The dynamics of central Main Ethiopian Rift waters: Evidence from δD, δO and Sr/Sr ratios

Water samples from cold and geothermal boreholes, hot springs, lakes and rivers were analyzed for δD, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr compositions in order to investigate lake water–groundwater mixing processes, water–rock interactions, and to evaluate groundwater flow paths in the central Main Ethiopian Rift (MER) of the Ziway–Shala basin. Different ranges of isotopic values were recorded for different water types: hot springs show δ¹⁸O −3.36 to +3.69 and δD −15.85 to +24.23, deep Aluto-Langano geothermal wells show δ¹⁸O −4.65 to −1.24 and δD −12.39 to −9.31, groundwater wells show δ¹⁸O −3.99 to +5.14 and δD −19.69 to +32.27, whereas the lakes show δ¹⁸O and δD in the range +3.98 to +7.92 and +26.19 to +45.71, respectively. The intersection of the Local Meteoric Water Line (LMWL: δD = 7 δ¹⁸O + 11.2, R² = 0.94, n = 42) and the Local Evaporation Line (LEL: δD = 5.63δ¹⁸O + 8, n = 14, R² = 0.82) was used to estimate the average isotopic composition of recharge water into the basin (δD = −5.15 and δ¹⁸O = −2.34). These values are depleted if compared with the modern-day average precipitation, presumably indicating paleo-groundwater components recharged during previous humid climatic phases. The measured stable isotope values indicate that the geothermal wells, some of the hot springs and groundwater wells mainly consist of meteoric water. The Sr isotopic signatures in all waters are within the range of the Sr isotopic composition of the rift basalts and rhyolites. The variability of Sr isotopic data also pinpoints complex water–rock interaction and mixing processes in groundwater and surface water. The ⁸⁷Sr/⁸⁶Sr ratio ranges from 0.70445 to 0.70756 in the hot springs, from 0.70426 to 0.70537 in two deep geothermal wells, and from 0.70673 to 0.70721 in the rift lakes Ziway, Langano, Shala and Awasa. The radiogenic composition recorded by the lakes indicates that the input water was predominantly affected by progressive interaction with rhyolitic volcanics and lacustrine sediments.     

Chlorine transfer out of a very low permeability clay sequence (Paris Basin, France): Cl and Cl evidence

The marine Callovo-Oxfordian clay formation is found at a depth around 410m in the eastern part of the Paris Basin (France). It is a very low permeability formation investigated by the French agency for nuclear waste management (ANDRA) to study the feasibility of a radioactive waste disposal. Examining hydrogeological and geochemical characteristics of the clay sequence may test confinement properties of this formation. This study uses chlorine isotopes to investigate long-term transport processes which may carry chemical elements out of the clay layer to the surrounding rocks. Detailed chlorine concentration and δ³⁷Cl depth profiles are examined using pore waters and aquifer waters sampled in the clay formation and its surrounding aquifers (the Dogger at the bottom and the Oxfordian/Kimmeridgian/Tithonian unit at the top). They are discussed in terms of chlorine budget and hydrogeological processes.Clay pore waters and aquifer waters show strong chlorine concentration depletion (<3000 mg/L) relative to the original marine interstitial water (∼19000 mg/L). This probably results from an early dilution by meteoric water in limestones (as also indicated by oxygen and hydrogen isotopes).A steep Cl-concentration gradient from the Dogger at ∼500m in depth (∼2500 mg/L) to the Oxfordian/Kimmeridgian/Tithonian aquifer near the surface (≈ 10 mg/L) is associated to a ‘v-shaped’ profile of the δ³⁷Cl values. Modelling Cl transport shows that a hydrodynamic dispersion process explains Cl concentration and δ³⁷Cl profiles in Oxfordian Limestone. This process implies a mean upward flux of chloride in the 2.6 10⁻⁸-8.2 10⁻⁸ mole/m²/yr range from the clay formation towards upper limestones where a westward advective flow disperses the chloride. The modelling and knowledge of underground water transfer suggest a maximum effective Cl-hydrodynamic vertical dispersion coefficient (= vertical Cl-transport coefficient) of ∼7.6 10⁻¹⁰ m²/s.Chlorine transfer through the Callovo-Oxfordian clay, since deposition 160My ago, can be mainly described by the interplay of an early dilution and a later hydrodynamic dispersion event which has apparently erased most of the isotopic effects of diagenetic events (such as early diffusion, ion filtration etc.).     

