Digital Commons Network^™

Validation Of The Global Distribution Of Co2 Volume Mixing Ratio In The Mesosphere And Lower Thermosphere From Saber, L. Rezac, Y. Jian, J. Yue, J. M. Russell Iii, A. Kutepov, R. Garcia, K. Walker, P. Bernath

Chemistry & Biochemistry Faculty Publications

The Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) instrument on board the Thermosphere Ionosphere Mesosphere Energetics and Dynamics satellite has been measuring the limb radiance in 10 broadband infrared channels over the altitude range from ~ 400 km to the Earth's surface since 2002. The kinetic temperatures and CO₂ volume mixing ratios (VMRs) in the mesosphere and lower thermosphere have been simultaneously retrieved using SABER limb radiances at 15 and 4.3 μm under nonlocal thermodynamic equilibrium (non-LTE) conditions. This paper presents results of a validation study of the SABER CO₂ VMRs obtained with a two-channel, self-consistent …

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 …

Simulation Of Energetic Particle Precipitation Effects During The 2003-2004 Arctic Winter, C. E. Randall, V. L. Harvey, L. A. Holt, D. R. Marsh, D. Kinnison, B. Funke, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Energetic particle precipitation (EPP) during the 2003-2004 Arctic winter led to the production and subsequent transport of reactive odd nitrogen (NO_x=NO+NO₂) from the mesosphere and lower thermosphere (MLT) into the stratosphere. This caused NO_x enhancements in the polar upper stratosphere in April 2004 that were unprecedented in the satellite record. Simulations of the 2003-2004 Arctic winter with the Whole Atmosphere Community Climate Model using Specified Dynamics (SD-WACCM) are compared to satellite measurements to assess our understanding of the observed NO_x enhancements. The comparisons show that SD-WACCM clearly displays the descent of NO_x produced …

Growth In Stratospheric Chlorine From Short-Lived Chemicals Not Controlled By The Montreal Protocol, R. Hossaoni, M. P. Chipperfield, A. Saiz-Lopez, J. J. Harrison, R. Von Glasow, R. Sommariva, E. Atlas, M. Navarro, S. A. Montzka, W. Feng, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

We have developed a chemical mechanism describing the tropospheric degradation of chlorine containing very short-lived substances (VSLS). The scheme was included in a global atmospheric model and used to quantify the stratospheric injection of chlorine from anthropogenic VSLS (Cl_y^VSLS) between 2005 and 2013. By constraining the model with surface measurements of chloroform (CHCl₃), dichloromethane (CH₂Cl₂), tetrachloroethene (C₂Cl₄), trichloroethene (C₂HCl₃), and 1,2-dichloroethane (CH₂ClCH₂Cl), we infer a 2013 Cl_y^VSLS mixing ratio of 123 parts per trillion (ppt). Stratospheric injection …

Investigation Of The Potential For Algaenan To Produce Hydrocarbon Based Fuels From Algae By Hydrous Pyrolysis, Wassim Adel Obeid

Chemistry & Biochemistry Theses & Dissertations

The use of algae as a feedstock for hydrous pyrolysis has a high potential for producing biofuels. The non-food nature of algae in addition to the various advantages associated with the hydrous pyrolysis process makes this combination for the production of biofuels of high interest. However, current results from algae processing have alluded to some challenges: byproducts arising from the thermal transformation of carbohydrates and proteins, which become incorporated in the oil fraction, result in high oxygen and nitrogen contents of the oil. Accordingly, this produces an oil of low quality for refineries. This dissertation investigates use of a pretreatment …

A Survey Of Aquatic Organisms For The Cyanotoxin Beta-Methylamino-L-Alanine (Bmaa), Ian M. Sammler

