Removal of EDCs and PPCPs by Oxidative Disinfection Shane Snyder, Eric Wert, and Dave Rexing Southern Nevada Water Authority AWWARF Project #278: Evaluation of Conventional and Advanced Treatment Processes to Remove EDCs and PhACs Literature Review of EDC/ PPCP Occurrence and Treatment (T1&2) Selection of Surrogate/ Target Compounds (T3) Paul Westerhoff and Yeomin Yoon Arizona State University Canvas Full-Scale Process Trains (T7.1) Bench-scale Testing (T) Pilot-scale Testing (T6) QSAR Development (T) Full-scale Testing (T7.2) Target Compounds Occurrence - based on literature review usage patterns (likelihood of occurrence) Classes/physical properties polarity, molecular size, acid, base, neutral volatility naphthalene vs. iopromide log K ow from -2.0 6.91 pka from 1.6 10. MW from 128 791 daltons Analytical Concerns availability of standards (and quantity) instrumental and extraction issues Erythromycin 710 Å 3 Iopromide 1 Å 3 Acetaminophen 138 Å 3 1
Steroids Antimicrobials Testosterone Ethinylestradiol Triclosan Trimethoprim Progesterone 17β Estradiol Estrone Androstenedione Estriol Sulfamethoxazole Erythromycin Analgesics Psychoactive Naproxen Hydrocodone Carbamazepine Dilantin Diazepam Acetaminophen Caffeine Ibuprofen Diclofenac Fluoxetine Meprobamate 2
Gemfibrozil Others 13 C surrogates Sample Collection 1L silanized bottle Pentoxifylline TCEP Iopromide Metolachlor Vanderford et Solid al. 2003 Phase Analytical Chemistry 7 Extraction (22):626-627 00 mg HLB Micro LLE 13 C internals 13 C internals Galaxolide Musk Ketone Atrazine GC/MS/MS LC/MS/MS Disinfection Removal Experimental Design Experimental Design Chlorine, UV, and Ozone disinfection Bench-scale: Spike conc. from 100-00 ng/l Three natural waters, synthetic, & DI Some quenched, some not Pilot-scale Dynamic & batch spiking 100-00 ng/l Full-scale NO spike, compounds below 100 ng/l 3
Water Quality Water Code ph DOC (mg/l) alkalinity (mg/l as CaCO3) Colorado River CR 8.2 2. 10.0 Passaic Valley PV 6.8 3. 2.0 Suwannee River NOM SR 7..0 N/A Louisville LsV 7.9 3. 79.0 Chlorination Chlorine dosed as sodium hypochlorite Experiments at ambient and ph. Chlorine dose established by demand curve (3. mg/l for CR) residual goal of 0. mg/l at 2-hours 2-hour simulated distribution system quenched with 0 mg ascorbic acid (?) Ozonation Decay Curve to Determine Ozone Dose (2. mg/l for Colorado River) 0.1-0.3 mg/l Ozone Residual Goal after min Stock solution injected into 1 L sample bottles and mixed No quenching of ozone residual For O 3 /H 2 O 2 experiments, 0.02 mg peroxide/mg ozone (0.062 mg/l for Colorado River AOP) peroxide added 1 min prior to ozone MUST KEEP SOLVENTS TO MINIMUM!
>9 by Cl or O 3 >9 by Cl or O 3 Oxybenzone 17β-Estradiol Sulfamethoxazole Naproxen Erythromycin Estrone Acetaminophen Octylphenol Estriol Trimethoprim Hydrocodone Diclofenac Cl ambient Cl ph. Ozone Ozone/Peroxide Cl ph ambient Cl ph. Ozone Ozone/Peroxide Testosterone Erythromycin Androstenedione Progesterone Sulfamethoxazole Estradiol Estriol Triclosan Estrone Trimethoprim Ethynylestradiol 0 20 0 60 80 100 0 20 0 60 80 100
