Journal of Water Process Engineering 31 (2019) 100839

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Journal of Water Process Engineering

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Removal of metals (Pb, Cd, Cu, Cr, Ni, and Co) from drinking water by T
oxidation-coagulation-absorption at optimized pH
⁎
Anup Jyoti Bora, Robin Kumar Dutta
Department of Chemical Sciences, Tezpur University, Napaam, Tezpur 784028, Assam, India

A R T I C LE I N FO A B S T R A C T

Keywords: Removal of some metals, viz., Cd, Pb, Ni, Cr, Cu, and Co by oxidation-coagulation-adsorption at optimized pH
Heavy metals removal (OCOP), an efficient and low cost method for simultaneous removal of As, Fe and Mn from groundwater has been
Oxidation-coagulation-adsorption studied. NaHCO3, KMnO4 and FeCl3 are used in OCOP as pH conditioner, oxidant and coagulant, respectively.
NaHCO3 The effects of variation of initial concentration and residence time on the removal of the heavy metal ions have
KMnO4
also been studied. The removal of the chosen metals from initial concentration of 2 mg/L by the method has been
FeCl3
found to increase in the order Cd (79.0%) < < Co (94.8%) < Ni (94.4%) < < Cu (98.0%) < Cr (98.3%) < Pb
(99.5%). Analyses by atomic adsorption spectrophotometer, Energy dispersed X-ray spectrophotometer and
powder X-ray diffraction indicate adsorption of the heavy metals on the surface of coagulates/precipitates as
oxides and complexes of the heavy metals. The highly active absorber coagulates/precipitates formed in FeOOH,
5Fe2O3.9H2O, MnO2, and Mn3O4, also strongly adsorb other metals in addition to removal by precipitations of
oxy-complexes in cases of Cd and Pb. The relatively lower removal of Cd has been attributed to its soft acidic
nature and higher removal of Cr is due to its hard acidic nature. The present study shows that the OCOP method
is capable of removing the heavy metals of Cd, Pb, Ni, Cr, Cu and Co, very well, in addition to efficiently
removing As, Fe and Mn from water.

1. Introduction Several metals concern us because of occupational or residential

Groundwater is the vital resource, necessary for all aspects of
mankind and ecosystem survival [1]. One of the most imperative en-
vironmental issues today is ground water contamination and among the
wide diversity of contaminants affecting water resources, heavy metals
receive particular concern considering their strong toxicity even at low
concentrations [2]. Metals or elements with an atomic density greater
than 6 g/cm3 are heavy metal which is one of the most tenacious pol-
lutants found in groundwater [3]. Unlike organic pollutants, the ma-
jority of heavy metals do not degrade and accumulate throughout the
food chain, producing potential risk to human health risks and ecolo-
gical balance [3,4]. Some metals generally exists nature due to erosion
and weathering of parent rocks spread into groundwater [5]. Release of
leachates in to groundwater from domestic and industrial solid waste is
another source of metal ion contamination in groundwater [5]. In-
dustries like metal plating, mining operations, fertilizer industries,
tanneries, batteries, paper industries and pesticides, pharmaceuticals,
hospitals, etc., directly or indirectly discharge heavy metal wastewaters
into the environment especially in developing countries polluting sur-
face water and groundwater [6,7].
exposure [8]. Although small amounts of these are common in our
environment and diet and some of them are necessary for good health,
large amounts of most of them may cause acute or chronic toxicity [8].
The common hazardous metals found in groundwater are As, Fe, Mn,
Hg, Pb, Cr, Cd, Ni and Cu [4,9–11]. Presently India is facing critical
water supply and drinking water quality problems. There is evidence of
prevailing contamination of water resources by heavy metals in many
areas of India [10]. The concentrations of metals in the surface water of
the river Ganga in West Bengal is reported to follow the order: Fe >
Mn > Ni > Cr > Pb > Zn > Cu > Cd [10]. The problem of ar-
senic and other heavy metals in groundwater and related health ha-
zards in Assam, a north-eastern state of India, is now receiving wide
attention [9]. Borah et al. reported that the ground water of the tea
garden belt of Darrang district of Assam is contaminated with cadmium,
lead, iron and manganese [12,13]. Buragohain et al. studied the sea-
sonal variations of heavy metals of groundwater in Dhemaji district
Assam and found the concentrations of aluminium, lead and cadmium
to be significantly elevated [14]. Singh reported very high arsenic
contamination in groundwater of Jorhat, Golaghat, and Lakhimpur
districts in Assam [15]. A high percentage of iron contamination (77%)

⁎
Corresponding author.
