Green Chemistry Letters and Reviews

ISSN: 1751-8253 (Print) 1751-7192 (Online) Journal homepage: https://www.tandfonline.com/loi/tgcl20

Removal of chromium from water using pea waste

– a green approach

Jamil Anwar , Umer Shafique , Waheed-uz-Zaman , Muhammad Salman ,

Zaib Hussain , Maria Saleem , Naeema Shahid , Saliha Mahboob , Samina
Ghafoor , Mehwish Akram , Rabia Rehman & Nadia Jamil

To cite this article: Jamil Anwar , Umer Shafique , Waheed-uz-Zaman , Muhammad Salman , Zaib
Hussain , Maria Saleem , Naeema Shahid , Saliha Mahboob , Samina Ghafoor , Mehwish Akram ,
Rabia Rehman & Nadia Jamil (2010) Removal of chromium from water using pea waste – a green
approach, Green Chemistry Letters and Reviews, 3:3, 239-243, DOI: 10.1080/17518251003730833

To link to this article: https://doi.org/10.1080/17518251003730833

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Green Chemistry Letters and Reviews
Vol. 3, No. 3, September 2010, 239
243

RESEARCH LETTER
Removal of chromium from water using pea waste

Jamil Anwara, Umer Shafiquea*, Waheed-uz-Zamana, Muhammad Salmana, Zaib Hussaina,
a green approach

Maria Saleema, Naeema Shahida, Saliha Mahbooba, Samina Ghafoora, Mehwish Akrama, Rabia Rehmana
and Nadia Jamilb

a
Institute of Chemistry, University of the Punjab, Lahore 54590, Pakistan; bCollege of Earth and Environmental Sciences,
University of the Punjab, Lahore 54590, Pakistan
(Received 6 January 2010; final version received 22 February 2010)

Agro-waste materials have carboxylic and phenolic groups that play the main role in metal adsorption. The
advantages of these materials include easy availability, low cost, and reasonable metal removal capacity. One of
the materials (usually considered as waste) is pea waste (pods). Present work comprises adsorption of chromium
from aqueous solution using powder of pods of garden peas (Pisum sativum) in batch. Important parameters like
adsorbent dose, pH, contact time, and agitation speed were studied. Adsorption equilibrium was explained by
Langmuir, Freundlich, and Temkin isotherms. Maximum chromium uptake (qm) was 3.56 mg/g of adsorbent.
Heat of adsorption, as evaluated by Temkin isotherm was 1.96 kJ/mol. It is proposed that pea pods can be an
effective and environmentally benign (green) adsorbents for removal of chromium from industrial effluents and
waste waters.
Keywords: biosorption; chromium; pea pods; Langmuir isotherm; Freundlich isotherm; Temkin isotherm

Introduction high cost and energy needs, and generation of toxic

Water pollution caused by heavy metals is a serious sludge or other waste products that need careful
problem for aquatic ecosystems, because some metals disposal associated with these procedures, have made
are toxic even at low levels and are not degradable it necessary to replace them with a cost-effective and
naturally. Metals can enter our bodies through food, efficient treatment method like biosorption. Advan-
water, and air. Although some heavy metals, in tages of biosorption for removal of heavy and toxic
traces, are essential to maintain the metabolism of metals are that it can be carried out in situ at the
the body, above certain levels they are toxic. Heavy contaminated site and is environmentally benign with
metals are dangerous as they can bio-accumulate. no secondary pollution. Factors that influence the
Thus, metals with longer biological half-lives are performance of adsorbent in water are the nature and
dangerous because of the risk of chronic poisoning, concentration of substance to be removed and the
even if the environmental levels are low (1). Tan- presence of interfering species, which may compete for
neries, electroplating plants, and textiles produce the available adsorption sites and pH (1).
large quantities of chromium-poisoned water. Triva- Agricultural waste has proven to be useful in
lent chromium decreases immune system activity and providing low-cost adsorbents for heavy metal re-
causes structural perturbation in the erythrocyte moval. Examples of few adsorbents used for removal
membrane. This structural perturbation changes the of chromium are seaweed biosorbent (4), alfalfa
biological membrane permeability affecting the func- biomass (5), wine processing waste sludge (6), and
tions of ion channels, receptors, and enzymes im- cow dung (7). The interaction between adsorbent and
mersed in the erythrocyte membranes (2,3). metal is due to the presence of polymeric groups like
Chemical precipitation, lime coagulation, ion ex- cellulose, hemi-cellulose, pectin, lignin, and proteins.
change, reverse osmosis, and solvent extraction are The present study is concerned with the use of pods of
usually employed for removal of metals from water. Pisum sativum (garden peas) as adsorbent for the
However, disadvantages, like incomplete removal, removal of Cr(III) from water.

