Physical Sciences and Mathematics Commons^™

Abiotic Formation Of Dissolved Organic Sulfur In Anoxic Sediments Of Santa Barbara Basin, Hussain A. Abdulla, David J. Burdige, Tomoko Komada

OES Faculty Publications

Sulfurization has been found to enhance organic matter preservation and petroleum formation in marine sediments. However, we do not yet have a comprehensive understanding of sulfurization mechanisms. In this study, we investigated several possible mechanisms of dissolved organic sulfur (DOS) formation in the top 4.5 m of anoxic sediments of Santa Barbara Basin (SBB), California Borderland. Using Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS), we identified chemical formulas of potential dissolved organic matter (DOM) precursors to these DOS compounds. We also examined how the formulas of abiotically formed DOS changed as a function of depth across a major redox …

Spectroscopic Characterization Of Oceanic Dissolved Organic Matter Isolated By Reverse Osmosis Coupled With Electrodialysis, John R. Helms, Jingdong Mao, Hongmei Chen, E. Michael Perdue, Nelson W. Green, Patrick G. Hatcher, Kenneth Mopper, Aron Stubbins

Chemistry & Biochemistry Faculty Publications

Oceanic dissolved organic matter (DOM) is one of the largest pools of reduced carbon on Earth, yet DOM remains poorly chemically characterized. Studies to determine the chemical nature of oceanic DOM have been impeded by the lack of efficient and non-fractioning methods to recover oceanic DOM. Here, a DOM fraction (~40 to 86% recovery) was isolated using reverse osmosis/electrodialysis (RO/ED) and analyzed by solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Samples were obtained from biogeochemically distinct environments: photobleached surface gyre, productive coastal upwelling zone, oxygen minimum, North Atlantic Deep Water, and North Pacific Deep Water. A ubiquitous ‘background’ refractory …

Spectroscopic Characterization Of Dissolved Organic Matter: Insights Into Composition, Photochemical Transformation And Carbon Cycling, John Robert Helms

Chemistry & Biochemistry Theses & Dissertations

This dissertation explores processes affecting the composition of dissolved organic matter (DOM) and how DOM composition changes in sunlit surface waters and in the dark interior ocean. Simulated solar irradiations were used to investigate the impact of photochemistry on terrestrial waters and deep ocean DOM. The photochemically mediated processes observed in Dismal Swamp samples included (i) light induced flocculation of up to 12% of the organic matter and 84% of the dissolved iron originally present; (ii) 74-88% mineralization of dissolved organic carbon (DOC) and 95-99% bleaching of chromophoric DOM (CDOM) during 110 days of irradiation; and (iii) nearly complete loss …

A Mini-Electrodialysis System For Desalting Small Volume Saline Samples For Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, Hongmei Chen, Aron Stubbins, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

An affordable, commercially available mini-electrodialysis (mini-ED) system has been evaluated for the efficient desalting of small volume samples of seawater before analysis by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). Mini-ED FT-ICR mass spectra were compared with spectra for samples that were treated by C₁₈ solid phase extraction, a commonly used method for rapid sample preparation for this type of analysis. In this comparison, it is clear that mini-ED provides more representative molecular information, compared with C₁₈ isolation, and recovers the overwhelming majority of peaks from salt-free samples, indicating that it adequately represents the …

Oxygen Isotopes As A Tracer Of Dom Processes In River-Estuary Systems, Joy Ashley Matthews

OES Theses and Dissertations

In the biogeochemical study of dissolved organic matter (DOM) in natural waters, stable isotopes are used to provide insight into both the sources of DOM and the processes affecting its alteration. Through the research presented here, oxygen isotopes are incorporated into the study of DOM through the adaptation of a pyrolysis elemental analysis isotope ratio mass spectrometer method, and sample preparation using two-stage ultrafiltration.

The application of oxygen isotopes to the study of DOM is demonstrated in two studies. First, natural abundance of δ¹⁸O in DOM is explored in the Delaware estuary. Using a two end-member mixing model, …

Reactivity And Chemical Characterization Of Dissolved Organic Matter In An Estuary, Hussain A. Abdulla

OES Theses and Dissertations

This dissertation used Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (¹³C-NMR) data to quantify the changes of major chemical compound classes in high molecular weight (HMW, >1kDa) DOM isolated along a transect from Great Dismal Swamp through the Elizabeth River/Chesapeake Bay system to the coastal Atlantic Ocean off Virginia, USA. Results show that both carboxylic acids and aromatic compounds are lost along the transect, while amide, and carbohydrate moieties could have a mid-transect source.

Addressing the seasonal and spatial changes in the chemical composition of high molecular weight DOM using C/N ratio and δ^{13 …}

Export Of Terrestrial Dissolved Organic Matter Along A River To Ocean Transect Of The Lower Chesapeake Bay Investigated By Advanced Analytical Techniques, Rachel Leigh Sleighter

Chemistry & Biochemistry Theses & Dissertations

Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proved essential for the complete separation of the thousands of peaks present in natural organic matter (NOM), a complex assemblage of organic molecules present in water, soils, and sediments. An improved understanding of its composition is crucial to understand how pollutants interact with NOM and how NOM cycles through global carbon cycles.

