AtmosphericPollutionResearch2(2011)477483

Atmospheric Pollution Research

www.atmospolres.com

ChemicalcompositionoffineparticlesinMexicoCityduring
20032004
ElizabethVega,HugoRuiz,SergioEscalona,AlmaCervantes,DiegoLopezVeneroni,
EugenioGonzalezAvalos,GabrielaSanchezReyna
InstitutoMexicanodelPetrleo,EjeCentralLzaroCrdenasNm.152.Col.SanBartoloAtepehuacan.DelegacinGustavoA.Madero.07730,
Mxico,D.F.

ABSTRACT

Ambient samples of PM2.5 collected at three different land use sites (industrial, commercial and residential) within
MexicoCityduringlatefallandearlyspringin2003and2004,werechemicallycharacterizedforwatersolubleionic
species, carbonaceous aerosols and trace elements to further determine their origin. The PM2.5 total mass
concentration was consistently lower during spring compared to late fall at the three sites. The total mass
3
3
concentration decreased from 453g/m at the industrial site, through 364g/m at the commercial site to
3
302g/m at the residential site. The largest component by mass was the organic fraction followed by sulfates,
elementalcarbon,nitrates,geologicalmaterial,traceelementsandsalts.Carbonaceousaerosolaccountedfor47%of
the PM2.5 total mass, (31% organic and 16% elemental carbon), suggesting an origin from incomplete combustion
processesandbiomassburningamongothers.Zincandleadwererelatedtoopenwasteburningandincineration,and
showed an overall average of 0.28% and 0.09%, respectively. The concentrations of nickel and vanadium, that are
related to fossil fuel combustion, were lower than 0.02%; these two elements were associated with sulfates. The
resultsshowthatAl,Cr,Ni,PbandVhaveaclearseasonalitywithhigherconcentrationsinthelatefallandlowerin
theearlyspring.ThehighestconcentrationsoftheseelementswereobservedatthenorthofMexicoCitywheremost
oftheindustrialactivitiestakeplace.

Author(s)2011.ThisworkisdistributedundertheCreativeCommonsAttribution3.0License.

Keywords:
PM2.5
Chemicalcomposition
Airpollution
MexicoCity

ArticleHistory:
Received:16July2010
Revised:24February2011
Accepted:28February2011

CorrespondingAuthor:
ElizabethVega
Tel:+525591756919
Email:evega@imp.mx

doi:10.5094/APR.2011.054

1.Introduction

Since 1990, air quality in Mexico City has improved

considerably.Asaresultofcontrolenforcementpolicies,between
1990 and 2008 concentrations of key pollutants, such as O3, Pb,
NO2, CO, SO2 and PM10 have decreased between 47% and 96%.
Additionally, from 2004 to 2008 PM2.5 average concentration has
diminishedby27%(SIMAT,2010).

Particulate matter air pollution control remains a challenge:

PM10annualaverageconcentrations(73g/m3 in2008;106g/m3
in2009)arestillabovethenationalambientairqualitystandardof
3
3
65g/m ,whilePM2.5(2009annualaverageof26g/m )isalmost
3
twotimeshigherthanthestandard(15g/m )(SIMAT,2010).

In urban areas, the increase of anthropogenic activities

generates high PM concentrations that both deteriorate the
environment and threaten human health. Several studies have
associatedhighlevelsofparticlestodifferenthealthproblemssuch
as respiratory and cardiovascular diseases, respiratory infections,
negative effects on the nervous system, cancer, and premature
death (Vedal, 1997; US EPA, 2010). The chemical composition of
thefinerfractionisespeciallyharmful(Dockeryetal.,1992;Chow
et al., 2002; Fernandez et al., 2003; Pope and Dockery, 2006;
Mauderly and Chow, 2008). Elemental carbon (EC) has been
associatedtocancer(Lauetal.,2003),andNi,V,FeandPb,cause
molecular damage if inhaled (Halliwell and Gutteridge, 1999). Ni
and V have been determinant for respiratory health effects and
cardiopulmonary injuries in rats (GutierrezCastillo et al., 2005).
These species are not well characterized in Mexico Citys

atmosphere, although some physical and chemical aspects of PM

havebeenreported(Vegaetal.,2002;Chowetal.,2002;Vegaet
al.,2004;Queroletal.,2008;Vegaetal.,2010).

Recent studies suggest that ambient particles of Mexico City

are greatly modulated by biomass burning and agricultural
practices,withcontributionsthatrangefrom40to80%duringthe
drymonthsofDecembertoApril(Yokelsonetal.,2007;Moffretet
al., 2008). Chemical composition studies suggest that approxi
mately50%ofPMiscarbonaceous(Johnsonetal.,2006).

