The isotopic composition of strontium in non-marine carbonate rocks: the Flagstaff Formation of Utah*

The isotopic composition of strontium in surface water in continental basins is determined primarily by the geology of the basin and to a lesser extent by climatic conditions. Consequently, the ⁸⁷Sr/⁸⁶Sr ratios of brines in such basins can change only as a result of changes in the geology or climate. This principle of isotope geology was studied by analysis of a suite of non-marine carbonate rocks from the Flagstaff Formation (Palaeocene-Eocene) of Utah. The samples were collected from a section in Fairview Canyon of Sanpete County. They include both limestone and dolomite and were selected to have low non-carbonate residues. The concentrations of strontium in calcites averages 383 ± 128 p.p.m., while those of dolomites increase from 354 ± 74 p.p.m. in the lower 43 m of section to a maximum of 2259 p.p.m. higher up. The increase in the strontium content of dolomite is interpreted as evidence for a change from steady-state to progressively more evaporitic conditions. Two dolomites have isotopic compositions of oxygen expressed as δ¹⁸O = -2.75‰ (relative to the PDB standard) and are enriched in ¹⁸O relative to two calcites whose average δ¹⁸O value is -9.9‰. The ⁸⁷Sr/⁸⁶Sr ratios of the carbonate minerals range from 0.70890 to 0.71260. These values are clearly greater than the ⁸⁷Sr/⁸⁶Sr ratio of marine carbonates of Early Eocene age which is 0.70744. The variation of the ⁸⁷Sr/⁸⁶Sr ratio in this section of the Flagstaff Formation is real and reflects the occurrence of geological events which changed the isotopic composition of Sr entering Lake Flagstaff. The non-carbonate fractions of six carbonate rocks and one sandstone fit a straight line on the strontium mixing diagram in co-ordinates of initial ⁸⁷Sr/⁸⁶Sr and 1/Sr concentration. These results suggest that the isotopic composition of strontium in Lake Flagstaff may have been modulated by periodic input of volcanogenic detritus of felsic composition.     

Application of the trace element and isotope geochemistry of strontium to studies of carbonate diagenesis

Carbonate rocks and natural waters exhibit a wide range in the concentration and isotopic composition of strontium. This wide range and the quantifiable covariation of these parameters can provide diagnostic tools for understanding processes of fluid-rock interaction. Careful consideration of the uncertainties associated with trace element partitioning, sample heterogeneity and fluid-rock interaction mechanisms is required to advance the application of the trace element and isotope geochemistry of strontium to studies of diagenesis, goundwater evolution, ancient seawater chemistry and isotope stratigraphy. A principal uncertainty involved in the application of Sr concentration variations to carbonate systems is the large range of experimental and empirical results for trace element partitioning of Sr between mineral and solution. This variation may be a function of precipitation rate, mineral stoichiometry, crystal growth mechanism, fluid composition and temperature. Calcite and dolomite in ancient limestones commonly have significantly lower Sr concentrations (20–70 p.p.m.) than would be expected from published trace element distribution coefficient values and Sr/Ca ratios of most modern sedimentary pore waters. This discrepancy probably reflects the uncertainties associated with determining distribution coefficient values. As techniques improve for the analytical measurement and theoretical modelling of Sr concentration and isotopic variations, the petrological analysis of carbonate samples becomes increasingly important. The presence of even small percentages of non-carbonate phases with high Rb concentrations and high ⁸⁷ Sr⁸⁶ Sr values, such as clay minerals, can have significant effects on the measured ⁸⁷ Sr/⁸⁶ Sr values of carbonate rocks, due to the decay of ⁸⁷Rb to ⁸⁷ Sr. For example, a Permian marine limestone with 50 p.p.m. Sr and 1 p.p.m. Rb will have a present-day ⁸⁷ Sr/⁸⁶ Sr value that is >2 × 10^?4 higher than its original value. This difference is an order of magnitude greater than the analytical uncertainty, and illustrates the importance of assessing the need for and accuracy of such corrections. A quantitative evaluation of the effects of water-rock interaction on Sr concentrations and isotope compositions in carbonates strengthens the application of these geochemical tracers. Geochemical modelling that combines the use of trace elements and isotopes can be used to distinguish between different mechanisms of water-rock interaction, including diffusive and advective transport of diagenetic constituents in meteoric pore fluids during the recrystallization of carbonate minerals. Quantitative modelling may also be used to construct diagnostic fluid-rock interaction trends that are independent of distribution coefficient values, and to distinguish between mixing of mineral end-members and fluid-rock interaction.     

