Spatial distribution of mean winter air temperatures in Siberian permafrost at 20−18 ka BP using oxygen isotope data

Palaeotemperature reconstruction for the period of 20?18 ka BP in Siberia is here based on δ¹⁸O analysis and ¹⁴C dating of large syngenetic ice wedges. Dozens of yedoma exposures, from Yamal Peninsula to Chukotka, have been studied. Snow meltwater is considered to be the main source of ice‐wedge ice. The modern relationship between δ¹⁸O composition of ice‐wedge ice and winter temperature is used as a base for reconstruction. In modern ice wedges (elementary veins that have accumulated during the last 60–100 years) δ¹⁸O fluctuates between ?14 and ?20‰ in western Siberia and between ?23 and ?28‰ in northern Yakutia. The trend in δ¹⁸O distribution in ice wedges dated at 20?18 ka BP is similar to the modern one. For example, the δ¹⁸O values in Late Pleistocene wedges are more negative going from west to east by 8–10‰, i.e. from ?19 to ?25‰ in western Siberian ice wedges to ?30 to ?35‰ in northern Yakutia. However, values are as high as ?28 to ?33‰ in north Chukotka and the central areas of the Magadan Region and even as high as ?23 to ?29‰ in the east of Chukotka. The same difference between the oxygen isotope composition of ice wedges in the eastern and western regions of Siberian permafrost (about 8–10‰) is also preserved from 20?18 ka BP to the present: δ¹⁸O values obtained from large ice wedges from the Late Pleistocene vary from ?19 to ?25‰ in western Siberia to ?30 to ?35‰ in northern Yakutia. We conclude that, at 20?18 ka BP, mean January temperatures were about 8–12°C lower (in Chukotka up to 17–18°C) than at present.     

A two-stage fluid history for the Orocopia Schist and associated rocks related to flat subduction and exhumation,southeastern California

ABSTRACT

Stable isotopes combined with pre-existing ⁴⁰Ar/³⁹Ar thermochronology at the Gavilan Hills and Orocopia Mountains in southeastern California record two stages of fluid–rock interaction: (1) Stage 1 is related to prograde metamorphism as Orocopia Schist was accreted to the base of the crust during late Cretaceous–early Cenozoic Laramide flat subduction. (2) Stage 2 affected the Orocopia Schist and is related to middle Cenozoic exhumation along detachment faults. There is no local evidence that schist-derived fluids infiltrated structurally overlying continental rocks. Mineral δ¹⁸O values from Orocopia Schist in the lower plate of the Chocolate Mountains fault and Gatuna normal fault in the Gavilan Hills are in equilibrium at 490–580°C with metamorphic water (δ¹⁸O = 7–11‰). Phengite and biotite δD values from the Orocopia Schist and upper plate suggest metamorphic fluids (δD ~ –40‰). In contrast, final exhumation of the schist along the Orocopia Mountains detachment fault (OMDF) in the Orocopia Mountains was associated with alteration of prograde biotite and amphibole to chlorite (T ~ 350–400°C) and the influx of meteoric-hydrothermal fluids at 24–20 Ma. Phengites from a thin mylonite zone at the top of the Orocopia Schist and alteration chlorites have the lowest fluid δD values, suggesting that these faults were an enhanced zone of meteoric fluid (δD < –70‰) circulation. Variable δD values in Orocopia Schist from structurally lower chlorite and biotite zones indicate a lesser degree of interaction with meteoric-hydrothermal fluids. High fluid δ¹⁸O values (6–12‰) indicate low water–rock ratios for the OMDF. A steep thermal gradient developed across the OMDF at the onset of middle Cenozoic slip likely drove a more vigorous hydrothermal system within the Orocopia Mountains relative to the equivalent age Gatuna fault in the Gavilan Hills.     

Carbon and Oxygen Isotope Compositions of Calcite and Rhodochrosite from Geothermal Exploratory Drills TH‐4 and TH‐6 near the Toyoha Deposit,Hokkaido, Japan

We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ¹⁸O_SMOW and δ¹³C_PDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ¹⁸O =?12‰, δ¹³C =?10‰) and a deep high temperature water (300°C, δ¹⁸O =?5‰, δ¹³C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ¹⁸O and δ¹³C indicate that the carbonates precipitated from H₂CO₃‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.     

