Individual and cumulative impacts of fire emissions and tobacco consumption on wildland firefighters’ total exposure to polycyclic aromatic hydrocarbons

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ContentslistsavailableatScienceDirect

Journal

of

Hazardous

Materials

j ou rn a l h om epa ge :w w w . e l s e v i e r . c o m / l o c a t e / j h a z m a t

Individual

and

cumulative

impacts

of

ﬁre

emissions

and

tobacco

consumption

on

wildland

ﬁreﬁghters’

total

exposure

to

polycyclic

aromatic

hydrocarbons

Marta

Oliveira

a,b

_,

_Klara

_Slezakova

a,b

_,

_Carlos

_Pires

_Magalhães

c

_,

_Adília

_Fernandes

c

_,

João

Paulo

Teixeira

d,e

_,

_Cristina

_{Delerue-Matos}

a

_,

_Maria

_do

_Carmo

_Pereira

b

_,

Simone

Morais

a,∗

a_{REQUIMTE-LAQV,}_Instituto_Superior_de_Engenharia,_Instituto_Politécnico_do_Porto,_Rua_Dr._António_Bernardino_de_Almeida_431,_4200-072_Porto,_Portugal

b_LEPABE,_Departamento_de_Engenharia_Química,_Faculdade_de_Engenharia,_Universidade_do_Porto,_Rua_Dr._Roberto_Frias,_4200-465_Porto,_Portugal

c_Escola_Superior_de_Saúde,_Instituto_Politécnico_de_Braganc¸_a,_Braganc¸_a,_Portugal

d_Instituto_Nacional_de_Saúde_Pública,_Departamento_de_Saúde_Ambiental,_Rua_Alexandre_Herculano_321,_4000-055_Porto,_Portugal

e_Universidade_do_Porto,_Instituto_de_Saúde_Pública,_Rua_das_Taipas_135,_4050-600_Porto,_Portugal

h

i

g

h

l

i

g

h

t

s

•Impactoffireemissionsandsmokingonfirefighters’exposuretoPAHswasassessed.

•Smokingincreased76–412%thelevelsoftotalurinarymetabolites(OH-PAHs).

•Fireﬁghtingactivitiesraised158–551%thetotalOH-PAHsconcentrations.

•2-hydroxyfluorenewasthemostaffectedmetabolitebyfirefightingactivities.

•1OHNaph+1OHAcepresentedthemorepronouncedincreaseduetotobaccoconsumption.

a

r

t

i

c

l

e

i

n

f

o

Articlehistory:

Received27December2016

Receivedinrevisedform19March2017

Accepted24March2017

Availableonline27March2017

Keywords: Biomonitoring Firemen

Occupationalexposure

Tobaccosmoking

Urinarymonohydroxylmetabolites

(OH-PAHs)

a

b

s

t

r

a

c

t

There is limited information about wildland firefighters’ exposure to polycyclic aromatic hydro-carbons(PAHs), beingscarcestudiesthat includedtheimpactof tobaccoconsumption.Thus, this work evaluated the individual and cumulative impacts of firefighting activities and smoking on wildlandfirefighters’totalexposure toPAHs. Six urinaryPAH metabolites(1-hydroxynaphthalene (1OHNaph),1-hydroxyacenaphthene(1OHAce),2-hydroxyfluorene(2OHFlu),1-hydroxyphenanthrene (1OHPhen),1-hydroxypyrene(1OHPy),and3-hydroxybenzo[a]pyrene(3OHB[a]P))werequantifiedby high-performanceliquidchromatographywithfluorescencedetection.Firefightersfromthreefire sta-tionswerecharacterizedandorganizedinthreegroups:non-smokingandnon-exposedtofireemissions (NSNExp),smokingnon-exposed(SNExp),andsmokingexposed(SExp)individuals.1OHNaph+1OHAce werethemostpredominantOH-PAHs(66–91%

OH-PAHs),followedby2OHFlu(2.8–28%),1OHPhen (1.3–7%),and1OHPy(1.4–6%).3OHB[a]P,thecarcinogenicityPAHbiomarker,wasnotdetected. Regu-larconsumptionoftobaccoincreased76–412%

OH-PAHs.Firecombatactivitiespromotedsigniﬁcant incrementsof158–551%

OH-PAHs.2OHFluwasthemostaffectedcompoundbyfirefighting activi-ties(111–1068%),while1OHNaph+1OHAcepresentedthemorepronouncedincrementsduetotobacco consumption(22–339%);1OHPhen(76–176%)and1OHPy(20–220%)weretheleastinfluencedones. OH-PAHlevelsofSExpfirefightersweresignificantlyhigherthaninothergroups,suggestingthatthese subjectsmaybemorevulnerabletodevelopand/oraggravatediseasesrelatedwithPAHsexposure.

∗ Correspondingauthor.

E-mailaddress:[email protected](S.Morais).

1. Introduction

Human biomonitoring allows assessment of total personal

exposure, including environmental and workplace hazardous

chemicals,throughtheanalysisofchemicalsand/ortheir

metabo-http://dx.doi.org/10.1016/j.jhazmat.2017.03.057

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litesinhumanexhaledair,blood,urine,milk,saliva,nails,hair,

faeces,andadiposetissue[1,2].Amongthemanyhumanmatrices,

urineisbyfarthemostcommonone[3–5].Thustheuseofhuman

biomonitoringisaprecioustoolasitestimatesthetotalinternal

doseregardlessofthesource,route,anddurationoftheexposure.

Occupationalexposureoffirefighters, i.e.firefightersdirectly

involvedinfirefightingactivities,wasclassifiedasapossible

car-cinogentohumansbytheInternationalAgencyforResearch on

Cancer(IARCgroup2B;[6])andtheUSNationalInstitutefor

Occu-pationalSafetyandHealth(NIOSH;[7]).Wildlandﬁreﬁghtersare

frequentlyexposed tonumerous pollutants (particulatematter,

carbonmonoxide,nitrogendioxide,volatileorganiccompounds

including polycyclic aromatic hydrocarbons(PAHs),

polybromi-nateddiphenylethers,polychlorinateddibenzo-p-dioxin,etc.)that

arereleasedduringﬁres[5,8–13].Exposuretowildﬁresmokeis

being associated with respiratory morbidity withgrowing

evi-dencesupportinganassociationwithall-cause mortality,being

consistentlyrelatedwithcardiovasculareffects,speciﬁccausesof

mortality,birthoutcomes,andmentalhealthdisorders[14].

