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Determination of heavy metal contents in water, sediments, and fish tissues of Shizothorax plagiostomus in river Panjkora at Lower Dir, Khyber Pakhtunkhwa, Pakistan Kabir Ahmad & Azizullah Azizullah & Shama Shama & Muhammad Nasir Khan Khattak Received: 24 February 2014 /Accepted: 4 July 2014 /Published online: 14 July 2014 # Springer International Publishing Switzerland 2014 Abstract The present study was conducted to investi- gate the contamination of water, sediments, and fish tissues with heavy metals in river Panjkora at Lower Dir, Khyber Pakhtunkhwa, Pakistan. Water, sediments, and fish (Shizothorax plagiostomus) samples were col- lected from September 2012 to January 2013 at three different sites (upstream site at Sharigut, sewage site at Timergara, and downstream site at Sadoo) of river Panjkora. The concentrations of heavy metals in water were in the order Zn>Cu Pb>Ni Cd with mean values of 0.30, 0.01, 0.01, 0.0 and 0.0 mg/l, respectively, which were below the maximum permissible limits of WHO for drinking water. In sediments, heavy metals were found in the order Cu>Zn>Ni>Pb>Cd with mean concentrations of 50.6, 38.7, 9.3, 8, and 0.4 mg/kg, respectively. Ni and Cd were not found in any fish tissues, but Zn, Cu, and Pb were detected with the mean concentration ranges of 0.041.19, 0.030.12, and 0.010.09 μg/g, respectively. The present study demonstrates that disposal of waste effluents causes a slight increase in the concentration of heavy metals in river Panjkora as revealed by variation in metal concen- trations from upstream to downstream site. Sewage disposal was also found to change physicochemical characteristics of Panjkora water. At present, water and fish of river Panjkora are safe for human consumption, but the continuous sewage disposal may create prob- lems in the future. Keywords Heavy metals . Sediments . Fish . Freshwater pollution . River Panjkora . Pakistan Introduction Pollution of aquatic environments is one of the serious environmental problems worldwide. Different classes of contaminants like inorganic substances (toxic metals, acids, and salts), organic compounds (organic solvents, fossil fuels, pesticides, etc.), anions and cations (phos- phate, nitrates, sulfates, Mg 2+ , Ca 2+ , and F ), water- soluble radioactive substances, and pathogenic microor- ganisms (bacteria, viruses, and protozoan) are consid- ered common pollutants of aquatic environments (Azizullah et al. 2011). Among the various pollutants, heavy metals are of serious concern because they enter to and accumulate in the food chain. Low concentrations of some heavy metals are essential for the growth and development of living organisms, but some of them like Hg, Pb, and Cd Environ Monit Assess (2014) 186:73577366 DOI 10.1007/s10661-014-3932-1 K. Ahmad : M. N. K. Khattak Department of Zoology, Hazara University, Mansehra, Pakistan M. N. K. Khattak e-mail: [email protected] A. Azizullah (*) Department of Botany, Kohat University of Science and Technology, Kohat 26000, Pakistan e-mail: [email protected] S. Shama Sector D, House no. 259, Mansehra Township, Pakistan

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Page 1: Determination of heavy metal contents in water, sediments, and fish tissues of Shizothorax plagiostomus in river Panjkora at Lower Dir, Khyber Pakhtunkhwa, Pakistan

Determination of heavy metal contents in water, sediments,and fish tissues of Shizothorax plagiostomus in river Panjkoraat Lower Dir, Khyber Pakhtunkhwa, Pakistan

Kabir Ahmad & Azizullah Azizullah & Shama Shama &

Muhammad Nasir Khan Khattak

Received: 24 February 2014 /Accepted: 4 July 2014 /Published online: 14 July 2014# Springer International Publishing Switzerland 2014

