Scotts Creek Marsh (SCM) is a small coastal wetland ecosystem in Davenport, CA. The vegetation of SCM is dominated by three halophytic zones comprised of saltgrass, salt rush, cattails. The objectives of the study were (i) to investigate the variables that influence the zoning of the three dominant halophyte communities in SCM and (ii) to the test the effectiveness of Indicator of Reduction in Soil (IRIS) tubes to indicate the reduction of S. The study examined the following parameters from April 6 to July 21, 2013: (i) the HGM of Scotts Creek Marsh, (ii) soil oxidation and reduction (redox) conditions, (iii) salinity, and (iii) the effectiveness of Adobe Photoshop CS 5.1 (AP5) to analyze IRIS images. All three halophytes were well suited for anoxic, redox, and saline conditions by utilizing morphological adaptations (arenchyma, adventitious roots) to their root systems. The study concluded that the spatial zoning of the three dominate halophyte species within SCM was most likely due to slight differences in the water levels and salinity. The halophytes within SCM were zoned with saltgrass occupying the areas with the lowest water table and highest EC (26.98 dS/m). The cattails dominated the low average saline areas (9.60 dS/m) near the marsh channels with the highest water level. The salt rush zones had a mild EC level of 15.24 dS/m and intermediate water level. The IRIS tubes that were installed as indicators of both sulfur and iron reduction were effective. The tubes that were withdrawn after the closure of Scott’s Creek all had more than 30% reduction of the Fe3+ paint. The results from the IRIS study indicate that they are effective at recording the reduction of sulfur. The use of AP5 seemed to be an effective tool for analyzing IRIS images. The analyzed data from the study suggests that changes to the HGM of SCM could potentially alter the ecology of the marsh.

No description available.

<p>SO₂ and NO_x (NO+NO₂) are important trace gases in the atmosphere as they adversely affect air quality and are precursors to sulfate and nitrate aerosols in the atmosphere. However, there are significant uncertainties in the emission inventories and the atmospheric chemistry processes of both gases. Addressing these uncertainties will help us to 1) better regulate their emissions from anthropogenic activities, 2) understand the formation mechanism of aerosol pollution events, during which rapid accumulation of nitrate and sulfate aerosols are commonly observed, and 3) better constrain the impact of SO₂, NO_x, sulfate aerosols and nitrate aerosols to the global radiation balance. Stable isotopes of nitrogen and sulfur are useful tools in understanding both the origins and chemistry of SO₂ and NO_x since different emission sources usually display distinct sulfur and nitrogen isotopic compositions, and different SO₂ and NO_xoxidation pathways fractionate sulfur and nitrogen isotopes differently. In this dissertation, five studies are conducted to 1) use sulfur isotopes to investigate the sources and chemistry of atmospheric sulfur, and 2) improve our understanding of the isotopic fractionation processes associated with the atmospheric chemistry of reactive nitrogen. </p><p>Using stable sulfur isotopes, we first analyzed the sources of sulfate aerosols collected at Baring Head, New Zealand and atmospheric deposition at the Atacama Desert. At Baring Head, we found that the secondary sulfate, i.e., sulfate formed from atmospheric oxidation of SO₂, is mainly observed in fine aerosols (<1 µm) while the sulfate in coarse aerosols (>1 µm) is mostly sea salt sulfate. 73-77% of the secondary sulfate is sourced from biogenic emissions by ocean phytoplankton, and the rest is originated from anthropogenic activities. The sulfate deposition across the Atacama Desert, on the other hand, is a mixture of sea salt sulfate (only near the coast), anthropogenic SO₂ emissions, local soil, and lake salts. Then, sulfur isotopes were used to investigate the formation chemistry of sulfate aerosols collected during a strong winter haze episode in Nanjing, China, where the sources of SO₂ were well-understood. We found that, although the sources of sulfur remain unchanged during the haze episode, the sulfur isotopic compositions of sulfate vary significantly, suggesting isotopic fractionation occurred during the formation of sulfate aerosols. We interpreted the variation using a Rayleigh distillation model to evaluate the contribution of sulfate formation pathways. The model suggested that the Transition Metal Ion catalyzed O₂ oxidation pathway contributed 49±10% of the total sulfate production, while the O₃/H₂O₂ oxidations accounted for the rest. </p><p>Next, we conducted experiments in an atmospheric simulation chamber to determine the isotopic fractionations between NO and NO₂. This isotopic fractionation is controlled by a combination of two factors: 1) the equilibrium isotopic exchange between NO and NO₂ molecules, and 2) the kinetic isotope effects of the NO_x photochemical cycle, namely the Leighton Cycle Isotope Effect (LCIE). Our experiments showed that the fractionation factor during the isotopic exchange is 1.0289±0.0019, and the fractionation factor of LCIE is 0.990±0.005. A model was constructed to assess the relative importance of the two factors, showing the isotopic exchange should be the dominant factor when NO_x >20 ppb, while LCIE should be more important at low NO_x concentrations (<1 ppb) and high rates of NO₂photolysis. Last, we quantified the overall nitrogen isotopic fractionation during the formation of nitrate aerosols collected at Baring Head, New Zealand. Our results showed that significant and variable (0-15‰) isotopic fractionations occurred during the formation of nitrate aerosols. The isotopic fractionation factors are lower in the summer and higher in the winter, which is mainly caused by seasonal variations in nitrate formation pathways. </p><p>Overall, this dissertation first applied stable sulfur isotopes in aerosol samples collected in different environments, demonstrating that isotopes are excellent tools in identifying the origins and chemistry of atmospheric sulfur. Then, we investigated the isotopic fractionation processes during the atmospheric nitrogen chemistry, which can be useful for future studies aimed at understanding the origins and chemistry of atmospheric nitrogen using stable nitrogen isotopes.</p>