Geochemistry of О, Н, C,S, and Sr isotopes in the water and sediments of the Aral basin

The paper presents original authors' data on the O, H, C, S, and Sr isotopic composition of water and sediments from the basins into which the Aral Sea split after its catastrophic shoaling: Chernyshev Bay (CB), the basin of the Great Aral in the north, Lake Tshchebas (LT), and Minor Sea (MS). The data indicate that the δ¹⁸О, δD, δ¹³C, and δ³⁴S of the water correlate with the mineralization (S) of the basins (as of 2014): for CB, S = 135.6‰, δ¹⁸О = 4.8 ± 0.1‰, δD = 5 ± 2‰, δ¹³C (dissolved inorganic carbon, DIC) = 3.5 ± 0.1‰, δ³⁴S = 14.5‰; for LT, S = 83.8‰, δ¹⁸О = 2.0 ± 0.1‰, δD =–13.5 ± 1.5‰, δ¹³C = 2.0 ± 0.1‰, δ³⁴S = 14.2‰; and for MS, S = 9.2‰, δ¹⁸О =–2.0 ± 0.1‰, δD =–29 ± 1‰, δ¹³C =–0.5 ± 0.5‰, δ³⁴S = 13.1‰. The oxygen and hydrogen isotopic composition of the groundwaters are similar to those in MS and principally different from the artesian waters fed by atmospheric precipitation. The mineralization, δ¹³С, and δ³⁴S of the groundwaters broadly vary, reflecting interaction with the host rocks. The average δ¹³С values of the shell and detrital carbonates sampled at the modern dried off zones of the basins are similar: 0.8 ± 0.8‰ for CB, 0.8 ± 1.4‰ for LT, and –0.4 ± 0.3‰ for MS. The oxygen isotopic composition of the carbonates varies much more broadly, and the average values are as follows: 34.2 ± 0.2‰ for CB, 32.0 ± 2.2‰ for LT, and 28.2 ± 0.9‰ for MS. These values correlate with the δ¹⁸O of the water of the corresponding basins. The carbonate cement of the Late Eocene sandstone of the Chengan Formation, which makes up the wave-cut terrace at CB, has anomalously low δ¹³С up to –38.5‰, suggesting origin near a submarine methane seep. The δ³⁴S of the mirabilite and gypsum (11.0 to 16.6‰) from the bottom sediments and young dried off zone also decrease from CB to MS in response to increasing content of sulfates brought by the Syr-Darya River (δ³⁴S = 9.1 to 9.9‰) and weakening sulfate reduction. The ⁸⁷Sr/⁸⁶Sr ratio in the water and carbonates of the Aral basins do not differ, within the analytical error, and is 0.70914 ± 0.00003 on average. This value indicate that the dominant Sr source of the Aral Sea is Mesozoic–Cenozoic carbonate rocks. The Rb–Sr systems of the silicate component of the bottom silt (which is likely dominated by eolian sediments) of MS and LT plot on the Т = 160 ± 5 Ma, I₀ = 0.7091 ± 0.0001, pseudochron. The Rb–Sr systems of CB are less ordered, and the silt is likely a mixture of eolian and alluvial sediments.     

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.     

New data on variations of stable isotopes in the pingo ice core in the southern part of the Tazovsky Peninsula

The aim of this work is to obtain the vertical isotopic profile of the thick Pestsovoe pingo ice core in the southern part of the Tazovsky Peninsula, to determine the oxygen and hydrogen isotopic composition of the ice, and to reveal its formation conditions. Two trends were identified for the isotopic profile of the pingo ice: an insignificant increase of the δ¹⁸O (~1.5‰) and δD (~9‰) values at depths of 12–15 m and a gradual decrease of isotopic values by 3.8 and 23‰ for δ¹⁸O and δD, respectively, at a depth of 15–26 m. The formation of the pingo ice core in the semiclosed system resulted in fractionation of the isotopic composition of oxygen and hydrogen by more than 4 and 20‰, respectively.     

Oxygen and Hydrogen Isotopes of Waters in the Ordos Basin,China: Implications for Recharge of Groundwater in the North of Cretaceous Groundwater Basin

Hundreds of precipitation samples collected from meteorological stations in the Ordos Basin from January 1988 to December 2005 were used to set up a local meteoric water line and to calculate weighted average isotopic compositions of modern precipitation. Oxygen and hydrogen isotopes, with averages of ?7.8‰ and ?53.0‰ for δ18O and δD, respectively, are depleted in winter and rich in spring, and gradually decrease in summer and fall, illustrating that the seasonal effect is considerable. They also show that the isotopic difference between south portion and north portion of the Ordos Basin are not obvious, and the isotope in the middle portion is normally depleted. The isotope compositions of 32 samples collected from shallow groundwater (less than a depth of 150 m) in desert plateau range from ?10.6‰ to ?6.0‰ with an average of ?8.4‰ for δ18O and from ?85‰ to ?46‰ with an average of ?63‰ for δD. Most of them are identical with modern precipitation. The isotope compositions of 22 middle and deep groundwaters (greater than a depth of 275 m) fall in ranges from ?11.6‰ to ?8.8‰ with an average of ?10.2‰ for δ18O and from ?89‰ to ?63‰ with an average of ?76‰ for δD. The average values are significantly less than those of modern precipitation, illustrating that the middle and deep groundwaters were recharged at comparatively lower air temperatures. Primary analysis of 14C shows that the recharge of the middle and deep groundwaters started at late Pleistocene. The isotopes of 13 lake water samples collected from eight lakes define a local evaporation trend, with a relatively flat slope of 3.77, and show that the lake waters were mainly fed by modern precipitation and shallow groundwater.     

