Environmental Chemistry Commons^™

Deep Soils Modify Environmental Consequences Of Increased Nitrogen Fertilizer Use In Intensifying Amazon Agriculture, Kathijo Jankowski, Christopher Neill, Eric A. Davidson, Marcia Macedo, Ciniro Costa Jr., Gillian L. Galford, Leonardo Maracahipes Santos, Paul Lefebvre, Darlisson Nunes, Carlos E. P. Cerri, Richard Mchorney, Christine S. O'Connell, Michael T. Coe

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Agricultural intensification offers potential to grow more food while reducing the conversion of native ecosystems to croplands. However, intensification also risks environmental degradation through emissions of the greenhouse gas nitrous oxide (N₂O) and nitrate leaching to ground and surface waters. Intensively-managed croplands and nitrogen (N) fertilizer use are expanding rapidly in tropical regions. We quantified fertilizer responses of maize yield, N₂O emissions, and N leaching in an Amazon soybean-maize double-cropping system on deep, highly-weathered soils in Mato Grosso, Brazil. Application of N fertilizer above 80 kg N ha⁻¹ yr⁻¹ increased maize yield and N …

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 …

Geochemistry Of Archaeological And Marine Environments In Southwest Maine, Heather L. Bushie

Thinking Matters Symposium Archive

Two archaeological excavations for the University of Southern Maine collected sediment columns from select units for geological and chemical analysis. The Spiller Farms site is a Native American site located in Wells, Maine marking a transition period between the Pleistocene and Holocene epochs, 12,000 BP. The Malaga Island site was a historic mixed-race community at the north end of Casco Bay where sediment columns were obtained in near-shore and subtidal zones. The samples obtained from Malaga Island have been radiocarbon dated to 3800 +/- 30 BP at 23 meters below the low-tide line. X-ray fluorescence (XRF) analysis is being conducted …

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 …

A Model To Predict Concentrations And Uncertainty For Mercury Species In Lakes, Ashley Hendricks

Dissertations, Master's Theses and Master's Reports

To increase understanding of mercury cycling, a seasonal mass balance model was developed to predict mercury concentrations in lakes and fish. Results indicate that seasonality in mercury cycling is significant and is important for a northern latitude lake. Models, when validated, have the potential to be used as an alternative to measurements; models are relatively inexpensive and are not as time intensive. Previously published mercury models have neglected to perform a thorough validation. Model validation allows for regulators to be able to make more informed, confident decisions when using models in water quality management. It is critical to quantify uncertainty; …

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 …

No Evidence For Trace Metal Limitation On Anaerobic Carbon Mineralization In Three Peatland Soils, Jason K. Keller, Jillian Wade

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Peatlands store roughly one-third of the terrestrial soil carbon and release the potent greenhouse gas methane (CH₄) to the atmosphere, making these wetlands among the most important ecosystems in the global carbon cycle. Despite their importance, the controls of anaerobic decomposition of organic matter to carbon dioxide (CO₂) and CH₄ within peatlands are not well understood. It is known, however, that the enzymes responsible for CH₄ production require cobalt, iron and nickel, and there is a growing appreciation for the potential role of trace metal limitation in anaerobic decomposition. To explore the possibility of …

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 …

The Clean Air Act And Its Impact On Ground Level Ozone Pollution Levels In Los Angeles, California, Rebecca G. Ford

Honors Theses

Ozone (O₃) occurs naturally as a protective, ultraviolet radiation-shielding “Ozone Layer” in the Stratosphere and as a photochemically produced pollutant in the Troposphere. The Clean Air Act (CAA) of 1970 regulates the emission and concentration of O₃ and five other atmospheric pollutants. Since the signing of the CAA, the ongoing question has been whether or not the National Ambient Air Quality Standards (NAAQS) and regulatory policies have had an effect on decreasing O₃ concentration. The Los Angeles metropolitan area is a prime example of how O₃ can be a public health hazard, and taint a …

Estimation Of Bubble-Mediated Air–Sea Gas Exchange From Concurrent Dms And Co2 Transfer Velocities At Intermediate–High Wind Speeds, Thomas G. Bell, Sebastian Landwehr, Scott D. Miller, Warren J. De Bruyn, Adrian H. Callaghan, Brian Scanlon, Brian Ward, Mingxi Yang, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Simultaneous air–sea fluxes and concentration differences of dimethylsulfide (DMS) and carbon dioxide (CO2/ were measured during a summertime North Atlantic cruise in 2011. This data set reveals significant differences between the gas transfer velocities of these two gases (1kw/ over a range of wind speeds up to 21ms􀀀1. These differences occur at and above the approximate wind speed threshold when waves begin breaking. Whitecap fraction (a proxy for bubbles) was also measured and has a positive relationship with 1kw, consistent with enhanced bubble-mediated transfer of the less soluble CO2 relative to that of the more soluble DMS. However, the correlation …

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 …

Nitrate Radicals And Biogenic Volatile Organic Compounds: Oxidation, Mechanisms And Organic Aerosol, Nga Lee Ng, Steven S. Brown, Alexander T. Archibald, Elliot Atlas, Ronald C. Cohen, John N. Crowley, Douglas A. Day, Neil M. Donahue, Juliane L. Fry, Hendrik Fuchs, Robert J. Griffin, Marcelo I. Guzman, Hartmut Hermann, Alma Hodzic, Yoshiteru Iinuma, José L. Jimenez, Astrid Kiendler-Scharr, Ben H. Lee, Deborah J. Luecken, Jingqiu Mao, Robert Mclaren, Anke Mutzel, Hans D. Osthoff, Bin Ouyang, Benedicte Picquet-Varrault, Ulrich Platt, Havala O. T. Pye, Yinon Rudich, Rebecca H. Schwantes, Manabu Shiraiwa, Jochen Stutz, Joel A. Thornton, Andreas Tilgner, Brent J. Williams, Rahul A. Zaveri

