research article study of selected metals distribution, source...

Research ArticleStudy of Selected Metals Distribution Source Apportionmentand Risk Assessment in Suburban Soil Pakistan

Javed Iqbal and Munir H Shah

Department of Chemistry Quaid-i-Azam University Islamabad 45320 Pakistan

Correspondence should be addressed to Javed Iqbal jianasyahoocomsg and Munir H Shah mhshahgqauedupk

Received 7 December 2014 Revised 8 March 2015 Accepted 26 May 2015

Academic Editor Rita Rosa Pla

Copyright copy 2015 J Iqbal and M H Shah This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Composite soil samples collected from suburban areaswere analyzed for Cd Co Cr Cu FeMn Pb Sr andZn by atomic absorptionspectrophotometry Based on pseudototal metal analysis Fe Mn Sr and Zn were the prevailing metals while Cd Co Cr and Pbwere the least participants However based on bioavailability Cd Co Pb and Sr were easily leachable and might pose adverseeffects to soil biota In ecological risk assessment contamination factor demonstrated moderate contamination by Co Sr and Znand high contamination by Cd Cu and Pb geoaccumulation index indicated heavy to extreme contamination by Cd and heavycontamination by Pb enrichment factor revealed significant enrichment by Co Cr Cu Mn Sr and Zn and extreme enrichmentby Cd and Pb Substantial human inputs for Cd Co Cr Cu Mn Pb Sr and Zn were also revealed by principal component analysisin the examined soil Overall the study area was found to be contaminated at considerablehigh degree

1 Introduction

Recently there has been considerable concern pertaining tosoil contamination due to rapid industrialization urbaniza-tion and intense human activities particularly contamina-tion by different heavy metals [1ndash4] Metals are the moststudied soil pollutants because of their ubiquity toxicity andpersistence Some metals are essential for the metabolismof living organisms at low concentrations but above certainlevels they become toxic [5ndash7] Major anthropogenic sourcesof themetals includemining waste disposal fertilizers trafficemission (vehicle exhaust tire wear and brake lining wear)industrial effluents domestic emissions and atmosphericdepositions [8ndash10] Metals accumulation in soil is of greatconcern due to their potential ecological risks and damagingeffects on soil ecosystems [1 11] Thus it is necessary toquantify the extent of metals contamination and associatedecological risks of soil to potential receptors

The pseudototaltotal concentrations of metals in soilare useful indicators of contamination and ecological riskassessment [12 13] However total contents do not provideenough information about potential mobility bioavailability

and toxicity of the metals [14 15] Recently bioavailabilityof the metals in soil has become an important considerationfor many researchers [14 16 17] Several methods have beendesigned to simulate and quantify the metal reactivity as wellas the physicochemical and biologically available pools ofthe metals in soil [17] One of the most popular methodsfor estimating metal bioavailability is chemical extraction bymeans of various mild to strong extracting agents resultingin operationally defined specific metal fractions [18] Theassumption in these chemical extraction approaches is thatthe extracted metals are mobile and easily available forplants and leaching to groundwater andor could possibly bedetrimental to soil biota [19]Therefore efforts should also befocused on measurement of bioavailable fractions of selectedmetals

The present study aimed to (1) investigate concentrationsof Cd Co Cr Cu Fe Mn Pb Sr and Zn in soil duringsummer and winter seasons (2) determine their associatedecological risks (3) identify pollution sources by principalcomponent analysis and (4) find out bioavailability of thesemetals to soil biota

Hindawi Publishing CorporationJournal of ChemistryVolume 2015 Article ID 481324 8 pageshttpdxdoiorg1011552015481324

2 Journal of Chemistry

Figure 1 Locations map of the study area

2 Materials and Methods

21 Site Description In present study soil samples werecollected around Khanpur Lake (72∘561015840 E 33∘481015840N) which islocated onHaroRiver near the town of Khanpur about 40 kmnorthwest of Islamabad Pakistan (Figure 1) It supplies drink-ing water to Islamabad and Rawalpindi and irrigation waterto the surrounding agricultural areas It was constructed in1983 with the storage capacity of 140 million m3 Its averagewater depth is about 15mThe gross storage of the reservoir is0132 km3 with a total catchment area of 798 km2The surfacearea of the reservoir varies from a maximum of 1806 ha toa minimum of 215 ha The surrounding area of the lake isplanted with flowering trees and set with gardens picnicpoints and isolated paths The water stored in Khanpur Lakeis fed bymelting snow seasonal rains and the natural springsof Margalla Hills Pakistan

22 Sampling Processing and Chemical Analysis A total of80 composite surface (1ndash10 cm top layer) soil samples (eachcontaining 5ndash10 subsamples) were collected from residentialand picnic areas around the lake in summer (June 2012)andwinter (January 2013) in precleaned zip-locked polythenebags using a plastic scoop To determine pseudototal metalcontents the soil sampleswere ovendried grounded homog-enized sieved through a 2mm plastic sieve to remove stonesgravels and coarse particles and then stored in zip-lockedpolythene bags before chemical analysis [6 20]

To find out the pseudototal metal concentrations the soilsample (1-2 g dryweight) was digested using freshly preparedacid mixture of HNO

3and HCl (3 1 vv) in a microwave

system [21] Each digested sample was then filtered throughfine filter paper (045 120583m pore size) and then diluted with1 HNO

3[22] A reagent blank was also prepared having the

same amount of acids without the sample with each batchA selective single step extraction procedure using 01M

Ca(NO3)2 was performed at room temperature to determine

the bioavailable metal contents [16] An aliquot of 50 g ofair dried soil sample was added to 50mL solution of 01MCa(NO

3)2and the extraction was performed in precleaned

glass vessel by shaking on an autoshaker 240 vibrationsper minute for 16 h A reagent blank was also prepared withthe same amount of 01M Ca(NO

3)2solution without soil

sample Solid residuewas separated from the extracts throughfiltration using fine filter papers [16 23 24] The extractionswere carried out in triplicate for each sample

Table 1 Metal concentrations (mgkg) and recoveries () instandard reference material (SRM-2711)

MetalCertified

concentration(mgkg)

Measuredconcentration

(mgkg)

Recovery()

Cd 417 4098 98Co 10 97 97Cr 47 4756 101Cu 114 1123 99Fe 28900 27601 96Mn 638 642 101Pb 1162 1180 102Sr 2453 2417 99Zn 3504 341 97

The concentrations of Cd Co Cr Cu Fe Mn Pb Sr andZn inCa(NO

3)2and acid-extracts weremeasured using flame

atomic absorption spectrophotometer (Shimadzu AA-670Japan) under optimum analytical conditions Selected metalsconcentrations were estimated by following calibration linemethod and dilutions were done duly whenever needed [2023]

