鄂尔多斯盆地早侏罗世富县期沉积演化: 大洋缺氧事件前后陆地气候变化的响应*

托阿尔期早期早侏罗世大洋缺氧事件(T-OAE,~183.8 Ma)是一次全球性的地质事件,鄂尔多斯盆地下侏罗统富县组记录了此次地质事件的陆地响应过程。主要基于盆地东缘野外地质调查、扫描电镜及薄片分析,本次研究描述了盆地东北部富县组岩性、颜色和沉积序列,利用前人研究成果总结了富县期岩相古地理变化规律及沉积模式,认为富县期经历了由干旱到湿润的古气候变化: 富县组下部含植物化石较为丰富的白色砂砾岩及黑色、灰色泥页岩沉积于湿润气候时期,对应着盆地下切河谷发育期和填平补齐期; 而上覆的罕见植物化石的杂色、红色泥页岩为(富县期晚期)相对平坦地形条件下的沉积,对应着早、中侏罗世湿润气候背景下的一次干旱气候脉动,为托阿尔期大洋缺氧事件在陆相环境的气候响应,可由此进行富县组区域等时性对比。研究认为“粗富县”为下切谷内河流充填沉积, “细富县”形成于湖泊环境或河漫环境, “黑富县”和“白富县”是湿润气候条件下沉积产物,而“红富县”和“杂富县”为T-OAE期后干旱条件下形成。     

Organic Geochemistry of the Early Jurassic Oil Shale from the Shuanghu Area in Northern Tibet and the Early Toarcian Oceanic Anoxic Event

This paper presents new geological and geochemical data from the Shuanghu area in northern Tibet, which recorded the Early Toarcian Oceanic Anoxic Event. The stratigraphic succession in the Shuanghu area consists mostly of grey to dark-colored alternating oil shales, marls and mudstones. Ammonite beds are found at the top of the Shuanghu oil shale section, which are principally of early Toarcian age, roughly within the Harplocearasfalciferrum Zone. Therefore,the oil shale strata at Shuanghu can be correlated with early Toarcian black shales distributing extensively in the European epicontinental seas that contain the records of an Oceanic Anoxic Event. Sedimentary organic matter of laminated shale anomalously rich in organic carbon across the Shuanghu area is characterized by high organic carbon contents, ranging from 1.8% to 26.1%. The carbon isotope curve displays the δ^13C values of the kerogen (δ^13Ckerogen) fluctuating from -26.22 to -23.53‰ PDB with a positive excursion close to 2.17‰, which, albeit significantly smaller, may also have been associated with other Early Toarcian Oceanic Anoxic Events (OAEs) in Europe. The organic atomic C/N ratios range between 6 and 43, and the curve of C/N ratios is consistent with that of the δ^13Ckerogen values. The biological assemblage,characterized by scarcity of benthic organisms and bloom of calcareous nannofossils (coccoliths), reveals high biological productivity in the surface water and an unfavorable environment for the benthic fauna in the bottom water during the Oceanic Anoxic Event. On the basis of organic geochemistry and characteristics of the biological assemblage, this study suggests that the carbon-isotope excursion is caused by the changes of sea level and productivity, and that the black shale deposition, especially oil shales, is related to the bloom and high productivity of coccoliths.     

Ocean acidification and photic‐zone anoxia at the Toarcian Oceanic Anoxic Event: Insights from the Adriatic Carbonate Platform

