Nanotechnology for environmental remediation

169 Pages·2010·2.36 MB·English

by  Sung Hee Joo

NanotechnologyforEnvironmentalRemediation
ModernInorganicChemistry
SeriesEditor:JohnP.Fackler,Jr.,TexasA&MUniversity
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NanotechnologyforEnvironmentalRemediation
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OrganometallicChemistryoftheTransitionElements
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D.M.Roundhill
Sung Hee Joo
I. Francis Cheng
Nanotechnology for
Environmental Remediation
With79Illustrations
SungHeeJoo I.FrancisCheng
EnvironmentalEngineeringProgram DepartmentofChemistry
CivilEngineeringDepartment UniversityofIdaho
AuburnUniversity Moscow,ID83844
Auburn,AL36849 USA
USA [email protected]
[email protected]
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Preface
Thebookcoverstherecentlydiscoveredoxidativeprocessdrivenbyzero-valent
iron (ZVI) in the presence of oxygen and a further developed system which is
namedZEA(Zero-valentiron,EDTA,Air).Futurepotentialapplicationsforenvi-
ronmentalremediationusingthisprocessarealsodiscussed.Theoxidativeprocess
wasdiscoveredduringthecourseofmolinate(athiocarbamateherbicide)degrada-
tionexperiments.Bothferrousironandsuperoxide(or,atpH<4.8,hydroperoxy)
radicalsappeartobegeneratedoncorrosionoftheZVIwithresultantproduction
ofstronglyoxidizingentitiescapableofdegradingthetracecontaminant.Fenton
oxidationandoxidativeby-productswereobservedduringnanosizedZVI(nZVI)-
mediateddegradationofmolinateunderaerobicconditions.Toassessthepotential
applicationofnZVIforoxidativetransformationoforganiccontaminants,thecon-
version of benzoic acid (BA) to p-hydroxybenzoic acid (p-HBA) was used as a
probereaction.WhennZVIwasaddedtoBA-containingwater,aninitialpulseof
p-HBAwasdetectedduringthefirst30minutes,followedbytheslowgeneration
ofadditionalp-HBAoverperiodsofatleast24hours.TheZEAsystemshowed
thatchlorinatedphenols,organophosphorusandEDTAhavebeendegraded.The
mechanism by which the ZEA reaction proceeds is hypothesized to be through
reactiveoxygenintermediates.TheZVI-mediatedoxidationandZEAsystemmay
beusefulforinsituapplicationsofnZVIparticlesandmayalsoprovideameans
ofoxidizingorganiccontaminantsingranularZVI-containingpermeablereactive
barriers.
Thepurposeofthisbookistoprovideinformationontherecentlydiscovered
chemicalprocess,whichcouldrevolutionizethetreatmentofpesticidesandcon-
taminated water. It also aims to offer significant insights to the knowledge for
potentialapplicationsofZVI-basedtechnology.
Oxidative degradation of herbicides (e.g., molinate) with its pathway, mecha-
nisticinterpretationofthedata,modelling/simulation,implicationforremediation
applications,experimentalmethodologysuitableforpesticidesanalysis,andZEA
(Zero-valent iron, EDTA, and Air) system with its degradation mechanism are
included.
v
Acknowledgments
WewouldliketodeeplyacknowledgeDr.ChristinaNoradounwhocontributedher
expertiseinChapter5.Dr.Joowishestothankformermentors,ProfessorDavid
WaiteandDr.AndrewFeitzfortheiradviceduringresearchonthistopic.Special
thanksgotoDr.JosephPignatellowhoprovidedinsightfulcommentsinpreparing
themanuscript.
Finally we would like to appreciate reviewers’ comments, which improve the
quality of this book and the senior editor, Kenneth Howell who supported us in
thepreparationofthisbook.
vii
Contents
Preface................................................................................... v
Acknowledgments..................................................................... vii
AbbreviationsandSymbols........................................................ xiii
Chapter1. Introduction........................................................... 1
1.1. Objectives....................................................................... 2
1.2. Outlines......................................................................... 3
Chapter2. LiteratureReview.................................................... 5
2.1. Zero-ValentIron(ZVI)....................................................... 5
2.1.1. IronUseintheEnvironment....................................... 5
2.1.2. NanoparticulateBimetallicandIronTechnology.............. 7
2.1.3. PermeableReactiveBarrier(PRB)UsingGranularZVI..... 8
2.1.4. PRBandZVIColloids.............................................. 9
2.1.5. UseofZVI,H O ,andComplexants............................ 10
2 2
2.1.6. NanosizedZVI(nZVI).............................................. 11
2.2. PesticidesandContamination............................................... 12
2.2.1. Introduction........................................................... 12
2.2.2. CharacteristicsofPesticidesandTheir
EnvironmentalEffects.............................................. 13
2.2.3. CommonlyUsedPesticides........................................ 16
2.2.4. PesticidesTreatmentandManagementPractices.............. 18
2.3. Summary........................................................................ 22
Chapter3. NanoscaleZVIParticlesManufacture
andAnalyticalTechniques.......................................................... 25
3.1. SynthesisofNanoscaleZVIParticles..................................... 25
3.1.1. ZVIParticleCharacterization...................................... 26
3.2. AnalyticalTechniques........................................................ 28
3.2.1. Solid-PhaseMicroextractionGC/MSD.......................... 28
3.2.2. HPLCAnalysisofBenzoicAcidandp-HydroxybenzoicAcid 34
ix
x Contents
3.2.3. MeasurementofFerrousIronConcentrations.................. 34
3.2.4. MeasurementofHydrogenPeroxide
(H O )Concentrations.............................................. 34
2 2
3.3. ProceduresUsedinnZVI-MediatedDegradationStudies............. 35
3.3.1. MolinateDegradation............................................... 35
