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Contaminants of Emerging Concern and their Use as Tracers of Bacterial Pollution Andy James Center for Urban Waters January 30, 2014. Outline. Contaminants of Emerging Concern (CECs) Kitsap County Tracer Study Characterize CECs in Water Entering Puget Sound

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Outline

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  1. Contaminants of Emerging Concern and their Use as Tracers of Bacterial PollutionAndy JamesCenter for Urban WatersJanuary 30, 2014

  2. Outline • Contaminants of Emerging Concern(CECs) • Kitsap County Tracer Study • Characterize CECs in Water Entering Puget Sound • Investigate Utility of CECs as Tracers of Septic Influence • Boise Creek CEC sampling • Short Term Variation • Evaluate relationships between CECs and: 1) fecal coliform2) nitrogen3) phosphorus Project Team: Justin Miller-Schulze Alex Gipe, Derek Overman, and Brian Hite (UW Tacoma students) Shawn Ultican and Stuart Whitford (Kitsap County Health) Funding: Russell Family FoundationEPA

  3. Contaminants of Emerging Concern(CEC) • Trace organics present at very low levels (μg/L or ng/L) • Previously unknown due to analytical limitations • Generally unregulated • May have biological impacts • Some associated with specific uses http://www.unb.ca/saintjohn/sase/research/kiddlab/_resources/ela.jpg

  4. Contaminants of Emerging Concern Human Food and Beverage Caffeine Paraxanthine (metabolite) Theobromine (metabolite) Caffeine ~10% ~80% Paraxanthine Theobromine

  5. Sucralose • Low-calorie sweetener (cannot be metabolized) • Has been shown to undergo little to no degradation in municipal wastewater treatment processes • Conservative tracer Buerge et al, 2009, Ubiquitous occurrence of the artificial sweetener acesulfame in the aquatic environment: an ideal chemical marker of domestic wastewater in groundwater. ES&T.

  6. Contaminants of Emerging Concern Agriculture Related Atrazine: herbicide • Mecoprop: • weed-and-feed • Ractopamine: • Livestock feed additive

  7. Contaminants of Emerging Concern Ensulizole: UV Filter (Sunscreen) Carbamazepine: Anti-seizure/anti-epileptic

  8. Contaminants of Emerging Concern Sulfonamide Antibiotics Livestock Humans Livestock(humans in Russia)

  9. CECs as Tracers of Bacterial Contamination • Pets • Wastewater ? https://upload.wikimedia.org/wikipedia/commons/e/e8/WWTP_Antwerpen-Zuid.jpg • Livestock • Septic Tanks • Wildlife http://floridaseptictank.com/wp-content/uploads/2013/03/1122.jpg http://www.nrcs.usda.gov/Internet/FSE_MEDIA/stelprdb1042913.jpg https://lh3.ggpht.com/_ftvY4W7_Y04/TIVCgnXpP6I/AAAAAAAABQo/XOU_5Ymygu4/s1600/Goofy+Raccoons.JPG

  10. CECs as Tracers of Bacterial Contamination • Pets • Wastewater • Can presence/absence/trends/patterns of CECs in water entering Puget Sound inform on source of bacterial contamination? • Can CECs be useful tracers? • Septic System Effluent ? https://upload.wikimedia.org/wikipedia/commons/e/e8/WWTP_Antwerpen-Zuid.jpg • Livestock • Septic Tanks • Wildlife http://floridaseptictank.com/wp-content/uploads/2013/03/1122.jpg http://www.nrcs.usda.gov/Internet/FSE_MEDIA/stelprdb1042913.jpg https://lh3.ggpht.com/_ftvY4W7_Y04/TIVCgnXpP6I/AAAAAAAABQo/XOU_5Ymygu4/s1600/Goofy+Raccoons.JPG

  11. Kitsap Sampling Plan • Focus on Septic Impacts • ~20 Sampling Locations • Two Control (not impacted) • Eight Confirmed OSS Impact(dye testing) • Three Presumed OSS Impact • Two Presumed Impact by Sewage • Two Impacted from Agriculture Source • Two with Unknown Impacts • Sample at two wet season events and two dry season events.

