Carbon and oxygen isotopes of Maastrichtian–Danian shallow marine carbonates: Yacoraite Formation, northwestern Argentina

The Maastrichtian–Danian limestones of the Yacoraite Formation (northwestern Argentina) show carbon and oxygen isotopic values consistent with shallow marine conditions. The members of the formation respond to different sedimentary environments and are characterised by distinctive stable isotopes and geochemistry. The basal Amblayo Member is composed of high-energy dolomitic limestones and limestones with positive isotopic values (+2‰ δ¹³C, +2‰ δ¹⁸O). The top of the member reveals an isotopic shift of δ¹³C (−5‰) and δ¹⁸O (−10‰), probably related to a descent in the sea level. The sandy Güemes Member has isotopically negative (−2‰ δ¹³C, −1‰ δ¹⁸O) limestones, principally controlled by water mixing, decreased organic productivity, and compositional changes in the carbonates. The isotopically lighter limestones are calcitic, with a greater terrigenous contribution and different geochemical composition (high Si–Mn–Fe–Na, low Ca–Mg–Sr). These isotopic and lithological changes relate to the Cretaceous–Palaeogene transition. The Alemanía Member, composed of dolomitic limestones and pelites, represents a return to marine conditions and shows a gradual increase in isotopic values, reaching values similar to those of the Amblayo Member. The Juramento Member, composed of stromatolite limestones, shows isotopic variations that can be correlated with the two well-defined, shallowing-upward sequences of the member.     

Response of North American Great Basin Lakes to Dansgaard–Oeschger oscillations

We correlate oscillations in the hydrologic and/or cryologic balances of four Great Basin surface-water systems with Dansgaard–Oeschger (D–O) events 2–12. This correlation is relatively strong at the location of the magnetic signature used to link the lake records, but becomes less well constrained with distance/time from the signature. Comparison of proxy glacial and hydrologic records from Owens and Pyramid lakes indicates that Sierran glacial advances occurred during times of relative dryness. If our hypothesized correlation between the lake-based records and the GISP2 δ¹⁸O record is correct, it suggests that North Atlantic D–O stades were associated with relatively cold and dry conditions and that interstades were associated with relatively warm and wet conditions throughout the Great Basin between 50,500 and 27,000 GISP2 yr B.P. The Great Basin lacustrine climate records reinforce the hypothesis that D–O events affected the climate throughout much of the Northern Hemisphere during marine isotope stages 2 and 3. However, the absolute phasing between lake-size and ice-core δ¹⁸O records remains difficult to determine.     

Petrological, geochemical, and stable isotope constraints on the genesis of the Miocene igneous rocks of Chetaibi and Cap de Fer (NE Algeria)

Miocene igneous rocks (diorites, andesites, dacites, rhyolites and microgranites) of Chetaibi and Cap de Fer massif, NE Algeria, are high-K calc-alkaline to shoshonitic rocks. Fresh diorites have δ³⁴S and δ¹⁸O values ranging between −2.5‰ and +5.9‰, +6.5‰ and +6.7‰ respectively, indicating a mantle origin. The relatively low δ³⁴S values (−5.4‰ to −12.2‰) and high δ¹⁸O (+8.3‰ to +9.0‰) of altered diorites indicate the input of a crustal component to the initial magma. The microgranites’ I-type signature is indicated by the geochemical data and the δ³⁴S and δ¹⁸O values of −1.2‰ and −3.6‰, and +7.8‰ to +10.4‰ respectively. The andesites show a large variation of δ³⁴S, between −33.2‰ and +25.7‰. Massive andesites with δ³⁴S between +6.8‰ and +7.6‰ preserve a ³⁴S-enriched mantle signature. The δ³⁴S of the lava flows between +25.7‰ and +25.8‰ are attributed to open system magma degassing, whereas the low δ³⁴S of two andesitic dyke samples (−13.7‰ and −33.2‰) strongly suggest a crustal sulphur input. High δ¹⁸O (+9.2‰ to +15.7‰) of andesites indicate post-magmatic alteration (mainly silicification); the flyschs with δ¹⁸O between of +13.3‰ and +21.7‰ are most likely the contaminant. Quartz veins within the andesites gave a δ¹⁸O value of +23.0‰ while silica-filling vesicles yielded a value of +13.8‰. Initial Sr-isotope data are rather high for all the rocks (diorites: 0.707–0.708, andesites: 0.707–0.710, and microgranites and rhyolites: 0.717–0.719), and because geochemical and stable isotope data do not indicate a substantial amount of crustal assimilation, an extensive enrichment of the mantle source by subducted sediments is called for. A metasomatized-mantle source, characterized by high radiogenic Sr and relatively high δ¹⁸O, has also been indicated for the genesis of similar Tertiary igneous rocks in the Western Mediterranean basin, e.g. the Volcanic Province of southeasten Spain [Benito, R., Lopez-Ruiz, J., Cebria, J.M., Hertogen, J., Doblas M., Oyarzun, R., Demaiffe, D., 1999. Sr and O isotope constraints on source and crustal contamination in the high-K calc-alkaline and shoshonitic neogene volcanic rocks of SE Spain. Lithos 46, 773–802] and some plutons of northeastern Algeria [Ouabadi, A., 1994. Pétrologie, géochimie et origine des granitoïdes peralumineux à cordiérite (Cap Bougaroun, Béni-Touffout et Filfila), Algérie nord-orientale. Thèse de Doctorat, Université de Rennes I, France, 257p; Fourcade, S., Capdevila, R., Ouabadi, A., Martineau, F., 2001. The origin and geodynamic significance of the Alpine cordierite-bearing granitoids of northern Algeria. A combined petrological, mineralogical, geochemical and isotopic (O, H, Sr, Nd) study. Lithos 57, 187–216].     

