- Email: [email protected]
Distribution of trace metals in the Hindon River system, India
Journal of Hydrology 253 (2001) 81±90
www.elsevier.com/locate/jhydrol
Distribution of trace metals in the Hindon River system, India C.K. Jain*, M.K. Sharma National Institute of Hydrology, Roorkee 247 667, India Received 20 September 2000; revised 22 May 2001; accepted 5 June 2001
Abstract The distribution of trace metals (Cu, Zn, Fe, Mn, Cd, Cr, Pb, and Ni) in water, suspended and bed sediments of the River Hindon, a highly polluted river in western Uttar Pradesh (India) has been studied. The river is polluted by municipal, industrial and agricultural ef¯uents, and ¯ows through the city of Saharanpur, Muzaffarnagar and Ghaziabad districts. The heavy metal concentrations in water were observed to depend largely on the amount of ¯owing water and are negatively correlated with ¯ow. Sediment analysis indicates that the large amount of heavy metals is associated with organic matter, the ®ne-grained sediment fraction and Fe/Mn hydrous oxides. A high positive correlation of most of the metal ions in sediments with iron, manganese and organic matter indicate that these constituents play a major role in transport of metal ions. The heavy metal concentrations generally increased with the decreasing particle size of the sediments. Lower metal concentrations in bed sediments during post-monsoon season established that monsoon had a slight effect on status of metals in sediments by causing renewal and mobilization of metals from the sediments. q 2001 Elsevier Science B.V. All rights reserved. Keywords: Trace metals; Distribution; Bed sediments; River system
1. Introduction In recent years, the ¯uxes of trace metals from terrestial and atmospheric sources to the aquatic environment have increased considerably (Forstner and Wittmann, 1981). Numerous studies have demonstrated that the determination of metal concentrations in suspended and bed sediments is more sensitive than the dissolved concentrations as indicators of contamination in hydrologic systems (Salomons and Forstner, 1984; Luoma, 1990). The presence of trace metals in sediments is affected by the particle size and composition of sediments (Yamagata and Shigematsu, 1970; Foster and Hunt, 1975; Hiraizumi et al., 1978; Asami and Sampei, 1979; Ogura et al., 1979; Forstner and Wittmann, 1981; Thorne and * Corresponding author. E-mail address: [email protected] (C.K. Jain).
Nickless, 1981; Kristensen, 1982; Thomson et al., 1984; Sakai et al., 1986; Raymahashay, 1987; Krumlgalz, 1989; Combest, 1991; Sabri et al., 1993). More than 97% of the mass transport of metals to oceans is associated with river sediments (Gibbs, 1977). A variety of factors such as basin geology, physiography, chemical reactivity, lithology, mineralogy, hydrology, vegetation, land use pattern and biological productivity regulate the metal load of a river system (Garrels et al., 1975; Warren, 1981; Aurada, 1983; Zhang and Huang, 1993). Martin and Meybeck (1979) studied elemental mass balance of material carried by major world rivers. Due to the relative mobility of metals during transport processes, sediment can re¯ect the present quality of the basin and the historical development of various hydrological and chemical parameters. The metal contribution from Indian rivers, which carry 20% of the global supply of sediments to the
0022-1694/01/$ - see front matter q 2001 Elsevier Science B.V. All rights reserved. PII: S 0022- 169 4( 01) 00484-X
82
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Fig. 1. Hindon River Basin showing location of sampling site.
oceans has not been properly assessed (Subramanian, 1979; Subramanian et al., 1985). Borole et al. (1982) and Subramanian et al. (1988) have reported metal concentrations in estuarine sediments on the West and East Coast of India. Recent geochemical studies of some basins have yielded additional data to improve and update information on the metal contribution of Indian rivers to the adjacent ocean (Subramanian et al., 1987; Biksham and Subramanian, 1988; Ramanathan et al., 1988; Subramanian and Jha, 1988; Ramesh et al., 1990). The river Yamuna contributes 64 £ 10 6 t year 21 of
suspended sediments and 42 £ 10 6 t year 21 of dissolved load to the Ganges (Jha et al., 1988). Bed sediments of the River Yamuna have higher concentrations of metals than other tributaries. Sediment grain size, mineralogical difference and varying amounts of anthropogenic contributions may be the prime factors controlling metal variation (Jha et al., 1990). Subramanian and Sitasawad (1984) reported that annually, 86 t Ni, 64 t Cr, 61 t Pb, 45 t Fe and 36 t Zn, derived from industrial ef¯uents and city wastes are disposed into the River Yamuna in the vicinity of Delhi alone.
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
The River Hindon is an important tributary of the River Yamuna and carries pollution load from industrial towns and agricultural areas of western Uttar Pradesh (India). Verma et al. (1980) conducted limnological studies of the River Hindon in relation to ®sh and ®sheries while Lokesh (1996) studied the fate of heavy metals in water and sediments of the river. In earlier publications, we have carried out in-depth investigations on water and sediments of the River Kali, a tributary of the River Hindon, (Jain, 1996; Jain and Ram, 1997a,b; Jain et al., 1997, 1998a,b). In view of the above observations it is of interest to study the distribution of trace metals in water, suspended sediments and bed sediments of river Hindon under different ¯ow conditions. 2. Study area The Hindon Basin is a part of Indogangetic Plains, composed of Pleistocene and subrecent alluvium and lies between latitude 28830 0 to 30815 0 N and longitude 77820 0 to 77850 0 . The river Hindon originates from Upper Shivaliks (Lower Himalayas) and ¯ows through four major districts, viz. Saharanpur, Muzaffarnagar, Meerut and Ghaziabad in western Uttar Pradesh and Joins the River Yamuna downstream of Delhi at Tilwara. (Fig. 1). The climate of the region is moderate subtropical monsoon type. The average annual rainfall is about 1000 mm, the major part of which is received during the monsoon period. The major land use in the basin is agriculture and there is no effective forest cover. The soil type of the basin is alluvial consisting of clay, silt and ®ne to coarse sand. The basin is densely populated because of the rapid industrialization and agricultural growth during last few decades. The discharge from municipal and industrial areas as well as runoff from agricultural areas affects the quantity and quality of the river water. The main sources, which create pollution in the River Hindon include municipal waste of Saharanpur, Muzaffarnagar and Ghaziabad districts and industrial ef¯uents of sugar, pulp and paper, distilleries and other miscellaneous industries through tributaries as well as direct outfalls. In non-monsoon months, the river is completely dry from its origin upto Saharanpur town. The ef¯uents of Nagdev nala
83
and Star Paper Mill at Saharanpur generate the ¯ow of water in the river. The municipal waste generated from Saharanpur is discharged to the Hindon River through Dhamola nala. The industrial ef¯uent from Cooperative Distillery also joins the river in this stretch. The River Kali meets the River Hindon on its left bank near the village of Atali, which is carrying municipal wastewater and ef¯uents of industries located in Muzaffarnagar. Another tributary called Krishni meets Hindon on its right bank at the village of Barnawa in Meerut district and carrying the waste water from sugar mill and distillery. In Ghaziabad district, the majority of the ¯ow of the river is diverted to the Hindon cut canal at Mohan Nagar. Thereafter, the river ¯ows downstream and joins the River Yamuna at the village of Tilwara (Fig. 1). The characteristics of the various waste ef¯uents/tributaries and their impact on river water quality have been discussed in an earlier report (Jain and Sharma, 1998). 3. Experimental methodology The water and sediment samples were collected from the Hindon River at Mohan Nagar. The water samples were collected in polyethylene bottles from 1/3, 1/2 and 2/3 width of the river using a standard water sampler (Hydro Bios, Germany) and then mixed together to obtain a composite sample. The sample bottles were soaked in 10% HNO3 for 24 h and rinsed several times with deionized water prior to use. The water samples were ®ltered through 0.45 mm membrane ®lters to obtain samples for dissolved metal estimations and preserved with ultra pure nitric acid to bring down the pH to ,2.0. The samples thus preserved were stored at 48C in sampling kits and brought to the laboratory for trace element analysis. The water samples for total metal analysis were preserved using ultra pure nitric acid and then digested on a hot plate. Suspended sediments were collected by ®ltering water samples through 0.45 mm membrane ®lters. Bed sediment samples were collected by an Ekman grab sampler, dried at 708C and sieved to obtain different particle fractions (0±75, 75±150, 150±200, 200±250, 250±300, 300±425 and 425±600 mm) and stored in polyethylene bags until further processing.
