Late Cenomanian to Middle Turonian high-resolution carbon isotope stratigraphy: New data from the Münsterland Cretaceous Basin,Germany

New high resolution carbon isotope stratigraphies from two basinal pelagic carbonate successions in northern Germany (Halle and Oerlinghausen, Münsterland Cretaceous Basin) resolve late Cenomanian to early Mid-Turonian carbon cycle variations at timescales of less than 100 kyr. Beside the major carbon isotope excursion of the late Cenomanian oceanic anoxic event (OAE 2), 11 small-scale distinct features are precisely resolved in the δ¹³C carbonate curve and related to boreal macrofossil zonations. The small-scale carbon isotope events correspond to secular δ¹³C carbonate variations identified previously in the English Chalk. The boreal high-resolution δ¹³C carbonate curve shows a detailed coincidence with two Tethyan δ¹³C curves from Italy, what demonstrates the interregional significance of the δ¹³C dates and allows their correlation within error limits of ± 40 kyr. Furthermore, the new δ¹³C curve enables the calibration of boreal and tethyan macro- and microfossil zonations. Accordingly, the Tethyan calcareous nannoplankton boundary NC13/NC14 corresponds to the boreal FO of C. woollgari, the index taxon for the Lower-Middle Turonian boundary. The cyclic appearance and the temporal spacing of the small-scale carbon isotope events suggest that orbital forcing exerted control on surface water productivity and organic matter preservation at the sea floor.     

Carbon isotopic compositions of organic matter across continental Cretaceous–Tertiary (K–T) boundary sections: Implications for paleoenvironment after the K–T impact event

To assess the environmental perturbation induced by the impact event that marks the Cretaceous–Tertiary (K–T) boundary, concentrations and isotopic compositions of bulk organic carbon were determined in sedimentary rocks that span the terrestrial K–T boundary at Dogie Creek, Montana, and Brownie Butte, Wyoming in the Western Interior of the United States. The boundary clays at both sites are not bounded by coals. Although coals consist mainly of organic matter derived from plant tissue, siliceous sedimentary rocks, such as shale and clay, may contain organic matter derived from microbiota as well as plants. Coals record δ¹³C values of plant-derived organic matter, reflecting the δ¹³C value of atmospheric CO₂, whereas siliceous sedimentary rocks record the δ¹³C values of organic matter derived from plants and microbiota. The microbiota δ¹³C value reflects not only the δ¹³C value of atmospheric CO₂, but also biological productivity. Therefore, the siliceous rocks from these sites yields information that differs from that obtained previously from coal beds.Across the freshwater K–T boundary at Brownie Butte, the δ¹³C values decrease by 2.6‰ (from − 26.15‰ below the boundary clay to − 28.78‰ above the boundary clay), similar to the trend in carbonate at marine K–T sites. This means that the organic δ¹³C values reflect the variation of δ¹³C of atmospheric CO₂, which is in equilibrium with carbon isotopes at the ocean surface. Although a decrease in δ¹³C values is observed across the K–T boundary at Dogie Creek (from − 25.32‰ below the boundary clay to − 26.11‰ above the boundary clay), the degree of δ¹³C-decrease at Dogie Creek is smaller than that at Brownie Butte and that for marine carbonate.About 2‰ decrease in δ¹³C of atmospheric CO₂ was expected from the δ¹³C variation of marine carbonate at the K–T boundary. This δ¹³C-decrease of atmospheric CO₂ should affect the δ¹³C values of organic matter derived from plant tissue. As such a decrease in δ¹³C value was not observed at Dogie Creek, a process that compensates the δ¹³C-decrease of atmospheric CO₂ should be involved. For example, the enhanced contribution of ¹³C-enriched organic matter derived from algae in a high-productivity environment could be responsible. The δ¹³C values of algal organic matter become higher than, and thus distinguishable from, those of plant organic matter in situations with high productivity, where dissolved HCO₃⁻ becomes an important carbon source, as well as dissolved CO₂. As the δ¹³C-decrease of atmospheric CO₂ reflected a reduction of marine productivity, the compensation of the δ¹³C decrease by the enhanced activity of the terrestrial microbiota means that the microbiota at freshwater environment recovered more rapidly than those in the marine environment.A distinct positive δ¹³C excursion of 2‰ in the K–T boundary clays is superimposed on the overall decreasing trend at Dogie Creek; this coincides with an increase in the content of organic carbon. We conclude that the K–T boundary clays include ¹³C-enriched organic matter derived from highly productive algae. Such a high biological productivity was induced by phenomena resulting from the K–T impact, such as nitrogen fertilization and/or eutrophication induced by enhanced sulfide formation. The high productivity recorded in the K–T boundary clays means that the freshwater environments (in contrast to marine environments) recovered rapidly enough to almost immediately (within 10 yr) respond to the impact-related environmental perturbations.     

