Earth Sciences Commons^™

Unraveling Sources Of Cyanate In The Marine Environment: Insights From Cyanate Distributions And Production During The Photochemical Degradation Of Dissolved Organic Matter, Rui Wang, Jihua Liu, Yongle Xu, Li Liu, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Cyanate is a nitrogen and energy source for diverse marine microorganisms, playing important roles in the nitrogen cycle. Despite the extensive research on cyanate utilization, the sources of this nitrogen compound remain largely enigmatic. To unravel the sources of cyanate, distributions and production of cyanate during photochemical degradation of natural dissolved organic matter (DOM) were investigated across various environments, including freshwater, estuarine, coastal areas in Florida, and the continental and slope regions of the North American mid-Atlantic Ocean (NATL). Cyanate production was also examined during the photochemical degradation of exudates from a typical strain of Synechococcus, an important phytoplankton …

Potentially Massive And Global Non-Pyrogenic Production Of Condensed "Black" Carbon Through Biomass Oxidation, Aleksandar I. Goranov, Hongmei Chen, Jianshu Duan, Satish C. B. Myneni, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

With the increased occurrences of wildfires worldwide, there has been an increase in scientific interest surrounding the chemistry of fire-derived "black" carbon (BC). Traditionally, wildfire research has assumed that condensed aromatic carbon (ConAC) is exclusively produced via combustion, and thus, ConAC is equated to BC. However, the lack of correlations between ConAC in soils or rivers and wildfire history suggests that ConAC may be produced non-pyrogenically. Here, we show quantitative evidence that this occurs during the oxidation of biomass with environmentally ubiquitous hydroxyl radicals. Pine wood boards exposed to iron nails and natural weather conditions for 12 years yielded a …

Molecular Evidence For The Export Of Terrigenous Organic Matter To The North Gulf Of Mexico By Solid-State 13C Nmr And Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Of Humic Acids, Sarah Ann Ware

Chemistry & Biochemistry Theses & Dissertations

Marine organic matter is mainly believed to originate from autochthonous organic matter, while terrigenous organic matter is assumed to be largely degraded prior to reaching the open ocean or more recently replaced by marine organic matter via a stripping process. Sediment samples along a transect extending from the Mississippi River Birdsfoot Delta to the Mississippi Canyon on the Louisiana continental shelf were examined by advanced analytical techniques, electrospray ionization coupled to a 12T Fourier transform ion cyclotron resonance mass spectrometer (ESI-FTICR-MS) and quantitative solid-state multiple cross polarization magic angle spinning (multi-CPMAS) ¹³C NMR in an effort to understand the …

Systemic Analyses Of Radiocarbon Ages Of Coexisting Planktonic Foraminifera, Jörg Lippold, Julia Gottschalk, Jean Lynch-Stieglitz, Matthew W. Schmidt, Sönke Szidat, Andre Bahr

OES Faculty Publications

We compare radiocarbon (¹⁴C) ages of coexisting planktonic foraminifera species from sediment cores VM12-107 and KNR166-2-26JPC from the Equatorial Atlantic Ocean for three time periods (Holocene, Heinrich Stadial 1, last glacial maximum). We find a maximum inter-species difference of 1200 ¹⁴C yr. On average, the ¹⁴C ages deviate by ∼300 yr between Globigerinoides ruber and other species. In most cases, this exceeds the analytical uncertainty range of the measurements and thus renders the choice of species for generating age models as important as sample weight. While modern stratified water-column profiles imply an increase in ¹⁴C …

Authigenic Iron Is A Significant Component Of Oceanic Labile Particulate Iron Inventories, Laura E. Sofen, Olga A. Antipova, Kristen N. Buck, Salvatore Caprara, Lauren Chacho, Rodney J. Johnson, Gabriella Kim, Peter Morton, Daniel C. Ohnemus, Sara Rauschenberg, Peter N. Sedwick, Alessandro Tagliabue, Benjamin S. Twining

