Current Research in Chemical Biology 1 (2021) 100005

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Current Research in Chemical Biology

journal homepage: www.journals.elsevier.com/current-research-in-chemical-biology

Removal of ammonia and nitrates from contaminated water by using solid

waste bio-adsorbents
S. Dey *, N. Haripavan, S.R. Basha, G.V. Babu
Department of Civil Engineering, Gudlavalleru Engineering College, Gudlavalleru, Andhra Pradesh, India

A R T I C L E I N F O A B S T R A C T

Keywords: The presence of pollutants in aqueous solution mainly from hazardous heavy metals and metalloids is creating an
Ammonia environmental and social problem. The ammonia and nitrates are one of the major groundwater contaminants
Nitrates present in the rural areas. A nitrate was regulated in drinking water quality mainly due to excess amounts can
Biosorptions
cause methemoglobinemia disease. Ammonia in both gaseous and liquid form can be irritating to the eyes, res-
Kinetic equilibrium
Isotherm data and regeneration
piratory tract failure and skin due to its alkaline nature. The biological effects of ammonia and nitrates in humans
after acute exposures are dose-related depend on their concentration; the amount is taken by the body and
duration of exposure. Biosorption is a physiochemical process that occurs naturally in certain biomass which
allows it to passively concentrate and bind contaminants onto its cellular structure. It is metabolically passive
process not require energy and amount of contaminants in sorbent can remove is dependent on kinetic equilib-
rium and composition of the sorbents at cellular surface. Every biosorbent had different physical, chemical and
biological properties for heavy metals removal by biosorption from the water. The oxygen functional groups are
very important characteristics of biosorbents because they measured the surface properties and hence their
quality as biosorbents. The analysis of isotherm data by fitting them to different models is important to find a
sustainable model that can be used. From the biosorption isotherms describe how the sorbate molecules are
distributed between the liquid phase and solid phase when the system reaches equilibrium. The process can be
made economical by regenerating and reusing of biosorbent after removing the metals. Various bioreactors can be
used in biosorption for the removal of metal ions from large volume of water.

1. Introduction needs for industrial processing, the separation and purification of

The hazardous heavy metals pollutants present in aqueous solution
are producing environmental problems in the worldwide. As many of
these elements are stable because they are bio-accumulative and making
their safe limits is very difficult in the ecosystem. Few metals, such as Fe,
Zn, Co, Cr, and Ni are required for biological metabolism in trace
amounts; however, their higher dosages may cause toxic effects. Toxicity
of these elements is of considerable concern worldwide because of their
environmental burden. During the past few decades scientists have been
developing cheap and environmentally friendly technologies for the
treatment of wastewater generated at the household and up to the in-
dustrial scale. In this regard, the methods like ion-exchange, membrane
filtration, catalysts including photo-catalysis, microbe-assisted phyto-
bioremediation and adsorption over low-cost biosorbents and non-
materials have been developed and demonstrated to be successful.
Because of the demand for water to feed the growing population and
wastewater by adsorption phenomena is gaining a major importance. The
adsorption over biomass-derived biosorbents has provided the capacity
to treat wastewater on large scale. Several low-cost biosorbents have
been synthesis and use for the removal of toxic metals and metalloids
from wastewater (Singh and Mishra, 2018; Suneetha and Ravindhranath,
2012a).
Nanomaterials and their analogues, such as magnetic nanosorbents
and layered double hydroxides, have been focus for development of
novel materials with high surface area and low-cost synthesis to develop
new generation super-adsorbents. Heavy metals in drinking water pose a
threat to human health. Populations are exposed to heavy metals pri-
marily through water consumption, but few heavy metals can bio-
accumulation in the human body (e.g., in lipids and gastrointestinal
system) and may induce cancer and other risks. To date, few thousand
publications have reported in different aspects of heavy metals in
drinking water, including the types and quantities of metals in drinking

* Corresponding author.
E-mail address: subhasdey633@gmail.com (S. Dey).

https://doi.org/10.1016/j.crchbi.2021.100005
2666-2469/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
S. Dey et al.
water, their sources and factors affecting their concentrations at exposure
points, human exposure, potential risks and their removal from drinking
water. Many developing countries are faced with the challenge of
reducing human exposure to heavy metals, mainly due to their limited
economic capacities to use advanced technologies for heavy metal
removal (Sumiya and Anu, 2016; Reddy et al., 2015).
1.1. Sources of heavy metals
The heavy metals are highly used in electronics, machines and arti-
facts of everyday life, as well as in high-tech applications. As a result they
are able to enter into the aquatic and food chains of humans and animals
from a variety of anthropogenic sources as well as from the natural
geochemical weathering of soil and rocks. The main sources of contam-
ination include mining wastes, land fill leaches, municipal wastewater,
urban runoff and industrial wastewaters, particularly from the electro-
plating, electronic and metal-finishing industries. With increasing the
generation of metals from technologies activities, the problem of waste
disposal has become one of paramount importance. Many aquatic envi-
ronments face metal concentrations that exceed water quality criteria
designed to protect the environment, animals and humans. The problems
are exacerbated because metals have a tendency to be transported with
sediments are persistent in the environment and can bioaccumulation in
the food chain. Some of the oldest cases of pollution in the world are due
to heavy metal use, for example Cu, Hg and Pb mining, smelting and
utilization by ancient civilizations. The heavy metals are among the most
common pollutants found in the wastewater. These metals pose a toxicity
threat to human beings and animals even at low concentration. Heavy
metals are found naturally in the earth and become concentrated as a
result of human activities, or in some cases geochemical processes, such
as accumulation in peat soils that are released when drained for agri-
culture. The common sources are mining and industrial wastes, vehicle
emissions, lead-acid batteries, fertilizers, paints, treated woods, infra-
structure and micro-plastics floating in the world's oceans (Mohseni--
Bandpi et al., 2013; Battas et al., 2019).
1.2. Nitrates
Nitrate is an inorganic compound that occurs under a variety of
conditions in the environment, both naturally and synthetically. Nitrate
is composed of one atom of nitrogen (N) and three atoms of oxygen (O),
the chemical symbol for nitrate is NO3. Nitrite (NO2) can be formed from
nitrate by a chemical process called reduction. The anion is conjugate
base of nitric acid, producing one central nitrogen atom surrounded by
three identically bonded oxygen atoms in the trigonal planar arrange-
ment. The nitrate ion carries a formal charge of
1. This charge results
from a combinations of formal charges in which carries a three oxygen

