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1.
Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian–Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, δ13Corg values lie mostly between −30‰ and −27‰, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C3 land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low δ13Corg values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian–Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.  相似文献   

2.
A reaction-transport model was used to infer the long-term evolution of anaerobic organic matter degradation in Cretaceous black shales from the distribution of authigenic barite in sediments drilled at Demerara Rise (ODP Leg 207, Site 1258). In these sediments, sulfate-reduction and methanogenesis are the major pathways of organic matter decomposition and the depth-distribution of authigenic barite serves as an indicator for the temporal evolution of the sulfate-methane transition zone (SMTZ), the strength of the biogenic methane flux and, ultimately, the organic matter reactivity in the black shales over geological timescales. Organic matter degradation is described according to the reactive continuum model approach and parameters values are determined by inverse modeling, based on present-day porewater and authigenic barite profiles. Fully transient simulations were performed over a period of 100 Myrs and indicate that important features of the biogeochemical dynamics are associated to changes in the boundary forcing. Hiatuses in sediment accumulation rate result in quasi-steady-state conditions and lead to distinct accumulations of authigenic barites in the SMTZ. The inversely determined parameters reveal that the reactivity of the organic matter was already low (apparent first order rate constant ) at the time of its deposition in the Cretaceous. The geochemical characteristics of sediments drilled at Demerara Rise, as well as the presence of specific biomarkers, suggest that this low reactivity is most likely due to the euxinic palaeo-conditions which favored the sulfurization of the organic matter. Simulation results predict average initial organic carbon contents between 8.1 and 9.5 wt%, implying a high preservation efficiency of the organic matter (between 79% and 89%). Calculated mass accumulation rates (between 0.43 and 0.5 ) compare well with estimations for the western basin of the Cretaceous southern North Atlantic. Simulation results thus indicate that the enhanced preservation of organic matter under euxinic conditions may have been the main cause for the formation of organic-rich Cretaceous black shales at Demerara Rise.  相似文献   

3.
Five sites located on a bathymetric transect of the distal Demerara Rise were studied by ODP Leg 207. Albian sediments of essentially terrigenous nature (clay, siltstone, sandstone) are the oldest drilled stratigraphic levels and form apparently the top of the synrift sequence. They are overlain by Cenomanian to Santonian finely laminated black shales, rich in organic matter of marine origin, which accumulated on a thermally subsiding ramp. Early Campanian hiatuses are thought to be the result of final disjunction of Demerara Rise (South America) from Africa and the onset of deep water communication between the two Atlantic basins (south and central). The overlying Uppermost Cretaceous–Oligocene chalk includes rich and diversified calcareous plankton assemblages, as well as two radiolarian-rich intervals (Late Campanian and Middle Eocene). A complex erosional surface developed during the Late Oligocene–Early Miocene. Sedimentation was impeded since then on the intermediate and deep sites of Demerara Rise, possibly due to the action of deep submarine currents. To cite this article: T. Danelian et al., C. R. Geoscience 337 (2005).  相似文献   

4.
Liquid chromatography, multi-stage mass spectrometry (LC-MSn) of acetone extracts confirms the presence of mesochlorophyllone in the mid-Cretaceous black shales of Demerara Rise. This finding represents molecular confirmation of the oldest primary chlorins in the geologic record and is evidence for a chlorophyll a source for bicycloalkanoporphyrins in the Demerara Rise black shales.  相似文献   