Severe global climate change led to the deterioration of environmental conditions in the oceans during the Toarcian Stage of the Jurassic. Carbonate platforms of the Western Tethys Ocean exposed in Alpine Tethyan mountain ranges today offer insight into this period of environmental upheaval. In addition to informing understanding of climate change in deep time, the effect of ancient carbon cycle perturbations on carbonate platforms has important implications for anthropogenic climate change; the patterns of early Toarcian environmental deterioration are similar to those occurring in modern oceans. This study focuses on the record of the early Toarcian Oceanic Anoxic Event (ca 183.1 Ma) in outcrops of the north‐west Adriatic Carbonate Platform in Slovenia. Amidst environmental deterioration, the north‐west Adriatic Platform abruptly transitioned from a healthy, shallow‐water environment with diverse metazoan ecosystems to a partially drowned setting with low diversity biota and diminished sedimentation. An organic carbon‐isotope excursion of ?2.2‰ reflects the massive injection of CO₂ into the ocean‐atmosphere system and marks the stratigraphic position of the Toarcian Oceanic Anoxic Event. A prominent dissolution horizon and suppressed carbonate deposition on the platform are interpreted to reflect transient shoaling of the carbonate compensation depth to unprecedentedly shallow levels as the dramatic influx of CO₂ overwhelmed the ocean’s buffering capacity, causing ocean acidification. Trace metal geochemistry and palaeoecology highlight water column deoxygenation, including the development of photic‐zone anoxia, preceding and during the Toarcian Oceanic Anoxic Event. Ocean acidification and reduced oxygen levels likely had a profoundly negative effect on carbonate‐producing biota and growth of the Adriatic Platform. These effects are consistent with the approximate doubling of the concentration of CO₂ in the ocean‐atmosphere system from pre‐event levels, which has previously been linked to a volcanic triggering mechanism. Mercury enrichments discovered in this study support a temporal and genetic link between volcanism, the Toarcian Oceanic Anoxic Event and the carbonate crisis.     

Spatial variability of watermass conditions within the European Epicontinental Seaway during the Early Jurassic (Pliensbachian–Toarcian)

In order to constrain spatial variability in watermass conditions within the European Epicontinental Seaway prior to, during and after the Toarcian Oceanic Anoxic Event, carbon (δ¹³C_bel, δ¹³C_carb) and oxygen (δ¹⁸O_bel, δ¹⁸O_carb) isotope records were obtained from three sections in the Grands Causses Basin (southern France). These data were then compared with similar records along a north–south transect across the European Epicontinental Seaway. As the conclusions reached here strongly depend on the reliability of belemnite calcites as archives of palaeoceanographic changes, an attempt was made to improve the understanding of isotope signals recorded in belemnite calcite. Intra‐rostral carbon and oxygen‐isotope data from six belemnite specimens belonging to the genus Passaloteuthis were collected. Intra‐rostral carbon‐isotopes are influenced by vital effects, whereas oxygen‐isotopes reflect relative changes in temperature and salinity. Palaeotemperatures calculated from δ¹⁸O_bel‐isotope records from the Grands Causses Basin confirm relatively low temperatures throughout the Late Pliensbachian. Similar cool water conditions have previously been shown in Germany, England, Spain and Portugal. A temperature increase of up to 6 °C is observed across the Pliensbachian–Toarcian boundary. A pronounced negative shift of at least ?3‰ (Vienna‐Pee Dee Belemnite) is recorded in bulk carbonate carbon during the lower Harpoceras serpentinum zone, typical of the Toarcian Oceanic Anoxic Event. Before and after the Toarcian Oceanic Anoxic Event, a good correlation between δ¹³C_carb and δ¹³C_bel exists, indicating well‐ventilated bottom‐waters and normal marine conditions. Instead, data for the Toarcian Oceanic Anoxic Event indicate the development of a strong north–south gradient in salinity stratification and surface‐water productivity for the Western Tethyan realm. This study thus lends further support to a pronounced regional overprint on carbon and oxygen‐isotope records in epicontinental seaways.     

白垩纪缺氧事件期间分子有机碳同位素偏移的二种不同机制

对我国业已发现的白垩纪大洋缺氧事件进行了对比研究.结果显示,我国河北滦平盆地高等植物叶腊碳同位素正偏,是weissert缺氧事件的陆地响应,weissert缺氧事件可能是全球性缺氧事件,而不是区域性的缺氧事件.叶腊烷烃单分子碳同位素正偏有两种不同的机制:早白垩世分子碳同位素正偏主要反映的是大气CO2水平增加;晚白垩世分子碳同位素正偏主要反映的是陆地植物类型的变化.     