23 Quality Control and Quality Assurance Analytical gradechemicals were used throughout the study All the reagentsand calibration standards were prepared using deionizedwater The preparation of calibration metal standards fromstock solutions of 1000mgL was carried out by succeedingdilutions with deionizedwater All glassware usedwas soakedovernight in HNO

3solution (10 vv) and then rinsed

thoroughly with several portions of distilled water priorto use [22] The reagent blanks were prepared throughoutchemical analysis and were used to correct the analyticalresults Reproducibility of the results was also ensured fol-lowing analysis sequence of calibration of standards andblind standard solution analysis as unknown (quality controlsolutions) Standard reference material (SRM 2711) was alsoanalyzed as part of the quality assurance and quality control(QAQC) procedure and good agreement was observedbetween the data got from present study and the certifiedvalues (Table 1) Some soil samples were also analyzed at anindependent laboratory for cross comparison and a maxi-mum of plusmn25 difference was observed in the two results Allthe measurements were made in triplicate

24 Statistical Analysis The analyzed data were summarizedusing basic statistical parameters such as minimum maxi-mum median arithmetic mean geometric mean harmonicmean skewness and coefficients of variation STATISTICAsoftware was used for multivariate statistical analysis suchas principal component analysis (PCA) of the obtained data[25] PCA was applied both to discriminate between variousgeogenic inputs that cause variations in soil compositionand to find out pollution sources affecting the metal levelsof soil [20 26ndash28] It was employed to investigate theassociations among selected metals and their grouping into

Journal of Chemistry 3

a small number of factors After grouping metals withineach factor are highly associated among themselves thanwithmetals in other factors Varimax rotation was applied as itminimizes the number of variables with a high loading oneach component and assists in the explication of results PCAwith Varimax rotation was performed on log-transformeddata

25 Ecological Risk Assessment Contamination levels of CdCo Cr Cu Fe Mn Pb Sr and Zn were assessed usingcontamination factor (CF) and degree of contamination(119862deg) The CF is calculated using the following equation assuggested by Hakanson [29]

CF =119862119899

119862119887

(1)

where 119862119899and 119862

119887are the average concentrations of a metal

in the studied and the preindustrial soil respectively The CFis the single-element index whereas 119862deg is a multielementindex which is computed by adding contamination factors ofall metals studied as

119862deg =119894=119899

sum

119894=1CF (2)

In this study mean concentrations of elements in continentalearthrsquos crust [30] were used as reference values as suggestedby Loska et al [31]The results were interpreted as [29] CF lt 1= low contamination 1 le CF lt 3 = moderate contamination3 le CF lt 6 = considerable contamination 6 le CF = very highcontamination 119862deg lt 8 = low degree of contamination 8le 119862deg lt 16 = moderate degree of contamination 16 le 119862deg lt32 = considerable degree of contamination and 32 le 119862deg =very high degree of contamination

The 119868geo estimates contamination by comparing preindus-trial and studied metal concentrations [32] It is calculatedusing the following equation

119868geo = log2 (119862119899

15119861119899

) (3)

where 119862119899is the mean content of element examined in soil

and 119861119899is the geochemical background concentration in con-

tinental earth crust The factor 15 was established to reducethe outcome of promising changes in the background levelsdue to natural inputs In this investigation 119861

119899designates

concentration of metal in earth crust [30 31] Accordingto Muller [32] the contamination levels can be categorizedas 119868geo le 0 = practically uncontaminated 0 lt 119868geo lt 1 =uncontaminated to moderately contaminated 1 lt 119868geo lt 2= moderately contaminated 2 lt 119868geo lt 3 = moderately toheavily contaminated 3 lt 119868geo lt 4 = heavily contaminated4 lt 119868geo lt 5 = heavily to extremely contaminated and 5 lt 119868geo= extremely contaminated

Enrichment factor (EF) represents the extent to whichmetals are enriched or reduced comparative to a partic-ular source and can be used to segregate between metalscontributed by human intrusions and those from geogenic

provenance [33ndash35] It is based on the normalization of ameasured metal against a reference metal Generally Al CaFe Mg and Mn are used as the reference elements In thisstudy EFs were computed using Fe as a reference metal usingthe following relationship

EF =(119862119909119862ref)Sample

(119862119909119862ref)Crust

(4)

where119862119909is the average concentration ofmetal of interest and

119862ref refers to mean concentration of reference element fornormalization EF values were interpreted as follows [36] EFlt 2 indicated minimal enrichment EF = 2ndash5 showed moder-ate enrichment EF = 5ndash20 exhibited significant enrichmentEF = 20ndash40 manifested very high enrichment and EF gt 40reflected extremely high enrichment

3 Results and Discussion

31 Soil Characteristics and Metals Distribution Hydrogenion concentration (pH) in the studied soil ranged 74ndash82and 72ndash78 with average values of 78 and 76 in summer andwinter respectively On the average basis the levels of pHwere observed slightly higher in summer than winter Table 2shows the statistical summary related to selected metalsdistribution based on pseudototal contents in surface soil insummer and winter The results related to the distribution ofthe metals based on pseudototal contents in soil in summerandwinter revealed that Fe (3993ndash5429 in summer and 2462ndash4171mgkg in winter) Mn (212ndash778 in summer and 179ndash561mgkg in winter) and Sr (47ndash1356 in summer and 62ndash739mgkg in winter) were the dominant contributors whileCd (035ndash61 in summer and lt001ndash52mgkg in winter) wasthe least participant in the studied soil in both seasonsOn thearithmetic mean basis the decreasing concentration orderof the metals was Fe gt Sr gt Mn gt Zn gt Pb gt Cr gt Cu gtCo gt Cd and Fe gt Mn gt Sr gt Zn gt Co gt Cu gt Cr gt Pb gtCd in summer and winter successively Total metal load ofthese selected metals varied as 4404ndash8376mgkg and 2784ndash5731mgkg with mean values of 6061mgkg and 4585mgkgin summer and winter respectively Moreover the averagelevels of these metals were also found to be higher in summerthan winter (119875 lt 005) Overall Cd Sr and Pb showedrelatively higher coefficients of variance (CV) demonstratingthat these metals were highly influenced by anthropogenicactivities in the study area

In comparison with the results of urban soils in theprevious study [20] it was found that the measured concen-trations of selected metals in the current study in suburbansoils were relatively higher than the reported levels in urbansoils indicating that therewere intensive human intrusions insuburban soils The order of selected metals distribution wasalso found different from that of previous study Furthermorethe estimated levels of selected metals were found higher insummer than winter in suburban soils whereas in previousstudy [20] the measured levels for most of the metals werenoted to be higher in winter than summer indicating thatthese results were entirely different from the reported resultsrelated to urban soils


