Chemistry of Ozone in Water and Wastewater Treatment

305 Pages·2012·20.635 MB·English

by  Clemens von Sonntag, Urs von Gunten

C
h
e
m
Even though ozone has been applied for a long time for disinfection and is
t
oxidation in water treatment, there is lack of critical information related to r
y
transformation of organic compounds. This has become more important in
o
recent years, because there is considerable concern about the formation f

o
of potentially harmful degradation products as well as oxidation products
z
from the reaction with the matrix components. In recent years, a wealth of o
n
information on the products that are formed has accumulated, and substantial
e

progress in understanding mechanistic details of ozone reactions in aqueous i
n
Chemistry of ozone in Water
solution has been made. Based on the latter, this may allow us to predict W
the products of as yet not studied systems and assist in evaluating toxic a
t
potentials in case certain classes are known to show such effects. Keeping e and WasteWater treatment
r

this in mind, Chemistry of Ozone in Water and Wastewater Treatment: a
n
From Basic Principles to Applications discusses mechanistic details of ozone
d
reactions as much as they are known to date and applies them to the large W From Basic Principles to Applications
body of studies on micropollutant degradation (such as pharmaceuticals a
s
and endocrine disruptors) that is already available. Extensively quoting the t
e
literature and updating the available compilation of ozone rate constants W
a
gives the reader a text at hand on which his research can be based. Moreover, t
e
those that are responsible for planning or operation of ozonation steps in r

