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Abstract

The water pollution problems are spreading thorough out the world. These world-wide
problems are increasing day by day. Among many contamination materials of wastewater, one
of them is heavy metals leach out through the wastewater by the industries like oil tanneries,
textile refineries, dyes, paper pulp industries, and petrochemical industries etc. The waste
industrial water contains by these industries is polluted due to leakage of synthetic organic
compounds, hydrocarbon salts, and heavy metals. To remove these pollutants conventional,
nano-based materials characterization, adsorbents, and Bismuth-based particles are being
practiced. The heavy metals lead to a very hazardous effect on the aquatic, human, agriculture
and wildlife. Because of toxic materials, the cause of health problems, the disorder of irrigation
to crops, the marine life in sea water is also destroying rapidly and the pollution is also
increasing up to 5% as per day. The use of Bismuth Vanadate, Bi-oxyhalide, and chalcogenide,
in the wastewater treatment is mostly used and as a result decrease of contamination at about
85% to purified water is reported in the literature.

Keywords: Nanoparticles; Heavy Metals; Pollution; Environment; Wastewater.

1. Introduction

Water is an essential part of our life on the earth and to sustain life every human being takes
several litters’ of water daily. All the aquatic life is dependent on water (Luo et al., 2014). With
increasing population day by day, the freshwater resources are decreasing quickly. Among
many reasons of decline in freshwater resources, polluting of water is one of them. Surface and
ground water are resources of fresh water and are vulnerable to contamination. There are
various ways to make toxic and impure water. One of them is wastewater flowing out through
industries. The industries like textile industries, ceramics industries, auto industries, leather
tanneries, oil refineries, paper industries, cosmetic industries are draining the wastewater in the
rivers, sea, canals that consist of many by-products and waste effluents (Deblonde, Cossu-
Leguille, & Hartemann, 2011). The industrial waste pollutants also accompanied by some
organic chemicals contain highly toxic organic byproducts, heavy metals, oils, and mineral
acids. This contaminated water which is polluted by toxic hydrocarbons compound, heavy
metals, toxic dyes, and metalloids is the main cause of polluting the surface as well as
groundwater. For removal of these toxic materials, different methods are adopted including
membrane filtration, electrodialysis, photocatalysis, adsorbent process, and nanomaterials
catalytic activities.
The contaminated water discharge through industries and factories are polluted and toxic to
our health as well as for agriculture and marine life. It is also the cause of irreversible
degradation of the atmosphere resulting in serious health problems (Deblonde et al., 2011). The
leather industries, fertilizers tanneries, oil refineries, textile, paper, rubber, and agrochemicals
etc. are producing wastewater that contains pollutants such as highly toxic synthetic organic
compound (O.C), oils, greases and mineral acids. These compounds are very dangerous and
injurious to all living organisms.

2. Heavy Metals and Their Toxicity


2.1 Heavy metals
Heavy metals have a density greater than water and are easily dissolved in water and produce
positive ions in the solution. Usually, the heavy metals have atomic number greater than 23
and density higher than 5 gm/cm3 (Deblonde et al., 2011). Heavy metals are Cadmium (Cd),
Arsenic (As), Mercury (Hg), Chromium (Cr), Lead (Pb), Nickel (Ni), Uranium (U), Aluminum
(Al), and Thorium (Th). Under the controlled condition, these are useful in chemical analysis.
The higher quantity than cellular metal accomplished value, these metal especially cadmium,
silver, and nickel cause the toxic effects on the environment (Sheoran & Sheoran, 2006). The
toxicities of three heavy metals named cadmium, mercury, and lead are very high even though
their presence of 0.05 mgm-3 can become serious problems such as Pulmonary Edema,
vomiting, nausea and affects directly to the gastric system of the humans. The specific limits
of heavy metals are in different quantities.
2.2 Sources of heavy metals
There are two types of sources of heavy metals like primary and secondary. In nature, these
heavy metals are found in the earth crust. The secondary sources of heavy metals are industry,
medical and domestic wastage of water. Heavy metals primary sources summary is shown
below in Table 1.

