Progress 10/01/10 to 09/30/15

Outputs
Target Audience:Scientists in academia (faculty and students) and government agencies, USEPA, concentrated feed operators, military-related personnel dealing with environmental management, industry, general public, engineering professionals, commercial biosolid, soil, and fertilizer companies, and the urban grower. Changes/Problems:Our bimetal work to transform perfluoroalkyl acids, particualry the sulfonates, has proven unsuccessful. We are now trying to find other reductive methods including the use of Vitamin B12, which is showing promise. What opportunities for training and professional development has the project provided?This research presented involves the training and professional development offive graduate students, 1 visiting scholar, 2 undergraduates, and one post doctoral associate which included conducting research, mentoring (post doc mentoring graduate students and undergraduates), writing abstracts and manuscript drafts, and presenting at professional meetings. How have the results been disseminated to communities of interest?Research results have been presented at7 conferences. What do you plan to do during the next reporting period to accomplish the goals?Future work under this HATCH includeswriting the soprtion and aerobic degradaton papers on BPA and BPA alternatives and conduct anaerobic studies for assessing fate in municipal wastewater treatment.We will alsowork on other reductive methods for transforming PFOS including the use of Vitamin B12, which is showing promise.Future work on TrOCs will become part of a new faculty member's HATCH and will include assessing degradation of selected TrOCs in urban-garden relevant matrices (potting mix, urban garden soil, commercial top soil) once products are applied, uptake potential in urban crops grown in container gardens, and further validation/confirmation of contaminants identified as well as an expansion to other TrOCs (e.g., PBDEs, pesticides, and hormones).

Impacts
What was accomplished under these goals? Objective 1: 33 contaminants of emerging concern (TOrCs) were quantified including 2 antimicrobials, 8 hormones, 4 bisphonol analogs, 4 parabens, PBDE, nonylphenol (4-NP), PFOS, PFOA, 10 pharmaceuticals, 4 synthetic fragrances, and 2 UV filters om 5 heat-dried biosolids, 6 composted biosolids, and 9 non-biosolid based ' soils/fertilzers'. Of the 33 TrOCs of interest, 21 were detected in at least 1 commercially available biosolid-based fertilizer and all values were within the ranges previously reported in municipal biosolids. Antimicrobials triclosan and triclocarbon concentrations were 285-19,987 mg/kg and 190-54,053 mg/kg, respectively, with the concentrations greater in heat-treated biosolids and cake. Triclosan concentrations consistent with the reference standard and higher in Milorganite than previously reported. The bisphenol analog concentration ranges were BPA 468-68,168 mg/kg, BPS: 38-4797 mg/kg, BPAF: 5-84 mg/kg, and TBBPA: 332 mg/kg, which were detectable in food waste. Methy and ethyl paraben concentrations were 214-3,048 mg/kg and 7.8-98.9 mg/kg, respectively, and propyl and benzyl parabens were not detected. Many parabens (e.g., methyl paraben) are found in nature, thus not surprising that there would be elevated concentrations in the non-biosolid based fertilizers as well; however, with the backlash against parabens, their ubiquitousness is interesting. For PFOA and PFOS concentrations, 6.3-69.1 mg/kg and 2.7-198.2 mg/kg, respectively were observed with detection in food wastes, but no measurable quantities in 4 of the heat-treated biosolids. For the pharmaceuticals we observed c Cimetidine: 210-2891 mg/kg, ibuprofen: 190-456 mg/kg, diphenhydramine: 52-2,326 mg/kg, ciprofloxacin: 6-843 mg/kg, miconazole: 159-2,258 mg/kg, and doxycycline with concentrations greater in heat-treated biosolids and cake. No detection of ofloxacin, simvastatin, sulfanilamide, and tetracycline was observed in any sample. 4-NP ranges of 3,288-44,017 mg/kg were observed. Of the synthetic musks, we observed primarily tonalide: 915-21,894 mg/kg and galaxolide: 1,656-72,827 mg/kg. Musk ketone and musk xylene were not detected in any samples. Lastly, the UV filters 2,4'-dihydroxybenzophenone and 2.2'-dihydroxy-4methoxybenzophenone concentration of 66-961 mg/kg and 8.5-1,153.9 mg/kg, respectively. Seasonal fluctuations likely given their use in sunscreens, however, they are also used as a UV protectant in food-grade plastics. Overall, all TOrC concentrations fell within ranges previously detected in municipal biosolids. TrOCs persist during the preparation of commercial growing products; however, detection in the cake and heat-treated samples were generally higher than in composted products or soils (unless attributable to an industrial input). Note that detection of TrOCs alone is not necessarily a reason for concern; however, for some compounds (i.e., musk fragrances, pharmaceuticals, and bisphenol alternatives), their use, thus detection, are likely to increase; likewise, for others (e.g., BPA), concentrations should decline. Detection does not suggest human health risks, but quantitative data are helpful in ecological risk assessments. We also did some preliminary desorption studies with 2 biosolids: Milorganite and Bay State Fertilizer. We hypothesized that the matrix of the heat-treated biosolids would slow the release of the contaminants into the water phase. Desorption behavior was compound and matrix specific. Triclocarban and BPA Kd values in general agreement with published sludge-water partitioning studies. Triclocarban desorption different between sources with mobilization potential greater from Milorganite. Little to no lag in release was observed in a slurry system with equilibrium reached for all 3 compounds within 12 h. No discernable difference in desorption for BPA between sources with BPA Kd (2.09-2.30) similar to published sludge studies. Methylparaben desorption different between sources with mobilization potential greater from the Bay State Fertilizer. TrOC-fertilizer specific Kd values and total TrOC initially present can be used to estimate maximum concentrations expected in pore water. TrOC release will likely be slower in a typical moist soil (not slurry) system giving time for microbial degradation to reduce concentrations in the media. Objective 2: We prepared and evaluated nanoscale ZVI-Pdº, Pdº/Mgº, and Pdº/Feº/Alº nanoparticles as well as iron oxide nanocomposite material for removal of PFOS and in most cases also PFOA. Trichlorophenol was used as our positive control in all systems and observed to degrade essentially completely in all systems. Extraction methods for PFOA and PFOS from Pdº/Feº particles were optimized by evaluating extraction efficiencies. All of our work with Pd/nZVI that indicated PFOA transformation was biased by Fe complexation with PFOS, PFOA, and PFHxA. Fe-complexed perfluoroalkyl acids did not elute with free PFOS, thus PFOS remaining after reactions was underestimated and assumed to be transformed. We then carefully investigated the role of Fe and PFOS concentrations as well as pH and other ligands in Fe-PFOS complexation. We learned increasing the pH to 10 releases the complexed PFOS allowing it to be properly quantified. New experiments conducted using this methodology revealed no PFOS reduction even after 21 days of contact time wit %Pd up to 1%. Therefore, further research on other methods that may allow PFOS transformation to occur are being sought. Overall, this past year was focused on getting out the publications from data collected in previous years. However, we alsomade progress onquantifying the fate of bisphenol A (BPA) and two BPA alternatives (BPS and BPAF). We completed sorption studies fora variety of soils that represent the more typical pH and organic carbon content range of nontropical soils. We also completed pH-dependent octanol-water partitioning studies for all three compounds andcompared them with pH-dependent OC-normalized partition coefficients. We completed aerobic soil degradation studies for all three compounds. Degradation rates were estimated, but we were unsuccessful at trying to identify metabolites.Lastly we completed degradation studies and quantifying kinetics of a PFOS-based surfactant di-SAmPAP.

Publications

• Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Park, S., Lee, L. S., Medina, V. F., Probing in-situ chemical reductive defluorination of perfluoroalkyl compounds in ground water impacted aqueous fire-fighting foams, 20th World Congress of Soil Science, Jeju, Korea, Jun. 8-13, 2014
• Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: John Hemmerling, Michael L. Mashtare, and Linda S. Lee, "Evaluating Contaminants of Emerging Concern in Commercial Biosolid-based Fertilizers" (September 30, 2014). The Summer Undergraduate Research Fellowship (SURF) Symposium. Paper 120. http://docs.lib.purdue.edu/surf/2014/presentations/120
• Type: Other Status: Submitted Year Published: 2014 Citation: Medina, V. and L.S. Lee. 2014. Technology News & Trends | a quarterly newsletter, Issue 66, Characterization and Testing: Bench-Scale Research on Options for In Situ Treatment of Perfluorinated Compounds, http://cluin.org/PRODUCTS/NEWSLTRS/tnandt/email/0814.html
• Type: Journal Articles Status: Awaiting Publication Year Published: 2015 Citation: Gall, H.E., N. B. Basu, P.S.C. Rao, M. Mashtare, and L.S. Lee. 2015. Assessing the Impacts of Anthropogenic and Hydro-Climatic Drivers on Estrogen Legacies and Trajectories, Advances in Water Resources, In press.
• Type: Journal Articles Status: Published Year Published: 2015 Citation: Leet, J.K., S. Sassman*, J.J. Amberg, A.W. Olmsteadd, L.S. Lee, G.T. Ankley, and M Sepulveda, 2015. Environmental Hormones and Their Impacts on Sex Differentiation in Fathead Minnows, Aquatic Toxicology, 158:98107.
• Type: Journal Articles Status: Published Year Published: 2105 Citation: Gall, H.E., S.A. Sassman*, B. Jenkinson, L.S. Lee, and C. Jafvert. 2015. Comparison of Export Dynamics of Nutrients and Animal-borne Estrogens from a Tile-Drained Midwestern Agroecosystem, Water Research, Water Research, 72:162-173.
• Type: Journal Articles Status: Published Year Published: 2015 Citation: Royer, L., L.S. Lee, M. Russell, L. Nies, and R. Turco. 2015. Microbial transformation of 8:2 fluorotelomer acrylate and methacrylate in aerobic soils. Chemosphere, 129:54-61.
• Type: Journal Articles Status: Awaiting Publication Year Published: 2015 Citation: Dasu, K. and L.S. Lee. 2015. Aerobic Biodegradation of Toluene-2,4-di(8:2 fluorotelomer urethane) and Hexamethylene-1,6-di(8:2 fluorotelomer urethane) Monomers in Soil. Chemosphere, In press.

Progress 10/01/13 to 09/30/14

Outputs
Target Audience: Target Audiences: Scientists in academia (faculty and students) and government agencies, USEPA, concentrated feed operators, military-related personnel dealing with environmental management, industry, general public, engineering professionals, commercial biosolid, soil, and fertilizer companies, and the urban grower. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? This research presented involves the partial training and professional development ofthree graduate students, 2 undergraduates, and one post doctoral associate which included conducting research, mentoring (post doc mentoring graduate students and undergraduates), writing abstracts and manuscript drafts, and presenting at professional meetings. How have the results been disseminated to communities of interest? Research results have been presented atthe Soils World Congress (Korea), Soils in the City (Chicago, IL), which had academics, industry, local community representatives, and government personnel present, and at the 3 other conferences/symposia at Purdue (ESE and SURF) as well peer-reviewed journal papers and 2 dissertations.. What do you plan to do during the next reporting period to accomplish the goals? Future work on TrOCs includes assessing degradation of selected TrOCs in urban-garden relevant matrices (potting mix, urban garden soil, commercial top soil) once products are applied, uptake potential in urban crops grown in container gardens, and further validation/confirmation of contaminants identified as well as an expansion to other TrOCs (e.g., PBDEs, pesticides, and hormones). Degradation studies with BPA alternatives have been initiated and will completed over the next year to complete our laboratory-based assessment of their environmental behavior. Over the next year, graphene-supported nFe3O4-Pd/Fe nanocomposite will be prepared to reduce agglomeration. Graphene has extraordinary electrical, thermal, mechanical, and chemical properties and a much higher theoretical surface area (2630 m2/g) than even carbon nanotubes. Furthermore, graphene exhibits high efficient utilization of its surface area due to the accessibility of the both sides of the nanosheets which makes it a promising material for catalytic applications. Therefore, we will use graphene oxide (GO) to support nFe3O4-Pd/Fe nanocomposite to enhance reactivity and decrease aggregation of our nanocomposite. We will also work on methods to prepare and evaluate nFe3O4-Ni/Fe and graphene-supported nFe3O4-Ni/Fe nanocomposite.

Impacts
What was accomplished under these goals? We conducted studies quantifying the partitioning behavior of bisphenol A and its manufacturing replacements including its analogues, 4,4'-sulfonyldiphenol (bisphenol S, BPS) and 4-[1,1,1,3,3,3-Hexafluoro-2-(4-hydroxyphenyl)propan-2-yl]phenol (bisphenol AF, BPAF). These alternatives, which are expected to increase in use as a result of the ban of BPA, were once considered safe substitutes; however, recent research demonstrates similar estrogenic activity to BPA. Octanol-water partition coefficients (Kow) and sorption coefficients (Kd, L/kg) in several agricultural soils representing a range in organic matter content and pH were determined. The partitioning and sorption behavior of BPS and BPAF were pH-dependent with increased sorption to soils observed with increasing organic matter content. BPS exhibited lower Kd and Kow values than BPA, thus will be more mobile in the environment. BPAF reflected higher Kd and Kow values than BPA, thus will be less mobile. BPA is more biodegradable in the soil than BPAF and BPS, and thus are more likely to accumulate in the aerobic environment. Overall, these results broaden our knowledge on BPS and BPAF fate in the environment, which can be coupled to ecotoxicity studies to assess potential risk to ecosystem and human health. We began quantifying the aerobic soil biotransformation in a forest soil and sandy student farm soil of N-ethyl perfluorooctane sulfonamidoethanol (N-EtFOSE) and EtFOSE-based phosphate diester (SAmPAP Diester), which have been determined or proposed as potential precursors of the perfluorooctanesulfonate (PFOS), which is not biodegradable. No changes in the concentrations of the starting materials were observed in autoclaved-sterilized soil microcosms to date (2 months). In the live soil amended with SAmPAP diester, EtFOSE concentrations decreased over time, EtFOSAA, perfluorooctane sulfonamide acetate (FOSAA) and FOSA increased over time, while EtFOSA concentrations appeared to remain fairly constant. A newly released high-purity standard of SAmPAP diester is being used to estimate SAmPAP diester degradation rates, which is slow, along with metabolite trends (stud still ongoing). We also observed what appears to be solvent-induced ester hydrolysis in the presence of live soil only similar to what we have observed with other monomers. To further estimate PFOS yield from SAmPAP diester, EtFOSE aerobic transformation were also explored in an identical systems with initial dosage 4.02 µg/g soil. The present data showed that almost 11.8 % EtFOSE were removed at day 6, and EtFOSAA and FOSA were also detected as degradation metabolites at day 6. This work provides evidence on consideration of SAmPAP and EtFOSE as the indirect source of PFOS in soil. For 2 biosolids: Milorganite and Bay State Fertilizer, we quantified desorption rates in aqueous batch slurries of BPA, methylparaben, and two antimicrobials (triclocarbon, and triclosan). Little to no lag in release was observed in a slurry system with equilibrium reached for all 3 compounds within 12 h. Desorption behavior was compound and matrix specific. Triclocarban and BPA Kd values are in general agreement with published sludge-water partitioning studies. Triclocarban desorption was different between sources with mobilization potential greater from Milorganite. No discernable difference in desorption for BPA between sources with BPA Kd (2.09-2.30) similar to published sludge studies. Methylparaben desorption different between sources with mobilization potential greater from the Bay State Fertilizer. Contaminant release from biosolids will likely be slower in a typical moist soil (not slurry) system giving time for microbial degradation to reduce concentrations in the media. In our studies assessing abiotic approaches to breakdown PFOS and POFA in groundwater, evaluated nanoscale ZVI-Pdº, Pdº/Mgº, and Pdº/Feº/Alº nanoparticles as well as iron oxide nanocomposite material. Trichlorophenol was used as our positive control and observed to degrade essentially completely in all systems. Extraction methods for PFOA and PFOS from Pdº/Feº particles were optimized by evaluating extraction efficiencies of acetonitrile (ACN), acidic acetonitrile (H-ACN), and ethyl acetate EA). Total recovery for PFOA and PFOS with 4 extractions using ACN was 66 % and 77%, respectively. Total recovery for PFOA and PFOS with 4 extractions using H-ACN was 90.8 % and 88.2%, respectively.Total recovery for PFOA and PFOS with 4 extractions using EA 96 % and 100%, respectively. Therefore, EA was selected for the extraction solution of choice. The effect of increasing %Pd (0.43% to 1.0%) on the nano-ZVI was evaluated. No statistical difference on the magnitude of PFOS removal was apparent with observed PFOS loss being 29 to 35%. However, increased amounts of particles (.1 g to 0.3 g) statistically reduced PFOS removal from 32% to 24%, likely due to its aggregation. An initial assessment on the effect of pH (unbuffered system, pH < 3.6, pH=6.3, and pH > 12.4) and temperature (25 and 50 C) on PFOS removal was also assessed for a 6-day reaction period. Highly acidic (pH < 3.6) and highly basic (pH > 12.4) enhanced PFOS removal. Up to 40% of PFOS removal was observed in both conditions. Acid condition may lead to rapid Fe corrosion which produces sufficient atomic H. Atomic H can also be produced even at highly basic conditions, thus enhancing PFOS removal. Elevated temperature (T= 50 °C) at pH=6 showed the highest PFOS removal of 43%, which was statistically higher than under the extreme pH conditions. Heat may have helped to achieve the energy needed for activation. The lowest removal was observed in the unbuffered system at 25 C (36%). To measure PFOS isomers, a method was developed for an API 3000 LC/MS/MS using an Ascentis Express F5 PFP column (2.7 µm, 90 Å, 10 cm x 2.1 mm, Sigma-Aldrich). For nanoscale Pdº/Mgº in unbuffered 25 C solutions, PFOA and PFOS removal was 35% and 15%. High reactivity resulted on passive films forming quickly on the surface limiting further degradation potential.Nanoscale Pdº/ Feº/Alº particles’under basic conditions removed up to 28%PFOS, which was achieved by 24 h. Removal of PFOS under acidic and unbuffered solutions was 36% and 32%, respectively. PFOS defluorination with nFe3O4 nanocomposites did not appear effective in our first study although positive controls showed particle activity. We hypothesize that aggregation of nanoparticles due to Van der Waals forces decreased their reactivity considerably. Using TEM, we confirmed the size of these nanocomposites were ~20 - 30 nm, but saw agglomeration as well. With regards to inorganic constituents of concern or emerging concern, we completed our work on mobilization of arsenic and selenium from fly ash facilitates and the ERDC field study on antimony migration from military small firing arm sites.

