Physical Sciences and Mathematics Commons^™

Molecular Fossils From Phytoplankton Reveal Secular Pco2 Trend Over The Phanerozoic, Caitlyn R. Witkowski, Johan W. H. Weijers, Brian S. Blais, Stefan Schouten, Jaap S. Sinninghe Damsté

Science and Technology Department Faculty Journal Articles

Past changes in the atmospheric concentration of carbon dioxide (PCO2) have had a major impact on earth system dynamics; yet, reconstructing secular trends of past PCO2 remains a prevalent challenge in paleoclimate studies. The current long-term PCO2reconstructions rely largely on the compilation of many different proxies, often with discrepancies among proxies, particularly for periods older than 100 million years (Ma). Here, we reconstructed Phanerozoic PCO2 from a single proxy: the stable carbon isotopic fractionation associated with photosynthesis (Ɛp) that increases as PCO2 increases. This concept has been widely applied to alkenones, but here, we …

Spatial Variation In Throughfall, Soil, And Plant Water Isotopes In A Temperate Forest, Gregory R. Goldsmith, Scott T. Allen, Sabine Braun, Nadine Engbersen, Clara Romero González-Quijano, James W. Kirchner, Rolf T. W. Siegwolf

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Studies of stable isotopes of water in the environment have been fundamental to advancing our understanding of how water moves through the soil‐plant‐atmosphere continuum; however, much of this research focuses on how water isotopes vary in time, rather than in space. We examined the spatial variation in the δ¹⁸O and δ²H of throughfall and bulk soil water, as well as branch xylem and bulk leaf water of Picea abies (Norway Spruce) and Fagus sylvatica (Beech), in a 1 ha forest plot in the northern Alps of Switzerland. Means and ranges of water isotope ratios varied considerably …

Aptamer-Based Assay For Detection Of Ochratoxin A, Amanda Nicole Bartley

FIU Electronic Theses and Dissertations

Ochratoxin A (OTA) is a potent mycotoxin found in a wide range of agricultural products that has been linked to mitochondrial damage and renal disease. The standard methods for OTA analysis currently rely on the use of high-performance liquid chromatography (HPLC) coupled to fluorescence detection or mass spectrometry. Toward a highthroughput analysis of OTA, a single-stranded DNA aptamer, modified with a fluorophore, coupled to a complementary sequence, modified with a FRET-based quencher that dissociates in the presence of the target toxin, is proposed. In order to integrate “target trapping,” aptamer immobilization methods were explored to mediate interference issues. Assays were …

Unrefined Humic Substances As A Potential Low-Cost Remediation Method For Groundwater Contaminated With Uranium In Acidic Conditions, Hansell Gonzalez Raymat

FIU Electronic Theses and Dissertations

Anthropogenic activities such as uranium mining and milling, nuclear weapons production, and nuclear reprocessing have left a legacy of groundwater and soil contaminated with uranium that needs to be addressed. Therefore, developing new remediation technologies to sequester uranium in situ is crucial. The objective of the study was to determine if low-cost commercially available unrefined humic substances, such as Huma-K, can be used to facilitate uranium sorption to minerals in soil and sediment. Sediments from the saturated zone beneath the F-Area seepage basins at the Savannah River Site (SRS) in South Carolina were used for the present study. The SRS …

Eddy Flux Measurements Of Sulfur Dioxide Deposition To The Sea Surface, Jack G. Porter, Warren J. De Bruyn, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Deposition to the sea surface is a major atmospheric loss pathway for many important trace gases, such as sulfur dioxide (SO2). The air–sea transfer of SO2 is controlled entirely on the atmospheric side of the air–sea interface due to high effective solubility and other physical– chemical properties. There have been few direct field measurements of such fluxes due to the challenges associated with making fast-response measurements of highly soluble trace gases at very low ambient levels. In this study, we report direct eddy covariance air–sea flux measurements of SO2, sensible heat, water vapor, and momentum. The measurements were made over …

Fundamental Mechanistic Studies On The Ultrasonic Treatment Of Problematic Water Pollutants And Toxins, Danni Cui

FIU Electronic Theses and Dissertations

Problematic organic pollutants in industrial and drinking water sources are a leading cause of water scarcity. Among the advanced oxidation processes, sonolytic degradation has received considerable attention because it combines oxidation processes initiated by reactive oxidant species and a pyrolysis processes associated with the high temperatures produced during cavitation.

