Daniel B. Montlucon

The effect of grain size and surface area on organic matter, lignin and carbohydrate concentration, and molecular compositions in Peru Margin sediments

A C-rich sediment sample from the Peru Margin was sorted into nine hydrodynamically- determined grain size fractions to explore the effect of grain size distribution and sediment surface area on organic matter content and composition. The neutral monomeric carbohydrate composition, lignin oxidation product yields, total organic carbon, and total nitrogen contents were determined independently for each size fraction, in addition to sediment surface area and abundance of biogenic opal. The percent organic carbon and percent total nitrogen were strongly related to surface area in these sediments. In turn, the distribution of surface area closely followed mass distribution among the textural size classes, suggesting hydrodynamic controls on grain size also control organic carbon content. Never- theless, organic compositional distinctions were observed between textural size classes. Total neutral carbohydrate yields in the Peru Margin sediments were found to closely parallel trends in total organic carbon, increasing in abundance among grain size fractions in proportion to sediment surface area. Coincident with the increases in absolute abundance, rhamnose and mannose increased as a fraction of the total carbohydrate yield in concert with surface area, indicating these monomers were preferentially represented in carbohydrates associated with surfaces. Lignin oxidation product yields varied with surface area when normalized to organic carbon, suggesting that the terrestrially-derived component may be diluted by sorption of marine derived material. Lignin-based parameters suggest a separate source for terrestrially derived material associated with sand-size material as opposed to that associated with silts and clays. Copyright 0 1997 Elsevier Science Ltd

Composition, age, and provenance of organic matter in NW African dust over the Atlantic Ocean

[1]xa0Eolian dust deposited on a meteorology buoy over the boreal winter and spring of 1992/1993 in the Northeast Atlantic off Northwest Africa (18°N, 22°W) afforded sufficient material for detailed assessment of its biogeochemical characteristics and provenance. The sample was subjected to microscopic examination and bulk, elemental, isotopic, black carbon, and molecular (lignin, lipid) analyses. The bulk elemental composition and organic carbon (OC) content (1.02% dry weight) establishes the dusts origin as continental upper crust and is typical of dusts that emanate from West Africa. These data are in accord with the extensive satellite imagery documenting the transit of dust clouds from the Sahara and Sahel regions (e.g., NASA TOMS aerosol index). Microscopic examination reveals that charcoal-like particles from vegetation fires (“black carbon” (BC)) are the most abundant morphologically distinct organic components. Accelerator mass spectrometry (AMS) 14C analysis yields conventional 14C ages for bulk OC of 1260 ± 40 years and BC of 2070 ± 35 years. Taken together with corresponding stable carbon isotopic compositions (δ13C, −18.9 and −15.1‰, respectively), these results suggest the presence of biomass and burning residues derived from predominantly C4 vegetation that accumulated in soils over the late Holocene. Molecular-level measurements are also consistent with this scenario. For example, lignin-derived phenols in the dustfall sample indicate a significant contribution of angiosperm grass-type tissue. The altered nature of the lignin suggests storage as residues in soils. Solvent extractable (lipid) constituents include a marked leaf wax type component with a molecular and stable carbon isotopic composition similar to those observed in surface marine sediments in this region. The hydrocarbon fraction contained some diesel-type contamination but the n-alkanes (C23–C33) retained a prominent odd/even distribution, with δ13C ranging from −26.7 to −28.5‰. The suite of even carbon numbered n-alkanols (C22–C32) is 14C dated at 647 ± 150 years, with δ13C values ranging from −23.9 to −30.4‰. The long-chain n-alkanoic acids (C22–C32) exhibited δ13C values ranging from −22.6 to −27.4‰. These waxes are evidently a mixed signal derived from contemporary C3 and C4 vegetation and from ablated soils and desiccated lake sediments of middle to late Holocene age. This molecular approach shows promise as a tool for continental paleoenvironmental assessment, particularly with respect to past vegetation cover, regional aridity, and wind systems.

