Environment International 28 (2002) 29 – 33


Removal of dyes from an artificial textile dye effluent by two
agricultural waste residues, corncob and barley husk
T. Robinson, B. Chandran, P. Nigam*
School of Biomedical Sciences, University of Ulster, Coleraine, Londonberry BT52 1SA, Northern Ireland, UK
Received 19 August 2001; accepted 21 November 2001

The use of a previously untried biosorbent, barley husk, for dye removal is compared to corncob. The effectiveness of adsorption as a
means of dye removal has made it an ideal alternative to other more costly treatments. This paper deals with two low-cost, renewable
biosorbents, which are agroindustrial by-products, for textile dye removal. Experiments at total dye concentrations of 10, 20, 30, 40, 50,
100, 150, and 200 mg l 1 were carried out with an artificial effluent consisting of an equal mixture of five textile dyes. The effects of
initial dye concentration, biosorbent particle size, dose of biosorbent, effective adsorbance, and dye removal kinetics were examined. One
gram (per 100 ml) of  600 mm corncob was found to be effective in removing a high percentage of dyes at a rapid rate (92% in 48 h).
One gram of 1  4 mm barley husk was found to be the most effective weight and particle size combination for the removal of dyes (92%
in 48 h). The results illustrate how barley husk and corncob are effective biosorbents concerning the removal of textile dyes from effluent.
D 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Adsorption; Barley husk; Corncob; Textile dyes

1. Introduction
The release of dyes into wastewaters by various industries poses serious environmental problems due to various
dyes’ persistent and recalcitrant nature. Textile industries are
responsible for the discharge of large quantities of dyes into
natural waterways due to inefficiencies in dyeing techniques. Up to 50% of dyes may be lost directly into waterways
when using reactive dyes (McMullan et al., 2001).
The presence of dyes in waterways is easily detectable
even when released in small concentrations (Nigam et al.,
2000). This is not only unsightly, but the colouration of the
water by the dyes may have an inhibitory effect on photosynthesis affecting aquatic ecosystems. Dyes may also be
problematic if they are broken down anaerobically in the
sediment, as toxic amines are often produced due to incomplete degradation by bacteria (Weber and Wolfe, 1987).
Hence, colour removal from textile wastewater is of major
environmental concern (Juang et al., 1996).

* Corresponding author. Tel.: +44-28-7032-4053; fax: +44-28-70324906.
E-mail address: p.nigam@ulst.ac.uk (P. Nigam).

Conventional physical and chemical treatments for dye
removal (Robinson et al., 2001) have been shown to be
either expensive, e.g., activated carbon and membrane
filtration (also incapable of treating large volumes), or
produce a concentrated sludge, e.g., Fentons Reagent.
In water reuse technology, various techniques have been
employed in the past for the removal of dyes from wastewater (Perineau et al., 1982; Singh et al., 1984; McKay et al.,
1985; Gupta and Bhattacharya, 1985; Khattri and Singh,
2000; Low et al., 2000; Liversidge et al., 1997; Mittal and
Gupta, 1996; Choy et al., 1999) Removal of dyes by
adsorption has been shown to be an effective way of treating
dye-containing effluent (Robinson et al., 2001; Kamel et al.,
1991; Keith et al., 1999; McKay, 1981).
Although the most widely used physical method for dye
removal is activated carbon (Nasser and El-Geundi, 1991),
due to its high degree of effectiveness, it has high running
costs (requires regeneration after sorption) and so there is a
need for an equally effective but cheaper sorbent (McKay,
1981). The use of agricultural residues for dye removal
using corncob has been investigated by El-Geundi (1991),
but no work has been carried out using barley husks. Barley
husks are renewable agricultural residues and are widely
available in many countries.

0160-4120/02/$ – see front matter D 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 6 0 - 4 1 2 0 ( 0 1 ) 0 0 1 3 1 - 3

