Innovative Infrastructure Solutions (2021) 6:198

https://doi.org/10.1007/s41062-021-00563-4

TECHNICAL PAPER

Detection prediction and mapping of Chromium through QGIS

and adsorption of hexavalent Chromium by modified bio‑adsorbents:
kinetic and adsorption study
Shivam Mani Tripathi1   · ShriRam Chaurasia1 · Pramod Kumar Sharma2

Received: 3 April 2021 / Accepted: 4 June 2021

© Springer Nature Switzerland AG 2021

Abstract
Toxicity due to the presence of heavy metals in ground and surface water due to the release of effluents from industries
holds the potency to cause temporary or permanent damage to the living organisms in the near vicinity of these industries.
This paper aims to assess the vulnerability of groundwater resources owing to its contamination in Banthar Industrial Area.
Using DRASTIC model in combination with quantum geographic information system (QGIS), a groundwater vulnerability
map was developed, which indicated that the dispersal of chromium was in the range of 300–1000 μg/l. In order to study
the impact of chromium dispersion, the authors proposed a batch adsorption testing of the hexavalent chromium (Cr(VI))
using different bio-adsorbent materials, keeping a pH range of 3–9 and the contact time between 0 and 80 min. Adsorption
isotherms and kinetic studies were also considered. All adsorbents followed the Langmuir isotherm (R2 > 0.986), whereas
Temkin isotherm stated the affinity of the adsorbents for the Cr(VI). The reactions between chromium and the bio-adsorbents
were found to follow pseudo-second-order kinetics, which indicated that the reactions were exothermic. The results proposed
that a modification in the bio-adsorbents caused an enhancement in the percent adsorption of Cr(VI) in comparison with
the natural available bio-adsorbents.

Keywords  QGIS mapping · Hexavalent chromium · Kinetic study · Langmuir isotherm · Freundlich isotherm · Temkin
isotherm

Introduction processes in lieu of which little or no effort is seen at times

Easiness, affordability and surplus availability of things
develop a tendency in people to take it for granted. Such
is the case with the natural resources provided to us by the
environment. Water being three-fourths of earth’s surface is
not an exception. India being a developing country is already
on its way to boost its manufacturing and other industrial
* Shivam Mani Tripathi
shivam.mani007@gmail.com
ShriRam Chaurasia
src_gkp@rediffmail.com
Pramod Kumar Sharma
drpksharma07@gmail.com
1
Department of Civil Engineering, Madan Mohan Malaviya
University of Technology, Gorakhpur, U. P. 273010, India
2
Department of Civil Engineering, Indian Institute
of Technology Roorkee, Roorkee, U. K. 247667, India
to make the processes go in a circular fashion. One of the
very serious problems is release of chemicals and waste in
nearby streams and water bodies. Thus, heavy metals like
chromium, lead, arsenic, etc., make their way to these water
bodies from industries like cement industry, paints and pig-
ment industry, paper mills, dyeing, tanneries, etc.
Chromium is mainly existent in two forms: trivalent chro-
mium (Cr(III)) and hexavalent chromium (Cr(VI)). Cr(III) is
less toxic and insoluble in water, whereas Cr(VI) is highly
toxic and soluble in water and exists as dense non-aqueous
phase liquid (DNAPLs) being denser than the water [1].
Depending on the concentration and acidity,
)hexavalent
chromium can exist either as chromate 2−
or dichro-
(
CrO 4
mate Cr2 O7  . The commonly found chromium species (all
2−
( )
hexavalent chromium) include HCrO−4  , CrO2− 4 and
Cr2 O2−
7
[2].
Chromium is one of the globally recognized carcino-
genic metals and one of the eight most harmful chemicals to
human beings [3]. Cr(VI) holds the potency to replace some

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proteins in blood of human body which can cause neuritis,
nephritis, anemia, ulcer and other diseases. If Cr(VI) is pre-
sent in blood for longer periods of time, certain respiratory
problems and lungs cancer may be detected [4]. Cr(VI) is
existent in groundwater where a cluster of industries is sited.
It has also been found that on an average of 6–7 km in their
vicinity, chromium traces are ought to be detected. Popula-
tion living in these area regularly consume the toxic sub-
stances of the industries which acts as the starting point of
serious health problems. Solid wastes from these industries
may also contain the toxic compounds which leaches into
groundwater and infiltrates to several kilometers through
capillary action of the soil. Cr(VI) also affects the flora and
fauna adversely. If water used for irrigation contains chro-
mium ions, then the plant parts have a tendency to absorb
the chromium ions in the descending order of roots, stems,
leaves and fruits. According to IS 10500:2012, the permis-
sible limit of chromium is 0.05 mg/l [5]. Therefore, consid-
ering the protection of aquatic environment and the require-
ments on the discharge limits, it is of significant importance
to reduce the Cr(VI) concentration from potential sources
before they are discharged into water [6].
Use of various metals in various industrial processes,
especially those having specific gravity of more than 5, acts
as potential contaminant for both surface and sub-surface
waters. In the region of Indo-Gangetic plain, near Unnao and
nearby areas, there is a presence of tannery industries which
constantly release chromium into the nearby water bodies
and contaminate them. An effort has been made to under-
stand the levels of contamination of chromium in the water
bodies and to do a pattern study of how its plume spreads
in nearby inhabited areas. Collection of different samples
from different places in Banthar region of Unnao Industrial
Area has been done and tested by ICP–MS. After the testing,
a plot of the groundwater contamination using DRASTIC
model in combination with QGIS has also been done, which
described the dispersal of chromium in the region.
Nowadays, the treatment of Cr(VI) in industrial efflu-
ents includes ion exchange process, chemical precipitation,
electrochemical generation, reverse osmosis, photo-catalytic
oxidation, etc. Generally, these processes are very complex
in nature, have low efficiency, unsuitable for multiple pol-
lutants and costly to perform. Among these technologies of
remediation, adsorption technology is one of the efficient
methods to treat the heavy metals from the water. Many low-
cost bio-adsorbents have been discovered which have good
metal binding capacity. Bio-wastes which are locally availa-
ble in bulk quantities such as wastes from agricultural activi-
ties, natural minerals and industrial byproducts can be used
as bio-adsorbents for the metal ions. Few bio-adsorbents
reported by the researchers are grape-bagasse, mango leaves,
orange waste, etc. Modified orange peel powder (MOPP) in
which orange peel powder is combined by ethylenediamine
13
Innovative Infrastructure Solutions (2021) 6:198
suggested a better efficiency of adsorption as compared to
raw orange peel having also been reported [7]. It has been
observed that a modification in the bio-adsorbents by the
addition of a few compounds like sulfur, polyamines and
esters can improve the efficiency of the adsorption [8].
In this paper, sawdust, rice husk, coir pith and vermicu-
lite have been utilized. Vermiculite is a naturally occurring
mineral, 1:2 type( of alumino-silicate clay( which
) contains
aluminum-oxide Al2 O3 and ferrous ion Fe2+ and helps
)
to achieve better efficiency as a bio-adsorbent [2, 9]. This
work aims to prepare new adsorbents and analyze the effect
of pH on the sorption and the effect of contact time of bio-
adsorbents and Cr(VI). Besides these, kinetic and adsorption
isotherms were also studied and different adsorption models
were used to evaluate the experimental data in order to illus-
trate the possible adsorption mechanism.
Materials and methods
Characteristics of study area
Unnao district of Uttar Pradesh, India, lies between 26° 05′
and 27° 02′ north latitudes and 80° 03′ and 81° 03′ east
longitudes. This location is situated in major physiographic
units of Indo Gangetic Plain-Low land or younger alluvial
plain, and upland or older alluvial plain. In this area, ground-
water is available at very small depth as the pre- and post-
monsoon depth of water level is in the range of 2.15 to 14.13
mbgl and 0.60 to 13.33 mbgl. The major rivers Ganga and
Sai are located near Unnao region which being perennial riv-
ers, have plentiful amount of water. Availability of adequate
quantity of water, land resources and easy connectivity to
major cities attracted the industrialists to set up factories at
this location. Area like Banthar, Jajmau in Unnao and nearby
contains a cluster of tanneries, handlooms and textiles indus-
tries. These types of industries require enormous quantity
of water and other chemicals for their processes and manu-
facturing of products. Effluents from such type of industries
lead to increase in pollutants in their nearby locations as they
discharge water without proper treatment, which contains
a large amount of heavy metals like lead, chromium and
other chemicals which are hazardous. As reported in report
of Central Ground Water Board report (2012), traces of fluo-
ride, chromium and arsenic were found beyond permissible
limits in groundwater at some places of Unnao [10].
Sampling plan and mapping of chromium
dispersion
A series of 25 India Mark II hand-pumps were selected from
the near vicinity of Banthar Leather Technology Park. It
covers an area of about 12 k­ m2 and is assumed to be the
Innovative Infrastructure Solutions (2021) 6:198 Page 3 of 14  198
potential sources of chromium. The park is assumed to have
contaminated the groundwater owing to the effluents of the
industry, which are ill-treated or untreated. These effluents
further percolate through surface and get mixed with the
sub-surface water and disperse further in groundwater.
Locations for sample collection were selected at different
locations around the sources as shown in the Fig. 1. Yellow
portion includes the area covered by Unnao district and red
portion depicts the sampling area from where the samples
were collected. Sample area covers around 12 villages where
the inhabited population was consuming this groundwater.
On an average, from a depth of 125 feet, water samples of
1 l and in 100 ml of torsion bottles were collected separately.
Torsion bottle used here was earlier washed by H ­ NO3–Ar
grade and double distilled water. Sample water for the test-
ing of physical parameters was collected after operating the
hand-pumps for 15 min. 1-l bottle was filled up to the neck
so that there was no presence of air bubbles. 100 ml torsion
bottle was filled with syringe coupled with 0.22-μm filter so
that the organic matters get filtered. Later, in the laboratory,
2 μl of suprapur HNO3 was added in 100 ml of water sample
and preserved for further metal testing.
Chromium was tested by inductively coupled plasma
mass spectrometry (ICP-MS) which has about 90% accu-
racy. The ICP is involved in generation of a high-temperature
plasma source at ~ 10,000 °C, through which the pre-treated
sample is passed. The elements in the sample at such high
Fig. 1  Selected sampling area Banthar region near Unnao, Uttar Pradesh India
temperature are ionized and directed further into the MS.
Then, MS sorts the ions according to their mass/charge ratio
followed by directing them to an electron multiplier tube
detector. This detector then identifies and quantifies each
ion. Other physical parameters like pH, TDS and conductiv-
ity were also measured.
In 1987, the United States Environmental Protection
Agency (USEPA) funded research to develop a method for
evaluating the pollution potential anywhere in the USA,
which led to the successful development of the DRASTIC
model [11]. The DRASTIC model was used to evaluate
the relative vulnerability of areas toward groundwater con-
tamination by focusing on the hydrogeological factors that
influence pollution potential. The hydrogeological factors
include depth to water, net recharge, aquifer media, soil
media, topography, impact of the vadose zone and hydrau-
lic conductivity which also happens to make up the acronym
DRASTIC. The rating schemes and weights assigned to the
seven hydrogeological factors that comprised the basis of
the DRASTIC method were also adopted [11]. DRASTIC
model has been used in detailed studies to delineate areas
where aquifer vulnerability is higher and land use suggests a
potential source of pollution [12]. It is an economical tool to
identify the zones of concern and as a tool to overcome the
problems of haphazard, uncontrolled development of land
and of undesirable activities having an impact on groundwa-
ter quality [13]. As the coordinates of the sample locations
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 198   Page 4 of 14
were known, chromium concentration and all other required
variable data helped to create the mapping of the chromium
dispersion. In order to assess the distance and direction of
the dispersion of the parameters and other geomorphology
of the location which affected the dispersion of the chro-
mium, DRASTIC model was combined with QGIS. As
the chromium was present beyond the permissible limit, it
was required to reduce the concentration and bring its level
below the permissible limit.
Materials and preparation of cationic adsorbent
Cr(VI) was prepared by using K2 Cr2 O7 and double-distilled
water (for dilution) in order to achieve the desired concen-
tration. Sawdust was collected from Timber Mill of Luc-
know, India; rice husk was collected from Jitendra Rice mill
Faizabad Road, Lucknow India; coir pith was collected from
Bhola Garden Solution Lucknow, India, and vermiculite was
sought from the Sakshi Fertilizer Pvt. Ltd. Lucknow, India.
All other reagents were bought from New Science Empo-
rium, Gorakhpur, India. All these chemicals were of analyti-
cal grade and were used as received.
Raw sawdust, rice husk, coir pith and vermiculite were
washed several times with double distilled water to remove
the impurities and other particulate matter. It was further
dried at 80 °C in a convection oven for 24 h. The dried raw
sawdust was sieved in the range of 45 to 150 μm and further
activated by H2 SO4 . 50 g of sawdust was activated by reflux-
ing it with 300 ml of 40 weight % H2 SO4 for 5 h in a flask.
The suspension was cooled and washed with double distilled
water, and 1% sodium bicarbonate was added to remove the
residual acid. Again sawdust was dried in oven at 80 °C for
24 h [14] and then stored in desiccator for further use.
Raw dried rice husk (20  g) was soaked with sodium
hydroxide solution (250 ml and 2.5 mol/l). The suspension
was agitated for 3 h, and rice husk was removed. The treated
rice husk was washed with distilled water until pH turned
to neutral. The activated rice husk was further oven dried at
60 °C for 24 h [15] and kept in desiccator for further use.
20 g of dried raw coir pith was added with 1 l of acrylic
acid and 500 ml of HNO3 in 2 l of flask; then, 25 ml of ceric
ammonium nitrate is added. Nitrogen bubble was introduced
into the suspension for 4 h. Then, the coir pith was washed
with hot water until its pH reached to its equilibrium. Then,
coir pith was oven dried for 24 h at 60 °C and stored in
desiccator [16].
Cleaned vermiculite was soaked into 40 ml solution of
Mg(NO3)2∙6H2O, Al(NO3)2∙9H2O, urea and then stirred for
30 min along with heating the solution in oven at 120 °C
for 24 h. After cooling it to room temperature, the sample
was filtered and washed with deionized water and dried in
oven for 8 h at 60 °C [17] and further stored in desiccator
for further use.
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Innovative Infrastructure Solutions (2021) 6:198
Batch experiment
Fixed amount of activated sawdust, rice husk, coir pith
and vermiculite was added to 250 ml sealed conical flask
containing 100 ml Cr(VI) solution having different initial
concentration. Flasks were put into the shaking thermostat
machine at a speed of 200 rpm. Aqueous sample of 10 ml
was withdrawn at equilibrium and filtered by using 0.25-
μm size filter. The capacity of Cr(VI) adsorption by differ-
ent adsorbing media was calculated under different con-
ditions to understand the changes in adsorption process.
The equilibrium adsorption concentration qe mg g−1 was
( )
determined by equation:
( )
V Co − Ce
(1)
qe =
W
The efficiency of adsorption (percentage of removal
efficiency) was determined by equation:
( )
Co − Ce
Adsorption (% of removal efficiency) = × 100
Co
(2)
where Co and Ce are the initial and equilibrium concentra-
tion of Cr(VI) in mg/l, respectively, V is the volume of the
solution in liter and W is the weight of the adsorbent in gram
and qe is the adsorption percentage in mg ­g−1.
Mechanism of Cr(VI) absorption
The surface molecule of bio-adsorbents has –C=O, –CHO,
–COOH, –CN, –OH, –CONH2, –NH2, –NH, –N, –C–O–C
functional groups. The probable mechanism for Cr(VI)
atoms is to bind with the heteroatoms having donor pair of
electrons in the functional groups present on the bio-adsor-
bent’s surface (as shown in the Fig. 2). The electron donor
present in the functional groups forms a weak coordinate
bond. The linking of hydrogen atom between two elec-
tronegative oxygen atoms attached to the Cr(VI) molecule
and the bio-adsorbent molecule leads to the formation of
hydrogen bonds on the surface. Similar findings of the
attachment of chromium moiety to the functional groups
present on the bio-adsorbents have also been reported [18,
19].
The smaller size of chromium ion and its enhanced
reactivity to attain a stable structural configuration facili-
tated it to adhere onto the surface of biomass containing
free functional groups which resulted in bio-adsorption.
This mechanism of adsorbent–adsorbate helps in the
removal of the metals effectively from Cr(VI) polluted
water.
Innovative Infrastructure Solutions (2021) 6:198 Page 5 of 14  198
Fig. 2  Probable mechanism of Cr(VI) absorption
Results and discussion
Detection prediction and mapping of chromium
It was found that the hand-pumps near the tanneries had
maximum electrical conductivity, i.e., 2089.6 μS/cm which
indicated that the groundwater is highly contaminated as
the permissible limit of electrical conductivity lies between
200 and 800 µS/cm. Total dissolved solid (TDS) was also
found to be maximum in near vicinity to the source which
is beyond the permissible limit (400–2000 mg/l); accept-
able limit of TDS is 500 mg/l. pH of the groundwater water
varied from 6 to 7.3. The presence of chromium was tested
from the samples of different locations using ICP-MS and
was found to be in the range of 1000–3000 μg/l. The distance
between these two points is 6.48 km as shown in Table 1. It
was also found that the chromium variation was not linear at
some places. A sudden surge in the levels of chromium was
also observed due to the presence of other mixing sources
in the region as well as the geological features.
Dispersion of chromium was observed with the help of
QGIS mapping. The investigated area consisted of various
soil types, namely clay, silt, sand, gravel, and kankar sedi-
ments of quaternary age as this area is the central Ganga
alluvial plain. Digital elevation model (DEM) of the inves-
tigated area was developed using QGIS. Using the Spatial
Analyst function of GIS, the slope of the ground surface
from the grid of the DEM was computed. Through the use
of Raster Extraction function of QGIS, the contour was
determined based on the DEM raster at 30 m resolution. It
was assumed that the unsaturated zone is a continuation and
extension of the aquifer media and thus the same GIS shape
file. The groundwater map with dispersal of chromium in
the investigated area (as shown in Fig. 3) showed moder-
ate to highly vulnerable areas prone to contamination. This
pattern is mainly dictated by the shallow water level and
the variation in soil media, aquifer media, vadose zone and
topography.
SEM analysis
To understand the surface morphology and composition of
ions on the bed of adsorbents, scanning electron microscopy
(SEM) and EDX analysis have been conducted. Analysis
has been done by electron microscope equipped with X-ray
analyzer. This study helps to understand the arrangements of
the particles in adsorbent samples. Back scattered electron
and secondary electron analyze the surface morphology of
conducting and non-conducting materials. X-ray analyzer
(EDX) finds the compositions of different ions present on
the bed of the adsorbent.
Raw sawdust was characterized as a highly oriented
structure; materials were highly fibrous which showed
the anisotropic character of the sawdust. This isotropy
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13
Table 1  Presence of chromium in the investigated area with physical parameters
Page 6 of 14

