Hydrological Sciences-Joumal-des Sciences Hydrologiques, 42(5) October 1997

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Adsorption of metal ions on bed sediments

C. K. JAIN & D. RAM
National Institute of Hydrology, Roorkee 247 667, India Abstract The adsorption of lead and zinc ions on bed sediments of the River Kali in western Uttar Pradesh, India, has been studied. The role of the coarser sediment fraction (210-250 jtm) in controlling metal pollution has been elucidated and compared to those of the clay and silt fractions. The parameters controlling metal uptake, viz., solution pH, sediment dose, contact time, and particle size have been evaluated. The optimum contact time needed to reach equilibrium is of the order of 45 min for both the metal ions. The extent of adsorption increases with an increase of pH. Furthermore, the adsorption of the metal ions increases with increasing adsorbent doses and decreases with adsorbent particle size. The two geochemical phases of iron and manganese oxide act as the active support material for the adsorption of the metal ions.

Adsorption d'ions mtalliques sur les sdiments de fond

Rsum Nous avons tudi 1'adsorption des ions plomb et zinc dans les sdiments du lit du fleuve Kali dans l'Uttar Pradesh occidental (Inde). Le rle fondamental de la fraction grossire des sdiments (210-250 fim) dans la pollution mtallique a pu tre lucid et compar ceux des fractions argileuses et silteuses. Les paramtres commandant l'adsorption des mtaux, savoir le pH, la quantit de sdiment, le temps de contact et la granulomtrie du sdiment ont t estims. Le temps de contact optimal permettant d'atteindre l'quilibre est de l'ordre de 45 min pour les deux ions mtalliques tudis. L'adsorption augmente avec le pH. De plus, l'adsorption augmente avec la quantit de sdiment et diminue avec la taille des particules adsorbantes. Les deux phases gochimiques que sont les oxydes de fer et de manganse constituent un matriel adsorbant trs efficace vis vis des ions mtalliques.

INTRODUCTION Suspended and bed sediments play an important role in the transport of metals in aquatic systems. The important components of the suspended load for geochemical transport are silt, clay, hydrous iron and manganese oxides and organic matter. In most publications, the clay and silt fractions of the sediments and organic matter have been considered as the main adsorbing agents, while the contribution of the coarser fraction of the sediments has been somewhat ignored. Adsorption of metal ions by soils and sediments involves the distribution of the ions among the surfaces of the component solid particles. Jenne (1976) reported that the most significant role of clay-size mineral in trace element sorption by soils and sediments is that of a mechanical substrate for the precipitation and flocculation of organics and secondary minerals. The adsorption interactions between trace metals on suspended clay minerals have been studied by Gagnon et al. (1992). Soong (1974) reported that lead has a special affinity for clay minerals. Palheiros et al. (1989) have studied the adsorption of cadmium onto a riverbed sediment and reported that pH is
Open for discussion until 1 April 1998

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C. K. Jain & D. Ram

the most important controlling parameter. Bajracharya & Barry (1996) studied the effect of zinc and ammonium ions on the adsorption of cadmium on sand and soil and reported that both ions suppress the adsorption capacity significantly. The adsorption behaviour of metals on oxides has been studied extensively (Anderson & Benjamin, 1990; Benjamin & Bloom, 1981; Benjamin & Leckie, 1980; Dempsey & Singer, 1980; Loganathan & Burau, 1973). These oxides constitute significant sinks of heavy metals in aquatic systems. Frstner and different coauthors (Frstner & Millier, 1973; Frstner, 1977; Frstner & Wittman, 1983) compiled the associations of heavy metals in particulate form in sediments and described the active constituents with the nature of association. Recently Meng & Letterman (1993a,b, 1996) studied the effect of component oxide interaction on the adsorption properties of mixed oxides. Although clay and silt components adsorb metal ions much better than sediment fractions of higher size, one should take into account that most river sediments contain 90-95% of sand and only 0-10% of clay and silt. Therefore, in river sediments with a high sand percentage and a low clay and silt content, the overall contribution of the sand content to adsorption of metal ions could be comparable to or even higher than that of the clay and silt fraction. In the present paper, the adsorption of lead and zinc ions on different fractions of the sediment of a highly polluted river in western Uttar Pradesh, India, has been studied. The objective was to determine the relative contribution of the coarser fraction of the sediments in controlling metal pollution. Both metal ions are toxic and relatively widespread in the environment (Frstner, 1979). The role of important geochemical phases has also been investigated.

