Fossil Organic Carbon Research Articles

Sources and high burial efficiency of fossil organic carbon in small bays and implication for coastal carbon cycle

Coastal seas receive and store large amounts of organic carbon (OC) from land and ocean, thereby playing a crucial role in the global carbon cycle. Understanding factors that influencing OC sources and burial efficiencies in coastal areas have been challenging. We selected the Jiaozhou Bay (JZB) and its surrounding rivers heavily affected by human activities as a case study small bay. We presented bulk parameters of grain size, sediment surface area (SSA), TOC content and carbon isotopes (δ13Corg and Δ14Corg), terrestrial biomarkers (∑C27 + C29 + C31n-alkanes) and marine biomarkers (brassicasterol and dinosterol) in surface sediments and suspended particulates. Our results showed low TOC and biomarker contents in the Dagu River Estuary from the west of the JZB associated with coarse sediments and lower SSA. To estimate the OC proportions, we applied a three-end member mixing model based on TOC δ13Corg and biomarker ratios and obtained the OC contribution from phytoplankton (average 52 %), soil (average 34 %) and wetlands (average 14 %). A transect from east to west of the JZB was selected to further assess the OC age composition based on radiocarbon isotopic (14C) measurements for a new perspective. The lower Δ14Corg values in the east revealed fossil OC contributions from human activities, such as petroleum pollutant inputs from sewage outlets. Based on a dual‑carbon isotope (δ13Corg and Δ14Corg) mass balance mixing model, the OC contributions were 40 %, 34 %, 14 %, 12 % from fossil carbon, phytoplankton, wetlands and soil, respectively. The very high burial efficiency of fossil OC in JZB (111 ± 19 %) indicated that small bays such as the JZB could be an important sedimentary carbon sink.

Fossil and Nonfossil Sources of Winter Organic Aerosols in the Regional Background Atmosphere of China.

Carbonaceous aerosols (CA) from anthropogenic emissions have been significantly reduced in urban China in recent years. However, the relative contributions of fossil and nonfossil sources to CA in rural and background regions of China remain unclear. In this study, the sources of different carbonaceous fractions in fine aerosols (PM2.5) from five background sites of the China Meteorological Administration Atmosphere Watch Network during the winter of 2019 and 2020 were quantified using radiocarbon (14C) and organic markers. The results showed that nonfossil sources contributed 44-69% to total carbon at these five background sites. Fossil fuel combustion was the predominant source of elemental carbon at all sites (73 ± 12%). Nonfossil sources dominated organic carbon (OC) in these background regions (61 ± 13%), with biomass burning or biogenic-derived secondary organic carbon (SOC) as the most important contributors. However, the relative fossil fuel source to OC in China (39 ± 13%) still exceeds those at other regional/background sites in Asia, Europe, and the USA. SOC dominated the fossil fuel-derived OC, highlighting the impact of regional transport from anthropogenic sources on background aerosol levels. It is therefore imperative to develop and implement aerosol reduction policies and technologies tailored to both the anthropogenic and biogenic emissions to mitigate the environmental and health risks of aerosol pollution across China.

Impact of organic carbon reworking upon GDGT temperature proxies during the Paleocene-Eocene Thermal Maximum

Glycerol dialkyl glycerol tetraethers (GDGTs) have been widely applied to coastal marine sediments to reconstruct past temperature variability. However, coastal environments are characterised by variability in the source, age and/or thermal maturity of different organic carbon (OC) pools and may bias various GDGT-based proxies. Here we analyse TEX86 and MBT5MEvalues within a shallow marine sediment core (South Dover Bridge, Maryland) from the Paleocene-Eocene Thermal Maximum (PETM; 56 million years ago (Ma)) to explore how changes in OC reworking influence GDGT-derived sea surface and terrestrial temperature estimates, respectively. We demonstrate that TEX86 values are unaffected by an increase in soil- and fossil organic carbon during the PETM. In contrast, we find large and unexpected variations in MBT5ME-derived temperature estimates (∼6 to 25 °C) during the onset and core of the PETM at some sites. This coincides with input of reworked terrestrial OC from the Cenomanian-aged Raritan Formation. However, there is also an increase in the degree of cyclisation of tetramethylated branched GDGTs, suggesting that branched GDGTs are also derived from marine in-situ production. These factors preclude terrestrial temperature reconstructions at this site. We explored whether OC reworking is problematic in other PETM-aged coastal environments. Using GDGT metrics and the Branched and Isoprenoid GDGT Machine learning Classification algorithm (BIGMaC), we demonstrate that TEX86 values are mostly unaffected by changes in OC sources. However, MBT5ME values are affected by marine and/or freshwater overprints, especially in environments with low terrestrial OC input. Taken together, this study highlights the importance of constraining the provenance of different GDGTs in marine and lacustrine environments.