Table 2 Descriptive statistics of pseudototal (119879 mgkg) and bioavailable (119861 ) concentrations of selected metals in summer and winter

Variable Min Max Median Arith mean Geo mean Har mean Skew CV ()

Summer

Cd119879

035 61 37 36 31 23 minus028 47Co119879

18 44 35 32 31 30 minus020 23Cr119879

33 86 54 54 53 52 048 22Cu119879

29 421 38 51 41 38 54 138Fe119879

3993 5429 4887 4863 4851 4839 minus064 70Mn119879

212 778 392 435 404 376 041 39Pb119879

099 112 54 57 45 18 021 52Sr119879

47 1356 251 468 289 183 11 96Zn119879

70 143 96 98 96 95 069 17

Winter

Cd119879

lt001 52 16 18 12 052 075 71Co119879

18 43 30 31 30 30 034 19Cr119879

25 32 24 23 21 17 minus13 30Cu119879

17 44 27 28 27 26 059 21Fe119879

2462 4171 3921 3802 3786 3766 minus25 86Mn119879

179 561 408 393 378 361 minus046 26Pb119879

24 45 16 19 15 10 047 67Sr119879

62 739 160 225 183 157 20 80Zn119879

41 91 61 62 60 59 047 22

Summer

Cd119861

011 70 22 56 23 12 46 235Co119861

039 25 13 13 11 10 032 46Cr119861

lt001 083 026 032 020 006 051 73Cu119861

003 062 039 037 033 024 minus045 37Fe119861

lt001 017 002 003 002 001 34 118Mn119861

lt001 004 001 001 001 001 11 64Pb119861

003 65 25 74 197 038 54 330Sr119861

011 29 070 076 062 049 23 70Zn119861

005 028 013 015 014 012 047 39

Winter

Cd119861

25 79 77 25 10 64 42 205Co119861

036 67 28 26 23 18 068 49Cr119861

002 14 031 046 033 020 12 76Cu119861

001 081 026 027 017 007 074 77Fe119861

lt001 002 001 001 lt001 lt001 094 61Mn119861

lt001 004 001 001 lt001 lt001 24 88Pb119861

061 23 29 44 30 21 26 106Sr119861

029 49 11 13 11 093 25 77Zn119861

001 055 009 009 007 004 41 103

32 Bioavailability Potential bioavailability of the metalswas also evaluated in the study area in summer and winter(Table 2) The results manifested the highest bioavailabilityby Cd (011ndash70 in summer and 25ndash79 in winter) Pb(003ndash65 in summer and 061ndash23 in winter) Co (039ndash25 in summer and 036ndash67 in winter) and Sr (011ndash29 in summer and 029ndash49 in winter) while Fe (lt001ndash017 in summer and lt001ndash002 in winter) Mn (lt001ndash004 in both seasons) and Zn (005ndash028 in summer and001ndash055 in winter) were the least contributors towardspotential bioavailability of the metals to soil biota in bothseasons Consequently Pb Cd Co and Sr showed higherbioavailability while Fe Mn and Zn indicated the least Onthe arithmeticmean basis themetals followed the decreasing

bioavailable concentrations order Pb gt Cd gt Co gt Sr gt Cugt Cr gt Zn gt Fe gt Mn and Cd gt Pb gt Co gt Sr gt Cr gt Cugt Zn gt Mn gt Fe in summer and winter respectively Theresults clearly revealed that the sequences of pseudototal andbioavailable contents of the metals were different from oneanother Furthermore the leachability for Cd Co Cr and Srwas quite higher in winter while Pb and Zn indicated higherbioavailability in summer (119875 lt 005) However total metalsload of these metals was relatively higher in summer thanwinter

33 Ecological Risk Evaluation The range andmean values ofCF of selected metals in acid-extract of the soils around thereservoir in summer and winter are portrayed in Figure 2(a)


001

01

1

10C

d (S

)C

d (W

)C

o (S

)C

o (W

)Cr

(S)

Cr (W

)Cu

(S)

Cu (W

)Fe

(S)

Fe (W

)M

n (S

)M

n (W

)Pb

(S)

Pb (W

)Sr

(S)

Sr (W

)Zn

(S)

Zn (W

)

Con

tam

inat

ion

fact

or (C

F) o

f met

al

MinMeanMax

(a)

1

3

5

7

Cd

(S)

Cd

(W)

Co

(S)

Co

(W)

Cr (S

)Cr

(W)

Cu (S

)Cu

(W)

Fe (S

)Fe

(W)

Mn

(S)

Mn

(W)

Pb (S

)Pb

(W)

Sr (S

)Sr

(W)

Zn (S

)Zn

(W)minus7

minus5

minus3

minus1

Geo

accu

mul

atio

n in

dex

(Ige

o) o

f met

al

MinMeanMax

(b)

01

1

10

100

1000

Cd

(S)

Cd

(W)

Co

(S)

Co

(W)

Cr (S

)Cr

(W)

Cu (S

)Cu

(W)

Mn

(S)

Mn

(W)

Pb (S

)Pb

(W)

Sr (S

)Sr

(W)

Zn (S

)Zn

(W)

Enric

hmen

t fac

tor (

EF) o

f met

al

MinMeanMax

(c)

Figure 2 Description of contamination factor (CF) geoaccumulation index (119868geo) and enrichment factor (EF) in soil in summer (S) andwinter (W)

In summer on the average basis Co Sr and Zn exhibitedmoderate contamination Pb could cause considerable con-tamination and Cd might pose very high contaminationThe highest CF values of Cd Cu Pb Sr and Zn were 40571 80 37 and 21 respectively thus indicating that thesoils were highly contaminated with Cd Cu and Pb Srmight cause considerable contamination and Zn moderatecontamination in the soils In winter on mean scale thesoils demonstrated moderate contamination by Co and Pbwhile Cd showed very high contamination and the rest ofthe metals indicated low or no contamination of the soilsThe CF manifested that Co Sr and Zn could cause moderatecontamination Pb showed considerable contamination andCd might pose very high contamination of the soils Ironand Mn showed low contamination in the studied soils inboth seasons However the highest CF values of Mn were06 and 08 in summer and winter respectively indicating

that it might cause contamination to the soils in the futureIn comparison with the results of CF in the previous study[20] it was found that there was more extent of metalscontamination in the suburban soils than urban soils dueto intensive human intrusions in these areas Moreover theextent of metals contamination was found relatively higher insummer than winter in suburban soils whereas it was greaterin winter than summer in urban soils [20]

The assessment of the soil based on the degree of contam-ination (119862deg) was also carried out as suggested by Hakanson[29] It is considered as more appropriate parameter to assessthe overall contamination by all measured metals in the soilsand hence act as a cumulative index The lowest to highestvalues of 119862deg in summer and winter were 66ndash697 and 35ndash464 with the average values of 372 and 189 respectively Onthe average basis the soils belonged to very high degree ofcontamination class in summer while considerable degree of