87Sr/86Sr composition of evaporitic carbonates and sulphates from Miocene sediment cores in the Mediterranean Sea (D.S.D.P., Leg 13)

The ⁸⁷Sr/⁸⁶Sr ratios of evaporitic carbonates and sulphates from Miocene sediment cored in the Mediterranean Sea show a depletion of ⁸⁷Sr when compared to the isotopic composition of the Miocene contemporaneous marine strontium: 0.70803 versus 0.70936. The arrival into the evaporitic environment of strontium brought by continental waters can explain this difference. The variation of the ⁸⁷Sr/⁸⁶Sr ratios is, nevertheless, noticeable only when the influence of the continental waters is already well marked. This is proved when one compares the results obtained with strontium, to the results of isotopic analysis made on oxygen, carbon, sulphur and hydrogen taken from the same samples.     

Fingerprinting a multistage metamorphic fluid–rock history: Evidence from grain scale Sr,O and C isotopic and trace element variations in high-grade marbles from East Antarctica

Granulite grade marble layers interlayered with metapelitic granulites from Lützow Holm Bay, East Antarctica, provide insight into fluid–rock interactions during burial to and exhumation from lower crustal levels. Sub-millimeter scale strontium, oxygen and carbon isotope variations along with LA-ICPMS trace element geochemistry and mineral chemistry of texturally characterized carbonates and associated minerals helped to reconstruct the multistage metamorphic fluid history.Fluid–rock interaction dating back to prograde metamorphism are still preserved in consistently low oxygen and high strontium isotope compositions (δ¹⁸O = 12‰; ⁸⁷Sr/⁸⁶Sr_(550Ma) = 0.7248) within a massif dolomitic marble layer that escaped significant later metasomatism. In most marbles, total re-crystallization and isotopic resetting occurred in the presence of “externally derived” hyper-saline fluids that circulated along the carbonate layers during the early stages of prograde metamorphism. This leads to a trend of increased radiogenic Sr in marbles towards the value of associated metapelitic rocks that have ⁸⁷Sr/⁸⁶Sr_(550Ma) of 0.764.LA-ICPMS studies on trace elements in carbonate and associated silicate minerals at different textural settings, distinguished using cathodoluminescence microscopy, revealed multiple metasomatic events during retrograde metamorphism. Trace element contents of Ba, Sr, Pb and U gave compelling evidence for metasomatic alteration that postdate the exsolution of carbonate at ~ 600 ºC, which can be correlated with the fluids released from the crystallization of anatectic melts and pegmatites. Subsequently, meteoric fluid infiltration occurred at a shallower level of the crust and caused extreme oxygen isotopic heterogeneity (δ¹⁸O = 14.7 ~ ? 4.9‰) and imprinted high concentration of fluid mobile elements. Taken together our results emphasize the importance of integrating textural and chemical heterogeneities to reveal the multiple episodes of fluid–rock interaction processes in a dynamic continental crust, which has major implications on migration of fluids and material and help in formulating models on the geodynamic evolution of crust.     

Strontium and oxygen isotope profiles across marble-silicate contacts,Lizzies Basin,East Humboldt Range,Nevada: constraints on metamorphic permeability contrasts and fluid flow

 Sr isotope profiles across marble-silicate rock contacts are used in conjunction with previously published oxygen isotope profiles to constrain fluid movement, porosity and permeability contrasts in migmatitic rocks from Lizzies Basin in the East Humboldt Range, Nevada. The ¹⁸O/¹⁶O systematics in the high-grade sequence have been interpreted to reflect infiltration of ∼2×10² m³/m² of a relatively low ¹⁸O hydrous fluid through the sequence, but with preservation of δ¹⁸O anomalies in thin marble bands due to a 30-fold lower porosity in the marble compared with silicate rocks (Wickham and Peters 1992). The Sr isotope profiles confirm that tracer exchange between marble and silicate rock was primarily by diffusion, and in one case, indicate that porosities differed by less than a factor of four in the ∼10 cm boundary layer which exhibits diffusive modification of ⁸⁷Sr/⁸⁶Sr ratios. This contrasts with modelling of the oxygen isotope profiles which imply porosity contrasts >10 for one marble band and >50 for a second marble band. Either strontium and oxygen isotope diffusion reflect different events (possible if fluid Sr contents varied with time) or porosity varied substantially with the silicate rocks. Oxygen isotope profiles in the deeper part of the metamorphic section in which δ¹⁸O values of silicate rocks have been homogenised and lowered, indicate similar diffusion distances (and thus porosity-time evolution) to oxygen isotopic profiles higher in the section. Comparison of strontium and oxygen isotope diffusion distances constrains fluid Sr contents to between ∼50 and ∼500 ppm deep in the section, but less than ∼10 ppm higher in the section. The difference is related to release of relatively saline, Sr-rich fluids, by the abundant leucogranites and associated skarns deep in the section (cf. Peters and Wickham 1995). Received: 9 December 1994/Accepted: 13 April 1995     

