The build up of the isotopic signal in skeletons of the stony coral Porites lutea

The build up of the isotopic signal in corals was followed by sampling the newly formed skeleton at a monthly resolution for a period of two years in order to establish the interrelations between the calcification processes and the skeletal isotopic composition. We deployed two underwater sampling schemes, which provide a monitor of the changes in water temperature and δ¹⁸O and in the corresponding newly accreted skeleton of undisturbed Porites lutea colonies under natural conditions and four transplanted colonies, which maintained the genetic identity throughout the experiment. The results indicate that δ¹⁸O of the newly accreted skeleton does not correlate with ambient temperature although the seasonal temperature variability at the site (winter to summer) is in the order of 6 °C and δ¹⁸O of seawater is constant throughout the year. In contrast to the newly formed surface skeleton, the isotopic compositions of the deep and older parts of the skeleton show the predicted annual isotopic pattern with highly significant correlation between δ¹⁸O_s and SST. The transformation between temperature-independent to temperature-dependent isotopic signal occurs several months after the skeleton was formed at the surface. The position of the skeleton in relation to the open sea may generate the difference between δ¹⁸O_s of the surface skeleton and that of the skeleton previously accreted further down the tissue layer. Our data support the general model of a multi-step skeletogenesis process, where the temperature independent skeleton is entails the first step, the production of skeletal scaffold, and the environmental temperature signature is captured by the next two other steps: the thickening and the periodic abrupt uplift occurring at the depth of the tissue layer. However, re-examination and development of the current isotopic models for coral calcification are required in order to explain the observed different temperature dependency during the growth’s sequence.     

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.     

Environmental control of the oxygen isotope composition of Porites coral microatolls

Understanding the influence of climatic and non-climatic factors on geochemical signals in corals is critical for assessing coral-derived records of tropical climate variability. Porites microatolls form large, disk-shaped colonies constrained in their upward growth by exposure at or close to mean spring low water level, and occur on Indo-Pacific reefs. Microatolls appear suitable for paleoclimate reconstruction, however the systematics of the microatoll chemistry-climate relationship are yet to be characterized. In this study, the δ¹⁸O signal in Porites microatolls from well-flushed reef flats on Kiritimati (Christmas) Island, central Pacific was investigated for intra-coral (growth aspect and extension rate effects) and between-coral effects, and to explore the climate signal contained within their skeletons. Samples for δ¹⁸O analysis were taken from six individual transects from different positions within Porites microatoll XM22. The results show that: (1) the average standard deviation for the mean δ¹⁸O values of transects that represent the same time periods is 0.03‰, and is within measurement error for a single analysis (0.04‰); (2) the average standard deviation for time-equivalent, near-monthly samples along the transects within the same microatoll is 0.07‰ and; (3) comparison of the average δ¹⁸O values of records for different microatolls from across Kiritimati Island show only a small between-coral differences of 0.04‰ and 0.11‰ for different time periods. These differences in mean δ¹⁸O are within the range for intra- and inter-colony differences in seasonal and interannual δ¹⁸O reported for dome-shaped Porites. Based on these results, a stacked microatoll δ¹⁸O record was constructed for the period 1978-2007 for comparison with published coral δ¹⁸O records for nearby dome-shaped Porites. There is a systematic offset between the two types of records, which is probably due to variations in δ¹⁸O seawater across Kiritimati Island. Despite the offset, all records show similar amplitudes for the seasonal-cycle of δ¹⁸O, and there is a strong correlation (r = −0.71) between microatoll δ¹⁸O and local sea surface temperature (SST). The δ¹⁸O-SST slope relationship for microatolls is −0.15‰/°C, very similar to that reported for fast-growing domed corals (−0.18‰ to −0.22‰/°C). Statistical analysis of the stacked microatoll δ¹⁸O record shows that it is correlated with both local and large-scale climate variables (primarily SST) at semiannual, annual and interannual timescales. Our results show that the signal reproducibility and fidelity of skeletal δ¹⁸O in coral microatolls is comparable to that observed for more conventional coral growth forms. Longer-lived, and fossil, Porites microatolls, where they have grown in suitably flushed environments, are likely to contain δ¹⁸O signals that can significantly extend instrumental records of tropical climate variability.     