Tobaccoconsumptionisanadditionalriskfactorforpotential

healtheffects,sinceprolongedexposuretotobaccosmokeis,by

itself,themajorcauseoflungcancer[15].Tobaccosmokeisa

com-plexmixtureofthousandsofchemicalsubstancesincludingover

69knowncarcinogens;therefore,tobaccosmokingandits

expo-sureareclassiﬁedasknownhumancarcinogensbymostofthe

internationalagencies[15,16].

Intermsofthemainconstituentsisolatedfromthemainstream

smokeofcigarettes andair emissionsreleasedduring wildland

and agriculturalﬁres, PAHsarea relevant groupofcompounds

thatcause carcinogeniceffects [15].PAHs areubiquitous

pollu-tantsthat are includedin thelists of prioritypollutants ofthe

EuropeanUnion[17]andUSEnvironmentalProtectionAgency[18]

duetotheirmutagenicandcarcinogenicproperties[19–21].They

areformedduringincompletecombustionoforganicmatterand

originatefromboth natural and anthropogenic sources [22,23].

HumanexposuretoPAHsoccursbyallroutesofexposure,namely

inhalation,ingestion,andskincontact[8,24–28].Onceabsorbed

intobloodstream,PAHsarebiotransformedanddistributedwithin

humanbody,beingmostlyeliminatedthroughurineasglucuronide

and/orsulfateconjugates[22,29,30].Thus,urinarymetabolitesof

PAHs(OH-PAHs)reﬂect amore accurateestimation ofthetotal

exposure.Urinary1-hydroxypyrene(1OHPy),themajormetabolite

ofpyrene,isthemostfrequentlyusedbiomarkertoassessPAHs

exposure [1,11,31–33]. 3-hydroxybenzo[a]pyrene (3OHB[a]P) is

oneofthemetabolitesofbenzo[a]pyrene,anditisconsideredas

thePAHbiomarkerofcarcinogenicity[32].1-hydroxynaphthalene

(1OHNaph)isfrequentlyusedtoassesstheexposureto

naphtha-lene[34],aPAH thatwasselectedasanimportantindicatorof

indoorairpollutionbytheWorldHealthOrganization(WHO)[35].

DuetotheubiquityofPAHs,theirvarioussourcesandroutesof

exposure,theuseofmorethanonePAHsbiomarkerbetter

charac-terizesthetotalexposureofasubject.

Despite the undeniable role that ﬁreﬁghters play in

main-tainingpopulationsafety,limitedinformationrelatedwiththeir

occupational exposure to PAHs is available in the literature

[4,5,11,31,33,34,36–38], being scarce studies that included the

impactoftobaccoconsumption[34,37].Moreover,biomonitoring

ofwildlandfirefighter’sexposuretoPAHsfromfireemissionshas

beenmostlyperformedduringtrainingexercises[11,34,37,38]and

typicallybasedexclusivelyon1OHPyanalysis[31,33,37,38].

Expo-suretoPAHshasbeenassociatedwiththedevelopmentand/or

aggravationoflungfunctionreduction,speciﬁcallywith

exacerba-tionsofasthmaandchronicobstructivepulmonarydisease,some

cardiovascularpathologiesandcancer[39–41].Excessmorbidity

andmortalityinﬁreﬁghtershavebeenrelatedwiththosediseases

andsomeselectedsite-speciﬁccancerscomparativelywithgeneral

population[42–47].

Thus, the present study aims to characterize the impact

of tobacco consumption and occupational exposure on

wild-land ﬁreﬁghters’ total exposure to PAHs. Six urinary PAH

metabolites (1OHNaph, 1-hydroxyacenaphthene (1OHAce),

2-hydroxyﬂuorene (2OHFlu), 1-hydroxyphenanthrene (1OHPhen),

1OHPyand3OHB[a]P)weredeterminedinthreedifferentgroupsof

subjects:i)non-smokingnon-exposedﬁreﬁghters(NSNExp)who

were not involved in ﬁreﬁghting activities withinthe previous

week ofurine sampling,ii) smoking ﬁreﬁghters who werenot

exposedtoanykindofﬁre emissions(SNExp),and iii)smoking

exposedﬁreﬁghters(SExp)whoactivelyparticipatedinwildland

ﬁrecombatactivities(knockdownand/oroverhaul)withinthe48h

priortheurinecollection.Comparisonbetweentheurinarylevels

ofindividualandtotalOH-PAHsamongthethreegroupswas

con-ductedinordertoevaluatetheindividualandcumulativeimpacts

ofthetobaccoconsumptionandparticipationinﬁreﬁghting

activ-itiesonwildlandﬁreﬁghters’totalexposuretoPAHs.

2. Materialsandmethods

2.1. Characterizationofthestudypopulation

Atotalof108healthyfirefightersservingatthreedifferentfire

stations,namelyVinhais(VNH), Mirandela(MDL) andBraganc¸a

(BRG) participated in this study. Fire stations were situated in

Trás-os-MontesandAltoDouroRegion,theNortheastareaofthe

countrythatiseveryyearstronglyaffectedbywildﬁres[48].This

geographicalareaischaracterizedbyveryhotanddrysummers,

andcoldwinters.Allfirefightersoftheselectedfirestationswere

requestedtoﬁlla structuredquestionnaire,whichwasadapted

fromavalidatedform[49].Thequestionnairewasusedtocollect

ﬁreﬁghters’personalinformationonage,weight,numberofyears

ofoccupationalexposureasﬁreﬁghters,timededicatedto

ﬁreﬁght-ingactivitiesinthelast48handtheuseofpersonalprotective

equipmentduringthatperiod;exposuretoenvironmentaltobacco

smoke,tobaccosmokinghabits(includingthenumberofcigarettes

smokedperdayforsmokers),andthemostfrequentlyconsumed

meals(boiled,roasted,andgrilled)duringtheweekbeforeurine

collection. Also, some clinical parameters, such as cardiac

fre-quency,individualdiastolicandsystolicbloodpressure(Geratherm

Desktop,GerathermMedicalAG,Geschwenda,Germany),andthe

arterialoxygensaturation(Oxy-100pulseoximeter,Gima,Italy)

weremeasuredineachparticipantattheendoftheworkshift.

Bodymassindex(BMI;kg/m2₎_was_determined_for_each_ﬁreman.

Accordingtotheinformationcollectedthroughthequestionnaires,

ﬁreﬁghterswereorganizedintothreedifferentgroups:NSNExp,

SNexpandSexp.Theprotocolwasreviewedandapprovedbythe

EthicCommitteeof Universityof Porto,Portugal(ProjectEthics

CommitteeNo.12/CEUP/2015)andallparticipantsgaveawritten

informedconsent.

