Microconstituents – Emerging Contaminants Joint Water Resources Symposium New York Water Environment Associations New York Section American Water Works

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:


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



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.


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



• 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


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)


• 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.



• 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.



• 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%


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


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?

Documents

Microconstituents – Emerging Contaminants Joint Water Resources Symposium New York Water Environment Associations New York Section American Water Works