Search

Hydrodynamic sorting has been shown to strongly influence the composition and age of organic carbon (OC) during sediment transport and burial in the marine environment, yet sorting effects on terrestrial OC (OCterr) in fluvial systems remain poorly understood. We conducted size fractionation of suspended particle samples from the lower Yellow River, China, and examined variations in mass distribution and carbon isotopic (δ13C and Δ14C) composition of bulk OC and specific biomarkers among grain size fractions in order to investigate the influence of hydrodynamic sorting and selective transport on organic matter export. In general, the 16–32 μm and 32–63 μm fractions contributed the most of sediment mass while the majority of the OC resided in the 16–32 μm fraction. Over 80% of OC and n-fatty acids (FAs) were concentrated in 32 μm), characterized by relatively low SA, OC%, and Δ14COC values, but higher Δ14C values of C26+28+30 FAs, are inferred to reflect a combination of bedrock-derived detrital sediment and fresh vascular-plant material (e.g., plant fragments). In contrast, finer particles (

Relatively little is known about the amount of time that lapses between the photosynthetic fixation of carbon by vascular land plants and its incorporation into the marine sedimentary record, yet the dynamics of terrestrial carbon sequestration have important implications for the carbon cycle. Vascular plant carbon may encounter multiple potential intermediate storage pools and transport trajectories, and the age of vascular plant carbon accumulating in marine sediments will reflect these different pre-depositional histories. Here, we examine down-core 14C profiles of higher plant leaf wax-derived fatty acids isolated from high fidelity sedimentary sequences spanning the so-called “bomb-spike” and encompassing a ca. 60-degree latitudinal gradient from tropical (Cariaco Basin), temperate (Saanich Inlet), and polar (Mackenzie Delta) watersheds to constrain integrated vascular plant carbon storage/transport times (“residence times”). Using a modeling framework, we find that, in addition to a “young” (conditionally defined as < 50 y) carbon pool, an old pool of compounds comprises 49 to 78 % of the fractional contribution of organic carbon (OC) and exhibits variable ages reflective of the environmental setting. For the Mackenzie Delta sediments, we find a mean age of the old pool of 28 ky (±9.4, standard deviation), indicating extensive pre-aging in permafrost soils, whereas the old pools in Saanich Inlet and Cariaco Basin sediments are younger, 7.9 (±5.0) and 2.4 (±0.50) to 3.2 (±0.54) ky, respectively, indicating less protracted storage in terrestrial reservoirs. The “young” pool showed clear annual contributions for Saanich Inlet and Mackenzie Delta sediments (comprising 24% and 16% of this pool, respectively), likely reflecting episodic transport of OC from steep hillside slopes surrounding Saanich Inlet and annual spring flood deposition in the Mackenzie Delta, respectively. Contributions of 5–10 year old OC to the Cariaco Basin show a short delay of OC inflow, potentially related to transport time to the offshore basin. Modeling results also indicate that the Mackenzie Delta has an influx of young but decadal material (20–30 years of age), pointing to the presence of an intermediate reservoir. Overall, these results show that a significant fraction of vascular plant C undergoes pre-aging in terrestrial reservoirs prior to accumulation in deltaic and marine sediments. The age distribution, reflecting both storage and transport times, likely depends on landscape-specific factors such as local topography, hydrographic characteristics, and mean annual temperature of the catchment, all of which affect the degree of soil buildup and preservation. We show that catchment-specific carbon residence times across landscapes can vary by an order of magnitude, with important implications both for carbon cycle studies and for the interpretation of molecular terrestrial paleoclimate records preserved in sedimentary sequences.

Precisely-dated stalagmites are increasingly important archives for the reconstruction of terrestrial paleoclimate at very high temporal resolution. In-depth understanding of local conditions at the cave site and of the processes driving stalagmite deposition is of paramount importance for interpreting proxy signals incorporated in stalagmite carbonate. Here we present a sub-decadally resolved dead carbon fraction (DCF) record for a stalagmite from Yok Balum Cave (southern Belize). The record is coupled to parallel stable carbon isotope (delta C-13) and U/Ca measurements, as well as radiocarbon (C-14) measurements from soils overlying the cave system. Using a karst carbon cycle model we disentangle the importance of soil and karst processes on stalagmite DCF incorporation, revealing a dominant host rock dissolution control on total DCF. Covariation between DCF, delta C-13, and U/Ca indicates that karst processes are a common driver of all three parameters, suggesting possible use of delta C-13 and trace element ratios to independently quantify DCF variability. A statistically significant multi-decadal lag of variable length exists between DCF and reconstructed solar activity, suggesting that solar activity influenced regional precipitation in Mesoamerica over the past 1500 years, but that the relationship was non-static. Although the precise nature of the observed lag is unclear, solar-induced changes in North Atlantic oceanic and atmospheric dynamics may play a role. (C) 2016 Elsevier Ltd. All rights reserved.

