Description: Author Posting. © Arizona Board of Regents on behalf of the University of Arizona, 2010. This article is posted here by permission of Dept. of Geosciences, University of Arizona for personal use, not for redistribution. The definitive version was published in Radiocarbon 52 (2010): 1322-1335.

Description: The Keck Carbon Cycle AMS facility at the University of California, Irvine (KCCAMS/UCI) has developed protocols for analyzing radiocarbon in samples as small as ~0.001 mg of carbon (C). Mass-balance background corrections for modern and 14C-dead carbon contamination (MC and DC, respectively) can be assessed by measuring 14C-free and modern standards, respectively, using the same sample processing techniques that are applied to unknown samples. This approach can be validated by measuring secondary standards of similar size and 14C composition to the unknown samples. Ordinary sample processing (such as ABA or leaching pretreatment, combustion/graphitization, and handling) introduces MC contamination of ~0.6 ± 0.3 μg C, while DC is ~0.3 ± 0.15 μg C. Today, the laboratory routinely analyzes graphite samples as small as 0.015 mg C for external submissions and ≅0.001 mg C for internal research activities with a precision of ~1% for ~0.010 mg C. However, when analyzing ultra-small samples isolated by a series of complex chemical and chromatographic methods (such as individual compounds), integrated procedural blanks may be far larger and more variable than those associated with combustion/graphitization alone. In some instances, the mass ratio of these blanks to the compounds of interest may be so high that the reported 14C results are meaningless. Thus, the abundance and variability of both MC and DC contamination encountered during ultra-small sample analysis must be carefully and thoroughly evaluated. Four case studies are presented to illustrate how extraction chemistry blanks are determined.

Description: Author Posting. © Arizona Board of Regents on behalf of the University of Arizona, 2005. This article is posted here by permission of Dept. of Geosciences, University of Arizona for personal use, not for redistribution. The definitive version was published in Radiocarbon 47 (2005): 413-424.

Description: 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 Δ14C 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.

Description: This research was funded by NSF grant # OCE-0327405 and DFG project # SCHN621 and a WHOI-NOSAMS postdoctoral scholarship to GM.

Description: © The Author(s), 2012. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 9 (2012): 1217-1224, doi:10.5194/bg-9-1217-2012.

Description: Arctic warming is projected to continue throughout the coming century. Yet, our currently limited understanding of the Arctic Ocean carbon cycle hinders our ability to predict how changing conditions will affect local Arctic ecosystems, regional carbon budgets, and global climate. We present here the first set of concurrent, full-depth, dual-isotope profiles for dissolved inorganic carbon (DIC), dissolved organic carbon (DOC), and suspended particulate organic carbon (POCsusp) at two sites in the Canada Basin of the Arctic Ocean. The carbon isotope composition of sinking and suspended POC in the Arctic contrasts strongly with open ocean Atlantic and Pacific sites, pointing to a combination of inputs to Arctic POCsusp at depth, including surface-derived organic carbon (OC), sorbed/advected OC, and OC derived from in situ DIC fixation. The latter process appears to be particularly important at intermediate depths, where mass balance calculations suggest that OC derived from in situ DIC fixation contributes up to 22% of POCsusp. As in other oceans, surface-derived OC is still a dominant source to Arctic POCsusp. Yet, we suggest that significantly smaller vertical POC fluxes in the Canada Basin make it possible to see evidence of DIC fixation in the POCsusp pool even at the bulk isotope level.

Description: The 2008 JOIS hydrographic program was supported by Fisheries and Oceans Canada, the Canadian International Polar Year Office, and the US National Science Foundation (OPP-0424864; lead-PI Andrey Proshutinsky).

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

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

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

Description: Author Posting. © Arizona Board of Regents on behalf of the University of Arizona, 2005. This article is posted here by permission of Dept. of Geosciences, University of Arizona for personal use, not for redistribution. The definitive version was published in Radiocarbon 47 (2005): 401-412.

