research article distribution pattern of metals in...

Research ArticleDistribution Pattern of Metals in Atmospheric Settling Dustalong Roads in Kano Metropolis Nigeria

O J Okunola1 A Uzairu2 S Uba2 C S Ezeanyanaso3 and Y Alhassan4

1Department of Applied Chemistry Federal University Dutsin-Ma PMB 5001 Dutsin-Ma Katsina Nigeria2Department of Chemistry Ahmadu Bello University PMB 810000 Zaria Nigeria3Textile Division Federal Institute of Industrial Research Oshodi PMB 21023 Ikeja Lagos Nigeria4National Research Institute for Chemical Technology PMB 1052 Basawa Zaria Nigeria

Correspondence should be addressed to O J Okunola okunolaojgmailcom

Received 20 August 2014 Revised 18 November 2014 Accepted 23 December 2014

Academic Editor Tianlong Deng

Copyright copy 2015 O J Okunola et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

The sequential extraction of Cd Cr Ni Pb Cu and Zn in atmospheric dust particles collected along ten high traffic roads in Kanometropolis was carried out Analyses of metals in the extracts were done using flame atomic absorption spectrometry (FAAS) Thesamples analyzed for metals indicated high levels of Cd Cr Ni Pb Cu and Zn in the atmospheric dust samples The sequentialextractions that showed significant amount of Cd were associated with CO

3

2minus and Fe-MnO fractions especially during the dryseasons ForCr andNi their occlusion in crystal lattice of the soil fraction exhibited the highest percentage Pb in the particulate dustsamples is significantly associated with the carbonate bound fraction with range of 881ndash6469 across the seasonThe behaviour ofCu is quite different from other metals in that percentage fractions are higher in the organic bound As for Zn significant amountswere associated with the residue fractions ranging from 096 to 8750 across the seasons This study revealed contamination ofthe particulate dust with Cd and Pb this implies health risks to human living or carrying out daily activities along the corridors ofthese roads

1 Introduction

The increase of health problems related to road dust arisingfrom urbanization and industrialization has especially dur-ing the last two centuries gradually created a demand formore efficient vehicle-associated emission controls Accord-ing to Cho et al [1] 50 of urban air particulate emis-sions are closely related to road traffic [1] Studies havealso reported association between traffic density closenessto roads and various respiratory symptoms in children[1ndash3]

From literature motor vehicles are known to introduce anumber of toxic metals into the atmosphere which are laterdeposited on roadsides [4] As a result of vehicle emissionsthe deposition of heavy metals on the road may result intheir incorporation into dust due to their size that rangesbetween 10minus9 and 10minus6m [5] Of all the types of dust foundin the urban environment one of the most highly toxicmetals is dust from road Since such dust may be inhaled via

airborne or discharged into rivers by storm-water wash-offdust from roadmay hence represent a major pollution sourcewithin the urban environment [6] These activities releasedust particulate which adversely affects human Thereforemonitoring of particulatematter especially with heavymetalsis imperative

Based on the above facts the present study aims to assessthe distribution ofmetals (Cd Cr Ni Pb Cu and Zn) speciesin atmospheric settling dust along roads using sequentialextraction

2 Materials and Methods

21 Study Area KanoMetropolis is located between latitudes11∘5910158405957 and 12∘0210158403957∘N of the equator and betweenlongitudes 8∘3310158401969 and 8∘3110158405969∘E The climate of theKano is dominated by the migration of the intertropicalconvergence zone Industrially it is one of the most devel-oped cities in Northern Nigeria and tannery and textile

Hindawi Publishing CorporationJournal of Applied ChemistryVolume 2015 Article ID 739325 12 pageshttpdxdoiorg1011552015739325

2 Journal of Applied Chemistry

Main roadRailwaySecondary road

Control point

0 2500

N

S

(m)

Sampling siteInternational airport

8∘33

9984001969

998400998400E

8∘31

9984005969

998400998400E 8∘33

9984001969

998400998400E 8∘34

9984003969

998400998400E

8∘34

9984003969

998400998400E

12∘02

9984003957

998400998400N 12∘02

9984003957

998400998400N

12∘01

9984001957

998400998400N

11∘59

9984005957

998400998400N

12∘01

9984001957

998400998400N

11∘59

9984005957

998400998400N

Figure 1 Kano Metropolis showing the sampling sites Source adapted and modified from Google Map Data 2010

are some of its dominating industries [7] Kano Metropolisattracts substantial number of immigrants being the seat ofgovernment and center of commerce industry and educa-tion In the city there are various large markets such asthe City (Kurmi) Market Sabon Gari Market and KatinKwari (cloth market) which attract people from all overthe country The major form of transportation within KanoMetropolis is by road Most common transport modesused include cars buses motorcycles and tricycles (KekeNAPEP)

22 Sample Collection and Pretreatment Sampling of dustsfor this studywas conducted fromDecember 2009 to Septem-ber 2010 across four named seasons cold and dry hot anddry warm and wet and warm and dry The criteria forselections of roads for the studywere based on foreknowledgeof the relative traffic density on each road and the desireto have each category of traffic density in different sectionsof the Metropolis Samples were collected from 10 roadsidelocations (1ndash10) and a control site (C) all over the Metropolisas shown in Figure 1 These sites were mainly located inresidential and commercial areas of the metropolis Controlsamples were obtained from a small garden within a resi-dential buildup area of farm center which is not closer to

any secondary or main road Average temperature across theseasons is 315ndash366∘C 300ndash391∘C 305ndash339∘C and 301ndash395∘C respectively