2⁄3 charge, whereas the nitrogen carries þ1 charge, all these adding up
to formal charge of polyatomic nitrate ion. This arrangement is
commonly used as an example of resonance. Nitrate does not normally
cause health problems unless it is reduced to nitrite (Suneetha and
Ravindhranath, 2012b; Khalil and Sergeevich, 2018). Like the isoelec-
tronic carbonate ion, the nitrate ion can be represented by the resonance
structures. In the natural rate at which nitrogen is deposited onto land
through the production and application of nitrogen fertilizers the com-
bustion of fossil fuels and replacement of natural vegetation with
nitrogen-fixing crops such as soybeans. The major anthropogenic source
of nitrogen in the environment is nitrogen fertilizer, the application of
which increased with the time. Most of the synthetic fertilizer applica-
tions in the agricultural land for increasing the production are drains
from agricultural fields to contaminate surface and ground water, nitrate
concentrations in our water resources have also increased. Nitrate salts
are found naturally on earth as large deposits, particularly of nitratine, a
major source of sodium nitrate. Nitrates are produced by a number of
species of nitrifying bacteria and nitrate compounds for gun powder were
historically produced, in the absence of mineral nitrate sources, by means
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Current Research in Chemical Biology 1 (2021) 100005
of various fermentation processes using urine and dung. As a byproduct
of lightning strikes in earth's nitrogen-oxygen rich atmosphere, nitric acid
is produced when nitrogen dioxide reacts with water vapor. Nitrates are
produced industrially from nitric acid (Gorre and Himabindu, 2015; Rani
and Ravindhranath, 2014a).
1.2.1. Sources of nitrates
Meat products account for less than 10% of nitrate in the diet, but
60–90% of the nitrite consumed. This is primarily because of sodium
nitrite added to foods such as hot dogs, bacon, or ham. Fruits, grains and
dairy products contribute almost no nitrate or nitrite to people's diets. It
is often difficult to pinpoint sources of nitrates because there are so many
possibilities. Sources of nitrogen and nitrates may include runoff or
seepage from fertilized agricultural lands, municipal and industrial waste
water, refuse dumps, animal feedlots, septic tanks and private sewage
disposal systems, urban drainage and decaying plant debris. The geologic
formations and direction of ground water flow also influence the nitrate
concentration (Gupta et al., 2015; Gao et al., 2015).
1.2.2. Effects of nitrates
I. Nitrate is one of the most common groundwater contaminants in
rural areas. It is regulated in drinking water quality primarily
because excess amounts can cause methemoglobinemia or “blue
baby” disease. Nitrate in groundwater originates primarily from
fertilizers, septic systems and manure storage or spreading
operations.
II. A potential cancer risk from nitrate (and nitrite) in water and food
has been reported. A possibility exists that nitrate can react with
amines or amides in the body to form nitrosamine which is known
to cause cancer. Nitrate must be converted to nitrite before
nitrosamine can be formed. The magnitude of cancer risk from
nitrate in drinking water is not known.
III. Nitrates have same effect on aquatic plant growth as phosphates
and thus the same negative effect on the water quality. The plants
and algae are stimulated, which provide food for fish. This may
cause an increase in the fish population. But, if algae grow too
wildly, oxygen levels in the water will be reduced and fish will die.
1.2.3. Physical properties of nitrates
Potassium nitrate is colorless transparent prisms or white, granular or
crystalline powder with cooling, saline pungent taste. It is stable com-
pound. However, at higher temperatures they decompose, and may be
explosive at extreme conditions (high temperature and pressure). Ni-
trates also decompose in weak acids. Generally, the presence of chlorides,
some metals and organic material destabilize both nitrates and nitrates.
Nitrates form NO and NO2 upon thermal decomposition, but ammonium
nitrate also forms N2O, N2 and H2O depending on temperature. Salts of
nitrate are odorless and colorless with a saline taste. They are generally
hygroscopic. The water solutions of nitrates usually have a pH in the
range of 5–8. KNO2: melting point ¼ 440  C; decomposes at 350  C a
solubility in water ¼ 281 ; soluble in hot alcohol. Ammonium nitrate is
odorless, transparent, hygroscope deliquescent crystals or white gran-
ules. Five solid phases exist at normal pressure and orthorhombic at room
temperature (Rani and Ravindhranath, 2014b; Anhwange et al., 2009).
1.3. Ammonia
Ammonia (NH3) is colorless, pungent gas composed of nitrogen and
hydrogen. It is simplest stable compound of elements and serves as a
starting material for production of many commercially nitrogen com-
pounds. NH3 is an irritant with a characteristic pungent odor that is
widely used in industry. In ammonia is highly soluble in water and upon
inhalation, is deposited in the upper airways, occupational exposures to
ammonia have commonly been associated with sinusitis, upper airway
irritation and eye irritation (Zahra and Mohammad, 2013; Rajoriya and
S. Dey et al.
Kaur, 2014). The acute exposures to high levels of ammonia have also
been associated with diseases of lower airways and interstitial lung.
Small amounts of ammonia are naturally formed in all tissues and organs
of the vertebrate organism. Ammonia is both a neurotoxin and metab-
otoxin. In fact, it is most common endogenous neurotoxin. A neurotoxin
is a compound that causes damage to neural tissue and neural cells. A
metabotoxin is an endogenously produced metabolite that causes adverse
health effects at chronically high levels. Ammonia is recognized to be
middle in the pathogenesis of a brain condition known as hepatic en-
cephalopathy, which arises from various liver diseases and leads to a
build up ammonia in the blood (hyper-ammonemia). Ammonia occurs
naturally and is produced by human activity. It is an important source of
nitrogen which is needed by plants and animals. Bacteria found in the
intestines can produce ammonia. Ammonia is a colorless gas with a very
high distinct odor. This odor is familiar to many people because ammonia
is used in smelling salts, many household and industrial cleaners and
window-cleaning products. Ammonia gas can be dissolved in water. This
kind of ammonia is called liquid ammonia or aqueous ammonia. Once
exposed to open air, liquid ammonia quickly turns into a gas. Ammonia is
applied directly into soil on farm fields and is used to make fertilizers for
farm crops, lawns and plants. Many household and industrial cleaners
contain ammonia (Limbachiya et al., 2012; Mithra et al., 2012).
1.3.1. Sources of ammonia
Ammonia is produced for commercial fertilizers and other industrial
applications. Natural sources of ammonia include the decomposition or
breakdown of organic waste matter, gas exchange with the atmosphere,
forest fires, animal and human waste and nitrogen fixation processes.
Ammonia can enter into the aquatic environment via direct means such
as municipal effluent discharges and excretion of nitrogenous wastes
from animals and indirect means such as nitrogen fixation, air deposition
and runoff from agricultural lands. Ammonia is a chemical found in trace
quantities in nature, being produced from nitrogenous animal and
vegetable matter. Ammonia and ammonium salts are also found in the
small quantities in rainwater, whereas ammonium chloride and ammo-
nium sulfate are found in volcanic districts; crystals of ammonium bi-
carbonate have been found in ronak guano. The kidney secretes NH3 to
neutralize excess acid. Ammonium salts are found distributed through
fertile soil and in seawater. Ammonia (CASRN 7664-41-7) is another
harmful chemical released by the paper industry. Ammonia example
anhydrous ammonia has a pungent odor and is usually found in gas form
due to its boiling point of
33  C. The most common use of ammonia is
the production of fertilizer 83% of all ammonia is used in fertilizers
(Chopin et al., 2011; Neori et al., 1998). The ammonia is also seen in
household cleaning products in the form of ammonium hydroxide, which
is simply ammonia dissolved in water. Producing the necessary amount
of ammonia for the modern world is not an easy task. Exposure to
ammonia from sources outside the body came from eating proteins and
certain foods containing ammonium salt additives and from air, water
and direct contact with the skin. Ammonia is used in food preparation as
a stabilizer, leavening agent and food additive. Ammonia concentrations
in water vary seasonally and regionally are also affected by the sur-
rounding land use, temperature and pH. The average human intake from
drinking water is about 1 mg/day in cities and less than 0.4 mg/day in
rural areas. Ammonia is a unique industrial chemical because it is pro-
duced by the body and used by all mammalian species. The breakdown of
proteins in food converted into amino acids (Duruibe et al., 2007; Young,
2005).
1.3.2. Effects of ammonia
I. Ammonia in both its gaseous and liquid form can be irritating to
the eyes, respiratory tract and skin due to its alkaline nature. The
biological effects of ammonia in humans after acute exposures are
dose-related they depend on the ambient concentration; the
amount is taken by the body and duration of exposure.
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Current Research in Chemical Biology 1 (2021) 100005
II. An ammonia level in the air is low as 5ppm can be measured by
odor. An average person detects ammonia by odor at around
17ppm. Most people can taste ammonia in water at levels of about
35ppm.
III. Ammonia can irritate the skin and cause chemical burns ranging
from mild to severe depending on the concentration of ammonia
solution. Concentrated vapor or solution may cause the victim to
experience pain, redness of the skin and blisters. Signs displayed
by skin exposed to liquefied ammonia can include frostbite, tissue
death or severe burns with deep ulcerations.
1.3.3. Physical properties of ammonia
Ammonia is a colorless gas with a sharp, penetrating odor. Its boiling
point is
33.35  C and its freezing point is
77.7  C. Ammonia is
miscible with water. In an aqueous solution, it can be expelled by boiling.
The aqueous solution of ammonia is basic. The maximum concentration
of ammonia in water (a saturated solution) has a density of 0.880 g/cm3.
Ammonia is a flammable gas and reacts with oxygen to form nitrogen and
water, or nitrogen (II) oxide and water. Oxidation of ammonia in solution
leads to hydrazine, a corrosive and volatile ingredient in fuels. Liquid
anhydrous ammonia weighs less than water. About eight gallons of
ammonia weighs the same as five gallons of water. It is highly soluble in
water: One volume of water dissolves about 1300 volumes of ammonia
gas. It is due to its high solubility in water that the gas cannot be collected
over water (Buono et al., 2015; Rivett et al., 2008).
1.4. Solid waste
Solid waste are garbage, refuse, sludge from a wastewater treatment
plant, water supply treatment plant control facility and other discarded
materials including solid, liquid, semi-solid resulting from industrial,
commercial, mining and agricultural operations and from community
activities, unwanted or useless solid materials generated from human
activities in residential, industrial or commercial areas. The generation of
solid waste is the inevitable consequence of all processes where materials
are used. Extraction of raw materials, manufacture of products, con-
sumption and waste management all generate wastes. The rate of ma-
terial use today is so large, both with regard to the total amounts and seen
as per capita average, that the waste generated will impact on the envi-
ronmental quality and human health worldwide if it is not managed
properly. A few centuries, or even decades ago, the solid waste generated
was a small fraction of what it is today, the drivers of the generation are
primarily the increased availability of energy and secondly the popula-
tion growth. Solid waste generation rates and composition vary from
country to country depending on the economic situation, industrial
structure, waste management regulations and life style. It may be cate-
gorized in three ways.
I. Origin (domestic, industrial, commercial, construction or
institutional)
II. Contents (organic material, glass, metal, plastic paper etc)
III. Hazard potential (toxic, non-toxin, flammable, radioactive, in-
fectious etc).
1.5. Biosorptions
Biosorption is a physiochemical process that occurs naturally in
certain biomass which allows it to passively concentrate and bind con-
taminants onto its cellular structure. Biosorption can be defined as the
capacity of biological materials to accumulate heavy metals from
wastewater through metabolically mediated or physico-chemical path-
ways of uptake. Though using biomass in environmental cleanup has
been in practice for a while, scientists and engineers are hoping this
phenomenon will provide an economical alternative for removing toxic
heavy metals from industrial wastewater and aid in environmental
remediation (Gooddy et al., 2014; Aruna et al., 2021). Industrialization
S. Dey et al.
Fig. 1. In the biosorptions processes for removal of heavy metals (Monge-Amya et al., 2015).
and urbanization have led to the release of increasing amounts of heavy
metals into the environment. Metal ion contamination of drinking water
and waste water is a serious problem especially with high toxic metals
such as lead and cadmium and less toxic metals such as copper and zinc.
Several biological materials have attracted many researchers and scien-
tists as they offer both cheap and effective removal of heavy metals from
the waste water. Therefore it is urgent to study and explore all possible
sources of agro based inexpensive adsorbents for their feasibility in the
removal of heavy metals (Mahmoud et al., 2012; Park and Kim, 2005).
Agricultural waste composite-activated carbon was developed and
characterized by the means of chemical activation to be utilized for the
uptake of heavy metals in a batch adsorption process. This study was
carried out to minimize the widespread of heavy metals within water
source. Batch adsorption studies were carried out with the consideration
of factors such as pH, temperature, initial concentration, adsorbent
dosage and contact time. The adsorption rate of heavy metals was faster
in the initial 30min but it attained equilibrium at 90 min for both metal
ions. The Isotherm models studied show that the adsorption process was
best fitted to the Langmuir model. The result of kinetic and thermody-
namic studies represents that the adsorption process followed a pseudo-
second-order i.e. physical, exothermic and spontaneous in nature. The
adsorption of heavy metals unto agricultural waste composite when
compared with other adsorbents in literature gave the highest adsorption
capacity. Based on the inaccessibility of water treatment equipment,
water pollution amongst other types of pollution became a major issue
for undeveloped and fast-growing countries who are more vulnerable.
Not only does the upsurge of contamination of aquatic sources with
different numbers of pollutants endanger the aquatic biota, it also leads
to reaching high amount of water scarcity. The increase in population
and industrial growth has negative impact on the environment due to
heavy metal discharged. Heavy metals, that is, metals with high density
