TOOLS,TECHNIQUES ANDPROTOCOLS FORMONITORING ENVIRONMENTAL CONTAMINANTS
Editedby
SATINDERKAURBRAR
KRISHNAMOORTHYHEGDE
VINAYAKLAXMANPACHAPUR
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Contributors
BalRamAdhikari
LaboratoryofBiosensorsandNanomachines,DepartmentofChemistry,UniversityofMontreal, Montreal,QC,Canada
ShadabAhmed
InstituteofBioinformaticsandBiotechnology,SavitribaiPhulePuneUniversity(Formerly UniversityofPune),Pune,India
V.Amrutha
ElectronicsandCommunicationEngineering,NationalInstituteofTechnologyRourkela, Rourkela,India
AntonioAvalos-Ramı ´ rez
NationalCenterinEnvironmentalTechnologyandElectrochemistry,Shawinigan,QC,Canada
RajMohanBalakrishnan
DepartmentofChemicalEngineering,NationalInstituteofTechnology,Surathkal,India
FatimaBendourou
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
SatinderKaurBrar
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
MonaChaali
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
JipingChen
CASKeyLaboratoryofSeparationScienceforAnalyticalChemistry,DalianInstituteof ChemicalPhysics,ChineseAcademyofSciences,Dalian,People’sRepublicofChina
AgnieszkaCuprys
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
AchleshDaverey
SchoolofEnvironmentandNaturalResources,DoonUniversity,Dehradun,India
BeatrizDelgado-Cano
NationalCenterinEnvironmentalTechnologyandElectrochemistry,Shawinigan,QC,Canada
Dhanjai
DepartmentofMathematicalandPhysicalSciences,ConcordiaUniversityofEdmonton; DepartmentofPhysicalSciences,MacEwanUniversity,Edmonton,AB,Canada;CASKey
LaboratoryofSeparationScienceforAnalyticalChemistry,DalianInstituteofChemicalPhysics, ChineseAcademyofSciences,Dalian,People’sRepublicofChina
DhrubaDhar
DepartmentofBio-Engineering,BirlaInstituteofTechnology,Mesra,Ranchi,India
KasturiDutta
DepartmentofBiotechnologyandMedicalEngineering,NationalInstituteofTechnology Rourkela,Rourkela,India
RosaGalvez-Cloutier
UniversiteLaval,DepartmentofCivilEngineeringandWaterEngineering,Quebec,QC, Canada
LauraGatel
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
NataliGo ´ mez-Falco ´ n
HigherTechnologicalInstituteofTierraBlanca(ITSTB),TierraBlanca,Veracruz,Mexico
KrishnamoorthyHegde
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
KaLokHong
WilkesUniversity,Wilkes-Barre,PA,UnitedStates
RekhaJain
DepartmentofMicrobiology,MarwadiUniversity,Rajkot,India
GuneetKaur
DepartmentofBiology,HongKongBaptistUniversity,KowloonTong,HongKong
GagandeepKaur
BiosensorTechnologyLaboratory,DepartmentofBiotechnology,PunjabiUniversity,Patiala, India
PratikKumar
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
XianboLu
CASKeyLaboratoryofSeparationScie nceforAnalyticalChemistry,Dalian InstituteofChemicalPhysics,Chinese AcademyofSciences,Dalian,People’s RepublicofChina
SamratMaratkar
InstituteofBioinformaticsandBiotechnology,SavitribaiPhulePuneUniversity(Formerly UniversityofPune),Pune,India
AraceliDalilaLariosMartı ´ nez
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
SabaMiri
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
SamuelM.Mugo
DepartmentofPhysicalSciences,MacEwanUniversity,Edmonton,AB,Canada
VinodKumarNigam
DepartmentofBio-Engineering,BirlaInstituteofTechnology,Mesra,Ranchi,India
CarlosS.Osorio-Gonza ´ lez
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
PreetikaKuknurPachapur
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
VinayakLaxmanPachapur
INRS-ETE,UniversityofQuebec;DepartmentofCivilEngineeringandWaterEngineering, LavalUniversity,Quebec,QC,Canada
VishalPandey
InstituteofBioinformaticsandBiotechnology,SavitribaiPhulePuneUniversity(Formerly UniversityofPune),Pune,India
NachiketPathak
InstituteofBioinformaticsandBiotechnology,SavitribaiPhulePuneUniversity(Formerly UniversityofPune),Pune,India
RamaPulicharla
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
KeyurRaval
