Thermochemical sulphate reduction in the Upper Devonian Cairn Formation of the Fairholme carbonate complex (South-West Alberta, Canadian Rockies): evidence from fluid inclusions and isotopic data

The Fairholme carbonate complex is part of the extensively dolomitized Upper Devonian carbonate reefs in west-central Alberta. The studied formations contain moulds (up to 10 cm in diameter), which are filled partially with (saddle) dolomite, quartz and calcite cements. These cements precipitated from a mixture of brines that acquired high salinity by dissolution of halite and brines derived from evaporated sea water. The fluids were warm (homogenization temperature of primary fluid inclusions of 76 to 200 °C) and saline (20 to 25 wt% NaCl equivalent) and testify to thermochemical sulphate reduction processes. The latter is deduced from S in solid inclusions, CO₂ and H₂S in volatile-rich aqueous inclusions and depleted δ¹³C values down to −26‰ Vienna Pee Dee Belemnite. High ⁸⁷Sr/⁸⁶Sr values (0·7094 to 0·7110) of the cements also indicate interaction of the fluids with siliciclastic sequences. The thermochemical sulphate reduction-related cements probably formed during early Laramide burial. Another (younger) calcite phase, characterized by depleted δ¹⁸O values (−23·9‰ to −13·9‰ Vienna Pee Dee Belemnite), low Na (27 to 37 p.p.m.) and Sr (39 to 150 p.p.m.) concentrations and non-saline (∼0 wt% NaCl equivalent) fluid inclusions, is attributed to post-Laramide meteoric water.     

Stable isotope study of carbonate sediments from the Coorong Area, South Australia

ABSTRACT
The mineralogy and isotope geochemistry of carbonate minerals in the Coorong area are determined by the water chemistry of different depositional environments ranging from seawater to evaporitically modified continental water. The different isotopic compositions of coexisting calcite and dolomite suggest that each of the above two minerals was formed from water of composition and origin unique to that specific mineral. In addition, the dolomite was not formed by simple solid state cation exchange.
The occurrence of two types of dolomite was shown by isotope analysis and SEM observations. The dolomite, which is isotopically light (δ¹³C = -1 to -2% 0 ; δ¹⁸O=+3 to +5%₀) and of fine grain size (˜ 0·5 μm) probably precipitated under the influence of evaporitically modified continental water. Coarser grained dolomite (up to 4 μm) is isotopically heavier (δ¹³C=+3 to +4%₀; δ¹⁸O=+5 to + 6%₀) contains Mg in excess of Ca and was formed in or close to equilibrium with atmospheric CO² probably by the dolomitization of aragonite.     

A widespread positive δ13Ccarb anomaly at around 2.33–2.06 Ga on the Fennoscandian Shield: a paradox?

Carbon isotope measurements carried out on 201 carbonate samples from the early Proterozoic of the Kola Peninsula, N. Karelia and Norway yield δ¹³C (PDB) spanning - 20.5% to + 11%. A general δ¹³C secular trend shows that prior to 2.33 Ga values are typically 'normal' marine, averaging around - 3%0. Between 2.33 and 2.06 Ga, in Jatulian time, there follows a rapid excursion to positive δ¹³C of around + 6%. Post-Jatulian time is characterized by δ¹³C of sedimentary carbonates fluctuating between - 5% and +3%; also it is remarkable for the first pronounced development of diagenetic carbonates, which have δ¹³C between - 14 % and - 6% . The c. 6% positive δ¹³C shift with a duration of about 270 Myr coincides with a maximum in the diversity and abundance of stromatolites, and with widespread development of 'red beds', but does not coincide with the maximum of buried C_org mass. The Fennoscandian Shield represents the largest isotoically anomalous carbonate province yet reported, and the positive δ¹³C excursion together with a series of major global palaeoenviromental changes seems to be more intense than the Precambrian/Cambrian transition events. However, it is still not clear what kind of mechanism this phenomenon could be attributed to. An increase of the 'Ronov ratio', and/or 'Broecker ratio' and other possible models are discussed as the target for future investigations.     

