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.     

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.     

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.     

Experimental hydrological forcing to illustrate water flow processes of a subarctic ladder fen peatland

Large peatland complexes dominate the landscape of the James Bay Lowland in subarctic Ontario, Canada. However, there is not a thorough understanding of the hydrological processes occurring in these important systems, particularly how ladder fens connect large domed bogs to the aquatic ecosystems that drain the peatland complex. Ladder fens consist of a pool‐rib topography where flow downgradient is controlled by the peat ribs. Within the ribs, low‐lying preferential flow paths typically enhance the transmission of water, whereas the elevated ridge microforms impede water flow to downgradient aquatic ecosystems. To assess the hydrological connectivity, we study the role of the water table, peat transmissivity, and microtopography of a small ladder fen for 3 summers (2013–2015) in the James Bay Lowland. The system was manipulated with a sustained hydrological forcing (water addition) to the upslope boundary of the fen during 2014 (38 m³/day) and 2015 (30 m³/day). There was an exponential increase in transmissivity towards the peat surface due to extremely high‐hydraulic conductivities within the upper few centimeters of the peat deposit. At the maximum water table, the saturated hydraulic conductivity of the 0.1 m layer of peat below the water table varied depending on peat microtopography (preferential flow paths = 42–598 m/day and ridges = 16–52 m/day), resulting in high‐hydrological connectivity periods. Furthermore, during 2015, there was an abnormally large amount of precipitation (300 mm vs. long‐term average ~ 100 mm) that resulted in complete surface water connectivity of the site. This caused rapid movement of water from the head of system to the outlet (~15 hr) and runoff ratios >1, compared to low‐water table periods (runoff ratio ~ 0.05). This study highlights the profound importance of the transmissivity–water table feedback mechanism in ladder fens, on controlling the water retention and drainage of large peatland complexes.     

Spatial–temporal changes in Andean plateau climate and elevation from stable isotopes of mammal teeth

Paleoelevation constraints from fossil leaf physiognomy and stable isotopes of sedimentary carbonate suggest that significant surface uplift of the northern Andean plateau, on the order of 2.5 ± 1 km, occurred between ～ 10.3 and 6.4 Ma. Independent spatial and temporal constraints on paleoelevation and paleoclimate of both the northern and southern plateau are important for understanding the distribution of rapid surface uplift and its relation to climate evolution across the plateau. This study focuses on teeth from modern and extinct mammal taxa (including notoungulates, pyrotheres, and litopterns) spanning ～ 29 Ma to present, collected from the Altiplano and Eastern Cordillera of Bolivia (16.2°S to 21.4°S), and lowland Brazil. Tooth enamel of large, water-dependent mammals preserves a record of surface water isotopes and the type of plants that animals ingested while their teeth were mineralizing. Previous studies have shown that the δ¹⁸O of modern precipitation and surface waters decrease systematically with increasing elevations across the central Andes. Our results from high elevation sites between 3600 and 4100 m show substantially more positive δ¹⁸O values for late Oligocene tooth samples compared to < 10 Ma tooth δ¹⁸O values. Late Oligocene teeth collected from low elevation sites in southeast Brazil show δ¹⁸O values similar (within 2‰) to contemporaneous teeth collected at high elevation in the Eastern Cordillera. This affirms that the Andean plateau was at a very low elevation during the late Oligocene. Late Oligocene teeth from the northern Eastern Cordillera also yield consistent δ¹³C values of about ? 9‰, indicating that the environment was semi-arid at that time. Latitudinal gradients in δ¹⁸O values of late Miocene to Pliocene fossil teeth are similar to modern values for large mammals, suggesting that by ～ 8 Ma in the northern Altiplano and by ～ 3.6 Ma in the southern Altiplano, both regions had reached high elevation and established a latitudinal rainfall gradient similar to modern.     