Table 3 Principal component loadings of selected metals in soil in summer and winter

Summer WinterPC1 PC2 PC3 PC1 PC2 PC3 PC4

Eigen value 28 23 15 23 18 15 12 total variance 36 25 17 25 21 17 13 cumulative variance 36 61 78 25 46 63 76Cd 080 minus013 minus020 minus018 minus008 076 minus021Co 087 minus007 007 005 012 090 010Cr 084 004 019 075 020 030 019Cu minus024 017 088 035 007 014 079Fe 017 068 minus002 minus003 087 minus007 minus023Mn minus036 082 011 088 minus006 003 minus009Pb 077 minus031 002 014 000 077 009Sr 091 008 minus002 074 009 033 007Zn 031 minus012 083 minus038 008 minus019 085

contamination category in winter Overall higher contami-nation by selected metals was observed in summer comparedto the winter in the studied soil In comparison with theresults of 119862deg in urban soils in our previous study [20] itwas noted that there was more degree of contamination inthe suburban soils around the Khanpur Lake Moreover inthis study the levels of 119862deg were observed to be higher insummer than winter while in our previous study the valuesof 119862deg were noted higher in winter than summer

The contamination levels of selectedmetals were assessedusing geoaccumulation index (119868geo) Any increase in thecurrent levels is envisaged to be anthropogenic in natureFigure 2(b) describes the lowest mean and highest 119868geo valuesof selected metals in acid-extract of the soils in summer andwinter In summer mean values of 119868geo indicated that the soilswere heavily to extremely contaminated by Cd Pb showedmoderate contamination and the remaining metals exhibitedpractically no contamination of the soilsMaximum 119868geo valueof Cd might cause heavy to extreme contamination Co andZn posed no contamination to moderate contamination Srcaused moderate contamination and Pb caused moderate toheavy contamination of the soils In winter on the averagebasis Cd might pose heavy contamination while the restof the metals showed practically no contamination of thesoils The maximum values of Cd might cause heavy toextreme contamination Co and Sr could pose moderatecontamination and Pb caused heavy contamination of thesoils Overall geoaccumulation index revealed accumulationof Cd Co Pb and Sr in both seasons while Zn showedaccumulation in soils in summer only In current study itwas noted that there was more geoaccumulation of selectedmetals in suburban soils around the Khanpur Lake than inurban soils around Rawal Lake [20] Moreover in this studymore geoaccumulation was observed in summer than winterwhereas in the previous study higher geoaccumulation wasobserved in winter than summer

Enrichment factor (EF) is a comparatively simple andeasy tool to assess enrichment extent of elements in soils [33ndash35] The minimum mean and maximum EF values of theselected metals in acid-extract of the soil around the lake

in summer and winter are shown in Figure 2(c) In summeraverage EF values of Co Cr Cu Mn Sr and Zn revealed thatthe soils were significantly enriched with these metals whileCd and Pb were observed to be extremelyhighly enriched inthe soilsThe rest of themetals were not significantly enrichedin the soils The highest EF values of Sr and Zn (EF = 20ndash40)graded the soils as very highly enriched and Cd (EF gt 400)Cu (EFgt 70) and Pb (EFgt 80) classified the soils as extremelyenriched However average EF results in winter showed thatCo Cu Mn Sr and Zn were significantly enriched Cr wasmoderately enriched Pb was very highly enriched and Cdwas found to be extremely enriched in the soils The rest ofthe metals showed deficiency to minimal enrichment in thesoils The highest EF values of Cd (EF gt 450) and Pb (EF gt40) categorized the soils as extremely enriched and Co andSr (EF gt 20) indicated that the soils were highly enrichedwith these metals Overall the mean EF values of Co CuMn Sr and Zn graded the soils as significantly enrichedin both seasons Cr categorized as significantly enriched insummer and moderately enriched in winter Pb classified asextremely enriched in summer and very highly enriched inwinter and Cd graded the soils as extremely enriched inboth seasons In comparison with the results of EF in urbansoils around Rawal Lake [20] the calculated levels of EF werefound relatively higher in the suburban soils aroundKhanpurLake than in urban soils in the previous study Moreoverin current study the extent of pollution was found relativelyhigher in summer thanwinter while in our previous study thedegree of pollution was found relatively higher in winter thansummer

34 Source Apportionment PCA was applied to find outthe sources of selected metals in the studied soil In thisstudy three principal components (PCs) and four PCs witheigenvalues greater than 1 were extracted which explainedabout 78 and 76 of the total variance in the analyzeddata in summer and winter respectively Principal compo-nent loadings of selected metals in summer and winter aredescribed in Table 3 In summer PC1 (36 of total variance)showed positive loadings of Cd Co Cr Pb and Sr PC2 (25


of total variance) exhibited higher loadings of Fe andMn andPC3 (17 of total variance) had elevated loadings in favor ofCu and Zn Nevertheless in winter PC1 (25 variance) hadpositive associations of Cr Mn and Sr PC2 (21 variance)indicated positive loading of Fe PC3 (17 variance) hadhigher loadings for Cd Co and Pb and PC4 (13 variance)exhibited elevated loadings for Cu and Zn Cadmium CoCr Cu Mn Pb Sr and Zn were likely to be contributed byanthropogenic intrusions such as agricultural and industrialactivities discharge of untreated domestic wastes sewagesludge road runoff and atmospheric deposition [1 37ndash40]ThoughFe showed close associationwithMn in summer eventhen it was supposed to be contributed mainly by geogenicinputs as it was not highlighted in ecological risk assessmentin both seasons

4 Conclusions

The present study showed divergent disparity of selectedmetals in surface soil around freshwater Khanpur LakePakistan in summer and winter On the arithmetic meanbasis Fe Sr Mn and Zn were the dominant metals whileCd Pb Co and Cr were in lower concentrations in acid-extract However Cd Co Sr and Pbwere easily leachable andbioavailable to soil biota in the study area In ecological riskassessment contamination factor demonstrated moderatecontamination by Co Sr and Zn and high contaminationby Cd Cu and Pb geoaccumulation index indicated heavyto extreme contamination by Cd and heavy contaminationby Pb enrichment factor revealed significant enrichment byCo Cr Cu Mn Sr and Zn and extreme enrichment by Cdand Pb Principal component analysis evidenced significantanthropogenic intrusions of Cd Cr Co Cu Mn Pb Srand Zn in the soil Overall considerablehigh degree ofcontamination was found in the soil

Conflict of Interests

The authors do not have any conflict of interests

Acknowledgments

The authors are grateful to the Administration of KhanpurLake Islamabad Pakistan for their help during samplecollection Technical and financial help by Quaid-i-AzamUniversity Islamabad Pakistan to execute this project is alsoacknowledged

