AtmosphericPollutionResearch3(2012)289Ͳ300 

Atmospheric Pollution Research



 www.atmospolres.com

ChemicalandmorphologicalcharacterizationofPM2.5collected
duringMILAGROcampaignusingscanningelectronmicroscopy
GladisLabradaͲDelgado1,AntonioAragonͲPina1,ArturoCamposͲRamos1,TelmaCastroͲRomero2,
OmarAmadorͲMunoz2,RafaelVillalobosͲPietrini2
1
InstitutodeMetalurgia,UniversidadAutonomadeSanLuisPotosí,AvenidaSierraLeona550,Col.LomasSegundaSeccion.,C.P.78180,
SanLuisPotosí,Mexico
2
CentrodeCienciasdelaAtmosfera,UniversidadNacionalAutonomadeMexico,CircuitoExteriors/n,CiudadUniversitaria,Del.Coyoacan,C.P.04510,
DistritoFederal,Mexico

ABSTRACT 
PM2.5 were collected in March 2006 during the MILAGRO campaign (Megacities Initiative: Local and Global Keywords:
Research Observations) carried out in the northern region of the Mexico City Metropolitan Area (MCMA), in PM2.5
order to realize an individual characterization of particulate matter through scanning electron microscopy Scanningelectronmicroscopy
coupled with an energy–dispersive X–Ray analyzer (SEM–EDX), acquiring information from around 6000 Individualcharacterization
particlesabouttheirmorphology,sizeandsuperficialchemicalcomposition.Measurementsoftheaerosolwere Elementalcomposition
obtainedatasitelocatedinthenorthernpartofMexicoCity(T0)andalsoatasitelocated30kmnortheast(T1) Regionalimpact
infourtimeintervals6:00–9:00;11:00–14:00;16:00–19:00and21:00–0:00hrs.Employingbackscattered
electron detector (BSD) anthropogenic phases were analyzed with the EDX and elemental composition of ArticleHistory:
individual particles showed mainly elemental composition of Fe–O (24% relative abundance) with spherical Received:06March2012
morphology congruent to emissions from metal–mechanic industrial process and soil re–suspension. Twenty Revised:20May2012
percentoftheaerosolwas"Pb–rich"particlesidentifiedasagglomerationsofnanometricspheresofindividual Accepted:26May2012
sizedistributionsamong1.0–600nmandtheyarerelatedtohightemperatureindustrialemissions.The"Ba–
rich" particles (16%) presented chemical associations of Ba–S–O and irregular morphologies and they were CorrespondingAuthor:
relatedtoemissionsfromthe mineralphaseofbarite thatconstitutestheasbestosoftheautomobilepieces. GladisLabradaͲDelgado
"C–rich" group was the fourth most abundant (12%) one with predominant morphology corresponds to Tel:+52Ͳ444Ͳ8252569
nanometric spheres (between 600 and 800 nm) of compact and continuous surface, this kind of particles are Fax:+52Ͳ444Ͳ8342010
mainlyrelatedtovehicleexhaustemissionsandtheirtemporaldistributionpresentedacleardecreaseduring EͲmail:gladis.labrada@ipicyt.edu.mx
weekendswhenvehicletrafficisreducedontheMCMA.ElementslikeCa,Zn,Cu,Sr,Sn,Al,Sb,NaandWwere
alsodetectedinlessrelativeabundance(28%ofthetotal),andtheirindividualmorphologyandpossiblesource
emissionsaredescribed.

©Author(s)2012.ThisworkisdistributedundertheCreativeCommonsAttribution3.0License. doi:10.5094/APR.2012.032


1.Introduction Sistembetween19°03´–19°54´northlatitudeand98°38´–99°31´
 west latitude with 2240 m above sea level of average elevation.
Particulate matter (PM) atmospheric pollution is currently an The MCMA altitude produces regularly deficient combustion
issueimpactingmainlythebigcitiesofdevelopedcountriesaround processes which emit major quantities of pollutants to the
the world. Diverse epidemiological studies have demonstrated a atmosphere due to the low oxygen content in the air, which is
correlation between PM exposure and adverse human health approximately 23% lower than at sea level (Molina and Molina,
effectsduetoparticlecharacteristicslikeitschemicalcomposition, 2002). Its latitudinal position causes an intense solar radiation
size, air concentration and exposure time. All of these determine reception which increases the speed of photochemical formation
the specific damage caused to the organism (Monn, 2001; ofpollutantslikeozoneandsecondaryparticles.Furthermore,the
Morawska and Zhang, 2002; WHO, 2003; Barrios, et al., 2004; mountains which enclose the MCMA cause the accumulation of
BrunekreefandForsberg,2005;PopeandDockery,2006). emissions.Itslocationatthecountrycentercausesthisareatobe
 affected by anticyclonic systems throughout the year and also
TheMexicoCityMetropolitanArea(MCMA)isconsideredasa maintains clear skies and consequently the photochemical
megacity because is an urban region with more than 10 million capability of the atmosphere is enhanced. Besides, these systems
habitants (WHO/UNEP, 1992), currently its population is close to reduce the wind speed nearby the ground surface inhibiting the
20 million and the implications about services demand and vertical and horizontal air movements causing decreasing
infrastructure related to its growth have shown a remarkable dispersionofthepollutants.
impacttotheairqualityoftheregion. 
 FederalDistrictEnvironmentalAgencythroughitsDirectionof
The MCMA is formed by Mexico Federal District (16 Programs on Air Quality, which designs prevention and control
delegations) and 59 municipalities of Mexico State, includes a strategies to reduce atmospheric pollution, establishes in its last
surface of 7732 km2, 19% of these corresponds to the Mexico EmissionsInventorypublishedin2008(EICP,2008)thatamongthe
FederalDistrictandtheother81%toMexicoState.Itissituatedon mainpollutantsemittedintheMCMA,andidentifiedas“principal
the east part of the region known as Transversal Neovolcanic pollutants”,aretheemissionsofcarbonmonoxide,volatileorganic
290
0 LabradaͲDeelgadoetal.–Atm
mosphericPollutiionResearch3(2012)289Ͳ300 