In this study the main objective was to measure and

chemically characterize PM2.5 to identify source categories. This
characterization will be further applied in receptor models to
quantify and apportion its sources. Additionally, attention was
giventothosechemicalspeciestoprovideaguidefortoxicological
studies.

2.ExperimentalMethod

2.1.Monitoringsiteslocationandbasicmeteorology

ThreesiteswithinMexicoCitywereselectedforthisstudy:(1)
Xalostoc (XAL) located in the northeast, close to heavily traveled
paved roads with light and heavy duty vehicles, influenced by
emissions of industrial activities and resuspended dust from
unpaved roads and from the dry Lake Texcoco; (2) La Merced
(MER) located near downtown, with residential and commercial
areas, with moderately traveled paved streets; and (3) Pedregal

478

Vegaetal.AtmosphericPollutionResearch2(2011)477483

(PED)locatedsouthwestinanaffluentresidentialareaadjacentto
lightlytraveledpavedroads.

Thesurfacemeteorologyofthebasinduringthestudyperiods
was characterized by slight variations in temperature (T), with an
averagevalueof15.1Cinlatefalland17.3Cinspring,whilethe
relative humidity (RH) showed slightly lower values during spring
(50.4% average) compared to late fall (54.0%). The wind speed
(WS)washigherduringspring(1.8m/s)whencomparedtolatefall
(1.0m/s). Stagnant atmospheric conditions in Mexico City are
frequent in late fall and winter, leading to the accumulation of
local emissions and production of secondary pollutants by
photochemical reactions; thus, air pollution levels are generally
higherinthistimeoftheyear.

2.2.Sampling

Atmospheric particles (PM2.5) were sampled during two late

fall(November24December7,2003;November22December5,
2004), and early spring periods (March 821, 2004). In each
period duplicate samples were collected simultaneously at XAL,
MERandPED,in24hsamplingcycles(0:0024:00h),foratotalof
576PM2.5 samples. Samples were collected with MiniVol PM2.5
samplers (Airmetrics) at a flow rate of 5L/min. Particles were
retained on 47mm Teflon membrane (2m pore size, Gelman
Scientific) and prefired quartzfiber (QATUP, Pallflex Products
Corp.) filters. Teflon filters were used to determine mass, trace
elements, and light transmission (babs), while quartz filters were
used for ion, elemental carbon (EC), and organic carbon (OC)
analyses. Teflon filters were stabilized during a 48h period in a
relativehumidity(355%)andtemperature(202C)controlled
atmosphere. Filter weights were recorded before and after
sampling using an AX Mettler Toledo microbalance (0.001mg
precision).

Allsampleswereanalyzedformassandchemicalcomposition.
An inductively coupled plasma mass spectrometer (ICPMS) was
usedtodeterminetraceelements(Li,Be,Na,Mg,Al,Si,K,Ca,Sc,
V,Cr,Fe,Co,Ni,Cu,Zn,As,Rb,Y,Mo,Ag,Cd,In,Sn,Sb,Ba,Ce,Tb,
Hg, Pb and Bi). Anions (chloride [Cl], nitrate [NO3], and sulfate
2
+
+
[SO4 ]) and cations (sodium [Na ], potassium [K ], ammonium
+
2+
2+
[NH4 ], calcium [Ca ], and magnesium [Mg ]) were analyzed by
ion exchange chromatography. Both OC and EC were analyzed by
thermalopticalreflectance(TOR).

2.3.Samplepreparationandanalysis

Ions. Ion samples were prepared using ASTM Type 1deionized

water(18.2Mcm,QuantumICPcartridgeandfilterof0.1m,
Millipore). Preset calibrated automatic dispensing pipettes were
usedforsampleandstandardpreparations.Allstandardsolutions
usedforcalibrationwereNISTcertifiedstandards(UltraScientific,
UltragradeTM).

Ions collected on quartz filters were extracted in deionized

water by sonication, shaking in an orbital shaker, and storing
overnightinrefrigeration.IonanalyseswereperformedinanHPLC
instrument(Waters,Alliance)providedwithseparationmodule
W2695andconductivitymoduledetectorW432.Theanioncolumn
wasastainlesssteel(WatersICPakTMAnionHR)of4.6x75mm
packed with polymethacrylate resin. A solution of sodium
borate/gluconate was used as the mobile phase. The cation
column was a stainless steel (Waters ICPakTM Cation M/D) of
3.9x150mm packed with silica base coated with
polybutadiene/maleicacid.AsolutionofdeEDTA/HNO3wasused
as the mobile phase. Prior to ion analyses mobile phases were
filtered,anddegassedinanultrasonicbath.Detectionlimitswere
7.8,24.5and46.3ng/mlforCl,NO3,andSO42,respectively,and
6.3,7.9,6.3,11.2and10.9ngml1forNa+,K+,NH4+,Ca2+andMg2+,
respectively.