Hydrochemistry and isotope compositions of groundwater from the Shihongtan sandstone-hosted uranium deposit, Xinjiang, NW China

Groundwaters and surface water in the Shihongtan sandstone-hosted U ore district, Xinjiang, NW China, were sampled and analyzed for their major-, and trace element concentrations and oxygen, hydrogen, boron and strontium isotope compositions in order to assess the possible origins of the waters and water–rock interactions that occurred in the deep aquifer system. The waters in the study district have been grouped into three hydrochemical facies: Facies 1, potable spring-water, is a pH neutral (7.0), Na–Ca–HCO₃ type water with low total dissolved solids (TDS; 0.2 g/l, fresh) and has δ¹⁸O of − 8.3‰, δD of − 48.2‰,δ¹¹B of 1.5‰, and ⁸⁷Sr/⁸⁶Sr of 0.70627. Facies 2 groundwaters are mildly acidic to mildly alkaline (pH of 6.5–8.0, mean 7.3), Na–Ca–Mg–Cl–SO₄ type waters with moderate TDS (8.2 g/l–17.2 g/l, mean 9.3 g/l, brackish) and haveδ¹⁸O values in the − 5.8‰ to − 9.3‰ range (mean − 8.1‰), δD values in the − 20.8‰ to − 85.5‰ range (mean − 47.0‰),δ¹¹B values in the + 9.5‰ to + 39.1‰ range (mean + 17.1‰), and ⁸⁷Sr/⁸⁶Sr values in the 0.70595 to 0.70975 range (mean 0.70826). Facies 3, Aiting Lake water, is a mildly alkaline (pH = 7.4), Na–Ca–Mg–Cl–SO₄ type water with the highest TDS (249.1 g/l, brine) and has δ¹⁸O of − 2.8‰, δD of − 45.8‰,δ¹¹B of 21.2‰, and ⁸⁷Sr/⁸⁶Sr of 0.70840. The waters from the study district show a systematic increase in major, trace element and TDS concentrations and δ¹¹B values along the pathway of groundwater migration which can only be interpreted in terms of water–rock interaction at depth and strong surface evaporation. The hydrochemical and isotopic data presented here confirm that the groundwaters in the Shihongtan ore district are the combined result of migration, water–rock interaction and mixing of meteoric water with connate waters contained in sediments.     

A 37-Meter Record of Paleoclimatological Events from Stable Isotope Data on Continental Molluscs in Valle di Castiglione, Near Rome, Italy

New stable isotope analyses on molluscan shells from a long core drilled in the crater lake of Valle di Castiglione, near Rome, extended the investigated portion of the core to 37 m. The succession of δ¹⁸O‰ values in the core interval 37–2.3 m ranges from −2.8 to +6.9‰ with only six samples below 0‰ _(PDB). These results point to arid climatic phases coupled with the high measured δ¹⁸O values of the biogenic carbonate. In contrast, depleted ¹⁸O samples correspond to wet climatic periods, in agreement with a strong evaporative control on the lake water isotopic composition. The ¹³C content of the shells shows sharp changes controlled by the dissolved inorganic carbon isotope budget. Isotopic data suggest that the whole body of water behaved as a closed system, thus resembling lacustrine systems located in arid and semiarid regions where hydrological control dominates the geochemical parameters.     

