Strontium isotopic evidence on the chemical evolution of pore waters in the Milk River Aquifer,Alberta, Canada

Strontium isotope ratios were measured on 13 rock, 18 leachate and 28 pore-water samples from the Milk River aquifer, the confining argillaceous formations, and the glacial till mantling the recharge area. Strontium isotope ratios (⁸⁷Sr/⁸⁶Sr) of pore waters from the aquifer, confining units, and the glacial till ranged from 0.7069 to 0.7082. The ⁸⁷Sr/⁸⁶Sr ratios in aquifer pore waters decrease with increasing distance from the aquifer recharge area, and this is interpreted to be the result of mixing and water–rock interaction within the aquifer.The solute composition of the recharging groundwater is modified by the local lithology, causing distinct geochemical patterns along different flow paths within the aquifer. Whole-rock ⁸⁷Sr/⁸⁶Sr ratios indicate that the shales and till are generally more radiogenic than the aquifer sandstone. The authigenic carbonate cements and rock-forming minerals comprising the major lithologic units had little apparent influence on the pore-water Sr chemistry. Carbonate cement leachates from the till and the aquifer sandstone are more radiogenic than those from the confining shale formations. Feldspar separates from the aquifer sandstone have relatively radiogenic Sr isotope ratios, whereas bentonites from the Milk River and Colorado Shale Formations have whole-rock and leachate Sr isotope ratios that are relatively unradiogenic. Ratios of most Milk River aquifer pore waters are lower than those of any leachates or whole rocks analyzed, except the bentonites.The ⁸⁷Sr/⁸⁶Sr ratios of exchangeable Sr in the bentonites are similar to ratios found in the more evolved pore waters. Simple rock–water interaction models calculated for the whole-rock, leachate, and exchangeable-ion/pore-water pairs indicate that ion exchange with bentonite clays within the Milk River and Colorado Shale Formations appears to influence the isotopic evolution of the pore-water Sr in each of these units.     

Determination of Sr/Sr mass-dependent isotopic fractionation and radiogenic isotope variation of Sr/Sr in the Neoproterozoic Doushantuo Formation

We measured both mass-dependent isotope fractionation of δ⁸⁸Sr (⁸⁸Sr/⁸⁶Sr) and radiogenic isotopic variation of Sr (⁸⁷Sr/⁸⁶Sr) for the Neoproterozoic Doushantuo Formation that deposited as a cap carbonate immediately above the Marinoan-related Nantuo Tillite. The δ⁸⁸Sr and ⁸⁷Sr/⁸⁶Sr compositions showed three remarkable characteristics: (1) high radiogenic ⁸⁷Sr/⁸⁶Sr values and gradual decrease in the ⁸⁷Sr/⁸⁶Sr ratios, (2) anomalously low δ⁸⁸Sr values at the lower part cap carbonate, and (3) a clear correlation between ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr values. These isotopic signatures can be explained by assuming an extreme greenhouse condition after the Marinoan glaciation. Surface seawater, mixed with a large amount of freshwater from continental crusts with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios, was formed during the extreme global warming after the glacial event. High atmospheric CO₂ content caused sudden precipitation of cap carbonate from the surface seawater with high ⁸⁷Sr/⁸⁶Sr and lighter δ⁸⁸Sr ratios. Subsequently, the mixing of the underlying seawater, with unradiogenic Sr isotope compositions and normal δ⁸⁸Sr ratios, probably caused gradual decrease of the ⁸⁷Sr/⁸⁶Sr ratios of the seawater and deposition of carbonate with normal δ⁸⁸Sr ratios. The combination of ⁸⁷Sr/⁸⁶Sr and δ⁸⁸Sr isotope systematics gives us new insights on the surface evolution after the Snowball Earth.     