Determining source-specific terrigenous organic carbon contributions in sediments from the Yellow River estuary, Northeast China: A test of source apportionment models

Molecular organic geochemistry has been used effectively to determine terrigenous organic carbon (OC) contributions from different sources in modern sediments. However, mathematic modelling using source-specific parameters could be a potentially simple-effective approach to identify the terrigenous OC signals. In this study, the Yellow River estuary was chosen to probe whether source apportionment models can determine source-specific OC contributions. The end-member mixing model suggests that terrigenous OC contributed 57.0% ± 10.2% to the sedimentary OC. n-Alkane distributions were used to perform Unmix and positive matrix factorization (PMF) to separate terrigenous and autochthonous OC into more specific sources. PMF modelling delineates the contributions of high terrigenous plants, fossil OC, macrophyte-sourced OC, and bacterial and algal-sourced OC as 22.9% ± 14.3%, 26.2% ± 19.4%, 26.5% ± 19.3%, and 24.4% ± 17.1%, respectively. In assessing terrigenous contributions, PMF results (48.7% ± 13.5%) almost agrees with the end-member mixing model (57.0% ± 10.2%), consistent and comparable with previously published data (~ 50%), while Unmix (73.9% ± 18.7%) is significantly overestimated. Interestingly, macrophyte-sourced OC from coastal wetland identified by PMF was less investigated previously and should call attention in the future study. Consequently, modelling results match well with previously published data, suggesting that mathematic modelling can be an effective approach to quantitatively evaluate source-specific terrigenous OC contributions to estuary sediments and other complex aqua-land systems. However, caution must be taken in respect to the modelling uncertainty, which could be mainly induced by sample number, diversity, and robust interpretation on chemical parameters.

Fossil organic carbon utilization in marine Arctic fjord sediments by subsurface micro-organisms

Rock-derived or petrogenic organic carbon has traditionally been regarded as being non-bioavailable and bypassing the active carbon cycle when eroded. However, it has become apparent that this organic carbon might not be so inert, especially in fjord systems where petrogenic organic carbon influxes can be high, making its degradation another potential source of greenhouse gas emissions. The extent to which subsurface micro-organisms use this organic carbon is not well constrained, despite its potential impacts on global carbon cycling. Here, we performed compound-specific radiocarbon analyses on intact polar lipid–fatty acids of live micro-organisms from marine sediments in Hornsund Fjord, Svalbard. By this means, we estimate that local bacterial communities utilize between 5 ± 2% and 55 ± 6% (average of 25 ± 16%) of petrogenic organic carbon for their biosynthesis, providing evidence for the important role of petrogenic organic carbon as a substrate after sediment redeposition. We hypothesize that the lack of sufficient recently synthesized organic carbon from primary production forces micro-organisms into utilization of petrogenic organic carbon as an alternative energy source. The input of petrogenic organic carbon to marine sediments and subsequent utilization by subsurface micro-organisms represents a natural source of fossil greenhouse gas emissions over geological timescales.

Properties of river organic carbon affected by wastewater treatment plants

Tracking the sources of organic carbon (OC) is critical not only for understanding riverine carbon dynamics but also for providing management options to improve water quality. We collected water samples from upland forest streams to the mainstream Geumho River (GHR) of South Korea, which included a variety of wastewater treatment plants (WWTP) effluents. We analyzed the concentrations, optical properties, and dual carbon isotope ratios of these samples to identify the sources of OC. Dissolved organic carbon (DOC) was the dominant form of OC in the GHR compared to particulate organic carbon (POC), as the former accounted for 87 % of OC. The concentrations of DOC and POC ranged from 1.2 to 11.2 mg L−1 and from 0 and 3.6 mg L−1, respectively, aside from the livestock WWTP effluent. Dominant fluorescence components were terrestrial humic substances in upper reaches whereas protein-like materials in lower reaches of the GHR whose watershed includes a large city with many WWTPs. Significantly lower Δ14C-DOC and Δ14C-POC were observed in industrial WWTP effluents than the other sites due to the contribution of fossil OC. Livestock WWTP effluents had higher δ13C-DOC and δ13C-POC than most of the sites, possibly due to the animal feed derived from C4 plants such as corn. Fossil OC contributed 29–52 % of [DOC] and 36–56 % of [POC] from industrial WWTP effluents, whereas C4-plants derived OC contributed about half of [DOC] and [POC] from a livestock WWTP effluent. The results suggest that anthropogenic sources of organic carbon could alter river carbon dynamics, and that caution is needed when we interpret isotope ratios of riverine organic carbon, particularly when the river passes through highly populated areas wherein WWTP effluents are large.