The degradation of the semi-volatile compound, MCHM, was rapid and followed pseudo-first order kinetics. The Freundlich kinetic model for heterogeneous systems was successfully applied to describe the non-uniform distribution of MCHM at the gas-liquid interface during ultrasonic treatment. Two primary products were confirmed by GC-MS. Computational studies were also applied to …

Photocatalytic Activity: Experimental Features To Report In Heterogeneous Photocatalysis, Md. Ariful Hoque, Marcelo I. Guzman

Chemistry Faculty Publications

Heterogeneous photocatalysis is a prominent area of research with major applications in solar energy conversion, air pollution mitigation, and removal of contaminants from water. A large number of scientific papers related to the photocatalysis field and its environmental applications are published in different journals specializing in materials and nanomaterials. However, many problems exist in the conception of papers by authors unfamiliar with standard characterization methods of photocatalysts as well as with the procedures needed to determine photocatalytic activities based on the determination of “apparent quantum efficiencies” within a wavelength interval or “apparent quantum yields” in the case of using monochromatic …

Data On Ion Composition And X-Ray Diffraction Patterns Of Biosolids From Wastewater Treatment Plants In Lufkin And Nacogdoches, Texas, Usa, Kefa Karimu Onchoke, Christopher M. Franclemont, Paul W. Weatherford

Faculty Publications

The data presented in this article is related to the research article entitled, “Structural Characterization and Evaluation of Municipal Wastewater Sludge (Biosolids) from two Rural Wastewater Treatment Plants in East Texas, USA”, Onchoke, KK, Franclemont, C.M., Spectrochim. Acta A, In press[1]. The XRD profiles and composition of biosolids from wastewater treatment plant is presented. This study describes the composition of XRD crystalline phase patterns of the wastewater sludge. After the removal of the Ka2 peaks the d-spacing and hkl values were determined. In addition, the ion chromatographic profile of the seven anions (NO₃^-, NO_{2 …}

Responses Of Daphnia Magna To Chronic Exposure Of Cadmium And Nickel Mixtures, Edgar Pérez, Tham C. Hoang

School of Environmental Sustainability: Faculty Publications and Other Works

The present study assessed the chronic toxicity of cadmium (Cd) and nickel (Ni) mixtures to Daphnia magna. Using a titration design, Ni concentrations of 20, 40, 80, 100, 120, 140, and 160 μg/L were tested alone and simultaneously titrated in increments against a constant concentration of 1.5 μg/L Cd. The results demonstrated that Cd at 1.5 μg/L was highly toxic to D. magna, and Ni alone concentrations ≥80 μg/L were toxic to D. magna survival, reproduction, and growth. No Ni alone concentration was found to induce a toxic effect on undeveloped embryos and the time to first brood. …

An Overview Of Dynamic Heterogeneous Oxidations In The Troposphere, Elizabeth A. Pillar-Little, Marcelo I. Guzman

Chemistry Faculty Publications

Due to the adverse effect of atmospheric aerosols on public health and their ability to affect climate, extensive research has been undertaken in recent decades to understand their sources and sinks, as well as to study their physical and chemical properties. Atmospheric aerosols are important players in the Earth’s radiative budget, affecting incoming and outgoing solar radiation through absorption and scattering by direct and indirect means. While the cooling properties of pure inorganic aerosols are relatively well understood, the impact of organic aerosols on the radiative budget is unclear. Additionally, organic aerosols are transformed through chemical reactions during atmospheric transport. …

Short-Term Low Salinity Mitigates Effects Of Oil And Dispersant On Juvenile Eastern Oysters: A Laboratory Experiment With Implications For Oil Spill Response Activities, Meagan N. Schrandt, Sean Powers, F.Scott Rikard, Wilawan Thongda, Eric Peatman

University Faculty and Staff Publications

Following the Deepwater Horizon oil spill, eastern oyster (Crassostrea virginica) reefs in the northern Gulf of Mexico were exposed to oil and various associated clean-up activities that may have compromised oyster reef health. Included in the exposure was oil, dispersant, and in some locales, atypical salinity regimes. Oil and dispersants can be detrimental to oysters and the effects of salinity depend on the level. In addition to these extrinsic factors, genetic diversity of oyster populations may help the oysters respond to stressors, as demonstrated in other systems. We used a 3×3×2 factorial design to experimentally examine the effects …

Assembling Of Niox/Mwcnts-Gc Anodic Nanocatalyst For Water Electrolysis Applications, Yaser M. Asal Mr., Islam M. Al-Akraa Dr, Saher D. Khamis Eng

Chemical Engineering

Glassy carbon (GC) electrode is intended to be modified with nickel oxide (NiOx) and multiwalled carbon nanotubes (MWCNTs) in the anodic reaction of water electrolysis. NiOx deposition time is optimized and a 5 min was enough to attain the maximum activity. A further modification of the catalyst with MWCNTs could greatly enhance its stability during continuous electrolysis. As an outcome, an energy amount of 21.7 kWh/KgO₂ is minimized. Several electrochemical and materials characterization setups will be utilized to test the catalyst activity and to know its geometry and structure.