References

[1] G-L Yuan T-H Sun P Han J Li and X-X Lang ldquoSourceidentification and ecological risk assessment of heavy metalsin topsoil using environmental geochemical mapping typicalurban renewal area in Beijing Chinardquo Journal of GeochemicalExploration vol 136 pp 40ndash47 2014

[2] X Chen X Xia Y Zhao and P Zhang ldquoHeavy metal concen-trations in roadside soils and correlation with urban traffic inBeijing Chinardquo Journal of Hazardous Materials vol 181 no 1ndash3 pp 640ndash646 2010

[3] D S Manta M Angelone A Bellanca R Neri and MSprovieri ldquoHeavy metals in urban soils a case study from thecity of Palermo (Sicily) Italyrdquo Science of the Total Environmentvol 300 no 1ndash3 pp 229ndash243 2002

[4] Y B Sun Q X Zhou X K Xie and R Liu ldquoSpatial sourcesand risk assessment of heavymetal contamination of urban soilsin typical regions of Shenyang Chinardquo Journal of HazardousMaterials vol 174 no 1ndash3 pp 455ndash462 2010

[5] G M Pierzynsky J T Sims and G F Vance Soils andEnvironmental Quality CRC Press Taylor amp Francis GroupNew York NY USA 2005

[6] L Poggio B Vrscaj R Schulin E Hepperle and F A MarsanldquoMetals pollution and human bioaccessibility of topsoils inGrugliasco (Italy)rdquo Environmental Pollution vol 157 no 2 pp680ndash689 2009

[7] C S C Wong X Li and I Thornton ldquoUrban environmentalgeochemistry of tracemetalsrdquo Environmental Pollution vol 142no 1 pp 1ndash16 2006

[8] Y Li X Gou G Wang Q Zhang Q Su and G XiaoldquoHeavymetal contamination and source in arid agricultural soilin central Gansu Province Chinardquo Journal of EnvironmentalSciences vol 20 no 5 pp 607ndash612 2008

[9] D Montagne S Cornu H N Bourennane D Baize C Ratieand D King ldquoEffect of agricultural practices on trace-elementdistribution in soilrdquo Communications in Soil Science and PlantAnalysis vol 38 no 3-4 pp 473ndash491 2007

[10] N Sezgin H K Ozcan G Demir S Nemlioglu and C BayatldquoDetermination of heavymetal concentrations in street dusts inIstanbul E-5 highwayrdquo Environment International vol 29 no 7pp 979ndash985 2004

[11] Y-J Cui Y-G Zhu R-H Zhai et al ldquoTransfer of metals fromsoil to vegetables in an area near a smelter in Nanning ChinardquoEnvironment International vol 30 no 6 pp 785ndash791 2004

[12] X Y Zhang F F Lin Y G Jiang K Wang and X L FengldquoVariability of total and available copper concentrations inrelation to land use and soil properties in Yangtze River Delta ofChinardquo Environmental Monitoring and Assessment vol 155 no1ndash4 pp 205ndash213 2009

[13] X-L Zhong S-L Zhou Q Zhu and Q-G Zhao ldquoFractiondistribution and bioavailability of soil heavy metals in theYangtze River Deltamdasha case study of Kunshan City in JiangsuProvince Chinardquo Journal of Hazardous Materials vol 198 pp13ndash21 2011

[14] M J McLaughlin R E Hamon R G McLaren T W Speirand S L Rogers ldquoReview a bioavailability-based rationale forcontrolling metal and metalloid contamination of agriculturalland in Australia and New Zealandrdquo Australian Journal of SoilResearch vol 38 no 6 pp 1037ndash1086 2000

[15] L Rodrıguez E Ruiz J Alonso-Azcarate and J Rincon ldquoHeavymetal distribution and chemical speciation in tailings and soilsaround a Pb-Zn mine in Spainrdquo Journal of EnvironmentalManagement vol 90 no 2 pp 1106ndash1116 2009

[16] Y-J An and D H Kampbell ldquoTotal dissolved and bioavailablemetals at Lake Texoma marinasrdquo Environmental Pollution vol122 no 2 pp 253ndash259 2003

[17] A L Nolan E Lombi and M J McLaughlin ldquoMetal bioaccu-mulation and toxicity in soilsmdashwhy bother with speciationrdquoAustralian Journal of Chemistry vol 56 no 2-3 pp 77ndash91 2003

[18] E Meers G Du Laing V Unamuno et al ldquoComparison ofcadmium extractability from soils by commonly used singleextraction protocolsrdquo Geoderma vol 141 no 3-4 pp 247ndash2592007


[19] X-S Luo J Ding B Xu Y-J Wang H-B Li and S YuldquoIncorporating bioaccessibility into human health risk assess-ments of heavy metals in urban park soilsrdquo Science of the TotalEnvironment vol 424 pp 88ndash96 2012

[20] J Iqbal and M H Shah ldquoDistribution correlation and riskassessment of selected metals in urban soils from IslamabadPakistanrdquo Journal of Hazardous Materials vol 192 no 2 pp887ndash898 2011

[21] USEPA Microwave Assisted Acid Digestion of SedimentsSludges Soils and Oils Method 3051A Office of Solid Wasteand Emergency Response US Government Printing OfficeWashington DC USA 2007

[22] G Shi Z Chen C Bi et al ldquoComprehensive assessment oftoxic metals in urban and suburban street deposited sediments(SDSs) in the biggest metropolitan area of Chinardquo Environmen-tal Pollution vol 158 no 3 pp 694ndash703 2010

[23] M Radojevic and V N Bashkin Practical EnvironmentalAnalysis The Royal Society of Chemistry London UK 1999

[24] S M Rodrigues B Henriques J Coimbra E Ferreira da SilvaM E Pereira and A C Duarte ldquoWater-soluble fraction ofmercury arsenic and other potentially toxic elements in highlycontaminated sediments and soilsrdquoChemosphere vol 78 no 11pp 1301ndash1312 2010

[25] StatSoft Inc STATISTICA for Windows Computer ProgrammeManual StatSoft Inc Tulsa Okla USA 1999

[26] J A Acosta A Faz and S Martinez-Martinez ldquoIdentificationof heavy metal sources by multivariable analysis in a typicalMediterranean city (SE Spain)rdquo Environmental Monitoring andAssessment vol 169 no 1ndash4 pp 519ndash530 2010

[27] S R Tariq M H Shah N Shaheen M Jaffar and A KhaliqueldquoStatistical source identification of metals in groundwaterexposed to industrial contaminationrdquo Environmental Monitor-ing and Assessment vol 138 no 1ndash3 pp 159ndash165 2008

