Description: Compound-specific radiocarbon (14C) dating often requires working with small samples of 〈 100 µg carbon (µgC). This makes the radiocarbon dates of biomarker compounds very sensitive to biases caused by extraneous carbon of unknown composition, a procedural blank, which is introduced to the samples during the steps necessary to prepare a sample for radiocarbon analysis by accelerator mass spectrometry (i.e., isolating single compounds from a heterogeneous mixture, combustion, gas purification and graphitization). Reporting accurate radiocarbon dates thus requires a correction for the procedural blank. We present our approach to assess the fraction modern carbon (F14C) and the mass of the procedural blanks introduced during the preparation procedures of lipid biomarkers (i.e. n-alkanoic acids) and lignin phenols. We isolated differently sized aliquots (6–151 µgC) of n-alkanoic acids and lignin phenols obtained from standard materials with known F14C values. Each compound class was extracted from two standard materials (one fossil, one modern) and purified using the same procedures as for natural samples of unknown F14C. There is an inverse linear relationship between the measured F14C values of the processed aliquots and their mass, which suggests constant contamination during processing of individual samples. We use Bayesian methods to fit linear regression lines between F14C and 1/mass for the fossil and modern standards. The intersection points of these lines are used to infer F14Cblank and mblank and their associated uncertainties. We estimate 4.88 ± 0.69 μgC of procedural blank with F14C of 0.714 ± 0.077 for n-alkanoic acids, and 0.90 ± 0.23 μgC of procedural blank with F14C of 0.813 ± 0.155 for lignin phenols. These F14Cblank and mblank can be used to correct AMS results of lipid and lignin samples by isotopic mass balance. This method may serve as a standardized procedure for blank assessment in small-scale radiocarbon analysis.

Description: Highlights • Continental margin-scale spatial variability in C values among grain size fractions is presented. • Two different hydrodynamic modes influencing in 14C heterogeneity are identified. • A new index (H14 index) is defined to describe overall 14C heterogeneity within marine surface sedimentary OC. Abstract The deposition and long-term burial of sedimentary organic matter (OM) on continental margins comprises a fundamental component of the global carbon cycle. A key unknown in interpretation of carbon isotope records of sedimentary OM is the extent to which OM accumulating in continental shelf and slope sediments is influenced by dispersal and redistribution processes. Here, we present results from an extensive survey of organic carbon (OC) characteristics of grain size fractions (ranging from 〈20 to 250 μm) retrieved from Chinese marginal sea surface sediments in order to assess the extent to which the abundance and isotope composition of OM in shallow shelf seas is influenced by hydrodynamic processes. Our findings show that contrasting relationships exist between 14C contents of OC and grain size in surface sediments associated with two different hydrodynamic modes, suggesting that transport pathways and mechanisms imparted by the different hydrodynamic conditions exert a strong influence on 14C contents of OM in continental shelf sediments. In deeper regions and erosional areas, we infer that bedload transport exerts the strongest influence on (decreases) OC 14C contents of the coarser fraction, while resuspension processes induce OC 14C depletion of intermediate grain size fractions in shallow inner-shelf settings. We use the inter-fraction spread in 14C values, defined here as 14H , to argue that the hydrodynamic processes amplify overall 14C heterogeneity within corresponding bulk sediment samples. The magnitude and footprint of this heterogeneity carries implications for our understanding of carbon cycling in shallow marginal seas.

Description: Long-chain diols (LCDs) occur widespread in marine environments and also in lakes and rivers. Transport of LCDs from rivers may impact the distribution of LCDs in coastal environments, however relatively little is known about the distribution and biological sources of LCDs in river systems. In this study, we investigated the distribution of LCDs in suspended particulate matter (SPM) of three river systems (Godavari, Danube, and Rhine) in relation with precipitation, temperature, and source catchments. The dominant long-chain diol is the C32 1,15-diol followed by the C30 1,15-diol in all studied river systems. In regions influenced by marine waters, such as delta systems, the fractional abundance of the C30 1,15-diol is substantially higher than in the river itself, suggesting different LCD producers in marine and freshwater environments. A change in the LCD distribution along the downstream transects of the rivers studied was not observed. However, an effect of river flow is observed; i.e., the concentration of the C32 1,15-diol is higher in stagnant waters such as reservoirs and during seasons with river low stands. A seasonal change in the LCD distribution was observed in the Rhine, likely due to a change in the producers. Eukaryotic diversity analysis by 18S rRNA gene sequencing of SPM from the Rhine showed extremely low abundances of sequences (i.e., 〈0.32% of total reads) related to known algal LCD producers. Furthermore, incubation of the river water with 13C-labeled bicarbonate did not result in 13C incorporation into LCDs. This indicates that the LCDs present are mainly of fossil origin in the fast-flowing part of the Rhine. Overall, our results suggest that the LCD producers in rivers predominantly reside in lakes or side ponds that are part of the river system.

