Issues with Emerging Contaminants in Water
What are “emerging contaminants”?
• PPCPs and EDCs– Pharmaceuticals – Personal Care Products– Endocrine Disrupting Compounds
• Emerging emerging contaminants?
Pharmaceuticals
• Human and veterinary substances taken in response to disease/maladies.– Cure disease– Alleviate disease associated symptoms– Prevent disease
• “The human impulse for a cure runs quite deep, and our first instinct whenever we feel sick or heading toward sickness is to medicate.” – Jjemba, 2008
Personal Care Products
• Compounds used in our daily lives– Soaps, detergents, perfumes, aftershaves– Cleaning agents, disinfectants, sprays,
deodorants– Bug sprays, sunscreens– Products are typically associated with hygiene
Endocrine Disrupting Compounds• Disrupt normal function of the endocrine system• Mimic hormones; agonize or antagonize
hormone activity, synthesis, or metabolism; modify hormone receptors
• Active at very low levels• Concern about additive or synergistic effects
caused by mixtures of EDCs• Synthetic Estrogens
– Ethinyl Estradiol, bisphenol-A• Synthetic Androgens
– 90% of US cattle receive growth hormone implants– Synthetic androgens remain environmentally active
for months
Emerging, emerging contaminants
• What’s next?– Technology will always get better
• New products• New ways to find chemicals at lower concentrations
– NDMA found in beer by accident– EDC activity of bisphenol-A (BPA) found by
accident– Green revolution dumped millions of tons of
pesticides and herbicides into the environment, but also created enough food for billions of people!!!
A Brief History of “Emerging” Contaminants
NH2O
N
HO
CH3CH3
CH3
CH3
HO
OH
CH3
Developments in Industrial Microbiology - 1970
EDC StoriesLake Mead Feminized Carp• Found vitellogenin in male carp
of Las Vegas wash and Bay in Lake Mead– Egg producing protein– Elevated levels in female fish
• Found elevated levels of several potential EDCs– Ethinyl Estradiol– Las Vegas wastewater treatment
plant outfall
"Synthetic Organic Compounds and Carp Endocrinology and Histology, Las Vegas Wash and Las Vegas and Callville Bays of Lake Mead, Nevada, 1992 and 1995, " by Hugh E. Bevans, et. al
EDC StoriesLake Apopka Alligators• A “Teeny Weenie” Problem
– Kyla Dunne for PBS (June 2, 1998)• http://www.pbs.org/wgbh/pages/frontline/shows/nature/gallery/alligators.html
• Lou Guillette from the University of Florida– 25% smaller phallus in the adult and juvenile male alligators of
lake Apopka– Low testosterone levels compared to levels in alligators from
healthy lake– Penis size did not reflect amount of testosterone in blood– Causes?
• 1980 DDT and dicofol spill into the lake• Chemical runoff from agriculture• Discharge from Sewage Treatment plant
– Proving the link• Took alligator eggs from “Clean” lake• Grew them in p,p’ DDE and found similar
results to Lake Apopka alligators
"Developmental Abnormalities of the Gonad and Abnormal Sex Hormone Concentrations in Juvenile Alligators from Contaminated and Control Lakes in Florida". Environmental Health Perspectives 102(8):680-688
"Reduction in Penis Size and Plasma Testosterone Concentrations in Juvenile Alligators Living in a Contaminated Environment". General and Comparative Endocrinology 101:32-42.
Where have EDCs/PPCPs been found?
