Full Scale and Pilot Scale Evaluation of Endocrine Disrupting Compound Removal Through WTP Processes Bob Raczko, P.E. United Water 1 PRESENTATION OUTLINE Background information Research projects: Water Research Foundation (WRF) United WERCs WRF project United WERCs project Summary 2 EDCs and PPCPs EDCs - endocrine disrupting chemicals PPCPs - pharmaceuticals and personal care products Includes wide range of daily-use products Pharmaceuticals Personal care products Pesticides Surfactants Plasticizers PAHs Manmade sources - synthetic chemicals Detected at ug/L and ng/L levels 3 Putting Things in Perspective 1 ppb or 1 ug/L 1 ppt or 1 ng/L
X 1,000 4 Toxicological Relevance of PPCPs and EDCs Drinking Max. Water Equiv. Finished Level Water Level (ug/L) (ug/L) Carbamazepine 12 0.018 Triclosan 2,600 0.0012 Sulfamethoxazole 18,000 0.003 Trimethoprim 6,700 <0.00025 Phenytoin 6.8 0.032 Diclofenac 2,300 <0.00025 Naproxen 20,000 <0.0005 Gemfibrozil 45 0.0021 Estradiol 0.58 <0.0005 5
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 6 WaterRF Project Sponsoring Utility: Passaic Valley Water Commission, NJ Principal Investigator: Black & Veatch, consulting engineer Co-PIs: Catherine Spencer, Black & Veatch Dr. 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. 7 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 8 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 9 WaterRF Project Findings Contaminants and levels varied Round 1 Round 2 Round 1 Round 3 Round 4 (May 2010) 23 raw water compounds (August 2010) 20 raw water compounds but not the same as (March 2011) 30 raw water compounds, many not found prior (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) 10 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 postcoagulation, 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) 11 Plant A Round 3 Tris(dichloroisopropyl) phosphate
1400 Tris(2-chloroethyl) phosphate 1200 Tris(2-butoxyethyl) phosphate Nanograms/liter Micrograms/liter 1000 Triethyl citrate 800 Tetrachloroethene 600 Hexahydrohexamethyl cyclopentabenzopyran Carbamazepine 400 Caffeine p-Cresol 200 DEET 0 Post Coag 1 Post Coag 2 Post Ozone 12 Filtered
Finished Plant B Round 1 1000 Tris(2-chloroethyl) phosphate Tris(2-butoxyethyl) phosphate Triethyl citrate 900 800 Tetrachloroethene Nanograms/liter Micrograms/liter 700 Fluoranthene 600 Cotin ine Cholesterol 500 Carbamazepine Caffeine 400 Acetaminophen 300 9,10-Anthraquinone Prometon 200
Metolachlor 100 DEET 0 Raw Post Aeratio n Post Coag 13 Filtered Post GAC Finished 3500 3000 Nanograms/liter 2500 2000 1500 1000 500 0 P
nt la B -R aw an Pl tB -F d re e t il t an l P 14 B - A tG s Po C P nt
la B -F ed sh i in Tris(dichloroisopropyl) phosphate Tris(2-chloroethyl) phosphate Tris(2-butoxyethyl) phosphate Triphenyl phosphate Triethyl citrate Tributyl phosphate Tetrachloroethene Pyrene Phenanthrene Isophorone Fluoranthene Cotinine Caffeine Benzophenone Anthracene 9,10-Anthraquinone 4-tert-Octylphenol 4-Nonylphenol (sum of all isomers) Prometon Metolachlor DEET Carbazole Carbaryl Bromacil Plant B Process Performance Category Removal
Polycyclic Aromatic Hydrocarbons 100% after filtration or GAC Pesticides chloroacetanilide triazine uracil type solvent Variable 66% after GAC Bind weakly to GAC? 100% after GAC Fragrance compound 100% after aeration Topically applied - DEET Metabolites caffeine cotinine cholesterol 0 65% after GAC <20% in finished water 100% post aeration Pharmaceuticals/Antibiotics Flame retardants only 1 of 3 removed Plasticizer Volatile 41 75% after GAC and chlorine 100% after GAC
