Indiana University-Purdue University Indianapolis (IUPUI) / Introduction: One of the main objectives of endodontic therapy is to reduce microbes and remove inflamed pulpal tissue within the root canal system (RCS). This is accomplished through chemomechanical debridement of the RCS using hand and rotary instrumentation along with an antimicrobial irrigant. Today, the most commonly used irrigant is sodium hypochlorite (NaOCl), often at concentrations toxic to human cells. The use of ozone as an endodontic irrigant is a novel technique that has been proven to be antimicrobial against several microorganisms. However, independent research is lacking on ozone’s efficacy against an established endodontic biofilm. If ozone’s efficacy against biofilms is confirmed, the use of toxic and potentially dangerous sodium hypochlorite could be replaced in some clinical situations (i.e., regeneration, immature teeth, resorption) with a safer and effective alternative. Objective: The aim of the current study was to evaluate the anti-biofilm activity of different concentrations of ozonated water compared to various concentrations of NaOCl against an established endodontic biofilm of Enterococcus faecalis in root canal treated teeth in vitro. Materials and Methods: The crowns of similarly sized, maxillary anterior teeth were removed, and the roots cut to a standard length (12 mm). All root canals were instrumented to a standard size. Specimens were sterilized and then inoculated with E. faecalis, which were allowed to grow for two weeks to form an established biofilm. There were six treatment groups: 1) 6% NaOCl; 2) 1.5% NaOCl; 3) 16µg/mL ozonated water; 4) 25µg/mL ozonated water; 5) 50µg/mL ozonated water, and 6) saline. Following treatment, samples were collected, plated, and incubated for two days. The number of CFU/mL were determined, and samples visualized using confocal imaging. The effect of treatment group on bacterial counts was made using one-way ANOVA followed by pair-wise comparisons. Null Hypothesis: Endodontically treated teeth irrigated with ozonated water will not demonstrate a statistically significant decrease in the E. faecalis biofilm compared to those treated with sodium hypochlorite Results: CFUs were converted to log10 and compared using Fisher’s Exact tests or one-way ANOVA followed by pair-wise tests. In all observations utilizing NaOCl irrigation, no colonies formed following treatment. The two NaOCl groups, with 0 CFU/mL, were significantly different than the other four groups (p=0.009). Saline showed a trend towards higher CFU/mL than 50 µg/ml O3 (p=0.068). None of the other comparisons approached statistical significance (p=0.453 25 µg/ml O3, p=0.606 16 µg/ml O3, p=0.999 25 µg/ml O3 vs 50 µg/ml O3, p=0.990 16 µg/ml O3 vs 50 µg/ml O3, p=1.000 16 µg/ml O3 vs 25 µg/ml O3). Confocal imaging helped illustrate effects of irrigation and confirm CFU findings. Conclusion: The results of this study failed to reject the null hypothesis. There was a statistically significant difference in the E. faecalis biofilm remaining in the groups treated with ozonated water compared to those treated with NaOCl. However, there was a trend towards higher CFU/mL in the saline group compared to the 50µg/mL ozonated water group. According to this finding, future studies should evaluate the effects of higher concentrations of ozonated water against an established E. faecalis biofilm. In addition, other follow-up studies might include ozonated water’s effect on human cells, such as the stem cells of the apical papilla that are so critical to the success of regenerative endodontic procedures. Due to university and laboratory closures caused by the COVID-19 pandemic, this project was stopped short and an insufficient sample size did not allow for proper statistical power. Additional occasions should be run upon the university’s re-opening to allow for proper statistical power.

