Geochemistry Commons^™

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 …

Dependence Of The Martian Radiation Environment On Atmospheric Depth: Modeling And Measurement, Jingnan Guo, Tony C. Slaba, Cary Zeitlin, Robert F. Wimmer-Schweingruber, Francis F. Badavi, Eckart Böhm, Stephan Böttcher, David E. Brinza, Bent Ehresmann, Donald M. Hassler

Physics Faculty Publications

The energetic particle environment on the Martian surface is influenced by solar and heliospheric modulation and changes in the local atmospheric pressure (or column depth). The Radiation Assessment Detector (RAD) on board the Mars Science Laboratory rover Curiosity on the surface of Mars has been measuring this effect for over four Earth years (about two Martian years). The anticorrelation between the recorded surface Galactic Cosmic Ray-induced dose rates and pressure changes has been investigated by Rafkin et al. (2014) and the long-term solar modulation has also been empirically analyzed and modeled by Guo et al. (2015). This paper employs the …

Spatial Patterns Of Sea Level Variability Associated With Natural Internal Climate Modes, Weiqing Han, Gerald A. Meehl, Detlef Stammer, Aixue Hu, Benjamin Hamlington, Jessica Kenigson, Hindumathi Palanisamy, Philip Thompson

OES Faculty Publications

Sea level rise (SLR) can exert significant stress on highly populated coastal societies and low-lying island countries around the world. Because of this, there is huge societal demand for improved decadal predictions and future projections of SLR, particularly on a local scale along coastlines. Regionally, sea level variations can deviate considerably from the global mean due to various geophysical processes. These include changes of ocean circulations, which partially can be attributed to natural, internal modes of variability in the complex Earth's climate system. Anthropogenic influence may also contribute to regional sea level variations. Separating the effects of natural climate modes …

Community Production Modulates Coral Reef Ph And The Sensitivity Of Ecosystem Calcification To Ocean Acidification, Thomas M. Decarlo, Anne L. Cohen, George T. F. Wong, Fuh-Kwo Shiah, Steven J. Lentz, Kristen A. Davis, Kathryn E. F. Shamberger, Pat Lohmann

OES Faculty Publications

Coral reefs are built of calcium carbonate (CaCO₃) produced biogenically by a diversity of calcifying plants, animals, and microbes. As the ocean warms and acidifies, there is mounting concern that declining calcification rates could shift coral reef CaCO3 budgets from net accretion to net dissolution. We quantified net ecosystem calcification (NEC) and production (NEP) on Dongsha Atoll, northern South China Sea, over a 2 week period that included a transient bleaching event. Peak daytime pH on the wide, shallow reef flat during the nonbleaching period was ~8.5, significantly elevated above that of the surrounding open ocean (~8.0-8.1) as …

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 …

Effects Of Nonaerated Circulation Water Velocity On Nutrient Release From Aquaculture Pond Sediments, Xiangju Cheng, Dantong Zhu, Xixi Wang, Deguang Yu, Jun Xie

Civil & Environmental Engineering Faculty Publications

Sustaining good water quality in aquaculture ponds is vital. Without an aerator, the dissolved oxygen in ponds comes primarily from mass transfer at the water-ambient atmosphere interface. As sediment can seriously affect water quality, this study used indoor experiments to examine the nutrient (nitrogen and phosphorus) release mechanisms and fluxes from sediment in aquaculture ponds with moving water but no aeration. The results showed that the ammonia nitrogen (NH₃-N) concentration in the overlying water was inversely proportional to flow velocity and that a higher flow velocity tended to result in a lower concentration in the overlying water, a …

A Tribute To Thomas M. Church: Exploring Chemical Oceanography In The Coastal Zone-The History And Future, Gregory A. Cutter, David J. Burdige

OES Faculty Publications

(First paragraph) One can find different historical perspectives on the development of studying the chemistry of oceans as well as names for this study—marine chemistry, chemistry of the sea, marine aquatic chemistry, marine biogeochemistry, or chemical oceanography. It could be argued that chemical oceanography is the most inclusive for an earth science since oceanography itself is an integrated discipline that links the biology, chemistry, geology, and physics together. Regardless of the name, perhaps the first intensive, modern/post-nineteenth century study of the ocean’s chemistry was the GEOSECS Program from ca. 1970–1978. The significance of GEOSECS was that it examined the chemistry …

Low-Temperature Artificial Maturation Studies Of Type Ii And Type Iii Kerogens: Implications For Biogenic Gas Production, Albert Willy Nguena Kamga

