Analytical Chemistry Commons^™

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). …

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, …

Toxicodynamics And Biotransformation Of Azaspiracids Incorporating Liquid Chromatography-Tandem-Mass Spectrometry (Lc-Ms/Ms) Techniques., Daniel O'Driscoll

Theses

Azaspiracids (AZAs) are a family of lipophilic polyether marine biotoxins, that have caused a number of human intoxication incidents in Europe since 1995, which was the first incident reported following the consumption by consumers of intoxicated shellfish {Mytilus edulis). This class of phycotoxins has been responsible for extended closures of shellfisheries in various locations around Europe, where levels of AZAl-3 are regulated in shellfish. Since their discovery in 1995, AZAs have become the focus of extensive research, resulting in the discovery of numerous analogues. Only AZAl and AZA2 have been found in phytoplankton and all the other analogues are believed …

Determination Of Lead, Cadmium, Zinc And Nickel Inedible Oil Products By Stripping Voltammetry., Ng Khan Loon

Student Works (2010-2019)

Edible oil products had become an everyday food that been consumed by most of the people either for dressing or for cooking purpose. Metal has become a common contamination to the food product, which it found the way into the edible oil through environment and processing contamination such as crushing, distillation, and hydrogenation. In this Study, the main focuses of metal analysis are only confined to 4 common metals which are the Cadmium, Lead, Zinc and Nickel. These elements are selected in this study due to reason that Cadmium and Lead are commonly known for their contamination from environment and …

Application Of Solid-Phase Microextraction For The Analysis Of Polycyclic Aromatic Hydrocarbons In Hyophila Involuta As A Natural Biosensor., Elizabeth Fong Yew Mei

Student Works (2010-2019)

This work describes a simple and rapid extraction method by using solid-phase microextraction (SPME) technique for the determination of polycyclic aromatic hydrocarbons (PAHs) from mosses of Hyophila involuta which is found commonly and abundantly throughout Peninsular Malaysia. Mosses have been chosen in our study since they are effective bioindicators as they take up nutrients and pollutants directly from the atmosphere and they have no root system. These properties make them ideal for evaluating pollutant levels in the air over a monitored period of time. This study has been developed and optimized based on the extraction of the analytes of interest …

Arsenic And Selenium Distribution In Coal-Fired Plant Samples, Pauline Rose Hack Norris

Masters Theses & Specialist Projects

Arsenic and selenium distributions in coal-fired plant samples are studied. This research includes arsenic and selenium concentrations in samples of coal, fly ash, bottom ash, economizer ash, Flue Gas Desulfurization (FGD) slurry and flue gas taken from four power plants with the goal being to examine the distribution of these metals in these materials and calculate a materials balance for the system. All samples were analyzed using ICP-ES.

This research shows that 60-80% of the arsenic in coal-fired plant samples will be associated with the fly ash. Approximately 35-55% of the selenium will be associated with the fly ash and …

Preparation And Characterization Of Some Substituted Benzyl N-Nitrosocarbamates Containing An N-2-(Methylthio)Ethyl Or A Bis(2-Aminoethyl)Sulfide Functionality, Satya Venkata, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

The synthesis and characterization of some substituted benzyl N-nitrosocarbamates with an N-2-(methylthio)ethyl or a bis(2-aminoethyl)sulfide functionality is reported, as a part of a long-term goal to design and prepare novel photolabile structures that could be used as substances for controlled release of alkylating and/or crosslinking agents. The synthesis was accomplished by reaction of benzyl chloroformates with the corresponding amines, resulting in the preparation of carbamates. The latter were subsequently nitrosated, utilizing two different N-nitrosation methods, to yield the target structures.

