Effect of intraband variability on stable isotope and density time series obtained from banded corals

Density, δ¹⁸O and δ¹³C were measured along two tracks, one close to the central growth axis and the other, ∼20ℴ off the axis, in a coral (Porites lutea) collected from the Stanley Reef, Central Great Barrier Reef, Australia. The δ¹⁸O variations in the coral are well correlated with sea surface temperature changes. The common variances between the two tracks were about 60% in the δ¹⁸O, δ{13}C, and the skeletal density variations. Part of the noise (40%) could be due to the difficulty of sampling exactly time contemporaneous parts of each band along the two tracks and part of it could be due to genuine intraband variability. In spite of the intraband variability, the time series obtained from the two tracks are similar, indicating that the dominant causative factor for the isotopic variations is external, i.e., the environmental conditions that prevail during the growth of the coral; density band formation does not appear to be directly controlled by the sea surface temperature.     

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.     

North Atlantic climate variability since AD 1350 recorded in δ 18O and skeletal density of Bermuda corals

The reconstruction of the climatic history during the past several hundred years requires a sufficient geographical coverage of combined climate proxy series. Especially in order to identify causal connections between the atmosphere and the ocean, inclusion of marine records into composite climate time series is of fundamental importance. We present two skeletal δ ¹⁸O chronologies of coral skeletons of Diploria labyrinthiformis from Bermuda fore-reef sites covering periods in the nineteenth and twentieth centuries and compare them with instrumental temperature data. Both time series are demonstrated to display sea-surface temperature (SST) variability on inter-annual to decadal time scales. On the basis of a specific modern δ ¹⁸O vs instrumental SST calibration we reconstruct a time series of SST anomalies between AD 1350 and 1630 covering periods during the Little Ice Age. The application of the coral δ ¹⁸O vs temperature relationship leads to estimates of past SST variability which are comparable to the magnitude of modern variations. Parallel to δ ¹⁸O chronologies we present time series of skeletal bulk density. Coral δ ¹⁸O and skeletal density reveal a strong similarity during Little Ice Age, confirming the reliability of both proxy climate indicators. The past coral records, presented in this study, share features with a previously published climate proxy record from Bermuda and a composite time series of reconstructed Northern Hemisphere summer temperatures. The coral proxy data presented here represent a valuable contribution to elucidate northern Atlantic subtropical climate variation during the past several centuries. Received: 9 November 1998 / Accepted: 13 September 1999     

Upwelling, species, and depth effects on coral skeletal cadmium-to-calcium ratios (Cd/Ca)

Skeletal cadmium-to-calcium (Cd/Ca) ratios in hermatypic stony corals have been used to reconstruct changes in upwelling over time, yet there has not been a systematic evaluation of this tracer’s natural variability within and among coral species, between depths and across environmental conditions. Here, coral skeletal Cd/Ca ratios were measured in multiple colonies of Pavona clavus, Pavona gigantea and Porites lobata reared at two depths (1 and 7 m) during both upwelling and nonupwelling intervals in the Gulf of Panama (Pacific). Overall, skeletal Cd/Ca ratios were significantly higher during upwelling than during nonupwelling, in shallow than in deep corals, and in both species of Pavona than in P. lobata. P. lobata skeletal Cd/Ca ratios were uniformly low compared to those in the other species, with no significant differences between upwelling and nonupwelling values. Among colonies of the same species, skeletal Cd/Ca ratios were always higher in all shallow P. gigantea colonies during upwelling compared to nonupwelling, though the magnitude of the increase varied among colonies. For P. lobata, P. clavus and deep P. gigantea, changes in skeletal Cd/Ca ratios were not consistent among all colonies, with some colonies having lower ratios during upwelling than during nonupwelling. No statistically significant relationships were found between skeletal Cd/Ca ratios and maximum linear skeletal extension, δ¹³C or δ¹⁸O, suggesting that at seasonal resolution the Cd/Ca signal was decoupled from growth rate, coral metabolism, and ocean temperature and salinity, respectively. These results led to the following conclusions, (1) coral skeletal Cd/Ca ratios are independent of skeletal extension, coral metabolism and ambient temperature/salinity, (2) shallow P. gigantea is the most reliable species for paleoupwelling reconstruction and (3) the average Cd/Ca record of several colonies, rather than of a single coral, is needed to reliably reconstruct paleoupwelling events.     

