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1.
This study explores the possibility of establishing Nd isotopic variations in seawater over geologic time. Calcite, aragonite and apatite are examined as possible phases recording seawater values of ?Nd. Modern, biogenic and inorganically precipitated calcite and aragonite from marine environments were found to have Nd concentrations of from 0.2 to 70 ppb, showing that primary marine CaCO3 contains little REE and that Nd/Ca is not greatly enhanced relative to seawater during carbonate precipitation. Very young marine limestone and dolomite containing no continental detritus have ~200 ppb Nd. All the carbonates are LREE enriched (?0.16 ≤fSmNd≤?0.45). Modern and very young Atlantic and Pacific carbonates have ?Nd in the range of shallow Atlantic and Pacific seawater respectively, implying that they derive their REE from local seawater. The Nd in well preserved carbonate fossils is ≤4 × 104 ppb, much greater than in their modern counterparts but like the high values found for carbonates in other studies. We believe the high REE contents (at the 500 ppb level) in some detritusfree carbonates are due to REE-rich Fe-hydroxide in/on the carbonate. In favorable cases, such material may record seawater ?Nd values, however introduction of extraneous REE may obscure the original isotopic composition of pure CaCO3 because of its very low intrinsic primary REE abundance.Modern biogenic apatite is also shown to have very low REE content (<150 ppb Nd) but appears to quickly scavenge REE from seawater. Inorganically precipitated apatite from phosphorites has high concentrations of seawater-derived REE. Young phosphorite apatite from the Atlantic and Pacific oceans has ?Nd in the range of the seawater from these oceans. Older apatite samples of similar age from different localities bordering common oceans record similar values of ?Nd(T). Sedimentary apatite has ?Sr(T) values in good agreement with the curves for 87Sr86Sr of seawater as a function of time. Individual conodonts from a single formation yield the same ?Sr(T) and ?Nd(T). Other workers have shown that sedimentary apatite preserves seawater REE patterns. These characteristics suggest that sedimentary apatite can be used to determine ?Nd(T) in ancient seawater. The seawater values so inferred range between ?1.7 and ?8.9 over the last 700 my and lie in the range of modern seawater, showing no evidence for drastic changes. High values of seawater ?Nd(T) in the Triassic and latest Precambrian may correlate with the breakup of large continental landmasses. The initial ?Nd(T) =?15.0 of a 2 AE old phosphorite implies the presence of ~ 1.5 AE old continental crust at 2 AE ago. The approach outlined here can be used to constrain the age of the exposed crust as a function of time.  相似文献   

2.
Aragonite and calcite single crystals can be readily transformed into polycrystalline hydroxyapatite pseudomorphs by hydrothermal treatment in a (NH4)2HPO4 solution. Scanning electron microscopy of the reaction products showed that the transformation of aragonite to apatite is characterised by the formation of a sharp interface between the two phases and by the development of intracrystalline porosity in the hydroxyapatite phase. In addition, electron backscattered diffraction (EBSD) imaging showed that the c-axis of apatite is predominantly oriented perpendicular to the reaction front with no crystallographic relationship to the aragonite lattice. However, the Ca isotopic composition of the parent aragonite, measured by thermal ionization mass spectrometry was inherited by the apatite product.Hydrothermal experiments conducted with use of phosphate solutions prepared with water enriched in 18O (97%) further revealed that the 18O from the solution is incorporated in the product apatite, as measured by micro-Raman spectroscopy. Monitoring the distribution of 18O with Raman spectroscopy was possible because the incorporation of 18O in the PO4 group of apatite generates four new Raman bands at 945.8, 932, 919.7 and 908.8 cm−1, in addition to the ν1(PO4) symmetric stretching band of apatite located at 962 cm−1, which can be assigned to four 18O-bearing PO4 species. The relative intensities of these bands reflect the 18O content in the PO4 group of the apatite product. By using equilibrated and non-equilibrated solutions, with respect to the 18O distribution between aqueous phosphate and water, we could show that the concentration of 18O in the apatite product is linked to the degree of 18O equilibration in the solution. The textural and chemical observations are indicative of a coupled mechanism of aragonite dissolution and apatite precipitation taking place at a moving reaction interface.  相似文献   

