1 full scale and pilot scale evaluation of endocrine disrupting compound removal through wtp...

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Full Scale and Pilot Scale Evaluation of Endocrine Disrupting Compound Removal Through WTP Processes

Bob Raczko, P.E.United Water

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PRESENTATION OUTLINE

Background information

Research projects:– Water Research Foundation (WRF)– United WERCs

WRF project

United WERCs project

Summary

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EDCs and PPCPs

• EDCs - endocrine disrupting chemicals• PPCPs - pharmaceuticals and personal care

products

• Includes wide range of daily-use productsPharmaceuticals Personal care productsPesticides SurfactantsPlasticizers PAHs

• Manmade sources - synthetic chemicals• Detected at ug/L and ng/L levels

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Putting Things in Perspective

1 ppb or 1 ug/L 1 ppt or 1 ng/L

X 1,000

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Toxicological Relevance of PPCPs and EDCs

Drinking Max.Water Equiv. FinishedLevel Water Level(ug/L) (ug/L)

Carbamazepine 12 0.018Triclosan 2,600 0.0012Sulfamethoxazole 18,000 0.003Trimethoprim 6,700 <0.00025Phenytoin 6.8 0.032Diclofenac 2,300 <0.00025Naproxen 20,000 <0.0005Gemfibrozil 45 0.0021Estradiol 0.58 <0.0005

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Research Projects – Endocrine Disrupting Compounds (EDCs) and Pharmaceuticals and Personal Care Products (PPCPs)

Water Research Foundation (WRF)– Removal of Unregulated Organic Chemicals in Full-Scale Water

Treatment Processes

United WERCs– Advanced Pilot Testing of Treatment Processes for Removal of EDCs

and PPCPs

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WaterRF Project

Sponsoring Utility: Passaic Valley Water Commission, NJ

Principal Investigator: Black & Veatch, consulting engineer

Co-PIs: Catherine Spencer, Black & VeatchDr. Judy Louis, NJDEP

Utility Participants: UWNJ, UWRahway, Brick Township

Objective: Investigate the effectiveness of full-scale conventional and advanced water treatment processes for removal of endocrine disrupting compounds.

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WRF Project - Research Approach

Sample each treatment plant 4 times – spring/summer/fall/winter

Collect samples after each unit treatment process

Samples were analyzed by USGS laboratory

Analyze for over 100 compounds

Pilot testing using Haworth pilot plant - United WERCs

project

Prepare project report summarizing the findings

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United WERCs - Research Approach

Participants - United Water and NJIT

Overall – supplement WRF project by obtaining additional performance data for a variety of conventional and advanced water treatment processes on the removal efficiency of EDCs and PPCPs from drinking water supplies.

Specific objectives:– Identify select unregulated compounds to investigate– Spike the Haworth pilot plant influent with the select compounds– Follow these compounds through the pilot plant unit treatment

processes– Evaluate their removal and degradation as a function of treatment

process– Evaluate potential synergies in treatment processes

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WaterRF Project Findings

Contaminants and levels varied – Round 1 (May 2010) – 23 raw water compounds– Round 2 (August 2010) – 20 raw water compounds but not the same as

Round 1– Round 3 (March 2011) – 30 raw water compounds, many not found prior– Round 4 (July 2011) - 30 raw water compounds, some not found prior

Classes of compounds found– Pharmaceuticals, few antibiotics, ingested metabolites– Flame retardants – Fragrance, flavor– Topically applied compounds– PAHs– Pesticides– Solvents/plasticizers– Detergents (nonyl- and octylphenols)

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Conclusions from the Data

Large range in concentration and types of compounds found with precipitation/source volume, seasonal patterns

Would be very difficult to regulate using a contaminant-by-contaminant approach

Advanced oxidation, especially post-coagulation, effective for oxidation/conversion of many aromatics, alkanes, and cyclic organics

GAC adsorption of more non-polar compounds (PAHs, flavor and fragrance compounds, many pharmaceuticals)

