Fossil pollen, molluscs, and stable isotopes in the Dättnau valley, Switzerland

Pollen and mollusc deposits in a sedimentation series laid down in the Dattnau valley during the Late Glacial and early Post-glacial were studied. For the first time δ¹³C and δ¹⁸O in land-snail shells were measured. It was possible to reconstruct vegetational and climatic developments from the Bölling ( c . 12,500 B.P.) until well into the early Boreal ( c . 9,000 B.P.). The two sets of findings agree well. The Late Glacial is seen to comprise two intervals: the continuous, locally rather moist, warm Bölling/Alleröd period, and the subsequent dry . cold Younger Dryas. The profile ceases after the changeover from the Late Glacial to the Post-glacial. The transitions from the Alleröd to the Younger Dryas and hence to the Preboreal and Boreal are both clearly identifiable in the pollen diagram; the mollusc record, however, ceases to be interpretable shortly before the climatic change to the Post-glacial. The δ¹⁸O curve shows a clear distinction between the AllerÖd and the Younger Dryas. The Gerzensee fluctuation, immediately before this transition. is evident as a negative deviation.     

Oxygen-isotope record of Late-Glacial climatic change in western Ireland

Oxygen-isotope profiles for the Late-Glacial carbonate sediments from Red Bog and adjacent Lough Gur in County Limerick in western Ireland are readily correlated with the classical hiozones delineated on pollen diagrams for the same cores. The estimated summer temperatures of the Bølling/Allerød were as high as those in the early Holocene and are correlated with increasing Milankovitch summer insolation. This warm phase was abruptly terminated in the Younger Dryas cold episode by a depletion of 4% in δ¹⁸O, suggesting a summer atmospheric temperature decrease of about 12°C, comparable to that inferred from fossil beetle data. The Younger Dryas phase is attributed to a major cooling of the sea-surface temperature by a postulated discharge of icebergs similar to that of the Heinrich events, for the icebergs were much more effective than simple meltwater in cooling the sea surface and thus the climate over Europe. Shorter-term cool phases (Older Dryas. Gerzensee. Preboreal oscillation) are also recognized.     

Pollen- and oxygen-isotope analyses of late- and postglacial sediments from the Schwemm raised bog near Walchsee in Tirol, Austria

Oxygen-isotope and pollen analyses were carried out on late- and postglacial (Late Weichselian and Holo-cene) sediment samples of the raised bog. The ¹⁸O/¹⁶O-ratio results provide the first unequivocal proof for the Eastern Alps of the climatic deterioration of the Younger Dryas period. High NAP-values in the pollen diagram and a strong negative deviation in the oxygen-isotope curve characterize this period. The earlier Gerzensee fluctuation is also indicated by small changes in the oxygen-isotope curve. During the postglacial the Frosnitz climatic deterioration (6,000–6,500 B.P.) is evidenced as a fluctuation in the lake-level. The oxygen-isotope values indicate that the air temperature conditions remained unchanged at that time.     

Composite stable isotope records from a Late Weichselian lacustrine sequence at Grrenge, Lolland, Denmark: evidence of Allerød and Younger Dryas environments

Stable oxygen and carbon isotope data from a lacustrine sequence at Grænge, southeast Denmark, revealed distinct cnvironmental changes related to Late Weichselian climatic development in the region. Comparison of isotopic records obtained from sedimentary carbonates and freshwater molluscs enabled reconstruction of changes in the lacustrine environment. The degree of thermal and chemical stratification of the lake was evaluated and supported by pollen data from an earlier study of the site. During the Allerød interstadial, dimictic and stagnant conditions characterized the lake, whereas the stratification was disturbed during thc Younger Dryas stadial probably as a result of deforestation and increased wind impact. The origin of sedimentary carbonates was examined by mineralogic and morphologic studies. A considerable input of clastics and detrital carbonates, associated with pronounced enrichment of ¹⁸O and ¹³C. wds recorded in the Younger Dryas sediments indicating soil degradation and increased erosion. A climatic warming preceding the Pleis-tocene/Holocene boundary is clearly reflected in the different stable isotope records and in the lithostratigraphy.     

