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.     

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.     

Fluid inclusion and stable isotope study of the Cobre–Babilonia polymetallic epithermal vein system, Taxco district, Guerrero, Mexico

The Cobre–Babilonia vein system formed during a single major hydrothermal stage and is part of the Taxco district in Guerrero, southern Mexico. Homogenization and ice melting temperatures range from 160 to 290 °C and from − 11.6 to − 0.5 °C, respectively. We determined an approximate thermal gradient of 17 to 20 °C per 100 m using fluid inclusions. A thermal peak marked by the 290 °C isotherm is interpreted as a major feeder channel to the veins. The highest content of Zn + Pb in ore coincides with the 220 and 240 °C isotherms. Salinities of mineralizing fluids range from 0.8 to 15.6 wt.% NaCl equiv, and are distributed in two populations that can be related with barren or ore-bearing vein sections, with 0.8 to 6 wt.% NaCl equiv and 7 to 15.6 wt.% NaCl equiv, respectively. δ¹³C and δ¹⁸O water values from calcite from the Cobre–Babilonia vein system and the Esperanza Vieja and Guadalupe mantos range − 5.4‰ to − 10.4‰ and 9.9‰ to 13.4‰, respectively. δ³⁴S values range from 0‰ to 3.2‰ and − 0.7‰ to − 4.3‰ in sphalerite, − 4‰ to 0.9‰ in pyrite, and − 1.4‰ to − 5.5‰ in galena. Both fluid inclusion and stable isotope data are compatible with magmatic and meteoric sources for mineralizing fluids. Also, sulfur isotope compositions suggest both magmatic and sedimentary sources for sulfur.     

Evolution of palaeofluids at the Variscan thrust front in eastern Belgium

The geochemical evolution of the fluids migra- ting at the Variscan thrust front in eastern Belgium has been investigated by a petrographic, mineralogical and geoche-mical study of ankerite, quartz and ferroan calcite veins hosted by lower Devonian rocks. Three vein generations have been recognized. The first generation consists of quartz, chlorite and ankerite filling pre- to early Variscan extensional fractures. The second generation is present as shear veins of Variscan age, and contains quartz, chlorite and ferroan calcite. The third generation consists of ankerite filling post-Variscan fractures. The oxygen and carbon isotopic composition of the two ankerite phases and of the ferroan calcites are respectively between –16.4 and –11.4‰ PDB between –17.8 and –1.7‰ PDB. This range is greater than that of calcite nodules in the lower Devonian siliciclastic sediments (δ¹⁸O= –15.6 to –11.1‰ PDB and δ¹³C= –13.4 to –10.2‰ PDB). This suggests precipitation of the carbonate veins from a fluid which was at most only partly isotopically buffered by the calcite nodules in the host rock. The calculated oxygen isotopic composition of the ambient fluid from which the calcite veins formed is between +7.8 and +10.0‰ SMOW. Two main fluid types have been recognized in fluid inclusions in the quartz and carbonates. The first fluid type is present as secondary fluid inclusions in the first and second vein generations. The fluid has a salinity of 0.5–7.2 eq. wt.% NaCl and a high, but variable, homogenization temperature (Th=124–188°C). Two origins can be proposed for this fluid. It could have been expelled from the lower Devonian or could have been derived from the metamorphic zone to the south of the area studied. Taking into account the microthermometric and stable-isotope data, and the regional geological setting, the fluid most likely originated from metamorphic rocks and interacted with the lower Devonian along its migration path. This is in agreement with numerical simulations of the palaeofluid and especially the palaeotempera-ture field, which is based on chlorite geothermometry and vitrinite reflectance data. The second fluid type occurs as secondary inclusions in the shear veins and as fluid inclusions of unknown origin in post-Variscan ankerite veins. Therefore, it has a post-Variscan age. The inclusions are characterized by a high salinity (18.6–22.9 eq. wt.% CaCl₂). The composition of the fluid is similar to that which caused the development of Mississippi Valley-type Pb–Zn deposits in Belgium.     

