Holocene climate variability in Sicily from a discontinuous stalagmite record and the Mesolithic to Neolithic transition

Fabric and stable isotopic composition of a Holocene stalagmite (CR1) from a cave in northern Sicily record changes in paleorainfall in the early Holocene. High δ¹³C stable isotope values in the calcite deposited from ca. 8500 to ca. 7500 yr ago are interpreted as reflecting periods of high rainfall. The wet phase was interrupted by two periods of multi-century duration characterized by relatively cool and dry winters centered at ca. 8200 and ca. 7500 yr ago, highlighted by low δ¹³C and δ¹⁸O values. A high variability of δ¹³C values is recorded from ca. 7500 to ca. 6500 yr ago and indicates that the transition from a pluvial early Holocene to the present-day climate conditions was punctuated by decadal-scale periods of relatively dry winters. In northern Sicily, the traditional elements of the Neolithic appear at ca. 7700 yr ago. It is possible that changes in rainfall influenced the passage from hunter-gathering to farming and sheep-herding economies.     

Geochemistry and occurrence of inorganic gas accumulations in Chinese sedimentary basins

Inorganic gases are commonly seen in eastern China and occasionally in southern China from the shallow water columns above hot and cold springs. The gases contain 68% to nearly 100% CO₂, with δ¹³C_CO2 and δ¹³C₁ values in the range of −1.18‰ to −6.00‰ and −19.48‰ to −24.94‰, respectively. All of the 34 large inorganic CO₂ and one inorganic methane accumulations discovered in China are distributed in eastern parts of the country, from both onshore and continental shelf basins. No commercial inorganic gas accumulation has been found in central and western China. This is a review of the occurrence and geochemical characteristics of inorganic gas accumulations in Chinese sedimentary basins. A detailed study of gas samples collected from four representative inorganic CO₂ pools and one possible inorganic methane pool indicates that inorganic alkane gases typically show δ¹³C₁ values greater than −10‰ versus PDB (mostly −30‰), with a positive stable carbon isotope sequence of δ¹³C₁ < δ ¹³C₂ < δ¹³C₃ < δ ¹³C₄. In contrast, the δ¹³C₁ values of biogenic alkane gases are lighter than −30‰, with a negative isotope sequence (i.e. δ¹³C₁ > δ¹³C₂ > δ ¹³C₃ > δ¹³C₄). Inorganic gases also tend to show less negative δ¹³C_CO2 values (−10‰) than biogenic gases (<−10‰).     

Moisture source in the Hyblean Mountains region (south-eastern Sicily, Italy): Evidence from stable isotopes signature

Here the authors present results of an isotope study on precipitation collected during a 2-a period from a rain-gauge network consisting of 6 stations located at different elevations in the Hyblean Mountains (HM) region, in south-eastern Sicily. The slope of the local meteoric water line (δD = 6.50 δ¹⁸O + 9.87) obtained for the region suggests that precipitation is affected by evaporation during rainfall events. The main variations in rainwater isotope composition are due to seasonal effects and elevation. An average ²H excess value of +21.2‰ was found for precipitation events less affected by evaporation (i.e. when the rainfall was >65 mm/month). The spatial distribution of O isotope composition of precipitation shows a negative gradient from east and south to the inner areas. The depositional rate of Cl, used as a tracer of the origin of air masses, is highest at the coastal rain-gauges (SR and MRG stations) and lowest on the northern flank of the HM region (SC station). Based on these findings, a model is proposed for the origin of precipitation in the HM region, which assumes that a Mediterranean-derived component is the main source of moisture in the studied area. D/H and ¹⁸O/¹⁶O ratios of inferred meteoric recharge waters were also compared with the isotope composition of waters collected from the main local springs and wells. The best linear fit of the δ¹⁸O vs δD relationship for Hyblean groundwater is δD = 4.85 δ¹⁸O–2.01. The enrichment of heavy isotopes in Hyblean groundwater is probably due to evaporation occurring after precipitation events or to a recharging contribution from surface waters (lakes or rivers) enriched in heavy isotopes.     

