Advanced Oxidation Process: Advanced Oxidation Process: Fundamentals & ProcessFundamentals & ProcessFundamentals & Process Fundamentals & Process Applications in Water and Applications in Water and Wastewater Treatment/ReuseWastewater Treatment/ReuseWastewater Treatment/ReuseWastewater Treatment/ReuseKhalil Z. Atasi, Ph.D., P.E., BCEE, F.ASCE Khalil Z. Atasi, Ph.D., P.E., BCEE, F.ASCE S i ViS i Vi P id tP id tSenior Vice Senior Vice PresidentPresidentCamp Dresser & McKee Inc.Camp Dresser & McKee Inc.&&Kathy A. Traexler, P.E. Kathy A. Traexler, P.E. Project Engineer Project Engineer Camp Dresser & McKee IncCamp Dresser & McKee IncCamp Dresser & McKee Inc.Camp Dresser & McKee Inc.

Air Products Technology SymposiumAir Products Technology Symposiumgy ygy yDeerfield Beach, FloridaDeerfield Beach, Florida

July July 22, 200922, 2009

Presentation OutlinePresentation Outline What is advanced oxidation (AO)?What is advanced oxidation (AO)?

Basic principle of AOBasic principle of AO ChemistryChemistry ChemistryChemistry KineticsKinetics Electrical Energy Dose(E ED)Electrical Energy Dose(E ED) Electrical Energy Dose(E ED)Electrical Energy Dose(E ED)

Type of AO processes (AOP)Type of AO processes (AOP) Type of AO processes (AOP)Type of AO processes (AOP)

AOP for treatment of emergingAOP for treatment of emerging AOP for treatment of emerging AOP for treatment of emerging contaminantscontaminants

Technology for AOPsTechnology for AOPs

Wh t i Ad d O id ti ?Wh t i Ad d O id ti ?What is Advanced Oxidation?What is Advanced Oxidation?

High rate kineticsHigh rate kinetics

Fast reactionFast reaction

Generates hydroxyl radicals (Generates hydroxyl radicals (●●OH)OH)

NonNon-- “discriminatory” reaction (non“discriminatory” reaction (non--y (y (selective)selective)

Wh t i Ad d O id ti ?Wh t i Ad d O id ti ? (C t )(C t )What is Advanced Oxidation? What is Advanced Oxidation? (Cont.)(Cont.)

E t l f tE t l f t i l ti l h ti l ti l h t Extremely fast Extremely fast –– requires relatively short requires relatively short time (on the order of seconds to minutes)time (on the order of seconds to minutes)

Small footprintsSmall footprints ideal for large flow ratesideal for large flow rates Small footprints Small footprints –– ideal for large flow ratesideal for large flow rates Detoxification/Transformation and/or Detoxification/Transformation and/or

mineralization of emerging contaminants ofmineralization of emerging contaminants ofmineralization of emerging contaminants of mineralization of emerging contaminants of concern (ECCs)concern (ECCs)

No Solid waste or residuals generation (e.g. No Solid waste or residuals generation (e.g. g ( gg ( gsludge; spent activated carbon; IX brine sludge; spent activated carbon; IX brine solution)solution)

NN l ti til ti ti id l f lti lid l f lti l NonNon--selective reaction selective reaction ideal for multiple ideal for multiple simultaneous treatment objectivessimultaneous treatment objectives

Wh t i Ad d O id ti ?Wh t i Ad d O id ti ? (C t )(C t )What is Advanced Oxidation? What is Advanced Oxidation? (Cont.)(Cont.)