Terrestrial organic carbon age and reactivity in the Yellow River fueling efficient preservation in marine sediments

The Yellow River is one of the largest suppliers of sediments and organic carbon (OC) to the ocean. Previous studies have revealed that OC transported by the Yellow River largely derives from the erosion of the Chinese Loess Plateau, which is dominated by pre-aged soil carbon and could be efficiently preserved in marine sediments. Here, we used ramped oxidation radiocarbon analysis (RPO-14C) to characterize the age and reactivity distribution of OC in two Yellow River suspended sediment samples and six Bohai Sea and Yellow Sea (BS–YS) surface sediments from a transect along the sediment transport pathway. RPO-14C independently characterizes the full spectrum of OC thermal stability and isotope compositions to reveal the source, age and reactivity structure of OC transported by the Yellow River and preserved in Chinese marginal sea sediments. We calculated the activation energy (E) distribution—a proxy for bonding environment and by extension reactivity—which, combined with 14C and stable carbon isotope (δ13C) compositions, reveals OC origin and stability. Our data suggest that 96% of OC in Yellow River suspended sediments is biospheric and weathered petrogenic, while unweathered petrogenic OC only accounts for 4% which is almost an order of magnitude lower than the fossil OC estimates (32%) based on compound specific 14C analysis. RPO data reveal the prevalence of aged biospheric loess OC in the Yellow River. We use δ13C, 14C and RPO-derived activation energy data to quantify the contribution of terrestrial OC to surface sediments in the BS–YS. The resulting estimates of terrestrial OC proto-burial efficiencies yield an average value of 89 ± 30%, revealing overall very high terrestrial OC preservation in the BS–YS. Additionally, and somewhat counter intuitively, we find that the preservation of terrestrial OC decreases with increasing E. This pattern may arise from an enhanced preservation of a pre-aged C4 plants derived fraction of the loess-derived OC associated with secondary clays characterized by smaller grain size and higher surface area. Alternatively, the high E component of the Yellow River OC might comprise partially weathered petrogenic carbon, undergoing further mineralization during transport from rivers to marginal sea sediments via marine organic matter priming.

Carbon isotopic constraints on the degradation and sequestration of organic matter in river‐influenced marginal sea sediments

AbstractOrganic matter degradation and sequestration in marine sediments are important processes involved in carbon cycling in the ocean. Here, we present the results of carbon isotope (14C and 13C) and concentration measurements of sedimentary organic carbon (SOC), pore‐water dissolved organic carbon (DOC), and dissolved inorganic carbon (DIC) in sediments collected from the East China Sea, Yellow/Bohai Sea, and South China Sea. Our results indicated that selective degradation and preservation of organic matter occurred in these sediments, and marine‐derived young organic carbon degraded preferentially and rapidly, resulting in high concentrations of pore‐water DOC and DIC with distinct carbon isotopic signatures. The average 14C age of pore‐water DOC was thousands of years younger than that of SOC in the sediment, suggesting that DOC was newly produced and cycled much faster than SOC. Aged SOC was refractory and preserved in sediments. Using a dual‐isotope three‐end‐member model, the contributions of potential sources to SOC, DOC, and DIC were estimated. Marine‐derived biomass organic carbon contributed the most to DOC, and dissolution of biogenic carbonate contributed the most to DIC. Riverine inputs of pre‐aged soil and fossil organic carbon dominated the SOC pool. Our study demonstrated that marginal sea sediments are important sites of young DOC and DIC fluxes into the water column, thus acting as a major pathway for carbon and nutrient cycling in the ocean.

