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

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

Pleistocene paleoclimate of the arid region of Israel as recorded in calcite deposits along regional transverse faults and in veins

The δ¹⁸O and δ¹³C values of the calcites associated with E-W and NE-SW transverse faults in the Negev, Israel, indicate that calcite was deposited from meteoric water. A regional change in the δ¹⁸O and δ¹³C values was observed. The ¹⁸O content in the calcite increases, from the southwestern (δ¹⁸O = −17.8‰) to the northeastern (δ¹⁸O = −2.9‰) part of the region. The δ¹³C values show the opposite trend of the ¹³C content decrease: from +2‰ in the south to −10‰ in the northeast. These trends had to reflect changes in regional paleoclimate, suggesting a change in the isotopic composition of the solution from which the calcite was deposited in different periods. The variations in the δ¹⁸O values reflect shifts in the δ¹⁸O values of precipitation and are associated with a change in the source of moist air masses which came from the equatorial Atlantic in the early Pleistocene and from the Mediterranean during a later period. Variations in δ¹³C values reflect changes from humid to arid conditions. Two modes of calcite deposition are suggested: (1) precipitation of calcite minerals in the unsaturated zone following the dissolution in the soil or (2) calcite deposition that occurred as CO₂ was lost during emergence of paleogroundwater from Lower Cretaceous and Jurassic aquifers.     

Stable carbon and oxygen isotope investigation in historical lime mortar and plaster – Results from field and experimental study

Lime mortar and plaster were sampled from Roman, medieval and early modern buildings in Styria. The historical lime mortar and plaster consist of calcite formed in the matrix during setting and various aggregates. The stable C and O isotopic composition of the calcite matrix was analyzed to get knowledge about the environmental conditions during calcite formation. The δ¹³C_matrix and δ¹⁸O_matrix values range from −31 to 0‰ and −26 to −3‰(VPDB), respectively. Obviously, such a range of isotope values does not represent the local natural limestone assumed to be used for producing the mortar and plaster. In an ideal case, the calcite matrix in lime mortar and plaster is isotopically lighter in the exterior vs. the interior mortar layer according to the relationship δ¹⁸O_matrix = 0.61 · δ¹³C_matrix − 3.3 (VPDB). Calcite precipitation by uptake of gaseous CO₂ into alkaline Ca(OH)₂ solutions shows a similar relationship, δ¹⁸O_calcite = 0.67 · δ¹³C_calcite − 6.4 (VPDB). Both relationships indicate that the ¹³C/¹²C and ¹⁸O/¹⁶O values of the calcite reflect the setting behaviour of the lime mortar and plaster. Initially, CO₂ from the atmosphere is fixed as calcite, which is accompanied by kinetic isotope fractionation mostly due to the hydroxylation of CO₂ (δ¹³C_matrix ≈  −25‰ and δ¹⁸O_matrix ≈ −20‰). As calcite formation continued the remaining gaseous CO₂ is subsequently enriched in ¹³C and ¹⁸O causing later formed calcite to be isotopically heavier along the setting path in the matrix. Deviations from such an ideal isotopic behaviour may be due to the evolution of H₂O, e.g. evaporation, the source of CO₂, e.g. from biogenic origin, relicts of the natural limestone, and secondary effects, such as recrystallization of calcite. The results of the field and experimental study suggest that isotope values can be used as overall proxies to decipher the origin of carbonate and the formation conditions of calcite in the matrix of ancient and recent lime mortar and plaster. Moreover, these proxies can be used to select calcite matrix from historical lime mortar and plaster for ¹⁴C dating.     

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

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

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

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

GISP2 Oxygen Isotope Ratios

The GISP2 oxygen isotope record, with its high-resolution detail, yields crucial information on past climate change. The glacial δ¹⁸O oscillations of the GISP2 core, with their very fast onsets, are templates of a prototype oscillation of variable duration with an amplitude of 3.9‰. The halfway mark of the cold–warm transition is reached in 2 years; the top is reached in 50 years. The δ¹⁸O–time gradient of the leading front is about 7.8‰ per 100 yr. After reaching the top, δ¹⁸O slowly declines by −0.14‰ per 100 yr. The duration of δ¹⁸O decline varies from a couple of centuries for fast oscillations to about 4000 yr for slower ones. The subsequent δ¹⁸O downturn during the warm–cold transition has a δ¹⁸O–time gradient of −3.2‰ per 100 yr and lasts about 80 yr.     