Cl ph ambient Cl ph. Ozone Ozone/Peroxide Cl ph ambient Cl ph. Ozone Ozone/Peroxide Naproxen Caffeine Diclofenac Fluoxetine Meprobamate Ibuprofen Diazepam Hydrocodone Dilantin Acetaminophen Carbamazepine 0 20 0 60 80 100 0 20 0 60 80 100 Cl ph ambient Cl ph. Ozone Ozone/Peroxide DEET Atrazine Metolachlor Galaxolide Musk Ketone TCEP Iopromide Pentoxifylline Gemfibrozil 0 20 0 60 80 100 Ozone Pilot Plant 23 L/min dynamic spike infused into raw 2x static mixtures 12 cells ozone cell 1 2 min/cell (2 min total) sampled cells 1, 3, & 12 2.39 mg/l O 3 dose 1.33 mg/l O 3 demand CT.2 mg-min/l 1.17 log Crytpo kill residual quenched coagulation (0.6 mg Fe) BAF and BAC columns 6
Solvent Mixture On 1 Raw Water Spike Mixture On Testosterone Pilot 2 Pilot 6 Pilot 2 Bench Cell#3 Dissolved Ozone Residual (mg/l) 0.9 0.8 0.7 0.6 0. 0. 0.3 0.2 0.1 0 0 20 0 60 80 100 120 10 Time (min) Androstenedione Progesterone Estradiol Estriol Estrone Ethynylestradiol 0 20 0 60 80 100 Pilot 2 Pilot 6 Pilot 2 Bench Pilot 2 Pilot 6 Pilot 2 Bench Erythromycin Naproxen Sulfamethoxazole Diclofenac Ibuprofen Triclosan Hydrocodone Trimethoprim Acetaminophen 0 20 0 60 80 100 0 20 0 60 80 100 7
Pilot 2 Pilot 6 Pilot 2 Bench Pilot 2 Pilot 6 Pilot 2 Bench Caffeine Fluoxetine Meprobamate Diazepam Dilantin Carbamazepine DEET Atrazine Metolachlor Galaxolide Musk Ketone TCEP Iopromide Pentoxifylline Gemfibrozil 0 20 0 60 80 100 0 20 0 60 80 100 UV Bench Medium pressure collimated beam Removal based on molar absorptivity 0 and 1000 mj/cm 2 AOP = 1000 mj/cm 2 + mg H 2 O 2 Quenched with 0.2 mg bovine catalase/l Spiked at ~ 300 ng/l using 100 µl MeOH/L H 2 O 100 µl ~ 100 mg MeOH, negated the AOP!!! MeOH scavages hydroxyl radicals Recently repeated at bench- and pilot- scale 0 mj 1000 mj Testosterone Androstenedione Progesterone Estradiol Estriol Estrone Ethynylestradiol 0 20 0 60 80 100 8
0 mj 1000 mj 0 mj 1000 mj Erythromycin Acetaminophen Hydrocodone Sulfamethoxazole Ibuprofen Triclosan Diclofenac Trimethoprim Naproxen 0 20 0 60 80 100 0 20 0 60 80 100 0 mj 1000 mj 0 mj 1000 mj Caffeine Gemfibrozil Pentoxifylline Fluoxetine Iopromide Meprobamate TCEP Musk Ketone Diazepam Galaxolide Dilantin Metolachlor Atrazine Carbamazepine DEET 0 20 0 60 80 100 0 20 0 60 80 100 9
UV Pilot UV Only UV + ppm Peroxide UV + 8 ppm Peroxide Medium pressure Androstenedione Flow rate to control UV dose (3x) Progesterone Testosterone 0,, & 8 mg H 2 O 2 /L Estradiol Peroxide quenched with 0.2 mg bovine catalase/l Spiked 8,000 L at 100-200 ng/l with <1mL MeOH spike solution had to be concentrated some compounds were lost during evaporation (i.e., galaxolide and musk ketone) Estrone Ethynylestradiol Estriol 0 20 0 60 80 100 UV Only UV + ppm Peroxide UV + 8 ppm Peroxide UV Only UV + ppm Peroxide UV + 8 ppm Peroxide Triclosan Diclofenac Acetaminophen Erythromycin Hydrocodone Sulfamethoxazole Ibuprofen Trimethoprim Naproxen 0 20 0 60 80 100 0 20 0 60 80 100 10
UV Only UV + ppm Peroxide UV + 8 ppm Peroxide UV Only UV + ppm Peroxide UV + 8 ppm Peroxide Carbamazepine Oxybenzone Dilantin Gemfibrozil Pentoxifylline Diazepam Iopromide Meprobamate TCEP Fluoxetine Metolachlor Atrazine Caffeine DEET 0 20 0 60 80 100 0 20 0 60 80 100 Full-scale Treatment Site selection likely occurrence treatment processes willingness to participate NO SPIKING limited to detectable compounds prescreening time of year important interpretations challenging simultaneous processes Conventional Chlorine Raw ng/l Finished % Predicted Hydrocodone 1.9 <1.0 >7 Trimethoprim 2.2 <1.0 > Acetaminophen 1. <1.0 >33 Caffeine 7 86 0 18 Erythromycin 3.2 <1.0 >69 Sulfamethoxazole 3 <1.0 >97 >90 Meprobamate 10 8.0 20 13 Dilantin 13 7.2 18 TCEP 19 17 11 Carbamazepine 20 3.6 82 2 DEET 28 32 0 1 Atrazine 2 27 0 Iopromide 6 17 63 2 Naproxen 16 1 >9 >93 Ibuprofen 10 21 0 39 Triclosan 2.7 <1.0 >63 Gemfibrozil.8 <1.0 >83 7 11
