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The accessories perovskite, pyrochlore, zirconolite, calzirtite and melanite from carbonatites and carbonate-rich foidites from the Kaiserstuhl are variously suited for the in situ determination of their U–Pb ages and Sr, Nd- and Hf-isotope ratios by LA-ICP-MS. The 143Nd/144Nd ratios may be determined precisely in all five phases, the 176Hf/177Hf ratios only in calzirtite and the 87Sr/86Sr ratios in perovskites and pyrochlores. The carbonatites and carbonate-rich foidites belong to one of the three magmatic groups that Schleicher et al. (1990) distinguished in the Kaiserstuhl on the basis of their Sr, Nd and Pb isotope ratios. Tephrites, phonolites and essexites (nepheline monzogabbros) form the second and limburgites (nepheline basanites) and olivine nephelinites the third. Our 87Sr/86Sr isotope data from the accessories overlap with the carbonatite and olivine nephelinite fields defined by Schleicher et al. (1990) but exhibit a much narrower range. These and the εNd and εHf values plot along the mantle array in the field of oceanic island basalts relatively close to mid-ocean ridge basalts. Previously reported K–Ar, Ar–Ar and fission track ages for the Kaiserstuhl lie between 16.2 and 17.8 Ma. They stem entirely from the geologically older tephrites, phonolites and essexites. No ages existed so far for the geologically younger carbonatites and carbonate-rich foidites except for one apatite fission track age (15.8 Ma). We obtained precise U–Pb ages for zirconolites and calzirtites of 15.66, respectively 15.5 Ma (± 0.1 2σ) and for pyrochlores of 15.35 ± 0.24 Ma. Only the perovskites from the Badberg soevite yielded a U–P concordia age of 14.56 ± 0.86 Ma while the perovskites from bergalites (haüyne melilitites) only gave 206Pb/238U and 208Pb/232Th ages of 15.26 ± 0.21, respectively, 15.28 ± 0.48 Ma. The main Kaiserstuhl rock types were emplaced over a time span of 1.6 Ma almost 1 million years before the carbonatites and carbonate-rich foidites. These were emplaced within only 0.32 Ma.
Holocene climate was characterised by variability on multi-centennial to multi-decadal time scales. In central Europe, these fluctuations were most pronounced during winter. Here we present a record of past winter climate variability for the last 10.8 ka based on four speleothems from Bunker Cave, western Germany. Due to its central European location, the cave site is particularly well suited to record changes in precipitation and temperature in response to changes in the North Atlantic realm. We present high-resolution records of δ18O, δ13C values and Mg/Ca ratios. Changes in the Mg/Ca ratio are attributed to past meteoric precipitation variability. The stable C isotope composition of the speleothems most likely reflects changes in vegetation and precipitation, and variations in the δ18O signal are interpreted as variations in meteoric precipitation and temperature. We found cold and dry periods between 8 and 7 ka, 6.5 and 5.5 ka, 4 and 3 ka as well as between 0.7 and 0.2 ka. The proxy signals in the Bunker Cave stalagmites compare well with other isotope records and, thus, seem representative for central European Holocene climate variability. The prominent 8.2 ka event and the Little Ice Age cold events are both recorded in the Bunker Cave record. However, these events show a contrasting relationship between climate and δ18O, which is explained by different causes underlying the two climate anomalies. Whereas the Little Ice Age is attributed to a pronounced negative phase of the North Atlantic Oscillation, the 8.2 ka event was triggered by cooler conditions in the North Atlantic due to a slowdown of the thermohaline circulation.