E-mail address: robind@tezu.ernet.in (R.K. Dutta).

https://doi.org/10.1016/j.jwpe.2019.100839
Received 24 December 2018; Received in revised form 23 March 2019; Accepted 21 April 2019
2214-7144/ © 2019 Published by Elsevier Ltd.
A.J. Bora and R.K. Dutta
Fig. 1. Plots of remaining concentrations of Cd, Pb, Ni, Cr, Cu, and Co in mg/L (primary Y-axis, closed diamond-♦) and % of removal (secondary Y-axis, open circle-
○) against initial concentration in mg/L after OCOP treatment.
in the tube well waters of the region indicates the severity of the heavy
metal pollution in the region [15].
Among the chemical contaminants of groundwater, arsenic has be-
come a major threat to the life of human being and useful micro-
organisms [16]. Manganese and iron are essential elements to a certain
level only but they are also unwanted due to aesthetic, plumbing or
health problems at higher concentrations [17,18]. Excessive con-
centrations of lead, cobalt, cadmium and nickel can cause variety of
harmful health effects even sometime cause death [19]. Cd (II) is a
potent neurotoxic metal and is known to cause kidney damage, renal
dysfunction, bone degeneration, lung inefficiency, liver damage and
hypertension in humans [20]. Though Cobalt (Co) is a key constituent
of cobalamin (vitamin B12); the excess intake of Co results toxic, car-
cinogenic and mutagenic effects on human health [19]. Excess con-
centration of hexavalent chromium (Cr (VI)) found in groundwater is
acutely toxic, carcinogenic, mutagenic and teratogenic [21–24]. In-
gestion of copper at high dose causes health effect on human body such
as lesions in the central nervous system, and liver and kidney damage or
Wilson’s disease [25]. Lead poisoning through drinking water in human
body causes damage of kidney, liver and brain, nervous system, re-
productive system, and causes anaemia, sickness or death [26]. Severe
exposure to lead has been associated with sterility, abortion, stillbirth
and neonatal deaths [27]. Nickel exposure to drinking water causes
allergic skin reaction, weight gain, weakness, and damage to lungs, the
nervous system and mucous membranes [28].
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Journal of Water Process Engineering 31 (2019) 100839
It is utmost necessary to remove heavy metals stated above from
groundwater before drinking. The World Health Organisation (WHO)
sets guideline values of the heavy metals of Pb, Cr, Ni, Cu and Cd as
0.01 mg/L, 0.05 mg/L, 0.07 mg/L, 2.0 mg/L, 0.003 mg/L, respectively,
for drinking water [29–33].
Among various processes reported for arsenic removal, process
based on adsorption, oxidation, coagulation, ion-exchange, electro-
coagulation, application of nanomaterials, etc., are commonly used
[34]. Kamaraj et al. reported that electrocoagulation process for the
removal of Pb2+ from water using magnesium and galvanized iron as
anode and cathode results in maximum removal efficiency of 99.3% at a
pH of 7.0 at a current density 0.8 A/dm2 with an energy consumption of
0.72 kW h/m3 [35]. Ion exchange is also a frequently used method to
remove metal ions from contaminated water [36]. In hydroxide pre-
cipitation process, the incorporation of coagulants like iron salts, alum
and some polymers may improve heavy metal separation from waste-
water and groundwater [36]. Electrocoagulation/electro-floatation/
electrodeposition is good process however they need application of
current with electrodes increasing the cost of the process for heavy
metals removal [36,37]. Amuda et al. reported that addition of ferric
chloride alone results significant removal of total Cr up to 91% which is
increased to 95% on addition of polymer with ferric chloride [38].