Neogene continental denudation and the beryllium conundrum

Reconstructing Cenozoic history of continental silicate weathering is crucial for understanding Earth's carbon cycle and greenhouse history. The question of whether continental silicate weathering increased during the late Cenozoic, setting the stage for glacial cycles, has remained controversial for decades. Whereas numerous independent proxies of weathering in ocean sediments (e.g., Li, Sr, and Os isotopes) have been interpreted to indicate that the continental silicate weathering rate increased in the late Cenozoic, beryllium isotopes in seawater have stood out as an important exception. Beryllium isotopes have been interpreted to indicate stable continental weathering and/or denudation rates over the last 12 Myr. Here we present a Be cycle model whose results show that variations in the 9Be weathering flux are counterbalanced by near-coastal scavenging while the cosmogenic 10Be flux from the upper atmosphere stays constant. As a result, predicted seawater 10Be/9Be ratios remain nearly constant even when global denudation and Be weathering rates increase by three orders of magnitude. Moreover, 10Be/9Be records allow for up to an 11-fold increase in Be weathering and denudation rates over the late Cenozoic, consistent with estimates from other proxies. The large increase in continental weathering indicated by multiple proxies further suggests that the increased CO2 consumption by continental weathering, driven by mountain-building events, was counterbalanced by other geological processes to prevent a runaway icehouse condition during the late Cenozoic. These processes could include enhanced carbonate dissolution via pyrite weathering, accelerated oxidation of fossil organic carbon, and/or reduced basalt weathering as the climate cooled.

The role of geochemistry in organic carbon stabilization against microbial decomposition in tropical rainforest soils

Abstract. Stabilization of soil organic carbon (SOC) against microbial decomposition depends on several soil properties, including the soil weathering stage and the mineralogy of parent material. As such, tropical SOC stabilization mechanisms likely differ from those in temperate soils due to contrasting soil development. To better understand these mechanisms, we investigated SOC dynamics at three soil depths under pristine tropical African mountain forest along a geochemical gradient from mafic to felsic and a topographic gradient covering plateau, slope and valley positions. To do so, we conducted a series of soil C fractionation experiments in combination with an analysis of the geochemical composition of soil and a sequential extraction of pedogenic oxides. Relationships between our target and predicting variables were investigated using a combination of regression analyses and dimension reduction. Here, we show that reactive secondary mineral phases drive SOC properties and stabilization mechanisms together with, and sometimes more strongly than, other mechanisms such as aggregation or C stabilization by clay content. Key mineral stabilization mechanisms for SOC were strongly related to soil geochemistry, differing across the study regions. These findings were independent of topography in the absence of detectable erosion processes. Instead, fluvial dynamics and changes in soil moisture conditions had a secondary control on SOC dynamics in valley positions, leading to higher SOC stocks there than at the non-valley positions. At several sites, we also detected fossil organic carbon (FOC), which is characterized by high C/N ratios and depletion of N. FOC constitutes up to 52.0 ± 13.2 % of total SOC stock in the C-depleted subsoil. Interestingly, total SOC stocks for these soils did not exceed those of sites without FOC. Additionally, FOC decreased strongly towards more shallow soil depths, indicating decomposability of FOC by microbial communities under more fertile conditions. Regression models, considering depth intervals of 0–10, 30–40 and 60–70 cm, showed that variables affiliated with soil weathering, parent material geochemistry and soil fertility, together with soil depth, explained up to 75 % of the variability of SOC stocks and Δ14C. Furthermore, the same variables explain 44 % of the variability in the relative abundance of C associated with microaggregates vs. free-silt- and-clay-associated C fractions. However, geochemical variables gained or retained importance for explaining SOC target variables when controlling for soil depth. We conclude that despite long-lasting weathering, geochemical properties of soil parent material leave a footprint in tropical soils that affects SOC stocks and mineral-related C stabilization mechanisms. While identified stabilization mechanisms and controls are similar to less weathered soils in other climate zones, their relative importance is markedly different in the tropical soils investigated.

Application of the ECT9 protocol for radiocarbon-based source apportionment of carbonaceous aerosols

