Relationships between carbon isotopic composition and mode of binding of natural organic matter in selected marine sediments

Author Posting. © Elsevier B.V., 2007. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Organic Geochemistry 38 (2007):1824-1837, doi:10.1016/j.orggeochem.2007.07.008.We have investigated the relationships between radiocarbon (14C) and stable carbon (13C) isotopic composition and the different modes of binding of organic matter (OM) present in surficial sediments from near-shore and continental margin sites that vary in terms of input and depositional conditions. To improve our understanding of the entire OM pool, isotopic analysis of sedimentary sub-fractions, as opposed to individual compounds, was performed. This was achieved by sequentially treating sediments by solvent extraction to examine unbound compounds, followed by saponification to cleave ester linked moieties. Isotopic analysis was then performed on the bulk sediment and resulting residues. The molecular composition of the extracts was examined using gas chromatography/mass spectrometry (GC/MS), and the relative contributions of terrestrial and marine biomarkers were assessed. Radiocarbon abundances (Δ14C) of the bulk sediment reflect a mixture of modern, pre-aged and fossil carbon. Offsets in Δ14C between the bulk sediment and sediment residues demonstrate varying associations of these carbon pools. For the majority of sites, a negative offset between extracted (EX2 RES) and saponified (SA-RES) sediment 1 residues results from the removal of relatively 4C-rich material during saponification. Saponification extracts (SAEs) are mainly composed of short chain (n-C12 to n-C24) alkanoic acids with an even/odd dominance indicating a predominantly marine algal or microbial source. This provides evidence for the protection of labile marine carbon by chemical binding. This study aims to bridge the gap between molecular level and bulk OM analyses in marine sediments.The work was supported by funds from the National Science Foundation (CHE-0089172; OCE-0526268)

Developing marker trait associations in the population Chieftan/Barque//Manley/VB9104 using novel techniques

G.L. McMichael, J.K. Eglinton, A.R. Barr and K.J. Chalmer

Compound-Specific Radiocarbon Analysis by Elemental Analyzer–Accelerator Mass Spectrometry: Precision and Limitations

[EN]We examine instrumental and methodological capabilities for microscale (10−50μg of C) radiocarbon analysisof individual compounds in the context of paleoclimate and paleoceanography applications, for which relatively high-precisionmeasurements are required. An extensive suite of data for14C-free and modern reference materials processed using differentmethods and acquired using an elemental-analyzer−accelerator-mass-spectrometry (EA-AMS) instrumental setup at ETHZurich was compiled to assess the reproducibility of specific isolation procedures. In order to determine the precision, accuracy,and reproducibility of measurements on processed compounds, we explore the results of both reference materials and threeclasses of compounds (fatty acids, alkenones, and amino acids) extracted from sediment samples. We utilize a MATLAB codedeveloped to systematically evaluate constant-contamination-model parameters, which in turn can be applied to measurementsof unknown process samples. This approach is computationally reliable and can be used for any blank assessment of small-sizeradiocarbon samples. Our results show that a conservative lower estimate of the sample sizes required to produce relativelyhigh-precision14C data (i.e., with acceptable errors of 0.5, a precision of 2% can be achieved for alkenone and fatty acid samples containing≥15 and 10μg of C, respectivel

Surface and subsurface manifestations of gas movement through a N–S transect of the Gulf of Mexico

Author Posting. © The Authors, 2004. This is the author's version of the work. It is posted here by permission of Elsevier B. V. for personal use, not for redistribution. The definitive version was published in Marine and Petroleum Geology 22 (2005): 479-497, doi:10.1016/j.marpetgeo.2004.08.008.Large volumes of gas have vented through a north-south transect of the offshore northern Gulf of Mexico. An overview of surface and subsurface manifestations of this gas venting is presented. This gas movement has caused extensive alteration of reservoired oils to the north of the transect which are estimated to have equilibrated with, or been gas washed by, as much as 30 volumes of gas for every volume of oil. This gas washing entrains and carries upward the most volatile oil components depositing them in either shallower reservoirs or venting them to the overlying sediments and the water column. A significant amount of this gas bypasses the reservoirs and vents upward into the overlying sediments and waters. In spite of the significant amounts of the gas involved, the venting at the seafloor appears to occur primarily through highly localized faults and fractures. This gas discharge is spatially and temporally heterogeneous, making it difficult to estimate the actual hydrocarbon fluxes involved. This upward gas movement leaves characteristic signatures at the sediment water interface including carbonate pavements in older seep areas, and chemosynthetic biological communities, methane hydrates, and gas seeps in more recent long-term seep areas. In some cases where gas venting is very recent, massive disruption of surface and subsurface sediments is observed to be occasionally accompanied by mud volcanoes. Venting can be vigorous enough to produce methane gas bubbles, which appear to be injected rapidly into surface waters and which may constitute a significant source of methane, a greenhouse gas, to the atmosphere. In the northern Gulf of Mexico, gas venting is sometimes accompanied by natural oil slicks at the sea surface, which can be tracked for many miles in non-productive areas. These gas-venting signatures are not unique to the Gulf of Mexico; similar seep features are observed in sediments worldwide. The widespread occurrence of these seep features, which may or may not be related to subsurface oil and gas deposits, may explain why use of surface seeps has often proved to be so controversial in oil exploration. Indeed, most seeps are probably not linked with economic subsurface petroleum reservoirs. The relationships between surface seep features and productive subsurface reservoirs along a N-S transect of the Northern Gulf of Mexico are presented as an example of how all surface and subsurface geochemical, geological, geophysical data might be used together to better constrain interpretations regarding the nature and dynamics of subsurface oil and gas deposits and their plumbing in frontier areas.Support for this work was provided by the Department of Energy, Grant No. DE-FG02-86EF13466 and U.S. Department of Energy Grant No. DE-FC26-00NT40920 through the University of Mississippi to Jean Whelan and; Gas Research Institute Contract GRI50972603787 to Larry Cathles, Cornell University with a subcontract to Jean Whelan

