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.     

Disentangling marine, soil and plant organic carbon contributions to continental margin sediments: A multi-proxy approach in a 20,000 year sediment record from the Congo deep-sea fan

A 20 kyr long sediment sequence from the Congo deep sea fan (core GeoB 6518-1), one of the world’s largest deep sea river fans, has been analysed for bulk and molecular proxies in order to reconstruct the marine, soil and plant organic carbon (OC) contributions to these sediments since the last glacial maximum. The bulk proxies applied, C/N ratio and δ¹³C_org, ranged from 10 to 12.5 and from −24.5 to −21‰ VPDB, respectively. As molecular proxies, concentrations of marine derived alkenones and terrestrial derived odd-numbered n-alkanes were used, which varied between 0.2 and 4 μg/g dry weight sediment. In addition, the branched vs. isoprenoid tetraether (BIT) index, a proxy for soil organic matter input, was used, which varied from 0.3 to 0.5 in this core.Application of binary mixing models, based on the different individual proxies, showed estimates for terrestrial OC input varying by up to 50% due to the heterogeneous nature of the OC. Application of a three end-member mixing model using the δ¹³C_org content, the C/N ratio and the BIT index, enabled the distinction of soil and plant organic matter as separate contributors to the sedimentary OC pool. The results show that marine OC accounts for 20% to 40% of the total OC present in the deep sea fan sediments over the last 20 kyr and that soil OC accounts for about half (∼45% on average) of the OC present. This suggests that soil OC represents the majority of the terrestrial OC delivered to the fan sediments.Accumulation rates of the plant and soil OC fractions over the last 20 kyr varied by a factor of up to 5, and are strongly related to sediment accumulation rates. They showed an increase starting at ca. 17 kyr BP, a decline during the Younger Dryas, peak values during the early Holocene and lower values in the late Holocene. This pattern matches with reconstructions of past central African humidity and Congo River discharge from the same core and revealed that central African precipitation patterns exert a dominant control on terrestrial OC deposition in the Congo deep sea fan. Marine OC accumulation rates are only weakly related to sediment accumulation rates and vary only little over time compared to the terrigenous fractions. These variations are likely a result of enhanced preservation during times of higher sedimentation rates and of relative small fluctuations in primary production due to wind-driven upwelling.     

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.     

The isotopic composition of particulate organic carbon in mountain rivers of Taiwan

Small rivers draining mountain islands are important in the transfer of terrestrial particulate organic carbon (POC) to the oceans. This input has implications for the geochemical stratigraphic record. We have investigated the stable isotopic composition of POC (δ¹³C_org) in rivers draining the mountains of Taiwan. In 15 rivers, the suspended load has a mean δ¹³C_org that ranges from −28.1±0.8‰ to −22.0±0.2‰ (on average 37 samples per river) over the interval of our study. To investigate this variability we have supplemented suspended load data with measurements of POC in bedrock and river bed materials, and constraints on the composition of the terrestrial biomass. Fossil POC in bedrock has a range in δ¹³C_org from −25.4±1.5‰ to −19.7±2.3‰ between the major geological formations. Using coupled δ¹³C_org and N/C we have found evidence in the suspended load for mixing of fossil POC with non-fossil POC from the biosphere. In two rivers outside the Taiwan Central Range anthropogenic land use appears to influence δ¹³C_org, resulting in more variable and lower values than elsewhere. In all other catchments, we have found that 5‰ variability in δ¹³C_org is not controlled by the variable composition of the biomass, but instead by heterogeneous fossil POC.In order to quantify the fraction of suspended load POC derived from non-fossil sources (F_nf) as well as the isotopic composition of fossil POC (δ¹³C_fossil) carried by rivers, we adapt an end-member mixing model. River suspended sediments and bed sediments indicate that mixing of fossil POC results in a negative trend between N/C and δ¹³C_org that is distinct from the addition of non-fossil POC, collapsing multiple fossil POC end-members onto a single mixing trend. As an independent test of the model, F_nf reproduces the fraction modern (F_mod) in our samples, determined from ¹⁴C measurements, to within 0.09 at the 95% confidence level. Over the sampling period, the mean F_nf of suspended load POC was low (0.29 ± 0.02, n = 459), in agreement with observations from other mountain rivers where physical erosion rates are high and fossil POC enters river channels. The mean δ¹³C_fossil in suspended POC varied between −25.2±0.5‰ and −20.2±0.6‰ from catchment to catchment. This variability is primarily controlled by the distribution of the major geological formations. It also covers entirely the range of δ¹³C_org found in marine sediments which is commonly thought to derive from mixing between marine and terrigenous POC. If land-sourced POC is preserved in marine sediments, then changes in the bulk δ¹³C_org observed offshore Taiwan could instead be explained by changes in the onshore provenance of sediment. The range in δ¹³C_org of fossil organic matter in sedimentary rocks exposed at the surface is large and given the importance of these rocks as a source of clastic sediment to the oceans, care should be taken in accounting for fossil POC in marine deposits supplied by active mountain belts.     