3.
Apatite (Ca10[PO4]6[OH]2) precipitation from aqueous solutions involves multiple steps, such as nucleation of a precursor calcium phosphate phase, cluster aggregation, crystal growth, and transformation to apatite, which are affected by the presence of other ions in solution. I report the mechanisms by which two ions common in natural solutions, Mg2+ and H+, affect heterogeneous calcium phosphate nucleation on the amorphous silica surface.  相似文献   

4.
The direct precipitation of apatite in seawater is inhibited by Mg ions. The action of various factors on this precipitation is studied: addition of Ca, addition of F, reduction of pH and simultaneous effect of reduction of pH and addition either of F or of Ca. It is established that the reduction of the pH of seawater to 7 allows the precipitation of the apatite with a Ca/Mg ratio in the water of 1.2. The favourable environment for the settlement of natural apatite must then be either neutral or acid. This result is corroborated by the re-study of Gulbrandsen's equation. Such an acid environment with a high phosphorus content may be the result of oxidation of large quantities of organic matter due to previous intense biological activity. The acidity is probably brought about by bubbling of CO2.  相似文献   

5.
Clay-rich mine tailings from phosphate mine operations in Florida are a major environmental and economic problem. Options for reclamation and restoration for these tailings are very limited and are fundamentally restricted by poor physical properties such as low mechanical strength, low hydraulic conductivity, and heavy metal content. The major control on these bulk physical properties is the mineralogy of the materials. Eight continuous push borings were obtained to investigate stratigraphy, mineralogy, aspects of geochemistry, and bulk properties of a deposit of clay-rich mine tailings from a phosphate mine near Bartow, Florida that ceased operations in the early 1970s. Stratigraphy is dominated by laminated clay-rich sediment with minor units of silt and sand. An intact kaolinite liner occurs near the impoundment walls and the impoundment floor has approximately 4 m of relief. Moisture content varies from 4.35 to 57.40 wt% and organic content varies from 0.41 to 9.53 wt%. Bulk XRF investigation indicates that the P2O5 concentrations vary from approximately 4 to 21 wt%. A very strong correlation (r 2 = 0.92) between CaO and P2O5 indicates that apatite is a major control on the phosphate. The strong correlation (r 2 = 0.77) of Al2O3 and TiO2 suggests that the source materials for this deposit are comparatively uniform. A number of heavy metal elements and trace elements occur. Cr, V, Ni, Cu are interpreted to be in phosphate minerals, largely apatite. Sr and Pb are interpreted to be in both phyllosilicates and phosphate minerals. Two populations of apatite were observed in the clay-sized fraction, one that was Fe and Si- bearing and another that was only Si-bearing. Fe-bearing apatite had Fe2O3 contents that varied from 0.38 to 5.32 wt% and SiO2 contents that varied from 0.90 to 3.32 wt%. The other apatite population had a wider range of SiO2 contents that varied from 0.77 to 8.80 wt%. TEM imaging shows that apatite grains are dominantly single crystals with lesser amounts of aggregates. Wavellite commonly occurs as individual or clusters of lath-like crystals and the chemical composition differs from the pure aluminium phosphate end member with average concentrations of components being that of CaO (1.57 wt%), Fe2O3 (1.98 wt%), SiO2 (5.94 wt%). In the clay-sized phosphate minerals investigated no fluorine was found above detection limit (approximately 0.15 wt%), nor was any uranium, radium, heavy metal, or REE element detected. The phyllosilicate mineralogy of the deposit is dominated by smectite (montmorillonite with lesser amounts of nontronite), palygorskite, illite and kaolinite. No systematic variation in the relative proportions of phyllosilicates was observed in the clay deposit. Energy dispersive spectroscopy EDS analysis indicates that chemical compositions of phyllosilicates are somewhat typical but overall are enriched with respect to Fe compared to theoretical end members. The relative enrichment of Fe is interpreted to be a primary sedimentary feature. Ca content in smectite minerals is high and may inhibit stabilization using lime or similar methods. The high percentages of montmorillonite and palygorskite explain the high bulk water contents observed. This investigation provides fundamentally new details regarding clay tailing deposits from closed phosphate mines in central Florida which can be used in restoration and reclamation efforts.  相似文献   