The strontium isotopic composition and origin of burial cements in the Lincolnshire Limestone (Bajocian) of central Lincolnshire, England

Strontium isotopic composition (⁸⁷Sr/⁸⁶Sr) of two petrographically, chemically and isotopically (δ¹⁸O and δ¹³C) distinct phases of burial calcites from the Lincolnshire Limestone are indistinguishable (0.70820± 26). The mean ⁸⁷Sr/⁸⁶Sr ratio of these phases is considerably more radiogenic than ⁸⁷Sr/⁸⁶Sr ratios of Bajocian marine waters (～0.70725). Neither Bajocian marine waters nor meteoric waters buffered by host marine carbonate in the Limestone could have precipitated the burial spars. Radiogenic strontium may have been contributed from K-feldspar dissolution and/or clay recrystallization, either within clastic portions of the Limestone itself, or from major clastic units adjacent to the Limestone. Alternatively, Palaeozoic marine waters or remobilized Palaeozoic marine carbonate and/or sulphate could have supplied the necessary radiogenic strontium.     

Strontium distribution and origins in a natural clayey formation (Callovian-Oxfordian, Paris Basin, France): A new sequential extraction procedure

Strontium is a good monitor of geochemical processes in natural clayey formations. In the Callovian-Oxfordian formation of Bure in France, strontium is sorbed on clay minerals and carried by carbonates, detrital minerals and accessory celestite. In order to determine the strontium distribution among these different phases, four-step sequential extractions (1. cobalt hexamine trichloride, 2. acetic acid, 3. EDTA and 4. tri-acid) were performed on samples from different levels of the clayey formation. The leachates were also analyzed for strontium isotopes, in order to determine the strontium origins. This sequential procedure is well suited to determining strontium distribution in claystones, although it is less efficient in clay-rich limestones and in celestite-rich samples. The carbonates (38-47% of the total strontium) show ⁸⁷Sr/⁸⁶Sr ratios (0.7070-0.7071) that have recorded the isotopic composition of the Callovian-Oxfordian seawater. Diagenetic carbonates (dolomite, ankerite and siderite) have almost not incorporated any strontium, which has been trapped by celestite during the late diagenesis. The major part of the celestite shows ⁸⁷Sr/⁸⁶Sr ratios (0.7069-0.7070) quite close to the primary carbonates. However, a second generation of celestite (0.7074) shows a slight ⁸⁷Sr-enrichment and is isotopically in equilibrium with the exchangeable strontium (27-48% of the total strontium with a mean ⁸⁷Sr/⁸⁶Sr value of 0.70745) and the present-day porewater (0.7074). This very low ⁸⁷Sr-enrichment could be explained by the partial destabilisation of detrital minerals (feldspars, micas, clays) which exhibit ⁸⁷Sr/⁸⁶Sr ratios consistent with their pristine Hercynian origin (0.7229-0.7350). Diffusion of strontium from the subjacent Dogger aquifers (0.7076-0.7082) could also be invoked to explain the slight ⁸⁷Sr-enrichment.     