[28] S R Tariq N Shaheen A Khalique and M H Shah ldquoDis-tribution correlation and source apportionment of selectedmetals in tannery effluents related soils and groundwatermdashacase study from Multan Pakistanrdquo Environmental Monitoringand Assessment vol 166 no 1ndash4 pp 303ndash312 2010

[29] L Hakanson ldquoAn ecological risk index for aquatic pollutioncontrol A sedimentological approachrdquoWater Research vol 14no 8 pp 975ndash1001 1980

[30] D R LideCRCHandbook of Chemistry and Physics GeophysicsAstronomy and Acoustics Abundance of Elements in the EarthsCrust and in the Sea Section 14 CRC Press Boca Raton FlaUSA 85th edition 2005

[31] K Loska D Wiechulła and I Korus ldquoMetal contamination offarming soils affected by industryrdquo Environment Internationalvol 30 no 2 pp 159ndash165 2004

[32] GMuller ldquoIndex of geoaccumulation in sediments of the RhineRiverrdquo GeoJournal vol 2 pp 108ndash118 1969

[33] C Reimann and P de Caritat ldquoDistinguishing between naturaland anthropogenic sources for elements in the environmentregional geochemical surveys versus enrichment factorsrdquo Sci-ence of the Total Environment vol 337 no 1ndash3 pp 91ndash107 2005

[34] S Dantu ldquoHeavy metals concentration in soils of southeasternpart of Ranga Reddy district Andhra Pradesh Indiardquo Environ-mentalMonitoring andAssessment vol 149 no 1ndash4 pp 213ndash2222009

[35] F A Vega E F Covelo B Cerqueira and M L AndradeldquoEnrichment of marsh soils with heavy metals by effect ofanthropic pollutionrdquo Journal of Hazardous Materials vol 170no 2-3 pp 1056ndash1063 2009

[36] R A Sutherland ldquoBed sediment-associated trace metals in anurban stream Oahu Hawaiirdquo Environmental Geology vol 39no 6 pp 611ndash627 2000

[37] T-B Chen Y-M Zheng M Lei et al ldquoAssessment of heavymetal pollution in surface soils of urban parks in BeijingChinardquo Chemosphere vol 60 no 4 pp 542ndash551 2005

[38] C Mico L Recatala M Peris and J Sanchez ldquoAssessing heavymetal sources in agricultural soils of an European Mediter-ranean area by multivariate analysisrdquo Chemosphere vol 65 no5 pp 863ndash872 2006

[39] L Zhao Y Xu H Hou Y Shangguan and F Li ldquoSourceidentification andhealth risk assessment ofmetals in urban soilsaround the Tanggu chemical industrial district Tianjin ChinardquoScience of the Total Environment vol 468-469 pp 654ndash6622014

[40] S Charlesworth M Everett R McCarthy A Ordonez and Ede Miguel ldquoA comparative study of heavy metal concentrationand distribution in deposited street dusts in a large and a smallurban area Birmingham and Coventry West Midlands UKrdquoEnvironment International vol 29 no 5 pp 563ndash573 2003

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


Figure 1 Locations map of the study area

2 Materials and Methods

21 Site Description In present study soil samples werecollected around Khanpur Lake (72∘561015840 E 33∘481015840N) which islocated onHaroRiver near the town of Khanpur about 40 kmnorthwest of Islamabad Pakistan (Figure 1) It supplies drink-ing water to Islamabad and Rawalpindi and irrigation waterto the surrounding agricultural areas It was constructed in1983 with the storage capacity of 140 million m3 Its averagewater depth is about 15mThe gross storage of the reservoir is0132 km3 with a total catchment area of 798 km2The surfacearea of the reservoir varies from a maximum of 1806 ha toa minimum of 215 ha The surrounding area of the lake isplanted with flowering trees and set with gardens picnicpoints and isolated paths The water stored in Khanpur Lakeis fed bymelting snow seasonal rains and the natural springsof Margalla Hills Pakistan

22 Sampling Processing and Chemical Analysis A total of80 composite surface (1ndash10 cm top layer) soil samples (eachcontaining 5ndash10 subsamples) were collected from residentialand picnic areas around the lake in summer (June 2012)andwinter (January 2013) in precleaned zip-locked polythenebags using a plastic scoop To determine pseudototal metalcontents the soil sampleswere ovendried grounded homog-enized sieved through a 2mm plastic sieve to remove stonesgravels and coarse particles and then stored in zip-lockedpolythene bags before chemical analysis [6 20]

To find out the pseudototal metal concentrations the soilsample (1-2 g dryweight) was digested using freshly preparedacid mixture of HNO

3and HCl (3 1 vv) in a microwave

system [21] Each digested sample was then filtered throughfine filter paper (045 120583m pore size) and then diluted with1 HNO

3[22] A reagent blank was also prepared having the

same amount of acids without the sample with each batchA selective single step extraction procedure using 01M

Ca(NO3)2 was performed at room temperature to determine

the bioavailable metal contents [16] An aliquot of 50 g ofair dried soil sample was added to 50mL solution of 01MCa(NO

3)2and the extraction was performed in precleaned

glass vessel by shaking on an autoshaker 240 vibrationsper minute for 16 h A reagent blank was also prepared withthe same amount of 01M Ca(NO

3)2solution without soil

sample Solid residuewas separated from the extracts throughfiltration using fine filter papers [16 23 24] The extractionswere carried out in triplicate for each sample

Table 1 Metal concentrations (mgkg) and recoveries () instandard reference material (SRM-2711)

MetalCertified

concentration(mgkg)

Measuredconcentration

(mgkg)

Recovery()

Cd 417 4098 98Co 10 97 97Cr 47 4756 101Cu 114 1123 99Fe 28900 27601 96Mn 638 642 101Pb 1162 1180 102Sr 2453 2417 99Zn 3504 341 97

The concentrations of Cd Co Cr Cu Fe Mn Pb Sr andZn inCa(NO

3)2and acid-extracts weremeasured using flame

atomic absorption spectrophotometer (Shimadzu AA-670Japan) under optimum analytical conditions Selected metalsconcentrations were estimated by following calibration linemethod and dilutions were done duly whenever needed [2023]

23 Quality Control and Quality Assurance Analytical gradechemicals were used throughout the study All the reagentsand calibration standards were prepared using deionizedwater The preparation of calibration metal standards fromstock solutions of 1000mgL was carried out by succeedingdilutions with deionizedwater All glassware usedwas soakedovernight in HNO