Abstract The present study was conducted to investi-gate the contamination of water, sediments, and fishtissues with heavy metals in river Panjkora at LowerDir, Khyber Pakhtunkhwa, Pakistan. Water, sediments,and fish (Shizothorax plagiostomus) samples were col-lected from September 2012 to January 2013 at threedifferent sites (upstream site at Sharigut, sewage site atTimergara, and downstream site at Sadoo) of riverPanjkora. The concentrations of heavy metals in waterwere in the order Zn>Cu≈Pb>Ni≈Cd with meanvalues of 0.30, 0.01, 0.01, 0.0 and 0.0 mg/l, respectively,which were below the maximum permissible limits ofWHO for drinking water. In sediments, heavy metalswere found in the order Cu>Zn>Ni>Pb>Cdwithmeanconcentrations of 50.6, 38.7, 9.3, 8, and 0.4 mg/kg,respectively. Ni and Cd were not found in any fishtissues, but Zn, Cu, and Pb were detected with the meanconcentration ranges of 0.04–1.19, 0.03–0.12, and0.01–0.09 μg/g, respectively. The present study

demonstrates that disposal of waste effluents causes aslight increase in the concentration of heavy metals inriver Panjkora as revealed by variation in metal concen-trations from upstream to downstream site. Sewagedisposal was also found to change physicochemicalcharacteristics of Panjkora water. At present, water andfish of river Panjkora are safe for human consumption,but the continuous sewage disposal may create prob-lems in the future.

Keywords Heavymetals . Sediments . Fish . Freshwaterpollution . River Panjkora . Pakistan

Introduction

Pollution of aquatic environments is one of the seriousenvironmental problems worldwide. Different classes ofcontaminants like inorganic substances (toxic metals,acids, and salts), organic compounds (organic solvents,fossil fuels, pesticides, etc.), anions and cations (phos-phate, nitrates, sulfates, Mg2+, Ca2+, and F−), water-soluble radioactive substances, and pathogenic microor-ganisms (bacteria, viruses, and protozoan) are consid-ered common pollutants of aquatic environments(Azizullah et al. 2011).

Among the various pollutants, heavy metals are ofserious concern because they enter to and accumulate inthe food chain. Low concentrations of some heavymetals are essential for the growth and development ofliving organisms, but some of them like Hg, Pb, and Cd

Environ Monit Assess (2014) 186:7357–7366DOI 10.1007/s10661-014-3932-1

K. Ahmad :M. N. K. KhattakDepartment of Zoology, Hazara University, Mansehra,Pakistan

M. N. K. Khattake-mail: [email protected]

A. Azizullah (*)Department of Botany, Kohat University of Science andTechnology, Kohat 26000, Pakistane-mail: [email protected]

S. ShamaSector D, House no. 259, Mansehra Township, Pakistan

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are biologically non-essential and very toxic to livingorganisms. Even the essential metals may becometoxic if they are present in a concentration above thepermissible level (Puttaiah and Kiran 2008). Factorslike non-biodegradability and mutagenic, cytotoxic,and carcinogenic potentials of heavy metals make thema serious threat to the living organisms (More et al.2003). Both essential and non-essential heavy metalsare of great concern in ecotoxicology as they adverselyaffect various functions in living organisms(Ebrahimpour and Mushrifah 2010). For example, theycause suffocation and block the gills of fish (Karadedeand Unlo, 2000) as well as adversely affect variousphysiological and biochemical processes in algae(Ahmad 2010). Domestic sewages, industrial effluents,atmospheric deposition, leaching from landfills/dumpsites, and storm runoff are the major sources ofheavy metal pollution in water (Storelli et al. 2006;Keskin et al. 2007; Kumar et al. 2011).

Nutritional advantages like the presence of enoughprotein contents, sufficient omega fatty acids, andlow level of saturated fats make the fish an importantsource of diet worldwide (Storelli et al. 2006; Keskinet al. 2007; Kumar et al. 2011). Since a couple ofdecades, the interest in the detection of heavy metalsin food materials has been increased due to theirpotential to cause diverse health problems (VonSchiruding et al. 1991; Ipinmoroti et al. 1997).Traditionally, muscles have been used as an indicatorof heavy metal contents in the fish body, but musclesalone may not be a good indicator of the whole fishbody contamination. Therefore, other tissues like liv-er and gills should be considered for getting detailinformation on fish contamination (Has-Schon et al.2006). In the liver, the presence of metallothioneinsmetal-binding proteins significantly increases the ac-cumulation of heavy metals as compared to muscleswhere such proteins are absent (Ploetz et al. 2007;Uysa et al. 2009).

