Speleothem record of the last 180 ka in Villars cave (SW France): Investigation of a large δ18O shift between MIS6 and MIS5

The Vil-car-1 flowstone core from Villars cave (SW France) provides one of the first European speleothem records extending back to 180 ka, based on U–Th TIMS and MC-ICP-MS measurements. The core offers a continuous record of Termination II and the Last Interglacial. The penultimate deglaciation is characterized by a prominent 5‰ depletion in calcite δ¹⁸O. Determining which specific environmental factors controlled such a large oxygen isotopic shift offers the opportunity to assess the impact of various factors influencing δ¹⁸O variations in speleothem calcite.Oxygen isotope analyses of fluid inclusions indicate that drip water δ¹⁸O remained within a very narrow range of ±1‰ from Late MIS6 to the MIS5 δ¹⁸O optimum. The possibility of such a stable behaviour is supported by simple calculations of various effects influencing seepage water δ¹⁸O.Although this could suggest that the isotopic shift in calcite is mainly driven by temperature increase, attempts to quantify the temperature shift from Late MIS6 to the MIS5 δ¹⁸O optimum by assuming an equilibrium relationship between calcite and fluid inclusion δ¹⁸O yield unreasonably high estimates of ～20 °C warming and Late MIS6 cave temperatures below 0 °C; this suggests that the flowstone calcite precipitated out of thermodynamic equilibrium at this site.Using a method proposed by Guo et al. (submitted for publication) combining clumped isotope measurements, fluid inclusion and modern calcite δ¹⁸O analyses, it is possible to quantitatively correct for isotopic disequilibrium and estimate absolute paleotemperatures. Although the precision of these absolute temperature reconstructions is limited by analytical uncertainties, the temperature rise between Late MIS6 and the MIS5 optimum can be robustly constrained between 13.2 ± 2.6 and 14.6 ± 2.6 °C (1σ), consistent with existing estimates from Western Europe pollen and sea-surface temperature records.     

Isotope geochemistry of Swan Lake Basin in the Nebraska Sandhills,USA: Large 13C enrichment in sediment-calcite records

This study presents isotope geochemical analyses conducted on water column samples and core sediments collected from the Swan Lake Basin. Water analyses include the dissolved methane (CH₄) content and the ratio of carbon-13 to carbon-12 (δ¹³C) in dissolved inorganic carbon (DIC). The core sediments – sandy muds containing inorganic calcite, organic matter, and opal phases ± ostracods – were examined by X-ray diffraction, dated by radiocarbon (¹⁴C), analyzed for wt% organic carbon, wt% organic nitrogen, wt% organic matter, wt% calcite, δ¹³C of bulk-sediment insoluble organic matter (kerogen), ¹⁸O:¹⁶O ratio (δ¹⁸O) and δ¹³C of bulk and ostracod calcite. Of particular significance is the large enrichment in carbon-13 (δ¹³C = +4.5 to +20.4‰ V-PDB) in the calcite of these sediments. The ¹³C-enriched calcite is primarily formed from DIC in the water column of the lake as a result of the following combined processes: (i) the incorporation of ¹³C enriched residual carbon dioxide (CO₂) after partial reduction to CH₄ in the sediments and its migration into the water column-DIC pool; (ii) the preferential assimilation of ¹²C by phytoplankton during photosynthesis; (iii) the removal of ¹³C-depleted CH₄ by ebullition and of organic matter by sedimentation and burial. The ¹³C enrichment was low between 3624 and 2470 yr BP; high between 2470 and 1299 yr BP; and moderate since 1299 yr BP. Low ¹³C enrichment was formed under low water-column carbon levels while higher ones were formed under elevated rates of biomass and calcite deposition. These associations seem to imply that biological productivity is the main reason for carbon-13 enrichments.     

