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

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

Variability of Indian monsoonal rainfall over the past 100 ka and its implication for C3–C4 vegetational change

Oxygen and carbon isotope ratios of soil carbonate and carbon isotope ratios of soil organic matter (SOM) separated from three cores, Kalpi, IITK and Firozpur, of the Ganga Plain, India are used to reconstruct past rainfall variations and their effect on ambient vegetation. The δ¹⁸O values of soil carbonate (δ¹⁸O_SC) analyzed from the cores range from ? 8.2 to ? 4.1‰. Using these variations in δ¹⁸O_SC values we are able, for the first time, to show periodic change in rainfall amount between 100 and 18 ka with three peaks of higher monsoon at about 100, 40 and 25 ka. The estimation of rainfall variations using δ¹⁸O value of rainwater-amount effect suggests maximum decrease in rainfall intensity (~ 20%) during the last glacial maximum. The δ¹³C values of soil carbonate (δ¹³C_SC) and SOM (δ¹³C_SOM) range from ? 6.3 to + 1.6‰ and ? 28.9 to ? 19.4‰, respectively, implying varying proportions of C₃ and C₄ vegetations over the Ganga Plain during the last 100 ka. The comparison between monsoonal rainfall and atmospheric CO₂ with vegetation for the time period 84 to 18 ka indicate that relative abundances of C₃ and C₄ vegetations were mainly driven by variations in monsoonal rainfall.     

The nappe-hosted Hoshbulak MVT Zn–Pb deposit,Xinjiang, China: A review of the geological,elemental and stable isotopic constraints

The Hoshbulak Zn–Pb deposit is located in South Tianshan, Xinjiang, China. The Zn–Pb orebody is tabular and stratoid in form and it is hosted in calcareous rocks of the Upper Devonian Tan'gaitaer Formation which were thrust over the Carboniferous system. The ores are mineralogically simple and composed mainly of sphalerite, galena, pyrite, calcite, dolomite and exhibit massive, banded, veinlets, colloidal, metasomatic, eutectic, concentric ring and microbial-like fabrics. The Co/Ni ratios of pyrite in the ores range from 0.46 to 0.90 by electron microprobe, which suggested that the Hoshbulak Zn–Pb mineralization was formed in a sedimentary environment. The REE patterns of the hydrothermal calcite coincide well with those of recrystallized micritic limestones, suggesting that the Hoshbulak Pb–Zn mineralization was closely genetically related to limestones of the Tan'gaitaer Formation. The C-, H- and O-isotopic compositions of hydrothermal calcite and dolomite in the ores yield δ¹³C(VPDB) values ranging from − 1.9‰ to + 2.6‰ (mean 0.79‰), δ¹⁸O(VSMOW) values from 22.41‰ to 24.67‰ (mean 23.04‰) and δD values from − 77‰ to − 102‰ for fluid inclusions. It is suggested that the ore-forming fluids, including CO₂, were derived from the calcareous strata of the Tan'gaitaer Formation in association with hydrocarbon brines. The δ³⁴S(VCDT) ranges from − 22.3‰ to − 8.5‰ for early ore-stage sulfides and from 5.9‰ to 24.2‰ with a cluster between 14.4‰ and 24.2‰ for the sulfides (pyrite, sphalerite, galena) in the main ore-stage. The ore sulfur may have been derived from evaporite rocks by thermochemical sulfate reduction (TSR) as the predominant mechanism for H₂S generation. The Pb-isotopic compositions of the sulfide minerals from the Hoshbulak ores yield ²⁰⁶Pb/²⁰⁴Pb ratios from 17.847 to 18.173, ²⁰⁷Pb/²⁰⁴Pb ratios from 15.586 to 15.873 and ²⁰⁸Pb/²⁰⁴Pb ratios from 37.997 to 38.905, which indicate that the metals were sourced mainly from the Tan'gaitaer Formation. We conclude that the genesis of the Hoshbulak Mississippi Valley-type deposit was closely related to thrust faulting in the South Tianshan orogen of China.     

Characterisation and isotopic evolution of saline waters of the Outokumpu Deep Drill Hole,Finland – Implications for water origin and deep terrestrial biosphere