Terrestrial carbon-isotope records from coastal deposits (Algarve, Portugal): a tool for chemostratigraphic correlation on an intrabasinal and global scale

ABSTRACT The carbon-isotope signature of terrestrial organic matter (OM) offers a valuable tool to develop stratigraphic correlations for near-shore deposits. A mid-Cretaceous coastal succession of the western Algarve Basin, Portugal, displays a marked negative δ¹³C excursion ranging from − 21.2‰ to − 27.8‰ in the Early Aptian followed by two shifts towards higher values (up to − 19.3‰) during the Early and Late Aptian, respectively. The dominance of cuticle and leaf debris in the bulk OM fraction is confirmed by optical studies, Rock-Eval pyrolysis and by comparison with the δ¹³C signature of four different types of fossilized land-plant particles. Correlation of two terrestrial δ¹³C_bulk OM records from different study sites leads to a significant enhancement of the intrabasinal stratigraphic correlation within the Algarve Basin. Three prominent excursions in the Portuguese records can be correlated with existing δ¹³C curves from pelagic and terrestrial environments. The general carbon-isotope pattern is superimposed by small-scale fluctuations which can be explained by compositional variations within the OM.     

The isotopic composition of oxygen and carbon in the subfossil mollusc shells of the Baltic Sea as an indicator of palaeosalinity

The carbon (δ¹³ C) and oxygen (δ¹⁸O) isotopic composistion in mollusc shells in mainly determined by the isotopic composition of water and dissolved bicarbonate. The δ¹⁸O values of water show a good correlation with the salinity of the Baltic. This correlation served as a basis for reconstructing palaeosalinity and for stratifying the marine sediments according to the δ¹⁸O values of the carbonate skeletons of subfossil shells. The δ¹³C values in shells are mainly determined by the isotopic composition of land-originating bicarbonate, especially in the carbonate skeleton of Lymnaea balthica , which inhabits the immediate coastal zone. According to the δ¹⁸O data, salinity in the investigated area (the coastal area of W and NW Estonia) was highest (about 9–11%) during the Littorina stage. The Limnae a stage had, in general, a salinity similar to the contemporary one, but during some phases possibly exceeding it by 2–3%.     

Stable chlorine isotope evidence for non-marine chloride in Badenian evaporites, Carpathian mountain region

Routine trace-element geochemistry suggests that components in putative marine halite evaporites may be partly of nonmarine origin, but such interpretations are commonly ambiguous. Stable chlorine isotopes may provide a less-ambiguous marker of chloride origin where δ³⁷Cl departs from the range predicted for evaporite formation from seawater. Bedded halite with primary sedimentary textures preserves original δ³⁷Cl values. Measurable change in δ³⁷Cl can be generated by incongruent dissolution of halite, but only if less than half the original halite remains. Badenian (middle Miocene) halite from the Forecarpathian and from the East Slovakian and Transcarpathian basins has a δ³⁷Cl range of – 0.2 to 0.8‰. Two phenomena cannot be explained by simple evaporation of 0.0‰ seawater. At Wieliczka, the Shaft Salt has distinctive δ³⁷Cl values (– 0.2 to 0.0‰) relative to neighbouring salt beds (0.2 to  0.6‰), requiring a large, abrupt input of brine with negative δ³⁷Cl. Halite with high (0.6 – 0.8‰) δ³⁷Cl near the base of the East Slovakian and Transcarpathian evaporites requires a large input of chloride with positive δ³⁷Cl into the basins. Expulsion of basin brine with non-0‰δ³⁷Cl into the evaporite basins may account for the nonmarine chloride sources.     

