Scholarship of ERC investigators is a critical component of their contributions to Missouri S&T and the UM System. Scholarly contributions enhance the reputation of the ERC, Missouri S&T and the UM System; enhance the ability to successfully compete for major external grants; and provide critically needed solutions to Missouri and the nation to pressing problems regarding emerging contaminants and related environmental issues.

Examples of scholarly contributions are provided below. Citations may be found in the Publications section further of this report.

Animal Agriculture in Missouri

• ERC researchers are working closely with the State of Missouri to address environmental, nuisance and potential health problems stemming from the state's animal production industry. The Department of Agriculture requested input on addressing lingering problems, leading to a number of initiatives.
  
  

• The Burken research group has optimized at laboratory scale the recovery of nutrients from livestock manure in the form of struvite, a crystalline magnesium-ammonia-phosphate solid that is a concentrated form of the nutrients. These nutrients are a top concern as the excess load is a top water quality concern in Missouri and throughout the agricultural Midwest. This waste-to-product technology will allow significant reduction in nitrogen and phosphorus pollution of streams in Missouri, while creating a valuable product from livestock (especially swine) waste. (Sponsor: USEPA)
  
  
• The Adams/Mormile research group is developing technology for the simultaneous removal of pathogens, anti-biotic resistant organisms, and antibiotics from wastewater slurry discharged into lagoons at livestock operations, and then periodically applied to surrounding crop fields. The aim of this work is to develop the means to prevent the release and spread of antibiotic resistance in pathogens that is making human (and veterinary) antibiotics increasingly ineffective. (Sponsor: USEPA) (See Macauley et al., 2006)
  
  
• The Fitch/Morrison research group examined the formation and control of gas-phase organic and inorganic compounds at concentrated animal feed operations (CAFO). The group studied lagoon covers and barn odor treatment technologies, including biofilters. (Sponsor: USEPA)
  
  
• The Burken/Mormile research group worked to evaluate odor production from open lagoons, commonly used at small to medium scale confined animal feed operations (CAFOs). Lagoons producing malodor were managed differently than functional lagoons (far less odor generation) and the impacts of mis-management were observable in the microbial populations present and active, as determined using molecular methods. The impacts were apparently related to overload conditions and poor solids management. (Sponsor: USEPA).
  
  
• The Burken/Morrison research group conducted work indicating that the low rate of mixing leads to optimized microbial consortia, improved treatment and thereby resulted in minimal odor production. A new research project, funded by USGS, is initiated to further investigate this process.
  
  
• The Adams/Mormile research group examined the fate and effects of veterinary antibiotics used at CAFOs in Missouri. The work showed that certain classes of antibiotics tend to degrade while others persist in lagoons, and that certain classes of antibiotics tend to remain in the mobile phase, while others are immobilized on particles. The work demonstrated that antibiotics at typical concentrations can have a significant negative impact on the anaerobic treatment effectiveness of treatment lagoons used at CAFOs, and the reduction of antibiotics in lagoons would allow much more effective treatment. (Sponsor: USEPA) (See Loftin et al., 2005.)

Safe Drinking Water

• Drs. Adams/Ma research groups are conducting a comprehensive study of the formation of disinfection byproducts from pesticides in drinking water. The study includes seven oxidants and 80 pesticides. It will provide the industry with both general information as to which disinfectants and pesticides are leading to disinfection byproducts in drinking water, as well as detailed information on their byproducts and the fate of the eight most critical pesticides. (Sponsor: AwwaRF)
  
  
• The Adams/Ludlow research group is investigating the optimization of the use of activated carbon to remove pharmaceuticals and endocrine disrupting compounds from drinking water. This work includes how integration of activated carbon and ozonation technologies can be integrated for optimal treatment effectiveness. (Sponsor: MDNR)
  
  
• Dr. Adams research group conducted technology evaluation and validation of enzyme linked immunoassay (ELISA) tests for endocrine-disrupting chloro-s-triazines for AWWA regulatory affairs and the USEPA. These tests demonstrated that the EPA-approved test (marketed by Beacon, as well as two others) can be inaccurate in many drinking waters, which resulted in the EPA removing its approval for the test, and reconsideration of the appropriateness of the use of ELISA for regulatory monitoring. (Sponsor: AWWA, AWWARF) (see Adams et al., 2004; Jiang et al., 2006)
  
  
• The Adams research group, conducted with McGuire/Malcolm Pirney, conducted a two-year study addressing analytical methods development and a nationwide occurrence study for total chloro-s-triazines which are proposed to be regulated as a group based on their endocrine disruption effects. Additional study on the treatability of chloro-s-triazines as a class at full-scale was assessed (Sponsors: AWWA, AWWARF, MDNR) (See Graziano et al., 2006; Jiang et al., 2006; Jiang and Adams, 2006; Jiang et al., 2004.)
  