Abstract. Carbonaceous aerosol is mainly composed of organic carbon (OC) and elemental carbon (EC). Both OC and EC originate from a variety of emission sources. Radiocarbon (14C) analysis can be used to apportion bulk aerosol, OC, and EC into their sources. However, such analyses require the physical separation of OC and EC. Here, we apply of ECT9 protocol to physically isolate OC and EC for 14C analysis and evaluate its effectiveness. Several reference materials are selected, including two pure OC (fossil “adipic acid” and contemporary “sucrose”), two pure EC (fossil “regal black” and “C1150”), and three complex materials containing contemporary and/or fossil OC and EC (“rice char”, NIST urban dust standards “SRM1649a” and “SRM8785”, i.e., fine fraction of resuspended SRM1649a on filters). The pure materials were measured for their OC, EC, and total carbon (TC) mass fractions and corresponding carbon isotopes to evaluate the uncertainty of the procedure. The average accuracy of TC mass, determined via volumetric injection of a sucrose solution, was approximately 5 %. Ratios of EC/TC and OC/TC were highly reproducible, with analytical precisions better than 2 % for all reference materials, ranging in size from 20 to 100 µg C. Consensus values were reached for all pure reference materials for both δ13C and fraction modern (F14C), with an uncertainty of < 0.3 ‰ and approximately 5 %, respectively. The procedure introduced 1.3 ± 0.6 µg of extraneous carbon, an amount compatible to that of the Swiss_4S protocol. In addition, OC and EC were isolated from mixtures of pure contemporary OC (sucrose) with pure fossil EC (regal black) and fossil OC (adipic acid) with contemporary EC (rice char EC) to evaluate the effectiveness of OC and EC separation. Consensus F14C values were reached for all OC (∼ 5–30 µg) and EC (∼ 10–60 µg) fractions with an uncertainty of ∼ 5 % on average. We found that the ECT9 protocol efficiently isolates OC or EC from complex mixtures. Based on δ13C measurements, the average contribution of charred OC to EC is likely less than 3 % when the OC loading amount is less than 30 µg C. Charring was further assessed by evaluating thermograms of various materials, including aerosol samples collected in the Arctic and from tailpipes of gasoline or diesel engines. These data demonstrate that the ECT9 method effectively removes pyrolyzed OC. Thus, the ECT9 protocol, initially developed for concentration and stable isotope measurements of OC and EC, is suitable for 14C-based apportionment studies, including µg C-sized samples from arctic environments.

Coal fly ash is a major carbon flux in the Chang Jiang (Yangtze River) basin

Fly ash-the residuum of coal burning-contains a considerable amount of fossilized particulate organic carbon (FOCash) that remains after high-temperature combustion. Fly ash leaks into natural environments and participates in the contemporary carbon cycle, but its reactivity and flux remained poorly understood. We characterized FOCash in the Chang Jiang (Yangtze River) basin, China, and quantified the riverine FOCash fluxes. Using Raman spectral analysis, ramped pyrolysis oxidation, and chemical oxidation, we found that FOCash is highly recalcitrant and unreactive, whereas shale-derived FOC (FOCrock) was much more labile and easily oxidized. By combining mass balance calculations and other estimates of fly ash input to rivers, we estimated that the flux of FOCash carried by the Chang Jiang was 0.21 to 0.42 Mt C⋅y-1 in 2007 to 2008-an amount equivalent to 37 to 72% of the total riverine FOC export. We attributed such high flux to the combination of increasing coal combustion that enhances FOCash production and the massive construction of dams in the basin that reduces the flux of FOCrock eroded from upstream mountainous areas. Using global ash data, a first-order estimate suggests that FOCash makes up to 16% of the present-day global riverine FOC flux to the oceans. This reflects a substantial impact of anthropogenic activities on the fluxes and burial of fossil organic carbon that has been made less reactive than the rocks from which it was derived.

Sources and formation of carbonaceous aerosols in Xi'an, China: primary emissions and secondary formation constrained by radiocarbon

Abstract. To investigate the sources and formation mechanisms of carbonaceous aerosols, a major contributor to severe particulate air pollution, radiocarbon (14C) measurements were conducted on aerosols sampled from November 2015 to November 2016 in Xi'an, China. Based on the 14C content in elemental carbon (EC), organic carbon (OC) and water-insoluble OC (WIOC), contributions of major sources to carbonaceous aerosols are estimated over a whole seasonal cycle: primary and secondary fossil sources, primary biomass burning, and other non-fossil carbon formed mainly from secondary processes. Primary fossil sources of EC were further sub-divided into coal and liquid fossil fuel combustion by complementing 14C data with stable carbon isotopic signatures. The dominant EC source was liquid fossil fuel combustion (i.e., vehicle emissions), accounting for 64 % (median; 45 %–74 %, interquartile range) of EC in autumn, 60 % (41 %–72 %) in summer, 53 % (33 %–69 %) in spring and 46 % (29 %–59 %) in winter. An increased contribution from biomass burning to EC was observed in winter (∼28 %) compared to other seasons (warm period; ∼15 %). In winter, coal combustion (∼25 %) and biomass burning equally contributed to EC, whereas in the warm period, coal combustion accounted for a larger fraction of EC than biomass burning. The relative contribution of fossil sources to OC was consistently lower than that to EC, with an annual average of 47±4 %. Non-fossil OC of secondary origin was an important contributor to total OC (35±4 %) and accounted for more than half of non-fossil OC (67±6 %) throughout the year. Secondary fossil OC (SOCfossil) concentrations were higher than primary fossil OC (POCfossil) concentrations in winter but lower than POCfossil in the warm period. Fossil WIOC and water-soluble OC (WSOC) have been widely used as proxies for POCfossil and SOCfossil, respectively. This assumption was evaluated by (1) comparing their mass concentrations with POCfossil and SOCfossil and (2) comparing ratios of fossil WIOC to fossil EC to typical primary OC-to-EC ratios from fossil sources including both coal combustion and vehicle emissions. The results suggest that fossil WIOC and fossil WSOC are probably a better approximation for primary and secondary fossil OC, respectively, than POCfossil and SOCfossil estimated using the EC tracer method.

