Removal of EDCs and AWWARF Project #2758: PPCPs by ...
Transcript of Removal of EDCs and AWWARF Project #2758: PPCPs by ...
1
Removal of Removal of EDCsEDCs and and PPCPsPPCPs by Oxidative by Oxidative
DisinfectionDisinfection
Shane Snyder, Eric Wert, and Dave Shane Snyder, Eric Wert, and Dave RexingRexingSouthern Nevada Water AuthoritySouthern Nevada Water Authority
Paul Paul WesterhoffWesterhoff and and YeominYeomin YoonYoonArizona State UniversityArizona State University
AWWARF Project #2758:AWWARF Project #2758:“Evaluation of Conventional and Advanced “Evaluation of Conventional and Advanced
Treatment Processes to Remove Treatment Processes to Remove EDCsEDCs and and PhACsPhACs””
Literature Review of EDC/PPCP Occurrence and
Treatment (T1&2)
Canvas Full-Scale ProcessTrains (T7.1)
Selection of Surrogate/Target Compounds (T3)
Bench-scale Testing (T4) QSAR Development (T5)
Pilot-scale Testing (T6)
Full-scale Testing (T7.2)
Target CompoundsTarget 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 Kow from -2.05 – 6.91– pKa from 1.6 – 10.5– MW from 128 – 791 daltons
• Analytical Concerns– availability of standards (and quantity)– instrumental and extraction issues
Iopromide514 Å3
Acetaminophen138 Å3
Erythromycin710 Å3
2
EstriolAndrostenedione
Progesterone
Testosterone
17β Estradiol
Ethinylestradiol
Estrone
SteroidsSteroids AntimicrobialsAntimicrobials
Triclosan
SulfamethoxazoleErythromycin
Trimethoprim
AnalgesicsAnalgesics
Ibuprofen
Naproxen Hydrocodone
Acetaminophen
Diclofenac
PsychoactivePsychoactive
Carbamazepine Diazepam
Fluoxetine
Caffeine
Meprobamate
Dilantin
3
OthersOthersGemfibrozil
Pentoxifylline
Iopromide
Metolachlor
Galaxolide
TCEP
Musk Ketone Atrazine
Sample Collection
1L silanized bottle
Solid Phase Extraction500 mg HLB
GC/MS/MS LC/MS/MS
Micro LLE
13C surrogates
13C internals13C internals
Vanderford et al. 2003 Analytical Chemistry75 (22):6265-6274
Disinfection RemovalDisinfection Removal Experimental DesignExperimental Design• Chlorine, UV, and Ozone disinfection• Bench-scale:
– Spike conc. from 100-400 ng/L– Three natural waters, synthetic, & DI– Some quenched, some not…
• Pilot-scale– Dynamic & batch spiking 100-400 ng/L
• Full-scale– NO spike, compounds below 100 ng/L
4
Water QualityWater Quality
Water Code pH DOC (mg/L)
alkalinity (mg/L as CaCO3)
Colorado River CR 8.2 2.5 140.0Passaic Valley PV 6.8 3.4 52.0
Suwannee River NOM SR 7.5 4.0 N/ALouisville LsV 7.9 3.5 79.0
ChlorinationChlorination• Chlorine dosed as sodium
hypochlorite• Experiments at ambient and pH 5.5• Chlorine dose established by
demand curve (3.5 mg/L for CR)– residual goal of 0.5 mg/L at 24-hours– 24-hour simulated distribution system– quenched with 50 mg ascorbic acid (?)
OzonationOzonation• Decay Curve to Determine Ozone Dose (2.5
mg/L for Colorado River)• 0.1- 0.3 mg/L Ozone Residual Goal after 5 min• Stock solution injected into 1 L sample bottles
and mixed• No quenching of ozone residual• For O3/H2O2 experiments, 0.025 mg
peroxide/mg ozone (0.0625 mg/L for Colorado River AOP)– peroxide added 1 min prior to ozone
• MUST KEEP SOLVENTS TO MINIMUM!
