Occurrence of Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters

Transcription

1 Occurrence of Pharmaceuticals, Hormones, and Organic Wastewater Compounds in Pennsylvania Waters U.S. Geological Survey Scientific Investigations Report Background Pharmaceuticals, Hormones, and Other Wastewater Contaminants in US Streams, : A National Reconnaissance. Koplan, et al / Pennsylvania State Section of the Summer 2013 Webinar Series 1 of 28

2 Background Concentrations of Selected Pharmaceuticals and Antibiotics in South-Central Pennsylvania Waters, March through September Occurrence of Pharmaceuticals, Hormones, and Organic Compounds in Pennsylvania Waters, What are Emerging Contaminants Substances that are characterized by a real or perceived threat to human health or the environment. Have only recently been able to detected. There is no currently published health standard. Pennsylvania State Section of the Summer 2013 Webinar Series 2 of 28

3 Extremely Low Concentrations No regulatory limits. Measured in nanograms. Concentrations in surface waters are minisule when compared to pharmaceutical doses Acetaminophen pharmaceutical 200 mg Acetaminophen in water mg/l Emerging Contaminants Human Drugs Vet. Drugs Antibiotics Hormones Steroids Detergents Plastics Antioxidants Fire retardants Disinfectants Fumigants Fragrances Insecticides/ Repellants Nanomaterials Pennsylvania State Section of the Summer 2013 Webinar Series 3 of 28

4 DEP-USGS Cooperative Study Three year study; March August sites across the state. Sampling was focused within 5 miles of drinking water intakes. Sampled quarterly for pharmaceuticals, antibiotics, hormones and wastewater cpds. Target Pharmaceuticals 16 compounds Acetaminophen Caffeine Carbamazepine Codeine Cotinine Dehydronifedipine Diltiazem Diphyenydramine Fluoxetine p-xanthine Rantidine Salbutamol Sulfamethoxazole Thiabendazole Trimethoprim Warfarin Pennsylvania State Section of the Summer 2013 Webinar Series 4 of 28

5 Macrolides Azithromycin Erythromycin Anhydro-erythromycin Roxithromycin Tylosin Virginiamycin Target Antibiotics 31 compounds 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 Target Hormones 17 compounds 11-ketotestosterone 17-alpha-ethynylestradiol 17-beta-estradiol Norethindrone 3-beta-coprostanol 4-androstene-3,17-dione Cholesterol Cis-androsterone Trans-diethylstilbestrol Epitestosterone Equilenin Estriol Mestranol Progesterone Dihydrotestosterone Testosterone Bisphenol A Pennsylvania State Section of the Summer 2013 Webinar Series 5 of 28

6 Contaminants of Emerging Concern in Pennsylvania Waters Data collection and analysis from surface-water and ground-water. Pennsylvania State Section of the Summer 2013 Webinar Series 6 of 28

7 USGS Contaminants of Emerging Concern Sampling in Pennsylvania. 2 major sampling efforts were conducted in Pa. Funded by PaDEP and USGS Occurrence of Contaminants of Emerging Concern in Pennsylvania Waters: Occurrence survey at various potential sources. Contaminants of Emerging Concern sampling near drinking water intakes at PaDEP Water Quality Network sites. Endocrine Disruptors External compounds that interferes with or mimics natural hormones. Can cause reproduction, development, and or behavior of an organism. Hormones estrogen, testosterone. Fish health issues intersex fish. Potential human health issues. Pennsylvania State Section of the Summer 2013 Webinar Series 7 of 28

8 Sources Human Wastewater treatment plants Combined sewer overflows Onsite septic systems Industrial Discharge Landfills Water Reuse Animal Waste lagoons, etc. Land application Processing plants Aquaculture All Teflon equipment Critically cleaned methanol rinsed. Two person field crew clean hands- dirty hands. Composite sample from 3-15 locations in the stream. All samples analyzed at USGS labs. Sampling Pennsylvania State Section of the Summer 2013 Webinar Series 8 of 28

9 QA samples Blanks 4 detections in 33 blanks submitted to the lab. Testosterone (0.001 g/l) Tylosin (0.006 g/l) Erythromycin (0.008 g/l) Salbutamol (0.011 g/l) Bisphenol A was eliminated from the report analysis based on blank results (27% detection frequency) Duplicates and Spikes Duplicate results were less than 30% relative percent difference for water samples and less than 45% for streambed-sediment samples. Spike samples had mean recoveries that ranged from 81% to 102% for water samples. Methods Development New lab capabilities for ECs: - Pharmaceuticals - Antibiotics - Hormones - Wastewater compounds Detection levels at expected ambient concentrations (ppb, ppt, ppq) Pennsylvania State Section of the Summer 2013 Webinar Series 9 of 28

