Research ArticleDistribution of Heavy Metals in the Soils Associated withthe Commonly Used Pesticides in Cotton Fields

Saadia Rashid Tariq1 Musharaf Shafiq1 and Ghayoor Abbas Chotana2

1Department of Chemistry Lahore College for Women University Lahore 54000 Pakistan2Department of Chemistry Syed Babar Ali School of Science amp Engineering LUMS Lahore 54792 Pakistan

Correspondence should be addressed to Saadia Rashid Tariq saadiarashid74gmailcom

Received 3 December 2015 Revised 10 February 2016 Accepted 11 February 2016

Academic Editor Zeng-Yei Hseu

Copyright copy 2016 Saadia Rashid Tariq et al 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

Agricultural soils contain both heavy metals and pesticides originating from various agricultural practices It is quite important tostudy the relationships between these two classes of compounds To accomplish this 52 soil samples were collected from cottonfields and analyzed for theirmetal contents (Ni Cu Co Pb Cr andCd) and levels ofmost commonly used pesticides (imidaclopridacetamiprid and emamectin) FAASwas used formetal estimation and the pesticides were determined byHPLC equippedwithUVdetector The results of the study revealed slightly enhanced levels of Ni and Cd in these samples while the rest of the metals werepresent within tolerable range Acetamiprid residues in soil were strongly positively correlated with Cu and negatively correlatedwith Cr Similarly imidacloprid in soil was negatively correlated with NiThus it was evidenced that Cu stabilizes acetamiprid whileCr and Ni facilitate the degradation of acetamiprid and imidacloprid in the soil

1 Introduction

Pesticides and heavymetals are the most hazardous contami-nants of agricultural soils In fact the agricultural sustainabil-ity has long been associated with the use of a broad spectrumof pesticides that control the disease causing pests and cropdestroying insects [1] According to an estimate in Pakistanalone about 20379 metric tons of pesticides is used annuallywith about 75 of these being used only for cotton crops[2] That is why cotton fields have been found to be morecontaminated than other modes of land use [3] A significantportion of these pesticides (about 19) find their way intothe soil through spray drifts or as wash-off from treatedfoliage [4] From the soil these pesticide residues may getdirectly vaporized along with the evaporating soil moistureor are leaked into the ground and surface waters throughleaching or run-off [5ndash8] The situation is more aggravatedif a mixture of pesticides is present in the soil because theyrender the remediation process to be more difficult [9]The pesticides cause various diseases among the exposedindividuals such as cancers of various types and impairmentof kidneys and thyroid glands [10]Moreover these pesticides

have also proved to be detrimental to nontarget beneficialsoil microorganisms That is why the determination of levelsof pesticides in soil groundwater and crops has always beenthe subject of interest [11ndash14]

Pesticide degradation is an important phenomenon thathelps in remediating the contaminated soils andwater bodiesIt is shown to be assisted by a number of factors such asmoisture content of soil soil texture and soil mineral con-tents [9] The presence of metals in the soil has also recentlybeen shown to affect the degradation of pesticides [15]Thesemetals either are added to the soil along with pesticidesor originate from the long-term application of wastewaterand animal manures to agricultural soils [16 17] In factmetals affect the pesticide degradation by catalyzing thephotolysishydrolysis of pesticides or influencing the activityof microorganisms [18] Similarly complexation interactionsbetween pesticides and metals may lead to a decrease in therate of degradation of pesticides [19]

Tian et al studied the influence of bimetallic NiFenanoparticles on the degradation of DDT in aqueous solu-tions at room temperature [20] Liu et al observed thatcoexisting Cu ions in the soil influence the degradation

Hindawi Publishing CorporationScientificaVolume 2016 Article ID 7575239 11 pageshttpdxdoiorg10115520167575239

2 Scientifica

of cypermethrin and cyhalothrin by affecting the activityof microorganisms [21] Complexation interactions betweenimazapyr pesticide andmetal ions were found to decrease theimazapyr photolysis [22] It has also been found that selectedmetal ions having paramagnetic property could inhibit theaquatic photodegradation of some pesticides with humicacids [23]

The present study focuses on tracing the correlationpatterns among the levels of coexistent metals and pesticidesin the soil The correlation model thus developed betweenpesticide and heavy metals will be useful for monitoring thepesticides in soil due to the measurement of heavy metalsbeing more available So the study may provide the basisfor the management of soils contaminated with pesticidessubsequent to successful monitoring

2 Materials and Methods

21 Quality Control and Quality Assurance High qualityPyrex glassware was used during the present study which wasthoroughly cleanedwith chromicmixture 5detergent solu-tion and finally distilled water All the volumetric apparatusemployed formeasurements sample processing and dilutionwas calibrated before use In order to deliver the small volume(ie lt10mL) of stock standard solutions pipettes of 100mLcapacity were used

Double distilled water was used for the preparation ofblanks standards and reagents Analytical grade reagentswith a 9999 certified purity were procured from E-Merck(Germany) and used for quantification The stock standardsolutions of selected metals (1000mgL) as provided byE-Merck (Germany) were utilized for the preparation ofworking standards after appropriate dilution with DDWThe inconsistencies in measurement likely to arise from theuse of highly concentrated stock solutions were avoided bythe use of an intermediate working standard of 100mgLconcentration HPLC grade chemicals provided by E-MerckGermany were used for the extraction of pesticides samplecleanup and mobile phase formation The analytical stan-dards of three pesticides were obtained from Riedel-deHaen(Germany)The chances of any photodegradation of reagentswere avoided by storing them in the dark

The levels of selected trace metals that is Co Pb Cr NiCu and Cd were determined by using HITACHI AAS Z-5000 spectrophotometer The calibration curve method wasused to quantify the results At least six standards were runcovering the absorption range of samples The precision ofquantitative results was ensured by analyzing the triplicatesamples

The residues of three selected pesticides that is imidaclo-prid emamectin and acetamiprid were determined by usingthe HPLC System of Waters 1500 The detector used for thepresent investigation wasWaters-2487 a dual wavelength ab-sorbance detector designed especially forHPLC applications

The extracted and cleaned pesticide residue samples wereinjected into the chromatographic system equipped with C-8 column at a rate of 1mLmin The eluent used was a 3 2mixture of water and acetonitrile At the retention timesof 493 minutes the signals for imidacloprid emamectin

and acetamiprid were recorded by UV detector at specifiedwavelengths of 270 nm 245 nm and 254 nm respectively

22 Sampling For the present investigation a total of 52 topsoil (1ndash15 cm) samples were collected from ten different fieldsof Pakpattan Pakistan A 300 g portion of each of the soilsamples was taken in zipmouthed polyethylene bags with thehelp of soil auger These samples were properly labeled andimmediately transferred to lab where they were stored at 4∘Cuntil analysis The electrical conductivity and pH of the sam-ples were determined by immersion probe technique whilemoisture content chloride nitrate and sulphate were deter-mined by appropriate standard methods [24] All sampleswere treated and analyzed at the laboratory of Department ofChemistry Lahore College forWomen University Lahore Inorder to get the reference data the background soil sampleswere collected from remotely located agricultural soil withsandy loam texture where no pesticides were used previouslyThese background soil samples were also processed quitesimilar to the samples from the fields

23 Description of Study Area The district Pakpattan is oneof the major cotton growing areas in Pakistan It coversan area of about 3084 km2 with a population density of417 persons per sqkm A highly fertile land and a climatethat is most suitable for sustaining the crops are the mainfeatures of the area The city is bounded by river Satluj andBias that constitute the main source for irrigation Therefore88 of the area is comprised of cultivated land Soil texturehere varies from silt loam to clay loam and average annualrainfall is 200ndash300mm The temperature ranges from 66∘Cinwinter to 417∘Cduring the summerThemain crops grownhere include wheat rice cotton maize (corn) and sugarcane In addition about 507 agriculture based industrialunits are present in the district that include fertilizer cottonpressing and ginning oil mills flour mills rice mills poultryfeed textile weaving and sugar mills The exports from thearea consist principally of cotton wheat and oilseeds Toaccomplish the present study a total of fifty-two sampleswere obtained from cotton growing areas of Pakpattan Thesampling sites location is shown in Figure 1

24 Determination of Physicochemical Parameters The col-lected soil samples were ground homogenized and sub-sequently sieved through a brass sieve with pore size of850 120583m in accordance with international standards for soilanalysis [24] The water extract of soil samples was preparedby stirring a 1 10 soil-water mixture for five minutes andallowing equilibration for thirty minutes The filtrate thusobtained was used for the determination of physicochemicalparameters such as chlorides and nitrates sulphates [25] Inorder to determine the soil bulk density undisturbed cores ofdimensions 005 times 0072mwere drawn from 5 to 10 cm depthof soil [26]

The pH of all the soil samples was determined by using aInolab-720 portable pH meter precalibrated by using stan-dard buffer solutions of pH 40 70 and 90The conductivityof water extract of soil samples was determined by usingWTW Inolab-720 conductivity meter

Scientifica 3

Chak 40

NA-166 Chak-149

Arifwala Chak-9

Chack Shan Karam

Baghu

Chak-97

Chak-67

River Sutlej

lowastlowastlowast

lowastlowast

Figure 1 Location map of sampling siteslowast

The chloride contents of the soil samples were deter-mined gravimetrically by using AgNO

3as precipitant [27]

In order to determine the sulphate ions a 100mL portionof water extract of soil samples was stirred for five minuteswith HCl and glycerol solutions along with approximately003 g of BaCl

2 Immediately after stirring the solution was

poured into a quartz cell with an optical path of 10 cmand the absorbance was measured at 420 nm on a UVspectrophotometer A series of calibration standards betweenconcentrations of 05 and 5mg SO

4

2minusL were prepared andused for drawing calibration curve [24]

Nitrate present in the soil samples was determined byusing the sodium salicylatemethod Here 100mL portions ofwater extract of each of the soil samples were evaporated with10mL of sodium salicylate and cooled to room temperatureSubsequently 10mL of concentrated H

2SO4was added to

dehumidify the entire residue and allowed to stand for 10minutes It was then quantitatively transferred to a 50mLvolumetric flask added with 70mL of NaOH and adjustedthe volume to 50mL with distilled water After 10 minutesthe absorbance was measured at 410 nm against the blankprepared in the same way Calibration curve was constructedby using the standard KNO

3solutions in the concentra-

tion range of 2ndash20mgL [28] The organic carbon contentsof the soil samples were determined by partial oxidationmethod that involved the titration of soil samples against1N (NH

4)2Fe(SO

4)2sdot6H2O solution by using diphenylamine

indicator [29]

Pesticide Analysis by HPLC The residues of selected pes-ticides that is imidacloprid acetamiprid and emamectinwere extracted from soil samples by using methanol as

solvent The extraction procedure adopted involved theshaking of the appropriate amount of soil samples with100mL of methanol on an orbital shaker for 30 minutesThe residual cake was extracted twice with 100mLmethanolThe methanol extracts were combined filtered and thenconcentrated under reduced pressure to dryness at 40∘C

Sample Cleanup The contaminated sample extracts cause theloss of detector sensitivity shorten the life time of columnproduce extraneous peaks and deteriorate peak resolutionand column efficiency [27]Therefore the extract was cleanedby using a Florasil packed column Briefly about 20 g ofFlorasil was added to a preconditioned chromatographiccolumn between two layers of anhydrous sodium sulphate (1to 2 cm deep) The concentrated extract was loaded onto thetop of the columnThe column was drained with acetonitrileuntil the sodium sulphate layer was exposed It was theneluted with mobile phase at a drip rate of about 5mLminMobile phase for HPLC analysis was prepared by mixing001 of acetic acid and acetonitrile in 60 40 ratio Theeluate was concentrated and residue was redissolved in 5mLof acetonitrile This cleaned extract was used for pesticideanalysis by HPLC

25 Metal Analysis by AAS Wet acid digestion method wasused for the analysis of metals present in soil samples Briefly10 g portions of air-dried and sieved soil samples were addedwith 15mL of 1 1 conc HNO

3and refluxed without boiling

at 95∘C for about 10ndash15 minutes It was further added with3mL of concentrated HNO

3and heating was continued for

about 30 minutes Subsequently the contents were cooled toroom temperature and added with about 5mL of 30 H

2O2

4 Scientifica

Table 1 Analytical parameters for the estimation of selected metals by AAS

Sr number Metal Wavelength (nm) Lamp current (mA) Slit width (nm) Fuel flow rate (Lmin) Detection limit (mgL)1 Pb 2833 90 13 22 0202 Cr 3593 90 13 28 0053 Co 2407 15 02 22 0204 Cu 3248 90 13 22 0025 Ni 2320 12 02 22 0106 Cd 2288 90 13 20 0005

in aliquots Digestion was continued until effervescencesubsided Then a 15mL portion of concentrated HCl wasadded and contents were cooled filtered through a sinteredglass crucible and finally diluted up to 50mL with distilledwater [30] This acid extract was aspirated directly onto AASfor metal estimation under optimum analytical conditions asgiven in Table 1

26 Statistical Analysis of Data The data set obtained forvarious physicochemical parameters metals and pesticideresidues in the representative soil samples was treated statis-tically by both univariate andmultivariate statistical analysesThe univariate statistical analysis involved the evaluationof basic statistical parameters like mean standard devia-tion standard error kurtosis and skewness and the linearcorrelation coefficient matrix Correlation coefficient matrixfurnished the correlation patterns among variousmetal pairsphysicochemical parameters and pesticides in the soilmediaMultiple correlation matrix was also developed in termsof metal-to-pesticide metal-to-physicochemical parametersand pesticide-to-physicochemical parameters to determinethe dependence of various parameters upon each other Themultivariate statistical analysis in terms of cluster analysis wasperformed to get an insight into the clustering behavior ofvarious parameters on mass scale by using Statistica software[31]

3 Results and Discussion

31 Distribution of Various Parameters of Soil Samples Phys-ical properties of the soil influence themobility and pathwaysof nutrients and pollutants within the soil Similarly the accu-mulation of the xenobiotics (foreign chemicals) in the soil isgoverned by a number of physicochemical parameters of soilsuch as its pH conductance and the amount of inorganicions (Clminus NO

3

minus SO4

2minus etc) It is therefore necessary toevaluate these physicochemical parameters and determinetheirmutual relationship so that a sustainable agriculturemaybe maintained

The basic statistics for the physicochemical parametersmetal levels and pesticide concentrations in fifty-two soilsamples collected from ten fields of Pakpattan Pakistan areenlisted in Table 2 The soil samples were grayish in colourand the texture of all the soil samples was sandy loam Thebulk density of soil samples was found to range from 153to 161Mgmminus3 with a mean value standing at 1568Mgmminus3pH another important parameter for the agricultural soilwas found to be present at narrow range of 76ndash85 with

a mean value of 81 Soils with these pH values exhibit higheravailability of metals such as Mg Ca and K while some othermetals such as Fe Zn and Cu are less available at this pH[32] It is also known that under alkaline conditions theadsorption of pesticides takes place to a lesser extent and thusthey degrade easily [33ndash35]

The organic matter content of soil is regarded as a majorfactor controlling the sorption transport and transformationof pesticides [36] For the present soil samples it was foundto vary from 129 to 1139 with a mean value of 4616 Anorganic carbon content of gt5 may enhance the sorptionof pesticides in soil depending on the nature of pesticidesand organic matter this in turn reduces the leaching andtransport properties of pesticides [37] In case of presentstudy the mean organic carbon content of soils was foundbelow 5 but slightly higher than background levelsThus inthese soils the extent of sorption of pesticides to the soil maynot be significant but this may be evidenced clearly on thebasis of amore comprehensive study based on chemometrics

The ionic strength of these soil samples is represented bya mean conductivity value of 1412 120583Scm signifying that alarger portion of solubilized cations and anions are presentin the water extracts of soil samples which were most likelyderived from the fertilizers and manure used to restore thefertility of soil It was further confirmed by the presence ofhigh concentration of anions such as chloride nitrate andsulphate in the soil samples

The mean chloride nitrate and sulphate levels recordedfor these soil samples were 129 3501 and 471mgg respec-tively with their sample variances of 377 times 107 1178 times 108and 466 times 108 respectivelyThe order of mean levels of theseanions thus remained SO

4

2minus

gt NO3

minus

gt Clminus Large values forstandard deviation projected a large spread of data set aroundthe mean value

The excessive sulphate concentration in the soil originatesfrom the use of zinc sulphate and urea in addition to decayedvegetablematter compost andmanure used to normalize thesoil pHThe enhanced levels of nitrate in the soil as comparedto background soil pointed towards an excessive use of nitratefertilizers such as nitrates of sodium potassium calcium andammonium in fields

The use of pesticides has contributed significantlytowards increased agricultural yield protection of livestockand the reduction of vector-transmitted diseases but theirimpacts on ecosystems and humans have always beenfocused on by scientific regulatory and policy communities[38ndash40] Imidacloprid acetamiprid and emamectin were

Scientifica 5

Table2Ba

sicstatisticsp

aram

etersfor

thed

istrib

utionof

selected

parameters(mgkg)insoilsamples

(119899=52)

Minim

umMaxim

umMean

Median

SDSE

Varia

nce

Kurtosis

Skew

ness

NEQ

SBClowast

Pb(m

gkg)

1093

2185

1618

1649

268

0372

7184

minus0639

minus0261

25189

Cr(m

gkg)

164

96586

5995

2238

031

5008

minus0902

minus0183

20503

Co(m

gkg)

293

124

7558

7595

2094

029

4386

minus0291

0077

100392

Cu(m

gkg)

1298

2190

1812

1856

2141

0297

4584

minus0332

minus0516

mdash276

Ni(mgkg)

153

2997

2216

2225

366

60508

1344

minus0572

0118

200135

Cd(m

gkg)

0347

1019

0585

0538

0175

0024

0031

0104

0961

05

014

Bulkdensity

(Mgmminus3

)15

3016

1015

6815

700028

0005

0001

minus13

33minus0003

mdashmdash

OC(

)12

911139

4616

3390

2894

0401

8376

minus0248

1074

mdash45

pH76

85

81

8055

02

0028

004

minus007

minus0206

mdash72

Con

ductivity

(120583Scm

)980

1887

1412

16005

3174

4402

1008times105

minus17

77minus0076

mdash108

Clminus

(mgkg)

4808

22438

12909

12338

61456

8522

3777times107

minus12

880271

mdash987

NO3

minus

(mgkg)

2879

94434

3500

934470

10852

1505

1178times108

1854

2807

mdash843

SO4

2minus

(mgkg)

400

9times103

9297times104

4710times104

40times104

2159times104

2993times103

466

0times108

1028

1447

mdash419

Imidacloprid

(120583gg)

23

2059

6445

556

6212

8613

3857

036

1229

mdashmdash

Emam

ectin

(120583gg)

0001

1305

2967

599

4312

598

1859times105

0414

1351

mdashmdash

Acetam

iprid

1140

12588

2643

704118

35711

169600

0968

1635

mdashmdash

lowast

BC=backgrou

ndlevels(m

eanof

three)

6 Scientifica

Moi

sture

cont

ent (

)

OC

()

pH

Box plot

Median

Nonoutlier range

Box plot

Imid

aclo

prid

Emam

ectin

Acet

amip

rid

Outliers

Cr Co Cu Ni CdPb

25ndash75

Median

Nonoutlier range 25ndash75

Median Nonoutlier range 25ndash75

OutliersMedian Nonoutlier range 25ndash75

minus5

0

5

10

15

20

25

30

35

minus200

0

200

400

600

800

1000

1200

1400

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

02468

101214161820

Clminus

(mg

kg)

NO3minus

(mg

kg)

SO42minus

(mg

kg)

Figure 2 Box and Whisker plots for the distribution of various parameters in soil

the pesticides that are being applied to the cotton crops ofPakpattan intermittently That is why these pesticides wereincluded in the study The data recorded a great variabilityin the concentrations of imidacloprid that was present ata minimum value of 23 120583gg and a maximum value of2059120583gg with a mean value standing at 6445 120583gg Thislarge variation in the recorded values reflected the differencesin the extent of exposure of soil to the pesticides Emamectinwas present in these samples at mean levels of 2967 120583ggwhile the mean levels for acetamiprid were 2643 120583gg Thelarge variation between themean andmedian values depictedthe nonnormal distribution of the data which was alsoreflected by high SD skewness and kurtosis values Thedistribution of these pesticides has also been depicted in Boxplots (Figure 2)

The data for the descriptive statistics of selected metals(ie Pb Cr Co Cu Ni and Cd Table 2 Figure 2) showedthat nickel in these samples was present at highest meanconcentration of 2216mgkg The major source of Ni inthese soils may be the Ni plating industry located nearbyNi was followed by Cu that exhibited a mean concentrationof 1812mgkg The minimum and maximum concentrationsrecorded for Cu were 1298 and 2190mgkg respectivelyCopper is required for various biochemical processes inplants thus it is an essential trace element but its enhancedconcentrations are hazardous for human populations [41]

Lead was another heavy metal that was present inthese samples at appreciable maximum concentration of1618mgkg Over the past few decades the vehicular emis-sions from leaded gasoline have been overcome due to ban

Scientifica 7

on leaded gasoline thus the source of this lead in soilwas traced in various fungicides and pesticides like leadarsenate and so forth that are used at various stages of cropproduction [2] Cadmium was the metal that was presentat trace level of 0585mgkg Chromium another hazardousmetal was found to be present at a mean level of 586mgkgIts maximum concentration was recorded to be 96mgkgwhich is quite higher than the limit set for agricultural soilsThis chromium not only is hazardous for soil biota butmay also contaminate the food chain through uptake andaccumulation by plants furthermore depending on the soilconditions like pH it may become soluble and thus enter thegroundwater the only source of drinking water in the area

The mean levels recorded for Co were 7558mgkg Theorder of themean concentrations ofmetals in the soil samplesremained Ni gt Cu gt Pb gt Co gt Cr gt Cd The symmetryparameters for the data that is standard deviation skewnessand kurtosis are also listed in Table 2

A comparison of mean metal levels with NationalEnvironmental Quality Standards (NEQS) is also depictedin Table 2 The average Pb concentration in soil sampleswas found to be 1618mgkg against the standard valueof 25mgkg The estimated value of lead in soil sampleswas lower than standard value which indicated that soil Pbwas below the contamination level and would not pose asignificant threat of contaminating the food chain MoreoverPb uptake by plants depends upon soil pH that is at higherpH lead becomes immobilized It is also known that due tosmall transfer factor Pb is not taken up by plants below aconcentration of 300120583gg in soil and if taken up it wouldaccumulate in leaves rather than the fruit [42 43]

Themean level of Cr recorded in soil was 586mgkgThisvalue is approximately four times less than standard value of20mgkg (NEQS) Co was present in the soil samples at themean level of 7558mgkg which is also less than standardvalue of 10mgkg The mean concentration of Cu in soilsamples was found to be 1812mgkg Ni was present in soilsamples at the mean level of 2216mgkg slightly higher thanthe recommended standard value of 20mgkg

The mean concentration of Cd was found to be0585mgkg a value slightly exceeding the standard valueof 05mgkg In fact fertilizers are added regularly to soilsto replenish N K and P for good crop growth Thesecompounds contain trace amounts of Cd as impuritieswhich after continued application are significantly increasedin the soil [44] Overall it was concluded that Pb Cr Cuand Co were present in tolerable range in the soil samples butNi and Cd surpassed the standard value but not to greaterextents Thus although the selected metals do not pose anythreat to the environment at their present levels but with thepassage of time the unwise use of agricultural activities maylead to a large buildup of metals in the soil that may endangerthe environment as well as human health

32 Correlation Coefficient Matrices of Various Parameters inthe Soil Table 3 depicted the correlation coefficient matrixfor the studied physicochemical parameters pesticides andmetal levels in the soil samples collected from the agriculturalfields The 119903-values were found to be significant at plusmn0231

(119901 lt 005) The data was characterized by both negative andpositive correlations between various pairs of parametersThe data was nonnormally distributed and also the anthro-pogenic activities led to a change in the natural concentrationof some of the parameters Thus all the observed correlationswere not high For the physicochemical parameters themost significant positive correlation was observed betweenelectrical conductivity and chloride levels with an 119903-value0292 evidencing that in about 292 cases the electricalconductivity of soil was observed to be increased with anincrease in chloride content and vice versa Similarly a strongpositive correlation was observed between pH and sulphatewith 119903-values of 0235 Organic carbon content of soil wasfound to be positively correlated with nitrate levels but thiscorrelation was not significant

The correlation coefficientmatrix for the levels of selectedmetals in the collected soil samples depicted the strongestpositive correlation between Cr and Ni at an 119903-value of 0460thereby showing that in 460 cases the concentration ofCr went in parallel with concentration of Ni thus sharing asimilar origin in the soil matrix The next strongest positivecorrelation was observed betweenNi and Cu pair (0431)Theother metal pair that was significantly positively correlatedincluded Cr-Co (119903-value 0343) Cr Ni and Cu were foundto be strongly negatively correlated with Cd (119903-values ofminus0407 minus0430 and minus0375 resp) depicting an increase inconcentration of one metal with a decrease in concentrationof other metals

No significant positive or negative correlation wasobserved among the selected pesticides depicting that thesources of pesticides in the soil were not the same Thisis also due to the fact that different pesticides are appliedto the crops at different stages of crop production Thusthey enter the soil at different periods of time The datacorresponding to the correlation coefficient matrix for thephysicochemical parameters and the various metals depictedonly few significant positivenegative correlations Ni ofthe soil exhibited the strongest positive correlation withits conductivity with 119903-value of 0342 Cu was also signifi-cantly positively correlated with the conductivity (119903-value of0286) Cd and electrical conductivitywere significantly nega-tively correlated Another significant negative correlationwasobserved between Cr and nitrate level of soil solution Theother correlations were too naıve to be discussed

The correlation coefficient matrix for the pesticides-to-physicochemical parameters depicted a significant neg-ative correlation between soil organic carbon content andemamectin thereby evidencing the influence of soil organiccarbon on the sorption of emamectin Soil EC values werealso found to be negatively correlated with imidacloprid andemamectin

Numerous metals are known to possess good catalysisability and they may affect the behavior of coexisting pes-ticides in the soil Thus the most important segment of thepresent investigation was to study the correlations among theselected pesticides and variousmetal levelsThe data depicteda strong positive correlation between acetamiprid and Cuwith 119903-value of 0239 A strong positive correlation pointedtowards an increase in the concentration of acetamiprid

8 Scientifica

Table3Correlationcoeffi

cientm

atrix

aforv

arious

parameterso

fsoilsam

ples

(119899=52)

PbCr

Co

CuNi

Cd

OCb

pHEC

cClminus

NO3

minus

SO4

2minus

Imd

Eme

Acf

Pb10

00Cr

0179

1000

Co

0019

034

310

00Cu

0018

0132minus0002

1000

Ni

0199

046

00074

0431

1000

Cd

minus0154minus040

7minus0045minus0375minus043

010

00OC(

)0124

0083

0092minus0136minus0039minus0075

1000

pH0080minus0162

0164minus0124minus0076

0118

0187

1000

EC(120583SCm

)minus000

9minus0045minus0047

028

6034

2minus024

50137

0059

1000

Clminus

(mgkg)minus0163minus0255minus0140minus0079

0034

0144

0083

0058

029

210

00NO3

minus

(mgkg)

0011

0018minus0221minus0065

0051minus0076

0213

0014

0153

0087

1000

SO4

2minus

(mgkg)minus0080minus0149minus0201minus0096minus0057

0146

000

40235minus0156

0212

0177

1000

Imlowast

0086minus0021

0012

0017minus0317

0021

0100

0175minus0314minus0122minus0103

0052

1000

Emlowast

0213minus0071

0161

000

9minus0012

0015minus0239

0084minus0265minus0163minus0183

0085minus0086

1000

Aclowast

minus0119

minus030

5minus0143

0239minus0102

0163minus0077

0099

0313

0038

0007minus0085

0050minus0174

1000

a 119903-valuesa

resig

nificantat0

231

at119901lt005

b OC=organicc

arbo

nc EC=ele

ctric

alcond

uctiv

itydIm

=im

idacloprideEm

=em

amectin

fAc

=acetam

iprid

lowast

Con

centratio

nin120583gg

Scientifica 9

Wardrsquos method

OC ()Imidacloprid

pH

CdAcetamiprid

Conductivity (120583Scm)CuCoNiCr

EmamectinPb

04 06 08 10 12 14 16 18 2002Linkage distance

Clminus (mgkg)

NO3minus (mgkg)

SO42minus (mgkg)

Figure 3 Cluster analysis for the determination of various parame-ters

with the presence of greater concentration of copper in thesoil On the other hand imidacloprid in soil was found tobe negatively correlated with Ni of soil (119903-value of minus0317)Similarly a significant negative correlation was observedbetween Cr and acetamiprid (119903-value minus0305) Thus it wasevidenced that Cu stabilizes acetamiprid while Cr and Nifacilitate the degradation of acetamiprid and imidacloprid inthe soil [45]

Similar results have been reported for pyrethroid pes-ticides whose degradation was shown to be inhibited bythe presence of copper ions Ellis et al reported that metalslike Cu present in soil may react with the sulfhydryl groupof enzymes and inhibit their activity Thus the pesticidesbecome more persistent thereby leading to an increase intheir concentration with time [21 46]

33 Cluster Analysis of Various Parameters in the Soil Sam-ples Cluster analysis has proved to be a milestone towardthe source apportionment studies of various pollutants likemetals and pesticides in the soil and other media [47 48]In this analysis (Figure 3) linkage distance is used as themeasure of degree of closeness and hence relation among thevarious parameters [49] A number of clusters were formedwithin a significant linkage distance The strongest clusterwas observed between Cr and Ni evidencing that high Crcontent of the soil was associated with the enhanced Nilevels These two metals were further associated with Co toform a second cluster within linkage distance of 10 Themost important cluster of the study was observed betweenacetamiprid and conductivity that was further associatedwith Cu It evidenced that Cu present in the soil may causethe persistence of acetamiprid whose concentration increaseswith time Similarly emamectin was closely associated withPd

Cluster analysis revealed a close association betweensulphate and pH which formed a primary cluster withinlinkage distance of 06 This primary cluster was furtherassociated with Cd and Clminus within linkage distance of 10 onone side and with imidacloprid in the soil on the other side

The organic carbon of soil was associated with nitrate withina linkage distance of 08 and this factor was further associatedwith previous cluster

Overall the study revealed that frequently used pesti-cides that is imidacloprid emamectin and acetamipridwere present in the soil of cotton fields and were influencedby factors such as soil pH and organic carbon The studyalso furnished correlations among pesticides and metals inthe soil It was shown that presence of certain metals such asNi caused the decreased levels of imidacloprid Similarly Crenhanced the degradation of acetamiprid and Cu caused thepersistence of this pesticide in the soil

4 Conclusions

The soil samples collected from the cotton growing area ofPakpattan Pakistan were slightly basic in nature The meanPb Cr Co and Cu levels were below NEQS while the levelsof Ni and Cd were slightly above NEQS These levels may betolerated by following precautionarymeasures in agriculturalactivities Among the pesticides emamectin exhibited a highpersistence in the soil that was closely associated with soilCu content It was also found that Cu stabilizes acetamipridwhile Cr and Ni facilitate the degradation of acetamipridand imidacloprid Thus the study provides basis for therisk assessment studies that are quite necessary to managethe contaminated sites in a cost effective manner whilepreserving the public and ecosystem health It also providesa management strategy for remediation of contaminatedsoil that is adding traces of Ni and Cr in the soil mayhelp in the degradation of frequently used acetamiprid andimidacloprid

Conflict of Interests

The authors declare no conflict of interests

References

[1] R A Cloyd and J A Bethke ldquoImpact of neonicotinoidinsecticides onnatural enemies in greenhouse and interiorscapeenvironmentsrdquo Pest Management Science vol 67 no 1 pp 3ndash92011

[2] P Khaliq L A Hashmi and M H Qazi ldquoAgriculture andenvironmentrdquo Progress Farming vol 15 pp 16ndash23 1995

[3] H Shiraishi F Pula A Otsuki and T Iwakuma ldquoBehaviourof pesticides in Lake Kasumugaura Japanrdquo Science of the TotalEnvironment vol 72 pp 29ndash42 1988

[4] R Rial Otero B Cancho Grande M Arias Estevez E LopezPeriago and J Simal Gandara ldquoProcedure for themeasurementof soil inputs of plant-protection agents washed off throughvineyard canopy by rainfallrdquo Journal of Agricultural and FoodChemistry vol 51 no 17 pp 5041ndash5046 2003

[5] H M G van der Werf ldquoAssessing the impact of pesticideson the environmentrdquo Agriculture Ecosystems and Environmentvol 60 no 2-3 pp 81ndash96 1996

[6] G W vanLoon and S J Duffy Environmental Chemistry AGlobal Perspective Oxford University Press Oxford UK 2ndedition 2005