Differential mobilization of terrestrial carbon pools in Eurasian Arctic river basins

Mobilization of Arctic permafrost carbon is expected to increase with warming-induced thawing. However, this effect is challenging to assess due to the diverse processes controlling the release of various organic carbon (OC) pools from heterogeneous Arctic landscapes. Here, by radiocarbon dating various terrestrial OC components in fluvially and coastally integrated estuarine sediments, we present a unique framework for deconvoluting the contrasting mobilization mechanisms of surface vs. deep (permafrost) carbon pools across the climosequence of the Eurasian Arctic. Vascular plant-derived lignin phenol 14C contents reveal significant inputs of young carbon from surface sources whose delivery is dominantly controlled by river runoff. In contrast, plant wax lipids predominantly trace ancient (permafrost) OC that is preferentially mobilized from discontinuous permafrost regions, where hydrological conduits penetrate deeper into soils and thermokarst erosion occurs more frequently. Because river runoff has significantly increased across the Eurasian Arctic in recent decades, we estimate from an isotopic mixing model that, in tandem with an increased transfer of young surface carbon, the proportion of mobilized terrestrial OC accounted for by ancient carbon has increased by 3–6% between 1985 and 2004. These findings suggest that although partly masked by surface carbon export, climate change-induced mobilization of old permafrost carbon is well underway in the Arctic.

A new look at old carbon in active margin sediments

Recent studies suggest that as much as half of the organic carbon (OC) undergoing burial in the sediments of tectonically active continental margins may be the product of fossil shale weathering. These estimates rely on the assumption that vascular plant detritus spends little time sequestered in intermediate reservoirs such as soils, freshwater sediments, and river deltas, and thus only minimally contributes to the extraneously old 14C ages of total organic matter often observed on adjacent shelves. Here we test this paradigm by measuring the Δ14C and δ13C values of individual higher plant wax fatty acids as well as the δ13C values of extractable alkanes isolated from the Eel River margin (California). The isotopic signatures of the long chain fatty acids indicate that vascular plant material has been sequestered for several thousand years before deposition. A coupled molecular isotope mass balance used to reassess the sedimentary carbon budget indicates that the fossil component is less abundant than previously estimated, with pre-aged terrestrial material instead composing a considerable proportion of all organic matter. If these findings are characteristic of other continental margins proximal to small mountainous rivers, then the importance of petrogenic OC burial in marine sediments may need to be reevaluated.

Spatial variability in the abundance, composition, and age of organic matter in surficial sediments of the East China Sea

[1]xa0Understanding the sources and fate of organic matter (OM) sequestered in continental margin sediments is of importance because the mode and efficiency of OM burial impact the carbon cycle and the regulation of atmospheric CO2 over long time scales. We carried out molecular (lignin-derived phenols from CuO oxidation), elemental, isotopic (δ13C, Δ14C), and sedimentological (grain size and mineral surface area) analyses in order to examine spatial variability in the abundance, source, age of surface sediments of the East China Sea. Higher terrigenous organic matter values were found in the main accumulating areas of fluvial sediments, including the Changjiang (Yangtze) Estuary and Zhejiang-Fujian coastal zone. Isotopic and biomarker data suggest that the sedimentary OM in the inner shelf region was dominated by aged (Δ14Cu2009=u2009−423u2009±u200942‰) but relatively lignin-rich OM (Λu2009=u20090.94u2009±u20090.57u2009mg/100u2009mg OC) associated with fine-grained sediments, suggesting important contributions from soils. In contrast, samples from the outer shelf, while of similar age (Δ14 Cu2009=u2009−450u2009±u200999‰), are lignin poor (Λu2009=u20090.25u2009±u20090.14u2009mg/100u2009mg OC) and associated with coarse-grained material. Regional variation of lignin phenols and OM ages indicates that OM content is fundamentally controlled by hydrodynamic sorting (especially, sediment redistribution and winnowing) and in situ primary production. Selective sorption of acid to aldehyde in clay fraction also modified the ratios of lignin phenols. The burial of lignin in East China Sea is estimated to be relatively efficient, possibly as a consequence of terrigenous OM recalcitrance and/or relatively high sedimentation rates in the Changjiang Estuary and the adjacent Zhejing-Fujian mud belt.