Nitrogen isotope studies of nitrate contamination of the thick vadose zones in the wastewater-irrigated area

The objective of this study was to investigate natural abundance and the distribution of nitrogen isotopic compositions to assess denitrification in two ~30 m thick vadose zones beneath the different land uses in the wastewater-irrigated area located in southern Shijiazhuang, China. Sediment samples were collected from cores of boreholes drilled in the vegetable growth plot and the wastewater-irrigated farmland for analyses of nitrogen isotopes, physical and chemical properties, respectively. The profile of borehole A drilled in the vegetable growth plot only applied animal wastes had lower δ¹⁵N values of mean +7.5 ‰ in the upper vadose zone, but higher values of mean +10.9 ‰ in the lower vadose zone. δ¹⁵N values in each part varied little with depth, indicating no or little denitrification occurred in the deep vadose zone below the soil zone. The profile of borehole B drilled in the wastewater-irrigated farmland had low δ¹⁵N values of mean +5.7 ‰ below the soil zone and little variations of δ¹⁵N values with depth, indicating no or little denitrification occurred in the deep vadose zone below the soil zone. This was also verified by consistent variations of NO₃ ^? and SO₄ ^2? contents with Cl^? contents. Our results suggested most of leachable nitrate from the soil zone was hardly subjected to biological attenuation into groundwater.     

Local distribution of oxygen isotopes and fluid exchange during genesis of the corundum-bearing rocks of Khitostrov Island

New data are presented on the distribution of oxygen isotopes and conditions of the local isotope equilibrium in high-Al rocks rocks of Khitostrov Island showing abnormally low δ¹⁸O values (below–25‰). The temperatures of isotope equilibrium are within 400–475°C. The minimum δ¹⁸O values have been registered in the in plagioclase, whereas the same phases in kyanite-bearing rocks lacking corundum demonstrate δ¹⁸O values usually 3–5‰ higher. The fluid δ¹⁸O value varies from–22 to–16‰ at 475 ± 15°C, from–18 to–23‰ at 425 ± 25°C, and from–17 to–22‰ at 380 ± 15°C. The results obtained do not require abnormal depletion of δ¹⁸O values owing to the infiltration of an external fluid under the Svecofennian transformations. The association of corundum-bearing rocks with the basic intrusions, the presence of zircon cores of older ages compared to these rocks, and the peculiarities of rock chemistry may be ascribed to the fact that lower crustal layers of ancient rocks depleted in δ¹⁸O before metamorphism were captured by basite melts.     

Protomylonite evolution potentially revealed by the 3D depiction and fractal analysis of chemical data from a feldspar