6.
Apparent partition coefficients of Sr and Ba between calcium phosphate and water were measured experimentally for temperature ranging from 5°C to 60°C. Calcium phosphates were precipitated from an aqueous mixture of Na2HPO4 · 2H2O (10−2 M) and CaCl2 · 2H2O (10−2 M). Spiked solutions of Sr or Ba were introduced into the CaCl2 · 2H2O solution at Sr/Ca and Ba/Ca ratios of 0.1. The experiment consisted in sampling the liquid and solid phases after 1, 6, 48, and 96 h of interaction. The amorphous calcium phosphate (ACP) precipitated early in the experiment was progressively replaced by hydroxylapatite (HAP), except at 5°C where brushite (di-calcium phosphate di-hydrate or DCPD) was formed. We observed that the crystallinity of the solid phase increased with time for a given temperature and increased with temperature for a given time of reaction. With the exception of the experiment at 5°C, yield (R%) and apparent partition coefficients (Ka-wSr/Ca and Ka-wBa/Ca) both decreased with increasing reaction time. After 96 h, R%, Ka-wSr/Ca and Ka-wBa/Ca were observed to be constant, suggesting that the solid phases were at steady-state with respect to the aqueous solutions. The thermodependence of Sr and Ba partitioning between apatite and water at low temperature could therefore be calculated:
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7.
The Ca isotope variation of 11 Miocene and Pleistocene, authigenic, marine phosphates is rather small compared to the corresponding variation in δ18O values. The δ44Ca values are not correlated with the δ18O values and, therefore, they are not temperature controlled. It is likely that the δ44Ca values of the phosphorites reflect the variation in the δ44Ca values of paleo-seawater but, in contrast to Sr, not the isotopic composition of seawater itself. Furthermore, Ca and Sr isotopic compositions are decoupled with decreasing stratigraphic age of the phosphate peloids with Sr isotopic compositions changing to more radiogenic values while Ca isotopic compositions remain rather stable. All samples have δ44Ca values below present-day seawater values, suggesting that phosphate formation discriminates against heavy Ca isotopes.Phosphorites and carbonaceous sediments have a similar Ca isotopic variation during the Miocene. A systematic and more or less constant shift between marine carbonates and phosphates is observed: the phosphate samples are slightly less enriched in 40Ca compared to carbonates. This shift has been related to a mineral-dependent kinetic mass fractionation during precipitation from seawater. The rather stable δ44Ca value for the 19 to 9 Ma old phosphorites points to a constant δ44Ca fractionation of about 1.1 between seawater and phosphorites during the past and suggests steady-state conditions for the Mid-Miocene seawater (sedimentation flux equals erosion flux).  相似文献   

