Research Article Bioavailability Studies of Metals in ...downloads.hindawi.com/archive/2014/648453.pdf · Research Article Bioavailability Studies of Metals in Surface Water of River

Research ArticleBioavailability Studies of Metals in Surface Water ofRiver Challawa Nigeria

A Uzairu1 O J Okunola2 R J Wakawa3 and S G Adewusi4

1 Department of Chemistry Ahmadu Bello University Zaria Nigeria2 National Research Institute for Chemical Technology PMB 1052 Zaria Nigeria3 Department of Chemistry School of Science Federal College of Education Zuba Nigeria4Department of Chemistry School of Science Federal College of Education Zaria Nigeria

Correspondence should be addressed to O J Okunola okunolaojgmailcom

Received 6 May 2014 Accepted 20 August 2014 Published 15 September 2014

Academic Editor Christos Kordulis

Copyright copy 2014 A Uzairu et alThis is an open access article distributed under theCreativeCommonsAttribution License whichpermits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Due to industrialization of Kano City more industries located within Challawa industrial estate have discharged waste informed ofeffluents into River Challawa which is the main source of irrigation water for agricultural land Hence this study is aim at assessingthe bioavailable fractions of the metals zinc (Zn) lead (Pb) copper (Cu) chromium (Cr) and cadmium (Cd) in surface water ofriver Challawa Kano Nigeria across seasons It was found that the concentrations of most metals increased significantly duringthe dry seasons Concentrations of Cu and Zn are within the standard limits of EPA and WHO for these metals in drinking waterwhile Pb Cr and Cd have their concentrations higher than EPA andWHO standard limits Analysis of relationship betweenmetalsindicated significant positive correlation (119875 lt 005) between Cr and Zn in all seasons with exception of warm and dry seasonThismight explain the consistent variation of these metals in the sites in a particular season Also significant negative correlation wasobserved between Cd and Cu (hot and dry season) The chemical fractionation trends were found to be dominated by particulatefractions ofmetals studied except Zn (cool and dry season) andCdThe highest percentages of all metals analysed were found in theparticulate fraction with exception of Cd This could reflect less availability of this metal to the immediate environment Howeveravailability of metals such as Cd Cr and Pb in the dissolved and mobile fractions reflects the greater tendency to become availableto the aquatic system and through the food chain to man

1 Introduction

The pollution of surface waters is significant though ona local scale However the heavy runoff associated withperennial rainfall may mitigate the impact Several smalland heavy industries involved in activities such as batterytextiles tanning and paint manufacturing are now beinglocated haphazardly mostly near metropolitan centers [1] Nocentralized sewage systems exist and the industrial effluentsfrom the factories are usually discharged untreated intostreams rivers and other water bodies This has resulted inhigh alarming levels of lead (Pb) cadmium (Cd) copper(Cu) and chromium (Cr) in some localized areas

Bichi [2] indicated that Kano is a booming industrialcenter in Nigeria with over 320 industrial establishments

comprising of chemical industries tanneries textiles andfood processing factories which release waste water intoriversThis according to Bichi has led to the deterioration ofwater quality with Challawa River one of the receiving riversDada [3] carried out industrial survey which showed that 60industries discharged untreated effluents into river and only6 surveyed industries (10) had primary treatment plantsranging from oxidation tanks to sedimentation tanks Thisis considered inadequate and water analysis showed excessamounts of heavy metals such as Pb Cr and iron (Fe) [4]

Pollution of water with heavy metals is of grave con-sequence because both terrestrial and aquatic lives may bepoisoned it may cause disease due to the presence of somehazardous substance which may distort the water qualityadd odours and significantly hinder economic activities

Hindawi Publishing CorporationJournal of Applied ChemistryVolume 2014 Article ID 648453 9 pageshttpdxdoiorg1011552014648453

2 Journal of Applied Chemistry

[5] According to Izonfuo and Bariweni [6] several humanactivities have been identified to result in water pollutionagriculture irrigation urbanization mining and industrial-ization Though several studies on Nigerian surface watershave been conducted [7ndash14] recently the understanding ofthe biogeochemistry of heavymetals inmarine environmentshas changed considerably during the last two decades [15]A more thorough comprehension of heavy metal cycling inthe environment could however require information on thechemical speciation of metals in solution that is the specificphysicochemical forms that are part of the total concentrationof metal in solution