com mpounds, sulfu ur dioxide, nitrrogen oxides and

a fine particculate partiicles in the airr) the MILAGR RO project (Me egacities Initiattive:
matter. In spite ofo the constantt governmentaal effort to maintain Local And Global Research
R Observations) was carried out du uring
thee acceptable po ollution limits established byy the Health Official
O Marcch 2006, with the objective of monitoringg air pollutants at
Meexican Norms (N NOMS, 2002) for
f air pollutannts to guaranteee the different distancess from an em mitting source to evaluate their
t
pop pulation’s health (Table 1), ambient
a contingency episodees still impaact to the globbal scale. In orrder to establish the monitooring
occcur in the MC CMA. However,, it has been demonstrated d that sitesonsurface,meeteorologicalm modelsandsate elliteanalysisw
were
con ntaminant emiissions do nott remain just inside the MCMA M utilizzed,locatingthreesamplingp pointswhichpe ermittedtoregiister
(Mo olina et al., 2007),
2 they could be spread d by the wind d and the pollutant plum me under three different conditions: (a) frresh
tran nsported through large disttances impactting diverse places, local emissions (TT0), (b) well mixed emissio ons (T1), and (c)
con nsequently the emissions imp pact study on regional and global
g emisssionschemicallytransformedbyphotochem micalreactions((T2).
scaleresultingofttheinteresttotthescientificco ommunity. Thesse sites were loocated at the M
Mexican Petrolleum Institute (T0)
 insid
de the MCMA and two otheer  outside; on ne of them at the
TTryingtounderstandtheevolu ution,transporrtandsignifican nceof Techhnological University of Tecam mac (UTTEC) in Mexico State (T1)
theeMCMAurban plumeformedbygasesandaaerosols(suspeended andttheotherattheeBiznagaRanchinHidalgoStaate(T2)(Figuree1).

Table1
1.Summaryofth heOfficialMexica
anNorms,EnvironnmentalHealthaandtheadmissibllelimits
forthe“principa
alpollutants”tha
atguaranteethep
population’sheallth(NOMS,2002))

POLLUTANT NORM PERMISSIBLLELIMIT

0.110ppm,inonehour
O3 NOM–020–SSA1––1993
0.080ppm,onmobileaverageofeighthours
C
CO NOM–021–SSA1––1993 11.00ppm(12595μg//m³),onmobileaverageofeighthhoursonceayearr
ppm(341μg/m³),averageof24 ho
0.13p oursonce ayear
S 2
SO NOM–022–SSA1––1993
0.03p
ppm(79μg/m³),aannualaverage
N 2
NO NOM–023–SSA1––1993 0.21p
ppm(395μg/m³),inonehouronceeayear
th
120μgg/m³,averageof24 hours. 98 Peercentilefromdedailyvalues
P 10
PM
50μg//m³,annualaveraage
th
NOM–025–SSA1––1993 65μg//m³,averageof2
24 hours. 98 Perrcentilefromded
dailyvalues
P 2.5
PM
15μg//m³,annualaveraage
th
PST
P 210μgg/m³,averageof24 hours. 98 Peercentilefromdedailyvalues
P
Pb NOM–026–SSA1––1993 1.5μgg/m³(threemonthsaverage)




Figure1.Samplingpointloca
ationsfromMILG
GROcampaign(M
MolinaCenterforEnergyandtheEEnvironment).




