CHED 1054
Investigation of photolysis of PCDD/F congeners in soil matrix
Rebecca G. Vidrine and Barry Dellinger, Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803, bvidri5@lsu.edu
Due to the structural similarities between PCDD and PCDF congeners, we studied exposure to UV light of wavelength greater than 305nm on PCDD/F congener transformation. Temperature effects on PCDD/Fs are commonly study, however photolytic transformation is not well studied. We carried an investigated with a variety of PCDD/F congeners in a soil matrix exposed to UV with wavelength greater than 305nm at temperatures less than 30ºC. We observed dechlorination and an overall increase in furan concentrations. As an extension to this research, the effects of TiO2 as a possible catalyst for the photolytic congener transformation was also investigated.
CHED 1055
Reduction of N-nitrosodimethylamine with nanophase nickel-boron catalysts
Claire E. Joseph, Andrew J. Frierdich, and Timothy J. Strathmann, Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, 4161 Newmark Lab, 205 North Mathews Ave., Urbana, IL 61801, cjoseph2@uiuc.edu
N-Nitrosodimethylamine (NDMA) and related N-nitrosamines are a class of potent carcinogens that are generated as byproducts of wastewater and drinking water disinfection with combined and free chlorine. Recent work from our laboratory shows that NDMA is rapidly reduced by porous Raney-type nickel catalysts in water using H2 as an electron donor. However, Raney Ni is pyrophoric, so more stable alternatives are sought for treatment applications. This work examines the kinetics of NDMA reduction in water by H2 in combination with nanophase nickel-boron (Ni-B) catalysts that are non-pyrophoric. Ni-B catalysts are highly active for NDMA reduction, with metal-normalized pseudo first order rate constants as high as 200 L gNi-1 h-1, which is significantly more active than Raney Ni (81 L gNi-1 h-1) and 5% Pd/Al2O3 (6 L gPd-1 h-1). The influence of solution pH and the Ni:B ratio on reaction rates will also be discussed. Nickel-boron's higher stability in the presence of oxygen combined with the low costs of nickel and boron suggest that Ni-B materials may be viable alternatives to Raney Ni and more expensive precious metal catalysts.
CHED 1056
Small scale production of renewable alternative fuels
Peter J Iles1, Luther Giddings2, Ron Valcarce2, Neil Bastian2, Sesh Seshadri2, Trevor Feagin2, Mark Hebert2, So Kang2, Spencer Bremmer2, and Mequi Arrendondo2. (1) Division Chair Natural Sciences, Salt Lake Community College, 4600 South Redwood Rd, PO Box 30808, Salt Lake City, UT 84130, peter.iles@slcc.edu, (2) Chemistry Department, Salt Lake Community College, Salt Lake City, UT 84130
The ACS student affiliates group at SLCC is comprised primarily of transfer students to the science disciplines. This project provided a research and chemical engineering project involving many specialties. Increasing fuel prices increase alternative fuel interest. Waste is another problem of today's society, thus producing fuel from waste would be an efficient solution to two major issues. Methane gas can be collected from wastes through acidification. Our project was designed to collect the highest percentage of methane from waste products on a small, inexpensive scale. The proper ratios of carbon to nitrogen (30:1 respectively) were identified and the methane collection apparatus was assembled.The collection system was designed for long-term production. To maximize production,passive carbon dioxide infusion was used to maintain a constant pressure and anaerobic respiration within the digester. The final product was treated to remove carbon dioxide and water.
CHED 1057
Toxicity of toluene exposure in a rat lung epithelial cell line
Femi E Felix-Ukwu, NASA University Research Center, Texas Southern University, 2111 Holly Hall, apt 1203, Houston, TX 77054, femifelix@gmail.com
Toluene is an aromatic, hydrophobic, volatile organic compound (VOC). Chronic exposure to toluene may lead to irreversible brain damage as well as occupational asthma. On the other hand, frequent acute toluene exposure, arising from the use of many household products such as paint thinners, nail polish, disinfectants and synthetic fragrances, has also been related to many health issues. Toluene toxicity in mammals is mostly attributed to its metabolism, since it's extreme hydrophobicity causes unusually difficult cellular excretion. In related studies, mice with acute exposure to toluene were shown to exhibit an increased tolerance to respiratory infection. Herein, we evaluated the relative stability of toluene in an established medium using gas chromatography, with data indicating that toluene is relatively unstable in the presence of aqueous media containing a rat lung epithelial cell line. Since cellular uptake was noted, we preliminarily quantified and assayed the cytotoxicity (LD50) of toluene to our rat lung epithelial cell line, with results disclosed within.
CHED 1058
Mercenaria mercenaria as an environmental biomonitor of cadmium pollution
Kellie McCartin, Veronica Ortiz, and Stephen K. O'Shea, Department of Chemistry, Roger Williams University, One Old Ferry Rd, Bristol, RI 02809, kmccartin814@hawks.rwu.edu, vortiz237@hawks.rwu.edu
Cadmium (Cd) contamination of the aqueous environment is rapidly increasing as this element enters the food web and bioaccumulates into the higher trophic levels at a greater rate. This research investigated the comparative metal bioaccumulation efficiency in Mercenaria mercenaria (quahogs) between chelated Cd2+ complexes (Acetate, EDTA) and free hydrated Cd2+ ions from a saline environment. Total bioaccumulated Cd tissue concentrations were determined by atomic absorption spectroscopy. The concentration of Cd in the gills, muscles, and feet were correlated to the concentration of the protein, metallothionein. Metallothionein activity is up-regulated even at low environmental concentrations of heavy metal exposure. At low concentration, levels of metal contamination are notably below instrumental detection limits; therefore it is easier to detect MT activity. The results of this research could possibly demonstrate the effective use MT activity in quahogs as biomonitors of heavy metal pollution.
CHED 1059
Accumulation of cadmium in sunflowers from calcium- and zinc-loaded hydroponic solutions
Emily G. Frost, Department of Chemistry, Chatham University, Woodland Road, Pittsburgh, PA 15228, efrost@chatham.edu, and Joseph MacNeil, Department of Chemistry, Chatham College, Pittsburgh, PA 15232
Heavy metals, including cadmium, accumulate in soil from many sources, including car exhaust, airborne particles, paints, acid mine drainage, and pesticide and fertilizer run-off. One of the most promising methods of removing these pollutants from soil involves phytoremediation via phytoextraction, where a plant absorbs the toxins and is harvested, reducing the concentration left in the soil. Previous research has shown that sunflowers are efficient at accumulating cadmium (Cd2+) from soil, especially when EDTA, a chelating agent, is added to make the Cd2+ more mobile. It is not yet fully understood how the Cd2+ crosses the plant membranes at the root. This study investigated this process by studying how Cd2+ absorption is affected by the presence of calcium (Ca2+) or zinc (Zn2+) ions, both of which are essential to the plant's development. Sunflowers grown hydroponically were treated with Cd2+, EDTA, and varying levels of Ca2+ or Zn2+. Results show that an interaction does exist, suggesting that Cd2+ may enter cells through the same channels as Ca2+ and/or Zn2+.
CHED 1060
Activity of pyridinoporphyrazine catalysts in the aerobic oxidation of thiols
Raymond Risley and Phillip D. Voegel, Department of Chemistry & Physics, Southeastern Louisiana University, SLU 10878, Hammond, LA 70402, phillip.voegel@selu.edu
The removal of sulfer from gasoline is becoming an increasingly important environmental issue as petrueluem feedstocks currently in use for gasoline production have higher levels of sulfer than those previously employed. As such, increased levels of sulfer in fuels lead to increasing levels of sulfer dioxide polution and could, ultimately, lead to greater levels of acid rain. Cobalt pyridinoporphyrazine catalysts are compared to cobalt phthalocyanine, a catalyst commonly employed in petroleum refining. Mixtures of linear, branched, and cyclic thiols are aerobically oxidized in alkaline solution in the presence of each of the catalysts and the product disulfides are extracted and analyzed by GC/MS for identification. GC/FID is employed for quantification of remaining thiols after reaction to determine catalytic efficiency. Cobalt-3,4-pyridinoporphyrazine shows the greatest efficiency in thiol removal with more than 90% of most thiols removed during a 30-minute reaction period compared to 60% removal by cobalt phthalocyanine. Cobalt-2,3-pyridinoporphyrazine also shows improved efficiency compared to cobalt phthalocyanine, but to a lesser extent.
CHED 1061
Adsorption of heavy metals from wastewater using crab, shrimp and crawfish shells
Jamal Alexander, Department of Physics & Engineering, Xavier University of Louisiana, 1 Drexel Dr, New Orleans, LA 70125, jalexan6@xula.edu, and Bryan Bilyeu, Department of Physics and Engineering, Xavier University of Louisiana, New Orleans, LA 70125
Heavy metals, like cadmium, lead, copper, and arsenic in industrial wastewater discharge are strictly limited by state and federal regulations due to the severe threat to the environment and can't be eliminated by traditional chemical and biological wastewater treatment techniques. Traditional techniques which selectively remove them are expensive and difficult to implement. Natural cellulose and chitin products have shown effectiveness in adsorbing or binding metal ions in solution. This project evaluates the effectiveness of shells from crabs, shrimp and crawfish from local seafood processors to adsorb heavy metal ions from aqueous solutions. The sorbents will be evaluated for both metal capacity and binding strength, as well as selectivity. The influence of cleaning methods and surface treatments done to the shells on adsorption effectiveness is also optimized.
CHED 1062
ATR-FTIR investigation of molybdenum cycling in the presence of organics
Kelly Murphy and Jennifer L. Morford, Department of Chemistry, Franklin & Marshall College, P.O. Box 3003, Lancaster, PA 17604-3003, jennifer.morford@fandm.edu
This study investigates the importance of organic molecules (salicylic acid and protocatechuic acid) for molybdenum removal from the aqueous phase. Various combinations (molybdate; organic; molybdate and organic) were combined with solid aluminum oxide at a constant ionic strength, equilibrated, and analyzed using ATR-FTIR. In order to determine organic species' changes in the presence of molybdenum, spectral comparisons of the supernatant and solid were performed. These suggest that salicylic acid forms a different surface complex via its carboxylic group in the presence of molybdenum; molybdenum interacts with the phenolic group on salicylic acid. The shift and formation of new peaks in the molybdenum region implies that organic interactions influence molybdenum adsorption. Molybdenum has no effect on the adsorption of phenolic groups of protocatechuic acid to the solid surface as evidenced by a lack of change in the spectra. Analysis of the supernatant showed the formation of an aqueous molybdenum-organic complex.
CHED 1063
Analysis of enrofloxacin degradation and photoproduct antibacterial activity
Jenna M. Schroeder, Rachel A. Lundeen, and Kristine H. Wammer, Department of Chemistry, University of St. Thomas, 2115 Summit Ave., OSS 402, St. Paul, MN 55410, jmschroeder@stthomas.edu
Enrofloxacin is a fluoroquinolone antibacterial that has been found in natural waters at low concentrations and is subject to photodegradation under sunlight. While loss by photolysis is usually assumed to mean mitigation of potential environmental impacts, problems may arise if the photoproducts themselves introduce additional antibacterial activity. The antibacterial activity of enrofloxacin's photoproducts was assessed by determining their ability to inhibit growth of Escherichia coli DH5α. The photoproducts greatly inhibited bacterial growth, suggesting the necessity to isolate photoproducts to examine their potential environmental impacts. A minor photoproduct was isolated and identified as ciprofloxacin, a different fluoroquinolone; formation of ciprofloxacin as an enrofloxacin photoproduct has been observed previously. Analysis of ciprofloxacin's antibacterial activity shows that it accounts for only a small fraction of the overall inhibition of bacterial growth by the enrofloxacin photoproducts. Work continues to isolate and identify additional photoproducts in order to account for the additional antibacterial activity observed.
CHED 1064
Analysis of low and high octane gasoline using gas chromatography/mass spectroscopy
Fred G. Walker, James Coffield, and Michael J Baird, Department of Chemistry, Wheeling Jesuit University, 316 Washington Ave., Box 844, Wheeling, WV 26003, Fax: 304-243-4441, baird@wju.edu, Baird@WJU.edu
The purpose of this research is to identify the major components in low vs high octane gasoline samples. Samples of 87 and 91 octane gasoline will be obtained from local gasoline stations and will analyzed using GC/MS. Identification will be made using the on-line NIST mass spectral library as well as analyzing known standards. Low and high octane gasoline will be compared from the same gas station as well as from different manufactures. It is expected that more aromatics will be found in the high octane gasolines.