10 Scientifica

[7] P K Goel Water Pollution (Causes Effects and Control) NewAge International (P) New Delhi India 2nd edition 2006

[8] M Arias-Estevez E Lopez-Periago E Martınez-Carballo JSimal-Gandara J-C Mejuto and L Garcıa-Rıo ldquoThe mobilityand degradation of pesticides in soils and the pollution ofgroundwater resourcesrdquo Agriculture Ecosystems amp Environ-ment vol 123 no 4 pp 247ndash260 2008

[9] P J Shea T A Machacek and S D Comfort ldquoAcceleratedremediation of pesticide-contaminated soil with zerovalentironrdquo Environmental Pollution vol 132 no 2 pp 183ndash188 2004

[10] A Isaiah and M Paul ldquoSynergistic effect of chemical pesticideson commonly grown vegetables in Northern Indiardquo Epidemiol-ogy vol 18 p S86 2007

[11] J Fenoll P Hellın C Marın C M Martınez and A PFlores ldquoMultiresidue analysis of pesticides in soil by gaschromatography with nitrogen-phosphorus detection and gaschromatography mass spectrometryrdquo Journal of Agriculturaland Food Chemistry vol 53 no 20 pp 7661ndash7666 2005

[12] S Seccia P FidenteDMontesano andPMorrica ldquoDetermina-tion of neonicotinoid insecticides residues in bovine milk sam-ples by solid-phase extraction clean-up and liquid chromatog-raphy with diode-array detectionrdquo Journal of ChromatographyA vol 1214 no 1-2 pp 115ndash120 2008

[13] S M Dem J M Cobb and D E Mullins ldquoPesticide residuesin soil and water from four cotton growing areas of Mali WestAfricardquo Journal of Agricultural Food amp Environmental Sciencesvol 1 no 1 pp 1ndash12 2007

[14] M W Aktar M Paramasivam D Sengupta S Purkait MGanguly and S Banerjee ldquoImpact assessment of pesticideresidues in fish of Ganga river around Kolkata in West BengalrdquoEnvironmental Monitoring and Assessment vol 157 no 1ndash4 pp97ndash104 2009

[15] T R Sandrin and R M Maier ldquoImpact of metals on thebiodegradation of organic pollutantsrdquo Environmental HealthPerspectives vol 111 no 8 pp 1093ndash1101 2003

[16] S Khan Q Cao Y M Zheng Y Z Huang and Y G ZhuldquoHealth risks of heavy metals in contaminated soils and foodcrops irrigated with wastewater in Beijing Chinardquo Environmen-tal Pollution vol 152 no 3 pp 686ndash692 2008

[17] M-K Zhang Z-Y Liu and H Wang ldquoUse of single extractionmethods to predict bioavailability of heavy metals in pollutedsoils to ricerdquo Communications in Soil Science amp Plant Analysisvol 41 no 7 pp 820ndash831 2010

[18] Y PWang J Y ShiHWangQ Lin X CChen andYXChenldquoThe influence of soil heavy metals pollution on soil microbialbiomass enzyme activity and community composition near acopper smelterrdquo Ecotoxicology amp Environmental Safety vol 67no 1 pp 75ndash81 2007

[19] A A Helal D M Imam S M Khalifa and H F AlyldquoInteraction of pesticides with humic compounds and theirmetal complexesrdquo Radiochemistry vol 48 no 4 pp 419ndash4252006

[20] H Tian J Li Z Mu L Li and Z Hao ldquoEffect of pH onDDT degradation in aqueous solution using bimetallic NiFenanoparticlesrdquo Separation amp Purification Technology vol 66no 1 pp 84ndash89 2009

[21] T-F Liu C Sun N Ta J Hong S-G Yang and C-X ChenldquoEffect of copper on the degradation of pesticides cypermethrinand cyhalothrinrdquo Journal of Environmental Sciences vol 19 no10 pp 1235ndash1238 2007

[22] E Quivet R Faure J Georges J-O Paısse and P LanterildquoInfluence of metal salts on the photodegradation of imazapyr

an imidazolinone pesticiderdquo Pest Management Science vol 62no 5 pp 407ndash413 2006

[23] M Kamiya andK Kameyama ldquoEffects of selectedmetal ions onphotodegradation of organophosphorus pesticides sensitizedby humic acidsrdquo Chemosphere vol 45 no 3 pp 231ndash235 2001

[24] M Radojevic and V N Bashkin Practical EnvironmentalAnalysis Royal Society of Chemistry Cambridge UK 1999

[25] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of selected metals in tan-nery effluents and related soilrdquo Journal of Hazardous Materialsvol 122 no 1-2 pp 17ndash22 2005

[26] G R Blake and K H Hartge ldquoBulk and particle densityrdquo inMethods of Soil Analysis Part 1 pp 363ndash382 Soil Science Societyof America Madison Wis USA 1986

[27] P Patnaik Handbook of Environmental Analysis ChemicalPollutants in Air Water Soil and SolidWastes CRC Lewis BocaRaton Fla USA 1997

[28] A Bartosova A Michalıkova M Sirotiak and M SoldanldquoComparison of two spectrophotometric techniques for nutri-ents analyses inwater samplesrdquoResearch Papers Faculty ofMate-rials Science and Technology SlovakUniversity of Technology vol20 no 32 pp 8ndash19 2013

[29] H Spiegel E Filcheva P Hegymegi A Gal and F G AVerheijen ldquoReview and comparison of methods used for soilorganic carbon determination part 2 laboratory studyrdquo SoilScience Agrochemistry and Ecology vol 41 no 4 pp 19ndash25 2007

[30] K H Tan Soil Sampling Preparation and Analysis CRC PressTaylor amp Francis Group Boca Raton Fla USA 2nd edition2005

[31] StatSoft Inc STATISTICA for Windows (Computer ProgramManual) StatSoft Tulsa Okla USA 1999

[32] USDA Soil Quality Indicator pH Natural Resources Conserva-tion Service 1998

[33] G E Lailach T DThompson and GW Brindley ldquoAbsorptionof pyrimidines purines and nucleosides by Co- Ni- Cu- andFe(III)-Montmorillonite (Clay-Organic Studies XIII)rdquo Claysand Clay Minerals vol 16 no 4 pp 295ndash301 1968

[34] R G NashW G Harris and C C Lewis ldquoSoil pH andmetallicamendment effects on DDT conversion to DDErdquo Journal ofEnvironmental Quality vol 2 no 3 pp 390ndash394 1973

[35] J G Konrad and G Chesters ldquoDegradation in soils of cioduman organophosphate insecticiderdquo Journal of Agricultural andFood Chemistry vol 17 no 2 pp 226ndash230 1969

[36] A Albarran R Celis M C Hermosın A Lopez-Pineiro and JCornejo ldquoBehavior of simazine in soil amended with the finalresidue of the olive-oil extraction processrdquo Chemosphere vol54 no 6 pp 717ndash724 2004

[37] J Dec and J-M Bollag ldquoDetermination of covalent and non-covalent binding interactions between xenobiotic chemicalsand soilrdquo Soil Science vol 162 no 12 pp 858ndash874 1997

[38] A Nawab A Aleem and A Malik ldquoDetermination oforganochlorine pesticides in agricultural soil with specialreference to 120574-HCH degradation by Pseudomonas strainsrdquoBioresource Technology vol 88 no 1 pp 41ndash46 2003

[39] M Bavcon P Trebse and L Zupancic-Kralj ldquoInvestigationsof the determination and transformations of diazinon andmalathion under environmental conditions using gas chro-matography coupled with a flame ionisation detectorrdquo Chemo-sphere vol 50 no 5 pp 595ndash601 2003

[40] S A Sassman L S Lee M Bischoff and R F Turco ldquoAssessingNN1015840-dibutylurea (DBU) formation in soils after application of

Scientifica 11

n-butylisocyanate and benlate fungicidesrdquo Journal of Agricul-tural and Food Chemistry vol 52 no 4 pp 747ndash754 2004

[41] E R Mouta M R Soares and J C Casagrande ldquoCopperadsorption as a function of solution parameters of variablecharge soilsrdquo Journal of the Brazilian Chemical Society vol 19no 5 pp 996ndash1009 2008

[42] M Arshad J Silvestre E Pinelli et al ldquoA field study oflead phytoextraction by various scented Pelargonium cultivarsrdquoChemosphere vol 71 no 11 pp 2187ndash2192 2008

[43] G Uzu S Sobanska Y Aliouane P Pradere and C DumatldquoStudy of lead phytoavailability for atmospheric industrialmicronic and sub-micronic particles in relation with leadspeciationrdquo Environmental Pollution vol 157 no 4 pp 1178ndash1185 2009

[44] L H P Jones and S C Jarvis ldquoThe fate of heavy metalsrdquo inTheChemistry of Soil Processes D J Green andMH B Hayes Edsp 593 John Wiley amp Sons New York NY USA 1981

[45] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of trace metal levels intannery effluents in relation to soil and water a case study fromPeshawar Pakistanrdquo Journal of EnvironmentalManagement vol79 no 1 pp 20ndash29 2006

[46] R J Ellis B Neish MW Trett et al ldquoComparison of microbialand meiofaunal community analyses for determining impact ofheavy metal contaminationrdquo Journal of Microbiological Meth-ods vol 45 no 3 pp 171ndash185 2001

[47] S R Tariq F Iqbal and A Ijaz ldquoAssessment and multivariateanalysis of metals in surgical instrument industry affected topsoils and groundwater for future reclamationrdquo InternationalJournal of Environment and Pollution vol 1 pp 54ndash71 2013

[48] S R Tariq and N Rashid ldquoMultivariate analysis of metal levelsin paddy soil rice plants and rice grains a case study fromShakargarh Pakistanrdquo Journal of Chemistry vol 2013 ArticleID 539251 10 pages 2013

[49] B S Everitt S Landau and M Leese Cluster Analysis Arnold4th edition 2001

Submit your manuscripts athttpwwwhindawicom

Nutrition and Metabolism

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Food ScienceInternational Journal of

Agronomy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

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Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

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PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Plant GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Biotechnology Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

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Veterinary Medicine International

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Cell BiologyInternational Journal of

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Evolutionary BiologyInternational Journal of

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2 Scientifica

of cypermethrin and cyhalothrin by affecting the activityof microorganisms [21] Complexation interactions betweenimazapyr pesticide andmetal ions were found to decrease theimazapyr photolysis [22] It has also been found that selectedmetal ions having paramagnetic property could inhibit theaquatic photodegradation of some pesticides with humicacids [23]

The present study focuses on tracing the correlationpatterns among the levels of coexistent metals and pesticidesin the soil The correlation model thus developed betweenpesticide and heavy metals will be useful for monitoring thepesticides in soil due to the measurement of heavy metalsbeing more available So the study may provide the basisfor the management of soils contaminated with pesticidessubsequent to successful monitoring

2 Materials and Methods

21 Quality Control and Quality Assurance High qualityPyrex glassware was used during the present study which wasthoroughly cleanedwith chromicmixture 5detergent solu-tion and finally distilled water All the volumetric apparatusemployed formeasurements sample processing and dilutionwas calibrated before use In order to deliver the small volume(ie lt10mL) of stock standard solutions pipettes of 100mLcapacity were used

Double distilled water was used for the preparation ofblanks standards and reagents Analytical grade reagentswith a 9999 certified purity were procured from E-Merck(Germany) and used for quantification The stock standardsolutions of selected metals (1000mgL) as provided byE-Merck (Germany) were utilized for the preparation ofworking standards after appropriate dilution with DDWThe inconsistencies in measurement likely to arise from theuse of highly concentrated stock solutions were avoided bythe use of an intermediate working standard of 100mgLconcentration HPLC grade chemicals provided by E-MerckGermany were used for the extraction of pesticides samplecleanup and mobile phase formation The analytical stan-dards of three pesticides were obtained from Riedel-deHaen(Germany)The chances of any photodegradation of reagentswere avoided by storing them in the dark

The levels of selected trace metals that is Co Pb Cr NiCu and Cd were determined by using HITACHI AAS Z-5000 spectrophotometer The calibration curve method wasused to quantify the results At least six standards were runcovering the absorption range of samples The precision ofquantitative results was ensured by analyzing the triplicatesamples

The residues of three selected pesticides that is imidaclo-prid emamectin and acetamiprid were determined by usingthe HPLC System of Waters 1500 The detector used for thepresent investigation wasWaters-2487 a dual wavelength ab-sorbance detector designed especially forHPLC applications

The extracted and cleaned pesticide residue samples wereinjected into the chromatographic system equipped with C-8 column at a rate of 1mLmin The eluent used was a 3 2mixture of water and acetonitrile At the retention timesof 493 minutes the signals for imidacloprid emamectin

and acetamiprid were recorded by UV detector at specifiedwavelengths of 270 nm 245 nm and 254 nm respectively

22 Sampling For the present investigation a total of 52 topsoil (1ndash15 cm) samples were collected from ten different fieldsof Pakpattan Pakistan A 300 g portion of each of the soilsamples was taken in zipmouthed polyethylene bags with thehelp of soil auger These samples were properly labeled andimmediately transferred to lab where they were stored at 4∘Cuntil analysis The electrical conductivity and pH of the sam-ples were determined by immersion probe technique whilemoisture content chloride nitrate and sulphate were deter-mined by appropriate standard methods [24] All sampleswere treated and analyzed at the laboratory of Department ofChemistry Lahore College forWomen University Lahore Inorder to get the reference data the background soil sampleswere collected from remotely located agricultural soil withsandy loam texture where no pesticides were used previouslyThese background soil samples were also processed quitesimilar to the samples from the fields

23 Description of Study Area The district Pakpattan is oneof the major cotton growing areas in Pakistan It coversan area of about 3084 km2 with a population density of417 persons per sqkm A highly fertile land and a climatethat is most suitable for sustaining the crops are the mainfeatures of the area The city is bounded by river Satluj andBias that constitute the main source for irrigation Therefore88 of the area is comprised of cultivated land Soil texturehere varies from silt loam to clay loam and average annualrainfall is 200ndash300mm The temperature ranges from 66∘Cinwinter to 417∘Cduring the summerThemain crops grownhere include wheat rice cotton maize (corn) and sugarcane In addition about 507 agriculture based industrialunits are present in the district that include fertilizer cottonpressing and ginning oil mills flour mills rice mills poultryfeed textile weaving and sugar mills The exports from thearea consist principally of cotton wheat and oilseeds Toaccomplish the present study a total of fifty-two sampleswere obtained from cotton growing areas of Pakpattan Thesampling sites location is shown in Figure 1

24 Determination of Physicochemical Parameters The col-lected soil samples were ground homogenized and sub-sequently sieved through a brass sieve with pore size of850 120583m in accordance with international standards for soilanalysis [24] The water extract of soil samples was preparedby stirring a 1 10 soil-water mixture for five minutes andallowing equilibration for thirty minutes The filtrate thusobtained was used for the determination of physicochemicalparameters such as chlorides and nitrates sulphates [25] Inorder to determine the soil bulk density undisturbed cores ofdimensions 005 times 0072mwere drawn from 5 to 10 cm depthof soil [26]

The pH of all the soil samples was determined by using aInolab-720 portable pH meter precalibrated by using stan-dard buffer solutions of pH 40 70 and 90The conductivityof water extract of soil samples was determined by usingWTW Inolab-720 conductivity meter

Scientifica 3

Chak 40

NA-166 Chak-149

Arifwala Chak-9

Chack Shan Karam

Baghu

Chak-97

Chak-67

River Sutlej

lowastlowastlowast

lowastlowast

Figure 1 Location map of sampling siteslowast

The chloride contents of the soil samples were deter-mined gravimetrically by using AgNO

3as precipitant [27]

In order to determine the sulphate ions a 100mL portionof water extract of soil samples was stirred for five minuteswith HCl and glycerol solutions along with approximately003 g of BaCl

2 Immediately after stirring the solution was

poured into a quartz cell with an optical path of 10 cmand the absorbance was measured at 420 nm on a UVspectrophotometer A series of calibration standards betweenconcentrations of 05 and 5mg SO

4

2minusL were prepared andused for drawing calibration curve [24]

Nitrate present in the soil samples was determined byusing the sodium salicylatemethod Here 100mL portions ofwater extract of each of the soil samples were evaporated with10mL of sodium salicylate and cooled to room temperatureSubsequently 10mL of concentrated H

2SO4was added to

dehumidify the entire residue and allowed to stand for 10minutes It was then quantitatively transferred to a 50mLvolumetric flask added with 70mL of NaOH and adjustedthe volume to 50mL with distilled water After 10 minutesthe absorbance was measured at 410 nm against the blankprepared in the same way Calibration curve was constructedby using the standard KNO

3solutions in the concentra-

tion range of 2ndash20mgL [28] The organic carbon contentsof the soil samples were determined by partial oxidationmethod that involved the titration of soil samples against1N (NH

4)2Fe(SO

4)2sdot6H2O solution by using diphenylamine

indicator [29]

Pesticide Analysis by HPLC The residues of selected pes-ticides that is imidacloprid acetamiprid and emamectinwere extracted from soil samples by using methanol as

solvent The extraction procedure adopted involved theshaking of the appropriate amount of soil samples with100mL of methanol on an orbital shaker for 30 minutesThe residual cake was extracted twice with 100mLmethanolThe methanol extracts were combined filtered and thenconcentrated under reduced pressure to dryness at 40∘C

Sample Cleanup The contaminated sample extracts cause theloss of detector sensitivity shorten the life time of columnproduce extraneous peaks and deteriorate peak resolutionand column efficiency [27]Therefore the extract was cleanedby using a Florasil packed column Briefly about 20 g ofFlorasil was added to a preconditioned chromatographiccolumn between two layers of anhydrous sodium sulphate (1to 2 cm deep) The concentrated extract was loaded onto thetop of the columnThe column was drained with acetonitrileuntil the sodium sulphate layer was exposed It was theneluted with mobile phase at a drip rate of about 5mLminMobile phase for HPLC analysis was prepared by mixing001 of acetic acid and acetonitrile in 60 40 ratio Theeluate was concentrated and residue was redissolved in 5mLof acetonitrile This cleaned extract was used for pesticideanalysis by HPLC

25 Metal Analysis by AAS Wet acid digestion method wasused for the analysis of metals present in soil samples Briefly10 g portions of air-dried and sieved soil samples were addedwith 15mL of 1 1 conc HNO

3and refluxed without boiling

at 95∘C for about 10ndash15 minutes It was further added with3mL of concentrated HNO

3and heating was continued for

about 30 minutes Subsequently the contents were cooled toroom temperature and added with about 5mL of 30 H

2O2

4 Scientifica

Table 1 Analytical parameters for the estimation of selected metals by AAS

Sr number Metal Wavelength (nm) Lamp current (mA) Slit width (nm) Fuel flow rate (Lmin) Detection limit (mgL)1 Pb 2833 90 13 22 0202 Cr 3593 90 13 28 0053 Co 2407 15 02 22 0204 Cu 3248 90 13 22 0025 Ni 2320 12 02 22 0106 Cd 2288 90 13 20 0005

in aliquots Digestion was continued until effervescencesubsided Then a 15mL portion of concentrated HCl wasadded and contents were cooled filtered through a sinteredglass crucible and finally diluted up to 50mL with distilledwater [30] This acid extract was aspirated directly onto AASfor metal estimation under optimum analytical conditions asgiven in Table 1

26 Statistical Analysis of Data The data set obtained forvarious physicochemical parameters metals and pesticideresidues in the representative soil samples was treated statis-tically by both univariate andmultivariate statistical analysesThe univariate statistical analysis involved the evaluationof basic statistical parameters like mean standard devia-tion standard error kurtosis and skewness and the linearcorrelation coefficient matrix Correlation coefficient matrixfurnished the correlation patterns among variousmetal pairsphysicochemical parameters and pesticides in the soilmediaMultiple correlation matrix was also developed in termsof metal-to-pesticide metal-to-physicochemical parametersand pesticide-to-physicochemical parameters to determinethe dependence of various parameters upon each other Themultivariate statistical analysis in terms of cluster analysis wasperformed to get an insight into the clustering behavior ofvarious parameters on mass scale by using Statistica software[31]

3 Results and Discussion

31 Distribution of Various Parameters of Soil Samples Phys-ical properties of the soil influence themobility and pathwaysof nutrients and pollutants within the soil Similarly the accu-mulation of the xenobiotics (foreign chemicals) in the soil isgoverned by a number of physicochemical parameters of soilsuch as its pH conductance and the amount of inorganicions (Clminus NO

3

minus SO4

2minus etc) It is therefore necessary toevaluate these physicochemical parameters and determinetheirmutual relationship so that a sustainable agriculturemaybe maintained

The basic statistics for the physicochemical parametersmetal levels and pesticide concentrations in fifty-two soilsamples collected from ten fields of Pakpattan Pakistan areenlisted in Table 2 The soil samples were grayish in colourand the texture of all the soil samples was sandy loam Thebulk density of soil samples was found to range from 153to 161Mgmminus3 with a mean value standing at 1568Mgmminus3pH another important parameter for the agricultural soilwas found to be present at narrow range of 76ndash85 with

a mean value of 81 Soils with these pH values exhibit higheravailability of metals such as Mg Ca and K while some othermetals such as Fe Zn and Cu are less available at this pH[32] It is also known that under alkaline conditions theadsorption of pesticides takes place to a lesser extent and thusthey degrade easily [33ndash35]

The organic matter content of soil is regarded as a majorfactor controlling the sorption transport and transformationof pesticides [36] For the present soil samples it was foundto vary from 129 to 1139 with a mean value of 4616 Anorganic carbon content of gt5 may enhance the sorptionof pesticides in soil depending on the nature of pesticidesand organic matter this in turn reduces the leaching andtransport properties of pesticides [37] In case of presentstudy the mean organic carbon content of soils was foundbelow 5 but slightly higher than background levelsThus inthese soils the extent of sorption of pesticides to the soil maynot be significant but this may be evidenced clearly on thebasis of amore comprehensive study based on chemometrics

The ionic strength of these soil samples is represented bya mean conductivity value of 1412 120583Scm signifying that alarger portion of solubilized cations and anions are presentin the water extracts of soil samples which were most likelyderived from the fertilizers and manure used to restore thefertility of soil It was further confirmed by the presence ofhigh concentration of anions such as chloride nitrate andsulphate in the soil samples

The mean chloride nitrate and sulphate levels recordedfor these soil samples were 129 3501 and 471mgg respec-tively with their sample variances of 377 times 107 1178 times 108and 466 times 108 respectivelyThe order of mean levels of theseanions thus remained SO

4

2minus

gt NO3

minus

gt Clminus Large values forstandard deviation projected a large spread of data set aroundthe mean value

The excessive sulphate concentration in the soil originatesfrom the use of zinc sulphate and urea in addition to decayedvegetablematter compost andmanure used to normalize thesoil pHThe enhanced levels of nitrate in the soil as comparedto background soil pointed towards an excessive use of nitratefertilizers such as nitrates of sodium potassium calcium andammonium in fields

The use of pesticides has contributed significantlytowards increased agricultural yield protection of livestockand the reduction of vector-transmitted diseases but theirimpacts on ecosystems and humans have always beenfocused on by scientific regulatory and policy communities[38ndash40] Imidacloprid acetamiprid and emamectin were

Scientifica 5

Table2Ba

sicstatisticsp

aram

etersfor

thed

istrib

utionof

selected

parameters(mgkg)insoilsamples

(119899=52)

Minim

umMaxim

umMean

Median

SDSE

Varia

nce

Kurtosis

Skew

ness

NEQ

SBClowast

Pb(m

gkg)

1093

2185

1618

1649

268

0372

7184

minus0639

minus0261

25189

Cr(m

gkg)

164

96586

5995

2238

031

5008

minus0902

minus0183

20503

Co(m

gkg)

293

124

7558

7595

2094

029

4386

minus0291

0077

100392

Cu(m

gkg)

1298

2190

1812

1856

2141

0297

4584

minus0332

minus0516

mdash276

Ni(mgkg)

153

2997

2216

2225

366

60508

1344

minus0572

0118

200135

Cd(m

gkg)

0347

1019

0585

0538

0175

0024

0031

0104

0961

05

014

Bulkdensity

(Mgmminus3

)15

3016

1015

6815

700028

0005

0001

minus13

33minus0003

mdashmdash

OC(

)12

911139

4616

3390

2894

0401

8376

minus0248

1074

mdash45

pH76

85

81

8055

02

0028

004

minus007

minus0206

mdash72

Con

ductivity

(120583Scm

)980

1887

1412

16005

3174

4402

1008times105

minus17

77minus0076

mdash108

Clminus

(mgkg)

4808

22438

12909

12338

61456

8522

3777times107

minus12

880271

mdash987

NO3

minus

(mgkg)

2879

94434

3500

934470

10852

1505

1178times108

1854

2807

mdash843

SO4

2minus

(mgkg)

400

9times103

9297times104

4710times104

40times104

2159times104

2993times103

466

0times108

1028

1447

mdash419

Imidacloprid

(120583gg)

23

2059

6445

556

6212

8613

3857

036

1229

mdashmdash

Emam

ectin

(120583gg)

0001

1305

2967

599

4312

598

1859times105

0414

1351

mdashmdash

Acetam

iprid

1140

12588

2643

704118

35711

169600

0968

1635

mdashmdash

lowast

BC=backgrou

ndlevels(m

eanof

three)

6 Scientifica

Moi

sture

cont

ent (

)

OC

()

pH

Box plot

Median

Nonoutlier range

Box plot

Imid

aclo

prid

Emam

ectin

Acet

amip

rid

Outliers

Cr Co Cu Ni CdPb

25ndash75

Median

Nonoutlier range 25ndash75

Median Nonoutlier range 25ndash75

OutliersMedian Nonoutlier range 25ndash75

minus5

0

5

10

15

20

25

30

35

minus200

0

200

400

600

800

1000

1200

1400

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

02468

101214161820

Clminus

(mg

kg)

NO3minus

(mg

kg)

SO42minus

(mg

kg)

Figure 2 Box and Whisker plots for the distribution of various parameters in soil

the pesticides that are being applied to the cotton crops ofPakpattan intermittently That is why these pesticides wereincluded in the study The data recorded a great variabilityin the concentrations of imidacloprid that was present ata minimum value of 23 120583gg and a maximum value of2059120583gg with a mean value standing at 6445 120583gg Thislarge variation in the recorded values reflected the differencesin the extent of exposure of soil to the pesticides Emamectinwas present in these samples at mean levels of 2967 120583ggwhile the mean levels for acetamiprid were 2643 120583gg Thelarge variation between themean andmedian values depictedthe nonnormal distribution of the data which was alsoreflected by high SD skewness and kurtosis values Thedistribution of these pesticides has also been depicted in Boxplots (Figure 2)

The data for the descriptive statistics of selected metals(ie Pb Cr Co Cu Ni and Cd Table 2 Figure 2) showedthat nickel in these samples was present at highest meanconcentration of 2216mgkg The major source of Ni inthese soils may be the Ni plating industry located nearbyNi was followed by Cu that exhibited a mean concentrationof 1812mgkg The minimum and maximum concentrationsrecorded for Cu were 1298 and 2190mgkg respectivelyCopper is required for various biochemical processes inplants thus it is an essential trace element but its enhancedconcentrations are hazardous for human populations [41]

Lead was another heavy metal that was present inthese samples at appreciable maximum concentration of1618mgkg Over the past few decades the vehicular emis-sions from leaded gasoline have been overcome due to ban

Scientifica 7

on leaded gasoline thus the source of this lead in soilwas traced in various fungicides and pesticides like leadarsenate and so forth that are used at various stages of cropproduction [2] Cadmium was the metal that was presentat trace level of 0585mgkg Chromium another hazardousmetal was found to be present at a mean level of 586mgkgIts maximum concentration was recorded to be 96mgkgwhich is quite higher than the limit set for agricultural soilsThis chromium not only is hazardous for soil biota butmay also contaminate the food chain through uptake andaccumulation by plants furthermore depending on the soilconditions like pH it may become soluble and thus enter thegroundwater the only source of drinking water in the area

The mean levels recorded for Co were 7558mgkg Theorder of themean concentrations ofmetals in the soil samplesremained Ni gt Cu gt Pb gt Co gt Cr gt Cd The symmetryparameters for the data that is standard deviation skewnessand kurtosis are also listed in Table 2

A comparison of mean metal levels with NationalEnvironmental Quality Standards (NEQS) is also depictedin Table 2 The average Pb concentration in soil sampleswas found to be 1618mgkg against the standard valueof 25mgkg The estimated value of lead in soil sampleswas lower than standard value which indicated that soil Pbwas below the contamination level and would not pose asignificant threat of contaminating the food chain MoreoverPb uptake by plants depends upon soil pH that is at higherpH lead becomes immobilized It is also known that due tosmall transfer factor Pb is not taken up by plants below aconcentration of 300120583gg in soil and if taken up it wouldaccumulate in leaves rather than the fruit [42 43]

Themean level of Cr recorded in soil was 586mgkgThisvalue is approximately four times less than standard value of20mgkg (NEQS) Co was present in the soil samples at themean level of 7558mgkg which is also less than standardvalue of 10mgkg The mean concentration of Cu in soilsamples was found to be 1812mgkg Ni was present in soilsamples at the mean level of 2216mgkg slightly higher thanthe recommended standard value of 20mgkg

The mean concentration of Cd was found to be0585mgkg a value slightly exceeding the standard valueof 05mgkg In fact fertilizers are added regularly to soilsto replenish N K and P for good crop growth Thesecompounds contain trace amounts of Cd as impuritieswhich after continued application are significantly increasedin the soil [44] Overall it was concluded that Pb Cr Cuand Co were present in tolerable range in the soil samples butNi and Cd surpassed the standard value but not to greaterextents Thus although the selected metals do not pose anythreat to the environment at their present levels but with thepassage of time the unwise use of agricultural activities maylead to a large buildup of metals in the soil that may endangerthe environment as well as human health

32 Correlation Coefficient Matrices of Various Parameters inthe Soil Table 3 depicted the correlation coefficient matrixfor the studied physicochemical parameters pesticides andmetal levels in the soil samples collected from the agriculturalfields The 119903-values were found to be significant at plusmn0231

(119901 lt 005) The data was characterized by both negative andpositive correlations between various pairs of parametersThe data was nonnormally distributed and also the anthro-pogenic activities led to a change in the natural concentrationof some of the parameters Thus all the observed correlationswere not high For the physicochemical parameters themost significant positive correlation was observed betweenelectrical conductivity and chloride levels with an 119903-value0292 evidencing that in about 292 cases the electricalconductivity of soil was observed to be increased with anincrease in chloride content and vice versa Similarly a strongpositive correlation was observed between pH and sulphatewith 119903-values of 0235 Organic carbon content of soil wasfound to be positively correlated with nitrate levels but thiscorrelation was not significant

The correlation coefficientmatrix for the levels of selectedmetals in the collected soil samples depicted the strongestpositive correlation between Cr and Ni at an 119903-value of 0460thereby showing that in 460 cases the concentration ofCr went in parallel with concentration of Ni thus sharing asimilar origin in the soil matrix The next strongest positivecorrelation was observed betweenNi and Cu pair (0431)Theother metal pair that was significantly positively correlatedincluded Cr-Co (119903-value 0343) Cr Ni and Cu were foundto be strongly negatively correlated with Cd (119903-values ofminus0407 minus0430 and minus0375 resp) depicting an increase inconcentration of one metal with a decrease in concentrationof other metals

No significant positive or negative correlation wasobserved among the selected pesticides depicting that thesources of pesticides in the soil were not the same Thisis also due to the fact that different pesticides are appliedto the crops at different stages of crop production Thusthey enter the soil at different periods of time The datacorresponding to the correlation coefficient matrix for thephysicochemical parameters and the various metals depictedonly few significant positivenegative correlations Ni ofthe soil exhibited the strongest positive correlation withits conductivity with 119903-value of 0342 Cu was also signifi-cantly positively correlated with the conductivity (119903-value of0286) Cd and electrical conductivitywere significantly nega-tively correlated Another significant negative correlationwasobserved between Cr and nitrate level of soil solution Theother correlations were too naıve to be discussed

The correlation coefficient matrix for the pesticides-to-physicochemical parameters depicted a significant neg-ative correlation between soil organic carbon content andemamectin thereby evidencing the influence of soil organiccarbon on the sorption of emamectin Soil EC values werealso found to be negatively correlated with imidacloprid andemamectin

Numerous metals are known to possess good catalysisability and they may affect the behavior of coexisting pes-ticides in the soil Thus the most important segment of thepresent investigation was to study the correlations among theselected pesticides and variousmetal levelsThe data depicteda strong positive correlation between acetamiprid and Cuwith 119903-value of 0239 A strong positive correlation pointedtowards an increase in the concentration of acetamiprid

8 Scientifica

Table3Correlationcoeffi

cientm

atrix

aforv

arious

parameterso

fsoilsam

ples

(119899=52)