OES Faculty Publications

Particulate phases transport trace metals (TM) and thereby exert a major control on TM distribution in the ocean. Particulate TMs can be classified by their origin as lithogenic (crustal material), biogenic (cellular), or authigenic (formed in situ), but distinguishing these fractions analytically in field samples is a challenge often addressed using operational definitions and assumptions. These different phases require accurate characterization because they have distinct roles in the biogeochemical iron cycle. Particles collected from the upper 2,000 m of the northwest subtropical Atlantic Ocean over four seasonal cruises throughout 2019 were digested with a chemical leach to operationally distinguish labile …

Interactions Of Bioactive Trace Metals In Shipboard Southern Ocean Incubation Experiments, Shannon M. Burns, Randelle M. Bundy, William Abbott, Zuzanna Abdala, Alexa R. Sterling, P. Dreux Chappell, Bethany D. Jenkins, Kristen N. Buck

OES Faculty Publications

In the Southern Ocean, it is well‐known that iron (Fe) limits phytoplankton growth. Yet, other trace metals can also affect phytoplankton physiology. This study investigated feedbacks between phytoplankton growth and dissolved Fe, manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), and cadmium (Cd) concentrations in Southern Ocean shipboard incubations. Three experiments were conducted in September–October 2016 near the West Antarctic Peninsula: Incubations 1 and 3 offshore in the Antarctic Circumpolar Current, and Incubation 2 inshore in Bransfield Strait. Additions of Fe and/or vitamin B₁₂ to inshore and offshore waters were employed and allowed assessment of metal (M) …

Abiotic Stress Mitigation: A Case Study From 21 Trials Using A Natural Organic Matter Based Biostimulant Across Multiple Geographies, Rachel L. Sleighter, Terry Hanson, David Holden, Kristen M. Richards

Chemistry & Biochemistry Faculty Publications

Crop productivity and yields can be greatly diminished by abiotic stress events including drought, extreme temperatures, excess moisture, and saline irrigation water. Multiple stressors occurring simultaneously can further exacerbate the strain on plants. Various types of biostimulants have been shown to mitigate abiotic stress and here, the results of 21 trials on corn, wheat, soybean, and various high-value crops are discussed in the context of the abiotic stress that either occurred naturally or was experimentally induced. Treatments in these trials included stressed and non-stressed plants, as well as either an untreated control or grower standard fertilizer applications alone and in …

Insights Into The Deglacial Variability Of Phytoplankton Community Structure In The Eastern Equatorial Pacific Ocean Using [231Pa/230Th]Xs And Opal-Carbonate Fluxes, Danielle Schimmenti, Franco Marcantonio, Christopher T. Hayes, Jennifer Hertzberg, Matthew Schmidt, John Sarao

OES Faculty Publications

Fully and accurately reconstructing changes in oceanic productivity and carbon export and their controls is critical to determining the efficiency of the biological pump and its role in the global carbon cycle through time, particularly in modern CO₂ source regions like the eastern equatorial Pacific (EEP). Here we present new high-resolution records of sedimentary ²³⁰Th-normalized opal and nannofossil carbonate fluxes and [²³¹Pa/²³⁰Th]xs ratios from site MV1014-02-17JC in the Panama Basin. We find that, across the last deglaciation, phytoplankton community structure is driven by changing patterns of nutrient (nitrate, iron, and silica) availability which, in …

Application Of Chemostratigraphic Methods To Floodplain Alluvial Deposits Within The Big Harris Creek Basin, North Carolina, Samantha N. Sullivan, Jerry R. Miller, Carmen L. Huffman

Chemistry & Biochemistry Faculty Publications

Big Harris Creek, North Carolina, possesses a geomorphic history and alluvial stratigraphic record similar to many drainages in southern Appalachian Piedmont. An approximately 1 km reach of Upper Stick Elliott Creek, a tributary to Big Harris Creek, was used herein to (1) explore the use of chemostratigraphic methods to define and correlate late Holocene alluvial deposits along this relatively uncontaminated rural stream containing legacy sediments (historic, anthropogenically derived deposits), and (2) interpret depositional floodplain processes within small (<10 km²), headwater drainages. The lithofacies within four floodplain sections were described in channel banks and sampled at about 5 cm intervals. …