P ibl hi h it l d O&M tP ibl hi h it l d O&M t Possible high capital and O&M costs Possible high capital and O&M costs (mainly power)(mainly power)

Issues with treated water stability due to Issues with treated water stability due to potential formation of AOC/BDOCpotential formation of AOC/BDOCpotential formation of AOC/BDOCpotential formation of AOC/BDOC

Generally difficult to predict the reactionsGenerally difficult to predict the reactions Generally difficult to predict the reactions Generally difficult to predict the reactions involved (mechanism and/or kinetics)involved (mechanism and/or kinetics)

Excess HExcess H22OO22 needs to be quenchedneeds to be quenched

T h lT h l AOPAOPTechnology Technology -- AOPAOP

Ad d O id ti P (AOP) fAd d O id ti P (AOP) f Advanced Oxidation Process (AOP) for Advanced Oxidation Process (AOP) for oxidizing, altering, or mineralization of oxidizing, altering, or mineralization of “Microconstituents” that otherwise can not “Microconstituents” that otherwise can not c oco st tue ts t at ot e se ca otc oco st tue ts t at ot e se ca otbe oxidized by “regular” oxidation processbe oxidized by “regular” oxidation process

Contaminants such as:Contaminants such as: EDCsEDCs PPCPsPPCPs Pesticides Pesticides HerbicidesHerbicides CyanotoxinsCyanotoxins Organoleptic compoundsOrganoleptic compounds Xenobiotic compoundsXenobiotic compounds

AOPAOP Ch i tCh i tAOP AOP -- ChemistryChemistry

Involves the generation of chemical radicalsInvolves the generation of chemical radicals Strong oxidizing reagentsStrong oxidizing reagents Hydroxyl radicals Hydroxyl radicals ●●OHOH

Highly accelerated reactionsHighly accelerated reactions Hydroxyl radicals react with many reduced Hydroxyl radicals react with many reduced

d t t t i f h i ld t t t i f h i lcompounds to start a series of chemical compounds to start a series of chemical degradation reactionsdegradation reactions

AOPs performance impacted by reactionAOPs performance impacted by reaction AOPs performance impacted by reaction AOPs performance impacted by reaction kinetics and reactor hydraulicskinetics and reactor hydraulics

AOPAOP Ch i tCh i t (C t )(C t )AOP AOP –– Chemistry Chemistry (Cont.)(Cont.)

Hydroxyl radicals react with Hydroxyl radicals react with organic organic contaminantscontaminants by different/several reaction by different/several reaction mechanisms including:mechanisms including:mechanisms, including:mechanisms, including: Hydrogen abstraction from aliphatic compounds Hydrogen abstraction from aliphatic compounds

(CH(CH33 OHOH CHCH22 OH), andOH), and(CH(CH33 OH OH CHCH22 OH), andOH), and Addition to unsaturated compoundsAddition to unsaturated compounds Followed by reaction with OFollowed by reaction with O22 initiating a seriesinitiating a series Followed by reaction with OFollowed by reaction with O22 initiating a series initiating a series

of degradation reactionsof degradation reactions In general sequence of reactions: contaminants In general sequence of reactions: contaminants

t t ft t f ld h dld h d th idi d tth idi d treact to form react to form aldehydesaldehydes, then are oxidized to , then are oxidized to carboxylic acids and ultimately become carboxylic acids and ultimately become COCO33

AOPAOP R ti Ki tiR ti Ki tiAOP AOP –– Reaction KineticsReaction Kinetics

Generation of chemical radicals Generation of chemical radicals –– strong strong id tid toxidantsoxidants

●●OH radicals are the most known and OH radicals are the most known and studiedstudied

“Advanced” as compared to “regular” “Advanced” as compared to “regular” REDOX reaction due to high rate kineticsREDOX reaction due to high rate kineticsREDOX reaction due to high rate kineticsREDOX reaction due to high rate kinetics

●●OH radicals generate series of reactionsOH radicals generate series of reactions ●●OH radicals generate series of reactionsOH radicals generate series of reactions

AOPAOP R ti Ki tiR ti Ki ti (C t )(C t )AOP AOP –– Reaction Kinetics Reaction Kinetics (Cont.)(Cont.)