Description: The chemical and isotopic compositions of long-chain (C36–C39) unsaturated ketones (alkenones), a unique class of algal lipids, encode surface ocean properties useful for paleoceanographic reconstruction. Recently, we have sought to extend the utility of alkenones as oceanic tracers through measurement of their radiocarbon contents. Here, we describe a method for isolation of alkenones from sediments as a compound class based on a sequence of wet chemical techniques. The steps involved, which include silica gel column chromatography, urea adduction, and silver nitrate-silica gel column chromatography, exploit various structural attributes of the alkenones. Amounts of purified alkenones estimated by GC/FID measurements were highly correlated with CO2 yields after sample combustion, indicating purities of greater than 90% for samples containing ≥100 μg C. The degree of alkenone unsaturation ( ) also varied minimally through the procedure. We also describe a high-performance liquid chromatography (HPLC) method to isolate individual alkenones for molecular-level structural and isotopic determination.

Description: This work was funded through grants from the National Science Foundation (OCE-9809624; OCE- 9907129) and the Japan Society for the Promotion of Science.

Description: Author Posting. © Arizona Board of Regents on behalf of the University of Arizona, 2005. This article is posted here by permission of Dept. of Geosciences, University of Arizona for personal use, not for redistribution. The definitive version was published in Radiocarbon 47 (2005): 425-432.

Description: As a result of the growing use of multiple geochemical proxies to reconstruct ocean and climate changes in the past, there is an increasing need to establish temporal relationships between proxies derived from the same marine sediment record and ideally from the same core sections. Coupled proxy records of surface ocean properties, such as those based on lipid biomarkers (e.g. alkenone-derived sea surface temperature) and planktonic foraminiferal carbonate (oxygen isotopes), are a key example. Here, we assess whether 2 different solvent extraction procedures used for isolation of molecular biomarkers influence the radiocarbon contents of planktonic foraminiferal carbonate recovered from the corresponding residues of Bermuda Rise and Cariaco Basin sediments. Although minor Δ14C differences were observed between solvent-extracted and unextracted samples, no substantial or systematic offsets were evident. Overall, these data suggest that, in a practical sense, foraminiferal shells from a solvent-extracted residue can be reliably used for 14C dating to determine the age of sediment deposition and to examine age relationships with other sedimentary constituents (e.g. alkenones).

Description: This work was financially supported by NSF grant 9809624. N Ohkouchi was supported by a fellowship from Japan Society for the Promotion of Science.

Description: © The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Carbon Balance and Management 12 (2017): 10, doi:10.1186/s13021-017-0077-x.

Description: Determining national carbon stocks is essential in the framework of ongoing climate change mitigation actions. Presently, assessment of carbon stocks in the context of greenhouse gas (GHG)-reporting on a nation-by-nation basis focuses on the terrestrial realm, i.e., carbon held in living plant biomass and soils, and on potential changes in these stocks in response to anthropogenic activities. However, while the ocean and underlying sediments store substantial quantities of carbon, this pool is presently not considered in the context of national inventories. The ongoing disturbances to both terrestrial and marine ecosystems as a consequence of food production, pollution, climate change and other factors, as well as alteration of linkages and C-exchange between continental and oceanic realms, highlight the need for a better understanding of the quantity and vulnerability of carbon stocks in both systems. We present a preliminary comparison of the stocks of organic carbon held in continental margin sediments within the Exclusive Economic Zone of maritime nations with those in their soils. Our study focuses on Namibia, where there is a wealth of marine sediment data, and draws comparisons with sediment data from two other countries with different characteristics, which are Pakistan and the United Kingdom. Results indicate that marine sediment carbon stocks in maritime nations can be similar in magnitude to those of soils. Therefore, if human activities in these areas are managed, carbon stocks in the oceanic realm—particularly over continental margins—could be considered as part of national GHG inventories. This study shows that marine sediment organic carbon stocks can be equal in size or exceed terrestrial carbon stocks of maritime nations. This provides motivation both for improved assessment of sedimentary carbon inventories and for reevaluation of the way that carbon stocks are assessed and valued. The latter carries potential implications for the management of human activities on coastal environments and for their GHG inventories.

Description: We acknowledge research support from ETH Zurich and the Swiss National Science Foundation.

Description: © The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 15 (2018): 3357-3375, doi:10.5194/bg-15-3357-2018.