Dolomites in the Tazekka Pb–Zn district, eastern Morocco: polyphase origin from hydrothermal fluids

Many different types of water and processes have been proposed for the formation of dolomites. The three phases of hydrothermal dolomites in the Middle Atlas Causse were investigated to elucidate their formation processes. The first two of these are associated with sphalerite and galena in stratiform and open space-filling deposits. These formed early in the history of the deposition of the Pb–Zn mineralization and commonly reveal a paragenetic overlap. A later phase, post-dating Pb–Zn mineralization, is reflected in saddle dolomite.
All three phases show a decrease in δ¹⁸O and δ¹³C values passing from sterile (unmineralized) to mineralized rocks, and isotopic signatures are independent of the carrier facies. However, early-formed dolomites can be separated into two distinct groups on the basis of δ¹⁸O values. Type 1 dolomites host stratiform ore deposits, whereas type 2 dolomites host an open space-filling ore-body. Later saddle dolomites are more depleted in ¹⁸O than either of these.
The early hydrothermal and saddle dolomites precipitated from similar fluids during three distinct events, but formed by two mechanisms: replacement (hydrothermal dolomite) and cement precipitation (saddle dolomite). They show different isotopic signatures and apparently formed at different temperatures. Field data, petrographic and stable isotope results suggest a continuum of replacement, during the Carixian for the early hydrothermal dolomite 1, and during the Toarcian for early hydrothermal dolomite 2, followed by a cement precipitation phase for saddle dolomite.     

Seasonal and interannual variability of Siberian river discharge in the Laptev Sea inferred from stable isotopes in modern bivalves

Stable oxygen and carbon isotope profiles from modern bivalve shells were investigated in order to reconstruct short-term hydrographical changes in the river-shelf system of the Laptev Sea. Oxygen isotopic profiles obtained from the aragonitic species Astarte borealis exhibit amplitude cycles interpreted as annual hydrographical cycles. These records reflect the strong contrast between summer and winter bottom water conditions in the Laptev Sea. The seasonal variations in δ¹⁸O are mainly controlled by the riverine freshwater discharge during summer with 0.5‰ per salinity unit. Corrected for a defined species-dependent fractionation offset of -0.37‰, time-dependent salinity records were reconstructed from these δ¹⁸O profiles. They indicate a good correspondence to seasonal hydrographic changes and synoptical data. Persistent trends with shell growth towards more negative δ¹³C values are observed in all specimens and appear to be related to metabolic changes of the bivalves during ontogeny. In contrast, short-term fluctuations are likely linked to seasonal variabilities of the river water outflow patterns and enhanced phytoplankton productivity during summer. This is corroborated by a clear watermass-related distinction of the various δ¹³C records made on the basis of water depth and distance from the riverine source.     

Carbon-isotope stratigraphy in shallow-water carbonates: implications for Cretaceous black-shale deposition

A Barremian to Albian succession on Mount Kanala, part of a Tethyan isolated carbonate platform, was investigated for its δ¹³C variations. The limestone sequence is composed of a series of peritidal shallowing-upward cycles with clear petrographic evidence for strong early diagenetic overprinting related to repeated subaerial exposure. Despite significant impact of diagenesis, the observed changes in δ¹³C can be very well correlated with deep-water sections from different ocean basins and shallow water carbonate platforms in the Middle East. This lends further support to the applicability of δ¹³C variations for stratigraphic purposes in shallow-water limestones. Using the δ¹³C signal, time resolution in Lower Cretaceous platform carbonates can be significantly increased, independent of bio-zonations often hampered by ecological variability.
Cyclostratigraphic analysis of the Aptian part of the section shows that strong positive excursions of the cumulative departure from mean cycle thickness of the peritidal shallowing-upward cycles coincide with global positive δ¹³C excursions. This, and the fact that positive shifts in the δ¹³C record are preserved within shallow water limestones, provide evidence that black-shale accumulation in the ocean basins occurred during sea-level rise and flooding of platform tops. Integration of carbon-isotope-, cyclo- and sequence-stratigraphic results from different carbonate platforms indicate that strong positive global δ¹³C shifts and concurrent organic-carbon burial during black-shale deposition are ultimately caused by rapid rises of eustatic sea level. Hence, the rate of change of eustatic sea level is considered to play a crucial role in black-shale accumulation in the global ocean basins during the Cretaceous.     