Marginal seas are estimated to account for up to 90% of organic carbon (OC) burial in marine sediments, and thus play an important role in global carbon cycle. However, comprehensive assessments of carbon budgets for marginal sea systems are challenging due to their inherent complexity, with spatial and temporal variability in carbon inputs and dispersal processes. We examine the Bohai Sea and Yellow Sea (BS–YS) in order to further our understanding of sedimentary OC delivery, translocation and accumulation in a shallow marginal sea system. Bulk properties and the content and isotopic compositions (Δ14C, δ13C) of source-specific plant wax n-alkyl lipid biomarkers were determined for a suite of surficial sediment samples. Variable δ13C values (−25.1‰ to −28.5‰) and contemporary radiocarbon ages of short-chain n-fatty acids (FAs; C16, C18) reflect modern autochthonous marine and/or fresh terrestrial plant input. In contrast, extremely depleted Δ14C values (−932‰ to −979‰) of short-chain n-alkanes (C16, C18) suggest a predominant input from sedimentary rocks (petrogenic OC) or petroleum. Abundance-weighted average δ13C and Δ14C values of long-chain leaf wax lipids (C26+28+30 n-FAs, C24+26+28 n-alkanols, C27+29+31 n-alkanes) are −29.1 ± 1.1‰ to −30.2 ± 0.3‰, and −286 ± 150‰ to −442 ± 119‰, respectively, illustrating that terrestrial OC delivery is dominated by pre-aged (∼3000–5000 14C yrs) C3 vegetation sources. A coupled carbon-isotopic mixing model, based on the bulk and compound-specific biomarker δ13C and Δ14C values, is used to partition the BS–YS sedimentary OC into three components that reflect both origins and transport processes. For all sampling sites, 31–64% is modern/contemporary OC, 24–49% is pre-aged terrestrial OC, and 7–26% is fossil OC, the latter likely derived from both physical erosion of ancient sedimentary rocks and fossil fuel sources. Pre-aged soil OC is most prominent in front of the modern and old Huanghe (Yellow River) delta (48% and 49%), and fossil OC is most significant north of the old Huanghe mouth (26%). Significant pre-aged soil contributions (33%) are also evident for sites further offshore, where transport and deposition of eolian dust supply may be important. For the three major deposition areas of the BS–YS system (Bohai Basin, sub-aqueous Huanghe delta and central south YS basin), we estimate that about 3.02 Mt/yr of refractory, plant-derived pre-aged soil OC and 0.98 Mt/yr of 14C-depleted fossil OC accumulates in surface sediments, corresponding to 35% and 11% of sediment TOC, respectively. Compared with estimates for fluxes from corresponding sources, the burial efficiency is close to 100% for pre-aged soil OC and 70% for fossil OC, implying efficient OC burial in delta and shelf environments. Re-burial of these two pools of terrigenous OC only affects carbon cycling on millennial and longer timescales respectively, and exerts little influence on the modern carbon cycle (

The Fraser River basin in southwestern Canada bears unique geologic and climatic features which make it an ideal setting for investigating the origins, transformations and delivery to the coast of dissolved riverine loads under relatively pristine conditions. We present results from sampling campaigns over three years which demonstrate the lithologic and hydrologic controls on fluxes and isotope compositions of major dissolved inorganic runoff constituents (dissolved nutrients, major and trace elements, 87 Sr/ 86 Sr, δD). A time series record near the Fraser mouth allows us to generate new estimates of discharge-weighted concentrations and fluxes, and an overall chemical weathering rate of 32 t km −2 y −1 . The seasonal variations in dissolved inorganic species are driven by changes in hydrology, which vary in timing across the basin. The time series record of dissolved 87 Sr/ 86 Sr is of particular interest, as a consistent shift between higher (“more radiogenic”) values during spring and summer and less radiogenic values in fall and winter demonstrates the seasonal variability in source contributions throughout the basin. This seasonal shift is also quite large (0.709–0.714), with a discharge-weighted annual average of 0.7120 (2 s.d. = 0.0003). We present a mixing model which predicts the seasonal evolution of dissolved 87 Sr/ 86 Sr based on tributary compositions and water discharge. This model highlights the importance of chemical weathering fluxes from the old sedimentary bedrock of headwater drainage regions, despite their relatively small contribution to the total water flux.