PbCr

Co

CuNi

Cd

OCb

pHEC

cClminus

NO3

minus

SO4

2minus

Imd

Eme

Acf

Pb10

00Cr

0179

1000

Co

0019

034

310

00Cu

0018

0132minus0002

1000

Ni

0199

046

00074

0431

1000

Cd

minus0154minus040

7minus0045minus0375minus043

010

00OC(

)0124

0083

0092minus0136minus0039minus0075

1000

pH0080minus0162

0164minus0124minus0076

0118

0187

1000

EC(120583SCm

)minus000

9minus0045minus0047

028

6034

2minus024

50137

0059

1000

Clminus

(mgkg)minus0163minus0255minus0140minus0079

0034

0144

0083

0058

029

210

00NO3

minus

(mgkg)

0011

0018minus0221minus0065

0051minus0076

0213

0014

0153

0087

1000

SO4

2minus

(mgkg)minus0080minus0149minus0201minus0096minus0057

0146

000

40235minus0156

0212

0177

1000

Imlowast

0086minus0021

0012

0017minus0317

0021

0100

0175minus0314minus0122minus0103

0052

1000

Emlowast

0213minus0071

0161

000

9minus0012

0015minus0239

0084minus0265minus0163minus0183

0085minus0086

1000

Aclowast

minus0119

minus030

5minus0143

0239minus0102

0163minus0077

0099

0313

0038

0007minus0085

0050minus0174

1000

a 119903-valuesa

resig

nificantat0

231

at119901lt005

b OC=organicc

arbo

nc EC=ele

ctric

alcond

uctiv

itydIm

=im

idacloprideEm

=em

amectin

fAc

=acetam

iprid

lowast

Con

centratio

nin120583gg

Scientifica 9

Wardrsquos method

OC ()Imidacloprid

pH

CdAcetamiprid

Conductivity (120583Scm)CuCoNiCr

EmamectinPb

04 06 08 10 12 14 16 18 2002Linkage distance

Clminus (mgkg)

NO3minus (mgkg)

SO42minus (mgkg)

Figure 3 Cluster analysis for the determination of various parame-ters

with the presence of greater concentration of copper in thesoil On the other hand imidacloprid in soil was found tobe negatively correlated with Ni of soil (119903-value of minus0317)Similarly a significant negative correlation was observedbetween Cr and acetamiprid (119903-value minus0305) Thus it wasevidenced that Cu stabilizes acetamiprid while Cr and Nifacilitate the degradation of acetamiprid and imidacloprid inthe soil [45]

Similar results have been reported for pyrethroid pes-ticides whose degradation was shown to be inhibited bythe presence of copper ions Ellis et al reported that metalslike Cu present in soil may react with the sulfhydryl groupof enzymes and inhibit their activity Thus the pesticidesbecome more persistent thereby leading to an increase intheir concentration with time [21 46]

33 Cluster Analysis of Various Parameters in the Soil Sam-ples Cluster analysis has proved to be a milestone towardthe source apportionment studies of various pollutants likemetals and pesticides in the soil and other media [47 48]In this analysis (Figure 3) linkage distance is used as themeasure of degree of closeness and hence relation among thevarious parameters [49] A number of clusters were formedwithin a significant linkage distance The strongest clusterwas observed between Cr and Ni evidencing that high Crcontent of the soil was associated with the enhanced Nilevels These two metals were further associated with Co toform a second cluster within linkage distance of 10 Themost important cluster of the study was observed betweenacetamiprid and conductivity that was further associatedwith Cu It evidenced that Cu present in the soil may causethe persistence of acetamiprid whose concentration increaseswith time Similarly emamectin was closely associated withPd

Cluster analysis revealed a close association betweensulphate and pH which formed a primary cluster withinlinkage distance of 06 This primary cluster was furtherassociated with Cd and Clminus within linkage distance of 10 onone side and with imidacloprid in the soil on the other side

The organic carbon of soil was associated with nitrate withina linkage distance of 08 and this factor was further associatedwith previous cluster

Overall the study revealed that frequently used pesti-cides that is imidacloprid emamectin and acetamipridwere present in the soil of cotton fields and were influencedby factors such as soil pH and organic carbon The studyalso furnished correlations among pesticides and metals inthe soil It was shown that presence of certain metals such asNi caused the decreased levels of imidacloprid Similarly Crenhanced the degradation of acetamiprid and Cu caused thepersistence of this pesticide in the soil

4 Conclusions

The soil samples collected from the cotton growing area ofPakpattan Pakistan were slightly basic in nature The meanPb Cr Co and Cu levels were below NEQS while the levelsof Ni and Cd were slightly above NEQS These levels may betolerated by following precautionarymeasures in agriculturalactivities Among the pesticides emamectin exhibited a highpersistence in the soil that was closely associated with soilCu content It was also found that Cu stabilizes acetamipridwhile Cr and Ni facilitate the degradation of acetamipridand imidacloprid Thus the study provides basis for therisk assessment studies that are quite necessary to managethe contaminated sites in a cost effective manner whilepreserving the public and ecosystem health It also providesa management strategy for remediation of contaminatedsoil that is adding traces of Ni and Cr in the soil mayhelp in the degradation of frequently used acetamiprid andimidacloprid

Conflict of Interests

The authors declare no conflict of interests

References

[1] R A Cloyd and J A Bethke ldquoImpact of neonicotinoidinsecticides onnatural enemies in greenhouse and interiorscapeenvironmentsrdquo Pest Management Science vol 67 no 1 pp 3ndash92011

[2] P Khaliq L A Hashmi and M H Qazi ldquoAgriculture andenvironmentrdquo Progress Farming vol 15 pp 16ndash23 1995

[3] H Shiraishi F Pula A Otsuki and T Iwakuma ldquoBehaviourof pesticides in Lake Kasumugaura Japanrdquo Science of the TotalEnvironment vol 72 pp 29ndash42 1988

[4] R Rial Otero B Cancho Grande M Arias Estevez E LopezPeriago and J Simal Gandara ldquoProcedure for themeasurementof soil inputs of plant-protection agents washed off throughvineyard canopy by rainfallrdquo Journal of Agricultural and FoodChemistry vol 51 no 17 pp 5041ndash5046 2003

[5] H M G van der Werf ldquoAssessing the impact of pesticideson the environmentrdquo Agriculture Ecosystems and Environmentvol 60 no 2-3 pp 81ndash96 1996

[6] G W vanLoon and S J Duffy Environmental Chemistry AGlobal Perspective Oxford University Press Oxford UK 2ndedition 2005

10 Scientifica

[7] P K Goel Water Pollution (Causes Effects and Control) NewAge International (P) New Delhi India 2nd edition 2006

[8] M Arias-Estevez E Lopez-Periago E Martınez-Carballo JSimal-Gandara J-C Mejuto and L Garcıa-Rıo ldquoThe mobilityand degradation of pesticides in soils and the pollution ofgroundwater resourcesrdquo Agriculture Ecosystems amp Environ-ment vol 123 no 4 pp 247ndash260 2008

[9] P J Shea T A Machacek and S D Comfort ldquoAcceleratedremediation of pesticide-contaminated soil with zerovalentironrdquo Environmental Pollution vol 132 no 2 pp 183ndash188 2004

[10] A Isaiah and M Paul ldquoSynergistic effect of chemical pesticideson commonly grown vegetables in Northern Indiardquo Epidemiol-ogy vol 18 p S86 2007

[11] J Fenoll P Hellın C Marın C M Martınez and A PFlores ldquoMultiresidue analysis of pesticides in soil by gaschromatography with nitrogen-phosphorus detection and gaschromatography mass spectrometryrdquo Journal of Agriculturaland Food Chemistry vol 53 no 20 pp 7661ndash7666 2005

[12] S Seccia P FidenteDMontesano andPMorrica ldquoDetermina-tion of neonicotinoid insecticides residues in bovine milk sam-ples by solid-phase extraction clean-up and liquid chromatog-raphy with diode-array detectionrdquo Journal of ChromatographyA vol 1214 no 1-2 pp 115ndash120 2008

[13] S M Dem J M Cobb and D E Mullins ldquoPesticide residuesin soil and water from four cotton growing areas of Mali WestAfricardquo Journal of Agricultural Food amp Environmental Sciencesvol 1 no 1 pp 1ndash12 2007

[14] M W Aktar M Paramasivam D Sengupta S Purkait MGanguly and S Banerjee ldquoImpact assessment of pesticideresidues in fish of Ganga river around Kolkata in West BengalrdquoEnvironmental Monitoring and Assessment vol 157 no 1ndash4 pp97ndash104 2009

[15] T R Sandrin and R M Maier ldquoImpact of metals on thebiodegradation of organic pollutantsrdquo Environmental HealthPerspectives vol 111 no 8 pp 1093ndash1101 2003

[16] S Khan Q Cao Y M Zheng Y Z Huang and Y G ZhuldquoHealth risks of heavy metals in contaminated soils and foodcrops irrigated with wastewater in Beijing Chinardquo Environmen-tal Pollution vol 152 no 3 pp 686ndash692 2008

[17] M-K Zhang Z-Y Liu and H Wang ldquoUse of single extractionmethods to predict bioavailability of heavy metals in pollutedsoils to ricerdquo Communications in Soil Science amp Plant Analysisvol 41 no 7 pp 820ndash831 2010

[18] Y PWang J Y ShiHWangQ Lin X CChen andYXChenldquoThe influence of soil heavy metals pollution on soil microbialbiomass enzyme activity and community composition near acopper smelterrdquo Ecotoxicology amp Environmental Safety vol 67no 1 pp 75ndash81 2007

[19] A A Helal D M Imam S M Khalifa and H F AlyldquoInteraction of pesticides with humic compounds and theirmetal complexesrdquo Radiochemistry vol 48 no 4 pp 419ndash4252006

[20] H Tian J Li Z Mu L Li and Z Hao ldquoEffect of pH onDDT degradation in aqueous solution using bimetallic NiFenanoparticlesrdquo Separation amp Purification Technology vol 66no 1 pp 84ndash89 2009

[21] T-F Liu C Sun N Ta J Hong S-G Yang and C-X ChenldquoEffect of copper on the degradation of pesticides cypermethrinand cyhalothrinrdquo Journal of Environmental Sciences vol 19 no10 pp 1235ndash1238 2007

[22] E Quivet R Faure J Georges J-O Paısse and P LanterildquoInfluence of metal salts on the photodegradation of imazapyr

an imidazolinone pesticiderdquo Pest Management Science vol 62no 5 pp 407ndash413 2006

[23] M Kamiya andK Kameyama ldquoEffects of selectedmetal ions onphotodegradation of organophosphorus pesticides sensitizedby humic acidsrdquo Chemosphere vol 45 no 3 pp 231ndash235 2001

[24] M Radojevic and V N Bashkin Practical EnvironmentalAnalysis Royal Society of Chemistry Cambridge UK 1999

[25] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of selected metals in tan-nery effluents and related soilrdquo Journal of Hazardous Materialsvol 122 no 1-2 pp 17ndash22 2005

[26] G R Blake and K H Hartge ldquoBulk and particle densityrdquo inMethods of Soil Analysis Part 1 pp 363ndash382 Soil Science Societyof America Madison Wis USA 1986

[27] P Patnaik Handbook of Environmental Analysis ChemicalPollutants in Air Water Soil and SolidWastes CRC Lewis BocaRaton Fla USA 1997

[28] A Bartosova A Michalıkova M Sirotiak and M SoldanldquoComparison of two spectrophotometric techniques for nutri-ents analyses inwater samplesrdquoResearch Papers Faculty ofMate-rials Science and Technology SlovakUniversity of Technology vol20 no 32 pp 8ndash19 2013

[29] H Spiegel E Filcheva P Hegymegi A Gal and F G AVerheijen ldquoReview and comparison of methods used for soilorganic carbon determination part 2 laboratory studyrdquo SoilScience Agrochemistry and Ecology vol 41 no 4 pp 19ndash25 2007

[30] K H Tan Soil Sampling Preparation and Analysis CRC PressTaylor amp Francis Group Boca Raton Fla USA 2nd edition2005

[31] StatSoft Inc STATISTICA for Windows (Computer ProgramManual) StatSoft Tulsa Okla USA 1999

[32] USDA Soil Quality Indicator pH Natural Resources Conserva-tion Service 1998

[33] G E Lailach T DThompson and GW Brindley ldquoAbsorptionof pyrimidines purines and nucleosides by Co- Ni- Cu- andFe(III)-Montmorillonite (Clay-Organic Studies XIII)rdquo Claysand Clay Minerals vol 16 no 4 pp 295ndash301 1968

[34] R G NashW G Harris and C C Lewis ldquoSoil pH andmetallicamendment effects on DDT conversion to DDErdquo Journal ofEnvironmental Quality vol 2 no 3 pp 390ndash394 1973

[35] J G Konrad and G Chesters ldquoDegradation in soils of cioduman organophosphate insecticiderdquo Journal of Agricultural andFood Chemistry vol 17 no 2 pp 226ndash230 1969

[36] A Albarran R Celis M C Hermosın A Lopez-Pineiro and JCornejo ldquoBehavior of simazine in soil amended with the finalresidue of the olive-oil extraction processrdquo Chemosphere vol54 no 6 pp 717ndash724 2004

[37] J Dec and J-M Bollag ldquoDetermination of covalent and non-covalent binding interactions between xenobiotic chemicalsand soilrdquo Soil Science vol 162 no 12 pp 858ndash874 1997

[38] A Nawab A Aleem and A Malik ldquoDetermination oforganochlorine pesticides in agricultural soil with specialreference to 120574-HCH degradation by Pseudomonas strainsrdquoBioresource Technology vol 88 no 1 pp 41ndash46 2003

[39] M Bavcon P Trebse and L Zupancic-Kralj ldquoInvestigationsof the determination and transformations of diazinon andmalathion under environmental conditions using gas chro-matography coupled with a flame ionisation detectorrdquo Chemo-sphere vol 50 no 5 pp 595ndash601 2003

[40] S A Sassman L S Lee M Bischoff and R F Turco ldquoAssessingNN1015840-dibutylurea (DBU) formation in soils after application of

Scientifica 11

n-butylisocyanate and benlate fungicidesrdquo Journal of Agricul-tural and Food Chemistry vol 52 no 4 pp 747ndash754 2004

[41] E R Mouta M R Soares and J C Casagrande ldquoCopperadsorption as a function of solution parameters of variablecharge soilsrdquo Journal of the Brazilian Chemical Society vol 19no 5 pp 996ndash1009 2008

[42] M Arshad J Silvestre E Pinelli et al ldquoA field study oflead phytoextraction by various scented Pelargonium cultivarsrdquoChemosphere vol 71 no 11 pp 2187ndash2192 2008

[43] G Uzu S Sobanska Y Aliouane P Pradere and C DumatldquoStudy of lead phytoavailability for atmospheric industrialmicronic and sub-micronic particles in relation with leadspeciationrdquo Environmental Pollution vol 157 no 4 pp 1178ndash1185 2009

[44] L H P Jones and S C Jarvis ldquoThe fate of heavy metalsrdquo inTheChemistry of Soil Processes D J Green andMH B Hayes Edsp 593 John Wiley amp Sons New York NY USA 1981

[45] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of trace metal levels intannery effluents in relation to soil and water a case study fromPeshawar Pakistanrdquo Journal of EnvironmentalManagement vol79 no 1 pp 20ndash29 2006

[46] R J Ellis B Neish MW Trett et al ldquoComparison of microbialand meiofaunal community analyses for determining impact ofheavy metal contaminationrdquo Journal of Microbiological Meth-ods vol 45 no 3 pp 171ndash185 2001

[47] S R Tariq F Iqbal and A Ijaz ldquoAssessment and multivariateanalysis of metals in surgical instrument industry affected topsoils and groundwater for future reclamationrdquo InternationalJournal of Environment and Pollution vol 1 pp 54ndash71 2013

[48] S R Tariq and N Rashid ldquoMultivariate analysis of metal levelsin paddy soil rice plants and rice grains a case study fromShakargarh Pakistanrdquo Journal of Chemistry vol 2013 ArticleID 539251 10 pages 2013

[49] B S Everitt S Landau and M Leese Cluster Analysis Arnold4th edition 2001

Submit your manuscripts athttpwwwhindawicom

Nutrition and Metabolism

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Food ScienceInternational Journal of

Agronomy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom

Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Plant GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Biotechnology Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Forestry ResearchInternational Journal of

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Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

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Veterinary Medicine International

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Cell BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Evolutionary BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Scientifica 3

Chak 40

NA-166 Chak-149

Arifwala Chak-9

Chack Shan Karam

Baghu

Chak-97

Chak-67

River Sutlej

lowastlowastlowast

lowastlowast

Figure 1 Location map of sampling siteslowast

The chloride contents of the soil samples were deter-mined gravimetrically by using AgNO

3as precipitant [27]

In order to determine the sulphate ions a 100mL portionof water extract of soil samples was stirred for five minuteswith HCl and glycerol solutions along with approximately003 g of BaCl

2 Immediately after stirring the solution was

poured into a quartz cell with an optical path of 10 cmand the absorbance was measured at 420 nm on a UVspectrophotometer A series of calibration standards betweenconcentrations of 05 and 5mg SO

4

2minusL were prepared andused for drawing calibration curve [24]

Nitrate present in the soil samples was determined byusing the sodium salicylatemethod Here 100mL portions ofwater extract of each of the soil samples were evaporated with10mL of sodium salicylate and cooled to room temperatureSubsequently 10mL of concentrated H

2SO4was added to

dehumidify the entire residue and allowed to stand for 10minutes It was then quantitatively transferred to a 50mLvolumetric flask added with 70mL of NaOH and adjustedthe volume to 50mL with distilled water After 10 minutesthe absorbance was measured at 410 nm against the blankprepared in the same way Calibration curve was constructedby using the standard KNO

3solutions in the concentra-

tion range of 2ndash20mgL [28] The organic carbon contentsof the soil samples were determined by partial oxidationmethod that involved the titration of soil samples against1N (NH

4)2Fe(SO

4)2sdot6H2O solution by using diphenylamine

indicator [29]

Pesticide Analysis by HPLC The residues of selected pes-ticides that is imidacloprid acetamiprid and emamectinwere extracted from soil samples by using methanol as

solvent The extraction procedure adopted involved theshaking of the appropriate amount of soil samples with100mL of methanol on an orbital shaker for 30 minutesThe residual cake was extracted twice with 100mLmethanolThe methanol extracts were combined filtered and thenconcentrated under reduced pressure to dryness at 40∘C

Sample Cleanup The contaminated sample extracts cause theloss of detector sensitivity shorten the life time of columnproduce extraneous peaks and deteriorate peak resolutionand column efficiency [27]Therefore the extract was cleanedby using a Florasil packed column Briefly about 20 g ofFlorasil was added to a preconditioned chromatographiccolumn between two layers of anhydrous sodium sulphate (1to 2 cm deep) The concentrated extract was loaded onto thetop of the columnThe column was drained with acetonitrileuntil the sodium sulphate layer was exposed It was theneluted with mobile phase at a drip rate of about 5mLminMobile phase for HPLC analysis was prepared by mixing001 of acetic acid and acetonitrile in 60 40 ratio Theeluate was concentrated and residue was redissolved in 5mLof acetonitrile This cleaned extract was used for pesticideanalysis by HPLC

25 Metal Analysis by AAS Wet acid digestion method wasused for the analysis of metals present in soil samples Briefly10 g portions of air-dried and sieved soil samples were addedwith 15mL of 1 1 conc HNO

3and refluxed without boiling

at 95∘C for about 10ndash15 minutes It was further added with3mL of concentrated HNO

3and heating was continued for

about 30 minutes Subsequently the contents were cooled toroom temperature and added with about 5mL of 30 H

2O2

4 Scientifica

Table 1 Analytical parameters for the estimation of selected metals by AAS

Sr number Metal Wavelength (nm) Lamp current (mA) Slit width (nm) Fuel flow rate (Lmin) Detection limit (mgL)1 Pb 2833 90 13 22 0202 Cr 3593 90 13 28 0053 Co 2407 15 02 22 0204 Cu 3248 90 13 22 0025 Ni 2320 12 02 22 0106 Cd 2288 90 13 20 0005

in aliquots Digestion was continued until effervescencesubsided Then a 15mL portion of concentrated HCl wasadded and contents were cooled filtered through a sinteredglass crucible and finally diluted up to 50mL with distilledwater [30] This acid extract was aspirated directly onto AASfor metal estimation under optimum analytical conditions asgiven in Table 1

26 Statistical Analysis of Data The data set obtained forvarious physicochemical parameters metals and pesticideresidues in the representative soil samples was treated statis-tically by both univariate andmultivariate statistical analysesThe univariate statistical analysis involved the evaluationof basic statistical parameters like mean standard devia-tion standard error kurtosis and skewness and the linearcorrelation coefficient matrix Correlation coefficient matrixfurnished the correlation patterns among variousmetal pairsphysicochemical parameters and pesticides in the soilmediaMultiple correlation matrix was also developed in termsof metal-to-pesticide metal-to-physicochemical parametersand pesticide-to-physicochemical parameters to determinethe dependence of various parameters upon each other Themultivariate statistical analysis in terms of cluster analysis wasperformed to get an insight into the clustering behavior ofvarious parameters on mass scale by using Statistica software[31]

3 Results and Discussion

31 Distribution of Various Parameters of Soil Samples Phys-ical properties of the soil influence themobility and pathwaysof nutrients and pollutants within the soil Similarly the accu-mulation of the xenobiotics (foreign chemicals) in the soil isgoverned by a number of physicochemical parameters of soilsuch as its pH conductance and the amount of inorganicions (Clminus NO

3

minus SO4

2minus etc) It is therefore necessary toevaluate these physicochemical parameters and determinetheirmutual relationship so that a sustainable agriculturemaybe maintained

The basic statistics for the physicochemical parametersmetal levels and pesticide concentrations in fifty-two soilsamples collected from ten fields of Pakpattan Pakistan areenlisted in Table 2 The soil samples were grayish in colourand the texture of all the soil samples was sandy loam Thebulk density of soil samples was found to range from 153to 161Mgmminus3 with a mean value standing at 1568Mgmminus3pH another important parameter for the agricultural soilwas found to be present at narrow range of 76ndash85 with

a mean value of 81 Soils with these pH values exhibit higheravailability of metals such as Mg Ca and K while some othermetals such as Fe Zn and Cu are less available at this pH[32] It is also known that under alkaline conditions theadsorption of pesticides takes place to a lesser extent and thusthey degrade easily [33ndash35]

The organic matter content of soil is regarded as a majorfactor controlling the sorption transport and transformationof pesticides [36] For the present soil samples it was foundto vary from 129 to 1139 with a mean value of 4616 Anorganic carbon content of gt5 may enhance the sorptionof pesticides in soil depending on the nature of pesticidesand organic matter this in turn reduces the leaching andtransport properties of pesticides [37] In case of presentstudy the mean organic carbon content of soils was foundbelow 5 but slightly higher than background levelsThus inthese soils the extent of sorption of pesticides to the soil maynot be significant but this may be evidenced clearly on thebasis of amore comprehensive study based on chemometrics

The ionic strength of these soil samples is represented bya mean conductivity value of 1412 120583Scm signifying that alarger portion of solubilized cations and anions are presentin the water extracts of soil samples which were most likelyderived from the fertilizers and manure used to restore thefertility of soil It was further confirmed by the presence ofhigh concentration of anions such as chloride nitrate andsulphate in the soil samples

The mean chloride nitrate and sulphate levels recordedfor these soil samples were 129 3501 and 471mgg respec-tively with their sample variances of 377 times 107 1178 times 108and 466 times 108 respectivelyThe order of mean levels of theseanions thus remained SO

4

2minus

gt NO3

minus

gt Clminus Large values forstandard deviation projected a large spread of data set aroundthe mean value

The excessive sulphate concentration in the soil originatesfrom the use of zinc sulphate and urea in addition to decayedvegetablematter compost andmanure used to normalize thesoil pHThe enhanced levels of nitrate in the soil as comparedto background soil pointed towards an excessive use of nitratefertilizers such as nitrates of sodium potassium calcium andammonium in fields

The use of pesticides has contributed significantlytowards increased agricultural yield protection of livestockand the reduction of vector-transmitted diseases but theirimpacts on ecosystems and humans have always beenfocused on by scientific regulatory and policy communities[38ndash40] Imidacloprid acetamiprid and emamectin were

Scientifica 5

Table2Ba

sicstatisticsp

aram

etersfor

thed

istrib

utionof

selected

parameters(mgkg)insoilsamples

(119899=52)

Minim

umMaxim

umMean

Median

SDSE

Varia

nce

Kurtosis

Skew

ness

NEQ

SBClowast

Pb(m

gkg)

1093

2185

1618

1649

268

0372

7184

minus0639

minus0261

25189

Cr(m

gkg)

164

96586

5995

2238

031

5008

minus0902

minus0183

20503

Co(m

gkg)

293

124

7558

7595

2094

029

4386

minus0291

0077

100392

Cu(m

gkg)

1298

2190

1812

1856

2141

0297

4584

minus0332

minus0516

mdash276

Ni(mgkg)

153

2997

2216

2225

366

60508

1344

minus0572

0118

200135

Cd(m

gkg)

0347

1019

0585

0538

0175

0024

0031

0104

0961

05

014

Bulkdensity

(Mgmminus3

)15

3016

1015

6815

700028

0005

0001

minus13

33minus0003

mdashmdash

OC(

)12

911139

4616

3390

2894

0401

8376

minus0248

1074

mdash45

pH76

85

81

8055

02

0028

004

minus007

minus0206

mdash72

Con

ductivity

(120583Scm

)980

1887

1412

16005

3174

4402

1008times105

minus17

77minus0076

mdash108

Clminus

(mgkg)

4808

22438

12909

12338

61456

8522

3777times107

minus12

880271

mdash987

NO3

minus

(mgkg)

2879

94434

3500

934470

10852

1505

1178times108

1854

2807

mdash843

SO4

2minus

(mgkg)

400

9times103

9297times104

4710times104

40times104

2159times104

2993times103

466

0times108

1028

1447

mdash419

Imidacloprid

(120583gg)

23

2059

6445

556

6212

8613

3857

036

1229

mdashmdash

Emam

ectin

(120583gg)

0001

1305

2967

599

4312

598

1859times105

0414

1351

mdashmdash

Acetam

iprid

1140

12588

2643

704118

35711

169600

0968

1635

mdashmdash

lowast

BC=backgrou

ndlevels(m

eanof

three)

6 Scientifica

Moi

sture

cont

ent (

)

OC

()

pH

Box plot

Median

Nonoutlier range

Box plot

Imid

aclo

prid

Emam

ectin

Acet

amip

rid

Outliers

Cr Co Cu Ni CdPb

25ndash75

Median

Nonoutlier range 25ndash75

Median Nonoutlier range 25ndash75

OutliersMedian Nonoutlier range 25ndash75

minus5

0

5

10

15

20

25

30

35

minus200

0

200

400

600

800

1000

1200

1400

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

02468

101214161820

Clminus

(mg

kg)

NO3minus

(mg

kg)

SO42minus

(mg

kg)

Figure 2 Box and Whisker plots for the distribution of various parameters in soil

the pesticides that are being applied to the cotton crops ofPakpattan intermittently That is why these pesticides wereincluded in the study The data recorded a great variabilityin the concentrations of imidacloprid that was present ata minimum value of 23 120583gg and a maximum value of2059120583gg with a mean value standing at 6445 120583gg Thislarge variation in the recorded values reflected the differencesin the extent of exposure of soil to the pesticides Emamectinwas present in these samples at mean levels of 2967 120583ggwhile the mean levels for acetamiprid were 2643 120583gg Thelarge variation between themean andmedian values depictedthe nonnormal distribution of the data which was alsoreflected by high SD skewness and kurtosis values Thedistribution of these pesticides has also been depicted in Boxplots (Figure 2)

The data for the descriptive statistics of selected metals(ie Pb Cr Co Cu Ni and Cd Table 2 Figure 2) showedthat nickel in these samples was present at highest meanconcentration of 2216mgkg The major source of Ni inthese soils may be the Ni plating industry located nearbyNi was followed by Cu that exhibited a mean concentrationof 1812mgkg The minimum and maximum concentrationsrecorded for Cu were 1298 and 2190mgkg respectivelyCopper is required for various biochemical processes inplants thus it is an essential trace element but its enhancedconcentrations are hazardous for human populations [41]

Lead was another heavy metal that was present inthese samples at appreciable maximum concentration of1618mgkg Over the past few decades the vehicular emis-sions from leaded gasoline have been overcome due to ban

Scientifica 7

on leaded gasoline thus the source of this lead in soilwas traced in various fungicides and pesticides like leadarsenate and so forth that are used at various stages of cropproduction [2] Cadmium was the metal that was presentat trace level of 0585mgkg Chromium another hazardousmetal was found to be present at a mean level of 586mgkgIts maximum concentration was recorded to be 96mgkgwhich is quite higher than the limit set for agricultural soilsThis chromium not only is hazardous for soil biota butmay also contaminate the food chain through uptake andaccumulation by plants furthermore depending on the soilconditions like pH it may become soluble and thus enter thegroundwater the only source of drinking water in the area

The mean levels recorded for Co were 7558mgkg Theorder of themean concentrations ofmetals in the soil samplesremained Ni gt Cu gt Pb gt Co gt Cr gt Cd The symmetryparameters for the data that is standard deviation skewnessand kurtosis are also listed in Table 2

A comparison of mean metal levels with NationalEnvironmental Quality Standards (NEQS) is also depictedin Table 2 The average Pb concentration in soil sampleswas found to be 1618mgkg against the standard valueof 25mgkg The estimated value of lead in soil sampleswas lower than standard value which indicated that soil Pbwas below the contamination level and would not pose asignificant threat of contaminating the food chain MoreoverPb uptake by plants depends upon soil pH that is at higherpH lead becomes immobilized It is also known that due tosmall transfer factor Pb is not taken up by plants below aconcentration of 300120583gg in soil and if taken up it wouldaccumulate in leaves rather than the fruit [42 43]

Themean level of Cr recorded in soil was 586mgkgThisvalue is approximately four times less than standard value of20mgkg (NEQS) Co was present in the soil samples at themean level of 7558mgkg which is also less than standardvalue of 10mgkg The mean concentration of Cu in soilsamples was found to be 1812mgkg Ni was present in soilsamples at the mean level of 2216mgkg slightly higher thanthe recommended standard value of 20mgkg

The mean concentration of Cd was found to be0585mgkg a value slightly exceeding the standard valueof 05mgkg In fact fertilizers are added regularly to soilsto replenish N K and P for good crop growth Thesecompounds contain trace amounts of Cd as impuritieswhich after continued application are significantly increasedin the soil [44] Overall it was concluded that Pb Cr Cuand Co were present in tolerable range in the soil samples butNi and Cd surpassed the standard value but not to greaterextents Thus although the selected metals do not pose anythreat to the environment at their present levels but with thepassage of time the unwise use of agricultural activities maylead to a large buildup of metals in the soil that may endangerthe environment as well as human health

32 Correlation Coefficient Matrices of Various Parameters inthe Soil Table 3 depicted the correlation coefficient matrixfor the studied physicochemical parameters pesticides andmetal levels in the soil samples collected from the agriculturalfields The 119903-values were found to be significant at plusmn0231

(119901 lt 005) The data was characterized by both negative andpositive correlations between various pairs of parametersThe data was nonnormally distributed and also the anthro-pogenic activities led to a change in the natural concentrationof some of the parameters Thus all the observed correlationswere not high For the physicochemical parameters themost significant positive correlation was observed betweenelectrical conductivity and chloride levels with an 119903-value0292 evidencing that in about 292 cases the electricalconductivity of soil was observed to be increased with anincrease in chloride content and vice versa Similarly a strongpositive correlation was observed between pH and sulphatewith 119903-values of 0235 Organic carbon content of soil wasfound to be positively correlated with nitrate levels but thiscorrelation was not significant

The correlation coefficientmatrix for the levels of selectedmetals in the collected soil samples depicted the strongestpositive correlation between Cr and Ni at an 119903-value of 0460thereby showing that in 460 cases the concentration ofCr went in parallel with concentration of Ni thus sharing asimilar origin in the soil matrix The next strongest positivecorrelation was observed betweenNi and Cu pair (0431)Theother metal pair that was significantly positively correlatedincluded Cr-Co (119903-value 0343) Cr Ni and Cu were foundto be strongly negatively correlated with Cd (119903-values ofminus0407 minus0430 and minus0375 resp) depicting an increase inconcentration of one metal with a decrease in concentrationof other metals

