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What’s in Our Water?

Concentrations of Selected Pharmaceuticals, Antibiotics, Hormones, and Wastewater Compounds In Pennsylvania’s Source Water. What’s in Our Water?. The Ninth Annual Conservation District Watershed Specialist Training Meeting October 13, 2009. Arianne Proctor PA DEP.

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What’s in Our Water?

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  1. Concentrations of Selected Pharmaceuticals, Antibiotics, Hormones, and Wastewater Compounds In Pennsylvania’s Source Water What’s in Our Water? The Ninth Annual Conservation District Watershed Specialist Training Meeting October 13, 2009 Arianne Proctor PA DEP

  2. Assessing Pennsylvania’s Watersheds and Fish Health • Origins • Environmental Concerns • EPA CCL 3 • PA DEP Phase I • PA DEP Phase II • Temple Univ. AOP Study

  3. OTC drugs Pharmaceuticals Veterinary drugs Nutriceuticals Plasticizers Fragrances Lotions Shampoos Flame retardants Antibacterial soaps Pesticides PCBs Detergents Sunscreens Cosmetics What Are Emerging Contaminants?

  4. Emerging Contaminants • Compounds that we are just now beginning to detect in the environment (SW, GW & DW) • Not only new compounds but any pharmaceutical or household chemical. • Also called personal care products or chemicals of emerging concern.

  5. Emerging Contaminants • Not a new phenomenon • Recent advancements in laboratory chemical analysis methodologies have lowered the limits of detection • Have existed in the environment for as long as they have been used commercially

  6. Origins of EC’s • Human activity • Metabolic excretion • Veterinary use • Livestock operations • Hospital pharmaceutical waste • Flushing unused or expired meds • Runoff from land applied biosolids

  7. http://www.epa.gov/ppcp/basic2.html

  8. Pharmaceutical Inputs • Medicines are produced and used in very large volumes • Nearly 50% use at least 1 prescription drug daily • 4 of every 5 patients leave doctor with a prescription • Almost 800 million prescription items were dispensed in 2007 - 59.2% more than in 1997 • Estimated that hospitals and long-term care centers intentionally discard an est. 250 million pounds a year • 40% of antibiotics manufactured are fed to livestock

  9. Endocrine System • A complex network of glands that release hormones and influence almost every cell, organ, and function of the body http://ec.europa.eu/research/endocrine/images/major-endo.gif

  10. Endocrine Disruptors • Interferes with or mimic natural hormones • Can have effects at lower levels • Hormones – estrogen, testosterone • Disruption in reproduction, development, and or behavior • Fish health issues – intersex fish • Potential human health issues?

  11. Environmental Concerns • May degrade quickly, but constant input • Disinfection By-products • Exposure risks for aquatic organisms are much larger than those for humans. • Potential for cumulative and synergistic effects from multiple exposures

  12. Concern for Human Health • Effects will first be seen in aquatic communities • Constant exposure – purposeful & inadvertent • Compounds not tested on humans • Ecological breakdown of parent compounds • Bioaccumulation • Unknown effects of minute concentrations • Unknown effects of mixtures & minute concentrations

  13. Concern for Human Health • Antibiotic Resistance • Endocrine Disruption • Developing fetuses and those with suppressed immunity may be particularly vulnerable to human health effects • Potential risks to public health and safety have yet to be determined

  14. Low Concentrations • Concentrations found are measured in nanograms (Parts Per Trillion). • Concentrations found in surface waters are miniscule when compared to pharmaceutical doses. • Acetaminophen pharmaceutical = 200mg • Acetaminophen in water = 0.00000005 mg/L • No regulatory limits set because there is little know about long term exposure in aquatic systems.

  15. Methods Development • Recent advancements in laboratory chemical analysis methodologies have lowered the limits of detection • New lab capabilities for ECs: - Pharmaceuticals - Antibiotics - Hormones - Wastewater compounds

  16. Why Can’t We Take the Compounds out of the Water? • POTWs are not designed to remove emerging contaminants • Promising technologies include: • Oxidation • Ozonation • Ultrasound • Activated carbon • Reverse osmosis • Focus on controlling disposal at source • Pollution Prevention

  17. EPA’s CCL3 • Required to make regulatory determinations of 5 contaminants every 5 years from a compiled list • 3 Criteria • Must be known to adversely affect human health • Is known or likely to occur in public water systems with frequency or levels which are of public health concern • Regulation presents a meaningful opportunity for health risk reduction