2.2. Urinesampling,extractionandchromatographicanalysis

Collectioncampaignswereperformedatthethreeﬁrestations

duringJunetoSeptember2015.Allﬁreﬁghterswereaskedto

col-lectaspoturinesampleattheendofaregularworkshiftbetween

TuesdayandThursdayinordertoavoidtheimpactofdifferent

per-sonalweekendactivities.Urinesampleswerecollectedinsterilized

50mLpolycarbonatecontainersandfrozenat−20◦_C_until_analysis.

ExtractionandchromatographicanalysisofurinaryOH-PAHs

were done according to Oliveira et al. [5] and

Chetiyanuko-rnkuletal.[50].CalibrationcurveswerepreparedwithOH-PAH

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that were quantiﬁed witha matrix-matched calibration curve;

theypresentedgoodcorrelationcoefﬁcients(6calibrationpoints;

R2_≥_0.9979)._The_methodology_was_validated_by_recovery

exper-imentswithvaluesrangingfrom70.0to117.5%.Detectionlimits

variedbetween0.0008␮g/Lurinefor2OHFluto0.195␮g/Lurine

for1OHNaph+1OHAcewithrespectivequantiﬁcationlimits

rang-ingfrom0.0028to0.650␮g/Lurine.Intraandinter-precisionassays

wereperformedduringsixconsecutivedayswithRSDvalues

rang-ingfrom1.3%(2OHFlu)to6.4%(1OHPhen)andbetween1.3%to8.1%

(1OHNaph+1OHAce,and1OHPy),respectively[5].Representative

chromatogramsareexhibitedinFig.1S(Supplementarymaterial).

Urinarycreatininelevels(␮mol/mol)werequantiﬁed

accord-ingtotheJaffcolorimetricmethod[51]andusedtonormalizethe

urinaryconcentrationsofOH-PAHs.

Alldeterminationswereperformedintriplicate.

2.3. Statisticaltreatment

StatisticalanalysiswasperformedusingSPSS(IBMSPSS

Statis-tics20)andStatistica(v.7,StatSoftInc.,USA)software.Median

valuesofindividualandOH-PAHswerecomparedthroughthe

nonparametricMann–Whitney Utest since normal distribution

wasnotobservedby Shapiro-Wilk’stest.Statisticalsigniﬁcance

wasdeﬁnedasp≤0.05.

3. Resultsanddiscussion

3.1. Characterizationofthestudypopulation

Theoverallmeanageswere34yearsforNSNExp(22–48years)

and SNExp (21–60 years) ﬁreﬁghters, while SExp subjects had

a meanage of31 years (21–53 years); nostatisticaldifference

(p>0.05)wasobservedbetweenthethreegroups.

BMI, the most commonly used index of weight-for-height,

isa tool commonlyusedtoclassify underweight(<18.5kg/m2_),

normal weight(18.5–25kg/m2_), _overweight _(25–30_kg/m2_), _and

obesity(degreeI:30–35kg/m2_;_degree_II:_35–40_kg/m2_;_degree_III:

≥40kg/m2₎_in_adults_[52]_._The_overall_BMI_values_ranged_between

19kg/m2_(SNExp_of_VNH_and_SExp_of_MDL)_to₃₆_kg/m2_(NSNExp

ofBRG)(mean25kg/m2₎₍_Table₁_)._A_total_of_61%_of_{ﬁreﬁghters}

hadnormal BMIvalues; 22%of NSNExp,3%of SNExp,and 14%

ofSExpindividualspresentedBMIvalues higherthan25kg/m2_,

suggesting an overweight. Signiﬁcantdifferences of BMI levels

wereobservedbetweenNSNExp(28kg/m2₎_and_SNExp₍₂₄_kg/m2_;

p=0.05)groups,andamongNSNExpandSExpsubjects(24kg/m2_;

p=0.013).NSNExpfirefightersservingatMDLandBRGfire

cor-porations had mean BMI levels indicative of overweight, with

someindividualsrevealingvaluesofdegreeIandIIofobesity[52]

(Table1).Obesityisanutritionalpathologythatmayconducttothe

developmentofhealthproblems[52].ThedeterminedBMIlevels

areinaccordancewiththenationalreport,whichindicatedthat

52.8%ofthePortugueseadultpopulationwasoverweightin2014

[53].

Arterial hypertensionis an asymptomatic disease

character-izedbycontinuallyelevatedbloodpressure,usuallydiastolicblood

pressure≥90mmHgand/orsystolicbloodpressure≥140mmHg

[54].Thevaluesofdiastolicandsystolicbloodpressurein

ﬁreﬁght-ersrangedbetween49and114and120–152mmHgforNSNExp,

61–97 and 108–152mmHg for SNExp and from 60 to 98 and

113–156mmHgforSExpsubjects,respectively.Atotalof83%of

NSNExpand SNExp,and61%ofSExpﬁreﬁghterspresented

nor-malvaluesof bloodpressure;17%(NSNExpand SNExp)to39%

(SExp)oftheparticipantsrevealedtohavelevelshigherthanthe

recommendedlimits(Table1).Thecardiacfrequencyobservedin

ﬁreﬁghterswasoverallwithintherecommendedrangeof60–100

heartbeats/min[55].Thearterialoxygensaturationvalueswere

alsowithinthenormalrangeof95–100%[55].

3.2. DetectionratesofOH-PAHs

Thedetection of urinaryOH-PAHs conﬁrms theexposureto

PAHs,regardlessofthesource.Thecollectionofspoturinesamples

in occupational biomonitoringstudies is frequentlyused,

how-everthevariabilityinthevolumeofurinecollectedanditstotal

watercontentneedstobetakenintoconsideration.Toovercome

theselimitations,thecreatinineadjustmentisthemostfrequently

usedmethodtonormalizetheconcentrationsofurinary

metabo-lites[56],thusitwasappliedinthisstudy.Creatininecanbealso

usedasacriterionofacceptabilityofthecollectedspoturine

sam-plesifitsconcentrationsrangebetween0.3g/Lto3.0g/L[57].In

this study, urinary creatinineconcentrations varied from 0.706

to2.90g/L forNSNExp individuals,between0.91 to2.77g/L for

SNExpﬁremen,and0.700to2.95forSExpsubjects.Nosigniﬁcant

differenceswerefoundbetweenthegroups (p>0.05).1OHPhen

wasquantiﬁedin allsamples,1OHNaph+1OHAce, 2OHFlu,and

1OHPyweredeterminedin 97%oftheurinesamples.3OHB[a]P

wasneverdetectedandthusitwasexcludedfromthefurther

anal-ysis.SomeauthorshaveobservedthatPAHswithlowmolecular

weight(2and 3 aromaticrings,suchasnaphthalene,

acenaph-thene,ﬂuorene,andphenanthrene)arepredominantlyeliminated

asmacromolecules conjugatesthrough theurine [4,5,23,58,59].

