Analytical Chemistry Commons^™

Chemical Removal Of Total Phosphorus From Wastewater To Low Levels And Its Analysis, Farah Ateeq

Theses and Dissertations (Comprehensive)

Numerous studies have been conducted on the removal of inorganic phosphorus (P) from wastewater, but a push towards lower effluent targets necessitates the additional removal of organic phosphorus as well. This study tested the ability of manganese oxide nanoparticles and iron oxide as potential catalysts for conversion of organic P into more readily removable inorganic forms, as well as the role of iron(III) chloride as coagulant to subsequently allow P to be removed by solids/liquid separation. Removals of 99-101% were obtained for model compounds at pH 5-7, 0.05-0.5 M H₂O₂, and Fe:P molar ratio of 5:1. …

Heterogeneous Oxidation Of Catechol, Elizabeth A. Pillar, Ruixin Zhou, Marcelo I. Guzman

Chemistry Faculty Publications

Natural and anthropogenic emissions of aromatic hydrocarbons from biomass burning, agro-industrial settings, and fossil fuel combustion contribute precursors to secondary aerosol formation (SOA). How these compounds are processed under humid tropospheric conditions is the focus of current attention to understand their environmental fate. This work shows how catechol thin films, a model for oxygenated aromatic hydrocarbons present in biomass burning and combustion aerosols, undergo heterogeneous oxidation at the air–solid interface under variable relative humidity (RH = 0–90%). The maximum reactive uptake coefficient of O₃(g) by catechol γ_O3 = (7.49 ± 0.35) × 10^–6 occurs for …

Artificial Maturation Studies Of Polymethylenic Plant Biopolymers: Investigating The Chemical Alterations From Plant Material To Coal, Blaine Elizabeth Hartman

Chemistry & Biochemistry Theses & Dissertations

The thermal maturation and alternation of vascular plant material into coals and as expelled petroleum-like compounds is the main focus of this dissertation. Utilizing artificial maturation studies, like hydrothermal liquefaction, yields useful information regarding how plant material is preserved in coals and the potential certain plant biopolymers possess to generate liquid fuels is acquired. The studies within this dissertation focus on utilizing the aliphatic biopolymers, cutin, cutan, and suberan, found in the epidermis of certain plants. These biopolymers contain minimal amounts of heteroatoms and are comprised of long polymethylenic chains, which are desirable characteristics in generating bio-oils. Additionally, understanding the …

Pyrolysis-Gc-Ms For The Rapid Environmental Forensic Screening Of Contaminated Brownfield Soil, Azucena Lara-Gonzalo, Michael A. Kruge, I Lores, B Gutiérrez, José Luis Gallego

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

An abandoned chemical plant in Asturias (Spain) was studied using a multi-faceted molecular fingerprinting approach, demonstrating that it is possible to: (1) carefully unravel tangled evidence resulting from multiple pollution sources, and (2) recognize major contaminants largely ignored by conventional analyses. This methodology employed a battery of GC-MS analyses of liquid chromatographic fractions of soil extracts, plus the pyrolysis products of the soil extract's asphaltene fraction and the whole soil itself. In this example, coal tar distillation and the subsequent production of naphthalene, phenols and polymer resins are responsible for most of the soil contamination. Styrene, naphthalene, indene, and their …

Analytical Pyrolysis Principles And Applications To Environmental Science, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Over the past half century, analytical pyrolysis has proven itself to be an effective means for the semiquantitative characterization of complex macromolecular organic substances. It has been demonstrated that instruments such as Py-FID, Py-MS, and in particular, Py-GC/MS can provide valuable geochemical insights when applied to a wide variety of problems in environmental science. The more widespread use of analytical pyrolysis methods in the evaluation of environmental pollution is recommended, because of their relatively low cost and information-rich results.

Pyrolysis is the heating of organic substances in an inert, oxygen-free atmosphere, thereby avoiding combustion. When performed on a large scale, …

Derivatization And Separation Of Natural Estrogens (Estrone, 17Β-Estradiol, And Estriol) Using Gas Chromatography With Flame Ionization Detection (Gc-Fid), Dena L. Guptill

Masters Theses

A major cause of concern for estrogens found in the environment is that even at very low concentrations (10-100 ng/L) they can have a negative effect on aquatic ecosystems by disrupting endocrine systems. Due to the increasing importance of monitoring the levels of estrogens in the environment, a detection method was developed to identify and quantify three natural estrogens (estrone, 17β-estradiol and estriol) using gas chromatography with flame ionization detection (GC-FID). In addition, the efficacy of two derivatizing agents, N,O-bis(trimethylsilyl) acetamide (BSTA) and N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), was evaluated. The GC detector (FID) was most responsive with E3, followed by E1 and …