DepartmentofChemicalEngineering,NationalInstituteofTechnology,Surathkal,India
RituRaval
DepartmentofBiotechnology,ManipalInstituteofTechnology,MAHE,Manipal,India
ShounakRoy
BioXCentreandSchoolofBasicSciences,IndianInstituteofTechnologyMandi,Himachal Pradesh,India
RahulSaini
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
AnganaSarkar
DepartmentofBiotechnologyandMedicalEngineering,NationalInstituteofTechnology Rourkela,Rourkela,India
KuntalDebSarkar
ElectronicsandCommunicationEngineering,NationalInstituteofTechnologyRourkela, Rourkela,India
SantanuSasidharan
DepartmentofBiotechnology,NationalInstituteofTechnology,Warangal,India
PrakashSaudagar
DepartmentofBiotechnology,NationalInstituteofTechnology,Warangal,India
NaeemShaikh
InstituteofBioinformaticsandBiotechnology,SavitribaiPhulePuneUniversity(Formerly UniversityofPune),Pune,India
SujataSinha
DepartmentofBiochemicalEngineeringandBiotechnology,IndianInstituteofTechnology Delhi,NewDelhi,India
AnkitaSinha
KeyLaboratoryofIndustrialEcologyandEnvironmentalEngineering(MinistryofEducation, China),SchoolofEnvironmentalScienceandTechnology,DalianUniversityofTechnology, Dalian,People’sRepublicofChina
AkshaySonawane
InstituteofBioinformaticsandBiotechnology,SavitribaiPhulePuneUniversity(Formerly UniversityofPune),Pune,India
NiranjanSuralikerimath
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
GayatriSuresh
INRS-ETE,UniversityofQuebec,Quebec,QC,Canada
PriyankaUddandarao
DepartmentofChemicalEngineering,NationalInstituteofTechnology,Surathkal,India
NeelamVerma
DivisionofResearchandDevelopment,LovelyProfessionalUniversity,Phagwara;Biosensor TechnologyLaboratory,DepartmentofBiotechnology,PunjabiUniversity,Patiala,India
MausamVerma
CO2SolutionsInc.,Quebec,QC,Canada
Emergingcontaminants(ECs)oremergingpollutants(EPs)orContaminantsofemergingconcern(CEC)aredefinedassyntheticornaturallyoccurringsubstancesorchemicals thatarenotincludedinroutineenvironmentalmonitoringprogramsbuthavethepotentialtoentertheenvironmentandcauseknownorsuspectedadverseecologicaland(or) humanhealtheffects.Suchsubstanceshavenoregulatorystandards(fewcountriesnow have)butmaybecandidateforfuturelegislationdependingontheirecotoxicity,potentialhealtheffects,publicperception,andfrequencyofoccurrenceintheenvironment [1] Occurrenceofthesecandidatesintheenvironmenthasbeeneitherdiscoveredrecently duetotheadvancementsintheanalyticaltoolsandtechniquesortheirenvironmental presenceandsignificanceareonlynowbeingevaluated.ECsincludeawiderangeof chemicals,suchaspersistentorganicpollutants,pharmaceuticalsandpersonalcareproducts(PPCPs),endocrinedisruptingcompounds(EDCs),nanomaterials [1].AsonFebruary2016,Norman [2] hascompiledalistofmorethan1000ECs,whichinclude surfactants,PPCPs,flameretardants,gasolineadditivesandtheirdegradationproducts,
biocides,pesticidesandtheirdegradationproducts,andvariousprovenorsuspected EDCs. Table1.1 presentscommonclassesofECsalongwiththeirexamplesandknown adverseenvironmentaleffects.
LimitedinformationisavailableinliteratureonthefateofthesebroadrangesofECs andtheirenvironmentaleffectsatthetracelevels.Thislimitsthepolicymakerstodraft regulationsforthelong-termimpactassessmentduetoexposureofECsatlowlevels.
ThereforeitisimperativetoanalyzeandmonitortheconcentrationsoftheseECsat theemissionsourceaswellaswithinthedifferentenvironmentalmatricesorcompartments(water,air,andsoil)forbetterunderstandingoftheirlong-termimpactassessment [12].AnalysisofECsisnotaneasytaskas [5]:
(a) Environmentalmatricesareverycomplexinnature.
(b) ECsareusuallypresentinverylowlevels(ppttoppb)inenvironmentalsystems.
(c) Multipleisomers/enantiomers/diastereomersoranalogsofECsarepresentinenvironmentalsystems.
(d) ECsare“emerging”innature,thatisrecentlyidentifiedintheenvironmentand lacksanalyticalmethodsforproperidentificationandquantification.