Holocene climate was characterised by variability on multi-centennial to multi-decadal time scales. In central Europe, these fluctuations were most pronounced during winter. Here we present a new record of past winter climate variability for the last 10.8 ka based on four speleothems from Bunker Cave, Western Germany. Due to its central European location, the cave site is particularly well suited to record changes in precipitation and temperature in response to changes in the North Atlantic realm. We present high resolution records of δ18O, δ13C values and Mg/Ca ratios. We attribute changes in the Mg/Ca ratio to variations in the meteoric precipitation. The stable C isotope composition of the speleothems most likely reflects changes in vegetation and precipitation and variations in the δ18O signal are interpreted as variations in meteoric precipitation and temperature. We found cold and dry periods between 9 and 7 ka, 6.5 and 5.5 ka, 4 and 3 ka as well as between 0.7 to 0.2 ka. The proxy signals in our stalagmites compare well with other isotope records and, thus, seem representative for central European Holocene climate variability. The prominent 8.2 ka event and the Little Ice Age cold events are both recorded in the Bunker cave record. However, these events show a contrasting relationship between climate and δ18O, which is explained by different causes underlying the two climate anomalies. Whereas the Little Ice Age is attributed to a pronounced negative phase of the North Atlantic Oscillation, the 8.2 ka event was triggered by cooler conditions in the North Atlantic due to a slowdown of the Thermohaline Circulation.
Acesta excavata (Fabricius, 1779) is a slow growing bivalve from the Limidae family and is often found associated with cold-water coral reefs along the European continental margin. Here we present the compositional variability of frequently used proxy elemental ratios (Mg/ Ca, Sr/Ca, Na/Ca) measured by laser-ablation mass spectrometry (LA-ICP-MS) and com- pare it to in-situ recorded instrumental seawater parameters such as temperature and salin- ity. Shell Mg/Ca measured in the fibrous calcitic shell section was overall not correlated with seawater temperature or salinity; however, some samples show significant correlations with temperature with a sensitivity that was found to be unusually high in comparison to other marine organisms. Mg/Ca and Sr/Ca measured in the fibrous calcitic shell section display significant negative correlations with the linear extension rate of the shell, which indicates strong vital effects in these bivalves. Multiple linear regression analysis indicates that up to 79% of elemental variability is explicable with temperature and salinity as independent pre- dictor values. Yet, the overall results clearly show that the application of Element/Ca (E/Ca) ratios in these bivalves to reconstruct past changes in temperature and salinity is likely to be complicated due to strong vital effects and the effects of organic material embedded in the shell. Therefore, we suggest to apply additional techniques, such as clumped isotopes, in order to exactly determine and quantify the underlying vital effects and possibly account for these. We found differences in the chemical composition between the two calcitic shell lay- ers that are possibly explainable through differences of the crystal morphology. Sr/Ca ratios also appear to be partly controlled by the amount of magnesium, because the small magne- sium ions bend the crystal lattice which increases the space for strontium incorporation. Oxi- dative cleaning with H2O2 did not significantly change the Mg/Ca and Sr/Ca composition of the shell. Na/Ca ratios decreased after the oxidative cleaning, which is most likely a leaching effect and not caused by the removal of organic matter.
The Yacoraite Formation (Salta rift, Argentina) consists of Maastrichtian–Danian lacustrine carbonate and siliciclastic deposits with interbedded volcanic ash layers, organized in four third-order stratigraphic sequences. It offers the exceptional opportunity to jointly apply in situ zircon and carbonate U-Pb geochronology that resulted in two distinct depositional age depth models. Ages of the youngest zircon population from ash layers were linearly interpolated to derive a zircon depositional age depth model. A carbonate depositional age depth model was instead obtained from dated carbonate phases including microbialites, ooids, oncoids of calcitic and dolomitic mineralogy as well as early lacustrine calcite cements. Mean ages were defined from different carbonate phases belonging to the same layer and then linearly interpolated. Sedimentation rates were calculated from both depth models between pairs of dated samples and used to estimate the age of sequence boundaries, as well as the duration of the four stratigraphic sequences. The zircon and carbonate depositional age depth models agree with biostratigraphic constraints and exhibit excellent consistency. The onset and end of sedimentation were estimated at 68.2 ± 0.9 Ma and 62.3 ± 0.6 Ma (duration ca 5.7 Ma) via zircon geochronology and at 67.9 ± 1.7 Ma and 61.9 ± 1.3 Ma (duration ca 6.0 Ma) via carbonate geochronology. Results from this study show that with suitable samples and a newly implemented working strategy, in situ U-Pb dating of depositional and early diagenetic carbonates represent a valuable chronostratigraphic tool for estimating sedimentation rate and duration in poorly time-framed depositional systems.