  
• The Adams research group conducted two comprehensive analyses of the occurrence of carcinogenic disinfection byproducts (i.e., trihalomethanes and haloacetic acids) in Missouri drinking waters. These studies showed that for the period 1997-2001 approximately half of the water utilities in Missouri were exceeding the regulatory limits for both THMs and HAAs. From 2001-2005, significant progress toward compliance has been achieved, though many plants still are out of compliance. Furthermore, these studies show that each of the methods used to reduce THMs and HAAs are ineffective in many situations and the solution to disinfection byproduct control must lie in an integrated treatment approach. (Sponsor: MDNR) (See Adams et al., 2005; Adams and Timmons, 2006.)
  
  
• The Adams research group is examining how Missouri water utilities can best remove algal toxins (toxic byproducts of algae) in drinking water treatment plants. Additionally, the group is studying how conventional drinking water treatment may actually increase the concentrations of these emerging contaminants. (Sponsor: MDNR)
  
  
• The Adams research group is developing computer models to simulate the treatment of pharmaceuticals and endocrine disrupting chemicals in drinking water and wastewater using oxidative, sorptive and other processes. These models allow the prediction and optimization of the control of these compounds in treatment processes (Sponsor: MDNR) (See Qiang and Adams, 2004a and 2004b; Qiang et al., 2004; Adams, 2006.)
  
  
• The Adams research group has performed treatment process evaluations and optimization for the treatment of fuel oxygenates contaminating groundwater and drinking water supplies in Missouri. This Missouri-based field- and lab-study was aimed at assisting local governments and professionals to determine the most economical means to remove MTBE and other emerging oxygenates (e.g., DIPE, TAME, ETBE, etc.) from drinking waters supplies and groundwater. (Sponsor: MDNR and Missouri Petroleum Storage Tank Insurance Fund) (See Sutherland et al., 2004; Yu et al., 2005; Sutherland et al., 2005.)

Atmospheric Particulates and Pollutants

• The Whitefield/Hagen research group is studying aerospace particulates in many different applications including jet engine and rocket engines, and in commercial and military applications. The work of this group is internationally recognized for excellence and innovation.
  
  
• The Morrison research group conducted the first chemical and mechanistic analysis of the influence of ammonia and carbon-dioxide on the sorption of indoor pollutants. The study evaluated typical indoor surfaces and found that ammonia, commonly emitted from cleaners or waste products (e.g. diapers), drives amines off surfaces and into indoor air. Carbon dioxide tends to reduce indoor air concentrations of amines by increasing the capacity of surfaces. (Sponsor: NSF) (See Ongwandee and Morrison, 2005; Ongwandee and Morrison, 2006)
  
  
• The Morrison research group conducted the first field study of smog chemistry with indoor surfaces. By challenging building surfaces, such as carpet, with ozone, they have quantified the chemical reactivity and product yields of secondary aldehydes. Their work shows that carpet is the most important ozone sink, and secondary aldehyde source, in new buildings. As buildings age, carpets retain the ability to consume ozone and exhibit lower secondary aldehyde yields. Occupant use of cleaners and cooking oils enhances surface reactivity of kitchen or other surfaces. (Sponsor: NSF) (No publications in press to date: see Wang et al., 2006 in review.)
  
  
• The Morrison research group conducted field studies of indoor pollutant transport characteristics to provide guidance on the use of indoor air quality models. Their work demonstrates the importance of measuring both the time-varying and space-varying nature of pollutant transport to improve estimates of occupant exposure. (Sponsor: NSF) (See Morrison and Wiseman, 2006; Morrison et al., 2006.)
  