Biochar application as a soil additive is gaining global acceptance. In this era of climate change, biochar use for improved soil productivity is not just a sustainable eco-friendly substitute to synthetic fertilizer, but a noble contributor to the fight against climate change. Although biochar has been accredited with some environmental and agricultural benefits, most studies concentrated on agricultural and biowaste products as feedstocks. This research was designed to explore P-enriched modified-Douglas fir biochar potential as a soil additive. Using corn as a test crop, greenhouse studies were performed on acidic sandy soil, comparing phosphorus enriched modified-Douglas fir biochar efficacy to a commercial synthetic triple superphosphate fertilizer and a control treatment. Incubation studies were also performed to evaluate the liming and heavy metal immobilization efficacies. Firstly, P-enriched modified-Douglas fir biochar’s ability to release plant soluble P was investigated. At various P enrichment concentration, soil plant availability P from P enriched modified-Douglas fir biochar treatments differed insignificantly from superphosphate fertilizer treatment. The direct correlations between both K and Mg recoveries with available soil P, suggested P enriched modified-Douglas fir biochar potential to supply multiple plant nutrients. Secondly, the influence of P uptake on plant growth and P use efficiency was examined. The greater agronomic P use efficiency obtained in P enriched modified-Douglas fir biochar (~32 kg kg-1) than the triple supper phosphate fertilizer (~17 kg kg-1) treatment confirmed P enriched modified-Douglas fir biochar potential as a multiple nutrient released soil additive. Thirdly, biochar-supported phosphate (BP) effectively reduced Pb2+ mobility in simulated contaminated soil. Pb2+reacted with phosphate from Ca10(PO4)6(OH)2 embedded in the biochar supported phosphate at pHPb10(PO4)6(OH)2. Finally, the amendment of acidic soils with modified P-enriched modified-biochar improved soil buffering capacity because of its enhanced ash contents, alkalinity, and surface functional groups. Spectroscopic methods were used to analyze biochar, soil, and plant materials extracts. Several other analytical methods including BET and thermogravimetric analyses were used to characterized biochar. These findings suggest that the use of phosphorus enriched modified-Douglas fir biochar in agricultural soil is a feasible relatively low-cost, effective, and environmentally sustainable soil management and P recycling strategy

M.Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology / Water contaminated with non-biodegradable organics is becoming increasing problematic as it has a hazardous effect on human health and the aquatic environment. Therefore, the removal of organic contaminants is of importance and an active heterogeneous Fenton catalyst is thus required. The literature indicates that a bimetallic oxide Fenton catalyst is more active than an iron oxide catalyst. This study focused on increasing the activity of iron-based Fenton catalysts with the addition of transition metals such as manganese, cobalt and copper and optimizing the preparation method. In this study, bimetallic oxide (Fe-Cu, Fe-Mn, Fe-Co) and monometallic oxide (Fe, Cu, Mn,Co) catalysts supported on silica SiO2 where prepared by incipient wetness impregnation. The total metal oxide contents were kept constant. The catalysts where calcined in two different ways, in a conventional oven and in a microwave. These catalysts were characterized with XRD, XPS and CV and were tested for the degradation of methylene blue dye at 27°C. The catalysts calcined in a microwave oven had a higher catalytic activity than those prepared in a conventional oven. The bimetallic oxide catalysts outperformed the mono- metallic oxide catalysts in the degradation of methylene blue. The Fe2MnOx prepared by microwave energy were the most active catalyst yielding the highest percentage of degradation of methylene blue dye (89.6%) after 60 minutes. The relative amounts of manganese and iron oxide were varied while keeping the total metal content in the catalyst the same. The optimum ratio of Fe to Mn was 1:7.5 since it yielded the most active catalyst. A 96.6 % removal of methylene blue was achieved after 1 hour of degradation. Lastly this ratio 1Fe:7.5Mn was prepared by varying different microwave power (600, 700 and 800 W) and irradiation time (10, 20 and 30 min). The optimum microwave power and irradiation time was 800W and 10 min with the methylene blue percentage removal of 96.6 % after 1 hour of degradation.