Chemistry & Biochemistry Theses & Dissertations

Ancient organic matter (OM) in shales and coals, known mainly as Type II and Type III OM are known to produce both biogenic, thermogenic gas and oil. In this dissertation, mild artificial maturation, via closed system pyrolysis, is employed to determine the thermal reactivity of Type II and Type III OM beyond diagenesis. We select three Type II kerogens: i) Type II kerogen isolated from recent cores (3.3 Ma, Ro = 0.28) recovered from an upwelling basin in Namibia, Africa referred to as ODP Sediment, ii) Type II-S isolated from sediments (150 Ma, Ro = 0.38) recovered from an outcrop …

Dynamics Of Plume-Triple Junction Interaction: Results From A Series Of Three-Dimensional Numerical Models And Implications For The Formation Of Oceanic Plateaus, Mladen Dordevic, Jennifer Georgen

OES Faculty Publications

Mantle plumes rising in the vicinity of mid-ocean ridges often generate anomalies in melt production and seafloor depth. This study investigates the dynamical interactions between a mantle plume and a ridge-ridge-ridge triple junction, using a parameter space approach and a suite of steady state, three-dimensional finite element numerical models. The top domain boundary is composed of three diverging plates, with each assigned half-spreading rates with respect to a fixed triple junction point. The bottom boundary is kept at a constant temperature of 1350°C except where a two-dimensional, Gaussian-shaped thermal anomaly simulating a plume is imposed. Models vary plume diameter, plume …

The Martian Surface Radiation Environment- A Comparison Of Models And Msl/Rad Measurements, Daniel Matthiä, Bent Ehresmann, Henning Lohf, Jan Köhler, Cary Zeitlin, Jan Appel, John W. Wilson

Mathematics & Statistics Faculty Publications

Context: The Radiation Assessment Detector (RAD) on the Mars Science Laboratory (MSL) has been measuring the radiation environment on the surface of Mars since August 6th 2012. MSL-RAD is the first instrument to provide detailed information about charged and neutral particle spectra and dose rates on the Martian surface, and one of the primary objectives of the RAD investigation is to help improve and validate current radiation transport models.

Aims: Applying different numerical transport models with boundary conditions derived from the MSL-RAD environment the goal of this work was to both provide predictions for the particle spectra and the radiation …

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 …

Growth And Nitrogen Uptake Kinetics In Cultured Procentrum Donghaiense, Zhangxi Hu, Shunshan Duan, Margaret R. Mulholland

OES Faculty Publications

We compared growth kinetics of Prorocentrum donghaiense cultures on different nitrogen (N) compounds including nitrate, ammonium urea, glutamic acid, dialanine, and cynate. P. donghaiense exhibited standard Monod-type growth kinetics over a range of nitrogen concentrations for all N. Compounds tested. Cultures grown on glu and urea had the highest maximum growth rates. However, cultures grown on cyanate had lower half saturation constants. Nitrogen uptake kinetics were measured in nitrate-deplete and replete batch cultures of P. donghaiense. In nitrate-deplete batch cultures, P. donghaiense exhibited Michaelis-Menten type uptake kinetics for nitrate, ammonium, urea and algal amino acids; uptake was saturated at …

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 …

A Coupled Geochemical And Biogeochemical Approach To Characterize The Bioreactivity Of Dissolved Organic Matter From A Headwater Stream, Rachel L. Sleighter, Rose M. Cory, Louis A. Kaplan, Hussain A.N. Abdulla, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

The bioreactivity or susceptibility of dissolved organic matter (DOM) to microbial degradation in streams and rivers is of critical importance to global change studies, but a comprehensive understanding of DOM bioreactivity has been elusive due, in part, to the stunningly diverse assemblages of organic molecules within DOM. We approach this problem by employing a range of techniques to characterize DOM as it flows through biofilm reactors: dissolved organic carbon (DOC) concentrations, excitation emission matrix spectroscopy (EEMs), and ultrahigh resolution mass spectrometry. The EEMs and mass spectral data were analyzed using a combination of multivariate statistical approaches. We found that 45% …

Molecular Characteristics Of The Water Soluable Organic Matter In Size Resolved Aerosols Collected Over The North Atlantic Ocean, Sarah Catherine Gurganus

Chemistry & Biochemistry Theses & Dissertations

Aerosol particulate matter is acknowledged to have effects on health and the environment and further investigation into the molecular characteristics of aerosols is necessary in order to fully understand the potential links between the molecular characteristics and the impacts that these particles have on health and the environment. Aerosols are often discussed with reference to their size because particles of different sizes can often be associated with different primary sources. This study presents a molecular-level chemical characterization of the water soluble organic matter fraction of 17 aerosol impactor samples representing 3 air mass influences (North American, North African, and marine) …