Large river systems accumulate, process, and transport huge quantities of organic matter (OM) from their catchments, part of which is exported to the ocean. Although this suite of processes comprises an important component of the global carbon cycle, integrated studies examining the nature and extent of OM processing on a basin-wide scale remain rare. Here, we provide an overview of provenance and composition of OM in suspended and deposited sediments within the Pearl River watershed in South China. We present new data on the organic carbon (OC) and total nitrogen (TN) contents, stable carbon and radiocarbon isotopic compositions of OC (δ 13 C and F m ), as well as grain size distribution and mineral-specific surface area of Pearl River sediments. These results are combined with published data on suspended particulate matter (SPM) and soil profiles in the Pearl River watershed in order to determine the provenance and transformation of OM in this large subtropical fluvial system. We find that the low 14 C contents, expressed as fraction modern (F m ) values, in suspended (F m : 0.58–0.87) and sedimentary OM (F m : 0.38–0.82) are attributed to contributions from 14 C-depleted soils, bedrock, as well as riverine primary productivity (R pp ) that utilizes 14 C-depleted sources of dissolved inorganic carbon (DIC). For SPM, soil OM (F m : 0.87±0.13) is inferred to be the dominant fraction during the wet season, whereas the contributions of R pp (F m : 0.86±0.04) and petrogenic OC (devoid of 14 C) are enhanced during the dry season. This manifests itself in differences in OC soil , OC Rpp , and OC petro contributions in SPM between wet and dry seasons (1.05±0.18 vs. 1.20±0.50%, 0.16±0.03 vs. 0.32±0.15% and 0.21±0.07 vs. 0.38±0.19%). During erosion and transport, the most labile OM in the top soil is rapidly degraded, as indicated by a stronger contribution from soil CO 2 into riverine DIC during the wet season and flood event (39±1% and 45±3%) compared to the dry season (31±2%). River sediments are primarily accumulated during the wet season when suspended sediment fluxes are high. Refractory deep soil OM (F m : 0.74±0.07) dominate in these sediments, whereas moderately labile soil OM components are further degraded during settling and storage. This sedimentary OM is predominantly composed of aged soil (92±4%), with a minor contribution from bedrock (7±4%) and negligible input from R pp (0.2±0%). The longitudinal changes in the composition of suspended and sedimentary OM are mainly controlled by input of R pp and ongoing degradation processes in the river system. The riverine particulate OC flux to the Pearl River estuary and ocean thus contains a mixture of soil, petrogenic and R pp OM, all exhibiting relatively low F m values. The riverine OM transformation and dynamics are important for the short-term carbon cycle, whereas the remaining signature and fate of the extensively processed, refractory OM has implications for the long-term carbon cycle.

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 Δ14C values (−204‰ to +2‰), suggesting varied inputs and/or continental storage and transport histories. In contrast, lignin phenols exhibited similar δ13C values (between −30‰ and −34‰) and a relatively narrow range of Δ14C values (−45‰ to −150‰; HPLC-based measurement) 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.

Northern, high latitude soils have stored vast amounts of organic carbon (OC) in permafrost and peats for many millennia, however, climate change may mobilize and release this particulate OC (POC) to arctic rivers. Deltaic and floodplain lakes that receive fluvial sediments, primarily during the spring freshet, may provide records of such changes in riverine POC. Here, we examine properties of OC in a sediment core from a lake in the lower floodplain of the Ob’ River, west Siberia, to determine how the properties of OC deposited in this lake varied over many decades and to evaluate use of this sedimentary OC as a recorder of riverine POC load and properties. The core predates the most recent, dramatic changes in arctic climate and hence may serve as a benchmark against which to contrast future variations in fluvial POC discharge. Elemental, stable carbon and radiocarbon isotopic analyses, along with nuclear magnetic resonance (NMR) spectroscopy and molecular-level information (lignin phenol composition), indicate two major sources of OC to most of the sediments in this lake: plant-derived OC and algal-derived OC. However, a mixing model indicates that the nature and 14 C content of these two sources change with depth in the sediment, resulting in three distinct layers: surface horizons, a “high-OC” layer and “mixing” horizons found above and below the high-OC layer. The plant-derived component is significantly aged throughout the core ( 14 C ages of 1300–3900 years) and appears to derive from primarily local, tundra sources, whereas the algal component is modern. Our analysis suggests that the usual mode of OC deposition, as exemplified by the “mixing” and surface horizons, involved mixing of varying amounts of new algal production (35–65%) with aged permafrost- or peat-derived OC. This deposition was interrupted by an event, such as the collapse of a riverbank, which laid down the compositionally distinct “high-OC” layer in which plant-derived OC mixes with aged mineral-soil-derived OC without clear input from algae. The relative amounts of the plant and algal components in the lake sediments appear to be controlled primarily by local hydrological conditions rather than by river-wide processes, suggesting that comparison of sediment records from multiple lakes within a floodplain will be important to assess changes in POC export by arctic rivers. However, the flux and nature of the higher plant-derived OC may carry important information on the sources and dynamics of OC stored within the drainage basin.