 LabradaͲDelgadoetal.–AtmosphericPollutionResearch3(2012)289Ͳ300
The monitoring activities were performed during a period of
30 days, 24 hours a day. Eight mobile units were installed in the
MCMA perimeter and six investigation aircrafts equipped with
measuringinstrumentsalsoparticipated,fiveofthemwerebased
inVeracruzStateandtheotherinHouston.Theairdataprovided
very extensive information at different altitudes. Satellite
instrumentswerealsousedwiththepurposeofcoveringalarger
geographicalarea.ThespatialarrangementofthesupersitesT0,T1
and T2 was designed to characterize the chemical/physical
transformations and to locate the ultimate destination of
pollutantsexportedfromtheurbanarea.
 populated agglomerations of around 172410 inhabitants,
According to Fast et al. (2007), the general meteorological
conditions during MILAGRO campaign can be classified into three
regimes:thefirstfrom1stto14th Marchwithsunnyanddrydays;
the second one beginning from 12th March with temperature
decrease,humidityincreaseandvariablewindsfromwesttoeast,
these conditions lasted until 19 March. From 21st March western
winds and a cold front were registered with precipitations in the
last days of the month. In the same fashion, De Foy et al. (2008)
carriedoutaclusteranalysisinordertoidentifythedominantwind
patterns during the campaign. Their results indicated that March
2006 was representative of typical flow patterns experienced in
the MCMA basin during the dry warm season, and six episode
types(thatdescribetransportandbasinventing)wererecognized
in order to understand atmospheric chemistry and to relate
meteorology and pollutant concentrations. Summarizing the six
ventilation episodes by intervals of dates: “South Venting”,
presented up to and includingMarch 7 with uniform transport to
thesouth;“O3–South”presentedon8,12and15–17Marchwhen
wind shift occurred, with transport initially to the south moving
back to the north, in these days ozone peaks presented in the
south of the city; “O3–North” for 9–11, 18–20 and 22 March, the
morningpollutantaccumulationswereventedtothenorthduring
the afternoon; “Cold Surges” on 14, 21 and 23 March having a
strong southward flushing of the basin late into the evening, as
discussed in Fast et al. (2007); “Convection–South” on 24–26 and
31 March, presenting south transport in the late afternoon with
rain in the southern part of the basin; and the last one
“Convection–North” during March 26 to 30 with weak southerly
windcomponentaloftwithagapflowandraininthenorthernpart
of the basin. These meteorological conditions have an important
influence in the pollutants transportation, and according to the
studies mentioned above, around March 22th main wind flux was
towards the north of the MCMA, generating a possible
transportationofthepollutantplumefromT0toT1andT2.
 interest(diameterlessorequalof2.5,1.8,1.0,0.56,0.32and0.18
2.SamplingSites
 
The environmental measurements performed during
MILAGRO campaign consisted in particles and aerosols analysis
such as total mass, ions, trace elements, elemental and organic
carbon, particles size distribution, absorption and dispersion
coefficients,opticalthicknessandparticlesmorphology.
 Potosi,Mexico.Oncethefiltersweretakenfromtheimpactortheir
In this research an individual characterization of particulate
matter emissions was performed for sampling sites T0 and T1 by
means of scanning electron microscopy, with the objective to
describeindetailthemorphologyandchemicalcompositionofthe
“fresh” PM2.5 emission (T0) and compare their characteristics
against those of particles collected upon pollutant plume
transportationduetotheMCMAweatherconditions(T1).
 SuppliesDivisionofStructureProbe,Inc).
The supersite T0 was located at the Mexican Petroleum
InstituteinthenorthofMexicoCityat19°29’Nlatitude,99°08’W
longitude and at altitude of 2240 m. This station is impacted by
urban,residentialandcommercialemissionsandisalsoinfluenced
byfreshroadtrafficemissionsbecauseissurroundedbyfourhigh
traffic roads mainly transited by light duty vehicles and diesel
buses and, an important regional bus station is located at
approximately500mSE,thus,trafficvolumeislarge.Itislocated
291
nexttotheVallejoindustrialzone,locatedat1kmnortheastfrom
this sampling point, so that is impacted by local industrial
emissions and from the Tula industrial area and Tula refinery
(around60kmtothenorth–northwest,intheHidalgoState).The
drylakebedofLakeTexcocowaslocatedtotheeastofT0.

ThestationT1 waslocatedattheTechnologicalUniversityof
Tecamac (UTTEC) in Mexico State, is a semi rural site located at
30km northeast of the Federal District. It is situated at 19°43’ N
latitudeand98°58’Wlongitudeandatanaltitudeof2273m.This
site is far from major urban agglomerations but close to small
according to the 2008 census. The main economical activity is of
commercial type with a total of 3070 small businesses, the
majority of them are food related. It is affected by vehicular
emissions coming from federal road number 85, that is around
500m far from this station and the main vehicles are passenger
diesel buses and light duty vehicles, which are the main mode of
transportationinthearea.

3.Methodology

3.1Particlescollection

PM2.5 sample collection was performed using the Andersen
cascadeimpactorsamplers,inthoseequipmentstheparticlestend
to deviatefrom the air flux due to their accumulated momentum
when airstream becomes curved as it passes through a solid or
semisolid surface. The particles become detached from the
airstream and impact onto the surface. Those samplers are
constitutedbyaseriesofsixaluminumplates,eachofthemwith
400perforationswithdecreasingdiameterswhichinturnincrease
the air velocity in every stage. Through an aspiration tube, an
airstream of 28.3L/min is sampled with a vacuum pump. The
particlesaretransportedintheairstreamandsortedbytheirsizes
in different fractions as they pass through the perforated plates
(diametersfrom0.18to10μm).Particleshavinglargemassesare
depositedinhigheststageswhilesmallerparticlesareabletostay
intheairfluxandaretransportedsuccessivelyatmajorvelocities
andimpactedonthecollectionsurfacesofthenextstages.Inthis
study polycarbonate and quartz filters were employed (Pallflex
ProductsCorp.,Putnam,CT,USA).