  
• The Morrison research group is presently conducting laboratory studies to quantify the heterogeneous kinetics of terpenes with ozone on indoor surfaces. Cleaners and other consumer products release large amounts of fragrances (terpenes) that react in air with ozone forming aerosols and irritating products. Surface chemistry with ozone is presently unknown, but is anticipated to be more important for many of the fragrance compounds found indoors. (Sponsor: NIOSH) (No publications in press to date)
  
  
• The Morrison research group is presently conducting laboratory studies to quantify ozone chemistry on human hair and in the near-head region. Individuals that use certain shampoos and conditioners are more heavily exposed to the byproducts of smog chemistry on their hair. Individuals wearing fragrances are more heavily exposed to aerosols and irritants due to ozone-terpene reactions. Morrison's group has learned that most human hair is very ozone-reactive and that some hair products generate secondary aldehydes that will be released into the breathing zone. (Sponsor: NSF) (No publications in press to date; see Karamalegos et al. 2006 in review.)
  
  
• The Morrison research group is conducting theoretical research to improve estimates of childhood exposure to asthma causing chemical agents. They find that a chemical signature remains in indoor materials, such as wood or plastics, long after exposure occurs. This signature can be used to "back-calculate" exposure that occurred years before. This is especially useful in studies of children and adolescents with asthma, because their exposure to the causative agent may have occurred when they were infants. (Sponsor: none) (No publications in press to date; see Morrison et al. 2006, in review.)
  
  
• The Chusuei/Morrison research group conducted surface vibrational studies of amines and carbon dioxide adsorbed onto polyethylene powders (simulating indoor surfaces) using attenuated-total reflection infrared (ATR-IR) spectroscopy. A custom ATR cell was designed and constructed to monitor the in situ gas adsorption onto the solid surfaces. [See Chusuei and Morrison, Contribution to Healthy Buildings Conference 2006 in Lisboa, PORTUGAL (to be presented in June 2006).].

Natural Treatment Systems

• The Burken research group is studying how to use plants such as poplar trees to remediate groundwater of a wide range of organic contaminants using phytoremediation technology.Several recent, important findings have increased the number of sites that can be remediated using phytoremediation. Additionally, work done in collaboration with BP has revealed that many contaminants from petroleum production can be destroyed in these systems, faster than had been previously thought.
  
  
• The Burken research group, in collaboration with the USGS, developed a tree-coring technology that allows delineation of contaminant plumes in groundwater without the need for drilling monitoring wells. Specifically, this discovery leads to conclusions that A) these plants can be sampled to indicate potential contamination in the subsurface and B) contaminants in the unsaturated zone can be removed by plants. A new sampling method using Solid Phase Microextration (SPME) can reduce the time and increase the sensitivity and target contaminant list.
  
  
• The Fitch/Burken research group is studying how to use constructed wetlands to remediate mine drainage and other waste streams of toxic heavy metals. These systems have proven to be robust and effective, and are being installed in full-scale operations by these research groups. This work has substantially increased understanding of removal mechanisms in such wetlands, and recently put forward a detailed and predictive model of how metals are removed. These developments allow for better design of wetlands. An example of such design is the full-scale high-flow wetland proposed to treat water draining from beneath developed areas of Park City, UT.

Environmental Impacts of Endocrine Disrupting Chemicals

• The Huang research group is examining the impacts of pesticide use in Missouri and elsewhere on the reproduction rates and endocrine impacts for amphibians. The work will help establish concentrations of pesticides that may pose significant reproductive impacts on struggling amphibian populations.
  
  
• The Adams/Huang/Gale research group examined correlations between concentrations of heavy metals in game fish and in sediments in Missouri rivers. The metals included endocrine disruptors (e.g., cadmium) as well as lead, zinc and copper. (Sponsor: Doe Run Corp) (See Gale et al., 2004.)
  
  
• The Maglia research group conducted preliminary surveys of mine-drainage exposed amphibian populations and began preliminary teratogenic assays of effects of mine drainage on frog development. The group also surveyed several Acris crepitans populations from Missouri with known malformations. The team described normal development in the species (to be used for baseline comparisons to malformations) and described and categorized several previously unidentified malformations in this declining species.
  
  
• The Wronkiewicz/Adams/Mendoza group is conducting a comprehensive study of the transport and bioavailability of heavy metals in the Big and Black Rivers. These streams have been impacted by mining activity. The heavy metals investigated included lead, zinc, copper, cadmium, cobalt and nickel. It has been found that the distribution and speciation due to metal contaminants in these streams is dominated by particulate material transport due to the slightly alkaline chemistry of the Missouri water systems and low solubility of many metal species. Also, it was found that high flows (floods) are responsible for the efficient transport of contaminated sediments (Sponsors: EPA, Missouri Water Resources Center) (See Faeth et al. 2003; Wronkiewicz et al., 2003; Faeth et al., 2004a; Faeth et al., 2004b.)