84
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Fig. 2. Monthly variation of dissolved, total and particulate metal concentrations.
The extraction of sediments was carried out using acid mixture (HNO3 1 HClO4). Organic matter in the sediment was determined by the wet oxidation±redox titration method using an acid dichromate solution followed back titration of remaining dichromate with ferrous ammonium
sulphate. The reported data are the sum of soluble and insoluble organic carbon. All chemicals and standard solutions used in the study were obtained from Merck, India/Germany and were of analytical grade. Deionized water was used throughout the study. All glassware and other
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Fig. 3. Relationship between dissolved metal concentrations and ¯ow.
85
86
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Table 1 Correlation coef®cients among metal concentrations in suspended sediments Flow
SS
Cu
Zn
Fe
Mn
Cd
Cr
Pb
Ni
OM
Flow SS Cu Zn Fe Mn Cd Cr Pb Ni OM
1.000 0.179 20.452 20.649 20.648 20.621 20.635 20.478 20.658 20.465 20.608
1.000 20.218 20.302 20.125 20.070 0.359 20.315 20.321 20.566 20.442
1.000 0.844 0.895 0.697 0.551 0.881 0.869 0.675 0.886
1.000 0.773 0.807 0.563 0.840 0.866 0.574 0.793
1.000 0.662 0.716 0.718 0.806 0.743 0.901
1.000 0.748 0.781 0.910 0.321 0.714
1.000 0.432 0.627 0.163 0.519
1.000 0.930 0.614 0.851
1.000 0.605 0.914
1.000 0.808
containers were thoroughly cleaned and ®nally rinsed with deionized water several times prior to use. Trace metal analysis was carried out using a Perkin Elmer Atomic Absorption Spectrometer (Model 3110). The metal standards prepared were checked with standard reference material obtained from National Bureau of Standards (NBS), USA before each metal analysis and the deviation found was insigni®cant. Average values of ®ve replicates were taken for each determination. Operational conditions were adjusted to yield optimal determination. Quanti®cation of metals was based upon calibration curves of standard solutions of metals. The detection limits for different metals were 0.003, 0.001, 0.001, 0.004, 0.0008, 0.002, 0.01, 0.0005 for Fe, Mn, Cu, Ni, Zn, Cr, Pb and Cd, respectively. The precision of the analytical procedures, expressed as the relative standard deviation (rsd) ranged from 5 to 10%. The precision for the analysis of standard solution was better than 5%.
4. Results and discussion 4.1. Trace metal concentrations in water The distribution of trace metals in dissolved, total and particulate matter and their seasonal changes is given in Fig. 2. The concentration of dissolved metals decreased in the monsoon months due to dilution effect of rainfall. The lower concentration in dissolved metals in the months of February/March is due to the release of substantial amount of water from the Ganga
1.000
canal. Fig. 3 shows relationships of dissolved metal concentration with ¯ow. The metal concentrations depend largely on the amount of ¯owing water and are negatively correlated with ¯ow. This may be attributed to the dilution effect of rainfall and/or release of water from the Ganga canal. Regression equations explaining the variation of concentration with ¯ow are also shown in the same plots along with respective coef®cients of determination (r 2). The level of signi®cance was taken as 0.05. As is evident from the values of r 2, the relationship is well de®ned for Cu, Cd and Ni and less well de®ned for Zn, Fe, Mn, Cr and Pb. The correlation coef®cients determined among various metals indicate that the metals are controlled by sediment component (Fe and Mn). The signi®cant correlation coef®cients among different dissolved metals also point to a weathering effect. The particulate fraction contains a higher concentration of metal ions during monsoon months (Fig. 2). This may be attributed to simple sediment transport functions, whereby increases in ¯ow are associated with increased water turbulence and sheer velocities resulting in an increased capacity to erode and transport particulates from the upstream catchment and channel network. However, the particulate metal concentrations did not show any pronounced trend with ¯ow. It is evident from the above discussion that the concentration of trace metals in water is highly in¯uenced by the ¯ow of the water. Numerous studies have also demonstrated that the determination of metal concentrations in suspended and bed sediments is
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Fig. 4. Relationship between metal concentrations in suspended sediments and organic matter.