S. No. Location of sites in Unnao region Latitude Longitude Distance (km) pH TDS (in ppm) Hydraulic conduc- Chromium (Cr) in ppm
tivity (μS/cm)
Total (VI) (III)

1 Banthar Industrial Area-I 26.486 80.468 3.74 7.0 590 465.7 0.089 0.021 0.068
2 Banthar Industrial Area-II 26.478 80.467 3.30 6.4 1160 922.4 0.168 0.043 0.122
3 Banthar Industrial Area-III 26.478 80.466 3.28 6.5 1010 828.4 0.120 0.020 0.100
4 Banthar Industrial Area-IV 26.476 80.468 3.37 6.5 1550 1283.6 0.208 0.135 0.073
5 Banthar Industrial Area-V 26.476 80.470 3.51 6.3 1350 1164.2 0.180 0.098 0.082
6 Banthar; near Durga Temple 26.476 80.468 3.40 6.2 1630 1425.4 0.220 0.109 0.111
7 Village Poni; Bramha 26.469 80.436 0.00 6 2000 2089.6 1.000 0.676 0.323
8 Village Gahara; Sikandarpur karn 26.477 80.450 1.72 6.8 950 761.2 0.115 0.054 0.061
9 Village Gahara; Sikandarpur 26.481 80.451 2.01 6.8 740 547.8 0.145 0.036 0.109
10 Village Gahara; Near Hanuman Temple 26.484 80.454 2.56 7.4 580 425.4 0.078 ND 0.078
11 Shekhpur Village 26.499 80.461 3.94 7.3 410 300.0 0.045 ND 0.045
12 Shekhpur Nari 26.500 80.461 4.15 6.3 1020 771.6 0.129 0.064 0.065
13 Nari Market 26.500 80.461 4.18 6.5 840 656.7 0.108 0.043 0.065
14 Gram Panchayat; Nari-I 26.500 80.463 4.36 6.5 560 417.9 0.076 0.004 0.07
15 Gram Panchayat; Nari-II 26.499 80.466 4.38 6.7 470 350.7 0.055 ND 0.055
16 Gram Panchayat; Shekhpur-I 26.510 80.469 5.71 6.5 770 579.1 0.095 ND 0.095
17 Gram Panchayat; Shekhpur-II 26.497 80.465 4.21 6.4 830 625.4 0.105 0.05 0.098
18 Gram Panchayat; Shekhpur-III 26.497 80.465 4.18 6.5 480 350.7 0.057 ND 0.057
19 Shekhpur 26.495 80.459 3.61 6.3 1460 1131.3 0.480 0.23 0.25
20 Shekhpur; near Shiv Temple 26.499 80.461 4.12 7.2 980 723.9 0.125 0.044 0.081
21 Himachal Kheda 26.497 80.473 4.57 7.4 520 373.1 0.074 ND 0.074
22 Himachal Kheda 26.497 80.473 4.77 7.3 490 346.3 0.049 ND 0.049
23 Himachal Kheda 26.497 80.474 4.88 7.2 520 353.7 0.063 ND 0.063
Innovative Infrastructure Solutions

24 Babu Kheda 26.495 80.477 4.97 7.4 440 314.9 0.047 ND 0.047
25 Amir Ali Kheda; Bhagwati Prasad; Vikas khand 26.507 80.486 6.48 7.1 400 283.6 0.030 ND 0.030

*ND = Not Detectable

(2021) 6:198
Innovative Infrastructure Solutions (2021) 6:198 Page 7 of 14  198
Fig. 3  Mapping of investigated area through QGIS showing dispersion of chromium
changed when sawdust was treated with sulfuric acid. It
produced modifications in the fibers and created void chan-
nels, thereby preserving a honeycomb structure as shown
in Fig. 4a, b. Modified sawdust was more porous as com-
pared to the raw sawdust. The chemical composition of
the raw sawdust and modified sawdust also amended as
raw sawdust contained C-45.54%, Zn-1.79%, O-30.62%,
Ca-0.64%, Cu-2.39% and Au-19.04%, whereas modi-
fied sawdust contained C-47.02%, Zn-1.21%, O-36.78%,
Ca-0.45%, Cu-1.89% Au-12.15% and S-0.5% by weight.
Sulfur ion was introduced in the modified sawdust because
the sawdust was treated by sulfuric acid. It also increased
the percentage of oxygen by weight which helped to acti-
vate the sawdust for Cr(VI).
Rice husk was modified by NaOH, which had a crystal-
line structure compared to raw rice husk as shown in Fig. 4c,
d. Surface composition of raw rice husk included C, O and
Si, whereas modified rice husk did not contain Si compo-
nent. The elimination of silica ions from rice husk resulted
in a better surface morphology in terms of surface becom-
ing more porous, crystalline and efficient as compared to
raw rice husk. This modification in surface morphology
characteristics of the activated rice husk made it an adsor-
bent of Cr(VI).
The surface morphology of the modified coir pith was
rougher as compared to the raw coir pith, as
( shown in Fig. 4e,
f. In the modified coir pith, acrylic acid C2 H3 COOH was
)
chemically bonded to the surface of the coir pith. Previ-
ously Deng and Ting [20] reported that surface morphology
was uneven and rougher after the graft co-polymerization of
acrylic acid on raw biomass as compared to raw biomass.
The surface composition of raw coir pith was composed of
C and O of 53.89% and 31.84%, respectively, whereas the
modified coir pith had increased percentage of C and O, i.e.,
62.121% and 39.81%, respectively. C and O got increased
due to reaction of acrylic acid with the coir pith which acti-
vated the coir pith and provided a better efficiency than the
raw coir pith.
From SEM, it was analyzed that the raw vermiculite has
typical flat, smooth and multi-layered structure, whereas
the modified structure of vermiculite (transformed by Mg
Al-LDH), a large number of hexagonal layers were present
on the interlayer surface and the external side of vermicu-
lite surface was covered by half hexagon of Mg Al-LDH as
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 198   Page 8 of 14
Fig. 4  SEM image of a raw (a)
sawdust, b activated sawdust, c
raw rice husk, d activated rice
husk, e raw coir pith, f activated
coir pith, g raw vermiculite, h
activated vermiculite
(c)
(e)
(g)
shown in Fig. 4g, h. Surface composition by X-ray analysis
(EDX analysis) showed the presence of Mg, Al and O with
an Mg/Al molar ratio of about 2. Therefore, it resulted that
Mg Al-LDH can be adjusted by means of concentration of
metal salts in reaction solution.
Effect of contact time on chromium adsorption
by different adsorbent
Contact time is one of the most vital factors in the batch
adsorption analysis. In this stage, the contact time of differ-
ent adsorbents varies and all other parameters like tempera-
ture, adsorbent dose, initial concentration of chromium and
pH remain constant. An optimum temperature of 25 °C, an
adsorbent dose of 1.5 g/l, pH equal to 3, initial concentration
of Cr(VI) as 100 mg/l and agitation time equal to 300 rpm
were kept constant and contact time of the different adsor-
bents was varied in the range of 5–80 min. The effect of
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Innovative Infrastructure Solutions (2021) 6:198
(b)
(d)
(f)
(h)
contact time on adsorption efficiency of Cr(VI) is shown in
Fig. 5. Adsorption rate increased rapidly, and the optimal
removal of Cr(VI) using adsorbents coir pith and sawdust
within 40 min reached 83.5% and 88.4%, respectively. Ver-
miculite within 20 min reached an adsorption limit of 47.5%.
Rice husk does not reach its equilibrium, as it was observed
in contact time period of 5 min to 1 h, adsorption was nearly
constant, but after 60 min it was observed that its efficiency
rapidly changed from 20.1 to 34.06%.
Effect of pH on chromium adsorption by different
adsorbent
Aqueous-regime pH plays a very important role to adsorb
the metal ion onto solid–liquid interface [21]. pH also con-
trols the degree of ionization and speciation of the adsorb-
ate. Experiments were carried under an optimized condition
of temperature = 25 °C, agitation speed = 300 rpm, contact
Innovative Infrastructure Solutions (2021) 6:198 Page 9 of 14  198

100 lead to the binding of negatively charged HCrO−4 ions. The

90 species of HCrO−4 is the most effortlessly exchanged with
80 OH− ions at the active surface of adsorbent, under acidic
Saw dust
70 Rice husk conditions as shown in following reactions [25].
Coir pith
% of Adsorption

60 Vermiculite H2 CrO4 → HCrO−4 + H+ (3)

50

40
HCrO−4 → CrO−4 + H+ (4)
30

20

10
HCrO−4 + HCrO−4 ⇌ Cr2 O2−
7
+ H2 O (5)
0
0 10 20 30 40 50 60 70 80
Cr2 O2−
7
+ 14H+ → 2Cr3+ + H2 O. (6)
Time (Minutes)

Fig. 5  Effect of contact time on Cr(VI) adsorption by different adsor- Effect of different adsorbent doses on chromium
bent
adsorption

Saw dust At this stage, it was examined that the effect of Cr(VI)
100 Rice husk adsorption by variation of doses of different adsorbents by
Coir pith
considering all other conditions constant at optimum level
Vermiculite
80
(pH of aqueous-regime 3, agitation speed 300 rpm, contact
time 60 min and temperature 25 °C). The adsorbent doses
of different materials, i.e., activated sawdust, rice husk, coir
% of Adsorption

60
40
20
0 den increase in adsorption of Cr(VI) was observed. As the
3 4 5 6 7 8
pH
Fig. 6  Effect of pH on Cr(VI) adsorption by different adsorbent
time = 60 min, adsorbent dose = 1.5 g/l and initial chromium
concentration = 100 mg/l. pH of the solution was adjusted
with ­H2SO4 and NaOH. Effect of pH on adsorption of Cr(VI)
by different adsorbent is shown in Fig. 6. An observation
in a pH range of 3 to 9 proved that at lower pH, adsorp-
tion was higher. In case of sawdust and coir pith, effective
adsorption in a pH range of 3 to 6 was observed. Compara-
ble pattern was also perceived in the case of rice husk and
vermiculite as formerly reported in study [22]. This might
be due to the weakening of electrostatic force of attraction
between the oppositely charged adsorbate and adsorbent
which finally leads to the reduction of the sorption effi-
ciency [23]. Adsorption of Cr(VI) varies as a function of pH
H2 CrO4 , HCrO−4 , Cr2 O−7 and CrO2−
4
ions appear as domi-
nant species [24]. At pH 3, HCrO−4 is the dominant species.
The surface of adsorbent is positive at low pH and this may
pith and vermiculite, were varied from 0.25 to 2.00 g/l in the
solution, where Cr(VI) was 100 mg/l. It was observed that
the sawdust and coir pith showed similar variations, when
the adsorbent dose was 0.25 g/l. Their adsorption percent-
age was calculated by Eq. (2), and the results obtained were
48.67% and 44.70%, respectively. As further increment was
done in the dose of sawdust from 0.50 to 1.00 g/l, a sud-
9
adsorbent dose of sawdust and coir pith was kept at 1.50 g/l,
the obtained adsorption percentage was 78.34% and 76.9%,
respectively, which on increment remains nearly constant (as
shown in Fig. 7). In the case of rice husk, when adsorbent
dose was kept at 0.25 g/l, the obtained adsorption percent-
age was 25.89%. As the dose of adsorbent was increased to
1.5 g/l, the adsorption percentage reached its optimum level.
In the case of vermiculite, effects of doses on adsorption
was nearly constant after 0.75 g/l; however, it was earlier
reported in study by [26] that as the adsorbent dose was
increased, adsorption percentage of metal ion also enhanced.
Adsorption isotherm
Adsorption isotherm describes the interaction of adsorbate
with adsorbent. The experimental adsorption data of Cr(VI)
ion with different adsorbents such as sawdust, rice husk,
coir pith and vermiculite were analyzed using Langmuir,
Freundlich and Temkin models. The initial concentration
of Cr(VI) affected the adsorption percentage of the test bio-
sorbents. An increasing trend in the adsorption percentage

13
 198   Page 10 of 14 Innovative Infrastructure Solutions (2021) 6:198

80 no lateral interaction between the adsorbed molecules [27].

70
The Freundlich model can be applied to multilayer adsorp-
tion with non-uniform distribution of adsorption and the
60 affinities over the heterogeneous surface [28]. The Temkin
isotherm model assumes that the adsorption of all molecules
% of Adsorption

50
Saw dust
Rice husk decreases linearly with the increase in coverage of the adsor-
40
Coir pith bent surface, and that the adsorption is characterized by a
Vermiculite uniform distribution of binding energies, up to a maximum
30
binding energy [29].
20
Adsorption isotherm (Langmuir, Freundlich and Tem-
10 kin models) was applied to know the equilibrium adsorp-
tion characteristics. Equation (7) represents the Langmuir
0
0.00 0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 isotherm.
Adsorbent Dose (g/L)
qmax KL Ce
qe = . (7)
1 + KL Ce
Fig. 7  Effect of different doses on Cr(VI) adsorption by different
adsorbent
The Langmuir isotherm was transformed into its linear
form as represented in Eq. (8) to determine the adsorption
parameter.
90
1 1 1 1
80
qe
= . +
KL qmax Ce qmax (8)
70
where qmax is the maximum adsorption percentage (mg/g)
60
and KL (mg/g) is Langmuir isotherm constant which shows
qe (mg/g)

50 that the binding affinity

( between Cr(VI) and adsorbent bead.
Separation factor RL is calculated by equation
)
40

30
1
RL =
1 + Co × KL (9)
Saw dust
20
Rice husk
Coir pith where RL is the dimensionless Langmuir constant which
10
Vermiculite indicates the adsorption nature to be either unfavorable, if
0 RL > 1, linear if RL = 1, favorable if 0 < RL.
0 10 20 30 40 50 60 70 80 90 100
Freundlich isotherm is represented by Eq. (10):
Ce (mg/L)
1

qe = Kf Cen . (10)
Fig. 8  Effect of initial concentration on Cr(VI) removal by different
adsorbents The linear form of Freundlich isotherm is shown in
Eq. (11).
of sawdust and coir pith can be seen from Fig. 8. Rice husk 1
was also found to follow the same pattern as that of saw dust logqe = logK f + logCe (11)
n
and coir pith but had lower adsorption percentage because
the surface morphology of rice husk is less porous and had where Kf is Freundlich’s constant and used to measure the
lower affinity with Cr(VI). In the case of vermiculite, the adsorption percentage and 1n is the adsorption intensity. The
adsorption percentage was more than the sawdust. After a value
( of n explains the
1
) adsorption process to be either favora-
further increase in the initial concentration of Cr(VI), the ble 0.1 < 1n < 0.5 or unfavorable.
adsorption percentage got decreased and finally was found to Temkin isotherm is represented by Eq. (12)
be less than that of rice husk. At this stage, it was observed
that the adsorption percentage was found to be in the order
( )
RT RT
qe = lnAT + lnCe (12)
as: coir pith > sawdust > rice husk > vermiculite. bT bT
Langmuir adsorption model is based on the assumption
that the maximum adsorption corresponds to a saturated where bT = slope of the graph between qe ln Ce .
monolayer of solute molecules on the adsorbent surface with

13
Innovative Infrastructure Solutions (2021) 6:198 Page 11 of 14  198

0.225 120
110
0.200
100
0.175 90

0.150 80
70
0.125
1/qe

60

qe
0.100 50
Saw dust
Rice husk 40
0.075 Sawdust
Coir pith Rice husk
30 Coir pith
0.050 Vermiculite Vermiculite
Linear Fit of Sheet1 D"1/qe" 20 Linear Fit of Sheet1 F"qe"
Linear Fit of Sheet1 B"1/qe" Linear Fit of Sheet1 B"qe"
0.025 10 Linear Fit of Sheet1 D"qe"
Linear Fit of Sheet1 F"1/qe" Linear Fit of Sheet1 H"qe"
Linear Fit of Sheet1 H"1/qe" 0
0.000 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55
ln Ce
1/Ce

Fig. 11  Temkin isotherm plots for the bio-sorption of Cr(VI) onto

Fig. 9  Langmuir’s isotherm plots for the bio-sorption of Cr(VI) onto different adsorbents
different adsorbents

Table 2  Isotherm parameters for the removal of Cr(VI) by different

2.0 adsorbents
Type of isotherm Sawdust Rice husk Coir pith Vermiculite
1.8
Langmuir
1.6
qmax (mg/g) 112.72 95.23 63.32 43.27
1.4 KL (L/mg) 0.0016 0.0015 0.0011 0.0385
log qe

RL 0.8626 0.8706 0.467 0.2061

1.2
R2 0.9951 0.9984 0.9861 0.9907
1.0 Freundlich
Sawdust Kf 1.4279 1.2702 2.1596 3.7102
0.8 Rice husk
Coir pith 1∕n 1.1533 1.0275 0.9253 0.7224
Vermiculite
0.6 Linear Fit of Sheet1 H"log qe" R2 0.9759 0.9942 0.9554 0.9748
Linear Fit of Sheet1 F"log qe"
Linear Fit of Sheet1 B"log qe"
Linear Fit of Sheet1 D"log qe"
0.4
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
log Ce
of adsorption sites, whereas Freundlich isotherm supports
that adsorption occurs on heterogeneous surface of the
Fig. 10  Freundlich isotherm plots for the bio-sorption of Cr(VI) onto adsorbent [30].
different adsorbents
The following results presented in Table 2 show that
the Langmuir isotherm model was the best fit because the
value of linear regression coefficient (R2 > 0.986 for all
( )
intercept
AT = exp cases) of this isotherm was observed to be higher than the
bT
Freundlich isotherm model (R2 > 0.955 for all cases) which
AT is the equilibrium binding constant (L m ­ ol−1) corre- shows monolayer adsorption of Cr(VI) on different adsor-
sponding to the maximum binding energy, bT is related bents. Maximum adsorption percentage (qmax) for Cr(VI)
to the adsorption heat, R is the universal gas constant observed that the sawdust has maximum adsorption per-
(8.314 J ­K−1 ­mol−1) and T is the temperature (K). centage followed by rice husk, coir pith and vermiculite.
In this study, three theoretical models Langmuir, Fre- The values of separation factor (RL) for all adsorbents are
undlich and Temkin isotherms were used to examine less than one, which favored the adsorption phenomenon.
the adsorption characteristics of different adsorbents for Temkin isotherm model explained that all adsorption took
Cr(VI) uptake as shown in Figs. 9, 10 and 11. The Lang- place as exothermic process as b T value is found to be
muir’s isotherm describes the monolayer adsorption of positive in all cases. AT describes the affinity of sorbents
pollutant onto the adsorbent surface having finite number for Cr(VI) and R2 > 0.62 in all cases (Table 3).

