Journal of Molecular Liquids 290 (2019) 111197

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Journal of Molecular Liquids

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

Review

A review on heavy metal pollution, toxicity and remedial measures:

Current trends and future perspectives
Kilaru Harsha Vardhan a, Ponnusamy Senthil Kumar a,⁎, Rames C. Panda b,⁎
a
Department of Chemical Engineering, SSN College of Engineering, Chennai, Tamilnadu, India
b
Department of Chemical Engineering, CSIR- CLRI, Adyar, Chennai 600 020, India

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

Article history: Water is an exceptionally essential source for the presence of life on the earth. The water quality has seriously
Received 27 March 2019 affected because of the overgrowth of the population, human activities, fast industrialization, unskilled utilization
Received in revised form 12 June 2019 of natural water resources and unplanned urbanization. Heavy metal is a group of metal and metalloids with an
Accepted 15 June 2019
atomic density higher than the 4000 kg/m3. The heavy metals are toxic in nature which causes serious health ill-
Available online 18 June 2019
ness to human beings and animals, even at very low concentration. These heavy metals enter into the aquatic sys-
Keywords:
tem through the agricultural runoff and industrial discharges. Different treatment methods are available to
Adsorption remove the heavy metals from the aquatic environment with a different degree of success. In any case, the defi-
Adsorbent ciencies of a large portion of these treatment methods are due to the production of secondary waste, high cost for
Heavy Metals operation and maintenance etc. Hence, it is important to develop robust, eco-friendly and economically viable
Toxicity treatment methods for the removal of heavy metals from the aquatic system and to safeguard the environment.
Treatment In this review article, definite data on the source and their belongings of substantial metal contamination to the
Wastewater plants, individuals and other living life forms have been clarified. The distinctive sorts of treatment strategies for
the removal of the toxic metals from wastewater had been explained. The numerous types of low-cost adsor-
bents utilized by different researchers/scientists for removal of heavy metals from wastewater have been
discussed in detail. The recommendations for further scope of research which can be done have been discussed
in detail.
© 2019 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Water pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. Heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.1. Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.2. Cadmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2.3. Zinc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3. Heavy metals toxicity in the environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3.1. Impact of heavy metals on plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3.2. Impact of heavy metals on human health . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.4. Treatment methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.4.1. Chemical precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.4.2. Chemical coagulation/flocculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.4.3. Electrochemical methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.4.4. Membrane filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.4.5. Ion-exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.4.6. Bioremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.4.7. Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2. Adsorbents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

⁎ Corresponding authors.
E-mail addresses: senthilkumarp@ssn.edu.in (P.S. Kumar), panda@clri.res.in (R.C. Panda).

https://doi.org/10.1016/j.molliq.2019.111197
0167-7322/© 2019 Elsevier B.V. All rights reserved.
2 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197

2.1. Adsorbents from industrial byproducts/wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

2.1.1. Adsorbents from lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.2. Adsorbents from fly ash . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.3. Adsorbents from sludge and blast furnace slag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.4. Adsorbents from red mud . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.2. Adsorbents from agricultural byproducts/wastes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2.1. Adsorbents from rice husk . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2.2. Adsorbents from waste peels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2.2.3. Adsorbents from wheat wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2.4. Adsorbents from clay materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2.5. Adsorbents from other agricultural wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3. Comparison of Langmuir adsorption capacities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4. Conclusion and scope for further research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

1. Introduction
1.1. Water pollution
Water is an exceptionally essential hot spot for the presence of life
on the earth. It is a wellspring of life and imperativeness, yet a consider-
able number of people worldwide are suffering with the absence of new
and clean drinking water. In the most recent century, the water demand
for anthropogenic activities has expanded sevenfold due to the quadru-
pled worldwide population [1]. A report on“Progress on Sanitation and
Drinking Water-2015 Update and MDG Assessment” by the World
Health Organization (WHO) indicates that, around 2.6 billion peoples
have accessed to enhanced drinking water source in the year 1990
may increase to 663 million people accessing to enhanced drinking
water source by the year 2015. The number of individuals living in
water scare areas will increase to around 3.9 billion by 2030, as assessed
by the World Water Council [2]. The present and the future demand for
water assets is expanding, because of increase in urban, industries and
natural needs, and it is important to search for the arrangements that
permit the effective cleaning of water for conceivable reuse in different
ways [3,4,7]. The fast pace of industrialization, population explosion,
furthermore, the spontaneous urbanization has leaded to serious con-
and arsenic are not essential for the growth of plants and animals. The
soil gets polluted due to the heavy metals because of the entry of the in-
dustrial wastewater, sewage sludge, fertilizers, utilization of treated
wastewater in land application and weathering of soil minerals
[24,35,36].
Heavy metals creates not only soil pollution, but it influence on food
generation, quality and well being also [38]. Some heavy metals are poi-
sonous to plants even at a very low concentration, while other heavy
metals may accumulate in plant tissues to moderately abnormal states
with no obvious side effects or decrease in yield [39–43]. The growing
of the plants in these heavy metal-contaminated areas, bring change
in their metabolism, physiological and biochemical means which results
in metal accumulation, lower biomass generation and reduction in the
biomass growth. Certain points need to be considered while doing re-
search on the toxicity of heavy metals in plants. To start with, the im-
pacts caused by contaminated soils are perpetual, and their sub-
atomic behaviors must be considered. Most examinations have been
done in hydroponic or in vitro culture, and have included the utilization
of greatly high metal concentrations in the development media. The
harmfulness of a heavy metal relies upon its oxidation state, for exam-
ple, Cr(VI) is viewed as the most poisonous type of Cr, and as a rule, hap-
pens related with oxygen as chromate (CrO2- 4 ) or dichromate (Cr2O7 )
2-

