Occurrence, Treatment, and Toxicological Relevance ofEndocrine Disruptors and Pharmaceuticals in Drinking
Water
Shane SNYDER
Water Quality Research & Development Division
Southern Nevada Water Authority
Las Vegas, Nevada USA

1. Introduction
Over the past decade a great amount of interest has arisen regarding theoccurrence and fate of trace organic contaminants in the aquatic environment.

Ofparticular concern are human hormones and pharmaceuticals, many of which are
ubiquitous contaminants in conventional municipal wastewater treatment plant effluents
when measured with ng/L detection limits.

As analytical procedures and bioassay

techniques become more readily available and increasingly sensitive, additional new
contaminants will be discovered.

The presence or absence of any chemical incommerce in a wastewater effluent is essentially a function of the analytical detection
capability.

This poses a unique challenge for water treatment processes intent on theremoval of organic contaminants, as complete removal is merely a reflection of ananalytical reporting limit.

The projects described here sought to was designed toinvestigate the attenuation of a group of structurally diverse emerging contaminants in avariety of commonly utilized conventional and advanced water treatment processes andto determine the concentration of these compounds in drinking water that would be
expected to invoke toxicological responses in humans.
This study shows that the majority of emerging contaminants can be readily
removed using ozone or UV-advanced oxidation.

However, some compounds arerecalcitrant and difficult to oxidize using commonly employed oxidant doses.

Magnetic

ion-exchange (MIEX ®) provided minimal contaminant removal; however, contaminants
that were negatively charged at ambient pH were well removed.

Activated carbon,

both in powdered and granular forms, was effective for contaminant absorption.
Carbon type, contact time, and dose or regeneration are influential parameters inremoval efficacy by activated carbon.

No single treatment process was capable ofremoving all contaminants consistently to less than the analytical method reporting
limits employed.

Moreover, each treatment process provided advantages anddisadvantages that will be discussed in this chapter.

- 197 -A multi-barrier approach would

provide the most comprehensive removal strategy for organic contaminant treatment.
The human health relevance of pharmaceuticals detected in full scale drinking
water facilities in the US was investigated.

A series of toxicological endpoints were

evaluated, and the most sensitive endpoint chosen as a point of departure.

In somecases, the most sensitive endpoint was not the therapeutic effect of the pharmaceutical.
For all pharmaceuticals investigated, the drinking water equivalent level (DWEL) ofconcern was in µg/L, or larger, concentrations.

Therefore, there appears to be no

human health relevance at the levels detected in drinking water.

A further componentof this study sought to investigate endocrine disrupting impacts of select EDCs.

The

EDC component also included an investigation into the estrogenicity of common fooditems as compared to drinking and reuse water.

The concentrations of selectedchemicals to induce EDC effects occurred at concentrations far above those found in
US drinking waters.

Moreover, the concentrations of these chemicals in food/beverage

items were often orders of magnitude greater than those find in water.

Using an in vitro

bioassay, it was determined that the estrogenicity of soy sauce, green tea, and milk
were orders of magnitude greater than estrogenicity of water (even wastewater).

It isunlikely the endocrine disruptive effects from trace organic chemicals are relevance in
US drinking waters.
2. Overview
2.1 History
In 1965 Stumm-Zollinger and Fair of Harvard University published the first
known report indicating that steroid hormones are not completely eliminated bywastewater treatment (Stumm-Zollinger and Fair 1965).

In an article published in 1970,

Tabak and Bunch investigated the fate of human hormones during wastewater
treatment and stated “since they (hormones) are physiologically active in very small
amounts, it is important to determine to what extent the steroids are biodegraded”(Tabak and Bunch 1970).

As early as the 1940s, scientists were aware that certain

chemicals had the ability to mimic endogenous estrogens and androgens (Schueler
1946; Sluczewski and Roth 1948).
published

the

first

known

In 1977, researchers from the University of Kansas

reportspecificallyaddressingthedischargeofpharmaceuticals from a wastewater treatment plant (Hignite and Azarnoff 1977).
Despite these early findings, the issue of steroids and pharmaceuticals in wastewater
outfalls did not gain significant attention until the 1990s, when the occurrence of naturaland synthetic steroid hormones in wastewater was linked to reproductive impacts in fishliving downstream of outfalls (Purdom, Hardiman et al. 1994; Desbrow, Routledge et al.
1998; Routledge, Sheahan et al. 1998).
Since the initial link between trace contaminants (sub-µg/L) in wastewater- 198 -

effluents and ecological impacts in receiving waters, many studies have focused on theoccurrence of these contaminants (Halling-Sorensen, Nielsen et al. 1998; Ternes,
Hirsch et al. 1998; Daughton and Ternes 1999; Snyder, Keith et al. 1999; Metcalfe,
Koenig et al. 2000; Ternes and Hirsch 2000; Snyder, Kelly et al. 2001; Kolpin, Furlong etal. 2002; Vanderford, Pearson et al. 2003).