Atmospherically deposited particulates were sampledaccording to indirect method of air sampling described byNabuloa [8] Similarly the traffic density was determined bymanual counting according to Okunola et al [9] as shown inTable 1

23 Quality Assurance All apparatus including glasswareand plastic tubes were sterilized according to Adnan etal [10] All reagents used were of analytical grade andthe instrument working calibration was made by dilutingthe commercial Scharlau Japan stock solution (1000mg Lminus1)standard with distilled-deionized water The detection limitsfor metal analysis were 001mg Lminus1 for Cd Cr Cu Ni and Pband 005mg Lminus1 for Zn

24 Metal Extraction of Atmospheric Settling Dust Totalmetal assessmentwas done according to Ogunfowokan etal [6] while sequential extraction was done using Finzgaret al [11] method The method modified Tessier et al [12]method

Journal of Applied Chemistry 3

Table 1 Mean traffic densityhour

Sampling site code Sampling site Average traffic volume per hrNumber of motorcycles Number of vehicles Number of truckslorries Total

1 Aminu Kano 1902 plusmn 12 2634 plusmn 10 196 plusmn 2 47322 Zoo 2011 plusmn 20 1504 plusmn 8 121 plusmn 5 36363 Dan Agundi 1206 plusmn 15 1935 plusmn 12 216 plusmn 2 28314 Kofar Nassarawa 1323 plusmn 13 1801 plusmn 19 46 plusmn 2 31705 Rimi Market 3005 plusmn 10 2008 plusmn 14 25 plusmn 2 50386 Sani Abacha 6857 plusmn 23 1292 plusmn 13 207 plusmn 2 83577 Ibo Road 2464 plusmn 19 1845 plusmn 19 35 plusmn 5 43448 CourtFrance 2651 plusmn 18 1041 plusmn 9 16 plusmn 2 37089 Kofar Mazugal 1995 plusmn 21 2836 plusmn 12 149 plusmn 2 418010 ZungeruAirport 1443 plusmn 11 2366 plusmn 17 198 plusmn 3 4007C Farm Center Nil Nil Nil Nil

Table 2 Concentrations (120583ggminus1) of metals in samples collected from different sites across the seasons

Metal SN Site Control1 2 3 4 5 6 7 8 9 10

Cd

A 489 574 289 1080 1049 89 668 1393 877 1288 000B 949 1081 527 2039 1884 1538 1189 2600 1527 1970 000C 1201 1358 706 2482 2518 1955 1492 3295 2072 2585 000D 276 339 153 759 686 643 530 881 559 869 000

Cr

A 1978 3696 6128 3389 2953 2000 2467 3885 8779 2814 000B 1978 5657 4450 4779 2996 4213 4707 17146 15182 5292 001C 2457 7098 9828 6685 3690 4369 6762 22076 18852 6494 000D 874 2761 2206 2155 1995 1680 1996 7258 6794 2073 000

Ni

A 13475 7191 8067 6683 9069 7982 6688 7288 4654 12114 001B 23661 3466 4373 2627 7229 4989 12913 18388 6480 8665 000C 32714 4798 5385 3763 9967 8886 19665 23754 9464 12152 000D 25485 3881 4755 3800 4710 3596 16695 17269 8950 7478 000

Pb

A 13371 16749 18905 12913 18889 15677 21539 21376 16123 21952 000B 9035 13522 15123 21858 106801 11897 13760 13506 14322 16408 000C 12753 18275 19628 29110 140857 17877 25369 24786 19724 25498 000D 6159 8089 9518 12179 64068 7580 7812 7862 8652 10198 000

Cu

A 2651 5071 4451 5510 5621 7154 13164 3671 3659 3744 000B 1615 3916 4021 20521 5734 6195 11676 3166 3054 2505 000C 2054 5387 5128 26739 6632 8184 14928 4105 4019 3147 000D 1330 2391 2151 9862 3172 3670 6479 1771 1825 1661 000

Zn

A 15398 29582 25985 50707 42923 37208 19213 202842 67545 21349 010B 231228 1171120 237119 1089270 943583 799974 569499 2351552 1467383 740533 028C 208370 878165 226352 845163 713512 635411 493263 1740177 1120480 550689 028D 21152 126107 20182 121131 88305 74149 60818 315232 149391 77006 032

SN season A cool and dry season B hot and dry season C warm and wet season D warm and dry season

3 Results and Discussion

The total concentrations of Cd Cr Ni Pb Cu andZn for the samples are presented in Table 2 In eachcase the presented value is a mean observed in threedeterminations Analysis of variance revealed significantdifference (119875 lt 005) in the contents of the studied heavymetals across sites across the studied seasons The concen-trations across the seasons varied to great extent among

the samples 505ndash2599 701ndash3290 157ndash872 and 277ndash1386 120583ggminus1 for Cd 1957ndash17143 2414ndash22051 848ndash7216 and1955ndash8757120583ggminus1 for Cr 2654ndash23521 3736ndash32529 3800ndash25470 and 6667ndash13450 120583ggminus1 for Ni 9071ndash106703 12705ndash140813 6119ndash64136 and 13342ndash21352 120583gmminus2 for Pb 1580ndash20473 2009ndash26977 1360ndash9924 and 2602ndash13327 120583ggminus1 forCu and 231436ndash2353103 208739ndash1740354 21304ndash315465and 15495ndash202984120583ggminus1 for Zn for cool and dry season