Oxygen isotope composition and geothermometry of granulite to greenschist facies metamorphic rocks: a study from the Neoproterozoic collision-related nappe system, south of São Francisco Craton, SE Brazil

Oxygen isotope studies were carried out across units of a Neoproterozoic nappe system, south of São Francisco Craton. A temperature decrease toward the base of the system is found, consistent with a previously recognized inverted metamorphic pattern. The tectonic contact of the basal unit and the reworked southern São Francisco craton show a steep temperature gradient, suggesting that low temperature thrusting acted as the dominant tectonic process. The contrasts between the δ¹⁸O values of the Três Pontas-Varginha and Carmo da Cachoeira nappes and the differences among the samples and minerals are consistent with the preservation of sedimentary isotopic composition during metamorphism. The small differences in the δ¹⁸O values between the undeformed and the deformed calc-silicate samples (1.6‰) suggest that the δ¹⁸O value of mylonitization fluids was close to that which equilibrated with the metamorphic assemblage. The distinct δ¹⁸O values of metapelitic and calc-silicate samples and the great temperature difference from one type to the other indicate that no large-scale fluid interaction processes occurred during metamorphism. Oxygen isotopic estimations of both Três Pontas-Varginha undeformed rocks and Carmo da Cachoeira unaltered equivalents indicate δ¹⁸O values of up to 18‰. Comparison between these values and those from the ‘basement’ orthogneisses (8.3–8.5‰) indicates the latter are not sources for the metapelites.     

Interhemispheric anti-phasing of rainfall during the last glacial period

We have obtained a high-resolution oxygen isotopic record of cave calcite from Caverna Botuverá (27°13′S, 49°09′W), southern Brazil, which covers most of the last 36 thousand years (ka), with an average resolution of a few to several decades. The chronology was determined with 46 U/Th ages from two stalagmites. Tests for equilibrium conditions show that oxygen isotopic variations are primarily caused by climate change. We interpret our record in terms of meteoric precipitation changes, hence the variability of South American Monsoon (SAM) intensity. The oxygen isotopic profile broadly follows local insolation changes and shows clear millennial-scale variations during the last glacial period with amplitudes as large as 3‰ but with smaller centennial-scale shifts (<1‰) during the Holocene. The overall record is strikingly similar to, but strongly anti-correlated with, a number of records from the Northern Hemisphere.We compared our record to other precisely dated contemporaneous records from Hulu Cave eastern China. Minima in δ¹⁸O (wet periods, intense SAM) at our site are synchronous with maxima in δ¹⁸O (dry periods, weak East Asian Monsoon, EAM) in eastern China (within precise dating errors) and vice versa. This anti-phased precipitation relationship between two low-latitude locations may be interhemispheric in extent, based on comparison with records from other sites. Precipitation anti-phasing may be related to north–south shifts in the mean position of the intertropical convergence zone (ITCZ) and asymmetry in Hadley circulation in two hemispheres, associated not with seasonal changes as observed today, but with millennial-scale climate shifts. The millennial-scale atmospheric see-saw patterns that we observe could have important controls and feedbacks on climate within hemispheres because of water vapor's greenhouse properties.     

Carbon and oxygen isotope zoning around Carlin-type gold deposits: a reconnaissance survey at Twin Creeks, Nevada