In Pakistan, surface water bodies like lakes, rivers,and streams are getting increasingly polluted with heavymetals due to improper disposal of municipal and in-dustrial effluents and agricultural runoff. Heavy metalslike As, Fe, Zn, Pb, Cd, Hg, Ni, and Cu have commonlybeen reported in water bodies of Pakistan, which ad-versely affect the aquatic biota as well as accumulate inthe food chain (Hussain et al. 2014). For example, heavypollution load in river Ravi due to sewage disposal fromthe city of Lahore claims the lives of over 5,000 tonnes

of fish every year (Kahlown and Majeed 2003). Manyrivers in the country have been stretched and have nolonger been able to support aquatic life (Aziz 2005).Moreover, these rivers and lakes are used as a source ofdrinking water supplies in the country, and their con-tamination with heavy metals can pose serious risks topublic health (Aziz 2005).

The present study was designed to determine heavymetal (Cd, Ni, Pb, Cu, and Zn) contamination in thewater, sediments, and fish tissues (muscles, liver, gills,and kidney) of river Panjkora in Lower Dir, KhyberPkhtunkhwa, Pakistan. River Panjkora rises in theHindu Kush Mountains, passes through different partsof the two districts of Dir (Lower Dir and Upper Dir),and joins river Swat near Chakdara. About 60 % of thepopulation in these two districts is dependent on itswater for everyday needs like irrigation, bathing, anddrinking. River Panjkora inhabits a diversity of fishspecies with Schizothorax plagiostomus, Schizothoraxesocinus , Triplophysa naziri , Crossocheilusdiplocheilus, Glyptosternum reticulatum , andTriplophysa choprai as the most commonly occurringspecies. S. plagiostomus, commonly known as snowtrout, is a commercially important fish belonging tothe family Cyprinidae and is frequently found in largenumber during the winter season. In winter, people ofthe area prefer to eat snow trout of river Panjkora andbuy it in double price as compared to other farm fish.The main objectives of this study were (1) to investigatethe effect of municipal wastes on heavy metal contentsin the water, sediments, and fish of river Panjkora and(2) to evaluate whether the water and fish of this riverare safe for human consumption.

Materials and methods

Study area

Lower Dir is a part of Malakand division located in theKhyber Pakhtunkhwa province of Pakistan. It lies in theHidukush range between 35° 10 to 35° 16 N latitudeand 71° 50 to 71° 83 E longitude. The total area ofLower Dir is 1,585 km2 with a total population of717,649 as per 1998 census report. It is bordered bySwat on the east, Afghanistan on the west, Dir Upperon the north, and Malakand agency on the south (Khanet al., 2010). River Panjkora is considered as the mainlife line of this area.

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Sample collection

Samples of water, sediments, and fish (S. plagiostomus)were collected in triplicates at three pre-located sites ofriver Panjkora, viz. site I (upstream site at Sharigut), siteII (sewage site at Timergara, where effluents aredischarged into the river), and site III (downstream siteat Sadoo) (Fig. 1). Upstream site is comparatively lesspopulated and receives smaller amount of wastes ascompared to sewage site which is a densely populatedarea and receives more sewage effluents. Samples werecollected from all the sites for three times, i.e., inSeptember 2012, November 2012, and January 2013.

Physicochemical analysis of water

Water samples were collected in plastic bottles withscrew caps and were taken to Pakistan Council ofScientific and Industrial Research (PCSIR) laboratoriesat Peshawar, Pakistan. Physicochemical parameters ofwater including temperature (by Red Alcohol thermom-eter), pH (by pH meter Mettler delta 320 UK), electricalconductivity (by LT LutronModel No. CD-4303HA ECmeter), and total dissolved solid (by TDS meter ModelNo. 98301) and dissolved oxygen (by oxymeter modelLutron DO-5510 Taiwan) were determined. The totalsuspended solid (TSS) was determined by filtration

Fig. 1 Map of Lower Dir indicating sampling sites at river Panjkora (modified from ACTED (2010))

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method. Total hardness (with EDTA), calcium hardness(with EDTA), total alkalinity (with H2SO4), and chlo-ride (with AgNO3) were determined using standardtitration methods. Sodium and potassium were mea-sured with flame photometer while sulfates were deter-mined using UV spectrometer.

