Endocrine Disruptors and Endocrine Disruptors and Pharmaceuticals: Implications Pharmaceuticals: Implications

for the Water Industryfor the Water Industry

Shane Snyder, Ph.D.Shane Snyder, Ph.D.Southern Nevada Water AuthoritySouthern Nevada Water Authority

Las Vegas Valley Water DistrictLas Vegas Valley Water District

Octylphenol17β-Estradiol

EstrogensEstrogens

Emerging Contaminants ???Emerging Contaminants ???

“Effects of androgenic and estrogenic compounds on the experimental metamorphosis of amphibians”

1948 Sluczewski and Roth: J. Gynecology & Obstetrics

1970 Tabak and Bunch: U.S. Dept. of the Interior “…since they are physiologically active in very small

amounts, it is important to determine to what extent the steroids are biodegraded…”

“Drugs, therefore, represent a potentially serious source of biologically active environmental contamination…”

1977 Hignite and Azarnoff: U. of Kansas USA

http://upload.wikimedia.org/wikipedia/commons/9/9c/2006_0814HistriaPlumbing20060390.jpg

- Las Vegas, Nevada – pop. ≈2,000,000- >40,000,000 visitors per year- VERY DRY - <7 cm rain & >2 M evap.- Water reuse critical for sustainability

X

XX

Three Advanced Wastewater PlantsThree Advanced Wastewater Plants≈≈1,200,000 cubic meters/day1,200,000 cubic meters/day

Lake Mead and the LowerLake Mead and the LowerColorado River provide water forColorado River provide water for

More than 22,000,000 peopleMore than 22,000,000 people

From: On Tap Magazine

http://www.lasvegassun.com/

Planned wastewater outfall anddrinking water intake

>$1,500,000,000

Do Do EDCsEDCs and Pharmaceuticals and Pharmaceuticals Pose A Real Threat to Pose A Real Threat to Water Sustainability?Water Sustainability?

Toxicological Relevance Toxicological Relevance AwwaRFAwwaRF #3085 & WRF 04#3085 & WRF 04--003003

US Drinking Water US Drinking Water (n=23, (n=23, ngng/L)/L)SOURCE WATERSOURCE WATER

Max Med Freq (%)Dilantin 40 13 91Meprobamate 73 10 91Sulfamethoxazole 173 20 91Atrazine 1011 44 87Carbamazepine 69 19 83Gemfibrozil 38 9.8 78Atenolol 48 10 74Trimethoprim 19 2.7 74Estrone 2.0 0.4 74Naproxen 44 16 70TCEP 534 115 65TCPP 721 175 57DEET 105 85 48Metolachlor 119 20 48Nonylphenol 141 89 48Triclosan 8.8 3.0 43Galaxolide 65 36 43EEq (ng/L) 6.18 0.091 75

Max Med Freq (%)Dilantin 40 13 91Meprobamate 73 10 91Sulfamethoxazole 173 20 91Atrazine 1011 44 87Carbamazepine 69 19 83Gemfibrozil 38 9.8 78Atenolol 48 10 74Trimethoprim 19 2.7 74Estrone 2.0 0.4 74Naproxen 44 16 70TCEP 534 115 65TCPP 721 175 57DEET 105 85 48Metolachlor 119 20 48Nonylphenol 141 89 48Triclosan 8.8 3.0 43Galaxolide 65 36 43EEq (ng/L) 6.18 0.091 75

SOURCE WATERSOURCE WATERMax Med Freq (%)

Atrazine 990 26 91Meprobamate 43 9.2 83Dilantin 32 9.4 74Carbamazepine 18 5.4 61Atenolol 26 2.8 57TCEP 470 121 48TCPP 508 177 48DEET 99 79 43Gemfibrozil 2.0 1.0 35Metolachlor 36 17 35Dioctyl phthalate 117 82 35Nonylphenol 104 84 17Galaxolide 34 31 17Linuron 8.1 6.2 17Sulfamethoxazole 3.0 0.39 13Triclosan 1.2 1.1 9Genistein 2.9 2.1 9EEq (ng/L) 0.077 0.077 5

FINISHED WATERFINISHED WATER

US Drinking Water US Drinking Water (n=23, (n=23, ngng/L)/L)

Relevance to Human HealthRelevance to Human Health

Treatment Processes Treatment Processes (>60 (>60 EDCs/PPCPsEDCs/PPCPs))

AwwaRFAwwaRF #2758#2758

Isotope Dilution

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Isotope DilutionIsotope DilutionSurface Water Impacted by Wastewater