3solution (10 vv) and then rinsed

thoroughly with several portions of distilled water priorto use [22] The reagent blanks were prepared throughoutchemical analysis and were used to correct the analyticalresults Reproducibility of the results was also ensured fol-lowing analysis sequence of calibration of standards andblind standard solution analysis as unknown (quality controlsolutions) Standard reference material (SRM 2711) was alsoanalyzed as part of the quality assurance and quality control(QAQC) procedure and good agreement was observedbetween the data got from present study and the certifiedvalues (Table 1) Some soil samples were also analyzed at anindependent laboratory for cross comparison and a maxi-mum of plusmn25 difference was observed in the two results Allthe measurements were made in triplicate

24 Statistical Analysis The analyzed data were summarizedusing basic statistical parameters such as minimum maxi-mum median arithmetic mean geometric mean harmonicmean skewness and coefficients of variation STATISTICAsoftware was used for multivariate statistical analysis suchas principal component analysis (PCA) of the obtained data[25] PCA was applied both to discriminate between variousgeogenic inputs that cause variations in soil compositionand to find out pollution sources affecting the metal levelsof soil [20 26ndash28] It was employed to investigate theassociations among selected metals and their grouping into




CF =119862119899

119862119887

(1)

where 119862119899and 119862



119862deg =119894=119899

sum

119894=1CF (2)



119868geo = log2 (119862119899

15119861119899

) (3)




119899designates




EF =(119862119909119862ref)Sample

(119862119909119862ref)Crust

(4)









Summer

Cd119879

035 61 37 36 31 23 minus028 47Co119879

18 44 35 32 31 30 minus020 23Cr119879

33 86 54 54 53 52 048 22Cu119879

29 421 38 51 41 38 54 138Fe119879

3993 5429 4887 4863 4851 4839 minus064 70Mn119879

212 778 392 435 404 376 041 39Pb119879

099 112 54 57 45 18 021 52Sr119879

47 1356 251 468 289 183 11 96Zn119879

70 143 96 98 96 95 069 17

Winter

Cd119879

lt001 52 16 18 12 052 075 71Co119879

18 43 30 31 30 30 034 19Cr119879

25 32 24 23 21 17 minus13 30Cu119879

17 44 27 28 27 26 059 21Fe119879

2462 4171 3921 3802 3786 3766 minus25 86Mn119879

179 561 408 393 378 361 minus046 26Pb119879

24 45 16 19 15 10 047 67Sr119879

62 739 160 225 183 157 20 80Zn119879

41 91 61 62 60 59 047 22

Summer

Cd119861

011 70 22 56 23 12 46 235Co119861

039 25 13 13 11 10 032 46Cr119861

lt001 083 026 032 020 006 051 73Cu119861

003 062 039 037 033 024 minus045 37Fe119861

lt001 017 002 003 002 001 34 118Mn119861

lt001 004 001 001 001 001 11 64Pb119861

003 65 25 74 197 038 54 330Sr119861

011 29 070 076 062 049 23 70Zn119861

005 028 013 015 014 012 047 39

Winter

Cd119861

25 79 77 25 10 64 42 205Co119861

036 67 28 26 23 18 068 49Cr119861

002 14 031 046 033 020 12 76Cu119861

001 081 026 027 017 007 074 77Fe119861

lt001 002 001 001 lt001 lt001 094 61Mn119861

lt001 004 001 001 lt001 lt001 24 88Pb119861

061 23 29 44 30 21 26 106Sr119861

029 49 11 13 11 093 25 77Zn119861

001 055 009 009 007 004 41 103





001

01

1

10C

d (S

)C

d (W

)C

o (S

)C

o (W

)Cr

(S)

Cr (W

)Cu

(S)

Cu (W

)Fe

(S)

Fe (W

)M

n (S

)M

n (W

)Pb

(S)

Pb (W

)Sr

(S)

Sr (W

)Zn

(S)

Zn (W

)

Con

tam

inat

ion

fact

or (C

F) o

f met

al

MinMeanMax

(a)

1

3

5

7

Cd

(S)

Cd

(W)

Co

(S)

Co

(W)

Cr (S

)Cr

(W)

Cu (S

)Cu

(W)

Fe (S

)Fe

(W)

Mn

(S)

Mn

(W)

Pb (S

)Pb

(W)

Sr (S

)Sr

(W)

Zn (S

)Zn

(W)minus7

minus5

minus3

minus1

Geo

accu

mul

atio

n in

dex

(Ige

o) o

f met

al

MinMeanMax

(b)

01

1

10

100

1000

Cd

(S)

Cd

(W)

Co

(S)

Co

(W)

Cr (S

)Cr

(W)

Cu (S

)Cu

(W)

Mn

(S)

Mn

(W)

Pb (S

)Pb

(W)

Sr (S

)Sr

(W)

Zn (S

)Zn

(W)

Enric

hmen

t fac

tor (

EF) o

f met

al

MinMeanMax

(c)
















4 Conclusions




Acknowledgments


References



















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




CF =119862119899

119862119887

(1)

where 119862119899and 119862



119862deg =119894=119899

sum

119894=1CF (2)



119868geo = log2 (119862119899

15119861119899

) (3)




119899designates




EF =(119862119909119862ref)Sample

(119862119909119862ref)Crust

(4)









Summer

Cd119879

035 61 37 36 31 23 minus028 47Co119879

18 44 35 32 31 30 minus020 23Cr119879

33 86 54 54 53 52 048 22Cu119879

29 421 38 51 41 38 54 138Fe119879

3993 5429 4887 4863 4851 4839 minus064 70Mn119879

212 778 392 435 404 376 041 39Pb119879

099 112 54 57 45 18 021 52Sr119879

47 1356 251 468 289 183 11 96Zn119879

70 143 96 98 96 95 069 17

Winter

Cd119879

lt001 52 16 18 12 052 075 71Co119879

18 43 30 31 30 30 034 19Cr119879

25 32 24 23 21 17 minus13 30Cu119879

17 44 27 28 27 26 059 21Fe119879

2462 4171 3921 3802 3786 3766 minus25 86Mn119879

179 561 408 393 378 361 minus046 26Pb119879

24 45 16 19 15 10 047 67Sr119879

62 739 160 225 183 157 20 80Zn119879

41 91 61 62 60 59 047 22

Summer

Cd119861

011 70 22 56 23 12 46 235Co119861

039 25 13 13 11 10 032 46Cr119861

lt001 083 026 032 020 006 051 73Cu119861

003 062 039 037 033 024 minus045 37Fe119861

lt001 017 002 003 002 001 34 118Mn119861

lt001 004 001 001 001 001 11 64Pb119861

003 65 25 74 197 038 54 330Sr119861

011 29 070 076 062 049 23 70Zn119861

005 028 013 015 014 012 047 39

Winter

Cd119861

25 79 77 25 10 64 42 205Co119861

036 67 28 26 23 18 068 49Cr119861

002 14 031 046 033 020 12 76Cu119861

001 081 026 027 017 007 074 77Fe119861

lt001 002 001 001 lt001 lt001 094 61Mn119861

lt001 004 001 001 lt001 lt001 24 88Pb119861

061 23 29 44 30 21 26 106Sr119861

029 49 11 13 11 093 25 77Zn119861

001 055 009 009 007 004 41 103





001

01

1

10C

d (S

)C

d (W

)C

o (S

)C

o (W

)Cr

(S)