Climatic variability during the last 90 ka of the southern and northern Levantine Basin as evident from marine records and speleothems

The influence of the northern Atlantic and tropical monsoonal systems, as recorded by the River Nile, on the climate variability of the southeastern Mediterranean was studied in two cores taken by the R/V Marion Dufresne: one core taken SE of Cyprus representing the northern Levantine Basin (core 9501, 980 m water depth) and the other located ˜380 km further south, represents the southeastern Levantine Basin in an area influenced by the River Nile plume (core 9509, 884 m water depth). The study was performed at relatively high resolution using several proxies: δ¹⁸O of Globigerinoides ruber, sediment characteristics and index colour parameters in core sections representing the last 86 ka. A low-resolution alkenone sea surface temperature record was also measured. The time frame in both cores was mostly constrained by ‘wiggle’ matching with the nearby well-dated δ¹⁸O and δ¹³C record of the Soreq Cave, which is mainly influenced by the eastern Mediterranean water vapor. The sedimentary record of the southern core is strongly influenced by the River Nile contribution throughout the last 86 ka, as evidenced by the higher sedimentation rates compared with the northern core (20 cm/ka vs. 5 cm/ka), continuously darker sediment colour, and higher TOC values (0.6–0.9 vs. 0.25 wt% not including sapropels). During sapropels S1 and S3, present in both cores, the influence of the River Nile became more widespread, reaching as far as Cyprus. Yet, the influence of the River Nile remained stronger in the south, as evident by the higher TOC values in the southern core throughout the entire 90 ka period and the longer duration of S1 in the southern core. An anomalous low δ¹⁸O interval that is not recorded in western Mediterranean occurred between 58 and 49 ka in the Levantine Basin and is more developed in the northern core. This period correlates with D-O interstadial 14 and maximum northern hemisphere insolation during the lastglacial cycle, suggesting that the warming mainly impacted the northern Levant.The Eastern Mediterranean Sea and land area was considerably warmer than the western Mediterranean throughout the LGM – Holocene transition, and the δ¹⁸O_{G. ruber} drop of 4.5‰ is significantly greater than the 3‰ shift found for the western Mediterranean δ¹⁸O_{G. bulloides}, both differences reflecting an increased continental effect from the western to eastern Mediterranean. Comparison between the marine and the land δ¹⁸O records suggests that the origin of rain over the land is composed of mixed signal from the southern and northern Levantine Basin. The study of Δδ¹⁸O_sea–land variations demonstrates that various factors have influenced the sea–land relationship during the last 90 ka. The ‘amount effect’ has an important influence on rainfall δ¹⁸O during interglacial periods (particularly sapropel periods), whereas during glacial periods, increased land distances and elevation differences arising from decrease in sea level may have brought about decrease in δ¹⁸O of rainfall due to Rayleigh distillation processes. These influences were superimposed on those of sea surface water δ¹⁸O changes brought about by continental ice melting, and the strong effects felt in the southern Levantine Basin of the high River Nile input during periods of enhanced monsoonal activity.     

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.     

Middle Pleistocene climate and habitat change at Zhoukoudian, China, from the carbon and oxygen isotopic record from herbivore tooth enamel

The Pleistocene deposits at Zhoukoudian, often referred to as the “Peking Man” site, contain dental remains from a diverse group of herbivores, including Equus sanmeniensis, Cervus elaphus, Cervus nippon, Megaloceros pachyosteus, Sus lydekkeri, and Dicerorhinus choukoutienensis. The carbon and oxygen isotopic compositions of structural carbonate within the enamel of these teeth are used to reconstruct the paleodiet and paleoenvironment of the mammals. The δ¹³C values of enamel from Zhoukoudian range from −2.3‰ to −13.0‰, indicating that these mammals consumed between 25% and 100% C₃ plants. The presence of significant amounts of C₄ plants in the diets of some herbivore species indicates that at the onset of the Middle Pleistocene local habitats included mixed C₃/C₄ vegetation. By approximately 470,000 yr ago, C₃ plants dominated the diets of herbivores studied, suggesting that the abundance of C₄ flora had decreased in the area. For all deer analyzed in this study, the values of δ¹³C and δ¹⁸O decrease substantially from about 720,000 to 470,000 yr ago. This trend may be due to a strengthening of the winter monsoon during the Middle Pleistocene.     