R t d t i ti i i t t fR t d t i ti i i t t f Rate determination is very important for:Rate determination is very important for: Evaluation of contaminants transformationEvaluation of contaminants transformation

R t d iR t d i Reactor designReactor design

G ll d l d ( it ifi )G ll d l d ( it ifi ) Generally modeled (site specific) as :Generally modeled (site specific) as : Zero order, orZero order, or

Fi t dFi t d First orderFirst order

M tl fi t d ki tiM tl fi t d ki ti Mostly first order kineticsMostly first order kinetics

AOPAOP R ti Ki tiR ti Ki ti (C t )(C t )AOP AOP –– Reaction Kinetics Reaction Kinetics (Cont.)(Cont.) First order:First order: First order:First order:

CCe e = C= Coo exp[exp[--k (V/Q)]k (V/Q)]

CCe e , C, Coo effluent/influent concentrationeffluent/influent concentrationk first order rate constant (tk first order rate constant (t--11 ))k, first order rate constant (tk, first order rate constant (t--11 ))V, reactor volumeV, reactor volumeQ fl tQ fl tQ, flow rateQ, flow rate

High k value High k value smaller V (for a given Q)smaller V (for a given Q) Treatability studies important to determine k Treatability studies important to determine k

and feasibility of the processand feasibility of the process

Why AOs are so potent?Thermodynamics Thermodynamics (energy/feasible)(energy/feasible)

Why AOs are so potent?

ΔΔGGoo = = -- n F n F EEoonetnet

EEoonetnet = = EEoo

oxox + + EEooredred

When When EEoonetnet > 0, > 0, ΔΔGGoo < < 0, and the reaction is 0, and the reaction is

spontaneousspontaneousTh hi h th d ti t ti lTh hi h th d ti t ti l EEoo thth The higher the reduction potential, The higher the reduction potential, EEoo

redred, the , the more probable more probable EEoo

netnet to be > 0 and to be > 0 and ΔΔGGoo to be < 0 to be < 0 KineticsKinetics (reaction rate)(reaction rate)Kinetics Kinetics (reaction rate)(reaction rate)

AtrazineAtrazine + O+ O33 k = 2.3 k = 2.3 -- 24 L/mol24 L/mol--ssAt iAt i OHOH k 1 2k 1 2 2 6 102 6 1099 L/ lL/ l AtrazineAtrazine + + OH OH k = 1.2 k = 1.2 -- 2.6 x102.6 x1099 L/molL/mol--ss

[Source: Radiation Chemistry Data Center of the Notre Dame Radiation Laboratory] [Source: Radiation Chemistry Data Center of the Notre Dame Radiation Laboratory] [ y y][ y y]

AOPAOP O id ti PO id ti PAOP AOP –– Oxidation PowerOxidation Power

AOPAOP C d idi d bC d idi d b OHOHAOP AOP ––Compounds oxidized by Compounds oxidized by ●●OHOH

AOP AOP –– REACTION RATE (1REACTION RATE (1STST ORDER) ORDER) (L MOL(L MOL--11 SECSEC--11 ))(L MOL(L MOL--11 SECSEC--11 ))

Normally , hydroxyl radical Normally , hydroxyl radical concentration ranges between concentration ranges between 101088 to 10to 101010 mol.Lmol.L--1 1

PseudoPseudo--first order rate first order rate constant is between 1 and 10constant is between 1 and 10--44

secsec--11 (Glaze and Kang 1989)(Glaze and Kang 1989)secsec 1 1 (Glaze and Kang, 1989)(Glaze and Kang, 1989)

AOP AOP –– Water Treatment Technologies Water Treatment Technologies Suitability based on CODSuitability based on COD(Rodriguez, 2003)(Rodriguez, 2003)

Contaminant Levels Evolution Contaminant Levels Evolution ––Sustainable DevelopmentSustainable Development(Rodriguez, 2003)(Rodriguez, 2003)

Industrial

FecalECCs

Nutrients

AOP AOP –– Emerging ContaminantsEmerging Contaminants

AOPAOP El t i l E D (EED)El t i l E D (EED)AOP AOP –– Electrical Energy Dose (EED)Electrical Energy Dose (EED)