CHED 1065
Analyzing for potential surface water lead contamination around a WWI firing range adjacent to the Greater Plains Elementary School, Oneonta, New York
Tyler Callnan, Department Chemistry, Hartwick College, One Hartwick Drive, Oneonta, NY 13820, Fax: 607-431-4374, callnant@hartwick.edu, John B. Dudek, Department of Chemistry, Hartwick College, Oneonta, NY 13820, and Dr. Eric L Johnson, Geology Department, Hartwick College, Oneonta, NY 13820
This project measures the amount of lead contamination within the watershed area of a WWI firing range in the city of Oneonta, NY. Samples from both surface water and ground water upstream and downstream from the site will be analyzed for lead content. Using local lead averages not within the WWI firing range watershed, we will determine the degree of hazard, if any, that maybe be coming from this area. Also, if there is lead contamination, the project will determine the movement of the lead contamination within the watershed. The amount of lead will be measured using atomic absorption spectroscopy and colorimetric tests
CHED 1066
Analyzing imported toys for possible lead contamination
Mary Beth R. Lewton, James Coffield, and Michael J Baird, Department of Chemistry, Wheeling Jesuit University, 316 Washington Ave., Box 674, Wheeling, WV 26003, baird@wju.edu
Historically, lead has been used in paint as a cost effective method for improving surface adherence and enhancing color. Concerns about lead poisoning, especially in children, has led to strict regulation of lead levels in paints, especially those used in toys. Young children are of particular concern due to their tendency to mouth and chew on toys. Recent recalls of toys manufactured in China due to lead contamination have caused grave concern among consumers. In this project several toys purchased from local department stores and imported from China will be tested for lead using atomic absorption spectroscopy. Methods will be investigated for digestive and extraction of lead from both paint scrapings as well as the whole toy sample. Lead levels will be compared to current regulated limits.
CHED 1067
Assessing the Langmuir and single-point phosphorus sorption maxima of select mollisol soils
Angela Gunlogson and Frank V. Schindler, Department of Chemistry, Southwest Minnesota State University, 1501 State Street, Marshall, MN 56258, gunloga@southwestMSU.edu
A single point phosphorus (P) sorption index (PSI) may be an effective alternative to the traditional Langmuir isotherm for determining the P sorption capacity of soil. Previous research indicates a positive correlation between the P sorption maxima as determined by the Langmuir isotherm and the PSI. This study continues to evaluate the efficacy of the PSI in determining the P sorption capacity of soil. Separate air-dry soil samples of select mollisols were subjected to: 1) a series of equilibrating solutions ranging in their P concentrations, and 2) a single solution of known P concentration. The P sorption maxima were determined by modeling the data to the linearized form of the Langmuir equation. The amount of variability in the Langmuir sorption maxima explained by the PSI method is presented. This study provides additional information regarding the use the PSI method as a routine test of a soil's P retention capacity.
CHED 1068
Bacterial community response to increased carbon dioxide levels as a consequence of an underground coal mine fire
Cristiana Baloescu1, Maria G. Georgieva1, Stacey-Ann Y. Benjamin2, and David C. Edwards3. (1) Department of Chemistry and Physics, Wesleyan College, 4760 Forsyth Road, Macon, GA 31210, cbaloescu@wesleyancollege.edu, (2) Department of Chemistry, University of Florida, Gainesville, FL 32611-7200, (3) Chemistry and Physics, Wesleyan College, Macon, GA 31210
This project investigates the effects of prolonged elevated temperature and CO2 exposure on the bacterial make-up of soil from Centralia, Pennsylvania. Centralia soil is exposed to high CO2 concentrations due to an underground coal fire. This site provides an example of a leaking underground CO2 deposit, with implications for assessing the feasibility of geologic carbon sequestration. Initial studies indicate exposure of soil to elevated levels of combustion gases increases metal availability, having detrimental effects on the ecosystem. To further characterize the soil conditions (increased heat and CO2 concentrations), this study also identifies the bacterial composition. Ideally, the concentration of nitrifying bacteria should increase with available ammonia as a result of the fire, while other bacterial types would disappear. The pure cultures of bacteria obtained from Centralia soil are undergoing microbiological testing and Bergey's Manual of Systematic Bacteriology will be used to identify the genus and species of the soil bacteria.
CHED 1069
Bartram project
Ben Barfield, Steven Rowland, David Wilson, and Jack H. Owens Jr., Department of Chemistry and Physics, Georgia College & State University, CBX 082, Milledgeville, GA 31061, benjamin_barfield@ecats.gcsu.edu, steven_rowland@ecats.gcsu.edu
The increasing price and scarcity of fossil fuels has instigated a worldwide search for a renewable source of energy. A research group of undergraduate chemistry majors from Georgia College and State University is teaming up with John Gormly of the Georgia Forestry Commission and Bartram Forest to explore the preparation of wood pellets from slash and loblolly pines, prevalent in middle and northern Georgia. Pelletized wood has shown promise for both small and large-scale usage in Sweden and Spain, where over one million metric tons are now being produced and consumed annually. Of that amount, more than thirty percent of the pellets are derived from various species of pine. The sawdust from age-specific trees was collected and analyzed using bomb calorimetry. Preparation methods will be described and an analysis of the results will be presented.
CHED 1070
Bioaccumulation of lead in aquatic plants from a natural wetland
Sergio J. Cardona-González1, Yadiel Vega-Pérez1, Vivianette Alicea-Vázquez1, Ariana I Calderón-Pagán1, Maiella Ramos-Fontán1, and José Arbelo-García2. (1) Department of Physics and Chemistry, University of Puerto Rico at Arecibo, P.O. Box 4010, Arecibo, PR 00614-4010, (2) Department of Biology, University of Puerto Rico at Arecibo, Arecibo, PR 00614-4010
Biological indicators, such as aquatic plants, have been used for monitoring water pollution by trace elements and toxic metal ions. There has been a growing interest in the use of metal-accumulating roots and rhizomes of aquatic vascular plants for the removal of heavy metals from contaminated aqueous streams. Aquatic plants such as Sagittaria lancifolia, Salvinia minima, Typha domingensis are suitable for this purpose. These emergent macrophytes are abundant in the wetland system, Caño Tiburones, located in the northern part of Puerto Rico. This natural tropical wetland has been exposed to contamination by aqueous effluents produced from industrial activities, waste disposal sites, local or municipal sewage, agricultural activities among others. The aim of the present work was to provide quantitative information on the concentration levels of lead in aquatic plants and surface water samples collected from the wetland, Caño Tiburones. Samples were obtained from three sampling stations. Plant samples were digested using a microwave laboratory oven (CEM MARS X). Analysis was performed by means of a flame-graphite furnace atomic absorption spectrometer (PE AAnalyst 800). Bioaccumulation factors for plant roots are reported. The results of this study can provide the basis for understanding the bioaccumulation and phytoremediation capabilities of the aquatic plants Sagittaria lancifolia, Salvinia minima and Typha domingensis for environmental cleanup purposes.
CHED 1071
Cadmium ion effect in developing zebrafish (Danio rerio)
Elizabeth H. LeMasters1, Ashley J. Goss2, Kerri S. Warren2, and Stephen K. O'Shea3. (1) Department of Biology and Marine Biology, Department of Chemistry, Roger Williams University, 1 Old Ferry Rd., Bristol, RI 02809, (2) Department of Biology and Marine Biology, Roger Williams University, Bristol, RI 02809, (3) Department of Chemistry, Roger Williams University, Bristol, RI 02809
A zebrafish larvae bioassay was developed to explore the biological impact of a cadmium environment on early stage development. Our previous research in the lab suggested that the presence of excess sodium acetate affects the accumulation of cadmium in four day old zebrafish. This study compares the effects of 1, 5 and 50 μM CdCl2 and Cd(CH3CO2)2 on larval morphology and physiology. The dose-dependent biological response to both forms of cadmium was determined, but there was no significant observable difference between larvae exposed to chloride versus acetate ion. Both cadmium species induced shortened body lengths, pronounced axis curvature, cardiovascular defects and a lethal failure to inflate the swim bladder. ICP-MS (111Cd) accumulation in the presence of acetate and other chelating ligands (NTA, EDTA) were investigated to find a correlation between accumulation, bioavailability, and phenotype. A correlation of total accumulated Cd ion versus physiological response was also observed. Supported by RI-INBRE NIH P20 RR016457.
CHED 1072
Cobalt catalyzed cyclohexane oxidations
L Shannon Davis and Jessica A. Gunn, Department of Chemisty, Georgia Southern University, PO Box 8064, Statesboro, GA Ga, Fax: 912-681-0699, sdavis@georgiasouthern.edu
The current production of adipic acid, a precursor to Nylon-6,6, involves the oxidation of cyclohexane in a two-step process that produces a large amount of waste and greenhouse gases. One way to overcome these problems would be to produce adipic acid in one step, preferably from the commodity chemical cyclohexane. A new, extremely cost efficient method for producing hydrogen peroxide has recently been announced, making a renewed study of peroxide-based oxidation chemistry worthwhile. The focus of this project is to determine the efficacy of a series of cobalt-encapsulated zeolite catalysts with hydrogen peroxide for the single step production of adipic acid from cyclohexane.
CHED 1073
Collecting and testing soil samples at the James River
Richard J. Mullenberg IV and Dominique E. Williams, American Chemical Society Student Affiliates, Virginia Commonwealth University, 1001 W. Main St., PO Box 842006, Richmond, VA 23284-2006, mullenbergrj@vcu.edu
Soil samples were collected at various sites along the James River. The samples were digested in aqua regia on a hot plate and analyzed using ICP-OES for As, Cd, Hg, and Pb.
CHED 1074
Color optimization of sweet potato bread for improved consumer acceptance
Lashawndra Lawrence1, Adelia C. Bovell-Benjamin2, Peter Gichuhi2, and Chellani Hathorn2. (1) Tuskegee University, Tuskegee Institute, AL 36088, lmlawren@aol.com, (2) Department of Food and Nutritional Sciences, Tuskegee University, Tuskegee Institute, AL 36088
Orange-fleshed sweetpotatoes are rich in Beta-carotene, which imparts its orange color to them. Previous work with newly developed sweetpotato breads (SPB) indicated that its color was unacceptable to consumers. The objectives of this study were to: i) modify the color of previously developed sweetpotato breads and evaluate the impact on the loaf volume, color, moisture, vitamin C and Beta-carotene contents of the breads; and ii) assess consumers perceptions of the modified SPBs. Eight bread formulations containing 50 and 65% sweetpotato flour (SPF); dough enhancers without (DE) and with sweetpotato starch (DES); and FDA approved food dyes (at 3:2 ratio of red: green) were prepared and baked in bread machines (subsequent to baking). The loaf volumes, moisture, vitamin C and color of the breads were determined using the seed displacement method, IR-200 moisture analyzer, a chroma meter and 2, 6-dichloro-phenol-indol-phenol titrimetric method, respectively. Beta-carotene was extracted from the samples with 7:3 hexane: acetone and measured spectrophotometrically at 450 nm. Consumers perceptions were assessed in a focus group (n=7). The color of the SPBs was successfully modified from bright yellow to a wheat bread-like color. For the SPBs, the loaf volumes ranged from 1000 to 1200mL, moisture contents were between 30 to 35%, the color L* values ranged from 50.6 to 58.4, and vitamin C content was between 1177.1 and 3251.3 micrograms/100 g. The consumers perceived the color of the 50% SPF bread with DES and dye as awesome. Focus group participants described the texture of the 50% SPF bread with DE and dye as normal. The texture of the breads with 65% SPF, DE, DES and dyes were perceived as too moist, dry, tough and stiff, respectively. Overall, the color of SPBs was successfully modified to a brown-wheat bread-like one, which was perceived as normal by consumers.
