1. Detection and Quantification of Trace Organic Compounds (EDC/PPCPs) from Aqueous Arizona Environments AZ Water Association – Wastewater Treatment Committee October 21, 2014 Leif Abrell Arizona Laboratory for Emerging Contaminates, Department of Soil, Water and Environmental Science, University of Arizona

2. Analytical comparison of Regional water sources - EDC/PPCPs - Dissolved Organic Matter Chorover, J; Abrell, L; Wickramasekara, S; Hernández-Ruiz, S; Kahl, A; Arnold, R. Detection & Quantification of EDC/PPCPS in Waters Containing Organic Matter, Water Research Foundation, 2014.

3. CAP pumping plant Central & Southern Avra Valley Storage and Recovery Projects (CAVSARP, SAVSARP)

4. Tucson Basin Watershed-level chemical characteristics may reflect the entire Colorado River Basin. Very little of the chemical load in water (as a consequence of municipal use) is flushed from the Tucson area (in surface or subsurface flow), hence persistent organic pollutants can accumulate within the watershed. Central/Southern Avra Valley Recharge Projects City of Tucson

5. CAVSARP SAVSARP ?

6. CAVSARP SAVSARP WWTPs NW wells City of Tucson

7. Effluent dependent reach of Lower Santa Cruz River with potable production wells down-gradient from wastewater treatment plants

8. NW Well Z013A – WWTP effects

9. Choosing appropriate indicators for water impairment Potential sources of contamination: Treated wastewater effluent Hospitals Storm run off Sucralose artificial sweetener, is a chlorinated sugar

10. Indicator Contaminants Levels in Tucson Waters Quanrud et al., Perfluorinated Compounds in Arizona Groundwater: Sources of Contamination, USGS, 2011.

11. Methodology

12. Method: SPE - LCMSMS UPLC (Ultra Performance Liquid Chromatography): Reverse phase ACN-H 2 O gradient, Acquity BEH C18 1.7 um, 2.1 x 50 mm Column, 5 ul injection. Electrospray Ionization – Tandem Mass Spectrometry MRM (multiple reaction monitoring) 250-300 ul min -1 Solid Phase Extraction (SPE) 0.5 – 1.0 ml 0.7um filtration 1 L

13. Selectivity increases as the number of analyses steps increases, e.g. LC vs. LC/MS vs. LC/MS/MS. While the absolute signal decreases with increasing number of analysis steps, the signal-to-noise ratio (S/N) increases. S/N is an empirical measure of the size of the analyte peak (signal) relative to the size of the baseline noise. Sensitivity achieved through Selectivity

14. Analytical sensitivity (signal) increase by removal of background (noise) Signal to Noise = 99:1 (hypothetical)

15. Analytical sensitivity (signal) increase by removal of background (noise) Signal to Noise = 99:1 (hypothetical)

16. Analytical sensitivity (signal) increase by removal of background (noise) Signal to Noise = 99:1 (hypothetical)

17. Analytical sensitivity (signal) increase by removal of background (noise) Signal to Noise = 99:1 (hypothetical)

18. Analytical sensitivity (signal) increase by removal of background (noise) Signal to Noise = 99:1 (hypothetical)

19. Ion optics inside tandem mass spectrometer (triple quadrupole)

20. Estrone fragmentation Transitions: 269 > 145 269 > 143 adapted from J Am Soc Mass Spectrom. 2005 February ; 16(2): 271–279. ion = charged species

21. MRM Conditions for the Selected Target Analytes (CV: Cone Voltage; CE: Collision Energy)

22. Environmentally burdened communities along the US-Mexico border

23. Significant correlation: concentration of TCE in breast milk and bathing water.

24. Microbial, Inorganic, and Organic Contaminants in Private Wells along the Santa Cruz River, Arizona Supported by an EPA Environmental Justice Grant Yoshira Ornelas 1, Kelly Reynolds 1, Leif Abrell 2, Jen Parks 3, and Paloma Beamer 1 The University of Arizona Mel and Enid Zuckerman College of Public Health 1, Arizona Laboratory of Emerging Contaminants 2, Friends of the Santa Cruz River 3 Tucson, AZ 85721

25. Contaminants of Emerging Concern in Arid and Semi-arid Environments: Occurrence, Source, and Fate of Pharmaceuticals and Hormones in the Mexicali Valley Region

26. Contaminants of Emerging Concern in Arid and Semi-arid Environments: Occurrence, Source, and Fate of Pharmaceuticals and Hormones in the Mexicali Valley Region Includes agriculture and delivery to adjacent communities

27. Antibiotic Resistance

28. Walston, McLain, Rock, Abrell

31. Harvested Rainwater Quality

32. Background: gap and solution Knowledge gap: – Harvested (recycled) water is most often used for garden and landscape irrigation, yet no water quality standards exist regarding the use of harvested rainwater. Solution – Monitor water quality over the 2013 monsoon season and discern what homeowners should be wary of and when. – Assess ability of simple, cheap filters to change water quality – Pass findings to utilities and municipalities in the western U.S. to draft plans for safe rainwater harvest and recycling.

33. 2013 Data: Experimental method

34. 2013 Data: Sample Preparation and Analysis Microbiology - Total coliforms, E. coli, and Enterococcus by Colilert and Enterolert quanti-tray technique (IDEXX). Metals analysis - samples filtered, acidified to pH<2; ICP-MS analysis of 16 metals Organic contaminants - samples filtered, extracted by SPE (solid phase extraction); LC-MSMS analysis of perfluorinated contaminants (PFCs)

35. Metals analysis Arsenic5 Barium100 Cadmium1 Chromium5 Lead5 Mercury0.2 Selenium*1 Silver5 * * Rural Urban

36. 2013 Data Metals analysis Rural Urban

37. Metals analysis B2 WRRC Urban Rural

38. Metals analysis Rural Urban

39. Liquid chromatography - tandem mass spectrometry (LC-MSMS) – PPCPs, EDCs, perfluorinated compounds

40. Arizona Laboratory for Emerging Contaminants Samples, lab tests, in kind support Data: emerging organic contaminants in ppt – ppb concentrations

41. ACKNOWLDEGEMENTS Prof.s Jon Chorover &, Shane Snyder – ALEC Directors Water RF Regional Contaminants Survey Dr. Samanthi Wickramasekara Dr. Selene Hernandez-Ruiz Prof. Robert Arnold Dr. Alandra Kahl Dr. David Quanrud Border Region Contaminants Prof. Paloma Beamer Yoshi Ornelas Thien Tran Vicki Chu Prof. Concepcion Carreon - Universidad Autónoma de Baja California Mexicali, Baja California, México Catherine Luik Prof. Eduardo Saez Antibiotic Resistance Prof. Channah Rock Prof. Jean McLain Stephen Walston Harvested Rainwater Quality Angela Knerl Nate Allen