High-resolution terrestrial carbon isotope and planktic foraminiferal records of the Upper Cenomanian to the Lower Campanian in the Northwest Pacific

Making Upper Cretaceous biostratigraphic correlations between the Northwest Pacific and Tethyan–Atlantic sections have been difficult because of rare frequencies of age-diagnostic macro- and microfossils in the sequences in the Northwest Pacific region. In order to correlate these sections precisely, an integrated planktic foraminiferal and bulk wood carbon-isotope stratigraphy from the upper Cenomanian to the lower Campanian succession (the middle–upper part of the Yezo Group) of Hokkaido, northern Japan is established with an average resolution of 50 k.y. The δ¹³C curves from bulk wood of the Yezo Group and from bulk carbonate of English Chalk show remarkably similar patterns of isotopic fluctuation, allowing the correlation of 22 carbon isotopic events between these sections. This high-resolution correlation greatly improves the previous micro- and macrofossil biostratigraphic schemes in the Northwest Pacific region, and reveals that global events, such as the oxygen depletion at the OAE 2 horizon, the constant decrease in pCO₂ during the Late Cretaceous, and the eustatic sea-level falls in the late middle Turonian, Santonian/Campanian Boundary and early Campanian, are recorded in the Upper Cretaceous sequence of the Northwest Pacific.     

Characterization of the negative carbon isotope shift in segment C2, its global implications as a harbinger of OAE1a

Lower Cretaceous C-isotope records show intermittent negative/positive spikes, and consistent patterns of coeval chemostratigraphic curves thus document shifts that signal simultaneous responses of temporal changes in the global carbon reservoir. The standard pattern registered by the δ ¹³C_org and δ ¹³C_carb in Lower Aptian sediments includes distinct isotope segments C1 to C8 (Menegatti et al., 1998). In the El Pui section, Organyà Basin, Spain, C-isotope segment C2 is the longest interval preceding segments C3–C6 associated with oceanic anoxic event 1a (OAE 1a), and reveals a distinct negative shift of ~1.8‰ to ~2.23‰ defining the C-isotope pattern within that interval. Total inorganic carbon (TIC), total organic carbon (TOC), δ ¹³C_org, microfacies, n-alkanes show no difference before, during, or after the negative inflection. The biomarkers indicate that organic matter (OM) mainly originates from algal/microbial sources because short-chain length homologues (≤nC₁₉) dominate. nC₂₀ through nC₂₅ indicate some contribution from aquatic vegetation, but little from higher plants (>nC₂₅), as also suggested by the terrestrial/aquatic ratio of n-alkanes or (TAR) = [(nC₂₇+nC₂₉+nC₃₁)/(nC₁₅+nC₁₇+nC₁₉)] (averages 0.085). We suggest that conjoint pulses of contemporaneous LIPs (Ontong Java) and massive explosive volcanism in northeast Asia, the Songliao Basin (SB-V), best conform to plausible causes of the negative intra-C2 carbon isotopic excursion (CIE) at that time. Because of its apparent common occurrence the intra-C2 inflection could be a useful marker harbinger to the more pronounced CIE C3, the hallmark of OAE1a.     

Chemostratigraphy of the Ediacaran basinal setting on the Yangtze platform,South China: Oceanographic and diagenetic aspects of the carbon isotopic depth gradient

The Ediacaran Yangtze platform in South China, which represents depositional settings ranging from coastal to basinal, provides valuable information for understanding climate changes and animal evolution during the Ediacaran Period. Although the shallower settings have been investigated, research on the basinal sections has been limited. This has hampered efforts to establish stratigraphic correlations and understand the oceanographic setting of the Yangtze platform. In this paper, the chemostratigraphy of a basinal section at Fengtan, Hunan Province, is reported based on analyses of stable carbon isotope profiles in carbonates (δ¹³C_carb), organic matter (δ¹³C_org), total organic carbon, ⁸⁷Sr/⁸⁶Sr ratios, and Mn, Rb, and Sr concentrations. The basinal section of the Doushantuo Formation, which is represented at Fengtan, provides data supporting regional correlations and oceanography. Three intervals in the Doushantuo Formation are correlated with the Three Gorges: (i) a negative δ¹³C_carb anomaly with stable δ¹³C_org values and altered ⁸⁷Sr/⁸⁶Sr ratios in the lower section can be correlated to the boundary between Doushantuo Members 2 and 3 (Interval A); (ii) a relatively high δ¹³C_carb anomaly with unaltered ⁸⁷Sr/⁸⁶Sr ratios (up to 0.7086) in the middle section corresponding to the lower part of Doushantuo Member 3 (Interval B); and (iii) a negative δ¹³C_carb anomaly with lowered δ values in the upper section can be correlated to the long interval of negative δ¹³C_carb (Interval C). The Gaskiers glaciation is likely represented in Interval A, and Interval C corresponds to the Shuram excursion reported for other Ediacaran localities. Our correlations confirm the depth gradient of δ¹³C_carb in the Yangtze platform and imply that reductive conditions prevailed in the basinal section from the Early to Middle Ediacaran. Under such conditions, anaerobic degradation of organic carbon or methane perturbed the inorganic carbon isotopic compositions and was at least partly responsible for the depth gradient of δ¹³C_carb.     