On the other hand metal speciation determines thebioavailability andor toxicity of themetals for aquatic organ-isms in addition to affecting the cycle of metals in aquaticenvironments and in thewater-sediment interface Accordingto Backstrom et al [16] three fractionation stages weredefined for heavy metals in runoff from roadside dissolvedfraction mobile fraction and total fraction particulate frac-tion is the difference between total fraction and dissolvedfraction The mobile fractions of heavy metals are moreavailable for environmental functions than other fractionsIn the ecological context the mobile fractions rather thanthe total metal content are important Further the chemicalspecies especially in aquatic medium play important role intransfer of metals along the water-sediment aquatic animalsand plants to human chain Hence this research was initiatedto study seasonal variations of impact of industrial effluentson total dissolved mobile and particulate concentrationsof some selected heavy metals in surface water of riverChallawa in attempts to establish both long- and short-termconcentrations effects

2 Materials and Methods

21 Description of Study Area Challawa River is located inChallawa industrial estate (11∘45101584042N longitude 8∘46101584017E)in Kumbotso local Government of Kano State Kano Stateis located in the Northern part of Nigeria covering an areaextending between latitudes 12∘401015840 and 10∘301015840 and longitudes7∘401015840 and 9∘401015840 Challawa River is one of the receiving riversof effluents from Challawa industrial estate The industriesin the Challawa industrial estate range from tanneries andtextile to foods and packaging industries The effluents fromthe industries in the estate were connected by a canal andchanneled directly into Challawa River as a point sourceTheclimate of the area is dominated by the cyclical migrationintertropical convergence zone which is marked with longerdry than wet season and the highest rainfall in July andAugust [17] The relevant human activities in the River arecommercial sand dredging fishing washing and recreationduring hot hour of the day

22 Sample Collection The River was divided into upstreamand downstream areas as shown in Figure 1 Five samplingsites were chosen on downstream (polluted sites) and onesampling site was chosen on upstream (control site) givinga total of six sampling points Each sampling site comprisesof five sampling points composite to form a core for a site

In choosing the sites for the polluted sites preference wasgiven to such factor as points of effluent discharge intothe river Surface water was collected at the six sites ona seasonal basis between October 2006 and August 2008Surface water was collected at the middle of the river andstored in clean polythene bottles prewashed with acid andrinsed thoroughly with deionized water Once collected thesamples were immediately stored on ice in an ice box andtransported to the laboratory for analysis

Seasons

Warm and dry seasonmdashSeptemberndashNovemberCold and dry seasonmdashDecemberndashFebruaryHot and dry seasonmdashMarchndashMayWarm and wet seasonmdashJunendashAugust

23 Analysis Chemical fractionation of water samples wascarried out on the principle proposed by Backstrom et al[16] Samples were subjected to extraction using 2 nitricacid separately The extraction was aimed at differentiatingfractions in three stages as follows

Fraction I (dissolved) 50mL was decanted from thesampling vessel and filtered through 050120583m Teflonfilters before acidification with 2 nitric acid

Fraction II (mobile) 50mL was decanted from thesample vessel and acidified with 2 nitric acid fol-lowed by filtration through 050 120583mTeflon filters after24 hrs

Fraction III (total) 2 nitric acid was added directlyinto the sample vessel and shaken rigorously tosuspend all particulate matters The solution wasfiltered after 24 hrs through 050 120583m Teflon filtersThe particulate concentration was calculated as thedifference between Fraction III and Fraction I

Analysis of Cu Zn Pb Cr and Cr was performed on anatomic absorption spectrophotometer (AAS) The validationof the procedure for metal determination and efficiency ofAAS was conducted by spiking a sample with multielementstandard solution containing 05mgL of all metals analysedAll acid and reagents used were of analytical grade qualitycontrol certified by the use of procedural blanks and spikesThe spike recovery for eachmetal wasgt96All sampleswererun in triplicates

3 Results

The results of total heavy metals concentration of surfacewater across the seasons were presented in Table 1 Zn valuesranged between 088mgL (Site D during the cool and dryseason) and 386 mgL (Site E during hot and dry season)Season variations were observed with the highest value ofZn obtained during the hot and dry season In the samevein Pb concentration varied between 110mgL (Site E

Journal of Applied Chemistry 3

To Panshekara

002001 04

06

0507

010

012 011013

014

017

018

015

019

020021

024

022

016

09 08

03

023

Central collectionpoint African

textileindustry

026

027

F

A BC D

E

A E

TsamawaHausawa

River ChallawaMagasawa

Challawabridge

Yandanko

Farming activitiesControl pointRiverWater worksWaste water routesDirection of flowSampling points

RoadsstreetsFishing activitiesMain waste drainageAbandoned farm landsSettlementsTannery

middot middot middot

Figure 1 Study area map

during wet season) and 900mgL (Site F during dry season)The distribution of Pb concentrations as shown in the tableshowed that Pb is higher in all sites during the dry seasonsSimilar reasons as Zn could also imply Cu Cr and Cdmean concentrations in the water body ranged between000mgLminus1 (Site F in all season) and 051mgLminus1 (Site Bduring dry season) 000mgLminus1 (Site F during dry season)and 1251mgLminus1 (Site A during dry season) and 000mgLminus1(Site F during wet season) and 071mgLminus1 (Site C duringdry season) respectively Also highest concentrations of Cuand Cr are recorded during the warm and dry season while