No significant positive or negative correlation wasobserved among the selected pesticides depicting that thesources of pesticides in the soil were not the same Thisis also due to the fact that different pesticides are appliedto the crops at different stages of crop production Thusthey enter the soil at different periods of time The datacorresponding to the correlation coefficient matrix for thephysicochemical parameters and the various metals depictedonly few significant positivenegative correlations Ni ofthe soil exhibited the strongest positive correlation withits conductivity with 119903-value of 0342 Cu was also signifi-cantly positively correlated with the conductivity (119903-value of0286) Cd and electrical conductivitywere significantly nega-tively correlated Another significant negative correlationwasobserved between Cr and nitrate level of soil solution Theother correlations were too naıve to be discussed

The correlation coefficient matrix for the pesticides-to-physicochemical parameters depicted a significant neg-ative correlation between soil organic carbon content andemamectin thereby evidencing the influence of soil organiccarbon on the sorption of emamectin Soil EC values werealso found to be negatively correlated with imidacloprid andemamectin

Numerous metals are known to possess good catalysisability and they may affect the behavior of coexisting pes-ticides in the soil Thus the most important segment of thepresent investigation was to study the correlations among theselected pesticides and variousmetal levelsThe data depicteda strong positive correlation between acetamiprid and Cuwith 119903-value of 0239 A strong positive correlation pointedtowards an increase in the concentration of acetamiprid

8 Scientifica

Table3Correlationcoeffi

cientm

atrix

aforv

arious

parameterso

fsoilsam

ples

(119899=52)

PbCr

Co

CuNi

Cd

OCb

pHEC

cClminus

NO3

minus

SO4

2minus

Imd

Eme

Acf

Pb10

00Cr

0179

1000

Co

0019

034

310

00Cu

0018

0132minus0002

1000

Ni

0199

046

00074

0431

1000

Cd

minus0154minus040

7minus0045minus0375minus043

010

00OC(

)0124

0083

0092minus0136minus0039minus0075

1000

pH0080minus0162

0164minus0124minus0076

0118

0187

1000

EC(120583SCm

)minus000

9minus0045minus0047

028

6034

2minus024

50137

0059

1000

Clminus

(mgkg)minus0163minus0255minus0140minus0079

0034

0144

0083

0058

029

210

00NO3

minus

(mgkg)

0011

0018minus0221minus0065

0051minus0076

0213

0014

0153

0087

1000

SO4

2minus

(mgkg)minus0080minus0149minus0201minus0096minus0057

0146

000

40235minus0156

0212

0177

1000

Imlowast

0086minus0021

0012

0017minus0317

0021

0100

0175minus0314minus0122minus0103

0052

1000

Emlowast

0213minus0071

0161

000

9minus0012

0015minus0239

0084minus0265minus0163minus0183

0085minus0086

1000

Aclowast

minus0119

minus030

5minus0143

0239minus0102

0163minus0077

0099

0313

0038

0007minus0085

0050minus0174

1000

a 119903-valuesa

resig

nificantat0

231

at119901lt005

b OC=organicc

arbo

nc EC=ele

ctric

alcond

uctiv

itydIm

=im

idacloprideEm

=em

amectin

fAc

=acetam

iprid

lowast

Con

centratio

nin120583gg

Scientifica 9

Wardrsquos method

OC ()Imidacloprid

pH

CdAcetamiprid

Conductivity (120583Scm)CuCoNiCr

EmamectinPb

04 06 08 10 12 14 16 18 2002Linkage distance

Clminus (mgkg)

NO3minus (mgkg)

SO42minus (mgkg)

Figure 3 Cluster analysis for the determination of various parame-ters

with the presence of greater concentration of copper in thesoil On the other hand imidacloprid in soil was found tobe negatively correlated with Ni of soil (119903-value of minus0317)Similarly a significant negative correlation was observedbetween Cr and acetamiprid (119903-value minus0305) Thus it wasevidenced that Cu stabilizes acetamiprid while Cr and Nifacilitate the degradation of acetamiprid and imidacloprid inthe soil [45]

Similar results have been reported for pyrethroid pes-ticides whose degradation was shown to be inhibited bythe presence of copper ions Ellis et al reported that metalslike Cu present in soil may react with the sulfhydryl groupof enzymes and inhibit their activity Thus the pesticidesbecome more persistent thereby leading to an increase intheir concentration with time [21 46]

33 Cluster Analysis of Various Parameters in the Soil Sam-ples Cluster analysis has proved to be a milestone towardthe source apportionment studies of various pollutants likemetals and pesticides in the soil and other media [47 48]In this analysis (Figure 3) linkage distance is used as themeasure of degree of closeness and hence relation among thevarious parameters [49] A number of clusters were formedwithin a significant linkage distance The strongest clusterwas observed between Cr and Ni evidencing that high Crcontent of the soil was associated with the enhanced Nilevels These two metals were further associated with Co toform a second cluster within linkage distance of 10 Themost important cluster of the study was observed betweenacetamiprid and conductivity that was further associatedwith Cu It evidenced that Cu present in the soil may causethe persistence of acetamiprid whose concentration increaseswith time Similarly emamectin was closely associated withPd

Cluster analysis revealed a close association betweensulphate and pH which formed a primary cluster withinlinkage distance of 06 This primary cluster was furtherassociated with Cd and Clminus within linkage distance of 10 onone side and with imidacloprid in the soil on the other side

The organic carbon of soil was associated with nitrate withina linkage distance of 08 and this factor was further associatedwith previous cluster

Overall the study revealed that frequently used pesti-cides that is imidacloprid emamectin and acetamipridwere present in the soil of cotton fields and were influencedby factors such as soil pH and organic carbon The studyalso furnished correlations among pesticides and metals inthe soil It was shown that presence of certain metals such asNi caused the decreased levels of imidacloprid Similarly Crenhanced the degradation of acetamiprid and Cu caused thepersistence of this pesticide in the soil

4 Conclusions

The soil samples collected from the cotton growing area ofPakpattan Pakistan were slightly basic in nature The meanPb Cr Co and Cu levels were below NEQS while the levelsof Ni and Cd were slightly above NEQS These levels may betolerated by following precautionarymeasures in agriculturalactivities Among the pesticides emamectin exhibited a highpersistence in the soil that was closely associated with soilCu content It was also found that Cu stabilizes acetamipridwhile Cr and Ni facilitate the degradation of acetamipridand imidacloprid Thus the study provides basis for therisk assessment studies that are quite necessary to managethe contaminated sites in a cost effective manner whilepreserving the public and ecosystem health It also providesa management strategy for remediation of contaminatedsoil that is adding traces of Ni and Cr in the soil mayhelp in the degradation of frequently used acetamiprid andimidacloprid

Conflict of Interests

The authors declare no conflict of interests

References

[1] R A Cloyd and J A Bethke ldquoImpact of neonicotinoidinsecticides onnatural enemies in greenhouse and interiorscapeenvironmentsrdquo Pest Management Science vol 67 no 1 pp 3ndash92011

[2] P Khaliq L A Hashmi and M H Qazi ldquoAgriculture andenvironmentrdquo Progress Farming vol 15 pp 16ndash23 1995

[3] H Shiraishi F Pula A Otsuki and T Iwakuma ldquoBehaviourof pesticides in Lake Kasumugaura Japanrdquo Science of the TotalEnvironment vol 72 pp 29ndash42 1988

[4] R Rial Otero B Cancho Grande M Arias Estevez E LopezPeriago and J Simal Gandara ldquoProcedure for themeasurementof soil inputs of plant-protection agents washed off throughvineyard canopy by rainfallrdquo Journal of Agricultural and FoodChemistry vol 51 no 17 pp 5041ndash5046 2003

[5] H M G van der Werf ldquoAssessing the impact of pesticideson the environmentrdquo Agriculture Ecosystems and Environmentvol 60 no 2-3 pp 81ndash96 1996

[6] G W vanLoon and S J Duffy Environmental Chemistry AGlobal Perspective Oxford University Press Oxford UK 2ndedition 2005

10 Scientifica

[7] P K Goel Water Pollution (Causes Effects and Control) NewAge International (P) New Delhi India 2nd edition 2006

[8] M Arias-Estevez E Lopez-Periago E Martınez-Carballo JSimal-Gandara J-C Mejuto and L Garcıa-Rıo ldquoThe mobilityand degradation of pesticides in soils and the pollution ofgroundwater resourcesrdquo Agriculture Ecosystems amp Environ-ment vol 123 no 4 pp 247ndash260 2008

[9] P J Shea T A Machacek and S D Comfort ldquoAcceleratedremediation of pesticide-contaminated soil with zerovalentironrdquo Environmental Pollution vol 132 no 2 pp 183ndash188 2004

[10] A Isaiah and M Paul ldquoSynergistic effect of chemical pesticideson commonly grown vegetables in Northern Indiardquo Epidemiol-ogy vol 18 p S86 2007

[11] J Fenoll P Hellın C Marın C M Martınez and A PFlores ldquoMultiresidue analysis of pesticides in soil by gaschromatography with nitrogen-phosphorus detection and gaschromatography mass spectrometryrdquo Journal of Agriculturaland Food Chemistry vol 53 no 20 pp 7661ndash7666 2005

[12] S Seccia P FidenteDMontesano andPMorrica ldquoDetermina-tion of neonicotinoid insecticides residues in bovine milk sam-ples by solid-phase extraction clean-up and liquid chromatog-raphy with diode-array detectionrdquo Journal of ChromatographyA vol 1214 no 1-2 pp 115ndash120 2008

[13] S M Dem J M Cobb and D E Mullins ldquoPesticide residuesin soil and water from four cotton growing areas of Mali WestAfricardquo Journal of Agricultural Food amp Environmental Sciencesvol 1 no 1 pp 1ndash12 2007

[14] M W Aktar M Paramasivam D Sengupta S Purkait MGanguly and S Banerjee ldquoImpact assessment of pesticideresidues in fish of Ganga river around Kolkata in West BengalrdquoEnvironmental Monitoring and Assessment vol 157 no 1ndash4 pp97ndash104 2009

[15] T R Sandrin and R M Maier ldquoImpact of metals on thebiodegradation of organic pollutantsrdquo Environmental HealthPerspectives vol 111 no 8 pp 1093ndash1101 2003

[16] S Khan Q Cao Y M Zheng Y Z Huang and Y G ZhuldquoHealth risks of heavy metals in contaminated soils and foodcrops irrigated with wastewater in Beijing Chinardquo Environmen-tal Pollution vol 152 no 3 pp 686ndash692 2008

[17] M-K Zhang Z-Y Liu and H Wang ldquoUse of single extractionmethods to predict bioavailability of heavy metals in pollutedsoils to ricerdquo Communications in Soil Science amp Plant Analysisvol 41 no 7 pp 820ndash831 2010

[18] Y PWang J Y ShiHWangQ Lin X CChen andYXChenldquoThe influence of soil heavy metals pollution on soil microbialbiomass enzyme activity and community composition near acopper smelterrdquo Ecotoxicology amp Environmental Safety vol 67no 1 pp 75ndash81 2007

[19] A A Helal D M Imam S M Khalifa and H F AlyldquoInteraction of pesticides with humic compounds and theirmetal complexesrdquo Radiochemistry vol 48 no 4 pp 419ndash4252006

[20] H Tian J Li Z Mu L Li and Z Hao ldquoEffect of pH onDDT degradation in aqueous solution using bimetallic NiFenanoparticlesrdquo Separation amp Purification Technology vol 66no 1 pp 84ndash89 2009

[21] T-F Liu C Sun N Ta J Hong S-G Yang and C-X ChenldquoEffect of copper on the degradation of pesticides cypermethrinand cyhalothrinrdquo Journal of Environmental Sciences vol 19 no10 pp 1235ndash1238 2007

[22] E Quivet R Faure J Georges J-O Paısse and P LanterildquoInfluence of metal salts on the photodegradation of imazapyr

an imidazolinone pesticiderdquo Pest Management Science vol 62no 5 pp 407ndash413 2006

[23] M Kamiya andK Kameyama ldquoEffects of selectedmetal ions onphotodegradation of organophosphorus pesticides sensitizedby humic acidsrdquo Chemosphere vol 45 no 3 pp 231ndash235 2001

[24] M Radojevic and V N Bashkin Practical EnvironmentalAnalysis Royal Society of Chemistry Cambridge UK 1999

[25] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of selected metals in tan-nery effluents and related soilrdquo Journal of Hazardous Materialsvol 122 no 1-2 pp 17ndash22 2005

[26] G R Blake and K H Hartge ldquoBulk and particle densityrdquo inMethods of Soil Analysis Part 1 pp 363ndash382 Soil Science Societyof America Madison Wis USA 1986

[27] P Patnaik Handbook of Environmental Analysis ChemicalPollutants in Air Water Soil and SolidWastes CRC Lewis BocaRaton Fla USA 1997

[28] A Bartosova A Michalıkova M Sirotiak and M SoldanldquoComparison of two spectrophotometric techniques for nutri-ents analyses inwater samplesrdquoResearch Papers Faculty ofMate-rials Science and Technology SlovakUniversity of Technology vol20 no 32 pp 8ndash19 2013

[29] H Spiegel E Filcheva P Hegymegi A Gal and F G AVerheijen ldquoReview and comparison of methods used for soilorganic carbon determination part 2 laboratory studyrdquo SoilScience Agrochemistry and Ecology vol 41 no 4 pp 19ndash25 2007

[30] K H Tan Soil Sampling Preparation and Analysis CRC PressTaylor amp Francis Group Boca Raton Fla USA 2nd edition2005

[31] StatSoft Inc STATISTICA for Windows (Computer ProgramManual) StatSoft Tulsa Okla USA 1999

[32] USDA Soil Quality Indicator pH Natural Resources Conserva-tion Service 1998

[33] G E Lailach T DThompson and GW Brindley ldquoAbsorptionof pyrimidines purines and nucleosides by Co- Ni- Cu- andFe(III)-Montmorillonite (Clay-Organic Studies XIII)rdquo Claysand Clay Minerals vol 16 no 4 pp 295ndash301 1968

[34] R G NashW G Harris and C C Lewis ldquoSoil pH andmetallicamendment effects on DDT conversion to DDErdquo Journal ofEnvironmental Quality vol 2 no 3 pp 390ndash394 1973

[35] J G Konrad and G Chesters ldquoDegradation in soils of cioduman organophosphate insecticiderdquo Journal of Agricultural andFood Chemistry vol 17 no 2 pp 226ndash230 1969

[36] A Albarran R Celis M C Hermosın A Lopez-Pineiro and JCornejo ldquoBehavior of simazine in soil amended with the finalresidue of the olive-oil extraction processrdquo Chemosphere vol54 no 6 pp 717ndash724 2004

[37] J Dec and J-M Bollag ldquoDetermination of covalent and non-covalent binding interactions between xenobiotic chemicalsand soilrdquo Soil Science vol 162 no 12 pp 858ndash874 1997

[38] A Nawab A Aleem and A Malik ldquoDetermination oforganochlorine pesticides in agricultural soil with specialreference to 120574-HCH degradation by Pseudomonas strainsrdquoBioresource Technology vol 88 no 1 pp 41ndash46 2003

[39] M Bavcon P Trebse and L Zupancic-Kralj ldquoInvestigationsof the determination and transformations of diazinon andmalathion under environmental conditions using gas chro-matography coupled with a flame ionisation detectorrdquo Chemo-sphere vol 50 no 5 pp 595ndash601 2003

[40] S A Sassman L S Lee M Bischoff and R F Turco ldquoAssessingNN1015840-dibutylurea (DBU) formation in soils after application of

Scientifica 11

n-butylisocyanate and benlate fungicidesrdquo Journal of Agricul-tural and Food Chemistry vol 52 no 4 pp 747ndash754 2004

[41] E R Mouta M R Soares and J C Casagrande ldquoCopperadsorption as a function of solution parameters of variablecharge soilsrdquo Journal of the Brazilian Chemical Society vol 19no 5 pp 996ndash1009 2008

[42] M Arshad J Silvestre E Pinelli et al ldquoA field study oflead phytoextraction by various scented Pelargonium cultivarsrdquoChemosphere vol 71 no 11 pp 2187ndash2192 2008

[43] G Uzu S Sobanska Y Aliouane P Pradere and C DumatldquoStudy of lead phytoavailability for atmospheric industrialmicronic and sub-micronic particles in relation with leadspeciationrdquo Environmental Pollution vol 157 no 4 pp 1178ndash1185 2009

[44] L H P Jones and S C Jarvis ldquoThe fate of heavy metalsrdquo inTheChemistry of Soil Processes D J Green andMH B Hayes Edsp 593 John Wiley amp Sons New York NY USA 1981

[45] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of trace metal levels intannery effluents in relation to soil and water a case study fromPeshawar Pakistanrdquo Journal of EnvironmentalManagement vol79 no 1 pp 20ndash29 2006

[46] R J Ellis B Neish MW Trett et al ldquoComparison of microbialand meiofaunal community analyses for determining impact ofheavy metal contaminationrdquo Journal of Microbiological Meth-ods vol 45 no 3 pp 171ndash185 2001

[47] S R Tariq F Iqbal and A Ijaz ldquoAssessment and multivariateanalysis of metals in surgical instrument industry affected topsoils and groundwater for future reclamationrdquo InternationalJournal of Environment and Pollution vol 1 pp 54ndash71 2013

[48] S R Tariq and N Rashid ldquoMultivariate analysis of metal levelsin paddy soil rice plants and rice grains a case study fromShakargarh Pakistanrdquo Journal of Chemistry vol 2013 ArticleID 539251 10 pages 2013

[49] B S Everitt S Landau and M Leese Cluster Analysis Arnold4th edition 2001

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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

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Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Plant GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Biotechnology Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Forestry ResearchInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Veterinary Medicine International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Cell BiologyInternational Journal of

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Evolutionary BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

4 Scientifica

Table 1 Analytical parameters for the estimation of selected metals by AAS

Sr number Metal Wavelength (nm) Lamp current (mA) Slit width (nm) Fuel flow rate (Lmin) Detection limit (mgL)1 Pb 2833 90 13 22 0202 Cr 3593 90 13 28 0053 Co 2407 15 02 22 0204 Cu 3248 90 13 22 0025 Ni 2320 12 02 22 0106 Cd 2288 90 13 20 0005

in aliquots Digestion was continued until effervescencesubsided Then a 15mL portion of concentrated HCl wasadded and contents were cooled filtered through a sinteredglass crucible and finally diluted up to 50mL with distilledwater [30] This acid extract was aspirated directly onto AASfor metal estimation under optimum analytical conditions asgiven in Table 1

26 Statistical Analysis of Data The data set obtained forvarious physicochemical parameters metals and pesticideresidues in the representative soil samples was treated statis-tically by both univariate andmultivariate statistical analysesThe univariate statistical analysis involved the evaluationof basic statistical parameters like mean standard devia-tion standard error kurtosis and skewness and the linearcorrelation coefficient matrix Correlation coefficient matrixfurnished the correlation patterns among variousmetal pairsphysicochemical parameters and pesticides in the soilmediaMultiple correlation matrix was also developed in termsof metal-to-pesticide metal-to-physicochemical parametersand pesticide-to-physicochemical parameters to determinethe dependence of various parameters upon each other Themultivariate statistical analysis in terms of cluster analysis wasperformed to get an insight into the clustering behavior ofvarious parameters on mass scale by using Statistica software[31]

3 Results and Discussion

31 Distribution of Various Parameters of Soil Samples Phys-ical properties of the soil influence themobility and pathwaysof nutrients and pollutants within the soil Similarly the accu-mulation of the xenobiotics (foreign chemicals) in the soil isgoverned by a number of physicochemical parameters of soilsuch as its pH conductance and the amount of inorganicions (Clminus NO

3

minus SO4

2minus etc) It is therefore necessary toevaluate these physicochemical parameters and determinetheirmutual relationship so that a sustainable agriculturemaybe maintained

The basic statistics for the physicochemical parametersmetal levels and pesticide concentrations in fifty-two soilsamples collected from ten fields of Pakpattan Pakistan areenlisted in Table 2 The soil samples were grayish in colourand the texture of all the soil samples was sandy loam Thebulk density of soil samples was found to range from 153to 161Mgmminus3 with a mean value standing at 1568Mgmminus3pH another important parameter for the agricultural soilwas found to be present at narrow range of 76ndash85 with

a mean value of 81 Soils with these pH values exhibit higheravailability of metals such as Mg Ca and K while some othermetals such as Fe Zn and Cu are less available at this pH[32] It is also known that under alkaline conditions theadsorption of pesticides takes place to a lesser extent and thusthey degrade easily [33ndash35]

The organic matter content of soil is regarded as a majorfactor controlling the sorption transport and transformationof pesticides [36] For the present soil samples it was foundto vary from 129 to 1139 with a mean value of 4616 Anorganic carbon content of gt5 may enhance the sorptionof pesticides in soil depending on the nature of pesticidesand organic matter this in turn reduces the leaching andtransport properties of pesticides [37] In case of presentstudy the mean organic carbon content of soils was foundbelow 5 but slightly higher than background levelsThus inthese soils the extent of sorption of pesticides to the soil maynot be significant but this may be evidenced clearly on thebasis of amore comprehensive study based on chemometrics

The ionic strength of these soil samples is represented bya mean conductivity value of 1412 120583Scm signifying that alarger portion of solubilized cations and anions are presentin the water extracts of soil samples which were most likelyderived from the fertilizers and manure used to restore thefertility of soil It was further confirmed by the presence ofhigh concentration of anions such as chloride nitrate andsulphate in the soil samples

The mean chloride nitrate and sulphate levels recordedfor these soil samples were 129 3501 and 471mgg respec-tively with their sample variances of 377 times 107 1178 times 108and 466 times 108 respectivelyThe order of mean levels of theseanions thus remained SO

4

2minus

gt NO3

minus

gt Clminus Large values forstandard deviation projected a large spread of data set aroundthe mean value

The excessive sulphate concentration in the soil originatesfrom the use of zinc sulphate and urea in addition to decayedvegetablematter compost andmanure used to normalize thesoil pHThe enhanced levels of nitrate in the soil as comparedto background soil pointed towards an excessive use of nitratefertilizers such as nitrates of sodium potassium calcium andammonium in fields

The use of pesticides has contributed significantlytowards increased agricultural yield protection of livestockand the reduction of vector-transmitted diseases but theirimpacts on ecosystems and humans have always beenfocused on by scientific regulatory and policy communities[38ndash40] Imidacloprid acetamiprid and emamectin were

Scientifica 5

Table2Ba

sicstatisticsp

aram

etersfor

thed

istrib

utionof

selected

parameters(mgkg)insoilsamples

(119899=52)

Minim

umMaxim

umMean

Median

SDSE

Varia

nce

Kurtosis

Skew

ness

NEQ

SBClowast

Pb(m

gkg)

1093

2185

1618

1649

268

0372

7184

minus0639

minus0261

25189

Cr(m

gkg)

164

96586

5995

2238

031

5008

minus0902

minus0183

20503

Co(m

gkg)

293

124

7558

7595

2094

029

4386

minus0291

0077

100392

Cu(m

gkg)

1298

2190

1812

1856

2141

0297

4584

minus0332

minus0516

mdash276

Ni(mgkg)

153

2997

2216

2225

366

60508

1344

minus0572

0118

200135

Cd(m

gkg)

0347

1019

0585

0538

0175

0024

0031

0104

0961

05

014

Bulkdensity

(Mgmminus3

)15

3016

1015

6815

700028

0005

0001

minus13

33minus0003

mdashmdash

OC(

)12

911139

4616

3390

2894

0401

8376

minus0248

1074

mdash45

pH76

85

81

8055

02

0028

004

minus007

minus0206

mdash72

Con

ductivity

(120583Scm

)980

1887

1412

16005

3174

4402

1008times105

minus17

77minus0076

mdash108

Clminus

(mgkg)

4808

22438

12909

12338

61456

8522

3777times107

minus12

880271

mdash987

NO3

minus

(mgkg)

2879

94434

3500

934470

10852

1505

1178times108

1854

2807

mdash843

SO4

2minus

(mgkg)

400

9times103

9297times104

4710times104

40times104

2159times104

2993times103

466

0times108

1028

1447

mdash419

Imidacloprid

(120583gg)

23

2059

6445

556

6212

8613

3857

036

1229

mdashmdash

Emam

ectin

(120583gg)

0001

1305

2967

599

4312

598

1859times105

0414

1351

mdashmdash

Acetam

iprid

1140

12588

2643

704118

35711

169600

0968

1635

mdashmdash

lowast

BC=backgrou

ndlevels(m

eanof

three)

6 Scientifica

Moi

sture

cont

ent (

)

OC

()

pH

Box plot

Median

Nonoutlier range

Box plot

Imid

aclo

prid

Emam

ectin

Acet

amip

rid

Outliers

Cr Co Cu Ni CdPb

25ndash75

Median

Nonoutlier range 25ndash75

Median Nonoutlier range 25ndash75

OutliersMedian Nonoutlier range 25ndash75

minus5

0

5

10

15

20

25

30

35

minus200

0

200

400

600

800

1000

1200

1400

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

02468

101214161820

Clminus

(mg

kg)

NO3minus

(mg

kg)

SO42minus

(mg

kg)

Figure 2 Box and Whisker plots for the distribution of various parameters in soil

the pesticides that are being applied to the cotton crops ofPakpattan intermittently That is why these pesticides wereincluded in the study The data recorded a great variabilityin the concentrations of imidacloprid that was present ata minimum value of 23 120583gg and a maximum value of2059120583gg with a mean value standing at 6445 120583gg Thislarge variation in the recorded values reflected the differencesin the extent of exposure of soil to the pesticides Emamectinwas present in these samples at mean levels of 2967 120583ggwhile the mean levels for acetamiprid were 2643 120583gg Thelarge variation between themean andmedian values depictedthe nonnormal distribution of the data which was alsoreflected by high SD skewness and kurtosis values Thedistribution of these pesticides has also been depicted in Boxplots (Figure 2)

The data for the descriptive statistics of selected metals(ie Pb Cr Co Cu Ni and Cd Table 2 Figure 2) showedthat nickel in these samples was present at highest meanconcentration of 2216mgkg The major source of Ni inthese soils may be the Ni plating industry located nearbyNi was followed by Cu that exhibited a mean concentrationof 1812mgkg The minimum and maximum concentrationsrecorded for Cu were 1298 and 2190mgkg respectivelyCopper is required for various biochemical processes inplants thus it is an essential trace element but its enhancedconcentrations are hazardous for human populations [41]

Lead was another heavy metal that was present inthese samples at appreciable maximum concentration of1618mgkg Over the past few decades the vehicular emis-sions from leaded gasoline have been overcome due to ban

Scientifica 7

on leaded gasoline thus the source of this lead in soilwas traced in various fungicides and pesticides like leadarsenate and so forth that are used at various stages of cropproduction [2] Cadmium was the metal that was presentat trace level of 0585mgkg Chromium another hazardousmetal was found to be present at a mean level of 586mgkgIts maximum concentration was recorded to be 96mgkgwhich is quite higher than the limit set for agricultural soilsThis chromium not only is hazardous for soil biota butmay also contaminate the food chain through uptake andaccumulation by plants furthermore depending on the soilconditions like pH it may become soluble and thus enter thegroundwater the only source of drinking water in the area

The mean levels recorded for Co were 7558mgkg Theorder of themean concentrations ofmetals in the soil samplesremained Ni gt Cu gt Pb gt Co gt Cr gt Cd The symmetryparameters for the data that is standard deviation skewnessand kurtosis are also listed in Table 2

A comparison of mean metal levels with NationalEnvironmental Quality Standards (NEQS) is also depictedin Table 2 The average Pb concentration in soil sampleswas found to be 1618mgkg against the standard valueof 25mgkg The estimated value of lead in soil sampleswas lower than standard value which indicated that soil Pbwas below the contamination level and would not pose asignificant threat of contaminating the food chain MoreoverPb uptake by plants depends upon soil pH that is at higherpH lead becomes immobilized It is also known that due tosmall transfer factor Pb is not taken up by plants below aconcentration of 300120583gg in soil and if taken up it wouldaccumulate in leaves rather than the fruit [42 43]

Themean level of Cr recorded in soil was 586mgkgThisvalue is approximately four times less than standard value of20mgkg (NEQS) Co was present in the soil samples at themean level of 7558mgkg which is also less than standardvalue of 10mgkg The mean concentration of Cu in soilsamples was found to be 1812mgkg Ni was present in soilsamples at the mean level of 2216mgkg slightly higher thanthe recommended standard value of 20mgkg

The mean concentration of Cd was found to be0585mgkg a value slightly exceeding the standard valueof 05mgkg In fact fertilizers are added regularly to soilsto replenish N K and P for good crop growth Thesecompounds contain trace amounts of Cd as impuritieswhich after continued application are significantly increasedin the soil [44] Overall it was concluded that Pb Cr Cuand Co were present in tolerable range in the soil samples butNi and Cd surpassed the standard value but not to greaterextents Thus although the selected metals do not pose anythreat to the environment at their present levels but with thepassage of time the unwise use of agricultural activities maylead to a large buildup of metals in the soil that may endangerthe environment as well as human health

32 Correlation Coefficient Matrices of Various Parameters inthe Soil Table 3 depicted the correlation coefficient matrixfor the studied physicochemical parameters pesticides andmetal levels in the soil samples collected from the agriculturalfields The 119903-values were found to be significant at plusmn0231

(119901 lt 005) The data was characterized by both negative andpositive correlations between various pairs of parametersThe data was nonnormally distributed and also the anthro-pogenic activities led to a change in the natural concentrationof some of the parameters Thus all the observed correlationswere not high For the physicochemical parameters themost significant positive correlation was observed betweenelectrical conductivity and chloride levels with an 119903-value0292 evidencing that in about 292 cases the electricalconductivity of soil was observed to be increased with anincrease in chloride content and vice versa Similarly a strongpositive correlation was observed between pH and sulphatewith 119903-values of 0235 Organic carbon content of soil wasfound to be positively correlated with nitrate levels but thiscorrelation was not significant

The correlation coefficientmatrix for the levels of selectedmetals in the collected soil samples depicted the strongestpositive correlation between Cr and Ni at an 119903-value of 0460thereby showing that in 460 cases the concentration ofCr went in parallel with concentration of Ni thus sharing asimilar origin in the soil matrix The next strongest positivecorrelation was observed betweenNi and Cu pair (0431)Theother metal pair that was significantly positively correlatedincluded Cr-Co (119903-value 0343) Cr Ni and Cu were foundto be strongly negatively correlated with Cd (119903-values ofminus0407 minus0430 and minus0375 resp) depicting an increase inconcentration of one metal with a decrease in concentrationof other metals

No significant positive or negative correlation wasobserved among the selected pesticides depicting that thesources of pesticides in the soil were not the same Thisis also due to the fact that different pesticides are appliedto the crops at different stages of crop production Thusthey enter the soil at different periods of time The datacorresponding to the correlation coefficient matrix for thephysicochemical parameters and the various metals depictedonly few significant positivenegative correlations Ni ofthe soil exhibited the strongest positive correlation withits conductivity with 119903-value of 0342 Cu was also signifi-cantly positively correlated with the conductivity (119903-value of0286) Cd and electrical conductivitywere significantly nega-tively correlated Another significant negative correlationwasobserved between Cr and nitrate level of soil solution Theother correlations were too naıve to be discussed

The correlation coefficient matrix for the pesticides-to-physicochemical parameters depicted a significant neg-ative correlation between soil organic carbon content andemamectin thereby evidencing the influence of soil organiccarbon on the sorption of emamectin Soil EC values werealso found to be negatively correlated with imidacloprid andemamectin

Numerous metals are known to possess good catalysisability and they may affect the behavior of coexisting pes-ticides in the soil Thus the most important segment of thepresent investigation was to study the correlations among theselected pesticides and variousmetal levelsThe data depicteda strong positive correlation between acetamiprid and Cuwith 119903-value of 0239 A strong positive correlation pointedtowards an increase in the concentration of acetamiprid

8 Scientifica

Table3Correlationcoeffi

cientm

atrix

aforv

arious

parameterso

fsoilsam

ples

(119899=52)

PbCr

Co

CuNi

Cd

OCb

pHEC

cClminus

NO3

minus

SO4

2minus

Imd

Eme

Acf

Pb10

00Cr

0179

1000

Co

0019

034

310

00Cu

0018

0132minus0002

1000

Ni

0199

046

00074

0431

1000

Cd

minus0154minus040

7minus0045minus0375minus043

010

00OC(

)0124

0083

0092minus0136minus0039minus0075

1000

pH0080minus0162

0164minus0124minus0076

0118

0187

1000

EC(120583SCm

)minus000

9minus0045minus0047

028

6034

2minus024

50137

0059

1000

Clminus

(mgkg)minus0163minus0255minus0140minus0079

0034

0144

0083

0058

029

210

00NO3

minus

(mgkg)