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.     

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.     

Global trench migration velocities and slab migration induced upper mantle volume fluxes: Constraints to find an Earth reference frame based on minimizing viscous dissipation

Since the advent of plate tectonics different global reference frames have been used to describe the motion of plates and trenches. The difference in plate motion and trench migration between different reference frames can be substantial (up to 4 cm/yr). This study presents an overview of trench migration velocities for all the mature and incipient subduction zones on Earth as calculated in eight different global reference frames. Calculations show that, irrespective of the reference frame: (1) trench retreat always dominates over trench advance, with 62–78% of the 244 trench segments retreating; (2) the mean and median trench velocity are always positive (retreating) and within the range 1.3–1.5 cm/yr and 0.9–1.3 cm/yr, respectively; (3) rapid trench retreat is only observed close to lateral slab edges (< 1500 km); and (4) trench retreat is always slow far from slab edges (> 2000 km). These calculations are predicted by geodynamic models with a varying slab width, in which plate motion, trench motion and mantle flow result from subduction of dense slabs, suggesting that trench motion is indeed primarily driven by slab buoyancy forces and that proximity to a lateral slab edge exerts a dominant control on the trench migration velocity. Despite these four general conclusions, significant differences in velocities between such reference frames remain. It is therefore important to determine which reference frame most likely describes the true absolute velocities to get an understanding of the forces driving plate tectonics and mantle convection. It is here proposed that, based on fluid dynamic considerations and predictions from geodynamic modelling, the best candidate is the one, which optimises the number of trench segments that retreat, minimizes the trench–perpendicular trench migration velocity (v_T) in the centre of wide (> 4000 km) subduction zones, maximizes the number of retreating trench segments located within 2000 km of the closest lateral slab edge, minimizes the average of the absolute of the trench–perpendicular trench migration velocity (|v_T|) for all subduction zones on Earth, and minimizes the global upper mantle toroidal volume flux (_To) that results from trench migration and associated lateral slab migration (i.e. slab rollback or slab roll-forward). Calculations show that these conditions are best met in one particular Indo-Atlantic hotspot reference frame, where 75% of the subduction zones retreat, v_T in the centre of wide subduction zones ranges between − 3.5 and 1.8 cm/yr, 83% of the trench segments located within 2000 km of the closest lateral slab edge retreat, the average of |v_T| is 2.1 cm/yr, and _To = 456 km³/yr (lower limit) and 539 km³/yr (upper limit). Inclusion of all the incipient subduction zones on Earth results in slightly greater fluxes of 465 km³/yr (lower limit) and 569 km³/yr (upper limit). It is also found that this reference frame is close to minimizing the total sub-lithospheric upper mantle volume flux (_K) associated with motion of continental keels located below the major cratons. It is stressed, however, that _K is an order of magnitude smaller than _To, and thus of subordinate importance. In conclusion, the Indo-Atlantic hotspot reference frame appears preferable for calculating plate velocities and plate boundary velocities.     

Tourmalinites from the Eastern Sierras Pampeanas, Argentina

In the eastern Sierras Pampeanas, Central Argentina, tourmalinites and coticules are found in close association with stratabound scheelite deposits in metamorphic terranes. In Sierra Grande (Agua de Ramón and Ambul districts) and Sierra de Altautina, tourmalinites are associated with stratabound scheelite deposits related to orthoamphibolites. In the Pampa del Tamboreo area, tourmalinites are located in biotite schists stratigraphically related to acid to intermediate metavolcanic rocks and scheelite-bearing quartzites.The mineral chemistry and boron isotopic compositions of tourmalinite-hosted and vein-hosted tourmalines are investigated. Overall, the tourmalines belong to the dravite-schorl series and are generally aluminous; Fe/(Fe+Mg) ranges from 0.33 to 0.85, Al/(Al+Fe+Mg) from 0.66 to 0.76 and the amount of X-site vacancy (0.12–0.48) indicates significant foitite components. Their boron isotopic compositions (δ¹¹B) are from −24.0‰ to−15.0‰.Similar mineral chemistries and boron isotopic values for tourmaline in tourmalinites related to stratabound scheelite mineralisation and in tungsten-bearing quartz veins suggest a common source for the boron and probably the tungsten. The field, chemical and isotopic relationships are consistent with tungsten and boron in quartz-vein deposits being remobilised from stratabound scheelite and tourmalinite, dominantly by liquid-state transfer associated with regional shear zones. Tungsten and boron in the original sedimentary sequence (now meta-exhalites) are ascribed to volcanogenic exhalations.     

