Direct measurement of riverine particulate organic carbon age structure

Author Posting. © American Geophysical Union, 2012. 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 39 (2012): L19703, doi:10.1029/2012GL052883.Carbon cycling studies focusing on transport and transformation of terrigenous carbon sources toward marine sedimentary sinks necessitate separation of particulate organic carbon (OC) derived from many different sources and integrated by river systems. Much progress has been made on isolating and characterizing young biologically-formed OC that is still chemically intact, however quantification and characterization of old, refractory rock-bound OC has remained troublesome. Quantification of both endmembers of riverine OC is important to constrain exchanges linking biologic and geologic carbon cycles and regulating atmospheric CO2 and O2. Here, we constrain petrogenic OC proportions in suspended sediment from the headwaters of the Ganges River in Nepal through direct measurement using ramped pyrolysis radiocarbon analysis. The unique results apportion the biospheric and petrogenic fractions of bulk particulate OC and characterize biospheric OC residence time. Compared to the same treatment of POC from the lower Mississippi-Atchafalaya River system, contrast in age spectra of the Ganges tributary samples illustrates the difference between small mountainous river systems and large integrative ones in terms of the global carbon cycle.This work was partially supported by U.S. National Science Foundation (NSF) Cooperative Agreement OCE-228996 to NOSAMS and NSF grants OCE-0851015 & OCE-0928582 to VG.2013-04-0

Accelerator mass spectrometry 14C determination in CO2 produced from laser decomposition of aragonite

Author Posting. © John Wiley & Sons, 2008. This is the author's version of the work. It is posted here by permission of John Wiley & Sons for personal use, not for redistribution. The definitive version was published in Rapid Communications in Mass Spectrometry 22 (2008): 3443-3449, doi:10.1002/rcm.3745.Determination of 14C in aragonite (CaCO3) decomposed thermally to CO2 using an yttrium‐aluminum‐garnet doped neodymium laser is reported. Laser decomposition accelerator mass spectrometer (LD‐AMS) measurements reproduce AMS determinations of 14C from conventional reaction of aragonite with concentrated phosphoric acid. The lack of significant differences between these sets of measurements indicate that LD‐AMS radiocarbon dating can overcome the significant fractionation that has been observed during stable isotope (C and O) laser decomposition analysis of different carbonate minerals. The laser regularly converted nearly 30% of material removed to CO2 despite being optimized for ablation, where laser energy breaks material apart rather than chemically altering it. These results illustrate promise for using laser decomposition on the front‐end of AMS systems that directly measure CO2 gas. The feasibility of such measurements depends on 1. the improvement of material removal and/or CO2 generation efficiency of the laser decomposition system and 2. the ionization efficiency of AMS systems measuring continuously flowing CO2.This work was funded on a competitive basis by the Cecil H. and Ida M. Green Technology Innovation Award of Woods Hole Oceanographic Institution

Salinity change in the subtropical Atlantic : secular increase and teleconnections to the North Atlantic Oscillation

Author Posting. © American Geophysical Union, 2005. 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 32 (2005): L02603, doi:10.1029/2004GL021499.Recent studies comparing shipboard data between the 1950's and the 1990's have shown significant, heterogeneous adjustments of the temperature-salinity structure of the N. Atlantic Ocean. Here, we present proxy records of temperature and salinity from aragonite sclerosponge skeletons, extending existing records of the Salinity Maximum Waters (SMW) of the N. Atlantic back to 1890. These proxy records show secular temperature increases of 1.6–2.0°C, higher than published global averages, and salinity increases of 0.35–0.5 psu, smaller than short-term secular trends recently measured. Salinity reconstructions vary more significantly on the decadal scale, showing changes that are related to low-frequency variations of the North Atlantic Oscillation (NAO). On both secular and decadal time scales, the records indicate significant thermohaline changes in the SMW, either via forcing at the surface or increasing depths of density surfaces in the Bahamas.This project was supported by National Science Foundation grants 9819147 and 0136941 (to P.K.S) and 9876565 and 0134998 (to S.R.T)

The 13C Suess Effect in Scleractinian Corals Mirror Changes in the Anthropogenic CO2 Inventory of the Surface Oceans