Stratospheric Aerosol Composition Observed By The Atmospheric Chemistry Experiment Following The 2019 Raikoke Eruption, Chris D. Boone, Peter F. Bernath, Keith Labelle, Jeff Crouse

Chemistry & Biochemistry Faculty Publications

Infrared aerosol spectra derived from Atmospheric Chemistry Experiment measurements following the June 2019 Raikoke volcanic eruption are used to evaluate the composition of stratospheric aerosols in the Arctic. A blanket of aerosols, spanning an altitude range from the tropopause (8–11 km) to 20 km, persisted in the stratosphere over northern latitudes for many months. The aerosols within this blanket were almost exclusively sulfates. The percentage of sulfuric acid in the aerosols decreased over time, dropping below 50% H₂SO₄ concentration at some altitudes by March 2020. Contrary to previous reports, the aerosol blanket was not comprised of smoke …

Radium Isotopes As Submarine Groundwater Discharge (Sgd) Tracers: Review And Recommendations, J. Garcia-Orellana, V. Rodellas, Joseph Tamborski, M. Diego-Feliu, P. Van Beek, Y. Weinstein, M. Charette, A. Alorda-Kleinglass, H.A. Michael, T. Stieglitz, J. Scholten

OES Faculty Publications

Submarine groundwater discharge (SGD) is now recognized as an important process of the hydrological cycle worldwide and plays a major role as a conveyor of dissolved compounds to the ocean. Naturally occurring radium isotopes (Ra-223, Ra-224, Ra-226 and Ra-228) are widely employed geochemical tracers in marine environments. Whilst Ra isotopes were initially predominantly applied to study open ocean processes and fluxes across the continental margins, their most common application in the marine environment has undoubtedly become the identification and quantification of SGD. This review focuses on the application of Ra isotopes as tracers of SGD and associated inputs of water …

Taxonomic And Nutrient Controls On Phytoplankton Iron Quotas In The Ocean, Benjamin S. Twining, Olga Antipova, P. Dreux Chappell, Natalie R. Cohen, Jeremy E. Jacquot, Elizabeth L. Mann, Adrian Marchetti, Daniel C. Ohnemus, Sara Rauschenberg, Alessandro Tagliabue

OES Faculty Publications

Phytoplankton iron contents (i.e., quotas) directly link biogeochemical cycles of iron and carbon and drive patterns of nutrient limitation, recycling, and export. Ocean biogeochemical models typically assume that iron quotas are either static or controlled by dissolved iron availability. We measured iron quotas in phytoplankton communities across nutrient gradients in the Pacific Ocean and found that quotas diverged significantly in taxon‐specific ways from laboratory‐derived predictions. Iron quotas varied 40‐fold across nutrient gradients, and nitrogen‐limitation allowed diatoms to accumulate fivefold more iron than co‐occurring flagellates even under low iron availability. Modeling indicates such “luxury” uptake is common in large regions of …

Advances In The Understanding Of Sourcing And Fate Of Pyrogenic Organic Matter In The Environment, Aleksandar Ivaylov Goranov

Chemistry & Biochemistry Theses & Dissertations

With higher occurrences of forest fires worldwide, there has been an increase in scientific interest surrounding the chemistry of pyrogenic organic matter (pyOM). The main structural components of pyOM, the condensed aromatic compounds (ConAC), exhibit intriguing physico-chemical properties and have been one of the main focuses of biogeochemical research. The overwhelmingly large number of scientific articles regarding pyOM and ConAC are guided by the assumption that ConAC in the environment are exclusively of pyrogenic origin, even though some recent studies have suggested that some of these ConAC could also be derived from non-pyrogenic radical-driven processes. To evaluate this controversial proposition, …

Structural Characterization Of Organic Matter In Oil Shales Using Multiple Nuclear Magnetic Resonance Spectroscopic Techniques, Wenying Chu

Chemistry & Biochemistry Theses & Dissertations

Oil shale is a promising source of hydrocarbon fuel that is distributed throughout the world. The petroleum generating potential of oil shale is related to the molecular structure of the organic matter in source rock. The major fraction of organic matter of oil shale is termed kerogen, and due to its insolubility in organic solvents, ¹³C solid-state nuclear magnetic resonance (NMR) spectroscopy is one of the best ways to directly measure the insoluble organic matter without changing its chemical structures. This dissertation investigated oil shale samples using advanced solid-state ¹³C NMR spectroscopy techniques and high resolution magic angle …