Ion microprobe measurement of strontium isotopes in calcium carbonate with application to salmon otoliths

The ion microprobe has the capability to generate high resolution, high precision isotopic measurements, but analysis of the isotopic composition of strontium, as measured by the ⁸⁷Sr/⁸⁶Sr ratio, has been hindered by isobaric interferences. Here we report the first high precision measurements of ⁸⁷Sr/⁸⁶Sr by ion microprobe in calcium carbonate samples with moderate Sr concentrations. We use the high mass resolving power (7000 to 9000 M.R.P.) of the SHRIMP-RG ion microprobe in combination with its high transmission to reduce the number of interfering species while maintaining sufficiently high count rates for precise isotopic measurements. The isobaric interferences are characterized by peak modeling and repeated analyses of standards. We demonstrate that by sample-standard bracketing, ⁸⁷Sr/⁸⁶Sr ratios can be measured in inorganic and biogenic carbonates with Sr concentrations between 400 and 1500 ppm with ∼2‰ external precision (2σ) for a single analysis, and subpermil external precision with repeated analyses. Explicit correction for isobaric interferences (peak-stripping) is found to be less accurate and precise than sample-standard bracketing. Spatial resolution is ∼25 μm laterally and 2 μm deep for a single analysis, consuming on the order of 2 ng of material. The method is tested on otoliths from salmon to demonstrate its accuracy and utility. In these growth-banded aragonitic structures, one-week temporal resolution can be achieved. The analytical method should be applicable to other calcium carbonate samples with similar Sr concentrations.     

Controls on the spatial and temporal variability of vadose dripwater geochemistry: Edwards aquifer, central Texas

A 4-yr study of spatial and temporal variability in the geochemistry of vadose groundwaters from caves within the Edwards aquifer region of central Texas offers new insights into controls on vadose groundwater evolution, the relationship between vadose and phreatic groundwaters, and the fundamental influence of soil composition on groundwater geochemistry. Variations in Sr isotopes and trace elements (Mg/Ca and Sr/Ca ratios) of dripwaters and soils from different caves, as well as phreatic groundwaters, provide the potential to distinguish between local variability and regional processes controlling fluid geochemistry, and a framework for understanding the links between climatic and hydrologic processes.The Sr isotope compositions of vadose cave dripwaters (mean ⁸⁷Sr/⁸⁶Sr = 0.7087) and phreatic groundwaters (mean ⁸⁷Sr/⁸⁶Sr = 0.7079) generally fall between values for host carbonates (mean ⁸⁷Sr/⁸⁶Sr = 0.7076) and exchangeable Sr in overlying soils (mean ⁸⁷Sr/⁸⁶Sr = 0.7088). Dripwaters have lower Mg/Ca and Sr/Ca ratios, and higher ⁸⁷Sr/⁸⁶Sr values than phreatic groundwaters. Dripwater ⁸⁷Sr/⁸⁶Sr values also inversely correlate with both Mg/Ca and Sr/Ca ratios. Mass-balance modeling combined with these geochemical relationships suggest that variations in fluid compositions are predominantly controlled by groundwater residence times, and water-rock interaction with overlying soils and host aquifer carbonate rocks. Consistent differences in dripwater geochemistry (i.e., ⁸⁷Sr/⁸⁶Sr, Mg/Ca, and Sr/Ca) between individual caves are similar to compositional differences in soils above the caves. While these differences appear to exert significant control on local fluid evolution, geochemical and isotopic variations suggest that the controlling processes are regionally extensive. Temporal variations in ⁸⁷Sr/⁸⁶Sr values and Mg/Ca ratios of dripwaters from some sites over the 4-yr interval correspond with changes in both aquifer and climatic parameters. These results have important implications for the interpretation of trace element and isotopic variations in speleothems as paleoclimate records, as well as the understanding of controls on water chemistry for both present-day and ancient carbonate aquifers.     

Correlation between strontium and oxygen isotopic compositions of rocks from the Adamello massif (Northern Italy)

Rock samples from the lithologic units forming the Adamello massif were analyzed for Rb and Sr concentrations and for⁸⁷Sr/⁸⁶Sr and¹⁸O/¹⁶O ratios. The most important features are as follows:

1. the strontium and oxygen isotopes show a systematic variation from south to northwest across the massif, the older units in the south being lower both in⁸⁷Sr and¹⁸O;
2. a good positive correlation was found between strontium and oxygen isotopic compositions.

Two genetic models are advanced for explaining the results: (1) the mixing of two magmas with different¹⁸O and⁸⁷Sr contents; (2) magma formation at different depths in a crust layered with respect to both oxygen and strontium isotope composition.     

