Progress 10/01/06 to 09/30/10
Outputs
OUTPUTS: A field-scale study was conducted to assess the potential for runoff of seventeen different hormones, including androgens, estrogens, and progestogens from an agricultural field applied with biosolids and the major mechanisms controlling hormone transport during simulated rainfall events. Whole water runoff samples prior to biosolids application had low concentrations of a few hormones. In contrast, significantly higher concentrations of multiple estrogens, androgens, and progesterone were observed in runoff samples taken 1, 8 and 35 days after biosolids application. A significant positive correlation was observed between rainfall amount and hormone mass fluxes. Overall, these results indicate that rainfall can mobilize hormones from biosolids amended agricultural fields, and they could be transported directly to surface waters via runoff. A study was conducted to enrich manure-borne bacteria capable of testosterone degradation and to elucidate their testosterone degradation/mineralization pathways. Six DNA sequences of bacteria from the Proteobacteria phylum widely distributed among six different genera - Acinetobacter, Brevundimonas, Comamonas, Sphingomonas, Stenotrophomonas, and Rhodobacter were identified in a testosterone-degrading enriched culture suggesting that Proteobacteria may play an important environmental role in the degradation of testosterone and other similar structural compounds. Six degradation products of testosterone were identified as 9α-hydroxytestosterone (9α-OH-T), ADD, 9α-hydroxyandrostadienedione (9α-OH-ADD), 9α-hydroxyandrostenedione (9α-OH-AD), DHT, and AD based on the proposed formula and molecular mass of compounds and by consideration of the known patterns of testosterone degradation. The seven enriched swine manure-borne bacteria identified in this study may also have the ability to degrade other hormones or organic compounds with a similar chemical structure. One important observation in this study is that more than 48% of the 14C-testosterone had been mineralized to 14CO2 within 8 d of incubation. The high percentage of 14C-testosterone converted to 14CO2 suggests that testosterone served as an energy source. The mineralization of 14C-testosterone followed pseudo first-order reaction kinetics in the enriched cultures with t1/2 ranging from 10−143 h. PARTICIPANTS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
Contamination of soil and water by endocrine disrupting compounds such as steroid hormones is of increasing environmental concern. The actual effects of these compounds are dependent on their bioavailability, which in turn is influenced by their mobility, among other factors. Our studies indicate that hormones applied via biosolids to soil have the potential to runoff and contaminate the water cycle. The results may be used by the regulatory communities in establishing water quality criteria and for improving current best management practices. These results also indicate that testosterone is rapidly degraded by manure-borne bacteria under a wide range of environmentally relevant conditions. The formed degradation products are still of potential concern due to their endocrine disrupting potential. However, under optimized conditions testosterone has the potential to be mineralized to carbon dioxide. Based on these findings, we suggest that the use of aerated lagoons or aerated caps to provide an oxygenated zone on the surface layer of anaerobic lagoons would be a potentially viable option for more effectively treating hormones in manure wastewater treatment systems.
Publications
- Yang, Y-Y. 2010. Degradation and Transport Pathways of Steroid Hormones from Animal and Human Waste. Colorado State University. (PhD dissertation)
- Blotevogel, J. 2010. Quantum Chemical Modeling of Redox Reactivity, Degradation Pathways and Persistence for Aqueous Phase Contaminants. Colorado State University. (PhD Dissertation)
- Yang, Y.-Y., Borch, T., Young, R. B., Goodridge, L. D., Davis, J. G. 2010. Degradation Kinetics of Testosterone by Manure-Borne Bacteria: Influence of Temperature, pH, Glucose Amendments, and Dissolved Oxygen. Journal of Environmental Quality. 39, 1153-1160.
- Blotevogel, J., Borch, T., Desyaterik, Y., Mayeno, A.N., Sale, T.C. 2010. Quantum Chemical Prediction of Redox Reactivity and Degradation Pathways for Aqueous Phase Contaminants: An Example with HMPA. Environ. Sci. Technol. 44, 5868-5874.
