Current and Previous Research and Teaching Grants and Contracts

National Science Foundation

1. "CAREER: Hydroxyl Radical and Sulfate Radical-Based Advanced Oxidation Nanotechnologies for the Destruction of Biological Toxins in Water, National Science Foundation, $400,000, July 1, 2005-June 30, 2010.
2. "NER (Nanotechnology Exploratory Research): Fabrication of TiO2 Nanoparticles and Films for Environmental Applications Using Ionic Liquid-Based Self Assembling Sol-Gel Methods," National Science Foundation, $ 100,000, June 1, 2003-May 31, 2005.
3. "The Use of Ionic Liquids for the Remediation of Wastewater Contaminated by Halogenated Organics," National Science Foundation (through Tufts University), $150,000, Sep. 1, 2000-Aug. 31, 2002, (G. D. Botsaris, PI; D. D. Dionysiou and R.-Y. Qian, Co-PIs), (Ranked # 1 by the Reviewer Panel), Effort 33%.

Competitive Federal Projects and Industry Projects

1. NSF Project number 1 shown above.
2. NSF Project number 2 shown above.
3. NSF Project number 3 shown above.
4. "High Performance TiO2 Photocatalytic Coatings and membranes for the Purification, Disinfection and Recycle of Water and Air in Space Applications," National Aeronautics and Space Administration (NASA), $ 324,753, Jan. 12 2003-Jan. 11 2006.
5. "Degradation of Organics in Sediments by Field Effect TiO2 Catalysis," U. S. Environmental Protection Agency, Contract No. 68-C-00-159, Task Order No. 73, $60,828, Effort 94% ($57,178), Nov. 3, 2004-Dec. 31, 2005.
6. "Hydroxyl Radical and Sulfate Radical-Based Advanced Oxidation Nanotechnologies for the Destruction of Biological Toxins in Water," Ohio Board of Reagents, $62,262, July 1, 2005-June 30, 2010.
7. "Use of Persulfate and Peroxymonosulfate Oxidants for the Destruction of Groundwater Contaminants," Water Resources Research Institute, Ohio State University Research Foundation, $ 15,000, March 1, 2005-Feb. 28, 2006.
8. "Use of Room Temperature Ionic Liquids as Solvent Media for the Treatment of Organic Contaminants from Sediments and Solid Matrices," The Cooperative Institute for Coastal and Estuarine Environmental Technology (CICEET), $ 25,000, May 1, 2004-May 31, 2005.
9. "P3 Award: A National Student Design Competition for Sustainability focusing on People, Prosperity, and the Planet-Biotemplating of Titanium Dioxide Nanoparticles for the Green Production of Photochemically Active Catalysts: Synthesis, Characterization, and Photocatalytic Evaluation," U.S. Environmental Protection Agency, Grant Number SU831824, $10,000, Sep. 1, 2004-May 31, 2005.
10. Cobalt/Oxone Advanced Oxidation Process," Du Pont De Nemours and Company, $22,000, Oct. 2003- Sep. 2004.
11. "Use of Novel Hydrophobic Ionic Liquids for Extraction and in-situ Destruction of Polycyclic Aromatic Hydrocarbons," The Cooperative Institute for Coastal and Estuarine Environmental Technology (CICEET), $ 15,000, Jan. 1, 2002-Dec. 31, 2002.
12. "Optimized Treatment of MTBE Contaminated Water Using Fenton's Reagent," U. S. Environmental Protection Agency (EPA), Contract No. 68-C-00-159, Task Order No. 5., $ 21,000, April 2001-Nov. 2001.
13. "Assessment of Effects of Risk Management Activities on the Speciation and Transport of Mercury in Aquatic Sediments," U. S. EPA, Contract No. 68-C-00-159, Task Order No. 16 (D. D. Dionysiou, PI; George A. Sorial, Co-PI), $66,205, Effort 45%, Dec. 2001-Aug. 2001.
14. "Preventing the Initiation of Biofouling of Membrane Bioreactors in Wastewater Treatment," Water Resources Research Institute, Ohio State University Research Foundation, (D. B. Oerther, PI; D. D. Dionysiou and George A. Sorial, Co-PIs), $ 79,810, Effort 33%, Sep. 2002- Aug. 2003.

International Projects

15. "Evaluate the Efficiency of RTILs as Solvents to Regenerate Three-Way Catalytic Converters," University of Cyprus, $ 12,500, July 2004-Nov. 2006.