ConventionalanalyticaltechniquesareavailabletodetecttheECsandtheirpossible metabolitesindifferentenvironment.However,suchanalyticaltechniquesaretime
Table1.1 Classificationofemergingpollutantswithtypicalexamplesandassociatedeffects
ClassExample
Endocrine disrupting chemicals
Phthalates(octylphenols, nonylphenols,di(2ethylhexyl)phthalate (DEHP))
BisphenolA;polychlorinated biphenyls(PCBs) Dioxins
PharmaceuticalsAntibiotics(tetracycline, erythromycin);steroidsand hormones;nonsteroidal antiinflammatorydrugs (NSAIDs)
Pesticidesand insecticides
Fipronil;permethrin; fenitrothion; Bacillus thuringiensisisraelensis
Knownenvironmental effectsReferences
• Interfereswithnormalprocessofnaturalbloodborne hormones
• Effectreproductive functions
• Effectcentralnervoussystem [3]
• Antibioticresistance intheenvironment
• Poisoningtobirds andanimals (Diclofenacpoisoningtovultures) [4,5]
• Possiblecarcinogen
• Highlytoxictolizard,bees,gallinaceousbirds
• Endocrine disruption [6,7]
Table1.1 Classificationofemergingpollutantswithtypicalexamplesandassociatedeffects cont’d
ClassExample
Personalcare products
Flame retardants and plasticizers
Fragrances(nitro,polycyclicand macrocyclicmusks, phthalates)
Sunscreenagents (benzophenone, methylbenzylidenecamphor) Insectrepellants(N,Ndiethyl-m-toluamide (DEET)); parahydroxybenzoates
Organophosphateesters (chlorinatedtri(2-chloroethyl) phosphate;and tri(chloropropyl)phosphate; tributylphosphate); polybrominateddiphenyl ethers;tetrabromobisphenol A;bisphenolA
Knownenvironmental effectsReferences
• Bacterialresistance
• Endocrine disruption
• Increasedriskof cancer [8,9]
Industrial additives
BisphenolA;alkylphenols; phthalateesters
Chelatingagents(EDTA), aromaticsulfonates
Hormonesand steroids
Surfactantsand their metabolites
Estradiol,estrone,estriol, diethylstilbestrol(DES)
Alkylphenolethoxylates, 4-nonylphnol 4-Octylphenol,alkylphenol carboxylates;sodiumlauryl sulfates
NanomaterialsCarbonnanotubes;nanowires; TiO2,ZnO,ironoxides, hydroxyapatite,andmetallic nanoparticles
• Endocrine disruption
• Indicationsof increasedriskfor cancer
• Meioticaneuploidy andsynaptic
• Abnormalitiesin animals
• Estrogenicand reproductiveeffects inbirds
• Endocrine disruption
• Canbetoxictoanimals,ecosystems, andhumans
[3,5–7, 10]
[3,5,6]
• Endocrine disruption [9]
Possibleendocrine disruptiveeffect
Possibletoxicityto animalsandaquatic species [6,9]
Ecotoxicityeffectsare atimmaturestate [11]
consuming,monitorpollutantoffline,andrequiresophisticatedandcostlyinstruments. Thereforealotofeffortshavebeenmadetodevelopbiosensor-basedanalyticaltechniques,whicharelessexpensive,quick,andhaveverylowdetectionlimitsforonline monitoringofECsintheenvironment.Thefollowingsectionsdiscussvarioustechniques(conventionalaswellasbiosensorbased)availableforthedetection,identification, andquantificationofECsalongwiththeiradvantagesandlimitations.
2.Conventionaltechniquesforthedetection,identification, andquantificationofECs
2.1Chromatography-basedmethods
Chromatography-basedseparationtechniquessuchasGasChromatography(GC)and LiquidChromatography(LC)coupledwithMassspectrometer(MS)aretheconventionalandmostfrequentlyappliedtoolsforthedetection,identification,andquantificationofECsintheenvironment.Therearevariousfactorswhichdeterminetheuseof eitherGCorLCfortheanalysisofECsindifferentenvironmentalmatrices.GCisadvantageousbecauseofitsfasteranalysisandbetterseparationefficiencythanLC [13]. However,themostimportantcharacteristicsofpollutant(analyte)tobeanalyzedby GCarevolatilityandstabilityathighertemperature.ThereforeGCisthebesttoolto analyzethevolatilepollutant [14]
2.1.1GCandGC-MS
TheapplicationofconventionalGC(one-dimensionalGCor1DGC)islimitedtothe analysisofmixtureshaving50–60pollutants [15].Also,1DGCisnotabletoseparate themixtureofhydrocarbons(>C10) [16].Theseissuesof1DGChavebeenresolved bythedevelopmentofmultidimensionalGCsuchas2DGC(GC GC).In2D GC,twocolumns(ingeneralnonpolarprimarycolumnfollowedbypolarsecondarycolumn)aresequentiallyconnected,whichenhancethepeakcapacityandseparationpower oftheinstrument [16].High-endmultidimensionalGCsystemsuse2DGC(GC GC) coupledwithMSandcanbeusedfortheanalysisofhighlycomplexsamples [13].