THE RIVER SYSTEM The Kali River in western Uttar Pradesh, India, is a small perennial river having a basin area of about 750 km2, and lies between latitude 2933'N to 2921'N and longitude 7743'E to 7739'E in the Muzaffarnagar district of Uttar Pradesh (Fig. 1). The climate in this region is moderate subtropical monsoonal. The average annual rainfall in the area is about 1000 mm, a major part of which is received during the monsoon period. The major land use is agriculture and there is no effective forest cover. The soils of the area are loam to silty loam and are normally free of carbonates. The river basin contains towns and villages surrounded by agricultural areas. The quantity and quality of the river water is affected by the discharge from municipal and industrial areas as well as runoff from agricultural areas. The River Kali is a typical water course containing municipal and industrial effluents. All those who have access to the river use it for bathing, laundry and even for defecating and are very difficult to regulate. The main pollution sources include Muzaffarnagar city, a variety of industries (steel, rubber, ceramic, chemical, plastic, dairy, pulp and paper, and laundries), and the Mansurpur sugar mill and distillery. The composite waste from a variety of industries is transferred through Muzaffarnagar main drain

Adsorption of metal ions on bed sediments

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into the river. The chemical characteristics of this river have been reported earlier with special reference to the disposal of municipal and industrial wastes (Jain, 1992). In another publication a mass balance approach has been utilized to discriminate between point and non-point sources of pollution to the river (Jain, 1996).

EXPERIMENTAL METHODOLOGY Sampling and storage For the adsorption studies of heavy metal ions (Pb2+ and Zn2+) freshly deposited sediments in shallow water near the river bank were collected in polyethylene bags from the upstream section of the river and brought to the laboratory. Samples were taken from the upper 5 cm of the sediments at places where flow rates were low and sedimentation was assumed to occur. Sakai et al. (1986) and Subramanian et al. (1987) adopted the same method in their work. The size distribution of the sediment samples was found by the dry sieving method using ASTM standard sieves to obtain various fractions, viz., 0-75, 75-150, 150-210, 210-250, 250-325 and 325-425 /mi. Sieved sediments were oven-dried overnight at 105C and, after cooling in a desiccator, stored in air-tight containers.

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Materials and reagents All chemicals used in the study were of analytical grade. Aqueous solutions of lead and zinc were prepared from lead nitrate and zinc sulphate respectively. Deionized water was used throughout the study. All glassware and other containers were thoroughly cleaned by soaking in detergent followed by soaking in 10% nitric acid for 48 h and finally rinsed with deionized water several times prior to use.

Adsorption experiments Adsorption experiments were conducted in Erlenmeyer flasks with ground-glass stoppers. Fifty ml of metal ion solution were transferred to 100 ml flasks together with the desired adsorbent doses (Ws in g l"1), and placed in a water bath shaker maintained at 25C. Adsorption tests were terminated after the attainment of equilibrium conditions. Aliquots were retrieved periodically, filtered through 0.45 /xm membrane filters and analysed for the residual concentration of the respective metal ions.

Metal ion analysis Metal ion concentrations were determined by flame atomic absorption spectrometry using a Perkin-Elmer Atomic Absorption Spectrometer (Model 3110) with an airacetylene flame. The detection limits for the two metal ions studied are 0.03 and 0.002 mg l"1 for lead and zinc, respectively. Operational conditions were adjusted to yield optimal determinations. Quantification of the metals was based upon calibration curves of standard solutions for the respective metals. These calibration curves were determined several times during the period of analysis.