Long-term carbon cycling and climate change are strongly dependent on organic carbon (OC) burial in marine sediments. Radiocarbon ( 14 C) has been widely used to constrain the sources, sinks, and processing of sedimentary OC. To elucidate the dominant controls on the radiocarbon content of total organic carbon ( 14 C TOC ) accumulating in surface sediments we construct a box model that predicts 14 C TOC in the sediment mixed layer (measured as fraction modern, Fm). Our model defines three distinct OC pools (“degradable,” “semi-labile,” and “refractory”) and assumes that 14 C TOC flux to sediments is exclusively derived from surface ocean primary productivity, and hence follows a “generic” surface ocean dissolved inorganic carbon (DIC) bomb curve. Model predictions are compared to a set of 75 surface sediment samples, which span a wide geographic range and reflect diverse water column and depositional conditions, and for which sedimentation rate and mixed-layer depth are well characterized. Our model overestimates the Fm value for a majority (65%) of these sites, especially at shallow water depths and for sites characterized by depleted δ 13 C TOC values. The model is most sensitive to sedimentation rate and mixed-layer depth. Therefore, slight changes to these parameters can lead to a match between modeled and measured Fm values at many sites. Yet, in some cases, we find that measured Fm values cannot be simulated without large and unrealistic changes to sedimentation rate and mixed-layer depth. These results point to sources of pre-aged OC to surface sediments and implicate soil-derived terrestrial OC, reworked marine OC, and/or anthropogenic carbon as important components of the organic matter present in surface sediments. This approach provides a valuable framework within which to explore controls on sedimentary organic matter composition and carbon burial over a range of spatial and temporal scales.

Understanding the supply and preservation of glycerol dibiphytanyl glycerol tetraethers (GDGTs) in marine sediments helps inform their use in paleoceanography. Compound-specific radiocarbon measurements of sedimentary alkenones from multiple environments have been used to gain insight into processes that affect U 37 K ′ paleotemperature reconstructions. Similar analyses are warranted to investigate how analogous processes affecting GDGTs impact TEX 86 paleotemperatures. Here we present radiocarbon measurements on individual GDGTs from Bermuda Rise and Santa Monica Basin sediments and discuss the results in the context of previous studies of co-depositional alkenones and foraminifera. The 14 C contents of GDGTs and planktonic foraminifera in Bermuda Rise are very similar, suggesting a local source; and TEX 86 -derived temperatures agree more closely with foraminiferal temperatures than do U 37 K ′ temperatures. In contrast, GDGTs in Santa Monica Basin are depleted in 14 C relative to both alkenones and foraminifera, and TEX 86 temperatures agree poorly with known surface water values. We propose three possible factors that could explain these results: (i) GDGTs may be labile relative to alkenones during advective transport through oxic waters; (ii) archaeal production deep in the water column may contribute 14 C-depleted GDGTs to sediments; and (iii) some GDGTs also may derive from sedimentary archaeal communities. Each of these three processes is likely to occur with varying relative importance depending on geographic location. The latter two may help to explain why TEX 86 temperature reconstructions from Santa Monica Basin do not appear to reflect actual sea surface temperatures. Terrigenous GDGTs are unlikely to be major contributors to Bermuda Rise or Santa Monica Basin sediments, based on values of the BIT index. The results also indicate that the crenarchaeol regioisomer is governed by processes different from other GDGTs. Individual measurements of the crenarchaeol regioisomer are significantly depleted in 14 C relative to co-occurring GDGTs, indicating an alternative origin for this compound that presently remains unknown. Re-examination of the contribution of crenarchaeol regioisomer to the TEX 86 index shows that it is a significant influence on the sensitivity of temperature reconstructions.

Radiocarbon analyses of bulk carbon and individual organic compounds are presented for the hydrothermal environment of the Rebecca’s Roost vent in the southern trough of the Guaymas Basin hydrothermal field. The Δ 14 C values of CO 2 and CH 4 in the hottest hydrothermal fluids (317°C) are nearly “radiocarbon dead” (−944‰ and −923‰, respectively). In contrast, the Δ 14 C values of sediments and individual fatty acids (−418‰ to −227‰) obtained from a bacterial mat located south of the vent site are similar to values previously reported for hydrothermal petroleum in this environment and are more depleted in 14 C than overlying waters. Hydrothermal fluids moving through the sediments appear to supply 14 C of intermediate age to the bacteria. This carbon may take the form of, or may be supplied by processes similar to, the generation of hydrothermal petroleum. Although the bacterial mat visibly was dominated by Beggiatoa spp., such mats are known to include numerous other species. Individual compound data show that preaged carbon is being consumed by the integrated bacterial assemblage. Values of δ 13 C and Δ 14 C indicate that petroleum-derived carbon is incorporated directly into fresh bacterial biomass. Subsequently, some of this newly synthesized material also is consumed by heterotrophs, as eukaryotic sterols from the same sample also have 14 C-depleted values (Δ 14 C = −136‰ to −110‰). Therefore, the entire system may operate as a complex consortium to transform relict carbon back into biomass. Bacterial consumption of relict carbon occurs despite the ample supply of fresh carbon delivered from the productive, overlying water column.