Sample preparation for heavy metal analysis

Water sample preparation

For heavy metal analysis, water samples were preparedaccording to standard procedure (APHA 1995). Allsamples were digested with concentrated nitric acid(100 ml water:5 ml HNO3). A 100 ml of water samplewas transferred to a beaker, and 5 ml of concentratedHNO3 was added in a fume hood. The beaker wascovered with a ribbed glass watch to minimize thechances of contamination. The sample was boiled andevaporated on a hot plate. Heating and adding HNO3

was continued until digestion was completed as indicat-ed by obtaining a light-colored or clear solution. Thesamplewas filtered in a clean beaker and was transferredto a 100-ml volumetric flask. After cooling, the volumeof sample was raised to 100ml by adding distilled water.The procedure was repeated for each sample. The pre-pared samples were then subjected to atomic absorptionspectrophotometer for heavy metal analysis.

Sediment sample preparation

Three grams of each sediment sample was air dried,crushed, and screened through a 1-mm sieve. One gramof the sieved sediment was taken, and 15 ml of HCl and5 ml of HNO3 were added. The mixture was boiled on ahot plate. The digested samples were filtered and 100 mlof distilled water was added.

Fish tissue sample preparation

Fish specimens were dissected for the required tissues(liver, gills, muscles, and kidneys). Each tissue wasdigested separately with concentrated nitric acid(HNO3) and perchloric acid (HClO4). One gram of eachorgan was transferred to digestion flasks. HNO3 (25 ml)was added, and the sample was boiled by hot plate in afume hood for 35 min. After cooling at room tempera-ture, HClO4 (15 ml) was added, and the solution wasgently boiled for 1 h to obtain a colorless solution. The

digest was diluted with distilled water to make the finalvolume of 100 ml.

Analysis of heavy metals

All samples were analyzed for heavy metal contentsincluding Pb, Cd, Ni, Cu, and Zn using atomic absorp-tion spectrophotometer (Model Z-2000 Hitachi). Alamp current of 7.5 mA was used for Pb, Ni, and Cueach whereas 10 and 5 mA lamp currents were used forCd and Zn, respectively. Burner height of 7.5 was usedfor each Pb, Ni, Cu, and Zn while a height of 5 was usedfor Cd. The wavelengths of 247.6, 228.8, 232, 324.8,and 213.9 nm were used for Pb, Cd, Ni, Cu, and Zn,respectively.

Statistical analysis

Statistical package programs SPSS (Version 16.0) andMS Word Excel were used for statistical analysis ofdata. One-way analysis of variance (ANOVA) followedby Scheffe post hoc comparisons test was applied todetermine significance of differences among variousdata sets. The difference was considered to be signifi-cant if p value was smaller than 0.05 (p<0.05).

Results

Physicochemical properties of water

Physicochemical characteristics of water samples at thethree different sites of river Panjkora are shown inTable 1. Mean temperatures of water at the upstream,sewage, and downstream sites were 19.7, 19.9, and19.7 °C, respectively. pH values were 7.7, 7.4, and7.6 at the upstream, sewage, and downstream sites,respectively. EC ranged as 236.4–286.9 μS/cm, withthe lowest being at the upstream and the highest at thedownstream site. TDS and TSS at the upstream, sewage,and downstream sites were 155.4, 157.3, and 210.9 mg/land 3.0, 3.3, and 4.2 mg/l, respectively. DO was thehighest at the upstream site (9 mg/l), but the other twosites had the same quantity of DO (8.7 mg/l). Ca wasfound reaching 93.4, 105.1, and 112.2 mg/l, while Mgwas 10.7, 16.9, and 16.4 mg/l at the upstream, sewage,and downstream sites, respectively. Total hardness(104.1, 122.0, and 128.7 mg/l), total alkalinity (2.8,2.5 and 3.3 mg/l), chloride (13.6, 14.7 and 15.4 mg/l),

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sodium (8.5, 9.3 and 10.8 mg/l), potassium (2.7, 3.0 and3.2 mg/l), and sulfates (7.1, 9.7 and 12.7 mg/l) werefound at all the three sites (values given for each param-eter in parentheses for upstream, sewage, and down-stream sites, respectively).

Heavy metal concentrations in water

Ni and Cd were not detected in any sample of water.The mean concentration of each Pb and Cu was0.01 mg/l at every sampling site (Fig. 2). There was agradual increase in the concentration of Zn from up-stream to downstream site with the mean concentrationof 0.06, 0.11, and 0.18 mg/l at upstream, sewage, anddownstream sites, respectively (Fig. 2). The increase inZn concentration at the downstream site was statistical-ly significant (p<0.05) as compared to upstream andsewage sites. No statistical difference was observed inheavy metal concentrations between upstream and sew-age sites.