Petrology and isotopic geochemistry of dawsonite-bearing sandstones in Hailaer basin, northeastern China

The CO₂ gas reservoir sandstones in the Hailaer Basin contain abundant dawsonite and provide an ideal laboratory to study whether any genetic relationship exists between dawsonite and the modern gas phase of CO₂. The origins of dawsonite and CO₂ in these sandstones were studied by petrographic and isotopic analysis. According to the paragenetic sequence of the sandstones, dawsonite grew later than CO₂ charging at 110–85 Ma. The dawsonite δ¹⁸O value is 7.4‰ (SMOW), and the calculated δ¹⁸O values of the water present during dawsonite growth are from −11.4‰ to −9.2‰ (SMOW). This, combined with the NaHCO₃-dominated water linked to dawsonite growth, suggests meteoric water being responsible for dawsonite growth. The δ¹³C values of gas phase CO₂ and the ratios of ³He/⁴He of the associated He suggest a mantle magmatic origin of CO₂-rich natural gas in Hailaer basin. Dawsonite δ¹³C values are −5.3‰ to −1.5‰ (average −3.4‰), and the calculated δ¹³C values of CO₂ gas in isotopic equilibrium with dawsonite are −11.4‰ to −7.3‰. These C isotopic values are ambiguous for the dawsonite C source. From the geological context, the timing of events, together with formation water conditions for dawsonite growth, dawsonite possibly grew in meteoric-derived water, atmospherically-derived CO₂ maybe, or at least the dominant, C source for dawsonite. It seems that there are few relationships between dawsonite and the modern gas phase of CO₂ in the Hailaer basin.     

Stable isotope evidence for multiple fluid regimes during carbonate cementation of the Upper Tertiary Hazeva Formation, Dead Sea Graben, southern Israel

Stable carbon- and oxygen-isotope compositions of calcite and dolomite cements have been used to understand porewater evolution in the Upper Tertiary Hazeva Formation within the Dead Sea Graben, southern Israel. Sandstone samples were obtained from four boreholes in three tectonic blocks of the graben over depths of 253–6448 m, a variation that largely reflects differential subsidence of individual fault-bounded blocks. Early carbonate cements dominate diagenesis. Calcite occurs at <1600 m, but was replaced by dolomite at greater depths. Dolomite at 1600–2700 m is Fe-poor (<0.8 mol% FeCO₃), and at 4700–6200 m, Fe-rich (0.5–7.2 mol% FeCO₃). Magnesite, anhydrite and halite are the final diagenetic phases. Calcite has positively correlated δ¹⁸O (+21‰ to +25‰) and δ¹³C (−6‰ to −2‰) values that generally decrease with depth. Dolomite has a wider variation in δ¹⁸O (+18‰ to +30‰) and δ¹³C (−8‰ to −1‰) values, which also generally are lower with increasing depth. However, the δ¹³C and δ¹⁸O values of dolomite from the uppermost 400 m of the Hazeva Formation in the Sedom Deep-1 borehole are anomalous in spanning the entire range of stable carbon and oxygen isotopic compositions over this relatively small interval.The decreasing dolomite δ¹³C values likely indicate an increased contribution of carbon from organic sources with increasing depth. Except for the uppermost 400 m, Hazeva Formation dolomite in the Sedom Deep-1 borehole has stable carbon-isotope compositions that imply initial dolomitization at much shallower levels, prior to the preferential subsidence of this tectonic block. The oxygen isotopic compositions of the calcite cement are best explained by equilibration at present burial temperatures (≤55 °C) with porewater of meteoric origin. Its δ¹⁸O values increased from −5‰ at the shallowest depths to 0‰ at 1600 m. The dolomite oxygen isotopic compositions also reflect equilibration at present burial temperatures with porewaters ranging from 0‰ at 1600 m to +7‰ at 3600 m (100 °C). In the deepest fault block (Sedom Deep-1 borehole), however, increasingly Fe-rich dolomite has (re)equilibrated with porewater whose δ¹⁸O values decreased from +9‰ at 4750 m (120 °C) to +1‰ to +2‰ by 6200 m (150 °C).Much of the dolomite likely formed at relatively shallow depths from saline brines derived from precursors to the Dead Sea. These infiltrated the Hazeva Formation, mixing with and largely displacing meteoric water, and dolomitizing calcite. Rock–water ratios tended to be high during these processes. However, the upper 400 m of the Hazeva Formation in the deepest fault block were likely deposited during its rapid tectonic subsidence, and largely escaped the initial style of dolomitization pervasive elsewhere in the study area. These sediments were also capped by evaporites. This relatively thin interval likely became a preferential conduit for brines that escaped underlying and overlying strata, including the Fe-rich, lower ¹⁸O fluids (evolved seawater?) present in the deepest part of the graben. These rocks present the most promising target for the passage and accumulation of hydrocarbons in the study area.     