Samplepretreatmentsuchasextractionofpollutantfromenvironmentalmatricesis prerequisiteforthechromatographicidentificationandanalysesofECs.Therearevarioustechniquessuchassolid-phaseextraction(SPE),liquid-liquidmicro-extraction (LLME),andmicrowave-assistedextraction(MAE)fortheextractionofpollutantfrom theenvironmentalmatrices [17].SPEmethodpriortoGC-MSanalysesforthescreening ofECssuchasneutralandacidicpharmaceuticals,bisphenolAandtheirchlorinated derivatives,endocrinedisruptingphenoliccompoundsandsteroidsinwater,andwastewatersampleshasbeenmostextensivelyusedbytheresearchersaroundtheworld [17–20].Kotowskaetal. [21] identified120compoundsincludingdrugremnantssuch asibuprofen,naproxen,andcaffeinefromwastewatersample.Antoniouetal. [22]
developedasolid-phasemicro-extraction(SPME)methodaspretreatmenttechniquefor theextractionofPPCPsandEDCsfromthewastewatertreatmentplanteffluentsand analyzedtheseECsbyGC-MS.Thedevelopedmethodbytheauthorsissimple,solvent free,andlowcost.However,theanalysistime(extractionprocedureandGC-MSanalysis)reportedbytheauthorsisabout2h.Graphene,acarbonnanomaterialduetoitshigh surfaceareahasbeenusedasadsorbentmatrixinSPEfortheanalysisofPPCPsinwastewatersamplesbyGC-MS [23].Upto87.6%recoveryoftheanalytehasbeenreportedby usingthegraphene-basedSPE.Ultrasound-assistedextractionhasalsobeenusedasa low-costmethodfortheextractionofECsfromtheenvironmentalsamples [17,24]
Theextractiontime(5–45min)andsolventconsumptioninultrasound-assistedextractionarelowerthantheclassicaltechniques [24].Recently,ultrasound-assistedextraction iscombinedwithSPMEcoupledwithGC-MSfortheanalysisofPPCPsinriversediments [24].Combinationofultrasound-assistedextractionandSPMEintegratesmultiple steps,thatis,extraction,cleaning,isolation,andenrichmentofanalytesinaminiaturized system,whichrequiredverysmallamountofsample(mL)withlimitsofdetectionand quantificationofPPCPs <0.25ng/gand <0.8ng/g,respectively,inriversediment [24]. PolarECsarelessvolatileandtherefore,derivatizationisnecessarytoanalyzethemby GC.DerivatizationreducesthepolarityandenhancesthevolatilityofpolarECbyconvertingpolargroupsintolesspolarmoieties [25,26].Thisstepenhancestheseparation, selectivity,andsensitivityofthepolarcontaminantbyGC [27].However,thisadditional derivatizationstepintheanalysisofpolarECsbyGC-MSistimeconsuming,tedious, laborious,anduseshighlytoxicandcarcinogenicchemicalssuchasdiazomethanefor derivatizationofchlorinatedphenoxyacidherbicides.Moreover,chancesofsamplecontaminationincreaseduringderivatization [28].Furthermore,temperature-sensitiveECs cannotbeanalyzedbyGC-basedtechniques.
2.1.2LCandLC-MS
LCsystemsarethepreferredoverGC-basedtechniquesfortheanalysisofpolarand temperature-sensitiveECsindifferentenvironmentalmatrices.However,theanalysis ofpollutantsbyLC-basedtechniquesismoretimeconsumingthanGC-basedtechniques.ThereforeLCsystemshavebeenupgradedintherecentpastthroughmodern approachesinordertoachievethefastseparationofECswhilemaintainingthehighresolutionandseparationefficiency.Ultra-high-pressureLC(UHPLC)usescolumns packedwith <2 μmparticles(sub-2 μmparticlespackedcolumns)comparedtoconventionalhigh-pressureLC(HPLC)columnshaving5or3 μmparticles.Advantagesof UHPLCoverconventionalHPLCinclude:(1)lesseramountofsolventsrequiredfor sampleelution,(2)muchnarrowerandconcentratedbandsareobtained,and(3)separationspeedincreasesuptoninefold [29,30].ThebestpartofUHPLC-MSsystemisvery quick(<5min)separationoftargetcompoundwithquantificationrangeof10–50ng/L [31].Duetotheseadvantages,UHPLCisoneofthemostpromisinganalyticaltoolsfor
theanalysisandmultiresiduescreeningoforganicECsinenvironmentalmatrices [32]. Forexample,analysisofantibioticresiduesandtheirmetabolites,drugsofabuseandtheir metabolitesinurbanwastewaterandsurfacewater [33,34] andpesticidesinwastewater havebeendetectedandanalyzedbyUHPLC [35].UHPLCcoupledwithMS(UHPLCMSsystems)isefficientinscreeningofsuspectandnontargetECsinwatersamples [36, 37].However,themaindrawbackofUHPLCsystemisincreaseinbackpressure(upto 27-fold)andtherefore,aspecialhardwareisrequiredtohandlethishighpressure,which increasesthecostofLCsystem [31,38]
Core-shellcolumnsorfused-corecolumnsinplaceofsub-2 μmparticlespackedcolumnsareusedinLCsystemstoovercomethehighbackpressureissueofUHPLC.Coreshellcolumnsusesuperficiallyporousparticles,whichenablehigh-speedanalysiswhile maintainingthehighseparationefficiencyequivalenttoUHPLCwithoutincreasingthe backpressure.ApplicationsofLCsystemsusingfused-corecolumnsforanalysisofEcs suchaspharmaceuticals(illicitdrugs,psychiatricdrugs,andselectedhumanmetabolites, etc.),bisphenolAandtheirmetabolitesinwastewateranddrinkingwater [39–42],naphthenicacidsinsurfacewaters [43],andpolarpesticidesanditsdegradationproductsand somenitro-phenolsinrainwater [44] areavailableinliterature.