00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site

Water solubleExchangeableCarbonate bound

Fe-Mn oxide and hydroxideOrganic boundResidual

Figure 2 Percentage of Cd in each operational fraction of atmo-spheric particulate dust (cool and dry season)

hot and dry season warm and wet season and warm anddry season respectively Irrespective of sampling site thedistribution of total metals in the atmospheric particulatedust samples generally followed the order Cd lt Cr lt Cult Ni lt Pb lt Zn Highest concentration of Cd Cr and Znwas found in site 8 while highest concentration of Ni Pband Cu was found in sites 1 5 and 4 respectively Alsohighest concentrations of all studied metals were recordedin hot and dry season with exception of Zn that has highestconcentration recorded in cool and dry season In generalhighest concentrations ofmetals studiedwere recorded in dryseasonsThis could be due to lowmoisture content of samplesduring this season Comparing the data of control site to thestudied sites lower concentrations of metals were obtainedfrom control site

Correlation analysis indicates positive significant corre-lation (119875 lt 005) between Zn and Cr (hot and dry season)and Zn Cd and Cr (warm and wet season and warm anddry season) Positive correlation of metals indicates commonsource of metals

The distribution of heavy metals Cd Cr Ni Pb Cuand Zn in the six fractions water soluble (FI) exchangeable(FII) carbonate bound (FIII) Fe-Mn oxide (FIV) organicbound (FV) and residual (FVI) for all studied samples issummarized in Figures 2ndash24 The results obtained showedthat the amounts of heavy metals extracted from eachfraction vary widely among the sites across seasons (119875 lt005)

Significant amount of Cd was associated with carbonateand Fe-Mn oxide fractions especially during the dry seasonsas shown in Figures 2ndash5 Highest percentage of Fe-Mn oxidewas obtained in site 3 during the warm and wet seasonAveragely Cd distribution among the geochemical fractionsof the particulate dust in the four seasons was

Frac

tion

()

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Figure 3 Percentage of Cd in each operational fraction of atmo-spheric particulate dust (hot and dry season)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site



Figure 4 Percentage of Cd in each operational fraction of atmo-spheric particulate dust (warm and wet season)

cool and dry season FIV gt FIII gt FVI gt FII gt FI gt FV

hot and dry season FIV gt FIII gt FVI gt FII gt FI gt FV

warm and wet season FIII gt FII gt FIV gt FV gt FI gtFVI

Journal of Applied Chemistry 5Fr

actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Figure 5 Percentage of Cd in each operational fraction of atmo-spheric particulate dust (warm and dry season)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()

Figure 6 Percentage of Cr in each operational fraction of atmo-spheric particulate dust (cool and dry season)

warm and dry season FIII gt FVI gt FIV gt FV gt FII gtFI

For Cr (Figures 6ndash9) the residual fraction exhibited thehighest percentage ranging from 8207 to 9278 in site 9in dry season The low level of Cr in water soluble andexchangeable fractions of the samples may be an indicationthat leaching of Cr from the particulate dust may not occur

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()

Figure 7 Percentage of Cr in each operational fraction of atmo-spheric particulate dust (hot and dry season)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site



Figure 8 Percentage of Cr in each operational fraction of atmo-spheric particulate dust (warm and wet season)

readily The patterns of Cr distribution among the fractionsof the atmospheric particulate dust in the four seasons are

cool and dry season FVI gt FV gt FIV gt FIII gt FII gtFIhot and dry season FVI gt FV gt FIV gt FIII gt FII gt FIwarm and wet season FVI gt FV gt FIV gt FII gt FI gtFIIIwarm and dry season FIII gt FVI gt FIV gt FV gt FII gtFI

6 Journal of Applied ChemistryFr

actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Figure 9 Percentage of Cr in each operational fraction of atmo-spheric particulate dust (warm and dry season)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()

Figure 10 Percentage of Ni in each operational fraction of atmo-spheric particulate dust (cool and dry season)

The Ni similar to Cr was concentrated in the residualfraction with exception of warm and wet season as shownin Figures 10ndash13 ranging from 762 to 7273 The organicfraction was second in proportion ranging from 000 to5692 followed by Fe-Mn oxide carbonate exchangeableand water soluble Based on the result found the profileobtained for Ni was

cool and dry season FVI gt FV gt FIV gt FIII gt FII gtFI

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()

Figure 11 Percentage of Ni in each operational fraction of atmo-spheric particulate dust (hot and dry season)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site



Figure 12 Percentage of Ni in each operational fraction of atmo-spheric particulate dust (warm and wet season)

hot and dry season FVI gt FV gt FIV gt FIII gt FI gt FIIwarm and wet season FV gt FII gt FIV gt FVI gt FI gtFIIIwarm and dry season FVI gt FIV gt FIII gt FV gt FI gtFII

