1. CRISTINA TILLBERRY SUMMER REU 2013 8/8/13 Impact of the High Park Fire on Water Quality in the Fort Collins Area A study in conjunction with Dr. Fernando Rosario-Ortiz, Kaelin Cawley, and Amanda Hohner

2. High Park Fire 87, 284 acres 1 fatality 259 homes destroyed Burned June 9 to July 1, 2012 Figure: Study area showing burned area and location of proposed sampling locations on the Poudre River

3. Cache La Poudre Watershed Poudre River is the main source of drinking water for three major water districts, including Fort Collins, CO Drinking water intake facility is within burn area Sampling river water at three different test sites  Control site upstream of burn area  Burn area downstream  Water intake facility in burn area Figure: Filters from control site water sample (left) and burn area site water sample (right)

4. Motivation Determine how wild fires affect water quality and drinking water treatment Characterize dissolved organic matter (DOM) in water  DOM may hinder the treatment facility to efficiently treat the water Analyze similarities and differences in data between before coagulation and after coagulation samples

5. What did we do? Surface water samples were collected from three sites on the Poudre River and filtered  Reference site  Impacted – upstream  Impacted – downstream (water intake facility) Used different techniques to gather data from samples  Size Exclusion Chromatography  UV-Visible Spectroscopy  Fluorescence Spectroscopy / Excitation and Emission Matrices Coagulated samples to compare data from before and after

6. Chromatography A technique used to discover chemical components in a mixture by passing it through or over something that separates the different components at different rates High performance liquid chromatography (HPLC)  Liquid, gas, or size exclusion chromatography (SEC) Figure: Diagram showing the components of an HPLC instrument [4]

7. SEC: Size Exclusion Chromatography Physically separates compounds based on size Measures hydrodynamic volume, not actual molecular weight Uses porous particles to separate different sized molecules in the sample Particles that are smaller than the pores in the column will enter the pores  longer path and longer transit time Figure: Diagram describing process of size exclusion chromatography

8. UV-Visible Spectroscopy Measures the absorbance from a sample Light is shined onto the cuvette  light absorbance for the sample is compared to the light absorbance of the water blank UV-Vis data used to correct EEMs data Figure: UV-Vis spectroscopy diagram

9. Fluorescence Spectroscopy A technique that measures the emission of radiation by a material that has been excited Once the output is determined, a fluorescence spectrum can be created From spectrum, fluorescence index (FI) can be used to determine type of DOM in the water  Higher FI: more microbial input  Lower FI: more terrestrial input Also referred to as excitation and emission matrices (EEMs) Figure: Fluorescence spectroscopy diagram

10. Coagulation Coagulant added to water to settle impurities Clear water at top is removed and filtered Figure: Coagulant added to water to remove impurities

11. Results - SEC Ran SEC samples before and after coagulation DOM: dissolved organic matter JT: jar test Figure: SEC data for control site and water intake facility in burn area before (DOM) and after (JT) coagulation

12. Results - SEC SampleM w (DOM)M w (JT) PBR1304011029710 PBR1304201086539 PBR130504970617 PBR1305141653750 PBR1306011939802 PNF1304011163831 PNF1304201078714 PNF13050412891056 PNF13051412031033 PNF1306018321032 PBR: control site PNF: water intake facility in burn area Date: 130401 (April 1, 2013) M w : Weight average molecular weight A: absorbance M: molecular weight Table: MW data for control site and water intake facility in burn area before (DOM) and after (JT) coagulation

13. Results - Molecular Weight Snow melt Figure: MW data for control site and water intake facility in burn area before (DOM) and after (JT) coagulation

14. Results - Fluorescence Excitation and Emission Matrix (EEMs) data Color: intensity Contour lines: peaks Figure: EEMs data for control site before (DOM) and after (JT) coagulation

15. Results - Fluorescence SampleFI (DOM)FI (JT) PBR130401 1.361.66 PBR130420 1.381.63 PBR130504 1.351.61 PBR130514 1.371.64 PBR130601 1.351.60 PNF130401 1.441.70 PNF130420 1.431.67 PNF130504 1.441.69 PNF130514 1.411.70 PNF130601 1.351.60 Higher FI: more microbial input Lower FI: more terrestrial input Table: Fluorescence Index for before (DOM) and after (JT) coagulation samples

16. Conclusions Molecular weight  Increased after snow melt for control site  Decreased after snow melt for impacted water intake facility Intensity of radiation emission wavelengths decreased after coagulation  According to EEMs contour plots More terrestrial input before coagulation  Coagulants removed most of terrestrial matter  Microbial input is more evident when terrestrial input is removed

17. What’s next? Collecting storm samples  Determine differences between storm run off and snow melt Determine differences between summer and winter samples Determine if more or less terrestrial input in water  More shrubs growing back in burn area  Stop terrestrial input

18. Sampling is fun! Gathering water samples from the Poudre River

19. References [1] Rosario-Ortiz, F. & Summers, R.S. (2013). The impact of the high park fire on the source water quality for utilities in fort collins area: Cache la poudre river watershed. (University of Colorado). [2] Coble, P. G. (1996). Fluorescence contouring analysis of doc intercalibration experiment samples: a comparison of techniques. (University of Washington). [3] International Humic Substances Society. (2007, December). What are humic substances?. Retrieved from http://www.humicsubstances.org/whatarehs.html [4] Iowa State University of Science and Technology. (2008). High performance liquid chromatography (hplc). Retrieved from http://www.protein.iastate.edu/hplc.html [5] Tissue, B. M. (2000). Size exclusion chromatography (sec). Retrieved from http://www.files.chem.vt.edu/chem- ed/sep/lc/size-exc.html [6] Gullapalli, S. (2010, June 26). Optical characterization of group 12-16 (ii-vi) semiconductor nanoparticles by fluorescence spectroscopy. Retrieved from http://cnx.org/content/m34656/1.1/ [7] Williams, M., McKnight, D., Simone, B., Cory, R., Miller, M., Gabor, R., Hood, E. (2011). PARAFAC workshop spring 2011. (University of Colorado). [8] Maie, N., Watanabe, A., Kimura, M. (2004). Chemical characteristics and potential source of fulvic acids leached from the plow layer of paddy soil. (Nagoya University). [9] Reusch, W. (2013). UV-Visible Spectroscopy. Retrieved from http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/UV-Vis/uvspec.htm#uv1 [10] Kauffman, J.M. (2005). Water fluoridation: A review of recent research and actions. Journal of American Physicians and Surgeons, 10(2): 38-44. Retrieved from http://www.usaus-h2o.org/modules/treatment-and-distribution/

20. Questions?