removal of edcs and awwarf project #2758: ppcps by

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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

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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

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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

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0 20 40 60 80 100

Acetaminophen

Hydrocodone

Ibuprofen

Diclofenac

Naproxen

% Removal


0 20 40 60 80 100

Carbamazepine

Dilantin

Diazepam

Meprobamate

Fluoxetine

Caffeine

% Removal


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

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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


0 20 40 60 80 100

Acetaminophen

Hydrocodone

Ibuprofen

Diclofenac

Naproxen

% Removal


8


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


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

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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

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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


0 20 40 60 80 100

Naproxen

Ibuprofen

Hydrocodone

Acetaminophen

Diclofenac

% Removal


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0 20 40 60 80 100

Caffeine

Fluoxetine

Meprobamate

Diazepam

Dilantin

Carbamazepine

% Removal


0 20 40 60 80 100

DEET

Atrazine

Metolachlor

TCEP

Iopromide

Pentoxifylline

Gemfibrozil

Oxybenzone

% Removal


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


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

%


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


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

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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

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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

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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

[email protected]

Questions

removal of edcs and awwarf project #2758: ppcps by

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