Paleoceanographic evolution and chronostratigraphy of the Aptian Oceanic Anoxic Event 1a (OAE1a) to oceanic red bed 1 (ORB1) in the Gorgo a Cerbara section (central Italy)

We performed a detailed study of the stratigraphic transition of Oceanic Anoxic Event 1a (OAE1a) to oceanic red bed 1 (ORB1) from the classic Gorgo a Cerbara section in the Umbria region of central Italy. We focused on a 25.5-m-thick stratigraphic succession, from which we analyzed 305 samples for total organic carbon (TOC), CaCO₃, magnetic susceptibility, diffuse reflectance spectrophotometry and the stable carbon and oxygen isotopic composition of both bulk samples and organic matter. In the Gorgo a Cerbara section, the Selli Level of OAE1a (∼1.81 m thick) consists of laminated to bioturbated dark gray to black mudstones and shales with medium to dark gray radiolarian-rich silty to sandy layers and a maximum TOC content of 20.22%. The carbon isotopic values show a negative excursion (C3 stage, ∼0.14 m) at the base of the Selli Level, followed by a stepwise positive excursion (C4–C6 stages, ∼1.67 m) in the upper part of the Selli Level. The transition from OAE1a to ORB1 (∼3.19 m thick) is characterized by bioturbated greenish gray cherty limestones and marly limestones with subordinate marls, corresponding to stable carbon isotopic C7 stage and lasts for ∼0.75 Ma. The ORB1 interval (∼13.15 m) consists of reddish marly claystones, dark-red marlstones, red marly limestones and red calcareous shales which indicate a highly oxic environment. Our results reveal a stepwise transition from a predominantly mesotrophic and dysoxic to anoxic environment at the time that the OAE1a black shales were deposited to an oligotrophic and oxic environment during the transitional interval and finally to highly oxic conditions during the ORB1 interval. The nannoconid crisis occurs at the top of the C2 stage, just 0.34 m below the negative excursion in δ¹³C isotopic values. The massive CaCO₃ dissolution phase occurs 0.25 m above the negative excursion; it persisted for 0.85 Ma and probably resulted from excess CO₂, ocean acidification, and carbonate compensation depth (CCD) shoaling. Deposition of massive black shales occurs at the base of the C6 stage and lasted for 0.4 Ma.     

Chemo- and Biostratigraphy of the Jurassic Oil Shales from the Qiangtang Basin, Northern Tibet, China: A Case Study of the Toarcian Oceanic Anoxic Event

The marine oil shales of the Qiangtang Basin, northern Tibet, exposed in the Biluo Co, Tuonamu, Shenglihe and Changsheshan areas are believed to be important petroleum source rocks. This work comprehensively analyzed the carbon isotopes, trace elements, and calcareous nannofosills, ammonites and bivalves of the Biluo Co section in the Qiangtang Basin. The organic carbon isotopes show a positive excursion close to 2.17‰(relative to PDB), which, albeit significantly smaller, may also be associated with other Early Toarcian Oceanic Anoxic Events(T-OAE) in the European epicontinental seas and the Tethyan continental margins. Coinciding with the Early Toarcian transgression, the oxygen deficiency in bottom water had led to dysoxic-anoxic conditions and deposition of black shales lacking benthic fauna. Under such condition, the redox-sensitive trace metals such as Mo, V, Ni, Cr, and U were enriched, in conjunction with high planktonic productivity of Watznaueriaceae calcareous nannofossils. Comparison of the results with the records of chemo-and biostratigraphy, as well as the palaeogeography during the Early Jurassic suggests that the anoxia linked to the Early Toarcian oceanic anoxic event was mainly caused by the high surface water temperature, sea-level rise and an increase of surface water productivity.     

Symplectite formation in the presence of a reactive fluid: insights from hydrothermal experiments

This study describes the microstructural and chemical development of symplectites, obtained in fluid‐mediated mineral replacement experiments. During the experiments polymineralic feldspar‐rich samples were exposed to aqueous Na–SiO₂ solution at 600 °C and 2 kbar confining pressures for durations of 12 h to 20 days. The resulting reaction rims display high mineralogical and structural complexity and contain two varieties of symplectites, represented by nanometre‐scale intergrowths of gehlenite–zeolite and grossular–zeolite grains. The experimental fluid was enriched in ¹⁸O isotope in order to trace oxygen redistribution during the reaction. The elevated ¹⁸O concentration in the reaction products and the heterogeneity in its distribution suggest that symplectite formation was controlled by dissolution–precipitation mechanisms rather than volume‐diffusion processes. Microstructural and chemical observations suggest that symplectite formation occurred in multiple stages in response to spatially heterogeneous and temporarily evolving fluid composition at the reaction interfaces. Hence, our results shed light on the fundamental processes involved in symplectite formation improving our ability to interpret symplectite microstructures.     

