microconstituents – emerging contaminants joint water resources symposium new york water...
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Microconstituents – Emerging ContaminantsMicroconstituents – Emerging Contaminants
Joint Water Resources SymposiumNew York Water Environment Associations
New York Section American Water Works AssociationIn Honor or Edwin C. Tifft, Jr.
Syracuse, NYNovember 14, 2007
Joseph G. Cleary, P.E., BCEEPrincipal
HydroQual, Inc.Mahwah, NJ
Presentation OutlinePresentation Outline
• WEF’s Community of Practice Activities• Microconstituents - What’s Included?• Terminology / Name Changes / Key Messages• Treatment Technologies• Approach to Develop Best Solution• Case Studies• Summary
WEF Community of Practice Activities
Why are Microconstituents a Concern?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.
WEF Community of Practice (CoP)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
WEF Key MessagesWEF Key Messages
• Committed to sharing clear, factual information
• Advancing understanding• Pursuing sound, sustainable solutions• Focusing on source control
Two Fundamental ChallengesTwo Fundamental Challenges
1. Technical challenges due to scientific uncertainties
2. Communication challenges related to public fears and perceptions.
Identified work products
• Technical Practice Updates
• Public & Press Communications
• Glossary of Terms
• Name for the issue
WEF Community of Practice (CoP)WEF Community of Practice (CoP)
WEFs Public Communication’s RoleWEFs Public Communication’s Role
Staff Products include:• Key Messages• Fact Sheets• Illustrations• Finding Expert Spokespersons• Building Consensus
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
Varying Communication Challenges Include:
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
Varying Communication Challenges Include:
Varying Communication Challenges Include:
Second challenge - Technical and communications experts
• Different audiences
• Different vocabulary
• Different approaches
Communication ChallengeCommunication Challenge
Microconstituents - What’s Included?
Courtesy of CH2M Hill
Micro Constituents in Water: Where Do They Come From?
Micro Constituents in Water: Where Do They Come From?
Reference: Kobylinski, Hunter and Scruggs, 2005
HYDROPHILIC
LIPOPHILIC
PO
LA
RIT
Y
pharmaceuticalsbetablockers, antibiotics,
contrast media,analgesics, antiepileptics, parasiticides, babiturates,
opioides
estrogenes
New Emerging CompoundsNew Emerging Compounds
VOLATILE NON VOLATILE
Volatility
from Walter Giger, in Ternes und Joss, IWA Publishing, 2006
musk fragrances
MTBE
phosphoric ester flame retardants
NDMA
corrosion inhibitorse.g. benzotriazole
UV filter
perfluorinatedcompounds (PFOA)
benzene, naphthalenesulfonates
surfactants
New Emerging CompoundsNew Emerging Compounds
Tri
met
ho
pri
m
Su
lfam
eth
oxa
zole
Ro
xith
rom
ycin
Ibu
pro
fen
Dic
lofe
nac
Clo
fib
ric
acid
Car
bam
azep
ine
Ate
no
lol
So
talo
l
Met
op
rolo
l
Pro
pra
no
lol
Gal
axo
lide
To
nal
ide
Iop
amid
ol
Dia
triz
oat
e
Iom
epro
l0,0
1.0
2.0
3.0
4.0
5.0
6.0 March
May
September
betablocker
antibiotics
diclofenac
musk frag.
contrast media
carbamazepine
conc.in µg/L
Ternes et al., Chemosphere 2007360‘000 Pop. Equiv.Nitrification/Denitrification
Diversity of Endocrine Disruptor Compounds (Falconer (2003) and Wren (2001))
Diversity of Endocrine Disruptor Compounds (Falconer (2003) and Wren (2001))
Pesticides & Herbicides
2,4-D
Endrin
Vinclozolin
Lindane
Chlordane
Heptachlor
Atrazine
DDT
Methoxychlor
Simazine
Endosulfan
Toxaphane
Dieldrin
Persistent Industrial Chemicals
Dioxins
PCP
Phthalates
Furans
Hexachlorobenzene
Bisphenol A
P-nonylphenol’s
Tributyl tin
PBBOctachlorostyrene
PCB’s
Heavy Metals
Cadmium Lead Mercury
Hormones Synthetic:
Biological:
Plant secondary metabolites
17-Ethinylestradiol
17-Estradiol
Progesterone
Lignans
Diethylstilbestrol
Estriol
Testerone
Sesquiterpenes
Isoflavonoids
Estrone
Phytosterols
Coumestans
Why are Microconstituents a Concern?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).
Terminology / Name Changes / Key Messages
Nov 2005Endocrine Disrupting Compounds (EDC)(goal was communicating with WEF membership)
Feb 2006Compounds 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)
WEF Terminology ChallengesWEF Terminology Challenges
May 2007More discussion about alarming the public – when we don’t 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 don’t know enough about.
Terminology ChallengeTerminology Challenge
These compounds are referred to in a multiplicity of ways including micro-constituents, trace constituentscompounds 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.