5
>95% Removal by >95% Removal by ClCl or Oor O33
17β-EstradiolOxybenzone
EstriolOctylphenol
Estrone
>95% Removal by >95% Removal by ClCl or Oor O33
Sulfamethoxazole
Erythromycin
Trimethoprim
Acetaminophen
Hydrocodone
Naproxen
Diclofenac
0 20 40 60 80 100
Ethynylestradiol
Estrone
Estriol
Estradiol
Progesterone
Androstenedione
Testosterone
% Removal
Ozone/PeroxideOzoneCl pH 5.5Cl ambient
0 20 40 60 80 100
Trimethoprim
Triclosan
Sulfamethoxazole
Erythromycin
% Removal
Ozone/PeroxideOzoneCl pH 5.5Cl pH ambient
6
0 20 40 60 80 100
Acetaminophen
Hydrocodone
Ibuprofen
Diclofenac
Naproxen
% Removal
Ozone/PeroxideOzoneCl pH 5.5Cl pH ambient
0 20 40 60 80 100
Carbamazepine
Dilantin
Diazepam
Meprobamate
Fluoxetine
Caffeine
% Removal
Ozone/PeroxideOzoneCl pH 5.5Cl pH ambient
0 20 40 60 80 100
Gemfibrozil
Pentoxifylline
Iopromide
TCEP
Musk Ketone
Galaxolide
Metolachlor
Atrazine
DEET
% Removal
Ozone/PeroxideOzoneCl pH 5.5Cl pH ambient Ozone Pilot PlantOzone Pilot Plant• 23 L/min dynamic
– spike infused into raw– 2x static mixtures– 12 cells – ozone cell 1– 2 min/cell (24 min total)– sampled cells 1, 3, & 12– 2.39 mg/L O3 dose– 1.33 mg/L O3 demand– CT 4.2 mg-min/L– 1.17 log Crytpo “kill”– residual quenched – coagulation (0.6 mg Fe)– BAF and BAC columns
7
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 20 40 60 80 100 120 140
Time (min)
Cel
l#3
Dis
solv
edO
zone
Res
idua
l (m
g/L)
Solvent Mixture On
SpikeMixture OnRaw Water
0 20 40 60 80 100
Ethynylestradiol
Estrone
Estriol
Estradiol
Progesterone
Androstenedione
Testosterone
% Removal
BenchPilot 24Pilot 6Pilot 2
0 20 40 60 80 100
Trimethoprim
Triclosan
Sulfamethoxazole
Erythromycin
% Removal
BenchPilot 24Pilot 6Pilot 2
0 20 40 60 80 100
Acetaminophen
Hydrocodone
Ibuprofen
Diclofenac
Naproxen
% Removal
BenchPilot 24Pilot 6Pilot 2
8
BenchPilot 24Pilot 6Pilot 2
0 20 40 60 80 100
Carbamazepine
Dilantin
Diazepam
Meprobamate
Fluoxetine
Caffeine
% Removal0 20 40 60 80 100
Gemfibrozil
Pentoxifylline
Iopromide
TCEP
Musk Ketone
Galaxolide
Metolachlor
Atrazine
DEET
% Removal
BenchPilot 24Pilot 6Pilot 2
UV BenchUV Bench
• Removal based on molar absorptivity
• 40 and 1000 mJ/cm2
• AOP = 1000 mJ/cm2 + 5 mg H2O2
– Quenched with 0.2 mg bovine catalase/L
• Spiked at ~ 300 ng/L using 100 µL MeOH/L H2O– 100 µL ~ 100 mg MeOH, negated the AOP!!!
• MeOH scavages hydroxyl radicals• Recently repeated at bench- and pilot- scale
• Medium pressure collimated beam
0 20 40 60 80 100
Ethynylestradiol
Estrone
Estriol
Estradiol
Progesterone
Androstenedione
Testosterone
% Removal
1000 mJ40 mJ
9
0 20 40 60 80 100
Trimethoprim
Triclosan
Sulfamethoxazole
Erythromycin
% Removal
1000 mJ40 mJ
0 20 40 60 80 100
Naproxen
Diclofenac
Ibuprofen
Hydrocodone
Acetaminophen
% Removal
1000 mJ40 mJ
0 20 40 60 80 100
Carbamazepine
Dilantin
Diazepam
Meprobamate
Fluoxetine
Caffeine
% Removal
1000 mJ40 mJ 1000 mJ40 mJ
0 20 40 60 80 100
DEET
Atrazine
Metolachlor
Galaxolide
Musk Ketone
TCEP
Iopromide
Pentoxifylline
Gemfibrozil
% Removal
10
UV PilotUV Pilot
• Flow rate to control UV dose (3x)
• 0, 5, & 8 mg H2O2 /L
• 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)
• Medium pressure
0 20 40 60 80 100
Estriol
Ethynylestradiol
Estrone
Estradiol
Testosterone
Progesterone
Androstenedione
% Removal
UV + 8 ppm PeroxideUV + 5 ppm PeroxideUV Only
0 20 40 60 80 100
Trimethoprim
Sulfamethoxazole
Erythromycin
Triclosan
% Removal
UV + 8 ppm PeroxideUV + 5 ppm PeroxideUV Only
0 20 40 60 80 100
Naproxen
Ibuprofen
Hydrocodone
Acetaminophen
Diclofenac
% Removal
UV + 8 ppm PeroxideUV + 5 ppm PeroxideUV Only