Oxygen isotope systematics in Diploastrea heliopora: new coral archive of tropical paleoclimate

Diploastrea heliopora forms dense, robust, dome-shaped coral colonies throughout the reef ecosystems of the tropical Pacific and Indian Oceans. This slow-growing (2 to 6 mm/yr) coral has the potential to yield continuous paleoclimate records spanning up to 1000 yr for the warmest waters on Earth, the Indo-Pacific Warm Pool, and has a long fossil history as a single recognizable species. Despite the potential of Diploastrea to be an important new paleoclimate archive, little is known about the systematics of geochemical tracers incorporated into its skeleton. To fill this knowledge gap, we compared skeletal δ¹⁸O signatures in live Diploastrea and Porites colonies from Southwest Lagoon, near Amédée Lighthouse, New Caledonia (at the southern latitudinal limit for Diploastrea) and Alor, Indonesia (in the core area of the Indo-Pacific Warm Pool). We designed a new microsampling technique to minimize smoothing and distortion of the isotopic records due to the complex calyx architecture and slow growth of Diploastrea. High-resolution isotope profiles from the septal portion of the Diploastrea corallite are attenuated, whereas those restricted to the central columella are similar in quality to those extracted from the well-established Porites coral archive. The δ¹⁸O-temperature relationship for the columellar portion of Diploastrea (−0.18‰/°C) is in good agreement with that derived for a nearby Porites (−0.19‰/°C; Quinn et al., 1996), on the basis of comparison with an in situ sea surface temperature record from Amédée Lighthouse. There is a measurable difference of 0.3 ± 0.1‰ between the kinetic/biological disequilibrium offsets from seawater δ¹⁸O composition for Diploastrea and Porites. Despite this offset in mean δ¹⁸O, Diploastrea accurately records the regional differences in mean temperature and salinity between New Caledonia and the Indo-Pacific Warm Pool. Additional tests show that Diploastrea records El Niño-Southern Oscillation (ENSO) interannual variability in sea surface temperature and salinity across the southwestern Pacific, indicating that it should yield dependable paleo-ENSO records. Based on these results, we propose that D. heliopora has the potential to provide an important new coral archive of tropical paleoclimate.     

Combining in situ isotopic, trace element and textural analyses of quartz from four magmatic-hydrothermal ore deposits

This study couples in situ ¹⁶O, ¹⁷O and ¹⁸O isotope and in situ trace element analyses to investigate and characterize the geochemical and textural complexity of magmatic-hydrothermal quartz crystals. Euhedral quartz crystals contemporaneous with mineralization were obtained from four magmatic-hydrothermal ore deposits: El Indio Au–Ag–Cu deposit; Summitville Au–Ag–Cu deposit; North Parkes Cu–Au deposit and Kingsgate quartz-Mo–Bi–W deposit. The internal features of the crystals were imaged using cathodoluminescence and qualitative electron microprobe maps. Quantitative isotopic data were collected in situ using 157 nm laser ablation inductively coupled plasma mass spectrometry (for 40 trace elements in quartz) and sensitive high-resolution ion microprobe (for 3 isotopes in quartz). Imaging revealed fine oscillatory zoning, sector zoning, complex “macromosaic” textures and hidden xenocrystic cores. In situ oxygen isotope analyses revealed a δ¹⁸O range of up to 12.4 ± 0.3 ‰ in a single crystal—the largest isotopic range ever ascribed to oscillatory zonation in quartz. Some of these crystals contain a heavier δ¹⁸O signature than expected by existing models. While sector-zoned crystals exhibited strong trace element variations between faces, no evidence for anisotropic isotope fractionation was found. We found: (1) isotopic heterogeneity in hydrothermal quartz crystals is common and precludes provenance analysis (e.g., δD–δ¹⁸O) using bulk analytical techniques, (2) the trace element signature of quartz is not an effective pathfinder toward noble metal mineralization and (3) in three of the four samples, both textural and isotopic data indicate non-equilibrium deposition of quartz.     

