BTech:

Chlorine:

The main chloride sources in water are industrial effluents, which usually contain high chloride
concentration and are discharged from metal smelting, flue gas desulfurization and inland seawater
desalination.

For chlorine:

Colorimetric Methods:

Principle: Reaction of chloride ions with specific reagents produces a color change.

Procedure: Various colorimetric reagents, such as ferric thiocyanate or o-toluidine, are added to the
water sample. The resulting color is then measured using a spectrophotometer.

Spectrophotometry is a procedure for determining how much light is reflected by a chemical material
by measuring the strength of light as a light beam travels through the sample solution. The
fundamental theory is that light is absorbed or emitted over a certain wavelength spectrum by each
compound.

Calculation: The intensity of the color is proportional to the chloride concentration.

For arsenic: 1. Principle:

AAS operates on the principle of atomic absorption, specifically measuring the absorption of light by
arsenic atoms in a sample.

When a ground-state atom absorbs light of a specific wavelength, it undergoes a transition to an

excited state. The absorption of light is directly proportional to the concentration of the absorbing
species.

2. Procedure:

Sample Preparation:

The water sample is typically subjected to sample preparation steps to extract or separate arsenic
from the matrix. This may involve techniques like digestion or extraction.

The resulting solution is then introduced into the AAS instrument.

Atomization:

In AAS, atomization is a crucial step. The sample is introduced into a flame (commonly an acetylene-
air flame) or other atomization source.

The heat of the flame causes the sample to vaporize, and the atoms of arsenic are formed in the
ground state.

Absorption Measurement:

A beam of light from a hollow cathode lamp (emitting light at the absorption wavelength of arsenic)
passes through the flame containing the atomized sample.
The atoms in the flame absorb light at the characteristic wavelength of arsenic.

Detection:

The intensity of the transmitted light beam is measured by a detector.

The instrument records the reduction in intensity caused by the absorption of light by the arsenic
atoms in the sample.

3. Calibration:

A calibration curve is constructed by measuring the absorbance at the characteristic wavelength for
known concentrations of standard arsenic solutions.

The relationship between absorbance and concentration is typically linear, allowing for the
quantification of unknown sample concentrations based on their absorbance values.

4. Calculation:

The absorbance (A) is related to the concentration (C) of arsenic in the sample by Beer's Law, which
states that absorbance is directly proportional to concentration.

The relationship is given by the equation:

A=ε⋅l⋅C, where

A is absorbance, ε is the molar absorptivity, l is the path length of the sample, and C is the
concentration.

For iron: AAS, SPECTROPHOTOMETRY(CALAORIMETRIC METHODS)

1. Removal of Chloride from Water and Wastewater through Chemical Precipitation
Chemical precipitation, formation of a separable solid substance from a solution, either by
converting the substance into an insoluble form or by changing the composition of the
solvent to diminish the solubility of the substance in it. The distinction between precipitation
and crystallization lies largely in whether emphasis is placed on the process by which the
 solubility is reduced or on that by which the structure of the solid substance becomes
organized.

1.1 Forming Metal Chloride Precipitates - 1.1.1 CuCl - 1.1.2 AgCl

1.2 Forming Metal Oxychloride Precipitates

1.3 Forming Friedel's Salt Precipitates

In water and wastewater, chloride can be converted to metal chloride, metal oxychloride and
Friedel's salt precipitates by adding metal-based precipitants. Chloride can also be
electrochemically precipitated by different electrodes such as Cu, Ag and Bi. Similar to
copper electrodes, silver electrodes can also be used for electrochemical precipitation of
Cl−.The removal efficiency depends on reaction temperature and Cu(II) concentration. High
reaction temperature and high Cu(II) concentration contribute to efficient Cl− removal.
Compared with the previous three chemical precipitation methods, Friedel's salt method is a
common chloride removal method in practical applications due to its low cost and relatively
mild reaction conditions. In Friedel's salt method, the precipitants Ca(OH)2 and NaAlO2 can
react with Cl− and H2O to form Friedel's salt precipitates (Ca2Al(OH)6Cl·2H2O or
Ca4Al2Cl2(OH)12).