Origin of CO2 and carbonate veins in mantle-derived xenoliths in the Pannonian Basin

The origin and evolution of CO₂ inclusions and calcite veins in peridotite xenoliths of the Pannonian Basin, Hungary, were investigated by means of petrographic investigation and stable isotope analyses. The fluid inclusions recovered in paragenetic olivine and clinopyroxene belong to distinct populations: type A (texturally early) inclusions with regular shapes (often with negative crystal forms) forming intragranular trails; type B (texturally late) inclusions defining randomly oriented trails that reach grain boundaries. Type B inclusions are often associated with silicate melt (type C) inclusions. Stable carbon isotope compositions in inclusion-hosted CO₂ were obtained by vacuum crushing followed by conventional dual inlet as well as continuous flow mass spectrometry in order to eliminate possible lab artifacts. Olivines, clino- and orthopyroxenes of the host peridotite have oxygen isotope compositions from 5.3 to 6.0‰ (relative to V-SMOW), without any relationship with xenolith texture. Some of the xenoliths contained calcite in various forms: veins and infillings in silicate globules in veins, secondary carbonate veins filling cracks and metasomatic veins with diffuse margins. The former two carbonate types have δ¹³C values around –13‰ (relative to V-PDB) and low Sr contents (< 0.5 wt.%), whereas the third type,veins with high-temperature metasomatic features have a δ¹³C value of –5.0‰ and high Sr contents up to 3.4 wt.%. In spite of the mantle-like δ¹³C value and the unusually high Sr content typical for mantle-derived carbonate, trace element compositions have proven a crustal origin. This observation supports the conclusions of earlier studies that the carbonate melt droplets found on peridotite xenoliths in the alkaline basalts represent mobilized sedimentary carbonate. The large δ¹³C range and the ¹²C-enrichment in the carbonates can be attributed to devolatilization of the migrating carbonate or infiltration of surficial fluids containing ¹²C-rich dissolved carbon.Carbon isotope compositions of inclusion-hosted CO₂ range from –17.8 to –4.8‰ (relative to V-PDB) with no relation to the amount of CO₂ released by vacuum crushing. Low-δ¹³C values measured by stepwise heating under vacuum suggest that the carbon component is pristine and not related to surficial contamination, and that primary mantle fluids with δ¹³C values around –5‰ were at least partly preserved in the xenoliths. Tectonic reworking and heating by the basaltic magma resulted in partial CO₂ release and local ¹³C-depletion.     

Hydro-geochemical and isotopic fluid evolution of the Los Azufres geothermal field,Central Mexico

Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (T_mi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (T_h)  = 325 ± 5 °C. The boiling zone shows T_h = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO₂. Positive clathrate melting temperatures (fusion) with T_h = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO₂ (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ¹⁸O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ¹⁸O is due to the rock–water interaction at relatively high temperatures. δ¹³C stable isotope data show a magmatic source with a minor meteoric contribution for CO₂. The initial isotopic value δ³⁴S_RES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ³⁴S (FeS₂) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ¹⁸O.     

Changing moisture sources over the last 330,000 years in Northern Oman from fluid-inclusion evidence in speleothems

Speleothems from Hoti Cave in northern Oman provide a record of continental pluvial periods over the last 330,000 yr. Periods of rapid speleothem deposition occurred from 6000 to 10,500, 78,000 to 82,000, 120,000 to 135,000, 180,000 to 200,000, and 300,000 to 330,000 yr ago, with little or no growth during the intervening periods. During each of these five pluvial periods, δD values of water extracted from speleothem fluid inclusions (δD_FI) are between −60 and −20‰ (VSMOW) and δ¹⁸O values of speleothem calcite (δ¹⁸O_C) are between −12 and −4‰ to (VPDB). These values are much more negative than modern rainfall (for δD) or modern stalagmites (for δ¹⁸O). Previous work on the isotopic composition of rainfall in Oman has shown that northern and southern moisture sources are isotopically distinct. Combined measurements of the δD values of fluid-inclusion water with calculated δ¹⁸O values from peak interglacial speleothems indicate that groundwater was predominantly recharged by the southern (Indian Ocean) moisture source, when the monsoon rainfall belt moved northward and reached Northern Oman during each of these periods.     