5.
The organic rich Safer shales exposed in the north-central part of onshore Marib-Shabowah Basin are evaluated and their depositional environments are interpreted. Total organic carbon contents (TOC) of the shales range from 1.02–16.8 wt%, and yield hydrogen index (HI) values ranging from 130 to 820 mg HC/g TOC, consistent with mainly Type II with minor contributions from Type I and mixed Types II–III kerogens. The Safer shale samples have vitrinite reflectance values in the range of 0.5–1.0 Ro%, indicating early mature to peak mature stage for oil generation. Tmax values range from 429–438 °C, which are in reasonably good agreement with vitrinite reflectance data. Kerogen microscopy shows that the Safer shales are characterized by high amounts of organic matter, consisting predominantly of yellow fluorescing amorphous organic matter and alginite of marine origin. This is supported by their high content of hydrogen rich Type II and I oil-prone kerogen.The biomarker distributions of the Upper Jurassic Safer extracts are characterized by dominant low to medium molecular weight compounds (n-C14 to n-C20), low Pr/Ph ratio (<1.0), high phytane/n-C18 ratios (0.82–2.68), and predominant regular sterane C27. All biomarker parameters clearly indicate that the organic matter was derived from marine algal inputs and deposited under anoxic (reducing) conditions. Hypersaline conditions also prevailed during deposition of these sediments, as indicated by the presence of gammacerane.  相似文献   

6.
A transport-reaction model was designed to identify the combination and importance of biogeochemical processes operating in four sites drilled during ODP Leg 207 (Demerara Rise, Equatorial Atlantic). Almost 100 Ma after their deposition, deeply buried Cretaceous black shales still act as active bioreactors in great sediment depths and control the biogeochemical reaction network of the whole sediment column. According to a model calibrated at the four drill sites through inverse modeling techniques, methanogenesis could be identified as a key process that dominates not only organic matter degradation but also sulfate availability through the anaerobic oxidation of methane above the black shales. A complete depletion of sulfate within the black shale sequences promotes the remobilization of biogenic barium that reprecipitates as authigenic barite at the top of the sulfate depletion zone. Temporal dynamics of degradation processes caused continuous shifts of the barite precipitation zone during burial, thus inhibiting the formation of an authigenic barite front or causing the dissolution of earlier formed fronts. Major deviations of pore water sulfate profiles from a linear gradient coincide with depths of decelerated or accelerated transport caused by local porosity minima or maxima. Model-determined reaction rates are by far lower than those found in shallower sediments due to the low metabolic activities that are characteristic for the Deep Biosphere. But even after almost 100 Ma, changing organic matter quality still influences the degradation within the black shale sequences, as it is indicated by model results.  相似文献   

7.
Suspended solids found in porewaters obtained in waterlogged soil sequences that included representative laterite–podzol transitions, associated brooks and major rivers of the Rio Negro watershed (Brazil) were studied using electron paramagnetic resonance (EPR) and Fourier-transform infrared spectroscopies. The main goal was to ascertain sources and track the evolution of suspended matter using a ubiquitous chemical species, FeIII complexed to organic matter (FeOM). Three size fractions were separated by tangential-flow (ultra)filtration: particulate (> 0.2 μm), dense (P) and light (Ps), and colloidal (5 kD < Col. < 0.2 μm) fractions. Quantitative results were acquired for Col. and Ps fractions which are predominantly organic in nature.FeOM concentration (in ‰ dry weight) was determined to be relatively low in suspended solids found in black waters from podzol porewaters and brooks whereas in the main rivers it was several times higher. FeOM concentrations were also correlated with Fe(II)/Fe(III) ratios in solution; these ratios were high in podzol porewaters and low in the rivers. Considering that organic complexation of Fe(II) is minor when compared to that of Fe(III), two interpretations were proposed to account for the above observation. First, [FeOM] was assumed to be distributed along a mixing line, with the clear waters from laterites and the black waters from podzols being its end-members. Consequently, [FeOM] can be used to trace the source of suspended material. Second, dissolved Fe(II) from podzol areas was considered to be progressively oxidized as pore waters move towards the mainstream. According to this mechanism, iron is complexed by organic matter or precipitated as oxides, thus producing an evolution of colloidal matter. As a result of these mechanisms' action, both the high production of Fe(II) and organic matter at the waterlogged podzol–laterite transition areas are major factors affecting iron export in the Rio Negro watershed.  相似文献   