Activated carbon and carbon nanotubes (CNT) have also been used as
adsorbent to remove heavy metals from water. Li et al. achieved 74.8%
removal efficiency of Cu by using CNTs and 83.3% by using CNTs/AC
A.J. Bora and R.K. Dutta
Fig. 2. Plots of remaining concentrations of Cd, Pb, Ni, Cr, Cu, and Co in mg/L measured after varying residence time in hour at initial concentration of 5 mg/L in
OCOP treatment.
from initial Cu2+ concentration of 20 mgL−1 at pH 5.0 and adsorbent
dose of 0.05 g [39].
Using chemically enhanced primary treatment with 40 mg/L of
FeCl3 and 0.5 mg/L of anionic polymer stretches the best removal of
chromium, copper, nickel, lead and zinc. This study by Johnson, et al.
(2008) [40] showed ferric chloride to be more effective than alum for
metal ion capture from wastewater. Aziz, et al. (2008) investigated that
more than 80% of Cd, Pb, Zn, Ni, Cu and Cr(III) with an initial con-
centration of 2 mg/L can be removed by limestone at a final pH of 8.5
[41]. Hydroxide precipitation process using Ca(OH)2 and NaOH in re-
moving Cu and Cr(III) ions from wastewater was evaluated by Mirba-
gheri and Hosseini (2005) [42]. Maximum precipitation of Cr (III) oc-
curred at pH 8.7 with the addition of Ca(OH)2 and the concentration of
chromate was reduced from 30 mg/L to 0.01 mg/L. The Cu was re-
moved by aeration and at an optimum pH of about 12.0 by Ca(OH)2 and
NaOH from 48.51 mg/L to 0.694 mg/L [43]. In hydroxide precipitation
process, the addition of coagulants such as alum, iron salts, and organic
polymers can enhance the removal of heavy metals from wastewater.
Zouboulis and Katsoyiannis (2002) [44] showed the coagulation by
alum or ferric chloride to be enhanced by some organic polymers for
99% removal of arsenic.
Though there are some successful methods for removal of different
heavy metals from water, they cannot efficiently remove arsenic pre-
sent as unionised H3AsO3 at normal pH. Ion exchange method also
removes heavy metals very well but the process needs high-cost resin
effective under specific conditions and electricity to push the inlet
water with required force. Moreover, as such, ion exchange cannot
remove arsenic present as unionised H3AsO3 at normal pH. Though
reverse osmosis (RO) can remove all dissolved contaminants from
water, it is unsuitable for treatment of water with moderate or low total
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Journal of Water Process Engineering 31 (2019) 100839
dissolved substance. In addition to that, RO is a costly method and
cannot be used without electricity. Thus, a simple method which can
remove the heavy metals together with As at an affordable cost without
needing electricity is not available.
A low-cost, efficient and safe method for removal of arsenic based
on oxidation-coagulation-adsorption at optimized pH (OCOP) with easy
operational procedure, reported by our research group, efficiently re-
moves Fe and Mn also simultaneously along with As [45–47]. The
OCOP method which involves addition of small doses of NaHCO3,
KMnO4 and FeCl3 to the contaminated water as pH-conditioner, oxidant
and coagulant, respectively, has been gaining popularity in India,
especially in rural Assam [46]. A modified OCOP by our research group
[37] and another method based on sequential addition of permanganate
and ferric iron by Ahmad et al 2018 [48], have shown removal of ar-
senic to undetectable level or below 1 μg/L.
The OCOP method was also reported to reduce the concentrations of
certain heavy metal ions such as iron, and manganese in the treated
water [49,50]. However, the removal of the other commonly found
heavy metals by the OCOP method was not studied in detail. Though,
similar methods, based on coagulation and adsorption are capable of
removing the heavy metals to satisfactory level, it will be better to have
a single method capable of removing heavy metals also along with ar-
senic. Thus, considering the relevance of a low-cost and simple method
that can comprehensively remove the heavy metals together with As in
arsenite state and the increasing popularity of the OCOP method for
removing As and Fe, it was thought worthwhile to carry out a detail
study of removal of the other heavy metals by the OCOP method.