Assessing the past thermal and chemical history of fluids in crystalline rock by combining fluid inclusion and isotopic investigations of fracture calcite

Fluid inclusion studies combined with the isotope geochemistry of several generations of fracture calcite from the Olkiluoto research site, Finland, has been used to better understand the past thermal and fluid history in the crystalline rock environment. Typically, fracture mineral investigations use O and C isotopes from calcite and an estimate of the isotopic composition of the water that precipitated the calcite to perform δ¹⁸O geothermometry calculations to estimate past temperature conditions. By combining fluid inclusion information with calcite isotopes, one can directly measure the temperature at which the calcite formed and can better determine past fluid compositions. Isotopic, petrologic and fluid inclusion studies at the Olkiluoto research site in Finland were undertaken as part of an investigation within the Finnish nuclear waste disposal program. The study revealed that four fluids were recorded by fracture calcites. From petrologic evidence, the first fluid precipitated crystalline calcite at 151–225°C with a δ¹³C signature of −21 to −13.9‰ PDB and a δ¹⁸O signature of 12.3–13.0‰ SMOW. These closed fracture fillings were found at depths greater than 500 m and were formed from a high temperature, low salinity, Na–Cl fluid of possible meteoric water altered by exchange with wallrock or dilute basinal origin. The next fluid precipitated crystalline calcite with clay at 92–210°C with a δ¹³C signature of −2.6 to +3.8‰ PDB and a δ¹⁸O signature of 19.4–20.7‰ SMOW. These closed fracture fillings were found at depths less than 500 m and were formed from a moderate to high temperature, low to moderate salinity, Na–Cl fluid, likely of magmatic origin. The last group of calcites to form, record the presence of two distinct fluid types. The platy (a) calcite formed at 95–238°C with a δ¹³C signature of −12.2 to −3.8‰ PDB and a δ¹⁸O signature of 14.9–19.6‰ SMOW, from a high temperature, low salinity, Na–Cl fluid of possible magmatic origin. The platy (b) calcite formed at 67–98°C with a δ¹³C signature of −13.0 to −6.2‰ PDB and a δ¹⁸O signature of 15.1–20.1‰ SMOW, from a low temperature, high salinity, Ca–Na–Cl fluid of possible basinal brine origin. The two calcites are related through a mixing between the two end members. The source of the fluids for the platy grey (a) calcites could be the olivine diabase dykes and sills that cut through the site. The source of fluids for the platy (b) calcites could be the Jotnian arkosic sandstone formations in the northern part of the site. At the Olkiluoto site, δ¹⁸O geothermometry does not agree with fluid inclusion data. The original source of the water that forms the calcite has the largest effect on the isotopic signature of the calcites formed. Large isotopic shifts are seen in any water by mineral precipitation during cooling under rock–water equilibrium fractionation conditions. Different calcite isotopic signatures are produced depending on whether cooling occurred in an open or closed system. Water–rock interaction, at varying W/R ratios, between a water and a host rock can explain the isotopic shifts in many of the calcites observed. In some cases it is possible to shift the δ¹⁸O of the water by +11.5‰ (SMOW) using a realistic water–rock ratio. This process still does not explain some of the very positive δ¹⁸O values calculated using fluid inclusion data. Several other processes, such as low temperature recrystallization, boiling, kinetic effects and dissolution of calcite from fluid inclusion walls can affect isotopic signatures to varying degrees. The discrepancy between fluid inclusion data and δ¹⁸O geothermometry at the Olkiluoto site was most likely due to poor constraint on the original source of the water.     

Paleohydrology of the upper Laurentian Great Lakes from the late glacial to early Holocene

Between 10,500 and 9000 cal yr BP, δ¹⁸O values of benthic ostracodes within glaciolacustrine varves from Lake Superior range from − 18 to − 22‰ PDB. In contrast, coeval ostracode and bivalve records from the Lake Huron and Lake Michigan basins are characterized by extreme δ¹⁸O variations, ranging from values that reflect a source that is primarily glacial ( − 20‰ PDB) to much higher values characteristic of a regional meteoric source ( − 5‰ PDB). Re-evaluated age models for the Huron and Michigan records yield a more consistent δ¹⁸O stratigraphy. The striking feature of these records is a sharp drop in δ¹⁸O values between 9400 and 9000 cal yr BP. In the Huron basin, this low δ¹⁸O excursion was ascribed to the late Stanley lowstand, and in the Lake Michigan basin to Lake Agassiz flooding. Catastrophic flooding from Lake Agassiz is likely, but a second possibility is that the low δ¹⁸O excursion records the switching of overflow from the Lake Superior basin from an undocumented northern outlet back into the Great Lakes basin. Quantifying freshwater fluxes for this system remains difficult because the benthic ostracodes in the glaciolacustrine varves of Lake Superior and Lake Agassiz may not record the average δ¹⁸O value of surface water.     