A compound-specific n-alkane δC and δD approach for assessing source and delivery processes of terrestrial organic matter within a forested watershed in northern Japan

We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ¹³C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ¹³C values of odd carbon numbered C₂₃-C₃₃n-alkanes ranged from −37.2‰ to −31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from −244‰ to −180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ¹³C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C₂₅-C₃₁n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment.     

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.     

Rayleigh distillation and the depth profile of C/C ratios of soil organic carbon from soils of disparate texture in Iron Range National Park, Far North Queensland, Australia

A depth- and particle size-specific analysis of soil organic carbon (SOC) and its isotopic composition was undertaken to investigate the effects of soil texture (or particle size) on the depth profile of stable carbon isotopic composition of SOC (δ¹³C_SOC) in two tropical soils. Depth-specific samples from two soil profiles of markedly different texture (coarse grained and fine grained) were separated into particle size classes and analyzed for the (mass/mass) concentration of SOC (C) and δ¹³C_SOC. Within 1 m of the soil surface, δ¹³C_SOC in the coarse-textured soil increases by 1.3 to 1.6‰, while δ¹³C_SOC from the fine-textured soil increase by as much as 3.8 to 5.5‰. This increasing depth trend in the coarse-textured soil is approximately linear with respect to normalized C, while the increase in the fine-textured soil follows a logarithmic function with respect to normalized C. A model of Rayleigh distillation describing isotope fractionation during decomposition of soil organic matter (SOM) accounts for the depth profile of δ¹³C_SOC in the fine-textured soil, but does not account for the depth profile observed in the coarse-textured soil despite their similar climate, vegetation, and topographic position. These results suggest that kinetic fractionation during humification of SOM leads to preferential accumulation of ¹³C in association with fine mineral particles, or aggregates of fine mineral particles in fine-textured soils. In contrast, the coarse-textured soil shows very little applicability of the Rayleigh distillation model. Rather, the depth profile of δ¹³C_SOC in the coarse-textured soil can be accounted for by mixing of soil carbon with different isotopic ratios.     

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.     

Distribution of nitrogen forms in surface sediments of lakes from different regions,China

