Chemistry Commons^™

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 …

A Program Aimed Toward Inclusive Excellence For Underrepresented Undergraduate Women In The Sciences, Laura A. Katz, Kathryn M. Aloisio, Nicholas J. Horton, Minh Ly, Sara B. Pruss, Kate Queeney, Cate Rowen, Patricia Marten Dibartolo

Biological Sciences: Faculty Publications

Created to foster inclusive excellence, Smith College’s Achieving Excellence in Mathematics, Engineering, and Science (AEMES) Scholars program provides early faculty-mentored research opportunities and other programming as a way to foster success in academic outcomes for underrepresented women in science. Using academic record data, we compared Scholars’ outcomes over time with those of underrepresented students before program launch and to relevant peer comparison groups. Since its launch, AEMES Scholars have achieved significantly higher gateway life sciences course grade point averages (GPAs), rates of persistence in life and natural sciences, and participation in natural sciences advanced research relative to baseline. Gains for …

Integrating The Field Of Prebiotic Chemistry Into A Christian Worldview, Matthew B. Anderson

Senior Honors Theses

This thesis will provide an overarching examination into the scientific field of prebiotic chemistry, the purported chemistry of the formation of life on earth. Prebiotic chemistry is a critical area of science particularly for Christian scientists to study since it is used by many evolutionists as evidence for the evolution of life, rather than the formation by an intelligent designer. Extensive literature-based research from previously published articles will be conducted on the formation of biologically necessary molecules, including amino acids. Primary focus will be placed on the formation of amino acids in a primordial earth environment, first demonstrated by the …

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 …

Stable Isotope Chemistry In Titan Haze Aerosol, Allison Wold, Thomas Gautier, Jennifer Stern, Joshua Sebree, Melissa Trainer

Research in the Capitol

Titan, a moon of Saturn, has a thick atmosphere made up of nitrogen and a few percent methane, with a surface pressure of 1.5x that of Earth. Titan’s atmosphere is believed to be that similar to that of early Earth before the rise of O2. One significant source of information on the history and evolution of the atmosphere is the measurement of stable isotopes of elements in the molecules of major gases such as nitrogen, methane, and higher order hydrocarbons. The fractionation associated with the formation of Titan aerosol analogs are explored in the laboratory as a function of environmental …

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, …

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 …

A Miniaturized Spectrophotometric In Situ Ph Sensor For Seawater, Reuben C. Darlington

Graduate Student Theses, Dissertations, & Professional Papers

Since the Industrial Revolution, the world's oceans have absorbed increasing amounts of CO2 and the resultant changes to the marine carbonate chemical system have reduced the pH by > 0.1 units (~ 30%) in surface waters. This acidification of the oceans has many far reaching impacts on marine life and there is great need of quality instrumentation to assess and follow the changing carbonate system. This MIS project aims to develop a low cost pH sensor with high precision and accuracy for open sea measurements with special emphasis on reduced size and cost. Design effort is based on the commercially available …

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 …

Assessing The Impact Of A Constructed Wetland Biome On The Ecosystem Health Of Cedar Run, Thomas Vasilopoulos, Casey Lee

Senior Honors Projects, 2010-2019

A wetlands ecosystem is defined as “an area saturated by surface or groundwater at a frequency or duration sufficient to support...a prevalence of vegetation typically adapted for life in saturated soil conditions” (Batzer and Sharitz, 2007). Wetlands serve as biofilters and thus have been used to treat sewage and wastewater, as well as to restore the health of polluted water systems. Solly Walker and Lorinda Palin, owners of a certified natural and biodynamic farm called Avalon Acres located in Broadway, Virginia, constructed a wetland two years ago, using the stream, Cedar Run, that flows through their property. Pollution from agricultural …

In Situ Ion Exchange In A Micro-Porous Transition Metal Silicate Framework, Jason M. Lively

Masters Theses & Specialist Projects

Ion selectivity of minerals has traditionally been utilized in industry as a catalyst, metal separation, and environmental reclamation/sequestration tool. There is an increased interest in understanding ion selectivity mechanisms of micro-porous minerals and mineral-like structures and how they can be applied in various industries: environmental and, potentially, pharmaceutical. This study seeks to understand the ion exchange mechanisms in micro-porous zirconosilicates using time-resolved Raman spectroscopy and X-ray diffraction. The thesis material was exchanged with H+, Na+, K+, and Cs+ in order to better understand structural changes as well as the influence of the H+-bonding during the exchange process. It is hypothesized …

A Complex Legacy Of Contamination In Urban Estuarine Systems, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Industrialized urban waterways have typically suffered decades of contamination, varying in source and intensity as manufacturing and transportation practices evolved. The U.S. Environmental Protection Agency designates locales with particularly severe contamination as Superfund sites. Among these, the Gowanus Canal and lower Passaic River in the New York/New Jersey harbor estuary illustrate a complex range of contamination types.