The Upper Valanginian (Early Cretaceous) positive carbon-isotope event recorded in terrestrial plants

Our understanding of the ancient ocean-atmosphere system has focused on oceanic proxies. However, the study of terrestrial proxies is equally necessary to constrain our understanding of ancient climates and linkages between the terrestrial and oceanic carbon reservoirs. We have analyzed carbon-isotope ratios from fossil plant material through the Valanginian and Lower Hauterivian from a shallow-marine, ammonite-constrained succession in the Crimean Peninsula of the southern Ukraine in order to determine if the Upper Valanginian positive carbon-isotope excursion is expressed in the atmosphere. δ¹³C_plant values fluctuate around − 23‰ to − 22‰ for the Valanginian-Hauterivian, except during the Upper Valanginian where δ¹³C_plant values record a positive excursion to ∼− 18‰. Based upon ammonite biostratigraphy from Crimea, and in conjunction with a composite Tethyan marine δ¹³C_carb curve, several conclusions can be drawn: (1) the δ¹³C_plant record indicates that the atmospheric carbon reservoir was affected; (2) the defined ammonite correlations between Europe and Crimea are synchronous; and (3) a change in photosynthetic carbon-isotope fractionation, caused by a decrease in atmospheric pCO₂, occurred during the Upper Valanginian positive δ¹³C excursion. Our new data, combined with other paleoenvironmental and paleoclimatic information, indicate that the Upper Valanginian was a cool period (icehouse) and highlights that the Cretaceous period was interrupted by periods of cooling and was not an equable climate as previously thought.     

Expression of the Early Toarcian negative carbon-isotope excursion in separated carbonate microfractions (Jurassic,Paris Basin)

The causes of the pronounced negative excursion in carbon-isotope values that was recorded during the Early Toarcian Oceanic Anoxic Event (T-OAE) are still under debate, particularly with regard to the local versus global pattern of the excursion, and the extent to which recorded signals are under a diagenetic control. In this study we employ a novel microseparation technique in order to investigate the isotopic and mineralogical characteristics of different size fractions of the carbonate content from a Toarcian section recovered from the Sancerre–Couy borehole, southern Paris Basin. Beyond the recognition of a ? 6‰ δ¹³C excursion in the bulk carbonate content, our data also demonstrate that biogenic particles (such as coccoliths) and inorganic grains precipitated as early diagenetic phases (including dolomite) both record the excursion with the same magnitude. Although several black shales occur through the Paris Basin Toarcian section, it is only that associated with the onset of the OAE that coincides with a large negative carbon-isotope excursion. Taken together these observations indicate that during this event, the entire water column was characterized by homogeneous carbon-isotope values; such a pattern is incompatible with the idea that the negative excursion was generated simply through the upwelling of bottom waters enriched in re-mineralized organic carbon (cf. “the Küspert model”), since this would have required a strong vertical gradient in the water column. Additionally, the Paris Basin data show that the decrease in carbonate δ¹³C values during the OAE occurred in several discrete steps (each of some ? 2‰), as has previously been found for organic carbon substrates in other European sections. The stepped nature of the isotopic profile, which is part of a stratigraphic signature previously ascribed to Milankovitch forcing, is compatible with regular pulsed input of light carbon into the whole atmosphere–ocean system from a climatically sensitive source such as gas hydrate, or from thermal methanogenesis of organic-rich sediments in the Karoo–Ferrar large igneous province. Contrasts in the amplitude of the negative carbon-isotope excursion on a regional scale remain an important unexplained aspect of the Toarcian record.     

