High-sensitivity measurement of diverse vascular plant-derived biomarkers in high-altitude ice cores

Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 36 (2009): L13501, doi:10.1029/2009GL037643.Semi-volatile organic compounds derived from burned and fresh vascular plant sources and preserved in high-altitude ice fields were detected and identified through use of recently developed analytical tools. Specifically, stir bar sorptive extraction and thermal desorption coupled with gas chromatography/time-of-flight mass spectrometry allowed measurement of multiple biomarkers in small sample volumes (≤30 ml). Among other compounds of interest, several diterpenoids, which suggest inputs from conifers and conifer burning, were identified in post-industrial era and older Holocene ice from the Sajama site in the Bolivian Andes, but not in a glacial period sample, consistent with aridity changes. Differences in biomarker assemblages between sites support the use of these compounds as regionally constrained recorders of vegetation and climate change. This study represents the first application of these analytical techniques to ice core research and the first indication that records of vegetation fires may be reconstructed from diterpenoids in ice.This project was supported in part by NSF-OCE (0402533), and NSF-EAR (0094475)

Arctic deltaic lake sediments as recorders of fluvial organic matter deposition

© The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Frontiers in Earth Science 4 (2016): 77, doi:10.3389/feart.2016.00077.Arctic deltas are dynamic and vulnerable regions that play a key role in land-ocean interactions and the global carbon cycle. Delta lakes may provide valuable historical records of the quality and quantity of fluvial fluxes, parameters that are challenging to investigate in these remote regions. Here we study lakes from across the Mackenzie Delta, Arctic Canada, that receive fluvial sediments from the Mackenzie River when spring flood water levels rise above natural levees. We compare downcore lake sediments with suspended sediments collected during the spring flood, using bulk (% organic carbon, % total nitrogen, δ13C, Δ14C) and molecular organic geochemistry (lignin, leaf waxes). High-resolution age models (137Cs, 210Pb) of downcore lake sediment records (n = 11) along with lamina counting on high-resolution radiographs show sediment deposition frequencies ranging between annually to every 15 years. Down-core geochemical variability in a representative delta lake sediment core is consistent with historical variability in spring flood hydrology (variability in peak discharge, ice jamming, peak water levels). Comparison with earlier published Mackenzie River depth profiles shows that (i) lake sediments reflect the riverine surface suspended load, and (ii) hydrodynamic sorting patterns related to spring flood characteristics are reflected in the lake sediments. Bulk and molecular geochemistry of suspended particulate matter from the spring flood peak and lake sediments are relatively similar showing a mixture of modern higher-plant derived material, older terrestrial permafrost material, and old rock-derived material. This suggests that deltaic lake sedimentary records hold great promise as recorders of past (century-scale) riverine fluxes and may prove instrumental in shedding light on past behavior of arctic rivers, as well as how they respond to a changing climate.Funding was provided by the US National Science Foundation as part of the Arctic Great Rivers Observatory (NSF-0732522 and NSF-1107774), as well as the Netherlands Organization for Scientific Research (Rubicon #825.10.022, and Veni #863.12.004). Additional funding for the lake coring was provided from WHOI through its Ocean and Climate Change Institute

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A radiocarbon-based assessment of the preservation characteristics of crenarchaeol and alkenones from continental margin sediments

Author Posting. © Elsevier B.V. , 2008. 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 39 (2008): 1039-1045, doi:10.1016/j.orggeochem.2008.02.006.Crenarchaeotal glycerol dibiphytanyl glycerol tetraether (GDGT) lipids and alkenones are two types of biomarkers derived from planktonic marine micro-organisms which are used for reconstruction of sea-surface temperatures. We determined the radiocarbon contents of the archaeal GDGT crenarchaeol and of alkenones isolated from continental margin sediments. Systematic differences were found between the two biomarkers, with higher radiocarbon contents in crenarchaeol than in the phytoplankton-derived alkenones. These differences can be explained by variable contributions of pre-aged, laterally advected material to the core sites. Crenarchaeol appears to be more efficiently degraded during transport in oxygen-replete environments than alkenones. Whether this reflects the influence of chemical structure or mode of protection (e.g., particle association) is not yet known.This work was funded by a Spinoza grant of NWO to J.S.S.D. and by NSF-grant OCE-0327405 to T.I.E.