Trace elements. For trace elements determination each sample

collected in Teflon filters was placed into PTFE microwave
digestion vessels and acid digested using a mixture of nitric,
hydrochloricacidanddeionizedwater.Priortodigestion,samples
werespikedwith100ng/mlofY,andafterdigestionsampleswere
spiked with 100ng/ml of In as internal standards. Total trace
elements were analyzed using an ICPMS (Agilent 7500a)
instrumentequippedwithincidentpowerof1.39kW,RFmatching
1.76V,nebulizergas(1.0L/minflow),spraychamber(temperature
of2C)andadiscriminator(9.5mV).Interferenceequationswere
used for corrections in all samples, using the following scan
parameters: 3scans, 32channels, 100passes. Detection limits
were:7.9(Li),1.3(Be),11.0(Na),2.3(Mg),8.5(Al),22.9(Si),15.4
(K),13.0(Ca),7.2(Sc),6.7(V),7.5(Cr),9.4(Fe),1.3(Co),1.5(Ni),
10.8(Cu),9.7(Zn),8.1(As),25.4(Rb),7.3(Y),1.6(Mo),8.6(Ag),8.6
(Cd),1.0(In),37.3(Sn),2.1(Sb),8.1(Ba),0.9(Ce),13.2(Tb),24.3
(Hg),0.9(Pb)and5.3(Bi)ng/ml.

Organicandelementalcarbon.OCandECsampleswereanalyzed
by TOR. A 0.49cm2 punch of each sample quartz filter was
analyzed for several carbon fractions following the Interagency
Monitoring of Protected Visual Environments (IMPROVE) protocol
using DRI Model 2001 Thermal/Optical Carbon Analyzer
(Atmoslytic Inc., Calabasas, CA, USA). The analyzer operates by
liberating carbon compounds under different temperature and
oxidation environments. These compounds are converted to CO2
bypassingthevolatilizedspeciesthroughanoxidizerandreducing
CO2 to CH4 by passing the flow through a methanator and
quantifyingCH4equivalentswithaflameionizationdetector.

Theanalyzerwasverifiedatthebeginningandendoftheday
withknownamountsofHe/5%CH4,acalibrationcheckattheend
of each sample with He/5% CH4 and a full instrument calibration
performed every six months by spiking prefired quartz punches
with1.0to10.0lofthe1800ppmpotassiumhydrogenphthalate
in2%HClandinjecting10to2000loftheCO2andCH4gasesin
5%He.Detectionlimitswere0.1gCforbothECandOC.

Calculation of OC/EC ratio and secondary organic carbon (SOC).

EC is a primary pollutant emitted during the incomplete
combustion of fossil fuels and biomass burning while OC may be
emitted directly as primary particles (highway vehicles, waste
burning,wildfiresandfireplaces)orformedintheatmosphereby
chemical reactions (Castro et al., 1999). Stone et al. (2008) have
reported a contribution of 49% from motor vehicles to the OC
fraction. Based on these facts, the OC/EC ratio has been used for
emission and transformation studies, and it is agreed that ratios
exceeding2.0indicatethepresenceofsecondaryorganicaerosols
(Cao et al., 2003), ratios between 0.71 and 0.57 suggest the
influence heavyduty diesel vehicles without emissions control
(Mazzera et al., 2001), while ratios from 0.26 to 0.42 are specific
fordieselfuelcombustion(Lowenthaletal.,1994).

Since there is no direct way to determine secondary organic

carbon (SOC), several indirect methods have been proposed,
although it is known that these approaches give only semi
quantitativeinformationduetothehighuncertaintyassociated.In
this work, calculations were performed according to Castro et al.
(1999)asfollows:

SOC=TOC ECx(OC/EC)min
(1)

where TOC is the total OC, and (OC/EC)min the minimum ratio
observed,assumingthatitrepresentsapureprimaryaerosol.

