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1 Pharmaceuticals and Personal Pharmaceuticals and Personal Care Products Care Products Literature Review, Treatment Technologies, Research Literature Review, Treatment Technologies, Research and Regulatory Process and Regulatory Process MWEA IPP Seminar MWEA IPP Seminar October 15, 2009 October 15, 2009 Rich Grant, P.E. Rich Grant, P.E. – Fleis & VandenBrink Engineering Fleis & VandenBrink Engineering Brian Rice, P.E. Brian Rice, P.E. – Fleis & VandenBrink Engineering Fleis & VandenBrink Engineering [email protected] [email protected] [email protected] [email protected] Pharmaceuticals & Personal Care Products (PPCPs) Background Example Compounds Research Treatment Regulatory Process Conclusions Initial need for data Initial need for data Wastewater treatment plants Wastewater treatment plants Pharmaceuticals & Personal Care Products (PPCPs) Background Interest PPCP/EDC Sources & Occurrence Example Compounds Wastewater treatment plants Wastewater treatment plants Risk assessment / Toxicology Risk assessment / Toxicology Increased microbial resistance to Increased microbial resistance to antibiotics antibiotics Research Treatment Regulatory Process Conclusions
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1

Pharmaceuticals and Personal Pharmaceuticals and Personal Care ProductsCare Products

Literature Review, Treatment Technologies, Research Literature Review, Treatment Technologies, Research and Regulatory Process and Regulatory Process

MWEA IPP SeminarMWEA IPP SeminarOctober 15, 2009October 15, 2009

Rich Grant, P.E. Rich Grant, P.E. –– Fleis & VandenBrink EngineeringFleis & VandenBrink Engineering

Brian Rice, P.E. Brian Rice, P.E. –– Fleis & VandenBrink EngineeringFleis & VandenBrink Engineering

[email protected]@fveng.com [email protected]@fveng.com

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Regulatory

Process

Conclusions

•• Initial need for dataInitial need for data

•• Wastewater treatment plantsWastewater treatment plants

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

• Interest

• PPCP/EDC

• Sources & Occurrence

Example

Compounds Wastewater treatment plantsWastewater treatment plants

•• Risk assessment / ToxicologyRisk assessment / Toxicology

•• Increased microbial resistance to Increased microbial resistance to antibioticsantibiotics

p

Research

Treatment

Regulatory

Process

Conclusions

2

PPCPPPCPs = s = PPharmaceuticals &harmaceuticals &

PPersonal ersonal CCare are PProductsroducts

AntibioticsAntibiotics FragrancesFragrances

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Interest

PPCP/EDC

Sources & Occurrence

Example

Compounds AntibioticsAntibiotics AntiAnti--inflammatory inflammatory

medicines medicines Antiepileptic medicinesAntiepileptic medicines Blood lipid regulatorsBlood lipid regulators Cough syrupCough syrup

FragrancesFragrances

HormonesHormones

Pain medicationPain medication

XX--ray contrast ray contrast mediamedia

p

Research

Treatment

Regulatory

Process

Conclusions

EDCEDCs = s = EEndocrine ndocrine DDisrupting isrupting CCompoundsompounds

•• PesticidesPesticides•• OrganohalogensOrganohalogens•• AlkyphenolsAlkyphenols•• Heavy metalsHeavy metals•• OrganotinsOrganotins•• PhthalatesPhthalates

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Interest

PPCP/EDC

Sources & Occurrence

Example

Compounds

•• Natural HormonesNatural Hormones

•• PharmaceuticalsPharmaceuticals

•• Phytoestrogens Phytoestrogens

•• PhenolsPhenols

•• Aromatic hydrocarbonsAromatic hydrocarbons

p

Research

Treatment

Regulatory

Process

Conclusions

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Interest

PPCP/EDC

Sources & Occurrence

Example

Compoundsp

Research

Treatment

Regulatory

Process

Conclusions

3

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Analytes

Dose –

Human

Analgesics Acetaminophen

Ibuprofen

Codeine

Lipid Regulators Clofibric Acid

Gemfibrozil

Antibiotics

Steroids 17b-estradiol

17a-ethinylestradiol

Estrone

Estriol

Coprostanol

Cholesterol

-adrenergic Blockers Atenolol

Research

Treatment

Regulatory

Process

Conclusions

Antibiotics Trimethoprim

Sulfamethoxazole

Lincomycin

Tylosin

Antidepressants Fluoxetine

Norfluoxetine

Atenolol

Metoprolol

Propranolol

Stimulants Caffeine

Antiepileptics Carbamazepine

•• AA “Dose” of Perspective

• Accomplish 200 mg/D Ibuprofen with 150 MGD water

• A “Sip” (synergic impact of some EDCs at lower doses)