RESULTS AND DISCUSSION The sediment under study was composed of more than 99% sand and less than 1% silt and clay. It was therefore felt worth studying the adsorption of metal ions on the sand fraction compared to the clay and silt fraction ( < 75 jtm particle size) in order to evaluate the importance of the coarser fraction in controlling metal pollution. The organic content of the sediment was of the order of 0-1%. The important geochemical constituents in the different particle size fractions, along with the weight percentages of the different fractions, are given in Table 1. It is evident from the data that the manganese and iron contents in the various fractions of the sediment decrease with increasing particle size. This indicates the possibility of the two geochemical phases acting as the active support material for the adsorption of lead and zinc ions. However, the relative contribution of individual components cannot be obtained from the present studies because in natural systems, the type and composition of the

Adsorption of metal ions on bed sediments

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Table 1 Characteristics of sediments. Particle fraction (/an) <75 75-450 150-210 210-250 250-300 300-425 425-600 Weight

(%)
0.6 3.9 19.1 35.6 15.0 24.3 1.5

Total Mn (mg g"1) 1.32 1.03 0.39 0.23 0.15 0.12

Total Fe (mg g"1) 32.41 21.48 10.75 7.88 7.87 7.05

mineral and organic fractions of sediments vary simultaneously and the effect of individual constituents cannot be isolated.

Contact time (t) The adsorption data for the uptake of metal ions vs contact time for a fixed adsorbent dose of 5 g l"1 and with an initial metal ion concentration of 10 mg l"1 are shown in Fig. 2 for the two particle sizes of adsorbent (0-75 and 210-250 /an) at pH 5.0. These plots indicate that the remaining concentration of metal ions becomes asymptotic to the time axis such that there is no appreciable change in the remaining metal ion concentration after 45 min in the case of the 210-250 /u,m fraction and 30 min in the case of the 0^75 fxm fraction. These times represent the equilibrium times at which an equilibrium metal ion concentration (Ce) is presumed to have been attained. An empirically found functional relationship, common to most adsorption processes, is that the uptake varies almost proportionally with tU2 rather than with the

30

60 90 120 150 Co n t a c t T i me ( m i n )

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60 90 120 Co n t o c t T I me (

Fig. 2 Plots of contact time vs percent adsorption of lead and zinc ions on bed sediments: (a) 0-75 fim fraction; and (b) 210-250 fim fraction.

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C. K. Jain & D. Ram

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contact time, t (Weber & Morris, 1963). Therefore, in Fig. 3, plots of metal ions adsorbed, C, vs tm are presented for both the metal ions under consideration for the two particle size fraction. It is evident that the adsorption of the two metal ions on the bed sediments follows two phases, a linear phase of adsorption and then an almost flat plateau section. This may be attributed to the instantaneous utilization of the most readily available adsorbing sites on the adsorbent surface. Visual observation clearly indicates the minor importance of any precipitation from ion exchange.

Initial metal ion concentration (C0) To evaluate the effect of the initial metal ion concentration (C0) on the adsorption behaviour of lead and zinc on the bed sediments of River Kali, studies were conducted with initial metal ion concentrations ranging from 2 to 25 mg l 1 with a fixed adsorbent dose of 5 g l"1 at a pH value of 5.0 0.1. Plots were prepared between the metal ion adsorbed ( Q versus the equilibrium metal ion concentration at particle sizes of 0-75 and 210-250 jim (Fig. 4). It is inferred that for the same equilibrium time, the metal ion adsorbed is higher for greater values of initial metal ion concentration or the percentage adsorption is more for lower concentration of metal ions and decreases with increasing initial metal ion concentration. This is obvious because a more efficient utilization of the adsorptive capacities of the adsorbent is expected due to a greater driving force (by a higher concentration gradient pressure). Comparing the two plots it is clearly evident that the affinity of the two metal ions is more for the <75 /mi fraction, i.e. clay and silt. It is also evident from Table 1 that the <75 /mi fraction contains more iron and manganese content than that of the 210-250 /xm fraction. This is responsible for the higher adsorption of the two metal ions on the clay and silt fraction. However, the clay and

