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ဟံၣ်My WebLink ဘၣ်ဃးဒီး04-2016 Emerging Pollutants in Our WatershedvEEEEEeeCornell UniversitySchool of Civil and Environmental IAWWTF EngineeringCoCCCCoCoCoCCCCCCCCCCCCCCCCCCCCCCCCCC CCC rnrnnrnrnrnrnrnrnrnrnrrnrrnrnrnrnrrn nrrnrnrnrrnrnnrnrrrnnrnrrrnn nnnneleeeeeeee l Unnnnnnnnnnnnnnnnnnnnn iversityyyyyyyyyy SSSSSSSSSSSSSSSS SScSSSSSSSSSSSSSSS hhhhhhohhhhhhh ol of CiCCCCCCCCCCCCCCC CCCCC CC CCCCCC vivivvivivivvvvivivivivvvivvivivivivvv vviviv vvivvivilllllllllllllllllllll and EnEEEEEEEEEEEEEEEEEEEEEEEEEvironmmmmmeneeeeeeeeeeeeeeeeeeeeee tal E Tompkins County Water Resources Council 18 April 2016 Emerging pollutants in our watershed and statewide monitoring plans Jose Lozano, Laboratory Director, Ithaca Area Wastewater Treatment Facility Susan Allen-Gil, Professor, Environmental Studies and Science, Ithaca College Damian E. Helbling, Assistant Professor, Civil and Environmental Engineering, Cornell University IAWWTF A Sampler: SH2440 ¾One of four USGS methods ¾Pharmaceuticals 110 compounds ¾One sampling event: July 2014 How much are we talking about? Top medications by prescriptions Medications 2014 - number of prescriptions (regardless of how many days) 1. Levothyroxin 120 million (thyroid medication) 2. Acetominophen/hyrdrocodone 119 million (Vicodin-pain medication) 7. Metformin 77 million (diabetes and obesity) 11. Amoxicillin 54 million (antibiotic) 18. Sertaline 44 million (antidepressant) 19. Tramadol 44 million (pain medication) Source: Medicine Use and Spending Shifts, IMS Institute for Healthcare Informatics Mysterious metformin • 7th most prescribed drug in US • Anti-diabetic, Also associated with weightloss – Obesity Treatment • High mg/dose (1000 mg) • 100% excretion • Very common in surface waters – 6 TONS PER YEAR INTO AQUATIC SYSTEMS • May have endocrine disrupting potential in young male fish Cornell Raw Water Groups June 2014July2014 September2014 December2014May2015July2015 ng/L 0 50 100 150 200 250 Antibiotic Anticonvulsant Antidepressant Antifungal Antihistamine Antiviral Benzodiazepine Diabetics (Metformin) Hypertensives Muscle Relaxants Opiates/Opiods Other (Non Pharmaceutical) Other Pharmaceuticals Stimulant Cornell Raw Water Breakdown July 2014 Atrazine Metformin Acetaminophen Fexofenadine Carbamazepine 0 5 101520 Antibiotic Anticonvulsant Antidepressant Antifungal Antihistamine Antiviral Benzodiazepine Diabetics (Metformin) Hypertensives Muscle Relaxants Opiates/Opiods Other (Non Pharmaceutical) Other Pharmaceuticals Stimulant ng/L Ithaca Drinking Water Breakdown July 2014 Atrazine Metformin 0 5 10 15 20 25 30 35 Antibiotic Anticonvulsant Antidepressant Antifungal Antihistamine Antiviral Benzodiazepine Diabetics (Metformin) Hypertensives Muscle Relaxants Opiates/Opiods Other (Non Pharmaceutical) Other Pharmaceuticals Stimulant ng/L July 2014 SH2440 Influent vs. Effluent Caffeine Acetaminophen Metformin Methyl-1H-benzotriazole 1,7-Dimethylxanthine Fexofenadine Acyclovir Nicotine Theophylline Pseudoephedrine + ephedrine3 Ranitidine Cotinine Atenolol Sulfamethoxazole Desvenlafaxine Diphenhydramine Famotidine Morphine Trimethoprim Tramadol Methocarbamol Cimetidine Sitagliptin Diltiazem Lidocaine Penciclovir Lamivudine Venlafaxine Citalopram Meprobamate Metoprolol Bupropion Metaxalone Amphetamine Carbamazepine Pentoxifylline Codeine Triamterene Oxycodone Fluconazole Quinine Nadalol Nizatidine Hydrocortisone Dextromethorphan Abacavir Propranolol Hydrocodone Verapamil Desmethyldiltiazem Thiabendazole Atrazine Carisoprodol Amitriptyline Sulfadimethoxine Sertraline Erythromycin 10-Hydroxy-amitriptyline Methadone Norverapamil Omeprazole + esomeprazole3 Paroxetine Chlorpheniramine Hydroxyzine Loratadine Glyburide 1 10 100 1000 10000 100000 ng/L Antibiotic Anticonvulsant Antidepressant Antifungal