The isotopic composition of water and dissolved Sr as well as other geochemical parameters at the 2516 m deep Outokumpu Deep Drill Hole, Finland were determined. The drill hole is hosted by Palaeoproterozoic turbiditic metasediments, ophiolite-derived altered ultramafic rocks and pegmatitic granitoids. Sodium–Ca–Cl and Ca–Na–Cl-rich waters (total dissolved solids up to ca. 70 g L⁻¹) containing significant amounts of gas, mainly CH₄ (up to 32 mmol L⁻¹), N₂ (up to 10 mmol L⁻¹), H₂ (up to 3.1 mmol L⁻¹) and He (up to 1.1 mmol L⁻¹) discharge from fracture zones into the drill hole. This water is distinct from the shallow fresh groundwater of the area, and has an isotopic composition typical of shield brines that have been modified during long-term water–rock interaction. Based on water stable isotopes and geochemistry, the drill hole water profile can be divided into five water types, each discharging from separate fracture systems and affected by the surrounding rocks. The δ²H varies from −90‰ to −56‰ (VSMOW) and δ¹⁸O from −13.5‰ to −10.4‰ (VSMOW), plotting clearly above the Global and Local Meteoric Water Lines on a δ²H vs. δ¹⁸O diagram. The ⁸⁷Sr/⁸⁶Sr ratios range between 0.72423 and 0.73668. Simple two-component mixing between ²H and ¹⁸O rich end-member brine and meteoric water cannot explain the water stable isotopic composition and trends observed. Instead, hydration of silicates by ancient groundwaters recharged under different climatic conditions, warmer than at present, is the most likely mechanism to have caused the variation of the δ²H and δ¹⁸O values. Water types correlate with changes in microbial communities implying that different ecosystems occur at different depths. The different water types and microbial populations have remained isolated from each other and from the surface for long periods of time, probably tens of millions of years.     

Late Pleistocene vegetation change in Korea and its possible link to East Asian monsoon and Dansgaard–Oeschger (D–O) cycles

Late Pleistocene carbon isotope (δ¹³C) records from a paleolithic sedimentary sequence collected from Baeki, Hongcheon, central Korea, show long-term changes with superimposed short-term isotopic excursions. The δ¹³C value of the sedimentary organic matter, a proxy for past vegetation change, varied from ? 26‰ to ? 23‰ for the period between 30 and 90 ka, with a long-term variation similar to insolation changes. High-amplitude (? 1‰ to approximately ? 1.5‰) fluctuations superimposed on the long-term changes in the δ¹³C values decreased during stronger summer monsoon intervals but increased during the weakened summer monsoon. This millennial-scale pattern is generally similar to Greenland Dansgaard–Oeschger (D–O) cycles. The possible connection between the Hongcheon area, Korea and high latitudes may be explained by atmospheric circulation changing in response to the D–O oscillations in the Northern Hemisphere.     

Late-glacial to Holocene transition in northern Spain deduced from land-snail shelly accumulations

Shells of the helicid Cepaea nemoralis were studied using taphonomic, isotopic and morphometric measurements to estimate late glacial–Holocene (~ 12.1–6.3 cal ka BP) environmental conditions in northern Spain. Higher taphonomic alteration among Holocene shells suggests lower sedimentation rates or higher shell-destruction rates than during glacial conditions. Shells preserved the aragonitic composition despite differing degree of skeleton damage. Shell δ¹³C values were ? 10.3 ± 1.1‰, ? 8.2 ± 2.3‰, and ? 7.3 ± 1.6‰ for modern, Holocene and late-glacial individuals, respectively. Higher δ¹³C values during the late-glacial and some Holocene periods imply higher water stress of C₃ plants and/or higher limestone contribution than today. Intrashell δ¹³C values were higher during juvenile stages suggesting higher limestone ingestion to promote shell growth. Shell δ¹⁸O values were ? 1.1 ± 0.7‰, ? 0.9 ± 0.8‰ and ? 0.1 ± 0.7‰ for modern, Holocene and late-glacial specimens, respectively. A snail flux-balance model suggests that during ~ 12.1 ? 10.9 cal ka BP conditions were drier and became wetter at ~ 8.4 ? 6.3 cal ka BP and today. Intrashell δ¹⁸O profiles reveal that glacial individuals experienced more extreme seasonality than interglacial shells, despite possible larger hibernation periods. Shell size correlated positively with δ¹⁸O values, suggesting that growth rates and ultimate adult size of C. nemoralis may respond to climate fluctuation in northern Spain.     

Isotope (C and O) composition of auriferous quartz carbonate veins,central lode system,Gadag Gold Field,Dharwar Craton,India: Implications to source of ore fluids