0011

0018minus0221minus0065

0051minus0076

0213

0014

0153

0087

1000

SO4

2minus

(mgkg)minus0080minus0149minus0201minus0096minus0057

0146

000

40235minus0156

0212

0177

1000

Imlowast

0086minus0021

0012

0017minus0317

0021

0100

0175minus0314minus0122minus0103

0052

1000

Emlowast

0213minus0071

0161

000

9minus0012

0015minus0239

0084minus0265minus0163minus0183

0085minus0086

1000

Aclowast

minus0119

minus030

5minus0143

0239minus0102

0163minus0077

0099

0313

0038

0007minus0085

0050minus0174

1000

a 119903-valuesa

resig

nificantat0

231

at119901lt005

b OC=organicc

arbo

nc EC=ele

ctric

alcond

uctiv

itydIm

=im

idacloprideEm

=em

amectin

fAc

=acetam

iprid

lowast

Con

centratio

nin120583gg

Scientifica 9

Wardrsquos method

OC ()Imidacloprid

pH

CdAcetamiprid

Conductivity (120583Scm)CuCoNiCr

EmamectinPb

04 06 08 10 12 14 16 18 2002Linkage distance

Clminus (mgkg)

NO3minus (mgkg)

SO42minus (mgkg)

Figure 3 Cluster analysis for the determination of various parame-ters

with the presence of greater concentration of copper in thesoil On the other hand imidacloprid in soil was found tobe negatively correlated with Ni of soil (119903-value of minus0317)Similarly a significant negative correlation was observedbetween Cr and acetamiprid (119903-value minus0305) Thus it wasevidenced that Cu stabilizes acetamiprid while Cr and Nifacilitate the degradation of acetamiprid and imidacloprid inthe soil [45]

Similar results have been reported for pyrethroid pes-ticides whose degradation was shown to be inhibited bythe presence of copper ions Ellis et al reported that metalslike Cu present in soil may react with the sulfhydryl groupof enzymes and inhibit their activity Thus the pesticidesbecome more persistent thereby leading to an increase intheir concentration with time [21 46]

33 Cluster Analysis of Various Parameters in the Soil Sam-ples Cluster analysis has proved to be a milestone towardthe source apportionment studies of various pollutants likemetals and pesticides in the soil and other media [47 48]In this analysis (Figure 3) linkage distance is used as themeasure of degree of closeness and hence relation among thevarious parameters [49] A number of clusters were formedwithin a significant linkage distance The strongest clusterwas observed between Cr and Ni evidencing that high Crcontent of the soil was associated with the enhanced Nilevels These two metals were further associated with Co toform a second cluster within linkage distance of 10 Themost important cluster of the study was observed betweenacetamiprid and conductivity that was further associatedwith Cu It evidenced that Cu present in the soil may causethe persistence of acetamiprid whose concentration increaseswith time Similarly emamectin was closely associated withPd

Cluster analysis revealed a close association betweensulphate and pH which formed a primary cluster withinlinkage distance of 06 This primary cluster was furtherassociated with Cd and Clminus within linkage distance of 10 onone side and with imidacloprid in the soil on the other side

The organic carbon of soil was associated with nitrate withina linkage distance of 08 and this factor was further associatedwith previous cluster

Overall the study revealed that frequently used pesti-cides that is imidacloprid emamectin and acetamipridwere present in the soil of cotton fields and were influencedby factors such as soil pH and organic carbon The studyalso furnished correlations among pesticides and metals inthe soil It was shown that presence of certain metals such asNi caused the decreased levels of imidacloprid Similarly Crenhanced the degradation of acetamiprid and Cu caused thepersistence of this pesticide in the soil

4 Conclusions

The soil samples collected from the cotton growing area ofPakpattan Pakistan were slightly basic in nature The meanPb Cr Co and Cu levels were below NEQS while the levelsof Ni and Cd were slightly above NEQS These levels may betolerated by following precautionarymeasures in agriculturalactivities Among the pesticides emamectin exhibited a highpersistence in the soil that was closely associated with soilCu content It was also found that Cu stabilizes acetamipridwhile Cr and Ni facilitate the degradation of acetamipridand imidacloprid Thus the study provides basis for therisk assessment studies that are quite necessary to managethe contaminated sites in a cost effective manner whilepreserving the public and ecosystem health It also providesa management strategy for remediation of contaminatedsoil that is adding traces of Ni and Cr in the soil mayhelp in the degradation of frequently used acetamiprid andimidacloprid

Conflict of Interests

The authors declare no conflict of interests

References

[1] R A Cloyd and J A Bethke ldquoImpact of neonicotinoidinsecticides onnatural enemies in greenhouse and interiorscapeenvironmentsrdquo Pest Management Science vol 67 no 1 pp 3ndash92011

[2] P Khaliq L A Hashmi and M H Qazi ldquoAgriculture andenvironmentrdquo Progress Farming vol 15 pp 16ndash23 1995

[3] H Shiraishi F Pula A Otsuki and T Iwakuma ldquoBehaviourof pesticides in Lake Kasumugaura Japanrdquo Science of the TotalEnvironment vol 72 pp 29ndash42 1988

[4] R Rial Otero B Cancho Grande M Arias Estevez E LopezPeriago and J Simal Gandara ldquoProcedure for themeasurementof soil inputs of plant-protection agents washed off throughvineyard canopy by rainfallrdquo Journal of Agricultural and FoodChemistry vol 51 no 17 pp 5041ndash5046 2003

[5] H M G van der Werf ldquoAssessing the impact of pesticideson the environmentrdquo Agriculture Ecosystems and Environmentvol 60 no 2-3 pp 81ndash96 1996

[6] G W vanLoon and S J Duffy Environmental Chemistry AGlobal Perspective Oxford University Press Oxford UK 2ndedition 2005

10 Scientifica

[7] P K Goel Water Pollution (Causes Effects and Control) NewAge International (P) New Delhi India 2nd edition 2006

[8] M Arias-Estevez E Lopez-Periago E Martınez-Carballo JSimal-Gandara J-C Mejuto and L Garcıa-Rıo ldquoThe mobilityand degradation of pesticides in soils and the pollution ofgroundwater resourcesrdquo Agriculture Ecosystems amp Environ-ment vol 123 no 4 pp 247ndash260 2008

[9] P J Shea T A Machacek and S D Comfort ldquoAcceleratedremediation of pesticide-contaminated soil with zerovalentironrdquo Environmental Pollution vol 132 no 2 pp 183ndash188 2004

[10] A Isaiah and M Paul ldquoSynergistic effect of chemical pesticideson commonly grown vegetables in Northern Indiardquo Epidemiol-ogy vol 18 p S86 2007

[11] J Fenoll P Hellın C Marın C M Martınez and A PFlores ldquoMultiresidue analysis of pesticides in soil by gaschromatography with nitrogen-phosphorus detection and gaschromatography mass spectrometryrdquo Journal of Agriculturaland Food Chemistry vol 53 no 20 pp 7661ndash7666 2005

[12] S Seccia P FidenteDMontesano andPMorrica ldquoDetermina-tion of neonicotinoid insecticides residues in bovine milk sam-ples by solid-phase extraction clean-up and liquid chromatog-raphy with diode-array detectionrdquo Journal of ChromatographyA vol 1214 no 1-2 pp 115ndash120 2008

[13] S M Dem J M Cobb and D E Mullins ldquoPesticide residuesin soil and water from four cotton growing areas of Mali WestAfricardquo Journal of Agricultural Food amp Environmental Sciencesvol 1 no 1 pp 1ndash12 2007

[14] M W Aktar M Paramasivam D Sengupta S Purkait MGanguly and S Banerjee ldquoImpact assessment of pesticideresidues in fish of Ganga river around Kolkata in West BengalrdquoEnvironmental Monitoring and Assessment vol 157 no 1ndash4 pp97ndash104 2009

[15] T R Sandrin and R M Maier ldquoImpact of metals on thebiodegradation of organic pollutantsrdquo Environmental HealthPerspectives vol 111 no 8 pp 1093ndash1101 2003

[16] S Khan Q Cao Y M Zheng Y Z Huang and Y G ZhuldquoHealth risks of heavy metals in contaminated soils and foodcrops irrigated with wastewater in Beijing Chinardquo Environmen-tal Pollution vol 152 no 3 pp 686ndash692 2008

[17] M-K Zhang Z-Y Liu and H Wang ldquoUse of single extractionmethods to predict bioavailability of heavy metals in pollutedsoils to ricerdquo Communications in Soil Science amp Plant Analysisvol 41 no 7 pp 820ndash831 2010

[18] Y PWang J Y ShiHWangQ Lin X CChen andYXChenldquoThe influence of soil heavy metals pollution on soil microbialbiomass enzyme activity and community composition near acopper smelterrdquo Ecotoxicology amp Environmental Safety vol 67no 1 pp 75ndash81 2007

[19] A A Helal D M Imam S M Khalifa and H F AlyldquoInteraction of pesticides with humic compounds and theirmetal complexesrdquo Radiochemistry vol 48 no 4 pp 419ndash4252006

[20] H Tian J Li Z Mu L Li and Z Hao ldquoEffect of pH onDDT degradation in aqueous solution using bimetallic NiFenanoparticlesrdquo Separation amp Purification Technology vol 66no 1 pp 84ndash89 2009

[21] T-F Liu C Sun N Ta J Hong S-G Yang and C-X ChenldquoEffect of copper on the degradation of pesticides cypermethrinand cyhalothrinrdquo Journal of Environmental Sciences vol 19 no10 pp 1235ndash1238 2007

[22] E Quivet R Faure J Georges J-O Paısse and P LanterildquoInfluence of metal salts on the photodegradation of imazapyr

an imidazolinone pesticiderdquo Pest Management Science vol 62no 5 pp 407ndash413 2006

[23] M Kamiya andK Kameyama ldquoEffects of selectedmetal ions onphotodegradation of organophosphorus pesticides sensitizedby humic acidsrdquo Chemosphere vol 45 no 3 pp 231ndash235 2001

[24] M Radojevic and V N Bashkin Practical EnvironmentalAnalysis Royal Society of Chemistry Cambridge UK 1999

[25] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of selected metals in tan-nery effluents and related soilrdquo Journal of Hazardous Materialsvol 122 no 1-2 pp 17ndash22 2005

[26] G R Blake and K H Hartge ldquoBulk and particle densityrdquo inMethods of Soil Analysis Part 1 pp 363ndash382 Soil Science Societyof America Madison Wis USA 1986

[27] P Patnaik Handbook of Environmental Analysis ChemicalPollutants in Air Water Soil and SolidWastes CRC Lewis BocaRaton Fla USA 1997

[28] A Bartosova A Michalıkova M Sirotiak and M SoldanldquoComparison of two spectrophotometric techniques for nutri-ents analyses inwater samplesrdquoResearch Papers Faculty ofMate-rials Science and Technology SlovakUniversity of Technology vol20 no 32 pp 8ndash19 2013

[29] H Spiegel E Filcheva P Hegymegi A Gal and F G AVerheijen ldquoReview and comparison of methods used for soilorganic carbon determination part 2 laboratory studyrdquo SoilScience Agrochemistry and Ecology vol 41 no 4 pp 19ndash25 2007

[30] K H Tan Soil Sampling Preparation and Analysis CRC PressTaylor amp Francis Group Boca Raton Fla USA 2nd edition2005

[31] StatSoft Inc STATISTICA for Windows (Computer ProgramManual) StatSoft Tulsa Okla USA 1999

[32] USDA Soil Quality Indicator pH Natural Resources Conserva-tion Service 1998

[33] G E Lailach T DThompson and GW Brindley ldquoAbsorptionof pyrimidines purines and nucleosides by Co- Ni- Cu- andFe(III)-Montmorillonite (Clay-Organic Studies XIII)rdquo Claysand Clay Minerals vol 16 no 4 pp 295ndash301 1968

[34] R G NashW G Harris and C C Lewis ldquoSoil pH andmetallicamendment effects on DDT conversion to DDErdquo Journal ofEnvironmental Quality vol 2 no 3 pp 390ndash394 1973

[35] J G Konrad and G Chesters ldquoDegradation in soils of cioduman organophosphate insecticiderdquo Journal of Agricultural andFood Chemistry vol 17 no 2 pp 226ndash230 1969

[36] A Albarran R Celis M C Hermosın A Lopez-Pineiro and JCornejo ldquoBehavior of simazine in soil amended with the finalresidue of the olive-oil extraction processrdquo Chemosphere vol54 no 6 pp 717ndash724 2004

[37] J Dec and J-M Bollag ldquoDetermination of covalent and non-covalent binding interactions between xenobiotic chemicalsand soilrdquo Soil Science vol 162 no 12 pp 858ndash874 1997

[38] A Nawab A Aleem and A Malik ldquoDetermination oforganochlorine pesticides in agricultural soil with specialreference to 120574-HCH degradation by Pseudomonas strainsrdquoBioresource Technology vol 88 no 1 pp 41ndash46 2003

[39] M Bavcon P Trebse and L Zupancic-Kralj ldquoInvestigationsof the determination and transformations of diazinon andmalathion under environmental conditions using gas chro-matography coupled with a flame ionisation detectorrdquo Chemo-sphere vol 50 no 5 pp 595ndash601 2003

[40] S A Sassman L S Lee M Bischoff and R F Turco ldquoAssessingNN1015840-dibutylurea (DBU) formation in soils after application of

Scientifica 11

n-butylisocyanate and benlate fungicidesrdquo Journal of Agricul-tural and Food Chemistry vol 52 no 4 pp 747ndash754 2004

[41] E R Mouta M R Soares and J C Casagrande ldquoCopperadsorption as a function of solution parameters of variablecharge soilsrdquo Journal of the Brazilian Chemical Society vol 19no 5 pp 996ndash1009 2008

[42] M Arshad J Silvestre E Pinelli et al ldquoA field study oflead phytoextraction by various scented Pelargonium cultivarsrdquoChemosphere vol 71 no 11 pp 2187ndash2192 2008

[43] G Uzu S Sobanska Y Aliouane P Pradere and C DumatldquoStudy of lead phytoavailability for atmospheric industrialmicronic and sub-micronic particles in relation with leadspeciationrdquo Environmental Pollution vol 157 no 4 pp 1178ndash1185 2009

[44] L H P Jones and S C Jarvis ldquoThe fate of heavy metalsrdquo inTheChemistry of Soil Processes D J Green andMH B Hayes Edsp 593 John Wiley amp Sons New York NY USA 1981

[45] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of trace metal levels intannery effluents in relation to soil and water a case study fromPeshawar Pakistanrdquo Journal of EnvironmentalManagement vol79 no 1 pp 20ndash29 2006

[46] R J Ellis B Neish MW Trett et al ldquoComparison of microbialand meiofaunal community analyses for determining impact ofheavy metal contaminationrdquo Journal of Microbiological Meth-ods vol 45 no 3 pp 171ndash185 2001

[47] S R Tariq F Iqbal and A Ijaz ldquoAssessment and multivariateanalysis of metals in surgical instrument industry affected topsoils and groundwater for future reclamationrdquo InternationalJournal of Environment and Pollution vol 1 pp 54ndash71 2013

[48] S R Tariq and N Rashid ldquoMultivariate analysis of metal levelsin paddy soil rice plants and rice grains a case study fromShakargarh Pakistanrdquo Journal of Chemistry vol 2013 ArticleID 539251 10 pages 2013

[49] B S Everitt S Landau and M Leese Cluster Analysis Arnold4th edition 2001

Submit your manuscripts athttpwwwhindawicom

Nutrition and Metabolism

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Food ScienceInternational Journal of

Agronomy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom

Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

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ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

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Plant GenomicsInternational Journal of

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Biotechnology Research International

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Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

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Veterinary Medicine International

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Cell BiologyInternational Journal of

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Evolutionary BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Scientifica 5

Table2Ba

sicstatisticsp

aram

etersfor

thed

istrib

utionof

selected

parameters(mgkg)insoilsamples

(119899=52)

Minim

umMaxim

umMean

Median

SDSE

Varia

nce

Kurtosis

Skew

ness

NEQ

SBClowast

Pb(m

gkg)

1093

2185

1618

1649

268

0372

7184

minus0639

minus0261

25189

Cr(m

gkg)

164

96586

5995

2238

031

5008

minus0902

minus0183

20503

Co(m

gkg)

293

124

7558

7595

2094

029

4386

minus0291

0077

100392

Cu(m

gkg)

1298

2190

1812

1856

2141

0297

4584

minus0332

minus0516

mdash276

Ni(mgkg)

153

2997

2216

2225

366

60508

1344

minus0572

0118

200135

Cd(m

gkg)

0347

1019

0585

0538

0175

0024

0031

0104

0961

05

014

Bulkdensity

(Mgmminus3

)15

3016

1015

6815

700028

0005

0001

minus13

33minus0003

mdashmdash

OC(

)12

911139

4616

3390

2894

0401

8376

minus0248

1074

mdash45

pH76

85

81

8055

02

0028

004

minus007

minus0206

mdash72

Con

ductivity

(120583Scm

)980

1887

1412

16005

3174

4402

1008times105

minus17

77minus0076

mdash108

Clminus

(mgkg)

4808

22438

12909

12338

61456

8522

3777times107

minus12

880271

mdash987

NO3

minus

(mgkg)

2879

94434

3500

934470

10852

1505

1178times108

1854

2807

mdash843

SO4

2minus

(mgkg)

400

9times103

9297times104

4710times104

40times104

2159times104

2993times103

466

0times108

1028

1447

mdash419

Imidacloprid

(120583gg)

23

2059

6445

556

6212

8613

3857

036

1229

mdashmdash

Emam

ectin

(120583gg)

0001

1305

2967

599

4312

598

1859times105

0414

1351

mdashmdash

Acetam

iprid

1140

12588

2643

704118

35711

169600

0968

1635

mdashmdash

lowast

BC=backgrou

ndlevels(m

eanof

three)

6 Scientifica

Moi

sture

cont

ent (

)

OC

()

pH

Box plot

Median

Nonoutlier range

Box plot

Imid

aclo

prid

Emam

ectin

Acet

amip

rid

Outliers

Cr Co Cu Ni CdPb

25ndash75

Median

Nonoutlier range 25ndash75

Median Nonoutlier range 25ndash75

OutliersMedian Nonoutlier range 25ndash75

minus5

0

5

10

15

20

25

30

35

minus200

0

200

400

600

800

1000

1200

1400

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

02468

101214161820

Clminus

(mg

kg)

NO3minus

(mg

kg)

SO42minus

(mg

kg)

Figure 2 Box and Whisker plots for the distribution of various parameters in soil

the pesticides that are being applied to the cotton crops ofPakpattan intermittently That is why these pesticides wereincluded in the study The data recorded a great variabilityin the concentrations of imidacloprid that was present ata minimum value of 23 120583gg and a maximum value of2059120583gg with a mean value standing at 6445 120583gg Thislarge variation in the recorded values reflected the differencesin the extent of exposure of soil to the pesticides Emamectinwas present in these samples at mean levels of 2967 120583ggwhile the mean levels for acetamiprid were 2643 120583gg Thelarge variation between themean andmedian values depictedthe nonnormal distribution of the data which was alsoreflected by high SD skewness and kurtosis values Thedistribution of these pesticides has also been depicted in Boxplots (Figure 2)

The data for the descriptive statistics of selected metals(ie Pb Cr Co Cu Ni and Cd Table 2 Figure 2) showedthat nickel in these samples was present at highest meanconcentration of 2216mgkg The major source of Ni inthese soils may be the Ni plating industry located nearbyNi was followed by Cu that exhibited a mean concentrationof 1812mgkg The minimum and maximum concentrationsrecorded for Cu were 1298 and 2190mgkg respectivelyCopper is required for various biochemical processes inplants thus it is an essential trace element but its enhancedconcentrations are hazardous for human populations [41]

Lead was another heavy metal that was present inthese samples at appreciable maximum concentration of1618mgkg Over the past few decades the vehicular emis-sions from leaded gasoline have been overcome due to ban

Scientifica 7

on leaded gasoline thus the source of this lead in soilwas traced in various fungicides and pesticides like leadarsenate and so forth that are used at various stages of cropproduction [2] Cadmium was the metal that was presentat trace level of 0585mgkg Chromium another hazardousmetal was found to be present at a mean level of 586mgkgIts maximum concentration was recorded to be 96mgkgwhich is quite higher than the limit set for agricultural soilsThis chromium not only is hazardous for soil biota butmay also contaminate the food chain through uptake andaccumulation by plants furthermore depending on the soilconditions like pH it may become soluble and thus enter thegroundwater the only source of drinking water in the area

The mean levels recorded for Co were 7558mgkg Theorder of themean concentrations ofmetals in the soil samplesremained Ni gt Cu gt Pb gt Co gt Cr gt Cd The symmetryparameters for the data that is standard deviation skewnessand kurtosis are also listed in Table 2

A comparison of mean metal levels with NationalEnvironmental Quality Standards (NEQS) is also depictedin Table 2 The average Pb concentration in soil sampleswas found to be 1618mgkg against the standard valueof 25mgkg The estimated value of lead in soil sampleswas lower than standard value which indicated that soil Pbwas below the contamination level and would not pose asignificant threat of contaminating the food chain MoreoverPb uptake by plants depends upon soil pH that is at higherpH lead becomes immobilized It is also known that due tosmall transfer factor Pb is not taken up by plants below aconcentration of 300120583gg in soil and if taken up it wouldaccumulate in leaves rather than the fruit [42 43]

Themean level of Cr recorded in soil was 586mgkgThisvalue is approximately four times less than standard value of20mgkg (NEQS) Co was present in the soil samples at themean level of 7558mgkg which is also less than standardvalue of 10mgkg The mean concentration of Cu in soilsamples was found to be 1812mgkg Ni was present in soilsamples at the mean level of 2216mgkg slightly higher thanthe recommended standard value of 20mgkg

The mean concentration of Cd was found to be0585mgkg a value slightly exceeding the standard valueof 05mgkg In fact fertilizers are added regularly to soilsto replenish N K and P for good crop growth Thesecompounds contain trace amounts of Cd as impuritieswhich after continued application are significantly increasedin the soil [44] Overall it was concluded that Pb Cr Cuand Co were present in tolerable range in the soil samples butNi and Cd surpassed the standard value but not to greaterextents Thus although the selected metals do not pose anythreat to the environment at their present levels but with thepassage of time the unwise use of agricultural activities maylead to a large buildup of metals in the soil that may endangerthe environment as well as human health

32 Correlation Coefficient Matrices of Various Parameters inthe Soil Table 3 depicted the correlation coefficient matrixfor the studied physicochemical parameters pesticides andmetal levels in the soil samples collected from the agriculturalfields The 119903-values were found to be significant at plusmn0231

(119901 lt 005) The data was characterized by both negative andpositive correlations between various pairs of parametersThe data was nonnormally distributed and also the anthro-pogenic activities led to a change in the natural concentrationof some of the parameters Thus all the observed correlationswere not high For the physicochemical parameters themost significant positive correlation was observed betweenelectrical conductivity and chloride levels with an 119903-value0292 evidencing that in about 292 cases the electricalconductivity of soil was observed to be increased with anincrease in chloride content and vice versa Similarly a strongpositive correlation was observed between pH and sulphatewith 119903-values of 0235 Organic carbon content of soil wasfound to be positively correlated with nitrate levels but thiscorrelation was not significant

The correlation coefficientmatrix for the levels of selectedmetals in the collected soil samples depicted the strongestpositive correlation between Cr and Ni at an 119903-value of 0460thereby showing that in 460 cases the concentration ofCr went in parallel with concentration of Ni thus sharing asimilar origin in the soil matrix The next strongest positivecorrelation was observed betweenNi and Cu pair (0431)Theother metal pair that was significantly positively correlatedincluded Cr-Co (119903-value 0343) Cr Ni and Cu were foundto be strongly negatively correlated with Cd (119903-values ofminus0407 minus0430 and minus0375 resp) depicting an increase inconcentration of one metal with a decrease in concentrationof other metals

No significant positive or negative correlation wasobserved among the selected pesticides depicting that thesources of pesticides in the soil were not the same Thisis also due to the fact that different pesticides are appliedto the crops at different stages of crop production Thusthey enter the soil at different periods of time The datacorresponding to the correlation coefficient matrix for thephysicochemical parameters and the various metals depictedonly few significant positivenegative correlations Ni ofthe soil exhibited the strongest positive correlation withits conductivity with 119903-value of 0342 Cu was also signifi-cantly positively correlated with the conductivity (119903-value of0286) Cd and electrical conductivitywere significantly nega-tively correlated Another significant negative correlationwasobserved between Cr and nitrate level of soil solution Theother correlations were too naıve to be discussed

The correlation coefficient matrix for the pesticides-to-physicochemical parameters depicted a significant neg-ative correlation between soil organic carbon content andemamectin thereby evidencing the influence of soil organiccarbon on the sorption of emamectin Soil EC values werealso found to be negatively correlated with imidacloprid andemamectin

Numerous metals are known to possess good catalysisability and they may affect the behavior of coexisting pes-ticides in the soil Thus the most important segment of thepresent investigation was to study the correlations among theselected pesticides and variousmetal levelsThe data depicteda strong positive correlation between acetamiprid and Cuwith 119903-value of 0239 A strong positive correlation pointedtowards an increase in the concentration of acetamiprid

8 Scientifica

Table3Correlationcoeffi

cientm

atrix

aforv

arious

parameterso

fsoilsam

ples

(119899=52)

PbCr

Co

CuNi

Cd

OCb

pHEC

cClminus

NO3

minus

SO4

2minus

Imd

Eme

Acf

Pb10

00Cr

0179

1000

Co

0019

034

310

00Cu

0018

0132minus0002

1000

Ni

0199

046

00074

0431

1000

Cd

minus0154minus040

7minus0045minus0375minus043

010

00OC(

)0124

0083

0092minus0136minus0039minus0075

1000

pH0080minus0162

0164minus0124minus0076

0118

0187

1000

EC(120583SCm

)minus000

9minus0045minus0047

028

6034

2minus024

50137

0059

1000

Clminus

(mgkg)minus0163minus0255minus0140minus0079

0034

0144

0083

0058

029

210

00NO3

minus

(mgkg)

0011

0018minus0221minus0065

0051minus0076

0213

0014

0153

0087

1000

SO4

2minus

(mgkg)minus0080minus0149minus0201minus0096minus0057

0146

000

40235minus0156

0212

0177

1000

Imlowast

0086minus0021

0012

0017minus0317

0021

0100

0175minus0314minus0122minus0103

0052

1000

Emlowast

0213minus0071

0161

000

9minus0012

0015minus0239

0084minus0265minus0163minus0183

0085minus0086

1000

Aclowast

minus0119

minus030

5minus0143

0239minus0102

0163minus0077

0099

0313

0038

0007minus0085

0050minus0174

1000

a 119903-valuesa

resig

nificantat0

231

at119901lt005

b OC=organicc

arbo

nc EC=ele

ctric

alcond

uctiv

itydIm

=im

idacloprideEm

=em

amectin

fAc

=acetam

iprid

lowast

Con

centratio

nin120583gg

Scientifica 9

Wardrsquos method

OC ()Imidacloprid

pH

CdAcetamiprid

Conductivity (120583Scm)CuCoNiCr

EmamectinPb

04 06 08 10 12 14 16 18 2002Linkage distance

Clminus (mgkg)

NO3minus (mgkg)

SO42minus (mgkg)

Figure 3 Cluster analysis for the determination of various parame-ters

with the presence of greater concentration of copper in thesoil On the other hand imidacloprid in soil was found tobe negatively correlated with Ni of soil (119903-value of minus0317)Similarly a significant negative correlation was observedbetween Cr and acetamiprid (119903-value minus0305) Thus it wasevidenced that Cu stabilizes acetamiprid while Cr and Nifacilitate the degradation of acetamiprid and imidacloprid inthe soil [45]

Similar results have been reported for pyrethroid pes-ticides whose degradation was shown to be inhibited bythe presence of copper ions Ellis et al reported that metalslike Cu present in soil may react with the sulfhydryl groupof enzymes and inhibit their activity Thus the pesticidesbecome more persistent thereby leading to an increase intheir concentration with time [21 46]

33 Cluster Analysis of Various Parameters in the Soil Sam-ples Cluster analysis has proved to be a milestone towardthe source apportionment studies of various pollutants likemetals and pesticides in the soil and other media [47 48]In this analysis (Figure 3) linkage distance is used as themeasure of degree of closeness and hence relation among thevarious parameters [49] A number of clusters were formedwithin a significant linkage distance The strongest clusterwas observed between Cr and Ni evidencing that high Crcontent of the soil was associated with the enhanced Nilevels These two metals were further associated with Co toform a second cluster within linkage distance of 10 Themost important cluster of the study was observed betweenacetamiprid and conductivity that was further associatedwith Cu It evidenced that Cu present in the soil may causethe persistence of acetamiprid whose concentration increaseswith time Similarly emamectin was closely associated withPd

Cluster analysis revealed a close association betweensulphate and pH which formed a primary cluster withinlinkage distance of 06 This primary cluster was furtherassociated with Cd and Clminus within linkage distance of 10 onone side and with imidacloprid in the soil on the other side

The organic carbon of soil was associated with nitrate withina linkage distance of 08 and this factor was further associatedwith previous cluster

Overall the study revealed that frequently used pesti-cides that is imidacloprid emamectin and acetamipridwere present in the soil of cotton fields and were influencedby factors such as soil pH and organic carbon The studyalso furnished correlations among pesticides and metals inthe soil It was shown that presence of certain metals such asNi caused the decreased levels of imidacloprid Similarly Crenhanced the degradation of acetamiprid and Cu caused thepersistence of this pesticide in the soil

4 Conclusions

The soil samples collected from the cotton growing area ofPakpattan Pakistan were slightly basic in nature The meanPb Cr Co and Cu levels were below NEQS while the levelsof Ni and Cd were slightly above NEQS These levels may betolerated by following precautionarymeasures in agriculturalactivities Among the pesticides emamectin exhibited a highpersistence in the soil that was closely associated with soilCu content It was also found that Cu stabilizes acetamipridwhile Cr and Ni facilitate the degradation of acetamipridand imidacloprid Thus the study provides basis for therisk assessment studies that are quite necessary to managethe contaminated sites in a cost effective manner whilepreserving the public and ecosystem health It also providesa management strategy for remediation of contaminatedsoil that is adding traces of Ni and Cr in the soil mayhelp in the degradation of frequently used acetamiprid andimidacloprid

Conflict of Interests

The authors declare no conflict of interests

References

[1] R A Cloyd and J A Bethke ldquoImpact of neonicotinoidinsecticides onnatural enemies in greenhouse and interiorscapeenvironmentsrdquo Pest Management Science vol 67 no 1 pp 3ndash92011

[2] P Khaliq L A Hashmi and M H Qazi ldquoAgriculture andenvironmentrdquo Progress Farming vol 15 pp 16ndash23 1995

[3] H Shiraishi F Pula A Otsuki and T Iwakuma ldquoBehaviourof pesticides in Lake Kasumugaura Japanrdquo Science of the TotalEnvironment vol 72 pp 29ndash42 1988

[4] R Rial Otero B Cancho Grande M Arias Estevez E LopezPeriago and J Simal Gandara ldquoProcedure for themeasurementof soil inputs of plant-protection agents washed off throughvineyard canopy by rainfallrdquo Journal of Agricultural and FoodChemistry vol 51 no 17 pp 5041ndash5046 2003

[5] H M G van der Werf ldquoAssessing the impact of pesticideson the environmentrdquo Agriculture Ecosystems and Environmentvol 60 no 2-3 pp 81ndash96 1996

[6] G W vanLoon and S J Duffy Environmental Chemistry AGlobal Perspective Oxford University Press Oxford UK 2ndedition 2005

10 Scientifica

[7] P K Goel Water Pollution (Causes Effects and Control) NewAge International (P) New Delhi India 2nd edition 2006

[8] M Arias-Estevez E Lopez-Periago E Martınez-Carballo JSimal-Gandara J-C Mejuto and L Garcıa-Rıo ldquoThe mobilityand degradation of pesticides in soils and the pollution ofgroundwater resourcesrdquo Agriculture Ecosystems amp Environ-ment vol 123 no 4 pp 247ndash260 2008

[9] P J Shea T A Machacek and S D Comfort ldquoAcceleratedremediation of pesticide-contaminated soil with zerovalentironrdquo Environmental Pollution vol 132 no 2 pp 183ndash188 2004

[10] A Isaiah and M Paul ldquoSynergistic effect of chemical pesticideson commonly grown vegetables in Northern Indiardquo Epidemiol-ogy vol 18 p S86 2007

[11] J Fenoll P Hellın C Marın C M Martınez and A PFlores ldquoMultiresidue analysis of pesticides in soil by gaschromatography with nitrogen-phosphorus detection and gaschromatography mass spectrometryrdquo Journal of Agriculturaland Food Chemistry vol 53 no 20 pp 7661ndash7666 2005

[12] S Seccia P FidenteDMontesano andPMorrica ldquoDetermina-tion of neonicotinoid insecticides residues in bovine milk sam-ples by solid-phase extraction clean-up and liquid chromatog-raphy with diode-array detectionrdquo Journal of ChromatographyA vol 1214 no 1-2 pp 115ndash120 2008