In situ Sr isotopic analyses of epidote: tracing the sources of multi-stage fluids in ultrahigh-pressure eclogite (Ganghe,Dabie terrane)

This study presents in situ strontium (Sr) isotope and Sr content data on multi-stage epidote crystals from ultrahigh-pressure (UHP) eclogites and omphacite–epidote veins therein at Ganghe (Dabie terrane, China), determined using LA-MC-ICP-MS. The Ganghe eclogites occur as lenses in mainly leucocratic UHP gneisses, and therefore, our data provide insights into the origin, composition, and transport scale of the discrete multi-stage fluids in UHP eclogites during the subduction and exhumation of a continental crust. Four textural types of epidote that record compositional and isotopic signatures of fluid at various metamorphic P–T conditions have been distinguished based on petrographic observations and compositional analyses. They are (1) fine-grained high-pressure (HP) epidote inclusions (Ep-In) in omphacite that define the earliest stage of epidote formation in the eclogite; (2) coarse-grained UHP epidote porphyroblasts (Ep-P) that contain omphacite with Ep-In inclusions in the eclogite; (3) fine-grained HP epidote in omphacite–epidote veins (Ep-V) as well as (4) the latest-stage epidote in disseminated amphibolite-facies veinlets (Ep-A), which crosscut the Ep-P or matrix minerals in the eclogite and HP vein. Both Ep-P and Ep-V crystals exhibit significant and complex chemical zonations with respect to the X_Fe (= Fe/(Fe + Al)) ratio and Sr content. In contrast to the varying Sr contents, Ep-In, Ep-P, and Ep-V have similar and narrow ranges of initial ⁸⁷Sr/⁸⁶Sr ratios (from 0.70692 to 0.70720 for Ep-In, from 0.70698 to 0.70721 for Ep-P, and from 0.70668 to 0.70723 for Ep-V), which are significantly different from those in Ep-A (from 0.70894 to 0.71172). The initial ⁸⁷Sr/⁸⁶Sr ratio of Ep-A is closer in value to the initial Sr isotopic composition of the gneisses (from 0.710790 to 0.712069) which enclose the UHP eclogite. These data indicate different sources of the eclogite-facies fluids and retrograde amphibolite-facies fluid in the Ganghe eclogites. The HP–UHP fluids responsible for the large amounts of hydrous minerals in the eclogites were internally derived and buffered. The omphacite–epidote veins were precipitated from the channelized solute-rich HP–UHP fluids released from the host eclogite. However, hydrated amphibolite-facies metamorphism during exhumation was mainly initiated by the low-Sr and high-⁸⁷Sr/⁸⁶Sr external fluid, which infiltrated into the eclogite from the surrounding gneisses. The eclogite-facies fluids in the Ganghe eclogites were locally derived, whereas the infiltration of the retrograde amphibolite-facies fluid from the gneisses required a long transport, most likely longer than 80 m. This study highlights that the in situ Sr isotopic analysis of multi-stage epidote can be employed as a powerful geochemical tracer to provide key information regarding the origin and behavior of various-stage subduction-zone metamorphic fluids.     

Anomalous unradiogenic 87Sr//86Sr ratios in ultrahigh‐pressure crustal carbonates – evidence for fluid infiltration during deep subduction?

Marbles from Changpu (Dabie Shan, eastern China), subducted to 4.4 GPa, have ⁸⁷Sr/⁸⁶Sr values < 0.7040. These low ⁸⁷Sr/⁸⁶Sr values, which would imply a sedimentation age > 2 Ga if considered as primary signature, reflect fluid–rock interaction with a fluid from a low‐⁸⁷Sr/⁸⁶Sr source. The introduction of low‐⁸⁷Sr/⁸⁶Sr was paralleled by introduction of Mg and loss of Si, K and Na in such a way that carbonates from the purest marbles have the least evolved Sr isotopic composition. Introduction of Mg is also indicated by the distribution of calcite and dolomite. Calcite forms inclusions in garnet, whereas dolomite is restricted to the matrix. These chemical changes, inferred from the mineralogy, in combination with textural evidence require a mobile metamorphic fluid. P–T–X constraints for fluid generation and for permeability increase related to mineral reactions and phase transitions suggest that the marbles acquired their anomalous Sr‐isotopic composition during subduction below 60 km. The marbles with the least radiogenic Sr isotopic composition demonstrate that crustal rocks may lose their isotopic fingerprint during deep subduction.     

