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

http://www.epa.gov/

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