Lithogeochemical,Re–Os and U–Pb Geochronological,Hf–Lu and S–Pb Isotope Data of the Ga'erqiong‐Galale Cu–Au Ore‐Concentrated Area: Evidence for the Late Cretaceous Magmatism and Metallogenic Event in the Bangong‐Nujiang Suture Zone,Northwestern Tibet,China

The Ga'erqiong‐Galale skarn–porphyry copper–gold ore‐concentrated area is located in the western part of the Bangong‐Nujiang suture zone north of the Lhasa Terrane. This paper conducted a systematic study on the magmatism and metallogenic effect in the ore‐concentrated area using techniques of isotopic geochronology, isotopic geochemistry and lithogeochemistry. According to the results, the crystallization age of quartz diorite (ore‐forming mother rock) in the Ga'erqiong deposit is 87.1 ± 0.4 Ma, which is later than the age of granodiorite (ore‐forming mother rock) in the Galale deposit (88.1 ± 1.0 Ma). The crystallization age of granite porphyry (GE granite porphyry) in the Ga'erqiong deposit is 83.2 ± 0.7 Ma, which is later than the age of granite porphyry (GL granite porphyry) in the Galale deposit (84.7 ± 0.8 Ma).The quartz diorite, granodiorite, GE granite porphyry and GL granite porphyry both main shows positive ε_Hf(t) values, suggesting that the magmatic source of the main intrusions in the ore‐concentrated area has the characteristics of mantle source region. The Re–Os isochron age of molybdenite in the Ga'erqiong district is 86.9 ± 0.5 Ma, which is later than the mineralization age of the Galale district (88.6 ± 0.6 Ma). The main intrusive rocks in the ore‐concentrated area have similar lithogeochemical characteristics, for they both show the relative enrichment in large‐ion lithophile elements(LILE: Rb, Ba, K, etc.), more mobile highly incompatible lithophile elements(HILE: U, Th) and relatively depleted in high field strength elements (HFSE: Nb, Ta, Zr, Hf, etc.), and show the characteristics of magmatic arc. The studies on the metal sulfides' S and Pb isotopes and Re content of molybdenite indicate that the metallogenic materials of the deposits in the ore‐concentrated area mainly come from the mantle source with minor crustal source contamination. Based on the regional tectonic evolution process, this paper points out that the Ga'erqiong‐Galale copper–gold ore‐concentrated area is the typical product of the Late Cretaceous magmatism and metallogenic event in the collision stage of the Bangong‐Nujiang suture zone.     

U–Pb Dating of Hydrothermal Zircons from the Neoproterozoic Liushanyan VMS Cu–Zn Deposit,Central China: Evidence for a Triassic Deformation Event

The Liushanyan deposit is an important volcanic‐host massive sulfide (VMS) Cu–Zn deposit in the Qinling‐Tongbai‐Dabie orogenic belt, central China, with reserve of 2.38 Mt Cu and 16.11 Mt Zn. Orebodies occur in the meta‐quartz keratophyre of the Liushanyan formation. In this paper, we present textural features and laser ablation ICP‐MS U–Pb dating results of zircons from the ore‐bearing mylonitized meta‐quartz keratophyre. The hydrothermal zircons are distinct from metamorphic zircons in this rock, showing low cathodoluminescence (CL) response and hydrothermal rims (black in CL images). They have relatively flat light rare earth element patterns and high La content and low (Sm/La)_N and Ce/Ce* values. These features are typical of hydrothermal zircons. The cores of metamorphic zircons yield a weighted mean ²⁰⁶Pb/²³⁸U age of 900 ± 26 Ma, interpreted as the volcanic and related VMS mineralizing age. Two much younger events are also recorded by zircons in this rock: (i) the Early Silurian amphibolites–greenschist facies metamorphism at 435 ± 26 Ma; and (ii) the growth of hydrothermal zircons at ca. 241 ± 1 Ma, associated with the ductile shear deformation. The Silurian metamorphic event is probably associated with the arc–continent collision, while the Triassic ductile deformation event formed in the final continent–continent collision setting.     