Cd recordedmaximum concentration during the hot and dryseason The highest concentrations of Cu Cr and Cd duringthe dry seasons could be due to the volume of water availablewhich is a function of pollutant concentration Analysis ofvariation across the seasons was significant (119875 lt 005) forall metals except Cu Correlation analysis as shown in Table 2indicates significant positive correlation (119875 lt 005) betweenCu and Pb across the seasons with exception of warm anddry season Cr and Zn Cr and Pb and Pb and Zn This mayexplain the consistent variation of these metals in the sitesin a particular season Also significant negative correlation


Table 1 Mean (plusmnSD) of total metal concentrations in surface water of River Challawa (mgLminus1)

A B C D E FWarm and dry season

Zn 044 plusmn 001 015 plusmn 000 014 plusmn 001 067 plusmn 001 031 plusmn 001 097 plusmn 001Pb 205 plusmn 007 905 plusmn 007 305 plusmn 007 434 plusmn 001 500 plusmn 000 900 plusmn 000Cu 035 plusmn 007 051 plusmn 001 041 plusmn 001 010 plusmn 000 009 plusmn 001 000 plusmn 000Cr 1251 plusmn 001 668 plusmn 001 1168 plusmn 001 1168 plusmn 001 000 plusmn 000 000 plusmn 000Cd 011 plusmn 001 022 plusmn 000 016 plusmn 001 016 plusmn 001 016 plusmn 001 011 plusmn 001

Cool and dry seasonZn 205 plusmn 001 312 plusmn 001 226 plusmn 001 088 plusmn 001 269 plusmn 001 164 plusmn 001Pb 263 plusmn 001 205 plusmn 007 215 plusmn 007 235 plusmn 007 220 plusmn 000 305 plusmn 007Cu 021 plusmn 001 014 plusmn 001 015 plusmn 001 007 plusmn 001 008 plusmn 000 000 plusmn 000Cr 310 plusmn 014 425 plusmn 001 330 plusmn 014 459 plusmn 002 247 plusmn 000 010 plusmn 000Cd 047 plusmn 001 040 plusmn 000 071 plusmn 001 024 plusmn 000 030 plusmn 000 008 plusmn 000

Hot and dry seasonZn 108 plusmn 001 090 plusmn 000 199 plusmn 001 092 plusmn 001 386 plusmn 001 183 plusmn 001Pb 345 plusmn 007 407 plusmn 001 251 plusmn 001 216 plusmn 001 215 plusmn 007 336 plusmn 001Cu 001 plusmn 000 001 plusmn 000 001 plusmn 001 031 plusmn 001 004 plusmn 001 000 plusmn 000Cr 315 plusmn 007 320 plusmn 000 310 plusmn 014 600 plusmn 000 055 plusmn 007 000 plusmn 000Cd 062 plusmn 000 015 plusmn 001 058 plusmn 001 019 plusmn 001 014 plusmn 001 006 plusmn 001

Warm and wet seasonZn 171 plusmn 001 130 plusmn 000 301 plusmn 001 156 plusmn 001 175 plusmn 001 285 plusmn 007Pb 143 plusmn 001 260 plusmn 000 215 plusmn 007 225 plusmn 001 110 plusmn 000 125 plusmn 007Cu 002 plusmn 000 001 plusmn 000 001 plusmn 000 002 plusmn 000 001 plusmn 000 000 plusmn 000Cr 375 plusmn 007 405 plusmn 007 425 plusmn 007 710 plusmn 014 061 plusmn 001 031 plusmn 001Cd 010 plusmn 001 007 plusmn 001 006 plusmn 001 014 plusmn 001 009 plusmn 001 000 plusmn 000

Standard limit Pb Cr Cu Zn CdWHO 01 01 mdash mdash 001EPA 005 01 13 5 001FEPA lt1 005 lt1 lt1 lt1

WHO [19] FEPA [20] and EPA [21]

was observed between Cd and Cu (hot and dry season)also this could explain the different sources of these metalsin the environmental samples Generally higher values wereobtained in the dry season than in wet season (Table 1) Thissituation is expected in view of the reduction in the pollutionin the wet season arising from increased dilution and waterflow This is also similar to report by Obasohan [18] that theriver is at its highest volume and flow in the wet season

From Figures 2 3 4 5 and 6 the chemical partitioningtrends were found to be dominated by particulate fractions ofmetal studied except Zn (cool and dry season) and Cd Dataobtained from the extraction procedure shows the followingmetal distribution pattern of the fractions across the seasons

