Terrestrial and marine biomarker estimates of organic matter sources and distributions in surface sediments from the East China Sea shelf

Revealing of the sources and distributions of sedimentary organic matter in the East China Sea (ECS) is important for understanding its carbon cycle, which has significant temporal and spatial variability due to the influences of recent climate changes and anthropogenic activities. In this study, we report the contents of both terrestrial and marine biomarkers including ∑C₂₇+C₂₉+C₃₁n-alkanes (38.6-580 ng/g), C₃₇ alkenones (5.6-124.6 ng/g), brassicasterol (98-913 ng/g) and dinosterol (125-1521 ng/g) from the surface sediments in the Changjiang River Estuary (CRE) and shelf areas of the ECS. Several indices based on biomarker contents and ratios are calculated to assess the spatial distributions of both terrestrial and marine organic matter in the ECS surface sediments, and these results are compared with organic matter distribution patterns revealed by the δ¹³C (−20.1‰ to −22.7‰) and C/N ratio (5-7.5) of total organic matter. The contents of terrestrial biomarkers in the ECS surface sediments decrease seaward, controlled mostly by Changjiang River (CR) inputs and surface currents; while higher contents of the two marine biomarkers (brassicasterol and dinosterol) occur in upwelling areas outside the CRE and in the Zhejiang-Fujian coastal zone, controlled mostly by marine productivity. Four proxies, f_Terr(δ¹³C) (the fraction of terrestrial organic matter in TOC estimated by TOC δ¹³C), odd-alkanes (∑C₂₇+C₂₉+C₃₁n-alkanes), 1/P_mar-aq ((C₂₃+C₂₅+C₂₉+C₃₁)/(C₂₃+C₂₅) n-alkanes) and TMBR (terrestrial and marine biomarker ratio) (C₂₇+C₂₉₊C₃₁n-alkanes)/((C₂₇+C₂₉+C₃₁) n-alkanes+(brassicasterol+dinosterol+alkenones)), reveal a consistent pattern showing the relative contribution of terrestrial organic matter (TOM) is higher in the CRE and along the Zhejiang-Fujian coastline, controlled mostly by CR inputs and currents, but the TOM contribution decreases seaward, as the influences of the CR discharge decrease.     

Methane-derived authigenic carbonates from the Ulleung basin sediments,East Sea of Korea

Authigenic carbonates were sampled in methane-enriched piston core sediments collected from gas venting sites on the western continental slope of the Ulleung Basin, East Sea of Korea. Multidisciplinary investigations on these carbonates, including the scanning electronic microscope (SEM) observations and mineralogical-geochemical compositions, were carried out to identify the carbon and oxygen sources and the forming mechanism of these carbonates. The authigenic carbonates from the study area correspond to semi-consolidated, compact concretions or nodules ranging from 2 to 9 cm in size. X-ray diffraction and electron microprobe analyses showed that most of the sampled carbonate concretions were composed of almost purely authigenic high-Mg calcite (10.7–14.3 mol% MgCO₃). Characteristically, microbial structures such as filaments and rods, which were probably associated with the authigenic minerals, were abundantly observed within the carbonate matrix. The carbonates were strongly depleted in δ¹³C (−33.85‰ to −39.53‰ Peedee Belemnite (PDB)) and were enriched in δ¹⁸O (5.16–5.60‰ PDB), indicating that the primary source of carbon is mainly derived from the anaerobic oxidation of methane. Such methane probably originated from the destabilization of the underlying gas hydrates as strongly supporting from the enriched ¹⁸O levels. Furthermore, the strongly depleted δ¹³C values (−60.7‰ to −61.6‰ PDB) of the sediment void gases demonstrate that the majority of the gas venting at the Ulleung Basin is microbial methane by CO₂ reduction. This study provides another example for the formation mechanism of methane-derived authigenic carbonates associated with gas-hydrate decomposition in gas-seeping pockmark environments.     

