Biogeochemistry Commons^™

Compositions And Structures Of Particulate And Colloidal Organic Matter In Aquatic Environment By Advanced Analytical Techniques, Yong Ran, Dainan Zhang, Shujie Hu, Yu Yang, Jingdong Mao

Chemistry & Biochemistry Faculty Publications

Dissolved, colloidal and particulate organic matter (DOM, COM and POM) is important in the global carbon cycle and knowledge of their sources and structures can be critical to understanding their roles in biogeochemical cycles. This study explored the sources and chemical structures of COM and POM samples from the Pearl River Basin, China by elemental, chlorophyll a (Chl a), radiocarbon and stable carbon isotopic analyses, NMR techniques, and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis. The chemical and nano-sclae structures of two ultrafiltered dissolved organic matter (UDOM) samples from surface seawater of the Pacific and Atlantic Ocean …

Compound-Specific Isotope Analysis Of Amino Acids In Biological Tissues: Applications In Forensic Entomology, Food Authentication And Soft-Biometrics In Humans, Mayara Patricia Viana De Matos

Graduate Theses, Dissertations, and Problem Reports (ETD)

In this work we demonstrate the power of compound-specific isotope analysis (CSIA) to analyze proteinaceous biological materials in three distinct forensic applications, including: 1) linking necrophagous blow flies in different life stages to their primary carrion diet; 2) identifying the harvesting area of oysters for food authentication purposes; and 3) the ability to predict biometric traits about humans from their hair.

In the first application, we measured the amino-acid-level fractionation that occurs at each major life stage of Calliphora vicina (Robineau-Desvoidy) (Diptera: Calliphoridae) blow flies. Adult blow flies oviposited on raw pork muscle, beef muscle, or chicken liver. Larvae, pupae …

Seasonal Soil Carbon Fluxes In Transitioning Agricultural Soils In Central Washington State: Relations To Land-Use, Environmental Factors And Soil Carbon-Nitrogen Characteristics, Brandon Kautzman

All Master's Theses

Changing agricultural land-use practices to increase soil carbon sequestration contributes to climate change mitigation and improved food security by moving CO₂ from the atmosphere into soil as soil organic carbon (SOC). In 2016, a farm in Thorp, Washington, Spoon Full Farm, began converting land historically farmed using conventional methods of tillage and synthetic fertilizers to conservation farming methods with direct seeding and organic soil amendments with a goal of sequestering carbon in the soil. This project evaluates relationships of soil CO₂ respiration and net ecological exchange (NEE) with land-use types, seasonal environmental factors (air temperature, relative humidity, soil …

Are The Oxygen Isotope Values Of The Late Cretaceous Western Interior Seaway Different From The Open Ocean?, Camille H. Dwyer, Corinne Myers, Viorel Atudorei

Shared Knowledge Conference

The Western Interior Seaway (WIS) was a North American epicontinental sea that was connected to the open ocean through the passage of the northern Boreal Sea and the southern Tethys Sea from the early Albian (~113 million years ago) to the early Paleogene (~65 million years ago). The WIS began to recced and lost its connection to the southern Tethys Sea in the late Campanian (~72 million years ago). In the early Paleogene, the WIS dried up completely. The oxygen isotopic composition (δ18O) of benthic bivalves was measured from the upper Campanian and lower Maastrichtian (75 million years ago to …

High-Dimensional Isotope Relationships, Yuyang He

LSU Doctoral Dissertations

High-dimensional isotope relationships describes the relationships of two or more element or position-specific (PS) elements in the same molecule or ion. It provides us more powerful tools to study reaction mechanisms and dynamics. Chapter 1 is about dual or multiple stable isotope relationship on δ-δ (or δ'-δ') space. While temporal data sampled from a closed-system can be treated by a Rayleigh Distillation Model (RDM), spatial data should be treated by a Reaction-Transport Model (RTM). Here we compare the results of a closed-system RDM to a RTM for systems with diffusional mass transfer by simulating the trajectories on nitrate's δ'^{18 …}

Predicting Spatial Patterns In Precipitation Isotope (Δ2h And Δ18o) Seasonality Using Sinusoidal Isoscapes, Scott T. Allen, James W. Kirchner, Gregory R. Goldsmith