The 2.2 km Gowanus Canal, with sluggish circulation driven mostly by tides, accumulated fine-grained sediments (average thickness of 3 m) highly enriched in organic carbon (OC, mean 11 % but up to 49 %) derived from hydrocarbons, sewage, coal, char, and biomass, along …

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 …

Petrographic And Geochemical Characteristics Of The Kiejo, Rungwe And Ngozi Volcanic Rocks, Southern Tanzania: Implication For Tectonic Activities And Magmatic Differentiation, Athanas S. Macheyeki

Tanzania Journal of Science

Rock samples were collected from the Kiejo, Rungwe and Ngozi volcanoes, southern Tanzania. Results show that, in the Ngozi and Rungwe volcanoes, magma cooled relatively fast. After large part of the magma had crystallized, nucleation of crystals at a relatively slow rate crystallized from interstitial fluids of the primary magma that had already crystallized fine grained minerals resulting into large grains of minerals. In the Kiejo volcano, both zoned and unzonned olivine crystals exist; unzoned crystals being primary and the zoned ones are secondary. Such observations also indicate that the magma responsible for these rocks had interstitial fluids that crystallized …

Understanding The Surface Induced Phosphorylation Of Prebiotic Molecules By Schreibersite, Danna Qasim

Master of Science in Chemical Sciences Theses

The study of the surface of a meteoritic mineral, schreibersite (Fe,Ni)₃P, was investigated to provide insight into the role of the mineral’s surface in aqueous-phase phosphorylation reactions. The optimization of a custom-designed ultrahigh vacuum (UHV) apparatus and Fe₂NiP (schreibersite) surface was performed to permit surface science analysis. The bare surface was characterized by scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS), which showed some oxidation and segregation of phosphorous within the near-surface region. The interaction and/or reaction of water (H₂O), methanol (CH₃OH), formic acid …

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 …

One Year Later: The Politics And Stories Of Post-Earthquake Nepal, Boyer Andrew

Independent Study Project (ISP) Collection

A 7.8 magnitude earthquake struck Nepal on April 25^th, 2015. This was followed by a second major earthquake of magnitude 7.3 on May 12^th , 2015. These disasters took the lives of thousands of Nepali people, destroyed hundreds of thousands of structures, and displaced an estimated two million people. Immediately following the disaster, there was an outpouring of humanitarian aid from around the world. This lead to a conference where $4.1 billion USD of reconstruction funds were pledged to Nepal by international donors. Five months later, a new constitution passed into law and an informal blockade of …

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 …

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 …

Nitrous Oxide In The Atmosphere: First Measurements Of A Lower Thermospheric Source, Patrick E. Sheese, Kaley A. Walker, Chris D. Boone, Peter F. Bernath, Bernd Funke

Chemistry & Biochemistry Faculty Publications

Nitrous oxide (N₂O) is an important anthropogenic greenhouse gas, as well as one of the most significant anthropogenic ozone-depleting substances in the stratosphere. The satellite-based instrument Atmospheric Chemistry Experiment-Fourier Transform Spectrometer has been observing the Earth's limb since 2004 and derives profiles of N₂O volume mixing ratios in the upper troposphere to the lower thermosphere. The resulting climatology shows that N₂O is continuously produced in the lower thermosphere via energetic particle precipitation and enhanced N₂O is present at all latitudes, during all seasons. The results are consistent with an N₂O …

Source Apportionment Of Atmospheric Particulate Matter In Developing Countries Using Trace Elements And Stable Metal Isotope Ratios, Nitika Dewan

Electronic Theses and Dissertations

The work presented herein details the source apportionment of atmospheric particulate matter in developing countries (Kyrgyzstan in Central Asia, metropolitan cities in Northern India, and Shenzhen in China) using trace elements and stable metal isotope ratios. The first study focused on the development of a novel method for the concomitant separation of rare-earth elements in environmental samples of any geological origin. The separation procedure is based on three extraction chromatographic materials, referred to as Sr.Spec, TRU.Spec, and Ln.Spec. This triple column arrangement enables the simultaneous isolation of pure Sr and Nd fractions in less than one day and with great …

Determination Of Volcanic Impact On Perchlorate Using Polar Ice Cores, Alex Georgiev, Collin Livingston, Cody Ward