The reef builder gastropod Dendropomapetreaum - A proxy of short and long term climatic events in the Eastern Mediterranean

High-resolution δ¹⁸O and δ¹³C records obtained from seven cores were drilled from ledges of the reef builder gastropod Dendropomapetreaum and used to reconstruct variations in the Levantine basin sea surface temperature, hydrology and productivity during the past 500 years. The δ¹⁸O of the aragonite shell of living D. petreaum indicate that skeletal deposition occurs under isotopic equilibrium and faithfully record the temperature and surface water δ¹⁸O during summer and autumn. The mean down core δ¹⁸O record clearly captures global and local climatic events, such as the Little Ice Age (LIA) and the recent warming of surface waters in the Eastern Mediterranean. Comparison to the Western Mediterranean vermetid δ¹⁸O record reveals changes in the freshwater/evaporation budgets of the two basins during cold and warm periods. The Eastern basin had lower surface temperatures and excess evaporation during the LIA and experienced a relatively larger warming and/or a decrease in freshwater/evaporation during the past 70 years. The D. petraeum δ¹³C is strongly related to δ¹³C of dissolved inorganic carbon and to the primary productivity of the surface water. The mean down core δ¹³C record exhibits enrichment during the LIA maximum and a strong depletion trend during the last century. The LIA δ¹³C enrichment is attributed to an increase in primary production and high nutrient levels which resulted from increased vertical mixing and upwelling. The last century δ¹³C depletion is mostly related to the increased anthropogenic emissions of ¹³C depleted carbon dioxide and to a certain decrease in primary production. The data indicate that D. petraeum isotopic signatures are unique proxies for last 500 years high-resolution reconstruction of paleo-oceanographic environments in the Mediterranean and potentially in the sub-tropical Atlantic regions.     

O/O and D/H ratios of pedogenic kaolinite in a North American Cenomanian laterite: Paleoclimatic implications

Kaolinite, gibbsite and quartz are the dominant minerals in samples collected from two outcrops of a Cenomanian (∼95 Ma) laterite in southwestern Minnesota. A combination of measured yields and isotope ratios permitted mass balance calculations of the δD and δ¹⁸O values of the kaolinite in these samples. These calculations yielded kaolinite δD values of about −73‰ and δ¹⁸O values of about +18.7‰. The δD and δ¹⁸O values appear to preserve information on the ancient weathering system.If formed in hydrogen and oxygen isotope equilibrium with water characterized by the global meteoric water line (GMWL), the kaolinite δD and δ¹⁸O values indicate a crystallization temperature of 22 (±5) °C. A nominal paleotemperature of 22 °C implies a δ¹⁸O value for the corresponding water of −6.3‰. The combination of temperature and meteoric water δ¹⁸O values is consistent with relatively intense rainfall at that mid-paleolatitude location (∼40°N) on the eastern shore of the North American Western Interior Seaway. The inferred Cenomanian paleosol temperature of ∼22 °C is in general accord with published mid-Cretaceous continental mean annual temperatures (MAT) estimated from leaf margin analyses of fossil plants.When compared with results from a published GCM-based Cenomanian climate simulation which specifies a latitudinal sea surface temperature (SST) gradient that was either near modern or smaller-than-modern, the kaolinite paleotemperature of 22 °C is closer to the GCM-predicted MAT for a smaller equator-to-pole temperature difference in the mid-Cretaceous. Moreover, the warm, kaolinite-derived, mid-paleolatitude temperature of 22 °C is associated with proxy estimates of high concentrations of atmospheric CO₂ in the Cenomanian. The overall similarity of proxy and model results suggests that the general features of Cenomanian continental climate in that North American locale are probably being revealed.     