Catechol Oxidation By Ozone And Hydroxyl Radicals At The Air-Water Interface, Elizabeth A. Pillar, Robert C. Camm, Marcelo I. Guzman

Chemistry Faculty Publications

Anthropogenic emissions of aromatic hydrocarbons promptly react with hydroxyl radicals undergoing oxidation to form phenols and polyphenols (e.g., catechol) typically identified in the complex mixture of humic-like substances (HULIS). Because further processing of polyphenols in secondary organic aerosols (SOA) can continue mediated by a mechanism of ozonolysis at interfaces, a better understanding about how these reactions proceed at the air–water interface is needed. This work shows how catechol, a molecular probe of the oxygenated aromatic hydrocarbons present in SOA, can contribute interfacial reactive species that enhance the production of HULIS under atmospheric conditions. Reactive semiquinone radicals are quickly produced upon …

Environmental Assessment Of Used Motor Oil In The Ciudad Juarez-El Paso Area, Alma Leticia Figueroa

Open Access Theses & Dissertations

As a hazardous waste generated in large amounts worldwide, used motor oil (UMO) is an important issue for environmental science. UMO contains the carcinogenic and mutagenic compounds Polycyclic Aromatic Hydrocarbons (PAHs). Unless properly managed and disposed of PAHs remain in the environment, principally in sediments and soil. From such environmental sinks, PAHs can migrate to watersheds contaminate drinking water, and damage ecosystems and human health.

Generators of used oil include "businesses that handle used oil through commercial or industrial operations or from the maintenance of vehicles and equipment," (United States Environmental Protection Agency (USEPA), 2013). An example of such a …

Impact Of Zinc Oxide Nanoparticles On Green Pea Plant & Seed Quality And Effects On Physiological Traits Of Green Peas, Corn, And Zucchini By Silver Nanoparticles, Arnab Mukherjee

Open Access Theses & Dissertations

The production and use of numerous engineered nanomaterials (ENMs) have increased exponentially over the past decade. Nanoparticles (NPs), ENMs possessing diameter between 1-100 nm, (NPs), are widely used in many applications. Worldwide consumption of NPs has increased their possible release into the environment. This, in turn, has elevated the extent of the potential impacts of NP exposure to living and non-living organisms. This is why the assessment of the impact of NPs on different environmental components, especially on plants, the producer in the food web, has become a very important aspect of nano-ecotoxicology. However, studies focusing on phytotoxicity and effects …

Effects Of Cerium Oxide Nanoparticles In Cereals: Insights Into The Toxicity Mechanisms And Macromolecular Modifications, Cyren Mendoza Rico

Open Access Theses & Dissertations

Despite the inundation of studies on the interaction of engineered nanomaterials (ENMs) with plants, investigations involving complete life cycle (i.e from seedling establishment to full maturity) are still lacking. Assessments on the nutritional value of plants cultivated to full maturity in ENMs-treated soil are also missing. Cerium oxide nanoparticles (nCeO2) have significant interactions with plants; however, there are no life cycle studies yet on their implications in cereals like rice (Oryza sativa L.), wheat (Triticum aestivum L.), and barley (Hordeum vulgare L.). These cereals are globally important crops that support the economic activity, and nutritional and health needs of billions …

Determination Of The Uptake And Effects Of Tio2 Nanoparticles In Cucumber (Cucumis Sativus), Alia D. Servin

Open Access Theses & Dissertations

The profuse use of nanoparticles (NPs) in consumer products has raised concerns about their impacts in environmental and human health and possible transfer into the food chain through plants. Cucumber (Cucumis sativus L.) is a widely cultivated garden vegetable that could be in contact with NPs through biosolids. In this Dissertation research, the impact of TiO2 NPs was evaluated in cucumber plants grown in hydroponics and sandy loam soil. Hydroponically grown plants were treated for 15 days with 0-4000 mg/L of TiO2 NPs, and their vegetative tissues were studied using synchrotron micro X-Ray Fluorescence (micro-XRF) and Micro X-ray Absorption Near …

Conversion Of Iodide To Hypoiodous Acid And Iodine In Aqueous Microdroplets Exposed To Ozone, Elizabeth A. Pillar, Marcelo I. Guzman, Jose M. Rodriguez