<10% (2) 100% (1) after GAC 100% removed by filtration 15 88 100% after aeration Tris(dichloroisopropyl) phosphate Tris(2-chloroethyl) phosphate Plant D Round 3 1400 Tris(2-butoxyethyl) phosphate Triphenyl phosphate 1200 Tributyl phosphate Tetrachloroethene 1000 Nanograms/liter Micrograms/liter Pyrene Phenanthrene 800 Isophorone 600 Hexahydrohexamethyl cyclopentabenzopyran Fluoranthene Cholesterol Caffeine
400 beta-Sitosterol Benzophenone 200 9,10-Anthraquinone 4-tert-Octylphenol DEET 0 Raw Post Ozone 16 Post chlorine Filtered Finished Camphor Plant D Process Performance Category Removal PAH/cresol Created with chlorine Pesticide - solvent inconclusive Fragrance compounds HHCB
camphor Variable 100% post flocculation Observed after chlorination Topically applied - DEET Metabolites caffeine cholesterol cotinine <10% <10% 100% post ozone 100 % post chlorine Pharmaceutical inconclusive Flame retardants (3) 0% Volatile solvent 50 to 100% after filtration 17 United WERCs Project Elements Task 1 - Preliminary Investigations 2010
Literature Review Surrogate or indicator parameters Other treatment processes Technical Memorandum - deliverable Task 2 - Pilot Tests Initial pilot runs Memorandum - deliverable Additional pilot runs Task 3 - Report Preparation December Draft report - deliverable Final report - deliverable 18 May-December November 2010 April 2011 July 2011 June 2011 September 2011 November 2011 December 2011 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 -Estradiol X-ray Contrast Agent Iopromide 19 Pilot Plant Flow Diagram Train B O2/UGAC Train A O2/VGAC Train C UV/H2O2 20 Results of Ozone Tests Note: 1. Number in each box denotes number of compounds removed at given percentage. Removal PreOzone Pre-Ozone/ H2O2 Intermediat e 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 21 Results of GAC Tests Note: 1. Number in each box denotes number of compounds removed at given percentage. Removal Virgin GAC Used GAC 13 2 75 90 % 0 2 75 99 % 13
4 50 75 % 0 3 < 50 % 2 8 0 75 % 2 11 > 90% 22 Results of Ozone/GAC Tests Note: 1. Number in each box denotes number of compounds removed at given percentage. Removal PreOzone Virgin GAC Inter. Ozone Virgin GAC Inter. Ozone Used GAC
> 90% 131 ND - 9 7 ND - 2 15 ND - 13 8 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 Pre-Ozone Used GAC 23 Results of UV/H2O2 Tests Note: 1. Number in each box denotes number of compounds removed at given percentage. (H2O2 mg/L) (UV mJ/Sq cm) Removal
UV 500 H2O2 - 20 UV - 500 H2O2 - 15 UV - 700 H2O2 - 15 UV 700 H2O2 - 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 24 Overall Test Results Note: 1. Number in each box denotes number of compounds removed at given percentage.
Remov al PreOzone Intermediat e Ozone/H2O2 Virgin GAC Intermediat e Ozone/VGAC UV/H2O2 700/15 > 90% 71 6 13 15 ND - 13 12 ND - 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 25 Treatability of Indicator Compounds Good (75%) to Very Good (>90%) Acetaminophen Ibuprofen Sulfamethoxazole Trimethoprim Carbamazepine Atenolol Gemfibrozil
Atrazine DEET Caffeine 17-Estradiol Iopromide 26 Fair (50%) to Poor (<50%) Erythromycin TCEP Cotinine DEET Caffeine 17-Estradiol Iopromide Indicates removal dependent on treatment process Good to Very Good and Fair to Poor applies to all treatment processes. Treatment Issues/Concerns Ozone - potential by-products formed GAC - carbon usage rate (or length of run) UV/H2O2 - potential by-products formed 27 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 28 THANK YOU! Any Questions? 29