Though oxidation may not be necessary for removal of some of the
heavy metals, we have retained the dose of KMnO4 for all of the chosen
heavy metals in order to examine their removal simultaneously along
A.J. Bora and R.K. Dutta Journal of Water Process Engineering 31 (2019) 100839

Fig. 3. Plots of concentration of the Cd, Pb, Ni, Cr, Cu, and Co against initial concentrations in mg/L found in the aqua-regia extract of coagulates obtained from the
OCOP experiments (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article).

Fig. 4. Plot of sum of concentrations of the metal in filtrate and in the extract of coagulate against the initial concentrations of Cd, Pb, Ni, Cr, Cu, and Co, respectively.
Experimental error limits: Cd (1.16%), Pb (1.14%), Ni (3.34%), Cr (0.91%), Cu (0.91%) and Co (3.36%).

4
A.J. Bora and R.K. Dutta
Fig. 5. EDX spectra of the solids obtained after OCOP treatment for removal of Cd, Pb, Ni, Cr, Cu and Co with initial concentrations of 5 mg/L.
with arsenic, iron and manganese in a single OCOP process. Removal of
six common heavy metals, viz, Pb, Cd, Cu, Cr, Ni, and Co is included in
this study.
2. Materials and method
2.1. Reagents
NaHCO3, FeCl3, KMnO4, FeSO4.7H2O, CuSO4.5H2O, CdCl2,
Cr2(SO4)3.6H2O, CoCl2.6H2O, NiCl2.6H2O and PbSO4, obtained from
Merck Specialities Private Limited, India, were of analytical grade and
used without further purification. Stock solutions of 1.0 g/L Cu2+,
Cd2+, Cr3+, Co2+, Ni2+ and Pb2+ were prepared by spiking tap water
with CuSO4.5H2O, CdCl2, Cr2(SO4)3.6H2O, CoCl2.6H2O, NiCl2.6H2O
and PbSO4, respectively. The approximate composition of the tap water
can be seen elsewhere [45,46]. Synthetic groundwater containing these
ions was prepared by mixing required volume of the freshly prepared
stock solutions with tap water. The stock solutions of 1.0 g/L FeCl3,
1.0 g/L KMnO4 and 9.0 g/L of NaHCO3 were prepared in doubly dis-
tilled water.
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Journal of Water Process Engineering 31 (2019) 100839
2.2. Instrumental analysis
The pH of the experimental water samples were measured in the
laboratory and in field using a multi parameter kit (model 5Star
pH.ISE.Cond.DO Benchtop, Orion, USA) and a pocket-sized pH metre
(model PH-222, Lutron Electronic Enterprise CO., LTD, Taiwan), re-
spectively. The concentrations of the heavy metals in influent and ef-
fluent water were determined using an Atomic Absorption
Spectrophotometer (AAS, model Analyst 200, Thermo iCE 3000 series,
USA) coupled with a hydride vapour generator (model VP100). The X-
ray spectra of coagulates or precipitates were recorded on a powder X-
ray diffractometer (XRD) model Miniflex, Rigaku, Japan with graphite
mono-chromated CuKa radiation (0.15 nm) at 30 kV and 15 rnA using a
scanning rate of 0.0500 /s. The Energy Dispersive X-ray Spectra (EDX)
were recorded on a Jeol Scanning Microscope model JSM 6390 L V at
room temperature at an accelerating voltage of 15.0 kV.
2.3. Experimental procedure
In this study a series of OCOP experiment with fixed doses of
A.J. Bora and R.K. Dutta
Fig. 6. XRD patterns of the coagulates obtained when treated water contains initial concentration of (a) Cd, (b) Pb, (c) Ni, (d) Cr, (e) Cu and (f) Co respectively.
NaHCO3, FeCl3 and KMnO4 was carried out in 1.5 L mug. A set of ex-
periments with variation of initial concentration of the metals is ver-
ified to see the capacity of removal of the selected metals by OCOP. The
initial concentrations of the metals were examined in the range from
2 mg/L to 10 mg/L with a fixed treatment time of 2 h. To each mug,
100 mg, 0.5 mg and 25 mg of aqueous 9% NaHCO3, 5% KMnO4 and
25% FeCl3, respectively, were added successively with gentle inter-
mittent stirring. After that the treated water was allowed to coagulate
and settle down. NaHCO3 was added to the solutions in two steps.