DevelopmentofautomatedinstrumentssuchasonlineSPEcoupledtoLCandMS (SPE-LC-MSorSPE-LC-MS/MS)isanotheradvancementinLC.Suchautomated instrumentsintegratethreesteps—extraction,purification,anddetectionandhave user-friendlyadvancedintegratedLC-MScontrolsoftwareandrequiresmallsamplevolume(aslowas1mL) [32,45].Thereforeautomatedinstrumentsarehighlyrecommended whensamplevolumeisverylow.SPE-LC-MSorSPE-LC-MS/MStechniqueshave becomemoreandmorepopularintherecentpastforthedetectionanddetermination ofEC [46,47].Forexample,Wodeetal. [48] usedamultiresidueanalyticalmethod forthesimultaneousdeterminationof72ECs(industrialchemicals,pharmaceuticals, psychoactivesubstances,flameretardants,neutralandacidicpesticides)inwatersamples withUHPLC-MS.Recently,anautomatedonlineSPEcoupledtoLC-tandemmass spectrometry(SPE-LC-MS/MS)hasbeenusedbyAnumolandSnyder [46] fortherapid analysisoftraceorganiccompoundssuchaspharmaceuticals,PCPs,hormones,andpesticidesinwater.Theauthorsusedpolymericreversed-phasecartridgesinSPE-LC-MS/ MS.Gorgaetal. [47,49] analyzedendocrinedisruptersandrelatedcompoundsinvarious environmentalmatrixes(river,sediments,wastewater,andsewagesludge).
Despitetheadvancementsinthetoolsandtechniquesandaccuracyandsensitivity, chromatographicmethods(LC-MSandGC-MS)havethefollowinglimitations [50,51]:
1. Theyarenotsuitableforon-siteandcontinuousanalysisofEC.
2. Thesemethodsarelimitedtocentralizedhigh-endlaboratories.
3. Instrumentationsystemsareverycostly.
4. Overallanalysis(includingsamplepretreatment)ofECsistimeconsuming.
5. Highlyskilledandtrainedpersonnelisneededtousethesemethods.
2.2Immunochemicaltechniques
Immunochemicaltechniquessuchasenzyme-linkedimmunosorbentassays(ELISA)and time-resolvedfluoroimmunoassay(TRFIA)havealsobeendevelopedforthedetection andquantificationofECssuchasEDCfromtheenvironmentalmatrices [52–56].ELISA isbasedontheprincipleofantigen-antibodyinteraction,whileTRFIAisbasedonthe fluorescencepropertiesofthelanthanideions [56].TRFIAisultrasensitivethanELISA butlanthanideionsusedinTRFIAareverycostly,whichdiscourageitsuseoverELISA. Immunochemicaltechniquesareadvantageousoverchromatographictechniquesdueto theirfastanalysistime,selectivity,sensitivity,reliability,simplicity(simpleornosample pretreatment),andlowsamplevolume [56].However,thelimitationsordrawbacksof immunochemicaltechniquesare [57] asfollows:
1. Biologicalmaterials(antibody)usedintheimmunochemicaltechniquesarelessstable.
2. Assayprocedureiscomplicatedandhavemultisteps.
3. Highlyskilledpersonisrequiredforpreparationofantibodyandanalysis.
4. Difficulttouseon-site.
3.Biosensorsforthedetection,identification,andquantificationofECs
Biosensorisdefinedas“adevicethatusesspecificbiochemicalreactionsmediatedbyisolatedenzymes,immunosystems,tissues,organellesorwholecellstodetectchemicalcompoundsusuallybyelectrical,thermaloropticalsignals”bytheInternationalUnionof PureandAppliedChemistry(IUPAC) [57].Inotherwords,biosensorssensethesignals producedbythebio/chemicalreactionsinvolvingtheanalyte.Thesesignalsareproportionaltotheconcentrationoftheanalyteinthereactionmixture [58].Thebiosensorsare gaininglotofattentioninthescreeninganddetectionofECsintheenvironmentalmatricesduetotheirselectivity,reproducibility,stability,sensitivity,portability,miniaturization,on-sitemonitoringandenablepermanentandunattendedoperationinthefield [57–59].ThebiomonitoringofECsbyusingbiosensorsisanotheradvantageover GC-LC-basedsystems.Determinationofeco-effects(cytotoxicity,genotoxicity,endocrinedisruptingeffects,etc.)ofenvironmentalcontaminantsisfeasiblebybiosensors [57]. Justinoetal. [60] summarizedtherecentapplicationsofdifferentbiosensorsinenvironmentalmonitoringofECssuchaspesticides(includingorganophosphorouspesticides), pathogens,andendocrinedisruptingchemicals.Thelimitofdetectionofbiosensorswas reportedtobeuptoppblevels [60].
Atypicalbiosensorhasthefollowingmaincomponents:analyte(thepollutant),bioreceptor(recognizetheanalytethroughbiochemicalreactionsandproducessignals), transducer(convertbiochemicalsignalstoelectronicsignals),anddisplay.Biosensors arebroadlyclassifiedintotwogroupsbasedonthetypeoftransducerandbioreceptor type. Fig.1.1 showsthedifferentclassesofbiosensors.
3.1Aptasensorsfordetectionofemergingcontaminants
Aptamersarethesingle-strandedDNAorRNAofknownsequences,havehighaffinity andspecificitytothetargetmoleculestobedetected.Aptamer-basedtechnologieshave gainedtremendousinterestinsensingapotentiallylargenumberofenvironmentalcontaminationinrecenttimeduetotheirhighersensitivity,selectivity,lessexpensiveinvitro system,andenhancedenvironmentalstability.Anaptasensorconsistsofknownoligonucleotidesequence,thatis,aptamerasthesensingelementeithercombinedwithinthe systemorcloselyassociatedwithaphysiochemicaltransducersystem [61].Besidethesignificantapplicationofaptasensorinmedicalfield,thistechniqueisnowmorepopularas thesensorsystemofseveralenvironmentalcontaminantsincludingheavymetals,toxins, pesticides,andotherharmfulsmallmolecules.Mycotoxins,themajorgroupoftoxins thatarepresentinourfoodhavebeendetectedbythisaptasensor [62].Recently,anumberofheavymetalsincludingAs3+,Cu2+,andPb2+ havebeendetectedfromcontaminatedwatersampleatverylowconcentrationbythistechnique [63].Aseriesofaptamers whichbindtowithhighaffinitytodifferentpoisonousorgano-phosphorouspesticides suchasphorate,profenofos,isocarbophos,andomethoateashasalreadybeendeveloped [64].Aptasensorscapableofrapidlydetectingpathogensincludingbothvirusandbacteria withimprovedanalyticalperformancehavebeendesignedwithoutpriorinformationof theirmolecularstructures [65].Intheenvironmentalmonitoring,theapplicationofelectrochemicalaptasensorsisimmense,andthisisoneofthefascinatingareas.Thefuture progressinaptasensorstechnologywillrevealthedetectionofunexploredtargetanalytes relevanttotheenvironmentalcontaminants.
Fig.1.1 Classificationofbiosensors.
3.2Enzymeandwholecellbiosensors
Enzymebiosensoremployedvariousgroupsofenzymessuchaslaccase,tyrosinase,peroxidases,acetylcholinesterase,cytochromeP450,monoamineoxidaseasrecognition element [65–68].Theyhavewideapplicationsinmonitoringenvironmentalcontaminantsincludingphenolsandtheirdegradativeproducts [65,66],pesticides [69],herbicides [70],andpharmaceuticals [67].Acoupleofportableenzyme-basedbiosensors havealsobeenreportedinliteratureforon-sitepesticidedetection [71,72]
Themainadvantagesofusingenzyme-basedbiosensorsincludeshortanalysistime (analysissamplewithinminutesorhours)andnoethicalissuesassociatedwiththem. However,theyarecostlierandcandetectnarrowerrangeofpollutantsthanwholecell biosensors.Enzymebiosensorsdetectagroupofpollutants,forexample,totalpesticides ratherthanindividualpollutant.Ontheotherhand,wholecell(bacteria,yeast,algae) basedbiosensorsareinexpensiveandeasybuthaveethicalissues.Theanalysistimeof wholecell-basedbiosensorsisinhourstodays [59].
