Marine sedimentary organic matter: delineation of marine and terrestrial sources through radiocarbon dating; and the role of organic sulfur in early petroleum generation

Thesis (M.S.)--Joint Program in Oceanography and Oceanographic Engineering (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), June 1996."May 1996."Includes bibliographical references (leaves 66-68).This thesis details two years of research conducted with the guidance and support of three advisors: Dr. J. K. Whelan, Dr. J. S. Seewald and Dr. T. I. Eglinton. Each of the three chapters represents a different, self-contained research project. All of the projects are related to the organic geochemistry of marine sediments, however, this is a fairly encompassing area of study. Chapters 1 and 2 stem from the same experimental study -- the use of hydrous-pyrolysis to investigate mechanisms leading to the production of petroleum-related products during kerogen maturation. Chapter 3, on the other hand, utilizes a recently developed technique of isolating and AMS-14C dating individual compounds from complex sedimentary organic mixtures. The samples used in each investigation came from all over the world. The first two chapters utilize ancient marine sediment samples obtained from an outcrop in California (Chpts. 1 and 2) and from a well in Alabama (Chpt. 2). In contrast, recent marine sediment samples were obtained from the Arabian and Black Seas for the third chapter. Several preparative and analytical methods are common to all three studies. Nevertheless, each employ techniques totally unique from one another and from previous investigations. In Chapter 1, for example, X-ray absorption spectroscopy (XANES) is used to determine the speciation of organic sulfur present in kerogen, bitumen, and bulk sediment samples. While Chapter 3 represents the first study in which the "4C ages of individual, known hydrocarbon biomarkers are determined after isolation by Preparative Capillary Gas Chromatography (PCGC). The insights gained by these investigations are discussed in detail in the following chapters. The common thread between the three chapters is that the source of organic matter, the rate at which it is delivered to marine sediments and the depositional environment, all set the stage for kerogen formation and eventual petroleum generation.by Bryan C. Benitez-Nelson.M.S

The Impacts of Flood, Drought, and Turbidites on Organic Carbon Burial Over the Past 2,000 years in the Santa Barbara Basin, California

Climate conditions and instantaneous depositional events can influence the relative contribution of sediments from terrestrial and marine environments and ultimately the quantity and composition of carbon buried in the sediment record. Here, we analyze the elemental, isotopic, and organic geochemical composition of marine sediments to identify terrestrial and marine sources in sediment horizons associated with droughts, turbidites, and floods in the Santa Barbara Basin (SBB), California, during the last 2,000 years. Stable isotopes (δ13C and δ15N) indicate that more terrestrial organic carbon (OC) was deposited during floods relative to background sediment, while bulk C to nitrogen (C/N) ratios remained relatively constant (~10). Long- chain n- alkanes (C27, C29, C31, and C33), characteristic of terrestrial OC, dominated all types of sediment deposition but were 4 times more abundant in flood layers. Marine algae (C15, C17, and C19) and macrophytes (C21 and C23) were also 2 times higher in flood versus background sediments. Turbidites contained twice the terrestrial n- alkanes relative to background sediment. Conversely, drought intervals were only distinguishable from background sediment by their higher proportion of marine algal n- alkanes. Combined, our data indicate that 15% of the total OC buried in SBB over the past 2,000 years was deposited during 11 flood events where the sediment was mostly terrestrially derived, and another 12% of deep sediment OC burial was derived from shelf remobilization during six turbidite events. Relative to twentieth century river runoff, our data suggest that floods result in considerable terrestrial OC burial on the continental margins of California.Key PointsTerrestrial organic carbon is the dominant source of carbon to the SBB with deposition significantly increasing during flood eventsEpisodic flood and turbidite remobilization events were responsible for over 25% of the OC buried in the SBB over the past 2,000 yearsDrought sedimentation had significantly lower sedimentation rates and had an n- alkane composition consistent with increased marine inputsPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/156217/4/palo20901-sup-0002-2020PA003849-fs01.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/156217/3/palo20901_am.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/156217/2/palo20901.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/156217/1/palo20901-sup-0003-2020PA003849-fs02.pd