Carbonate clumped isotope thermometry of deep-sea corals and implications for vital effects

Here we calibrate the carbonate clumped isotope thermometer in modern deep-sea corals. We examined 11 specimens of three species of deep-sea corals and one species of a surface coral spanning a total range in growth temperature of 2-25 °C. External standard errors for individual measurements ranged from 0.005‰ to 0.011‰ (average: 0.0074‰) which corresponds to ∼1-2 °C. External standard errors for replicate measurements of Δ₄₇ in corals ranged from 0.002‰ to 0.014‰ (average: 0.0072‰) which corresponds to 0.4-2.8 °C. We find that skeletal carbonate from deep-sea corals shows the same relationship of Δ₄₇ (the measure of ¹³C-¹⁸O ordering) to temperature as does inorganic calcite. In contrast, the δ¹³ C and δ¹⁸O values of these carbonates (measured simultaneously with Δ₄₇ for every sample) differ markedly from equilibrium with seawater; i.e., these samples exhibit pronounced ‘vital effects’ in their bulk isotopic compositions. We explore several reasons why the clumped isotope compositions of deep-sea coral skeletons exhibit no evidence of a vital effect despite having large conventional isotopic vital effects.     

The potential origins and palaeoenvironmental implications of high temporal resolution δO heterogeneity in coral skeletons

δ¹⁸O was determined at high spatial resolution (beam diameter ∼30 μm) by secondary ion mass spectrometry (SIMS) across 1-2 year sections of 2 modern Porites lobata coral skeletons from Hawaii. We observe large (>2‰) cyclical δ¹⁸O variations that typically cover skeletal distances equivalent to periods of ∼20-30 days. These variations do not reflect seawater temperature or composition and we conclude that skeletal δ¹⁸O is principally controlled by other processes. Calcification site pH in one coral record was estimated from previous SIMS measurements of skeletal δ¹¹B. We model predicted skeletal δ¹⁸O as a function of calcification site pH, DIC residence time at the site and DIC source (reflecting the inputs of seawater and molecular CO₂ to the site). We assume that oxygen isotopic equilibration proceeds at the rates observed in seawater and that only the aqueous carbonate ion is incorporated into the precipitating aragonite. We reproduce successfully the observed skeletal δ¹⁸O range by assuming that DIC is rapidly utilised at the calcification site (within 1 h) and that ∼80% of the skeletal carbonate is derived from seawater. If carbonic anhydrase catalyses the reversible hydration of CO₂ at the calcification site, then oxygen isotopic equilibration times may be substantially reduced and a larger proportion of the skeletal carbonate could be derived from molecular CO₂. Seasonal skeletal δ¹⁸O variations are most pronounced in the skeleton deposited from late autumn to winter (and coincide with the high density skeletal bands) and are dampened in skeleton deposited from spring to summer. We observed no annual pattern in sea surface temperature or photosynthetically active radiation variability which could potentially correlate with the coral δ¹⁸O. At present we are unable to resolve an environmental cue to drive seasonal patterns of short term skeletal δ¹⁸O heterogeneity.     

