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.     

The evolution of modern corals and their early history

Scleractinians are a group of calcified anthozoan corals, many of which populate shallow-water tropical to subtropical reefs. Most of these corals calcify rapidly and their success on reefs is related to a symbiotic association with zooxanthellae. These one-celled algal symbionts live in the endodermal tissues of their coral host and are thought responsible for promoting rapid calcification. The evolutionary significance of this symbiosis and the implications it holds for explaining the success of corals is of paramount importance. Scleractinia stands out as one of the few orders of calcified metazoans that arose in Triassic time, long after a greater proliferation of calcified metazoan orders in the Paleozoic. The origin of this coral group, so important in reefs of today, has remained an unsolved problem in paleontology. The idea that Scleractinia evolved from older Paleozoic rugose corals that somehow survived the Permian mass extinction persists among some schools of thought. Paleozoic scleractiniamorphs also have been presented as possible ancestors. The paleontological record shows the first appearance of fossils currently classified within the order Scleractinia to be in the Middle Triassic. These earliest Scleractinia provide a picture of unexpectedly robust taxonomic diversity and high colony integration. Results from molecular biology support a polyphyletic evolution for living Scleractinia and the molecular clock, calibrated against the fossil record, suggests that two major groups of ancestors could extend back to late Paleozoic time. The idea that Scleractinia were derived from soft-bodied, “anemone-like” ancestors that survived the Permian mass extinction, has become a widely considered hypothesis. The 14-million year Mesozoic coral gap stands as a fundamental obstacle to verification of many of these ideas. However, this obstacle is not a barrier for derivation of scleractinians from anemone-like, soft-bodied ancestors. The hypothesis of the ephemeral, “naked coral”, presents the greatest potential for solution of the enigma of the origin of scleractinians. It states that different groups of soft-bodied, unrelated “anemone-like” anthozoans gave rise to various calcified scleractinian-like corals through aragonitic biomineralization. Although there is evidence for this phenomenon being more universal in the mid-Triassic interval, following a lengthy Early Triassic post-extinction perturbation, it appears to have occurred at least three other times prior to this interval. This idea suggests that, because of ephemeral characteristics, the skeleton does not represent a clade of zoantharian evolution but instead represents a grade of organization. In the fossil record, skeletons may have appeared and disappeared at different times as some clades reverted to soft-bodied existence and these phenomena could account for notable gaps in the taxonomic and fossil record. A fuller understanding and possible solution to the problem of the origin of modern corals may be forthcoming. However, it will require synthesis of diverse kinds of data and an integration of findings from paleobiology, stratigraphy, molecular biology, carbonate geochemistry, biochemistry and invertebrate physiology.     

Distribution and nature of incorporation of trace elements in modern aragonitic corals*

The objective of this study is to locate as closely as possible the sites of strontium, magnesium, sodium, and potassium in modern aragonitic corals, specifically whether these cations are adsorbed, or are substituted in the carbonate lattice or are incorporated in organic components. In addition to locating the sites of each of these four elements we wanted to find out quantitatively how much of each element occurs at each site. The experiments in this study are based on the dissolution rate of aragonite in distilled water and on the substitution of strontium and magnesium by calcium and sodium. Special attention has been given to the occurrence of strontium, magnesium, sodium, and potassium in the organic components of the corals. The main site for strontium in the corals is in the aragonite lattice. Twenty-five per cent of the total magnesium occurs in adsorbed sites and in organic compounds. The rest of the magnesium may be located in the aragonite lattice, but it is easily removed by repeated leaching or by replacement with calcium ions. Another possibility is that magnesium may occur in a dispersed mineral phase more soluble than aragonite because magnesium was released at a higher Mg to Ca ratio than is found in the solid coral; also because no local concentration of magnesium could be detected with an electron microprobe. About 12% of the total sodium is in adsorbed sites and is included in the organic compounds. The rest of the sodium might be in the lattice replacing calcium, but the low total exchange capacity is not enough to provide the needed charge balance. Another possibility is that sodium is located in a proposed mineral phase. Potassium is in adsorbed sites and incorporated in the organic compounds to an extent greater than all the other elements studied (30% of the total potassium), but again the evidence suggests that the remaining potassium is in a proposed mineral phase. Calcite is detected on the surfaces of aragonite corals after 5 months in the substitution experiment. The change of argonite to calcite took place after the inhibitor magnesium was exchanged from the surface sites and replaced by calcium. The organic compounds in corals contain small amounts of strontium, magnesium, sodium and potassium. Strontium is preferentially enriched in the organic compounds over magnesium.     

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.     

