Evaluation of Drinking Water Treatment Technologies for
Removal of Endocrine Disrupting Chemicals
上水道における内分泌かく乱化学物質の除去技術

Kathleen Schenck, U.S. EPA
米国環境保護庁 キャサリン・シェンク‑ 339 ‑Evaluation of Drinking Water
Treatment Technologies
for Removal of Endocrine
Disrupting Chemicals

Endocrine disrupting chemicals (EDCs) areexogenous agents that interfere with thesynthesis, secretion, transport, binding, action,or elimination of natural hormones in the bodythat are responsible for the maintenance of
homeostasis, reproduction, development,and/or behavior.

Kathleen Schenck, Thomas Speth andChristopher Parrett, U.S. EPA
Laura Rosenblum, Steve Wendelken, Barry Pepich,and Radha Krishnan, Shaw, Inc.
Thomas Wiese, Xavier University of Louisiana

Many of the compounds identified as potential
endocrine disrupting chemicals (EDCs) may bepresent in surface or ground waters used as
drinking water sources due to their introduction
from:Legislation Associated withEndocrine Disrupting
Chemicals
Food Quality Protection Act of 1996

Domestic and industrial sewage treatment
systems.

Safe Drinking Water Act Amendmentsof 1996

Wet-weather runoff.

Occurrence of EDCs in U.S. streams
CompoundNumberofsamples

Reporting
limit
μg/L

Freq. ofdetection%

Maximum
conc.
μg/LMediandetectableconc. μg/L

estradiol

700.005

10.0

0.093

0.009

ethynylestradiol

70

0.005

5.7

0.273

0.094

testosterone

700.005

2.8

0.214

0.116

nonylphenol

85

0.50

50.6

40

a0.8

Basic strategies to decrease the potential risk ofadverse health effects associated with thepresence of EDCs in drinking water:
Protect drinking water sources fromcontamination by EDCs.
Remove EDCs, that may be present in source
waters, during drinking water treatment.

aa: concentration estimated – reference standard from technical mixture
From: Environ. Sci. Technol. 36,1202 – 1211, 2002,Environ. Sci. Technol. 36,4007 – 4008, 2002

Compounds to be evaluatedCompounds to be evaluatedCH3Estradiol

CH3

OHEstriol

CH3

OH

Progesterone
OH

CH3C

O

Testosterone

CH3CH3OHO

HO

Ethynylestradiol

CH3O

Dihydrotestosterone OHCH3OH
C

CH
CH3O
HO‑ 340 ‑HOH
CH3

Analytical method for steroid compounds

Technical approach
Solid phase extraction:
Baker C18 XF speed disks eluted withmethanol

Develop analytical methods to identify
and quantify the target compounds.
The approach includes concentration bysolid-phase extraction, followed byLC/MS.

Quantitation:
Waters ZQ LC/MS, electrosprayXterra C18 column
Single step gradient, 50 – 65% methanol inammonium hydroxide in waterSingle ion mode

Technical approach (cont.)Evaluate the use of a reporter geneassay, the MVLN assay, to detect thepresence/removal of estrogenic activity.
This assay uses a human breast cellline (MCF-7) which has been stablytransfected with the firefly luciferasegene.

MVLN Cells

MVLN AssayMVLN cells, previously withdrawn fromestrogens, are seeded into 96 well plates(day 1).
Media is removed from wells and replaced withmedia containing treatments (samples, andpositive and negative controls) in ethanol carrier
solvent. All treatments are done in quadruplicate(day 2).
Treatment media is removed and replaced withfresh treatments (day 3).

MVLN Reporter Gene Assay ofControl Compounds

MVLN Assay (cont.)

140
130120110
100
9080
7060
5040

Treatment media is removed, the cells arewashed, and lysed. The luciferase activity (lightproduction) is then determined using aluminometer. (day 4)
Estrogenic activity is determined by comparing
the average luciferase activity for each treatmentgroup to the activity of estradiol or the doseresponse curve of the analyte used.

3020
100-10-20
10-14 10-13 10 -12 10 -11 10-10 10-9 10 -8 10 -7 10 -6 10-5
Log Con M
Estradiol
EthE2E3 -5
Progesterone
Testosterone
DHT
Bisphenol A‑ 341 ‑EtOH
ICI -7
ICI -7 + E2 -9

Technical approach (cont.)

Modeling Requirements

Conduct bench-scale evaluations ofvarious drinking water treatment
technologies, including granular activatedcarbon (GAC), conventional treatment,
softening and nanofiltration.
Pilot-scale evaluations may be conductedon the treatment technologies that appear
promising at bench-scale.