Publications

• Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Park, S., Lee, L. S., Medina, V. F., Probing in-situ chemical reductive defluorination of perfluoroalkyl compounds in ground water impacted aqueous fire-fighting foams, 20th World Congress of Soil Science, Jeju, Korea, Jun. 8-13, 2014
• Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: John Hemmerling, Michael L. Mashtare, and Linda S. Lee, "Evaluating Contaminants of Emerging Concern in Commercial Biosolid-based Fertilizers" (September 30, 2014). The Summer Undergraduate Research Fellowship (SURF) Symposium. Paper 120. http://docs.lib.purdue.edu/surf/2014/presentations/120
• Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Lee, L.S., S. Park, and V. Media. Chemical Oxidation and Reduction of Perfluoroalkyl Substances. Groundwater Remediation Associations, Oakland, CA, Feb. 2014.
• Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Mashtare, J. Hemmerling, and L.S. Lee. 2014. Evaluating Contaminants of Emerging Concern in Commercial Biosolid-Based Fertilizers. IN Soils in the City: Enhancing Urban Soils for Living Landscapes and Healthy Communities, June 29  July 2, 2014, Chicago, IL 60611
• Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Lee, L.S. Greening the City Perspective. IN Soils in the City: Enhancing Urban Soils for Living Landscapes and Healthy Communities, June 29  July 2, 2014, Chicago, IL 60611
• Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Choi, Y. and L.S. Lee, " Comparing the Partitioning Behavior and Sorption to Agricultural Soils of Bisphenol A (BPA) and Two Currently Used BPA Alternatives BPS and BPAF". IN Soils in the City: Enhancing Urban Soils for Living Landscapes and Healthy Communities, June 29  July 2, 2014, Chicago, IL 60611
• Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Choi, Y. and L.S. Lee. Sorption behavior of bisphenol S (4,4'-sulfonyldiphenol) on agricultural soils. 20th World Congress of Soil Science, Jeju, Korea, Jun. 8-13, 2014
• Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Choi, Y. and L.S. Lee, 2014. Sorption Behavior of BPS (4,4-Sulfonyldiphenol) and BPAF (HexafluorobisphenolA) on Agricultural Soils. EmCon 2014, Iowa City, Iowa.
• Type: Conference Papers and Presentations Status: Published Year Published: 2014 Citation: Lilan Zhang, Linda S. Lee, and Jinxia Liu. 2014. Aerobic Soil Biotransformation of N-ethyl Perfluorooctane Sulfonamidoethanol (N-EtFOSE) and EtFOSE-Based Phosphate Diester (SAmPAP Diester). EmCon 2014, Aug. 19-21, 2014. Iowa City, Iowa.
• Type: Journal Articles Status: Published Year Published: 2013 Citation: Hyun, S. and L.S. Lee. 2013. Soil Attenuation of As(III, V) and Se(IV, VI) Seepage Potential at Ash Disposal Facilities. Chemosphere, 93(9), 21322139 http://dx.doi.org/10.1016/ j.chemosphere.2013.07.064.
• Type: Journal Articles Status: Published Year Published: 2013 Citation: Martin*, W.A., L.S. Lee, and P. Schwab. 2013. Antimony migration trends from a small arms firing range compared to lead, copper, and zinc. Sci. of the Total Environ., 463464:222228.
• Type: Journal Articles Status: Accepted Year Published: 2014 Citation: Royer*, L., L.S. Lee, M. Russell, L. Nies, and R. Turco. 2014. Microbial transformation of 8:2 fluorotelomer acrylate and methacrylate in aerobic soils. Chemosphere, In press.
• Type: Journal Articles Status: Under Review Year Published: 2014 Citation: Martin*, W.A., S. L. Larson, C.C. Nestler, and L.S. Lee. 2014. The leaching fate of antimony and lead under dynamic loading conditions. J. of Hazardous Mat., In review.
• Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Mashtare, M. L. and L. S. Lee. 2013. Transformation of Natural Estrogens Under Anaerobic Conditions. 2013 ASA, CSSA, and SSSA International Annual Meetings, Tampa, FL. Presented November 5, 2013.
• Type: Conference Papers and Presentations Status: Published Year Published: 2013 Citation: Lee, Linda S., 2013. Sorption, Degradation, and Transformation in Soils and Sediments: Sinks or Sources? SSSA Invited Speaker, Nov 4, 2013.
• Type: Theses/Dissertations Status: Published Year Published: 2013 Citation: Fate of 17?-Estradiol, 17?-Estradiol, and Estrone in Agricultural Soils and Sediments. Dissertation. Purdue University, West Lafayette, IN
• Type: Theses/Dissertations Status: Published Year Published: 2014 Citation: Antimony Environmental Interactions and Sequestration Associated with Amendments at Small Arms Firing Ranges. Dissertation. Purdue University, West Lafayette, IN

Progress 10/01/12 to 09/30/13

Outputs
Target Audience: Scientists in academia (faculty and students) and government agencies, USEPA, concentrated feed operators, military-related personnel dealing with environmental management, industry, general public, and engineering professionals. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? This research presented involves the training and professional development of three graduate students and 2 undergraduates, which included conducting research, mentoring (graduate students mentoring undergraduates), writing abstracts and manuscript drafts, and presenting at professional meetings. How have the results been disseminated to communities of interest? Research results have been presented at conferences, five universities in Florida, Colorado, China, and Korea, Agricultural Roundtable at Purdue, and as lectures in 3 courses at Purdue. What do you plan to do during the next reporting period to accomplish the goals? We will continue research to develop a remediation technology suitable for cleaning up groundwater contaminated with PFOS and PFOA from the repeated use of fire-fighting foams at with military sites. We will also move forward on additional research on fluorotelomer acrylate monomers that are precursors to PFOA. Research will include cosolvency solubility studies and characterizing the production of PFOA from persulfate oxidation as a way to characterize total PFOA formation from biosolids that contain precursors to PFOA. We will start new research to characterize another class of PFASs referred to as SamPAPs, which will include biotransformation potential and similar to the PFOA precursors, we will assess PFOS formation potential using persulfate oxidation. We will also start new research on the environmental fate of bisphenol replacements and the leaching/bioavailability studies of selected contaminants of concern in municipal WWTP biosolids and commercially available biosolids.

Impacts
What was accomplished under these goals? Given our finding in our heat-activated persulfate oxidation that PFOS remained unaltered, we moved to investigating reductive techniques. We hypothesized that PFOS is conducive to reduction, thus, we assessed the potential of dithionite (S2O42, E°= -0.66 V), sulfide, nanoscale zero valent bimetals Fe°/Pd° (Fe°, E°= -0.447 V) and microscale Mg°/Pd° (Mg°, E°= -2.37 V) to defluorinate PFOA and PFOS in aqueous systems. Sodium dithionite (Na2S2O4) and sulfide which are inexpensive and safe reducing agent are conducive to in-situ injection and have been used for in-situ dechlorination. Fe° has been extensively studied and accepted as an attractive approach for remediation of persistent organic compounds given it is inexpensive, readily available, and has minimal environmental risk. Nano-particles have greater surface area, thus enhanced reactivity potential and palladization serves to catalyze the defluorination reaction by enhancing iron corrosion. The use of Mg°/Pd° has additional potential advantages such as a higher reduction potential, reduced development of a passivation layer on the metal surface due to the higher solubility of Mg-oxides compared to Fe-oxide, and Mg°/Pd° can be applied to both under aerobic and anaerobic conditions. The PFOA and PFOS were quantified by high performance reverse phase liquid chromatography tandem electrospray ionization mass spectrometry. The amounts of Pd loading were measured by inductively coupled mass spectrometry after acid digestion. However, analysis of fluoride using both ion chromatography and F-specific electrode was challenging due to adsorption of fluoride to Mg-oxide and Fe-oxide. Preliminary work with both dithionite and sulfide at concentrations 50 mg/L to 2,500 mg/L and temperatures approaching 90 °C showed that neither PFOA nor PFOS were degraded over a 7 day period. However, Fe°/Pd° degraded 30 % of PFOA and 15 % of PFOS after 7 days. The removal PFOA and PFOS increased with increasing Pd loading and Fe amount. Mg°/Pd° degraded 35% of PFOA and 15% of PFOS in 48 hours. Both of them have something commons that the effect of cosolvent and temperature did not enhance to degrade PFOA and PFOS since they inhibited the sorption of PFOA and PFOS to bimetals. However, it is obvious that Mg°/Pd° degraded PFOA and PFOS faster than Fe°/Pd°. For the future works, we will focus on determining reductive reaction mechanisms and degradation pathways (identify metabolites), optimal working conditions, and potential interferences for developing a strategy for in-situ employment. In our hormone work, we focused our work on the anaerobic biotransformation of 17α-E2, 17β-E2, and E1 in sediments under nitrate-reducing, iron-reducing, sulfate-reducing, and methanogenic conditions, which reported on under Accession No. 219835-Project No. IND010831R2-Multistate No. W2170.We are also finishing the development and testing of our Hormone Export Restoration Dynamic (HERD) and Stream Transport model with a focus on hormones as well as our passive flux meter work, which will be reported under IND010818G and not dual reported here.

Publications

• Type: Journal Articles Status: Published Year Published: 2013 Citation: Mashtare, M. L.S. Lee, L.F. Nies, and R.F. Turco. 2013. Transformation of 17?-estradiol, 17?-estradiol, and estrone in sediments under nitrate- and sulfate-reducing conditions. Environ. Sci. Technol. 47(13):7178-7185, DOI: 10.1021/es4008382.
• Type: Journal Articles Status: Published Year Published: 2013 Citation: Mashtare, M., Green, D., and L.S. Lee. 2013. Biotransformation of 17? and 17?-Estradiol in Aerobic Soils Chemosphere, 90(2), 647-652.
• Type: Journal Articles Status: Published Year Published: 2013 Citation: Leet, J., L.S. Lee, H. Gall, R. Goforth, S. Sassman, D. Gordon, J. Lazorchak, M. Smith, C. Jafvert, M. Sepulveda. 2012. Assessing impacts of land-applied manure from concentrated animal feeding operations on fish populations and communities. Environ. Sci. Technol., 46(24):13440-7.
• Type: Journal Articles Status: Published Year Published: 2013 Citation: Dasu, K., L.S. Lee, R.F. Turco, and L. Nies. 2013. Aerobic Biodegradation of 8:2 Fluorotelomer Stearate Monoester and 8:2 Fluorotelomer Citrate Triester in Forest Soil. Chemosphere, 91, 399-405
• Type: Journal Articles Status: Published Year Published: 2013 Citation: Gall, H., S. Sassman*, B. Jenkinson, L.S. Lee, and C. Jafvert. 2013. Hormone Loads Exported by a Tile- Drained Agroecosystem Receiving Animal Manure Wastes. Hydrological Processes, In press (online Jan. 2013), DOI: 10.1002/hyp.9664
• Type: Journal Articles Status: Published Year Published: 2013 Citation: Khan, B. and L.S. Lee. 2012. Estrogens and Synthetic Androgens in Manure Slurry from Trenbolone Acetate/Estradiol Implanted Cattle and in Waste-Receiving Lagoons Used for Irrigation, Chemosphere, 89, 14431449.
• Type: Journal Articles Status: Awaiting Publication Year Published: 2013 Citation: Meyer, J.L., S. Rogers, L.S. Lee, D.L. Villeneuve, G.T. Ankley, K.M. Jensen, J.K. Leet, M.S. Sep�lveda. 2013. Vitellogenin and testosterone in common snapping turtles (Chelydra serpentina) from a Concentrated Animal Feeding Operation (CAFO) Site. J. Wildlife Diseases, 49(4), In press, DOI: 10.7589/2012-10-248.