8.
Total organic carbon content (TOC), trace element and platinum-group element (PGE) concentrations were determined in the black shales of the Lower Cambrian Niutitang Formation in the Nayong area, Guizhou Province, South China, in order to study the polymetallic Ni–Mo–PGE mineralization. The results demonstrate that numerous elements are enriched in the polymetallic ores compared to those of the nearby black shale, particularly Ni, Mo, Zn, TOC and total PGE, which can reach up to 7.03 wt.%, 8.49 wt.%, 11.7 wt.%, 11.5 wt.% and 943 ppb, respectively. The elemental enrichment distribution patterns are similar to those in the Zunyi and Zhangjiajie areas except that the Nayong location is exceptionally enriched in Zn. Whereas positive correlations are observed between the ore elements of the polymetallic ores, no such correlations are observed in the black shale. These positively correlated metallic elements are classified into three groups: Co–Ni–Cu–PGE, Zn–Cd–Pb and Mo–Tl–TOC. The geological and geochemical features of these elements suggest that Proterozoic and Early Palaeozoic mafic and ultramafic rocks, dolomites and/or Pb–Zn deposits of the Neoproterozoic Dengying Formation and seawater could be the principal sources for Co–Ni–Cu–PGE, Zn–Cd–Pb, and Mo–Tl–TOC, respectively. Furthermore, the chondrite-normalized patterns of PGEs with Pd/Pt, Pd/Ir and Pt/Ir indicate that PGE enrichment of the polymetallic ores is most likely related to hydrothermal processes associated with the mafic rocks. In contrast, PGE enrichment in the black shale resembles that of the marine oil shale with terrigenous and seawater contributions. Our investigations of TOC, trace elements and PGE geochemistry suggest that multiple sources along with submarine hydrothermal and biological contributions might be responsible for the formation of the polymetallic Ni–Mo–PGE mineralization in the black shales of the Lower Cambrian Niutitang Formation across southern China.  相似文献   

9.
The Early Cambrian black shale sequence of the Niutitang Formation in South China hosts a synsedimentary, organic carbon-rich, polymetallic sulfide layer with extreme metal concentrations, locally mined as polymetallic Ni–Mo–PGE–Au ore. In combination with previously reported data, we present Mo isotope, platinum-group element (PGE), and trace and rare-earth element (REE) data for the polymetallic sulfide ores and host black shales from four mine sites (Dazhuliushui and Maluhe in Guizhou Province, and Sancha and Cili in Hunan Province, respectively), several hundred kilometers apart. The polymetallic sulfide ores have consistently heavy δ98/95Mo values of 0.94 to 1.38‰ (avg. 1.13 ± 0.14‰, 1σ, n = 11), and the host black shale and phosphorite have slightly more variable δ98/95Mo values of 0.81‰ to 1.70‰ (n = 14). This latter variation is due to variable paleoenvironmental conditions from suboxic to euxinic, and partly closed-system fractionation in isolated marine sedimentary basins. Both the polymetallic sulfides and host black shales show PGE distribution patterns similar to that of present-day seawater, but different from those of ancient submarine-hydrothermal deposits and modern submarine hydrothermal fluids. The polymetallic sulfide bed has a generally consistent metal enrichment by a factor of 107 compared to present-day seawater. PAAS-normalized REE + Y patterns of the polymetallic sulfide bed are characterized by a remarkably positive Y anomaly, consistent with an origin of the REE predominantly from seawater. Small positive Eu anomalies in some of the sulfide ores could reflect minor hydrothermal components involved. The Mo isotope, PGE, and trace and rare-earth element geochemical data suggest that metals in the polymetallic Ni–Mo–PGE–Au sulfide ore layer were scavenged mostly from Early Cambrian seawater, by both in-situ precipitation and local re-deposition of sulfide clasts.  相似文献   