Chemistry Faculty Publications

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO₃) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO₃-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number …

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 Review Of The Occurrence Of Pharmaceuticals And Personal Care Products In Indian Water Bodies, Keshava Balakrishna, Amlan Rath, Yerabham Praveenkumarreddy, Keerthi Siri Guruge, Bikram Subedi

Faculty & Staff Research and Creative Activity

Little information exists on the occurrence and the ultimate fate of pharmaceuticals in the water bodies in India despite being one of the world leaders in pharmaceutical production and consumption. This paper has reviewed 19 published reports of pharmaceutical occurrence in the aquatic environment in India [conventional activated sludge wastewater treatment plants (WTPs), hospital WTPs, rivers, and groundwater]. Carbamazepine (antipsychoactive), atenolol (antihypertensive), triclocarban and triclosan (antimicrobials), trimethoprim and sulfamethoxazole (antibacterials), ibuprofen and acetaminophen (analgesics), and caffeine (stimulant) are the most commonly detected at higher concentrations in Indian WTPs that treat predominantly the domestic sewage. The concentration of ciprofloxacin, sulfamethoxazole, amoxicillin, …

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 …

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

Senior Honors Projects, 2010-2019

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

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 …

Methane Emissions As Energy Reservoir: Context, Scope, Causes And Mitigation Strategies, Xiaoli Chai, David J. Tonjes, Devinder Mahajan

Technology & Society Faculty Publications

Methane (CH4) is now considered a bridge fuel between present fossil (carbon) economy and desired renewables and this energy molecule is projected to play an important role in the global energy mix well beyond 2035. The atmospheric warming potential of CH4 is 28-36 times, when averaged over a 100-year period, that of carbon dioxide (CO2) and this necessitates a close scrutiny of global CH4 emissions inventory. As the second most abundant greenhouse gas (GHG), the annual global CH4 emissions were 645 million metric tons (MMT), accounting for 14.3% of the global anthropogenic GHG emissions. Of this, five key anthropogenic sources: …

Evaluation Of Veterinary Pharmaceuticals And Iodine For Use As A Groundwater Tracer In Hydrologic Investigation Of Contamination Related To Dairy Cattle Operations, Larry Boot Pierce, Honglin Shi

Sinkhole Conference 2015

Standard groundwater tracers such as Rhodamine WT, Fluorescein, Eosin and Tinopal CBX effectively provide a snapshot of hydrological conditions over a brief period of time and in a tightly controlled setting. However, in complex environmental situations with multiple potential sources, groundwater hydrologists are often seeking groundwater tracers that have extended longevity in the natural environment and the ability to directly pinpoint source locations. After reviewing operations of the nearby dairy it was determined that emerging contaminants, specifically two bovine veterinary pharmaceuticals (antibiotics), cephapirin sodium (CEPNa) and cephapirin benzathine (CEPB), and a sanitation agent, elemental Iodine (I) may have potential as …

Using Nitrate, Chloride, Sodium, And Sulfate To Calculate Groundwater Age, Kimm Crawford, Terry Lee

Sinkhole Conference 2015

Regression analysis is used to identify monotonic trends to assign water age using ion data from two large well water databases from southeast Minnesota (SE MN). Nitrate (NO3-N), chloride (Cl), sodium (Na), and sulfate (SO4) ions in the commonly used aquifers in SE MN can be used as groundwater tracers since they are either entirely or partly anthropogenic in their sources, their loading occurs on a regional scale, and they are almost entirely conserved. Ion concentrations over time are used to establish six trend patterns. Two patterns are unchanging (background and stable above background), and four are changing (linear up, …

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 …

Nutrient Addition Effects On Tropical Dry Forests: A Mini-Review From Microbial To Ecosystem Scales, Jennifer S. Powers, Kristen K. Becklund, Maria G. Gei, Siddharth B. Iyengar, Rebecca Meyer, Christine S. O'Connell, Erik M. Schilling, Christina M. Smith, Bonnie G. Waring, Leland K. Werden

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Humans have more than doubled inputs of reactive nitrogen globally and greatly accelerated the biogeochemical cycles of phosphorus and metals. However, the impacts of increased element mobility on tropical ecosystems remain poorly quantified, particularly for the vast tropical dry forest biome. Tropical dry forests are characterized by marked seasonality, relatively little precipitation, and high heterogeneity in plant functional diversity and soil chemistry. For these reasons, increased nutrient deposition may affect tropical dry forests differently than wet tropical or temperate forests. Here, we review studies that investigated how nutrient availability affects ecosystem and community processes from the microsite to ecosystem scales …

Comparing Three Methods For Estimating Ozone Depleting Substance Substitute Greenhouse Gases: Case Study Of The New York City Region, Wallace A. Murray Iii

Theses and Dissertations

This thesis evaluates the United States Environmental Protection Agency (EPA) method for estimating emissions from one source, Ozone Depleting Substances Substitutes (ODS substitutes) by comparing results for the New York City Metropolitan Statistical Area (NYC-MSA) with results from two other methodologies. The EPA’s method utilizes population data and GDP data to estimate and geographically allocate emissions, with little regard for the geographies of industrial activity. The two alternative methods use data for industrial employment and activity to provide results for comparison and perhaps a more accurate accounting and allocation of emissions throughout the NYC-MSA.

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, …