Author Posting. © The Authors, 2005. 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 Geochimica et Cosmochimica Acta 69 (2005): 2547-2558, doi:10.1016/j.gca.2005.01.001.

A high-resolution record of Pb deposition in Rhode Island over the past 250 yr was constructed using a sediment core from the anoxic Pettaquamscutt River basin. The sedimentary Pb concentration record shows the well-described maximum associated with leaded gasoline usage in the United States. Diminished Pb variability during recorded periods of local industrial activity (1735 to 1847) supports the greater importance of regional atmospheric lead transport vs. local inputs. The Pb isotopic composition at this site shows a clear maximum in anthropogenic 206 Pb/ 207 Pb in the mid-1800s. Similar peaks have also been observed in sediments from Chesapeake Bay and the Great Lakes, suggesting a common source. Possible causes for this event include mining and smelting of Pb ores in the Upper Mississippi Valley district, which accounted for almost all Pb production in the United States in that period. The timing of this event can provide an important stratigraphic marker for sediments deposited in the past 200 yr in the Northeastern United States. The downcore profile of anthropogenic 206 Pb/ 207 Pb provides a classic example of how changes in the mixture of ores for production of tetraethyl lead caused a regional-scale shift in the sedimentary record, and suggests that coal could have played a secondary role in Pb emissions after 1920. Copyright © 2005 Elsevier Ltd

Cesium-137 derived from the explosion of the Chernobyl reactor in 1986 was preserved in anoxic sediments from a coastal environment in southern Rhode Island. Although the radioactive plume was detected in surface air samples at several locations in the United States, this is the first known record of a Chernobyl 137 Cs peak in sediments from North America. The inventory of Chernobyl 137 Cs that was preserved in the Pettaquamscutt River is small compared to European counterparts and should only be detectable for the next 15–20 yr. However, the presence of two 137 Cs peaks (1963 and 1987) identifies a well-dated segment of the sediment column that could be exploited in understanding the decomposition and preservation of terrestrial and aquatic organic matter. Different methods for calculating the 210 Pb chronology were also evaluated in this study and checked against independent varve counting. The end result is a detailed chronology of a site well suited for reconstruction of historical records of environmental change.

Radiocarbon stratigraphy is an essential tool for high resolution paleoceanographic studies. Age models based on radiocarbon ages of foraminifera are commonly applied to a wide range of geochemical studies, including the investigation of temporal leads and lags. The critical assumption is that temporal coupling between foraminifera and other sediment constituents, including specific molecular organic compounds (biomarkers) of marine phytoplankton, e.g. alkenones, is maintained in the sediments. To test this critical assumption in the Benguela upwelling area, we have determined radiocarbon ages of total C37-C39 alkenones in 20 samples from two gravity cores and three multicorer cores. The cores were retrieved from the continental shelf and slope off Namibia, and samples were taken from Holocene, deglacial and Last Glacial Maximum core sections. The alkenone radiocarbon ages were compared to those of planktic foraminifera, total organic carbon, fatty acids and fine grained carbonates from the same samples. Interestingly, the ages of alkenones were 1000 to 4500 yr older than those of foraminifera in all samples. Such age differences may be the result of different processes: Bioturbation associated with grain size effects, lateral advection of (recycled) material and redeposition of sediment on upper continental slopes due to currents or tidal movement are examples for such processes. Based on the results of this study, the age offsets between foraminifera and alkenones in sediments from the upper continental slope off Namibia most probably do not result from particle-selective bioturbation processes. Resuspension of organic particles in response to tidal movement of bottom waters with velocities up to 25 cm/s recorded near the core sites is the more likely explanation. Our results imply that age control established using radiocarbon measurements of foraminifera may be inadequate for the interpretation of alkenone-based proxy data. Observed temporal leads and lags between foraminifera based data and data derived from alkenone measurements may therefore be secondary signals, i.e. the result of processes associated with particle settling and biological activity.