Late Glacial stable isotope record, radiocarbon stratigraphy, pollen and mollusc analyses from the Geiseltal area, Central Germany

Combined investigations of isotopes, pollen, and molliisc shells were carried out on a Latc Glacial limnic high-resolution sediment sequence from the Geiseltal open-cast mine in Central Gcrmany. The dala confirm thc division of the Late Glacial biozones into two colder (Older and Younger Dryas) and two warmer periods (Bølling, Allcrød), which have already bccn cstablishcd lor the Central and Northern German area. Radiocarbon data, mainly based on wood material, cover a time span between c , 10 800 BP and 12 760 BP, indicating a mean sedimentation rate of c . 2 mm/yr. The stable isotope data (δ¹⁸O, δ¹³C) reflect the transition periods between the climatic phases as changes in relative air humidity (transition from dry, cold to warmer. more humid conditions). The dominance of evaporation effects, however, is superimposed on any ternpcratiirc aignal throughout the profile. Repeated conversions of the hydrologic regime (silting-up phases. lake-level variations) characterize the specific history of the lake development.     

Pollenanalytische und geochronologische Untersuchungen zur Piottino-Schwankung (Jüngere Dryas)

New pollen-analytical investigations and two ¹⁴C series indicate that, at the Bedrina on Mount Piottino (Tessin, Switzerland), the post-Allerød NAP phase (Piottino oscillation) represents the well-marked Younger Dryas at least for the most part. The late-glacial part of the profile is re-classified, and the term Piottino oscillation is rejected, as it is largely identical with the Younger Dryas. Individual ¹⁴C dates from the transition between the Younger Dryas and the Preboreal should be considered critically. Considerable fluctuations in the ¹⁴C level are supposed for this period.     

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.     

Geochemical Process of Gas Hydrate Formation in the Nankai Trough Based on Chloride and Isotopic Anomalies in Interstitial Water

Abstract: Interstitial water expelled from gas hydrate-bearing and -free sediments in the Nankai Trough are analyzed in terms of Cl-, SO₄²-, δ¹⁸O and δD. The baselines for the Cl- concentration and δ¹⁸O value are close to seawater values (530 mM and 0%), indicating that the interstitial water is of seawater origin. The δD values decrease with depth, implying isotopic exchange of hydrogen between upwelling biogenic methane depleted in D and interstitial water. The Cl- concentrations in gas hydrate-bearing sediments are anomalously low, while the δ¹⁸O and δD values are both high, suggesting that the water forming these gas hydrates was poor in Cl- and enriched in ¹⁸O and D during gas hydrate formation. Calculation of the gas hydrate saturations using Cl "and δ¹⁸O anomalies gives results of up to 80 % in sand, and shows that the δ¹⁸O baseline is not consistent with the Cl" baseline. The δ¹⁸O baseline increases by +1% in gas hydrate-free clay and silt. This is considered to be caused by clustering of water molecules after gas hydrate dissociation in response to the upward migration of the base of gas hydrate stability, as indicated by the presence of a double bottom-simulating reflector at this site. The water clusters enriched in ¹⁸O are responsible for the increase in the δ¹⁸O baseline with normal Cl". The abrupt shallowing of the base of gas hydrate stability may induce the dissociation of gas hydrates and the accumulation of gases in the new stability zone, representing a geological process that increases gas hydrate saturation.     