Baseline determination of the atmospheric Pb,Sr and Nd isotopic compositions in the Rhine valley,Vosges mountains (France) and the Central Swiss Alps

The Pb, Sr and Nd isotopic compositions of biomonitors (lichen, moss, bark) and soil litter from different regions in the Rhine valley, as well as of <0.45 μm particles separated out of ice of the Rhône and Oberaar glaciers and lichens from the Swiss Central Alps, have been determined in order to deduce the natural baseline of the atmospheric isotopic compositions of these regions, which are suggested to be close to the isotopic compositions of the corresponding basement rocks or soils at the same sites. ²⁰⁶Pb/²⁰⁷Pb and ⁸⁷Sr/⁸⁶Sr isotope ratios are positively correlated. Most polluted samples from traffic-rich urban environments have the least radiogenic Pb and Sr isotopic compositions with ²⁰⁶Pb/²⁰⁷Pb and ⁸⁷Sr/⁸⁶Sr ratios of 1.11 and 0.7094, respectively. These ratios are very different from those of the atmospheric baseline for the Vosges mountains and the Rhine valley (²⁰⁶Pb/²⁰⁷Pb: 1.158–1.167; ⁸⁷Sr/⁸⁶Sr: 0.719–0.725; ε_Nd: −7.5 to −10.1). However, this study indicates that the baseline of the atmospheric natural Pb and Sr isotopic compositions is affected by anthropogenic (traffic, industrial and urban) emissions even in remote areas. Lichen samples from below the Rhône and Oberaar glaciers reflect the baseline composition close to the Grimsel pass in the Central Swiss Alps (⁸⁷Sr/⁸⁶Sr: 0.714 − 0.716; ε_Nd: −3.6 to −8.1). The ¹⁴³Nd/¹⁴⁴Nd isotope ratios are highly variable (8ε units) and it is suggested that the variation of the ¹⁴³Nd/¹⁴⁴Nd is controlled by wet deposition and aerosols originating from the regional natural and industrial urban environments and from more distant regions like the Sahara in North Africa. The least anthropogenetically affected samples collected in remote areas have isotopic compositions closest to those of the corresponding granitoid basement rocks.     

Evidence for mass-dependent isotopic fractionation of strontium in a glaciated granitic watershed

The stable isotope composition of strontium (expressed as δ^88/86Sr) may provide important constraints on the global exogenic strontium cycle. Here, we present δ^88/86Sr values and ⁸⁷Sr/⁸⁶Sr ratios for granitoid rocks, a 150 yr soil chronosequence formed from these rocks, surface waters and plants in a small glaciated watershed in the central Swiss Alps. Incipient chemical weathering in this young system, whether of inorganic or biological origin, has no resolvable effect on the ⁸⁷Sr/⁸⁶Sr ratios and δ^88/86Sr values of bulk soils, which remain indistinguishable from bedrock in terms of Sr isotopic composition. Although due in part to the chemical heterogeneity of the forefield, the lack of a resolvable difference between soil and bedrock isotopic composition indicates that these soils have thus far witnessed minimal net loss of Sr; a low degree of chemical weathering is also implied by bulk soil chemistry. The isotopic composition of Sr in streamwater is more radiogenic than median soil, reflecting the preferential weathering of biotite in the catchment; streamwater δ^88/86Sr values, however, are indistinguishable from bulk soil δ^88/86Sr values, implying that no resolvable fractionation of Sr isotopes takes place during release to the weathering flux in the Damma forefield. Analyses of plant tissue reveal that plants (Rhododendron and Vaccinium) preferentially assimilate the lighter isotopes of Sr such that their δ^88/86Sr values are significantly lower than those of the soils in which they grow. Additionally, δ^88/86Sr values of foliar and floral tissues are lower than those of roots, contrary to observations for Ca, for which Sr is often used as an analogue in weathering studies. We suggest that processes that discriminate against Sr in favour of Ca, due to the different nutritional requirement of plants for these two elements, are responsible for the observed contrast.     