Low-temperature hydrothermal alteration of intra-caldera tuffs,Miocene Tejeda caldera,Gran Canaria,Canary Islands

The Miocene Tejeda caldera on Gran Canaria erupted ~ 20 rhyolite–trachyte ignimbrites (Mogán Group 14–13.3 Ma), followed by ~ 20 phonolitic lava flows and ignimbrites (Fataga Group 13–8.5 Ma). Upper-Mogán tuffs have been severely altered immediately within the caldera margin, whereas extra-caldera Mogán ignimbrites, and overlying Fataga units, are apparently unaltered. The altered intra-caldera samples contain minerals characteristic of secondary fluid–rock interaction (clays, zeolites, adularia), and relics of the primary mineral assemblage identified in unaltered ignimbrites (K-feldspar, plagioclase, pyroxene, amphibole, and groundmass quartz). Major and trace-element data indicate that Si, Na, K, Pb, Sr, and Rb, were strongly mobilized during fluid–rock interaction, whereas Ti, Zr, and Nb behaved in a more refractory manner, experiencing only minor mobilization. The δ¹⁸O values of the altered intra-caldera tuffs are significantly higher than in unaltered extra-caldera ignimbrites, consistent with an overall low-temperature alteration environment. Unaltered extra-caldera ignimbrites have δD values between − 110‰ and − 173‰, which may reflect Rayleigh-type magma degassing and/or post-depositional vapour release. The δD values of the altered intra-caldera tuffs range from − 52‰ to − 131‰, with ambient meteoric water at the alteration site estimated at ca. − 15‰. Interaction and equilibration of the intra-caldera tuffs with ambient meteoric water at low temperature can only account for whole-rock δD values of around − 45‰, given that ?D_clay–water is ca. − 30‰ at 100 °C, and decreases in magnitude at higher temperatures. All altered tuff samples have δD values that are substantially lower than − 45‰, indicating interaction with a meteoric water source with a δD value more negative than − 15‰, which may have been produced in low-temperature steam fumaroles. Supported by numerical modeling, our Gran Canaria data reflect the near-surface, epithermal part of a larger, fault-controlled hydrothermal system associated with the emplacement of the high-level Fataga magma chamber system. In this near-surface environment, fluid temperatures probably did not exceed 200–250 °C.     

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.     

Biological and environmental changes in Lake Baikal during the late Quaternary inferred from carbon, nitrogen and sulfur isotopes

An 8-m continuous sediment core, approximately 250-ky-old at the bottom, from Academician Ridge in Lake Baikal, has been analyzed for the stable isotopes of carbon, nitrogen and sulfur, in order to study the paleoclimatic and paleobiological changes that occurred in the Eurasian continental interior. These isotopic changes are closely related to changes in vertical lake-water circulation between glacial and interglacial periods. Sedimentary organic carbon in cool periods is more enriched in ¹³C (−23.8‰ on average) than that in warm periods (−27.0‰ on average). The ¹³C-enrichment of organic carbon suggests a decrease of land-derived organic matter influx to the lake, less precipitation, and loss of terrestrial vegetation around Lake Baikal in cool periods. Pyrite in high total sulfur/total organic carbon (TS/TOC) layers shows strong depletion in ³⁴S (−20.8‰ to −32.4‰) during climate transitions from glacial to interglacial periods at the beginning of oxygen isotope stages (OIS) 1, 5 and 7. The ³⁴S-depleted pyrite indicates augmentation of dissimilatory sulfate reduction by sulfate reducing bacteria (SRB) at the sediment-water interface. Enhancement of aqueous sulfate concentrations and limitation of oxygen circulation to the surface sediments might also occur in the climate transition periods. The δ¹⁵N values of total nitrogen increase abruptly by ∼2‰ just after the δ³⁴S negative peaks, which may result from low nutrient concentrations in the euphotic zone associated with water circulation changes in Lake Baikal.     

Origin and evolution of two contrasting thermal groundwaters (CO2-rich and alkaline) in the Jungwon area,South Korea: Hydrochemical and isotopic evidence

In the Jungwon area, South Korea, two contrasting types of deep thermal groundwater (around 20–33 °C) occur together in granite. Compared to shallow groundwater and surface water, thermal groundwaters have significantly lower δ¹⁸O and δD values (> 1‰ lower in δ¹⁸O) and negligible tritium content (mostly < 2 TU), suggesting a relatively high age of these waters (at least pre-thermonuclear period) and relatively long subsurface circulation. However, the hydrochemical evolution yielded two distinct water types. CO₂-rich water (P_CO2 = 0.1 to 2 atm) is characterized by lower pH (5.7–6.4) and higher TDS content (up to 3300 mg/L), whereas alkaline water (P_CO2 = 10^− 4.1–10^− 4.6 atm) has higher pH (9.1–9.5) and lower TDS (< 254 mg/L). Carbon isotope data indicate that the CO₂-rich water is influenced by a local supply of deep CO₂ (potentially, magmatic), which enhanced dissolution of silicate minerals in surrounding rocks and resulted in elevated concentrations of Ca²⁺, Na⁺, Mg²⁺, K⁺, HCO₃⁻ and silica under lower pH conditions. In contrast, the evolution of the alkaline water was characterized by a lesser degree of water–rock (granite) interaction under the negligible inflow of CO₂. The application of chemical thermometers indicates that the alkaline water represents partially equilibrated waters coming from a geothermal reservoir with a temperature of about 40 °C, while the immature characteristics of the CO₂-rich water resulted from the input of CO₂ in Na–HCO₃ waters and subsequent rock leaching.     