tamination of water and soils. The primary wellsprings of freshwater
contamination can be ascribed to the release of untreated clean and poi-
sonous industrial wastes, dumping of industrial wastewater, and runoff
from agrarian fields. It is remarkable that 70– 80% of all problems in de-
veloping countries are identified with water pollution, especially help-
less for ladies and youngsters. The toxic pollutants released in
wastewaters can be harmful to aquatic organisms which also cause
the regular waters to be unfit as consumable water sources [5,6,8–12].
A substantial number of poisons substances, for example, toxic metals,
pharmaceuticals, pesticides, dyes, surfactants, and others have polluted
the water resources and are ecologically dangerous to individuals and
creatures [13–22].
1.2. Heavy metals
Heavy metals are a general term which applies to the group of
metals and metalloids and it has an atomic density more prominent
than 4000 kg/m3 [23,24]. Almost all the heavy metals are toxic to
human beings even at low metal ions concentrations [25–34]; [21];
[37]. Some of the examples for the heavy metals include copper, cad-
mium, zinc, chromium, arsenic, boron, cobalt, titanium, strontium, tin,
vanadium, nickel, molybdenum, mercury, lead, etc. The heavy metals
like copper, zinc, nickel, boron, iron, molybdenum are the basic needs
for the growth of the plants but these heavy metals are harmful to the
creatures and plants when their concentrations go beyond the permis-
sible limits. Other few heavy metals such as lead, mercury, cadmium,
oxyanions. Cr(III) is less portable, less harmful, and prevalently bound
to organic matter in soil and aquatic systems [44–46]. The capacity of
heavy metals to endure in the soil in the form which is bioavailable to
the roots was affected by their adsorption, desorption, and complexa-
tion in the soil matrix. These processes were strongly affected by soil
composition, pH, and structure. Heavy metals have a tendency to be
more portable in acidic soils. The heavy metal poisonous quality is spe-
cies dependent. For example, metal-tolerant plants and certain plants
known as hyper accumulators [able to gather no less than 100 mg/g
Cd, As, and some other metals, 1000 mg/g Co, Cu, Cr, Ni, and Pb and
10,000 mg/g Mn and Ni [47]] have barrier mechanisms that dodge
harm caused by the heavy metal-initiated pressure, despite the fact
that the span and magnitude of exposure and other natural conditions,
adds to heavy metal affectability [48].
The people exposed to high amounts of heavy metals may experi-
ence the ill effects of different ailments, for example, gastrointestinal
and renal toxicity, cardiovascular issues, tumors, hematic, melancholy,
tubular and glomerular dysfunctions, and osteoporosis. Newborn
children's, kids, and young people are especially immune to heavy
metal, bringing about formative difficulties and low insight remainders.
Most of the countries have framed the norms for the heavy metals al-
lowable limit in the food to avoid its consumption. The large portion
of the heavy metal contaminations are from industrial wastewater
which includes mining, pharmaceuticals, electroplating, rubber and
plastics, metal finishing, tanneries, organic chemicals, pesticides, timber
and wood items, and so forth [49–53]. The heavy metals are transported
 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197
by runoff water and defile the water sources due to the industrial activ-
ities. Every single living including plants, animals, and microorganisms
rely upon water forever. Toxic metals can attach to the surface of micro-
organisms by bioaccumulation activities and it may even infiltrate in-
side the cell and can be chemically changed as the microorganism
utilizes biochemical reactions to digest the food materials.
Most heavy metals which include copper, cadmium, and zinc are
generally connected with pollution and toxic issues, especially when
they are available in dissolved form. The presence of any of these
heavy metals in extreme level is dangerous to people and can interfere
with numerous beneficials of the earth due to their harmfulness and
portability. Moreover, these heavy metals are nonbiodegradable,
which makes them harder to clean. Thus, it is Important to measure,
comprehend, and control of these heavy metal pollution in nature. The
details on these three heavy metals are as follows:
1.2.1. Copper
Copper (Cu) is one of the regularly utilized heavy metals for different
applications. It is generally utilized in electronic chips, batteries, cell
phones, semiconductors, water pipes, fertilizer industry, pulp, and
paper industry, fungicides, insecticides, catalysts, and metal processing
products [54–58]. Copper can enter the environment from the mining
of Cu and other metals and from industries which make or utilize the
metallic Cu or Cu compounds. Cu is an essential element for human be-
ings. Its quality is essential in the creation of hemoglobin in red platelets.
Cu(I) is found in enzymes fit for conveying oxygen which is similar to
the activity of haemoglobin. It can help fortify tendons and cartilage.
Cu is also utilized in the correct working of a few enzymes. Like iron
and zinc, it works as a micronutrient for human beings.
Cu is basic for healthy development. In any case, high dosages of cop-
per to living organisms can be to a great degree of unsafe. It can enter
the human body through food, residue, and water. The lack of Cu in peo-
ple can cause anemia, bone, and cardiovascular issues, weakening in
mental and sensory systems, defective keratinization of hair, a decrease
in levels of synapses, dopamine, and norephedrine, and imperfect
myelination in the mind stem and spinal line. Free copper ions, Cu2+,
is one of the most harmful types of copper in amphibian life. Utilization
of copper-polluted water or foods can cause intense gastrointestinal
side effects [59–62]. An intake of high measures of copper salt can
cause queasiness and intense gastric aggravation.
Numerous instances of detailed intense copper harming are regu-
larly connected with suicide endeavors. Ingestion of a lot of Cu with a
dosage surpassing 20 g may result in dazedness, laziness, and cerebral
pain at a beginning period. The consequent side effects are epigastric
torment, gastrointestinal bleeding, diarrhea, spewing, tachycardia, he-
maturia, respiratory challenges, hemolytic anemia, hepatocellular pu-
trefaction in the liver, intense tubular rot in the kidney, and demise
[63–76]. Patients with Wilson's sickness may hold expanded measures
of copper in the liver amid childhood. The side effects typically show
up between the ages of 6 and 40 years and if untreated results in liver
failure. The permissible limit of copper in drinking water as given by
the Bureau of Indian Standards (BIS) is 0.05 mg/L [77].
1.2.2. Cadmium
Cadmium (Cd) has been utilized broadly in batteries, ceramics, elec-
tronic and metal-finishing industries, electroplating industries, pig-
ments, petroleum products, textiles, insecticides, solders, television
sets, metallurgical industries, synthetic chemicals and photography
[78–85,87,88]. The raised concentrations of cadmium in air, water, and
soil happen near industrial sources, especially those of nonferrous min-
ing and metal handling activities. Cd is a profoundly harmful metal that
can accumulate in the human body and cause irreversible harms to var-
ious organic biological systems even at very low concentration. It has
been accounted for that Cd is more successfully retained in the aviation
routes than in the gastrointestinal tract. As the levels of cadmium in the
open air are for the most part underneath 10 ng/m3, the presentation
3
through the air isn't an issue of incredible worry, with the exception
of in intensely industrialized territories [89].
The Cd will enter into a human being easily through eating routine
and tobacco smoking. The high aggregation levels of cadmium are
found in offal results of mammals, for example, the kidneys and liver
[90–92]. The higher cadmium concentrations are available in a few
types of fish, mussels, and clams, which are gotten in the contaminated
seaside regions. For instance, the Cd levels in some consumable crabs
purportedly came to around 30–50 mg/L [93]. Non-smoking people
are highly affected by the consumption of cadmium-contaminated
food materials. Tobacco smoking is a basic wellspring of introduction
for smokers. It is the most critical human course of Cd allows in non-
contaminated regions. One cigarette contains roughly 1 to 2 μg Cd,
which is subject to the sort, the brand, and the area of production. A
man smoking a pack for each day may retain around 1 μg cadmium.
The Cd once entered into the human body, it is bound firmly to
metallothioneins. Over half, Cd in the human body accumulates in the
liver and kidney as a result of their capacity to orchestrate metallothio-
nein [94]. Cd may, at last, be disposed of through urine [95–97]. In any
case, the measure of Cd discharged day by day in urine is extremely
constrained (0.005% to 0.01% of the entire Cd content). The low dis-
charge rates of cadmium results in high retention in the body. Cd is out-
standing as a tireless poison with a natural half-existence of over 20
years. As the principle stockpiling organ of toxicants, the kidney is de-
pendably the basic target organ that showcases early indications of poi-
sonous quality [98]. Chronic presentation to hoisted levels of cadmium
can cause liver harm, bone degeneration, blood damage, and renal dys-
function. There are adequate confirmations in people for the cancer-
causing nature that outcomes from the presentation of both Cd and Cd
compound [99]. The allowable limit of cadmium in drinking water as
prescribed by the BIS is 0.003 mg/L [120].
1.2.3. Zinc
Zinc (Zn) is generally uncommon in nature, however, has a long his-
tory of utilization due to its available in restricted deposits and simplic-
ity of extraction from ores. Zn available in various minerals which
includes ZnO, ZnS, ZnCO3, Zn2SiO4, etc. Economically imperative ores
are for the most part those of carbonate and sulfide. Despite the fact
that zinc metallurgy is no less than 1000 years of age, zinc (depicted
as false silver) has been known for nearly 2000 years. Smelting opera-
tion was conveyed to Europe from India and China around the eigh-
teenth century and today zinc is mined and delivered in more than 30
nations. It positions fourth among the metals alongside steel, aluminum,
and copper in yearly worldwide utilization. The principal ore, ZnS, avail-
able worldwide alongside lead deposits. ZnS oxidizes promptly to pro-
duce various optional minerals, for example, ZnCO3. The trace metals
which include Ga, Ge, and Cd related with the ZnS minerals are sepa-
rated during the extraction operation. A large number of the major
zinc-lead deposits of the world are named strata-bound stores in car-
bonate rocks and generally available along and inside dolomite and cal-
cite minerals. Most Zn generation on the planet starts with ZnS
minerals. In the wake of mining and processing the ore, zinc sulfide con-
centrates are changed over into metallic Zn by either pyrometallurgical
or a mix of pyrometallurgical and electrolytic operations.
The most industrial utilization of Zn originates from its chemical and
metallurgical characteristics. The biggest utilization of zinc is in galva-
nizing iron and steel items. This gives a corrosion resistant coating
which can be done with an electroplated metal coating or natural coat-
ings. Such items are utilized in construction, siding, apparatus housings,
office hardware, heating and ventilation conduits, vehicle and building
enterprises for roofing, vehicle door boards, and underbody parts. Zn
is substituted by copper and plastic items in residential plumbing sys-
tems. New combinations, for example, zinc-aluminum alloy have been
created as protective coatings. The zinc-based alloy, are utilized for in-
door and window handles, grills, trim pieces, pumps, carburettors,
door locks and in other automobile components. The greater part of
4 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197
zinc oxide delivered was utilized as a catalyst for the vulcanization of
rubbers. Zinc oxide is likewise required for cosmetics, photocopy
paper, agricultural products, paints, and medicinal products. Zn dust, a
finely isolated type of the metal, is utilized in separating the silver and
gold from the cyanide solution, colouring the textile materials, printing
and fats purification. Climate safe paints in view of zinc oxide and zinc
dust give a standout amongst the best and strong coatings on the exte-
rior surfaces. The different applications of Zn which includes wood pre-
servative (ZnCl2), pigment (ZnS) and rayon fibre manufacture (ZnSO4).
Generally, Zn is a basic micronutrient and a considerably less dan-
gerous metal. But an extreme level of Zn consumption which includes
breathing Zn vapors and ingesting Zn-defiled foods and water can pro-
duce system dysfunctions, which causes a disability of growth and pro-
liferation [101–103]. Zinc is discharged into the environment mainly
due to the industrial operations which include steel manufacturing in-
dustries, mining, burning of coal and waste burning operations
[104–111]. The zinc poisoning showed the acute symptoms which in-
clude diarrhea, liver failure, bloody urine, icterus, kidney failure, stom-
ach cramps, abdominal cramps, epigastric pain, nausea, and vomiting.
The zinc poisoning also showed the chronic symptoms which include
pancreatic harm, anemia, and lower levels of high-density lipoprotein
cholesterol [112–119]. The permissible level of zinc in the drinking
water was suggested by the BIS is 5 mg/L [100].
1.3. Heavy metals toxicity in the environment
The release of heavy metals into the aquatic systems may result in
various physical, chemical, and biological processes [121]. These can
be isolated into two general classifications which include the effects of
the heavy metals on the environment and the effects of environment
on the heavy metals [122,123]. The first classification depends upon
the natural conditions, there might be an adjustment in diversity, den-
sity, species composition of population and structure of the community.
The nature and the degree of change depend to a great extent on the
concentration of heavy metal species in the water and dregs. Hence,
the physicochemical processes within the effluents and aquatic systems
have a noteworthy, albeit indirect, impact on the biological responses
[124,125]. The second classification stresses that the conditions in re-
ceiving waters may prompt an adjustment in the speciation and harm-
fulness of heavy metals. Such conditions incorporate differential
contribution of anthropogenic and geochemical material, nature of in-
dustrial effluents, and suspended solids and concentration of chelators.
The aquatic environment is described by [1] longitudinal varieties in
colloidal particles, suspended solids, and natural/synthetic ligands and
[2] vertical varieties in redox conditions, level of blending, and densities
of living life forms [126]. The destiny of metals in characteristic waters is
intensely reliant upon these factors. Changes, for example, methylation
and decrease to the metallic shape establish impacts of the environment
on metals. Likewise, descending development of metals to the base of
regular water bodies results from rummaging by suspended solids and
associative sedimentation. Organic ligands and chlorides complex
metals, diminishing the sorption procedure and expanding habitation
time in the water. Fundamentally, the speciation of metals is dictated
by nature, and changes in speciation are responses to modifications
[127].
The effects of heavy metal on the aquatic plants are profoundly var-
iable [128]. Albeit the characteristic responses, for example, diminished
diversity and density of populations, for the most part, happen in ex-
ceedingly defiled zones there are substantially more conflicting impact
intolerably or softly contaminated regions. Likewise, the population re-
sponses to the toxic heavy metals are altogether impacted by the varie-
ties in common natural parameters, for example, light and temperature
[129,130]. Subsequently, biological observing programs in view of com-
munity criteria are liable to extensive characteristic problem. This sug-
gests that the evaluation of heavy metals impact and management of
these toxic heavy metal releases must not be exclusively based on the
density and diversity measures. The release of heavy metal may like-
wise create changes in physical conditions in receiving aquatic environ-
ment. These incorporate changes in water pH, organic content of the
substrate and size of the particles in water. The plants in aquatic systems
react to such bothers by a decline in density, diversity, and composition
of species. Thus, the problem can be experienced in depicting impacts of
heavy metal pollution from those physical impacts which are actuated
indirectly [131–134].
1.3.1. Impact of heavy metals on plants
The plants are sessile life forms which must be adapted to different
composition of the soils with respect to their living and reproduction.
Soils are frequently contained with unnecessary levels of essential and