CHED 1075
Conversion of triglyceride to methyl ester in improved process for production of biodiesel
Kara Marie Strickland and Donald L Wharry Jr., Department of Chemistry, Saint Edwards University, 3001 South Congress, Austin, TX 78704, kstrick@stedwards.edu
The current process for converting triglycerides to methyl esters yields glycerin as a waste product which is inconsistent with principles of green chemistry. The research will explore modifying the current process by using alternative methanol sources in an effort to recover the glycerin in a form that can be utilized in other chemical processes. Another possible outcome would be leaving it in the final product for use as biodiesel. The process consists of reacting 2,2-dimethoxy propane (methanol acetal of acetone) with triglyceride to make 1,2-isopropylidene glyceryl fatty ester and methyl fatty esters. The effects of variations in the amount of reactants, co-catalysts and catalysts will be explored to find a combination that creates the maximum conversion. Reaction progress is monitored by taking samples from the reaction flasks and analyzing by GC.
CHED 1076
Copper catalyzed cyclohexane oxidation
L Shannon Davis and Christopher R. Riley, Department of Chemisty, Georgia Southern University, PO Box 8064, Statesboro, GA Ga, Fax: 912-681-0699, sdavis@georgiasouthern.edu, sdavis@georgiasouthern.edu
The current production of adipic acid, a precursor to Nylon-6,6, involves the oxidation of cyclohexane in a two-step process that produces a large amount of waste and greenhouse gases. One way to overcome these problems would be to produce adipic acid in one step, preferably from the commodity chemical cyclohexane. A new, extremely cost efficient method for producing hydrogen peroxide has recently been announced, making a renewed study of peroxide-based oxidation chemistry worthwhile. The focus of this project is to determine the efficacy of a series of copper-encapsulated zeolite catalysts with hydrogen peroxide for the single step production of adipic acid from cyclohexane.
CHED 1077
Correlating total and extractable phosphorus for select mollisol soils
Nicholas Schneider and Frank V. Schindler, Department of Chemistry, Southwest Minnesota State University, 1501 State Street, Marshall, MN 56258, schnein@southwestMSU.edu
Phosphorus (P) is an essential nutrient input parameter for soil P loss indices, and its determination is necessary to develop Best Management Practices (BMPs). Knowledge of total soil P is useful in developing environmental management strategies that minimize loading of P to water resources. Total P is not routinely conducted in soil testing laboratories due to the rigors of digestion. Consequently, evaluating the correlation between standard soil test P indices and total P as a means of estimating total P from easily extractable P is of interest. Total P of select Mollisol soils was determined using mixed sulfuric and hydrofluoric acid digestion and ascorbic acid colorimetric procedures. Extractable P was determined by extracting a known quantity of soil with either: 1) 0.025 M hydrochloric acid plus 0.03 M ammonium fluoride, 2) sodium bicarbonate, or 3) a mixture of acetic acid, 0.25 N ammonium nitrate, 0.013 N nitric acid, 0.015 N ammonium fluoride, and 0.001 M EDTA. Total and extractable P relationships were analyzed using the method of least squares through standard SAS regression analysis. The significance of the relationships are discussed.
CHED 1078
Determination of biodiesel purity through near- and mid-range FTIR spectroscopy
Patrick M. Knapp and Edward Maslowsky Jr., Division of Molecular and Life Sciences, Loras College, 1450 Alta Vista, Lorsas College Box 875, Dubuque, IA 52001, patrick.knapp@loras.edu
As the United States attempts to reduce its dependency on foreign oil, there is the need to search for alternative types of fuel. One practicable alternative is biodiesel that can be produced from different types of plant oils. The oils are converted to biodiesel though a transesterification reaction involving the use of methanol. Both near- and mid-range FTIR spectroscopy have been used to monitor the transformation of plant oils into the methyl esters of fatty acids through the reaction of these oils with methanol. The spectra were recorded using both transmission and ATR techniques.
CHED 1079
Determination of pharmaceuticals in biosolids used for cropland soil amendment
Ashley D. LaMontagna, Department of Chemistry, Carroll College, 100 North East Avenue, Waukesha, WI 53186, Fax: 262-524-7112, alamonta@cc.edu, and Joseph J. Piatt, Department of Chemistry and Biochemistry, Carroll College, Waukesha, WI 53186
This study investigated the occurrence of pharmaceuticals in biosolids, local biosolid-amended crop soils, and Fox River sediments located near the discharge points of Waukesha County wastewater treatment plants. Recent studies have verified the presence of pharmaceuticals in the wastewater influent and effluent; therefore it is likely they are accumulating in solids produced during treatment or from subsequent exposure to those solids or effluent. The biosolids have been anerobically digested and dewatered and are applied as an organic-rich amendment to local cropland soils. The river sediments are exposed to the treated effluent and were sampled above and below the discharge points to the river. The solids were liquid/solid extracted and cleaned up and concentrated using solid-phase-extraction. The extracts were then analyzed for acetaminophen, atorvastatin, carbamazepine, caffeine, cimetidine, diltiazem, fluoxetine, hydrocodone, and erythromycin using LC/MS analysis in MS (+1) mode.
CHED 1080
Dissolved oxygen levels for East Texas streams
Justin Treas and Mike Buttram, Chemistry Department, Texarkana College, 2500 North Robison Road, Texarkana, TX 75599
This study compares dissolved oxygen levels for East Texas streams during the index and critical periods and the impacts of these conditions on fish assemblages.
CHED 1081
Do fabrics in stuffed toys absorb pesticides and flame retardants from residential homes
Alexa R. New, Department of Biology, Chatham University, Woodland Road, Pittsburgh, PA 15232, anew@chatham.edu, and Renee L. Falconer, Department of Chemistry, Chatham University, Pittsburgh, PA 15232
In recent studies, the levels of polybrominated diphenylethers (PBDEs) and organochlorine pesticides (OCs) in stuffed children's toys showed substantial levels of PBDEs in the outer shells of the toys, while OC pesticide levels were significant throughout most toys studied. Significant levels of both these chemical types have also been found in indoor air in residential homes. The current project was designed to further examine the presence of these chemicals in children's stuffed toys by determining if absorption from indoor air is a possible source onto the toys. Concurrent indoor air samples and stuffed toy samples were placed in homes in western Pennsylvania for two weeks then analyzed for concentrations of OCs and PBDEs. Preliminary data suggests that absorption of both PBDEs and OC pesticides from indoor air onto stuffed toys occurs. Levels due to absorption may be significant but further study of other sources needs to be done.
CHED 1082
Effects of nontarget water constituents on the oxidative treatment of pharmaceutical micropollutants with KMnO4
Matthew Sugihara, Lanhua Hu, Osmarily Arce-Bulted, and Timothy J. Strathmann, Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, 205 North Mathews Avenue, Urbana, IL 61801, msugiha2@uiuc.edu
Recent studies report the widespread occurrence of pharmaceutically active compounds in effluent-impacted surface waters, raising concerns about the quality and safety of drinking water drawn from such sources. This has raised additional questions about the fate and removal of pharmaceuticals during drinking water treatment processes. Potassium permanganate (KMnO4) is a powerful oxidizing agent commonly used in water treatment (e.g., for manganese removal), and kinetic studies performed in our lab indicate KMnO4 has great potential for oxidizing many pharmaceutical micropollutants during water treatment. However, the treatment efficiency of pharmaceuticals with KMnO4 in different source water will be influenced by a variety of non-target water constituents that are present at concentrations that are orders-of-magnitude greater than the pharmaceutical compounds. This report presents the results of experiments performed to document the effects of common non-target ions (NH4+, SO42+, NO-3, Ca2+, Mn2+ and natural organic matter on KMnO4 reactions with carbamazepine (an antiepileptic drug) and chlortetracycline (a common antibiotic).
CHED 1083
Effects of prescribed burning on the availability of phosphorus levels in grassland soils
Jeanette T Minah and Leslie A. Sherman, Department of Chemistry, Washington College, 300 Washington Ave, Chestertown, MD 21620, Fax: 410-778-7275, jminah3@washcoll.edu, lsherman2@washcoll.edu
Fire has been a part of natural ecosystems and is a way of managing grasslands, creating stability in the systems by removing decaying vegetation. Lack of fires deprive plants of enough space and light in order to grow, therefore some grasslands become unproductive. The total concentration of phosphorus in soils is usually low, ranging from 0.02 and 0.10%. Burning of grasslands influence soil nutrients by directly adding nutrients from the burned biomass and by altering the activity of microbes in the soil environment. In previous studies, phosphorus showed an increase in the soil after prescribed burns. Soil samples from a grassland restoration in Maryland were analyzed for phosphorus after a prescribed burn via dilute-acid extraction and colorimetric analysis. An increase in levels of phosphorus is expected as phosphorus gets regenerated in the soil after a burn due to ash from the burn and microbes that turn organic phosphorus into phosphate.
CHED 1084
Effects of prescribed burns on soil nitrogen levels of a coastal plain ultisol grassland restoration
Katricia M Stevens and Leslie A. Sherman, Department of Chemistry, Washington College, 300 Washington Avenue, Chestertown, MD 21620, Fax: 410-778-7275, kstevens2@washcoll.edu, lsherman2@washcoll.edu
The Chester River Field Research Center in Maryland is the site of a 92-ha grassland restoration project. It became part of the Conservation Reserve Program in 1998 and was drill-seeded with warm-season grasses in the spring of 1999. Prescribed burns in April 2003, November 2004 and March 2006 were used to manage the field. In previously conducted studies, soil cations and cation exchange capacity were analyzed. The current study focuses on the effects of prescribed burns on soil nitrogen content, as it is essential for plant growth. A 13-ha plot within the field was chosen to take 25 cores before and after each burn. The top 5 cm of each core were investigated for total nitrogen content using the Kjeldahl method with a block digester. It is expected that total soil nitrogen levels will decrease with each subsequent burn because of excess litter accumulation and decreases in denitrification and mineralization.
CHED 1085
Electrochemical synthesis of ammonia using a recyclable room temperature ionic liquid as an electrolyte solution
Kyung-mee Lee and Ted M. Pappenfus, Division of Science and Mathematics, University of Minnesota, Morris, 600 East Fourth Street, Morris, MN 56267, leex2208@morris.umn.edu, pappe001@morris.umn.edu
Ammonia is the most demanding chemical compound in agriculture. To meet the high demand, ammonia has been produced by the Haber process. However, the Haber process utilizes methane, a fossil fuel, as a starting material to synthesize ammonia. In this project, we explored an alternative way to synthesize ammonia. We performed electrochemical synthesis of ammonia using a room temperature ionic liquid (RTIL) as an electrolyte solvent in the presence of lithium. The electrochemical condition has been optimized, and ammonia has been successfully synthesized utilizing the characteristics of the RTIL. The amount of ammonia synthesized was quantified by performing the Berthelot reaction. The electrochemical synthesis of ammonia was confirmed by analysis of the amount of coulombs applied and ammonia produced in the electrolysis.
CHED 1086
Endocrine disruptors: An analysis of the rates of photooxidative degradation and determination of products
Angela M. Curran, Krystal Z. Munoz, and Stephen K. O'Shea, Department of Chemistry, Roger Williams University, One Old Ferry Rd., Bristol, RI 02809, acurran365@hawks.rwu.edu, kmunoz979@hawks.rwu.edu
Daidzein and genistein are a class of water soluble phytoestrogens found increasingly in the environment. The release of these compounds into the aquatic environment have direct detrimental effects on fish development; the extent of these effects is related to the compounds' rate of decay. The main decay pathway of the estrogens is by 1O2. Two photo-oxidative procedures were investigated for the conversion of 3O2 to the higher energy 1O2. The first method utilizes methylene blue to absorb red light (HeNe laser), the second method employs titanium oxide in a U.V. photoreactor. Rates of reactions were determine from U.V./Vis repetive scans analysis; from the rate of oxidative decay of these photestrogens we are able to elucidate an expected life time of these species in the water column. Our predicted photooxidative mechanism is cleavage of the conjugated groups by 1O2. NMR (1H, 13C) and HPLC/MS analysis was used to determine the products.
CHED 1087
Environmental photochemical fate of the antibacterials ofloxacin and norfloxacin
Andrew R. Korte and Kristine H. Wammer, Department of Chemistry, University of St. Thomas, 2115 Summit Ave. Mail #OSS 402, St. Paul, MN 55105, arkorte@stthomas.edu
In the interest of determining environmental persistence and impact, the photodegradation of two fluoroquinolone-class antibacterials, norfloxacin and ofloxacin, was studied. Two major norfloxacin photoproducts and one major ofloxacin photoproduct were characterized using a combination of mass spectrometry and NMR data and are expected to be environmentally benign. Previously, we determined that indirect photochemical processes were insignificant for both ofloxacin and norfloxacin and that there is a strong dependence of direct photodegradation rate on pH. Here, photolysis experiments were conducted in deionized water under sunlight at a range of pH. Using decay constants calculated from these photolyses, experimentally determined pKas, and deconvoluted absorbance spectra, direct photolysis quantum yields were calculated for each of three protonation species of each fluoroquinolone. Quantum yields were found to be significantly greater for the species dominant at neutral pH. For this reason, we can predict wide variations in rate of degradation for different natural water bodies.