Pleistocene–Holocene environmental change in the Canary Archipelago as inferred from the stable isotope composition of land snail shells

The isotopic composition of land snail shells was analyzed to investigate environmental changes in the eastern Canary Islands (28–29°N) over the last ~ 50 ka. Shell δ¹³C values range from −8.9‰ to 3.8‰. At various times during the glacial interval (~ 15 to ~ 50 ka), moving average shell δ¹³C values were 3‰ higher than today, suggesting a larger proportion of C₄ plants at those periods. Shell δ¹⁸O values range from −1.9‰ to 4.5‰, with moving average δ¹⁸O values exhibiting a noisy but long-term increase from 0.1‰ at ~ 50 ka to 1.6–1.8‰ during the LGM (~ 15–22 ka). Subsequently, the moving average δ¹⁸O values range from 0.0‰ at ~ 12 ka to 0.9‰ at present. Calculations using a published snail flux balance model for δ¹⁸O, constrained by regional temperatures and ocean δ¹⁸O values, suggest that relative humidity at the times of snail activity fluctuated but exhibited a long-term decline over the last ~ 50 ka, eventually resulting in the current semiarid conditions of the eastern Canary Islands (consistent with the aridification process in the nearby Sahara). Thus, low-latitude oceanic island land snail shells may be isotopic archives of glacial to interglacial and tropical/subtropical environmental change.     

Establishing constraints on groundwater ages with Cl,C, H,and noble gases: A case study in the eastern Paris basin,France

Groundwaters from the Tithonian/Kimmeridgian, Oxfordian and Upper Dogger aquifers, within the eastern part of the Paris basin (France), were characterised using ³H, ¹⁴C and ³⁶Cl, and noble gases tracers, to evaluate their residence times and determine their recharge period. This information is an important prerequisite to evaluating the confinement properties of the Callovo-Oxfordian clay formation sandwiched between the Oxfordian aquifer and the Dogger aquifer, currently being investigated by the French nuclear waste management agency (Andra) for radioactive waste disposal. Data presented in this paper are used to test 4 hypotheses.     

Stable isotope composition of CO2 outgassed from cores of argillites: a simple method to constrain δ18O of porewater and δ13C of dissolved carbon in mudrocks

Stable isotope characterization of porewater, and dissolved species, in mudrocks and argillaceous rocks is notoriously difficult. Techniques based on physical or chemical extraction of porewater can generate significant analytical artefacts. The authors report a novel, simple approach to determine the δ¹⁸O of porewater and δ¹³C of dissolved C in argillites. The method uses core samples placed in specifically-designed outgassing cells, sealed shortly after drilling and stored in well-controlled conditions. After 1–2 months, CO₂ naturally outgassed by argillite porewater is collected, purified and analyzed for C and O isotopes. Porewater δ¹⁸O and dissolved C δ¹³C are calculated from CO₂ isotope data using appropriate fractionation factors. This methodology was successfully applied to the Callovo-Oxfordian argillites from Bure (eastern Paris Basin, France) and the Opalinus Clay formation from Mont Terri (Switzerland). In both clay formations, results indicate that porewater is meteoric and dissolved C is of marine origin. The main advantage of the approach is that it does not induce any major physical or chemical disturbance to the clay–water system investigated. Further testing on argillaceous rocks of variable composition and organic content is needed to assess extent of applicability.     

Modelling of bentonite–granite solutes transfer from an in situ full-scale experiment to simulate a deep geological repository (Grimsel Test Site, Switzerland)

The FEBEX experiment is a 1:1 simulation of a high level waste disposal facility in crystalline rock according to the Spanish radwaste disposal concept. This experiment has been performed in a gallery drilled in the underground laboratory Grimsel Test Site (Switzerland). Two boreholes parallel to the FEBEX drift were drilled 20 and 60 cm away from the granite–bentonite interface to provide data on potential bentonite–granite solutes transfer. Periodic sampling and analysis of the major ions showed: (a) the existence of solutes transfer from the bentonite porewater towards the granite groundwater, explaining the Cl⁻ and Na⁺ contents of the latter; (b) that the concentration of the natural tracers coming into the granite groundwater from the bentonite porewater increased over time. This bentonite–granite solutes transfer was modelled in order to predict the increase in the Cl⁻ and Na⁺ concentrations of the granite groundwater. The modelled results seem to confirm that the mechanism of solute migration in this scenario is that of diffusive transport. An effective diffusion coefficient of D_e = 5 × 10⁻¹¹ m²/s was that which best fitted the data obtained.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.     