Heavy metal concentrations in sediments

In sediment samples, mean concentrations of Ni, Cd,Pb, Cu, and Zn at the upstream site were 4.57, 4.57,6.58, 35.10, and 24.37 mg/kg, while at the sewagesite, the concentrations of these metals were 12.24,

11.58, 8.25, 40.92, and 24.56 mg/kg, respectively. Atthe downstream site, their concentrations were 15.79,16.32, 11.63, 45.13, and 28.43 mg/kg, respectively(Fig. 3). An increase in the concentration of all stud-ied metals was observed from the upstream to down-stream site. Pb and Ni concentrations in sedimentswere significantly higher at the sewage site as com-pared to the upstream site; however, no statisticaldifference was found in Cd, Cu, and Zn betweenthese sites. A significant increase in Ni, Cd, Pb, andZn concentrations was observed at the downstreamsite, but no statistical difference was found in Cuconcentration as compared to the upstream and sew-age sites.

Table 1 Physicochemical properties of water at different sites ofriver Panjkora. Values given are mean±standard deviation

Upstreamsite

Sewagesite

Downstreamsite

Temperature (°C) 19.7±2.7 19.9±2.8 19.7±3.0

pH 7.7±0.5 7.4±0.7 7.6±0.5

EC (μS/cm) 236.4±52.7 251.6±58.8 286.9±76.1

TDS (mg/l) 155.4±20.1 157.3±21.5 210.9±57.2

TSS (mg/l) 3.0±0.1 3.3±0.8 4.2±0.5

DO (mg/l) 9±0.2 8.7±0.3 8.7±0.4

Ca (mg/l) 93.4±10.3 105.1±3.7 112.2±4.7

Mg (mg/l) 10.7±2.2 16.9±2.4 16.4±5.3

TH (mg/l) 104.1±12.4 122.0±5.3 128.7±9.5

Total alkalinity (mg/l) 2.8±0.3 2.5±1.2 3.3±1.1

Chloride (mg/l) 13.6±1.0 14.7±0.9 15.4±2.2

Sodium (mg/l) 8.5±1.2 9.3±1.3 10.8±2.9

Potassium (mg/l) 2.7±0.2 3.0±0.1 3.2±0.5

Sulfate (mg/l) 7.1±0.8 9.7±0.6 12.7±2.7

Fig. 2 Concentrations of heavy metals in water (mg/l) at differentsites of river Panjkora. The column bars represent mean concen-tration while the error bars show standard error. Asterisks indicatea significant difference among different sites

Fig. 3 Concentration of heavy metals (mg/kg) in sediments col-lected at three different sites from river Panjkora. The columnbars represent mean concentration while the error bars showstandard error. Asterisks indicate a significant difference amongdifferent sites

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Heavy metal concentrations in tissuesof S. plagiostomus

Heavy metal concentrations in liver

In the liver of S. plagiostomus, Cd and Ni were notdetected at any site, but Pb, Cu, and Zn were found inthe liver of all specimens. The mean concentrations ofPb, Cu, and Zn in the liver were 0.01, 0.03, and 0.41 μg/g at the upstream site; 0.04, 0.12, and 1.19 μg/g at thesewage site; and 0.06, 0.07, and 0.41 μg/g at the down-stream site, respectively (Fig. 4). Cu and Zn in the liverwere found significantly higher at the sewage site ascompared to the upstream site, but no significant differ-ence was observed in Pb concentration. Pb was alsosignificantly higher in the liver of fish at the downstreamsite than at the upstream site, but no significance differ-encewas observed in Cu and Zn concentrations betweenthese two sites. There was no significant difference in Pband Cu contents in the fish liver between downstreamand sewage sites, but Zn was significantly higher at thedownstream than at the sewage site.