Warm and Dry SeasonZn Particulate gtMobile gt DissolvedPb Particulate gtMobile gt DissolvedCu Particulate gtMobile gt Dissolved

Cr Particulate gtMobile gt DissolvedCd Dissolved gt Particulate gtMobile

Cool and Dry Season

Zn Dissolved gtMobile gt ParticulatePb Particulate gtMobile gt DissolvedCu Particulate gt Dissolved gtMobileCr Particulate gt Dissolved gtMobileCd Particulate gtMobile gt Dissolved

Hot and Dry Season

Zn Particulate gt Dissolved gtMobilePb Particulate gtMobile gt DissolvedCu Particulate gtMobile gt Dissolved


Table 2 Intermetal relationships in surface water across seasons

Metals Zn Pb Cu Cr CdWarm and dry season

Zn 1000Pb minus0020 1000Cu 0100 0070 1000Cr 0312 0400 0407 1000Cd minus0233 minus0200 minus0100 0100 1000

Cool and dry seasonZn 1000Pb minus0112 1000Cu minus0298 0416lowast 1000Cr 0512lowast 0123 minus0121 1000Cd 0314 0142 minus0344 0298 1000

Hot and dry seasonZn 1000Pb minus0109 1000Cu minus0113 0500lowast 1000Cr minus0333 0616lowast 0414 1000Cd 0102 minus0211 minus0512lowast minus0314 1000

Warm and wet seasonZn 1000Pb 0500lowast 1000Cu 0109 0522lowast 1000Cr 0222 0200 0010 1000Cd minus0100 0100 minus0111 minus0126 1000lowastSignificantly at 119875 lt 005

Cr Particulate gtMobile gt DissolvedCd Particulate gt Dissolved gtMobile

Warm and Wet Season

Zn Particulate gtMobile gt DissolvedPb Particulate gtMobile gt DissolvedCu Particulate gtMobile gt DissolvedCr Particulate gtMobile gt DissolvedCd Dissolved gtMobile gt Particulate

The highest percentages of all metals analysed are foundin the particulate fraction with exception of Cd This couldreflect less availability of this metal to the immediate envi-ronment However availability of metals such as Cd Cr andPb in the dissolved and mobile fraction reflects the greatertendency to become available to the immediate environment

4 Discussion

As identified from various literaturesmain source of Pb is thealkyl derivatives in petroleum which is gradually phasing off

Also it comes from other sources like metal manufacturingsewages paints fertilizer pesticides and ashes [22] Leadedgasoline was used in Nigeria until recently This is probablycould be the mechanism of anthropogenic Pb contributionsinto the river In particular in dry season nearly in allsites from where samples were taken Pb levels were foundto be higher than mean values reported for polluted andunpolluted sites in a similar study inNigeria rivers [5 23]Theelevated levels of Pb in Site F (control) could indicate othersources than effluents discharged from industries withinChallawa As shown in Table 1 high level of Cr was obtainedfrom Site A point of discharge of tanning effluents into theriver Cr being amajor constituent of chemicals use in tanningindustries in this area may explain reason for the high levelof Cr Pb and Cr levels observed in this study far exceededthe WHO [19] EPA [21] and FEPA [20] recommendedlimits for Pb and Cr Pb is the most ubiquitous toxicant inthe environment [24] Pb may impair renal function redblood cell production and the nervous system and causesblindness [5] Though Cr is an essential trace nutrient and avital component for the glucose tolerance factor Cr toxicitydamages the livers and lungs and causes organ hemorrhages[25] The high value of Cr might be attributed to the careless


Warm and dry season

000

2000

4000

6000

8000

10000

A B C D E F

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

Sites

A B C D E FSites

A B C D E FSites

A B C D E FSites

DissolvedMobile

Particulate

Hot and dry season

Warm and wet season

Cool and dry season

Figure 2 Percentage of Zn in fractions

discharged of tannery and textile effluent from industrieslocated within this area into the river

All samples contained Zn However values obtainedin the study indicated that Zn does not seem to be con-centrated in water samples since the levels were belowWHO and EPA standards limit though higher than FEPAstandard limits The observed levels tend to agree with thosereported elsewhere in Nigeria rivers [23 26 27] But itis important to mention Zn pollution in rivers There aremany sources of Zn like fossil fuels metal manufacturingand fertilizers [22] Excessive Zn has also been known to

Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000Fr

actio

n (

)

000

2000

4000

6000

8000

10000

Frac

tion

()