*Corresponding author. Email: [email protected]

ISSN 1751-8253 print/ISSN 1751-7192 online

# 2010 Taylor & Francis
DOI: 10.1080/17518251003730833
http://www.informaworld.com
240 J. Anwar et al.

Results and discussion

The release of toxic metals in water has disastrous
effects on the aqueous ecosystem. Although various
chemical and physical methods are being employed
for removal of toxic heavy metals from effluents,
these methods are either cost prohibited or not
practicable on account of operational shortcomings.
Agro-wastes have proven to be cost-effective adsor-
bents for the removal of heavy metals from aqueous
streams (8
11). In the present study, powder of
pods of P. sativum (garden peas) has been employed
as adsorbent for the removal of Cr(III) from aqueous
solutions.

Process parameters
The effect of adsorbent dose on adsorption of
chromium is shown in Figure 1. Metal removal Figure 2. Effect of contact time (min) on adsorption of
efficiency increases with an increase in the adsorbent chromium. Adsorbent dose 2 g; metal concentration, 50 mg/l;
dose. This is because of the greater availability of the volume, 50 ml; agitation speed, 100 rpm; pH, 6 and tempera-
ture, 258C.
exchangeable sites or surface area at the higher
concentrations of the adsorbent (12). Beyond the
optimal mass, little decrease in adsorption was on the external surface of the adsorbent (15). It has
observed by increasing the amount of adsorbent. At also been noticed that equilibrium is established in les
higher adsorbent doses, the adsorbent
adsorbent time for higher adsorbent doses. Figure 3 summarizes
interaction may have increased in comparison to the removal of chromium as a role of pH. Maximum
adsorbent
adsorbate interaction (13) that led to less removal has taken place at pH 4. Slightly acidic
adsorption (14) assemblage of adsorbent. conditions are favorable, however, at very low pH as
Equilibrium time is one of the most important H competes with metal cations for the available
parameters for an effective wastewater treatment adsorption site.
system. The effect of contact time on adsorption is Figure 4 reveals that agitation speed significantly
shown in Figure 2. The majority of metal ions were affects the process of adsorption. Optimum agitation
removed in the first 30 min. The behavior suggests speed is 100 rpm. If shaking speed is too slow, powder
that at the initial stage adsorption takes place rapidly

Figure 3. Effect of pH on adsorption of chromium.

Figure 1. Effect of adsorbent dose (g/l) on adsorption of Adsorbent dose, 2 g; metal concentration, 50 mg/l; volume,
chromium. Metal concentration, 50 mg/l; agitation speed, 100 50 ml; agitation speed, 100 rpm; time, 30 min and
rpm; time, 40 min; pH, 6 and temperature, 258C. temperature, 258C.
 Green Chemistry Letters and Reviews 241

for chromium (Table 1). The adsorption coefficient,

b, is related to apparent energy of adsorption. The
value of b is 0.043 dm3/g. R2 (correlation coefficient)
values approaching to 1 clearly suggest that the
Langmuir isotherm provides a good linear model
for adsorption of Cr(III).
The values of 1/n and KF, which roughly corre-
spond to the adsorption intensity and maximum
adsorption capacity, respectively, were evaluated
with the help of slope and intercept of the linear
Freundlich plot. 1/n can be used for the measurement
of adsorption intensity of metal cations on pea pods.
It was 0.739 for chromium (Table 1). Taking reci-
procal of 1/n, the n value obtained is in the range 1

10, showing favorable adsorptions (16). Eventual
adsorption capacity, KF, as calculated from Freun-
dlich isotherm is 0.192. R2 value approaching to 1
Figure 4. Effect of agitation speed on adsorption of
chromium. Adsorbent dose, 2 g; metal concentration, 50
points out good linearity of the Freundlich model for
mg/l; volume, 50 ml; time, 30 min; pH, 4 and temperature, adsorption of chromium on pea pods.
258C. Temkin adsorption potential, KT, for Cr(III) is
2.04 (Table 1). It marks the good potential of pea
of pea pods instead of spreading in the solution pods for Cr(III). BT, related to heat of adsorption,
gathers at bottom and various active sites got buried is 1.96 kJ/mol for chromium. Values less than 8
under the above layers of adsorbent. Since adsorption suggested a weak interaction between metal and pea
is surface phenomenon, under-buried layers do not pods (17). The process, as indicated by BT, can be
take part in adsorption. Thus, the shaking rate should termed physiosorption as for chemical bonding, since
be enough to enssure that all the binding sites are the value of BT is above 8 kJ/mol (17). Linearity of
readily available for metal uptake (1). However, high Temkin model holds well as pointed out by R2 value
speed makes adsorption difficult as it does not allow in Table 1, however, slightly less in comparison to
enough time to metal ions to be taken up by Langmuir and Freundlich models.
adsorbent.

