The role of disseminated calcite in the chemical weathering of granitoid rocks

Accessory calcite, present at concentrations between 300 and 3000 mg kg⁻¹, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO₂, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57–98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering.The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport-limited weathering. These results indicate that the weathering of accessory calcite may strongly influence Ca and alkalinity fluxes from silicate rocks during and following periods of glaciation and tectonism but is much less important for older stable geomorphic surfaces.     

Sr isotopic and elemental characteristics of calcites in the Chinese deserts: Implications for eolian Sr transport and seawater Sr evolution

Calcite content, Sr concentrations, and isotopes of calcites in the Chinese deserts are systematically studied in this paper. Calcite contents, which are calculated according to acid-soluble Ca contents in the deserts, are generally higher in the sandy deserts than in the sandy lands and decrease roughly from northwest to northeast of China. Acid-soluble Sr is well correlated with calcite in the Chinese deserts, implying acid-soluble Sr comes mainly from the calcite dissolution. Sr concentrations in calcites, calculated on the basis of calcite contents and acid-soluble Sr concentrations in the deserts, have an inverse relation to calcite contents, essentially mirroring the degree of Sr substitution for Ca in the calcite development. Desert calcites have regional variations in Sr isotopic ratios. Calcite Sr isotopic ratios depend on geological settings and chemical weathering. The Badain Jaran, and Tengger deserts are probably affected by additional factors such as the remote groundwater cycle or overturning of underlying sand deposits.Only four deserts (Taklimakan, Qaidam, Badain Jaran, and Tengger) appear to be potential sources of eolian deposits in the Chinese Loess Plateau (CLP). Isotopic signatures of calcite Sr and silicate Nd further indicate that the Tengger desert was not an important source for eolian deposits in the CLP. Eolian calcite was probably enriched due to wind sorting from the potential sources to the CLP and suffered weathering–leaching after it accumulated in the CLP. Sr isotopic compositions and Ca/Sr molar ratios of calcites are different between the deserts and the Lingtai profile, due to the integrated effect of wind sorting and weathering–leaching.It is essential to calculate accurately the ⁸⁷Sr/⁸⁶Sr ratio and Sr concentration of eolian calcite entering the oceans according to geochemical data of the Chinese deserts, because of the importance of the Chinese deserts in the global dust cycle. The calculated Sr concentration and ⁸⁷Sr/⁸⁶Sr ratio of eolian calcite entering the North Pacific Ocean, are 11.75 μmol/g and 0.71032, respectively. The calculated values in this study are close to the recommended values by Jacobson [Jacobson A. D. (2004) Has the atmospheric supply of dissolved calcite dust to seawater influenced the evolution of marine ⁸⁷Sr/⁸⁶Sr ratios over the past 2.5 million years? Geochem. Geophys. Geosyst. 5(12), 1–9, Q12002. doi:10.1029/2004GC000750]. Using the same model as that of Jacobson (2004), the effect of Asia dust on the evolution of seawater Sr isotopes is evaluated. (⁸⁷Sr/⁸⁶Sr)_seawater increases by 0.3 × 10⁻⁵ if the lower dust flux of 2.34 × 10⁸ mol Sr/yr is used in the model, suggesting the little effect of Asian dust on the seawater Sr record in the Quaternary. The increase in (⁸⁷Sr/⁸⁶Sr)_seawater is 1.5 × 10⁻⁵ if the higher value of 1.17 × 10⁹ mol Sr/yr is used, as observed in the Quaternary Sr record. These results further support the suggestions of Jacobson (2004).     

Relative contributions of silicate and carbonate rocks to riverine Sr fluxes in the headwaters of the Ganges

Exhumation of the Himalayan-Tibetan orogen is implicated in the marked rise in seawater ⁸⁷Sr/⁸⁶Sr ratios since 40 Ma. However both silicate and carbonate rocks in the Himalaya have elevated ⁸⁷Sr/⁸⁶Sr ratios and there is disagreement as to how much of the ⁸⁷Sr flux is derived from silicate weathering. Most previous studies have used element ratios from bedrock to constrain the proportions of silicate- and carbonate-derived Sr in river waters. Here we use arrays of water compositions sampled from the head waters of the Ganges in the Indian and Nepalese Himalaya to constrain the end-member element ratios. The compositions of tributaries draining catchments restricted to a limited range of geological units can be described by two-component mixing of silicate and carbonate-derived components and lie on a plane in multicomponent composition space. Key elemental ratios of the carbonate and silicate components are determined by the intersection of the tributary mixing plane with the planes Na = 0 for carbonate and constant Ca/Na for silicate. The fractions of Sr derived from silicate and carbonate sources are then calculated by mass-balance in Sr-Ca-Mg-Na composition space. Comparison of end-member compositions with bedrock implies that secondary calcite deposition may be important in some catchments and that dissolution of low-Mg trace calcite in silicate rocks may explain discrepancies in Sr-Ca-Na-Mg covariation. Alternatively, composition-dependent precipitation or incongruent dissolution reactions may rotate mixing trends on cation-ratio diagrams. However the calculations are not sensitive to transformations of the compositions by incongruent dissolution or precipitation processes provided that the transformed silicate and carbonate component vectors are constrained. Silicates are calculated to provide ∼50% of the dissolved Sr flux from the head waters of the Ganges assuming that discrepancies between Ca-Mg-Na covariation and the silicate rock compositions arise from addition of trace calcite. If the Ca-Mg-Na mixing plane is rotated by composition-dependent secondary calcite deposition, this estimate would be increased. Moreover, when ⁸⁷Sr/⁸⁶Sr ratios of the Sr inputs are considered, silicate Sr is responsible for 70 ± 16% (1σ) of the ⁸⁷Sr flux forcing changes in seawater Sr-isotopic composition. Since earlier studies predict that silicate weathering generates as little as 20% of the total Sr flux in Himalayan river systems, this study demonstrates that the significance of silicate weathering can be greatly underestimated if the processes that decouple the water cation ratios from those of the source rocks are not properly evaluated.     