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0

200

400

600

800

1000

1200

1400

Post Coag 1 Post Coag 2 Post Ozone Filtered Finished

Mic

rogr

ams/

liter

Plant A Round 3Tris(dichloroisopropyl) phosphate

Tris(2-chloroethyl) phosphate

Tris(2-butoxyethyl) phosphate

Triethyl citrate

Tetrachloroethene

Hexahydrohexamethyl cyclopentabenzopyran

Carbamazepine

Caffeine

p-Cresol

DEET

Nan

og

ram

s/l

iter

13

0

100

200

300

400

500

600

700

800

900

1000

Raw Post Aeration

Post Coag Filtered Post GAC Finished

Mic

rogr

ams/

liter

Plant B Round 1

Tris(2-chloroethyl) phosphateTris(2-butoxyethyl) phosphateTriethyl citrate

Tetrachloroethene

Fluoranthene

Cotinine

Cholesterol

Carbamazepine

Caffeine

Acetaminophen

9,10-Anthraquinone

Prometon

Metolachlor

DEET

Nan

og

ram

s/l

iter

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Plant B

- Raw

Plant B

- Filt

ered

Plant B

- Pos

t GAC

Plant B

- F

inish

ed0

500

1000

1500

2000

2500

3000

3500

Tris(dichloroisopropyl) phosphateTris(2-chloroethyl) phosphateTris(2-butoxyethyl) phosphateTriphenyl phosphateTriethyl citrateTributyl phosphateTetrachloroethenePyrenePhenanthreneIsophoroneFluorantheneCotinineCaffeineBenzophenoneAnthracene9,10-Anthraquinone4-tert-Octylphenol4-Nonylphenol (sum of all isomers)PrometonMetolachlorDEETCarbazoleCarbarylBromacil

Nan

ogra

ms/

liter

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Category RemovalPolycyclic Aromatic Hydrocarbons 100% after filtration or GAC

Pesticides chloroacetanilide triazine uracil type solvent

Variable66% after GAC

Bind weakly to GAC?100% after GAC

Fragrance compound 100% after aeration

Topically applied - DEET 41 – 75% after GAC and chlorine

Metabolites caffeine cotinine cholesterol

0 – 65% after GAC<20% in finished water

100% post aeration

Pharmaceuticals/Antibiotics 100% after GAC

Flame retardants – only 1 of 3 removed

<10% (2) 100% (1) after GAC

Plasticizer 100% removed by filtration

Volatile 88 – 100% after aeration

Plant B Process Performance

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0

200

400

600

800

1000

1200

1400

Raw Post Ozone Post chlorine Filtered Finished

Mic

rogr

ams/

liter

Plant D Round 3 Tris(dichloroisopropyl) phosphateTris(2-chloroethyl) phosphate

Tris(2-butoxyethyl) phosphate

Triphenyl phosphate

Tributyl phosphate

Tetrachloroethene

Pyrene

Phenanthrene

Isophorone

Hexahydrohexamethyl cyclopentabenzopyranFluoranthene

Cholesterol

Caffeine

beta-Sitosterol

Benzophenone

9,10-Anthraquinone

4-tert-Octylphenol

DEET

Camphor

Nan

og

ram

s/l

iter

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Category Removal

PAH/cresol Created with chlorine

Pesticide - solvent inconclusive

Fragrance compounds HHCBcamphor

Variable100% post flocculation

Observed after chlorination

Topically applied - DEET <10%

Metabolitescaffeinecholesterolcotinine

<10%100% post ozone

100 % post chlorine

Pharmaceutical inconclusive

Flame retardants (3) 0%

Volatile solvent 50 to 100% after filtration

Plant D Process Performance

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United WERCs Project Elements

Task 1 - Preliminary Investigations May-December 2010– Literature Review– Surrogate or indicator parameters– Other treatment processes– Technical Memorandum - deliverable November 2010

Task 2 - Pilot Tests April 2011 – July 2011– Initial pilot runs– Memorandum - deliverable June 2011

– Additional pilot runs Task 3 - Report Preparation September

- December 2011– Draft report - deliverable November 2011– Final report - deliverable December 2011

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Priority Indicator Compounds(12 Groups, 16 Compounds)

