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

Assessing Pennsylvania’s Watersheds and Fish Health OriginsOrigins Environmental ConcernsEnvironmental Concerns EPA CCL 3EPA CCL 3 PA DEP Phase IPA DEP Phase I PA DEP Phase IIPA DEP Phase II Temple Univ. AOP StudyTemple Univ. AOP Study

What Are Emerging Contaminants? OTC drugsOTC drugs PharmaceuticalsPharmaceuticals Veterinary drugsVeterinary drugs NutriceuticalsNutriceuticals PlasticizersPlasticizers FragrancesFragrances LotionsLotions ShampoosShampoos Flame retardantsFlame retardants Antibacterial soapsAntibacterial soaps PesticidesPesticides PCBsPCBs DetergentsDetergents SunscreensSunscreens CosmeticsCosmetics

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

Not a new phenomenonNot a new phenomenon Recent advancements in laboratory chemical analysis methodologies have lowered the limits of detectionRecent 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 commerciallyHave existed in the environment for as long as they have been used commercially

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

Medicines are produced and used in very large volumesMedicines are produced and used in very large volumes Nearly 50% use at least 1 prescription drug dailyNearly 50% use at least 1 prescription drug daily 4 of every 5 patients leave doctor with a prescription4 of every 5 patients leave doctor with a prescription Almost 800 million prescription items were dispensed in % more than in 1997Almost 800 million prescription items were dispensed in % more than in 1997 Estimated that hospitals and long-term care centers intentionally discard an est. 250 million pounds a yearEstimated that hospitals and long-term care centers intentionally discard an est. 250 million pounds a year 40% of antibiotics manufactured are fed40% of antibiotics manufactured are fed to livestock to livestock Pharmaceutical Inputs

Endocrine System A complex network of glands that release hormones and influence almost every cell, organ, and function of the bodyA complex network of glands that release hormones and influence almost every cell, organ, and function of the body

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

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

Effects will first be seen in aquatic communitiesEffects will first be seen in aquatic communities Constant exposure – purposeful & inadvertentConstant exposure – purposeful & inadvertent Compounds not tested on humansCompounds not tested on humans Ecological breakdown of parent compoundsEcological breakdown of parent compounds BioaccumulationBioaccumulation Unknown effects of minute concentrationsUnknown effects of minute concentrations Unknown effects of mixtures & minute concentrationsUnknown effects of mixtures & minute concentrations Concern for Human Health

Antibiotic ResistanceAntibiotic Resistance Endocrine DisruptionEndocrine Disruption Developing fetuses and those with suppressed immunity may be particularly vulnerable to human health effectsDeveloping 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 determinedPotential risks to public health and safety have yet to be determined Concern for Human Health

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

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

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

Required to make regulatory determinations of 5 contaminants every 5 years from a compiled listRequired to make regulatory determinations of 5 contaminants every 5 years from a compiled list 3 Criteria3 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 EPA’s CCL3

EPA selected 116 candidates (104 chemicals and 12 microbiologicals)EPA selected 116 candidates (104 chemicals and 12 microbiologicals) 10 pharmaceuticals were added to the list between the draft and final form10 pharmaceuticals were added to the list between the draft and final form The 10 substances consist of nine hormone compounds and one antibioticThe 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 SDWAFirst time EPA will consider pharms for potential regulation under the SDWA

National Recon Study USGS “Reconnaissance” study in was 1 st nationwide investigation of pharms, hormones, & other organic contaminants in 139 streams in 30 states:USGS “Reconnaissance” study in was 1 st 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 “Pharmaceuticals, hormones, & other organic wastewater contaminants in U.S. streams, : A national reconnaissance.” Environmental Science & Technology. 36(6):

DEP Project Overview Phase I Purpose:Purpose: –To document the occurrence and distribution of selected pharmaceuticals and antibiotics in streams and well water in South Central PA

DEP Project Overview Phase I Screen for pharmaceutical and antibiotic compounds in South-Central PAScreen 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 operationsSamples were collected at locations upstream and downstream of the municipal effluents or animal feeding operations –6 wells

PharmaceuticalsPharmaceuticals –Suite of 15 compounds –USGS National Water Quality Laboratory (NWQL) in Denver, CO AntibioticsAntibiotics –Suite of 31 compounds –USGS Organic Geochemistry Research Laboratory (OGRL) in Lawrence, KS Data Analysis

AcetaminophenAcetaminophen CaffeineCaffeine CarbamazepineCarbamazepine CodeineCodeine CotinineCotinine DehydronifedipineDehydronifedipine DiltiazemDiltiazem DiphyenydramineDiphyenydramine Target Pharmaceuticals FluoxetineFluoxetine p-Xanthinep-Xanthine RantidineRantidine SalbutamolSalbutamol SulfamethoxazoleSulfamethoxazole ThiabendazoleThiabendazole TrimethoprimTrimethoprim WarfarinWarfarin