Compound-specific radiocarbon dating of the varved Holocene sedimentary record of Saanich Inlet, Canada

Author Posting. © American Geophysical Union, 2004. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 19 (2004): PA2012, doi:10.1029/2003PA000927.The radiocarbon contents of various biomarkers extracted from the varve-counted sediments of Saanich Inlet, Canada, were determined to assess their applicability for dating purposes. Calibrated ages obtained from the marine planktonic archaeal biomarker crenarchaeol compared favorably with varve-count ages. The same conclusion could be drawn for a more general archaeal biomarker (GDGT-0), although this biomarker proved to be less reliable due to its less-specific origin. The results also lend support to earlier indications that marine crenarchaeota use dissolved inorganic carbon (DIC) as their carbon source. The average reservoir age offset ΔR of 430 years, determined using the crenarchaeol radiocarbon ages, varied by ±110 years. This may be caused by natural variations in ocean-atmosphere mixing or upwelling at the NE Pacific coast but variability may also be due to an inconsistency in the marine calibration curve when used at sites with high reservoir ages.This work was supported by the Netherlands Organization for Scientific Research (NWO) and NSF grants OCE-9907129 and OCE-0137005 (Eglinton)

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)

14C and 13C characteristics of higher plant biomarkers in Washington margin surface sediments

Author Posting. © The Author(s), 2012. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 105 (2013): 14-30, doi:10.1016/j.gca.2012.11.034.Plant wax lipids and lignin phenols are the two most common classes of molecular markers that are used to trace vascular plant-derived OM in the marine environment. However, their 13C and 14C compositions have not been directly compared, which can be used to constrain the flux and attenuation of terrestrial carbon in marine environment. In this study, we describe a revised method of isolating individual lignin phenols from complex sedimentary matrices for 14C analysis using high pressure liquid chromatography (HPLC) and compare this approach to a method utilizing preparative capillary gas chromatography (PCGC). We then examine in detail the 13C and 14C compositions of plant wax lipids and lignin phenols in sediments from the inner and mid shelf of the Washington margin that are influenced by discharge of the Columbia River. Plant wax lipids (including n-alkanes, n-alkanoic (fatty) acids, n-alkanols, and n-aldehydes) displayed significant variability in both δ13C (-28.3 to -37.5 ‰) and ∆14C values (-204 to +2 ‰), suggesting varied inputs and/or continental storage and transport histories. In contrast, lignin phenols exhibited similar δ13C values (between -30 to -34 ‰) and a relatively narrow range of ∆14C values (-45 to -150 ‰; HPLC-based mesurement) that were similar to, or younger than, bulk OM (-195 to -137 ‰). Moreover, lignin phenol 14C age correlated with the degradation characteristics of this terrestrial biopolymer in that vanillyl phenols were on average ~500 years older than syringyl and cinnamyl phenols that degrade faster in soils and sediments. The isotopic characteristics, abundance, and distribution of lignin phenols in sediments suggest that they serve as promising tracers of recently biosynthesized terrestrial OM during supply to, and dispersal within the marine environment. Lignin phenol 14C measurements may also provide useful constraints on the vascular plant end member in isotopic mixing models for carbon source apportionment, and for interpretation of sedimentary records of past vegetation dynamics. Key words: 14C and 13C composition, radiocarbon age, plant wax lipids, lignin phenols, Washington margin, marine carbon cycling, terrestrial organic matterGrants OCE-9907129, OCE-0137005, and OCE-0526268 (to TIE) from the National Science Foundation (NSF) supported this research

Timescales of lateral sediment transport in the Panama Basin as revealed by radiocarbon ages of alkenones, total organic carbon and foraminifera