Pb in the particulate dust samples is significantly associ-ated with the carbonate bound fraction with range of 881ndash6469 across the season as shown in Figures 14ndash17 whichsuggested that Pb had a preference for carbonate fractions at


00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site



Figure 13 Percentage of Ni in each operational fraction of atmo-spheric particulate dust (warm and dry season)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site



Figure 14 Percentage of Pb in each operational fraction of atmo-spheric particulate dust (cool and dry season)

the expense of Fe-Mn oxides Of the ten samples site 1 samplehas high fraction of Pb in the residual fraction Howeveron the average percent of total Pb associated with differentfractions across the site was in the following order

cool and dry season FIII gt FVI gt FIV gt FV gt FI gtFIIhot and dry season FIII gt FVI gt FIV gt FV gt FI gt FIIwarm and wet season FIII gt FVI gt FIV gt FV gt FI gtFIIwarm and dry season FIII gt FVI gt FIV gt FV gt FII gtFI

Frac

tion

()

00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site



Figure 15 Percentage of Pb in each operational fraction of atmo-spheric particulate dust (hot and dry season)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site



Figure 16 Percentage of Pb in each operational fraction of atmo-spheric particulate dust (warm and wet season)

The behaviour of Cu is quite different from other metalsin that percentage fractions are higher in the organic boundranging from 362 to 8962 (Figures 18ndash21) Based on theresult found the profile obtained for Cu was

cool and dry season FVgt FVIgt FIVgt FIgt FIIgt FIIIhot and dry season FV gt FVI gt FIV gt FI gt FII gt FIIIwarm and wet season FV gt FVI gt FIV gt FI gt FIII gtFIIwarm and dry season FV gt FVI gt FIV gt FI gt FIII gtFII


actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Figure 17 Percentage of Pb in each operational fraction of atmo-spheric particulate dust (warm and dry season)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site



Figure 18 Percentage of Cu in each operational fraction of atmo-spheric particulate dust (cool and dry season)

As for Zn significant amount of Zn was associatedwith the residue fractions ranging from 096 to 8750across the seasons (Figures 22ndash25) Zn association with thechemically reactive fractions such as Zn in water soluble andexchangeable forms generally represented less than 10of thetotal fractions of Zn in the samples The distribution of Znamong the particulate dust fractions across the seasons is

cool and dry season FVI gt FIV gt FIII gt FV gt FI gtFII

hot and dry season FVI gt FIV gt FIII gt FV gt FII gt FI

Frac

tion

()

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Figure 19 Percentage of Cu in each operational fraction of atmo-spheric particulate dust (hot and dry season)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()



Figure 20 Percentage of Cu in each operational fraction ofatmospheric particulate dust (warm and wet season)

warm and wet season FVI gt FIV gt FIII gt FV gt FI gtFII

warm and dry season FIV gt FII gt FV gt FVI gt FII gtFI

Heavy metal speciation studies are important since slightchanges inmetal availability and in environmental conditionscan cause these elements to be toxic to animals andplants [13]From the results presented above Cd was found in its highestproportion in the formbound to Fe-Mn oxide (6031) in site3 sample


00

100

200

300

400

500

600

700

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900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site



Figure 21 Percentage of Cu in each operational fraction of atmo-spheric particulate dust (warm and dry season)

00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()



Figure 22 Percentage of Zn in each operational fraction ofatmospheric particulate dust (cool and dry season)

The highest percentage of this fraction is relatively highand constitutes a large portion of nonresidual CdHeavymet-als enwrapped by Fe-Mn oxides or precipitated as hydroxidehave been reported by Wang et al [14]

Metals bound to Fe-Mn oxides would be released underreductive conditions [15] and therefore are unstable underanaerobic condition Similar to this study Feng et al [16]reported high percentage of Cd in carbonate and Fe-MnOfractions Also Cd in samples agrees with the findings ofHarrison et al [17] Baron et al [18] and Yusuf [19] The high

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()



Figure 23 Percentage of Zn in each operational fraction ofatmospheric particulate dust (hot and dry season)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()



Figure 24 Percentage of Zn in each operational fraction ofatmospheric particulate dust (warm and wet season)

amount of Cd associated with nonresidual fractions showsthat it may be easily transferred into the food chain Theminor role for organic fraction in the fractionation of Cd inthis study is consistent with the low adsorption constant ofCd to organic matter [20] and with evidence that Cd does notappear to form strong organic complexes [21]

The high percentage of Cr (3115ndash8488) across theseasons was found in the residual fraction indicating that


00

100

200

300

400

500

600

700

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900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()




Cr shows little risk to environment Metal in this fractionis mainly fixed in the primary and secondary minerals [22]and is chemically stable and biologically inactiveThe greaterthe percentage of metals present in this fraction the smallerthe risk of the metal because this portion of metal cannotbe rereleased to environment under normal conditions [14]Furthermore the stable nature of the metal and the factthat the metal are bonded firmly within a mineral latticerestricting the bioavailability of this metal [23] The trend inNi is similar to that in Ni in the fact that residual fraction isthe major carriers of Ni in the atmospheric particulate dustSimilar trend was reported by Ma and Rao [24]