A B C D E FSites

A B C D E FSites

A B C D E FSites

A B C D E FSites

DissolvedMobile

Particulate

Figure 3 Percentage of Pb in fractions

induce vomiting dehydration abdominal pains dizzinessand lack of muscular coordination in man [28] For Cu therecommended standard limits in water are 13mgLminus1 (EPA)and lt1 (FEPA) For all samples analysed Cu was generallywithin the recommended limits Though widely distributedand being an essential element acute toxicity of Cu results inhypotension coma and death From research Cu has beenknown to participate in the ecosystem frommany sources likehousehold tools wood and metal manufacturing pesticidesapplications fertilizers and septic tanks waste [29]


Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

A B C D E FSites

A B C D E FSites

A B C D E FSites

A B C D E FSites

DissolvedMobile

Particulate

Figure 4 Percentage of Cu in fractions

For all the samples Cd was detected to be higher whencompared toWHO and EPA standard limits althoughwithinthe FEPA [20] standard limits Cd has a long biological lifeof 20ndash30 years in the kidney [19] Chronic exposure mayeventually accumulate to toxic levels as a result of high levelobtained in this study This may lead to anaemia damage ofproximal tubules severe bone pain and mineral loss [30]

As observed from Table 1 concentrations of metalsobtained from this study showed increase in metal concen-tration of surface water of river Challawa compared to report

Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000Fr

actio

n (

)

000

2000

4000

6000

8000

10000

Frac

tion

()

A B C D E FSites

A B C D E FSites

A B C D E FSites

A B C D E FSites

DissolvedMobile

Particulate

Figure 5 Percentage of Cr in fractions

of Akan et al [13] in the same river water with exceptionof Cu and Zn The increase could arise due to increase inindiscriminate discharge of waste into the river

5 Conclusion

From the results metals concentrations in the mobile anddissolved fractions which are easily bioavailable were highThis metal could leach during changes in environmentalconditions and pose threat to the surrounding groundwaterquality Also with elevated levels of some metals in Site F


Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

A B C D E FSites

A B C D E FSites

A B C D E FSites

A B C D E FSites

DissolvedMobile

Particulate

Figure 6 Percentage of Cd in fractions

(control) it is indicated that sources other than industrialeffluents could be responsibleWith the continuous dischargeof waste and waste water pollution event especially with CrPb and Cd with the study area is likely to have a severe butlocalized effect

Conflict of Interests

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

References

[1] M A Olade ldquoHeavy metal pollution and the need for moni-toring illustrated for developing countrie s in West Africardquo inLead Mercury Cadmium and Arsenic in the Environment T CHutchinson and K M Meema Eds pp 335ndash341 JohnWiley ampSons 1987

[2] M H Bichi ldquoSurface water quality in the Kano IndustrialEnvironmentrdquo in Proceedings of the NationalWorkshop on LandAdministration and Development in Northern Nigeria J AFalola K Ahmed M A Liman and A Maiwada Eds pp305ndash313 Department of Geography Bayero University KanoNigeria 2000

[3] A Y Dada Evaluation of Kano State Environmental Man-agement Programme 1995 on industrial pollution case studyof Challawa and Sharada Industrial areas unpublished post-graduate Department of Geography Bayero University KanoNigeria 1997

[4] K Ahmed andA I Tanko ldquoAssessment of water quality changesfor irrigation in the river Hadejia Catchmentrdquo Journal of AridAgriculture vol 10 pp 89ndash94 2000

[5] C C Asonye N P Okolie E E Okenwa and U GIwuanyanwu ldquoSome physico-chemical characteristics andheavymetal profiles of Nigerian rivers streams and waterwaysrdquoAfrican Journal of Biotechnology vol 6 no 5 pp 617ndash624 2007

[6] L W A Izonfuo and A P Bariweni ldquoThe effect of urbanrunoff water and human activities on some physic-chemicalparameters of the Epie Creek in the Niger Deltardquo Journal ofApplied Sciences and Environmental Management vol 5 no 1pp 47ndash55 2001

[7] A M A Imevbore ldquoHydrology and plankton of eleiyelereservoir Ibadan NigeriardquoHydrobiologia vol 30 no 1 pp 154ndash176 1967

[8] A A Adebisi ldquoThe physico-chemical hydrology of a tropicalseasonal river-upper Ogun riverrdquo Hydrobiologia vol 79 no 2pp 157ndash165 1981

[9] E N Onyeike S I Ogbuja and N M Nwinuka ldquoInorganic ionlevels of soils and streams in some areas of Ogoniland Nigeriaas affected by crude oil spillagerdquo Environmental Monitoring andAssessment vol 73 no 2 pp 191ndash204 2002

[10] O T V Nefor and C Obiukwu ldquoImpact of refinery effluenton the physic-chemical properties of a water body in the NigerDeltardquo Applied Ecology and Environmental Research vol 3 no1 pp 61ndash72 2005

