Microconstituents Emerging Contaminants

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Microconstituents Emerging Contaminants

• Joint Water Resources Symposium
• New York Water Environment Associations
• New York Section American Water Works Association
• In Honor or Edwin C. Tifft, Jr.
• Syracuse, NY
• November 14, 2007
• Joseph G. Cleary, P.E., BCEE
• Principal
• HydroQual, Inc.
• Mahwah, NJ

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Presentation Outline

• WEFs Community of Practice Activities
• Microconstituents - Whats Included?
• Terminology / Name Changes / Key Messages
• Treatment Technologies
• Approach to Develop Best Solution
• Case Studies
• Summary

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• WEF Community of Practice Activities

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Why are Microconstituents a Concern?

• Better analytical methods and more monitoring are
  finding them in numerous receiving waters
• Feminized fish discovered in Europe in mid 1990s
• Steroids are implicated in Europe in late 1990s
• Treatment studies on POTWs (2002-2003) show POTWs
  are a collection point and one source to
  receiving waters
• USGS study of 139 streams in 2002 detected
  pharmaceuticals in 80 of samples
• More media coverage public awareness and
  concerns.

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WEF Community of Practice (CoP)

• Began at WEFTEC 2005 in Washington DC
• Deals with hot topics
• Broad, diverse membership a benefit and
  challenge
• 150 Members and growing

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WEF Key Messages

• Committed to sharing clear, factual information
• Advancing understanding
• Pursuing sound, sustainable solutions
• Focusing on source control

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Two Fundamental Challenges

• Technical challenges due to scientific
  uncertainties
• Communication challenges related to public fears
  and perceptions.

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WEF Community of Practice (CoP)

• Identified work products
• Technical Practice Updates
• Public Press Communications
• Glossary of Terms
• Name for the issue

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WEFs Public Communications Role

• Staff Products include
• Key Messages
• Fact Sheets
• Illustrations
• Finding Expert Spokespersons
• Building Consensus

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Varying Communication Challenges Include
What to call the compounds without negatively
branding them as a worry or concern? Media
accounts and technical publications already using
a multiplicity of terms
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Varying Communication Challenges Include
Scientists wanting to communicate with precision
to scientists WEF needs also to communicate with
the scientific community, its membership and the
general public The required vernacular must vary
to suit the audience so the language must be
tailored
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Communication Challenge

• Second challenge - Technical and communications
  experts
• Different audiences
• Different vocabulary
• Different approaches

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• Microconstituents - Whats Included?

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Micro Constituents in Water Where Do They Come
From?
Courtesy of CH2M Hill
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Reference Kobylinski, Hunter and Scruggs, 2005
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New Emerging Compounds
benzene, naphthalenesulfonates
HYDROPHILIC
surfactants
pharmaceuticalsbetablockers, antibiotics,
contrast media, analgesics, antiepileptics,
parasiticides, babiturates, opioides
perfluorinatedcompounds (PFOA)
corrosion inhibitorse.g. benzotriazole
POLARITY
NDMA
phosphoric ester flame retardants
estrogenes
MTBE
UV filter
from Walter Giger, in Ternes und Joss, IWA
Publishing, 2006
musk fragrances
Volatility
NON VOLATILE
LIPOPHILIC
VOLATILE
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New Emerging Compounds
conc. in µg/L
360000 Pop. Equiv. Nitrification/Denitrification
Ternes et al., Chemosphere 2007
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Diversity of Endocrine Disruptor Compounds
(Falconer (2003) and Wren (2001))
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Why are Microconstituents a Concern?

• A review by the World Health Organization has
  concluded that low-level environmental exposure
  to Endocrine Disruptors has not yet been
  demonstrated to cause harm to human health
  (Damstra et al., 2002).
• Uptake of Endocrine Disruptors by humans from
  treated drinking water is relatively low in
  comparison to other sources such as food (GWRC,
  2003).

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• Terminology / Name Changes / Key Messages

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WEF Terminology Challenges
Nov 2005 Endocrine Disrupting Compounds
(EDC) (goal was communicating with WEF
membership) Feb 2006 Compounds of Emerging
Concern (CEC) (because not just about endocrine
issues) Oct 2006 Compounds of Potential
Concern (how to respond to the public diligence
in studying the issue)
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Terminology Challenge
May 2007 More discussion about alarming the
public when we dont have a basis to ring the
alarm bells Micro-constituents No, not little
voters but really small things in the water
environment that we can now detect (at ppb and
ppt) and we dont know enough about.
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WEF Key Messages
These compounds are referred to in a multiplicity
of ways including micro-constituents, trace
constituents compounds of emerging concern, etc.
  WEF is calling them micro-constituents. We
continue to study them as a prudent, conservative
course of action reflecting our commitment to
continue to assess the potential impact on human
health and the environment.
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WEF Key Messages
Low levels of compounds remain but in
concentrations that we believe are safe to return
to the environment There are differing levels of
Wastewater Treatment and Water Treatment We are
studying the issue of even the trace amounts of
these chemicals that remain after wastewater
treatment
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WEF Key Messages