Compound-specific Δ 14 C values are reported for 31 different lipid biomarker molecules obtained from Santa Monica Basin and Santa Barbara Basin surface sediments. These organic compounds represent phytoplanktonic, zooplanktonic, bacterial, archaeal, terrestrial higher plant, and fossil carbon sources. The lipid classes include the following: long-chain n -alkanes, fatty acids (as methyl esters; FAMEs), n -alcohols, C 30 midchain ketols and diols, sterols, hopanols, and C 40 isoprenoid side chains from the ether-linked glycerols of Archaea . The data show that the carbon source for the majority of the biomarkers is marine euphotic zone primary production or subsequent heterotrophic consumption of this biomass. A small amount of benthic incorporation of 14 C-depleted dissolved inorganic carbon was identified for the bacterial hopanols and C 15 linear and branched-chain fatty acids. However, there is no apparent uptake of 14 C-depleted dissolved inorganic carbon in Santa Monica Basin by the bacteria, including filamentous Beggiatoa spp., that produce C 18:1ω7 fatty acid. Two of the lipid classes did not reflect carbon originally fixed by marine photoautotrophs. These were the n -alkanes, for which the Δ 14 C data are consistent with mixed fossil carbon and contemporary terrestrial higher plant sources, and the archaeal isoprenoids, for which the Δ 14 C data are consistent with chemoautotrophic growth below the euphotic zone.

Solid state 13C nuclear magnetic resonance (NMR) spectroscopy is used to examine kerogen composition in weathering profiles of the Monterey, Green River, Woodford, and New Albany formations. Techniques include cross polarization (CP) and Bloch decay (BD) spectral acquisition, dipolar dephasing (DD), spin counting, experiments to provide estimates of relaxation times (T1ρH and T1H), and proton spin relaxation editing (PSRE). It is demonstrated that CP/MAS (cross polarization/magic angle spinning) spectra obtained on isolated kerogens provide reliable characterization of kerogen composition (compared with BD spectra and whole-rock samples). Highly aliphatic (polymethylenic) kerogens are not appreciably altered during weathering. Aromatic and/or branched aliphatic kerogens accumulate oxidation products and preferentially lose aliphatic relative to aromatic carbon during weathering. No relation is observed between T1ρH times and either kerogen composition or degree of weathering; T1H times correlate with aromaticity. Two distinct components within kerogens are discerned by PSRE: one highly aliphatic (largely polymethylenic) component and one mixed aliphatic/aromatic component. During weathering, the highly aliphatic component remains largely unaltered, while the mixed component loses aliphatic carbon and accumulates carbonyl oxidation products. Thus it appears that kerogen weathering is dominated by two separate processes: Linear alkyl fragments are cleaved without oxidation, and aromatic/branched alkyl fragments are oxidized while attached to the kerogen macromolecule and then cleaved.

Hydrogen isotope ratios (D/H) of lipid biomarkers extracted from aquatic sediments were measured to determine whether they can be used as a proxy for D/H of environmental water. Values of δD were determined by using a recently developed isotope-ratio-monitoring gas chromatograph-mass spectrometer system (irmGCMS) and were confirmed by conventional hydrogen isotopic measurements (i.e., combustion followed by reduction) on individual compounds isolated by preparative capillary gas chromatography. Diverse lipids (alkanes, n-alkanols, sterols, and pentacyclic triterpenols) were analyzed to examine hydrogenisotopic controls on lipids of varying origin and biosynthetic pathway. For algal sterols (24-methylcholest- 3β-ol, 24-ethylcholest-5,22-dien-3β-ol, and 4,23,24-trimethylcholesterol, or dinosterol), the fractionation between sedimentary lipids and environmental water was -201 ± 10‰ and was similar in both marine and freshwater sites. In a sediment from a small lake in a forested catchment, triterpenols from terrestrial sources were enriched in D by 30‰ relative to algal sterols. Apparent fractionation factors for n-alkyl lipids were smaller than those of triterpenols and were more variable, probably reflecting multiple sources for these compounds. We conclude that hydrogen-isotopic analyses of algal sterols provide a viable means of reconstructing D/H of environmental waters. Results are less ambiguous than reconstructions based on analyses of kerogen or other operationally defined organic matter fractions.

Organic matter in surface sediments from two onshore-offshore transects in the northwestern Gulf of Mexico was characterized by a variety of techniques, including elemental, stable carbon, radiocarbon, and molecular-level analyses. In spite of the importance of the Mississippi River as a sediment source, there is little evidence for a significant terrigenous input based on the low carbon:nitrogen ratios (8 -5) and the enriched d 13 C values of bulk sedimentary organic carbon (219.7‰ to 221.7‰). Radiocarbon analyses, on the other hand, yield depleted D 14 C values (2277‰ to 2572‰) which indicate that a significant fraction of the sedimentary organic carbon (OC) in all these surface sediments must be relatively old and most likely of allochthonous origin. CuO oxidations yield relatively low quantities of lignin products (0.4 -1.4 mg/100 mg OC) along with compounds derived from proteins, polysaccharides, and lipids. Syringyl:vanillyl and cin- namyl:vanillyl ratios (averaging 1.6 and 0.5, respectively) and acid:aldehyde ratios for both vanillyl and syringyl phenols (averaging 0.8 and 1.2, respectively) indicate that the lignin present in sediments originates from nonwoody angiosperm sources and is highly degraded. The d 13 C values of lignin phenols in shelf sediments are relatively depleted in 13 C (averaging 226.3‰) but are increasingly enriched in 13 C at the slope sites (averaging 217.5‰ for the two deepest stations). We interpret these molecular and isotopic compositions to indicate that a significant fraction ($50%) of the lignin and, by inference, the land-derived organic carbon in northwestern Gulf of Mexico sediments ultimately originated from C4 plants. The source of this material is likely to be soil organic matter eroded from the extensive grasslands of the Mississippi River drainage basin. Notably, the mixed C4 and C3 source and the highly degraded state of this material hampers its recognition and quantification in shelf and slope sediments. Our data are consistent with higher than previously estimated inputs of land-derived organic carbon to regions of the ocean, such as the Gulf of Mexico, with significant sources of terrigenous C4-derived organic matter. Copyright © 1998 Elsevier Science Ltd