3.3.2. BenzoicAcidDegradation......................................... 36
3.4. ExperimentalSetupUsedinZEASystemStudies ..................... 37
3.5. DeterminationofZVISurfaceProductsbyXRD....................... 39
3.5.1. MeasurementsinthePresenceofMolinate..................... 40
3.5.2. MeasurementsintheAbsenceofMolinate..................... 40
Chapter4. OxidativeDegradationoftheThiocarbamate
Herbicide,Molinate,UsingNanoscaleZVI..................................... 41
4.1. Introduction.................................................................... 41
4.2. Results........................................................................... 41
4.2.1. EffectofthePresenceofAir/Oxygen............................ 41
4.2.2. EffectofMolinateandZVIConcentration...................... 42
4.2.3. EffectofpH........................................................... 44
4.2.4. FerrousIronGeneration............................................ 45
4.2.5. EffectofDO.......................................................... 52
4.2.6. HydrogenPeroxideGeneration................................... 53
4.2.7. CatalaseandButanolCompetition................................ 55
4.2.8. DegradationBy-products .......................................... 56
4.3. MolinateDegradationbyCombinedZVIandH O .................... 58
2 2
4.3.1. EffectofZVIatFixedHydrogen
PeroxideConcentration ............................................ 60
4.3.2. EffectofHydrogenPeroxideatConstantZVI................. 60
4.3.3. DegradationBy-productsbyCombinedZVIandH O ...... 61
2 2
4.3.4. Fe(II)GenerationfromCoupledZVI/H O inthe
2 2
PresenceofMolinate................................................ 64
4.4. MolinateDegradationUsingFenton’sReagent.......................... 64
4.4.1. DegradationBy-productsofMolinateUsing
Fenton’sReagents................................................... 67
4.5. ComparisonofZVI,CoupledZVI/H O andFenton’s
2 2
ProcessatHighpH............................................................ 69
4.6. XRDandXPSAnalysis...................................................... 69
4.6.1. ResultsofXRDAnalysis........................................... 69
4.6.2. XPSResults........................................................... 73
4.7. Discussion...................................................................... 73
4.7.1. EvidenceofOxidationPathway................................... 73
4.7.2. ReactionMechanism................................................ 75
4.7.3. KineticsofFe(II)andH O Generation......................... 79
2 2
4.7.4. OverviewoftheZVI-MediatedOxidativeTechnology ...... 79
4.8. Conclusion...................................................................... 80
Contents xi
Chapter5. MolecularOxygenActivationbyFeII/IIIEDTA
asaFormofGreenOxidationChemistry∗..................................... 83
5.1. OxygenActivation............................................................ 83
5.2. XenobioticDegradationbyZEASystem................................. 85
5.3. MechanismofDegradation.................................................. 87
5.4. Rate-DeterminingStep....................................................... 88
5.5. IronChelationandChelateGeometryInfluenceReactivity........... 91
5.6. FormofReactiveOxygenIntermediateSpecies ........................ 94
5.7. Conclusion...................................................................... 95
Chapter6. QuantificationoftheOxidizingCapacityof
NanoparticulateZero-ValentIronandAssessmentof
PossibleEnvironmentalApplications............................................ 97
6.1. Introduction.................................................................... 97
6.2. Results........................................................................... 98
6.2.1. p-Hydroxybenzoicacid(p-HBA)Formation................... 98
6.2.2. CumulativeHydroxylRadicalFormationover
LongTerm............................................................. 98
6.2.3. EffectofFe(II)asOxidantScavenger............................ 100
6.2.4. EffectofZVIConcentrationsonOxidantYield................ 101
6.2.5. EffectofpH........................................................... 103
6.2.6. SelectivityofOxidant............................................... 103
6.2.7. EffectofZVITypeonOxidantYields........................... 109
6.2.8. ComparisonStudyonStandardFentonOxidationof
BenzoicAcid ......................................................... 109
6.2.9. EffectofPureO onOxidantYield.............................. 110
2
6.2.10.Discussion............................................................. 113
6.2.11.ConceptualKineticModeling..................................... 115
6.3. Conclusion...................................................................... 120
Chapter7. ConclusionsandFutureResearchNeeds...................... 123
7.1. ColumnStudies................................................................ 123
7.2. FurtherApplicationsoftheZVI-MediatedOxidativeProcess........ 124
7.3. SummaryofResults.......................................................... 125
7.4. OverviewofnZVIResearchandFurtherResearchNeeds............ 127
Chapter8. References............................................................. 129
AppendixA:XRDAnalysisofZVICollectedfrom
FourDifferentSamples.............................................................. 147
AppendixB:XRDAnalysisofZVICollectedfrom
FourDifferentSamples.............................................................. 149
xii Contents
AppendixC:ELISAAnalysisMethodology.................................... 151
AppendixD:OvenProgramsforGC/MSAnalysisofPesticides.......... 155
AppendixE:ExperimentalConditionsforPesticidesand
PreliminaryScreeningStudiesUsingNanoscaleZVI........................ 157
Index...................................................................................... 163