Diagenesis and Sr isotopic evolution of seawater using data from DSDP 590B and 575

New Sr isotopic and concentration analyses of bulk carbonate and porewaters from a carbonate-rich Miocene section sampled at DSDP Site 575 are reported and used, along with our earlier data from a section of similar age at DSDP Site 590B, in a numerical model to determine for each site the rate of Sr exchange during diagenesis and the degree to which this amount of exchange has shifted the⁸⁷Sr⁸⁶Sr of the bulk carbonate from the ratio each increment of sediment had when first deposited. Despite the fact that the two sites have very different water depth (4536 m at 575 vs. 1299 m at 590B), different sedimentation rate ( 10 m/My at 575 vs. 40 m/My at 590B), and significantly different porewater Sr²⁺ gradients, we find that the rate of Sr exchange as a function of sediment age is almost indistinguishable between the two sites. The rate of Sr exchange determined at the two sites is such that the resulting shift in bulk carbonate⁸⁷Sr⁸⁶Sr due to diagenesis is small compared to the total range of⁸⁷Sr⁸⁶Sr values measured, but large compared to the analytical uncertainty of the individual isotopic ratio measurements. By taking this shift into account we reconstruct the original⁸⁷Sr⁸⁶Sr of each increment of carbonate sampled, which when plotted as a function of age becomes our best estimate of the Sr isotopic evolution of seawater. Because Sr is very well mixed in the ocean, at any given time there is a single worldwide value of seawater⁸⁷Sr⁸⁶Sr. Therefore, if we are quantitatively accounting for the effect Sr exchange, we should find the same seawater evolution curve regardless of what DSDP Site is used. When we compare the observed bulk carbonate⁸⁷Sr⁸⁶Sr vs. age at the two sites they are seen to differ by amounts that are sometimes large compared to the analytical uncertainties of the measurements. However, when these data are corrected for the post-depositional Sr isotopic shifts predicted by our diagenetic model, we find almost perfect agreement. This agreement suggests that we have made a realistic determination of the rate of Sr exchange and its consequences in terms of shifting the⁸⁷Sr⁸⁶Sr of the bulk carbonate, and more importantly, that Sr isotopes can be used to correlate marine sediments with an accuracy comparable to the very small analytical uncertainties of modern isotopic measurements.     

Strontium and its isotopic composition in interstitial waters of marine carbonate sediments

The concentrations and isotopic compositions of strontium in interstitial waters from several DSDP sites, where sediments consist chiefly of carbonate oozes and chalks, are used as indicators of carbonate diagenesis by reference to a recently-produced curve showing detailed variations in the⁸⁷Sr/⁸⁶Sr ratio of seawater with time. Carbonate sediments of the Walvis Ridge show increases in interstitial Sr²⁺ concentrations in the upper carbonate-ooze sections with the highest concentrations near the ooze-chalk boundary where maximum rates of carbonate recrystallization occur. Below this, in situ production of Sr²⁺ diminishes and there is a diffusive flux of Sr to an underlying sink, presumably volcanogenic sediments or basalts, leading to Sr isotopic disequilibrium between carbonates and interstitial waters. In some other sites, however, there is no apparent Sr sink at depth and isotopic equilibrium is retained. Overall, diffusive smoothing of profiles exerts an important control on the⁸⁷Sr/⁸⁶Sr ratios, although lower ratios than contemporaneous seawater values in the carbonate oozes often correlate with zones of Mg²⁺ loss and reflect a combination of a flux of Sr²⁺ from the zone of maximum recrystallization rates together with a contribution from the in situ alteration of volcanic matter.     

The strontium isotopic composition of seawater,and seawater-oceanic crust interaction