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Understanding how precipitation isotopes vary spatially and temporally is important for tracer applications. We tested how well month‐to‐month variations in precipitation δ18O and δ2H were captured by sinusoidal cycles, and how well spatial variations in these seasonal cycles could be predicted, across Switzerland. Sine functions representing seasonal cycles in precipitation isotopes explained between 47% and 94% of the variance in monthly δ18O and δ2H values at each monitoring site. A significant sinusoidal cycle was also observed in line‐conditioned excess. We interpolated the amplitudes, phases, and offsets of these sine functions across the landscape, using multiple linear …

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 …

Stable Bromine Isotope Signature Of Bromoform From Enzymatic And Abiotic Formation Pathways And Its Application In Identifying Sources Of Environmental Bromoform In The Damariscotta River, Chengyang Wang

Honors Theses

Bromoform is a major source of atmospheric bromine. Most bromoform is produced by marine organisms including macroalgae and phytoplankton, using the enzyme bromoperoxidase (BPO). Bromoform can also be a byproduct of industrial processes such as water disinfection. Identifying sources of environmental bromoform is still a challenge. A novel technique of using quadrupole mass spectrometry coupled to a gas chromatography (GCqMS) was developed and optimized for Br isotope analyses. The study shows that GCqMS in single ion monitoring (SIM) mode can measure 81Br with precision of around ±0.7‰ (60pmol bromoform injected). This study aims to investigate stable Br isotopes of bromoform …

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.

Geostatistical And Geospatial Distribution Of Multiple Metallic Elements In Agricultural Regions Of The Mid-Continental Usa, Najwah Alssaeidi Ahmed Almesleh

Open Access Theses & Dissertations

Regional geochemical mapping constitute the chemistry of the surface of the earth in a large scale and relatively low sample density. It is widely accepted scientific activity and man uses some cases to identify contamination. In the present study, data present in national geochemical survey database was used to investigate the chemical loading loading of the agricultural soil. In the mid-continent region of the United States. Several traditional parameters were used mainly the enrichment factor (EF), and geoaccumulation index (I geo). Total chemical influence (TCI) maps were used to guide sampling. In addition, regional trace element chemistry of bedrock was …

Wildfire Emissions In The Context Of Global Change And The Implications For Mercury Pollution, Aditya Kumar

Dissertations, Master's Theses and Master's Reports

Wildfires are episodic disturbances that exert a significant influence on the Earth system. They emit substantial amounts of atmospheric pollutants, which can impact atmospheric chemistry/composition and the Earth’s climate at the global and regional scales. This work presents a collection of studies aimed at better estimating wildfire emissions of atmospheric pollutants, quantifying their impacts on remote ecosystems and determining the implications of 2000s-2050s global environmental change (land use/land cover, climate) for wildfire emissions following the Intergovernmental Panel on Climate Change (IPCC) A1B socioeconomic scenario.

A global fire emissions model is developed to compile global wildfire emission inventories for major atmospheric …

Catalyzed Synthesis Of Zinc Clays By Prebiotic Central Metabolites, Marcelo I. Guzman, Ruixin Zhou, Kaustuv Basu, Hyman Hartman, Christopher J. Matocha, S. Kelly Sears, Hajatollah Vali

Chemistry Faculty Publications

How primordial metabolic networks such as the reverse tricarboxylic acid (rTCA) cycle and clay mineral catalysts coevolved remains a mystery in the puzzle to understand the origin of life. While prebiotic reactions from the rTCA cycle were accomplished via photochemistry on semiconductor minerals, the synthesis of clays was demonstrated at low temperature and ambient pressure catalyzed by oxalate. Herein, the crystallization of clay minerals is catalyzed by succinate, an example of a photoproduced intermediate from central metabolism. The experiments connect the synthesis of sauconite, a model for clay minerals, to prebiotic photochemistry. We report the temperature, pH, and concentration dependence …

Effects Of Silvopasture Establishment On Aqueous And Gaseous Soil N Losses At The University Of New Hampshire Organic Dairy Research Farm, Kathryn Ann Slebodnik

Honors Theses and Capstones

The expansion of local agriculture in the New England region is putting increased pressure on farmers to expand their arable land base. While clear-cutting is a traditional method of converting forested land to agriculture, it is known for having adverse ecological impacts. To minimize these impacts, farmers can create a silvopasture which incorporates a portion of the original forest canopy into pastures or crop fields. This study evaluates the impact of land-use changes for agriculture on soil nitrogen (N) retention. In particular, this study investigates the differences in soil N turnover, gaseous loss, and aqueous loss among an established forest, …