8.
The partitioning behavior of Cl among apatite, mafic silicate melt, and aqueous fluid and of F between apatite and melt have been determined in experiments conducted at 1066 to 1150 °C and 199-205 MPa. The value of DClapatite/melt (wt. fraction of Cl in apatite/Cl in melt) ≈0.8 for silicate melt containing less than ∼3.8 wt.% Cl. At higher melt Cl contents, small increases in melt Cl concentration are accompanied by large increases in apatite Cl concentration, forcing DClapatite/melt to increase as well. Melt containing less than 3.8% Cl coexists with water-rich vapor; that containing more Cl coexists with saline fluid, the salinity of which increases rapidly with small increases in melt Cl content, analogous to the dependency of apatite composition on melt Cl content. This behavior is due to the fact that the solubility of Cl in silicate melt depends strongly on the composition of the melt, particularly its Mg, Ca, Fe, and Si contents. Once the melt becomes “saturated” in Cl, additional Cl must be accommodated by coexisting fluid, apatite, or other phases rather than the melt itself. Because Cl solubility depends on composition, the Cl concentration at which DClapatite/melt and DClfluid/melt begin to increase also depends on composition. The experiments reveal that DFapatite/melt ≈3.4. In contrast to Cl, the concentration of F in silicate melt is only weakly dependent on composition (mainly on melt Ca contents), so DFapatite/melt is constant for a wide range of composition.The experimental data demonstrate that the fluids present in the waning stages of the solidification of the Stillwater and Bushveld complexes were highly saline. The Cl-rich apatite in these bodies crystallized from interstitial melt with high Cl/(F + OH) ratio. The latter was generated by the combined processes of fractional crystallization and dehydration by its reaction with the relatively large mass of initially anhydrous pyroxene through which it percolated.  相似文献   

9.
Calcium and magnesium concentrations in seawater have varied over geological time scales. On short time scales, variations in the major ion composition of seawater influences coccolithophorid physiology and the chemistry of biogenically produced coccoliths. Validation of those changes via controlled laboratory experiments is a crucial step in applying coccolithophorid based paleoproxies for the reconstruction of past environmental conditions. Therefore, we examined the response of two species of coccolithophores, Emiliania huxleyi and Coccolithus braarudii, to changes in the seawater Mg/Ca ratio (≈0.5 to 10 mol/mol) by either manipulating the magnesium or calcium concentration under controlled laboratory conditions. Concurrently, seawater Sr/Ca ratios were also modified (≈2 to 40 mmol/mol), while keeping salinity constant at 35. The physiological response was monitored by measurements of the cell growth rate as well as the production rates of particulate inorganic and organic carbon, and chlorophyll a. Additionally, coccolithophorid calcite was analyzed for its elemental composition (Sr/Ca and Mg/Ca) as well as isotope fractionation of calcium and magnesium (Δ44/40Ca and Δ26/24Mg). Our results reveal that physiological rates were substantially influenced by changes in seawater calcium rather than magnesium concentration within the range estimated to have occurred over the past 250 million years when coccolithophores appear in the fossil record. All physiological rates of E. huxleyi decreased at a calcium concentration above 25 mmol L−1, whereas C. braarudii displayed a higher tolerance to increased seawater calcium concentrations. Partition coefficient of Sr was calculated as 0.36 ± 0.04 (±2σ) independent of species. Partition coefficient of Mg2+ increased with increasing seawater Ca2+ concentrations in both coccolithophore species. Calcium isotope fractionation was constant at 1.1 ± 0.1‰ (±2σ) and not altered by changes in seawater Mg/Ca ratio. There is a well-defined inverse linear relationship between calcium isotope fractionation and partition coefficient of Sr2+ in all experiments, suggesting similar controls on both proxies in the investigated species. Magnesium isotope ratios were relatively stable for seawater Mg/Ca ratios ranging from 1 to 5, with a higher degree of fractionation in Emiliania huxleyi (by ≈0.2‰ in Δ26/24Mg). Although Mg/Ca ratios in the calcite of coccolithophores and foraminifera are similar, the former have considerably higher Δ26/24Mg (by >+3‰), presumably due to differences in calcification mechanisms between the two taxa. These observations suggest, a physiological control over magnesium elemental and isotopic fractionation during the process of calcification in coccolithophores.  相似文献   