The⁸⁷Sr/⁸⁶Sr ratio of seawater strontium (0.7091) is less than the⁸⁷Sr/⁸⁶Sr ratio of dissolved strontium delivered to the oceans by continental run-off (～0.716). Isotope exchange with strontium isotopically lighter oceanic crust during hydrothermal convection within spreading oceanic ridges can explain this observation. In quantitative terms, the current⁸⁷Sr/⁸⁶Sr ratio of seawater (0.7091) may be maintained by balancing the continental run-off flux of strontium (0.59 × 10¹² g/yr) against a hydrothermal recirculation flux of 3.6 × 10¹² g/yr, during which the⁸⁷Sr/⁸⁶Sr ratio of seawater drops by 0.0011. A concomitant mean increase in the⁸⁷Sr/⁸⁶Sr ratio of the upper 4.5 km of oceanic crust of 0.0010 (0.7029–0.7039) should be produced. This required⁸⁷Sr enrichment has been observed in hydrothermally metamorphosed ophiolitic rocks from the Troodos Massif, Cyprus.The post-Upper Cretaceous increase in the strontium isotopic composition of seawater(～0.7075–0.7091) covaries smoothly with inferred increase in land area. This suggests that during this period the main factor which has caused variability in the⁸⁷Sr/⁸⁶Sr ratio of seawater strontium could have been variation in the magnitude of the continental run-off flux caused by variation in land area. Variations in land area may themselves have been partly a consequence of variations in global mean sea-floor spreading rate.     

Evaluation and application of the ion microprobe in the strontium isotope geochemistry of carbonates

A modified AEI-IM20 ion microprobe has been used to measure⁸⁷Sr/⁸⁶Sr ratios in carbonates. A suite of carbonates with varying major elements (Ca, Mg, Fe, Mn) was studied at low and high (M/ΔM ? 3000) mass resolution to determine the types and intensities of molecular species isobaric with Sr peaks; Sr data collected at low mass resolution must be corrected for Ca₂ and CaMgO species. Rb/Sr ratios are extremely low, and correction for⁸⁷Rb is not required (< 0.1‰ of⁸⁷Sr).Usable Sr isotopic data may be obtained from calcite givenSr≥ 400ppm, and for Sr > 5000 ppm a precision of ～ ± 1‰ (± 0.0007) in⁸⁷Sr/⁸⁶Sr (2σ mean) can be achieved under optimum conditions. The corrections for Ca₂ and CaMgO are smaller than the within-run precision in calcite, but in dolomite the correction for CaMgO is + 1.5%. Mass fractionation corrections to⁸⁷Sr/⁸⁶Sr (based on⁸⁶Sr/⁸⁸Sr= 0.1194) are typically +8 to +10‰. Good agreement between ion probe and solid source mass spectrometer results was found for calcites of known Sr isotopic composition: ST4a (～ 400ppm Sr), average ion probe⁸⁷Sr/⁸⁶Sr= 0.7267 ± 0.0015, solid source⁸⁷Sr/⁸⁶Sr= 0.72680 ± 0.00008 [14]; JCG36 (～ 6000ppm Sr), average ion probe⁸⁷Sr/⁸⁶Sr= 0.7056 ± 0.0009, solid source⁸⁷Sr/⁸⁶Sr= 0.70588 ± 0.00009 [16]; JCG44 (～ 6000ppm Sr), average ion probe⁸⁷Sr/⁸⁶Sr= 0.7057 ± 0.0006, solid source⁸⁷Sr/⁸⁶Sr= 0.70540 ± 0.00008 [16]. The ability of the ion microprobe to measure⁸⁷Sr/⁸⁶Sr for 10-μm spots in calcite was used: (1) to measure variation in⁸⁷Sr/⁸⁶Sr of ～ 0.01 on a centimetre scale in a hydrothermally altered basalt from the Isle of Skye, northwestern Scotland; and (2) to determine the Sr isotopic composition of tiny (< 35 μm) calcite grains in a veined mantle lherzolite from Bultfontein, South Africa. Because of calcite's ubiquitous occurrence in many parageneses this technique may offer many opportunities for the measurement of fine scale heterogeneities in⁸⁷Sr/⁸⁶Sr.     

Geochemical evidence for non-marine depositional environment of foraminiferal fossils from the Nihewan Basin, China

From the first finding in 1970s, the findings of foraminiferal fossil assemblages in inland basins have been reported from time to time, especially in recent years. The debates on the depositional environment of foraminiferal fossils have become the hot spot of researches again in China. Based on the researches of trace element geochemistry and electron scanning microscope of shells of Quaternary foraminiferal fossils from the Xiaodukou section in the inland Nihewan basin, the original ⁸⁷Sr/⁸⁶Sr and other geochemical information of shells were believed to be preserved well and could be used to rebuild the geochemistry of contemporary waters where foraminifera deposited, although there existed some effects of burial diagenesis on the geochemistry of shells to a certain extent. The ⁸⁷Sr/⁸⁶Sr ratios of well-preserved Xiaodukou foraminiferal shells were measured, giving a range of 0.711190±25–0.712018±14, apparently higher than the value of contemporary seawater (0.709087–0.709147) and similar to that of the Sanggan River, proving that it represented the value of the ancient lacustrine water. The hyperbolic mixing models of ⁸⁷Sr/⁸⁶Sr-palaeosalinity and ⁸⁷Sr/⁸⁶Sr-Sr/Ca indicated that the contemporary waters where Xiaodukou foraminifera inhabited was an inland lake and there was no seawater input to the depositional environment.     