On the Origin of Aged Sedimentary Organic Matter Along a River‐Shelf‐Deep Ocean Transect

AbstractTo assess the influences of carbon sources and transport processes on the 14C age of organic matter (OM) in continental margin sediments, we examined a suite of samples collected along a river‐shelf‐deep ocean transect in the East China Sea (ECS). Ramped pyrolysis‐oxidiation was conducted on suspended particulate matter in the Yangtze River and on surface sediments from the ECS shelf and northern Okinawa Trough. 14C ages were determined on OM decomposition products within different temperature windows. These measurements suggest that extensive amounts of pre‐old (i.e., millennial age) organic carbon (OC) are subject to degradation within and beyond the Yangtze River Delta, and this process is accompanied by an exchange of terrestrial and marine OM. These results, combined with fatty acid concentration data, suggest that both the nature and extent of OM preservation/degradation as well as the modes of transport influence the 14C ages of sedimentary OM. Additionally, we find that the age of (thermally) refractory OC increases during across‐shelf transport and that the age offset between the lowest and highest temperature OC decomposition fractions also increases along the shelf‐to‐trough transect. Amplified interfraction spread or 14C heterogeneity is the greatest in the Okinawa Trough. Aged sedimentary OM across the transect may be a consequence of several reasons including fossil OC input, selective degradation of younger OC, hydrodynamic sorting processes, and aging during lateral transport. Consequently, each of them should be considered in assessing the 14C results of sedimentary OM and its implications for the carbon cycle and interpretation of sedimentary records.

The Oxidative Metabolism of Fossil Hydrocarbons and Sulfide Minerals by the Lithobiontic Microbial Community Inhabiting Deep Subterrestrial Kupferschiefer Black Shale.

Black shales are one of the largest reservoirs of fossil organic carbon and inorganic reduced sulfur on Earth. It is assumed that microorganisms play an important role in the transformations of these sedimentary rocks and contribute to the return of organic carbon and inorganic sulfur to the global geochemical cycles. An outcrop of deep subterrestrial ~256-million-year-old Kupferschiefer black shale was studied to define the metabolic processes of the deep biosphere important in transformations of organic carbon and inorganic reduced sulfur compounds. This outcrop was created during mining activity 12 years ago and since then it has been exposed to the activity of oxygen and microorganisms. The microbial processes were described based on metagenome and metaproteome studies as well as on the geochemistry of the rock. The microorganisms inhabiting the subterrestrial black shale were dominated by bacterial genera such as Pseudomonas, Limnobacter, Yonghaparkia, Thiobacillus, Bradyrhizobium, and Sulfuricaulis. This study on black shale was the first to detect archaea and fungi, represented by Nitrososphaera and Aspergillus genera, respectively. The enzymatic oxidation of fossil aliphatic and aromatic hydrocarbons was mediated mostly by chemoorganotrophic bacteria, but also by archaea and fungi. The dissimilative enzymatic oxidation of primary reduced sulfur compounds was performed by chemolithotrophic bacteria. The geochemical consequences of microbial activity were the oxidation and dehydrogenation of kerogen, as well as oxidation of sulfide minerals.

Advanced source apportionment of carbonaceous aerosols by coupling offline AMS and radiocarbon size-segregated measurements over a nearly 2-year period