The characteristics of nitrogen fractions in the surface sediments of lakes from Eastern Plain Region, Yunnan-Guizhou Plateau Region, Northeast China Region, Qinghai-Tibet Plateau Region and Mongolia-Xinjiang Plateau Region were investigated and the differences of five lake regions on nitrogen fractionation were discussed. The results indicated that organic nitrogen (N_org) was the major nitrogen fraction accounting for 76.38–92.02 % of N_tot in sediments. The rank order of average N_org and N_tot of sediments in five lake regions was: Yunnan-Guizhou Plateau Region > Northeast China Region > Mongolia-Xinjiang Plateau Region > Qinghai-Tibet Plateau Region > Eastern Plain Region. The exchangeable nitrogen had a similar distribution as organic nitrogen in the studied sediments. NH₄ ⁺–N is the main exchangeable nitrogen of sediments in the studied lakes except in Lake Qinghai and Lake Yamdrok which contained higher nitrate concentrations than ammonium. Fixed ammonium (N_fix) in the sediments of studied lakes was irregularly distributed with the values ranging from 99.45 to 329.02 mg/kg. TOC was significantly and positively correlated with ammonium, nitrate, N_org and N_tot, while N_fix was negatively correlated with nitrate probably due to electrostatic attraction between N_fix and nitrate in layers of sediments.     

Early diagenetic remineralization of sedimentary organic C in the Gulf of Papua deltaic complex (Papua New Guinea): Net loss of terrestrial C and diagenetic fractionation of C isotopes

Oceania supplies ∼40% of the global riverine flux of organic carbon, approximately half of which is injected onto broad continental shelves and processed in shallow deltaic systems. The Gulf of Papua, on the south coast of the large island of New Guinea, is one such deltaic clinoform complex. It receives ∼4 Mt yr⁻¹ particulate terrestrial organic carbon with initial particle C_org loading ∼0.7 mg m⁻². C_org loading is reduced to ∼0.3 mg m⁻² in the topset-upper foreset zones of the delta despite additional inputs of mangrove and planktonic detritus, and high net sediment accumulation rates of 1-4 cm yr⁻¹. Carbon isotopic analyses (δ¹³C, Δ¹⁴C) of ΣCO₂ and C_org demonstrate rapid (<100 yr) remineralization of both terrestrial (δ¹³C <−28.6) and marine C_org (δ¹³C ∼−20.5) ranging in average age from modern (bomb) (Δ¹⁴C ∼60) to ∼1000 yr (Δ¹⁴C ∼−140). Efficient and rapid remineralization in the topset-upper foreset zone is promoted by frequent physical reworking, bioturbation, exposure, and reoxidation of deposits. The seafloor in these regions, particularly <20 m, apparently functions as a periodically mixed, suboxic batch reactor dominated by microbial biomass. Although terrestrial sources can be the primary metabolic substrates at inshore sites, relatively young marine C_org often preferentially dominates pore water ΣCO₂ relative to bulk C_org in the upper foreset. Thus a small quantity of young, rapidly recycled marine organic material is often superimposed on a generally older, less reactive terrestrial background. Whereas the pore water ΣCO₂ reflects both rapidly cycled marine and terrestrial sources, terrestrial material dominates the slower overall net loss of C_org from particles in the topset-upper foreset zone (i.e. recycled marine C_org leaves little residue). Preferential utilization of C_org subpools and diagenetic fractionation of C isotopes supports the reactive continuum model as a conceptual basis for net decomposition kinetics. Early diagenetic fractionation of C isotopes relative to the bulk sedimentary C_org composition can produce changes in ¹⁴C activity independent of radioactive decay. In the Gulf of Papua topset-upper foreset, Δ¹⁴C of pore water ΣCO₂ averaged ∼ 300‰ greater than C_org sediment between ∼1-3 m depth in deposits. Diagenetic fractionation and decomposition aging of sedimentary C_org compromises simple application of ¹⁴C for determination of sediment accumulation rates in diagenetically reactive deposits.     

Sediment Organic Carbon in Todos Santos Bay, Baja California, Mexico

Sediment grain size and organic carbon (OC) data collected over the past 50 years, together with δ¹³C values of OC in recently collected samples, were analyzed to improve understanding of sediment OC distribution and abundance in Todos Santos Bay. Sediments in the submarine canyon at the mouth of the bay and in quiet-water locations along the shore are fine grained, high in OC, and have generally low δ¹³C values; sediments in high-energy environments are low in OC and have high δ¹³C values. A bivariate isotopic mixing model indicates that none of the sediments contain >50% terrigenous OC (average ~30%), and that the terrigenous OC content of the sediments is a small proportion of the OC content of local soils. Sediment OC composition is apparently controlled by energy-related sorting and deposition, oxidation of much of the original terrigenous OC, and replacement of some terrigenous OC by marine OC.     