In a study by Flores-Rodriguez et al [25] on the bioavail-able and stable forms of atmospheric particulate dust Fe-MnO and carbonate fractions of suspended solids are themost important in terms of metal binding irrespective ofheavy metal This finding is in general agreement with theresults of this study for Pb Studies on the fractionation ofatmospheric particulate dust have suggested that Pb has ahigh affinity for carbonates [16] As such Pb is generallyconsidered to be relatively mobile with the dust particlesprimarily as a result of its small soluble component Highamount of Pb in the carbonate fractions is also reported inother studies on roadside soils Howard and Sova [26] notedfor example a larger part of Pb in the carbonate fraction inthe most heavily contaminated roadside soil

The predominant form of Cu available in the entirefraction is organic fraction The higher stability constant ofCu complexes with organic matter leads to higher organicfractions Tessier et al [12] indicated that Cu exhibits thehighest stability constants for most ligand among the heavymetals studied Based on this Ho [27] suggested that the highaffinity of organic ligands with heavy metals makes Cu inriver sediments more stable leading to the suppression ofdiffusion and dispersion of Cu though dust samples were

considered in this study similar reasons could be responsibleHowever under strong oxidizing conditions Cu be leachedinto the environment [14] In this fraction the metal ionacts as the central ion and the active organic matter groupacts as the ligand or perhaps through the reaction of thesulphide ion and Cu The organic fraction released in thisstep is hardly considered very mobile or available becausethe Cu is associated with stable high-molecular weight humicsubstances that decompose slowly [28] A high percentage(362ndash8962) of Cu was found in the oxidizable fractionindicating that high organicmatter and sulphide absorbedCuand played a significant role in controlling the mobilizationof this element Cu is usually reported to dominate in theorganic and residual fractions [17 24 29 30]

From the results Zn fraction is considered to be occludedinside the crystalline structures and not readily availablefor plant absorption The findings are different with thatof Shuman [31] who reported that soil Zn was mainlyassociatedwith crystalline Fe-Mnoxide andwith nonresidualextractable residual fraction though atmospheric particulatedust was used in this study Usero et al [32] and Mashal etal [33] using Tessierrsquos method found that Zn is bound toresidual fraction Maskall and Thornton [34] indicate thatin contaminated soils Zn is mainly found in the residualfractions The results for atmospheric particulate dust aresimilar but with less association with Fe-Mn oxides anda higher percentage with the residual fraction For Cr theresidual fraction exhibited the highest percentage

4 Conclusion

Theatmospheric dust collected from roads in KanoMetropo-lis shows high concentrations of heavy metals which couldlead to serious environmental hazards Correlation analysisindicates common source of metals Znp and Cr (hot anddry season) and Zn Cd and Cr (warm and wet season andwarm and dry season) The sequential extraction showedthat significant amount of Cd was associated with carbonateand Fe-Mn oxide fractions especially during the dry seasonsFor Cr and Ni the residual fraction exhibited the highestpercentage Pb in the particulate dust samples is significantlyassociated with the carbonate bound fraction with range of881ndash6469 across the season The behaviour of Cu is quitedifferent from other metals in that percentage fractions arehigher in the organic bound As for Zn significant amountwas associated with the residue fractions ranging from 096to 8750 across the seasons This study indicated that airparticle pollution due tometal such as Cd and Pbmay possessserious health risks to the residents in this rapidly developingand populated city

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgments

The authors appreciate the support of Mursquoazu and Khadijatboth of Department of Chemistry Kaduna State University


Nigeria for analyzing the samples Thanks are due to MalAhmad Mohammed of Kano Pollution Control Unit KanoNigeria for his assistance especially in the field work Mem-bers of staff of Chemistry Department of Ahmadu BelloUniversity are also acknowledged for their immense supportgiven to realization of this project

References

[1] S-H Cho H Tong J K McGee R W Baldauf Q T Krantzand M I Gilmour ldquoComparative toxicity of size-fractionatedairborne particulate matter collected at different distances froman urban highwayrdquo Environmental Health Perspectives vol 117no 11 pp 1682ndash1689 2009

[2] J Edwards S Walters and R K Griffiths ldquoHospital admissionsfor asthma in preschool children relationship to major roadsin Birmingham United Kingdomrdquo Archives of EnvironmentalHealth vol 49 no 4 pp 223ndash227 1994

[3] A J Venn S A Lewis M Cooper R Hubbard and J BrittonldquoLiving near a main road and the risk of wheezing illness inchildrenrdquo American Journal of Respiratory and Critical CareMedicine vol 164 no 12 pp 2177ndash2180 2001

[4] A O Ogunfowokan O I Asubiojo A A Adeniyi and EA Oluyemi ldquoTrace lead zinc and copper levels in Barbulalambarenensis as amonitor of local atmospheric pollution in Ile-Ife Nigeriardquo Journal of Applied Sciences vol 4 no 3 pp 380ndash383 2004

[5] H J Annergarn S J Moja J Malahela P Kgashane and B deLange ldquoVanderbijlpark-Golden highway project dust fall-outmonitoring reportrdquo AER 22178S GHP 2002