Stratification and mixing of a post-glacial Neoproterozoic ocean: Evidence from carbon and sulfur isotopes in a cap dolostone from northwest China

To improve our knowledge about the geochemical and environmental aftermath of Neoproterozoic global glaciations, we analyzed stable isotopes (δ¹³C, δ¹⁸O, δ³⁴S) and elemental concentrations (Ca, Mg, S, Sr, Fe, and Mn) of the ～ 10-m-thick Zhamoketi cap dolostone atop the Tereeken diamictite in the Quruqtagh area, eastern Chinese Tianshan. Available chemostratigraphic data suggest that the Tereeken diamictite is probably equivalent to the Marinoan glaciation. Our new data indicate that organic and carbonate carbon isotopes of the Zhamoketi cap dolostone show little stratigraphic variations, averaging ? 28.2‰ and ? 4.6‰, respectively. In contrast, sulfur isotopes show significant stratigraphic variations. Carbonate associated sulfate (CAS) abundance decreases rapidly in the basal cap dolostone and δ³⁴S_CAS composition varies between + 9‰ and + 15‰ in the lower 2.5 m. In the overlying interval, CAS abundance remains low while δ³⁴S_CAS rises ～ 5‰ and varies more widely between + 10‰ and + 21‰. The range of δ³⁴S_py of the cap dolostone overlaps with that of δ³⁴S_CAS, but direct comparison shows that δ³⁴S_py is typically greater than δ³⁴S_CAS measured from the same samples. Hypotheses to explain the observations must account for both the remarkable sulfur isotope enrichment of pyrites and the inverse fractionation. We propose that CAS and pyrite were derived from two isotopically distinct reservoirs in a chemically stratified basin or a basin with a sulfate minimum zone. In this model, CAS was derived from shallow, oxic surface waters with moderate sulfate concentration and depleted in ³⁴S due to the post-glacial influx of sulfur from continental weathering. In contrast, pyrite was derived from anoxic bottom waters (or a sulfate minimum zone) with low sulfate concentration and ³⁴S enrichment due to long-term syn-glacial sulfate reduction. The rapid shift in CAS abundance and sulfur isotope composition within the cap dolostone is interpreted to reflect the mixing of the two reservoirs after initial deglaciation. Comparison with other post-Marinoan cap carbonates shows significant spatial heterogeneity in δ³⁴S_CAS, which together with strong temporal variation in δ³⁴S_CAS, points to generally low sulfate concentrations in post-Marinoan oceans.     

Differences in stable isotope compositions of freshwater snails from surface sediments of two Polish shallow lakes

The study reports and discusses the differences in δ¹³C and δ¹⁸O values of shells between several species of freshwater snails. Shells were derived from sediment samples collected from depths of 0.5, 1, 2 and 3 m along transects in two shallow eutrophic lakes located in mid-western Poland. Mean δ¹³C values of the shells ranged between −7.5 and −3.8‰ in Lake Jarosławieckie and between −8.1 and −5.2‰ in Lake Rosnowskie Duże, whereas mean δ¹⁸O values ranged between −2.2 and −0.2‰ and between −2.2 and 0.4‰ respectively in the studied lakes. A similar order of species in terms of shell isotope values, from least to most ¹³C and ¹⁸O-depleted was observed in both lakes and seems to indicate constancy of the factors controlling the stable isotope compositions of snail shells. We postulate that the nearly 4‰ difference in the mean carbon stable isotope values between the species was primarily controlled by the amount of metabolic carbon incorporated into the shells and the δ¹³C values of the snail food. Different growth cessation temperatures and microhabitats of the species studied result in temporally and spatially varied DIC δ¹³C values, water δ¹⁸O values and water temperature of shell precipitation, and may thus differentiate the δ¹³C and δ¹⁸O values of shells. The range of δ¹³C and δ¹⁸O values of individual shells from a sediment sample (mean 2.35 and 2.15‰, respectively) is interpreted as reflecting an intraspecific variability of isotope compositions in shells from a population and changes of the ambient conditions during the accumulation of the sediment layer. The species-specificity and intraspecific variability in C and O isotopic compositions of shells allow concluding that in palaeolimnological studies, stable isotope analyses should be performed on a set of mono-specific shells representing mean isotope compositions of the species for the interval studied rather than single shells or multispecific bulk shell material.     