t
drinking water and wastewater treatment plants will find salient information
r
e
in a compact form that otherwise is quite disperse. a
t
m
A critical compilation of rate constants for the various classes of compounds
e
is given in each chapter, including all the recent publications. This is a very n
t
useful source of information for researchers and practitioners who need
kinetic information on emerging contaminants. Furthermore, each chapter
C
contains a large selection of examples of reaction mechanisms for the lem
e
n
transformation of micropollutants such as pharmaceuticals, pesticides, fuel s
v
o
additives, solvents, taste and odor compounds, cyanotoxins. n
S
o
n
n
ta
g
a
n
d
U
r
s
v
o
n
G
u
n
te
n
Clemens von Sonntag
www.iwapublishing.com
ISBN: 9781843393139 (Hardback) Urs von Gunten
ISBN: 9781780400839 (eBook)
ChemistryofOzone_layout_4.0 1 01/08/2012 10:47
Chemistry of Ozone in Water and
Wastewater Treatment
Chemistry of Ozone in Water and
Wastewater Treatment
From Basic Principles to Applications
Clemens von Sonntag and Urs von Gunten
Publishedby IWAPublishing
AllianceHouse
12CaxtonStreet
LondonSW1H0QS,UK
Telephone:[phone]
Fax:[phone]
Email:[email protected]
Web:www.iwapublishing.com
Firstpublished2012
©2012IWAPublishing
Coverimage:OzoneGeneratorOzonia,DegrementTechnologies,withpermission.
Photograph:UrsvonGunten.
CoverDesign:TimovonGuntenandSixteenDesign(www.sixteen-design.co.uk)
Apartfromanyfairdealingforthepurposesofresearchorprivatestudy,orcriticismorreview,aspermittedundertheUK
Copyright,DesignsandPatentsAct(1998),nopartofthispublicationmaybereproduced,storedortransmittedinany
form or by any means, without the prior permission in writing of the publisher, or, in the case of photographic
reproduction, in accordance with the terms of licenses issued by the Copyright Licensing Agency in the UK, or in
accordance with the terms of licenses issued by the appropriate reproduction rights organization outside the UK.
EnquiriesconcerningreproductionoutsidethetermsstatedhereshouldbesenttoIWAPublishingattheaddressprinted
above.
Thepublishermakesnorepresentation,expressorimplied,withregardtotheaccuracyoftheinformationcontainedinthis
bookandcannotacceptanylegalresponsibilityorliabilityforerrorsoromissionsthatmaybemade.
Disclaimer
TheinformationprovidedandtheopinionsgiveninthispublicationarenotnecessarilythoseofIWAandshouldnotbeacted
uponwithoutindependentconsiderationandprofessionaladvice.IWAandtheAuthorwillnotacceptresponsibilityforany
lossordamagesufferedbyanypersonactingorrefrainingfromactinguponanymaterialcontainedinthispublication.
BritishLibraryCataloguinginPublicationData
ACIPcataloguerecordforthisbookisavailablefromtheBritishLibrary
ISBN9781843393139(Paperback)
ISBN9781780400839(eBook)
Contents
About the Authors .......................................................... xi
Chapter 1
Historical background and scope of the book ................................ 1
Chapter 2
Physical and chemical properties of ozone .................................. 7
2.1 IntroductoryRemarks ......................................................... 7
2.2 GenerationofOzone ......................................................... 8
2.3 OzoneSolubilityinWater ..................................................... 9
2.4 UV–VISSpectrumofOzone .................................................. 10
2.5 DeterminationoftheOzoneConcentration ..................................... 12
2.5.1 TheN,N-diethyl-p-phenylenediamine(DPD)method ....................... 12
2.5.2 Theindigomethod .................................................... 13
2.6 MethodsforMeasuringOzoneKinetics ........................................ 14
2.6.1 Ozonedecaymeasurements ........................................... 15
2.6.2 Quenchingofozonewithbuten-3-ol ..................................... 16
2.6.3 Reactiveabsorption ................................................... 16
2.6.4 Competitionkinetics .................................................. 17
2.7 ReductionPotentialsofOzoneandOtherOxygenSpecies ....................... 18
2.8 StabilityofOzoneSolutions .................................................. 19
2.9 ReactivityofOzone ......................................................... 19
2.9.1 pHdependenceofozonereactionsandthe“reactivitypK” ................. 20
2.9.2 Multiplereactionsiteswithinonemolecule ............................... 21
Chapter 3
Ozone kinetics in drinking water and wastewater ........................... 23
3.1 StabilityofOzoneinVariousWaterSources .................................... 23
vi ChemistryofOzoneinWaterandWastewaterTreatment
3.2 MolecularWeightDistributionofDissolvedOrganicMatter ........................ 31
3.3 MineralisationandChemicalOxygenDemand .................................. 33
3.4 FormationofAssimilableOrganicCarbon ...................................... 33
3.5 FormationandMitigationofDisinfectionBy-products ............................. 35
3.6 UVAbsorbanceofDissolvedOrganicMatter .................................... 36
3.7 RelevanceofOzoneKineticsfortheEliminationofMicropollutants ................. 37
(cid:129)
3.8 HydroxylRadicalYieldand OH-ScavengingRateofDissolved
OrganicMatter ............................................................. 39
3.9 EliminationofOzone-RefractoryMicropollutantsbythe†OHRoute ................ 40
3.10 Ozone-basedAdvancedOxidationProcesses .................................. 42
3.10.1 Peroxoneprocess ................................................... 42
3.10.2 UVphotolysisofozone ............................................... 45
3.10.3 Reactionofozonewithactivatedcarbon ................................ 46
Chapter 4
Inactivation of micro-organisms and toxicological assessment of
ozone-induced products of micropollutants ................................ 49