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.     

Assessment of MTBE biodegradation in contaminated groundwater using C and C analysis: Field and laboratory microcosm studies

Radiolabelled assays and compound-specific stable isotope analysis (CSIA) were used to assess methyl tert-butyl ether (MTBE) biodegradation in an unleaded fuel plume in a UK chalk aquifer, both in the field and in laboratory microcosm experiments. The ¹⁴C-MTBE radiorespirometry studies demonstrated widespread potential for aerobic and anaerobic MTBE biodegradation in the aquifer. However, δ¹³C compositions of MTBE in groundwater samples from the plume showed no significant ¹³C enrichment that would indicate MTBE biodegradation at the field scale. Carbon isotope enrichment during MTBE biodegradation was assessed in the microcosms when dissolved O₂ was not limiting, compared with low in situ concentrations (2 mg/L) in the aquifer, and in the absence of O₂. The microcosm experiments showed ubiquitous potential for aerobic MTBE biodegradation in the aquifer within hundreds of days. Aerobic MTBE biodegradation in the microcosms produced an enrichment of 7‰ in the MTBE δ¹³C composition and an isotope enrichment factor (ε) of −1.53‰ when dissolved O₂ was not limiting. However, for the low dissolved O₂ concentration of up to 2 mg/L that characterizes most of the MTBE plume fringe, aerobic MTBE biodegradation produced an enrichment of 0.5-0.7‰, corresponding to an ε value of −0.22‰ to −0.24‰. No anaerobic MTBE biodegradation occurred under these experimental conditions. These results suggest the existence of a complex MTBE-biodegrading community in the aquifer, which may consist of different aerobic species competing for MTBE and dissolved O₂. Under low O₂ conditions, the lower fractionating species have been shown to govern overall MTBE C-isotope fractionation during biodegradation, confirming the results of previous laboratory experiments mixing pure cultures. This implies that significant aerobic MTBE biodegradation could occur under the low dissolved O₂ concentration that typifies the reactive fringe zone of MTBE plumes, without producing detectable changes in the MTBE δ¹³C composition. This observed insensitivity of C isotope enrichment to MTBE biodegradation could lead to significant underestimation of aerobic MTBE biodegradation at field scale, with an unnecessarily pessimistic performance assessment for natural attenuation. Site-specific C isotope enrichment factors are, therefore, required to reliably quantify MTBE biodegradation, which may limit CSIA as a tool for the in situ assessment of MTBE biodegradation in groundwater using only C isotopes.     

Oxygen,hydrogen and carbon isotope studies of the franciscan formation,Coast Ranges,California

