Electron Beam Technology:Electron Beam Technology:Environmental ApplicationsEnvironmental Applications

William J. CooperWilliam J. Cooper

Director and ProfessorDirector and ProfessorUrban Water Research CenterUrban Water Research Center

Department of Civil and Environmental EngineeringDepartment of Civil and Environmental EngineeringUniversity of California, IrvineUniversity of California, Irvine

Irvine, CA 92697Irvine, CA 92697

wcooper@uci.edu

Overview of WaterOverview of Water Water availability/sustainabilityWater availability/sustainability

Water reuseWater reuse

Water treatment through the COWater treatment through the CO22 lens lens

ConsiderationsConsiderations Pharmaceuticals and other emerging chemicals of concernPharmaceuticals and other emerging chemicals of concern Biosolids/sludge treatmentBiosolids/sludge treatment RO Retentate TreatmentRO Retentate Treatment Engineered nanoparticles in waterEngineered nanoparticles in water Agricultural Production – food and waterAgricultural Production – food and water Economic models for assessing options in waterEconomic models for assessing options in water Salinity and agricultural practicesSalinity and agricultural practices InfrastructureInfrastructure Smart Water SystemsSmart Water Systems Reinvestigation of innovative water treatment processesReinvestigation of innovative water treatment processes

Historical PerspectiveHistorical Perspective 1988 – received funds from the NSF to refurbish 1988 – received funds from the NSF to refurbish

and operate the Electron Beam Research and operate the Electron Beam Research Facility, Miami, FL (1988 – 2001)Facility, Miami, FL (1988 – 2001)

1989 – incorporated High Voltage Environmental 1989 – incorporated High Voltage Environmental Applications (1989 – 2011)Applications (1989 – 2011)

Conducted large scale and pilot scale studies on Conducted large scale and pilot scale studies on over 150 compounds.over 150 compounds.

To my surprise – published 59 papers and 22 To my surprise – published 59 papers and 22 chapters in bookschapters in books

On the team that had On the team that had B. anthraces B. anthraces data before data before the letters were receivedthe letters were received

Electron Beam Research Electron Beam Research Facility – Miami, FLFacility – Miami, FL

Large Scale Studies

Large Scale Studies - Electron Beam Research Facility

Large Scale Studies - Electron Beam Research Facility

Large Scale Studies - Electron Beam Research Facility

Operating Electron BeamOperating Electron BeamAccelerator = 1.5 MeV; 75 kW

Scanned to penetrate water or vapor 100 – 150 gallons per minute

EBRF – Miami, FLEBRF – Miami, FL Located at a wastewater treatment plantLocated at a wastewater treatment plant Had four input lines (up to 150 gpm)Had four input lines (up to 150 gpm)

Drinking waterDrinking water Secondary treated wastewaterSecondary treated wastewater Digested sludge (now referred to as biosolids)Digested sludge (now referred to as biosolids) Tanker/2500 gallon tank in yard to receive any sample Tanker/2500 gallon tank in yard to receive any sample

that was shipped to the facilitythat was shipped to the facility

Separate electrical line to measure energy Separate electrical line to measure energy consumptionconsumption

Problem – we called it a research facilityProblem – we called it a research facility

Mobile Electron BeamMobile Electron BeamSavannah River Site – EPA Savannah River Site – EPA

Demonstration – 1994 Sept – Nov.Demonstration – 1994 Sept – Nov.

Cross Section thru Mobile UnitCross Section thru Mobile Unit

Research ApproachChemistry

Laboratory Experiments Large Scale Studies “Real World”

Kinetic Information Product Identification Removal Information

Contaminant Removal Understanding/AOP Application

Initial StudiesInitial Studies

ChloroformTCEPCEBenzeneToluenePhenolCarbon Tetrachloride

ConditionsConditions

Three influent concentrationsThree pH’s – to test effect of carbonate

– 5 or less– 7– 9

With and without solids (3 % kaolin)4 doses (including a zero dose)

ConclusionsConclusionsCarbonate/bicarbonate effects

treatment– used pH to study this– has different effects on different

compoundsSolids (3 % clay) did not effect

treatmentEach compound is different in it removal

pattern

Organic Compound Removal using Organic Compound Removal using the the

E-Beam ProcessE-Beam Process

0

10

20

30

40

50

60

70

80

90

100

Experiment A

MTBE

TCE

PCE

Benzene

Toluene

E-Benzene

o-Xylene

CHCL3

EDB

NDMA

Atrazine

Simazine

Advantages of E-BeamAdvantages of E-Beam

The most efficient process for generating The most efficient process for generating hydroxyl radicals, •OH, the defining hydroxyl radicals, •OH, the defining reactive species for Advanced Oxidation reactive species for Advanced Oxidation Processes (AOPs)Processes (AOPs)Measured 72 % efficiency from wall power to Measured 72 % efficiency from wall power to

chemistrychemistryNo need of additives – only the electronsNo need of additives – only the electronsSolids do not interfere with the processSolids do not interfere with the process