Burial-dominated cementation in non-tropical carbonates of the Oligocene Te Kuiti Group, New Zealand

Cementation of bryozoan-echinoid-benthic foraminiferal temperate shelf carbonates of the Oligocene Te Kuiti Group, North Island, New Zealand, occurred mainly during subsurface burial. The calcite cements in the limestones are dominated by equant and syntaxial rim spar which typically becomes ferroan (given an iron supply) and, compared to the skeletal material with normal marine δ¹⁸O values from +2 to −1‰, more depleted in ¹⁸O with depth of burial, the δ¹⁸O composition of bulk cement samples ranging from −1 to −7‰. These trends reflect the establishment in pore waters during sediment burial of reducing conditions and gradually increasing temperatures (20–50°C), respectively. The δ¹³C values (0 to +3‰) of the cements remain the same as the host marine shells, suggesting the source of carbon in the cements was simply redistributed marine carbonate derived from shell dissolution.

Two gradational burial diagenetic environments influenced by marine-derived porewaters are arbitrarily distinguished: shallow burial phase and moderate burial phase. During the shallow burial phase, down to 500–600 m sub-bottom depth, the carbonates lost at least 25% of their original porosity by mechanical compaction and were selectively cemented by non-ferroan or usually ferroan, variably luminescent, slightly ¹⁸O-depleted sparry calcite cement (δ¹⁸O −2 to −4‰), mainly as syntaxial rims about echinoid grains. These shallow-burial cements form less than about 10% of total cement in the majority of the limestones and their source was probably mainly mild intergranular dissolution of calcitic skeletal fragments accompanying the onset of chemical compaction. During the moderate burial phase, between about 600 and 1100 m sub-bottom depth, porosity loss continued (typically to about 70% of its original value) as a result of pressure-solution of calcitic bioclasts associated with more advanced stages of chemical compaction. This involved development of a wide variety of non-sutured and microstylolitic solution seams, including both single and composite, wispy or continuous, bedding-parallel types and non-parallel reticulate forms. The released carbonate was precipitated as ferroan (or non-ferroan where iron supply was negligible), dull luminescent, strongly ¹⁸O-depleted (δ¹⁸O −4 to −7‰), mainly equant calcite spar cement, occluding available pore space in the limestones.     

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.     

Geological features and origin of gold deposits occurring in the Baotou–Bayan Obo district, south-central Inner Mongolia, People's Republic of China