This study was undertaken to determine whether wallrocks around the Twin Creeks Carlin-type gold deposits exhibit oxygen isotope haloes similar to those found around other types of hydrothermal deposits. Mineralization at Twin Creeks is hosted by Ordovician Sequence shales containing some carbonate minerals and by Pennsylvanian–Permian Etchart Formation limestone. Analysis of orthophosphate-soluble carbonate from these rocks shows that oxygen isotope haloes are detectable in Ordovician Sequence shales but not in Etchart Formation limestone. The soluble fraction of Ordovician Sequence shales at Twin Creeks has δ¹⁸O values of 12 to 24‰ and δ¹³C values of 0 to −10‰. Most samples fall along a poorly defined trend that extends from δ¹⁸O of about 24‰ and δ¹³C values of about 0, which are typical of unaltered limestones, toward lower values for both isotope systems, which are typical of rocks that have undergone alteration by hydrothermal fluids. Plots of these values along two sections through the ore body show that δ¹⁸O values of wallrocks are lowest in the ore zone and increase outward, forming a halo several hundred meters in size. In the same plots, δ¹³C values of the wallrocks do not show systematic spatial variations. The soluble fraction of Etchart Formation limestones at Twin Creeks have δ¹⁸O values of 25 to 5‰ and δ¹³C values of 4 to −10‰, but do not show any systematic spatial variation relative to mineralization at the scale of our samples. Failure of the Etchart Formation samples to show detectable haloes is probably related to deposition of post-ore carbonate minerals or lower ore fluid : rock ratios. Material balance calculations used to model the isotopic composition of average Ordovician Sequence shales indicate that changes in temperature and water : rock ratio were probably not sufficient to account for the wide range of isotope compositions observed in these rocks. The most likely additional factor contributing to this range of values was a change in the composition of the altering fluid, probably by mixing of the ore fluid with surrounding meteoric water. These results suggest that Carlin-type gold deposits are surrounded by haloes of low δ¹⁸O values, but that detection of these haloes could be complicated by local compositional variations and post-ore modification of the wallrocks.     

Regional oxygen isotope systematics of felsic volcanics; a potential exploration tool for volcanogenic massive sulphide deposits in the Iberian Pyrite Belt

Regional oxygen isotopic sytematics have been performed mainly on the felsic volcanic footwall rocks of the orebodies but also on purple schist characteristic of the hanging wall series, around two giant VMS deposits in the Spanish Iberian Pyrite Belt, Riotinto and La Zarza. As the terranes of the Iberian Pyrite Belt, these two giant deposits have been affected by the Hercynian tectono-metamorphic events, strongly modifying their geometry. About 60 and 40 samples were collected over a 10×4 km² area at Riotinto and a 3×2 km² area at La Zarza, respectively. Whole-rock powders were analysed for oxygen by CO₂-laser fluorination. At both sites, a same type of low-δ¹⁸O anomaly down to +3.6‰, well differentiated from the regional background (up to 20‰), was identified near the orebodies. The lowest δ¹⁸O values (+4 to +11‰) correspond to the chlorite hydrothermal halo, essentially restricted to the feeder zones of the orebody. Intermediate δ¹⁸O values (+9 to +15‰) correspond to the sericite hydrothermal halo, mostly developed laterally to the orebody until 0.5–1 km. The regional background (+16 to +20‰) is represented by spilitised volcanic rocks. A same kind of low anomaly, but with less contrast, was defined in purple schist in the immediate hanging wall of the orebodies. All these results demonstrate that, despite high geometrical modifications of the orebodies related to the Hercynian tectonics, oxygen isotopic anomalies recorded by volcanic host rocks during the emplacement of the mineralising hydrothermal systems are still identified. This strongly suggests that oxygen isotopic systematics could be useful to identify target areas in the Iberian Pyrite Belt, as already demonstrated on other VMS targets in the world.     

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

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

S- and O-isotopic character of dissolved sulphate in the cover rock aquifers of a Zechstein salt dome

Sulfur and O isotope analyses of dissolved SO₄ were used to constrain a hydrogeological model for the area overlying the Gorleben–Rambow Salt Structure, Northern Germany. Samples were collected from 80 wells screened at different depth-intervals. The study area consists of a set of two vertically stacked aquifer systems. Generally, the isotope data show a good spatial correlation, outlining well-defined groundwater zones containing SO₄ of characteristic isotopic composition. Highly saline waters from deeper parts of the lower aquifer system are characterized by rather constant SO₄ isotopic compositions, which are typical of Permian Zechstein evaporites (δ³⁴S=9.6–11.9‰; δ¹⁸O=9.5–12.1‰). Above this is a transition zone containing ground waters of intermediate salinity and slightly higher isotopic values (average δ³⁴S=16.6‰; δ¹⁸O=15.3‰). The confined groundwater horizon on the top of the lower aquifer system below the low permeable Hamburg Clays is low in total dissolved solids and is characterized by an extreme ³⁴S enrichment (average δ³⁴S=39.1‰; δ¹⁸O=18.4‰), suggesting that bacterially mediated SO₄ reduction is a dominant geochemical process in this zone. Two areas of distinct isotopic composition can be identified in the shallow ground water horizons of the upper hydrogeological system. Sulfate in groundwaters adjacent to the river Elbe and Löcknitz has a typical meteoric isotopic signature (δ³⁴S=5.2‰; δ¹⁸O=8.2‰), whereas the central part of the area is characterized by more elevated isotopic ratios (δ³⁴S=12.7‰; δ¹⁸O=15.6‰). The two major SO₄ pools in the area are represented by Permian seawater SO₄ and a SO₄ of meteoric origin that has been mixed with SO₄ resulting from the oxidation of pyrite. It is suggested that the S-isotope compositions observed reflect the nature of the SO₄ source that have been modified to various extent by bacterial SO₄ reduction. Groundwaters with transitional salinity have resulted from mixing between brines and low-mineralized waters affected by bacterial SO₄ reduction.     