Tourmalinization associated with peraluminous granitic intrusions in metapelitic host-rocks has been widely recorded in the Iberian Peninsula, given the importance of tourmaline as a tracer of granite magma evolution and potential indicator of Sn-W mineralizations. In the Penamacor-Monsanto granite pluton (Central Eastern Portugal, Central Iberian Zone), tourmaline occurs: (1) as accessory phase in two-mica granitic rocks, muscovite-granites and aplites, (2) in quartz (±mica)-tourmaline rocks (tourmalinites) in several exocontact locations, and (3) as a rare detrital phase in contact zone hornfels and metapelitic host-rocks. Electron microprobe and stable isotope (δ¹⁸O, δD, δ¹¹B) data provide clear distinctions between tourmaline populations from these different settings: (a) schorl–oxyschorl tourmalines from granitic rocks have variable foititic component (^X□ = 17–57 %) and Mg/(Mg + Fe) ratios (0.19–0.50 in two-mica granitic rocks, and 0.05–0.19 in the more differentiated muscovite-granite and aplites); granitic tourmalines have constant δ¹⁸O values (12.1 ± 0.1 ‰), with wider-ranging δD (?78.2 ± 4.7 ‰) and δ¹¹B (?10.7 to ?9.0 ‰) values; (b) vein/breccia oxyschorl [Mg/(Mg + Fe) = 0.31–0.44] results from late, B- and Fe-enriched magma-derived fluids and is characterized by δ¹⁸O = 12.4 ‰, δD = ?29.5 ‰, and δ¹¹B = ?9.3 ‰, while replacement tourmalines have more dravitic compositions [Mg/(Mg + Fe) = 0.26–0.64], close to that of detrital tourmaline in the surrounding metapelitic rocks, and yield relatively constant δ¹⁸O values (13.1–13.3 ‰), though wider-ranging δD (?58.5 to ?36.5 ‰) and δ¹¹B (?10.2 to ?8.8 ‰) values; and (c) detrital tourmaline in contact rocks and regional host metasediments is mainly dravite [Mg/(Mg + Fe) = 0.35–0.78] and oxydravite [Mg/(Mg + Fe) = 0.51–0.58], respectively. Boron contents of the granitic rocks are low (<650 ppm) compared to the minimum B contents normally required for tourmaline saturation in granitic melts, implying loss of B and other volatiles to the surrounding host-rocks during the late-magmatic stages. This process was responsible for tourmalinization at the exocontact of the Penamacor-Monsanto pluton, either as direct tourmaline precipitation in cavities and fractures crossing the pluton margin (vein/breccia tourmalinites), or as replacement of mafic minerals (chlorite or biotite) in the host-rocks (replacement tourmalinites) along the exocontact of the granite. Thermometry based on ¹⁸O equilibrium fractionation between tourmaline and fluid indicates that a late, B-enriched magmatic aqueous fluid (av. δ¹⁸O ~12.1 ‰, at ~600 °C) precipitated the vein/breccia tourmaline (δ¹⁸O ~12.4 ‰) at ~500–550 °C, and later interacted with the cooler surrounding host-rocks to produce tourmaline at lower temperatures (400–450 °C), and an average δ¹⁸O ~13.2 ‰, closer to the values for the host-rock. Although B-metasomatism associated with some granitic plutons in the Iberian Peninsula seems to be relatively confined in space, extending integrated studies such as this to a larger number of granitic plutons may afford us a better understanding of Variscan magmatism and related mineralizations.     

Seasonal variability of oxygen and hydrogen isotopes in a wetland system of the Yunnan-Guizhou Plateau,southwest China: a quantitative assessment of groundwater inflow fluxes

The Caohai Wetland serves as an important ecosystem on the Yunnan–Guizhou Plateau and as a nationally important nature reserve for migratory birds in China. In this study, surface water, groundwater and wetland water were collected for the measurement of environmental isotopes to reveal the seasonal variability of oxygen and hydrogen isotopes (δ¹⁸O, δD), sources of water, and groundwater inflow fluxes. Results showed that surface water and groundwater are of meteoric origin. The isotopes in samples of wetland water were well mixed vertically in seasons of both high-flow (September) and low-flow (April); however, marked seasonal and spatial variations were observed. During the high-flow season, the isotopic composition in surface wetland water varied from ?97.13 to ?41.73‰ for δD and from ?13.17 to ?4.70‰ for δ¹⁸O. The composition of stable isotopes in the eastern region of this wetland was lower than in the western region. These may have been influenced by uneven evaporation caused by the distribution of aquatic vegetation. During the low-flow season, δD and δ¹⁸O in the more open water with dead aquatic vegetation ranged from ?37.11 to ?11.77‰, and from ?4.25 to ?0.08‰, respectively. This may result from high evaporation rates in this season with the lowest atmospheric humidity. Groundwater fluxes were calculated by mass transfer and isotope mass balance approaches, suggesting that the water sources of the Caohai Wetland were mainly from groundwater in the high-flow season, while the groundwater has a smaller contribution to wetland water during the low-flow season.     

Stable isotopes (2H, 18O and 13C) in groundwaters from the northwestern portion of the Guarani Aquifer System (Brazil)

The groundwater flow pattern of the western part of the Guarani Aquifer System (GAS), Brazil, is characterized by three regional recharge areas in the north, and a potentiometric divide in the south, which trends north–south approximately. Groundwater flow is radial from these regional recharge areas toward the center of Paraná Sedimentary Basin and toward the western outcrop areas at the border of the Pantanal Matogrossense, because of the potentiometric divide. The isotopic composition of GAS groundwater leads to understanding the paleoclimatic conditions in the regional recharge areas. The δ¹⁸O and δ²H isotopic ratios of GAS groundwaters vary, respectively, from –9.1 to –4.8‰ V-SMOW and –58.4 to –21.7‰ V-SMOW. In the recharge zones, enriched δ¹⁸O values are observed, while in the confined zone lighter δ¹⁸O values are observed. These suggest that climatic conditions were 10°C cooler than the present during the recharge of these waters. The δ¹³C ratios in groundwater of GAS, in the study area, vary from –19.5 to –6.5‰ VPDB, increasing along the regional flow lines toward the confined zone. This variation is related to dissolution of carbonate cement in the sandstones.     