Surface interactions and reactivity are of critical importance in current biomedical technologies, for example, satisfactory cell attachment and long term viability are essential for optimal in vitro tissue culture and for successful implantation and stability of cardiovascular medical implants such as stents and grafts. To achieve this, the control of fundamental forces and the resulting molecular interactions between the relevant surface and absorbing or adhering species in the physiological system is compulsory. This work utilised the surface modification technique of Ultra-Violet/ Ozone to improve the polystyrene biocompatibility by oxidising the surface with additional polar oxygen functional groups without damaging the surface bulk property. UV/Ozone treatment utilised throughout this study produced controllable oxygen functional groups and led to an increase in surface atomic oxygen level to 41% on unwashed and 35% on washed polystyrene surfaces, washing resulted in the removal of low molecular weight oxidised materials. Surface energy was increased by the addition of oxygen functional groups with the combination of alcohol (C-OR), carbonyl (C=O) and carboxyl (O-C=O); Saturation state was reached after 300s of UV/Ozone treatment where no more oxygen functionalities were incorporated to the surface. Moreover, UV/ozone treatment did not show an effect on the surface roughness studied by atomic force microscopy. The biological responses of human endothelial umbilical vein cells (HUVECs) were studied at the different level of UV/Ozone treated surfaces. HUVEC adhesion, proliferation and migration were significantly improved by the treatment compared to untreated and tissue cultures plastics (TCPs). Among the levels of UV/ozone treatment studied, 120s and 180s were found to be the most effective and HUVEC proliferation did not seem to be affected by the high level of oxygen. Similarly, the surface oxygen level did not affect the migration over UV/Ozone treated over 60s. Hypoxic condition significantly increased HUVECs migration on UV/Ozone treated, TCPs and untreated surfaces compared to normoxia, the oxygen rich surface did not favour to HUVECs that underwent regulatory process to enable the cells to increase migration. Under laminar flow conditions, HUVECs did not only grow, proliferate and migrate but also showed standard responses on UV/Ozone treated polystyrene surface. A decrease in cell size was observed at all shear stress intensities studied (1 dyn/cm2, 9 dyn/cm2 and 25 dyn/cm2) and the decrease was more obvious at higher shear stress. High shear stress intensity also induced high cell turnovers, which may be related to air bubbles induced at high flow rate. The overall findings of this study clearly illustrate that UV/Ozone surface treatment can be applied on polystyrene to improve human endothelial cells functionalities in term of adhesion, proliferation and migration in both static and laminar flow environment.

This work was concerned with the determination of mass transfer and kinetic parameters of ozone reactions with four organic compounds from different families, namely reactive dye RO16, triclocarban, naphthalene and methanol. In order to understand the mechanisms of ozone reactions with the organic pollutants, a radical scavenger (t-butanol) was used and the pH was varied from 2 to 9. Ozone solubility (CAL*) is an important parameter that affects both mass transfer rates and chemical reaction kinetics. In order to determine accurate values of the CAL* in the current work, a set of experiments were devised and a correlation between CAL* and the gas phase ozone concentration of the form CAL*(mol/L) = 0.0456 CO3 (g/m3 NTP) was obtained at 20°C. This work has also revealed that t-butanol did not only inhibit hydroxyl radical reactions but also increased mass transfer due to it increasing the specific surface area (aL). Values of the aL were determined to be 2.7 and 3.5 m2/m3 in the absence and presence of t-butanol respectively. It was noticed that the volumetric mass transfer coefficient (kLa) has increased following the addition of t-butanol. Ozone decomposition was studied at pH values of 2 to 9 in a 500 mL reactor initially saturated with ozone. Ozone decomposition was found to follow a second order reaction at pH values less than 7 whilst it was first order at pH 9. When the t-butanol was added, the decomposition of ozone progressed at a lower reaction order of 1.5 for pH values less than 7 and at the same order without t-butanol at pH 9. Ozone decomposition was found significant at high pHs due to high hydroxide ion concentration, which promotes ozone decomposition at high pHs. The reaction rate constant (k) of RO16 ozonation in the absence of t-butanol was determined. The result suggests that RO16 degradation occurs solely by molecular ozone and indirect reactions by radicals are insignificant. The chemical reaction of triclocarban with ozone was found to follow second order reaction kinetics. The degradation of naphthalene using the liquid/gas-ozone (LGO) system was studied. This result showed that hydroxyl radicals seemed to have limited effect on naphthalene degradation which was also observed when a radical scavenger (t-butanol) was used. Reaction rate constants were calculated and were found around 100 times higher than values reported in the literature due to differences in experimental conditions. From the results of the experimental investigation on the degradation of methanol by ozone it was found that the rate constant (k) of the degradation reaction increased at pH 9. The reaction stoichiometry was found to have a value of 1 mol/mol. The two steps of the liquid/solid-ozone (LSO) system were studied on beds of silica gel and a zeolitic material (D915) and the ozone adsorption process was modeled and found that particle rate controls ozone adsorption step but liquid rate controls the water treatment step. Ozone desorption with pure deionised water was studied. The water flow rate was found to accelerate the desorption rates but pH was found to decrease the desorption rates. In contrast, the effect of pH was insignificant in the presence of t-butanol. Determination of the adsorption isotherms for RO16, naphthalene and methanol revealed that RO16 did not exhibit adsorption on silica gel, but both naphthalene and methanol showed adsorption on D915 described by Langmuir model.