Table-1: Primary Sources of Heavy Metals (Pb, Ar, Cd, Hg)

Heavy metals Primary and secondary sources

Fuel combustion, oil refinery, petroleum and gasoline, auto-exhaust,


Lead
lead solder food can lead plumbing pipes, lead storage paints, lead
storage batteries, electrical equipment.
Antiseptic, refinery system, scientific devices, glowing light, plastic
Mercury
and as paints.

Scrubber, battery, tannery system, mining equipment, electroplating


Cadmium
machines, dyes

Insecticide and pesticide, wood preservative, combustion fuel, copper


Arsenic
smelter

2.3 Toxicity of heavy metals


Out of 80 metal elements throughout the 118 recognized elements, the more toxic elements are
heavy metals. These metals are soluble in the water and in food nutrients. When industrial
waste water leaches into the soil and flows out through rivers and sea, it turns the fresh water
into polluted water. The annual casting amount of lead is 3 million tons. A controlled amount
of lead is used in lead storage batteries, gasoline refineries, sanitary system and cable coatings.
Cadmium is used in the electroplating system, dyes and pigments, transport objects, television
equipment, a nickel-cadmium battery and solar systems (Naja & Volesky, 2009). Chromium
salts and chromium-VI are very serious and injurious elements for plants and water living
things. The mg/L values of toxicity for heavy metals are given in Table 2.
Table-2: Representation of Toxicities of Heavy Metals in Mg/L (Naja & Volesky, 2009).

Heavy Metal Mg/L Toxicities

Arsenic (Ar) 0.05 Skin infection, cancer, vascular diseases

Cadmium (Cd) 0.01 Headache, renal and cortex problems

Chromium (Cr) 0.05 Headache, diarrhea, dermatitis

Copper (Cu) 0.25 Liver diseases, insomnia

Nickel (Ni) 0.20 Asthma, coughing, carcinogen, nausea

Zinc (Zn) 0.80 Thirst increasing, neurological disease, headache and


anxiety

Lead (Pb) 0.06 Destruction of brain nerve, kidney, and nerve related
diseases
Mercury (Hg) 0.0003 A cause for kidney, circulatory, nervous problems

2.4 Heavy metals and their impact on the environment


The water extracted from industry contains polluted contamination including the heavy metals
and other toxic synthetic organic compounds (Gadd & Griffiths, 1977). The origin of heavy
metals is ores like iron sulfide, arsenic sulfide, lead sulfide, aluminum sulfide, selenium sulfide
and gold sulfide. This metal contamination is becoming very serious now-a-days in every
country especially in Asian countries like Pakistan. These heavy metals consist of cadmium
(Cd), copper (Cu), lead (Pb), chromium (Cr) and their oxides. The mercury from industry reacts
with dyes and chemical and converts into methyl and dimethyl mercury resulting in the cause
of the toxic component. These transition rare metals exhibit biotic, aquatic, agricultural toxic
and hazardous effect on human beings. The resulting symptoms cause many diseases in living
organisms because of wastewater polluted water usage air spoliation, and land waste materials
leaching (Barakat, 2011). The numbers of patients had been increasing in hospitals during the
last 5 years. Sudden death has now become common.

2.5 Effect of heavy metals on aquatic life


Marine and other living organisms in the ocean and rivers are dependent on the water. Without
water, their lives would be impossible. The wastewater including dangerous toxic metals,
extracted from hospitals, industry and chemical laboratories flow through rivers, canals, oceans
and as a result in sea leach out. This water in oil spillage converts definite dyes into acids. The
heavy metals also present in this wastewater are soluble in water, resulting in an acidic solution.
The solubility of mercury is due to its compound formation (Tyagi, Gupta, Sadegh,
Ghoshekandi, & Makhlouf, 2017).
The mercury elements leach out from industry waste effluents are deposited in rivers reacted
directly to microorganism anaerobic reparations of marine. Consequently, the dimethyl
mercury and methyl mercury result in marine life to toxic food web and affects the ocean life.
Likewise, mercury the other heavy metals are soluble in water and becomes the sources of
acidic salt solution in water and when this water is used by the fishes, amphibians, brush, and
plants even for man chores is also dangerous to their health. Thus, the food chain of marine life
is also poisoned and toxic (Wang et al., 2008).