Genesis of organic and carbonate carbon in sediments of the North and Middle Caspian basins inferred from the isotope data

Isotopic compositions of organic (δ¹³C-C_org) and carbonate (δ¹³C-C_carb) carbon were analyzed in the particulate matter (hereafter, particulates) and sediments from the North and Middle Caspian basins. Isotopic composition of C_org was used for assessing proportions of the allochthonous and autochthonous organic matter in the particulates. Difference between the δ¹³C-C_org values in surface sediments and particulates is explained by the aerobic and anaerobic diagenetic transformations. Isotopic composition of C_org in sediments may be used as a tool for reconstructing the Quaternary transgressive-regressive history of the Caspian Sea.     

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.     

Recycling of Organic Matter in the Sediments of Santa Monica Basin,California Borderland

Geochemical and isotopic data for the uppermost 1.2 m of the sediments of the central Santa Monica Basin plain were examined to better understand organic matter deposition and recycling at this site. Isotopic signatures (Δ¹⁴C and δ¹³C) of methane (CH₄) and dissolved inorganic carbon (DIC) indicate the occurrence of anaerobic oxidation of CH₄ that is fueled by CH₄ supplied from a relict reservoir that is decoupled from local organic carbon (C_org) degradation and methanogenesis. This finding was corroborated by a flux budget of pore-water solutes across the basal horizon of the profile. Together these results provide a plausible explanation for the anomalously low ratio between alkalinity production and sulfate consumption reported for these sediments over two decades ago. Shifts in Δ¹⁴C and δ¹³C signatures of C_org have previously been reported across the 20-cm depth horizon for this site and attributed to a transition from oxic to anoxic bottom water that occurred ~350 years BP. However, we show that this horizon also coincides with a boundary between the base of a hemipelagic mud section and the top of a turbidite interval, complicating the interpretation of organic geochemical data across this boundary. Radiocarbon signatures of DIC diffusing upward into surface sediments indicate that remineralization at depth is supported by relatively ¹⁴C-enriched C_org within the sedimentary matrix. While the exact nature of this C_org is unclear, possible sources are hemipelagic mud sections that were buried rapidly under thick turbidites, and ¹⁴C-rich moieties dispersed within C_org-poor turbidite sections.     

Sources of fine-sized organic matter in North Atlantic Heinrich Layers: δC and δN tracers

Organic carbon (OC) and total nitrogen (TN) concentrations and stable isotope ratios (δ¹³C, δ¹⁵N) of fine (<50 μm) size fractions of deep-sea sediments from the central North Atlantic were employed to identify changes in sources of organic matter over the past 50 ka BP. Ambient glacial sediments are characterised by values that reflect mixtures of marine and terrestrial inputs (averages ± 1σ: OC/TN = 7.6 ± 0.8; δ¹³C = −22.8 ± 1.0‰; δ¹⁵N = 5.5 ± 0.6‰). δ¹³C, OC, and TN concentrations shift to higher values during the Holocene, indicating a gradual decrease of fine terrigenous supply to the North Atlantic. The unchanged δ¹⁵N record between last glacial and Holocene stages indicates that the central North Atlantic region remained oligotrophic at least during the past 50 ka BP, but additional studies are required to support this result in terms of nitrogen oceanic budget. During the phases of enhanced ice-rafted detrital supply corresponding to prominent Heinrich events (HL₁, HL₂, HL₄, and HL₅), fine-sized sedimentary organic matter has lower OC and TN concentrations, contrasting sharply with those of ambient glacial sediments. Lower δ¹³C (down to −28‰) and δ¹⁵N (down to 1.6‰) values and high OC:TN ratios (up to 14.7 ± 1.1) are found for HL₁, HL₂, and with lesser extent for HL₄. These values reflect enhanced detrital supply originating from poorly differentiated soil horizons that characterise periglacial climate conditions and from organic matter-bearing rock sources of the underlying geological basement. During HL₅, only the δ¹³C offset records the input of fine size ice-rafted organic matter. Gradually changing soil development conditions during the time interval covering HL₅ to HL₁ (marine isotope stages 5 to 2), as well as varying erosion levels, have been hypothesized on the basis of constant δ¹³C, increasing OC/TN and decreasing δ¹⁵N values.     