2.4.Qualityassurance

Type I deionized water blanks, extraction blanks and filter

blanks were analyzed with each set of extracted filters, and
sampleswerecorrectedbysubtractingtheblankamountfromthe
sample. Replicates were run in at least 10% of the samples with

Vegaetal.AtmosphericPollutionResearch2(2011)477483

results of less than 5% differences. Calibration curves were

acceptable when correlation coefficients were greater than 0.99.
Check standards were analyzed before samples runs, after each
groupoftenanalysesandattheendoftheanalysis.Repeatability
was checked up by analyzing 10times a sample and a mixture of
elements. For trace elements analyses In was used as an internal
standardandforcarbonanalysesaloopof1mlofHe/5%CH4was
used. Results were submitted to three levels of data validation
whichisasdetailedbyWatsonetal.(1995)andChowetal.(1994,
1996).

Data validation was done by means of plotting variables that

areknowntohavelinearrelationshipas:electroneutralityofsum
ofanionsversuscations;sumofindividualchemicalspeciesversus
calculatedmass;ECversuslighttransmission(babs);K+versusK;Na+
versusNa;Ca2+versusCaandMg2+versusMg.Inallcasesexcept
forCa,correlationcoefficientshigherthan0.91andslopecloseto
1.0wereobserved.

479

measured. Overall, these results reflect both the location and

distance of the sites in reference to the main sources (e.g.
emissions from industries and heavyduty vehicle exhaust) at the
north of the city (Vega et al., 2004; de Foy et al., 2009), and the
windflowpatternthathasbeenstudiedindetailbydeFoyetal.
(2005).

3.ResultsandDiscussion

3.1.Massconcentrationandcomparisonwithotherstudies

Average PM2.5 total mass concentration (in g/m3) for the

three sampling campaigns showed concentration during the late
fall campaigns was statistically higher compared to those from
spring. These values are lightly lower than those reported
previously (Vega et al., 2002; Vega et al., 2004) for Mexico City,
and suggest that results from this study are representative of
conditions for this time of the year. On the other hand these
concentrations are comparable to those recorded in Sao Paulo in
1986 (Alonso et al., 1997) and Los Angeles in the 1980s
(Christoforouetal.,2000)whenlessstrictairpollutioncontroltook
place.MexicoCityaveragevaluesareintermediatebetweenother
urbanareaswithlowerconcentrationscomparedtoElCairo,(Abu
AbuAllaban,2002),Thessaloniki(Manolietal.,2002),Manglatore
(Hegde et al., 2007), and Agra in India (Kulshrestha et al., 2009),
but higher than those reported for Dundee in the UK (Qin and
Oduyemi,2003)andSaoPaulo(Bourotteetal.,2007).Thesevalues
aresimilartothoseforPM10,whereMexicoCityliesintermediate
when compared to other megacities (Parrish and Zhu, 2009). In
general, the high levels of PM2.5 observed in cities of the
developing countries point to the need for more stringent
environmental legislation and to take more effective measures to
controlemissionsources.

The babs measurements, which are used to evaluate the

attenuation of light transmitted through particles, specifically by
EC, showed a seasonal trend with higher values during late fall
decreasinginspring.Temporalbabsaverageswere117.7,97.4and
60.1M/matXAL,MERandPED,respectively,whichwasconsistent
withtheconcentrationsofECatallsites.

Effect of meteorology on PM2.5 concentrations. Correlation

coefficients of T, RH, WS, and wind direction (WD) versus PM2.5
were calculated to examine the effect of meteorology on the
particle concentrations. However, only WS and WD showed clear
relationships.

Figure1describestheeffectofWSonPM2.5atPEDasXALand
MER showed similar results. Minimum levels of PM2.5 were
observed at high WS (>3.0m/s), which mostly occurred in the
spring. Correlation (R2) were 0.79, 0.85 and 0.83 for winter
2003,spring2004andwinter2004,respectively.

A series of PM2.5 pollution roses were constructed using

WRPLOTview software (Lakes Environmental Software) selecting
two cases, one with PM2.5 concentrations above the average and
theotherwithlevelsbelowtheaverage.AsFigure2shows,NNE
winds at XAL, NE winds at MER and SW winds at PED were
registered when PM2.5 concentrations above the average were

Figure1.PM2.5concentrationandwindspeedatPEDsite.

(A)

(B)

(C)

Figure2.RelationshipofwinddirectionandPM2.5concentration(g/m )at
(A)XAL,(B)MERand(C)PED.