87Sr/86Sr ratios in hydrothermal waters and deposits from the East Pacific Rise at 21°N

⁸⁷Sr/⁸⁶Sr ratios of three hydrothermal waters collected on the East Pacific Rise at 21°N define a mixing line between seawater and a hydrothermal end-member at 0.7030 which is derived by seawater-basalt interaction at ca. 350°C and water/rock ratio of about 1.5. Sr concentrations are not affected in the process while Mg uptake from seawater is almost complete. Up to2/3 of this hydrothermal component is involved in anhydrite precipitation while the Sr isotopic ratio in sulfides (chalcopyrite + sphalerite) cannot be distinguished from that of sulfate. It is estimated that ca. 1 × 10¹⁰ moles of strontium are yearly cycled in the hydrothermal systems of mid-oceanic ridges, thereby affecting the⁸⁷Sr/⁸⁶Sr budget of seawater. Mass balance between river runoff, limestone precipitation and ridge basalt alteration suggests that the⁸⁷Sr/⁸⁶Sr ratios of the river runoff are in the range 0.7097–0.7113, and are largely dominated by limestone alteration.     

Sr fluxes and isotopic compositions of the eleven rivers originating from the Qinghai-Tibet Plateau and their contributions to <Superscript>87</Superscript>Sr/<Superscript>86</Superscript>Sr evolution of seawater

To evaluate influence of chemical weathering of the Qinghai-Tibet Plateau (QTP) on seawater ⁸⁷Sr/⁸⁶Sr variation, river water and sediment samples were collected, and their Sr concentrations and isotopic compositions analyzed, from the seven large rivers that originated from the QTP. By combining these with the data of the Ganges, Brahmaputra, Indus and Irrawaddy originated in the southern QTP, the total Sr flux of the eleven rivers reaches 3.47×10⁹ mol·a⁻¹, which accounts for 10.2% of the total Sr flux transported by the global rivers. The weighted mean ⁸⁷Sr/⁸⁶Sr is 0.71694, higher than the average value of the global rivers. The ⁸⁷Sr_ex (⁸⁷Sr flux in excess of the seawater ⁸⁷Sr/⁸⁶Sr ratio) of the Chinese seven rivers is 1.55×10⁶ mol·a⁻¹, only accounting for about 6% of the value of the eleven rivers originated from QTP, and the Ganges-Brahmaputra system accounts for 86%. We assume that the QTP rivers have no strontium contributions to the oceans before ∼40 Ma and the Sr fluxes of the global rivers, except the QTP eleven rivers, are constant, then a maximum linear increase in Sr fluxes of the QTP rivers from zero to the modern value in response to tectonic uplift can explain ∼69% increase of seawater ⁸⁷Sr/⁸⁶Sr over the past ∼40 Ma and the remainder of 31% is perhaps provided from other factors. Supported by National Natural Science Foundation of China (Grant Nos. 40473009, 40331001, 40873001)     

Strontium and oxygen isotopic composition of some basalts from Hole 504B,Costa Rica Rift,DSDP Legs 69 and 70