non-essential elements, which may be harmful at high concentrations
based upon the plant species and the soil qualities [109]. Numerous
metals are commonly shared their basic lethality mechanisms, and the
plants manage these metals by utilizing general removal routes. The ef-
fects due to the metal toxicity are made more intricate by rivalry, since
the elevated amounts of one metal may imbalance the removal and
movement of others and which provides the toxicity behavior
[135–137]. The plants procure minerals from soil fundamentally in the
form of inorganic ions. The expanded root and its capacity to assimilate
ionic compounds even at low concentrations which makes mineral up-
take to be more effective. The mineral compounds can be classified into
two categories: (i) essential nutrients (macro and micronutrients) and
(ii) non-essential nutrients. The essential macronutrients (nitrogen,
phosphorus, potassium, magnesium, calcium, silicon and sulfur) and
the micronutrients (sodium, manganese, iron, chlorine, boron, molyb-
denum, copper, zinc and nickel) are important elements to the plant
structure and its metabolism [138]. The absence or deficiency of these
nutrients may decrease the fitness and hinders the growth and develop-
ment. Micronutrients are required in just little amounts and their excess
amount in the soil (particularly Zn, Ni, and Cu) due to either natural
availability or due to industrial activities. The different minerals, for ex-
ample, chromium, cadmium, lead, mercury, antimony, silver, and arse-
nic, are dangerous to plants even at low concentrations [139–141].
The increase number of focuses for the toxicity of heavy metal im-
plies that the negative impacts have a tendency to be seen in those
cells that are exposed at first (cells in charge of the metal take-up)
[142]. Heavy metals interfere with ionic homeostasis and the activity
of enzymes, and these impacts are obvious in physiological procedures
including single organs, (for example, supplement take-up by the
roots) trailed by more broad procedures, for example, germination, de-
velopment, photosynthesis, plant water balance, essential digestion,
and multiplication. In reality, unmistakable side effects of heavy metal
harmfulness incorporate chlorosis, senescence, leaf rolling and putre-
faction, low biomass generation, shriveling and hindered development,
restricted quantities of seeds, and in the long run demise [143–145].
Heavy metal pollution in an agricultural soil is a serious environ-
mental problem due to the wide distribution of the heavy metals in
the environment and its effects (acute and chronic) on the growth of
the plant [24]. The higher concentration of Cu exposure in the plants
leads to produce the reactive oxygen species and oxidative stress
[146,147]. The growth of the plant and its metabolic activities and ac-
ceptance of oxidative harm in different species was observed due to
the phytotoxicity of Cd and Zn [148,149]. The higher concentration of
Pb in the soil instigate irregular morphology in many plant species
[150]. The higher concentration of Ni content in plant tissues demon-
strates disability of nutrient balance and results in scatters of cell mem-
brane capacities [151]. The exposure of excess Cr to the plants leads to
affect the photosynthesis process in respect to carbon dioxide fixation,
activities of enzymes, photophosphorylation and electron transport. In-
dications of As phytotoxicity incorporate leaf putrefaction and shrink-
ing, trailed by root staining and hindrance of shoot development
[152–156]. Many literature showed that the likelihood of As activity
through enlistment of flagging pathways, particularly those associated
 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197
with membrane harm, electrolyte spillage, and the production of reac-
tive oxygen species [157–159]. The physiological issues and the visible
damage were observed in the plants due to the high-level exposure of
Hg [160,161]. The toxicity of Mn in the few species begins with chlorosis
of the more seasoned leaves which moves to the more youthful leaves
with time [162]. The excess amount of Fe generates the free radicals
which irreversibly weaken the cell structure and harms the membrane,
proteins, and DNA.
1.3.2. Impact of heavy metals on human health
The heavy metals in a concentration higher than the critical values
can produce serious health issues. The toxicity due to heavy metals
may harm or decrease the mental and central nervous activities, dam-
age the lungs, liver, kidneys, blood compositions and other fundamental
organs. The long period of exposure of toxic heavy metals may cause
muscular dystrophy, Alzheimer's disease, different types of cancers
and multiple sclerosis. The exposure of heavy metals into human beings
mainly observed through the three noteworthy routes which include
the oral ingestion, inhalation and the dermal exposure [163,164]. The
essential route of heavy metals exposure to human being relies upon
the characteristics of heavy metals.
The oral ingestion is the essential pathway of copper enters into
human body because of its water solubility in nature. Likewise, inges-
tion is the essential pathway of mercury by means on the intake of ma-
rine living beings in which organic appearance of Hg (methyl mercury)
have bioaccumulated at high concentrations in the living tissues
[165–167]. The mercury intake into the human being is mainly due to
the consumption of dietary fish. A few variables influence the ingestion
of heavy metals by means of the gastrointestinal tract which includes
metal solubility, chemical structures and availability of different com-
pounds. The food intake is considered as one of the essential routes of
these heavy metal exposures while it was compared with inhalation
and dermal exposures. Inhalation is considered an essential route of oc-
cupational exposure. A few metals importantly affect its potential for in-
halation exposure and exist in nature as vapors. Mercury is one of these
classifications, which exists in the climate in vaporous state establishing
80% of total atmospheric mercury [168]. The skin is the successful bar-
rier against retention because of the structure of the external most
keratinized layer of epidermal cells [169,170]. Along these lines, the
heavy metals exposure through the skin path is just a worry for a few
metals. A few metals have the capability to penetrate into the human
skin when it was combined with other compounds. These days, heavy
metals have become most well-known contact sensitizers in people, es-
pecially nickel, increases the rate of nickel hypersensitivity in kids, par-
ticularly in developed countries [171,172]. One of the essential
wellsprings of contamination with heavy metals is road dust, which is
portrayed by fine particles with gigantic surface regions that are effec-
tively exchanged and stores the miniaturized scale contaminations
(heavy metals).
The food chain is perceived as one of the major pathways for human
exposure to soil pollution [173,174]. The generation of heavy metals
into the food chain is of unique worry because of the variously related
wellbeing dangers in humans and animals. Heavy metals are extremely
poisonous and can possibly cause serious harm, even at low concentra-
tions [175]. The different concentration of heavy metals has been
identified in different food items which include juices, beverages,
wines, etc. The exposure of heavy metals on human beings provide
the health impacts which include cancer, developmental retardation,
kidney damage, immunological impact, endocrine disruption and neu-
rological impacts [176–179]. The removal of toxic heavy metals from
water/wastewater is important in light of the fact that they provide se-
rious health dangers to people and in addition to other living creatures.
In perspective of this, it is important to develop treatment strategies to
remove harmful metal ions from various networks to decrease the pol-
lution load to nature.
5
1.4. Treatment methods
The heavy metals enter into human food chains through bioaccumu-
lation mechanism and provide toxicity to the biological systems due to
increased metal ion concentration over the time period. These heavy
metals can easily enter into the aquatic system due to industrial waste-
water, agricultural runoff, household, and commercial applications. The
different treatment methods available for removal of toxic heavy metals
from the water/wastewater includes chemical precipitation, chemical
coagulation and flocculation, electrochemical methods, membrane fil-
tration, ion exchange, bioremediation, and adsorption (shown in Fig. 1).
1.4.1. Chemical precipitation
Chemical precipitation is widely used in the removal of heavy metals
from the wastewater because it is inexpensive and it is relatively simple
to operate [180–182]. The pH of the wastewater will adjusted to the
basic conditions at the start, then the precipitating agent will be
added. It reacts with the heavy metal ions in the wastewater to form
the insoluble precipitates. The formed precipitates can be separated ei-
ther by sedimentation or filtration operations. The traditional chemical
precipitation processes includes sulfide precipitation and hydroxide
precipitation. The hydroxide precipitation process is the most widely
used chemical precipitation techniques in the treatment on the removal
of heavy metals from the industrial wastewater because of its low cost,
simplicity and easy to control the pH [183]. The solubility of the differ-
ent metal hydroxides is limited in the pH range of 8.0 - 11.0. The formed
metal hydroxides can be separated by flocculation followed by the sed-
imentation operations. The different types of hydroxides had been used
to precipitate the heavy metals from the wastewater based on the easy
to handle and low cost [184]. The lime was used as an important hy-
droxide precipitating agent in most of the industrial wastewater treat-
ment [185].
The heavy metals such as copper and chromium were removed from
the wastewater using hydroxide precipitating agents such as Ca(OH)2
and NaOH [186]. In hydroxide precipitation process, the addition of
chemical coagulants such as alum, salts of iron and organic polymers
can able to increase the removal of heavy metals from the water/waste-
water. Even though the hydroxide precipitation was widely used but
this has limitation in industrial application due production of large vol-
ume of the low-density sludges which creates the dewatering and dis-
posal issues [187]. Furthermore, few metal hydroxides are amphoteric,
and the mixed metals make an issue in utilizing the hydroxide precipi-
tation since the ideal pH for one metal may return another metal into
the solution. Also, while complexing agents are in the wastewater,
they will restrain the metal hydroxide precipitation.
The sulfide precipitation is likewise a successful procedure for the
treatment of harmful heavy metals [188]. One of the essential important
on utilizing the sulfides is the solubilities of the metal sulfide precipi-
tates are significantly lower than hydroxide precipitates and sulfide pre-
cipitates are not amphoteric. The sulfide precipitation process can
accomplish a high level of metal removal over a wide pH range com-
pared with the hydroxide precipitation methods [189]. Metal sulfide
sludges likewise display preferable thickening and dewatering qualities
over the metal hydroxide sludges. In any case, there are potential perils
in the utilization of the sulfide precipitation process [190]. Generally,
the heavy metal ions are regularly in acid conditions and sulfide precip-
itants in acidic conditions can result in the increase of dangerous hydro-
gen sulfide vapour. It is basic that this precipitation process is performed
in the neutral or basic conditions. Besides, metal sulfide precipitation
tends to frame colloidal precipitates that provides some separation is-
sues in either filtration or sedimentation processes. The chemical pre-
cipitation requires a lot of chemicals to decrease the metals to an
adequate level for release into the environment [191]. Other disadvan-
tages include a large amount of sludge generation, increasing sludge
disposal cost, slower metal precipitation, poor settling and the long
haul ecological effects of sludge disposal [192].
6 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197
Fig. 1. Treatment methods for the removal of heavy metals from wastewater
1.4.2. Chemical coagulation/flocculation
Coagulation/flocculation can be utilized to treat the heavy metal
contaminated wastewater [193–195]. Essentially, the coagulation treat-
ment destabilizes the colloidal particles by using a chemical coagulant
and results in sedimentation. Generally, the coagulation is followed by
flocculation of the unstable particles into massive floccules to increase
the size of the particle [196]. Finally, the massive floccules will be settled
in the sedimentation tank. Numerous coagulants broadly utilized in the
traditional wastewater treatment technologies includes alum, ferric
chloride, ferrous sulfate, etc for the removal of pollutants from the
wastewater [197]. Coagulation is a standout amongst the most vital
techniques for wastewater treatment, however, the principal objects
of coagulation treatment are for the suspended solids and hydrophobic
colloids. Flocculation is the activity of polymers to make the connection
between the flocs and tie the particles into huge agglomerates.
Suspended solids are flocculated into bigger particles and are easily re-
moved by sedimentation, filtration, and floatation or straining. The nu-
merous types of flocculants includes poly-aluminum chloride,
polyacrylamide, and polyferric sulfate are utilized in the wastewater
treatment but these flocculants cannot be directly utilized for the re-
moval of toxic metal ions from wastewater. Macromolecule flocculants
have been utilized as an effective flocculant for the removal of heavy
metals from the wastewater [198–201]. Generally, the heavy metals
cannot be completely removed by the coagulation/flocculation treat-
ment units alone, but it can be completely removed by considering
other treatment along with this treatment [202–206]. Though it has ad-
vantages, coagulation/flocculation has restrictions, for example, high
operational costs due to a large amount of chemical utilization.
1.4.3. Electrochemical methods
The electrochemical methods have been known as an extremely ef-
fective wastewater treatment methods particularly for the removal of
heavy metal ions from industrial wastewater. This method involves
the recovery of the heavy metals in the elemental metallic state by
using the anodic and cathodic reactions in the electrochemical cell.
This method required a large amount of capital investment and more
power supply which limits its wide industrial applications. Due to the
stringent environmental rules and regulations for the wastewater dis-
charge into the environment, the electrochemical methods have been
attracted many scientists and researchers to work in this research
field. Some of the electrochemical methods include electrocoagulation,
electrodeposition, and electroflotation techniques have been employed
in the removal of heavy metal ions from wastewater.
Electrocoagulation process comprises of electrodes which act as the
anode and cathode where the oxidation and reduction reactions taking
place, respectively [207]. Numerous physicochemical processes which
include oxidation, reduction, coagulation, and adsorption govern the
electrocoagulation process. Similar to other treatment methods,
electrocoagulation process for the removal of heavy metals provides
the easy handling and cost-effective methods on an industrial scale op-
eration. This process involves in the production of coagulants in situ by
dissolving electrically either iron or aluminium ions from iron or alu-
minium electrodes [208]. The anode produces the metal ion and the
cathode releases the hydrogen gas during the process. This produced
hydrogen gas used to float the flocculated particles from the water
[209,210]. This treatment method has already applied for the removal
of heavy metals, dyes, fluorides, nitrates, sulfates, pharmaceuticals and
phenolic compounds from wastewater [211–214]. Electrocoagulation
process is thought to be intended for any treatment capacity which
gives better removal efficiency for the toxic heavy metals. In
the electrocoagulation process, no need to add the chemicals because
the electron is the essential reagent. This method is indicated as an
eco-friendly technology when it was compared with the coagulation
process because the electrocoagulation process produces a lower
quantity of sludge, which is more stable. But few limitations in the
electrocoagulation process which include higher operating and capital
investment cost [215,216].
Electrodeposition method is widely used in the recovery of toxic
metal ions from the wastewater by using suitable electrode [217]. It is
a clean treatment method for the recovery of heavy metals from the
wastewater without the presence of permanent residues. The major ad-
vantages of this method include the recovery of metal in the purest
form, operating cost is low and no problem in the disposal of sludges
 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197