Oxygen isotope map of the giant metamorphic-hydrothermal system around the northern part of the Idaho batholith, U.S.A.

Determinations of δ¹⁸O values from 100 outcrops of Belt Supergroup (Wallace Fm.) metasedimentary rocks in the Idaho panhandle reveal a regular regional pattern that was produced by pervasive fluid infiltration and isotopic exchange. Low grade argillites at large distances (60 km) from the Idaho batholith have high δ¹⁸O values +15, compatible with their probable primary values. Pelitic rocks with anomalously low δ¹⁸O values of + 8.7 to + 12.7‰ occur in the following zones: (1) in a 5000 km² zone of schist and gneiss peripheral to the Idaho batholith, generally coincident with high-grade (sillimanite-bearing) assemblages; (2) in high-grade metasedimentary roof pendants within the Idaho batholith; (3) peripheral to small Cretaceous stocks; and (4) within and near the scapolite-bearing zone south-west of St. Regis. On δ¹⁸O−δ¹⁸O plots, data from coexisting minerals define trends with unit slopes, indicating that the reductions in ¹⁸O occurred under high-grade metamorphic conditions. This metamorphism culminated in the emplacement of the Idaho batholith, probably as a consequence of profound crustal thickening associated with the Cretaceous accretion of the Wallowa-Seven Devils arc terranes with North America. The huge low-¹⁸O region is bounded by a “steep” δ¹⁸O gradient (0.1–0.5‰/km) that occurs in low-grade rocks along and near the Lewis and Clark Line, well below the biotite isograd. This boundary zone may be analogous to, but is not nearly as sharp as, those of meteoric-hydrothermal systems in many regions. The important ore deposits of the Coeur d'Alene district are located in this peripheral zone, suggesting that the metamorphic-hydrothermal system may have been intimately involved in their formation. In addition, the metamorphic-hydrotermal system in Idaho is larger, deeper and higher in temperature than typical meteoric-hydrothermal systems, and it involved fluids with much higher δ¹⁸O values that were probably dominantly derived from formation waters. Accordingly, this system produced rocks with δ¹⁸O values similar to those of the Idaho batholith, and mineral assemblages that approach isotopic equilibrium under high temperature conditions.     

Fluid inclusion and stable isotope study of the Cobre–Babilonia polymetallic epithermal vein system, Taxco district, Guerrero, Mexico

The Cobre–Babilonia vein system formed during a single major hydrothermal stage and is part of the Taxco district in Guerrero, southern Mexico. Homogenization and ice melting temperatures range from 160 to 290 °C and from − 11.6 to − 0.5 °C, respectively. We determined an approximate thermal gradient of 17 to 20 °C per 100 m using fluid inclusions. A thermal peak marked by the 290 °C isotherm is interpreted as a major feeder channel to the veins. The highest content of Zn + Pb in ore coincides with the 220 and 240 °C isotherms. Salinities of mineralizing fluids range from 0.8 to 15.6 wt.% NaCl equiv, and are distributed in two populations that can be related with barren or ore-bearing vein sections, with 0.8 to 6 wt.% NaCl equiv and 7 to 15.6 wt.% NaCl equiv, respectively. δ¹³C and δ¹⁸O water values from calcite from the Cobre–Babilonia vein system and the Esperanza Vieja and Guadalupe mantos range − 5.4‰ to − 10.4‰ and 9.9‰ to 13.4‰, respectively. δ³⁴S values range from 0‰ to 3.2‰ and − 0.7‰ to − 4.3‰ in sphalerite, − 4‰ to 0.9‰ in pyrite, and − 1.4‰ to − 5.5‰ in galena. Both fluid inclusion and stable isotope data are compatible with magmatic and meteoric sources for mineralizing fluids. Also, sulfur isotope compositions suggest both magmatic and sedimentary sources for sulfur.     