A strontium,neodymium and oxygen isotope study of hydrothermal metamorphism and crustal anatexis in the Trois Seigneurs Massif,Pyrenees, France

Nd, Sr, and O isotope analyses have been made on metamorphic and igneous rocks and minerals from a 310–340 Ma Hercynian-age metamorphic terrane in the Pyrenees, France. Lower Paleozoic shales and phyllites have ⁸⁷Sr/⁸⁶Sr values of 0.707–0.717 at 310 Ma, but model values at 310 Ma of 0.709–0.736 (based on assumed depositional age of 450 Ma and an initial ⁸⁷Sr/⁸⁶Sr=0.707). On a regional scale, ⁸⁷Sr/⁸⁶Sr was homogenized to about 0.713 to 0.717 in the higher-grade pelitic schists during metamorphism. Much of this ⁸⁷Sr/⁸⁶Sr exchange occurred at very low grades (below the biotite isograd), but significant changes also accompanied the δ ¹⁸O lowering of the phyllites (+13 to +16) during their transformation to andalusite- and sillimanite-grade schists (δ ¹⁸O=+11 to +12); all of these effects are attributed to pervasive interactions with hydrothermal fluids (Wickham and Taylor 1985). The data also show that a syn-metamorphic plutonic complex, dominated by a biotite granite body, was derived by mixing of a relatively mafic magmatic end-member (⁸⁷Sr/⁸⁶Sr～ 0.7025–0.7050 and δ ¹⁸O～ +7.5 to +8.0) with two metasedimentary sources, both having ⁸⁷Sr/⁸⁶Sr～0.715 and δ ¹⁸O～ +10.0 to +12.0, but with one being more homogeneous than the other. The more homogeneous component and the (mantle-derived?) magmatic end-member dominate at low structural levels within the complex. The less homogeneous end-member that dominates at high levels is clearly derived from the local Paleozoic pelitic schists. A Rb-Sr age of 330±20 Ma was obtained on hornblende from a deep level within the complex, which fixes this age for the regional metamorphism, as well. Although a post-metamorphic granodiorite magma body at Trois Seigneurs also displays heterogeneities in δ ¹⁸O and ⁸⁷Sr/⁸⁶Sr (and thus does not give a clear-cut Rb-Sr isochron), the data are consistent with an emplacement age between 260 and 310 Ma, similar to ages of other late granodiorites in the Pyrenees. ¹⁴³Nd/ ¹⁴⁴Nd is very uniform within the Hercynian crust, both at Trois Seigneurs (? _Nd=?3 to ?7) and elsewhere in the Pyrenees; almost all igneous lithologies have depleted-mantle, mid-Proterozoic model ages, consistent with efficient recycling of crustal material following original crustal accretion in this area at about 1600 Ma or earlier. Rb-Sr mineral ages exhibit a complex cooling history reflecting late Hercynian and Mesozoic thermal events. Our results show that profound homogenization of the ⁸⁷Sr/⁸⁶Sr and ¹⁸O/¹⁶O ratios of large volumes of the crust can occur during regional metamorphism and crustal anatexis, particularly in regions undergoing extensional tectonics. Such processes can significantly modify the isotopic compositions of the protoliths of granitic magmas; this may explain why many peraluminous Hercynian granitoids of Western Europe have anomalously low (⁸⁷Sr/⁸⁶Sr) initial values compared to their probable sedimentary parent rocks.     

四川盆地东部地区早中三叠世蒸发岩的锶同位素特征及其地质意义

锶同位素已经成为全球海平面变化、造山运动、古气候和古环境等全球地质事件研究与对比的有效工具之一。本文以四川盆地东部地区早中三叠世蒸发岩的野外剖面和钻孔岩心为主要研究对象,测试了碳酸盐岩、硫酸盐岩和石盐岩的锶同位素组成,并建立了相应的锶同位素演化曲线。研究结果显示,碳酸盐岩的⁸⁷Sr/⁸⁶Sr值平均为0.707 895,硬石膏岩的⁸⁷Sr/⁸⁶Sr值平均为0.708 174,石盐岩的⁸⁷Sr/⁸⁶Sr值平均为0.708 177,同时碳酸盐岩的⁸⁷Sr/⁸⁶Sr值从早三叠世的0.707 413快速增加到中三叠世早期的0.708 515,而后呈现下降趋势。从总体上看,这些⁸⁷Sr/⁸⁶Sr值与全球早中三叠世同期的⁸⁷Sr/⁸⁶Sr值数据接近,说明四川盆地东部地区早中三叠世钾盐的物质来源大部分为海水,并沉积于海相沉积环境,同时由于火山...     