As a result, pharmaceuticals and steroid

hormones have been detected in many water bodies around the world (Kolpin, Furlong
et al. 2002; Cargouet, Perdiz et al. 2004; Petrovic, Eljarrat et al. 2004).

One major

contributor of such widespread contamination is municipal wastewater discharge, which
impacts surface water quality by contaminating receiving water bodies with chemicals
not completely removed by current treatment processes.

Indirect potable water reuse,

either planned or unplanned, can occur when wastewater treatment plant discharge
comprises a significant portion of the receiving stream’s total flow.

In some cases,

effluent dominated surface waters are used as source waters for drinking water
treatment facilities.
water.

Global water sustainability depends in part upon effective reuse of

In particular, the reuse of municipal wastewater for irrigation and augmentationof potable water supplies is critical.

Public perception and concern regarding trace

hormones and pharmaceuticals is creating resistance to reuse projects.

It isnecessary to obtain accurate information on the attenuation or elimination of thesecontaminants from wastewater, the impact of wastewater discharge on surface water orgroundwater supplies, and the removal efficiency of the remaining contaminants bydrinking water treatment processes.
A significant number of articles have investigated the fate of trace hormones andpharmaceuticals in water treatment processes (Ternes, Kreckel et al. 1999; Ternes,
Stumpf et al. 1999; Snyder, Westerhoff et al. 2003; Huber, Korhonen et al. 2005;
Westerhoff, Yoon et al. 2005; Snyder, Adham et al. 2006; Snyder, Wert et al. 2006; Yoon,
Westerhoff et al. 2006).

The ability of a particular treatment process to remove organic

contaminants depends mostly on the structure and concentration of the contaminant.
In addition, the operational parameters of the process (e.g., oxidant dose and contacttime) will also determine the degree of attenuation of a particular contaminant.
3. Results
The results from US drinking water testing for select EDCs andpharmaceuticals are shown in Table 1.

The insect repellant N,N diethyl-m-toluamide(DEET), the suspected endocrine disrupting herbicide atrazine, and the anti-anxiety
pharmaceutical meprobamate were the top three occurring contaminants, respectively,in this study.

In raw waters, the profile was quite different.

The greatest impact inmost water treatment systems occurs during disinfection.

Disinfection with ozone

provided, by far, the greatest removal of contaminants, followed by free chlorine,- 199 -

chloramine, and UV, respectively (Tables 2-5).

In full scale plants, removal by

disinfection was quite comparable to that predicted in bench and pilot scale testing.
Removal by activated carbon and membranes can be highly efficient depending upon
the operation parameters (Snyder, Adham et al. 2006); however, these processes are
far less common in US drinking water treatment facilities. While ozone was found tobe highly-efficient oxidizing selected contaminants in both drinking and reuse waters(Snyder, Wert et al. 2006), the formation of oxidation products must be considered.
The human health consideration of selected trace contaminants was evaluated.
Table 6 provides the DWEL values for some of the contaminants considered.

Using

the MCF-7 in vitro bioassay, it was demonstrated that estrogenicity of recommended
serving sizes of soy sauce, green tea, and cows milk provided far greater estrogenicity
than did any wastewater or drinking water.

These data show that using an in vitro

measure of estrogenicity may not be suitable for extrapolation to health risk.

Oxidationby ozone and chlorine readily degraded any observed estrogenicity, and subsequent
byproducts were no longer estrogenic.
4. Conclusions
Trace levels of hormones and pharmaceuticals are ubiquitous contaminants ofmunicipal wastewater effluents.
analytical detection limits.
to be discovered.

The detection of these chemicals is a direct function of

Therefore, more and more trace contaminants will continue

Water treatment processes have various levels of efficacy in theattenuation of these contaminants.

In drinking water, oxidation provides a

cost-effective means for disinfection and simultaneous contaminant removal.

Those

compounds which are resilient to oxidation are often detected in finished US drinking
waters.

However, the concentration at which these occur is extremely small, and far

below the concentrations that would be expected to be of human health concern.