Stromatolites And Miss—Differences Between Relatives, N. Noffke, S. M. Awramik

OES Faculty Publications

Benthic microorganisms form highly organized communities called “biofilms.” A biofilm consists of the individual cells plus their extracellular polymeric substances (EPS). In marine and non-marine environments, benthic microbial communities interact with the physical sediment dynamics and other factors in the environment in order to survive. This interaction can produce distinctive sedimentary structures called microbialites. Binding, biostabilization, baffling, and trapping of sediment particles by microorganisms result in the formation of microbially induced sedimentary structures (MISS); however, if carbonate precipitation occurs in EPS, and these processes happen in a repetitive manner, a multilayered build-up can form—stromatolites. Stromatolites and MISS are first found …

The Relative Contribution Of Methanotrophs To Microbial Communities And Carbon Cycling In Soil Overlying A Coal-Bed Methane Seep, Christopher T. Mills, Gregpry F. Slater, Robert F. Dias, Stephanie A. Carr, Christopher M. Reddy, Raleigh Schmidt, Kevin W. Mandernack

Chemistry & Biochemistry Faculty Publications

Seepage of coal-bed methane (CBM) through soils is a potential source of atmospheric CH₄ and also a likely source of ancient (i.e. ¹⁴C-dead) carbon to soil microbial communities. Natural abundance ¹³C and ¹⁴C compositions of bacterial membrane phospholipid fatty acids (PLFAs) and soil gas CO₂ and CH₄ were used to assess the incorporation of CBM-derived carbon into methanotrophs and other members of the soil microbial community. Concentrations of type I and type II methanotroph PLFA biomarkers (16:1ω8c and 18:1ω8c, respectively) were elevated in CBM-impacted soils compared with a control site. Comparison …

Glacial Shortcut Of Arctic Sea-Ice Transport, Michael Stärz, Xun Gong, Rüdiger Stein, Dennis A. Darby, Frank Kauker, Gerrit Lohmann

OES Faculty Publications

Due to the lack of data, the extent, thickness and drift patterns of sea ice and icebergs in the glacial Arctic remains poorly constrained. Earlier studies are contradictory proposing either a cessation of the marine cryosphere or an ice drift system operating like present-day. Here we examine the marine Arctic cryosphere during the Last Glacial Maximum (LGM) using a high-resolution, regional ocean-sea ice model. Whereas modern sea ice in the western Arctic Basin can circulate in the Beaufort Gyre for decades, our model studies present an extreme shortcut of glacial ice drift. In more detail, our results show a clockwise …

A New Phase Speciation Leaching Procedure For The Determination Of Metals In Oxic And Anoxic Sediments, Brandon R. Gipson

OES Theses and Dissertations

Toxic trace elements such as cadmium, lead, chromium, and arsenic released by human activities can accumulate in marine and estuarine sediments, where these metals are often sequestered until local environmental changes (e.g., redox, salinity, and/or pH) allow these elements to be reintroduced into the food web. In order to assess the extent of toxic trace element contamination in sediment, numerous leaching schemes have been developed that separate sediment-bound trace metals into operationally defined geochemical phases. These "phase speciation" leaching schemes are typically designed with the purpose of being used on either oxic or anoxic sediments. However, natural sediments often contain …

Identifying And Tracking Proteins Through The Marine Water Column: Insights Into The Inputs And Preservation Mechanisms Of Protein In Sediments, Eli K. Moore, Brook L. Nunn, David R. Goodlett, H. Rodger Harvey

OES Faculty Publications

Proteins generated during primary production represent an important fraction of marine organic nitrogen and carbon, and have the potential to provide organism-specific information in the environment. The Bering Sea is a highly productive system dominated by seasonal blooms and was used as a model system for algal proteins to be tracked through the water column and incorporated into detrital sedimentary material. Samples of suspended and sinking particles were collected at multiple depths along with surface sediments on the continental shelf and deeper basin of the Bering Sea. Modified standard proteomic preparations were used in conjunction with high pressure liquid chromatography-tandem …

Insights Into Chemical Structure Changes Of Kerogen From Bituminous Coal In Response To Dike Intrusions Investigated By Advanced Solid-State 13C Nmr, Yuan Li

Chemistry & Biochemistry Theses & Dissertations

Variations in the chemical structures of kerogens From highly volatile bituminous coal located near two igneous dike intrusions in the Illinois Basin were examined in detail by advanced solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Spectral-editing techniques were used to identify specific functional groups. Direct polarization was used to quantify different functional groups. ¹H-¹³C two- dimensional heteronuclear NMR was used to examine connectivities and proximities, and ¹H-¹³C long-range recoupled dipolar dephasing was used to estimate aromatic cluster sizes. With decreasing distance to dike contacts and increasing thermal maturity (vitrinite reflectance R₀ from …

The Nature, Origin And Preservation Of Amide Organic Nitrogen In Organic Matter, Georgina Anne Mckee

Chemistry & Biochemistry Theses & Dissertations

Past studies have found much of nonliving sedimentary/aqueous nitrogen-containing organic matter (NCOM) is composed of amides, assumed to be peptides/proteins. Their lability calls into question their survival, and several hypotheses have been suggested to explain this. Using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and nuclear magnetic resonance (NMR) spectroscopy I investigated the molecular amide composition in sedimentary/aqueous systems while reassessing their preservation and formation routes.