Seismicity and fluid geochemistry at Lassen Volcanic National Park,California: Evidence for two circulation cells in the hydrothermal system

Seismic analysis and geochemical interpretations provide evidence that two separate hydrothermal cells circulate within the greater Lassen hydrothermal system. One cell originates south to SW of Lassen Peak and within the Brokeoff Volcano depression where it forms a reservoir of hot fluid (235–270 °C) that boils to feed steam to the high-temperature fumarolic areas, and has a plume of degassed reservoir liquid that flows southward to emerge at Growler and Morgan Hot Springs. The second cell originates SSE to SE of Lassen Peak and flows southeastward along inferred faults of the Walker Lane belt (WLB) where it forms a reservoir of hot fluid (220–240 °C) that boils beneath Devils Kitchen and Boiling Springs Lake, and has an outflow plume of degassed liquid that boils again beneath Terminal Geyser. Three distinct seismogenic zones (identified as the West, Middle, and East seismic clusters) occur at shallow depths (< 6 km) in Lassen Volcanic National Park, SW to SSE of Lassen Peak and adjacent to areas of high-temperature (≤ 161 °C) fumarolic activity (Sulphur Works, Pilot Pinnacle, Little Hot Springs Valley, and Bumpass Hell) and an area of cold, weak gas emissions (Cold Boiling Lake). The three zones are located within the inferred Rockland caldera in response to interactions between deeply circulating meteoric water and hot brittle rock that overlies residual magma associated with the Lassen Volcanic Center. Earthquake focal mechanisms and stress inversions indicate primarily N–S oriented normal faulting and E–W extension, with some oblique faulting and right lateral shear in the East cluster. The different focal mechanisms as well as spatial and temporal earthquake patterns for the East cluster indicate a greater influence by regional tectonics and inferred faults within the WLB. A fourth, deeper (5–10 km) seismogenic zone (the Devils Kitchen seismic cluster) occurs SE of the East cluster and trends NNW from Sifford Mountain toward the Devils Kitchen thermal area where fumarolic temperatures are ≤ 123 °C. Lassen fumaroles discharge geothermal gases that indicate mixing between a N₂-rich, arc-type component and gases derived from air-saturated meteoric recharge water. Most gases have relatively weak isotopic indicators of upper mantle or volcanic components, except for gas from Sulphur Works where δ¹³C–CO₂, δ³⁴S–H₂S, and δ¹⁵N–N₂ values indicate a contribution from the mantle and a subducted sediment source in an arc volcanic setting.     

Influence of climate and hydrology on carbon in an early Miocene peatland

Our understanding of the hydrodynamic response of peatland to climate change is restricted to the Holocene, which confines our knowledge of the fundamental controls on this important carbon reservoir to recent sedimentary successions. To understand the interaction of peatland hydrodynamics, climate and the carbon cycle on longer time scales, a 95.4 m record from lower Miocene lignite from the Gippsland Basin, Australia is considered. δ¹³C and colour records for the lignite were created by analysing samples every 0.1 m. Solid-state ¹³C NMR results indicate that lignite colour is related to the relative abundance of aliphatic carbon. The lack of a direct correlation between colour and δ¹³C demonstrates that the δ¹³C signal has not been significantly influenced by the diagenetic processes that produce the colour. An offset correlation occurs between δ¹³C and colour with the degree of offset decreasing from 4.5 m at the base to about 0 m at the top. This offset is considered to represent a zone of surface influence that extends up to 20 m below the peat surface. Using numerical modelling we demonstrate that this zone of surface influence and its gradual decline in thickness could arise as a consequence of enhanced fluid flow in regions of high tensile stress within the unconfined peat body. The removal of lignin and its derivatives from the zone of surface influence will be favoured by cooler drier periods, with lower sea level and high hydraulic gradients across the peatland. Therefore in the early Miocene this peatland acted as a carbon source during global cooling.     

Himalayan metamorphic CO2 fluxes: Quantitative constraints from hydrothermal springs

Hot springs in the Marsyandi Valley, Nepal, vent CO₂ sourced from metamorphic fluids that mix with shallow groundwaters before degassing near the Earth's surface. The δ¹³C of spring waters ranges up to + 13‰, while that of the coexisting free gas phase is close to ? 4‰. Empirical and thermodynamic modelling of this isotopic fractionation suggests > 97 ± 1% CO₂ degassing. The calculated minimum total CO₂ degassing in the Marsyandi catchment is 5.4 × 10⁹ mol/yr from a Cl-based estimate of the spring water discharge to the Marsyandi River and the fraction of CO₂ degassed. Extrapolated to the whole of the Himalayas, this implies a probable minimum metamorphic CO₂ flux of 0.9 × 10¹² mol/yr, or ～ 13% of solid Earth CO₂ degassing. The calculated flux is a factor of three greater than the estimated CO₂ drawdown by silicate weathering in the Himalayas. Himalayan metamorphic degassing contributes a significant fraction of the global solid Earth CO₂ flux and implies that metamorphism may cause changes in long-term climate that oppose those resulting from the orogenic forcing of chemical weatherability.     

