Loading and fate of particulate organic carbon from the Himalaya to the Ganga-Brahmaputra delta

We use the evolution of river sediment characteristics and sedimentary C_org from the Himalayan range to the delta to study the transport of C_org in the Ganga-Brahmaputra system and especially its fate during floodplain transit.A detailed characterisation of both mineral and organic particles for a sampling set of river sediments allows taking into account the sediment heterogeneity characteristic of such large rivers. We study the relationships between sediment characteristics (mineralogy, grain size, specific area) and C_org content in order to evaluate the controls on C_org loading. Contributions of C3 and C4 plants are estimated from C_org stable isotopic composition (δ¹³C_org). We use the evolution of δ¹³C_org values from the Himalayan range to the delta in order to study the fate of C_org during floodplain transit.Ganga and Brahmaputra sediments define two distinct linear relations with specific area. In spite of 4-5 times higher specific area, Ganga sediments have similar C_org content, grain size and mineralogy as Brahmaputra sediments, indicating that specific area does not exert a primary control on C_org loading. The general correlation between the total C_org content and Al/Si ratio indicates that C_org loading is mainly related to: (1) segregation of organic particles under hydrodynamic forces in the river, and (2) the ability of mineral particles to form organo-mineral aggregates.Bed and suspended sediments have distinct δ¹³C_org values. In bed sediments, δ¹³C_org values are compatible with a dominant proportion of fossil C_org derived from Himalayan rocks erosion. Suspended sediments from Himalayan tributaries at the outflow of the range have low δ¹³C_org values (−24.8‰ average) indicating a dominant proportion of C3 plant inputs. In the Brahmaputra basin, δ¹³C_org values of suspended sediments are constant along the river course in the plain. On the contrary, suspended sediments of the Ganga in Bangladesh have higher δ¹³C_org values (−22.4‰ to −20.0‰), consistent with a significant contribution of C4 plant derived from the floodplain. Our data indicate that, during the plain transit, more than 50% of the recent biogenic C_org coming from the Himalaya is oxidised and replaced by floodplain C_org. This renewal process likely occurs during successive deposition-erosion cycles and river course avulsions in the plain.     

Variation and paleoclimatic significance of organic carbon isotopes of Ili loess in arid Central Asia

As an indicator for terrestrial paleovegetation, the stable isotopic composition of total organic matter (δ¹³C_org) in loess sediments has been widely used for paleoclimatic reconstruction in western Europe, the Great Plains of North America and the Chinese Loess Plateau (CLP). However, little is known about the variation and paleoclimatic significance of the loess δ¹³C_org in arid Central Asia (ACA). We report δ¹³C_org data from an Axike (AXK) loess/paleosol profile from the eastern Ili Basin, eastern Central Asia. Along the profile, the δ¹³C_org values were more negative in the paleosol layers observed in the field and were confirmed by environmental magnetic proxies and a higher concentration of total organic carbon (TOC), consistent with results for western Europe and the northwestern CLP. Our results demonstrate that the loess δ¹³C_org in this region documents mainly the response of δ¹³C of locally predominant C₃ plants to paleoclimatic variation, especially paleoprecipitation. Our results also suggest that the loess δ¹³C_org values in the area have the potential for quantitative paleoprecipitation reconstruction on the basis of detailed δ¹³C_org results from modern plants and surface soils in the future.     

Transformation of particulate organic matter at the water-bottom boundary in the Russian Arctic seas: Evidence from isotope and radioisotope data