13
 198   Page 12 of 14 Innovative Infrastructure Solutions (2021) 6:198

Table 3  Temkin isotherm model for the removal of Cr(VI) by differ- 2 Sawdust

ent adsorbents Rice husk
Coir pith
Vermiculite
Temkin isotherm Sawdust Rice husk Coir pith Vermiculite Linear Fit of Sheet1 B"ln (qe-qt)"
Linear Fit of Sheet1 D"ln (qe-qt)"
1 Linear Fit of Sheet1 F"ln (qe-qt)"
Linear Fit of Sheet1 H"ln (qe-qt)"
BT (J/mol) 32.474 29.052 27.758 48.959
KT (L/mg) 0.2341 0.2006 0.2738 0.2553
R2 0.6917 0.7694 0.7906 0.9376 0

ln (qe-qt)
-1
Kinetic isotherm

Kinetic study has been carried out to find out the reaction -2

time in order to achieve the equilibrium using the opti-

mum amount of bio-adsorbents and maintaining the pH
level simultaneously. The equilibrium adsorption study
was conducted with Cr(VI) solution of concentration,
Co = 10–200  mg/l with different adsorbents in optimum
doses of 1.5 g/l. Initial pH of the solution was set at 3 using
0.1 M H2 SO4/0.1 M NaOH. 250 ml of Cr(VI) sample was
then shaken at 300 rpm at 25 °C for 60 min. After the main-
tenance of the state of equilibrium, different adsorbents were
separated from the solution through 2 μm filtration, the fil-
trate was then analyzed using spectrophotometer. Adsorption
rate of Cr(VI) was analyzed by using pseudo-first-order and
pseudo-second-order kinetic models by different adsorbents.
The pseudo-first-order model is represented in Eq. (13) and
pseudo-second-order model is represented by Eq. (14).
(13)
( )
ln qe − qt = lnqe − K1 t
t 1 1
qe
= +
K2 q2e qe (14)
-3
0 20 40 60 80
Time (Minutes)
Fig. 12  Pseudo-first-order kinetic plots for the bio-sorption of Cr(VI)
onto different adsorbents
There exists a rational agreement between
( the
) experimen-
tal and calculated adsorption percentage qe values which
favors the pseudo-second-order kinetic model. The results
showed that the concentration of bio-sorbents and Cr(VI)
was responsible for the rate determining step during the
binding of Cr(VI) with the different adsorbents. This also
suggests that the adsorption of Cr(VI) on beds takes place
through chemisorption mechanism. This study has also
been also verified previously [32].

where qt represents the adsorption percentage (mg/g) at

time t, K1 ­(min−1) is the equilibrium rate constant K2 (g
­mg−1 ­min−1) is the equilibrium rate constant. 1.75
The rapid-kinetic behavior indicated that the adsorption
process was dependent on the available number of binding 1.50

sites on the adsorbents for the uptake of Cr(VI). After equi-

1.25
librium time, the adsorbent surface is achieved [31]. In the
present study, the pseudo-first- and second-order rates men-
1.00
tioned in Eqs. (13) and (14), respectively, were employed
t/qt

for further evaluation of the kinetic parameters of Cr(VI) 0.75

adsorption on different adsorbents.
Sawdust
The fitting of equilibrium data of two kinetic models 0.50 Rice husk
Coir pith
with the Cr(VI) and different adsorbents are shown in Vermiculite
Linear Fit of Sheet1 H"t/qt"
Figs. 12 and 13, respectively, and the results of respec- 0.25
Linear Fit of Sheet1 F"t/qt"

tive kinetic parameters in Table 4. A pseudo-second-order Linear Fit of Sheet1 D"t/qt"

Linear Fit of Sheet1 B"t/qt"
0.00
kinetic model was observed to be the best fit in the expla- 0 10 20 30 40 50 60 70 80
nation of the kinetics of Cr(VI) adsorption with different Time (Minutes)
adsorbents because it exhibited higher values of linear
regression coefficient (R2 > 0.999 in all cases) in compari- Fig. 13  Pseudo-second-order kinetic plots for the bio-sorption of
son with pseudo-first-order model (R2 < 0.799 in all cases). Cr(VI) onto different adsorbents

13
Innovative Infrastructure Solutions (2021) 6:198 Page 13 of 14  198

Table 4  Kinetic parameters for the removal of Cr(VI) by different Considering the adsorption isotherms and kinetic stud-
adsorbents ies, the reactions between chromium and the bio-adsorbents
Sawdust Rice husk Coir pith Vermiculite were found to follow pseudo-second-order kinetics and the
reactions were exothermic as the B ­ T value was found to be
Order of reaction
greater than 0. The adsorption followed kinetic isotherm of
qe,exp (mg/g) 48.5 44.8 50.2 47.2
pseudo-second order in which regression value varied from
Pseudo-first order kinetic model
0.994 to 0.999. The affinity of the different adsorbents for
qe,cal (mg/g) 3.32 3.51 3.41 2.82
the Cr(VI) was also observed, which exhibited that the ver-
−1 − 0.00065 − 0.00066 − 0.0007 − 0.0007
( )
K1 min miculite bed showed higher interaction with the metal ions
R2 0.8424 0.8324 0.7998 − 0.8338 where value of R2 (correlation coefficient) was found to be
Pseudo-second-order kinetic model 0.937. For adsorption isotherm, Freundlich and Langmuir
qe,cal (mg/g) 48.7 45.0 50.5 47.4 models were applied, Langmuir linear isotherm was estab-
K2 (g ­mg−1 ­min−1) 0.04048 0.03703 0.03733 0.04643 lished to be more accurate. The adsorption percentage qmax
R 2 0.99992 0.99985 0.999989 0.99994 (mg ­g−1) of sawdust was found to be maximum and that of
vermiculite was minimum.
This works holds a clear vision to develop and imple-
Conclusion ment such low-cost, affordable and environmental friendly
measures to deal the problems of chromium toxicity in and
This work utilizes ICP-MS for the detection and measure- around tannery industries. It also welcomes other people of
ment of chromium. Based upon the study of 5 different the industry and academia for future contributions.
zones using QGIS, the maximum value of chromium in
groundwater was found to be 1000 μg/l. The depletion Acknowledgements  This work was supported by the Madan Mohan
Malaviya University of Technology, Gorakhpur and Uttar Pradesh Jal
of chromium from the source was found to be nonlinear. Nigam.
DRASTIC model suggested that the possible reasons
behind this could be the presence of industries (although Author’s contribution  The manuscript has been written through the
closed many years ago) in the region, anthropogenic contributions of all the authors. All authors have given approval to the
activities and the geological topographies. The levels of final version of the manuscript.
chromium were found under permissible limit only after
Funding Nil.
a distance of 6.48 km from the source as suggested by
QGIS. Other parameters like TDS, hydraulic conductiv- Declaration 
ity and others as mentioned in IS 10500:2012 were also
found beyond the permissible limits in nearby areas of Conflict of interest  On behalf of all authors, the corresponding author
the source. This calls for an action to tackle the water states that there is no conflict of interest.
quality parameters in a simple and affordable manner and
find methods to create a circular process for the reuse and
recycle of the heavy metals (chromium, etc.) which are
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 Engineering Science and Technology, an International Journal 23 (2020) 1153–1161

Contents lists available at ScienceDirect

Engineering Science and Technology,

an International Journal
journal homepage: www.elsevier.com/locate/jestch

Full Length Article

Detection of Chromium in surface and groundwater and its

bio-absorption using bio-wastes and vermiculite
Shivam Mani Tripathi ⇑, ShriRam Chaurasia
Department of Civil Engineering, Madan Mohan Malaviya University of Technology, Gorakhpur (U.P.) 273010, India

a r t i c l e i n f o a b s t r a c t

Article history: Unnao has a large number of tanneries and huge amount of waste water is generated and there effluents
Received 5 October 2019 contain Chromium, which infiltrates and percolates below the ground and contaminate the surface and
Revised 4 December 2019 subsurface water, thereby creating a possibility of becoming a potent carcinogenic. Chromium is present
Accepted 13 December 2019
in different forms, trivalent and hexavalent being the prevalent ones. Cr(III) has low solubility whereas Cr
Available online 22 January 2020
(VI) has high solubility and can easily move through the groundwater and get mixed with it. Present
paper is based upon the collection of 47 samples from Unnao district of Uttar Pradesh (India), which were
Keywords:
tested for pH, Electrical Conductivity, hexavalent Chromium and total Chromium. The concentration of Cr
Hexavalent Chromium (Cr6+)
Diphenylcarbazide method
(VI) for one of the sites (Dharamkata) was found to be 2070 mg/l; which has a high efficacy to contaminate
Sawdust the unlined channels, thereby causing contamination of surface and groundwater. In order to remediate
Coir pith the problem, different bio-waste materials were used for the removal of Cr(VI). The concentration of Cr
Rice husk (VI) and total Chromium were determined by Diphenylcarbazide method and ICP-OES. Hexavalent
Vermiculite Chromium is highly oxidizing in nature and requires electron donor materials for reduction. The research
utilized bio-wastes like coir pith, sawdust, rice husk and vermiculite (natural mineral) to reduce
Chromium. An effluent sample having Chromium concentration, 184.8 mg/l was passed through columns
having different bio-absorbent medium, out of which bio-absorbents and vermiculite combination was
found to be more capable of reducing hexavalent Chromium from the sample. An outstanding decrease
in concentration of total Chromium (184.8–4.48 mg/l) is accomplished by the combination of vermiculite
and coir pith. This shows that natural wastes are very likely the absorbents of Cr(VI), which can be used to
decrease the concentrations of Chromium from the contaminated water.
Ó 2019 Karabuk University. Publishing services 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/).

1. Introduction freshwater and a variety of chemicals. About 350 L of fresh water

India is a developing country where increase in the industrial-
ization would create more jobs as well as to improve its economic
condition. India is full of resources and low-cost land as compared
to the other developed countries which attracts investors and
industrialist to establish their setup in India.
Unnao is a district of Uttar Pradesh situated between Kanpur
and Lucknow having Ganga, Kalyani and Sai as main streams. It
is a large industrial city having a bulk of tanneries and chemical
industries which discharge their effluents into these water bodies
and pollute the surface water thus affecting the flora and fauna
present in their vicinity. Solid waste materials are dumped on open
ground area without treating or with improper treatment which
causes leaching in groundwater leading to the contamination of
groundwater. Tannery industries require huge quantity of
⇑ Corresponding author.
Peer review under responsibility of Karabuk University.
is required for 10 kg of raw skin. Different chemicals used in tan-
ning are lime, sodium carbonate, sodium bi-carbonate, sodium sul-
phate, common salt, fat liquors, chrome sulphate, vegetable oils
and dyes. Common salt is the most polluting material which can-
not be easily removed. Every 10 tonnes of salted buries and skin
processed, 2–3 tonnes of salt is removed and in addition another
1 ton of salt is removed. Characteristics of tannery water are strong
dull reddish-brown color having high pH, high Biological Oxygen
Demand (BOD) and low Dissolve Oxygen (DO). Tannery effluents
are very bulky and highly puerile, which is hazardous to the receiv-
ing stream. When it is discharged untreated, it enters below the
ground and comes in contact with groundwater, affecting the
water quality of the aquifer in the area. Other main chemical com-
ponents of the tannery wastes are sulphide and Chromium. These
chemicals intermix with water and permanently pollute the
groundwater, thereby making water non potable and unfit for irri-
gation. Single tannery can contaminate surface water as well as
groundwater of about 6–7 km radius around it.

https://doi.org/10.1016/j.jestch.2019.12.002
2215-0986/Ó 2019 Karabuk University. Publishing services 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/).
1154 S. Mani Tripathi, S. Chaurasia / Engineering Science and Technology, an International Journal 23 (2020) 1153–1161
Chromium is 21st most abundant element in nature. It is found
in rocks, animals, volcanic dust, plants, etc. It mainly exists in the
forms of trivalent and hexavalent Chromium. Chromium (III) pre-
sent in our blood cells is an essential nutrient for the body. Cr
(VI) is generally used in industrial processes and is established as
carcinogen. Chromium metals and Cr(III) are insoluble in water
hence are not harmful to human body. In India BIS [2] has recom-
mended a limit of 0.05 mg/l for Chromium (VI). Rainwater may
contain average Chromium concentration of 0.2–1 g/l whereas in
seawater the natural Chromium concentration is about 0.04–0.5 m
g/l. In surface water natural content of Chromium is about 0.5–
2 mg/l and the dissolved Chromium content 0.02–0.3 mg/l. Chro-
mium concentrations in Antarctic lakes increase with depth
from < 0.6–30 mg/l. Mostly the surface water content 1–10 mg/l of
Cr in USA has levels up to 84 mg/l whereas in central Canada it
ranges from 0.2 to 44 mg/l (Source: National Water Quality Data
Bank (NAQUADAT), Inland Waters Directorate, Environment
Canada, 1985). In India 50% of natural streams have concentration
below 2 mg/l. Overall groundwater Chromium concentration is low
(<1mg/l). In Netherlands, the mean concentration of Cr has been
recorded as 0.7 mg/l. In India, 50% of 1473 water samples from
dug wells contained Chromium <2 mg/l. The maximum permissible
limits by different agencies throughout the world are as: Chro-
mium (mg/l): [19] CPCB no relaxation. There is great confusion
to the researcher, public health officers, and doctors to following
the permissible limits when they do research. The WHO and MCI
should fix the uniformity of permissible limit which may be helpful
to the society. The presence of Chromium in surface water is an
indicator of the extent to which industrial activities have been per-
formed. The Chromium compounds (Cr3+ and Cr6+) leaching
through groundwater depends on initial concentration, direction,
gradient flow and presence of effluent. Cr(VI) primarily exist as
bichromate (HCrO
2