above 5 g/cm3, amid other pollutants have the most harmful effect
because of their tenacity and non-biodegradability in the environment.
The biosorptions process for removal of heavy metals is shown in Fig. 1.
Environmental pollution and grave poisoning symptoms are caused by
the release of metals (toxic) including arsenic, lead, nickel, copper,
mercury and chromium in wastewater. This is as a result of great
industrialized operations, which is the reason for complications experi-
enced in wastewater treatment (World Health Organization, 2004). A
certain amount of practices like oxidation, osmosis, reduction, precipi-
tation, ultra filtration, electro-dialysis, ion exchange and electrochemical
are being engaged to help in the adsorption of these toxic metals from
wastewater. However, their shortcomings include higher quantity of
sludge produced, poor efficiency and incapability to remove metals at
higher concentrations. Researchers have viewed adsorption method as
low-cost, effective and proficient for metal ions' uptake in wastewater
and it is overall preference when accessing a good number of waste
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Current Research in Chemical Biology 1 (2021) 100005
products and natural materials (Peez-Corona et al., 1998; Tian et al.,
2010).
Efficacy of activated carbon is one of the best adsorbents for heavy
metal uptake from wastewater. Since activated carbon can be prepared
from agrarian waste, it is not only considered to be highly effective but
also easily accessible and cost-effective. Activated carbon apply from
commercial-based products has been typically employed for adsorption
processes but its restriction with reference to cost (high) has motivated
researchers to look for substitutes and represents a good prospect in
respect to the reusability and cost-effective nature (Sinha and Walker,
1972; Yavuz et al., 2006).
1.5.1. Biosorption mechanisms
The complex structure of microorganisms represents that there are
many ways the metal has to be taken up by the microbial cell. The bio-
sorption mechanisms are different and are not fully understood. They
may be classified according to various criteria. According to the depen-
dence on the cell's metabolism, biosorption mechanisms can be divided
into:
1. Metabolism dependent and
2. Non -metabolism dependent
According to the location where the metal removed from solution is
found, biosorption can be classified as
1. Extra cellular accumulation/precipitation
2. Cell surface sorption/precipitation
3. Intracellular accumulation
Transport of metal across the cell membrane yields intracellular
accumulation, which is dependent on the cell's metabolism. This means
that this kind of biosorptions may take place only with viable cells. It is
often associated with an active defense system of the microorganism,
which reacts in the presence of toxic metal. During non-metabolism
dependent biosorption, metal uptake is by physico-chemical interaction
between the metal and different functional groups are present on the
microbial cell surface. This is based on the physical adsorption, ion ex-
change and chemical sorption, which is not dependent on the cells'
metabolism. Cell walls of microbial biomass, mainly composed of poly-
saccharides, proteins and lipids have abundant metal binding groups
such as carboxyl, sulphate, phosphate and amino groups. This type of
biosorption, i.e., non-metabolism dependent is relatively rapid and can
be reversible. In the case of precipitation, the metal uptake may take
place both in the solution and on the cell surface. Further, it may be
dependent on the cell's' metabolism if, in the presence of toxic metals, the
microorganism produces compounds that favor the precipitation process.
S. Dey et al.
Fig. 2. Adsorption of heavy metals on the biological cell of biosorbents (Qin et al., 2020).
Precipitation may not be dependent on the cells' metabolism, if it occurs
after a chemical interaction between the metal and cell surface (Tsezos
et al., 1988; Volesky and Naja, 2005).
1.5.1.1. Transport across cell membrane. Heavy metal transport across
microbial cell membranes may be mediated by the same mechanism used
to convey metabolically important ions such as potassium, magnesium
and sodium. The metal transport systems may become confused by the
presence of heavy metal ions of the same charge and ionic radius asso-
ciated with the important ions. This kind of mechanism is not associated
with metabolic activity. The adsorptions of heavy metals on the biolog-
ical cell of biosorbents are shown in Fig. 2. Basically biosorption by the
living organisms comprises of two steps. First metabolisms are inde-
pendent binding where the metals are bound to the cell walls and second,
metabolism dependent intracellular uptake whereby the metal ions are
transported across the cell membrane.
1.5.1.2. Physical adsorption. In this category, the physical adsorption
takes place with the help of van der Waals' forces. They hypothesized
that uranium, cadmium, zinc, copper and cobalt biosorption by dead
biomasses of algae, fungi and yeasts takes place through electrostatic
interactions between the metal ions in solutions and cell walls of mi-
crobial cells.
1.5.1.3. Ion Exchange. Cell walls of microorganisms contain poly-
saccharides and bivalent metal ions exchange with the counter ions of
polysaccharides. For example, the alginates of marine algae occur as salts
of Kþ, Naþ, Ca2þ and Mg2þ. These ions can exchange with counter ions
such as Co2þ, Cu2þ, Cd2þ and Zn2þ resulting in the biosorptive uptake of
heavy metals. The biosorption of copper by fungi Ganoderma lucidium
and as per gillus niger was also up taken by ion exchange mechanism.
1.5.1.4. Complexation. The heavy metal removal from solution may also
take place by complex formation on the cell surface after that the inter-
action between metal and active groups. They hypothesized that bio-
sorption of copper by C. vulgarisms and Z. ramigera takes place through
both adsorption and formation of coordination bonds between metals
and amino and carboxyl groups of cell wall polysaccharides. The
complexation was found to be the only mechanism responsible for cal-
cium, magnesium, cadmium, zinc, copper and mercury accumulation by
Pseudomonas syringae. Microorganisms may also produce organic acids
(e.g., citric, oxalic, gluonic, fumaric, lactic and malic acids), which may
chelate toxic metals result in the formation of metalloid-organic
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Current Research in Chemical Biology 1 (2021) 100005
molecules. These organic acids help in the solubilisation of metal com-
pounds and their leaching from surfaces. Metals may be biosorbed or
complexed by carboxyl groups found in microbial polysaccharides and
other polymers.
1.5.1.5. Precipitation. Precipitation may be either dependent on the
cellular metabolism or independent of it. In the former case, the metal
removal from solution is often associated with active defense system of
the microorganisms. They react in the presence of toxic metal producing
compounds, which favor the precipitation process. In the case of pre-
cipitation not dependent on the cellular metabolism, it may be a conse-
quence of the chemical interaction between the metal and cell surface.
1.5.1.6. Use of recombinant bacteria for metal removal. Metal removal by
adsorbents from water and wastewater is strongly influenced by the
physico-chemical parameters such as ionic strength, pH and concentra-
tion of competing organic and inorganic compounds (Morse et al., 1998;
Dawson and Hilton, 2011).
1.5.2. Factors affecting the adsorptions processes
Over the past 20 years there has been an exponential growth in the
world's population. This has led to the environmental buildup of waste
products, among which heavy metals are the major concern. Heavy
metals can be biodegradable which are being added to the soil, water and
air in increasing amounts as well as no biodegradable. Some metals like
zinc, magnesium and copper are required for animal and plant life as
micronutrients but the same would become more hazardous if they are
taken up by the plants or animals in large amounts. The various factors on
which the adsorption process depends are.
1.5.2.1. Temperature. As the temperature increases, the adsorption ca-
pacity is found to decrease and vice versa. It is an exothermic process.
1.5.2.2. pH. As pH increases from 7.0 to 7.5, the retention capacity of
the adsorbing surface increased significantly, whereas in lower pH the
adsorption process was affected.
1.5.2.3. Pressure. With increase in pressure, the adsorption increases up
to a certain extent till saturation level is reached but after that no more
adsorption takes place no matter how high the pressure is.
1.5.2.4. Adsorbent activation. To provide higher number of vacant sites
on the surface of adsorbent, this can be done by breaking solid crystal in
S. Dey et al.
small pieces, heating charcoal at high temperature, breaking lump of
solid into powder, or other methods suitable for particular adsorbent.
Contaminants are adsorbed onto the cellular structure. Since the bio-
sorption is determined by the equilibrium, it is strongly influenced by pH,
concentration of biomass and interaction between different metallic ions.
Transport of metal across the cell membrane yields intracellular accu-
mulation, which is dependent on the cell's metabolism. This means that
this kind of biosorption may take place only with the viable cells. During
non-metabolism dependent biosorption, metal uptake is by physico-
chemical interaction between the metal and functional groups present
on the biosorbent cell surface. This is based on the physical adsorption,
ion exchange and chemical sorption. This type of biosorption, i.e., non-
metabolism dependent is relatively high and can be reversible. In the
case of precipitation, the metal uptake may take place both in solution
and on the cell surface (Nakamura et al., 1992; Xu et al., 2010).
2. Nitrates and ammonia removal from contaminated water
This section describes in brief about the different methods applied to
find out the concentration of nitrates and ammonia in laboratory as
discussed in Table 1 and Table 2 sensitivity of these methods. It also
includes the work reported on biological (Biosorption) remediation of
nitrate contamination in different part of the world. There are different
methods available for detection of nitrate in laboratory and new detec-
tion techniques are continuously under research. Some of the technolo-
gies used for detection of nitrates and ammonia in laboratory are given
below. Many millions cubic meters of groundwater along with nitrates
and other heavy metals are coming out from both the hand tube wells,
detailed study was carried out, in both micro and macro level to get an
idea about the magnitude of soil contamination in this area. The mean
concentrations (mg/kg) of nitrate in sallow land soils are within the
normal range. Nitrate concentrations are high in those agricultural and
soils where irrigated groundwater contains high amount of nitrogen.
Nitrate poisoning of tube well water, which constitutes the primary
source of drinking water, has become the greatest health threat to the
people of rural India (Biswas et al., 2007; Zhang et al., 2012).
According to Mohseni-Bandpi et al., the nitrate toxicity in ground
water in this the “mausmi” peel biosorbent powder is used to remove the
nitrate present in ground water and found that these bio adsorbent is best
at removal of nitrate up to 84% at 0.2 gm of the biosorbent. Mausmi peels
are collected and washed with distilled water. Later they are sun dried
and made into powder which was used for removing the nitrate in ground
Table 1
Nitrates removal from contaminated water by using biosorbents.
S.N. Bio-adsorbent Removal method
1. Bael leaves Bael leaves were washed with distilled
(Aegle water and sun dried for 3–4 h and
marmelos) crushed manually that powder is sieved
later used as bio-adsorbent.
2. Mausmi peel Taken from domestic waste and washed
powder with distilled water and kept under sun
dried made into powder manually up to a
certain partial size.
3. Green algal Healthy and fresh algal is collected from
powder kollam and it is powder by using
domestic blender and sieve through 500
microns.
4. Barks and stems Freshly scraped from trees and washed
of annoma with distilled water and powdered sieved
squamosa into partials.
5. Banana peels Banana peels were dried and turned into
fine powder particles
6. Greenish clay Local clays are used to remove the
rich in free silica nitrates in water
Current Research in Chemical Biology 1 (2021) 100005
water by the addition of different dosages (Mohseni-Bandpi et al., 2013).
According to Suneetha et al., this process of removal involve in barks and
stems of annona squamosa which are freshly cut or scraped from the trees
and washed with distilled water and powdered, sieved into particles and
it's observed that the removal of nitrates increase with decrease in pH,
while it is inversely proportional to the number of electrodes. However,
the highest nitrite removal was achieved at a current 2A and complete
removal was attained after duration of 10 min (Suneetha and Rav-
indhranath, 2012a).
In Reddy et al., the banana peels are dried and turned into fine
powdered particles used as bio adsorbent where it was found that
decrease of nitrates increase with contact time of water with bio adsor-
bent. The effect of different parameters like contact time, adsorbent size
fraction, adsorbent dosage, nitrite concentration was studied. The high-
est efficiency was 80% achieved over 0.05g of banana peel powder of
106 μm size fraction was used as a adsorbent to treat 100 ml of water
sample with 200 mg/l nitrite concentration for contact time of 0.5h,
removal with contact time of 1 h. Greenish clay rich in free silica. Local
clays are used to remove the nitrates in water (Sumiya and Anu, 2016;
Reddy et al., 2015). The removal of nitrates from biosorbents processes is
shown in Fig. 3. According to Battas et al., 2019 observed in Table 1 that
the nitrate concentration decreased with increase of dosage of bio
adsorbent. The dosage has effect on the nitrate and pH also shows the
differences in nitrate content. The physico-chemical parameters such as
pH, time of equilibration and sorbent concentration have been optimized
for the maximum removal of nitrates. More than 86% of ammonia
removal is noted from simulated waters in all these sorbents at optimum
conditions of removal (Battas et al., 2019). According to Singh et al.,
2008 this process involve collecting bael leaves are dried under sun light
and turned into fine powder which was used to remove the nitrates and
optimum removal is seen at 2 gm i.e. 89% at 6.5 pH maximum nitrate
removal was obtained and contact time of 60 min was sufficient. There
was an increase in the removal efficiency with the increase in tempera-
ture. Bael leaves are easily available in any season (Singh and Mishra,
2018). This review focuses on the occurrence and treatment of nitrate in
the arid region of northern India. High nitrate concentrations were found
mainly in groundwater, their source being mostly from natural origin
related to volcanic processes with significant anthropogenic contribu-
tions near mining and smelting of ores containing nitrate.
According to Suneetha and ravindhranath, the powders of leaves and
barks of phyllanthus niruri, annona squamosa, calotropis gigantean, tri-
dax procumbens, morinda tinctoria and azadiracht indica have been
Experimental conditions Result References