4.1 DisinfectionKinetics ......................................................... 49
4.2 InactivationMechanisms:RoleofMembranesandDNA .......................... 52
4.3 ReactionswithNucleicAcidComponents ...................................... 53
4.4 ReactionwithDNA .......................................................... 54
4.5 ApplicationofOzoneforDisinfectioninDrinkingWaterandWastewater ............ 55
4.6 ToxicologicalAssessmentofOzoneInducedTransformationProducts ............. 55
4.7 EndocrineDisruptingCompounds ............................................. 56
4.7.1 Laboratorystudies .................................................... 58
4.7.2 Full-scalestudies ..................................................... 59
4.8 AntimicrobialCompounds .................................................... 60
4.9 Toxicity .................................................................... 62
Chapter 5
Integration of ozonation in drinking water and wastewater
process trains ............................................................. 65
5.1 HistoricalAspects ........................................................... 65
5.1.1 Drinkingwater ....................................................... 65
5.1.2 Municipalwastewater ................................................. 65
5.2 DrinkingWaterTreatmentSchemesIncludingOzonation ......................... 66
5.3 MicropollutantsinWaterResources,DrinkingWaterandWastewater .............. 70
5.4 EnhancedWastewaterTreatmentwithOzone ................................... 72
5.5 EnergyRequirementsforMicropollutantTransformationinDrinkingWater
andWastewater ............................................................ 73
5.6 SourceControl ............................................................. 74
5.7 ReclamationofWastewater .................................................. 75
5.8 ComparisonoftheApplicationofOzoneintheUrbanWaterCycle ................. 77
Contents vii
Chapter 6
Olefins .................................................................... 81
6.1 ReactivityofOlefins ......................................................... 81
6.2 TheCriegeeMechanism ..................................................... 84
6.3 PartialOxidation ............................................................ 87
6.4 DecayoftheOzonideviaFreeRadicals ........................................ 88
6.5 Detectionofa-Hydroxyalkylhydroperoxides ..................................... 88
6.6 OzoneReactionsofOlefins–ProductsandReactionsofReactiveIntermediates .... 89
6.6.1 Methyl-andhalogen-substitutedolefins .................................. 89
6.6.2 Acrylonitrile,vinylacetate,diethylvinylphosphonate,vinylphenylsulfonate,
vinylsulfonicacidandvinylenecarbonate ................................ 91
6.6.3 Acrylic,methacrylic,fumaric,maleicandmuconicacids .................... 92
6.6.4 Muconicacids ....................................................... 96
6.6.5 Cinnamicacids ....................................................... 98
6.6.6 Dichloromaleicacid ................................................... 99
6.6.7 Pyrimidinenucleobases ............................................... 99
6.7 MicropollutantswithOlefinicFunctions ........................................ 102
Chapter 7
Aromatic compounds ..................................................... 109
7.1 ReactivityofAromaticCompounds ........................................... 109
7.2 DecayofOzoneAdducts .................................................... 116
7.3 OzoneReactionsofAromaticCompounds–ProductsandReactionsofReactive
Intermediates .............................................................. 118
7.3.1 Methoxylatedbenzenes .............................................. 118
7.3.2 Phenols ............................................................ 121
7.4 MicropollutantswithAromaticFunctions ....................................... 124
Chapter 8
Nitrogen-containing compounds .......................................... 131
8.1 ReactivityofNitrogen-containingCompounds .................................. 131
8.2 GeneralMechanisticConsiderations .......................................... 138
8.2.1 Aliphaticamines ..................................................... 138
8.2.2 Aromaticamines(anilines) ............................................ 143
8.2.3 Nitrogen-containingheterocycliccompounds ............................ 145
8.3 MicropollutantswithNitrogen-containingFunctions ............................. 146
8.3.1 TheN-nitrosodimethylamine(NDMA)puzzle ............................ 156
Chapter 9
Reactions of sulfur-containing compounds ................................ 161
9.1 ReactivityofSulfur-containingCompounds .................................... 161
9.2 Thiols .................................................................... 162
viii ChemistryofOzoneinWaterandWastewaterTreatment
9.3 Sulfides,DisulfidesandSulfinicAcids ......................................... 163
9.4 Sulfoxides ................................................................ 165
9.5 MicropollutantsContaininganOzone-reactiveSulfur ............................ 166
Chapter 10
Compounds with C–H functions as ozone-reactive sites .................... 169
10.1 ReactivityofCompoundswithC–HFunctionsasOzone-reactiveSites ........... 169
10.2 GeneralMechanisticConsiderations ......................................... 171
10.3 FormateIon .............................................................. 173
10.4 2-Methyl-2-Propanol(TertiaryButanol) ....................................... 175
10.5 2-Propanol ............................................................... 176
10.6 Carbohydrates ........................................................... 180
10.7 DihydrogenTrioxide–PropertiesofaShort-livedIntermediate .................. 182
10.8 SaturatedMicropollutantsLackingOzone-reactiveHeteroatoms ................. 184