Analyses of 230 Franciscan rock and mineral samples, including the San Luis Obispo ophiolite, show that metamorphism produces no change in the δ¹⁸O of the graywackes (+11 to +14), but that igneous rocks become enriched in ¹⁸O by 2–6% and the cherts depleted by 5–10%. The shales are of two types, a high-¹⁸O type (+16 to +20) associated with chert and a low-¹⁸O type isotopically and mineralogically similar to the graywackes. The vein quartz (δ = + 15 to + 20) is invariably richer in ¹⁸O than the host rock quartz and in most of the rocks the δ¹⁸O of the clastic quartz is similar to the δ¹⁸O of the whole rock. Mineral assemblages are typically not in isotopic equilibrium. Although the δ¹⁸O values are very uniform (+13 to +16). the δ¹³C of vein aragonite and calcite is widely variable (0 to ? 14), implying that a major source of the carbon is oxidized organic material. The δD values of 83 igneous and sedimentary rocks are -45 to -80, exceptions are the Fe-rich minerals howieite and deerite, which have δD = ?100. All of these samples could have equilibrated with H₂O having δD ≈ +10 to ?20 and δ¹⁸O ≈ ?3 to +8. assuming temperatures of 100–300°C. However, the serpentines (δD ≈ ?85 to ?110) and the vein minerals (δD = ?23 to ?55) are exceptions. The vein minerals are 10–20%, richer in deuterium than the adjacent wall rocks; they formed from a relatively D-rich metamorphic water, typically at lower temperatures than did their host rocks. The isotopic compositions of the other Franciscan rocks were affected by three distinct events: (1) hydrothermal alteration of the ophiolite complexes and volcanic rocks as a result of submarine igneous activity at a spreading center or in an island-arc environment; (2) low-temperature, high-pressure regional metamorphism and diagenesis; and (3) a late-stage, very low temperature (<100°C) alteration of the ultramafic bodies by meteoric ground waters, producing lizardite-chrysotile serpentine. In the first two cases, the pore fluid involved in the alteration of the Franciscan rocks was sea water. However, this water became somewhat depleted in D and enriched in ¹⁸O during blueschist metamorphism, evolving to values of δD ≈ ? 20 and δ¹⁸O ≈ + 6 to + 8 at the highest grades. Except for one graywacke sample, the meteoric waters that affected the serpentinites did not significantly change the $\text{D}\text{H}$ ratios of the OH-bearing minerals in any other Franciscan rock.The δ¹⁸O values of orogenic andesites are too low for such magmas to have formed by direct partial melting of Franciscan-type materials in a subduction zone. Andesites either form in some other fashion, or the melts must undergo thorough isotopic exchange with the upper mantle. The great Cordilleran granodiorite-tonalite batholiths, however, are much richer in ¹⁸O and may well have formed by large-scale melting or assimilation of Franciscan-type rocks. The range of δD values of Franciscantype rocks is identical to the ?50 to ?80 range shown by most igneous rocks. This suggests that ‘primary magmatic H₂O’ throughout the world may be derived mainly by partial melting of Franciscantype materials, or by dehydration of such rocks in the deeper parts of a Benioff zone.     

Investigation on the hydrodynamics of Ganga Alluvial Plain using environmental isotopes: a case study of the Gomati River Basin, northern India

An investigation using environmental isotopes (δ¹⁸O and δD) was conducted to gain insight into the hydrological processes of the Ganga Alluvial Plain, northern India. River-water, shallow-groundwater and lake-water samples from the Gomati River Basin were analyzed. During the winter season, the δ¹⁸O and δD compositions of the Gomati River water ranged from ?1.67 to ?7.62 ‰ and ?25.08 to ?61.50 ‰, respectively. Deuterium excess values in the river water (+0.3 to ?13 ‰) and the lake water (?20 ‰) indicate the significance of evaporation processes. Monthly variation of δ¹⁸O and δD values of the Gomati River water and the shallow groundwater follows a similar trend, with isotope-depleted peaks for δ¹⁸O and δD synchronized during the monsoon season. The isotopically depleted peak values of the river water (δ¹⁸O?=??8.30 ‰ and δD?=??57.10 ‰) can be used as a proxy record for the isotopic signature of the monsoon precipitation in the Ganga Alluvial Plain.     

Isotope geochemistry of fluid inclusions in Permian halite with implications for the isotopic history of ocean water and the origin of saline formation waters

δD and δ¹⁸O values have been determined for fluid inclusions in 45 samples of Permian halite. The inclusions are enriched in ¹⁸O relative to the meteoric water line but are depleted in D relative to ocean water. Inclusions with the more positive δ-values coincide with the isotopic composition expected for evaporating sea water which follows a hooked trajectory on a δD-δ¹⁸O diagram. Inclusions with more negative δ-values may represent more highly evaporated sea water but probably reflect synsedimentary or diagenetic mixing of meteoric water with evaporite brines. The isotope systematics in these inclusions are sufficiently similar to those of a modern evaporite pan to indicate that Permian sea water was isotopically similar to modern sea water.Connate evaporite brines can have negative δ-values because of the probable hooked isotope trajectory of evaporating sea water and/or synsedimentary mixing of evaporite brines with meteoric waters. Subsurface formation waters composed of mixtures of remnant primary evaporite brines and later meteoric waters may be more common than previous isotopic evidence has suggested.     

USGS46 Greenland Ice Core Water – A New Isotopic Reference Material for δ2H and δ18O Measurements of Water

Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual‐inlet isotope‐ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary isotopic reference waters for daily normalisation of stable hydrogen (δ²H) and stable oxygen (δ¹⁸O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The measured δ²H and δ¹⁸O values of this reference water were ?235.8 ± 0.7‰ and ?29.80 ± 0.03‰, respectively, relative to VSMOW on scales normalised such that the δ²H and δ¹⁸O values of SLAP reference water are, respectively, ?428 and ?55.5‰. Each uncertainty is an estimated expanded uncertainty (U = 2u_c) about the reference value that provides an interval that has about a 95‐percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.     