87
88
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
more sensitive than dissolved concentrations as indicators of contamination in hydrologic systems (Salomons and Forstner, 1984; Luoma, 1990). 4.2. Trace metal concentrations in suspended sediments The monthly distribution of trace metals in suspended sediments indicates that the metal concentrations slightly decreased in the monsoon months due to the dilution effect of rainfall. The lower metal concentrations in suspended sediments during the monsoon season may also be attributed to the dilution of the contaminated sediments by uncontaminated sediments from the watershed and/or bed of the river. The correlation coef®cients developed among various metal ions (Table 1) indicate negative correlation between amount of suspended sediments and the metal concentrations for most of the metals. Similar ®ndings were also reported by Houba et al. (1983) for Vesdre River in eastern Belgium. A high positive correlation of most of the metals with iron, manganese and organic matter suggests that these constituents play a major role in transport of metal ions. The highest correlation coef®cient observed between organic matter and Pb suggests the possibility of formation of strong complexes with organic matter. In sediments of polluted streams, the largest amounts of trace metals are associated with organic matter (humic and fulvic acids, colloids, synthetic organic substances), the ®negrained sediment fraction (clay, silt and ®ne sand) and Fe/Mn hydrous oxides, or are precipitated as hydroxides, sulphites or carbonates (Forstner, 1983). Similar ®ndings were also reported by many authors (Yamagata and Shigematsu, 1970; Asami and Sampei, 1979; Thorne and Nickless, 1981; Coquery and Welbourn, 1995). The relationship between organic matter and metal concentrations in suspended sediments are shown in Fig. 4 along with regression equations explaining the variation of metal concentration with organic matter. The relationship is well de®ned for all the metals except Mn and Cd. In river waters there is a strong af®nity between metals and organic matter (Forstner and Wittmann, 1981). Dissolved and particulate organic carbon in the water column act as scavengers for metals, and the scavenged metals may then be incorporated into the sediments.
4.3. Trace metal concentrations in bed sediments The concentration of metals in bed sediments was, in general, lower than in suspended sediments. This could be attributed to the prevention of sedimentation process by water currents. The highest concentrations of metals were observed in the summer season and the lowest were observed during the monsoon season. During the monsoon season, polluted particles (especially the ®ne fraction) is supposed to disperse through suspension in the bottom sediment layer, and, thus, their distribution in the surface sediment was expected to become similar to ef¯uent dilution or dispersion in the water of the river. Similar ®ndings were also reported by Geesey et al. (1984). Following peak discharge, the presence of the metals in bed sediments increased as the ¯ow again decreased. Therefore, sediment analysis should be carried out in low ¯ow conditions, where the highest accumulation of metal takes place from water to sediments. The correlation coef®cients observed among various metals in bed sediments are signi®cantly lower those observed in suspended sediments. This is due to the fact that most pollutants are generally concentrated in the ®ne particle fraction of the sediments due to large surface area (Yamagata and Shigematsu, 1970; Asami and Sampei, 1979; Thomson et al., 1984; Duzzin et al., 1988). The relationship between organic matter and metal concentrations in bed sediments is not well de®ned for most of the metals. The distribution of metals in different fractions of the bed sediments for the pre- and post-monsoon seasons indicated lower concentrations during the post-monsoon season. The decrease in the ®ne sediment fractions, organic matter and concentration of metal ions in ®ne fraction during the post-monsoon season indicates that a large amount of particulate matter is transported to the river as a consequence of high precipitation during the monsoon season. Excess ¯ow washes away the more contaminated super®cial sediments, which settle in the low ¯ow conditions during summer, substituting them with other less contaminated sediments from the basin. It is clearly evident from the results that the concentration of different metals was dramatically different in different fractions of the sediments and generally increased with the decreasing particle size of the sediments.
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
5. Conclusion It is evident from the study that the concentration of trace metals in water is highly in¯uenced by the ¯ow of the water. The content of ®ne fraction, organic matter and Fe/Mn plays an important role in the transport of metal ions. The sediment analysis should be carried out in low ¯ow conditions because trace metal pollution may be highest during this period and it may be accumulated from water to sediments. Under conditions of high water discharge, erosion of riverbed takes place. However, within the dry periods of reduced rate of ¯ow, a fraction of suspended sediments in polluted stream water is partially incorporated into the bottom sediment. Further studies are also needed on metal speciation and effects on metal uptake by organisms. The effective exposure of organisms to different metals is in¯uenced by both changes in metal speciation and relative distribution of metals between particles of different sizes and densities.
References Asami, T., Sampei, H., 1979. Distribution of heavy metals in the sediments of lake Kasumigaura and rivers ¯owed into the lake (part 3); Distribution of heavy metals in the sediments of rivers ¯owed into lake Kasumigaura. Jap. J. Soil Sci. Plant Nutr. 50, 183±188. Aurada, K.D. 1983. Physiographic and anthropogenic controls of global and regional ionic runoff, In: Webb, B.W. (Ed.), Dissolved Loads of Rivers and Surface Water Qantity/Qality Rlationship, Proc. Symp., Hamburg, IAHS Publ. No. 141, 31± 39. Biksham, G., Subramanian, V., 1988. Elemental composition of Godavari sediments (central and southern Indian subcontinent). Chem. Geol. 70, 270±286. Borole, D.V., Sarin, M.M., Somayajulu, M., 1982. Composition of Narmada and Tapti estuarine particles. Indian J. Mar. Sci. 11, 51±62. Combest, K.B., 1991. Trace metals in sediment: spatial trends and sorption processes. Wat. Resour. Bull. 27, 19±28. Coquery, M., Welbourn, P.M., 1995. The relationship between metal concentration and organic matter in sediment and metal concentration in the aquatic macrophyte Eriocaulon Septangulare Wat. Res. 29, 2094±2102. Duzzin, B., Pavoni, B., Donazzolo, R., 1988. Macroinvertebrate communities and sediments as pollution indicators for heavy metals in the river Adige (Italy). Wat. Res. 22, 1353±1363. Forstner, U., 1983. Assessment of metal pollution in rivers and estuaries. In: Thornton, I. (Ed.). Applied Environmental Geochemistry. Academic Press, London, pp. 395±423.