Metallogenesis and ore-forming time of the Changtuxili Mn–Ag–Pb–Zn deposit in Inner Mongolia: Evidence from C–O–S isotopes and U–Pb geochronology

This paper reports new geochronological (U–Pb) and isotope (C, O, and S) data to investigate the timing of mineralization and mode of ore genesis for the recently discovered Changtuxili Mn–Ag–Pb–Zn deposit, located on the western slopes of the southern Great Hinggan Range in NE China. The mineralization is hosted by intermediate–acidic lavas and pyroclastic rocks of the Baiyingaolao Formation. Three stages of mineralization are identified: quartz–pyrite (Stage I), galena–sphalerite–tetrahedrite–rhodochrosite (Stage II), and quartz–pyrite (Stage III). δ¹³C and δ¹⁸O values for carbonate from the ore vary from −8.51‰ to −4.96‰ and 3.97‰ to 15.90‰, respectively, which are indicative of a low-temperature alteration environment. δ³⁴S_V-CDT values of sulfides range from −1.77‰ to 4.16‰ and show a trend of equilibrium fractionation (δ³⁴S_Py ​> ​δ³⁴S_Sp ​> ​δ³⁴S_Gn). These features indicate that pyrite, sphalerite, and galena precipitated during the period of mineralization. The alteration mineral assemblage and isotope data indicate that the weakly acidic to weakly alkaline ore-forming fluid was derived largely from meteoric water and the ore-forming elements C and S originated from magma. During the mineralization, a geochemical barrier was formed by changes in the pH of the ore-forming fluid, leading to the precipitation of rhodochrosite. On the basis of the mineralization characteristics, new isotope data, and comparison with adjacent deposits, we propose that the Changtuxili Mn–Ag–Pb–Zn deposit is an intermediate-to low-sulfidation epithermal deposit whose formation was controlled by fractures and variability in the pH of the ore-forming fluid. The surrounding volcanic rocks yield zircon U–Pb ages of 160−146 ​Ma (Late Jurassic), indicating that the mineralization is younger than 146 ​Ma.     

Controls on calcium isotope fractionation in cultured planktic foraminifera, Globigerinoides ruber and Globigerinella siphonifera

Specimens of two species of planktic foraminifera, Globigerinoides ruber and Globigerinella siphonifera, were grown under controlled laboratory conditions at a range of temperatures (18-31 °C), salinities (32-44 psu) and pH levels (7.9-8.4). The shells were examined for their calcium isotope compositions (δ^44/40Ca) and strontium to calcium ratios (Sr/Ca) using Thermal Ionization Mass Spectrometry and Inductively Coupled Plasma Mass Spectrometry. Although the total variation in δ^44/40Ca (∼0.3‰) in the studied species is on the same order as the external reproducibility, the data set reveals some apparent trends that are controlled by more than one environmental parameter. There is a well-defined inverse linear relationship between δ^44/40Ca and Sr/Ca in all experiments, suggesting similar controls on these proxies in foraminiferal calcite independent of species. Analogous to recent results from inorganically precipitated calcite, we suggest that Ca isotope fractionation and Sr partitioning in planktic foraminifera are mainly controlled by precipitation kinetics. This postulation provides us with a unique tool to calculate precipitation rates and draws support from the observation that Sr/Ca ratios are positively correlated with average growth rates. At 25 °C water temperature, precipitation rates in G. siphonifera and G. ruber are calculated to be on the order of 2000 and 3000 μmol/m²/h, respectively. The lower δ^44/40Ca observed at ?29 °C in both species is consistent with increased precipitation rates at high water temperatures. Salinity response of δ^44/40Ca (and Sr/Ca) in G. siphonifera implies that this species has the highest precipitation rates at the salinity of its natural habitat, whereas increasing salinities appear to trigger higher precipitation rates in G. ruber. Isotope effects that cannot be explained by precipitation rate in planktic foraminifera can be explained by a biological control, related to a vacuolar pathway for supply of ions during biomineralization and a pH regulation mechanism in these vacuoles. In case of an additional pathway via cross-membrane transport, supplying light Ca for calcification, the δ^44/40Ca of the reservoir is constrained as −0.2‰ relative to seawater. Using a Rayleigh distillation model, we calculate that calcification occurs in a semi-open system, where less than half of the Ca supplied by vacuolization is utilized for calcite precipitation. Our findings are relevant for interpreting paleo-proxy data on δ^44/40Ca and Sr/Ca in foraminifera as well as understanding their biomineralization processes.     