AOP d i b l t i lAOP d i b l t i l AOP are driven by electrical energyAOP are driven by electrical energy

Basis of Comparison: Electrical Energy Dose Basis of Comparison: Electrical Energy Dose EEDEED

Units of kWUnits of kW--hr/1,000galhr/1,000gal

EED = P/(Q*0.06) EED = P/(Q*0.06) (P i R t P i kW Q i R t(P i R t P i kW Q i R t (P is Reactor Power in kW, Q is Reactor (P is Reactor Power in kW, Q is Reactor

Flow in gpm)Flow in gpm)

AOP AOP –– Electric Energy per Order (EEO)Electric Energy per Order (EEO)gy p ( )gy p ( )

Electrical Energy per Order, EEOElectrical Energy per Order, EEO Electrical Energy per Order, EEOElectrical Energy per Order, EEO

EEO is the EED required to achieve oneEEO is the EED required to achieve one--loglog EEO is the EED required to achieve oneEEO is the EED required to achieve one--log log removal of a particular chemicalremoval of a particular chemical

EEO = EED * log(Co/EEO = EED * log(Co/CeCe)])](Co &(Co & CeCe are influent & effluent concentrations)are influent & effluent concentrations)(Co & (Co & CeCe are influent & effluent concentrations)are influent & effluent concentrations)

AOP AOP –– Electric Energy per Order Electric Energy per Order (EEO)(EEO) UVUV(EEO) (EEO) -- UVUV

EEO is a function of particular chemical, and UVEEO is a function of particular chemical, and UV EEO is a function of particular chemical, and UV EEO is a function of particular chemical, and UV reactor hydraulics, optical & electrical reactor hydraulics, optical & electrical efficienciesefficiencies

Lower EEO desiredLower EEO desired Higher EEO implies that greater electrical Higher EEO implies that greater electrical

i i d t hi l l fi i d t hi l l fenergy is required to achieve same level of energy is required to achieve same level of removalremoval

First Order Reaction: Plot of EED vs LogFirst Order Reaction: Plot of EED vs Log First Order Reaction: Plot of EED vs. Log First Order Reaction: Plot of EED vs. Log Removal is linear; slope of this plot will give Removal is linear; slope of this plot will give EEOEEO

Reactor hydraulics will affect EEOReactor hydraulics will affect EEO Use “Rated” power draws to calculate EEO’sUse “Rated” power draws to calculate EEO’spp 2 kW for LPHO2 kW for LPHO--UV, and 4 kW for MPUV, and 4 kW for MP--UVUV

AOPAOP TTAOPs AOPs -- TypesTypes

Fenton’s ProcessFenton’s Process

Ozone/Peroxide Ozone/Peroxide

UV/OzoneUV/Ozone

UV/PeroxideUV/Peroxide

UV/Peroxide/OzoneUV/Peroxide/Ozone U / e o de/O o eU / e o de/O o e

AOPAOP F t ’ PF t ’ PAOPs AOPs -- Fenton’s ProcessFenton’s Process

Ferric complexes can adsorb in the near UV andFerric complexes can adsorb in the near UV and Ferric complexes can adsorb in the near UV and Ferric complexes can adsorb in the near UV and up to 500 nm visible rangeup to 500 nm visible range

Fe(II) +peroxide at pH= 3Fe(II) +peroxide at pH= 3--4 will generate 4 will generate ●●OHOH

Fenton Reaction occurs without photochemical Fenton Reaction occurs without photochemical initiationinitiation

Effective with:Effective with:hi h t i t t tihi h t i t t ti high contaminant concentration high contaminant concentration

low UVT water, orlow UVT water, or High natural concentrationHigh natural concentration High natural concentrationHigh natural concentration