Enhanced Acidity Of Acetic And Pyruvic Acids On The Surface Of Water, Alexis J. Eugene, Elizabeth A. Pillar, Agustín J. Colussi, Marcelo I. Guzman

Chemistry Faculty Publications

Understanding the acid–base behavior of carboxylic acids on aqueous interfaces is a fundamental issue in nature. Surface processes involving carboxylic acids such as acetic and pyruvic acids play roles in (1) the transport of nutrients through cell membranes, (2) the cycling of metabolites relevant to the origin of life, and (3) the photooxidative processing of biogenic and anthropogenic emissions in aerosols and atmospheric waters. Here, we report that 50% of gaseous acetic acid and pyruvic acid molecules transfer a proton to the surface of water at pH 2.8 and 1.8 units lower than their respective acidity constants pK_{a …}

Fabrication Of Mnox/Mwcnts-Gc Nanocatalyst For Oxygen Evolution Reaction, Yaser M. Asal Mr, Islam M. Al-Akraa Dr, Amr M. Arafa Eng.

Chemical Engineering

Manganese oxide (MnOx) and multiwalled carbon nanotubes (MWCNTs) are intended to modify the GC electrode for oxygen evolution reaction (OER). Optimization of MnOx loading is carried out and the deposition of 55 cycles was sufficient to obtain the highest activity toward OER. The stability of the catalyst is enhanced by the addition of MWCNTs. As a result, an amount of 22 kWh/Kg of O₂ of energy is saved. Several techniques including cyclic voltammetry, linear sweep voltammetry, chronoamperometry, chronopotentiometry, field-emission scanning electron microscopy, and energy dispersive X-ray spectroscopy will be combined to track the catalyst activity and to determine its …

Removal Of Acid Yellow 25 From Aqueous Solution By Chitin Prepared From Waste Snow Crab Legs, Chin-Chuan Wei, Inoka K. Pathiraja, Emily Fabry, Kyle Schafer, Nick Schimp, Tuo-Ping Hu, Lawrence P. Norcio

SIUE Faculty Research, Scholarship, and Creative Activity

Acid Yellow 25 (AY25) is used in the textile industry for dyeing of natural and synthetic fibers, and is also used as a coloring agent in paints, inks, plastics, and leathers. Effluents from such industries are major sources of water pollution. Hence, it is important to find simple, efficient, and inexpensive ways to remove these dyes from wastewater. Here, we determined the suitability of chitin extracted from waste crab legs as an adsorbent for removing AY25 dye. The adsorption kinetics was modeled using pseudo-first order, pseudo-second order, and intraparticle diffusion equations to determine the rate controlling step. Results showed that …

Characterization Of The Uranium-Bearing Phases Produced By Novel Remediation Technologies For Sequestration Of Mobile Radiological Contaminants In The Hanford 200 Area Vadose Zone, Robert Michael Lapierre

FIU Electronic Theses and Dissertations

Of the many toxic chemicals released into the Hanford vadose zone over the decades of nuclear weapons production, uranium has emerged as a contaminant of significant interest. The ammonia gas injection remediation method has been identified as a promising approach towards mitigating the risks to the ecosystem by limiting the mobility of the radionuclide in the vadose zone. The remediation method was replicated using synthetic porewater solutions with a range of constituent concentrations equal to that of the Hanford 200 Area vadose zone. The uranium-bearing products of the remediation method were characterized using kinetic phosphorescence analysis for aqueous uranium, scanning …

Cross Photoreaction Of Glyoxylic And Pyruvic Acids In Model Aqueous Aerosol, Sha-Sha Xia, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

Aerosols of variable composition, size, and shape are associated with public health concerns as well as with light-particle interactions that play a role in the energy balance of the atmosphere. Photochemical reactions of 2-oxocarboxylic acids in the aqueous phase are now known to contribute to the total secondary organic aerosol (SOA) budget. This work explores the cross reaction of glyoxylic acid (GA) and pyruvic acid (PA) in water, the two most abundant 2-oxocarboxylic acids in the atmosphere, under solar irradiation and dark thermal aging steps. During irradiation, PA and GA are excited and initiate proton-coupled electron transfer or hydrogen abstraction …

The Investigation Of Photocatalytic And Adsorptive Properties Of Humic Acid Grafted Magnetite Nanoparticles For The Remediation Of Arsenic, Selenium And Phosphorous From Water, Mohammad Mamunur Rashid

FIU Electronic Theses and Dissertations

The crisis of freshwater has been a big concern worldwide. Water contamination that occurs through the discharge of toxic pollutants from different natural and anthropogenic sources have worsened the situation. Adsorption has emerged as a simple and economical water treatment procedure although the challenge is to find the right adsorbent that can efficiently remove the target contaminant followed by their easy recovery from the reaction vessel. In this dissertation, I have focused on the synthesis, characterizations and applications of environmentally compatible and magnetic humic acid coated magnetite nanoparticles (HA-MNP) as a potential adsorbent for water purification.