Quaternary corals from reefs in the Wakatobi Marine National Park,SE Sulawesi,Indonesia, show similar growth rates to modern corals from the same area

We have used digital photography, image analysis and measurements in the field to determine the growth rates of Quaternary corals in the Wakatobi Marine National Park, Indonesia, and compared them to growth rates of similar corals in the same area. In the Quaternary deposits it was possible to measure the growth rates of two massive coral genera Porites and Favites. For each genus, the corals reworked from better‐illuminated upslope environments had higher growth rates than the in situ fossil corals. The calculated radial growth rates for the in situ Porites are slightly lower than, but of the same order of magnitude as, the modern Porites growing in 10 m water depth at Hoga (10.04 ± 3.34 mm yr^?1 ± 1 s.d.; n = 3) and Kaledupa (15.26 ± 4.83 mm yr^?1 ± 1 s.d.; n = 3). Sedimentation rates and underwater visibility are inferred to have been similar in the fossil site to that at the modern Kaledupa site. Decreasing light penetration due to increased water depth is inferred to have been a major influence on growth rates. The in situ massive corals with good growth banding are inferred to have grown in a comparable environment to modern Kaledupa and Hoga. The study highlights that it is possible to compare coral growth rates, and their influencing parameters, from modern and well‐preserved ancient examples. Copyright © 2006 John Wiley & Sons, Ltd.     

Diagenetic effects on the distribution of uranium in live and Holocene corals from the Gulf of Aqaba

We investigated the effects of diagenetic alteration (dissolution, secondary aragonite precipitation and pore filling) on the distribution of U in live and Holocene coral skeletons. For this, we drilled into large Porites lutea coral-heads growing in the Nature Reserve Reef (NRR), northern Gulf of Aqaba, a site close to the Marine Biology Laboratory, Elat, Israel, and sampled the core material and porewater from the drill-hole. In addition, we sampled Holocene corals and beachrock aragonite cements from a pit opened in a reef buried under the laboratory grounds. We measured the concentration and isotopic composition of U in the coral skeletal aragonite, aragonite cements, coral porewater and open NRR and Gulf of Aqaba waters.Uranium concentration in secondary aragonite filling the skeletal pores is significantly higher than in primary biogenic aragonite (17.3 ± 0.6 compared to 11.9 ± 0.3 nmol · g⁻¹, respectively). This concentration difference reflects the closed system incorporation of uranyl tri-carbonate into biogenic aragonite with a U/Ca bulk distribution coefficient (K_D) of unity, versus the open system incorporation into secondary aragonite with K_D of 2.4. The implication of this result is that continuous precipitation of secondary aragonite over ∼1000 yr of reef submergence would reduce the coral porosity by 5% and can produce an apparent lowering of the calculated U/Ca - SST by ∼1°C and apparent age rejuvenation effect of 7%, with no measurable effect on the calculated initial U isotopic composition.All modern and some Holocene corals (with and without aragonite cement) from Elat yielded uniform δ²³⁴U = 144 ± 5, similar to the Gulf of Aqaba and modern ocean values. Elevated δ²³⁴U values of ∼180 were measured only in mid-Holocene corals (∼5000 yr) from the buried reef. The values can reflect the interaction of the coral skeleton with ²³⁴U-enriched ground-seawater that washes the adjacent granitic basement rocks.We conclude that pore filling by secondary aragonite during reef submergence can produce small but measurable effects on the U/Ca thermometry and the U-Th ages. This emphasizes the critical importance of using pristine corals where the original mineralogy and porosity are preserved in paleooceanographic tracing and dating.     

The isotopic composition of respired carbon dioxide in scleractinian corals: Implications for cycling of organic carbon in corals