Carbon (δ¹³C_PDB) and oxygen (δ¹⁸O_SMOW) isotopic compositions of auriferous quartz-carbonate veins (QCVs) of gold deposits from Sangli, Kabuliyatkatti, Nagavi, Nabapur and Mysore mining areas developed on the Central Lode system of the Gadag Gold Field (GGF) in the Neoarchaean Gadag schist belt of the Dharwar Craton, southern India have been examined for the first time to understand the origin of the mineralising fluids. In majority of the samples (46 out of 49), δ¹³C_pdb of carbonates of the QCVs fall in the range from − 2.2‰ to − 9.7‰ and the δ¹⁸O values range from 12.0‰ to 30.5‰ SMOW. The calculated fluid δ¹³C_∑ C compositions for these deposits range from − 2.1‰ to − 9.6‰ and δ¹⁸O_H2O from 6.8‰ to 25.9‰, respectively. Carbonate δ¹³C and fluid δ¹³C_∑ C compositions of the carbonates of the QCVs of the GGF are not only distinct from the carbon isotope range of marine carbonates or meta-sedimentary carbonates of the Chitradurga schist belt, but are consistent with C-isotope values of magmatic (− 5 ± 3‰, Burrows et al., 1986) and/or mantle (− 6 ± 2‰, Ohmoto, 1986) carbonates. As dissolution/decarbonation reactions during metamorphism of pre-existing carbonate/carbonated rocks produce CO₂ with δ¹³C values similar to or more enriched than parent rock, the carbonate or fluid δ¹³C ratios of the QCVs (which fall in the compositional range of mantle/magmatic derived CO₂ or carbonates) obtained in this work cannot be the result of metamorphism. The present study corroborates our previous reports from Ajjanahalli and G.R. Halli gold deposits (Sarangi et al., 2012) occurring in the vicinity of the southern extension of the same crustal scale shear zone on which all the GGF deposits are located.The age of gold mineralisation in this area has been reported to be 2522 ± 6 Ma by Sarma et al., 2011. Chardon et al. (2011) have proposed large-scale remobilization of the older gneissic basement, as well as, emplacement of juvenile granites between 2559 Ma and 2507 Ma, close to the crustal scale shear zone along the eastern margin of the Chitradurga schist belt. Based on these observations and our isotope studies, it is proposed that gold mineralising fluids were derived from mantle/juvenile magmatic melts and were channelled through crustal scale shear zones to give rise to the gold deposits in the GGF.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

Using dual isotopic data to track the sources and behaviors of dissolved sulfate in the western North China Plain

This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ³⁴S_SO4 with the median value of 10.3‰ (n = 4) and 7.9‰ to 15.6‰ for δ¹⁸O_SO4 with the median value of 14.3‰ (n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ³⁴S_SO4 and δ¹⁸O_SO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II₁) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II₂) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II₃) group with moderate sulfate concentration (median values of 2.13 mM and 1.17 mM for UGW and CGW, respectively) and more positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 10.7‰ and 7.7‰ for UGW, 20.1‰ and 8.8‰ for CGW). In the present study, three major sources of sulfate could be differentiated as following: sulfate dissolved from Ordovician to Permian rocks (δ³⁴S_SO4 = 10–35‰ and δ¹⁸O_SO4 = 7–20‰), soil sulfate (δ³⁴S_SO4 = 5.9‰ and δ¹⁸O_SO4 = 5.8‰) and sewage water (δ³⁴S_SO4 = 10.0‰ and δ¹⁸O_SO4 = 7.6‰). Kinetic fractionations of sulfur and oxygen isotopes as a result of bacterial sulfate reduction (BSR) were found to be evident in the confined aquifer in stagnant zone (II₃), and enrichment factors of sulfate–sulfur and sulfate–oxygen isotopes calculated by Rayleigh equation were −12.1‰ and −4.7‰ respectively along the flow direction of groundwater at depths of 60–100 m. The results obtained in this study confirm that detailed hydrogeological settings and identification of anthropogenic sources are critical for elucidating evolution of δ³⁴S_SO4 and δ¹⁸O_SO4 values along with groundwater flow path, and this work also provides a useful framework for understanding sulfur cycling in alluvial plain aquifers.     

Intermediate sulfidation epithermal gold-base metal deposits in Tertiary subaerial volcanic rocks,Sahinli/Tespih Dere (Lapseki/Western Turkey)

