Endocrine Disruptors and Persistent Organics in Ithaca NY.

Susan Allen-Gil, Jose L. Lozano Ithaca College and Ithaca Area Wastewater Treatment Facility.

1 • PAT PHILLIPS AND TIA-MARIA SCOTT (USGS ALBANY) • NYS DEPARTMENT OF HEALTH • ITHACA COLLEGE (SUSAN ALLEN-GIL) • CORNELL (DAMIAN HELBLING AND AMY POCHODYLO) • CORNELL COOPERATIVE EXTENSION • CAYUGA FLOATING CLASSROOM

2 IAWWTF

3 THE STARTING POINT: DRINKING WATER INTAKE

Six Mile Creek Fall Creek 50 250

Antibiotic 40 200 Anticonvulsant Antidepressant Antifungal 30 150 Antihistamine Atrazine Antiviral ng/L ng/L ng/L Benzodiazepine 20 100 Diabetics (Metformin) Hypertensives Mescle Relaxants Nicotine 10 50 Opiates/Opiods Other (Non Pharmaceutical) Other Pharmaceuticals 0 Metformin 0 Stimulant

July 2014 July 2014 July 2015 June 2014 May 2015 June 2014 May 2015

December 2014 December 2014 September 2014 September 2014

• Six Mile Creek water is cleaner than Fall Creek Water (note scales differ)

• Metformin, atrazine, nicotine, and acetaminophen found most often and at highest concentrations

• Detectable, reportable, but less than 1 pinch of salt on 10 tons of potato chips 4 • Doesn’t mean that is what comes out of your sink! (just atrazine! 35 nanograms/L)

AFTER HUMAN USE: INFLUENT

Antibiotic Anticonvulsant 350000 Antidepressant Antifungal 300000 Antihistamine Antiviral Benzodiazepine 250000 Diabetics (Metformin) Hypertensives Mescle Relaxants 200000 Opiates/Opiods Other (Non Pharmaceutical) ng/L ng/L Other Pharmaceuticals 150000 Stimulant

100000 • Much higher levels that

50000 raw water

0 • More compounds

July 2014 June 2014 May 8 2015May 9 2015 May 7 2015 May 10 2015May 12 2015May 13 2015May 14 2015 December 2014 September 2014 5 INFLUENT: Caffeine Acetaminophen Metformin Methyl-1H-benzotriazole 1,7-Dimethylxanthine MAY 9, 2015 Fexofenadine Pseudoephedrine + ephedrine3 Acyclovir Nicotine Theophylline Atenolol Ranitidine Desvenlafaxine Antibiotic Diphenhydramine Morphine Anticonvulsant Trimethoprim Cotinine Antidepressant Sitagliptin Methocarbamol Antifungal Sulfamethoxazole Antihistamine Lidocaine Amphetamine Antiviral Tramadol Venlafaxine Benzodiazepine Citalopram Meprobamate Diabetics (Metformin) Diltiazem Cimetidine Hypertensives Metoprolol Quinine Mescle Relaxants Lamivudine Carbamazepine Opiates/Opiods Famotidine Piperonyl butoxide Other (Non Pharmaceutical) Codeine Bupropion Other Pharmaceuticals Fluconazole Dextromethorphan Stimulant Oxycodone Fluoxetine Metaxalone Pentoxifylline Abacavir Penciclovir Nadalol Triamterene Ketoconazole Nizatidine Verapamil Desmethyldiltiazem Thiabendazole Amitriptyline Propranolol Sertraline Promethazine 10-Hydroxy-amitriptyline Atrazine Carisoprodol Chlorpheniramine Norverapamil Methadone 6 Loratadine Fluvoxamine