Particle fluxes associated with mesoscale eddies in the Sargasso Sea

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 Deep Sea Research Part II: Topical Studies in Oceanography 55 (2008): 1426-1444, doi:10.1016/j.dsr2.2008.02.007.We examined the impact of a cyclonic eddy and mode-water eddy on particle flux in the Sargasso Sea. The primary method used to quantify flux was based upon measurements of the natural radionuclide, 234Th, and these flux estimates were compared to results from sediment traps in both eddies, and a 210Po/210Pb flux method in the mode-water eddy. Particulate organic carbon (POC) fluxes at 150m ranged from 1 to 4 mmol C m-2 d-1 and were comparable between methods, especially considering differences in integration times scales of each approach. Our main conclusion is that relative to summer mean conditions at the Bermuda Atlantic Time-series Study (BATS) site, eddy-driven changes in biogeochemistry did not enhance local POC fluxes during this later, more mature stage of the eddy life cycle (>6 months old). The absence of an enhancement in POC flux puts a constraint on the timing of higher POC flux events, which are thought to have caused the local O2 minima below each eddy, and must have taken place >2 months prior to our arrival. The mode-water eddy did enhance preferentially diatom biomass in its center where we estimated a factor of 3 times higher biogenic Si flux than the BATS summer average. An unexpected finding in the highly depth resolved 234Th data sets are narrow layers of particle export and remineralization within the eddy. In particular, a strong excess 234Th signal is seen below the deep chlorophyll maxima which we attribute to remineralization of 234Th bearing particles. At this depth below the euphotic zone, de novo particle production in the euphotic zone has stopped, yet particle remineralization continues via consumption of labile sinking material by bacteria and/or zooplankton. These data suggest that further study of processes in ocean layers is warranted not only within, but below the euphotic zone.The EDDIES project was funded by the National Science Foundation Chemical, Biological, and Physical Oceanography Programs. Additional support for HPLC pigment analysis (Dr. Charles Trees, CHORS) was provided by NASA

Calcification of the Planktonic Foraminiferaglobigerinabulloidesand Carbonate Ion Concentration Resultsfrom the Santa Barbara Basin

Planktonic foraminiferal calcification intensity, reflected by shell wall thickness, has been hypothesized to covary with the carbonate chemistry of seawater. Here we use both sediment trap and box core samples from the Santa Barbara Basin to evaluate the relationship between the calcification intensity of the planktonic foraminifera species Globigerina bulloides, measured by area density (µg/µm2), and the carbonate ion concentration of seawater ([CO32−]). We also evaluate the influence of both temperature and nutrient concentration ([PO43−]) on foraminiferal calcification and growth. The presence of two G. bulloides morphospecies with systematically different calcification properties and offset stable isotopic compositions was identified within sampling populations using distinguishing morphometric characteristics. The calcification temperature and by extension calcification depth of the more abundant “normal” G. bulloides morphospecies was determined using δ18O temperature estimates. Calcification depths vary seasonally with upwelling and were used to select the appropriate [CO32−], temperature, and [PO43−] depth measurements for comparison with area density. Seasonal upwelling in the study region also results in collinearity between independent variables complicating a straightforward statistical analysis. To address this issue, we use additional statistical diagnostics and a down core record to disentangle the respective roles of each parameter on G. bulloides calcification. Our results indicate that [CO32−] is the primary variable controlling calcification intensity while temperature influences shell size. We report a modern calibration for the normal G. bulloides morphospecies that can be used in down core studies of well‐preserved sediments to estimate past [CO32−]

Biogenic Nitrogen Gas Production at the Oxic–Anoxic Interface in the Cariaco Basin, Venezuela