Advantages of E-BeamAdvantages of E-Beam

•Simultaneously generates oxidizing (•OH) and reducing (e-, •H) radicals

• Based on aqueous radiation chemistry

H2O \/\/\/\/\/ 2.7 •OH + 0.6 •H + 2.6 e-

+ 0.45 H2 + 0.7 H2O2 + 2.6 H+

Advantages of E-BeamAdvantages of E-Beam

Dose(kGy)

Concentration(mM)

•OH e-aq H• H2O2

1 0.28 0.27 0.06 0.07

5 1.4 1.4 0.3 0.4

10 2.8 2.7 0.7 0.7

Advantages of E-BeamAdvantages of E-Beam

Equipment is reliable – with Insulated Equipment is reliable – with Insulated Core Transformers (ICTs) having 98 – 99 Core Transformers (ICTs) having 98 – 99 % uptime% uptimeMobile trailer machine built in 1963Mobile trailer machine built in 1963

No residuals – e.g. sludge's etc.No residuals – e.g. sludge's etc.

Advantages of E-Beam;Advantages of E-Beam;Design ConsiderationDesign Consideration

Early ApproachEarly Approach

We obtained a lot of phenomenological We obtained a lot of phenomenological data on contaminant removaldata on contaminant removalEffect of pH – really the impact of the Effect of pH – really the impact of the

carbonate/bicarbonate system on pollutant carbonate/bicarbonate system on pollutant removalremoval

Dose destruction curves – all first order (conc. Dose destruction curves – all first order (conc. vsvs dose) dose)

Effect of solidsEffect of solids

Early ApproachEarly Approach

Mid-1990’s we started to model the system Mid-1990’s we started to model the system using AECL’s MAKISIMA CHEMISTusing AECL’s MAKISIMA CHEMISTPC’s back then were slow – 2 hours a run PC’s back then were slow – 2 hours a run

(now 5 – 10 seconds on lap tops)(now 5 – 10 seconds on lap tops)

Modeling showed that pulsed beams (with Los Modeling showed that pulsed beams (with Los Alamos) were not as efficient as continuous Alamos) were not as efficient as continuous beamsbeamsHad to do with recombination of radicals at Had to do with recombination of radicals at

high doses of pulsed systemshigh doses of pulsed systems

Large Scale Studies - Example: Thioanisole Removal

pH 5 pH 9

Laboratory Conditions - Kinetic Information

Rate Constant Results For Each Initial Radical Reacting WithThioanisole (TA):

kIIobs = 1.2 x 109 M-1s-1

kIIobs = 3.1 x 108 M-1s-1

kIIobs = 1.1 x 1010 M-1s-1

Removal Simulation - Comparison of Simulation and Large Scale Results

pH 5 pH 9

Red = SimulationBlack = Exp. Values

Early ApproachEarly Approach

Then measuring new reaction rate constants at Then measuring new reaction rate constants at NDRL – opened more detailed modelingNDRL – opened more detailed modeling

More recently have started to deal with by-More recently have started to deal with by-products of reactions using gamma – photons as products of reactions using gamma – photons as the source (NDRL, INL, and UCI)the source (NDRL, INL, and UCI)

Pharmaceutical and Personal Care Products have been studied

Pharmaceutical Pharmaceutical and Personal and Personal

Care Products Care Products CompoundCompound

Reaction RatesReaction Rates

ReferencesReferences••OHOH (M(M-1-1 s s-1-1)) ee--aqaq (M(M-1-1 s s-1-1))

Lipid RegulatorsLipid Regulators

Clofibric AcidClofibric Acid (6.98(6.980.12) × 100.12) × 1099 (6.59(6.590.43) ×100.43) ×1088 B. Razavi, W. Song, B. Razavi, W. Song, William J. Cooper et alWilliam J. Cooper et al J. J. Phys. Chem. A.Phys. Chem. A. 2009, 2009, 113113, 1287 , 1287

BenzafibrateBenzafibrate (8.00(8.000.22) × 100.22) × 1099 (1.12(1.120.03) × 100.03) × 101010