[13] S M Dem J M Cobb and D E Mullins ldquoPesticide residuesin soil and water from four cotton growing areas of Mali WestAfricardquo Journal of Agricultural Food amp Environmental Sciencesvol 1 no 1 pp 1ndash12 2007

[14] M W Aktar M Paramasivam D Sengupta S Purkait MGanguly and S Banerjee ldquoImpact assessment of pesticideresidues in fish of Ganga river around Kolkata in West BengalrdquoEnvironmental Monitoring and Assessment vol 157 no 1ndash4 pp97ndash104 2009

[15] T R Sandrin and R M Maier ldquoImpact of metals on thebiodegradation of organic pollutantsrdquo Environmental HealthPerspectives vol 111 no 8 pp 1093ndash1101 2003

[16] S Khan Q Cao Y M Zheng Y Z Huang and Y G ZhuldquoHealth risks of heavy metals in contaminated soils and foodcrops irrigated with wastewater in Beijing Chinardquo Environmen-tal Pollution vol 152 no 3 pp 686ndash692 2008

[17] M-K Zhang Z-Y Liu and H Wang ldquoUse of single extractionmethods to predict bioavailability of heavy metals in pollutedsoils to ricerdquo Communications in Soil Science amp Plant Analysisvol 41 no 7 pp 820ndash831 2010

[18] Y PWang J Y ShiHWangQ Lin X CChen andYXChenldquoThe influence of soil heavy metals pollution on soil microbialbiomass enzyme activity and community composition near acopper smelterrdquo Ecotoxicology amp Environmental Safety vol 67no 1 pp 75ndash81 2007

[19] A A Helal D M Imam S M Khalifa and H F AlyldquoInteraction of pesticides with humic compounds and theirmetal complexesrdquo Radiochemistry vol 48 no 4 pp 419ndash4252006

[20] H Tian J Li Z Mu L Li and Z Hao ldquoEffect of pH onDDT degradation in aqueous solution using bimetallic NiFenanoparticlesrdquo Separation amp Purification Technology vol 66no 1 pp 84ndash89 2009

[21] T-F Liu C Sun N Ta J Hong S-G Yang and C-X ChenldquoEffect of copper on the degradation of pesticides cypermethrinand cyhalothrinrdquo Journal of Environmental Sciences vol 19 no10 pp 1235ndash1238 2007

[22] E Quivet R Faure J Georges J-O Paısse and P LanterildquoInfluence of metal salts on the photodegradation of imazapyr

an imidazolinone pesticiderdquo Pest Management Science vol 62no 5 pp 407ndash413 2006

[23] M Kamiya andK Kameyama ldquoEffects of selectedmetal ions onphotodegradation of organophosphorus pesticides sensitizedby humic acidsrdquo Chemosphere vol 45 no 3 pp 231ndash235 2001

[24] M Radojevic and V N Bashkin Practical EnvironmentalAnalysis Royal Society of Chemistry Cambridge UK 1999

[25] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of selected metals in tan-nery effluents and related soilrdquo Journal of Hazardous Materialsvol 122 no 1-2 pp 17ndash22 2005

[26] G R Blake and K H Hartge ldquoBulk and particle densityrdquo inMethods of Soil Analysis Part 1 pp 363ndash382 Soil Science Societyof America Madison Wis USA 1986

[27] P Patnaik Handbook of Environmental Analysis ChemicalPollutants in Air Water Soil and SolidWastes CRC Lewis BocaRaton Fla USA 1997

[28] A Bartosova A Michalıkova M Sirotiak and M SoldanldquoComparison of two spectrophotometric techniques for nutri-ents analyses inwater samplesrdquoResearch Papers Faculty ofMate-rials Science and Technology SlovakUniversity of Technology vol20 no 32 pp 8ndash19 2013

[29] H Spiegel E Filcheva P Hegymegi A Gal and F G AVerheijen ldquoReview and comparison of methods used for soilorganic carbon determination part 2 laboratory studyrdquo SoilScience Agrochemistry and Ecology vol 41 no 4 pp 19ndash25 2007

[30] K H Tan Soil Sampling Preparation and Analysis CRC PressTaylor amp Francis Group Boca Raton Fla USA 2nd edition2005

[31] StatSoft Inc STATISTICA for Windows (Computer ProgramManual) StatSoft Tulsa Okla USA 1999

[32] USDA Soil Quality Indicator pH Natural Resources Conserva-tion Service 1998

[33] G E Lailach T DThompson and GW Brindley ldquoAbsorptionof pyrimidines purines and nucleosides by Co- Ni- Cu- andFe(III)-Montmorillonite (Clay-Organic Studies XIII)rdquo Claysand Clay Minerals vol 16 no 4 pp 295ndash301 1968

[34] R G NashW G Harris and C C Lewis ldquoSoil pH andmetallicamendment effects on DDT conversion to DDErdquo Journal ofEnvironmental Quality vol 2 no 3 pp 390ndash394 1973

[35] J G Konrad and G Chesters ldquoDegradation in soils of cioduman organophosphate insecticiderdquo Journal of Agricultural andFood Chemistry vol 17 no 2 pp 226ndash230 1969

[36] A Albarran R Celis M C Hermosın A Lopez-Pineiro and JCornejo ldquoBehavior of simazine in soil amended with the finalresidue of the olive-oil extraction processrdquo Chemosphere vol54 no 6 pp 717ndash724 2004

[37] J Dec and J-M Bollag ldquoDetermination of covalent and non-covalent binding interactions between xenobiotic chemicalsand soilrdquo Soil Science vol 162 no 12 pp 858ndash874 1997

[38] A Nawab A Aleem and A Malik ldquoDetermination oforganochlorine pesticides in agricultural soil with specialreference to 120574-HCH degradation by Pseudomonas strainsrdquoBioresource Technology vol 88 no 1 pp 41ndash46 2003

[39] M Bavcon P Trebse and L Zupancic-Kralj ldquoInvestigationsof the determination and transformations of diazinon andmalathion under environmental conditions using gas chro-matography coupled with a flame ionisation detectorrdquo Chemo-sphere vol 50 no 5 pp 595ndash601 2003

[40] S A Sassman L S Lee M Bischoff and R F Turco ldquoAssessingNN1015840-dibutylurea (DBU) formation in soils after application of

Scientifica 11

n-butylisocyanate and benlate fungicidesrdquo Journal of Agricul-tural and Food Chemistry vol 52 no 4 pp 747ndash754 2004

[41] E R Mouta M R Soares and J C Casagrande ldquoCopperadsorption as a function of solution parameters of variablecharge soilsrdquo Journal of the Brazilian Chemical Society vol 19no 5 pp 996ndash1009 2008

[42] M Arshad J Silvestre E Pinelli et al ldquoA field study oflead phytoextraction by various scented Pelargonium cultivarsrdquoChemosphere vol 71 no 11 pp 2187ndash2192 2008

[43] G Uzu S Sobanska Y Aliouane P Pradere and C DumatldquoStudy of lead phytoavailability for atmospheric industrialmicronic and sub-micronic particles in relation with leadspeciationrdquo Environmental Pollution vol 157 no 4 pp 1178ndash1185 2009

[44] L H P Jones and S C Jarvis ldquoThe fate of heavy metalsrdquo inTheChemistry of Soil Processes D J Green andMH B Hayes Edsp 593 John Wiley amp Sons New York NY USA 1981

[45] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of trace metal levels intannery effluents in relation to soil and water a case study fromPeshawar Pakistanrdquo Journal of EnvironmentalManagement vol79 no 1 pp 20ndash29 2006

[46] R J Ellis B Neish MW Trett et al ldquoComparison of microbialand meiofaunal community analyses for determining impact ofheavy metal contaminationrdquo Journal of Microbiological Meth-ods vol 45 no 3 pp 171ndash185 2001

[47] S R Tariq F Iqbal and A Ijaz ldquoAssessment and multivariateanalysis of metals in surgical instrument industry affected topsoils and groundwater for future reclamationrdquo InternationalJournal of Environment and Pollution vol 1 pp 54ndash71 2013

[48] S R Tariq and N Rashid ldquoMultivariate analysis of metal levelsin paddy soil rice plants and rice grains a case study fromShakargarh Pakistanrdquo Journal of Chemistry vol 2013 ArticleID 539251 10 pages 2013

[49] B S Everitt S Landau and M Leese Cluster Analysis Arnold4th edition 2001

Submit your manuscripts athttpwwwhindawicom

Nutrition and Metabolism

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Food ScienceInternational Journal of

Agronomy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom

Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Plant GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Biotechnology Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Forestry ResearchInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Veterinary Medicine International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Cell BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Evolutionary BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

6 Scientifica

Moi

sture

cont

ent (

)

OC

()

pH

Box plot

Median

Nonoutlier range

Box plot

Imid

aclo

prid

Emam

ectin

Acet

amip

rid

Outliers

Cr Co Cu Ni CdPb

25ndash75

Median

Nonoutlier range 25ndash75

Median Nonoutlier range 25ndash75

OutliersMedian Nonoutlier range 25ndash75

minus5

0

5

10

15

20

25

30

35

minus200

0

200

400

600

800

1000

1200

1400

0

5000

10000

15000

20000

25000

30000

35000

40000

45000

02468

101214161820

Clminus

(mg

kg)

NO3minus

(mg

kg)

SO42minus

(mg

kg)

Figure 2 Box and Whisker plots for the distribution of various parameters in soil

the pesticides that are being applied to the cotton crops ofPakpattan intermittently That is why these pesticides wereincluded in the study The data recorded a great variabilityin the concentrations of imidacloprid that was present ata minimum value of 23 120583gg and a maximum value of2059120583gg with a mean value standing at 6445 120583gg Thislarge variation in the recorded values reflected the differencesin the extent of exposure of soil to the pesticides Emamectinwas present in these samples at mean levels of 2967 120583ggwhile the mean levels for acetamiprid were 2643 120583gg Thelarge variation between themean andmedian values depictedthe nonnormal distribution of the data which was alsoreflected by high SD skewness and kurtosis values Thedistribution of these pesticides has also been depicted in Boxplots (Figure 2)

The data for the descriptive statistics of selected metals(ie Pb Cr Co Cu Ni and Cd Table 2 Figure 2) showedthat nickel in these samples was present at highest meanconcentration of 2216mgkg The major source of Ni inthese soils may be the Ni plating industry located nearbyNi was followed by Cu that exhibited a mean concentrationof 1812mgkg The minimum and maximum concentrationsrecorded for Cu were 1298 and 2190mgkg respectivelyCopper is required for various biochemical processes inplants thus it is an essential trace element but its enhancedconcentrations are hazardous for human populations [41]

Lead was another heavy metal that was present inthese samples at appreciable maximum concentration of1618mgkg Over the past few decades the vehicular emis-sions from leaded gasoline have been overcome due to ban

Scientifica 7

on leaded gasoline thus the source of this lead in soilwas traced in various fungicides and pesticides like leadarsenate and so forth that are used at various stages of cropproduction [2] Cadmium was the metal that was presentat trace level of 0585mgkg Chromium another hazardousmetal was found to be present at a mean level of 586mgkgIts maximum concentration was recorded to be 96mgkgwhich is quite higher than the limit set for agricultural soilsThis chromium not only is hazardous for soil biota butmay also contaminate the food chain through uptake andaccumulation by plants furthermore depending on the soilconditions like pH it may become soluble and thus enter thegroundwater the only source of drinking water in the area

The mean levels recorded for Co were 7558mgkg Theorder of themean concentrations ofmetals in the soil samplesremained Ni gt Cu gt Pb gt Co gt Cr gt Cd The symmetryparameters for the data that is standard deviation skewnessand kurtosis are also listed in Table 2

A comparison of mean metal levels with NationalEnvironmental Quality Standards (NEQS) is also depictedin Table 2 The average Pb concentration in soil sampleswas found to be 1618mgkg against the standard valueof 25mgkg The estimated value of lead in soil sampleswas lower than standard value which indicated that soil Pbwas below the contamination level and would not pose asignificant threat of contaminating the food chain MoreoverPb uptake by plants depends upon soil pH that is at higherpH lead becomes immobilized It is also known that due tosmall transfer factor Pb is not taken up by plants below aconcentration of 300120583gg in soil and if taken up it wouldaccumulate in leaves rather than the fruit [42 43]

Themean level of Cr recorded in soil was 586mgkgThisvalue is approximately four times less than standard value of20mgkg (NEQS) Co was present in the soil samples at themean level of 7558mgkg which is also less than standardvalue of 10mgkg The mean concentration of Cu in soilsamples was found to be 1812mgkg Ni was present in soilsamples at the mean level of 2216mgkg slightly higher thanthe recommended standard value of 20mgkg

The mean concentration of Cd was found to be0585mgkg a value slightly exceeding the standard valueof 05mgkg In fact fertilizers are added regularly to soilsto replenish N K and P for good crop growth Thesecompounds contain trace amounts of Cd as impuritieswhich after continued application are significantly increasedin the soil [44] Overall it was concluded that Pb Cr Cuand Co were present in tolerable range in the soil samples butNi and Cd surpassed the standard value but not to greaterextents Thus although the selected metals do not pose anythreat to the environment at their present levels but with thepassage of time the unwise use of agricultural activities maylead to a large buildup of metals in the soil that may endangerthe environment as well as human health

32 Correlation Coefficient Matrices of Various Parameters inthe Soil Table 3 depicted the correlation coefficient matrixfor the studied physicochemical parameters pesticides andmetal levels in the soil samples collected from the agriculturalfields The 119903-values were found to be significant at plusmn0231

(119901 lt 005) The data was characterized by both negative andpositive correlations between various pairs of parametersThe data was nonnormally distributed and also the anthro-pogenic activities led to a change in the natural concentrationof some of the parameters Thus all the observed correlationswere not high For the physicochemical parameters themost significant positive correlation was observed betweenelectrical conductivity and chloride levels with an 119903-value0292 evidencing that in about 292 cases the electricalconductivity of soil was observed to be increased with anincrease in chloride content and vice versa Similarly a strongpositive correlation was observed between pH and sulphatewith 119903-values of 0235 Organic carbon content of soil wasfound to be positively correlated with nitrate levels but thiscorrelation was not significant

The correlation coefficientmatrix for the levels of selectedmetals in the collected soil samples depicted the strongestpositive correlation between Cr and Ni at an 119903-value of 0460thereby showing that in 460 cases the concentration ofCr went in parallel with concentration of Ni thus sharing asimilar origin in the soil matrix The next strongest positivecorrelation was observed betweenNi and Cu pair (0431)Theother metal pair that was significantly positively correlatedincluded Cr-Co (119903-value 0343) Cr Ni and Cu were foundto be strongly negatively correlated with Cd (119903-values ofminus0407 minus0430 and minus0375 resp) depicting an increase inconcentration of one metal with a decrease in concentrationof other metals

No significant positive or negative correlation wasobserved among the selected pesticides depicting that thesources of pesticides in the soil were not the same Thisis also due to the fact that different pesticides are appliedto the crops at different stages of crop production Thusthey enter the soil at different periods of time The datacorresponding to the correlation coefficient matrix for thephysicochemical parameters and the various metals depictedonly few significant positivenegative correlations Ni ofthe soil exhibited the strongest positive correlation withits conductivity with 119903-value of 0342 Cu was also signifi-cantly positively correlated with the conductivity (119903-value of0286) Cd and electrical conductivitywere significantly nega-tively correlated Another significant negative correlationwasobserved between Cr and nitrate level of soil solution Theother correlations were too naıve to be discussed

The correlation coefficient matrix for the pesticides-to-physicochemical parameters depicted a significant neg-ative correlation between soil organic carbon content andemamectin thereby evidencing the influence of soil organiccarbon on the sorption of emamectin Soil EC values werealso found to be negatively correlated with imidacloprid andemamectin

Numerous metals are known to possess good catalysisability and they may affect the behavior of coexisting pes-ticides in the soil Thus the most important segment of thepresent investigation was to study the correlations among theselected pesticides and variousmetal levelsThe data depicteda strong positive correlation between acetamiprid and Cuwith 119903-value of 0239 A strong positive correlation pointedtowards an increase in the concentration of acetamiprid

8 Scientifica

Table3Correlationcoeffi

cientm

atrix

aforv

arious

parameterso

fsoilsam

ples

(119899=52)

PbCr

Co

CuNi

Cd

OCb

pHEC

cClminus

NO3

minus

SO4

2minus

Imd

Eme

Acf

Pb10

00Cr

0179

1000

Co

0019

034

310

00Cu

0018

0132minus0002

1000

Ni

0199

046

00074

0431

1000

Cd

minus0154minus040

7minus0045minus0375minus043

010

00OC(

)0124

0083

0092minus0136minus0039minus0075

1000

pH0080minus0162

0164minus0124minus0076

0118

0187

1000

EC(120583SCm

)minus000

9minus0045minus0047

028

6034

2minus024

50137

0059

1000

Clminus

(mgkg)minus0163minus0255minus0140minus0079

0034

0144

0083

0058

029

210

00NO3

minus

(mgkg)

0011

0018minus0221minus0065

0051minus0076

0213

0014

0153

0087

1000

SO4

2minus

(mgkg)minus0080minus0149minus0201minus0096minus0057

0146

000

40235minus0156

0212

0177

1000

Imlowast

0086minus0021

0012

0017minus0317

0021

0100

0175minus0314minus0122minus0103

0052

1000

Emlowast

0213minus0071

0161

000

9minus0012

0015minus0239

0084minus0265minus0163minus0183

0085minus0086

1000

Aclowast

minus0119

minus030

5minus0143

0239minus0102

0163minus0077

0099

0313

0038

0007minus0085

0050minus0174

1000

a 119903-valuesa

resig

nificantat0

231

at119901lt005

b OC=organicc

arbo

nc EC=ele

ctric

alcond

uctiv

itydIm

=im

idacloprideEm

=em

amectin

fAc

=acetam

iprid

lowast

Con

centratio

nin120583gg

Scientifica 9

Wardrsquos method

OC ()Imidacloprid

pH

CdAcetamiprid

Conductivity (120583Scm)CuCoNiCr

EmamectinPb

04 06 08 10 12 14 16 18 2002Linkage distance

Clminus (mgkg)

NO3minus (mgkg)

SO42minus (mgkg)

Figure 3 Cluster analysis for the determination of various parame-ters

with the presence of greater concentration of copper in thesoil On the other hand imidacloprid in soil was found tobe negatively correlated with Ni of soil (119903-value of minus0317)Similarly a significant negative correlation was observedbetween Cr and acetamiprid (119903-value minus0305) Thus it wasevidenced that Cu stabilizes acetamiprid while Cr and Nifacilitate the degradation of acetamiprid and imidacloprid inthe soil [45]

Similar results have been reported for pyrethroid pes-ticides whose degradation was shown to be inhibited bythe presence of copper ions Ellis et al reported that metalslike Cu present in soil may react with the sulfhydryl groupof enzymes and inhibit their activity Thus the pesticidesbecome more persistent thereby leading to an increase intheir concentration with time [21 46]

33 Cluster Analysis of Various Parameters in the Soil Sam-ples Cluster analysis has proved to be a milestone towardthe source apportionment studies of various pollutants likemetals and pesticides in the soil and other media [47 48]In this analysis (Figure 3) linkage distance is used as themeasure of degree of closeness and hence relation among thevarious parameters [49] A number of clusters were formedwithin a significant linkage distance The strongest clusterwas observed between Cr and Ni evidencing that high Crcontent of the soil was associated with the enhanced Nilevels These two metals were further associated with Co toform a second cluster within linkage distance of 10 Themost important cluster of the study was observed betweenacetamiprid and conductivity that was further associatedwith Cu It evidenced that Cu present in the soil may causethe persistence of acetamiprid whose concentration increaseswith time Similarly emamectin was closely associated withPd

Cluster analysis revealed a close association betweensulphate and pH which formed a primary cluster withinlinkage distance of 06 This primary cluster was furtherassociated with Cd and Clminus within linkage distance of 10 onone side and with imidacloprid in the soil on the other side

The organic carbon of soil was associated with nitrate withina linkage distance of 08 and this factor was further associatedwith previous cluster

Overall the study revealed that frequently used pesti-cides that is imidacloprid emamectin and acetamipridwere present in the soil of cotton fields and were influencedby factors such as soil pH and organic carbon The studyalso furnished correlations among pesticides and metals inthe soil It was shown that presence of certain metals such asNi caused the decreased levels of imidacloprid Similarly Crenhanced the degradation of acetamiprid and Cu caused thepersistence of this pesticide in the soil

4 Conclusions

The soil samples collected from the cotton growing area ofPakpattan Pakistan were slightly basic in nature The meanPb Cr Co and Cu levels were below NEQS while the levelsof Ni and Cd were slightly above NEQS These levels may betolerated by following precautionarymeasures in agriculturalactivities Among the pesticides emamectin exhibited a highpersistence in the soil that was closely associated with soilCu content It was also found that Cu stabilizes acetamipridwhile Cr and Ni facilitate the degradation of acetamipridand imidacloprid Thus the study provides basis for therisk assessment studies that are quite necessary to managethe contaminated sites in a cost effective manner whilepreserving the public and ecosystem health It also providesa management strategy for remediation of contaminatedsoil that is adding traces of Ni and Cr in the soil mayhelp in the degradation of frequently used acetamiprid andimidacloprid

Conflict of Interests

The authors declare no conflict of interests

References

[1] R A Cloyd and J A Bethke ldquoImpact of neonicotinoidinsecticides onnatural enemies in greenhouse and interiorscapeenvironmentsrdquo Pest Management Science vol 67 no 1 pp 3ndash92011

[2] P Khaliq L A Hashmi and M H Qazi ldquoAgriculture andenvironmentrdquo Progress Farming vol 15 pp 16ndash23 1995

[3] H Shiraishi F Pula A Otsuki and T Iwakuma ldquoBehaviourof pesticides in Lake Kasumugaura Japanrdquo Science of the TotalEnvironment vol 72 pp 29ndash42 1988

[4] R Rial Otero B Cancho Grande M Arias Estevez E LopezPeriago and J Simal Gandara ldquoProcedure for themeasurementof soil inputs of plant-protection agents washed off throughvineyard canopy by rainfallrdquo Journal of Agricultural and FoodChemistry vol 51 no 17 pp 5041ndash5046 2003

[5] H M G van der Werf ldquoAssessing the impact of pesticideson the environmentrdquo Agriculture Ecosystems and Environmentvol 60 no 2-3 pp 81ndash96 1996

[6] G W vanLoon and S J Duffy Environmental Chemistry AGlobal Perspective Oxford University Press Oxford UK 2ndedition 2005

10 Scientifica

[7] P K Goel Water Pollution (Causes Effects and Control) NewAge International (P) New Delhi India 2nd edition 2006

[8] M Arias-Estevez E Lopez-Periago E Martınez-Carballo JSimal-Gandara J-C Mejuto and L Garcıa-Rıo ldquoThe mobilityand degradation of pesticides in soils and the pollution ofgroundwater resourcesrdquo Agriculture Ecosystems amp Environ-ment vol 123 no 4 pp 247ndash260 2008

[9] P J Shea T A Machacek and S D Comfort ldquoAcceleratedremediation of pesticide-contaminated soil with zerovalentironrdquo Environmental Pollution vol 132 no 2 pp 183ndash188 2004

[10] A Isaiah and M Paul ldquoSynergistic effect of chemical pesticideson commonly grown vegetables in Northern Indiardquo Epidemiol-ogy vol 18 p S86 2007

[11] J Fenoll P Hellın C Marın C M Martınez and A PFlores ldquoMultiresidue analysis of pesticides in soil by gaschromatography with nitrogen-phosphorus detection and gaschromatography mass spectrometryrdquo Journal of Agriculturaland Food Chemistry vol 53 no 20 pp 7661ndash7666 2005

[12] S Seccia P FidenteDMontesano andPMorrica ldquoDetermina-tion of neonicotinoid insecticides residues in bovine milk sam-ples by solid-phase extraction clean-up and liquid chromatog-raphy with diode-array detectionrdquo Journal of ChromatographyA vol 1214 no 1-2 pp 115ndash120 2008

[13] S M Dem J M Cobb and D E Mullins ldquoPesticide residuesin soil and water from four cotton growing areas of Mali WestAfricardquo Journal of Agricultural Food amp Environmental Sciencesvol 1 no 1 pp 1ndash12 2007

[14] M W Aktar M Paramasivam D Sengupta S Purkait MGanguly and S Banerjee ldquoImpact assessment of pesticideresidues in fish of Ganga river around Kolkata in West BengalrdquoEnvironmental Monitoring and Assessment vol 157 no 1ndash4 pp97ndash104 2009

[15] T R Sandrin and R M Maier ldquoImpact of metals on thebiodegradation of organic pollutantsrdquo Environmental HealthPerspectives vol 111 no 8 pp 1093ndash1101 2003

[16] S Khan Q Cao Y M Zheng Y Z Huang and Y G ZhuldquoHealth risks of heavy metals in contaminated soils and foodcrops irrigated with wastewater in Beijing Chinardquo Environmen-tal Pollution vol 152 no 3 pp 686ndash692 2008

[17] M-K Zhang Z-Y Liu and H Wang ldquoUse of single extractionmethods to predict bioavailability of heavy metals in pollutedsoils to ricerdquo Communications in Soil Science amp Plant Analysisvol 41 no 7 pp 820ndash831 2010

[18] Y PWang J Y ShiHWangQ Lin X CChen andYXChenldquoThe influence of soil heavy metals pollution on soil microbialbiomass enzyme activity and community composition near acopper smelterrdquo Ecotoxicology amp Environmental Safety vol 67no 1 pp 75ndash81 2007

[19] A A Helal D M Imam S M Khalifa and H F AlyldquoInteraction of pesticides with humic compounds and theirmetal complexesrdquo Radiochemistry vol 48 no 4 pp 419ndash4252006

[20] H Tian J Li Z Mu L Li and Z Hao ldquoEffect of pH onDDT degradation in aqueous solution using bimetallic NiFenanoparticlesrdquo Separation amp Purification Technology vol 66no 1 pp 84ndash89 2009

[21] T-F Liu C Sun N Ta J Hong S-G Yang and C-X ChenldquoEffect of copper on the degradation of pesticides cypermethrinand cyhalothrinrdquo Journal of Environmental Sciences vol 19 no10 pp 1235ndash1238 2007

[22] E Quivet R Faure J Georges J-O Paısse and P LanterildquoInfluence of metal salts on the photodegradation of imazapyr

an imidazolinone pesticiderdquo Pest Management Science vol 62no 5 pp 407ndash413 2006

[23] M Kamiya andK Kameyama ldquoEffects of selectedmetal ions onphotodegradation of organophosphorus pesticides sensitizedby humic acidsrdquo Chemosphere vol 45 no 3 pp 231ndash235 2001

[24] M Radojevic and V N Bashkin Practical EnvironmentalAnalysis Royal Society of Chemistry Cambridge UK 1999

[25] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of selected metals in tan-nery effluents and related soilrdquo Journal of Hazardous Materialsvol 122 no 1-2 pp 17ndash22 2005

[26] G R Blake and K H Hartge ldquoBulk and particle densityrdquo inMethods of Soil Analysis Part 1 pp 363ndash382 Soil Science Societyof America Madison Wis USA 1986

[27] P Patnaik Handbook of Environmental Analysis ChemicalPollutants in Air Water Soil and SolidWastes CRC Lewis BocaRaton Fla USA 1997

[28] A Bartosova A Michalıkova M Sirotiak and M SoldanldquoComparison of two spectrophotometric techniques for nutri-ents analyses inwater samplesrdquoResearch Papers Faculty ofMate-rials Science and Technology SlovakUniversity of Technology vol20 no 32 pp 8ndash19 2013

[29] H Spiegel E Filcheva P Hegymegi A Gal and F G AVerheijen ldquoReview and comparison of methods used for soilorganic carbon determination part 2 laboratory studyrdquo SoilScience Agrochemistry and Ecology vol 41 no 4 pp 19ndash25 2007

[30] K H Tan Soil Sampling Preparation and Analysis CRC PressTaylor amp Francis Group Boca Raton Fla USA 2nd edition2005

[31] StatSoft Inc STATISTICA for Windows (Computer ProgramManual) StatSoft Tulsa Okla USA 1999

[32] USDA Soil Quality Indicator pH Natural Resources Conserva-tion Service 1998

[33] G E Lailach T DThompson and GW Brindley ldquoAbsorptionof pyrimidines purines and nucleosides by Co- Ni- Cu- andFe(III)-Montmorillonite (Clay-Organic Studies XIII)rdquo Claysand Clay Minerals vol 16 no 4 pp 295ndash301 1968

[34] R G NashW G Harris and C C Lewis ldquoSoil pH andmetallicamendment effects on DDT conversion to DDErdquo Journal ofEnvironmental Quality vol 2 no 3 pp 390ndash394 1973

[35] J G Konrad and G Chesters ldquoDegradation in soils of cioduman organophosphate insecticiderdquo Journal of Agricultural andFood Chemistry vol 17 no 2 pp 226ndash230 1969

[36] A Albarran R Celis M C Hermosın A Lopez-Pineiro and JCornejo ldquoBehavior of simazine in soil amended with the finalresidue of the olive-oil extraction processrdquo Chemosphere vol54 no 6 pp 717ndash724 2004

[37] J Dec and J-M Bollag ldquoDetermination of covalent and non-covalent binding interactions between xenobiotic chemicalsand soilrdquo Soil Science vol 162 no 12 pp 858ndash874 1997

[38] A Nawab A Aleem and A Malik ldquoDetermination oforganochlorine pesticides in agricultural soil with specialreference to 120574-HCH degradation by Pseudomonas strainsrdquoBioresource Technology vol 88 no 1 pp 41ndash46 2003

[39] M Bavcon P Trebse and L Zupancic-Kralj ldquoInvestigationsof the determination and transformations of diazinon andmalathion under environmental conditions using gas chro-matography coupled with a flame ionisation detectorrdquo Chemo-sphere vol 50 no 5 pp 595ndash601 2003

[40] S A Sassman L S Lee M Bischoff and R F Turco ldquoAssessingNN1015840-dibutylurea (DBU) formation in soils after application of

Scientifica 11

n-butylisocyanate and benlate fungicidesrdquo Journal of Agricul-tural and Food Chemistry vol 52 no 4 pp 747ndash754 2004

[41] E R Mouta M R Soares and J C Casagrande ldquoCopperadsorption as a function of solution parameters of variablecharge soilsrdquo Journal of the Brazilian Chemical Society vol 19no 5 pp 996ndash1009 2008

[42] M Arshad J Silvestre E Pinelli et al ldquoA field study oflead phytoextraction by various scented Pelargonium cultivarsrdquoChemosphere vol 71 no 11 pp 2187ndash2192 2008

[43] G Uzu S Sobanska Y Aliouane P Pradere and C DumatldquoStudy of lead phytoavailability for atmospheric industrialmicronic and sub-micronic particles in relation with leadspeciationrdquo Environmental Pollution vol 157 no 4 pp 1178ndash1185 2009

[44] L H P Jones and S C Jarvis ldquoThe fate of heavy metalsrdquo inTheChemistry of Soil Processes D J Green andMH B Hayes Edsp 593 John Wiley amp Sons New York NY USA 1981

[45] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of trace metal levels intannery effluents in relation to soil and water a case study fromPeshawar Pakistanrdquo Journal of EnvironmentalManagement vol79 no 1 pp 20ndash29 2006

[46] R J Ellis B Neish MW Trett et al ldquoComparison of microbialand meiofaunal community analyses for determining impact ofheavy metal contaminationrdquo Journal of Microbiological Meth-ods vol 45 no 3 pp 171ndash185 2001

[47] S R Tariq F Iqbal and A Ijaz ldquoAssessment and multivariateanalysis of metals in surgical instrument industry affected topsoils and groundwater for future reclamationrdquo InternationalJournal of Environment and Pollution vol 1 pp 54ndash71 2013

[48] S R Tariq and N Rashid ldquoMultivariate analysis of metal levelsin paddy soil rice plants and rice grains a case study fromShakargarh Pakistanrdquo Journal of Chemistry vol 2013 ArticleID 539251 10 pages 2013

[49] B S Everitt S Landau and M Leese Cluster Analysis Arnold4th edition 2001

Submit your manuscripts athttpwwwhindawicom

Nutrition and Metabolism

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Food ScienceInternational Journal of

Agronomy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom

Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Plant GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Biotechnology Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Forestry ResearchInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Veterinary Medicine International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Cell BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Evolutionary BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Scientifica 7

on leaded gasoline thus the source of this lead in soilwas traced in various fungicides and pesticides like leadarsenate and so forth that are used at various stages of cropproduction [2] Cadmium was the metal that was presentat trace level of 0585mgkg Chromium another hazardousmetal was found to be present at a mean level of 586mgkgIts maximum concentration was recorded to be 96mgkgwhich is quite higher than the limit set for agricultural soilsThis chromium not only is hazardous for soil biota butmay also contaminate the food chain through uptake andaccumulation by plants furthermore depending on the soilconditions like pH it may become soluble and thus enter thegroundwater the only source of drinking water in the area