AOPAOP F t ’ PF t ’ PAOPs AOPs –– Fenton’s ProcessesFenton’s Processes

the Fenton Reagentthe Fenton ReagentHalf ReactionsHalf Reactions

HH22OO22 + 2H+ 2H++ + 2e+ 2e-- 2H2H22OOHH OO OH OHOH OHHH22OO22 + e+ e-- OH + OHOH + OH--

FeFe2+ 2+ FeFe3+3+ + e+ e--

OverallOverallOverallOverall

FeFe2+2+ + H+ H OO FeFe3+3+ ++ OH + OHOH + OH--FeFe22 + H+ H22OO22 FeFe33 + + OH + OHOH + OH

AOPAOP O /P id (“O /P id (“PP ”)”)AOPs AOPs –– Ozone/Peroxide (“Ozone/Peroxide (“PeroxonePeroxone”)”)

OO OHOH OO33 OHOH–– in neutral to basic solutions Oin neutral to basic solutions O33 will decompose will decompose

to OHto OHto OHto OH

HH22OO22 + O+ O33 ●●OHOH–– HH OO accelerates the decompositionaccelerates the decomposition–– HH22OO22 accelerates the decompositionaccelerates the decomposition

Issues with bromate formation (depending on Issues with bromate formation (depending on the source water); however, controllablethe source water); however, controllable); ,); ,

Very attractive cost as compared to other Very attractive cost as compared to other AOPs processesAOPs processes

Meets LT2ESWTR and S2DBP requirementsMeets LT2ESWTR and S2DBP requirements

AOPSAOPS UV/OUV/OAOPS AOPS –– UV/OzoneUV/Ozone Ozone absorbs UV in the 200Ozone absorbs UV in the 200--300 nm300 nm Ozone absorbs UV in the 200Ozone absorbs UV in the 200 300 nm 300 nm

resulting in a singlet Oresulting in a singlet O22 generation, which generation, which results in results in ●●OH formationOH formation

UVUV--C (C ( = 200 = 200 –– 280 nm)280 nm) HH22OO22 2 2 ●● OHOH

Rarely used due to high cost and can not Rarely used due to high cost and can not compete with other AOPscompete with other AOPs

Inefficient method to produce Inefficient method to produce ●●OHOH

AOPs AOPs –– UV/PeroxideUV/Peroxide

Has received a lot of interest in drinking Has received a lot of interest in drinking ggwater due to the LT2 ESWTR barrier against water due to the LT2 ESWTR barrier against Cryptosporidium and Giardia Cryptosporidium and Giardia (disinfection) (disinfection) concurrently with organic compoundconcurrently with organic compoundconcurrently with organic compound concurrently with organic compound oxidation. Attractive with adenovirus.oxidation. Attractive with adenovirus.

Organic pollutant “removal” is achievedOrganic pollutant “removal” is achieved Organic pollutant removal is achieved Organic pollutant removal is achieved either by photolysis or AO (hydroxyl radical)either by photolysis or AO (hydroxyl radical)

Significant concentrations (>5 mg/L) of HSignificant concentrations (>5 mg/L) of H22OO2222 22are required due to molar absorption are required due to molar absorption coefficients of peroxide at 200coefficients of peroxide at 200--300 nm300 nm

UVUV C (C ( 200200 280 ) ( t i ld i280 ) ( t i ld i UVUV--C (C ( = 200 = 200 –– 280 nm) (quantum yield is 280 nm) (quantum yield is optimal) up to optimal) up to HH OO 22 ●● OHOH HH22OO22 2 2 ●● OHOH

AOPAOP UV/P idUV/P idAOPs AOPs –– UV/PeroxideUV/Peroxide

Key water quality parameters have impacts:Key water quality parameters have impacts: pHpH TemperatureTemperature TOCTOC UVT UVT Carbonate alkalinityCarbonate alkalinity IronIron ManganeseManganese