Heavy metal concentrations in gills

Cd and Ni were not detected in gills of S. plagiostomus.The mean concentrations of Pb, Cu, and Zn in gills ofspecimens at the upstream site were 0.01, 0.04 and0.25 μg/g; 0.04, 0.07, and 0.74 μg/g at the sewage site;and 0.06, 0.05, and 0.66 μg/g at the downstream site,respectively (Fig. 5). Pb, Cu, and Zn contents in gills of

fish were significantly higher at the sewage site than atthe upstream site. Cu and Zn concentrations were alsosignificantly higher in fish gills at the downstream sitewhen compared to the upstream site; however, no sig-nificant difference was observed in Pb concentrationsbetween upstream and downstream sites. A significantincrease in Pb concentration in gills was observed at thedownstream site as compared to the sewage site. Cuconcentration was significantly higher at the sewage siteas compared to the downstream site; however, no sig-nificant difference was found in Zn between sewage siteand downstream site.

Heavy metal concentrations in muscles

Both Cd and Ni were also not detected in the muscles ofS. plagiostomus, but Pb, Cu, and Zn were detected withthe mean concentrations of 0.01, 0.03, and 0.31 μg/g atthe upstream site; 0.03, 0.05, and 0.80 μg/g at thesewage site; and 0.09, 0.05, and 0.041 μg/g at thedownstream site, respectively (Fig. 6). Cu and Zn con-centrations in the muscles were significantly higher inthe fish at sewage site as compared to the upstream site,but no statistical difference was observed in Pb concen-tration between these two sites. A significant increase inPb and Cu contents in the muscles of fish was observedat the downstream site as compared to upstream site, butthere was no significance difference in Zn contentsbetween these sites. Pb in fish muscles was significantlyhigher at the downstream site as compared to the sewagesite. Zn was significantly higher at the sewage site as

Fig. 4 Concentrations of heavy metals (μg/g) in the liver ofS. plagiostomus at different sites in river Panjkora. The columnbars represent mean concentration while the error bars showstandard error. Asterisks indicate significant difference amongdifferent sites

Fig. 5 Concentrations of heavy metals (μg/g) in the gills ofS. plagiostomus at different sites in river Panjkora. The columnbars represent mean concentration while the error bars showstandard error. Asterisks represent significance difference amongdifferent sites

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compared to the downstream site. No significant differ-ence was observed in Cu concentration between sewagesite and downstream site.

Heavy metal concentration in kidney

Like other tissues of S. plagiostomus, Cd and Ni werealso not detected in any sample of fish kidney. The meanconcentrations of Pb, Cu, and Zn in fish kidney were0.01, 0.03, and 0.32 μg/g at the upstream site; 0.03,0.06, and 0.65 μg/g at the sewage site; and 0.07, 0.05,and 0.60 μg/g at the downstream site, respectively(Fig. 7). Cu and Zn concentrations in the kidney were

significantly higher in fish at the sewage site as com-pared to the upstream site, but the difference in Pbconcentration was not significant. In comparison tothe upstream site, fish kidney had significantly highercontents of Pb, Cu, and Zn at the downstream site. Pb inthe kidney was also significantly higher in fish at thedownstream site when compared to sewage site. Acomparison of sewage and downstream sites revealsthat fish at the sewage site had higher Cu in their kidneythan those at the downstream site, but there was nosignificant difference in Zn concentrations in theirkidneys.

Discussion

The physicochemical characteristics of water at all thethree sites of river Panjkora were found within thepermissible range of WHO for drinking water(pH 6.5–8.5, hardness 200 mg/l, sodium 200 mg/l,sulfate 250 mg/l, TDS 1,000 mg/l, TSS 500 mg/l, andchloride 250 g/l). However, the concentrations of TDS,TSS, total hardness, Ca hardness, Mg hardness, Cl−,Na+, and K+ were comparatively higher at the sewageand downstream sites than at the upstream site, whichreflects the contribution of sewage effluents to riverpollution. These results are in accordance with previousreports revealing indiscriminate disposal of waste efflu-ents as a major source of increased pollution in certainrivers of the country (Khan et al. 2012; Yousafzai et al.2008; Azizullah et al. 2013; Nergis et al. 2013).

