Chiral Pollutants: Distribution, Toxicity and Analysis by Chromatography and Capillary Electrophoresis

353 Pages·2004·1.54 MB·English

by  Imran Ali

Chiral Pollutants:
Distribution, Toxicity
and Analysis by
Chromatography
and Capillary
Electrophoresis
Imran Ali
National Institute of Hydrology, Roorkee, India
and
Hassan Y. Aboul-Enein
King Faisal Specialist Hospital, Riyadh, Saudi Arabia
Copyright2004 JohnWiley&SonsLtd,TheAtrium,SouthernGate,Chichester,
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LibraryofCongressCataloging-in-PublicationData
Aboul-Enein,HassanY.
Chiralpollutants:distribution,toxicity,andanalysisby
chromatographyandcapillaryelectrophoresis/HassanY.Aboul-Eneinand
ImranAli.
p.cm.
Includesbibliographicalreferencesandindex.
ISBN0-470-86780-9(cloth:alk.paper)
1.Environmentaltoxicology.2.Enantiomers--Toxicology.3.
Enantiomers--Separation.4.Chromatographicanalysis.5.Capillary
electrophoresis.I.Ali,Imran.II.Title.
RA1226.A262004
615.9(cid:1)02--dc22
2003024672
BritishLibraryCataloguinginPublicationData
AcataloguerecordforthisbookisavailablefromtheBritishLibrary
ISBN0-470-86780-9
Typesetin11/13ptTimesNewRomanbyLaserwordsPrivateLimited,Chennai,India
PrintedandboundinGreatBritainbyAntonyRoweLtd,Chippenham,Wiltshire
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Dedication
Dedicatedtothememoriesofmylateparents:
BasheerAhmedandMehmudanBegum
ImranAli
Tomylovingfamily:
Nagla,Youssef,FaisalandBasil
fortheirsupportandencouragement
HassanY.Aboul-Enein
Contents
Preface xiii
Acknowledgements xv
AbouttheBook xvii
AbouttheAuthors xix
1 Introduction 1
1.1 TheImportanceoftheEnvironment 1
1.2 EnvironmentalPollutants 2
1.3 ChiralityanditsOccurrence 3
1.4 TheChemicalEvolutionofChirality 4
1.5 TheElectronicTheoryofChirality 6
1.6 TheImportanceofChirality 7
1.7 NomenclatureforChiralPollutants 8
1.8 ChiralityinEnvironmentalPollutants 10
1.9 ChiralityanditsConsequencesintheEnvironment 12
1.10 TheEnantiomericRatioandFractionsofChiralPollutants 13
1.11 MethodsfortheSeparationofChiralPollutants 15
1.11.1 ChromatographicMethods 16
1.11.2 TheCapillaryElectrophoreticMethod 21
viii Contents
1.12 ChiralSelectorsinChromatographyandCapillary
Electrophoresis 23
1.13 DetectioninChromatographyandCapillary
Electrophoresis 27
1.14 OtherMethodsofSeparationofChiralPollutants 28
References 30
2 ChiralPollutants:SourcesandDistribution 37
2.1 Introduction 37
2.2 SourcesofContamination 39
2.3 TheDistributionofChiralPollutants 44
2.3.1 DistributioninWater 44
2.3.2 DistributioninSediment 49
2.3.3 DistributioninSoil 50
2.3.4 DistributioninAir 53
2.3.5 DistributioninAquaticandAmphibianBiota 55
2.3.6 DistributioninTerrestrialBiota 60
2.3.7 DistributioninFoodProducts 67
2.4 Conclusions 67
References 68
3 ChiralPollutants:Biotransformation,Biodegradation
andMetabolism 75
3.1 Introduction 75
3.2 TheMechanismsoftheInteractionsofChiralXenobiotics
inBiologicalSystems 77
3.3 TheFateofChiralPollutantsintheEcosystem 81
3.3.1 Biotransformation 81
3.4 PhotochemicalConversion 95
3.5 Metabolism 96
3.6 Conclusions 102
References 103
4 TheEnantioselectiveToxicitiesofChiralPollutants 109
4.1 Introduction 109
4.2 TheEnantioselectiveToxicitiesofPCBs 110
4.3 TheEnantioselectiveToxicitiesofHCH 116
Contents ix
4.4 TheEnantioselectiveToxicitiesofOtherChlorinated
Pesticides 117
4.5 TheEnantioselectiveToxicitiesofPhosphorousPesticides 121
4.6 TheEnantioselectiveToxicitiesofPolyaromatic
Hydrocarbons(PAHs) 121
4.7 TheEnantioselectiveToxicitiesofOtherXenobiotics 134
4.8 TheEnantioselectiveToxicitiesofDrugsand
Pharmaceuticals 136
4.9 Conclusions 139
References 140
5 SamplePreparation 145
5.1 Introduction 145
5.2 Sampling 147
5.3 Filtration 148
5.4 Homogenization 149
5.5 Extraction 150
5.5.1 TheExtractionofSolidSamples 150
5.5.2 TheExtractionofLiquidSamples 161
5.6 MembraneMethodsinSamplePreparation 172
5.7 Clean-up 173
5.8 Pre-concentration 174
5.9 Conclusions 176
References 176
6 TheAnalysisofChiralPollutantsbyGasChromatography 185
6.1 Introduction 185
6.2 ChiralSelectors 186
6.2.1 StructuresandProperties 187
6.2.2 PreparationandCommercialization 189
