Geochemistry of the dissolved load of the Changjiang Basin rivers: Anthropogenic impacts and chemical weathering

This study focuses on the chemical and Sr isotopic compositions of the dissolved load of the rivers of the Changjiang Basin, one of the largest riverine systems in the world. Water samples were collected in August 2006 from the main tributaries and the main Changjiang channel. The chemical and isotopic analyses indicated that four major reservoirs (carbonates, silicates, evaporites and agriculture/urban effluents) contribute to the total dissolved solutes. The overall chemical weathering (carbonate and silicate) rate for the Changjiang is approximately 40 ton/km²/year or 19 mm/kyr, similar to that of the Ganges-Brahmaputra system, and the basin is characterized by carbonate and silicate weathering rates ranging from 17 to 56 ton/km²/year and from 0.7 to 7.1 ton/km²/year, respectively. In the lower reach of the Changjiang main channel, the weathering rates are estimated to be 36 and 2.2 ton/km²/year for carbonates and silicates, respectively. It appears that sulphuric acid may dominate chemical weathering reactions for some sub-basins. The budgets of CO₂ consumption are estimated to be 646 × 10⁹ and 191 × 10⁹ mol/year by carbonate and silicate weathering, respectively. The contribution of the anthropogenic inputs to the cationic TDS of the Changjiang is estimated to be 15-20% for the most downstream stations. Our study suggested that the Changjiang is strongly impacted by human activities and is very sensitive to the change of land use.     

Stable isotopes of pedogenic carbonates from the Somma–Vesuvius area,southern Italy,over the past 18 kyr: palaeoclimatic implications

Stable isotopes were measured in the carbonate and organic matter of palaeosols in the Somma–Vesuvius area, southern Italy in order to test whether they are suitable proxy records for climatic and ecological changes in this area during the past 18000 yr. The ages of the soils span from ca. 18 to ca. 3 kyr BP. Surprisingly, the Last Glacial to Holocene climate transition was not accompanied by significant change in δ¹⁸O of pedogenic carbonate. This could be explained by changes in evaporation rate and in isotope fractionation between water and precipitated carbonate with temperature, which counterbalanced the expected change in isotope composition of meteoric water. Because of the rise in temperature and humidity and the progressive increase in tree cover during the Holocene, the Holocene soil carbonates closely reflect the isotopic composition of meteoric water. A cooling of about 2°C after the Avellino eruption (3.8 ka) accounts for a sudden decrease of about 1‰ in δ¹⁸O of pedogenic carbonate recorded after this eruption. The δ¹³C values of organic matter and pedogenic carbonate covary, indicating an effective isotope equilibrium between the organic matter, as the source of CO₂, and the pedogenic carbonate. Carbon isotopes suggest prevailing C₃ vegetation and negligible mixing with volcanogenic or atmospheric CO₂. Copyright © 2000 John Wiley & Sons, Ltd.     

Stable calcium isotopic compositions of Hawaiian shield lavas: Evidence for recycling of ancient marine carbonates into the mantle

We report high-precision ⁴⁴Ca/⁴⁰Ca measurements (2σ_m < 0.06‰) of Hawaiian shield stage tholeiites. Our data reveal ∼0.3‰ variation in their ⁴⁴Ca/⁴⁰Ca, which comprises ∼20% of the ⁴⁴Ca/⁴⁰Ca variation observed in global carbonates. The ⁴⁴Ca/⁴⁰Ca variation is correlated with Sr/Nb and ⁸⁷Sr/⁸⁶Sr, and this pattern is best explained by adding up to 4% ancient carbonate into the Hawaiian plume. Mass-balance calculations show that up to 40% of the Ca budget and 65% of the Sr budget in some Hawaiian (Makapuu-stage Koolau) lavas are derived from recycled carbonates. Our finding demonstrates, for the first time with the application of Ca isotopes, that ancient recycled carbonates are important components of mantle plumes which feed some of the largest terrestrial volcanoes. Thus, recycling of carbonates into the mantle is an essential part of the global Ca and C cycles.     

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.     