Progress 10/01/11 to 09/30/12

Outputs
OUTPUTS: We continue to conduct research on manure-born hormones and biosolid-born pharmaceuticals, which we have reported under (IND050018R2) and will not dual report here. We continue to conduct research on manure-born hormones and biosolid-born pharmaceuticals, which we have reported under (IND050018R2) and will not dual report here. Likewise our work on predicting the propagation of hormone from a CAFO source zone into a watershed and assessing in-stream biogeochemical processes attenuating hormones during transport will be reported under (IND010818G) and not dual reported here. We continue our research on perfluoroalkyl substances (PFASs) with our current focus being abiotic remediation. PFASs have been widely used in industrial and commercial application for about 50 years as surfactants, emulsifiers, stain resistant coatings, fire retardants, and polymer additives. The PFASs of greatest current concern in the environment are perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA), which have been shown to be environmentally persistent, bioaccumulative and potentially toxic. PFOS and PFOA may enter the environment through direct industrial discharges or fighting fires, from residuals in commercial products, or as terminal end products of the microbial degradation of other PFASs. We have quantified the use of heat and base activated persulfate and probed the use of dithionite, nanoscale bimetal palladium-zero iron (Pd-ZVI) and smectite-based Pd-ZVI for defluorinating perfluoroocatanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). The overall goal is to find a suitable in situ chemical oxidation method for environmentally relevant concentrations. For persulfate, we quantified the effect of temperature 20 C - 60 C, persulfate concentration (1,000 to 20,000 mg/L), reaction time (up to 225 hours for lower temperatures), and the presence of other co-contaminants (e.g., chlorinated solvents and fuel constituents) on the efficacy of persulfate to defluorinate PFOS and PFOA. PARTICIPANTS: Linda S. Lee, Professor, AGRY - project PI Suresh C. Rao, Professor, CE/AGRY - supported work on the surface water flux meter development; Ron Turco, Professor, AGRY - supported work on biotransformation studies; Larry Nies, Professor, Civil - supported work on biotransformation studies; Michael Mashtare, PhD student, AGRY, Purdue - conducted aerobic and anaerobic biodegradation studies with hormones; Stephen Sassman, Analytical Chemist, AGRY, Purdue. TARGET AUDIENCES: Target Audiences include regulators, farmers, industry personnel, and military personnel in addition to research scientists and students. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Base activation was not successful for either PFOA or PFOS; however, heat activation was very successful for PFOA degradation. The apparent removal of PFOA increased with increasing temperature with 75% removal at 40 C in 138 hours and complete loss of PFOA at 50 in 72 hours and at 60 C in 48 hours. Increasing initial persulfate concentrations at 50 C increased the rate of PFOA degradation. Low levels of shorter perfluorinated chained metabolites including perfluorobutanoic, perfluoropentanoic, perfluorohexanoic, and perfluoroheptanoic acids were generated and then subsequently degraded. Analysis of fluoride using both ion chromatography and an F-specific electrode was challenging due to the large amounts of sulfate present. Persulfate oxidation did not appear to impact PFOS concentrations, thus other techniques needed to be probed. Dithionite, nanoscale bimetal palladium-zero iron (Pd-ZVI) and smectite-based Pd-ZVI all appeared to have some success in defluorinating perfluoroocatanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in our preliminary studies. However, shorter perfluorinated chained metabolites were not observed not was fluoride concentration in the bimetal studies sufficient to close mass balance. Fluoride could not be measured in the dithionite reactions due to high concentrations of sulfate that are produced similar to the persulfate reactions. Additional work to optimize these approaches and measure potential byproducts will be conducted.

Publications

• Card, Marcella L., Yu-Ping Chin, and Linda S. Lee. 2012. Prediction and experimental evaluation of soil sorption by natural hormones and hormone mimics. J. Food Agric. Chem., 60, 1480-1487.
• Dasu, K., J. Liu and L.S. Lee. 2011. Aerobic Soil Biodegradation of 8:2 Fluorotelomer Stearate Monoester Degradation. Environ. Sci. Technol., Web-released, DOI: 10.1021/es203978g.
• Gall, H., S. Sassman, L.S. Lee, and C. Jafvert. 2011. Hormone Chemograph Behavior in a Tile Drained Agroecosystem Receiving Animal Wastes. Environ. Sci. Technol., 45:8755-8764.

Progress 10/01/10 to 09/30/11

Outputs
OUTPUTS: We continue to conduct research on manure-born hormones and biosolid-born pharmaceuticals, which we have reported under (IND050018R2) and will not dual report here. We continue to conduct research on manure-born hormones and biosolid-born pharmaceuticals, which we have reported under (IND050018R2) and will not dual report here. Likewise our work on predicting the propagation of hormone from a CFAO source zone into a watershed and assessing in-stream biogeochemical processes attenuating hormones during transport will be reported under (IND010818G) and not dual reported here. We have recently concluded our experimental efforts in elucidating the potential sources of global perfluorochemical contamination with a focus on biotransformation of model fluorotelomer-based monomers representative of the monomers used commercially in producing polymers and stain guard resistant coatings among other uses. These products are suspected to contain or degrade into fluorotelomer alcohols (FTOHs) and subsequently into perfluorocarboxylates (PFCAs) including perfluorooctanoate (PFOA), which has been globally detected in wildlife, humans and the environment. We concluded our evaluation of the stability and aerobic transformation potential in soils of several perfluorotelomers including 8:2 fluorotelomer ester stearate (FTS), 8:2 fluorotelomer acrylate (PFA), fluorotelomer methyl acrylate (PFMA), toluene-2,4-di(8:2 fluorotelomer urethane) (FTU) and hexamethylene-1,6-di(8:2 fluorotelomer urethane) (HMU). Rates of aerobic biotransformation for these different monomers were quantified in different soils, and analog-induced biotransformation was probed for FTU using a non-fluorinated urethane with the same backbone. At each sampling time, triplicate soil microcosms were extracted by sequential extraction and analyzed with LC/MS/MS or GC-MS/EI for FT monomers, FTOHs and acid metabolites. For all these monomers, biodegradation is hypothesized to occur by cleavage of the ester or urethane bond releasing 8:2 FTOH, which subsequently degrades to a series of perfluorinated acids. PARTICIPANTS: Linda S. Lee, Professor, GRY - project PI Suresh C. Rao, Professor, CE/AGRY - supported work on the surface water flux meter delvopment Ron Turco, Professor, AGRY - supported work on biotransformation studies Larry Nies, Professor, AGRY - supported work on biotransformation studies Laurel Royer, PhD student, AGRY, Purdue - conducted aerobic biodegradation studies with decafluoroacrylate and methacrylates. Kavitha Dasu, PhD student, AGRY, Purdue - conducted aerobic biodegradation studies with fluorotelomer urethane monomers Stephen Sassman, Analytical Chemist, AGRY, Purdue - developed analytical methods; conducted analysis on field samples; developing surface water flux meter. TARGET AUDIENCES: Target Audiences include regulators, farmers, industry personnel, and military personnel in addition to research scientists and students. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
Relative rates of biotransformation followed: FTA>> FTMA> FTS >>> TBC > FTU and HMU. FTA half lives are 3 to 6 days, FTMA half lives approaching 2 weeks, and FTS half-lives ranged from 5 d to 28 d depending on soil type and conditions. Slower degradation of TBC, FTU, and HMU is likely due to enzyme access hindered by the additional FT chains. Biodegradation of urethane linkages also appeared slower compared to the ester linkages and a half-life was not reached within the 6-month studies. PFOA was the dominant persistent acid metabolite produced in all studies and overall metabolite production was higher in the forest soil. Biotransformation of FTU in forest soil, where a non-fluorinated toluene-2,4-dicarbamic acid diethyl ester, TDAEE was added, enhanced degradation of FTU was not observed; however, PFOA production was greatly enhanced with each addition. Results of this research clearly show that FT monomers used as surfactants and in producing polymers can serve as an indirect source of persistent perfluorinated acids in the environment. The rates of cleavage were shown to be affected by the type of hydrocarbon backbone and the number of FT chains present. In addition, although these studies were not conducted long enough to see PFOA concentrations plateau, PFOA production was much less than observed in FTOH biotransformation studies. This mitigation is directly associated to the rate of cleavage, thus FTOH release rates, multiple competing metabolite pathways, increases in irreversible binding with increasing residence time, and microbial community diversity. Hence, overall PFOA production is likely to be much less from monomers, and therefore, even less from polymers. The data for these FT monomers will aid in estimating expected PFOA loads from such monomer residuals that may be present in FT polymers or formed by polymer breakdown as well as aiding in the prediction of FT polymer stability in soils.

Publications

• Dasu, K. 2011. EVALUATING THE BIOTRANSFORMATION POTENTIAL OF COMMERCIAL MODEL FLUOROTELOMER MONOMERS IN SOIL. PhD Dissertation, Purdue University,West Lafayette, IN
• Royer, L. 2011. An Investigation of the Biodegradation Potential of 8:2 Fluorotelomer Esters in Environmentally Relevant Systems, PhD Dissertation, Purdue University, West Lafayette, IN.
• Dasu, K.; Liu, J.; Lee, L. S. 2010. Biotransformation of 8:2 Fluorotelomer Monomers with Ester and Urethane Linkages in Aerobic Soils. 2010. Society of Environmental Toxicology and Chemistry (SETAC) North America 31st Annual meeting, Portland, Nov.7-11.
• Lee,L.S.; Dasu, K.; Royer, L.A., Liu, J.. 2011. Quantifying the Biotransformation Potential of Commercial Model Fluorotelomer Monomers in Aerobic Soils. 2010. Society of Environmental Toxicology and Chemistry (SETAC) North America 32nd Annual meeting, Boston, MA, Nov. 10-17, 2011.

Progress 11/29/09 to 11/30/10

Outputs
OUTPUTS: We continue to conduct research on manure-born hormones, which we have reported under (IND050018R2) and will not dual report here. We continued to make substantial progress on elucidating the potential sources of global perfluorochemical contamination with a focus on characterizing the physico-chemical properties of this chemical class as well as their microbial and fungal enzyme-based transformation in soils. Fluorotelomer-based compounds are highly fluorinated organics that are uniquely both hydrophobic and oleophobic, thus widely utilized in industrial and consumer products to change surface properties (e.g., rendering textile fabrics stain-resistant). These products are suspected to contain or degrade into fluorotelomer alcohols (FTOHs) and subsequently into perfluorocarboxylates (PFCAs) including perfluorooctanoate (PFOA), which has been globally detected in wildlife, humans and the environment. We evaluated the stability and aerobic transformation potential in soils of several perfluorotelomers including 8:2 fluorotelomer ester stearate (FTS), 8:2 fluorotelomer acrylate (PFA), fluorotelomer methyl acrylate (PFMA), 2,4-toluenediamine 8:2 fluorotelomer urethane (FTU) and 1,6-hexamethylene diamine 8:2 fluorotelomer urethane (HMU). For all these monomers, biodegradation is hypothesized to occur by cleavage of the ester or urethane bond releasing 8:2 FTOH, which subsequently degrades to a series of perfluorinated acids. Both parent and metabolites were measured. PMA had the shortest half life at 3 to 6 days followed by FTS and PFMA with half lives approaching 2 weeks. The urethane monomers appear to be relatively stable with no measurable biodegradation observed for FTU while degradation of HMU is very slow with only a small % of metabolites observed after 3 months. Solvent induced abiotic hydrolysis in the presence of residual enzymes was only significant for FTS even though both FTS and FTMA have similar biodegradation potential. Recently we initiated work on quantifying the release of selected organic compounds from the human pharmaceuticals and personal care products (PPCPs) group that may be present in biosolids that are land-applied. We have done some initial analysis of what PPCPs are present in some biosolid samples obtained from a wastewater treatment plant in Chicago. We also have conducted preliminary experiments to assess the release rate of triclocarban and triclosan (two antimicrobials) from the biosolids into an aqueous solution. Data is currently being processed. PARTICIPANTS: Linda S. Lee, Professor, GRY - project PI Suresh C. Rao, Professor, CE/AGRY - supported work on the surface water flux meter delvopment Ron Turco, Professor, AGRY - supported work on biotransformation studies Larry Nies, Professor, AGRY - supported work on biotransformation studies Laurel Royer, PhD student, AGRY, Purdue - conducted aerobic biodegradation studies with decafluoroacrylate and methylacrylates. Kavitha Dasu, PhD student, AGRY, Purdue - conducted aerobic biodegradation studies with fluortelomer urethan monomers Stephen Sassman, Analytical Chemist, AGRY, Purdue - developed anlaytical methds; conducted analysis on field samples; developing surface water flux meter. TARGET AUDIENCES: Target Audiences include regulators, farmers, industry personnel, and military personnel in addition to research scientists and students. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

Impacts
A variety of fluorotelomer monomers are commonly used directly or incorporated into polymeric materials that are used for oil and stain repellency in multiple commercial products. The ester linkages present in fluorotelomer surfactants and polymers are suspected to be unstable. In environmental media, slow rates of conversion to persistent perfluorinated carboxylates (PFCAs) have been noted. In our studies, we found that the selected fluorotelomer stearate esters and acrylates were highly biodegradable in aerobic soils with fluorotelomer alcohols (FTOHs) being released via biotic/abiotic hydrolysis followed by further transformation to PFCAs. The fluorotelomer urethanes appear to be relatively resistant to degradation especially the on associated to an aromatic hydrocarbon backbone. This study confirms that estimations of global PFCA emissions must include breakdown of at least low molecular weight FTOH-derived compounds, which to date have been ignored.

Publications

• Publications Dasu, K., L.A. Royer, J. Liu and L.S. Lee. 2010. Hydrolysis of Fluorotelomer Compounds Leading to Fluorotelomer Alcohol Production During Solvent Extractions of Soils. Chemosphere, 81:911-917.
• Presentation Abstracts Sassman, S.A., L.S. Lee, P. S. C. Rao, N. B. Basu, and S. J. Boland. 2010. A Passive Flux Meter for Estimation of Contaminant Flux in Streams, Ecological Sciences & Engineering Symposium: Bridging the Gap from Science to Policy: Technology, Environment, and Sustainable Development, West Lafayette, IN, October 27, 2010.
• Royer, L. A. and L.S. Lee. 2010. Degradation Potential of Fluorotelomer Acrylate and Methacrylate in Soil. SETAC 31st North America Annual Meeting, Portland, Oregon, Nov. 6-9, 2010.
• Dasu, K. and L.S. Lee. 2010. Biotransformation of 8:2 Fluorotelomer Monomers with Ester and Urethane Linkages in Aerobic Soils. SETAC 31st North America Annual Meeting, Portland, Oregon, Nov. 6-9, 2010.
• Sassman, S. A., L. S. Lee, P. S. C. Rao, and C. A. Stinson. 2010. A New Passive Flux Meter for Sampling Environmental Contaminants in Surface Waters. SETAC 31st North America Annual Meeting, Portland, Oregon, Nov. 6-9, 2010. Lee, L.S., H. Gall, C. Jafvert, S. Sassman1, J. Leet, and M. Sepulveda. 2010. Endocrine Disrupting Compounds from Agricultural Fields under Various Manure Management Practices. What is in Our Water: The Significance of Trace Organic Compounds. The 3rd Australian Symposium on Endocrine Disrupting Chemicals (EDCs), Pharmaceuticals and Personal Care Products (PPCPs). Nov. 8-10, 2010.