89
Forstner, U., Wittmann, G.T.W., 1981. Metal Pollution in the Aquatic Environment. . 2nd eddSpringer Verlag, Berlin. Foster, P., Hunt, D.T.E., 1975. Geochemistry of surface sediments in an acid stream estuary. Mar. Geol. 18, 13±21. Garrels, R.M., Mackenzie, F.T., Hunt, C., 1975. Chemical Cycles and the Global Environment. William Kaufmann, Inc, Los Altos, CA. Geesey, G.G., Borstad, L., Chapman, M.P., 1984. In¯uence of ¯ow related events on concentration and phase distribution of metals in the lower Fraser river and a small tributary stream in British Columbia, Canada. Wat. Res. 18, 233±238. Gibbs, R.J., 1977. Transport phases of transition metals in the Amazon and Yukon rivers. Geol. Soc. Am. Bull. 88, 829±843. Hiraizumi, Y., Manabe, T., Nishimura, H., 1978. Some regular patterns in the distribution of sediment contamination in the coastal waters along Japan. Oceanogr. Soc., Japan 34, 222±232. Houba, C., Remacle, J., Dubois, D., Thorez, J., 1983. Factors affecting the concentrations of cadmium, zinc, copper and lead in the sediments of the Vesdre river. Wat. Res. 17, 1281±1286. Jain, C.K., 1996. Application of chemical mass balance to upstream/ downstream river monitoring data. J. Hydrol. 182, 105±115. Jain, C.K., Ram, D., 1997a. Adsorption of lead and zinc on bed sediments of the river Kali. Wat. Res. 31, 154±162. Jain, C.K., Ram, D., 1997b. Adsorption of metal ions on bed sediments. Hydrol. Sci. J. 42, 713±723. Jain, C.K., Bhatia, K.K.S., Seth, S.M., 1997. Characterization of waste disposals and their impact on water quality of river Kali, Uttar Pradesh, Indian J. Environ. Prot. 17, 287±295. Jain, C.K., Bhatia, K.K.S., Seth, S.M., 1998a. Assessment of point and non-point sources of pollution using a chemical mass balance approach. Hydrol. Sci. J. 43, 379±390. Jain, C.K., Bhatia, K.K.S., Seth, S.M., 1998b. Effect of waste disposals on the water quality of river Kali. Indian J. Environ. Hlth. 40, 372±375. Jain, C.K., Sharma, M.K., 1998. Hydro-chemical studies of river Hindon, Technical Report, CS(AR)-21/98-99, National Institute of Hydrology, Roorkee, India. Jha, P.K., Subramanian, V., Sitasawad, R., 1988. Chemical and sediment mass transfer in the Yamuna riverÐa tributary of the Ganges system. J. Hydrol. 104, 237±246. Jha, P.K., Subramanian, V., Sitasawad, R., Van Grieken, R., 1990. Heavy metals in sediments of the Yamuna river (a tributary of the Ganges). The Science of the Total Environment 95, 7±27. Kristensen, P., 1982. Time dependent variation of mercury in a stream sediment and the effect upon mercury content in Gammarus pulex (L.). Wat. Res. 16, 759±764. Krumlgalz, B.S., 1989. Unusual grain size effect on trace metals and organic matter in contaminated sediments. Mar. Poll. Bull. 20, 608. Lokesh, K.S., 1996. Studies of Heavy Metals in Water and Sediment of Hindon River, PhD Thesis, Department of Civil Engineering, University of Roorkee, Roorkee, India. Luoma, S.N., 1990. Processes affecting metal concentrations in estuarine and coastal marine sediments. In: Rainbow, P.S., Furness, R.W. (Eds.). Heavy Metals in the Marine Environment. CRC Press, Cleveland, OH.
90
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Martin, J.M., Meybeck, M., 1979. Elemental mass balance of material carried by major world rivers. Mar. Chem. 7, 173±206. Ogura, H., Yarita, I., Kobayashi, S., Nakajima, J., 1979. Mechanism of metal accumulation of sediments of Edogawa and Muratagawa rivers; a consideration on the basis of grain size distributions. Jap. J. Wat. Pollut. Res. 2, 173±180. Ramanathan, A.L., Subramanian, V., Vaithiyanathan, P., 1988. Chemical and sediment characteristics of the upper reaches of Cauvery estuary, east coast of India. Indian J. Mar. Sci. 17, 114± 120. Ramesh, R., Subramanian, V., Van Grieken, R., 1990. Heavy metal distribution in sediments of Krishna river basin, India. Environ. Geol. Water Sci. 15, 207±216. Raymahashay, B.C., 1987. A comparative study of clay minerals for pollution control. J. Geol. Soc. India 30, 408±413. Sabri, A.W., Rasheed, K.A., Kassim, T.I., 1993. Heavy metals in the water, suspended solids and sediment of the river Tigris impoundment at Samarra. Wat. Res. 27, 1099±1103. Sakai, H., Kojima, Y., Saito, K., 1986. Distribution of heavy metals in water and sieved sediments in the Toyohira river. Wat. Res. 20, 559±567. Salomons, W., Forstner, U., 1984. Metals in the Hydrocycle. Springer, Berlin. Subramanian, V., 1979. Chemical and suspended sediments characteristics of rivers of India. J. Hydrol. 44, 37±55. Subramanian, V., Jha, P.K., 1988. Geochemical studies on the Hooghly (Ganges) Estuary. In: Degens, F.T., Kempe, S., Sathy Naidu, A. (Eds.). Transport of carbon and minerals in major world rivers, lakes and estuaries, part A. Mitt. Geol. Palocent. Inst, Hamburg, pp. 267±288.
Subramanian, V., Sitasawad, R., 1984. A study on water quality in the river Yamuna around Delhi, India. Water Qual. Bull. 9, 219±222. Subramanian, V., Van't dack, L., Van Grieken, R., 1985. Chemical composition of river sediments from the Indian sub-continent. Chem. Geol. 48, 271±279. Subramanian, V., Van Grieken, R., Van't dack, L., 1987. Heavy metal distribution in the sediments of Ganges and Brahmaputra rivers. Environ. Geol. Water Sci. 9, 93±108. Subramanian, V., Jha, P.K., Van Grieken, R., 1988. Heavy metal in Ganges estuary. Mar. Poll. Bull. 19, 290±293. Thomson, E.A., Luoma, S.N., Johnsson, C.E., Cain, D.J., 1984. Comparison of sediments and organisms in identifying sources of biologically available trace metal concentration. Wat. Res. 18, 755±765. Thorne, L.T., Nickless, G., 1981. The relation between heavy metals and particle size fractions within the Severn estuary (UK) inter-tidal sediments. The Science of the Total Environment 19, 207±213. Verma, S.R., Shukla, G.R., Dalela, R.C., 1980. Studies on the pollution of Hindon river in relation to ®sh and ®sheries. Limnologica (Berlin) 12, 33±75. Warren, L.J., 1981. Contamination of sediments by lead, zinc and cadmiumÐa review. Environ. Pollution, ser. B 2, 401±436. Yamagata, N., Shigematsu, I., 1970. Cadmium pollution in perspective. Bull. Inst. Publ. Hlth. 19, 1±27. Zhang, J., Huang, W.W., 1993. Dissolved trace metals in the Huanghe: the most turbid large river in the world. Wat. Res. 27, 1±8.