• Surface waters throughout the world– Europe, Asia, Canada, USA
• USGS report “Pharmaceuticals, hormones, and other organic wastewater contaminants in US streams 1999-2000: A national reconnaissance”– 95 compounds– 139 streams throughout
US sampled• 80% tested positive
– ES&T 36 (6), 1202
Koplin et al., 2002
EDC Stories (Hermaphroditic Frogs)• Tyrone Hayes
– “Feminization of male frogs in the wild” (Nature, 419: 895-896)
• Investigated the effects of exposure to waterborne atrazine contaminiation on Leopard Frogs
• Examined different regions of US (Iowa – Utah)
• Found 10-92% of males showed gonadal abnormalities
– “Atrazine-induced hermaphroditism at 0.1ppb in American Leopard Frogs (Rana pipiens): Laboratory and field evidence” (EHP, 111:568-575)
Government Regulations
• Compounds are not currently regulated in the United States as EDCs– Process started in 1996– Endocrine Disrupting Screening Program (EDSP)
• Assay development and validation team– Scientific and Technical validation of EDC screens
• Priority setting workgroup– Develop and prioritize which compounds are tested as EDCs
• Regulatory activities workgroup– Working on regulatory procedures needed to implement EDSP
http://www.epa.gov/scipoly/oscpendo/
19543 88
Samples collected per time zone
17 Participating Utilities
Target CompoundsPharmaceuticals (20) Potential EDCs (26) Steroid Hormones (5) Phytoestrogens (11)
Atenolol Atrazine Estradiol ApigeninAtorvastatin Benzophenone Estrone Biochanin Ao-Hydroxy atorvastatin BHA Ethinylestradiol Chrysinp-Hydroxy atorvastatin BHT Progesterone CoumestrolCarbamazepine -BHC Testosterone DaidzeinDiazepam -BHC EquolDiclofenac -BHC FormononetinDilantin -BHC GenisteinEnalapril Bisphenol A GlyciteinFluoxetine Butylbenzyl phthalate MatairesinolNorfluoxetine DEET NaringeninGemfibrozil DiazinonMeprobamate Dioctyl phthalateNaproxen GalaxolideRisperidone LinuronSimvastatin MethoxychlorSimvastatin hydroxy acid MetolachlorSulfamethoxazole Musk ketoneTriclosan NonylphenolTrimethoprim Octachlorostyrene
OctylphenolTCEPTCPPTonalideTraseolideVinclozolin
Pharmaceuticals Potential EDCs Steroid Hormones Phytoestrogens
Detected in Raw Water* (24/62)
Atenolol Atrazine Estradiol ApigeninAtorvastatin Benzophenone Estrone Biochanin Ao-Hydroxy atorvastatin BHA Ethinylestradiol Chrysinp-Hydroxy atorvastatin BHT Progesterone CoumestrolCarbamazepine -BHC Testosterone DaidzeinDiazepam -BHC EquolDiclofenac -BHC FormononetinDilantin -BHC GenisteinEnalapril Bisphenol A GlyciteinFluoxetine Butylbenzyl phthalate MatairesinolNorfluoxetine DEET NaringeninGemfibrozil DiazinonMeprobamate Dioctyl phthalateNaproxen GalaxolideRisperidone LinuronSimvastatin MethoxychlorSimvastatin hydroxy acid MetolachlorSulfamethoxazole Musk ketoneTriclosan NonylphenolTrimethoprim Octachlorostyrene
OctylphenolTCEPTCPPTonalideTraseolideVinclozolin
EstradiolAtorvastatin Benzophenone Biochanin Ao-Hydroxy atorvastatin BHA Ethinylestradiol Chrysinp-Hydroxy atorvastatin BHT Coumestrol
-BHC Testosterone DaidzeinDiazepam -BHC Equol
-BHC-BHC
Enalapril Bisphenol A GlyciteinFluoxetine Butylbenzyl phthalate MatairesinolNorfluoxetine Naringenin
Diazinon
RisperidoneSimvastatin MethoxychlorSimvastatin hydroxy acid
Musk ketone
OctachlorostyreneOctylphenol
TonalideTraseolideVinclozolin * In at least 20% of samples
Atenolol Atrazine Estradiol ApigeninAtorvastatin Benzophenone Estrone Biochanin Ao-Hydroxy atorvastatin BHA Ethinylestradiol Chrysinp-Hydroxy atorvastatin BHT Progesterone CoumestrolCarbamazepine -BHC Testosterone DaidzeinDiazepam -BHC EquolDiclofenac -BHC FormononetinDilantin -BHC GenisteinEnalapril Bisphenol A GlyciteinFluoxetine Butylbenzyl phthalate MatairesinolNorfluoxetine DEET NaringeninGemfibrozil DiazinonMeprobamate Dioctyl phthalateNaproxen GalaxolideRisperidone LinuronSimvastatin MethoxychlorSimvastatin hydroxy acid MetolachlorSulfamethoxazole Musk ketoneTriclosan NonylphenolTrimethoprim Octachlorostyrene
OctylphenolTCEPTCPPTonalideTraseolideVinclozolin
Estradiol ApigeninAtorvastatin Benzophenone Estrone Biochanin Ao-Hydroxy atorvastatin BHA Ethinylestradiol Chrysinp-Hydroxy atorvastatin BHT Progesterone Coumestrol
-BHC Testosterone DaidzeinDiazepam -BHC EquolDiclofenac -BHC Formononetin
-BHC GenisteinEnalapril Bisphenol A GlyciteinFluoxetine Butylbenzyl phthalate MatairesinolNorfluoxetine Naringenin
DiazinonDioctyl phthalate
Naproxen GalaxolideRisperidone LinuronSimvastatin MethoxychlorSimvastatin hydroxy acid
Musk ketoneTriclosan NonylphenolTrimethoprim Octachlorostyrene
Octylphenol
TonalideTraseolideVinclozolin
Detected in Drinking Water* (11/62)
Pharmaceuticals Potential EDCs Steroid Hormones Phytoestrogens
* In at least 20% of samples
Finished Water for 18 Drinking Water Treatment Facilities
Compound Max (ng/L) Median (ng/L) Frequency (%)
Atrazine 870 49 83
Meprobamate 42 5.7 78
Dilantin 19 6.2 56
Atenolol 18 1.2 44
Carbamazepine 18 6.0 44
Gemfibrozil 2.1 0.48 39
TCEP 470 120 39
DEET 93 63 33
Metolachlor 27 16 33
TCPP (Fyrol PCF) 510 210 28
Sulfamethoxazole 3.0 0.39 22
US Drinking Water
AP Story (March, 2008)
Relevance to Human HealthRelevance to Human Health
How much would you have to How much would you have to consume??consume??
