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

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

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

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

High‐resolution lithostratigraphy and organic carbon isotope stratigraphy of the Lower Triassic pelagic sequence in central Japan

After the severest mass extinction event in the Phanerozoic, biotic recovery from the extinction at the Permian–Triassic boundary required approximately 5 my, which covers the entire Early Triassic. It is important to obtain information on the superocean Panthalassa, which occupied most of the world ocean, to explore paleoenvironmental changes during the Early Triassic at the global scale. In order to establish the continuous lithostratigraphy of pelagic sediments in Panthalassa during the Early Triassic, high‐resolution reconstruction of the Lower Triassic pelagic sequence in Japan was conducted for the first time based on detailed field mapping and lithostratigraphic correlation in the Inuyama area, central Japan. The reconstructed Early Triassic sequence is approximately 9.5 m thick, consists of five rock types, and is divided into eight lithological units. For the reconstructed continuous sequence, measurement of carbon isotopic composition of sedimentary organic matter (δ¹³C_org) was carried out. Stratigraphic variation of the δ¹³C_org value shows large‐amplitude fluctuations between ?34.4 and ?21.0‰ throughout the sequence. In order to establish a higher resolution age model for the reconstructed Lower Triassic pelagic sequence, we correlated δ¹³C_org records in the Inuyama area with high‐resolution isotopic profiles of carbonate carbon (δ¹³C_carb) from shallow‐marine carbonate sequences in southern China based on the similarity in general variation patterns with age constraints by radiolarian and conodont biostratigraphy. The result provides a high‐resolution time scale for the pelagic sequence of Panthalassa during the Smithian and Spathian. The age model suggests a drastic increase in sedimentation rate during the late Smithian, which should have been caused by the increase in terrigenous input to this site.     

Geochemical constraints on the depositional environment of the 1.84 Ga Embury Lake Formation,Flin Flon Belt,Canada

The Flin Flon Belt of Canada contains Paleoproterozoic volcanic–sedimentary sequences that are related to the Trans‐Hudson Orogeny. The sequences include island arc volcanic and volcaniclastic rocks (Amisk Group) that are unconformably overlain by subaerial sedimentary rocks (Missi Group), and younger deep facies sediments. In the Flin Flon area, several north–south trending faults divide the sequences into blocks and obscure the depositional environment of the deep facies sediments. Locally, within the Flin Flon area, the Embury Lake Formation is in fault contact with island arc volcanic–sedimentary sequences of the Amisk and Missi Groups. To identify the depositional environment of the Embury Lake Formation, we used lithologic and geochemical approaches. Here, we report carbon isotopic values in organic matter (δ¹³C_org) and sulfur isotopes (δ³⁴S), as well as total organic carbon and total sulfur measurements for the black shale in the formation. Samples were taken from a drill core that contains alternating bands of sandstone and black shale. Pyrite in the black shale is divided into four textural types: euhedral, vein‐type, elliptical, and microcrystalline. Microcrystalline pyrite is typically generated by microbially mediated sulfate reduction. An extremely low S/C ratio (avg. = 0.04) is consistent with lacustrine deposition. The ranges of δ¹³C_org (?36 ‰ to ?27 ‰) and δ³⁴S (+3.0 ‰ to +7.7 ‰) values can be explained by bacterial photosynthesis that involved Calvin cycle and acetyl CoA pathways, and sulfate reduction in a low‐sulfate environment. Considering the depositional age reported in a previous study of < 1.84 Ga, the Embury Lake Formation was likely emplaced in a lacustrine setting during the Trans‐Hudson Orogeny.     