Antihistamine Antiviral Benzodiazepine Diabetics (Metformin) Hypertensives Muscle Relaxants Opiates/Opiods Other (Non Pharmaceutical) Other Pharmaceuticals Stimulant Hydroxyzine Glyburide Loratadine Verapamil Norverapamil Omeprazole + esomeprazole3 Abacavir Albuterol 10-Hydroxy-amitriptyline Acetaminophen Erythromycin Temazepam Desmethyldiltiazem Hydrocodone Carisoprodol Thiabendazole Atrazine Dextromethorphan Propranolol Nadalol Oxycodone Lamivudine Pentoxifylline Citalopram Fluconazole Metaxalone Triamterene Quinine Cotinine Caffeine Codeine Carbamazepine Metoprolol Diltiazem Nicotine Phenytoin Penciclovir Morphine Meprobamate Sitagliptin Venlafaxine Bupropion Lidocaine Tramadol Trimethoprim Pseudoephedrine + ephedrine3 Methocarbamol Diphenhydramine Acyclovir Sulfamethoxazole Atenolol Desvenlafaxine Fexofenadine Methyl-1H-benzotriazole Metformin 1 10 100 1000 10000 100000 ng/L Influent Effluent Influent Breakdown July 2014 Antibiotic Anticonvulsant Antidepressant Antifungal Antihistamine Antiviral Benzodiazepine Diabetics (Metformin) Hypertensives Muscle Relaxants Opiates/Opiods Other (Non Pharmaceutical) Other Pharmaceuticals Stimulant Caffeine Acetaminophen Metformin Methyl-1H-benzotriazole 1,7-Dimethylxanthine Fexofenadine Acyclovir Nicotine Theophylline Pseudoephedrine + ephedrine3 Ranitidine Cotinine Atenolol Sulfamethoxazole Desvenlafaxine Diphenhydramine Famotidine Morphine Trimethoprim Tramadol Methocarbamol Cimetidine Sitagliptin Diltiazem Lidocaine Penciclovir Lamivudine Venlafaxine Citalopram Meprobamate Metoprolol Bupropion Metaxalone Amphetamine Carbamazepine Pentoxifylline Codeine Triamterene Oxycodone Fluconazole Quinine Nadalol Nizatidine Hydrocortisone Dextromethorphan Abacavir Propranolol Hydrocodone Verapamil Desmethyldiltiazem Thiabendazole Atrazine Carisoprodol Amitriptyline Sulfadimethoxine Sertraline Erythromycin 10-Hydroxy-amitriptyline Methadone Norverapamil Omeprazole + esomeprazole3 Paroxetine Chlorpheniramine Hydroxyzine Loratadine Glyburide 10 100 1000 10000 100000 ng/L Effluent Breakdown July 2014 Antibiotic Anticonvulsant Antidepressant Antifungal Antihistamine Antiviral Benzodiazepine Diabetics (Metformin) Hypertensives Muscle Relaxants Opiates/Opiods Other (Non Pharmaceutical) Other Pharmaceuticals Stimulant Metformin Methyl-1H-benzotriazole Fexofenadine Desvenlafaxine Atenolol Sulfamethoxazole Acyclovir Diphenhydramine Methocarbamol Pseudoephedrine + ephedrine3 Trimethoprim Tramadol Lidocaine Bupropion Venlafaxine Sitagliptin Meprobamate Morphine Penciclovir Phenytoin Nicotine Diltiazem Metoprolol Carbamazepine Codeine Caffeine Cotinine Quinine Triamterene Metaxalone Fluconazole Citalopram Pentoxifylline Lamivudine Oxycodone Nadalol Propranolol Dextromethorphan Atrazine Thiabendazole Carisoprodol Hydrocodone Desmethyldiltiazem Temazepam Erythromycin Acetaminophen 10-Hydroxy-amitriptyline Albuterol Abacavir Omeprazole + esomeprazole3 Norverapamil Verapamil Loratadine Glyburide Hydroxyzine 1 10 100 1000 10000 100000 ng/L Cayuga Lake Breakdown July 2014 Metformin Atrazine Fexofenadine Cotinine 0 20 40 60 80 100 120 140 Antibiotic Anticonvulsant Antidepressant Antifungal Antihistamine Antiviral Benzodiazepine Diabetics (Metformin) Hypertensives Muscle Relaxants Opiates/Opiods Other (Non Pharmaceutical) Other Pharmaceuticals Stimulant ng/L + contrast media veterinary medicines lifestyle chemicals Emerging chemical contaminants – types and sources pesticides flame retardants biocides Illicit drugs personal care products pharmaceuticals 13 oil and gas chemicals plasticizers DBPs PFOA UV filters 14 pesticides, pharmaceuticals, personal care products, industrial chemicals… 2,740 Full-scan high-resolution MS acquisition H3C N CH3 CH3 O CH3 O Cl metolachlor [M+H]+ 283.1339 Predicted Retention Time: 10.5 min C15 H22 Cl N O2 Predicted