Gold in the Sahinli and Tespih Dere intermediate sulfidation gold-base metal deposits in Western Turkey occurs in relatively deep epithermal quartz veins along with base metal minerals which have epithermal textures, including plumose quartz, vug infills, comb and cockade textures and matrix-supported milled breccias. The total sulfide content of the veins in the area is variable ranging from < 1% to 60% and is dominated by pyrite, galena, sphalerite and chalcopyrite. Sphalerite is Fe-poor (0.6 to 1.4 mol% FeS). Minor amounts of Ag-rich tetrahedrite are present. Primary hydrothermal alteration minerals include illite/muscovite, mixed-layer illite/smectite (11.6 Å) and clinochlore towards the east and, alunite, dickite/nacrite and pyrophyllite towards the west at Sahinli; major illite/muscovite and dickite occur at Tespih Dere and Sarioluk, respectively.Fluid inclusions in main-stage quartz at Sahinli are only liquid-rich, with homogenization temperatures ranging from 220 to 322 °C and the majority of T_h values between 250 and 300 °C. Salinity ranges from 4.3 to 6.9 wt.% NaCl equiv. First ice-melting temperatures (T_mf) between ?24.5 and ?19.0 °C indicate that the fluids were dominated by NaCl – H₂O during mineralization. The relatively higher average T_h at the Tespih Dere deposit (295 °C) is attributed to a relatively deeper level of exposure.Calculated δ¹⁸O values indicate that ore-forming hydrothermal fluids in the study area had δ¹⁸O_H2O ranging from + 1.1 to + 9.7‰ (average = 3.8‰), strongly ¹⁸O-enriched compared with present-day hydrothermal meteoric water in the area (δ¹⁸O = ?8.5‰). δD values of fluid inclusions in quartz range from ?58 to ?93‰ and δD values of clay minerals and alunite from ?40 to ?119‰. δD values from intermediate argillic alteration (average = ?68‰) in the study area are very similar to δD values of the present-day local geothermal system (average δD = ?54‰) whereas δD values from advanced-argillic alteration (average δD = ?33‰) are very different from the present-day local geothermal system.The δ³⁴S values in samples from the Sahinli and Tespih Dere deposits average ?2.9‰ for pyrite; ?3.3‰ for chalcopyrite; ?5.4‰ for sphalerite and ?7.6‰ for galena. These data are consistent with derivation of the sulfur from either igneous rocks or possibly from local wallrock.     

Geochemical and isotopic evidence for a magmatic-hydrothermal origin of the polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen,South China

Polymetallic vein-type Zn-Pb deposits are located in the Xiangxi–Qiandong zinc-lead metallogenic belt (XQMB) of the northwestern margin of the Jiangnan Orogen, South China. Ores are mainly found in fault-bounded quartz veins hosted in the upper part of the Banxi Group that consists of low-grade metamorphic sandstone, siltstone with minor tuff interbeds. The Zn-Pb deposits primarily contain sphalerite, galena, chalcopyrite and pyrite, accompanied by quartz and minor calcite. Zinc, lead, copper, indium and gallium are enriched in these ores. Investigation of the ore fluid reveals low temperature (87–262 °C) with scattered salinity (range from 2.73 to 26.64 wt% NaCl_eqv.). Hydrogen and oxygen isotopic compositions of fluid inclusions in quartz indicate mixing of magmatic hydrothermal fluid and meteoric water (δ¹⁸O_{H2O SMOW} = 0.2‰ to 4.2‰; δD_{H2O SMOW} = −126‰ to −80‰). Carbon and oxygen isotopic composition of carbonate samples indicate the magmatic hydrothermal origin of CO₃²⁻ or CO₂ in ore-forming fluid (δ¹³C_PDB = −6.9‰ to −5.7‰, δ¹⁸O_SMOW = 11.3‰ to 12.7‰). Sulfur and lead isotopic compositions (δ³⁴S_VCDT = 8.8–14.2‰ and ²⁰⁶Pb/²⁰⁴Pb = 17.156–17.209, ²⁰⁷Pb/²⁰⁴Pb = 15.532–15.508, ²⁰⁸Pb/²⁰⁴Pb = 37.282–37.546) demonstrate that sulfur sources were relatively uniform, and low radiogenic lead isotopic compositions indicate that ore metals were derived from a relatively unradiogenic source, probably by mixing of mantle with crust. Therefore, polymetallic vein-type Zn-Pb mineralization in this area probably arose from a magmatic-related hydrothermal system, and the deposition of sulfides occurred in response to cooling and boiling of magmatic hydrothermal fluids (high salinity, high δ¹⁸O_H2O and δD_H2O and metal-bearing), and is mainly the result of emplacement into open space and mixing with meteoric water (low salinity, low δ¹⁸O_H2O and δD_H2O). This study provides direct evidence that magmatism was involved in the ore-forming processes of the low temperature metallogenic district, South China, and it raises awareness about the presence of polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen and their potential as a source of zinc, copper, indium and gallium.     

Origin and evolution of hydrothermal fluids in epithermal Pb-Zn-Cu ± Au ± Ag deposits at Koru and Tesbihdere mining districts, Çanakkale,Biga Peninsula,NW Turkey