4 ) or chromate (CrO4 ) which are quite soluble
over much of environmental pH range 6.5–7.5 CrO2
4 is an oxidant,
mutagenic, carcinogenic and is toxic to a variety of flora and fauna
even at concentrations below 50 lg /kg (Turner and Rust, 1971). Cr
(III) is relatively non-toxic and forms sparingly soluble hydroxide
and mixed (Fe, Cr) hydroxide precipitates at circum neutral pH
and above. It is weakly mobile in groundwater because of low sol-
ubility, and precipitated Cr(OH)3 reacts slowly with molecular oxy-
gen. The ions and dissolved metal play a vital role in various
physiological processes of the flora and fauna. During the reduction
process of hexavalent to trivalent Chromium by generation of free
radicals, may damage the cellular components and can also affect
the DNA. Health effects of Chromium toxicity may result as der-
matitis, ulcer etc. reported by [2].
Three means have been projected to explain the geno-toxicity
of Cr(VI) which are as discussed below.-
1. The first mechanism includes the results of the reduction
from Cr(VI) to Cr(III) by highly reactive hydroxyl radicals
and other reactive radicals;
2. The second mechanism includes the direct binding of Chro-
mium (V), produced by reduction in the cell, and Chro-
mium (IV) compounds to the DNA; and
3. The third mechanism is attributed to the geno-toxicity of
the binding DNA which results in the end product of the
Chromium (III) reduction.
In the present work, toxic hexavalent Chromium is converted to
non-toxic trivalent Chromium. Hexavalent Chromium is more
toxic than trivalent Chromium. The reason behind this is as follow:
1. Structural similarity between sulphate and chromate is
responsible for entrance of chromate into the cell.,
2. In biological pH, trivalent Chromium undergoes precipita-
tion as hydroxide but hexavalent Chromium remains in
the solution.
3. Hexavalent Chromium is labile centre (t02ge0g) but trivalent
Chromium is (t32ge0g) is inert [11,13–14].
Total 47 samples that were collected from tube wells,
handpumps, surface water and tanneries effluent from eight sites
of Unnao near to tannery industrial area (shown in the Fig. 1)
and further analyzed for hexavalent Chromium and total
Chromium, pH and electrical conductivity.
2. Study area
Unnao district of Uttar Pradesh, having an area of about 4,558
sq. Km., population 2,700,324 as per 2011 census. It is enclosed
in the North by Safipur block, in the East by the Bichhia block, in
the South by Sikandarpur Karon block, whereas the Ganga River
in the West separates it from the district Kanpur.
More than 50 industries mainly tanneries, serving the need of
nation were evaluated for discharge effluents after treatment from
common effluent treatment plant. From these industries approxi-
mately 70% untreated effluent is released into the Ganga River
via drains which is completely banned now a days.
The quality of groundwater in the industrial areas is under a
constant risk of contamination directly or indirectly. Higher con-
centration of Chromium in few parts of Unnao districts is a com-
mon characteristic of the region.
Soil found in Unnao and surroundings shows large difference in
composition and appearance. The major part of area consists of
normal soils known locally as matiar or clay in the topographic
lows, bhur or sand on the ridges and dumat or loam on the plains.
3. Methods and process
3.1. Detection of Chromium
Samples which were collected from eight sites (as shown in Fig. 1)
present near the industrial area from surface water, dug well, tube
well and effluent; to find out the presence of hexavalent Chromium
(Cr6+) and total Chromium. Total Chromium is determined by ICP-
OES (Inductively Coupled Plasma - Optical Emission Spectrometry).
Cr(VI) samples were collected in poly propylene bottle (TORSON Bot-
tle) and were kept in ice box during transport of samples and by
maintaining a throughout temperature 4 °C. These samples were also
analyzed for the pH and electrical conductivity. All the chemicals
used are of analytical reagent grade. Hexavalent Chromium is esti-
mated by using Diphenylcarbazide process. This process analyzes
the hexavalent Chromium in the range of 0.5–50 mg/l.
Hexavalent Chromium can be resolute by colorimetrically, by
with Diphenylcarbazide in acid solution. In the absence of interfer-
ing amount of Vanadium, Molybdenum and Mercury, a red violet
color of unknown composition is formed. Reactions are very sensi-
tive as absorbency index per gram atom of Chromium is about
40,000 at 540 nm. Red violet color is formed due to excess addition
of Diphenylcarbazide, and its absorbance is measured photometri-
cally at 540 nm. Generally, reaction of Diphenylcarbazide and Chro-
mium is free from any type of interference but some interference like
hexavalent molybdenum and mercury salts may be present and
causes generation of red violet color in the presence of reagent at
specified pH but these have low intensity of color than chromium.
Concentrations of molybdenum and mercury up to 200 mg/l can
be tolerated. Vanadium interferes strongly, but concentrations up
to 10 times that of Chromium will not cause any trouble.
 S. Mani Tripathi, S. Chaurasia / Engineering Science and Technology, an International Journal 23 (2020) 1153–1161
Fig. 1. Selected sites for study of Chromium detection in Unnao.
In the present study, we have used a spectrometer at 540 nm
which provides the path of light for 1 cm or more. In this experi-
ment, reagent water free as well as any other impurities. We take
141.4 mg dry potassium dichromate (K2Cr2O7) in reagent water
and dilute to 1 L. Dilute 10.00 ml of potassium dichromate solution
to 100 ml (1 ml = 5mgCr). We dilute 10 ml of distilled reagent grade
sulfuric acid (H2SO4) to 100 ml with reagent water. We dissolved
250 mg 1, 5-Diphenylcarbazide in 50 ml acetone which is stored
in brown bottle; remove when the solution becomes discolored.
We add 95 ml of collected samples to 100 ml of volumetric flask
2 ml of Diphenylcarbazide solution is mixed for making solution of
pH 2.00.5. We add H2SO4 in reagent water and wait for 5–10 min
for full color development. We transfer the appropriate portion of
solution to a 1-cm absorption cell and measure its absorbance at
540 nm. Absorbance reading is corrected by deducting the absor-
bance of a blank. Chemical analysis of the sample contains all
reagents except Diphenylcarbazide. Blank sample is prepared to
correct the sample for turbidity. We determine the chromium con-
centration from the corrected sample as per the process discussed
in earlier paragraph.
3.1.1. Observations
By these test, we observe that the samples of surface and
groundwater has higher electrical conductivity and concentration
of Chromium than the permissible limit as per BIS (IS: 10500, [2]
in some places area of study Unnao district. The effluent sample
near CEPT at Dahi Chauki has 3980 mg/l as total Chromium. Mirza
tannery effluent has 435000 mg/l as total Chromium whereas in
Lalau Khera (46 lg/l), Dakary (54 lg/l) and Masnagar (58 lg/l),
hexavalent Chromium is below the BIS limit (i.e. 50 mg/l), but in
1155
future, concentration is expected to rise as it can be seen in sites
like Maswasi (104 lg/l), Shivnagar (145 lg/l) and J R Inter College,
Dharamkanta (600 lg/l). As we have discussed earlier, Cr(VI) is
highly oxidizing in nature and when it comes in contact with the
top layer of soil, it can be converted into Cr(III). Therefore, Cr(VI)
cannot be detected in many places and only Cr(III) is observed.
Many industries dump their solid wastes into open ground, due
to which Chromium gets mixed with surface water and infiltrates
through unlined drains, which contaminates the groundwater
quality. Dharamkata area is a dumping ground for industrial waste
and this area shows yellow patches of Chromium salt on the outer
side of the wall of a building as shown in Fig. 2. Table 1 shows
water quality of study area of Unnao district in terms of Chromium.
The presence of total Chromium indicates that the surface and
groundwater of study area is highly contaminated. Although the
presence of Cr(VI) is not found in many places but the places where
industrial solid waste is being dumped (near Dharamkata) but Cr
(VI) is detectable in low concentration; although in future it may
be devastating if it is not checked and the contaminated percolat-
ing water gets mixed with groundwater and degrade its quality. It
cannot be easily removed; only a transformation of Cr(VI) can be
done by getting it oxidized to Cr(III) which does not get dissolved
in water. Thus, hexavalent Chromium must be remediated to save
groundwater from being contaminated.
3.2. Bio-absorption of chromium
Hexavalent Chromium is highly soluble and mobile in nature
whereas trivalent Chromium is insoluble and immobile in nature.
It has been observed that the oxidation of Cr(III) to Cr(VI) is
1156 S. Mani Tripathi, S. Chaurasia / Engineering Science and Technology, an International Journal 23 (2020) 1153–1161

exceptional occurrence in soil. The existence of microbial strains

and MnO2 in soil may oxidize Cr(III) to Cr(VI). Hexavalent Chro-
mium Cr(VI) exists in solution as monomeric ions HCrO
4 (bichro-
mate) and CrO2
2

4 or as dimeric ion Cr2 O7 (Palmeg and Wittbrodt,
1991; Richard and Bourg, 1991). The monomeric species impart
yellow color when Cr(VI) is greater than 1 mg/l, while high level
of Cr2 O2

7 has orange color of contaminated water. As Cr
6+
is easily
soluble in water, it percolates down in the soil profile and could
contaminate groundwater. There are many methods of removing
Chromium. Many physico-chemicals processes like filtration, coag-
ulation, precipitation ion exchange and oxidation/reduction etc.
can be used in one or more combinations of different methods.
These physico-chemicals are very complex and require high cost
of treatment, so many tannery industries cannot afford the treat-
ment of these effluent. Other method is Bio-Remediation which
can be used to reduce the Cr(VI) by natural process or by different
bio-materials. This technology is more efficient and does not have
complex methods. Better result can be obtained by using one or
Fig. 2. Contaminated Surface Water showing yellow patches of Chromium salt at more combination of methods. By product of this method is not
Dharamkata.
harmful, but it takes longer time period to remove the Cr(VI).

Table 1
Ground Water Quality of Study Area in Unnao district.

S.No Location Type pH EC in ms/cm Cr VI in mg/l Total Cr in mg/l

1 Left Effluent Banthar Effluent 7.67 1315 ND 14
2 Right Effluent Banthar Effluent 7.78 4007 ND 25
3 Mixed Effluent Banthar Effluent 7.60 1865 ND –
4 Tube well near CEPT Surface water 7.53 666 ND –
5 J S slaughter house Effluent 7.63 699 ND 10
6 Banthar India Mark II 7.22 756 ND 8
7 Lalau Khera Tube Well 8.00 5870 ND 48
8 Gaya Prasad, Lalau Khera India Mark II 7.25 4175 ND 32
9 Sambhu, Lalau Khera India Mark II 7.42 788 ND 2
10 Manglal, Lalau Khera India Mark II 7.26 983 1.38 3
11 Shushil, Lalau Khera Hand Pump 7.28 768 ND 11
12 Jagannath, Jalimkhera Drain Water 7.39 2339 ND 25
13 Ramkumar, Jalimkhera Hand Pump 7.23 1635 ND 24
14 Jagawath, Jalimkhera Hand Pump 7.20 1489 ND 25
15 Raj Bahadur, Dakary Hand Pump 6.99 6125 ND 50
16 Mahesh, Dakary Hand Pump 7.03 3339 ND –
17 Khadibhawan, Shuklaganj Hand Pump 7.49 1889 ND –
18 Ayurvedik hospital, Maswasi India Mark II 7.05 2048 ND –
19 Maswasi India Mark II 7.48 4318 ND –
20 Drain in side, Maswasi Drain 7.76 1710 ND –
21 Shankar Singh, Maswasi India Mark II 6.95 3048 0.26 102
22 Horilal, Maswasi India Mark II 7.35 1869 ND 145
23 Kanya Vidyalaya, Maswasi India Mark II 7.18 4601 ND 54
24 Mirza tannery drain, Unnao Drain 7.58 1330 184,800 435,000
25 Unnao distillery Drain 7.96 795 174,980 448,900
26 Munna Awasthi, Rishinagar Hand Pump 7.06 1665 ND 34
27 New Krishna sweet India Mark II 7.45 905 ND 16
28 DC Dwivedi, Rishinagar Hand Pump 7.82 1206 ND 39
29 JL Bajaj, Rishinagar Hand Pump 7.65 1446 ND 5
30 Pal Traders, Shubasnagar Hand Pump 7.62 1229 ND 21
31 Hanuman Temple Ambikapuram India Mark II 7.75 650 ND 18
32 Vinod, Shuklaganj Hand Pump 7.49 1667 ND 17
33 JHS Singrausi, Dharamkata India Mark II 7.78 889 ND 65
34 JAR Inter college, Dharamkata Surface Water 7.79 3586 2070 4015
35 JAR Inter college, Dharamkata Tube Well 7.79 2982 356 606
36 Pintu Gupta, Shivnagar Hand Pump 7.9 3550 ND 141
37 Effluent CEPT, DahiChowki Effluent 7.29 7365 ND 3980
38 Effluent CEPT, DahiChowki Effluent 7.26 19,506 ND 25
39 CEPT, DahiChaowki India Mark II 7.65 1785 ND 18
40 Garhi, Nr tower Hand Pump 7.52 1068 ND 54
41 Jhanjhari Drain Water 7.71 2765 ND 89
42 Central School India Mark II 7.75 679 ND 41
43 Masnagar India Mark II 7.52 1259 ND 25
44 Masnagar in village Drain Water 7.26 2765 ND 58
45 Masnagar on road Drain Water 7.06 952 ND 21
46 CEPT Effluent 7.05 23,480 ND –
47 J S slaughter house Effluent 7.90 1780 ND –
 S. Mani Tripathi, S. Chaurasia / Engineering Science and Technology, an International Journal 23 (2020) 1153–1161 1157

3.2.1. Previous studies for absorption of Cr(VI) Table 3

Now a days bio-remediation or bio-absorbents are used as an Method use to find Characteristics.

alternative method of remediation. These methods are uncompli- S. Characteristic Method Use
cated and cheaper than the other physicochemical methods, but No
it takes more time. For Chromium rich wastewater effluents from 1 pH By pH meter and electrode
tannery industries, we used the bio-absorbent method to reduce 2 Electrical By using four terminal ohmmeters
the Chromium concentration. Several absorbents have been exam- Conductivity
3 Moisture By weighing initial weight and weighing after oven
ined to reduce the Chromium. Zhipei et al. [21] mention that Chi- Content drying the material.
nese peat is used for the absorption of hexavalent Chromium Cr(VI) 4 Exchangeable By titration
from solution. The use of sawdust [16], exhausted coffee, waste tea, Acidity
walnut shells and nut [7] and coconut husk and palm pressed 5 Total Chromium By ICP-OES
fibers [17] in eliminating Cr from aqueous solutions has also been
reported. Reduction of Cr(VI) to Cr(III) is isolated from a long-term
tannery waste contaminated soil by Arthrobacter sp. and a Bacillus Table 4
sp. by Megharaj et al. [5]. Reduction of Cr(VI) ion to Cr(III) ion is Important Characteristics of the Sample collected.

done by using Spent Tea and Coffee Dust by Prabhakaran et al.
[9]. Vinodhini et al. [20] used different bio-absorbents like Neem
Sawdust (NS), Wheat Shell (WS), Mango Sawdust (MS), Orange
Peel (OP) and Sugarcane Bagasse (SB) found that Neem Sawdust
has higher efficiency to reduce the Cr(VI) ion to Cr(III) ion. Saha
et al. [13,14] used Chattim Tree (Devil Tree dust) which success-
fully removed Cr(VI) from polluted water and the absorption
capacity was found to be 333.33 mg/g at pH 2.0 and temperature
35 °C. Saha and Saha [12] found mango leaves as an efficient bio-
absorbent for removal of hexavalent Chromium from polluted
water at maximum pH of 2 with 91% removal at 30 °C. Mukherjee
et al. [6] used sugar cane bagasse which contained reducing con-
tent in the form of sugar, which removed the hexavalent
Chromium.
3.2.2. Bio-absorption material and Cr(VI) sample
The purpose of this is to estimate the efficiency of different
absorbents in terms of percentage of Chromium removal such as
rice husk, sawdust and coir pith and a mineral sorbent – (vermi-
culite) Sawdust it obtained from teak; coir pith is a byproduct from
coconut coir industry; rice husk is collected from rice mill, vermi-
culite, a 1:2 type Aluminosilicate clay mineral is used as a mineral
sorbent. All these are kept at 80 °C for 24 h so that all other impu-
rities and moisture get evaporated. After oven-drying, these mate-
rials are crushed and passed through 2 mm sieve to get consistent
and uniform size. These materials are sealed in polyethylene bags
and stored till further use. Characteristics of the materials are
shown as in Table 2 and method used to find their characteristics
are as shown below in Table 3.
Sample for the test has been collected from the Mirza tannery
industry situated at Dharamkata Unnao, here the effluents released
by cluster of tanneries contain high concentration of Chromium.
The main characteristics of chrome tan liquor which is collected
as sample are as given in Table 4.
S. No Characteristics Value
1 pH 4.42
2 Electrical Conductivity (dSm
1) 7.54
3 Total Dissolved Solids (mg/l) 4831
4 Total Chromium (mg/l) 184.8
5 Sulphate (mg/l) 1679
6 Sodium (mg/l) 2901
7 Chloride (mg/l) 2411
materials which are used to reduce the Chromium concentration.
This experiment is done by locally fabricated glass cylinders of
dimension 50 cm height and 5 cm internal diameter (as shown
in Fig. 3). The bottom of the glass column is covered by wire mesh
of size 0.1 mm and Whatman no. 1 filter paper whereas top of the
column is sealed with rubber cork having a glass tube place as an
air outlet. The column has a closed end from the bottom side. Out-
let of the column was attached to a conical flask for the collection
of treated effluents.
In first slot, two columns for each material of absorbents are
filled up to 30 cm with rice husk, coir pith, sawdust and vermi-
culite. Due to different type of grains of the material columns have
different bulk densities ranging from 0.470gm/cc to 2.378gm/cc.
Sample from Mirza tannery effluent have total Chromium concen-
tration of 184.8 mg/l is allowed to move from end to end in the col-
umn at the rate of 1.1 ml per minute. The rate of flow is maintained
uniform throughout the experiment.
Conical flask is used for collecting the treated water after pass-
ing through the column in 12 h and then the concentration of Chro-
mium is determined as per process shown in Fig. 3. Different

3.2.3. Column experiment method

The objective of this method is to reduce the chrome tan liquor
concentration of the tannery effluent by different bio-absorbent
materials. These are low-cost materials as compared to other

Table 2
Important Characteristics of Absorbent Material.