Evaluating the use of strontium isotopes in tree rings to record the isotopic signal of dust deposited on the Wasatch Mountains

Dust cycling from the Great Basin to the Rocky Mountains is an important component of ecological and hydrological processes. We investigated the use of strontium (Sr) concentrations and isotope ratios (⁸⁷Sr/⁸⁶Sr) in tree rings as a proxy for dust deposition. We report Sr concentrations and isotope ratios (⁸⁷Sr/⁸⁶Sr) from atmospherically deposited dust, soil, bedrock, and tree rings from the Wasatch Mountains to investigate provenance of dust landing on the Wasatch Mountains and to determine if a dust Sr record is preserved in tree rings. Trees obtained a majority of their Sr from dust, making them a useful record of dust source and deposition. Dust contributions of Sr to soils were more than 94% over quartzite, 63% over granodiorite, and 50% over limestone. Dust contributions of Sr to trees were more than 85% in trees growing over quartzite, 55% over granodiorite, and between 0% and 92% over limestone. These findings demonstrate that a dust signal was preserved in some tree rings and reflects how Sr from dust and bedrock mixes within the soil. Trees growing over quartzite were most sensitive to dust. Changes in Sr isotope ratios for a tree growing over quartzite were interpreted as changes in dust source over time. This work has laid the foundation for using tree rings as a proxy for dust deposition over time.     

Speciation of strontium in particulates and sediments from the Mississippi River mixing zone

Sequential extractions were performed on small amounts of particulate and sediment samples (6 to10 mg) from the Mississippi River mixing zone. The leachates were analyzed for Sr concentration and ⁸⁷Sr/⁸⁶Sr isotope ratio. Mn and Fe contents were also measured as their oxyhydroxides are potential carrier phases for Sr. The largest fraction of Sr in the solid phase (particulates and sediments) was found to be present in the residual, refractory fraction (>70% of total). By comparison with the corresponding sediment, particulates appear to have higher concentrations of nonresidual, labile Sr (30% vs. 15%). Carbonate components seem to play an important role as carriers for labile Sr in particulates and sediments. Changes in the composition and content of the solid phase may significantly modify both the ⁸⁷Sr/⁸⁶Sr isotope ratio of the total labile fractions and that of the bulk components. However, such modifications, under normal conditions, exert little measurable influence on the Sr isotope composition of the dissolved phase.     

Multiple fluid components of salt diapirs and salt dome cap rocks, Gulf Coast, U.S.A.

Salt diapirs contain a few percent of anhydrite that accumulated as residue to form anhydrite cap rocks during salt dissolutions. Reported ⁸⁷Sr/⁸⁶Sr ratios of these salt-hosted and cap rock anhydrites in the Gulf Coast, U.S.A., indicate their derivation from Middle Jurassic seawater. However, a much wider range of ⁸⁷Sr/⁸⁶Sr ratios, incorporating a highly radiogenic component in addition to the Middle Jurassic component, has been found in several Gulf Coast salt domes. This wide range of ⁸⁷Sr/⁸⁶Sr ratios of anhydrite within the salt stocks records Sr contributions from both marine water and formation water that has equilibrated with siliciclastics. During cap rock formation this anhydrite either recrystallized in the presence of, or was cemented by, a low-Sr fluid with a Late Cretaceous seawter-type Sr isotope ratio or simply lost Sr during recrystallization. Later, the cap rock was invaded by warm saline brines with high Sr isotope ratios from which barite and metal sulfides were precipitated. Subsequently, low-salinity water hydrated part of the anhydrite bringing to six the total number of fluids that interacted througout the history of salt dome and cap rock growth. The progenitor of these salt diapirs, the Louann Formation, is generally thought to have formed from marine water evaporated to halite and, rarely, higher evaporite facies. Salt domes in the East Texas, North Louisiana, and Mississippi Salt Basins have ⁸⁷Sr/⁸⁶Sr and δ³⁴S values that corroborate a Mid-Jurassic age for the mother salt. However, salt domes in the Houston and Rio Grande Embayments of the Gulf Coast Basin have ⁸⁷Sr/⁸⁶Sr ration ranging to values higher than both Middle Jurassic seawater and all Rb-free marine Phanerozoic rocks. These anomalous ⁸⁷Sr/⁸⁶Sr ratios are probably derived from radiogenic Sr-bearing fluids that equilibrated with siliciclastic rocks and invaded the salt either prior to, or during, diapirism. Potential sources of the radiogenic ⁸⁷Sr component include clay and/or feldspar (located either in older units beneath the Louann Formation or younger units flanking the salt diapirs) and K-salts within the Louann evaporites. Because partial Sr exchange in anhydrite had to take place in a fluid medium, admittance of radiogenic ⁸⁷Sr-bearing fluids into the salt may have led to diapirism by lowering the shear strength of the crystalline salt. The slight number of anomalous ⁸⁷Sr/⁸⁶Sr values in the interior basins indicates that anomalous values are related to areally discrete structural or stratigraphic controls that affected only the Gulf Coast Basin.     