Informationrelated with pharmacokinetics of OH-PAHs is very

scarce, reasonwhy theeliminationkineticsof PAH metabolites

foreachrouteofexposureremainunclear.For 1OHPy,themost

characterizedOH-PAH,thehalf-lifeexcretionratevariesbetween

6and35h[60,61],from4.4–12h[58,62]andupto13h[62–64]

afterinhalation,ingestion,anddermalexposures,respectively.For

theotherOH-PAHs,Lietal.[59]reportedahalf-lifeexcretionrate

of3.3–6.2hfor1OHNaph,2.3–4.0hfor2OHFlu,and4.3–6.1hfor

1OHPhenforingestioninnon-smokingvolunteerswithno

occu-pationalexposuretoPAHs.Withincreasingmolecularweightof

PAHs,thecomplexityoftheirmetabolismalsoincreasesso

metabo-litesofhighmolecularweightPAHsarepredominantlyeliminated

throughthefecesratherthaninurine[59,65].Fernandoetal.[34]

detected1OHPyand3-hydroxyﬂuorantheneinlessthan50%ofthe

totalsamples.Otherauthorshavealsoreportedverylowdetection

ratesfor3OHB[a]Pinexposed(smokingandnon-smoking)workers

[59,66,67].

3.3. Impactoftobaccosmoke

Theconcentrations of individualcompoundsin NSNExp and

SNExpgroups,organizedperﬁrestation,arepresentedinFig.1.The

levels of 1OHNaph+1OHAce (0.033–0.98␮mol/mol creatinine;

0.138–4.19␮g/Lurine),1OHPhen(0.002–0.077␮mol/mol

creati-nine;0.007–0.362␮g/Lurine),and1OHPy(0.004–0.089␮mol/mol

creatinine; 0.022–0.369␮g/L urine) (Fig. 1) determined in this

studyforNSNExpindividualswerewellbelowthereference

val-uesdeﬁnedbytheGermanHumanBiomonitoringCommissionfor

thegeneralnon-smokingpopulation:<30␮g/Lurinefor1OHNaph

[68], 0.6␮g/L urine for 1OHPhenand 0.5␮g/L urine for 1OHPy

[68–70].Thelevelswereinasimilarrangeasthosereportedby

Haineset al. [71] forthe Canadianpopulationduring thethird

cycle(2012–2013)ofalargeongoingstudy(2007–2019)conducted

bytheCanadianHealthMeasureSurveys,andalsoinagreement

withtheconcentrationspreviouslyreportedforotherNSNExp

Por-tugueseﬁreﬁghters[4].InEuropeancountries,theconsumptionof

anykindoftobaccowasrestrictedand/orforbiddeninenclosed

publicplaces,onpublictransport andin workplaces,withonly

limitedexceptionsallowedforsomeparticulareconomicsectors

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Fig.1. Concentrationsofurinarymonohydroxyl-PAHs(median,25–75percentilesandrange;␮mol/molcreatinine;1OHNaph+1OHAce:1-hydroxynaphthaleneand

1-hydroxyacenaphthene;2OHFlu:2-hydroxyﬂuorene;1OHPhen:1-hydroxyphenanthrene;1OHPy:1-hydroxypyrene)determinedinnon-smokingnon-exposed(NSNExp)and

insmokingnon-exposed(SNExp)firefighters’fromthreedifferentfirestations(Vinhais(VNH),Mirandela(MDL),andBragança(BRG)).*_{Statistically}_significant_differences

atp≤0.05betweennon-smokingnon-exposedandsmokingnon-exposedﬁreﬁghters(non-parametricMann–WhitneyUtest).ThevalueofLOD/√2wasusedwheneverthe

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Table1

Characterizationoffirefighters(n=108)fromVinhais(VNH),Mirandela(MDL)andBragança(BRG)firestationsthatparticipatedinthestudy.NSNExp:non-smoking

non-exposed;SNExp:smokingnon-exposed;SExp:Smokingexposedindividuals.

Characteristic VNH MDL BRG

NSNExp SNExp SExp NSNExp SNExp SExp NSNExp SNExp SExp

Fireﬁghters(n) 9 6 15 9 6 9 18 6 30

Age(mean±SD;min–max;years) 27±6.7 (23–35) 38±12 (30–47) 29±4.0 (25–35) 29±7.0 (22–36) 43±24 (26–60) 33±12 (25–48) 40±5.6 (34–48) 22±1.4 (21–23) 31±9.4 (21–53) Bodymassindex(mean±SD;

min–max;kg/m2₎ 24±3.2 (21–26) 22±3.3 (19–24) 23±1.7 (21–24) 29±5.0 (26–35) 24±1.2 (23–25) 22±2.8 (19–25) 29±4.2 (25–36) 26±2.4 (24–28) 26±2.3 (22–29) Diastolicbloodpressure

(mean±SD;min–max;mmHg) 81±4.5 (77–86) 65±5.7 (61–69) 87±7.6 (81–96) 80±33 (49–114) 73±1.4 (72–74) 84±18 (60–96) 86±11 (72–106) 92±7.1 (87–97) 83±9.9 (68–98) Systolicbloodpressure

(mean±SD;min–max;mmHg) 136±2.5 (133–138) 110±3.5 (108–113) 138±6.3 (129–144) 128±9.7 (120–139) 127±0.71 (127–128) 132±23 (113–156) 137±11 (127–152) 138±19 (125–152) 132±11 (118–150) Cardiacfrequency(mean±SD;

min–max;heartbeats/min)

69±9.9 (58–76) 73±1.4 (72–74) 74±16 (54–87) 76±25 (56–105) 77±1.4 (76–78) 83±19 (54–112) 72±9.4 (62–84) 79±5.7 (75–83) 78±12 (64–101) Arterialoxigensaturation

(mean±SD;min–max;%) 98±1.2 (97–99) 99a ₉₈_±_0.7 (97–99) 99a ₉₇_±_0.7 (97–98) 98±0.6 (97–99) 97±1.2 (95–98) 97±0.7 (97–98) 97±1.4 (95–99) Respiratorypathologies(n) No 1 No 2 No No 1 No No rhinitis; sinusitis allergicto pollens, dust,dust mites, varnishes sinusitis sinusitis

Numberofcigarettessmokedper

day(mean±SD;min–max)

n.a. 8±3 (6–10) 21±2.2 (20–25) n.a. 15±7.1 (10–20) 16±7.6 (5–25) n.a. 11±1.4 (10–12) 16±5.6 (4–20)