Other Projects

16. "Destruction of Microcystin-LR Cyanobacteria Toxin in Sources of Drinking Water Using UV-Based Advanced Oxidation Technologies," University of Cincinnati Research Council, $ 5,000, May 2003-May 2004.
17. "Innovative Method for the Generation of Hydroxyl Radicals to Oxidize and Eliminate Recalcitrant Organic Contaminants and Arsenic Species in Contaminated Water," University of Cincinnati Research Council, $ 5,000, May 2001-May 2002.
18. "Advanced Training for Learning State of the Art Instrumentation for Measuring Environmentally Hazardous Organic and Inorganic Contaminants in Water," University of Cincinnati Faculty Development Council, (Dionysios D. Dionysiou, PI; George Sorial and Daniel B. Oerther, Co-PIs), $7,500, 34%, March 2001-March 2002.
19. "Advanced Laboratory Series for Environmental Engineering and Science Education, Integrating Discipline-Based Labs in Cross-Cutting Education," Department of Civil and Environmental Engineering, University of Cincinnati, Jan. 2001, (D. B. Oerther, D. D. Dionysiou, George A. Sorial, Co-PIs), $ 24,000, Effort 33.3%.

Total Individual External Funding Received ((9/2000-1/2005): $1,086,210
Total Individual Internal Funding Received (9/2000-1/2005): $12,550
Total Collaborative Funding Received (9/2000-1/2005): $1,317,565

Summary of Research Projects:

"CAREER: Hydroxyl Radical and Sulfate Radical-Based Advanced Oxidation Nanotechnologies for the Destruction of Biological Toxins in Wat
er"
Dionysios D. Dionysiou (Single PI) National Science Foundation
$400,000, July 1, 2005-June 30, 2010.
Ohio Board of Reagents
$62,262, July 1, 2005-June 30, 2010

In this NSF CAREER project, Dr. Dionysiou and his group will apply novel nanotechnological methods for the development of robust technologies based on hydroxyl and sulfate radicals for the destruction of biological toxins in water. Dr. Dionysiou proposal includes both fundamental understanding of the underlying radical chemistry and novel engineering aspects that will play a critical role for the development of efficient water purification systems. The proposal also includes a strong educational component such as synergistic activities to (i) promote drinking water education in the Greater Cincinnati Area, (2) enhance course and curriculum development and cooperative education, especially in the fields of Advanced Oxidation Technologies, Environmental Nanotechnology, and Drinking Water, (3) develop educational initiatives for high school students, female students and students of underrepresented groups, and (4) establish an international student exchange program. Finally, in his proposed work, Dr. Dionysiou emphasizes collaboration with other scientists from Cincinnati, other cities in Ohio, the University of Notre Dame and other universities in Mexico, Switzerland, Korea, Greece and other countries.

"NER (Nanotechnology Exploratory Project): Fabrication of TiO2 Nanoparticles and Films for Environmental Applications Using Ionic Liquid-Based Self Assembling Sol-Gel Methods"
National Science Foundation
Dionysios D. Dionysiou (Single PI),
$ 100,000, June 1, 2003-May 31, 2005

In this project funded by National Science Foundation, Division of Ocean Sciences, Dr. Dionysiou and his group are investigating a novel method for the preparation of novel TiO2 nanoparticles and coatings that can be used to treat contaminated water and air. In this study, Dr. Dionysiou has proposed a novel modification of the traditional sol-gel methods which has the potential to make highly nanoporous TiO2 particles and films with high surface area. The modification is based on fundamental concepts on how to reduce the rates of hydrolysis and condensation reactions during sol-gel morphosynthesis and how to modify the properties of the solvent. In addition, the synthetic procedures involve novel concepts of Green Chemistry and Green Engineering that are of interest and among new initiatives of the Office of Research of the White House, the US EPA, and NSF.

"High Performance TiO2 Photocatalytic Coatings and membranes for the Purification, Disinfection and Recycle of Water and Air in Space Applications"
National Aeronautics and Space Administration (NASA)
Dionysios D. Dionysiou (Single PI),
$ 324,753, Jan. 12 2003-Jan. 11 2007.

In this project funded by NASA, Dr. Dionysiou's group is developing efficient water and air purification systems using novel nanotechnological ideas to enhance safety and self-sustainability of space missions. Dr. Dionysiou believes that more reliable and more cost effective technologies are required to purify, recycle, and reuse water and air in space missions, especially those that are designed for long duration, such as research in the International Space Station and future explorations to Mars and beyond. More efficient treatment systems for purification and reuse of environmental resources in space platforms will allow better life conditions for the crew members and will assist NASA's efforts to push further the frontiers of space exploration. In this project, Dr. Dionysiou and his group are working on basic and applied research to develop novel photocatalytic reactors and processes (alone or in combination with other technologies) for the continuous-mode treatment and purification of water. In a first phase of a three-phase project, they investigate novel pore engineering techniques for the preparation of supported TiO2 catalytic films and membranes. They investigate the role of various conditions of the fabrication routes for the preparation of immobilized TiO2 catalyst with tailor designed crystal phase, pore structure and size, mechanical stability and durability, and enhance catalytic activity. In a second phase, these supported catalysts are used for the development of meaningful continuous-mode photocatalytic reactors and membranes. In a third phase, these systems are used to purify contaminated water with properties of that of the wastewater of the International Space Station (hygienic, shower, urine) and that generated in other space platforms (current and future). Alternative systems are also being developed for the purification of cabin air in the ISS and other planetary platforms. These systems are also being evaluated and used for the purification of different contaminated waters in terrestrial applications.