1 10 100 1000 10000 100000 1000000 ng/L JULY 2014 SH2440 INFLUENT VS. EFFLUENT

Caffeine Metformin Acetaminophen Methyl-1H-benzotriazole Metformin Fexofenadine Methyl-1H-benzotriazole Desvenlafaxine 1,7-Dimethylxanthine Atenolol Fexofenadine Acyclovir Sulfamethoxazole Nicotine Acyclovir Theophylline Diphenhydramine Pseudoephedrine + ephedrine3 Methocarbamol Ranitidine Pseudoephedrine + ephedrine3 Cotinine Trimethoprim Atenolol Sulfamethoxazole Tramadol Desvenlafaxine Lidocaine Diphenhydramine Bupropion Famotidine Venlafaxine Morphine Sitagliptin Trimethoprim Tramadol Meprobamate Methocarbamol Morphine Cimetidine Penciclovir Sitagliptin Phenytoin Diltiazem Nicotine Lidocaine Penciclovir Diltiazem Lamivudine Metoprolol Venlafaxine Carbamazepine Citalopram Codeine Meprobamate Caffeine Metoprolol Bupropion Cotinine Metaxalone Quinine Amphetamine Triamterene Carbamazepine Metaxalone Pentoxifylline Fluconazole Codeine Citalopram Triamterene Oxycodone Antibiotic Pentoxifylline Fluconazole Lamivudine Quinine Anticonvulsant Oxycodone Nadalol Antidepressant Nadalol Nizatidine Antifungal Propranolol Hydrocortisone Dextromethorphan Antihistamine Dextromethorphan Abacavir Antiviral Atrazine Propranolol Benzodiazepine Thiabendazole Hydrocodone Diabetics (Metformin) Carisoprodol Verapamil Hydrocodone Desmethyldiltiazem Hypertensives Thiabendazole Muscle Relaxants Desmethyldiltiazem Atrazine Opiates/Opiods Temazepam Carisoprodol Other (Non Pharmaceutical) Erythromycin Amitriptyline Acetaminophen Sulfadimethoxine Other Pharmaceuticals 10-Hydroxy-amitriptyline Sertraline Stimulant Erythromycin Albuterol 10-Hydroxy-amitriptyline Abacavir Methadone Omeprazole + esomeprazole3 Norverapamil Norverapamil Omeprazole + esomeprazole3 Verapamil Paroxetine Loratadine Chlorpheniramine Hydroxyzine Glyburide Loratadine Hydroxyzine Glyburide 1 10 100 1000 710000 100000 1 10 100 1000 10000 100000 ng/L ng/L Influent Effluent 8 9 Treatment trend:

Polar escapes

Lipophilic stays

10 THE ENDING POINT: CAYUGA LAKE

400

Caffeine 300 Much lower Atzrazine • Lidocaine concentrations than influent/effluent 200 ng/L (100,000 to 300 ng/l) Metformin • But some 100 pharmaceuticals detectable 0

July 2014 June 2014 May 2015

September 2014

11 CAYUGA LAKE PHARMACEUTICALS SEPTEMBER 2014

Lidocaine

Metformin

Atrazine

Methyl-1H-benzotriazole Deicing fluid additive

Caffeine

Nicotine

Cotinine

12 0 20 40 60 80 100 120 140 160 ng/L Compounds Always Detected

• Bis(2-ethylhexyl)phthalate – Common plasticizer, classified as a High Production Volume Chemical

• Caffeine

• DEET

• Prometon – Herbicide used for landscaping; not used for food crops

• Sucralose

• Venlafaxine – Antidepressant

13 14 Alternatives:

Avoidance

UV-O3 / Filtration

Selective adsorption/desorption (cyclodextrins)

EAG Technology

15 Also of Concern: Microplastics Crowbar Sample

Near East Shore Sailing Dock, 2016, appears to be in GI tract 18 All USGS data will be on the NWIS data base

http://waterdata.usgs.gov/nwis

Phillips, Patrick Damian E Helbling Susan Allen-Gil Jose Luis Lozano

https://drive.google.com/file/d/0BwqAUDio7q27b2JpQjJVTDk 0R2c/view?usp=sharing

19 THE ENDING POINT: CAYUGA LAKE HORMONES

1000 • 300 -1000 ng/l

800 • Very low synthetic estrogens

600 ng/L Cholesterol 400

200 Androgens

0 June 2014 July 2014 September 2014 May 2015 July 2015

20 CAYUGA LAKE: WASTEWATER COMPOUNDS

Personal Care/Domestic Use 0.4 Polycyclic Aromatic Hydrocarbon Pesticide/Herbicide Plant/Animal Biochemical Plasticizer/Phosphorous Based Flame Retardant Other

0.3

0.2 µg/L

0.1

0.0

June 2014 July 2014 May 2015 21

September 2014 CAYUGA LAKE: WASTEWATER COMPOUNDS

Tris(2-chloroethyl) phosphate (TCEP)

Metolachlor

Caffeine

Camphor Personal Care/Domestic Use Polycyclic Aromatic Hydrocarbon Pesticide/Herbicide Isophorone Plant/Animal Biochemical Plasticizer/Phosphorous Based Flame Retardant Other

0.00 0.01 0.02 0.03 0.04 0.05 0.06 µg/L 22