SORPTION OF Cu AND Zn BY BONE CHARCOAL

J.A. WILSON1, , I.D. PULFORD1 and S. THOMAS2 1 Department of Chemistry, University of Glasgow, Glasgow, G12 8QQ, Scotland; 2 Brimac Charcoals Limited, 21 Dellingburn St, Greenock, PA15 4TP, Scotland ( author for correspondence: e-mail: jonathaw@chem.gla.ac.uk)

Received 10 June 2001; accepted in revised form 10 April 2002

Abstract. Bone charcoal is being developed as a treatment for decontaminating polluted water. In particular, its potential to adsorb metal species from contaminated water supplies is being examined. In this study, bone charcoal was used in batch and column experiments designed to investigate the sorption of two cationic metals Cu and Zn. The data from batch experiments tted the Langmuir isotherm and so theoretical maximum binding capacities could be obtained. These values were compared with experimental values derived from the column experiments. The mechanisms involved in the immobilisation were also investigated. Key words: adsorption, bone charcoal, breakthrough curves, copper, water treatment, zinc

1. Introduction Bone charcoal is being developed as a treatment for decontaminating polluted water. An inexpensive yet efcient adsorbent of heavy metals is desired in efuent cleanup. Specically designed adsorbents or high surface area activated charcoals tend to be expensive, whereas bone charcoal, although not as cheap as some natural adsorbents (e.g. wood bark), is relatively inexpensive. The ability of bone charcoal to remove colour has been realised since the early 19th century, and in 1815 John Martineau patented the use of bone charcoal for the rening and clarication of sugar. It is still widely used in the sugar industry. More recently, interest has been shown in the possibility of using bone charcoal as a water cleanup treatment (Lewis, 1995). Bone charcoal is produced by the pyrolysis of ground bone at 800 C in a limited supply of oxygen (O2 ). Unlike most other carbonaceous adsorbents, bone charcoal contains only around 10% carbon (C) by weight with the remainder comprising mainly hydroxyapatite, but also a signicant percentage calcium carbonate (CaCO3 ). The carbon, however, accounts for half the total surface area of the product and CaCO3 gives bone charcoal alkaline properties (Table I). It is the unique composition of bone charcoal and its ability to remove a wide variety of compounds, which has led to the development of its use in cleaning up contaminated water (Lewis, 1995). The hydroxyapatite has a good ability to remove inorganic cations (Xu, 1994; Wilson, 2000) and to a lesser extent anions, while the carbon component can also remove some organic components.
Environmental Geochemistry and Health 25: 5156, 2003. 2003 Kluwer Academic Publishers. Printed in the Netherlands.

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TABLE I Composition of bone charcoal Chemical composition Hydroxyapatite Carbon CaCO3 CaSO4 Fe2 O3 Acid insoluble ash Total surface area Carbon surface area 7076 wt.% 911 wt.% 79 wt.% 0.10.2 wt.% <0.3 wt.% 3 wt.% max 100 m2 g1 50 m2 g1

The main aims of this study were to examine the ability of bone charcoal to remove copper (Cu) and zinc (Zn) from aqueous solution and therefore evaluate its potential to be used in real world systems. The usefulness of batch studies in designing real world systems was also examined and from this, the possibility of using data from batch studies and small-scale column studies for scale up work was considered. The mechanisms of adsorption were also investigated. The study was carried out to allow optimisation of parameters for a full-scale immobilisation process.

2. Materials and methods 2.1. MATERIALS The bone charcoal used was Brimac 216 20/60 Tyler mesh (250850 m) supplied by Brimac Carbon Services. A typical analysis has been shown in Table I. Before use, the charcoal was washed with deionised water until the pH of the wash water was 7 0.2. It was then dried at 100 C for 24 h, then cooled before use. Copper and zinc solutions were made from Analar copper(II)nitrate 3-hydrate, Cu(NO3 )2 3H2 O (BDH Chemicals) and Analar zinc nitrate hexahydrate, Zn(NO3 )2 6H2 O (Avocado Chemicals). Stock solutions (4000 mg L1 ) of both metal ions were prepared using deionised water and subsequently diluted. The pH of the solutions was not adjusted. 2.2. BATCH STUDIES A 1 g sample of bone charcoal was shaken with 50 mL of metal solution, in triplicate, of varying concentration (04000 mg L1 Cu and 02000 mg L1 Zn) on

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an end-over-end shaker for 120 min. After shaking, the solution was immediately ltered through Whatmans No. 2 lter paper into 60 mL plastic bottles. The initial and nal concentrations of the solutions were measured by ame atomic absorption spectroscopy on a Perkin Elmer 1100B. Calcium concentration was measured in the same way, phosphate concentration was measured by ICP-OES, and pH in solution was also measured. 2.3. COLUMN STUDIES A 3.5 cm diameter column was plugged with glass wool and 200 g bone charcoal added as a slurry to give a bed depth of 30 cm. The column was then vibrated for 5 min at high frequency to ensure even packing and then was lled with deionised water for 24 h to ensure all the air was expelled from and between the bone char particles. Twelve litres of 2000 mg L1 Cu or Zn solution was then pumped at a constant ow rate (10 mL min1 or 0.62 m h1 linear velocity) through the column and 5 mL samples were collected at regular time intervals. Eluent concentration was analysed by ame atomic absorption spectroscopy.

3. Results and discussion 3.1. BATCH STUDIES 3.1.1. Adsorption isotherms Adsorption of both Cu and Zn increases rapidly at low concentrations (Figure 1) showing bone charcoal has a good afnity for both metals, especially for Cu. At high concentrations the slope of the adsorption isotherm decreases and the capacity of bone charcoal for the metal can be assessed. The shape of the curve suggests that the Langmuir isotherm equation, which is widely used to describe monolayer adsorption onto various surfaces (Sposito, 1986) should provide a suitable quantication of the data (Table II).