10.
Late Cretaceous shales of the Fika Formation in the Chad (Bornu) Basin, northeastern Nigeria, were analysed to define paleoenvironment and source of the organic matter, and their relation to tectonic setting. The organic carbon and sulphur contents of Fika shale samples are in the range of 0.51–2.13 and 0.31–1.65 wt.%, respectively, pointing that these shales were deposited in suboxic-anoxic marine conditions. The biomarker and chemical compositions provide evidence for a major contribution of aquatic algae and microorganisms with minor terrigenous organic matter input. Moderate salinity stratification and relatively anoxic-suboxic bottom water conditions are also likely in the Fika shales. Therefore, stratified water column with moderate salinity and relatively anoxic-suboxic bottom water conditions have contributed to organic matter (OM) preservation in the Fika shale layer. Fika shale samples are rich in SiO2 (54.80 wt.%), followed by Al2O3 (23.75 wt.%) and Fe2O3 (10.19 wt.%). Compared with average shale, the analysed shale samples are obviously enriched in Al2O3 (23.75 wt.%), TiO2 (1.34 wt.%), and P2O5 (0.30 wt.%), indicating that these sediments are rich in clay minerals and represent a good possibility for enhanced organic matter production and enrichment.Plots of Fika shale on bivariate discriminant function diagram suggest an active continental margin setting for the provenance. The inferred tectonic setting for the late Cretaceous shales of the Fika Formation of the Chad (Bornu) Basin is in agreement with the tectonic evolutionary history of the west and central Africa during the Cretaceous period.  相似文献   

11.
S.M. Lev  J.K. Filer  P. Tomascak 《Earth》2008,86(1-4):1-14
Black shales from the southern Appalachian Basin and the southwest Welsh Basin have anomalous U–Pb and Nd model ages suggesting syn- and post-depositional resetting of the Sm–Nd and U–Pb isotopic systems. This alteration to the primary detrital signature of these two shale sequences is indicative of black shale diagenetic/depositional processes that obscure paleo-environmental and provenance information recorded prior to and during deposition. The trace element and isotopic signatures of these two shale sequences reveal a syn-/post-depositional history that is de-coupled from the coeval orogenic history of the region making it difficult to reconstruct the tectonic and oceanographic conditions present at the time of deposition.Both the Ordovivian Welsh Basin and the Devonian Appalachian Basin sequences host REE- and U-bearing diagenetic phosphate minerals that play a critical role in the whole rock REE and U budgets. In the Welsh Basin shales, early diagenetic apatite and a later monazite phase dominate the REE budget and cause the redistribution of REE early in the basin's history (ca. 460 Ma). This redistribution is recorded by the Sm–Nd system (450 ± 90 Ma) and the Nd model ages that are anomalously old by as much as 20% (TDM > 2.0 Ga). This early history is complicated by a Permo-Triassic fluid event affecting the whole rock U-budget and resetting the U–Pb isotopic system at 193 ± 45 Ma. The Appalachian Basin sequence appears to have a much less complicated history yet still records a significant disturbance in both the Sm–Nd isotopic system (392 ± 76 Ma) and the Pb isotopic system (340 ± 50 Ma) at about the time of deposition (ca. 365 Ma).These two sequences suggest a pattern of diagenetic disturbance common to black shales. These processes are unique to black shales and must be considered when interpreting provenance and paleo-environmental information from the black shale sequences. Although these rocks are susceptible to alteration, the alteration may provide extensive information on the post-depositional history of the basin while still retaining some primary depositional information. If black shale processes are considered during the interpretation of isotopic and trace element signatures from organic-rich shales, it may be possible to recover an extensive basin history.  相似文献   