Complex biogeochemical studies including the determination of isotopic composition of C_org in both suspended particulate matter and surface horizon (0–1 cm) of sediments (more than 260 determinations of δ¹³C-C_org) were carried out for five Arctic shelf seas: White, Barents, Kara, East Siberian, and Chukchi. The aim of this study is to elucidate causes that change the isotopic composition of particulate organic carbon at the water-sediment boundary. It is shown that the isotopic composition of C_org in sediments from seas with a high river runoff (White, Kara, and East Siberian) does not inherit the isotopic composition of C_org in particles precipitating from the water column, but is enriched in heavy ¹³C. Seas with a low river runoff (Barents and Chukchi) show insignificant difference between the value of δ¹³C-C_org in both suspended load and sediment because of a low content of the isotopically light allochthonous organic matter (OM) in particulates. Complex biogeochemical studies with radioisotope tracers (¹⁴CO₂, ³⁵S, and ¹⁴CH₄) revealed the existence of specific microbial filter formed from heterotrophic and autotrophic organisms at the water-sediment boundary. This filter prevents the mass influx of products of OM decomposition into water column, as well as reduces the influx of a part of OM contained in the suspended particulate matter from water into sediment.     

Soil organic matter as an important contributor to Late Quaternary sediments of the tropical West African continental margin

The contribution of soil organic matter (SOM) to continental margins is largely ignored in studies on the carbon budget of marine sediments. Detailed geochemical investigations of late Quaternary sediments (245-0 ka) from the Niger and Congo deep-sea fans, however, reveal that C_org/N_tot ratios and isotopic signatures of bulk organic matter (δ¹³C_org) in both fans are essentially determined by the supply of various types of SOM from the river catchments thus providing a fundamentally different interpretation of established proxies in marine sciences. On the Niger fan, increased C_org/N_tot and δ¹³C_org (up to −17‰) were driven by generally nitrogen-poor but ¹³C-enriched terrigenous plant debris and SOM from C₄/C₃ vegetation/Entisol domains (grass- and tree-savannah on young, sandy soils) supplied during arid climate conditions. Opposite, humid climates supported drainage of C₃/C₄ vegetation/Alfisol/Ultisol domains (forest and tree-savannah on older/developed, clay-bearing soils) that resulted in lower C_org/N_tot and δ¹³C_org (< −20‰) in the Niger fan record. Sediments from the Congo fan contain a thermally stable organic fraction that is absent on the Niger fan. This distinct organic fraction relates to strongly degraded SOM of old and highly developed, kaolinite-rich ferallitic soils (Oxisols) that cover large areas of the Congo River basin. Reduced supply of this nitrogen-rich and ¹²C-depleted SOM during arid climates is compensated by an elevated input of marine OM from the high-productive Congo up-welling area. This climate-driven interplay of marine productivity and fluvial SOM supply explains the significantly smaller variability and generally lower values of C_org/N_tot and δ¹³C_org for the Congo fan records. This study emphasizes that ignoring the presence of SOM results in a severe underestimation of the terrigenous organic fraction leading to erroneous paleoenvironmental interpretations at least for continental margin records. Furthermore, burial of SOM in marine sediments needs more systematic investigation combining marine and continental sciences to assess its global relevance for long-term sequestration of atmospheric CO₂.     

A mid-late Holocene sapropelic sediment unit from the southern Marmara sea shelf and its palaeoceanographic significance

A sapropelic layer, having an age of ca 4750 and 3500 ¹⁴C y BP, was discovered at 0.90–2.35 m below the sea floor (mbsf) in gravity cores from the southern shelf of the Marmara Sea. It is a 15–50 cm thick, phosphorescent green to grey, plastic, clayey hemipelagic mud horizon, containing 1.5–2.9% organic carbon (C_org). The increase in C_org and biogenic carbonate, together with a rich planktonic foraminiferal fauna, indicate increased organic productivity and warm surface waters during the deposition of the sapropelic layer. The down-core profiles of Mn, Fe, Cu, Zn, Pb, Cr, Ni and Co suggest that the sapropelic layer was deposited through an essentially oxic water column. The benthonic foraminiferal fauna indicates reduced oxygen levels in bottomwaters. The sapropelic unit was deposited during a high stand of global sea level. Its deposition was initiated by a large input of terrestrial organic matter and nutrient-rich fresh waters under a relatively warm and wet climate. The fresh water supply caused a strong water stratification, which, in turn, together with high organic matter input, resulted in reduced oxygen levels in the bottomwaters.     