Initially about 60 mg/L of NaHCO3 was added to increase initial pH of
the treated water to approximately 8.5( ± 0.1) which provides a fa-
vourable condition for KMnO4 to oxidise the heavy metals forming itself
to MnO2. NaHCO3 was added again after addition of FeCl3 to adjust the
final pH at approximately 7.3( ± 0.1). The OCOP experiments with
variation of initial metal ion concentration and with variation of re-
sidential time were done in triplicates to check reproducibility and data
presented are averages of three.
The top clear water was then filtered through Whatman 42 filter
paper. Another set of experiment with mug containing 1 L synthetic
contaminated water with a fixed 5 mg/L initial concentrations of each
of Cu(II), Cr(VI), Ni(II), Cd(II), Pb(II), and Co(II), respectively, in se-
parate mugs. The filtrate was collected after varying residence time
from 1 to 4 h. All the filtrates obtained after the experiments were
analysed by AAS to determine the remaining concentrations of the
heavy metals. The filtrates were preserved after acidifying with HCL
acid to keep the pH below 2 for determination of metal ion con-
centrations by AAS. The solids obtained during the OCOP experiments
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Journal of Water Process Engineering 31 (2019) 100839
were collected in petri dish after filtration, allowed to dry in hot air
circulating oven at 70 °C for 5 min and kept overnight in a desiccator at
room temperature. Finally, solid powder samples were prepared by
grinding the dried solid with the help of a glass mortar.
3. Results and discussions
3.1. Removal of the heavy metals
Fig. 1 shows removal of the hazardous heavy metal, namely, Cd, Pb,
Ni, Cr, Co, and Co from contaminated groundwater with variation of
initial concentration of the metal ions from 2 mg/L to 10 mg/L. Inter-
estingly, all six metal ions have been found to be removed considerably
after the OCOP treatment. The percentage of removal of all heavy
metals increased with decrease in the initial concentration of the heavy
metals. The removal of the metals from equal initial concentration of
2 mg/L was found to increase in the order Cd (79.0%) < < Co
(94.8%) < Ni (94.4%) < < Cu (98.0%) < Cr (98.3%) < Pb (99.5%).
The removal of Pb is competitive with 99.3% reported with elec-
trocoagulation [35]. The observed 98.3% removal of total Cr is far
better than 91% reported with ferric chloride alone and 95% reported
with ferric chloride and polymer [37]. 98% Cu removal by the present
method is also far better than reported 74.8% removal with CNTs and
83.3% removal with CNTs/AC [39]. In OCOP method, the mild alkaline
pH provided by NaHCO3 may favour precipitation of the heavy metals
[36]. The present results are also better than reported 80% removal of
Cd, Pb, Zn, Ni, Cu and Cr (III) from an initial concentration of 2 mg/L by
A.J. Bora and R.K. Dutta
limestone, with a final pH of 8.5, which is in the higher side of the
acceptable range of pH for drinking water [41]. Thus, the OCOP
method, with a removal efficiency of 94.4–99.5% and with a final pH of
7.3, removes Cd, Pb, Ni, Cr, Cu and Co also very well from drinking
water.
The observed low removal of Cd may be attributed to weaker
binding/adsorption to oxygen of FeOOH coagulates or MnO2 pre-
cipitates formed during OCOP treatment due to its soft acidic nature
[50]. On the other hand Cr, being a hard acid [50], is removed very
well due to its strong binding FeOOH and MnO2. Further evidences are
required to explain the observed order of ease of removal of the other
heavy metal ions. The initial concentration ranges of the heavy metals
used in this study were above the concentration range in which they
occur in groundwater due to limitation of the atomic absorption spec-
trophotometer in detecting the metal ions in microgram per litre level.
However, the percentage removals of the metal ions were found to
increase gradually with decrease in initial concentrations of the metal
ions.