PM2.5 samples were collected alternately during March 2006
(3or4samplesaweek)infourtimeintervals(6:00–9:00;11:00–
14:00;16:00–19:00and21:00–0:00hrs)with6cutdiametersof
μm).
3.2SamplepreparationforSEM

For the individual characterization by electron scanning
microscopy a Phillips XL30 of tungsten filament was utilized at
Metallurgy Institute of the Autonomous University of San Luis
central part was extracted using a cylindrical cutter of 1.0cm of
diameter, in this portion was the major accumulation of the
collectedmaterial.ThesamplewasplacedinaluminumSEMholder
with an adherent conductive carbon tape and then, the sample
surfacewascoatedwithafilmofconductingcoaltoeliminateany
possible static charge that could affect the images quality, the
equipmentusedtocover wasanSPI–Module CarbonCoater(SPI

3.3PM2.5analysisbySEM

ThesampleswereplacedintheSEMchamberathighvacuum
to analyze their surfaces with secondary electron detector (SED)
and so register data about their morphology, texture and shape.
The general SEM operation conditions were 20 kV and 10 mm of
workingdistance.Backscatteredelectrondetector(BSD)coupledin
292 LabradaͲDelgadoetal.–AtmosphericPollutionResearch3(2012)289Ͳ300 

the SEM wasused to the superficial chemical analysis (qualitative 4.1.Chemicalcomposition
and semi quantitative). A punctual micro analysis was performed 
with an energy–dispersive X–ray (EDX) analyzer adapted to the According to the characteristic X ray detection performed by
SEM, mainly selecting phases with heavy metals and secondary the energy–dispersive X–ray (EDX) analyzer adapted to the SEM,
inorganic compounds (sulfate phases), due to the BSD image that the most abundant elements detected were Fe, Pb, Ba, C, Ca, Zn
shows major contrast in the areas with major average atomic andCu,presentinthe87%ofthetotalparticles,beingFethemost
number. The microanalysis were obtained with 60 seconds of abundant one. Around 13% of the total particles registered
capture time, 1000 to 2000 counts per second and 30% of dead contents of other elements like Sr, W, Sb, Na, Sn and Al.
time,recordingtheEDXanalysisatthecentralpartoftheparticles. Considering the major abundance of the particles as function of
The morphological and chemical information from the overall the main constitutive elements and their possible health impact,
particlesanalyzed(around6000)wasorganizedinadatabasefor thesephaseswillbedescribedondetail.
thediscussionsoftheobtainedresults. 
 Fe: This element was present in the 24% of the total particles
4.Results (a1450 individual particles). The most abundant phase was iron
 oxides, 77% of this group, (Figure 2a) with irregular and spherical
Anthropogenic particles were the aim of the SEM shapes (ferrites), 13% was of metallic Fe particles and the rest of
characterization of the 275 polycarbonate and 20 quartz filters theparticlesshowedassociationsofFe–Si–Al–Ni–Zn,theelements
analyzed, gathering information of around 6000 individual differentfromFerepresentedaroundthe18%byweightobtained
particles (i.e., their morphology, size and superficial chemical bytheEDXsemiquantitativeanalysis.TheirregularFe–Oparticles
composition).Accordingtothenumberofanthropogenicparticles are associated with corrosion and abrasion of exposed metallic
analyzed by sampling day, a tendency of abundance per day was structuresoutdoors(Aragon,1999;CamposͲRamos,2005;CamposͲ
obtained to determine the most impacted day by number of Ramos et al., 2009), the “ferrites” are associated with emissions
anthropogenicPM2.5. fromindustrialprocesseslikemelting,weldingandsteelindustry
 



Figure2.Characteristicmicrographsandspectrumsofphaseswithmajorcontentofiron(a)andlead(b).
 LabradaͲDelgadoetal.–AtmosphericPollutionResearch3(2012)289Ͳ300 293


emissions (CamposͲRamos, 2005; Aragon et al., 2006; CamposͲ
Ramos et al., 2009). Emissions with high iron concentration have
been reported as well from the abrasion of vehicle parts, mainly
from their breaks and this is especially true for heavy vehicles
(Schaueretal.,2006).
 (between 600 and 800nm) of compact and continuous surface
Pb:TwentypercentoftheparticlespresentedcontentsofPband
the predominant morphology was spherical nanoparticles (Figure
2b). These particles mainly registered EDX spectra corresponding
to lead oxides. It has been reported that this lead phase can be
associated with emissions from garbage incineration, breaks and
tires abrasion, muffler emissions of gasoline and diesel vehicles
andfromdustre–suspensionofhighlytraffickedroads(Schaueret
al.,2006;Moffetetal.,2008a).
 Considering that EC particles from T1 experienced a transport
Ba: The phases rich in Ba (Figure 3) presented chemical
associations of Ba–S–O and irregular morphologies (16% relative
abundance). The presence of this element in the air has been
related to vehicular emissions (Querol et al., 2008) mainly from
braking pads abrasion emissions and, given that barite (BaSO4)
substitutedtheasbestosinthecompositionsofthoseautomobile
pieces, it could be explained the sulfur and oxide content
associated to these phases rich in barium (Sternbeck et al., 2002;
Adachi and Tainosho, 2004). As T0 and T1 have high vehicular
traffic,itcanbeassumedthatthisisthemainemissionsourcefor
these kinds of particles. Also, the Ba–S–O associations could be
related to the painting industry because there is a compound
formed by BaSO4 (70%) and ZnS (30%), called lithopone, that is
employed as a surface covering. In this group, particles of the
mineral phase of barite (BaSO4) was found as well, mainly in T1,
thatisclassifiedasasemiruralsiteanditsglobalchemicalanalysis
estimates that 45% from the PM2.5 comes from T1 soil re–

suspension due to high wind and vehicular traffic on unpaved
roads(EICP,2008;Queroletal.,2008;Molinaetal.,2010).