Minor and trace element incorporation into branching coral Acropora nobilis skeleton

Chemical and isotopic compositions of the Acropora nobilis skeleton were analyzed at various spatial resolutions to investigate the mechanism by which elements are incorporated into the skeleton. Chemical and isotopic profiles along growth axes of axial and radial corallites did not show seasonal variation, with the exception of the δ¹⁸O profile of the axial corallite. Detailed observations of the skeletal structure revealed that the skeletal density increased with distance from the tip because secondarily precipitated aragonite (here called the “infilling” skeleton) filled pore spaces in the “framework” skeleton. Microscale element analyses revealed that main part of the infilling skeleton had lower Mg/Ca and higher Sr/Ca and U/Ca than the framework skeleton. At microscale, Sr/Ca and U/Ca were positively correlated with each other, and negatively correlated with Mg/Ca but only weakly. The results showed that the infilling skeleton differed significantly from the adjacent framework skeleton in terms of not only formation chronology but also chemical composition, and that the bulk composition was influenced by the infilling/framework skeletal ratio. In order to use the Acropora skeleton as a paleoclimate archive, the relationship between environmental factors and the chemical composition of each skeletal component needs to be established.     

The stable isotopic composition of coral skeletons: control by environmental variables

The reef corals Pocillopora damicornis and Montipora verrucosa were cultured under various controlled temperature and light conditions. The corals were analyzed for growth rate, tissue pigment content and skeletal ¹³C and ¹⁸O. Coral skeletal δ¹³C values varied with light dose and correlated with changes in zooxanthellar pigment. The δ¹³C values of skeletal aragonite seem to be modified by oxidation of photosynthetically produced organic matter.Functionally significant relationships between coral skeletal δ¹⁸O values and temperature have been determined. The temperature coefficients of the δ¹⁸O values [?4.4°C (%.)^?1] are similar to the first order coefficient in the equilibrium paleotemperature equation, but the δ¹⁸O values have taxonomically consistent offsets from equilibrium. The offsets may be attributed to the coral metabolism with slight but statistically significant differences between the two genera. Environmental and metabolic variables other than temperature have little or no effect on skeletal δ¹⁸O.     

Geochemical characteristics from tests of four modern planktonic foraminiferal species in the Indonesian Throughflow region and their implications

Test geochemistry of planktonic foraminifera is an indispensable tool in reconstructing past ocean hydrological changes. It is essential to investigate region-specific implications of test geochemistry,although those established from other regions can be broadly applied. In this study, characteristics of6180 and Mg/Ca from tests of four planktonic foraminiferal species, Globigerinoides ruber sensu stricto(s.s.), Globigerinoides sacculifer, Pulleniatina obliquiloculata and Neogloboquadrina dutertrei, from 60 coretop sediment samples retrieved from the Indonesian Throughflow(ITF) region were studied. These geochemical data were compared with modern hydrographic profiles in order to assess their relations and to investigate potential implications of test geochemical parameters in reconstructing past oceanographic change in the ITF region. Calcification depths of these four species were first estimated based on comparison between measured test δ180 and predicted calcite δ¹⁸O that was calculated from modern temperature and salinity. The results indicate that G. ruber s.s. and G. sacculifer calcify within the mixedlayer at 0-50 m and 20-75 m, respectively, whereas P. obliquiloculata and N. dutertrei calcify within the thermocline at around 75 to 125 m. A combined study of excess Mg/Ca(difference between measured and predicted Mg/Ca) and salinity suggests that salinity exerts a negligible impact on test Mg/Ca of these foraminiferal species in the ITF region. Comparison of test Mg/Ca-derived temperatures with temperature profiles of the upper 200 m of the water column from the seas of the ITF region also indicate calcification depths of these species, which match well with the above estimations using test δ¹⁸O. It further indicates that G. sacculifer may be more sensitive in reflecting changes in the depth of the mixedlayer, highlighting a potential use of Mg/Ca temperature difference between G. ruber s.s. and G. sacculifer in reconstructing the depth of the mixed-layer in the ITF region.     