Energy Industry

• The Wang research group studied the impact of ammonia on the leachability of cationic metals such as Cu and Cd from fly ash. As a result of air pollutant emission control requirements, most fly ash in the future will contain ammonia. This research is to investigate the leaching behavior for the future fly ash, so that pollutant prevention measures can be taken before it happens. Results indicated than ammonia can form complexes with these metals and enhance their leaching. A mathematical model was developed to quantify the leaching behavior and effects of ammonia. One paper was accepted by Chemosphere (sponsor: EPRI).
  
  
• The Wang research group developed a protocol to quantify the intrinsic leaching parameters for trace elements from solid particles. This approach includes a lab experimental procedure and a modeling procedure. Eventually the total availability and the stability of cationic trace elements in solid particles can be determined. One paper was accepted (conditionally) by Waste Management (Sponsor: EPRI.)
  
  
• The Chusuei/Wang research group conducted arsenic absorption studies from aqueous solution environments onto fly ash. The As-Fly Ash interface was surface analyzed using attenuated-total reflection infrared (ATR-IR), extended X-ray absorption fine structure (EXAFS) and X-ray photoelectron (XPS) spectroscopies to delineate chemical oxidation state changes during the absorption and chemical speciation of arsenic on the solid surface. EXAFS were performed at the National Synchrotron Light Source at Brookhaven National Laboratory [See Chusuei and Wang, Geochim. et Cosmochim. Acta (in review).]
  
  
• The Wang research group conducted the leachability of arsenic and selenium from fly ash, and developed a speciation-based model to describe the leaching behavior. These research and modeling activities provided us with fundamental understandings of the metals leaching behavior. Results indicated that arsenic can be leached under low and high pH conditions. Selenium can be leached when pH is in neutral and alkaline pH range. Results also indicated that calcium can reduce the leaching of arsenic under very high pH conditions through the formation of calcium arsenate. Results also indicated that ammonia can enhance arsenic release. One manuscript on the modeling part was submitted to Geochemica Cosmochemica Acta for review and possible publication (sponsors: USGS and EPRI).
  
  
• The Wang research group conducted the mercury leachability studies for fly ash. In the future, most fly ashes will be contaminated by ammonia. In addition, the mercury air emission control requirement will result in elevated concentrations of mercury. This research deals with the leaching behavior of mercury in future fly ash. Results confirmed that ammonia can enhance the mercury leaching in the alkaline pH condition through the formation of less adsorbable mercury-ammonia complexes. Research also indicated that the injected activated carbon has stronger affinity to mercury than unburned carbon in fly ash. This information is important in assessing the potential environmental impact of mercury leaching as results of air emission control regulations. One manuscript will soon be ready to submit (sponsors: EPRI and Missouri S&TB).
  
  
• The Wang research group investigated the potential to use the brewery solids to generate methane gas (energy source) while reducing solids discharge. Operation parameters were determined in lab bench scale (sponsor: Anheuser-Busch foundation).

Nanoparticle Toxicity and Treatment

• The Ma/Huang groups are conducting research on the cytotoxicity of nanomaterials. Nano-technology has grown significantly in the past several years and will revolutionize the current technology in the near future. However, its environmental impact has not been well investigated, including that in Missouri. In our study, we are investigating the possible cytotoxicity of metal oxides (such as CeO2, Al2O3, TiO2, Fe2O3, ZnO) and non-metal oxide (such SiO2) at different sizes. Preliminary data have demonstrated that these nanomaterials are cytotoxic at the nano-diameter level. This study can be used by federal agencies to make regulatory policies for nanomaterial manufacturers. Three manuscripts that were produced for this study are either under review or in the submission process).

Specialized Water, Wastewater, and Food Treatment

• The Ercal/Adams research group is investigating the formation and control of disinfection byproducts formed during the disinfection of fruits, vegetables and meats. Additionally, the research focuses on the removal of beneficial oxidants (e.g., biothiols) during disinfection. The goal of this research is to help the agriculture industry in Missouri and elsewhere to achieve required disinfection of pathogens and rot fungus, without removal of beneficial antioxidant nutrients. (See Wu et al., 2006 ; Demirkol et al., 2004; Qiang et al., 2005.)
  
  
• The Adams research group is studying the enzymatic removal of synthetic and natural estrogens from municipal wastewater using a novel treatment process. The work will help to prevent the release of these highly active endocrine disrupting chemicals into the environment. (Conducted in cooperation with the Univ. of Quebec) (See Auriol et al., 2006.)