Author Posting. © The Author(s), 2009. 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 Earth and Planetary Science Letters 290 (2010): 340-350, doi:10.1016/j.epsl.2009.12.030.Paired radiocarbon measurements on haptophyte biomarkers (alkenones) and on cooccurring tests of planktic foraminifera (Neogloboquadrina dutertrei and Globogerinoides sacculifer) from late glacial to Holocene sediments at core locations ME0005-24JC, Y69- 71P, and MC16 from the south-western and central Panama Basin indicate no significant addition of pre-aged alkenones by lateral advection. The strong temporal correspondence between alkenones, foraminifera and total organic carbon (TOC) also implies negligible contributions of aged terrigenous material. Considering controversial evidence for sediment redistribution in previous studies of these sites, our data imply that the laterally supplied material cannot stem from remobilization of substantially aged sediments. Transport, if any, requires syn-depositional nepheloid layer transport and redistribution of low-density or fine-grained components within decades of particle formation. Such rapid and local transport minimizes the potential for temporal decoupling of proxies residing in different grain size fractions and thus facilitates comparison of various proxies for paleoceanographic reconstructions in this study area. Anomalously old foraminiferal tests from a glacial depth interval of core Y69-71P may result from episodic spillover of fast bottom currents across the Carnegie Ridge transporting foraminiferal sands towards the north.This study was funded by the Helmholtz Young Investigators Group „Applications of molecular 14C analysis for the study of sedimentation processes and carbon cycling in marine sediments”. G.M. acknowledges financial support from WHOI postdoctoral scholarship program. T.I.E. was supported by NSF grant OCE-0526268. A.C.M. was supported by NSF grant ATM0602395

Global-scale evidence for the refractory nature of riverine black carbon

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.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.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

Antiplatelet therapy with aspirin, clopidogrel, and dipyridamole versus clopidogrel alone or aspirin and dipyridamole in patients with acute cerebral ischaemia (TARDIS): a randomised, open-label, phase 3 superiority trial

Background: Intensive antiplatelet therapy with three agents might be more effective than guideline treatment for preventing recurrent events in patients with acute cerebral ischaemia. We aimed to compare the safety and efficacy of intensive antiplatelet therapy (combined aspirin, clopidogrel, and dipyridamole) with that of guideline-based antiplatelet therapy. Methods: We did an international, prospective, randomised, open-label, blinded-endpoint trial in adult participants with ischaemic stroke or transient ischaemic attack (TIA) within 48 h of onset. Participants were assigned in a 1:1 ratio using computer randomisation to receive loading doses and then 30 days of intensive antiplatelet therapy (combined aspirin 75 mg, clopidogrel 75 mg, and dipyridamole 200 mg twice daily) or guideline-based therapy (comprising either clopidogrel alone or combined aspirin and dipyridamole). Randomisation was stratified by country and index event, and minimised with prognostic baseline factors, medication use, time to randomisation, stroke-related factors, and thrombolysis. The ordinal primary outcome was the combined incidence and severity of any recurrent stroke (ischaemic or haemorrhagic; assessed using the modified Rankin Scale) or TIA within 90 days, as assessed by central telephone follow-up with masking to treatment assignment, and analysed by intention to treat. This trial is registered with the ISRCTN registry, number ISRCTN47823388. Findings: 3096 participants (1556 in the intensive antiplatelet therapy group, 1540 in the guideline antiplatelet therapy group) were recruited from 106 hospitals in four countries between April 7, 2009, and March 18, 2016. The trial was stopped early on the recommendation of the data monitoring committee. The incidence and severity of recurrent stroke or TIA did not differ between intensive and guideline therapy (93 [6%] participants vs 105 [7%]; adjusted common odds ratio [cOR] 0·90, 95% CI 0·67–1·20, p=0·47). By contrast, intensive antiplatelet therapy was associated with more, and more severe, bleeding (adjusted cOR 2·54, 95% CI 2·05–3·16, p<0·0001). Interpretation: Among patients with recent cerebral ischaemia, intensive antiplatelet therapy did not reduce the incidence and severity of recurrent stroke or TIA, but did significantly increase the risk of major bleeding. Triple antiplatelet therapy should not be used in routine clinical practice