  12. Kitsap Sampling Plan • JMS and others have evaluated different extraction methods to optimize recovery.

  13. CEC Summary Data

  14. Sampling Results Control

  15. Sampling Results Confirmed Impact by Septic

  16. Sampling Results Confirmed Impact by Septic

  17. Sampling Results Positive Dye Surface Flow

  18. Sampling Results Positive Bacteria Unknown Source

  19. PreliminaryFindings • Sucralose may be a good conservative tracer of human wastewater • A suite of commonly-used compounds may be able to indicate proximity of human wastewater source • Sites with no CEC strongly suggests no human wastewater • Flow path conditions (subsurface or surface flow, for example) appear to be important • CEC “fingerprints” vary by time but may be consistent at a given location.

  20. Boise CreekSurface Water SamplingBacteria and CECs

  21. Boise Creek Watershed • Puyallup River watershed on 303(d) list for fecal coliform • Boise Creek identified as largest FC loading source of any tributary in the TMDL study area • Exceeds water quality standards in both wet and dry season Mathieu and James, 2011

  22. Boise Creek Watershed

  23. Boise Creek Watershed

  24. Boise Creek Watershed

  25. PreliminaryFindings (cont.)Boise Creek Boise Creek sampling supports some previous conclusion: • A suite of commonly-used compounds may be able to indicate proximity of human wastewater source • Sites with no CEC strongly suggests no human wastewater Additionally: • Repeated detection of animal antibiotics in creek branch suggests livestock influence • Supports “fingerprint” approach

  26. Next Steps • Repeat sampling at corrected sites to evaluate CEC persistence (no data exists on this) • Increase range of sites with septic/sewage tracers • septic/subsurface flow samples • WWTP • stormwater/streams/etc • Evaluate effectiveness of pet waste tracers • Evaluate livestock tracer compounds • Evaluate presence of human tracers at livestock positive controls • Reevaluate use/application patterns • Investigate in field/laboratory settings

  27. Next Steps • Feedback? • Other potential needs? Andy James jamesca@uw.edu Justin Miller-Schulze jschulze@u.washington.edu

  28. Bonus Material

  29. Potential Agricultural or Livestock Tracers

  30. Potential Pet Waste Tracers

  31. Short Term Variation(are pulses important?) • Spatial Variation – between sampling location • Temporal Variation – between sampling events • What is time scale of variation? Sampling Location Groundwater Flow http://floridaseptictank.com/wp-content/uploads/2013/03/1122.jpg

  32. Short Term Variation(are pulses important?) • Alex Gipe– UWT Summer Intern (also SoundCitizen) • Choose several sites in Kitsap project area • Take 24-hour composite sample and repeated grab samples Sampling Location Groundwater Flow http://floridaseptictank.com/wp-content/uploads/2013/03/1122.jpg

  33. High degree of connectivity between single source and sample location High variability

  34. Potentially longer travel time between source and sample location. Variability associated with storm event?

  35. Elution + Evaporation pH Stabilize pH Filtration remove dissolved matter and some biological material Samples collected in 1liter LDPE cubitainers Filtration Extraction Final Sample Matrix Preparation 150 µl sample is brought up to 1500 µl with pH = 2.8 acetic acid and spiked with 10 µl Internal standard mixture Samples are eluted with organic solvent (methanol and/or methanol/MTBE mixture) and then concentrated to ~150 µl Extraction with nonpolar “Oasis HLB” solid phase extraction cartridge concentrates analytes and removes (some) sample matrix interferences JMS, 2013

  36. Bacterial Tracers • General culture methods (e.g., fecal coliform test) • Genetic markers. • specific sequences in 16S rRNA. Highly conserved and useful for bacterial identification. • Bacteroidales spp. • Anaerobic • Expected to have limited viability outside of host • Known markers for many animals (e.g., humans, dogs, cows, horses, etc.) • Do not have markers for all animals (e.g., wildlife) and is often horizontal transfer of bacteria of species in close contact (e.g., humans and their pets) • Fate and transport of genetic material is difficult to predict (sediments can act as a reservoir of genetic material)

  37. Are CECs at Levels of Concern? Approach or Exceed Predicted No Effects Concentrations

  38. Are CECs at Levels of Concern?Unknown Contribution of Metabolites

  39. Detection Frequency and MDL

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