Phosphate is an essential …

The Cyclodextrin-Perfluorinated Surfactant Host-Guest Complex: Fundamental Studies For Potential Environmental Remediation And Therapeutic Applications, Mary J. Errico

FIU Electronic Theses and Dissertations

Perfluoroalkyl substances (PFASs) are contaminants of emerging concern, and have been detected in drinking water, wildlife, humans, and the environment. Cyclodextrins (CDs), cyclic sugars composed of glucose monomers, are proposed as a potential remediation strategy. CDs can form host-guest complexes with hydrophobic molecules; this complexation could be capitalized on for PFAS removal and sequestration. These dissertation projects aim to study the fundamental host-guest interactions between a variety of PFASs and CDs for eventual applications in environmental and biological remediation. 1D and 2D Nuclear magnetic resonance (NMR) spectroscopic methods were employed to determine the strength, dynamics, and structure of the CD:PFAS …

Environmental Dynamics Of Dissolved Organic Matter And Dissolved Black Carbon In Fluvial Systems: Effects Of Biogeochemistry And Land Use, J. Alan Roebuck Jr.

FIU Electronic Theses and Dissertations

Black carbon (BC) is an organic residue formed primarily from biomass burning (e.g., wildfires) and fossil fuel combustion. Until recently, it was understood that BC was highly recalcitrant and stabilized in soils over millennial scales. However, a fraction of the material can be solubilized and transported in fluvial systems as dissolved BC (DBC), which represents on average 10% of the global export of dissolved organic carbon (DOC) from rivers to coastal systems. The composition of DBC controls its reactivity, and it has been linked with a variety of in-stream processes that induce both carbon sequestration and evasion of CO₂ from …

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 …

Hydrodeoxygenation Of Pinyon-Juniper Catalytic Pyrolysis Oil Using Red Mud-Supported Nickel Catalysts, Hossein Jahromi, Foster Agblevor

Biological Engineering Faculty Publications

Red mud (RM) is an alkaline waste generated in the Bayer process of alumina production. In the present study red mud supported nickel catalysts (Ni/RM) were prepared at different concentrations of nickel (10, 20, 30, 40, 50, and 65 wt.%) and used to hydrodeoxygenate (HDO) pinyon-juniper (PJ) catalytic pyrolysis oil. Increasing the nickel content improved the activity of Ni/RM catalysts for HDO reactions. Maximum organic liquid yield (68.6%) was obtained when 40%Ni/RM was used. The upgraded oil had oxygen content of 1.35 wt.% and higher heating value of 45.77 MJ/kg compared to 24.88 wt.% and 28.41 MJ/kg, respectively, for the …

Kinetic Modeling Of The Atmospheric Photooxidation Of Reduced Sulfur And Nitrogen Compounds, Jesus Alejandro Berlanga

Masters Theses & Specialist Projects

Atmospheric aerosols encapsulate a wide variety of particles with different compositions, sizes and sources of origin. They also directly and indirectly affect climate by their interactions with sunlight, clouds, atmospheric chemical species, and even other suspended particles. To understand the atmospheric aerosol processes and the effects they have in global and regional climate is of utmost importance for the future establishment of environmental regulations and emission policies that affect aerosol precursor compounds in an effective and beneficial manner. In particular, aerosols are known to be formed from emissions from human activities, such as fossil fuel burning, agriculture, or concentrated animal …

Imidazolium Ionic Liquids As Multifunctional Solvents, Ligands, And Reducing Agents For Noble Metal Deposition Onto Well-Defined Heterostructures And The Effect Of Synthetic History On Catalytic Performance, Michael Drake Ballentine

Masters Theses & Specialist Projects

1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM]Tf2N) was investigated as a multifunctional solvent, ligand, and reducing agent for platinum deposition onto well-defined CdSe@CdS nanorods. Platinum deposition was carried out thermally and photochemically using Pt(acac)2 as the metal precursor. Thermal deposition was investigated in [BMIM]Tf2N with and without addition of a sacrificial reducing agent, and product topology was compared with the products obtained from polyol reduction using 1,2-hexadecanediol, oleic acid, and oleylamine in diphenyl ether. Photochemically induced platinum deposition was carried out at room temperature in [BMIM]Tf2N, and product topology was compared with the photodeposition products obtained from a toluene dispersion. Thermal deposition of platinum …