Relative contributions of crust and mantle to the generation of the Tianshan Carboniferous rift-related basic lavas, northwestern China

The Tianshan Carboniferous–Permian rift-related volcanism in northwestern China represents a newly recognized large igneous province extending over at least 1.5 × 10⁶ km². The volcanic successions comprise thick piles of basaltic lavas and subordinate intermediate and silicic lavas and pyroclastics, and are interpreted to result from a mantle plume head with component of ε_Nd(t) ≈ +5, ⁸⁷Sr/⁸⁶Sr(t) ≈ 0.704 and La/Nb ≈ 0.9. On the basis of petrogeochemical data, the Carboniferous basic lavas can be generally incorporated into low-Ti/Y (LT, Ti/Y < 500) magma type that can be further divided into three subtypes: LT1, LT2 and LT3. The chemical evolution of the LT1, LT2 (in central Tianshan) and LT3 (in western Tianshan and Jungar) lavas is controlled by an olivine (ol) + clinopyroxene (cpx) fractionation, but gabbroic fractionation accounts for the chemical variation of the LT3 lavas from eastern Tianshan. Elemental and isotopic data suggest that the chemical variation of Tianshan Carboniferous basic lavas cannot be explained by crystallization from a common parental magma.The Sr–Nd isotopic variation of the crustally contaminated LT3 lavas is related to the nature of lithosphere through which the plume-derived melts have erupted. The involvement of an older (Precambrian) lithosphere led the LT3 lavas in western Tianshan to have lower to negative ε_Nd(t) (−1.2 to +6.1) and variable ⁸⁷Sr/⁸⁶Sr(t) (0.7036–0.7061), whereas the LT3 lavas from eastern Tianshan and Jungar are characterized by high ε_Nd(t) (+4.2 to +9.7) and low ⁸⁷Sr/⁸⁶Sr(t) (0.7035–0.7044), that are related to the contamination of upper crust containing early Paleozoic and Devonian arc-basin volcanic rocks and/or to a pre-Carboniferous subduction enrichment of the lithospheric mantle source region. The observed geochemical variations in the Tianshan data are consistent with an AFC process.The Tianshan Carboniferous rift-related volcanic rocks display a spatial petrogeochemical variation in which predominantly uncontaminated LT1 and less-contaminated LT2 tholeiitic lavas erupted in central Tianshan rift and predominantly the strongly contaminated LT3 tholeiites erupted in the circumjacent regions of the central Tianshan rift. The LT1 and LT2 lavas were generated by a higher degree (10–30%) of partial melting in the garnet stability field of the mantle plume compared to the LT3 lavas. The lower degree (<10%) of partial melting in the spinel–garnet transition zone of the mantle plume, as is characteristic of the LT3 lavas, may be the result of a relatively lower geotherm.     

Geology and geochemistry of the adjacent Changkeng gold and Fuwang silver deposits, Guangdong Province, South China