Phenytoin (Dilantin)
Phenobarbital (Luminal)
Carbamazepine (Tegretol)
Primidone (Myidone)
Hydrocodone
Codeine
Diazepam (Valium)
Guaifenesin (Robitussin)
Pentoxifylline (Trental)
1,200,000
770,000
23,000,000
5,800,000
1,500,000
980,000
190,000
23,000,000
16,000,000
Compound Daily Dose (mg) Liters
300 - 400
30 - 300
800 - 1200
750 - 1000
20 - 38
120 - 180
12 - 120
1200 - 2400
800 - 1200
NOTENOTE: : EPA Reference Intake = 2L/dayEPA Reference Intake = 2L/day
Human Impacts?• Nelson and Bunge, 1974:
– Missouri men have lower sperm counts than men in LA, NY, and Minneapolis
– No reason found
• Swan et al., 2003:– Confirmed earlier study– Missouri low-sperm count men had higher levels
of Atrazine, Alachlor, and Diazanon– Link between pesticides and reproductive effect– No occupational exposure– Source Identified: Drinking water contamination
More Human Cases• DES Daughters• Hypospadias doubled from 1970-1991
(Paulozzi et al, 1997)• Dioxins and endometriosis in monkeys
(Rier and Foster, 2002)• Link between increases in breast,
testicular and prostate cancers over past 40 years??? (Krishnan and Safe, 1993; Carlsen et al., 1995; EPA, 1997; more)
• All linked to hormone mimicking or disrupting compounds
AwwaRF/WateReuse Foundation
Tailored Collaboration:“Toxicological Relevance of EDCs and
Pharmaceuticals in Water”Projects 3085/04-003
- Dr. Djanette Khiari – AwwaRF- Mr. Joshua Dickinson - WRF
E-screen Assay
• MCF-7 breast cancer cells proliferate in response to estrogenic compounds
• Developed by oncologists Ana Soto & Carlos Sonnenschein at Tufts University
0
50
100
150
200
250
300
350
E-screen Results (EEq ng/L)
nd 0.8 2.5 2.9 4.6 6.0 13
300
4000
0.6
1700
0.7
1 cup coffee
(17 ng/L, 240 mL)
EEq Comparison(“Worst” WWTP)
890 mL Secondary Wastewater
(4.6 ng/L)
EEq Comparison
Teaspoon of Soy Sauce (300 ng/L, 15 mL)
1 Liter Secondary Wastewater
(4.6 ng/L)
Soy Baby Formula(1700 ng/L, 4 oz Bottle)
EEq Comparison
44 Liters of Secondary Wastewater(4.6 ng/L)
Daily Intake of EEq (ng) Comparison• “Typical” day for average adult, per serving
Glass of milk = 0.1 ng2 Cups coffee = 8.2 ng
Glass of Juice = 0.2 ng
Breakfast Lunch Dinner
Sushi w/ soy sauce = 4.5 ng
Glass of beer = 2.2 ng
Cup of tea = 0.7 ng• Est. Total Daily intake of EEq = 15.9 ng
What is the Context for Risk?