Monitoring Metal Containing Particulates Distribution On A College Campus Using Dandelion (Taraxacum Officinale) Leaves As Receptors., Suresh Chandra Regmi

Electronic Theses and Dissertations

This study aims to determine the distribution of particulates carrying heavy metals at selected sites on a college campus using dandelion leaves as collectors. As a comparison, sites far away from the campus surrounding Bristol Motor Speedway Car Racing Stadium were also monitored. To reduce the probability of memory effects from the long-term atmospheric deposition or absorption of metals from soil a seasonal plant, dandelion, was used to monitor the metal contents. The metals monitored are cadmium, calcium, copper, chromium, iron, lead, and zinc. Fourteen sites were monitored and samples were collected once a week initially (growing time of the …

Preparation Of Halogenated Derivatives Of Thiazolo[5,4-D]Thiazole Via Direct Electrophilic Aromatic Substitution, Vladimir Benin, Alan T. Yeates, Douglas Dudis

Chemistry Faculty Publications

Chlorination and bromination reactions of thiazolo[5,4-d]thiazole led to the generation of its mono- and dihalogenated derivatives. These are the first instances of successful direct electrophilic aromatic substitution in the thiazolo[5,4-d]thiazole ring system. X-ray analysis demonstrates that both 2-bromothiazolo[5,4-d]-thiazole and 2,5-dibromothiazolo[5,4-d]thiazole are planar structures, with strongly manifested π-stacking in the solid state. Theoretical analysis of the pyridine-catalyzed halogenation (MP2/6-31+G(d) and B3LYP/6-31+G(d)calculations) reveals that introduction of one halogen actually leads to a slightly enhanced reactivity towards further halogenation. Several halogenation mechanisms have been investigated: 1) The direct C-halogenation with N-halopyridine as electrophile; …

C–N Bond Rotation And E–Z Isomerism In Some N-Benzyl-N-Methylcarbamoyl Chlorides: A Dft Study, Michael Horwath, Vladimir Benin

Chemistry Faculty Publications

The current report presents the first theoretical study of the restricted CN bond rotation in carbamoyl chlorides. Several N-benzyl-N-methylcarbamoyl chlorides were investigated, with varying pattern of substitution in the aromatic ring. Optimizations and frequency calculations were conducted employing DFT at the B3LYP/6-31+G(d) level of theory. Each of the studied structures exhibits a pair of rotamers (s-Z and s-E), generated upon rotation around the C(O)N bond. The s-E isomer is the global minimum in every case, but the preference for it is usually less than 1 kcal/mol. Two possible transition state structures were identified …

Organic Geochemical Investigation Of A Highly Contaminated Urban Waterway: The Gowanus Canal, Brooklyn, New York, Usa, Michael A. Kruge, Kevin K. Olsen, Eric A. Stern

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The Gowanus Canal is an industrial waterway constructed in the mid-19^th century by widening and deepening a natural tidal channel. It is ca. 3 km in length and empties into Gowanus Bay, an arm of New York Harbor. Its banks, reinforced by bulkheads and piers, became the site of intensive industrial activity, including oil refining, coal gasification, soap making and tanning. Even though much of the industrial activity along the canal has ceased, its sediments remain highly enriched in organic and inorganic contaminants, with combined sewer outfalls continuing to transport pollutants into the canal. The canal area remains densely …

An Experiment Using A Simple Photoassisted Fuel Cell Designed To Remediate Simulated Wastewater, John Cassidy, Faisa Touati, Kevin Mcguigan

Articles

Work in photochemistry work peaked in the 1980’s where there was the prospect of using sunlight shining on suspensions of titanium dioxide in order to catalytically cleave water into hydrogen and oxygen [1-5]. In this way a clean and efficient method of producing hydrogen as a fuel was envisaged. However, there was a requirement to use a rather high energy light to achieve the splitting and it was not as efficient with visible light[5]. Doped TiO2 layers have been used in a three electrode system for formic acid degradation[6]. In this work, the system uses an electrode coated with TiO2 …

Improved Nitrate Sensing Using Ion Selective Electrodes Based On Urea–Calixarene Ionophores, Benjamin Schazmann, Dermot Diamond