www.elsevier.com/locate/jhydrol
Distribution of trace metals in the Hindon River system, India C.K. Jain*, M.K. Sharma National Institute of Hydrology, Roorkee 247 667, India Received 20 September 2000; revised 22 May 2001; accepted 5 June 2001
Abstract The distribution of trace metals (Cu, Zn, Fe, Mn, Cd, Cr, Pb, and Ni) in water, suspended and bed sediments of the River Hindon, a highly polluted river in western Uttar Pradesh (India) has been studied. The river is polluted by municipal, industrial and agricultural ef¯uents, and ¯ows through the city of Saharanpur, Muzaffarnagar and Ghaziabad districts. The heavy metal concentrations in water were observed to depend largely on the amount of ¯owing water and are negatively correlated with ¯ow. Sediment analysis indicates that the large amount of heavy metals is associated with organic matter, the ®ne-grained sediment fraction and Fe/Mn hydrous oxides. A high positive correlation of most of the metal ions in sediments with iron, manganese and organic matter indicate that these constituents play a major role in transport of metal ions. The heavy metal concentrations generally increased with the decreasing particle size of the sediments. Lower metal concentrations in bed sediments during post-monsoon season established that monsoon had a slight effect on status of metals in sediments by causing renewal and mobilization of metals from the sediments. q 2001 Elsevier Science B.V. All rights reserved. Keywords: Trace metals; Distribution; Bed sediments; River system
1. Introduction In recent years, the ¯uxes of trace metals from terrestial and atmospheric sources to the aquatic environment have increased considerably (Forstner and Wittmann, 1981). Numerous studies have demonstrated that the determination of metal concentrations in suspended and bed sediments is more sensitive than the dissolved concentrations as indicators of contamination in hydrologic systems (Salomons and Forstner, 1984; Luoma, 1990). The presence of trace metals in sediments is affected by the particle size and composition of sediments (Yamagata and Shigematsu, 1970; Foster and Hunt, 1975; Hiraizumi et al., 1978; Asami and Sampei, 1979; Ogura et al., 1979; Forstner and Wittmann, 1981; Thorne and * Corresponding author. E-mail address: [email protected] (C.K. Jain).
Nickless, 1981; Kristensen, 1982; Thomson et al., 1984; Sakai et al., 1986; Raymahashay, 1987; Krumlgalz, 1989; Combest, 1991; Sabri et al., 1993). More than 97% of the mass transport of metals to oceans is associated with river sediments (Gibbs, 1977). A variety of factors such as basin geology, physiography, chemical reactivity, lithology, mineralogy, hydrology, vegetation, land use pattern and biological productivity regulate the metal load of a river system (Garrels et al., 1975; Warren, 1981; Aurada, 1983; Zhang and Huang, 1993). Martin and Meybeck (1979) studied elemental mass balance of material carried by major world rivers. Due to the relative mobility of metals during transport processes, sediment can re¯ect the present quality of the basin and the historical development of various hydrological and chemical parameters. The metal contribution from Indian rivers, which carry 20% of the global supply of sediments to the
0022-1694/01/$ - see front matter q 2001 Elsevier Science B.V. All rights reserved. PII: S 0022- 169 4( 01) 00484-X
82
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Fig. 1. Hindon River Basin showing location of sampling site.
oceans has not been properly assessed (Subramanian, 1979; Subramanian et al., 1985). Borole et al. (1982) and Subramanian et al. (1988) have reported metal concentrations in estuarine sediments on the West and East Coast of India. Recent geochemical studies of some basins have yielded additional data to improve and update information on the metal contribution of Indian rivers to the adjacent ocean (Subramanian et al., 1987; Biksham and Subramanian, 1988; Ramanathan et al., 1988; Subramanian and Jha, 1988; Ramesh et al., 1990). The river Yamuna contributes 64 £ 10 6 t year 21 of
suspended sediments and 42 £ 10 6 t year 21 of dissolved load to the Ganges (Jha et al., 1988). Bed sediments of the River Yamuna have higher concentrations of metals than other tributaries. Sediment grain size, mineralogical difference and varying amounts of anthropogenic contributions may be the prime factors controlling metal variation (Jha et al., 1990). Subramanian and Sitasawad (1984) reported that annually, 86 t Ni, 64 t Cr, 61 t Pb, 45 t Fe and 36 t Zn, derived from industrial ef¯uents and city wastes are disposed into the River Yamuna in the vicinity of Delhi alone.
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
The River Hindon is an important tributary of the River Yamuna and carries pollution load from industrial towns and agricultural areas of western Uttar Pradesh (India). Verma et al. (1980) conducted limnological studies of the River Hindon in relation to ®sh and ®sheries while Lokesh (1996) studied the fate of heavy metals in water and sediments of the river. In earlier publications, we have carried out in-depth investigations on water and sediments of the River Kali, a tributary of the River Hindon, (Jain, 1996; Jain and Ram, 1997a,b; Jain et al., 1997, 1998a,b). In view of the above observations it is of interest to study the distribution of trace metals in water, suspended sediments and bed sediments of river Hindon under different ¯ow conditions. 2. Study area The Hindon Basin is a part of Indogangetic Plains, composed of Pleistocene and subrecent alluvium and lies between latitude 28830 0 to 30815 0 N and longitude 77820 0 to 77850 0 . The river Hindon originates from Upper Shivaliks (Lower Himalayas) and ¯ows through four major districts, viz. Saharanpur, Muzaffarnagar, Meerut and Ghaziabad in western Uttar Pradesh and Joins the River Yamuna downstream of Delhi at Tilwara. (Fig. 1). The climate of the region is moderate subtropical monsoon type. The average annual rainfall is about 1000 mm, the major part of which is received during the monsoon period. The major land use in the basin is agriculture and there is no effective forest cover. The soil type of the basin is alluvial consisting of clay, silt and ®ne to coarse sand. The basin is densely populated because of the rapid industrialization and agricultural growth during last few decades. The discharge from municipal and industrial areas as well as runoff from agricultural areas affects the quantity and quality of the river water. The main sources, which create pollution in the River Hindon include municipal waste of Saharanpur, Muzaffarnagar and Ghaziabad districts and industrial ef¯uents of sugar, pulp and paper, distilleries and other miscellaneous industries through tributaries as well as direct outfalls. In non-monsoon months, the river is completely dry from its origin upto Saharanpur town. The ef¯uents of Nagdev nala
83
and Star Paper Mill at Saharanpur generate the ¯ow of water in the river. The municipal waste generated from Saharanpur is discharged to the Hindon River through Dhamola nala. The industrial ef¯uent from Cooperative Distillery also joins the river in this stretch. The River Kali meets the River Hindon on its left bank near the village of Atali, which is carrying municipal wastewater and ef¯uents of industries located in Muzaffarnagar. Another tributary called Krishni meets Hindon on its right bank at the village of Barnawa in Meerut district and carrying the waste water from sugar mill and distillery. In Ghaziabad district, the majority of the ¯ow of the river is diverted to the Hindon cut canal at Mohan Nagar. Thereafter, the river ¯ows downstream and joins the River Yamuna at the village of Tilwara (Fig. 1). The characteristics of the various waste ef¯uents/tributaries and their impact on river water quality have been discussed in an earlier report (Jain and Sharma, 1998). 3. Experimental methodology The water and sediment samples were collected from the Hindon River at Mohan Nagar. The water samples were collected in polyethylene bottles from 1/3, 1/2 and 2/3 width of the river using a standard water sampler (Hydro Bios, Germany) and then mixed together to obtain a composite sample. The sample bottles were soaked in 10% HNO3 for 24 h and rinsed several times with deionized water prior to use. The water samples were ®ltered through 0.45 mm membrane ®lters to obtain samples for dissolved metal estimations and preserved with ultra pure nitric acid to bring down the pH to ,2.0. The samples thus preserved were stored at 48C in sampling kits and brought to the laboratory for trace element analysis. The water samples for total metal analysis were preserved using ultra pure nitric acid and then digested on a hot plate. Suspended sediments were collected by ®ltering water samples through 0.45 mm membrane ®lters. Bed sediment samples were collected by an Ekman grab sampler, dried at 708C and sieved to obtain different particle fractions (0±75, 75±150, 150±200, 200±250, 250±300, 300±425 and 425±600 mm) and stored in polyethylene bags until further processing.