Optimizing the acquisition and handling of the FTICR mass spectra is the first step to obtaining high quality data. A simple method to internally calibrate the peaks in the complex spectra, using naturally present fatty …

The Observation, Modeling, And Retrieval Of Bio-Optical Properties For Coastal Waters Of The Southern Chesapeake Bay, Xiaoju Pan

OES Theses and Dissertations

The primary purpose of this study was to develop an inverse method to retrieve the inherent optical properties (IOPs) and biogeochemical parameters (e.g. chlorophyll a concentration and salinity) appropriate to monitor the water quality and biogeochemical processes from remote sensing of the coastal waters in the southern Chesapeake Bay and coastal Mid-Atlantic Bight region (MAB) dominated by Case 2 waters. For this purpose, knowledge of the relationship between remote sensing reflectance (R_rs) and IOPs and the effect from bottom reflectance on R_rs, is required.

A substantial investigation of IOPs has been conducted for the coastal …

Red And Black Tides: Quantitative Analysis Of Water-Leaving Radiance And Perceived Color For Phytoplankton, Colored Dissolved Organic Matter, And Suspended Sediments, Heidi M. Dierssen, Raphael M. Kudela, John P. Ryan, Richard C. Zimmerman

OES Faculty Publications

Using field measurements and quantitative modeling, we demonstrate that red coloration of the sea surface is not associated with any particular group of phytoplankton and is strongly dependent on the physiology of the human visual system. Red or brown surface waters can be produced by high concentrations of most types of algae, colored dissolved organic matter, or suspended sediment. Even though light reflected by red tides commonly peaks in the yellow spectral region (570–580 nm), human color perception requires consideration of the entire spectrum of light relative to receptors within the human eye. The color shift from green to red …

Open-Ocean Carbon Monoxide Photoproduction, Aron Stubbins, Günther Uher, Cliff S. Law, Kenneth Mopper, Carol Robinson, Robert C. Upstill-Goddard

Chemistry & Biochemistry Faculty Publications

Sunlight-initiated photolysis of chromophoric dissolved organic matter (CDOM) is the dominant source of carbon monoxide (CO) in the open-ocean. A modelling study was conducted to constrain this source. Spectral solar irradiance was obtained from two models (GCSOLAR and SMARTS2). Water-column CDOM and total light absorption were modelled using spectra collected along a Meridional transect of the Atlantic ocean using a 200-cm pathlength liquid waveguide UV-visible spectrophotometer. Apparent quantum yields for the production of CO (AQY_CO) from CDOM were obtained from a parameterisation describing the relationship between CDOM light absorption coefficient and AQY_CO and the CDOM spectra collected. …

Black Carbon In Estuarine And Coastal Ocean Dissolved Organic Matter, Antonio Mannino, H. Rodger Harvey

OES Faculty Publications

We measured black carbon (BC) in ultrafiltered, high-molecular weight dissolved organic matter (UDOM) in surface waters of Delaware Bay, Chesapeake Bay, and the adjacent Atlantic Ocean (U.S.A.) to investigate the importance of riverine and estuarine dissolved organic matter (DOM) as a source of BC to the ocean. BC was 5-72% of UDOM-C (27 ± 17%), which corresponds to 8.9 ± 6.5% of dissolved organic carbon (DOC), with higher values in the heavily urbanized midbay region of the Delaware Estuary and lower yields in the river and coastal ocean. The spatial and seasonal distributions of BC along the salinity gradient of …

An Investigation Of Dissolved Organic Matter In A Shallow Coastal Bay Subject To Aureococcus Anophagefferens Blooms, Jean-Paul Simjouw

OES Theses and Dissertations

Aureococcus anophagefferens, the pelagophyte responsible for brown tide blooms, was identified in Chincoteague Bay in 1997 and has “bloomed” there since at least 1998. Aureococcus anophagefferens is capable of using dissolved organic nitrogen (DON) and dissolved organic carbon (DOC) substrates to support growth, and this utilization is hypothesized to give the organism a competitive advantage relative to other phytoplankton when inorganic nutrient concentrations are low or depleted. Because previous studies suggest dissolved organic matter (DOM) is important in initiating and sustaining brown tide blooms, a field study of the variations in DOC concentration and DOM composition was performed at …

Biochemical Composition Of Particles And Dissolved Organic Matter Slong An Estuarine Gradient: Sources And Implications For Dom Reactivity, Antonio Mannino, H. Rodger Harvey

OES Faculty Publications

The chemical composition of high molecular weight dissolved organic matter (DOM) and particulate organic matter (POM) was examined along the salinity gradient of the Delaware Estuary. DOM was collected and fractionated by tangential-flow ultrafiltration into 1-30 kDa (HDOM; high molecular weight) and 30 kDa to 0.2 μm (VHDOM; very high molecular weight) and compared to particles collected in parallel. Polysaccharides comprised 12-43% of particulate organic carbon (POC), 30-56% of VHDOM carbon, and 7.5-19% of HDOM carbon. Hydrolyzable amino acids comprised 17-38% of POC, 5.4-12% of VHDOM carbon, and 1.5-4.2% of HDOM carbon. Only 7-43% of dissolved organic nitrogen in VHDOM …