Located at western portion of northern margin of North China craton, the Baotou–Bayan Obo district is one of the most important Fe–REE–Nb and Au metallogenic provinces in China. Presently, about 52 gold deposits and prospects have been discovered, explored and mined, among which Shibaqinhao, Laoyanghao, Houshihua, Saiyinwusu, Wulashan and Donghuofang are the most important ones. All these gold occurrences can be subdivided into three groups (or types) according to its host rocks: (1) hosted by Archean high-grade metamorphic rocks; (2) hosted by Proterozoic sedimentary rocks; (3) hosted by or related to Hercynian alkaline intrusive rocks. The first group contains the Shibaqinhao, Laoyanghao and Houshihua gold deposits. Gold mineralization at these three deposits occurs within Archean amphibolite, gneiss and granulite as gold-bearing quartz veins and veinlet groups containing native gold, electrum, pyrite and chalcopyrite. The Saiyinwusu deposit belongs to the second group, and occurs within Proterozoic sandstone, quartzite and carbonaceous slate as quartz veins and replacement bodies along the fracture zones. Pyrite, marcasite, arsenopyrite, native gold and electrum are identified. The third group includes the Wulashan, Donghuofang and Luchang deposits. Gold mineralization at these three deposits occurs predominantly within the Hercynian alkaline syenite or melagabbro stocks and dyke swarms or along their contacts with Archean metamorphic wall rocks as K-feldspar–quartz veins, dissemination and veinlets. Pyrite, galena, chalcopyrite, native gold and calaverite are major metallic minerals.δ³⁴S value of sulfides (pyrite, galena and pyrrhotite) separates from groups 1 and 2 varies from −4.01‰ to −0.10‰ and −3.01‰ to 2.32‰, respectively. δ³⁴S values of Archean and Proterozoic metamorphic wall rocks for groups 1 and 2 deposits range from −20.2‰ to −17.0‰ and −15.8‰ to −16.2‰, respectively. The values are much lower than their hosted gold deposits. All these pyrite separates from Hercynian alkaline intrusions associated with the gold deposits show positive δ³⁴S values of 1.3‰ to 4.8‰, which is higher than those Precambrian metamorphic wall rocks and their hosted gold deposits. δ³⁴S values of the sulfides (pyrite and galena) from the Donghuofang and Wulashan deposits (group 3) increase systematically from veins (−14.8‰ to −2.4‰) to the Hercynian alkaline igneous wall rocks (2.8‰ to 4.8 ‰). All of these deposits in groups 1, 2 and 3 show relatively radiogenic lead isotopic compositions compared to mantle or lower crust curves. Most lead isotope data of sulfides from the gold ores plot between the Hercynian alkaline intrusions and Precambrian metamorphic wall rocks. Data are interpreted as indicative of a mixing of lead from mantle-derived alkaline magma with lead from Precambrian metamorphic wall rocks.Isotopic age data, geological and geochemical evidence suggest that the ore fluids for the groups 1 and 2 deposits were generated during the emplacement of the Hercynian alkaline syenite and mafic intrusions. The Hercynian alkaline magma may provide heat, volatiles and metals for these groups 1 and 2 deposits. Evolved metamorphic fluids produced by the devolatilization, which circulated the wall rocks, were also progressively involved in the alkaline magmatic hydrothermal system, and may have dominate the ore fluids during late stage of ore-forming processes. Most of these gold deposits hosted by Archean high-grade metamorphic rocks occur at or near the intersections of the NE- and E–W-trending fracture systems. The ore fluid of the group 3 deposits may have resulted from the mixing of Hercynian alkaline magmatic fluids and evolved meteoric waters. The deposits are believed to be products of Hercynian alkaline igneous processes along deep-seated fault zones within Archean terrain.     

Oxygen and carbon isotope composition of cold-water Berriedale Limestone (Lower Permian), Tasmania, Australia

The Berriedale Limestone formed at about 80°S paleolatitude and contains many glacial dropstones. It formed during a period of major Gondwana deglaciation.

The Berriedale Limestone contains mostly bryozoans, brachiopods and bivalves, with some intraclasts and rare pellets. The faunal diversity is low and the fauna are similar to the modern cold-water foramol faunal assemblage. Micrite, microspar and spar occur as equant to well developed rhombs of calcite. The coarse spar cements are bored and are ruptured by dropstones, indicating submarine origin of low-Mg calcite at water-temperatures of around 3°C. The mixing zone cementation was preceded by erosion of early formed crystals. The eroded crystals occur as inclusions in mixing zone cements.

The fauna are characterized by heavy δ¹³C and light δ¹⁸O. The whole-rock field of δ¹⁸O-δ¹³C falls at the edge of “Normal Marine Limestone” and deviates to lighter δ¹⁸O values (down to −16.7‰ PDB). Lightest δ¹⁸O values ( −22‰ PDB) of fresh-water sparry calcite cement are similar to those in the Early Permian continental tillites, suggesting that the Permian sea was diluted by isotopically light melt waters. Micrite δ¹⁸O values (−9.2 to −12.6‰ PDB) are within the range of whole-rock values. The δ¹⁸O values of calcite in shales are lighter than limestone values.

The δ¹⁸O values of the fauna give an unrealistic range of sea-water temperatures because the fauna have equilibrated with variable amounts of melt waters. However, calculated original δ¹⁸O values of the fauna indicate temperatures < 4°C. The heaviest δ¹⁸O of fauna gives cold temperatures of 9°C (with δ_w −2.8‰) and −3°C (with δ_w −6‰). The lightest values of sparry calcite cements (−22‰ PDB) indicate that the limestone reacted with cold melt waters.

