Pharmaceuticals and Endocrine Disrupting Compounds in Cape Cod Surface Waters and Groundwater

Transcription

1 Pharmaceuticals and Endocrine Disrupting Compounds in Cape Cod Surface Waters and Groundwater Laurel Schaider, Ph.D. Silent Spring Institute Wastewater and Emerging Contaminants of Concern February 24, 2010 Falmouth, MA 2008

2 Recent media coverage Pollutants in D.C. area drinking water Intersex fish a problem in Potomac River watershed Group wants action on drug residue in river (Newburyport, MA) Study finds traces of drugs in Indiana waterways

3 Outline What are emerging contaminants? How do they get into the environment? What have previous studies found? What has Silent Spring Institute found? What are the implications for ecological and human health? Emerging contaminants Improved analytical techniques let us measure chemicals at lower and lower levels Scientific understanding of effects hasn t caught up with our ability to measure these low levels of chemicals

4 Pharmaceuticals and personal care products (PPCPs) Classified by their intended uses Pharmaceuticals: over-the-counter medications prescription medications caffeine, nicotine veterinary drugs Personal care products: ingredients in soaps, shampoos, sunscreen, bug sprays, cosmetics, etc. examples: DEET, triclosan, phthalates Endocrine disrupting compounds (EDCs) Classified by their mode of action Interfere with natural hormones Some pharmaceuticals & personal care products are also hormone disruptors - for example: natural and synthetic estrogens alkylphenol ethyoxylates (from detergents) triclosan (antimicrobial soaps) parabens (preservatives) PPCPs EDCs

5 Outline What are emerging contaminants? How do they get into the environment? What have previous studies found? What has Silent Spring Institute found? What are the implications for ecological and human health? Pharmaceuticals and personal care products in the environment

6 Outline What are emerging contaminants? How do they get into the environment? What have previous studies found? What has Silent Spring Institute found? What are the implications for ecological and human health? Previous studies 2002: nationwide reconnaissance of US streams by US Geological Survey Tested for 95 chemicals (including 33 EDCs) in 139 streams What was found?

7 USGS nationwide study (Kolpin et al., 2002) 82 of 95 chemicals detected at least once 80% of streams had at least one detected chemical 7 compounds detected in >50% of streams cholesterol and coprostanol (steroids) DEET (bug spray active ingredient) caffeine triclosan (antimicrobial products, EDC) TCEP (flame retardant) 4-nonylphenol (detergent breakdown product, EDC) USGS study on Cape Cod (Zimmermann 2005) Tested wastewater and drinking water supplies (public, semi-public and private) 13 of 85 chemicals detected in high nitrate drinking water supplies tetrachloroethylene ( perc, solvent) acetaminophen (Tylenol) sulfamethoxazole (antibiotic) carbamazepine (anti-convulsant)

8 Outline What are emerging contaminants? How do they get into the environment? What have previous studies found? What has Silent Spring Institute found? What are the implications for ecological and human health? Why are Cape Cod drinking water supplies vulnerable? Reliance on shallow aquifer as source of drinking water Septic systems are predominant wastewater treatment (80-85%) Porous sandy soils allow relatively fast movement of groundwater Septic system tank Leaching field Increasing development puts water quantity and quality stresses on the Cape s aquifers

9 Highlights of SSI water research Contaminants in drinking water wells and septage 1 Alkylphenols (detergent breakdown products) and bisphenol A found in drinking water and septage 1 Rudel et al. Environmental Science & Technology, 1998 Highlights of SSI water research Contaminants in drinking water wells and septage 1 Alkylphenols (detergent breakdown products) and bisphenol A found in drinking water and septage Contaminant migration from a septic system through groundwater 2 Contaminants detected 20 feet downstream of septic system Little breakdown in oxygen-depleted part of aquifer 1 Rudel et al. Environmental Science & Technology, Swartz et al. Environmental Science & Technology, 2006

10 Example: Estrone (E1) concentrations with distance Land surface 62 ng/l from distribution box Leach pit 2.5 ft 10.3 ft 19.3 ft 11 ft Water table Oxygen-depleted zone Groundwater flow ng/l 24 ng/l ND Well Cluster 1 30 ng/l ND Well Cluster ng/l Well Cluster 3 Swartz et al., ES&T, 2006 Highlights of SSI water research Breast cancer status and historic indicators of wastewater impact to individual s drinking water 3 Reconstruct historic exposure using nitrate, land use No association found between water and breast cancer, but limitations to approach 3 Brody et al. Environmental Health, 2007; Swartz et al. JEAEE, 2003

11 Highlights of SSI water research Breast cancer status and historic indicators of wastewater impact to individual s drinking water 3 Reconstruct historic exposure using nitrate, land use No association found between water and breast cancer, but limitations to approach Pharmaceuticals and hormones in Cape Cod ponds 4 Cape ponds are fed by groundwater Are there detectable levels of hormones and pharmaceuticals in these ponds, and what is the effect of residential density? 3 Brody et al. Environmental Health, 2007; Swartz et al. JEAEE, Standley et al. Environmental Toxicology & Chemistry PPCPs in ponds on Cape Cod - 3 in low residential density areas - 3 in high residential density areas - each pond sampled up to 3 times in 2006