Iron isotope fractionation during planetary differentiation

The Fe isotope composition of samples from the Moon, Mars (SNC meteorites), HED parent body (eucrites), pallasites (metal and silicate) and the Earth's mantle were measured using high mass resolution MC-ICP-MS. These high precision measurements (δ⁵⁶Fe ≈ ± 0.04‰, 2 S.D.) place tight constraints on Fe isotope fractionation during planetary differentiation.Fractionation during planetary core formation is confined to < 0.1‰ for δ⁵⁶Fe by the indistinguishable Fe isotope composition of pallasite bulk metal (including sulfides and phosphides) and olivine separates. However, large isotopic variations (≈ 0.5‰) were observed among pallasite metal separates, varying systematically with the amounts of troilite, schreibersite, kamacite and taenite. Troilite generally has the lightest (δ⁵⁶Fe ≈ − 0.25‰) and schreibersite the heaviest (δ⁵⁶Fe ≈ + 0.2‰) Fe isotope composition. Taenite is heavier then kamacite. Therefore, these variations probably reflect Fe isotope fractionation during the late stage evolution and differentiation of the S- and P-rich metal melts, and during low-temperature kamacite exsolution, rather than fractionation during silicate-metal separation.Differentiation of the silicate portion of planets also seems to fractionate Fe isotopes. Notably, magmatic rocks (partial melts) are systematically isotopically heavier than their mantle protoliths. This is indicated by the mean of 11 terrestrial peridotite samples from different tectonic settings (δ⁵⁶Fe = + 0.015 ± 0.018‰), which is significantly lighter than the mean of terrestrial basalts (δ⁵⁶Fe = + 0.076 ± 0.029‰). We consider the peridotite mean to be the best estimate for the Fe isotope composition of the bulk silicate Earth, and probably also of bulk Earth. The terrestrial basaltic mean is in good agreement with the mean of the lunar samples (δ⁵⁶Fe = + 0.073 ± 0.019‰), excluding the high-Ti basalts. The high-Ti basalts display the heaviest Fe isotope composition of all rocks measured here (δ⁵⁶Fe ≈ + 0.2‰). This is interpreted as a fingerprint of the lunar magma ocean, which produced a very heterogeneous mantle, including the ilmenite-rich source regions of these basalts.Within uncertainties, samples from Mars (SNC meteorites), HED (eucrites) and the pallasites (average olivine + metal) have the same Fe isotope compositions as the Earth's mantle. This indicates that the solar system is very homogeneous in Fe isotopes. Its average δ⁵⁶Fe is very close to that of the IRMM-014 standard.     

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.     

Geochemical characteristics and origin of gases from the Upper,Lower Paleozoic and the Mesozoic reservoirs in the Ordos Basin,China

The Ordos Basin, the second largest sedimentary basin in China, contains the broad distribution of natural gas types. So far, several giant gas fields have been discovered in the Upper and Lower Paleozoic in this basin, each having over 1000×10⁸m³ of proven gas reserves, and several gas pools have also been discovered in the Mesozoic. This paper collected the data of natural gases and elucidated the geochemical characteristics of gases from different reservoirs, and then discussed their origin. For hydrocarbons preserved in the Upper Paleozoic, the elevated δ ¹³C values of methane, ethane and propane indicate that the gases would be mainly coal-formed gases; the singular reversal in the stable carbon isotopes of gaseous alkanes suggests the mixed gases from humic sources with different maturity. In the Lower Paleozoic, the δ ¹³C₁ values are mostly similar with those in the Upper Paleozoic, but the δ ¹³C₂ and δ ¹³C₃ values are slightly lighter, suggesting that the gases would be mixing of coal-type gases as a main member and oil-type gases. There are multiple reversals in carbon isotopes for gaseous alkanes, especially abnormal reversal for methane and ethane (i.e. δ ¹³C₁>δ ¹³C₂), inferring that gases would be mixed between high-mature coal-formed gases and oil-type gases. In the Mesozoic, the δ ¹³C values for gaseous alkanes are enriched in ¹²C, indicating that the gases are mainly derived from sapropelic sources; the carbon isotopic reversal for propane and butane in the Mesozoic is caused by microbial oxidation and mixing of gases from sapropelic sources with different maturity. In contrast to the Upper Paleozoic gases, the Mesozoic gases are characterized by heavier carbon isotopes of iso-butane than normal butane, which may be caused by gases generated from different kerogen types. Finally, according to δ ¹³C₁-R ₀ relationship and extremely low total organic carbon contents, the Low Paleozoic gases would not be generated from the Ordovician source as a main gas source, bycontrast, the Upper Paleozoic source as a main gas source is contributed to the Lower Paleozoic gases.     