12.
Organic matter is an important factor that cannot be neglected when considering global carbon cycle. New data including organic matter geochemistry at the small watershed scale are needed to elaborate more constrained carbon cycle and climatic models. The objectives are to estimate the DOC and DIC yields exported from small tropical watersheds and to give strong constraints on the carbon hydrodynamic of these systems. To answer these questions, we have studied the geochemistry of eleven small watersheds around Basse-Terre volcanic Island in the French West Indies during different hydrological regimes from 2006 to 2008 (i.e. low water level versus floods). We propose a complete set of carbon measurements, including DOC and DIC concentrations, δ13C data, and less commonly, some spectroscopic indicators of the nature of organic matter. The DOC/DIC ratio varies between 0.07 and 0.30 in low water level and between 0.25 and 1.97 during floods, indicating that organic matter is mainly exported during flood events. On the light of the isotopic composition of DOC, ranging from ? 32.8 to ? 26.2‰ during low water level and from ? 30.1 to ? 27.2‰ during floods, we demonstrate that export of organic carbon is mainly controlled by perennial saprolite groundwaters, except for flood events during which rivers are also strongly influenced by soil erosion. The mean annual yields ranged from 2.5 to 5.7 t km? 2 year? 1 for the DOC and from 4.8 to 19.6 t km? 2 year? 1 for the DIC and exhibit a non-linear relationship with slopes of watersheds. The flash floods explain around 60% of the annual DOC flux and between 25 and 45% of the DIC flux, highlighting the important role of these extreme meteorological events on global carbon export in small tropical volcanic islands. From a carbon mass balance point of view the exports of dissolved carbon from small volcanic islands are important and should be included in global organic carbon budgets.  相似文献   

13.
The Jurassic–Lower Cretaceous aged carbonate sequence is widely exposed in the southern zone of Eastern Pontides. Aptian black bituminous limestone is found in the upper part of this sequence in the Kale area (Gümüşhane). This limestone contains faunal remains (e.g., gastropod, ostracod, characean stems and miliolid type benthic foraminifera) that indicate a freshwater, lacustrine depositional environment.The total organic carbon (TOC) values of the bituminous limestone samples range from 0.11–1.30% with an average TOC value of 0.54%. The hydrogen index (HI) varies from 119–448 mg HC/g TOC (average HI 298 mg HC/g TOC) indicating that the limestone contains gas prone as well as oil prone organic matter. Pyrolysis data prove that the organic matter content in the bituminous limestone consists of Type II kerogen. The average Tmax value for bituminous limestone samples is 438 °C (434–448 °C). Bitumen/TOC ratios for bituminous limestone are 0.05 and 0.04. The Tmax values and the ratios indicate that the bituminous limestone samples contain early mature to mature organic matter.Analysis of solvent extracts from the two richest bituminous limestones show a predominance of high carbon number (C26–C30) n-alkanes. The Pr/Ph ratio and CPI value are 1.34 and 0.96, respectively. C29 is the dominant sterane, with C29 > C27 > C28. The bituminous limestone samples have low C22/C21 ratios, high C24/C23 tricyclic terpane ratios and very low C31R/C30 hopane ratios (<0.25). These data are consistent with the bituminous limestones being deposited in a lacustrine environment.  相似文献   

14.
The organic geochemical methods of hydrocarbon prospecting involve the characterization of sedimentary organic matter in terms of its abundance, source and thermal maturity, which are essential prerequisites for a hydrocarbon source rock. In the present study, evaluation of organic matter in the outcrop shale samples from the Semri and Kaimur Groups of Vindhyan basin was carried out using Rock Eval pyrolysis. Also, the adsorbed low molecular weight hydrocarbons, methane, ethane, propane and butane, were investigated in the near surface soils to infer the generation of hydrocarbons in the Vindhyan basin. The Total Organic Carbon (TOC) content in shales ranges between 0.04% and 1.43%. The S1 (thermally liberated free hydrocarbons) values range between 0.01–0.09 mgHC/gRock (milligram hydrocarbon per gram of rock sample), whereas the S2 (hydrocarbons from cracking of kerogen) show the values between 0.01 and 0.14 mgHC/gRock. Based on the Tmax (temperature at highest yield of S2) and the hydrogen index (HI) correlations, the organic matter is characterized by Type III kerogen. The adsorbed soil gas, CH4 (C1), C2H6 (C2), C3H8 (C3) and nC4H10, (nC4), concentrations measured in the soil samples from the eastern part of Vindhyan basin (Son Valley) vary from 0 to 186 ppb, 0 to 4 ppb, 0 to 5 ppb, and 0 to 1 ppb, respectively. The stable carbon isotope values for the desorbed methane (δ13C1) and ethane (δ13C2) range between −45.7‰ to −25.2‰ and −35.3‰ to −20.19‰ (VPDB), respectively suggesting a thermogenic source for these hydrocarbons. High concentrations of thermogenic hydrocarbons are characteristic of areas around Sagar, Narsinghpur, Katni and Satna in the Son Valley. The light hydrocarbon concentrations (C1–C4) in near surface soils of the western Vindhyan basin around Chambal Valley have been reported to vary between 1–2547 ppb, 1–558 ppb, 1–181 ppb, 1–37 ppb and 1–32 ppb, respectively with high concentrations around Baran-Jhalawar-Bhanpur-Garot regions (Kumar et al., 2006). The light gaseous hydrocarbon anomalies are coincident with the wrench faults (Kota – Dholpur, Ratlam – Shivpuri, Kannod – Damoh, Son Banspur – Rewa wrench) in the Vindhyan basin, which may provide conducive pathways for the migration of the hydrocarbons towards the near surface soils.  相似文献   