Calcification rate and the stable carbon, oxygen, and nitrogen isotopes in the skeleton, host tissue, and zooxanthellae of bleached and recovering Hawaiian corals

We tested the effectiveness of stable isotopes as recorders of physiological changes that occur during coral bleaching and recovery. Montipora capitata and Porites compressa fragments were bleached in outdoor tanks with seawater temperature raised to 30 °C (treatment corals) for one month. Additional fragments were maintained at 27 °C in separate tanks (control corals). After one month, (0 months recovery), buoyant weight was measured and a subset of fragments was frozen. Remaining fragments were returned to the reef for recovery. After 1.5, 4, and 8 months, fragments were collected, measured for buoyant weight, and frozen. Fragments were analyzed for stable carbon and oxygen isotopic compositions of the skeleton (δ¹³C_s; δ¹⁸O_s) and nitrogen and carbon isotopic compositions of the host tissue (δ¹⁵N_h; δ¹³C_h) and zooxanthellae (δ¹⁵N_z; δ¹³C_z). δ¹³C_s decreased immediately after bleaching in M. capitata, but not in P. compressa. δ¹⁸O_s of both species failed to record the warming event. During the remaining months of recovery, δ¹³C_s and δ¹⁸O_s were more enriched in treatment than control corals due to decreases in calcification and metabolic fractionation during that time. Increased δ¹⁵N_h of treatment P. compressa may be due to expelled zooxanthellae during bleaching and recovery. Increased δ¹⁵N_z at 1.5 months in treatment fragments of both species reflects the increased incorporation of dissolved inorganic nitrogen to facilitate mitotic cell division and/or chl a/cell recovery. Changes in δ¹³C_h and δ¹³C_z at 1.5 months in treatment M. capitata indicated a large increase in heterotrophically acquired carbon relative to photosynthetically fixed carbon. We experimentally show that isotopes in coral skeleton, host tissue and zooxanthellae can be used to verify physiological changes during bleaching and recovery, but their use as a proxy for past bleaching events in the skeletal record is limited.     

The use of proxy chemical records in Coral skeletons to ascertain past environmental conditions in Florida Bay

This paper will discuss the use of chemical proxies in coral skeletons to reconstruct the history of salinity (from the δ¹⁸O of the skeleton) and nutrients in the water (from the δ¹³C) in Florida Bay between 1824 and 1994. Monthly salinity and water temperature data collected since 1989 were used to establish a correlation between salinity, temperature, and the δ¹⁸O of the skeleton of the coralSolenastrea bournoni from Lignumvitae Basin in Florida Bay. This relationship explains over 50% of the variance in the δ¹⁸O of the skeleton. Assuming that interannual variations in the temperature of the water are small, we have applied this relationship to the δ¹⁸O measured in the coral skeleton collected from Lignumvitae Basin which has a record between 1824 and 1993. These data provide a revised estimate of salinity variation in Lignumvitae Basin for the period when historical records for salinity were not available, and show that the highest salinity events occurred in the past 30 yr. Using the relationships between the salinity in Lignumvitate Basin and other basins, obtained using a modern dataset, we are able to estimate ranges in salinity for other portions of Florida Bay. Skeletons of specimens of the coral speciesSiderastrea radians collected from other areas of Florida Bay show similar patterns in the δ¹⁸O over the past 10 yr, indicating that corals in most portions of Florida Bay are recording salinity variations in their skeletons and therefore support the idea that salinity variations in different portions of Florida Bay can be related. Fluorescence analysis of the coral from Lignumvitae Basin shows a large change in the magnitude of the 10-yr signal coincident with the construction of the railway, confirming that this event had a significant impact upon Florida Bay. The δ¹³C of the coral skeletons reveals a long-term history of the oxidation of organic material, fixation of carbon by photosynthesis (algal blooms), and the intrusion of marine water into the bay. Since the construction of the railway from Miami to Key West there has been a long-term decrease in the δ¹³C of the coral skeleton from Lignumvitae Basin, suggesting the increased oxidation of organic material in this area. This decrease in δ¹³C appears to have reached a minimum value around 1984 and has increased since this time in the western portions of Florida Bay. The increase may be related to the algal blooms prevalent in the area or alternatively could result from intrusion of more marine water. In the eastern areas, a small increase in the δ¹⁸C between 1984 and 1988 was followed by further decline suggesting more oxidation of organic material. We have also attempted to use the concentration of barium in the coral skeleton as a proxy indicator of the nutrient status in Florida Bay.     