[6] A O Ogunfowokan J A O Oyekunle L M Durosinmi AI Akinjokun and O D Gabriel ldquoSpeciation study of lead andmanganese in roadside dusts frommajor roads in Ile-Ife SouthWesternNigeriardquoChemistry and Ecology vol 25 no 6 pp 405ndash415 2009

[7] O O Faboya ldquoIndustrial pollution and waste managementrdquoin Dimensions of Environmental Problems in Nigeria A Osun-tokun Ed pp 26ndash35 Ibadan Davidson Press Ibadan Nigeria1997

[8] G Nabuloa ldquoAssessment of heavymetal contaimination of foodcrops and vegetables from motor vehicle emission in KampalaCity Ugandardquo A technical report submitted to IDRC-Agrop-olis Idrinfo Idc Caarchievecordocs119964AGROPLIS-TECHRPT 2004

[9] O J Okunola A Uzairu C E Gimba and J A Kagbu ldquoMetalsin roadside soils of different grain sizes from high traffic roadsin Kano metropolis Nigeriardquo Toxicological and EnvironmentalChemistry vol 93 no 8 pp 1572ndash1590 2011

[10] M Adnan A Foras and J Qasem ldquoDetermination of cadmiumand lead in different cigarette brands in Jordanrdquo Acta ChimicaSlovenica vol 50 pp 375ndash381 2003

[11] N Finzgar P Tlustos and D Lestan ldquoRelationship of soilproperties to fractionation bioavailability and mobility of leadand zinc in soilrdquo Plant Soil and Environment vol 53 no 5 pp225ndash238 2007

[12] A Tessier P G C Campbell and M Blsson ldquoSequentialextraction procedure for the speciation of particulate tracemetalsrdquo Analytical Chemistry vol 51 no 7 pp 844ndash851 1979

[13] K M Banat F M Howari and A A Al-Hamad ldquoHeavymetalsin urban soils of central Jordan should we worry about theirenvironmental risksrdquoEnvironmental Research vol 97 no 3 pp258ndash273 2005

[14] LWang R Yu G Hu and X Tu ldquoSpeciation and assessment ofheavy metals in surface sediments of Jinjiang River tidal reachSoutheast of Chinardquo EnvironmentalMonitoring and Assessmentvol 165 no 1ndash4 pp 491ndash499 2010

[15] A K Singh S I Hasnain and D K Banerjee ldquoGrain sizeand geochemical partitioning of heavy metals in sediments ofthe Damodar Rivermdasha tributary of the lower Ganga IndiardquoEnvironmental Geology vol 39 no 1 pp 90ndash98 1999

[16] X D Feng Z Dang W L Huang and C Yang ldquoChemicalspeciation of fine particle bound trace metalsrdquo InternationalJournal of Environmental Science amp Technology vol 6 no 3 pp337ndash346 2009

[17] R M Harrison D P H Laxen and S J Wilson ldquoChemicalassociations of lead cadmium copper and zinc in street dustsand roadside soilsrdquo Environmental Science and Technology vol15 no 11 pp 1378ndash1383 1981

[18] J Baron M Legret and M Astruc ldquoStudy of interactionsbetween heavy metals and sewage sludges Determination ofstability constants and complexation capacities of complexesformed with Cu and Cdrdquo Environmental Technology vol 11 no2 pp 151ndash162 1990

[19] K A Yusuf ldquoSequential extraction of Pb Cu Cd and Zn in soilsnearOjota waste siterdquo Journal of Agronomy vol 6 no 2 pp 331ndash337 2007

[20] A Chlopecka J R Bacon M J Wilson and J Kay ldquoForms ofcadmium lead and zinc in contaminated soils from SouthwestPolandrdquo Journal of Environmental Quality vol 25 no 1 pp 69ndash79 1996

[21] G Sposito L J Lund and A C Chang ldquoTrace metal chemistryin arid-zone field soils amendedwith sewage sludge I Fraction-ation of Ni Cu Zn Cd and Pb in solid phasesrdquo Soil ScienceSociety of America Journal vol 46 no 2 pp 260ndash264 1982

[22] P Wu C Q Liu G P Zhang and Y G Yang ldquoChemicalforms and ecological risks of heavy metals in river sediment atcarbonatite mining areardquo Rural Eco-Environment vol 20 no 3pp 28ndash31 2004

[23] P P Coetzee ldquoDetermination and speciation of heavy metalsin sediments of the Hartbeespoort Dam by sequential chemicalextractionrdquoWater SA vol 19 no 4 pp 291ndash300 1993

[24] L Q Ma and G N Rao ldquoChemical fractionation of cadmiumcopper nickel and zinc in contaminated soilsrdquo Journal ofEnvironmental Quality vol 26 no 1 pp 259ndash264 1997

[25] J Flores-Rodriguez A L Bussy and D R Thevenot ldquoToxicmetals in urban runoff physico-chemical mobility assessmentusing speciation schemesrdquo Water Science and Technology vol29 pp 83ndash93 1994

[26] J L Howard and J E Sova ldquoSequential extraction analysis oflead inMichigan roadside soils mobilization in the vadose zoneby deicing saltrdquo Journal of Soil Contamination vol 2 pp 361ndash378 1993

[27] T L T Ho Heavy metal pollution of agricultural soil and riversediment in Hanoi Vietnam [PhD thesis] Kyushu UniversityFukuoka Japan 2000