Progress 12/15/08 to 12/14/09

Outputs
OUTPUTS: We continue to conduct research on manure-born hormones as well as on one antibiotic ciprofloxacin, which we have reported under (IND050018R2) and will not dual report here. We continued to make substantial progress on elucidating the potential sources of global perfluorochemical contamination with a focus on characterizing the physico-chemical properties of this chemical class as well as their microbial and fungal enzyme-based transformation in soils. Fluorotelomer-based compounds are highly fluorinated organics that are uniquely both hydrophobic and oleophobic, thus widely utilized in industrial and consumer products to change surface properties (e.g., rendering textile fabrics stain-resistant). These products are suspected to contain or degrade into fluorotelomer alcohols (FTOHs) and subsequently into perfluorocarboxylates (PFCAs) including perfluorooctanoate (PFOA), which has been globally detected in wildlife, humans and the environment. We evaluated the stability and potential transformation in soils of a purified 8:2 FTS derived from only 8:2 FTOH, fluorotelomer stearate mono-ester (FTS), citrate tri-ester (FTC) mixtures, perfluorodecyl acrylate (PFDA), and a fluorotelomer urethane monomer to FTOHs and subsequently PFCAs. Cleavage did occur for 8:2 FTS, the FTS mixture, and the PFDA generating FTOHs above residual levels, and, subsequently, a series of fluorinated acids typical of 8:2 FTOH biotransformation. Estimated half lives for FTS ranged between 0.5 and 1 year, about one week for PFDA, and close to 3 years for FTCs. The much higher stability of FTCs is attributed to steric hindrances invoked by the higher perfluorochain density, thus reducing accessibility to ester linkages. FTU also exhibited a high stability, which is attributed to the higher stability of carbamic acid ester bond. During our studies, we observed a rare solvent-enhanced hydrolysis of the ester linkage in the presence of soil, and the phenomenon was found to be dependent upon solvent type, soil type and soil moisture content. Results between unsterile, autoclaved soils, irradiated soils, no-soil controls, and addition of FTS after in soil extracts support our hypothesis that soil surfaces and extracellular microbial enzymes catalyze ester hydrolysis which can be solvent-enhanced. Acetonitrile and methanol greatly enhanced these catalysis reactions whereas MTBE and ethyl acetate did not enhance hydrolysis significantly. The impact of the solvent was also very dependent on the particular fluorotelomer surfactant with FTS being the most sensitive similar to its higher biotransformation potential. PARTICIPANTS: Laurel Royer, PhD student, AGRY, Purdue - conducted aerobic biodegradation studies with decafluoroacrylate and methylacrylates. Kavitha Daus, PhD student, AGRY, Purdue - conducted aerobic biodegradation studies with fluortelomer urethan monomers Michael Mashtare, NRES undergraduate and now PhD student, AGRY, Purdue - conducted sorption studies of the estradiol isomers Jillian Brown, NRES, undergraduate - conducted studies on photlysis of ciproflooxacin Nadia Carmosini, PhD student, AGRY, Purdue - conducted studies involving antibiotic and fluorotelomer alcohol assoication with dissolved organic matter; measured octanol-water partition coefficients for a series of telomer alcohols. Stephen Sassman, Analytical Chemist, AGRY, Purdue - developed anlaytical methds; conducted hormone analysis on field samples; conducted sorption and degradaiton studies of antibiotics. Byron Jenkinson, PhD, Jenkinson Environmental Services, LLC, West Lafayette, IN 47906 - aided in design and installation of stream and tile water sampling stations in the field at the ASREC and the WQFS. Chad Jafvert, Professor, CIVIL, Purdue - designed water flow monitoring stations for stream and tile flow and wireless network for collecting data remotely. Heather Preisandez, Summer Research Student and subsequently an MS graduate student, CIVIL, Purdue - assisted Dr. Javfert (above) and prepared and installed data logger programs for auotmated sample and data collection. Marisol Sepulveda, Assistant Professor, FNR - oversees all work on fish communities and biomarker impacts CAFO-derived constituents Animal Science Research and Education Center (ASREC) Staff, Purdue - facilitated research on the farm associated with ASREC. TARGET AUDIENCES: Target Audiences include regulators, farmers, and industry personnel in addition to research scientists and students. PROJECT MODIFICATIONS: We recently had a USDA Water and Watersheds project funded that will investigate how hormone loads discharged to streams from tile drains propagate into the watershed and if the there are significant changes in the hormone metabolites during residence in stream sediments.

Impacts
Fluorotelomer surfactants (FTS) and polymeric materials are commonly used for oil and stain repellency in multiple commercial products. The ester linkages present in fluorotelomer surfactants and polymers are suspected to be unstable. In environmental media, slow rates of conversion to persistent perfluorinated carboxylates (PFCAs) have been noted. In our studies, we found that the selected fluorotelomer stearate esters and the perfluorodecyl acrylate were unstable in aerobic soils with fluorotelomer alcohols (FTOHs) being released via biotic/abiotic hydrolysis followed by further transformation to PFCAs. The fluorotelomer citrate esters and the fluorotelomer urethane monomer appear to be at least an order of magnitude more stable. This study confirms that estimations of global PFCA emissions must include breakdown of at least low molecular weight FTOH-derived compounds, which to date have been ignored. Fluorotelomer surfactants (FTS) and polymeric materials are commonly used in multiple commercial products as a stain guard as well as reduced flammability (clothing, fire-fighting foams, etc.). The ester linkages present in fluorotelomer surfactants and polymers are suspected to be unstable. In environmental media, slow conversion to persistent perfluorinated carboxylates (PFCAs) have been noted, which has sparked several laboratory-based studies that are trying to quantify the persistence of these perfluorinated materials in soils and biosolids for which fluorotelomer alcohol (FTOH) is the first metabolite produced, which rapidly biotranforms to persistent perfluorinated carboxylates (PFCAs). During our biotransformation work, we learned of a rare solvent-enhanced hydrolysis of the ester linkages in some of the perfluorinated materials during soil extraction causing release of FTOHs. Such experimental artifacts, if unidentified, lead to biased conclusions. Also there are clear implications regarding the potential for producing mobile perfluorinated products at sites where solvents are also present or used in solvent flushing remediation such as military fire-training areas where fire-fighting foams containing perfluorinated surfactants were used repeatedly to put out fuel fires.

Publications

• Publications Khan, B. and L. S. Lee. 2009. Soil Temperature and Moisture Effects on the Persistence of Synthetic Androgen 17alpha-Trenbolone, 17beta-Trenbolone and Trendione, Chemosphere, (Accepted with minor revisions).
• Hyun, S. and L.S. Lee. 2009. Phenanthrene and 2, 2', 5, 5'-PCB Sorption by Several Soils from Methanol-water Solutions: The Effect of Weathering and Solute Structure. Chemosphere, (In press).
• Khan, Bushra, Xianliang Qiao, and Linda S. Lee. 2009. Stereo-selective Sorption by Agricultural Soils and Liquid-Liquid Partitioning of Trenbolone (17alpha and 17beta) and Trendione. Environ. Sci. Technol. 43:8827-8833.
• Carmosini, N. and L.S. Lee. 2009. Sorption of an Amphoteric Pharmaceutical Ciprofloxacin by Diverse Types of Dissolved Organic Carbon. Chemosphere (Web released, July 2008).
• Ralston-Hooper, K., J. Hardy, L. Hahn, H. Ochoa-Acuna, L.S. Lee, R. Mollenhauer, and M. S. Sepulveda. 2009. Acute and Chronic Toxicity of Atrazine and its Metabolites Deethylatrazine and Deisopropylatrazine on Aquatic Organisms, Ecotoxicology, (In Press). Carmosini, N. and L.S. Lee. 2008. Partitioning of Fluorotelomer Alcohols to Different Sources of Dissolved Organic Carbon. Environ. Sci. Technol. 42: 6550-6556.
• Goldberg, S., S, Hyun, and L.S. Lee. 2008. Chemical Modeling of As(III,V) and Se(IV,VI) adsorption by soils surrounding ash disposal facilities. Vadose Zone J., 7(4):1231-1238.
• Presentations Gall, H.E., Jafvert, C.T., Lee, L.S. Nutrient Fluxes in Agricultural Tile-Drains and Ditches, poster presented at the Indiana Environmental Health Summit, Indianapolis, IN, May 15, 2009.
• Gall, H.E., Jafvert, C.T., Lee, L.S., Jenkinson, B. Real-Time Monitoring and Automated Sampling of Tile-Drains and Near-Field Streams, poster presented at the Ohio Valley Chapter of Science of Environmental Toxicology and Chemistry (SETAC), Oct. 3, 2008.
• Lee, L.S. (2009) Discharge from and Persistence in Hormones from Tile‐drained Fields Receiving Animal Wastes, EmCon2009, , Fort Collins, CO, USA. August 4-7, 2009.
• Khan, B. and L. S. Lee (2009) Monitoring Androgens, Estrogens, and their Metabolites in Manure from Trenbolone Acetate Implanted Cattle and Manure-Receiving Lagoons. SETAC 30th North America Annual Meeting, New Orleans, Louisiana, November 19-23.
• Rogers, S., J.L. Meyer, L.S. Lee, D. Villeneuve, G. Ankley, and M.S. Sepulveda (2009) Plasma vitellogenin and hormone levels in common snapping turtles (Chelydra serpentina) from concentrated animal feeding operation (CAFO) ponds versus a reference site. SETAC 30th North America Annual Meeting, New Orleans, Louisiana, November 19-23.
• Dasu, K. And L.S. Lee (20009) Hydrolysis of Fluorotelomer Compounds During Soil Extraction. SETAC 30th North America Annual Meeting, New Orleans, Louisiana, November 19-23.
• Mashtare, M. And L.S. Lee (2009) Evaluating Stereospecific Sorption by Soils of 17alpha and 17beta-estradiol. SETAC 30th North America Annual Meeting, New Orleans, Louisiana, November 19-23.
• Leet, J.K., A. McAlexander, L. S. Lee, R. R. Goforth, and M. S. Sepulveda. (2009) Impacts of Land-Applied Wastes from Concentrated Animal Feeding Operations on Fish Communities. 70th Fish and Wildlife Conference, Foundation for the Future of Fish and Wildlife Management.

Progress 10/01/07 to 09/30/08

Outputs
OUTPUTS: We continue to conduct research on manure-born hormones as well as on one veterinary antibiotic ciprofloxin, which we have reported under (IND050018R2) and will not dual report here. We continued to make substantial progress on elucidating the potential sources of global perfluorochemical contamination with a focus on characterizing the physico-chemical properties of this chemical class as well as their microbial and fungal enzyme-based transformation in soils. Fluorotelomer-based compounds are highly fluorinated organics that are uniquely both hydrophobic and oleophobic, thus widely utilized in industrial and consumer products to change surface properties (e.g., rendering textile fabrics stain-resistant). These products are suspected to contain or degrade into fluorotelomer alcohols (FTOHs) and subsequently into perfluorocarboxylates (PFCAs) including perfluorooctanoate (PFOA), which has been globally detected in wildlife, humans and the environment. Interest in the environmental fate of fluorotelomer alcohols (FTOHs) has spurred efforts to understand their partitioning behavior. We measured the partitioning of 8:2 and 6:2 FTOH between one or more types of DOC and water (Kdoc) using enhanced solubility or dialysis bag techniques, and also quantified octanol/water partition coefficients (Kow) for 4:2 to 8:2 FTOH using a batch equilibration method. The range in measured log Kdoc values for 8:2 FTOH with DOC derived from two soils, two biosolids, and three reference humic acids is 2.00 to 4 with the lowest values obtained for the biosolids and for a value for 6:2 FTOH and Aldrich humic acid is 1.96 +/- 0.45. These average values (biosolid DOC excluded) are ~1 to 2 log units lower than previous indirect estimates. Overall, the affinity for DOC tends to be slightly lower than that for particulate soil organic carbon. Measured log Kow values for 4:2 (3.30 +/- 0.04), 6:2 (4.54 +/- 0.01), and 8:2 FTOH (5.58 +/- 0.06) was in good agreement with previously reported estimates. Using relationships between experimentally-measured partition coefficients and C-atom chain length, we estimated Kdoc and Kow values for shorter and longer chain FTOHs, respectively, that we were unable to measure experimentally. We evaluated the stability and potential transformation in soils of a purified 8:2 FTS derived from only 8:2 FTOH, fluorotelomer stearate mono-ester (FTS), citrate tri-ester (FTC) mixtures, and perfluorodecyl acrylate (PFDA) to FTOHs and subsequently PFCAs. Cleavage did occur for 8:2 FTS, the FTS mixture, and the PFDA generating FTOHs above residual levels, and, subsequently, a series of fluorinated acids typical of 8:2 FTOH biotransformation. The FTCs exhibited much higher stability, which is likely due to steric hindrances invoked by their larger molecular size, thus reducing accessibility to ester linkages. Concurrent degradation of residual FTOHs confounded a definitive determination of if and how much cleavage of the tri-ester occurred. Air-borne FTOHs resulting from the ester cleavage were found to be insignificant, which we attribute to the static nature of batch systems and the strong FTOH-interaction with soils. PARTICIPANTS: Jin Liu - conducted fluorotelomer alcohol sorption and solubility experiments; conducted aerobic biodegradation studies with fluorotelomer alcohol and three fluorotelomer stearate esters and citrate esters. Laurel Royer - conducted aerobic biodegradation studies with decafluoroacrylate and methylacrylates. Bushra Khan, PhD student, AGRY, Purdue - conducted sorption and degradation studies of the synthetic androgen. Nadia Carmosini, PhD student, AGRY, Purdue - conducted studies involving antibiotic and fluorotelomer alcohol assoication with dissolved organic matter; measured octanol-water partition coefficients for a series of telomer alcohols. Stephen Sassman, Analytical Chemist, AGRY, Purdue - developed anlaytical methds; conducted hormone analysis on field samples; conducted sorption and degradaiton studies of antibiotics. Byron Jenkinson, PhD, Jenkinson Environmental Services, LLC, West Lafayette, IN 47906 - aided in design and installation of stream and tile water sampling stations in the field at the ASREC and the WQFS. Chad Jafvert, Professor, CIVIL, Purdue - designed water flow monitoring stations for stream and tile flow and wireless network for collecting data remotely. Heather Preisandez, Summer Research Student and subsequently an MS graduate student, CIVIL, Purdue - assisted Dr. Javfert (above) and prepared and installed data logger programs for auotmated sample and data collection. Aaron McAlexander, Undergraduate, FNR - assessed the diversity of the fish communities Marisol Sepulveda, Assistant Professor, FNR - oversees all work on fish communities and biomarker impacts CAFO-derived constituents Animal Science Research and Education Center (ASREC) Staff, Purdue - facilitated research on the farm associated with ASREC. TARGET AUDIENCES: Federal regulators, solid waste partners, and science peers. PROJECT MODIFICATIONS: None except that B. Engel and G.S. Rao listed as a collaborating faculty member on this project should be removed.

Impacts
Fluorotelomer surfactants (FTS) and polymeric materials are commonly used for oil and stain repellency in multiple commercial products. The ester linkages present in fluorotelomer surfactants and polymers are suspected to be unstable. Slow rates of FTOH conversion to persistent perfluorinated carboxylates (PFCAs) have been noted. In our studies, we found that the selected fluorotelomer stearate esters and the perfluorodecyl acrylate were unstable in aerobic soils with fluorotelomer alcohols (FTOHs) being released via biotic/abiotic hydrolysis followed by further transformation to PFCAs. Stability of the larger fluorotelomer citrate esters was greater. This study confirms that estimations of global PFCA emissions must include breakdown of at least low molecular weight FTOH-derived compounds, which to date have been ignored. Perfluorinated compounds are used in the manufacturing of multiple products of which one product line is stain-guard products. Telomer alcohols (FTOHs), which are starting blocks in the production of stain-guard products, can be inadvertently released to the environment in manufacturing process or as non-point source pollution in the use, cleaning, and disposal of carpets. From our studies, sorption of FTOHs to various dissolved organic carbon (DOC) sources can span two orders of magnitude. Given the typical range of DOC in soils and biosolids, in most cases, DOC-enhanced mobility will be small to negligible. However, DOC concentrations up to 1000 mg DOC/L have been measured for landfill leachates, which leads to potential reductions ranging from ~10% to 90% based on our lowest and highest DOC-water partition coefficient measured. The overall impact of DOC will be attenuated by degradation and irreversible binding processes to soils and materials in the landfill.