Pleistocene speleothems of Mallorca: implications for palaeoclimate and carbonate diagenesis in mixing zones

The Pleistocene speleothems of Sa Bassa Blanca cave, Mallorca, are excellent indicators of palaeoclimate variations, and are samples that allow evaluation of the products and processes of mixing‐zone diagenesis in an open‐water cave system. Integrated stratigraphic, petrographic and geochemical data from a horizontal core of speleothem identified two main origins for speleothem precipitates: meteoric‐marine mixing zone and meteoric‐vadose zone. Mixing‐zone precipitates formed at and just below the water–air interface of cave pools during interglacial times, when the cave was flooded as a result of highstand sea‐level. Mixing‐zone precipitates include bladed and dendritic high‐Mg calcite, microporous‐bladed calcite with variable Mg content, and acicular aragonite; their presence suggests that calcium‐carbonate cementation is significant in the studied mixing‐zone system. Fluid inclusion salinities, δ¹³C and δ¹⁸O compositions of the mixing‐zone precipitates suggest that mixing ratio was not the primary control on whether precipitation or dissolution occurred, rather, the proximity to the water table and degassing of CO₂ at the interface, were the major controls on precipitation. Thus, simple two‐end‐member mixing models may apply only in mixing zones well below the water table. Meteoric‐vadose speleothems include calcite and high‐Mg calcite with columnar and bladed morphologies. Vadose speleothems precipitated during glacial stages when sea level was lower than present. Progressive increase in δ¹³C and δ¹⁸O of the vadose speleothems resulted from cooling temperatures and more positive seawater δ¹⁸O associated with glacial buildup. Such covariation could be considered as a valid alternative to models predicting invariant δ¹⁸O and highly variable δ¹³C in meteoric calcite. Glacio‐eustatic oscillations of sea‐level are recorded as alternating vadose and mixing‐zone speleothems. Short‐term climatic variations are recorded as alternating aragonite and calcite speleothems precipitated in the mixing zone. Fluid‐inclusion and stable‐isotope data suggest that aragonite, as opposed to calcite, precipitated during times of reduced meteoric recharge.     

Paleohydrogeological events recorded by stable isotopes,fluid inclusions and trace elements in fracture minerals in crystalline rock,Simpevarp area,SE Sweden

Fracture minerals calcite, pyrite, gypsum, barite and quartz, formed during several events have been analysed for δ¹³C, δ¹⁸O, δ³⁴S, ⁸⁷Sr/⁸⁶Sr, trace element chemistry and fluid inclusions in order to gain knowledge of the paleohydrogeological evolution of the Simpevarp area, south-eastern Sweden. This area is dominated by Proterozoic crystalline rocks and is currently being investigated by the Swedish Nuclear Fuel and Waste Management Co. (SKB) in order to find a suitable location for a deep-seated repository for spent nuclear fuel. Knowledge of the paleohydrogeological evolution is essential to understand the stability or evolution of the groundwater system over a time scale relevant to the performance assessment for a spent nuclear fuel repository. The ages of the minerals analysed range from the Proterozoic to possibly the Quaternary. The Proterozoic calcite and pyrite show inorganic and hydrothermal-magmatic stable isotope signatures and were probably formed during a long time period as indicated by the large span in temperatures (c. 200–360 °C) and salinities (0–24 wt.% eq. CaCl₂), obtained from fluid inclusion analyses. The Paleozoic minerals were formed from organically influenced brine-type fluids at temperatures of 80–145 °C. The isotopic results indicate that low temperature calcite and pyrite may have formed during different events ranging in time possibly from the end of the Paleozoic until the Quaternary. Formation conditions ranging from fresh to brackish and saline waters have been distinguished based on calcite crystal morphologies. The combination of δ¹⁸O and crystal morphologies show that the fresh–saline water interface has changed considerably over time, and water similar to the present meteoric water and brackish seawater at the site, have most probably earlier been residing in the bedrock. Organic influence and closed system in situ microbial activity causing disequilibrium are indicated by extremely low δ¹³C (down to −99.7‰), extreme variation in δ³⁴S (−42.5‰ to +60.8‰) and trace element compositions. The frequency of calcite low in δ¹³C and high in Mn, as well as pyrite with biogenically modified δ³⁴S decreases with depth. Strontium isotopes have been useful to separate the different generations and the Sr isotope ratios in the groundwaters have been determined mainly by in situ water–rock interaction processes. The difficulty of separating late Paleozoic calcite from possibly recent calcite, and the fact that these calcites are usually found in the same fracture systems indicate that water conducting structures have been intermittently conductive from the Paleozoic and onwards. The methodology used has been successful in separating the different generations and characterising their formation conditions.     