[11] O O Emoyan F E Ogban and E Akarah ldquoEvaluation of heavymetals loading of river Ijana in Ekpan-Warri Nigeriardquo Journalof Applied Sciences and Environmental Management vol 10 no2 pp 121ndash127 2006

[12] J C Nnaji A Uzairu G F S Harrison and M L BalarabeldquoEvaluation of Cd Cr Cu Pb and Zn in the fish headvisceraof oreochromis niloticus and synodonts schall of River Galma ZariaNigeriardquoElectronic Journal of Environmental Agriculturaland Food Chemistry vol 6 no 10 pp 2420ndash2426 2007

[13] J C kan V O Ogugbuaja F I Abdulrahman and J T AyodeleldquoDetermination of pollutant levels in water of river Challawaand in Tap water from Kano Industrial Area Kano StateNigeriardquo Research Journal of Environmental Sciences vol 1 no5 pp 211ndash219 2007

[14] O K AdeyemoO A Adedokun R K Yusuf and E A AdeleyeldquoSeasonal changes in physic-chemical parameters and nutrientload of river sediments in Ibadan City Nigeriardquo Global NESTJournal vol 10 no 3 pp 326ndash336 2008


[15] G Martinez W Senior and A Marquez ldquoHeavy metal specia-tion in the surface water dissolved fraction of the lowwatershedand plume of theManzanares River Sucre Venezuelardquo CienciasMarinas vol 32 no 2 pp 239ndash257 2006

[16] M Backstrom U Nilsson K Hakansson B Allard and SKarlsson ldquoSpeciation of heavy metals in road runoff androadside total depositionrdquoWater Air amp Soil Pollution vol 147no 1ndash4 pp 343ndash366 2003

[17] A KabiruTheKano Physical Environment Department of Geo-graphy Bayero University Kano Nigeria 2007 httpwwwkanoolinecom

[18] E E Obasohan ldquoThe use of heavy metals load as an indicatorof the suitability of the water and fish of Ibiekuma streamfor domestic and consumption purposesrdquo African Journal ofBiotechnology vol 7 no 23 pp 4345ndash4348 2008

[19] WHO Guideline for Drinking Water Quality vol 1 WorldHealth Organization Geneva Switzerland 2nd edition 1993

[20] Federal Environmental Protection Agency (FEPA) Guidelinesand Standards for Environmental Pollution Control in Nigeria1991

[21] EPA 2003 httpwwwepagovsafewaterstandardshtml[22] N G Tug G Sezen and F Duman ldquoSeasonal changes of some

heavy metal concentrations in Sapanca Lake water TurkeyrdquoInternational Journal of Natural and Engineering Sciences vol1 no 3 pp 25ndash28 2007

[23] S O Fakayode ldquoImpact assessment of industrial effluent onwater quality of the receiving Alaro River in Ibadan NigeriardquoAfrican Journal of Environmental Assessment and Managementvol 10 pp 1ndash13 2005

[24] R A Goyer ldquoLead toxicity current concernsrdquo EnvironmentalHealth Perspectives vol 100 pp 177ndash187 1993

[25] E J QrsquoFlaherty ldquoChromium toxickineticsrdquo in Toxicology ofMetals Biochemical Aspects R A Goyer and M G ClerianEds pp 315ndash328 Springer Heidelberg Germany 1995

[26] S E Kakulu and O Osibanjo ldquoPollution studies of NigeriaRivers Tracemetal levels of surface water inNigeria Delta areardquoInternational Journal of Environmental Studies vol 41 pp 287ndash292 1992

[27] S O Adefemi S S Asaolu and O Olaofe ldquoDetermination ofheavymetals inTilapiamossambicuis Fish associatedwater andsediment from Ureje Dam in South-Western Nigeriardquo ResearchJournal of Environmental Sciences vol 2 no 2 pp 151ndash155 2008


[29] B Markert ldquoPlant as bioindicators indicators for heavy metalsin the terrestrial environmentrdquo B Markert Ed VCH Wein-heim New York NY USA 1993

[30] E Hodgson and P E Levi A Textbook of Modern ToxicologyElsevier London UK 2002

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[5] According to Izonfuo and Bariweni [6] several humanactivities have been identified to result in water pollutionagriculture irrigation urbanization mining and industrial-ization Though several studies on Nigerian surface watershave been conducted [7ndash14] recently the understanding ofthe biogeochemistry of heavymetals inmarine environmentshas changed considerably during the last two decades [15]A more thorough comprehension of heavy metal cycling inthe environment could however require information on thechemical speciation of metals in solution that is the specificphysicochemical forms that are part of the total concentrationof metal in solution