Yeastbiosensors(anexampleofwholecellbiosensors)havebeendevelopedforselected endocrinedisruptors(EDC)suchasestrogens [73],glucocorticoids [74],bisphenolA [75], serotonin [76],andsoon,andselectedheavymetals [77,78].Thereforeyeastbiosensorfor otherECsneedstobedevelopedforitswiderandrealworldapplications.Long-termstorageofyeastbiosensorsischallengingandneedsfurtheradvancements.Fewauthorssuggestedandtestedthestorageofyeastbiosensorsatlowtemperature( 18or 20°C)to maintaintheviabilityofcellsforupto10–12months [79,80].However,reactivation ofyeastcellsfromdeepfreezestoragebeforeon-siteanalysismayneedseveralhours [59]
3.3Immunosensors
ImmunosensorsarebasedontheimmunochemicaltechniquessuchasELISAtodetect theECsintheenvironment.Theyutilizetheantibodyorantigenasbioreceptortoproducesignalsandatransducer(electrochemical,optical,piezoelectric,etc.)toconvertthe biosignalsintoreadableform.Immunosensorsarehighlyselectiveandcanbeusedto studythetoxicityofanindividualpollutant [81].Maurizetal. [82] hadcontinuously monitoredthechlorpyrifos,anorganophosphatepesticideatpartpertrillionlevelsinreal watersamples(groundwater,surfacewater,anddrinkingwater)usingaportableimmunosensor.Theportableimmunosensortookonly20minfortheanalysiswithoutsample preparationsuchasextractionorcleanup.
3.4Molecularlyimprintedpolymer(MIP)biosensors
MIP-basedsensorshavebeengaininghugeattentioninrecenttimes.Thebasicworking principleofMIPisthecreationofhighlystableligandwithspecificandselectivecratersina 3D-polymericnetwork,complementarytothetargetanalyticsbypolymerizationofa monomerandacross-linker.Thecavitynotonlyiscomplementarywithrespecttotarget
molecule’sshape,size,andconformationbutalsoprovidescovalentandnoncovalentinteractionpointsandacoordinationsphereforproperconjugationofthetemplatemolecule [83].MIPsaresyntheticpolymers,whichcanonlybeusedasaffinitysensorsbutnotasa catalyticbiochemicalenzymemimickingsensors [84].Thistechnologyhasbeendescribed aspromisinganalyticaldevicesindiversefields,includingenvironmental,food,pharmaceutical,andclinicalanalysis [84].MIPtechnologyisadvantageouswithrespecttoits desiredportability,quickresponse,highspecificity,acutesensitivity,andlessprice.For effectivedetection,MIP-basedsensorsshouldbecoupledwithvarioustransducerssystems includingelectrochemical,optical,conductometric,fluorescence,andpiezoelectric [85] MIPsarealongwithotheranalyticaltechniquessuchasLC,capillaryelectrochromatography,SPE,bindingassays,andsoon,alsousedasselectivetoolsforthedetectionofvarious inorganicandorganicenvironmentalpollutants [86].
TheapplicationsofMIPbiosensorshavealreadybeeninsuccessinanalyzingvolatile organicsfromtheirmixtures,studyingdegradationofhydrocarbon,detectingpesticides, pharmaceuticalcompoundsinpollutedenvironmentalsample,inevaluatingoxidationreductionreactions,inbio-analyzingofsignalingmolecules/drugsbytargetingwholecells, viruses,orbacteria [87–91].AcombinationofMIPsandtransducersformasynergistic device.MIPsshouldhavefulfilledcertaincriteriaduringfabrication.Theyshouldhave properselectivity,bindingstrength,regenerationabilityandstabilityintermsofwithstandingextremepH,organicbase,hightemperatureandpressureduringoperationalcondition aswellasduringstorage [87,92].Moreover,thistechnologyisquitesuitableandadvantageousforthedetectionofnonelectroactivemoleculessuchaspesticides,drugs,andsoon. DespitetheplentifuladvantagesofMIPstherateofcommercialactivityisstilllimited.
3.5Nanomaterial-basedbiosensors
Nanomaterial-basedbiosensorsarealsoattractingalotofattentionduetoitsuniquecharacteristicsandadvantagesoverotherbiosensors.Nanomaterialsofferaveryhighsurface area-to-volumeratio,whichenhancesthecatalyticfunctionandsensingresponse [93] Theyalsooffergreatbiochemicalcompatibilitywithverylowdetectablelimits.Silver nanoparticle-basedelectrochemicalbiosensorshavebeendevelopedforthedetection andmonitoringofestrogenicsubstancesinwatersampleswithdetectionlimitsofup to1ng/L [94].Recently,Pdwormlikenanochains/graphiticcarbonnitridenanocompositesandacetylcholinesterase-basedbiosensorsweredevelopedforthedetectionof organophosphatepesticideswithgoodreproducibilityandstability [95].Hassaanetal. [96] developedopticalnano-biosensorsforthedetectionofpharmaceuticalsandother contaminants.Theauthorsusedhorseradishperoxidaseenzymeasabioreceptorfor thedetectionandquantificationofphenol,resorcinol,epinephrine,andacetaminophen. However,applicationofsuchopticalnano-biosensorsforrealenvironmentalmatrices needstobeverified.