Stable isotope and geochemical evidence of formation pore fluid evolution during diagenesis of Tertiary sandstones and mudrocks of the Niger Delta

Petrological data provide evidence that framboidal pyrite, Fe-carbonates and kaolinite are the major diagenetic minerals developed during burial diagenesis in the Tertiary Niger Delta sandstones and associated mudrocks. The pyrite sulphur, carbonate carbon and oxygen and kaolinite oxygen and hydrogen isotope compositions have been determined. These data (pyrite, δ³⁴S = −24.8 to 21.0‰; “siderite”, δ¹³C(PDB) = −14.7 to +5.0‰, δ¹⁸O(PDB) = −19.1 to −0.6‰; Fe-calcite, δ¹³C(PDB) = +17.5 to 17.9‰, δ¹⁸O(PDB) = −8.3 to −8.0‰; kaolinite, δ¹⁸O(SMOW) = +14.7 to 17.5‰, δD (SMOW) = −86 to −43‰) have been used to interpret the isotopic compositions of the precipitating pore fluids and/or the temperatures of mineral formation. The interpretation of these results indicate that in the deltaic depositional setting the syndepositional pore waters had a significant but variable marine influence that favoured the early formation of pyrite. Subsequently the subsurface influence of meteoric waters, showing varying degrees of modification involving organic and/or water-rock reactions, played an increasingly significant role in the development of later diagenetic cements in the sediments when abundant authigenic carbonates and kaolinites were formed.     

Do Stable Isotope Data from Calcrete Record Late Pleistocene Monsoonal Climate Variation in the Thar Desert of India?

Late Pleistocene terrestrial climate records in India may be preserved in oxygen and carbon stable isotopes in pedogenic calcrete. Petrography shows that calcrete nodules in Quaternary sediments of the Thar Desert in Rajasthan are pedogenic, with little evidence for postpedogenic alteration. The calcrete occurs in four laterally persistent and one nonpersistent eolian units, separated by colluvial gravel. Thermoluminescence and infrared- and green-light-stimulated luminescence of host quartz and feldspar grains gave age brackets for persistent eolian units I–IV of ca. 70,000–60,000, ca. 60,000–55,000, ca. 55,000–43,000, and ca. 43,000–25,000 yr, respectively. The youngest eolian unit (V) is <10,000 yr old and contains no calcrete. Stable oxygen isotope compositions of calcretes in most of eolian unit I, in the upper part of eolian unit IV, and in the nonpersistent eolian unit, range between −4.6 and −2.1‰ PDB. These values, up to 4.4‰ greater than values from eolian units II and III, are interpreted as representing nonmonsoonal¹⁸O-enriched “normal continental” waters during climatic phases when the monsoon weakened or failed. Conversely, 25,000–60,000-yr-old calcretes (eolian units II and III) probably formed under monsoonal conditions. The two periods of weakened monsoon are consistent with other paleoclimatic data from India and may represent widespread aridity on the Indian subcontinent during isotope stages 2 and 4. The total variation in δ¹³C is 1.7‰ (0.0–1.7‰), and δ¹³C covaries positively and linearly with δ¹⁸O. δ¹³C values are highest when δ¹⁸O values indicate the most arid climatic conditions. This is best explained by expansion of C₄grasses at the expense of C₃plants at low latitudes during glacial periods when atmosphericpCO₂was lowered. C₄dominance was overridingly influenced by global change in atmosphericpCO₂despite the lowered summer rainfall.     

A biogenic-silica δO record of climatic change during the last glacial–interglacial transition in southwestern Alaska

Despite growing evidence for environmental oscillations during the last glacial–interglacial transition from high latitude, terrestrial sites of the North Pacific rim, oxygen-isotopic records of these oscillations remain sparse. The lack of data is due partially to the paucity of lakes that contain carbonate sediment suitable for oxygen-isotopic analysis. We report here the first record of oxygen-isotopic composition in diatom silica (δ¹⁸O_Si) from a lake in that region. δ¹⁸O_Si increases gradually from 19.0 to 23.5‰ between 12,340 and 11,000 ¹⁴C yr B.P., reflecting marked climatic warming at the end of the last glaciation. Around 11,000 ¹⁴C yr B.P., δ¹⁸O_Si decreases by 1.7‰, suggesting a temperature decrease of 3.5–8.9 °C at the onset of the Younger Dryas (YD) in southwestern Alaska. Climatic recovery began ca. 10,740 ¹⁴C yr B.P., as inferred from the increase of δ¹⁸O_Si to a maximum of 23.9‰ near the end of the YD. Our data reveal that a YD climatic reversal in southwestern coastal areas of Alaska occurred, but the YD climate did not return to full-glacial conditions.     