Assessing DOC export from a Sphagnum‐dominated peatland using δ13C and δ18O–H2O stable isotopes

Dissolved organic carbon (DOC) originating in peatlands can be mineralized to carbon dioxide (CO₂) and methane (CH₄), two potent greenhouse gases. Knowledge of the dynamics of DOC export via run‐off is needed for a more robust quantification of C cycling in peatland ecosystems, a prerequisite for realistic predictions of future climate change. We studied dispersion pathways of DOC in a mountain‐top peat bog in the Czech Republic (Central Europe), using a dual isotope approach. Although δ¹³C_DOC values made it possible to link exported DOC with its within‐bog source, δ¹⁸O_H2O values of precipitation and run‐off helped to understand run‐off generation. Our 2‐year DOC–H₂O isotope monitoring was complemented by a laboratory peat incubation study generating an experimental time series of δ¹³C_DOC values. DOC concentrations in run‐off during high‐flow periods were 20–30 mg L^?1. The top 2 cm of the peat profile, composed of decaying green moss, contained isotopically lighter C than deeper peat, and this isotopically light C was present in run‐off in high‐flow periods. In contrast, baseflow contained only 2–10 mg DOC L^?1, and its more variable C isotope composition intermittently fingerprinted deeper peat. DOC in run‐off occasionally contained isotopically extremely light C whose source in solid peat substrate was not identified. Pre‐event water made up on average 60% of the water run‐off flux, whereas direct precipitation contributed 40%. Run‐off response to precipitation was relatively fast. A highly leached horizon was identified in shallow catotelm. This peat layer was likely affected by a lateral influx of precipitation. Within 36 days of laboratory incubation, isotopically heavy DOC that had been initially released from the peat was replaced by isotopically lighter DOC, whose δ¹³C values converged to the solid substrate and natural run‐off. We suggest that δ¹³C systematics can be useful in identification of vertically stratified within‐bog DOC sources for peatland run‐off.     

Nitrogen and carbon isotopic composition in the diamonds of Mbuji Mayi (Zaïre)

The concentration and isotopic composition of nitrogen, measured in large diamonds (gram size) from the Mbuji Mayi kimberlite district (Zaïre) show a large range of variation (100<N<2100 ppm, ?11.2<δ¹⁵N< +6.0). The¹⁵N-depleted nitrogen is associated with the higher nitrogen concentrations. The large diamonds are individually rather homogeneous in¹³C (range ofδ¹³C < 0.9‰) while variations occur within small octahedral diamonds from the same district (range up to 5.8‰). The total range ofδ¹³C variation is about the same for the large diamonds (?10.5 <δ¹³C < ?5.5), the small octahedral diamonds (?10 <δ¹³C < ?4.6), and the carbonates from local kimberlites (?11.8 < δ¹³C < ?5.5). The diamond carbon isotopic data could indicate a complex story of crystallization within a deep-seated system fractionating its carbon isotopes.The nitrogen results indicate that nitrogen in diamonds is, on the average, markedly depleted in¹⁵N (weighted average ?5.15‰) relative to atmosphere, sediments and upper mantle.     

Temporal variations of C,N, δC,and δN in organic matter collected by a sediment trap at Cuenca Alfonso,Bahía de La Paz,SW Gulf of California

To monitor the composition and the vertical flux of particulate matter from the sea surface, a sediment trap was moored in Cuenca Alfonso, Bahía de La Paz, a zone of high productivity in the southwestern Gulf of California. Carbonate-free samples from 2002 to 2005 were analyzed for C_org, N, δ¹³C, and δ¹⁵N. The results show seasonal and interannual variability, with the δ¹³C and δ¹⁵N values larger in spring and summer than in fall and winter. The C:N ratio and δ¹³C increased by 1.5 units from 2002 to 2003–2005, suggesting a change in the supply of organic matter and-or the use or preferential degradation of N_org. There was no interannual variation in δ¹⁵N. The occasional high δ¹⁵N values suggest that physical mechanisms, such as the shoaling and advection into the bay of ¹⁵N-rich subsurface equatorial water, occur over short time periods. The latter is presumed to be related to the periodic development of a significant cyclonic gyre in the southern Gulf.     

