Analysis of five benzophenone-type UV filters in human urine by liquid chromatography-tandem mass spectrometry

[摘要] Benzophenone(BP)-typeUV(ultraviolet)filters,especially2-hydroxy-4-methoxybenzophenone(2OH–4MeO–BP),arewidelyusedintheU.S.,toprotecttheskinandhairfromUVirradiation.DespitehumanexposurestoUVfiltersthroughthedermalapplicationofproductscontainingsunscreenagents,fewstudieshaveexaminedtheoccurrenceofUVfiltersinhumans.Thusfar,fewsensitivemethodsareavailableforthedeterminationof2OH–4MeO–BPinhumanurine.Furthermore,methodsforthedeterminationofotherBPderivatives,including2,4-dihydroxybenzophenone(2,4OH–BP),whichisformedfrom2OH–4MeO–BPviametabolicactivitiesofthecytochromeP450enzymes,havenotbeenavailable.Inthisstudy,wehavedevelopedamethodfortheanalysisoffiveBPderivatives:2OH–4MeO–BP,2,4OH–BP,2,2′-dihydroxy-4-methoxybenzophenone(2,2′OH–4MeO–BP),2,2′,4,4′-tetrahydroxybenzophenone(2,2′,4,4′OH–BP),and4-hydroxybenzophenone(4OH–BP)inhumanurine,usingliquid–liquidextractionandliquidchromatograph(LC)-tandemmassspectrometer(MS/MS)analysis.TheinstrumentalcalibrationrangeforeachoftheBPderivativesrangedfrom0.05to100ngml−1,andshowedexcellentlinearity(r>0.99).Therespectivelimitsofdetection(LODs)andlimitsofquantification(LOQs)weredeterminedtobe0.082and0.28ngml−1forboth2,4OH–BPand4OH–BP;0.13and0.44ngml−1for2,2′OH–4MeO–BP;and0.28and0.90ngml−1forboth2OH–4MeO–BPand2,2′,4,4′OH–BP.RecoveriesofBPderivativesthroughtheentireanalyticalprocedurewerebetween85.2and99.6%.Thecoefficientsofvariation(CVs)offivereplicateanalyseswithin1day,andacross5days,wererespectively1.4and3.7%for2,4OH–BP;1.7and3.0%for2OH–4MeO–BP;and2.8and4.5%for4OH–BP.WhenBPderivativesweredeterminedinurinesamplesfrom23U.S.(Albany,NewYork)and22Japanese(Matsuyama,Ehime)volunteers,higherconcentrationsof2,4OH–BP,2OH–4MeO–BP,and4OH–BPwerefoundinsamplescollectedfromfemalesintheAlbanycohort,probablyreflectinggreatusagebyU.S.females.Theurinesamplefromaknownsunscreenusercontainedveryhighconcentrationsof2,4OH–BPand2OH–4MeO–BP.2,2′,4,4′OH–BPand2,2′OH–4MeO–BPwerenotdetectedinanyoftheurinesamplesanalyzed.Ourresultsindicateconsiderableexposuretohighlyestrogenic2,4OH–BPand2OH–4MeO–BPbyfemalesintheU.S.,andsuggesttheneedforfurtherstudiesonpotentialhealtheffects...

[学科分类] 分析化学