Holocene hydrological reconstructions from stable isotopes and paleolimnology, Cordillera Real, Bolivia

Multiproxy analyses of sediment cores from Lago Taypi Chaka Kkota (LTCK) Cordillera Real, Bolivia, provide a record of drier conditions following late Pleistocene deglaciation culminating in pronounced aridity between 6.2 and 2.3 ka B.P. Today LTCK is a glacial-fed lake that is relatively insensitive to changes in P–E because it is largely buffered from dry season draw-down through the year-round supply of glacial meltwater. This was not the case during the middle to late Holocene when glaciers were absent from the watershed. Lake-water δ¹⁸O values inferred from δ¹⁸O analysis of sediment cellulose range from −12.9 to −5.3‰ and average −8.7‰ between 6.2 and 2.3 ka B.P. Modern lake-water δ¹⁸O from LTCK averages −14.8‰ which is compatible with the δ¹⁸O_lw value of −14.3‰ for the surface sediment cellulose. Analyses of δ¹⁸O from modern surface waters in 23 lakes that span the range from glacial-fed to closed basin vary from −16.6 to −2.5‰. This approximates the magnitude of the down-core shift in δ¹⁸O_lw values in LTCK during the middle to late Holocene from −12.9 to −5.3‰. Strong paleohydrologic change during the middle Holocene is also evident in diatom assemblages that consist of shallow-water, non-glacial periphytic taxa and bulk organic δ¹³C and δ¹⁵N that show increases likely resulting from degradation of lacustrine organic matter periodically exposed to subaerial conditions. Neoglaciation began after 2.3 ka B.P. as indicated by changes in the composition of the sediments, lower δ¹⁸O values, and a return to diatom assemblages characteristic of the glacial sediments that formed during the Late Pleistocene. Collectively, these data indicate that the past 2.3 ka B.P. have been the wettest interval during the Holocene. Millennial-scale shifts in the paleohydrologic record of LTCK during the early to middle Holocene conform to other regional paleoclimatic time-series, including Lake Titicaca and Nevado Sajama, and may be driven by insolation and resultant changes in atmospheric circulation and moisture supply. In contrast, an apparent 1200-year lag in the onset of wetter conditions at LTCK (2.3 ka B.P.) compared to Lake Titicaca (3.5 ka B.P.) provides evidence for variable sub-regional hydrologic response to climate change during the middle to late Holocene.     

Fluid flow, alteration and polysulphide mineralisation associated with a low-angle reverse shear zone in the Lower Palaeozoic of the Anglo-Brabant fold belt, Belgium

In the Lower Palaeozoic rocks of the Brabant Massif (Belgium), a recently discovered polysulphide mineralisation is related to a low-angle reverse shear zone. This shear zone has been attributed to the main early Devonian deformation event. Data from boreholes and outcrops allow a detailed investigation of the alteration pattern and palaeofluid flow along this shear zone. Macroscopic observations of the mineralogy and quantitative changes in the phyllosilicate mineralogy indicate that this shear zone is characterised by an envelope of intense sericitisation and silicification. In addition, chloritisation is associated with this alteration. The alteration zone may reach a thickness of 250 m. Ore mineralisation occurred synkinematically and is spatially related to the shear zone. The mineralisation consists of pyrite, marcasite, arsenopyrite, pyrrhotite, chalcopyrite, sphalerite, galena, stibnite and smaller amounts of tetrahedrite and other sulphosalts. It is concentrated in quartz–sulphide veins or occurs diffusely in the host rock. The mineralising fluids have a low-salinity H₂O–CO₂–CH₄–NaCl–(KCl) composition and a minimum temperature of 250–320 °C. The δ¹⁸O values of quartz vary between +12.3‰ and +14.5‰ SMOW, and δD compositions of the fluid inclusions in the quartz crystals range from −65‰ to −35‰ V-SMOW. The δD and the calculated δ¹⁸O values of the mineralising fluids fall in the range typical for metamorphic fluids and partly overlap with that for primary magmatic fluids. The δ³⁴S values, between +4.7‰ and +10.6‰ CDT, fall outside the interval typical for I-type magmas. Important migration of likely metamorphic fluids, causing a widespread alteration and a polysulphide mineralisation along a low-angle shear zone, has, thus, been identified for the first time in the Caledonian Anglo-Brabant fold belt.     