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.     

Molecular and isotopic characterization of the particulate organic matter from an eutrophic coastal bay in SE Brazil

The present work aimed at studying the origin of particulate organic matter in Guanabara Bay and in some rivers of the Guanabara basin by using elemental composition, isotopic ratios (δ¹³C and δ¹⁵N) and molecular markers (sterols) in samples collected in two periods (winter and summer). Elemental and isotopic compositions were determined by dry combustion and mass spectrometry, respectively, while sterols were investigated by GC–FID and GC–MS. Higher sterol concentrations were present in the north-western part of the bay in winter (5.10–23.5 μg L^–1). The high abundance of algal sterols (26–57% of total sterols), the elemental composition (C/N=6–8) and the isotopic signatures (δ¹³C=−21.3‰ to −15.1‰ and δ¹⁵N=+7.3‰ to +11.1‰) suggested the predominance of autochthonous organic matter, as expected for an eutrophic bay, although seasonal variation in phytoplankton activity was observed. Coprostanol concentration (fecal sterol) was at least one order of magnitude higher in the particulate material from fluvial samples (4.65–55.98 μg L^–1) than in the bay waters (<0.33 μg L^–1). This could be ascribed to a combination of factors including efficient particle removal to sediments in the estuarine transition zone, dilution with bay water and bacterial degradation during particle transport in the water column.     

The oxygen isotopic composition and temperature of Southern Ocean bottom waters during the last glacial maximum

We provide two new determinations of the oxygen isotopic composition of seawater during the last glacial maximum (LGM). High-resolution oxygen isotopic measurements were made on interstitial waters from Ocean Drilling Program (ODP) Sites 1168 and 1170 in the southeast Indian Ocean sector of the Southern Ocean. We use a diffusion-advection numerical model to calculate the glacial-interglacial change in bottom-water δ¹⁸O_sw from the pore water δ¹⁸O profiles; the first such determinations from this part of the oceans. Statistical analyses of the model runs indicate that Circumpolar Deep Water (CDW) δ¹⁸O_sw changed by 1.0-1.1±0.15‰ since the last glacial maximum (LGM). Our results are consistent with a previous calculation from a South Atlantic Southern Ocean location (ODP Site 1093) also situated within CDW. The new values determined in this study, together with previous estimates, are converging on a global average Δδ¹⁸O_sw of 1.0-1.1‰.Using the calculated bottom-water δ¹⁸O_sw, we have extracted the temperature component from the benthic foraminiferal δ¹⁸O record at Sites 1168 and 1170. Since the LGM, bottom waters at these two sites warmed by 2.6 and 1.9°C, respectively. The absolute temperature estimates for the LGM (−0.5°C [Θ=−0.6°C] at Site 1168 and −0.2°C [Θ=−0.4°C] at Site 1170) are slightly warmer than those reported from previous studies using the same technique, but are consistent with more homogenous deep-ocean temperatures during the LGM relative to the modern.     

Sulfur and carbon isotopic systematics of Guadalupian‐Lopingian (Permian) mid‐Panthalassa: δ34S and δ13C profiles in accreted paleo‐atoll carbonates in Japan