MS2 fragments: 252.11 176.14 134.10 146.10 254.11 Expected isotope (MS) pattern: [M+H+1]+ 284.1367 (15%) [M+H+2]+ 285.1304 (32%) [M+H+3]+ 286.1338 (5%) Suspect screening in the Ithaca urban water system 15 Data processing – confirmation of a suspect hit 3 4 5 6 Time (min) 0 10 20 30 40 50 60 70 80 90 100 Relative Abundance 3.97 4.49 5.16 5.56 HPLC Chromatogram Authentic Standard 3 4 5 6 Time (min) 0 10 20 30 40 50 60 70 80 90 100 Relative Abundance 3.99 4.44 5.61 4.96 3.06 HPLC Chromatogram IAWWTF Effluent December 2015 50 100 150 200 250 300 m/z 0 20 40 60 80 100 Relative Abundance 168.1020 105.0336 290.1385 82.0655 150.0914 119.0492 272.1279 67.0548 314.6166 176.0856 0 20 40 60 80 100 Relative Abundance 168.1020 105.0336 290.1383 82.0655 150.0914 124.1121272.1281 76.0399 198.0910 216.0603 183.0812 312.0994 MS2 Spectra Authentic Standard MS2 Spectra IAWWTF Effluent December 2015 290 291 292 m/z 0 20 40 60 80 100 Relative Abundance 290.1385 291.1418 292.1456290.7261 0 20 40 60 80 100 Relative Abundance 290.1387 291.1419 292.1181290.6310 MS Spectra IAWWTF Effluent December 2015 MS Spectra Authentic Standard cocaine metabolite confirmed in all wastewater samples [M+H]+ 290.1387 C16 H19 N O4 16 Confirmed suspects in Ithaca water samples veterinary medicines artificial sweeteners pesticides biocides personal care products pharmaceuticals Illicit drugs plasticizers PFOA UV filters flame retardants Concentrations of confirmed micropollutants in 2015 17 18 Example: Six Mile Creek watershed 19 Example: Six Mile Creek watershed vEEEEEeeCornell UniversitySchool of Civil and Environmental Engineering CoCoCoCCCCCrnrnnrnrnrnrnrnrnrnrnrnell UnnnnnniversitySchool of CiCCCCCCCvivivivivil land EnEEvironmeneeeetal E eeeeeeee SSSSSSSSSSSSSSSSSSSSSSSSSSSSSSSS hhhhhhhhhhhhCCCoCCCCCCCCCC rrrrrnrnrrnrnrnrnrnrnrnrnrrnnnnnnn nnnnn CCCCCCCCCCCCCC vvvvvvivivivivivivivvvvvv llllllllll EEEEEEE mmeeeeeeeeeeCCCCCCCCrrrrnn nnnnnnnCCCC vvivivvivivilllEEEEEEEEEEEEE mmeeeeCCCCCCC rnrnn nnnCCC viviv llllll EEEeeeeyyyyyyyyy New York Times February 28, 2016 - Since 1851 Fears About Water Supply Grip Village That Made Teflon Products Jesse McKinley HOOSICK FALLS, N.Y. — One resident called 911 asking whether the village’s water would burn his skin off. Families have lined up to have their blood drawn and their wells tested. Banks stopped giving out mortgages, and some local residents stopped washing their dishes, their clothes and themselves. Erin Brockovich has been to town. Such are the unpleasant contours of a public health emergency that is playing out in Hoosick Falls, a quiet river-bend village near the New York-Vermont border that has been upended by disclosures that the public water supply was tainted with high levels of perfluorooctanoic acid, or PFOA, a toxic chemical linked in some studies to an increased risk for cancer, thyroid disease and serious complications during pregnancy. 21 Statewide monitoring: developing a rapid response program Develop a state-wide coordination of water analysis laboratories and strategies for collecting water samples Convene a working group to identify critical contaminants that need to be part of the assessment Develop a protocol for updating the list as new contaminants are identified Launch a demonstration program in 2016 over a small area (1 or 2 counties) Propose a state-wide program in 2017 with committed participants ready to engage 22 Summary of key points 2. Suspect screening is a powerful new tool that helps emerging contaminants “emerge” 4. A statewide rapid response program has been proposed and is currently under review. Tompkins County is under consideration as a potential demonstration site 3. Septic systems are an underexplored source of emerging chemical contaminants 1. A collaborative monitoring program has been underway for two years