of Ireland.1. The percentage of dye removal was low for lower dye concentrations of 10 to 40 mg l 1 (results not shown).000 rpm. 200 mg l 1 –  – . 150 mg l 1 – ~ – . 150. Effect of dose of sorbent Although 5 g of barley husk was able to remove a very high percentage (85% at a Co of 100 mg l 1) of dyes from Fig.. Rep. and 42% when the initial concentrations were 50. 20. The effect of initial dye concentration on the rate of adsorption is shown in Fig. 50. The effect of the performance of various operating parameters on adsorption such as adsorbent dose. 150. and  600 mm particle sizes which were obtained using a 600-mm sieve. The percentage of dye adsorbed increased as the initial dye concentration increased with 82% of dye being removed with a Co of 50 mg l 1. respectively. The substrates were dried to a constant weight. (1976). Kinetic parameters were also studied for the removal of dyes by these substrates. when compared to that for the higher concentration range (as in Fig. 3. concentration of dyes. This showed that the equilibrium capacity of the barley husks increased as the initial concentration increased. Robinson et al. and carried out in duplicate. Percentage of artificial effluent adsorbed by 5 g of corncob (1  4 mm) at concentrations of 50 mg l 1 – ^ – . 2 shows that the percentage dye removal by corncob decreased from 81%. they have been studied for their effectiveness in the removal of dyes from an artificial effluent containing five dyes. 1. 100. 100 mg l 1 – & – . Materials and methods The reactive dyes used in this study were Cibacron Yellow C-2R. From this. 200 mg l 1 –  – . 20 ± 2 C. As corncob and barley husk meet the above criteria. in distilled deionized water to produce a stock solution of 1000 mg l 1. Londonderry. 30. The artificial effluent was prepared by dissolving the five dyes. who reported that the initial concentration of dyes had only a small influence on the time of contact necessary to reach equilibrium in the sorption study of Telon Blue by peat (Keith et al. and decolourisation calculated from lmax readings (600 nm). 100 ml volumes containing initial concentrations (Co) of 10. and Remazol Red RB. 3. This finding is supported by work carried out by Poots et al. The corncobs were purchased from a local supermarket and the barley husks were a gift from Bushmills Distillery. 150 mg l 1 – ~ – . 2. 1999). 200 mg l 1 were made. The main aim of the present study was to develop a cheap and suitable method for the removal of dyes from an artificial effluent. Remazol Black B. which was 48 h. Cibacron Red C-2G. Percentage of artificial effluent adsorbed by 5 g of barley husk (1  4 mm) at concentrations of 50 mg l 1 – ^ – . 40. 2. the time taken to reach equilibrium was equal for all the initial dye concentrations. 1) for the same 24 h. 85% at 100 mg l 1. / Environment International 28 (2002) 29–33 ments were carried out statically at room temperature. 100. 89% at 150 mg l 1. The substrates were tested for their adsorbance capacities at two different sizes: 1  4 mm. Northern Ireland. and 200 mg l 1. which was obtained by coarsely milling dried strips of corncob (barley husk were already of that approximate size). One milliliter samples were taken at regular intervals.2. Different doses (dry weight) of each substrate were added to 100 ml of the artificial effluent at the varying concentrations. 62%. Effect of contact time and concentration Fig. Decolourisation was recorded using a spectrophotometer. in equal amounts. However. 100 mg l 1 – & – . Results and discussion 3. The dyes were a gift from Fruit of the Loom. 1. .30 T. and 91% at 200 mg l 1 after 24 h. Buncrana. and particle sizes were monitored. 71%. centrifuged in a microcentrifuge at 13. Experi- Adsorption of dyes from an artificial effluent onto barley husk was measured at given contact times for four different initial dye concentrations at an adsorbent dose of 5 g (1  4 mm of particle size per 100 ml). Cibacron Blue C-R. Fig.

1 g – ~ – . . By reducing the particle size Fig. Effect of particle size Fig. This dose also had the highest percentage of dye removal. 3 that it is definitely not the most efficient per gram of substrate. By reducing the sorbent dose to 2 g there is a slight increase in effective dye removal. The selection of 1 g barley husk is significant if the process is to be scaled up. 1 g of barley husk was selected as the sorbent dose. 2 g – & – . It is evident from Fig. and this is increased further to 92% by reducing the dose to 1 g/100 ml 1. 3. it is evident from Fig. 31 ). 5 g – ^ – . 2 g of corncob was more efficient at removing the dyes but 1 g of corncob had higher q values from t36 onwards. 1  4 mm. having a dramatic effect on cost and sheer bulk. Therefore. the q values are much lower than that displayed by the barley husk. Robinson et al. In the initial period of the experiment. the use of a smaller sorbent dose may be a more economically viable option. Effect of various weights of barley husk on removal of artificial effluent (Co 100 mg l the effluent. 1). The q values obtained by 5 g of 1  4 mm corncob compare well with barley husks at similar adsorbent dose.3. 1 g – ~ – . 4 that corncobs (1  4 mm) are not as effective at removing dyes per gram of substrates as barley husk. as it bound more dyes per gram of substrate throughout the duration of the experiment.T. It also had the adsorptive capacity to remove more dyes at a faster rate in the initial stages. 5 g – ^ – . Effect of various weights of corncob on removal of artificial effluent (Co 100 mg l 1 ). 1  4 mm. 92% at a Co of 100 mg l 1 in comparison to 85% removal by 5 g of barley husk (Fig. The difference in the q values of 1 and 2 g is small until t36 and if scale-up factors such as cost and bulk are taken into account. / Environment International 28 (2002) 29–33 1 Fig. For 2 and 1 g doses. 3. 4. 5 shows the effect that milling had on the removal of dyes from an artificial effluent. 2 g – & – .

