Fateofpharmaceuticalsandtheirtransformationp

ContentslistsavailableatScienceDirectChemicalEngineeringJournaljournalhomepage:ía-Galána,b,c,⁎,1,M.Stefania,S.Rodríguez-Mozazb,D.Barcelób,d,H.Monclúsa,I.Rodriguez-Rodaa,b,J.Comasa,baLEQUIA,InstituteoftheEnvironment,UniversityofGirona,CampusMontilivi,c/MariaAurèliaCapmany,69,E-17003Girona,Catalonia,SpainbCatalanInstituteforWaterResearch(ICRA),ParcCientíficITecnològicdelaUniversitatdeGirona,H2OBuilding,c/EmiliGrahit101,17003Girona,Catalonia,SpaincGEMMA:EnvironmentalEngineeringandMicrobiologyResearchGroup,DepartmentofHydraulic,MaritimeandEnvironmentalEngineering,UniversitatPolitècnicadeCatalunya,c/JordiGirona1-3,BuildingD1,E-08034Barcelona,SpaindWaterandSoilQualityResearchGroup,DepartmentofEnvironmentalChemistry,IDAEA-CSIC,c/JordiGirona18-26,08034Barcelona,SpainARTICLEINFOKeywords:MetabolitesDegradationMembranebioreactorReverseosmosisNanofiltrationAntibioticsABSTRACTTheremovalofpharmaceuticals(PhACs)presentinurbanwastewaterbymembranebioreactors(MBRs)fol-lowedbyreverseosmosis(RO)ornanofiltration(NF)membraneshasbeenfrequentlyaddressedintheliterature.However,dataregardingtheremovaloftheirmainhumanmetabolitesandtransformationproducts(TPs)isstillscarce.Inthisstudy,thepresenceof13PhACsand20oftheirmetabolitesandTPswasmonitoredduring2consecutiveyearsinthedifferenttreatmentstepsofurbanrawwastewater(sewer,primarytreatment,MBRandRO/NF).RejectionoftheselectedcontaminantswhenusinglowpressureNFmembranes(NF-90)orROmembranes(ESPA2)aftertheMBRstepwasalsoinvestigated.Theanalgesicacetaminophen,whichwasfoundatthehighestconcentrationsinthesewerandinfluentsamples(18–74µgL−1)overthetwoexperimentalperiods,wasfullyeliminatedduringMBRtreatment.ThosePhACsthatwereonlypartiallyremovedaftertheMBR,werealmostcompletelyremoved(99%)bytheROmembraneworkingunderdifferentprocesscon-ditions.Atasimilaraveragepermeatefluxes(18Lm−2h−1),theNFmembraneshowedhighremovaleffi-ciencies(90%)forallofthePhACsandtheirmetabolites,thoughlowerthanthoseachievedbytheROmembrane.WhenthefluxoftheNF90membranewasincreasedto30Lm−2h−1(whilestilloperatingatafeedpressurelowerthantheROmembraneat18Lm−2h−1)theperformanceofthemembraneincreased,achieving98%rejectionofPhACs.1.IntroductionAshumanhealthisincreasinglydependingonpharmaceuticalproducts,thescientificcommunitytogetherwithenvironmentalandpublichealthauthoritieshavemadeasignificanteffortinunder-standingthefateofpharmaceuticallyactivecompounds(PhACs)boththroughengineeredurbanwastewatertreatmentprocessesaswellasinthenaturalenvironment.Thishasbeenreflectedinthehighnumberofscientificpublicationsdevotedtothissubjectinthelasttwodecades.Onthecontrary,modificationoflegalregulationsuptonowisbasicallyinexistent.However,waterscarcityandwaterreusehavebecomees-sentialissuesinwaterresourcemanagementworldwide,alwayscon-sideringtheconservationofaquaticecosystemsasafinalgoalandmaindriveroftheinvolvementofthescientificcommunity.Sofar,mostoftheresearchcarriedoutregardingthefateofPhACsthroughMBRprocesseshasmainlyfocusedonthestudyofparentcompounds,neglectingtheirmetabolites.Onlyrecently,theenviron-mentalpresenceofhumanmetabolitesanddifferenttransformationproducts(TPs)ofthesePhACshasbeenincludedwithinthescopeofremovalefficiencystudiesofdifferentwastewatertreatmentstechnol-ogies[1–3].Itshouldbeconsideredthat,oncereleasedontotheen-vironment,thesemetabolitesandTPscanbebothinnocuous[4],butalsonocuousandevenmoretoxicthantheoriginalsubstanceagainstdifferentaquaticorganisms.Furthermore,thecoexistenceoftheori-ginaldrugswiththesemetabolitesandTPscouldleadtoadditive,an-tagonisticand/orsynergeticeffectswhicharehardtopredictandthatshouldbeinvestigated.Forinstance,theassessmentoftheecotoxicityofthephotoproductsoftheanti-inflammatorydiclofenac(DCF)orna-proxenhasprovidedtheevidencethatacuteandchronictoxicitycanbegreaterforthesephotoproductsthanfortheparentcompounds[1].⁎Correspondingauthor.Tel.:[phone]J.MamoandM.J.Garciacontributedequallytothiswork.E-mailaddress:[e-mail](M.J.García-Galán).ChemicalEngineeringJournal331(2018)450–461Availableonline04September20171385-8947/©2017ElsevierB.V.Allrightsreserved.MARKEffectiveconcentrationvalues(EC50)obtainedafter15minassaysfortheantibioticsulfapyridine(SPY)anditsacetylatedmetabolite,N4-acetylsulfapyridine(acSPY),demonstratedthatthemarinebacteriaVibriofischeriwasmoresensitivetothepresenceofthemetabolitethantotheoriginaldrug,andaccordingtheEUlegislation(Directive93/67/EEC),theformercouldbecategorizedastoxic[2].Ontheotherhand,ithasbeendemonstratedthatconventionalac-tivatedsludge(CAS)treatmentprocessesinwastewatertreatmentplants(WWTPs)donotadequatelyremovemanyofthemostcommonlyusedPhACssuchasDCF,theanticonvulsantcarbamazepine(CBZ)ortheantibioticsulfamethoxazole(SMX)[5,6].Differentstudieshavedemonstratedthatmembranebioreactors(MBRs)arecapableofre-movingmoderatelybiodegradablean