AOPsAOPs-- UV/PeroxideUV/PeroxideF ti f UV Ab b d b 10 /L HF ti f UV Ab b d b 10 /L H OOFraction of UV Absorbed by 10 mg/L HFraction of UV Absorbed by 10 mg/L H22OO22Anipsitakis, FWEAAnipsitakis, FWEA 20082008

25%

20%UV254 abs = 0.05 cm-1

10%

15%

1

5%

10% UV254 abs = 0.2 cm-1

0%Drinking Water Wastewater

AOPsAOPs-- UV / PeroxideUV / PeroxideAOPsAOPs UV / Peroxide UV / Peroxide Overcoming Low Overcoming Low ●●OH YieldOH Yield

Increasing HIncreasing H22OO2 2 dose ( min 5 dose ( min 5 ppmppm))

AOPsAOPs-- UV / PeroxideUV / PeroxideAOPsAOPs UV / Peroxide UV / Peroxide Overcoming Low Overcoming Low ●●OH YieldOH Yield

Increasing HIncreasing H22OO2 2 dose ( min 5 ppm)dose ( min 5 ppm) Increasing UV Increasing UV fluencefluence

AOPsAOPs-- UV / PeroxideUV / PeroxideAOPsAOPs UV / Peroxide UV / Peroxide Overcoming Low Overcoming Low ●●OH YieldOH Yield

Increasing HIncreasing H22OO2 2 dose ( min 5 ppm)dose ( min 5 ppm) Increasing UV fluenceIncreasing UV fluence Reducing UVReducing UV254 254 absorbance (increasing absorbance (increasing

UVT):UVT): MixedMixed--media filtrationmedia filtration Membrane processesMembrane processes

AOPsAOPs-- UV / PeroxideUV / PeroxideAOPsAOPs UV / Peroxide UV / Peroxide Overcoming Low Overcoming Low ●●OH YieldOH Yield

Increasing HIncreasing H22OO2 2 dose ( min 5 ppm)dose ( min 5 ppm) Increasing UV fluenceIncreasing UV fluence Reducing UVReducing UV254 254 absorbance (increasing absorbance (increasing

UVT):UVT): MixedMixed--media filtrationmedia filtration Membrane processesMembrane processes

Alternatives to HAlternatives to H22OO22

Peracetic acid (Acetic acid with peroxide)Peracetic acid (Acetic acid with peroxide)

AOPsAOPs-- UV / PeroxideUV / PeroxideAOPsAOPs UV / Peroxide UV / Peroxide Overcoming Low Overcoming Low ●●OH YieldOH Yield

Increasing HIncreasing H22OO2 2 dose ( min 5 ppm)dose ( min 5 ppm) Increasing UV fluenceIncreasing UV fluence Reducing UVReducing UV254 254 absorbance (increasing absorbance (increasing

UVT):UVT): MixedMixed--media filtrationmedia filtration Membrane processesMembrane processes

Alternatives to HAlternatives to H22OO22

Peracetic acid (Acetic acid with peroxide)Peracetic acid (Acetic acid with peroxide) HOClHOCl

UV/HOClUV/HOCl UV/HUV/H OOUV/HOCl UV/HOCl vsvs UV/HUV/H22OO22

Rapid photochemical conversion of HOCl to OHRapid photochemical conversion of HOCl to OH Rapid photochemical conversion of HOCl to OHRapid photochemical conversion of HOCl to OH

●●OH from HOCl/OClOH from HOCl/OCl-- and Hand H22OO2222 22

Yield of Yield of ●●OHOHOClOCl-- < < < H< < < H22OO22 < HOCl< HOCl22 22

Energy required for Energy required for ●●OH generation and organics OH generation and organics id tiid tioxidationoxidation

–– At lowAt low--mgmg--LL--11 oxidant doses in surface wateroxidant doses in surface waterEnergyEnergyHOClHOCl ≤ Energy≤ EnergyH2O2H2O2 <<<< EnergyEnergyOClOClEnergyEnergyHOClHOCl ≤ Energy≤ EnergyH2O2H2O2 EnergyEnergyOClOCl--