Reconciling the elemental and Sr isotope composition of Himalayan weathering fluxes: insights from the carbonate geochemistry of stream waters

Determining the relative proportions of silicate vs. carbonate weathering in the Himalaya is important for understanding atmospheric CO₂ consumption rates and the temporal evolution of seawater Sr. However, recent studies have shown that major element mass-balance equations attribute less CO₂ consumption to silicate weathering than methods utilizing Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations. To investigate this problem, we compiled literature data providing elemental and ⁸⁷Sr/⁸⁶Sr analyses for stream waters and bedrock from tributary watersheds throughout the Himalaya Mountains. In addition, carbonate system parameters (P_CO2, mineral saturation states) were evaluated for a selected suite of stream waters. The apparent discrepancy between the dominant weathering source of dissolved major elements vs. Sr can be reconciled in terms of carbonate mineral equilibria. Himalayan streams are predominantly Ca²⁺-Mg²⁺-HCO₃⁻ waters derived from calcite and dolomite dissolution, and mass-balance calculations demonstrate that carbonate weathering contributes ∼87% and ∼76% of the dissolved Ca²⁺ and Sr²⁺, respectively. However, calculated Ca/Sr ratios for the carbonate weathering flux are much lower than values observed in carbonate bedrock, suggesting that these divalent cations do not behave conservatively during stream mixing over large temperature and P_CO2 gradients in the Himalaya.The state of calcite and dolomite saturation was evaluated across these gradients, and the data show that upon descending through the Himalaya, ∼50% of the streams evaluated become highly supersaturated with respect to calcite as waters warm and degas CO₂. Stream water Ca/Mg and Ca/Sr ratios decrease as the degree of supersaturation with respect to calcite increases, and Mg²⁺, Ca²⁺, and HCO₃⁻ mass balances support interpretations of preferential Ca²⁺ removal by calcite precipitation. On the basis of patterns of saturation state and P_CO2 changes, calcite precipitation was estimated to remove up to ∼70% of the Ca²⁺ originally derived from carbonate weathering. Accounting for the nonconservative behavior of Ca²⁺ during riverine transport brings the Ca/Sr and ⁸⁷Sr/⁸⁶Sr composition of the carbonate weathering flux into agreement with the composition of carbonate bedrock, thereby permitting consistency between elemental and Sr isotope approaches to partitioning stream water solute sources. These results resolve the dissolved Sr²⁺ budget and suggest that the conventional application of two-component Ca/Sr and ⁸⁷Sr/⁸⁶Sr mixing equations has overestimated silicate-derived Sr²⁺ and HCO₃⁻ fluxes from the Himalaya. In addition, these findings demonstrate that integrating stream water carbonate mineral equilibria, divalent cation compositional trends, and Sr isotope inventories provides a powerful approach for examining weathering fluxes.     

Mineral dissolution in the Cape Cod aquifer, Massachusetts, USA: I . Reaction stoichiometry and impact of accessory feldspar and glauconite on strontium isotopes, solute concentrations, and REY distribution