C:Forthecaseofcarbonrichphases,12%ofthetotalparticles,the
predominant morphology corresponds to nanometric spheres
(Figure4a)thatbelongtophasesofelementalcarbon(EC)andare
considered as tracers of combustion sources (Schauer, 2003) and
asoneofthemainprotagonistoftheclimateforcingduetotheir
optical properties. As opposed to the EC phases characterized in
T0,thosecorrespondingtoT1presentedacoveringofaround300
nm (Figure 4b) which was easily degraded with the SEM electron
beam interaction, however, the EDS chemical analysis detected S
and O signals that represented around 4% of the particle weight.
processduetotheclimaticconditionsreportedfortheMCMAand
alsoduetothepresenceofSandOintheparticleedges,itcanbe
assumed that those refer to secondary phases formed on the
primary particles emitted on T0 as a result of the superficial
interfacereactionwithsubstancespresentsintheatmospherelike
SO2.ThecoveringcouldbeaphaseofSO4–generatedbyreaction
withtheparticleorbycondensationonitssurface,dependingon
the ambient relative humidity and temperature (De Icaza, 2003;
Doranetal.,2008).

Ca: The particles with Ca content presented S and O associations
and irregular morphologies (Figure 5a) and so it can be assumed
that they refer to secondary phases of calcium sulfate since this
material is commonly found in the atmosphere because of the
calcite(CaCO3)sulfation,bySO2deposition,andforitshygroscopic
character (McGovern et al., 2002). This group of particles
representedthe6.0%ofthetotalanalyzed.


Figure3.Micrographsandspectrumsofparticlesmainlycomposedofbarium.


294 LabradaͲDelgadoetal.–AtmosphericPollutionResearch3(2012)289Ͳ300 

Figure4.Characteristicmicrographsandspectrumsofphaseswithmajorcontentofelementalcarbon(a)andcarbonwithSandOtraces(b).


Zn,Cu:TheparticleswithcontentofZnandCurefereithertothe
oxidizedphasesortothemetalliconesoftheseelements(Figures
5band5c),beingmoreabundantinT0.Theparticlesrichinthese
twoelementssummarizethe8.0%ofthetotalPM2.5characterized
by SEM. The zinc–copper oxides are mainly originated by basic
metallic industrial activity, and these are close to T0 sample site.
Moreover, their presence in the air results from metallic pieces
abrasion and from melting; and this explain their characteristic

spherical shape. This kind of particles has also been related to
emissions from worn tires, especially in heavily trafficked roads
(Adachi and Tainosho, 2004). Precisely T1 site is impacted by
passenger buses circulation through federal road number 85, and
thisrepresentsanimportantsourceofthatkindofparticles.



 LabradaͲDelgadoetal.–AtmosphericPollutionResearch3(2012)289Ͳ300 295

Figure5.MicrographsandspectrumsofparticleswithhighcontentofCabeingcalciumsulfatethemostabundant
(a),Zincoxideswithirregularmorphology(b)andsphericalCopperoxides(c).

Inregardsoftheminorityphasesanalyzed,Figure6showsthe
morerepresentativeshapesforeachgroup.Theparticleswithhigh
SrcontentpresentedSO4–associationsandtheirmorphologyshow
definedcleavages(Figure6a)thatarecongruentwiththemineral
phase of celestite (SrSO4), which is commonly found in solid
solutionwithbariteand,asthislastoneislargelyindustriallyused,
that can explains the presence of Sr particles in the air. The Sn
particles presented spherical morphologies (Figure 6b) and their
source is attributed to the welding processes emissions and from
combustion of petroleum products, which could explain their
roundness when condense they from high temperature gaseous
emissions. Particles with high Al content showed mainly irregular
forms (Figure 6c) and low oxygen concentrations related to the
superficial oxidation generated by the environmental conditions,
thismaterialmainlycomesfromoutdoorstructuresabrasion.The
Sb particles presented morphologies oriented as tetrahedral
pyramids (Figure 6d) which corresponds to antimony trioxide and
theirprincipalsourcereferstofugitiveemissionsoftheprocessof
asphalt mixture fabrication, petroleum combustion and melting
and molding of metallic pieces, ferrous and non ferrous; all of

these are punctual sources refereed to industrial combustion
processes (EITP, 2008). The particles “Na–rich” correspond to the
mineral phase of NaCl and their cubic morphology coincides with
the cristallinity of this phase (Figure 6e) that is present in the
atmosphere because this mineral is largely used in the basic
chemical industry. The metallic W particles presented irregular
forms (Figure 6f) and their source is assumed to be from polish
machinery abrasion and from steel industries emissions, due to
tungstenisusedtomakehighhardnessalloys.