S. No Absorbent pH Electrical Moisture Exchangeable Total

Conductivity content Acidity Chromium
(dSm
1) (%) (cmol(+) (mg/kg)

1
kg )
1. Sawdust 5.96 0.61 4.05 131.0 BDL
2. Rice husks 6.69 0.85 4.81 29.9 BDL
3. Coir pith 7.34 0.56 2.87 109.9 3.375
4. Vermiculite 8.99 0.08 0.01 4.9 34.4
Fig. 3. Diagram of Glass Column setup used in absorption study.
1158 S. Mani Tripathi, S. Chaurasia / Engineering Science and Technology, an International Journal 23 (2020) 1153–1161

combinations in columns of different materials are used. The first When pH is high, oxidation rate of Fe2+ by dissolved oxygen
slot of column used as mentioned below: exceeds the oxidation rate of Cr(VI). When groundwater pH is
greater than 4, Cr(III) precipitates with Fe(III) in a solid solution
1. 100% saw dust (176 g) column; with common composition ofCrx Fe1
x ðOHÞ3 . If the decrease of hex-
2. 100% rice husks (277 g) column; avalent Chromium by ferrous iron is the only source of Fe(III) and
3. 100% coir pith (115 g) column and; Cr(III), a solid solution with the composition of Cr0:25 Fe0:75 ðOHÞ3 is
4. 100% vermiculite (700 g) column formed as per following reaction:

Second slot column are filled by different absorbent material HCrO
4 þ 3Fe2þ þ 3H2 O þ 5OH
! 4Cr0:25 Fe0:75 ðOHÞ3
and vermiculite in equal percentage of volume are as mentioned
Natural mineral vermiculite and bio-waste materials which
below:
hold the ferrous iron have greater tendency to decrease the hex-
avalent Chromium.
1. 50% saw dust (110 g) + 50% vermiculite (110 g);
2. 50% rice husks (190 g) + 50% vermiculite (190 g) and;
3. 50% coir pith (120 g) + 50% vermiculite (120 g). 4. Results and discussion

Third slot column are filled by different absorbent material and The effluent from Mirza Tannery containing 184.8 mg/l of Chro-
vermiculite in 3:1 ratio of volume means 75% of material and 25% mium is allowed to move through column containing only absor-
of vermiculite are as mentioned below: bent materials or a combination of absorbents and vermiculite.
The efficiency of different materials in lowering the concentration
1. 75% saw dust (150 g) + 25% vermiculite (170 g); of Cr has been evaluated. Due to bio-absorbent treatment, pH and
2. 75% rice husks (200 g) + 25% vermiculite (170 g) and; Electrical Conductivity both increases. When sample is treated
3. 75% coir pith (100 g) + 25% vermiculite (170 g). with sawdust, pH of the raw sample is 4.42 which increases up
to 5.73, 5.06 with rice husk, 7.17 with coir pith and 7.75 with ver-
Effluent samples from the column are absorbed with aqua-regia miculite whereas electrical conductivity increases from 7.54 to
(3:1 HCl: HNO3) and the total Chromium was calculated by using 10.8. But in case of vermiculite, an exception is observed, electrical
spectrophotometer with air–acetylene flame. Monomeric chro- conductivity decreases from 7.54 to 5.3 and total dissolved solids
mate classes are connected through a series of acidic dissociation decrease from 4831 to 3329 mg/l. Coir pith and sawdust did not
reactions. affect the TDS. However, in second and third slot, where the mix-
tures of absorbent and vermiculite are present in the column, it
H2 CrO4 ! HCrO
4 þ Hþ is observed that the efficiency of coir pith with vermiculite
improves. By similar process with other mixtures and vermiculite
is performed and similar trend is observed. Result is shown in
HCrO
4
CrO2

4 þH
þ
Table 5 below.
Dichromate is the product of polymerization of the monomeric Electrical Conductivity and pH are widely varied between influ-
ents and effluents of the column. pH of the effluent is increasing
bichromate ions to form the dimer Cr2 O2

7
whether it is treated in mono-column or mixed column with bio-
absorbents and vermiculite. The rise in pH is due to following reason:
HCrO
4 þ HCrO
4
Cr2 O2

7 þ H2 O

1. The displacement of hydroxyl ions from the exchange sites;

The comparative concentration of all of these groups depends
on both the pH and total Chromium. H2 CrO4 only occurs at pH 1
and above pH 6.5; CrO2

4 (chromate anion) usually dominate below
pH 6.5 whereas HCrO
4 dominates when the Cr(VI) concentration is
low (<30 mM); Cr2 O2

7 becomes noteworthy when concentration
are greater than 1 mM it may also dominate where Cr(VI) is greater
than 30 mM Palmer and Puls (1994).
3.2.4. Reduction of hexavalent chromium by bio-waste and mineral
Hexavalent Chromium is a strong oxidizing agent and electron
donors and it can remove Cr(VI). Electron donors like Fe(II) are pre-
sent in lower quantities in vermiculite mineral whereas the combi-
nation of bio-waste and vermiculite increases the reduction of
hexavalent Chromium. In this work, rice husk, coir pith and saw-
dust are different types of bio-absorbents and have different bulk
densities ranging from 0.470 g/cc to 2.378 g/cc. When the water
sample was passed through the individual columns, keeping a time
frame of 12 h, the concentration of Chromium in the contaminated
water sample reduced but when the same bio-absorbents were
mixed with vermiculite, which contains Fe(II), the concentration
removal efficiency was considerably enhanced in the similar time
frame as above.
The decrease of Cr(VI) by ferrous iron gives a fast reaction as
given below:
HCrO
4 þ 3Fe2þ þ 7Hþ ! Cr3þ þ 3Fe3þ þ 4H2 O
and
2. Positive charge of the surface decreases due to the absorp-
tion of hexavalent Chromium with a subsequent rise in
positive ions in the equilibrium solution.
The rise in the Total Dissolve Solids and Electrical Conductivity
of treated sample can be recognized to liberate the soluble salts of
absorbents in the equilibrium solution. As rice husk contains huge
amount of cellulose material and is effortlessly degradable than the
coir pith and sawdust, in this case it gives higher amount of elec-
trical conductivity and total dissolve solid compared to both bio-
absorbents.
Third slot contains the layered column of absorbent and vermi-
culite in (1:2v/v ratio) having better efficiency of removing the
Chromium from 184.4 to 4.48 mg/l. This is achieved by coir pith
and vermiculite combination; coir pith is at the bottom of the col-
umn and vermiculite at the top layer of the column. With a view to
remove the total Chromium from the sample, various minerals and
the combination of minerals with vermiculite is evaluated. It is
found that the concentration of reduced total Cr is ranging 14.4–
4.48 mg/l whereas the initial sample concentration is 184.4 mg/l.
Vermiculite is naturally occurring clayey mineral which is an Alu-
minosilicate having very high exchangeable capacity of 120.8cmol
(+) kg
1 and as a result of this it could absorb a large amount of
Chromium in the exchange sites. It is observed that it is very well
capable of reducing the concentration of Chromium from the
 S. Mani Tripathi, S. Chaurasia / Engineering Science and Technology, an International Journal 23 (2020) 1153–1161 1159

Table 5
Efficiency of bio-absorbents in reducing salts and Chromium in tannery effluent.

Absorbent pH Electrical Total Dissolve Total Chromium (mg/l) Absorption

Conductivity (dSm
1) Solid (mg/l) Capacity (mg/kg)
Before treatment After treatment
First Slot (Monomer Column)
100% Sawdust 5.73 8.01 5121 184.8 14.4 893.2
100% Rice husk 5.06 10.21 6529 184.8 10.52 633.6
100% Coir pith 7.15 8.00 5121 184.8 10.40 1204.6
100% Vermiculite 7.75 5.21 3329 184.8 8.19 262.9
Second Slot (Mixed Column)
50%Sawdust + 50%Vermiculite 6.08 7.71 4929 184.8 8.42 789.2
50% Rice husk + 50%Vermiculite 4.94 8.71 5569 184.8 8.24 508.3
50%Coir pith + 50%Vermiculite 7.34 7.01 4481 184.8 12.81 1386.2
Third Slot (Layered Column)
75%Sawdust + 25%Vermiculite 6.46 8.91 5691 184.8 10.89 467.3
75%Rice husk + 25%Vermiculite 4.75 8.16 5249 184.8 7.21 472.1
75%Coir pith + 25%Vermiculite 7.25 6.71 4289 184.8 4.48 578.1

sample. It also improves the removal efficiency of coir pith, rice
husk and sawdust.
Biological wastes like coir pith in both mono and mixed column
with vermiculite is also very effective in reducing the Chromium
from the sample (Fig. 4). It is observed that coir pith has highest
absorption of Chromium 1204.6 mg/kg which is lesser than the
previous values reported [1,17]. Results show that sawdust
increases only the capacity of absorbent from 467.4 to 893.2 mg/
kg. Higher value was reported by [15,16]. Conversely, in the third
slot of layered column which contains coir pith and vermiculite,
Chromium is noticeably reduced.
The net Chromium reduction (calculated based on passing efflu-
ent volume from column and weight coir pith) is 578.1 mg/kg. It
recommends that layer column of coir pith has efficiency of only
41.7% as in the mixed column; an analogous tendency is also seen
for rice husk and saw dust.
Removal efficiency of Chromium can be calculated from the
total volume of influent to the total amount of Chromium passed
through the column. Weight absorbent in the column ranges from
262.8 to 1386.1 mg/kg. Column which contains coir pith (50%) +
vermiculites (50%) has highest value of absorption capacity. Coir
pith alone has 1204.6 mg/kg efficiency as shown in Table 5. In saw-
dust absorption capacity of Chromium tannery effluent sample
varies from 467.4 to 893.2 mg/kg and when saw dust is mixed with
vermiculite in second and third slot the absorption capacity
decreases. On the other hand, reasonable absorption capacity of
(472.1 to 633.6 mg/kg) is observed by rice husk alone and rice
husk-vermiculite mixture in the layered columns.
In the above graph the numbering from 1 to 10 of the absorbent
materials and its absorbing capacity are as follows-
1. 100% saw dust (176 g),
2. 100% rice husks (277 g),
3. 100% coir pith (115 g),
4. 100% vermiculite (700 g),
5. 50% saw dust (110 g) + 50% vermiculite (110 g),
6. 50% rice husks (190 g) + 50% vermiculite (190 g),
7. 50% coir pith (120 g) + 50% vermiculite (120 g),
8. 75% saw dust (150 g) + 25% vermiculite (170 g),
9. 75% rice husks (200 g) + 25% vermiculite (170 g) and
10. 75% coir pith (100 g) + 25% vermiculite (170 g).
After the bio-absorption of sample through different bio-media.
Cr(VI) may be present on their surface; Cr(VI) can be reduced by
treating media with Fe(II) as we know that Cr(VI) is a strong oxi-
dant and is reduced in the presence of electron donor.
The existence of wastes are of two types: one being the only
bio-wastes used for bio-absorption, (say A) and the other one being
the combination of bio-wastes with vermiculite (the mineral con-
taining Fe(II)), (say B). The treatment of both ‘‘A” and ‘‘B” depends

Fig. 4. Bio-absorption potential of various absorbents in different combination.

1160 S. Mani Tripathi, S. Chaurasia / Engineering Science and Technology, an International Journal 23 (2020) 1153–1161
on their typology. ‘‘A” contains both forms of Chromium, i.e. Cr(III)
and Cr(VI) whereas ‘‘B” contains the reduced form only Cr(III).
‘‘B” can be dealt in majorly two ways:
1. Direct disposal;
2. Use of bio-wastes like sawdust, rice-husk, coir-pith as a base mate-
rial for plantation purposes.
The approximate intake of Cr(III) from different sources of air,
water and food is about 0.2 lg–0.4 lg, 2 lg, 60 lg, respectively
on a daily basis. Cr(III) also acts one of the nutrients which is essen-
tial for the bodies of human beings with an approximate recom-
mendation of about 50–200 lg/d. Carcinogenic potential of Cr(III)
is also unknown.(Source: Agency for Toxic Substances and Disease
Registry (ASTDR)). Toxicological Profile for Chromium, U.S. Public
Health Service, U.S. Department of Health and Human Services,
Atlanta, G.A. [3]. Thus, both of the methods listed above can be
used for the treatment, disposal or use.
‘‘A” which contains Cr(III) and Cr(VI), poses the main problem
for the treatment and disposal of Cr(VI) as already stated in the
paper. ‘‘A” can be tackled in following ways:
1. Selective disposal
It has been reported by Tiwari et al. (2009) that presence of high
organic matter in the soil, e.g. peat stabilizes Cr(VI) as it contains
many reductants. Photoremediation also reduces the Cr(VI) and it
combination with Fe(II) acts as a photocatalyst (Hug et al., 1997).
Thus, disposal of ‘‘A” in combination with ‘‘B” may offer to provide
fruitful results.
2. Phytoremediation
‘‘A” can be used as a base material for plants that hyper accu-
mulate. It has been reported by Tiwari et al. (2009) that the accu-
mulation of Chromium takes place in the order of
roots > stem > leaves > seed. Two parameters, namely bio-
concentration factor (BCF) and translocation factor (TF) can be used
to evaluate plants ability to deal with heavy metals. (Rafati et al.,
2011), BCF > 1 and TF < 1 holds good for phytoremediation. Some
examples include Pluchea indica, Amaranthus dublius [4,10] etc.
3. Recovery and Reuse
The Chromium can be recovered from ‘‘A” and ‘‘B” and used as a
raw material for the chrome plating industry or for production of
chrome leather etc.
Bioremediation of Chromium from wastewater or polluted
water is kind of waste management process. The process of treat-
ment and disposal of materials used for the above discussed
methodology (here bio-wastes) is an extended study. This paper
presents a limited discussion on the methods of treatment and dis-
posal of bio-wastes and leaves a scope for future works and study.
5. Conclusions
Tannery industries in Unnao for making appreciable quality and
quantity of product, uses huge amount of chemicals and fresh
water in lieu of which heavy metals like Chromium are found in
the vicinity of which get released from the effluents when passed
through drains. Yellow patches of Chromium can be seen easily
on the walls of the buildings at Dharamkata which has been the
result of dumping solid waste on open lands. Chromium contami-
nates subsurface water, when it comes in contact with water in
aquifer after seepage through various layers of the earth. Chro-
mium is observed mainly in two forms Cr(VI) and Cr(III) out of
which Cr(III) and Chromium metal is not harmful as it is insoluble
in water. Hexavalent Chromium is a strong oxidant and electron
donor like vermiculite reduced the Cr(VI). It has been found that
there are certain percentages of Cr(VI) in groundwater and surface
water both, near these industries. It can be detected by using
Diphenylcarbazide process by spectrophotometer. Chromium has
been detected at multiple sites in Unnao, both on surface as well
as in subsurface water, thereby clearly suggesting that if not reme-
diated, it may prove to be disastrous for the human being and other
creatures at Unnao. There are many other methods to reduce Chro-
mium concentration like oxidation, reduction, ion exchange
method. Many physiochemical methods are used but they are very
costly and complex in nature. Cr(VI) is highly oxidizing in nature
and can be reduced by ferrous iron which present in the soil as
minerals acts as a reducing agent. Different columns are used
which have different absorbents and combination of absorbent
and vermiculite of different ratio. It has been found that biological
waste can be used as absorbent materials and the efficiency for
reduction of Cr(VI) gets better by the combination of vermiculite
with the bio-absorbent which is dependent upon pH, Electrical
Conductivity and TDS of the sample. Column which contains coir
pith and vermiculite in ratio (1:2v/v ratio) is observed to be more
efficient than the other bio-waste or combination of bio-waste and
vermiculite in reducing concentration of Chromium. Therefore, this
study shows that the low-cost and easily available absorbents can
be used to remove the Chromium from the tannery effluents
within a certain limits which can be further removed by other effi-
cient method.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
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See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/334947222

Bioremediation of Groundwater: An Overview

Article  in  International Journal of Applied Engineering Research · November 2018