Publications

• Khan, B., S.A. Sassman, and L.S. Lee. 2008. Degradation 17α- and 17β-Trenbolone and Trendione in Agricultural Soils. Environ. Sci. Technol., 42:3570-3574.
• Carmosini, N. and L. S. Lee. 2007. Sorption and Degradation of Selected Pharmaceuticals in Soil and Manure, IN: Fate of Pharmaceuticals in the Environment and Water Treatment Systems. CRC Press, pp. 139-166.
• Carmosini, N. and L.S. Lee. 2008. Partitioning of Fluorotelomer Alcohols to Different Sources of Dissolved Organic Carbon. Environ. Sci. Technol. Web released, July 2008.
• Liu, J., L.S. Lee, L.F. Nies, C.H. Nakatsu and R.F. Turco. 2007. Biotransformation of 8:2 Fluorotelomer Alcohol in Soil and by Soil Bacteria Isolates. Environ. Sci. Technol. 2007; 41(23); 8024-8030. DOI: 10.1021/es0708722.
• Lee, L.S. 2008. Emerging Environmental Concerns with Manure Management: Antimicrobials, Antibiotic-Resistant Bacteria, and Hormones. Crops and Soils Magazine (for the Practicing Professional), March.
• Presentations Khan, B. and Lee, L.S. (2007) Soil Temperature and Moisture Effects on Persistence of 17-Trenbolone and Trendione. SETAC 29th North America Annual Meeting, Tampa, FL, Nov. 16-20.
• Carmosini, N and Lee, L.S. (2008) Sorption of an Ionizable Antibioitc Ciprofloxacin to Environmetnally Relevant Dissolved Organic Carbon Materials. SETAC 29th North America Annual Meeting, Tampa, FL, Nov. 16-20.
• Durhan, E., V. Wilson, M. Sepulveda, D. Martinović, L. Lee, J. Lazorchak, C. Lambright, J. Cavallin, L. Blake, and G. Ankley. (2008) Sorption of an Ionizable Antibioitc Ciprofloxacin to Environmetnally Relevant Dissolved Organic Carbon Materials.Newer Anlaytical and Fractionation Apporaches for Detecting Endocrine-Active Chemcials in CATOs SETAC 29th North America Annual Meeting, Tampa, FL, Nov. 16-20.
• L.S. Lee, M Sepulveda, C. Jafvert, H. Gall, B. Khan, B. Jenkinson, and S. Sassman. (2008) Persistence and Discharge of Hormones from Tile-drained Fields Receiving Animal Wastes and their Impact to Aquatic Organisms. EPA STAR EDC Progress Review, Tampa, FL, Nov. 16.
• Lee, L.S. (2008). Stereo-specific Sorption of Trenbolone and Estradiol Isomers. Invited symposium talk in: Organic Contaminants: The Soil and Sediment Reserve. Joint 2008 Meeting of the Trisocieties (ASA, CSSA, SSSA) and Geological Societies (GSA, GSHGS, HGS), Houston, TX, Oct. 5-9
• Gall, H., C. Jafvert, L.S. Lee, and B. Jenkinson. (2008). Real-Time Monitoring and Automated Sampling in Agricultural Tile-Drains and Near-Field Streams. OVC SETAC meeting. Pharmaceuticals and Personal CareProducts in the Environment:What are the risks, and are actions needed Oct. 3.
• McAlexander, A. L.S. Lee, R. Goforth, and M. Sepulveda. (2008). Impacts of Concentrated Animal Feeding Operations on Fish Communities. 69th Fish and Wildlife Conference, Foundation for the Future of Fish and Wildlife Mangament, Columbus, OH, Dec. 14-17.

Progress 10/01/06 to 09/30/07

Outputs
OUTPUTS: We completed most of the work we have planned for sorption and degradation of antibiotics, but we continue to conduct research on manure-born hormones, which we have reported under (IND050018R2) and will not dual report here. We also continue to make substantial progress on elucidating the potential sources of perfluorochemical contamination observed globally with a focus on characterizing the unique properties of this chemical class and their fate in soils including sorption and microbial biotransformation. The fluorotelomer-based compounds are highly fluorinated organics that are uniquely both hydrophobic and oleophobic, thus widely utilized in industrial and consumer products to change surface properties (e.g., rendering textile fabrics stain-resistant). These products are suspected to contain or degrade into fluorotelomer alcohols (FTOHs) and subsequently into perfluorocarboxylates (PFCAs) including perfluorooctanoate, which has been globally detected in wildlife, humans and the environment. The solubility and sorption of 4:2 and 6:2 FTOHs were measured adequately in aqueous systems, while the higher homologues required the validation and use of a log-linear cosolvency model. The aqueous solubility of FTOHs and the non-fluorine homologues (n-alkanols) followed a single log-linear correlation with modified McGowan molar volumes. However, 8:2 and 10:2 FTOHs (solids at 25 C) exhibited smaller entropy of melt values than expected for long chain molecules. Sorption increased with increasing soil organic carbon (OC) and perfluorocarbon chain length. The aerobic microbial degradation of 8:2 FTOH was assessed by monitoring metabolites over time using liquid chromatography tandem mass spectrometry and included assessing the effect of carrier solvents (ethanol, octanol and 1,4-dioxane). With octanol (the structural analogue of 8:2 FTOH), transformation was temporarily inhibited until depletion of octanol. Similar results were observed with soil bacteria enriched from soil using sole octanol carbon source. In all cases biodegradation pathways appeared the same. Aerobic degradation behavior of perfluorodecyl methacrylate and acrylate monomers in soils was similar to 8:2 FTOH. For a subset of esters, cleavage of the fluorotelomer stearate mono-ester linkage with release of FTOHs occurred in soils with the subsequent generation of the fluorinated acids typical of 8:2 FTOH biotransformation, whereas the fluorotelomer citrate tri-esters appeared more stable. Novel solvent and soil-dependent abiotic hydrolysis was also observed. A handful of numerical studies have gleaned information on FTOH equilibrium partition coefficients between water, soil, and (DOC), direct measurements are lacking. We measured Kdoc/w values of 4:2 to 8:2 FTOH using solubility enhancement and dialysis techniques and environmentally-relevant DOC. Mean log Kdoc/w values for FTOH ranged between 0.37 and 5.54 with DOC derived from peats, biosolids, and soils. Mean log of the octanol-water partition coefficients (Kow) ranged from 3.33 to 6.63. These are the first reported Kdoc/w and Kow values ever reported for these compounds. PARTICIPANTS: Jin Liu - conducted fluorotelomer alcohol sorption and solubility experiments; conducted aerobic biodegradation studies with fluorotelomer alcohol and three fluorotelomer stearate esters and citrate esters. Laurel Royer - conducted aerobic biodegradation studies with decafluoroacrylate and methylacrylates. Bushra Khan, PhD student, AGRY, Purdue - conducted sorption and degradation studies of the synthetic androgen. Nadia Carmosini, PhD student, AGRY, Purdue - conducted studies involving antibiotic and fluorotelomer alcohol assoication with dissolved organic matter; measured octanol-water partition coefficients for a series of telomer alcohols. Stephen Sassman, Analytical Chemist, AGRY, Purdue - developed anlaytical methds; conducted hormone analysis on field samples; conducted sorption and degradaiton studies of antibiotics. Byron Jenkinson, PhD, Jenkinson Environmental Services, LLC, West Lafayette, IN 47906 - aided in design and installation of stream and tile water sampling stations in the field at the ASREC and the WQFS. Chad Jafvert, Professor, CIVIL, Purdue - designed water flow monitoring stations for stream and tile flow and wireless network for collecting data remotely. Heather Preisandez, Summer Research Student and subsequently an MS graduate student, CIVIL, Purdue - assisted Dr. Javfert (above) and prepared and installed data logger programs for auotmated sample and data collection. Animal Science Research and Education Center (ASREC) Staff, Purdue - facilitated research on the farm assoicated with ASREC. TARGET AUDIENCES: Scientists, industry, and regulatory agencies.

Impacts
Fluorotelomer surfactants (FTS) and polymeric materials are commonly used for oil and stain repellency in multiple commercial products. The ester linkages present in FTS and polymers are suspected to be unstable. Slow rates of fluorotelomer alcohol (FTOH) conversion to persistent perfluorinated carboxylates (PFCAs) have been noted. In our studies, we found that the selected fluorotelomer stearate ester surfactants were unstable in aerobic soils with FTOHs being released via biotic/abiotic hydrolysis followed by further transformation to PFCAs. This study confirms that estimations of global PFCA emissions must include breakdown of at least low molecular weight FTOH-derived compounds, which to date have been ignored. Perfluorinated compounds are used in the manufacturing of multiple products of which one product line is stain-guard products. Fluorotelomer alcohols (FTOHs), which are starting blocks in the production of stain-guard products, can be inadvertently released to the environment in manufacturing process or as non-point source pollution in the use, cleaning, and disposal of carpets. From our studies, sorption by soils of FTOHs appears high and solubility in water low, thus mobility in aqueous-soil systems will generally be minimal. However, these compounds were also found to highly associate with some sources of dissolved organic carbon, thus potential for facilitated transport exists.

Publications

• Lee, L.S., N. Carmosini, S.A. Sassman, H.M. Dion, and M. S. Sepuveda. 2007. Agricultural Contributions of Antimicrobials and Hormones on Soil and Water Quality, Adv. Agron. Volume 93, Chapter, pp. 1-68.
• Hyun, S. and L.S. Lee. 2007. Pentachlorophenol sorption by variable-charge soils in methanol-water mixtures: pH effect at the low solvent volume fraction. Chemosphere. (Web-released, July 2007).
• Liu, J., L.S. Lee, L.F. Nies, C.H. Nakatsu and R.F. Turco. 2007. Biotransformation of 8:2 Fluorotelomer Alcohol in Soil and by Soil Bacteria Isolates. Environ. Sci. Technol. (Web released, Nov 2007).
• Liu, J. and L.S. Lee. 2007. Effect of Perfluorocarbon Chain Length on Solubility and Sorption by Soils of Fluorotelomer Alcohols. Environ. Sci. Technol. 41(23): 8024-8030.
• Sassman, S. and L.S. Lee. 2007. Sorption and Degradation in Soil of Veterinary Ionophore Antibiotics: Monensin and Lasalocid. Environ. Toxicol. Chem. 26(8),1614-1621.
• Sassman, S., A.K. Sarmah, and L.S. Lee. 2007. Sorption and Degradation of Tylosin A, Tylosin D., and Tylosin A-Aldol in Soils. Environ. Toxicol. Chem. 26(8),1629-1635.
• von Kiparski, Guntram R., L. S. Lee, and A.R. Gillespie. 2007. Occurrence and Fate of the Phytotoxin Juglone in Alley Soils Under Black Walnut Trees. J. Environ. Qual., 36:709-717. Khan, B., Sassman, S.A., and Lee, L.S. (2007) Aerobic Degradation Rates and Pathways of 17alpha- and 17beta- Trenbolone in Agricultural Soils. SETAC 28th North America Annual Meeting, Milwaukie, Wisconsin, November 4-8.
• Royer, L. and Lee, L.S. (2007) Biotransformation of Perflourodecyl Acrylate and Perfluorodecyl Methacrylate in Aerobic Soils. SETAC 28th North America Annual Meeting, Milwaukie, Wisconsin, November 4-8.
• Carmosini, N and Lee, L.S. (2007) Partitioning of Fluorotelomer Alcohols to Octanol and Different Sources of Dissolved Organic Carbon. SETAC 28th North America Annual Meeting, Milwaukie, Wisconsin, November 4-8.
• Lee, L.S. and Sepulveda, M. 2007. Fate of Hormones in Tile-drained Fields and Impact to Aquatic Organisms Under Different Animal Waste Land-Applicaton Practices. EPA STAR CAFO Public Meeting, Chicago, IL, August 20-22, 2007. http://es.epa.gov/ncer/science/endocrine/reportspub.html
• Sassman, S.A. and L.S. Lee. (2007) Investigating the fate of the veterinary antibiotics monensin, lasalocid, and tylosin in agricultural soils. American Chemical Society 233rd National Meeting & Exposition, Chicago, IL USA, March 25-29.

Progress 10/01/05 to 09/30/06

Outputs
We continue to investigate the sorption and degradation of veterinary pharmaceuticals and perfluorinated including a synthetic androgen used in the beef industry (trenbolone) and its primary metabolite (trendione); two ionophore antibiotics monensin and lasalocid common to CAFOs and their primary metabolites, and three perfluorinated telomer surfactants (FTSs) in with cobalt-radiated and untreated soil systems. Both trenbolone isomers followed similar degradation pathways with degradation primarily, but not completely, being microbial, Concentration-dependent rates were observed with applied concentrations of 1 mg/kg giving half lives of 5-14 h whereas applied concentrations of 10 mg/kg resulted in longer half lives of 2-3 d. Some concentration dependence seemed apparent for trendione as well with half lives ranging from 3 to 4 d. Degradation of trendione generated from trenbolone was well predicted using rates estimated from independent trendione degradation studies. We recently monitored hormones in manures excreted by cattle implanted with Ravoler-S (140 mg TBA and 28 mg estradiol). Manure from the pits was sampled after mixing immediately prior to flushing to lagoons, which were sampled every 2 wks starting with the 4th wk after implanting. Trenbolone exhibited the highest hormone concentration in both the manure ( > 2 ug/L) and the lagoon (> 0.12 ug/L). Hormone concentrations in cell 2 were the greatest at 4 weeks after implants, but below 0.03 ug/L except for trendione ( 0.14 ug/L). For the antibiotics, organic carbon normalized sorption coefficients (log Koc) ranged from 1.53 - 3.67 for monensin and 2.89 - 4.30 for lasalocid and were negatively correlated to soil pH. Microbial degradation of both antibiotics occurred rapidly in soils with and without manure amendments with half lives of 1 to 2.1 d for monensin and 1.8 - 4.3 d for lasalocid. Preliminary testing of surface water and beef lagoon effluents showed monensin in the aqueous portion of the beef lagoon sample was found to be 40 ug/L while the suspended solids fraction contained 2000 ug/kg with 0.1 ug/L in the drainage ditch waters. Aerobic biotransformation of FTSs with ester linkages was assessed in soils using the purified 8:2 fluorotelomer stearate, a commercial mixture of fluorotelomer stearates (Zonyl FTS) and s commercial mixture of fluorotelomer citrates (Zonyl TBC). Breakdown to fluoroteleomer alcohols (FTOHs) in aerobic soils occurred at the ester linkage via biotic hydrolysis followed by and further transformed to perfluorocarboxylates. Increasing molecular size of the FTS slowed transformation. Most, but not all, 8:2 FTOH and metabolites produced in soil from Zonyl TBC was from residuals within the 2-mo incubation. Half-life of C-8 FTS is estimated to be < 213 ds based on only wt% recovered metabolite relative to applied parent. We also continue to evaluate the interactions of environmentally-relevant dissolved organic carbon (DOC) with emerging contaminants towards understanding facilitated transport of highly sorbed compounds. Mean log DOC-binding constants for FTOH ranged between 3.25 and 3.5 with various DOC derived from peats, biosolids, and soils.

Impacts
Fluorotelomer surfactants (FTS) and polymeric materials are commonly used for oil and stain repellency in multiple commercial products. The ester linkages present in fluorotelomer surfactants and polymers are suspected to be unstable. Slow rates of FTOH conversion to persistent perfluorinated carboxylates (PFCAs) have been noted. In our studies, we found that the selected fluorotelomer ester surfactants were unstable in aerobic soils with fluorotelomer alcohols (FTOHs) released via biotic/abiotic hydrolysis followed by further transformation to PFCAs. Slow production of PFCs from fluortelomer surfactants was observed; however, significant release from large polymer coatings on carpets seems unlikely given the observed trend of decreased transformation with increasing molecular size of the fluorotelomer-based compound.

Publications

• Liu, J. and L.S. Lee. 2005. Solubility and Sorption by Soils of 8:2 Fluorotelomer Alcohol in Water and Cosolvent Systems. Environ. Sci. Technol. 39:7535-7540.