[218,219]. Electroflotation is also widely applied in the removal of heavy
metals from industrial wastewater [220–222]. It is a solid-liquid separa-
tion process which floats the toxic heavy metals to the water surface by
small bubbles of oxygen and hydrogen gases produced from the water
electrolysis [223]. Many heavy metals which include lead, copper,
zinc, nickel, iron and etc. have been successfully removed from the
wastewater by this treatment technique [224,225]. Electrochemical
methods are quick and well-controlled treatment methods for the re-
moval of heavy metals from industrial wastewater, which needs lesser
chemicals, generate less sludge and provide the maximum metal ions
removal. In any case, the electrochemical methods required higher ini-
tial capital speculation and the costly power supply, which confines its
improvement.
1.4.4. Membrane filtration
Membrane filtration treatment methods showed excellent results
for the removal of heavy metals from the wastewater [226]. Membranes
are in the form of complex structure which contains dynamic elements
on the nanometer scale. The membranes of the recent reverse osmosis
system are commonly a homogeneous polymer thin films bolstered by
a permeable support structure. The permeability of the water through
the membrane and the rejection of heavy metal ions in the membrane
mainly depend upon the chemical and physical properties of the mem-
brane [227,228]. The main advantage of this method is higher removal
efficiency, lesser space requirement and operation is easier. The differ-
ent types of membranes which include reverse osmosis, ultrafiltration,
nanofiltration, and electrodialysis have been successfully employed for
the removal of toxic metal ions from the wastewater.
The reverse osmosis consists of a semi-permeable membrane which
allows the water to pass through in it and rejects the toxic heavy metals
from the wastewater. This method is one of the finest treatment
methods for the removal of dissolved metals from the water/wastewa-
ter. The required membrane was used in reverse osmosis to remove the
different toxic metals from the wastewater [229–232]. The important
disadvantage of this method is handling of the rejection, membrane
fouling, and high power cost. Ultrafiltration method is operating at
low transmembrane pressures for the recovery of dissolved and colloi-
dal solids [233]. Generally, the dissolved solids are easy passes through
the ultrafiltration membrane due to the fact that the pore sizes of the ul-
trafiltration membrane were larger than the dissolved solids. The effec-
tive removal of heavy metal ions was achieved by the polymer
enhanced ultrafiltration and micellar enhanced ultrafiltration methods
[234–237].
Nanofiltration is the intermediate operation between reverse osmo-
sis and ultrafiltration. This treatment method is employed for the re-
moval of toxic heavy metals from the wastewater [238–241]. This
treatment method has advantages which include high efficiency, rela-
tively lower energy requirements, reliability and easy operation [242].
Electrodialysis is the type of membrane operation for the separation of
ions from one solution to another solution using charged ion exchange
membranes under an electric field. The anion-exchange and cation-
exchange membranes are the two types of ion exchange membranes
used in the applications. Generally, this treatment method was success-
fully employed for the treatment of industrial wastewater, generation of
drinking and process water from seawater, recovery of useful materials
from industrial effluents and manufacture of salts [243]. This treatment
method was also adopted for the removal of toxic heavy metals from
the industrial wastewater [244–247]. Membrane treatment methods
can able to successfully remove the toxic heavy metals from the waste-
water but these methods have an issue which includes complexity in
the process, higher cost, membrane fouling, and lower permeate flux.
1.4.5. Ion-exchange
Ion-exchange process has been extensively employed in the removal
of heavy metals from the wastewater due to its excellent removal rate,
higher treatment capacity and rapid kinetics [248–252]. In this process,
7
the ions (cations or anions) in the solution are replaced by the same
kind of ions (cations or anions) on the insoluble material (called as
ion-exchange resin). The heavy metal wastewater is entered into the
ion-exchange column at the one end and is travelled through the bed,
which actually removes the heavy metals in the wastewater. If the col-
umn is saturated with the heavy metals then the column is backwashed
to remove the deposited heavy metals and the column was regenerated
[253–256]. The ion-exchange resin may be of either natural or synthetic
resin, has the specific role to remove the heavy metals from the waste-
water. Among the different natural and synthetic resin materials used in
heavy metal removal from the wastewater, the synthetic resins are
mostly preferred because they are effective for the removal of heavy
metals from the wastewater [257]. The cation exchange resin is most
widely used to remove the heavy metals from the wastewater. The
most general cation exchangers are a strong acidic resin with sulfonic
acid groups and weak acidic resin with carboxylic acid groups. The pres-
ence of hydrogen ions in the acidic groups of the resins can act as an ex-
changeable ion with the cationic forms of metal ions from the
wastewater. Other than synthetic resins, natural zeolites and natural sil-
icate minerals have been widely applied to remove the heavy metals
from the wastewater due to their large availability in the environment
and its low cost [258–260]. Though the natural materials have applied
in the removal of heavy metals, its application is limited as compared
with the synthetic resins because it is employed in lab scale system
only but not in industrial scale level. Even though ion-exchange method
is widely used, the chemicals used to regenerate the ion-exchange
resins produce serious secondary pollutants. These secondary pollut-
ants must be handled properly. Ion-exchange process is expensive be-
cause it requires a large amount of resin to treat the large volume of
the wastewater which consists of lower metal ions concentration.
1.4.6. Bioremediation
Bioremediation process is a treatment method whereby the biologi-
cal systems, plants, and animals which includes the microorganisms to
remove the toxic pollutants from the aquatic environment [261–264].
Recently, microbe assisted bioremediation process has been widely
used in the removal of heavy metals from the wastewater. The tradi-
tional treatment methods for the removal of heavy metals are not finan-
cially effective and may create unfavourable effects on the aquatic
systems. The microbe assisted bioremediation and phytoremediation
methods for the removal of toxic heavy metals are financially effective
treatment methods [265–269]. Aquatic plants such as wetland ecosys-
tems have exceptional properties to remove the heavy metals from
the wastewater. Wetland ecosystems are much unrivaled in the exam-
ination with other traditional strategies due to the low cost, easy to han-
dle, regular microorganisms growth and low cost for maintenance
[270]. The rhizospheres in wetland ecosystems give an upgraded sup-
plements supply to the microbial environments of plants, which effec-
tively convert and remove the heavy metals in their biological
functions [271]. Constructed wetlands have been effectively utilized
for the treatment of toxic metals from rural overflow, municipal squan-
ders and mine seepage [272]. Numerous aquatic plants which include
Typha, Eichhornia, Phragmites, Azolla and Lemna have been utilized for
the removal of toxic metals from the wastewater ([273,275–281],562).
Phytoremediation is the low-cost method for the treatment of
wastewater, groundwater and polluted soil [561]. Plants are extremely
touchy to heavy metals however in phytoremediation wild and heredi-
tarily altered plants, including herbs, grasses, woody species, and forbs,
are for the most part utilized. The plants consume the metals through
the method of phytoextraction, phytostabilization, rhizoremediation
or phytofiltration [283–287]. Generally, the organic compounds are me-
tabolized but the heavy metals are not metabolized but instead, it is ac-
cumulated in the plant biomass [288]. The biomass produced by
phytoremediation stays exceptionally constrained in sum and holds
on, while all the biomass can be used as forage, manure, mulch or for
the generation of biogas [289,290]. Despite the fact that it is notable
8 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197
that metals are harmful to numerous plants, they have built up some in-
side components that permit the take-up, resistance, and collection of
high concentrations of metals that would be lethal to different living be-
ings. Being a low cost and easy process, phytoremediation can be exe-
cuted for their improvement to metal aggregations and translocations.
By and large, two systems of phytoextraction have been produced,
which are: (i) ordinary phytoremediation of heavy metals from aquatic
system through the plants in their whole development cycle and (ii)
chemically instigated phytoextraction systems to clean up polluted
water by utilizing metal-tolerant plants to evacuate the heavy metals
[291–296].
The effectiveness of phytoextraction can be expanded by utilizing
more biomass creating plant species and with the use of reasonable che-
lates. Hyperaccumulators or hyperaccumulating plants are equipped for
aggregating a lot of heavy metals which includes lead, cadmium, zinc,
nickel, and arsenic, in their over-the-ground tissues with no poisonous
side effects [297–300]. Metals take-up in connection to the outside con-
centration of the harmful heavy metals may contrast because of the di-
verse genotypes of plants. The plants in which have low take-up of
metals at very high metal concentrations are called excluders. These
plants have some sort of boundary to stay away from take-up of heavy
metals, in any case, when metal concentrations are at a high level this
obstruction misfortunes its capacity, presumably because of the lethal
activity of the metals. A few plants have certain detoxification system
inside their tissue, which enables the plant to the aggregate higher
quantity of metals [301–304]. In any case, phytoremediation on an in-
dustrial scale is constrained due to its low biomass generation,
constrained growth rate, and time utilization.
Algae, unicellular or multicellular organisms which are normally
available in terrestrial, fresh and marine environments. These algae
can also be available in the snow and the rocks in beneficial interaction
with fungus, for example, lichen. Some important applications of algae
such as vitality sources, fertilizers, pollution abatement, nourishment,
etc. The algae have been effectively utilized in the removal of organic
and inorganic pollutants from wastewater. Many research works have
been already reported on the removal of heavy metals from wastewater
using the different types of algae [305–316]. The algae cell wall consists
of different functional groups such as amino, hydroxyl, carboxyl, and
sulfate are act as the main binding sites for the removal of heavy metals
from wastewater [317]. The properties of the algae, characteristics of
the heavy metals and wastewater characteristics mainly affect the re-
moval of heavy metals by the algae. Some of the major types of algae
which includes green microalgae (in freshwater) and macroalgae (ma-
rine green, red and brown) have been effectively applied for the re-
moval of different kinds of heavy metals from wastewater. The heavy
metals generally enter into the cell wall of the algae (rapid process)
followed by entering into the inside of the cell (slow process). Few
green microalgae includes Chlorella Vulgaris, Chlorella miniata,
Chlamydomonas reinhardtii, Cladonia rangiformis, Fucus spiralis, Lami-
naria Hyperborea, Sargassum filipendula, Sargassum filipendula, Sargas-
sum wightii, Sphaeroplea, Turbinaria conoides, Spirulina platensis, etc.,
the green macroalgae (Caulerpa lentillifera, Cladophora fascicularis,
etc.), the marine red macroalgae (Galaxaura oblongata, Gelidium
sesquipedale, Corallina Mediterranea, Pterocladia capillacea, Jania rubens,
etc.) and the marine brown macroalgae (Laminaria japonica,
Ascophyllum nodosum, Pomacea canaliculata, etc.) have been successfully
adopted for the removal of toxic heavy metals from the wastewater
[318–322].
Bacteria (Escherichia coli, Bacillus cereus, Pseudomonas fluorescens,
Bacillus cereus, Bacillus firmus, Kocuria rhizophila, Bacillus
licheniformis, Micrococcus luteus, Cupriavidus metallidurans, Staphylo-
coccus xylosus, Bacillus megaterium, Enterobacter cloacae, Streptomy-
ces rimosus, Pantoea agglomerans, Salmonella typhi, Pseudomonas
aeruginosa, Ochrobactrum intermedium, Desulfovibrio desulfuricans
G20, Desulfovibrio vulgaris, Desulfovibrio desulfuricans, Desulfovibrio
sp., etc.) and Fungi (Aspergillus niger, Aspergillus sydoni, Ganoderma
lucidum, Cephalosporium aphidicola, Pleurotus sapidus, Tolypocladium
inflatum, Neurospora crassa, Trichoderma longibrachiatum, Saccharo-
myces cerevisiae, Mucar rouxii, Penicillium janthinellum, Rhizopus
arrhizus, Rhizopus oryzae, Saccharomyces cerevisiae, Lepiota hystrix,
Aspergillus brasiliensis, Aspergillus flavus, Penicillium cirtinum, Penicil-
lium oxalicum, Aspergillus terreus, Pleurotus platypus, Phanerochaete
chrysosporium, Penicillium citrinum, etc) species have also been effec-
tively utilized for the treatment of heavy metal contaminated wastewa-
ter [323–327]. Bacteria (prokaryotes) is a single cell organism. This
single cell organism may have a membrane-bounded nucleus or
maybe a membrane-bounded organelle similar to chloroplasts and mi-
tochondria. Fungi is a eukaryotic organism. Almost all the fungi species
develop as tubular fibers called as hyphae. The interlaced mass of hy-
phae is called as mycelium. The surface of the walls and envelopes of
these two organisms have the adequate functional groups to remove
the heavy metals from the wastewater [328–332]. Most of the bio-
masses have the capacity to remove the heavy metals from wastewater
but all of them cannot act as alternative materials in real industrial
wastewater treatment.
1.4.7. Adsorption
The adsorption process is currently perceived as most economic, ef-
ficient and selective treatment method for the removal of heavy metals
from wastewater [333–338]. This process provides flexibility in opera-
tion and design in the complete recovery of heavy metals from waste-
water. Adsorption is a solid-liquid mass transfer operation, where the
heavy metal (adsorbate) is migrated from the wastewater to the solid
surface (called adsorbent) and then bonded due to chemical or physical
adsorption over the adsorbent surface. Physical adsorption is due to the
weak Van der Waals forces' of attraction and the chemical adsorption is
due to the strong covalent bond between the adsorbent and adsorbate.
Sometimes, the heavy metal adsorption is a reversible process which
makes the adsorbent to be regenerated by using the proper desorption
methods. Activated carbon (AC) is a most widely used and popular ad-
sorbent for the removal of heavy metals from the wastewater due to its
higher surface area and its higher affinity towards the heavy metals
[339–343]. The different forms of the AC which include granular acti-
vated carbon (GAC), powdered activated carbon (PAC) and woven car-
bon (also called activated carbon cloth (ACC)) have been employed in
the water treatment [344,345]. AC is generally produced for the treat-
ment of organic pollutants but it can also be used for the removal of
heavy metals from wastewater. The commercially produced activated
carbons are divided into two types which include H and L type adsor-
bents [346,347]. If the carbon is activated at high temperature and
removes H+ ions then these type of material is called H type AC. The ex-
amples for the H type activated carbons are dust coal AC and coconut
shell based AC (Filtrasorb 200 and Filtrasorb 400) [348,349]. If the car-
bon is oxidized at low temperature and remove OH- ions then these
type of material is called L type AC (Ex: AC from wood-based materials).
GAC is mainly used in both batch and column mode of operation for the
removal of heavy metals from wastewater [350,351]. Sometimes, PAC is
applied but it is not possible to completely recover the adsorbent for its
regeneration [352]. The important surface properties of the AC such as
surface area, functional groups, surface charge, size and porosity (micro-
pore and mesopore) are the main reason for the removal of heavy
metals from wastewater. The application of AC is restricted due to its
high cost and limited regeneration behaviour. From the economic as-
pect, it is not feasible to utilize the AC for commercial or industrial
wastewater treatment. To overcome this issue, the waste materials
from agricultural operations that are available in large quantities can
act as an alternative material to the AC for the treatment of the heavy
metal contaminated wastewater. This treatment technique has
emerged as low cost and effective alternative materials for the removal