Numberofyearsasﬁreﬁghters

≤10years(%) 33 50 20 33 50 67 17 100 70

10–20years(%) 67 50 80 67 0 0 33 0 20

≥20years(%) 0 0 0 0 50 33 50 0 10

Timededicatedtoﬁreﬁghting

activities(48hbeforesampling;

mean±SD;min–max;h) n.a. n.a. 3.2±1.1 (2–4) n.a. n.a. 2.0±0.6 (1–4) n.a. n.a. 3.1±2.2 (0.5–8) na–Notapplicable.

a_All_{ﬁreﬁghters}_from_this_group_presented_the_same_value_of_arterial_oxygen_saturation_at_the_end_of_their_work_shift.

environmentaltobaccosmokeinthefacilitiesoftherespectiveﬁre

stations.Non-smokingﬁreﬁghtersalsoreportedintheir

question-nairethattheywerenotexposedtoenvironmentaltobaccosmoke

outsideoftheirﬁrecorporationintheweekprecedingtheurine

collections. Thequantiﬁcation of urinarycotinine, theprincipal

metaboliteofnicotine(biomarkerofexposuretotobaccosmoke)

allowsvalidatingdata(obtainedbythequestionnaires)concerning

thesmokinghabitsofﬁreﬁghters;however,itwasnotdetermined

in this study. Still, there is generally a highconcordance level

betweentheinformationreportedinthequestionnairesof

smok-ingindustrialworkersandtheurinaryconcentrationsofcotinine

[73],beingthedifferencesobservedbetweenNSNExpandSNExp

ﬁreﬁghtersattributedtotobaccoconsumption.Also,itshouldbe

takeninconsiderationthatthestudiedindividualsreporteddiets

exclusiveofcharbroiledanddeep-friedfoodswithintheﬁvedays

beforeurinecollection,sothecontributionoffoodtotheoverall

PAHsexposurecanbeconsideredasnegligible.

LevelsoftotalOH-PAHs(

OH-PAHs)inPortuguese

firefight-ersareexhibitedinTable2.Atthethreefirestations,themedian

concentrations of individual (Fig. 1) and total (Table 2)

com-poundsin SNExpwere overallhigher thanin NSNExpsubjects.

Urinaryconcentrationsof1OHNaph+1OHAceforSNExp

ﬁreﬁght-erswereincreasedfrom22%(VNH:0.097versus1.18␮mol/mol

creatinine;p>0.05)to339%(MDL:0.67versus2.96␮mol/mol

cre-atinine;p=0.024) comparatively withNSNExp individuals. The

urinarylevelsoftheotherPAHmetabolitesfollowedthesame

ten-dency:29%(BRG:0.017versus0.022␮mol/molcreatinine;p>0.05)

to188%(VNH:0.118versus0.340␮mol/molcreatinine;p=0.009)

for2OHFlu,76% (VNH:0.029versus0.051␮mol/molcreatinine;

p=0.002)to176%(MDL:0.074versus0.204␮mol/molcreatinine;

p>0.05)for1OHPhen,and20%(VNH:0.020versus0.024␮mol/mol

creatinine;p>0.05)to167%(BRG:0.009versus0.024␮mol/mol

Table2

TotalurinaryPAHmetabolites(

OH-PAHs)concentrations(medianandrange;

␮mol/molcreatinine)determinedinnon-smokingnon-exposed(NSNExp),smoking

non-exposed(SNExp),andsmokingexposed(SExp)ﬁreﬁghtersfromtheselected

ﬁrestations:Vinhais(VNH),Mirandela(MDL)andBraganc¸a(BRG).

Firestation

OH-PAHs(␮mol/molcreatinine)

NSNExp SNExp SExp

VNH 0.16 0.82* _5.34* (0.12–1.12) (0.05–1.67) (2.20–8.59) MDL 0.82 2.06* _5.71* (0.56–1.24) (0.59–3.59) (5.44–5.94) BRG 0.42# _0.74#,* _1.91* (0.05–0.47) (0.49–1.02) (0.09–52.4)

#_{Statistically}_signiﬁcant_(p_<_0.05)_between_non-smoking_non-exposed_and

smok-ingnon-exposedﬁreﬁghters.

*_{Statistically}_signiﬁcant_(p_<_0.05)_between_smoking_non-exposed_and_smoking

exposedﬁreﬁghters.

creatinine;p=0.005)for1OHPy(Fig.1).Feunekesetal.[37]also

foundconcentrationsof1OHPythatwere213%higherintheurine

ofsmokerscomparedwithnon-smokingﬁreﬁghters(0.47versus

0.15␮mol/molcreatinine;p=0.01)duringasetofcontrolledﬁres

inaconﬁnedtrainingarea.Overall,tobaccoconsumptionpromoted

a

OH-PAHsconcentrationincreaseof76%(BRG)to412%(VNH)

(Table2).Inagreement,Fernandoetal.[34]previouslyreported

higher levels of urinary OH-PAHs for smoking ﬁreﬁghters

dur-ingtraining exercisesatCanadian burnhouses.Inaddition,the

majorityofavailablestudies(mostlynon-occupationalones)also

concludedthatsmokerspossesshigherlevelsofurinaryOH-PAHs

thannon-smokingsubjects[74,75],whichmaybeattributedtothe

occurrenceofgeneticpolymorphismsinthecarcinogen

(6)

0 20 40 60 80 100 VNH MDL BRG Dis tributio n (% ) 1OHNaph+1OHAce 2OHFlu 1OHPhen 1OHPy 0 20 40 60 80 100 VNH MDL BRG Dis tributio n (% ) 1OHNaph+1OHAce 2OHFlu 1OHPhen 1OHPy 0 20 40 60 80 100 VNH MDL BRG Dis tributio n (% ) 1OHNaph+1OHAce 2OHFlu 1OHPhen 1OHPy

a)

b)

c)

Fig. 2.Distribution of monohydroxyl-PAHs (1OHNaph+1OHAce:

1-hydroxynaphthaleneand1-hydroxyacenaphthene;2OHFlu:2-hydroxyﬂuorene;

1OHPhen:1-hydroxyphenanthrene; 1OHPy:1-hydroxypyrene)in theurine of

non-smokingnon-exposedﬁreﬁghters(a),smokingnon-exposed(b)andsmoking

exposed(c)firefightersfrom differentfirestations(Vinhais(VNH),Mirandela

(MDL),andBraganc¸a(BRG)).

