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.     

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.     

Strontium heterogeneity and speciation in coral aragonite: implications for the strontium paleothermometer

Sea surface temperatures (SSTs) have been inferred previously from the Sr/Ca ratios of coral aragonite. However, microanalytical studies have indicated that Sr in some coral skeletons is more heterogeneously distributed than expected from SST data. Strontium may exist in two skeletal phases, as Sr substituted for Ca in aragonite and as separate SrCO₃ (strontianite) domains. Variations in the size, quantity, or both of these domains may account for small-scale Sr heterogeneity. Here, we use synchrotron X-ray fluorescence to map Sr/Ca variations in a Porites lobata skeleton at a 5 μm scale. Variations are large and unrelated to changes in local seawater temperature or composition. Selected area extended X-ray absorption fine structure (EXAFS) spectroscopy of low- and high-Sr areas indicates that Sr is present as a substitute ion in aragonite i.e., domains of Sr carbonate (strontianite) are absent or in minor abundance. Variations in strontianite abundance are not responsible for the Sr/Ca fluctuations observed in this sample. The Sr microdistribution is systematic and appears to correlate with the crystalline fabric of the coral skeleton, suggesting Sr heterogeneity may reflect nonequilibrium calcification processes. Nonequilibrium incorporation of Sr complicates the interpretation of Sr/Ca ratios in terms of SST, particularly in attempts to extend the temporal resolution of the technique. The micro-EXAFS technique may prove to be valuable, allowing the selection of coral microvolumes for Sr/Ca measurement where strontium is incorporated in a known structural environment.     

Compositional variations at ultra-structure length scales in coral skeleton

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.     

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.     

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.     

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.     

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.     

Deep-sea coral aragonite as a recorder for the neodymium isotopic composition of seawater

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.     

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.     

Identification and composition of secondary meniscus calcite in fossil coral and the effect on predicted sea surface temperature

This study uses electron backscatter diffraction (EBSD) and atomic force microscopy (AFM) to identify secondary calcite in coral skeletons. Secondary calcite appears to have nucleated on the original aragonite dissepiments, producing horizontal structures that mimic the morphology of the original coral aragonite, forming dissepiment-like meniscus structures. The Sr/Ca and δ¹⁸O of the pristine aragonite and secondary calcite were analysed by secondary ion mass spectrometry (SIMS). The effect of calcite inclusion on the mean geochemistry of the coral carbonate and subsequent sea surface temperature (SST) calculations were determined for both Sr/Ca and δ¹⁸O. Inclusion of as little as 1% secondary calcite within the primary coral aragonite elevates the Sr/Ca-derived SST by 1.2 °C and could markedly offset estimates of past tropical climate. Conversely, inclusion of 10% secondary calcite has little effect on the SST estimated from δ¹⁸O (+ 0.6 °C) indicating that this proxy is relatively robust to even large amounts of calcite. The different extents to which the two proxies would be influenced by inadvertent inclusion of such meniscus calcite demonstrate the importance of a multi-proxy approach.     

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.     

Thermochemistry of strontium incorporation in aragonite from atomistic simulations

We have investigated the thermodynamics of mixing between aragonite (orthorhombic CaCO₃) and strontianite (SrCO₃). In agreement with experiment, our simulations predict that there is a miscibility gap between the two solids at ambient conditions. All Sr_xCa_1−xCO₃ solids with compositions 0.12 < x < 0.87 are metastable with respect to separation into a Ca-rich and a Sr-rich phase. The concentration of Sr in coral aragonites (x ∼ 0.01) lies in the miscibility region of the phase diagram, and therefore formation of separated Sr-rich phases in coral aragonites is not thermodynamically favorable. The miscibility gap disappears at around 380 K. The enthalpy of mixing, which is positive and nearly symmetric with respect to x = 0.5, is the dominant contribution to the excess free energy, while the vibrational and configurational entropic contributions are small and of opposite sign. We provide a detailed comparison of our simulation results with available experimental data.     

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.     

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.     

Element partitioning during precipitation of aragonite from seawater: A framework for understanding paleoproxies

This study presents the results from precipitation experiments carried out to investigate the partitioning of the alkaline earth cations Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ between abiogenic aragonite and seawater as a function of temperature. Experiments were carried out at 5 to 75 °C, using the protocol of Kinsman and Holland [Kinsman, D.J.J., Holland, H.D., 1969. The coprecipitation of cations with CaCO₃ IV. The coprecipitation of Sr²⁺ with aragonite between 16 and 96 °C. Geochim. Cosmochim. Acta33, 1-17.] The concentrations of Mg Sr and Ba were determined in the fluid from each experiment by inductively coupled plasma-mass spectrometry, and in individual aragonite grains by secondary ion mass spectrometry. The experimentally produced aragonite grains are enriched in trace components (“impurities”) relative to the concentrations expected from crystal-fluid equilibrium, indicating that kinetic processes are controlling element distribution. Our data are not consistent with fractionations produced kinetically in a boundary layer adjacent to the growing crystal because Sr²⁺, a compatible element, is enriched rather than depleted in the aragonite. Element compatibilities, and the systematic change in partitioning with temperature, can be explained by the process of surface entrapment proposed by Watson and Liang [Watson, E.B., Liang, Y., 1995. A simple model for sector zoning in slowly grown crystals: implications for growth rate and lattice diffusion, with emphasis on accessory minerals in crustal rocks. Am. Mineral.80, 1179-1187] and Watson [Watson, E.B., 1996. Surface enrichment and trace-element uptake during crystal growth. Geochim. Cosmochim. Acta60, 5013-5020; Watson, E.B., 2004. A conceptual model for near-surface kinetic controls on the trace-element and stable isotope composition of abiogenic calcite crystals. Geochim. Cosmochim. Acta68, 1473-1488]. This process is thought to operate in regimes where the competition between crystal growth rate and diffusivity in the near-surface region limits the extent to which the solid can achieve partitioning equilibrium with the fluid. A comparison of the skeletal composition of Diploria labyrinthiformis (brain coral) collected on Bermuda with results from precipitation calculations carried out using our experimentally determined partition coefficients indicate that the fluid from which coral skeleton precipitates has a Sr/Ca ratio comparable to that of seawater, but is depleted in Mg and Ba, and that there are seasonal fluctuations in the mass fraction of aragonite precipitated from the calcifying fluid (“precipitation efficiency”). The combined effects of surface entrapment during aragonite growth and seasonal fluctuations in “precipitation efficiency” likely forms the basis for the temperature information recorded in the aragonite skeletons of Scleractinian corals.     