4.Conclusion
Despitevariousadvantages(suchasselectivity,portability,fasteranalysis,costeffectiveness.andreal-timemonitoringofpollutants)overconventionalanalyticaltechniques,biosensorsforenvironmentalapplicationsarestillinthedevelopingstageandface variouschallengesduetothecomplexityoftheenvironment.Thepresenceofothercontaminantsintheenvironmentalmatricesinterfereswiththeanalysisoftargetpollutantby biosensorsandaffectsthedetectionlimits [68].MIPandnanomaterial-basedbiosensors wouldbeanalternativeoption.However,applicationsofMIPbiosensorsaremainly focusedonbiomedicalfield.Ontheotherhand,variousdifficultiesrelatedtotheconstructionofbiosensorsbasedonnanomaterialshavebeenpointedoutbyMaduraiveeran andJin [93].Forexample,controlledsynthesisofnanoparticles,optimizationofmultimetallicnanoparticlesforbetterspecificityandstabilityinrealworldsamples,designing ofsuitableinterfaceforimprovedsensitivity,andsoon,arestillchallengingforthedevelopmentofnanomaterial-basedbiosensors.Commercializationofbiosensorsforon-site monitoringofEPsintheenvironmentshouldbethefocusoffutureresearch.
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RajMohanBalakrishnan
Intherecentyearsenvironmentalsecurityhasbeenthreatenedbyawiderangeofenvironmentalpollutantsduetovariousindustrial,agricultural,land,andotheranthropogenicactivities.Thereforeamajorconcernliesinmonitoring/detectingwater,soil, andairpollutants [1].Further,thedetectionofthesepollutantsessentiallyshouldbe inthelevelofassessingthesafetyoftheenvironment.RecentliteraturesreportthedetectionofpollutantsintherangeofmolL 1 tomgL 1 orevenlower [2,3].Althoughthe existinganalyticalmethodssuchashighperformanceliquidchromatography(HPLC), inductivelycoupledplasmaopticalemissionspectrometry(ICP-OES),atomicabsorptionspectrometry(AAS),inductivelycoupledplasmamassspectrometry(ICP-MS), andsoon,areaccurate,thereisaneedforsimple,portable,andrapidmethodsforpollutantdetection [4]
Biosensorsareanalyticalhybriddevicesthatcanprovidespecificqualitativeorsemiquantitativedatabyintegratingbiologicalorbiomimeticdetectionelement.Thedetectionelementisusuallybiologicalinnaturealongwithatransducer.Thetransducer convertsabiochemicalphenomenonintoanelectricalsignal [5,6].Thisapproach exploitsthemolecularbindingeventandalsobringsresearchersfromdifferentareas ofscienceandengineeringtogetheronacommonplatform.Pastdecadehasseentremendousriseindevelopmentofnoveltoolsforefficientenvironmentalmonitoring.Clark andLyonswerepioneersinbiosensorsdevelopmentresearch.Later,UpdikeandHicks developedthefirstenzyme-basedbiosensorintheyear1967,whereanoxygenelectrode hadpolyacrylamideimmobilizedwithenzymeglucoseoxidaseonitssurfacetofacilitate rapidandquantitativedeterminationofglucose [7–9].
2.Classificationofbiosensors
Atypicalbiosensorconsistsofabiologicalsensingcomponent/bioreceptorandaphysical transducer/messenger [10] (Fig.2.1).Thebioreceptoristhekeycomponentinthebiosensor,whichisresponsibleforthespecificity,responsetime,affinity,andlifetimeofthe biosensor.Thesebioreceptorsincludemicroorganisms,enzymes,antibodies,DNA,oligonucleotides,aswellasanimalandplantcellsortissuesthatbindtoaspecificanalyteina givenenvironment [11].Thebioreceptorisintegratedwithorimmobilizedonatransducersurface,whichrespondstothesensingactivityofthereceptor.Thetransducerelementsareworkingontheelectrochemicalandopticalprinciplesthattransforma chemical/physicaleventintoaquantifiablesignal.Theeventcouldbeapotentialdifference,current,conductivity,luminescence,fluorescence,pHchange,andsoon.
Fig.2.1 Schematicrepresentationoftypicalbiosensor.
Bioreceptor Transducer
Sample analyte
