1. 2008-2011 Summary Report Emerging Contaminants Program

2. Overview of Presentation  Monitoring Program  Why, Who, Where  Analytical Methods  QAQC  Study Results  2008-2011

3. Monitoring Program Overview Why Monitor?  Shift from agriculture to municipal water use  Increased awareness of water quality  Increased awareness of emerging contaminants in water supplies Antidepressants, Endocrine disruptors Impacts on aquatic life  Strengthening of the regulatory framework  Baseline of data for drinking water supplies  Assess changes in the future

4. Monitoring Program Overview Cooperative Monitoring Program  Began in 2008  Co-funded Boulder, Broomfield, Fort Collins, Greeley, Longmont, Loveland, Estes Park, Northern Water and U.S. Bureau of Reclamation  Pharmaceuticals, Personal Care Products, Endocrine Disruptors, Pesticides and Herbicides  Analysis done at CU Boulder, Center for Environmental Mass Spectrometry

5. Sampling Sites  19 Sites Reservoirs, canals, streams, raw and finished water C-BT and non-C-BT water supplies Evolving  Four events yearly Seasonal influences Runoff Recreation Reservoir processes

6. Monitoring Program Overview Sample Collection  Shared by co-funders  Protocol Use of gloves No DEET No caffeine No nicotine  Collection Method Grab Sample Kemmerer QAQC  Trip and field blanks

7. Analytical Methods  Sample Preparation by Solid Phase Extraction  Low Level Method by LC/MS-MS(EPA 1694)  Hormone Method by LC/MS-MS (EPA 1698)  Differences of Hormone Method with UL labs  Screening Method by LC/TOF-MS  QA/QC Program CU (CEMS)

8. Low Level Analysis (LC-MS-MS) Liquid Chromatography (HPLC) Mass Spectrometer (MS) Selective analysis of individual compounds, based on: Some new compounds were added to the low level method in 2011: lamotrigine, sucralose, triclosan, venlafaxine… In 2012: atrazine…

9. Hormone Method (LC-MS-MS)  Hormones ionize poorly in LC-MS.  Need a more sensitive method (low ng/L).  Low level method was modified (adding NH 3 to mobile phase) to increase detection.

10. Hormone Analysis Difference in reporting limits between CEMS and UL Comparison of findings between CEMS and UL Compound Reporting Limit (ng/L) Hormone Type CEMSUL 17 alpha-Ethynyl estradiol 100.5 Birth Control Pill 17 beta-Estradiol 50.5 Natural Female Bisphenol A 20100 Phenolic Endocrine Disruptor Estrone 10.5 Natural Metabolite Progesterone 10.1 Natural Female Testosterone 10.1 Natural Male

11. QA-QC Data (LC-MS-MS) Field samples were spiked at 40 ppt and extracted and analyzed with the LC-MS-MS Method to calculate Standard Deviations of the methodology. EDCs were spiked at 80 ppt to be above LOD's. n.a. = not analyzed for that sampling event Field blanks also included in each sampling set (< LOD)

12. Screening Method by LC/TOF-MS  Analyze Vial in TOF Mode  Database Search Pesticides  Database Search Pharmaceuticals  Verify Positives by Manual Inspection  Search for Unknowns—Fluridone, Lamotrigine…  Standard Analysis where Necessary The LC/TOF-MS instrument (Agilent 6220) is our tool for identification of non-target compounds and unknowns. It provides accurate masses below 2 ppm error and it has been succesfully used for many of our current projects. The high resolving power of 4 GHz allows the separation of isobaric interferences from compounds of interest. Linearity of response is over 2 orders of magnitude. 4,000,000,000 times/second

13. Study Results Overview  Characterization of WWTP Influence  Pharmaceuticals and Personal Care Products  WWTP inputs  Herbicides and Pesticides  Canal maintenance  Weed control adjacent to waterways  Recreational Influences  Streams and reservoirs  Summer months

14. WWTP Inputs  Fraser River Four WWTPs above Windy Gap  Willow Creek Three Lakes SD  Big Thompson River Estes Park SD Upper Thompson SD  Barker Reservoir Nederland WWTP

15. Characterization of WWTP Influence Sampling of WWTP effluent  Sample representative of all WWTP in study area  Provide baseline of compounds found in study area  June 2009 and August 2010 June 2009 – LC/TOF method for analysis August 2010 – LC/MS low-level method for analysis