Target Antibiotics Macrolides Azithromycin Erythromycin Anhydro-erythromycin Anhydro-erythromycin Roxithromycin Roxithromycin Tylosin Tylosin Virginiamycin VirginiamycinQuinolines Ciprofloxacin Lomefloxacin LomefloxacinNorfloxacinOfloxacinSarafloxacin Enrofloxacin EnrofloxacinSulfonamidesSulfachloropyridazine Sulfadiazine Sulfadiazine Sulfadimethoxine SulfadimethoxineSulfamethazine Sulfamethoxazole Sulfamethoxazole Sulfathiazole Sulfathiazole Tetracyclines Chlorotetracycline Epi-chlorotetracycline Epi-chlorotetracycline Iso-chlorotetracycline Iso-chlorotetracycline Epi-iso-chlorotetracycline Epi-iso-chlorotetracycline Doxycycline Doxycycline Oxytetracycline Oxytetracycline Epi-oxytetracycline Epi-oxytetracycline Tetracycline Tetracycline Epi-tetracycline Epi-tetracycline Other Antibiotics Lincomycin Trimethoprim Trimethoprim Chloramphenicol Chloramphenicol Ormetoprim Ormetoprim

Streams Receiving Wastewater Effluent Spring Creek, Berks CountySpring Creek, Berks County Lititz Run, Lancaster CountyLititz Run, Lancaster County Killinger Creek, Lebanon CountyKillinger Creek, Lebanon County Middle Spring Creek, Franklin CountyMiddle Spring Creek, Franklin County Mountain Creek, Cumberland CountyMountain Creek, Cumberland County *Conoy Creek, Lancaster County*Conoy Creek, Lancaster County*disqualified

Streams in Agricultural Areas Dominated by AFOs Muddy Run, Chester CountyMuddy Run, Chester County Bachman Run, Lebanon CountyBachman Run, Lebanon County Snitz Creek, Lancaster CountySnitz Creek, Lancaster County Trout Run, Lebanon CountyTrout Run, Lebanon County Little Chickies Creek, Lancaster CountyLittle Chickies Creek, Lancaster County Three Square Hollow Run, Cumberland CountyThree Square Hollow Run, Cumberland County

Wells 6 locations in Adams, Huntington, Lancaster and Union Counties6 locations in Adams, Huntington, Lancaster and Union Counties Primarily represent agricultural areasPrimarily represent agricultural areas Not used for drinking waterNot used for drinking water

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

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

Streams Receiving Runoff from AFOsStreams Receiving Runoff from AFOs –Pharmaceuticals: (max. conc. of μg/L) AcetaminophenAcetaminophen CaffeineCaffeine CotinineCotinine DiphenhydramineDiphenhydramine CarbamazepineCarbamazepine –Antibiotics: (max. conc. of μg/L) OxoxytetracyclineOxoxytetracycline SulfadimethoxineSulfadimethoxine SulfamethoxazoleSulfamethoxazole TylosinTylosin Phase I Results

5 detections total in 24 samples. 5 detections total in 24 samples. Four compounds were detected 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. Tylosin is the only compound detected that is used in agriculture. Others related to human uses. Phase I Results Livestock Wells

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

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

Concentrations of Selected Pharmaceuticals and Antibiotics in South-Central Pennsylvania Waters, March through September 2006 Concentrations of Selected Pharmaceuticals and Antibiotics in South-Central Pennsylvania Waters, March through September 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

PART 1: Continuation of Phase IPART 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 stream5 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 watershedThere 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 DEP Project Overview Phase II:

PART 2: Evaluate Sourcewater for EC ’ sPART 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. DEP Project Overview Phase II

Preliminary Results Indicate all 27 sites had at least 1 compound detectedIndicate all 27 sites had at least 1 compound detected 12 of the 15 (80%) pharmaceutical compounds analyzed were detected at least once12 of the 15 (80%) pharmaceutical compounds analyzed were detected at least once 16 of 32 (50%) antibiotic compounds were detected at least once16 of 32 (50%) antibiotic compounds were detected at least once 9 of 19 (47%) hormone compounds were detected at least once9 of 19 (47%) hormone compounds were detected at least once

Commonly Detected Pharmaceuticals Caffeine – StimulantCaffeine – Stimulant Carbamazepine - Mood stabilizing (epileptic)Carbamazepine - Mood stabilizing (epileptic) Acetaminophen- AnalgesicAcetaminophen- Analgesic Diphenhydramine - Antihistamine (Benadryl)Diphenhydramine - Antihistamine (Benadryl) Cotinine - Metabolite of nicotineCotinine - Metabolite of nicotine

Pharmaceuticals Detected

Commonly Detected Antibiotics Sulfamethoxazole - Human useSulfamethoxazole - Human use Trimethoprim - Human useTrimethoprim - Human use Azithromycin - Human useAzithromycin - Human use Ofloxacin - Human useOfloxacin - Human use Tylosin - Used for cattle, swine, and poultryTylosin - Used for cattle, swine, and poultry