The mean levels recorded for Co were 7558mgkg Theorder of themean concentrations ofmetals in the soil samplesremained Ni gt Cu gt Pb gt Co gt Cr gt Cd The symmetryparameters for the data that is standard deviation skewnessand kurtosis are also listed in Table 2

A comparison of mean metal levels with NationalEnvironmental Quality Standards (NEQS) is also depictedin Table 2 The average Pb concentration in soil sampleswas found to be 1618mgkg against the standard valueof 25mgkg The estimated value of lead in soil sampleswas lower than standard value which indicated that soil Pbwas below the contamination level and would not pose asignificant threat of contaminating the food chain MoreoverPb uptake by plants depends upon soil pH that is at higherpH lead becomes immobilized It is also known that due tosmall transfer factor Pb is not taken up by plants below aconcentration of 300120583gg in soil and if taken up it wouldaccumulate in leaves rather than the fruit [42 43]

Themean level of Cr recorded in soil was 586mgkgThisvalue is approximately four times less than standard value of20mgkg (NEQS) Co was present in the soil samples at themean level of 7558mgkg which is also less than standardvalue of 10mgkg The mean concentration of Cu in soilsamples was found to be 1812mgkg Ni was present in soilsamples at the mean level of 2216mgkg slightly higher thanthe recommended standard value of 20mgkg

The mean concentration of Cd was found to be0585mgkg a value slightly exceeding the standard valueof 05mgkg In fact fertilizers are added regularly to soilsto replenish N K and P for good crop growth Thesecompounds contain trace amounts of Cd as impuritieswhich after continued application are significantly increasedin the soil [44] Overall it was concluded that Pb Cr Cuand Co were present in tolerable range in the soil samples butNi and Cd surpassed the standard value but not to greaterextents Thus although the selected metals do not pose anythreat to the environment at their present levels but with thepassage of time the unwise use of agricultural activities maylead to a large buildup of metals in the soil that may endangerthe environment as well as human health

32 Correlation Coefficient Matrices of Various Parameters inthe Soil Table 3 depicted the correlation coefficient matrixfor the studied physicochemical parameters pesticides andmetal levels in the soil samples collected from the agriculturalfields The 119903-values were found to be significant at plusmn0231

(119901 lt 005) The data was characterized by both negative andpositive correlations between various pairs of parametersThe data was nonnormally distributed and also the anthro-pogenic activities led to a change in the natural concentrationof some of the parameters Thus all the observed correlationswere not high For the physicochemical parameters themost significant positive correlation was observed betweenelectrical conductivity and chloride levels with an 119903-value0292 evidencing that in about 292 cases the electricalconductivity of soil was observed to be increased with anincrease in chloride content and vice versa Similarly a strongpositive correlation was observed between pH and sulphatewith 119903-values of 0235 Organic carbon content of soil wasfound to be positively correlated with nitrate levels but thiscorrelation was not significant

The correlation coefficientmatrix for the levels of selectedmetals in the collected soil samples depicted the strongestpositive correlation between Cr and Ni at an 119903-value of 0460thereby showing that in 460 cases the concentration ofCr went in parallel with concentration of Ni thus sharing asimilar origin in the soil matrix The next strongest positivecorrelation was observed betweenNi and Cu pair (0431)Theother metal pair that was significantly positively correlatedincluded Cr-Co (119903-value 0343) Cr Ni and Cu were foundto be strongly negatively correlated with Cd (119903-values ofminus0407 minus0430 and minus0375 resp) depicting an increase inconcentration of one metal with a decrease in concentrationof other metals

No significant positive or negative correlation wasobserved among the selected pesticides depicting that thesources of pesticides in the soil were not the same Thisis also due to the fact that different pesticides are appliedto the crops at different stages of crop production Thusthey enter the soil at different periods of time The datacorresponding to the correlation coefficient matrix for thephysicochemical parameters and the various metals depictedonly few significant positivenegative correlations Ni ofthe soil exhibited the strongest positive correlation withits conductivity with 119903-value of 0342 Cu was also signifi-cantly positively correlated with the conductivity (119903-value of0286) Cd and electrical conductivitywere significantly nega-tively correlated Another significant negative correlationwasobserved between Cr and nitrate level of soil solution Theother correlations were too naıve to be discussed

The correlation coefficient matrix for the pesticides-to-physicochemical parameters depicted a significant neg-ative correlation between soil organic carbon content andemamectin thereby evidencing the influence of soil organiccarbon on the sorption of emamectin Soil EC values werealso found to be negatively correlated with imidacloprid andemamectin

Numerous metals are known to possess good catalysisability and they may affect the behavior of coexisting pes-ticides in the soil Thus the most important segment of thepresent investigation was to study the correlations among theselected pesticides and variousmetal levelsThe data depicteda strong positive correlation between acetamiprid and Cuwith 119903-value of 0239 A strong positive correlation pointedtowards an increase in the concentration of acetamiprid

8 Scientifica

Table3Correlationcoeffi

cientm

atrix

aforv

arious

parameterso

fsoilsam

ples

(119899=52)

PbCr

Co

CuNi

Cd

OCb

pHEC

cClminus

NO3

minus

SO4

2minus

Imd

Eme

Acf

Pb10

00Cr

0179

1000

Co

0019

034

310

00Cu

0018

0132minus0002

1000

Ni

0199

046

00074

0431

1000

Cd

minus0154minus040

7minus0045minus0375minus043

010

00OC(

)0124

0083

0092minus0136minus0039minus0075

1000

pH0080minus0162

0164minus0124minus0076

0118

0187

1000

EC(120583SCm

)minus000

9minus0045minus0047

028

6034

2minus024

50137

0059

1000

Clminus

(mgkg)minus0163minus0255minus0140minus0079

0034

0144

0083

0058

029

210

00NO3

minus

(mgkg)

0011

0018minus0221minus0065

0051minus0076

0213

0014

0153

0087

1000

SO4

2minus

(mgkg)minus0080minus0149minus0201minus0096minus0057

0146

000

40235minus0156

0212

0177

1000

Imlowast

0086minus0021

0012

0017minus0317

0021

0100

0175minus0314minus0122minus0103

0052

1000

Emlowast

0213minus0071

0161

000

9minus0012

0015minus0239

0084minus0265minus0163minus0183

0085minus0086

1000

Aclowast

minus0119

minus030

5minus0143

0239minus0102

0163minus0077

0099

0313

0038

0007minus0085

0050minus0174

1000

a 119903-valuesa

resig

nificantat0

231

at119901lt005

b OC=organicc

arbo

nc EC=ele

ctric

alcond

uctiv

itydIm

=im

idacloprideEm

=em

amectin

fAc

=acetam

iprid

lowast

Con

centratio

nin120583gg

Scientifica 9

Wardrsquos method

OC ()Imidacloprid

pH

CdAcetamiprid

Conductivity (120583Scm)CuCoNiCr

EmamectinPb

04 06 08 10 12 14 16 18 2002Linkage distance

Clminus (mgkg)

NO3minus (mgkg)

SO42minus (mgkg)

Figure 3 Cluster analysis for the determination of various parame-ters

with the presence of greater concentration of copper in thesoil On the other hand imidacloprid in soil was found tobe negatively correlated with Ni of soil (119903-value of minus0317)Similarly a significant negative correlation was observedbetween Cr and acetamiprid (119903-value minus0305) Thus it wasevidenced that Cu stabilizes acetamiprid while Cr and Nifacilitate the degradation of acetamiprid and imidacloprid inthe soil [45]

Similar results have been reported for pyrethroid pes-ticides whose degradation was shown to be inhibited bythe presence of copper ions Ellis et al reported that metalslike Cu present in soil may react with the sulfhydryl groupof enzymes and inhibit their activity Thus the pesticidesbecome more persistent thereby leading to an increase intheir concentration with time [21 46]

33 Cluster Analysis of Various Parameters in the Soil Sam-ples Cluster analysis has proved to be a milestone towardthe source apportionment studies of various pollutants likemetals and pesticides in the soil and other media [47 48]In this analysis (Figure 3) linkage distance is used as themeasure of degree of closeness and hence relation among thevarious parameters [49] A number of clusters were formedwithin a significant linkage distance The strongest clusterwas observed between Cr and Ni evidencing that high Crcontent of the soil was associated with the enhanced Nilevels These two metals were further associated with Co toform a second cluster within linkage distance of 10 Themost important cluster of the study was observed betweenacetamiprid and conductivity that was further associatedwith Cu It evidenced that Cu present in the soil may causethe persistence of acetamiprid whose concentration increaseswith time Similarly emamectin was closely associated withPd

Cluster analysis revealed a close association betweensulphate and pH which formed a primary cluster withinlinkage distance of 06 This primary cluster was furtherassociated with Cd and Clminus within linkage distance of 10 onone side and with imidacloprid in the soil on the other side

The organic carbon of soil was associated with nitrate withina linkage distance of 08 and this factor was further associatedwith previous cluster

Overall the study revealed that frequently used pesti-cides that is imidacloprid emamectin and acetamipridwere present in the soil of cotton fields and were influencedby factors such as soil pH and organic carbon The studyalso furnished correlations among pesticides and metals inthe soil It was shown that presence of certain metals such asNi caused the decreased levels of imidacloprid Similarly Crenhanced the degradation of acetamiprid and Cu caused thepersistence of this pesticide in the soil

4 Conclusions

The soil samples collected from the cotton growing area ofPakpattan Pakistan were slightly basic in nature The meanPb Cr Co and Cu levels were below NEQS while the levelsof Ni and Cd were slightly above NEQS These levels may betolerated by following precautionarymeasures in agriculturalactivities Among the pesticides emamectin exhibited a highpersistence in the soil that was closely associated with soilCu content It was also found that Cu stabilizes acetamipridwhile Cr and Ni facilitate the degradation of acetamipridand imidacloprid Thus the study provides basis for therisk assessment studies that are quite necessary to managethe contaminated sites in a cost effective manner whilepreserving the public and ecosystem health It also providesa management strategy for remediation of contaminatedsoil that is adding traces of Ni and Cr in the soil mayhelp in the degradation of frequently used acetamiprid andimidacloprid

Conflict of Interests

The authors declare no conflict of interests

References

[1] R A Cloyd and J A Bethke ldquoImpact of neonicotinoidinsecticides onnatural enemies in greenhouse and interiorscapeenvironmentsrdquo Pest Management Science vol 67 no 1 pp 3ndash92011

[2] P Khaliq L A Hashmi and M H Qazi ldquoAgriculture andenvironmentrdquo Progress Farming vol 15 pp 16ndash23 1995

[3] H Shiraishi F Pula A Otsuki and T Iwakuma ldquoBehaviourof pesticides in Lake Kasumugaura Japanrdquo Science of the TotalEnvironment vol 72 pp 29ndash42 1988

[4] R Rial Otero B Cancho Grande M Arias Estevez E LopezPeriago and J Simal Gandara ldquoProcedure for themeasurementof soil inputs of plant-protection agents washed off throughvineyard canopy by rainfallrdquo Journal of Agricultural and FoodChemistry vol 51 no 17 pp 5041ndash5046 2003

[5] H M G van der Werf ldquoAssessing the impact of pesticideson the environmentrdquo Agriculture Ecosystems and Environmentvol 60 no 2-3 pp 81ndash96 1996

[6] G W vanLoon and S J Duffy Environmental Chemistry AGlobal Perspective Oxford University Press Oxford UK 2ndedition 2005

10 Scientifica

[7] P K Goel Water Pollution (Causes Effects and Control) NewAge International (P) New Delhi India 2nd edition 2006

[8] M Arias-Estevez E Lopez-Periago E Martınez-Carballo JSimal-Gandara J-C Mejuto and L Garcıa-Rıo ldquoThe mobilityand degradation of pesticides in soils and the pollution ofgroundwater resourcesrdquo Agriculture Ecosystems amp Environ-ment vol 123 no 4 pp 247ndash260 2008

[9] P J Shea T A Machacek and S D Comfort ldquoAcceleratedremediation of pesticide-contaminated soil with zerovalentironrdquo Environmental Pollution vol 132 no 2 pp 183ndash188 2004

[10] A Isaiah and M Paul ldquoSynergistic effect of chemical pesticideson commonly grown vegetables in Northern Indiardquo Epidemiol-ogy vol 18 p S86 2007

[11] J Fenoll P Hellın C Marın C M Martınez and A PFlores ldquoMultiresidue analysis of pesticides in soil by gaschromatography with nitrogen-phosphorus detection and gaschromatography mass spectrometryrdquo Journal of Agriculturaland Food Chemistry vol 53 no 20 pp 7661ndash7666 2005

[12] S Seccia P FidenteDMontesano andPMorrica ldquoDetermina-tion of neonicotinoid insecticides residues in bovine milk sam-ples by solid-phase extraction clean-up and liquid chromatog-raphy with diode-array detectionrdquo Journal of ChromatographyA vol 1214 no 1-2 pp 115ndash120 2008

[13] S M Dem J M Cobb and D E Mullins ldquoPesticide residuesin soil and water from four cotton growing areas of Mali WestAfricardquo Journal of Agricultural Food amp Environmental Sciencesvol 1 no 1 pp 1ndash12 2007

[14] M W Aktar M Paramasivam D Sengupta S Purkait MGanguly and S Banerjee ldquoImpact assessment of pesticideresidues in fish of Ganga river around Kolkata in West BengalrdquoEnvironmental Monitoring and Assessment vol 157 no 1ndash4 pp97ndash104 2009

[15] T R Sandrin and R M Maier ldquoImpact of metals on thebiodegradation of organic pollutantsrdquo Environmental HealthPerspectives vol 111 no 8 pp 1093ndash1101 2003

[16] S Khan Q Cao Y M Zheng Y Z Huang and Y G ZhuldquoHealth risks of heavy metals in contaminated soils and foodcrops irrigated with wastewater in Beijing Chinardquo Environmen-tal Pollution vol 152 no 3 pp 686ndash692 2008

[17] M-K Zhang Z-Y Liu and H Wang ldquoUse of single extractionmethods to predict bioavailability of heavy metals in pollutedsoils to ricerdquo Communications in Soil Science amp Plant Analysisvol 41 no 7 pp 820ndash831 2010

[18] Y PWang J Y ShiHWangQ Lin X CChen andYXChenldquoThe influence of soil heavy metals pollution on soil microbialbiomass enzyme activity and community composition near acopper smelterrdquo Ecotoxicology amp Environmental Safety vol 67no 1 pp 75ndash81 2007

[19] A A Helal D M Imam S M Khalifa and H F AlyldquoInteraction of pesticides with humic compounds and theirmetal complexesrdquo Radiochemistry vol 48 no 4 pp 419ndash4252006

[20] H Tian J Li Z Mu L Li and Z Hao ldquoEffect of pH onDDT degradation in aqueous solution using bimetallic NiFenanoparticlesrdquo Separation amp Purification Technology vol 66no 1 pp 84ndash89 2009

[21] T-F Liu C Sun N Ta J Hong S-G Yang and C-X ChenldquoEffect of copper on the degradation of pesticides cypermethrinand cyhalothrinrdquo Journal of Environmental Sciences vol 19 no10 pp 1235ndash1238 2007

[22] E Quivet R Faure J Georges J-O Paısse and P LanterildquoInfluence of metal salts on the photodegradation of imazapyr

an imidazolinone pesticiderdquo Pest Management Science vol 62no 5 pp 407ndash413 2006

[23] M Kamiya andK Kameyama ldquoEffects of selectedmetal ions onphotodegradation of organophosphorus pesticides sensitizedby humic acidsrdquo Chemosphere vol 45 no 3 pp 231ndash235 2001

[24] M Radojevic and V N Bashkin Practical EnvironmentalAnalysis Royal Society of Chemistry Cambridge UK 1999

[25] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of selected metals in tan-nery effluents and related soilrdquo Journal of Hazardous Materialsvol 122 no 1-2 pp 17ndash22 2005

[26] G R Blake and K H Hartge ldquoBulk and particle densityrdquo inMethods of Soil Analysis Part 1 pp 363ndash382 Soil Science Societyof America Madison Wis USA 1986

[27] P Patnaik Handbook of Environmental Analysis ChemicalPollutants in Air Water Soil and SolidWastes CRC Lewis BocaRaton Fla USA 1997

[28] A Bartosova A Michalıkova M Sirotiak and M SoldanldquoComparison of two spectrophotometric techniques for nutri-ents analyses inwater samplesrdquoResearch Papers Faculty ofMate-rials Science and Technology SlovakUniversity of Technology vol20 no 32 pp 8ndash19 2013

[29] H Spiegel E Filcheva P Hegymegi A Gal and F G AVerheijen ldquoReview and comparison of methods used for soilorganic carbon determination part 2 laboratory studyrdquo SoilScience Agrochemistry and Ecology vol 41 no 4 pp 19ndash25 2007

[30] K H Tan Soil Sampling Preparation and Analysis CRC PressTaylor amp Francis Group Boca Raton Fla USA 2nd edition2005

[31] StatSoft Inc STATISTICA for Windows (Computer ProgramManual) StatSoft Tulsa Okla USA 1999

[32] USDA Soil Quality Indicator pH Natural Resources Conserva-tion Service 1998

[33] G E Lailach T DThompson and GW Brindley ldquoAbsorptionof pyrimidines purines and nucleosides by Co- Ni- Cu- andFe(III)-Montmorillonite (Clay-Organic Studies XIII)rdquo Claysand Clay Minerals vol 16 no 4 pp 295ndash301 1968

[34] R G NashW G Harris and C C Lewis ldquoSoil pH andmetallicamendment effects on DDT conversion to DDErdquo Journal ofEnvironmental Quality vol 2 no 3 pp 390ndash394 1973

[35] J G Konrad and G Chesters ldquoDegradation in soils of cioduman organophosphate insecticiderdquo Journal of Agricultural andFood Chemistry vol 17 no 2 pp 226ndash230 1969

[36] A Albarran R Celis M C Hermosın A Lopez-Pineiro and JCornejo ldquoBehavior of simazine in soil amended with the finalresidue of the olive-oil extraction processrdquo Chemosphere vol54 no 6 pp 717ndash724 2004

[37] J Dec and J-M Bollag ldquoDetermination of covalent and non-covalent binding interactions between xenobiotic chemicalsand soilrdquo Soil Science vol 162 no 12 pp 858ndash874 1997

[38] A Nawab A Aleem and A Malik ldquoDetermination oforganochlorine pesticides in agricultural soil with specialreference to 120574-HCH degradation by Pseudomonas strainsrdquoBioresource Technology vol 88 no 1 pp 41ndash46 2003

[39] M Bavcon P Trebse and L Zupancic-Kralj ldquoInvestigationsof the determination and transformations of diazinon andmalathion under environmental conditions using gas chro-matography coupled with a flame ionisation detectorrdquo Chemo-sphere vol 50 no 5 pp 595ndash601 2003

[40] S A Sassman L S Lee M Bischoff and R F Turco ldquoAssessingNN1015840-dibutylurea (DBU) formation in soils after application of

Scientifica 11

n-butylisocyanate and benlate fungicidesrdquo Journal of Agricul-tural and Food Chemistry vol 52 no 4 pp 747ndash754 2004

[41] E R Mouta M R Soares and J C Casagrande ldquoCopperadsorption as a function of solution parameters of variablecharge soilsrdquo Journal of the Brazilian Chemical Society vol 19no 5 pp 996ndash1009 2008

[42] M Arshad J Silvestre E Pinelli et al ldquoA field study oflead phytoextraction by various scented Pelargonium cultivarsrdquoChemosphere vol 71 no 11 pp 2187ndash2192 2008

[43] G Uzu S Sobanska Y Aliouane P Pradere and C DumatldquoStudy of lead phytoavailability for atmospheric industrialmicronic and sub-micronic particles in relation with leadspeciationrdquo Environmental Pollution vol 157 no 4 pp 1178ndash1185 2009

[44] L H P Jones and S C Jarvis ldquoThe fate of heavy metalsrdquo inTheChemistry of Soil Processes D J Green andMH B Hayes Edsp 593 John Wiley amp Sons New York NY USA 1981

[45] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of trace metal levels intannery effluents in relation to soil and water a case study fromPeshawar Pakistanrdquo Journal of EnvironmentalManagement vol79 no 1 pp 20ndash29 2006

[46] R J Ellis B Neish MW Trett et al ldquoComparison of microbialand meiofaunal community analyses for determining impact ofheavy metal contaminationrdquo Journal of Microbiological Meth-ods vol 45 no 3 pp 171ndash185 2001

[47] S R Tariq F Iqbal and A Ijaz ldquoAssessment and multivariateanalysis of metals in surgical instrument industry affected topsoils and groundwater for future reclamationrdquo InternationalJournal of Environment and Pollution vol 1 pp 54ndash71 2013

[48] S R Tariq and N Rashid ldquoMultivariate analysis of metal levelsin paddy soil rice plants and rice grains a case study fromShakargarh Pakistanrdquo Journal of Chemistry vol 2013 ArticleID 539251 10 pages 2013

[49] B S Everitt S Landau and M Leese Cluster Analysis Arnold4th edition 2001

Submit your manuscripts athttpwwwhindawicom

Nutrition and Metabolism

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Food ScienceInternational Journal of

Agronomy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom

Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Plant GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Biotechnology Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Forestry ResearchInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Veterinary Medicine International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Cell BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Evolutionary BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

8 Scientifica

Table3Correlationcoeffi

cientm

atrix

aforv

arious

parameterso

fsoilsam

ples

(119899=52)

PbCr

Co

CuNi

Cd

OCb

pHEC

cClminus

NO3

minus

SO4

2minus

Imd

Eme

Acf

Pb10

00Cr

0179

1000

Co

0019

034

310

00Cu

0018

0132minus0002

1000

Ni

0199

046

00074

0431

1000

Cd

minus0154minus040

7minus0045minus0375minus043

010

00OC(

)0124

0083

0092minus0136minus0039minus0075

1000

pH0080minus0162

0164minus0124minus0076

0118

0187

1000

EC(120583SCm

)minus000

9minus0045minus0047

028

6034

2minus024

50137

0059

1000

Clminus

(mgkg)minus0163minus0255minus0140minus0079

0034

0144

0083

0058

029

210

00NO3

minus

(mgkg)

0011

0018minus0221minus0065

0051minus0076

0213

0014

0153

0087

1000

SO4

2minus

(mgkg)minus0080minus0149minus0201minus0096minus0057

0146

000

40235minus0156

0212

0177

1000

Imlowast

0086minus0021

0012

0017minus0317

0021

0100

0175minus0314minus0122minus0103

0052

1000

Emlowast

0213minus0071

0161

000

9minus0012

0015minus0239

0084minus0265minus0163minus0183

0085minus0086

1000

Aclowast

minus0119

minus030

5minus0143

0239minus0102

0163minus0077

0099

0313

0038

0007minus0085

0050minus0174

1000

a 119903-valuesa

resig

nificantat0

231

at119901lt005

b OC=organicc

arbo

nc EC=ele

ctric

alcond

uctiv

itydIm

=im

idacloprideEm

=em

amectin

fAc

=acetam

iprid

lowast

Con

centratio

nin120583gg

Scientifica 9

Wardrsquos method

OC ()Imidacloprid

pH

CdAcetamiprid

Conductivity (120583Scm)CuCoNiCr

EmamectinPb

04 06 08 10 12 14 16 18 2002Linkage distance

Clminus (mgkg)

NO3minus (mgkg)

SO42minus (mgkg)

Figure 3 Cluster analysis for the determination of various parame-ters

with the presence of greater concentration of copper in thesoil On the other hand imidacloprid in soil was found tobe negatively correlated with Ni of soil (119903-value of minus0317)Similarly a significant negative correlation was observedbetween Cr and acetamiprid (119903-value minus0305) Thus it wasevidenced that Cu stabilizes acetamiprid while Cr and Nifacilitate the degradation of acetamiprid and imidacloprid inthe soil [45]

Similar results have been reported for pyrethroid pes-ticides whose degradation was shown to be inhibited bythe presence of copper ions Ellis et al reported that metalslike Cu present in soil may react with the sulfhydryl groupof enzymes and inhibit their activity Thus the pesticidesbecome more persistent thereby leading to an increase intheir concentration with time [21 46]

33 Cluster Analysis of Various Parameters in the Soil Sam-ples Cluster analysis has proved to be a milestone towardthe source apportionment studies of various pollutants likemetals and pesticides in the soil and other media [47 48]In this analysis (Figure 3) linkage distance is used as themeasure of degree of closeness and hence relation among thevarious parameters [49] A number of clusters were formedwithin a significant linkage distance The strongest clusterwas observed between Cr and Ni evidencing that high Crcontent of the soil was associated with the enhanced Nilevels These two metals were further associated with Co toform a second cluster within linkage distance of 10 Themost important cluster of the study was observed betweenacetamiprid and conductivity that was further associatedwith Cu It evidenced that Cu present in the soil may causethe persistence of acetamiprid whose concentration increaseswith time Similarly emamectin was closely associated withPd

Cluster analysis revealed a close association betweensulphate and pH which formed a primary cluster withinlinkage distance of 06 This primary cluster was furtherassociated with Cd and Clminus within linkage distance of 10 onone side and with imidacloprid in the soil on the other side

The organic carbon of soil was associated with nitrate withina linkage distance of 08 and this factor was further associatedwith previous cluster

Overall the study revealed that frequently used pesti-cides that is imidacloprid emamectin and acetamipridwere present in the soil of cotton fields and were influencedby factors such as soil pH and organic carbon The studyalso furnished correlations among pesticides and metals inthe soil It was shown that presence of certain metals such asNi caused the decreased levels of imidacloprid Similarly Crenhanced the degradation of acetamiprid and Cu caused thepersistence of this pesticide in the soil

4 Conclusions

The soil samples collected from the cotton growing area ofPakpattan Pakistan were slightly basic in nature The meanPb Cr Co and Cu levels were below NEQS while the levelsof Ni and Cd were slightly above NEQS These levels may betolerated by following precautionarymeasures in agriculturalactivities Among the pesticides emamectin exhibited a highpersistence in the soil that was closely associated with soilCu content It was also found that Cu stabilizes acetamipridwhile Cr and Ni facilitate the degradation of acetamipridand imidacloprid Thus the study provides basis for therisk assessment studies that are quite necessary to managethe contaminated sites in a cost effective manner whilepreserving the public and ecosystem health It also providesa management strategy for remediation of contaminatedsoil that is adding traces of Ni and Cr in the soil mayhelp in the degradation of frequently used acetamiprid andimidacloprid

Conflict of Interests

The authors declare no conflict of interests

References

[1] R A Cloyd and J A Bethke ldquoImpact of neonicotinoidinsecticides onnatural enemies in greenhouse and interiorscapeenvironmentsrdquo Pest Management Science vol 67 no 1 pp 3ndash92011

[2] P Khaliq L A Hashmi and M H Qazi ldquoAgriculture andenvironmentrdquo Progress Farming vol 15 pp 16ndash23 1995

[3] H Shiraishi F Pula A Otsuki and T Iwakuma ldquoBehaviourof pesticides in Lake Kasumugaura Japanrdquo Science of the TotalEnvironment vol 72 pp 29ndash42 1988

[4] R Rial Otero B Cancho Grande M Arias Estevez E LopezPeriago and J Simal Gandara ldquoProcedure for themeasurementof soil inputs of plant-protection agents washed off throughvineyard canopy by rainfallrdquo Journal of Agricultural and FoodChemistry vol 51 no 17 pp 5041ndash5046 2003

[5] H M G van der Werf ldquoAssessing the impact of pesticideson the environmentrdquo Agriculture Ecosystems and Environmentvol 60 no 2-3 pp 81ndash96 1996

[6] G W vanLoon and S J Duffy Environmental Chemistry AGlobal Perspective Oxford University Press Oxford UK 2ndedition 2005

10 Scientifica

[7] P K Goel Water Pollution (Causes Effects and Control) NewAge International (P) New Delhi India 2nd edition 2006

[8] M Arias-Estevez E Lopez-Periago E Martınez-Carballo JSimal-Gandara J-C Mejuto and L Garcıa-Rıo ldquoThe mobilityand degradation of pesticides in soils and the pollution ofgroundwater resourcesrdquo Agriculture Ecosystems amp Environ-ment vol 123 no 4 pp 247ndash260 2008

[9] P J Shea T A Machacek and S D Comfort ldquoAcceleratedremediation of pesticide-contaminated soil with zerovalentironrdquo Environmental Pollution vol 132 no 2 pp 183ndash188 2004

[10] A Isaiah and M Paul ldquoSynergistic effect of chemical pesticideson commonly grown vegetables in Northern Indiardquo Epidemiol-ogy vol 18 p S86 2007

[11] J Fenoll P Hellın C Marın C M Martınez and A PFlores ldquoMultiresidue analysis of pesticides in soil by gaschromatography with nitrogen-phosphorus detection and gaschromatography mass spectrometryrdquo Journal of Agriculturaland Food Chemistry vol 53 no 20 pp 7661ndash7666 2005

[12] S Seccia P FidenteDMontesano andPMorrica ldquoDetermina-tion of neonicotinoid insecticides residues in bovine milk sam-ples by solid-phase extraction clean-up and liquid chromatog-raphy with diode-array detectionrdquo Journal of ChromatographyA vol 1214 no 1-2 pp 115ndash120 2008

[13] S M Dem J M Cobb and D E Mullins ldquoPesticide residuesin soil and water from four cotton growing areas of Mali WestAfricardquo Journal of Agricultural Food amp Environmental Sciencesvol 1 no 1 pp 1ndash12 2007

[14] M W Aktar M Paramasivam D Sengupta S Purkait MGanguly and S Banerjee ldquoImpact assessment of pesticideresidues in fish of Ganga river around Kolkata in West BengalrdquoEnvironmental Monitoring and Assessment vol 157 no 1ndash4 pp97ndash104 2009

[15] T R Sandrin and R M Maier ldquoImpact of metals on thebiodegradation of organic pollutantsrdquo Environmental HealthPerspectives vol 111 no 8 pp 1093ndash1101 2003

[16] S Khan Q Cao Y M Zheng Y Z Huang and Y G ZhuldquoHealth risks of heavy metals in contaminated soils and foodcrops irrigated with wastewater in Beijing Chinardquo Environmen-tal Pollution vol 152 no 3 pp 686ndash692 2008

[17] M-K Zhang Z-Y Liu and H Wang ldquoUse of single extractionmethods to predict bioavailability of heavy metals in pollutedsoils to ricerdquo Communications in Soil Science amp Plant Analysisvol 41 no 7 pp 820ndash831 2010

[18] Y PWang J Y ShiHWangQ Lin X CChen andYXChenldquoThe influence of soil heavy metals pollution on soil microbialbiomass enzyme activity and community composition near acopper smelterrdquo Ecotoxicology amp Environmental Safety vol 67no 1 pp 75ndash81 2007

[19] A A Helal D M Imam S M Khalifa and H F AlyldquoInteraction of pesticides with humic compounds and theirmetal complexesrdquo Radiochemistry vol 48 no 4 pp 419ndash4252006

[20] H Tian J Li Z Mu L Li and Z Hao ldquoEffect of pH onDDT degradation in aqueous solution using bimetallic NiFenanoparticlesrdquo Separation amp Purification Technology vol 66no 1 pp 84ndash89 2009

[21] T-F Liu C Sun N Ta J Hong S-G Yang and C-X ChenldquoEffect of copper on the degradation of pesticides cypermethrinand cyhalothrinrdquo Journal of Environmental Sciences vol 19 no10 pp 1235ndash1238 2007

[22] E Quivet R Faure J Georges J-O Paısse and P LanterildquoInfluence of metal salts on the photodegradation of imazapyr

an imidazolinone pesticiderdquo Pest Management Science vol 62no 5 pp 407ndash413 2006

[23] M Kamiya andK Kameyama ldquoEffects of selectedmetal ions onphotodegradation of organophosphorus pesticides sensitizedby humic acidsrdquo Chemosphere vol 45 no 3 pp 231ndash235 2001

[24] M Radojevic and V N Bashkin Practical EnvironmentalAnalysis Royal Society of Chemistry Cambridge UK 1999

[25] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of selected metals in tan-nery effluents and related soilrdquo Journal of Hazardous Materialsvol 122 no 1-2 pp 17ndash22 2005

[26] G R Blake and K H Hartge ldquoBulk and particle densityrdquo inMethods of Soil Analysis Part 1 pp 363ndash382 Soil Science Societyof America Madison Wis USA 1986