16. Compound TypeCompound Detection Limit (ng/L) Classification Herbicides and Pesticides 2,4-D5Herbicide Diazinon1Insecticide Diuron5Herbicide Fluridone5Herbicide Household Products Sucralose15Artificial Sweetener Personal Care Products DEET20Bug Repellant Triclosan20Antibacterial Endocrine Disruptor Bisphenol A20Plasticizer Pharmaceutical and Drugs Acetaminophen5Analgesic Atenolol5Blood Pressure Bupropion1Antidepressant Caffeine10Stimulant Carbamazepine2Antidepressant Clarithromycin2Antibiotic Cotinine1Stimulant Diltiazem5Blood Pressure Diphenhydramine5Antihistamine Erythromycin10Antibiotic Gemfibrozil5Analgesic Lamotrigine5Antidepressant Metoprolol1Blood Pressure Propranolol1Blood Pressure Sulfamethoxazole5Antibiotic Trimethoprim5Antibiotic Venlafaxine1Antidepressant

17. Characterization of WWTP Influence Endocrine Disrupting Compounds  Analysis at Underwriters Laboratory 17 compounds analyzed, 5 compounds detected  Low number of detections at very low concentrations at all sites during study period

18. Characterization of WWTP Influence  Samples of WWTP effluent no longer collected  New sampling site in 2011 1 mile downstream of Lake Estes Influence from Estes Park and Upper Thompson SDs  LC/MS low-level method can capture compounds of concern

19. Upstream to Downstream

20.  August 2010 WWTP effluent  August 2011 site in Big Thompson River below WWTP  In general, same compounds at a lower concentration  August 2011 added lamotragine, sucralose, triclosan and venlafaxine  Compounds that persist downstream: Carbamazepine, gemfibrozil, lamotrigine, metoprolol, sucralose, sulfamethoxazole and venlafaxine

21. Pharmaceuticals and Personal Care Products  No apparent spatial variation, compounds stable in reservoir due to constant influx  Some variability with depth but no apparent pattern Horsetooth Reservoir  Samples collected at three depths: Top, Metalimnion, and Bottom  Compounds consistent with those found in the Hansen Feeder Canal Metoprolol detected at every sampling event Elevated sucralose concentrations

22. Pharmaceuticals and Personal Care Products Boulder Reservoir  Less detections and lower concentrations  More detections of cotinine compared to other sites  Cotinine and sucralose persist in the finished water Very low concentrations

23. Herbicides and Pesticides  Widely used throughout study area  Agriculture, private land owners, parks and golf courses  2,4-D most common ingredient  Often applied adjacent to waterbodies  Northern Water Operations  Control of terrestrial weed, algae and aquatic plants in and around canals  Hansen Feeder Canal, Saint Vrain Supply Canal and Boulder Feeder Canal  Weed control around Carter Lake and Horsetooth Reservoir

24. Herbicides and Pesticides Big Thompson River  Some influence from WWTP for 2,4-D diazinon and diuron  2,4-D most frequently detected  August 2011 at BT-DLU, highest 2,4-D concentration for all the sampling sites for the study period Low concentration upstream BT-DLU next to park

25. Herbicides and Pesticides Boulder Reservoir  Different weed control efforts in Boulder Feeder Canal Earth-lined Vascular aquatic plants Sonar © Applied in fall when canal is dewatered Active ingredient fluridone

26. Herbicides and Pesticides Boulder Reservoir  2,4-D, diuron and fluridone all detected  Most detections with highest concentrations at sites closest to Boulder Reservoir  Detections in finished water

27. Recreational Activities  Detections of caffeine, DEET and triclosan can be attributed to WWTP but can be increased by recreational activities  Boulder Reservoir, Carter Lake and Horsetooth Reservoir  Cache la Poudre and Big Thompson Rivers

28. Recreational Activities Big Thompson River  Caffeine and DEET in WWTP effluent Caffeine highest concentrations Generally higher than PPCPs and herbicides  Downstream concentrations that are higher than or equal to the WWTP sites suggest additional source

29. Recreational Activities Horsetooth Reservoir  Caffeine detected at all sampling events  No apparent spatial pattern  No pattern at different depths Boulder Reservoir  Spike in caffeine in BFC in August 2011 may suggest additional source  Caffeine and DEET detected in the finished water at very low concentrations

30. Conclusions  Drinking water sources in study area have very clean water  Some compounds were found to persist throughout the study area  Influence of WWTPs is apparent but dilution is significant  Boulder Feeder Canal is impacted by herbicide applications  The program should continue to evolve to include more compounds currently being considered for regulation by the EPA

31. Thank You  Co-Funders  City of Boulder  City of Broomfield  City of Fort Collins  City of Greeley  City of Longmont  City of Loveland  Town of Estes Park  US Bureau of Reclamation  CU Boulder Center of Environmental Mass Spectrometry  Imma Ferrer  Michael Thurman

32. Jen Stephenson Northern Water jstephenson@northenwater.org 970 (622-2334) Questions? Report available online at: http://www.northernwater.org/WaterQuality/WaterQualityReports