Hydrogen and oxygen isotopic compositions of sedimentary kaolin deposits,Egypt: Paleoclimatic implications

The clay fractions of sedimentary kaolin deposits representing different ages (Carboniferous and Cretaceous), types (pisolitic flint and plastic), and localities (Sinai and Aswan) from Egypt were analyzed for their H and O isotopic compositions to examine the paleoclimate conditions during their formation. The δD values of the Carboniferous deposits in Sinai range between −67‰ and −88‰, while the values for the Cretaceous deposits in Sinai range between −59‰ and −75‰. The δ¹⁸O values of the Carboniferous deposits range from 17.9‰ to 19.4‰ and the values for the Cretaceous deposits range between 19.2‰ and 20.4‰. The relatively low δD and δ¹⁸O values of the Carboniferous deposit at the Abu Natash area (−67‰ and 17.9‰, respectively) compared to other Carboniferous deposits (averages of −83.3‰, and 18.8‰ for δD and δ¹⁸O, respectively) could be due to isotopic exchange between this deposit and the adjacent dolomite and/or the enclosed hydrothermally-formed Mn ores of the Carboniferous Um Bogma Formation. The δD and δ¹⁸O values of the Cretaceous pisolitic flint kaolin deposit from Aswan (averages of −65‰ and 20.3‰, respectively) and plastic kaolin from the same area (averages of −66‰ and 19.5‰, respectively) are almost identical. The differences in the δ¹⁸O values between the clay fractions of the pisolitic flint kaolin (20.3‰) and the previously analyzed bulk kaolin of the same deposit (average of 17.5‰) suggest a significant effect of non-clay minerals on the isotopic compositions of the kaolin deposits.The H and O isotopic compositions plot close to the kaolinite line that marks the isotopic composition of kaolinite in equilibrium with meteoric water at 20 °C. This indicates that the kaolinite from both the Carboniferous and Cretaceous deposits in Egypt formed by meteoric water weathering of the source rock(s). The δD and δ¹⁸O values also suggest that kaolinite of these deposits formed under warm-temperate to tropical conditions. The slight deviations of some samples from the kaolinite line suggest post-depositional modifications of the isotopic compositions of studied deposits probably due to the interaction between earlier-formed kaolinite and downward percolating meteoric water.The δD and δ¹⁸O values of the Cretaceous and Carboniferous deposits from all localities suggest that both deposits formed under similar climatic conditions due to the location of Egypt at almost the same distance from the equator either to the south during the Carboniferous or to the north during the Cretaceous.     

Fluid regime and origin of gold-bearing rodingites from the Karabash alpine-type ultrabasic massif,Southern Ural

The rodingites of the Karabash Massif are distinguished by the presence of native cupriferous gold. This zonal hydrothermal-metasomatic complex was formed in three stages. The inner zone of rodingite proper is made up of chlorite-andradite-diopside rocks of stage 1, which are cut by diopside veinlets of stage 2 and calcite veinlets of stage 3. The intermediate zone consists of chloritolites, which give way to the antigorite and chrysotile-lizardite serpentinites of the outer zone. Thermometric and cryometric studies and gas chromatography showed that the gold-bearing rodingites of stages 1 and 2 were formed at t = 420–470°C, P = 2–3 kbar, and \(X_{CO_2 } \) = 0.001–0.02, i.e., under conditions typical of rodingite formation. The final stage was accompanied by a decrease in P-T parameters (0.5–1.0 kbar and 230–310°C) and an increase in \(X_{CO_2 } \) up to 0.04. The rodingite-forming fluid was extremely rich in water (\(X_{H_2 O} \) = 0.942–0.981) and contained hydrogen as the major gas component (\(X_{H_2 } \) = 0.012–0.023); its composition was essentially chloride-magnesium with minor amounts of CaCl₂ and FeCl₂ and a low salinity of 2.6–8.0 wt % NaCl equiv. The rodingite minerals showed the following isotopic characteristics (‰): δ¹⁸O from 5.5 to 6.6 and δD from 42.8 to ?44.3 for chlorite, δ¹⁸0 from 2.0 to 3.8 for andradite, δ¹⁸O from 6.0 to 6.6 for diopside, and δ¹⁸O from 10.6 to 11.4 and δ¹³C from 0.1 to ?1.8 for calcite. The chloritolite is characterized by δ¹⁸O from 5.9 to 6.6 and δD from ?49.8 to ?64.4; the antigorite serpentinite shows δ¹⁸O=6.5 and δD=?65.2; and the antigoritized chrysotile-lizardite serpentinite shows δ¹⁸O from 6.8 to 6.9 and δD from ?127 to ?128. The calculated isotopic composition of fluid in equilibrium with various rocks suggested its metamorphic origin. It was formed from the water released during dehydration of oceanic serpentinites, from the components of ultrabasic and basic magmatic rocks, and, at the final stage, from marine carbon.     