WEF Key MessagesWEF 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
WEF Key MessagesWEF Key Messages
WEF Key MessagesWEF 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
• Effects depend on:
- Nature of compound- Type of exposure
- Concentration- Quantity/duration of exposure
WEF Key MessagesWEF Key Messages
Some Facts to Keep in MindSome 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
Treatment Technologies
Physical/Chemical Properties – Keys to Treatment
Physical/Chemical Properties – Keys to Treatment
Water Solubility (mg/L) Henry’s 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
Applicable Treatment Technologies for EDCs
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
Summary of Poseidon Project in Europe (Thomas Ternes)
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
Activated SludgeActivated Sludge
Aeration Tank #1
Aeration Tank #2
Clarifier
EQTank
DenitrificationSelector
FilterPress
Return Activated Sludge
Waste Activated Sludge
Effluent
Process Wastewater
Jet Aeration
Jet Aeration
Membrane Bioreactor ProcessMembrane Bioreactor Process
Fixed Film TechnologyFixed Film Technology
Other Treatment StudiesOther 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 <5 days• No additional removal was attributed to MBR, media filters
or longer HRTs• Removal of musk fragrances required SRTs of at least 25
days
Results from Two-Stage MBR & Ozone Treatment in Pilot Study
Results from Two-Stage MBR & Ozone Treatment in Pilot Study
Influent MBR Permeate Ozone Effluent API(1) DL(2) Average Range Average Range Average Range
17-α-estradiol 0.23 0.36 ND(3) – 1.1 0.18 ND – 0.41 ND ND 17-β-estradiol 0.23 1.7 0.62 – 2.6 0.30 ND – 0.68 ND ND 17-α-dihydroequilin 0.23 1.7 0.22 – 6.4 0.30 ND – 0.63 ND ND Estrone 0.23 3.8 2.8 – 4.9 3.30 0.54 – 6.0 0.20 0.17 – 0.25
(1) APIs concentrations are listed in g/L
(2) DL: Detection limit
(3) ND: Not detected
Reference: Helmig, Edward et al., WEFTEC 2005
HN
HOOCCl
Cl
CH3
HO
OH
C CH
N
NH2O
Carbamazepine
O
R1
OH
O
O
OR2
O
O
OCH3
OHO
N
OH
HO
S
O
O
H2NHN
N O
Diclofenac
17 -Ethinylestradiol
Sulfamethoxazole
Roxithromycin
Huber et al., 2003, Env.Sci.Technol.
Ozone TreatmentOzone Treatment
WEF Technical Practice Update on Treatment
• EDC Committee Formed @ 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
What Has Been Done and What Do We KnowWhat 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”
What Has Been Done and What Do We Know(continued)
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.
What Has Been Done and What Do We Know(continued)
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.
What Has Been Done and What Do We Know(continued)
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.
What is Needed or Not Known?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/biotransformation, partitioning to solids, volatilization.
What is Needed or Not Known?(continued)
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.
Integrated / Holistic Approach to Develop Best
Solution
Water/Sediment
Industry
STP
Urban Water Cycle
bank filtrate
Waterworks Drinking water
Irrigation (soil/aquifer)
“Run off“
infiltration groundwater
SecondaryWastewaterTreatment
TertiaryWastewaterTreatment
Production
UtilitiesSludge
RawWaterSupply
WellWaterSupply
Water Reuse
Brine Disposal
To POTW
End of Pipe Approach
Integrated vs. End-of-Pipe ApproachIntegrated vs. End-of-Pipe Approach
Collaborative TeamApproach is Best
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
• 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
ApproachSequence of Tasks
ApproachSequence of Tasks
Case Studies
Case Study #1Case 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.
Chemical Oxidation Technology EvaluationChemical Oxidation Technology Evaluation
Run Number Treatment Process Compound Reduction
Toxicity Reduction
1 UV, hydrogen peroxide
99.5% 58%
2 Catalyzed UV, hydrogen peroxide
99.8% 88.2%
3 UV, ozone 99.4% 99.1%
4 UV, ozone, hydrogen peroxide
99.5% 95%
Case Study #2Case 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
COOLING – 2
COOLING – 1
CTF – 1
PRASA 2
PROCESS – 1
PROCESS – 1
Boiler
PRASA 1
CTF – 2
Sanitary 005
009
001
CIP
PROCESS – 2
92,000 gpd
31,000 gpd
25,000 gpd
58,000 gpd
21,000 gpd
2,500 gpd
10,500 gpd
2,000 gpd
1,000 gpd
6,000 gpd
17,000 gpd
7,000 gpd
WastewaterTreatment
WastewaterTreatment
CafeteriaSanitary
004
5,500 gpd
8,00
0 gp
d
AHUCondensate
Miscellaneous
300,000gallons
300,000gallons
12,000gallons
50,000gallons
43,000 gpd
12,500 gpd
5,500 gpd
2,500 gpd
41,000 gpd
15,000 gpd
1,500 gpd
Process User
Utility User
Sanitary User
18,000 gpd
EXAMPLE WATER BALANCE
Case Study #3Case 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.
Bench-Scale Anoxic and Aerobic ReactorsBench-Scale Anoxic and Aerobic Reactors
SUMMARYSUMMARY
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.
Thank you!
QUESTIONS?