480

Vegaetal.AtmosphericPollutionResearch2(2011)477483

3.2.Chemicalcompositionandmassbalance

Table 1 shows the 24h PM2.5 concentrations (g/m3) and

chemicalcompositionatXAL,MERandPED.Chemicalcomponents
were classified as (NH4)2SO4 and NH4NO3, OC, EC, geological
material, trace elements (nogeological material), and mineral
salts. To account for unmeasured hydrogen and oxygen, NH4NO3

wasestimatedas1.29xNO3 ,(NH4)2SO4wascalculatedas1.375x
SO42, and OC was estimated as 1.2xOC. Trace elements are
consideredhereasallelementsfromtheperiodictablebetweenLi
andPbexcludinggeologicalmaterial(Al,Si,Ca,Fe,Cl,K,Na,andS).
Oxides of geological material were considered as 1.89xAl,
2.14xSi,1.4xCaand1.43xFetoaccountforunmeasuredoxides.
Mineral salts were estimated as 1.65xCl. Twentyfourhour mass
balanceaveragesofPM2.5areshowninFigure3.

Watersoluble ions. Water soluble ions accounted for 35.8% of

PM2.5 total mass with 25.2% being anions and 10.6% cations.
Sulfate accounted for 25.0% of the mass, 12.0% were nitrates
(which mostly originate from highway vehicles as previously
reported by Vega et al., 2009), and minor contribution of salts
(1%). This is in contrast with reported values for Sao Paulo
(Bourotteetal.,2007)withconcentrationsofSO42(48.4%),NO3
(19.6%),NH4+(12.5%)andCl(12.5%)wheresulfuremissionswere
related to anthropogenic sources such as fossil fuel combustion
andindustrialactivitiesusingfossilfuel.Nitrateswerealsorelated
tomotorvehicleemissionsandthesignificantcontributionofsea
salt(Bouretteetal.,2007).Moreover,inthestudytheK/Naratio
of0.9wasattributedtovehicularemissions.InthisstudytheK/Na
ratio was 1.4 which is within the range (1.14.4) reported for
vehicularemissions(Ookietal.,2002).

Additionally, in Istanbul, Turkey, it was reported that SO42

account for 53% and NO3 with 22% of the total particles, which
reflects the rapid and uncontrolled growth in urbanization and
industrialization(Theodosietal.,2010).

Theresultsshowedthatsulfatewasthedominantionandits
strong correlation (0.96) with NH4+ indicates that these species
have a secondary origin due to the atmospheric gastoparticle
conversion processes. Temporal average concentration of
(NH4)2SO4 was higher when compared to nitrates. These were

homogeneouslydistributedslightlyincreasingfromnorthtosouth,
consistent with SO2 emissions from the industrial area which are
transported from its northern source to the south (Vega et al.,
2004; De Foy et al., 2009). Seasonal variations in sulfate were
observed; with higher values in late fall (29.6%) compare to early
spring (23.5%), in contrast to ammonium nitrate with 10.7% and
13.2%, respectively. Average sulfate and nitrate concentrations
decreased from south to north (20.6%, 18.9% and 15.2%, and
7.8%,7.2%and6.0%respectively,atPED,MERandXAL).

Carbonaceous aerosols. Carbonaceous aerosol accounted for

47.0% of PM2.5 total mass, in agreement with recent results for
Mexico City (Johnson et al., 2006). This carbonaceous fraction is
composed of 31% of OC and 16% of EC, indicating an origin from
biomassburningandincompletecombustionprocesses.OCandEC
average concentrations for late fall were 12.61.2g/m3 and
3
6.51.2g/m , respectively, while in early spring these averages
decreased to 9.51.1g/m3 and 5.11.0g/m3. EC showed
higherconcentrationsatXALandMERrelativetoPED,mostlikely
due to emissions from industries and heavily travelled roads by
dieselpoweredvehicles.

The results showed that the levels of OC have a clear

seasonalitywithhigherconcentrationsinthelatefallandlowerin
the early spring, suggesting that longrange transport is a major
carbonaceousaerosolsourceinMexicoCity.SeasonalityofECwas
similartotheoneobservedforOC,althoughitwasvariableforthe
MERsite.

AverageOC/ECratioswere1.4,2.0and2.9forXAL,MERand
PED, respectively, with an overall average of 2.1, suggesting the
presenceofsecondaryorganicaerosols,whichissimilartovalues,
reportedforMcMurdoinAntarcticaandFresno,CaliforniainUSA
(Watson et al., 2000; Mazzera et al., 2001). The highest ratio at
PED may be due to formation of secondary OC during
transportation, while the lowest value at XAL may the result of
industrialandvehicularemissions.