The Role Of Organic Matter In The Fate And Transport Of Antibiotic Resistance, Metals, And Nutrients In The Karst Of Northwest Arkansas, Victor Lee Roland Ii

Graduate Theses and Dissertations

Organic matter (OM) in the environment acts as a nutrient, but may also act as a transport vector for harmful chemical compounds and bacteria. Acetate is a labile form of OM produced during fermentation in anaerobic lagoons used to store animal fecal-waste from concentrated animal feeding operations (CAFOs). Dry and liquid fertilizers from CAFOs pose a threat to groundwater by introducing excessive amounts of nutrients (e.g. OM, nitrate and ammonia), metals, and antibiotic compounds. In the epikarst of Northern Arkansas in the Buffalo River watershed additional input of labile dissolved organic carbon (DOC) from liquid CAFO waste-fertilizers was hypothesized to …

Photocatalytic Reduction Of Fumarate To Succinate On Zns Mineral Surfaces, Ruixin Zhou, Marcelo I. Guzman

Chemistry Faculty Publications

The reductive tricarboxylic acid (rTCA) cycle is an important central biosynthetic pathway that fixes CO₂ into carboxylic acids. Among the five reductive steps in the rTCA cycle, the two-electron reduction of fumarate to succinate proceeds nonenzymatically on the surface of photoexcited sphalerite (ZnS) colloids suspended in water. This model reaction is chosen to systematically study the surface photoprocess occurring on ZnS in the presence of [Na₂S] (1–10 mM) hole scavenger at 15 °C. Experiments at variable pH (5–10) indicate that monodissociated fumaric acid is the primary electron acceptor forming the monoprotic form of succinic acid. The following …

The Marine Cyanate Cycle, Brittany Widner

OES Theses and Dissertations

Cyanate (OCN-) is a reduced nitrogen compound with the potential to serve as a nitrogen and carbon source for marine microbes. Evidence from genomes and culture studies indicated that several marine cyanobacterial groups, including representatives of the globally important genera Synechococcus and Prochlorococcus, might be capable of cyanate assimilation. However, prior to this study, the distribution, bioavailability, and production pathways of cyanate were unknown in natural systems due to the absence of a sensitive cyanate assay; and the ability of organisms to assimilate cyanate on relevant timescales was unknown because we lacked a suitable tracer for measuring uptake. I developed …

Perchlorate Variations Over 300 Years: Influence Of Human Activities, Volcanic Eruptions And Bolide Events, Kari Peterson

Electronic Theses and Dissertations

Perchlorate, which derives from both anthropogenic and natural sources in the current environment, constitutes a significant health risk to humans because it competitively inhibits iodine uptake by the thyroid gland. Thus, there has been considerable interest in reducing the human exposure to environmental perchlorate by limiting the release of perchlorate from anthropogenic sources. However, a lack of understanding of the relative contributions from anthropogenic and natural sources has prevented widespread regulation. A 300-year ice core perchlorate record from Summit Station, Greenland (1700-2007 C.E.) that extends beyond the onset of the Industrial Revolution (1850 C.E.) is used to assess the anthropogenic …

Source-Specific Molecular Signatures For Light-Absorbing Organic Aerosols, Amanda Susan Willoughby

Chemistry & Biochemistry Theses & Dissertations

Organic aerosols (OA) are universally regarded as an important component of the atmosphere based on quantitative significance as well as the far-reaching impact they have on global climate forcing and human health. Despite the acknowledged importance, OA amounts and impacts remain the largest uncertainties regarding radiative forcing estimates. Incomplete chemical characterization of aerosol organic matter (OM) and a lack of concrete source apportionment is a major source of this uncertainty. The primary focus of this study is to provide much needed molecular details regarding ambient OA from key emission sources, and establish links between molecular and optical properties.