Progress 10/01/04 to 09/30/05

Outputs
We continue to investigate the environmental fate of several chemical classes. Sorption and aerobic degradation with cobalt-radiated (sterile) and untreated soil-water slurries and moist microcosms of synthetic androgen used in the beef industry (trenbolone and its primary metabolite) and three antibiotics common to CAFOs were measured. Microbial degradation of trenbolone led to trendione with limited transformation in sterile soils. Trenbolone half lives across soils are less than 12 h. Subsequent degradation of trendione was slower than trenbolone degradation with a half lives for trendione of about 4 d across soils. Sorption of both trenbolone and trendione is reversible with equilibrium achieved in less than 20 h with rapid re-distribution of parent and metabolites as degradation proceeded. Sorption is primarily to soil organic carbon (OC) with organic-carbon normalized sorption coefficients (Koc) of 2000 to 4000 L/kg OC. Monensin and lasalocid sorption is pH-dependent with sorption being greater in acidic soils, but overall Koc values similar to the androgens. Half lives for monensin and lasalocid were 2 d and 4.3 d, respectively. Tylosin A, tylosin D, and tylosin aldol sorption is dependent on soil clay content and cation exchange capacity with sorption being similar for all forms of tylosin. Degradation experiments were conducted at room temperature (23 C) in moist soil microcosms with soil collected from an agricultural field which receives periodic manure application. After incubation, soils were extracted with methanol and the extracts were analyzed by LC-ESI-MS/MS. Tylosin A and tylosin D degrade had a similar half life of 7 - 8 d. Telomer-based polymers and surfactants serve as excellent surface modification and protective chemicals. However, they are suspected to degrade into perfluorinated acids (PFOA) during disposal and contribute to the global contamination in humans, wild life and environmental compartments. Sorption, solubility, and degradation of selected FTOHs were measured. Solubility and sorption were both log-linearly related to carbon number. The presences of dissolved organic carbon (DOC) was found to substantially reduce sorption of the 8:2 FTOH. Aerobic biotransformation of 8:2 FTOH in the presence of different organic co-substrates (methanol, ethanol, octanol, acetone, ethyl acetate, and 1,4-dioxane) led to 8:2 saturated and unsaturated acids in all cases. Degradation was fastest in the presence of dioxane, which did not degrade and slowest in the presence of octanol; degradation was limited until n-octanol was gone indicating similar enzymes in the degradation process and direct rather than co-metabolism of the FTOH. Cosolvent-enhanced nanoscale zero-valent and bimetal-zero valent iron dechlorination of PCBs in Aroclor 1242 contaminated sediments was evaluated. Nano-scale Fe/Pd (0.5% Pd) in 30%acetone completely dechlorinated Aroclor 1242 mixtures to biphenyl and chloride in solution within 2 min, and < 3 d in sediment. Bench-scale feasibility tests of in-situ injection of acetone-Fe/Pd in confined sediment facilities showed considerable promise for use of this approach for PCB remediation.

Impacts
Antibiotics and synthetic hormones used in animal production are excreted in the urine and feces, which are commonly land-applied. Some of these antibiotics have been found to be quite persistent in manure systems or present in water bodies. Our studies on the androgen trenbolone and the antibiotics tylosin, monension, and lasalocid indicate that these compounds are highly sorbed to soils or have relatively short half lives once applied to soils, thus entry into water bodies is likely to be small or only at low concentrations. Telomer alcohols are starting blocks in the production of stain-guard products, and can be inadvertently released to the environment in the manufacturing process or in the use, cleaning, and disposal of carpets. From our studies, sorption by soils of telomer alcohols is high and undergoes irreversible binding to the soils within short times suggesting that low mobility of the parent compounds. Some degradation to smaller and more mobile metabolites of potential concern was observed and is currently under further investigation. PCB contamination of soils and sediments remains widespread. Due to the low aqueous solubility, high sorption affinity, recalcitrance and environmental persistence of PCBs, remediation of PCBs from soils continues to be economically prohibitive. We developed a acetone-enhanced Pd coated nanoscale zero valent iron particle system that fully dechlorinated field aged PCB-contaminated sediments in less than 3 days in slurry systems. Bench-scale feasibility tests are now underway.

Publications

• Liu, J. and L.S. Lee. 2005. Determining Aqueous Solubility of Fluorotelomer Alcohols Using the Log-linear Cosolvency Model, SETAC North America 26th Annual Meeting, Baltimore, MD. November 13-17, 2005, Session B7, Invited Talk.
• Liu, J. and L.S. Lee. 2005. Determining Aqueous Solubility of Fluorotelomer Alcohols Using the Log-linear Cosolvency Model, FLUOROS Conference, Toronto, Canada, August 2005, Invited Poster.
• Liu, J. and L.S. Lee. 2005. Solubility and Sorption by Soils of 8:2 Fluorotelomer Alcohol in Water and Cosolvent Systems, Environ. Sci. Technol. 39:7535-7540.
• Liu, J., L. Nies, C. Nakatsu, L.S. Lee. 2005. Sorption and Biotransformation of 8:2 Fluorotelomer Alcohol by Surface Soils, SETAC North America 26th Annual Meeting, Baltimore, MD. November 13-17, 2005, Session B20, Invited Talk
• Murarka, Iswar P., Meiers, J, and Lee, Linda S. 2005. Leaching of Constituents inside a Coal Ash Filled Mine Pit and the Resulting Groundwater Quality in the Surrounding Environment.2005 World of Coal Ash, April 11-15, 2005, Lexington, Kentucky, USA.
• Sassman, S.A. and L.S. Lee. 2005. Sorption of Three Tetracyclines by Several Soil: Role of pH and Cation Exchange. Environ. Sci. Technol. 39: 7452-7459.
• Strock, T.J., S.A. Sassman, and L.S. Lee. 2005. Swine Antibiotic Carbadox and Associated N-Oxide Reduced Metabolites. Environ. Sci. Technol. 39:3134-3142.
• Xu, Tianbo. 2005. Effect of Zero Valent Metals and Water Miscible Solvents on Reductive Dechlorination of Polychlorinated Biphenyls. December 2005, Dissertation, Purdue University.
• Hyun, S. and L.S. Lee. 2004. Factors controlling sorption of prosulfuron by variable-charge soils and model Sorbents. J. Environ. Qual. 33:1354-1361.
• Hyun, S. and L.S. Lee. 2005. Quantifying the Contribution of Different Sorption Mechanisms for 2,4-Dichlorophenoxyacetic Acid Sorption by Variable-Charge Soils. Environ. Sci. Technol. 39:2522-2528.
• Khan, B., S. Sassman, and L.S. Lee. 2005. Sorption and Degradation of Trenbolone. SETAC North America 26th Annual Meeting, Baltimore, MD. November 13-17, 2005, Session B7, Poster.
• Lee, L.S. and S. Sassman. 2005. Investigating the Fate of Ionophore Antibiotics in Environmental Systems, SETAC North America 26th Annual Meeting, Baltimore, MD. November 13-17, 2005, Session B7, Poster.

Progress 10/01/03 to 09/29/04

Outputs
Using column and batch techniques we continue to investigate the environmental fate of various chemical classes including steroid hormones, antibiotics, and industrial chemicals. The fate of testosterone, trenbolone, and 17beta-estradiol were measured in unsterile (untreated) and cobalt-radiated (sterile) soil-water slurries for several soils to assess the role of biological versus abiotic processes in hormone transformation. For the androgens, degradation to the first major metabolite (androstenedione and trendione) appears primarily microbial whereas for estradiol, conversion to estrone appears primarily abiotic. We also attempted assess if the sorption coefficient we estimated previously in systems where substantial degradation occurred during equilibration approached near equilibrium. Although some differences were noted in sorption by sterile soil equilibrated for short times and unsterile soils equilibrated for long times, generally sorption coefficients were not statistically different. We also completed our work of the sorption of the swine antibiotic carbadox (CBX) and its primary metabolites by soils and CBX degradation in manure from CBX-fed swine. The organic carbon normalized sorption coefficients (Koc) of both CBX and bis-desoxycarbadox (DCBX) from 5 mM CaCl2 was measured to approach 10,000 L/kg. Although sorption appeared well correlated to soil OC, log-log correlations between Koc and octanol-water partition coefficients were poor. In addition, sorption of both CBX and DCBX is greater from a KCl solution than from CaCl2, and some competitive sorption between CBX and the reduced metabolites was observed indicating site-specific contributions to sorption comparable to electron-donor-acceptor type interactions. No CBX was detected in the fresh manure. DCBX was detected at no more than approximately 2.1 ug/kg manure and had a half-life in manure of one to two weeks. In a related study, we detected low-level concentrations of Deccox in recent beef lagoon effluent sampling and will be studying the fate of this compound over the next year. We have also been investigating the sorption by soils and solubility in cosolvent-water systems of Telomer alcohols (perfluorinated compounds used in the production of stain-guard products) in preparation for longer term degradation studies. We measured organic-carbon normalized sorption was in the 10,000+ L/kg range and confirmed that aqueous solubility is low as was previously reported. Low aqueous solubility and high sorption coefficients suggest minimal mobility of the parent compounds in aqueous-soil systems.

Impacts
Antibiotics used in animal production are excreted in the urine and feces, which are commonly applied to agricultural fields after an incubation period in a manure pond. Several of these antibiotics, e.g., chlortetracycline and oxytetracycline, have been found to be quite persistent in soil and manure systems. Our studies on tetracylcines, tylosin, and carbadox show that these compounds are highly sorbed to soils, thus their most likely entry into water bodies will be through spills, surface runoff, erosion, preferential flow, and facilitated transport. Perfluorinated compounds are used in the manufacturing of multiple products of which one product line is stain-guard products. Telomer alcohols, which are starting blocks in the production of stain-guard products, can be inadvertently released to the environment in manufacturing process or as non-point source pollution in the use, cleaning, and disposal of carpets. Form our studies, sorption by soils of Telomer alcohols appears high and solubility in water low suggesting that mobility of the parent compounds in aqueous-soil systems will be minimal.

Publications

• Lee, L.S., S.A. Sassman, R. F. Turco, and M. Bischoff. 2004. Degradation of N,N'-Dibutylurea (DBU) in soils treated with only DBU and DBU Fortified Benlate Fungicides, J. Environ. Qual., 33, 1771-1778.
• Sassman, S.A., L. S. Lee, M. Bischoff, and R. F. Turco. 2004. Assessing N,N'-Dibutylurea formation in soils after application of n-butylisocyanate and Benlate fungicides, J. Food Agric. Chem., 52:747-754.
• Pu, X., L.S. Lee, R.E. Galinsky, and G.P. Carlson. 2003. Evaluation of a rat model versus a physiologically based extraction test for assessing phenanthrene bioavailability from soils. J. Toxicol. Sci. 79:10-17.

Progress 10/01/02 to 09/30/03

Outputs
Using column and batch techniques we continue to investigate the environmental fate of various chemical classes including steroid hormones, antibiotics, pesticides, and industrial chemicals. Fate and transport of testosterone and 17 -estradiol were studied during steady, saturated water flow in columns packed with a surface soil, fresh-water sediment, and two sands. Degradation rate coefficients (k) for the hormones ranged from 0.003 to 0.015 h-1 for testosterone, and from 0.0003 to 0.075 for estradiol, similar to those observed in batch studies. Large sorption by soils of the parent and metabolites did not appear to hinder degradation. For veterinary pharmaceuticals, sorption studies were conducted with Tylosin A, Tylosin A aldol, chlortetracycline, oxytetracycline, and tetracycline in several soils representing a wide range in soil properties. Sorption was most influenced by cation exchange capacity and pH, and in some cases clay type. Currently, we are conducting a reconnaissance survey of streams and sediments in the Wabash and White River watersheds for pharmaceuticals. Sorption of 2,4-D, prosulfuron, and 5 chlorinated phenols were measured on several variable-charge soils from various electrolyte solutions as a function of pH. Relative contribution of anion exchange to the total amount sorbed was inversely proportional to chemical pKa and was significant even when pH>ZPC. Ca-bridging was found to be important for 2,4-D sorption by kaolinitic soils. Sorption of pi-electron donor compounds, pentamethylbenzene, naphthalene and phenanthrene, in a number of soils was found to increase with decreasing pH in the range of approximately pH 2.5 to 5.5. No significant effect of pH was observed for several non pi-donor hydrophobic compounds. Several factors were considered including pH-dependent alteration of the hydrophobic character of humic substances, H-bonding, compound coplanarity, and interaction with mineral surfaces; however, none were sufficient to explain the magnitude of acid-enhanced sorption. It is proposed that the pi-donors interact with pi-acceptor sites in soil organic matter (SOM), including aromatic rings with multiple carboxyl groups and N-heteroaromatic compounds, whose pi-accepting ability increases with protonation. The site-specific fate of ash leachate constituents and attenuation by soils is being investigated with a focus on quantifying the role of speciation, soil properties, and electrolyte composition (specifically calcium and sulfate typically present in ash leachate on the sorption of As, Se, and B from ash leachate. Both As(III) and As(V) are observed in ash leachate monitoring wells. Our studies indicate that As(V) is sorbed much greater than As(III) consistent with both field and column studies. Sorption is best correlated to easily reduced iron as determined by a 30 second mix with a dithionite citrate buffer. Sulfate decreases the sorption of As(V), As(III) and B sorption with the magnitude of the sulfate impact as follows: B >>> Se(VI) >> As(III) > As(V). High concentrations of calcium enhance As(V) sorption which tends to negate the small suppression by sulfate.

Impacts
Antibiotics used in animal production are excreted in the urine and feces, which are commonly applied to agricultural fields after an incubation period in a manure pond. Several of these antibiotics, e.g., chlortetracycline and oxytetracycline, have been found to be quite persistent in soil and manure systems. Our studies on tetracylcines, tylosin, and carbadox show that these compounds are highly sorbed to soils, thus their most likely entry into water bodies will be through spills, surface runoff, erosion, preferential flow, and facilitated transport. Our results show that for acidic pesticides used in variable charge soils typical of tropic and subtropic regions, the presence of inorganic anions such as calcium and phosphate, which are typically used to enhance soil fertility, have the potential to change pesticide mobility and must be considered in optimizing environmental stewardship. Arsenic in fly ash is expected to be primarily As(V), which is highly sorbed given the coal combustion process. However, As(III) is observed in fly ash leachate. We have shown that As(III) is much more mobile than As(V) and As(III) mobility is further enhanced in the presence of high sulfate concentrations typical of leachate from many ashes. Therefore, differentiating between As(III) and As(V) and considering ash leachate composition is imperative in assessing off-site transport of arsenic.

Publications

• Li, H., L.S. Lee, D.G. Schulze, and C. A. Guest. 2003. Role of Soil Manganese in the Oxidation of Aromatic Amines. Environ. Sci. Technol. , 37:2686-2793.
• Pu, X., L.S. Lee, and G.P. Carlson. 2003. Oral bioavailability of pentachlorophenol from soils of varying characteristics using a rat model. J. Toxicol. Environ. Health, 66:2001-2013.
• Lee, L.S., T. Strock, A. Sarmah, P.S.C. Rao. 2002. Simultaneous Sorption and Degradation of Reproductive Hormones and Their metabolites in Soils and Sediment, Environ. Sci. Technol. 37:4098-4105.
• Hyun, S., Lee, L.S, and P.S.C. Rao. 2003. Significance of Anion Exchange in Pentachlorophenol Sorption by Variable-Charge Soils. J. Environ. Qual. 32: 966-976.
• Sassman, S.A., and L.S. Lee. 2003. The effects of soil physical properties on sorption of tetracylcines. Annual American Society of Agronomy Conference, Denver, CO, November 2-6, 2003, p. 238.
• Sassman, S.A., L.S. Lee, A. Sarmah, and M. Oliveira. 2003. Sorption of tylosin A and tyloisn aldol in soils. Annual American Society of Agronomy Conference, Denver, CO, November 2-6, 2003, p. 240.
• Das, B.S., Lee, L.S., P.S.C. Rao. 2003. Lab-scale evaluation and modeling of steroid hormone fate during transport in soil columns. Annual American Society of Agronomy Conference, Denver, CO, November 2-6, 2003, p 238.
• Lee, L.S. 2003. Assessing the contribution of mineral surfaces in the sorption and transformation of ionizable organic chemicals. American Chemical Society 226th National Meetings, New York, New York, September 7-11, 2003.

