contaminants of emerging concern (cecs) and arid west...

Contaminants of Emerging Concernand Arid West Water Resources

Shane Snyder, Ph.D.Professor & Co-Director

Chem. & Environ. EngineeringUniversity of Arizona

Three Key PointsI. Trace contaminants are ubiquitous in water

II. Ecological impacts demonstrated, human unlikely

III. Public perception and trust are critical for water reuse

“We know the value of water when the

well runs dry.”

Benjamin Franklin

Poor Richard’s Almanac - 1732

“I am convinced that, under present conditions and with the way water is being managed, we will run out of water long before we run out of fuel.”

Peter Brabeck-Letmathe

Chairman of NestléThe Economist – November 2008

Fishing Dock at Lake MeadFishing Dock at Lake MeadFishing Dock at Lake Mead

Lake Lanier - GeorgiaLake Lanier Lake Lanier -- GeorgiaGeorgia

Lake Wivenhoe – AustraliaLake Wivenhoe Lake Wivenhoe –– AustraliaAustralia

U.S. Population Could ExceedU.S. Population Could Exceed400,000,000 by 2050400,000,000 by 2050

=Approximately 2.5M people/year for the next 40 years=Approximately the population of Houston TX each year

Low Growth in Water Storage

Adapted from Graf, 1999

De Facto or Unplanned ReuseDe Facto or Unplanned Reuse

Trinity River, TexasTrinity River, Texas

Many US Cities Already Reuse Water for Many US Cities Already Reuse Water for Potable SuppliesPotable Supplies

Source: http://www.hcn.org/issues/354/17227

“Analytical Arms Race”

GC-FID Sensitivity: ppm

Selectivity: Ret Time

GC MSD Sensitivity: ppb

Selectivity: Ret Timeunit resolution, SIM

LC-MS/MS Sensitivity: ppt

Selectivity: Ret Timeunit resolution, MRM

FTMS Sensitivity: ppb-pptSelectivity: Ret Timeaccurate mass, MRM

Snyder et al., 1999. Environmental Science & Technology, pgs. 2814-2829

Interlaboratory Comparison (WaterRF 4167) 22 compounds & 24 labs

104-tert-octylphenol16Bisphenol A

11Primidone16Acetaminophen

114-nonylphenol17Naproxen

11Erythromycin18Trimethoprim

12Testosterone1817α-Ethynylestradiol

12Progesterone20Triclosan

13Ciprofloxacin20Gemfibrozil

15Fluoxetine21Sulfamethoxazole

16Estrone22Caffeine

1617β-Estradiol23Ibuprofen

16Diclofenac24Carbamazepine

Number of LaboratoriesTarget CompoundsNumber of

LaboratoriesTarget Compounds

Interlaboratory comparison (DI water)Sulfamethoxazole

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

5A 16A 10B 23D 1C 4 11 26 27 7 22A 12B 24 20B 9B 25 8C 18C 10A 3 14A 9A 20A 17A

Laboratory

Ave

rage

Abs

olut

e B

ias

Good

Erythromycin

0%

10%

20%

30%

40%

50%

60%

70%

80%

10B 3 27 26 23 4 12B 20B 24 20A 16A 1C 9B 17A 8C

Laboratory

Ave

rage

Abs

olut

e B

ias

Bad

1210%

Ciprofloxacin

0%

20%

40%

60%

80%

100%

120%

140%

10B 10A 1C 22A 27 24 4 20B 20A 3 12B 23 17A 8C

Laboratory

Ave

rage

Abs

olut

e B

ias

Ugly

All

All compounds

0

10

20

30

40

50

60

Proges

terone

Estradiol

Testo

stero

ne

Sulfamethoxa

zole

Estrone

Carbam

azepine

Ibuprofe

n

Trimeth

oprim

Ethynyle

stradiol

Caffeine

Triclos

an

Acetaminoph

enGem

fibro

zilDicl

ofenac

Bisphen

ol ANapro

xen

Erythro

mycin

Primidon

eOcty

lphenol

Fluoxeti

neNonylphen

ol

Ciproflo

xacin

Ave

rage

Abs

olut

e B

ias

(%)

Med

ian

Abs

olut

e B

ias

(%)

Interlaboratory comparison (DI water)

Three Key PointsI. Trace contaminants are ubiquitous in water

II. Ecological impacts demonstrated, human unlikely

III. Public perception and trust are critical for water reuse

Hudson River Anglers in the 1940sNoticed that fish caught below a pharmaceutical plant were far larger than other parts of the river.

Fish had been exposed to significant concentrations of tetracycline.

Later experiments determine the effect was also reproducible in chickens and cows.