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Progress 01/01/09 to 12/31/09
Outputs
OUTPUTS: A study was completed to characterize the mobility of hormones and their degradation products in field studies using a rainfall simulator. The study has determined steroid sex hormone concentrations in whole-water (unfiltered) runoff samples during a single rainfall simulation event, and during a series of simulated rainfall events over approximately a one-month period. During the single rainfall simulation event, androgen runoff concentrations generally followed runoff rates, peaking at the maximum runoff rate, while estrone runoff concentrations appeared to increase after the maximum runoff rate occurred. During the series of rainfall simulation events, androgen runoff concentrations generally decreased with each simulated rainfall event, while estrogen runoff concentrations (excluding estriol) generally peaked during the second rainfall event after biosolids application. The study also determined steroid sex hormone concentrations in filtered runoff samples (0.7 um GFF), in order to determine the distribution of steroid sex hormones between the filtrate (including particles < 0.7 um) and the particle fraction (particles > 0.7 μm). In general, the distribution varied by analyte. A study was also completed to determine 17beta-estradiol, testosterone, and progesterone degradation rates and products, formed in batch incubations with swine manure. The study has determined rates and half-lives for the degradation of testosterone, 17beta-estradiol, and progesterone by manure-borne bacteria in batch incubation experiments using two media: (a) swine manure mixed with minimal growth media, and (b) a pre-enriched culture of swine manure-borne bacteria. In the pre-enriched culture, where degradation rates and half-lives were not influenced by lag phases or sorption, half-lives ranged from 4.63 h (progesterone) to 24.6 h (17beta-estradiol). The study also examined testosterone degradation in the pre-enriched culture to determine the effects of oxygen (aerobic vs. anaerobic conditions), pH, temperature, and glucose amendments. The half-life of testosterone was observed to be 5-6 times longer under aerobic conditions (27.1 h) than under anaerobic conditions (5.29 h), and the degradation rate was 17% slower at 22C than at 37C. Glucose amendments and pH had little effect under the conditions studied. The study also detected and identified 3 products of testosterone degradation in the pre-enriched culture (dehydrotestosterone, androstenedione, and androstadienedione) which might have, or are already known to have, endocrine disrupting potential. PARTICIPANTS: Nothing significant to report during this reporting period. TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
Impacts
The data suggest that the mobility of steroid sex hormones and their degradation products will vary considerably depending on the compound's identity and a variety of environmental factors and conditions. Androgens and progesterone were generally found in higher concentrations than estrogens in runoff. The study has determined that steroid sex hormones can be degraded by manure-borne bacteria. However, some of the formed degradation products are still of potential concern due to their endocrine disrupting potential.
Publications
- Yang, Y.-Y.; Borch, T.; Young, R. B.; Goodridge, L. D.; Davis, J. G. 2010. Degradation Kinetics of Testosterone by Manure-Borne Bacteria: Influence of Temperature, pH, Glucose Amendments, and Dissolved Oxygen. J. Environ. Qual., 39, doi:10.2134/jeq2009.0112.
- Young, R.B.; Borch, T. 2009. Sources, Presence, Analysis, and Fate of Steroid Sex Hormones In Freshwater Ecosystems - A Review. In Aquatic Ecosystem Research Trends, Nairne, G. H., Ed. Nova Science Publishers, Inc. : Hauppauge, New York, pp 103-164.
- Young, R.B., Borch, T., Snyder, S.A. 2009. Photochemical Transformation of Steroid Sex Hormones in the Presence of Ultraviolet (UV) Light and Selected Natural Photosensitizers. 2nd International Conference on Occurrence, Fate, Effects, and Analysis of Emerging Contaminants in the Environment (EmCon2009), August 4-7, 2009, Fort Collins, Colorado, USA.
- Yang, Y-Y., Borch, T., Young, R.B., Davis, J.G., Goodridge, L.D. 2009. Biodegradation of Steroid Hormones in Swine Manure. 2nd International Conference on Occurrence, Fate, Effects, and Analysis of Emerging Contaminants in the Environment (EmCon2009), August 4-7, 2009, Fort Collins, Colorado, USA.
- Lyons, C.E., Klingenstein, S., Gaulke, R., Lade, S.B., Smith, E., Rice, P., Young, R.B., Borch, T. 2009. Addressing Pharmaceuticals and Personal Care Product Contamination: A Unique Opportunity to Link Science to Effective Policy and Action. 2nd International Conference on Occurrence, Fate, Effects, and Analysis of Emerging Contaminants in the Environment (EmCon2009), August 4-7, 2009, Fort Collins, Colorado, USA.
- Borch, T., Yang, Y-Y., Gray, J.L., Furlong, E.T., Yager, T.J.B., Davis, J.G. 2009. Steroid Hormone Runoff from an Agricultural Field Applied with Biosolids. The 2009 Rocky Mountain Reuse Workshop, Aug 13, 2009, Golden, Colorado, USA.
- Blotevogel, J., Borch, T., Mayeno, A., Sale, T.C. 2009. Quantum Mechanical Degradation Pathway Prediction for New and Emerging Contaminants. 2nd International Conference on Occurrence, Fate, Effects, and Analysis of Emerging Contaminants in the Environment (EmCon2009), August 4-7, 2009, Fort Collins, Colorado, USA.