Calcite fracture fillings as indicators of paleohydrology at Laxemar at the Äspö Hard Rock Laboratory,southern Sweden

Isotopic compositions of C (δ¹³C), O (δ¹⁸O) and Sr (δ⁸⁷Sr) were determined for calcite fracture fillings in the crystalline rock penetrated by a 1.6 km drill hole at Laxemar, near the Äspö Hard Rock Laboratory (ÄHRL) in southern Sweden. These calcites precipitated from groundwater some time in the past, and their δ¹³C, δ¹⁸O and δ⁸⁷Sr values reflect those of the source waters. The present-day groundwater system is hydrochemically stratified with highly saline water underlying more shallow brackish and fresh water. The origin of this stratified system is probably related to past glaciations although the ultimate origin of the deep, highly saline water is still problematical. None of the calcite fracture fillings sampled below 900 m could have precipitated from any of the present-day ground waters which in view of the glacial history of the region is not surprising. However, several shallow calcite fracture fillings are formed by precipitation from the present-day groundwater. Coupled variations in δ¹³C, δ¹⁸O and δ⁸⁷Sr isotopes at depths in excess of 900 m suggest that these isotope systems in calcite are recording a time-dependent evolution of groundwater composition.     

Climatic and environmental controls on speleothem oxygen-isotope values

Variations in speleothem oxygen-isotope values (δ¹⁸O) result from a complicated interplay of environmental controls and processes in the ocean, atmosphere, soil zone, epikarst, and cave system. As such, the controls on speleothem δ¹⁸O values are extremely complex. An understanding of the processes that control equilibrium and kinetic fractionation of oxygen isotopes in water and carbonate species is essential for the proper interpretation of speleothem δ¹⁸O as paleoclimate and paleoenvironmental proxies, and is best complemented by study of site-specific cave processes such as infiltration, flow routing, drip seasonality and saturation state, and cave microclimate, among others. This review is a process-based summary of the multiple controls on δ¹⁸O in the atmosphere, soil, epikarst, and speleothem calcite, illustrated with case studies. Primary controls of δ¹⁸O in the atmosphere include temperature and relative humidity through their role in the multiple isotope “effects”. Variability and modifications of water δ¹⁸O values in the soil and epikarst zones are dominated by evaporation, mixing, and infiltration of source waters. The isotopically effective recharge into a cave system consists of those waters that participate in precipitation of CaCO₃, resulting in calcite deposition rates which may be biased to time periods with optimal dripwater saturation state. Recent modeling, experimental, and observational data yield insight into the significance of kinetic fractionation between dissolved carbonate phases and solid CaCO₃, and have implications for the ‘Hendy’ test. To assist interpretation of speleothem δ¹⁸O time series, quantitative and semi-quantitative δ¹⁸O-climate calibrations are discussed with an emphasis on some of the difficulties inherent in using modern spatial and temporal isotope gradients to interpret speleothems as paleoclimate proxy records. Finally, several case studies of globally significant speleothem paleoclimate records are discussed that show the utility of δ¹⁸O to reconstruct past climate changes in regions that have been typically poorly represented in paleoclimate records, such as tropical and subtropical terrestrial locations. The new approach to speleothem paleoclimatology emphasizes climate teleconnections between regions and attribution of forcing mechanisms. Such investigations allow paleoclimatologists to infer regional to global-scale climate dynamics.     