Seventeen whole-rock samples, generally taken at 25–50 m intervals from 5 to 560 m sub-basement in Hole 504B, drilled in 6.2 m.y. old crust, were analysed for⁸⁷Sr/⁸⁶Sr ratios, Sr and Rb concentrations, and¹⁸O/¹⁶O ratios. Sr isotope ratios for 8 samples from the upper 260 m of the hole range from 0.70287 to 0.70377, with a mean of 0.70320. In the 330–560 m interval, 5 samples have a restricted range of 0.70255–0.70279, with a mean of 0.70266, the average value for fresh mid-ocean ridge basalts (MORB). In the 260–330 m interval, approximately intermediate Sr isotopic ratios are found.δ¹⁸O values (‰) range from 6.4 to 7.8 in the upper 260 m, 6.2–6.4 in the 270–320 m interval, and 5.8–6.2 in the 320–560 m interval. The values in the upper 260 m are typical for basalts which have undergone low-temperature seawater alteration, whereas the values for the 320–560 m interval correspond to MORB which have experienced essentially no oxygen isotopic alteration.The higher⁸⁷Sr/⁸⁶Sr and¹⁸O/¹⁶O ratios in the upper part of the hole can be interpreted as the result of a greater overall water/rock ratio in the upper part of the Hole 504B crust than in the lower part. Interaction of basalt with seawater(⁸⁷Sr/⁸⁶Sr=0.7091) increased basalt⁸⁷Sr/⁸⁶Sr ratios and produced smectitic alteration products which raised whole-rock δ¹⁸O values. Seawater circulation in the lower basalts may have been partly restricted by the greater number of relatively impermeable massive lava flows below about 230 m sub-basement. These flows may have helped to seal off lower basalts from through-flowing seawater.     

Multi-approach characterization of shallow-water carbonates off Minamitorishima and their depositional settings/history

Sedimentological, geochemical, and chronological analyses were carried out on 18 carbonate rock samples collected at depths of 938, 1085, and 3354 m on the western slope of Minamitorishima (Marcus Island), which is located near the western margin of the Pacific Plate. Four groups of carbonate rocks were distinguished: a mollusk-rich limestone, a coral-rich dolomite, a foraminiferal-nannofossil packstone, and a phosphatized mudstone/wackestone. The mollusk-rich limestone is characterized by the dominance of bivalves (including rudists) and gastropod shells. Strontium isotope ratios (⁸⁷Sr/⁸⁶Sr) and Mesorbitolina ex gr. texana (a large benthic foraminifer) indicate that the shallow-water carbonates were deposited during the late Aptian–early Albian (ca. 123–111 Ma). The coral-rich dolomite is characterized by abundant scleractinian corals and nongeniculate coralline algae associated with encrusting acervulinid foraminifers. The biotic composition is similar to that of the Oligocene–Pleistocene carbonates reported from other seamounts in the northwestern Pacific. Geochemical data show that the coral-rich carbonates were dolomitized at 9.5–6.8 Ma (Tortonian–Messinian) and that normal seawater was the most likely parent fluid. The foraminiferal-nannofossil packstone is a semi-consolidated foraminiferal-nannofossil ooze and was deposited during the Pleistocene (0.99–0.45 Ma). The phosphatized mudstone/wackestone is marked by the absence of macrofossils and the presence of traces of planktic foraminifers. Although its depositional age is not constrained, the Sr isotope ratios indicate that the phosphatization occurred at 33.2–28.9 Ma. After the deposition of the Cretaceous shallow-water carbonates, including the mollusk-rich limestone, Minamitorishima was drowned and its top was covered with a pelagic cap, represented by the mudstone/wackestone. The late Eocene–early Oligocene volcanism (40.2–33.2 Ma) caused episodic uplift and returned the top of Minamitorishima to a shallow-water environment. After the early Oligocene phosphatization of the pelagic cap, coral reefs flourished on the top of this island. The reef limestone was dolomitized during the Tortonian–Messinian.     

Subaqueous volcanism in the Paleo-Pacific Ocean based on Jurassic basaltic tuff and pillow basalt in the Raohe Complex,NE China

On-land records of subaqueous explosive volcanic eruptions are rarely reported.To understand this phenomenon and discuss its global significance,we studied the geochronology and geochemistry of basaltic tuff and pillow basalt in the Raohe Complex,NE China.The basaltic tuff consists of well-sorted vitreous,crystal(mostly clinopyroxene),and minor lithic fragments.It is characterized by a high Mg O(15.7–15.9%)content and zero Eu anomalies(Eu/Eu~*=99–102).The tuff erupted at 172±1 Ma based on SHRIMP zircon U-Pb dating,coeval with the previously reported age of the pillow basalt.The pillow basalt has intermediate Mg O content and weakly negative Eu anomalies(Eu/Eu~*=90–99).Based on immobile trace element discrimination,the basaltic tuff and pillow basalt belong to alkali basalt displaying an OIB-type trace element pattern,and consistent Nd isotope signatures ofε_(Nd)(t)=4.4–6.2,indicating an identical mantle source.The pillow basalt has coupled Sr-Nd isotopic values,whereas the basaltic tuff has significantly higher initial~(87)Sr/~(86)Sr values that are similar to synchronous seawater.This indicates that the elemental exchange between the mantle-derived material and seawater most likely occurred in a subaqueous explosive volcanic eruption,rather than in an effusive eruption.Detailed calculations suggest that the high efficiency of the Sr-isotope exchange between seawater and the mantle-derived material triggered by a subaqueous explosive volcanic eruption is likely one of the main reasons for the rapid decrease of the global seawater~(87)Sr/~(86)Sr value.     