Origin of pedogenic needle-fiber calcite revealed by micromorphology and stable isotope composition—a case study of a Quaternary paleosol from Hungary

Pedogenic needle-fiber calcite was studied regarding its morphology, texture and stable isotope composition from the paleosol of the Quaternary Várhegy travertine (Budapest, Hungary). The needle-fiber calcite is composed of 40–200 μm long monocrystals. Smooth rods as well as serrated-edged crystals with calcite overgrowths were identified by SEM. Needles have several textural varieties: randomly distributed crystals in vugs and pores with calcite hypocoatings, bundles of subparallel crystals forming coatings around grains and alveolar structure with bridging needles in vugs.The morphological study of needle-fiber calcite suggests that needles are calcified fungal sheaths and produced by fungal biomineralization, a common process in recent and fossil soils and calcretes. The stable isotope composition of needle-fiber calcite (average: δ¹⁸O=-7.1‰ and δ¹³C=-7.3‰ vs. V-PDB) indicates significant incorporation of organically derived CO₂ and probably biological influence on needle genesis. Dissolved host rock travertine and/or atmospheric CO₂ could also contribute some carbon to the acicular calcite.     

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

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

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

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

Hydrology of a spring complex, studied by geochemical time-series data, Acquarossa, Switzerland

A case study of three springs in Switzerland is used to demonstrate the value of geochemical time-series data as a powerful tool to study the dynamics of groundwater systems. Values of repeatedly measured parameters revealed intermixings of two water types: (a) a 29°C water, circulating to a depth of 1100 m and containing approximately 700 mg/l Ca, 2000 mg/l SO₄, 700 mg/l HCO₃, 20 mg/l of Na and Cl, 6 mg/l Fe, at least 47 mg/l SiO₂, and with an isotopic composition of δD = − 73.0‰ and δ¹⁸ O = −10.9‰, and (b) a 12°C or colder water, shallow, and of a post-1953 age, containing 420 mg/l TDI or less, very low in Na and Cl (4 mg/l or less), isotopic values of δD = −71.0‰ and δ¹⁸ O = −10.5‰ and tritium as in recent (post-bomb) precipitation.     

A new protocol for oxygen isotope analysis of authigenic and biogenic fine silica grains using laser-extraction technique

We report here a 30 W CO₂ laser heating protocol for analyzing oxygen isotope composition (δ¹⁸O in ‰ vs. V-SMOW) of quartz and amorphous silica grains lower than 50 and 2 μm with a good external precision (1σ < 0.15‰). This technique is used to investigate δ¹⁸O composition of macro-, micro- and crypto-crystalline quartz cements of quartzite levels occurring in a sand sequence from the South of France (Apt Series), after a physical separation of the quartz cements. δ¹⁸O data obtained from this technique are compared with δ¹⁸O data obtained from in situ ion microprobe analyses. This study also presents promising results on δ¹⁸O analysis of phytoliths obtained with the laser heating protocol (1σ < 0.1‰).     

Variations of stable isotopes with depth in regolith calcite cements in the Broken Hill region, Australia: Palaeoclimate evolution signal?