12 Wastewater and Emerging Contaminants of Concern Lewis Pond (higher residential density) 225 m Flax Pond (lower residential density) 200 m

13 Frequency of detections Frequency detected in samples Frequency detected in samples 60% 50% 40% 30% 20% 10% 0% Low residential density ponds (n=7) hormones pharmaceuticals hormones pharmaceuticals 60% Androstenedione 17beta-estradiol Estrone Progesterone Carbamazepine Meprobamate Pentoxifylline Sulfamethoxazole Trimethoprim Frequency detected in samples Ibuprofen detected, not shown on graphs 50% 40% 30% 20% 10% 0% High residential density ponds (n=9) Androstenedione 17beta-estradiol Estrone Progesterone Carbamazepine Meprobamate Pentoxifylline Sulfamethoxazole Trimethoprim Standley et al., ET&C, 2008 Maximum detected concentrations Maximum concentration (ng/l) Concentration (ng/l) Low residential High residential density ponds (n=7) density ponds (n=9) hormones pharmaceuticals hormones pharmaceuticals 12 Androstenedione Androstenedione 17beta-estradiol 17beta-estradiol Estrone Estrone Progesterone Progesterone Carbamazepine Carbamazepine Meprobamate Meprobamate Pentoxifylline Pentoxifylline Sulfamethoxazole Sulfamethoxazole Trimethoprim Trimethoprim Concentration (ng/l) Androstenedione Androstenedione 17beta-estradiol 17beta-estradiol Estrone Estrone Progesterone Progesterone Carbamazepine Carbamazepine Meprobamate Meprobamate Pentoxifylline Pentoxifylline Sulfamethoxazole Sulfamethoxazole Trimethoprim Trimethoprim Ibuprofen detected, not shown on graphs Standley et al., ET&C, 2008

14 Cape Cod drinking water study 9 public supply districts, 20 groundwater wells Testing for wide range of chemicals Pharmaceuticals - Perfluorinated compounds Hormones - Alkylphenol ethoxylates Personal care products - Flame retardants Fragrances - Herbicides Indicators of WW (nitrate, boron, caffeine) Results are relevant to wastewater and drinking water infrastructure planning Outline What are emerging contaminants? How do they get into the environment? What have previous studies found? What has Silent Spring Institute found? What are the implications for ecological and human health?

15 Ecological implications Feminization of fish observed in streams downstream of wastewater treatment plants Lab studies have demonstrated effects of hormones in fish Slightly elevated incidence of intersex fish at 10 ng/l estrone or 17beta-estradiol Limited field studies 5-6 ng/l synthetic estrogen led to crash in fathead minnow population in experimental lake study Mixtures important observed effects a lower concentrations in combinations than individually Other animals may also be susceptible Human Health Many Unanswered Questions Reported levels are far below therapeutic levels However, many are endocrine disruptors Timing is key: exposures at wrong time Mixtures: additive, other interactions demonstrated in cell culture and animal models Drugs also have side effects, e.g. carcinogenicity, developmental toxicity Large gaps in our understanding of effects

16 Putting it all together Some chemicals are effectively removed in traditional wastewater treatment systems (centralized and septic tanks), others persist Ongoing research to understand: How chemicals move through the environment Health effects Which chemicals to prioritize Minimizing inputs Drug take-back programs Maintenance of wastewater treatment systems Long-term planning Improved treatment technologies Green chemistry Acknowledgements Centers for Disease Control Babylon Breast Cancer Coalition Agua Fund The Susan S. Bailis Breast Cancer Research Fund Mass. Environmental Trust Contact info: Laurel Schaider w w w. s s i i l l e e n n t t s s p p r i r n i g n. g o. r o g r g

17 24 Feb 2010 Wastewater and Emerging Contaminants of fconcern Dave Reckhow Department t of Civil il & Environmental Engineering University of Massachusetts David A. Reckhow Falmouth Meeting 1 Municipal Wastewater Treatment Incorporating 1 and 2 treatment May also need 3 treatmentt t David A. Reckhow Falmouth Meeting 2 1

18 24 Feb 2010 Small WWT Systems From a few hundred people to several thousand David A. Reckhow Falmouth Meeting 3 On-site disposal Septic Systems Classical Layout David Reckhow CEE 370 L#32 4 2

19 24 Feb 2010 Biological (Secondary) Treatment Activated sludge Q = flow of WW X = bacteria conc. S = organic compounds X o Q S o Influent Aeration Basin V,X X S Settling Tank X e S Effluent Q r X r Return activated sludge Separation and Recycle of bacteria Helps to elevate bacterial numbers and allow for retention of slower growing strains David A. Reckhow Falmouth Meeting 5 PPCP Removal by 2 o Treatment Treatment Bins T1 = >80% T2 = 50-80% T3 = <50% Stephenson & Oppenheimer, 2007 WERF report 20 target compounds David A. Reckhow Falmouth Meeting 6 3