To compare relative reaction rates of mineral dissolution in a mineralogically simple groundwater aquifer, we studied the controls on solute concentrations, Sr isotopes, and rare earth element and yttrium (REY) systematics in the Cape Cod aquifer. This aquifer comprises mostly carbonate-free Pleistocene sediments that are about 90% quartz with minor K-feldspar, plagioclase, glauconite, and Fe-oxides. Silica concentrations and pH in the groundwater increase systematically with increasing depth, while Sr isotopic ratios decrease. No clear relationship between ⁸⁷Sr/⁸⁶Sr and Sr concentration is observed. At all depths, the ⁸⁷Sr/⁸⁶Sr ratio of the groundwater is considerably lower than the Sr isotopic ratio of the bulk sediment or its K-feldspar component, but similar to that of a plagioclase-rich accessory separate obtained from the sediment. The Si-⁸⁷Sr/⁸⁶Sr-depth relationships are consistent with dissolution of accessory plagioclase. In addition, solutes such as Sr, Ca, and particularly K show concentration spikes superimposed on their respective general trends. The K-Sr-⁸⁷Sr/⁸⁶Sr systematics suggests that accessory glauconite is another major solute source to Cape Cod groundwater. Although the authigenic glauconite in the Cape Cod sediment is rich in Rb, it is low in in-grown radiogenic ⁸⁷Sr because of its young Pleistocene age. The low ⁸⁷Sr/⁸⁶Sr ratios are consistent with equilibration of glauconite with seawater. The impact of glauconite is inferred to vary due to its variable abundance in the sediments. In the Cape Cod groundwater, the variation of REY concentrations with sampling depth resembles that of K and Rb, but differs from that of Ca and Sr. Shale-normalized REY patterns are light REY depleted, show negative Ce anomalies and super-chondritic Y/Ho ratios, but no Eu anomalies. REY input from feldspar, therefore, is insignificant compared to input from a K-Rb-bearing phase, inferred to be glauconite. These results emphasize that interpretation of groundwater chemistry, even in relatively simple aquifers, may be complicated by solute contributions from “exotic” accessory minerals such as glauconite. To detect such peculiarities, groundwater studies should combine the study of elemental concentration and isotopic composition of several solutes that show different geochemical behavior.     

Ca/Sr and Sr isotope systematics of a Himalayan glacial chronosequence: carbonate versus silicate weathering rates as a function of landscape surface age

We explored changes in the relative importance of carbonate vs. silicate weathering as a function of landscape surface age by examining the Ca/Sr and Sr isotope systematics of a glacial soil chronosequence located in the Raikhot watershed within the Himalaya of northern Pakistan. Bedrock in the Raikhot watershed primarily consists of silicate rock (Ca/Sr ≈ 0.20 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.77 to 1.2) with minor amounts of disseminated calcite (Ca/Sr ≈ 0.98 to 5.3 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.79 to 0.93) and metasedimentary carbonate (Ca/Sr ≈ 1.0 to 2.8 μmol/nmol, ⁸⁷Sr/⁸⁶Sr ≈ 0.72 to 0.82). Analysis of the exchangeable, carbonate, and silicate fractions of seven soil profiles ranging in age from ∼0.5 to ∼55 kyr revealed that carbonate dissolution provides more than ∼90% of the weathering-derived Ca and Sr for at least 55 kyr after the exposure of rock surfaces, even though carbonate represents only ∼1.0 wt% of fresh glacial till. The accumulation of carbonate-bearing dust deposited on the surfaces of older landforms partly sustains the longevity of the carbonate weathering flux. As the average landscape surface age in the Raikhot watershed increases, the Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios released by carbonate weathering decrease from ∼3.6 to ∼0.20 μmol/nmol and ∼0.84 to ∼0.72, respectively. The transition from high to low Ca/Sr ratios during weathering appears to reflect the greater solubility of high Ca/Sr ratio carbonate relative to low Ca/Sr ratio carbonate. These findings suggest that carbonate weathering controls the dissolved flux of Sr emanating from stable Himalayan landforms comprising mixed silicate and carbonate rock for tens of thousands of years after the mechanical exposure of rock surfaces to the weathering environment.     

Magnesium isotope systematics of the lithologically varied Moselle river basin, France

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.     

Silicate and carbonate weathering in the drainage basins of the Ganga-Ghaghara-Indus head waters: Contributions to major ion and Sr isotope geochemistry

The role of silicate and carbonate weathering in contributing to the major cation and Sr isotope geochemistry of the headwaters of the Ganga-Ghaghara-Indus system is investigated from the available data. The contributions from silicate weathering are determined from the composition of granites/ gneisses, soil profiles developed from them and from the chemistry of rivers flowing predominantly through silicate terrains. The chemistry of Precambrian carbonate outcrops of the Lesser Himalaya provided the data base to assess the supply from carbonate weathering. Mass balance calculations indicate that on an average ∼ 77% (Na + K) and ∼ 17% (Ca + Mg) in these rivers is of silicate origin. The silicate Sr component in these waters average ∼40% and in most cases it exceeds the carbonate Sr. The observations that (i) the⁸⁷Sr/⁸⁶Sr and Sr/Ca in the granites/gneisses bracket the values measured in the head waters; (ii) there is a strong positive correlation between⁸⁷Sr/⁸⁶Sr of the rivers and the silicate derived cations in them, suggest that silicate weathering is a major source for the highly radiogenic Sr isotope composition of these source waters. The generally low⁸⁷Sr/⁸⁶Sr (< 0.720) and Sr/Ca (∼ 0.2 nM/ μM) in the Precambrian carbonate outcrops rules them out as a major source of Sr and⁸⁷Sr/⁸⁶Sr in the headwaters on a basin-wide scale, however, the high⁸⁷Sr/⁸⁶Sr (∼ 0.85) in a few of these carbonates suggests that they can be important for particular streams. The analysis of⁸⁷Sr/⁸⁶Sr and Ca/Sr data of the source waters show that they diverge from a low⁸⁷Sr/⁸⁶Sr and low Ca/Sr end member. The high Ca/Sr of the Precambrian carbonates precludes them from being this end member, other possible candidates being Tethyan carbonates and Sr rich evaporite phases such as gypsum and celestite. The results of this study should find application in estimating the present-day silicate and carbonate weathering rates in the Himalaya and associated CO₂ consumption rates and their global significance.     