Optimizing radiocarbon chronologies in peat profiles with examples from Xinjiang,China

Reliable chronological frameworks are crucial to paleoenvironmental studies, and high precision ¹⁴C dating is the foundation, but many factors, such as dating materials, surficial deposition (influenced by nuclear bomb), and the ¹⁴C age plateau, will affect the reliability of the ¹⁴C ages and chronology frameworks. In this paper, we present 87 ¹⁴C dates of different peat fractions from three peat sites in Xinjiang, China. Plant macrofossils, rootlets, the fine fraction of <90 μm, the mid-size fraction of 90–250 μm and the coarse fraction of >250 μm from selected peat samples were measured to investigate the alternative suitable fraction for dating except for plant macrofossils. We discovered that the 90–250 μm component of peat can provide alternative and reliable results in case of plant macrofossils are not available. Additionally, more dating samples from surficial peat deposition were collected, and accurate surface chronological control points were produced by comparing ¹⁴C results of plant macrofossils with atmospheric ¹⁴C bomb data. Furthermore, multiple data sets with wiggle matching were used along the radiocarbon age plateau to minimize calibrated errors when dates on the ¹⁴C age plateau were shown. Finally, radiocarbon chronology frameworks in peat profiles were optimized. In conclusion, we not only focus on the reliable dating materials, but also highlight that the importance of surficial deposition (after 1950AD) and the anomalous ¹⁴C dates when establishing the dating framework in peat profiles. Furthermore, we propose that the obtaining chronological control points of surficial peat is an important part of the establishing and improving of peat chronological framework in future research.     

Spatio‐temporal changes in bog pool bottom topography – temperature effect and its influence on pool development: an example from a raised bog in Estonia

Increases in pool water and peat temperature in summer accelerate peat decomposition and production of biogenic gases, which can be trapped in peat pores and cause oscillation of peatland surfaces and the rise of peat from the bottom of bog pools. Associated changes in peat water conductivity, holding capacity and transpiration also affect bog hydrology. Our multi‐year study is the first to show in detail the extent and dynamics of changes in bog pool depth and bottom topography associated with changes in temperature, peat type and other factors. The true seasonal rise of peat from the pool bottom begins once the water temperature at the pool bottom exceeds 13–14 °C, although the speed and extent of the rise depends on peat properties, making the rise more erratic than its subsequent descent. The more rapid descent occurs after the first large drop in the temperature of the pool's surface water at the end of summer, resulting from the combination of reduced methane production and increased gas solubility with less influence by peat properties. Much higher dissolved organic carbon concentrations (216 ± 26 mg l^?1) in the pore water of peat risen from the bottom to the pool surface compared with that in the same type of peat at the pool bottom (62 ± 20 mg l^?1) indicate an acceleration of peat decomposition at the warmer pool surface. We show the extent and character of changes in pool depth and bottom topography and how annual differences relate to temperature. Only a few degrees' increase in pool water temperature could induce the pool bottom to rise faster and more extensively for a longer period and enhance decomposition in the peat at the pool surface. This should be evaluated in greater detail to assess the effects of temperature increase on the carbon budget and hydrology of peatlands. Copyright © 2012 John Wiley & Sons, Ltd.     