Composition and origin of organic matter in surface sediments of Lake Sarbsko: A highly eutrophic and shallow coastal lake (northern Poland)

We present an organic geochemical study of surface sediments of Lake Sarbsko, a shallow coastal lake on the middle Polish Baltic coast. The aim was to provide evidence concerning the origin of the organic matter (OM) and its compositional diversity in surface deposits of this very productive, highly dynamic water body. The content and composition of the OM in the bottom sediments were investigated at 11 sampling stations throughout the lake basin. OM sources were assigned on the basis of bulk indicators [total organic carbon (TOC), total nitrogen (TN), δ¹³C_TOC and δ¹⁵N and extractable OM yield], biomarker composition of extractable OM and compound-specific C isotope signatures. The source characterization of autochthonous compounds was verified via phytoplankton analysis. The distribution of gaseous hydrocarbons in the sediments, as well as temporal changes in lake water pH, the concentration of DIC (dissolved inorganic carbon) and δ¹³C_DIC were used to trace OM decomposition.The sedimentary OM is composed mainly of well preserved phytoplankton compounds and shows minor spatial variability in composition. However, the presence of CH₄ and CO₂ in the bottom deposits provides evidence for microbial degradation of sedimentary OM. The transformation of organic compounds in surface, bottom and pore waters via oxidative processes influences carbonate equilibrium in the lake and seasonally favours precipitation or dissolution of CaCO₃.The data enhance our understanding of the relationships between the composition of sedimentary OM and environmental conditions within coastal ecosystems and shed light on the reliability of OM proxies for environmental reconstruction of coastal lakes.     

Composition and genesis of the organic matter in the bottom sediments of the East Siberian Sea

The chemical composition of organic matter (C_org, N_org, δ¹³C, δ¹⁵N, and n-alkanes) was studied in the top layer of bottom sediments of the East Siberian Sea. Possible ways were proposed to estimate the amount of the terrigenous component in their organic matter (OM). The fraction of terrigenous OM estimated by the combined use of genetic indicators varied from 15% in the eastern part of the sea, near the Long Strait, to 95% in the estuaries of the Indigirka and Kolyma rivers, averaging 62% over the sea area.     

Influence of the ratio of planktonic to benthic diatoms on lacustrine organic matter δ13C from Erlongwan maar lake,northeast China

Carbon isotope ratio (δ¹³C_org) values of organic matter in lake sediments are commonly used to reconstruct environmental change, but the factors which influence change are varied and complex. Here we report δ¹³C values for sediments from Erlongwan maar lake in northeast China. In this record, changes in δ¹³C cannot be explained by simple changes in aquatic productivity. Instead, values were likely influenced by differences in the ratio between planktonic and benthic algae, as indicated by the remains of diatoms. This is because the variation of δ¹³C_org in algae from different habitats is controlled by the thickness of the diffusive boundary layer, which is dependent on the turbulence of the water. Compared with benthic algae, which grow in relatively still water, pelagic algae are exposed to greater water movement. This is known to dramatically reduce the thickness of the boundary layer and was found to cause even more severe δ¹³C depletion. In Erlongwan maar lake, low values were linked to the dominance of planktonic diatoms during the period commonly known as the Medieval Warm Period. Values gradually increased with the onset of the Little Ice Age, which we interpret as being driven by an increase in the proportion of benthic taxa, due to effect of the colder climate. The increase in planktonic diatoms at the end of the Little Ice Age, linked to higher temperature and a reduction in ice cover, resulted in a further decline in δ¹³C_org.     