On the other hand metal speciation determines thebioavailability andor toxicity of themetals for aquatic organ-isms in addition to affecting the cycle of metals in aquaticenvironments and in thewater-sediment interface Accordingto Backstrom et al [16] three fractionation stages weredefined for heavy metals in runoff from roadside dissolvedfraction mobile fraction and total fraction particulate frac-tion is the difference between total fraction and dissolvedfraction The mobile fractions of heavy metals are moreavailable for environmental functions than other fractionsIn the ecological context the mobile fractions rather thanthe total metal content are important Further the chemicalspecies especially in aquatic medium play important role intransfer of metals along the water-sediment aquatic animalsand plants to human chain Hence this research was initiatedto study seasonal variations of impact of industrial effluentson total dissolved mobile and particulate concentrationsof some selected heavy metals in surface water of riverChallawa in attempts to establish both long- and short-termconcentrations effects

2 Materials and Methods

21 Description of Study Area Challawa River is located inChallawa industrial estate (11∘45101584042N longitude 8∘46101584017E)in Kumbotso local Government of Kano State Kano Stateis located in the Northern part of Nigeria covering an areaextending between latitudes 12∘401015840 and 10∘301015840 and longitudes7∘401015840 and 9∘401015840 Challawa River is one of the receiving riversof effluents from Challawa industrial estate The industriesin the Challawa industrial estate range from tanneries andtextile to foods and packaging industries The effluents fromthe industries in the estate were connected by a canal andchanneled directly into Challawa River as a point sourceTheclimate of the area is dominated by the cyclical migrationintertropical convergence zone which is marked with longerdry than wet season and the highest rainfall in July andAugust [17] The relevant human activities in the River arecommercial sand dredging fishing washing and recreationduring hot hour of the day

22 Sample Collection The River was divided into upstreamand downstream areas as shown in Figure 1 Five samplingsites were chosen on downstream (polluted sites) and onesampling site was chosen on upstream (control site) givinga total of six sampling points Each sampling site comprisesof five sampling points composite to form a core for a site

In choosing the sites for the polluted sites preference wasgiven to such factor as points of effluent discharge intothe river Surface water was collected at the six sites ona seasonal basis between October 2006 and August 2008Surface water was collected at the middle of the river andstored in clean polythene bottles prewashed with acid andrinsed thoroughly with deionized water Once collected thesamples were immediately stored on ice in an ice box andtransported to the laboratory for analysis

Seasons

Warm and dry seasonmdashSeptemberndashNovemberCold and dry seasonmdashDecemberndashFebruaryHot and dry seasonmdashMarchndashMayWarm and wet seasonmdashJunendashAugust

23 Analysis Chemical fractionation of water samples wascarried out on the principle proposed by Backstrom et al[16] Samples were subjected to extraction using 2 nitricacid separately The extraction was aimed at differentiatingfractions in three stages as follows

Fraction I (dissolved) 50mL was decanted from thesampling vessel and filtered through 050120583m Teflonfilters before acidification with 2 nitric acid

Fraction II (mobile) 50mL was decanted from thesample vessel and acidified with 2 nitric acid fol-lowed by filtration through 050 120583mTeflon filters after24 hrs

Fraction III (total) 2 nitric acid was added directlyinto the sample vessel and shaken rigorously tosuspend all particulate matters The solution wasfiltered after 24 hrs through 050 120583m Teflon filtersThe particulate concentration was calculated as thedifference between Fraction III and Fraction I

Analysis of Cu Zn Pb Cr and Cr was performed on anatomic absorption spectrophotometer (AAS) The validationof the procedure for metal determination and efficiency ofAAS was conducted by spiking a sample with multielementstandard solution containing 05mgL of all metals analysedAll acid and reagents used were of analytical grade qualitycontrol certified by the use of procedural blanks and spikesThe spike recovery for eachmetal wasgt96All sampleswererun in triplicates

3 Results

The results of total heavy metals concentration of surfacewater across the seasons were presented in Table 1 Zn valuesranged between 088mgL (Site D during the cool and dryseason) and 386 mgL (Site E during hot and dry season)Season variations were observed with the highest value ofZn obtained during the hot and dry season In the samevein Pb concentration varied between 110mgL (Site E


To Panshekara

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textileindustry

026

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A BC D

E

A E

TsamawaHausawa


Challawabridge

Yandanko




















Cool and Dry Season


Hot and Dry Season










Warm and Wet Season



4 Discussion




Warm and dry season

000

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A B C D E F

Frac

tion

()

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2000

4000

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tion

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Sites

A B C D E FSites

A B C D E FSites

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Hot and dry season

Warm and wet season

Cool and dry season




Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

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Frac

tion

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2000

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2000

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6000

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2000

4000

6000

8000

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tion

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Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