Adsorption of metal ions on bed sediments

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Fig. 4 Percent adsorption of lead and zinc ions on bed sediments: (a) 0-75 ixm fraction; and (b) 210-250 /im fraction.

silt constitute only 0.6% of the total sediment load and therefore, comparing the two weight percentage of the two fractions and their corresponding adsorption capacities for the metal ions, it is clear that the contribution of the sediment fraction of size 210-250 jum is more in controlling the metal pollution as compared to the clay and silt content. Among the two ions, lead and zinc, the affinity is more pronounced in the case of lead as compared to zinc ions. A special affinity of lead ions on clay mineral structures was also reported by Soong (1974).

Effect of pH The adsorption of lead and zinc ions on the bed sediments of the River Kali was studied over a pH range of 2-6 for a fixed adsorbent dose of 5 g 1"' at particle sizes of 0-75 and 210-250 yum (Fig. 5). The pH was adjusted using dilute nitric acid and sodium hydroxide solutions. The pH was measured before and after the attainment of equilibrium, the difference between the two values being generally less than 0.1 unit in the case of sediment of size 210-250 ptm and 0.2 unit in the case of sediment of size < 75 jxm. A general increase in adsorption with increasing pH of solution was observed for both fractions and for both the metal ions up to a pH value of 6.0. Beyond this pH the determination could not be performed due to the low solubility of the metal ions. A similar behaviour has been reported by many authors (Christensen, 1984; Farrah & Pickering, 1976a,b, 1979; Netzer & Wilkinson, 1976; Benjamin & Leckie, 1980) for the uptake of metal ions on various adsorbents. It is evident from the results that the pH for maximum uptake (or removal) of lead and zinc ions is 6.0 for the coarser sediment fraction with the corresponding adsorption values being 530 and 206 ngAg for lead and zinc ions respectively. At this pH the concentration of both the ions in solution reduced appreciably due to pH adjustments. Further, it was found that the adsorption of lead rises from 13.8% at a pH of 4.0

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C. K. Jain & D. Ram

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Fig. 5 Plot of pH vs percent adsorption of lead and zinc ions on bed sediments: (a) 0-75 fjm fraction; and (b) 210-250 ^m fraction.

to 42% at a pH of 6.0 for the coarser fraction of the sediments which reveals the sediment's capacity for adsorbing lead ions even in acidic media. The adsorption of zinc rose from about 2% at a pH of 3.0 to 15% at a pH of 6.0 for the same fraction of the sediments. The percentage adsorption was found to be more for the <75 /xm fraction as compared to the 210-250 (am fraction.

Adsorbent dose (Ws) The effect of adsorbent dose on the adsorption properties of the bed sediments of the River Kali was studied at a pH of 5.0 with different adsorbent doses varying from 2

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Fig. 6 Plot of adsorbent dose vs percent adsorption of lead and zinc ions on bed sediments; (a) 0-75 fim fraction; and (b) 210-250 fim fraction.

Adsorption of metal ions on bed sediments

721

to 10 g l"1 and at a fixed initial metal ion concentration of 10 mg 1 ' (Fig. 6). It may be observed that for a fixed initial metal ion concentration (C0 = 10 mg l"1), the adsorption of metal ions per unit weight of adsorbent decreased with increasing adsorbent dose. The adsorption increased from 15% to 31% in the case of lead and from 6% to 15% in the case of zinc for the 210-250 /xm fraction with an increasing adsorbent dose for both the metal ions under study. However, the percent adsorption (or removal) of metal ions was about 3-5 times more for the 0-75 /xm fraction as compared to the 210-250 pxa. fraction. This is because of the higher content of iron and manganese in the 0-75 /xm fraction, which act as the active support material for the adsorption of metal ions.