4.2.Sizedistribution

The complete size range of the total particles analyzed
oscillated between 2.5μm and particles less than 600nm. To
classifythesizedistribution,fourintervalswereestablished:(1)2.5
–2.0μm;(2)lessthan2.0–1.0μm;(3)lessthan1.0μm–600nm
and (4) less than 600 nm. The predominant size distribution was
the third interval, where the 60% of the particles were classified
(Figure7).Joinedtothesmallcutdiametershowedbythemajority
oftheparticles,wasthesphericalmorphologyofthemostphases
296 LabradaͲDelgadoetal.–AtmosphericPollutionResearch3(2012)289Ͳ300 

lessthan800nm,thesebothcharacteristicsincreasethepossible In the case of “Ba–rich”, 45% of this group was in the third
human health implications that they could represent, because interval of size being predominant, the particles with size of 900
particlesofthatsizeeasilyentertothelungsalveolarregion(Pope nm,theremaining55%ofthebariumphaseswereintheinterval
andDockery,2006). ofparticleslessthan600nm.
 
With respect to the “Fe–rich” particles, the phase of Fe–O ThetotalsphericalECparticlesregisteredinsizesbetween600
presented size in the third interval included the “ferrites” (the and800nm,theonesfromT1madeevidenceofthebiggestsizein
spherical iron oxides) and the irregular oxides. The metallic iron this group, and this can be attributed to the condensation of
particlesweremainlyaround2.5μmandthe90%oftheparticles secondaryphasesontotheoriginalsurfaceareawhenparticlesare
withassociationsofFe–Si–Al–Ni–Znshowedsizelessthan2.0–1.0 transportedfromT0toT1.
μm. 
 Referringtothe“Ca–rich”particlesthe65%ofthegroupwas
The majority of the “Pb–rich” particles presented sizes in the first interval size even was the main contributing phase to
between1.0μmto600nm,butisimportanttomentionthatmost this interval size (2.5 – 2.0 μm). This can be explained due to the
ofthenanoesphereswereagglomeratedinclustersofaround1.5 predominantspeciationoftheCaphase,thatwasconsideredfrom
μm and just around 7.0% of the lead particles were between 200 CaCO3orsulfatedCaCO3,andthefractionedmineralphasepersists
and300nm. inbiggersizes.Theremaining20and15%ofthecalciumparticles
 wereinthesecondandthirdsizeintervalsrespectively.



Figure6.MicrographsandspectrumsofparticlesmainlycomposedofSrbeingSrSO4themostabundantphases(a),sphericalSnoxides,(b)Alirregular
particles(c),“SbͲrich”particleswithtetrahedralpyramidsmorphologiesassociatedtoantimonytrioxide(d),cubicNaClparticles(e)andmetallicW(f).




Figure7.Particlessizedistributiononthefoursizeintervalsestablished,indicatedbypercentagesofthetotalanalyzedparticles.

 LabradaͲDelgadoetal.–AtmosphericPollutionResearch3(2012)289Ͳ300

Theparticlessizeofthe“Zn–rich”groupwaspredominantless
than600nm,aroundthe61%ofthisphase,whiletherestofthese
particles(a109)presentedsizebetween800and950nm(thethird
interval).
 centers and schools takes place during those hours, and also the
The spherical particles with high Cu content represented the
45%ofthesekindsofparticlesandshowedsizelessthan600nm;
however the irregular oxide phases of copper (35% of this group)
presentedasizebiggerthan2.0μmandtherestofthemwerein
thesecondsizeinterval.

Among the minority phases (13% relative abundance) “Al–
rich”particlescontributedtothefirstintervalsizeandthisisowing
to their most probable origin related to outdoor structures
abrasion, this kind of particles represented the 1.4% of the total
particles.ParticleswithSbcontentcontributedtothe2.0%ofthe
totalanalysisandthiswastheonlygroupfromtheminorityphases
thatregisteredinsizelessthan600nm,theremained9.6%(phases
ofSr,Sn,NaandW)wasinthesecondintervalsize,lessthan2.0–
1.0μm.
 abundance tendency shows a decrease of 13% in weekend days
4.3.Particlesabundance
 asheavyvehiclesandparticularones.
Figure 8 shows the total number of anthropogenic particles
analyzed per sampling day in the four time intervals. Asit can be
observed, the major number of particles was obtained on March
17,19and22,accumulatinginthesethreedaysaroundofthe26%
ofthetotalparticlesanalyzedandbeingtheintervalsfrom6:00–
9:00hrsand16:00–19:00hrstheoneswiththemainregisterof
the global anthropogenic phases described in Section 4.1 (14%
relativeabundance).
 T0(around70%fromthetotalofthisphase)prevailinginthetime
Figure 8. March´s time series ofthe total number of particles analyzed by
eachhourintervalofthecollectedsamples.
 analyzeradaptedtotheSEM,allowsobtaininginformationofsome
The particles abundance distribution shows and important
incrementonT1duringMarch19thand22nd ofaround35%above
to the daily average (40 anthropogenic particles) in the time
intervalfrom16:00–19:00hrs,whichcouldconfirmtheresearch
suggesting that March 22nd represented an effective pollutant
plumetransportdayofemissionsfromT0,sincethewinddirection
was northeast to MCMA, these meteorological conditions were
modeled in The Weather Research and Forecasting (WRF) by
employingafour–dimensionaldataassimilationtechnique,andthe
results congruently reproduced the trajectories indicating that
particlesflowedfromT0toT1andT2(Doranetal.,2007;Fast et
al., 2009). In a similar way Lagrangian particles dispersion models
were performed and showed that the air mass retro–trajectories
impactedT1andT2effectivelycomefromT0(Doranetal.,2008;
FastandEaster,2006).
 canbealsorelatedtoemissionsfromhightemperatureprocesses.
297
The interval times with the major PM2.5 quantities of
anthropogenic phases (6:00 – 9:00 and 16:00 – 19:00 hrs)
coincidedwiththehoursofmajorvehicularandindustrialactivity
of the MCMA, because the population commute to the working
industries activities begin. This pattern coincides with the
information described on the Emissions Inventory of Criterion
PollutantsoftheMCMAthatlistsadailygenerationofaround14
tons of PM2.5 in this region, where 45% is emitted between 7:00
and12:00hrs(EICP,2008).