CHED 1088
Evaluating a biodiesel cloud point reduction additive synthesized from waste glycerin
Stephan C. Jahn, Megan L. Fojtik, and David S. Karpovich, Chemistry Department, Saginaw Valley State University, 7400 Bay Road, University Center, MI 48710
An inherent problem with biodiesel is its relatively high cloud point, the temperature at which the freezing process begins. This is marked by the first sign of solid crystals in the fuel which can plug fuel filters and injectors, hindering cold weather engine operation. A compound was sought for use as an additive to depress this cloud point. Selected compounds were screened both qualitatively and quantitatively for their efficacy. And a target molecule, 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane, was sought and successfully produced via an acid catalyzed ketalization reaction between glycerin and acetone. This process, utilizing waste byproduct glycerin from the production of biodiesel, yielded an economical and low waste synthesis.
CHED 1089
Evaluation of effectiveness between two different processes in wastewater treatment
Humberto Arredondo, Crystal Shipp, Edward E. Gonzalez, and Alakananda R. Chaudhuri, Department of Chemistry, University of the Incarnate Word, 4301 Broadway, San Antonio, TX 78209, Fax: 210-829-3153, alakanan@uiwtx.edu, cshipp@uiwtx.edu, gonzalee@uiwtx.edu, alakanan@uiwtx.edu
Every day millions of gallons of recycled water are produced at four Water Recycling Centers (WRC) owned and operated by the San Antonio Water System delivering recycled water to customers for non-drinking purposes. The purpose of the study is to evaluate the different parameters in order to assess and compare the effectiveness of the recycling processes of the DOS Rios and Medio Creek WRC. The contaminants analyzed were ammonia nitrogen; total suspended solids (TSS); E. coli; and trihalomethanes (THM). The water samples were analyzed using semi-automated colorimetry and GC-MS. The levels of ammonia nitrogen, TSS and E. coli of Medio Creek were consistently above those of Dos Rios. Although the THM levels were higher in Dos Rios than in Medio Creek but all the contaminants studied were well below the detrimental level in both Centers. Correlation between the treatment processes and the levels of the contaminants in the final effluents of the two Recycling Centers were also discussed.
CHED 1090
Factors influencing bioaccumulation of trace heavy metals by the blue mussel (Mytilus edulis)
Stacey A. Helming1, Stephen K. O'Shea1, and David L. Taylor2. (1) Department of Chemistry, Roger Williams University, One Old Ferry Road, Bristol, RI 02809, shelming209@hawks.rwu.edu, (2) Department of Biology, Roger Williams University, Bristol, RI 02809
To model the bioavailable concentration of toxic heavy metals in sediments and water in an estuarine environment, the sedentary blue mussel (Mytilus edulis) was chosen as an indicator species. Sediments (0-2 cm) and M. edulis were collected from six sites in Narragansett Bay, Rhode Island, and examined for trace heavy metal concentration. Metal contaminants in sediments were correlated with the total organic carbon content and grain size distribution of the sediments. Mean differences in M. edulis and sediment metal concentrations were examined across sites using analysis of variance models. Moreover, correlations between site-specific M. edulis and sediment concentrations were investigated using regression analysis. Heavy metal analysis was completed on a DMA-80 (total mercury) and ICP-MS (lead, cadmium, silver, and selenium). Grain size was differentiated by dry sieving, while total organic carbon was determined by ashing sediments in a Muffle Furnace (800 °C, 5 hr).
CHED 1091
Fate and transport of PCBs in rural New Hampshire
Jaclyn Bergeron, Anil Bhalchandra Waghe, and Susan Swope, Chemical, Earth, Atmospheric and Physical Sciences Department, Plymouth State University, 17 High Street MSC48, Plymouth, NH 03264, Fax: 603-535-2723, awaghe@plymouth.edu, awaghe@plymouth.edu
Polychlorinated biphenyls (PCBs) are present in the environment, and are known to be toxic. The EPA has banned the production of such toxic compounds in 1970's, but PCBs in soil and water is continued to be a problem. Analysis of soil and water samples from various sites around Plymouth and Campton, NH provide fate and transport of PCBs in environment around rapidly developing areas in rural New Hampshire. The screen samples were tested at the Plymouth State University using GC-MS while the follow up samples analyzed using standard EPA method at the EPA laboratory.
CHED 1092
Field monitoring of environmental contaminant lead around New Orleans by a portable instrument
Ju Chou1, Adriana Dantin2, Lutasshi Green1, and Yixiang Duan3. (1) Department of Chemistry and Physics, Southeastern Louisiana University, Hammond, LA 70402, Ju.Chou@selu.edu, (2) Chemistry and Physics, Southeastern Louisiana University, Hammond, LA 70402, (3) C-ACS, MS K-484, Los Alamos National Laboratory
Lead, a ubiquitous and versatile metal, is considered a significant environmental threat in the global region. Even at low levels of lead exposure, there are serious side effects in children including learning disabilities, and brain damage. The lead exposure increased in New Orleans after Katrina. Environmental threats from lead are a serious problem in New Orleans and pose long term threats to the communities. It is important to monitor lead concentrations. Quantitative analysis of toxic metals is commonly analyzed by inductively coupled plasma-mass spectroscopy or inductively coupled plasma–atomic emission spectroscopy and performed in labs. A portable instrument called Element Presence Detector is employed to monitor hazardous lead on-site around New Orleans. EPD is the world's first plasma source based portable instrument which instantly detects elements with functions of continuous, on-line, and in real-time. Data collected around New Orleans on lead contaminations will be presented based on on-site, real-time analysis.
CHED 1093
Green and low-cost hydrogen production from aluminum and water
Christyn Thibodeaux1, Desiree Smith1, Nsoki Phambu2, and Anderson Sunda Meya1. (1) Department of Physics and Dual Engineering, Xavier University of Louisiana, 1 Drexel Dr, New Orleans, LA 70125, cthibod1@xula.edu, (2) Department of Chemistry, Tennessee State University, Nashville, TN 37209
Interest in hydrogen fuel production has grown dramatically, along with advances in hydrogen production, storage and utilization technologies. Hydrogen has great potential as a carbon-free fuel source. However, hydrogen is still three to four times as expensive to produce as gasoline. In this work, hydrogen has been produced using cheap raw materials such as tap water and recycled waste aluminum. The hydrogen production has been monitored and quantified as a function of time, temperature, and pH value of water. The physical properties of the aluminum samples used to produce hydrogen gas have been characterized using AFM, SEM, IR and Raman spectroscopy. The effects of mass transfer, migration, gas evolution, kinetics of electrodes, parasitic reaction and ohmic losses in the electrolyte are considered. Furthermore, to optimize the design and operation of an aluminum–water battery system, a mathematical model that can predict the aluminum–water unit cell performance has been proposed
CHED 1094
Ground level survey of radon in a two county area
Heather C. Collier, Chemistry, Henderson State University, 1100 Henderson Street, Arkadelphia, AR 71999, hc150920@reddies.hsu.edu, and Bryan D. Palmer, Department of Chemistry, Henderson State University, Arkadelphia, AR 71923
Radon-222 is a naturally occurring radioactive decay product of uranium-238. The World Health Organization reports radon-222 to be the cause of 15% of lung cancer deaths worldwide. The Environmental Protection Agency (EPA) provides an online map of the United States which shows zones of potential radon levels. The EPA report cautions that radon levels may be highly variable within any particular area due to a number of factors such as geology and soil permeability. The Arkansas map of radon zones by county shows Henderson State University to be located in a county with a low radon potential. An adjoining county is shown to be within a zone of moderate radon potential. My project involves developing an inexpensive means of measuring the radon level of a large number of high occupancy sites in the two county area. Experimental procedures and results to date will be discussed.
CHED 1095
Industrial water and material testing internship
Autumn C. Himes, Division of Natural and Health Sciences, Chemistry Program, Seton Hill University, 1Seton Hill Dr, Greensburg, PA 15601, and Janice Teleford, Q-Chem Laboratories, Latrobe, PA
This poster will feature the duties involved in an internship experience as a laboratory technician at Q-Chem Labs in Latrobe, Pa. Q-Chem Labs is an environmental quality control testing center. Procedures accommodate for a variety of samples that are reported to DEP and various municipalities and companies. A description of the company and the daily routine of an intern will be included. An explanation of the key chemical concepts behind the tests of interest will be outlined.
CHED 1096
Investigating and comparing the occurrence of alkaloid leaching in Coptis trifolia and Hydrastis canadensis rhizospheres
Shreya A. Kamath, Department of Biochemistry, St.Lawrence University, Blk.138, Jalan Bukit Merah, #03-1392, 160138 Singapore, Singapore, sakama04@stlawu.edu, Aswini Pai, Department of Biology, St.Lawrence University, Canton, NY 13617, and Matthew C. Skeels, Department of Chemistry, St.Lawrence University, 23 Romoda Drive, Canton, NY 13617, mskeels@stlawu.edu
Alkaloids are nitrogen-rich compounds found in several plant species.They are important to both plants and humans.In plants, they serve to protect against pathogens and herbivory.Leaching of plant compounds through the roots into surrounding soil has been observed in several plant species.We worked with two related plant species well known for their medicinal properties in Native American ethnopharmacoepia : Coptis trifolia (Goldthread) and Hydrastis canadensis (Goldenseal). Microwave assisted extraction of plant and soil samples followed by HPLC analysis of the alkaloids on reverse phase-C18 column provided an accurate method for the determination of key alkaloids in Goldenthread and Goldenseal; including palmatine, berberine, canadine,coptisine,hydrastinine and hydrastine. We are currently investigating leaching of these alkaloids into the soil rhizospheres of both C.trifolia and H.canadensis, and will compare the occurrence and scale of alkaloid leaching for both plant species.
CHED 1097
Investigating high levels of arsenic found in soils around West Anniston, Alabama and their impact on human health
Nixon Mwebi, David A. Steffy, Alfred C. Nichols, and Bryan Delauney, Department of Physical and Earth Sciences, Jacksonville State University, 700 Pelham Road North, Jacksonville, AL 36265, Fax: 256 782 5336, nmwebi@jsu.edu, jsu1827m@jsu.edu
Arsenic is ubiquitous mainly due to its past extensive use over 100 years as an essential ingredient in animal feeds, herbicides, pesticides, wood preservatives, semiconductors, alloys and even in smelting. Disposal of arsenic in the past was in many instances not done with impermeable linings to contain leaches; this poses potential exposure to the element through the air, food or water. Because of its known effects to human health, arsenic has been at the top of the EPA National Priority List and inorganic arsenic branded as a proven human carcinogen. It is therefore essential to monitor the arsenic disposal either from treated wood or other industrial uses. A 14-acre abandoned manufacturing site in west Anniston Alabama has been shown to have potential for high levels of arsenic. This study investigated potential leaching and movement the arsenic and its impact on the adjacent residential neighborhood.
CHED 1098
Investigation of lead and arsenic contamination in New Orleans parish school soils
Lovell Agwaramgbo, Jerrard Smith-Hopkins, Adriana Hawkins, and Deneyelle Wilson, Chemistry, Dillard University, 2601 Gentilly Blvd., New Orleans, LA 70122, Fax: 504-816-4724, lagwaramgbo@dillard.edu, lagwaramgbo@dillard.edu
Chronic lead exposure leads to mental retardation and damage to the central nervous system, reproductive systems, and developing fetus while Arsenic is known to cause cancer (kidney, lungs, & bladder. New Orleans sat in flood water for days & it was feared that receding water deposited contaminated sediments allover the city. EPA/LDEQ & NRDC conducted extensive sediment sampling to assess the effect of Hurricane Katrina on soil contamination. Although these two bodies sampled the same sites, yet their results and conclusions couldn't be farther apart. Thus, we decided to resample those sites reported by NRDC to have high levels of arsenic. We report here a part of our investigation aimed at re-examining the ill-effect levels of Arsenic and lead in New Orleans Parish Schools. The data from both X-ray Fluorescent spectrophotometer and inductively coupled plasma suggest that majority of the school sites sampled have arsenic levels above EPA cleanup levels.