In situ Sr/Sr investigation of igneous apatites and carbonates using laser-ablation MC-ICP-MS

In situ Sr isotopic compositions of coexisting apatite and carbonate for carbonatites from the Sarfartoq alkaline complex, Greenland, have been determined by laser-ablation multicollector inductively coupled plasma mass spectrometry. This study is the first to examine the extent of Sr isotopic homogeneity among coexisting igneous minerals containing high Sr (>3000 ppm) and low Rb (?1 ppm) contents within a single ∼50-μm-thick thin-section mount. This technique is capable of producing measured ⁸⁷Sr/⁸⁶Sr values with analytical precision (∼0.005%, 2σ) approaching those obtained by thermal ionization mass spectrometry but in a much shorter interval of time (100 s vs. >1 h, respectively). The combined total analyses (n = 107) of apatite and carbonate yield ⁸⁷Sr/⁸⁶Sr compositions ranging from ∼0.7025 to ∼0.7031. This relatively large variation in Sr isotopic compositions (∼0.0006) is ∼1 order of magnitude larger than the estimated external reproducibility (∼0.00005, 2σ) of the method. The large range in ⁸⁷Sr/⁸⁶Sr values suggests that apatite and carbonate precipitated predominantly under nonequilibrium conditions. The isotopic variations observed within individual hand specimens may therefore reflect larger (regional) scale open-system processes, possibly involving mixing of carbonatitic melts derived from distinct mantle sources or from a common isotopically heterogeneous mantle.     

The Origin of Paleokarst in the Huanglong Formation of the Eastern Sichuan Basin: Evidence from δ13C, δ18O and 87Sr/86Sr

Karst rocks from the Huanglong Formation exposed at the margin of the Eastern Sichuan Basin can be divided into four types:slightly corroded, moderately corroded porous, intensely corroded brecciated and intensely corroded and replaced secondary calcic karstic rocks. The carbon, oxygen and strontium isotope compositions of the various karst rocks are analyzed systematically and compared to rocks without karst corrosion. The results indicate that(1) the Huanglong Formation in the eastern Sichuan Basin was a restricted bay supplied and controlled by freshwater in which mudmicrite and mud-dolomicrite exhibit low δ13C and δ18O values and high 87Sr/86 Sr ratios;(2) all types of karstic rocks in the paleokarst reservoirs of the Huanglong Formation in the research area are affected by atmospheric freshwater with the δ13C and δ18O values and 87Sr/86 Sr ratios in the original formation approaching those of atmospheric freshwater, which reflects ancient hydrological conditions, fluid properties, isotopic source and the fractionation effect;(3) the intensely corroded and replaced secondary limestone is affected by a variety of diagenetic fluids, often reflected by δ13C and δ18O values, while the 87Sr/86 Sr ratios exhibit the strong degree of the corrosion;(4) after comparing the 87Sr/86 Sr ratios of each type of karst rock, the diagenetic fluids are determined to be mainly atmospheric freshwater, and depending on the strength of corrosion, and the low 87Sr/86 Sr ratio fluids in the layer will participate in the karst process. The carbon, oxygen, and strontium isotopes of different karstic reservoirs can provide meaningful geochemical information for forecasting and evaluating the development and distribution rules of the Huanglong Formation at the margin of the eastern Sichuan Basin in time and space.     

Environmental isotopes (18O, 2H, and 87Sr/86Sr) as a tool in groundwater investigations in the Keta Basin, Ghana

Analyses of environmental isotopes (¹⁸O, ²H, and ⁸⁷Sr/⁸⁶Sr) are applied to groundwater studies with emphasis on saline groundwater in aquifers in the Keta Basin, Ghana. The ⁸⁷Sr/⁸⁶Sr ratios of groundwater and surface water of the Keta Basin primarily reflect the geology and the mineralogical composition of the formations in the catchments and recharge areas. The isotopic compositions of ¹⁸O and ²H of deep groundwater have small variations and plot close to the global meteoric water line. Shallow groundwater and surface water have considerably larger variations in isotopic compositions, which reflect evaporation and preservation of seasonal fluctuations. A significant excess of chloride in shallow groundwater in comparison to the calculated evaporation loss is the result of a combination of evaporation and marine sources. Groundwaters from deep wells and dug wells in near-coastal aquifers are characterized by relatively high chloride contents, and the significance of marine influence is evidenced by well-defined mixing lines for strontium isotopes, and hydrogen and oxygen stable isotopes, with isotopic compositions of seawater as one end member. The results derived from environmental isotopes in this study demonstrate that a multi-isotope approach is a useful tool to identify the origin and sources of saline groundwater. Electronic Publication     