Heated in the muffle furnace at 500 C for 2 h. The The 0.4 mg biosorbents Singh et al., 2008
pH adjustment using 1 ml NaOH. removed 89% nitrates is best
result obtained.
Adjustment of pH by using 1 ml NaOH or 1 ml HCL The 0.2 gm of biosorbent can Maheshwari and
and removal increased with increase in pH from 2 remove 84% of nitrates Gupta, 2012
to 10 due to the electrode–static interaction
between adsorbents.
Temperature 30  C and shaker speed at 200rpm. For 1 mg/l biosorbents has Sumiya and Anu,
Then filtered through 47 mm filter paper. removed 40% nitrates at its 2016
best.
Nitrates decrease with decrease in pH pH 10 ¼ 19.4% Suneetha and
pH 8 ¼ 20.8% Ravindhranath,
pH 6 ¼ 72.6% 2012b
pH 4 ¼ 95%
Nitrate decrease with increase in contact time with The nitrates removal Reddy et al., 2015
the bio-adsorbent. efficiency was 79% at
contact time of 1hr.
Adsorbent dosage effect pH. Initial concentration The nitrate concentration Battas et al., 2019
effect of the particle size decreased with increase of
dosage of bio adsorbent.
6
S. Dey et al. Current Research in Chemical Biology 1 (2021) 100005