- Borch, T., Yang, Y-Y., Gray, J.L., Furlong, E.T., Yager, T.J.B., Davis, J.G. 2009. Steroid Hormone Runoff from an Agricultural Field Applied with Biosolids. 2nd International Conference on Occurrence, Fate, Effects, and Analysis of Emerging Contaminants in the Environment (EmCon2009), August 4-7, 2009, Fort Collins, Colorado, USA.
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Progress 01/01/08 to 12/31/08
Outputs
OUTPUTS: The presence of steroid hormones in Colorado's Cache la Poudre River water is being investigated by solid-phase extraction, derivatization, and gas chromatography-tandem mass spectrometry (GC-MS/MS). Multiple-reaction monitoring and isotope dilution procedures are being used for improved sensitivity and reliable compound quantification. Rainfall simulations were conducted on an agricultural field applied with municipal biosolids to investigate the potential for steroid hormone runoff and leaching. Laboratory experiments also are being conducted to investigate the potential for steroid hormone biodegradation and photodegradation under simulated natural conditions, including experiments to investigate the potential for indirect photodegradation through reactions with nitrate and humic acid (acting as photosensitizers). Estrogens and androgens were observed at multiple sites along the river. Preliminary data from our rainfall simulation study shows significant concentrations of estrogens, androgens and progestins in the runoff. Androgens and progesterone were found to a larger extent in the runoff than estrogens. Biodegradation of 17β-estradiol, testosterone and progesterone by manure-borne microorganisms in pig manure was observed and multiple degradation products were detected by liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS). Using UV-A lamps (i.e., lamda > 315 nm), direct photodegradation of testosterone and progesterone was observed, and indirect photodegradation of testosterone and 17β-estradiol was observed in the presence of 5 mg/L humic acid. Several novel photodegradation products were observed by mass spectrometry. This work was presented at several major meetings such as the American Chemical Society meeting, SETAC meeting, and the Soil Science Society of America meeting and several smaller meetings and workshops such as the "Biosolids, PPCPs and the Environment" Workshop organized by the Rocky Mountain Water Environment Association (RMWEA) Biosolids Committee and at a board meeting for the Colorado Water Institute (CWI) and at the Colorado Water Congress, 50th Annual Convention, Denver, CO. PARTICIPANTS: Dr. Thomas Borch (CSU) Dr. Jessica G. Davis (CSU) Graduate Students: Robert B. Young (CSU) Yun-Ya Yang (CSU) Collaborators: James Gray (USGS) Ed Furlong (USGS) Partner Organization: U.S. Geological Survey in Denver (USGS) TARGET AUDIENCES: Nothing significant to report during this reporting period. PROJECT MODIFICATIONS: Not relevant to this project.
Impacts
These findings suggest that steroid hormones are present in the Cache la Poudre River of Colorado, and have the potential to undergo biodegradation and photodegradation. In addition, humic acid (acting as a photosensitizer) can facilitate the indirect photodegradation of some steroid hormones. Finally, our preliminary data shows that steroid hormones have the potential to runoff from agricultural fields applied with biosolids during a heavy rainfall event.
Publications
- Young, R.B., Borch, T., Yang, Y.-Y. and Davis, J.G.: 2008. 'Occurrence and Fate of Steroid Hormones in Sewage Treatment Plant Effluent, Animal Feeding Operation Wastewater and the Cache la Poudre River of Colorado', Colorado Water - Newsletter of the Water Center of Colorado State University 25, 10-14.
- Gray, J.L., Young, R.B., Borch, T., Foreman, W.T., Yang, Y-Y. 2008. Presence and Fate of Steroid Hormones in a Colorado River. The Society of Environmental Toxicology and Chemistry (SETAC) North America 29th Annual Meeting, November 16-20, 2008, Tampa, Florida, USA.
- Borch, T., Young, R.B., Gray, J.L., Foreman, W.T., Davis, J.G., Yang, Y-Y. 2008. Presence and Fate of Steroid Hormones in a Colorado River. The GSA-ASA-CSSA-SSSA Joint Annual Meeting, October 5-9, 2008, Houston, TX.
- Borch, T., Young, R.B., Gray, J.L., Foreman, W.T., Yang, Y-Y. 2008. Presence and Fate of Steroid Hormones in a Colorado River. Division of Environmental Chemistry - American Chemical Society Meeting August 17-21, 2008, Philadelphia, PA.