Abstract. Carbonaceous aerosols are related to adverse human health effects. Therefore, identification of their sources and analysis of their chemical composition is important. The offline AMS (aerosol mass spectrometer) technique offers quantitative separation of organic aerosol (OA) factors which can be related to major OA sources, either primary or secondary. While primary OA can be more clearly separated into sources, secondary (SOA) source apportionment is more challenging because different sources – anthropogenic or natural, fossil or non-fossil – can yield similar highly oxygenated mass spectra. Radiocarbon measurements provide unequivocal separation between fossil and non-fossil sources of carbon. Here we coupled these two offline methods and analysed the OA and organic carbon (OC) of different size fractions (particulate matter below 10 and 2.5 µm – PM10 and PM2.5, respectively) from the Alpine valley of Magadino (Switzerland) during the years 2013 and 2014 (219 samples). The combination of the techniques gave further insight into the characteristics of secondary OC (SOC) which was rather based on the type of SOC precursor and not on the volatility or the oxidation state of OC, as typically considered. Out of the primary sources separated in this study, biomass burning OC was the dominant one in winter, with average concentrations of 5.36 ± 2.64 µg m−3 for PM10 and 3.83 ± 1.81 µg m−3 for PM2.5, indicating that wood combustion particles were predominantly generated in the fine mode. The additional information from the size-segregated measurements revealed a primary sulfur-containing factor, mainly fossil, detected in the coarse size fraction and related to non-exhaust traffic emissions with a yearly average PM10 (PM2.5) concentration of 0.20 ± 0.24 µg m−3 (0.05 ± 0.04 µg m−3). A primary biological OC (PBOC) was also detected in the coarse mode peaking in spring and summer with a yearly average PM10 (PM2.5) concentration of 0.79 ± 0.31 µg m−3 (0.24 ± 0.20 µg m−3). The secondary OC was separated into two oxygenated, non-fossil OC factors which were identified based on their seasonal variability (i.e. summer and winter oxygenated organic carbon, OOC) and a third anthropogenic OOC factor which correlated with fossil OC mainly peaking in winter and spring, contributing on average 13 % ± 7 % (10 % ± 9 %) to the total OC in PM10 (PM2.5). The winter OOC was also connected to anthropogenic sources, contributing on average 13 % ± 13 % (6 % ± 6 %) to the total OC in PM10 (PM2.5). The summer OOC (SOOC), stemming from oxidation of biogenic emissions, was more pronounced in the fine mode, contributing on average 43 % ± 12 % (75 % ± 44 %) to the total OC in PM10 (PM2.5). In total the non-fossil OC significantly dominated the fossil OC throughout all seasons, by contributing on average 75 % ± 24 % to the total OC. The results also suggested that during the cold period the prevailing source was residential biomass burning while during the warm period primary biological sources and secondary organic aerosol from the oxidation of biogenic emissions became important. However, SOC was also formed by aged fossil fuel combustion emissions not only in summer but also during the rest of the year.

An alternative method to determine the share of fossil carbon in solid refuse-derived fuels – Validation and comparison with three standardized methods

Today different types of wastes are used as refuse-derived fuels (RDF) either in waste-to-energy plants or as fuel substitutes in energy-intensive industrial processes. In order to quantify their greenhouse-gas relevance (fossil carbon content), reliable and practical analytical methods are required, which allow differentiation between biogenic and fossil organic carbon. In the present paper, an alternative method to determine the fossil share in RDFs is examined and validated. The so-called “adapted Balance Method” (aBM) is applied to three different RDFs and the results are compared to three standardized methods, namely the Radiocarbon Method (14C-Method), the Selective Dissolution Method (SDM), and the Manual Sorting Method (MS). The aBM is based on the distinctly different elemental composition of water-and-ash-free biogenic and of fossil matter (TOXBIO and TOXFOS). Within the study, these compositional data are derived by manual sorting of the RDFs. The results show that the values obtained by the aBM are in excellent agreement with the results of the 14C-Method (considered as reference method). Mean deviations between the two methods of −0.9 to +1.9% absolute for the share of fossil carbon are found which are statistically insignificant. High trueness and reliability of the aBM can be expected, independent of the RDF type. In contrast, the reliability of the other standardized methods (SDM and MS) appears to strongly depend on the type and composition of the RDF. The results further indicate that the generation of RDF-specific data on TOXFOS is important for the aBM if significant shares of polymers with comparably high oxygen content might be present in the RDF and if low uncertainties of the results (<3% relative) are required. The findings demonstrate that the alternative method has advantages compared to standardized methods with respect to reliability and/or costs.

Late Cretaceous marine arthropods relied on terrestrial organic matter as a food source: Geochemical evidence from the Coon Creek Lagerstätte in the Mississippi Embayment.