The δ¹⁸O of Permian sea is estimated to be about +1.2‰ and was diluted by melt waters as light as −27‰ SMOW.     

Dolomite formation in breccias at the Musandam Platform border, Northern Oman Mountains, United Arab Emirates

The presence of dolomite breccia patches along Wadi Batha Mahani suggests large-scale fluid flow causing dolomite formation. The controls on dolomitization have been studied, using petrography and geochemistry. Dolomitization was mainly controlled by brecciation and the nearby Hagab thrust. Breccias formed as subaerial scree deposits, with clay infill from dissolved platform limestones, during Early Cretaceous emergence. Cathodoluminescence of the dolostones indicates dolomitization took place in two phases. First, fine-crystalline planar-s dolomite replaced the breccias. Later, these dolomites were recrystallized by larger non-planar dolomites. The stable isotope trend towards depleted values (δ¹⁸O: − 2.7‰ to − 10.2‰ VPDB and δ¹³C: − 0.6‰ to − 8.9‰ VPDB), caused by mixing dolomite types during sampling, indicates type 2 dolomites were formed by hot fluids. Microthermometry of quartz cements and karst veins, post-dating dolomites, also yielded high temperatures. Hot formation waters which ascended along the Hagab thrust are invoked to explain type 2 dolomitization, silicification and hydrothermal karstification.     

The Daduhe gold field at the eastern margin of the Tibetan Plateau: He, Ar, S, O, and H isotopic data and their metallogenic implications

The Daduhe gold field comprises several shear-zone-controlled Tertiary lode gold deposits distributed at the eastern margin of the Tibetan Plateau. The deposits are hosted in a Precambrian granite–greenstone terrane within the Yangtze Craton. The gold mineralization occurs mainly as auriferous quartz veins with minor sulphide minerals. Fluid inclusions in pyrite have ³He/⁴He ratios of 0.16 to 0.86 R_a, whereas their ⁴⁰Ar/³⁶Ar ratios range from 298 to 3288, indicating a mixing of fluids of mantle and crust origins. The δ³⁴S values of pyrite are of 0.7–4.2‰ (n = 12), suggesting a mantle source or leaching from the mafic country rocks. δ¹⁸O values calculated from hydrothermal quartz are between − 1.5‰ and + 6.0‰ and δD values of the fluids in the fluid inclusions in quartz are − 39‰ and − 108‰. These ranges demonstrate a mixing of magmatic/metamorphic and meteoric fluids. The noble gas isotopic data, along with the stable isotopic data suggest that the ore-forming fluids have a dominantly crustal source with a significant mantle component.     

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.     

Comparison of microbial gases from the Middle America Trench and Scripps Submarine Canyon: implications for the origin of natural gas

Chemical and isotopic compositions have been measured on 62 microbial gases from Tertiary hemipelagic sediments in the Middle America Trench off Guatemala and from decaying kelp and surf grass currently accumulating in Scripps Submarine Canyon off southern California. Gases from the Middle America Trench have been generated primarily by the reduction of carbon dioxide; methane δ¹³C varies from −84‰ to −39‰, methane δD varies from −208‰ to −145‰, and carbon dioxide δ¹³ C varies from −27‰ to +28‰. Gases from Scripps Submarine Canyon have been generated primarily by acetate dissimilation; methane δ¹³ C varies from −63‰ to −43‰, methane δD varies from −331‰ to −280‰, and carbon dioxide δ¹³C varies from −17‰ to +3‰.Methane δ¹³C values as heavy as −40‰ appear to be uncommon for gases produced by carbon dioxide reduction and, in the Middle America Trench, are associated with unusually positive carbon dioxide δ¹³C values. However, based on the 25‰ intramolecular fractionation between acetate car☐yl carbon and methyl carbon estimated from the Scripps Submarine Canyon data, methane produced by acetate dissimilation may commonly have heavy δ¹³C values. The δD of methane derived from acetate is more negative than natural methanes from other origins. Microbial methane δD values appear to be controlled primarily by interstitial water δD and by the relative proportions of methane derived from carbon dioxide and acetate.The chemical and isotopic compositions of microbial gas and thermogenic gas overlap, making it difficult to determine the origins of many commercial natural gases from methane δ¹³C and C₂₊ hydrocarbon concentrations alone. Measurements of methane δD and carbon dioxide δ¹³C can provide useful additional information, and together with ethane δ¹³C data, help identify gases with mixed microbial and thermogenic origins.     