The Gumeshevo skarn-porphyry copper deposits in the Central Urals,Russia: Evolution of the ore-magmatic system as deduced from isotope geochemistry (Sr,Nd, C,O, H)

The Early Devonian Gumeshevo deposit is one of the largest ore objects pertaining to the dioritic model of the porphyry copper system paragenetically related to the low-K quartz diorite island-arc complex. The (⁸⁷Sr/⁸⁶Sr)_t and (ɛ_Nd)_t of quartz diorite calculated for t = 390 Ma are 0.7038–0.7045 and 5.0–5.1, respectively, testifying to a large contribution of the mantle component to the composition of this rock. The contents of typomorphic trace elements (ppm) are as follows: 30–48 REE sum, 5–10 Rb, 9–15 Y, and 1–2 Nb. The REE pattern is devoid of Eu anomaly. Endoskarn of low-temperature and highly oxidized amphibole-epidote-garnet facies is surrounded by the outer epidosite zone. Widespread retrograde metasomatism is expressed in replacement of exoskarn and marble with silicate (chlorite, talc, tremolite)-magnetite-quartz-carbonate mineral assemblage. The ⁸⁷Sr/⁸⁶Sr ratios of epidote in endoskarn and carbonate in retrograde metasomatic rocks (0.7054–0.7058 and 0.7053–0.7065, respectively) are intermediate between the Sr isotope ratios of quartz dioritic rocks and marble (⁸⁷Sr/⁸⁶Sr = 0.70784 ± 2). Isotopic parameters of the fluid equilibrated with silicates of skarn and retrograde metasomatic rocks replacing exoskarn at 400°C are δ¹⁸O = +7.4 to +8.5‰ and δD = −49 to −61‰ (relative to SMOW). The δ¹³C and δ¹⁸O of carbonates in retrograde metasomatic rocks after marble are −5.3 to +0.6 (relative to PDB) and +13.0 to +20.2% (relative to SMOW), respectively. Sulfidation completes metasomatism, nonuniformly superimposed on all metasomatic rocks and marbles with formation of orebodies, including massive sulfide ore. The δ³⁴S of sulfides is 0 to 2‰ (relative to CDT);⁸⁷Sr/⁸⁶Sr of calcite from the late calcite-pyrite assemblage replacing marble is 0.704134 ± 6. The δ¹³C and ⁸⁷Sr/⁸⁶Sr of postore veined carbonates correlate positively (r = 0.98; n = 6). The regression line extends to the marble field. Its opposite end corresponds to magmatic (in terms of Bowman, 1998b) calcite with minimal δ¹³C, δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr values (−6.9 ‰, +6.7‰, and 0.70378 ± 4, respectively). The aforementioned isotopic data show that magmatic fluid was supplied during all stages of mineral formation and interacted with marble and other rocks, changing its Sr, C, and O isotopic compositions. This confirms the earlier established redistribution of major elements and REE in the process of metasomatism. A contribution of meteoric and metamorphic water is often established in quartz from postore veins.     

Use of Sr isotopes as a tool to decipher the soil weathering processes in a tropical river catchment,southwestern India

River water composition (major ion and ⁸⁷Sr/⁸⁶Sr ratio) was monitored on a monthly basis over a period of three years from a mountainous river (Nethravati River) of southwestern India. The total dissolved solid (TDS) concentration is relatively low (46 mg L⁻¹) with silica being the dominant contributor. The basin is characterised by lower dissolved Sr concentration (avg. 150 nmol L⁻¹), with radiogenic ⁸⁷Sr/⁸⁶Sr isotopic ratios (avg. 0.72041 at outlet). The composition of Sr and ⁸⁷Sr/⁸⁶Sr and their correlation with silicate derived cations in the river basin reveal that their dominant source is from the radiogenic silicate rock minerals. Their composition in the stream is controlled by a combination of physical and chemical weathering occurring in the basin. The molar ratio of SiO₂/Ca and ⁸⁷Sr/⁸⁶Sr isotopic ratio show strong seasonal variation in the river water, i.e., low SiO₂/Ca ratio with radiogenic isotopes during non-monsoon and higher SiO₂/Ca with less radiogenic isotopes during monsoon season. Whereas, the seasonal variation of Rb/Sr ratio in the stream water is not significant suggesting that change in the mineral phase being involved in the weathering reaction could be unlikely for the observed molar SiO₂/Ca and ⁸⁷Sr/⁸⁶Sr isotope variation in river water. Therefore, the shift in the stream water chemical composition could be attributed to contribution of ground water which is in contact with the bedrock (weathering front) during non-monsoon and weathering of secondary soil minerals in the regolith layer during monsoon. The secondary soil mineral weathering leads to limited silicate cation and enhanced silica fluxes in the Nethravati river basin.     