The origin of δ¹³C variations within the skeletons of zooxanthellate scleractinian corals is still a matter of considerable debate. In particular, the role respired CO₂ plays in controlling the eventual δ¹³C of the skeleton remains unclear. In this study, the temporal variability of the δ¹³C of respired CO₂ produced by Montastraea faveolata has been measured at approximately monthly intervals over a 1-year period. In these experiments, three corals maintained on a platform at 8 m depth near Molasses Reef in the Florida Keys were incubated in closed chambers for 24-h periods and samples of the incubation water analyzed for the δ¹³C of the dissolved inorganic carbon (ΣCO₂) at ∼3-h intervals. Throughout the incubation, the concentration of O₂ was measured continuously within the chamber. Our results show that during daylight, the δ¹³C of the ΣCO₂ in the incubation water becomes enriched in ¹³C as a result of fractionation during the fixation of C by photosynthesis, whereas at night the δ¹³C of the ΣCO₂ becomes more negative. The δ¹³C of the respiratory CO₂ ranges from −9‰ in the late spring to values as low as −17‰ in the autumn. The lighter values are significantly more negative than those reported by previous workers for coral tissue and zooxanthellae. An explanation for this discrepancy may be that the corals respire a significant proportion of isotopically negative substances, such as lipids, which are known to have values up to 10‰ lighter compared to the bulk δ¹³C of the tissue. The clear seasonal cycle in the δ¹³C of the respiratory CO₂ suggests that there is also seasonal variability in either the δ¹³C of the coral tissue or the type and/or amount of organic material being respired. A similar temporal pattern and magnitude of change was observed in the δ¹³C of the coral tissue samples collected from a nearby reef at monthly intervals between 1995 and 1997. These patterns are similar in timing to the δ¹³C measured in the coral skeletons. We have also calculated an annual mean value for the fractionation factor between dissolved CO₂⁻ in the external environment and photosynthate fixed by the zooxanthellae of 1.0121 (±0.003). This value is inversely correlated with the ratio of photosynthesis to respiration (P/R) of the entire organism and shows the highest values during the summer months.     

鹿井铀矿床铀矿物学特征

鹿井矿床位于南华活动带华夏褶皱带武功—诸广断隆区,闽、赣后加里东褶皱地块西缘,诸广山复式岩体中段,受遂川断裂及热水断裂组成的地堑式断陷带控制。本文主要对鹿井矿床内铀矿物的赋存状态、成分特征及组合特征进行了研究。     

中国泥盆纪珊瑚的生物地理区系

<正> 古生物地理学是研究地质历史时期生物化石的地理分布及其变化的一门学科。古生物地理区系是判断古板块位置、重建古地理最有力的证据,因此它与古地磁学和古气候学是构成现代古地理学的三大支柱。     

开鲁坳陷钱家店铀矿床铀的赋存状态及铀矿形成时代研究

本文对开鲁坳陷钱家店铀矿床铀的存在形式及铀矿成矿作用进行了研究。钱家店铀矿床矿石中铀的存在形式有铀矿物、吸附铀及含铀矿物,其中以铀矿物和吸附铀形式为主。U6 /U4 比值为0.266～1.116,平均为0.761。铀矿石中铀在各种粒级碎屑中均有分布,但集中分布在0.1～0.25mm粒级中,铀分布率27.89%～76.98%,平均为46.55%。钱家店砂岩型铀矿床UPb等时线年龄为53±3Ma和7±0Ma。     

松辽盆地地浸砂岩型铀成矿铀源分析

通过研究松辽盆地钱家店铀矿床和盆地南部铀矿化认为,松辽盆地砂岩型铀成矿作用独特,其成因可归结为双混合叠造型。其铀源也具有多源性,既有蚀源区铀源,又有盖层铀源,还有深部铀源,它们共同组成松辽盆地铀成矿的铀源。     

砂岩型铀矿床硫化物还原富集铀的机制

砂岩型铀矿中含大量不同形态、不同阶段的黄铁矿。仅凭矿相学对黄铁矿产状及电子探针对黄铁矿形态的观察难以准确地判别成矿期、成矿前及成矿后形成的黄铁矿。而成矿期黄铁矿是铀矿床成因和形成过程的重要信息载体,对其准确识别具有特别重要的意义。以往国内外研究采用激光剥蚀电感耦合等离子体质谱(LA-MC-ICP-MS)方法分析Pb同位素,但该方法对于低含量Pb样品分析精度较低且较难获得²⁰⁴Pb数据。本文对铀矿石中的黄铁矿利用微区原位的手段进行更加精准的飞秒级质谱(fs-LA-MC-ICP-MS)的Pb同位素测试,发现大量黄铁矿存在Pb同位素异常,从中可能区分出成矿期与非成矿期的黄铁矿。经U-Th-Pb放射性衰变原理分析并结合黄铁矿矿相学特点可以发现,矿相学镜下明确是成矿期的黄铁矿,其²⁰⁶Pb/²⁰⁴Pb比正常克拉克值大十几倍甚至数十倍,²⁰⁷Pb/²⁰⁴Pb稍有异常,而²⁰⁸Pb/²⁰⁴Pb基本不变。矿相学中产状呈草莓状,以及铀矿物围绕其生长但未有穿插关系的非成矿期黄铁矿,其²⁰⁶Pb/²⁰⁴Pb正常;矿相学镜下难以确定形成阶段的、与铀矿物没有任何接触关系的黄铁矿,其Pb同位素没有明显的规律性。这些结果证明了利用Pb同位素异常来判断黄铁矿形成阶段的准确性。因此,利用黄铁矿微区原位Pb同位素差异,适当配合矿相学形态和产状观察,可较为精准地识别出成矿期黄铁矿。

     

Monitoring of terrestrial input by massive corals

Human-induced pollution in coastal areas can significantly increase the concentration of some trace elements in the marine environment. In the tropics, scleractinian corals incorporate these trace elements in their living parts and skeleton. The potential of corals to monitor pollution through time is reviewed in this contribution. The strength and weakness of corals as pollution indicators are discussed, and a few examples are shown. Although some progress should be made in the understanding of the processes ruling the incorporation of trace elements in coralline aragonite, it is concluded that large environmental changes are well recorded by coral skeletons.     