Origin of methane in high-arsenic groundwater of Taiwan – Evidence from stable isotope analyses and radiocarbon dating

Groundwaters in the confined aquifers of the Chianan and Ilan coastal plains of Taiwan are rich in dissolved methane (CH₄). Serious endemic “blackfoot disease”, which occurred in the Chianan plain, especially during AD1950-1970, has been demonstrated to have arisen from drinking highly reducing groundwater with abnormal arsenic and humic substance levels. In order to explore the origin of CH₄ and its hydrological implications, stable carbon isotope ratios (δ¹³C) and radiocarbon (¹⁴C) ages of exsolved CH₄, dissolved inorganic carbon (DIC), and sedimentary biogenic sediments from a total of 34 newly completed water wells at 16 sites were determined. The main results obtained are as follows: (1) The δ¹³C_CH4 (−65‰ to −75‰) values indicate that, except for one thermogenic sample (δ¹³C_CH4=38.2‰) from the Ilan plain, all CH₄ samples analyzed were produced via microbially mediated CO₂ reduction. Many δ¹³C_DIC values are considerably greater than −10‰ and even up to 10‰ due to Rayleigh enrichment during CO₂ reduction. (2) Almost all the ¹⁴C ages of CH₄ samples from the shallow aquifer (I) (<60 m depth) are greater than the ¹⁴C ages of coexisting DIC and sediments, suggesting the presence of CH₄ from underlying aquifers. (3) The ¹⁴C ages of coexisting CH₄, DIC and sediments from aquifer (II) of the Chianan plain are essentially equal, reflecting in-situ generation of CH₄ and DIC from decomposition of sedimentary organic matter and sluggishness of the groundwater flow. On the other hand, both CH₄ and DIC from each individual well of the relatively deep aquifers (III) and (IV) in the Chianan plain are remarkably younger than the deposition of their coexisting sediments, indicating that current groundwaters entered these two aquifers much later than the deposition of aquifer sediments. (4) Each CH₄ sample collected from the Ilan plain is older than coexisting DIC, which in turn is distinctly older than the deposition of respective aquifer sediments, demonstrating the presence of much older CO₂ and CH₄ from underlying strata.     

Isotopic identification of the source of methane in subsurface sediments of an area surrounded by waste disposal facilities

The major source of methane (CH₄) in subsurface sediments on the property of a former hazardous waste treatment facility was determined using isotopic analyses measured on CH₄ and associated groundwater. The site, located on an earthen pier built into a shallow wetland lake, has had a history of waste disposal practices and is surrounded by landfills and other waste management facilities. Concentrations of CH₄ up to 70% were found in the headspace gases of several piezometers screened at 3 different depths (ranging from 8 to 17 m) in lacustrine and glacial till deposits. Possible sources of the CH₄ included a nearby landfill, organic wastes from previous impoundments and microbial gas derived from natural organic matter in the sediments.Isotopic analyses included δ¹³C, δD, ¹⁴C, and ³H on select CH₄ samples and δD and δ¹⁸O on groundwater samples. Methane from the deepest glacial till and intermediate lacustrine deposits had δ¹³C values from −79 to −82‰, typical of natural “drift gas” generated by microbial CO₂-reduction. The CH₄ from the shallow lacustrine deposits had δ¹³C values from −63 to −76‰, interpreted as a mixture between CH₄ generated by microbial fermentation and the CO₂-reduction processes within the subsurface sediments. The δD values of all the CH₄ samples were quite negative ranging from −272 to −299‰. Groundwater sampled from the deeper zones also showed quite negative δD values that explained the light δD observed for the CH₄. Radiocarbon analyses of the CH₄ showed decreasing ¹⁴C activity with depth, from a high of 58 pMC in the shallow sediments to 2 pMC in the deeper glacial till. The isotopic data indicated the majority of CH₄ detected in the till deposits of this site was microbial CH₄ generated from naturally buried organic matter within the subsurface sediments. However, the isotopic data of CH₄ from the shallow piezometers was more variable and the possibility of some mixing with oxidized landfill CH₄ could not be completely ruled out.     