Table 2
Ammonia removal from contaminated water by using biosorbents.
S.N. Bio-adsorbent Removal method Experiment conditions Result References

1. Barks of phyllanthus niruri,
Annona squamosa, Calotropis
gigantean, Tridax procumbens,
and Azadirachta indica.
2. Rice straw
3. The biosorbents derived from
achyranthes aspera, hsibisuc
rosa-sinensis and tribulus
terrestris.
4. Leaves and their ashes of
Cassia auriculata, Celastrus
paniculata and Carmona
retusa
5. Biochars derived from
agricultural residues such as
straw, bagasse, and animal
manure
Leaves of these plants are
collected and washed with
distilled water and turned
into fine powdered
particles
Rice straw is also an
economic waste of rice,
using for removal of
ammonia from water.
Leaf of plants are collected
and washed with distilled
water and turned into fine
powdered particles
Leaves of these plants are
collected and washed with
distilled water and turned
into fine powdered
Biochar is a pyrogenic
carbon material that has
attracted much attention
recently
Optimum pH was adjusted with dil. HCl or The removal % increases with time Suneetha and
NaOH using pH meter. The samples were for a fixed adsorbent at a fixed pH and Ravindhranath,
shaken in shaking machines for certain certain duration. 2012b
optimum periods then the samples were
filtered and analyzed for NH3% of removal.
The kinetic and isothermal adsorptions The removal efficiency of NH4 Khalil and
were investigated, including the NH3 recorded 43, 53.7, and 69.5%, with Sergeevich, 2018
removal efficiency, the contact time of maximum adsorption values of 2.9,
adsorbent, amount of adsorbent and initial 3.5 and 4.5 mg/g at temp. of 25, 35,
concentration of NH4. and 45  C at pH 7.5.
Physico-chemical parameters such as pH, The percentage removal increases Rani and
sorbent concen. and equilibration time. with time for a fixed adsorbent at a Ravindhranath,
fixed pH at certain duration. 2014a
Physico-chemical parameters such as pH, More than 86% of NH3 remove is Rani and
equilibration time and sorbent concen. have measured from simulated waters in Ravindhranath,
been optimized for the maximum removal all sorbents at the optimum 2014a
of ammonia from polluted waters conditions of removal.
The biochar with the highest sorption of The biochars showed good sorption Rani and
NH3 in the initial evaluation was selected to ability to NH3 in aqueous soln Ravindhranath,
test the effects of pH, temperature and ionic however the biochars produce at 2014a
strength. lower temp. was better

found best towards ammonia adsorption, it gave best percentages of
ammonia removal is pH sensitive and also depends on the sorption
concentration and time of equilibrium. More than 90% of ammonia can
be removed by using this bio-sorbent dosage at pH ¼ 5 and at optimum
equilibrium time and sorbent concentrations. The adoptability method-
ologies developed in this work are tested with various samples collected
from industries effluents and naturally polluted lakes and it's found that
the procedures are remarkable successfully (Suneetha and Rav-
indhranath, 2012b). According to Rani et al., 2014 has been observed
that the leaves and their ashes of cassia auriculata, Celastrus paniculata
and carmona retusa have affinity towards the ammonia ions. It was found
that the decrease percentages of Celastrus paniculata biosorbents the
ammonia removal percentages were increases. More than 86% of NH3
removal was noted from simulated waters in all sorbents are at optimum
conditions of extraction (Rani and Ravindhranath, 2014a). The meth-
odologies developed are successfully applied to samples collected from
industrial effluents and naturally polluted lakes. According to Gupta
et al., 2015 the absorbents used in the experiments namely sulfuric acid
based solution and pH of absorbents was 2.3. Wastewater was flowed
through the shell side of contactor, whilst absorbent solution flowed
through the lumen side of fibers (Gupta et al., 2015).
These results show that the ability of solution can compensate the
sulfuric acid solution to absorb NH3 through the hollow fiber membrane
contactor at the same pH of wastewater (Gao et al., 2015; Rani and
Ravindhranath, 2014b). According to Prameela Rani et al., 2014, the
biochars derived from agricultural residues such as rice straw, bagasse
and animal manure showed strong binding affinity to various heavy
metal ions in the aqueous solutions. Biochar is a pyrogenic carbon ma-
terial that has attracted much attention recently. The biochar with
highest sorption of ammonium in the initial evaluation was selected to
test the effects of pH, temperature and ionic strength. All biochars were
prepared from the agricultural residuals at different pyrolysis tempera-
tures. All of them showed good sorption ability to ammonium in aqueous
solutions; however, the biochars produced at lower temperature were
better (Rani and Ravindhranath, 2014b). According to Khalil et al., 2018,
the rice straw is also an economic waste of rice, with millions of tons
produced per year around the world. The kinetic and isothermal
adsorption trends were investigated, including the ammonium removal
efficiency, contact time of adsorbent, amount of adsorbent and initial
concentration of NH4þ. The effect of temperature and pH are also dis-
cussed. The removal efficiency of NH4 was recorded 43, 53.7 and 69.5%
with maximum adsorption values of 2.9, 3.5 and 4.5 mg/g at
temperatures of 25, 35 and 45  C respectively, at pH 7.5 (Khalil and
Sergeevich, 2018; Gorre and Himabindu, 2015; Rani and Ravindhranath,
2014a). According to Suneetha et al., 2012, the leaves and their ashes of
cassia auriculata, celastrus paniculata and carmona retusa. Leaves of
these plants are collected and washed with distilled water and turned
into fine powdered particles. Physico-chemical parameters such as pH,
time of equilibration and sorbent concentration have been optimized for
the maximum removal of ammonia. More than 86% of ammonia removal
is noted from simulated waters in all these sorbents at optimum condi-
tions of removal (Suneetha and Ravindhranath, 2012b; Khalil and Ser-
geevich, 2018).
3. Mechanism of ammonia and nitrates removal from
contaminated water by the biosorptions processes
Adsorption is a physicochemical process that commonly involves mass
transfer of a substance (i.e. adsorbate) from gas or liquid phase to the
surface and/or interface of solid phase (i.e. adsorbent). In the adsorption
process occurs in four consecutive steps: (i) Bulk diffusion, (ii) Film
diffusion or external mass diffusion: transportation from bulk solution to
adsorbent surface by diffusion through the boundary layer, (iii) Pore
diffusion or intraparticle diffusion: diffusion from the external surface into
the pores of adsorbents, and (iv) physical and/or chemical reaction:
adsorption between adsorbate and active sites of adsorbent (Namasi-
vayam and Sangeetha, 2004; Frisoni et al., 2001). The initial bulk diffu-
sion step can be ignored if an evenly stirring is applied to the solution,
because a homogeneous distribution of adsorbent and adsorbate in the
solution can decrease the impact of mass transfer resistance. The final step,
i.e., physical/chemical reaction has done fast, thus the adsorption kinetic
is mainly controlled by film diffusion and/or pore diffusion. The film
diffusion rate is proportional to the liquid concentration and surface area
(i.e. liquid membrane area) of the adsorbent. Increasing the relative ve-
locity between the liquid and particles, i.e., make the fixed liquid film on
the surface of particles thinner and accelerate the film diffusion rate. The
pore diffusion rate depends on the fluidity of pollutants in the pores, which
is related to the pore structure and pore distribution of the adsorbents, the
molecular size and structure of adsorbates, while less affected by the liquid
concentration or the surface area of adsorbent particles. The mechanism of
ammonia and nitrates adsorptions by the biosorbents processes is shown
in Fig. 4. The pore diffusion rate is directly related to the square root of
adsorption time (t0.5). Therefore, if a linear relationship is obtained be-
tween the adsorption rate and t0.5, it can be concluded that the pore