OES Theses and Dissertations

Cyanobacteria blooms are increasing globally as a result of eutrophication. Many cyanobacteria are potentially harmful, not only because of the oxygen depleted zones created when they decay, but also because of the toxins they produce. β- Methylamino-L-alanine (BMAA), reportedly produced by many species of cyanobacteria, is a non-proteinogenic amino acid that has been linked to the development of neurodegenerative diseases (amyotrophic lateral sclerosis (ALS) and Alzheimer's) in humans. This study presents results from an assessment of BMAA in cyanobacteria and their grazers from the lower Chesapeake Bay and Lake Erie regions. BMAA was analyzed in samples prepared with the EZ:Faast™ …

Dissolved Oxygen Dynamics During A Phytoplankton Bloom In The Ross Sea Polyna, Bastien Y. Queste, Karen J. Heywood, Walker O. Smith Jr., Daniel E. Kaufman, Timothy D. Jickells, Michael S. Dinniman

CCPO Publications

The Ross Sea polynya is one of the most productive regions in the Southern Ocean. However, limited access and high spatio-temporal variability of physical and biological processes limit the use of conventional oceanographic methods to measure early season primary productivity. High-resolution observations from two Seagliders provide insights into the timing of a bloom in the southern Ross Sea polynya in December 2010. Changes in chlorophyll and oxygen concentrations are used to assess bloom dynamics. Using a ratio of dissolved oxygen to carbon, net primary production is estimated over the duration of the bloom showing a sensitive balance between net autotrophy …

Chesapeake Bay Nitrogen Fluxes Derived From A Land-Estuarine Ocean Biogeochemical Modeling System: Model Description, Evaluation, And Nitrogen Bonds, Yang Feng, Marjorie A.M. Friedrichs, John Wilkin, Hanqin Tian, Qichun Yang, Eileen E. Hofmann

CCPO Publications

The Chesapeake Bay plays an important role in transforming riverine nutrients before they are exported to the adjacent continental shelf. Although the mean nitrogen budget of the Chesapeake Bay has been previously estimated from observations, uncertainties associated with interannually varying hydrological conditions remain. In this study, a land-estuarine-ocean biogeochemical modeling system is developed to quantify Chesapeake riverine nitrogen inputs, within-estuary nitrogen transformation processes and the ultimate export of nitrogen to the coastal ocean. Model skill was evaluated using extensive in situ and satellite-derived data, and a simulation using environmental conditions for 2001-2005 was conducted to quantify the Chesapeake Bay nitrogen …

Molecular Level Characterization Of Diatom-Associated Biopolymers That Bind 234th, ²³³Pa, ²¹°Pb, And 7be In Seawater: A Case Study With Phaeodactylum Tricornutum, Chia-Ying Chuang, Peter H. Santschi, Chen Xu, Yuelu Jiang, Yi-Fang Ho, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

In order to investigate the importance of biogenic silica associated biopolymers on the scavenging of radionuclides, the diatom Phaeodactylum tricornutum was incubated together with the radionuclides Th-234, Pa-233, Pb-210, and Be-7 during their growth phase. Normalized affinity coefficients were determined for the radionuclides bound with different organic compound classes (i.e., proteins, total carbohydrates, uronic acids) in extracellular (nonattached and attached exopolymeric substances), intracellular (ethylene diamine tetraacetic acid and sodium dodecyl sulfate extractable), and frustule embedded biopolymeric fractions (BF). Results indicated that radionuclides were mostly concentrated in frustule BF. Among three measured organic components, Uronic acids showed the strongest affinities to …

Characterization Of Terrestrial Dissolved Organic Matter Fractionated By Ph And Polarity And Their Biological Effects On Plant Growth, Rachel L. Sleighter, Paolo Caricasole, Kristen M. Richards, Terry Hanson, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Background: Humic substances are ubiquitous in the environment, complex mixtures, and known to be beneficial to plant growth. To better understand and identify components responsible for plant growth stimulation, a terrestrial aquatic DOM sample was fractionated according to pH and polarity, obtaining acid-soluble and acid-insoluble portions, as well as acid-soluble hydrophobic and hydrophilic fractions using C18. The various fractions were characterized then evaluated for their biological effects on plant growth using bioassays with corn at two carbon rates.