CHED 1099
Investigation of lead mobility in three Louisiana soils
Lovell Agwaramgbo, Jennifer Hamilton, and Deneyelle Wilson, Chemistry, Dillard University, 2601 Gentilly Blvd., New Orleans, LA 70122, Fax: 504-816-4724, lagwaramgbo@dillard.edu, aorta751@yahoo.com
Lead exposure has serious human health consequences. Numerous studies after hurricane Katrina suggest that some New Orleans' Neighborhoods have lead levels above 1700mg/kg. EPA and LADEQ cleanup lead level is 400mg/kg. The disparity in Pb levels reported by various agencies was attributed to variation in soil type and sampling depths. We therefore decided to investigate the depth of migration of lead solution in three Coushatta, Louisiana soils (humus, red and brown clay). Lead nitrate (100ml of 3210 ppm)was poured into sieving vessels containing 100g of each type of soil, respectively. The soil samples were divided into top and bottom 1.5 cm layers, dried, homogenized, and prepared for XRF analysis. The results showed that the top 1.5cm soil layer for each soil type contained 3936, 3702, 2963mg/kg of lead, respectively while the next 1.5 cm soil layer contained 970, 1177, and 1247 mg/kg of lead.
CHED 1100
Investigation of the effects of hillslope properties on carbon and nitrogen biogeochemistry in a semi-arid New Mexico ecosystem
Michael J. Pullin, Department of Chemistry, New Mexico Institute of Mining and Technology, 801 Leroy Place, Socorro, NM 87801, mpullin@nmt.edu, Margaret Tammaro, Department of Chemistry, Lafayette College, Hugel Science Center, Easton, PA 18042, tammarom@lafayette.edu, Yaika Echevarría Román, Universidad Metropolitana, San Juan, PR 00928, Randall D. John, Diné College, Shiprock, NM 87420, Steven D. Scholle, New Mexico Institute of Mining and Technology, Socorro, NM 87801, and Thomas L. Kieft, Department of Biology, New Mexico Institute of Mining and Technology, Socorro, NM 87801
The roles of runoff, microbial mineralization, and denitrification on the export and biogeochemical cycling of carbon and nitrogen in desert soils are not understood. Two opposing hillslopes (north vs. south-facing) in the Sevilleta National Wildlife Refuge (central New Mexico) were investigated to illustrate the importance of hillslope aspect. Additionally, the effects of hillslope elevation and soil depth were also investigated. Samples were collected at four elevations and analyzed for organic carbon and nitrogen, nitrate, ammonium, carbon and nitrogen biomass, respiration, and denitrification activity. Our results indicate that the wetter north-facing hillslope has more organic nutrients than the drier south-facing slope. Additionally, our results indicate that Juniper plant litter is an important source of these nutirents to the ecosystem. Finally, the results indicate that hillslope hydrology has an effect on the amount and rates of biogeochemical cycling of carbon and nitrogen.
CHED 1101
Investigation of the lack of cytochrome P450 1A1 gene expression in paddlefish (Polyodon spathula)
Bob C. Fitzmorris, Chemistry Department, Pacific University, 2043 College Way, Forest Grove, OR 97116, fitz8186@pacificu.edu, Deke T. Gundersen, Department of Environmental Science, Pacific University, Forest Grove, OR 97116, and Lisa Sardinia, Biology Department, Pacific University, Forest Grove, OR 97116
Paddlefish are a long-lived primitive fish species with a cartilaginous skeleton, inhabiting the Mississippi River drainage. Previous work in our laboratory indicated that PCB-contaminated paddlefish collected from the Ohio River did not have measurable hepatic microsomal EROD activity. In addition, we were unable to detect CYP1A1 protein in these paddlefish in a western blotting analysis using rabbit anti-trout CYP1A1 (LM4b) IgG antibody. The objective of this study was to investigate the lack of CYP1A1 expression in paddlefish. Using primers derived from the first and last exons of rainbow trout CYP1A1 gene, the polymerase chain reaction was used to amplify trout, sturgeon and paddlefish genomic DNA. PCR products of the correct size were generated for each species. Our results indicate that the paddlefish genome contains the CYP1A1 gene, but the previous evidence would suggest that it is not being expressed. Currently we are trying to detect the presence of the Ah-receptor necessary for promoting CYP1A1 production.
CHED 1102
Investigation of the photocatalytic properties of a family of calcium bismuth oxides
Byron H. Farnum1, Thomas Vogt2, Sangmoon Park2, and John L. Ferry1. (1) Department of Chemistry and Biochemistry, University of South Carolina, 631 Sumter St, Columbia, SC 29208, farnumb@mailbox.sc.edu, (2) NanoCenter, University of South Carolina, Columbia, SC 29208
A series of calcium bismuth oxides was synthesized and assayed for photocatalytic activity against a Bi2O3 standard. All oxides were visibly colored, with band edges falling in the 400nm-500nm region. A family of potential substrates (1-adamantol, benzanilide, diethyl phthalate, diphenylamine, and 2,4,6-trimethylphenol,) were photodegraded in aqueous, 0.03 wt% suspensions of the photocatalysts. A Suntest XLS+ system (Xe lamp) was used to illuminate the suspensions. Substrate degradation was followed using liquid-liquid extraction followed by GC-MS techniques. Generically, photocatalytic oxidation increased with increasing Ca/Bi ratio, with Ca6Bi6O15 being the most effective photocatalyst at an equal wt% loading. The observed rates of photocatalytic degradation (fastest to slowest for Ca6Bi6O15) ranked: 2,4,6-trimethylphenol > diphenylamine > benzanilide > diethyl phthalate > 1-adamantol. The photostabilities of the catalysts are also reported, and the effects of common photocatalyst poisons (bicarbonate, sulfate, dissolved organic matter) discussed.
CHED 1103
Isolation and identification of microcystin variants from a south Florida estuary
Carlos A Miranda1, Weihua Song2, and Kevin O'Shea2. (1) Department of Chemistry, Florida International University, 11200 SW 8th street, Miami, FL 33199, cmira003@fiu.edu, (2) Department of Chemistry and Biochemistry, Florida International University, Miami, FL 33199
Blue-green algae (BGA) produce microcystin (MC), which are toxic cyclic heptapeptides. Relatively high levels of MC are released into the surface water during a bloom of BGA creating a threat to public safety. We collected the biomass during a large bloom of BGA in South Florida. The biomass was sonicated, filtered, and pigment removed through a solid phase extraction (SPE) using C18 cartridge. The resulting solution was refined using preparative HPLC by monitoring at 238 nm, typical absorption maximum of MC variants. The HPLC chromatograph had several peaks, which are indicative of different MC variants. The major peak was isolated and identified as MC-LR by MS and proton NMR. MC-LR accounts for ~ 80 % of the MC content. An additional 2-3 peaks were observed in the chromatogram. Studies are underway to characterize the remaining MC variants. A number of studies on the remediation and therapeutic technologies are planned.
CHED 1104
LC-MS analysis of biogenic carbonyl compounds using novel derivatization agents
Anna A. Volkert and James E. Boulter, Department of Chemistry, University of Wisconsin-Eau Claire, 105 Garfield Avenue, Eau Claire, WI 54702, Fax: 715-836-4979, volkeraa@uwec.edu, boulteje@uwec.edu
Carbonyl compounds play important roles in diverse atmospheric concerns ranging from smog formation to the carbon budgets of natural ecosystems. Many of these compounds are released into the atmosphere by plants for reasons that are incompletely understood. A common method for analyzing atmospheric carbonyls involves trapping them on cartridges containing 2,4-dinitrophenylhydrazine (DNPH) coated on a silica stationary support. The resulting hydrazones are eluted and analyzed by HPLC-UV/Vis. This method suffers from well-documented interferences and is unable to easily identify more complex carbonyl compounds. Conversely, analysis by LC-MS affords greater sensitivity, improved identification of analytes and exclusion of interferences. However, this method requires the use of alternative agents to trap carbonyls and form products that are readily ionized in an electrospray inlet. We will report the use of novel carbonyl derivatization agents such as hydrazine to form azine analytes and 4-carboxy phenyl hydrazine to form the corresponding hydrazones.
CHED 1105
Measuring natural radioactivity in aerosols: Lead-210 and beryllium-7 as tracers for aerosol washout
Michael J. Tackett1, Gunawan Gunawan1, Nancy A. Marley2, and Jeffrey S. Gaffney1. (1) Department of Chemistry, University of Arkansas at Little Rock, Little Rock, AR 72204, Fax: 501-569-8838, mjtackett@ualr.edu, (2) Graduate Research Institute, University of Arkansas at Little Rock, Little Rock, AR 72204
Atmospheric aerosols are important in climate and air quality considerations. Their impacts depend on their chemical and physical properties and their residence times in the atmosphere. Accumulation mode aerosols (0.1-1.0 micron size range) are likely to have the longest atmospheric residence times with water uptake and washout or gravitational settling (dry-deposition) dominating their removal. Discussed will be measurements of 210-Pb and its daughters (210-Bi and 210-Po) as well as 7-Be as atmospheric aerosol tracers. Laboratory experiments looking at the effects of “washing” of aerosol samples collected at a number of different urban sites are described that address the strength of the radionuclide tracer association with carbonaceous aerosols. Experiments using dry and wet sampling methods are also described that indicate carbonaceous aerosols are not rapidly removed from the troposphere. This research was supported by the Office of Science (BER), U.S. Dept. of Energy, Atmospheric Science Program under Grant No. DE-FG02-07ER64328.
CHED 1106
Mechanistic studies on the chemical fate of three N-methyl carbamate pesticides
Demar Pitter and Clare N. Muhoro, Department of Chemistry, Towson University, Towson, MD 21252, dpitte1@towson.edu
Carbamate compounds are useful pest control agents because they are an alternative to ozone-depleting organochlorine pesticides, and because they are active against organophosphate-resistant pests. Accurate descriptions of the chemical fate of carbamates under environmental conditions are increasingly important as the use of these pest-control agents becomes widespread. We report studies on the aquatic fate of the three N-methyl carbamate pesticides propoxur, carbofuran and carbaryl. Aqueous solutions of these compounds were monitored by UV-vis and NMR spectroscopies to identify products of decomposition under various conditions. We will present results on characterization of degradation products and relative stability of the three compounds, and propose tentative pathways for the decomposition of the parent compounds. Additionally, preliminary findings on the influence of ambient metals on degradation will be discussed.
CHED 1107
Mercury concentrations in earthworms lumbricus terresteris as related to soil concentrations of the metal
Jennifer Wallach1, Amy McLaughlin1, Alfred C. Nichols2, and David A. Steffy2. (1) Department of Chemistry, Jacksonville State University, 700 Pelham Road North, Jacksonville, AL 36265, (2) Department of Physical and Earth Sciences, Jacksonville State University, Jacksonville, AL 36265
Earthworms can bioaccumulate mercury (Hg) when grown in Hg contaminated soil (Ernst and Frey, 2007). Earthworms, Lumbricus terresteris, were grown in soils with different Hg concentrations. At two week intervals, worms grown at the different concentrations were analyzed for total Hg using USEPA method 245.1, manual cold vapor atomic absorption spectrometry. Worms grown in soil with an Hg concentration of 0.031 µg/g had a tissue Hg concentration of 0.073 ± 0.094 (mean ± S.D.) µg of Hg per g of freeze-dried tissue. Worms grown in soil with an Hg concentration of 2.15 µg/g had a mean Hg tissue concentration of 219.030 ± 42.920 µg/g. Worms exposed to a soil Hg concentration of 4.37 µg/g had a tissue concentration of 319.030 ± 72.807 µg/g. ANOVA analysis of the data produced a P value of <0.0001. Tukey-Kramer multiple comparison test produced a P value of <0.001 for comparisons between any two of the three groups.