Experimental
Adsorption isotherms
To describe the chromium adsorption behavior by Preparation of adsorbent
pods of peas, isotherms data obtained were fitted to Pea seeds were separated and the pods were washed
the Langmuir, Freundlich, and Temkin adsorption with distilled water thoroughly. Pods were dried in
models. Maximum adsorption capacity, qm, corre- sunlight for two days and then in an oven (Memmert,
sponding to complete monolayer coverage revealed Model 100
800) at 808C overnight. Dried pods were
that mass capacity of powder of pea pods is 3.56 mg/g ground and sieved to 60 mesh (ASTM).

Table 1. Langmuir, Freundlich, and Temkin isotherm data.

Langmuir isotherm parameters (y 6.53x0.28)

Slope Intercept b (dm3/g) qm (mg/g) R2
6.53 0.28 0.043 3.56 0.99
Freundlich isotherm parameters (y 0.739x
0.716)
Slope Intercept 1/n KF R2
0.739
0.716 1.35 0.192 0.98
Temkin isotherm parameters (y 1.263x0.906)
Slope Intercept BT (kJ/mol) KT R2
1.263 0.906 1.96 2.04 0.95

Notes: Adsorbent dose, 2 g; metal concentration, 30
80 mg/l; volume, 50 ml; time, 30 min; agitation speed, 100 rpm; pH, 4 and temperature,
258C.
242 J. Anwar et al.

Stock solutions and standards 1

log qe  log KF  log Ce (2)
Stock solution of chromium (1000 mg/l) was pre- n
pared with appropriate weighed quantity of chro- RT RT
mium chloride (Sigma
Aldrich). Standard solutions qe  ln KT  ln Ce ; (3)
BT BT
of the desired concentrations (5
100 mg/l) were
prepared by successive dilutions of the stock solution. where qe (mg/g of adsorbent) is the amount of metal
adsorbed, whereas Ce (mg/l) is concentration at
equilibrium. qm (mg/g) and b (dm3/g) are Langmuir
Equipment and apparatus isotherm parameters. KF and n are Freundlich
Digital pH-meter (HANNA, Model-8417) was used isotherm parameters. BT (kJ/mol) is heat of sorption.
for pH adjustments. HCl (0.1 M) and NaOH (0.1 M) BT and KT are Temkin isotherm parameters.
were used for adjustment of pH, while standard
buffers were used to keep the pH constant. Perkin
Conclusion
Elmer atomic absorption spectrometer (Model-AA-
nalyst 100) was used for determination of chromium Detailed isotherm analysis of experimental data was
concentrations in the solutions at 357.9 nm. carried out to explain the adsorption of Cr(III) on
powder of pea pods. It has been found that pea pods
possess a good tendency to adsorb chromium.
Study of process parameters Optimum conditions for removal of chromium are
A series of experiments was carried out to study the 2 g adsorbent for 50 ml solution (50 mg/l) with
effects of four parameters (adsorbent dose, pH, contact time 30 min and agitation speed 100 rpm.
contact time, and agitation speed) on adsorption of Four is the most suitable pH to work with. The
chromium by pea pods, for the solution of initial present study evaluates the efficiency of pea pods, an
concentration 50 mg/l. To study the effect of a certain agricultural waste material, to remove heavy metals
parameter, that parameter has been varied gradually from aqueous ecosystems, to overcome water pollu-
keeping the other three constant. All the glassware tion by economical means. The proposed method is
used during the study were washed and dried in an no doubt green, economical, and capable to over-
oven at 1058C for 1 h. After adsorption under certain come metal pollution without using any hazardous
conditions, contents of the flasks were filtered and chemicals.
filtrates were subjected to atomic absorption for
determination of chromium.
The effect of the adsorbent dose on adsorption of
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