2.6 Effects of heavy metals on human beings and agriculture

Overdose of heavy metals leads to hazardous and poisoned impacts on human beings. Within
limit these metals are suitable for human, the excessive and recess amount can also become the
cause of even the death of human (Jeong, Jeon, Jang, Choi, & Park, 2013). The symptoms to
the food web of man are peptide disarrangement, diarrhea, tremor, hemoglobinuria and many
other serious diseases as discussed below:
The agricultural uses of this wastewater that flow out through the rivers and canals toxins the
fertility of soil which leads the fresh water into an acidic solution that is to irrigate the fields
by the peasants. The highly poisoned metals are absorbed in soil and water and ultimately
injected into the grains during their development (Khulbe & Matsuura, 2018). As a result, when
the water is planted to crops most of the plants are dead and some of them go through the
growth process. These are deadly harmful to health and to pollute the environment. High blood
pressure, Anemia, Vomiting, Irritation, Gastric system, Immune system disorders, Blindness,
Headache. Nausea, Asthma like diseases are increasing day by day due to drinking the
wastewater and by taking the poison food.

3. Conventional Process for Removal of Heavy Metals


The adsorption process, chemical decomposition, ion exchange, electroplating, floatation is the
conventional process to remove the heavy metals effluents. The chemical precipitation process,
as described in equation 3.1, is a process using at a large commercial scale.
𝑀2+ + 2(𝑂𝐻 − ) → 𝑀(𝑂𝐻)2 (3.1)
where the ions M2+ and (OH-) are dissolved in the solution to form the impure M(OH) 2 that are
insoluble in water. This reaction is strongly dependent on the pH level of the solution. Lime
water consists of calcium hydroxide, due to low cost and high facilitated it is used frequently.
It is used in excessive amounts as in 1000mg/L. but, it requires the high availability of metal.
The low amount cannot perform the mechanism. Another method like electroplating is used to
pass the current to flow through the hydrous solution. The resulting ions move towards their
respective electrodes like cathode and anode. Consequently, the resulting products in the form
of metals crystal formed. But, it is a corrosive method. Ion exchange is a process to exchange
the cations and the anions in the atmosphere. The ions, that are transferred to air is in the form
of hydrocarbons.

3.1 Filtration process


Membrane filtration, based on the ultra-filtration, nano-filtration and reverse process of
osmoregulation, are the processes to remove the heavy metals effluents from the contaminated
wastewater. The ultra-filtration uses the semi-permeable membrane to separate all pollutants
having size up to 5-20nm. In literature measured values of free-pollutants by this process is up
to 95% especially for Cu and Zn. The filtration process is repeated to 5-6 times. It is done by
the amino group that is present in the resulting suspension. The amino group action is presented
in equation 3.2.
𝑅𝑁𝐻 2 + 𝐻 + → 𝑅𝑁𝐻3+ (3.2)
The functional group with donor atom is attracted towards the metals. By reacting with metals,
the product is the formation of a complex structure which is strongly dependent on pH as shown
in equation 3.3
𝑀2+ + 𝑛𝑅𝑁𝐻3+ → 𝑛𝐻 + + (𝑀 − 𝑅𝑁𝐻2 )+2
𝑛 (3.3)
To remove the cadmium and chromium metals, the ZnAl2O3-TiO2 is being used widely and
attained the precipitation of 93% of Cd and 86% of Cr. This can filter by the ultra-filtration
membrane. The membrane filtration can pull the metals up to 80-90% removal from
wastewater at a concentration rate of 10-12mg/L with pH value level of 5-9.5. Due to fouling
it has a hazardous effect on the membrane caused by the turgor pressure, and flux low rate. The
process is also performed for reverse osmosis and nano-filtration for copper and cadmium. The
osmosis process is suitable to achieve 98-99% concentration of free metals (Sivakumar, Suresh,
Giribabu, & Narayanan, 2015).