The Upper Cretaceous Coon Creek Lagerstätte of Tennessee, USA, is known for its extremely well-preserved mollusks and decapod crustaceans. However, the depositional environment of this unit, particularly its distance to the shoreline, has long been equivocal. To better constrain the coastal proximity of the Coon Creek Formation, we carried out a multiproxy geochemical analysis of fossil decapod (crab, mud shrimp) cuticle and associated sediment from the type section. Elemental analysis and Raman spectroscopy confirmed the presence of kerogenized carbon in the crabs and mud shrimp; carbon isotope (δ13 C) analysis of bulk decapod cuticle yielded similar mean δ13 C values for both taxa (-25.1‰ and -26‰, respectively). Sedimentary biomarkers were composed of n-alkanes from C16 to C36 , with the short-chain n-alkanes dominating, as well as other biomarkers (pristane, phytane, hopanes). Raman spectra and biomarker thermal maturity indices suggest that the Coon Creek Formation sediments are immature, which supports retention of unaltered, biogenic isotopic signals in the fossil organic carbon remains. Using our isotopic results and published calcium carbonate δ13 C values, we modeled carbon isotope values of carbon sources in the Coon Creek Formation, including potential marine (phytoplankton) and terrestrial (plant) dietary sources. Coon Creek Formation decapod δ13 C values fall closer to those estimated for terrigenous plants than marine phytoplankton, indicating that these organisms were feeding primarily on terrigenous organic matter. From this model, we infer that the Coon Creek Formation experienced significant terrigenous organic matter input via a freshwater source and thus was deposited in a shallow, nearshore marine environment proximal to the shoreline. This study helps refine the paleoecology of nearshore settings in the Mississippi Embayment during the global climatic shift in the late Campanian-early Maastrichtian and demonstrates for the first time that organic δ13 C signatures in exceptionally preserved fossil marine arthropods are a viable proxy for use in paleoenvironmental reconstructions.

The color of refractory organic carbon

Organic matter studies find an echo within different topics such as biogeochemical cycles, processes occurring in continental surfaces, anthropogenic activities, climate science, earth and planetary sciences, etc. Today’s challenges include finding and developing the most appropriate method(s) supporting the differentiation and characterisation of various types of recalcitrant organic matter in modern environments. In this study, we focus on combustion residues and coals as these two types of organic matter contain a significant amount of so-called recalcitrant organic carbon (black carbon and fossil organic carbon). Both these materials are ubiquitous, broadly stem from the same living organisms and have similar polyaromatic structures. In this respect, we tested a spectrophotometry method, classically used for sedimentology, as a very fast method for preliminary investigations. Analyses were performed with a wide range of standards and referenced samples. The results discriminate three different spectral signatures related to the degree of transformation of organic matter related to the degree of aromaticity (i.e. carbonisation). Using calibration curves, total organic carbon content can be estimated in experimental mixes with mineral matter and in a real context using subsurface sample (Gironville 101 borehole, Paris Basin, France). This method has particularly high sensitivity to very low organic matter content and is shown to be promising for a rapid evaluation of the organic carbon content.

Sources and radiocarbon ages of aerosol organic carbon along the east coast of China and implications for atmospheric fossil carbon contributions to China marginal seas

Aerosol deposition is an important mechanism for the delivery of terrestrial organic carbon (OC) to marginal seas, but OC age characteristics of aerosols are not well constrained and their contributions to sediment OC burial have not been quantified. Total suspended particle samples were collected along the east coast of China at Changdao (CD), Qingdao (QD) and Huaniao Island (HNI), and were analyzed for total organic carbon (TOC) isotopes (13C and 14C) in order to bridge this information gap. TOC δ13C and Δ14C values ranged from −23.6 to −30.5‰, and −153 to −687‰, respectively, with the latter corresponding to 14C ages ranging from 1280 to 9260yr. Estimated contributions of fossil carbon to TOC based on 14C mass balance approach ranged from 26 to 73%, with strong seasonal variations in fossil carbon observed at CD. Fossil carbon at CD showed the highest proportion (73%) in winter, reflecting anthropogenic emissions and the lowest proportion (26%) in summer, caused by biomass contribution (annual ave., 52%±17%). In contrast, the fossil carbon at both QD (57–64%) and HNI (57–67%) dominated throughout the year, reflecting local anthropogenic influences and long-range transport. Mass balance estimates indicate that atmospheric deposition and riverine export accounted for 31% and 69% of fossil carbon inputs to the China marginal seas (CMS) respectively, with fossil carbon burial efficiencies approaching 100% in the CMS. On a global scale, an atmospheric fossil carbon deposition flux of 17.2TgCyr−1 was estimated, equivalent to 40% of the estimated fluvial flux to the ocean, and potentially accounting for 24–41% of fossil OC burial in marine sediments. Therefore, the atmospheric deposition constitutes an important source of fossil carbon to marine sediments, and could play a key role in regional and global scale OC budgets and biogeochemical cycles.