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Water Resources and Industry 17 (2017) 16

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Water Resources and Industry


journal homepage: www.elsevier.com/locate/wri

Remediation of chromium and copper on water hyacinth (E. crassipes)


shoot powder

MARK

M. Sarkara, , A.K.M.L. Rahmana, N.C. Bhoumikb


a
b

Department of Chemistry, Jagannath University, Dhaka 1100, Bangladesh


Wazed Miah Science Research Centre, Jahangirnagar University, Dhaka 1342, Bangladesh

A R T I C L E I N F O

A BS T RAC T

Keywords:
Adsorbent
Water hyacinth
Tannery euent
Physicochemical parameters, ltration

Tannery euent characterization and removal eciency of Chromium (Cr) and Copper (Cu) on water hyacinth
has been observed by ltration process. The euent was contaminated by deep blue color, acidic pH, higher
value of total dissolve solid (TDS), electrical conductivity (EC), chemical oxygen demand (COD) and lower value
of dissolve oxygen (DO). After ltration, the euent shows that the permissible limit of investigated metals.
Adsorbent capacity of water hyacinth shoot powder for Cr and Cu ion was found to be 99.98% and 99.96% for
standard solution (SS) and 98.83% and 99.59% for tannery euent (TE), respectively.

1. Introduction
Bangladesh is a south Asian developing country with its unplanned
industrial and urban area. In most of the cases the euent is
discharged into the nearby River or water body without any pretreatment and thereby deteriorating aquatic environment. From this
euent, the enrichment of heavy metal concentration in the water
body is the most growing concern in the present era. The Buriganga is a
historical and commercially important River for Bangladesh owing at
the southern edge of Dhaka Metropolitan area. But from last couple of
decades the Buriganga River has been polluted by heavy metals
(especially Cr and Cu) coming from tannery euents [1]. People
staying on the bank of the Buriganga River are facing various health
problems by using the polluted water in their household purpose as the
Buriganga is a vital source of water for nomad of Dhaka city. The
properties of water are changed by heavy metal contamination and has
a detrimental eect on sheries life and habitats [2,3]. The heavy
metals have high mobility in aquatic systems and expose high toxicity
[4]. The discharge from electroplating, tannery, metallurgical industries, paints, pigments, printing and graphics, waste disposal, agricultural waste and sewage are the main sources of chromium pollution [5].
The industries which widely used Copper are metal cleaning and
plating, paper board, printed circuit board, wood pulp, fertilizer, paints
and pigments [6,7]. The copper and chromium enriched euent from
these industries mixed into the water streams without any pretreatment. Heavy metals released from dierent sources into the environment have a propensity to persist and eventually are accumulating
throughout the food chain that imposing a serious threat to the animal

health and environment [8,9]. Therefore, the removal of heavy metal


from industrial and municipal euent is one of the growing concerns.
The commonly applied methods for the treatment of industrial
euents are precipitation, ion exchange, electrochemical process,
membrane processes and adsorption [10]. However, most of these
techniques have some drawbacks such as complicated treatment
process and high cost. Adsorption is the most viable and eective
method for removing heavy metal. In recent years adsorption is
considered as a much preferable technique [11,12]. Nowadays, it is a
growing demand to nd out a locally available, low cost, environmentally friendly and ecient adsorbent for the removal of heavy metal
from industrial and municipal waste. In the recent past, some
researchers emphasize using aqua vascular weed for removal of heavy
metals like water hyacinth. Hasan et al. [13] used water hyacinth root
for the removal of Cd and Zn and observed higher removal eciency.
Water hyacinth (Eichhornia crassipes) is grown abundantly throughout the tropical and subtropical region [14] in the world and also
available in the Bangladesh. As a consequence, we select water hyacinth
as a low cost adsorbent to study the removal eciency of chromium
and copper using ltration process. The aim of this study is to observe
the removal eciency of water hyacinth shoot powder.
2. Materials and methods
2.1. Preparation of standard chromium and copper solution
An amount of 500 mg/l standard solution of Cr and Cu were
prepared. Accurately weighted 1.4135 g K2Cr2O7 and 1.9661 g

Corresponding author.
E-mail address: akash.mamon@gmail.com (M. Sarkar).

http://dx.doi.org/10.1016/j.wri.2016.12.003
Received 7 March 2015; Received in revised form 29 October 2016; Accepted 14 December 2016
2212-3717/ 2016 The Authors. Published by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/BY-NC-ND/4.0/).