New δ13C data are presented from 10 coral skeletons collected from Florida and elsewhere in the Caribbean (Dominica, Dominican Republic, Puerto Rico, and Belize). These corals range from 96 to 200 years in age and were collected between 1976 and 2002. The change in the δ13C of the skeletons from these corals between 1900 and 1990 has been compared with 27 other published coral records from the Atlantic, Pacific, and Indian Oceans. The new data presented here make possible, for the first time, a global comparison of rates of change in the δ13C value of coral skeletons. Of these records, 64% show a statistically significant (p \u3c 0.05) decrease in δ13C towards the modern day (23 out of 37). This decrease is attributable to the addition of anthropogenically derived CO2 (13C Suess effect) to the atmosphere. Between 1900 and 1990, the average rate of change of the δ13C in all the coral skeletons living under open oceanic conditions is approximately −0.01‰ yr−1. In the Atlantic Ocean the magnitude of the decrease since 1960,−0.019 yr−1 ±0.015‰, is essentially the same as the decrease in the δ13C of atmospheric CO2 and the δ13C of the oceanic dissolved inorganic carbon (−0.023 to −0.029‰ yr−1), while in the Pacific and Indian Oceans the rate is more variable and significantly reduced (−0.007‰ yr−1 ±0.013). These data strongly support the notion that (i) the δ13C of the atmosphere controls ambient δ13C of the dissolved inorganic carbon which in turn is reflected in the coral skeletons, (ii) the rate of decline in the coral skeletons is higher in oceans with a greater anthropogenic CO2inventory in the surface oceans, (iii) the rate of δ13C decline is accelerating. Superimposed on these secular variations are controls on theδ13C in the skeleton governed by growth rate, insolation, and local water masses

Software development for continuous-gas-flow AMS

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 Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms 266 (2008): 2233-2237, doi:10.1016/j.nimb.2008.03.001.The National Ocean Sciences Accelerator Mass Spectrometry (NOSAMS) Facility at Woods Hole Oceanographic Institution is presently completing installation of a novel continuous-flow AMS system. A multi-year development of an AMS microwave gas ion source in collaboration with Atomic Energy Canada Limited (AECL), Chalk River, has preceded this final step of an implementation that is expected to add a new dimension to 14C AMS. National Instruments, NIM, and CAMAC modules have been programmed with LabVIEW on a Windows XP platform to form the basis for data acquisition. In this paper we discuss possible applications and include simulations of expected data acquisition scenarios like real-time AMS analysis of chromatograms. Particular attention is given to issues of synchronization between rapidly changing input amplitudes and signal processing cycles in hardware and software.This work is supported by the United States National Science Foundation under Cooperative Agreement OCE-0228996

Stylasterid corals: a new paleotemperature archive

Stylasterids are a ubiquitous deep-sea coral taxon that build their skeletons from either calcite, aragonite, or both. Yet, robust geochemical proxy data from these corals are limited. In this study, 95 modern stylasterids, spanning a wide range of depths (63 to 2894 m) and ambient seawater temperatures (0 to 17 °C), were tested for their potential use as paleoceanographic archives. Stable oxygen and carbon isotopic composition (O and C) were measured from the main trunk of all specimens and five specimens were further sub-sampled to assess internal chemical variability. The isotope data show non-equilibrium precipitation from seawater for both O and C, with the growing tips of colonies yielding the isotopically lowest values. Overall, the calcitic corals showed lower isotope values for O and C than aragonitic specimens. Within the aragonite corals, we present a O:temperature calibration that exhibits a significant linear relationship with the equation Ocoral-seawater = −0.22(°C) + 3.33(±0.06) across a temperature range of 0 to 30 °C, using samples from this study and published data. This work highlights the potential application of stylasterid coral O data to reconstruct paleo seawater temperature

Biogeochemical and historical drivers of microbial community composition and structure in sediments from Mercer Subglacial Lake, West Antarctica