• Consider - Potency at Low Dose

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Analytes

Dose –

Human

• Consider - Potency at Low Dose– Bioaccumulative, persistent

(PBC, THFs, DDT, etc)– Immunity build-up (antibiotics)– Designed for low-dose potency

(atrazines, triazines)

Research

Treatment

Regulatory

Process

Conclusions

USGS National USGS National Reconnaissance StudyReconnaissance Study

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

Treatment

Regulatory

Process

Conclusions

4

PPCPs/EDCs in MichiganPPCPs/EDCs in MichiganPharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

Treatment

Regulatory

Process

Conclusions

Water Cycle:Mean Concentrations - PPCPs

100.000

Huron River

Drinking Water

Wastewater Influent

Wastewater Effluent

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

•• 44--Season SamplingSeason Sampling

•• Lakes and RiversLakes and Rivers

•• SimilarSimilar

0.001

0.010

0.100

1.000

10.000

Sulfam

ethox

azole

Linco

myc

in

Tylosin

Trimet

hoprim

Aceta

mino

phen

Carbam

azepine

Ibup

rofe

n

Caffeine

Cotinin

e

1,4

Dioxan

e

Co

nc

en

tra

tio

n (

pp

b) Water Cycle:

Mean Concentrations - Hormones and Steroids

0.001

0.010

0.100

1.000

10.000

100.000

1000.000

Stigm

aste

rol

Sitoste

rol

Stigm

asta

nol

Copro

stano

l

Chole

stero

l

Dihydro

chloe

stero

l

Co

nc

en

tra

tio

n (

pp

b)

Huron River

Drinking Water

Wastewater Influent

Wastewater Effluent

Treatment

Regulatory

Process

Conclusions

Water Treatment ProcessWater Treatment ProcessAnn Ann ArborArbor Grand Grand RapidsRapids MonroeMonroe

Lime Lime SofteningSoftening

ClarifierClarifier

OzoneOzone

FlocculationFlocculation//SedimentationSedimentation

Rapid Rapid MixMix

Source Source WaterWater

FiltrationFiltration

Distribution Distribution SystemSystem

Final Final TreatmentTreatmentChloraminesChloramines

Final Final TreatmentTreatmentFree ChlorineFree Chlorine

Sand Sand FiltrationFiltrationGAC GAC FiltrationFiltration

OzoneOzone

Final Final TreatmentTreatmentFree Free ChlorineChlorine

SedimentationSedimentationSedimentationSedimentation

5

3

1 1

25

30

35

40

45

50

55

60

Co

nce

ntr

atio

n (

pp

t)

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

24

4 1 1 1

3

2

3

33

11 1

6

6

3

1

0

5

10

15

20

Mea

n

Antibio

tics

Antidep

ress

ants

Antiepil

eptic

s

Analgesics

Beta Blo

ckers

Lipid R

egulat

ors

Steroid

s

Stimulan

ts

Ann ArborGrand RapidsMonroe

Treatment

Regulatory

Process

Conclusions

Drinking WaterDrinking Water

25

30

35

40

45

50

55

60

on

cen

trat

ion

(p

pt)

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

1 1 1 11

66 3

11

10

5

10

15

20

Mea

n C

o

Antibio

tics

Antidep

ress

ants

Antiepi

leptic

s

Analges

ics

Beta B

lock

ers

Lipid

Reg

ulato

rs

Stero

ids

Stimula

nts

Ann ArborGrand RapidsMonroe

Treatment

Regulatory

Process

Conclusions

Water Treatment RemovalWater Treatment Removal

40%

50%

60%

70%

80%

90%

100%

rcen

t R

emo

val

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

0%

10%

20%

30%

Per

Antibio

tics

Antidep

ressa

nts

Antiepile

ptics

Analgesic

s

Beta B

lock

ers

Lipid

Reg

ulato

rs

Stero

ids

Stimula

nts

Ann ArborGrand RapidsMonroe

Treatment

Regulatory

Process

Conclusions

6

Surface/Ground Water InteractionSurface/Ground Water Interaction

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

Treatment

Regulatory

Process

Conclusions

Helena Valley Ground Water: Pharmaceuticals, Personal Care Products, Endocrine Disruptors (PPCPs) and Microbial Indicators of Fecal Contamination

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwaterof Fecal Contamination

Kathleen (Kate) J. Miller and Joseph Meek, both of the Montana Department of Environmental Quality, 2005

