Analytical Chemistry Commons^™

Applications Of Drones In Atmospheric Chemistry, Travis J. Schuyler

Theses and Dissertations--Chemistry

The emission of greenhouse gases (GHGs) has changed the composition of the atmosphere during the Anthropocene. A major technical and scientific challenge is quantifying the resulting fugitive trace gas fluxes under variable meteorological conditions. Accurately documenting the sources and magnitude of GHGs emission is an important undertaking for discriminating contributions of different processes to radiative forcing. Therefore, the adverse environmental and health effects of undetected gas leaks motivates new methods of detecting, characterizing, and quantifying plumes of fugitive trace gases. Currently, there is no mobile platform able to quantify trace gases at altitudes(UASs), or drones, can be deployed on-site in …

Near Real-Time Determination Of The Prevalence Of Cannabinoids, Cathinones, And Synthetic Opioids, Catherine O'Rourke, Bikram Subedi

Scholars Week

Unregulated new psychoactive substances (NPS) in “pure” or “preparation” forms are designed to mimic the effects of controlled substances, and are introduced and reintroduced in the market as a cheap substitute of established regulated drugs in quick succession to loophole the law enforcement efforts on combating drugs. For example, carfentanil, a synthetic opioid activates the opioid receptors similar to morphine but it is astoundingly potent compared to a typical drug of abuse (100 times more potent than fentanyl and 10,000 times more powerful than morphine). Based on the cost- and time-intensive forensic analysis, National Drug Early Warning System reported the …

Determination Of Cannabinoids, Cathinones, And Synthetic Fentanyls Using Wastewater-Based Epidemiology, Catherine O'Rourke, Bikram Subedi

Posters-at-the-Capitol

Unregulated new psychoactive substances (NPS) in “pure” or “preparation” forms are designed to mimic the effects of controlled substances, and are introduced and reintroduced in the market as a cheap substitute for established regulated drugs in quick succession to loophole the law enforcement efforts on combating drugs. For example, carfentanil, a synthetic opioid activates the opioid receptors similar to morphine but it is astoundingly potent compared to a typical drug of abuse (100 times more potent than fentanyl and 10,000 times more powerful than morphine). Based on the cost- and time-intensive forensic analysis, National Drug Early Warning System reported the …

Hour-Level Resolution On Consumption Pattern Of Substance Abuse, Jarrett Mauk, Rhiannon Huffines, Brittney Nelson, Tara Croft, Bikram Subedi

Scholars Week

Conventional survey-based approaches of determining the consumption statistics of drugs in communities are suffered from non-response biases, and typically underestimate the actual consumption. Time and cost-intensive conventional approaches, therefore, can’t be utilized to determine high-resolution temporal variability in drug consumption. In this study, the temporal trend of consumption of 10 illicit and 26 prescribed neuropsychiatric drugs was determined at hour-level resolution utilizing wastewater-based epidemiology. The hourly composite raw wastewater (every 10 minutes) samples were collected for three consecutive days in a typical week (total of 72 samples), analyzed for target drug residues using UPLC-MS/MS, and back-calculated the consumption rate of …

Environmental Forensic Characterization Of Former Rail Yard Soils Located Adjacent To The Statue Of Liberty In The New York/New Jersey Harbor, Diane Hagmann, Michael A. Kruge, Matthew Chi-Hymn Cheung, Maria Mastalerz, José Luis Gallego, Jay Prakash Singh, Jennifer Krumins, Xiaona N. Li, Nina M. Goodey

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Identifying inorganic and organic soil contaminants in urban brownfields can give insights into the adverse effects of industrial activities on soil function, ecological health, and environmental quality. Liberty State Park in Jersey City (N.J., USA) once supported a major rail yard that had dock facilities for both cargo and passenger service; a portion remains closed to the public, and a forest developed and spread in this area. The objectives of this study were to: 1) characterize the organic and inorganic compounds in Liberty State Park soils and compare the findings to an uncontaminated reference site (Hutcheson Memorial Forest); and 2) …

Consumption Profiles Of Illicit And Neuropsychiatric Drugs In Urban And Rural Communities In Kentucky Using Sewage Epidemiology, Tara Croft, Katelyn Foppe, Rhiannon Huffines, Bikram Subedi

Posters-at-the-Capitol

The drug overdose deaths in the USA increased by ~20% from 2015 to 2016 to the total >63,600 drug overdose deaths in 2016. Kentucky is among the highest rate of drug overdose death states in the USA. The current estimates of the prevalence of substance abuse are based on the self-reported surveys, overdose/toxicological reports, and drug-related crime statistics. Survey-based conventional approaches are not only cost and time-intensive but also underestimate the actual consumption of drugs. As “wastewater never lie,” the drug residues in raw wastewater collected from the centralized wastewater treatment plants were utilized to determine the consumption rate of …