One gram of barley husk (1  4 mm) showed an overall higher efficiency of dye removal through out the experiment and continued removing dyes at a steady and rapid rate. Conclusions Fig. The unmilled barley does not. Fig. Unlike  600 mm barley husk. but unlike the barley husks. become quickly saturated. The milling of corncob was necessary in order to achieve better performance for dye removal. however. It is evident that the particle size of  600 mm. 7 illustrates how the rate of dye removal increased with an increase in initial concentration and is shown by plotting Co vs. it is apparent that more dye molecules are bound per gram of substrate in the first 5 h. continued to effectively bind with dye molecules at a much more efficient rate. and continues to effectively bind to dye molecules until t35. This is supported by Figs. The 1 g (  600 mm) corncob also allowed a higher efficiency in dye adsorption as more dye per gram of substrate was bound.  600 mm – & – . 1  4 mm particle size – ^ – . 1 ) removal removal in the first 5 h by the  600-mm particle sizes. but is subsequently quickly saturated. the change in concentration (dc). 5 and 6. no milling was required to achieve a high degree of effective adsorption. Although the  600-mm particle sizes facilitated rapid binding for barley husk. ultimately producing a higher percentage of dye removal at the end of the given retention period. . 3. dye binding is reasonably efficient in the first 5 h.32 T. constant removal. Effect of particle size on artificial effluent (Co 100 mg l by corncob. the  600 mm particles quickly become saturated. 6. had the higher rate of removal for the initial concentrations tested. There was no reduction in the total percentage of dyes removed by not milling (both particle sizes removed 92% of the dyes). 6 illustrates the effect of milling corncob. For barley husk however. For the unmilled barley husks. Increasing the surface area has the effect of allowing a more efficient removal of dyes in the first 5 h. Fig. it was nonetheless reasonably fast. Effect of particle size on artificial effluent (Co 100 mg l 1) removal by barley husk. and increasing the surface area available for the binding. Although the rate of dye binding was not as rapid as that by  600 mm particle size.  600 mm – & – . over change in time (dt). Co 100 mg l 1) and further removal occurred at a much slower rate. Robinson et al. as the dye molecules were gradually bound over a period of time to the larger particle sizes. they quickly became saturated (e. before continuing at a steady rate until t50. Kinetics of dye removal 4. As time increases and more dye molecules are quickly bound to the barley husks. between t10 and t24.. and would also reduce the cost of use Fig. corncob does not become quickly saturated and had the capacity to continue to steadily bind to dye molecules throughout the duration. One gram (1  4 mm) of barley husk was selected as the best combination due to its high percentage of dye removal from the effluent. There is a period of 14 h. This particle size and weight allowed the highest percentage dye removal (92% in comparison to 62% by 1  4 mm particle size) at a rapid rate. which show the rapid rate of dye This study has shown the effectiveness of two widely available agroindustrial by-products for the removal of dyes from an artificial effluent. for both substrates. / Environment International 28 (2002) 29–33 to  600 mm.4. 5. ultimately removing more dyes from solution per gram of substrate. in comparison to the unmilled corncob. with a small increase in binding towards t50. The  600 mm particle size dramatically increased the effectiveness of corncob for dye removal. The experimental results show that 1 g of corncob (  600 mm) was the most appropriate weight and particle size for dye removal from the artificial effluent. 1  4 mm particle size – ^ – . The smaller particle size allowed a much steeper rate of effective removal in the first 5 h.g. Unmilled barley husks allow a steady. The accelerated rate of removal can be attributed to extra binding sites made available through milling. The 1  4 mm particle size for both substrates showed a much slower rate of removal. when very little adsorption takes place. The higher surface area not only allowed an initial period of highly effective dye removal.

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