[27] P Patnaik Handbook of Environmental Analysis ChemicalPollutants in Air Water Soil and SolidWastes CRC Lewis BocaRaton Fla USA 1997

[28] A Bartosova A Michalıkova M Sirotiak and M SoldanldquoComparison of two spectrophotometric techniques for nutri-ents analyses inwater samplesrdquoResearch Papers Faculty ofMate-rials Science and Technology SlovakUniversity of Technology vol20 no 32 pp 8ndash19 2013

[29] H Spiegel E Filcheva P Hegymegi A Gal and F G AVerheijen ldquoReview and comparison of methods used for soilorganic carbon determination part 2 laboratory studyrdquo SoilScience Agrochemistry and Ecology vol 41 no 4 pp 19ndash25 2007

[30] K H Tan Soil Sampling Preparation and Analysis CRC PressTaylor amp Francis Group Boca Raton Fla USA 2nd edition2005

[31] StatSoft Inc STATISTICA for Windows (Computer ProgramManual) StatSoft Tulsa Okla USA 1999

[32] USDA Soil Quality Indicator pH Natural Resources Conserva-tion Service 1998

[33] G E Lailach T DThompson and GW Brindley ldquoAbsorptionof pyrimidines purines and nucleosides by Co- Ni- Cu- andFe(III)-Montmorillonite (Clay-Organic Studies XIII)rdquo Claysand Clay Minerals vol 16 no 4 pp 295ndash301 1968

[34] R G NashW G Harris and C C Lewis ldquoSoil pH andmetallicamendment effects on DDT conversion to DDErdquo Journal ofEnvironmental Quality vol 2 no 3 pp 390ndash394 1973

[35] J G Konrad and G Chesters ldquoDegradation in soils of cioduman organophosphate insecticiderdquo Journal of Agricultural andFood Chemistry vol 17 no 2 pp 226ndash230 1969

[36] A Albarran R Celis M C Hermosın A Lopez-Pineiro and JCornejo ldquoBehavior of simazine in soil amended with the finalresidue of the olive-oil extraction processrdquo Chemosphere vol54 no 6 pp 717ndash724 2004

[37] J Dec and J-M Bollag ldquoDetermination of covalent and non-covalent binding interactions between xenobiotic chemicalsand soilrdquo Soil Science vol 162 no 12 pp 858ndash874 1997

[38] A Nawab A Aleem and A Malik ldquoDetermination oforganochlorine pesticides in agricultural soil with specialreference to 120574-HCH degradation by Pseudomonas strainsrdquoBioresource Technology vol 88 no 1 pp 41ndash46 2003

[39] M Bavcon P Trebse and L Zupancic-Kralj ldquoInvestigationsof the determination and transformations of diazinon andmalathion under environmental conditions using gas chro-matography coupled with a flame ionisation detectorrdquo Chemo-sphere vol 50 no 5 pp 595ndash601 2003

[40] S A Sassman L S Lee M Bischoff and R F Turco ldquoAssessingNN1015840-dibutylurea (DBU) formation in soils after application of

Scientifica 11

n-butylisocyanate and benlate fungicidesrdquo Journal of Agricul-tural and Food Chemistry vol 52 no 4 pp 747ndash754 2004

[41] E R Mouta M R Soares and J C Casagrande ldquoCopperadsorption as a function of solution parameters of variablecharge soilsrdquo Journal of the Brazilian Chemical Society vol 19no 5 pp 996ndash1009 2008

[42] M Arshad J Silvestre E Pinelli et al ldquoA field study oflead phytoextraction by various scented Pelargonium cultivarsrdquoChemosphere vol 71 no 11 pp 2187ndash2192 2008

[43] G Uzu S Sobanska Y Aliouane P Pradere and C DumatldquoStudy of lead phytoavailability for atmospheric industrialmicronic and sub-micronic particles in relation with leadspeciationrdquo Environmental Pollution vol 157 no 4 pp 1178ndash1185 2009

[44] L H P Jones and S C Jarvis ldquoThe fate of heavy metalsrdquo inTheChemistry of Soil Processes D J Green andMH B Hayes Edsp 593 John Wiley amp Sons New York NY USA 1981

[45] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of trace metal levels intannery effluents in relation to soil and water a case study fromPeshawar Pakistanrdquo Journal of EnvironmentalManagement vol79 no 1 pp 20ndash29 2006

[46] R J Ellis B Neish MW Trett et al ldquoComparison of microbialand meiofaunal community analyses for determining impact ofheavy metal contaminationrdquo Journal of Microbiological Meth-ods vol 45 no 3 pp 171ndash185 2001

[47] S R Tariq F Iqbal and A Ijaz ldquoAssessment and multivariateanalysis of metals in surgical instrument industry affected topsoils and groundwater for future reclamationrdquo InternationalJournal of Environment and Pollution vol 1 pp 54ndash71 2013

[48] S R Tariq and N Rashid ldquoMultivariate analysis of metal levelsin paddy soil rice plants and rice grains a case study fromShakargarh Pakistanrdquo Journal of Chemistry vol 2013 ArticleID 539251 10 pages 2013

[49] B S Everitt S Landau and M Leese Cluster Analysis Arnold4th edition 2001

Submit your manuscripts athttpwwwhindawicom

Nutrition and Metabolism

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Food ScienceInternational Journal of

Agronomy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom

Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Plant GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Biotechnology Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Forestry ResearchInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Veterinary Medicine International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Cell BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Evolutionary BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Scientifica 9

Wardrsquos method

OC ()Imidacloprid

pH

CdAcetamiprid

Conductivity (120583Scm)CuCoNiCr

EmamectinPb

04 06 08 10 12 14 16 18 2002Linkage distance

Clminus (mgkg)

NO3minus (mgkg)

SO42minus (mgkg)

Figure 3 Cluster analysis for the determination of various parame-ters

with the presence of greater concentration of copper in thesoil On the other hand imidacloprid in soil was found tobe negatively correlated with Ni of soil (119903-value of minus0317)Similarly a significant negative correlation was observedbetween Cr and acetamiprid (119903-value minus0305) Thus it wasevidenced that Cu stabilizes acetamiprid while Cr and Nifacilitate the degradation of acetamiprid and imidacloprid inthe soil [45]

Similar results have been reported for pyrethroid pes-ticides whose degradation was shown to be inhibited bythe presence of copper ions Ellis et al reported that metalslike Cu present in soil may react with the sulfhydryl groupof enzymes and inhibit their activity Thus the pesticidesbecome more persistent thereby leading to an increase intheir concentration with time [21 46]

33 Cluster Analysis of Various Parameters in the Soil Sam-ples Cluster analysis has proved to be a milestone towardthe source apportionment studies of various pollutants likemetals and pesticides in the soil and other media [47 48]In this analysis (Figure 3) linkage distance is used as themeasure of degree of closeness and hence relation among thevarious parameters [49] A number of clusters were formedwithin a significant linkage distance The strongest clusterwas observed between Cr and Ni evidencing that high Crcontent of the soil was associated with the enhanced Nilevels These two metals were further associated with Co toform a second cluster within linkage distance of 10 Themost important cluster of the study was observed betweenacetamiprid and conductivity that was further associatedwith Cu It evidenced that Cu present in the soil may causethe persistence of acetamiprid whose concentration increaseswith time Similarly emamectin was closely associated withPd

Cluster analysis revealed a close association betweensulphate and pH which formed a primary cluster withinlinkage distance of 06 This primary cluster was furtherassociated with Cd and Clminus within linkage distance of 10 onone side and with imidacloprid in the soil on the other side

The organic carbon of soil was associated with nitrate withina linkage distance of 08 and this factor was further associatedwith previous cluster

Overall the study revealed that frequently used pesti-cides that is imidacloprid emamectin and acetamipridwere present in the soil of cotton fields and were influencedby factors such as soil pH and organic carbon The studyalso furnished correlations among pesticides and metals inthe soil It was shown that presence of certain metals such asNi caused the decreased levels of imidacloprid Similarly Crenhanced the degradation of acetamiprid and Cu caused thepersistence of this pesticide in the soil

4 Conclusions

The soil samples collected from the cotton growing area ofPakpattan Pakistan were slightly basic in nature The meanPb Cr Co and Cu levels were below NEQS while the levelsof Ni and Cd were slightly above NEQS These levels may betolerated by following precautionarymeasures in agriculturalactivities Among the pesticides emamectin exhibited a highpersistence in the soil that was closely associated with soilCu content It was also found that Cu stabilizes acetamipridwhile Cr and Ni facilitate the degradation of acetamipridand imidacloprid Thus the study provides basis for therisk assessment studies that are quite necessary to managethe contaminated sites in a cost effective manner whilepreserving the public and ecosystem health It also providesa management strategy for remediation of contaminatedsoil that is adding traces of Ni and Cr in the soil mayhelp in the degradation of frequently used acetamiprid andimidacloprid

Conflict of Interests

The authors declare no conflict of interests

References

[1] R A Cloyd and J A Bethke ldquoImpact of neonicotinoidinsecticides onnatural enemies in greenhouse and interiorscapeenvironmentsrdquo Pest Management Science vol 67 no 1 pp 3ndash92011

[2] P Khaliq L A Hashmi and M H Qazi ldquoAgriculture andenvironmentrdquo Progress Farming vol 15 pp 16ndash23 1995

[3] H Shiraishi F Pula A Otsuki and T Iwakuma ldquoBehaviourof pesticides in Lake Kasumugaura Japanrdquo Science of the TotalEnvironment vol 72 pp 29ndash42 1988

[4] R Rial Otero B Cancho Grande M Arias Estevez E LopezPeriago and J Simal Gandara ldquoProcedure for themeasurementof soil inputs of plant-protection agents washed off throughvineyard canopy by rainfallrdquo Journal of Agricultural and FoodChemistry vol 51 no 17 pp 5041ndash5046 2003

[5] H M G van der Werf ldquoAssessing the impact of pesticideson the environmentrdquo Agriculture Ecosystems and Environmentvol 60 no 2-3 pp 81ndash96 1996

[6] G W vanLoon and S J Duffy Environmental Chemistry AGlobal Perspective Oxford University Press Oxford UK 2ndedition 2005

10 Scientifica

[7] P K Goel Water Pollution (Causes Effects and Control) NewAge International (P) New Delhi India 2nd edition 2006

[8] M Arias-Estevez E Lopez-Periago E Martınez-Carballo JSimal-Gandara J-C Mejuto and L Garcıa-Rıo ldquoThe mobilityand degradation of pesticides in soils and the pollution ofgroundwater resourcesrdquo Agriculture Ecosystems amp Environ-ment vol 123 no 4 pp 247ndash260 2008

[9] P J Shea T A Machacek and S D Comfort ldquoAcceleratedremediation of pesticide-contaminated soil with zerovalentironrdquo Environmental Pollution vol 132 no 2 pp 183ndash188 2004

[10] A Isaiah and M Paul ldquoSynergistic effect of chemical pesticideson commonly grown vegetables in Northern Indiardquo Epidemiol-ogy vol 18 p S86 2007

[11] J Fenoll P Hellın C Marın C M Martınez and A PFlores ldquoMultiresidue analysis of pesticides in soil by gaschromatography with nitrogen-phosphorus detection and gaschromatography mass spectrometryrdquo Journal of Agriculturaland Food Chemistry vol 53 no 20 pp 7661ndash7666 2005

[12] S Seccia P FidenteDMontesano andPMorrica ldquoDetermina-tion of neonicotinoid insecticides residues in bovine milk sam-ples by solid-phase extraction clean-up and liquid chromatog-raphy with diode-array detectionrdquo Journal of ChromatographyA vol 1214 no 1-2 pp 115ndash120 2008

[13] S M Dem J M Cobb and D E Mullins ldquoPesticide residuesin soil and water from four cotton growing areas of Mali WestAfricardquo Journal of Agricultural Food amp Environmental Sciencesvol 1 no 1 pp 1ndash12 2007

[14] M W Aktar M Paramasivam D Sengupta S Purkait MGanguly and S Banerjee ldquoImpact assessment of pesticideresidues in fish of Ganga river around Kolkata in West BengalrdquoEnvironmental Monitoring and Assessment vol 157 no 1ndash4 pp97ndash104 2009

[15] T R Sandrin and R M Maier ldquoImpact of metals on thebiodegradation of organic pollutantsrdquo Environmental HealthPerspectives vol 111 no 8 pp 1093ndash1101 2003

[16] S Khan Q Cao Y M Zheng Y Z Huang and Y G ZhuldquoHealth risks of heavy metals in contaminated soils and foodcrops irrigated with wastewater in Beijing Chinardquo Environmen-tal Pollution vol 152 no 3 pp 686ndash692 2008

[17] M-K Zhang Z-Y Liu and H Wang ldquoUse of single extractionmethods to predict bioavailability of heavy metals in pollutedsoils to ricerdquo Communications in Soil Science amp Plant Analysisvol 41 no 7 pp 820ndash831 2010

[18] Y PWang J Y ShiHWangQ Lin X CChen andYXChenldquoThe influence of soil heavy metals pollution on soil microbialbiomass enzyme activity and community composition near acopper smelterrdquo Ecotoxicology amp Environmental Safety vol 67no 1 pp 75ndash81 2007

[19] A A Helal D M Imam S M Khalifa and H F AlyldquoInteraction of pesticides with humic compounds and theirmetal complexesrdquo Radiochemistry vol 48 no 4 pp 419ndash4252006

[20] H Tian J Li Z Mu L Li and Z Hao ldquoEffect of pH onDDT degradation in aqueous solution using bimetallic NiFenanoparticlesrdquo Separation amp Purification Technology vol 66no 1 pp 84ndash89 2009

[21] T-F Liu C Sun N Ta J Hong S-G Yang and C-X ChenldquoEffect of copper on the degradation of pesticides cypermethrinand cyhalothrinrdquo Journal of Environmental Sciences vol 19 no10 pp 1235ndash1238 2007

[22] E Quivet R Faure J Georges J-O Paısse and P LanterildquoInfluence of metal salts on the photodegradation of imazapyr

an imidazolinone pesticiderdquo Pest Management Science vol 62no 5 pp 407ndash413 2006

[23] M Kamiya andK Kameyama ldquoEffects of selectedmetal ions onphotodegradation of organophosphorus pesticides sensitizedby humic acidsrdquo Chemosphere vol 45 no 3 pp 231ndash235 2001

[24] M Radojevic and V N Bashkin Practical EnvironmentalAnalysis Royal Society of Chemistry Cambridge UK 1999

[25] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of selected metals in tan-nery effluents and related soilrdquo Journal of Hazardous Materialsvol 122 no 1-2 pp 17ndash22 2005

[26] G R Blake and K H Hartge ldquoBulk and particle densityrdquo inMethods of Soil Analysis Part 1 pp 363ndash382 Soil Science Societyof America Madison Wis USA 1986

[27] P Patnaik Handbook of Environmental Analysis ChemicalPollutants in Air Water Soil and SolidWastes CRC Lewis BocaRaton Fla USA 1997

[28] A Bartosova A Michalıkova M Sirotiak and M SoldanldquoComparison of two spectrophotometric techniques for nutri-ents analyses inwater samplesrdquoResearch Papers Faculty ofMate-rials Science and Technology SlovakUniversity of Technology vol20 no 32 pp 8ndash19 2013

[29] H Spiegel E Filcheva P Hegymegi A Gal and F G AVerheijen ldquoReview and comparison of methods used for soilorganic carbon determination part 2 laboratory studyrdquo SoilScience Agrochemistry and Ecology vol 41 no 4 pp 19ndash25 2007

[30] K H Tan Soil Sampling Preparation and Analysis CRC PressTaylor amp Francis Group Boca Raton Fla USA 2nd edition2005

[31] StatSoft Inc STATISTICA for Windows (Computer ProgramManual) StatSoft Tulsa Okla USA 1999

[32] USDA Soil Quality Indicator pH Natural Resources Conserva-tion Service 1998

[33] G E Lailach T DThompson and GW Brindley ldquoAbsorptionof pyrimidines purines and nucleosides by Co- Ni- Cu- andFe(III)-Montmorillonite (Clay-Organic Studies XIII)rdquo Claysand Clay Minerals vol 16 no 4 pp 295ndash301 1968

[34] R G NashW G Harris and C C Lewis ldquoSoil pH andmetallicamendment effects on DDT conversion to DDErdquo Journal ofEnvironmental Quality vol 2 no 3 pp 390ndash394 1973

[35] J G Konrad and G Chesters ldquoDegradation in soils of cioduman organophosphate insecticiderdquo Journal of Agricultural andFood Chemistry vol 17 no 2 pp 226ndash230 1969

[36] A Albarran R Celis M C Hermosın A Lopez-Pineiro and JCornejo ldquoBehavior of simazine in soil amended with the finalresidue of the olive-oil extraction processrdquo Chemosphere vol54 no 6 pp 717ndash724 2004

[37] J Dec and J-M Bollag ldquoDetermination of covalent and non-covalent binding interactions between xenobiotic chemicalsand soilrdquo Soil Science vol 162 no 12 pp 858ndash874 1997

[38] A Nawab A Aleem and A Malik ldquoDetermination oforganochlorine pesticides in agricultural soil with specialreference to 120574-HCH degradation by Pseudomonas strainsrdquoBioresource Technology vol 88 no 1 pp 41ndash46 2003

[39] M Bavcon P Trebse and L Zupancic-Kralj ldquoInvestigationsof the determination and transformations of diazinon andmalathion under environmental conditions using gas chro-matography coupled with a flame ionisation detectorrdquo Chemo-sphere vol 50 no 5 pp 595ndash601 2003

[40] S A Sassman L S Lee M Bischoff and R F Turco ldquoAssessingNN1015840-dibutylurea (DBU) formation in soils after application of

Scientifica 11

n-butylisocyanate and benlate fungicidesrdquo Journal of Agricul-tural and Food Chemistry vol 52 no 4 pp 747ndash754 2004

[41] E R Mouta M R Soares and J C Casagrande ldquoCopperadsorption as a function of solution parameters of variablecharge soilsrdquo Journal of the Brazilian Chemical Society vol 19no 5 pp 996ndash1009 2008

[42] M Arshad J Silvestre E Pinelli et al ldquoA field study oflead phytoextraction by various scented Pelargonium cultivarsrdquoChemosphere vol 71 no 11 pp 2187ndash2192 2008

[43] G Uzu S Sobanska Y Aliouane P Pradere and C DumatldquoStudy of lead phytoavailability for atmospheric industrialmicronic and sub-micronic particles in relation with leadspeciationrdquo Environmental Pollution vol 157 no 4 pp 1178ndash1185 2009

[44] L H P Jones and S C Jarvis ldquoThe fate of heavy metalsrdquo inTheChemistry of Soil Processes D J Green andMH B Hayes Edsp 593 John Wiley amp Sons New York NY USA 1981

[45] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of trace metal levels intannery effluents in relation to soil and water a case study fromPeshawar Pakistanrdquo Journal of EnvironmentalManagement vol79 no 1 pp 20ndash29 2006

[46] R J Ellis B Neish MW Trett et al ldquoComparison of microbialand meiofaunal community analyses for determining impact ofheavy metal contaminationrdquo Journal of Microbiological Meth-ods vol 45 no 3 pp 171ndash185 2001

[47] S R Tariq F Iqbal and A Ijaz ldquoAssessment and multivariateanalysis of metals in surgical instrument industry affected topsoils and groundwater for future reclamationrdquo InternationalJournal of Environment and Pollution vol 1 pp 54ndash71 2013

[48] S R Tariq and N Rashid ldquoMultivariate analysis of metal levelsin paddy soil rice plants and rice grains a case study fromShakargarh Pakistanrdquo Journal of Chemistry vol 2013 ArticleID 539251 10 pages 2013

[49] B S Everitt S Landau and M Leese Cluster Analysis Arnold4th edition 2001

Submit your manuscripts athttpwwwhindawicom

Nutrition and Metabolism

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Food ScienceInternational Journal of

Agronomy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom

Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Plant GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Biotechnology Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Forestry ResearchInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Veterinary Medicine International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Cell BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Evolutionary BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

10 Scientifica

[7] P K Goel Water Pollution (Causes Effects and Control) NewAge International (P) New Delhi India 2nd edition 2006

[8] M Arias-Estevez E Lopez-Periago E Martınez-Carballo JSimal-Gandara J-C Mejuto and L Garcıa-Rıo ldquoThe mobilityand degradation of pesticides in soils and the pollution ofgroundwater resourcesrdquo Agriculture Ecosystems amp Environ-ment vol 123 no 4 pp 247ndash260 2008

[9] P J Shea T A Machacek and S D Comfort ldquoAcceleratedremediation of pesticide-contaminated soil with zerovalentironrdquo Environmental Pollution vol 132 no 2 pp 183ndash188 2004

[10] A Isaiah and M Paul ldquoSynergistic effect of chemical pesticideson commonly grown vegetables in Northern Indiardquo Epidemiol-ogy vol 18 p S86 2007

[11] J Fenoll P Hellın C Marın C M Martınez and A PFlores ldquoMultiresidue analysis of pesticides in soil by gaschromatography with nitrogen-phosphorus detection and gaschromatography mass spectrometryrdquo Journal of Agriculturaland Food Chemistry vol 53 no 20 pp 7661ndash7666 2005

[12] S Seccia P FidenteDMontesano andPMorrica ldquoDetermina-tion of neonicotinoid insecticides residues in bovine milk sam-ples by solid-phase extraction clean-up and liquid chromatog-raphy with diode-array detectionrdquo Journal of ChromatographyA vol 1214 no 1-2 pp 115ndash120 2008

[13] S M Dem J M Cobb and D E Mullins ldquoPesticide residuesin soil and water from four cotton growing areas of Mali WestAfricardquo Journal of Agricultural Food amp Environmental Sciencesvol 1 no 1 pp 1ndash12 2007

[14] M W Aktar M Paramasivam D Sengupta S Purkait MGanguly and S Banerjee ldquoImpact assessment of pesticideresidues in fish of Ganga river around Kolkata in West BengalrdquoEnvironmental Monitoring and Assessment vol 157 no 1ndash4 pp97ndash104 2009

[15] T R Sandrin and R M Maier ldquoImpact of metals on thebiodegradation of organic pollutantsrdquo Environmental HealthPerspectives vol 111 no 8 pp 1093ndash1101 2003

[16] S Khan Q Cao Y M Zheng Y Z Huang and Y G ZhuldquoHealth risks of heavy metals in contaminated soils and foodcrops irrigated with wastewater in Beijing Chinardquo Environmen-tal Pollution vol 152 no 3 pp 686ndash692 2008

[17] M-K Zhang Z-Y Liu and H Wang ldquoUse of single extractionmethods to predict bioavailability of heavy metals in pollutedsoils to ricerdquo Communications in Soil Science amp Plant Analysisvol 41 no 7 pp 820ndash831 2010

[18] Y PWang J Y ShiHWangQ Lin X CChen andYXChenldquoThe influence of soil heavy metals pollution on soil microbialbiomass enzyme activity and community composition near acopper smelterrdquo Ecotoxicology amp Environmental Safety vol 67no 1 pp 75ndash81 2007

[19] A A Helal D M Imam S M Khalifa and H F AlyldquoInteraction of pesticides with humic compounds and theirmetal complexesrdquo Radiochemistry vol 48 no 4 pp 419ndash4252006

[20] H Tian J Li Z Mu L Li and Z Hao ldquoEffect of pH onDDT degradation in aqueous solution using bimetallic NiFenanoparticlesrdquo Separation amp Purification Technology vol 66no 1 pp 84ndash89 2009

[21] T-F Liu C Sun N Ta J Hong S-G Yang and C-X ChenldquoEffect of copper on the degradation of pesticides cypermethrinand cyhalothrinrdquo Journal of Environmental Sciences vol 19 no10 pp 1235ndash1238 2007

[22] E Quivet R Faure J Georges J-O Paısse and P LanterildquoInfluence of metal salts on the photodegradation of imazapyr

an imidazolinone pesticiderdquo Pest Management Science vol 62no 5 pp 407ndash413 2006

[23] M Kamiya andK Kameyama ldquoEffects of selectedmetal ions onphotodegradation of organophosphorus pesticides sensitizedby humic acidsrdquo Chemosphere vol 45 no 3 pp 231ndash235 2001

[24] M Radojevic and V N Bashkin Practical EnvironmentalAnalysis Royal Society of Chemistry Cambridge UK 1999

[25] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of selected metals in tan-nery effluents and related soilrdquo Journal of Hazardous Materialsvol 122 no 1-2 pp 17ndash22 2005

[26] G R Blake and K H Hartge ldquoBulk and particle densityrdquo inMethods of Soil Analysis Part 1 pp 363ndash382 Soil Science Societyof America Madison Wis USA 1986

[27] P Patnaik Handbook of Environmental Analysis ChemicalPollutants in Air Water Soil and SolidWastes CRC Lewis BocaRaton Fla USA 1997

[28] A Bartosova A Michalıkova M Sirotiak and M SoldanldquoComparison of two spectrophotometric techniques for nutri-ents analyses inwater samplesrdquoResearch Papers Faculty ofMate-rials Science and Technology SlovakUniversity of Technology vol20 no 32 pp 8ndash19 2013

[29] H Spiegel E Filcheva P Hegymegi A Gal and F G AVerheijen ldquoReview and comparison of methods used for soilorganic carbon determination part 2 laboratory studyrdquo SoilScience Agrochemistry and Ecology vol 41 no 4 pp 19ndash25 2007

[30] K H Tan Soil Sampling Preparation and Analysis CRC PressTaylor amp Francis Group Boca Raton Fla USA 2nd edition2005

[31] StatSoft Inc STATISTICA for Windows (Computer ProgramManual) StatSoft Tulsa Okla USA 1999

[32] USDA Soil Quality Indicator pH Natural Resources Conserva-tion Service 1998

[33] G E Lailach T DThompson and GW Brindley ldquoAbsorptionof pyrimidines purines and nucleosides by Co- Ni- Cu- andFe(III)-Montmorillonite (Clay-Organic Studies XIII)rdquo Claysand Clay Minerals vol 16 no 4 pp 295ndash301 1968

[34] R G NashW G Harris and C C Lewis ldquoSoil pH andmetallicamendment effects on DDT conversion to DDErdquo Journal ofEnvironmental Quality vol 2 no 3 pp 390ndash394 1973

[35] J G Konrad and G Chesters ldquoDegradation in soils of cioduman organophosphate insecticiderdquo Journal of Agricultural andFood Chemistry vol 17 no 2 pp 226ndash230 1969

[36] A Albarran R Celis M C Hermosın A Lopez-Pineiro and JCornejo ldquoBehavior of simazine in soil amended with the finalresidue of the olive-oil extraction processrdquo Chemosphere vol54 no 6 pp 717ndash724 2004

[37] J Dec and J-M Bollag ldquoDetermination of covalent and non-covalent binding interactions between xenobiotic chemicalsand soilrdquo Soil Science vol 162 no 12 pp 858ndash874 1997

[38] A Nawab A Aleem and A Malik ldquoDetermination oforganochlorine pesticides in agricultural soil with specialreference to 120574-HCH degradation by Pseudomonas strainsrdquoBioresource Technology vol 88 no 1 pp 41ndash46 2003

[39] M Bavcon P Trebse and L Zupancic-Kralj ldquoInvestigationsof the determination and transformations of diazinon andmalathion under environmental conditions using gas chro-matography coupled with a flame ionisation detectorrdquo Chemo-sphere vol 50 no 5 pp 595ndash601 2003

[40] S A Sassman L S Lee M Bischoff and R F Turco ldquoAssessingNN1015840-dibutylurea (DBU) formation in soils after application of

Scientifica 11

n-butylisocyanate and benlate fungicidesrdquo Journal of Agricul-tural and Food Chemistry vol 52 no 4 pp 747ndash754 2004

[41] E R Mouta M R Soares and J C Casagrande ldquoCopperadsorption as a function of solution parameters of variablecharge soilsrdquo Journal of the Brazilian Chemical Society vol 19no 5 pp 996ndash1009 2008

[42] M Arshad J Silvestre E Pinelli et al ldquoA field study oflead phytoextraction by various scented Pelargonium cultivarsrdquoChemosphere vol 71 no 11 pp 2187ndash2192 2008

[43] G Uzu S Sobanska Y Aliouane P Pradere and C DumatldquoStudy of lead phytoavailability for atmospheric industrialmicronic and sub-micronic particles in relation with leadspeciationrdquo Environmental Pollution vol 157 no 4 pp 1178ndash1185 2009

[44] L H P Jones and S C Jarvis ldquoThe fate of heavy metalsrdquo inTheChemistry of Soil Processes D J Green andMH B Hayes Edsp 593 John Wiley amp Sons New York NY USA 1981

[45] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of trace metal levels intannery effluents in relation to soil and water a case study fromPeshawar Pakistanrdquo Journal of EnvironmentalManagement vol79 no 1 pp 20ndash29 2006

[46] R J Ellis B Neish MW Trett et al ldquoComparison of microbialand meiofaunal community analyses for determining impact ofheavy metal contaminationrdquo Journal of Microbiological Meth-ods vol 45 no 3 pp 171ndash185 2001

[47] S R Tariq F Iqbal and A Ijaz ldquoAssessment and multivariateanalysis of metals in surgical instrument industry affected topsoils and groundwater for future reclamationrdquo InternationalJournal of Environment and Pollution vol 1 pp 54ndash71 2013

[48] S R Tariq and N Rashid ldquoMultivariate analysis of metal levelsin paddy soil rice plants and rice grains a case study fromShakargarh Pakistanrdquo Journal of Chemistry vol 2013 ArticleID 539251 10 pages 2013

[49] B S Everitt S Landau and M Leese Cluster Analysis Arnold4th edition 2001

Submit your manuscripts athttpwwwhindawicom

Nutrition and Metabolism

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Food ScienceInternational Journal of

Agronomy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom

Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Plant GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Biotechnology Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Forestry ResearchInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Veterinary Medicine International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Cell BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Evolutionary BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Scientifica 11

n-butylisocyanate and benlate fungicidesrdquo Journal of Agricul-tural and Food Chemistry vol 52 no 4 pp 747ndash754 2004

[41] E R Mouta M R Soares and J C Casagrande ldquoCopperadsorption as a function of solution parameters of variablecharge soilsrdquo Journal of the Brazilian Chemical Society vol 19no 5 pp 996ndash1009 2008

[42] M Arshad J Silvestre E Pinelli et al ldquoA field study oflead phytoextraction by various scented Pelargonium cultivarsrdquoChemosphere vol 71 no 11 pp 2187ndash2192 2008

[43] G Uzu S Sobanska Y Aliouane P Pradere and C DumatldquoStudy of lead phytoavailability for atmospheric industrialmicronic and sub-micronic particles in relation with leadspeciationrdquo Environmental Pollution vol 157 no 4 pp 1178ndash1185 2009

[44] L H P Jones and S C Jarvis ldquoThe fate of heavy metalsrdquo inTheChemistry of Soil Processes D J Green andMH B Hayes Edsp 593 John Wiley amp Sons New York NY USA 1981

[45] S R Tariq M H Shah N Shaheen A Khalique S Manzoorand M Jaffar ldquoMultivariate analysis of trace metal levels intannery effluents in relation to soil and water a case study fromPeshawar Pakistanrdquo Journal of EnvironmentalManagement vol79 no 1 pp 20ndash29 2006

[46] R J Ellis B Neish MW Trett et al ldquoComparison of microbialand meiofaunal community analyses for determining impact ofheavy metal contaminationrdquo Journal of Microbiological Meth-ods vol 45 no 3 pp 171ndash185 2001

[47] S R Tariq F Iqbal and A Ijaz ldquoAssessment and multivariateanalysis of metals in surgical instrument industry affected topsoils and groundwater for future reclamationrdquo InternationalJournal of Environment and Pollution vol 1 pp 54ndash71 2013

[48] S R Tariq and N Rashid ldquoMultivariate analysis of metal levelsin paddy soil rice plants and rice grains a case study fromShakargarh Pakistanrdquo Journal of Chemistry vol 2013 ArticleID 539251 10 pages 2013

[49] B S Everitt S Landau and M Leese Cluster Analysis Arnold4th edition 2001

Submit your manuscripts athttpwwwhindawicom

Nutrition and Metabolism

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Food ScienceInternational Journal of

Agronomy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom

Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Plant GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Biotechnology Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Forestry ResearchInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Veterinary Medicine International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Cell BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Evolutionary BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Submit your manuscripts athttpwwwhindawicom

Nutrition and Metabolism

Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Food ScienceInternational Journal of

Agronomy

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

International Journal of

Microbiology

The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Hindawi Publishing Corporationhttpwwwhindawicom

Applied ampEnvironmentalSoil Science

Volume 2014

AgricultureAdvances in

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

PsycheHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

BiodiversityInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Plant GenomicsInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Biotechnology Research International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Forestry ResearchInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of BotanyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

EcologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Veterinary Medicine International

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Cell BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Evolutionary BiologyInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014