Spike @ 25 ppt

0%10%20%30%40%50%60%70%80%90%

100%110%120%130%

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Isotope DilutionExternal Calibration Method

Isotope Dilution Comparison

Recoveries in Various WatersUsing Isotope Dilution

0%20%40%60%80%

100%120%

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Wastewater InfluentWastewater EffluentSurface Water w/ WW InfluenceFinished Drinking Water

Isotope DilutionIsotope DilutionConsequences of Matrix Effects

On Data Interpretation

0100200300400500600700800900

1000

Raw Water TreatmentProcess 1

TreatmentProcess 2

TreatmentProcess 3

Finished Water

True Concentration (ng/L)

Observed Concentration (ng/L)

Blanks and Blanks and ngng/L/LSNWA

• Caffeine: 1 – 5 ng/L• TCEP: 5 – 10 ng/L• Galaxolide: 5 – 10 ng/L• Dibutylphthalate: 200 – 300 ng/L• Diethylhexylphthalate: 20 – 30 ng/L• BHT (plastic SPE cartridge): 1000 – 2000 ng/L

USGS National Reconnaissance (% detected, mean, max)• Acetaminophen: 59%, 16 ng/L, 33 ng/L• Nonylphenol: 12%, 500 ng/L, 1000 ng/L• Triclosan: 16%, 150 ng/L, 560 ng/L• Bis (2-ethylhexyl) phthalate: 9%, 7000 ng/L, 14000 ng/L•Diethyl phthalate: 9%, 39000 ng/L, 74000 ng/L

http://toxics.usgs.gov/regional/est_errata.html

<30% Removal 30-70% Removal >70% RemovalTestosterone SulfamethoxazoleProgesterone Triclosan

Androstenedione DiclofenacEstriol Acetaminophen

EthynylestradiolEstrone

EstradiolErythromycin-H2O

TrimethoprimNaproxen

HydrocodoneIbuprofenCaffeine

FluoxetineMeprobamate

DiazepamDilantin

CarbamazepineDEET

AtrazineGalaxolide

TCEPIopromide

PentoxifyllineMetolachlorGemfibrozil

Musk Ketone

UV 40mJ/cmUV 40mJ/cm22

<30% Removal 30-70% Removal >70% RemovalTestosterone Ibuprofen EstriolProgesterone Metolachlor Ethynylestradiol

Androstenedione Gemfibrozil EstroneCaffeine Estradiol

Fluoxetine Erythromycin-H2OMeprobamate Sulfamethoxazole

Diazepam TriclosanDilantin Trimethoprim

Carbamazepine NaproxenDEET Diclofenac

Atrazine HydrocodoneGalaxolide Acetaminophen

TCEP Musk KetoneIopromide

Pentoxifylline

Chlorine 3.5 mg/L 24 hrChlorine 3.5 mg/L 24 hr

<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/LOzone 2.5 mg/L

Computer Modeling - QSPR

QPlogPow (LigPrep)-2 0 2 4 6 8

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Project 03-CTS-21UR “Household Chemical Fate”

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Average chlorine removal (%)

Project 03-CTS-21UR “Household Chemical Fate”

Wastewater Wastewater OzonationOzonation

Projects 04-007 & 06-012 “Advanced Oxidation”

Jun-05 Jan-06 Jan-06 Jun-05 Jan-06 Jan-06

Target Compound ng L-1 ng L-1 ng L-1 Target Compound ng L-1 ng L-1 ng L-1

Androstenedione <1 1.6 2.4 Ibuprofen 19 5.6 15Caffeine 51 21 31 Iopromide 22 139 45Carbamazepine 210 139 139 Meprobamate 332 796 737DEET 188 133 123 Musk Ketone 133 NM NMDiclofenac 54 73 71 Naproxen 13 25 71Dilantin 154 143 110 Oxybenzone 6 <1 3.0Erythromycin 133 162 149 Sulfamethoxazole 841 669 695Estriol <5 5.7 <5 TCEP 373 235 187Estrone <1 5.4 20 Testosterone <1 1.8 <1Fluoxetine <1 14 11 Triclosan <10 35 58Galaxolide 1170 NM NM Trimethoprim 35 191 229Gemfibrozil <1 16 567Hydrocodone 240 199 161 EEq* 0.63 1.00 3.17

Las Vegas WWTP Av. Conc.