Cenomanian (Upper Cretaceous) carbon isotope stratigraphy of terrestrial organic matter for the Yezo Group, Hokkaido, Japan

Abstract Carbon isotope fluctuations of sedimentary organic matter along the two geological traverses in the Yezo Group, Hokkaido, northern Japan, elucidate a detailed chemostratigraphy for the Cenomanian Stage on the northwestern Pacific margin. Visual characterization of the kerogen from mudstone samples shows that the major constituents of sedimentary organic matter originated as terrestrial higher plants. The atomic hydrogen/carbon ratios of the kerogen suggest that the original δ¹³C values of terrestrial organic matter (TOM) have not been affected significantly by thermal diagenesis. The patterns in two δ¹³C_TOM curves are similar and independent of changes in lithology and total organic carbon contents, which suggests that TOM was mixed sufficiently before the deposition in the Yezo forearc basin for the δ¹³C composition having been homogenized. In addition, this implies that the Hokkaido δ¹³C_TOM profiles represent the averaged temporal δ¹³C variations of terrestrial higher‐plant vegetation in the hinterlands of northeast Asia during Cenomanian time. Three shorter‐term (ca. 0.1 my duration) positive‐and‐negative δ¹³C_TOM fluctuations of ∼1‰ are present in the Lower to Middle Cenomanian interval in the Yezo Group. On the basis of the age‐diagnostic taxa (ammonoids, inoceramids and planktic foraminifers), these discrete δ¹³C_TOM events are interpreted to be correlated with those in the δ¹³C curves of pelagic carbonates from European basins. The correlation of δ¹³C events between the European and Yezo Group sections suggests that the shorter‐term δ¹³C fluctuations in Cenomanian ocean‐atmosphere carbon reservoirs are useful for global chemostratigraphic correlation of marine strata. In particular, the correlation of δ¹³C fluctuations of the so‐called ‘Mid‐Cenomanian event’ (MCE) implies: (i) the δ¹³C variations of global carbon reservoir during the MCE are precisely recorded in the δ¹³C_TOM records; and (ii) the MCE δ¹³C_TOM event is an efficient chronostratigraphic index for the Lower/Middle Cenomanian boundary of the Mid‐Cretaceous sequences.     

Spatial distributions of δ13C, δ15N and C/N ratios in suspended particulate organic matter of a bay under serious anthropogenic influences: Daya Bay,China

Stable isotopic signatures (δ¹³C and δ¹⁵N) and C/N ratios of suspended particulate organic matter (POM) were investigated from the surface water of Daya Bay during summer and winter of 2015. The relatively high δ¹³C_POM values suggested the input of ¹³C-depleted terrigenous organic matter was low in Daya Bay. There were significant correlations between δ¹³C_POM values and chlorophyll a concentrations both during summer and winter, suggesting the δ¹³C_POM values were mainly controlled by the phytoplankton biomass in the surface water. The distribution of δ¹⁵N_POM values was more complicated than that of δ¹³C_POM and displayed low values in the outer bay and the Dan'ao River estuary. ¹⁵N-depleted ammonia originating from industrial wastewater might have strongly influenced the water quality and stable isotopic signatures of POM near the Dan'ao River estuary. The δ¹³C_POM and δ¹⁵N_POM values strongly reflect the influences of anthropogenic activity and eutrophication in Daya Bay.     

Distribution and sources of sedimentary organic matter in a tropical estuary,south west coast of India (Cochin estuary): A baseline study

Surface sediments samples were collected from 9 stations of the Cochin estuary during the monsoon, post-monsoon and pre-monsoon seasons and were analyzed for grain size, total organic carbon (OC), total nitrogen (TN) and stable isotopic ratios of carbon (δ¹³C) and nitrogen (δ¹⁵N) to identify major sources of organic matter in surface sediments. Sediment grain size is found to be the key factor influencing the organic matter accumulation in surface sediments. The δ¹³C values ranges from ?27.5‰ to ?21.7‰ in surface sediments with a gradual increase from inner part of the estuary to the seaward side that suggest an increasing contribution of marine autogenous organic matter towards the seaward side. The δ¹⁵N value varies between 3.1‰ and 6.7‰ and it exhibits complex spatial and seasonal distributions in the study area. It is found that the dynamic cycling of nitrogen through various biogeochemical and organic matter degradation processes modifies the OC/TN ratios and δ¹⁵N to a considerable degree. The fraction of terrestrial organic matter in the total organic matter pool ranges from 13% to 74% in the surface sediments as estimated by δ¹³C based two end member mixing model.     