Complete chemical …

Nutrient Addition Effects On Tropical Dry Forests: A Mini-Review From Microbial To Ecosystem Scales, Jennifer S. Powers, Kristen K. Becklund, Maria G. Gei, Siddharth B. Iyengar, Rebecca Meyer, Christine S. O'Connell, Erik M. Schilling, Christina M. Smith, Bonnie G. Waring, Leland K. Werden

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Humans have more than doubled inputs of reactive nitrogen globally and greatly accelerated the biogeochemical cycles of phosphorus and metals. However, the impacts of increased element mobility on tropical ecosystems remain poorly quantified, particularly for the vast tropical dry forest biome. Tropical dry forests are characterized by marked seasonality, relatively little precipitation, and high heterogeneity in plant functional diversity and soil chemistry. For these reasons, increased nutrient deposition may affect tropical dry forests differently than wet tropical or temperate forests. Here, we review studies that investigated how nutrient availability affects ecosystem and community processes from the microsite to ecosystem scales …

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 …

Long-Term Litter Decomposition Controlled By Manganese Redox Cycling, Marco Keiluweit, Peter Nico, Mark E. Harmon, Jingdong Mao, Jennifer Pett-Ridge, Markus Kleber

Chemistry & Biochemistry Faculty Publications

Litter decomposition is a keystone ecosystem process impacting nutrient cycling and productivity, soil properties, and the terrestrial carbon (C) balance, but the factors regulating decomposition rate are still poorly understood. Traditional models assume that the rate is controlled by litter quality, relying on parameters such as lignin content as predictors. However, a strong correlation has been observed between the manganese (Mn) content of litter and decomposition rates across a variety of forest ecosystems. Here, we show that long-term litter decomposition in forest ecosystems is tightly coupled to Mn redox cycling. Over 7 years of litter decomposition, microbial transformation of litter …

Carbon And Nitrogen Dynamics From Slow Pools Of Soil Organic Matter In A Temperate Forest: Pyrogenic Organic Matter And And Root Litter, Fernanda Dos Santos

Dissertations, Theses, and Capstone Projects

Soil organic matter (SOM) is the dominant reservoir of organic carbon (OC) in terrestrial ecosystems, storing approximately three times the size of the C pool in the atmosphere. In temperate forests, a major fraction of the SOM consists of slowly decaying soil organic C (SOC) pools. While slowly cycling C pools constitute a large reservoir of stable C in soils, the dominant environmental factors controlling this C pool remain unresolved. This research investigates two significant, but poorly characterized slowly decaying C pools: fine root litter (< 2mm) and thermally altered plant biomass (pyrogenic organic matter, PyOM). Specifically, I used compound-specific stable isotope analysis (¹³C and ¹⁵N) as my main methodological approach to examine the (1) …

Ice Caves On Extraterrestrial Bodies: What Are The Prospects For Speleogenesis And Detection?, Penelope J. Boston

The International Workshop on Ice Caves

Potential mechanisms for creating cavities in icy extraterrestrial bodies have been tentatively explored by several authors. On one hand we have examples of mechanisms that create caves in water ice here on Earth. In addition, there may be unique mechanisms on other Solar System objects that do not occur on Earth but might produce cavities, e.g. sublimation of comets upon perihelion passage. The methods of detecting such cavities depend upon the nature of the icy body in question, the potential for orbital or landed missions to visit those bodies in the future, and remote or landed methods for detecting the …

Carbon Sequestration In Tidal Salt Marshes And Mangrove Ecosystems, Carlos Eduardo Quintana-Alcantara

Master's Projects and Capstones

Wetlands are dynamic systems that provide support to vital environmental functions and services. Wetlands take part in the global carbon cycle by holding organic carbon in biomass, soils and sediments. In recent years, the wetland carbon sequestration capacity has been researched worldwide due to the increase of the concentrations of greenhouse gasses implicated in global warming and climate change. Although coastal wetlands release the greenhouse gasses carbon dioxide, methane and nitrous oxide, these ecosystems maintain high performance in offsetting significant amounts of atmospheric carbon. This paper investigated the carbon sequestration capacity of coastal wetland ecosystems summarizing the environmental conditions and …

A Review Of The Hyporheic Zone, Stream Restoration, And Means To Enhance Denitrification, Leanne Merill, David J. Tonjes