10 General Results Low number of compounds detected Low concentrations (ppt) Concentrations influenced by: Number of sources Concentration at source Distance from source Flow Unknown effects on human and ecosystem health Commonly Detected Compounds Caffeine - Stimulant Carbamazepine - Mood stabilizing (epileptic) Acetaminophen- Analgesic Diphenhydramine - Antihistamine (Benadryl) Cotinine - Metabolite of nicotine Sulfamethoxazole - Human use Trimethoprim - Human use Azithromycin - Human use Erythromycin Human use Ofloxacin - Human use Estrone Natural estrogen hormone Cis-Androstone - Natural androgen hormone 4-Androstene-3,17-dione - Natural androgen hormone Pennsylvania State Section of the Summer 2013 Webinar Series 10 of 28

11 Phase I sampling Surface-water sites Ag affected upstream downstream WWT affected upstream downstream Ground-water wells in agricultural areas Quarterly samples for 1 year. Base flow samples. Sites located in southcentral Pa. Sampled for pharmaceuticals and antibiotics in water. No hormones in Pennsylvania State Section of the Summer 2013 Webinar Series 11 of 28

12 Results from Phase I Most compounds were rarely detected. Low concentrations of some compounds detected below WWTPs: Occurrence dependent on: Flow % of flow from WWTP Number of detections Acetaminophen Caffeine Codeine Diphenhydramine Carbamazepine Diltiazeme Salbutamol Upstream Downstream Pennsylvania State Section of the Summer 2013 Webinar Series 12 of 28

13 Results from Phase I Streams with a large % of flow from a WWTP had more compounds detected at higher concentrations. Site Number of detections % flow from WWTP Spring Creek 19 7 Middle Spring Creek Mountain Creek 7 5 Killinger Creek Lititz Run Pennsylvania State Section of the Summer 2013 Webinar Series 13 of 28

14 Results Phase I (Occurrence Survey): Very few detections upstream from WWTPs. More detections downstream from WWTPs. All concentrations are low (sub microgram/liter levels) Few detections in agricultural streams Almost no detections in stock wells Emerging Contaminants Project Phase II Focus on downstream of WWTPs. Added Hormone analysis. Added Organic Wastewater Compound analysis Added sediment sampling Pennsylvania State Section of the Summer 2013 Webinar Series 14 of 28

15 Hormone detections Percent detection Water Sediment Estrone 4-Androstene- 3,17-dione 17-beta- Estradiol cis- Androsterone Equilenin Estriol Most hormones were rarely detected. Commonly detected hormones included: 4-Androstene and estrone. Very low concentrations. OWC detections Similar pattern to other compounds most compounds were rarely detected a few compounds were commonly detected. Some OWC were found exclusively in water and others only in sediment. Polycyclic aromatic compounds were found concentrated in sediment samples. Flame retardants and plasticizers were detected primarily in water samples. Pennsylvania State Section of the Summer 2013 Webinar Series 15 of 28

16 Results Phase II (Occurrence Survey): Hormones and wastewater compounds had a similar pattern of detection as the pharmaceuticals in Mostly non-detects with a few commonly detected compounds. Some compounds were found primarily in the water or sediment. Some compounds were found in both sediment and water. Estrone and 4-Androstene-3,17-dione were the most commonly detected hormones. DEET and the flame retardants Tri(dichloroisopropyl)phosphate and Tri(2- chloroethyl)phosphate were the most commonly detected wastewater compounds. Pennsylvania State Section of the Summer 2013 Webinar Series 16 of 28

17 Drinking water intake sites Started in March Three years of sampling (Completed in August 2009). 27 sites across the state. Sampling is focused near drinking water intakes. Sampling quarterly for pharmaceuticals, antibiotics and hormones. Pennsylvania State Section of the Summer 2013 Webinar Series 17 of 28

18 Drinking water intake sites Samples collected at various flows. (Low flows are not targeted) Regular WQN QW sample collected at all sites along with EC sample. E-coli, Enterococci, Giardia, Cryptosporidium samples collected quarterly. Various size streams including 5 reference sites. Results 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. Pennsylvania State Section of the Summer 2013 Webinar Series 18 of 28

19 Commonly Detected Pharmaceuticals Caffeine - Stimulant Carbamazepine - Mood stabilizing (epileptic) Acetaminophen- Analgesic Diphenhydramine - Antihistamine (Benadryl) Cotinine - Metabolite of nicotine Pharmaceuticals detected 90 percent detection Pennsylvania State Section of the Summer 2013 Webinar Series 19 of 28