Ozone (O₃) and terpenoids react to produce secondary organic aerosol (SOA). This work explored novel ways that these reactions form SOA indoors, with five investigations, in two categories: investigations of (i) the impacts of particle controls on indoor SOA formation, and (ii) two fundamental aspects of indoor SOA formation. For category (i), two investigations examined the particle control devices of ion generators, which are air purifiers that are ineffective at removing particles and emit ozone during operation. With a terpenoid source present (an air freshener), ion generators acted as steady-state SOA generators, both in a 15 m³ chamber and 27 m³ room. The final investigation in category (i) modeled how heating, ventilating, and air-conditioning (HVAC) systems influence SOA formation. Influential HVAC parameters were flow rates, particle filtration, and indoor temperature for residential and commercial models, as well as ozone removal by particle-laden filters for the commercial model. For category (ii), the first investigation measured SOA formation from ozone reactions with single terpenoids and terpenoid mixtures in a 90 L Teflon-film chamber, at low and high ozone concentrations. For low ozone, experiments with only d-limonene yielded the largest SOA number formation, relative to other mixtures, some of which had three times the effective amount of reactive terpenoids. This trend was not observed for high ozone experiments, and these results imply that ozone-limited reactions with d-limonene form byproducts with high nucleation potential. The second investigation in category (ii) explored SOA formation from ozone reactions with surface-adsorbed terpenoids. A model framework was developed to describe SOA formation due to ozone/terpenoid surface reactions, and experiments in a 283 L chamber determined the SOA yield for ozone/d-limonene surface reactions. The observed molar yields were 0.14–0.16 over a range of relative humidities, and lower relative humidity led to higher SOA number formation from surface reactions. Building materials on which ozone/d-limonene surface reactions are predicted to lead to substantial SOA formation are those with initially low surface reactivity, such as glass, sealed materials, or metals. The results from category (ii) suggest significant, previously unexplored mechanisms of SOA number formation indoors. / text

Photochemical grid models are used to evaluate air pollution control strategies by simulating the physical and chemical processes that influence pollutant concentrations. Their accuracy depends on the accuracy of input data used for anthropogenic and biogenic emissions, land surface characteristics, initial and boundary conditions and meteorological conditions. Evaluation of model performance requires sufficient ambient data. This work develops approaches for applying satellite data to allow more frequent and timely estimates of parameters required to estimate emissions and pollutant removal processes for regional air quality modeling. Land use and land cover (LULC) data prepared from remote sensing satellite data were evaluated for use as inputs to photochemical grid models for estimating dry deposition velocities and biogenic emissions. The results indicated that satellite-based data derived from the Moderate Resolution Imaging Spectroradiometer instrument can be used to provide periodic updates to LULC information used in photochemical models. The sensitivity of predicted ozone concentrations to LULC data used for biogenic emission estimates was examined by comparing the database currently used for modeling in southeastern Texas with a