Treatment

Regulatory

Process

Conclusions

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

Treatment

Regulatory

Process

Conclusions

7

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

•32 of 38 PPCP analytes detected in GW•Sulfamethoxazole (SMX) 80%•Atrazine 40%

Treatment

Regulatory

Process

Conclusions

• High Density = 300 septic systems /mi2

• Moderate Density = 50 - 300 septic systems /mi2

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

Treatment

Regulatory

Process

Conclusions

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

Treatment

Regulatory

Process

Conclusions

8

• Occurrence and Fate of Pharmaceuticals and Personal Care Products in Groundwater Environments, EPA funded research by Stony Brook University, 2005

• Distribution of PPCPs

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

• Migration of PPCPs Treatment

Regulatory

Process

Conclusions

• Upper drift aquifer on Long Island, New York

• 18 sampling sites

• Septic tank plume

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

Treatment

Regulatory

Process

Conclusions

• Some pharmaceuticals detected in GW from drainfield plume

• Sorption and migration

• Drainfield is not the end to

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Surface Water

Groundwater

migration of PPCPs, EDCs Treatment

Regulatory

Process

Conclusions

9

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t tWastewater

Drinking Water

Regulatory

Process

Conclusions

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Wastewater

• Goals - halt, minimize

Contamination by Pass-Through

Biosolids Contamination

DestructionDestruction

vsvsWastewater

Pass Thru

Biosolids

Treatment

Drinking Water

Regulatory

Process

Conclusions

RemovalRemoval

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t t

Physical, BioChemicalTreatment

WWTP WWTP Sorption Removal and Pass ThroughSorption Removal and Pass Through

BiosolidsBiosolids impactimpact

Limited BiodegradationLimited Biodegradation

Wastewater

Pass Thru

Biosolids

Treatment

Drinking Water

Regulatory

Process

Conclusions

10

WHAT WORKS?

Recent Studies:

“REDUCTION OF EMERGING CONTAMINANTS THROUGH CONVENTIONAL ANDADVANCED WASTEWATER TREATMENT PROCESSES”Joan Oppenheimer, Roger Stephenson, Samer Adham, James DeCarolis 2007

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t tWastewater

Pass Thru

Biosolids

Treatment

Drinking Water

Regulatory

Process

Conclusions

• Six full-scale treatment facilities

• Twenty target PPCPs

• Percentage removal of each compound versus the solids retention time (SRT)

• Benchmark: SRT80%

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t tWastewater

Pass Thru

Biosolids

Treatment

Drinking Water

Regulatory

Process

Conclusions

SO… WHAT WORKS?

AWWA Research Foundation (AWWARF)

R l f EDC d Ph ti l

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t t Removal of EDCs and Pharmaceuticals in Drinking Water and Reuse Treatment Processes, 2007

Wastewater

Drinking Water

Regulatory

Process

Conclusions

11

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t t

RECENT FINDINGS

-“SRT80%” not achievable for most compounds

Best biological removal performance noted with nitrification/denitrification system

Wastewater

Pass Thru

Biosolids

Treatment

Drinking Water

Regulatory

Process

Conclusions

-Microfiltration reverse osmosis (MF/RO)Optimal Removal, little/no destruction, high $

OBSERVATIONS

1) Bio-sorption

2) Advanced Oxidation

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t t 70%

80%

90%

100%

Wastewater

Pass Thru

Biosolids

Treatment

Drinking Water

Regulatory

Process

Conclusions

0%

10%

20%

30%

40%

50%

60%

70%

Per

cen

t R

emo

val

Ann Arbor

Grand Rapids

•Free chlorinePharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t tWastewater

Drinking Water

Regulatory

Process

Conclusions

12

•Free chlorine•Ozone

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t tWastewater

Drinking Water

Regulatory

Process

Conclusions

•Free chlorine•Ozone•Ultraviolet irradiation

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t tWastewater

Drinking Water

Regulatory

Process

Conclusions

•Free chlorine•Ozone•Ultraviolet Disinfection•Advanced Oxidation

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t tWastewater

Drinking Water

Regulatory

Process

Conclusions

13

•Free chlorine•Ozone•Ultraviolet Disinfection•Advanced Oxidation•Activated Carbon

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t tWastewater

Drinking Water

Regulatory

Process

Conclusions

•Free chlorine•Ozone•Ultraviolet Disinfection•Advanced Oxidation•Activated CarbonR O i

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t t •Reverse OsmosisWastewater

Drinking Water

Regulatory

Process

Conclusions

•Free chlorine•Ozone•Ultraviolet Disinfection•Advanced Oxidation•Activated CarbonR O i

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

W t t •Reverse Osmosis•Biological Removal

Wastewater

Drinking Water

Regulatory

Process

Conclusions

14

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Regulatory ProcessEndocrine Disruptor Screening Program Section 408(p) of the Federal Food, Drug, and Cosmetic Act (FFDCA.