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.     

Carbon and Oxygen Isotope Geochemistry of the Amba Dongar Carbonatite Complex, Gujarat, India

A carbon and oxygen isotope survey based on 42 samples from the Amba Dongar carbonatite complex of Gujarat, India, indicates that the magmatic differentiation series sövite → alvikite → ankeritic carbonatite is beset with a distinct isotope trend characterized by a moderate rise in ¹³C coupled with a sizeable increase in ¹⁸O. From an average of −4.6 ± 0.4 ‰ [PDB] for the least differentiated (coarse) sövite member, δ¹³C values slowly increase in the alvikite (−3.7 ± 0.6 ‰) and ankeritic fractions (−3.0 ± 1.1 ‰), whereas δ¹⁸O rises from 10.3 ± 1.7 ‰ [SMOW] to 17.5 ± 5.8 ‰ over the same sequence, reaching extremes between 20 and 28 ‰ in the latest generation of ankeritic carbonatite. While an apparent correlation between δ¹³C and δ¹⁸O over the δ¹⁸O range of 7–13 ‰ conforms with similar findings from other carbonatite complexes and probably reflects a Rayleigh fractionation process, the observed upsurge of ¹⁸O notably in the ankeritic member is demonstrably related to a late phase of low-temperature hydrothermal activity involving large-scale participation of ¹⁸O-depleted groundwaters. As a whole, the Amba Dongar carbonatite province displays the characteristic ¹³C/¹²C label of deep-seated (primordial) carbon, reflecting the carbon isotope composition of the subcontinental upper mantle below the Narmada Rift Zone of the Indian subcontinent.     

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.     

Influence of localised igneous activity on cleat dawsonite formation in Late Permian coal measures, Upper Hunter Valley, Australia

Stable (δ¹³C and δ¹⁸O) and radiogenic ⁸⁷Sr/⁸⁶Sr isotopic data have been used to investigate the origin of cleat dawsonite (NaAlCO₃(OH)₂) in the Late Permian Wittingham Coal Measures of the Upper Hunter region in the Sydney Basin, New South Wales. The δ¹³C_PDB values have a narrow range (− 1.7‰ to + 2.4‰), with an average of + 0.3‰, suggesting a magmatic source for the carbon. In contrast, δ¹⁸O_SMOW values have a wide range (+ 13.6‰ to + 19.8‰), and decrease systematically with decreasing distance from a major intrusion. This systematic variation reflects establishment of localised hydrothermal cells. Water–rock interaction between fluids associated with these hydrothermal cells, and Rb-poor volcaniclastic detritus in the coal measures, produced mantle-like ⁸⁷Sr/⁸⁶Sr (0.705032 to 0.706464) in the dawsonite.     

Pyrite of distinctive isotopic composition from the Hemlo deposit: A potential tool to identify this type of gold mineralization in Archean terrain

Most sulphides from various rock types and mineralization of Archean age exhibit sulphur isotope values (δ³⁴S) near 0‰. This is due to a general absence of conditions suitable for the oxidation-reduction reactions essential for isotopic fractionation. However, some important occurrences of Archean Au mineralization do display significant variations in δ³⁴S). One such occurrence with unusual isotopic compositions is the Hemlo gold deposit: pyrite from the ore typically has δ³⁴S < −6‰ to a minimum value of −17.5‰ The isotopic composition of the pyrite is correlated with the content of Au, indicating that they are genetically related.The sulphur isotope data suggest that sulphur compounds experienced redox reactions in the hydrothermal system at Hemlo and that sulphate was present prior to the Au mineralization. This sulphate may be of exogenic origin from a restricted basin, or of endogenic origin from magmatic-hydrothermal fluids. Other characteristic features of the deposit, such as enrichment in Sb, Tl and Hg, may also be explained by ore deposition under moderately oxidizing conditions.Distinctive δ³⁴S values were also observed in pyrite from Au mineralization at Heron Bay, 30 km west of Hemlo, and from baritic strata 21 to 27 km west and on approximate strike from Hemlo. These occurrences also represent sulphate-bearing hydrothermal systems and, as such, give distant information on the unusual environment of the mineralization at Hemlo. Since the isotopes of sulphur are sensitive to oxidation conditions they may be used to identify hydrothermal activities characteristic of this type of Au mineralization and to explore for other unusual areas of sulphate accumulation in Archean terrains.     