Isotopic constraints on growth conditions of multiphase calcite–pyrite–barite concretions in Carboniferous mudstones

Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ¹³C=?28·7‰ PDB and δ¹⁸O=?1·6‰ PDB through to δ¹³C=?6·9‰ PDB and δ¹⁸O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ¹³C=?12·0 to ?10·1‰ PDB and δ¹⁸O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ³⁴S=+24·8‰ CDT and δ¹⁸O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ³⁴S=+6 to +11‰ CDT and δ¹⁸O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.     

Oxygen isotope speedometry in granulite facies garnet recording fluid/melt–rock interaction (Sør Rondane Mountains,East Antarctica)

In situ analysis of a garnet porphyroblast from a granulite facies gneiss from Sør Rondane Mountains, East Antarctica, reveals discontinuous step‐wise zoning in phosphorus and large δ¹⁸O variations from the phosphorus‐rich core to the phosphorus‐poor rim. The gradually decreasing profile of oxygen isotope from the core (δ¹⁸O = ~15‰) to the rim (δ¹⁸O = ~11‰) suggests that the ¹⁸O/¹⁶O zoning was originally step‐wise, and modified by diffusion after the garnet rim formation at ~800°C and 0.8 GPa. Fitting of the ¹⁸O/¹⁶O data to the diffusion equation constrains a duration of the high‐T event (~800°C) to c. 0.5–40 Ma after the garnet rim formation. The low δ¹⁸O value of the garnet rim, together with the previously reported low δ¹⁸O values in metacarbonates, indicates regional infiltration, probably along a detachment fault, of low δ¹⁸O fluid/melt possibly derived from meta‐mafic to ultramafic rocks.     

Karst springs as “natural” pluviometers: Constraints on the isotopic composition of rainfall in the Apennines of central Italy

This paper describes an indirect method to calculate the isotopic composition of rainfall by using the isotopic composition of karst springs fed by waters circulating in the most important regional aquifer of central Italy, i.e. the Mesozoic limestone sequence that forms the backbone of the Apennines. By using δ¹⁸O and δD data and the δ¹⁸O (and/or δD) average gradient for elevation, evaluated through the use of literature rainfall data and new measurements from a typical Alpine valley in northern Italy, the altitude of precipitation of their parent water has been re-calculated. Vertical descents of more than 2000 m, from recharge to discharge, have been assessed in some high flow-rate cold springs in the morphologically steep Adriatic sector of central Italy. A clear correlation between the vertical descents and more negative isotopic compositions at their relative emergence elevations is highlighted. In contrast, in the Tyrrhenian sector lower karstic drops (generally lower than 500 m) correlate with less negative isotopic composition of recharge areas.The δ¹⁸O iso-contour map of the “recalculated” parent rainfall in central Italy is more detailed than any possible isotopic map of rainfall made using pluviometers, unless large number of rainfall collectors were deployed on mountaintops. The data also show that the isotopic composition of rainfall depends on the source of the storm water. In particular, precipitation is isotopically heavier when originating in the Mediterranean Sea, and lighter when formed in the Atlantic Ocean. Consequently, the collision between air masses with such a different isotopic signature results in a relatively small latitudinal fractionation effect. The peninsular part of central Italy is very narrow, with several mountains and massifs more that 2000 m high, and any latitudinal variation in the isotopic composition between rainfall sourced in the Atlantic Ocean and in the Mediterranean Sea is much lower than that due to the isotopic fractionation due to elevation.     