Description: Compound-specific radiocarbon (14C) dating often requires working with small samples of 〈 100 μg carbon (μgC). This makes the radiocarbon dates of biomarker compounds very sensitive to biases caused by extraneous carbon of unknown composition, a procedural blank, which is introduced to the samples during the steps necessary to prepare a sample for radiocarbon analysis by accelerator mass spectrometry (i.e., isolating single compounds from a heterogeneous mixture, combustion, gas purification and graphitization). Reporting accurate radiocarbon dates thus requires a correction for the procedural blank. We present our approach to assess the fraction modern carbon (F14C) and the mass of the procedural blanks introduced during the preparation procedures of lipid biomarkers (i.e. n-alkanoic acids) and lignin phenols. We isolated differently sized aliquots (6–151 μgC) of n-alkanoic acids and lignin phenols obtained from standard materials with known F14C values. Each compound class was extracted from two standard materials (one fossil, one modern) and purified using the same procedures as for natural samples of unknown F14C. There is an inverse linear relationship between the measured F14C values of the processed aliquots and their mass, which suggests constant contamination during processing of individual samples. We use Bayesian methods to fit linear regression lines between F14C and 1/mass for the fossil and modern standards. The intersection points of these lines are used to infer F14Cblank and mblank and their associated uncertainties. We estimate 4.88 ± 0.69 μgC of procedural blank with F14C of 0.714 ± 0.077 for n-alkanoic acids, and 0.90 ± 0.23 μgC of procedural blank with F14C of 0.813 ± 0.155 for lignin phenols. These F14Cblank and mblank can be used to correct AMS results of lipid and lignin samples by isotopic mass balance. This method may serve as a standardized procedure for blank assessment in small-scale radiocarbon analysis.

Description: Sedimentary high molecular weight (HMW) n-alkyl lipids derived from the waxes of terrestrial plants are common target compounds in biogeochemical and paleoenvironmental research. These plant waxes derive predominantly from the epicuticular cover of vascular plant leaves and their relative and absolute abundances and stable isotopic composition can be used as proxies to decipher, e.g., continental climate and land-ocean carbon transfer processes. In marine sediments, however, compound-specific radiocarbon analysis has revealed that plant waxes are often not syn-depositional, but instead are substantially 14C-depleted (‘pre-aged’) upon deposition. This 14C-depletion can be caused by various processes that either promote retention of plant waxes during transport from source to sink such as storage in soils or entrainment in deposition-resuspension loops in rivers and on continental shelves or, alternatively, by processes that add HMW n-alkyl lipids from other sources (e.g., petrogenic inputs). Here, we review the intrinsic and extrinsic processes affecting the sedimentary plant wax 14C composition (ranging from chemical processes to continental-scale environmental conditions), how plant wax 14C compositions translate into mean ages, and which processes control plant wax mean ages in marine sediments. Finally, we use a compilation of available and new compound-specific plant wax 14C data to provide a synthesis and evaluate the major controls on plant wax mean ages in marine sediments at the global scale.

Description: © The Author(s), 2015. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 12 (2015): 4841-4860, doi:10.5194/bg-12-4841-2015.

Description: Hydrolyzable organic carbon (OC) comprises a significant component of sedimentary particulate matter transferred from land into oceans via rivers. Its abundance and nature are however not well studied in Arctic river systems, and yet may represent an important pool of carbon whose fate remains unclear in the context of mobilization and related processes associated with a changing climate. Here, we examine the molecular composition and source of hydrolyzable compounds isolated from sedimentary particles derived from nine rivers across the pan-Arctic. Bound fatty acids (b-FAs), hydroxy FAs, n-alkane-α,ω-dioic acids (DAs) and phenols were the major components released upon hydrolysis of these sediments. Among them, b-FAs received considerable inputs from bacterial and/or algal sources, whereas ω-hydroxy FAs, mid-chain substituted acids, DAs, and hydrolyzable phenols were mainly derived from cutin and suberin of higher plants. We further compared the distribution and fate of suberin- and cutin-derived compounds with those of other terrestrial biomarkers (plant wax lipids and lignin phenols) from the same Arctic river sedimentary particles and conducted a benchmark assessment of several biomarker-based indicators of OC source and extent of degradation. While suberin-specific biomarkers were positively correlated with plant-derived high-molecular-weight (HMW) FAs, lignin phenols were correlated with cutin-derived compounds. These correlations suggest that, similar to leaf-derived cutin, lignin was mainly derived from litter and surface soil horizons, whereas suberin and HMW FAs incorporated significant inputs from belowground sources (roots and deeper soil). This conclusion is supported by the negative correlation between lignin phenols and the ratio of suberin-to-cutin biomarkers. Furthermore, the molecular composition of investigated biomarkers differed between Eurasian and North American Arctic rivers: while lignin dominated in the terrestrial OC of Eurasian river sediments, hydrolyzable OC represented a much larger fraction in the sedimentary particles from Colville River. Hence, studies exclusively focusing on either plant wax lipids or lignin phenols will not be able to fully unravel the mobilization and fate of bound OC in Arctic rivers. More comprehensive, multi-molecular investigations are needed to better constrain the land–ocean transfer of carbon in the changing Arctic, including further research on the degradation and transfer of both free and bound components in Arctic river sediments.