Stable carbon isotope ratios in Astrangia danae: evidence for algal modification of carbon pools used in calcification

Stable carbon isotope ratios have been measured in skeletons of the temperature shallow water scleractinian coral, Astrangia danae. δ¹³C values ranging from ?5.42 to ?7.30%. revealed the expected depletion of ¹³C in skeletal carbonate relative to sea water bicarbonate. Differences among the ratios could not be attributed to collection site and were not correlated to skeletal morphology. Values of δ¹³C were directly related to zooxanthellae density for all colonies, so that as zooxanthellae concentration increased, δ¹³C valued increased. Colonies maintained under high temperature conditions were offset from the normal, exhibiting ratios less enriched in ¹³C than similar colonies from natural conditions. These trends supported the models of Weber and Goreau in which the carbon pools used in calcification are modified by algal photosynthesis. Direct evidence of physiological differences between symbiotic and asymbiotic colonies of A. danae has also been provided.     

Strontium in coral aragonite: 3. Sr coordination and geochemistry in relation to skeletal architecture

Use of the coral Sr palaeothermometer assumes that the Sr in coral skeletons is substituted randomly for Ca in the aragonite structure. The presence of Sr in additional phases e.g., strontianite, or the non random distribution of Sr across metal sites in aragonite, would complicate the Sr/Ca-sea surface temperature relationship. We have used Sr K-edge microEXAFS (extended X-ray absorption fine structure) to determine the structural state of Sr across selected microvolumes of four coral skeletons (Porites lobata, Acropora palmata, Pavona clavus, and Montastrea annularis). We used a 5 × 3 μm beam to analyse specific areas of the coral skeletal architecture, i.e., centres of calcification, fasciculi, and dissepiments. All EXAFS analyses refine, within error, to an ideally substituted Sr in aragonite, and we found no evidence of strontianite or partly ordered structural states. Anisotropy in the first shell responses results from the fact that the analysed microvolumes are not necessarily averaged for the responses of all crystal orientations in the aragonite. Although secondary ion mass spectrometry confirmed that Sr/Ca composition can vary substantially between skeletal components, we find no evidence for any contrast in Sr structural state. Sr heterogeneity may result from kinetic effects, reflecting complex disequilibrium processes during crystal precipitation, or biological effects, resulting from variations in the composition of the calcifying fluid which are biologically mediated.     

Annual fluctuation in the stable carbon isotope ratio of coral skeletons: The relative intensities of kinetic and metabolic isotope effects

Stable carbon and oxygen isotope measurements of biogenic carbonate provide information for reconstructing past oceanic environments. In particular, ¹⁸O/¹⁶O ratios correlate with the temperature and salinity of seawater and ¹³C/¹²C is a proxy for dissolved inorganic carbon in seawater and symbiont photosynthesis. Here, we report ¹³C/¹²C and ¹⁸O/¹⁶O values for skeletons of corals (genus Porites) with various growth rates. In faster-growing corals, ¹³C/¹²C and ¹⁸O/¹⁶O showed out-of-phase annual fluctuations. In slower-growing corals, the isotopes fluctuated in phase. We developed a simple vector notation to show two patterns of ¹³C/¹²C annual fluctuation, each with a different offset in relation to ¹⁸O/¹⁶O annual fluctuation. The phase offset between ¹³C/¹²C and ¹⁸O/¹⁶O annual fluctuations depends on the relative intensities of kinetic isotope effects on calcification and metabolic isotope effects such as photosynthesis. This model might improve our ability to infer past climate and oceanographic conditions from coral skeletons.     