GemfibrozilGemfibrozil (10.0(10.00.60) × 100.60) × 1099 (6.26(6.260.58) × 100.58) × 1088

Insect repellentInsect repellent DEETDEET (4.95±0.18) × 10(4.95±0.18) × 1099 ((1.34±0.04) × 101.34±0.04) × 1099W. Song, W. Cooper et. W. Song, W. Cooper et. al.al. Water Research.Water Research. 2009, 2009, 4343, 635, 635

Beta-blockerBeta-blockerAtenololAtenolol (7.05(7.050.27) × 100.27) × 1099 (5.91(5.910.21) ×100.21) ×1088 W. Song W. Cooper et. W. Song W. Cooper et.

al. al. Environ. Sci. Technol.Environ. Sci. Technol. 20082008, , 4242, 1256, 1256

MetoprololMetoprolol (8.39(8.390.06) × 100.06) × 1099 (1.73(1.730.03) ×100.03) ×1088

PropranololPropranolol (1.07(1.070.02) × 100.02) × 101010 (1.26(1.260.02) ×100.02) ×101010

Beta-lactamBeta-lactam(Antibio(Antibiotics)tics)

Penicillin GPenicillin G (7.97(7.970.11) ×100.11) ×1099 (3.92(3.920.10) ×100.10) ×1099 W. SongW. Song,, W. Cooper et. al. W. Cooper et. al. J. Phys. Chem. A.J. Phys. Chem. A. 2008 2008, , 112112 ,7411 ,7411

Penicillin VPenicillin V (8.76(8.760.28) ×100.28) ×1099 (5.76(5.760.24) ×100.24) ×1099

AmoxicillinAmoxicillin (6.94(6.940.44) ×100.44) ×1099 (3.47(3.470.07) ×100.07) ×1099

FluoroquinolonesFluoroquinolones

DanofloxacinDanofloxacin (6.15(6.150.11) ×100.11) ×1099 (1.68(1.680.02) ×100.02) ×101010

H. Santoke, W. Song, W. H. Santoke, W. Song, W. Cooper et al.Cooper et al. J. Phys. J. Phys. Chem. AChem. A. . 20092009 113113, 7846 , 7846

OrbifloxacinOrbifloxacin (6.94(6.940.08) ×100.08) ×1099 (2.25(2.250.02) ×100.02) ×101010

MarbofloxacinMarbofloxacin (9.03(9.030.39) ×100.39) ×1099 (2.41(2.410.02) ×100.02) ×101010

EnrofloxacinEnrofloxacin (7.95(7.950.23) ×100.23) ×1099 (1.89(1.890.02) ×100.02) ×101010

FlumequineFlumequine (8.26(8.260.28) ×100.28) ×1099 (1.83(1.830.01) ×100.01) ×101010

Pharmaceutical Pharmaceutical and Personal and Personal

Care Products Care Products CompoundCompound

Reaction RatesReaction Rates

ReferencesReferences••OHOH

(M(M-1-1 s s-1-1))ee--

aqaq

(M(M-1-1 s s-1-1))

AntibioticsAntibiotics

TetracyclineTetracycline (6.34(6.340.11) × 100.11) × 1099 (2.16(2.160.08) × 100.08) × 101010J. Jeong, W. SongJ. Jeong, W. Song W. J. Cooper, et al W. J. Cooper, et al Chemosphere 2010, Chemosphere 2010, 78, 53378, 533

ChlortetracyclineChlortetracycline (5.20(5.200.23) × 100.23) × 1099 (1.32(1.320.18) × 100.18) × 101010

OxytetracyclineOxytetracycline (5.63(5.630.03) × 100.03) × 1099 (2.32(2.320.05) × 100.05) × 101010

DoxycyclineDoxycycline (7.58(7.580.12) × 100.12) × 1099 (2.52(2.520.02) × 100.02) × 101010

Non-Steroidal Non-Steroidal anti-anti-

inflammatoryinflammatory

DiclofenacDiclofenac (9.29 ± 0.11) × 10(9.29 ± 0.11) × 1099 (1.53 ± 0.03) × 10(1.53 ± 0.03) × 1099

Manuscripts in Manuscripts in Prepare Prepare IbuprofenIbuprofen (5.97 ± 0.22) × 10(5.97 ± 0.22) × 1099 (4.76 ± 0.18) × 10(4.76 ± 0.18) × 1088

NaproxenNaproxen (7.53 ± 0.26) × 10(7.53 ± 0.26) × 1099 (2.43 ± 0.13) × 10(2.43 ± 0.13) × 1099