new database prepared from Landsat satellite imagery and field data. The satellite data and image classification techniques provide useful tools for mapping and monitoring changes in LULC. However, field validation is necessary to link species and biomass densities to the classification system needed for accurate biogenic emissions estimates, especially in areas that have dense concentrations of species that emit high levels of biogenic hydrocarbons. The application of NO2 measurements from the Ozone Monitoring Instrument (OMI) to validation of NOx emission estimates and identification of emission sources for regional air quality modeling for Texas was examined. OMI observations can be used to identify regions with changes in emissions over time or where estimates have large uncertainties and to evaluate the effectiveness of emission reduction strategies. For example, in the Dallas-Fort Worth area, observed NO2 column densities from OMI indicate that emission controls are less effective than anticipated due to increased area source emissions. The techniques developed in this work have broad applicability in the advancement of methods for including satellite remote sensing data in regional air quality modeling. / text

Work hypothesis: Different pea (Pisum sativum L.) morphotypes respond differently to various anthropogenic factors. This can be related with an alteration of plant metabolism and with changes of photosynthetic pigments and biochemical indexes. Work aim and the tasks: To investigate the effects of ozone and UV-B radiation on different pea (Pisum sativum L.) morphotypes under changing climatic conditions and to measure plant reaction to the effects of ozone and UV-B radiation. 1.To investigate the effects of ozone and UV-B radiation on the morphometric parameters of different pea morphotypes under changing climatic conditions; 2.To investigate the effects of ozone and UV-B radiation on the photosynthetic pigments of different pea morphotypes under changing climatic conditions; 3.To investigate the effects of ozone and UV-B radiation on the biochemical indexes of different pea morphotypes under changing climatic conditions. Novelty of the scientific work. For the first time the effects of the near-ground ozone and UV-B radiation on two different pea (Pisum sativum L.) morphotypes (leafy ‘Ilgiai‘ and semi-leafless ‘Profi‘) were investigated under changing climate conditions. The response of these plants to the effects of ozone and UV-B radiation was measured. Defended propositions The different pea morphotypes respond differently to the effect of anthropogenic factors; The morphometric parameters of the different pea morphotypes alters unequally when responding to the... [to full text] / Darbo hipotezė: Skirtingų morfotipų žirniai (Pisum sativum L.) nevienodai reaguoja į įvairius antropogeninius veiksnius. Tai gali būti susiję su augalų metabolizmo pakitimu, fotosintetinių pigmentų, bei biocheminių rodiklių kitimu. Darbo tikslas: Ištirti ozono ir UV-B spinduliuotės poveikį skirtingų morfotipų žirniams (Pisum sativum L.) kintančiomis klimato sąlygomis, bei nustatyti jų reakciją į ozono ir UV-B spinduliuotės poveikį. Uždaviniai: 1.Kintančiomis klimato sąlygomis ištirti ozono bei UV-B spinduliuotės poveikį, skirtingų morfotipų žirnių morfometriniams parametrams; 2.Kintančiomis klimato sąlygomis ištirti ozono ir UV-B spinduliuotės poveikį, skirtingų morfotipų žirnių fotosintetiniams pigmentams; 3.Kintančiomis klimato sąlygomis ištirti ozono poveikį, skirtingų morfotipų žirnių biocheminiams rodikliams. Mokslinis darbo naujumas. Pirmą kartą buvo ištirtas priežemio ozono ir UV-B spinduliuotės