Ice streams that flow into Ross Ice Shelf are underlain by water-saturated sediments, a dynamic hydrological system, and subglacial lakes that intermittently discharge water downstream across grounding zones of West Antarctic Ice Sheet (WAIS). A 2.06 m composite sediment profile was recently recovered from Mercer Subglacial Lake, a 15 m deep water cavity beneath a 1087 m thick portion of the Mercer Ice Stream. We examined microbial abundances, used 16S rRNA gene amplicon sequencing to assess community structures, and characterized extracellular polymeric substances (EPS) associated with distinct lithologic units in the sediments. Bacterial and archaeal communities in the surficial sediments are more abundant and diverse, with significantly different compositions from those found deeper in the sediment column. The most abundant taxa are related to chemolithoautotrophs capable of oxidizing reduced nitrogen, sulfur, and iron compounds with oxygen, nitrate, or iron. Concentrations of dissolved methane and total organic carbon together with water content in the sediments are the strongest predictors of taxon and community composition. δ¹³C values for EPS (−25 to −30‰) are consistent with the primary source of carbon for biosynthesis originating from legacy marine organic matter. Comparison of communities to those in lake sediments under an adjacent ice stream (Whillans Subglacial Lake) and near its grounding zone provide seminal evidence for a subglacial metacommunity that is biogeochemically and evolutionarily linked through ice sheet dynamics and the transport of microbes, water, and sediments beneath WAIS

A high-performance 14C accelerator mass spectrometry system

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): 228-235.A new and unique radiocarbon accelerator mass spectrometry (AMS) facility has been constructed at the Woods Hole Oceanographic Institution. The defining characteristic of the new system is its large-gap optical elements that provide a larger-than-standard beam acceptance. Such a system is ideally suited for high-throughput, high-precision measurements of 14C. Details and performance of the new system are presented

Antarctic sediment chronology by programmed-temperature pyrolysis : methodology and data treatment

Author Posting. © American Geophysical Union, 2008. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 9 (2008): Q04005, doi:10.1029/2007GC001816.We report a detailed programmed-temperature pyrolysis/combustion methodology for radiocarbon (14C) dating of Antarctic sub-ice shelf sediments. The method targets the autochthonous organic component in sediments that contain a distribution of acid-insoluble organic components from several sources of different ages. The approach has improved sediment chronology in organic-rich sediments proximal to Antarctic ice shelves by yielding maximum age constraints significantly younger than bulk radiocarbon dates from the same sediment horizons. The method proves adequate in determining isotope ratios of the pre-aged carbon end-member; however, the isotopic compositions of the low-temperature measurements indicate that no samples completely avoided mixing with some proportion of pre-aged organic material. Dating the unresolved but desired young end-member must rely on indirect methods, but a simple mixing model cannot be developed without knowledge of the sedimentation rate or comparable constraints. A mathematical approach allowing for multiple mixing components yields a maximum likelihood age, a first-order approximation of the relative proportion of the autochthonous component, and the temperature at which allochthonous carbon begins to volatilize and mix with the autochthonous component. It is likely that our estimation of the cutoff temperature will be improved with knowledge of the pyrolysis kinetics of the major components. Chronology is improved relative to bulk acid-insoluble organic material ages from nine temperature interval dates down to two, but incorporation of inherently more pre-aged carbon in the first division becomes more apparent with fewer and larger temperature intervals.The project was paid for in part by NSF research grants OPP 02-30089 and OPP 03-38142 to Hamilton College (E. Domack) and NSF Cooperative Agreement OCE- 0228996 to Woods Hole Oceanographic Institution

A method for successful collection of multicores and gravity cores from Antarctic subglacial lakes

During the 2018–2019 Antarctic field season, the Subglacial Antarctic Lakes Scientific Access project team cleanly accessed Mercer Subglacial Lake, West Antarctica, to sample water and sediments beneath 1087 m of overlying ice. A multicorer was successful in sampling the sediment–water interface, with 4 deployments retrieving 10 cores between 0.3 and 0.4 m in length. Gravity coring was also successful, retrieving cores of 0.97 and 1.78 m in glacial diamict. However, sediment cores retrieved by the gravity cores were shorter than the core barrel penetration (as measured by mud streaks on the outside of the coring system), indicating that the system can likely be improved. This manuscript describes the design, implementation, successes, and lessons learned while coring sediments in a subglacial lake