7
S. Dey et al. Current Research in Chemical Biology 1 (2021) 100005

Fig. 3. Removal of nitrates from water by the biosorbents processes (Niazi et al., 2016).

Fig. 4. Mechanism of adsorptions and desorption's of ammonia and nitrates in biosorbents (O'Connell et al., 2008).

diffusion process dominates adsorption at these times (Liu et al., 2011;
Tian et al., 2009).
The biosorption of ammonia and nitrates from contaminated water
show a great potential due to its environmental compatibility and cost-
effectiveness. To get the experimental values, which can be applied for
design of treatment plant in the field, may be taken the help of various
experiments conducted in the laboratory. However, the impact of
different system conditions such as effect of temperature, pH and pres-
ence of other metal compounds need to be further studied (Luo et al.,
2010; Mehta et al., 2021). Surface modification of the biosorbents can
also be an important factor affecting the removal performance and needs
to be characterized further. The various steps of biosorptions in ammonia
and nitrates removal is shown in Fig. 5. By the usage of solid waste
bio-sorbent the chemicals in treatment of water and waste water may be
reduced. The biosorptions processes have been carried out in a batch type
of reactor system (Wang et al., 2020; Gupta et al., 2012).
A continuous reactor system may be considered for results, which can
be applied under field conditions more effectively. Studies on removal of
ammonia and nitrates (in various forms) in presence of other related
pollutants need to be done. Effects of time, temperature, light, dissolved
oxygen other mineral concentrations, which are encountered under open
natural conditions need to be understood. This study help in initially
screening various bio-sorbent media for setting up treatment plants may
at community level or house hold levels in developed, developing and

8
S. Dey et al. Current Research in Chemical Biology 1 (2021) 100005

Fig. 5. Different steps involved in the biosorptions of ammonia and nitrates (Ramírez et al., 2020).

Fig. 6. Kinetics modeling of the ammonia and nitrates biosorptions processes (Karapantsios, 2012; Figueroa-Torres et al., 2016).

under developed countries. The effects of time, temperature, light, dis- the surface of biosorbent can be single or multiple layers. When mono-
solved oxygen other mineral concentrations etc, which are encountered layer adsorption occurs, the adsorbates can only cover a single molecular
under open natural conditions need to be understood (Varshney et al., layer on the adsorbent surface and chemical adsorption is a typical
1996; Benaissa and Benguella, 2004). monolayer adsorption. While for multilayer adsorption, the adsorbent
In a batch system, certain amounts of sorbent are mixed with solu- surface adsorbs more than one molecular layer of adsorbates. Physical
tions containing a known concentration of ammonia and nitrates in adsorption can be multi-layer adsorption and multiple layers of physical
containers for a fixed contact time and subsequently sorbate is separated adsorption can be performed onto the chemically adsorbed monolayer
by sedimentation or filtration. The batch mode of sorption is shown in (Aksu, 2001; Mehta et al., 2017; Babarinde et al., 2009).
Fig. 6, the static and conducted in closed system and therefore the data The adsorption rate of aqueous solution on the adsorbent is based on
obtained are generally not applicable to real systems. The batch method
is used to examine the mechanism of sorption and to compare the sorp-
tion capacity of various sorbents. For instance, the charged contaminants Table 3
(inorganic and organic pollutants) tend to adsorb on adsorbents with Kinetics models of metals biosorptions processes.
oppositely charged surface through electrostatic attraction; heavy metals Adsorptions Models Equations Assumptions
produced exhibit high affinity with adsorbents with abundant surface Models
hydroxyl groups or other functional groups; for organic pollutants with Adsorption Pseudo-first- dqt Adsorption kinetics
¼ kp1 ðqe
qt Þ
larger sizes, the adsorbents with mesoporous structures generally show reaction order dt models depend upon
high adsorption capacities and kinetics. In addition, because adsorption models the adsorption
is reversible sometimes, adsorbents can be regenerated by suitable capacity.
Pseudo- dqt Kinetics models
desorption process (Ho et al., 2000; Dey et al., 2019). The efficient ¼ kp2 ðqe
qt Þ2
second-order dt depends upon the
removal of contaminants in the low concentration range is very impor- chemisorptions
tant because the content of some pollutants in most natural contaminated processes.
waters is not high. The adsorbents should have the potential to reduce Third-order dCt Applied in solid-liquid
¼
k2 Ct2
dt reaction systems
contaminants at very low concentrations. The regeneration of lower  
Adsorption Liquid film qt The film diffusion rate
loading adsorbents is necessary to achieve the maximum utilization of ln 1
¼
kfdt
diffusion diffusion qe controlling step
adsorbents. The study of biosorption process can improve the adsorption model Intraparticle 1 The intraparticle
rate, which can be improved by rational design of adsorbents and opti- diffusion qt ¼ kid t 2 þ C diffusion controls the
mization of experimental conditions. The nitrate molecules adsorbed on final adsorption rate