The Fossvogur marine sediments in SW Iceland - confined to the Allerød/Younger Dryas transition by AMS 14 C dating

An exhaustive ¹⁴C dating programme of molluscs from the Fossvogur sediments in Reykjavik. Iceland is presented. For the first time all the fossiliferous units of the sediments are dated. The results confirm earlier conclusions of a widespread occurrence of marine sediments of Allerød age in Reykjavik. The set of dates from the Fossvogur sediments shows a narrow ¹⁴C age distribution (standard deviation of ±235 years) of molluscs from all localities and from successive marine units in vertical sections. The weighted mean conventional ¹⁴C age is 11,400 BP. Assuming a reservoir effect of 400 years. this corresponds to a reservoir-corrected age of I1,000 BP. i.e. the Allerød- Younger Dryas transition for the sampled units, These new ¹⁴C dates from Fossvogur confirm the need for a revision of the Upper Pleistocene chronology of the Reykjavik region. They also have a bearing on the Late Weichselian record of glacier readvances and sea-level changes in the area. The dates suggest that the marine units in Fossvogur accumulated within a restricted time-span of a few hundred years. The sediments in Fossvogur are of volcaniclastic origin and are extremely lithified, indicating local geothermal activity soon after their deposition. This may explain anomalously high D/L amino acid ratios measured in molluscs from the Fossvogur sediments. δ¹³C and δ¹⁸O results suggest that temperatures may have ranged up to 60°C.     

Climate variability in the SE Alps of Italy over the past 17 000 years reconstructed from a stalagmite record

Stalagmite SV1 from Grotta Savi, located at the SE margin of the European Alps (Italy), is the first Alpine speleothem that continuously spans the past c . 17kyr. Extension rate and δ¹⁸O_c record for the Lateglacial probably reflect a combination of temperature and rainfall, with rainfall exerting the dominant effect. Low speleothem calcite δ¹⁸ O_c values were recorded from c . 14.5 and 12.35 kyr, during GI-1 (Bølling— Allerød) interstadial, which in our interpretation, was warm and wet. The GS-1 (Younger Dryas) was characterized by a shift to heavier δ¹⁸ O_c, coinciding with δ¹³C_c enrichment and extremely low extension rate (<8 μm/year). These characteristics indicate that GS-1 climate was cool and dry in the SE Alps. Calibration using historical data revealed that there is a positive δ¹⁸O_c/dT relationship. A 1°C rise in mean annual temperature should correspond to c . 2.85% increase of SV-1 δc¹⁸O_c. We reconstructed a slow and steady temperature rise of c . 0.5°C since 10 kyr BP, in broad agreement with reconstructions from pollen data for SE Europe. Stalagmite SV1 indicates that climate variability in the SE Alps has been influenced by the Mediterranean Sea for the past c . 17 kyr.     

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%.     

Oxygen isotope exchange and closure temperatures in cooling rocks

Retrograde exchange of oxygen isotopes between minerals in igneous and metamorphic rocks by means of diffusion is explored using a finite difference computer model, which predicts both the zonation profile of δ¹⁸O within grains, and the bulk δ¹⁸O value of each mineral in the rock. Apparent oxygen isotope equilibrium temperatures that would be observed in these rocks are calculated from the δ¹⁸O values of each mineral pair within the rock. In systems which cool linearly from a sufficiently high temperature or at a low enough cooling rate, such that the final oxygen isotope values are not dependent upon the initial oxygen isotope values ('slow cooling'), the apparent oxygen isotope temperature derived for a rock composed of a single mineral pair can be shown to be simply related to the Dodson closure temperatures ( T _c) for the two phases and the mode of the rock. Adding a third phase into a system which undergoes 'slow' cooling will cause the apparent temperature derived for the two minerals already present to differ from the simple relationship for a two-phase system. In some systems oxygen isotope reversals can be developed. If cooling is not 'slow', then the mineral δ¹⁸O values resulting from cooling will be partly dependent upon the initial temperature of the system concerned. The model successfully simulates the mineral δ¹⁸O values that are often observed in granitic rocks. Application of the model will help in assessing the validity of oxygen isotope thermometry in different geological settings, and allows quantitative prediction of the oxygen isotope fractionations that are developed in cooling closed systems.     