Hydrologic controls on radiogenic Sr in meltwater from an alpine glacier system: Athabasca Glacier,Canada

Filtered subglacial meltwater samples were collected daily during the onset of melt (May) and peak melt (July) over the 2011 melt season at the Athabasca Glacier (Alberta, Canada) and analyzed for strontium-87/strontium-86 (⁸⁷Sr/⁸⁶Sr) isotopic composition to infer the evolution of subglacial weathering processes. Both the underlying bedrock composition and subglacial water–rock interaction time are the primary influences on meltwater ⁸⁷Sr/⁸⁶Sr. The Athabasca Glacier is situated atop Middle Cambrian carbonate bedrock that also contains silicate minerals. The length of time that subglacial meltwater interacts with the underlying bedrock and substrate is a predominant determining factor in solute concentration. Over the course of the melt season, increasing trends in Ca/K and Ca/Mg correspond to overall decreasing trends in ⁸⁷Sr/⁸⁶Sr, which indicate a shift in weathering processes from the presence of silicate weathering to primarily carbonate weathering.Early in the melt season, rates of carbonate dissolution slow as meltwater approaches saturation with respect to calcite and dolomite, corresponding to an increase in silicate weathering that includes Sr-rich silicate minerals, and an increase in meltwater ⁸⁷Sr/⁸⁶Sr. However, carbonate minerals are preferentially weathered in unsaturated waters. During the warmest part of a melt season the discharged meltwater is under saturated, causing an increase in carbonate weathering and a decrease in the radiogenic Sr signal. Likewise, larger fraction contributions of meltwater from glacial ice corresponds to lower ⁸⁷Sr/⁸⁶Sr values, as the meltwater has lower water–rock interaction times in the subglacial system. These results indicate that although weathering of Sr-containing silicate minerals occurs in carbonate dominated glaciated terrains, the continual contribution of new meltwater permits the carbonate weathering signal to dominate.     

Petrogenesis of Sierra Nevada plutons inferred from the Sr, Nd, and O isotopic signatures of mafic igneous complexes in Yosemite Valley, California

Mafic complexes in the central Sierra Nevada batholith record valuable geochemical information regarding the role mafic magmas play in arc magmatism and the generation of continental crust. In the intrusive suite of Yosemite Valley, major and trace element compositions of the hornblende-bearing gabbroic rocks from the Rockslides mafic complex and of the mafic dikes in the North America Wall are compositionally similar to high-alumina basalt. Of these rocks, two samples have higher Ni and Cr abundances as well as higher ε_Nd values than previously recognized for the intrusive suite. Plagioclase crystals in rocks from the North America Wall and the Rockslides have prominent calcic cores and sharply defined sodic rims, a texture commonly associated with mixing of mafic and felsic magmas. In situ analyses of ⁸⁷Sr/⁸⁶Sr in plagioclase show no significant isotopic difference from the cores to the rims of these grains. We propose that the high ⁸⁷Sr/⁸⁶Sr (~0.7067) and low ε_Nd (~?3.4) of bulk rocks, the homogeneity of ⁸⁷Sr/⁸⁶Sr in plagioclase, and the high δ¹⁸O values of bulk rocks (6.6–7.3 ‰) and zircon (Lackey et al. in J Petrol 49:1397–1426, 2008) demonstrate that continental crust was assimilated into the sublithospheric mantle-derived basaltic precursors of the mafic rocks in Yosemite Valley. Contamination (20–40 %) likely occurred in the lower crust as the magma differentiated to high-alumina basalt prior to plagioclase (and zircon) crystallization. As a consequence, the isotopic signatures recorded by whole rocks, plagioclase, and zircon do not represent the composition of the underlying lithospheric mantle. We conclude that the mafic and associated felsic members of the intrusive suite of Yosemite Valley represent 60–80 % new additions to the crust and include significant quantities of recycled ancient crust.     

A strontium isotopic study of the volcanic rocks of the Myoko volcano group,central Japan