Progress 10/01/01 to 09/30/02

Outputs
Using column and batch techniques we continue to investigate the environmental fate of various chemical classes including estrogens, androgens, antibiotics, pesticides, and industrial chemicals. For estradiol, ethynyl estradiol, and testosterone, sorption equilibrium was reached within a few hours and isotherms were generally linear, and organic carbon normalized sorption coefficients (Koc) were consistent with reported aqueous solubilities. Estimated half-lives for the parent compounds ranged from just a few hours to a few days. Similar studies were conducted for the swine antibiotic carbadox and its major metabolites. Carbadox sorption was well correlated to soil carbon, although preliminary evidence of competitive sorption, low Kow values, and unusual cosolvency behavior, suggests sorption mechanisms other than simple partitioning. Large log Koc values for all these compounds (3 to 4) suggest that retardation is likely to limit leaching losses in soils, and that a significant mass fraction of these compounds will be associated with sediments. Simulated swine manure pit studies wee conducted with manure from, tylosin- and carbadox-fed swine. Tylosin A aldol and OMT were the dominant metabolites in the manure and urine when first collected. The half-life for tylosin was 2-3 days. Metabolite concentrations continued to increase over much of the incubation period; thus they are most likely present in field-applied manure. After about 10 days in the simulated manure pits, primary metabolites began to dissipate. For carbadox-fed swine, desoxy carbadox was the only carbadox-derived compound found in measurable concentration in manure (40 to 80 ug/kg). Sorption of 2,4-D, prosulfuron, and five chlorinated phenols were measured on several variable-charge soils from aqueous solutions of CaCl2, CaSO4, and Ca(H2PO4)2 as a function of pH. Relative contribution of anion exchange to the total amount sorbed was inversely proportional to chemical pKa and was significant even when soil-solution pH > zero point of charge; thus, anionic interactions must be included to predict fate of acidic pesticides in tropical soils. Feasibility of using biofriendly solvents ethyl lactate and limonene for in-situ flushing of chlorinated solvents, gasoline, and diesel fuel is being investigated. The use of basic fly ash in reclamation of acid mine drainage impacted land is being evaluated using materials and monitoring well data from a strip mine site near Terre Haute, IN. Laboratory studies characterizing the processes controlling Mn release in soils and ash at three ash impoundment sites in Illinois suggests that Mn can be present in significant concentrations in coal ash leachate and in the pore-water of native soils, and both sources contributed to elevated Mn concentrations observed in groundwater near the impoundments.

Impacts
Desoxycarbadox is the only metabolite found in manure from carbadox-fed swine. Tylosin A and the primary metabolites tylsoin aldol and mycaminosyltylonolide (OMT) are present in manure from Tylan-fed swine. Compounds generally have relatively high sorption coefficients, making them unlikely candidates for normal leaching through typical agricultural soils. Our research suggests that any future reconnaissance of residual manure-applied antibiotics and associated metabolites should focus on the role of surface runoff, erosion, preferential flow, and facilitated transport to ecosystem loadings. Typical mammalian estrogens and androgens generally have relatively high sorption coefficients and short half-lives in soils and sediments from just a few hours to a few days. Leaching losses in soils are likely to be limited. On a mass fraction basis, such hormones will be associated with sediments, soils in manure-applied fields, and land-applied wastewater treatment biosolids. We have long understood that organic carbon content strongly influences the fate of pesticides in soils. Our results show that for acidic pesticides used in variable charge soils typical of tropic and subtropic regions, the presence of inorganic anions such as phosphate, which are typically used to enhance soil fertility, have the potential to increase pesticide mobility and must be considered in optimizing environmental stewardship.

Publications

• Hyun. S., L.S. Lee, P.S.C. Rao. 2002. Electrostatic Sorption of Acidic Organic Chemicals by Variable-Charge Soils as a Function of Chemical and Soil Charge Properties. Annual American Society of Agronomy Conference, Indianapolis, IN, November 10-14, 2002, p. 83. Abstract.
• Kolbe, J.L., L.S. Lee, C.T. Jafvert, I. Murarka, I.P. 2002. Use of Fly Ash in Acid Mine Reclamation: Arsenic Behavior" Annual American Society of Agronomy Conference, Indianapolis, IN, November 10-14, 2002, p. 300. Abstract.
• Lee, JS, L.S. Lee, P.S.C. Rao, L. Nies. 2002. Laboratory Assessment of Soil Flushing of Nonaqueous Phase Liquids with Ethyl Lactate and Limonene Solutions, Annual American Society of Agronomy Conference, Indianapolis, IN, November 10-14, 2002, p. 384. Abstract.
• Lee, L.S. 2002. Bioavailability of Organic Chemicals and Implications. Invited to be presented at the Bouyoucos Conference "Molecular Level Processes on Availability of Chemical Species to Plants and Microbes in Soil", Sani Halkidiki, Greece, June 23-28, 2002, p. 53. Abstract.
• EPRI. 2002. Manganese Occurrence Near Three Coal Ash Impoundments in Illinois. (Hensel, B., L.S. Lee, P. Burns, I. Murarka) Final Report # 1005257. - CD-ROM
• Lee, L.S., P.S.C. Rao. 2002. Sorption and Transport of Hormonally Active Agents in Soils. Annual American Society of Agronomy Conference, Indianapolis, IN, November 10-14, 2002, p. 187. Abstract.
• Oliveira, M., A.K. Sarmah, L.S. Lee, P.S.C. Rao. 2002. Fate of Tylosin in Aqueous Manure-Soil Systems, Annual American Society of Agronomy Conference, Indianapolis, IN, November 10-14, 2002, p. 386. Abstract.
• Oliveira, M., Prates, Santanna, Sans, L.S. Lee. 2002. Behavior of Imazaquin and Flazasulfuron in Brazilian soils. - Annual American Society of Agronomy Conference, Indianapolis, IN, November 10-14, 2002, p. 386. Abstract.
• Pu, XZ, Y.J. Zhao, L.S. Lee, A.P. Schwab, G.P. Carlson. 2002. Bioavailablity of Pentachlorophenol from Different Types of Soils, 41st Annual Meeting of the Society of Toxicology, March 18-22, 2002, The Toxicologist-Supplement of Toxicological Sciences. Vol. 66(1-S):138.
• Rao, P.S.C. and L.S. Lee. 2001. Investigations of Sorption and Transport of Hormones and Animal Pharmaceuticals: Initial Laboratory Results. EPA Workshop on "Effective Risk Management of Endocrine Disrupting Chemicals", Sept. 18-19, Cincinnati, OH. CD-ROM.
• Strock, T., R. Hultgren, L.S. Lee, P.S.C. Rao. 2002. Assessing the Mobility of Carbadox and Metabolites Through Soils: Batch Partitioning and Column Studies. Annual American Society of Agronomy Conference, Indianapolis, IN, November 10-14, 2002, p. 391. Abstract.
• Xu, T., L.S. Lee, P.S.C. Rao, C. Enfield, L, Nies. 2002. In-situ Oxygen Sensors for Use in Biotreatment of Fuel Oxygenates in Groundwater. Annual American Society of Agronomy Conference, Indianapolis, IN, November 10-14, 2002, p. 89. Abstract.

Progress 10/01/00 to 09/30/01

Outputs
Using column, batch, and spectroscopic techniques we have continued to investigate the environmental behavior of various chemical classes in soils. For pharmaceutical compounds tylosin, carbadox, B-estradiol and testosterone we have observed high sorption affinity to several soils representing a range of soil properties. Carbadox sorption correlates well to soil organic carbon (OC) content. Tylosin sorption correlates to a combination of soil OC, cation exchange capacity, and pH. For B-estradiol and testosterone, compound transformation was observed with increasing contact time with the soil. For tylosin, transformation was only observed in acid soils. Results suggest that downward mobility of these compounds as dissolved compounds in the pore-water is limited given sufficient time to interact with the soil when first applied, and likewise, compounds may reside in the soil profile for an extended period. For animal pharmaceuticals that are applied to the soil through manure application, the role of dissolved organic carbon on the mobility of theses compounds in soils is being investigated. We have characterized the role of anion exchange in sorption of acidic pesticides to several variable charge soils using phosphate as a competitor for anion exchange sites. The contribution of anion exchange to the overall sorption process is not a direct function of the soil's anion exchange capacity (AEC), but rather to the ratio of AEC to CEC. As the ratio of AEC to CEC increases, the contribution of anion exchange to the sorption process increases and AEC must be considered to make reasonable estimates of sorption to these soils. Previous work considered only OC and pH in predicting sorption. Application of phosphates is often needed for increasing fertility of highly weathered soils, thus potentially enhancing the mobility of previously applied acidic pesticides. Degradation and formation in soils of N,N'-dibutylurea (DBU), known to form during production and storage of benomyl, was investigated in moist soil microcosms as a function of concentration, temperature, moisture content, and soil type using C-14 labeled material. DBU half-lives were generally less than 2 weeks; however, degradation was much slower in high clay soils especially at lower moisture contents (1 bar). Sterile experiments indicate that DBU degradation is primarily microbial. Formation of DBU in soils from precursors was not observed under the conditions investigated. Feasibility of using biofriendly solvents ethyl lactate and limonene for in-situ flushing of both dense and light nonaqueous-phase liquids is being investigated. As part of this work the impacts of residual flushing solvents on microbial processes attenuating contaminant residuals not removed in the flushing process will be evaluated.

Impacts
The contamination potential of water supplies by animal pharmaceuticals present in manure applied to agricultural fields appears small except under cases of facilitated transport or preferential flow. Anion exchange of acidic pesticides must be considered in the management of variable-charge soils. DBU in soils is most likely from application of DBU-containing benomyl formulations and not from DBU production in soils, and that persistence of DBU in soils is short-lived.

Publications

• Li, H. L.S. Lee, C.T. Jafvert, and J. Fabrega. 2001. "Role of pH in Partitioning and Cation Exchange of Aromatic Amines on Soils, Chemosphere, 44:627-635.
• Seol, Y. and L.S. Lee. 2001. Coupled Effects of treated effluent irrigation and wetting/drying cycles on transport of triazines through unsaturated soil columns. J. Environ. Qual., 64:1976-1983.
• Fabrega, J., C.T. Jafvert, H. Li, and L.S. Lee. 2001. Modeling competitive cation exchange of aromatic amines in water-saturated soils. Environ. Sci. Technol., 35(13):2727-2733.
• Lee, L.S., C.T. Jafvert, H. Li, and J.R. Fabrega. 2000. Modeling soil-water distribution of aromatic amines in water saturated soil systems. EPA/600/S-99/005.
• Lee, L.S., H. Li, and D. G. Schulze. The role of clay-catalyzed reactions with aromatic amines in whole soils. Invited poster, Bouyoucus Conference "Environmental Chemistry at the Clay-Water Interface", Honolulu, Hawaii, March 6-9, 2000, p.11.
• Li, H., Lee, L.S., C. Guest, and D.G. Schulze. Role on Mn in Whole Soils on Abiotic Transformation of Aromatic Amines. Amer. Soc. Agronomy, Minneapolis, MN, November 5-9, 2000.
• Huang, X. and L.S. Lee. 2001. Effect of Dissolved Organic Matter from Animal Waste Effluent on Chlorpyrifos Sorption by Soils. J. of Environ. Qual., 30:1258-1256.

Progress 10/01/99 to 09/30/00

Outputs
Using column, batch, and spectroscopic techniques we have continued to investigate the environmental behavior of various chemical classes in soils. We have demonstrated for both polycyclic aromatic hydrocarbons and aromatic amines that as their residence time in the soil profile increases, the extractability, mobility, and bioavailability decreases. For polyaromatic hydrocarbons, decreased availability is primarily due to very slow desorption kinetics. For aromatic aromatic amines, covalent binding to organic matter occurs as well as soil manganese-catalyzed formation of aromatic amine polymers that are highly sorbed to soils and essentially immobile for all practical purposes. We have also focused on the use of bio-friendly solvents for the simultaneous extraction of both aromatic and chlorinated hydrocarbons as well as metals from contaminated soils. Recent work with ethyl lactate/water/lactic acid solutions have demonstrated its capacity to solubilize both chlorinated hydrocarbons and aromatic hydrocarbons, while also having a high propensity to extract metals from mixed metal-NAPL waste site soils. Addition of EDTA enhanced metal cation extraction, which was optimal at 0.02 M in 50 to 60% ethyl lactate solutions. Aqueous d-limonene/EZ-Mulse solutions (limonene is a biofriendly solvent derived from citrus peels) was assessed for its ability to extract residual tar from coal tar contaminated soils. Viscosity of the aqueous limonene solutions was within the acceptable limits for use as an in-situ flushing solvent.. The interfacial tensions between tar and the limonene solutions were in the range amenable for tar solubilization versus mobilization in soil systems. Aqueous solutions of approximately 5% limonene/EZ-Mulse removed as much tar as dichloromethane, an organic solvent used for analysis of total polyaromatic hydrocarbons from tar contaminated soils.

Impacts
Results of this research are applicable to optimizing soil remediation strategies, improving our assessment as to whether or not remediation is needed, defining environmentally acceptable endpoints with regards to soil clean up, and in better defining regulations with regards to chemical use.

Publications

• Li, H. and L.S. Lee. 1999. Sorption and abiotic transformation of aniline and a-naphthylamine by surface soils. Environmental Science & Technology, 33:1864-1870.
• Fabrega, J., C.T. Jafvert, H. Li, and L.S. Lee. 2000. Modeling abiotic processes of aniline in saturated soils. Environmental Science & Technology, 34:1687-1693.
• Li, H., L.S. Lee, C.T. Jafvert, and J.J. Graveel. 2000. Effect of substitution on irreversible binding and transformation of aromatic amines with soils in aqueous systems, Environmental Science & Technology, 34: 3674-3680.
• Huang, X., L. S. Lee, and C. Nakatsu. 2000. Impact of animal waste lagoon effluents on chlorpyrifos degradation in soils. Environmental Toxicology & Chemistry, Vol. 19, No. 12.
• Seol, Y. and L.S. Lee. 2000. Effect of dissolved organic matter from treated effluents of sorption of atrazine and prometryn by soils, Soil Science Society of America Journal, Vol. 64, No. 6.
• Li, H., L.S. Lee, C.T. Jafvert, and J. Fabrega. 2000. Role of pH in partitioning and cation exchange of aromatic amines on soils, Chemosphere. (In press).
• Lee, L.S. and I. Murarka. 1999. Estimating aqueous Release Concentrations of Multi-ring Aromatic Hydrocarbons from MGP Soils. EPRI Report, TR-110516 Vol. 2.
• Fabrega, J. 1999. Modeling Distribution of Aromatic Amines in Saturated Aqueous Systems. Ph.D. dissertation, Purdue University, West Lafayette, IN.
• Li, Hui. 1999. Sorption and Transformation of Aromatic Amines by Surface Soils in Aqueous Systems. Ph.D. dissertation, Purdue University, West Lafayette, IN.

Progress 10/01/98 to 09/30/99

Outputs
The magnitude and rates of various soil processes greatly affect the residence time of a contaminant within a reactive soil profile. Our work has focused on quantifying the magnitude and rates of the primary soil processes impacting aromatic amines, polyaromatic hydrocarbons (PAHs), and selected pesticides. For aromatic amines, reversible cation exchange and hydrophobic sorption processes reached equilibrium within the one-day for all soil-solute combinations. Both irreversible covalent binding and transformation became increasingly more significant with increasing contact times. Desorption of PAHs from several contaminated soils has been assessed using batch-rate, multiple flow-interrupt column, and steady-state flow column techniques. Currently, estimates of desorption rates are being obtained using both bicontinuum and distributed parameter sorption models. The potential impact of treated effluent irrigation on the fate and transport of two weakly basic triazines atrazine and prometryne, an organophosphate chlorpyrifos, and an organic acid 3,5,6-trichloro-2-pyridinol (TCP) a major chlorpyrifos metabolite was evaluated. The effects of DOM complexation correlated well to the polarity of both the DOM and pesticides with complexation increasing with decreasing polarity. Complexation with effluent DOM on enhanced transport was only significant for the most nonpolar pesticide chlorpyrifos; however, under most soil-effluent field conditions retardation of chlorpyrifos will still be sufficiently large such that chlorpyrifos will remain in the upper few inches of the soil profile. For the moderately polar pesticides, facilitated transport through complexation with effluent DOM is unlikely. However, some potential for enhanced transport can arise from effluent-induced increases in soil-solution pH resulting in a spciation shift to the more mobile specie, and decreases in pore-water velocity resulting in enhanced desorption of the soil-borne pesticides.