Description: The modern-day Godavari River transports large amounts of sediment (170 Tg per year) and terrestrial organic carbon (OCterr; 1.5 Tg per year) from peninsular India to the Bay of Bengal. The flux and nature of OCterr is considered to have varied in response to past climate and human forcing. In order to delineate the provenance and nature of organic matter (OM) exported by the fluvial system and establish links to sedimentary records accumulating on its adjacent continental margin, the stable and radiogenic isotopic composition of bulk OC, abundance and distribution of long-chain fatty acids (LCFAs), sedimentological properties (e.g. grain size, mineral surface area, etc.) of fluvial (riverbed and riverbank) sediments and soils from the Godavari basin were analysed and these characteristics were compared to those of a sediment core retrieved from the continental slope depocenter. Results show that river sediments from the upper catchment exhibit higher total organic carbon (TOC) contents than those from the lower part of the basin. The general relationship between TOC and sedimentological parameters (i.e. mineral surface area and grain size) of the sediments suggests that sediment mineralogy, largely driven by provenance, plays an important role in the stabilization of OM during transport along the river axis, and in the preservation of OM exported by the Godavari to the Bay of Bengal. The stable carbon isotopic (δ13C) characteristics of river sediments and soils indicate that the upper mainstream and its tributaries drain catchments exhibiting more 13C enriched carbon than the lower stream, resulting from the regional vegetation gradient and/or net balance between the upper (C4-dominated plants) and lower (C3-dominated plants) catchments. The radiocarbon contents of organic carbon (Δ14COC) in deep soils and eroding riverbanks suggests these are likely sources of "old" or pre-aged carbon to the Godavari River that increasingly dominates the late Holocene portion of the offshore sedimentary record. While changes in water flow and sediment transport resulting from recent dam construction have drastically impacted the flux, loci, and composition of OC exported from the modern Godavari basin, complicating reconciliation of modern-day river basin geochemistry with that recorded in continental margin sediments, such investigations provide important insights into climatic and anthropogenic controls on OC cycling and burial.

Description: This project was supported by the Swiss National Science Foundations (“CAPS LOCK” grant no. 200021-140850 and “CAPS-LOCK2” grant no. 200021-163162). Francien Peterse received funding from NWO-Veni grant (grant no. 863.13.016). Liviu Giosan thanks grants from the National Science Foundation (OCE-0841736) and Woods Hole Oceanographic Institution.

Description: © 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): 3153-3166, doi:10.5194/bg-7-3153-2010.

Description: Climate warming in northeastern Siberia may induce thaw-mobilization of the organic carbon (OC) now held in permafrost. This study investigated the composition of terrestrial OC exported to Arctic coastal waters to both obtain a natural integration of terrestrial permafrost OC release and to further understand the fate of released carbon in the extensive Siberian Shelf Seas. Application of a variety of elemental, molecular and isotopic (δ13C and Δ14C) analyses of both surface water suspended particulate matter and underlying surface sediments along a 500 km transect from Kolyma River mouth to the mid-shelf of the East Siberian Sea yielded information on the sources, degradation status and transport processes of thaw-mobilized soil OC. A three end-member dual-carbon-isotopic mixing model was applied to deduce the relative contributions from riverine, coastal erosion and marine sources. The mixing model was solved numerically using Monte Carlo simulations to obtain a fair representation of the uncertainties of both end-member composition and the end results. Riverine OC contributions to sediment OC decrease with increasing distance offshore (35±15 to 13±9%), whereas coastal erosion OC exhibits a constantly high contribution (51±11 to 60±12%) and marine OC increases offshore (9±7 to 36±10%). We attribute the remarkably strong imprint of OC from coastal erosion, extending up to ~500 km from the coast, to efficient offshoreward transport in these shallow waters presumably through both the benthic boundary layer and ice-rafting. There are also indications of simultaneous selective preservation of erosion OC compared to riverine OC. Molecular degradation proxies and radiocarbon contents indicated a degraded but young (Δ14C ca. −60‰ or ca. 500 14C years) terrestrial OC pool in surface water particulate matter, underlain by a less degraded but old (Δ14C ca. −500‰ or ca. 5500 14C years) terrestrial OC pool in bottom sediments. We suggest that the terrestrial OC fraction in surface water particulate matter is mainly derived from surface soil and recent vegetation fluvially released as buoyant organic-rich aggregates (e.g., humics), which are subjected to extensive processing during coastal transport. In contrast, terrestrial OC in the underlying sediments is postulated to originate predominantly from erosion of mineral-rich Pleistocene coasts (i.e., yedoma) and inland mineral soils. Sorptive association of this organic matter with mineral particles protects the OC from remineralization and also promotes rapid settling (ballasting) of the OC. Our findings corroborate recent studies by indicating that different Arctic surface soil OC pools exhibit distinguishing susceptibilities to degradation in coastal waters. Consequently, the general postulation of a positive feedback to global warming from degradation of permafrost carbon may be both attenuated (by reburial of one portion) and geographically displaced (degradation of released terrestrial permafrost OC far out over the Arctic shelf seas).