Pb and Cd are reported to be present up to 0.215 mg/L and
0.110 mg/L, respectively, in groundwater. Considering the percentage
removals of Pb and Cd to be at least equal to that observed at initial
concentration of 2 mg/L, the estimated remaining concentrations of the
metal ions after OCOP treatment are 0.001 mg/L and 0.024 mg/L
against their WHO guideline values of 0.01 mg/L and 0.003 mg/L, re-
spectively. The heavy metal ions of Pb, Cr, Cu, Ni and Cd are estimated
to be removed below their respective WHO guideline values from initial
concentrations of at least 2 mg/L, 7.5 mg/L, 80 mg/L, 0.81 mg/L and
0.014 mg/L, respectively. Literatures reveals that heavy metal con-
centration in natural groundwater is usually found below 2 mg/L
[28–33], and therefore the OCOP method, with 94.4–99.5% of removal,
is highly efficient for removal of heavy metals from groundwater. Thus,
OCOP is capable of removing Pb, Cr, Cu, Co and Ni to safe level from
their respective ranges of concentrations in which they generally occur
in groundwater except for Cd.
Fig. 2 shows the results of removal of these heavy metals from initial
concentration of 5 mg/L by OCOP method with variation of residence
time up to 4 h. Removal was found to increase with increase in re-
sidence time. The removal levelled off above 3 h for Cd and Co which is
the optimum residence time for most adsorption methods [51,52] but
continued to decrease up to 4 h in the case of Pb, Cr, Ni and Cu. This
experiment indicates that more residence time is required for maximum
removal of these heavy metal ions than that of 2 h, normally required
for OCOP treatment for removal of arsenic and iron.
3.2. Analysis of the precipitate
For AAS analysis of the heavy metals present in the coagulates of
OCOP, the solid obtained from the process was dissolved in aqua Regia
(mixture of nitric acid and hydrochloric acid, optimally in a molar ratio
of 1:3). The volume of each solution was adjusted to 1 L with distilled
water. Fig. 3 shows the plots of the concentrations of the heavy metals
in the aqua regia extract of coagulates obtained after the removal ex-
periment of heavy metals by OCOP at varying initial concentrations.
The concentrations of the heavy metals in the extracts of the solid ob-
tained in OCOP process have shown good correlation with the initial
concentrations of the heavy metals. Plot of sum of concentrations of the
metal in filtrate and in the extract of coagulate against the initial
concentrations of the metals have been shown in Fig. 4. It is interesting
to note that the sums of remaining concentration and the concentration
observed in the extract were in good agreement with the corresponding
initial concentrations for the heavy metal ions within experimental
error limits. The observed experimental error limits were 1.16, 1.14,
3.43, 0.91, 0.42, and 3.36 percent for Cd, Pb, Ni, Cr, Cu, and Co, re-
spectively. This indicates a very little escaping of detection by AAS by
any of the heavy metal.
The EDX estimation of the heavy metals in the solid obtained from
7
Journal of Water Process Engineering 31 (2019) 100839
the OCOP experiment with performed separately for individual metal
ions with initial concentration of the metal ions as 5 mg/L and re-
sidence time of 2 h are shown in Fig. 5. The spectra obtained for each
metal ion showed the presence of the respective elements. While the
percentage composition with respect to weight of the Cd, Pb, Ni, Cr, Cu
and Co in the precipitates or coagulates were 6.39, 21.82, 2.32, 2.13,
13.87 and 7.54 percent, respectively; the atomic percentage were 1.15,
2.33, 0.82, 0.70, 3.95 and 2.90 percent, respectively (Supporting In-
formation, Table S1). The observed disagreement in atomic percentage
may be attributed to difference in removal of the individual metal ions
and inhomogeneous nature of the mixtures.
The XRD pattern of the solid coagulates of OCOP method in the
absence of the heavy metals can be seen elsewhere [45] (Supporting
Information, figure S1). While the XRD pattern of the solid obtained from
OCOP treatment in the presence of Co (Fig. 6f) showed a highly
amorphous nature of the coagulated solid like that obtained in absence
of any of the heavy metals, the XRD spectra of the solids obtained in the
presence of Ni, Cr and Cu indicated formation of partially amorphous
solids, and the XRD patterns of the solid formed in the presence of Cd
and Pb indicated highly crystalline solids (Fig. 6a–f).