Isotopic partitioning between scallop shell calcite and seawater: effect of shell growth rate

The relationship between molluscan shell growth rate and skeletal δ¹⁸O and δ¹³C was investigated in a detailed field study for the scallop, Pecten maximus. Seasonal variation in shell growth rate was found to be a governing factor influencing shell δ¹⁸O and δ¹³C. At low shell growth rates, shell δ¹⁸O were more positive (of the order +0.4‰) and δ¹³C more negative (up to −2‰) as compared with predicted values for precipitation of inorganic calcite in isotopic equilibrium with seawater. The deviations in δ¹⁸O were hypothesized as reflecting possible differences in solution carbonate chemistry at the site of mineralization in the extrapallial fluid as compared with that of the external seawater medium. The deviations in shell δ¹³C were consistent with incorporation of isotopically depleted respiratory ¹³C (i.e., a metabolic effect). A trend toward more depleted shell δ¹⁸O and δ¹³C values occurred at higher shell growth rates, with negative δ¹⁸O values as compared with predicted equilibrium at shell growth rates above 0.13 mm per day. These simultaneous negative deviations in skeletal δ¹⁸O and δ¹³C were interpreted as resulting from a kinetic effect. The implications for environmental reconstruction from molluscan isotopic records are discussed in light of a model of isotopic behavior based on the findings of the study.     

Geochemistry of Triassic Carbonates: Exploration Guide to Pb–Zn Mineralization in North Tunisia

The Triassic carbonate rocks in Northern Tunisia (Nappes, Domes, Jurassic Mountains zones), consist of massive carbonates, clays and gypsum with authigenic minerals. These are associated with several Pb–Zn deposits and occurrences. At Jebel Ichkeul, Bechateur and Oum Edeboua, these Triassic carbonates exhibit enrichment in Pb (0.32 to 228 ppm), Zn (17 to 261 ppm), Cd (5 to 6 ppm) and Co (0.3 to 89.5 ppm), with respect to their average contents in crustal carbonates. The enrichment is more pronounced at Oum Edeboua (near the ore zone). Permeability is one of the most effective factors of dispersion of metallic trace elements, causing the development of geochemical halos. The genetic relationship of the Triassic carbonate rocks with the ore deposits was controlled by diapirism and tectonic movements, which favored mineralization along the Triassic‐cover contact as well as the remobilization of metals from the mineralized rocks. Analysis of metallic trace elements in Triassic rocks provides clues to the presence of possible mineral deposits. These could be effectively used for both geochemical interpretation and mineral exploration. Carbon and O‐isotope data (– 9.3‰ < δ¹³C < +3‰; +21.9 < δ¹⁸O < +31‰) suggest that the Triassic carbonates of all study areas have marine carbonates as their origin; some of them show significantly lower δ¹⁸O values indicating some exchange with hydrothermal fluids. Calcites associated with mineralization at Oum Edeboua have δ¹³C of –6.2‰ to –8.22‰ and δ¹⁸O of +24.88‰ to +25‰. The C‐isotope compositions of these calcites are ¹³C depleted, indicating an organic origin.     

Controls on Sr/Ca and Mg/Ca in scleractinian corals: The effects of Ca-ATPase and transcellular Ca channels on skeletal chemistry

The Sr/Ca of aragonitic coral skeletons is a commonly used palaeothermometer. However skeletal Sr/Ca is typically dominated by weekly-monthly oscillations which do not reflect temperature or seawater composition and the origins of which are currently unknown. To test the impact of transcellular Ca²⁺ transport processes on skeletal Sr/Ca, colonies of the branching coral, Pocillopora damicornis, were cultured in the presence of inhibitors of Ca-ATPase (ruthenium red) and Ca channels (verapamil hydrochloride). The photosynthesis, respiration and calcification rates of the colonies were monitored throughout the experiment. The skeleton deposited in the presence of the inhibitors was identified (by ⁴²Ca spike) and analysed for Sr/Ca and Mg/Ca by secondary ion mass spectrometry. The Sr/Ca of the aragonite deposited in the presence of either of the inhibitors was not significantly different from that of the solvent (dimethyl sulfoxide) control, although the coral calcification rate was reduced by up to 66% and 73% in the ruthenium red and verapamil treatments, respectively. The typical precision (95% confidence limits) of mean Sr/Ca determinations within any treatment was <±1% and differences in skeletal Sr/Ca between treatments were correspondingly small. Either Ca-ATPase and Ca channels transport Sr²⁺ and Ca²⁺ in virtually the same ratio in which they are present in seawater or transcellular processes contribute little Ca²⁺ to the skeleton and most Ca is derived from seawater transported directly to the calcification site. Variations in the activities of Ca-ATPase and Ca-channels are not responsible for the weekly-monthly Sr/Ca oscillations observed in skeletal chronologies, assuming that the specificities of Ca transcellular transport processes are similar between coral genera.     