Geochemical Characteristics of the Akiyoshi Limestones, Japan and Their Bearing on Exploration for Blind Skarn Deposits

Abstract. Carboniferous-Permian limestones of the Akiyoshi Plateau, in the Inner Zone of southwestern Japan, are composed of essentially pure calcium carbonate containing only small amounts of other elements, and they are accompanied by marble and copper skarn deposits near the contact with late Cretaceous granitoids. The δ¹⁸O values of the Akiyoshi limestones range widely from 7.6 to 28.3% and are mostly lower than those of other areas of the same age (23–29%), whereas the differences among the δ¹³C values are small. The δ¹⁸O values are negatively correlated with Mn and Fe contents. Samples with high δ¹⁸O (>25%) and δ¹³C (>2%) values do not contain Fe, Zn, or Pb, but those with low δ¹⁸O values tend to be rich in these elements, indicating that these elements were introduced by interaction with H₂O dominant fluids, possibly of magmatic origin. Potential scores for evaluating the degree of interaction with hydro thermal fluids were calculated for δ¹⁸O, δ¹³C, Fe, Mn, Zn, Pb, and Sr. Higher scores implying much hydrothermal interaction were evident in the Mt. Hananoyama area, where there are many skarn deposits, and along faults oriented mainly NNW-SSE. Therefore, these are promising areas for exploring for blind deposits. It is likely that the hydrothermal fluid traveled through the limestones along fractures at the time of the granitic intrusions. However, the potential scores here are much smaller than those in the Pb-Zn mineralized area of the Kamioka mine, so more detailed petrological and mineralogical investigations are necessary.     

A distinct δ13C decline in organic lake sediments at the Pleistocene-Holocene transition in southern Sweden

Values of δ¹³C obtained from conventional bulk sediment radiocarbon dates encompassing the Pleistocene Holocene boundary have been compiled and plotted against ¹⁴C age. In all. 286 lake sediment dates from southern Sweden in the range 8.000 to 13.000 BP have been evaluated. A significant decrease in δ¹³C values, initiated shortly before 10.000 RP and amounting to 5%, is distinguished. This change is accompanied by increased limnic productivity. decreased erosive input and increased organic carbon content of the sediments. A probable explanation for the δ¹³C decline in organic material is decreased importance of dissolution of silicates at the transition to the Holocene. During the Late Weichselian. extensive weathering of exposed minerogenic material with subsequent input of bicarbonate to the lake water may have caused a relative enrichment of ¹³C in dissolved inorganic carbon. Furthermore, the early Holocene increase in terrestrial vegetation cover probably led to an increased supply of ¹³C depleted carbon dioxide to the lake water by root respiration. Altered limnic vegetation, presumably towards increased production of phytoplankton. could also have contributed to the observed decreasing δ¹³C trend. The importance of these processes compared to other possible influencing factors. mainly endogenic carbonate production and changes in the global carbon cycle. is discussed.     

Chemical Separation and Isotopic Variations of Cu and Zn From Five Geological Reference Materials

This paper presents an adapted anion exchange column chemistry protocol which allowed separation of high-purity fractions of Cu and Zn from geological materials. Isobaric and non-spectral interferences were virtually eliminated for consequent multiple-collector ICP-MS analysis of the isotopic composition of these metals. The procedure achieved ∼ 100% recoveries, thus ensuring the absence of column-induced isotopic fractionation. By employing these techniques, we report isotopic analyses for Cu and Zn from five geological reference materials: BCR-027 blende ore (BCR), δ⁶⁵Cu = 0.52 ± 0.15‰ (n = 10) and δ⁶⁶Zn = 0.33 ± 0.07‰ (n = 8); BCR-030 calcined calamine ore (BCR), δ⁶⁶Zn = -0.06 ± 0.09‰ (n = 8); BCR-1 basalt (USGS), δ⁶⁶Zn = 0.29 ± 0.12‰ (n = 8); NOD-P-1 manganese nodule (USGS), δ⁶⁵Cu = 0.46 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.78 ± 0.09‰ (n = 9); SU-1 Cu-Co ore (CCRMP), δ⁶⁵Cu = -0.018 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.13 ± 0.17‰ (n = 6). All uncertainties are ± 2s; copper isotope ratios are reported relative to NIST SRM-976, and zinc isotope ratios relative to the Lyon-group Johnson Matthey metal (batch 3-0749 L) solution, JMC Zn. These values agree well with the limited data previously published, and with results reported for similar natural sample types. Samples were measured using a GVi IsoProbe MC-ICP-MS, based at the Natural History Museum, London. Long-term measurement reproducibility has been assessed by repeat analyses of both single element and complex matrix samples, and was commonly better than ± 0.07‰ for both δ⁶⁶Zn and δ⁶⁵Cu.     