Sr fluxes and Sr/Sr characterization of river waters from a karstic versus granitic watershed in the Yangtze River

The watershed in the southern Jiangxi Province (Jiangxi Province is called simply Gan) (SGW) and the watershed in the central Guizhou Province (Guizhou Province is called simply Qian) (CQW) are two subtropical watersheds of the Yangtze River in China. Both watersheds have similar latitudes and climate, but distinct differences in basin lithology. These similarities and differences provide a good natural laboratory in which to investigate weathering processes and Sr end-members in river waters. This work aims to identify and contrast the sources, fluxes and controls on Sr isotopic composition in the river waters of these two areas. Results showed that the ⁸⁷Sr/⁸⁶Sr in the SGW waters ranged from 0.716501 to 0.724931, with dissolved Sr averaging 27 μg l^− 1. Rhyolites and granites are two major sources for the dissolved Sr. The SGW waters receive 42% of their Sr from silicates weathering, 32% from carbonates and 3.2% from evaporites. ⁸⁷Sr/⁸⁶Sr in the CQW waters has a lesser variation from 0.707694 to 0.710039, but higher Sr contents (average of 208 μg l^− 1). Dolomite, limestone and dolomitic limestone are major sources of Sr in the waters. The CQW waters receive 69% of their Sr from carbonates, 1.7% from silicates and 0.9% from evaporites. The chemical erosion rate and Sr flux in the CQW are 122 t km^− 2 a^− 1 and 0.079 t km^− 2 a^− 1, respectively, which are higher than those of the SGW (56 t km^− 2 a^− 1 and 0.021 t km^− 2 a^− 1, respectively). These data suggest that the intensive carbonates weathering occurred in the karstic area in the upper-reach of the Yangtze River exert great influence on the high Sr concentration and low Sr isotopic ratios in the River.     

Geochemical and C, O, Sr, and U-series isotopic evidence for the meteoric origin of calcrete at Solitario Wash, Crater Flat, Nevada, USA

Calcite-rich soils (calcrete) in alluvium and colluvium at Solitario Wash, Crater Flat, Nevada, USA, contain pedogenic calcite and opaline silica similar to soils present elsewhere in the semi-arid southwestern United States. Nevertheless, a ground-water discharge origin for the Solitario Wash soil deposits was proposed in a series of publications proposing elevation-dependent variations of carbon and oxygen isotopes in calcrete samples. Discharge of ground water in the past would raise the possibility of future flooding in the unsaturated zone at Yucca Mountain, Nevada, site of a proposed high-level nuclear waste repository. New geochemical and carbon, oxygen, strontium, and uranium-series isotopic data disprove the presence of systematic elevation-isotopic composition relations, which are the main justification given for a proposed ground-water discharge origin of the calcrete deposits at Solitario Wash. Values of δ¹³C (−4.1 to −7.8 per mil [‰]), δ¹⁸O (23.8–17.2‰), ⁸⁷Sr/⁸⁶Sr (0.71270–0.71146), and initial ²³⁴U/²³⁸U activity ratios of about 1.6 in the new calcrete samples are within ranges previously observed in pedogenic carbonate deposits at Yucca Mountain and are incompatible with a ground-water origin for the calcrete. Variations in carbon and oxygen isotopes in Solitario Wash calcrete likely are caused by pedogenic deposition from meteoric water under varying Quaternary climatic conditions over hundreds of thousands of years.     

Sr isotopic composition of Paleoproterozoic C-rich carbonate rocks: The Tulomozero Formation,SE Fennoscandian Shield

Rb–Sr systematics has been studied in ¹³C-rich carbonate rocks of the Paleoproterozoic (2.09 ± 0.07 Ga) Tulomozero Formation in the northern Onega Lake area, the SE Fennoscandian Shield. The formation is divided into eight members (A–F) consisting of greenschist-facies-grade, variegated sandstones, siltstones, mudstones, stromatolitic dolostones and subordinate crystalline limestones. Samples of carbonate rocks were obtained from two overlapping drillholes intersecting the entire thickness of the Tulomozero Formation. Prior to isotope analysis, the rocks powders were treated with 1N ammonium acetate for partial removal of the late epigenetic carbonate phases. Major resetting of the Rb–Sr systems in the Tulomozero carbonate rocks appears to take place during the Svecofennian regional metamorphic event, and it was screened by using Mn/Sr, Fe/Sr, Mg/Ca, and ¹⁸O/¹⁶O ratios. High Sr content (up to 2080 μg/g in limestones, and 530 μg/g in dolostones) coupled with low Fe/Mn (<0.40) ratios in the Tulomozero carbonate rocks of Members A, B (the lower part), D, F, and E are consistent with accumulation of original carbonate sediments in evaporitic lacustrine, playa, and sabkha environments. A decrease in the Sr content with concurrent increase in the Fe/Mn ratio (>0.40) in dolostones of the upper part of Member B, and of Members G and H is indicative of seawater influxes (sea transgression) into the Tulomozero basin. The ⁸⁷Sr/⁸⁶Sr values in the least altered (Mn/Sr < 2.0) marine dolostones are 0.70418–0.70442 and 0.70343–0.70409 for the earlier and late phases of the marine transgression, respectively. The decrease in the ⁸⁷Sr/⁸⁶Sr ratio in ca. 2.1 Ga seawater is attributable to an increase in hydrothermal flux Sr into the Palaeoproterozoic ocean.     