CHED 1108
Metal concentrations in soil, water, and sediment in the Rodeo Lagoon Watershed
Karen L. Butler1, Shanice D Dyer1, Sarah J. Crim1, Darren Fong2, and David C. Edwards3. (1) Department of Chemistry and Physics, Wesleyan College, 4760 Forsyth Road, Macon, GA 31210, klbutler@wesleyancollege.edu, (2) Golden Gate National Recreation Area, Sausalito, CA 94965, (3) Chemistry and Physics, Wesleyan College, Macon, GA 31210
The Rodeo Lagoon Watershed in Sausalito, California has been subjected to many human impacts, most notably the building of a weir that separated the lagoon from the upstream watershed. Due to this ecosystem alteration, eutrophication, along with high toxic metal concentrations, has been found within the watershed. The National Parks Service is considering removing the weir to help restore the area, and the objective of this study was to analyze the concentrations of a variety of micro and macronutrients and trace contaminants in water, soil and sediment cores to evaluate the condition of the ecosystem using atomic absorption spectroscopy. Initial results show high concentrations of Pb and Cd in the water and soil samples. The sediment cores indicate varying metal concentrations with depth and correlate well with deposition rates. These results will aid in the remediation of the area and demonstrate the effects these metals have on the ecosystem.
CHED 1109
Mobilization and leachability of heavy metals from compost manure
Nixon Mwebi, Jacob W. Boydston, and Megan Dingler, Department of Physical and Earth Sciences, Jacksonville State University, 700 Pelham Road North, Jacksonville, AL 36265, Fax: 256 782 5336, nmwebi@jsu.edu, jsu9768m@jsu.edu
Use of compost manure for lawn gardens has become increasingly attractive since it is inexpensive and has the added advantage of recycling a large waste. Compost is however believed to contain heavy metals such as lead, cadmium, and chromium among others, emanating from their use in various manufacturing industries and household commodities. Depending on the origin of the compost, heavy metal concentrations and types present may vary. Furthermore, the possible mobilization and leaching of the metals may depend on the organic content of the compost. In most cases, the levels of these heavy metals and their possible mobilization under normal or severe weather conditions are rarely addressed. This study investigates the levels of heavy metals such as Pb, Cr, and Cd in compost used for lawn gardens in Northeastern Alabama and their possible mobilization by weathering activities. Results depicting the metal concentrations and their possible mobilization will be presented.
CHED 1110
Nutrient and metal contamination in a man-made lake: Effects and implications
Kritika Thapa, Kriti Rai, and David C. Edwards, Department of Chemistry and Physics, Wesleyan College, 4760 Forsyth Road, Macon, GA 31210, kxthapa@wesleyancollege.edu
Man-made lakes are often susceptible to environmental stress because of their small volumes, shallow depths, and relatively large volume of drainage to them. Foster Lake, a man-made lake on the campus of Wesleyan College, is a sink for drainage from multiple parking lots, a horse barn, residential buildings and city roads. However, the impacts of the aforementioned on the lake have not been quantified. This project attempts to evaluate the health of the lake based on chemical indicators (pH, alkalinity), nutrient (nitrate, phosphorous, sodium, calcium) and trace metal concentrations (lead, zinc, iron). The detection of these ions was completed by titrametic and spectrophotometric (UV/vis and AAS) methods. The initial results indicate elevated concentrations of ions from the road drain are deposited uniformly in the lake. These results will aid in the remediation process of Foster Lake and determine preventative measures for further pollution.
CHED 1111
Nutrient levels in Lake Maurepas before and after Hurricane Katrina
Kellie Silcio, Kristy Ball, and Phillip D. Voegel, Department of Chemistry & Physics, Southeastern Louisiana University, SLU 10878, Hammond, LA 70402, phillip.voegel@selu.edu
Following Hurricane Katrina, parishes to the north of Lake Maurepas experience significant population growth, particularly in rural areas with limited water treatment capacity. Nine sites were selected to examine nutrient and algal levels. These sites include three sites where water enters the lake from parishes north and east of the lake and a fouth where water enters from the south. Three sites near the center of the lake where significant mixing of incoming water would have been achieved and two sites where water exit the lake were also monitored. Nutrient monitoring includes phosphate and silicate and nitrate and ammonia levels are being added.Routinely, the pH and temperature are monitored as well. The level of phospahte and pH are somewhat variable where water enters the lake but is relatively consistent at other sites and, compared to historical data available from USGS has not changed since the hurricane. On the other hand, levels of phosphate have increased by 5 - 10 times over historical levels.
CHED 1112
Okra seed oil biodiesel: Investigating underutilized seed oils as potential biofuels
Matthew R. Austin, Rebecca Z. Havens, Irvin J. Levy, Jennifer L. Soerensen, and Dwight J. Tshudy, Department of Chemistry, Gordon College, 255 Grapevine Road, Wenham, MA 01984, rebecca.havens@gordon.edu, jennifer.soerensen@gordon.edu
Okra seed abounds in tropical and sub-tropical regions, and has a protein and fat profile similar to that of conventional vegetable oils used for both food and biodiesel production. Okra seed, however, is underutilized and understudied. Here we present a laboratory-scale extraction of oil from okra seed and preparation of biodiesel from okra seed oil. Further we present a comparison of properties of okra seed biodiesel to conventional biodiesel and comment on the viability of okra seed as a potential fuel source. We also examine the potential use of liquid CO2 to replace Soxhlet extraction of the oil, reducing energy consumption and use of non-renewable resources. Finally, we discuss the outcomes of this project in light of the "12 Principles of Green Chemistry."
CHED 1113
Oxygen and pH levels in Wright Patman Lake
Sarah Khoury, Department of Chemistry, Texarkana College, 2500 N. Robison Road, Texarkana, TX 75599
This presentation details a study of Wright Patman Lake at three sites. Dissolved oxygen and pH were measured over twenty four hour time periods and plots were made of these parameters vs. time. Project goals were to determine levels of photosynthetic activity in the lake as depicted by changes in oxygen and pH levels. Maximum levels for pH and minimum levels of dissolved oxygen are used to determine if lake conditions meet EPA standards.
CHED 1114
Permanganate degradation of 1-ethyl-3-methylimidazolium tetrafluoroborate: Intermediates and mechanism
Jacob Matthew Skeans and Clifford E. Harris, Chemistry Department, Albion College, 611 E. Porter Street, Albion, MI 49224, charris@albion.edu
The reaction of 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) with potassium permanganate has been studied in aqueous solution. The oxidation proceeds through at least two stable organic intermediates which have been isolated and completely characterized. They are: 1-ethyl-3-methyl-2,4,5-trioxoimidazolidine and N-ethyl, N'-methylethanediamide. Kinetic studies of this degradation process will also be discussed.
CHED 1115
Photocatalyzed oxidation of alcohols for water purification
David Huang, Phillip R. Burkholder, and John C. DiCesare, Department of Chemistry and Biochemistry, The University of Tulsa, 600 S. College Ave, Tulsa, OK 74104
This research project is to develop a water reclamation system for use in long-term shuttle missions, such as NASA's planned mission to Mars. A side goal of this project is to develop a system which can be utilized on Earth as a water purification system. Our goal is to develop a silica pellet to be incorported into a packed-bed photoreactor. The silica/titania pellet will be capable of providing the titania photocatalyst sufficient contact with impurities in the water as well as allowing UV light penetration. The pellet design being analyzed is a capped pellet. Not only does this allow sufficient surface titania to be available to react, but it also allows more titania to be incorporated into the matrix without reducing UV penetration. Currently we are optimizing total titania composition and the percent coverage. Optimization is being tested by single and multi-pass systems and analyzed with a gas chromatograph. Currently all matrixes made are only active in the UV range of light.
CHED 1116
Photocatalytic enhancement of SODIS bottle
Jonathan M. Carey, Luke H. Loetscher, and Joel E. Boyd, Department of Chemistry, Wayland Baptist University, 1900 W. 7th Street #226, Plainview, TX 79072
Titania was solvent deposited on the interior walls of a polyethylene terephthalate (PET) bottle for the purpose of studying its photocatalytic activity in the sterilization of water containing E. coli. The bactericidal action, under direct solar illumination, of the titania-modified bottle was assessed in comparison with an unmodified PET bottle. The unmodified PET bottle is representative of the bottles utilized in the SODIS project of the World Health Organization. The titania-enhanced PET bottle showed a significant increase in the sterilization rate and resulted in a lower rate of bacterial re-growth than the unmodified PET bottle.
CHED 1117
Photocatalytic inactivation of bacteria with titanium dioxide
Leah R. Quisenberry, Luke H. Loetscher, and Joel E. Boyd, Department of Chemistry, Wayland Baptist University, 1900 W 7th St #226, Plainview, TX 79072
Metal modified TiO2 was investigated as a means of water disinfection using Escherichia coli as a model bacteria. Pd modified TiO2 was found to work many times faster than Pt, V, and Ag/AgBr modified TiO2. Pd/TiO2 was also active in the absence of light; therefore, an alternative mechanism was investigated. It was found that the catalyst does not work more than once, unless exposed to air for a period of time prior to its re-use. Also, sodium thiosulfate was used as a sacrificial electron donor to probe the presence of oxidizing species in the solution. The use of the electron donor drastically inhibited bactericidal activity, indicating the presence of strongly oxidizing species. It is proposed that the reduction of Pd2+ on the surface of the samples resulted in the formation of Cl2 in solution. The Cl 2 is postulated to be the source of the bactericidal properties of Pd/TiO2.
CHED 1118
Photocatalytic system utilizing LEDs for the sterilization of drinking water
Luke H. Loetscher, Leah R. Quisenberry, and Joel E. Boyd, Department of Chemistry, Wayland Baptist University, 1900 W 7th St #226, Plainview, TX 79072
A photocatalytic reactor system was developed which used titanium dioxide immobilized on acrylic, and light emitting diodes as the illumination source. A series of tests were performed to determine the optimum optical spectrum and illumination intensity. These tests provided the necessary information to design and optimize this reactor system. The final design is based on a modified tubular geometry which provides the optimal balance between illuminated surface area and the illumination intensity. This system for drinking water treatment produced sufficient oxidative species to inactivate Escherichia coli cells within the reactor water.
CHED 1119
Photochemical production of hydrogen peroxide in an Antarctic coastal lake water
Karen E. Kirchman, CM 1716, Rose-Hulman Institute of Technology, 5500 Wabash Ave, Terre Haute, IN 47803, kirchmke@rose-hulman.edu, and Dr. Penney L. Miller, Department of Chemistry, Rose-Hulman Institute of Technology, Terre Haute, IN 47803
A fluorescence assay (Miller and Kester, 1988) was adapted to study the hydrogen peroxide production rate in water sampled from Pony Lake, a coastal pond located on Cape Royds, Antarctica. Because Pony Lake is hypereutrophic, dissolved organic matter accumulates throughout the austral summer, leading dissolved organic carbon levels exceeding 20 mg C/L, depending on the season. Therefore, we hypothesized that hydrogen peroxide production in this lake water would be high. Photochemical production of hydrogen peroxide was measured in filtered Pony Lake Water samples (DOC = 22.9 mgC/L, collected 1/24/06) at three pHs, 6.2, 9.1, and 9.5 and in a reconstituted Pony Lake Fulvic Acid solution (DOC = 10 mg/L) at a pH of 7.99. The initial production rate was largest (0.33 micromolar/hr/mgC/L) at a pH representative of the natural lake conditions (9.5) and decreased with a decrease in pH. Further studies were performed to investigate the nature of this dependency.
CHED 1120
Photolytic breakdown of trace level pharmaceuticals in the environment
Scott A. Kindelberger1, Justin M. Conley2, Sean M. Richards2, and Steven J. Symes1. (1) Department of Chemistry, University of Tennessee-Chattanooga, 615 McCallie Avenue, Chattanooga, TN 37403, scott-kindelberger@utc.edu, (2) Department of Environmental Science, University of Tennessee-Chattanooga, Chattanooga, TN 37403
The fate of both prescription and over-the-counter pharmaceuticals in the environment are largely unknown. Previous studies have shown that these compounds may be present in watershed concentrations high enough to have detrimental biological effects. Current waste water treatment methods are not designed to break down these small organic molecules. Since up to 90% of these compounds can be excreted unchanged by humans, the potential exists for a continuing source of environmental replenishment. It may be that photolytic breakdown is an important mechanism of degradation in the environmental fate of these compounds. In this study, 100 ng/mL solutions of 13 target compounds comprising 6 different drug classes were analyzed over a 72 hour period and normalized to unexposed solutions of the same composition for possible evidence of accelerated breakdown via photolysis. Instrumentation utilized a Waters UPLC coupled with a Quattro micro triple quadrupole mass spectrometer operated in ESI+ mode.