84
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Fig. 2. Monthly variation of dissolved, total and particulate metal concentrations.
The extraction of sediments was carried out using acid mixture (HNO3 1 HClO4). Organic matter in the sediment was determined by the wet oxidation±redox titration method using an acid dichromate solution followed back titration of remaining dichromate with ferrous ammonium
sulphate. The reported data are the sum of soluble and insoluble organic carbon. All chemicals and standard solutions used in the study were obtained from Merck, India/Germany and were of analytical grade. Deionized water was used throughout the study. All glassware and other
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Fig. 3. Relationship between dissolved metal concentrations and ¯ow.
85
86
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Table 1 Correlation coef®cients among metal concentrations in suspended sediments Flow
SS
Cu
Zn
Fe
Mn
Cd
Cr
Pb
Ni
OM
Flow SS Cu Zn Fe Mn Cd Cr Pb Ni OM
1.000 0.179 20.452 20.649 20.648 20.621 20.635 20.478 20.658 20.465 20.608
1.000 20.218 20.302 20.125 20.070 0.359 20.315 20.321 20.566 20.442
1.000 0.844 0.895 0.697 0.551 0.881 0.869 0.675 0.886
1.000 0.773 0.807 0.563 0.840 0.866 0.574 0.793
1.000 0.662 0.716 0.718 0.806 0.743 0.901
1.000 0.748 0.781 0.910 0.321 0.714
1.000 0.432 0.627 0.163 0.519
1.000 0.930 0.614 0.851
1.000 0.605 0.914
1.000 0.808
containers were thoroughly cleaned and ®nally rinsed with deionized water several times prior to use. Trace metal analysis was carried out using a Perkin Elmer Atomic Absorption Spectrometer (Model 3110). The metal standards prepared were checked with standard reference material obtained from National Bureau of Standards (NBS), USA before each metal analysis and the deviation found was insigni®cant. Average values of ®ve replicates were taken for each determination. Operational conditions were adjusted to yield optimal determination. Quanti®cation of metals was based upon calibration curves of standard solutions of metals. The detection limits for different metals were 0.003, 0.001, 0.001, 0.004, 0.0008, 0.002, 0.01, 0.0005 for Fe, Mn, Cu, Ni, Zn, Cr, Pb and Cd, respectively. The precision of the analytical procedures, expressed as the relative standard deviation (rsd) ranged from 5 to 10%. The precision for the analysis of standard solution was better than 5%.
4. Results and discussion 4.1. Trace metal concentrations in water The distribution of trace metals in dissolved, total and particulate matter and their seasonal changes is given in Fig. 2. The concentration of dissolved metals decreased in the monsoon months due to dilution effect of rainfall. The lower concentration in dissolved metals in the months of February/March is due to the release of substantial amount of water from the Ganga
1.000
canal. Fig. 3 shows relationships of dissolved metal concentration with ¯ow. The metal concentrations depend largely on the amount of ¯owing water and are negatively correlated with ¯ow. This may be attributed to the dilution effect of rainfall and/or release of water from the Ganga canal. Regression equations explaining the variation of concentration with ¯ow are also shown in the same plots along with respective coef®cients of determination (r 2). The level of signi®cance was taken as 0.05. As is evident from the values of r 2, the relationship is well de®ned for Cu, Cd and Ni and less well de®ned for Zn, Fe, Mn, Cr and Pb. The correlation coef®cients determined among various metals indicate that the metals are controlled by sediment component (Fe and Mn). The signi®cant correlation coef®cients among different dissolved metals also point to a weathering effect. The particulate fraction contains a higher concentration of metal ions during monsoon months (Fig. 2). This may be attributed to simple sediment transport functions, whereby increases in ¯ow are associated with increased water turbulence and sheer velocities resulting in an increased capacity to erode and transport particulates from the upstream catchment and channel network. However, the particulate metal concentrations did not show any pronounced trend with ¯ow. It is evident from the above discussion that the concentration of trace metals in water is highly in¯uenced by the ¯ow of the water. Numerous studies have also demonstrated that the determination of metal concentrations in suspended and bed sediments is
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Fig. 4. Relationship between metal concentrations in suspended sediments and organic matter.