A novel approach for construction of radiocarbon-based chronologies for speleothems

Robust chronologies are crucial for the correct interpretation of climate proxy records and for detailed reconstructions of palaeoclimate. Stalagmites have garnered strong interest as recorders of past climate in part due to their amenability to U-series dating. However, many stalagmites are not dateable using this technique due to low 238U and/or high detrital Th concentrations (e.g., many tropical cave systems (Adkins et al., 2013)), and occasionally these issues affect stalagmites across wide geographical regions (e.g., large parts of Australia (Green et al. 2013)) complicating the use of stalagmites in these areas. Radiocarbon (14C) offers an alternative method of dating stalagmites, but issues associated with the ‘dead carbon fraction’ (DCF) have historically hindered this approach. Here, a novel 14C-based method for dating stalagmites is presented and discussed. The technique calculates a best-fit growth rate between a time-series of stalagmite 14C data and known atmospheric 14C variability. The new method produces excellent results for stalagmites that satisfy four requirements: i) the absence of long-term secular variability in DCF (i.e., stalagmite DCF varies around a mean value with no long-term trend), ii) stalagmite growth rate does not vary significantly (the technique identifies stalagmites with substantial growth rate variability), iii) the stalagmite record is long enough that measurable 14C decay has occurred, and iv) one ‘anchor’ point exists where the calendar age is known. The model produces good results for a previously U–Th dated stalagmite from Heshang Cave, China, and is then applied to an undated stalagmite from southern Poland. The new method will not replace high-precision U–Th measurements, because the precision of the technique is difficult to quantify. However, it provides a means for dating certain stalagmites undateable by conventional U–Th methods and for refining coarse U–Th chronologies

To what extent can online mapping be decolonial? A journey throughout Indigenous cartography in Canada

In this paper, we describe and reflect upon our journey through Indigenous online mapping in Canada. This journey has been planned according to an academic goal: assessing the potential of online cartography for decolonial purposes. To reach this goal, we have followed methodological directions provided by Indigenous scholar Linda Tuhiwai Smith to review 18 Indigenous web-mapping sites across Canada. Supported by a series of ten interviews, this content analysis enabled us to sketch some of the contours of contemporary Indigenous cartography. On one hand, Indigenous communities largely control the data that are shared on these websites. They also partially control the way these data are represented through the mobilization of digital storytelling technologies that are better aligned with Indigenous ways of envisioning relationships to places than conventional maps. On the other hand, they do not have much control over the technological aspects of these projects, for which they remain heavily dependent on non-Indigenous partners. Throughout this journey, we noticed that women’s voices remained marginal in most of these mapping projects, but we also identified evidence supporting the idea that these voices are starting to play a vital role in the on-going effort of decolonizing mapping processes

Selective preservation of organic matter in marine environments; processes and impact on the sedimentary record