相山铀矿田中一种值得关注的铀矿化类型

龙巴岭铀矿床矿化类型不同于相山铀矿田已知的水云母-萤石型和钠长石型铀矿化类型,它以石英-晶质铀矿矿物群产于碎斑流纹岩中。根据铀矿化产出形式、矿化岩石的化学组成和矿物群的组成及生成顺序,这种铀矿化类型既区别于已知的铀矿化类型,又与这两种铀矿化类型存在某些关联。介绍这种矿化类型可能会有益于对相山铀矿田的铀成矿认识和找矿评价。     

Evidence of uranium biomineralization in sandstone-hosted roll-front uranium deposits, northwestern China

We show evidence that the primary uranium minerals, uraninite and coffinite, from high-grade ore samples (U₃O₈>0.3%) in the Wuyiyi, Wuyier, and Wuyisan sandstone-hosted roll-front uranium deposits, Xinjiang, northwestern China were biogenically precipitated and psuedomorphically replace fungi and bacteria. Uranium (VI), which was the sole electron acceptor, was likely to have been enzymically reduced. Post-mortem accumulation of uranium may have also occurred through physio-chemical interaction between uranium and negatively-charged cellular sites, and inorganic adsorption or precipitation reactions. These results suggest that microorganisms may have played a key role in formation of the sandstone- or roll-type uranium deposits, which are among the most economically significant uranium deposits in the world.     

川北砂岩型铀矿稀土元素特征及铀成矿作用

在大量取样分析的基础上 ,本文系统分析研究了围岩、矿石、方解石脉和铀矿物的稀土元素组成 ,讨论了岩石、矿石沉积和成岩过程中的稀土元素变化规律 ,总结了川北砂岩型铀矿床的稀土元素地球化学特征。通过与典型的火山岩型和变质岩型热液成因铀矿床进行对比 ,认为川北砂岩型铀矿具有热液 (水 )改造成矿作用的稀土元素地球化学特点 ;铀矿化经历了沉积成岩和热液改造富集两个阶段。     

相山矿田铀的中和还原成矿作用”

该文以相山矿田为例介绍了铀的中和还原成矿作用的概念和机理。     

砂岩型铀矿床中铀矿物的形成机理

本文通过对砂岩型铀矿床中铀在不同地球化学环境中的行为、存在形式及铀矿物种类的分析，论述了主要工业铀矿物——沥青铀矿的形成机理：(1)铀是变价元素，在氧化环境中活化迁移，在还原环境中还原沉淀；(2)来自于氧化环境的[UO2(CO3)3]^4-、[UO2(CO3)2]^2-在氧化还原过渡带与有机质、硫化物及低价铁等还原剂发生反应，形成铀的简单氧化物——沥青铀矿；(3)有机质、粘土矿物等吸附UO2^2 ，加快了其被还原的速度，有利于铀的富集。因此认为：有机质还原UO2^2 形成H2S和H2S还原UO2^2 的作用是沥青铀矿形成的主要原因，这一反应在中性和弱碱性碳酸盐溶液中广泛和普遍存在。H2S等还原剂的存在是环境Eh值下降的主要原因，从而使水中的UO2^2 在氧化还原过渡带处于过饱和状态，加速了铀的吸附和沉淀。     

铀矿大型矿集区与成矿作用

大型矿集区的形成，是在地质历史演化进程中，多矿种大矿量超常聚集的结果。不同的矿集区有不同的典型矿种和典型矿床。本文仅以铀矿为例，在世界范围内厘定出14个铀矿大区矿集区。本文研究铀矿大型矿集区时空分布规律与地球动力学演化的关系，在此基础上探讨了铀矿大型矿集区元素超常聚集规律，提出多矿种“点区超常聚集”和“短时限爆发成矿”特征。本文按照“源、运、积”3个环节，探讨铀矿大型矿集区的成矿作用，其中有关深源成矿、特殊碱质流体的水岩反应以及元素沉积环境的研究，为建立铀矿大型矿集区的找矿模式奠定基础。