Water Resources and Industry 17 (2017) 16

M. Sarkar et al.

2.5. Digestion of sample and heavy metal analysis


An aliquot of 100 ml of each sample for heavy metal analysis
(specically, Cr & Cu) was taken in a 100 ml of Pyrex volumetric ask.
Then 1.0 N concentrated HCl (9 ml) was added followed by 1.0 N
concentrated nitric acid (3 ml). The content of the volumetric ask was
carefully heated in sand bath nearly to dryness in fume hood. After
cooling the volumetric ask at room temperature, deionized water was
added to the sample up to the mark of ask. Then, the sample was
ltered through a nylon membrane lter (Whatman, pore size 0.8 m,
diam. 47 mm) and the ltrate was collected in a 250 ml screw cap
plastic bottle (Type- HDPE container, LDPE-lined Polypropylene Cap,
Brand-Thermo Scientic). Finally, they were preserved for the determination of Cr and Cu. The AAS was calibrated for all the metals by
running dierent concentration of standard solutions. Average values
of three replicates were taken for each determination. The detection
limit for Cr and Cu was 0.003 mg/l. The euent after ltration process
was directly determined by AAS.

Fig. 1. Water Hyacinth (E. crassipes).

CuSO45H2O was taken and diluted to 500 m1. These standard


solutions were used in ltration process. All chemicals were purchased
from Kanto Chemical Co. Japan required for using AASpectrophotometer.

2.6. Treatment process


Filtering column was made of Pyrex glass tube of 1.5 cm inner
diameter and 50 cm height. The experiment was conducted with
vertical down ow fashion. An amount of 2.0 g WHSP was less tightly
packed in a column up to 15 cm height between 2 cm supporting layer
of glass wool per 500 ml solution. The adsorption eect was observed
for 472.56 mg/l Cr and 482.06 mg/l Cu concentrated standard solution
(SS) and 10.4749 mg/l Cr and 2.445 mg/l Cu concentrated tannery
euent (TE). The study was conducted at room temperature (28
2 C) and pH of Cr and Cu SS as well as TE was 7.4 0.2. Inlet of the
column was connected to the 1.0 l feed bucket with the plastic tubing.
The solution was passed through the WHSP column by gravimetric
ow. After passing through the column, the samples were collected at
every 1 min interval for rst 20 min and then 5 min interval up to 1 h.
For second hours samples were collected after 10 min interval and
30 min interval for third hours. The ow rate was maintained through
the experiment using an equipped with a stopper. The TE was collected
after 1 min interval for rst 20 min and then 10 min interval up to one
hour, 20 min interval for second hour and 30 min interval for third
hour. All samples (Eluate) solutions were collected at the bottom of the
column. The residual concentration of Cr and Cu was analyzed using
AAS. The schematic diagram of ltration process is shown in Fig. 3.

2.2. Preparation of adsorbent


The adsorbent materials Water Hyacinth (Fig. 1) were collected
from a basin of suburb Konapara, near Dhaka city. After collecting the
adsorbent materials were transported to the laboratory. The shoot of
the Water Hyacinth weed was segregated from rest parts and washed
ten times by deionized water, cut into small pieces and dried in sunlight
for 72 h. After sun drying the small spices of shoot were dried in oven
at 70 5 C for 48 h and grind by mortar. The shoot particles were
sieved and a certain size 150 m was collected and stored in a plastic
bottle for further use.

2.3. Sampling
After chrome tanning, the tannery euent is drained out into the
Buriganga River along with household euent in the same drain. The
samples were collected from that drain at Kalunagar in Hazaribagh
thana (Fig. 2) in non transparent plastic bottle. Some physicochemical
parameters like color, pH, TDS, EC and DO were recorded instantly
and the samples were transported to the laboratory as soon as possible.
After that COD was measured in the laboratory. The collected sample
were stored into separate plastic container previously washed with 2%
(v/v) HNO3 and stored by adding 10 ml of 0.1 N HNO3 per litter to the
euent to prevent the growth of microbial bacteria. Then the sample
was sealed to prevent air oxidation and stored in a refrigerator to
prevent the microbial decomposition of organic and inorganic compounds present in the euent. All the experimental solutions were
brought to room temperature before use.