Isotopic tracers of paleohydrologic change in large lakes of the Bolivian Altiplano

We have developed an ⁸⁷Sr/⁸⁶Sr, ²³⁴U/²³⁸U, and δ¹⁸O data set from carbonates associated with late Quaternary paleolake cycles on the southern Bolivian Altiplano as a tool for tracking and understanding the causes of lake-level fluctuations. Distinctive groupings of ⁸⁷Sr/⁸⁶Sr ratios are observed. Ratios are highest for the Ouki lake cycle (120-95 ka) at 0.70932, lowest for Coipasa lake cycle (12.8-11.4 ka) at 0.70853, and intermediate at 0.70881 to 0.70884 for the Salinas (95-80 ka), Inca Huasi (~ 45 ka), Sajsi (24-20.5 ka), and Tauca (18.1-14.1 ka) lake cycles. These Sr ratios reflect variable contributions from the eastern and western Cordilleras. The Laca hydrologic divide exerts a primary influence on modern and paleolake ⁸⁷Sr/⁸⁶Sr ratios; waters show higher ⁸⁷Sr/⁸⁶Sr ratios north of this divide. Most lake cycles were sustained by slightly more rainfall north of this divide but with minimal input from Lake Titicaca. The Coipasa lake cycle appears to have been sustained mainly by rainfall south of this divide. In contrast, the Ouki lake cycle was an expansive lake, deepest in the northern (Poópo) basin, and spilling southward. These results indicate that regional variability in central Andean wet events can be reconstructed using geochemical patterns from this lake system.     

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.     

An extraterrestrial He-based timescale for the Paleocene-Eocene thermal maximum (PETM) from Walvis Ridge, IODP Site 1266

In the deep-sea, the Paleocene-Eocene Thermal Maximum (PETM) is often marked by clay-rich condensed intervals caused by dissolution of carbonate sediments, capped by a carbonate-rich interval. Constraining the duration of both the dissolution and subsequent cap-carbonate intervals is essential to computing marine carbon fluxes and thus testing hypotheses for the origin of this event. To this end, we provide new high-resolution helium isotope records spanning the Paleocene-Eocene boundary at ODP Site 1266 in the South Atlantic. The extraterrestrial ³He, ³He_ET, concentrations replicate trends observed at ODP Site 690 by Farley and Eltgroth (2003). By assuming a constant flux of ³He_ET we constrain relative changes in accumulation rates of sediment across the PETM and construct a new age model for the event. In this new chronology the zero carbonate layer represents 35 kyr, some of which reflects clay produced by dissolution of Paleocene (pre-PETM) sediments. Above this layer, carbonate concentrations increase for ∼165 kyr and remain higher than in the latest Paleocene until 234 ⁺⁴⁸/₋₃₄ kyr above the base of the clay. The new chronology indicates that minimum δ¹³C values persisted for a maximum of 134 ⁺²⁷/₋₁₉ kyr and the inflection point previously chosen to designate the end of the CIE recovery occurs at 217 ⁺⁴⁴/₋₃₁ kyr. This allocation of time differs from that of the cycle-based age model of Röhl et al. (2007) in that it assigns more time to the clay layer followed by a more gradual recovery of carbonate-rich sedimentation. The new model also suggests a longer sustained δ¹³C excursion followed by a more rapid recovery to pre-PETM δ¹³C values. These differences have important implications for constraining the source(s) of carbon and mechanisms for its subsequent sequestration, favoring models that include a sustained release of carbon after an initial pulse.     

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.     