10.
The mineral composition and U-Pb and Rb-Sr systematics of phosphorites from the Satka Formation of Lower Riphean carbonates, the Burzyan Group of Southern Urals, are studied. Phosphorites occurring as small lenses between stromatolite layers are composed largely of fluorapatite with admixture of detrital quartz, feldspars, illite, and chlorite. Phosphorite samples have been subjected to stepwise dissolution in 1 N (fraction L-1) and 2 N (fraction L-2) HCl. As is established, the maximum apatite content is characteristic of fraction L-1, while fraction L-2 is enriched in products of dolomite and sulfide dissolution and in elements leached from siliciclastic components. The Sr content in the Satka apatites (280–560 ppm) is substantially lower as compared with that in unaltered marine apatite. The 87Sr/86Sr “initial ratio in the phosphorites studied (0.71705–0.72484) and host dolomites from the lower part of the Satka Formation is significantly higher than in the Early Riphean seawater that indicates a reset of the Rb-Sr original systems in sediments. The Pb-Pb age of 1340 ± 30 Ma (MSWD = 6.4) estimated based on 7 data points characterizing fractions L-1 and L-2 is younger than the formation time of overlying Burzyan sediments, being consistent, within the error range, with date of the Mashak rifting event recorded at the Early-Middle Riphean boundary. The comparative U-Pb characteristics of two soluble fractions (L-1 and L-2) and silicate residue of phosphorites show that epigenetic redistribution of Pb and U was characteristic of the phosphorite horizon only. The initial Pb isotope composition and μ (238U/204Pb) estimated according to model by Stacey and Kramers for the early diagenetic fluids in carbonate and phosphate sediments of the Satka Formation suggest that they were in isotopic equilibrium with erosion products of the Taratash crystalline complex.  相似文献   

11.
A geochemical proxy for surface ocean nutrient concentrations recorded in coral skeleton could provide new insight into the connections between sub-seasonal to centennial scale nutrient dynamics, ocean physics, and primary production in the past. Previous work showed that coralline P/Ca, a novel seawater phosphate proxy, varies synchronously with annual upwelling-driven cycles in surface water phosphate concentration. However, paired contemporaneous seawater phosphate time-series data, needed for rigorous calibration of the new proxy, were lacking. Here we present further development of the P/Ca proxy in Porites lutea and Montastrea sp. corals, showing that skeletal P/Ca in colonies from geographically distinct oceanic nutrient regimes is a linear function of seawater phosphate (PO4 SW) concentration. Further, high-resolution P/Ca records in multiple colonies of Pavona gigantea and Porites lobata corals grown at the same upwelling location in the Gulf of Panamá were strongly correlated to a contemporaneous time-series record of surface water PO4 SW at this site (r2 = 0.7-0.9). This study supports application of the following multi-colony calibration equations to down-core records from comparable upwelling sites, resulting in ±0.2 and ±0.1 μmol/kg uncertainties in PO4 SW reconstructions from P. lobata and P. gigantea, respectively.
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12.
A numerical model of chemical weathering in soil horizons and underlying bedrock (WITCH) has been coupled to a numerical model of water and carbon cycles in forest ecosystems (ASPECTS) to simulate the concentration of major species within the soil horizons and the stream of the Strengbach granitic watershed, located in the Vosges Mountains (France). For the first time, simulations of solute concentrations in soil layers and in the catchment river have been performed on a seasonal basis. The model is able to reproduce the concentrations of most major species within the soil horizons, as well as catching the first-order seasonal fluctuations of aqueous calcium, magnesium and silica concentrations. However, the WITCH model underestimates concentrations of Mg2+ and silica at the spring of the catchment stream, and significantly underestimates Ca2+ concentration. The deficit in calculated calcium can be compensated for by dissolution of trace apatite disseminated in the bedrock. However, the resulting increased Ca2+ release yields important smectite precipitation in the deepest model layer (in contact with the bedrock) and subsequent removal of large amount of silica and magnesium from solution. In contrast, the model accurately accounts for the concentrations of major species (Ca, Mg and silica) measured in the catchment stream when precipitation of clay minerals is not allowed. The model underestimation of Mg2+ and H4SiO4 concentrations when precipitation of well crystallized smectites is allowed strongly suggests that precipitation of well crystallized clay minerals is overestimated and that more soluble poorly crystallized and amorphous materials may be forming. In agreement with observations on other watersheds draining granitic rocks, this study indicates that highly soluble trace calcic phases control the aqueous calcium budget in the Strengbach watershed.  相似文献   