An assessment of solubility profiling as a decontamination procedure for the 87Sr/86Sr analysis of archaeological human skeletal tissue

⁸⁷Sr/⁸⁶Sr of archaeological skeletal tissues are increasingly used to reconstruct residential mobility and migration, but the post mortem preservation of biogenic Sr is often uncertain. Sample pre-treatment regimes, notably ‘solubility profiling’, have been used to remove diagenetic Sr prior to analysis, but doubts remain over their effectiveness. The investigation examines the effectiveness of solubility profiling by comparing the Sr content and ⁸⁷Sr/⁸⁶Sr composition of bone, dentine and enamel from two archaeological juveniles (Blackfriars, UK) before and after attempted decontamination. For both individuals leached samples of cortical bone and dentine had similar ⁸⁷Sr/⁸⁶Sr to those of soil leachates from the burial site, and are therefore thought to represent diagenetic ⁸⁷Sr/⁸⁶Sr. For both individuals samples of treated dental enamel have ⁸⁷Sr/⁸⁶Sr considerably more or less radiogenic than the soil leachates and other tissues. These are considered representative of biogenic Sr, i.e. Sr acquired in vivo. In effect, solubility profiling should have resulted in ⁸⁷Sr/⁸⁶Sr that were similar for all 3 tissues types and close to those of the untreated enamel. Experimental results show that tooth enamel ⁸⁷Sr/⁸⁶Sr remained largely unaffected by solubility profiling, and the process did not significantly alter the final ⁸⁷Sr/⁸⁶Sr of either dentine or cortical bone. It is concluded that the technique was ineffective in facilitating the recovery of biogenic Sr from these tissues.     

Strontium isotope systematics of base flow in Piedmont Province watersheds,Georgia (USA)

⁸⁷Sr/⁸⁶Sr ratio variations were analyzed in rainfall, shallow ground water and base flow collected from 4 Piedmont streams within the Middle Oconee River basin in northeastern Georgia during the period between March, 2003 and March, 2004. They Sr isotope ratio analyses were accompanied by measurements of stream discharge, rainfall, stable O isotope ratios and major ion and ³H concentrations. The average Sr ion concentration and ⁸⁷Sr/⁸⁶Sr ratio for the terminal stream basin (the Middle Oconee River) were 23.6 μg/L and 0.7172, respectively. The average ⁸⁷Sr/⁸⁶Sr ratios of the rainwater and shallow ground water were below 0.7125, indicating that most of the Sr in this stream water is input by weathering reactions in deeper ground water, rather than by ion exchange in shallow soil horizons. This is consistent with the higher alkalinity concentrations (∼23–47 mg/L) and specific conductance values (60–113 μS/cm) that characterize stream base flow. Piedmont streams are characterized by lower concentrations of Sr and higher ⁸⁷Sr/⁸⁶Sr ratios than average global stream flow.Base flow rates decreased by a factor of 2–3 during the summer months and this is accompanied by increased alkalinity concentrations. ⁸⁷Sr/⁸⁶Sr ratios, however, were temporally invariant for a given stream basin and were independent of season, antecedent rainfall, and discharge. ⁸⁷Sr/⁸⁶Sr ratios were unique for each of the 4 basins and a general trend toward higher ratios with increasing basin area was apparent. The inferred contribution from minerals with high Rb contents such as K feldspar and muscovite may have resulted from the greater integration of flow from mineralogically diverse pathways afforded by a larger basin area. The basin specificity and temporal or seasonal invariability make ⁸⁷Sr/⁸⁶Sr ratios an invaluable hydrological tracer that can be readily employed in mass balance studies of stream flow within the Piedmont Province.     