Response to the Lomagundi-Jatuli Event in the southwestern margin of the Yangtze Plate: Evidence from the carbon and oxygen isotopes of the Paleoproterozoic Yongjingshao Formation

The Lomagundi-Jatuli Event (LJE) refers to the significant positive carbon isotope excursion in seawater constituents that occurred immediately after the increase in atmospheric oxygen content during the Paleoproterozoic (2.22–2.06 Ga). The δ¹³C values of 46 dolostone samples collected from the Paleoproterozoic Yongjingshao Formation varied in the range of 0.05 ‰–4.95 ‰ (V-PDB; maximum: 4.95‰) in this study, which may be related to the multicellular eukaryotes in the Liangshan Formation in the Yimen Group. They are much higher than the δ¹³C values of marine carbonates (?1.16‰ on average). The δ¹³C values of other formations in the Paleoproterozoic Yimen Group are negative. The notable positive carbon isotope anomalies of the Yongjingshao Formation indicate the response to the LJE at the southwestern margin of the Yangtze Block, which is reported for the first time. Furthermore, they are comparable to the δ¹³C values of carbonates in the Dashiling Formation of the Hutuo Group in the Wutaishan area in the North China Craton, the Wuzhiling Formation of the Songshan Group in the Xiong’ er area, Henan Province, and the Dashiqiao Formation of the Liaohe Group in the Guanmenshan area, Liaoning Province. Therefore, it can be further concluded that the LJE is a global event. This study reveals that LJE occurred in Central Yunnan at 2.15–2.10 Ga, lasting for about 50 Ma. The macro-columnar, bean-shaped, and microfilament fossils and reticular ultramicrofossils of multicellular eukaryotes in this period were discovered in the Liangshan Formation of the Yimen Group. They are the direct cause for the LJE and are also the oldest paleontological fossils ever found. The major events successively occurring in the early stage of the Earth include the Great Oxygenation Event (first occurrence), the global Superior-type banded iron formations (BIFs), the Huronian glaciation, the Great Oxygenation Event (second occurrence), the explosion of multicellular eukaryotes, the positive carbon isotope excursion, and the global anoxic and selenium-rich sedimentary event. The authors think that the North China Craton and the Yangtze Craton were possibly in different tectonic locations of the same continental block during the Proterozoic.©2023 China Geology Editorial Office.     

Middle Carboniferous crustal melting in the Variscan Belt: New insights from U–Th–Pbtot. monazite and U–Pb zircon ages of the Montagne Noire Axial Zone (southern French Massif Central)

In France, the Devonian–Carboniferous Variscan orogeny developed at the expense of continental crust belonging to the northern margin of Gondwana. A Visean–Serpukhovian crustal melting has been recently documented in several massifs. However, in the Montagne Noire of the Variscan French Massif Central, which is the largest area involved in this partial melting episode, the age of migmatization was not clearly settled. Eleven U–Th–Pb_tot. ages on monazite and three U–Pb ages on associated zircon are reported from migmatites (La Salvetat, Ourtigas), anatectic granitoids (Laouzas, Montalet) and post-migmatitic granites (Anglès, Vialais, Soulié) from the Montagne Noire Axial Zone are presented here for the first time. Migmatization and emplacement of anatectic granitoids took place around 333–326 Ma (Visean) and late granitoids emplaced around 325–318 Ma (Serpukhovian). Inherited zircons and monazite date the orthogneiss source rock of the Late Visean melts between 560 Ma and 480 Ma. In migmatites and anatectic granites, inherited crystals dominate the zircon populations. The migmatitization is the middle crust expression of a pervasive Visean crustal melting event also represented by the “Tufs anthracifères” volcanism in the northern Massif Central. This crustal melting is widespread in the French Variscan belt, though it is restricted to the upper plate of the collision belt. A mantle input appears as a likely mechanism to release the heat necessary to trigger the melting of the Variscan middle crust at a continental scale.     