Trace elements and stable isotopic geochemistry of an Early Cambrian chert-phosphorite unit from the lower Yurtus Formation of the Sugetbrak section in the Tarim Basin

A chert-phosphorite unit from the Sugetbrak section in the Tarim Basin was analyzed for rare earth elements (Ce, Eu), redox sensitive proxies, and carbon isotopic compositions (δ¹³C_carb and δ ¹³C_org) in the lower Yurtus Formation of the Early Cambrian period. Redox sensitive element ratios (Th/U, V/Cr, Ni/Co, and V/Sc) were employed to determine the palaeoenvironmental conditions during this period. The ratios indicated that the depositional environment of the chert-phosphorite-black shale unit ranged from suboxic to anoxic. Negative Ce and positive Eu anomalies in the chert-phosphorite assemblages of the studied Yurtus Formation indicated the existence of a redox-stratified ocean, similar to that of South China. Overturn or upward expansion of the deep water-mass probably reached the shallow marine zone after the formation of the Yurtus phosphorites. The characteristics of the negative Ce anomaly may be due to phosphoritic inheritance from the Ce-depleted signature of the overlying water column. Subsequent hydrothermal inputs and reduced detrital supplies of the deep water caused by the upwelling affected certain redox sensitive elements in the sedimentary basin. δ ¹³C_carb and δ¹³C_org negative excursions in the Yurtus chert-phosphorite unit may be related to a transgression phase when episodic basinal upwelling moved ¹²C- and P-rich waters from the pelagic basin floor to the continental shelf. Although carbon isotopic compositions in the Yurtus chert-phosphorite assemblages may have suffered from diagenetic alteration, they can be used to probe diagenetic conditions. Multi-proxy geochemical studies indicated that the δ ¹³C_carb values of the Yurtus chert-phosphorite assemblages might be considered reflections of a predominantly suboxic environment that was subsequently affected by hydrothermal inputs due to the upwelling.     

Carbon remineralization in the Amazon–Guianas tropical mobile mudbelt: A sedimentary incinerator

The Amazon River spawns a vast mobile mudbelt extending ∼1600 km from the equator to the Orinoco delta. Deposits along the Amazon–Guianas coastline are characterized by some of the highest C_org remineralization rates reported for estuarine, deltaic, or shelf deposits, however, paradoxically, except where stabilized by mangroves or intertidal algal mats, they are usually suboxic and nonsulfidic. A combination of tides, wind-driven waves, and coastal currents forms massive fluid muds and mobile surface sediment layers ∼0.5–2 m thick which are dynamically refluxed and frequently reoxidized. Overall, the seabed functions as a periodically mixed batch reactor, efficiently remineralizing organic matter in a gigantic sedimentary incinerator of global importance. Amazon River material entering the head of this dynamic dispersal system carries an initial terrestrial sedimentary C_org loading of ∼ 0.7 mg C m⁻² particle surface area. Total C_org loading is lowered to ∼ 0.2 mg C m⁻² in the proximal delta topset, ∼60–70% of which remains of terrestrial origin. Loading decreases further to 0.12–0.14 mg C m⁻² (∼60% terrestrial) in mudbanks ∼600 km downdrift along French Guiana, values comparable to those found in the oligotrophic deepsea. DOC/ΣCO₂ ratios in pore waters of French Guiana mudbanks indicate that >90% of metabolized organic substrates are completely oxidized. Within the Amazon delta topset at the head of the dispersal system, both terrestrial and marine organic matter contribute substantially to early diagenetic remineralization, although reactive marine substrate dominates (∼60–70%). The conditional rate constant for terrestrial C_org in the delta topset is ∼0.2 a⁻¹. As sedimentary C_org is depleted during transit, marine sources become virtually the exclusive substrate for remineralization except very near the mangrove shoreline. The δ¹³C and Δ¹⁴C values of pore water ΣCO₂ in mudbanks demonstrate that the primary source of remineralized organic matter within ∼1 km of shore is a small quantity of bomb signature marine plankton (+80‰). Thus, fresh marine organic material is constantly entrained into mobile deposits and increasingly drives early diagenetic reactions along the transit path. Relatively refractory terrestrial C_org is lost more slowly but steadily during sedimentary refluxing and suboxic diagenesis. Amazon Fan deposits formed during low sea level stand largely bypassed this suboxic sedimentary incinerator and stored material with up to ∼3X the modern high stand inner shelf C_org load (Keil et al., 1997b. Proceedings of the Ocean Drilling Program, Scientific Results. Vol. 155. pp. 531–537). Sedimentary dynamics, including frequency and magnitude of remobilization, and the nature of dispersal systems are clearly key controls on diagenetic processes, biogeochemical cycling, and global C storage along the continental margins.     