3.2 Electrodialysis
Electrodialysis is another process in which current is passed through the solution to separate
the ion from the membrane. Membranes are the ionic solution comprising of the ion species.
When the current passes through the solution, the ions move to their irrespective electrodes.
Polyvinylflouride-membrane and perflourosulphonic-Nafon-117 membranes are used as
cations. When flow rate is increased, the separation rate decreased. At more than 500 ppm
concentration, separation is ceased. The Electrodialysis (ED) process was established in
chemistry to remove the toxic metals from solution. This process requires the precautionary
measurements like contaminated air avoidance, specific temperature, voltage and pressure
control.

3.3 Photocatalysis
In photocatalysis, the sunlight falls on the aqueous solution of the semiconductor. This light
energy is converted into the charged particle if the band-gap is less than the light energy. These
charges are removed by the semiconductor wafers like TiO2, ZnO, CdO, etc., responsible for
oxidation and reduction as shown in equation 3.4-3.6 as an example.
TiO2 + hv → iO2 + e-CB + h+VB (3.4)
TiO2 + OH- + h+ → TiO2 – OH· (3.5)
O2 + e-→ O2 (3.6)
The UV-light has to irradiate on the prepared solution to transform it into ionic solution and
then the redox reaction started (Hashmi et al., 2013).
The chromium reduction is possible by using the UV-radiation on titanium dioxide catalyst in
combination with Neodymium catalyst. The Nd ions that make a layer on the TiO2 surfaces act
like a layer deposited on the electrons. The separation of positive and negative charges
increases the oxidation-reduction reaction and the recombination reaction does not take place.
The electron acts like donor and chromium as an acceptor to the TiO2. Powder TiO2 limitation
is improved by the process of immobilization. The immobile process converts the toxic
chromium Cr(VI) to non-toxic chromium (III) under UV-characterization.

3.4 Adsorption Process


The adsorption process is a mass exchange mechanism between solution (water) and
soil/surface. Different agricultural waste adsorbents, industrial by-product adsorbents, natural
material, synthesized biopolymers, and less-cost adsorbents are used to remove the heavy
metals from wastewater. The sorption method consists of three basic processes: 1) transfer of
pollutant on the adsorbent substrate/surface, 2) adsorption on the surface and 3) transport
within the adsorbent molecule (Tchounwou, Yedjou, Patlolla, & Sutton, 2012).
The zeolite material is a natural ion-exchange particle. Among the zeolites, the clinoptilolite is
used for selection of Pb, Cd, Zn, and Cu. Cation ability for this zeolite is dependent on the pre-
treating conditions. The pH factor is very important in the selection of adsorption of the heavy
metals. For removal of Cr, NaA zeolite is used at pH 7. The copper and zinc are absorbed by
the 4A-zeolite at neutral and basic pH values. Manganese is adsorbed at the alkaline pH.
Magnetically modified zeolite (MMZ) adsorbs the Pb(II) and Zn(II) at pH 5-10.
Research revealed that rice husk, pecan shells, jackfruit, maize cob, and hazelnut cover have
properties of the removal of heavy metals. The process to remove heavy metal using
agricultural products is called bio-sorption. Rice shells are used to extract the heavy metal
Cr(VI) at pH 2, Potato peel charcoal adsorbed the Cu(II) and Zn(II), and coconut shell charcoal
is used to remove the Cr(VI-) (Bourke, Carty, Crowe, & Lambert, 1995).