[28] S P Singh F M Tack and M G Verloo ldquoHeavy metalfractionation and extractability in dredged sediment derivedsurface soilsrdquoWater Air and Soil Pollution vol 102 no 3-4 pp313ndash328 1998

[29] R S D Hamilton D M Revitt and R S Warren ldquoLevels andphysico-chemical associations of Cd Cu Pb and Zn in roadsedimentsrdquo Science of the Total Environment vol 33 no 1ndash4 pp59ndash74 1984


[30] L Ramos L M Hernandez and M J Gonzalez ldquoSequentialfractionation of copper lead cadmium and zinc in soils from ornear Donana National Parkrdquo Journal of Environmental Qualityvol 23 no 1 pp 50ndash57 1994

[31] L M Shuman ldquoFractionation method for soil microelementsrdquoSoil Science vol 140 no 1 pp 11ndash22 1985

[32] J Usero M Gamero J Morillo and I Gracia ldquoComparativestudy of three sequential extraction procedures for metals inmarine sedimentsrdquo Environment International vol 24 no 4 pp487ndash496 1998

[33] K Mashal M Al-Qinna and A Yahya ldquoSpatial distributionand environmental implication of lead and zinc in urban soilsand street dust samples in Al-Hashimeyehmunicipalityrdquo JordanJournal of Mechanical and Industrial Engineering vol 3 no 2pp 141ndash150 2009

[34] J E Maskall and I Thornton ldquoChemical partitioning of heavymetals in soils clays and rocks at historical lead smelting sitesrdquoWater Air and Soil Pollution vol 108 no 3-4 pp 391ndash409 1998

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


Main roadRailwaySecondary road

Control point

0 2500

N

S

(m)

Sampling siteInternational airport

8∘33

9984001969

998400998400E

8∘31

9984005969

998400998400E 8∘33

9984001969

998400998400E 8∘34

9984003969

998400998400E

8∘34

9984003969

998400998400E

12∘02

9984003957

998400998400N 12∘02

9984003957

998400998400N

12∘01

9984001957

998400998400N

11∘59

9984005957

998400998400N

12∘01

9984001957

998400998400N

11∘59

9984005957

998400998400N

Figure 1 Kano Metropolis showing the sampling sites Source adapted and modified from Google Map Data 2010

are some of its dominating industries [7] Kano Metropolisattracts substantial number of immigrants being the seat ofgovernment and center of commerce industry and educa-tion In the city there are various large markets such asthe City (Kurmi) Market Sabon Gari Market and KatinKwari (cloth market) which attract people from all overthe country The major form of transportation within KanoMetropolis is by road Most common transport modesused include cars buses motorcycles and tricycles (KekeNAPEP)

22 Sample Collection and Pretreatment Sampling of dustsfor this studywas conducted fromDecember 2009 to Septem-ber 2010 across four named seasons cold and dry hot anddry warm and wet and warm and dry The criteria forselections of roads for the studywere based on foreknowledgeof the relative traffic density on each road and the desireto have each category of traffic density in different sectionsof the Metropolis Samples were collected from 10 roadsidelocations (1ndash10) and a control site (C) all over the Metropolisas shown in Figure 1 These sites were mainly located inresidential and commercial areas of the metropolis Controlsamples were obtained from a small garden within a resi-dential buildup area of farm center which is not closer to

any secondary or main road Average temperature across theseasons is 315ndash366∘C 300ndash391∘C 305ndash339∘C and 301ndash395∘C respectively

Atmospherically deposited particulates were sampledaccording to indirect method of air sampling described byNabuloa [8] Similarly the traffic density was determined bymanual counting according to Okunola et al [9] as shown inTable 1

23 Quality Assurance All apparatus including glasswareand plastic tubes were sterilized according to Adnan etal [10] All reagents used were of analytical grade andthe instrument working calibration was made by dilutingthe commercial Scharlau Japan stock solution (1000mg Lminus1)standard with distilled-deionized water The detection limitsfor metal analysis were 001mg Lminus1 for Cd Cr Cu Ni and Pband 005mg Lminus1 for Zn

24 Metal Extraction of Atmospheric Settling Dust Totalmetal assessmentwas done according to Ogunfowokan etal [6] while sequential extraction was done using Finzgaret al [11] method The method modified Tessier et al [12]method







Cd

A 489 574 289 1080 1049 89 668 1393 877 1288 000B 949 1081 527 2039 1884 1538 1189 2600 1527 1970 000C 1201 1358 706 2482 2518 1955 1492 3295 2072 2585 000D 276 339 153 759 686 643 530 881 559 869 000

Cr

A 1978 3696 6128 3389 2953 2000 2467 3885 8779 2814 000B 1978 5657 4450 4779 2996 4213 4707 17146 15182 5292 001C 2457 7098 9828 6685 3690 4369 6762 22076 18852 6494 000D 874 2761 2206 2155 1995 1680 1996 7258 6794 2073 000

Ni

A 13475 7191 8067 6683 9069 7982 6688 7288 4654 12114 001B 23661 3466 4373 2627 7229 4989 12913 18388 6480 8665 000C 32714 4798 5385 3763 9967 8886 19665 23754 9464 12152 000D 25485 3881 4755 3800 4710 3596 16695 17269 8950 7478 000