The Journal of Undergraduate Research

Arctic (Greenland) ice core samples covering the time period of 1638-1646 were analyzed for perchlorate and sulfate concentrations. The sulfate data show a signal corresponding to the 1640 eruption of the Komaga-Take volcano in Japan. Perchlorate concentrations show a significant increase at the time of the Komaga-Take eruption. It is concluded that a positive correlation likely exists between stratospheric volcanic eruptions and perchlorate concentration in the environment. When a volcano has enough explosive force to inject substances into the stratosphere, some of the substances, such as sulfate, can remain in the stratosphere for months and spread all over the global …

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 …

Adsorption Of Antibiotics By Vermiculite, Mosa J. Ferdous

Dissertations and Theses

The occurrence of residual antibiotics in the environment has been a worldwide issue and warrants the development of inexpensive yet effective methods for antibiotics removal from contaminated water. In this thesis work, the adsorption of four antibiotics, namely chlorotetracycline (CTC), oxytetracycline (OTC), ofloxacin (OFL), and enrofloxacin (ENR), onto natural vermiculite has been studied using batch (static) and column (dynamic) adsorption techniques. The Langmuir and Freundlich isotherm models were initially used to explain the adsorption processes. The separation factor (RL) values derived from the Langmuir model and the 1/n values derived from Freundlich model in the present investigation were less than …

Measurement Of Antioxidant Activity Toward Superoxide In Natural Waters, D. Whitney King, Emma Berger, Zachary Helm, Eleanor Irish, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Antioxidants are a class of molecules that provide a protective function against reactive oxygen species (ROS) in biological systems by out competing physiologically important molecules for ROS oxidation. In natural waters, the reactivity of antioxidants gives an estimate of oxidative stress, and may determine the reactivity and distribution of reactive oxidants. We present an analytical method to measure antioxidant activity in natural waters through the competition between ascorbic acid, an antioxidant, and MCLA, a chemiluminescent probe for superoxide. A numerical kinetic model of the analytical method has been developed to optimize analytical performance. Measurements of antioxidant concentrations in pure and …

Water Vapour Variability In The High-Latitude Upper Troposphere- Part 2: Impact Of Volcanic Eruptions, Christopher E. Sioris, Jason Zou, C. Thomas Mcelroy, Chris D. Boone, Patrick E. Sheese, Peter F. Bernath

Chemistry & Biochemistry Faculty Publications

The impact of volcanic eruptions on water vapour in the high-latitude upper troposphere is studied using deseasonalized time series based on observations by the Atmospheric Chemistry Experiment (ACE) water vapour sensors, namely MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) and the Fourier Transform Spectrometer (ACE-FTS). The two eruptions with the greatest impact on the high-latitude upper troposphere during the time frame of this satellitebased remote sensing mission are chosen. The Puyehue-Cordón Caulle volcanic eruption in June 2011 was the most explosive in the past 24 years and is shown to be able to account …

Seasonal Evolution Of Active Layer Formation In Subarctic Peat Plateaux And Implications For Dissolved Organic Matter Composition And Transfer, Jennifer L. Hickman

Theses and Dissertations (Comprehensive)

Peat-accumulating wetlands are ecosystems whose rate of photosynthetic production of organic matter is greater than that of its decomposition, resulting in a build up of soil organic matter that may take centuries to fully decompose. Carbon (C) stocks within these ecosystems are a function of inputs from photosynthesis, and losses from heterotrophic decomposition. Due to the short growing season and overall cold climate of boreal and tundra regions, C has been accumulating within these landscapes, mostly in soil organic matter, since the last glaciation. Climate change, predicted to result in rising temperatures and increased precipitation, has begun to degrade the …

The Role Of Organic Matter In The Surface Chemistry Of Arsenic Compounds On Iron−(Oxyhydr)Oxides Studied By Atr-Ftir, Arthur Situm

Theses and Dissertations (Comprehensive)

The interaction of organic matter with the interfaces of active soil components such as iron oxides is ubiquitous within soil environments. The presence of organics at these interfaces may have implications for other soil constituents whose mobility is controlled by their ability to bind to active soil components. Most of the studies performed to date which look at these interactions are bulk/batch studies performed ex-situ. Attenuated total internal reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was utilized within this work to study interactions between select model organics (citrate, oxalate and pyrocatechol) and iron−(oxyhydr)oxides, as well as their effect on the surface …

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 …

Erratum To: Zn (Ii) And Cu (Ii) Adsorption And Retention Onto Iron Oxyhydroxide Nanoparticles: Effects Of Particle Aggregation And Salinity, Rebecca B. Chesne, Christopher S. Kim

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

In the original version of this article errors in Figs. 5 and 9 were identified by the authors. The corrected figures are given.