20 Commonly Detected Antibiotics Sulfamethoxazole - Human use Trimethoprim - Human use Azithromycin - Human use Ofloxacin - Human use Tylosin - Used for cattle, swine, and poultry. Antibiotics detected percent detection Pennsylvania State Section of the Summer 2013 Webinar Series 20 of 28

21 Commonly Detected Hormones Estrone - Female - Estrogen 4-androstene 3,17 dione Male testosterone precursor) 17 beta estradiol - Female - Estrogen Cis-androsterone Male Testosterone metabolite Hormones detected percent detection Pennsylvania State Section of the Summer 2013 Webinar Series 21 of 28

22 Reference Sites Sites were established on small watersheds used for drinking water that had limited disturbance in the basin. Used to validate the results and to look for contamination in non-point source areas. Reference Sites 5 Reference sites Average # detections per sample = 1 Max = 4 Number of compounds detected = 5 Max concentration (acetaminophen) =.03 g/l 21 other sites Average # detections per sample = 4 Max = 10 Number of compounds detected = 12 Max concentration (acetaminophen) =.21 g/l Pennsylvania State Section of the Summer 2013 Webinar Series 22 of 28

23 Patterns of Occurrence Hydrologic conditions Number of discharges Land use Seasonal variability Hydrologic Conditions Concentrations were generally highest during low flow conditions. Some compounds were detected more frequently during low flow conditions and were not detected during high flow conditions. Pennsylvania State Section of the Summer 2013 Webinar Series 23 of 28

24 Chemical Results Detection frequencies of selected compounds in samples collected from sites downstream from wastewater-effluent-discharge sites, and sites near drinkingwater intakes, in Pennsylvania. [ng/l, nanograms per liter] Compound Number of detections at Number of detections at Percent detections at Number of analyses concentrations greater concentrations less than any concentration than reporting level reporting level Concentration range (ng/l) Sites located downstream from wastewater-effluent-discharge sites ( ) Carbamazepine Diphenhydramine Sulfamethoxazole ,150 Trimethoprim Estrone Sites located near drinking-water intake ( ) Carbamazepine Diphenhydramine Sulfamethoxazole Trimethoprim Estrone Number of Discharges Sites located in watersheds that had greater than 0.28 permitted discharges per drainage area had the greatest number of detections. Sites that had less than 0.28 permitted discharges per drainage area had similar number of detections. Pennsylvania State Section of the Summer 2013 Webinar Series 24 of 28

25 Land Use Watersheds that had high percentages of forested lands had the lowest number of detections. Watersheds that had high percentages of urban and or agricultural lands had the highest number of detections. Seasonality In general the occurrence of contaminants of emerging concern did not vary consistently by season. Some compounds did show a seasonal effect but it was not consistent. Variation in use and in instream biological uptake can effect concentrations. Pennsylvania State Section of the Summer 2013 Webinar Series 25 of 28

26 Only a few compounds are commonly detected and concentrations are in the PPT range. Concentrations lower than at sites downstream of WWTPs. Detections and concentrations are flow related. Compounds were concentrated at low flow. Findings Findings Detections related to number of discharges upstream basin size. Land use related to detection pattern forested basins had low detection frequencies. Pennsylvania State Section of the Summer 2013 Webinar Series 26 of 28

27 Ecological Effects Our ability to measure contaminants currently exceeds our understanding of their environmental effects. Reports Available at the USGS PaWSC web site (pa.water.usgs.gov) under publications. Also available from the USGS Pubs warehouse. Concentrations of Selected Pharmaceuticals and Antibiotics in South-Central Pennsylvania Waters, March through September 2006 (pubs.er.usgs.gov/publication/ ds300) Occurrence of Pharmaceuticals, Hormones and Wastewater Compounds in Pennsylvania Waters, (pubs.er.usgs.gov/publication/sir Pennsylvania State Section of the Summer 2013 Webinar Series 27 of 28

28 Additional Reports Duris, J., 2013, Factors Related to Occurrence and Distribution of Selected Bacterial and Protozoan Pathogens in Pennsylvania Streams: Water Research 47 pp Vicki Blazer from the USGS Leetown Science Center is publishing a related fish health article. See: for info. Questions/Thank You Rhonda Manning rmanning@pa.gov Drew Reif agreif@usgs.gov Pennsylvania State Section of the Summer 2013 Webinar Series 28 of 28