of heavy metals from wastewater. The advantageous of these materials
over the conventional materials such as low cost, higher efficiency,
higher adsorption capacity, easy operation, no sludge production, no
 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197
extra nutrients needed, the possibility of regeneration and recovery of
attached metals from the spent adsorbent.
2. Adsorbents
The heavy metals from the different industries include
electroplating, batteries, electrical, tanneries, pesticides, mining opera-
tion, fertilizers, ore refining, etc. were entered into the aquatic system
and pose serious environmental issues to the living organism even at
very low metal ions concentration. Even though, AC is widely employed
in the removal of these heavy metals from the wastewater its usage is
limited due to the high cost and limited regeneration ability of these
materials. Many researchers/scientists worked/working on the prepara-
tion of low cost and efficient adsorbent to replace the available commer-
cial AC for the removal of heavy metals from wastewater. Recently the
attention has been focussed towards the utilization of biomaterials
which are available in a huge amount such as the agricultural waste
products and the byproducts or the industrial wastes, for the treatment
of heavy metal contained wastewater. The natural resources in the en-
vironment are grown in a shorter period due to agricultural activities
and these natural resources are considered as the inexhaustible assets.
Furthermore, the greater part of the agricultural waste biomasses con-
tains chemical compounds that have high carbon constituents, which
make them reasonable antecedent for adsorbent preparation. Accessi-
bility of low-cost by-products from biomass generation and preparing
industry has ended up being a potential precursor for the preparation
of adsorbent. A few endeavours have been made to recognize financially
savvy strategies and antecedents to deliver adsorbents.
2.1. Adsorbents from industrial byproducts/wastes
The industrial byproducts/wastes are one of the low cost and effi-
cient adsorbents for the removal of heavy metals from wastewater.
These materials are produced either as byproducts or leftover materials
from the industrial operations. These industrial byproducts/wastes
often required less processing to improve its adsorption capacities. Be-
cause of the large availability, higher adsorption capacity, higher effi-
ciency, and low cost these materials can be utilized as an effective
alternative adsorbent as compared with the commercial adsorbents
for the removal of heavy metals from wastewater. Industrial
byproducts/wastes include lignin, fly ash, sludge, blast furnace slag,
and red mud have been applied for the removal of heavy metals from
water/wastewater.
2.1.1. Adsorbents from lignin
Lignin is a natural polymer, which is the second most plentiful natu-
ral polymer after the cellulose polymer. This lignin is essentially found
in the cell mass of woody tree species [353,354]. The fundamental well-
spring of lignin promptly accessible for use on a bigger scale originates
from spent pulping alcohols and chemical freedom of wood strands
from the paper and pulp enterprises. Lignin has not yet been changed
over into high-esteemed items on an expansive scale and today lignin
is fundamentally utilized for vitality recuperation at the pulp plants.
The conventional pulping methods include Kraft and sulphite cooking
processes. Kraft lignin is typically separated by the precipitation that re-
maining parts subsequent to cooking via acidification and protonation
of phenolic groups. Contingent upon the value of pH to which the
black liquor is acidified, a various composition and yield of the lignin
is acquired. A hydrosoluble type of lignin that contains an increase num-
ber of charged groups, the lignosulfonates, is readied from the
byproducts of the sulfite pulping process where the lignins are
sulfonated, debased and solubilized. The organosolv procedure is a
pulping procedure utilizing liquid organic solvents with the lignocellu-
losic biomass isolating the lignin piece by means of solubilization. The
homogeneity of the organosolv handled lignin is larger than that of lig-
nosulfonates and Kraft lignins. The extracted lignin from black liquor
9
has been applied for the removal of heavy metals from wastewater
[355–367]. The important functional groups are available in the lignin
materials to include hydroxyl, phenolic, methoxy, benzyl alcohol, alde-
hyde, carboxyl, and sulfonate groups but it varies with the pulping oper-
ations [368]. The mechanism on the removal of heavy metals by the
lignin was predicted many researchers and this may be due to the sur-
face adsorption, ion exchange, and complexation. But the detailed ad-
sorption mechanism for the specific removal of heavy metals from
wastewater by lignin must be reported. The adsorption influencing pa-
rameters like pH, temperature, contact time, initial metal ions concen-
tration and adsorbent dose have been experimented and many kinetic
and isotherm models have been analyzed by the various researchers.
2.1.2. Adsorbents from fly ash
The thermal plant is generally producing a large amount of fly ash
during the combustion of coal [369]. The fly ash provides the two im-
portant solutions for the environmental problems which include the re-
moval of pollutants from the wastewater and the solid waste
management. The fly ash mainly consists of silica, alumina, calcium
oxide, ferric oxide and carbon [370]. The composition of the fly ash is
varied with the operational behaviour and quality of the coal during
its combustion operation. The low adsorption capability of the fly ash
has been improved by the surface modification procedure which in-
cludes chemical or physical modification procedures [371]. The impor-
tance of the surface modification procedure was to improve the
surface properties of the adsorbent, particularly, surface area and sur-
face affinity towards the heavy metals removal from wastewater. Fly
ash is a strongly alkaline material and which provides the pH of 10-13
when it was added to the water. The surface of the fly ash was acquired
negatively charged at higher pH values. Generally, the removal of heavy
metal ions from wastewater by the fly ash was either may be due to the
electrostatic adsorption or precipitation. The fly ash is in raw or surface
modified form has been effectively utilized for the removal of different
heavy metals from wastewater [26,372–380].
2.1.3. Adsorbents from sludge and blast furnace slag
The sludge is generated from the wastewater treatment plants and
electroplating industries. The produced sludge is dried and becomes
the solid waste, which is being utilized as an effective adsorbent for
the removal of heavy metals from wastewater [365,381–385]. Blast fur-
nace slag is generally produced in large quantities from the steel pro-
cessing industries [386,387]. These wastes have attracted many
scientists/researchers to utilize these materials as an efficient adsorbent
for the treatment of heavy metal contained wastewater [388–392]. This
blast furnace slag has a higher adsorption capacity because this consists
of aluminium and iron oxides with them [393–395]. The different ad-
sorption affecting parameters such as pH, contact time, temperature,
adsorbent dosage, and initial metal ions concentration have been stud-
ied to observe the optimum conditions for the highest removal of heavy
metals from wastewater. The adsorption kinetics, equilibrium, and ther-
modynamic analysis have been experimented to predict the nature of
the adsorption process [390,396,397]. The column analysis on the re-
moval of heavy metals from the wastewater by these waste materials
has also been experimented by many researchers [398].
2.1.4. Adsorbents from red mud
Red mud is a solid waste generated from the bauxite ores during the
process of alumina extraction [399]. It has a corroded red tint emerges
from the presence of ferric oxide. Approximately, 120 million tons of
this dangerous material delivered far and wide annually [400,401].
Red mud is a standout amongst the most vital disposal issues in the
mining and metallurgical industries. The amount of generation varies
enormously relying upon the kind of bauxite and method utilized in
the refining procedure. The release of red mud is harming to the earth
as a result of its high alkalinity, various substantial metals and a little
measure of radioactive components [401,402]. In this manner, it is a
10 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197
gigantic task for the alumina ventures. The bauxite residue has limited
applications in paving, construction materials and land reclamation
[403]. Store and dumped adrift are the primary disposal strategies for
handling this waste. The huge tract of land utilized by red mud
stockpiling raises the financial expense as well as strengthens the dan-
ger of natural contamination, for example, surface/groundwater con-
tamination and fog, for neighbouring networks [404]. In this manner,
endeavours and government should give careful consideration to
reusing and dealing with the sharp increase and huge volume of this
strong waste. The advancements have been made in utilizing red mud
as low-cost adsorbents for fumes gas and wastewater treatment and
also it was utilized as catalysts for catalytic reactions [405,406]. The
red mud is effectively used as low cost material either is in raw form
or surface modified form for the removal of toxic heavy metals from
wastewater [407–414].
2.2. Adsorbents from agricultural byproducts/wastes
Agricultural byproducts/wastes, residues are generated from the ag-
ricultural and forestry activities. The primary kinds are agricultural and
forestry biomass which includes mainly straw, dross, grouts, husks, and
morsels. The enormous measure of agricultural waste has numerous
focal points in wastewater treatment which includes low cost, bounte-
ous source, short recovery cycle, chemical stability, inexhaustible
cycle, green energy and eco-friendly. In addition, these materials have
a high porosity and larger surface area, which makes these materials,
can act as efficient adsorbent to remove the toxic heavy metals from
the wastewater [80,415–422]. The straw is an agricultural byproduct,
generated from the agricultural harvest which includes sugar cane,
rice, beans, wheat, oil, cotton, and corn. The produced byproducts
have been effectively applied for the treatment of heavy metal
contained wastewater. In this manner, the use of agricultural waste as
an adsorbent to treat heavy metal contamination in water is a promising
technique. Specifically, this not just serves to completely use a large
amount of straw resources, yet in addition, gives a long haul improve-
ment course of green cutting edge and natural protection.
Agricultural waste generally consists of cellulose, lignin and hemi-
cellulose compounds in it [423,424]. The composition of the agricultural
wastes of these components is varied and which depends upon the
types of waste and its local environmental conditions. Generally, it is
the range of 35–50% of cellulose, 20–30% of lignin and 15–30% of hemi-
cellulose in the agricultural wastes [424,425]. Lignocellulose is largely
available in agricultural waste [563]. Cellulose is a linear syndiotactic
polymer of glucose and which is formed by β-(l→4)- glycosidic bonds
[415]. The primary objective of the cellulose extraction is to expel the
lignin and hemicellulose from the agricultural wastes [426]. Generally,
in the industry, the cellulose is collected from the chemical pulping
methods by using alkali and sulfite treatment procedures [427]. Lignin
is a crosslinked aromatic polymer which is comprised of coniferyl alco-
hol, p-coumaryl alcohol, and sinapyl alcohol. Hemicellulose is com-
prised of different uronic acid groups. It is a heteropolymer of D-
xylose, D-glucose, D-galactose, D-mannose, L-arabinose and D-
glucuronic acid. Agricultural by-products are mainly consists of lignin
and cellulose as major constituents. This may also consist of other
polar functional groups of lignin such as aldehydes, alcohols, ketones,
ether, phenolic and carboxylic groups. These functional groups are hav-
ing the ability to remove the heavy metals from the wastewater
[428,429]. Some of the agricultural byproducts/wastes being widely
employed in the removal of heavy metals from wastewater include
rice husk, waste peels, wheat wastes, and clay.
2.2.1. Adsorbents from rice husk
Rice has developed on each landmass aside from Antarctica and po-
sitions second just to wheat as far as overall region and generation
[430]. when rice or paddy is husked, the rice husk is produced as a
waste and for the most part, every 100 kg of paddy rice generates
20 kg of rice husk [431]. Obviously, the production of rice husk may fluc-
tuate with various rice species. Hence, in many rice generating nations,
the use of this large amounts of waste is of awesome importance. Rice
husk is considered as lignocellulosic materials of agricultural byproduct
which contains roughly lignin (21.44%), cellulose (32.24%), hemicellu-
loses (21.34%) and mineral slag (15.05%) [432]. The level of silica in its
mineral slag remains is around 96.34% [433]. This high level of silica
combined with most of the lignin content, an auxiliary polymer, is ex-
tremely strange in nature. It has made rice husk not just impervious to
water infiltration, contagious disintegration and it does not biodegrade
effortlessly. Compared to other cereal byproducts, the rice husk has the
most minimal level of total digestible supplements which is approxi-
mately less than 10%. It likewise contains low carbohydrates and protein
and also it contains a higher amount of unrefined fiber and ash
[432–434]. Rice husk is a solid waste generated from the rice
manufacturing process. From the waste utilization point of view, the
rice husk is an asset yet to be completely used and abused.
The researchers/scientists are interested in working to utilize the
rice husk completely. Endeavours have been made to use rice husk as
a building material [435,436]. Rice husk is utilized to protect dividers,
floors, and rooftop depressions on account of its magnificent properties,
for example, great warmth protection, does not radiate smell or gases,
and it isn't destructive [437–439]. Shockingly, the expense of building
materials made utilizing rice husk as the aggregate is not good as com-
pared with the other aggregates in the market. Hence, another intrigu-
ing probability for using this modest and promptly accessible resource
may be as an ease adsorbent in the removal of toxic metals from waste-
water [440]. The magnificent attributes of the rice husk which includes
good chemical stability, insolubility in water, high mechanical quality
and granular structure allow this probability to be higher [441]. Many
researchers have been worked on the utilization of rice husk in its native
or modified form for the treatment of toxic metals contained wastewa-
ter [442–446].
2.2.2. Adsorbents from waste peels
The waste peels from the agricultural activities mainly consist of a
lignocellulosic constituent in it. Generally, these waste peels are consid-
ered as an environmental burden to the community. The waste peels
which include vegetables and fruit peels comprise the most elevated
level of waste in most kitchens refuse containers. Besides, these wastes
are being generated in large quantity from the industries during its pro-
cessing particularly during the selection, sorting operation and boiling
operations [447,448]. The vegetables and fruits processing industries
generate the various types of solid peel wastes. A large number of the
vegetable and fruits peels are disposed of in the waste or nourished to
domesticated animals [5]. The vegetable wastes, fruits wastes, and
byproducts from the food processing industries produce serious issues
in the living environment. These wastes must be properly handled or
utilized. Since a decade ago, endeavours have been made to enhance
techniques and methods for reusing vegetables and fruits wastes. Gen-
erally, these wastes are frequently used as a feed or manure. They are
high esteem items and their recuperation will be financially appealing.
Recently, the useful products are produced from these wastes which
include edible oils, essential oils, pigments, food additives, dietary fibres,
bio-degradable plastic, polyphenolic compounds, enzymes, anti-
carcinogenic compounds, bio-ethanol and other miscellaneous items
[449–454]. The waste peels from agricultural activities are natural, envi-
ronmentally friendly, renewable resources and low-cost materials and
can be utilized as effective adsorbents either in native or surface modi-
fied form for the removal of heavy metals from water/wastewater.
Some of waste peels include citrus waste peels (lemon peels, citrus
peels, pomelo peels and grapefruit peels), cassava peels, banana peels,
pomegranate peels, jackfruit peels, garlic peels, yellow passion fruit
peels, potato peels, mandarin peels, ponkan peels, watermelon peels,
mango peels, lychee peels, Cucumis sativus peels and mangosteen
peels [419,448,455–464].
 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197 11