Carbon and hydrogen isotope ratio characterization of methane dynamics for Fluxnet Peatland Ecosystems

Methane concentration [CH₄] and stable isotope ratio values (δ¹³C) characterize methanogenic and methanotrophic processes within two contrasting peatland ecosystems of the Fluxnet Canada Research Network: (i) a western Canada peatland fen in northern Alberta (Fen) and (ii) an eastern Canada peatland bog in southeastern Ontario (Bog). We use carbon isotope ratio discrimination of produced methane (δ¹³C_CH4) from the precursor carbon compounds (δ¹³C_preC) to estimate the relative proportions of archaebacterial acetoclastic methanogenesis (AM) and hydrogenotrophic carbonate reduction methanogenesis (HM) in these terrestrial ecosystems. The [CH₄] and δ¹³C_CH4 signatures describe contrasts in the methanogenic and methanotrophic processes between the Fen and the Bog. The differences are substantiated by stable hydrogen isotope ratio (δD) separation between the dissolved δD_CH4 and co-existing δD_H2O. Methanogenesis at the Fen is dominated by AM, in contrast to the Bog, which is essentially HM. We suggest that this is potentially a result of differences in type/quality of organic substrates. The trajectory of ¹³C enrichment in δ¹³C_CH4 values with depth at the Bog reflects a closed system, substrate depletion effect. Our Rayleigh distillation model estimates 58-76% depletion in the source dissolved inorganic carbon (DIC).     

Assessing the factors controlling high sedimentation rates from the latest Barremian–earliest Aptian in the hemipelagic setting of the restricted Organyà Basin,NE Spain

The Organyà Basin, south–central Spanish Pyrenees, developed as a marginal depocenter during a rapid extensional phase of anticlockwise rotation of the Iberian plate. As a result of increased subsidence, an important change in sedimentation occurred from the late Barremian to the Aptian leading to unusually high sediment accumulation rates. Approximately 1000 m of hemipelagic marls and limestones accumulated during this time interval.Here we studied the basal 85 m of the hemipelagic facies of the El Pui section, Organyà Basin, that are characterized by alternating 15 cm – ∼3 m thick beds of limestone and marls. Geochemical analyses indicate high total inorganic carbon (TIC) values (average 70%) suggesting enhanced CaCO₃ production and deposition. SEM analyses of the samples indicate high abundance of calcareous nannofossils, which together with the absence of shallow water taxa characteristic of the Urgonian Carbonate platform of Organyà, and the lack of sedimentary facies attributable to carbonate platform components point to nannofossils as the main source for the elevated TIC. Organic-rich levels (total organic carbon (TOC) up to 1.74%) concurrent with positive excursions up to 2‰ in δ¹³C_org, imply enhanced preservation of organic matter (OM) in the basin. In addition, pronounced peaks of δ¹³C_org higher than the global average suggest superimposed local factors related to intensified ¹²C removal due to primary productivity. Biomarker analyses and the δ¹³C_org profile suggest an autochthonous origin of the OM from phytoplankton and possible additional contributions from microbial communities.X-ray diffraction (XRD) results attest for sustained terrestrial fluxes as the source of nutrients to the basin because of a 30% average non-carbonate bulk mineral content in the sediment. The non-carbonate fraction is dominated by quartz (average, 14%) whereas the clay mineral assemblages are characterized by high illite content (>73 relative%) with minor concentrations of kaolinite (<5%), illite /smectite mixed layers (<17%) and chlorite (<15%), consistent with a provenance from the Paleozoic metamorphic terranes adjacent to the Organyà Basin.The integrated results suggest a high sediment accumulation rate (5 cm/ky–7.5 cm/ky) and enhanced carbon burial during the latest Barremian–earliest Aptian in the hemipelagic setting of the El Pui section.     