10.2

3.5

10.2

7.83.5

Estradiol

Nonylphenol

X

XX

Three Advanced WWTPs: ≈300 mgdThree Advanced WWTPs: ≈300 mgd

0 2 4 6 8 10 12 14 16

Estrone (ng/L)

-150-130-110-90-70-50-30-10

Dept

h(m

)

0

5

10

15

20

25

30

0 2 4 6 8 10 12 14 16

Kilometers from WWTP effluent confluence to Hoover Dam

DEET (ng/L)

-150-130-110-90-70-50-30-10

Dept

h(m

)

0

5

10

15

20

25

30

0 2 4 6 8 10 12 14 16

Meprobamate (ng/L)

-150-130-110

-90-70-50-30-10

Dep

th(m

)

0

10

20

30

40

50

0 2 4 6 8 10 12 14 16

Sulfamethoxazole (ng/L)

-150-130-110

-90-70-50-30-10

Dep

th(m

)

0

5

10

15

20

25

30

LV Wash kilometers Hoover Dam

LV Wash kilometers Hoover Dam

SHN O

ON

O

NH2

O

O

H2N

ONH2

O

01/2003

07/2003

01/2004

07/2004

01/2005

07/2005

01/2006

07/2006

01/2007

07/2007

01/2008sum

of p

harm

aceu

tical

and

ED

C c

once

ntra

tions

(ng/

L)

0

20

40

60

80

100

Lake Mead volum

e (106 acre-ft)

12

13

14

15

16

17

18source water concentrationLake Mead Volum e

Drought: Drought: Effect on Pharmaceuticals and EDCs

Las Vegas Wash monitoring – 5 years

Lake Mead monitoring – 6+ years

Finished drinking water monitoring – 6+ years

3,000+

Most used

300 39 16

Drug groups

Final candidates

Prescription drugs

PharmaceuticalsPharmaceuticals

Detection; Public interest

321

Potential for

toxicity

4

5

Occurrence & exposure

13 EDCs

Final candidates

Status as an EDC 32

1

Potential for toxicity

4

5

•Hundreds of purported EDCs

•Selected data compilations screened

Criteria:

•In vivo

•Relevant species

•Endocrine mediated effect

•Adverse effect

•Occurrence in drinking water, especially U.S.

•Resistance to conventional drinking water treatment

•Availability of method for analysis

•Severity of effects

•Potency

•Pharmaco-kinetics

•Availability of studies suitable for risk assessment Endocrine

Mode of Action

PAC, public,

scientific interest

Suspected EDCsSuspected EDCs

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 α-BHC Testosterone DaidzeinDiazepam β-BHC EquolDiclofenac γ-BHC FormononetinDilantin δ-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 α-BHC Testosterone DaidzeinDiazepam β-BHC EquolDiclofenac γ-BHC FormononetinDilantin δ-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

α-BHC Testosterone DaidzeinDiazepam β-BHC Equol

γ-BHCδ-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 α-BHC Testosterone DaidzeinDiazepam β-BHC EquolDiclofenac γ-BHC FormononetinDilantin δ-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

α-BHC Testosterone DaidzeinDiazepam β-BHC EquolDiclofenac γ-BHC Formononetin

δ-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 FacilitiesCompound Max (ng/L) Median (ng/L) Frequency (%)

Atrazine 870 49 83Meprobamate 42 5.7 78

Dilantin 19 6.2 56Atenolol 18 1.2 44

Carbamazepine 18 6.0 44Gemfibrozil 2.1 0.48 39

TCEP 470 120 39DEET 93 63 33

Metolachlor 27 16 33TCPP (Fyrol PCF) 510 210 28Sulfamethoxazole 3.0 0.39 22

US Drinking Water

Detected in systems with chloramination or UV

DWEL DWEL ≈≈ MCLGMCLGDrinking Water Equivalent Level (DWEL) = ADI * 70 kg

2 L

Pharmaceutical Evaluation

Drug Class

ADI-DWEL (µg/L)

Max. conc. (µg/L)

Sites with Detection

(n=18)Liters per Day to

Exceed DWEL

Risperidone Antipsychotic 0.49 0.0029 1 340

Phenytoin Anticonvulsant 6.8 0.019 10 700

Carbamazepine Anticonvulsant 12 0.018 8 1,300

Atenolol Beta-blocker 70 0.018 8 7,800

Meprobamate Antianxiety agent 260 0.042 14 13,000

Gemfibrozil Antilipidemic 45 0.0021 7 43,000

FluoxetineSSRI

antidepressant 34 0.00082 2 82,000

Norfluoxetine Metabolite 34 0.00077 1 88,000

DiazepamBenzodiazepine

tranquilizer 35 0.00033 1 210,000

Sulfamethoxazole Anti-infective 18,000 0.003 4 12,000,000

Bruce, Pleus, & Snyder, 2010 Environ. Sci. Technol. 44:5619-5626

E-screen Assay• MCF-7 breast cancer cell line proliferates in

response to estrogenic compounds• Developed by oncologists Ana Soto & Carlos

Sonnenschein at Tufts University

EEq Comparison (“Worst” WWTP)

