Thesis: Ph. D., Joint Program in Marine Chemistry and Geochemistry (Massachusetts Institute of Technology, Department of Civil and Environmental Engineering; and the Woods Hole Oceanographic Institution), 2015. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Hydrophobic organic chemicals (HOCs) are a class of environmental contaminants responsible for numerous acute and chronic health effects in humans and wildlife. This thesis illustrates three applications of polyethylene (PE) passive sampling, which enhance our toolbox for estimating environmental hazards associated with HOCs. First, we present a methodology that can be used to estimate the bioaccumulation potential of numerous organic chemicals based on passive sampling and comprehensive two dimensional gas chromatography (GC x GC). Using GC x GC retention times, we show that lipid-water and samplerwater partition coefficients can be estimated within a factor of 2 and 3, respectively. The method was then applied to estimate body burdens of various HOCs in benthic organisms from GC x GC analysis of PE equilibrated with contaminated sediment. Empirical observations of accumulation in the Nereis virens polychaete were in good agreement with PE-based predictions for PCBs, but were lower by at least an order of magnitude for other classes of HOCs (such as PAHs) presumably due to metabolism. Second, we applied the same methodology to a set of contaminated sediments and estimated the cumulative baseline toxicity associated with environmental mixtures of HOCs. The predictions were compared against empirical measurements of baseline toxicity using the water flea Daphnia magna. The estimated total body burdens of HOCs were in good agreement with measured toxicity, with toxicity occurring at body burdens larger than 30 mg/gipid. In contrast, the toxicity estimated based on priority pollutants severely underestimated the observed toxicity, emphasizing the importance of cumulative effects. Lastly, to advance our understanding of the processes that affect passive sampling results in situ (when they are operating away from equilibrium), a mathematical model was developed for reactive chemicals transferring between PE and sediment beds. The reaction diffusion model was used to infer in situ degradation rates of dichlorodiphenyltrichloroethane (DDT), which in the sediments of a freshwater lake were found to be between 0.09 and 0.9 d-1. A second mathematical model describing the kinetics of exchange between passive samplers and water was also developed, which can be used in both field (infinite baths) and laboratory (finite baths) conditions. / by Alexandra Patricia Tcaciuc. / Ph. D.

Thesis: Ph. D., Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2017. / Cataloged from PDF version of thesis. / Includes bibliographical references (pages 169-190). / Terrestrial organic carbon (OC) erosion, remineralization, transport through river networks, and burial in marine sediments is a major pathway of the global carbon cycle. However, our ability to constrain these processes and fluxes is largely limited by (i) analytical capability and (ii) temporal sampling resolution. To address issue (i), here I discuss methodological advancements and data analysis techniques for the Ramped PyrOx serial oxidation isotope method developed at WHOI. Ramped-temperature pyrolysis/oxidation coupled with the stable carbon (¹²C, ¹³C) and radiocarbon (¹⁴C) analysis of evolved CO₂ is a promising tool for understanding and separating complex OC mixtures. To quantitatively investigate distributions of OC source, reservoir age, and chemical structure contained within a single sample, I developed a kinetic model linking RPO-derived activation energy, ¹³C composition, and radiocarbon content. This tool provides a novel method to fundamentally address the unknown relationship between OC remineralization rates and chemical structure in various environmental settings. To address issue (ii), I additionally present results from time-series sample sets collected on two end-member systems: the Congo River (Central Africa) and the LiWu River (Taiwan). For the Congo River, bulk and plant-wax-lipid ¹³C compositions indicate that a majority of particulate OC is consistently derived from downstream, C₃-dominated rainforest ecosystems. Furthermore, bulk radiocarbon content and microbial lipid molecular distributions are strongly correlated with discharge, suggesting that pre-aged, swamp-forest-derived soils are preferentially exported when northern hemisphere discharge is highest. Combined, these results provide insight into the relationship between hydrological processes and fluvial carbon export. Lastly, I examined the processes controlling carbon source and flux in a set of soils and time-series fluvial sediments from the LiWu River catchment located in Taiwan. A comparison between bedrock and soil OC content reveals that soils can contain significantly less carbon than the underlying bedrock, suggesting that this material is remineralized to CO₂ prior to soil formation. Both the presence of bacterial lipids and a shift toward lower activation energy of ¹⁴C-free OC contained in soil saprolite layers indicate that this process is microbially mediated and that microbial respiration of rock-derived OC likely represents a larger geochemical flux than previously thought. The results presented in this thesis therefore provide novel insight into the role of rivers in the global carbon cycle as well as their response to environmental perturbations. / by Jordon Dennis Hemingway / Ph. D.