CHED 1121
Preliminary characterization of environmental estrogens in wastewater effluents
Reba L. Scott1, Katoria Tatum-Gibbs2, Taun Phan3, Renard L. Thomas3, and Bobby L. Wilson3. (1) Department of Chemistry, Texas Southern University, 3100 Cleburne, Houston, TX 77004, rlscott32@yahoo.com, (2) Department of Chemistry, Environmental Toxicology Ph.D Program, Texas Southern Unversity, (3) Department of Chemistry, NASA University Research Center,Texas Southern University, Houston, TX 77004
Abstract
In this study, the objective is to identify estrogens in sewage effluents. Estrogens are a group of steroid compounds that function as the primary female sex hormone. Estrogens are used as oral contraceptives and estrogen replacement therapy in postmenopausal women. Sewage effluents may contain many different estrogens, including estrogens that are endocrine disrupting compounds (ECDs). ECDs are both natural and man-made and they can interfere with the endocrine glands and their hormones that alter the functioning of the endocrine system. It is important to identify theses estrogens to have a better understanding of the effects of theses estrogens in the environment. The procedure includes a solid-phase extraction (SPE) of approximately 500 milliliters of water samples. The SPE absorbent used for sample preparation was an octadecyl (C18)-bonded silica sorbent. High Performance Liquid Chromatography with ultraviolet detector (HPLC - UV) was used to characterize the estrogens in the sewage effluents. HPLC - UV was used for its specific detection and potential identification of estrogens in the presence of other chemicals. The preliminary analysis showed the presence of three compounds at levels between .0206 mgL-1 (estradiol) to .2257(ethinyl estradiol) mgL-1. The EPA does not regulate the levels of estrogens that are released into the water but even at low concentration levels the estrogens have been observed harmful on the reproduction, growth, and development of certain species of wildlife [4, 5].
CHED 1122
Quantification of heavy metals in liver and heart tissue of harbor seals (Phoca vitulina) from Alaska
Kady B Marino1, Stephen K. O'Shea2, and Dale F. Leavitt2. (1) Department of Chemistry, Department of Biology, Roger Williams University, Box 7315, One Old Ferry Rd, Bristol, RI 02809, kmarino072@hawks.rwu.edu, (2) Department of Chemistry, Roger Williams University, Bristol, RI 02809
Harbor seal populations in Alaska have dramatically decreased since the 1980's. Anthropogenic pollution is believed to be a significant factor in this decline. Heavy metals have been found to be rapidly increasing in the environment from accidental release and leaching events. These pollutants have large bioaccumulation factors with deposition in higher trophic level species. This research quantified heavy metals in liver and heart tissue of harbor seals from Prince Williams Sound and Kodiak Island, Alaska. Heavy metal concentrations were determined on a DMA-80 Total Mercury Analyzer and ICP-MS (Cd, Pb, Se, As, and Sn). Heavy metal concentrations were statistically related with seal age, harvest location, sex, reproductive status, and comparative organ bioaccumulation. Metal levels showed higher accumulation in liver compared to the heart tissue.
CHED 1123
Quantification of volatile fatty acid emissions from California dairy facilities
Phillip Alanis1, Mark Sorenson1, Brian Shamp1, and Alam S. Hasson2. (1) Department of Chemistry, California State University Fresno, 2555 East San Ramon Avenue M/S SB70, Fresno, CA 93740, philly86@csufresno.edu, (2) Department of Chemistry, California State University, Fresno, Fresno, CA 93740-8034
The San Joaquin Valley in Central California suffers from high ozone levels during the summer. According to the California Air Resources Board, dairy facilities are the largest source of VOCs in the valley and volatile fatty acids (VFAs) account for over 50% of these emissions. However, these estimates are controversial because fluxes of VFAs from California dairies have not been accurately measured. In this work, a method has been developed to quantify emissions of VFAs using a flux chamber coupled to solid phase microextraction (SPME) fibers, with analysis by gas chromatography with mass spectrometry The method was used to characterize emissions from various sources in six regional dairies. VFAs were present in all samples, with acetic acid being the dominant species present. Fluxes from animal feed were found to be much higher than from animal waste. The data suggest that dairies are a major source of VFAs in the region.
CHED 1124
Radiocarbon measurements of carbonaceous aerosols from Mexico City in 2003
Amanda C. MacMillan1, Karen L. Steelman1, Nancy A. Marley2, Jeffrey S. Gaffney3, and Thomas P Guilderson4. (1) Department of Chemistry, University of Central Arkansas, 205 Laney Hall, 201 Donaghey Ave., Conway, AR 72035, Fax: 501-450-3623, future_scientist22@yahoo.com, (2) Graduate Research Institute, University of Arkansas at Little Rock, Little Rock, AR 72204, (3) Department of Chemistry, University of Arkansas at Little Rock, Little Rock, AR 72204, (4) Center for AMS, LLNL, Livermore, CA 94551
Carbonaceous aerosol samples, collected at an urban site in Mexico City during April 2003, were analyzed for radiocarbon content to determine their biomass-to-fossil fuel ratios. Using high-volume samplers, collection of less than one-micron particulates on glass-fiber filters occurred for continuous twelve-hour intervals. Our laboratory converted organic material in the aerosol samples to carbon dioxide and water using a custom-built plasma oxidation apparatus, followed by accelerator mass spectrometry radiocarbon measurement. For twenty-three samples, values ranged from 0.5552 to 0.8613 indicating a substantial contribution from modern carbon. A fire in the Yucatan impacted the city during the last seven days of the month with AM and PM fraction modern averages of 0.69735 and 0.76996. A slight increase in the 14C content during the fire event is consistent with biomass burning impact. Data clearly indicate that biomass sourced carbonaceous aerosols are a major contributor to the aerosol in this important megacity.
CHED 1125
Reaction mechanisms and proof of structure for decontamination of VX, sarin and HD simulants in 1,2-dimethyl-3-propylimidazolium and Cu(II) bis(trifluoromethylsulfonyl)amide
Paul Joseph Cote1, Donald M. Bird2, John S. Wilkes1, Joseph A. Levisky1, Adrian Hermosillo1, Patrick J. Castle1, Ralph Hutchinson2, and Christina Wamsley2. (1) Department of Chemistry, US Air Force Academy, 2355 Fairchild Drive, USAF Academy, CO 80840, Fax: 719-333-2947, C08Paul.Cote@usafa.edu, (2) Department of Chemistry, United States Air Force Academy, Colorado Springs, CO 80841
Since 9/11, the decontamination of chemical warfare agents has received considerable attention. There are few reports describing reaction systems in which all CWA simulants are neutralized. In this presentation we describe the results of our efforts to develop a universal matrix in which three chemical agents are neutralized. Mechanisms and proof of structure for the reaction products of processes carried out in an alcoholic solution of a common ion binary ionic liquid are presented.
CHED 1126
Removal of aqueous phosphate, organic compounds, and organic phosphates using iron oxide produced from abandoned coal mine drainage
Stefan O. Ochiana and Daryle Fish, Department of Chemistry, Saint Vincent College, 300 Fraser Purchase Road, Box 571, Latrobe, PA 15650, stefan.ochiana@email.stvincent.edu
This study will explore the feasibility of utilizing iron oxide produced from abandoned coal mine drainage from one discharge in western Pennsylvania to sequester phosphate, organic phosphates and aromatic compounds in laboratory experiments. The iron oxide is expected to adsorb different amounts of phosphate, organic phosphates and aromatic compounds since they have different binding affinities to iron oxide. The impact of the pH on the amount of phosphate, organic phosphate and organic compounds that can be adsorbed by iron oxide is a critical factor that shall be investigated. To determine how efficient iron oxide is at removing contaminants, the amount of iron oxide concentration will be varied to determine binding affinities.
CHED 1127
Significance of highly toxic secondary emissions from on-road vehicles
Daryl Key1, Marc M. Baum2, James Kilgore2, and John A. Moss2. (1) Department of Environmental Science, Oak Crest Institute of Science, 2275 E. Foothill Blvd., Pasadena, CA 91107, fenderhighlife@gmail.com, (2) Oak Crest Institute of Science, Pasadena, CA 91107
Catalytic converters have been instrumental in reducing major pollutant exhaust emissions from on-road vehicles and have played a significant role in improving air quality. However, secondary reactions on the catalyst may produce unregulated emissions (e.g., hydrogen cyanide, and ammonia) that could have an adverse impact on human health and the environment. These compounds have received little attention in the past and their presence in vehicle exhaust, even at low concentrations, could lead to significant adverse health effects. The goal of this project is to investigate (chemically-)reduced nitrogen compound (RNC) emission rates from in-use light duty motor vehicles and to estimate the associated health risks in terms of exposure. We have designed and tested methods and instrumentation for the collection and measurement of trace amounts of amines in car exhaust. Amines are collected using impingers, derivatized, and then analyzed using GC/MS. Results from on-road studies will be presented.
CHED 1128
Size-segregated measurements of organic compounds in particulate matter in central California
Kennedy Vu, Enrique Lopez, Myeong Chung, and Alam S. Hasson, Department of Chemistry, California State University, Fresno, 2555 E. San Ramon Ave, Fresno, CA 93740-8034, kennedykvu@gmail.com
A number of studies have implicated quinones in the toxicological effects of particulate matter (PM), and levels of these compounds are high in Central California. In this work, levels of about seventy organic compounds (including quinones, polyaromatic hydrocarbons (PAHs), alkanes and carboxylic acids) were quantified in Fresno CA. Samples were collected at two sites using both Teflon filters and a Lundgren impactor during 2006 and 2007. Organics were then extracted and analyzed by gas chromatography-mass spectrometry. Mass loadings of quinones were consistent with previous measurements in the region, with up to 70 % of the quinones found in fine PM. The measurements are consistent with traffic and wood burning as the predominant sources of these compounds. The data suggest that the quinones are directly emitted into the air and that atmospheric oxidation of PAHs does not contribute significantly to the mass loadings of these compounds in the region.
CHED 1129
Solubility as a mechanism for CSMR effects on lead leaching
Brandi N Clark, Department of Chemistry, Missouri S&T, Rolla, MO 65401, bncww4@umr.edu
The solution chemistry of Pb(II) at relatively low pH (~ 3-5) was examined in the presence of chloride, sulfate, and phosphate. Lead sulfate solids are relatively insoluble even at pH 3. Pb(II) forms soluble complexes with Cl- that can significantly increase the solubility of lead. Since lead solubility can be correlated to lead contamination problems in drinking water, the data suggest that chloride will worsen lead problems at low pH, whereas sulfate will decrease lead problems. The contradictory trends for the two anions may provide a mechanistic explanation for the success of the empirical chloride:sulfate mass ratio in explaining lead contamination of potable water. Specifically, the trends explain why lead contamination sometimes worsens when changing from alum (higher sulfate) to ferric chloride (higher chloride) coagulants.
CHED 1130
Sorption of natural organic matter (NOM) onto mineral sands
Amy M. Thomas1, Lindsay Seders2, and Patricia A. Maurice2. (1) Chemistry Department, Westminster College, New Wilmington, PA 16172, thomasam@westminster.edu, (2) Department of Civil Engineering and Geological Sciences, University of Notre Dame, South Bend, IN 46556
This project was designed to study the effects of various sands on the adsorption of natural organic matter (NOM) in order to create an accurate laboratory model of groundwater systems. A hydrological tracer was used in order to refine experimental parameters and to ensure experimental reproducibility among trials involving different sands. The sands used in this study were commercially produced hematite, corundum, and quartz, and a naturally-coated sand. All experiments were performed using a gravity-flow column apparatus with a flow rate of 2.0 mL/min, and the measurement of NOM eluate by UV-VIS spectroscopy was measured at 254, 280, and 350 nm. Results indicated that naturally-coated sand causes the greatest adsorption of NOM at both pH 5 and 8. The results of this study may be applied to natural groundwater systems in the study of organic and inorganic molecule transport and procedures used for contaminant removal.