The Changkeng Au and Fuwang Ag deposits represent an economically significant and distinct member of the Au–Ag deposit association in China. The two deposits are immediately adjacent, but the Au and Ag orebodies separated from each other. Ores in the Au deposit, located at the upper stratigraphic section and in the southern parts of the orefield, contain low Ag contents (< 11 ppm); the Ag orebodies, in the lower stratigraphic section, are Au-poor (< 0.2 ppm). Changkeng is hosted in brecciated cherts and jasperoidal quartz and is characterized by disseminated ore minerals. Fuwang, hosted in the Lower Carboniferous Zimenqiao group bioclastic limestone, has vein and veinlet mineralization associated with alteration comprised of quartz, carbonate, sericite, and sulfides. Homogenization temperatures of fluid inclusions from quartz veinlets in the Changkeng and Fuwang deposits are in the range of 210 ± 80 °C and 230 ± 50 °C, respectively. Salinities of fluid inclusions from the two deposits range from 1.6 to 7.3 wt.% and 1.6 to 2.6 wt.% equiv. NaCl, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of the fluid inclusions from the Changkeng deposit range from − 80‰ to − 30‰, − 7.8‰ to − 3.0‰, − 16.6‰ to − 17.0‰ and 0.0100 to 0.0054 Ra, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of fluid inclusions from the Fuwang deposit range from − 59‰ to − 45‰, − 0.9‰ to 4.1‰, − 6.7‰ to − 0.6‰ and 0.5930 to 0.8357 Ra, respectively. The δD_H2O, δ¹⁸O_H2O, δ¹³C_CO2 and ³He/⁴He values of the fluid inclusions suggest the ore fluids of the Changkeng Au-ore come from the meteoric water and the ore fluids of the Fuwang Ag-ore are derived from mixing of magmatic water and meteoric water. The two deposits also show different Pb-isotopic signatures. The Changkeng deposit has Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb: 18.580 to 19.251, ²⁰⁷Pb/²⁰⁴Pb: 15.672 to 15.801, ²⁰⁸Pb/²⁰⁴Pb: 38.700 to 39.104) similar to those (²⁰⁶Pb/²⁰⁴Pb: 18.578 to 19.433, ²⁰⁷Pb/²⁰⁴Pb: 15.640 to 15.775, ²⁰⁸Pb/²⁰⁴Pb: 38.925 to 39.920) of its host rocks and different from those (²⁰⁶Pb/²⁰⁴Pb: 18.820 to 18.891, ²⁰⁷Pb/²⁰⁴Pb: 15.848 to 15.914, ²⁰⁸Pb/²⁰⁴Pb: 39.579 to 39.786) of the Fuwang deposit. The different signatures indicate different sources of ore-forming material. Rb–Sr isochron age (68 ± 6 Ma) and ⁴⁰Ar–³⁹Ar age (64.3 ± 0.1 Ma) of the ore-related quartz veins from the Ag deposit indicate that the Fuwang deposit formed during the Cenozoic Himalayan tectonomagmatic event. Crosscutting relationships suggests that Au-ore predates Ag-ore. The adjacent Changkeng and Fuwang deposits could, however, represent a single evolved hydrothermal system. The ore fluids initially deposited Au in the brecciated siliceous rocks, and then mixing with the magmatic water resulted in Ag deposition within fracture zones in the limestone. The deposits are alternatively the product of the superposition of two different geological events. Age evidence for the Fuwang deposit, together with the Xiqiaoshan Tertiary volcanic-hosted Ag deposit in the same area, indicates that the Pacific Coastal Volcanic Belt in the South China Fold Belt has greater potential for Himalayan precious metal mineralization than previous realized.     

Porphyry Cu–Au and associated polymetallic Fe–Cu–Au deposits in the Beiya Area, western Yunnan Province, south China

The Alkaline porphyries in the Beiya area are located east of the Jinshajiang suture, as part of a Cenozoic alkali-rich porphyry belt in western Yunnan. The main rock types include quartz-albite porphyry, quartz-K-feldspar porphyry and biotite–K-feldspar porphyry. These porphyries are characterised by high alkalinity [(K₂O + Na₂O)% > 10%], high silica (SiO₂% > 65%), high Sr (> 400 ppm) and ⁸⁷Sr/⁸⁶Sr (> 0.706)] ratio and were intruded at 65.5 Ma, between 25.5 to 32.5 Ma, and about 3.8 Ma, respectively. There are five main types of mineral deposits in the Beiya area: (1) porphyry Cu–Au deposits, (2) magmatic Fe–Au deposits, (3) sedimentary polymetallic deposits, (4) polymetallic skarn deposits, and (5) palaeoplacers associated with karsts. The porphyry Cu–Au and polymetallic skarn deposits are associated with quartz–albite porphyry bodies. The Fe–Au and polymetallic sedimentary deposits are part of an ore-forming system that produced considerable Au in the Beiya area, and are characterised by low concentrations of La, Ti, and Co, and high concentrations of Y, Yb, and Sc.The Cenozoic porphyries in western Yunnan display increased alkalinity away from the Triassic Jinshajiang suture. Distribution of both the porphyries and sedimentary deposits in the Beiya area are interpreted to be related to partial melting in a disjointed region between upper mantle lithosphere of the Yangtze Plate and Gondwana continent, and lie within a shear zone between buried Palaeo-Tethyan oceanic lithosphere and upper mantle lithosphere, caused by the subduction and collision of India and Asia.     