13.
Experimental studies have been performed to constrain sulfur behavior during apatite crystallization and to determine sulfur partition coefficient between apatite and melt (KdSapatite/melt) at oxidizing conditions. Crystallization experiments have been conducted with a hydrous rhyolitic melt and different bulk sulfur contents (0.15 to 2 wt.% S) at 900 and 1,000°C, 200 MPa and Δlog =NNO+3.6. The sulfur content in the glass increases with increasing amount of added S. Anhydrite crystallizes for S added = 0.75 wt.% (0.10 and 0.13 wt.% SO3 in glass at 900 and 1,000°C, respectively). The amount of anhydrite increases and the amount of apatite decreases with increasing amount of added sulfur. The sulfur exchange reaction in apatite is influenced by the bulk composition of the melt (e.g., P content). However, changing melt composition has only little effect on KdSapatite/melt for the investigated rhyolitic composition. The KdSapatite/melt does not depend directly on temperature, decreases from 14.2 to 2.7 with increasing S content in glass from SO3=0.03 to 0.19 wt.%, respectively, and can be predicted from the following equation: ln Kd = −0.0025×S in melt (in ppm)+2.9178. The combination of experimental data obtained for rhyolitic and andesitic melts reveals that the sulfur partition coefficient tends toward a value of 2 for high-sulfur content in the glass (>0.2 wt.% SO3). Using S in apatite as proxy for determining S content in melt is promising but additional experimental data are needed to clarify the individual effects of T, , and P and Ca content in the melt on S partitioning.  相似文献   

14.
矿渣磷酸镁水泥的力学性能和水化机理   总被引：1，自引：0，他引：1  
以高炉矿渣作为磷酸镁水泥(MPC)的活性混合材料,研究了MPC的凝固时间、力学性能、物相组成和显微结构,并探讨了矿渣MPC的作用机理。实验固定磷镁比为25%,硼镁比为7.5%,矿渣掺量分别为磷镁总质量的0%、10%、20%、30%和40%。结果表明,矿渣参与了水化反应并提高了MPC的胶凝性能,随着矿渣掺量增大,矿渣MPC的抗压强度提高,但矿渣水化产生的膨胀应力会破坏MPC的内部结构,因此其抗折强度随矿渣掺量增大而降低。矿渣MPC的主要水化产物为六水合磷酸镁铵(MgNH4PO4.6H2O),矿渣的掺入使凝胶相增加,并有部分Ca2+进入MgNH4PO4.6H2O晶格,使水化产物的形貌、大小发生变化。样品中剩余较多死烧镁和矿渣颗粒,可起骨料作用。  相似文献   

15.
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 (DSr and DBa, 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. ∂DSr/∂T and ∂DBa/∂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 ∂DSr/∂T and ∂DBa/∂T in bone and enamel indicate that DSr and DBa 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   

16.
Results of pore water and sediment analyses from the western Mexican continental margin strongly suggest the present day formation of apatite. The interstitial water phosphate and fluoride profiles indicate chemical removal at a depth which corresponds to a large maximum in the phosphorus content of the sediments. Apatite is identified within this maximum via X-ray diffraction but is elsewhere undetectable in the core. Radioisotopic thorium, uranium, and radium data support the conclusion that this deposit is modern. The present day depositional environment is consistent with those reported by other workers for phosphorite formation with the exception that pore water magnesium is not depleted below its seawater value.  相似文献   