Characteristics of δ13CDIC in lakes on the Tibetan Plateau and its implications for the carbon cycle

Dissolved inorganic carbon isotope (δ¹³C_DIC) is an important tool to reveal the carbon cycle in lake systems. However, there are only few studies focusing on the spatial variation of δ¹³C_DIC of closed lakes. Here we analyze the characteristics of δ¹³C_DIC of 24 sampled lakes (mainly closed lakes) across the Qiangtang Plateau (QTP) and identify the driving factors for its spatial variation. The δ¹³C_DIC value of these observed lakes varies in the range of ? 15·0 to 3·2‰, with an average value of ? 1·2‰. The δ¹³C_DIC value of closed lakes is close to the atmospheric isotopic equilibrium value, much higher than that in rivers and freshwater lakes reported before. The high δ¹³C_DIC value of closed lakes is mainly attributed to the significant contribution of carbonate weathering in the catchment and the evasion of dissolved CO₂ induced by the strong evaporation of lake water. The δ¹³C_DIC value of closed lakes has a logarithmic correlation with water chemistry (TDS, DIC and pCO₂), also suggesting that the evapo‐concentration of lake water can influence the δ¹³C_DIC value. The δ¹³C_DIC value shows two opposite logarithmic correlations with lake size depending on the δ¹³C_DIC range. This study suggests that the δ¹³C in carbonates in lacustrine sediments can be taken as an indicator of lake volume variation in closed lakes on QTP. Copyright © 2011 John Wiley & Sons, Ltd.     

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.     

Two episodes of C-depletion in organic carbon in the latest Permian: Evidence from the terrestrial sequences in northern Xinjiang, China

New analyses reveal two intervals of distinctly lower δ¹³C values in the terrestrial organic matter of Permian–Triassic sequences in northern Xinjiang, China. The younger negative δ¹³C_org spike can be correlated to the conspicuous and sharp δ¹³C drops both in carbonate carbon and organic carbon near the Permian–Triassic event boundary (PTEB) in the marine section at Meishan. The geochemical correlation criteria are accompanied by a magnetic susceptibility pulse and higher abundances of distinctive, chain-like organic fossil remains of Reduviasporonites.The older negative δ¹³C_org spike originates within a latest Permian regression. Significant changes in organic geochemical proxies are recorded in the equivalent interval of the marine section at Meishan. These include relatively higher concentrations of total organic carbon, isorenieratane, C₁₄–C₃₀ aryl isoprenoids and lower ratios of pristane/phytane that, together, indicate the onset of anoxic, euxinic and restricted environments within the photic zone. The massive and widespread oxidation of buried organic matter that induced these euxinic conditions in the ocean would also result in increased concentrations of ¹³C-depleted atmospheric CO₂. The latest Permian environmental stress marked by the older negative δ¹³C_org episode can be correlated with the distinct changeover of ostracod assemblages and the occurrences of morphological abnormalities of pollen grains. These observations imply that biogeochemical disturbance was manifested on the land at the end of the Permian and that terrestrial organisms responded to it before the main extinction of the marine fauna.     

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

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

Siliceous productivity changes in Gulf of Ancud sediments (42°S, 72°W), southern Chile,over the last ∼150 years