The lateral boundary of a metamorphic core complex: The Moutsounas shear zone on Naxos,Cyclades, Greece

We describe the structure, microstructures, texture and paleopiezometry of quartz-rich phyllites and marbles along N-trending Moutsounas shear zone at the eastern margin of the Naxos metamorphic core complex (MCC). Fabrics consistently indicate a top-to-the-NNE non-coaxial shear and formed during the main stage of updoming and exhumation between ca. 14 and 11 Ma of the Naxos MCC. The main stage of exhumation postdates the deposition of overlying Miocene sedimentary successions and predates the overlying Upper Miocene/Pliocene conglomerates. Detailed microstructural and textural analysis reveals that the movement along the Moutsounas shear zone is associated with a retrograde greenschist to subgreenschist facies overprint of the early higher-temperature rocks. Paleopiezometry on recrystallized quartz and calcite yields differential stresses of 20–77 MPa and a strain rate of 10⁻¹⁵–10⁻¹³ s⁻¹ at 350 °C for quartz and ca. 300 °C for calcite. Chlorite geothermometry of the shear zone yields two temperature regimes, 300–360 °C, and 200–250 °C. The lower temperature group is interpreted to result from late-stage hydrothermal overprint.     

Mass spectrometric U-series dating of the Chaoxian hominin site at Yinshan,eastern China

The fossils of Chaoxian hominin, widely accepted as representing archaic Homo sapiens in eastern China, were recovered from the middle or slightly higher levels of Layer 2 deposits of a collapsed cave at Yinshan, Anhui Province. Results of mass spectrometric U-series dating of intercalated speleothem calcites are presented. Based mainly on four broadly coeval calcite samples, the hominin fossils should be bracketed in the range of 310–360 ka or somewhat older. These ages are much older than the previous estimate at 160–200 ka based on the U-series dating of fossil teeth and bones, and may be cited as supporting evidence for an earlier H. erectus–archaic H. sapiens interface in China.     

Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments

The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ²⁶Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ²⁶Mg values of loess-derived soil above the cave (−1.0 ± 0.5‰), soil water (−1.2 ± 0.5‰), the carbonate hostrock (−3.8 ± 0.5‰), dripwater in the cave (−1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; −4.3 ± 0.6‰), cave loam (−0.6 ± 0.1‰) and runoff water (−1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000lnα_Mg-cc-Mg(aq) = −2.4‰. A similar Mg-isotope fractionation (1000lnα_Mg-cc-Mg(aq) ≈ −2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, ²⁶Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg²⁺ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for inorganic precipitation experiments.     

Effect of temperature on the dissolution and thermal alteration of combined amino acids fixed in natural sediment under simulated hydrothermal conditions

Seafloor sediment containing biogenic amino acids was heated with NaCl solutions at 50–200 °C for 240 h to investigate the dissolution process of amino acids and evaluate their stabilities under hydrothermal conditions. Dissolved amino acids in the combined phase (dissolved combined amino acids, DCAAs) and free phase (dissolved free amino acids, DFAAs) were rapidly released into the solution during heating. The amount of DCAAs in the solutions was 4–9 times higher than the amount of DFAAs at each temperature. When heated at ⩽ 100 °C, most of the total dissolved hydrolyzable amino acids (TDHAAs) were in the combined form (DCAAs/TDHAAs ratios > 0.9). The compositions of the DCAAs in solutions heated at ⩽ 100 °C were similar to that of the total hydrolyzable amino acids (THAAs) of the initial sediment, indicating that the DCAAs, which are derived from organisms and biodebris in the sediment, are barely altered during the hydrothermal reaction at these temperatures. On the other hand, the DCAAs/TDHAAs ratios were 0.72 and 0.57 at 150 and 200 °C, respectively, and the compositions of the DCAAs at 150 and 200 °C were significantly different from that of the initial THAAs. In addition, non-protein amino acids (β-alanine and γ-aminobutyric acid), which are sensitive biochemical indicators of the diagenetic alteration of natural organic matter, drastically increased to 80.9% of the DCAAs after heating at 200 °C. These results suggests that DCAAs are thermally unstable in the hydrothermal solutions at ⩾ 150 °C. These DCAA would be transformed into thermally stable geo-polymers such as humic-like substances and hydrolyzable kerogens.     