  18. EPA’s CCL3 • EPA selected 116 candidates (104 chemicals and 12 microbiologicals) • 10 pharmaceuticals were added to the list between the draft and final form • The 10 substances consist of nine hormone compounds and one antibiotic • 17α estradiol, 17β estradiol, equilenin, equilin, estriol, estrone, ethinyl estradiol, mestranol, norethindrone and the antibiotic erythromycin. • First time EPA will consider pharms for potential regulation under the SDWA

  19. National Recon Study • USGS “Reconnaissance” study in 1999-2000 was 1st nationwide investigation of pharms, hormones, & other organic contaminants in 139 streams in 30 states: • 82 of 95 antibiotics, prescription & non-prescrip drugs, steroids, & hormones were found in at least 1 sample • 80% streams had 1 or more contaminant • 75% streams contained 2 or more • 54% had more than 5 • 34% had more than 10 • 13% tested positive for more than 20 targeted contaminants Kolpin, D.W. et al. 2002. “Pharmaceuticals, hormones, & other organic wastewater contaminants in U.S. streams, 1999-2000: A national reconnaissance.” Environmental Science & Technology. 36(6):1202-1211.

  20. DEP Project OverviewPhase I • Purpose: • To document the occurrence and distribution of selected pharmaceuticals and antibiotics in streams and well water in South Central PA

  21. DEP Project OverviewPhase I • Screen for pharmaceutical and antibiotic compounds in South-Central PA • 6 streams—effluent dominated • 6 streams—agricultural areas • Samples were collected at locations upstream and downstream of the municipal effluents or animal feeding operations • 6 wells

  22. Data Analysis • Pharmaceuticals • Suite of 15 compounds • USGS National Water Quality Laboratory (NWQL) in Denver, CO • Antibiotics • Suite of 31 compounds • USGS Organic Geochemistry Research Laboratory (OGRL) in Lawrence, KS

  23. Target Pharmaceuticals • Acetaminophen • Caffeine • Carbamazepine • Codeine • Cotinine • Dehydronifedipine • Diltiazem • Diphyenydramine • Fluoxetine • p-Xanthine • Rantidine • Salbutamol • Sulfamethoxazole • Thiabendazole • Trimethoprim • Warfarin

  24. Target Antibiotics Macrolides Azithromycin Erythromycin Anhydro-erythromycin Roxithromycin Tylosin Virginiamycin Quinolines Ciprofloxacin Lomefloxacin Norfloxacin Ofloxacin Sarafloxacin  Enrofloxacin Sulfonamides Sulfachloropyridazine Sulfadiazine Sulfadimethoxine Sulfamethazine Sulfamethoxazole Sulfathiazole Tetracyclines Chlorotetracycline Epi-chlorotetracycline Iso-chlorotetracycline Epi-iso-chlorotetracycline Doxycycline Oxytetracycline Epi-oxytetracycline Tetracycline Epi-tetracycline Other Antibiotics Lincomycin Trimethoprim Chloramphenicol Ormetoprim

  25. Streams Receiving Wastewater Effluent • Spring Creek, Berks County • Lititz Run, Lancaster County • Killinger Creek, Lebanon County • Middle Spring Creek, Franklin County • Mountain Creek, Cumberland County • *Conoy Creek, Lancaster County *disqualified

  26. Streams in Agricultural Areas Dominated by AFOs • Muddy Run, Chester County • Bachman Run, Lebanon County • Snitz Creek, Lancaster County • Trout Run, Lebanon County • Little Chickies Creek, Lancaster County • Three Square Hollow Run, Cumberland County

  27. Wells • 6 locations in Adams, Huntington, Lancaster and Union Counties • Primarily represent agricultural areas • Not used for drinking water

  28. Data Analysis • Samples collected in March/April, May, July and September 2006 • Analyses were completed on 120 environmental samples and 21 quality-control samples

  29. Phase I Results • Streams Receiving Wastewater Effluent • Pharmaceuticals: • Caffeine (4.75 μg/L) (micrograms per liter) • Para-xanthine (0.853 μg/L) • Carbamazepine (0.516 μg/L) • Ibuprofen (0.227 μg/L) • Antibiotics: • Azithromycin (1.65 μg/L) • Sulfamethoxazole (1.34 μg/L) • Ofloxacin (0.329 μg/L) • Trimethoprim (0.256 μg/L)