Chronology and organic chemistry of the Black Creek Swamp Megafauna site (Late Pleistocene), Kangaroo Island, Australia

The timing of the extinction of the Australian Megafauna and whether it was simultaneous and widespread has been a much researched topic in Quaternary geoscience. The Black Creek Swamp Megafauna site on Kangaroo Island was thought to be a refugium for Megafauna; however, recent and multidiscipline age determinations have established that the fossils are considerably older than the well-quoted extinction age of 45 kyr. Further radiocarbon age determinations, δ¹³C isotope analysis and ¹³C-NMR spectroscopy of the fossil containing organic matter demonstrates that it is highly soluble and accumulated as recently as 31–18 cal. kyr BP. These radiocarbon ages are much younger than the 100–50 kyr age bracket ascertained for the fossil material itself, implying separate episodes of death, deposition and burial. The soluble nature of the organic matter and increasing radiocarbon ages with depth suggests lateral accumulation, probably transported by subsurface waters from elevated areas proximal to the low-lying swamp. Such depositional conditions and ¹⁴C age range implies that the site may have experienced an unusually wet Last Glacial Maximum, due maybe to its proximity to the continental shelf and thus to maritime conditions. C3 vegetation dominates the Black Creek Swamp and its organic matter (δ¹³C; −30‰ and −23‰); however, variations in δ¹³C may indicate climatic shifts. ¹³C-enrichment and an abundance of salt-tolerant gastropods within the site's final phase of sediment accumulation (<6 cal. kyr BP) suggest that conditions during this most recent period were not as wet as those of the Last Glacial Maximum.     

Sulfur Content and Isotopic Ratio of Cambro-Ordovician Carbonate Rocks from South Korea: A Possible Source for Mesozoic Magmatic-hydrothermal Ore Sulfur

Abstract: Carbonate rocks of Cambrian (18 samples) and lower-middle Ordovician (11 samples) ages from South Korea were analyzed for sulfur contents of structurally substituted sulfate (SSS) and sulfides and their δ³⁴S values. The δ³⁴S values of SSS ranging from +25.9 to +45.2 permil, are averaged as +33.6 and +33.5 permil for the Cambrian and Ordovician rocks, respectively, which indicate high δ³⁴S values of the Cambro-Ordovician seawater. The SSS contents in the carbonate rocks are low being 2.9 to 17.3 ppm S (averaged as 7.0 ppm S). Sulfide sulfur, on the contrary, is much abundant containing 3 to 1,880 ppm S and the δ³⁴S values range widely between –17.6 and +31.1 permil. Sulfide sulfur of the studied rocks excluding impure carbonates has an average content of 187 ppm S and δ³⁴S value of +12.8 permil (n=24). The estimated δ³⁴S (sulfate–sulfide) values, which range from 13.8 to 25.4 permil in general with a few exceptions from 36.5 up to 52.3 permil for some impure carbonates, may provide evidence for the persistent oceanic anoxia with its temporary recovery during the Cambro-Ordovician time.
The SSS and sulfide sulfurs have often higher δ³⁴S values than the Mesozoic-Cenozoic ore sulfur (Ishihara et al., 2000). Since carbonate rocks are very reactive with circulating hydrothermal ore solution, high δ³⁴S values of the Korean ore deposits might be caused to some extent by ³⁴S enrichment from the host carbonates, resulting in the low SSS contents observed.     