Radiocarbon age anomalies of land snail shells in the Chinese Loess Plateau

In the Chinese Loess Plateau, land snail shells are often the only material available for dating in paleoenvironmental and archaeological research. However, the geochronological suitability of land snail shells is limited because of poor knowledge about their deposition dynamics, particularly with regards to the incorporation of inorganic carbonate and the resulting age anomalies. To evaluate the factors controlling these age anomalies, radiocarbon and stable carbon analyses were carried out on surface soils, as well as the shells and organic bodies of different modern snail species from different ecological habitats. The results showed that all specimens were depleted in ¹⁴C, indicating the influence of inorganic, radiocarbon-free carbonate on the ¹⁴C-activity of the snail shells. The apparent ¹⁴C-deficiencies and the resultant age anomalies of both the Cathaica and the Bradybaena snail shells were within close ranges across the Chinese Loess Plateau, indicating that the shells of these species could, after corrections for radiocarbon anomalies, provide reliable age estimates. The apparent ¹⁴C-deficiencies were closely associated with the ecological habitats of the snails. The shells of the ground-dwelling Bradybaena had the smallest age offsets (533 ± 150 a), followed grass-dwelling Cathaica (1107 ± 138 a) and Cathaica living on trees (1550 ± 345 a). These results suggest that the availability of calcium in the respective ecological habitats is an important factor in explaining the apparent ¹⁴C-deficiencies. The influence of carbonate on the stable carbon isotope composition of shells is overwhelmed by the organic diets of snails, making δ¹³C unsuitable for identifying and correcting shell age anomalies. The radiocarbon activities of surface soils (A_calc) increase with weathering intensity. Thus, a significant uncertainty could be caused by assuming that A_calc is zero when estimating the proportions of different carbon sources in shells, as has been the case in most previous studies.     

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.     

Quantification of peatland water storage capacity using the water table fluctuation method

Peat specific yield (S_Y) is an important parameter involved in many peatland hydrological functions such as flood attenuation, baseflow contribution to rivers, and maintaining groundwater levels in surficial aquifers. However, general knowledge on peatland water storage capacity is still very limited, due in part to the technical difficulties related to in situ measurements. The objectives of this study were to quantify vertical S_Y variations of water tables in peatlands using the water table fluctuation (WTF) method and to better understand the factors controlling peatland water storage capacity. The method was tested in five ombrotrophic peatlands located in the St. Lawrence Lowlands (southern Québec, Canada). In each peatland, water table wells were installed at three locations (up‐gradient, mid‐gradient, and down‐gradient). Near each well, a 1‐m long peat core (8 cm × 8 cm) was sampled, and subsamples were used to determine S_Y with standard gravitational drainage method. A larger peat sample (25 cm × 60 cm × 40 cm) was also collected in one peatland to estimate S_Y using a laboratory drainage method. In all sites, the mean water table depth ranged from 9 to 49 cm below the peat surface, with annual fluctuations varying between 15 and 29 cm for all locations. The WTF method produced similar results to the gravitational drainage experiments, with values ranging between 0.13 and 0.99 for the WTF method and between 0.01 and 0.95 for the gravitational drainage experiments. S_Y was found to rapidly decrease with depth within 20 cm, independently of the within‐site location and the mean annual water table depth. Dominant factors explaining S_Y variations were identified using analysis of variance. The most important factor was peatland site, followed by peat depth and seasonality. Variations in storage capacity considering site and seasonality followed regional effective growing degree days and evapotranspiration patterns. This work provides new data on spatial variations of peatland water storage capacity using an easily implemented method that requires only water table measurements and precipitation data.     

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.     

Century-long record of Mo isotopic composition in sediments of a seasonally anoxic estuary (Chesapeake Bay)

A double-spike method was used to obtain Mo isotope data for sediments and waters of the seasonally anoxic Chesapeake Bay, and its primary tributary, the Susquehanna River. The dissolved Mo distribution in the estuary is non-conservative, reflecting minor Mo loss to the sediments, although removal of Mo to the sediments does not have a large influence on the isotopic composition of the water column. The δ⁹⁸Mo of dissolved Mo in most of the estuary is dominated by seawater. Six samples with salinity > 15 have an average δ⁹⁸Mo = + 2.17‰ (± 0.12), which agrees well with a δ⁹⁸Mo value for the CASS-4 seawater standard of + 2.23‰. A single sample of Susquehanna River water has a δ⁹⁸Mo of + 1.02‰, consistent with recent findings of positive δ⁹⁸Mo in rivers worldwide. Susquehanna river sediments, in contrast, have δ⁹⁸Mo ～ ? 0.1‰. The difference between the river water and sediment values implies that isotopic fractionation occurs within the river basin. The δ⁹⁸Mo values for estuarine sediments are offset from values in the overlying water. Most samples deposited before 1925 have δ⁹⁸Mo less than 0‰, similar to the Susquehanna sediments. Subsequently, there is an increase in the variability of δ⁹⁸Mo, with values ranging up to + 0.8‰. The transition to increased variability coincides with the onset of authigenic Mo deposition, which was previously attributed to escalating summertime anoxia. Authigenic Mo concentrations correlate poorly with δ⁹⁸Mo in core samples, suggesting that independent mechanisms influence the two parameters. Authigenic Mo concentrations may be controlled by shifting pore water H₂S levels, while δ⁹⁸Mo may be primarily affected by annual variations in Mn refluxing.     