Assessing scleractinian corals as recorders for paleo-pH: Empirical calibration and vital effects

Laboratory experiments on the branching, symbiont-bearing coral genus Porites and Acropora have been carried out to determine the dependence of the skeletal boron isotopic composition (δ¹¹B) on the pH of seawater. The results show a clear relationship similar to previously established empirical calibrations for planktonic foraminifera and inorganic calcite. A −0.6‰ offset exists between P. cylindrica and A. nobilis which is systematic over the pH range of 7.7-8.2. To test whether the δ¹¹B of coral skeletons changes with physiological processes such as photosynthesis and respiration, corals were grown along a depth transect in their natural environment and under controlled conditions in the laboratory at varying light intensities and food supply. Although we also observe an isotopic offset between P. compressa and Montipora verrucosa, neither experimental treatment systematically changed the δ¹¹B of the two species. These findings are encouraging for using the boron isotope paleo-pH proxy in corals, because it appears that seawater pH is the dominant control on the boron isotopic composition in corals.     

Monsoon-induced sea surface temperature changes recorded in Indian corals

The South Asian Summer Monsoon induces vertical mixing in the surface Arabian Sea, leading to a reduction in the Sea Surface Temperature (SST) of the order of 3–4°C. This reduction in temperature is recorded by modern corals (Porites) that grow in the Lakshadweep Islands (coralline islands located at about 350 km off the south-west coast of India) in their stable oxygen isotope ratios (denoted by δ¹⁸O). As large coral colonies of this genus are available, our results show that palaeomonsoon records for a few centuries back in time, a crucial input for climatic models aimed at predicting the Asian Monsoon, can be obtained from these corals. We also show that two corals separated by ? 60 km show similar (518O variations as does a giant clam (Tridacna maximus) that grew near one end of the coral colonies. As this clam is known to precipitate CaCO3 in isotopic equilibrium with the ambient sea-water, it is possible to estimate the isotopic offset of coralline δ¹⁸O from that of the CaCO3 precipitated in isotopic equilibrium. This ‘disequilibrium effect’ appears to be constant around 4.5±0.2%0. Our calculations show that SST (t, °C) is related to the coral δ¹⁸O (δ_c) and the sea-water δ¹⁸O (δ_w) by the equation t = 3.0–4.68 (δ_c - δ_w), which is in good agreement with such relationships for corals from the Pacific and Atlantic.     

海南岛沙老岸礁区滨珊瑚氧、碳同位素对气候的记录

通过对海南岛沙老岸礁中正在连续生长的澄黄滨珊瑚骨骼进行氧，碳同位素的测定，对9年生长的珊瑚骨骼依次分析了352个样品，平均每旬有1－2个控制样品，以此来分析珊瑚生长期间的气候变化。首先分析出每年雨季和旱季的差别，得到雨季和旱季曲线的特征，并得出雨季在每年夏季，旱季在每年的秋冬季，表明海南岛礁区是典型的季风气候区。同时将珊瑚骨骼的氧同位素分析数值与相关记录的气温资料做比较，它们的相关系数为0．97和0．79，并得出以氧同位素分析数值求气温的公式。     

Effect of light and brine shrimp on skeletal δC in the Hawaiian coral Porites compressa: a tank experiment

Previous experimental fieldwork showed that coral skeletal δ¹³C values decreased when solar intensity was reduced, and increased in the absence of zooplankton. However, actual seasonal changes in solar irradiance levels are typically less pronounced than those used in the previous experiment and the effect of increases in the consumption of zooplankton in the coral diet on skeletal δ¹³C remains relatively unknown. In the present study, the effects of four different light and heterotrophy regimes on coral skeletal δ¹³C values were measured. Porites compressa corals were grown in outdoor flow-through tanks under 112%, 100%, 75%, and 50% light conditions at the Hawaii Institute of Marine Biology, Hawaii. In addition, corals were fed either zero, low, medium, or high concentrations of brine shrimp. Decreases in light from 100% resulted in significant decreases in δ¹³C that is most likely due to a corresponding decrease in photosynthesis. Increases in light to 112% also resulted in a decrease in δ¹³C values. This latter response may be a consequence of photoinhibition. The overall curved response in δ¹³C values was described by a significant quadratic function. Increases in brine shrimp concentrations resulted in increased skeletal δ¹³C levels. This unexpected outcome appears to be attributable to enhanced nitrogen supply associated with the brine shrimp diet which led to increased zooxanthellae concentrations, increased photosynthesis rates, and thus increased δ¹³C values. This result highlights the potential influence of nutrients from heterotrophically acquired carbon in maintaining the zooxanthellae-host symbiosis in balance. In addition, evidence is presented that suggests that coral skeletal growth and δ¹³C are decoupled. These results increase our knowledge of how light and heterotrophy affects the δ¹³C of coral skeletons.     

