Synthesis of In‐House Produced Calibrated Silver Phosphate with a Large Range of Oxygen Isotope Compositions     

Christophe Lcuyer  Franois Fourel  Magali Seris  Romain Amiot  Jean Goedert  Laurent Simon 《Geostandards and Geoanalytical Research》2019,43(4):681-688

The large range of stable oxygen isotope values of phosphate‐bearing minerals and dissolved phosphate of inorganic or organic origin requires the availability of in‐house produced calibrated silver phosphate of which isotopic ratios must closely bracket those of studied samples. We propose a simple protocol to synthesise Ag₃PO₄ in a wide range of oxygen isotope compositions based on the equilibrium isotopic fractionation factor and the kinetics and temperature of isotopic exchange in the phosphate–water system. Ag₃PO₄ crystals were obtained from KH₂PO₄ that was dissolved in water of known oxygen isotope composition. Isotopic exchange between dissolved phosphate and water took place at a desired and constant temperature into PYREX? tubes that were placed in a high precision oven for defined run‐times. Samples were withdrawn at desired times, quenched in cold water and precipitated as Ag₃PO₄. We provide a calculation sheet that computes the δ¹⁸O of precipitated Ag₃PO₄ as a function of time, temperature and δ¹⁸O of both reactants KH₂PO₄ and H₂O at t = 0. Predicted oxygen isotope compositions of synthesised silver phosphate range from ?7 to +31‰ VSMOW for a temperature range comprised between 110 and 130 °C and a range of water δ¹⁸O from ?20 to +15‰ VSMOW.  相似文献   

Stable isotope fractionation between mollusc shells and marine waters from Martinique Island   总被引：1，自引：0，他引：1  

Christophe Lécuyer  Bruno Reynard 《Chemical Geology》2004,213(4):293-305

Forty-nine aragonitic and calcitic shells from 14 species of marine tropical molluscs (Bivalvia, Gastropoda, Polyplacophora) and ambient waters from Martinique have been analyzed for their carbon and oxygen isotope compositions. Mineralogy of shells was systematically determined by Raman spectroscopy that reveals composite shell structures and early processes of diagenetic alteration. In mangrove, brackish waters result from the mixing between 89±1% of seawater and 11±1% of freshwater, a hydrological budget quantified by both oxygen isotope and salinity mass balance calculations. Mollusc shells from the mangrove environment (S=31‰; δ¹⁸O=0.5‰) are characterized by mean δ¹³C values (−1.2‰) lower than those (+2.6‰) living in the open sea (S=35‰; δ¹⁸O=1‰). These low carbon isotope compositions result from the oxidation of organic matter into bicarbonate ions used in the building of mollusc shells. The oxygen isotope compositions of the studied mollusc species are mainly controlled by the temperature and composition of seawater whereas the role of the so-called “vital effects” is negligible. Contrasting with carbon isotopes, variability in the δ¹⁸O values among and within species of mollusc shells is very low (1σ=0.15) for a given littoral environment. Using ambient temperatures of seawater (28-30 °C), oxygen isotope fractionations between all studied living species and environmental waters match those extrapolated from the fractionation equation established for molluscs by Grossman and Ku [Chem. Geol., Isot. Geosci. Sect. 59 (1986) 59] in the range 3-20 °C. By analyzing calcite and aragonite layers from the same shell or by comparing shells from different species living in the same environment, there is no evidence that oxygen isotope fractionation between aragonite and water differs from that between calcite and water. On the basis of these results, we conclude that the oxygen isotope compositions of shells from most fossil mollusc species are suitable to estimate past seawater temperatures at any paleolatitude.  相似文献   

Seawater-sediment-basalt interactions: stable isotope (H,O) and elemental fluxes within the Ordovician volcano-sedimentary sequence of Erquy (Brittany,France)     