Table 2 shows the temporal average of TOC, SOC, and EC at

three sites. The estimated SOC was 0.9g/m3 (2.0%), 3.4g/m3
3
(9.6%) and 4.6g/m (15.3%) for XAL, MER and PED, respectively
andanoverallaverageof3.0g/m3(8.0%).

Figure3.TwentyfourhouraveragematerialbalanceofPM2.5forXAL,MERandPEDduring20032004.

Vegaetal.AtmosphericPollutionResearch2(2011)477483
3 a

481

Table1.Averageandmaximum24hPM2.5concentrations(g/m , ng/m )inXalostoc,LaMercedandPedregal,during20032004

XALNov03 XALMarch04 XALNov04

Ave

Max

Ave

Max

Ave

Max

Ave

MERNov03 MERMarch04 MERNov04

Ave

Max

Ave

Max

Ave

Max

Mass

46.9

69.9

37.1

60.2

52.9

65.0

45.6

39.4

60.1

28.9

43.6

39.6

58.8

72.1 125.4 107.3 144.1

babs(M/m) 122.8 178.2 104.7 147.3 125.7 159.9 117.7 112.9 708.4

NO3

Ave

PEDNov03 PEDMarch04 PEDNov04

Ave

Max

Ave

36.0

34.8

61.9

25.3

97.4

69.1 117.5 50.9

Max

Ave

Ave

Max

46.5

29.9

52.3

30.0

85.9

60.3 101.1

60.1

3.12

8.60

2.04

4.81

2.98

5.87

2.71

3.11

9.54

1.87

5.30

2.84

5.12

2.61

2.86

7.48

1.48

4.38

2.64

5.00

2.33

SO42

7.49 14.83 6.55 13.02 6.82 18.57 6.95

6.90 18.69

6.69 13.28 6.85 21.46

6.81

6.94 15.08 5.99 13.73 5.64 15.86

6.19

NH4+

3.68

9.39

2.77

5.99

3.23

7.97

3.23

3.49

8.94

2.89

6.17

3.42

9.65

3.27

3.49

7.34

2.66

6.08

2.96

7.90

3.03

Na+

0.23

0.37

0.28

0.45

0.35

0.47

0.28

0.16

0.29

0.22

0.28

0.18

0.33

0.18

0.10

0.19

0.12

0.19

0.07

0.11

0.10

K+

0.29

0.56

0.22

0.40

0.43

0.70

0.31

0.24

0.33

0.21

0.33

0.40

0.66

0.28

0.20

0.60

0.16

0.21

0.23

0.37

0.19

OC

11.32 19.02 8.80 14.34 12.08 17.29 10.73 8.64 13.20

EC

9.36 16.78 7.47 13.21 9.91 12.82 8.91

TC

20.68 35.80 16.26 27.56 21.99 30.11 19.64 13.48 21.00 12.70 20.44 20.11 29.92 15.43 12.59 23.49 10.16 16.14 12.90 17.31 11.88

4.84

7.81

7.63 11.53 12.90 19.84

9.72

8.80 18.04 7.31 11.89 9.13 12.02

8.41

5.07

5.71

3.79

3.47

8.91

7.21 10.08

5.45

2.85

4.25

3.78

5.29

Cl

0.69

3.68

0.38

1.09

0.90

1.86

0.66

0.12

0.40

0.08

0.18

0.09

0.20

0.09

0.04

0.13

0.03

0.05

0.02

0.05

0.03

Mg2+

0.08

0.12

0.10

0.16

0.11

0.19

0.10

0.05

0.07

0.05

0.07

0.06

0.08

0.05

0.05

0.07

0.04

0.07

0.04

0.06

0.04

2+

Ca

0.40

0.56

0.51

1.88

0.53

0.75

0.48

0.19

0.31

0.19

0.41

0.25

0.32

0.21

0.14

0.25

0.07

0.16

0.13

0.30

0.11

Na

0.14

0.45

0.15

0.28

0.20

0.30

0.17

0.07

0.16

0.09

0.14

0.08

0.19

0.08

0.02

0.08

0.05

0.10

0.01

0.05

0.03

Mg

110.2 153.4 109.9 154.8 121.4 196.4 113.8 37.08 60.61 44.56 73.36 54.04 69.45 45.23 27.73 42.91 30.96 38.56 11.85 18.57 23.51

Al

96.06 153.7 36.73 68.53 91.08 146.0 74.62 35.97 103.0 14.49 144.1 39.79 73.93 30.08 36.13 87.31 16.34 32.22 16.43 32.91 22.97