Classes Compounds

Analgesics Acetaminophen

Ibuprofen

Antibiotics Erythromycin

Sulfamethoxazole

Trimethoprim

Antidepressants Diazepam

Antiepileptic Carbamazepine

Beta-Blockers Atenolol

Blood Lipid Regulators Gemfibrozil

Fire Retardant Tris(2-chloroethyl)phosphate (TCEP)

Nicotine Metabolite Cotinine

Pesticides Atrizine

N,N-Diethyl-meta-toluamide (DEET)

Psychomotor Stimulant Caffeine

Steroids 17 β-Estradiol

X-ray Contrast Agent Iopromide

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Pilot Plant Flow Diagram

Train A – O2/VGAC

Train B – O2/UGAC

Train C – UV/H2O2

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Results of Ozone Tests

Removal Pre-Ozone

Pre-Ozone/H2O2

Intermediate Ozone

Intermediate Ozone/H2O2

> 90% 7 3 5 6

75 – 90 % 1 2 1 3

75 – 99 % 8 5 6 9

50 – 75 % 2 2 2 0

< 50 % 5 8 7 6

0 – 75 % 7 10 9 6

Note: 1. Number in each box denotes number of compounds removed at given percentage.

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Results of GAC Tests

Removal VirginGAC

Used GAC

> 90% 13 2

75 – 90 % 0 2

75 – 99 % 13 4

50 – 75 % 0 3

< 50 % 2 8

0 – 75 % 2 11

Note: 1. Number in each box denotes number of compounds removed at given percentage.

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Results of Ozone/GAC Tests

Removal Pre-OzoneVirgin GAC

Pre-Ozone Used GAC

Inter. OzoneVirgin GAC

Inter. Ozone Used GAC

> 90% 131

ND - 97

ND - 215

ND - 138

ND - 4

75 – 90 % 2 1 0 2

75 – >99 %

15 8 15 10

50 – 75 % 0 1 0 3

< 50 % 0 6 0 2

0 – 75 % 0 7 0 5

Note: 1. Number in each box denotes number of compounds removed at given percentage.

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Results of UV/H2O2 Tests

Removal UV – 500H2O2 - 20

UV - 500H2O2 - 15

UV - 700H2O2 - 15

UV – 700H2O2 - 15

> 90% 6 7 12 12

75 – 90 % 3 2 1 1

75 – 99 % 9 9 13 13

50 – 75 % 1 1 1 0

< 50 % 5 5 1 2

0 – 75 % 6 6 2 2

(UV – mJ/Sq cm) (H2O2 – mg/L)

Note: 1. Number in each box denotes number of compounds removed at given percentage.

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Overall Test Results

Removal

Pre-Ozone

Intermediate

Ozone/H2O2

VirginGAC

Intermediate

Ozone/VGAC

UV/H2O2

700/15

> 90% 71 6 13 15ND - 13

12ND - 9

75 – 90 %

1 3 0 0 1

75 – 99 %

8 9 13 15 13

50 – 75 %

2 0 0 0 1

< 50 % 5 6 2 0 1

0 – 75 % 7 6 2 0 2

Note: 1. Number in each box denotes number of compounds removed at given percentage.

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Treatability of Indicator Compounds

Acetaminophen Ibuprofen Sulfamethoxazole Trimethoprim Carbamazepine Atenolol Gemfibrozil Atrazine DEET Caffeine 17β-Estradiol Iopromide

Erythromycin TCEP Cotinine DEET Caffeine 17β-Estradiol Iopromide

Good (75%) to Very Good (>90%) Fair (50%) to Poor (<50%)

Indicates removal dependent on treatment process

“Good to Very Good” and “Fair to Poor” applies to alltreatment processes.

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Treatment Issues/Concerns

Ozone - potential by-products formed

GAC - carbon usage rate (or length of run)

UV/H2O2 - potential by-products formed

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Summary

Advanced processes (oxidation, AOP, GAC) most effective

AOP - UV/H2O2 - may not be practical

Future work– Range of effective dosages for ozone– Range of dosages for ozone and H2O2

– GAC contact time and usage rate– By-product formation– Confirm indicator compounds

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THANK YOU!

Any Questions?