C. Lécuyer  P. Grandjean  F. Martineau 《Contributions to Mineralogy and Petrology》1995,120(3-4):249-264

The Ordovician volcano-sedimentary succession of Erquy (northern Brittany) is made of immature sediments thermally metamorphosed at the contact of intruding basic sills. Pillow lavas constitute the upper part of the sequence. The trace element geochemistry of sills and pillow lavas suggests that they were derived from a tholeiitic source located beneath a passive margin. This volcanic sequence was metamorphosed under low to moderate greenschist facies conditions. In this study the direction and amplitude of chemical and isotopic fluxes in the basalt-sediment-water system were established and the oxygen and hydrogen isotope compositions of the aqueous fluid that reacted with the volcanic rocks were characterized. Cationic thermometry on chlorites and isotopic thermometry on plagioclase-chlorite pairs indicate closure metamorphic temperatures in the range 200–250°C for the basaltic sills. Stable isotope compositions of iron-rich chlorites (¹⁸O-5.5; D from-60 to-50) and plagioclases (¹⁸O from +9 to +10) reveal that the source of the fluid was certainly seawater. The ¹⁸O variations within the sills are strongly correlated with the rate of progress of the main metamorphic reaction:clinopyroxene+plagioclase+ilmenite chlorite+albite+epidote+quartz+sphene that produced major element mobility at the scale of the volcanosedimentary sequence. Calculation of elemental fluxes by mass balance combined with oxygen isotopic compositions of basalts shows that the highest water-rock ratios (1) were at sill-sediment boundaries and within pillow lavas at the top of the pile. The volcanosedimentary sequence of Erquy was a net sink for Na and a source for Ca. No Mg uptake could be detected whereas the hydrothermal alteration of the sediments released Fe, Si, and K trapped by the volcanic rocks. The ¹⁸O value of the fluid reacting with sills appears to have shifted no more than +4 after percolation at low temperature through immature sediments (¹⁸O12). The Erquy volcano-sedimentary sequence represents a marine hydrothermal system dominated by low-temperature exchange which allowed a general ¹⁸O-enrichment of the volcanic rocks and a ¹⁸O-depletion of sediments.  相似文献   

Determination of Sr and Ba partition coefficients between apatite from fish (Sparus aurata) and seawater: The influence of temperature     

Vincent Balter  Christophe Lécuyer 《Geochimica et cosmochimica acta》2010,74(12):3449-138

The Sr/Ca and Ba/Ca ratios in inorganic apatite are strongly dependent on the temperature of the aqueous medium during precipitation. If valid in biogenic apatite, these thermometers would offer the advantage of being more resistant to diagenesis than those calibrated on biogenic calcite and aragonite. We have reared seabreams (Sparus aurata) in tanks with controlled conditions during experiments lasting for more than 2 years at 13, 17, 23 and 27 °C, in order to determine the variations in Sr and Ba partitioning relative to Ca (D^Sr and D^Ba, respectively) between seawater and fish apatitic hard tissues (i.e. teeth and bones), as a function of temperature. The sensitivity of the Sr and Ba thermometers (i.e. ∂D^Sr/∂T and ∂D^Ba/∂T, respectively), are similar in bone (/∂T = 0.0036 ± 0.0003 and /∂T = 0.0134 ± 0.0026, respectively) and enamel (/∂T = 0.0037 ± 0.0005 and /∂T = 0.0107 ± 0.0026, respectively). The positive values of ∂D^Sr/∂T and ∂D^Ba/∂T in bone and enamel indicate that D^Sr and D^Ba increase with increasing temperature, a pattern opposite to that observed for inorganic apatite. This distinct thermodependent trace element partitioning between inorganic and organic apatite and water highlights the contradictory effects of the crystal-chemical and biological controls on the partitioning of Ca, Sr and Ba in vertebrate organisms. Taking into account the diet Sr/Ca and Ba/Ca values, it is shown that the bone Ba/Ca signature of fish can be explained by Ca-biopurification and inorganic apatite precipitation, whereas both of these processes fail to predict the bone Sr/Ca values. Therefore, the metabolism of Ca as a function of temperature still needs to be fully understood. However, the biogenic Sr thermometer is used to calculate an average seawater temperature of 30.6 °C using the Sr/Ca compositions of fossil shark teeth at the Cretaceous/Tertiary boundary, and a typical seawater Sr/Ca ratio of 0.02. Finally, while the present work should be completed with data obtained in natural contexts, it is clear that Sr/Ca and Ba/Ca ratios in fossil biogenic apatite already constitute attractive thermometers for marine paleoenvironments.  相似文献   

Oxygen isotope variability in calcite shells of the ostracod Cyprideis torosa in Akyatan Lagoon,Turkey     

Anne-Marie Bodergat  Christophe Lécuyer  François Martineau  Atike Nazik  Kemal Gürbüz  Serge Legendre 《Journal of Paleolimnology》2014,52(1-2):43-59