Relating to the carbon particles, for example, the major
abundance of this phase (48% of the “C–rich”) was in the time
intervalfrom6:00–9:00hrsandthiscoincideswithMCMAhighest
vehicular traffic hours reported by the EICP (2008) that
corresponds from 6:00 to 11:00 hrs, presenting the maximum at
10:00hrs.ThiscorrelatesthemainemissionsourceofCparticlesto
internal combustion engines as it is reported by bulk chemical
analysis that associate the PM2.5 to particular sources (Querol et
al., 2008; Mugica et al., 2009). For this group of particles the
andthiscouldbeattributedtotheaminorvehiclefleetcirculation,

ThetendencyoftheT1ultrafineparticlesanalyzedshowedan
increase during days that presented air fluxes from the MCMA
southwest (March 19 and 22), and this can be related to the
pollutantplumetransportphenomenon,speciallytheT0emissions
regionalimpact,whichisaffectedbydirectindustrialandvehicular
emissionsinfluencedbyitssurroundingconditions.Itisimportant
tomentionthatthemajorityoftheleadparticleswerelocatedin
intervalof6:00–9:00hrs,meanwhileforT116:00–19:00hrswas
thepredominantperiod,thisbehaviorsuggestsatransportationof
the lead emissions from T0 to T1 and this difference of the
impacting hours of the “Pb–rich” particles could confirm the
phenomenon.ThetimeseriesforPbparticlesinthetimeinterval
of6:00–9:00forT0showedacleardecreaseintheweekendsand
mainlyinaholidayweekendfromMarch18th–21th,thiscorrelate
theindustrialemissionsimpactontheamountofparticlesemitted
to the atmosphere. Another line tendency that demonstrate the
clear correlation between meteorological conditions and the
presenceofparticulatematterintheatmosphereisthenumberof
EC phases decreased in the last days of March, similarly for lead
phases,thisbehaviorcoincideswiththepresenceofhumidityand
rainfall registered in the MCMA from March 24–30, and this
conditions generate the “troposphere washing” that implies the
decreaseofparticulatematterintheair.