Identifying low-temperature hydrothermal karst and palaeowaters using stable isotopes: a case study from an alpine cave,Entrische Kirche,Austria

The area south of the prominent east–west trending Salzach Valley at the northern rim of the Central Alps of Austria has long been known to host anomalously warm springs emerging from a highly deformed calcite marble (Klammkalk). This unit also hosts cavities whose shapes suggest a hydrothermal karst origin and which are lined by calcite spar. We report here petrographic and isotopic evidence suggesting that dissolution by ascending low-temperature thermal waters also played an important role in the origin of a large cave in this region, Entrische Kirche. A paleo cave wall, preserved behind a thick flowstone in the interior of this cave, revealed a brownish bleaching zone which contrasts to the medium grey colour of the unaltered marble beneath. Across this zone the C and O isotope values gradually decrease by 3 and 11‰, respectively. These compositions are very different from those of the speleothem above but are similar to phreatic calcite spar from hydrothermal karst cavities in other outcrops in the area, where the absence of two-phase fluid inclusions suggests a low-temperature (less than ca. 50°C) hydrothermal origin. U/Th dating of the flowstone capping the alteration zone yielded a minimum age of the thermal water invasion in Entrische Kirche of ca. 240 kyr. There is no evidence in Entrische Kirche that these palaeowaters reached the point of calcite precipitation, but it is physically conceivable that higher and as yet unexplored parts of this deep (ca. 900 m) cave contain cavities lined by phreatic cave spar.     

An absolute paleotemperature record from 10 to 6 Ka inferred from fluid inclusion D/H ratios of a stalagmite from Vancouver Island, British Columbia, Canada

By using continuous helium flow during the crushing of calcite speleothem samples, we are able to recover liberated inclusion waters without isotopic fractionation. A paleotemperature record for the Jacklah Jill Cave locality, Vancouver Island, BC, was obtained from a 30-cm tall stalagmite that grew 10.3-6.3 Ka ago, using δ¹⁸O values of the crushed calcite and of the inclusion water as inferred from its δD. It is found that the locality experienced mean annual temperature variations up to 11 °C over a 4-Ka period in the early Holocene. At the beginning of the period, local temperature quickly increased from a minimum of ∼1 °C to around 10 °C, but this early climate optimum, about 3 °C warmer than today, only lasted for ∼1200 years. About 8.6 Ka ago, temperature had declined to ∼7 °C, approximately the same as the modern cave temperature. Since then, the study area has experienced only minor temperature fluctuations, but there was a brief fall to ∼4 °C at around 7 Ka ago, which might be caused by a short lived expansion of local alpine glaciers. The long-term T-dependence of δD was 1.47‰/°C, identical to the value in modern precipitation.     

Stable isotopic and elemental characteristics of recent tufa from a karstic Krka River (south‐east Slovenia): useful environmental proxies?

Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO₂ degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ¹³C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO₂ degassing and tufa precipitation rate downstream. The Δ¹³C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous ¹²CO₂ degassing downstream leaving the carbon pool enriched in ¹³C. In the case of oxygen, the isotope fractionation (Δ¹⁸O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ¹⁸O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ¹⁸O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.     

Determination of the stress conditions of the ductile-to-brittle regime along the Asuke Shear Zone,SW Japan

