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  • 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

  • Octylphenol17-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 - 2 M evap.- Water reuse critical for sustainability

  • X

    XX

    Three Advanced Wastewater PlantsThree Advanced Wastewater Plants1,200,000 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

    N

    O NH2

    Carbamazepine

    N

    O NH2D

    D

    D

    DD D

    D

    D

    D

    D

    Carbamazepine-d10

  • Isotope DilutionIsotope DilutionSurface Water Impacted by Wastewater

    Spike @ 25 ppt

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

    100%110%120%130%

    Sulfa

    metho

    xazo

    leAt

    enolo

    l

    Trim

    ethop

    rimFlu

    oxeti

    ne

    Norflu

    oxeti

    ne

    Mepro

    bama

    teDil

    antin

    Carba

    maze

    pine

    Atraz

    ineDia

    zepa

    mLin

    uron

    Atorv

    astat

    in

    o-Hyd

    roxy a

    torva

    statin

    p-Hyd

    roxy a

    torva

    statin

    Rispe

    ridon

    eEn

    alapri

    lGe

    mfibr

    ozil

    Bisph

    enol

    A

    Simva

    statin

    - H2O

    Simva

    statin

    hydro

    xy ac

    idDi

    clofen

    acNa

    proxe

    nTr

    iclos

    an

    Isotope DilutionExternal Calibration Method

  • Isotope Dilution Comparison

    Recoveries in Various WatersUsing Isotope Dilution

    0%20%40%60%80%

    100%120%

    Ateno

    lol

    Sulfa

    metho

    xazo

    leTri

    metho

    prim

    Mepro

    bama

    teEn

    alapri

    l

    p-Hyd

    roxy a

    torva

    statin

    Dilan

    tin

    Carba

    maze

    pine

    Rispe

    ridon

    eFlu

    oxeti

    neNo

    rfluox

    etine

    o-Hyd

    roxy a

    torva

    statin

    Atraz

    ineAto

    rvasta

    tinLin

    uron

    Diaze

    pam

    Napro

    xen

    Bisph

    enol

    ADic

    lofen

    acGe

    mfibr

    ozil

    Simva

    statin

    hydro

    xy ac

    idTri

    closa

    nSim

    vasta

    tin

    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/LDiethyl phthalate: 9%, 39000 ng/L, 74000 ng/L

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

  • 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

  • 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

  • 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

    LogK

    ow(e

    xp)

    -2

    0

    2

    4

    6

    8

    QPlogS (LigPrep)-10 -8 -6 -4 -2 0

    LogS

    (exp

    )-10

    -8

    -6

    -4

    -2

    0

    Log Kow S (mg/L)

    Project 03-CTS-21UR Household Chemical Fate

    http://www.werf.org/AM/Template.cfm?Section=Home&Template=/Custom/home.cfm

  • Chlorine Model QSARChlorine Model QSARPr

    edic

    ted

    chlo

    rine

    rem

    oval

    (%)

    0 20 40 60 80 100

    0

    20

    40

    60

    80

    100

    Average chlorine removal (%)

    Project 03-CTS-21UR Household Chemical Fate

    http://www.werf.org/AM/Template.cfm?Section=Home&Template=/Custom/home.cfm

  • 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

  • Las Vegas WWTP: shade =

  • Before Ozonation After Ozonation

  • AmbientAmbient vs. vs. ReuseReuse

    Sulfamethoxazole

  • 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

  • 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, gg/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