Organic carbon isotope gradient and ocean stratification across the late Ediacaran-Early Cambrian Yangtze Platform

Organic carbon isotope(δ13Corg) data from two well-preserved sections across a shallow-to-deep water transect of the late Ediacaran-Early Cambrian Yangtze Platform in South China show significant temporal and spatial variations. In the shallow-water Jiulongwan-Jijiapo section, δ13Corg values of the late Ediacaran Dengying Formation range from -29‰ to -24‰. In the deep-water Longbizui section, δ13Corg values from time-equivalent strata of the Dengying Formation are mostly between –35‰ and -32‰. These new data, in combination with δ13Corg data reported from other sections in South China, reveal a 6‰–8‰ shallow-to-deep water δ13Corg gradient. High δ13Corg values(-30‰) occur mostly in shallow-water carbonate rocks, whereas low δ13Corg values(-32‰) dominate the deep-water black shale and chert. The large temporal and spatial δ13Corg variations imply limited buffering effect from a large dissolved organic carbon(DOC) reservoir that was inferred to have existed in Ediacaran-Early Cambrian oceans. Instead, δ13Corg variations between platform and basin sections are more likely caused by differential microbial biomass contribution to total organic matter. High δ13Corg values(-30‰) documented from shallow-water carbonates are within the range of typical Phanerozoic δ13Corg data and may record the isotope signature of organic matter from primary(photosynthetic) production. In contrast, low δ13Corg values(-32‰) from deep-water sections may have resulted from higher chemoautotrophic or methanotrophic biomass contribution to bulk organic matter in anoxic environments. The δ13Corg data provide indirect evidence for ocean stratification and episodic chemocline fluctuations in the Ediacaran-Early Cambrian Yangtze Platform.     

Mantle-derived carbon in Hercynian granites. Stable isotopes signatures and C/He associations in the thermomineral waters,N-Portugal

Na–HCO₃–CO₂-rich thermomineral waters issue in the N of Portugal, within the Galicia-Trás-os-Montes region, linked to a major NNE-trending fault, the so-called Penacova-Régua-Verin megalineament. Along this tectonic structure different occurrences of CO₂-rich thermomineral waters are found: Chaves hot waters (67 °C) and also several cold (16.1 °C) CO₂-rich waters. The δ²H and δ¹⁸O values of the thermomineral waters are similar to those of the local meteoric waters. The chemical composition of both hot and cold mineral waters suggests that water–rock reactions are mainly controlled by the amount of dissolved CO₂ (g) rather than by the water temperature. Stable carbon isotope data indicate an external CO₂ inorganic origin for the gas. δ¹³C_CO2 values ranging between ? 7.2‰ and ? 5.1‰ are consistent with a two-component mixture between crustal and mantle-derived CO₂. Such an assumption is supported by the ³He/⁴He ratios measured in the gas phase, are between 0.89 and 2.68 times the atmospheric ratio (Ra). These ratios which are higher than that those expected for a pure crustal origin (≈ 0.02 Ra), indicating that 10 to 30% of the He has originated from the upper mantle. Release of deep-seated fluids having a mantle-derived component in a region without recent volcanic activity indicates that extensive neo-tectonic structures originating during the Alpine Orogeny are still active (i.e., the Chaves Depression).     

Low-degree melting of a metasomatized lithospheric mantle for the origin of Cenozoic Yulong monzogranite-porphyry,east Tibet: Geochemical and Sr–Nd–Pb–Hf isotopic constraints

SHRIMP zircon U–Pb dating, mineral chemical, element geochemical and Sr–Nd–Pb–Hf isotopic data have been determined for the Yulong monzogranite-porphyry in the eastern Tibet, China. The Yulong porphyry was emplaced into Triassic strata at about 39 Ma. The rocks are weakly peraluminous and show shoshonitic affinity, i.e., alkalis-rich, high K₂O contents with high K₂O / Na₂O ratios, enrichment in LREE and LILE. They also show some affinities with the adakite, e.g., high SiO₂ and Al₂O₃, and low MgO contents, depleted in Y and Yb, and enrichment in Sr with high Sr / Y and La / Yb ratios, and no Eu anomalies. The Yulong porphyry has radiogenic ⁸⁷Sr / ⁸⁶Sr (0.7063–0.7070) and unradiogenic ¹⁴³Nd / ¹⁴⁴Nd (ε_Nd = − 2.0 to − 3.0) ratios. The Pb isotopic compositions of feldspar phenocrysts separated from the Yulong porphyry show a narrow range of ²⁰⁶Pb / ²⁰⁴Pb ratios (18.71–18.82) and unusually radiogenic ²⁰⁷Pb / ²⁰⁴Pb (15.65–15.67) and ²⁰⁸Pb / ²⁰⁴Pb (38.87–39.00) ratios. In situ Hf isotopic composition of zircons that have been SHRIMP U–Pb dated is characterized by clearly positive initial ε_Hf values, ranging from + 3.1 to + 5.9, most between + 4 and + 5. Phenocryst clinopyroxene geothermometry of the Yulong porphyry indicates that the primary magmas had anomalously high temperature (> 1200 °C). The source depth for the Yulong porphyry is at least 100 km inferred by the metasomatic volatile phase (phlogopite–carbonate) relations. Detailed geochemical and Sr–Nd–Pb–Hf isotopic compositions not only rule out fractional crystallization or assimilation-fractional crystallization processes, but also deny the possibility of partial melting of subducted oceanic crust or basaltic lower crust. Instead, low degree (1–5%) partial melting of a metasomatized lithosphere (phlogopite–garnet clinopyroxenite) is compatible with the data. This example gives a case study that granite can be derived directly by partial melting of an enriched lithospheric mantle, which is important to understand the source and origin of diverse granites.     