9
S. Dey et al.
Fig. 7. Ammonia and nitrates removal using nanostructure hydrated biosorbents in a polymeric anion exchanger.
the adsorption capacity and following the first-order equation as dis-
cussed in Table 3. Where qt (mg.g
1) is the adsorption capacity at time t,
qe (mg.g
1) is the equilibrium adsorption capacity, and k1 (min
1) is the
first-order constant. The expression of second-order was used to describe
the kinetics of adsorption processes. Where k2 (g.mg
1. min
1) is the rate
constant of pseudo second order and C is the constant. The adsorption
capacity increases with the increase of pollutant concentration at first,
owing to the high driving force of mass transfer and large amounts of
present vacant binding sites and then slowly reaches a plateau due to the
saturation of adsorption sites on the adsorbent surface. While the
removal percentage decreases as the initial pollutant concentration in-
creases, due to the limited available sites. The kinetics models of metals
biosorption processes are shown in Table 3. The increase in amount of
adsorbent decreases the adsorption capacity due to the increasing pro-
portion of unoccupied binding sites. The decreasing of adsorption ca-
pacity is the aggregation of particles may occur at high adsorbent
concentration, which would lead to a decrease in the total surface area of
adsorbent. Kinetics studies provide important information about the
adsorption process, which are necessary to depict the adsorption rate and
control the residual time (O'Connell et al., 2008; Lee et al., 2009; Cao
et al., 2010; Boeykens et al., 2017; Ward and Brender, 2011).
To better understand the adsorption process is shown in Fig. 7, several
mathematical models have been proposed to test kinetic data from batch
adsorption experiments to ascertain the best-fitting kinetic model, which
can be applied into adsorption reaction model and adsorption diffusion
model. The equations used in the kinetics models as the adsorption rate
constant for pseudo first-order, pseudo-second-order, liquid film diffu-
sion and intraparticle diffusion model, respectively. Among which, the
pseudo-first-order, the pseudo-second order kinetic model and intra-
particle diffusion model are most widely used models (Daud et al.,
2015; Srinivasan, 2011). In order to explain the equilibrium adsorption
isotherms, several models illustrated relationships between the equilib-
rium concentration of adsorbate in the solid phase (qe) and that in the
liquid phase (Ce) have been constructed at the constant temperature. The
equilibrium isothermal equations comprised of adsorption properties and
equilibrium data can be applied to optimize the use of adsorbents and
design of adsorption systems. Additionally, the different equation pa-
rameters and underlying thermodynamic assumptions of these
isothermal models often provide reliable prediction of the sorption
mechanism, the surface properties and affinity of adsorbent. The mag-
netic properties of biosorbents depend on various parameters such as the
composition, size and shape of particles. The surface area, porous
structures, surface active sites and possible redox characteristics of ni-
trogen oxides as shown in Fig. 8 are prominent reasons for their
improvement of adsorption performance. The biosorbents materials with
small particle sizes, especially in nanosizes, tend to have a unique set of
physical and chemical properties that are different from their
10
Current Research in Chemical Biology 1 (2021) 100005
Fig. 8. Bio-derived materials as a green route for metal recovery and re-use
purposes (Dodson et al., 2015).
corresponding bulk materials due to the quantum effect (Abou Taleb
et al., 2008; Bhatnagar and Sillanp, 2011).
For instance, the biosorbents with nanosized particles and/or pores
can strongly adsorb ammonia and nitrates substances from the aqueous
solution, since most of the unsaturated atoms and ligands with high
adsorption activity present on the surface of nanosized adsorbents, which
can bind tightly to the pollutants through strong static electricity. The
lower size biosorbents particles show faster adsorption kinetic due to the
lower diffusion resistance. While from an energy point of view, a
decrease in particle size results in an increase in the surface energy
fraction, thus nanoparticles tend to aggregate easily. The addition of low
dielectric medium, such as ethanol, to the aqueous solution can alter the
thermodynamics of reaction system and nucleation kineics, further
reduce the particle sizes (Baes et al., 1997; Ozcan et al., 2005). The
biosorbents species may be transported from bulk solution onto the
sorbents through intra-particle diffusion/transport processes. The rate
limited step was taken into consideration and intra-particle diffusion
model was introduced. Based on the diffusion rate constant, the
adsorption process could be divided into three phases, the boundary
layer adsorption phase, intraparticle diffusion phase and equilibrium
adsorption phase. The boundary layer adsorption phase was rapid; the
intraparticle diffusion phase reflected ammonia and nitrates adsorption
onto the biosorbent surfaces (Borislav et al., 2007; Mehta et al., 2018).
The readily accessible sites reacted with ammonia and nitrates through
mass transferring, followed by the same reaction occurring at progres-
sively less accessible sites controlled by diffusion. The intraparticle
diffusion may govern by the reaction of adsorption kinetics. The
ammonia and nitrates biosorption capacity increased with the increasing
temperature; this is explained by the increasing penetration of ionic ni-
trogen into micropores of biosorbents or the formation of new active sites
at higher temperatures. The thermodynamic parameters such as ΔG ,
S. Dey et al. Current Research in Chemical Biology 1 (2021) 100005

Fig. 9. The ion exchange and diffusion mechanism involved in the biosorptions processes (Abdel Maksoud et al., 2019; Gaur et al., 2014).

ΔH and ΔS measure by using the following equations to measure the the formation of covalent chemical bond with a metallic cation (such as
thermodynamic feasibility and type of adsorption process. From Eqs. Ca2þ) resulting to release of other ions (such OH
) previously bonded to
(1)–(4) analysis the kinetics reactions mechanism of various biosorbents the metallic (M) cation. The surface precipitation in the liquid phase
for removal of nitrates present in water (Tien and Ramarao, 2014; which is absorbs into the pores of adsorbent. Hydrogen bonding refers to
Chatterjee and Woo, 2009). the sorption of –N on metal oxides and/or organic molecules, while the
diffusion occurs when –N is moved into the interior body of sorbent and
ΔG0 ¼
RTlnKd (1) sorbed inside the pores and cavities of the surface. The significant
desorption on water shows that the –N was physically sorbed and
lnKd ¼ ΔSo R
ΔHo RT (2) bonding was easily reversible (Bulut et al., 2008; Richards et al., 2010;
Cengeloglu et al., 2006).
Kd ¼ aqe Ce (3) From the practical point of view the advantageous in case by using N-
loaded fertilizer due to easier N desorption and its uptake by the plants.
ΔGo ¼ ΔHo
TΔSo (4) The decrease of biosorbents as shown in Fig. 9 at higher dosages was
  
attributed to unsaturated binding sites during the adsorption process.
In these equations, ΔG , ΔH and ΔS are the free energy of adsorp-
Besides, the possible aggregation of biosorbent particles can lead to a
tion (kJ/mol), the standard enthalpy change (kJ/mol) and standard en-
decrease of specific surface area of the sorbent and to an increase of the
tropy change (J/(mol.K)), respectively; T (K) is the absolute temperature
diffusion path length. The support materials are introduced prior to the
in Kelvin; R (8.314 J/(mol.K)) was the universal gas constant; K d is the
biosorptions and are left inside the continuous culture for a period of
thermodynamic equilibrium constant; α is the adsorbent dose (g⋅L
1).
time, after which the film of microorganisms is apparent on the support
The positive value of enthalpy change demonstrates that the endothermic
surfaces. The chemisorptions suggesting that both mechanisms, i.e.
nature of reaction, which was supported by increases in qm as temper-
physisorption and chemisorptions may be involved in the ammonia and
ature increases. The ΔG values decreased with the increasing reaction
nitrates sorption. The wastewaters contain various ions which increase
temperature, a result of the positive entropic contribution
the solution ionic strength and may compete with ammonia anions for
(ΔG ¼ ΔH —TΔS ) (Kuila et al., 2014; Chiou et al., 1993). The ammonia
binding sites. The adverse effect of ionic strength on ammonia and ni-
and nitrates sorption to biosorbents modified materials might be the
trates uptake suggests a possible involvement of ion exchange mecha-
overall entropy variation decreases when the equilibrium state was
nism (Cui et al., 2015; Erdem et al., 2004).
attained, as species are adsorbed onto the biosorbent surface. The pH
At lower ion concentrations, the presence of Naþ or Kþ in the solution
value is important in the adsorption, because it affects the species of
from the added salts may reduce the repulsion of ammonia and nitrates
nitrates ions and ionization of active functional groups on the biosorbent
anions improving the ammonia and nitrates biosorption. An increase of
surfaces. The kinetic studies were helpful for predicting the adsorption
ionic strength can decrease the coulombic attraction between the positive
rate with time and explaining the active interactions of nitrate ions with
and negative charge. This weaker interaction inhibits the sorbent parti-
adsorbents which gave important information for designing and
cles and ammonia and nitrates species from approaching each other. The
modeling the processes. The Thomas model was used to describe the
central composite design was found to be a good approach to optimize
performance of adsorption process in a fixed-bed column. This model
the variable affecting nitrates adsorption (Dey and Dhal, 2020; Grote and
assumed plug-flow behavior in the bed and used Langmuir isotherm for
Kettrup, 1985). Biosorption is being demonstrated as a useful alternative
equilibrium and second-order reversible kinetics. Pseudo-second-order
to conventional systems for the removal of toxic metals from industrial
model has been involved to describe the adsorption of pollutants on
effluents. Future investigations shall be directed to ammonia and nitrates
biomaterials (Mehta et al., 2019; Sun et al., 2016; Konan et al., 2012).
removal from wastewater that will give better insight into the effect of
The OH
ion could complex with functional groups, such as cellulose
coexisting anions. The surface area is an important parameter that in-
to form cellulose OH
links. This would reduce OH
concentrations and
fluences the adsorbance performance. The pore distribution also
ligand exchange to promote adsorption and keep the final pH increasing
appeared to be random in the structure as shown in Fig. 10. Physical
slowly from 6.8 to 7.9, while the initial solution pH increased from 4.0 to
adsorption is mainly caused by Van der Waals forces the value of surface
9.5. The sorption kinetics followed a pseudo first-order model and
area is an important parameter that influences the absorbance perfor-
intraparticle diffusion model; the endothermic adsorption process could
mances (Zhao et al., 2011; Gupta et al., 2011).
be divided into three phases. The ligand exchange mechanism refers to

11
S. Dey et al.
Fig. 10. Adsorption of nitrate and ammonia from aqueous solution using amine cross-linked (Qiao et al., 2019).
The particle size of scoria was finer, the specific surface area was
higher and removal of NHþ
3

