Transcript Endocrine Disruption

Estrogenic Compounds in
Wastewater
Presentation to the Metropolitan Council
Environment Committee
September 23, 2008
Paige Novak, Deb Swackhamer, Mike Semmens,
Megan Ogdahl, Matt Wogen, Mark Lundgren
University of Minnesota
What is the problem?
Endocrine disruptors,
estrogenic compounds,
and other
pharmaceuticals have
been observed in
streams and
wastewater treatment
plant discharges
throughout the United
States, Europe, and
Asia
Hormones

Chemical signals pass through the blood and bind to
cells in the target organ; initiates physiochemical
response

Crucial for reproductive function and development
Natural hormone
Receptor
Physiochemical
response
Secreting cell
Target cell
Hormones

Chemical signals pass through the blood and bind to
cells in the target organ; initiates physiochemical
response

Crucial for reproductive function and development
External chemical
Receptor
Physiochemical
response
Secreting cell
Target cell
Hormones

Chemical signals pass through the blood and bind to
cells in the target organ; initiates physiochemical
response

Crucial for reproductive function and development
External hormone or estrogen mimic
Receptor
Target cell
Unintended
Physiochemical
response
Research question:
How do estrogens or estrogen
mimics behave across a wastewater
treatment plant?
If we have a body of data we are better
able to gauge risk, know which
compounds are problematic, how to
monitor them, better treat the material, etc.
What we analyze
1. Binding assays: total sample “estrogenicity”
(including unknown compounds)
2. Analytical (LC-MS): specific compounds only
Phytoestrogens
Genistein
Industrial compounds
(+breakdown products)
Nonylphenol
Octylphenol
Bisphenol A
Antimicrobial
Triclosan
Synthetic or natural
estrogenic hormones
Estradiol
Estrone
Ethynylestradiol
Estriol
Methods for analysis
Collect samples
Specific compounds
quantified
(40 L concentrated
to 150-300 uL)
Processing
& cleanup
Incubate with samples
and quantify binding
Yeast cells: alive,
human estrogen receptor
Trout liver cells: not “alive,”
trout estrogen receptor
receptors
Cells (yeast or
trout liver)
Sample locations
Primary treatment
Screens, grit
removal, and
primary settling
Secondary treatment
Recycle
streams
Primary
sludge
Settling
Seasonal
chlorination
Activated sludge
Recycle activated
sludge
Solids processing
Blended thickened sludge
Centrifugation
Centrate
Biosolids
Results
Estradiol Equiv. Mass Throughput (g/day)
Total “estrogenicity”
60
Primary Influent
Secondary Influent
Pre-Chlorination Effluent
Post-Chlorination Effluent
Not
Chlorinating
50
40
Chlorinating
30
Not
Chlorinating
Chlorinating
Chlorinating
20
Chlorinating
10
<1<1
0
Apr-06
Jul-06
Nov-06
Feb-07
Date of Sampling Event
May-07
Jul-07
Total “estrogenicity”
Overall the influent and effluent estrogenicity
data were consistent with time
Removal occurs across the activated sludge
tank
Specific compounds
 Some compounds are removed effectively and are
present in low concentrations in the effluent (e.g.,
Bisphenol A)
Sampling
Date
Primary
influent
(g/day)
Secondary
influent
(g/day)
Pre-Cl
effluent
(g/day)
Post-Cl
effluent
(g/day)
7/2006
390
640
5
12
11/2006
820
1,050
12
10
5/2007
730
690
29
12
7/2007
430
640
17
10
Specific compounds
Other compounds appear to recycle internally
and removals vary (e.g., nonylphenol)
Sampling
Date
Primary
influent
(g/day)
Secondary
influent
(g/day)
Pre-Cl
effluent
(g/day)
Post-Cl
effluent
(g/day)
7/2006
22,000
30,000
970
860
11/2006
44,000
225,000
300
780
5/2007
2,000
9,100
3,300
1,900
7/2007
11,000
1,400
3,300
240
Specific compounds
 Interpretation of estrone data is complicated since
it can be formed through the oxidation of estradiol
conjugates and subsequently transformed
Sampling
Date
Primary
influent
(g/day)
Secondary
influent
(g/day)
Pre-Cl
effluent
(g/day)
Post-Cl
effluent
(g/day)
7/2006
9
108
12
41
11/2006
6
74
1
7
5/2007
9
57
6
4
7/2007
4
7
10
6
Specific compounds
 Occasionally highly estrogenic compounds such
as estriol and ethynylestradiol were detected in
the effluent
 Estriol:
7/2006, 410 ng/L
11/2006, 0 ng/L
5/2007, 0 ng/L
7/2007, 0 ng/L
 Ethynylestradiol: 7/2006, 0 ng/L
11/2006, 0 ng/L
5/2007, 18 ng/L
7/2007, 0 ng/L
Summary of results & conclusions
Influent estrogenicity does not vary
significantly at the Metro Plant
Estrogenic compounds are treated; the
effluent appears to contain primarily
nonylphenol, bisphenol A, and estrone (solids
contain nonylphenol, bisphenol A, and
triclosan)
Binding assays have utility but you have to
use them carefully
What we don’t know
How do we optimize removal under standard
plant conditions in a cost-effective way?
How do plant conditions change on a
weekly/daily basis and how does this change
removal?
What other compounds are in the solids? Are
they stable? How are they best treated (other
than at Metro…)?
What other compounds are present that could be
problematic (Sertraline, other pharmaceuticals)?
On-going and future work
Investigating the
presence, effect, and
transformation of
estrogens in septic
discharges (N shore of
Lake Superior)
Investigating the
presence and
transformation of
phytoestrogens in
industrial wastewaters
Currently proposed work
Proposed investigation of
BPA, NP, estrone, triclosan,
and triclocarban
transformation under realistic
conditions
Proposed investigation to
determine how to stop the
use of non-necessary
endocrine disruptors
Other possible projects/questions
Investigate other
compounds
(particularly
pharmaceuticals)
Pilot-scale studies
Investigate solids (what
compounds are
present, how mobile
are they, how should
they be treated?)
Future partnership?
We have the ability to help the MCES
address long-range, larger-scale
challenges and mitigate future risk
The University has:
Highly-trained, cost-effective labor and
expertise (graduate students and faculty)
Exceptional research facilities
Acknowledgements
 Students: Megan Ogdahl, Matt Wogen, Mark Lundgren
 Collaborators: Mike Semmens, Deb Swackhamer
 WWTP Staff (Metropolitan Plant, St. Paul, WLSSD
Plant, Duluth)
 Funding: Legislative-Citizen Commission on Minnesota
Resources
 Other research: Paul L. Busch Award (Water
Environment Research Foundation), EPA GLNPO, DC
Water and Sewer Authority, Heiko Schoenfuss, Bill
Arnold, David Fulton