87
88
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
more sensitive than dissolved concentrations as indicators of contamination in hydrologic systems (Salomons and Forstner, 1984; Luoma, 1990). 4.2. Trace metal concentrations in suspended sediments The monthly distribution of trace metals in suspended sediments indicates that the metal concentrations slightly decreased in the monsoon months due to the dilution effect of rainfall. The lower metal concentrations in suspended sediments during the monsoon season may also be attributed to the dilution of the contaminated sediments by uncontaminated sediments from the watershed and/or bed of the river. The correlation coef®cients developed among various metal ions (Table 1) indicate negative correlation between amount of suspended sediments and the metal concentrations for most of the metals. Similar ®ndings were also reported by Houba et al. (1983) for Vesdre River in eastern Belgium. A high positive correlation of most of the metals with iron, manganese and organic matter suggests that these constituents play a major role in transport of metal ions. The highest correlation coef®cient observed between organic matter and Pb suggests the possibility of formation of strong complexes with organic matter. In sediments of polluted streams, the largest amounts of trace metals are associated with organic matter (humic and fulvic acids, colloids, synthetic organic substances), the ®negrained sediment fraction (clay, silt and ®ne sand) and Fe/Mn hydrous oxides, or are precipitated as hydroxides, sulphites or carbonates (Forstner, 1983). Similar ®ndings were also reported by many authors (Yamagata and Shigematsu, 1970; Asami and Sampei, 1979; Thorne and Nickless, 1981; Coquery and Welbourn, 1995). The relationship between organic matter and metal concentrations in suspended sediments are shown in Fig. 4 along with regression equations explaining the variation of metal concentration with organic matter. The relationship is well de®ned for all the metals except Mn and Cd. In river waters there is a strong af®nity between metals and organic matter (Forstner and Wittmann, 1981). Dissolved and particulate organic carbon in the water column act as scavengers for metals, and the scavenged metals may then be incorporated into the sediments.
4.3. Trace metal concentrations in bed sediments The concentration of metals in bed sediments was, in general, lower than in suspended sediments. This could be attributed to the prevention of sedimentation process by water currents. The highest concentrations of metals were observed in the summer season and the lowest were observed during the monsoon season. During the monsoon season, polluted particles (especially the ®ne fraction) is supposed to disperse through suspension in the bottom sediment layer, and, thus, their distribution in the surface sediment was expected to become similar to ef¯uent dilution or dispersion in the water of the river. Similar ®ndings were also reported by Geesey et al. (1984). Following peak discharge, the presence of the metals in bed sediments increased as the ¯ow again decreased. Therefore, sediment analysis should be carried out in low ¯ow conditions, where the highest accumulation of metal takes place from water to sediments. The correlation coef®cients observed among various metals in bed sediments are signi®cantly lower those observed in suspended sediments. This is due to the fact that most pollutants are generally concentrated in the ®ne particle fraction of the sediments due to large surface area (Yamagata and Shigematsu, 1970; Asami and Sampei, 1979; Thomson et al., 1984; Duzzin et al., 1988). The relationship between organic matter and metal concentrations in bed sediments is not well de®ned for most of the metals. The distribution of metals in different fractions of the bed sediments for the pre- and post-monsoon seasons indicated lower concentrations during the post-monsoon season. The decrease in the ®ne sediment fractions, organic matter and concentration of metal ions in ®ne fraction during the post-monsoon season indicates that a large amount of particulate matter is transported to the river as a consequence of high precipitation during the monsoon season. Excess ¯ow washes away the more contaminated super®cial sediments, which settle in the low ¯ow conditions during summer, substituting them with other less contaminated sediments from the basin. It is clearly evident from the results that the concentration of different metals was dramatically different in different fractions of the sediments and generally increased with the decreasing particle size of the sediments.
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
5. Conclusion It is evident from the study that the concentration of trace metals in water is highly in¯uenced by the ¯ow of the water. The content of ®ne fraction, organic matter and Fe/Mn plays an important role in the transport of metal ions. The sediment analysis should be carried out in low ¯ow conditions because trace metal pollution may be highest during this period and it may be accumulated from water to sediments. Under conditions of high water discharge, erosion of riverbed takes place. However, within the dry periods of reduced rate of ¯ow, a fraction of suspended sediments in polluted stream water is partially incorporated into the bottom sediment. Further studies are also needed on metal speciation and effects on metal uptake by organisms. The effective exposure of organisms to different metals is in¯uenced by both changes in metal speciation and relative distribution of metals between particles of different sizes and densities.
References Asami, T., Sampei, H., 1979. Distribution of heavy metals in the sediments of lake Kasumigaura and rivers ¯owed into the lake (part 3); Distribution of heavy metals in the sediments of rivers ¯owed into lake Kasumigaura. Jap. J. Soil Sci. Plant Nutr. 50, 183±188. Aurada, K.D. 1983. Physiographic and anthropogenic controls of global and regional ionic runoff, In: Webb, B.W. (Ed.), Dissolved Loads of Rivers and Surface Water Qantity/Qality Rlationship, Proc. Symp., Hamburg, IAHS Publ. No. 141, 31± 39. Biksham, G., Subramanian, V., 1988. Elemental composition of Godavari sediments (central and southern Indian subcontinent). Chem. Geol. 70, 270±286. Borole, D.V., Sarin, M.M., Somayajulu, M., 1982. Composition of Narmada and Tapti estuarine particles. Indian J. Mar. Sci. 11, 51±62. Combest, K.B., 1991. Trace metals in sediment: spatial trends and sorption processes. Wat. Resour. Bull. 27, 19±28. Coquery, M., Welbourn, P.M., 1995. The relationship between metal concentration and organic matter in sediment and metal concentration in the aquatic macrophyte Eriocaulon Septangulare Wat. Res. 29, 2094±2102. Duzzin, B., Pavoni, B., Donazzolo, R., 1988. Macroinvertebrate communities and sediments as pollution indicators for heavy metals in the river Adige (Italy). Wat. Res. 22, 1353±1363. Forstner, U., 1983. Assessment of metal pollution in rivers and estuaries. In: Thornton, I. (Ed.). Applied Environmental Geochemistry. Academic Press, London, pp. 395±423.