Thirty-one selected volcanic rocks from the Myoko volcano group which comprises a volcanic chain of four independent volcanoes of Quaternary to Recent age are analyzed for ⁸⁷Sr/⁸⁶Sr ratios. The rocks of the lizuna volcano, the oldest among the Myoko volcano group, have higher ⁸⁷Sr/⁸⁶Sr ratios and show a larger scatter ranging from 0.7043₇ to 0.7055₆ than those of other volcanoes. The Kurohime volcanic rocks have a restricted range of ⁸⁷Sr/⁸⁶Sr ratios (0.7040₃∼0.7043₅). ⁸⁷Sr/⁸⁶Sr ratios of the Myoko volcanic rocks are almost the same in average to those of the Kurohime volcanic rocks, although somewhat varied ranging from 0.7037₈ to 0.7046₁. A single analysis of the Yakeyama volcanic rock yielded a ⁸⁷Sr/⁸⁶Sr ratio of 0.7042₇. A characteristic pattern in ⁸⁷Sr/⁸⁶Sr ratios is observed through the volcanic activity of the Myoko volcano group; ⁸⁷Sr/⁸⁶Sr ratios are high in the early stage of the volcanic activity and then decrease to low values, the late eruptives being characterized by constant ⁸⁷Sr/⁸⁶Sr ratios. The negative correlation between ⁸⁷Sr/⁸⁶Sr and Rb/Sr, and positive correlation between ⁸⁷Sr/⁸⁶Sr and Sr found in the rocks of the Iizuna volcano are interpreted to show the occurrence of contamination by materials with high ⁸⁷Sr/⁸⁶Sr ratios (>0.7056), low Rb/Sr ratios (<0.01) and high Sr contents (>300 ppm). Sialic crustal contamination may have played only a minor role.     

Climatic and tectonic controls on chemical weathering in the New Zealand Southern Alps

Climatic and tectonic controls on the relative abundance of solutes in streams draining the New Zealand Southern Alps were investigated by analyzing the elemental and Sr isotope geochemistry of stream waters, bedload sediment, and hydrothermal calcite veins. The average relative molar abundance of major cations and Si in all stream waters follows the order Ca²⁺ (50%) > Si (22%) > Na⁺ (17%) > Mg²⁺ (6%) > K⁺ (5%). For major anions, the relative molar abundance is HCO₃⁻ (89%) > SO₄²⁻ (7%) > Cl⁻ (4%). Weathering reactions involving plagioclase and volumetrically small amounts of hydrothermal calcite define the ionic chemistry of stream waters, but nearly all streams have a carbonate-dominated Ca²⁺ and HCO₃⁻ mass-balance. Stream water Ca/Sr and ⁸⁷Sr/⁸⁶Sr ratios vary from 0.173 to 0.439 μmol/nmol and from 0.7078 to 0.7114, respectively. Consistent with the ionic budget, these ratios lie solely within the range of values measured for bedload carbonate (Ca/Sr = 0.178 to 0.886 μmol/nmol; ⁸⁷Sr/⁸⁶Sr = 0.7081 to 0.7118) and hydrothermal calcite veins (Ca/Sr = 0.491 to 3.33 μmol/nmol; ⁸⁷Sr/⁸⁶Sr = 0.7076 to 0.7097).Streams draining regions in the Southern Alps with high rates of physical erosion induced by rapid tectonic uplift and an extremely wet climate contain ∼10% more Ca²⁺ and ∼30% more Sr²⁺ from carbonate weathering compared to streams draining regions in drier, more stable landscapes. Similarly, streams draining glaciated watersheds contain ∼25% more Sr²⁺ from carbonate weathering compared to streams draining non-glaciated watersheds. The highest abundance of carbonate-derived solutes in the most physically active regions of the Southern Alps is attributed to the tectonic exhumation and mechanical denudation of metamorphic bedrock, which contains trace amounts of calcite estimated to weather ∼350 times faster than plagioclase in this environment. In contrast, regions in the Southern Alps experiencing lower rates of uplift and erosion have a greater abundance of silicate- versus carbonate-derived cations. These findings highlight a strong coupling between physical controls on landscape development and sources of solutes to stream waters. Using the Southern Alps as a model for assessing the role of active tectonics in geochemical cycles, this study suggests that rapid mountain uplift results in an enhanced influence of carbonate weathering on the dissolved ion composition delivered to seawater.     

An overview on geochemistry of Proterozoic massif-type anorthosites and associated rocks

A critical study of 311 published WR chemical analyses, isotopic and mineral chemistry of anorthosites and associated rocks from eight Proterozoic massif anorthosite complexes of India, North America and Norway indicates marked similarities in mineralogy and chemistry among similar rock types. The anorthosite and mafic-leucomafic rocks (e.g., leuconorite, leucogabbro, leucotroctolite, anorthositic gabbro, gabbroic anorthosite, etc.) constituting the major part of the massifs are characterized by higher Na₂O + K₂O, Al₂O₃, SiO₂, Mg# and Sr contents, low in plagioclase incompatible elements and REE with positive Eu anomalies. Their δ ¹⁸O‰ (5.7–7.5), initial ⁸⁷Sr/⁸⁶Sr (0.7034–0.7066) and ɛ _Nd values (+1.14 to +5.5) suggest a depleted mantle origin. The Fe-rich dioritic rocks occurring at the margin of massifs have isotopic, chemical and mineral composition more close to anorthosite-mafic-leucomafic rocks. However, there is a gradual decrease in plagioclase content, An content of plagioclase and X_Mg of orthopyroxene, and an increase in mafic silicates, oxide minerals content, plagioclase incompatible elements and REE from anorthosite-mafic-leucomafic rocks to Fe-rich dioritic rocks. The Fe-rich dioritic rocks are interpreted as residual melt from mantle derived high-Al gabbro melt, which produced the anorthosite and mafic-leucomafic rocks. Mineralogically and chemically, the K-rich felsic rocks are distinct from anorthosite-mafic-leucomafic-Fe-rich dioritic suite. They have higher δ ¹⁸O values (6.8–10.8‰) and initial ⁸⁷Sr/⁸⁶Sr (0.7067–0.7104). By contrast, the K-rich felsic suites are products of melting of crustal precursors.     