CHED 1131
Stability of palladium nanoparticles under simulated environmental conditions
Ali M. Bramson, Department of Soil Science, University of Wisconsin, 1555 Observatory Dr, Madison, WI 53706, Kevin M. Metz, Environmental Chemistry and Technology, University of Wisconsin-Madison, Madison, WI 53706, and Joel A. Pedersen, Department of Soil Science and Molecular and Environmental Toxicology Center, University of Wisconsin-Madison, Madison, WI 53706-1299
Nanoscale palladium is commonly used as a catalyst and holds promise for many other applications. Environmental exposure to nanoscale palladium could have profound effects due to its reactivity. We investigated the stability of palladium nanoparticles (PdNPs) under simulated oxidative environmental conditions. We synthesized PdNPs via a modified aqueous reduction procedure and examined their stability using an in vitro biomimetic oxidative assay. Palladium nanoparticle transformation was characterized using a variety of analytical methods. Our results will be presented.
CHED 1132
Structural comparison of two iron-bearing clays using infrared spectroscopy
Bryan Richard Bzdek and Molly M. McGuire, Department of Chemistry, Bucknell University, Lewisburg, PA 17837, bbzdek@bucknell.edu
Attenuated total internal reflection Fourier-transform infrared spectroscopy (ATR-FTIR) was used to compare changes in the structures of two hydrothermal nontronite clays as they were reduced. NAu-1 is a bright yellowish-green clay containing Fe3+ in only the octahedral sheet; NAu2- is a dark brown clay containing Fe3+ in both the octahedral and tetrahedral sheets. Oriented clay films were studied under plane polarized light in order to qualitatively determine changes in the orientation of OH and Si-O bonds as the iron in each was reduced. The results of this study aid in understanding the role of tetrahedral iron and changes in clay structure upon reduction.
CHED 1133
Sub-ethal effects of atrazine on Japanese medaka fish
Jordan Theriot1, Carla B. Rosales2, Bernard B. Rees2, and Matthew A. Tarr3. (1) Advanced Materials Research Institute, University of New Orleans, 2000 Lakeshore Drive, New Orleans, LA 70148, Fax: 504-280-6860, jctheriot@gmail.com, (2) Department of Biological Sciences, University of New Orleans, New Orleans, LA 70148, (3) Department of Chemistry, University of New Orleans, New Orleans, LA 70148
The herbicide atrazine could have severe impacts on organisms exposed to contaminated runoff. The EPA maximum contaminant level (MCL) for atrazine is 3 ppb. We observed atrazine's effect on embryonic development, hatching, and mortality rates of the Japanese medaka fish (Oryzias latipes). Fertilized eggs were exposed to 1-25 ppm atrazine and monitored daily for one month. Rearing solutions were removed every six days to verify atrazine levels, which did not change appreciably over the duration of the experiment. Hatching of embryos was delayed relative to controls at all levels of atrazine tested. A low frequency of abnormal cardiovascular and morphological development and higher embryonic mortality were observed in medaka exposed to 10 ppm and 25 ppm atrazine. Thus, subtle (delayed hatching) and dramatic (morphological abnormalities and mortality) effects on development were observed at atrazine levels of 1 to 25 ppm, approximately 3 orders of magnitude higher than the EPA MCL.
CHED 1134
Synthesis and characterization of fluorescent polymer chemosensors for the detection of aqueous endocrine disrupting compounds
Jack M. Fuller and Clifford B. Murphy, Department of Chemistry, Roger Williams University, One Old Ferry Road, Bristol, RI 02809
Endocrine disrupting compounds (EDCs) are linked to the development of cancers breast, gonads, and prostate in humans as well as endocrine disorders in aquatic organisms and their predators. EDCs as environmental contaminants are currently monitored via sampling, with workup occuring off-site using techniques including GC, HPLC, and ELISA. Owing to the low natural concentration of EDCs ( < 1.0 nM), samples require pre-concentration. Here we present the design and characterization of a fluorescent polymer chemosensor for EDCs that is sensitive enough for direct sampling of aqueous environments without pre-concentration. Energy-transfer along the polymer backbone will increase sensitivity of the fluorescence queching response. We have synthesized a polymer of poly-(2-transvinyl-â-cyclodextrophenyl)-alt-(para-9,10-di(1,4-dienthynyl)phenyl)-anthracene. This polymer has been characterized my NMR (1H, 13C), MS, UV-Vis, and fluorescence spectrosopy. The sensitivity of the polymer to steroidal and non-steroidal EDCs in solution will be assessed by Stern-Volmer analysis.
CHED 1135
Environmental fate of lead: Uptake, translocation, and remediation by tomato plants
Lovell Agwaramgbo, Deneyelle Wilson, and Dr. Jose Ramirez, Chemistry, Dillard University, 2601 Gentilly Blvd., New Orleans, LA 70122, Fax: 504-816-4724, lagwaramgbo@dillard.edu, aorta751@yahoo.com
Reports after hurricane Katrina revealed major lead contamination in sediments found in most districts in New Orleans. To further understand lead uptake and to address residents' concerns about the safety of their home grown vegetables and fruits, we decided to investigate if tomato plant can uptake, accumulate, and sequester lead from a contaminated hydroponics medium. Triplicate sets of tomato plants were exposed to 1665 and 827 ppm of lead-miracle grow solutions. After 28 days, the plants in the 1655 PPM lead solution suffered necrosis and died. The plants in each triplicate were washed and separated into leaves, stems, and roots. The plant parts for each triplicate were dried and analyzed using Niton XRF metal analyzer. The results suggest that the stem and root contained lead levels above 86,000, and 100,000 ppm, respectively. No lead was found in the leaves and control plant parts.
CHED 1136
Experimental determination of iron(II) oxidation rate constants in natural waters
Michael J. Pullin, Andrea Higdon, and Eric Osantowski, Department of Chemistry, New Mexico Institute of Mining and Technology, 801 Leroy Place, Socorro, NM 87801, mpullin@nmt.edu, higdona@nmt.edu
The iron chemistry in natural waters is dominated by redox reactions that convert iron(II) to iron(III) and visa versa. One major reaction of this type is the oxidation of iron(II) to iron(III) by dissolved oxygen. The most currently available and detailed iron(II) oxidation model has had only limited success in predicting the rate of this reaction. While this model is able to calculate the oxidation rates for solutions containing carbonic acid, it is does not accurately predict the rates for solutions that exclude it. This research presents an iron redox model that can accurate predict the oxidation rates of iron in a wider range of natural waters. The greater success of this model is in part due to new, experimentally-determined rate constants for the iron(II) hydrolysis species. These rate constants were determined using a novel iron(II)-specific flow injection analysis system.
CHED 1137
Role of organics on the adsorption of molybdate onto aluminum oxide
Caitlin M. Carney, Jennifer L. Morford, Peter H. Helman, and Daniel S. Kritzer, Department of Chemistry, Franklin & Marshall College, P.O. Box 3003, Lancaster, PA 17604-3003, jennifer.morford@fandm.edu
Research has shown that certain humic material can adsorb onto solid surfaces, providing additional sites than may bond trace metals and remove them from solution. In this research the removal of molybdenum from the aqueous phase to the solid phase and the possible influence of organic molecules were investigated. Salicylic acid and protocatechuic acid were chosen as simple models for humic material. Equilibrium experiments were done where both the pH and the amount of aluminum oxide were kept constant, while molybdate concentrations were varied in the presence and absence of salicylic acid. The resulting data were fit with Langmuir curves to quantify the number of surface sites and the saturation point of aluminum oxide, as well as to define the differences in adsorption due to the presence of organic molecules in solution. Preliminary results suggest that the presence of the organic effects molybdate adsorption onto the solid surface.
CHED 1138
Time-series evolution of tertiary structures in bacterial biofilms
Lames Basilyous1, Marc M. Baum1, and Paul Webster2. (1) Oak Crest Institute of Science, 2275 E. Foothill Blvd., Pasadena, CA 91107, l.basilyous@yahoo.com, (2) Ahmanson Advanced Imaging and EM Center, House Ear Institute, Los Angeles, CA 90057
The main objective of the present research was to investigate the development of bacterial biofilm structures as a function of time. Two different methods of preparing the biofilms for examination under SEM were used, namely: propane freezing, and chemical fixation. The same results were obtained from those different methods when looking at the first three days of biofilm assembly. The results showed how long bacterial rods (ca. 10 by 0.2 µm) in day one divide to smaller cells (ca. 2 by 0.2 µm) in day two and three. It also shows how the amorphous matrix of the biofilm is built over harder sheets that support its growth. The bacterial flagellum was also studied under TEM using 1% neutral phosphotungestic acid as a stain. The results obtained showed that some bacteria had up to three flagella. Results showed that most of the bacteria lose their flagella by the third day of growth. This research can be useful for future biofilm studies by proving that the biofilm structure observed by SEM is real and not artificial since it is shown to be the same in different methods of preparation. It is also useful in understanding how the biofilm grow on the hard sheets, and how important is the flagellum lost in building the biofilm.
CHED 1139
Trace element content of leaves from trees growing in an acid mine drainage impacted environment
Jennifer McKillop1, Ryan C. Galloway1, Perry J. Hardin2, Mark W. Jackson2, Matthew Bekker2, Ryan R. Jensen2, Sandra S. Brake3, and Stephen F. Wolf1. (1) Department of Chemistry, Indiana State University, Terre Haute, IN 47809, jmckillop@mymail.indstate.edu, rgalloway@indstate.edu, (2) Department of Geography, Brigham Young University, Provo, UT 84602, (3) Department of Geography, Geology, and Anthropology, Indiana State University, Terre Haute, IN 47809
We are studying the impact of acid mine drainage (AMD) on trees growing at or near the recovered Green Valley Coal Mine site in Vigo County, IN with the goal to better understand how AMD affects tree health and to determine whether methods of remote sensing can be used to identify affected trees. To achieve these goals, 88 soil and 155 leaf samples from Ash and Locust trees were collected from 120 pre-mapped points on the site. Soil pH and leaf spectral reflectance were determined at the site. Soil and leaf samples were prepared for trace elemental analysis using extraction and total dissolution procedures, respectively. The concentrations of 46 trace elements were determined in samples, duplicates, controls, and standard samples using ICPMS. The results of these analyses and the efficacy of XRF for leaf sample analysis will be evaluated.
CHED 1140
Ultraviolet µ-raman analysis of methane sulfonic acid
M. Paul Herring and Robert E. Barletta, Department of Chemistry, University of South Alabama, 307 University Blvd N, Mobile, AL 36688
Methane sulfonic acid (MSA) and other marine sulfur compounds (dimethyl sulfide (DMS) and dimethylsulfonioproprionate (DMSP)), are found at trace concentrations in the open ocean. Their distribution in the glacial record provides insight into the climatological history of our planet. For ice cores, current analytical methods involve sectioning followed by destructive analysis. Methods, e.g., Raman spectroscopy, which determine composition and concentration nondestructively with high spatial resolution, are of great interest. To evaluate the potential of Raman for the trace detection of marine sulfur compounds, laboratory measurements have been made using 248 and 488 nm excitation. Assignments of characteristic Raman bands have been made: n(C-S) = 656 n cm-1 (DMSP); n(C-S) = 686 n cm-1 (DMS); n (C-S) = 770 n cm-1 (MSA). The detection sensitivity of MSA at 488 nm was found to be ~52.0 ppm. Finally, resonance enhancement of MSA has also been found.
CHED 1141
Using gas chromatography/mass spectroscopy to assess pollutant emissions from motorcycles
Alexander J. Zoelle, James Coffield, and Michael J Baird, Department of Chemistry, Wheeling Jesuit University, 316 Washington Ave., Wheeling, WV 26003, baird@wju.edu
Since motorcycles are not the primary means of transportation in most countries, motorcycles emissions have been ignored in legislation on emission standards.
It has been reported that motorcycles collectively emit approximately 16 times more hydrocarbons and 3 times more carbon monoxide than automobiles. To introduce students to an environmental issue and also to instrumental analysis, a laboratory experiment is being developed to analyze the emissions from Honda motorcycles (1100 and 1800 cc's) and a Honda automobile. A technique will be developed to obtain a representative gaseous sample from the exhaust and a method will be developed for GC/MS analysis. Product identification will be made using the NIST library and using standard compounds. The flow rate of emissions will be measured for each vehicle and utilized with the GC/MS data to obtain grams of CO and hydrocarbons per hour. The results from 12 students performing this experiment in an Instrumental Analysis Laboratory class will presented. Since current legislation is pending in the U.S. to regulate motorcycle emissions, this experiment will be beneficial to the student's education.
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