Multimolecular tracers of terrestrial carbon transfer across the pan‐Arctic: 14C characteristics of sedimentary carbon components and their environmental controls

Distinguishing the sources, ages, and fate of various terrestrial organic carbon (OC) pools mobilized from heterogeneous Arctic landscapes is key to assessing climatic impacts on the fluvial release of carbon from permafrost. Through molecular 14C measurements, including novel analyses of suberin- and/or cutin-derived diacids (DAs) and hydroxy fatty acids (FAs), we compared the radiocarbon characteristics of a comprehensive suite of terrestrial markers (including plant wax lipids, cutin, suberin, lignin, and hydroxy phenols) in the sedimentary particles from nine major arctic and subarctic rivers in order to establish a benchmark assessment of the mobilization patterns of terrestrial OC pools across the pan-Arctic. Terrestrial lipids, including suberin-derived longer-chain DAs (C24,26,28), plant wax FAs (C24,26,28), and n-alkanes (C27,29,31), incorporated significant inputs of aged carbon, presumably from deeper soil horizons. Mobilization and translocation of these old terrestrial carbon components was dependent on nonlinear processes associated with permafrost distributions. By contrast, shorter-chain (C16,18) DAs and lignin phenols (as well as hydroxy phenols in rivers outside eastern Eurasian Arctic) were much more enriched in 14C, suggesting incorporation of relatively young carbon supplied by runoff processes from recent vegetation debris and surface layers. Furthermore, the radiocarbon content of terrestrial markers is heavily influenced by specific OC sources and degradation status. Overall, multitracer molecular 14C analysis sheds new light on the mobilization of terrestrial OC from arctic watersheds. Our findings of distinct ages for various terrestrial carbon components may aid in elucidating fate of different terrestrial OC pools in the face of increasing arctic permafrost thaw.

RADIOCARBON DATING OF ALKENONES FROM MARINE SEDIMENTS: I. ISOLATION PROTOCOL

The chemical and isotopic compositions of long-chain (C36C39) unsaturated ketones (alkenones), a uniquennclass of algal lipids, encode surface ocean properties useful for paleoceanographic reconstruction. Recently, we have soughtnnto extend the utility of alkenones as oceanic tracers through measurement of their radiocarbon contents. Here, we describe annmethod for isolation of alkenones from sediments as a compound class based on a sequence of wet chemical techniques. Thennsteps involved, which include silica gel column chromatography, urea adduction, and silver nitrate-silica gel column chromatography,nnexploit various structural attributes of the alkenones. Amounts of purified alkenones estimated by GC/FID measurementsnnwere highly correlated with CO2 yields after sample combustion, indicating purities of greater than 90% fornnsamples containing =100 g C. The degree of alkenone unsaturation ( ) also varied minimally through the procedure. Wennalso describe a high-performance liquid chromatography (HPLC) method to isolate individual alkenones for molecular-levelnnstructural and isotopic determination.

RADIOCARBON DATING OF ALKENONES FROM MARINE SEDIMENTS: II. ASSESSMENT OF CARBON PROCESS BLANKS

We evaluate potential process blanks associated with radiocarbon measurement of microgram to milligram quantities of alkenones at the National Ocean Sciences Accelerator Mass Spectrometry (NOSAMS) facility. Two strategies to constrain the contribution of blanks to alkenone 14C dates were followed: 1) dating of samples of known age and 2) multiple measurements of identical samples. We show that the potential contamination associated with the procedure does not lead to a systematic bias of the results of alkenone dating to either younger or older ages. Our results indicate that alkenones record ∆14C of ambient DIC with an accuracy of approximately 10‰. A conservative estimate of measurement precision is 17‰ for modern samples. Alkenone 14C ages are expected to be reliable within 500 yr for samples younger than 10,500 14C yr.

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

[1]xa0Semi-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.

Arctic Deltaic Lake Sediments As Recorders of Fluvial Organic Matter Deposition

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, uf06413C, uf04414C) 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 behaviour of arctic rivers, as well as how they respond to a changing climate.