Preservation of organic matter in mound-forming coral skeletons

This study demonstrates that intracrystalline organic matter in coral skeletons is well preserved over century timescales. The extent of preservation of organic matter in coral skeletons was investigated by measuring total organic carbon (TOC), total hydrolyzable amino acid (THAA), chloropigment, and lipid concentrations in 0-300 year old annual growth bands from Montastraea annularis (Florida Keys) and Porites lutea (Red Sea). Organic matter intrinsic to the calcium carbonate mineral (intracrystalline) was analyzed separately from total skeletal organic matter. The Red Sea coral had less TOC (0.02-0.04 wt%) than the Florida Keys coral (0.04-0.11 wt%), but a higher percent of intracrystalline organic matter in all annual bands measured. Carbon in the form of THAA, most likely from mineral-precipitating proteins, contributed 30-45% of the TOC in both corals. Carbon in lipids represented about 3% of the TOC in the coral skeletons. Chlorophyll-a and b were present in annual bands where endolithic algae were present, but these compounds were minor contributors to TOC. The distribution of specific organic compounds showed that organic matter was well preserved throughout the time period sampled in both the total and intracrystalline pools. Variations in THAA were not correlated with TOC over time, suggesting that organic matter that is involved in biomineralization, like amino acids, may be deposited in response to different environmental factors than are other components of skeletal organic matter. Differences in the quantity and composition of organic matter between the two corals investigated here were assessed using principal components analysis and suggest that location, species and skeletal structure may all influence organic matter content and possibly the degree of physical protection of organic matter by the coral skeleton. Further, our study suggests that intracrystalline organic matter may be better protected from diagenesis than non-intracrystalline organic matter and may therefore be a more reliable source of organic matter for paleoceanographic studies than total skeletal organic matter.     

The marine oxygen isotope record in Pleistocene coral,Barbados, West Indies

The reef-crest coral Acropora palmata from late Pleistocene reefs on Barbados has recorded the same global variations in oxygen isotopes as planktonic and benthonic foraminifera. Although the record of oxygen isotopes in Acropora palmata is discontinuous, it offers several advantages over the isotope records from deep-sea sediments: (1) the coral grows at water depths of less than 5 m; (2) the samples are unmixed; (3) specimens may be sampled from various elevations of paleo-sea level; and (4) aragonitic corals are suitable for ${}^{230}\text{Th}{}^{234}\text{U}$ and $\text{He}\text{U}$ dating techniques. The latter advantage means that direct dating of the marine oxygen isotope record is possible. Oxygen isotope stage 5e corresponds to Barbados III, dated at 125,000 ± 6000 yr BP. Petrographic and geochemical evidence from five boreholes drilled into the south coast of Barbados indicates a major eustatic lowering (greater than 100 m below present sea level) occurred between 180,000 and 125,000 yr BP. The age and isotopic data suggest correlation of this change in sea level to Emiliani's oxygen isotope stage 6. Acropora palmata deposited at various elevations of sea level during oxygen isotope stage 6 vary by 0.11 ‰ δ¹⁸O for each 10 m of change in sea level. We further hypothesize a minimum drop of 2°C in the average temperature occurred during the regressive phase of oxygen isotope stage 6. These data indicate that temperature lowering of surface water near Barbados lagged behind a major glacial buildup during this time period. Using the δ¹⁸O vs sea level calibration herein derived, we estimate the relative height of sea stands responsible for Barbados coral reef terraces in the time range 80,000 to 220,000 yr BP.     

Rayleigh-based, multi-element coral thermometry: A biomineralization approach to developing climate proxies

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.     

