Water Resources and Industry 17 (2017) 16

Contents lists available at ScienceDirect

Water Resources and Industry

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

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

shoot powder

M. Sarkara, , A.K.M.L. Rahmana, N.C. Bhoumikb
a
Department of Chemistry, Jagannath University, Dhaka 1100, Bangladesh
b
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: Tannery euent characterization and removal eciency of Chromium (Cr) and Copper (Cu) on water hyacinth
Adsorbent has been observed by ltration process. The euent was contaminated by deep blue color, acidic pH, higher
Water hyacinth value of total dissolve solid (TDS), electrical conductivity (EC), chemical oxygen demand (COD) and lower value
Tannery euent of dissolve oxygen (DO). After ltration, the euent shows that the permissible limit of investigated metals.
Physicochemical parameters, ltration
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 pretreat-
ment 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 indus-
tries, paints, pigments, printing and graphics, waste disposal, agricul-
tural 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 pretreat-
ment. Heavy metals released from dierent sources into the environ-
ment 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, environmen-
tally 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 through-
out 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/).
M. Sarkar et al.
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 AA-
Spectrophotometer.
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 com-
pounds present in the euent. All the experimental solutions were
brought to room temperature before use.
2.4. Sample analysis
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 CTS-
406K 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.
2
Water Resources and Industry 17 (2017) 16
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 deter-
mination 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.
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.
2.7. 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).
3. Results and discussion
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.
M. Sarkar et al. Water Resources and Industry 17 (2017) 16

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

Table 1:
Physicochemical parameters of untreated tannery effluent.

Parameters Value

Color Deep blue

Odor Acrid
pH 7.4
Cr Conc. (mg/l) 10.475
Cu Conc. (mg/l) 2.445
TDS (mg/l) 13350
EC (mS) at 28 C 61.94
DO (mg/l) 0.3
COD (mg/l) 3460

*TDS=Total Dissolve Solid, EC=Electrical Conductivity, DO=Dissolve Oxygen, COD=-

Chemical Oxygen Demand.

(Shimadzu, Japan) spectrophotometer in the range 4000400 cm1.

Fig. 3. Schematic representation of column.
3.2. Characterization of adsorbent
Pressed KBr pellets were prepared by grinding sample with KBr in
1.0% w/w ratio. FT-IR spectra were recorded with IRPrestige-21
The comparative FT-IR spectrum of before and after adsorption on
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
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

3
M. Sarkar et al. Water Resources and Industry 17 (2017) 16

Fig. 5. SEM image of WHSP.

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)
respectively. Within 10 min time, WHSP showed the highest removal
after passing euent.
capacity of Cr for SS. This could be attributed to the availability of more
number of adsorption sites. Availability of specic surface area on
instead of 1250 cm1 is appeared. Similarly, in case of Cu adsorption,
adsorbent plays a vital role for the surface metal adsorption process
two new band at 1163 and 1110 cm1 are appeared instead of
[19-21]. With progress of time the adsorption capacity of WHSP will
1250 cm1. It is suspected that due to chemisorption the band at
decrease due to saturation resulting into high concentration of metal
1250 cm1 is disappeared. The spectra after adsorption obtained with
ion in eluent. This might be attributed to the fact that each adsorbent
decreasing the intensity indicate physical adsorption predominately
has a specic active surface site that would saturated at a certain
occurred. DellaGrece et al., (2009), [18] showed that, E. crassipes
adsorbent concentration [22]. In case of TE, WHSP took higher time
composed of a chemical structure as -COOCH3. Thereby, we suspect
that Cr3+ and Cu2+ replace the CH3 group and form COOCr and
COOCu and hence C-O band at 1250 cm1 disappeared.
O
O
CH3 Cr
O O
O O

+ Cr3+ + -CH3
O O
O O
H3C H
H3C H
O
O O
O
O
O Cu
CH3
O
O
O O

+ Cu2+ + -CH3
O O
O O
H3C H
H3C H
O
O O
O

3.3. Morphological study
SEM image of WHSP was taken by and electron microscope
(model-SSOQLD9111, Netherland). For SEM image pellets were pre-
pared 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.
3.4. Removal of Cr and Cu
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,
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 concen-
tration 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

4
M. Sarkar et al. Water Resources and Industry 17 (2017) 16

Fig. 6. Cr conc. Vs. time plot for standard solution (SS).

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

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

Fig. 10. Removal % Vs. Time plot for Cr from SS.

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

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

(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].

3.5. Removal percentage of Cr and Cu

The percentage of Cr removal from SS and TE depicted in Figs. 10 Fig. 11. Removal % Vs. Time plot for Cr from TE.