- Young, R.B., Borch, T., Yang, Y-Y. 2008. Occurrence and Fate of Steroid Hormones in the Environment. CSU Global Water Colloquium, March 26-28, 2008, Colorado State University, Fort Collins, CO.
- Archibeque, S.L., Borch, T., Davis, J.G. 2008. Impact of Growth Hormones on Nutrient Excretion. The Great Plains Soil Fertility Conference March 4-5, 2008, Denver, CO.
- Archibeque, S.L., Borch, T., Engle, T.E., Wagner, J.J., Han, H. 2008. Potential endocrine disruptors from dairies and feedlots, and environmental implications. 2008 Intermountain Nutrition Conference January 29-30, 2008, Salt Lake City, UT.
- Yang, Y-Y., Borch, T., Davis, J.G. 2008. Degradation of Steroid Hormones in Pig Manure. The GSA-ASA-CSSA-SSSA Joint Annual Meeting, October 5-9, 2008, Houston, TX.
- Young, R.B., Borch, T., Yang, Y-Y., Davis, J.G. 2008. Occurrence and Fate of Steroid Hormones in the Environment. CSU Global Water Colloquium. March 25, 2008. Colorado State University, Fort Collins, CO.
- Makedonski, A. 2008. Fate and Transport of Steroidal Hormones in the Environment. MS Thesis: Colorado State University, pg. 124.
- Borch, T., Young, R.B., Gray, J.L., Foreman, W.T. and Yang, Y.-Y.: 2008. 'Presence and fate of steroid hormones in a Colorado River', 236th American Chemical Society National Meeting & Exposition ACS, Philadelphia, pp. 689-694.
- Archibeque, S.L., Borch, T., Davis, J.G. 2008. Impact of Growth Hormones on Nutrient Excretion. The Great Plains Soil Fertility Conference March 4-5, 2008, Denver, CO (6 pages).
- Archibeque, S.L., Borch, T., Engle, T.E., Wagner, J.J., Han, H. 2008. Potential endocrine disruptors from dairies and feedlots, and environmental implications. 2008 Intermountain Nutrition Conference January 29-30, 2008, Salt Lake City, UT (14 pages).
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Progress 01/01/07 to 12/31/07
Outputs
OUTPUTS: This research was disseminated via one news letter article ("Colorado Water"), one peer-reviewed proceedings paper, one non-peer-reviewed proceedings paper, three invited seminars at Colorado State University, five oral and two poster presentations at national and international conferences.
PARTICIPANTS: Prof. Thomas Borch is the PI and Prof. Jessica G. Davis is the co-PI on this project. Jennifer Jones worked as an undergraduate honors student on this project from May 2006 to until her graduation in May 2007 (focus area photodegradation of steroid hormones). Catherine R. Simpson worked as Ph.D. student on this project from August 2006 to 2007 (focus area river study and biodegradation studies of steroid hormones). Robert B. Young is a current (July 2007 - present) Ph.D. student working on this project (focus area photodegradation and river study of steroid hormones). Yun Ya Yang is a current(August 2007 - present) Ph.D. student working on this project (focus area river study, runoff study and biodegradation study of steroid hormones). We work in close collaboration with the researchers from the USGS Water Quality Laboratory in Denver on this project. Shannon D. Phelps, President, Water Goat Enterprises, Inc., d/b/a The SeaCrest Group, 1341 Cannon Street, Louisville, CO
80027 donated a gift of $3000 to help support our project in 2007. Colorado Water Resources Research Institute (CWRRI) supports this project financially. Prof. Jessica G. Davis is my main collaborator within CSU. This project has supported and educated two undergraduate and three graduate students (Ph.D. students).
TARGET AUDIENCES: The target audience of this project are water managers, farmers, under graduate and graduate students (both females, including a single mom and an asian woman, and males), and scientists around the world. Efforts from this project include: formal classroom instruction, laboratory instruction; internships; extension and outreach.