We evaluated changes in siliceous export production and the source of organic matter preserved in sediment core MD07-3109H recovered from the Gulf of Ancud, Chiloé Inner Sea (42°S, 72°W, water column depth: 328 m), southern Chile. We analyzed the abundance of siliceous microfossils (diatoms, silicoflagellates, sponge spicules, Chrysophyte cysts, phytoliths), geochemical proxies (weight percent silicon %Si_OPAL, organic carbon, total nitrogen, C/N molar), and sediment stable isotopes (δ¹³C_org, δ¹⁵N). Chronology based on ²¹⁰Pb and ¹⁴C provided an accumulated age of 144 years at the base of the core.Sediments of core MD07-3109H are predominantly marine in origin, averaging δ¹³C_org=–20.75‰±0.82, δ¹⁵N=8.7±0.35‰, and C/N=8.76±0.36. Marine diatoms compose 94% of the total assemblage of siliceous microfossils. Our record of productivity based on the mass accumulation rates of organic carbon, total nitrogen, Si_OPAL, and total diatoms showed high values between 1863 and 1869 AD followed by a declining trend until 1921 AD, a transition period from 1921 to 1959 AD with fluctuating values, and a clear decreasing pattern from 1960 AD to the present. This marked reduction in productivity was associated with decreased precipitation and Puelo River streamflow (41°S), as well as a warmer and more stratified water column, especially since the 1980s.     

Efficient trapping of organic carbon in sediments on the continental margin with high fluvial sediment input off southwestern Taiwan

Accumulation rates of marine and terrigenous organic carbon in the continental margin sediments off southwestern Taiwan were estimated from the measured concentrations and isotopic compositions of total organic carbon (TOC) and previously reported sedimentation rates. Surficial sediments were collected from the study area spanning from the narrow shelf near the Kaoping River mouth to the deep slope with depths reaching almost 3000 m. The average sediment loading of Kaoping River is 17 Mt/yr, which yields high sediment accumulation rates ranging from 0.08 to 1.44 g cm⁻² yr⁻¹ in the continental margin. About half of the discharged sediments were deposited on the margin within 120 km of the river mouth. Carbon isotopic compositions of terrestrial and marine end-members of organic matter were determined, respectively, based on suspended particulate matter (SPM) collected from three major rivers in the southwestern Taiwan and from an offshore station. All samples were analyzed for the TOC content and its isotopic composition (δ¹³C_org). The SPM samples were also analyzed for the total nitrogen (TN) content. TOC content in marine sediments ranges from 0.45% to 1.35% with the highest values on the upper slope near the Kaoping River mouth. The TOC/TN ratio of the SPM samples from the offshore station is 6.8±0.6, almost identical to the Redfield ratio, indicating their predominantly marine origin; their δ¹³C_org values are also typically marine with a mean of −21.5±0.3‰. The riverine SPM samples exhibit typical terrestrial δ¹³C_org values around −25‰. The δ¹³C_org values of surficial sediments range from −24.8‰ to −21.2‰, showing a distribution pattern influenced by inputs from the Kaoping River. The relative contributions from marine and terrestrial sources to sedimentary organic carbon were determined by the isotope mixing model with end-member compositions derived from the riverine and marine SPM. High fluvial sediment inputs lead to efficient trapping of organic carbon over a wide range of water depth in this continental margin. The marine organic accumulation rate ranges from 1.6 to 70 g C m⁻² yr⁻¹ with an area weighted mean of 4.2 g C m⁻² yr⁻¹, which is on a par with the mean terrestrial contribution and accounts for 2.3% of mean primary production. The depth-dependent accumulation rate of marine organic carbon can be simulated with a function involving primary productivity and mineral accumulation rate, which may be applicable to other continental margins with high sedimentation rates. Away from the nearshore area, the content of terrigenous organic carbon in surficial sediments decreases with distance from the river mouth, indicating its degradation in marine environments.     

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

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

Dissolved inorganic carbon evolution in neutral discharge from mine tailings piles