Long-term (105) or short-term (103) δ13C excursion near the Palaeocene-Eocene transition: evidence from the Tethys

Expanded sedimentary records from the Tethys reveal unique faunal and isotopic changes across the Palaeocene-Eocene (P-E) transition. Unlike in the open oceans, the Tethys exhibits a gradual decrease of 1.5% in δ¹³C values prior to the rapid δ¹³C excursion. Associated with the 6¹³C excursion is a decrease in calcite burial, increase in detrital content and appearance of a unique opportunistic planktic foraminifera1 assemblage (e.g. compressed acarininids). The existence of a prelude decrease in δ¹³C values in the Tethys suggests that the P-E δ¹³C excursion may have occurred in two steps and over a few hundred thousand years, rather than as one step over a few thousand years as previously suggested. This slower excursion rate is readily explained by changing organic carbon weathering or burial rates and avoids the need of invoking ad hoc scenarios.     

Stable isotopic signature of a palaeoaquifer, Mississippian Alamogordo Member limestones, Sacramento Mountains, New Mexico, USA

Nine stratigraphic sections, each ≈5 m thick, were sampled from the Alamogordo Member limestones of the Lake Valley Formation, Sacramento Mountains, New Mexico, USA. Four stratigraphic sections consist entirely of lime mudstone and wackestone, whereas the other five sections have a prominent layer of crinoidal packstone about 1 m thick at their base. Stable isotopic analyses reveal that the lime muds in the sections with basal packstone layers show a downward decrease in δ¹⁸O and constant δ¹³C values, whereas those in the sections solely composed of lime mudstone and wackestone have, in general, relatively uniform δ¹⁸O and δ¹³C values. The diagenesis of the Alamogordo Member limestones was previously believed to have been governed by the downward percolation of meteoric water from a regional pre-Pennsylvanian exposure surface ≈100 m above this unit. However, the uniform δ¹³C and downward decrease in δ¹⁸O values in the lime muds in the sections with basal packstones indicate that the meteoric water ascended within the Alamogordo Member, rather than descended from the overlying exposure surface. This indicates that the basal packstones were probably a conduit for meteoric water. This is further supported indirectly by the relatively uniform δ¹⁸O and δ¹³C values of the lime mud in the sections without basal packstones. The implications are that the oxygen isotopic gradients may be used to identify palaeoaquifers, flow directions within these aquifers and that meteoric diagenesis below an exposure surface could be governed by flow through a palaeoaquifer.     

Field geometry, petrography and geochemistry of a dolomitization front (Late Jurassic, central Lebanon)

This contribution describes the field geometry, petrography and geochemistry of a well-exposed dolomitization front in Upper Jurassic carbonates, and attempts to highlight the sedimentological, structural and relative sea-level controls on multiphase dolomitization and related diagenetic events. The data presented reflect the superposition of various diagenetic phases which have resulted in a single dolostone body, whose dimensions are well defined in the field. Local microbial intraclastic dolomites of Late Tithonian age accumulated in a hypersaline lagoon during relative sea-level fall. These pre-date beige hydrothermal dolostones (51 to 55 mol% CaCO₃; δ ¹⁸O: −9·3 to −4·0‰ V-PDB; δ ¹³C: −1·5 to +2·1‰ V-PDB; ⁸⁷Sr/⁸⁶Sr: 0·70742; matrix porosity: ≈6%; Klinkenberg permeability: ≈0·5 mD), whose dolomitizing fluid circulated along faults and invaded the nearby facies. First, the burrows were dolomitized, then the bulk rocks, resulting in the investigated 'tongue'-shaped dolomite body. Upon Late Jurassic–Early Cretaceous uplift, near-surface water percolated through – and altered – the underlying beige dolostones. This event was followed by a ferroan dolomite cement phase, which occurred during further burial. This contribution, featuring a well-defined geometric pattern of a dolomitization front with a large petrographic and geochemical data set, may also serve as a case study illustrating the complexity of superimposed diagenetic processes which have to be taken into account in modelling exercises of multiphase hydrothermal dolomitization.     