"Cobalt/Oxone Advanced Oxidation Process" Du Pont De Nemours and Company
Dionysios D. Dionysiou (Single PI),
$22,000, Oct. 2003- Sep. 2004

Dr Dionysiou and one of his Ph.D. students (George Anipsitakis) worked together on the development of effective oxidation technologies based on novel alternative transition-metal based oxidants by modifying the Fenton's (Fe2+ +H2O2), Photo-Fenton's (Fe 2++H2O2+UV), and Fenton-like (UV-vis+ferrioxalate+H2O2) reagents. The modification concerns the replacement of iron with other transition metals and hydrogen peroxide with potassium peroxymonosulfate (KHSO5) and potassium persulfate (K2S2O8). The rationale for this modification is based on a careful analysis of the oxidation and reduction potentials of the components of each oxidation system. This modified oxidant is being utilized to oxidize and completely mineralize organic contaminants in water including pesticides, herbicides, and endocrine disrupting chemicals. The effectiveness of the novel oxidant is compared to that of the Fenton's, Photo-Fenton's, and Fenton-like reagents and H2O2/UV-assisted TiO2 photocatalysis. So far, the group discovered that peroxymonosulfate can couple synergistically with cobalt resulting in a more powerful oxidation system than Fenton's reagent and with a much broader range of application with respect of solution pH and mineral species (i.e., buffer, ionic strength).

"Use of Room Temperature Ionic Liquids as Solvent Media for the Treatment of Organic Contaminants from Sediments and Solid Matrices" The Cooperative Institute for Coastal and Estuarine Environmental Technology (NOAA/CICEET)
Dionysios D. Dionysiou (Single PI),
$ 25,000, May 1, 2004-December 31, 2005.

In this project funded by NOAA/CICEET, Dr. Dionysiou and his students are exploring the role of a New Generation of Solvents, known as Room Temperature Ionic Liquids (RTILs) in extraction of organic contaminants from solid matrices following by the in-situ destruction of the contaminants in the RTILs phase, resulting thus in the regeneration of the extractant. Dr. Dionysiou is among the first Environmental Engineers to perform research in the field of RTILs. In contrast to volatile organic solvents (VOCs), which are the source of major environmental problems, RTILs are made entirely of ions, are non-volatile and exhibit a unique array of physicochemical properties including extremely high temperature stability, high electrical conductivity, large electrochemical window (i.e., resistance to oxidation/reduction), and miscibility with certain solvents. As a result, RTILs are currently considered as novel solvents in applications dealing with pollution prevention (i.e., Green Engineering) in chemical synthesis, catalysis, electrochemistry and liquid-liquid separations. While the opinions in the scientific community are divided for the future of RTILs due to the higher cost and lack of comprehensive studies on the toxicity of these chemicals, Dr. Dionysiou believes that RTILs have several "Green" features and if they are used properly in selected processes, they can minimize pollution and they can enhance the efficiency and safety of certain environmental and chemical processes. One M.S. student is involved with this project.

"The Use of Ionic Liquids for the Remediation of Wastewater Contaminated by Halogenated Organics"
National Science Foundation
Gregory D. Botsaris, Dionysios D. Dionysiou and Ru-Ying Qian (33%/33%/33%)
$ 150,000, Sep. 1, 2000-Aug. 31, 2002

This project dealt with the coupling of novel emerging technology and a serious environmental problem. The technology is based on the use of the minimally explored class of solvents, the room temperature ionic liquids (RTILs). In contrast to the molten inorganic salts, that have a high melting point, RTILs are melts of salts that are liquids at or below room temperature. These solvents are comprised entirely of ions and constitute a new class of solvents that are different in properties from two classes of molecular solvents currently in use: water and organic liquids. The environmental problem concerns industrial wastewater effluents and groundwater contaminated by halogenated organic compounds. These pollutants are highly toxic polychlorinated organics, such as polychlorinated phenols, dioxins, furans, PCBs, chlorobenzenes, etc. They are usually in very low concentrations in the contaminated water; nevertheless they need to be removed with high efficiency. This investigation examines the selective extraction and concentration of these organic halogenated aromatics by RTILs. The unique properties of ionic liquids provide the high selectivity and the large partition coefficients necessary for a very efficient extraction and concentration. In one of the subsequent options to be considered, the extracted contaminants are removed by back extraction to a concentrated aqueous phase or by adsorption into a solid, where they are destroyed by known advanced oxidation technologies (AOTs). The most interesting idea to be studies, however, is the in-situ destruction of the pollutants inside the ionic liquid, either by AOTs or electrochemically. The unique properties of the ionic liquids may provide a particularly favorable environment for these destruction processes. During this project the PIs, among other aspects, were able (1) to develop analytical procedures for measuring environmental pollutants in ionic liquid, (2) to compare the photolytic degradation rates of all chlorinated phenols and several polycyclic aromatic hydrocarbons in ionic liquids, (3) to develop techniques for the purification of ionic liquids and explore the role of ionic liquid purity on the photodegradation rates, (4) to examine the potential for the recyclability of the ionic liquids, and (5) to unveil the detail photodegradation mechanisms of chlorinated phenols and PAHs in ionic liquids. .