Early Mesozoic Southward Subduction of the Eastern Mongol–Okhotsk Oceanic Plate: Evidence from Zircon U–Pb–Hf Isotopes and Whole‐rock Geochemistry of Triassic Granitic Rocks in the Mohe Area,NE China

In this paper, we present new U–Pb zircon ages, Hf isotope data and major and trace elements for Early Mesozoic granitic rocks in Mohe area in the Erguna Massif of northeast China to elucidate the southward subduction of the eastern Mongol–Okhotsk Oceanic plate in Early Mesozoic. Zircons from two representative intrusions, syenogranites and monzogranites, in the Mohe area are euhedral–subhedral in shape, display oscillatory growth zoning in cathodoluminescence (CL) images, and have Th/U ratios of 0.10–0.72, and in combination these features indicating that the zircons are of igneous origin. U–Pb zircon dating results demonstrate that the syenogranites formed at 245.1 ± 1.4 Ma and monzogranites formed at 212.2 ± 1.7 Ma. These granitic rocks are characterized by high SiO₂, Al₂O₃ and (Na₂O + K₂O), low TFeO, MgO, TiO₂ and P₂O₅ concentrations, belonging to the high‐K calc‐alkaline series. They are enriched in LREE and large ion lithophile elements (e.g., Rb, K, and Sr), depleted in HREE and high field strength elements (e.g., Nb, Ta, Th, and Ti), as well as very weak negative Eu anomalies (Eu/Eu* = 0.48 ~ 1.01). Their zircon εHf(t) values range from −7.9 to −2.0 and range from 0.20 to 0.49, in response to their two‐stage Hf model ages (T_DM2) range from 1.40 Ga to 1.77 Ga range from 0.94 Ga to 1.24 Ga, respectively, indicating that primary magmas of syenogranites were derived from partial melting of newly accreted juvenile crustal material that formed from the enriched mantle during the Mesoproterozoic, monzogranites are generated by partial melting of newly accreted juvenile crustal material that formed from the depleted mantle during the Meso‐ to Neoproterozoic. We conclude, therefore, that the early Mesozoic granitic rocks of the Mohe area are associated with the continuous southward subduction of the Mongol–Okhotsk oceanic plate rather than the Paleo‐Asian and circum‐Pacific tectonic regimes.     

U–Th–Pb–REE systematics of organic-rich shales from the ca. 2.15 Ga Sengoma Argillite Formation, Botswana: Evidence for oxidative continental weathering during the Great Oxidation Event

The redox-sensitive geochemical behavior of uranium permits the use of Th/U ratios as a geochemical proxy for the oxidation state of the atmosphere during deposition. Due to the effects of post-depositional uranium mobility on Th/U ratios during events involving oxygenated fluids, direct measurements of Th/U ratios are often misleading even for drill core samples. Because both of these elements radioactively decay and produce lead isotopes, the Pb isotope composition may reflect the depositional Th/U ratio, although the Th/U ratios induced by changes shortly after deposition may not be distinguished from the true depositional Th/U ratios. In order to effectively evaluate the time-integrated Th/U ratio (κ_a), values for the initial depositional Pb isotope composition must be determined or accepted from the models for the whole Earth.While the timing for the rise of atmospheric oxygen is reasonably well constrained now, its effect on continental weathering and ocean redox state remains poorly constrained and debated. The ca. 2.15 Ga Sengoma Argillite Formation of Botswana contains organic-rich shales deposited during the Great Oxidation Event. The slope of the ²⁰⁷Pb/²⁰⁴Pb–²⁰⁶Pb/²⁰⁴Pb array of shales from the Sengoma Argillite Formation corresponds to a Pb–Pb age that is within analytical error of the depositional age and is, therefore, inferred to be the time by which the time-integrated thorogenic and uranogenic lead growth started. The time-integrated lead growth corresponds to an average κ_a of 2.63 (± 0.62, 1σ) for the organic-rich shales of the Sengoma Argillite Formation. This is lower than Th/U ratios measured in Archean shale suites or estimated for the Archean–Proterozoic average upper continental crust [Taylor, S.R. and McLennan, S.M., 1985. The Continental Crust: Its Composition and Evolution. Blackwell, Oxford, 312 pp.], which indicates that these samples were enriched in uranium with respect to thorium (and perhaps lead) at the time of deposition. In the modern ocean, sediments are enriched in uranium under reducing conditions by reduction of the water-soluble uranyl ion, which is delivered to the ocean by oxidative weathering of continental crust. To evaluate the potential mobility of Th, U, and Pb during post-depositional processes, the concentrations of the rare earth elements (REE) were also determined. Interelement ratios of the largely immobile REE (in this study, La/Nd and Gd/Er) can be used as a proxy for the Th/U ratio, as the geochemical behavior of the lanthanide and actinide elements is similar under a variety of conditions. Furthermore, close similarity in the chondrite-normalized REE patterns and small range in La/Nd and Gd/Er ratios in studied samples indicate that variations in κ_a values are not likely to have been controlled by mixing of one or more REE-, Th-, and U-rich heavy minerals from the multiple detrital sources. Our study of shales from the ca. 2.15 Ga Sengoma Argillite Formation indicates that decoupling of U from Th, most likely related to the oxidative continental weathering, began by 2.15 Ga, at the latest.     