  30. Phase I Results • Streams Receiving Runoff from AFOs • Pharmaceuticals: (max. conc. of 0.053 μg/L) • Acetaminophen • Caffeine • Cotinine • Diphenhydramine • Carbamazepine • Antibiotics: (max. conc. of 0.157 μg/L) • Oxoxytetracycline • Sulfadimethoxine • Sulfamethoxazole • Tylosin

  31. Phase I Results Livestock Wells • 5 detections total in 24 samples. • Four compounds were detected – 2 pharmaceuticals: cotinine and diphenhydramine – 2 antibiotics: tylosin (2) and sulfamethoxazole • Tylosin is the only compound detected that is used in agriculture. Others related to human uses.

  32. Phase I Results Stream Sampling • 12 of 16 (81%) pharmaceuticals were detected at least once. • 12 of 32 (38%) antibiotics were detected at least once. • 78% of all detections were downstream from wastewater discharges. • Few detections above discharges and concentrations were lower than the downstream samples.

  33. Phase I Results Stream Sampling • The average number of compounds detected downstream of: • Animal feeding operation = 3 • Municipal-wastewater discharges = 13 • Carbamazepine (Mood stabilizing, epileptic drug) was the most frequently detected compound below both AFO and WWT discharges. • All concentrations are low – PPT

  34. Concentrations of Selected Pharmaceuticals and Antibiotics in South-Central Pennsylvania Waters, March through September 2006http://pubs.usgs.gov/ds/300/ U.S. Geological Survey Data Series 300 By Connie A. Loper, J.Kent Crawford, Kim L. Otto, Rhonda L. Manning, Michael T. Meyer, and Edward T. Furlong

  35. DEP Project OverviewPhase II: 2007-2010 • PART 1: Continuation of Phase I • Continue to characterize surface water downstream of wastewater treatment plants • 5 locations from Phase I plus 3 new sites and 1 reference stream • There are 6 sampling sites are in the Susquehanna watershed, 2 sites in the Potomac watershed, and one sampling site in the Delaware watershed • Analysis will include additional suites for hormone analytes and wastewater compounds in water and streambed sediment • Sampling will occur one time per year for 3 years beginning May 2007

  36. DEP Project OverviewPhase II • PART 2: Evaluate Sourcewater for EC’s • Chemical analysis of surface water at 27 Water Quality Network (WQN) Stations • Stations were chosen based on their proximity to Public Water Supply surface water intakes (within 3 miles) • Samples will be analyzed quarterly for pharmaceuticals, antibiotics, and hormones as well as pathogens and bacteria • There are 11 sampling locations in the Susquehanna watershed, 11 in the Ohio watershed, 4 in the Delaware watershed and 1 in the Potomac watershed.

  37. Preliminary Results • Indicate all 27 sites had at least 1 compound detected • 12 of the 15 (80%) pharmaceutical compounds analyzed were detected at least once • 16 of 32 (50%) antibiotic compounds were detected at least once • 9 of 19 (47%) hormone compounds were detected at least once

  38. Commonly Detected Pharmaceuticals • Caffeine – Stimulant • Carbamazepine - Mood stabilizing (epileptic) • Acetaminophen- Analgesic • Diphenhydramine - Antihistamine (Benadryl) • Cotinine - Metabolite of nicotine

  39. Pharmaceuticals Detected

  40. Commonly Detected Antibiotics • Sulfamethoxazole - Human use • Trimethoprim - Human use • Azithromycin - Human use • Ofloxacin - Human use • Tylosin - Used for cattle, swine, and poultry

  41. Antibiotics Detected

  42. Commonly Detected Hormones • Estrone - Female – Estrogen • 4-androstene 3,17 dione Male – testosterone precursor) • 17 beta estradiol - Female – Estrogen • Cis-androsterone Male – Testosterone metabolite

  43. Hormones Detected

  44. Preliminary Findings • Detections and concentrations are flow related • Seasonal component to some compounds – use related • Some compounds are related to specific sites • Many compounds attach to sediment and may bio accumulate

  45. FISH KILLS • Fish Kills of Smallmouth Bass and Sunfish • South Branch Potomac, WV - 2002 • North Fork, Shenandoah, VA – 2004, 2006 • South Fork, Shenandoah – 2005 • Juniata River, Susquehanna, PA - 2005 • Intersex in Smallmouth Bass • Immature eggs are found in the testes • Exposure to natural & synthetic estrogens may stimulate vitellogenin production by males

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