87Sr enrichment of ophiolitic sulphide deposits in Cyprus confirms ore formation by circulating seawater

The hypothesis that seawater was the source of the hydrothermal fluid which formed the Upper Cretaceous ophiolitic cupriferous pyrite ore desposits of the Troodos Massif (Cyprus) has been tested by analysing the strontium isotopic composition of thirteen mineralized samples from four mines. Initial⁸⁷Sr/⁸⁶Sr ratios range from 0.7052 ± 0.0001 to 0.7075 ± 0.0002, the latter value being indistinguishable from that of Upper Cretaceous seawater at 0.7076 ± 0.0006 (2σ). Hence, the mineralized metabasalt samples have been contaminated with⁸⁷Sr, relative to initial magmatic strontium isotope ratios of the Troodos ophiolitic complex (0.70338 ± 0.00010 to 0.70365 ± 0.00005).Since seawater was the only source of strontium available during formation of the Troodos Complex which was isotopically relatively enriched in⁸⁷Sr, the data confirm that seawater was the source of the hydrothermal oreforming fluid.     

Weathering,Sr fluxes,and controls on water chemistry in the Lake Qinghai catchment,NE Tibetan Plateau

Strontium (Sr) concentrations and isotopic ratios have been measured in a series of water and rock samples from most of the major tributaries of the Lake Qinghai basin on the north‐eastern Tibetan Plateau. Dissolved Sr and ⁸⁷Sr/⁸⁶Sr show ranges of 488–12 240 nmol/l and 0·710497–0·716977, respectively. These data, together with measurements of major cations and anions in rivers and their tributaries and various lithologies of the catchment, were used to determine the contributions of Sr and its isotopic expense to rivers and lakes. Our results demonstrate that the chemical components and ⁸⁷Sr/⁸⁶Sr ratios of the alkaline waters are derived from mixing of carbonate and silicate sources, with the former contributing 72 ± 18% dissolved Sr to rivers. The difference in tributary compositions stems from the lithology of different river systems and low weathering intensity under a semi‐arid condition. Variation in ⁸⁷Sr/⁸⁶Sr ratios places constraint on the Sr‐isotopic compositions of the main tributaries surrounding Lake Qinghai. The water chemistry of the Buha River, the largest river within the catchment underlain by the late Paleozoic marine limestone and sandstones, dominates Sr isotopic composition of the lake water, being buffered by the waters from the other rivers and probably by groundwater. However, the characteristic chemical composition of the lake itself differs remarkably from the rivers, which can be attributed to precipitation of authigenic carbonates (low‐magnesium calcite, aragonite, and dolomite), though this does not impact the Sr isotope signature, which may remain a faithful indicator in paleo‐records. Regarding the potential role of groundwater input within the Lake Qinghai systems in the water budget and water chemistry, we have also determined the Sr concentration and ⁸⁷Sr/^S6Sr ratio of groundwater from diverse environments. This has allowed us to further constrain the Sr isotope systematic of this source. A steady‐state calculation gives an estimate for the groundwater flux of 0·19 ± 0·03 × 10⁸ m³/yr, accounting for about 8% of contemporary lake Sr budget. Copyright © 2010 John Wiley & Sons, Ltd.     