Carbon Information
Isotherms
Film Transfer CoefficientInternal Diffusion Coefficient

Carbon Information
Norit
1240

Hydrodarco
4000

Superdarco

Bulk Density(g/ml)

0.48

0.40

0.33

Apparent
Density (g/ml)

0.66

0.59

0.41

Bed Void
Fraction

0.26

0.32

0.21

Particle
Diameter (mm)

1.04

1.14

1.00

Granular activated carbon (GAC) isothermstudies
Organic–free filter sterilized water buffered topH 7 with phosphate buffer (0.005 M)
Target compound (100 μg/L) added to bufferand mixed for approximately 24 hours
Solution added to isotherm bottles containing
various amounts of GAC
After various treatment times, solution ispumped out through a 0.22 μm filter
Initial and final concentration data used todetermine adsorption capacity of GAC

Adsorption of Ethynylestradiol (EE2)
on Hydrodarco 4000 GAC

Adsorption of Ethynylestradiol (EE2)
on Norit GAC 1240
Liquid-Phase Concentration μg/L

Liquid-Phase Concentration μg/L

Capacity μg/gb

100-200 Mesh
Week 10.57 ± 0.039a

13400 ± 43

Week 20.14 ± 0.014

13500 ± 40

Week 30.060 ± 0.011

13500 ± 33

0.076 ± 0.0042

13500 ± 72

Week 20.034 ± 0.0066

Week 313500 ± 46

0.011 ± 0.0015

Week 1

0.12 ± 0.013a

15700 ± 480

Week 20.022 ± 0.0052

16000 ± 13

Week 30.011 ± 0.0054

16000 ± 58

Week 1

0.091 ± 0.066

16000 ± 46

Week 20.019 ± 0.0074

16000 ± 14

Week 30.0076 ± 0.0029

16000 ± 0200-400 Mesh

200-400 Mesh
Week 1

Capacity μg/gb

100-200 Mesh

13500 ± 50

a Meana Mean ± standard deviation of four replicate treatment samples (N=4)

b C± standard deviation of four replicate treatment samples (N=4)

o was determined by averaging the untreated samples (N=44)

b C was determined by averaging the untreated samples (N=44)
01000

1/n

Superdarco, K=378,000 Pg/g(L/Pg)
1/n
Norit-1240, K=198,000 Pg/g(L/Pg)
1/n
HD-4000 K=45,300 Pg/g(L/Pg)

10 40.001

relative EE2 conc. by MVLN assay (ug/LSolid-Phase Concentration (Pg/g)

Comparison of analytical and estrogenic activity results
10 5

Ethynylestradiol Isotherms
200x400-mesh carbon
3 week equilibration
0.01

0.1

1

Liquid-Phase Concentration (Pg/L)

10

0.1

0.001
0.001

0.1

10

EE2 conc. by LC/MS (ug/L)‑ 342 ‑

1000

Short-Bed Adsorber Studies

Effluent Concentration (ug/L)

Influent: 100 μg/L ethynylestradiol inorganic free water buffered to
pH 7 with phosphate buffer(0.005 M)
Column: 44g or 88g of granular activatedcarbon
Flow rate: 350 ml/min
Length of run: 10 hrs (210 L)
Sampling: Influent samples were collected
at 0 min, 1, 2, 4, 6, 8 and 10 hrs.
Effluent samples were collected
at 10, 20, 30, 40 and 50 min; 1,2, 4, 6, 8, and10 hrs.

Average Film Transfer
Determination

30

Ethynylestradiol Short-Bed Adsorber
44 g of 12x40-mesh HD-4000 carbon
10 m/hr, EBCT=19 sec

25Carbonkfilm (cm/sec)Datakfilm (cm/sec)
Gnielinski
Correlation

Superdarco

3.4x10-3

2.6x10-3

Hydrodarco
4000

2.1x10-3

1.8x10-3

Norit12402.4x10-3

2.2x10-3

2015Prediction, kf=2.4E-3 cm/s, Ds=0, Dp=3.3E-6 cm2/s
105Effluent Data
00200

400600800

Time (minutes)

Future Study Options

This study will provide information on:
Currently available drinking water
treatment technologies that can remove
EDCs, specifically the steroidhormones.

Run batch-recirculating study todetermine internal diffusion
Run RSSCTApproaches to optimize these treatment
technologies for EDC removal.

Run pilot columns‑ 343 ‑