The Koru and Tesbihdere mining districts in Biga Peninsula, Northwestern Turkey, consist of twelve deposits covering approximately 12 km². The epithermal Au-Ag enriched base metal veins and associated low-grade breccia and stockwork at Koru and Tesbihdere are hosted by Oligocene subaerial and calc-alkaline volcanic rocks including basaltic andesite lavas, dacitic lava-tuffs, rhyolitic lava-domes and tuffs. NW- to N-trending strike-slip faults and E- and NE-trending faults constitute the most important ore-controlling structures in the Koru and Tesbihdere districts respectively. In the Koru mining district, galena is the dominant ore mineral in barite-quartz veins containing sphalerite, chalcopyrite, pyrite, bornite, enargite and tennantite. According to base metal content, the Tesbihdere mining district can be subdivided into sphalerite-galena dominated Tesbihdere mineralization and chalcopyrite-pyrite dominated Bakır and Kuyu Zones mineralization. Gold is present in small quantities with maximum 3.14 g/t Au values either as free grains in quartz or as micro inclusions in pyrite and galena. The most widespread silver minerals are polybasite, pearceite, argentite and native silver which commonly occur as replacements of galena, sphalerite and pyrite, and other sulfides, or as fillings of microfractures in sulfides and quartz.Microthermometric measurements of primary liquid-rich fluid inclusions in sphalerite, barite and quartz in Koru indicate that the veins were formed at temperatures between 407 and 146 °C from fluids with salinities between 0.7 and 12.5 wt.% equiv. NaCl. Barite from the Tahtalıkuyu, Kuyutaşı and 5^th Viraj mineralization show the highest homogenization temperatures. Fluid inclusion data for ore-stage quartz and sphalerite from the Tesbihdere mining district, indicate that these minerals were deposited at temperatures between 387 and 232 °C from more diluted fluids with moderate salinities between 0.2 and 10.6 wt.% NaCl equiv. Tahtalıkuyu and 5^th Viraj mineralization show only boiling trends while Kuyutaşı, Tesbihdere, Bakır and Kuyu Zones mineralization show both boiling and isothermal mixing trends. The O and H isotope compositions of ore fluids from the Tahtalıkuyu (δ¹⁸O = − 1.40 to 0.25‰; δD = − 72.49 to − 52.68‰) and Kuyutaşı (δ¹⁸O = − 2.29 to 3.59‰; δD = − 90.70 to − 70.93‰) mineralization indicate that there was a major contribution from a magmatic component to ore genesis. Based on 9 quartz samples associated with orebodies at the Tesbihdere mining district, the relatively higher δ¹⁸O and lower δD isotope compositions from hydrothermal fluids could be attributed to a relatively dilute fluid derived by the mixing with meteoric water. The Pb isotope compositions also reveal that most of the lead in both mining districts is derived from the Oligocene-Miocene magmatic rocks, possibly with smaller contributions from the Eocene magmatic rocks.     

Paragenesis of Cretaceous to Eocene carbonate reservoirs in the Ionian fold and thrust belt (Albania): relation between tectonism and fluid flow

ABSTRACT This paper examines the diagenetic history of dual (i.e. matrix and fracture) porosity reservoir lithologies in Cretaceous to Eocene carbonate turbidites of the Ionian fold and thrust belt, close to the oil‐producing centre of Fier–Ballsh (central Albania). The first major diagenetic event controlling reservoir quality was early cementation by isopachous and syntaxial low‐Mg calcite. These cements formed primarily around crinoid and rudist fragments, which acted as nucleation sites. In sediments in which these bioclasts are the major rock constituent, this cement can make up 30% of the rock volume, resulting in low effective porosity. In strata in which these bioclasts are mixed with reworkedmicrite, isopachous/syntaxial cements stabilized the framework, and matrixporosity is around 15%. The volumetric importance of these cements, their optical and luminescence character (distribution and dull orange luminescence) and stable isotopic signal (δ¹⁸O and δ¹³C averaging respectively; ?0·5‰ VPDB and +2‰ VPDB) all support a marine phreatic origin. Within these turbidites and debris flows, several generations of fractures alternated with episodes of cementation. A detailed reconstruction of this history was based on cross‐cutting relationships of fractures and compactional and layer‐parallel shortening (LPS) stylolites. The prefolding calcite veins possess orange cathodoluminescence similar to that of the host rock. Their stable isotope signatures (δ¹⁸O of ?3·86 to ?0·85‰ VPDB and δ¹³C of – 0·14 to + 2·98‰ VPDB) support a closed diagenetic rock‐buffered system. A similar closed system accounts for the selectively reopened and subsequently calcite‐cemented LPS stylolites (δ¹⁸O of ?1·81 to ?1·14‰ VPDB and δ¹³C of +1·52 to +2·56‰ VPDB). Within the prefolding veins, brecciated host rock fragments and complex textures such as crack and seal features resulted from hydraulic fracturing. They reflect expulsion of overpressured fluids within the footwall of the frontal thrusts. After folding and thrust sheet emplacement, some calcite veins are still rock buffered (δ¹⁸O of ?0·96 to +0·2‰ VPDB and δ¹³C of +0·79 to +1·37‰ VPDB), whereas others reflect external (i.e. extraformational) and thus large‐scale fluid fluxes. Some of these veins are linked to basement‐derived fluid circulation or originated from fluid flow along evaporitic décollement horizons (δ¹⁸O around +3·0‰ VPDB and δ¹³C around +1·5‰ VPDB). Others are related to the maturation of hydrocarbons in the system (δ¹⁸O around ?7·1‰ VPDB and δ¹³C around +9·3‰ VPDB). An open joint system reflecting an extensional stress regime developed during or after the final folding stage. This joint system enhanced vertical connectivity. This open joint network can be explained by the high palaeotopographical position and the folding of the reservoir analogue within the deformational front. The joint system is pre‐Burdigalian in age based upon a dated karstified discordance contact. Sediment‐filled karst cavity development is linked to meteoric water infiltration during emergence of some of the structures. Despite its sediment fill, the karst network is locally an important contributor to reservoir matrix porosity in otherwise tight lithologies. Development of secondary porosity along bed‐parallel and bed‐perpendicular (i.e. layer‐parallel shortening) stylolites is interpreted as a late‐stage diagenetic event associated with migration of acidic fluids during hydrocarbon maturation. Development of porosity along the LPS system enhanced the vertical reservoir connectivity.     