塔东地区古城4井上寒武统—中、上奥陶统流体地球化学示踪

通过对塔东地区古城4井上寒武统和中、上奥陶统碳酸盐岩围岩及充填物的碳、氧、锶同位素地球化学和流体包裹体成分的对比研究表明,充填于中、上奥陶统和上寒武统的流体分属于2个不同来源的流体体系。充填于中、上奥陶统灰岩裂缝中方解石脉的w(87Sr)/w(86Sr)介于0.7084~0.7088,它与早奥陶世海水的w(87Sr)/w(86Sr)相近;流体体系为CH4-H2O体系;充填物与围岩间具有明显的碳、氧同位素差异,表明上部流体体系中的流体来自于奥陶系地层本身。上寒武统白云岩裂缝中方解石脉的w(87Sr)/w(86Sr)为0.7138,明显地高于同时代海水的锶同位素值;流体体系为CO2-H2O体系;下部流体体系中的流体为外来富锶流体。上、下流体体系间互不连通暗示着上寒武统地层具有相对较好的保存条件。     

Rubidium,strontium and the isotopic composition of strontium in ultramafic nodule minerals and host basalts

The concentrations of rubidium and strontium and the isotopic composition of strontium have been determined in minerals separated from ultramaflc nodules occurring in late Tertiary and Quaternary basalts of wide geographic distribution. Clinopyroxene, orthopyroxene and olivine from each of three Iherzolite nodules show a relatively wide range of ⁸⁷Sr/⁸⁶Sr disequilibrium and none of the minerals is in isotopic equilibrium with its host basalt. In two cases there is a correlation between ⁸⁷Sr/⁸⁶Sr and ⁸⁷Rb/⁸⁶Sr ratios of the nodule minerals, indicating apparent isochron relationships which may represent relict mantle events. Clinopyroxene and olivine from each of two wehrlite nodules are not in isotopic equilibrium, although the magnitude of the disequilibrium is smaller than that observed in the Iherzolite nodules. None of these ultramafic nodules can be a crystal cumulate from its host basalt, and it is doubtful that any type of genetic relationship exists. The strontium isotopic disequilibrium between nodule minerals seems to be a primary feature inherited from past mantle histories.     

Isotopic constraints on the genesis and age of autochthonous glaucony in the Oligo-Miocene Torquay Group, south-eastern Australia

The Oligo‐Miocene Torquay Group at Bird Rock in south‐eastern Australia comprises a sequence of fine‐grained skeletal carbonates and argillaceous and glauconitic sandstones, deposited in a cool‐water, mid‐shelf environment. The Bird Rock glaucony is autochthonous and consists predominantly of randomly interstratified glauconitic smectite, which constitutes bioclast infills and faecal pellet replacements. The results of Rb–Sr and oxygen isotopic analysis of samples taken from a single glauconitic horizon (the BW horizon) indicate that the glaucony developed through a series of simultaneous dissolution–crystallization reactions, which occurred during very early diagenesis in a closed or isochemical system, isolated from the ambient marine environment. The constituent ions of the glaucony were derived primarily from terrigenous clay minerals, but considerable potassium may have been sourced indirectly from sea water, through potassium enrichment of clay precursors. The pore fluids associated with glauconitization were marine derived, but progressively modified by the dissolution–crystallization of detrital clay minerals and autochthonous glaucony. Rb–Sr data for the BW horizon indicate that dating glauconies may be somewhat problematic, as co‐genetic glauconitic minerals can show a range of initial strontium compositions, which reflect the incorporation of strontium derived from mineralogical precursors and/or contemporaneous sea water. Rb–Sr isochrons indicate that the glaucony of the BW horizon formed at 23 ± 3 Ma. This age is in good agreement with both the established biostratigraphy and a ⁸⁷Sr/⁸⁶Sr age for the horizon (23 ± 1 Ma), but could only be determined using the independent age constraint and the estimate of the ⁸⁷Sr/⁸⁶Sr ratio of contemporaneous sea water provided by analysis of associated biogenic carbonate.