What s in Your Sewage? Dave Humphries, Jeff Charrois, Kristina Stefanizyn Alberta Innovates Technology Futures Vegreville, Alberta

Transcription

1 What s in Your Sewage? Dave Humphries, Jeff Charrois, Kristina Stefanizyn Alberta Innovates Technology Futures Vegreville, Alberta

2 Why do we care? (courtesy of J. Lavengood, U of Illinois)

3 B. Wilson, University of Kansas Envir. Sci. Technology 2003 our results suggest that these 3 PPCPs {triclosan, ciprofloxacin, tergitol} may potentially influence both structure a function of algal communities in streams receiving WWTP effluents

4 Where does sewage come from? Direct Deposit Down the Drain Disposal Unused medicine Bathing & Showering Creams, lotions, skin patches, sweat glas Mostly Human

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6 Some History 2002 Trent University Metcalfe et al 9 Acidic drugs in sewage effluents {Canada} Includes: Ibuprofen, Naproxen, Gemfibrozil 2004 University of Hamburg Weigel et al Selected Pharmaceuticals a caffeine in sewage {Norway} DEET, Caffeine, Ibuprofen, Triclosan

7 Some More History 2006 Abo Akademi Univ Vieno et al Neural a basic pharmaceuticals in STPs a recipient rivers { Finla} Carbamazepine, 4 fluoroquinoline antibiotics 2010 Touro University Ruhoy et al Bathing a Showering: Uerappreciated sources of water pollution from medicines {USA} Topically applied creams, lotions, ointments, DEET

8 What Did We Look For? Antibiotics + Sulfa Drugs Antibacterials Hormones Artificial Sweeteners Nonylphenol Ethoxylates Analgesics (Ibuprofen, etc) Caffeine, DEET, Musks Illegal Drugs Metabolites 71 compous in all

9 Many scans DRUGA - GC DRUGN - LC Hormones -LC NPE - LC Sweeteners - LC Musks - GC

10 Compous DrugA Scan 19 Compous & Metabolites ASA Clofibric Acid Ibuprofen Gemfibrizol Fenoprofen Naproxen Ketoprofen Diclofenac Bezafibrate 0.01 µg/l 0.01 µg/l µg/l µg/l µg/l µg/l 0.01 µg/l 0.01 µg/l 0.1 µg/l

11 Compous DrugA Scan (cont d.) Iomethacin Carbamazapine Tolfenamic Acid Caffeine Triclosan Methyl Triclosan 3,3,4-Trichlorocarbanilide Meclofenamic Acid DEET 0.05 µg/l 0.01 µg/l µg/l 0.02 µg/l µg/l 0.01 µg/l µg/l 0.01 µg/l µg/l

12 DrugA Scan (Method) Surrogates Ibuprofen-d3 Gemfibrizol-d6 Caffeine-d9 Carbamazepine-d10 Methyl Triclosan 13C12 Triclosan-13C12 DEET-d7

13 DrugA Scan (Method) Liquid / Liquid Extraction Salt out with NaCl Acidify ph <2 Dry with acidified sodium sulphate Diazomethane Derivatization GC/Iontrap-MS DB5 column

14 Compous DrugN Scan Cotinine {Metabolite of Nicotine} Cocaine & Benzoylecgonine 9 Sulfa Drugs 11 Antibiotics Codeine Methamphetamine Prozac & Metabolite Acetaminophen

15 DrugN Scan (Method) SPE Oasis HLB Waters LC/MS/MS C18 water/methanol/formic acid Deuterated Surrogates Cotinine-d4 Norfluoxetine-d5 Methamphetamine-d9 Benzoylecgonine-d3 Chloramphetamine-d5 Acetaminophen-13C2

16 Compous Hormone Scan Estrone B-Estradiol 17a-Ethynylestradiol Estriol Progesterone Testosterone 0.05 µg/l 0.50 µg/l 1.0 µg/l 0.5 µg/l µg/l µg/l

17 Hormone Scan (Method) 500 ml Sample Size ph 2 SPE Oasis HLB Waters LC/MS/MS Water/acetonitrile/ammonium acetate C8 column Surrogates B-Estradiol-d2 Progesterone-d9

18 Compous Musk Scan Cashmeran Celestolide Phantolide Musk Ambrette, Ketone Galaxolide Traesolide Musk Xylene Tonalide Musk Moskene, Tibetene 0.02 µg/l 0.02 µg/l 0.02 µg/l 0.02 µg/l 0.02 µg/l 0.02 µg/l 0.02 µg/l 0.02 µg/l 0.02 µg/l

19 Liquid / Liquid Saltout with NaCl ph adjust to 6.0 GC/Iontrap-MS DB5 column Surrogates Tonalide-d3 Musk Xylene-d15 Musk Scan (Method)

20 Compous NPE Scan Nonylphenol Isomers Nonylphenol Monoethoxylate Nonylphenol Diethoxylate Nonylphenol Triethoxylate Nonylphenol Tetraethoxylate Nonylphenol Pentaethoxylate Bisphenol A 0.1 µg/l 1.0 µg/l 0.2 µg/l 0.2 µg/l 0.2 µg/l 0.2 µg/l 0.1 µg/l

21 Methods Nonylphenol Ethoxylate Scan SPE Oasis HLB 500 ml sample size ph 7-8 Waters LC/MS/MS C18 water/acetonitrile/ammonium acetate Surrogate BisphenolA-13C12

22 Compous Artificial Sweeteners Cyclamate Sucralose Acesulfame Saccharin Aspartame Neotame 0.5 µg/l 2.0 µg/l 0.5 µg/l 0.5 µg/l 0.5 µg/l 0.1 µg/l

23 Methods Artificial Sweeteners Scan SPE Oasis HLB 500 ml sample ph 2 Waters LC/MS/MS C18 Water/acetonitrile/acetic acid

24 Did We Fi Anything?

25 Caffeine Partial Processed Effluent Final Effluent After Membrane Filter

26 Headache

27 Pain Relievers Partial Processed Effluent Final Effluent After Membrane Filter Salicylic acid 47.8 Diclofenac Ibuprofen Acetaminophen Codeine

28 Artificial Sweeteners Partial Processed Effluent Final Effluent After Membrane Filter Sucralose Acesulfame Saccharin 0.2 Cyclamate Sucralose

29 Antibacterials Partial Processed Effluent Final Effluent After Membrane Filter Triclosan Methyl Triclosan

30 Nonylphenol Ethoxylates Partial Processed Effluent Final Effluent After Membrane Filter NPE NPE NPE NPE NPE NP isomers

31 MISC Partial Processed Effluent Final Effluent After Membrane Filter Cotinine Cocaine Benzoylcgonine DEET Methamphetamine Bisphenol A

32 Questions?