6.2.3 OtherChiralGCCSPs 190
6.3 Applications 195
6.4 TheOptimizationofGCConditions 206
6.4.1 MobilePhases 207
6.4.2 Temperature 208
6.4.3 TheColumnDimensions 211
6.4.4 StructuresandTypesofChiralSelectors 212
6.4.5 TheStructuresofChiralPollutants 215
x Contents
6.4.6 Detection 215
6.4.7 OtherParameters 216
6.5 TheReverseElutionOrder 217
6.6 ErrorsandProblemsinEnantioresolution 218
6.7 TheDerivatizationofChiralEnvironmentalPollutants 219
6.8 MechanismsofChiralResolution 219
6.9 Conclusions 221
References 222
7 TheAnalysisofChiralPollutantsbyHighPerformance
LiquidChromatography 229
7.1 Introduction 229
7.2 ChiralSelectors 230
7.3 Applications 233
7.4 TheOptimizationofHPLCConditions 238
7.4.1 PolysaccharideCSPs 239
7.4.2 CyclodextrinCSPs 245
7.4.3 MacrocyclicGlycopeptideAntibioticCSPs 249
7.4.4 ProteinCSPs 253
7.4.5 ChiralCrownEtherCSPs 258
7.4.6 LigandExchangeCSPs 260
7.4.7 Pirkle-typeCSPs 262
7.5 Detection 265
7.6 ChiralRecognitionMechanisms 265
7.7 Conclusions 266
References 268
8 TheAnalysisofChiralPollutantsbyMicellarElectrokinetic,
CapillaryElectrochromatographic,SupercriticalFluidand
ThinLayerChromatographicTechniques 273
8.1 Introduction 273
8.2 ChiralSelectors 274
8.3 MicellarElectrokineticChromatography(MEKC) 274
8.4 CapillaryElectrochromatography (CEC) 281
8.5 SupercriticalFluidChromatography(SFC) 284
8.6 ThinLayerChromatography(TLC) 287
8.7 LCversusGC 289
8.8 Conclusions 289
References 290
Contents xi
9 TheAnalysisofChiralEnvironmentalPollutants
byCapillaryElectrophoresis 295
9.1 Introduction 295
9.2 ChiralSelectors 296
9.3 Applications 297
9.4 TheOptimizationofCEConditions 302
9.4.1 TheCompositionoftheBackgroundElectrolyte 304
9.4.2 ThepHoftheBackgroundElectrolyte 305
9.4.3 TheIonicStrengthoftheBackgroundElectrolyte 306
9.4.4 StructuresandTypesofChiralSelectors 308
9.4.5 TheAppliedVoltage 308
9.4.6 Temperature 310
9.4.7 TheStructuresofChiralPollutants 311
9.4.8 OrganicModifiers 312
9.4.9 OtherParameters 312
9.4.10 OptimizationbyDependentVariables 315
9.5 Detection 315
9.6 ValidationofMethods 317
9.7 MechanismsofChiralResolution 318
9.8 CEversusHPLC 319
9.9 Conclusions 320
References 321
10 PerspectivesontheAnalysisofChiralPollutants 325
10.1 Introduction 325
10.2 RegulationsonChiralityintheUSA 326
10.3 RegulationsonChiralityinEurope 327
10.4 RegulationsonChiralityinJapan 328
10.5 RegulationsonChiralityinOtherCountries 328
10.6 TheCapabilitiesofChiralAnalysisTechnologies 329
10.7 TheLarge-scaleProductionofPureEnantiomers 329
10.8 TheImpactofChiralityonEconomicGrowth 330
10.9 Conclusions 331
References 332
Index 335
Preface
One of the two enantiomers of a chiral pollutant may be more toxic than
theother,andabout25%ofagrochemicalsarechiralinnature–including
pesticides, which are applied in agricultural and forestry activities in the
form of their racemates. The biological transformation of chiral pollutants
can be stereoselective, such that the uptake, metabolism and excretion
of the enantiomers may be very different. Therefore, the enantiomeric
composition of chiral pollutants may be changed during these processes.
Themetabolitesofchiralcompoundsareoftenchiral.Therefore,topredict
the exact toxicities of pollutants, determination of the concentrations
of both enantiomers is essential, and hence environmental scientists are
eagerly seeking techniques for their analysis. Moreover, diverse groups of
people–ranging from regulators tothe materials industries,clinicians and
nutritional experts, agriculturalists and environmentalists–are also now
demandingdataontheratioofpollutantenantiomers,ratherthantheirtotal
concentrations.
Various approaches to chiral resolution have been developed for the
analysis of pharmaceuticals and drugs but, unfortunately, few reports and
monographs areavailableonthechiralseparationofpollutants.Therefore,
we have set out to write this book, which deals with the distribution,
toxicities and art of analysis of chiral pollutants by gas chromatography
and liquid chromatography; that is, by high performance liquid chro-
matography (HPLC), sub- and supercritical fluid chromatography (SFC),