Thesis (Ph. D.)--Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2007. / Includes bibliographical references. / A 225-year old coral from the south shore of Bermuda (64°W, 320N) provides a record of decadal-to-centennial scale climate variability. The coral was collected live, and sub-annual density bands seen in x-radiographs delineate cold and warm seasons allowing for precise dating. Coral skeletons incorporate strontium (Sr) and calcium (Ca) in relative proportions inversely to the sea surface temperature (SST) in which the skeleton is secreted. [Delta]180 of the coral skeleton changes based on both temperature and the [delta]180 of sea water ([delta]Ow), and 6Ow is proportional to sea surface salinity (SSS). Understanding long-term climate variability requires the reconstruction of key climate parameters, such as sea surface temperature (SST) and salinity, in records extending beyond the relatively short instrumental period. The high accretion rates, longevity, and skeletal growth bands found in coral skeletons make them an ideal resource for well-dated, seasonal climate reconstructions. Growing between 2 and 6 mm/year and reaching more than im in length, slow-growing corals provide multi-century records from one colony. Additionally, unlike the fast growing (10-20 mm/year) species Porites, slow-growing species are generally found in both tropical and sub-tropical locations greatly expanding the geographical location of these records. A high resolution record (HRR, ~11 samples per year) was drilled for the entire length of the coral record (218 years). Samples were split and Sr/Ca, [delta]180, and [delta]13C were measured for each sample. Sr/Ca was used to reconstruct winter time and mean-annual SST. Oxygen isotopic measurements were used to determine directional salinity changes, in conjunction with Sr/Ca based SST reconstructions. / (cont.) Winter-time and mean annual SSTs show SSTs -1.5 'C colder during the end of the Little Ice Age (LIA) relative to today. Simultaneously, SSS is fresher during that time. Sr/Ca based climate reconstructions from coral skeletons have been met with some skepticism because some reconstructions show temperature changes back in time that are 2-4 times greater than the reconstructions of other marine proxies. In this study, we show that when using bulk-sampled, slow-growing corals, two steps are critical to producing accurate reconstructions: 1) incorporating growth rate into multi-variant regressions with SST and Sr/Ca and 2) using multiple colonies that grew at the same time with varying average growth rates and Sr/Ca. Application of these novel methods over the period of the instrumental record from Hydrostation S (monthly since 1954, 32°10'N, 64°30'W) reduces the root mean square of the residuals between the reconstructed SST and the instrumental SST by as much as 1.52'C to 0.460C for three coral colonies. Winter-time SSTs at Bermuda are correlated to phases of the North Atlantic Oscillation (NAO), a meridional oscillation in atmospheric mass. Much uncertainty remains about the relationship between the NAO and the ocean, and one critical outstanding question is whether anthropogenic changes are perturbing the system. Using winter Sr/Ca as a proxy for temperature, we show strong coherence to the NAO at multi-decadal and inter-annual frequencies. These coral records show significant changes in variance in the NAO during the late 20th century compared to the cooler LIA, but limited changes in the mean phase (positive or negative) of the NAO, implying that climate change may be pushing the NAO to extremes but not to a new mean position. / by Nathalie Fairbank Goodkin. / Ph.D.

Thesis: Ph. D., Joint Program in Chemical Oceanography (Massachusetts Institute of Technology, Department of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 2014. / Cataloged from PDF version of thesis. / Includes bibliographical references. / Marine particles include all living and non-living solid components of seawater, representing an extremely dynamic and chemically diverse mixture of phases. The distributions of these phases are poorly constrained and undersampled in the oceans, despite interactions between living organisms and non-living minerals having central roles within many globally relevant biogeochemical processes. Through a combination of method development, basin-scale particulate collection and analyses, modeling, and field experiments, this thesis examines both the distributions of marine particulate trace metals and the underlying processes-inputs, scavenging, vertical and horizontal transport, and biotic uptake-in which marine particles participate. I first present the results of an intercalibration exercise among several US laboratories that analyzed filtered particles on shared polyethersulfone filters. We use inter-lab and intra-lab total elemental recoveries of these particles to determine our state of our intercalibration (</= 21% one-sigma inter-lab uncertainty for most elements; 9% intra-lab) and to identify means of future improvement. We also present a new chemical method for complete dissolution of polyethersulfone filters and compare it to other total particle digestion procedures. I then present the marine particulate distributions of the lithogenic elements Al, Fe, and Ti in the North Atlantic GEOTRACES section. Inputs of lithogenic particles from African dust sources, hydrothermal systems, benthic nepheloid layers and laterally-sourced margin influences are observed and discussed. Lithogenic particle residence times, size-fractionation patterns, Ti-mineral speciation, and relationships to biological aggregation processes are calculated and described. A one-dimensional, size-fractionated, multi-box model that describes lithogenic particle distributions is also proposed and its parameter sensitivities and potential implications are discussed. The thesis concludes with the presentation of results from a series of bottle incubations in naturally iron-limited waters using isotopically labeled Fe-minerals. We demonstrate both biotic and abiotic solubilization of the minerals ferrihydrite and fayalite via transfer of isotopic label into suspended particles. These results are the first of their kind to demonstrate that minerals can be a source of bioavailable iron to euphotic communities and that spatial and ecological variations in mineral Fe-bioavailability may exist. / by Daniel Chester Ohnemus. / Ph. D.