Traces of brine and hydrocarbon migration in carbon,oxygen, and sulfur isotopic compositions of reservoir rocks in the Talakan petroleum field,Southwestern Yakutia

Dolomites from the productive Osa horizon (upper subformation of the Lower Cambrian Bilir Formation) in the Talakan petroleum field show a prominent 1–2‰ decrease in δ¹⁸O (from 23–24 to 21–22‰), which presumably marks a zone of relatively high water/rock ratios. Productive boreholes are characterized by moderate δ³⁴S values (from 25.1 to 30.6‰) and negative correlation between δ³⁴S in anhydrite and δ¹⁸O in associated dolomite, which points to a partial sulfate reduction during catagenesis. In nonproductive borehole, δ³⁴S values increase significantly (from 31.4 to 35.6‰) and show positive correlation with δ¹⁸O in dolomite. Rocks recovered by nonproductive borehole possibly recrystallized during early diagenesis, and, correspondingly lost their permeability and capacity to form pores. Limestones and dolomites of the Osa horizon have a carbon isotopic composition within the range of normal marine carbonates (δ¹³C = 0 ± 1 ‰), which does not indicate a significant role of organic matter in postsedimentary recrystallization of carbonate sediments. A positive δ¹³C excursion up to 4.5‰ recorded in the lower subformation of the Bilir Formation presumably occurred at the sedimentation stage under conditions of high rates of bioproductivity and organic matter burial in sediments.     

Volcanic arc of Kamchatka: a province with high-δO magma sources and large-scale O/O depletion of the upper crust

We present the results of a regional study of oxygen and Sr-Nd-Pb isotopes of Pleistocene to Recent arc volcanism in the Kamchatka Peninsula and the Kuriles, with emphasis on the largest caldera-forming centers. The δ¹⁸O values of phenocrysts, in combination with numerical crystallization modeling (MELTS) and experimental fractionation factors, are used to derive best estimates of primary values for δ¹⁸O(magma). Magmatic δ¹⁸O values span 3.5‰ and are correlated with whole-rock Sr-Nd-Pb isotopes and major elements. Our data show that Kamchatka is a region of isotopic diversity with high-δ¹⁸O basaltic magmas (sampling mantle to lower crustal high-δ¹⁸O sources), and low-δ¹⁸O silicic volcanism (sampling low-δ¹⁸O upper crust). Among one hundred Holocene and Late Pleistocene eruptive units from 23 volcanic centers, one half represents low-δ¹⁸O magmas (+4 to 5‰). Most low-δ¹⁸O magmas are voluminous silicic ignimbrites related to large >10 km³ caldera-forming eruptions and subsequent intracaldera lavas and domes: Holocene multi-caldera Ksudach volcano, Karymsky and Kurile Lake-Iliinsky calderas, and Late Pleistocene Maly Semyachik, Akademy Nauk, and Uzon calderas. Low-δ¹⁸O magmas are not found among the less voluminous products of stratovolcano eruptions and these volcanoes do not show drastic changes in δ¹⁸O during their evolution. Additionally, high-δ¹⁸O(magma) of +6.0 to 7.5‰ are found among basalts and basaltic andesites of Bezymianny, Shiveluch, Avachinsky, and Koryaksky volcanoes, and dacites and rhyolites of Opala and Khangar volcanoes (7.1-8.0‰). Phenocrysts in volcanic rocks from the adjacent Kurile Islands (ignimbrites and lavas) define normal-δ¹⁸O magmas. The widespread and volumetric abundance of low-δ¹⁸O magmas in the large landmass of Kamchatka is possibly related to a combination of near-surface volcanic processes, the effects of the last glaciation on high-latitude meteoric waters, and extensive geyser and hydrothermal systems that are matched only by Iceland. Sr and Pb isotopic compositions of normal and low-δ¹⁸O, predominantly silicic, volcanic rocks show negative correlation with δ¹⁸O, similar to the trend in Iceland. This indicates that low-δ¹⁸O volcanic rocks are largely produced by remelting of older, more radiogenic, hydrothermally altered crust that suffered δ¹⁸O-depletion during >2 My-long Pleistocene glaciation. The regionally-distributed high-δ¹⁸O values for basic volcanism (ca. + 6 to +7.5‰) in Kamchatka cannot be solely explained by high-δ¹⁸O slab fluid or melt (± sediment) addition in the mantle, or local subduction of hydrated OIB-type crust of the Hawaii-Emperor chain. Overall, Nd-Pb isotope systematics are MORB-like. Voluminous basic volcanism (in the Central Kamchatka Depression in particular) requires regional, though perhaps patchy, remobilization of thick (30-45 km) Mesozoic-Miocene arc roots, possibly resulting from interaction with hot (ca. 1300°C), wedge-derived normal-δ¹⁸O, low-⁸⁷Sr/⁸⁶Sr basalts and from dehydration melting of lower crustal metabasalts, variably high in δ¹⁸O and ⁸⁷Sr/⁸⁶Sr.