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. Nevertheless, 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.

Neodymium isotopes are becoming widely used as a palaeoceanographic tool for reconstructing the source and flow direction of water masses. A new method using planktonic foraminifera which have not been chemically cleaned has proven to be a promising means of avoiding contamination of the deep ocean palaeoceanographic signal by detrital material. However, the exact mechanism by which the Nd isotope signal from bottom waters becomes associated with planktonic foraminifera, the spatial distribution of rare earth element (REE) concentrations within the shell, and the possible mobility of REE ions during changing redox conditions, have not been fully investigated. Here we present REE concentration and Nd isotope data from mixed species of planktonic foraminifera taken from plankton tows, sediment traps and a sediment core from the NW Atlantic. We used multiple geochemical techniques to evaluate how, where and when REEs become associated with planktonic foraminifera as they settle through the water column, reside at the surface and are buried in the sediment. Analyses of foraminifera shells from plankton tows and sediment traps between 200 and 2938 m water depth indicate that only ∼20% of their associated Nd is biogenically incorporated into the calcite structure. The remaining 80% is associated with authigenic metal oxides and organic matter, which form in the water column, and remain extraneous to the carbonate structure. Remineralisation of these organic and authigenic phases releases ions back into solution and creates new binding sites, allowing the Nd isotope ratio to undergo partial equilibration with the ambient seawater, as the foraminifera fall through the water column. Analyses of fossil foraminifera shells from sediment cores show that their REE concentrations increase by up to 10-fold at the sediment–water interface, and acquire an isotopic signature of bottom water. Adsorption and complexation of REE3+ ions between the inner layers of calcite contributes significantly to elevated REE concentrations in foraminifera. The most likely source of REE ions at this stage of enrichment is from bottom waters and from the remineralisation of oxide phases which are in chemical equilibrium with the bottom waters. As planktonic foraminifera are buried below the sediment–water interface redox-sensitive ion concentrations are adjusted within the shells depending on the pore-water oxygen concentration. The concentration of ions which are passively redox sensitive, such as REE3+ ions, is also controlled to some extent by this process. We infer that (a) the Nd isotope signature of bottom water is preserved in planktonic foraminifera and (b) that it relies on the limited mobility of particle reactive REE3+ ions, aided in some environments by micron-scale precipitation of MnCO3. This study indicates that there may be sedimentary environments under which the bottom water Nd isotope signature is not preserved by planktonic foraminifera. Tests to validate other core sites must be carried out before downcore records can be used to interpret palaeoceanographic changes.

X-ray absorption near-edge structure spectroscopy (XANES) used to measure sulfur speciation in a variety of organic-rich marine sediments has established sulfonates as a novel and major component of sedimentary organic sulfur. The origins of sulfonates in sediments are not clear, although both biological and geochemical mechanisms are possible. The accumulation of oxidized sulfonate sulfur in reducing marine sediments was not known previously; hence, a new perspective in sulfur geochemistry is established. The biogeochemical implications of the presence of sulfonates in marine sediments are discussed.

C1-C6 alkylated pyrroles were identified as major constituents of the flash pyrolysate of a kerogen from the Miocene Monterey Formation (California, USA) using gas chromatography with an N-selective detector and gas chromatography-mass spectrometry. The major alkylpyrroles identified are 2,3,4-trimethylpyrrole; 3-ethyl-4-methylpyrrole; 2,3-dimethyl-4-ethylpyrrole; 2,4-dimethyl-3-ethylpyrrole; and 3-ethyl-2,4,5-trimethylpyrrole. The alkyl substitution patterns of the alkylpyrroles strongly suggest an origin from tetrapyrrole pigments. Evidence for this hypothesis was provided by flash pyrolysis of the tetrapyrrole pigments chlorophyll-a, protoporphyrin-IX dimethyl ester, and bilirubin, which yielded alkylpyrroles with a similar isomer distribution. Quantitative pyrolysis using a polymer internal standard of both the kerogen and the tetrapyrrole pigments revealed that ca. 5% of the kerogen consists of macromolecularly bound tetrapyrrole pigments or that this fraction contains ca. 5% insoluble tetrapyrrole salts. These results show that in specific cases tetrapyrrole pigments can contribute significantly to the sedimentary organic matter.