Temporal variations in Sr and 87Sr/86Sr of the Ganga headwaters: estimates of dissolved Sr flux to the mainstream

The headwaters of the Ganga (the Alaknanda, Bhagirathi and the Ganga) were analysed for their dissolved major ions, Sr and ⁸⁷Sr/⁸⁶Sr on a biweekly to monthly basis over a period of one year to determine their temporal variations and the factors contributing to them. The concentrations of major ions and Sr show significant seasonal variation with lower values during monsoon period in all the three rivers. A similar trend is also observed for ⁸⁷Sr/⁸⁶Sr and Na*/Ca (Na* = Na_r? Cl_r) suggesting relatively lower contribution of Sr and Na from silicates (which are more radiogenic in Sr) during monsoon. Budget calculations show that silicate derived dissolved Sr (Sr_s) in the river Ganga, Alaknanda and the Bhagirathi varied from 10 ± 4 to 27 ± 11, 7 ± 3 to 30 ± 12, 16 ± 6 to 57 ± 23% of measured Sr respectively with lower values during monsoon. The relative decrease in silicate erosion compared to carbonate during monsoon can result from several factors, these include higher dissolution kinetics of the carbonates, lower water–rock interaction time and availability of larger area for weathering. The annual discharge weighted Sr flux derived from the time series data is higher by ～20% from that based on peak flow Sr, and lower by ～40% compared to that derived from lean flow Sr concentration. The area‐normalized annual flux of dissolved Sr from the Ganga at Rishikesh is about five times its flux at Rajshahi (Bangladesh) and a few other major global rivers, such as the Amazon, indicating higher erosion rate over the Himalaya. Copyright © 2010 John Wiley & Sons, Ltd.     

Evidence for fluid flow in the Japan Trench forearc using isotope geochemistry (Cl, Sr, B): Results from ODP Site 1150

Abstract Interstitial pore waters from Ocean Drilling Program Site 1150, where ～1200 m of sub‐sea‐floor sediment from the upper Japan Trench forearc were recovered, were analyzed for element concentrations and Cl, Sr and B isotopes. Although chlorinity showed profound down‐hole freshening to values as low as ～310 mm (0.55 × seawater) in the deeper part of the claystone‐dominated succession, both Sr and B concentrations showed an overall increase. Sr reached concentrations of up to >250 µm (～3.00 × seawater), whereas B‐enrichment was even stronger (3920 µm; i.e. 9.30 × seawater). The strong variations in concentration correspond to fractionation reactions in the deep, tectonically deformed part of the forearc. The heavily fractured portion of Site 1150 (from ～700 m to the total depth of the hole) has two shear zones that very likely act as conduits that expel deep‐seated fluids to the sea floor. These fluids not only showed the strongest freshening of Cl, but were also characterized by low δ³⁷Cl measurements (down to ?1.1‰), the heaviest δ¹¹B measurements (～40–46‰) and the least radiogenic ⁸⁷Sr/ ⁸⁶Sr measurements. The profound isotope anomalies together with the excursions in element concentrations suggest that diagenetic processes operate at that depth. These include clay mineral diagenesis, alteration of tephra from the Japan and Izu Arcs, and possibly transformation of biogenic silica from abundant diatoms. Given the strong enrichment of some mobile elements (e.g. Sr, B, Li), enhanced fluid flow through permeable penetrative faults through the forearc (like the shear zones at Site 1150) could be an efficient mechanism for back‐flux of those elements from the deep forearc into the hydrosphere.     

Sr isotope evolution during chemical weathering of granites —Impact of relative weathering rates of minerals

The Sr isotopic systematics in the weathering profiles of biotite granite and granite porphyry in southern Jiangxi Province were investigated. The results showed that during the chemical weathering of granites, remarked fractionation occurred between Rb and Sr. During the early stages of chemical weathering of granites, the released Sr/Si and Sr/Ca ratios are larger than those of the parent rocks, and the leaching rate of Sr is higher than those of Si, Ca, K, Rb, etc. Dynamic variations in relative weathering rates of the main Sr-contributing minerals led to fluctuation with time in⁸⁷Sr/⁸⁶Sr ratios of inherent and released Sr in the weathering crust of granite. Successive weathering of biotite, plagioclase and K-feldspar made⁸⁷Sr/⁸⁶Sr ratios in the weathering residues show such a fluctuation trend as to decrease first, increase, and then decrease again till they maintain stable. This work further indicates that when Sr isotopes are used to trace biogeochemical processes on both the catchment and global scales, one must seriously take account of the preferential release of Sr from dissolving solid phase and the fluctuation of⁸⁷Sr/⁸⁶Sr ratios caused by the variations of relative weathering rates of Sr-contributing minerals.     