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.     

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.     

Evidence for multiple, episodic, mid-Holocene Hypsithermal recorded in two soil profiles along an alluvial floodplain catena, southeastern Tennessee, USA

Floodplain soil-paleosol successions are valuable archives for reconstructing Pleistocene-Holocene climate changes but have been relatively unstudied in the southern Appalachian region. Two soil profiles on a small floodplain in southeastern Tennessee, USA were described and sampled in detail using both pedological and geological approaches, including stable carbon isotope analysis of soil organic matter (SOM). Correlation between the 2 profiles was constrained by uncalibrated AMS ¹⁴C ages of bulk humates, and using SOM δ¹³C values, both mobile and immobile elements. Four distinct 2.5-4‰ shifts towards less negative δ¹³C values for SOM suggest ∼ 300-yr cyclicity and transient warmer and drier climate events, with either water-stressed C₃ vegetation or as much as 35% C₄ plants present during the mid-Holocene. These postulated multi-episodic drier climate conditions have never before been documented in the southern Appalachian region and are tentatively correlated with mid-Holocene warming and drying in the eastern US, the nearly time-equivalent mid-Holocene events documented in Texas, the US High Plains and in the Gulf of Mexico. High rates of floodplain sediment accumulation (0.5-3 mm/yr), high clay content and maintenance of poorly drained soil conditions favor preservation of high-resolution climate archives in floodplain deposits by inhibiting oxidation and translocation of organic C.     

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.     

Stable carbon isotopic evidence for differences in the dietary origin of bone cholesterol, collagen and apatite: implications for their use in palaeodietary reconstruction

Rats were raised on a variety of isotopically controlled diets comprising 20% C₃, C₄ or marine protein and C₃ and/or C₄ non-protein or energy (i.e. sucrose, starch and oil) macronutrients. Compound specific stable carbon isotope (δ¹³C) analysis was performed on the cholesterol isolated from the diet (n=7 ) and bone (n=15 ) of these animals and the values compared with bulk δ¹³C measurements of bone collagen and apatite. The dietary signals reflected by these three bone biochemical components were investigated using linear regression analysis. δ¹³C values of bone cholesterol were shown to reflect whole diet δ¹³C values, collagen to reflect mainly dietary protein values and apatite to reflect whole diet values. Further correlations between dietary protein-to-energy spacings (Δ¹³C_prot-engy = δ¹³C_protein - δ¹³C_energy) and whole diet-to-bone component fractionations (Δ¹³C_bcomp-wdiet = δ¹³C_{bone component} - δ¹³C_{whole diet}) indicates that for hypothetical diets where protein δ¹³C values are equal to energy values, fractionations between whole diet and bone biochemical fractions are -3.3‰ for cholesterol, +5.4‰ for collagen and +9.5‰ for apatite. Moreover, the narrow range of variation observed in apatite-to-cholesterol spacings (Δ¹³C_apat-bchol) suggests that cholesterol δ¹³C values can potentially also be used as an independent test for the isotopic integrity of apatite δ¹³C values. These insights into bone cholesterol, collagen and apatite dietary signals, diet-to-bone fractionations and bone component-to-bone component spacings provide the basis for more accurate interpretations of the dietary behaviour of archaeological populations and food webs when the δ¹³C analysis of bone is employed.