Isotope shifts in the Late Permian of the Delaware Basin,Texas, precisely timed by varved sediments

Closely spaced samples (285 in number) of varved sediments from the Upper Permian in Delaware Basin, Texas, have been analyzed for δ¹³C_carb, δ¹³C_org, δ¹⁸O_carb, C_org, C_carb, and calcite/dolomite. δ¹³C records a dramatic rise from ?2.8 to +5.7‰ in only 4400 years, detected in three sections across the basin, extrapolating smoothly through a 600-year interruption by a local (west side of the basin) fresh-water inflow evidenced by low δ¹⁸O. This continuity and low C_org within the basin, both indicate that the excess net deposition of C_org, necessary to generate the rise in δ¹³C, took place in the ocean external to the Delaware Basin. Correlation with similar records from the Zechstein Basin suggest that the event was world-wide, although this poses obvious difficulties for the carbon cycle. The rate of rise of δ¹³C, and its sustained high level, must imply conversions of oxidized carbon to reduced carbon that are very large depending on which reservoirs were involved.     

Geochemical characteristics of pyrolysis gas from epimetamorphic rocks in the northern basement of Songliao Basin,Northeast China

The Xushen gas field, located in the north of Songliao Basin, is a potential giant gas area for China in the future. Its proved reserves have exceeded 1000×10⁸ m³ by the end of 2005. But, the origin of natural gases from the deep strata is still in debating. Epimetamorphic rocks as a potential gas source are widely spreading in the northern basement of Songliao Basin. According to pyrolysis experiments for these rocks in the semi-confined system, gas production and geochemistry of alkane gases are discussed in this paper. The Carboniferous-Permian epimetamorphic rocks were heated from 300°C to 550°C, with temperature interval of 50°C. The gas production was quantified and measured for chemical and carbon isotopic compositions. Results show that δ ¹³C₁ is less than ?20‰, carbon isotope trend of alkane gas is δ ¹³C₁<δ ¹³C₂<δ ¹³C₃ or δ ¹³C₁<δ ¹³C₂>δ ¹³C₃, these features suggest that the gas would be coal-type gas at high-over maturity, not be inorganic gas with reversal trend of gaseous alkanes (δ ¹³C₁>δ ¹³C₂>δ ¹³C₃). These characteristics of carbon isotopes are similar with the natural gas from the basin basement, but disagree with gas from the Xingcheng reservoir. Thus, the mixing gases from the pyrolysis gas with coal-typed gases at high-over maturity or oil-typed gases do not cause the reversal trend of carbon isotopes. The gas generation intensity for epimetamorphic rocks is 3.0×10⁸–23.8×10⁸ m³/km², corresponding to R _o from 2.0% to 3.5% for organic matter.     

Latitudinal patterns of export production recorded in surface sediments of the Chilean Patagonian fjords (41–55°S) as a response to water column productivity