AOPAOP UV/O /P idUV/O /P idAOPs AOPs –– UV/Ozone/PeroxideUV/Ozone/Peroxide

Addition of peroxide will further enhance the Addition of peroxide will further enhance the f ti f h d l di lf ti f h d l di lformation of hydroxyl radicalsformation of hydroxyl radicals

Not used in drinking water or wastewater Not used in drinking water or wastewater treatment due to costtreatment due to cost

Mainly used in the detoxification of RCRA Mainly used in the detoxification of RCRA types of waste materials such as PAHstypes of waste materials such as PAHstypes of waste materials, such as PAHs types of waste materials, such as PAHs

T h lT h l AOP/AOP/ HiPOXHiPOXTechnology Technology –– AOP/ AOP/ HiPOXHiPOX

T h lT h l AOP/AOP/ HiPOXHiPOX (C t )(C t )Technology Technology –– AOP/ AOP/ HiPOXHiPOX (Cont.)(Cont.)

T h lT h l AOP/AOP/ HiPOXHiPOX (C t )(C t )Technology Technology –– AOP/ AOP/ HiPOXHiPOX (Cont.) (Cont.)

Meets California Meets California Tile 22 for total Tile 22 for total coliform of 2.2 coliform of 2.2 MPN/100mLMPN/100mLMPN/100mLMPN/100mL

AOPAOP O l tiO l ti C dC dAOP AOP –– OrganolepticOrganoleptic CompoundsCompounds

A- Geosmin B- MIB

F t Aff ti O ti fF t Aff ti O ti fFactors Affecting Ozonation of Factors Affecting Ozonation of Odorants Odorants (Atasi et. al, 2001)(Atasi et. al, 2001)

200

100

150

Effe

ct, %

Test A error bars represent

50

100

dard

ized

E Test B standard errors for effect estimation

0Sta

nd

-50

atur

e

dose

2O2

atio

nnt do

se

H2O

2

poin

t

Tem

pera

O3

d H2

Ozo

napo

in

Tem

p-d

Tem

p-H

Tem

p-p

AOP AOP –– Ozone/PeroxideOzone/PeroxideG iG iGeosminGeosmin(Atasi et.al. 1999)(Atasi et.al. 1999)

150

R2 = 0.9958100c., n

g/L O3, raw

O3/H2O2, raw

R2 = 0.878850

100

min

Con

,

O3, settled

R2 = 0.9628

0

50

Geo

sm

00 1 2 3 4

T f d O D /LTransferred Ozone Dose, mg/L

AOP AOP –– Ozone/PeroxideOzone/PeroxideMIB, MIB, GeosminGeosmin, and IPMP Treatment, and IPMP Treatment(Atasi et.al., 2001) Isopropyl (Atasi et.al., 2001) Isopropyl MethanopirazineMethanopirazine

100 100

80

val,

%

80

val,

%

40

60

nt R

emov

MIB C 100 /L40

60

ant R

emov

MIB 1 5 /L O3

20

40

Odo

ra MIB, Co = 100 ng/L

Geosmin, Co = 125 ng/L

IPMP, Co = 182 ng/L 20

40

Odo

ra MIB,1.5 mg/L O3Geosmin, 1.5 mg/L O3IPMP, 1.5 mg/L O3

00.5 1 1.5 2 2.5

0200 300 400 500 600

Transferred Ozone Dose, mg/L Total Odorant Spike, ng/L

AOPAOP UV/P idUV/P idAOP AOP –– UV/PeroxideUV/Peroxide

AOPAOP UV/P idUV/P idAOP AOP –– UV/PeroxideUV/Peroxide

AOP AOP –– UV/PeroxideUV/PeroxideMIB treatment LPHO UVMIB treatment LPHO UV(Atasi et. al. 2004)(Atasi et. al. 2004)

100

80

H2O2 = 6 mg/L

60

egrada

tion

H2O2 = 4 mg/L

40

Percent De

H2O2 = 0 mg/L

20

0

0.0 0.2 0.4 0.6 0.8 1.0EED (kW-Hr/1,000 gal)