We measured the concentrations of dissolved inorganic carbon (DIC) and major ions and the stable carbon isotope ratios of DIC (δ¹³C_DIC) in two creeks discharging from carbonate‐rich sulphide‐containing mine tailings piles. Our aim was to assess downstream carbon evolution of the tailings discharge as it interacted with the atmosphere. The discharge had pH of 6.5–8.1 and was saturated with respect to carbonates. Over the reach of one creek, the DIC concentrations decreased by 1.1 mmol C/l and δ¹³C_DIC increased by ~4.0‰ 200 m from the seep source. The decrease in the DIC concentrations was concomitant with decreases in the partial pressure of CO_2(aq) because of the loss of excess CO_2(aq) from the discharge. The corresponding enrichment in the δ¹³C_DIC is because of kinetic isotope fractionation accompanying the loss of CO_2(g). Over the reach of the other creek, there was no significant decrease in the DIC concentrations or notable changes in the δ¹³C_DIC. The insignificant change in the DIC concentrations and the δ¹³C_DIC is because the first water sample was collected 160 m away from the discharge seep, not accessible during this research. In this case, most of the excess CO_2(aq) was lost before our first sampling station. Our results indicate that neutral discharges from tailings piles quickly lose excess CO_2(aq) to the atmosphere and the DIC becomes enrich in ¹³C. We suggest that a significant amount of carbon cycling in neutral discharges from tailings piles occur close to the locations where the discharge seeps to the surface. Copyright © 2015 John Wiley & Sons, Ltd.     

Sources and distribution of organic matter in northern Patagonia fjords,Chile (∼44–47°S): A multi-tracer approach for carbon cycling assessment

We investigated the provenance of organic matter in the inner fjord area of northern Patagonia, Chile (～44–47°S), by studying the elemental (organic carbon, total nitrogen), isotopic (δ¹³C, δ¹⁵N), and biomarker (n-alkanoic acids from vascular plant waxes) composition of surface sediments as well as local marine and terrestrial organic matter. Average end-member values of N/C, δ¹³C, and δ¹⁵N from organic matter were 0.127±0.010, ?19.8±0.3‰, and 9.9±0.5‰ for autochthonous (marine) sources and 0.040±0.018, ?29.3±2.1‰, and 0.2±3.0‰ for allochthonous (terrestrial) sources. Using a mixing equation based on these two end-members, we calculated the relative contribution of marine and terrestrial organic carbon from the open ocean to the heads of fjords close to river outlets. The input of marine-derived organic carbon varied widely and accounted for 13–96% (average 61%) of the organic carbon pool of surface sediments. Integrated regional calculations for the inner fjord system of northern Patagonia covered in this study, which encompasses an area of ～4280 km², suggest that carbon accumulation may account for between 2.3 and 7.8×10⁴ ton C yr^?1. This represents a storage capacity of marine-derived carbon between 1.8 and 6.2×10⁴ ton yr^?1, which corresponds to an assimilation rate of CO₂ by marine photosynthesis between 0.06 and 0.23×10⁶ ton yr^?1. This rate suggests that the entire fjord system of Patagonia, which covers an area of ～240,000 km², may represent a potentially important region for the global burial of marine organic matter and the sequestration of atmospheric CO₂.     

Biomarker evidence for biotic and environmental change across the Cambrian Series 2–Series 3 boundary at the Wuliu- Zengjiayan section,Guizhou, China

The Wuliu-Zengjiayan section in Jianhe County, Guizhou Province, China has been suggested as a potential Global Stratotype Section and Point(GSSP) for the defined base of Cambrian Series 3. A molecular organic geochemical study on the Cambrian Series 2Series 3 boundary interval was carried out to reveal the biotic and environmental change during this transition. The hydrocarbons extracted from the Kaili Formation were proved to be indigenous. The various geochemical proxies such as biomarker parameter, δ13Corg, atomic H/C value of kerogen, and TOC content, co-vary along with the sedimentary column, and show a quick and significant change just across the Cambrian Series 2Series 3 boundary. The less abundance of isoprenoid hydrocarbons, the relative enrichment of midchain monomethyl branched alkanes(mmb-alkanes), the relatively negative value of δ13Corg, and the higher TOC contents may suggest that the upper Cambrian Series 2 was deposited in a relatively reducing environment with a higher organic input from cyanobacteria-predominated benthic microbial mats. On the other hand, the relative enrichment of isoprenoid hydrocarbons, the less abundance of mmb-alkanes, the relatively positive value of δ13Corg, the lower TOC contents, and the lower atomic H/C values of kerogen are combined to indicate an enhanced phytoplankton production and an increased oxygen content and nutrients in the ocean during the early Cambrian Series 3, which could have benefited the explosion of the Kaili Biota. The Wuliu-Zengjiayan section may provide a typical case to understand the co-variation of marine microbe, animal, and environment.     