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2000

4000

6000

8000

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tion

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2000

4000

6000

8000

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tion

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2000

4000

6000

8000

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tion

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A B C D E FSites

A B C D E FSites

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Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

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000

2000

4000

6000

8000

10000

Frac

tion

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000

2000

4000

6000

8000

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actio

n (

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2000

4000

6000

8000

10000

Frac

tion

()

A B C D E FSites

A B C D E FSites

A B C D E FSites

A B C D E FSites

DissolvedMobile

Particulate



5 Conclusion



Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

A B C D E FSites

A B C D E FSites

A B C D E FSites

A B C D E FSites

DissolvedMobile

Particulate





References









































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


To Panshekara

002001 04

06

0507

010

012 011013

014

017

018

015

019

020021

024

022

016

09 08

03

023


textileindustry

026

027

F

A BC D

E

A E

TsamawaHausawa


Challawabridge

Yandanko




















Cool and Dry Season


Hot and Dry Season










Warm and Wet Season



4 Discussion




Warm and dry season

000

2000

4000

6000

8000

10000

A B C D E F

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

Sites

A B C D E FSites

A B C D E FSites

A B C D E FSites

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Particulate

Hot and dry season

Warm and wet season

Cool and dry season




Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

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000

2000

4000

6000

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Frac

tion

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000

2000

4000

6000

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000

2000

4000

6000

8000

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tion

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Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

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Frac

tion

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2000

4000

6000

8000

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tion

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2000

4000

6000

8000

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tion

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2000

4000

6000

8000

10000

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tion

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A B C D E FSites

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Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

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2000

4000

6000

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2000

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2000

4000

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tion

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5 Conclusion



Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

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2000

4000

6000

8000

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2000

4000

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tion

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A B C D E FSites

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References









































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of














Cool and Dry Season


Hot and Dry Season










Warm and Wet Season



4 Discussion




Warm and dry season

000

2000

4000

6000

8000

10000

A B C D E F

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

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2000

4000

6000

8000

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tion

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2000

4000

6000

8000

10000

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tion

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Sites

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Particulate

Hot and dry season

Warm and wet season

Cool and dry season




Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

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Frac

tion

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2000

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2000

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000

2000

4000

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2000

4000

6000

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Cool and dry season

Hot and dry season

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000

2000

4000

6000

8000

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Frac

tion

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2000

4000

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5 Conclusion



Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

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tion

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A B C D E FSites

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A B C D E FSites

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References









































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of









Warm and Wet Season



4 Discussion




Warm and dry season

000

2000

4000

6000

8000

10000

A B C D E F

Frac

tion

()

000

2000

4000

6000

8000

10000

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tion

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2000

4000

6000

8000

10000

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tion

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2000

4000

6000

8000

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tion

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Sites

A B C D E FSites

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Warm and wet season

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2000

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5 Conclusion



Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

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tion

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2000

4000

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References









































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Warm and dry season

000

2000

4000

6000

8000

10000

A B C D E F

Frac

tion

()

000

2000

4000

6000

8000

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tion

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2000

4000

6000

8000

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tion

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2000

4000

6000

8000

10000

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tion

()

Sites

A B C D E FSites

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Particulate

Hot and dry season

Warm and wet season

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Warm and dry season

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000

2000

4000

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8000

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tion

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2000

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2000

4000

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Warm and dry season

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Warm and wet season

000

2000

4000

6000

8000

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tion

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2000

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tion

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2000

4000

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2000

4000

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8000

10000

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A B C D E FSites

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A B C D E FSites

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5 Conclusion



Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

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2000

4000

6000

8000

10000

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tion

()

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2000

4000

6000

8000

10000

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tion

()

A B C D E FSites

A B C D E FSites

A B C D E FSites

A B C D E FSites

DissolvedMobile

Particulate





References









































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

A B C D E FSites

A B C D E FSites

A B C D E FSites

A B C D E FSites

DissolvedMobile

Particulate




Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

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n (

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2000

4000

6000

8000

10000

Frac

tion

()

A B C D E FSites

A B C D E FSites

A B C D E FSites

A B C D E FSites

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Particulate



5 Conclusion



Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

A B C D E FSites

A B C D E FSites

A B C D E FSites

A B C D E FSites

DissolvedMobile

Particulate





References









































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Warm and dry season

Cool and dry season

Hot and dry season

Warm and wet season

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

000

2000

4000

6000

8000

10000

Frac

tion

()

A B C D E FSites

A B C D E FSites

A B C D E FSites

A B C D E FSites

DissolvedMobile

Particulate





References









































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



























Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Documents

Research Article Bioavailability Studies of Metals in ...downloads.hindawi.com/archive/2014/648453.pdf · Research Article Bioavailability Studies of Metals in Surface Water of River