The Izu–Bonin–Mariana volcanic arc is situated at a convergent plate margin where subduction initiation triggered the formation of MORB-like forearc basalts as a result of decompression melting and near-trench spreading. International Ocean Discovery Program (IODP) Expedition 352 recovered samples within the forearc basalt stratigraphy that contained unusual macroscopic globular textures hosted in andesitic glass (Unit 6, Hole 1440B). It is unclear how these andesites, which are unique in a stratigraphic sequence dominated by forearc basalts, and the globular textures therein may have formed. Here, we present detailed textural evidence, major and trace element analysis, as well as B and Sr isotope compositions, to investigate the genesis of these globular andesites. Samples consist of K2O-rich basaltic globules set in a glassy groundmass of andesitic composition. Between these two textural domains a likely hydrated interface of devitrified glass occurs, which, based on textural evidence, seems to be genetically linked to the formation of the globules. The andesitic groundmass is Cl rich (ca. 3000 µg/g ), whereas globules and the interface are Cl poor (ca. 300 µg/g ). Concentrations of fluid-mobile trace elements also appear to be fractionated in that globules and show enrichments in B, K, Rb, Cs, and Tl, but not in Ba and W relative to the andesitic groundmass, whereas the interface shows depletions in the latter, but is enriched in the former. Interestingly, globules and andesitic groundmass have identical Sr isotopic composition within analytical uncertainty ( 87Sr∕86Sr of 0.70580 ± 10 ), indicating that they likely formed from the same source. However, globules show high δ11 B (ca. + 7 ‰ ), whereas their host andesites are isotopically lighter (ca. – 1 ‰ ), potentially indicating that whatever process led to their formation either introduced heavier B isotopes to the globules, or induced stable isotope fractionation of B between globules and their groundmass. Based on the bulk of the textural information and geochemical data obtained from these samples, we conclude that these andesites likely formed as a result of the assimilation of shallowly altered oceanic crust (AOC) during forearc basaltic magmatism. Assimilation likely introduced radiogenic Sr, as well as heavier B isotopes to comparatively unradiogenic and low δ11B forearc basalt parental magmas (average 87Sr∕86Sr of 0.703284). Moreover, the globular textures are consistent with their formation being the result of fluid-melt immiscibility that was potentially induced by the rapid release of water from assimilated AOC whose escape likely formed the interface. If the globular textures present in these samples are indeed the result of fluid-melt immiscibility, then this process led to significant trace element and stable isotope fractionation. The textures and chemical compositions of the globules highlight the need for future experimental studies aimed at investigating the exsolution process with respect to potential trace element and isotopic fractionation in arc magmas that have perhaps not been previously considered.
Garnet xenocrysts from kimberlites provide unique insights into the composition, structure and evolution of the subcontinental lithospheric mantle (SCLM). For example, different metasomatic events in the SCLM are reflected in compositional differences between garnet xenocrysts. As mantle metasomatism largely controls the physical and chemical properties of the SCLM, it exerts first order control over the genesis of kimberlitic magmas and diamond formation. However, dating mantle lithologies and processes is complicated by high ambient temperatures that allow the equilibration of most isotopic systems up to the time of kimberlite eruption. As a consequence, the temporal connection between metasomatic events in the mantle and kimberlite genesis is commonly ambiguous.
In this study, we applied LA-ICPMS U-Pb dating to 43 harzburgitic, lherzolithic and megacrystic garnet xenocrysts from the ~376 Ma diamondiferous V. Grib kimberlite, Russia, in order to investigate the link between different types of mantle metasomatism and kimberlite genesis.
