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
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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?