Immediately before the extinction of the end‐Guadalupian (Middle Permian; ca 260 Ma), a significant change to the global carbon cycle occurred in the superocean Panthalassa, as indicated by a prominent positive δ¹³C excursion called the Kamura event. However, the causes of this event and its connection to the major extinction of marine invertebrates remain unclear. To understand the mutual relationships between these changes, we analyzed the sulfur isotope ratio of the carbonate‐associated sulfate (CAS) and HCl‐insoluble residue, as well as the carbon isotope ratio of bulk organic matter, for the Middle‐Upper Permian carbonates of an accreted mid‐oceanic paleo‐atoll complex from Japan, where the Kamura event was first documented. We detected the following unique aspects of the stable carbon and sulfur isotope records. First, the extremely high δ¹³C values of carbonate (δ¹³C_carb) over +5 ‰ during the Capitanian (late Guadalupian) were associated with large isotopic differences between carbonate and organic matter (Δ¹³C = δ¹³C_carb ? δ¹³C_org). We infer that the Capitanian Kamura event reflected an unusually large amount of dissolved organic matter in the expanded oxygen minimum zone at mid‐depth. Second, the δ³⁴S values of CAS (δ³⁴S_CAS) were inversely correlated with the δ¹³C_carb values during the Capitanian to early Wuchiapingian (early Late Permian) interval. The Capitanian trend may have appeared under increased oceanic sulfate conditions, which were accelerated by intense volcanic outgassing. Bacterial sulfate reduction with increased sulfate concentrations in seawater may have stimulated the production of pyrite that may have incorporated iron in pre‐existing iron hydroxide/oxide. This stimulated phosphorus release, which enhanced organic matter production and resulted in high δ¹³C_carb. Low δ³⁴S_CAS values under high sulfate concentrations were maintained and the continuous supply of sulfate cannot by explained only by the volcanic eruption of the Emeishan Trap, which has been proposed as a cause of the extinction. The Wuchiapingian δ³⁴S_CAS–δ¹³C_carb correlation, likely related to low sulfate concentration, may have been caused by the removal of oceanic sulfate through the massive evaporite deposition.     

C-isotope stratigraphy and paleoenvironmental changes across OAE2 (mid-Cretaceous) from shallow-water platform carbonates of southern Mexico

The stratigraphic and geochemical record of the mid-Cretaceous (Cenomanian–Turonian) Oceanic Anoxic Event 2 (OAE2) has been studied in numerous Tethyan and proto-Atlantic hemi-pelagic/pelagic successions, but little data comes from nearshore carbonate successions from the proto-Pacific region. Here we present the results of a combined stratigraphic and δ¹³C study of C–T platform carbonates from southern Mexico, which were deposited within the proto-Pacific. Two scales of sedimentary cyclicity are recognized. High-frequency peritidal and subtidal cycles (0.4–8 m) display little evidence of cycle-capping subaerial exposure and are not correlative between sections; these relationships suggest that the amplitudes of high-frequency sea-level changes were minimal during the peak mid-Cretaceous greenhouse. Longer-term transgressive-regressive sequences (18–40⁺ m) are correlated between sections, and using δ¹³C trends, can be correlated with sequences developed in northern Europe and India.The Mexican successions were sampled at a high resolution (~ 10 ky) for stable isotopes (inorganic, organic carbon and oxygen), total organic carbon, insoluble residues, and trace metals. The δ¹³C_carb curve matches global trends (including 6 distinct isotopic stages) permitting identification of OAE2 despite the lack of characteristic anoxic facies. Using the δ¹³C_carb trends, we tie the previously identified ammonite, planktonic foram, and nannofossil biostratigraphy from England and the Western Interior seaway of Colorado into the Mexican sections. The initiation of OAE2, defined by an abrupt positive 3–4‰ δ¹³C shift, coincides with a long-term sea-level rise, though the sedimentary expression of the deepening is no greater than that observed for any of the other sea-level events across the studied interval. OAE2 termination (transition from gradually decreasing to background δ¹³C values) is not associated with a particular sea-level trend. Stratigraphic changes in insoluble residues (proxy for continental sediment discharge) across OAE2 are not correlative between sections and do not show consistent systematic relationships with δ¹³C or sea-level variations, therefore do not support the hypothesis that OAE2 was associated with increased continental-derived nutrient influx. Two peaks in trace metal concentrations coincide with the abrupt increase in δ¹³C ratios (onset of OAE2) and during the transition from elevated-to-decreasing δ¹³C values (near the C–T stage boundary). These trends are similar to those recorded in coeval deposits of the Western Interior seaway, and are consistent with the hypothesis that OAE2 development was related to the release of reduced metals during the short-lived (< 1 My) Caribbean oceanic plateau basalt eruption. In this scenario, oxidation of the metals depleted the existing low dissolved-O₂ concentrations and thermally-buoyant plumes of seawater enriched in biolimiting elements mixed with surface waters, stimulated primary productivity, and further reduced O₂ concentrations leading to widespread anoxia and a large positive δ¹³C shift.     