Particle size (dp) The adsorption data for the two metal ions with a fixed adsorbent dose of 5 g 1"1 and at a pH value of 5.0 are shown in Fig. 7 for different sizes of adsorbent. The plots between percent adsorption of metal ions at equilibrium vs adsorbent size reveals that for a fixed adsorbent dose (Ws = 5 g 11), the metal ion adsorbed was higher for smaller adsorbent size. Further, it may be observed that the percent metal ion adsorbed decreased from 90% to 20% in the case of lead and from 50% to 8% in the case of zinc with the increasing geometric mean of adsorbent size. This is because, adsorption being a surface phenomenon, the smaller adsorption sizes offered comparatively larger surface area and hence higher adsorption occurs at equilibrium. In addition to the particle size of adsorbent, the geochemical phases, namely iron and manganese oxides, also act as the active support material for the adsorption of the metal ions under study.

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40 80 120 160 200 240 280 320 360 Ge o me L r I c me an s i z e (micron)

Fig. 7 Plot of adsorbent size on percent adsorption of lead and zinc ions on bed sediments.

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C. K. Jain & D. Ram

CONCLUSION The present study has shown the potentiality of freshly deposited sediments to control metal pollution which may enter a river system through the disposal of municipal and industrial effluents. The lead and zinc metal ions have more affinity for the clay and silt fraction of the sediment, but the overall contribution of the coarser fraction (210-250 ^im) to adsorption is more as compared to clay and silt fraction. The adsorption data further suggest that the pH of the solution is the most important parameter controlling adsorption of metal ions on sediments. The percent metal ion removal increases with increasing adsorbent dose, and such removal increases with decreasing size of the adsorbent material. Among the two ions studied, the bed sediments of the River Kali have greater affinity for lead as compared to zinc ions. The two important geochemical phases, namely iron and manganese oxide, may act as the active support material for the adsorption of the two metal ions in addition to the particle size of the sediments. However, in natural river systems, salinity and pH highly affect the speciation of the metal ions and greatly interfere with their fixation on clay minerals. Adsorption/desorption equilibria and complexation with fulvic and humic acids also play an important role on speciation and further studies are needed to better understand processes affecting the sorption of metal ions in natural systems. REFERENCES
Anderson, P. R. & Benjamin, M. M. (1990) Constant capacitance surface complexation model: Adsorption in silica-iron binary suspensions. In: Chemical Modelling of Aqueous Systems II, ed. by D. C. Melchior & R. L. Bassett, 272281. ACS Symposium Series 416, American Chemical Society, Washington, DC. Bajracharya, K. & Barry, D. A. (1996) Heavy metal adsorption in soils: comparison of bisolute adsorption models and laboratory experiments. In: Water Quality Hydrology, ed. by V. P. Singh & B. Kumar, 19-26. Kluwer Academic Publishers, The Netherlands. Benjamin, M. M. & Bloom, N. S. (1981) Effect of strong binding of anionic adsorbates on adsorption of trace metals on amorphous iron oxyhydroxide. In: Adsorption from Aqueous Solutions, ed. by P. H. Tewari, 41-60. Plenum Press, New York. Benjamin, M. M. & Leckie, J. O. (1980) Adsorption of metals at oxide surface: Effects of the concentrations of adsorbate and competing metals. In: Contaminants and Sediments, ed. by R. A. Baker, vol. 2, 305-322. Ann Arbor Science, Ann Arbor, Michigan, USA. Christensen, T. H. (1984) Cadmium soil sorption at low concentrations: I. Effect of time, cadmium load, pH, and calcium. Water, Air Soil Poll. 21, 105-114. Dempsey, B. A. & Singer, P. C. (1980) The effect of calcium on the adsorption of zinc by Mn02 and Fe(OH)3. In: Contaminants and Sediments, ed. by R. A. Baker, vol. 2, 333-353. Ann Arbor Science, Ann Arbor, Michigan, USA. Farrah, H. & Pickering, W. F. (1976a) The sorption of copper species by clays, I. Kaolinite. Aust. J. Chem. 29, 11671176. Farrah, H. & Pickering, W. F. (1976b) The sorption of copper species by clays, II. Illite and montmorillonite. Aust. J. Chem. 29, 1167-1184. Farrah, H. & Pickering, W. F. (1979) The sorption of zinc species by clays minerals. Chem. Geol. 25, 317-326. Frstner, U. (1977) Metal concentration in freshwater sedimentsnatural background and cultural effects. In: Interaction Between Sediments and Freshwater, ed. by H. L. Golterman, 94-103. Pudoc/Junk, Wageningen, The Netherlands. Frstner, U. (1979) Metal transfer between solid and aqueous phases. In: Metal Pollution in the Aquatic Environment, ed. by U. Forstner & G. T. W. Wittmann, 197-270. Springer-Verlag, New York. Frstner, U. & Miiller, G. (1973) Heavy metal accumulation in river sediments, a response to environmental pollution. Geoforum 14, 53-62. Frstner, U. & Wittman, G. T. W. (eds) (1983) Metal Pollution in the Aquatic Environment, 2nd ed., Springer-Verlag, Germany. Gagnon, C , Arnac, M. & Brindle, J. R. (1992) Sorption interactions between trace metals (Cd and Ni) and phenolic substances on suspended clay minerals. Wat. Res. 26, 1067-1072.