Our results indicate that, with two possible exceptions, only harzburgitic garnet overlaps in age with the kimberlite eruption, whereas lherzolitic and megacrystic garnet crystals are ~20 to 130 million years older. Furthermore, garnet U-Pb ages and Ni-in-garnet temperatures of ~820 to 1200 °C do not correlate. This, and the high closure temperature of U-Pb in garnet (≥900 °C) suggests that the garnet U-Pb ages indeed reflect metasomatic events in the SCLM. However, the U-Pb ages could also reflect cooling ages. In this case, the metasomatic events recorded in the garnet crystals must still have occurred up to ~130 million years prior to the eruption of the V. Grib kimberlite.
These findings have far-reaching implications for the genesis of (diamondiferous) kimberlites, as they clearly show that the time lag between metasomatic events in the SCLM, as recorded in kimberlitic garnet xenocrysts, and kimberlite eruption may extend to tens of millions of years.
The continental expression of global cooling during the Miocene Climate Transition in Central Asia is poorly documented, as the tectonically active setting complicates the correlation of Neogene regional and global climatic developments. This study presents new geochemical data (CaSO4 content, carbonate δ13C and δ18O) from the endorheic alluvial‐lacustrine Aktau succession (Ili Basin, south‐east Kazakhstan) combined with findings from the previously published facies evolution. Time series analysis revealed long‐eccentricity forcing of the paleohydrology throughout the entire succession, split into several facies‐dependent segments. Orbital tuning, constrained by new laser ablation U‐Pb dates and a preexisting magnetostratigraphy, places the succession in a 5.0 Ma long interval in the middle to late Miocene (15.6 to 10.6 Ma). The long‐term water accumulation in the Ili Basin followed the timing of the Miocene Climate Transition, suggesting increased precipitation in the catchment area in response to climate cooling and stronger westerly winds. This was paced by minima of the 2.4 Ma eccentricity cycle, which favored the establishment of a discharge playa (~14.3 Ma) and a perennial lake (12.6 to 11.8 Ma). Furthermore, low obliquity amplitudes (nodes) caused a transient weakening of the westerlies at ~13.7 to 13.5 Ma and at ~12.7 Ma, resulting in negative hydrological budgets and salinization. Flooding of the windward Ili Basin coeval with aridification in the leeward basins suggests that the Tian Shan was a climate boundary already in the middle Miocene. Our results emphasize the impact of climate fluctuations on the westerlies' strength and thus on Central Asian hydrology.
Metasomatic evolution of coesite-bearing diamondiferous eclogite from the Udachnaya Kimberlite
(2020)
A coesite-bearing diamondiferous eclogite from the Udachnaya kimberlite (Daldyn field, Siberian craton) has been studied to trace its complex evolution recorded in rock-forming and minor mineral constituents. The eclogite sample is composed of rock-forming omphacite (60 vol%), garnet (35 vol%) and quartz/coesite (5 vol%) and contains intergranular euhedral zoned olivine crystals, up to 200 µm long, coexisting with phlogopite, orthopyroxene, clinopyroxene (secondary), K-feldspar, plagioclase, spinel, sodalite and djerfisherite. Garnet grains are zoned, with a relatively homogeneous core and a more magnesian overgrowth rim. The rim zones further differ from the core in having higher Zr/Y (6 times that in the cores), ascribed to interaction with, or precipitation from, a kimberlite-related melt. Judging by pressure-temperature estimates (~1200 °C; 6.2 GPa), the xenolith originated at depths of ~180–200 km at the base of the continental lithosphere. The spatial coexistence of olivine, orthopyroxene and coesite/quartz with K-Na-Cl minerals in the xenolith indicates that eclogite reacted with a deep-seated kimberlite melt. However, Fe-rich olivine, orthopyroxene and low-pressure minerals (sodalite and djerfisherite) likely result from metasomatic reaction at shallower depths during transport of the eclogite by the erupting kimberlite melt. Our results demonstrate that a mixed eclogitic-peridotitic paragenesis, reported previously from inclusions in diamond, can form by interaction of eclogite and a kimberlite-related melt.