LA-MC-ICPMS and SHRIMP U-Pb dating of complex zircons from Quaternary tephras from the French Massif Central: Magma residence time and geochemical implications

Analyses of zircon grains from the Queureuilh Quaternary tephras (pumice) provide new information about their pre-eruptive history. U-Pb dating was performed in situ using two methods: SHRIMP and LA-MC-ICPMS equipped with a multi-ion counting system. Both methods provided reliable ²⁰⁷Pb/²⁰⁶Pb and ²⁰⁶Pb/²³⁸U ratios as well as U and Th abundances required for U-Pb Concordia intercept age determination, after initial ²³⁰Th disequilibrium correction. The new LA-MC-ICPMS method was validated by dating a reference zircon (61.308B) and zircons from a phonolitic lava dated independently with the two techniques. A time resolution of about 20 kyr for 1 Ma zircon crystals was achieved for both methods.The clear euhedral zircon population from Queureuilh tephras is quite complex from several points of view: (1) some grains are reddish or yellowish while others are colorless; (2) the U and Th composition changes by more than an order of magnitude and Th/U is generally high (∼1-2); (3) there are three discrete ages recorded at 2.35 ± 0.04, 1.017 ± 0.008 and 0.640 ± 0.010 Ma.From the previously determined ⁴⁰Ar/³⁹Ar age at 0.571 ± 0.060 Ma [Duffell H. (1999) Contribution géochronologique à la stratigraphie volcanique du Massif des Monts Dore par la méthode ⁴⁰Ar/³⁹Ar. D.E.A. Univ. Clermont-Ferrand, 56 p.], the discontinuous zircon age populations, the color of the grains and their composition, we favor the following model as explanation: The oldest, less numerous group of reddish zircons represents xenocrystic grains resulting from assimilation of the local material during magma ascent. A primitive magma chamber, perhaps deep in crustal level, was formed at 1.0 Ma. The related magma, previously characterized by high Th/U ratio (2.2 ± 1.1), underwent rejuvenation during ascent to a new chamber at shallow depth and/or during injection of more mafic magmas. During this stage, at 0.64 Ma, the colorless zircon grains of lower Th/U ratio (1.3 ± 0.5) crystallized. This last stage defined the magma residence time of 70 kyr prior to eruption dated by the ⁴⁰Ar/³⁹Ar method. However, if the primitive magma is considered, the magma residence time as a whole from this first stage reached 446 kyr.In the light of the complex history of such magmas, which commonly involves recycling of zircon grains that precipitated tens to hundreds of kyr earlier than eruptions, the use of Zr concentration in geochemical modeling of whole rock compositional data can be problematic.     

Terrestrial and freshwater carbonates in Hoxnian interglacial deposits, UK: micromorphology, stable isotopic composition and palaeoenvironmental significance

MIS 11 is often considered to be the best climatic analogue for the Holocene. Many studies have suggested, however, that it is a period of extreme climate warmth comparable in temperatures to the Middle and Late Pliocene. In Britain deposits of the Hoxnian interglacial are correlated to MIS 11 and multi-proxy techniques can be used to reconstruct the climate of this interglacial. Soil, groundwater and freshwater carbonates are common in Hoxnian deposits and the stable isotopic composition of these precipitates can be used to increase our understanding of MIS 11 environments in Britain. Carbonates from Marks Tey, Clacton, Swanscombe, Elveden and West Stow are studied, the stratigraphic context of which indicates that their formation is broadly synchronous (in the mid-Hoxnian, pollen zones Ho II to Ho III). The carbon isotopic composition of groundwater and pedogenic carbonates is typically depleted with respect to δ¹³C (ca −9 to −8‰ VPDB) reflecting uptake of plant respired CO₂ during water migration/recharge. The carbon isotopic composition of lacustrine carbonate is more enriched with respect to δ¹³C (ca 0-1‰VPDB) reflecting the equilibration of lake waters with atmospheric CO₂. The δ¹⁸O of groundwater and pedogenic carbonates is slightly more enriched than modern soil carbonates but not as enriched as soil carbonates formed under interglacials that were warmer than the Holocene (i.e. the Cromerian). The stable isotopic composition of Hoxnian carbonates does not, therefore, indicate that this interglacial was characterised by uniquely warm climates in the context of other Middle Pleistocene interglacials and the Holocene. This is contrary to many marine and littoral records from around the world but consistent with environmental records from Britain and Europe.     