Determination of germanium isotopic compositions of sulfides by hydride generation MC-ICP-MS and its application to the Pb–Zn deposits in SW China

Determining Ge isotopic compositions of sulfides is important to understand the ore-forming processes. Single step anion-exchange chromatography was previously used to recover Ge from silicates and lignites. We apply this procedure to recover Ge from sulfides before determining Ge isotopic compositions by hydride generation (HG)-MC-ICP-MS. Germanium is quantitatively recovered by the proposed sample preparation method. There are no obvious isotope biases for Ge-bearing solutions containing significant amounts of Cu, Sn, and W. However, δ⁷⁴Ge values show obvious shifts if the solutions contain high Zn, Pb, and Sb, which is possibly attributed to suppression of germane formation that fractionates Ge isotopes. The long-term reproducibility for Ge standard solution is about ± 0.18‰ for δ⁷⁴Ge. Spex and Merck standard solutions yield mean δ⁷⁴Ge values of − 0.70 ± 0.19‰ and − 0.36 ± 0.08‰, respectively. The calculated δ⁷⁴Ge value (− 5.13‰) of sphalerite standard based on doping experiments is indistinguishable from those of sphalerite without doping (− 5.05‰ and − 5.01‰). Sulfides from the Jinding, Shanshulin, and Tianqiao Pb–Zn deposits in SW China have δ⁷⁴Ge values of − 4.94‰ to + 2.07‰. The paragenetic sequence of sulfides from the Shanshulin and Tianqiao Pb–Zn deposits is pyrite, sphalerite and galena from early to late. Sulfides from the same ore show a trend of δ⁷⁴Ge_pyrite < δ⁷⁴Ge_sphalerite < δ⁷⁴Gegalena, which may be controlled by the kinetic or Rayleigh fractionation.     

Hydrothermalism in the Tyrrhenian Sea: Inorganic and microbial sulfur cycling as revealed by geochemical and multiple sulfur isotope data

The Palinuro volcanic complex and the Panarea hydrothermal field, both located in the Tyrrhenian Sea (Italy), are associated with island arc magmatism and characterized by polymetallic sulfide mineralization. Dissolved sulfide concentrations, pH, and Eh measured in porewaters at both sites reveal a variable hydrothermal influence on porewater chemistry.Multiple sulfur isotopic measurements for disseminated sulfides (CRS: chromium reducible sulfur) extracted from sediments at Palinuro yielded a broad range in δ³⁴S range between ?29.8 and + 10.2‰ and Δ³³S values between + 0.015 and + 0.134‰. In contrast, sediments at Panarea exhibit a much smaller range in δ³⁴S_CRS with less negative values between ?11.3 and ?1.8‰. The sulfur isotope signatures are interpreted to reflect a mixture between hydrothermal and biogenic sulfide, with a more substantial biogenic contribution at Panarea.Multiple sulfur isotope measurements were performed on sulfides and elemental sulfur from drill core material from the Palinuro massive sulfide complex. δ³⁴S and Δ³³S values for pyrite between ?32.8 and ?1.1‰ and between ?0.012 to + 0.042‰, respectively, as well as for elemental sulfur with δ³⁴S and Δ³³S values between ?26.7 and ?2.1‰ and between + 0.035 and + 0.109‰, respectively, point to a microbial origin for much of the sulfide and elemental sulfur studied. Moreover, data suggest a coupling of bacterial sulfate reduction, sulfide oxidation and sulfur disproportionation. In addition, δ³⁴S values for barite between + 25.0 and + 63.6‰ are also in agreement with high microbial turnover of sulfate at Palinuro.Although a magmatic SO₂ contribution towards the formation of the Palinuro massive sulfide complex is very likely, the activity of different sulfur utilizing microorganisms played a fundamental role during its formation. Thus, porewater and multiple sulfur isotope data reveal differences in the hydrothermal activity at Palinuro and Panarea drill sites and underline the importance of microbial communities for the origin of massive sulfide mineralizations in the hydrothermal subsurface.     