X-ray contrast X-ray contrast agentsagents

DiatrizoateDiatrizoate (9.58 (9.58 0.23) × 10 0.23) × 1088 (2.13 (2.13 0.03) × 10 0.03) × 101010

J. Jeong, W. SongJ. Jeong, W. Song **, , W. J. Cooper, et al W. J. Cooper, et al Water ResearchWater Research

IohexolIohexol (3.21 (3.21 0.13) × 10 0.13) × 1099 (3.35 (3.35 0.03) × 10 0.03) × 101010

IopromideIopromide (3.34 (3.34 0.14) × 10 0.14) × 1099 (3.25 (3.25 0.05) × 10 0.05) × 101010

IomeprolIomeprol (2.03 (2.03 0.13) × 10 0.13) × 1099 (3.47 (3.47 0.02) × 10 0.02) × 101010

IopamidolIopamidol (3.42 (3.42 0.28) × 10 0.28) × 1099 (3.37 (3.37 0.05) × 10 0.05) × 101010

AntibioticAntibiotic TrimethoprimTrimethoprim (8.34 (8.34 0.47) × 10 0.47) × 1099 (1.36 (1.36 0.01) × 10 0.01) × 101010 Luo et al., Luo et al., Wat. ResWat. Res. . 2012, 46, 1327 2012, 46, 1327

On going projects related with PPCPs

Early ApproachEarly Approach

More More recently – due to lack of a pilot facility recently – due to lack of a pilot facility we have turned to gamma sources (NDRL, we have turned to gamma sources (NDRL, INL, and UCI) to work on INL, and UCI) to work on mechanismmechanismAlso requires extensive mass spec capabilityAlso requires extensive mass spec capability

From a chemical point of view – we have From a chemical point of view – we have explored the efficiency of the actual explored the efficiency of the actual reactionsreactions

300 350 400 450 5000.000

0.005

0.010

0.015

0.020

0.025

Ab

sorb

an

ce

Wavelength (nm)

1 s 5 s 50 s 100 s 250 s

HN

Cl

O

ONaCl

300 350 400 450 500

0.000

0.005

0.010

0.015

0.020

0.025

Ab

sorb

an

ce

Wavelength (nm)

1 s 5 s 50 s 100 s 250 s

NH2

Cl

Cl

Compare transit Spectra of diclofenac with model Compare transit Spectra of diclofenac with model compoundcompound

HN

Cl

ONa

O

Cl

OH rate constant(6.97 0.24) x 109

75%

ee--aqaq rate constant rate constant

(1.61 ± 0.03) × 10(1.61 ± 0.03) × 1099

105% 105%

Portion of OH and ePortion of OH and e--aqaq reaction with diclofenac and function group reaction with diclofenac and function group

HN

OH

O

Cl

Cl

Diclofenac

HN

OH

O

Cl OH

Cl HN

OH

O

ClHO

Cl

HN

OH

O

O

Cl

N

Cl

Cl

O

OH

O

HN

OH

O

Cl

Cl

HO

HN

OH

O

Cl

OH

MW 311 MW 311MW 311

MW 275MW 309

MW 277

Degradation Mechanism of OH radical oxidation of Diclofenac

NH

OH

O

Cl

Cl

NH

OH

O

Cl

NH

OH

O

Cl

NHOH

O

Cl

NHOH

O

Diclofenac

MW 261MW 261 MW 259

MW 225

Degradation Mechanism of e-aq Reduction of diclofenac

0 2 4 6 80.0

0.1

0.2

0.3

0.4

0.5

0.6

a

Co

nce

ntr

atio

n o

f G

em

fib

rozil

(mM

)

Irradiation dose (kGy) 0 1 2 3 4 5 6 7 8

0.0

0.1

0.2

0.3

0.4

0.5

0.6

b

Co

nce

ntr

atio

n o

f C

lofib

ric A

cid

(m

M)

Irradiation dose (kGy)

0 1 2 3 4 5 6 7 8

0.0

0.1

0.2

0.3

0.4

0.5

0.6

c

Co

nce

ntr

atio

n o

f B

eza

fib

rate

(m

M)

Irradiation dose (kGy)

Gemfibrozil (a) slope= -1.87 x 10-4 M kGy-1

Clofibric acid (b)slope= -3.47 x 10-4 M kGy-1

Bezafibrate (c) Slope= -4.85 x 10-4 M kGy-1

Efficiency reaction of both Efficiency reaction of both ••OH OH and eand e--

aqaq with clofibrates: with clofibrates:

98 % with bezafibrate98 % with bezafibrate

95 % with clofibric acid 95 % with clofibric acid

62 % with gemfibrozil62 % with gemfibrozil

ApplicationsApplications

Have ‘played’ in the chemical and Have ‘played’ in the chemical and biological warfare arenabiological warfare arena

ChemicalsChemicals

Chemical DestructionChemical Destruction

Biological DestructionBiological Destruction

Biological SummaryBiological Summary

  MEAN DOSE REQUIRED (kGy)

AGENT 1 log kill 4 log kill

Bacillus subtillis var globigii (BG) spores

1.34 6.00

Bacillus anthracis sterne spores

3.27 10.40

Influenza virus 5.65 22 (approximately)

Serratia marcescens 0.043 0.174

MarketsMarkets

Environmental market is enormous and will Environmental market is enormous and will remain that wayremain that way

Environmental markets are very fragmentedEnvironmental markets are very fragmented

Environmental markets are VERY risk adverseEnvironmental markets are VERY risk adverse

PROBLEM – no one wants to be first to PROBLEM – no one wants to be first to install a full scale plantinstall a full scale plant

VERY risk adverse – opportunities for VERY risk adverse – opportunities for out of the box thinkingout of the box thinking

There are no installed E-Beams for environmental There are no installed E-Beams for environmental applications in the US?applications in the US?

The industry will NOT take a chance – at all – and that in The industry will NOT take a chance – at all – and that in part stems from the regulatory oversightpart stems from the regulatory oversight

Whenever you are talking environmental remediation – it Whenever you are talking environmental remediation – it is always a “red” on the bottom lineis always a “red” on the bottom line

The remediation market is totally regulatory drivenThe remediation market is totally regulatory driven

Water – Food = A Market?Water – Food = A Market?

World food production will have to increase 70 % World food production will have to increase 70 % by 2050by 2050

A very large market exists in food irradiation for A very large market exists in food irradiation for pest control – in the import and export marketspest control – in the import and export marketsJust visited a fruit pacing facility in the CA Just visited a fruit pacing facility in the CA

central valley not totally sure this is a target central valley not totally sure this is a target BUT there are possibilities – water and food BUT there are possibilities – water and food

E-Beam TechnologyE-Beam TechnologyWhat are the Markets?What are the Markets?

Wastewater treatment – Wastewater treatment – biosolidsbiosolids Working with Arlington WWTP to show that process Working with Arlington WWTP to show that process

can eliminate endocrine disruptorscan eliminate endocrine disruptors Then they have agreed to put in a full scale Then they have agreed to put in a full scale

demonstration plantdemonstration plant

Water Reuse – Water Reuse – RO retentates or reject waterRO retentates or reject water

Food IrradiationFood Irradiation

Agricultural – Agricultural – pest managementpest management

CommercializationCommercializationOnly one company has made it through the Only one company has made it through the

valley of death – EB Tech of Korea – Dr. valley of death – EB Tech of Korea – Dr. Bumsoo HanBumsoo HanMajor area is that he has reduced the capital Major area is that he has reduced the capital

cost of equipment tremendouslycost of equipment tremendouslyWe paid for e-beam (75 kW system in 1980) - We paid for e-beam (75 kW system in 1980) -

$1.5 million$1.5 millionEB Tech has a 400 kW system for around $2 EB Tech has a 400 kW system for around $2

M M

CommercializationCommercialization

Radiation Dynamics – Dynamitron - now a Radiation Dynamics – Dynamitron - now a member of IBA is around (Long Island)member of IBA is around (Long Island)

Jacob Applebaum – in central Florida is Jacob Applebaum – in central Florida is very interested – was involved in food very interested – was involved in food irradiationirradiation

Biggest problem with many E “beamers” is Biggest problem with many E “beamers” is that always want to build a new systemthat always want to build a new system

ThoughtsThoughts We have never quite figured out how to REALLY We have never quite figured out how to REALLY

assist ‘start-up’ companies commercialize new assist ‘start-up’ companies commercialize new processesprocesses

There needs to have thought given to a location There needs to have thought given to a location for testing and validation (third party)for testing and validation (third party)

Nobody wants to be first in the environmental Nobody wants to be first in the environmental field – especially where capital costs are high field – especially where capital costs are high

E Beam – no clients could get over the initial E Beam – no clients could get over the initial cost – even though O & M was minimalcost – even though O & M was minimal

Need to develop a system where biological Need to develop a system where biological treatment is last step and testedtreatment is last step and tested