Strontium isotope geochemistry of groundwater affected by human activities in Nandong underground river system, China

The Nandong Underground River System (NURS) is located in a typical karst area dominated by agriculture in SE Yunnan Province, China. Groundwater plays an important role in the social and economical development in the area. The effects of human activities (agriculture and sewage effluents) on the Sr isotope geochemistry were investigated in the NURS. Seventy-two representative groundwater samples, which were collected from different aquifers (calcite and dolomite), under varying land-use types, both in summer and winter, showed significant spatial differences and slight seasonal variations in Sr concentrations and ⁸⁷Sr/⁸⁶Sr ratios. Agricultural fertilizers and sewage effluents significantly modified the natural ⁸⁷Sr/⁸⁶Sr ratios signature of groundwater that was otherwise dominated by water-rock interaction. Three major sources of Sr could be distinguished by ⁸⁷Sr/⁸⁶Sr ratios and Sr concentrations in karst groundwater. Two sources of Sr are the Triassic calcite and dolomite aquifers, where waters have low Sr concentrations (0.1-0.2 mg/L) and low ⁸⁷Sr/⁸⁶Sr ratios (0.7075-0.7080 and 0.7080-0.7100, respectively); the third source is anthropogenic Sr from agricultural fertilizers and sewage effluents with waters affected having radiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.7080-0.8352 for agricultural fertilizers and 0.7080-0.7200 for sewage effluents, respectively), with higher Sr concentrations (0.24-0.51 mg/L). Due to the overlapping ⁸⁷Sr/⁸⁶Sr ratios, it is difficult to distinguish the sources of Sr in groundwater samples contaminated by agricultural fertilizers or sewage effluents based only on their ⁸⁷Sr/⁸⁶Sr ratios. However, ⁸⁷Sr/⁸⁶Sr ratios do provide key information for natural and anthropogenic sources in karst groundwater.     

On ‘spurious’ correlations in Rb-Sr isochron diagrams

A general null hypothesis for isotope geochemistry states that the isotopic composition of an element is independent of its concentration or any other geochemical property of the population. ‘Spurious’ correlations between the ratios ⁸⁷Sr/⁸⁶Sr and ⁸⁷Rb/⁸⁶Sr (orRb/Sr), due to the common denominator effect, may be ruled out because they contradict this null hypothesis. Mixing processes may be regarded as geochemical counterparts of the common denominator effect. In geochronological systems which satisfy the basic assumptions of the Rb-Sr isochron method observed correlations between Sr isotope abundance and Sr concentration must be secondary to the direct causal dependence of ⁸⁷Sr/⁸⁶Sr upon Rb/Sr ratios.     

Constraining the marine strontium budget with natural strontium isotope fractionations (Sr/Sr∗, δSr) of carbonates, hydrothermal solutions and river waters

We present strontium (Sr) isotope ratios that, unlike traditional ⁸⁷Sr/⁸⁶Sr data, are not normalized to a fixed ⁸⁸Sr/⁸⁶Sr ratio of 8.375209 (defined as δ^88/86Sr = 0 relative to NIST SRM 987). Instead, we correct for isotope fractionation during mass spectrometry with a ⁸⁷Sr-⁸⁴Sr double spike. This technique yields two independent ratios for ⁸⁷Sr/⁸⁶Sr and ⁸⁸Sr/⁸⁶Sr that are reported as (⁸⁷Sr/⁸⁶Sr∗) and (δ^88/86Sr), respectively. The difference between the traditional radiogenic (⁸⁷Sr/⁸⁶Sr normalized to ⁸⁸Sr/⁸⁶Sr = 8.375209) and the new ⁸⁷Sr/⁸⁶Sr∗ values reflect natural mass-dependent isotope fractionation. In order to constrain glacial/interglacial changes in the marine Sr budget we compare the isotope composition of modern seawater ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_Seawater) and modern marine biogenic carbonates ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_Carbonates) with the corresponding values of river waters ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_River) and hydrothermal solutions ((⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_HydEnd) in a triple isotope plot. The measured (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_River values of selected rivers that together account for ∼18% of the global Sr discharge yield a Sr flux-weighted mean of (0.7114(8), 0.315(8)‰). The average (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_HydEnd values for hydrothermal solutions from the Atlantic Ocean are (0.7045(5), 0.27(3)‰). In contrast, the (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_Carbonates values representing the marine Sr output are (0.70926(2), 0.21(2)‰). We estimate the modern Sr isotope composition of the sources at (0.7106(8), 0.310(8)‰). The difference between the estimated (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_input and (⁸⁷Sr/⁸⁶Sr∗, δ^88/86Sr)_output values reflects isotope disequilibrium with respect to Sr inputs and outputs. In contrast to the modern ocean, isotope equilibrium between inputs and outputs during the last glacial maximum (10-30 ka before present) can be explained by invoking three times higher Sr inputs from a uniquely “glacial” source: weathering of shelf carbonates exposed at low sea levels. Our data are also consistent with the “weathering peak” hypothesis that invokes enhanced Sr inputs resulting from weathering of post-glacial exposure of abundant fine-grained material.     