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 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 13, Number 24 (2018) pp. 16825-16832
© Research India Publications. http://www.ripublication.com
Bioremediation of Groundwater: An Overview
Shivam Mani Tripathi 1, Shri Ram2
1 ,2
Civil Engineering Department, MMMUT Gorakhpur, India
Abstract
In past, we have large open area and abundant land resources
and groundwater. But after the industrialization the use of
hazardous chemicals increased due to unmanageable
conditions. The chemical disposed on the ground surface &
many other anthropogenic activities by humans like use of
pesticides and oil spillage contaminated the soil and
groundwater. The different type of contaminant by percolation
through the ground reach to the aquifer and get affected which
causes serious problem. We spend lot of money and use many
technologies to extract and remediate the contamination. In
spite of different methods, bioremediation is a technology
which is cost efficient and effective by using natural microbes
and degrades the contaminants the conditions and different
bioremediation technologies like in-situ, ex-situ,
phytoremediation technology are described. Some
contaminates like LNAPLS, DNAPLS, BTEX, TCE,
Ammonia etc. also briefly described. The different sources, &
condition & technologies of remediation are also discussed.
INTRODUCTION
Water beneath the ground which saturates the pores of
subsurface is known as groundwater. Huge populations of
world depend upon the groundwater as the source of their
livelihood. About 1.69 percent of total water present in ground
are highly mineralized groundwater they don’t require much
treatment before use. They get filtered and mineralized by
their movement in ground. But after industrialization and
increase in anthropogenic activity of human, many industrial
effluents percolate the ground and reach to the water table
which contaminates the groundwater some chemicals like
Methyl Tert-Butyl Ether (MTBE), Benzene, toluene, and the
three xylene isomers (BTEX),etc. percolates to the
groundwater and causes serious problem there are some heavy
metals like chromium,
cadmium, mercury, cobalt, lead, arsenic can cause various
disease such as cancer, cardiovascular and neurological
diseases etc. for extraction or treatment of these contamination
world are using different techniques and investing million
billions of money. Bioremediation is the one of the technique
by which we can easily and feasibly extract or treat such type
of contamination. It is a process by which organic wastes are
biologically degraded under controlled conditions to a mild
state, or to levels below concentration limits established by
regulatory authorities for bioremediation to be effective;
microorganisms must enzymatically attack the pollutants and
alter them to harmless products. Bioremediation can be
successful only where environmental conditions allow
microbial growth and activity, its purpose often includes the
changes in environmental parameters to allow microbial
growth and degradation to proceed at a faster rate.
Bioremediation techniques are typically more economical
than other methods such as incineration, and some pollutants
16825
can be treated on site, thus reducing exposure risks for clean-
up personnel, or potentially wider exposure as a result of
transportation accidents. Methodology of this process is not
technically difficult, considerable experience and knowledge
may require implementing this process, by thoroughly
investigating the site and to know required condition to
achieve.
The usual technique of remediation is to plow up
contaminated soil and take away to the site, or to cover or cap
the contaminated area. There are some drawbacks. The first
method simply transport the contaminated materials which
create major risks is excavation, handling, and transport of
hazardous material. It is very difficult to find the new landfill
sites for disposal. The cover or cap method is only temporary
solution whereas contaminants remain on site which requires
monitoring and maintaining the engineered barrier for a long
time which increase the cost and the liabilities. The superior
and advanced methods than those previous methods which
completely eliminate the pollutants or least transformation to
innocuous substances. Some technologies that have been used
are high-temperature incineration and various types of
chemical decomposition (e.g., base-catalyzed de-chlorination,
UV oxidation). They can be very effective at reducing levels
of a range of contaminants, but have several drawbacks,
principally their technological complexity, the cost for small-
scale application, and the lack of public acceptance, especially
for incineration that may increase the exposure to
contaminants for both the workers at the site and nearby
residents.
FACTORS OF BIO-REMEDIATION
Bio-remediation is a complex method to optimize this method
it requires several factors to work in appropriate manner
environmental factors such as pH, temperature, type of soil,
presence of oxygen etc. These conditions required to
biological growth of micro-organism which treat the
contamination is control manner. Some of the factors and
acceptable condition on which bioremediation work are
shown below in Table1:
Table 1: Factors of Bioremediation
Factors Required Condition
Micro-organism Aerobic and Anaerobic
Biological Process Catabolism and Anabolism
Environmental Temperature, pH, Oxygen content,
Factor Electron acceptor or donor
Nutrient Carbon, Nitrogen, Oxygen etc
Soil Moisture 25-28% of water holding capacity
Type of Soil Clay and silty soil
 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 13, Number 24 (2018) pp. 16825-16832
© Research India Publications. http://www.ripublication.com

Micro-organism can be grown in almost in all environmental Low concentration of contaminants can be directly treated by
conditions. Microbes will accumulates and grow at sub zero bioremediation. It is time taking process & it takes about 6
temperature as well as at very high temperature or in water month to a 1 year or more to purify soil containing 2 % of
medium or in presence or in absence of oxygen it can be oils, but if the concentration is 0.8 or less percentage of heavy
grown in presence of any hazardous compound or is waste oil present it purify within 1 to 2 months. These methods help
stream. The presence of carbon source as the energy of in recycling and reuse the soil with some efforts it is a
enzyme that can be used to remediate or degrade the environmentally friendly process.
contaminants are required for microbial growth. We can
subdivide these micro-organisms into following groups:
Table 2: Environmental Condition
Aerobic like Pseudomonas, Alcaligenes,
Sphingomonas, Rhodococcus, and Mycobacterium. These Environmental Optimum Condition required
microbes remediate the hydrocarbon and pesticides, both Factors Concentration for microbial
alkanes and compounds. Lots of these bacteria are the main Activity
source of energy and carbon it accumulate in presence of
Soil Moisture Water holding 25-28% water
oxygen.
capacity 25-85% holding capacity
Anaerobic are not much use as the aerobic bacteria. pH 6.5-8.0 5.5-8.5
It can be used to bio-remediate the polychlorinated biphenyls
(PCBs) in river sediments, dechlorination of the solvent Nutrient C:N:P 120:10:1 N and P for growth
Trichloroethylene (TCE), and chromium. It works in the of microbes
absence of oxygen. Temperature 20-30°C 15-45°C
Ligninolytic fungi they are use to degrade the Oxygen >0.2 mg/l DO, 10% Aerobic, minimum
extremely unlike range of importunate or toxic environmental air-filled pore for air-filled pore
pollutants. Common substrates used include straw, saw dust, aerobic degradation space of 10%
or corn cobs. Example white rot fungus Redox potential Eh > 50 mill volts
Methylotrophs bacteria that utilized methane for Heavy metals 700ppm Total content
carbon and energy as their growth source it is an aerobic 2000ppm
bacteria. The initial enzyme in the pathway for aerobic Contaminants Hydrocarbon 5-10% Not too toxic
degradation, methane mono-oxygenase, has a broad substrate of dry weight of soil
range and is active against a wide range of compounds,
including the chlorinated aliphatics trichloroethylene and 1,2-
dichloroethane Groundwater Pollution
When the pollutants released on the ground it percolates
through different interfaces of ground layer which comes in
ENVIRONMENTAL FACTORS contact or mixed with the groundwater table. These substance
1. Nutrient: changes their physical and chemical properties like
temperature, pH, color, total dissolve solids (TDS), dissolve
The most important element which require in large quantity is oxygen (DO) etc. more than the tolerance limits causes due to
Carbon that helps in the growth of microbes. Other than this anthropogenic activity of human or due to release of
oxygen, hydrogen and nitrogen and is constituent about 95% chemicals by industries and use different chemicals like
of the weight are required. Type of soil and its contamination pesticides in agriculture practice. Water pollution can also
helps to decide the type of bioremediation required the occur due to presence of unwanted substance or the impurity
concentration of sulfur and phosphorous helps to remediate in the groundwater.
the 70% of the contaminants. The nutritional requirement of
carbon to nitrogen ratio is 10:1, and carbon to phosphorous is It affects the plume within an aquifer. Dispersion and
30:1 movement of water within the aquifer pollute the large area of
the ground. Its advancing boundary, often called plume edge,
2. Soil: which get contacts with groundwater well or springs river etc
Concentration of 5% contaminants or more highly into surface water which make water toxic for humans and
contaminated water can be treated by passing water to wildlife. Plume front i.e. movement of plume can be analyzed
different interface of the soil strata. Interface having active by groundwater model. Soil properties, hydrology, geology
agents that partially separate contaminates from the oils. After and nature of contaminants help to analyze the groundwater
passing to this, we can set up bioremediation to clean up the pollution.
soil. At the experimental stage, this process is only one which Toxicity of groundwater can be illustrated as foreign material
turns the contaminated soil into suitable soil for site & present in the groundwater which may have risk to the human
landscaping. Many other modifications are applying for or wildlife health. These can be chronicle neurological
making this process more effective. disorder or other health issue or psychologically not
acceptable by human, it can be further sub divided into two
toxicity i.e. acute toxicity and chronic toxicity. Acute toxicity

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© Research India Publications. http://www.ripublication.com
is the toxicity as a result of short term exposure to a toxicant
quantified by LD50. The LD50 is defined as the lethal dose at
which 50% of the population if killed in a given period of
time; an LC50 is the lethal concentration required to kill 50%
of the population. There can be a wide range of tolerance
to toxic agents among different populations of a species which
should be taken into account. Whereas chronic toxicity is that
toxicity as a result of long term exposures to a toxicant which
can cause serious issues like carcinogenicity, mutagenicity,
teratogenicity problem which can cause death by bio-
accumulation. Bioaccumulation is the accumulation of
substances, such as pesticides, or other chemicals in an
organism. Bioaccumulation occurs when an organism absorbs
a substance at a rate faster than that at which the substance is
lost by catabolism and excretion. No Observed Effect Level
(NOEL), Lowest Observed Effect Level (LOEL) and other are
the examples of this. The NOEL (no observable effect level)
is the highest dose or exposure level of a substance or material
that produces no noticeable (observable) toxic effect on tested
animals. The LOAEL is the lowest dosage level at which
chronic exposure to the substance shows adverse effects on
tested animals.
It is more difficult to stop groundwater as the surface water
because of movement of groundwater through unseen aquifer
through a large area. Clayey soils are non-porous aquifer
which partially purifies the water by filtration (adsorption and
absorption), dilution, and in some cases chemical reaction and
biological activity; some pollutants changes to soil
contaminants. Contaminants which percolate through
fractures cannot be filtered and can be easily contact with the
surface water.
By using different techniques we can remove the pollutants or
contaminants. Ground water remediation by using physical,
biological and chemical or the combination of technologies
we can apply and change the property of contaminated
groundwater. Some of the biological treatment techniques
include bio-augumentation, bioventing, biosparging,
bioslurping, and phytoremediation. Some chemical treatment
techniques include ozone and oxygen gas injection, chemical
precipitation, membrane separation, ion exchange, carbon
absorption, aqueous chemical oxidation, and surfactant
enhanced recovery. Some chemical techniques may be
implemented using nano-material.
GROUNDWATER REMEDIATION
Pollutant removes or remediates by using physical, chemical
and biological or combination of these processes helps to
remediate the water, is said to be groundwater remediation. It
can be sub-divided into two categories ex-situ and in-situ.
Ex-Situ Technology
Ex-Situ Technology involves treatment of groundwater by
dewatering the polluted aquifer (pumping out), then treating
the water on surface by Physical, chemical or biological
technology and finally re-injecting the treated water to the
aquifer. Extraction of groundwater from aquifer, treat above
16827
ground and return the treated water to the aquifer. Extraction
is done by pumping groundwater from the well or trench and
treat them.
Figure1: Ex-situ Remediation
In-situ Technology
In-Situ Technology involves treatment of groundwater within
the aquifer (in the sub-surface) by using thermal, chemical
and biological treatment technology. Involve treatment of
groundwater (in-place) without extracting the water from
aquifer.
Some contaminants like DNAPL (Dense Non Aqueous Phase
Liquids), LNAPL (Light Non Aqueous Phase Liquids),
Inorganic Chemicals (Ammonia, Cyanide, and Fluoride),
Metals, Bacteria and Virus
DNAPL: Dense Non Aqueous Phase Liquids are organic
compounds heavier than water and having less absolute
solubility. These compounds include chlorinated solvents
(EDC) and halogenated aromatics (TCB) DNAPLs migrate
very fast through the soil formation and reach water table
because of their high density and low viscosity. They sink
steeply to the bottom of the aquifer till they reach the
impermeable bed rock.
LNAPL: Light Non Aqueous Phase Liquids are organic
compounds lighter than water and having low solubility.
These liquids include Gasoline, fuel oil and other petroleum
products. Remediation may require the use of more than one
technology. It is likely that several remediation techniques,
used in series and/or parallel applications, will be required for
maximum contaminant removal. This collaborative effort may
be referred to as a treatment train approach.
Treatment of DNAPL
The following types of technologies are increasingly being
used to treat DNAPLs:
• In situ thermal treatment
• In situ chemical oxidation
• Surfactant/co-solvent flushing
• In situ bioremediation
• Ground water extraction (P&T or recirculation)
• Excavation containment (Engineered caps and slurry
walls
 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 13, Number 24 (2018) pp. 16825-16832
© Research India Publications. http://www.ripublication.com

Figure 2: In-situ Remediation

Table 3: Some DNAPL sources and Treatment Technology

Contaminants Main Source Treatment Technology
Trichloroethylene Degreasing of Metal and Electronic parts, Pump and Treat
(TCE) Extract for oil and waxes, fumigant, carries in Activated Carbon
paints and adhesives Thermal and Biological
Ammonia Ammonia Storage Tanks, Landfill leaks, Pump and Treat
Waste stockpile, etc. Combination of Air Stripping, Nitrification, Ion
Exchange.

Bioremediation strategies Bio-venting

In-Situ Bioremediation: It is a new in-situ biodegradation technology which degrades
the NAPL aerobically by providing oxygen to the microbes
To eliminate the toxic chemicals or substance from the
within the soil. By comparing the soil-vapor extraction and
subsurface of the ground we setup the biological treatment. To
bioventing we get this technology require low air-flow rates to
give the appropriate conditions required for the growth of
provide only enough oxygen to sustain microbial activity. By
microbes and convert the organic matters into toxic less
supplying air we can easily provide oxygen to the lasting
matter we require the combination of many scientific and
contamination in soil through the wells. Adsorbed fuel
engineering disciplines.
residuals are biodegraded, and volatile compounds also are
biodegraded as vapors move slowly through biologically
active soil [13].
Biosparging.
Increase the rate of biodegradation of contaminants by
naturally occurring microbes. We oxidize the aquifer by Bio-augmentation
injecting air under pressure below the water table which
The introduction of a group of natural microbial strains or a
increase the oxygen concentration and enhance the rate of
genetically engineered variant to treat contaminated soil or
reaction. It increases the assimilation in the zone of saturation
water. It is use to restart the activated sludge process of
and thus increases the contact between the groundwater and
bioreactor to treat the municipal wastewater. Most cultures
soil. The simplicity and optimal cost of setup of small-
available contain a research based consortium of Microbial
diameter air injection points allow significant elasticity in
cultures, containing all necessary microorganisms At sites
designing and construction of system.

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where soil and groundwater are contaminated with chlorinated
ethenes, such as tetra-chloro-ethylene and trichloroethylene,
bio-augmentation is used to ensure that the in situ
microorganisms can completely degrade these contaminants
to ethylene and chloride, which are non-toxic [9]. Monitoring
of this system is difficult.
Bio-piling
Biopile treatment is a complete technology in which aeration
is done by under pressure injecting air and excavated soils are
mixed with improved soil. The contaminants are turns to
carbon dioxide and water. The basic biopile system includes a
treatment bed, an aeration system, an irrigation/nutrient
system and a leach ate collection system. Physical parameter
like heat, moisture, nutrient, pH and oxygen are controlled to
optimize the biodegradation. By applying positive pressure or
vacuum from passing air and nutrients the irrigation/nutrient
system is covered. It can be high up to 20 feet and caped with
plastic to control evaporation, runoff, and volatilization, and
encourage solar heating. . If Volatile Organic compounds
(VOCs) in the soil volatilize into the air stream, the air leaving
the soil may be treated to remove or destroy the VOCs before
they are discharged into the atmosphere. Treatment time is
typically 3 to 6 months [25].
Ex-Situ Bio-remediation
It is a type of bioremediation in which contaminates are
treated on other location from the contaminated site. When the
organic matters degrade by micro-organisms at very high
temperature is known as composting. On average compost
temperature is in between 55° to 65°C. The degradation of
organic matter to the waste increases by increasing in
temperature. Windrow composting has been demonstrated
using the following basic steps. First, contaminated soils are
excavated and screened to remove large rocks and debris [2,
3].
Bio-reactors
It is an ex-situ process treatment is done by pumped up
contaminated water or soil it is also known as slurry reactors
or aqueous reactors. By engineered contaminated system it
bio-remediate the contaminated water or material (soil,
sediment, sludge) by reactors. A containment vessel and
apparatus used to establish three phase i.e. solid, liquid and
gas combined condition to enhance the rate of bioremediation
of soil bound and water soluble pollutants as water slurry of
the biomass and contaminated soil and capable of eliminating
the particular contaminated from it is known as slurry
bioreactors. As the physical environment is easily controlled
and manageable the bioremediation rate is more as compare to
in situ or solid-phase system. In spite of advantage there are
some disadvantages. Pre treatment o contaminated soil is
required (excavation) or instead of this we exposed the
contaminant from the soil from soil washing or physical
extraction (vacuum extraction) prior to place in a bioreactor.