Chemistry Faculty Publications

Halides are incorporated into aerosol sea spray, where they start the catalytic destruction of ozone (O₃) over the oceans and affect the global troposphere. Two intriguing environmental problems undergoing continuous research are (1) to understand how reactive gas phase molecular halogens are directly produced from inorganic halides exposed to O₃ and (2) to constrain the environmental factors that control this interfacial process. This paper presents a laboratory study of the reaction of O₃ at variable iodide (I^–) concentration (0.010–100 μM) for solutions aerosolized at 25 °C, which reveal remarkable differences in the reaction intermediates …

Separation Of Tc From U And Development Of Metallic Tc Waste Forms, Edward Mausolf

UNLV Theses, Dissertations, Professional Papers, and Capstones

The isotope Technetium-99 (⁹⁹Tc) is a major fission product of the nuclear industry. In the last decade, approximately 20 tons of 99Tc have been produced by the US nuclear industry. Due to its long half-life (t_1/2 = 214,000 yr), beta radiotoxicity, and high mobility as pertechnetate [TcO₄]^-, Tc represents long-term concern to the biosphere. Various options have been considered to manage ⁹⁹Tc. One of them is its separation from spent fuel, conversion to the metal and incorporation into a metallic waste form for long-term disposal. After dissolution of spent fuel in nitric …

Investigation Of Drinking Water/Beverage Contaminants Within The Beverage Industry, Elizabeth Hobbs

Theses

The impact of water resource quality has influenced the community worldwide. It is an on-going target for water suppliers to produce suitable drinking water and the beverage industry to provide suitable water for the production of beverages. This diligence will ensure the consumer is provided with a product safe for consumption. The research and analytical techniques explored in this thesis may be of benefit to the beverage industry for the monitoring of inorganic contaminants present in water and carbonated soft drinks. The occurrence of certain contaminants in drinking water has become a major issue in the water industry in recent …

Treatment Of Reverse Osmosis Brine With Advanced Oxidative Processes For Enhanced Phosphorus Removal, Petrease Patton

Theses and Dissertations (Comprehensive)

Current regulations for sensitive receiving waters are approaching the limit of technology for phosphorus removal and improved methods are required. Existing methods target removal of the orthophosphate form of phosphorus, but to achieve low effluent limits other non-reactive (NRP) forms, such as condensed phosphate and organic phosphorus, must be removed as well. This could be accomplished by developing a quaternary step in wastewater treatment that utilizes reverse osmosis (RO) followed by advanced oxidation processes (AOP) on the produced brine (RO concentrate). The objective during advanced treatment is to convert NRP in the brine to reactive phosphorus for removal by traditional …

Concentration Effects And Ion Properties Controlling The Fractionation Of Halides During Aerosol Formation, Marcelo I. Guzman, Richa R. Athalye, Jose M. Rodriguez

Chemistry Faculty Publications

During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO(2), NaNO(3), NaClO(4), and NaIO(4). The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of …

Enhancement In Degradation Of Environmental Pollutants: Fenton Degradation Of 2,4,6-Trinitrotoluene And Photodegradation Of Deepwater Horizon Crude Oil, Sarah M. King

LSU New Orleans Theses and Dissertations

Pollution poses serious threats to both the environmental and the organisms that depend on their environment for survival. Due to the toxicity of most contaminants, there is a dire need for remediation of polluted sites. Remediation studies were conducted on two high priority pollutants: 2,4,6-trinitrotoluene (TNT) and crude oil.

TNT was the most common explosive used in the 20^th century. Continuous contamination has resulted in an urgent need for remediation. Fenton reagent provides an advanced oxidation process that is capable of remediating recalcitrant explosives, such as TNT. One drawback of Fenton chemistry is that the reaction requires acidic pH …

Analysis Of Biodiesel Quality Using Reversed Phase High-Performance Liquid Chromatography, Kellyann M. Murphy

Pomona Senior Theses

The alternative fuel biodiesel is produced from the transesterification of vegetable oils or animal fat to fatty acid methyl esters. Pomona has a reactor on campus that can be used to run this reaction and produce biodiesel. The use of biodiesel has been found to lower air pollutant and greenhouse gas emissions, but can be potentially harmful to the engines if it contains impurities. This paper proposes a method using high-performance liquid chromatography to test the quality of biodiesel. This method utilizes instrumentation and materials that are available in Pomona College's Chemistry Department, requires very little sample preparation, and is …

Microscopic And Spectroscopic Analysis Of Wo3 And Ti-Doped Wo3 Thin Films, Young Taek Yun