The euryhaline ostracod Cyprideis torosa lives in Akyatan Lagoon, Turkey, which is exposed to large spatial and seasonal variations in water salinity, δ¹⁸O, and temperature. Hydrogen and oxygen isotope measurements of waters reveal that the large range of salinity (15–80 g L^?1) in the lagoon results from a combination of evaporation and mixing between Mediterranean seawater and Seyhan River input. Round sieve-pore relative abundance in C. torosa provides a robust proxy for water salinity (S) from 15 to 80 g L^?1, according to the equation: S = 161.41 (±4.52) * log₁₀(% rounded pores) ? 94.04 (±3.44) (R² = 0.937; p = 10^?31). Seasonal sampling and isotope analysis of C. torosa in waters of known δ¹⁸O values (?4.7 to +6.9 ‰ V-PDB) and temperatures (15–35 °C) yielded a weak positive correlation (r = 0.71) between 1000 lnα_{(calcite–water)} ‰ V-SMOW) and 10³ * T^?1. Specimens of C. torosa collected during the mild and warm seasons have oxygen isotope compositions close to those of inorganic calcite precipitated in equilibrium with ambient water. The large oxygen-isotope variability observed during any season of the year most likely results from shell calcification in water bodies of highly variable salinity, alkalinity, Mg/Ca and water saturation relative to calcite. Indeed, distinct water bodies in the Akyatan Lagoon are generated by mixing of fresh and marine waters, which are exposed to different evaporation rates at the seasonal scale.  相似文献   

Boron isotope geochemistry of Paleozoic brachiopod calcite: Implications for a secular change in the boron isotope geochemistry of seawater over the Phanerozoic   总被引：1，自引：0，他引：1  

Michael M. Joachimski  Laurent Simon  Christophe Lécuyer 《Geochimica et cosmochimica acta》2005,69(16):4035-4044

Boron isotope composition of marine carbonates has been proposed as a paleo-pH proxy and potential tool to reconstruct atmospheric pCO₂. The precise knowledge of the boron isotopic composition of ancient seawater represents the fundamental prerequisite for any paleo-pH reconstruction. This contribution presents boron isotope values for Silurian to Permian brachiopod calcite that might be used to reconstruct pH or boron isotope composition of past oceans. All brachiopod shells were screened for diagenetic recrystallization by means of cathodoluminescence microscopy, trace element geochemistry (B, Fe, Mn, Sr) as well as SEM. Only nonluminescent shells revealing well-preserved microstructures, high strontium and boron concentrations as well as low iron and manganese contents were accepted for boron isotope analysis. The boron isotope ratios of Silurian, Devonian, Pennsylvanian and Permian brachiopod calcite range from 6.8 to 11.0‰, 7.3 to 14.9‰, 12.4 to 15.8‰ and 10.1 to 11.7‰, respectively. These δ¹¹B values are significantly lower in comparison to δ¹¹B values of modern biogenic carbonates and indicate that the Paleozoic oceans were depleted in ¹¹B by up to 10‰. Box modeling of the boron geochemical cycle suggests that the significant depletion of ¹¹B in the oceanic reservoir may have been initiated by an enhanced continental boron discharge. Our data support the earlier made conclusion that boron isotopes may not be used in the geological past as reliable paleo-pH proxy unless the boron isotopic composition of ancient oceans can be constrained by further studies.  相似文献   

The high temperature reaction zone of the Oman ophiolite: new field data,microthermometry of fluid inclusions,PIXE analyses and oxygen isotopic ratios     

Juteau  Thierry  Manac'h  Gilles  Moreau  Olivier  Lécuyer  Christophe  Ramboz  Claire 《Marine Geophysical Researches》2000,21(3-4):351-385

Marine Geophysical Research - The present study is focused on the so-called High Temprature Reaction Zone of the Oman ophiolite, a thin zone located between the roots of the sheeted dyke complex...  相似文献   

Water concentrations and hydrogen isotope compositions of alkaline basalt-hosted clinopyroxene megacrysts and amphibole clinopyroxenites: the role of structural hydroxyl groups and molecular water     

István Kovács  Attila Demény  György Czuppon  Christophe Lécuyer  Francois Fourel  Qun-Ke Xia  Jia Liu  Zsanett Pintér  Edit Király  Kálmán Török  Ábel Szabó  Etienne Deloule  György Falus  Tamás Fancsik  Zoltán Zajacz  Judit Sándorné Kovács  Beatrix Udvardi 《Contributions to Mineralogy and Petrology》2016,171(5):38