Electrooxidation has been used to deposit thin film polyaniline as well as its derivative - thin film poly (ortho-phenylenediamine) (POPD) and poly (meta-phenylenediamine) (PMPD) on carbon electrodes, which are subsequently used to monitor the environmental heavy metal ions (Hg2+, Pb2+ ,Cd2+) through a rather unusual "blocking" of anodic stripping for these metals. Using Hg2+ as a model, its cyclic voltammogram for a modified glassy carbon electrode with the resultant polymer shows an enhanced cathodic peak that increases linearly with the analyte ion concentration. POPD also exhibits unique selective detection for organic species. Acetaminophen and uric acid can be preferentially detected over ascorbic acid from a mixture of these three compounds. In addition, the effect of carbon nanotubes incorporated in polyaniline (PAN) film is observed to have enhanced electrochemical catalytic activities on the remedy of environmental dichromate.

A Comparison of Solvent and Water-Borne Alkyd Coatings Abstract Conventional solvent based alkyd coatings have gone out of favor due to concerns over volatile organic compound (VOC) content. However, due to recent focus on renewable raw materials, alkyds are making a comeback in waterborne form. Water based alkyd coatings are known to have poor shelf stability and corrosion resistance, as well as other problems during the formulation process. This project focused on comparing solvent borne to two types of water-borne alkyds, water reducible alkyds and alkyds emulsions. The purpose was to understand the differences between the three types of alkyds in terms of their production and final properties. It was ultimately hoped that the formulations used for this project would prove to solve the problems normally experienced by waterborne alkyds. After testing several chemical and physical properties, it was determined that the solvent borne alkyd coatings performed better than both water based systems in corrosion resistance, accelerated weathering, and shelf stability but the water reducible and emulsion alkyd coatings performed similarly to the solvent borne alkyd in gloss, contrast ratio, and durability. The VOC emissions for all three alkyd types were as expected; the solvent borne had the highest emission at 253 g/L, followed by water reducible with 166 g/L, and emulsion with 34 g/L. The History of VOC Regulations in the United States Abstract In another solvent based alkyd coating focused project within my research group, the question of the how volatile organic compound (VOC) regulation in the United States (U.S.) evolved came up. It quickly became apparent that no comprehensive answer to this question existed. Part two of this project is an attempt to answer this question in a comprehensive manner. VOC regulations started in California in the late 1970s, and paints and coatings became a nationally regulated emission source by the 1990s. The U.S. government limited harmful emissions, such as smog and compounds contributing to ozone depletion, through Clean Air Acts. The first Clean Air Act was enacted in 1965, but it wasn’t until the Clean Air Act of 1990 that VOC emissions became a focus. VOCs are not inherently hazardous but are a source of concern because they serve as a precursor to the formation of damaging ground level ozone. The Environmental Protection Agency (EPA) has established the minimum VOC emission limits in the Architectural and Industrial Maintenance (AIM) federal rule, but each state or state subdivision can enforce stricter limits within their borders. The strictest limits are set by the South Coast Air Quality Management District (SCAQMD) in Southern California, but other entities exist. This report thoroughly documents the history of VOC regulation in the United States by collecting, combining, organizing, and summarizing information gathered from various industries and government publications, agency members, and industrial and academic professionals.