Open Access Theses & Dissertations

Tungsten oxide (WO3) has been a subject of high interest for its unique properties, and recently for its importance in different types of industrial applications which ranges from non-emissive displays, optical, microelectronic, catalytic/photocatalytic, humidity, temperature, gas, and biosensor devices. In this study, WO3 and Ti doped thin films were prepared using radio frequency magnetron reactive sputtering at different substrate temperatures ranging from room temperature to 500 ºC in increments of 100 ºC. After forming a hypothesis based on knowledge of established WO3 properties, we attempt in this work to investigate how the doping influences the roughness and the mean grain …

Effects Of Weathering On Aromatic Compounds In Beach Tars From The Deepwater Horizon Disaster, Gulf Of Mexico Coast, Usa, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Operators aboard the Deepwater Horizon drilling platform lost control of the Macondo No. 1 well about 90 km southwest of the Louisiana coast on April 20, 2010, leading to a catastrophic release of ca. 550 Gg of crude oil over the next 86 days [1]. Oil from the spill soon found its way to nearby coastal areas, leaving tarry deposits on beaches and marshes. Oil was reported on the beach at Gulf Shores, Alabama (180 km northeast of the well) on June 5 and the relatively fresh sample discussed herein (GSA) was collected that same day. Oil reached the beach …

The Vinylguaiacol/Indole Or Vgi ("Veggie") Ratio: Assessing Relative Contributions Of Terrestrial And Aquatic Organic Matter To Sediments, Michael A. Kruge, Kevin K. Olsen, Jaroslaw W. Slusarczyk, Elaine Gomez

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

In studies of the organic matter (OM) fraction of marine, estuarine, fluvial, or lacustrine sediments, one of the most fundamental distinctions to be made is that between terrestrial and aquatic OM. To supplement the parameters commonly used for this purpose (e.g., C/N and stable isotope ratios), we proposed the Vinylguaiacol/Indole or VGI ("Veggie") ratio, defined as [vinylguaiacol / (indole + vinylguaiacol)] using data produced by analytical pyrolysis-gas chromatography/mass spectrometry of dried, homogenized sediment samples [1]. The ratio employs the peak areas of these two compounds on the mass chromatograms of their molecular ions (m/z 150 and 117, respectively). Major pyrolysis …

Determination Of 237np In Bioassay Fecal Samples, Bettylou M. Wahl

All Capstone Projects

²³⁷Np, a long-lived alpha-emitting actinide, is present in the environment due to releases from atmospheric nuclear weapons tests, reactor accidents, and nuclear reprocessing plants. The determination of long-lived actinides, such as neptunium, is essential for worker monitoring and environmental control. In bioassay and environmental samples, a radiochemical separation is necessary before measurement in order to eliminate any inferences that may occur in a mixture of actinides. In this paper, a method for determining ²³⁷Np in fecal samples using TEVA resin is investigated. Using ²³⁹Pu as a tracer, tetravalent plutonium and neptunium were successfully separated from other actinides. …

Determination Of Caffeine As A Marker For Septic Tank Contamination Of Wilgreen Lake, Rosemary Onjiko, Susan Godbey, Walter S. Borowski, Darrin Smith, Lori Wilson

EKU Faculty and Staff Scholarship

Wilgreen Lake in Richmond, Kentucky, has been listed by both the state and the Environmental Protection Agency as an “impaired” lake due to excess nutrients, which may be in part contributed by domestic septic systems. Caffeine can be used as an anthropogenic marker to estimate the contribution of septic tank effluent to the lake. We have modified existing analytical methods to produce a viable method for the determination of caffeine in environmental water samples and applied the method to water samples collected from Wilgreen Lake. The modified method allows determination of caffeine in a concentration range of 75 to 10,000 …

Variations In Concentrations And Compositions Of Polycyclic Aromatic Hydrocarbons (Pahs) In Coals Related To The Coal Rank And Origin, Susanne Laumann, Vesna Micic Batka, Michael A. Kruge, Christine Achten, Reinhard Sachsenhofer, Jan Schwarzbauer, Thilo Hofmann

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The release of unburnt coal particles and associated polycyclic aromatic hydrocarbons (PAHs) may cause adverse impacts on the environment. This study assessed variations in the concentration and composition of PAHs in a set of fifty coal samples from eleven coal basins worldwide. The maximum PAH concentrations at high volatile bituminous rank were recorded in samples from a single basin. Considering the entire sample, the highest PAH concentrations were in fact found outside of this rank range, suggesting that the maceral composition and thus the coal's origin also influenced PAH concentrations. The examination of the PAH compositions revealed that alkylated 2-3 …

Accumulation, Speciation, And Distribution Of Metal(Loids) In Plants: Applications Of Synchrotron Techniques In Environmental Sciences, Hiram Castillo-Michel