2.7. Data analysis


The percentage of adsorption of Cr and Cu was calculated according
to the following equation:

Removal% = (Co Ce)/Co *100


Where Co is the initial Cr and Cu ion concentration (mg/l) and Ce is the
nal Cr and Cu ion concentration (mg/l).

2.4. Sample analysis


3. Results and discussion
Samples were analyzed in the Inorganic Research laboratory,
Department of Chemistry, Jagannath University. Color was observed
through eye sight. pH, EC, TDS and DO were measured instrumentally
and COD was measured by condensation and potassium dichromate
oxidation. The EC and TDS parameters were measured by using CTS406K model meter, Taiwan; pH was measured by using Twin, B-221
pH meter, Horiba, Japan and DO was measured by using YK-22
model meter, Taiwan. Heavy metal concentration was determined by
SHIMADZU, AA-7000 Shimadzu Corporation, Japan model atomic
absorption spectrometer.

3.1. Physicochemical parameters of euent


Physicochemical parameters of TE were analyzed before adsorption
through enormous laboratory analysis and the quality of the raw euents is
shown in Table 1. Here, we found that the euent was slightly basic in
nature and the other parameters such as TDS, EC and COD were also very
high which indicate that the euent sample collected from the drain at
Kalunagar in Hazaribagh thana was highly polluted. The collected samples
were deep blue in color due to the use of copper salt for chrome tanning.

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M. Sarkar et al.

O
CH3
O

Cr
O

+ -CH3

+ Cr3+
H3C

O
H3C

H
O

O
O

Cu

CH3
O

O
+ Cu2+

H3C

O
H

+ -CH3

O
H3C

H
O

3.2. Characterization of adsorbent


WHSP are shown in following Fig. 4. The OH band was found at
3422 cm1, the C-H stretch for methylene was found at 2921 cm1. C-O
stretching vibration of ester was observed at 1250 cm1 [15,16]. Beside
these N-H bend for amines spectrum was observed at 1635 cm1, -CH3
bend for alkanes was observed at 1431 cm1. After adsorption most of

Pressed KBr pellets were prepared by grinding sample with KBr in


1.0% w/w ratio. FT-IR spectra were recorded with IRPrestige-21
(Shimadzu, Japan) spectrophotometer in the range 4000400 cm1.
The comparative FT-IR spectrum of before and after adsorption on

Fig. 2. Map of Hazaribagh thana and viewing its location.

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M. Sarkar et al.

Fig. 5. SEM image of WHSP.


Fig. 3. Schematic representation of column.

Table 1:
Physicochemical parameters of untreated tannery effluent.
Parameters

Value

Color
Odor
pH
Cr Conc. (mg/l)
Cu Conc. (mg/l)
TDS (mg/l)
EC (mS) at 28 C
DO (mg/l)
COD (mg/l)

Deep blue
Acrid
7.4
10.475
2.445
13350
61.94
0.3
3460

*TDS=Total Dissolve Solid, EC=Electrical Conductivity, DO=Dissolve Oxygen, COD=Chemical Oxygen Demand.
Fig. 6. Cr conc. Vs. time plot for standard solution (SS).

Fig. 7. Cr conc. Vs. time plot for tannery euent (TE).

the adsorption bands shifts or decreases their intensity. The slight


changes occur in the bands of FT-IR spectra of the WHSP adsorption
peak due to the binding of the metal ions on the active sites [17]. After
Cr and TE adsorption the band at 1250 cm1 and 1383 cm1 were
disappeared whereas, after Cr SS adsorbed, a new band at 1150 cm1
instead of 1250 cm1 is appeared. Similarly, in case of Cu adsorption,
two new band at 1163 and 1110 cm1 are appeared instead of

Fig. 4. FTIR spectrum of before and after adsorption of Cu and Cr on WHSP from
bottom to up: a) before adsorption b) After Cr adsorption Cr c) After Cu adsorption d)
after passing euent.

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M. Sarkar et al.