4 -N, NO2 -N and NO -N was increased. This is
because increases in the specific surface area led to increased adsorption
binding sites of unit mass. Then, Van der Waals forces played an
important role and had stronger effect. Therefore, the physical adsorp-
tion on the surface is one of the mechanisms of adsorption for scoria
which has a huge amount of surface energy (Imamoglu and Tekir, 2008;
Macias et al., 1995).
Adsorption is a phenomenon of adhesion of ions or molecules from
one phase in to another. The surface biosorbents ions are adhered to the
surface of another media in mono or multilayer. Nitrate is a polyatomic
compound of nitrogen with three molecules of oxygen and one molecule
of nitrogen bonded by a ligand. Most of the nitrate is in the form of
ammonium nitrates or magnesium nitrates which are found in commonly
used agricultural fertilizers. The cations in the salts are adsorbed by the
clay particles having negative surface charge. This negative charge re-
pulses the anions like nitrate (Mahmoud et al., 2010; Monge-Amya et al.,
2015). Thus the nitrate readily mixes with pore water. For removing
nitrate from water, adsorbents with positive surface charge are employed
which gives more removal efficiency. Biological denitrification is a
cost-effective and promising method of biological nitrate removal is
reviewed in terms of its removal process, applicability, efficiency and
associated disadvantages. The various pathways during biological nitrate
removal, including assimilatory and dissimulator nitrate reduction (Qin
et al., 2020; Niazi et al., 2016).
4. Deactivation and regeneration of various biosorbents
materials
The ammonia and nitrates sorption capacity of biosorbent was signifi-
cantly increased by the modification of biosorbent materials. The phyto-
toxicity tests and concentration of heavy metals in the spent biosorbent was
concluded that the nitrates-saturated peat (spent sorbent) can be utilized in
land application, which would remove the need of costly disposal of ma-
terial in landfills. The amount of metal sorbed depends on the kinetic
equilibrium and composition of metal at the cellular surface. Advances in
the understanding of metabolic pathways of microorganisms are respon-
sible for metal sequestration, improving microbial survival rates and their
12
Current Research in Chemical Biology 1 (2021) 100005
stability. The biosorbents materials deactivation and failure over time in
their performances is creating problem in the practice of adsorption process
(Ramírez et al., 2020; Karapantsios, 2012). The suitable life of biosorbents
is very important, which can be defined as the time over which the bio-
sorbents material performance over ammonia and nitrates metals adsorp-
tion must be maintained. The major reason for biosorbents materials
deactivation is divided into three parts: Chemically, mechanically and
thermally. The dispersion of active phase rapidly decreases, which is one of
the major reason for biosorbents deactivation. Desorption and regeneration
capacities are very important in proper biosorbent selection for the bio-
sorption process. The deactivation of biosorbents materials are main reason
for failure of surface area due to the crystalline development of their phase.
The main reason of biosorbents materials poisoning is due to the highly
adsorption of feed impurities; therefore, the poisoned materials are very
tough to regenerate. The deactivation mechanism occurs when the poison
molecules become reversibly or irreversibly chemisorbed to the active sites,
thereby reducing the number of active sites available for the reaction
(Figueroa-Torres et al., 2016; Dodson et al., 2015).
The poisoning molecule may be a reactant and/or product in the main
reaction or produced impurity in the feed stream. The poisoning is highly
effects of reactants, impurities present on the sites or presenting for the
biosorbents materials. The ammonia and nitrates deposited on the bio-
sorbents surface blocks the active sites and prevents further reactions from
taking place, thus “poisoning” and ultimately deactivating the bio-
sorbents. The metal poisoning is highly effects of reactants, impurities
present on the biosorbents sites or representing for the biosorptions pro-
cesses. The deposition of poisoning on the biosorbent material surfaces
cause of deactivation is shown in Fig. 11. The metal deposited on the
biosorbents surface blocks the active sites and prevents further reactions
from taking place, thus “poisoning” and ultimately deactivating of the
biosorbents materials (Abdel Maksoud et al., 2019; Gaur et al., 2014).
The deactivation of biosorbent materials can be used in theoretical
and practical foundations for design of high-performance materials for
ammonia and nitrates adsorptions. A lot of efforts have been made to
improve the stability of biosorbents materials including the support
materials. The regeneration process reduces the metal content with no
significant change in the biosorbent materials dispersion and restores the
activity. The various studies have been performed on the regeneration
S. Dey et al.
Fig. 11. Deposition of poisoning on the biosorbent material surfaces (Dey and Dhal, 2020).
Fig. 12. Regeneration of biosorbents by using various treatments (Gautam et al., 2014).
and reuse of pretreated biomass after metal loading. The desorption's
studies also help to determine the biosorption mechanisms such as ion
exchange, complexation and physisorption (Qiao et al., 2019; Gautam
et al., 2014). The most common materials used are diluted HCl, NaOH,
HNO3 and EDTA solutions, usually in concentration up to 0.1 mol/L.
Through desorption and recovery of adsorbed metals by using materials,
the stability of biosorbent also tested. Repeated exposure of biosorbents
to acidic conditions comprised of strong desorption agents such as HCl
can affect the biomass rigidity, due to biomass degradation and decrease
in the binding sites. Finally, the regeneration of biosorbents to improved
use takes into the account. So, the regeneration of biosorbent with a
minimum amount of residual heavy metal and consequently reusing of
biomass are important for cost-effective implementations of the process.
The purpose of this research is to optimize the use of biosorbent in
ammonia and nitrates remove from aqueous solutions by the successive
biosorption–desorption cycles in a fixed-bed column. In exhaustion and
breakthrough times it was observed that the behavior was similar to the
biosorption capacity. The regeneration of exhausted biosorbent as shown
in Fig. 12 which presented the best biosorption capacity in continuous
mode was measured in several sorption–desorption cycles by using an
optimal desorption solution (Shi et al., 2021; Liu et al., 2018).
The regeneration of biosorbent and reuse in several bio-
sorption–desorption cycles is an important aspect from the point of view
13
Current Research in Chemical Biology 1 (2021) 100005
of its real applications. However, the interest of regeneration of bio-
sorbent depends on the lot of aspects as cost of the process, dispensability
of biosorbent, value of recovery metal etc. These results are very inter-
esting from an industrial point of view to choose the optimum opera-
tional time of the desorption process. The process of biosorption is
advantageous because it is reversible does not require nutrients a single
process of quick range and has no longer of toxic effects and cellular
growth (Ramírez et al., 2020; Karapantsios, 2012). The regeneration is
usually carrying out by various eluting agents (acids or base) by different
desorption mechanisms to release the adsorbed heavy metal ions into the
solution. The reusability of biosorbents provides an economic advantage
and is desired for the practical and commercial utility in wastewater
treatment processes. The use of biological denitrification for removal of
nitrate from drinking water is well established. Inactivated, non-living
microbial biomass can serve as a basis for development of potent bio-
sorbent materials for concentration and recovery of strategic or valuable
heavy metals, nuclear fuel or radioactive elements (Mustafa et al., 2021;
Wen et al., 2020).
5. Conclusions
The removal of ammonia and nitrates from contaminated water by the
biosorption processes is a simple and sensitive method. Biosorption is an
S. Dey et al.
economical and environment-friendly method for removal of toxic materials
from contaminated water. The various functional groups are present in the
biosorbents divided into acidic or basic, which affect the surface charge and
consequently the biosorption capacity of biosorbents. The biomass can be
modified by the physical and chemical treatment before use. The process can
be made economical by regenerating and reusing of the biosorbent after
removing the heavy metals. Various bioreactors can be used in biosorption
for removal of metal ions from large volume of water. From the biosorption
isotherms describe how the sorbate molecules are distributed between the
liquid phase and solid phase when the system reaches equilibrium. The
analysis of isotherm data by fitting them to different models is important to
find a sustainable model that can be used. The variation in temperature had
two major effects on the sorption process. An increase in the temperature is
known to increase the rate of diffusion of adsorbate molecules across the
surface boundary layer and in the internal pores of adsorbent particles as a
result of reduced viscosity of the solution. In recent years, biosorption/bio-
accumulation process have been considered as novel, economical, efficient
and eco-friendly alternative treatment technologies for removal of
contaminated from wastewaters produced from various industries.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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