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What’s in Your Sewage?Dave Humphries, Jeff Charrois, Kristina Stefanizyn
Alberta Innovates – Technology FuturesVegreville, Alberta
Why do we care?(courtesy of J. Lavengood, U of Illinois)
B. Wilson, University of KansasEnvir. Sci. Technology 2003
■ “our results suggest that these 3 PPCPs{triclosan, ciprofloxacin, tergitol} may potentially influence both structure and function of algal communities in streams receiving WWTP effluents”
Where does sewage come from?
■ Direct Deposit■ Down the Drain Disposal
■ Unused medicine■ Bathing & Showering
■ Creams, lotions, skin patches, sweat glands■ Mostly Human
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 and caffeine in
sewage {Norway}■ DEET, Caffeine, Ibuprofen, Triclosan
Some More History
■ 2006 Abo Akademi Univ – Vieno et al■ Neural and basic pharmaceuticals in STPs
and recipient rivers { Finland}■ Carbamazepine, 4 fluoroquinoline antibiotics
■ 2010 Touro University – Ruhoy et al■ Bathing and Showering: Underappreciated
sources of water pollution from medicines {USA}
■ Topically applied creams, lotions, ointments, DEET
What Did We Look For?■ Antibiotics + Sulfa Drugs■ Antibacterials■ Hormones■ Artificial Sweeteners■ Nonylphenol Ethoxylates■ Analgesics (Ibuprofen, etc)■ Caffeine, DEET, Musks■ Illegal Drugs■ Metabolites■ 71 compounds in all
Many scans
■ DRUGA - GC■ DRUGN - LC■ Hormones -LC■ NPE - LC■ Sweeteners - LC■ Musks - GC
Compounds DrugA Scan19 Compounds & Metabolites
■ ASA 0.01 µg/l■ Clofibric Acid 0.01 µg/l ■ Ibuprofen 0.005 µg/l■ Gemfibrizol 0.005 µg/l■ Fenoprofen 0.005 µg/l■ Naproxen 0.005 µg/l■ Ketoprofen 0.01 µg/l■ Diclofenac 0.01 µg/l■ Bezafibrate 0.1 µg/l
Compounds DrugA Scan (cont’d.)
■ Indomethacin 0.05 µg/l■ Carbamazapine 0.01 µg/l■ Tolfenamic Acid 0.005 µg/l■ Caffeine 0.02 µg/l■ Triclosan 0.025 µg/l■ Methyl Triclosan 0.01 µg/l■ 3,3,4-Trichlorocarbanilide 0.025 µg/l■ Meclofenamic Acid 0.01 µg/l■ DEET 0.025 µg/l
DrugA Scan(Method)
■ Surrogates■ Ibuprofen-d3■ Gemfibrizol-d6■ Caffeine-d9■ Carbamazepine-d10■ Methyl Triclosan 13C12■ Triclosan-13C12■ DEET-d7
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
Compounds DrugN Scan
■ Cotinine {Metabolite of Nicotine}■ Cocaine & Benzoylecgonine■ 9 Sulfa Drugs■ 11 Antibiotics■ Codeine■ Methamphetamine■ Prozac & Metabolite■ Acetaminophen
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
Compounds Hormone Scan
■ Estrone 0.05 µg/l■ B-Estradiol 0.50 µg/l■ 17a-Ethynylestradiol 1.0 µg/l■ Estriol 0.5 µg/l■ Progesterone 0.002 µg/l■ Testosterone 0.002 µg/l
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
Compounds – Musk Scan
■ Cashmeran 0.02 µg/l■ Celestolide 0.02 µg/l■ Phantolide 0.02 µg/l■ Musk Ambrette, Ketone 0.02 µg/l■ Galaxolide 0.02 µg/l■ Traesolide 0.02 µg/l■ Musk Xylene 0.02 µg/l■ Tonalide 0.02 µg/l■ Musk Moskene, Tibetene 0.02 µg/l
Musk Scan(Method)
■ Liquid / Liquid■ Saltout with NaCl■ pH adjust to 6.0■ GC/Iontrap-MS
■ DB5 column■ Surrogates
■ Tonalide-d3■ Musk Xylene-d15
Compounds – NPE Scan
■ Nonylphenol Isomers 0.1 µg/l■ Nonylphenol Monoethoxylate 1.0 µg/l■ Nonylphenol Diethoxylate 0.2 µg/l■ Nonylphenol Triethoxylate 0.2 µg/l■ Nonylphenol Tetraethoxylate 0.2 µg/l■ Nonylphenol Pentaethoxylate 0.2 µg/l■ Bisphenol A 0.1 µg/l
MethodsNonylphenol Ethoxylate Scan
■ SPE – Oasis HLB■ 500 ml sample size■ pH 7-8
■ Waters LC/MS/MS■ C18 water/acetonitrile/ammonium acetate
■ Surrogate■ BisphenolA-13C12
Compounds – Artificial Sweeteners
■ Cyclamate 0.5 µg/l■ Sucralose 2.0 µg/l■ Acesulfame 0.5 µg/l■ Saccharin 0.5 µg/l■ Aspartame 0.5 µg/l■ Neotame 0.1 µg/l
MethodsArtificial Sweeteners Scan
■ SPE – Oasis HLB■500 ml sample■pH 2
■ Waters LC/MS/MS■C18■Water/acetonitrile/acetic acid
Did We Find Anything?
Caffeine
0.0570.04526.2
µg/Lµg/Lµg/L
After Membrane FilterFinal Effluent
Partial Processed Effluent
Headache
Pain Relievers
7.8817.413.8Codeine
ndnd107.3Acetaminophen0.2190.0869.65Ibuprofen
2.11.610.998Diclofenac
ndnd47.8Salicylic acid
µg/Lµg/Lµg/L
After Membrane
FilterFinal Effluent
Partial Processed
Effluent
Artificial Sweeteners
ndndndSucralose
ndndndCyclamate
ndnd0.2Saccharin0.30.30.1Acesulfame
ndndndSucralose
µg/Lµg/Lµg/L
After Membrane
FilterFinal Effluent
Partial Processed
Effluent
Antibacterials
0.0480.0210.469Methyl Triclosan
0.1400.1882.63Triclosanµg/Lµg/Lµg/L
After Membrane
FilterFinal Effluent
Partial Processed
Effluent
Nonylphenol Ethoxylates
1.822.174.95NP isomers
ndnd1800NPE17700079000126000NPE2
137000125000172000NPE3
10000800011000NPE4
140001000030000NPE5
µg/Lµg/Lµg/L
After Membrane
FilterFinal Effluent
Partial Processed
Effluent
MISC
0.2550.2272.62Bisphenol A
0.0500.0560.296Methamphetamine0.0470.0490.250DEET
0.0440.0452.69Benzoylcgonine
nd0.0261.58Cocaine
nd0.4528.4Cotinine
µg/Lµg/Lµg/L
After Membrane
FilterFinal Effluent
Partial Processed
Effluent
Questions ?