Strontium and neodymium isotopic evidence for the heterogeneous nature and development of the mantle beneath Afar (Ethiopia)

Neodymium isotope and REE analyses of recent volcanic rocks and spinel lherzolite nodules from the Afar area are reported. The¹⁴³Nd/¹⁴⁴Nd ratios of the volcanic rocks range from 0.51286 to 0.51304, similar to the range recorded from Iceland. However, the⁸⁷Sr/⁸⁶Sr ratios display a distinctly greater range (0.70328–0.70410) than those reported from the primitive rocks of Iceland. Whole rock samples and mineral separates from the spinel lherzolite nodules exhibit uniform¹⁴³Nd/¹⁴⁴Nd ratios (ca. 0.5129) but varied⁸⁷Sr/⁸⁶Sr ratios in the range 0.70427–0.70528.The SrNd isotope variations suggest that the volcanic rocks may have been produced by mixing between two reservoirs with distinct isotopic compositions. Two possible magma reservoirs in this area are the source which produced the “MORB-type” volcanics in the Red Sea and Gulf of Aden and the anomalous source represented by the nodule suite. The isotopic composition of the volcanics is compatible with mixing between these two reservoirs.It is shown that the anomalous source with a high⁸⁷Sr/⁸⁶Sr ratio cannot have been produced by simple processes of partial melting and mixing within normal mantle. Instead the high⁸⁷Sr/⁸⁶Sr is equated with a fluid phase. A primitive cognate fluid, subducted seawater or altered oceanic lithosphere may have been responsible for the generation of the source with a high⁸⁷Sr/⁸⁶Sr ratio.     

The δ13C–δ18O variations in marble in the Hida Belt,Japan

Marble has a great potential to understand a history of various geological events occurring during tectonic processes. In order to decode metamorphic–metasomatic records on C–O isotope compositions of marble at mid-crustal conditions, we conducted a C–O–Sr isotope study on upper amphibolite-facies marbles and a carbonate–silicate rock from the Hida Belt, which was once a part of the crustal basement of the East Asian continental margin. Carbon and oxygen isotope analyses of calcite from marbles (Kamioka area) and a carbonate–silicate rock (Wadagawa area) show a large variation of δ¹³C [VPDB] and δ¹⁸O [VSMOW] values (from −4.4 to +4.2 ‰ and +1.6 to +20.8 ‰, respectively). The low δ¹³C values of calcites from the carbonate–silicate rock (from −4.4 to −2.9 ‰) can be explained by decarbonation (CO₂ releasing) reactions; carbon–oxygen isotope modeling suggests that a decrease of δ¹³C strongly depends on the amount of silicate reacting with carbonates. The occurrence of metamorphic clinopyroxene in marbles indicates that all samples have been affected by decarbonation reactions. All δ¹⁸O values of calcites are remarkably lower than the marine-carbonate values. The large δ¹⁸O variation can be explained by the isotope exchange via interactions between marble, external fluids, and/or silicates. Remarkably low δ¹⁸O values of marbles that are lower than mantle value (~+5 ‰) suggest the interaction with meteoric water at a later stage. Sr isotope ratios (⁸⁷Sr/⁸⁶Sr = 0.707255–0.708220) might be close to their protolith values. One zircon associated with wollastonite in a marble thin-section yields a U–Pb age of 222 ± 3 Ma, which represents the timing of the recrystallization of marble, triggered by H₂O-rich fluid infiltration at a relatively high-temperature condition. Our isotope study implies that the upper amphibolite-facies condition, like the Hida Belt, might be appropriate to cause decarbonation reactions which can modify original isotope compositions of marble if carbonates react with silicates.     

Pb and Sr isotopic systematics of some basalts and sulfides from the East Pacific Rise at 21°N (project RITA)