The main objective of this study was the determina-tion of selected heavy metals (Cd, Ni, Pb, Cu, and Zn) inthe water, sediments, and fish tissues at different sites ofthe river. Cd, Ni, and Pb were selected due to theirecotoxicological importance while Zn and Cu wereselected because of their expected high availability inthe study area. At all three sites of the river, concentra-tions of these metals in the water were within the per-missible limits of WHO for drinking water (3, 0.02, 2,0.003, and 0.01 mg/l for Zn, Ni, Cu, Cd and Pb, respec-tively). The guidelines of WWF for propagation andbalance growth of fish and other aquatic organisms are0.01, 0.007, 0.086, 0.05, and 0.002 mg/l for Pb, Cu, Zn,Ni, and Cd, respectively (WWF 2007). In the currentstudy, Cu and Zn exceeded these limits, but the remain-ing heavy metals were found within the permissiblelimits. Heavy metals in water of river Panjkora alsofulfilled the guidelines for heavy metals in water for

Fig. 7 Concentrations of heavy metals (μg/g) in the kidney ofS. plagiostomus at different sites in river Panjkora. The columnbars represent mean concentration while the error bars showstandard error. Asterisks represent significance difference amongdifferent sites

Fig. 6 Concentrations of heavy metals (μg/g) in the muscles ofS. plagiostomus at different sites in river Panjkora. The columnbars represent mean concentration while the error bars showstandard error. Asterisks represent significant difference amongdifferent sites

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irrigation and livestock watering, which are 0.2 mg/l foreach Cu, Zn, and Ni; 0.1 mg/l for Pb; and 0.01 mg/l forCd (WWF 2007).

The higher concentration of Zn in river Panjkorawater as compared to other metals can be attributed tothe existence of varying amounts of Zn in majority ofrocks and minerals (Malle 1992). A recently publishedstudy revealed that concentrations of Zn and Cu in waterof river Ravi at Balloki Headworks in Punjab provinceof Pakistan ranged 0.172–0.480 mg/l and 0.145–0.371 mg/l, respectively (Tabinda et al. 2013). Theconcentrations of Ni, Zn, Cu, and Pb in Shah Alam riverat Peshawar were found reaching 0.65, 0.2, 0.08, and0.9 mg/l, respectively (Khan et al., 2011). The compar-atively higher concentrations of heavy metals in theserivers have been attributed to the disposal of large quan-tity of domestic sewage and industrial effluents fromdifferent sources. Disposal of industrial and municipaleffluents has been regarded as a major source of heavymetal pollution in surface water across the world(Polprasert 1982; Manga 1983; Oguzie andOkhagbuzo 2010). In the current study too, sewagedisposal proved to be the major cause of increase inheavy metal concentrations in river Panjkora, as re-vealed by an increase in heavy metal contents fromupstream to downstream site. No doubt at present thesemetals in water are within the permissible limits, but ifsewage disposal continues, it may create problems in thefuture.

In sediments, the permissible limits of Ni, Cd, Pb,Cu, and Zn are 35, 0.8, 85, 36, and 140 mg/kg, respec-tively, as recommended by Dutch Target Limits(Tabinda et al. 2013). In the present study, Ni, Pb, andZn concentrations were well below, but Cu and Cdexceeded these limits. In comparison to our findings,Zn, Cu, and Ni in sediments of river Ravi ranged be-tween 125.68–133.16, 38.4–47.93, and 23.5–25.21 mg/kg in the winter season and 138.58–147.20,55.44–60.13, and 28.99–32.53 mg/kg in the summerseason, respectively (Tabinda et al. 2013), which weremuch higher, except Cu, than in sediments of riverPanjkora observed in the present survey. A possiblereason for comparatively high contents of Cu in sedi-ments of Panjkora is that Cu ores exist in Sheringal andother parts of Dir through which River Panjkora passes.Like water, in sediments also, an increase in metalconcentrations was observed from the upstream todownstream site due to sewage effluents that dischargesinto the river.

The physicochemical characteristics of riverPanjkora mostly fulfills the permissible standards; how-ever, it may not necessarily guarantee the safety toaquatic organisms because various pollutants in waterand wastewater, even if they meet the permissible stan-dards, could still cause negative effects on aquatic or-ganisms (Danilov and Ekelund 2000; Movahedian et al.2005). For example, wastewater and river water sampleshaving physicochemical characteristics within the per-missible range still had adverse effects on various phys-iological and morphological parameters of the greenalga Euglena gracilis (Azizullah et al. 2013).