Results: Approximately 43% and 57% of the carbon, and 31% and 69% of the iron, was found in the acid-insoluble and acid-soluble …

Theoretical Foundation Of Cyclostationary Eof Analysis For Geophysical And Climatic Variables: Concepts And Examples, Kwang-Yul Kim, Benjamin Hamlington, Hanna Na

CCPO Publications

Natural variability is an essential component of observations of all geophysical and climate variables. In principal component analysis (PCA), also called empirical orthogonal function (EOF) analysis, a set of orthogonal eigenfunctions is found from a spatial covariance function. These empirical basis functions often lend useful insights into physical processes in the data and serve as a useful tool for developing statistical methods. The underlying assumption in PCA is the stationarity of the data analyzed; that is, the covariance function does not depend on the origin of time. The stationarity assumption is often not justifiable for geophysical and climate variables even …

Vapor Flow Resistance Of Dry Soil Layer To Soil Water Evaporation In Arid Environment: An Overview, Xixi Wang

Civil & Environmental Engineering Faculty Publications

Evaporation from bare sandy soils is the core component of the hydrologic cycle in arid environments, where vertical water movement dominates. Although extensive measurement and modeling studies have been conducted and reported in existing literature, the physics of dry soil and its function in evaporation is still a challenging topic with significant remaining issues. Thus, an overview of the previous findings will be very beneficial for identifying further research needs that aim to advance our understanding of the vapor flow resistance (VFR) effect on soil water evaporation as influenced by characteristics of the dry soil layer (DSL) and evaporation zone …

Iron Supply And Demand In Antarctic Shelf Ecosystem, D. J. Mcgillicuddy Jr., Peter N. Sedwick, Michael S. Dinniman, K. R. Arrigo, T. S. Bibby, B. J. W. Greenan, Eileen E. Hofmann, John M. Klinck, W. O. Smith Jr., S. L. Mack, C. M. Marsay, B. M. Sohst, G. L. Van Dijken

OES Faculty Publications

The Ross Sea sustains a rich ecosystem and is the most productive sector of the Southern Ocean. Most of this production occurs within a polynya during the November-February period, when the availability of dissolved iron (dFe) is thought to exert the major control on phytoplankton growth. Here we combine new data on the distribution of dFe, high-resolution model simulations of ice melt and regional circulation, and satellite-based estimates of primary production to quantify iron supply and demand over the Ross Sea continental shelf. Our analysis suggests that the largest sources of dFe to the euphotic zone are wintertime mixing and …

Use Of Esi-Fticr-Ms To Characterize Dissolved Organic Matter In Headwater Streams Draining Forest-Dominated And Pasture-Dominated Watersheds, Yuehan Lu, Xiaping Li, Rajaa Mesfioui, James E. Bauer, R. M. Chambers, Elizabeth A. Canuel, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) has proven to be a powerful technique revealing complexity and diversity of natural DOM molecules, but its application to DOM analysis in grazing-impacted agricultural systems remains scarce. In the present study, we presented a case study of using ESI-FTICR-MS in analyzing DOM from four headwater streams draining forest-or pasture-dominated watersheds in Virginia, USA. In all samples, most formulas were CHO compounds (71.8-87.9%), with other molecular series (CHOS, CHON, CHONS, and CHOP (N, S)) accounting for only minor fractions. All samples were dominated by molecules falling in the lignin-like region (H/C …

Spatio-Temporal Patterns Of Water Table And Vegetation Status Of A Deserted Area, Limin Duan, Tingxi Liu, Xixi Wang, Yanyun Luo