Pb

A 13371 16749 18905 12913 18889 15677 21539 21376 16123 21952 000B 9035 13522 15123 21858 106801 11897 13760 13506 14322 16408 000C 12753 18275 19628 29110 140857 17877 25369 24786 19724 25498 000D 6159 8089 9518 12179 64068 7580 7812 7862 8652 10198 000

Cu

A 2651 5071 4451 5510 5621 7154 13164 3671 3659 3744 000B 1615 3916 4021 20521 5734 6195 11676 3166 3054 2505 000C 2054 5387 5128 26739 6632 8184 14928 4105 4019 3147 000D 1330 2391 2151 9862 3172 3670 6479 1771 1825 1661 000

Zn

A 15398 29582 25985 50707 42923 37208 19213 202842 67545 21349 010B 231228 1171120 237119 1089270 943583 799974 569499 2351552 1467383 740533 028C 208370 878165 226352 845163 713512 635411 493263 1740177 1120480 550689 028D 21152 126107 20182 121131 88305 74149 60818 315232 149391 77006 032






00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site








Frac

tion

()

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site








actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()


00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()


00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site






Frac

tion

()

00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







Frac

tion

()

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()








00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()






00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()









4 Conclusion




Acknowledgments




References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of







Cd

A 489 574 289 1080 1049 89 668 1393 877 1288 000B 949 1081 527 2039 1884 1538 1189 2600 1527 1970 000C 1201 1358 706 2482 2518 1955 1492 3295 2072 2585 000D 276 339 153 759 686 643 530 881 559 869 000

Cr

A 1978 3696 6128 3389 2953 2000 2467 3885 8779 2814 000B 1978 5657 4450 4779 2996 4213 4707 17146 15182 5292 001C 2457 7098 9828 6685 3690 4369 6762 22076 18852 6494 000D 874 2761 2206 2155 1995 1680 1996 7258 6794 2073 000

Ni

A 13475 7191 8067 6683 9069 7982 6688 7288 4654 12114 001B 23661 3466 4373 2627 7229 4989 12913 18388 6480 8665 000C 32714 4798 5385 3763 9967 8886 19665 23754 9464 12152 000D 25485 3881 4755 3800 4710 3596 16695 17269 8950 7478 000

Pb

A 13371 16749 18905 12913 18889 15677 21539 21376 16123 21952 000B 9035 13522 15123 21858 106801 11897 13760 13506 14322 16408 000C 12753 18275 19628 29110 140857 17877 25369 24786 19724 25498 000D 6159 8089 9518 12179 64068 7580 7812 7862 8652 10198 000

Cu

A 2651 5071 4451 5510 5621 7154 13164 3671 3659 3744 000B 1615 3916 4021 20521 5734 6195 11676 3166 3054 2505 000C 2054 5387 5128 26739 6632 8184 14928 4105 4019 3147 000D 1330 2391 2151 9862 3172 3670 6479 1771 1825 1661 000

Zn

A 15398 29582 25985 50707 42923 37208 19213 202842 67545 21349 010B 231228 1171120 237119 1089270 943583 799974 569499 2351552 1467383 740533 028C 208370 878165 226352 845163 713512 635411 493263 1740177 1120480 550689 028D 21152 126107 20182 121131 88305 74149 60818 315232 149391 77006 032






00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site








Frac

tion

()

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site








actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()


00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()


00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site






Frac

tion

()

00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







Frac

tion

()

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()








00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()






00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()









4 Conclusion




Acknowledgments




References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site








Frac

tion

()

00

100

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400

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600

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900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

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900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site








actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

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1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()




00

100

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600

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800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()


00

100

200

300

400

500

600

700

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900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

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500

600

700

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900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()




00

100

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300

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500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()


00

100

200

300

400

500

600

700

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900

1000

1 2 3 4 5 6 7 8 9 10

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tion

()

Site







00

100

200

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600

700

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900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

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tion

()

Site






Frac

tion

()

00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







actio

n (

)

00

100

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300

400

500

600

700

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900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

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600

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900

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1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







Frac

tion

()

00

100

200

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600

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900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

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600

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900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()








00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()






00

100

200

300

400

500

600

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900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()




00

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1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()









4 Conclusion




Acknowledgments




References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

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Frac

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Frac

tion

()


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tion

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actio

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700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site






Frac

tion

()

00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







Frac

tion

()

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()








00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()






00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()









4 Conclusion




Acknowledgments




References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site



Frac

tion

()


00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site






Frac

tion

()

00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







Frac

tion

()

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()








00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()






00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()









4 Conclusion




Acknowledgments




References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site






Frac

tion

()

00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







Frac

tion

()

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()








00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()






00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()









4 Conclusion




Acknowledgments




References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


actio

n (

)

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site







Frac

tion

()

00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()








00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()






00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()









4 Conclusion




Acknowledgments




References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10

Frac

tion

()

Site




00100200300400500600700800900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()






00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()




00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()







00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()









4 Conclusion




Acknowledgments




References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


00

100

200

300

400

500

600

700

800

900

1000

1 2 3 4 5 6 7 8 9 10Site

Frac

tion

()









4 Conclusion




Acknowledgments




References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of
















Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

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