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 …}

Legacy Contaminants In The Northern Gulf Of Mexico Shelf, Jessica N. Landry

LSU Master's Theses

The Mississippi River watershed is the third largest in the world and drains from 31 states in the United States. Due to its route through the U.S., it passes through hundreds of EPA labeled Superfund sites as well as agricultural and suburban watersheds. These sites are known to have historical chemical contamination, and as a result chemicals can be transported by runoff down the Mississippi River into the Gulf of Mexico where their ultimate fate is unknown. Organochlorine chemicals are known to be persistent and are found in agricultural land as well as US EPA Superfund sites, especially DDT, PCBs, …

Environmental Forensics Study Of Crude Oil And Petroleum Product Spills In Coastal And Oilfield Settings: Combined Insights From Conventional Gc-Ms, Thermodesorption-Gc-Ms And Pyrolysis-Gc-Ms, Michael A. Kruge, José Luis Gallego, Azucena Lara-Gonzalo, Noemi Esquinas

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

A representative set of five oil spill samples from four different regions displayed different product characteristics and different levels of weathering. Three of them were taken along shorelines affected by marine oil spill events, viz., Aboño and Prestige (Spain) and Deepwater Horizon (USA) and the other two were taken at inland oil spill sites (Angola and Kuwait). A multi-faceted environmental forensics approach revealed key molecular features. In addition to the conventional GC/MS analysis of saturated and aromatic fractions, the polar fractions also were analyzed, revealing a complex series of linear alkanones in those oil samples particularly enriched in aliphatics. Thermodesorption-GC-MS …

Multivariate Statistical Analyses Of Air Pollutants And Meteorology In Chicago During Summers 2010–2012, Katrina Binaku, Martina Schmeling

Chemistry: Faculty Publications and Other Works

Aerosol, trace gas, and meteorological data were collected in Chicago, Illinois during 2010–2012 summer air studies. Ozone, nitrogen oxides, acetate, formate, chloride, nitrate, sulfate, and oxalate concentrations as well as temperature, wind speed, wind direction, and humidity data were explored by both principal component analysis (PCA) and canonical correlation analysis (CCA). Multivariate statistical techniques were applied to uncover existing relationships between meteorology and air pollutant concentrations and also reduce data dimensions.

In PCA, principal components (PC) revealed a relationship of ozone and nitrate concentrations with respect to temperature and humidity, coupled with transport of species from the south in relation …

Unmanned Aerial Systems For Monitoring Trace Tropospheric Gases, Travis J. Schuyler, Marcelo I. Guzman

Chemistry Faculty Publications

The emission of greenhouse gases (GHGs) has changed the composition of the atmosphere during the Anthropocene. Accurately documenting the sources and magnitude of GHGs emission is an important undertaking for discriminating the contributions of different processes to radiative forcing. Currently there is no mobile platform that is able to quantify trace gases at altitudes(UASs) can be deployed on-site in minutes and can support the payloads necessary to quantify trace gases. Therefore, current efforts combine the use of UASs available on the civilian market with inexpensively designed analytical systems for monitoring atmospheric trace gases. In this context, this perspective introduces the …

Evaluation Of A Filtration Sorbent For Remediation Of Arsenic In Groundwater, Clement Do

Electronic Theses, Projects, and Dissertations

A commercially available product, PURA PhosLock, was identified and evaluated for use as a sorbent to remove dissolved arsenic (As) from drinking water. Although marketed as a product to remove phosphate in aquaria, it is composed of iron oxide hydroxide (i.e., FeO(OH)), which is also known to adsorb dissolved As species from water. Arsenic was measured using standard methods and Graphite Furnace Atomic Absorption Spectroscopy. A first rough filtration test was performed to see if the PhosLock adsorbed As well. About 50 g of PhosLock was used to filter 10 L of tap water containing 100 ppb As. No detectable …

Phthalate And Non-Phthalate Plasticizers In Indoor Dust From Childcare Facilities, Salons, And Homes Across The Usa, Bikram Subedi, Kenneth D. Sullivan, Birendra Dhungana

Faculty & Staff Research and Creative Activity

The quality of indoor environment has received considerable attention owing to the declining outdoor human activities and the associated public health issues. The prolonged exposure of children in childcare facilities or the occupational exposure of adults to indoor environmental triggers can be a culprit of the pathophysiology of several commonly observed idiopathic syndromes. In this study, concentrations of potentially toxic plasticizers (phthalates as well as non-phthalates) were investigated in 28 dust samples collected from three different indoor environments across the USA. The mean concentrations of non-phthalate plasticizers [acetyl tri-n-butyl citrate (ATBC), di-(2-ethylhexyl) adipate (DEHA), and diisobutyl adipate (DIBA)] were found …

Mass Loading And Removal Of Pharmaceuticals And Personal Care Products Including Psychoactives, Antihypertensives, And Antibiotics In Two Sewage Treatment Plants In Southern India, Bikram Subedi, Keshava Balakrishna, Derrick Ian Joshua, Kurunthachalam Kannan