15.
A series of methane (CH4) adsorption experiments on bulk organic rich shales and their isolated kerogens were conducted at 35 °C, 50 °C and 65 °C and CH4 pressure of up to 15 MPa under dry conditions. Samples from the Eocene Green River Formation, Devonian–Mississippian Woodford Shale and Upper Cretaceous Cameo coal were studied to examine how differences in organic matter type affect natural gas adsorption. Vitrinite reflectance values of these samples ranged from 0.56–0.58 %Ro. In addition, thermal maturity effects were determined on three Mississippian Barnett Shale samples with measured vitrinite reflectance values of 0.58, 0.81 and 2.01 %Ro.For all bulk and isolated kerogen samples, the total amount of methane adsorbed was directly proportional to the total organic carbon (TOC) content of the sample and the average maximum amount of gas sorption was 1.36 mmol of methane per gram of TOC. These results indicate that sorption on organic matter plays a critical role in shale-gas storage. Under the experimental conditions, differences in thermal maturity showed no significant effect on the total amount of gas sorbed. Experimental sorption isotherms could be fitted with good accuracy by the Langmuir function by adjusting the Langmuir pressure (PL) and maximum sorption capacity (Γmax). The lowest maturity sample (%Ro = 0.56) displayed a Langmuir pressure (PL) of 5.15 MPa, significantly larger than the 2.33 MPa observed for the highest maturity (%Ro > 2.01) sample at 50 °C.The value of the Langmuir pressure (PL) changes with kerogen type in the following sequence: type I > type II > type III. The thermodynamic parameters of CH4 adsorption on organic rich shales were determined based on the experimental CH4 isotherms. For the adsorption of CH4 on organic rich shales and their isolated kerogen, the heat of adsorption (q) and the standard entropy (Δs0) range from 7.3–28.0 kJ/mol and from −36.2 to −92.2 J/mol/K, respectively.  相似文献   

16.
We evaluated the structure of planktonic communities and paleoenvironmental conditions throughout the Cenomanian–Turonian Oceanic Anoxic Event (OAE2) by studying bulk geochemical properties and the molecular isotopic composition of source-specific hydrocarbons from organic-rich sediments deposited in an intrashelf basin at the Levant Platform, central Jordan. High concentrations of desmethyl and 4-methylsteranes as well as dinosteranes indicate that marine algae including dinoflagellates were the main primary producing organisms. The presence of 2-methylhopanes and 13C-enriched hopanes, in addition to isotopically enriched aryl isoprenoids, evidenced the contribution of cyanobacteria and green sulfur bacteria, respectively. Additionally, variable but fairly low δ15N values during OAE2 suggest the occurrence of diazotrophy as a likely important process fueling primary production during OAE2 in this stratified/anoxic continental platform. Variations in the relative contribution of biomarkers revealed changes in planktonic communities associated with sea level change and water column stratification. OAE2 was characterized by strong stratification, anoxic bottom waters and a deep chemocline, as evidenced by high gammacerane and homohopane indices and the absence of photic zone euxinia (PZE) markers, respectively. However, the presence of isorenieratane and its derivatives in post-OAE black shales points to a shoaling of the chemocline and to PZE. This interval was also characterized by an exceptionally high abundance of chlorophyll-derived pristane and phytane (up to 2 mg g?1 TOC), likely as a result of highly enhanced primary production and organic matter preservation. Remarkably, this high productivity event co-occurs with an exceptionally high abundance of calcispheres reported elsewhere to be part of a global bio-event.  相似文献   