Geology and isotope geochemistry (C–O–S) of the Diyadin gold deposit,Eastern Turkey: A newly-discovered Carlin-like deposit

Diyadin mineralization is the first reported gold deposit located in a collisional tectonic environment in Eastern Anatolia. The mineralization is related to N–S and N10–20°W-trending fault systems and hosted within the Paleozoic metamorphic basement rocks of the Anatolide–Toride microcontinent. Calc-schist, dolomitic marble and Miocene and Quaternary volcanic rocks comprise the exposed units in the mineralized area. Geochemical signatures, alteration types and host rock characteristics of the Diyadin gold deposit resemble those of Carlin-type deposits. Mineralization is constrained by alteration of overlying volcanic rocks to younger than ~ 14 Ma (K–Ar).Carbon and oxygen stable isotope measurements of carbonate rocks were made on six drill holes (n = 81) with an additional four samples of fresh carbonate rocks from surface outcrops. Background carbonate rocks have δ¹³C_V-PDB ~ 1.8‰ and δ¹⁸O_V-SMOW ~ 27‰. Isotopically-altered host rock samples have decreased δ¹⁸O (down to ~+11.4‰) and variable δ¹³C (from − 3.6 to + 4.8‰). Postore carbonate veins and cave-fill material have distinctly different isotopic signatures, particularly carbon (from δ¹³C = + 8.4 to + 9.8‰). Whether this post-ore carbonate is simply very late in mineralization associated with the gold system, or is a completely different, younger system utilizing the same pathways, is unclear at present. Within the host rock sample set, there is no correlation between gold and δ¹³C, and a weak correlation between gold and δ¹⁸O, indicative of water–rock interaction and isotopic alteration. Both the isotopic data and structural mapping suggest that the main upflow zone for the deposit is near the northern portion of the drill fence. Additional data at multiple scales are required to clarify the relationship(s) between fluid flow and mineralization.     

Coupled lithium- and iron isotope fractionation during magmatic differentiation

In this study, we investigated Fe and Li isotope fractionation between mineral separates of olivine pheno- and xenocrysts (including one clinopyroxyene phenocryst) and their basaltic hosts. Samples were collected from the Canary Islands (Teneriffa, La Palma) and some German volcanic regions (Vogelsberg, Westerwald and Hegau). All investigated bulk samples fall in a tight range of Li and Fe isotope compositions (δ⁵⁶Fe_wr = 0.06–0.17‰ and δ⁷Li_ma = 2.5–5.2‰, assuming δ⁷Li of the olivine-free matrix is virtually identical to that of the bulk sample for mass balance reasons). In contrast, olivine phenocrysts display highly variable, but generally light Fe and mostly light Li isotope compositions compared to their respective olivine-free basaltic matrix, which was considered to represent the melt (with δ⁵⁶Fe_ol = ? 0.24 to 0.14‰ and δ⁷Li_ol = ? 10.5 to + 6.5‰, respectively). Single olivine crystals from one sample display even a larger range of δ⁵⁶Fe_ol between ? 0.7 and + 0.1‰. One single clinopyroxene phenocryst displays the lightest Li isotope composition (δ⁷Li_cpx = ? 17.7‰), but no Fe isotope fractionation relative to melt. The olivine phenocrysts show variable Mg# and Ni (correlated in most cases) that range between 0.89 and 0.74 and between 300 and 3000 μg/g, respectively. These olivines likely grew by fractional crystallization in an evolving magma. One sample from the Vogelsberg volcano contained olivine xenocrysts (Mg# > 0.89 and Ni > 3000 μg/g), in addition to olivine phenocrysts. This sample displays the highest Li- and the second highest Fe-isotope fractionation between olivine and melt (Δ⁷Li_ol-melt = ? 13; Δ⁵⁶Fe_ol-melt = ? 0.29).Our data, i.e. the variable olivine- at constant whole rock and matrix isotope compositions, strongly indicate disequilibrium, i.e. kinetic Fe and Li isotope fractionation between olivine and melt (for Li also between cpx and melt) during fractional crystallization. Δ⁷Li_ol-melt is correlated with the Li partitioning between olivine and melt (i.e. with Li_ol/Li_melt), indicating Li isotope fractionation due to preferential (faster) diffusion of ⁶Li into olivine during fractional crystallization. Olivine with low Δ⁷Li_ol-melt, also have low Δ⁵⁶Fe_ol-melt, indicating that Fe isotope fractionation is also driven by diffusion of isotopically light Fe into olivine, potentially, as Fe–Mg inter-diffusion. The lowest Δ⁵⁶Fe_ol-melt (? 0.40) was observed in a sample from Westerwald (Germany) with abundant magnetite, indicating relatively oxidizing conditions during magma differentiation. This may have enhanced equilibrium Fe isotope fractionation between olivine and melt or fine dispersed magnetite in the basalt matrix may have shifted its Fe isotope composition towards higher δ⁵⁶Fe. The decoupling of Li- and Fe isotope fractionation in cpx is likely due to faster diffusion of Li relative to Fe in cpx, implying that the large investigated cpx phenocryst resided in the magma for only a short period of time which was sufficient for Li- but not for Fe diffusion. The absence of any equilibrium Fe isotope fractionation between the investigated cpx phenocryst and its basaltic host may be related to the similar Fe^3 +/Fe^2 + of cpx and melt. In contrast to cpx, the generally light Fe isotope composition of all investigated olivine separates implies the existence of equilibrium- (in addition to diffusion-driven) isotope fractionation between olivine and melt, on the order of 0.1‰.     