Petrogenetic links between lepidolite-subtype aplite-pegmatite,aplite veins and associated granites at Segura (central Portugal)

In the Segura area, Variscan S-type granites, aplite veins and lepidolite-subtype granitic aplite-pegmatite veins intruded the Cambrian schist-metagraywacke complex. The granites are syn D3. Aplite veins also intruded the granites. Two-mica granite and muscovite granite have similar ages of 311.0 ± 0.5 Ma and 312.9 ± 2.0 Ma but are not genetically related, as indicated by their geochemical characteristics and (⁸⁷Sr/⁸⁶Sr)₃₁₁ values. They correspond to distinct pulses of magma derived by partial melting of heterogeneous metapelitic rocks. Major and trace elements suggest fractionation trends for: (a) muscovite granite and aplite veins; (b) two-mica granite and lepidolite-subtype aplite-pegmatite veins, but with a gap in most of these trends. Least square analysis for major elements, and modeling of trace elements, indicate that the aplite veins were derived from the muscovite granite magma by fractional crystallization of quartz, plagioclase, K-feldspar and ilmenite. This is supported by the similar (⁸⁷Sr/⁸⁶Sr)₃₁₁ and δ¹⁸O values and the behavior of P₂O₅ in K-feldspar and albite. The decrease in (⁸⁷Sr/⁸⁶Sr)₃₁₁ and strong increase (1.6‰) in δ¹⁸O from two-mica granite to lepidolite-subtype aplite-pegmatite veins, and the behaviors of Ca, Mn and F of hydroxylapatite indicate that these veins are not related to the two-mica granite.     

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.     

Isotopic and chemical constraints on the crustal evolution and source signature of Ferrar magmas,north Victoria Land,Antarctica

Isotopic (Nd and Sr) and chemical compositions of the 177 Ma Kirkpatrick Basalt and Ferrar Dolerite from north Victoria Land, Antarctica, are examined in order to address the role of crustal assimilation and the characteristics of their mantle source. Results for the Scarab Peak chemical type (SPCT) that constitutes the flow unit capping the lava sequence [Mg-number, Mg/(Mg+Fe⁺²)=24, MgO=2.4%, SiO₂=57.1%, initial⁸⁷Sr/⁸⁶Sr=0.7087–0.7097, (ε_Nd=−4.3) conform previous reports that attribute variations in the concentrations of the more mobile elements and calculated initial⁸⁷Sr/⁸⁶Sr to mid-Cretaceous alteration and elevated δ¹⁸O to low-temperature interaction with meteoric water. The underlying lavas and the sills that are of the Mt. Fazio chemical type (MFCT) display a much wider range of both chemical and isotopic compositions (Mg-number=40–65, MgO=3.7 7.5%; SiO₂=52.6–58.3%, initial⁸⁷Sr/⁸⁶Sr=0.7087–0.7117, ε_Nd=−5.6 to −4.8). The effects of rock alteration on apparent initial⁸⁷Sr/⁸⁶Sr are demonstrated by large differences between the initial ratio of mineral separates or leached fractions and whole rocks. Cretaceous alteration produced Rb and Sr redistribution within the lava sequence that results in erroneous calculated initial⁸⁷Sr/⁸⁶Sr ratios. These effects are responsible for the large initial⁸⁷Sr/⁸⁶Sr variations previousl7 proposed which, combined with the large range in whole-rock δ¹⁸O, were purported to show very large degrees of crustal assimilation. The variations in ε_Nd are restricted and indicate much smaller degrees of assimilation. The least altered of the MFCT rocks show good chemical and isotopic correlations that can be integrated into a model involving fractionation of pyroxene and plagioclase coupled with assimilation of material similar to early Paleozoic basement. The lower⁸⁷Sr/⁸⁶Sr and higher ε_Nd of the SPCT suggest that they were derived by extensive fractionation of a more primitive, less contaminated, precursor of the MFCT. The most isotopically primitive Ferrar rocks from the region still have a high initial⁸⁷Sr/⁸⁶Sr and low initial¹⁴³Nd/¹⁴⁴Nd; this may reflect either earlier assimilation or an enriched source. The chemical and isotopic similarities, as well as the close geographic correspondence of the Ferrar Group to granitoids produced during the early Paleozoic Ross Orogeny suggest that in either case Ross-type material may have been involved in the development of the enriched isotopic signature. Editorial responsibility: I. Parsons     

Sr and Sr/Sr in the Yamuna River System in the Himalaya: sources, fluxes, and controls on sr isotope composition

