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1.
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.  相似文献   

2.
祝仲蓉 Marsh.  J 《沉积学报》1992,10(1):133-145
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.  相似文献   

3.
Incorporation of uranium in modern corals   总被引：1，自引：0，他引：1  
Uranium occurs in corals at three sites: 1, in organic matter; 2, adsorbed on the surfaces of skeletal aragonite; and 3, in the aragonite lattice. Organic matter incorporates from sea water by chelation 40–70 ppm uranium; skeletal aragonite incorporates only 3 ppm. However, as the organic fraction is low (0·1%), its high concentration of uranium does not significantly affect the total concentration of uranium in the coral. A negligible concentration of uranium, 40–60 ppb, is adsorbed on skeletal aragonite from which it is readily leached or exchanged. This low concentration of adsorbed uranium (<2% of the total uranium in skeletal aragonite) is related to the very small specific surface area (1·5–1·8 m2/g of the corals.  相似文献   

4.
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 (KD) of unity, versus the open system incorporation into secondary aragonite with KD 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.  相似文献   

5.
Deep-sea corals have been shown to be useful archives of rapid changes in ocean chemistry during the last glacial cycle. Their aragonitic skeleton can be absolutely dated by U-Th data, freeing radiocarbon to be used as a water-mass proxy. For certain species of deep-sea corals, the growth rate allows time resolution that is comparable to ice cores. An additional proxy is needed to exploit this opportunity and turn radiocarbon data into rates of ocean overturning in the past.Neodymium isotopes in seawater can serve as a quasi-conservative water-mass tracer and initial results indicate that deep-sea corals may be reliable archives of seawater Nd isotopes. Here we present a systematic study exploring Nd isotopes as a water-mass proxy in deep-sea coral aragonite. We investigated five different genera of modern deep-sea corals (Caryophyllia, Desmophyllum, Enallopsamia, Flabellum, Lophelia), from global locations covering a large potential range of Nd isotopic compositions. Comparison with ambient seawater measurements yields excellent agreement and suggests that deep-sea corals are reliable archives for seawater Nd isotopes.A parallel study of Nd concentrations in these corals yields distribution coefficients for Nd between seawater and coral aragonite of 1-10, omitting one particular genus (Enallopsamia). The corals and seawater did however not come from exactly the same location, and further investigations are needed to reach robust conclusions on the incorporation of Nd into deep-sea coral aragonite.Lastly, we studied the viability of extracting the Nd isotope signal from fossil deep-sea corals by carrying out stepwise cleaning experiments. Our results show that physical removal of the ferromanganese coating and chemical pre-cleaning have the highest impact on Nd concentrations, but that oxidative/reductive cleaning is also needed to acquire a seawater Nd isotope signal.  相似文献   

6.
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.  相似文献   

7.
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.  相似文献   

8.
This study presents a new approach to coral thermometry that deconvolves the influence of water temperature on skeleton composition from that of “vital effects”, and has the potential to provide estimates of growth temperatures that are accurate to within a few tenths of a degree Celsius from both tropical and cold-water corals. Our results provide support for a physico-chemical model of coral biomineralization, and imply that Mg2+ substitutes directly for Ca2+ in biogenic aragonite. Recent studies have identified Rayleigh fractionation as an important influence on the elemental composition of coral skeletons. Daily, seasonal and interannual variations in the amount of aragonite precipitated by corals from each “batch” of calcifying fluid can explain why the temperature dependencies of elemental ratios in coral skeleton differ from those of abiogenic aragonites, and are highly variable among individual corals. On the basis of this new insight into the origin of “vital effects” in coral skeleton, we developed a Rayleigh-based, multi-element approach to coral thermometry. Temperature is resolved from the Rayleigh fractionation signal by combining information from multiple element ratios (e.g., Mg/Ca, Sr/Ca, Ba/Ca) to produce a mathematically over-constrained system of Rayleigh equations. Unlike conventional coral thermometers, this approach does not rely on an initial calibration of coral skeletal composition to an instrumental temperature record. Rather, considering coral skeletogenesis as a biologically mediated, physico-chemical process provides a means to extract temperature information from the skeleton composition using the Rayleigh equation and a set of experimentally determined partition coefficients. Because this approach is based on a quantitative understanding of the mechanism that produces the “vital effect” it should be possible to apply it both across scleractinian species and to corals growing in vastly different environments. Where instrumental temperature records are available, a Rayleigh-based framework allows the effects of stress on coral calcification to be identified on the basis of anomalies in the skeletal composition.  相似文献   

