CRISTINA TILLBERRYSUMMER 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

High Park Fire

87, 284 acres1 fatality259 homes

destroyedBurned June 9

to July 1, 2012

Figure: Study area showing burned area and location of proposed sampling locations on the Poudre River

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)

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 waterAnalyze similarities and differences in data

between before coagulation and after coagulation samples

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

MatricesCoagulated samples to compare data from before

and after

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

timeFigure: Diagram describing process of size exclusion chromatography

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

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

Coagulation

Coagulant added to water to settle impuritiesClear water at top is removed and filtered

Figure: Coagulant added to water to remove impurities

Results - SEC

Ran SEC samples before and after coagulation

DOM: dissolved organic matterJT: jar test

0 5 10 15 20 25 30 35-1

0

1

2

3

4

5

6

PBR 5/4/13

DOMJT

Time (min)

UV

254

0 5 10 15 20 25 30 35-202468

10121416

PNF 5/4/13

DOMJT

Time (min)

UV

254

Figure: SEC data for control site and water intake facility in burn area before (DOM) and after (JT) coagulation

Results - SEC

Sample Mw (DOM) Mw (JT)

PBR130401 1029 710

PBR130420 1086 539

PBR130504 970 617

PBR130514 1653 750

PBR130601 1939 802

PNF130401 1163 831

PNF130420 1078 714

PNF130504 1289 1056

PNF130514 1203 1033

PNF130601 832 1032

PBR: control sitePNF: water intake facility in burn areaDate: 130401 (April 1, 2013)Mw: Weight average molecular weight

A: absorbanceM: molecular weight

Table: MW data for control site and water intake facility in burn area before (DOM) and after (JT) coagulation

𝑀𝑤=∑ 𝐴𝑖 𝑀 𝑖

∑ ( 𝐴𝑖 )

Results - Molecular Weight

3/27/2013 4/6/2013 4/16/20134/26/2013 5/6/2013 5/16/20135/26/2013 6/5/20130

500

1000

1500

2000

2500

PBR Mw

mw (dom)mw (jt)

Date

Mole

cula

r W

eig

ht

3/27/2013 4/6/2013 4/16/20134/26/2013 5/6/2013 5/16/20135/26/2013 6/5/20130

200400600800

100012001400

PNF Mw

mw (dom)mw (jt)

Date

Mole

cula

r W

eig

ht

Snow melt

Snow melt

Figure: MW data for control site and water intake facility in burn area before (DOM) and after (JT) coagulation

Results - Fluorescence

Excitation and Emission Matrix (EEMs) dataColor: intensityContour lines: peaks

Figure: EEMs data for control site before (DOM) and after (JT) coagulation

Results - Fluorescence

Sample FI (DOM) FI (JT)

PBR130401 1.36 1.66

PBR130420 1.38 1.63

PBR130504 1.35 1.61

PBR130514 1.37 1.64

PBR130601 1.35 1.60

PNF130401 1.44 1.70

PNF130420 1.43 1.67

PNF130504 1.44 1.69

PNF130514 1.41 1.70

PNF130601 1.35 1.60

Higher FI: more microbial inputLower FI: more terrestrial input

Table: Fluorescence Index for before (DOM) and after (JT) coagulation samples

Conclusions

Molecular weight Increased after snow melt for control site Decreased after snow melt for impacted water intake

facilityIntensity 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

What’s next?

Collecting storm samples Determine differences between storm run off and

snow meltDetermine differences between summer and

winter samplesDetermine if more or less terrestrial input in

water More shrubs growing back in burn area

Stop terrestrial input

Sampling is fun!

Gathering water samples from the Poudre River

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/

Questions?