carcinogenicPAH[17]hasbeendetectedincigarettesmokeonlyin

smallquantitiesandthereforeitisdifﬁculttodetectits

metabo-lites in theurine of smoking people [15,61]. Haines et al. [71]

detectedbenzo[a]pyrene,chrysene,andﬂuoranthenemetabolites

inlessthan2%oftheurinesamplescollectedinCanadiancitizens

withintheCanadianHealthMeasuresSurveyduringthethirdcycle

ofthestudy.Nosigniﬁcantdifferenceswereobservedbetweenthe

distributionproﬁlesofOH-PAHsinNSNExpandSNExpsubjects,

with1OHNaph+1OHAce accountingfor 66–91%of

OH-PAHs,

followedby2OHFlu(4.9–21%),1OHPhen(1.8–6.9%),and1OHPy

(1.5–6.3%)(Fig.2aandb).Still,LuandZhu[76]describedasimilar

proﬁlefor17airbornePAHsinthetobaccosmokeof12commercial

brandcigarettes(2–3aromaticringsaccountedwith74%ofPAHs;

4-ringcompoundsrepresented11%ofPAHsandPAHswith5and

morearomaticringscontributedwith15%ofPAHs).

Therelationbetweentheurinarylevelsofindividualandtotal

OH-PAHswiththenumberofsmokedcigarettesforeachSNExp

subject was explored through the determination of Spearman

correlationcoefﬁcients(r).Theattainedcorrelationswere

predom-inantlymediumtohigh(r≥0.878andp≤0.021atBRG;r≥0.603

andp≤0.205atVNH;r=0.878andp≤0.021atMDL,exceptfor

1OHNaph+1OHAce and 2OHFluat VNH and MDLﬁre

corpora-tions).Hagedornetal.[74]alsoobservedsigniﬁcantcorrelations

(r=0.34–0.63andp<0.001)betweenthelevelsofurinaryOH-PAHs

withthedailycigarette consumptioninsmokers,revealingthat

smokersofcigaretteswithhighertaryieldexcretedsigniﬁcantly

higheramountsofurinary1-and2OHNaph,2OHFlu,1+9OHPhen,

2+3OHPhen,and1OHPythannon-smokers.

3.4. Impactofﬁreemissions

Since no signiﬁcant differences were observed between the

number ofcigarettesconsumed bySNExpand SExpﬁreﬁghters

(p>0.05),thesetwogroupswereusedtostudytheinﬂuenceof

fire emissions on firefighter’s PAHs exposure. Fig.3 presents

the medianconcentrations of each OH-PAHand the respective

rangesforSNExpandSExpﬁreﬁghtersperstation,whilethe

respec-tivedistribution(%)isexhibitedinFig.2(bandc).Firemenwho

weredirectlyinvolvedinwildlandﬁrecombatsreportedtheuse

ofself-protectiveequipmentwithﬂame-retardantproperties,

hel-metwitheyeprotection,ﬂashhoodandgloves,asrequiredbythe

Portugueselegislation[77].However,theurinarymedian

concen-trationsofindividual(Fig.3)and

OH-PAHs(Table2)wasoverall

higherinSExpthaninSNExpﬁreﬁghters.1OHNaph+1OHAcewere

byfarthemostpredominantOH-PAHs,accountingfor72–91%and

66–84%of

OH-PAHsfor (smoking)non-exposedandexposed

subjects,respectively(Fig.2bandc).Theirconcentrationsincreased

between 48% (MDL: 2.96versus 4.38␮mol/mol creatinine) and

268%(VNH:1.18versus4.35␮mol/molcreatinine)forSExp

ﬁre-ﬁghterscomparedwithSNExpsubjects(p≤0.024;Fig.3).2OHFlu

wasthesecondmostabundantPAHmetabolite(2.8–21%of

OH-PAHs forSNExp and 13–28%for SExpﬁreﬁghters), followedby

1OHPy(1.5–4.2%versus1.4–3.1%)and1OHPhen(1.3–3.4%versus

1.6–2.6%). Urinary 2OHFlu was the compound with the

high-estincrement in SExpindividuals, increasingfrom 111% (VNH:

0.340versus0.718␮mol/molcreatinine;p=0.031)to1068%(BRG:

0.022versus0.257␮mol/molcreatinine;p≤0.001)while1OHPy

(83%(BRG:0.044versus0.024␮mol/molcreatinine,p=0.001)to

220% (MDL: 0.462 versus 0.144␮mol/mol creatinine, p>0.05))

and 1OHPhen were the least affected (87% (BRG: 0.016 versus

0.030␮mol/molcreatinine;p=0.005)to112%(VNH:0.051versus

0.108␮mol/molcreatinine;p>0.05))byﬁreﬁghters’sexposureto

emissionsreleasedduringﬁreﬁghtingactivities(Fig.3).These

ﬁnd-ingsareinaccordancewiththesmallbutsigniﬁcantincreaseof

1OHPyconcentrationsdeterminedintheurineof13individualsat

aﬁreﬁghtingtrainingschool[38].Edelmanetal.[36]reported

uri-nary1-,2-,and3OHPhenand1OHPyincrementsrangingfrom22

to61%and76to81%inﬁremenwhoactivelyparticipatedin

ﬁre-ﬁghtingactivitiesduringandaftertheWorldTradeCentercollapse.

Laitinenetal.[11]alsoobservedurinary1OHPyconcentrationsthat

were50–537%higherinEuropeanﬁreﬁghtingtrainersatgasand

ﬁrehousedivingsimulators.Morerecently,Fernandoetal.[34]

foundsigniﬁcantlyelevatedconcentrations(upto40-foldincrease

whencomparedwiththebaseline,0.6␮g/gofcreatinine)oftotal

postexposureurinary1-and2OHNaph,2-,3-,and9OHFlu,and

2-,3-,and4OHPhenin25ﬁreﬁghtersduringtrainingexercisesat

Canadianburnhouses;similartrendwasalsoreportedbyOliveira

etal.[5]fornon-smokingﬁreﬁghtersthatweredirectlyinvolved

inﬁrecombat(knockdownandoverhaul).BRGwastheﬁre

sta-tionwherethedifferencesbetweenSNExpandSExpindividuals

wereallstatisticallysigniﬁcantforindividual(Fig.3c)and total

(Table2)OH-PAHs(p≤0.05).WithintheSExpﬁreﬁghtersserving

atBRGﬁrecorporation,threeindividualspresentedmuchhigher

levelsof1OHNaph+1OHAce(49.6–52.2_␮mol/molcreatinine)in

comparisonwiththeotherexposedcolleagues;nospeciﬁcsource

(7)