• Treated wastewater is not the only pathway for
  these substances to enter the environment
• Many items we can detect have beneficial effects
  (i.e. medicines and pest control)
• Some improvement quality longevity of life

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WEF Key Messages

• Effects depend on
• - Nature of compound
• - Type of exposure
• - Concentration
• - Quantity/duration of exposure

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Some Facts to Keep in Mind

• Some compounds are naturally occurring
• Society chooses to ingest, bathe in and apply
  constituents at much higher concentrations than
  ever found in the environment

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• Treatment Technologies

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Physical/Chemical Properties Keys to Treatment

• Water Solubility (mg/L)
• Henrys Constant (atm m3/mole)
• Octonal Water Coefficient Log Kow (Partitioning
  to Solids)
• Vapor Pressure, Vp
• Distribution Coefficient, Kd
• Biotransformation Ratio (K bio in soil, water,
  sludge and sediment)
• Biodegradability
• Photolysis Rate
• Oxidation Rate
• Reduction Rate Reference
  Williams, 2006

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Applicable Treatment Technologies for EDCs

• Aerobic Biological Treatment Processes including
  Nitrogen Removal (e.g. Activated Sludge, Membrane
  Bioreactors)
• Chlorination (e.g. bleach, alkaline chlorination)
• Advanced Oxidation (UV/Peroxide, Ozone/Peroxide,
  UV/Ozone
• Carbon Adsorption
• Membrane Filtration and Reverse Osmosis
• Thermal Oxidizers
• Anaerobic Biological Treatment

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Summary of Poseidon Project in Europe (Thomas
Ternes)

• PPCPs and Estrogens removal focus in Europe

• Membranes Ozonation in combination with
  Activated Sludge Biofilters were evaluated

• Sludge treatment and urine separation was
  evaluated

• Sorption is an important mechanism for
  hydrophobic and positively charged compounds

• Biodegradation is a key mechanism

• Stripping was not effective

• Chemical oxidation was an effective polishing
  step for some PPCPs

• Some PPCPs are degraded in anaerobic sludge
  digestion

• Available process models can be used using rate
• coefficients developed

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Activated Sludge
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Membrane Bioreactor Process
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Fixed Film Technology
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Other Treatment Studies

• MLE Plant in San Diego (WERF Study, Oppenheimer,
  2005)
• Six full-scale WWTPs in the U.S. and two pilot
  scale MBRs (WERF Study, Oppenheimer, 2006)
• Half of the 20 PPCPs were removed to greater than
  80 at SRT lt5 days
• No additional removal was attributed to MBR,
  media filters or longer HRTs
• Removal of musk fragrances required SRTs of at
  least 25 days

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Results from Two-Stage MBR Ozone Treatment in
Pilot Study

• APIs concentrations are listed in ?g/L
• DL Detection limit
• ND Not detected
• Reference Helmig, Edward et al., WEFTEC 2005

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Ozone Treatment
Carbamazepine
Huber et al., 2003, Env.Sci.Technol.
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WEF Technical Practice Update on Treatment

• EDC Committee Formed _at_ WEFTEC October 2005
• List of TPUs was developed (? 13 topics)
• Treatment was done first
• Draft for comment in January 2006
• Review meeting in February 2006
• Committee name changed to Contaminants of
  Emerging Concern now Microconstituents
• Comments received in March 2006 on Treatment
  White Paper Change to Technical Practice Update
• Final draft April 2007
• Final version now on WEF website along with
  others

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What Has Been Done and What Do We Know

• Many studies have demonstrated that activated
  sludge processes have the potential to remove a
  large fraction of several suspected EDCs, often
  to below detection limits (Ying, 2002).
• Johnson and Darton (2003) state that the EDCs
  generally implicated in endocrine disruption in
  fish the estrogens E1, E2, EE2, and NP are
  all inherently biodegradable

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What Has Been Done and What Do We Know(continued)

• Siegrist estimates that about a 10 to 15 day SRT
  would be required for appreciable EDC removal
  (Siegrist et al., 2005).
• Estrogens can be eliminated in WWTPs by applying
  a nitrification/denitrification step (SRTs ?15
  days), or by effluent ozonation, nanofiltraton,
  or activated carbon.
• Anaerobic sludge digestion leads to a degradation
  of some PPCPs.