Description: The ISSS-08 program was supported by the Knut and Alice Wallenberg Foundation, Headquarters of the Far Eastern Branch of the Russian Academy of Sciences, the Swedish Research Council (VR Contract No. 621-2004-4039 and 621-2007-4631), the US National Oceanic and Atmospheric Administration (Siberian Shelf Study), the Russian Foundation of Basic Research (08-05-13572, 08-05-00191-a, and 07-05-00050a), the Swedish Polar Research Secretariat, the Arctic Co-Op Program of the Nordic Council of Ministers (331080-70219) and the National Science Foundation (OPP ARC 0909546). O¨ . G. also acknowledges financial support as an Academy Research Fellow from the Swedish Royal Academy of Sciences, L. S. a Marie Curie grant (contract no. PIEF-GA-2008-220424), T. E. an NSF grant (ARC-0909377) and A. A. support from the Knut and Alice Wallenberg Foundation.

Description: © The Author(s), 2013. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 10 (2013): 7065-7080, doi:10.5194/bg-10-7065-2013.

Description: In recent decades, the Canada Basin of the Arctic Ocean has experienced rapidly decreasing summer sea ice coverage and freshening of surface waters. It is unclear how these changes translate to deeper waters, particularly as our baseline understanding of organic carbon cycling in the deep basin is quite limited. In this study, we describe full-depth profiles of the abundance, distribution and carbon isotopic composition of fatty acids from suspended particulate matter at a seasonally ice-free station and a semi-permanently ice-covered station. Fatty acids, along with suspended particulate organic carbon (POC), are more concentrated and 13C-enriched under ice cover than in ice-free waters. But this influence, apparent at 50 m depth, does not propagate downward below 150 m depth, likely due to the weak biological pump in the central Canada Basin. Branched fatty acids have δ13C values that are similar to suspended POC at all depths and are more 13C-enriched than even-numbered saturated fatty acids at depths above 3000 m. These are likely to be produced in situ by heterotrophic bacteria incorporating organic carbon that is isotopically similar to total suspended POC. Below surface waters, there is also the suggestion of a source of saturated even-numbered fatty acids which could represent contributions from laterally advected organic carbon and/or from chemoautotrophic bacteria. At 3000 m depth and below, a greater relative abundance of long-chain (C20–24), branched and unsaturated fatty acids is consistent with a stronger influence of re-suspended sedimentary organic carbon. At these deep depths, two individual fatty acids (C12 and iso-C17) are significantly depleted in 13C, allowing for the possibility that methane oxidizing bacteria contribute fatty acids, either directly to suspended particulate matter or to shallow sediments that are subsequently mobilized and incorporated into suspended particulate matter within the deep basin.

Description: The WHOI Postdoctoral Scholar Program and NSF Cooperative Agreement for the Operation of a National Ocean Sciences Accelerator Mass Spectrometry Facility (OCE-0753487) supported S. R. Shah and the WHOI Arctic Research Initiative funded compound-specific isotopic analysis. The 2008 JOIS hydrographic program was supported by Fisheries and Oceans Canada, the Canadian International Polar Year Office, and the US National Science Foundation (OPP-0424864; lead-PI Andrey Proshutinsky).