Refinements in BaSO4 to CO2 Preparation and δ18 O Calibration of the Sulfate Reference Materials NBS-127, IAEA SO-5 and IAEA SO-6

Refinements have been made to achieve over 99% yield in the conversion of CO to CO₂ in order to improve the reproducibility and accuracy of δ¹⁸ O measurements in sulfates. BaSO₄ (10-15 mg) was mixed with an identical amount of spectrographic-grade graphite and loaded into a Pt boat. The mixture was gradually heated to 1100 °C to reduce sulfate to CO and CO₂; the former gas was simultaneously converted to CO₂ by a glow discharge between Pt electrodes immersed in a magnetic field (produced by a pair of external neodymium magnets). A small memory effect was noticed during the analysis (less than 0.3‰ per 10‰ difference in δ¹⁸ O between two subsequently analysed samples). The memory effect, however, was suppressed by repetitive preparation of the same specimen. CO₂ produced in this way from sulfate reference samples was analysed on a dual inlet and triple collector mass spectrometer along with CO₂ equilibrated with VSMOW, GISP and SLAP water reference samples. To avoid large departures of measured isotope ratios from ¹⁸O/¹⁶O of the working calibrator we used CO₂ gas prepared from ocean water sulfate for this purpose. The calibrated δ¹⁸ O values (in ‰) obtained in this way for NBS-127, IAEA SO-5 and IAEA SO-6 reference materials were 8.73 ± 0.05, 12.20 ± 0.07 and -10.43 ± 0.12, respectively.     

Distinguishing between seafloor alteration and fluid flow during subduction using stable isotope geochemistry: examples from Tethyan ophiolites in the Western Alps

Large amounts of fluid, bound up in the hydrated upper layers of the ocean crust, are consumed at convergent margins and released in subduction zones through devolatilization. The liberated fluids may play an integral role in subduction zone processes, including the generation of arc-magmas. However, exhumed subduction zone rocks often record little evidence of large-scale fluid flow, especially at deeper levels within the subduction zone. Basaltic pillows from the high-pressure Corsican and Zermatt-Saas ophiolites show a range of δ¹⁸O values that overall reflect seafloor alteration prior to subduction. However, comparison between the δ¹⁸O values of the cores and rims of the pillows suggests that the δ¹⁸O values of the pillow rims at least have been modified during subduction and high-pressure metamorphism. Pillows that have not undergone high-pressure metamorphism generally have rims with higher δ¹⁸O values than their cores, whereas the converse is the case in pillows that have undergone high-pressure metamorphism. This reversal in the core to rim oxygen isotope relationship between unmetamorphosed and metamorphosed pillows is strong evidence for fluid–rock interaction occurring during subduction and high-pressure metamorphism. However, the preservation of different δ¹⁸O values in the cores and rims of individual pillows and within and between different pillows suggests that fluid flow within the subduction zone was strongly channelled. Resetting of the δ¹⁸O values in the pillow rims was probably due to fluid-hosted diffusion that occurred over relatively short time-scales (<1 Myr).     

Exposure age dating and Equilibrium Line Altitude reconstruction of an Egesen moraine in the Maritime Alps, Italy

Four boulder samples from the Piano del Praiet frontal moraine in the Gesso della Barra Valley (Maritime Alps) have been ¹⁰Be dated. The results give a weighted mean age of 11 340±370 (870) yr, constraining the frontal moraine to the Egesen glacial stadial, during the Younger Dryas cold phase. By applying the same ¹⁰Be production rate to other Egesen moraines previously dated in the Alps, we obtain similar ages for all of them. This suggests a synchroneity of the Egesen deglaciation in the European Alps at the end of the Younger Dryas. From the palaeoshape of the Egesen glacier, reconstructed by means of geomorphological mapping, an Equilibrium Line Altitude depression (δELA) of −520 to −530 m, with respect to the present-day ELA, and of −260 to −320 m, with respect to the Little Ice Age ELA, has been calculated. Comparison with other Alpine sector δELAs indicates that the Maritime Alps experienced humid climatic conditions during the Younger Dryas.     