Stratotype of the Lower Riphean, the Burzyan Group of the Southern Urals: Lithostratigraphy, paleontology, geochronology, Sr- and C-isotopic characteristics of its carbonate rocks

The main objective of this work is the generalization of lithostratigraphic, biostratigraphic and isotopic-geochronological data characterizing carbonate rocks from type succession of the broadly acknowledged chronostratigraphic subdivision of the Lower Riphean, such as the Burzyan Group of the Southern Urals and its analogs. Using an original approach to investigation of the Rb-Sr and Pb-Pb isotopic systems in carbonates and strict criteria of their retentivity, we studied the least altered (“best”) samples of the Burzyan carbonates, which retain the ⁸⁷Sr/⁸⁶Sr ratio of the sedimentation environment. As long ago as 1550 ± 30 and 1430 ± 30 Ma, that ratio corresponded to 0.70460–0.70480 and 0.70456–0.70481. The results confirm the influx of the mantle material predominantly into the World Ocean of the Early Riphean. The influence of meteoric diagenesis was likely responsible for local declines of δ¹⁸O in the Burzyan carbonates down to the values of −2.5 to −1.5‰ V-PDB. In the “best” samples, this parameter ranges from −0.7 to 0‰, which is consistent with the assumption that δ¹⁸O values (0 ± 1‰) characterized the stasis of the carbonate carbon isotopic composition in oceanic water 2.06–1.25 Ga ago. C-isotopic data on carbonate from the Paleoproterozoic-Lower Riphean boundary formations of the Urals, India, North America and Siberia suggest that the mentioned stasis ended by the commencement of the Early Riphean ca. 1.6–1.5 Ga ago. In the least altered carbonates of the Early Riphean, the δ¹⁸O variation range corresponds to 4.0–4.5‰.     

Carbon,oxygen and strontium isotope geochemistry of Proterozoic carbonate rocks of the Vindhyan Basin,central India

Carbon, oxygen and strontium isotope compositions of carbonate rocks of the Proterozoic Vindhyan Supergroup, central India suggest that they can be correlated with the isotope evolution curves of marine carbonates during the latter Proterozoic. The carbonate rocks of the Lower Vindhyan Supergroup from eastern Son Valley and central Vindhyan sections show δ¹³C values of ∼0‰ (V-PDB) and those from Rajasthan section are enriched up to +2.8‰. In contrast, the carbonate rocks of the Upper Vindhyan succession record both positive and negative shifts in δ¹³C compositions. In the central Vindhyan section, the carbonates exhibit positive δ¹³C values up to +5.7‰ and those from Rajasthan show negative values down to –5.2‰. The δ¹⁸O values of most of the carbonate rocks from the Vindhyan Supergroup show a narrow range between –10 and –5‰ (V-PDB) and are similar to the ‘best preserved’ ¹⁸O compositions of the Proterozoic carbonate rocks. In the central Vindhyan and eastern Son Valley sections, carbonates from the Lower Vindhyan exhibit best-preserved ⁸⁷Sr/⁸⁶Sr compositions of 0.7059±6, which are lower compared to those from Rajasthan (0.7068±4). The carbonates with positive δ¹³C values from Upper Vindhyan are characterized by lower ⁸⁷Sr/⁸⁶Sr values (0.7068±2) than those with negative δ¹³C values (0.7082±6). A comparison of C and Sr isotope data of carbonate rocks of the Vindhyan Supergroup with isotope evolution curves of the latter Proterozoic along with available geochronological data suggest that the Lower Vindhyan sediments were deposited during the Mesoproterozoic Eon and those from the Upper Vindhyan represent a Neoproterozoic interval of deposition.     

Global nature of the Paleoproterozoic Lomagundi carbon isotope excursion: A review of occurrences in Brazil,India, and Uruguay

