from the northeast Atlantic

Deep-sea coral has proved useful for paleoceanographic reconstructions and for documenting ¹⁴C-ages of water masses using ²³⁰Th-ages. However, for precise and accurate U-series dating, further information on coral-age structure, growth rate and diagenetic evolution is still needed. To document such processes, we used U-Th-²²⁶Ra systematics in a 40 cm diameter, Lophelia pertusa specimen collected in 1912 from the Eastern Atlantic (Sea of the Hebrides). External parts of the specimen are thought to have been alive when collected whereas more internal parts were likely dead. The “live-collected” and “dead” parts of the skeleton were sampled and analyzed for their ²³⁰Th, ²³²Th, ²³⁴U, ²³⁸U, ²²⁶Ra and Ba contents by thermal ionization and multicollector inductively coupled plasma mass spectrometry. ²³⁰Th/²³⁴U ratios in the most recent parts yielded ages of 86 ± 6 a and 92 ± 9 a, in agreement with the date of recovery. The older parts yielded ²³⁰Th ages ranging from 169 ± 15 to 211 ± 10 a (n = 5), but had a 31% higher U content than more recent parts of the skeleton. This raises concerns about the possibility of secondary diagenetic U uptake, although an environmentally controlled U/Ca shift between coral growth stages cannot be ruled out. ²²⁶Ra/Ba measurements were made, and model- ²²⁶Ra/Ba ages averaging 250 ± 12 yr were calculated for the older part, assuming a constant initial ²²⁶Ra/Ba ratio in bottom waters. These ages are slightly older than ²³⁰Th-ages, suggesting either that ²²⁶Ra/Ba ratios of ambient-seawater changed over time or that a diagenetic phenomenon have affected the U-series system, or both. Scanning electron microscope observations revealed bioerosion and secondary biomineralization in the older part of the coral skeleton, supporting the hypothesis that diagenetic processes may have influenced the ages obtained by the U-series toolbox. Modeled U-series ages for such an open system are discussed. However, a comparison between ¹⁴C- and ²³⁰Th-ages performed on both pristine and bioeroded parts of the coral gives coherent values (ca 450 a) for the preindustrial ¹⁴C-reservoir age of North Atlantic waters. It remains to be determined, however, whether diagenesis occurs rapidly over a short period of time, or whether it continues for longer periods. In the latter case, diagenetic processes would hamper paleoceanographic interpretations as well as the precise calculation of ¹⁴C ages of deep-water masses, based on comparative U/Th- and ¹⁴C-chronologies.