The XRD spectra with the plane value (h k l) of the solid coagulates
obtained in presence of the heavy metals with initial concentrations of
5 mg/L obtained during the present OCOP experiments are shown in
Fig. 6. The XRD of the solid obtained in the presence of Cd showed
sharp peaks at 2θ = 30.42 (1 0 3), 60.8 (2 1 5), and 63.07 (1 1 6) due to
Mn3O4 complex (JCPDS No: 652776; 800382, 652776; and 800382,
651298, respectively), as can be seen in Fig. 6a. Peaks observed at
2θ = 36.49 (4 0 0), 43.8 (4 0 1), 49.89 (3 0 2), and 58.1 (5 2 1) were
due to the presence of MnO2 compound in the coagulates (JCPDS No:
721982; 651298; 721982, 651298; and 530633, respectively). The
pattern at 2θ = 40.17 (2 1 0), 48.06 (4 1 1) and 75.12 (2 0 2) confirms
the existence of geothite, FeOOH (JCPDS No: 810464). Cadmium oxide,
CdO2 formation resembles with the XRD pattern at 2θ = 65.69 (3 2 1)
(JCPDS No: 781125) and complexes Cd0.1Mn0.9O and Cd2Mn3O8 also
resembles with XRD pattern at 2θ = 40.19 (2 1 0) (JCPDS No: 896000)
and 61.56 (3 3 1) (JCPDS No: 721428), respectively.
The XRD spectra of the solid obtained in the presence of Pb (Fig. 6b)
shows peaks at 2θ = 20.10 (1 1 0), 35.62 (1 1 0), 40.82 (1 1 3), 43.50 (1
1 4), 45.83 (1 3 3), 47.04 (2 1 3) and 49.04 (1 4 2) (JCPDS No: 897047;
898103, 898104, 897047; 898103, 897047; 898103, 897047; 897407;
897407; 897407; and 897407, respectively) as evidences of formation
of iron oxide, Fe2O3 in the solid. XRD peaks at 2θ = 34.65 (0 2 1)
(JCPDS No: 810463) indicates presence of goethite, FeOOH. XRD peak
at 2θ = 29.12 (1 0 0), 36.19 (2 0 0), 62.67 (3 1 1) and 64.10 (2 0 1)
(JCPDS No: 440872; 652873, 040686; 870663 and 440872, respec-
tively) are the evidences for the elemental precipitation/co-precipita-
tion of Pb with coagulates. XRD pattern at 2θ = 56.40 (3 0 4) and 59.2
(5 2 1) (JCPDS No: 898912) reveals the formation of the compound Pb
(Fe,Mn)12O19.
The XRD spectra obtained in the presence of Ni (Fig. 6c) shows
peaks at 2θ = 30.20 (2 2 0) and 30.25 (2 2 0) (JCPDS No: 862267,
893080) indicative of formation of NiFe2O4 and NiO compound, re-
spectively. XRD pattern at 2θ = 34.6 (0 2 1) (JCPDS No: 810463) evi-
dences the formation of FeOOH in the coagulates. Fig. 6d represents the
XRD pattern in the presence of Cr. The XRD peak at 2θ = 26.89 (0 11 0)
(JCPDS No: 361330) indicates formation of chromium oxide, Cr3O8
during the experiment. XRD pattern at 2θ = 35.62 (1 1 0) (JCPDS No:
898103) is due to iron oxide Fe2O3. Fig. 6e represents the XRD pattern
of coagulates obtained in the presence of Cu. XRD peak at 2θ = 31.28
(0 6 6) (JCPDS No: 752146, 791546 and 390246) is due to the for-
mation of Cu(FeO2). XRD peak at 2θ = 35.22 (1 1 1) (JCPDS No:
892530) evidences co-precipitation of the Cu ions with coagulates.