Soil Labile Organic Carbon Fractions And Soil Enzyme Activities After 10 Years Of Continuous Fertilization And Wheat Residue Incorporation, Ligan Zhang, Xi Chen, Yujun Xu, Mengcan Jin, Xinxin Ye, Hongjian Gao, Wenying Chu, Jingdong Mao, Michael L. Thompson

Chemistry & Biochemistry Faculty Publications

Labile organic carbon (LOC) fractions and related enzyme activities in soils are considered to be early and sensitive indicators of soil quality changes. We investigated the influences of fertilization and residue incorporation on LOC fractions, enzyme activities, and the carbon pool management index (CPMI) in a 10-year field experiment. The experiment was composed of three treatments: (1) no fertilization (control), (2) chemical fertilizer application alone (F), and (3) chemical fertilizer application combined with incorporation of wheat straw residues (F + R). Generally, the F + R treatment led to the highest concentrations of the LOC fractions. Compared to the control …

Microplastic Fragment And Fiber Contamination Of Beach Sediments From Selected Sites In Virginia And North Carolina, Usa, Gabrielle Z. Dodson, A. Katrina Shotorban, Patrick G. Hatcher, Derek Waggoner, Sutapa Ghosal, Nora Noffke

OES Faculty Publications

Microplastic particles (<5 >mm) constitute a growing pollution problem within coastal environments. This study investigated the microplastic presence of estuarine and barrier island beaches in the states of Virginia and North Carolina, USA. Seventeen sediment cores were collected at four study sites and initially tested for microplastic presence by pyrolysis-gas chromatography–mass spectrometry. For the extraction, microplastic particles were first separated from the sediment using a high-density cesium chloride solution (1.88 g/mL). In a second step, an oil extraction collected the remaining microplastic particles of higher densities. Under the light microscope, the extracted microplastic particles were classified based on their morphologies …

Measured Optical Absorption Cross Sections Of Tio, Peter Bernath

Chemistry & Biochemistry Faculty Publications

A laboratory emission spectrum of TiO in the visible and near-infrared regions (476–1176 nm) has been calibrated and corrected. High-resolution experimental absorption cross sections for TiO with natural isotopic abundance are provided at a temperature of about 2300 K. These cross sections have been compared with those derived from the ExoMol line list. The experimental cross sections can be used directly as a template for cross correlation TiO detection in hot Jupiter exoplanets.

Lipid Biomarkers Of Bering And Chukchi Sea Euphausiids And Their Application To Diet History, Rachel L. Pleuthner

OES Theses and Dissertations

In the eastern Bering Sea, Thysanoessa raschii are the most abundant krill species and a keystone trophic member that serve as both an important grazer and link to upper level consumers. In this system krill experience large annual variation in food resources, especially during ice advance and retreat; multiple lipid classes are used to temper the effects of those fluctuations, as well as to fuel reproduction and growth. Two shipboard feeding experiments that occurred during late spring and early summer of 2010, respectively, monitored the lipid retention in adult T. raschii and examined the fluctuation of specific lipid biomarkers under …

Phosgene In The Upper Troposphere And Lower Stratosphere: A Marker For Product Gas Injection Due To Chlorine-Containing Very Short Lived Substances, Jeremy J. Harrison, Martyn P. Chipperfield, Ryan Hossaini, Christopher D. Boone, Sandip Dhomse, Wuhu Feng, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Abstract: Phosgene in the atmosphere is produced via the degradation of carbon tetrachloride, methyl chloroform, and a number of chlorine‐containing very short lived substances (VSLS). These VSLS are not regulated by the Montreal Protocol even though they contribute to stratospheric ozone depletion. While observations of VSLS can quantify direct stratospheric source gas injection, observations of phosgene in the upper troposphere/lower stratosphere can be used as a marker of product gas injection of chlorine‐containing VSLS. In this work we report upper troposphere/lower stratosphere measurements of phosgene made by the ACE‐FTS (Atmospheric Chemistry Experiment Fourier Transform Spectrometer) instrument and compare with results …

