Upload
others
View
0
Download
0
Embed Size (px)
Citation preview
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 [email protected]
AZ Laboratory for Emerging Contaminantswww.alec.arizona.edu