Carbon and oxygen stable isotopes in the middle-upper miocene and lower pliocene carbonates of the Eastern Paratethys (Kerch-Taman Region): Palaeoenvironments and post-sedimentation changes

C and O isotope composition of Middle-Upper Miocene and Lower Pliocene carbonates from Kerch-Taman Region (Eastern Paratethys) have been studied in order to reconstruct palaeoenvironmental variability and post-sedimentation changes. The δ¹³C and δ¹⁸О values of the Upper Sarmatian to Lower Pliocene organogenic carbonates reflect the desalinization of paleobasins, global Late Miocene Cooling, and increase in seasonal temperature fluctuations. Isotopic composition of the Middle Sarmatian organogenic carbonates was strongly influenced by evaporation processes, high bioproductivity, and local submarine methane emissions. Warm climate and low bioproductivity together with unstable hydrological regime during the Late Chokrakian and the Karaganian times influenced the isotope composition of primary carbonates. Calcite shell of Spiratella sp. (δ¹³C =–0.4‰ and δ¹⁸О =–0.4‰) from Tarkhanian sediments was formed in warm marine environment. Dolomitization prevails over other secondary mineralization in the studied carbonate rocks. Two groups of secondary dolomites that are characterized by negative and positive δ¹³C values have been recognized. Lowe δ¹³C values (up to–31.4‰) in dolomites indicate the influence of both dissolved inorganic carbon (DIC) from oxidized organic matter (С_org) and methane. Dolomites with positive δ¹³C values (7.0 and 7.8‰) associat with migration of CO₂- and CH₄-containing saline groundwater.     

Lacustrine sedimentary record of early Aptian carbon cycle perturbation in western Liaoning,China

The early Aptian abrupt carbon isotope excursion in marine carbonate and sedimentary organic matter reflects a major perturbation in the global carbon cycle. However, until now almost all the evidences of this event came from marine deposits. Here we present organic-carbon isotope (δ¹³C_org) data from the non-marine Jehol Group in western Liaoning, China. The lacustrine δ¹³C_org curve is marked by a relative long-lasting δ¹³C_org minimum followed by two stages of positive δ¹³C_org excursions that are well correlated with contemporaneous marine records. The carbon isotope correlation shows that the lacustrine strata of the Jehol Group were deposited at the same time of the early Aptian Oceanic Anoxic Event (OAE1a). The relative long-lasting δ¹³C_org minimum supports the hypothesis that volcanic CO₂ emission may have played the main role in triggering the negative δ¹³C excursion and global warming at the onset of this event. In addition, the onset of δ¹³C_org minimum is concomitant with the radiation of the Jehol Biota, implying that the evolutionary radiation of the Jehol Biota may have been closely related with the increase in atmospheric CO₂ and temperature.     

Isotopic evidence of enhanced carbonate dissolution at a coal mine drainage site in Allegheny County,Pennsylvania, USA

Stable isotopes were used to determine the sources and fate of dissolved inorganic C (DIC) in the circumneutral pH drainage from an abandoned bituminous coal mine in western Pennsylvania. The C isotope signatures of DIC (δ¹³C_DIC) were intermediate between local carbonate and organic C sources, but were higher than those of contemporaneous Pennsylvanian age groundwaters in the region. This suggests a significant contribution of C enriched in ¹³C due to enhanced carbonate dissolution associated with the release of H₂SO₄ from pyrite oxidation. The Sr isotopic signature of the drainage was similar to other regional mine waters associated with the same coal seam and reflected contributions from limestone dissolution and cation exchange with clay minerals. The relatively high δ³⁴S_SO4 and δ¹⁸O_SO4 isotopic signatures of the mine drainage and the presence of presumptive SO₄-reducing bacteria suggest that SO₄ reduction activity also contributes C depleted in ¹³C isotope to the total DIC pool. With distance downstream from the mine portal, C isotope signatures in the drainage increased_, accompanied by decreased total DIC concentrations and increased pH. These data are consistent with H₂SO₄ dissolution of carbonate rocks, enhanced by cation exchange, and C release to the atmosphere via CO₂ outgassing.     