In anevaluation of estrogenicity as a class of toxicity, the estrogenicity of common food items
is far beyond that of any wastewater or drinking water evaluated.

The relative risk

factors of common exposure to EDCs through foods and beverages appears to be far
greater than the exposure through drinking water.

More research is needed toadequately address human health relevance of EDCs and pharmaceuticals, but it islikely that most drinking waters do not provide a substantial exposure and theconcentrations expected to have human health detriment.

5. References
Cargouet, M., D. Perdiz, et al. (2004). "Assessment of river contamination by estrogenic
compounds in Paris area (France)." Science Of The Total Environment 324(1-3):- 200 -

55-66.
Daughton, C. G. and T. A. Ternes (1999). "Pharmaceuticals and Personal Care Products inthe Environment: Agents of Subtle Change?" Environmental Health Perspectives
107(6): 907-938.
Desbrow, C., E. J. Routledge, et al. (1998). "Identification of Estrogenic Chemicals in STW
Eflleunt. 1. Chemical Fractionation and in Vitro Biological Screening."
Environmental Science & Technology 32(11): 1549-1558.
Halling-Sorensen, B., S. N. Nielsen, et al. (1998). "Occurence, Fate and Effects ofPharmaceutical Substances in the Environment - A Review." Chemosphere 36(2):357-393.
Hignite, C. and D. L. Azarnoff (1977). "Drugs and drug metabolites as environmental
contaminants: chlorophenoxyisobutyrate and salicylic acid in sewage water
effluent." Life Sciences 20(2): 337-341.
Huber, M. M., S. Korhonen, et al. (2005). "Oxidation of pharmaceuticals during water
treatment with chlorine dioxide." Water Research Water Research 39: 3607-3617.
Kolpin, D. W., E. T. Furlong, et al. (2002). "Pharmaceuticals, Hormones, and Other Organic
Waste Contaminants in U.S. Streams, 1999-2000: A National Reconnaissance."
Environmental Science & Technology 36(6): 1202-1211.
Metcalfe, C. D., B. Koenig, et al. (2000). Drugs in sewage treatment plant effluents in
Canada. ACS National Meeting, American Chemcial Society.
Petrovic, M., E. Eljarrat, et al. (2004). "Endocrine disrupting compounds and other emerging
contaminants in the environment: A survey on new monitoring strategies andoccurrence data." Analytical and Bioanalytical Chemistry 378(3): 549-562.
Purdom, C. E., P. A. Hardiman, et al. (1994). "Estrogenic effects of effluents from sewage
treament works." Chemistry and Ecology 8: 275-285.
Routledge, E. J., D. Sheahan, et al. (1998). "Identification of estrogenic chemicals in STW
effluent. 2. In vivo responses in trout and roach." Environmental Toxicology andChemistry 32(11): 1559-1565.
Schueler, F. W. (1946). "Sex-hormonal action and chemical constitution." Science 103:
221-223.
Sluczewski, A. and P. Roth (1948). "Effects of androgenic and estrogenic compounds on theexperimental metamorphoses of amphibians." Gynecology and obstetrics 47:
164-176.
Snyder, S. A., S. Adham, et al. (2006). "Role of Membranes and Activated Carbon in the
Removal of Endocrine Disruptors and Pharmaceuticals." Desalination 202: 156-181.
Snyder, S. A., T. L. Keith, et al. (1999). "Analytical methods for detection of selectedestrogenic compounds in aqueous mixtures." Environmental Science & Technology
33(16): 2814-2820.