Positive carbon isotope excursion is reported from Paleoproterozoic carbonates of the Aravalli Supergroup (northwestern India), the Minas Supergroup (Brazil), and new sections of the Paso Severino Formation (Uruguay). The 2.42 Ga Gandarela Formation, Minas Gerais, Brazil, contains red carbonate-facies BIF grading into dolostones and limestones and yielding δ¹³C values ranging from −1.6 to +0.4‰ V-PDB. The positive C-isotope excursion (up to + 11‰ V-PDB) in marine shallow-water carbonates in India and Brazil (Jhamarkotra Formation in northwestern India, and Cercadinho and Fecho do Funil formations in Minas Gerais State, Brazil) is comparable to that observed in 2.22–2.1 Ga carbonate successions worldwide that were deposited during the Lomagundi excursion. In Uruguay, δ¹³C values up to +11.6‰ V-PDB in the deep-water Paso Severino Formation of the Piedra Alta Terrane are compatible with deposition at ca. 2.15 Ga, as indicated by the 2146 ± 7 Ma U–Pb age of dacites occurring at the top of the unit. Negative δ¹³C values are also present in carbonates of the Paso Severino Formation, but an origin related to organic-matter remineralization cannot be ruled out. Thin carbonate beds in the Rio Itapicuru greenstone belt, Bahia State, Brazil, are associated, as in the Paso Severino Formation, with deep-water black shales and have carbon isotope values up to +9‰ V-PDB. High metamorphic grade carbonates of the Jacurici terrane in the Medrado-Ipueira area, Bahia, Brazil, have carbon isotope values up to +6.9‰ V-PDB, consistent with their minimum age of 2085 ± 5 Ma inferred from the intrusive contact with and the age of the Medrado norite. No evidence was found in India, Brazil, or Uruguay for Paleoproterozoic glacial events recognized in the 2.45–2.22 Ga sedimentary successions worldwide. Unconformities between the Gandarela and Cercadinho formations in Brazil and the banded gneissic Complex and the Lower Aravalli Supergroup in India might explain the absence of glacial record. Compositional and isotopic data presented here for studied Paleoproterozoic carbonate successions allow their integration into the global record of the Paleoproterozoic evolution as well as correlation with other successions of similar age. The study highlights the global nature of the Lomagundi excursion. Furthermore, it indicates that the Lomagundi excursion is recorded in both shallow-water (Aravalli and Minas supergroups) and deep-water carbonates (Paso Severino Formation and Rio Itapicuru greenstone belt) negating a significant impact of stromatolite productivity and hypersaline conditions on carbon isotope values of carbonates deposited in shallow-water, open-marine and isolated basins.     

Timescales of magma differentiation from basalt to andesite beneath Hekla Volcano, Iceland: Constraints from U-series disequilibria in lavas from the last quarter-millennium flows

Measurements of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria, Sr-Nd-Pb-Hf isotopes and major-trace elements have been conducted for lavas erupted in the last quarter-millennium at Hekla volcano, Iceland. The volcanic rocks range from basalt to dacite. Most of the lavas (excluding dacitic samples) display limited compositional variations in radiogenic Sr-Nd-Pb-Hf isotopes (⁸⁷Sr/⁸⁶Sr = 0.70319-0.70322; ¹⁴³Nd/¹⁴⁴Nd = 0.51302-0.51305; ²⁰⁶Pb/²⁰⁴Pb = 19.04-19.06; ²⁰⁷Pb/²⁰⁴Pb = 15.53-15.54; ²⁰⁸Pb/²⁰⁴Pb = 38.61-38.65; ¹⁷⁶Hf/¹⁷⁷Hf = 0.28311-0.28312). All the samples possess (²³⁰Th/²³⁸U) disequilibrium with ²³⁰Th excesses, and they show systematic variations in (²³⁰Th/²³²Th) and (²³⁸U/²³²Th) ratios. The highest ²²⁶Ra excesses occur in the basalt and most differentiated andesite lavas, while some basaltic-andesite lavas have (²²⁶Ra/²³⁰Th) ratio that are close to equilibrium. The ²³⁸U-²³⁰Th-²²⁶Ra disequilibria variations cannot be produced by simple closed-system fractional crystallization with radioactive decay of ²³⁰Th and ²²⁶Ra in a magma chamber. A closed-system fractional crystallization model and assimilation and fractional crystallization (AFC) model indicate that the least differentiated basaltic andesites were derived from basalt by fractional crystallization with a differentiation age of ∼24 ± 11 kyr, whereas the andesites were formed by assimilation of crustal material and fractionation of the basaltic-andesites within 2 kyr. Apatite is inferred to play a key role in fractionating the parent-daughter nuclides in ²³⁰Th-²³⁸U and ²²⁶Ra-²³⁰Th to make the observed variations. Our proposed model is that several batches of basaltic-andesite magmas that formed by fractional crystallization of a basaltic melt from a deeper reservoir, were periodically injected into the shallow crust to form individual magma pockets, and subsequently modifying the original magma compositions via simultaneous assimilation and fractional crystallization. The assimilant is the dacitic melt, which formed by partial melting of the crust.     