Articles

Urea–calix[4]arenes 1 and 2 were synthesised and incorporated into ISE membranes for assessment as sensors for inorganic anions in water. 1 revealed a strong response to all anions following the Hofmeister selectivity order. For ISEs of 2, the response to a portion of the anion series was suppressed, increasing the margin of selectivity of nitrate over chloride, a common interferant of nitrate in fresh and marine water samples. The performance of ISEs containing 2 was compared to commercially available alkylammonium nitrate ion-exchange salts used for nitrate sensing. Our ISEs performed favourably in terms of sensitivity, linear range and LOD performing …

Significance Of Polycyclic Aromatic Hydrocarbons (Pahs) And Petroleum Biomarker Compounds In Contaminated Passaic River Sediments, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The lower Passaic River (northeastern New Jersey) flows through one of the most densely populated regions of the United States. The area’s long history of industrial activity is reflected in the complex and variable hydrocarbon composition of the river sediments. Sediments from river bottom grab samples at Newark and a 30 cm deep core at Kearny were subjected to thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). This technique offers a practical alternative for rapid, inexpensive analysis, simply employing milligram quantities of dry, disaggregated sediment, avoiding the use of hazardous organic solvents. For each sample, a total of 181 hydrocarbons and organosulfur compounds …

Secondary N-Nitrosocarbamate Anions: Structure And Alkylation Reactions. A Dft Study, Vladimir Benin

Chemistry Faculty Publications

The current article reports theoretical studies (DFT: B3LYP/6-31+G(d)) on the structure and alkylation reactions of the anions of some secondary N-nitrosocarbamates, a class of ambident nucleophiles whose chemistry has been little explored. Several anions (1–4), with an increasing size of the carbamate alkyl (aryl) group were investigated, in an attempt to establish the influence of the size of that group on the thermal stability and regioselectivity of alkylation of the title anions. The conclusion is that thermal stability and the mode of reaction are affected significantly only in the presence of very large and branched carbamate groups. The thermal …

Development Of A Calix[4]Arene Sensor For Soft Metals Based On Nitrile Functionality, Benjamin Schazmann, Dermot Diamond

Articles

The current work is amongst the first to examine the potential usefulness of the nitrile functional group in potentiometric analytical sensors for soft metals. Nitrile functionality has hereby been incorporated into a calix[4]arene skeleton to give a series of new cation selective hosts. The analytical sensing behaviour of these hosts was examined by Ion Selective Electrode (ISE) based potentiometry. In all cases a preference for soft metals was observed, explained primarily in terms of soft–soft compatibility between calix[4]arene nitrile hosts and metal guests in combination with a classical ‘lock and key’ best fit mechanism. Hosts 2, 3 and 4 showed …

Preparation Of Some Substituted Terephthalic Acids, Susanna Branion, Vladimir Benin

Chemistry Faculty Publications

We report in detail the preparation of two substituted terephthalic acids: 2‐sulfomethylterephthalic acid (1) and 2‐phosphonoterephthalic acid (2). Efficient, short syntheses have been developed for both compounds. They are potentially useful monomers for construction of acid‐pendant polymer chains.

Preparation, Characterization And Dft Studies Of Some New N-Nitrosocarbamates And N-Nitrosoureas, Ragavan Narayanan, Helene Hedian, Eric Shamo, Vladimir Benin

Chemistry Faculty Publications

We are presenting the preparation, characterization and density functional theory (DFT) studies {B3LYP/6-31+G(d)) of several reiated classes of N-nitrosocarbamates and N-nitrosoureas. The iong-range goal is the design and preparation of compounds, which would undergo photochemical or hydrolytic decomposition, to yield stabilized cyclic cations that can serve as alkylating agents at various nucleophilic centers, including DNA bases.