Heavy metal contents in different tissues ofS. plagiostomus observed in the present study werewithin the permissible limits recommended by differentagencies. In fish muscles, the permissible limits ofCanadian Standards (CS) for Zn and Cu are 100 μg/gwhereas the UK permissible limit for Pb in food is 1 μg/g. The maximum permissible concentration of Ni infood is 1 μg/g, as recommended by USEPA and thatof Cd is 0.1 μg/g as per Turkish legislation (Korai et al.2008; Aktan and Tekin-Ozan 2012; Tabinda et al. 2013).The maximum allowable level of Zn (50 μg/g) in foodmaterials established by the Turkish legislation is higherthan that recommended byWHO (30 μg/g) and may notbe safe for human consumption (Aktan and Tekin-Ozan2012). The higher accumulation of Zn in fish tissues ascompared to other metals in the current study can be dueto the increased availability of this metal in water. Theaccumulations of Zn, Pb, Cu, and Ni in Cyprinus carpioat river Kabul in Nowshera were 826, 74.7, 303, 53.3,and 266 μg/g, respectively (Yousafzai et al. 2012). Theconcentrations of Pb, Cu, and Zn in the liver of Torputitora from river Kabul ranged as 93.66–136.8,109.5–146.9, and 1,694.0–1,935.5 μg/g, respectively,whereas in gills, these metals ranged as 219.3–321,44.7–76.7, and 1993.9–2,414 μg/g, respectively(Yousafzai and Shakoori 2008; Yousafzai et al. 2009).The order of metal concentrations (Zn>Cu>Pb>Ni) inthe liver and gills in the present study was similar to thatin T. putitora at river Kabul (Yousafzai and Shakoori2008; Yousafzai et al. 2009). A recent report revealedthat heavy metals including Zn, Cu, and Ni in musclesof Cirrhinus mrigala from river Ravi ranged as 58.74–77.86, 5.94–7.14, and 1.33–2.19 μg/g, respectively(Tabinda et al. 2013). Some recent analyses showed thatfive different fish species including C. carpio,T. putitora, C. mrigala, Labeo calbasu, and Channapunctatus from Rawal Lake at the Capital Islamabad

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had various heavy metals beyond the permissible limits(Iqbal and Shah 2013; Malik et al. 2014). The highercontents of heavy metals in fish in these previous studieshave been attributed to higher contamination of thesereservoirs due to indiscriminate disposal of municipaland industrial effluents. Surface water pollution due tosewage disposal has been regarded as a major factorresponsible for heavy metal accumulation in fish as wellas for adverse effects in fish (Singh et al. 2014; Zeitounand Mehana 2014). A review of literature shows thatmore than 50 % of studies addressing heavy metal-contaminated fish have been reported from the Punjabprovince, followed by Sindh and Khyber Pakhtunkhwaprovinces in Pakistan (Hussain et al. 2014).

The comparison of present results with previousstudies indicates that river Panjkora is less contaminatedas compared to many other rivers in Pakistan, and heavymetal contents in fish of this river are within the permis-sible limits with no apparent threat to human health. Itcan be due to the fact that industries in the area are fewand population density is low. At present, the river canafford the sewage water of the area. However, if agri-culture runoff and waste effluents discharging continueto the river at this magnitude, problems will arise in thefuture. Therefore, there is a need for monitoring ofproper treatment and disposal of waste effluents in thearea so as to protect the water of river Panjkora fromdeterioration in the future.

Conclusion

The apparent sources of pollution in the area are anthro-pogenic activities like improper agricultural practicesand disposal of waste effluents. At present, the waterof river Panjkora fulfills the drinking water standards ofWHO. In sediments of Panjkora, Zn, Pb, and Ni werewithin the permissible limits, but Cd and Cu concentra-tions exceeded these limits. Concentrations of heavymetals in tissues of the analyzed fish were also withinthe permissible limits, and the fish of river Panjkora aresafe for human consumption. Zn concentration wascomparatively higher in all analyzed tissues followedbyCu, Pb, and Ni≈Cd. At present, the quality of water inriver Panjkora is good for human consumption, but Cuand Zn exceeded the limits of WWF for the propagationand balance growth of fish and aquatic organisms.Proper management is needed to sustain the quality ofthis river for the coming generations.

Acknowledgments We acknowledge Higher Education Com-mission of Pakistan for financially supporting the analytical workof this project under “access to scientific instrumentationprogramme”.

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