Formation Of Water-Soluble Organic Matter Through Fungal Degradation Of Lignin, Seyyedhadi Khatami, Ying Deng, Ming Tien, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Lignin is a major component of decaying terrestrial vegetation in soils and has been reported to contribute substantially to the formation of soil carbon humus and associated water extracts of soil. To better understand this process of humification, lignin from brown-rot degraded wood is subjected to a white-rot fungus (Phanerochaete chrysosporium)whose enzymes are particularly effective in lignin degradation. This enzymatic attack was monitored by ultrahigh resolution mass spectrometry of water soluble extracts of the fungal cultures. The ensuing molecular level characterizations showed that the P. chrysosporium fungi induced aromatic ring oxidations followed by ring opening as expected. However, …

Advances In Amino Acid Analysis For Marine Related Matrices And Its Application To Coastal Shelf Settings In The Canadian Arctic, Rachel M. Mcmahon

OES Theses and Dissertations

Amino acids comprise up to 50% of organic matter in cellular material and are a major fraction of oceanic organic carbon. Amino acids are also considered highly labile during organic matter recycling, making them useful proxies for organic carbon cycling. Nevertheless, analysis of individual amino acids has been burdened by lengthy derivatization and complex analysis since the 1950s. In this thesis, I describe the modification of advanced analytical techniques, developed in the biomedical field, for analysis of marine matrices which allow the determination of at least 40 amino acids without the need for lengthy sample preparation and derivatization, twice the …

Production And Composition Of Pyrogenic Dissolved Organic Matter From A Logical Series Of Laboratory-Generated Chars, Kyle W. Bostick, Andrew R. Zimmerman, Andrew S. Wozniak, Siddhartha Mitra, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Though pyrogenic carbon (pyC) has been assumed to be predominantly stable, degradation and transfers of pyC between various pools have been found to influence its cycling and longevity in the environment. Dissolution via leaching may be the main control on loss processes such as microbial or abiotic oxidation, mineral sorption, or export to aquatic systems. Yet, little is known about the controls on pyrogenic dissolved organic matter (pyDOM) generation or composition. Here, the yield and composition of pyDOM generated through batch leaching of a thermal series of oak and grass biochars, as well as several non-pyrogenic reference materials, was compared …

Biogeochemical Cycling Of Selenium In The Arctic Ocean, Kyle M. Mcquiggan

OES Theses and Dissertations

Changes in the global climate may have a pronounced effect on the biogeochemical cycling of trace elements like selenium (Se) in the Arctic Ocean. This study described the first quantitative examination of the biogeochemical cycle of selenium in the Amerasian Basin, providing the baseline from which future changes can be identified. Aerosol, dissolved and particulate water samples were collected for Se determinations during the U.S. GEOTRACES GN01 Arctic expedition that sampled the two parts of the Amerasian Basin in 2015: The Makarov Basin on the way to the North Pole and the Canada Basin on the return trip to Dutch …

Surface Oxygenation Of Biochar Through Ozonization For Dramatically Enhancing Cation Exchange Capacity, Matthew D. Huff, Sarah Marshall, Haitham A. Saeed, James Weifu Lee

Chemistry & Biochemistry Faculty Publications

Background

Biochar cation exchange capacity (CEC) is a key property that is central to biochar environmental applications including the retention of soil nutrients in soil amendment and removal of certain pollutants in water-filtration applications.

Results

This study reports an innovative biochar-ozonization process that dramatically increases the CEC value of biochars by a factor of 2. The ozonized biochars also show great improvement on adsorption of methylene blue by as much as a factor of about 5. In this study, biochar samples treated with and without ozone were analyzed by means of pH and CEC assays, water field capacity measurement, elemental …

Interpreting Mosaics Of Ocean Biogeochemistry, Andrea Fassbender, A. Bourbonnais, Sophie Clayton, P. Gaube, M. Ormand, P.J.S. Franks, M. A. Altabet, D.J. Mcgillicuddy Jr.