Mug of Beer (6 ng/L, 500 mL)

1.4 L Wastewater(4.6 ng/L)

≈ +

≈1 cup coffee

(17 ng/L, 240 mL)

EEq Comparison(“Worst” WWTP)

890 mL Secondary Wastewater

(4.6 ng/L)

EEq Comparison“Worst” WWTP

≈

Teaspoon of Soy Sauce (300 ng/L, 15 mL)

1 Liter Secondary Wastewater

(4.6 ng/L)

Three Key PointsI. Trace contaminants are ubiquitous in water

II. Ecological impacts demonstrated, human unlikely

III. Public perception and trust are critical for water reuse

US Regulatory History• 1962: 28 discrete “chemical” contaminants regulated

US Regulatory History• 1962: 28 discrete “chemical” contaminants regulated

Universe

PCCL

PCCL Expert Review

Preliminary CCL

CCL Expert Review

CCL Contaminant Validation

CCL

Algorithm, training set, criteria

(Attribute scoring protocol)

Screening

Classification

Defend how and why thesecontaminants made it to the list

CCL Process - Chemicals

Nomination

Surveillance

CCL3 – Key Highlights• Draft CCL3 – essentially no pharmaceuticals or steroids

– Did include PFOA and PFOS

– Did include nitroglycerine (but not for pharmaceutical reasons)

• Final CCL3 – addition of 9 estrogens, 1 progestin, & 1 antibiotic

– Estrogens (17a-estradiol, 17b-estradiol, equilenin, equilin, estriol, estrone, ethynylestradiol, estriol, estrone, mestranol)

– Progestin (norethindrone)

– Antibiotic (erthythromycin)

• Steroid hormones on CCL3 largely due to:

– Kolpin 2002 (USGS) – hormones at hundreds of ng/L

– California E2 Cancer Risk – DWEL = 0.9 ng/L

Contaminant: Estradiol (17-beta estradiol)

Potency Severity Prevalence Magnitude8 8 10 5

Attribute Scores

HRL Ratio(s)NC HRL/Kolpin MAX: 1.75

CAR HRL/Kolpin MAX: 0.0045

3-model Categorical Prediction

L

Water Data % Detects

Maximum value of Detects

Median value of Detects

90% of Detects

Units for Mag data

Snyder, et al., 2007 FINISHED 0.0 Not detected Not detected Not detected ug/LSnyder, et al., 2007 RAW 0.0064 ug/LKolpin, et al., 2002 10.6 0.2 0.16 ug/L

Health Reference Level (HRL)2 cancer 0.0009ug/L

http://jecfa.ilsi.org

= 50 ng/Kg = 3500 ng/70 Kg person= 50 ng/Kg = 3500 ng/70 Kg person

BUT What about the MIXTURES?WHO – Drinking Water Quality Guidelines

• Dosed entire lake with ≈6 ng/L of ethynylestradiol (EE2)– Compared to two reference Lakes (pristine)

– Seven years of monitoring, three years of dosing EE2

• Fathead minnow population dwindled to near extinction– Male fish had VTG levels 1000x higher than controls

– Histological impacts, including intersex, observed

– Reproductive failure persisted 2-year after exposure ceased

• Only study showing pop. impact of a pharm. in water

0

0.5

1

1.5

2

2.5

DrinkingWater

6.25%WW

12.5%WW

25% WW 50% WW 100%WW

EE2 +DW

EE2 +WW

Num

ber o

f Spa

wni

ng E

vent

s

0

20

40

60

80

100

120

Perc

ent W

aste

wat

er C

ompo

sitio

n

Spawning Events, Trial 1

Spawning Events, Trial 2

Percent Wastewater Influence

1969, Transactions of the American Fisheries Society;

Zn 50% Spawning Reduction = 88 μg/L

Drinking Water Zn > 150 μg/L

Wastewater Zn < 50 μg/L

• All water has been, or will be, reused– Global sustainability depends on recycling water

– Analytical instruments can detect nearly any substance

• Pharmaceuticals can be measured ubiquitously– But, analytical methods are not yet standardized

– Lists if pharmaceuticals are largely arbitrary

• Public perception and trust are critical – Human and fish exposure is dramatically different

– Help fish through reuse of surface discharge for potable reuse

– We have challenges, but should focus on those that matter

– Regulations MAY help with public perception, but move slowly

Three Key Points

The Path ForwardIncreased reuse of water-Especially in coastal cities-More efficient technologies-Direct reuse

-Not just in African anymore-Cloudcroft, NM-Amarillo, TX-Your town?

-What does the environmental buffer contribute to safety?

-Right quality of water for use-Toilet flushing vs. drinking-Lawn irrigation vs. bathing

Life Cycle of Water

http://icosse11.org/

Shane SnyderUniversity of Arizonasnyders2@email.arizona.edu

AZ Laboratory for Emerging Contaminantswww.alec.arizona.edu