17.
《Gondwana Research》2014,25(3):1057-1069
The appearance of multicellular animals and subsequent radiation during the Ediacaran/Cambrian transition may have significantly changed the oceanic ecosystem. Nitrogen cycling is essential for primary productivity and thus its connection to animal evolution is important for understanding the co-evolution of the Earth's environment and life. Here, we first report on coupled organic carbon and nitrogen isotope chemostratigraphy from the entire Ediacaran to Early Cambrian period by using drill core samples from the Yangtze Platform, South China. The results show that δ15NTN values were high (~ + 6‰) until middle Ediacaran, gradually dropping down to − 1‰ at the earliest Cambrian, then rising back to + 4‰ in the end of the Early Cambrian. Organic carbon and nitrogen contents widely varied with a relatively constant C/N ratio in each stratigraphic unit, and do not apparently control the carbon and nitrogen isotopic trends. These observations suggest that the δ15NTN and C/N trends mainly reflect secular changes in nitrogen cycling in the Yangtze Platform. Onset of the observed negative N isotope excursion coincided with a global carbon isotope excursion event (Shuram excursion). Before the Shuram event, the high δ15N probably reflects denitrification in a nitrate-limited oceanic condition. Also, degradation of dissolved and particulate organic matter could be an additional mechanism for the 15N-enrichment, and may have been significant when the ocean was rich in organic matter. At the time of the Shuram event, both δ13Ccarb and δ15NTN values were dropped probably due to massive re-mineralization of organic matter. This scenario is supported by an anomalously low C/N ratio, implying that enhanced respiration resulted in selective loss of carbon as CO2 with recycled organic nitrogen. After the Shuram event, the δ15N value continued to decrease despite that δ13Ccarb rose back to + 4‰. The continued δ15N drop appears to have coincided with a decreasing phosphorus content in carbonate. This suggests that ocean oxygenation may have generated a more nitrate-rich condition with respect to phosphorus as a limiting nutrient. Similar to the Shuram event, another negative δ13Ccarb event in the Canglanpuan stage of the Early Cambrian is also characterized by carbon isotopic decoupling as well as the low C/N ratio. The results strongly support that the two stages of the decoupled negative δ13Ccarb excursions reflect a disappearance of a large organic carbon pool in the ocean. The two events appear to relate with the appearance of new metazoan taxa with novel feeding strategies, suggesting a link between ocean oxygenation, nutrient cycling and the appearance and adaptation of metazoans. The nitrogen isotope geochemistry is very useful to understand the link between the environmental, ecological and biological evolutions.  相似文献   