Cu–Mo Differential Mineralization Mechanism of the Dabate Polymetallic Deposit in Western Tianshan,NW China: Evidence from Geology,Fluid Inclusions,and Oxygen Isotope Systematics

Classic porphyry Cu–Mo deposits are mostly characterized by close temporal and spatial relationships between Cu and Mo mineralization. The northern Dabate Cu–Mo deposit is a newly discovered porphyry Cu–Mo polymetallic deposit in western Tianshan, northwest China. The Cu mineralization postdates the Mo mineralization and is located in shallower levels in the deposit, which is different from most classic porphyry Cu–Mo deposits. Detailed field investigations, together with microthermometry, laser Raman spectroscopy, and O‐isotope studies of fluid inclusions, were conducted to investigate the origin and evolution of ore‐forming fluids from the main Mo to main Cu stage of mineralization in the deposit. The results show that the ore‐forming fluids of the main Mo stage belonged to an NaCl + H₂O system of medium to high temperatures (280–310°C) and low salinities (2–4 wt% NaCl equivalent (eq.)), whereas that of the main Cu stage belonged to an F‐rich NaCl + CO₂ + H₂O system of medium to high temperatures (230–260°C) and medium to low salinities (4–10 wt% NaCl eq.). The δ¹⁸O values of the ore‐forming fluids decrease from 3.7–7.8‰ in the main Mo stage to ?7.5 to ?2.9‰ in the main Cu stage. These data indicate that the separation of Cu and Mo was closely related to a large‐scale vapor–brine separation of the early ore‐forming fluids, which produced the Mo‐bearing and Cu‐bearing fluids. Subsequently, the relatively reducing (CH₄‐rich) Mo‐bearing, ore‐forming fluids, dominantly of magmatic origin, caused mineralization in the rhyolite porphyry due to fluid boiling, whereas the relatively oxidizing (CO₂‐rich) Cu‐bearing, ore‐forming fluids mixed with meteoric water and precipitated chalcopyrite within the crushed zone at the contact between rhyolite porphyry and wall rock. We suggest that the separation of Cu and Mo in the deposit may be attributed to differences in the chemical properties of Cu and Mo, large‐scale vapor–brine separation of early ore‐forming fluids, and changes in oxygen fugacity.     

Petrology and thermobarometry of mafic granulites and migmatites from the Chafalote Metamorphic Suite: New insights into the Neoproterozoic P–T evolution of the Uruguayan—Sul-Rio-Grandense shield

This paper reports a study of the metamorphic evolution of pelitic, semi-pelitic migmatites and mafic granulites of the Chafalote Metamorphic Suite (CMS), Uruguay, which represents the southernmost exposures of high-grade metamorphic rocks in the Dom Feliciano Belt, Uruguain—Sul-Rio-Grandense shield, South America. This belt is one of the Brasiliano orogens that crop out along the Brazilian and Uruguayan Atlantic margin, and the CMS is one of several disconnected segments of supracrustal rock in a dominantly granitic terrain. Petrological evidence from CMS mafic granulites and semi-pelitic migmatites indicates four distinct metamorphic assemblages. The early prograde assemblage (M₁) is preserved only as inclusions in porphyroblasts of the peak-metamorphic (M₂) assemblage. Peak-metamorphism was followed by near-isothermal decompression (M₃), which resulted in symplectites and coronitic textures in the mafic granulites and compositional zoning of Ca in garnet (decreasing rimwards) and plagioclase (increasing rimwards) in the semi-pelitic migmatites. The retrograde metamorphic assemblage (M₄) is represented by hydration reaction textures replacing minerals of the M₂ and M₃ assemblages. Average P–T calculations using the program THERMOCALC and conventional thermobarometric methods yield peak-metamorphic (M₂) P–T conditions of 7–10 kbar and 830–950 °C, near-decompressional (M₃) P–T conditions of 4.8–5.5 kbar and 788–830 °C and M₄ retrograde P–T conditions of 3–6 kbar and 600–750 °C. The calculated P–T path for the CMS rocks is ‘clockwise’ and incorporates a near-isothermal decompression segment followed by minor cooling, consistent with a history of crustal thickening followed by extensional collapse at ca. 650–600 Ma. The metamorphism recorded by rocks of this crustal segment may be correlated with 650 Ma metamorphism in the Coastal Terrane of the Kaoko Belt in Namibia, being the first unequivocal match between South America and Africa provided by crystalline rocks south of the Congo Craton.     