- 201 -Snyder, S. A., K. L. Kelly, et al. (2001). Pharmaceuticals and personal care products in thewaters of Lake Mead, Nevada. Pharmaceuticals and Personal Care Products in theEnvironment: Scientific and Regulatory Issues. C. G. Daughton and T. L.
Jones-Lepp. Washington,D.C., American Chemical Society. Symposium Series 791:
116-140.
Snyder, S. A., E. C. Wert, et al. (2006). "Ozone oxidation of endocrine disruptors andpharmaceuticals in surface water and wastewater." Ozone Science & Engineering
28: 445-460.
Snyder, S. A., P. Westerhoff, et al. (2003). "Pharmaceuticals, Personal Care Products, andEndocrine Disruptors in Water: Implications for the Water Industry." Environmental
Engineering Science 20(5): 449-469.
Stumm-Zollinger, E. and G. M. Fair (1965). "Biodegradation of steroid hormones." Journal of
the Water Pollution Control Federation 37: 1506-1510.
Tabak, H. H. and R. L. Bunch (1970). "Steroid hormones as water pollutants. I. Metabolism
of natural and synthetic ovulation-inhibiting hormones by microorganisms ofactivated sludge and primary settled sewage." Dev. Ind. Microbiol. 11: 367-376.
Ternes, T. A. and R. Hirsch (2000). "Occurrence and behavior of x-ray contrast media insewage facilities and the aquatic environment." Environmental Science &Technology 34: 2741-2748.
Ternes, T. A., R. Hirsch, et al. (1998). "Methods for the determination of neutral drugs aswell as betablockers and β2-sympathomimetics in aqueous matrices using GC/MSand LC/MS/MS." Fresenius' Journal of Analytical Chemistry 362: 329-340.
Ternes, T. A., P. Kreckel, et al. (1999). "Behaviour and occurrence of estrogens in municipal
sewage treatment plants - II. Aerobic batch experiments with activated sludge." The
Science of the Total Environment 225: 91-99.
Ternes, T. A., M. Stumpf, et al. (1999). "Behavior and occurence of estrogens in municipal
sewage treatment plants - I. Investigations in Germany, Canada and Brazil." The
Science of the Total Environment 225: 81-90.
Vanderford, B. J., R. A. Pearson, et al. (2003). "Analysis of Endocrine Disruptors,
Pharmaceuticals, and Personal Care Products in Water Using Liquid
Chromatography/Tandem Mass Spectrometry." Analytical Chemistry 75(22):6265-6274.
Westerhoff, P., Y. Yoon, et al. (2005). "Fate of endocrine-disruptor, pharmaceutical, andpersonal care product chemicals during simulated drinking water treatment
processes " Environmental Science & Technology 39(17): 6649-6663.
Yoon, Y., P. Westerhoff, et al. (2006). "Removal endocrine disrupting compounds andpharmaceuticals by nanofiltration and ultrafiltration membranes." Desalination
202: 16-23.

- 202 -

Table 1.

Occurrence of EDCs and Pharmaceuticals in 20 US Drinking Waters

Compound
DEET
Atrazine
Meprobamate
Dilantin
Ibuprofen
Iopromide
Caffeine
Carbamazepine
TCEP
Gemfibrozil
Metalochlor
EstroneProgesterone
Erythromycin
Musk Ketone
Naproxen
Sulfamethoxazole
Triclosan
Trimethoprim

Hits
18
15
15
14
13
13
12
11
7
5
4
2
2
1
1
1
1
1
1

% Freq Min (ng/L) Max (ng/L) Median (ng/L) Ave (ng/L)
90
2.1
30
5.1
8.2
75
1.4
430
29
74
75
1.6
13
3.8
6.1
70
1.1
6.7
2.3
2.7
65
1
32
3.8
7.9
65
1.1
31
6.5
8.5
60
2.6
83
23
25
55
1.1
5.7
2.8
2.8
35
3
19
5.5
10.1
25
1.3
6.5
4.2
3.9
20
14
160
86
86
10
1.1
2.3
1.7
1.7
10
1.1
1.1
1.1
1.1
5
1.3
1.3
1.3
1.3
5
17
17
17
17
5
8
8
8
8.0
5
20
20
20
20
5
43
43
43
43
5
1.3
1.3
1.3
1.3

Table 2. Summary of Removal by Ozone Disinfection> 80% Removal
Acetaminophen
Androstenedione
Caffeine
Carbamazepine
Diclofenac
Erythromycin
Estradiol
Estriol
EstroneEthynylestradiol
Fluoxetine
Gemfibrozil
Hydrocodone
Naproxen
Oxybenzone
Pentoxifylline
Progesterone
Sulfamethoxazole
Triclosan
Trimethoprim
Testosterone

24 Minutes Contact Time
50-80% Removal
20-50% Removal
DEET
Atrazine
Diazepam
Iopromide
Dilantin
Meprobamate
Ibuprofen- 203 -

< 20% Removal
TCEP

Table 3. Summary of Removal by Free Chlorine
Chlorine Dose = 3 mg/L, Contact Time = 24 hours, pH=7.9-8.5> 80% Removal
50-80% Removal
20-50% Removal< 20% Removal
Acetaminophen
Gemfibrozil
Diazepam
Androstenedione
Benzo(a)pyrene
Galaxolide
Atrazine
Diclofenac
Pentoxifylline
Caffeine
Erythromycin
Carbamazepine
Estradiol
DDT
Estriol
DEET
EstroneDilantin
Ethynylestradiol
Fluorene
Hydrocodone
Fluoxetine
Musk Ketone
g-BHC
Naproxen
Ibuprofen
Oxybenzone
IopromideSulfamethoxazole
Meprobamate
Triclosan
Metolachlor
Trimethoprim
Progesterone
TCEP
Testosterone