Excess nitrogen gas (N2xs) was measured in samples collected at six locations in the eastern and western sub-basins of the Cariaco Basin, Venezuela, in September 2008 (non-upwelling conditions) and March 2009 (upwelling conditions). During both sampling periods, N2xs concentrations were below detection in surface waters, increasing to ~ 22 μmol N kg−1 at the oxic–anoxic interface ([O2] \u3c ~ 4 μmol kg−1, ~ 250 m). Below the oxic–anoxic interface (300–400 m), the average concentration of N2xs was 24.7 ± 1.9 μmol N kg−1 in September 2008 and 27.5 ± 2.0 μmol N kg−1 in March 2009, i.e., N2xs concentrations within this depth interval were ~ 3 μmol N kg−1 higher (p \u3c 0.001) during the upwelling season compared to the non-upwelling period. These results suggest that N-loss in the Cariaco Basin may vary seasonally in response to changes in the flux of sinking particulate organic matter. We attribute the increase in N2xs concentrations, or N-loss, observed during upwelling to: (1) higher availability of fixed nitrogen derived from suspended and sinking particles at the oxic–anoxic interface and/or (2) enhanced ventilation at the oxic–anoxic interface during upwelling

Mercury Cycling in the North Pacific Subtropical Gyre as Revealed by Mercury Stable Isotope Ratios

The oceans are an important global reservoir for mercury (Hg), and marine fish consumption is the dominant human exposure pathway for its toxic methylated form. A more thorough understanding of the global biogeochemical cycle of Hg requires additional information on the mechanisms that control Hg cycling in pelagic marine waters. In this study, Hg isotope ratios and total Hg concentrations are used to explore Hg biogeochemistry in oligotrophic marine environments north of Hawaii. We present the first measurements of the vertical water column distribution of Hg concentrations and the Hg isotopic composition in precipitation, marine particles, and zooplankton near Station ALOHA (22°45′N, 158°W). Our results reveal production and demethylation of methylmercury in both the euphotic (0–175 m) and mesopelagic zones (200–1,000 m). We document a strong relationship between Hg isotopic composition and depth in particles, zooplankton, and fish in the water column and diurnal variations in Δ199Hg values in zooplankton sampled near the surface (25 m). Based on these observations and stable Hg isotope relationships in the marine food web, we suggest that the Hg found in large pelagic fish at Station ALOHA was originally deposited largely by precipitation, transformed into methyl‐Hg, and bioaccumulated in situ in the water column. Our results highlight how Hg isotopic compositions reflect abiotic and biotic production and degradation of methyl‐Hg throughout the water column and the importance of particles and zooplankton in the vertical transport of Hg

Mercury Cycling in the North Pacific Subtropical Gyre as Revealed by Mercury Stable Isotope Ratios

The oceans are an important global reservoir for mercury (Hg), and marine fish consumption is the dominant human exposure pathway for its toxic methylated form. A more thorough understanding of the global biogeochemical cycle of Hg requires additional information on the mechanisms that control Hg cycling in pelagic marine waters. In this study, Hg isotope ratios and total Hg concentrations are used to explore Hg biogeochemistry in oligotrophic marine environments north of Hawaii. We present the first measurements of the vertical water column distribution of Hg concentrations and the Hg isotopic composition in precipitation, marine particles, and zooplankton near Station ALOHA (22°45â ²N, 158°W). Our results reveal production and demethylation of methylmercury in both the euphotic (0â 175 m) and mesopelagic zones (200â 1,000 m). We document a strong relationship between Hg isotopic composition and depth in particles, zooplankton, and fish in the water column and diurnal variations in Î 199Hg values in zooplankton sampled near the surface (25 m). Based on these observations and stable Hg isotope relationships in the marine food web, we suggest that the Hg found in large pelagic fish at Station ALOHA was originally deposited largely by precipitation, transformed into methylâ Hg, and bioaccumulated in situ in the water column. Our results highlight how Hg isotopic compositions reflect abiotic and biotic production and degradation of methylâ Hg throughout the water column and the importance of particles and zooplankton in the vertical transport of Hg.Key PointsMMHg bioaccumulated in fish is derived primarily from Hg (II) deposited in atmospheric precipitationMarine particles host the majority of Hg available for production of MMHg in the open oceanMethylation and demethylation of Hg occurs throughout the euphotic and mesopelagic zones in the North Pacific Subtropical GyrePeer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/150543/1/gbc20883.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/150543/2/gbc20883_am.pd