The endemic eelgrass (Zostera marina) community of Morro Bay Estuary, located on the central coast of California, has experienced an estimated decline of 95% in occupied area (reduction of 344 acres to 20 acres) from 2008 to 2017 for reasons that are not yet definitively clear. One possible driver of degradation that has yet to be investigated is the role of herbicides from agricultural fields in the watershed that feeds into the estuary. Thus, the primary research goal of this project was to better understand temporal and spatial trends of herbicide use within the context of San Luis Obispo (SLO) County and Morro Bay Watershed by analyzing data of application by mass, area, and intensity to identify herbicides with the highest potential for local environmental pollution. California Pesticide Use Annual Summary Reports (PUASR) from the years 2000 to 2017 were used to obtain data for conducting a meta-analysis to estimate total herbicide application by weight within every township, range, and section for each of the eight selected herbicides: oxyfluorfen, glyphosate, diuron, chlorthal-dimethyl, simazine, napropamide, trifluralin, and oryzalin. A second goal was to select an analytical laboratory that would be best suited for herbicide analysis of estuary sediments to determine the presence, or lack thereof, of the eight selected herbicides. Criteria of consideration in laboratory selection included herbicides detection capabilities, detection/reporting limits, testing prices, chain of custody protocols, turnaround times, and laboratory site locations. The meta-analysis yielded results showing high herbicide application rates in SLO County with glyphosate, oxyfluorfen, and chlorthal-dimethyl being identified as three herbicides of elevated risk for local environmental contamination due high rates of use by mass, by area, and/or intensity during the study timeframe. Additionally, Morro Bay Watershed exhibited moderate rates of herbicide application with chlorthal-dimethyl and glyphosate being of highest risk for contamination and accumulation within the estuary because of high application rates by mass, by area, and/or intensity. Finally, Environmental Micro Analysis (EMA) and Primus Group, Inc. (PrimusLabs) were identified as the top candidates for analytical laboratory testing of Morro Bay Estuary sediment samples to be obtained and tested for the selected herbicides. These laboratories provide superior analytical capabilities of the eight herbicides, impressive reporting limits or lower detection limits, competitive testing prices for detecting multiple constituents in multiple samples, robust chain of custody protocols, options for quick turnaround times, and laboratory site locations within California.

Electrosorption-based capacitive deionization (CDI) has become a viable process for brackish water desalination and defluoridation. In this study, activated Douglas fir biochar is used as a low-cost electrode material with adsorption capacity comparable to activated carbon obtained from biomass precursors. Adding functional groups to the activated biochar enhanced salt removal capacity, providing cation and anion selectivity. The functionalized electrodes were prepared by Nafion, titanium isopropoxide, and p-phenylenediamine treatment, respectively, which introduced sulfonate, titanium dioxide and amine functional groups to the electrode surface. These modification methods are versatile and can be easily performed without sophisticated laboratory environment. Modified biochar electrodes were characterized by TEM, SEM-EDX, XRD, and XPS. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were performed to analyze the electrochemical properties of the electrodes. The salt adsorption capacity (SAC) was evaluated in a 3D-printed capacitive deionization flow cell using a chloride and fluoride ion sensor. It was found that functionalized biochar electrodes had increased SAC and charge efficiency in asymmetrical setup due to reduced co-ion effect. For example, the asymmetrical CDI cell with Nafion cathode and amine biochar anode improved NaCl removal capacity by 54% over the activated biochar symmetrical cell (identical anode and cathode), with SAC 6.01 mg NaCl/g biochar at the symmetrical cell and 9.25 mg/g for the asymmetrical cell. The charge efficiency also increased by ≈ 67% from symmetric AcB cell to asymmetric TB-05 cathode and AmB anode. This work shows that biochar can be engineered and explored broadly as an inexpensive sustainable electrode material for asymmetrical capacitive deionization.

<p dir="ltr">Mass spectrometry (MS) is a powerful and versatile technique that is useful for addressing a wide range of complex analytical challenges. In this work, mass spectrometry-based assays were developed to address issues relating to environmental contamination and for detecting analytes of interest to the defense industry. Chapter one is an overview of the history of mass spectrometry, the fundamental operation of a mass spectrometer, as well as, advancements in chromatographic separation and ionization methods. Chapter two focuses on the development of an assay that uses blow flies as environmental sensors of chemical weapon release. In that work, a liquid chromatography – tandem mass spectrometry (LC-MS/MS) method was developed to detect chemical warfare agent simulants and chemical warfare agent hydrolysis products in flies exposed to the chemicals in controlled feeding experiments. The work in chapter three describes the development of a surface enhanced Raman spectroscopy assay coupled to paper spray mass spectrometry for a more fieldable and environmentally friendly approach to detect organophosphorus compounds. Chapter four describes the development of a paper spray mass spectrometry assay for the detection and semi-quantitation of per- and polyfluoroalkyl substances in whole blood without sample cleanup or chromatographic separations. This method would be useful in detecting high levels of these carcinogenic compounds in individuals highly exposed via their occupations. The final chapter (chapter five) returns to using blow flies as environmental sensors, but this time to detect insensitive munitions in the environment. The work focuses on the development of two different liquid chromatography mass spectrometry methods for the detection of insensitive munitions, which are less shock sensitive explosives, and their transformation products in the environment. Controlled feeding experiments were also performed where flies were exposed to contaminated soil and water sources to show the feasibility of this method in a more realistic scenario. The projects detailed herein show the extensive range with which mass spectrometry can be used for the detection of harmful chemistries of environmental concern.</p>