A Lateglacial and Holocene organic carbon isotope record of lacustrine palaeoproductivity and climatic change derived from varved lake sediments of Lake Holzmaar,Germany

A composite varve-dated 11.4 m long sediment sequence from Lake Holzmaar, situated in the Eifel region of western Germany, was investigated for total organic matter content, total nitrogen content and stable organic carbon isotopes. Mean time resolution is 75 years for TN and 14 years for δ¹³C_org. On millennial time scales primary production of lacustrine algae strongly depends on the delivery of nutrients from the catchment. The respective carbon isotope record is characterized by marked variations of δ¹³C_org ranging from −36.0‰ to −27.0‰ and includes a number of pronounced shifts. Reactions of the lacustrine system and the catchment to changes of environmental parameters, e.g. runoff, solar radiation and temperature, induce changes of algal associations and of lacustrine primary production which are reflected in the sediments as carbon isotope variations. Clear evidence of ecosystem reorganizations is detected by the carbon isotope record around 14,200, 10,400, 9600, 5500, 2700, 1700 and 900 varve years BP. In particular, the Holocene events of 9600, around 5500 and 2700 are interpreted as the expression of massive changes of the climate system. The steady rise of δ¹³C_org values during the mid-Holocene is interpreted as a continuous climatic amelioration reaching an optimum around 6500 varve years BP. Rapid and large changes of δ¹³C_org values from 2700 varve years BP to the present indicate major disturbances in the catchment area. These are most probably related to deforestation or reforestation and runoff changes, presumably in conjunction with human impact. Carbon isotopes, thus, characterize the Holzmaar ecosystem in time revealing lacustrine palaeoproductivity as well as providing palaeoenvironmental and palaeoclimatic information.     

Paired δ13Ccarb and δ13Corg records of the Ordovician on the Yangtze platform,South China

During the Ordovician, huge biological revolutions and environmental changes happened in Earth’s history, including the Great Ordovician Biodiversification Event, global cooling and so on, but the cause of these events remains controversial. Herein, we conducted a paired carbon isotopic analysis of carbonate (δ¹³C_carb) and organic matter (δ¹³C_org) through the Ordovician in the Qiliao section on the Yangtze platform of South China. Our results showed that the δ¹³C_carb trend of the Qiliao section can be correlated with local and global curves. The δ¹³C_org trend seems is less clear than the δ¹³C_carb trend for stratigraphic correlations, but some δ¹³C_org positive excursions in the Middle and Upper Ordovician may be used for correlation studies. These carbon isotopic records may have global significance rather than local significance, revealing several fluctuations to the global carbon cycle during the Ordovician. Several known δ¹³C_carb and δ¹³C_org negative and positive excursions have been recognised in this study, including the early Floian Negative Inorganic Carbon (δ¹³C_carb) Excursion (EFNICE), as well as the early Floian Positive Organic Carbon (δ¹³C_carb) Excursion, the mid-Darriwilian Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (MDICE), and the early Katian Guttenberg Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (GICE). These positive excursions and a smooth decline trend of δ¹³C_org values during the early to mid-Floian may imply multiple episodes of enhanced organic carbon burial that began at the early Floian stage, probably resulting in further decline in atmospheric pCO₂ and then global cooling.     

Atmospheric weathering of Scandinavian alum shales and the fractionation of C,N and S isotopes