Las Vegas WWTP: shade = <MRL @ 3 mg/L O3

Jun-05 Jan-06 Jan-06 Jun-05 Jan-06 Jan-06

Target Compound ng L-1 ng L-1 ng L-1 Target Compound ng L-1 ng L-1 ng L-1

Androstenedione <1 1.6 2.4 Ibuprofen 19 5.6 15Caffeine 51 21 31 Iopromide 22 139 45Carbamazepine 210 139 139 Meprobamate 332 796 737DEET 188 133 123 Musk Ketone 133 NM NMDiclofenac 54 73 71 Naproxen 13 25 71Dilantin 154 143 110 Oxybenzone 6 <1 3.0Erythromycin 133 162 149 Sulfamethoxazole 841 669 695Estriol <5 5.7 <5 TCEP 373 235 187Estrone <1 5.4 20 Testosterone <1 1.8 <1Fluoxetine <1 14 11 Triclosan <10 35 58Galaxolide 1170 NM NM Trimethoprim 35 191 229Gemfibrozil <1 16 567Hydrocodone 240 199 161 EEq* 0.63 1.00 3.17

Before Ozonation After Ozonation

““AmbientAmbient”” vs. vs. ““ReuseReuse””

Sulfamethoxazole <0.25 <0.25 0.38Atenolol 20 0.42 0.35

Trimethoprim <0.25 <0.25 <0.25Meprobamate 12 24 35

Dilantin 13 7.4 11Carbamazepine 8.2 10 9.9

Atrazine 76 138 1080Linuron 8.1 <0.50 <0.50

Gemfibrozil 0.48 0.51 0.33

Drinking Water (ng/L)<0.25 <0.25 <0.25

1.7 2.6 2.10.41 0.60 0.500.58 <0.25 0.34<1.0 <1.0 <1.0

<0.50 <0.50 <0.50<0.25 <0.25 <0.25<0.50 <0.50 <0.500.62 <0.25 0.53

Reuse Water (ng/L)

Soy Sauce vs. WastewaterSoy Sauce vs. WastewaterEstrogenicityEstrogenicity ((EEqEEq))

Kikkoman 147Tabasco 257Kimlan 70

La Choy 14

SOY SAUCE

WWTP-1 70WWTP-2 41WWTP-3 53

RAW WASTEWATER

WWTP-1 4.6WWTP-2 0.05WWTP-3 0.61

WASTEWATER EFFLUENT

Utility-1 <0.03Utility-2 <0.03Utility-3 0.07

DRINKING WATER

http://jecfa.ilsi.org

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

What will we find at pg/L, What will we find at pg/L, fgfg/L, /L, åågg/L?/L?

We must determineWe must determinetoxicological relevance! toxicological relevance!

Why do we view Why do we view EDC/EDC/PPCPsPPCPs differently?differently?

Why is Why is perchlorateperchloratedifferent?different?

The public has difficulty with the concept of The public has difficulty with the concept of relative concentrationsrelative concentrations

- Instead, they apply the “present/absent” litmus test

- Adverse health effects are presumed if present

Nanograms per liter ?

Picograms per liter ?

Micrograms per liter ?

Zeptograms per liter ?

EDCs/PPCPs are NOT the only water issues…– Infrastructure failures– Water resources– Disinfection byproducts

We must use public $ effectively– Schools, hospitals, parks,

etc.– Cost & consequences of

more treatment– Public health vs. perception

ConclusionsConclusions• EDCs and Pharmaceuticals are ubiquitous

– Present since ancient times• Treatment can reduce but NOT eliminate• Contaminant removal should be

considered in new infrastructure• Surface water generally contains more

“EDCs/PPCPs” than IPR systems• Reuse is critical for sustainability

– Australia, Singapore, Las Vegas, Phoenix, Los Angeles, Florida, etc.

• Non-detect ≠ Safe• Safe ≠ Non-detect• Non-detect ≠ Zero• We have Federal Regulations for water

– CCL Process– EDSP – Responsibility for EDC exposure?

• IF EDCs are a human health issue– Then food will be the greatest contributor (by far)

• Pharmaceuticals in water are not likely to pose human health risk– Copious data on health effects of pharms– ADIs orders of magnitude higher than detections

Take Home Thoughts…• IF perception is the only tangible issue, then

how do we cope with sensitive analytics• There is NO silver bullet

– Oxidation = Byproducts– Membranes = Brines– Activated Carbon = Disposal/Regeneration– ALL processes use energy = air quality issues

• Source water protection is the key– Protects aquatic ecosystem– Protects drinking water resources– Prevents dilution - treatment and analytics

Shane Snydershane.snyder@snwa.com