Table 4. Summary of Removal by Chloramine> 80% Removal
Acetaminophen
Estradiol
Estriol
EstroneEthynylestradiol
Triclosan

Chloramine Dose = 3 mg/L, Contact Time = 24 hours
50-80% Removal
20-50% Removal< 20% Removal
Benzo(a)pyrene
Hydrocodone
Androstenedione
Diclofenac
Galaxolide
Atrazine
Oxybenzone
Caffeine
Carbamazepine
DDT
DEET
DiazepamDilantin
Erythromycin
Fluorene
Fluoxetine
g-BHC
Gemfibrozil
Ibuprofen
Iopromide
Meprobamate
Metolachlor
Musk Ketone
Naproxen
Pentoxifylline
Progesterone
Sulfamethoxazole
TCEP
Testosterone
Trimethoprim- 204 -

Table 5. Summary of Removal by UV disinfection (40 mJ/cm2)> 80% Removal

Table 6.

50-80% Removal
Diclofenac
Sulfamethoxazole
Triclosan

20-50% Removal
Acetaminophen< 20% Removal
Androstenedione
Atrazine
Caffeine
Carbamazepine
DEET
DiazepamDilantin
Erythromycin-H2O
Estradiol
Estriol
EstroneEthynylestradiol
Fluoxetine
Gemfibrozil
Hydrocodone
Ibuprofen
Iopromide
Meprobamate
Naproxen
Oxybenzone
Pentoxifylline
Progesterone
TCEP
Testosterone
Trimethoprim

Human Health Evaluation of Select ContaminantsComposite
SafetyFactor

DWEL(ng/L)

300

81,000

20

4,100

1,000

96,000

<0.25
<0.50
<0.50

380,000
190,000
190,000

Carbamazepine

3,000

330,000

18

18,000

Diazepam

1,000

4,800

<0.25

19,000Drug
Atenolol
Atorvastatino-hydroxy atorvastatino-hydroxy atorvastatin

Max Finished
Water Conc.
(ng/L)

Margin of
SafetyDiclofenac

300

66,000<0.25

260,000

Enalapril300

33,000<0.25

130,000

Fluoxetine

1,000

36,000<0.50

66,000Gemfibrozil

1,000

450,000

2.1

210,000

Meprobamate

1,000

480,000

43

11,000

Naproxen

300

330,000<0.50

960,000

Phenytoin

1,000

2,400,000

15

160,000

Risperidone

1,000

780

Simvastatin

3,000

57,000

0.34
<0.25
<0.25

230,000
230,000

Sulfamethoxazole

300

3,900,000

3

1,300,000

Triclosan

1,000

29,0001.2

24,000

Trimethoprim

300

1,100,000<0.25

4,400,000

Simvastatin hydroxy acid- 205 -

2,300

Occurrence, Treatment, andToxicological Relevance of
EDCs and Pharmaceuticals in
Drinking Water

EDCs:
EDCs: A Tale of Sin Cityor
EDCEDC-CSI Las Vegas

Shane Snyder, Ph.D.
Southern Nevada Water Authority
University of Nevada, Las Vegas- Las Vegas, Nevada – pop. ≈2,000,000- ≈35,000,000 visitors per year
- VERY DRY - <7 cm rain & >2 M evap.
- Water reuse critical for sustainability≈ 5,500 new people/month
600,000≈ 1,200 new homes/month

500,000

Acre-feet per year

≈ 1 new school/month≈ 100 teachers/month> $3,000,000,000 in water projects

400,000

ASR Program

300,000
200,000

Colorado Riverwater(from Lake Mead)Land subsidence
100,000
spring flow

≈ $5,000,000,000 expected projects

01900

groundwater

1910

1920

1930

1940

1950

1960

1970

1980

1990

2000

Year

WATER CONTROLS LAS VEGEAS!