Antibiotics Detected

Commonly Detected Hormones Estrone - Female – EstrogenEstrone - Female – Estrogen 4-androstene 3,17 dione Male – testosterone precursor)4-androstene 3,17 dione Male – testosterone precursor) 17 beta estradiol - Female – Estrogen17 beta estradiol - Female – Estrogen Cis-androsterone Male – Testosterone metaboliteCis-androsterone Male – Testosterone metabolite

Hormones Detected

Preliminary Findings Detections and concentrations are flow relatedDetections and concentrations are flow related Seasonal component to some compounds – use relatedSeasonal component to some compounds – use related Some compounds are related to specific sitesSome compounds are related to specific sites Many compounds attach to sediment and may bio accumulateMany compounds attach to sediment and may bio accumulate

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

Published Research Intersex (Testicular Oocytes) in Smallmouth Bass from the Potomac River and Selected Nearby DrainagesIntersex (Testicular Oocytes) in Smallmouth Bass from the Potomac River and Selected Nearby Drainages –V. S. Blazer, L. R. Iwanowicz, D. D. Iwanowicz, D. R. Smith, J. A. Young, J. D. Hedrick, S. W. Foster, and S. J. Reeser –Journal of Aquatic Animal Health 2007;19:242–253 The prevalence of testicular oocytes is discussed in terms of human population and agricultural intensity.The prevalence of testicular oocytes is discussed in terms of human population and agricultural intensity.

Our ability to measure contaminants currently exceeds our understanding of their environmental effects

PART 3: Comprehensive Fish Health AssessmentPART 3: Comprehensive Fish Health Assessment –16 sites statewide –Target species include white suckers and smallmouth bass –Water and bed sediment will also be analyzed for pharmaceuticals, antibiotics, hormones, and waste water compounds –A final report is anticipated early 2010 DEP Project Overview Phase II

Part 4: Identification of Pathogenic BacteriaPart 4: Identification of Pathogenic Bacteria –USGS Michigan Water Science Center has developed assays for actual bacterial pathogens such as E. coli O157, a broad class of pathogenic E. coli called Shiga- toxin producing E. coli (STEC) and Enterococci that carry the esp gene –These DNA-based methods may be used to identify the source of fecal pollution –The USGS MI WCS and the DEP BOL will analyze for pathogenic and fecal source markers from E. coli and enterococci in a side by side PCR method comparison DEP Project Overview Phase II

Advanced Treatment of Drinking Water to Remove Trace Emerging Contaminants DEP –Temple University Steroid hormonesSteroid hormones 17α estradiol17α estradiol 17β estradiol17β estradiol 17α dihydroequilin17α dihydroequilin 17α ethinylestradiol17α ethinylestradiol EstriolEstriol EstroneEstrone EquilinEquilin EquilinenEquilinen Norethindrone acetateNorethindrone acetate 19-norethisterone19-norethisterone MestranolMestranol Bisphenol ABisphenol A TechnologiesTechnologies –UV –UV/Peroxide –Ozone/Peroxide –Ozone/UV

What Have We Learned? Present at sub-ppb concentrations in water.Present at sub-ppb concentrations in water. - Streams and Groundwater Present as complex mixtures.Present as complex mixtures. Reflect a wide range of human activities.Reflect a wide range of human activities. Some compounds mobile and persistent.Some compounds mobile and persistent. Detectable concentrations related to fate and transport not just the amount used.Detectable concentrations related to fate and transport not just the amount used.

Summary of Results Several compounds are commonly detected but most are rarely foundSeveral compounds are commonly detected but most are rarely found -Acetaminophen, caffeine, carbamazepine, sulfamethyloxozale Found at large and small sites in various settings.Found at large and small sites in various settings. Distance from point discharges related to detectionsDistance from point discharges related to detections - Higher concentrations near wastewater treatment discharges.

Summary of Results Groundwater less effected than surface waterGroundwater less effected than surface water Look for patterns in seasonality – land use – flow conditions in data.Look for patterns in seasonality – land use – flow conditions in data. Other sources – Landfills – pharmaceutical manufacturingOther sources – Landfills – pharmaceutical manufacturing

Closing Thoughts Drinking water is only one route of exposureDrinking water is only one route of exposure Humans are exposed to some compounds at far greater concentrations through other contact:Humans are exposed to some compounds at far greater concentrations through other contact: –food, food preparation, the intended purpose of the product, dermal absorption, inhalation (overspray), etc.

“I can tell you with absolute certainty that, if we regulate contaminants based upon detection rather than health effects, we are embarking on a futile journey without end” - Dr. Shane Snyder In his statement before the Senate Subcommittee on Transportation Safety, Infrastructure Security, and Water Quality

Acknowledgements US EPAUS EPA PA DEP Safe Drinking Water FundPA DEP Safe Drinking Water Fund USGS Water Science CenterUSGS Water Science Center

Questions?? Arianne Proctor (717) Program Analysis and Support Bureau of Water Standards and Facility Regulation PA Department of Environmental Protection Thank You