Endocrine Disruption

1
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
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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
• e.g., Jobling et al., 1998 Ternes et al., 1999
  Holbrook et al., 2002 Kolpin et al., 2002 Joss
  et al., 2004 Pojana et al., 2004

3
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
Target cell
Secreting cell
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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
Target cell
Secreting cell
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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
Unintended Physiochemical response
Target cell
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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.
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What we analyze

• Binding assays total sample estrogenicity
  (including unknown compounds)
• 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

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Methods for analysis
Collect samples
Specific compounds quantified (40 L concentrated
to 150-300 uL)
Processing cleanup
Sample processing
Yeast cells alive, human estrogen receptor Trout
liver cells not alive, trout estrogen receptor
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Sample locations
Seasonal chlorination
Primary treatment

Settling
Secondary treatment

Screens, grit removal, and primary settling
Activated sludge
Recycle streams
Recycle activated sludge

Primary sludge
Solids processing
Centrifugation
Blended thickened sludge
Centrate
Biosolids
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Results
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Total estrogenicity
Not Chlorinating
Chlorinating
Not Chlorinating
Chlorinating
Chlorinating
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Total estrogenicity

• Overall the influent and effluent estrogenicity
  data were consistent with time
• Removal occurs across the activated sludge tank

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Specific compounds

• Some compounds are removed effectively and are
  present in low concentrations in the effluent
  (e.g., Bisphenol A)

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Specific compounds

• Other compounds appear to recycle internally and
  removals vary (e.g., nonylphenol)

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Specific compounds

• Interpretation of estrone data is complicated
  since it can be formed through the oxidation of
  estradiol conjugates and subsequently transformed

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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

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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

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What we dont 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)?

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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

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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

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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?)

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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

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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