OH-Fig.3. Concentrationsofurinarymonohydroxyl-PAHs(median,25–75percentilesandrange;␮mol/molcreatinine;1OHNaph+1OHAce:1-hydroxynaphthaleneand

1-hydroxyacenaphthene;2OHFlu:2-hydroxyﬂuorene;1OHPhen:1-hydroxyphenanthrene;1OHPy:1-hydroxypyrene)determinedinsmokingnon-exposed(SNExp)and

smokingexposed(SExp)firefighters’fromthreedifferentfirestations(Vinhais(VNH),Mirandela(MDL),andBragança(BRG)).*_{Statistically}_significant_differences_at_p_≤_0.05

betweensmokingnon-exposedandsmokingexposedﬁreﬁghters(non-parametricMann–WhitneyUtest).ThevalueofLOD/√2wasusedwhenevertheconcentrationof

(8)

PAHconcentrationsrangedbetween0.74(BRG)and2.06␮mol/mol

creatinine(MDL)forSNExpandfrom1.91(BRG)to5.71␮mol/mol

creatinine(MDL)forSExp(Table2).Thedeterminedlevelsof

OH-PAHsincreasedbetween158(BRG)and551%(VNH)(p≤0.02)in

exposedfiremen,reflectingtheimpactoffirefightingactivitieson

thetotalPAHsexposure(Table2).

Theinter-relationbetweenindividualandtotalOH-PAHswas

also estimated. Overall, moderate to strong correlations were

observed among individual compounds and between

individ-ual OH-PAHs with

OH-PAHs for SExp individuals working

at VNH (r≥0.737; p≤0.006, except between 1OHPhen with

1OHNaph+1OHAce and with

OH-PAHs) and BRG (r≥0.514;

p≤0.050,except between2OHFlu and 1OHNaph+1OHAce and

with1OHPy)ﬁrestations.Theseﬁndingsindicatedthe

predomi-nantimpactofcommonsourcesofPAHsexposure.Inaddition,the

correlationbetweentheurinarylevelsofindividualandOH-PAHs

withthenumberofhoursthateachﬁreﬁghterdedicatedto

com-batactivitieswerealsoestimated.Ingeneral,moderatetostrong

correlationswereobservedforallﬁreﬁghtersfromthe

character-izedﬁre stations:r≥0.760and p≤0.028atVNH; r≥0.878and

p≤0.021exceptfor2OHFluand1OHPhenatMDL;r≥0.413and

p_≤0.023exceptfor1OHNaph+1OHAceand1OHPyatBRG.These

resultsshowtheinﬂuenceofparticipationinﬁrecombat

activi-tiesonPAHsexposureofﬁremen.Despitetheshortperiodof

exposure,theuseofself-protectiveequipmentrevealedtobe

insuf-ficienttoprotectfiremenfromtheemissionsreleasedduringfires

andthuspreventiveactionmeasuresshouldbeimplementedto

reduceinhalationanddermalexposuretoPAHsduringﬁrecombat.

In a view of the scarce information regarding ﬁreﬁghters’

occupational exposure, comparisonwiththe reportedresultsis

extremelydifﬁcult.Furthermore,thereporteddataarefrequently

not normalized withcreatinine concentrations [11,33,36]. Still,

theurinary levelsof 1OHPy in SExpﬁreﬁghters (overallrange:

0.025␮mol/molcreatinineatVNHto0.462␮mol/molcreatinineat

MDL)werelowerthanthosereportedfor43Canadianﬁreﬁghters

involvedinaﬁrecombat(0.080–3.63␮mol/molcreatinine;[31]).

TheconcentrationsinSExpﬁreﬁghtersdeterminedinthisstudy

wereoverallhigherthanthelevelsobservedforNSNExpﬁreﬁghters

servingatotherPortugueseﬁrestations[5].

Limitedinformationisavailableconcerningthereference

stan-dards and guidelines for urinary levels of OH-PAHs. In 2010,

theAmericanConferenceofGovernmental IndustrialHygienists

recommendeda1OHPylimitof0.5␮mol/molcreatininefor

occu-pationalPAHsexposure[78].Onlythreeexposedﬁreﬁghtersfrom

MDLﬁrestationexceededthatreferenceguideline,theurinary

OH-PAHconcentrationsofthoseﬁremenbeingmuchlowerthanthe

no-biologicaleffectlimitof1.4␮mol/molcreatinineproposedby

Jongeneelen[29].

3.5. Cumulativeeffectsoftobaccosmokeandﬁreemissions

Themajorityofoccupationalhealtheffects,includingthe

devel-opment of cancers, are predominantly caused by exposure to

a multiple causal factors rather than to a speciﬁc agent; as a

consequence, peopleexposed to more than one risk factor are

moreprompttopresentthesymptomsand developtheillness.

Smoking ﬁreﬁghters are simultaneously exposed to the

poten-tial health effects of tobacco consumption and the hazardous

fireemissions.Incomparison withNSNExpfirefighters,the

uri-naryconcentrationsof

OH-PAHsinSExpindividualsincreased

from355%(BRG:1.91versus0.42␮mol/molcreatinine;p≤0.001)

to3237%(VNH:5.34versus0.16␮mol/molcreatinine;p≤0.001)

(Table2).Themedianurinaryconcentrationsofindividual

com-poundswereaugmentedashighas308%(BRG:0.394_␮mol/mol

creatinineinNSNExpsubjectsversus1.61␮mol/molcreatininein

SExp;p≤0.001)to550%(MDL:0.674versus4.38␮mol/mol

crea-tinine;p=0.002)for1OHNaph+1OHAce,from508%(VNH:0.118

versus0.718␮mol/molcreatinine;p≤0.001)to1412%(BRG:0.017

versus0.257␮mol/molcreatinine;p≤0.001)for2OHFlu,andfrom

97%(MDL:0.074versus0.146␮mol/molcreatinine;p=0.009)to

275%(BRG:0.008versus0.030␮mol/molcreatinine;p≤0.001)for

1OHPhen.Urinary1OHPy presenteda similartrend with

incre-mentsrangingbetween25%(VNH:0.020versus0.025; p>0.05)

to579%(MDL:0.068versus0.462␮mol/molcreatinine;p≤0.001).