18.
《Gondwana Research》2014,25(3-4):1276-1282
Concentrations of total organic matter (TOC), carbon isotopic compositions of carbonate and organic matter (δ13Ccarb, δ13Corg), and sulfur isotopic compositions of carbonate associated sulfate (δ34Ssulfate) across the Guadalupian–Lopingian (G–L) boundary were analyzed from identical samples of Tieqiao section, Laibin, Guangxi province, South China. The δ13Ccarb values show a positive excursion from − 0.45‰ to the peak of 3.80‰ in the Laibin limestone member of the Maokou Formation, followed by a drastic drop to − 2.60‰ in the lowest Heshan formation, then returned to about 1.58‰. Similar to the trends of the δ13Ccarb values, Δ13Ccarb–org values also show a positive excursion followed by a sharp negative shift. The onset of a major negative carbon isotope excursion postdates the end Guadalupian extinction that indicates subsequent severe disturbance of the ocean–atmosphere carbon cycle. The first biostratigraphic δ34Ssulfate values during the G–L transition exhibit a remarkable fluctuation: a dramatic negative shift followed by a rapid positive shift, ranging from 36.88‰ to − 37.41‰. These sulfate isotopic records suggest that the ocean during the G–L transition was strongly stratified, forming an unstable chemocline separating oxic shallow water from anoxic/euxinic deep water. Chemocline excursions, together with subsequent rapid transgression and oceanic anoxia, were likely responsible for the massive diversity decline of the G–L biotic crisis.  相似文献   

19.
The several-hundred-m-thick Miocene Upper Red Formation in northwestern Iran hosts stratiform and fault-controlled copper mineralization. Copper enrichment in the percent range occurs in dm-thick carbonaceous sandstone and shale units within the clastic redbed sequence and consists of fine-grained disseminated copper sulfides (chalcopyrite, bornite, chalcocite) and supergene alteration minerals (covellite, malachite and azurite). The copper mineralization formed after calcite cementation of the primary rock permeability. Copper sulfides occur mainly as replacement of diagenetic pyrite, which, in turn, replaced organic matter. Electron microprobe analysis on bornite, chalcocite and covellite identifies elevated silver contents in these minerals (up to 0.12, 0.72 and 1.21 wt%, respectively), whereas chalcopyrite and pyrite have only trace amounts of silver (<0.26 and 0.06 wt%, respectively). Microthermometric data on fluid inclusions in authigenic quartz and calcite indicate that the Cu mineralization is related to a diagenetic fluid of moderate-to low temperature (Th = 96–160 °C) but high salinity (25–38 wt% CaCl2 equiv.). The range of δ34S in pyrite is −41.9 to −16.4‰ (average −31.4‰), where framboidal pyrite shows the most negative values between −41.9 and −31.8‰, and fine-grained pyrite has relatively heavier δ34S values (−29.2 to −16.4‰), consistent with a bacteriogenic derivation of the sulfur. The Cu-sulfides (chalcopyrite, bornite and chalcocite) show slightly heavier values from −14.6 to −9.0‰, and their sulfur sources may be both the precursor pyrite-S and the bacterial reduction of sulfate-bearing basinal brines. Carbonates related to the ore stage show isotopically light values of δ13CV-PDB from −8.2 to −5.1‰ and δ18OV-PDB from −10.3 to −7.2‰, indicating a mixed source of oxidation of organic carbon (ca. −20‰) and HCO3− from seawater/porewater (ca. 0‰). The copper mineralization is mainly controlled by organic matter content and paleopermeability (intragranular space to large fracture patterns), enhanced by feldspar and calcite dissolution. The Cheshmeh-Konan deposit can be classified as a redbed-type sediment-hosted stratiform copper (SSC) deposit.  相似文献   

20.
Black carbon (BC) is a poorly understood type of organic carbon but it is present in almost all environmental systems (i.e., atmosphere, soil and water). This work focuses on soot BC in desert soils and, in particular, urban soils from the Phoenix, Arizona metropolitan area. Soot BC is that fraction of black carbon formed from the condensation of gas phase molecules produced during burning. Soot BC in Phoenix area soils exhibits a range in both concentration and isotopic composition. Soot BC concentration in 52 soils (desert, agricultural and urban) ranges from 0.02–0.54 wt% and comprises from < 1 to as much as 89% of the soil organic carbon (OC). Soot BC concentrations are higher in urban soils than in desert or agricultural soils. The average isotopic composition of soot BC is −18‰ ± 3‰; this is an enrichment of 5.5‰ relative to bulk soil organic carbon. The distribution in concentration and variation in isotopic composition across the study area suggests soot BC in this arid-land city has multiple sources, including a significant fossil fuel component.  相似文献   

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