The stress conditions of the ductile-to-brittle regime have been assessed along the Asuke Shear Zone (ASZ), which strikes NE–SW in the Cretaceous Ryoke granite terrain in SW Japan. Along the ASZ, pseudotachylyte and mylonitized pseudotachylyte are locally developed together with cataclasite. The simultaneous operation of dislocation creep and grain-size-sensitive creep, as indicated by the coexistence of the Z-maximum and relatively random c-axis lattice preferred orientations as well as the sizes of dynamically recrystallized quartz grains (6.40–7.79 μm) in the mylonitized pseudotachylyte, suggest differential stresses of 110–130 MPa at ∼300 °C. The e-twin morphology, twinning ratio, and distribution of the glide direction on the e-twin plane of the twinned calcite in the amygdules of the pseudotachylyte suggest the stress conditions of the σ₁ and σ₃ axes trend 228° and 320° and plunge 55° and 1°, respectively, and indicate differential stresses of 40–80 MPa at 150–200 °C. Based on kinematic indicators in the fault rocks, the stress conditions estimated from calcite twins, and the cooling history of the granitic protolith, the ASZ is inferred to have been activated under a stress state that caused sinistral normal movements before and after pseudotachylyte formation at 70–50 Ma.     

Evidence for episodic cementation and diagenetic recording of seismic pumping events,North Coles Levee,California, U.S.A.

Bands of calcite and dolomite cements alternating with zones of nearly carbonate-free sand occur in the Stevens sandston aat North Coles Levee, San Joaquin, Valley, California. Temperatures calculated from O isotopes suggest that the calcite cement bands were emplaced episodically as a result of repeated injections of hot water from deeper in the section. Burial analysis suggests that these cements precipitated from 7 Ma to the present over the temperature range of 45 to ∼95°C.Carbon isotope data suggest that the C in the cements is a mixture derived from two sources, detrital shell material (δ¹³C(PDB)≈) and CO₂ liberated from maturing kerogen (δ¹³C ≈ −24). Plots of δ¹³C vs time and depth of crystallization show that the cementation sequence was: (1) dolomite cements, possibly concretionary, precipitated at depths <1–2 km and at temperatures <45°C; (2) calcite cements with δ¹³C(PDB) values as low as −13, crystallized from depths between 1220 and 1820 m (4000 and 6000 ft) and at temperatures between 45 and 80°C; (3) calcite cements with δ¹³C(PDB) values approaching zero and calculated temperatures of crystallization up to the present reservoir temperature of 95±3°C.A log of δ¹³C vs calculated depth of crystallization correlates with the stratigraphic column at North Coles Levee. If the correlation is valid the light δ¹³ in each cement sample can be tied to its source. A model based on this interpretation suggests that the early, light C was derived from maturing kerogen in the Kreyenhagen Formation (Eocene) as it passed through the oil window between 4 and 5 Ma. The subsequent passage of younger sediments with less organic material produced correspondingly smaller amounts of light CO₂ which was reflected in the relatively heavier C isotopes in the later cements.It is suggested that the epidsodic injections of hot water carried dissolved gases and minerals, principally calcite, upward from rocks as deep as 2–3 km below the Stevens sandstone and reprecipitated the calcite in more permeable zones in the rock. Degassing of CO₂ from rising pore waters likely triggered the precipitation and accounts for the relatively large volumes of cement. The Sibson model for seismic pumping of pore fluids is considered a likely explanation for the observed cementation.     

The speleothem record of climate variability in Southern Arabia

Uranium-series dated stalagmites from Oman indicate that pluvial conditions prevailed from 6.3 to 10.5, 78 to 82, 120 to 130, 180 to 200 and 300 to 330 kyr B.P.; all of these periods coincide with peak interglacials. Oxygen (δ¹⁸O) and hydrogen (δD) isotope ratios of speleothem calcite and fluid inclusions reveal the source of moisture and provide information on the amount of precipitation, respectively. δ¹⁸O and δD values of stalagmites deposited during peak interglacials vary between ?8 and ?4 ‰ (VPDB) and ?53 and ?20‰ (Vienna Standard Mean Ocean Water [VSMOW]) respectively, whereas modern stalagmites range from ?2.6 to ?1.1‰ in δ¹⁸O (VPDB) and ?7.6 and ?3.3‰ in δD (VSMOW), respectively. The growth and isotopic records indicate that during peak interglacial periods, the limit of the monsoon rainfall was shifted far north of its present location and each pluvial period was coinciding with an interglacial stage of the marine oxygen isotope record.