Faculty & Staff Research and Creative Activity

Environmental contamination by pharmaceuticals and personal care products (PPCPs) is barely studied in India despite being one of the largest global producers and consumers of pharmaceuticals. In this study, 29 pharmaceuticals and six metabolites were determined in sewage treatment plants (STPs) in Udupi (STP_U: population served ~150,000) and Mangalore (STP_M: population served ~450,000); the measured mean concentrations ranged from 12 to 61,000 ng/L and 5.0 to 31,000 ng/L, respectively. Atorvastatin (the most prescribed antihypercholesterolemic in India), mefenamic acid, and paraxanthine were found for the first time in wastewater in India at the mean concentrations of 395 …

Assessment Of Surface Water Contamination From Coalbed Methane Fracturing-Derived Volatile Contaminants In Sullivan County, Indiana, Usa, Nicholas Meszaros, Bikram Subedi, Tristan Stamets, Naima Shifa

Faculty & Staff Research and Creative Activity

There is a growing concern over the contamination of surface water and the associated environmental and public health consequences from the recent proliferation in hydraulic fracturing in the USA. Petroleum hydrocarbon-derived contaminants of concern [benzene, toluene, ethylbenzene, and xylene (BTEX)] and various dissolved cations and anions were spatially determined in surface waters around 14 coalbed methane fracking wells in Sullivan County, IN, USA. At least one BTEX was detected in 69% of sampling sites (n=13) and 23% of sampling sites were found to be contaminated with all of the BTEX. Toluene was the most common BTEX compound detected across all …

A Novel Method For Determination Of Ammonium Isotope Ratios With Electrospray Ionization Mass Spectrometry, Rebecca J. Chmiel

Honors Theses

Nitrogen (¹⁵N) isotope tracer studies are an invaluable tool for understanding the rate of N transformations in the environment. A mechanistic understanding of N cycling is critical to management of excess N availability in freshwater and marine ecosystems. Conventional methods for measuring ¹⁵N:¹⁴N of dissolved inorganic nitrogen species are time consuming and require large sample volumes. Here, we present a technique for measuring ¹⁵N:¹⁴N in ammonium (NH₄⁺) using electrospray ionization mass spectrometry (ESI-MS). NH₄⁺ present in small volumes of sample (3 ml) is complexed with phenol via …

Caffeine Used As A Tracer Of Wastewater Contamination In South Florida, Stephanie Spence

Honors Program Theses

In this study, a method was developed to analyze caffeine levels of water samples collected in Miami, Florida. The method was used to determine caffeine concentrations in reclaimed water samples and environmental water samples using on-line solid phase extraction (SPE) high pressure liquid chromatography (HPLC) high resolution mass spectrometry (HRMS). The rising use and disposal of pharmaceuticals and personal care products are becoming a concern as contaminants increasingly enter lakes, streams, and rivers without proper removal by traditional wastewater treatment processes. Caffeine may be used as a chemical tracer to indicate the presence of contamination in water samples and to …

Environmental Emission Of Pharmaceuticals From Wastewater Treatment Plants In The Usa, Bikram Subedi, Bommanna G. Loganathan

Faculty & Staff Research and Creative Activity

The residual drugs, drug bioconjugates, and their metabolites, mostly from human and veterinary usage, are routinely flushed down the drain, and enter wastewater treatment plants (WWTP). Increasing population, excessive use of allopathic medicine, continual introduction of novel drugs, and existing inefficient wastewater treatment processes result in the discharge of large volumes of pharmaceuticals and their metabolites from the WWTPs into the environment. The effluent from the WWTPs globally contaminate ~25% of rivers and the lakes. Pharmaceuticals in the environment, as contaminants of emerging concerns, behave as pseudo-persistent despite their relatively short environmental half-lives in the environment. Therefore, residual levels of …

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 …

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 …

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, …

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 …

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 …

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, …

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 …

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 …

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 …

Preliminary Geochemical Evaluation Of Groundwaters From Wells Of The Nye County Early Warning Drilling Program, Irene Farnham, Klaus J. Stetzenbach, Amy J. Smiecinski

Publications (YM)

As part of the Yucca Mountain Oversight program, the Nye County Nuclear Waste Repository Project Office (NWRPO) has established a groundwater monitoring program to protect groundwater resources for the residents of Nye County in Amargosa and Pahrump Valleys. This groundwater monitoring program, referred to as the Nye County Early Warning Drilling Program (NCEWDP), involves drilling a series of wells down-gradient from Yucca Mountain for long term groundwater monitoring and also to provide much needed geologic and hydrologic information in this area. A comprehensive database of aquifer parameters in the alluvial, volcanic, and carbonate aquifers down-gradient hydrogeologically of Yucca Mountain is …