Pleistocene geochemical stratigraphy of the borehole 1317E (IODP Expedition 307) in Porcupine Seabight,SW of Ireland: applications to palaeoceanography and palaeoclimate of the coral mound development

Stable isotopes and element compositions of the fine‐grained matrix were measured for IODP Expedition 307 Hole U1317E drilled from the summit of Challenger Mound in Porcupine Seabight, northeast Atlantic, to explore the palaeoceanographic and palaeoclimatic background to development of the deep‐water coral mound. The 155 m long mound section was divided into two units by an unconformity at 23.6 mbsf: Unit M1 (2.6–1.7 Ma) and Unit M2 (1.0–0.5 Ma). Results from 519 specimens show a difference in δ¹³C value between Unit M1 (?0.6‰ to ?5.0‰) and Unit M2 (?1.0‰ to 1.0‰), but such a distinct difference was not seen in δ¹⁸O values (1.0‰–2.5‰), CaCO₃ content (40–60 wt%), Sr/Ca ratio (2.0–8.0 mmol mol^?1), and Mg/Ca ratio (10.0–20.0 mmol mol^?1) through the mound. Positive δ¹⁸O and negative δ¹³C shifts at the mound base are consistent with the oceanographic changes in the northeast Atlantic at the beginning of the Quaternary. The positive δ¹³C regression in Unit M2 suggests a linkage to the mid Pleistocene intensified glaciation in the Northern Hemisphere. Warm Mediterranean Upper Core Water of Mediterranean Outflow Water, Eastern North Atlantic Water and cold Labrador Sea Water of North Atlantic Deep Water are key oceanographic features that cause spikes and shifts in stable isotope and element composition. However, the stable isotope values of the sediment matrix could not primarily record the glacial–interglacial eustatic/temperature change, but indirectly indicate current regimes of the intermediate oceanic layer where the coral mound grew. Similarly, elemental ratios and CaCO₃ content may not represent the productivity and temperature of surface sea water, respectively, but superpose the fractions from both surface and bottom water. It is concluded that palaeoceanographic change coupled to the Pleistocene glacial/interglacial cycles is a key control on the geochemical stratigraphy of the matrix sediments of the carbonate mound developed in Porcupine Seabight. Copyright © 2011 John Wiley & Sons, Ltd.     

Interpreting prograde-growth histories of Al2SiO5 triple-point rocks using oxygen-isotope thermometry: an example from the Truchas Mountains, USA

Oxygen‐isotope compositions of kyanite, andalusite, prismatic sillimanite and fibrolite from the Proterozoic terrane in the Truchas Mountains, New Mexico differ from one another, suggesting that these minerals did not grow in equilibrium at the Al₂SiO₅ (AS) polymorph‐invariant point as previously suggested. Instead, oxygen‐isotope temperature estimates indicate that growth of kyanite, andalusite and prismatic sillimanite occurred at c. 575, 615 and 640 °C respectively. Temperature estimates reported in this paper are interpreted as those of growth for the different AS polymorphs, which are not necessarily the same as peak metamorphic temperatures for this terrane. Two distinct temperature estimates of c. 580 °C and c. 700 °C are calculated for most fibrolite samples, with two samples yielding clear evidence of quartz‐fibrolite oxygen‐isotope disequilibrium. These data indicate that locally, and potentially regionally, oxygen‐isotope disequilibrium between quartz and fibrolite may have resulted from rapid fibrolite nucleation. Pressures of mineral growth that were extrapolated from oxygen‐isotope thermometry results and calculated using petrological constraints suggest that kyanite and one generation of fibrolite grew during M1 at 5 kbar, and that andalusite, prismatic sillimanite and a second generation of fibrolite grew during M2 at 3.5 kbar. M1 and M2 therefore represent two distinct metamorphic events that occurred at different crustal levels. The ability of the AS polymorphs to retain δ¹⁸O values of crystallization make these minerals ideal to model prograde‐growth histories of mineral assemblages in metamorphic terranes and to understand more clearly the pressure–temperature histories of multiple metamorphic events.