Cr (W

)Cu

(S)

Cu (W

)Fe

(S)

Fe (W

)M

n (S

)M

n (W

)Pb

(S)

Pb (W

)Sr

(S)

Sr (W

)Zn

(S)

Zn (W

)

Con

tam

inat

ion

fact

or (C

F) o

f met

al

MinMeanMax

(a)

1

3

5

7

Cd

(S)

Cd

(W)

Co

(S)

Co

(W)

Cr (S

)Cr

(W)

Cu (S

)Cu

(W)

Fe (S

)Fe

(W)

Mn

(S)

Mn

(W)

Pb (S

)Pb

(W)

Sr (S

)Sr

(W)

Zn (S

)Zn

(W)minus7

minus5

minus3

minus1

Geo

accu

mul

atio

n in

dex

(Ige

o) o

f met

al

MinMeanMax

(b)

01

1

10

100

1000

Cd

(S)

Cd

(W)

Co

(S)

Co

(W)

Cr (S

)Cr

(W)

Cu (S

)Cu

(W)

Mn

(S)

Mn

(W)

Pb (S

)Pb

(W)

Sr (S

)Sr

(W)

Zn (S

)Zn

(W)

Enric

hmen

t fac

tor (

EF) o

f met

al

MinMeanMax

(c)
















4 Conclusions




Acknowledgments


References



















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




Summer

Cd119879

035 61 37 36 31 23 minus028 47Co119879

18 44 35 32 31 30 minus020 23Cr119879

33 86 54 54 53 52 048 22Cu119879

29 421 38 51 41 38 54 138Fe119879

3993 5429 4887 4863 4851 4839 minus064 70Mn119879

212 778 392 435 404 376 041 39Pb119879

099 112 54 57 45 18 021 52Sr119879

47 1356 251 468 289 183 11 96Zn119879

70 143 96 98 96 95 069 17

Winter

Cd119879

lt001 52 16 18 12 052 075 71Co119879

18 43 30 31 30 30 034 19Cr119879

25 32 24 23 21 17 minus13 30Cu119879

17 44 27 28 27 26 059 21Fe119879

2462 4171 3921 3802 3786 3766 minus25 86Mn119879

179 561 408 393 378 361 minus046 26Pb119879

24 45 16 19 15 10 047 67Sr119879

62 739 160 225 183 157 20 80Zn119879

41 91 61 62 60 59 047 22

Summer

Cd119861

011 70 22 56 23 12 46 235Co119861

039 25 13 13 11 10 032 46Cr119861

lt001 083 026 032 020 006 051 73Cu119861

003 062 039 037 033 024 minus045 37Fe119861

lt001 017 002 003 002 001 34 118Mn119861

lt001 004 001 001 001 001 11 64Pb119861

003 65 25 74 197 038 54 330Sr119861

011 29 070 076 062 049 23 70Zn119861

005 028 013 015 014 012 047 39

Winter

Cd119861

25 79 77 25 10 64 42 205Co119861

036 67 28 26 23 18 068 49Cr119861

002 14 031 046 033 020 12 76Cu119861

001 081 026 027 017 007 074 77Fe119861

lt001 002 001 001 lt001 lt001 094 61Mn119861

lt001 004 001 001 lt001 lt001 24 88Pb119861

061 23 29 44 30 21 26 106Sr119861

029 49 11 13 11 093 25 77Zn119861

001 055 009 009 007 004 41 103





001

01

1

10C

d (S

)C

d (W

)C

o (S

)C

o (W

)Cr

(S)

Cr (W

)Cu

(S)

Cu (W

)Fe

(S)

Fe (W

)M

n (S

)M

n (W

)Pb

(S)

Pb (W

)Sr

(S)

Sr (W

)Zn

(S)

Zn (W

)

Con

tam

inat

ion

fact

or (C

F) o

f met

al

MinMeanMax

(a)

1

3

5

7

Cd

(S)

Cd

(W)

Co

(S)

Co

(W)

Cr (S

)Cr

(W)

Cu (S

)Cu

(W)

Fe (S

)Fe

(W)

Mn

(S)

Mn

(W)

Pb (S

)Pb

(W)

Sr (S

)Sr

(W)

Zn (S

)Zn

(W)minus7

minus5

minus3

minus1

Geo

accu

mul

atio

n in

dex

(Ige

o) o

f met

al

MinMeanMax

(b)

01

1

10

100

1000

Cd

(S)

Cd

(W)

Co

(S)

Co

(W)

Cr (S

)Cr

(W)

Cu (S

)Cu

(W)

Mn

(S)

Mn

(W)

Pb (S

)Pb

(W)

Sr (S

)Sr

(W)

Zn (S

)Zn

(W)

Enric

hmen

t fac

tor (

EF) o

f met

al

MinMeanMax

(c)
















4 Conclusions




Acknowledgments


References



















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


001

01

1

10C

d (S

)C

d (W

)C

o (S

)C

o (W

)Cr

(S)

Cr (W

)Cu

(S)

Cu (W

)Fe

(S)

Fe (W

)M

n (S

)M

n (W

)Pb

(S)

Pb (W

)Sr

(S)

Sr (W

)Zn

(S)

Zn (W

)

Con

tam

inat

ion

fact

or (C

F) o

f met

al

MinMeanMax

(a)

1

3

5

7

Cd

(S)

Cd

(W)

Co

(S)

Co

(W)

Cr (S

)Cr

(W)

Cu (S

)Cu

(W)

Fe (S

)Fe

(W)

Mn

(S)

Mn

(W)

Pb (S

)Pb

(W)

Sr (S

)Sr

(W)

Zn (S

)Zn

(W)minus7

minus5

minus3

minus1

Geo

accu

mul

atio

n in

dex

(Ige

o) o

f met

al

MinMeanMax

(b)

01

1

10

100

1000

Cd

(S)

Cd

(W)

Co

(S)

Co

(W)

Cr (S

)Cr

(W)

Cu (S

)Cu

(W)

Mn

(S)

Mn

(W)

Pb (S

)Pb

(W)

Sr (S

)Sr

(W)

Zn (S

)Zn

(W)

Enric

hmen

t fac

tor (

EF) o

f met

al

MinMeanMax

(c)
















4 Conclusions




Acknowledgments


References



















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of












4 Conclusions




Acknowledgments


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

research article study of selected metals distribution, source...

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