5
M. Sarkar et al.
Fig. 12. Removal % Vs. Time plot for Cu from SS.
Fig. 13. Removal % Vs. Time plot for Cu from TE.
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.
Acknowledgements
We gratefully acknowledge the support of Inorganic research
Water Resources and Industry 17 (2017) 16
laboratory, Jagannath University and nancial support of the
Jagannath University Development Project on the Pollution of the
Buriganga River.
References
[1] M. Sarkar, A.K.M.L. Rahman, J.B. Islam, K.S. Ahmed, M.N. Uddin, N.C. Bhoumik,
Study of hydrochemistry and pollution status of Buriganga river, Bangladesh,
Bangladesh J. Sci. Ind. Res. 50 (2) (2015) 123134.
[2] K.S. Ahmed, A.K.M.L. Rahman, M. Sarkar, J.B. Islam, I.A. Jahan,
M. Moniruzzaman, B. Saha, N.C. Bhoumik, Assessment on the level of contam-
ination of Turag river at Tongi area in Dhaka, Bangladesh J. Sci. Ind. Res. 51 (3)
(2016) 193202.
[3] J.B. Islam, M. Sarkar, A.K.M.L. Rahman, K.S. Ahmed, Quantitative assessment of
toxicity in the Shitalakkhya River, Bangladesh, Egypt. J. Aquat. Res. 41 (1) (2015)
2530.
[4] A. Blazquez, M.A. Martin, M.C. Lara, R. Marti, Y. Campos, A. Cabello, A. cabello,
R. Garesse, J. Bautista, A.L. Andreu, J. Arenas, Removal of cadmium ions with olive
stones: the eect of some parameters, Process Biochem. 40 (8) (2005) 26492654.
[5] C. Modrogan, A.R. Miron, O.D. Orbulet, C. Costache, M. Anghel, Hexavalent
chromium removal from wastewaters, Bull. UASVM Agric. 68 (2) (2011) 94.
[6] Z. Aksu, I.A. Isoglu, Removal of copper (II) ions from aqueous solution by
biosorption onto agricultural waste sugar beet pulp, Process Biochem. 40 (2005)
30313044.
[7] A. Ozer, D. Ozer, A. Ozer, The adsorption of copper (II) ions onto dehydrated wheat
bran (DWB): determination of the equilibrium and thermodynamic parameters,
Process Biochem. 39 (2004) 21832191.
[8] B. Volesky, Biosorption of metal recovery, Trends Biotechnol. 5 (1987) 96101.
[9] M. Sarkar, J.B. Islam, S. Akter, Pollution and ecological risk assessment for the
environmentally impacted Turag river, Bangladesh, J. Mater. Environ. Sci. 7 (7)
(2016) 22952304.
[10] R.S. Uang, R.C. Shiau, Metal removal from aqueous solution using chitosan-
enhanced membrane lteration, J. Mem. Sci. 165 (2) (2000) 159167.
[11] B.H. Hameed, J.M. Salman, A.L. Ahmad, Adsorption isotherm and kinetic
modeling of 2, 4-D pesticide on activated carbon derived from date stones, J.
Hazard. Mater. 163 (2009) 121126.
[12] S.E. Bailey, T.J. Olin, R.M. Bricka, D.D. Adrian, A review of potentially low cost
Sorbents for heavy metals, Water Res. 33 (1999) 24692479.
[13] S.H. Hasan, M. Talat, S. Rai, Sorption of cadmium and zinc from aqueous solution
by water hyacinth (Eichhornia crassipes), Bioresour. Technol. 98 (2007) 918928.
[14] Wm.T. Penfound, T.T. Earle, The biology of the water hyacinth, Ecol. Monogr. 18
(1948) 447472.
[15] M. Ibrahim, M. Abd-El-Aal, Spectroscopic study of heavy metals intereaction with
organic acid, Int. J. Environ. Pollut. 35 (2008) 99110.
[16] M. Ibrahim, A.J. Hameed, A. Jalbout, Molecular spectroscopic study of river Nile
sediment in the greater cairo revgion, Appl Spectr. 62 (2008) 306311.
[17] A. Babarinde, J.O. Babalola, J. Adegoke, A.O. Osundeko, T.J. Ibidapo,
C.A. Nwabugwu, O.F. Ogundimu, Kinetic, equilibrium and Thermodynamic studies
of the biosorption of Ni (II), Cr (III) and Co (II) from aqueous solutions using
cocoyam (Colocasia esculenta) leaf, Pac. J. Sci. Technol. 13 (2012) 272283.
[18] M. DellaGreca, L. Previtera, A. Zarrelli, Structure of new phenylphenalene-related
compounds from Eichhornia crassipes (water hyacinth), Tetrahedron 65 (39)
(2009) 82068208.
[19] Z. Zulfadhly, M.D. Mashitah, S. Bhatia, Heavy metals removal in xed-bed column
by the macro fungus Pycnoporus sanguineus, Environ. Pollut. 112 (3) (2001)
463470.
[20] U. Kumar, M. Bandyopadhyay, Fixed bed column study for Cd (II) removal from
wastewater using treated rice husk, J. Hazard. Mater. 129 (2006) 253259.
[21] S. Mandal, M.K. Sahu, R.K. Patel, Adsorption studies of arsenic (III) removal from
water by zirconium polyacrylamide hybrid material (ZrPACM-43), Water Resour.
Ind. 4 (2013) 5167.
[22] R. Gottipati, Preparation and characterization of micro porous activated carbon
from biomass and its application in the removal of chromium (VI) from aqueous
phase, 2012. Available at: http://ethesis.nitrkl.ac.in/4468/1/Ph.D_Thesis_
Ramakrishna_Gottipati_507ch001.pdf.
[23] F.D. Natale, A. Erto, A. Lancia, D. Musmarra, Experimental and modeling analysis
of As (V) ions adsorption on granular activated carbon, Water Res. 42 (2008) 89.