Sr and ⁸⁷Sr/⁸⁶Sr have been measured in the Yamuna river headwaters and many of its tributaries (YRS) in the Himalaya. These results, with those available for major ions in YRS rivers and in various lithologies of their basin, have been used to determine their contributions to riverine Sr and its isotopic budget. Sr in the YRS ranges from 120 to 13,400 nM, and ⁸⁷Sr/⁸⁶Sr from 0.7142 to 0.7932. Streams in the upper reaches, draining predominantly silicates, have low Sr and high ⁸⁷Sr/⁸⁶Sr whereas those draining the lower reaches exhibit the opposite resulting from differences in drainage lithology. ⁸⁷Sr/⁸⁶Sr shows significant co-variation with SiO₂/TDS and (Na^* + K)/TZ⁺ (indices of silicate weathering) in YRS waters, suggesting the dominant role of silicate weathering in contributing to high radiogenic Sr. This is also consistent with the observation that streams draining largely silicate terrains have the highest ⁸⁷Sr/⁸⁶Sr, analogous to that reported for the Ganga headwaters. Evaluation of the significance of other sources such as calc-silicates and trace calcites in regulating Sr budget of these rivers and their high ⁸⁷Sr/⁸⁶Sr needs detailed work on their Sr and ⁸⁷Sr/⁸⁶Sr. Preliminary calculations, however, indicate that they can be a significant source to some of the rivers.It is estimated that on an average, ∼25% of Sr in the YRS is derived from silicate weathering. In the lower reaches, the streams receive ∼15% of their Sr from carbonate weathering whereas in the upper reaches, calc-silicates can contribute significantly (∼50%) to the Sr budget of rivers. These calculations reveal the need for additional sources for rivers in the lower reaches to balance their Sr budget. Evaporites and phosphorites are potential candidates as judged from their occurrence in the drainage basin. In general, Precambrian carbonates, evaporites, and phosphorites “dilute” the high ⁸⁷Sr/⁸⁶Sr supplied by silicates, thus making Sr isotope distribution in YRS an overall two end member mixing. Major constraints in quantifying contributions of Sr and ⁸⁷Sr/⁸⁶Sr from different sources to YRS rivers are the wide range in Sr and ⁸⁷Sr/⁸⁶Sr of major lithologies, limited data on Sr and ⁸⁷Sr/⁸⁶Sr in minor phases and on the behavior of Sr, Na, and Ca during weathering and transport.The Ganga and the Yamuna together transport ∼0.1% of the global Sr flux at the foothills of the Himalaya which is in the same proportion as their contribution to global water discharge. Dissolved Sr flux from the Yamuna and its mobilization rate in the YRS basin is higher than those in the Ganga basin in the Himalaya, a result consistent with higher physical and chemical erosion rates in the YRS.     

Carbonate alteration associated with talc-chlorite mineralization in the eastern Pyrenees, with emphasis on the St. Barthelemy Massif

Summary The eastern Pyrenees host a large number of talc-chlorite mineralizations of Albian age (112–97 Ma), the largest of which occur in the St. Barthelemy massif. There talc develops by hydrothermal replacement of dolostones, which were formed by alteration of calcite marbles. This alteration is progressive. Unaltered calcite marbles have oxygen isotope composition of about 25‰ (V-SMOW). The δ¹⁸O values decrease down to values of 12‰ towards the contact with dolostones. This ¹⁸O depletion is accompanied by Mg enrichment, LREE fractionation and systematic shifts in the Sr isotope compositions, which vary from ⁸⁷Sr/⁸⁶Sr = 0.7087–0.7092 in unaltered calcite marbles to slightly more radiogenic compositions with ⁸⁷Sr/⁸⁶Sr = 0.7094 near dolomitization fronts. Dolostones have δ¹⁸O values (about 9‰) lower than calcitic marbles, higher REE content and more radiogenic Sr isotope composition (⁸⁷Sr/⁸⁶Sr = 0.7109 to 0.7130). Hydrothermal calcites have δ¹⁸O values close to dolostones but substantially lower δ¹³C values, down to −6.5‰, which is indicative of the contribution of organic matter. The REE content of hydrothermal calcite is one order of magnitude higher than that of calcitic marbles. Its highly radiogenic Sr composition with ⁸⁷Sr/⁸⁶Sr = 0.7091 to 0.7132 suggests that these elements were derived from silicate rocks, which experienced intense chlorite alteration during mineralization. The chemical and isotopic compositions of the calcite marbles, the dolostones and the hydrothermal calcites are interpreted as products of successive stages of fluid-rock interaction with increasing fluid-rock ratios. The hydrothermal quartz, calcite, talc and chlorite are in global mutual isotopic equilibrium. This allows the calculation of the O isotope composition of the infiltrating water at 300 °C, which is in the δ¹⁸O = 2–4.5‰ range. Hydrogen isotope compositions of talc and chlorite indicate a δD = 0 to −20‰. This water probably derived from seawater, with minor contribution of evolved continental water.