2.2.3. Adsorbents from wheat wastes
Wheat is a noteworthy nourishment harvest of the world, which
generates a lot of straw and bran during its agricultural activities as a
waste or byproducts [465]. Wheat straw has been utilized as feed and
in the paper industry to generate low-quality sheets or packing mate-
rials. In some places of the world, the stems are fired directly for the pur-
pose to produce the energy but a large number of air pollutants are
being generated into the environment. The wheat straw mainly consists
of 37-39% of cellulose, 30-35% of hemicellulose, approximately 14% of
lignin and little amount of sugar [466–469]. Wheat straw typically com-
prises different functional groups which include hydroxyl, carboxyl,
amide, sulfhydryl, and amine. The composition of the wheat straw
varies all over the world due to many factors but the components will
be remaining the same. The wheat straw and wheat bran have been
widely tested for the removal of different heavy metals from wastewa-
ter [470–473].
2.2.4. Adsorbents from clay materials
Clay materials are largely available in the environment and it is also
cheap material. It is mainly comprised of silica, alumina, weathered rock
and water [474,475]. Clay has a property to indicate plasticity through a
variable scope of water content, which can solidify when dried [476].
The clays have discovered applications in different industries, for exam-
ple, foundry sand, drilling liquid, characteristic fillers in papermaking,
separating and freshening up specialists in the oil refineries, decoloriz-
ing operators in the oil enterprises, extenders in fluid-based paints, ad-
sorbent, building material and catalyst [477]. The source of clays might
be from steady surface weathering and optional sedimentary operations
of an assortment of minerals, regularly silicate-alumina bearing rocks or
low-temperature aqueous adjustment over extended stretches of time
[478,479]. The properties of various clays such as swelling ability, elas-
ticity, plasticity, specific gravity, hardness, crystallinity, etc. fluctuate ex-
tensively, contingent upon the place of the source and local
environmental conditions [480]. The water is added to the clay material
and it becomes a mud. This mud can be mould into the desired shape
and size of the product after the material was dried at a proper temper-
ature. In view of this property, the ceramic and the pottery industries
used to deliver the products like children's toys, bowls, cups, pipes,
plates and so forth [481,482]. The different forms of clays and clay min-
erals have been utilized as an effective adsorbent for the removal of
toxic heavy metals from the wastewater [483,484].
The clay materials have important advantages as compared with
other conventional adsorbents which include higher adsorption capac-
ity, low cost, non-dangerous nature, high potential for ion exchange,
large availability and high specific area [422]. Clays likewise contain in-
terchangeable cations and anions held to the surface and therefore, the
consideration of researchers worldwide has been centered on utilizing
natural or surface modified clay materials as an adsorbent for the treat-
ment of heavy metals contained in wastewater [485]. The clay minerals
mostly consist of negatively charged on its surface and which is excep-
tionally powerful and widely used to remove the cations from the
wastewater because of its cation exchange behaviour, pore volume
and larger specific surface area [422,486]. The adsorption of heavy
metals by clay minerals includes a progression of complex adsorption
mechanisms, for example, ion exchange, coordinate holding between
metal cations and the negatively charged surface of the clay minerals,