A multi‐proxy record of changing environments from ca. 30 000 to 9000 cal. a BP: Onepoto maar palaeolake,Auckland, New Zealand

We present a high‐resolution record of lacustrine sedimentation spanning ca. 30 000 to 9000 cal. a BP from Onepoto maar, northern North Island, New Zealand. The multi‐proxy record of environmental change is constrained by tephrochronology and accelerator mass spectrometric ¹⁴C ages and provides evidence for episodes of rapid environmental change during the Last Glacial Coldest Period (LGCP) and Last Glacial–Interglacial Transition (LGIT) from northern New Zealand. The multi‐proxy palaeoenvironmental record from Onepoto indicates that the LGCP was cold, dry and windy in the Auckland region, with vegetation dominated by herb and grass in a beech forest mosaic between ca. 28 500 and 18 000 cal. a BP. The LGCP was accompanied by more frequent fires and influx of clastic sediment indicating increased erosion during the LGCP, with a mid‐LGCP interstadial identified between ca. 25 000 and 23 000 cal. a BP. Rapid climate amelioration at ca. 18 000 cal. a BP was accompanied by increased terrestrial biomass exemplified by the expansion of lowland podocarp forest, especially Dacrydium cupressinum. Increasing biomass production is reversed briefly by LGIT perturbations which are apparent in many of the proxies that span ca. 14 000–10 500 cal. a BP, suggesting generally increased wetness and higher in situ aquatic plant productivity with reduced terrestrial organic matter and terrigenous detrital influx. Furthermore, conditions at that time were probably warmer and frosts rare based on the increasing importance of Ascarina. The subsequent early Holocene is characterised by podocarp conifer forest and moist mild conditions. Postglacial sea‐level rise breached the crater rim and deposited 36 m of estuarine mud after ca. 9000 cal. a BP. Copyright © 2011 John Wiley & Sons, Ltd.     

Determination of the Concentration of Carbonic Species in Natural Waters: Results from a World‐Wide Proficiency Test

The results of an international interlaboratory proficiency test for the determination of carbonic species are presented. Eight laboratories analysed twelve water samples (four synthetic waters, one lake water, four geothermal waters, one seawater and two petroleum waters) by two methods: (a) individual laboratory analytical procedure and (b) acid–base titration curves in tabular form following a standardised protocol. In case (b), the concentrations of carbonic species were calculated by the organiser using the (1) Hydrologists' method, (2) Geochemists' method and/or (3) initial pH and total alkalinity method. For synthetic waters, the averaged % trueness and precision of measurement of the two methods were (trueness = 7.6, precision = 9.4) and (9.0, 3.4) for total alkalinity, and (6.6, 31.0) and (7.8, 6.1) for carbonic alkalinity, respectively. This indicates that the total alkalinity calculation procedure is in general correct in the individual laboratory method, but the carbonic alkalinity calculation procedure has serious problems. The measurements of total alkalinity for lake and seawaters were in agreement in both the methods; however, the individual laboratory measurement method for geothermal and petroleum waters was conceptually incorrect. Thus, the analytical procedures for the determination of carbonic species were reviewed. To apply the Hydrologists' and/or Geochemists' methods, the location of NaHCO₃EP and H₂CO₃EP is necessary, even for samples with pH lower than that of NaHCO₃EP, and a backward titration curve after complete removal of CO₂ must be performed. The initial pH and total alkalinity method is appropriate where a complete analysis of species that contribute to the alkalinity is known.