This study describes the analysis of sulphur-containing products from Curie-point pyrolysis (Py) of eighty-five samples (kerogens, bitumen, and petroleum asphaltenes and coals) using gas chromatography (GC) in combination with sulphur-selective detection. Peak areas of approximately forty individual organic sulphur pyrolysis products (OSPP) were measured, and the results analysed with the aid of multivariate data reduction techniques (principal components analysis, (PCA)). The structural relationships proposed in an earlier publication ( Sinninghe Damste et al., 1989a) in which OSPP can be grouped according to common “carbon skeletons” are supported by PCA. The distribution of OSPP varies both as a function of kerogen type (as defined by elemental composition) and maturity, reflecting differences in the relative abundance of the various carbon skeleton types. Sulphur-containing products from Type I, Type II, and, to some extent, Type II-S kerogens are dominated by OSPP derived from “moieties” (i.e., discrete structural components within the macromolecule) possessing linear carbon skeletons, while coals and Type III kerogens give rise to higher relative abundances of OSPP with branched carbon skeletons. Type I kerogens are distinguished from Type II kerogens due to the type of linear carbon skeleton, the former yielding higher relative amounts of 2-n-alkylthiophenes and thiolanes and the latter 2,5-di-substituted sulphur-containing products. Products from sulphur-rich (Type II-S) kerogens differ by higher relative abundances of OSPP derived from precursors with isoprenoid and/or steroidal side-chain carbon skeletons, and by higher absolute abundances of all OSPP. Petroleum and, to a lesser extent, bitumen asphaltenes give rise to OSPP with longer carbon skeletons than do kerogens or coals. This observation supports the models proposed by Sinninghe Damste et al. (1990a) in which sulphur-containing moieties in asphaltenes are bound by fewer intermolecular bridges (i.e., are less extensively cross-linked) and, consequently, more readily yield longer chain products on pyrolysis. From these observations, we suggest that Py-GC in combination with PCA provides useful information concerning the chemical nature of organically bound sulphur in geomacromolecules. This information can be rationalised based on carbon skeleton relationships established for low molecular weight organic sulphur compounds, and in terms of kerogen type and overall sulphur content

Recent analytical advances now make it feasible to determine multiple isotopic characteristics of individual organic compounds within complex mixtures. In particular, hydrogen isotopic compositions and radiocarbon contents can now be readily determined to complement information derived from stable carbon isotopic analysis. When used in concert, these lines of geochemical information can yield important new insights into the origins and histories of the biomarker compounds, and lead to new and refined interpretation of molecular proxy records of paleoenvironmental variability. We present multi-isotopic data on n-alkyl lipids isolated from a range of recent aquatic sediments in order to demonstrate both the complexity of geochemical signals preserved in environmental matices, and the utility of multi-isotopic information in constraining inputs. In particular, we focus on long-chain lipids derived from terrestrial and marine precursors. Marked radiocarbon age and stable isotopic variability is apparent, even within closely related homologous series of compounds recovered from the same sample. Based on multi-isotope characteristics, we interpret these variations in terms of differences in source versus reactivity of individual organic compounds, and discuss implications for interpretation of the sedimentary record.

The distributions of sulphur-containing compounds generated by flash pyrolysis of macromolecular sedimentary organic matter (kerogen, coal, asphaltenes) were studied by gas chromatography in combination with Sselective flame photometric detection or mass spectrometry. The abundance of S-containing pyrolysis products in the pyrolysates relative to other products was highly variable depending on the sample but the types of products were generally similar, being mainly composed of “gaseous” compounds (e.g., hydrogen sulphide) and low molecular weight alkylthiophenes and alkylbenzothiophenes. The distribution patterns of the alkylated thiophenes were dominated by a limited number of all theoretically possible isomers. The alkyl substitution patterns of the dominant isomers bear a strong similarity to those of the organic S compounds present in the GC-amenable fractions of bitumens and immature oils. Therefore, it is suggested that these S-containing pyrolysis products are formed by pyrolysis of related thiophenic and benzothiophenic moieties present in the macromolecular sedimentary substances. Specific examples include those with linear alkyl, iso and anteiso alkyl, isoprenoid alkyl and steroidal carbon skeletons. The presence of higher molecular weight alkylthiophenes and alkylbenzothiophenes with these same carbon skeletons in pyrolysates of S-rich kerogens provided further evidence for the presence of these S-containing moieties. It is likely that these moieties have been formed by abiogenic S incorporation into sedimentary organic matter during early diagenesis.