AOP AOP –– UV/PeroxideUV/PeroxideATZ Degradation LPHO UVATZ Degradation LPHO UV(Atasi, et. al., 2004)(Atasi, et. al., 2004)

100H2O2 = 6 mg/L

80

on

H2O2 = 4 mg/L

60

t Deg

rada

tio

H2O2 = 0 mg/L

20

40

Perc

ent

0

20

0.0 0.2 0.4 0.6 0.8 1.0

EED (kW-Hr/1,000 gal)

AOP AOP –– UV/PeroxideUV/PeroxideMIB D d ti MP UVMIB D d ti MP UVMIB Degradation MP UVMIB Degradation MP UV(Atasi et. al., 2004)(Atasi et. al., 2004)

100

H2O2 = 6 mg/L

80

tion H2O2 = 4 mg/L

60

nt D

egra

dat

H2O2 = 0 mg/L

H2O2 4 mg/L

20

40

Perc

en

2 2 g

0

20

0

0.0 0.4 0.8 1.2 1.6 2.0

EED (kW-Hr/1,000 gal)

AOP AOP –– UV/PeroxideUV/PeroxideMIB Degradation MP UVMIB Degradation MP UV(Atasi et.al., 2004(Atasi et.al., 2004

100

80

tion

H2O2 = 4 mg/L

H2O2 = 6 mg/L

60

nt D

egra

dat

H2O2 = 0 mg/L

40

Perc

en

0

20

0

0.0 0.4 0.8 1.2 1.6 2.0

EED (kW-Hr/1,000 gal)

AOPAOP C l iC l iAOP AOP -- ConclusionsConclusions

Very effective in detoxifying ECC by Very effective in detoxifying ECC by transformation/ breakdown and/or transformation/ breakdown and/or mineralizationmineralizationmineralizationmineralization

Hi h t ki ti lti i ll f t i tHi h t ki ti lti i ll f t i t High rate kinetics resulting in small foot printHigh rate kinetics resulting in small foot print

N id l t dN id l t d No residuals are generatedNo residuals are generated

Can address multiple contaminants Can address multiple contaminants simultaneously simultaneously

AOP – Conclusions (Cont )Energy requirements for UV systemsEnergy requirements for UV systems

AOP – Conclusions (Cont.) gy q ygy q y

DisinfectionDisinfection–– Depending upon upstream filtration, UV dose needs Depending upon upstream filtration, UV dose needs p g p p ,p g p p ,

to be 60 to be 60 –– 100 100 mJmJ/cm/cm22

–– A 3A 3--6 MGD WWTP requires 132.8 kW input to the UV 6 MGD WWTP requires 132.8 kW input to the UV f di i f if di i f isystem for disinfectionsystem for disinfection

Chemical decontaminationChemical decontamination–– Energy to activate the peroxidesEnergy to activate the peroxides

–– More energy (~ by one order of magnitude) than just More energy (~ by one order of magnitude) than just disinfectiondisinfectiondisinfectiondisinfection

– Larger reactors or bigger and more lamps–– Electrical energy per order is the figure of merit usedElectrical energy per order is the figure of merit usedElectrical energy per order is the figure of merit used Electrical energy per order is the figure of merit used

in this casein this case

Th k Y !Th k Y !Thank You!Thank You!

Khalil Z. Atasi, P.E.: Khalil Z. Atasi, P.E.: AtasiKZ@cdm.comAtasiKZ@cdm.com

Kathy A. Traexler, P.E.: Kathy A. Traexler, P.E.: TraexlerKA@cdm.comTraexlerKA@cdm.com

Camp Dresser & McKee Inc.Camp Dresser & McKee Inc.2301 Maitland Center Parkway, Suite 3002301 Maitland Center Parkway, Suite 300y,y,Maitland, FL 32751 Maitland, FL 32751