poveikis, kintančiomis klimato sąlygomis, skirtingų morfotipų sėjamajam žirniui (Pisum sativum L.) lapuotiems ‘Ilgiai‘ bei pusiau belapiams ‘Profi‘, bei nustatyta jų reakcija į ozono ir UV-B spinduliuotės poveikį. Ginamieji teiginiai Skirtingų morfotipų žirniai nevienodai reaguoja į antropogeninių veiksnių poveikį; Skirtingų morfotipų žirnių morfometriniai parametrai, nevienodai skirtingai kinta nuo poveikio laiko, bei poveikio stiprumo; Skirtingų morfotipų žirnių fotosintezės mechanizmai yra nevienodi, sąlygojantys apsaugą nuo fotooksidacinio streso; Skirtingų morfotipų žirnių... [toliau žr. visą tekstą]

Baigiamajame magistro darbe nagrinėjama trumpalaikė ozono koncentracijos kaita ir jos priklausomybė nuo meteorologinių parametrų. Literatūros apžvalgoje aptariama ozono susidarymas, cheminės savybės, poveikis žmogaus sveikatai ir augalams. Atlikta 2000-2009 metais Preilos monitoringo stotyje gautų duomenų (vienos valandos vidurkiai) analizė. 2009 metų šiltuoju sezonu atliktas eksperimentas, sudaryta dešimties ir dviejų minučių vidurkių ozono koncentracijos ir meteorologinių parametrų duomenų bazė. Parametrų tarpusavio priklausomybė nustatyta panaudojant tiesinės regresijos metodą, apskaičiuoti koreliacijos koeficientai. Pasinaudojant Furje metodu atlikta ozono bei meteorologinių parametrų spektrinė analizė. Buvo rasti pagrindiniai dažnių pikai, kurie labiausiai išryškėja. Darbą sudaro 6 dalys: įvadas, literatūros apžvalga, matavimo prietaisai ir metodika, eksperimentinių tyrimų rezultatai, išvados ir literatūros sąrašas. Darbo apimtis – 57 p. teksto be priedų, 38 paveikslai., 3 lentelės, 53 bibliografiniai šaltiniai. Atskirai pridedami darbo priedai. / In master final work the variation of short-term ozone concentration variations were analyzed. Ozone formation, chemical characteristics, impact on human health and plants were described. The study of the short- and long-term ozone concentration variations dependence on meteorological parameters is presented. The data of hourly parameters obtained at the monitoring station Preila during 2000-2009 years were analyzed. The 2 and 10 minutes average values of the ozone concentration and meteorological parameters were collected during experiment in warm season of 2009 year. The regression analysis was applied for the determination of the correlation coefficients between variables. The strongest relationship from the long-term variations was found between ozone concentration and temperature. The strongest relationship from the short-term variations was found between ozone concentration and wind speed. Structure: introduction, literary review, measurements instruments and methodology, experimental research results, conclusions and references. Thesis consists of: 57 p. text without appendixes, 38 pictures, 3 tables, 53 bibliographical entries. Appendixes included.

The Lewisville Lake Environmental Learning Area (LLELA) is a wildlife management area with tallgrass prairie, an endangered ecosystem. Essential ecosystem processes, especially fire, are part of restoration. To support fire management efforts at LLELA and surrounding areas, this project evaluated and developed tools for fire restoration. The four primary prairie grasses respond favorably to burning. Fuel loads and fuel models vary by scale and survey method. One- and 10-hour fuel moisture can be predicted using a statistical model; 100- and 1,000-hour fuel moisture cannot. Historic weather data suggests that burning can occur when it is most effective. The production of ozone precursors produced by burning is comparable to those emitted every six minutes by regional automobiles.

