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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
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Octylphenol17β-Estradiol
EstrogensEstrogens
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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
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- 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
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X
XX
Three Advanced Wastewater PlantsThree Advanced Wastewater Plants≈≈1,200,000 cubic meters/day1,200,000 cubic meters/day
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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
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From: On Tap Magazine
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Planned wastewater outfall anddrinking water intake
>$1,500,000,000
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Do Do EDCsEDCs and Pharmaceuticals and Pharmaceuticals Pose A Real Threat to Pose A Real Threat to Water Sustainability?Water Sustainability?
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Toxicological Relevance Toxicological Relevance AwwaRFAwwaRF #3085 & WRF 04#3085 & WRF 04--003003
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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
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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)
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Relevance to Human HealthRelevance to Human Health
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Treatment Processes Treatment Processes (>60 (>60 EDCs/PPCPsEDCs/PPCPs))
AwwaRFAwwaRF #2758#2758
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Isotope Dilution
N
O NH2
Carbamazepine
N
O NH2D
D
D
DD D
D
D
D
D
Carbamazepine-d10
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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%
Sulfam
ethox
azole
Atenolo
l
Trimeth
oprim
Fluoxe
tine
Norfluo
xetin
e
Meprob
amate
Dilanti
n
Carbam
azep
ineAtra
zine
Diazep
amLin
uron
Atorva
statin
o-Hyd
roxy a
torva
statin
p-Hyd
roxy a
torva
statin
Risperi
done
Enalap
rilGem
fibroz
il
Bisphe
nol A
Simva
statin
- H2O
Simva
statin
hydro
xy ac
idDiclo
fenac
Naprox
enTric
losan
Isotope DilutionExternal Calibration Method
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Isotope Dilution Comparison
Recoveries in Various WatersUsing Isotope Dilution
0%20%40%60%80%
100%120%
Atenolol
Sulfameth
oxazo
leTrim
ethopri
mMep
robamate
Enalapril
p-Hyd
roxy a
torvasta
tinDila
ntin
Carbamaze
pineRisp
erido
neFluo
xetin
eNorf
luoxe
tine
o-Hyd
roxy a
torvasta
tinAtra
zine
Atorva
statin
Linuro
nDiaz
epam
Naproxe
nBisp
henol
ADiclo
fenac
Gemfibroz
il
Simva
statin
hydro
xy ac
idTric
losan
Simva
statin
Wastewater InfluentWastewater EffluentSurface Water w/ WW InfluenceFinished Drinking Water
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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)
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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
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http://toxics.usgs.gov/regional/est_errata.html
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<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
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<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
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<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
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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”
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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”
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Wastewater Wastewater OzonationOzonation
Projects 04-007 & 06-012 “Advanced Oxidation”
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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.
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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
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Before Ozonation After Ozonation
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““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)
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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
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http://jecfa.ilsi.org
= 50 = 50 ngng/Kg = 3500 ng/70 Kg person/Kg = 3500 ng/70 Kg person
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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?
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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 ?
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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
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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.
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• 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
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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
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Shane [email protected]