Diagenesis and its impact on Sr/Ca ratio in Holocene Acropora corals

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.     

Sequestration of Sr(II) by calcium oxalate—A batch uptake study and EXAFS analysis of model compounds and reaction products

Calcium oxalate monohydrate (CaC₂O₄·H₂O—abbreviated as CaOx) is produced by two-thirds of all plant families, comprising up to 80 wt.% of the plant tissue and found in many surface environments. It is unclear, however, how CaOx in plants and soils interacts with metal ions and possibly sequesters them. This study examines the speciation of Sr(II)_aq following its reaction with CaOx. Batch uptake experiments were conducted over the pH range 4-10, with initial Sr solution concentrations, [Sr]_aq, ranging from 1 × 10⁻⁴ to 1 × 10⁻³ M and ionic strengths ranging of 0.001-0.1 M, using NaCl as the background electrolyte. Experimental results indicate that Sr uptake is independent of pH and ionic strength over these ranges. After exposure of CaOx to Sr_aq for two days, the solution Ca concentration, [Ca]_aq, increased for all samples relative to the control CaOx suspension (with no Sr added). The amount of Sr_aq removed from solution was nearly equal to the total [Ca]_aq after exposure of CaOx to Sr. These results suggest that nearly 90% of the Sr is removed from solution to a solid phase as Ca is released into solution. We suggest that the other 10% is sequestered through surface adsorption on a solid phase, although we have no direct evidence for this. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the molecular-level speciation of Sr in the reaction products. Deconvolutions of the Sr K-edge EXAFS spectra were performed to identify multi-electron excitation (MEE) features. MEE effects were found to give rise to low-frequency peaks in the Fourier transform before the first shell of oxygen atoms and do not affect EXAFS fitting results. Because of potential problems caused by asymmetric distributions of Sr-O distances when fitting Sr K-edge EXAFS data using the standard harmonic model, we also employed a cumulant expansion model and an asymmetric analytical model to account for anharmonic effects in the EXAFS data. For Sr-bearing phases with low to moderate first-shell (Sr-O pair correlation) anharmonicity, the cumulant expansion model is sufficient for EXAFS fitting; however, for higher degrees of anharmonicity, an analytical model is required. Based on batch uptake results and EXAFS analyses of reaction products, we conclude that Sr is dominantly sequestered by a solid phase at the CaOx surface, likely the result of a dissolution-reprecipitation mechanism, to form SrC₂O₄ of mixed hydration state (i.e. SrOx·nH₂O, where n = 0, 1, or 2). Surprisingly, no spectroscopic or XRD evidence was found for a (Sr,Ca)Ox solid solution or for a separate SrCO₃ phase. In addition, we found no evidence for Sr(II) inner-sphere sorption complexes on CaOx surfaces based on lack of Sr-Ca second-neighbor pair correlations in the EXAFS spectra, although some type of Sr(II) surface complex (perhaps a type B Sr-oxalate ternary complex or an outer-sphere Sr(II) complex) or some as yet undetected Sr-bearing solid phases are needed to account for approximately 10% of Sr uptake by CaOx. The formation of a hydrated SrOx phase in environments under conditions similar to those of our experiments should retard Sr mobility and could be a significant factor in the biogeochemical cycling of Sr in soils and sediments or in plants and plant litter where CaOx is present.     

西沙珊瑚锶温度计：便捷高精度海洋古水温代用指标

西沙群岛现代滨珊瑚1976－1994年生长期间Sr含量的高精度热电离质谱测定结果表明，Sr含量随季节发生周期性的变化，并与当地同期实测海水月平均温度变化相吻合，其Sr含量与实测海水温度相关系数为－0．94。这18年冬夏极端Sr含量与同期月温的相关系数可高达－0．98。Sr温度计误差小于0．5℃。     

High pressure phase transformations in aragonite-type carbonates

High-temperature and high-pressure experiments conducted in a diamond-anvil cell revealed phase transformations in the aragonite-type carbonates of strontianite (SrCO₃), cerussite (PbCO₃), and witherite (BaCO₃) at pressures below 4 GPa and ～1000?°C. The powder X-ray diffraction patterns of these high-pressure phases can be reasonably indexed with the same type of orthorhombic cell having a space group of P2₁22 (17). By assuming 16 MCO₃ (M=Sr, Ba or Pb) molecules in a unit cell, the transition from the aragonite form to a new phase was concomitant with a volume contraction of 4.23, 2.38, and 2.34% for SrCO₃, PbCO₃, and BaCO₃, respectively. If the same phase transition were to occur in CaCO₃, it has been estimated that the transition would accompany a 7% volume contraction.