Environmental Chemistry Commons^™

Effect Of Electronegativity On Environmentally Persistent Free Radical (Epfr) Formation, Persistence, And Toxicity On Transition Metal Oxides, Syed Monjur Ahmed

LSU Doctoral Dissertations

Environmentally persistent free radicals (EPFRs) are a group of emerging environmental pollutants. Owing to their resonance structures, EPFRs have significantly higher lifetimes than typical free radicals, and can induce the formation of reactive oxygen species (ROS) known to cause pulmonary and cardiovascular dysfunction. EPFRs form by the adsorption of organic precursors on a transition metal oxide (TMO) surface and exhibit enough stability to cause negative health and environmental effects. While aromatic and substituted aromatic precursors form EPFRs on TMO surface at elevated temperatures and numerous substituted organics are ubiquitous in various industrial processes and household products, studies have largely overlooked …

Competitive Sorption And Transport Of Heavy Metals In Soil And Mn Oxide-Coated Sand, Joshua Tyler Padilla

LSU Doctoral Dissertations

This study investigated the competitive sorption of Ni, Pb, and Zn as well as synergistic interactions between Ni and phosphate (P) in soils and Mn oxide-coated sand. During stirred-flow experiments, the sorption of heavy metal cations by Olivier soil was mutually reduced when applied simultaneously. When applied consecutively, the cation of higher affinity was able to displace the cation of lower affinity from the soil surface, however, no evidence for the reverse case was observed. A novel general exchange kinetics model was able to correctly describe such displacement. Competition between Ni and Zn mutually increased mobility in Olivier and Windsor …

Development Of Engineered Soil Surrogates For Modeling Natural Soil Sorption Behavior, Ghada Yehia Abdalla

LSU Doctoral Dissertations

The land produces more than 95% of the global food supply, and with a continuously growing population, we need to optimize the use of the available agricultural land. Soil organic matter (SOM) is an essential component of soils, especially concerning their fertility and sorption behavior. The chemical composition of the SOM consists of lipids, lignin, and cellulose. However, the heterogeneous and complex nature of SOM, and real soils, makes their study challenging and introduces uncontrollable factors.

Therefore, structural mimics of natural soils with increasing complexity representing the real soil functionality were synthesized and evaluated for bulk properties related to their …

Synthesis, Characterization, And Investigation Of Metal Ion Quenching In Fluorescent Carbon Dot Surrogates For Particulate Matter Black Carbon And Evaluation Of Cellular Health Effects Due To The Surrogate Materials, Christopher Lee Sumner Jr

LSU Doctoral Dissertations

Black carbon (BC) is an environmental pollutant of particular concern to many international organizations for both its health effects and environmental effects. Probing health effects of BC as produced in the environment is difficult due to the complex nature of environmental pollutants found in their naturally occurring state. Fluorescent carbon dots (FCDs) were chosen to be used as a surrogate for BC. In the process of examining FCDs and their behavior as surrogates, information was gained on the health effects and behavior of FCDs as a class of nanomaterials for cell and tissue studies, which is outlined in this dissertation. …

Behavior Of Iron Species And Free Radicals In Ambient Pm2.5 And Pm Surrogates, Cholena Russo Ren

LSU Doctoral Dissertations

Air pollution, consisting of ambient particulate matter (PM), has been a rising health concern to the public. PM contains free radicals and have been known to damage human cells; however, their free radical chemistry is not well understood. This study utilized various vacuum and/or heat treatments to study free radical behavior in PM_2.5 (particulate matter with an aerodynamic diameter of 2.5 mm or less) and PM surrogates and simulated sunlight effects on PM_2.5. To mimic PM, iron-silica catalysts (i.e. PM surrogates) were synthesized and real-world ambient PM_2.5 was selected. The free radicals in PM_{2.5 …}

Assessment Of Soil Protein And Refractory Soil Organic Matter Across Two Chronosequences Of Newly Developing Marshes In Coastal Louisiana, Usa, Stuart Alexander Mcclellan

LSU Doctoral Dissertations

The impacts of sea-level rise and hydrologic manipulation are threatening the stability of coastal marshes throughout the world, thereby increasing the potential for re-mineralization of soil organic matter (SOM) in these systems. Such threats have prompted marsh restoration efforts, particularly in coastal Louisiana, yet it is unclear how the slowly decomposing (refractory) and quickly decomposing (labile) fractions of SOM may be differentially affected by different approaches to marsh restoration. Additionally, otherwise labile compounds may accumulate in the soil via a range of protective mechanisms, including rapid burial and association with organic compounds that are thought to enhance soil aggregation, such …

Evaluating Seasonal Nutrient Fluxes In Emerging And Eroding Wetlands Of The Louisiana Delta Plain, Kiran Upreti

LSU Doctoral Dissertations

Deltaic wetlands can ameliorate high NO₃^- loads via denitrification, a dominant NO₃^- reduction pathway in inland and coastal habitats. Dissimilatory Nitrate Reduction to Ammonia (DNRA), in contrast to denitrification, conserves N within the system and has been found to be favored over denitrification with increase in salinity and temperature. There are no studies in the Louisiana Deltaic plain with simultaneous estimation of denitrification and DNRA. Increased P availability has been shown to increase denitrification so it is essential to understand P biogeochemistry when studying N cycle. Here, we evaluated net denitrification using N₂:Ar and …

Toward The Impact Of Particulate Matter On Human Health: Evaluation Of Fluorescent Environmentally Persistent Free Radical (Epfr) Surrogates, Ansonia Badgett

LSU Doctoral Dissertations

Environmentally persistent free radicals (EPFRs)—a newly discovered pollutant associated with particulate matter (PM)—form during combustion and thermal processes, such as the incineration of hazardous waste. Various chlorine- and hydroxy-substituted benzenes chemisorb on the surface of metal oxides (e.g., NiO, CuO, and Fe₂O₃) and then form EPFRs, stabilized radical species, as the result of the transfer of electrons between the adsorbate and the metal ion of the metal oxide. Previous studies have shown direct correlations between ultra-fine (d < 0.1 mm) particulate matter (PM_0.1) exposure and adverse pulmonary health effects. PM_0.1 has the potential …

Influence Of Salinity, Sunlight, And Sediment On The Toxicity Of Pesticides In Three Non-Target Organisms, Emily Noelle Vebrosky

LSU Doctoral Dissertations

Pesticides used in the United States must undergo registration by the United States Environmental Protection Agency (USEPA), after a multitude of analyses ranging from environmental fate to aquatic toxicological impacts to human risk exposure. Testing varies for each chemical, some requiring more testing than others. In many cases, environmental factors are restricted in the analysis of chemical behavior and organismal testing is limited to larvae. Many pesticides are formulated to breakdown in the environment by means of photolysis, hydrolysis, or oxidation, either to ensure low-persistence, limited transport, or to form the active ingredient (pro-pesticides). Environmental influences on chemical behaviors include …

High-Dimensional Isotope Relationships, Yuyang He

LSU Doctoral Dissertations

High-dimensional isotope relationships describes the relationships of two or more element or position-specific (PS) elements in the same molecule or ion. It provides us more powerful tools to study reaction mechanisms and dynamics. Chapter 1 is about dual or multiple stable isotope relationship on δ-δ (or δ'-δ') space. While temporal data sampled from a closed-system can be treated by a Rayleigh Distillation Model (RDM), spatial data should be treated by a Reaction-Transport Model (RTM). Here we compare the results of a closed-system RDM to a RTM for systems with diffusional mass transfer by simulating the trajectories on nitrate's δ'^{18 …}