9.
Pinxian Wang 《地球科学进展》2019,34(12):1222-1233
The discovery of deep sea coral forests in the spring of 2018 filled a significant gap in the benthos research and even in carbon cycling in the South China Sea. Previously, the researches of deep-sea benthos were restricted to the sediment-covered soft bottom due to the technical limitations, and the rocky hard bottom was believed to be barren of life. Using submersible technique in the mid-1990s, deep-water coral reefs were first discovered in the Atlantic Ocean, which opened a new research direction in marine sciences. Two groups of deep sea corals have been recognized: scleractinian hexacorals and gorgonian octocorals. The aragonite skeleton of the former group build up deep sea coral reefs, while the latter make up deep sea coral forests with high-Mg calcite skeleton in many gorgonian corals. All kinds of carbonate coral skeletons can record environment changes of the deep sea and provide excellent material for high-resolution paleoceanography. Although the development of deep sea coral reefs in the Pacific Ocean is hampered by its extremely shallow aragonite compensation depth, deep sea coral forests are ubiquitous in the ocean. Up to now, most parts of the Pacific have not yet explored in this respect, and deep sea corals remain outside the research scope. The present paper is a literature review and calls for attention to the deep sea forests. It starts with the composition and distribution of deep sea coral reefs and forests, followed by discussions on the significance of deep sea coral forests in marine ecology and in paleoceanographic reconstructions.  相似文献   

10.
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.  相似文献   

11.
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, δ44/40Ca 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.  相似文献   

12.
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.  相似文献   

13.
Marine aragonite, in the form of corals and/or shells, provides useful markers of geological and archaeological events. It is, therefore, important to have simple and accurate methods of dating these materials. Electron spin resonance (ESR) has previously been shown to be a reliable method for establishing the age of aragonitic coral samples in the time period approximately 100 ka B.P. The primary purpose of the present work is to discuss the problems encountered in extending this method to considerably older samples, up to 600 ka BP in age. In this time period there are questions about the stability of the ESR signal. The samples investigated are aragonitic corals from reef terraces of Barbados, West Indies, all of which have previously been dated by the methods, and by U-series disequilibrium, for samples below the limit of this method. There is generally good agreement for samples up to about 300 ka in age; older samples, even unrecrystallized, appear younger when dated by ESR than by . The source of this discrepancy is not clear. The explanation of thermal fading is not adequate. However, it appears likely that in most cases ESR will be able to be used to date materials up to this age. Further investigation is needed to determine tests that will distinguish datable samples from non-datable ones.  相似文献   

14.
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.  相似文献   

15.
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.  相似文献   

16.
Compositional variations at ultra-structure length scales in coral skeleton   总被引：1，自引：0，他引：1  
Distributions of Mg and Sr in the skeletons of a deep-sea coral (Caryophyllia ambrosia) and a shallow-water, reef-building coral (Pavona clavus) have been obtained with a spatial resolution of 150 nm, using the NanoSIMS ion microprobe at the Muséum National d’Histoire Naturelle in Paris. These trace element analyses focus on the two primary ultra-structural components in the skeleton: centers of calcification (COC) and fibrous aragonite. In fibrous aragonite, the trace element variations are typically on the order of 10% or more, on length scales on the order of 1-10 μm. Sr/Ca and Mg/Ca variations are not correlated. However, Mg/Ca variations in Pavona are strongly correlated with the layered organization of the skeleton.These data allow for a direct comparison of trace element variations in zooxanthellate and non-zooxanthellate corals. In both corals, all trace elements show variations far beyond what can be attributed to variations in the marine environment. Furthermore, the observed trace element variations in the fibrous (bulk) part of the skeletons are not related to the activity of zooxanthellae, but result from other biological activity in the coral organism. To a large degree, this biological forcing is independent of the ambient marine environment, which is essentially constant on the growth timescales considered here.Finally, we discuss the possible detection of a new high-Mg calcium carbonate phase, which appears to be present in both deep-sea and reef-building corals and is neither aragonite nor calcite.  相似文献   