5.Discussions

The individual characterization of the PM2.5 by scanning
electron microscopy and the energy–dispersive X–ray (EDX)
individual aspects from particulate matter. The chemical
composition showed that the three most abundant groups of
particles are constituted by iron oxides, lead oxides and barium
sulfate,thesespeciesarecleartracersoftheemissionsfromroad
trafficandindustrialactivities(Queroletal.,2008;CamposͲRamos
etal.,2011),andthesearetwoofthemaincharacteristicsofthe
northern MCMA, where T0 and T1 are located. The chemical
phasesanalyzedarecongruentwithotherglobalchemicalanalysis
performed by different researcher groups in the same study
region. The large relative abundance of “Fe–rich” particles is
explained with the corrosion and abrasion of exposed metallic
structures and from emissions of metal–mechanic industrial
processes,andasisindicatedontheEICP(2008)atthenortharea
of the MCMA are mainly located industries of smelting and
moldingofmetallicproducts.ThesphericalFe–Ophases“ferrites”
298 LabradaͲDelgadoetal.–AtmosphericPollutionResearch3(2012)289Ͳ300
Mamane et al. (1986) analyzed individual particles emitted from
coal–firedpowerplantsandfoundthatcoalflyashparticleswere
predominantlysmoothmineralspheres(>95%)consistingmainlyof
Al,SiandFe.Asitwasmentionedbefore,T0isimpactedbylocal
industrialemissionsandfromTularefinerywherecoalisthemain
fuelused,andaccordingtothemeteorologicalpatterns(Moffetet
al.,2008b)thatestablishlowwindspeedscomingmostlyfromthe
northduringtheearlymorning(3:30–10:00a.m.)itispossibleto
understand the source of the “ferrite” particles. Fe is also
consideredasatracerofthesoilcomponent,presentintheairby
soil re–suspension. In the elemental component analysis by ICP–
AES (Inductively Coupled Plasma–Atomic Emission Spectrometry)
performed by Mugica et al. (2009), Fe was, as similar to this
research, the most abundant metal in PM2.5 (1.61 μg/m3, 2.3%
relative abundance) estimating an 26% average contribution to
PM2.5 from re–suspended soil. Similarly, Querol et al. (2008)
classifiedFeasacomponentofthecrustalmaterial,presentinthe
airduetodustre–suspensionandestablishedthecontribution of
this factor as the 15–28% of the PM2.5. These results support the
relative abundance of “Fe–rich” particles characterized by SEM–
EDSinthepresentstudy.
 was demonstrated that the T0 emissions affect T1 pollution, Pb
Moffetetal.(2008a)measuredparticlesizeandcomposition
withhourlytimeresolutionbytechniquesofprotoninducedX–ray
emission(PIXE)andtheaerosoltime–of–flightmassspectrometer
(ATOFMS),presentingaveragePM2.5concentrationtimeseriesfor
Pb particles. Those results are very congruent with the individual
SEM–EDS characterization presented in this research, both made
evidentthedecreaseofthispollutantonweekends,mostlyinthe
official Mexican holiday weekend during March 18th – 20th, when
most of the industries stopped their activities and the regional
vehicletrafficwasminimized.Aikenetal.(2009)alsoreportedlead
particles with Zn associations related to industrial emissions from
the north area of the MCMA, and described decreasing of this
phases on weekends, mentioning march 26th as a lower
concentrationpeak.Althoughthese“Pb–rich”phasesalreadyhave
been detected in MILAGRO samples throughout bulk chemical
analysisandbyscanningmicroscopy(Moffetetal.,2008a;Moffet
etal.,2008b;Queroletal.,2008),thenanometricagglomerationof
spheres characterized by SEM were not shown before. This
pollutantraised health concerns by the ATSDRand in general the
PM2.5 fraction has been shown to be an important health risk
factor in terms of inflammatory and toxicological markers in
relationtothesourcecontributors(Duvalletal.,2008).
 We also thank to the personal of the Centro de Ciencias de la
Anotherinterestinggroupisthe“C–rich”particleswhichalso
presentedsphericalshapesandtheirpredominantsizewasaround
700 nm. The EC phases are related to vehicle exhaust emissions
andaccordingtotheEICP(2008)the52%ofthePM2.5 isattributed
tomobilesources,beingtheheavydutydieselvehicleswhichemit
the 43% of this mobile emissions followed by the particular light
dutyvehicleswiththe18%.InthisEmissionsInventory,adecrease
inaround2tons/dayofPM2.5wasshownduringweekendsrelated,
amongothers,tovehicletrafficreduction.InasimilarwayMugica
etal.(2009)concludedthatvehicleemissionscontributedto42%
ofthePM2.5concentrationandconsideredthatthissourcewasthe
main contributor of carbonaceous material contained in PM2.5.
They have reported that during the long holiday (March 18–21),
thecontributionofvehiclestothetotalmasswasaround13%less
than during the weekdays. According to Salcedo et al. (2006) on
Sundaysthetrafficreductionismorenoticeable(a25%)butduring
holiday weekends, a holy weekend for that investigating period,
the reduction could be 45% less compared to weekdays. With
respecttothesizedistributionfor“C–rich”particles,asmentioned
above,thetotalsphericalECparticlesregisteredsizesbetween600
and800nmandthiswascoincidentwiththeresultspresentedby
Aiken et al. (2009) using high resolution time–of–flight aerosol
mass spectrometer (HR–ToF–AMS) to determine the size
distribution and showed that the majority of the particles are in
the range of 200–800 nm. It is important to mention that the
resolutionoftheSEMusedforthisresearchisaround400nmon

idealconductiveparticles,andthiscouldbealimitfortheanalysis
ofsmallerparticles.

6.Conclusions

By employing scanning electron microscopy it could be
obtainedfurtherdetailsfromparticulatematterlessthan2.5μm,
registering information about morphology, texture, cleavage and
superficial chemical composition (qualitative and semi–
quantitative) using an energy–dispersive X–ray (EDX) analyzer
adapted to the SEM. The information allowed establishing
temporalandabundancedistributionsofthePM2.5anthropogenic
phases.ForT0site,themajorpollutantemissionswereearlyinthe
morninghoursandfrom16:00–19:00hrs,andthiscoincideswith
the start of the working hours for the industries surrounding the
samplingsiteandalsocoincideswiththemajorvehiclevolumesat
thenearbyroads.ForthecaseT1,thetimeintervalthatpresented
the major particles accumulation, mainly “EC–rich” ones, was
16:00–19:00 hrs. These particles exhibited secondary phases
deposition due to T0 emission transportation. Although T1 PM2.5
concentrationsaremainlyattributedtoparticlesre–suspension,it
phasesareaclearexampleofthis,becausethoseparticlesdonot
present an emission source in T1 and showed a remarkable
increase during 22nd of March, a date clearly identified as an
effectivepollutiontransportdayfromT0toT1andT2.

As can be appreciated that, the individual characterization
performed by SEM–EDX on the anthropogenic PM2.5 was
consistent with the bulk chemical analysis and this made evident
the influence of the meteorological conditions on pollutant
distribution as well as the socio–economical regional activities.
SEM–EDX as an individual characterization technique of PM2.5,
allows identifying specific details such as superficial chemical
composition, size and morphology from air suspended particles.
The individual particle details could contribute to establish
pollution tracers emitted by specific sources and therefore follow
thegeneratedphasetrajectoriesinastudiedregiontoverifytheir
impactintheregionaldomain.

Acknowledgements

This study was supported by Mexico’s Consejo Nacional de
Ciencia y Tecnología (CONACYT) with the fellowship No. 161778.
Atmosfera, of the Universidad Nacional Autonoma de Mexico for
theirgreatcollaborationinsamplescollectingforthedevelopment
ofthisproject.

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