Ore genesis and hydrothermal evolution of the Huanggang skarn iron–tin polymetallic deposit,southern Great Xing'an Range: Evidence from fluid inclusions and isotope analyses

The southern Great Xing'an Range is one of the most important metallogenic belts in northern China, and contains numerous Pb–Zn–Ag–Cu–Sn–Fe–Mo deposits. The Huanggang iron–tin polymetallic skarn deposit is located in the Sn-polymetallic metallogenic sub-belt. Skarns and iron orebodies occur as lenses along the contact between granite plutons and the Lower Permian Huanggangliang Formation marble or Dashizhai Formation andesite. Field evidence and petrographic observations indicate that the three stages of hydrothermal activity, i.e., skarn, oxide and sulfide stages, all contributed to the formation of the Huanggang deposit.The skarn stage is characterized by the formation of garnet and pyroxene, and high-temperature, hypersaline hydrothermal fluids with isotopic compositions that are similar to those of typical magmatic fluids. These fluids most likely were generated by the separation of brine from a silicate melt instead of being a product of aqueous fluid immiscibility. The iron oxide stage coincides with the replacement of garnet and pyroxene by amphibole, chlorite, quartz and magnetite. The hydrothermal fluids of this stage are represented by L-type fluid inclusions that coexist with V-type inclusions with anomalously low δD values (approximately − 100 to − 116‰). The decrease in ore fluid δ¹⁸O_H2O values with time coincides with marked decreases in the fluid salinity and temperature. Based on the fluid inclusion and stable isotopic data, the ore fluid evolved by boiling of the magmatic brine. The sulfide stage is characterized by the development of sphalerite, chalcopyrite, fluorite, and calcite veins, and these veins cut across the skarns and orebodies. The fluids during this stage are represented by inclusions with a variable but continuous sequence of salinities, mainly low-salinity inclusions. These fluids yield the lowest δ¹⁸O_H2O values and moderate δD values ( − 1.6 to − 2.8‰ and − 101 to − 104‰, respectively). The data indicate that the sulfide stage fluids originated from the mixing of residual oxide-stage fluids with various amounts of meteoric water. Boiling occurred during this stage at low temperatures.The sulfur isotope (δ³⁴S) values of the sulfides are in a narrow range of − 6.70 to 4.50‰ (mean = − 1.01‰), and the oxygen isotope (δ¹⁸O) values of the magnetite are in a narrow range of 0.1 to 3.4‰. Both of these sets of values suggest that the ore-forming fluid is of magmatic origin. The lead isotope compositions of the ore (²⁰⁶Pb/²⁰⁴Pb = 18.252–18.345, ²⁰⁷Pb/²⁰⁴Pb = 15.511–15.607, and ²⁰⁸Pb/²⁰⁴Pb = 38.071–38.388) are consistent with those of K-feldspar granites (²⁰⁶Pb/²⁰⁴Pb = 18.183–18.495, ²⁰⁷Pb/²⁰⁴Pb = 15.448–15.602, ²⁰⁸Pb/²⁰⁴Pb = 37.877–38.325), but significantly differ from those of Permian marble (²⁰⁶Pb/²⁰⁴Pb = 18.367–18.449, ²⁰⁷Pb/²⁰⁴Pb = 15.676–15.695, ²⁰⁸Pb/²⁰⁴Pb = 38.469–38.465), which also suggests that the ore-forming fluid is of magmatic origin.     

Origins of non-equilibrium lithium isotopic fractionation in xenolithic peridotite minerals: Examples from Tanzania

Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ⁷Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ⁷Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ⁷Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ⁷Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ⁷Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ⁷Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ⁷Li), while non mantle-like, low δ⁷Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.