Chapter 11
Inorganic anions and the peroxone process ............................... 185
11.1 IntroductoryRemarks ...................................................... 185
11.2 HydroxideIon ............................................................ 187
11.3 HydroperoxideIon–PeroxoneProcess ...................................... 188
11.4 Fluoride ................................................................. 189
11.5 Chloride ................................................................. 190
11.6 Hypochlorite .............................................................. 191
11.7 Chlorite .................................................................. 192
11.8 Bromide ................................................................. 192
11.9 Hypobromite ............................................................. 193
11.10 Bromite .................................................................. 194
11.11 Iodide ................................................................... 194
11.12 Nitrite ................................................................... 195
11.13 Azide .................................................................... 196
11.14 HydrogenSulfide ......................................................... 197
11.15 HydrogenSulfite .......................................................... 198
11.16 BromateFormationandMitigationinWaterTreatment ......................... 198
11.17 Bromide-catalysedReactions ............................................... 201
11.18 MitigationofIodide-relatedProblems ........................................ 202
Chapter 12
Reactions with metal ions ................................................. 205
12.1 ReactivityofMetalIons .................................................... 205
12.2 Arsenic .................................................................. 206
12.3 Cobalt ................................................................... 207
12.4 Copper .................................................................. 207
Contents ix
12.5 Iron ..................................................................... 207
12.6 Lead .................................................................... 208
12.7 Manganese .............................................................. 208
12.8 Selenium ................................................................ 209
12.9 Silver ................................................................... 209
12.10 Tin ...................................................................... 211
12.11 MetalIonsasMicropollutants ............................................... 211
Chapter 13
Reactions with free radicals ............................................... 213
13.1 ReactivityofRadicals ..................................................... 213
13.2 OzoneReactionswithReducingRadicals .................................... 214
13.3 OzoneReactionswithCarbon-centeredRadicals .............................. 215
13.4 OzoneReactionswithOxygen-centeredRadicals ............................. 217
13.5 OzoneReactionswithNitrogen-andSulfur-centredRadicals ................... 219
13.6 OzoneReactionswithHalogen-centredRadicals .............................. 220
Chapter 14
Reactions of hydroxyl and peroxyl radicals ................................ 225
14.1 IntroductoryRemarks ..................................................... 225
14.2 HydroxylRadicalReactions ................................................ 225
14.2.1 Additionreactions ................................................. 225
14.2.2 H-abstractionreactions ............................................. 227
14.2.3 Electrontransferreactions .......................................... 228
(cid:129)
14.3 Determinationof OHRateConstants ........................................ 229
(cid:129)
14.4 Detectionof OHinOzoneReactions ........................................ 230
(cid:129)
14.5 Determinationof OHYieldsinOzoneReactions .............................. 232
14.6 FormationofPeroxylRadicals .............................................. 233
14.7 RedoxPropertiesofPeroxylRadicalsandReactionwithOzone ................. 233
14.8 UnimolecularDecayofPeroxylRadicals ..................................... 234
14.9 BimolecularDecayofPeroxylRadicals ...................................... 235
14.10 ReactionsofOxylRadicals ................................................. 236
(cid:129)
14.11 Involvementof OHRadicalsinChlorateandBromateFormation ................ 237
14.11.1 Chlorateformation ................................................ 237
14.11.2 Bromateformation ................................................ 238
14.12 DegradationofOzone-refractoryMicropollutantsby(cid:129)OH/PeroxylRadicals ........ 241
14.12.1 Saturatedaliphaticcompounds ..................................... 241
14.12.2 Aromaticcompounds ............................................. 243
14.12.3 Chlorinatedolefins ............................................... 245
14.12.4 Perfluorinatedcompounds ......................................... 248
References ............................................................... 249
Index ..................................................................... 287
About the Authors
Prof.DrClemensvonSonntag
Max-Plack-InstitutfürBioanorganischeChemie,D-45470MülheimanderRuhr,Germany,
(retired:postaladdress:Bleichstr.16,D-45468MülheimanderRuhr)
and
InstitutfürInstrumentelleAnalytik,UniversitätDuisburg-Essen,D-45117Essen.
(email:[email protected])
Prof.DrUrsvonGunten
DepartmentofWaterResourcesandDrinkingWater,Eawag,SwissFederalInstituteof
AquaticScienceandTechnology,CH-8600Dübendorf,Switzerland
and
InstituteofEnvironmentalEngineering,SchoolofArchitecture,CivilandEnvironmental
Engineering,ENAC,EcolePolytechniqueFédéraleLausanne,EPFL,CH-1012Lausanne.
(email:[email protected])