Twenty two samples of calcretes from seven depth-profiles in the Menindee catchment, Broken Hill region, Australia were analysed for their inorganic and organic carbon contents and inorganic carbon and oxygen isotopes. The organic carbon content is very low (from 0.06 to 0.31 wt.%) while inorganic carbon (carbonate) is up to 3.9 wt.%. Both δ¹³C and δ¹⁸O become more positive closer to the surface. Carbon isotopes vary from − 8.5‰ to −5.5‰ PDB. Oxygen isotopes vary from − 6‰ to − 1.8‰ V-PDB. Depth-related δ¹³C and δ¹⁸O variations correlate over at least 15 km and show no significant variation along the flow path. δ¹³C values increase by 3‰ and δ¹⁸O values increase by 4‰ with decreasing depth in a 1.40 m thick soil profile. The variation is interpreted to indicate an increasingly elevated air temperature, greater water stress and subsequently an aridification of the area through time. The Broken Hill calcrete data confirm that climatic evolution can be deduced from isotopic series and be applied successfully to the Broken Hill region.     

Loss of primary texture and geochemical signatures in speleothems due to diagenesis: Evidences from Castañar Cave, Spain

Geochemical signals from speleothems are commonly used in the investigation of palaeoenvironments. In most cases, however, little attention is paid to whether or not these signals are primary or altered by diagenesis. The speleothems of the Castañar Cave (Cáceres, Spain), which are initially formed of calcite or aragonite, have undergone a variety of meteoric diagenetic processes such as micritization and neomorphism (inversion), that collectively modify their primary features (textures, mineralogy, geochemical signals). The mean δ¹³C and δ¹⁸O values of the aragonites in the cave are −8.66 and −4.64 respectively, whereas the primary calcites have mean δ¹³C and δ¹⁸O values of −9.99 and −5.77, respectively. Following the diagenetic process of micritization, the aragonite isotopic signals averaged −7.63 δ¹³C and −4.74 δ¹⁸O and the calcite micrite signals −9.53 δ¹³C and −5.21 δ¹⁸O. Where inversion took place, some secondary calcites after the aragonite show preserved aragonite, whereas others do not. The secondary calcites without aragonite relics show isotopic values slightly higher than those of the primary calcite due to the inheritance of the aragonite signal. Where aragonite relics are preserved, the isotopic signatures are very similar to those of the aragonite micrite.In addition, the stable isotopic values and Sr and Mg contents of the speleothems became also modified by micritization and/or inversion. These diagenetic processes were driven by the changes in composition of the cave waters over time and space, but also, in the case of aragonite, by its initial unstable mineralogy.The present results highlight how important diagenesis is in caves and how the initial features of cave minerals may be lost. These changes alter the geochemical signals shown by speleothems, which may have an impact on the interpretation of the results obtained in palaeoenvironmental studies.     

Evaluation of oxygen isotopes in carbonate as an indicator of lake evolution in arid areas: The modern Qinghai Lake, Qinghai–Tibet Plateau

The oxygen isotopic composition of carbonate in lakes has been used as a useful indicator in Palaeolimnological research, and has made some important contributions to our understanding of lacustrine systems. For modern lakes in arid or cold areas, however, there are few data available to test the effect of lake salinity and temperature on the oxygen isotopic composition of various carbonate sources such as ostracod, bulk carbonate, and fine-grained carbonate (< 60 μm). Here we examined the oxygen isotopic composition of ostracods, bulk carbonate, and fine-grained carbonates, as well as that of coexisting water from Lake Qinghai and the smaller surrounding lakes and ponds on the Qinghai–Tibet Plateau. Our investigation highlights three key effects. First, the oxygen isotopic composition of ostracods, bulk carbonate, and fine-grained carbonate in the lakes and ponds shows a clear response to lake water δ¹⁸O values, and these vary with water salinity. The relationship between lake water δ¹⁸O and salinity is not only dominated by the evaporation/freshwater input ratios, but is also controlled by the distance to the mouth of the major rivers supplying to the lake. Second, the ostracod, bulk carbonate, and fine-grained carbonate show similar isotopic change trends in the study area, and oxygen isotopic differences between ostracods and authigenic carbonate may be explained by the different water temperatures and very small ‘vital offsets’ of ostracods. Finally, the effect of water depth on temperature leads to increasing δ¹⁸O values in carbonates as water depth increases, both in benthic ostracods living on the lake bottom, as well as in bulk carbonate precipitated at the water surface.For arid, high-altitude Lake Qinghai, our results suggest that variations in the δ¹⁸O values of carbonate in Lake Qinghai are mainly controlled by the oxygen-isotope ratio of the lake water changing with water salinity. As a secondary effect, increasing water depth leads to cooler bottom and surface water, which may result in more positive δ¹⁸O values of ostracod and bulk carbonate.