Figure 1. Adsorption isotherms for Cu and Zn on bone charcoal.

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TABLE II Langmuir values Cu Langmuir equation correlation Theoretical capacity of metal on 1 g of bone charcoal (from Langmuir equation) R 2 = 0.99 27 1.3 mg g1 Zn R 2 = 0.97 24 3.0 mg g1

3.1.2. Mechanisms Release of calcium (Ca) into solution as M2+ is sorbed shows a linear relationship for both metals, with R 2 > 0.9. For 1 mol of Cu-sorbed 0.72 mol of Ca is released, whereas for Zn 0.2 mol is released. The change in pH was from 8 to 5. Calcium dissolution due to the change in pH, however, was negligible with only 0.010.02 mmol Ca measured at pH 5 in a blank solution. Phosphate concentrations were low, being below the limit of detection for the majority of samples. Bone charcoal has hydroxyapatite, C and CaCO3 as major components (Table I). Hydroxyapatite is not just a source for adsorption but also enables ion-exchange to occur (Suzuki and Hatsushika, 1981; Takeuchi and Arai, 1990). Measurement of the Ca concentration in solution suggests that ion-exchange is a signicant mechanism for the removal of Cu from solution with 0.72 mol released for every mol of Cu-sorbed. This is relative to a 1:1 mol ratio of Ca:Cu that would be expected if ion-exchange is the only mechanism. For Zn this ratio (Ca:Zn) is considerably lower (0.2) so ion-exchange may not be a dominant mechanism. Other mechanisms such as chemisorption may be more signicant in the removal of Zn from solution. The reasons for the differences between Cu and Zn sorption are still not clear, but electronegativity, speciation, ion-size and amount of space in the d-orbitals are all thought to have an inuence (Raouf and Daifullah, 1997; Takeuchi and Arai, 1990). 3.2. COLUMN STUDIES Breakthrough curves were plotted for each of the metals as solutions of each metal were passed through the columns (Figure 2). Initially most of the added metal is sorbed with little being left in solution. Approaching 10 bed volumes, both metals breakthrough. Zinc breakthrough is slightly earlier than for Cu. At approximately 1520 bed volumes less metal than expected is eluted in solution, especially noticeable in the removal of Zn. A differing adsorption mechanism may be causing more metal to be held on bone charcoal (Ferro-Garcia, 1988). Perhaps several mechanisms are operating over different time scales a rapid ion-exchange step and a slower diffusion stage. In reality, the mechanisms of sorption are likely to be more complex involving different interactions with hydroxyapatite, C and CaCO3 .

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Figure 2. Breakthrough curves for Cu and Zn.

TABLE III Comparison of capacities between batch and column studies Batch (mg g1 ) Copper capacity Zinc capacity 27.5 1.3 24.5 3.0 Column (mg g1 ) 32.4 3.5 27.8 4.5

If the area under the graph is integrated, a gure for the amount of metal sorbed can be calculated, and from this a capacity for 1 g of charcoal for that particular metal can be inferred. Comparing capacities for batch and column work (Table III), consistently more metal is sorbed in the column system. A t-test shows that there is a difference between data sets signicant at the 5% level. There is, however, greater variability in column studies due to problems in obtaining uniform packing and difculties in estimating the start and, in particular, the end of the breakthrough curve for calculation of the capacity. The batch systems provide a capacity gure which is approximately 80% of the column gure. Batch systems are, therefore, very useful in the designing of the columns to ensure basic parameters are met. Longer time scale columns with lower concentrations of inuent should be run to ensure conditions and capacities are comparable at more commonly found environmental levels.

4. Conclusions Bone charcoal has a high capacity for the removal of Cu and Zn from water relative to many adsorbents. Copper is removed more efciently than Zn and to a greater capacity. The batch studies can provide capacity gures and other basic variables necessary for column studies, however, there is still further work to be done in the understanding of sorption mechanisms and the effect of real-world concentration levels on sorption kinetics onto bone charcoal.

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References
Ferro-Garcia, M.A.: 1988, Adsorption of zinc, cadmium and copper on activated carbons obtained from agricultural by-products, Carbon 26, 363373. Lewis, J.: 1995, The use of bone charcoal in the treatment of rural water supplies, Journal of the Chartered Institute of Water and Environmental Management 9, 385395. Raouf, M.W.A. and Daifullah, A.A.M.: 1997, Potential use of bone charcoal in the removal of antimony and europium radioisotopes from radioactive wastes, Adsorption Science and Technology 15, 559569. Sposito, G.: 1989, The Chemistry of Soils, Oxford University Press, New York, pp. 150154. Suzuki, T. and Hatsushika, T.: 1981, Synthetic hydroxyapatites employed as inorganic cation exchangers, Journal of Chemical Society Faraday Transcripts I 77, 10591061. Takeuchi, Y. and Arai, H.: 1990, Removal of co-existing Pb2+ , Cu2+ and Cd2+ ions from water by addition of hydroxyapatite powder, Journal of Chemical Engineering of Japan 23, 3447. Wilson, J.A.: 2000, Adsorption of heavy metals by natural charcoal (bone charcoal): its potential as a water treatment cleanup, in: Nriagu, J. (ed.), Breeding of the 11th Annual International Conference on Heavy Metals in the Environment, Contribution No. 1436, School of Public Health, University of Michigan, Ann Arbor, MI (CD-ROM). Xu, Y.: 1994, Sorption of zinc and cadmium on hydroxyapatite surfaces, Environmental Science and Technology 28, 14721480.