Graphite–sulfide deposits in Ronda and Beni Bousera peridotites (Spain and Morocco) and the origin of carbon in mantle-derived rocks

This paper describes unusual graphite–sulfide deposits in ultramafic rocks from the Serranía de Ronda (Spain) and Beni Bousera (Morocco). These deposits occur as veins, stockworks and irregular masses, ranging in size from some centimeters to a few meters in thickness. The primary mineral assemblage mainly consists of Fe–Ni–Cu sulfides (pyrrhotite, pentlandite, chalcopyrite and cubanite), graphite and chromite. Weathering occurs in some sulfide-poor deposits that consist of graphite (up to 90%), chromite and goethite. Texturally, graphite may occur as flakes or clusters of flakes and as rounded, nodule-like aggregates. Graphite is highly crystalline and shows light carbon isotopic signatures (δ¹³C≈− 15‰ to − 21‰). Occasionally, some nodule-like graphite aggregates display large isotopic zoning with heavier cubic forms (probably graphite pseudomorphs after diamond with δ¹³C up to − 3.3‰) coated by progressively lighter flakes outwards (δ¹³C up to − 15.2‰).Asthenospheric-derived melts originated the partial melting (and melt–rock reactions) of peridotites and pyroxenites generating residual melts from which the graphite–sulfide deposits were formed. These residual melts concentrated volatile components (mainly CO₂ and H₂O), as well as S, As, and chalcophile elements. Carbon was incorporated into the melts from the melt–rock reactions of graphite-bearing (formerly diamonds) garnet pyroxenites with infiltrated asthenospheric melts. Graphite-rich garnet pyroxenites formed through the UHP transformation of subducted kerogen-rich crustal material into the mantle. Thus, graphite in most of the studied occurrences has light (biogenic) carbon signatures. Locally, reaction of the light carbon in the melts with relicts of ¹³C-enriched graphitized diamonds (probably generated from hydrothermal calcite veins in the subducting oceanic crust) reacted with the partial melts to form isotopically zoned nodule-like graphite aggregates.     

The origin and evolution of mineralizing fluids in the Cretaceous Gyeongsang Basin, Southeastern Korea

Ferroalloy, base-metal and precious-metal deposits in or around the Gyeongsang Basin, which is located in the Cretaceous volcano-sedimentary terrain at the southeastern Korea, displays a genetic relationship with subvolcanic activities of Late Cretaceous to Tertiary age. Diverse mineralization, which occurs as vein, breccia-pipe, porphyry-style and skarn deposits, took place from 108 to 45 Ma that overlapped with polyphase episodes of igneous activity. Based on the mineralogy, host rock, fluid inclusion and stable isotope data of the deposits, the systematic variation of physicochemical conditions is thought to be due to their relative positions with respect to a magma source that is genetically related to a low to intermediate-sulfidation porphyry system. There appears to be a systematic decrease towards δ¹⁸O_H2O values from copper (-gold) and ferroalloy deposits through polymetallic to precious-metal ones. However, Cu (-Au) or Fe–Mo–W deposits are proximal to a magmatic source, whereas polymetallic or precious-metal deposits are more distal to transitional.     