Tholeiitic basalts and sulfide deposits from the “Cyana” and “Alvin” diving programs (RITA project) on the East Pacific Rise were analyzed for Pb and Sr isotopes. The basalt data plot within the field defined previously by other East Pacific Rise basalts (²⁰⁶Pb/²⁰⁴Pb: 18.35–18.58;²⁰⁷Pb/²⁰⁴Pb: 15.48–15.53;²⁰⁸Pb/²⁰⁴Pb: 37.8–38.1;⁸⁷Sr/⁸⁶Sr: 0.7022–0.7025). Pb, U and Sr contents (～0.5, ～0.05 and ～110 ppm, respectively) and μ values (～6) are typical of MORB, whereas Th/U ratios (～3.5) are significantly higher.The Pb isotopic ratios of the sulfide samples are very homogeneous (²⁰⁶Pb/²⁰⁴Pb～18.47²⁰⁷Pb/²⁰⁴Pb～15.49²⁰⁸Pb/²⁰⁴Pb～37.90), and plot in the middle of the basalt field. This indicates that (1) the sulfide Pb was derived from the basaltic crust without any significant contribution from either seawater or hemipelagic sediments, and (2) the solutions from which the sulfides were deposited had uniform Pb isotopic composition. The Pb contents of three sulfide samples is relatively high (170–1310 ppm).The Sr contents of five sulfide samples are widely scattered from 12 to 210 ppm, with⁸⁷Sr/⁸⁶Sr ratios intermediate between basaltic and seawater values (0.70554±0.00005 to0.70795±0.00011). Leaching experiments show that both basalt-derived Sr and seawater Sr were present in the solutions which deposited the sulfides. In some cases, Sr was also adsorbed from seawater onto the sulfides following their deposition. Basalt-derived Sr and seawater Sr are also present in associated non-sulfide phases.     

Strontium in rivers of the Baltic Basin

The rivers in the Baltic Basin drain a mixture of bedrocks ranging from Mesozoic-Paleozoic sediments in the south to Proterozoic-Archean intrusives in the north. The rivers in the sedimentary basin in the south have high concentrations of Sr, in the interval 100–500 µg l^–1 while the⁸⁷Sr/⁸⁶Sr ratio is close to that of seawater, i.e. 0.71. The northern rivers in the Precambrian shield area on the other hand have low Sr concentrations of 15–50 µg l^–1 with high⁸⁷Sr/⁸⁶Sr ratios of about to 0.73 (0.721–0.745). The riverine input of dissolved Sr to the brackish Baltic Sea approaches 60 tons year^–1, with a weighted mean concentration approaching 130 µg l^–1 and a weighted mean⁸⁷Sr/⁸⁶Sr ratio close to 0.712. Although the sedimentary area in the south supplies only about 43% of the total river discharge, it gives about 88% of the total Sr input. Because of this and the strong regional riverine variation in⁸⁷Sr/⁸⁶Sr ratio, Sr and its isotopes seem to be a convenient tool to unveil mixing relations of water masses in the northern Baltic Sea, provided high resolution analyses are applied. For an overall characterization of water mixing in the Baltic Sea, the Nd system will be superior to that of Sr.     

Dissolved major ions,Sr and 87Sr/86Sr of coastal lakes from Larsemann hills,East Antarctica: Solute sources and chemical weathering in a polar environment

Dissolved major ions, Sr concentrations and ⁸⁷Sr/⁸⁶Sr ratios of 10 coastal lakes from the Larsemann Hills, East Antarctica have been studied to constrain their solute sources, transport and glacial weathering patterns in their catchments. In absence of perennial river/streams, lakes serve as only reliable archive to study land surface processes in these low-temperature regions. The lake water chemistry is mostly Na-Cl type and it does not show any significant depth variations. Sr isotope compositions of these lakes vary from 0.7110 to 0.7211 with an average value of 0.7145, which is higher than modern seawater value. In addition to oceanic sources, major ions and Sr isotopic data show appreciable amount of solute supply from chemical weathering of silicate rocks in lake catchments and dissolution of Ca-Mg rich salts produced during the freezing of seawaters. The role of sulphide oxidation and carbonate weathering are found to be minimal on lake hydro-chemistry in this part of Antarctica. Inverse model calculations using this chemical dataset provide first-order estimates of dissolved cations and Sr; they are mostly derived from oceanic (seawater + snow) sources (cations approximately 76%) and (Sr approximately 92%) with minimal supplies from weathering of silicates (cations approximately 15%); (Sr approximately 2%) and Ca-rich minerals (cations approximately 9%); (Sr approximately 7%). The silicate weathering rate and its corresponding atmospheric CO₂ consumption rate estimates for Scandrett lake catchment (3.6 ± 0.3 tons/km²/year and 0.5 × 10⁵ moles/km²/year), are lower than that of reported values for the average global river basins (5.4 tons/km²/year and 0.9 × 10⁵ tons/km²/year) respectively. The present study provides a comprehensive report of chemical weathering intensity and its role in atmospheric CO₂ consumption in low-temperature pristine environment of Antarctica. These estimates underscore the importance of Antarctica weathering on atmospheric CO₂ budget, particularly during the past warmer periods when the large area was exposed and available for intense chemical weathering.