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Jain, C. K. (1992) Effect of waste disposals on quality of water of river Kali (Uttar Pradesh), Tech. Report TR-148, National Institute of Hydrology, Roorkee, India. Jain, C. K. (1996) Application of chemical mass balance approach to upstream/downstream river monitoring data. J. Hydrol. 182, 105-115. Jenne, E. A. (1976) Trace element sorption by sediments and soilssites and processes. In: Symposium on Molybdenum, ed. by W. Chappel & K. Petersen, vol. 2, 425-553. Marcel Dekker, New York. Loganathan, P. & Burau, R. G. (1973) Sorption of heavy metal ions by hydrous manganese oxide. Geochim Cosmochim Acta 37, 1277. Meng, X. G. & Letterman, R. D. (1993a) Effect of component oxide interaction on the adsorption properties of mixed oxides. Environ. Sci. Technol. 27, 970-975. Meng, X. G. & Letterman, R. D. (1993b) Modelling ion adsorption on aluminium hydroxide modified silica. Environ. Sci. Technol. 27, 1924-1929. Meng, X. G. & Letterman, R. D. (1996) Modelling cadmium and sulfate adsorption by Fe(OH)3/Si02. Wat. Res. 30(9), 2148-2154. Netzer, A. & Wilkinson, P. (1976) Removal of heavy metal from waste water by adsorption on sands. Proc. 29th Waste Conference, Purdue, 841-845. Palheiros, B., Duarte, A. C , Oliveira, J. P. & Hall, A. (1989) The influence of pH, ionic strength and chloride concentration of the adsorption of cadmium by a sediment. Wat. Sci. Technol. 21, 1873-1876. Sakai, H., Kojima, Y. & Saito, K. (1986) Distribution of metals in water and sieved sediments in the Toyohira River. Wat. Res. 20, 559-567. Soong, K. L. (1974) Versuche zur adsorptiven Bindung von Schwermetall Ionen an ktmstlichen Tongemischen. Unpubl. PhD Thesis, University of Heidelberg, Germany. Subramanian, V., Grieken, R. V. & Vant, D. L. (1987) Heavy metal distribution in the sediments of Ganges and Brahmaputra Rivers. Environ. Geol. Water Sci. 9(2), 93-103. Weber, W. J. Jr. & Moris, J. C. (1963) /. Sanit. Engng. Div., ASCE, SA2, 31, cited in S. D. Faust & O. M. Aly. (1987) Adsorption Processes for water treatment. 65-122, Butterworth, London. Received 18 November 1996; accepted 4 February 1997