The oxygen and carbon isotope composition of Carboniferous fossil components: sea-water effects

The aragonitic molluscs and lime-mud of the Pennsylvanian Buckhorn asphalt (Deese Group) of southern Oklahoma precipitated calcium carbonate in oxygen and carbon isotopic equilibrium with ambient sea-water. In addition, δ¹⁸O values indicate that the pelecypods precipitated their shells during the warmer months of the year. The coiled nautiloids probably precipitated their shells in the warm surface water and throughout the year. For the orthocone nautiloids, the δ¹⁸O values suggest that they precipitated their shells in deeper/cooler water. The low-Mg calcite brachiopods of the Mississippian Lake Valley Formation of New Mexico precipitated shells in oxygen and carbon isotopic equilibrium with ambient sea-water. The δ¹⁸O and δ¹³C values of the Buckhorn and Lake Valley faunas, in conjunction with other published results, suggest that Carboniferous sea-water was, on a average, depleted in δ¹⁸O by 1·5 ± 2‰, PDB, relative to Recent sea-water. However, the δ¹³C value of +2.6 ± 2‰, PDB, for average Carboniferous sea-water is similar to that of Recent ocean water. Early diagenetic alteration of metastable carbonates probably occurs in a meteoric-sea-water mixing zone. In this zone the oxygen and carbon isotopic compositions of these components are increased by about 2-4‰, PDB over their marine composition.     

Mineral compositions and fluid evolution of the Tonglushan skarn Cu–Fe deposit,SE Hubei,east-central China

The Tonglushan Cu–Fe deposit (1.12 Mt at 1.61% Cu, 5.68 Mt at 41% Fe) is located in the westernmost district of the Middle–Lower Yangtze River metallogenic belt. As a typical polymetal skarn metallogenic region, it consists of 13 skarn orebodies, mainly hosted in the contact zone between the Tonglushan quartz-diorite pluton (140 Ma) and Lower Triassic marine carbonate rocks of the Daye Formation. Four stages of mineralization and alterations can be identified: i.e. prograde skarn formation, retrograde hydrothermal alteration, quartz-sulphide followed by carbonate vein formation. Electron microprobe analysis (EMPA) indicates garnets vary from grossular (Ad_20.2–41.6Gr_49.7–74.1) to pure andradite (Ad_47.4–70.7Gr_23.9–45.9) in composition, and pyroxenes are represented by diopsides. Fluid inclusions identify three major types of fluids involved during formation of the deposit within the H₂O–NaCl system, i.e. liquid-rich inclusions (Type I), halite-bearing inclusions (Type II), and vapour-rich inclusions (Type III). Measurements of fluid inclusions reveal that the prograde skarn minerals formed at high temperatures (>550°C) in equilibrium with high-saline fluids (>66.57 wt.% NaCl equivalent). Oxygen and hydrogen stable isotopes of fluid inclusions from garnets and pyroxenes indicate that ore-formation fluids are mainly of magmatic-hydrothermal origin (δ¹⁸O = 6.68‰ to 9.67‰, δD = –67‰ to –92‰), whereas some meteoric water was incorporated into fluids of the retrograde alteration stage judging from compositions of epidote (δ¹⁸O = 2.26‰ to 3.74‰, δD= –31‰ to –73‰). Continuing depressurization and cooling to 405–567°C may have resulted in both a decrease in salinity (to 48.43–55.36 wt.% NaCl equivalent) and the deposition of abundant magnetite. During the quartz-sulphide stage, boiling produced sulphide assemblage precipitated from primary magmatic-hydrothermal fluids (δ¹⁸O = 4.98‰, δD = –66‰, δ³⁴S values of sulphides: 0.71–3.8‰) with an extensive range of salinities (4.96–50.75 wt.% NaCl equivalent), temperatures (240–350°C), and pressures (11.6–22.2 MPa). Carbonate veins formed at relatively low temperatures (174–284°C) from fluids of low salinity (1.57–4.03 wt.% NaCl equivalent), possibly reflecting the mixing of early magmatic fluids with abundant meteoric water. Boiling and fluid mixing played important roles for Cu precipitation in the Tonglushan deposit.     