Table 4: Methods Develop in Bio-remediation [24, 12]

Technique Examples Benefits Applications References
In Situ Biosparging; Most efficient, Non insidious; Biodegradative abilities of [4, 9, 19]
Bioventing; Relative passive; indigenous microorganisms.
Bioaugmentation Naturally attenuated process, Presence of metals and inorganic
treat soil and water compounds
Environmental parameters
Biodegradability of pollutants
Chemical solubility Geological
factors Distribution of pollutants
Ex situ Land farming (Solid- Cost efficient ,Simple, Surface application, aerobic [2,3]
phase treatment Inexpensive ,self-heating. process, application of organic
system). Low cost Rapid reaction rate, materials to natural soils followed
Composting Inexpensive, self heating. by irrigation and tilling
(Anaerobic, converts Can be done on site. To make plants healthier good
solid organic wastes alternative to land filling or
into humus-like incinerating practical and
material) convenient. Surface application,
Biopiles agricultural to municipal waste
Bioreactors Slurry reactors Rapid degradation kinetic Bioaugmentat Toxicity of [20]
Optimized environmental amendments
Aqueous reactors parameters.
Enhances mass transfer
Effective use of inoculants and Toxic concentrations of
surfactant contaminants

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© Research India Publications. http://www.ripublication.com

Technique Examples Benefits Applications References

Precipitation Non-directed physico- Cost-effective Removal of heavy Metals [16]
or chemical complex -
Flocculation ation reaction between
dissolved contaminants
and charged cellular
components (dead
Biomass)
Micro- Microfiltration Remove dissolved solids Waste water treatment; recovery -
filtration membranes are used at a rapidly and reuse of more than 90% of
constant pressure original waste water
Electro Uses cataion and anion Withstand high temperature Efficiently remove the dissolved -
dialysis exchange membra-ne and can be reused solid
pairs

Advantages of Bio-remediation Drawbacks of Bio-remediation

 It takes less time comparing to other techniques to accept
the waste treatment process for contaminate material or
soil it is a naturally process. Micro-organisms are capable
to eliminate the contaminants, when contaminants
degrades it decrease the biomass population. The final
parts of the treatment are typically harmless product.
 Bioremediation can be practice without causing
interference in natural activities it can be easily
performed with very less efforts. Transportation of wastes
from the site to off-sites is eliminated from this there is
no risk to the human health which can be arises due to the
transportation.
 It requires optimal cost to degrade the hazardous wastes
compare to the other traditional methods.
 Bioremediation completely eliminate the pollutant matter,
many toxic compounds changes to harmless products.
This process also make free from future liabilities of the
sites and disposal of contaminated materials.
 It uses the natural microbes which is harmless to
environment compare to the use of hazardous chemicals.
It changes toxic chemicals into harmless gases or into
water toxicity of chemical completely eliminated.
 Bioremediation is applicable only on those compounds
which are bio-degradable. All compounds cannot be
degraded completely.
 There are some anxieties that the products of
biodegradation may be more continual or toxic than the
parent compound. Biological processes are often highly
explicit. Important site factors required for success
include the presence of metabolically capable microbial
populations, suitable environmental growth conditions,
and appropriate levels of nutrients and contaminants.
 It is difficult to extrapolate from bench and pilot-scale
studies to full-scale field operations.
 There are needs of improvement and developments and
engineer bioremediation technologies are required to
develop for appropriate sites with typical combinations of
contamination that are not evenly detached in the
environment. Contaminants may be present as solids,
liquids, and gases.
 Bioremediation habitually takes long period of time than
other traditional treatment options, such as excavation
and removal of soil or incineration.
 Regulatory uncertainty remains regarding acceptable
performance criteria for bioremediation

Table 5: Some Contaminants Source and Process of Bio-remediation [9]

Class of Contaminants Example Source Process of Bio-remediation
Chlorinated solvents Trichloroethylene Drycleaners Anaerobic
Polychlorinated biphenyls 4-Chlorobiphenyl Electrical manufacturing Anaerobic
“BTEX” Benzene, Toluene, Ethylbenzene Oil production and storage Both Aerobic and Anaerobic
and Xylene Gas work sites Airports
Paint manufacture
Polyaromatic Naphthlene,Anthracen Oil production and Aerobic
hydrocarbons e,Pyrene Storage, Engine works
Pesticides Atrazine, 2 4 D , Agriculture. Pesticides Both Aerobic and Anaerobic
Parathon manufacture

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Table 6: Some other Contaminants Sources and Treatment Technology

Contaminants Sources Treatment Technology

1,2 Dichloroethene EDC From EDC and VCM Plants, storage tanks, In-situ Bioremediation
(DNAPL) pipelines etc

Gasoline (LNAPL) Gasoline and other petroleum fuels tanks, petrol In-situ Bioremediation; Vapor extraction
stations, storage tanks and pipelines

Ammonia Ammonia Storage Tanks, Landfill leaks, Waste Pump and Treat; Combination of Air Stripping,
stockpile, etc. Nitrification, Ion Exchange

Phyto-remediation Overview of Phyto-remediation applications

Microorganisms are not the only species that can be improved
by genetic alteration for bio-remediatory purposes. Plants
have also been used and studied. Bioremediation by plants is
called phytoremediation. Phytoremediation is a rising
technology that uses a variety of plants to degrade, extract,
contain, or immobilize contaminants from soil and water. This
technology has been receiving noticeable lately as a modern
technology, cost-effective alternative to the more established
treatment methods used at hazardous waste sites.
 Cost of phytoremediation is very minimal as compare to
the other typical methods like in-situ and en-situ process
of bioremediation
 Monitoring of plants is very easy.
 There is chance to re-use and recycle the compound.
 It uses naturally occurring organisms and preserves the
natural state of the environment.
 The low cost of phytoremediation (up to 1000 times
cheaper than excavation and reburial) is the main
advantage of phytoremediation.

Table 7: Types of Phytoremediation:

Process Function Pollutant Medium Plants References

Phytoextraction Remove metals pollutants that Cd, Pb, Zn, Soil & Viola baoshanensis, [14, 26]
accumulate in plants. Remove As, Petroleum, Groundwater Sedum alfredii, Rumex
organics from soil by Hydrocarbos crispus
concentrating them in plant parts and
Radionuclies

Phytotranformation Plant uptake and degradation of Xenobiotic Soil Cannas [15]

organic Compounds substances

Phytodegradation Plants and associated DDT, Groundwater Elodea [8, 17]

microorganisms degrade organic Explosives, Canadensis,Pueraria
pollutants waste and
Nitrates

Rhizofiltration Roots absorb and Zn, Pb, Cd, As Zn, Pb, Cd, As Groundwater Brassica juncea [6, 22]
Groundwateradsorb pollutants,
mainly metals, from water and
aqueous waste streams

Phytostabilization Use of plants to reduce the Cu, Cd, Cr, Soil Anthyllis vulneraria, [21]
(Immobilization) bioavailability of pollutants in the Ni,Pb, Zn Festuca arvernensis
Environment

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Performance Evaluation and Efficiency of Sewage Treatment Plant Using

Surface Aerator and Air Diffuser

Article · April 2007

DOI: 10.15680/IJIRSET.2016.0504108

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 ISSN(Online) : 2319-8753
ISSN (Print) : 2347-6710

International Journal of Innovative Research in Science,

Engineering and Technology
(An ISO 3297: 2007 Certified Organization)

Vol. 5, Issue 4, April 2016

Performance Evaluation and Efficiency of

Sewage Treatment Plant Using Surface
Aerator and Air Diffuser
Shivam Mani Tripathi 1 , Dr. Govind Pandey 2
P.G. Student, Department of Civil Engineering, MMM University of Technology, Gorakhpur, Uttar Pradesh, India1
Professor, Department of Civil Engineering, MMM University Of Technology, Gorakhpur, Uttar Pradesh, India2

ABSTRACT: Allahabad city host Wastewater Treatment Plant (WTP) based on activated sludge process with surface
aerator and air diffuser along the side of GANGA River, located in Naini, Allahabad, U.P, India. This plant is
constructed and design with an aim to manage wastewater so as to minimize disease-causing organisms, organic matter,
solids, nutrients, and other pollutants. It was revealed from the performance study that efficiency of the treatment plant
was good enough with respect to removal of total dissolved solids in contrast to the reduction in other parameters like,
total suspended solids, BOD and COD. In Naini plant, BOD, COD and TSS removal efficiency of three month were,
79.81, 87.79 and 87.66% respectively. The order of reduction efficiency was BOD < TSS < COD STP. In addition to
this, the problem associated with the maintenance and operation of wastewater treatment plants is discussed. The
research work presents the results of the evaluation carried out for the efficiency analysis of STP based on activated
sludge process with surface aerator and air diffuser located in Allahabad for handling and treating the municipal
wastewater.

KEYWORDS: Performance Evaluation, activated sludge process with surface aerator and air diffuser, Total
Suspended Solid, Chemical Oxygen Demand, Biochemical oxygen demand.

I. INTRODUCTION

Every community produces both solid and liquid wastes. The liquid portion -wastewater - is essentially the water
supply of the community after it has been fouled by a variety of uses. From the standpoint of sources of generation,
wastewater may be defined as a combination of the liquid - or water-carried wastes removed from residences,
institutions, commercial and industrial establishments together with such groundwater, surface water and storm water
as may be present. If untreated wastewater is allowed to accumulate, the decomposition of the organic materials it
contains can lead to the production of large quantities of malodorous gases. In addition, untreated wastewater usually
contains numerous pathogenic, or disease-causing, microorganisms that dwell in the human intestinal tract or that may
be present in certain industrial waste. Wastewater also contains toxic compounds. For these reasons, the immediate and
nuisance-free removal of wastewater from it sources of generation, followed by treatment and disposal, is not only
desirable but also necessary in an industrialized society. There are several methods of treating the domestic / municipal
/industrial wastewater. Certain parameters, which are on higher side in raw wastewater needs to be, reduced according
to the pollution control board's norms by giving specific treatment. One of them is to supply the oxygen for removal of
BOD i.e. Bio-chemical Oxygen Demand. This is achieved by different methods of Aeration like surface aeration or by
diffused aeration etc. The type of Air diffuser use in Naini plant is Complete mix aeration. In this the influent and the
returned sludge are mixed and applied at several points along the length and width of the basin. The contents are mixed
and the MLSS flow across the tank to the effluent channel. The oxygen demand and organic loading are uniform along
entire length of basin. Flow regime in complete mix flow the sludge retention time is about 5-15 day, food to micro-
organism ratio is about 0.2-0.6 d-1 aerator loading is about 0.8-2.0 kg/m3d, MLSS is about 3000-6000 mg/l, aeration
period is about 3-5 hours, recirculation ratio (Qr/Q) is 0.25-1.00. Aeration system is coarse bubble is which various

Copyright to IJIRSET DOI:10.15680/IJIRSET.2016.0504108 5146

 ISSN(Online) : 2319-8753
ISSN (Print) : 2347-6710

International Journal of Innovative Research in Science,

Engineering and Technology
(An ISO 3297: 2007 Certified Organization)

Vol. 5, Issue 4, April 2016

nozzles or orifices with check-valve feature; Spurger air escapes from periphery of a flexible disc that may lift over.
The transfer efficiency of coarse bubble aeration is 4-8%, the transfer rate is about 0.6-1.2 kgO2/kW.h.
Advantages of coarse bubble aeration system are-
1. Non-clogging
2. Low maintenance
3. Air filter not needed
4. Used to produce spiral flow
Disadvantages of coarse bubble aeration system are-
1. High initial cost
2. Low oxygen transfer
3. High power cost
Mechanical aerator or surface aerators in this the oxygen is entrained from the atmosphere. The aerators consist of
submerged or partially submerged impellers that are attached to motors mounted on float or fixed structures. Surface
aerators are classified according to the rotational speed of impeller there are four types of surface aerators
1. Radial flow, low speed 20-60 rpm
2. Axial flow high speed 300-1200rpm
3. Brush rotor
4. Submerged turbine
The mechanical aerators fall into two major groups: surface impeller and submerged turbine. In Naini plant the
mechanical aerator use is surface impeller with axial flow high speed 300-1200rpm this aerator having high speed, use
smaller dia propeller and floating structure. The transfer rate is 1.2 - 2.4 kgO2/kW.h
Advantages of mechanical aerator of axial flow high speed-
1. Low initial cost
2. It can be adjusted to varying water level,
3. Flexible operation
Disadvantages of mechanical aerator of axial flow high speed-
1. Icing in cold climate
2. Poor accessibility for maintenance
3. Mixing inadequate

II. STUDY AREA

The study area covers Sewage Treatment Plant (STP) based on activated sludge process with surface aerator and air
diffuser and situated on the north bank of Situated on the right bank of river Ganga in North –west of Allahabad city.
Process Flow Diagram of Sewage Treatment Plant of Naini working on the principle of activated sludge process with
surface aerator and air diffuser given in Fig. 1. The STP is of the capacity of Naini is 80 MLD. It has surface aerator
and air diffuser in which surface aerator contain 60 MLD capacity and air diffuser contain 20 MLD capacity of
wastewater. By which wastewater get aerated and further used for treatment. As Naini plant was firstly has capacity of
only 60 MLD by surface aerator after expansion of the city and population it require to expand the treatment plant then
20 MLD of air diffuser is attached to the Naini plant for getting the better result. This STP work on improving the
quality of wastewater by reducing the value of the total suspended solids (TSS), chemical oxygen demand (COD),
biological oxygen demand (BOD), and increasing the value of dissolve oxygen (DO). Allahabad Naini plant has
chemical oxygen demand (COD) of raw wastewater 239mg/l and after treatment 122mg/l. Biological oxygen demand
(BOD) of raw wastewater is 60 mg/l and after treatment 17mg/l. Total suspended solid (TSS) of raw wastewater is
231mg/l and after treatment 19mg/l. Average wastewater received by STP is about 57MLD, the efficiency of total
suspended solid (TSS) of STP is about 87.54% and the efficiency of biological oxygen demand (BOD) is about
79.98%. As per information given by the Ganga Pollution Control Board (U.P.) to Central Pollution Control Board
(CPCB) the expenditure of operation and maintenance cost of sewage treatment plant of Allahabad Naini is about
229.038 lakh. Total area captured by Naini is 11 hectare. This research work evaluated the performance of the

Copyright to IJIRSET DOI:10.15680/IJIRSET.2016.0504108 5147

 ISSN(Online) : 2319-8753
ISSN (Print) : 2347-6710

International Journal of Innovative Research in Science,

Engineering and Technology
(An ISO 3297: 2007 Certified Organization)

Vol. 5, Issue 4, April 2016

STP based on surface aerator and air diffuser in terms of wastewater characterization to derive a comparative account
between the pollution load before and after the treatment processes, besides, discerning their efficiency.

Fig1`: Process Flow Diagram of Sewage Treatment Plant of Naini

III. RESULT

The study carries out the parameters such as pH, BOD, TSS and COD of both the plants followed by overall
Efficiencies of three months i.e. October to December shown in figure.

pH OF pH OF
pH OF pH OF
PH OF PRIMARY SECODARY pH OF AIR
MONTH SURFACE RETURN
INFLUENT SETTLING SETTLING DIFFUSER
AERATOR SLUDGE
TANK TANK

OCTOBER 7.15 7.24 7.35 7.24 7.37 7.25

NOVEMBER 7.16 7.26 7.36 7.66 7.81 7.26
DECEMBER 7.19 7.31 7.44 7.24 7.43 7.25

Copyright to IJIRSET DOI:10.15680/IJIRSET.2016.0504108 5148

 ISSN(Online) : 2319-8753
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International Journal of Innovative Research in Science,

Engineering and Technology
(An ISO 3297: 2007 Certified Organization)

Vol. 5, Issue 4, April 2016

pH OF PER MONTH

PH OF INFLUENT
pH OF PRIMARY SETTLING TANK
pH OF SECODARY SETTLING TANK
7.35
7.15
7.24 7.36
7.16
7.26 7.44
7.31
7.19
OCTOBER NOVEMBER DECEMBER

pH OF SURFACE AERATOR &

AIR DIFFUSER
pH OF SURFACE AERATOR pH OF AIR DIFFUSER

7.81
7.66
7.37 7.43
7.24 7.24

OCTOBER NOVEMBER DECEMBER

AVERAGE SEWAGE AVERAGE BOD AVERAGE BOD EFFICIENCY

MONTH RECEIVED IN STP IN MLD INFLUENT IN MG/L EFFLUENT IN MG/L FOR BOD
OCTOBER 36.05 116.52 23.43 79.9
NOVEMBER 58.07 117.5 23.8 79.74
DECEMBER 55.87 117.48 23.52 79.78

Copyright to IJIRSET DOI:10.15680/IJIRSET.2016.0504108 5149

 ISSN(Online) : 2319-8753
ISSN (Print) : 2347-6710

International Journal of Innovative Research in Science,

Engineering and Technology
(An ISO 3297: 2007 Certified Organization)

Vol. 5, Issue 4, April 2016

AVERAGE SEWAGE RECEIVED IN STP

IN MLD
AVERAGE SEWAGE RECEIVED IN STP IN MLD

58.07 55.87
36.05

OCTOBER NOVEMBER DECEMBER

AVERAGE BOD
AVERAGE BOD INFLUENT IN MG/L
AVERAGE BOD EFFLUENT IN MG/L

116.52 117.5 117.48

23.43 23.8 23.52

OCTOBER NOVEMBER DECEMBER

EFFICIENCY FOR BOD

EFFICIENCY FOR BOD

79.9

79.78
79.74

OCTOBER NOVEMBER DECEMBER

Copyright to IJIRSET DOI:10.15680/IJIRSET.2016.0504108 5150

 ISSN(Online) : 2319-8753
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International Journal of Innovative Research in Science,

Engineering and Technology
(An ISO 3297: 2007 Certified Organization)

Vol. 5, Issue 4, April 2016

AVERAGE TSS INFLUENT IN AVERAGE TSS EFFICIENCY

MONTH STP IN MG/L EFFLUENT IN MG/L FOR TSS
OCTOBER 361.94 44 87.84
NOVEMBER 361.63 44.9 87.58
DECEMBER 362.68 45.16 87.55

AVERAGE TSS
AVERAGE TSS INFLUENT IN STP IN MG/L AVERAGE TSS EFFLUENT IN MG/L

361.94 361.63 362.68

44 44.9 45.16

OCTOBER NOVEMBER DECEMBER

EFFICIENCY FOR TSS

EFFICIENCY FOR TSS

87.84

87.58
87.55

OCTOBER NOVEMBER DECEMBER

Copyright to IJIRSET DOI:10.15680/IJIRSET.2016.0504108 5151

 ISSN(Online) : 2319-8753
ISSN (Print) : 2347-6710

International Journal of Innovative Research in Science,

Engineering and Technology
(An ISO 3297: 2007 Certified Organization)

Vol. 5, Issue 4, April 2016

AVERAGE COD OF AVERAGE COD OF

AVERAGE COD OF AVERAGE SLUDGE
MONTH PRIMARY SLUDGE SECONDARY EFFICIENCY
INFLUENT VOLUME INDEX
TREATMENT SLUDGE PROCOSS
OCTOBER 360.83 143.9 43.77 63.09 87.87
NOVEMBER 361.26 145.26 44.96 65.3 87.55
DECEMBER 362.03 144.12 43.67 65 87.94

AVERAGE COD PER MONTH

400

300

200

100

0
OCTOBER NOVEMBER DECEMBER

AVERAGE COD OF INFLUENT

AVERAGE COD OF PRIMARY SLUDGE TREATMENT
AVERAGE COD OF SECONDARY SLUDGE PROCOSS

AVERAGE COD OF SECONDARY SLUDGE

PROCOSS
45.5

45

44.5
AVERAGE COD OF SECONDARY
44 SLUDGE PROCOSS

43.5

43
OCTOBER NOVEMBER DECEMBER

Copyright to IJIRSET DOI:10.15680/IJIRSET.2016.0504108 5152

 ISSN(Online) : 2319-8753
ISSN (Print) : 2347-6710

International Journal of Innovative Research in Science,

Engineering and Technology
(An ISO 3297: 2007 Certified Organization)

Vol. 5, Issue 4, April 2016

AVERAGE SLUDGE VOLUME INDEX

65.5
65
64.5
64
63.5 AVERAGE SLUDGE
63 VOLUME INDEX
62.5
62
61.5
OCTOBER NOVEMBER DECEMBER

EFFICIENCY FOR COD

88.00

87.90
87.80
87.70

87.60 EFFICIENCY
87.50
87.40

87.30
OCTOBER NOVEMBER DECEMBER

IV. CONCLUSIONS

Allahabad city was selected for the study of the performance of STP in running condition i.e. the 80MLD based STP at
Naini and 10MLD. The conclusions drawn from the study are as follows:
 Presently the existing sewage treatment plant is working satisfactory and the results of treated water are
observed as per the central pollution control board norms. It has been observed that 100 % of the waste water
generated is not treated; thus more plants are required.
 All treated water is disposed into the Ganga River. The treated water may also be used for agricultural and
industrial purposes.
 Several important Water Quality Parameters like Fecal Coliform, Oil, Sulphate and Grease are not measured
on a regular basis.