Si

0.41

0.68

0.22

0.33

0.38

0.63

0.34

0.14

0.36

0.11

0.20

0.21

0.32

0.16

0.29

0.55

0.11

0.19

0.12

0.22

0.22

0.42

0.18

0.31

0.30

0.50

0.23

0.17

0.30

0.13

0.18

0.26

0.40

0.19

0.16

0.48

0.11

0.18

0.15

0.25

0.14

Ca

0.24

0.34

0.27

0.40

0.31

0.44

0.27

0.10

0.19

0.11

0.23

0.15

0.19

0.12

0.13

0.29

0.11

0.22

0.10

0.18

0.11

4.43 53.59 0.00

0.00

4.67 53.92 3.03

3.14 15.96

0.00

0.00

6.81 61.17

3.32

1.22

9.27

0.00

0.00

1.57 20.43

0.93

0.17

Cr

15.03 22.25 0.31

0.81 81.67 170.9 32.34 5.98

9.13

7.13

9.66 52.29 73.52 21.80 15.01 19.94 6.93 14.52 13.54 24.53 11.83

Fe

0.38

0.55

0.28

0.16

0.23

0.23

0.33

0.19

0.14

0.14

0.20

0.15

Ni

6.85 19.60 6.08 19.62 6.75 16.13 6.56

6.96 20.72

4.85

9.24

5.73 18.60

5.85

6.98 14.95 4.35

7.30

4.84 17.15

5.39

Zn

0.16

0.17

0.07

0.11

0.06

0.10

0.04

0.04

0.01

0.02

Pb

0.58

0.34

0.32

0.15

0.57

0.39

0.26

0.65

0.72

0.36

0.19

0.17

0.59

0.14

0.23

0.10

0.02

0.26

0.04

0.15

58.75 169.9 24.83 62.75 47.56 82.52 43.71 37.38 103.4 27.04 45.59 46.86 80.85 37.09 19.18 32.92 13.78 39.95 10.68 24.40 14.55

Table 2. Temporal average of total organic carbon, primary, secondary

3
organic carbon and elemental carbon (g/m ) at Xalostoc, La Merced and
Pedregalduring20032004

XAL

MER

PED

Average

Mass

45.6

36.0

30.0

37.2

TOC

12.9

11.7

10.1

11.6

POC

12.0

8.3

5.5

8.6

SOC

0.9

3.4

4.6

3.0

EC

8.9

5.7

3.5

6.0

Relationship between organic fraction and carbon monoxide. A

preliminaryapproachusefulto discriminatebetweenprimaryand
secondaryOCconsistsindeterminingtheassociationbetweenOC
with CO and O3, which are surrogates for combustion emissions
and photochemical activity, respectively (Alfarra et al., 2004).
2
Significant correlations of OC with CO (R >0.65) at XAL and MER
were determined. No relationship was observed for O3 and OC
2
(R <0.20) at the three sites, suggesting that combustionrelated
emissionswerethemainsourceoforganics.It wasalsoobserved
thatthosedayswithCOlevelsabovetheaveragedidincreasethe
concentrations ofOCandECbymorethan30%.Incontrast,days
with O3 above the average showed a less defined increment in
NO3andOC.

Traceelements.Traceelementsaccountedfor0.6%ofPM2.5total
mass,withaveragesof0.8%,0.6%and0.4%forXAL,MERandPED,
respectively. Trace elements that are related to industrial
processes such as Fe and Cr contributed with low concentrations
(0.63%and0.06%,respectively).ZnandPb,relatedtoopenwaste
burning and incineration (Vega et al., 2009), showed an overall
averageof0.28%and0.09%,respectively.NiandVrelatedtofossil
fuel combustion (Vega et al., 2009) showed concentrations lower
than0.02%,andaccordingtotheTukeytest,wereassociatedwith
secondary species indicative of regional sources (Viana et al.,
2007). In contrast, lower levels of these markers have been
reported for Amsterdam (TheNetherlands), Erfurt (Germany) and
Helsinki(Finland)(Valliusetal.,2005).

Therearesomeelementalspeciesthataretoxicairpollutants
such as Al, As, Be, Cd, Cr, Hg, Mn, Ni, Pb, V and Zn, and some of
thesealsoarecarcinogenic(As,Cr,andNi).Someofthesespecies
were found to be below the detection limits and were not
reported. The results show that Al, Cr, Ni, Pb and V have a clear
seasonalitywithhigherconcentrationsinthelatefallandlowerin
the early spring. No seasonality could be discerned for Zn as
concentrations were very low at PED possibly reflecting values
closetodetectionlimitsorwithhighuncertainty.Forallcasesthe
highest concentrations of these elements were observed at the
north of Mexico City where most of the industrial activities take
place. The highest concentrations of Pb and Zn were observed at
theindustrialsiteandthelowestattheresidentialsite(PED)atthe

482

Vegaetal.AtmosphericPollutionResearch2(2011)477483

south of the city, indicating that local vehicular traffic is not an

importantsourceoftheseelements.