Impacts
In recent years, scientists have become increasingly concerned about the exposure of humans and wildlife to chemicals in the environment that may disrupt the normal function of their endocrine systems, even at extremely low concentrations. Suspected endocrine-disrupting chemicals (EDCs) include (i) organic chemicals e.g., pharmaceuticals and pesticides, (ii) heavy metals, and (iii) natural compounds e.g., steroid hormones. Therefore, an understanding of the occurrence, fate and transport of EDCs is imperative to human and environmental health. We evaluated the potential occurrence of steroid hormones and their degradation products (e.g., 17-beta-estradiol, estrone, testosterone, androstenedione, cis-androsterone and progesterone) in the Cache la Poudre river of Colorado and the potential for photodegradation of these compounds. In July 2007, samples were collected from six locations along the river. The sampling locations, range in character from pristine (Site 1) to
urban (Site 4) to heavy agricultural environments (Sites 5 and 6). Between sites 4 and 6, for example, there are over 90 confined animal feeding operations, dairies and ranches. The collected water samples were filtered through glass fiber filters, a solid phase extraction process was used to concentrate steroids in the samples, and the samples were analyzed with gas chromatography and mass spectrometry. The detection limits varied from site to site, but all were in the low parts-per-trillion (ng/L) range. 17-beta-estradiol was present at every site except Site 5 (heavy agriculture). Interestingly, estrone, a typical degradation product of 17-beta-estradiol, was only observed at Sites 5 and 6 (urban & heavy agriculture). This may be due to limited degradation of 17-beta-estradiol in the river, or due to higher concentrations of 17-beta-estradiol at Sites 4 and 6. Progesterone was not detected in the current study. Due to analysis related problems, no data are currently available for
testosterone. However, androstenedione, a potential degradation product of testosterone, was observed downstream of the Mulberry WWTP (Site 4) and in Greeley (Site 6). Cis-androsterone, a potential testosterone metabolite, was only observed at site 4, suggesting that this compound is either retained in the sediment or being rapidly degraded. Laboratory experiments were conducted to study the potential photodegradation of steroids under UVA light and the possibility of reactions with photosensitizers such as nitrate (10 mg/L) and humic acid (5 mg/L). Testosterone degraded under UVA light, and the rate of degradation increased by approximately 200% in the presence of humic acid. Progesterone degraded under UVA light, but the rate of degradation was unaffected by the presence of humic acid. Finally, 17-β estradiol did not degrade under UVA light, but degraded rapidly in the concurrent presence of humic acid. The effect of nitrate was insignificant. Photodegradation of testosterone
was also observed in water samples taken from the Poudre River (site 6) and the Suwannee River. These results suggest the potential for endocrine disruption and steroid hormone photodegradation in the Poudre River.
Publications
- Archibeque, S.L., Borch, T., Engle, T.E., Wagner, J.J., Han, H. 2007. Endocrine Disruptor Residues in Feedlot and Dairy Waste Streams. 68th Minnesota Nutrition Conference and University of Minnesota Research and Update Session: Modern Concepts in Livestock Production for 2007 (15 pages).
- Borch, T., Davis, J.G., Simpson, C.R., Young, R.B., Jones, J.M. 2007. Impact of Photolysis and Manure-Borne Bacteria on the Fate of Steroid Hormones. The American Water Resources Association (AWRA) Summer Specialty Conference on Emerging Contaminants of Concern in the Environment: Issues, Investigations and Solutions, June 25-27, 2007, Vail Cascade Resort & Spa, Vail, CO.
- Borch, T., Young, R.B., Jones, J.M., Davis, J.G., Simpson, C.R. 2007. Degradation of Steroid Hormones in the Environment. The ASA-CSSA-SSSA International Annual Meetings November 4-8, 2007, New Orleans, LA.
- Jones, J.M., Borch, T., Young, R.B., Davis, J.G., Simpson, C.R. 2007. Photolysis of testosterone, progesterone, and 17-beta-estradiol by UVA light In Emerging Contaminants of Concern in the Environment: Issues, Investigations, and Solutions; Drewes, J. E., Battaglin, W. A., Kolpin, D. W., Eds.; American Water Resources Association, Middleburg, Virginia,: Vail, Colorado, 2007; Vol. Proceedings of the AWRA 2007 summer specialty conference, TPS-07-2, CD-ROM (5 pages).
- Jones, J.M., Borch, T., Hansen, N.C., Davis, J.G., and Simpson, C.R. 2006. Photodegradation of Manure-Borne Steroid Hormones. The ASA-CSSA-SSSA International Annual Meetings November 12-16, 2006, Indianapolis, IN.
- Simpson, C.R., Borch, T., Davis, J.G., Jones, J.M. 2007. Fate of Testosterone in Manures from Various Livestock. The AWRA Summer Specialty Conference on Emerging Contaminants of Concern in the Environment: Issues, Investigations and Solutions, June 25-27, 2007, Vail Cascade Resort & Spa, Vail, CO.
- Young, R.B., Borch, T. 2007. Impact of Photolysis and Photosensitizers on the Fate of 17β-Estradiol, Progesterone and Testosterone. American Chemical Society 20th Rocky Mountain Regional Meeting - Chemistry and Engineering for Sustainability. August 29 - September 1, 2007, Denver, CO.
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