$2.85 to $6 billion to fully screen EDC chemicals

Regulatory

Process

Regulate

Manage

Future

Conclusions

EDC chemicals(University of Minnesota, 2004)

If a substance is found to have an endocrine effect on humans, FFDCA section 408(p)(6) directs the Administrator to take action under available statutory authority to ensure protection of public health.

Should We Regulate Should We Regulate a Specific Chemical?a Specific Chemical?

Persistent and/or bioaccumulative?

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Evidence of antibiotic resistance?

Evidence of endocrine disruption?

Potential for allergic reactions?

Risks to environment, human health?

Regulatory

Process

Regulate

Manage

Future

Conclusions

Likely Regulatory TargetsLikely Regulatory Targets

Cardiovascular agents

Anxiolytic sedatives

hypnotics & antipsychotics

Gastrointestinal meds

Antivirals Based on combination of:

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Corticosteroids Based on combination of:

– Predicted relative

clinical dose

– Log Kow

– Removal in WWTPs

– Number of compounds

in class

Daphnid > Fish > Algae

- Sanderson et al., 2004

Regulatory

Process

Regulate

Manage

Future

Conclusions

15

What is happening now?What is happening now?

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Regulatory

Process

Regulate

Manage

Future

Conclusions

What is What is REALLY REALLY happening now?happening now?

“Potential Releases of Unused Medicines In Landfill Leachate”

Lial Tischler, Tischler/Kocurek, Virginia Cunningham, Doug Finan GSK, Mary Buzby, Merck & Co., Inc. Neil Parke, Eli Lilly & Co., Inc.

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Regulatory

Process

Regulate

Manage

Future

Conclusions

What is What is REALLY REALLY happening now?happening now?

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Direct Disposal  (Toilet/Landfill)

Regulatory

Process

Regulate

Manage

Future

Conclusions

Trash

Flush

Store

16

CONSIDER THIS QUOTE:

“Landfill disposal of unused medicines will result in much lower surface water discharges of pharmaceutical active ingredients than flushing unused medicines to sewers.”

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

WHENconsidering the 20% or so that is not excreted

Regulatory

Process

Regulate

Manage

Future

Conclusions

Landfill Disposal of Unused Medicines Gaining Momentum & Publicity

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Regulatory

Process

Regulate

Manage

Future

Conclusions

PPCPs, PPCPs, EDCs, EDCs, SurvivalSurvival

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Biosolids to Biosolids to Landfill? Landfill?

Regulatory

Process

Conclusions

17

Historical Historical EPA methodsEPA methods

EDCs lowEDCs low--dose activitydose activity

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Regulatory

Process

Conclusions

Previous work missed EDC impacts

Ecologically, which is appropriate? “Innocent until proven guilty”

vs.

“U f til S f ”

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

“Unsafe until proven Safe”

87,000 compounds

Current tracking

Regulatory

Process

Conclusions

Need: ControlNeed: Control

Unacceptable discharge = Unacceptable discharge = unmanageable riskunmanageable risk

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Regulatory

Process

Conclusions

18

Pharmaceuticals& Personal CareProducts (PPCPs)

Background

Example Compounds

Research

Treatment

Necessary: 5Necessary: 5--10 10 year plans.year plans.

ConsiderConsider Efforts to Optimize EDC Efforts to Optimize EDC & PPCP & PPCP Destruction Destruction at the at the POTWPOTW

Consider AlsoConsider Also at Water Treatmentat Water Treatment Regulatory

Process

Conclusions

Consider Also Consider Also at Water Treatment at Water Treatment FacilitiesFacilities

AOP Upgradable?AOP Upgradable?

Pharmaceuticals and Personal Pharmaceuticals and Personal Care ProductsCare Products

Literature Review, Treatment Technologies, Research Literature Review, Treatment Technologies, Research and Regulatory Process and Regulatory Process

MWEA IPP SeminarMWEA IPP SeminarOctober 15, 2009October 15, 2009

Rich Grant, P.E. Rich Grant, P.E. –– Fleis & VandenBrink EngineeringFleis & VandenBrink Engineering

Brian Rice, P.E. Brian Rice, P.E. –– Fleis & VandenBrink EngineeringFleis & VandenBrink Engineering

[email protected]@fveng.com [email protected]@fveng.com

800.494.5202 or 616.977.1000800.494.5202 or 616.977.1000


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