Synthesis, Structural Studies And Desilylation Reactions Of Some N-2-(Trimethylsilyl)Ethyl-N-Nitrosocarbamates, Arpitha Thakkalapally, Vladimir Benin

Chemistry Faculty Publications

The present report describes the preparation and characterization of several N-2-(trimethylsilyl)ethyl-N-nitrosocarbamates, designed as precursors to thermally unstable secondary N-nitrosocarbamate anions via fluoride-assisted cleavage. X-ray structural studies demonstrate that the core N-nitrosocarbamate moiety has a nearly planar geometry, with an s-E orientation at the N–N bond. DFT calculations (B3LYP/6-31+G(d)) reproduce accurately the structural features of the title compounds and detailed conformational analysis at the same level of theory addresses the long-standing issue of preferred geometries for three classes of related structures: N-nitrosocarbamates, N-nitrosoureas and N-nitrosoamides. Desilylation studies demonstrate that both the …

Application Of Pyrolysis-Gc/Ms For Rapid Assessment Of Organic Contamination In Sediments From Barcelona Harbor, Michael A. Kruge, Albert Permanyer

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Pyrolysis-GC/MS is advantageous as a tool for rapid sediment contamination assessment because of the small sample size required, minimal sample preparation, and its ability to detect a wide variety of organic pollutants as well as naturally-occurring biological materials. Py-GC/MS was applied, together with determination of organic carbon, and major and minor element concentrations, to evaluate potentially contaminated sediments in the port of Barcelona (Spain) and the adjacent Llobregat River delta. Detected contaminant markers, most evident in the Old Port (Port Vell) area, included hopanes and alkylated PAHs (petroleum), sterenes (sewage), C₁₆-C₁₉ phenylalkanes (detergents) and parent …

Development And Optimization Of Hplc-Icpms For The Determination Of Iodine Speciation In Groundwater, Yun Qiu

All-Inclusive List of Electronic Theses and Dissertations

High performance liquid chromatography has been coupled with online inductively coupled plasma mass spectrometry detection for the determination of iodine speciation in drinking and groundwaters. Using ion exchange chromatography, the method is applied to quantify the concentrations of iodine species in groundwaters. The HPLC-UV detection was used first to examine the separation efficiency of the HPLC method. The limit of quantification was obtained for the HPLC-UV analysis. Direct ICPMS analysis of iodine species has been validated and optimized using an HC03"/C03 2 - aqueous solvent. HPLC was then interfaced to the ICPMS T-shape connection to allow online addition of internal …

Support For The Nye County Early Warning Drilling Program, Irene Farnham, Klaus J. Stetzenbach, Amy J. Smiecinski

Publications (YM)

This final report details the activities completed for Task 8 of the University and Community College System of Nevada (UCCSN) Cooperative Agreement with the US Department of Energy (DOE). Task 8, titled "Support for the Nye County Early Warning Drilling Program" provided for a variety of hydrochemical analyses. The requirements of the University and Community College System of Nevada (UCCSN) Quality Assurance (QA) Program were followed for all work performed on this task. The primary activity performed by the Harry Reid Center for Environmental Studies (HRC) for Task 8 was to provide hydrochemical analyses of the groundwater samples collected from …

Organic Geochemical Analysis Of Late-Glacial And Early-Holocene Ecosystem Changes: A Case Study From Northern New England Lakes, Michael A. Kruge, Andrea Lini

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The lacustrine sedimentary archive of organic remains provides important evidence for the reconstruction of the environmental histories of lakes and their watersheds, recording the response of the Earth's biota to changes on scales varying from the local to the global. The last Glacial-Interglacial transition presents an opportunity to investigate how, and at what rates, watershed and lake ecosystems were established on once glaciated, carbon and nutrient-poor landscapes. The small lakes of northern Vermont (USA) provide an appropriate setting in which to investigate such changes.

As part of a multidisciplinary study of three Vermont lake sediment cores, samples ranging in age …

Analysis Of Fuel Additives And Impurities In Gasoline, Nicholas Lentz

Honors Capstones

Capstone submitted as a graduation requirement for the BSU Honors Program.