Thesis (Ph.D.)--Massachusetts Institute of Technology, Dept. of Earth and Planetary Science, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND LINDGREN / Bibliography: leaves 269-280. / by Marjorie Styrt Goldfarb. / Ph.D.

The global ocean currently absorbs over a third of anthropogenic carbon dioxide (CO₂) emissions, slowing down the growth of atmospheric CO₂, and thus moderating climate change. However, there is significant variability in the strength of the ocean carbon sink on interannual to decadal timescales. There are also uncertainties in the ocean carbon sink, a source of which lies in the coastal ocean. Coastal carbon fluxes are globally relevant and highly variable, but due to the paucity of observations, the coastal ocean remains largely unconstrained. Quantifying and understanding the variability of the ocean carbon sink, and constraining its uncertainties, is essential for supporting climate policy and predicting how the ocean will continue to moderate climate change in the future. This is challenging due to the complex physical and biogeochemical processes in the ocean, as well as the limited observations of ocean carbon. The goal of this thesis is to contribute to the understanding of the ocean carbon cycle and its variability with observations of CO₂ fluxes in the coastal ocean (Chapter 2), a multi-model study of surface carbon interannual variability (Chapter 3), and a mechanistic investigation of decadal variability of air-sea CO₂ fluxes in the global ocean (Chapter 4). (Chapter 2) Jamaica Bay is a hypereutrophic coastal urban estuary within the land-ocean aquatic continuum. Anthropogenic perturbations to the carbon cycle of the continuum are often excluded from global carbon budgets. Studies have shown that not accounting for the lateral transport of anthropogenic carbon through the continuum can lead to an overestimation of land carbon sinks and an underestimation of ocean carbon sinks. In this study, we used the direct covariance method to make direct estimates of CO₂ fluxes in Jamaica Bay. Over a 587-day observational study, Jamaica Bay emitted CO₂ to the atmosphere at an average rate of 130 gC/m2/yr. However, we find that the waters within the estuary are a strong CO₂ sink (-170 gC/m2/yr). Thus, on average, air-water CO₂ fluxes damp estuary emissions. We find that the water CO₂ sink is strongest in the summer due to the growth of intense algal blooms which likely drawdown CO₂ via photosynthesis. Although the direction of air-water CO₂ flux is ultimately a function of surface carbon concentrations, we find that in the summer, sea-breeze is a near-daily forcing agent for air-water CO₂ fluxes, contributing up to 43% of the mean summer water CO₂ sink rate. (Chapter 3) The El Nino-Southern Oscillation (ENSO) in the equatorial Pacific is the dominant mode of global air-sea CO₂ flux interannual variability (IAV). Air-sea CO2 fluxes are driven by the difference between atmospheric and surface ocean pCO₂, with variability of the latter driving flux variability. Previous studies found that models in Coupled Model Intercomparison Project Phase 5 (CMIP5) failed to reproduce the observed ENSO-related pattern of CO₂ fluxes and had weak pCO₂ IAV, which were explained by both weak upwelling IAV and weak mean vertical DIC gradients. We assess whether the latest generation of CMIP6 models can reproduce equatorial Pacific pCO₂ IAV by validating models against observations-based data products. We decompose pCO₂ IAV into thermally and non-thermally driven anomalies to examine the balance between these competing anomalies, which explain the total pCO₂ IAV. The majority of CMIP6 models underestimate pCO₂ IAV, while they overestimate SST IAV. Insufficient compensation of non-thermal pCO₂ to thermal pCO₂ IAV in models results in weak total pCO₂ IAV. We compare the relative strengths of the vertical transport of temperature and DIC and evaluate their contributions to thermal and non-thermal pCO₂ anomalies. Model-to-observations-based product comparisons reveal that modeled mean vertical DIC gradients are biased weak relative to their mean vertical temperature gradients, but upwelling acting on these gradients is insufficient to explain the relative magnitudes of thermal and non-thermal pCO₂ anomalies. (Chapter 4) The ocean carbon sink has absorbed about 25% of anthropogenic emissions, thus mitigating the effects of climate change. Over time, the ocean carbon sink has grown almost proportionally with the growth of atmospheric CO₂ concentrations. However, natural variability in the ocean carbon sink combined with large uncertainties, makes it hard to distinguish changes in the ocean sink due to natural variability versus the forced-trend. Thus, there is a need to understand and quantify the variability in the ocean carbon sink. Using the LDEO-Hybrid Physics Data product (1959-2020), we assess the decadal variability of global air-sea CO₂ fluxes. Here, we compare regional contributions to the decadal variability of the global ocean carbon sink and evaluate global patterns of decadal changes to elucidate the mechanisms that drive the dominant mode of global air-sea CO₂ flux decadal variability. We find that the dominant mode of decadal air-sea CO₂ flux variability exhibits strong synchronous signals over the tropical Pacific and Southern Ocean. We suggest that the synchronicity between the tropical Pacific and the Southern Ocean is modulated by the Pacific Decadal Oscillation (PDO) index, which is connected to the Multivariate ENSO Index (MEI). The composite patterns over the tropical Pacific can be explained by ENSO-like mechanisms operating on the decadal timescale, while the composite patterns over the Southern Ocean show a different regime where the westerly winds weakened over the composite period, the mixed layer shoaled, and the Southern Ocean sink weakened. Using a box model, we show that this reduction in mixed layer entrainment drives an accumulation of DIC in the mixed layer, which, when amplified by the high Revelle factor in the Southern Ocean, results in a 14-fold amplification in the surface pCO₂, reducing the ocean's capacity to uptake CO₂.