17.
Oxygen isotope ratios of well-preserved brachiopod calcite and conodont apatite were used to reconstruct the palaeotemperature history of the Middle and Late Devonian. By assuming an oxygen isotopic composition of –1 V-SMOW for Devonian seawater, the oxygen isotope values of Eifelian and early Givetian brachiopods and conodonts give average palaeotemperatures ranging from 22 to 25 °C. Late Givetian and Frasnian palaeotemperatures calculated from 18O values of conodont apatite are close to 25 °C in the early Frasnian and increase to 32 °C in the latest Frasnian and early Famennian. Oxygen isotope ratios of late Givetian and Frasnian brachiopods are significantly lower than equilibrium values calculated from conodont apatite 18O values and give unrealistically warm temperatures ranging from 30 to 40 °C. Diagenetic recrystallization of shell calcite, different habitats of conodonts and brachiopods, as well as non-equilibrium fractionation processes during the precipitation of brachiopod calcite cannot explain the 18O depletion of brachiopod calcite. Moreover, the 18O depletion of brachiopod calcite with respect to equilibrium 18O values calculated from conodont apatite is too large to be explained by a change in seawater pH that might have influenced the oxygen isotopic composition of brachiopod calcite. The realistic palaeotemperatures derived from 18O apatite may suggest that biogenic apatite records the oxygen isotopic composition and palaeotemperature of Palaeozoic oceans more faithfully than brachiopod calcite, and do not support the hypothesis that the 18O/16O ratio of Devonian seawater was significantly different from that of the modern ocean.  相似文献   

18.
The composition of S-rich apatite, of volatile-rich glass inclusions in apatite, and of interstitial glasses in alkaline xenoliths from the 1949 basanite eruption in La Palma has been investigated to constrain the partitioning of volatiles between apatite and alkali-rich melts. The xenoliths are interpreted as cumulates from alkaline La Palma magmas. Apatite contains up to 0.89 wt% SO3 (3560 ppm S), 0.31 wt% Cl, and 0.66 wt% Ce2O3. Sulfur is incorporated in apatite via several independent exchange reactions involving (P5+, Ca2+) vs. (S6+, Si4+, Na+, and Ce3+). The concentration of halogens in phonolitic to trachytic glasses ranges from 0.15 to 0.44 wt% for Cl and from <0.07 to 0.65 wt% for F. The sulfur concentration in the glasses ranges from 0.06 to 0.23 wt% SO3 (sulfate-saturated systems). The chlorine partition coefficients (DClapatite/glass) range from 0.4 to 1.3 (average DClapatite/glass = 0.8), in good agreement with the results of experimental data in mafic and rhyolitic system with low Cl concentrations. With increasing F in glass inclusions DFapatite/glass decreases from 35 to 3. However, most of our data display a high partition coefficient (~30) close to DFapatite/glass determined experimentally in felsic rock. DSapatite/glass decreases from 9.1 to 2.9 with increasing SO3 in glass inclusions. The combination of natural and experimental data reveals that the S partition coefficient tends toward a value of 2 for high S content in the glass (>0.2 wt% SO3). DSapatite/glass is only slightly dependent on the melt composition and can be expressed as: SO3 apatite (wt%) = 0.157 * ln SO3 glass (wt%) + 0.9834. The phonolitic compositions of glass inclusions in amphibole and haüyne are very similar to evolved melts erupted on La Palma. The lower sulfur content and the higher Cl content in the phonolitic melt compared to basaltic magmas erupted in La Palma suggest that during magma evolution the crystallization of haüyne and pyrrhotite probably buffered the sulfur content of the melt, whereas the evolution of Cl concentration reflects an incompatible behavior. Trachytic compositions similar to those of the (water-rich) glass inclusions analyzed in apatite and clinopyroxene are not found as erupted products. These compositions are interpreted to be formed by the reaction between water-rich phonolitic melt and peridotite wall-rock.  相似文献   