20 24 Feb 2010 Bacterial Age or SRT Oxybenzone: Sunscreen David A. Reckhow Falmouth Meeting 7 Average Bacterial Age Bacterial Age (cont.) Triclosan: Germacide David A. Reckhow Falmouth Meeting 8 Average Bacterial Age 4

21 24 Feb 2010 Bacterial Age (cont.) Galaxolide: Fragrance Average Bacterial Age David A. A. Reckhow Falmouth Meeting 9 Notes on WERF study Higher SRT was more effective - why? Slow growing bacteria can thrive More diverse microbial population broader degradation capacities Good for slow biodegradation kinetics HRT was strongly correlated to SRT Galaxolide Not toxic? Could bioaccumulate? May be lost upon UV disinfection David A. Reckhow Falmouth Meeting 10 5

22 24 Feb 2010 Removal by Advanced Treatment Secondary Treatment (Baseline case) All steroids & hormones plus caffeine, ibuprophen, naproxen, acetaminophen, penicillin Coagulation + filtration (CA+F) Also tetracyclines, oxofloxacin, gemfribrozil, sulfamethoxazole Bio Nutrient removal + membrane filt (EBNR + MF) Above + erythromycin, albuterol, cimetidine, trimethoprim, warfarin Bio Nutrient removal + coag + filtration (EBNR + F) Above + fluoxetine, dehydronifedipine David A. Reckhow Falmouth Meeting 11 Puget Sound Study Detail I Many are found in sludge (biosolids) Not really destroyed Fraction Removed AS AD EBNR AS + N CA+F EBNR +MF EBNR+F Acetaminophen Albuterol Androsterone Azithromycin David A. Reckhow Falmouth Meeting 12 Bis(2-ethylhexyl) phthalate Bisphenol A Butylbenzylphthalate Caffeine Campesterol Carbamazepine 6

23 24 Feb 2010 Advanced Treatment (cont.) Why does enhanced biological nutrient removal work so well? Incorporates both aerobic and anaerobic zones (nitrification-denitrification) Different bacteria High wastewater recycling rate Longer time for removal Concern: some are in sludge Control of Toxic Chemicals in Puget Sound, Phase 3: PPCPs in Municipal WW and their Removal by Nutrient Treatment Technologies Lubliner et al., 2010 David A. Reckhow Falmouth Meeting 13 NP Septic Systems I SF ATU Wilcox study (2009) David A. Reckhow Falmouth Meeting 14 7

24 24 Feb 2010 Septic System Performance II Wilcox Study: Performance vs Design Wilcox et al., 2009 [J. Env. Quality 38: ] David A. Reckhow Falmouth Meeting 15 Septic System Performance III Wilcox David A. Reckhow Falmouth Meeting 16 8

25 24 Feb 2010 Soil Subsurface transport and persistence Fate of Pharmaceutical and Trace Organic Compounds in Three Septic System Plumes, Ontario, Canada Carrara et al., 2008 [ES&T 42:8: ] David A. Reckhow Falmouth Meeting 17 Cont. Fate of Pharmaceutical and Trace Organic Compounds in Three Septic System Plumes, Ontario, Canada Carrara et al., 2008 [ES&T 42:8: ] David A. Reckhow Falmouth Meeting 18 9

26 24 Feb 2010 Removal by Residual Disinfectants Snyder et al., 2007 [AwwaRF report] Re emoval by Chloramines 20-50% 50-80% >80% <20% Androstenedione Atrazine g-bhc Caffeine Ibuprofen Carbamazepine Iopromide DDT Meprobamate DEET Metolachlor Dilantin Progesterone Fluorene TCEP Fluoxetine Testosterone Galaxolide Diazepam Pentoxifylline Gemfibrozil Acetaminophen Estradiol Estriol Estrone Ethynyestradiol Triclosan Benzo(a)pyrene Diclofenac Oxybenzone Hydrocodone <20% 20-50% 50-80% >80% Removal by Free Chlorine Erythromycin Musk Ketone Naproxen Sulfamethoxazole Trimethoprim David A. Reckhow Falmouth Meeting 19 Oxidation of PPCPs Average percentage removal of LC/MS/MS and GC/MS/MS compounds by ozone and chlorine across four waters spiked with EDC/PPCPs (PVW, ORW, SRW, CRW). Solid line represents 1:1 removal between ozonation and chlorination experiments. Error bars represent one standard deviation in percentage removal based on experiments in the four waters. Westerhoff et al., 2005 [ES&T, 39:6649] David A. Reckhow Falmouth Meeting 20 10

27 24 Feb 2010 Estradiol: loss means what? Proposed pathway David A. Reckhow Falmouth Meeting 21 11