3.3. Mechanism of removal
Co being very similar to iron gave amorphous solids like that
A.J. Bora and R.K. Dutta
containing iron alone produced in absence of any heavy metal. Presence
of Ni, Cr and Cu in the water leads to formation of some crystalline
compounds of NiFe2O4 and NiO, Cr3O8, and Cu(FeO2), respectively. The
presence of Cd leads to formation of highly crystalline compounds of
CdO2, Cd0.1Mn0.9O and Cd2Mn3O8 in addition to facilitating formation
of crystalline FeOOH, MnO2 and Mn3O4. Similarly, the presence of Pb in
the solid coagulates indicates formation of Pb(Fe,Mn)12O19 in addition
to facilitating formation of crystalline Fe2O3 and FeOOH.
The XRD analysis complements the understanding of the order of
ease of removal of the heavy metals in the OCOP treatment:
Cd < < Co < Ni < < Cu < Cr < Pb. As mentioned earlier in
Section 3.1, Cd2+ ion, being a soft acid [51] is least adsorbed onto
FeOOH and MnO2 and is removed mainly through precipitation of
crystalline CdO2, Cd0.1Mn0.9O, and Cd2Mn3O8 resulting in least removal
among the chosen heavy metals. Formation of CdO2 may be possible
due to the oxidation of Cd2+ to Cd4+ by addition KMnO4 because
KMnO4 which is well known strong oxidising agent. Formations of the
complexes Cd0.1Mn0.9O and Cd2Mn3O8 are possible because in these
complexes oxidation state of Cd is +2 and in water generally heavy
metals precipitates as oxides and hydroxides [53,54].
Co is removed only by adsorption onto amorphous FeOOH and
MnO2, and therefore removed much more than Cd but comparatively
less than the other moderately hard acid metal ions. Ni is removed
better than Co due to formation of come crystalline NiFe2O4 and NiO in
addition to adsorption. In water heavy metals like Ni2+ form hydroxide
or oxide at higher pH [55]. The formation of NiFe2O4 may result from
conversion of NiO due during heating and drying of the coagulates
before analysis. This heating effect is also reported in several articles
according to the following Eq. (1) [55,56].
2FeOOH + Ni(OH)2 → α-Fe2O3+Ni0 → NiFe2O4. (1)
2+ 2+ 2+
The removal of Cu , Pb and Cd may also be facilitated by co-
precipitations with the iron hydroxides or oxide such as FeOOH and
Fe2O3 [57,58]. Cu is probably adsorbed stronger than Co and Ni due to
its smaller size. Cr is adsorbed very strongly due to its hard acidic
nature as mentioned earlier. The highest removal of Pb may be attrib-
uted to co-precipitation along with precipitation of highly crystalline Pb
(Fe,Mn)12O19 in addition to moderate adsorption as a moderately hard
acid [50].
4. Conclusion
The present study shows that the low-cost OCOP method, which
efficiently removes arsenic, iron and manganese from water, can also
remove other heavy metals very well. The removal of the chosen heavy
metals from initial concentration of 2 mg/L by the method has been
found to increase in the order Cd (79.0%) < < Co (94.8%) < Ni
(94.4%) < < Cu (98.0%) < Cr (98.3%) < Pb (99.5%). Adsorption of
the heavy metal ions with the amorphous coagulates of iron oxides is
the major mechanism for removal of Ni, Cr, Cu and Co. On the other
hand, while Cd and Pb are themselves removed predominantly through
precipitation, the presence of these ions also facilitates precipitation of
crystalline compounds of iron and manganese. A relatively lower re-
moval percentage of Cd by OCOP is due to the soft acidic character as
Cd2+ ion forms weak bonding with the oxide coagulates. While OCOP
can remove As, Fe and Mn within 2 h, the removal of the heavy metals
take a longer time 3–4 h. The most interesting finding of the present
study is that the low-cost and simple OCOP method is capable of effi-
ciently removing heavy metals of Cd, Co, Ni, Cu, Cr and Pb along with
removal of As, Fe and Mn in one goes.
Acknowledgements
RKD thanks the DST-WTI, New Delhi for financial support (DST/
TM/WTI/2K16/95, 2017). AJB thanks Tezpur University for an
8
Journal of Water Process Engineering 31 (2019) 100839
institutional fellowship.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jwpe.2019.100839.
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