19.
Using single-crystal X-ray diffraction from a diamond anvil cell, the compressibility of a synthetic fluorapatite was determined up to about 7?GPa. The compression pattern was anisotropic, with greater change along a than c. Unit cell parameters varied linearly with β a =3.32(8)?10?3 and β c =2.40(5)?10?3 GPa?1, giving a ratio β a :β c =1.38:1. Data fitted with a third-order Birch-Murnaghan EOS yielded a bulk modulus of K 0=93(4)?GPa with K′=5.8(1.8). The evolution of the crystal structure of fluorapatite was analysed using data collected at room pressure, at 3.04 and 4.72?GPa. The bulk modulus of phosphate tetrahedron is about three times greater than the bulk modulus of calcium polyhedra. The values were 270(10), 100(4) and 86(3) GPa for P, Ca1 (nine-coordinated) and Ca2 (seven-coordinated) respectively. While the calcium polyhedra became more regular with pressure, the distortion of the phosphate tetrahedron remained unchanged. The size of the channel extending along the [001] direction represented the most compressible direction. The Ca2–Ca2 distance decreased from 3.982 to 3.897?Å on compression from 0.0001 to 4.72?GPa. The anisotropic compressional pattern may be understood in terms of the greater compressibility of the channel size over the polyhedral units. The reduction of the channel volume was measured by the evolution of the trigonal prism, having the Ca2–Ca2–Ca2 triangle as its base and the c lattice parameter as its height. This prism volume changed from 47.3?Å3 at room pressure to 44.78?Å3 at 4.72?GPa. Its relatively high bulk moduli, 86(3) GPa, indicated that the channel did not collapse with pressure and the apatite structure could remain stable at very high pressure.  相似文献   

20.
Two types of phosphorite recovered from the continental slope off western India are described. The first type, phosphorite 1, comprises a hard, grey nodule composed of carbonate fluorapatite (CFA) and calcite as major minerals. The phosphorite consists of light‐brown microcrystalline apatite containing a few skeletal fragments and planktonic foraminifera. Scanning electron microscope (SEM) studies show evidence of dissolution of skeletal calcite and filling of the resulting cavities by phosphate composed of ovoid to rod‐shaped apatite microparticles. Apatite also occurs as coatings on these particles. The P2O5 content of the phosphorite is 29%, and the CO2 content of the CFA is about 4·5%. The rare‐earth element (REE) abundance (ΣREE=2·02 μg g–1) is lower than in other modern phosphorites. The 87Sr/86Sr ratio and ?Nd value of this sample are 0·70921 and –9·9 respectively. The 14C age found through accelerator mass spectrometry (AMS) dating (18 720 ± 120 years BP) is much younger than that determined by the U‐series method (100 ka). The second type, phosphorite 2, comprises a friable, light‐brown nodule consisting of CFA as the only major mineral, with a CO2 content of the CFA of 4·5%. In thin section, the phosphate is light brown and homogeneous, and a few bone fragments are present. The P2O5 content is 33%, and REE contents (ΣREE = 0·18 μg g–1) are lower than in phosphorite 1. The age of phosphorite 2 is >300 ka. Phosphorite 1 appears to have formed during the late Pleistocene through replacement of carbonate by phosphate; phosphorite 2 is also of Pleistocene age but is much older than phosphorite 1. The initial substrate for phosphorite 2 was a fish coprolite, which was subsequently phosphatized during slow sedimentation under low‐energy conditions. Microbial mediation is evident in both phosphorites. The colour, density and P2O5 content of the phosphorites are found to be dependent on the nature of the initial substrates and physico‐chemical conditions during phosphatization. The CO2 content of the CFA is not related to the precursor carbonate phase. The nature of sediments, rates of sedimentation and the time spent undergoing phosphogenesis at the sediment–water interface may control REE concentrations in phosphorites.  相似文献   

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