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Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Earth and Planetary Science, 1979. / Microfiche copy available in Archives and Science. / Bibliography: leaves 68-71. / by Sarah S. Huested. / M.S.

Thesis: Ph. D., Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Department of Civil and Environmental Engineering; and the Woods Hole Oceanographic Institution), 2013. / Pages 181 and 182 blank. Cataloged from PDF version of thesis. / Includes bibliographical references. / Steroidal estrogens are potent endocrine disrupting chemicals that are naturally excreted by vertebrates (e.g., humans and fish) and can enter natural waters through the discharge of treated and raw sewage. Because estrogens are detrimental to aquatic organisms at picomolar concentrations, many studies have measured so-called "free" estrogen concentrations in wastewater effluents, rivers, and lakes. Yet, to our knowledge, no studies have characterized the broader range of estrogens that includes free, conjugated, and halogenated forms. Conjugated estrogens are important because they can be easily converted to potent free forms by bacteria in wastewater treatment plants and receiving waters. And halogenated estrogens, produced during wastewater disinfection, are only slightly less potent than free estrogens but much more likely to bioaccumulate. We have developed a tandem mass spectrometry method that is capable of simultaneously quantifying free, conjugated, and halogenated estrogens at picomolar levels in wastewater effluent and coastal seawater. The method was validated using treated effluent from the greater Boston metropolitan area, where we found that halogenated estrogens represented over 50 % of the total estrogen discharge flux. A kinetic model of estrogen halogenation was used to predict the distribution of free and halogenated forms in wastewater effluent and suggested that chlorinated estrogens may be formed en route to the wastewater treatment plant. In the receiving waters of Massachusetts Bay, we detected a range of conjugated, free, and halogenated forms at concentrations that were well-predicted by dilution near the sewage outfall. Farther downstream, we found significantly higher estrone concentrations which points to large inputs of estrogens from sources other than sewage. Finally, we have used compound-specific measurements of 13C and 14C in commercial and pharmaceutical estrogen preparations to evaluate the potential for using carbon isotopes to distinguish between synthetic and endogenous steroids in wastewater and other environmental matrices. Our results show that synthetic estrogens and progestogens exhibit significantly depleted [delta]13 C values (~30 0/00) compared to endogenous steroids (-16 0/00 to -26 0/00). This isotopic difference should make it possible to apportion synthetic and endogenous hormone sources in complex environments. / by David R. Griffith. / Ph. D.