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.     

Environmental and tectonic influences on the formation and distribution of carbonate nodules above the Springfield coal seam, southern Illinois Basin

Carbonate nodules have been encountered for many years in the southern Illinois Basin, in parts of southern Illinois, southern Indiana, and southwestern Kentucky. The nodules occur as oblate spheroids of calcium carbonate that are isolated in the shale immediate roof of coal mines. They are common in the Springfield coal seam, known as the No. 5 seam in Illinois, and as the No. 9 seam in western Kentucky. Several different mechanisms have been proposed for the formation of various semi-spherical objects in coal measure rocks. The distribution and association with rooted horizons suggest that carbonate nodules in black fossiliferous shale observed in the roof of a studied mine in the Springfield seam represent pedogenic carbonate paleosols, which formed in a caliche-favoring environment subsequent to Springfield mire deposition. This interpretation is supported by ⁸⁷Sr/⁸⁶Sr isotope ratios of 0.710893 ± 13 to 0.711035 ± 12, which indicate a freshwater rather than seawater source.Petrographic examination of rock textures and mineral grains indicates that nodules collected from two Illinois Basin coal mines are composed of subangular grains of fine-grained, crystalline microspar. Although the carbonate is not ferroan, iron hydroxide stains interstices between microspar grains. The rounded, commonly pinched boundaries of nodules truncate commonly imbricated microspar grains. In contrast, concentric growth patterns are not observed except as defined by secondary, subhedral to euhedral pyrite crystals that form a diffuse, concentric replacement zone around the nodule's outer rind. Polished slickensides, with well-developed radial slickenlines, are developed at highly compacted margins in black shale or mudstone that commonly encases the carbonate nodules.Of the 450 carbonate nodules documented at a study mine in the southern Illinois Basin, the long axes of 36% are preferentially aligned parallel to regional structures such as anticline axes and drag folds that are interpreted to have formed in response to compression during the Late Pennsylvanian-Permian Alleghanian orogeny. Mapping also suggests that clusters of carbonate nodules are spatially associated with the trends of low-angle drag folds in the immediate roof of the Springfield seam at the study mine. The preferential elongation and distribution with respect to tectonic structures suggest that regional compression influenced the shape and distribution of carbonate nodules, and that nodule lithification may have been approximately contemporaneous with regional deformation.     

U-Sr isotopic speedometer: Fluid flow and chemical weathering rates in aquifers

Both chemical weathering rates and fluid flow are difficult to measure in natural systems. However, these parameters are critical for understanding the hydrochemical evolution of aquifers, predicting the fate and transport of contaminants, and for water resources/water quality considerations. ⁸⁷Sr/⁸⁶Sr and (²³⁴U/²³⁸U) activity ratios are sensitive indicators of water-rock interaction, and thus provide a means of quantifying both flow and reactivity. The ⁸⁷Sr/⁸⁶Sr values in ground waters are controlled by the ratio of the dissolution rate to the flow rate. Similarly, the (²³⁴U/²³⁸U) ratio of natural ground waters is a balance between the flow rate and the dissolution of solids, and α-recoil loss of ²³⁴U from the solids. By coupling these two isotope systems it is possible to constrain both the long-term (ca. 100’s to 1000’s of years) flow rate and bulk dissolution rate along the flow path. Previous estimates of the ratio of the dissolution rate to the infiltration flux from Sr isotopes (⁸⁷Sr/⁸⁶Sr) are combined with a model for (²³⁴U/²³⁸U) to constrain the infiltration flux and dissolution rate for a 70-m deep vadose zone core from Hanford, Washington. The coupled model for both (²³⁴U/²³⁸U) ratios and the ⁸⁷Sr/⁸⁶Sr data suggests an infiltration flux of 5 ± 2 mm/yr, and bulk silicate dissolution rates between 10^−15.7 and 10^−16.5 mol/m²/s. The process of α-recoil enrichment, while primarily responsible for the observed variation in (²³⁴U/²³⁸U) of natural systems, is difficult to quantify. However, the rate of this process in natural systems affects the interpretation of most U-series data. Models for quantifying the α-recoil loss fraction based on geometric predictions, surface area constraints, and chemical methods are also presented. The agreement between the chemical and theoretical methods, such as direct measurement of (²³⁴U/²³⁸U) of the small grain size fraction and geometric calculations for that size fraction, is quite good.