© The Authors, 2010. This article is distributed under the terms of the Creative Commons Attribution 3.0 License. The definitive version was published in Biogeosciences 7 (2010): 483-511, doi: 10.5194/bg-7-483-2010The present paper is the result of a workshop sponsored by the DFG Research Center/Cluster of Excellence MARUM "The Ocean in the Earth System", the International Graduate College EUROPROX, and the Alfred Wegener Institute for Polar and Marine Research. The workshop brought together specialists on organic matter degradation and on proxy-based environmental reconstruction. The paper deals with the main theme of the workshop, understanding the impact of selective degradation/preservation of organic matter (OM) in marine sediments on the interpretation of the fossil record. Special attention is paid to (A) the influence of the molecular composition of OM in relation to the biological and physical depositional environment, including new methods for determining complex organic biomolecules, (B) the impact of selective OM preservation on the interpretation of proxies for marine palaeoceanographic and palaeoclimatic reconstruction, and (C) past marine productivity and selective preservation in sediments. It appears that most of the factors influencing OM preservation have been identified, but many of the mechanisms by which they operate are partly, or even fragmentarily, understood. Some factors have not even been taken carefully into consideration. This incomplete understanding of OM breakdown hampers proper assessment of the present and past carbon cycle as well as the interpretation of OM based proxies and proxies affected by OM breakdown. To arrive at better proxy-based reconstructions "deformation functions" are needed, taking into account the transport and diagenesis-related molecular and atomic modifications following proxy formation. Some emerging proxies for OM degradation may shed light on such deformation functions. The use of palynomorph concentrations and selective changes in assemblage composition as models for production and preservation of OM may correct for bias due to selective degradation. Such quantitative assessment of OM degradation may lead to more accurate reconstruction of past productivity and bottom water oxygenation. Given the cost and effort associated with programs to recover sediment cores for paleoclimatological studies, as well as with generating proxy records, it would seem wise to develop a detailed sedimentological and diagenetic context for interpretation of these records. With respect to the latter, parallel acquisition of data that inform on the fidelity of the proxy signatures and reveal potential diagenetic biases would be of clear value.We acknowledge generous financial support by the DFG Research Center/Cluster of Excellence MARUM “The Ocean in the Earth System”, the International Graduate College EUROPROX and the Alfred Wegener Institute for Polar and Marine Research enabling the realisation of the “Workshop on Selective Preservation of Organic Matter: Processes and Impact on the Fossil Record” which formed the basis of this paper. GJMV acknowledges support by the German Science Foundation (DFG grant VE486/2)

The Modern Ocean Sediment Archive and Inventory of Carbon (MOSAIC): version 2.0

Marine sediments play a crucial role in the global carbon cycle by acting as the ultimate sink of both terrestrial and marine organic carbon. To understand the spatiotemporal variability in the content, sources, and dynamics of organic carbon in marine sediments, a curated and harmonized database of organic carbon and associated parameters is needed, which has prompted the development of the Modern Ocean Sediment Archive and Inventory of Carbon (MOSAIC) database (http://mosaic.ethz.ch/, last access: 26 July 2023; https://doi.org/10.5281/zenodo.8322094, Paradis, 2023; https://doi.org/10.5168/mosaic019.1, Van der Voort et al., 2019​​​​​​​). MOSAIC version 2.0 has expanded the spatiotemporal coverage of the original database by &gt;400 % and now holds data from more than 21 000 individual sediment cores from different continental margins on a global scale. Additional variables have also been incorporated into MOSAIC v.2.0 that are crucial to interpret the quantity, origin, and age of organic carbon in marine sediments globally. Sedimentological parameters (e.g. grain size fractions and mineral surface area) help understand the effect of hydrodynamic sorting and mineral protection on the distribution of organic carbon, while molecular biomarker signatures (e.g. lignin phenols, fatty acids, and alkanes) can help constrain the specific origin of organic matter. MOSAIC v.2.0 also stores data on specific sediment and molecular fractions, which provide further insight into the processes that affect the degradation and ageing of organic carbon in marine sediments. Data included within MOSAIC are continuously expanding, and version control will allow users to benefit from updated versions while ensuring reproducibility of their findings.</p

Direct application of compound-specific radiocarbon analysis of leaf waxes to establish lacustrine sediment chronology

Author Posting. © Springer, 2007. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Journal of Paleolimnology 39 (2008): 43-60, doi:10.1007/s10933-007-9094-1.This study demonstrates use of compound-specific radiocarbon analysis (CSRA) for dating Holocene lacustrine sediments from carbonate-hosted Ordy Pond, Oahu, Hawaii. Long-chain odd-numbered normal alkanes (n-alkanes), biomarkers characteristic of terrestrial higher plants, were ubiquitous in Ordy Pond sediments. The δ13C of individual n-alkanes ranged from −29.9 to −25.5‰, within the expected range for n-alkanes synthesized by land plants using the C3 or C4 carbon fixation pathway. The 14C ages of n-alkanes determined by CSRA showed remarkably good agreement with 14C dates of rare plant macrofossils obtained from nearby sedimentary horizons. In general, CSRA of n-alkanes successfully refined the age-control of the sediments. The sum of n-alkanes in each sample produced 70–170 μg of carbon (C), however, greater age errors were confirmed for samples containing less than 80 μg of C. The 14C age of n-alkanes from one particular sedimentary horizon was 4,155 years older than the value expected from the refined age-control, resulting in an apparent and arguable age discrepancy. Several lines of evidence suggest that this particular sample was contaminated by introduction of 14C-free C during preparative capillary gas chromatography. This study simultaneously highlighted the promising potential of CSRA for paleo-applications and the risks of contamination associated with micro-scale 14C measurement of individual organic compounds.This project was funded by Petroleum Research Fund (PRF #40088-ACS) and in part by Sigma Xi, The Scientific Research Society (Grants in aid of research, 2003)