Development of a suitable methodology is essential for successful NCOM study due to electrospray ionisation source requirements: sediment samples need to be rendered into solution. Based on NMR and FT-ICR-MS analysis, I determined …

Early Season Depletion Of Dissolved Iron In The Ross Sea Polynya: Implications For Iron Dynamics On The Antarctic Continental Shelf, Peter N. Sedwick, C. M. Marsay, B. M. Sohst, A. M. Aguilar-Islas, M. C. Lohan, M. C. Long, K. R. Arrigo, R. B. Dunbar, M. A. Saito, W. O. Smith, G. R. Ditullio

OES Faculty Publications

The Ross Sea polynya is among the most productive regions in the Southern Ocean and may constitute a significant oceanic CO₂sink. Based on results from several field studies, this region has been considered seasonally iron limited, whereby a "winter reserve" of dissolved iron (dFe) is progressively depleted during the growing season to low concentrations (~ 0.1 nM) that limit phytoplankton growth in the austral summer (December-February). Here we report new iron data for the Ross Sea polynya during austral summer 2005-2006 (27 December-22 January) and the following austral spring 2006 (16 November-3 December). The summer 2005-2006 data show …

Kinematic And Dynamic Pair Collision Statistics Of Sedimenting Inertial Particles Relevant To Warm Rain Initiation, Bogdan Rosa, Hossein Parishani, Orlando Ayala, Lian-Ping Wang, Wojciech W. Grabowski

Engineering Technology Faculty Publications

In recent years, direct numerical simulation (DNS) approach has become a reliable tool for studying turbulent collision-coalescence of cloud droplets relevant to warm rain development. It has been shown that small-scale turbulent motion can enhance the collision rate of droplets by either enhancing the relative velocity and collision efficiency or by inertia-induced droplet clustering. A hybrid DNS approach incorporating DNS of air turbulence, disturbance flows due to droplets, and droplet equation of motion has been developed to quantify these effects of air turbulence. Due to the computational complexity of the approach, a major challenge is to increase the range of …

Towards An Integrated Multiscale Simulation Of Turbulent Clouds On Petascale Computers, Lian-Ping Wang, Orlando Ayala, Hossein Parishani, Wojciech W. Grabowski, Andrzej A. Wyszogrodzki, Zbigniew Piotrowski, Guang R. Gao, Chandra Kambhamettu, Xiaoming Li, Louis Rossi

Engineering Technology Faculty Publications

The development of precipitating warm clouds is affected by several effects of small-scale air turbulence including enhancement of droplet-droplet collision rate by turbulence, entrainment and mixing at the cloud edges, and coupling of mechanical and thermal energies at various scales. Large-scale computation is a viable research tool for quantifying these multiscale processes. Specifically, top-down large-eddy simulations (LES) of shallow convective clouds typically resolve scales of turbulent energy-containing eddies while the effects of turbulent cascade toward viscous dissipation are parameterized. Bottom-up hybrid direct numerical simulations (HDNS) of cloud microphysical processes resolve fully the dissipation-range flow scales but only partially the inertial …

Comparison Of Ice Core Dissolved Organic Matter From A Greenland Ice Core By Nanospray Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, Joshua Jeremiah Shiloh Marsh

Chemistry & Biochemistry Theses & Dissertations

Recent studies of ice cores have embarked on the task of determining the classes of dissolved organic matter (DOM) present in melt-water from the cores collected in numerous locations in the northern and southern hemispheres. This DOM originally derives from wet precipitation and is thought to reflect atmospheric organic matter derived from anthropogenic and non-anthropogenic sources. Because the amount of DOM is so low, previous studies have necessarily used large sample volumes (greater than 500 mL) to concentrate sufficient ice core DOM necessary for mass spectral analysis. Solid phase extraction (SPE) with C₁₈ resins was followed by evaporative concentration …

Trace Metal Biogeochemistry In The Western North Pacific, Peter Lynn Morton

OES Theses and Dissertations

Dissolved and suspended particulate samples collected during the Intergovernmental Oceanographic Commission 2002 Contaminant Baseline Survey were analyzed to determine the surface and vertical distributions of Cd, Co, Cu, Mn, Ni Zn and Pb across the western and central North Pacific.

Dissolved trace metal concentrations were measured using a novel isotope dilution-ICP-MS method after extraction over an 8-hydroxyquinoline resin column and validated through the use of the SAFe consensus reference materials. Filtered suspended particulate matter was digested using an HCl/HNO3/HF mixture and analyzed by HR-ICP-MS to obtain total particulate concentrations for the trace metals and other tracer elements such as Al, …