Fig. 11. Removal % Vs. Time plot for Cr from TE.

Fig. 8. Cu conc. Vs. time plot for standard solution (SS).

Fig. 12. Removal % Vs. Time plot for Cu from SS.

Fig. 9. Cu conc. Vs. time plot for tannery euent (TE).

Fig. 13. Removal % Vs. Time plot for Cu from TE.

that Cr3+ and Cu2+ replace the CH3 group and form COOCr and
COOCu and hence C-O band at 1250 cm1 disappeared.
Fig. 10. Removal % Vs. Time plot for Cr from SS.

3.3. Morphological study


1250 cm1. It is suspected that due to chemisorption the band at
1250 cm1 is disappeared. The spectra after adsorption obtained with
decreasing the intensity indicate physical adsorption predominately
occurred. DellaGrece et al., (2009), [18] showed that, E. crassipes
composed of a chemical structure as -COOCH3. Thereby, we suspect

SEM image of WHSP was taken by and electron microscope


(model-SSOQLD9111, Netherland). For SEM image pellets were prepared by an apparatus using only hand pressure. The SEM image of
WHSP in Fig. 5 shows the rough surface area which is suitable for
adsorption.
5

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M. Sarkar et al.

3.4. Removal of Cr and Cu

Acknowledgements

The removal of Cr using SS and TE through the ltration column of


WHSP at predetermined time interval is shown in Figs. 6 and 7,
respectively. Within 10 min time, WHSP showed the highest removal
capacity of Cr for SS. This could be attributed to the availability of more
number of adsorption sites. Availability of specic surface area on
adsorbent plays a vital role for the surface metal adsorption process
[19-21]. With progress of time the adsorption capacity of WHSP will
decrease due to saturation resulting into high concentration of metal
ion in eluent. This might be attributed to the fact that each adsorbent
has a specic active surface site that would saturated at a certain
adsorbent concentration [22]. In case of TE, WHSP took higher time
for obtaining saturation (Fig. 7). This might be attributed that in TE,
there were present dierent metals and reactive dye. As dierent
metals and dyes have dierent reactivity order and atomic size, thereby
competition may occur towards the adsorbent sties [23]. Therefore, the
smallest metal or dye ion adsorbed rst than bigger sized one. This
might be the reason for delaying the saturation state of xed bed
column in case of TE.
Similarly, in case of Cu, within 14 min time, ltration column of
WHSP shows the highest removal capacity. However, we found, about
99.96% Cu was removed within 14 min (Fig. 8). After reaching
minimum Cu concentration of eluate solution in 14 min, Cu concentration in elutes solution is being to increase after that time. In case of
Cu, we nd that sharp removal capacity of Cu as time progressed
(Fig. 9). The removal of Cu is continued up to three hours. Such long
time might be taken due to the presence of ion competition among the
metals and also, dye ions in the tannery euent towards active site of
WHSP adsorbent [23].

We gratefully acknowledge the support of Inorganic research


laboratory, Jagannath University and nancial support of the
Jagannath University Development Project on the Pollution of the
Buriganga River.
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3.5. Removal percentage of Cr and Cu


The percentage of Cr removal from SS and TE depicted in Figs. 10
and 11, respectively. In case of SS, 99.8% Cr was removed within
13 min time but after 13 min the removal percentage decreases and fall
at 68.9% up to 3 h (Fig. 10). This may be occurred for the saturation of
active site. In case of TE, 98.8% Cr was removed at 3 h period (Fig. 11).
Figs. 12 and 13 represents the percentage of Cu removal from SS
and TE, respectively. In case of SS, Cu shows the highest removal
percentage (99.9%) within 14 min but after that the removal eciency
decreases and fall at 64.8% up to 3 h (Fig. 12). In case of TE, 99.6% Cu
was removed at 3 h period.

4. Conclusion
The aim of this present study is to establish a locally available and
economically viable adsorbent for the removal of Cr and Cu from
aqueous solution. The nding indicates that Cr and Cu removing
capacity of WHSP were satisfactory. The study also depicts that raw
WHSP can remove about 99% Cr and Cu from SS as well as TE. Thus
WHSP is a potential adsorbent which can be used as alternative in the
sustainable Cr and Cu removal technology for wastewater purication
system.