Table 1
Langmuir monolayer adsorption capacity of the adsorbents for the removal of Cu(II) ions.

Adsorbents Langmuir monolayer adsorption capacity, qm pH Temperature Time References

(mg/g) (oC) (min)

Ultrasonic assisted Spirulina platensis 817.7 6.0 30 60 [551]

Sulphuric acid modified Spirulina platensis 431.4 6.0 30 60 [551]
Surface modified graphene oxide 357.14 6.0 25 60 [497]
Chemically modified orange peel 289 6.0 30 180 [498]
Graphene oxide 277.77 6.0 25 60 [497]
Ultrasonic assisted jujube seeds 259 5.0 30 30 [548]
Sulphuric acid modified Strychnos potatorum seeds 248 5.0 30 40 [543]
Chitosan coated magnetic nanoparticles 236.7 6.0 30 30 [547]
Nanoporous metal-organic framework 236.12 5.2 25 30 [69]
Crosslinked chitosan 200 5.0-6.0 35 60 [499]
Cellulose-graft polyacrylamide/ hydroxyapatite composite hydrogel 175 4.0 45 1440 [500]
Chitosan/polyvinyl alcohol magnetic composite 143 5.0 45 200 [501]
Graphene oxide-CdS composite 137.174 6.0 25 60 [502]
Fly ash/iron ore tailing geopolymer 113.41 6.0 40 90 [503]
Ca-DTCS/ALG beads 103.3 3.0 28 2160 [504]
DTPA-modified chitosan micro-gels (DTCS) 102.7 3.0 28 2160 [504]
Plain alginate (ALG) beads 102.0 3.0 28 2160 [504]
sulfuric acid-modified Eucalyptus seeds 76.94 5.0 30 10 [545]
Porphyra tenera-derived biochar 75.1 5.5 20 2880 [505]
Hydroxyapatite nanoparticles 70.92 6.0 30 90 [506]
Cellulose hydrogel 52.3 4.7 30 360 [75]
Nano-scale zero valent iron supported on rubber seed shell 48.18 6.0 30 30 [550]
Nano-scale zero-valent iron impregnated cashew nut shell 48.05 5.0 30 30 [549]
Biochars derived through farmyard manure (DBC-FYM) 44.50 2.0 25 1440 [55]
Grape bagasse activated carbon 43.47 5.0 45 180 [507]
Biochars derived through poultry manure (DBC-PM) 43.68 2.0 25 1440 [55]
Guazuma ulmifolia seeds activated carbon 36.496 6.0 30 60 [542]
Active coal pecan shell 31.70 4.8 30 1440 [348]
Untreated pomegranate peel 30.12 5.8 40 120 [508]
Raw Spirulina platensis 26.24 6.0 30 120 [551]
Sulphuric acid modified Caryota urens seeds 24.92 5.0 30 60 [546]
Granular activated carbon 20.833 5.0 30 30 [541]
Cashew nut shell 20.00 5.0 30 30 [540]
Luffa Actangula Carbon 12.47 6.0 30 120 [509]
Unmodified Strychnos potatorum seeds 8.649 5.0 30 60 [544]
Raw Caryota urens seeds 5.056 5.0 30 120 [546]
Activated alumnia 4.32 4.0 20 120 [57]
12 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197

Table 2
Langmuir monolayer adsorption capacity of the adsorbents for the removal of Cd(II) ions.