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.     

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.     

Nitrogen isotope ratios of nitrate as a clue to the origin of nitrogen on the Pacific coast of Japan

To clarify the sources and transformation of NO₃⁻ on the Pacific coast of Japan, observations over the continental shelf were conducted during the summer in 2005 and 2006 when the Kuroshio flowed close to and away from the coastal area, respectively. Below the halocline, there are two prominent salinity peaks that originated in two different waters. In the subsurface layer, the salinity maximum (S_max) was indicative of the Kuroshio Water (KW), while the salinity minimum (S_min) in the middle layer at ∼400 m depth was indicative of the North Pacific Intermediate Water (NPIW). δ¹⁵N_NO3 ranged from 4.1‰ to 5.1‰ with a mean of 4.8±0.4‰ in the deeper water around S_min. Below 50 m depth over the shelf break, δ¹⁵N_NO3 values (3.1±0.8‰ in 2005 and 4.6±0.3‰ in 2006) clearly increased as contribution of NPIW increased in 2006. On the contrary, subsurface δ¹⁵N of NO₃⁻ values (−1.1±0.1‰) remained unchanged in both years, although the contribution of the KW to the subsurface water changed significantly. This suggests that the source of NO₃⁻ has little effect on the δ¹⁵N of NO₃⁻ in this layer. The negative δ¹⁵N values also coincided with the base of the chlorophyll maximum layer suggesting that these isotopic signals must be evidence of active nitrification in the upper layer.     

Effect of salinity on acute copper and zinc toxicity to Tigriopus japonicus: The difference between metal ions and nanoparticles

We investigated the effects of salinity (5‰, 15‰, 25‰ and 35‰) on metal ion (Cu and Zn) and nanoparticle (NP) CuO and ZnO toxicity to Tigriopus japonicus. Increasing the test media volume without renewal increased the 96-h LC₅₀ for Cu (32.75 mg L⁻¹) compared to the reported value (3.9 mg L⁻¹). There was no significant difference in acute toxicity at different salinities between acclimated and unacclimated T. japonicus (p > 0.05). Increasing salinity decreased the dissolved concentrations of Cu and Zn ions due to the precipitation of the metal ions, consequently reducing the acute toxicity to T. japonicus. The effect of salinity on acute CuO and ZnO NP toxicity was similar to that on metal ion toxicity. Since the aggregation of NPs generally enhanced at higher salinities, both the dissolution and aggregation of CuO and ZnO NPs may control the effect of salinity on acute toxicity to T. japonicus.     

Preliminary study on the origin identification of natural gas by the parameters of light hydrocarbon

The light hydrocarbon composition of 209 natural gas samples and individual light hydrocarbon carbon isotopes of 53 natural gas samples from typical humic-sourced gas and sapropelic-sourced gas in the four basins of China have been determined and analyzed. Some identification parameters for humic-sourced gas and sapropelic-sourced gas are proposed or corrected. The differences of compound-specific δ ¹³C value of individual light hydrocarbon between humic-sourced gas and sapropelic-sourced gas have been founded. The humic-sourced gas has the distribution of δ ¹³C_benzene> ?24‰, δ ¹³C_toluene >?23‰, δ ¹³C_cyclohexane > ?24‰ and δ ¹³C_{methyl cyclohexane}> ?24‰, while the sapropelic-sourced gas has the distribution of δ ¹³C_benzene <?24‰, δ ¹³C_toluene< ?24‰, δ ¹³C_cyclohexane< ?24‰ and δ ¹³C_{methyl cyclohexane}< ?24‰. Among the components of C₇ light hydrocarbon compound, such as normal heptane (nC₇), methyl cyclohexane (MCH) and dimethyl cyclopentane (ΣDMCP), etc, relative contents of nC₇ and MCH are influenced mainly by the source organic matter type of natural gas. Therefore, it is suggested that the gas with relative content of nC₇ of more than 30% and relative content of MCH of less than 70% is sapropelic-sourced gas, while gas with relative content of nC₇ of less than 35% and relative content of MCH of more than 50% is humic-sourced gas. Among components of C_5–7 aliphatics, the gas with relative content of C_5–7 normal alkane of more than 30% is sapropelic-sourced gas, while the gas with relative content of C_5–7 normal alkane of less than 30% is humic-sourced gas. These paremeters have been suggested to identify humic-sourced gas and sapropelic-sourced gas.