Characteristics and accumulation mechanisms of the Dongfang 13-1 high temperature and overpressured gas field in the Yinggehai Basin,the South China Sea

The Dongfang 13-1 is located in the diapiric structure belt of the Yinggehai Basin. The formation pressure of its main gas reservoir in the Miocene Huangliu Formation is up to 54.6 MPa(pressure coefficient=1.91) and the temperature is as high as 143°C(geothermal gradient 4.36°C/100 m), indicating that it is a typical high-temperature and overpressured gas reservoir. The natural gas is interpreted to be coal-type gas derived from the Miocene mature source rocks containing type II2-III kerogens as evidenced by high dryness index of up to 0.98 and heavy carbon isotopes, i.e., the δ13C1 ranging from -30.76‰ to -37.52‰ and δ13C2 ranging from -25.02‰ to -25.62‰. The high temperature and overpressured Miocene petroleum system is related mainly to diapir in the Yinggehai Basin and contains more pore water in the overpressured reservoirs due to undercompaction process. The experimental and calculated results show that the solubility of natural gas in formation water is as high as 10.5 m3/m3 under the temperature and pressure conditions of the Sanya Formation, indicating that at least part of the gas may migrate in the form of water-soluble phase. Meanwhile, the abundant gas source in the Basin makes it possible for the rapid saturation of natural gas in formation water and exsolution of soluble gas. Therefore, the main elements controlling formation of the Dongfang 13-1 gas pool include that(1) the diapir activities and accompanying changes in temperature and pressure accelerate the water-soluble gas exsolution and release a lot of free gas;(2) submarine fan fine sandstone in the Huangliu Formation provides good gas-water segregation and accumulation space; and(3) the overlying overpressured mud rocks act as effective caps. The accumulation mechanism reveals that the high temperatural and high pressure structure belt near the diapir structures has a good potential for large and medium-sized gas field exploration.     

The effects of ditch dams on water-level dynamics in tropical peatlands

A significant proportion of tropical peatlands has been drained for agricultural purposes, resulting in severe degradation. Hydrological restoration, which usually involves blocking ditches, is therefore a priority. Nevertheless, the influence of ditch blocking on tropical peatland hydrological functioning is still poorly understood. We studied water-level dynamics using a combination of automated and manual dipwells, and also meteorological data during dry and wet seasons over 6 months at three locations in Sebangau National Park, Kalimantan, Indonesia. The locations were a forested peatland (Forested), a drained peatland with ditch dams (Blocked), and a drained peatland without ditch dams (Drained). In the dry season, water tables at all sites were deeper than the Indonesian regulatory requirement of 40 cm from the peat surface. In the dry season, the ditches were dry and water did not flow to them. The dry season water-table drawdown rates — solely due to evapotranspiration — were 9.3 mm day⁻¹ at Forested, 9.6 mm day⁻¹ at Blocked, but 12.7 mm day⁻¹ at Drained. In the wet season, the proportion of time during which water tables in the wells were deeper than the 40 cm limit ranged between 16% and 87% at Forested, 0% at Blocked, and between 0% and 38% at Drained. In the wet season, water flowed from the peatland to ditches at Blocked and Drained. The interquartile range of hydraulic gradients between the lowest ditch outlet and the farthest well from ditches at Blocked was 3.7 × 10⁻⁴ to 7.8 × 10⁻⁴ m m⁻¹, but 1.9 × 10⁻³ to 2.6 × 10⁻³ m m⁻¹ at Drained. Given the results from Forested, a water-table depth limit policy based on field data may be required, to reflect natural seasonal dynamics in tropical peatlands. Revised spatial designs of dams or bunds are also required, to ensure effective water-table management as part of tropical peatland restoration.     

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.