11
0 20 40 60 80 100
Caffeine
Fluoxetine
Meprobamate
Diazepam
Dilantin
Carbamazepine
% Removal
UV + 8 ppm PeroxideUV + 5 ppm PeroxideUV Only
0 20 40 60 80 100
DEET
Atrazine
Metolachlor
TCEP
Iopromide
Pentoxifylline
Gemfibrozil
Oxybenzone
% Removal
UV + 8 ppm PeroxideUV + 5 ppm PeroxideUV Only
FullFull--scale Treatmentscale 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 ChlorineConventional Chlorine
Raw Finished % RemovalHydrocodone 1.9 <1.0 >47Trimethoprim 2.2 <1.0 >55
Acetaminophen 1.5 <1.0 >33Caffeine 74 86 0
Erythromycin 3.2 <1.0 >69Sulfamethoxazole 35 <1.0 >97
Meprobamate 10 8.0 20Dilantin 13 7.2 45TCEP 19 17 11
Carbamazepine 20 3.6 82DEET 28 32 0
Atrazine 25 27 0Iopromide 46 17 63Naproxen 16 1 >94Ibuprofen 10 21 0Triclosan 2.7 <1.0 >63
Gemfibrozil 5.8 <1.0 >83
ng/L Predicted>99>99>9918
>99>9013184
25144
25>9339
>9975
%
12
Conventional ChlorineConventional Chlorine
Raw Finished RemovalAtrazine 42 40 5
Sulfamethoxazole 27 <1.0 >96Ibuprofen 24 32 0Caffeine 11 10 9
TCEP 11 6.5 41Gemfibrozil 11 4.2 62Naproxen 10 <1.0 >90
Carbamazepine 9.6 5.7 41DEET 8.8 7.5 15
Dilantin 5.3 4.4 17Meprobamate 4.0 3.8 5Erythromycin 3.0 <1.0 >67Trimethoprim 2.3 <1.0 >57
Triclosan 1.1 <1.0 >9
ng/L% Predicted
4>9039194
75>9325151813
>96>98>97
%
Conventional ChlorineConventional Chlorine
Raw Post Clarification % RemovalSulfamethoxazole 44 <1.0 >97
Caffeine 30 27 10DEET 15 14 7TCEP 11 10 9
Carbamazepine 5.8 4.8 17Dilantin 2.2 2.0 9
Ibuprofen 1.9 1.9 0Naproxen 1.1 <1.0 >9
Predicted>9018154
251740
>93
Conventional ChlorineConventional Chlorine
Raw Finished % RemovedCaffeine 31 20 35
Sulfamethoxazole 5.6 <1.0 >82Meprobamate 2.6 2.3 12
Dilantin 3.7 2.2 41TCEP 42 5.8 86
Carbamazepine 1.2 <1.0 >17DEET 17 16 6
Atrazine 457 431 6Iopromide 6.6 7.8 0Naproxen 1.8 <1.0 >44Ibuprofen 3.6 3.0 17
Gemfibrozil 1.7 <1.0 >41
Predicted18
>9913184
25154
25>934075
Full Scale OzoneFull Scale Ozone
Raw Finished % RemovalCaffeine 4.1 <1.0 >99
Sulfamethoxazole 11 <1.0 >99Meprobamate 13 9.4 28
Dilantin 3.1 1.5 52TCEP 5.0 6.5 0
Carbamazepine 3.5 <1.0 >99DEET 4.0 2.0 50
Atrazine 1.4 <1.0 >50Estrone 1.4 <1.0 >50
Testosterone 1.0 <1.0 >50
Predicted>99>99508010
>997050
>99>99
13
Full Scale OzoneFull Scale Ozone
Raw Finished % RemovalSulfamethoxazole 9.7 <1 >90
Meprobamate 11 5.8 47Dilantin 3.2 <1 >70TCEP 4.2 4.2 0
Carbamazepine 2.4 <1 >60DEET 3.4 1.4 59
Atrazine 1.4 <1 >30
Predicted>99508010
>9970
>40
Full Scale UVFull Scale UV
Pre-UV Post-UV % RemovalCaffeine 25 27 0
Erythromycin 2.5 2.6 0Sulfamethoxazole 1.7 2.1 0
Meprobamate 10 12 0Dilantin 1.5 2.1 0TCEP 21 22 0
Carbamazepine 2.2 2.8 0DEET 3.9 4.6 0
Atrazine 8.0 8.5 0Iopromide 7.3 7.8 0Ibuprofen 6.2 8.1 0
Gemfibrozil 9.5 10 0
Predicted32435503551172
Full Scale UVFull Scale UV
Raw Finished % RemovalAtrazine 28 29 0Caffeine 24 12 50
TCEP 19 15 21Meprobamate 8.0 8.0 0Gemfibrozil 7.4 2.4 68
Sulfamethoxazole 5.8 <1.0 83DEET 5.0 4.1 18
Iopromide 4.1 4.6 0Ibuprofen 2.4 2.7 0
Acetaminophen 1.8 <1.0 44Dilantin 1.3 1.1 15
Carbamazepine 1.2 <1.0 17Erythromycin 1.0 <1.0 0
Predicted53052
435
117
1853
10
SummarySummary• Removal related to structure (and dose)
– Chlorine good for phenolics, less effective for ketones• E2, EE2, octylphenol well removed (90 - >99%)• 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
14
SummarySummary• 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…
EDCs/PPCPs can be reduced by treatment
Treatment strategies that combineprocesses 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 #3085)
CO$T:Benefit ???
Final ThoughtsFinal Thoughts
Questions