Production And Composition Of Pyrogenic Dissolved Organic Matter From A Logical Series Of Laboratory-Generated Chars, Kyle W. Bostick, Andrew R. Zimmerman, Andrew S. Wozniak, Siddhartha Mitra, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Though pyrogenic carbon (pyC) has been assumed to be predominantly stable, degradation and transfers of pyC between various pools have been found to influence its cycling and longevity in the environment. Dissolution via leaching may be the main control on loss processes such as microbial or abiotic oxidation, mineral sorption, or export to aquatic systems. Yet, little is known about the controls on pyrogenic dissolved organic matter (pyDOM) generation or composition. Here, the yield and composition of pyDOM generated through batch leaching of a thermal series of oak and grass biochars, as well as several non-pyrogenic reference materials, was compared …

Using Spectral Methods To Obtain Particle Size Information From Optical Data: Applications To Measurements From Cares 2010, Dean B. Atkinson

Chemistry Faculty Publications and Presentations

Multi-wavelength in situ aerosol extinction, absorption and scattering measurements made at two ground sites during the 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES) are analyzed using a spectral deconvolution method that allows extraction of particle-sizerelated information, including the fraction of extinction produced by the fine-mode particles and the effective radius of the fine mode. The spectral deconvolution method is typically applied to analysis of remote sensing measurements. Here, its application to in situ measurements allows for comparison with more direct measurement methods and validation of the retrieval approach. Overall, the retrieved finemode fraction and effective radius compare well with …

Automating Data Analysis For Two-Dimensional Gas Chromatography/Time-Of-Flight Mass Spectrometry Non-Targeted Analysis Of Comparative Samples, Ivan A. Titaley, O. Maduka Ogba, Leah Chibwe, Eunha Hoh, Paul H.-Y. Cheong, Staci L. Massey Simonich

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Non-targeted analysis of environmental samples, using comprehensive two‐dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC × GC/ToF-MS), poses significant data analysis challenges due to the large number of possible analytes. Non-targeted data analysis of complex mixtures is prone to human bias and is laborious, particularly for comparative environmental samples such as contaminated soil pre- and post-bioremediation. To address this research bottleneck, we developed OCTpy, a Python™ script that acts as a data reduction filter to automate GC × GC/ToF-MS data analysis from LECO^® ChromaTOF^® software and facilitates selection of analytes of interest based on peak area …

Concentration, Amount And Counting By Weighing, Julian Tyson

Science and Engineering Saturday Seminars

Concentration, Amount and Counting by Weighing

UMass Amherst STEM Ed Institute Saturday Workshop 2/3/2018

Julian Tyson, Professor Emeritus, Department of Chemistry. Tyson@chem.umass.edu

Session 1. Introductions.

Ice-breaker: The elementarity contest.

Setting the scene: “How much arsenic do we eat?” Why do we want to know? The Consumer Reports articles (Nov 2012 and Nov 2014)

Dealing with really big and really small numbers.

Session 2. Amount, concentration

Solids, liquids and gases. The “parts per” concept.

Session 3. Counting by weighing

The count equation. Rice grains (the bottle content problem), atoms and molecules.. Chemical formulas and balanced chemical expressions. The numbers in the …

Quantitative Three-Dimensional Basal Ice Roughness From Scanning Electron Microscopy (Sem), Katie Gray, Shreeti Patel

Summer Research

A method for analyzing the three-dimensional surface roughness on the basal facets of polar ice crystals is presented. A functional form of backscattered electron intensity as a function of ice facet orientation is adapted for the use of the basal facet. Using the Gauss-Newton inversion within a Bayesian framework a three dimensional representation of rough surfaces are retrieved at roughly micrometer resolution. Following the development of new statistical measures allow for higher statistical confidence and the connection to a scaling growth mechanism for crystal development. In a collection of results from temperatures ranging from -29 degrees celsius to -35 degrees …

Experiential Learning Activity: Biodiesel Inquiry Project, Ji Kim

Open Educational Resources

The activity described herein can be implemented in introductory chemistry and high school chemistry courses. The main goal of the project is to integrate a ubiquitous biodiesel production with experiential learning by providing a community-based project. The students work in groups, research the benefits of using biodiesel over petroleum-based diesel, collect waste cooking oil from home or restaurants, develop simple and cost-effective methods to produce biodiesel.