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.     

Petrological, geochemical, and stable isotope constraints on the genesis of the Miocene igneous rocks of Chetaibi and Cap de Fer (NE Algeria)

Miocene igneous rocks (diorites, andesites, dacites, rhyolites and microgranites) of Chetaibi and Cap de Fer massif, NE Algeria, are high-K calc-alkaline to shoshonitic rocks. Fresh diorites have δ³⁴S and δ¹⁸O values ranging between −2.5‰ and +5.9‰, +6.5‰ and +6.7‰ respectively, indicating a mantle origin. The relatively low δ³⁴S values (−5.4‰ to −12.2‰) and high δ¹⁸O (+8.3‰ to +9.0‰) of altered diorites indicate the input of a crustal component to the initial magma. The microgranites’ I-type signature is indicated by the geochemical data and the δ³⁴S and δ¹⁸O values of −1.2‰ and −3.6‰, and +7.8‰ to +10.4‰ respectively. The andesites show a large variation of δ³⁴S, between −33.2‰ and +25.7‰. Massive andesites with δ³⁴S between +6.8‰ and +7.6‰ preserve a ³⁴S-enriched mantle signature. The δ³⁴S of the lava flows between +25.7‰ and +25.8‰ are attributed to open system magma degassing, whereas the low δ³⁴S of two andesitic dyke samples (−13.7‰ and −33.2‰) strongly suggest a crustal sulphur input. High δ¹⁸O (+9.2‰ to +15.7‰) of andesites indicate post-magmatic alteration (mainly silicification); the flyschs with δ¹⁸O between of +13.3‰ and +21.7‰ are most likely the contaminant. Quartz veins within the andesites gave a δ¹⁸O value of +23.0‰ while silica-filling vesicles yielded a value of +13.8‰. Initial Sr-isotope data are rather high for all the rocks (diorites: 0.707–0.708, andesites: 0.707–0.710, and microgranites and rhyolites: 0.717–0.719), and because geochemical and stable isotope data do not indicate a substantial amount of crustal assimilation, an extensive enrichment of the mantle source by subducted sediments is called for. A metasomatized-mantle source, characterized by high radiogenic Sr and relatively high δ¹⁸O, has also been indicated for the genesis of similar Tertiary igneous rocks in the Western Mediterranean basin, e.g. the Volcanic Province of southeasten Spain [Benito, R., Lopez-Ruiz, J., Cebria, J.M., Hertogen, J., Doblas M., Oyarzun, R., Demaiffe, D., 1999. Sr and O isotope constraints on source and crustal contamination in the high-K calc-alkaline and shoshonitic neogene volcanic rocks of SE Spain. Lithos 46, 773–802] and some plutons of northeastern Algeria [Ouabadi, A., 1994. Pétrologie, géochimie et origine des granitoïdes peralumineux à cordiérite (Cap Bougaroun, Béni-Touffout et Filfila), Algérie nord-orientale. Thèse de Doctorat, Université de Rennes I, France, 257p; Fourcade, S., Capdevila, R., Ouabadi, A., Martineau, F., 2001. The origin and geodynamic significance of the Alpine cordierite-bearing granitoids of northern Algeria. A combined petrological, mineralogical, geochemical and isotopic (O, H, Sr, Nd) study. Lithos 57, 187–216].