Thee Advanced Wastewater Plants≈1,200,000 cubic meters/day

Lake Mead and the Lower
Colorado River provide water for
More than 22,000,000 people

X
X
X- 206 -

Las Vegas Wash Area
(2002 Data)
100 ppm
1 ppm

Wash gravel
area

Athens Road wells
PEPCON
plume
Kerr-McGee
plume- 207 -

Depth (m)August 9, 2004, Meprobamate (ng/L)
-10
-30
-50
-70
-90
-110
-130
-150

50
40
NH2

O

O
O

30

O

20

H2N

10

0

2

4

6

LV Wash

8

10

12

LV Basin (Km)14

16

Hoover Dam

0

Depth (m)August, 9, 2004, Sulfamethoxazole (ng/L)
-10
-30
-50
-70
-90
-110
-130
-150

30
O

25
O

N
HN

S

15
10
NH2

5

0

2

LV WashDepth (m)June 3, 2004, Meprobamate
150

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

INTAKE 1 x

135

INTAKE 2 x

120
105
90
75
60
45
30

0

2

4

6

8

10

12

14

16

LV Wash>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>Hoover Dam

150

Depth (m)June 3, 2004, TCEP
-10
-30
-50
-70
-90
-110
-130
-150

50

INTAKE 1 x
INTAKE 2 x

40
30
20
10

0

2

4

6

8

10

12

14

16

LV Wash>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>>Hoover Dam0- 208 -

20

O

4

6

8

LV Basin (Km)

10

12

14

Hoover Dam

160On Tap Winter 2003

Cost of these projects is>$1,500,000,000

Phoenix New Times, August 9, 2001

“They're in the Water... They Make Fish
Change Sex...
Endocrine Disruptors-What are they
doing to you?”“Nevada's wastewater iscausing sex problems in fish.
But will Arizona get screwed by
the solution?”

EDCs and Pharmaceuticals
Pose Major Threats toWater Sustainability!

The US Fish & Wildlife Service
is requesting a flowflow-through fish
exposure study to compare ourcurrent wastewater towastewater after advanced
treatment processes (i.e.,
membranes, ozone, UVUV-AOP)

Treatment Processes

Treatment Processes(>60 EDCs/PPCPs)
EDCs/PPCPs)
AwwaRF #2758• Coagulation and Softening• Activated Carbon (GAC and PAC)
• Membranes (UF, NF, RO, MBR, e-dialysis)• Magnetic Ion-Exchange (MIEX)• Biological Processes– Biologically active filtration (carbon and anthracite)– River Bank Filtration– MBR– ASR/SAT• Chlorination (ambient and pH 5.5)
• Ozonation (and AOP with peroxide)• UV (and AOP with peroxide)

Steroids
Testosterone

Progesterone

Androstenedione- 209 -

Ethinyl estradiol

17β Estradiol

EstroneEstriolUV 40 mJ

Chlorine 3.5 mg/L

Steroids

Ozone 2.5 mg/L

Testosterone

Testosterone

Androstenedione

Ethinyl estradiol

Progesterone

Estradiol

17β Estradiol

Progesterone

Estriol

EstroneEstroneEthynylestradiol
0

20

40

60

80

EstriolAndrostenedione100% Removal

Psychoactive

UV 40 mJ

Chlorine 3.5 mg/L

20

40

Ozone 2.5 mg/L

Caffeine

Fluoxetine

Carbamazepine

Dilantin

Meprobamate

Diazepam

DiazepamDilantin

Caffeine
Carbamazepine

Meprobamate

Fluoxetine

0<30% Removal

30-70% Removal

Testosterone
Progesterone
Androstenedione
Estriol
Ethynylestradiol
EstroneEstradiol
Erythromycin-H2O
Trimethoprim
Naproxen
Hydrocodone
Ibuprofen
Caffeine
Fluoxetine
Meprobamate
DiazepamDilantin
Carbamazepine
DEET
Atrazine
Galaxolide
TCEP
Iopromide
Pentoxifylline
MetolachlorGemfibrozil
Musk Ketone

Sulfamethoxazole
Triclosan
Diclofenac
Acetaminophen

80>70% Removal

Chlorine 3.5 mg/L 24 hr

UV 40mJ/cm2<30% Removal

30-70% Removal>70% Removal

Musk Ketone
TCEP

Meprobamate
Atrazine
Iopromide

Testosterone
Progesterone
Androstenedione
Estriol
Ethynylestradiol
EstroneEstradiol
Erythromycin-H2O
Sulfamethoxazole
Triclosan
Trimethoprim
Naproxen
Diclofenac
Ibuprofen
Hydrocodone
Acetaminophen
Carbamazepine
DilantinDiazepam
Caffeine
Fluoxetine
DEET
Metolachlor
Galaxolide
Pentoxifylline
Gemfibrozil