Technology & Society Faculty Publications

The hyporheic zone is the subsurface area below and adjacent to a stream where groundwater mixes with stream water, through vertical, lateral, and longitudinal flows. The hyporheic zone connects the stream to uplands and other terrestrial environments. It is a zone of distinct faunal communities, high biological diversity and ecological complexity, and is the site of chemical processing and transformations of ground- and stream waters. The hyporheic zone is important to the overall ecosystem ecology of the stream, and it can influence stream water chemistry. Flows, reactions, and biota in the hyporheic zone are heterogeneous and patchy, making it difficult …

Molecular Characterization And Photochemical Transformation Of Dissolved Organic Matter From Land To Ocean, Hongmei Chen

Chemistry & Biochemistry Theses & Dissertations

Molecular characterization and photochemical transformation of dissolved organic matter (DOM) in both rivers and the ocean is the main research focus of this dissertation. Chemical characterization of DOM is hampered by the limited application of advanced techniques to desalt, concentrate, isolate and then molecularly characterize DOM. An affordable, commercially available mini-electrodialysis (mini-ED) system has been evaluated and recommended for the efficient desalting of small volume samples of seawater prior to analysis by electrospray Fourier transform ion cyclotron resonance mass spectrometry (ESI FTICR-MS).

A high-recovery technique of DOM isolation – reverse osmosis coupled with electrodialysis (RO/ED) – was used to isolate …

Spectroscopic Characterization Of Dissolved Organic Matter: Insights Into The Linkage Between Sources And Chemical Composition, Xiaoyan Cao

Chemistry & Biochemistry Theses & Dissertations

This dissertation investigated the chemical structure of DOM by advanced solid-state nuclear magnetic resonance (NMR) spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) techniques, as well as isotopic measurements and UV-visible spectroscopy, to shed light on the linkages between DOM sources and DOM composition. Unique and extensive sets of DOM samples studied here were isolated from various aquatic systems, covering end-member environments in which DOM is considered either microbially derived or terrestrially derived, and areas in which DOM has characteristics intermediate between the two end members. Important insights into specific site-related questions were also gained such as …

Monitoring The Influence Of Acid Deposition On Soil And Implications To Forest Health In The Daniel Boone National Forest, Tyler M. Sanderson

Theses and Dissertations--Forestry and Natural Resources

Combustion of fossil fuels has contributed to many environmental problems including acid deposition. The Clean Air Act (CAA) was created to reduce ecological problems by cutting emissions of sulfur and nitrogen. Reduced emissions and rainfall concentrations of acidic ions have been observed since the enactment of the CAA, but soils continue to receive some acid inputs. Soils sensitive to acid deposition have been found to have low pH, a loss of base cations and a shift in the mineral phase controlling the activity of Al³⁺ and/or SO₄^2-. If inputs continue, soil may be depleted of base …

Compositions And Constituents Of Freshwater Dissolved Organic Matter Isolated By Reverse Osmosis, Yulong Zhang, Wen Huang, Jingdong Mao

Chemistry & Biochemistry Faculty Publications

Dissolved organic matter (DOM) from riverine and lacustrine water was isolated using a reverse osmosis (RO) system. Solid-state ¹³C nuclear magnetic resonance (¹³C NMR) was used to quantitatively evaluate the compositions and constituents of DOM, which are compared with previous investigations on marine DOM. Results indicated that concentration factor (CF) was a key metric controlling yield and sorption of DOM on the RO system. The sorption was likely non-selective, based on the ¹³C NMR and δ¹³C analyses. Carbohydrates and lipids accounted for 25.0–41.5% and 30.2–46.3% of the identifiable DOM, followed by proteins (18.2–19.8%) and …

Wavelength And Temperature-Dependent Apparent Quantum Yields For Photochemical Formation Of Hydrogen Peroxide In Seawater, David J. Kieber, Gary W. Miller, Patrick J. Neale, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Wavelength and temperature-dependent apparent quantum yields (AQYs) were determined for the photochemical production of hydrogen peroxide using seawater obtained from coastal and oligotrophic stations in Antarctica, the Pacific Ocean at Station ALOHA, the Gulf of Mexico, and at several sites along the East Coast of the United States. For all samples, AQYs decreased exponentially with increasing wavelength at 25 °C, ranging from 4.6 × 10−4 to 10.4 × 10−4 at 290 nm to 0.17 × 10−4 to 0.97 × 10−4 at 400 nm. AQYs for different seawater samples were remarkably similar irrespective of expected differences in the composition and concentrations …