"Optimized Treatment of MTBE Contaminated Water Using Fenton's Reagent"
U. S. Environmental Protection Agency
Contract No. 68-C-00-159, Task Order No. 5.
Dionysios D. Dionysiou (Single PI)
$ 21,000, April 2001-Nov. 2001

This project concerns the use of Fenton's Reagent for the degradation of methyl tert-butyl ether (MTBE) in groundwater aquifers. The Fenton's reagent is a mixture of ferrous iron and hydrogen peroxide. When these two chemical species are brought together, they form ferric iron, hydroxyl ions and hydroxyl radicals. These radicals are unstable and have high oxidation potential. When formed in an aqueous phase, hydroxyl radicals attack unselectively all organic contaminants in water. MTBE has been added as an octane enhancer to premium grade fuels to replace tetraethyl lead. In the last decade, the use of MTBE has been grown dramatically in an effort to reduce air pollution. However, during the last few years, MTBE has been detected in groundwater aquifers at relatively high concentrations due to leaks of gasoline storage tanks. MTBE is suspected to have adverse health effects and has extremely small threshold odor and taste concentrations. This study examined the effect of method of contact of the two Fenton's components and the dose of Fenton's reagent. The study also included identification of major reaction intermediates and their amenability towards hydroxyl radical attack. Several other parameters were examined including the molar ratio of the Fenton's components and the speciation of ferrous and ferric iron.

"Assessment of Effects of Risk Management Activities on the Speciation and Transport of Mercury in Aquatic Sediments"
Dionysios D. Dionysiou, George A. Sorial, Makram T. Suidan (45%/45%/10%)
$ 66,205, Dec. 2001-Aug. 2002.

The objective of this project was to provide a better understanding on the behavior of mercury during and after the implementation of a risk management option. The project concerned prediction the distribution of inorganic and organometallic mercury species in the sediment water based on (i) mercury concentration and speciation data prior to the remediation activity, (ii) physicochemical, biological, and hydro-geological data and analysis of the water/sediment system, and (iii) type, extent and purpose of the remedial action. The study considered three individual scenarios (and combinations between them) of mercury contamination: (1) urban, (2) industrial, and (3) mining. For each scenario, the effects of three remedies were evaluated: (1) dredging (spoils and remaining sediment), (2) in-situ capping, and (3) natural attenuation. Since each remedy can result in a change in the physical, chemical, and biological conditions of the sediment, it is expected that the speciation and transport of mercury can affect the result of implementing a remedy. This task relied on both literature and existing models to provide information on the fate of mercury during and after the implementation of each of the three proposed remedies. The analysis provided a critical literature review considering the extent of mercury contamination, mercury speciation, water and sediment physicochemical characteristics, level of microbial activity, geological and hydrological characteristics of the contaminated site and extent of sediment disturbance during the remediation process. To achieve this however, a clear understanding on the physicochemical interactions of mercury in water, sediments, soil, and atmosphere was required. Existing models were modified to study these interactions.

"Preventing the Initiation of Biofouling of Membrane Bioreactors in Wastewater Treatment"
Ohio State Water Resources Center
Daniel B. Oerther, Dionysios D. Dionysiou and George A. Sorial (33%/33%/33%)
$ 79,810, Sep. 2002- Aug. 2003.

The objective of this project was to investigate the problem of biofouling on membranes and examine the conditions that prevent the initiation of biofouling of membrane bioreactors in wastewater treatment. To accomplish this objective, the research team investigated the mechanisms of the initiation of biofilm formation on membrane surfaces through a synergistic study of (a) membrane physicochemical properties, (b) physicochemical and biochemical effect of the chemical composition of a typical wastewater treated with membrane bioreactors such as the pulp and paper mill wastewater, (c) biochemical interactions of the membrane material with the microorganisms, and (d) the role of microbial ecology of microbial populations on initiating biofouling. If the initiation of biofouling is eliminated, the costs associated with operating and cleaning the membranes should be dramatically reduced. Lower costs for membrane bioreactor technology should help in the widespread application of this technology for protecting the quality of the water environment in the state of Ohio and the protection of human health.