Elemental and stable isotopic constraints on river influence and patterns of nitrogen cycling and biological productivity in Hudson Bay

Elemental (carbon and nitrogen) ratios and stable carbon and nitrogen isotope ratios (δ¹³C and δ¹⁵N) are examined in sediments and suspended particulate matter from Hudson Bay to study the influence of river inputs and autochthonous production on organic matter distribution. River-derived particulate organic matter (POM) is heterogeneous, nitrogen-poor and isotopically depleted, consistent with expectations for OM derived from terrestrial C3 vascular plant sources, and distinct from marine OM sources. Both δ¹³C and C/N source signatures seem to be transmitted to sediments with little or no modification, therefore making good tracers for terrigenous OM in Hudson Bay. They suggest progressively larger contributions from marine sources with distance from shore and secondarily from south to north, which broadly corresponds to the distribution of river inputs to Hudson Bay. Processes other than mixing of marine and terrigenous OM influence sedimentary δ¹⁵N values, including variability in the δ¹⁵N of phytoplankton in the Bay's surface waters due to differences in relative nitrate utilization, and post-production processes, which bring about an apparently constant ¹⁵N-enrichment between surface waters and underlying sediments. Variability in the δ¹⁵N of phytoplankton in the Bay's surface waters, in contrast, seems to be organized spatially with a pattern that suggests an inshore–offshore difference in surface water nitrogen conditions (open- vs. closed-system) and hence the δ¹⁵N value of phytoplankton. The δ¹⁵N patterns, supported by a simple nitrate box-model budget, suggest that in inshore regions of Hudson Bay, upwelling of deep, nutrient-rich waters replenishes surface nitrate, resulting in ‘open system’ conditions which tend to maintain nitrate δ¹⁵N at low and constant values, and these values are reflected in the sinking detritus. River inflow, which is constrained to inshore regions of Hudson Bay, appears to be a relatively minor source of nitrate compared to upwelling of deep waters. However, river inflow may contribute indirectly to enhanced inshore nutrient supply by supporting large-scale estuarine circulation and consequently entrainment and upwelling of deep water in this area. In contrast to previous proposals that Hudson Bay is oligotrophic because it receives too much fresh water (Dunbar, 1993), our results support most of the primary production being organized around the margin of the Bay, where river flow is constrained.     

Carbon and its isotopes in mid-oceanic basaltic glasses

Three carbon components are evident in eleven analyzed mid-oceanic basalts: carbon on sample surfaces (resembling adsorbed gases, organic matter, or other non-magmatic carbon species acquired by the glasses subsequent to their eruption), mantle carbon dioxide in vesicles, and mantle carbon dissolved in the glasses. The combustion technique employed recovered only reduced sulfur, all of which appears to be indigenous to the glasses. The dissolved carbon concentration (measured in vesicle-free glass) increases with the eruption depth of the spreading ridge, and is consistent with earlier data which show that magma carbon solubility increases with pressure. The total glass carbon content (dissolved plus vesicular carbon) may be controlled by the depth of the shallowest ridge magma chamber. Carbon isotopic fractionation accompanies magma degassing; vesicle CO₂ is about 3.8‰ enriched in ¹³C, relative to dissolved carbon. Despite this fractionation, δ¹³C_PDB values for all spreading ridge glasses lie within the range ?5.6 and ?7.5, and the δ¹³C_PDB of mantle carbon likely lies between ?5 and ?7. The carbon abundances and δ¹³C_PDB values of Kilauea East Rift glasses apparently are influenced by the differentiation and movement of magma within that Hawaiian volcano. Using ³He and carbon data for submarine hydrothermal fluids, the present-day mid-oceanic ridge mantle carbon flux is estimated very roughly to be about 1.0 × 10¹³ g C/yr. Such a flux requires 8 Gyr to accumulate the earth's present crustal carbon inventory.     

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.