TheincrementsintheurinarylevelsofOH-PAHsreﬂectthe

poten-tialcumulativeeffectsofsmokingconsumptionandoccupational

activitiestothetotalPAHsexposure.Ingeneral,urinary2OHFlu

and 1OHNaph+1OHAce werethe mostaffected compoundsby

the impactof both factors. The Bartlett sphericitytest showed

thatthesemetaboliteswerestronglycorrelatedwitheach other

(r=0.600;p<0.001).Principalcomponentanalysis(PCA)was

per-formedbased onurinary concentrationsof thosetwo OH-PAHs

for NSNExp, SNExp, and SExp ﬁreﬁghters (Fig. 2S,

Supplemen-tarymaterial).TheKaiser–Meyer–Olkinvalueswere≥0.5forboth

variables. The ﬁrstfunction (F1)issued fromPCA explainedup

to80.01% ofthetotal variance, presenting thehighestloadings

forbothvariables (squarecosinesvalues>0.800).Itallowedthe

differentiation ofthe majorityof SExpand NSNEXP ﬁreﬁghters

fromtheothers,highlightingthediscriminatingpowerofurinary

1OHNaph+1OHAce and 2OHFlu.The second function(F2)

con-tributedwith 19.99% of theoriginal data.NSNEXP subjectsare

groupedtogetherwithmostlynegativeF1and(ornearzero)F2

scores.Still,ahighernumberofsubjectswouldbepreciousto

cor-roboratetheﬁndingsachievedinthisstudy.

Previously,Feunekesetal.[37]alsofoundsigniﬁcantinﬂuences

ofbothtobaccosmokingandexposuretosmokereleasedduring

ﬁresontheurinarylevelsof1OHPyintrainersandinstructorsfrom

aﬁreﬁghtingschool.Morerecently,Fernandoetal.[34]observed

higherlevelsofurinaryOH-PAHsandmethoxyphenolsinsmoking

ﬁreﬁghterscomparedwithnon-smokingsubjectsworkingatfour

Canadianﬁrestationsduringtrainingexercisesatburnhouses.The

concentrationsofurinaryOH-PAHsinPortugueseSExpﬁreﬁghters

weremainlymuch lowerthanthelevelsreportedforother

rel-evantoccupationsconcerningPAHsexposure,suchascoke-oven

workers,ironfoundryandaluminumproductionworkers,mining

workers,aswellasemployeesfromgraphiteelectrodes,

refrac-torymaterials,andspecialcarbonproductsindustrialproductions

[67,73,79,80].

Littleinformationisavailableconcerningtheimpactof

short-andlong-termexposuretofireemissionsinfirefighters’health.It

hasbeenreportedthatcardiovasculardiseaseistheleadingcause

ofexcessmorbidityandmortalityinﬁreﬁghters[9,42,43].Some

investigatorshavenoticeahigherincidenceofrespiratoryand

pul-monarysymptomsaswellasairwayshyper-responsivenessand

decay inlung function offirefighters duringfire combat

activi-ties [9,81,82].In addition,tobaccosmokeis associatedwiththe

developmentof lung canceramong other typesof cancers and

diseases,namelyleukemiaandcancersoftheurinaryand

aerodi-gestivetractsaswellasofstomach,pancreas,liver,breast,prostate,

andcolorectaltissues[15].Someauthorshavealsodescribedan

increasedriskofdevelopingrespiratory,inﬂammatoryand

cardio-vascularillnessesinsmokers[83–85].ThusSExpﬁreﬁghtersare

morevulnerabletothedevelopmentand/oraggravationof

cardio-respiratorydiseases;cumulativeandsynergisticeffectsmayoccur.

Certainlifestylesmayalsopotentiatethehealthrisksassociated

withﬁreﬁghters’exposuretoPAHs.Indeed,PAHsareelectrophilic

substancesthathavebeenassociatedwithcardiovasculardisease

andadversereproductiveoutcomes[86].UnmetabolizedPAHsare

knownfor theirteratogenic,mutagenic, and carcinogenic

prop-ertiesand therefore constituteaseriousthreat tothehealthof

humans[19,20].Positiveassociationbetweentheurinarylevelsof

(9)

OH-PAHswithdiabetesmellitushavealsobeenreportedinAmerican

adults[87].Moreover,signiﬁcantassociationshavebeendescribed

betweenthelevelsofurinary1OHPywithasymmetric

dimethy-larginineintheplasmaandalsowithadipocyte-fattyacidbinding

proteinpresentin theserumof Mexicanwomen[27,28].

How-ever,themajorconcernistheabilityofPAHreactivemetabolites

(intheformofepoxidesanddihydrodiols)tobindtosome

pro-teinsandDNAmolecules,thusleadingtobiochemicaldisruptions

andcelldamagethatmayoriginatemutations,tumorsand

can-cers[88].Regardingtheincidenceofcancerinﬁreﬁghters,some

studiesreportedanelevatedriskof developingseveraltypesof

cancers,includingurothelial,skin,lung,kidneyandtesticular

can-cersthroughouttheirprofessionalcareer;however,someﬁndings

remaincontradictory[89–91].

4. Conclusions

ThisstudyassessedthetotalexposuretoPAHsinthreedifferent

groupsofwildlandﬁreﬁghters(NSNExp,SNExp,andSExp)serving

atthreePortugueseﬁrestationsthroughthedeterminationofsix

urinarymetabolites.SExpindividualspresentedlevelsof

OH-PAHsthatwere355–3237%higherthanforNSNExpsubjects,with

occupationalexposuretoﬁrecombatactivitiespromoting

signiﬁ-cantincrementsof158–551%in

OH-PAHs.Tobaccoconsumption

increased76–412%thelevelsof

OH-PAHsforSNExpﬁreﬁghters.

Themain ﬁndingsofthisresearchindicatedthatindividualand

cumulativePAHsexposureoccursbyparticipationinﬁreﬁghting

activitiesandtobaccoconsumption.Morestudiesconcerningboth

occupationalexposureandcharacterizationofothercausalfactors

inﬁreﬁghters,aswellas,toxicologicalandepidemiologicalstudies

areneededtobetterestimatetheoverallrisksandthepotential

healtheffectsofﬁreﬁghter’sexposuretoPAHs.

Acknowledgments

Authors are grateful for the cooperation with Escola

Supe-rior de Saúde-Instituto Politécnico de Braganc¸a and particularly

from all participants. This work received ﬁnancial support

from European (FEDER funds through COMPETE)and National

(Fundac¸ãoparaaCiênciaeTecnologiaprojectUID/QUI/50006/2013)

funds and in the scope of the P2020 Partnership Agreement

ProjectPOCI-01-0145-FEDER-006939(LEPABE)fundedbyFEDER

funds through COMPETE2020.M Oliveira and K. Slezakova are

also grateful for their fellowships, SFRH/BD/80113/2011 and

SFRH/BPD/105100/2014,respectively.

AppendixA. Supplementarydata

Supplementarydataassociatedwiththisarticlecanbefound,in

theonlineversion,athttp://dx.doi.org/10.1016/j.jhazmat.2017.03.

057.

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