Sr isotopes as a tracer of weathering processes and dust inputs in a tropical granitoid watershed, Luquillo Mountains, Puerto Rico

Sr isotope data from soils, water, and atmospheric inputs in a small tropical granitoid watershed in the Luquillo Mountains of Puerto Rico constrain soil mineral development, weathering fluxes, and atmospheric deposition. This study provides new information on pedogenic processes and geochemical fluxes that is not apparent in watershed mass balances based on major elements alone. ⁸⁷Sr/⁸⁶Sr data reveal that Saharan mineral aerosol dust contributes significantly to atmospheric inputs. Watershed-scale Sr isotope mass balance calculations indicate that the dust deposition flux for the watershed is 2100 ± 700 mg cm⁻² ka⁻¹. Nd isotope analyses of soil and saprolite samples provide independent evidence for the presence of Saharan dust in the regolith. Watershed-scale Sr isotope mass balance calculations are used to calculate the overall short-term chemical denudation velocity for the watershed, which agrees well with previous denudation rate estimates based on major element chemistry and cosmogenic nuclides. The dissolved streamwater Sr flux is dominated by weathering of plagioclase and hornblende and partial weathering of biotite in the saprock zone. A steep gradient in regolith porewater ⁸⁷Sr/⁸⁶Sr ratio with depth, from 0.70635 to as high as 0.71395, reflects the transition from primary mineral-derived Sr to a combination of residual biotite-derived Sr and atmospherically-derived Sr near the surface, and allows multiple origins of kaolinite to be identified.     

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.     

The contribution of the Emeishan large igneous province to the strontium isotope evolution of the Capitanian seawater

ABSTRACT

The ⁸⁷Sr/⁸⁶Sr minimum of the Capitanian seawater is one of the most significant features in the Phanerozoic seawater ⁸⁷Sr/⁸⁶Sr history. In order to assess possible contribution of the Emeishan large igneous provinces (LIPs) to strontium isotope evolution of the Capitanian seawater, ⁸⁷Sr/⁸⁶Sr ratios were measured from the Capitanian limestones which are locally interlayered with the Emeishan basalts. The limestones underlying the Emeishan basalts have high ⁸⁷Sr/⁸⁶Sr ratios (0.7070–0.7074). However, extremely low ⁸⁷Sr/⁸⁶Sr ratios (0.7068–0.7070) were identified in the late Capitanian Jinogondolella prexuanhanensis–J. xuanhanensis zones, which correspond to the eruption time of the Emeishan LIP. The temporal coincidence of these two phenomena supports the idea of a potential linkage between Capitanian ⁸⁷Sr/⁸⁶Sr minimum and eruption of this igneous province. The strong submarine hydrothermal activity and erosion of the Emeishan LIP could have released large amounts of non-radiogenic Sr to the oceans and play an important role in strontium isotope evolution of the seawater.     

Groundwater mixing and mineralization processes in a mountain–oasis–desert basin,northwest China: hydrogeochemistry and environmental tracer indicators