Impacts
For several organic compounds, release is greatly reduced over time such that soil contamination left on site without risk to the environment may be much greater than originally presumed. Irrigation with treated effluents can be optimized as a function of soil, pesticide and effluent properties such that the potential for enhanced transport from effluent dissolved organic matter, or effluent-induced changes in soil-solution pH and water flow is minimized.

Publications

• Seol, Y. 1998. An Inquiry into the Phenomenon of Enhanced Transport of Triazines with Treated Effluents. Ph.D. Dissertation, Purdue University, W. Lafayette, IN.
• Li, H. 1999. Sorption and Abiotic Reactions of Aromatic Amines in Aqueous Soil Systems. Ph.D. Dissertation, Purdue University, W. Lafayette, IN.
• Huang, X. 1999. Impact of Animal Derived Lagoon Effluents on the Fate of Chlorpyrifos and Metabolites in Soils. Ph.D. Dissertation, Purdue University, W. Lafayette, IN.
• Fabrega, J. 1999. Modeling Soil-Water Phase Transfer Processes of Aromatic Amines. Ph.D. Dissertation, Purdue University, W. Lafayette, IN.
• Lee, L.S. and I. Murarka. 1999. Estimating aqueous Release Concentrations of Multi-ring Aromatic Hydrocarbons from MGP Soils. EPRI Report, TR-110516 Vol. 2.

Progress 10/01/97 to 09/30/98

Outputs
The magnitude and rates of various soil processes greatly affect the residence time of a contaminant within a reactive soils profile, thus migration to a potable water supply and bioavailability. Our work has focused on identifying the primary soil processes, quantifying the magnitude and rates of these processes, and correlating these processes to easily obtainable soils and chemical properties for aromatic amines and polyaromatic hydrocarbons (PAHs). For aromatic amines, reversible sorption processes reached equilibrium within the one-day for all soil-solute combinations while irreversible binding and transformation proceeded for much longer times. Apparent increases in reversible sorption after one day were shown to primarily result from nonlinear sorption coupled to decreasing aqueous solute concentrations from irreversible binding/transformation. Sorption within a one-day contact time was successfully predicted with a distributed parameter model considering only cation exchange and hydrophobic sorption processes. Both irreversible covalent binding and transformation became increasingly more significant with increasing contact times. Reduction in aromatic amine solution concentrations by fast reversible sorption processes retarded irreversible reactions. For a few aromatic amines evidence of mineral-catalyzed dimerization was confirmed with GC/MS and UV-Vis detection. The rate and extent of both covalent binding and irreversible transformation reactions were correlated to solute nucleophilic activity and redox potential as well as soil pH, OC, and clay content. Desorption of PAHs from several contaminated soils has been assessed using both traditional batch and multiple flow-interrupt column techniques. Currently, estimates of desorption rates are being obtained using both bicontinuum and distributed parameter sorption models. Desorption rates obtained from batch and column techniques will be compared and correlated to soil and contaminant properties.

Impacts
(N/A)

Publications

• Lee, L.S., N.D. Priddy, and D.C.M. Augustijn. 1998. Estimating mass-transfer of polyaromatic hydrocarbons from coal-tar contaminated soil. IN: Soil and Aquifer Pollution: Non-Aqueous Phase Liquids - Contamination and Reclamation, H. Rubin and J. Carberry (eds.) Springer-Verlaag, Berlin, Germany, Chapter 6, p. 91-108
• Lee, L.S. 1998. Estimating release of polyaromatic hydrocarbons from coal tar contaminated soil at manufactured-gas plant sites. EPRI Report, TR-110516.
• Fabrega, J., C.T. Jafvert, H. Li, and L.S. Lee, 1998. Modeling soil-water phase transfer processes of organic bases. The First International Conference on Remediation of Chlorinated and Recalcitrant Compounds. Battelle Northwest, WA (May 18-21, 1998).
• Lee, L.S., E. Heyse, K. Gushurst, C. Biegel. 1998. Estimating the mass-transfer of polyaromatic hydrocarbons from coal-tar contaminated soils using batch-rate and flow interrupt techniques. American Geophysical Union, Special session "Sorption of organic pollutants to soil, sediment, and other geologic solids. Boston, MA. (May 26-29, 1998), p. S92.
• Li, H. and L.S. Lee. 1998. Long term sorption and reaction of selected aromatic amines by surface soils. American Geophysical Union, Special session "Sorption of organic pollutants to soil, sediment, and other geologic solids. Boston, MA. (May 26-29, 1998), p. S97.
• Li, H., L.S. Lee, J. Graveel, J. Fabrega, and C. Jafvert. 1998. Effect of substitution on the interaction of aromatic amines with soils in aqueous systems. Proceedings of the Environmental Sciences and Engineering Institute Symposium, Purdue University, West Lafayette, IN, (September 25, 1998), p. 16.
• Fabrega, J.R., C.T. Jafvert, H. Li, and L.S. Lee. 1998. Modeling soil-water distributions of aromatic amines at equilibrium. Environmental Sciences and Engineering Institute Symposium, Purdue University, West Lafayette, IN, (September 25, 1998), p. 17.
• Li, H., J. Fabrega, L.S. Lee, C. Jafvert, and J. Graveel. 1998. Effect of Substitution on the Interaction of Aromatic Amines with Soils in Aqueous Systems. 21st Midwest Environmental Chemistry Workshop, University of Michigan, Ann Arbor, MI, (October 16-18, 1998).
• Fabrega, J.R., C.T. Jafvert, H. Li, and L.S. Lee. 1998. Modeling soil-water distributions of aromatic amines at equilibrium. 21st Midwest Environmental Chemistry Workshop, University of Michigan, Ann Arbor, MI, (October 16-18, 1998).
• Fabrega, J., C.T. Jafvert, H. Li, and L.S. Lee. 1998. Modeling short-term soil-water phase distribution of aromatic amines. Environmental Science & Technology, 32:2788-2794.

Progress 10/01/96 to 09/30/97

Outputs
The magnitude and rates of various soil processes greatly affect the residence time of a contaminant within a reactive soils profile, thus migration to a potable water supply and bioavailability. Our work has focused on identifying the primary soil processes, quantifying the magnitude and rates of these processes, and correlating these processes to easily obtainable soils and chemical properties for organic bases and polyaromatic hydrocarbons (PAHs). For organic bases, soil solution pH appears to be the most significant factor controlling sorption in soil/water systems at early times (less than 24 hours) with cation exchange being the dominant sorption mechanism. As residence time proceeds, irreversible sorption becomes significant. We are currently looking at long time sorption of a set of four aromatic amines and five soils that represent a wide range of amine and soil properties. Results should enable us to correlate intrinsic solute reactivity and key soil properties to the magnitude and possibly rate of irreversible binding. Our work with several soils contaminated with PAHs the manufactured gas process (MGP) has suggested that sorption by these soils is up to an order of magnitude greater, and mass-transfer constraints as much three orders of magnitude lower relative to what may be predicted from short-term laboratory studies with artificially spiked natural soils. In order to more accurately define environmentally acceptable endpoints, regulators and personnel responsible for site clean-up need better assessment tools for evaluating the hazard potential of pesticides and industrial chemicals. Environmentally Acceptable Endpoints (EAE) refers to the level of contamination in the soil that is not harmful to the biological targets within the environment. Both the work with the organic amines and the PAHs suggest that the health risk potential for several compounds may be greatly reduced over time; therefore, the levels of soil contamination that can be left on site without risk to the environment may be much greater than originally presumed which would lower the cost of site remediation.

Impacts
(N/A)

Publications

• Li, H., A.K. Nyman, L.S. Lee, and C.T. Jafvert. 1997. Competitive sorption of selected aromatic amines by soils. Amer. Soc. Agronomy, CA (October 26-30, 1997), p. 187.
• Li, H., A.K. Nyman, L.S. Lee, and C.T. Jafvert. 1997. Sorption of aniline and 1-naphthylamine by five soils. 20th Midwest Environmental Chemistry Workshop, Indiana University, Bloomington, IN, (November 8-9, 1997).
• Li, H., A.K. Nyman, L.S. Lee, and C.T. Jafvert. 1997. Sorption of aniline and 1-naphthylamine by five soils. 20th Midwest Environmental Chemistry Workshop, Indiana University, Bloomington, IN, (November 8-9, 1997).
• Nyman, M.C., A. Nyman, L.S. Lee, L. Nies and E. Blatchley. 1997. Fate of 3,3'-dichlorobenzidine in lake systems. Environmental Science & Technology, 31:1068-1073.
• Regitano, J.B., M. Bischoff, L.S. Lee, M. Reichert, and R.F. Turco. 1997. Retention of imazaquin in soil. Environmental Toxicology & Chemistry, 16:397-404. Lee, L.S., A. K. Nyman, H. Li, M.C. Nyman, and C. Jafvert. 1997. Initial sorption of aromatic amines by surface soils. Environmental Toxicology & Chemistry, Vol. 16:1575-1582.
• Augustijn, D.C.M., L.S. Lee, R.E. Jessup, M. D. Annable, and P.S.C. Rao. 1997. Remediation of Soils Contaminated with Hydrophobic Organic Chemicals: Theoretical Basis for the Use of Cosolvents. In: Subsurface Restoration Handbook, C.H. Ward, J.A. Cherry, and M.R. Scalf (eds.), Ann Arbor Press, Inc., Chelsea, MI, Chapter 15, p. 227-244.
• Lee, L.S., N.D. Priddy, and D.C.M. Augustijn. 1997. Estimating mass-transfer of polyaromatic hydrocarbons from coal-tar contaminated soil. IN: Soil and Aquifer Pollution: Non-Aqueous Phase Liquids - Contamination and Reclamation, H. Rubin and J. Carberry (eds.) Springer-Verlaag, Berlin, Germany, (In Press).

Progress 10/01/95 to 09/30/96

Outputs
Long-term residence of coal-tar wastes within the soil profile and the slow desorption kinetics of organic chemicals from soils has resulted in much lower than expected release concentrations of polyaromtic hydrocarbons (PAHs)from coal-tar contaminated soils. Currently, site-specific assessments are being used to determine the level of soil contamination that can be allowed to remain on a site without posing a significant risk of contaminating the groundwater. Research on the interaction of organic contaminants with soils has been extended to include aromatic amines. Sorption mechanisms relevant to aromatic amines include cation-exchange of the organic cation; hydrophobic partitioning of the neutral organic base; and covalent bonding to functional groups on soil organic matter. The latter reaction can be irreversible, thus rendering the contaminants immobile. During relatively short residence times (24 hours)normalizing sorption to the cation-exchange capacity of the protonated species compensated for most of the differences observed between soils at different pH values suggesting that cation-exchange is the primary process occurring during initial contact times. In selected experiments, sorbed aromatic amines were extracted from soils with different solvents after a one-day incubation. At low initial concentrations (<0.01 mM) only a few percent of each amine was extractable; whereas 85% to 98% was recoverable at higher initial concentrations (1 mM). In long-term studies, sorption of aniline ap.

Impacts
(N/A)

Publications

• Nyman, M.C., A. Nyman, L.S. Lee, L. Nies and E. Blatchley. 1996. Fate of 3,3[-dichlorobenzidine in lake systems. Environmental Science & Technology, (In Press).
• Lee, L.S.*, N.D. Priddy, and D.C.M. Augustijn. 1996. Estimating mass-transfer of polyaromatic hydrocarbons from coal-tar contaminated soil. IN: Nonaqueous Phase Liquids: Contamination and Reclamation, H. Rubin and J. Carberry (eds.) Springe
• Priddy, N.D. 1996. Estimating release rates of polyaromatic hydrocarbons from coal-tar contaminated soil. M.S. Thesis, Purdue University, West Lafayette, IN. 107 pp.
• Lee, L.S. and Priddy, N. 1996. Estimating mass-transfer of polyaromatic hydrocarbons from coal-tar contaminated soil. Amer. Soc. Agronomy, Indianapolis,IN, (November 3-8, 1996), p. 193.
• Li, H., A.K. Nyman, and L.S. Lee. 1996. Long-term sorption of aniline and 1-naphthylamine by soils, Amer. Soc. Agronomy, Indianapolis, IN, (November 3-8, 1996), p. 212.
• Nyman, M.C., L.S. Lee, and E.R. Blatchley. 1996. Sorption of benzidine and DCB by lake sediment, Amer. Soc. Agronomy, Indianapolis, IN, (November 3-8, 1996), p. 211.

Progress 10/01/94 to 09/30/95

Outputs
Long-term residence of coal-tar wastes within the soil profile and the slow desorption kinetics of organic chemicals from soils has resulted in much lower than expected release concentrations of polyaromtic hydrocarbons from coal-tar contaminated soils. Currently, site-specific assessments are being used to determine the level of soil contamination that can be allowed to remain on a site without posing a significant risk of contaminating the groundwater. Research on the interaction of organic contaminants with soils has been extended to include aromatic amines. Sorption mechanisms relevant to aromatic amines include cation-exchange of the organic cation; hydrophobic partitioning of the neutral organic base; and covalent bonding to functional groups on soil organic matter. The latter reaction can be irreversible, thus rendering the contaminants immobile. Recent batch studies with aniline and 1-naphthylamine showed that substantial amounts of both compounds were unextractable within a single day equilibration indicative of rapid irreversible bond formation. Therefore, even for relatively short residence times within the reactive soil profile, the potential hazard of these contaminants could be reduced.

Impacts
(N/A)

Publications

Progress 10/01/93 to 09/30/94

Outputs
Equilibrium concentrations and release rates of several organic contaminants arebeing assessed for two coal-tar contaminated soils using low pressure chromatography systems and GC/FID analysis. Release rates of polyaromatic hydrocarbons from a soil matrix that has been in contact with coal-tar for several decades appear to be much slower than release of organic compounds from an uncontaminated soil matrix. Estimated release concentrations are also less than what would be predicted assuming mole fraction solubility. Slow rates of release and lower than expected equilibrium concentrations suggest that the coal tar does not reside as coatings on soil particles, but has become incorporated into the soil matrix. Research on the impact of the long term interaction of organic contaminants with soils will continue and be extended to include ionogenic organic chemicals such as the triazines and nitrogen heterocyclics.

Impacts
(N/A)

Publications

• LEE, L.S. 1994. Chemodynamics of Complex Mixtures. Abstract, Amer. Soc. Agronomy, Seattle, WA, (Nov. 13-18, 1994).
• PRIDDY, N.; LEE, L.S. 1994. Release of Polyaromatic Hydrocarbons from Coal-Tar Contaminated Soil. Abstract, Amer. Soc. Agronomy, Seattle, WA, (Nov. 13-18, 1994).

Progress 10/01/92 to 09/30/93

Outputs
A new laboratory equipped with an automated high performance liquid chromatograph and an automated gas chromatograph was set-up to initiate studies on equilibrium and nonequilibrium processes controlling organic contaminant behavior in soils and groundwater. Testing of the analytical systems in regards to standard operating procedures, accuracy, precision, and limits of detection for several organic compounds is currently in progress. Specific research on the impact of the long term interaction of organic contaminants with soils has been initiated. Preliminary results suggest that the longer an organic chemical has been in contact with the soil matrix prior to desorption, the slower the rates of release.

Impacts
(N/A)

Publications

• No publications reported this period.