Adsorbents Langmuir monolayer adsorption capacity, qm (mg/g) pH Temperature (oC) Time (min) References

Milled eggshell 329 7.0 25 120 [510]

Mesoporous activated carbon from oil palm shell 227.27 6.0 30 180 [79]
ultrasonic-assisted Caryota urens seeds 183.4 5.0 30 60 [559]
Ultrasonic assisted jujube seeds 182.5 5.0 30 30 [548]
Ligand-based nano-composite material 148.32 5.5 25 15 [511]
Surfactant-modified chitosan 125 7.0 25 600 [82]
Lentil husk 107.31 5.0 30 60 [80]
Garbage ash 100.25 6.0 25 60 [512]
Hybrid hydrogel composite 78.13 6.0 25 60 [81]
Surface modified Eucalyptus seeds by sulphuric acid 71.15 5.0 30 10 [557]
Olive cake 65.40 6.0 28 1440 [513]
Surface modified Eucalyptus seeds by hydrochloric acid 64.16 5.0 30 14 [557]
Graft copolymerization of acrylamide (AAm) onto GL (GL–cl–PAAm) 54.95 6.0 25 60 [81]
Scolymus hispanicus 54.05 6.5 25 60 [514]
Grapefruit peel 42.09 5.0 30 150 [515]
Pen shells 37.63 4.0 25 60 [84]
Banana peel 35.52 8.0 30 30 [516]
Jatropha seed coat 22.83 6.0 30 180 [274]
Jatropha fruit coat 21.97 6.0 30 180 [274]
Sugarcane bagasse 14.80 6.0 30 60 [517]
Commercial activated carbon 32 6.0 30 60 [518]
Freshwater mussel shells (FMS) 26 6.0 30 60 [518]
Thermal activated serpentine 15.21 6.0 25 1440 [519]
Treated fly ash 14.33 5.0 30 30 [520]
Unmodified Strychnos potatorum seeds 7.023 5.0 30 90 [544]
Cork 6.0 5.0 30 4200 [521]
Peat 5.0 5.0 30 4200 [521]
Pine bark 4.0 5.0 30 4200 [521]
Chemically modified wheat straw 3.833 6.0 30 60 [522]
Eggshell 3.8 6.0 25 4200 [523]
Alhaji maurorum seed 3.748 6.5 30 45 [524]
Spruce wood 2.0 5.0 30 4200 [521]
Bael tree leaf powder 1.890 6.0 30 60 [553]
Bagasse fly ash 1.20 6.0 30 60 [525]

surface complexation and so forth. In numerous examinations, the sur-
face of the clay is modified to improve its adsorption capacity for the re-
moval of metals ions from the wastewater. This surface modification
methods were used to improves the surface area, pore volume and ac-
tive sites of the adsorbent [488]. Due to this surface modification
methods, the clay minerals become organophilic and hydrophobic for
the removal of non-ionic organic species. In this manner, use of muds
and its materials would take care of disposal issue, and furthermore ac-
cess to more affordable material in the wastewater treatment. Due to
the low cost for the generation of clays, there is no compelling reason
to recover them and also it gives more points of interest in utilizing
clays as an effective adsorbent for the removal of toxic heavy metals
from wastewater [264,422,489–491].
2.2.5. Adsorbents from other agricultural wastes
Many agricultural waste materials other than above have been
discussed for the removal of various heavy metals from the wastewater.
The different operating parameters have been studied and it is opti-
mized for the maximum removal of metal ions from wastewater. The
adsorption mechanism, kinetics, isotherms, thermodynamics on the re-
moval of heavy metals by these adsorbents have been analyzed and the
results are presented by the various researchers. Few researchers have

Table 3
Langmuir monolayer adsorption capacity of the adsorbents for the removal of Zn(II) ions.

Adsorbents Langmuir monolayer adsorption capacity, qm (mg/g) pH Temperature (oC) Time (min) References

Sulphuric acid treated cashew nut shell 455.7 5.0 30 30 [554]

Aspergillus flavus 287.8 5.0 30 360 [526]
modified eucalyptus bark 250.0 5.1 30 100 [527]
Amino-functionalized Fe3O4@SiO2 magnetic nano-adsorbent 169.5 5.0 25 120 [528]
Sulphurised activated carbon 147 6.5 30 300 [529]
Mesoporous geopolymeric powder 138.98 8.0 25 120 [111]
Mesoporous modified chitosan 107.21 6.0 40 180 [530]
surface modified Strychnos potatorum seeds 98.75 5.0 30 30 [555]
nano zero-valent iron impregnated cashew nut shell 94.46 6.0 30 30 [560]
Ultrasonic assisted Caryota urens seeds 80.91 5.0 30 60 [531]
Eucalyptus seeds activated carbon 80.37 5.0 30 16 [558]
Natural bentonite 68.4931 6.76 30 120 [532]
Rosa centifolia 73.8 5.0 30 1440 [533]
Activated carbon prepared from palm oil mill effluent 59.8802 5.5 30 360 [534]
Sodium dodecyl sulphate-coated Fe3O4 59.52 6.0 30 5 [535]
Fly ash coated by chitosan 55.52 6.0 20 180 [536]
Physic seed hull 12.79 6.0 24 240 [538]
Chitosan–PVA Blend 5.917 5.0 30 30 [556]
Cedar leaf ash 4.79 5.0 20 720 [539]
Bael tree leaf powder 2.083 5.0 25 60 [552]
 K.H. Vardhan et al. / Journal of Molecular Liquids 290 (2019) 111197
been reported the column analysis on the removal of different heavy
metals from the wastewater by the agricultural waste materials either
in its natural or surface modified form. Some of these agricultural
wastes include bagasse, white ash, neem bark, pine sawdust, plum ker-
nel, apricot shell, almond shell, coconut shells, cottonseed shell, gingelly
seed shell, olive stone, garden grass, hazelnut shell, lentil shell, wood-
derived biochar, walnut shell, cane pith, coir pith, pongam seed shell,
sunflower stalk, white rice husk ash, rice shell, cashew nut shell, soya
meal hull, groundnut shell etc. [420,492–496]. The studied materials
by the different researchers are not able to show the high adsorption ca-
pacity for the different heavy metals and also fail to show the regenera-
tion ability after few cycles of adsorption operations. Still, many
researchers/scientists are working in the process to select the suitable
adsorbent materials for the removal of heavy metals from the
wastewater.
3. Comparison of Langmuir adsorption capacities
The results of the isotherm studies done by various researchers were
compared for the removal of heavy metals from aqueous solution to
check the feasibility and adsorption efficiency of the adsorbents. The
comparison was made based on the important isotherm parameter
such as Langmuir monolayer adsorption capacity of the adsorbents.
The comparison was given in Tables 1–3. The results of the comparison
table give an input that the studied adsorbent has an excellent adsorp-
tion capacity. The maximum adsorption capacity of the adsorbent
leads to indicate the highest quality of the adsorbent.
4. Conclusion and scope for further research
The importance of low-cost adsorbents for the removal of toxic
metals from wastewater have been reported. The different adsorbents
which include industrial and agricultural wastes have been studied ex-
tensively for the removal of heavy metals from aquatic environment.
However, authors identified that many issues and shortcoming must
be addressed in resolving the removal of heavy metals from wastewater
by different treatment methods.
It is important that the surface modified agricultural waste has
started enthusiasm is apparent as substantial volume of published
paper in this research focus. In spite of the huge collection of literature,
more research will be expected to completely comprehend the physical
and chemical properties of the surface modified adsorbent. There are
challenges in the generation and refining of surface modified agricul-
tural waste, the antecedent of the adsorbent. The production of the ad-
sorbent through the surface modified procedure is as yet difficult and
not reasonable for substantial scale production. For instance, this tech-
nique requires a concentrated acid or base or heat treatment, which
may not be down to earth for large scale production of adsorbent and
its subordinates. In this manner, the production techniques reasonable
for substantial scale production should be produced. Also, since there
are distinctive methodologies in the production of surface modified ag-
ricultural waste, with every strategy influencing the attributes of the
prepared adsorbent, there is an important need to refine these
techniques.
It is an important research step to predict the structure of surface
modified adsorbent to upgrade its fantastic adsorption properties. The
considerable amounts of literature are already available on the surface
modification procedures of agricultural waste but more studies will be
expected to comprehend the mechanism of surface modification proce-
dures. More research will be required towards seeing how the available
functional groups impact the stability and the active sites of the surface
modified adsorbent. Regardless of the huge research exertion being
accounted for, the connection between the useful functional groups
and the adsorption capacity of the adsorbent is yet to be completely
comprehended. Additionally, the important active functions groups
present on the adsorbent surface should be clearly identified and its
13
removal mechanism for the removal of heavy metals must be explained
with proper technical inputs.
In this review, the studied adsorbents showed excellent adsorption
potential for the removal of metal ions from the aqueous solution. How-
ever, more toxic pollutants such as dyes, pharmaceuticals, phenolic
compounds, oil and grease, and other toxic pollutants must be
experimented with the same prepared adsorbent. The surface modified
adsorbent must also focus on the selectivity of the pollutants in the mul-
ticomponent system. The present review explained mostly on the re-
moval of single pollutant from the model wastewater using batch and
column adsorption techniques. Further research must be important to
validate the finding on the real industrial wastewaters for single and
multi-pollutants. The distinctive wellsprings of waste materials must
be considered to set up the powerful minimal effort adsorbent for the
removal of lethal poisons from the wastewater. The surface modifica-
tion techniques must be streamlined in the amalgamation of the practi-
cal adsorbent. It is essential to incorporate more active functional
groups on the adsorbent that can evacuate an extensive variety of con-
taminants, keep up great movement for quite a while, and meet the ne-
cessities for the down to earth treatment of wastewater. Some dynamic
substances with great proclivity have been utilized to alter the adsor-
bent surface and improve their toxin removal efficiencies toward an ex-
tensive variety of contaminants. The life cycle analysis of the adsorbent
must be carried out to ensure the effective reuse, reduce and disposal of
the adsorbents. It is also important to do much research works on the
selection and optimization of the regenerating agents for the better-
ment of the regeneration operation.
Acknowledgments
Authors would like to thank SSN College of Engineering, Chennai,
India for providing the research facilities to write this review paper
and also would like to thank the freepik website.
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