Conventional Chlorine Conventional Chlorine ng/l Raw Finished % Predicted Atrazine 2 0 Sulfamethoxazole 27 <1.0 >96 >90 Ibuprofen 2 32 0 39 Caffeine 11 10 9 19 TCEP 11 6. 1 Gemfibrozil 11.2 62 7 Naproxen 10 <1.0 >90 >93 Carbamazepine 9.6.7 1 2 DEET 8.8 7. 1 1 Dilantin.3. 17 18 Meprobamate.0 3.8 13 Erythromycin 3.0 <1.0 >67 >96 Trimethoprim 2.3 <1.0 >7 >98 Triclosan 1.1 <1.0 >9 >97 Raw Post Clarification Sulfamethoxazole <1.0 >97 Caffeine 30 27 10 DEET 1 1 7 TCEP 11 10 9 Carbamazepine.8.8 17 Dilantin 2.2 2.0 9 Ibuprofen 1.9 1.9 0 Naproxen 1.1 <1.0 >9 Predicted >90 18 1 2 17 0 >93 Conventional Chlorine Full Scale Ozone Raw Finished % Removed Caffeine 31 20 3 Sulfamethoxazole.6 <1.0 >82 Meprobamate 2.6 2.3 12 Dilantin 3.7 2.2 1 TCEP 2.8 86 Carbamazepine 1.2 <1.0 >17 DEET 17 16 6 Atrazine 7 31 6 Iopromide 6.6 7.8 0 Naproxen 1.8 <1.0 > Ibuprofen 3.6 3.0 17 Gemfibrozil 1.7 <1.0 >1 Predicted 18 13 18 2 1 2 >93 0 7 Raw Finished Caffeine.1 <1.0 Sulfamethoxazole 11 <1.0 Meprobamate 13 9. 28 Dilantin 3.1 1. 2 TCEP.0 6. 0 Carbamazepine 3. <1.0 DEET.0 2.0 0 Atrazine 1. <1.0 >0 Estrone 1. <1.0 >0 Testosterone 1.0 <1.0 >0 Predicted 0 80 10 70 0 12
Full Scale Ozone Full Scale UV Raw Finished Sulfamethoxazole 9.7 <1 >90 Meprobamate 11.8 7 Dilantin 3.2 <1 >70 TCEP.2.2 0 Carbamazepine 2. <1 >60 DEET 3. 1. 9 Atrazine 1. <1 >30 Predicted 0 80 10 70 >0 Pre-UV Post-UV Caffeine 2 27 0 Erythromycin 2. 2.6 0 Sulfamethoxazole 1.7 2.1 0 Meprobamate 10 12 0 Dilantin 1. 2.1 0 TCEP 21 22 0 Carbamazepine 2.2 2.8 0 DEET 3.9.6 0 Atrazine 8.0 8. 0 Iopromide 7.3 7.8 0 Ibuprofen 6.2 8.1 0 Gemfibrozil 9. 10 0 Predicted 3 2 3 0 3 11 7 2 Full Scale UV Raw Finished Atrazine 28 29 0 Caffeine 2 12 0 TCEP 19 1 21 Meprobamate 8.0 8.0 0 Gemfibrozil 7. 2. 68 Sulfamethoxazole.8 <1.0 83 DEET.0.1 18 Iopromide.1.6 0 Ibuprofen 2. 2.7 0 Acetaminophen 1.8 <1.0 Dilantin 1.3 1.1 1 Carbamazepine 1.2 <1.0 17 Erythromycin 1.0 <1.0 0 Predicted 3 0 2 3 11 7 18 3 10 Summary Removal related to structure (and dose) Chlorine good for phenolics, less effective for ketones E2, EE2, octylphenol well removed (90 - %) testosterone, progesterone, androstendione poorly removed Ozone generally more effective than chlorine Ozone/peroxide (AOP) slightly more effective than ozone alone Higher peroxide doses likely would improve removal UV ineffective at disinfection doses, but highly effective as an AOP using peroxide 13
Summary Pitfalls and Snare Traps: Solvents used for spiking Must be kept at a minimum or removed Should verify solvent demand Quenching and preservation Some quenching agents remove target analytes Must quench CHLORINE, less important for ozone and UV (peroxide quenching less critical) Must conduct holding studies preservative? Surrogates and Internal standards Critical can learn a great deal from their behavior chlorine example Final Thoughts EDCs/PPCPs can be reduced by treatment Treatment strategies that combine processes would be most effective Oxidation can be very effective But, what % removal is appropriate? Detection does not infer toxicity! We MUST understand the toxicological relevance! (AWWARF/WRF #308) CO$T:Benefit??? Questions shane.snyder@snwa.com 1