OES Faculty Publications

Advances in technology and modeling capabilities are driving a surge in progress in our understanding of how ocean ecosystems mix and mingle on medium to small scales.

A Near-Global Atmospheric Distribution Of N2o Isotopologues, Peter F. Bernath, Mahdi Yousefi, Eric Buzan, Chris D. Boone

Chemistry & Biochemistry Faculty Publications

The distributions of the four most abundant isotopologues and isotopomers (N₂O, ¹⁵NNO, N¹⁵NO, and NN¹⁸O of nitrous oxide have been measured in the Earth's stratosphere by infrared remote sensing with the Atmospheric Chemistry Experiment (ACE) Fourier transform spectrometer. These satellite observations have provided a near-global picture of N₂O isotopic fractionation. The relative abundances of the heavier species increase with altitude and with latitude in the stratosphere as the air becomes older. The heavy isotopologues are enriched by 20-30% in the upper stratosphere and even more over the poles. These observations are …

Selenium Distribution And Cycling In The Eastern Equatorial Pacific Ocean, Zoe Wambaugh

OES Theses and Dissertations

Oxygen minimum zones in oceanic waters have become increasingly important to the marine environment and society. Low oxygen waters affect not only the distribution and abundance of marine organisms, but also impact the solubility and transport of trace elements that are of biological importance, with the chemical speciation and solubility depending on the actual redox poise of the waters. One redox sensitive trace element of interest is selenium, which can be both toxic and essential for organisms, depending on its chemical speciation. In 2013, the US GEOTRACES program completed the GP16 transect from Peru to Tahiti, going through the oxygen …

Alicyclic And Aromatic Carboxylic Acids In Soil Organic Matter: An Investigation Of Potential Origin And Association With Plutonium Using Advanced Analytical Techniques, Nicole Didonato

Chemistry & Biochemistry Theses & Dissertations

Carboxylic acids are a defining component of soil organic matter, responsible for many of the physical and chemical properties, including metal-organic matter interactions, which govern its role as an important constituent of soils. However, there is a shortage of detailed molecular level information regarding orientation and structural arrangement of carboxylic acids within soil organic matter. This dissertation utilizes electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) as well as solid-state and multi-dimensional nuclear magnetic resonance (NMR) to investigate the molecular formula composition within several organic matter sources and the primary structures that feature carboxylic acids. Soil organic matter …

New And Improved Infra-Red Absorption Cross Sections And Ace-Fts Retrievals Of Carbon Tetrachloride (Ccl4), Jeremy J. Harrison, Christopher D. Boone, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

Carbon tetrachloride (CCl₄) is one of the species regulated by the Montreal Protocol on account of its ability to deplete stratospheric ozone. As such, the inconsistency between observations of its abundance and estimated sources and sinks is an important problem requiring urgent attention (Carpenter et al., 2014) [5]. Satellite remote-sensing has a role to play, particularly limb sounders which can provide vertical profiles into the stratosphere and therefore validate stratospheric loss rates in atmospheric models. This work is in two parts. The first describes new and improved high-resolution infra-red absorption cross sections of carbon tetrachloride/dry synthetic air over …

Introducing Global Peat-Specific Temperature And Ph Calibrations Based On Brgdgt Bacterial Lipids, B.D.A. Naafs, G. N. Imglis, Y. Zheng, M. J. Amesbury, H. Biester, R. Bindler, J. Blewett, M. A. Burrows, D. Del Castillo Torres, F. M. Chambers, P. G. Hatcher

Chemistry & Biochemistry Faculty Publications

Glycerol dialkyl glycerol tetraethers (GDGTs) are membrane-spanning lipids from Bacteria and Archaea that are ubiquitous in a range of natural archives and especially abundant in peat. Previous work demonstrated that the distribution of bacterial branched GDGTs (brGDGTs) in mineral soils is correlated to environmental factors such as mean annual air temperature (MAAT) and soil pH. However, the influence of these parameters on brGDGT distributions in peat is largely unknown. Here we investigate the distribution of brGDGTs in 470 samples from 96 peatlands around the world with a broad mean annual air temperature (−8 to 27 °C) and pH (3–8) range …