Description: X. Feng acknowledges support from the Chinese National Key Development Program for Basic Research (2014CB954003, 2015CB954201). The ISSS program is supported by the Knut and Alice Wallenberg Foundation, headquarters of the Russian Academy of Sciences, the Swedish Research Council, the US National Oceanic and Atmospheric Administration, the Russian Foundation of Basic Research (#13-05-12028, 13-05-12041), the Swedish Polar Research Secretariat and the Nordic Council of Ministers (Arctic Co-Op and TRI-DEFROST programs). Collection of the Mackenzie sediment samples was supported by Fisheries and Oceans Canada and Indian and Northern Affairs Canada as part of the NOGAP B.6 project. Ö. Gustafsson acknowledges an Academy Research Fellow grant from the Swedish Royal Academy of Sciences. I. P. Semiletov and O. V. Dudarev thank the Government of the Russian Federation (#2013-220-04-157) for support as well as A. I. Khanchuk personally. T. I. Eglinton acknowledges support from Swiss National Science foundation (SNF) grant no. 200021_140850, and grants OCE-9907129, OCE-0137005, and OCE-0526268 from the US National Science Foundation (NSF), the Stanley Watson Chair for Excellence in Oceanography, and ETH Zurich. J. E. Vonk is thankful for support from NWO Rubicon (#825.10.022) and Veni (#863.12.004). B. E. van Dongen is thankful for support from the UK NERC (NE/I024798/1). R. M. Holmes acknowledges support from NSF 0436118, NSF 0732555, and NSF 1107774. X. Feng thanks WHOI for a postdoctoral scholar fellowship and for postdoctoral support from ETH Zurich.

Description: Author Posting. © The Author(s), 2014. This is the author's version of the work. It is posted here by permission of National Academy of Sciences for personal use, not for redistribution. The definitive version was published in Proceedings of the National Academy of Sciences of the United States of American 112 (2015): 5607-5612, doi: 10.1073/pnas.1419133112.

Description: Paleoclimate records indicate a series of severe droughts was associated with societal collapse of the Classic Maya during the Terminal Classic period (approximately 800 to 950 CE). Evidence for drought largely derives from the drier, less populated northern Maya Lowlands, but does not explain more pronounced and earlier societaldisruption in the relatively humid southern Maya Lowlands. Here we apply hydrogen and carbon isotope compositions of plant-wax lipids in two lake sediment cores to assess changes in water availability and land use in both the northern and southern Maya lowlands. We show that relatively more intense drying occurred in the southern lowlands than in the northern lowlands during the Terminal Classic period, consistent with earlier and more persistent societal decline in the south. Our results also indicate a period of substantial drying in the southern Maya Lowlands from ~200 to 500 CE, during the Terminal Preclassic and Early Classic periods. Plant-wax carbon isotope records indicate a decline in C4 plants in both lake catchments during the Early Classic period, interpreted to reflect a shift from extensive agriculture to intensive, water-conservative maize cultivation that was motivated by a drying climate. Our results imply that agricultural adaptations developed in response to earlier droughts were initially successful, but failed under the more severe droughts of the Terminal Classic period.

Description: This work was partially funded by the Italian Ministry of the Environment and by the U.S. National Science Foundation Graduate Research Fellowship.

Description: Author Posting. © The Author(s), 2018. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Nature Geoscience 11 (2018): 584-588, doi:10.1038/s41561-018-0159-8.

Description: Wildfires and incomplete combustion of fossil fuel produce large amounts of black carbon. Black carbon production and transport are essential components of the carbon cycle. Constraining estimates of black carbon exported from land to ocean is critical, given ongoing changes in land use and climate, which affect fire occurrence and black carbon dynamics. Here, we present an inventory of the concentration and radiocarbon content (∆14C) of particulate black carbon for 18 rivers around the globe. We find that particulate black carbon accounts for about 15.8 ± 0.9% of river particulate organic carbon, and that fluxes of particulate black carbon co-vary with river-suspended sediment, indicating that particulate black carbon export is primarily controlled by erosion. River particulate black carbon is not exclusively from modern sources but is also aged in intermediate terrestrial carbon pools in several high-latitude rivers, with ages of up to 17,000 14C years. The flux-weighted 14C average age of particulate black carbon exported to oceans is 3,700 ± 400 14C years. We estimate that the annual global flux of particulate black carbon to the ocean is 0.017 to 0.037 Pg, accounting for 4 to 32% of the annually produced black carbon. When buried in marine sediments, particulate black carbon is sequestered to form a long-term sink for CO2.

Description: A.C. acknowledges financial support from the University of Zurich Forschungskredit Fellowship and the University of Zurich (grant No. STWF-18-026). M.R., S.A. and M.S. acknowledge support from the University Research Priority Projection Global Change and Biodiversity (URPP-GCB). M.Z. acknowledges support from the National Natural Science Foundation of China (No. 41521064). T.E. acknowledges support from the Swiss National Science Foundation (“CAPS-LOCK” and “CAPS-LOCK2” #200021_140850). V.G. acknowledges financial support from an Independent Study Award from the Woods Hole Oceanographic Institution.