Hydrogeochemistry and environmental tracers (²H, ¹⁸O, ⁸⁷Sr/⁸⁶Sr) in precipitation, river and reservoir water, and groundwater have been used to determine groundwater recharge sources, and to identify mixing characteristics and mineralization processes in the Manas River Basin (MRB), which is a typical mountain–oasis–desert ecosystem in arid northwest China. The oasis component is artificial (irrigation). Groundwater with enriched stable isotope content originates from local precipitation and surface-water leakage in the piedmont alluvial–oasis plain. Groundwater with more depleted isotopes in the north oasis plain and desert is recharged by lateral flow from the adjacent mountains, for which recharge is associated with high altitude and/or paleo-water infiltrating during a period of much colder climate. Little evaporation and isotope exchange between groundwater and rock and soil minerals occurred in the mountain, piedmont and oasis plain. Groundwater δ²H and δ¹⁸O values show more homogeneous values along the groundwater flow direction and with well depths, indicating inter-aquifer mixing processes. A regional contrast of groundwater allows the ⁸⁷Sr/⁸⁶Sr ratios and δ¹⁸O values to be useful in a combination with Cl, Na, Mg, Ca and Sr concentrations to distinguish the groundwater mixing characteristics. Two main processes are identified: groundwater lateral-flow mixing and river leakage in the piedmont alluvial–oasis plain, and vertical mixing in the north oasis plain and the desert. The ⁸⁷Sr/⁸⁶Sr ratios and selected ion ratios reveal that carbonate dissolution and mixing with silicate from the southern mountain area are primarily controlling the strontium isotope hydrogeochemistry.     

Petrogenesis of isotopically unusual Pliocene olivine leucitites from Deep Springs Valley, California

High-K mafic alkalic lavas (5.4 to 3.2 wt% K₂O) from Deep Springs Valley, California define good correlations of increasing incompatible element (e.g., Sr, Zr, Ba, LREE) and compatible element contents (e.g., Ni, Cr) with increasing MgO. Strontium and Nd isotope compositions are also correlated with MgO; ⁸⁷Sr/⁸⁶Sr ratios decrease and ɛ_Nd values increase with decreasing MgO. The Sr and Nd isotope compositions of these lavas are extreme compared to most other continental and oceanic rocks; ⁸⁷Sr/⁸⁶Sr ratios range from 0.7121 to 0.7105 and ɛ_Nd values range from −16.9 to −15.4. Lead isotope ratios are relatively constant, ²⁰⁶Pb/²⁰⁴Pb ∼17.2, ²⁰⁷Pb/²⁰⁴Pb ∼15.5, and ²⁰⁸Pb/²⁰⁴Pb ∼38.6. Depleted mantle model ages calculated using Sr and Nd isotopes imply that the reservoir these lavas were derived from has been distinct from the depleted mantle reservoir since the early Proterozoic. The Sr-Nd-Pb isotope variations of the Deep Springs Valley lavas are unique because they do not plot along either the EM I or EM II arrays. For example, most basalts that have low ɛ_Nd values and unradiogenic ²⁰⁶Pb/²⁰⁴Pb ratios have relatively low ⁸⁷Sr/⁸⁶Sr ratios (the EM I array), whereas basalts with low ɛ_Nd values and high ⁸⁷Sr/⁸⁶Sr ratios have radiogenic ²⁰⁶Pb/²⁰⁴Pb ratios (the EM II array). High-K lavas from Deep Springs Valley have EM II-like Sr and Nd isotope compositions, but EM I-like Pb isotope compositions. A simple method for producing the range of isotopic and major- and trace-element variations in the Deep Springs Valley lavas is by two-component mixing between this unusual K-rich mantle source and a more typical depleted mantle basalt. We favor passage of MORB-like magmas that partially fused and were contaminated by potassic magmas derived from melting high-K mantle veins that were stored in the lithospheric mantle. The origin of the anomalously high ⁸⁷Sr/⁸⁶Sr and ²⁰⁸Pb/²⁰⁴Pb ratios and low ɛ_Nd values and ²⁰⁶Pb/²⁰⁴Pb ratios requires addition of an old component with high Rb/Sr and Th/Pb ratios but low Sm/Nd and U/Pb ratios into the mantle source region from which these basalts were derived. This old component may be sediments that were introduced into the mantle, either during Proterozoic subduction, or by foundering of Proterozoic age crust into the mantle at some time prior to eruption of the lavas. Received: 28 February 1997 / Accepted: 9 July 1998     

Strontium isotope ratios in volcanic rocks from the south-eastern part of the Hellenic arc