Very high 18o enrichment in Archean cherts from South India: implications for Archean ocean temperature

Stable carbon and oxygen isotopic compositions of essentially unmetamorphosed Archean (> 2.6 Gyr old) cherts and carbonates of the Dharwar Sequence of southern India, from the northernmost part of the Dharwar-Shimoga supracrustal belt (Kalche and Nagargali), have been determined. The cherts from the Nagargali area, which preserve oolitic texture and cryptocrystalline silica, show highly enriched δ¹⁸O values ranging from 28 to 31.4%o relative to SMOW. Such values are the highest yet reported from Archean nondetrital sediments, but are similar to those of modern marine cherts. On the assumption of a seawater δ¹⁸O of 0%₀, calculation of temperature based on the maximum δ¹⁸O value of 31.4%₀ yields a value of 40°C. This is significantly less than 70–80°C reported for the Archean oceans based on cherts and chert-phosphate pairs. Diagenetically recrystallized microcrystalline chert-dolomite pairs of Kalche area exhibit a range of oxygen isotopic ratios similar to those reported for Archean cherts and carbonates from other parts of the world. The temperature of diagenesis is estimated to be about 68°C.     

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.     

Chronology and paleoenvironments during the late Weichselian deglaciation of the southwest Iceland shelf

Foraminifera, sedimentology, and tephra geochemistry in core 93030-006 LCF from the southwestern Iceland shelf were used to reconstruct paleoenvironments between 12.7 and 9.4 ¹⁴C ka BP. Seismic-reflection profiles place the core in glacial-marine and marine sediments within one meter of the underlying glacial till. Foraminifers in the earliest glacial-marine sediments provide a record of ice-distal conditions and immigration of slope species onto the shelf in association with warm Atlantic water. Meltwater increased during the Allerød under a weakened Atlantic water influence. Arctic conditions began by 11.14 ₁₄C ka BP with an abrupt increase in meltwater and near exclusion of boreal fauna from the shelf. Meltwater diminished in the early Younger Dryas, coinciding with sea-surface cooling between 11.14 and 10.5 ¹⁴C ka BP. A slight warming recorded in the uppermost glacial-marine sediments was interrupted by an inferred jökulhlaup event emanating from glacier ice on the Western Volcanic Zone. Retreat of the ice margin from the sea sometime between c. 10.3 and 9.94 ¹⁴C ka BP coincided with this event. The onset of postglacial marine sedimentation occurred along with increasing evidence of Atlantic water c. 9.94 ¹⁴C ka BP and was interrupted by a short-lived Pre-boreal cooling of the Irminger Current c. 9.91 ¹⁴C ka BP. Conditions similar to those today were established by 9.7 ¹⁴C ka BP.     

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.     

Oxygen Isotopic Characteristics of Granitic Intrusions Related to Haobugao Zn-Pb-Cu-Sn Skarn Deposit, East Inner Mongolia, China

Abstract. Granitic rocks related to the formation of Haobugao Zn-Pb-Cu-Sn skarn deposit, Inner Mongolia, China, show unusual low whole-rock δ¹⁸O values down to -8.8 % (V-SMOW), whereas separated quartz crystals from those rocks give positive δ¹⁸O values of+4.1 to +9.9 %. Chemical analyses and microscopic observation of those granitic rocks confirm that they suffered hydrothermal alteration. Some skarn specimens and quartz from the Haobugao deposit also show negative δ¹⁸O values. The isotopic evidence indicates that intensive meteoric water circulation occurred at the time of granitic intrusion, and caused the pervasive hydrothermal alteration of granitic rocks and the precipitation of skarn deposit in this area.