The Valanginian carbon isotope event: a first episode of greenhouse climate conditions during the Cretaceous

Lower Cretaceous pelagic carbonates outcropping along the Southern Alps of northern Italy provide a record of Tethyan palaeoceanography as well as of low frequency fluctuations in the global carbon cycle. The carbonate C-isotope stratigraphy established at five selected localities in the Southern Alps allows an accurate picture to be drawn of the duration and amplitude of the Valanginian C-isotope event. δ¹³C values near 1.25–1.50% determined in Berriasian and lower Valanginian sediments are replaced by more pdsitive δ¹³C values near 3% in the late Valanginian. The carbonate C-isotope excursion ends in the early Hauterivian with values fluctuating between 1.5% and 2%. The carbonate C-isotope excursion is accompanied by a positive excursion in the total organic carbon C-isotope curve. The Valanginian C-isotope excursion identified in Tethyan sediments correlates with a C-isotope excursion recorded in the western North Atlantic, in the Gulf of Mexico, and in the Central Pacific (DSDP Sites 534,391,535 and 167). By analogy with the Aptian stage, also marked by a significant positive C-isotope excursion, the time of positive δ¹³C values is regarded as a time of accelerated carbon cycling coupled with increased burial rates of organic carbon and detrital material in oceanic sediments. A warm and humid climate, possiblycoupled with a high atmospheric CO₂ content and a high global sea-level, may have triggered the acceleration of the global carbon cycling. In this case the Valanginian C-isotope event would reflect a first episode of Greenhouse Earth conditions during the Cretaceous.     

A Simplified, Accurate and Fast Method for Lithium Isotope Analysis of Rocks and Fluids, and δ7Li Values of Seawater and Rock Reference Materials

We report a new approach to conduct fast and accurate lithium isotope ratio measurements by MC-ICP mass spectrometry after wet chemical sample preparation. In contrast to most previously published methods our MC-ICP-MS set-up did not use a desolvating system to achieve appropriate ion beam intensities and, therefore, was less affected by matrix-induced shifts of the instrumental mass bias. As the total lithium background and build-up in the sample introduction system was low, previous sample residues could be washed out by an extended uptake of the new sample. Elimination of a nitric acid rinse step increased the sample throughput by a factor of two and allowed the instrumental mass bias drift to be tracked more precisely. δ⁷Li values of powdered silicate rock reference materials and seawater obtained in this study revealed good accuracy and an overall analytical uncertainty of typically 0.5‰ (2s). On the basis of a comparison between our lithium isotope data and compiled literature data, we recommend preliminary average δ⁷Li values for seawater (+30.8‰) and several silicate rock reference materials (BHVO-1: +5.0‰; JA-1: +5.6‰; JB-2: +4.8‰). The compilation of published δ⁷Li values for seawater suggests that the observed large lithium isotope differences are due to inter-method and/or interlaboratory bias. Most recently published δ⁷Li values for seawater show little variation and confirm a constant lithium isotope composition (at the sub ‰ level) of seawater in well mixed ocean basins.     

Stable isotopic and fluid inclusion evidence for meteoric fluid penetration into an active mountain belt; Alpine Schist, New Zealand

Calcite and quartz veins have formed, and are forming, in steeply dipping fissures in the actively rising Alpine Schist metamorphic belt of New Zealand. The fluids that deposited these minerals were mostly under hydrostatic pressure almost down to the brittle-ductile transition, which has been raised to 5-6 km depth by rapid uplift. Some fluids were trapped under lithostatic pressures. Fluids in the fissure veins were immiscible H₂O + NaCl-CO₂ mixtures at 200-350 C. Bulk fluid composition is 15-20 mol% CO₂ and <4.3 total mol CH₄+ N₂+ Ar/100mol H₂O. Water hydrogen isotopic ratio δD_H2O in the fissure veins spans -29 to -68‰, δ¹⁸O_H2O -0.7 to 8.5‰, and bulk carbon isotopic ratio δ¹³C ranges from -3.7 to -11.7‰. The oxygen and hydrogen isotopic data suggest that the water has a predominantly meteoric source, and has undergone an oxygen isotope shift as a result of interaction with the host metamorphic rock. Similar fluids were present during cooling and uplift. Dissolved carbon is not wholly derived from residual metamorphic fluids; part may be generated by oxidation of graphite.