17.
This study focuses on the diagenetic sequence under marine and meteoric conditions as well as isotopes and trace metals contamination in Quseir and Gebel Zeit areas along the Egyptian Red Sea coast through a series of modern and fossil corals, Porites lutea and Favites pentagona. The diagenetic sequence begins with deposition of thin fringes of syntaxial aragonite and micritic high-magnesian calcite in the modern corals to completely altered Porites and partially altered Favites to low-magnesium calcite in the oldest Pleistocene unit. Average δ18O and δ13C values of Pleistocene corals in the two studied areas were lower than those of modern corals. Values of modern corals and lower fossil unit indicated coralline limestone, while those of middle and upper fossil units indicated fresh water influences. Average values of trace metals in modern corals were higher than those of Pleistocene counterpart except for Mn. Modern coral samples recorded enrichment in the average values of Pb, Zn, and Mn at Quseir area and enrichment in Co, Cu, and Ni at Gebel Zeit area. This may be attributed mostly to different tourist activities, landfill due to increase urbanization and nearby of Quseir area from the old phosphate harbor at El Hamrawin area, as well as oil exploration and production activities in the Gulf of Suez area. Also, results indicated that most samples of Porites have high concentration of trace metals than in Favites, especially in Cu, Zn, Mn, and Pb. This may due to high amounts of intergranular porosity and high total surface area of Porites in contrast to Favites.  相似文献   

18.
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.  相似文献   

19.
In this study we have used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), to produce a high resolution coral record of rare earth elements (REE), Mn and Ba from coastal Porites corals from the Great Barrier Reef of Australia. Validation of the LA-ICP-MS technique indicated that the method provides accurate and reproducible (RSD = 13-18%) analysis of low concentration REE in corals (∼1 to 100 ppb). The REE composition in coral samples was found to closely reflect that of the surrounding seawater and distribution coefficients of ∼1-2 indicated minimal fractionation of the series during incorporation into coral carbonate. To explore the idea that coral records of REE can be used to investigate dissolved seawater composition, we analyzed two coastal corals representing a total of ∼30 yr of growth, including a 10-yr overlapping period. Comparable results were obtained from the two samples, particularly in terms of elemental ratios (Nd/Yb) and the Ce anomaly. Based on this evidence and results from the determination of distribution coefficients, we suggest that useful records of seawater REE composition can be obtained from coral carbonates. When compared to the REE composition of a mid shelf coral, coastal corals showed a significant terrestrial influence, characterized by higher REE concentrations (greater than 10 times) and light REE enrichment. The REE composition of coastal seawater inferred from the coral record was dependent on seasonal factors and the influence of flood waters. REE fractionation displayed a strong seasonal cycle that correlated closely with Mn concentration. We suggest that higher Nd/Yb ratios and higher Mn concentrations in summer result from scavenging of heavy REE by particulate organic ligands and Mn reductive dissolution respectively, both processes displaying higher rates during periods of high primary productivity. The Ce anomaly also displayed a strong seasonal cycle showing an enhanced anomaly during summer and during flood events. This is consistent with the Ce anomaly being primarily controlled by the abundance of Ce oxidizing bacteria. Based on these arguments, we suggest that the coral record of dissolved REE and Mn may be regarded as a useful proxy for biological activity in coastal seawater.  相似文献   

20.
The effect of early diagenesis on Sr/Ca ratios encapsulated in coral skeletons was evaluated by comparing mineralogical, structural and geochemical characteristics of modern and Holocene, branching Acropora colonies. The modern specimens (Acropora danai, Acropora formosa) come from Réunion island (Western Indian Ocean) and the Great Barrier Reef of Australia respectively. The Sr/Ca ratios of modern specimens range from 9.08 to 9.37 mmol/mol. The fossil acroporids (Acropora group danai-robusta) were collected from a 50-m core drilled through a barrier reef in Tahiti island; their C-14 ages range from 3,200 to 10,200 calendar years B.P. Fossil skeletons are 100% aragonite. Earlier diagenesis has occurred in the marine environment; it is expressed by growth of secondary inorganic aragonite over primary skeletal aragonite needles, development of syntaxial aragonite cements within intraskeletal cavities and decrease in size of original 1-1,050-µm-wide pores (residual porosity ranges from 25 to 28%), which results in a volume reduction by 34 to 49%. Cementation increases with increasing age of the corals. Later diagenesis has occurred in a mixed marine-freshwater environment. It includes partial dissolution of skeletal and growth of cement aragonite fibres in the form of spherolites, irregular meshes of large squarely terminated laths; this results in an increase in porosity from 30 to 59%. By reference to modern well-preserved acroporids, this diagenetic alteration has led to an increase of Sr/Ca values (from 9.08-9.37 to 8.89-10.55 mmol/mol). This variation in Sr/Ca ratio can be linked to the increase in the amount of Sr-enriched cements relative to the volume of the skeletal aragonite and to a more homogeneous distribution of these cements throughout the skeleton. The uncritical use of Sr/Ca ratios as paleothermometers from diagenetically altered skeletons may cause serious misinterpretations. Accordingly, estimate of the degree of diagenetic alteration in skeletons is a prerequisite to any paleoclimatic reconstruction based on coral records.  相似文献   

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