On the stable carbon and oxygen isotopic composition of some shallow water,ahermatypic, scleractinian coral skeletons

The δC¹³ and δO¹⁸ values of skeletons of shallow water, ahermatypic scleractinian corals from Jamaica show an excellent correlation over a wide range of isotopic composition. Within individual specimens there are large differences in the isotopic composition of separate skeletal elements. Some of these ahermatypes are enriched in O¹⁸ relative to equilibrium precipitates of calcium carbonate from Jamaican sea water. Therefore our data do not support a two-reservoir mixing model for calcification if one of these reservoirs consists of dissolved marine (inorganic) bicarbonate. As some of these ahermatypic species are enriched in both C¹³ and O¹⁸ relative to hermatypic corals from the same reefs, calcification models based on withdrawal of metabolic CO₂ by photosynthesizing zooxanthellae must also be modified.     

The giant Dexing porphyry Cu–Mo–Au deposit in east China: product of melting of juvenile lower crust in an intracontinental setting

The Dexing porphyry Cu–Mo–Au deposit in east China (1,168 Mt at 0.45 % Cu) is located in the interior of the South China Craton (SCC), made up of two lithospheric blocks, the Yangtze and Cathaysia blocks. The Cu–Mo–Au mineralization is associated with mid-Jurassic granodioritic porphyries with three high-level intrusive centers, controlled by a series of lineaments at the southeastern edge of the Yangtze block. Available age data define a short duration (172–170 Ma) of the felsic magmatism and the mineralization (171?±?1 Ma). The deposit shows broad similarities with deposits in volcanoplutonic arcs, although it was formed in an intracontinental setting. Porphyries associated with mineralization are mainly granodiorites, which contain abundant phenocrysts (40–60 %) and carry contemporaneous microgranular mafic enclaves (MMEs). They are mainly high-K calc-alkaline and show geochemical affinities with adakite, characterized by relatively high MgO, Cr, Ni, Th, and Th/Ce ratios. The least-altered porphyries yielded relatively uniform ε _Nd(t) values from ?0.9 to +0.6, and wide (⁸⁷Sr/⁸⁶Sr)_i range between 0.7046 and 0.7058 partially overlapping with the Sr–Nd isotopic compositions of the MMEs and mid-Jurassic mafic rocks in the SCC. Zircons from the porphyries have positive ε _Hf(t) values (3.4 to 6.9), and low δ¹⁸O values (4.7 to 6.3?‰), generally close to those of depleted mantle. All data suggest an origin by partial melting of a thickened juvenile lower crust involving mantle components (e.g., Neoproterozoic mafic arc magmas), triggered by invasion of contemporaneous mafic melts at Dexing. The MMEs show textural, mineralogical, and chemical evidence for an origin as xenoliths formed by injection of mafic melts into the felsic magmas. These MMEs usually contain magmatic chalcopyrite, and have original, variable contents of Cu (up to 500 ppm). Their geochemical characteristics suggest that they were derived from an enriched mantle source, metasomatized by Proterozoic slab-derived fluids, and supplied a part of Cu, Au, and S for the Dexing porphyry system during their injection into the felsic magmas. The 171?±?1 Ma magmatic-hydrothermal event at Dexing is contemporaneous with the mid-Jurassic extension in the SCC, followed by 160–90 Ma arc-like magmatism in southeastern China. With respect to the tectono-magmatic evolution of the SCC, the emplacement of Cu-bearing porphyries and the associated Cu mineralization occurred in response to the transformation from a tensional regime, related to mid-Jurassic extension, to a transpressional regime, related to the subduction of the Paleo-Pacific oceanic lithosphere.     