Ozone 2.5 mg/L

60

% Removal- 210 -

<30% Removal

30-70% Removal>70% Removal

Testosterone
Progesterone
Androstenedione
Caffeine
Fluoxetine
Meprobamate
DiazepamDilantin
Carbamazepine
DEET
Atrazine
Galaxolide
TCEP
Iopromide
Pentoxifylline

Ibuprofen
MetolachlorGemfibrozil

Estriol
Ethynylestradiol
EstroneEstradiol
Erythromycin-H 2O
Sulfamethoxazole
Triclosan
Trimethoprim
Naproxen
Diclofenac
Hydrocodone
Acetaminophen
Musk Ketone100

Predicted chlorine removal (%)

Chlorine Model QSAR

Glide

– Estradiol dock with 1GWR

100
80
60
40
20
0
0

20

40

60

80

100

Average chlorine removal (%)

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

Las Vegas WWTP Ave Conc.

Wastewater Ozonation

Jun-05 Jan-06 Jan-06

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

Jun-05 Jan-06 Jan-06

Target Compound ng L-1

ng L-1ng L-1

Target Compoundng L-1ng L-1ng L-1Androstenedione
Caffeine
Carbamazepine
DEET
Diclofenac
Dilantin
Erythromycin
Estriol
EstroneFluoxetine
Galaxolide
Gemfibrozil
Hydrocodone

1.6
21
139
133
73
143
162
5.7
5.4
14
NM
16
199

2.4
31
139
123
71
110
149
<5
20
11
NM
567
161

Ibuprofen
Iopromide
Meprobamate
Musk Ketone
Naproxen
Oxybenzone
Sulfamethoxazole
TCEP
Testosterone
Triclosan
Trimethoprim

19
22
332
133
13
6
841
373
<1
<10
35

5.6
139
796
NM
25
<1
669
235
1.8
35
191

15
45
737
NM
71
3.0
695
187
<1
58
229

EEq*

0.63

1.00

3.17

<1
51
210
188
54
154
133
<5
<1
<1
1170
<1
240

Las Vegas WWTP:
shade = <MRL @ 3 mg/L O3
Jun-05 Jan-06 Jan-06
ng L

-1

ng L

-1

Target Compound

ng L

-1

ng L

-1

ng L

Androstenedione
Caffeine
Carbamazepine
DEET
Diclofenac
Dilantin
Erythromycin
Estriol
EstroneFluoxetine
Galaxolide
Gemfibrozil
Hydrocodone

1.6
21
139
133
73
143
162
5.7
5.4
14
NM
16
199

2.4
31
139
123
71
110
149
<5
20
11
NM
567
161

Ibuprofen
Iopromide
Meprobamate
Musk Ketone
Naproxen
Oxybenzone
Sulfamethoxazole
TCEP
Testosterone
Triclosan
Trimethoprim

19
22
332
133
13
6
841
373
<1
<10
35

5.6
139
796
NM
25
<1
669
235
1.8
35
191

15
45
737
NM
71
3.0
695
187
<1
58
229

EEq*

0.63

1.00

3.17

<1
51
210
188
54
154
133
<5
<1
<1
1170
<1
240

Before Ozonation

Jun-05 Jan-06 Jan-06

Target Compound ng L-1-1Bromate Formation/Mitigation
35
No Chemical
30

US patent No. US 6,602,426 B2

0.5 Cl2 & 0.1 NH3
0.5 Cl2 & 0.3 NH3Bromate (ug/L)

25

0.5 Cl2 & 0.5 NH3

20
15
10
5
0
1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

Transferred Ozone Dose (mg/L)- 211 -

After Ozonation

Perchlorate in Commercial Bleach – Sodium Hypochlorite
100

ug/mL Perchlorate

80

12.50%
6.00%
10.00%

60

40

20

0
Apr-05Jul-05

Oct-05Jan-06

Apr-06

Jul-06

Toxicological Relevance
AwwaRF #3085 & WRF 0404-003

Emerging Contaminants in US Drinking Waters (n=20)
Compound
DEET
Atrazine
Meprobamate
Dilantin
Ibuprofen
Iopromide
Caffeine
Carbamazepine
TCEP
Gemfibrozil
Metalochlor
EstroneProgesterone
Erythromycin
Musk Ketone
Naproxen
Sulfamethoxazole
Triclosan
Trimethoprim