Civil & Environmental Engineering Faculty Publications

Understanding groundwater-vegetation interactions is crucial for sustaining fragile environments of desert areas such as the Horqin Sandy Land (HSL) in northern China. This study examined spatio-temporal variations in the water table and the associated vegetation status of a 9.71 km² area that contains meadowland, sandy dunes, and intermediate transitional zones. The depth of the water table and hydrometeorologic parameters were monitored and Landsat Thematic Mapper (TM) and Moderate Resolution Imaging Spectroradiometer (MODIS) data were utilized to assess the vegetation cover. Spatio-temporal variations over the six-year study period were examined and descriptive groundwater-vegetation associations developed by overlaying a water table …

Divergent Responses Of Atlantic Coastal And Oceanic Synechococcus To Iron Limitation, Katherine R. M. Mackey, Anton F. Post, Matthew R. Mcilvin, Gregory A. Cutter, Seth G. John, Mak A. Saito

OES Faculty Publications

Marine Synechococcus are some of the most diverse and ubiquitous phytoplankton, and iron (Fe) is an essential micronutrient that limits productivity in many parts of the ocean. To investigate how coastal and oceanic Atlantic Synechococcus strains acclimate to Fe availability, we compared the growth, photophysiology, and quantitative proteomics of two Synechococcus strains from different Fe regimes. Synechococcus strain WH8102, from a region in the southern Sargasso Sea that receives substantial dust deposition, showed impaired growth and photophysiology as Fe declined, yet used few acclimation responses. Coastal WH8020, from the dynamic, seasonally variable New England shelf, displayed a multitiered, hierarchical cascade …

The Relative Importance Of Methanogenesis In The Decomposition Of Organic Matter In Northern Peatlands, J. Elizabeth Corbett, Malak M. Tfaily, David J. Burdige, Paul H. Glaser, Jeffrey P. Chanton

OES Faculty Publications

Using an isotope-mass balance approach and assuming the equimolar production of CO₂ and CH₄ from methanogenesis (e.g., anaerobic decomposition of cellulose), we calculate that the proportion of total CO₂ production from methanogenesis varies from 37 to 83% across a variety of northern peatlands. In a relative sense, methanogenesis was a more important pathway for decomposition in bogs (80 ± 13% of CO₂ production) than in fens (64 ± 5.7% of CO₂ production), but because fens contain more labile substrates they may support higher CH4 production overall. The concentration of CO₂ produced from methanogenesis (CO …

Tropical North Atlantic Subsurface Warming Events As A Fingerprint For Amoc Variability During Marine Isotope Stage 3, Andrew O. Parker, Matthew W. Schmidt, Ping Chang

OES Faculty Publications

The role of Atlantic Meridional Overturning Circulation (AMOC) as the driver of Dansgaard-Oeschger (DO) variability that characterized Marine Isotope Stage 3 (MIS 3) has long been hypothesized. Although there is ample proxy evidence suggesting that DO events were robust features of glacial climate, there is little data supporting a link with AMOC. Recently, modeling studies and subsurface temperature reconstructions have suggested that subsurface warming across the tropical North Atlantic can be used to fingerprint a weakened AMOC during the deglacial because a reduction in the strength of the western boundary current allows warm salinity maximum water of the subtropical gyre …

Heterotrophic And Autotrophic Contribution To Dinitrogen Fixation In The Gulf Of Aqaba, Eyal Rahav, Barak Herut, Margaret R. Mulholland, Natalia Belkin, Hila Elifantz, Ilana Berman-Frank

OES Faculty Publications

We evaluated the seasonal contribution of heterotrophic and autotrophic diazotrophy to the total dinitrogen (N₂) fixation in the photic zone of a pelagic station in the northern Gulf of Aqaba, Red Sea. N₂ fixation rates were highest during a Trichodesmium bloom in winter (0.7 nmol N l^-1 d^-1), decreased 7-fold 1 wk later throughout the upper 200 m (~0.1 nmol N l^-1) d^-1), and were significantly coupled with both primary and bacterial productivity. N₂ fixation rates were generally higher in the upper 200 m (~0.4 nmol N l^{-1 …}

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 …

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 …