Biostratigraphic and isotopic record of the Cenomanian–Turonian deposits in the Ohaba-Ponor section (SW Haţeg, Romania)

The middle Cenomanian–lower Turonian deposits of Ohaba-Ponor section (Southern Carpathians) were studied from biostratigraphic and isotopic points of view. Both the qualitative and semiquantitative nannofloral analyses, as well as the stable isotope (δ¹³C and δ¹⁸O) data support significant palaeoenvironmental changes in the investigated interval. Two δ¹³C positive excursions were recognized: (1) an excursion up to 1.8‰ (PDB) within the middle/late Cenomanian boundary; (2) an excursion up to 2.2‰ (PDB) in the Cenomanian/Turonian boundary interval. The oldest δ¹³C positive excursion recorded (placed within the Acanthoceras jukes-brownei/Eucalycoceras pentagonum Ammonite Zone boundary interval, and in the NC11 Calcareous Nannofossil Zone respectively) could be assigned to the middle Cenomanian Event II (MCEII). During the above-mentioned event, significant increase in abundance of Watznaueria barnesae, followed by successive blooms of Biscutum constans and Eprolithus floralis, were observed. The youngest δ¹³C positive excursion was identified in the Cenomanian/Turonian boundary interval (in the NC12 and lower part of the NC13 Calcareous Nannofossil Zones). Even the amplitude of this δ¹³C positive excursion is lower in the Ohaba-Ponor section, as generally reported, this may represent the regional record of the OAE2. The successive peaks of the nannofossils Biscutum constans, Zeugrhabdotus erectus and Eprolithus floralis indicate episodes of cooler surface water and high fertility, which preceded and lasted the Cenomanian/Turonian boundary event. Additionally, fluctuations of δ¹⁸O values between −2 and −6‰ suggest also cooler conditions within the Cenomanian/Turonian boundary interval.     

Α high-resolution late Holocene speleothem record from Kaite Cave, northern Spain: δO variability and possible causes

A high-resolution calcite oxygen stable isotopic (δ¹⁸O) record, covering the past 4000 years, was obtained from Kaite Cave, northern Spain. The record has a mean δ¹⁸O value of -6.25‰ VPDB and a range of 2‰. Spectral analysis of the δ¹⁸O data shows significant periodicities of 2400–1900, 600, 150, 27, and 22 years. The amplitudes during these periods range from 0.2‰ to 2‰. Factors controlling the isotopic ratio in the speleothem were evaluated. The calcite is most likely precipitated under equilibrium conditions, with the cave calcite δ¹⁸O interpreted as a proxy of oxygen isotopic composition in local rainwater. Other factors such as temperature or fractionation in the karst system prior to calcite precipitation are considered of negligible or of minor importance. Mechanisms affecting rainfall isotopic composition were also investigated on different time scales. Precipitation amount is the primary factor controlling the high-frequency δ¹⁸O oscillations. Other climate parameters, such as changes of storm tracks may have significant contributions on centennial and millennial time scales.     

Interhemispheric anti-phasing of rainfall during the last glacial period

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

Mineralogical Significance of Fluids in Channels of Colombian Emeralds: A Mass-Spectrometric Study

Quadrupolar mass-spectrometric study of fluids trapped in inclusions and channels is used to characterize the qualitative and quantitative composition of fluids within emeralds from 10 deposits located on the eastern and western margins of the Eastern Cordillera of Colombia. Fluids in channels and in fluid inclusions have the same qualitative composition. The bulk composition of the fluid phase is: H₂O (80 to 92 mol%), N₂ (3 to 10%), CO₂ (2.5 to 5%), H₂ (1 to 5%), CO (0.1 to 1.5%), CH₄ (<0.5%), organic compounds (<0.05%), and inert gases. Hydrogen and carbon monoxide in large part come from water and carbon dioxide reduction. Fluids trapped during emerald growth belong to an aquo-carbonic fluid phase with CO₂/N₂ ratios near 1 (0.8 to 0.84 in fluid inclusions, 1 to 1.3 in channels). Fluid contents in channels are higher by ～20% in emeralds from the western group compared to those in the eastern deposits. The concentration of H₂O in channels in emeralds from the eastern group is lower (1.35 < H₂O < 1.45 wt%) than in those of the western group (1.63 < H₂O < 2.19 wt%), and it corresponds to the lowest contents of H₂O found worldwide for emeralds from different deposit types. Colombian emeralds are quite different because their hydrothermal-sedimentary genesis is unique.