Open Access Theses & Dissertations

In the last two decades, synchrotron based techniques have gained popularity and been increasingly used in environmental sciences. The present dissertation has relied significantly in the use of synchrotron based techniques to study the speciation, coordination, and distribution of toxic metal(loids) in plants. This study included three plant species: Parkinsonia florida, Prosopis juliflora, and Zea mays. P. florida is a plant species native to the semi-desert regions of North America. The cultivation characteristics of this shrub/tree suggest that it could be used for phytoremediation purposes in semiarid regions. P. florida plants were tested for their capacity to remove arsenic (As) …

Quality Of Wastewater In The El Paso, Texas Region--Analysis Of Pharmaceuticals And Personal Care Products Using High Performance Liquid Chromatography Tandem Mass Spectrometry, Rodolfo Guerrero Jr.

Open Access Theses & Dissertations

Pharmaceuticals and Personal Care Products (PPCPs), such as household cleaning materials, prescription medication, and personal hygiene products, are pollutants of emerging concern that are found in 80% of our water system. Because of their applications, PPCPs are subsequently being released into wastewater; however, current wastewater treatment facilities are not regulated or designed to remove PPCPs. Therefore, these compounds are discharged into the environment on a continual basis. The effects of PPCPs on human health are not yet well known; however, recent research has found that exposure to these chemicals has some adverse developmental effects on aquatic species at low concentrations …

The Vinylguaiacol/Indole Or Vgi ("Veggie") Ratio: A Novel Molecular Parameter To Evaluate The Relative Contributions Of Terrestrial And Aquatic Organic Matter To Sediments., Michael A. Kruge, Kevin K. Olsen, Jaroslaw W. Slusarczyk, Elaine Gomez

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The organic matter (OM) fraction of estuarine sediments is often distinctive and thus diagnostically useful in determinations of sedimentary provenance. Among the most fundamental distinctions to be made is that between terrestrial and aquatic OM. To supplement the parameters commonly used for this purpose (e.g., C/N and stable isotope ratios), we proposed the Vinylguaiacol/Indole or VGI ("Veggie") ratio, defined as [vinylguaiacol / (indole + vinylguaiacol)] using data produced by analytical pyrolysis-gas chromatography/mass spectrometry of dried, homogenized sediment samples. The ratio employs the peak areas of these two compounds on the mass chromatograms of their molecular ions (m/z 150 and 117). …

Physical And Biochemical Assessment Of Mexican Palo Verde Response To Chromium Toxicity, Yong Zhao

Open Access Theses & Dissertations

In the United States, about 1/3 of the 1400 superfund sites have been reported to be chromium contaminated, making chromium the second most common metal found in superfund chemical contamination sites. Chromium removal from soil has commonly been carried out via chemical, physical, and thermal processes. However, these methods are expensive and/or invasive to local ecosystems. In contrast to these techniques, phytoremediation (the use of plants to remove toxic substances from areas containing contamination at low or medium levels) appears to be a cost-effective and environmentally friendly process for chromium removal. However, most reports on chromium phytoremediation suggest that this …

Geochemical Investigation Of An Offshore Sewage Sludge Deposit, Barcelona, Catalonia, Spain, Michael A. Kruge, Albert Permanyer, Jordi Serra, Danlin Yu

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

For 20 years ending in the 1990’s the city of Barcelona discharged the products from a large primary sewage treatment plant directly into the Mediterranean Sea via underwater conduits. About ca. 3 million m³ of relict sewage sludge, rich in organic matter and heavy metals, has spread over an elongated area offshore, due to successive ruptures of the conduits. The use of the discharge pipes ceased, but he sludge deposit remains in place for the time being.

To understand the history and present state of the sludge deposit in advance of future remediation, a program of geophysical mapping, sampling, …

Optimization Of Solid-Phase Microextraction For The Determination Of Organo-Phosphorus And Organo-Chlorine Pesticide Residues In Natural Water Near Aquaculture Farms., Chan Chun Foong

Student Works (2010-2019)

The global shrimp farming industry had a rapid growth in the 1980s due to the high demand for shrimp. Apart from the destruction of mangroves and wetlands, the intensive operation of shrimp aquaculture deteriorated the water quality in the region. Variety of chemicals and biological products were used to prevent the outbreaks of diseases in the intensively managed shrimp ponds. Pesticides were used as disinfectands to kill unwanted organisms in the pond. SPME-GC-ECD method was developed for the determination of azinphos-ethyl, chlorphyrifos-methyl, diazinon, dichlorvos, endosulfan-I, endosulfan-II, endosulfan sulfate and malathion from water samples of shrimp aquaculture area in Manjung district, …