Geological material and salts. The average contribution of

geological material was 0.56%, with a northtosouth decreasing
gradient (XAL 0.74%, MER 0.60% and PED 0.34%). In general, the
contributionofgeologicalmaterialwashigherduringthecolddry
season (late fall) for all sites, where low pluvial precipitations
(1.6310.82mm)takeplace.InadditionXALhastheinfluenceof
resuspended dust from unpaved roads and from the dry Lake
Texcoco.

SaltswereonlysignificantatXALwithanaverageof1.4%.On
the other hand, low concentrations were determined for most
cationswithlessthat1%,exceptforammonium,whichshoweda
homogeneousspatialandtemporaldistributionwithanaverageof
8.8%.

4.Conclusions

Samples of fine particles collected every 24h during field

campaignsinlatefallandearlyspringatthreesiteswithdifferent
land uses within Mexico City were chemically characterized for
water soluble ions, organic and elemental carbon and trace
elements.ThePM2.5totalmassconcentrationsaresimilartothose
reportedpreviouslyforMexicoCity(Vegaetal.,2002;Vegaetal.,
2004)withhighestconcentrationsattheindustrialsiteandlowest
at the residential site, suggesting these results represent typical
conditionsforthistimeoftheyear.

Chemical composition showed that OC is the largest

component by mass followed by sulfates, EC, nitrates, geological
material,traceelementsandsalts.Incontrast,inUSAithasbeen
reported that sulfate is the largest component followed by OC,
nitrate, EC and crustal material, although the composition varies
geographically(USEPA,2010).

Carbonaceous aerosol accounted for nearly half of the PM2.5

total mass, suggesting an origin from incomplete combustion of
fossil fuels and biomass burning among other potential sources.
Organic carbon accounted for one third of the PM2.5 total mass.
The levels of OC have a clear seasonality with higher
concentrations in the late fall and lower in the early spring,
suggesting that longrange transport is a major carbonaceous
aerosolsourceinMexicoCity.TheaverageOC/ECratiosuggested
thepresenceofSOC,whichwasestimatedtoaccountfor8%ofthe
PM2.5totalmass.ThecorrelationofOCwithCO,ratherthanwith
O3, suggests that combustionrelated emissions dominated over
photochemicalprocesses.

The results show that Al, Cr, Ni, Pb and V have a clear
seasonalitywithhigherconcentrationsinthelatefallandlowerin
the early spring. The highest concentrations of these elements
were observed at the north of Mexico City where most of the
industrial activities take place. Trace elements such as Zn and Pb
werehigherattheindustrialsiteandfrequentlyshowedasimilar
variation with other metals related to industrial emissions. V and
Ni showed association with secondary species, indicating their
regional nature. In addition, it was found that for some trace
elements considered as toxic and carcinogenic air pollutants such
as Al, As, Be, Cd, Cr, Hg, Mn, Ni, Pb, V and Zn, the amount of
samplecollectedwasnotenoughforchemicalanalysis,sotosolve
thislimitationstheauthorssuggestthecombineduseofsampling
equipments for instance high volume samplers or more robust
analyticaltechniquesforelementssuchasAs,CdandHgwhereno
samplepreparationisneeded.

It was observed that pollution roses show that north/

northwesterlytransportisoftenassociatedwithsomeofthetoxic
elements.Withtheuncontrolledgrowthoftheindustrialactivities
atthenorthofMexicoCity,thisinturnsuggeststheimportanceof

more continuous sampling periods and more locations during

futurestudies.

While it is beyond the scope of this paper to evaluate the

health impact of particles, this study provides quantitative
chemical speciation for further evaluation of health impact.
Additionally,itisnecessarytoidentifyandassessthecontribution
of local sources emitting the aforementioned species, in order to
suggest strengthened control strategies on several emitters.
Meanwhile,asresultsofthisstudyindicatedthepresenceoftoxic
species (Ni, V, Zn, Pb and EC), it is crucial to establish local
strategies to reduce their emissions, rather than controlling only
thePM2.5totalmassemissions.

Acknowledgement

This research project was supported by SEMARNAT (2002

CO10296)andIMPundercontractY.0006.

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