Use Of Py-Gc/Ms Analysis Techniques In Animal Waste Management: A Preliminary Survey Of Dairy Manures, Daniel L. Vaughn, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The increasing practice of industrial-scale agriculture tends to concentrate large masses of animal waste in relatively compact areas, potentially leading to excessive release of polluting nutrients into waterways during major storms. Anaerobic treatment conditions are generally favored to conserve nitrate N as an agricultural commodity. However, overall N contents in waste are often in excess of crop fertilization needs: storing excess N in soluble nitrate form increases pollution potential. Thus the perceived needs of agriculture and society-at-large become at odds. Organic nitrogen forms (e.g., proteins) are more environmentally stable and are less subject to unintentional release. Although U.S. farmers tend …

Biogeochemistry And Contaminant Geochemistry Of Marine And Estuarine Sediments, New Haven, Connecticut (Usa), Michael A. Kruge, Gaboury Benoit

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The urbanized shore areas of Long Island Sound in the vicinity of New Haven, Connecticut (USA) have a long history of exposure to point and non-point sources of pollution, New Haven having been one of the birthplaces of the industrial revolution. As an unintended consequence of such activities, the region's sedimentary systems have incorporated a complex mixture of organic and inorganic contaminants. With its long and varied pollution history and the multiplicity of sedimentary environments (fluvial, estuarine, intertidal, marsh, etc.) present in a compact geographical area, the region is ideal natural laboratory for field testing new contamination assessment techniques. The …

Direct Titrimetric Determination And Of Sulphate, Chee Kin Tan

Student Works (2000-2009)

Interference by foreign ions in direct titrimetric determination of sulphate with barium perchlorate using dimethylsulphonazo III (DMSA Ill) as indicator were studied in this research project. The use of certain water miscible solvents as titration medium has enhanced the determination of end-point. Among the methanol, ethanol, n-propanol and acetone used in the investigation, it was found that medium containing 40 to 50% n-propanol or acetone delivered distinct end-points. The effects of nine cations and eight anions were studied in the above sulphate titration. It was found that the interference caused by Li",Na",K",Mg2"·Mn2", Cd2", NH4", CI and Br are not significant. …

Humic Substances As Interferences In The Analysis Of Nitrite In Water, Stephanie Ann Tebault

Chemistry & Biochemistry Theses & Dissertations

Humic substances are of current interest because of their roles in environmental processes involving pollutants. It is also becoming recognized that humic substances may interfere in analysis of environmental samples though the possible adverse effects do not appear to be fully appreciated. The present effort focuses on determining whether humic materials interfere in the analysis of nitrite in water using the Griess reaction. This is a well-known reaction using nitrosation to gjve a diazonium salt followed by coupling with an appropriate reagent to form a dye. This colorimetric method continues to be applied in the laboratory and the field for …

Environmental And Botanical Controls On Peatification - A Comparative Study Of Two New Zealand Restiad Bogs Using Py-Gc/Ms, Petrography And Fungal Analysis, Tomasz K. Kuder, Michael A. Kruge, J C. Shearer, S L. Miller

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

This study shows that chemical properties of two restiad species, Empodisma minus and Sporadanthus traversii, may contribute to their success as peat-formers in a climate of the North Island of New Zealand which is not conducive to raised mire development. Unlike Sphagnum, the equivalent northern hemisphere peat-former, restiads possess lignin in their tissues. In addition, the presence of non-lignin polyphenols (including tannins and phenolic acids) in restiads may be an important factor in peat formation due to the allelopathic decay retardation. Patterns of degradation of plant biopolymers have been examined and the pathway of degradation of monocotyledons (loss …

A Molecular Evaluation Of Contaminants And Natural Organic Matter In Surface Sediments From Western Lake Ontario, Michael A. Kruge, Prasanta K. Mukhopadhyay, C.F. Michael Lewis

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) analysis of bottom sediment from Lake Ontario was shown to be effective in assessing organic contaminants, especially attractive as it is a rapid technique requiring little sample preparation. Pyrolyzates of samples richer in organic matter (OM) were relatively enriched in aliphatic hydrocarbons and pyrrolic nitrogen compounds, while leaner samples were more aromatic and pyridinic. Alkylbenzene and alkylphenol distributions in the pyrolyzates were most compatible with derivation from aquatic (algal, bacterial) OM. The organonitrogen compounds indicated the presence of degraded proteinaceous material from aquatic sources and/or sewage. Normal and polycyclic aromatic hydrocarbon distributions indicate, at least in …