Copyright to IJIRSET DOI:10.15680/IJIRSET.2016.0504108 5153

 ISSN(Online) : 2319-8753
ISSN (Print) : 2347-6710

International Journal of Innovative Research in Science,

Engineering and Technology
(An ISO 3297: 2007 Certified Organization)

Vol. 5, Issue 4, April 2016

REFERENCES

1. Central Public Health and Environmental Engineering Organisation, 2012, Manual on sewerage and sewage treatment, Ministry of urban
development, New Delhi.
2. Environmental Protection Agency, Manual on Procedures for Evaluating of Wastewater Treatment Plants, Office of Water Programs,
Washington D.C.
3. Metcalf and Eddy Inc., 2003, “Wastewater Engineering”, 4th Edition, Tata Mc Graw Hill Publishing C. Ltd., New Delhi.
4. D.G. Rao., 2013, “Wastewater treatment: Advance Process and Technologies”, CRC Press., New York
5. Wastewater technology factsheet - Sequencing batch reactor,” EPA, 1999.
6. A. Gallego, A. Hospido, M. T. Moreira and G. Feijoo, “Environmental Performance of Wastewater Treatment Plant,” Resources, Conservation
and Recycling, vol. 52, pp. 931-940, 2008.
7. D. Nolasco, D. Irvine, M. Manoharan and E. Giroux, “Evaluation and Optimization of Design/ Operation of Sequencing batch Reactors for
Wastewater treatment”.
8. A. H. Mahvi, “Sequencing Batch Reactor- A Promising Technology in Wastewater Treatment,” Iran Journal of Environmental Health Sciences
and Engineering, vol. 5, no. 2, pp. 79-90, 2008.
9. EPA, “Manual on Procedures for evaluating performance of wastewater treatment plants”.
10. C.P.H.E.E. Organization, “Manual on Sewerage and Sewage Treatment,” Ministry of Urban Development, New Delhi.
11. N. E. I. W. P. Control, “Sequencing Batch Reactor Design and Operational Consideration,” Sept, 2005.

Copyright to IJIRSET DOI:10.15680/IJIRSET.2016.0504108 5154

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Analysis of Performance Evaluation and Efficiency of Sewage Treatment Plant of

Naini Plant, Allahabad

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www.ijraset.com Volume 4 Issue IV, April 2016
IC Value: 13.98 ISSN: 2321-9653
International Journal for Research in Applied Science & Engineering
Technology (IJRASET)
Analysis of Performance Evaluation and Efficiency
of Sewage Treatment Plant of Naini Plant,
Allahabad
Shivam Mani Tripathi1, Dr. Govind Pandey2
1
P.G. Student, 2Professor, Department of Civil Engineering,
MMM University of Technology, Gorakhpur, Uttar pradesh, India

Abstract - Allahabad city host Wastewater Treatment Plant (WTP) based on activated sludge process with surface aerator and air
diffuser along the side of GANGA River, located in Naini, Allahabad, U.P, India. This plant is constructed and design with an
aim to manage wastewater so as to minimize disease-causing organisms, organic matter, solids, nutrients, and other pollutants.
It was revealed from the performance study that efficiency of the treatment plant was good enough with respect to removal of
total dissolved solids in contrast to the reduction in other parameters like, total suspended solids, BOD and COD. In Naini plant,
BOD, COD and TSS removal efficiency of three month were, 87.74, 87.46 and 87.80% respectively. The order of reduction
efficiency was COD < BOD < TSS STP. In addition to this, the problem associated with the maintenance and operation of
wastewater treatment plants is discussed. The research work presents the results of the evaluation carried out for the efficiency
analysis of STP based on activated sludge process with surface aerator and air diffuser located in Allahabad for handling and
treating the municipal wastewater.
Keywords - Performance Evaluation, activated sludge process with surface aerator and air diffuser, Total Suspended Solid,
Chemical Oxygen Demand, Biochemical oxygen demand.

I. INTRODUCTION
Every community produces both solid and liquid wastes. The liquid portion -wastewater - is essentially the water supply of the
community after it has been fouled by a variety of uses. From the standpoint of sources of generation, wastewater may be defined as
a combination of the liquid - or water-carried wastes removed from residences, institutions, commercial and industrial
establishments together with such groundwater, surface water and storm water as may be present. If untreated wastewater is allowed
to accumulate, the decomposition of the organic materials it contains can lead to the production of large quantities of malodorous
gases. In addition, untreated wastewater usually contains numerous pathogenic, or disease-causing, microorganisms that dwell in the
human intestinal tract or that may be present in certain industrial waste. Wastewater also contains toxic compounds. For these
reasons, the immediate and nuisance-free removal of wastewater from it sources of generation, followed by treatment and disposal,
is not only desirable but also necessary in an industrialized society. There are several methods of treating the domestic / municipal
/industrial wastewater. Certain parameters, which are on higher side in raw wastewater needs to be, reduced according to the
pollution control board's norms by giving specific treatment. One of them is to supply the oxygen for removal of BOD i.e. Bio-
chemical Oxygen Demand. This is achieved by different methods of Aeration like surface aeration or by diffused aeration etc. The
type of Air diffuser use in Naini plant is Complete mix aeration. In this the influent and the returned sludge are mixed and applied at
several points along the length and width of the basin. The contents are mixed and the MLSS flow across the tank to the effluent
channel. The oxygen demand and organic loading are uniform along entire length of basin. Flow regime in complete mix flow the
sludge retention time is about 5-15 day, food to micro-organism ratio is about 0.2-0.6 d-1 aerator loading is about 0.8-2.0 kg/m3d,
MLSS is about 3000-6000 mg/l, aeration period is about 3-5 hours, recirculation ratio (Qr/Q) is 0.25-1.00. Aeration system is coarse
bubble is which various nozzles or orifices with check-valve feature; Spurger air escapes from periphery of a flexible disc that may
lift over. The transfer efficiency of coarse bubble aeration is 4-8%, the transfer rate is about 0.6-1.2 kgO2/kW.h.

A. Advantages of coarse bubble aeration system are:

1) Non-clogging
2) Low maintenance
3) Air filter not needed

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4) Used to produce spiral flow

B. Disadvantages of coarse bubble aeration system are:

1) High initial cost
2) Low oxygen transfer
3) High power cost

Mechanical aerator or surface aerators in this the oxygen is entrained from the atmosphere. The aerators consist of submerged or
partially submerged impellers that are attached to motors mounted on float or fixed structures. Surface aerators are classified
according to the rotational speed of impeller there are four types of surface aerators

1) Radial flow, low speed 20-60 rpm

2) Axial flow high speed 300-1200rpm
3) Brush rotor
4) Submerged turbine

The mechanical aerators fall into two major groups: surface impeller and submerged turbine. In Naini plant the mechanical aerator
use is surface impeller with axial flow high speed 300-1200rpm this aerator having high speed, use smaller dia propeller and
floating structure. The transfer rate is 1.2 - 2.4 kgO2/kW.h

C. Advantages of mechanical aerator of axial flow high speed:

1) Low initial cost
2) It can be adjusted to varying water level,
3) Flexible operation

D. Disadvantages of mechanical aerator of axial flow high speed:

1) Icing in cold climate
2) Poor accessibility for maintenance
3) Mixing inadequate
II. STUDYAREA
The study area covers Sewage Treatment Plant (STP) based on activated sludge process with surface aerator and air diffuser and
situated on the north bank of Situated on the right bank of river Ganga in North –west of Allahabad city. Process Flow Diagram of
Sewage Treatment Plant of Naini working on the principle of activated sludge process with surface aerator and air diffuser given in
Fig. 1. The STP is of the capacity of Naini is 80 MLD. It has surface aerator and air diffuser in which surface aerator contain 60
MLD capacity and air diffuser contain 20 MLD capacity of wastewater. By which wastewater get aerated and further used for
treatment. As Naini plant was firstly has capacity of only 60 MLD by surface aerator after expansion of the city and population it
require to expand the treatment plant then 20 MLD of air diffuser is attached to the Naini plant for getting the better result. This STP
work on improving the quality of wastewater by reducing the value of the total suspended solids (TSS), chemical oxygen demand
(COD), biological oxygen demand (BOD), and increasing the value of dissolve oxygen (DO). Allahabad Naini plant has chemical
oxygen demand (COD) of raw wastewater 239mg/l and after treatment 122mg/l. Biological oxygen demand (BOD) of raw
wastewater is 60 mg/l and after treatment 17mg/l. Total suspended solid (TSS) of raw wastewater is 231mg/l and after treatment
19mg/l. Average wastewater received by STP is about 57MLD, the efficiency of total suspended solid (TSS) of STP is about
87.54% and the efficiency of biological oxygen demand (BOD) is about 79.98%. As per information given by the Ganga Pollution
Control Board (U.P.) to Central Pollution Control Board (CPCB) the expenditure of operation and maintenance cost of sewage
treatment plant of Allahabad Naini is about 229.038 lakh. Total area captured by Naini is 11 hectare. This research work evaluated
the performance of the STP based on surface aerator and air diffuser in terms of wastewater characterization to derive a comparative
account between the pollution load before and after the treatment processes, besides, discerning their efficiency

©IJRASET: All Rights are Reserved 675

www.ijraset.com Volume 4 Issue IV, April 2016
IC Value: 13.98 ISSN: 2321-9653
International Journal for Research in Applied Science & Engineering
Technology (IJRASET)

Fig1: Process Flow Diagram of Sewage Treatment Plant of Naini

III. RESULT
The study carries out the parameters such as COD, TSS and BOD of both the plants followed by overall Efficiencies of three
months i.e. July to September shown in figure.

AVERAGE COD AVERAGE COD

AVERAGE
AVERAGE COD OF PRIMARY OF SECONDARY
MONTH SLUDGE VOLUME EFFICIENCY
OF INFLUENT SLUDGE SLUDGE
INDEX
TREATMENT PROCOSS
JULY 352.83 141.29 43.74 62.96 87.60
AUGUST 352.9 140.19 42.58 62.7 87.93
SEPTEMBER 361.8 144.8 44.53 64.13 87.69

AVERAGE COD PER MONTH

400

200

0
JULY AUGUST SEPTEMBER

AVERAGE COD OF INFLUENT

AVERAGE COD OF PRIMARY SLUDGE TREATMENT
AVERAGE COD OF SECONDARY SLUDGE PROCOSS

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IC Value: 13.98 ISSN: 2321-9653
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Technology (IJRASET)
AVERAGE COD OF SECONDARY
SLUDGE PROCOSS
45

44
AVERAGE COD OF
43
SECONDARY SLUDGE
42 PROCOSS

41
JULY AUGUST
SEPTEMBER

Efficiency for COD

88.00

87.80
efficiency
87.60

87.40
JULY AUGUST
SEPTEMBER

AVERAGE SLUDGE VOLUME

INDEX
64.5
64
63.5
63
62.5 AVERAGE SLUDGE
62 VOLUME INDEX
61.5
JULYAUGUST
SEPTEMBER

AVERAGE SEWAGE AVERAGE BOD AVERAGE BOD

EFFICIENCY
MONTH RECEIVED IN STP IN INFLUENT IN MG/L EFFLUENT IN
FOR BOD
MLD MG/L
JULY 32.27 115.16 22.06 80.84
AUGUST 29.52 105.84 20.52 80.62
SEPTEMBER 27.71 117 24 79.49

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IC Value: 13.98 ISSN: 2321-9653
International Journal for Research in Applied Science & Engineering
Technology (IJRASET)
AVERAGE SEWAGE RECEIVED
IN STP IN MLD
AVERAGE SEWAGE RECEIVED IN STP IN MLD

32.27

29.52
27.71

JULY AUGUST SEPTEMBER

EFFICIENCY FOR BOD

EFFICIENCY FOR BOD
80.84
80.62

79.49

JULY AUGUST SEPTEMBER

AVERAGE BOD
AVERAGE BOD INFLUENT IN MG/L
AVERAGE BOD EFFLUENT IN MG/L

115.16 117
105.84

22.06 20.52 24

JULY AUGUST SEPTEMBER

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www.ijraset.com Volume 4 Issue IV, April 2016
IC Value: 13.98 ISSN: 2321-9653
International Journal for Research in Applied Science & Engineering
Technology (IJRASET)
AVERAGE TSS INFLUENT AVERAGE TSS EFFICIENCY
MONTH IN STP IN MG/L EFFLUENT IN MG/L FOR TSS

JULY 362.32 44.74 87.65

AUGUST 338.52 41.58 87.72
SEPTEMBER 364.03 43.5 88.05

AVERAGE TSS
AVERAGE TSS INFLUENT IN STP IN MG/L
AVERAGE TSS EFFLUENT IN MG/L
362.32 364.03
338.52

44.74 41.58 43.5

JULY AUGUST SEPTEMBER

EFFICIENCY FOR TSS

EFFICIENCY FOR TSS

88.05

87.72
87.65

JULY AUGUST SEPTEMBER

IV. CONCLUSIONS
Allahabad city was selected for the study of the performance of STP in running condition i.e. the 80MLD based STP at Naini and
10MLD. The conclusions drawn from the study are as follows:
Presently the existing sewage treatment plant is working satisfactory and the results of treated water are observed as per the central
pollution control board norms. It has been observed that 100 % of the waste water generated is not treated; thus more plants are

©IJRASET: All Rights are Reserved 679

www.ijraset.com Volume 4 Issue IV, April 2016
IC Value: 13.98 ISSN: 2321-9653
International Journal for Research in Applied Science & Engineering
Technology (IJRASET)
required.

All treated water is disposed into the Ganga River. The treated water may also be used for agricultural and industrial purposes.
Several important Water Quality Parameters like Fecal Coliform, Oil, Sulphate and Grease are not measured on a regular basis.

REFERENCES
[1] Central Public Health and Environmental Engineering Organisation, 2012, Manual on sewerage and sewage treatment, Ministry of urban development, New
Delhi.
[2] Environmental Protection Agency, Manual on Procedures for Evaluating of Wastewater Treatment Plants, Office of Water Programs, Washington D.C.
[3] Metcalf and Eddy Inc., 2003, “Wastewater Engineering”, 4th Edition, Tata Mc Graw Hill Publishing C. Ltd., New Delhi.
[4] D.G. Rao., 2013, “Wastewater treatment: Advance Process and Technologies”, CRC Press., New York
[5] Wastewater technology factsheet - Sequencing batch reactor,” EPA, 1999.
[6] A. Gallego, A. Hospido, M. T. Moreira and G. Feijoo, “Environmental Performance of Wastewater Treatment Plant,” Resources, Conservation and Recycling,
vol. 52, pp. 931-940, 2008.
[7] D. Nolasco, D. Irvine, M. Manoharan and E. Giroux, “Evaluation and Optimization of Design/ Operation of Sequencing batch Reactors for Wastewater
treatment”.
[8] A. H. Mahvi, “Sequencing Batch Reactor- A Promising Technology in Wastewater Treatment,” Iran Journal of Environmental Health Sciences and
Engineering, vol. 5, no. 2, pp. 79-90, 2008.
[9] EPA, “Manual on Procedures for evaluating performance of wastewater treatment plants”.
[10] C.P.H.E.E. Organization, “Manual on Sewerage and Sewage Treatment,” Ministry of Urban Development, New Delhi.
[11] N. E. I. W. P. Control, “Sequencing Batch Reactor Design and Operational Consideration,” Sept, 2005.

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