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What Has Been Done and What Do We Know(continued)

• Substances that are difficult to biodegrade may
  be oxidized by AOPs, and the oxidized byproducts
  may be more amenable to biodegradation (Ried and
  Mielcke, 2003).
• Advanced oxidation process (AOP) are combinations
  of UV plus hydrogen peroxide, ozone plus hydrogen
  peroxide, and UV plus ozone, that are
  specifically designed to increase the formation
  of powerful hydroxyl radicals to oxidize EDCs and
  provide disinfection. Ozone shows similar
  potential to the AOPs for EDC removal.

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What Has Been Done and What Do We Know(continued)

• 100 removal of EDCs from WWTP effluent will not
  be possible, so the goal should be reduction to
  levels with no adverse environmental effects.
• Source control (e.g., ecolabelling) and source
  separation (e.g., urine or rain water
  segregation) are important measures for reducing
  the PPCP load entering the environment.

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What is Needed or Not Known?

• Toxicological and other environmental impacts are
  not known for most EDCs.
• Risk assessment studies are needed to develop
  appropriate regulatory actions (Schoenberg,
  Helmig et al., 2005).
• Fate studies are needed describing removals of
  compounds and pathways biodegradation/biotransfor
  mation, partitioning to solids, volatilization.

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What is Needed or Not Known?(continued)

• Analytical procedures are needed to detect lower
  levels of estrogens and to distinguish between
  various forms.
• Research to better understand the performance of
  engineered and natural treatment systems for
  reduction of these compounds (Oppenheimer et al.,
  2005).
• The hazard potential of the byproducts formed
  through treatment with advanced oxidation
  requires additional investigation.

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• Integrated / Holistic Approach to Develop Best
  Solution

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Urban Water Cycle
STP
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Integrated vs. End-of-Pipe Approach
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Collaborative TeamApproach is Best

• Mobilize a Team Include People Closest to
  Problems and Stakeholders
• Include Production, Water and Wastewater
  Operations, Environmental Compliance Managers
• Outside Consultant
• Commitment of Management and Team
• Frequent Communications and Meetings

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ApproachSequence of Tasks

• Flow Balance Wastewater Characteristics
• Design Basis (flow wasteloads)
• Screen Technologies
• Develop Initial Alternatives
• Alternative Comparison (cost non-costs
  criteria)
• Narrow List of Alternatives
• Treatability Studies Process Modeling
• Refine Comparison
• Select Best Solution

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• Case Studies

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Case Study 1

• Pharmaceutical Company in U.S.
• New Product from Europe Chlorination (bleach)
  used for destruction
• Initial testing showed it was non-biodegradable,
  would pass through existing treatment plant and
  result in effluent toxicity violations.
• Treatability Studies were conducted to evaluate
  Advanced Oxidation treatment technology
  UV/hydrogen peroxide, catalyst/UV/hydrogen
  peroxide, UV/ozone and UV/hydrogen
  peroxide/ozone.
• Two technologies also reduced effluent toxicity
  by 95 (UV/ozone and UV/ozone/hydrogen peroxide.
• Product was never brought to the plant from
  Europe.

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Chemical Oxidation Technology Evaluation
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Case Study 2

• Pharmaceutical Company in Puerto Rico
• New Product
• Active Pharmaceutical Ingredients (API) in
  cleaning wastewaters
• Company had Corporate Guidelines (from Europe)
  for discharge to the Atlantic Ocean
• Discharge through POTW to Atlantic Ocean
• Best solution was holding tank with controlled
  release to POTW no treatment was needed

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Case Study 3

• Pharmaceutical Company in Ireland.
• Considering production of an antifungal compound.
• Compound is relatively insoluble and
  non-biodegradable.
• Potential to accumulate in sludge and impact
  composting.
• Concern was potential impact on activated sludge
  plant and sludge composting at POTW.
• Treatability Studies simulated activated sludge
  and sludge composting to determine process
  impacts and concentrations present in sludge and
  compost material.
• There was no impact on activated sludge
  performance including nitrification.
• Mass balance showed 70 of compound was
  biodegradable.
• There was no impact on composting process.

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Bench-Scale Anoxic and Aerobic Reactors
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SUMMARY

• Microconstituents are now being detected more in
  water and wastewater.

• Analytical methods are specialized.

• Information is developing on treatment/destruction
  of Microconstituents in both POTWs and
  pharmaceutical wastewaters.

• Applicable treatment technologies include
  biological and advanced oxidation processes.

• EDCs removal in POTWs and Industrial Wastewater
  Plants varies based on wastewater characteristics
  and process design operating parameters such as
  sludge age.

• Treatability studies are very helpful for
  site-specific wastewater projects.

• Stay tuned as more Technical Practice Updates
  are developed by WEF and specially conferences
  are planned.

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Thank you! QUESTIONS?