Light and temperature effects on Sr/Ca and Mg/Ca ratios in the scleractinian coral Acropora sp.

This study was designed to investigate the effect of light and temperature on Sr/Ca and Mg/Ca ratios in the skeleton of the coral Acropora sp. for the purpose of evaluating temperature proxies for paleoceanographic applications. In the first experiment, corals were cultivated under three light levels (100, 200, 400 μmol photons m⁻² s⁻¹) and constant temperature (27 °C). In the second experiment, corals were cultivated at five temperatures (21, 23, 25, 27, 29 °C) and constant light (400 μmol photons m⁻² s⁻¹). Increasing the water temperature from 21 to 29 °C, induced a 5.7-fold increase in the rate of calcification, which induced a 30% increase in the Mg/Ca ratio. In contrast, by increasing the light level by a factor of 4, the rate of calcification was increased only by a factor of 1.7, with a corresponding 9% increase in the Mg/Ca ratio. Thus, the relative change in the calcification rate in the two experiments (5.7 vs. 1.7) scales with the corresponding relative change in Mg/Ca ratio (30% vs. 9%). We conclude that there is a strong biological control on the incorporation of Mg.For Sr/Ca, good correlations were also observed with water temperature and the calcification rate induced by temperature changes. However, in sharp contrast with the Mg/Ca ratio, a temperature-induced 5.7-fold increase in the calcification rate only induced a 4.5% change (decrease) in the Sr/Ca ratio. An important finding for paleoceanographic applications is that the Sr/Ca ratio did not appear to be sensitive to changes in the light level, or to changes in calcification rate induced by changes in the light level. Thus, in this study, water temperature was found to be the dominant parameter controlling the skeletal Sr/Ca ratio.     

Environmental and biological controls on elemental (Mg/Ca, Sr/Ca and Mn/Ca) ratios in shells of the king scallop Pecten maximus

The relationship between potential elemental proxies (Mg/Ca, Sr/Ca and Mn/Ca ratios) and environmental factors was investigated for the bivalve Pecten maximus in a detailed field study undertaken in the Menai Strait, Wales, U.K. An age model constructed for each shell by comparison of measured and predicted oxygen-isotope ratios allowed comparison on a calendar time scale of shell elemental data with environmental variables, as well as estimation of shell growth rates. The seasonal variation of shell Mn/Ca ratios followed a similar pattern to one previously described for dissolved Mn²⁺ in the Menai Strait, although further calibration work is needed to validate such a relationship. Shell Sr/Ca ratios unexpectedly were found to co-vary most significantly with calcification temperature, whilst shell Mg/Ca ratios were the next most significant control. The temporal variation in the factors that control shell Sr/Ca ratios strongly suggest the former observation most likely to be the result of a secondary influence on shell Sr/Ca ratios by kinetic effects, the latter driven by seasonal variation in shell growth rate that is in turn influenced in part by seawater temperature. P. maximus shell Mg/Ca ratio to calcification temperature relationships exhibit an inverse correlation during autumn to early spring (October to March-April) and a positive correlation from late spring through summer (May-June to September). No clear explanation is evident for the former trend, but the similarity of the records from the three shells analysed indicate that it is a real signal and not a spurious observation. These observations confirm that application of the Mg/Ca proxy in P. maximus shells remains problematic, even for seasonal or absolute temperature reconstructions. For the range of calcification temperatures of 5-19 °C, our shell Mg/Ca ratios in P. maximus are approximately one-fourth those in inorganic calcite, half those in the bivalve Pinna nobilis, twice those in the bivalve Mytilus trossulus, and four to five times higher than Mg/Ca ratios in planktonic and benthonic foraminifera. Our findings further support observations that Mg/Ca ratios in bivalve shell calcite are an unreliable temperature proxy, as well as substantial taxon- and species-specific variation in Mg incorporation into bivalves and other calcifying organisms, with profound implications for the application of this geochemical proxy to the bivalve fossil record.