The Chilean Patagonian fjords region (41–56°S) is characterized by highly complex geomorphology and hydrographic conditions, and strong seasonal and latitudinal patterns in precipitation, freshwater discharge, glacier coverage, and light regime; all of these directly affect biological production in the water column. In this study, we compiled published and new information on water column properties (primary production, nutrients) and surface sediment characteristics (biogenic opal, organic carbon, molar C/N, bulk sedimentary δ¹³C_org) from the Chilean Patagonian fjords between 41°S and 55°S, describing herein the latitudinal pattern of water column productivity and its imprint in the underlying sediments. Based on information collected at 188 water column and 118 sediment sampling sites, we grouped the Chilean fjords into four main zones: Inner Sea of Chiloé (41° to ～44°S), Northern Patagonia (44° to ～47°S), Central Patagonia (48–51°S), and Southern Patagonia (Magellan Strait region between 52° and 55°S). Primary production in the Chilean Patagonian fjords was the highest in spring–summer, reflecting the seasonal pattern of water column productivity. A clear north–south latitudinal pattern in primary production was observed, with the highest average spring and summer estimates in the Inner Sea of Chiloé (2427 and 5860 mg C m^?2 d^?1) and Northern Patagonia (1667 and 2616 mg C m^?2 d^?1). This pattern was closely related to the higher availability of nutrients, greater solar radiation, and extended photoperiod during the productive season in these two zones. The lowest spring value was found in Caleta Tortel, Central Patagonia (91 mg C m^?2 d^?1), a site heavily influenced by glacier meltwater and river discharge loaded with glacial sediments. Biogenic opal, an important constituent of the Chilean fjord surface sediments (Si_OPAL ～1–13%), reproduced the general north–south pattern of primary production and was directly related to water column silicic acid concentrations. Surface sediments were also rich in organic carbon content and the highest values corresponded to locations far away from glacier influence, sites within fjords, and/or semi-enclosed and protected basins, reflecting both autochthonous (water column productivity) and allochthonous sources (contribution of terrestrial organic matter from fluvial input to the fjords). A gradient was observed from the more oceanic sites to the fjord heads (west–east) in terms of bulk sedimentary δ¹³C_org and C/N ratios; the more depleted (δ¹³C_org ?26‰) and higher C/N (23) values corresponded to areas close to rivers and glaciers. A comparison of the Chilean Patagonian fjords with other fjord systems in the world revealed high variability in primary production for all fjord systems as well as similar surface sediment geochemistry due to the mixing of marine and terrestrial organic carbon.     

Carbon-isotope record of the Early Jurassic (Toarcian) Oceanic Anoxic Event from fossil wood and marine carbonate (Lusitanian Basin,Portugal)

The Toarcian Oceanic Anoxic Event (OAE) in the Early Jurassic (∼ 183 Ma ago) was characterized by widespread near-synchronous deposition of organic-rich shales in marine settings, as well as perturbations to several isotopic systems. Characteristically, two positive carbon-isotope excursions in a range of materials are separated by an abrupt negative shift. Carbon-isotope profiles from Toarcian fossil wood collected in England and Denmark have previously been shown to exhibit this large drop (∼ − 7‰) in δ¹³C values, interpreted as due to an injection of isotopically light CO₂ into the ocean–atmosphere system. However, the global nature of this excursion has been challenged on the basis of carbon-isotope data from nektonic marine molluscs (belemnites), which exhibit heavier than expected carbon-isotope values. Here we present new data, principally from fossil wood and bulk carbonate collected at centimetre scale from a hemipelagic section at Peniche, coastal Portugal. This section is low in organic carbon (average TOC = ∼ 0.5%), and the samples should not have suffered significant diagenetic contamination by organic carbon of marine origin. The carbon-isotope profile based on wood shows two positive excursions separated by a large and abrupt negative excursion, which parallels exactly the profile based on bulk carbonate samples from the same section, albeit with approximately twice the amplitude (∼ − 8‰ in wood versus ∼ − 3.5‰ in carbonate). These data indicate that the negative carbon-isotope excursion affected the atmosphere and, by implication, the global ocean as well. The difference in amplitude between terrestrial organic and marine carbonate curves can be explained by greater water availability in the terrestrial environment during the negative excursion, for which there is independent evidence from marine osmium-isotope records and, plausibly, changes in atmospheric CO₂ content, for which independent evidence is also available. The Peniche succession is also notable for the occurrence of re-deposited sediments: their lowest occurrence coincides with the base of the negative excursion and their highest occurrence coincides with its top. Thus, slope instability and sediment supply could have been strongly linked to the global environmental perturbation, an association that may misleadingly simulate the effects of sea-level fall.     

Stable carbon and hydrogen isotopes of gases from the large tight gas fields in China

By the end of the year 2010,a total of 15 large tight gas fields have been found in China,located in the Ordos,Sichuan,and Tarim basins.The annual production and total reserves of these fields in 2010 were 222.5×108and 28657×108m3,respectively,accounting for 23.5%and 37.3%,respectively,of the total annual production and reserves of natural gases in China.They took a major part of all natural gas production and reserves in China.According to the analyses of 81 gas samples,the stable carbon and hydrogen isotopic compositions of tight gases in China have following characteristics:(1)Plots of 13C1-13C2-13C3,13C1-C1/C2+3and 13C1-13C2demonstrate the coal-derived origin of tight gases in China;(2)For the primary alkane gases,both carbon and hydrogen isotopic values increase with increasing molecular mass,i.e.,13C113C213C313C4and2H12H22H3;(3)The isotopic differences of 13C2-13C1,13C3-13C1,2H2-2H1and 2H3-2H1decrease with increasing Ro(%)and C1/C1–4;(4)There are seven causes for the carbon and hydrogen isotopic reversal,however,the carbon and hydrogen isotopic reversal of tight gases in China is caused mainly by multiple stages of gas charge and accumulation.