Watershed Chemical Signaling and Endocrine Disruption A Modeling Opportunity

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1 Watershed Chemical Signaling and Endocrine Disruption A Modeling Opportunity Larry Barber Dana Kolpin Alan Vajda and many other colleagues

2 Contaminant Geochemistry Organic and Inorganic Comprehensive and Contemporaneous Chemical, Hydrological, and Biological Analysis Hierarchical Approach Barber 1992, Hierarchical analytical approach to evaluating the transport and biogeochemical fate of organic compounds in sewage-contaminated ground water, Cape Cod, Massachusetts. in Lesage and Jackson eds., Ground Water Contamination and Analysis at Hazardous Waste Sites, Mercel Dekker, Inc., New York, NY, 73.

3 Consumer Product Cycle Active Ingredient Starting Products Reaction Pathway Parent Compound Contaminants such as drugs differ from industrial contaminants such as solvents Product Formulation Wastewater Treatment Consumer Use Discharge Parent Degradates Adjuvants Water Supply

4 Emerging Contaminants in US Waters 139 Streams in 30 States 62 Intense AFO Activities 52 Intense Urbanization 17 Mixed Land Use 8 Minimally Developed 22 Antibiotics 14 Prescription Drugs 5 Nonprescription Drugs 15 Hormones and Steroids 39 Household and Industrial Widespread occurrence of biologically active chemicals - Kolpin et al. 2002, Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. Streams, : A national Reconnaissance. Environ. Sci. Technol. 36, 1202.

5 Sex Hormones Contraception 58 million women practice contraception 10 million use oral contraceptives = 88 kg/yr HO H H OH CH 3 C H CH Biogenic 98 million excrete ~0.1 mg/day/person = 3577 kg/yr H 17-α-Ethynylestradiol OH CH 3 H H H HO H 17-β-Estradiol Arcand-Hoy and others, 1998

6 The Human Endocrine System Glands that produce hormones and the corresponding receptors govern every aspect of the life of vertebrate animals Colborn and others, 1996

7 Boulder Creek Watershed Colorado Front Range 25 MEAN DAILY STREAMFLOW, IN CUBIC METERS PER SECOND WATER YEAR 1200 Rural Crystalline Bedrock Urban Urban / Agric. Sandstones and Shales Specific Conductance (µs/cm) BC High-Flow BC Low-Flow Inflows High-Flow Inflows Low-Flow Nederland Wastewater Dry Creek Coal Creek St. Vrain Boulder Wastewater Fourmile Creek Eben Fine Distance from MBC-Eldora (m) - Barber et al., 2006, Chemical loading into surface water along a hydrological, biogeochemical, and land use gradient - A holistic watershed approach: Environ. Sci. Technol.., 40,

8 Pharmaceuticals in Boulder Creek Compound Acetaminophen Caffeine Carbamazapine Cimetidine Codeine Cotinine Diltiazem Dimethylxanthene Diphenhydramine Ibuprofen Ranitidine Sulfamethoxazole Trimethoprim Use Analgesic Stimulant Antiepiletic Antacid Cough suppressant Nicotine metabolite Antiangial Caffeine metabolite Antihistamine Analgesic Antacid Antibiotic Antibiotic Greater frequency/concentrations at low flow Concentrations <1 ppb but complex mixtures Indicative of related compounds of concern Occur primarily below WWTP but also upper watershed Persist for kilometers in stream

9 Endocrine Disruption in Boulder Creek Reference Downstream White Sucker (Catostomus commersoni) <0.8 ng/l 17β-Estradiol 2.9 ng/l 2.1 ng/l 1.2 ng/l 1.4 ng/l

10 Reproductive Disruption in White Suckers Downstream from the WWTP 1. Female-biased sex 2. Gonadal Intersex 3. Decreased testicular sperm abundance Fraction of males n=27 * * χ 2,p< % 90% Percent abundance 80% 70% 60% 50% 40% 30% 20% 10% 0% Ref Eff Ref Eff Fall 2003 Spring 2004 Abundance Very Strong Strong Moderate Weak Absent Vajda et al. 2008, Reproductive disruption in fish downstream from an estrogenic wastewater effluent. Environ. Sci. Technol. 42,

11 Digital Elevation Model Quadrangles completely or partially in Boulder Creek Watershed Boulder Black Hawk Central City East Portal Eldorado Springs Empire Erie Gold Hill Lafayette Longmont Louisville Monarch Lake Nederland Niwot Ralston Buttes Tungsten Ward Additional quadrangles Allenspark Arvada Commerce City Eastlake Golden Gowanda Hygiene Isolation Peak Lyons Raymond

12 Characteristics of Boulder Creek and Sub-Watersheds Sub-watershed Drainage Area km 2 Relief km Mean Elevation km Mean Slope degree North Facing Aspect % Boulder Creek Fourmile Creek N Boulder Creek M Boulder Creek S Boulder Creek Coal Creek Rock Creek Lower Boulder Creek

13 Precipitation and Soil Organic Matter

14 Sources of Endocrine Disrupting Chemicals Wastewater Treatment Plants Row Crop Agriculture Forestry Management Practices On-site Wastewater Disposal Animal Feeding Operations Natural Biogenic Sources Solid Wastes Disposal Land Application of Biosolids Outdoor Recreational Activities

15 In-stream Fate Barber et al., 1996, Organic contamination of the Mississippi River from municipal and industrial wastewater: USGS Circular 1133, p