One main goal of ecological research is to understand nature´s complexity, in order to predict the potential impact of environmental perturbations. In this thesis, I investigate the ecological interactions between some of the most ancient organisms living on our planet: plants and insects. Focus of my research is the interaction between the wild brassicaceous plant black mustard (Brassica nigra L.) and its specialist insect herbivore, the large white cabbage butterfly (Pieris brassicae L). Both organisms are well characterized model species used in chemical ecology research. Using different analytical techniques, such as liquid and gas chromatography coupled to mass-spectrometry (LC- and GC-MS) and headspace collection of volatile organic compounds (VOCs), I apply the approach of metabolomics and systems biology to the field of ecology to explore the metabolic changes occurring inside the plants exposed to biotic and abiotic stresses. Particularly, I study the plant metabolic responses against P. brassicae chewing caterpillars during sequential treatment exposure to: abiotic stress by the oxidative air pollutant ozone (O3); dual herbivory with specialist Brevicoryne brassicae piercing-sucking aphids; and chemical induction of plant defences with the oxylipin phytohormone methyl-jasmonate (MeJA). Results show how during herbivore-induced responses, changes in defence- and growth-metabolic processes are tightly connected to stress protection mechanisms, indicating that plants actively reprogram their inner metabolic networks in order to adapt to consecutive changes in the environment. This thesis illustrates how evaluating the plant metabolome in its entirety rather than single metabolites, can help us understanding plant responses towards abiotic and biotic stresses, and improve our ability to predict how constant shifts in the environment affect plant physiology and ecology. / Ett huvudsyfte för ekologisk forskning är att förstå naturens komplexitet för att kunna förutse effekter av störningar i miljön. I min avhandling har jag fokuserat på ekologiska interaktioner mellan växter och insekter, två av de äldsta terrestra organismgrupperna på jorden. I mina studier har jag undersökt interaktioner mellan den korsblommiga växten svartsenap (Brassica nigra L.) och den specifika herbivoren kålfjäril (Pieris brassicae L.). Båda är väl karaktäriserade modellarter i kemisk-ekologisk forskning. De metaboliska förändringar som sker när växten utsätts för biotisk och abiotisk stress har analyserats hjälp av metabolomik, det vill säga analyser av metabolomet i sin helhet med hjälp av tekniker som vätske- och gaskromatografi kopplad till masspektrometri (LC- och GC-MS), och så kallad headspace-uppsamling av flyktiga organiska föreningar (VOCs). Jag har särskilt undersökt de metaboliska förändringar som sker när växten betas av kålfjärilslarver vid samtidig exponering för: abiotisk stress i form av ozon (O3), en oxidativ luftförorening; ytterligare betning i form av stickande och sugande bladlus (Brevicoryne brassicae); tillsats av oxylipinfytohormon metyl-jasmonat (MeJA), ett ämne som inducerar växtens försvar. Resultaten visar att de metaboliska förändringar som sker i växten vid herbivori med konsekvenser för dess försvar och tillväxt är nära kopplade till de metaboliska förändringar som sker vid stress, vilket visar att växten kan fortlöpande och aktivt omprogrammera sina metaboliska nätverk för att anpassa sig till förändringar i miljön. Avhandlingen visar att genom att utvärdera växtmetabolomet i sin helhet, snarare än att studera enskilda metaboliter, vi kan få bättre förståelse för hur växter reagerar på olika former av stress och därmed också bidra till att vi kan göra förutsägelser för hur förändringar i miljön kan påverka växters fysiologi och ekologi.

The surface climate response to 11-yr solar forcing during northern winter is first reestimated by applying a multiple linear regression (MLR) statistical model to Hadley Centre sea level pressure (SLP) and sea surface temperature (SST) data over the 1880–2009 period. In addition to a significant positive SLP response in the North Pacific found in previous studies, a positive SST response is obtained across the midlatitude North Pacific. Negative but insignificant SLP responses are obtained in the Arctic. The derived SLP response at zero lag therefore resembles a positive phase of the Arctic Oscillation (AO). Evaluation of the SLP and SST responses as a function of phase lag indicates that the response evolves from a negative AO-like mode a few years before solar maximum to a positive AO-like mode at and following solar maximum. For comparison, a similar MLR analysis is applied to model SLP and SST data from a series of simulations using an atmosphere–ocean general circulation model with a well-resolved stratosphere. The simulations differed only in the assumed solar cycle variation of stratospheric ozone. It is found that the simulation that assumed an ozone variation estimated from satellite data produces solar SLP and SST responses that are most consistent with the observational results, especially during a selected centennial period. In particular, a positive SLP response anomaly is obtained in the northeastern Pacific and a corresponding positive SST response anomaly extends across the midlatitude North Pacific. The model response versus phase lag also evolves from a mainly negative AO-like response before solar maximum to a mainly positive AO response at and following solar maximum.