Carbon and Oxygen Isotope Geochemistry of the Amba Dongar Carbonatite Complex, Gujarat, India

A carbon and oxygen isotope survey based on 42 samples from the Amba Dongar carbonatite complex of Gujarat, India, indicates that the magmatic differentiation series sövite → alvikite → ankeritic carbonatite is beset with a distinct isotope trend characterized by a moderate rise in ¹³C coupled with a sizeable increase in ¹⁸O. From an average of −4.6 ± 0.4 ‰ [PDB] for the least differentiated (coarse) sövite member, δ¹³C values slowly increase in the alvikite (−3.7 ± 0.6 ‰) and ankeritic fractions (−3.0 ± 1.1 ‰), whereas δ¹⁸O rises from 10.3 ± 1.7 ‰ [SMOW] to 17.5 ± 5.8 ‰ over the same sequence, reaching extremes between 20 and 28 ‰ in the latest generation of ankeritic carbonatite. While an apparent correlation between δ¹³C and δ¹⁸O over the δ¹⁸O range of 7–13 ‰ conforms with similar findings from other carbonatite complexes and probably reflects a Rayleigh fractionation process, the observed upsurge of ¹⁸O notably in the ankeritic member is demonstrably related to a late phase of low-temperature hydrothermal activity involving large-scale participation of ¹⁸O-depleted groundwaters. As a whole, the Amba Dongar carbonatite province displays the characteristic ¹³C/¹²C label of deep-seated (primordial) carbon, reflecting the carbon isotope composition of the subcontinental upper mantle below the Narmada Rift Zone of the Indian subcontinent.     

The origin of dolomite associated with salt diapirs in central Tunisia: Preliminary investigations of field relationships and geochemistry

Black and white dolomite crystals (mm to cm width) of different isotopic composition are associated with Triassic diapirism in central Tunisia, as well as with evaporite minerals and clays. The white dolomites occur mostly in the Jabal Hadifa diapir near the contact with Cretaceous limestones, whereas the smaller black dolomites occur in the Jabal Hamra diapir. The former dolomite has a narrow range of δ¹⁸O and δ¹³C values (− 3.83‰ to − 6.60‰ VPDB for δ¹⁸O; − 2.11‰ to − 2.83‰ VPDB for δ¹³C), whereas the latter dolomite has a wider range and more depleted values (− 4.92‰ to − 9.97‰ for δ¹⁸O; − 0.55‰ to − 6.08‰ for δ¹³C). However, the ⁸⁷Sr / ⁸⁶Sr ratios of most of the samples are near Triassic seawater values. Dolomite formation is due to at least two different fluids. The main fluid originated from deeper hydrothermal or basinal sources related to the Triassic saliferous rocks and ascended through faults during the diapiric intrusion. The second, less important fluid source is related to meteoric water originating from Cretaceous rocks.     

Lower Eocene carbonate-cemented “chimney” structures (Varna, Bulgaria) — Control of seepage rates on their formation and stable isotopic signature

The genesis of Lower Eocene calcite-cemented columns, “pisoid”-covered structures and horizontal interbeds, clustered in dispersed outcrops in the Pobiti Kamani area (Varna, Bulgaria) is related to fossil processes of hydrocarbon migration. Field observations, petrography and stable isotope geochemistry of the cemented structures and associated early-diagenetic veins, revealed that varying seepage rates of a single, warm hydrocarbon-bearing fluid, probably ascending along active faults, controlled the type of structure formed and its geochemical signature. Slow seepage allowed methane to oxidize within the sediment under ambient seafloor conditions (δ¹⁸O = − 1 ± 0.5‰ V-PDB), explaining columns' depleted δ¹³C ratios of − 43‰. Increasing seepage rates caused methane to emanate into the water column (δ¹³C = − 8‰) and raised precipitation temperatures (δ¹⁸O = − 8‰). Calcite-cemented conduits formed and upward migrating fluids also affected interbed cementation. Even higher-energy fluid flow and temperatures likely controlled the formation of “pisoids”, whereby sediment was whirled up and cemented.     

Α high-resolution late Holocene speleothem record from Kaite Cave, northern Spain: δO variability and possible causes

A high-resolution calcite oxygen stable isotopic (δ¹⁸O) record, covering the past 4000 years, was obtained from Kaite Cave, northern Spain. The record has a mean δ¹⁸O value of -6.25‰ VPDB and a range of 2‰. Spectral analysis of the δ¹⁸O data shows significant periodicities of 2400–1900, 600, 150, 27, and 22 years. The amplitudes during these periods range from 0.2‰ to 2‰. Factors controlling the isotopic ratio in the speleothem were evaluated. The calcite is most likely precipitated under equilibrium conditions, with the cave calcite δ¹⁸O interpreted as a proxy of oxygen isotopic composition in local rainwater. Other factors such as temperature or fractionation in the karst system prior to calcite precipitation are considered of negligible or of minor importance. Mechanisms affecting rainfall isotopic composition were also investigated on different time scales. Precipitation amount is the primary factor controlling the high-frequency δ¹⁸O oscillations. Other climate parameters, such as changes of storm tracks may have significant contributions on centennial and millennial time scales.