• Food Exposure
• Air Exposure
• Water Exposure
• Health Endpoints– Cancer– Non-Cancer
Max Concentrations, ng/L
Bisphenol A Atrazine Nonylphenol Estradiol
Raw 14 870 130 17
Finished 25 930 100 <0.5
Bottled Water <5 <0.25 <80 <0.5
Apple Juice <50 <10 26,000 <100
Vegetable Juice <250 <20 1300 <5
Green Tea <50 <10 1600 <10
Beer <1000 <50 2400 <100
Cow's Milk <125 <10 <1250 <100
Soy Milk <125 <10 4500 <20
Dairy Formula 5600 <50 <10,000 <20
Soy Formula 5400 <50 11,000 <20
Soy Sauce <2.5 <0.25 21,000 <1
Breastmilk* 1900* ?? ?? 8,000 to 19,000**
*Ye, 2006 **Choi, 2002
Note Atrazine MCL = 3000 ng/L in Water; RfD = 2.45 mg/day for Ave. Adult
WATER INDOOR AIR
Conc.Exposure (2 L/day)
Conc.Exposure
(24 m3/day)
(μg/L) (μg) (μg/m3) (μg)
BHT 0.05 0.10 36 864
TCPP (Fyrol PCF)
0.53 1 1.3 30
Galaxolide 0.28 0.6 0.12 3
Butylbenzyl phthalate
0.055 0.1 0.018 0.4
Nonylphenol 0.11 0.3 0.11 3
““No substance is a No substance is a poison by itself. It is poison by itself. It is the dose that makesthe dose that makes
a substance a a substance a poison...”poison...”
Paracelsus Paracelsus (1493-1541)(1493-1541)
Risk = Toxicity + ExposureRisk = Toxicity + Exposure
Method Reporting Limits based on 100x <DWEL
Max Drinking Water Conc.
(µg/L)
DWEL (µg/L)
Liters per day to meet DWEL
Method MRL (µg/L)
Recommended MRL (µg/L)
Phenytoin 0.019 6.8 700 0.001 0.1
Carbamazepine 0.018 12 1,300 0.0005 0.1
Fluoxetine 0.0082 34 82,000 0.0005 0.3
Diazepam 0.00033 35 210,000 0.00025 0.4
Gemfibrozil 0.0021 45 43,000 0.00025 0.5
Atenolol 0.018 70 7,800 0.00025 0.7
Meprobamate 0.042 260 13,000 0.00025 3.0
Bisphenol A 0.025 1,800 140,000 0.005 20
4-Nonylphenol 0.10 1,800 35,000 0.08 20
Sulfamethoxazole 0.003 18,000 12,000,000 0.00025 200
Finished Water for 18 Drinking Water Treatment Facilities
Compound Max (ng/L) Median (ng/L) Frequency (%)
Atrazine* 870 49 83
Meprobamate 42 5.7 78
Dilantin 19 6.2 56
Atenolol 18 1.2 44
Carbamazepine 18 6.0 44
Gemfibrozil 2.1 0.48 39
TCEP 470 120 39
DEET 93 63 33
Metolachlor 27 16 33
TCPP (Fyrol PCF) 510 210 28
Sulfamethoxazole 3.0 0.39 22
MRL > 10 ng/L
MRL > 10 ng/L
MRL > 20 ng/L
MRL > 20 ng/L
MRL > 20 ng/L
MRL > 50 ng/L
MRL > 50 ng/L
MRL > 100 ng/LMRL > 500 ng/L
MRL > 1000 ng/L
MRL > 1000 ng/L
US Drinking Water
Effects on Water Industry
http://www.pacinst.org/
NYC Water ~ $3.50/ 1000 galLas Vegas ~ $1.50/ 1000 galBottled Water ~ $350 - $8,000/ 1000 gal
Given Enough Energy Input, Any Chemical Can Be Removed
From Water…Is the Benefit Worth the Impact?