89
Forstner, U., Wittmann, G.T.W., 1981. Metal Pollution in the Aquatic Environment. . 2nd eddSpringer Verlag, Berlin. Foster, P., Hunt, D.T.E., 1975. Geochemistry of surface sediments in an acid stream estuary. Mar. Geol. 18, 13±21. Garrels, R.M., Mackenzie, F.T., Hunt, C., 1975. Chemical Cycles and the Global Environment. William Kaufmann, Inc, Los Altos, CA. Geesey, G.G., Borstad, L., Chapman, M.P., 1984. In¯uence of ¯ow related events on concentration and phase distribution of metals in the lower Fraser river and a small tributary stream in British Columbia, Canada. Wat. Res. 18, 233±238. Gibbs, R.J., 1977. Transport phases of transition metals in the Amazon and Yukon rivers. Geol. Soc. Am. Bull. 88, 829±843. Hiraizumi, Y., Manabe, T., Nishimura, H., 1978. Some regular patterns in the distribution of sediment contamination in the coastal waters along Japan. Oceanogr. Soc., Japan 34, 222±232. Houba, C., Remacle, J., Dubois, D., Thorez, J., 1983. Factors affecting the concentrations of cadmium, zinc, copper and lead in the sediments of the Vesdre river. Wat. Res. 17, 1281±1286. Jain, C.K., 1996. Application of chemical mass balance to upstream/ downstream river monitoring data. J. Hydrol. 182, 105±115. Jain, C.K., Ram, D., 1997a. Adsorption of lead and zinc on bed sediments of the river Kali. Wat. Res. 31, 154±162. Jain, C.K., Ram, D., 1997b. Adsorption of metal ions on bed sediments. Hydrol. Sci. J. 42, 713±723. Jain, C.K., Bhatia, K.K.S., Seth, S.M., 1997. Characterization of waste disposals and their impact on water quality of river Kali, Uttar Pradesh, Indian J. Environ. Prot. 17, 287±295. Jain, C.K., Bhatia, K.K.S., Seth, S.M., 1998a. Assessment of point and non-point sources of pollution using a chemical mass balance approach. Hydrol. Sci. J. 43, 379±390. Jain, C.K., Bhatia, K.K.S., Seth, S.M., 1998b. Effect of waste disposals on the water quality of river Kali. Indian J. Environ. Hlth. 40, 372±375. Jain, C.K., Sharma, M.K., 1998. Hydro-chemical studies of river Hindon, Technical Report, CS(AR)-21/98-99, National Institute of Hydrology, Roorkee, India. Jha, P.K., Subramanian, V., Sitasawad, R., 1988. Chemical and sediment mass transfer in the Yamuna riverÐa tributary of the Ganges system. J. Hydrol. 104, 237±246. Jha, P.K., Subramanian, V., Sitasawad, R., Van Grieken, R., 1990. Heavy metals in sediments of the Yamuna river (a tributary of the Ganges). The Science of the Total Environment 95, 7±27. Kristensen, P., 1982. Time dependent variation of mercury in a stream sediment and the effect upon mercury content in Gammarus pulex (L.). Wat. Res. 16, 759±764. Krumlgalz, B.S., 1989. Unusual grain size effect on trace metals and organic matter in contaminated sediments. Mar. Poll. Bull. 20, 608. Lokesh, K.S., 1996. Studies of Heavy Metals in Water and Sediment of Hindon River, PhD Thesis, Department of Civil Engineering, University of Roorkee, Roorkee, India. Luoma, S.N., 1990. Processes affecting metal concentrations in estuarine and coastal marine sediments. In: Rainbow, P.S., Furness, R.W. (Eds.). Heavy Metals in the Marine Environment. CRC Press, Cleveland, OH.
90
C.K. Jain, M.K. Sharma / Journal of Hydrology 253 (2001) 81±90
Martin, J.M., Meybeck, M., 1979. Elemental mass balance of material carried by major world rivers. Mar. Chem. 7, 173±206. Ogura, H., Yarita, I., Kobayashi, S., Nakajima, J., 1979. Mechanism of metal accumulation of sediments of Edogawa and Muratagawa rivers; a consideration on the basis of grain size distributions. Jap. J. Wat. Pollut. Res. 2, 173±180. Ramanathan, A.L., Subramanian, V., Vaithiyanathan, P., 1988. Chemical and sediment characteristics of the upper reaches of Cauvery estuary, east coast of India. Indian J. Mar. Sci. 17, 114± 120. Ramesh, R., Subramanian, V., Van Grieken, R., 1990. Heavy metal distribution in sediments of Krishna river basin, India. Environ. Geol. Water Sci. 15, 207±216. Raymahashay, B.C., 1987. A comparative study of clay minerals for pollution control. J. Geol. Soc. India 30, 408±413. Sabri, A.W., Rasheed, K.A., Kassim, T.I., 1993. Heavy metals in the water, suspended solids and sediment of the river Tigris impoundment at Samarra. Wat. Res. 27, 1099±1103. Sakai, H., Kojima, Y., Saito, K., 1986. Distribution of heavy metals in water and sieved sediments in the Toyohira river. Wat. Res. 20, 559±567. Salomons, W., Forstner, U., 1984. Metals in the Hydrocycle. Springer, Berlin. Subramanian, V., 1979. Chemical and suspended sediments characteristics of rivers of India. J. Hydrol. 44, 37±55. Subramanian, V., Jha, P.K., 1988. Geochemical studies on the Hooghly (Ganges) Estuary. In: Degens, F.T., Kempe, S., Sathy Naidu, A. (Eds.). Transport of carbon and minerals in major world rivers, lakes and estuaries, part A. Mitt. Geol. Palocent. Inst, Hamburg, pp. 267±288.
Subramanian, V., Sitasawad, R., 1984. A study on water quality in the river Yamuna around Delhi, India. Water Qual. Bull. 9, 219±222. Subramanian, V., Van't dack, L., Van Grieken, R., 1985. Chemical composition of river sediments from the Indian sub-continent. Chem. Geol. 48, 271±279. Subramanian, V., Van Grieken, R., Van't dack, L., 1987. Heavy metal distribution in the sediments of Ganges and Brahmaputra rivers. Environ. Geol. Water Sci. 9, 93±108. Subramanian, V., Jha, P.K., Van Grieken, R., 1988. Heavy metal in Ganges estuary. Mar. Poll. Bull. 19, 290±293. Thomson, E.A., Luoma, S.N., Johnsson, C.E., Cain, D.J., 1984. Comparison of sediments and organisms in identifying sources of biologically available trace metal concentration. Wat. Res. 18, 755±765. Thorne, L.T., Nickless, G., 1981. The relation between heavy metals and particle size fractions within the Severn estuary (UK) inter-tidal sediments. The Science of the Total Environment 19, 207±213. Verma, S.R., Shukla, G.R., Dalela, R.C., 1980. Studies on the pollution of Hindon river in relation to ®sh and ®sheries. Limnologica (Berlin) 12, 33±75. Warren, L.J., 1981. Contamination of sediments by lead, zinc and cadmiumÐa review. Environ. Pollution, ser. B 2, 401±436. Yamagata, N., Shigematsu, I., 1970. Cadmium pollution in perspective. Bull. Inst. Publ. Hlth. 19, 1±27. Zhang, J., Huang, W.W., 1993. Dissolved trace metals in the Huanghe: the most turbid large river in the world. Wat. Res. 27, 1±8.