Hydrogen and oxygen isotopic compositions of meteoric waters in the eastern part of China

42 meteoric water samples were analyzed for their δ¹⁸O and δD values. It can be seen that both δ¹⁸O and δD values vary synchronously with latitude along our investigation-tour route from Guangxi (22.7 NL°) to Heilongjiang (48.8 NL°). Their relationship is presented as follows: δ¹⁸O(‰)=?0.24 NL° + 0.04 and δD(‰)=?1.84 NL° + 6.88. The relationship between δ¹⁸O, δD and altitude in the southeastern part of the Guizhou Plateau is: $$ - \delta ^{1{\rm B}} O(\% o) = 0.003H(m) + 5.24 and - \delta D(\% o) = 0.0134H(m) + 39.8.$$      

The Laqiong Sb-Au deposit: Implications for polymetallic mineral systems in the Tethys-Himalayan zone of southern Tibet,China

The Himalayan mineral field includes over 50 quartz-vein type Sb-Au deposits, and placer Au deposits. The poorly documented Laqiong deposit is a typical example of quartz-vein type Sb-Au mineralisation in Tethys Himalayan sequence. The orebody are controlled by shallow north-dipping normal faults and north–south trending faults. Magmatic zircons extracted from muscovitic leucocratic granite from the southern part of the Laqiong mine area yield a Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry U-Pb age of 14 ± 1 Ma (n = 12, MSWD = 0.9) that is similar to the ⁴⁰Ar/³⁹Ar age of ca. 14 Ma from hydrothermal sericite in auriferous sulphide-quartz veins. The ε_Hf(t) values for the magmatic zircon rims range from −5.4 to −1.9, corresponding to two-stage Hf model ages of 1403–1214 Ma. Quartz from the mineralised veins has δ¹⁸O_H2O-SMOW values varying from +4.97 to +9.59‰ and δD_H2O-SMOW values ranging from −119.7 to −108.1‰. The δ¹³C_V-PDB values for calcite from the ore Stage III range from −6.9 to −5.3‰, and calcite from Stage IV are −3.5 to −1.7‰. The δ¹⁸O_V-SMOW values for calcite from Stage III are +20.3 to +20.6‰ and for Stage IV are −6.3 to −4.9‰. The stibnite and pyrite samples have ²⁰⁸Pb/²⁰⁴Pb ratios of 38.158 to 39.02, ²⁰⁷Pb/²⁰⁴Pb ratios of 15.554 to 15.698, and ²⁰⁶Pb/²⁰⁴Pb ratios of 17.819 to 18.681, and bulk and in-situ δ³⁴S_V-CDT values for stibnite, arsenopyrite and pyrite range from −1.1 to +2.3‰. The calcite from the orebodies are enriched in MREE and depleted in LREE and HREE. Fieldwork, petrological, and geochemical data collected during our study leads to the following salient findings: the mineralising fluid is a mix of magmatic and meteoric fluids; and the deposit is closely related to the emplacement of Miocene granites originating from a thickened continental crust.     

Fluid Inclusions and Hydrogen,Oxygen, Sulfur Isotopes of Nuri Cu‐W‐Mo Deposit in the Southern Gangdese,Tibet