Sulfamethoxazole – Chlorine/ChloramineRaw:
59 ng/L
ng/L

Hits
18
15
15
14
13
13
12
11
7
5
4
2
2
1
1
1
1
1
1

% Freq Min (ng/L) Max (ng/L) Median (ng/L) Ave (ng/L)
90
2.1
30
5.1
8.2
75
1.4
430
29
74
75
1.6
13
3.8
6.1
70
1.1
6.7
2.3
2.7
65
1
32
3.8
7.9
65
1.1
31
6.5
8.5
60
2.6
83
23
25
55
1.1
5.7
2.8
2.8
35
3
19
5.5
10.1
25
1.3
6.5
4.2
3.9
20
14
160
86
86
10
1.1
2.3
1.7
1.7
10
1.1
1.1
1.1
1.1
5
1.3
1.3
1.3
1.3
5
17
17
17
17
5
8
8
8
8.0
5
20
20
20
20
5
43
43
43
43
5
1.3
1.3
1.3
1.3

Three Example US Drinking Water Facilities

PostPost-coagulation:
59 ng/L
ng/L

400

Plant #1

300

Raw
Finished

200
100

PostPost-filtration:
0.78 ng/L
ng/L

Concentration (ng/L)

PrePre-filtration:
2.7 ng/L
ng/L

Finished:
0.38 ng/L
ng/L

0
300

Plant #2

200
100
0
30

Plant #3

20
Two distribution sites:<0.25, 0.38 ng/L
ng/L

- 212 -

P

P
TC
P

ne

TC
E

DE

zi
At
ra

M
ET
et
ol
ac
hl
or

Ca
r

0

At
en
ol
ol
ba
m
az
ep
in
e
Di
la
nt
M
i
n
ep
ro
ba
m
at
e

10

Relevance to Human HealthIntentional vs. Unintentional
Sulfamethoxazole
Atenolol
Trimethoprim
Meprobamate
Dilantin
Carbamazepine
Atrazine
LinuronGemfibrozil

Drinking Water (ng/L)<0.25 <0.25
0.38
20
0.42
0.35
<0.25 <0.25 <0.25
12
24
35
13
7.4
11
8.2
10
9.9
76
138
1080
8.1
<0.50 <0.50
0.48
0.51
0.33

Reuse Water (ng/L)<0.25 <0.25 <0.25
1.7
2.6
2.1
0.41
0.60
0.50
0.58 <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 <0.50
0.62 <0.25
0.53

What will we find at pg/L, fg/L,
fg/L, åg/L?

Soy Sauce vs. Wastewater
Estrogenicity (EEq)
EEq)
SOY SAUCE
KikkomanTabascoKimlanLa Choy

147
257
70
14

RAW WASTEWATER
WWTP-1
WWTP-2
WWTP-3Why do we view
EDC/PPCPs
EDC/PPCPs differently?

WASTEWATER EFFLUENT
WWTP-1
WWTP-2
WWTP-3

4.6
0.05
0.61

Why is perchlorate
different?

DRINKING WATER
Utility-1
Utility-2
Utility-3

70
41
53

<0.03
<0.03
0.07

We must determine
toxicological relevance!

The public has difficulty with the concept ofrelative concentrations- Instead, they apply the “present/absent” litmus test

- Adverse health effects are presumed if present

Nanograms

s
gram
Micro

ter ?
per liper liter ?

per
rams
Picog
Zeptograms
per liter ?

liter ?

Conclusions

How Low can We Go?

• EDCs and Pharmaceuticals are ubiquitous• Removal related to structure (and dose)– Chlorine good for phenolics, less effective forketones– Ozone more effective than chlorine– UV ineffective at disinfection doses• Effective with high-energy UV & AOP using peroxide• Ozone eliminates in vitro estrogenicity• Surface water under influence of

conventional WWTPs will have more tracecontaminants than IPR system

Sodium and Iodine Atoms on Copper- 213 -

Take Home Thoughts…

2007 – SNWA opened a new
Laboratory & Applied R&D Center

Non-detect ≠ Safe
• Safe ≠ Non-detect• Non-detect ≠ Zero
• Consider public perception• Consider public dollars
•

–
–

•

The public will pay for monitoring programs
The public will pay for additional treatment

There is NO silver bullet––––

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

Las Vegas will…

FaceFace-Face Communication¾ Leaders in sustainability¾ Model City for conservation¾ Model City for research¾ Explore cutting-edge

conservation practices¾ International destination“water tourism/science”¾ Establish collaborations

globally

Only through collaborative
sustainability research will
our city survive!

Shane Snyder, Ph.D.
shane.snyder@snwa.com- 214 -