Impact of eddy–wind interaction on eddy demographics and phytoplankton community structure in a model of the North Atlantic Ocean

Author Posting. © The Author(s), 2010. 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 Dynamics of Atmospheres and Oceans 52 (2011): 80-94, doi:10.1016/j.dynatmoce.2011.01.003.Two eddy-resolving (0.1-degree) physical-biological simulations of the North Atlantic Ocean are compared, one with the surface momentum flux computed only from wind velocities and the other using the difference between air and ocean velocity vectors. This difference in forcing has a significant impact on the intensities and relative number of different types of mesoscale eddies in the Sargasso Sea. Eddy/wind interaction significantly reduces eddy intensities and increases the number of mode-water eddies and “thinnies” relative to regular cyclones and anticyclones; it also modifies upward isopycnal displacements at the base of the euphotic zone, increasing them in the centers of mode water eddies and at the edges of cyclones, and decreasing them in the centers of cyclones. These physical changes increase phytoplankton growth rates and biomass in mode-water eddies, bringing the biological simulation into better agreement with field data. These results indicate the importance of including the eddy/wind interaction in simulations of the physics and biology of eddies in the subtropical North Atlantic. However, eddy intensities in the simulation with eddy/wind interaction are lower than observed, which suggests a decrease in horizontal viscosity or an increase in horizontal grid resolution will be necessary to regain the observed level of eddy activity.LAA and DJM gratefully acknowledge the support of NASA grant 07-CARBON07-17. SCD and IDL gratefully acknowledge support from the NSF Center for Microbial Oceanography, Research and Education (C-MORE; NSF EF-0424599)

Prediction of the export and fate of global ocean net primary production : the EXPORTS Science Plan

© The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Frontiers in Marine Science 3 (2016): 22, doi:10.3389/fmars.2016.00022.Ocean ecosystems play a critical role in the Earth's carbon cycle and the quantification of their impacts for both present conditions and for predictions into the future remains one of the greatest challenges in oceanography. The goal of the EXport Processes in the Ocean from Remote Sensing (EXPORTS) Science Plan is to develop a predictive understanding of the export and fate of global ocean net primary production (NPP) and its implications for present and future climates. The achievement of this goal requires a quantification of the mechanisms that control the export of carbon from the euphotic zone as well as its fate in the underlying “twilight zone” where some fraction of exported carbon will be sequestered in the ocean's interior on time scales of months to millennia. Here we present a measurement/synthesis/modeling framework aimed at quantifying the fates of upper ocean NPP and its impacts on the global carbon cycle based upon the EXPORTS Science Plan. The proposed approach will diagnose relationships among the ecological, biogeochemical, and physical oceanographic processes that control carbon cycling across a range of ecosystem and carbon cycling states leading to advances in satellite diagnostic and numerical prognostic models. To collect these data, a combination of ship and robotic field sampling, satellite remote sensing, and numerical modeling is proposed which enables the sampling of the many pathways of NPP export and fates. This coordinated, process-oriented approach has the potential to foster new insights on ocean carbon cycling that maximizes its societal relevance through the achievement of research goals of many international research agencies and will be a key step toward our understanding of the Earth as an integrated system.The development of the EXPORTS Science Plan was supported by NASA Ocean Biology and Biogeochemistry program (award NNX13AC35G)