Emeralds from the western zone also have higher Na₂O contents than those from the eastern zone. A strong correlation exists between channel H₂O and Na₂O in the emeralds, which also is the case for beryls and emeralds from different geological environments. Such an enrichment is indicative of the presence of Na⁺ in the structural channels of beryl. This correlation between channel H₂O and Na₂O of the crystal is evidence for the introduction of channel H₂O as Type-II water molecules in beryls.     

Sn-polymetallic greisen-type deposits associated with late-stage rapakivi granites, Brazil: fluid inclusion and stable isotope characteristics

Tin-polymetallic greisen-type deposits in the Itu Rapakivi Province and Rondônia Tin Province, Brazil are associated with late-stage rapakivi fluorine-rich peraluminous alkali-feldspar granites. These granites contain topaz and/or muscovite or zinnwaldite and have geochemical characteristics comparable to the low-P sub-type topaz-bearing granites. Stockworks and veins are common in Oriente Novo (Rondônia Tin Province) and Correas (Itu Rapakivi Province) deposits, but in the Santa Bárbara deposit (Rondônia Tin Province) a preserved cupola with associated bed-like greisen is predominant. The contrasting mineralization styles reflect different depths of formation, spatial relationship to tin granites, and different wall rock/fluid proportions. The deposits contain a similar rare-metal suite that includes Sn (±W, ±Ta, ±Nb), and base-metal suite (Zn–Cu–Pb) is present only in Correas deposit. The early fluid inclusions of the Correas and Oriente Novo deposits are (1) low to moderate-salinity (0–19 wt.% NaCl eq.) CO₂-bearing aqueous fluids homogenizing at 245–450 °C, and (2) aqueous solutions with low CO₂, low to moderate salinity (0–14 wt.% NaCl eq.), which homogenize between 100 and 340 °C. In the Santa Bárbara deposit, the early inclusions are represented by (1) low-salinity (5–12 wt.% NaCl eq.) aqueous fluids with variable CO₂ contents, homogenizing at 340 to 390 °C, and (2) low-salinity (0–3 wt.% NaCl eq.) aqueous fluid inclusions, which homogenize at 320–380 °C. Cassiterite, wolframite, columbite–tantalite, scheelite, and sulfide assemblages accompany these fluids. The late fluid in the Oriente Novo and Correas deposit was a low-salinity (0–6 wt.% NaCl eq.) CO₂-free aqueous solution, which homogenizes at (100–260 °C) and characterizes the sulfide–fluorite–sericite association in the Correas deposit. The late fluid in the Santa Bárbara deposit has lower salinity (0–3 wt.% NaCl eq.) and characterizes the late-barren-quartz, muscovite and kaolinite veins. Oxygen isotope thermometry coupled with fluid inclusion data suggest hydrothermal activity at 240–450 °C, and 1.0–2.6 kbar fluid pressure at Correas and Oriente Novo. The hydrogen isotope composition of breccia-greisen, stockwork, and vein fluids (δ¹⁸O_quartz from 9.9‰ to 10.9‰, δD_H2O from 4.13‰ to 6.95‰) is consistent with a fluid that was in equilibrium with granite at temperatures from 450 to 240 °C. In the Santa Bárbara deposit, the inferred temperatures for quartz-pods and bed-like greisens are much higher (570 and 500 °C, respectively), and that for the cassiterite-quartz-veins is 415 °C. The oxygen and hydrogen isotope composition of greisen and quartz-pods fluids (δ¹⁸O_qtz-H2O=5.5–6.1‰) indicate that the fluid equilibrated with the albite granite, consistent with a magmatic origin. The values for mica (δ¹⁸O_mica-H2O=3.3–9.8‰) suggest mixing with meteoric water. Late muscovite veins (δ¹⁸O_qtz-H2O=−6.4‰) and late quartz (δ¹⁸O_mica-H2O=−3.8‰) indicate involvement of a meteoric fluid. Overall, the stable isotope and fluid inclusion data imply three fluid types: (1) an early orthomagmatic fluid, which equilibrated with granite; (2) a mixed orthomagmatic-meteoric fluid; and (3) a late hydrothermal meteoric fluid. The first two were responsible for cassiterite, wolframite, and minor columbite–tantalite precipitation. Change in the redox conditions related to mixing of magmatic and meteoric fluids favored important sulfide mineralization in the Correas deposit.