Subaerial exposure and oxidation of organic carbon (C_org)-rich rocks is believed to be a key mechanism for the recycling of buried C and S back to Earth's surface. Importantly, processes coupled to microbial C_org oxidation are expected to shift new biomass δ¹³C_org composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting δ¹³C_org at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, C_org-rich alum shale units of the Baltoscandian Basin believed to constitute a strong source of metal contaminants to the natural environment, following subaerial exposure and weathering. Consistent with independent support, we show that atmospheric oxidation of the sulfidic, C_org-rich alum shale sequence of the Cambrian-Devonian Baltoscandian Basin induces intense acid rock drainage at the expense of progressive oxidation of Fe sulfides. Sulfide oxidation takes priority over microbial organic matter decomposition, enabling quantitative massive erosion of C_org without producing a δ¹³C shift between acid rock drainage precipitates and shale. Moreover, ¹³C enrichment in inorganic carbon of precipitates does not support microbial C_org oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Δ³⁴S = δ³⁴S_shale − δ³⁴S_precipitates ≈ 0, accompanied by elevated S levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales, provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering. Slight δ¹⁵N depletion in the new surface precipitates relative to shale, coincides with dramatic loss of N from shales. Collectively, the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock-atmosphere interface, indicating that quantitative mass release of C_org, N, S, and key metals to the environment is a response to intense sulfide oxidation. Consequently, large-scale acidic weathering of the sulfide-rich alum shale units is suggested to influence the fate and redistribution of the isotopes of C, N, and S from shale to the immediate environment.     

C and O stable isotope variability in recent freshwater carbonates (River Krka, Croatia)

Three types of recent carbonate precipitates from the River Krka, Croatia, were analysed: (1) bulk tufa from four main cascades in a 34 km long section of the river flow through the Krka National Park; (2) a laminar stromatolite‐like incrustation formed in the tunnel of a hydroelectric power plant close to the lowest cascade; and (3) recent precipitates collected on artificial substrates during winter, spring and summer periods. Stable isotope compositions of carbon (δ¹³C) and oxygen (δ¹⁸O) in the carbonate and organic carbon (δ¹³C_org) were determined and compared with δ¹⁸O of water and δ¹³C of dissolved inorganic carbon (DIC). The source of DIC, which provides C for tufa precipitation, was determined from the slope of the line ([DIC]/[DIC₀]?1) vs. (δ¹³C‐DIC × ([DIC]/[DIC₀])) ( Sayles & Curry, 1988 ). The δ¹³C value of added DIC was ?13·6‰, corresponding to the dissolution of CO₂ with δ¹³C between ?19·5 and ?23·0‰ Vienna Pee Dee Belemnite (VPDB). The observed difference between the measured and calculated equilibrium temperature of precipitation of bulk tufa barriers indicates that the higher the water temperature, the larger the error in the estimated temperature of precipitation. This implies that the climatic signals may be valid only in tufas precipitated at lower and relatively stable temperatures. The laminar crust comprising a continuous record of the last 40 years of precipitation shows a consistent trend of increasing δ¹³C and decreasing δ¹⁸O. The lack of covariation between δ¹³C and δ¹⁸O indicates that precipitation of calcite was not kinetically controlled for either of the elements. δ¹³C and δ¹⁸O of precipitates collected on different artificial substrates show that surface characteristics both of substrates and colonizing biota play an important role in C and O isotope fractionation during carbonate precipitation.     

Recurrent uranium relocations in distal turbidites emplaced in pelagic conditions

The sediments of the Madeira Abyssal Plain, east of Great Meteor Seamount, are dominated by distal turbidite deposition. While the turbidites exhibit a wide compositional range (25–80% CaCO₃), individual examples can be correlated over a wide area and are relatively homogenous. Organic C oxidation, by bottom water oxygen, proceeds from the turbidite tops downwards after emplacement in pelagic conditions, and the progress of this oxidation front is marked by a sharp colour contrast in the sediments (Wilsonet al., 1985). In turbidites with C_org ? 0.5%, redistribution of authigenic U occurs to form a concentration peak (4–9 ppm U), just below the oxidation front or colour change. Several tens μg U/cm² may be mobilised, and in all examples studied ?60% of the remobilised U is relocated into the peak. Following burial by subsequent turbidites, such U concentration peaks are persistent as relict indicators of their extinct oxidation fronts for at least 2 × 10⁵ years. In the case of thin turbidites where labile C_org is almost exhausted, the U peaks may be located in underlying sedimentary units because of their relationship to the oxidation front. A redox mechanism for U peak formation is suggested from these data rather than a complexation with organic matter.