Historical and Forecast Lake Mead Elevation
Top of Spillway
DroughtDrought
1,000
1,040
1,080
1,120
1,160
1,200
1,240Ja
n-0
0
Jan
-01
Jan
-02
Jan
-03
Jan
-04
Jan
-05
Jan
-06
Jan
-07
Jan
-08
Jan
-09
Ele
vati
on
Ab
ove
Se
a L
eve
l (fe
et)
Historical
Forecast
Drinking & Hydroelectric Minimal Level
Pharm’s and EDCs in Lake Mead
Benotti, Stanford, and Snyder, JEQ, in press
UVUV40mJ/cm40mJ/cm22
<30% Removal 30-70% Removal >70% RemovalTestosterone SulfamethoxazoleProgesterone Triclosan
Androstenedione DiclofenacEstriol Acetaminophen
EthynylestradiolEstroneEstradiol
Erythromycin
TrimethoprimNaproxen
HydrocodoneIbuprofenCaffeine
FluoxetineMeprobamate
DiazepamDilantin
CarbamazepineDEET
AtrazineGalaxolide
TCEPIopromide
PentoxifyllineMetolachlorGemfibrozil
Musk Ketone
Chlorine 3.5 mg/L 24 hrChlorine 3.5 mg/L 24 hr<30% Removal 30-70% Removal >70% Removal
Testosterone Ibuprofen EstriolProgesterone Metolachlor Ethynylestradiol
Androstenedione Gemfibrozil EstroneCaffeine Estradiol
Fluoxetine Erythromycin
Meprobamate SulfamethoxazoleDiazepam TriclosanDilantin Trimethoprim
Carbamazepine NaproxenDEET Diclofenac
Atrazine HydrocodoneGalaxolide Acetaminophen
TCEP Musk KetoneIopromide
Pentoxifylline
<30% Removal 30-70% Removal >70% RemovalMusk Ketone Meprobamate Testosterone
TCEP Atrazine ProgesteroneIopromide Androstenedione
EstriolEthynylestradiol
EstroneEstradiol
Erythromycin-H2OSulfamethoxazole
TriclosanTrimethoprim
NaproxenDiclofenacIbuprofen
HydrocodoneAcetaminophenCarbamazepine
DilantinDiazepamCaffeine
FluoxetineDEET
MetolachlorGalaxolide
PentoxifyllineGemfibrozil
Ozone 2.5 mg/L orOzone 2.5 mg/L orUV-HUV-H22OO22
≈ 700 mJ + 5 mg/L≈ 700 mJ + 5 mg/L
RO Membranes: Most compounds removed >>70%
Water Reuse Facility
Wastewater Effluent
MF Effluent RO EffluentUV-AOP Effluent
Pharmaecuticals ng/L ng/L ng/L ng/LSulfamethoxazole 1300 719 2.6 <0.25
Atenolol 2460 1970 20 1.7Trimethoprim 601 604 4.3 0.46
Fluoxetine 38 32 <0.50 <0.50Norfluoxetine 11 9.7 <0.50 <0.50Meprobamate 339 316 1.6 0.63
Dilantin 283 258 1.3 <1.0Carbamazepine 304 295 1.5 <0.50
Diazepam 3.8 3.4 <0.25 <0.25Atorvastatin 67 142 <0.25 <0.25
o-Hydroxy atorvastatin 66 129 <0.50 <0.50p-Hydroxy atorvastatin 107 180 <0.50 <0.50
Risperidone 3.3 0.38 <0.25 <0.25Enalapril 2.8 16 <0.25 <0.25
Gemfibrozil 2420 2510 7.8 0.65Diclofenac 134 174 0.58 <0.25Naproxen 235 245 1.0 <0.50
Energy per Unit Volume for Water Treatment
0.001
0.01
0.1
1
10
kWh
/m3
Climate Change
Drought
IncreasedWW
InfluenceOn DW
NovelTreatment
Technologies
GreenhouseGas
Emissions
Population Growth
Impact Cycle
What issues ARE important?
What compounds should we be worried about?
Microbes?
CCL 1, 2, & 3?
Utility Size/Pop.?
Key Messages•Pharm/EDCs documented in water for >40
years
•If we look hard enough, we will find contaminants
–No treatment process is “perfect”
–Contaminant reduction vs. pollution relocation
–Cleaner water vs. carbon footprint
–Should DW Utilities be proactive???
Key Messages•Method reporting limits and treatment goals
must be health-based
•If MRLs were 1 μg/L, we would have detected no contaminants
•If MRLs were 0.1 μg/L, we would have detected only two target compounds - NO pharmaceuticals
•If MRLs were 0.01 μg/L, only ½ of the compounds detected would have been reported
•Detection does not = risk, just as ND does not = safe!
Key Messages•Ecological concerns must be addressed
•We should strive for cleaner & safer water
– the public will bear the costs
•The world will depend on water reuse•Trace contaminants WILL be detected
•If treatment needed, wastewater makes the most sense
•More efficient treatment = more greenhouse gases and costs to the public