Isotopic ratios of strontium in 9 volcanic rocks from the south-eastern part of the Hellenic arc range from 0.7037 to 0.7075. Within individual series of differentiation, there seems to be a correlation between Sr⁸⁷/Sr⁸⁶ and K₂O/SiO₂.All strontium isotope data for the Hellenic arc are reviewed. Comparable (but slightly smaller) ranges of Sr isotope ratios are found in other island arcs with continental basement. To explain the high values of Sr⁸⁷/Sr⁸⁶ ratio for the Hellenic arc, a selective addition of Sr⁸⁷ from the wall rock, and a process of assimilation involving water, perhaps from subducted sediments, are suggested. Since closely-spaced individual volcanic centres of similar ages have very different Sr isotope ratios, and since the range of Sr isotopic composition in individual centres is quite large, the variation is unlikely to be due to primary variation in mantle composition.     

Hydrogeochemistry and strontium isotopes of spring and mineral waters from Monte Vulture volcano,Italy

This paper describes the results of a study that was conducted to determine the relationship between hydrogeochemical composition and ⁸⁷Sr/⁸⁶Sr isotope ratios of the Mt. Vulture spring waters. Forty samples of spring waters were collected from local outcrops of Quaternary volcanites. Physico-chemical parameters were measured in the field and analyses completed for major and minor elements and ⁸⁷Sr/⁸⁶Sr isotopic ratios. A range of water types was distinguished varying from alkaline-earth bicarbonate waters, reflecting less intense water–rock interaction processes to alkali bicarbonate waters, probably representing interaction with volcanic rocks of Mt. Vulture and marine evaporites. The average ⁸⁷Sr/⁸⁶Sr isotope ratios suggest at least 3 different sources. However, some samples have average Sr isotope ratios (0.70704–0.70778) well above those of the volcanites. These ratios imply interaction with other rocks having higher ⁸⁷Sr/⁸⁶Sr ratios, probably Triassic evaporites, which is substantiated by their higher content of Na, SO₄ and Cl. The Sr isotope ratios for some samples (e.g. Toka and Traficante) are intermediate between the value for the Vulture volcanites and that for the local Mesozoic rocks. The salt content of these samples also lies between the value for waters interacting solely with the volcanites and the value measured in the more saline samples. These waters are thus assumed to result from the mixing of waters circulating in volcanic rocks with waters presumably interacting with the sedimentary bedrock (marine evaporites).     

Pb and Sr isotope and geochemical data from the Pb–Zn deposit Bleiberg (Austria): constraints on the age of mineralization

Summary The timing of Zn–Pb mineralization hosted by early dolomitized lagoonal limestones (Crest facies) at Bleiberg (Carinthia, Austria) has been constrained using Sr-isotopes. This late stage Zn–Pb mineralization is a special feature of the Bleiberg deposit. Samples of the mineralized Crest facies are characterized by higher concentrations of minor and trace elements (except Ba and Sr) compared to samples from the weakly mineralized Wetterstein limestone of the lagoonal facies. The samples from the Crest facies indicate that a fluid with a minimum ⁸⁷Sr/⁸⁶Sr ratio of 0.7083 reacted at 210±30 Ma with carbonate rocks having ⁸⁷Sr/⁸⁶Sr ratios of approximately 0.7077 during a late stage of ore formation. The ⁸⁷Sr/⁸⁶Sr ratios correlate with the Mn and Cl concentrations. Lead isotope data of whole rock samples of Bleiberg yielded an isochron age of 180±40 Ma. They furthermore confirm the presence of two types of common lead; an isotopically distinct ore lead component is present within and close to the ore bodies. The other common Pb component is present in host rocks and in gangue minerals and is distinguished from the ore lead by lower ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios. The Sr and the Pb ages are consistent with geological evidence indicating a Triassic age of Pb–Zn mineralization and support genetic models emphasizing the role of bacteriogenic sulfate reduction at low temperatures prior to subsidence and burial. Elevated ⁸⁷Sr/⁸⁶Sr values (>0.7080) of gangue minerals indicate an epigenetic origin of strontium. Our results are consistent with a genetic model postulating formation of the ore-bearing hydrothermal fluids “at depth” where they leached lead from pre-Upper Carboniferous basement rocks.