  相似文献   

Extreme Nd isotopic variation in the Trinity Ophiolite Complex and the role of melt/rock reactions in the oceanic lithosphere     

G. Gruau  J. Bernard-Griffiths  C. Lécuyer  O. Henin  J. Macé  M. Cannat 《Contributions to Mineralogy and Petrology》1995,121(4):337-350

 Peridotites, dykes and gabbros from the 470–420 Ma Trinity Ophiolite Complex of northern California exhibit large geochemical rare earth element (REE) and Nd isotopic variations on the small scales which are indicative of a complex history. The Trinity Ophiolite, which covers an area of ≈1600 km², consists of three distinct units: (1) a ∼2–4 km-thick sheet of plastically deformed peridotites, including various ultrabasic lithologies (plagioclase and spinel lherzolite, harzburgite, wherlite and dunite); the peridotite unit is a fragment of mantle lithosphere of oceanic affinity; (2) a series of small (∼1 km diameter) undeformed gabbroic massifs; (3) several generations of basic dykes. The peridotites display the largest geochemical and isotopic variations, with ɛ_Nd(T) values ranging from +10 down to 0. In the gabbroic massifs and intrusive dykes, the variation in model ɛ_Nd(T) values is reduced to 7 ɛ_Nd units: 0 to +7. As a general rule, peridotites, gabbros and dykes with ɛ_Nd(T) values around 0 or +3 give less depleted L(light)REE patterns than do those with ɛ_Nd(T) values in the range +7 to +10. In the peridotites, the Nd isotopic variations take place over very short distances, with jumps as large as 7 ɛ_Nd units occurring on scales of less than 20 m. Comparison with available age data indicates that the peridotites with ɛ_Nd(T)≈+10 could be slightly older than the intrusive gabbro massifs and basic dykes (470 Ma vs. 420 Ma). Strontium isotopic data used in connection with Sm-Nd results demonstrate that the 10 ɛ_Nd units variation displayed by the Trinity Peridotite is a primary feature and not an artefact due to REE mobility during seawater interaction. The variable Nd isotopic signatures and variable LREE patterns in the Trinity Peridotite cannot represent mantle source characteristics as there is evidence that this unit was partially melted when it rose as part of the upwelling convecting mantle. Field, petrographic, geochemical and isotopic data rather suggest that the observed heterogeneity is due to local reactions between a 470 Ma proto-peridotite with ɛ_Nd(T)=+10 and younger (420 Ma) basaltic melts with lower ɛ_Nd(T) values (i.e. the gabbroic massifs and the dykes). The gabbros and basic dykes of the Trinity Complex have geochemical and isotopic compositions similar to the arc basalts from the adjacent Copley Formation, so it is proposed that the younger melts are related to arc magmatism. Received: 13 January 1995/Accepted 5 May 1995  相似文献   

Measurement of 34S/32S Ratios of NBS 120c and BCR 32 Phosphorites Using Purge and Trap EA‐IRMS Technology          下载免费PDF全文

François Fourel  François Martineau  Magali Seris  Christophe Lécuyer 《Geostandards and Geoanalytical Research》2015,39(1):47-53

Measurements of sulfur stable isotope ratios (³⁴S/³²S) have suffered from technical difficulties in analysing low‐S materials reducing their use despite their undeniable scientific interest. The measurement of ³⁴S/³²S ratios is a powerful tool for deciphering problems such as determining the sources of environmental pollutants, to detect adulteration, tracking the evolution of the redox state of the oceans and quantifying the role of the bacterial activity in sulfide minerals genesis. We have used a high‐precision method of sulfur isotope determination using a new type of elemental analyser based on ‘purge and trap’ technology. This new technique demonstrates the high quality of ³⁴S/³²S measurements for samples with S concentrations lower than 1% m/m. International calibrated references of diverse sulfur‐bearing materials were used to calibrate two low (< 1%) S‐bearing phosphorites used as compositional reference material for future use as isotopic references: BCR 32 and NBS 120c. δ³⁴S_CDT values of, respectively, 18.2‰ (1s = 0.3; n = 23) and 18.3‰ (1s = 0.4; n = 20) are proposed for these. Calibration of both phosphorites with international reference materials led to calculation of a mean standard error close to 0.4‰. The demonstration of a capability to reliably measure S isotope ratios in low‐S phosphate minerals or rocks opens up new fields of palaeoenvironmental reconstructions.  相似文献