The Nuri Cu‐W‐Mo deposit is located in the southern subzone of the Cenozoic Gangdese Cu‐Mo metallogenic belt. The intrusive rocks exposed in the Nuri ore district consist of quartz diorite, granodiorite, monzogranite, granite porphyry, quartz diorite porphyrite and granodiorite porphyry, all of which intrude in the Cretaceous strata of the Bima Group. Owing to the intense metasomatism and hydrothermal alteration, carbonate rocks of the Bima Group form stratiform skarn and hornfels. The mineralization at the Nuri deposit is dominated by skarn, quartz vein and porphyry type. Ore minerals are chalcopyrite, pyrite, molybdenite, scheelite, bornite and tetrahedrite, etc. The oxidized orebodies contain malachite and covellite on the surface. The mineralization of the Nuri deposit is divided into skarn stage, retrograde stage, oxide stage, quartz‐polymetallic sulfide stage and quartz‐carbonate stage. Detailed petrographic observation on the fluid inclusions in garnet, scheelite and quartz from the different stages shows that there are four types of primary fluid inclusions: two‐phase aqueous inclusions, daughter mineral‐bearing multiphase inclusions, CO₂‐rich inclusions and single‐phase inclusions. The homogenization temperature of the fluid inclusions are 280°C–386°C (skarn stage), 200°C–340°C (oxide stage), 140°C–375°C (quartz‐polymetallic sulfide stage) and 160°C–280°C (quartz‐carbonate stage), showing a temperature decreasing trend from the skarn stage to the quartz‐carbonate stage. The salinity of the corresponding stages are 2.9%–49.7 wt% (NaCl) equiv., 2.1%–7.2 wt% (NaCl) equiv._, 2.6%–55.8 wt% (NaCl) equiv. and 1.2%–15.3 wt% (NaCl) equiv., respectively. The analyses of CO₂‐rich inclusions suggest that the ore‐forming pressures are 22.1 M Pa–50.4 M Pa, corresponding to the depth of 0.9 km–2.2 km. The Laser Raman spectrum of the inclusions shows the fluid compositions are dominated in H₂O, with some CO₂ and very little CH₄, N₂, etc. δD values of garnet are between ?114.4‰ and ?108.7‰ and δ¹⁸O_H2O between 5.9‰ and 6.7‰; δD of scheelite range from ?103.2‰ to ?101.29‰ and δ¹⁸O_H2O values between 2.17‰ and 4.09‰; δD of quartz between ?110.2‰ and ?92.5‰ and δ¹⁸O_H2O between ?3.5‰ and 4.3‰. The results indicate that the fluid came from a deep magmatic hydrothermal system, and the proportion of meteoric water increased during the migration of original fluid. The δ³⁴S values of sulfides, concentrated in a rage between ?0.32‰ to 2.5‰, show that the sulfur has a homogeneous source with characteristics of magmatic sulfur. The characters of fluid inclusions, combined with hydrogen‐oxygen and sulfur isotopes data, show that the ore‐forming fluids of the Nuri deposit formed by a relatively high temperature, high salinity fluid originated from magma, which mixed with low temperature, low salinity meteoric water during the evolution. The fluid flow through wall carbonate rocks resulted in the formation of layered skarn and generated CO₂ or other gases. During the reaction, the ore‐forming fluid boiled and produced fractures when the pressure exceeded the overburden pressure. Themeteoric water mixed with the ore‐forming fluid along the fractures. The boiling changed the pressure and temperature, oxygen fugacity, physical and chemical conditions of the whole mineralization system. The escape of CO₂ from the fluid by boiling resulted in scheelite precipitation. The fluid mixing and boiling reduced the solubility of metal sulfides and led the precipitation of chalcopyrite, molybdenite, pyrite and other sulfide.     

Mid- to lower-crustal architecture of the northern Lachlan and southern Thomson orogens: evidence from O–Hf isotopes

Abstract

The nature of the substrate below the northern Lachlan Orogen and the southern Thomson Orogen is poorly understood. We investigate the nature of the mid- to lower-crust using O and Lu–Hf isotope analyses of zircons from magmatic rocks that intrude these regions, and focus on the 440–410 Ma time window to minimise temporal effects while focussing on spatial differences. Over the entire region, weighted mean δ¹⁸O values range from 5.5 to 9.8‰ (relative to VSMOW, Vienna Standard Mean Oceanic Water), and weighted mean ?Hf_t range from ?8.8 to +8.5. In the northern Lachlan Orogen and much of the southern Thomson Orogen, magmatic rocks with unradiogenic ?Hf_t (～?7 to ?4) and elevated δ¹⁸O values (～9 to 10‰) reflect a supracrustal source component that may be common to both orogens. Magmatic rocks intruding the Warratta Group in the western part of the Thomson Orogen also have unradiogenic ?Hf_t (～?9 to ?6) but more subdued δ¹⁸O values (～7‰), indicating a distinct supracrustal source component in this region. Some regions record radiogenic ?Hf and mantle-like δ¹⁸O values, indicative of either a contribution from arc-derived rocks or a direct mantle input. In the northeast Lachlan Orogen Hermidale Terrane, magmatic rocks record mixing of the supracrustal source component with input from a infracrustal or mantle source component (?Hf_t as high as +8.5, δ¹⁸O values as low as 5.5‰), possibly of Macquarie Arc affinity. Samples in the west-southwestern Thomson Orogen also record some evidence of radiogenic input (?Hf_t as high as ?0.5, δ¹⁸O values as low as 6.4‰), possibly from the Mount Wright Arc of the Koonenberry Belt. Overall, our results demonstrate a strong spatial control on isotopic compositions. We find no isotopic differences between the bulk of the Lachlan Orogen and the bulk of the Thomson Orogen, and some indication of similarities between the two.