4 Remedies of Heavy Metals Using Nano-Particles

Carbon and oxide-based nano-particles have the capability to adsorb the heavy metals from the
aqueous solution. The carbon nanotubes (CNT’s) are the nano-range materials that are widely
used in different fields of life. To remove pollutants from the wastewater, the nanotechnology
is playing a vital role. The adsorption, redox, photo-catalyzation, and size exclusion process
are the widely used processes to remove the heavy metals ions from the solution. Size exclusion
is one of the processes used to remove the impurities in the form of filtration as discussed
before. The adsorption processes the nano-particles such as CNT’s, FeO3, charcoal, graphene,
MnO2, TiO2, ZnO2 are being used to remove the heavy metals. These particles are present in
the form of particles, tubes, powder etc. These nanomaterials are low cost and reliable particles
to eradicate the heavy metals (Borchers, Gray, & Thompson, 2013). Recent research has shown
that the nanomaterials as adsorbents are used in the purification of water. The polluted particles
that are characterized are Ni2+, Cr3+, Cr6+ Cu2+, Cd2+, Co2+, Hg2+, Pb2+, As3+, As2+, Th2+, Eu3+,
Sr2+, Zn2+ and U6+.

4.1 Bismuth Nano-Particles


The bismuth nanoparticles show the electrical, optical and non-resistive properties (Soltani &
Entezari, 2013). These are Bismuth vanadate, Bismuth oxyhalides, and Bismuth chalcogenides.
Bismuth Chalcogenide is photoelectric compound with 6th group elements. These are
represented as Bi2E3 (O, S, Se, Te) and consist of bismuth oxide (Bi2O3), bismuth sulfide
(Bi2S3), bismuth selenide (Bi2Se3) and bismuth telluride (Bi2T3). These materials are
semiconductor materials with specific bandgap. When the sunlight or the electrical light source
falls on the polluted water, these are converted into ions to extract heavy metals from aqueous
solution.
BiVO4, exists in three stages namely; monoclinic scheelite, tetragonal scheelite, and the
tetragonal zircon. Through the photocatalytic process, the harmful products are removed.
Photodegradation of hydrocarbons occurs when a photocatalyst absorbs the light of suitable
wavelength and converts the substrate into the cation and anions. Hydroxyl ion in water then
reacts to remove the pollutants.

4.2 Strategies to increase the photo catalytic Properties of BiVO4


To improve the efficiency of BiVO4 nanoparticles, there are three methods. These are 1)
doping, 2) heterojunction and 3) catalyst deposition. These methods are performed by the earth-
crust elements that are in abundance (Niu, Fernández-Sánchez, Gich, Ayora, & Roig, 2015).
When these three processes are performed for hexavalent heavy metals ion like Mo6+, Cr6+,
W6+, then the doping of Mo6+ is found to be more significant at photo-current generation and
2-times higher than electrode potential. Further, the resistance is decreased and an increase in
efficiency is observed to be about 25%. To increase the efficiency of Mo6+-BiVO4, the WO3
was deposited on the layer of BiVO4. This has to increases the photocurrent about 50% with 3
times higher generation of photocurrent. The observed photocurrent for this heterojunction was
2.4 mA/cm2 with weight 60-90% (Asghar, Hussain, Roberts, Campen, & Brown, 2013).

5. Conclusion

Herein, numerous sources of wastewater including industries, factories, mining and tanneries
in the form of organic compounds, heavy metals, dyes, and chemical textures have been
reviewed and discussed. The heavy metals like Pb, Zn, Cr, Hg etc. were found to be more
hazardous for human livings, aquatic system, wild animals, plants and crops. With the passage
of time, numerous techniques like filtration, electrolysis, electrodialysis were used to treat the
hazardous wastewater that contain heavy metals. However, high cost and low efficiency limited
their wide use. The photocatalysis, being a green approach, was observed to be the most
efficient and stable technique to completely degrade the heavy metals present in wastewater.
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