2. Removal of Chloride from Water and Wastewater through Adsorption

2.1 Ion Exchangers

What Exactly Is Ion Exchange?

Ion exchange describes a specific chemical process in which unwanted dissolved ions in
water and wastewater — like nitrate, fluoride, sulfate, and arsenic — are exchanged for
other ions with a similar charge. Ions are atoms or molecules containing a total number of
electrons that are not equal to the total number of protons.

There are two different groups of ions:

Positively charged cations

Negatively charged anions

 We have Michael Faraday to thank for these names, which he devised based on cations’
attraction to cathodes and anions’ attraction to anodes in a galvanic device.

Removing Ionic Contaminants

This attraction is used to remove dissolved ionic contaminants from water. The exchange
process occurs between a solid (resin or a zeolite) and a liquid (water). In the process, the
less desired compounds are swapped for those that are considered more desirable. These
desirable ions are loaded onto the resin material. These resins can be used alone or in
concert to remove ionic contaminants from water.

In the exchange of cations during water treatment, positively charged ions that come into
contact with the ion exchange resin are exchanged with positively charged ions available on
the resin surface, usually sodium.

In the anion exchange process, negatively charged ions are exchanged with negatively
charged ions on the resin surface, usually chloride. Various contaminants — including
nitrate, fluoride, sulfate, and arsenic — can all be removed by anion exchange.

Compared to other technologies, including continuous electrodeionization (CEDI),

chromatography, ultrafiltration, and biological treatments, ion exchange is particularly
suitable when trying to remove a specific low concentration pollutant, for example,
removing boron from well water.

Recharging Resins

Resin materials have a finite exchange capacity. Each of the individual exchange sites will
become full with prolonged use. When unable to exchange ions any longer, the resin must
be recharged or regenerated to restore it to its initial condition. The substances used for this
can include sodium chloride, as well as hydrochloric acid, sulfuric acid, or sodium hydroxide.

2.2 Bimetal Oxides

Bimetal oxides used in chloride removal include Ca-Al oxide and Mg-Al oxide. The Ca-Al oxide
adsorbent was prepared by solid-state heating of CaO and Al2O3 (Paul and Chang, 2020).
The adsorbent is rich in mayenite and can remove chloride from saline groundwater by the
mayenite-tohydrocalumite transformation

2.3 Carbon-based Electrodes

Electrosorption is a technology to remove ions from water by applying an electrical voltage

difference between two porous carbon electrodes, in which ions will be temporarily stored.
Graphite is used here.

3.Removal of Chloride from Water and Wastewater through Oxidation

 Advanced oxidation processes (AOPs), in a broad sense, are a set of chemical treatment
procedures designed to remove organic (and sometimes inorganic) materials in water and
wastewater by oxidation through reactions with hydroxyl radicals (·OH).[1] In real-world
applications of wastewater treatment, however, this term usually refers more specifically to
a subset of such chemical processes that employ ozone (O3), hydrogen peroxide (H2O2)
and/or UV light.

3.1 Ozone-based AOPs

The reaction of chloride with ozone in aqueous solutions has been extensively studied
(Hoigné et al., 1985; Haag and Hoigné, 1983; Razumovskii et al., 2010). In acidic conditions,
chlorine gas is the dominant product (Levanov et al., 2019). The reaction is formulated as:

This reaction can be accelerated by H+ (Levanov et al., 2003). Transitional metal ions can also
promote the reaction through coordination and charge-transfer catalysis (Levanov et al.,
2005). In neutral and alkaline conditions, chlorate ClO3 − is the main product and perchlorate
ClO4 − is the byproduct (Levanov et al., 2019; Levanov and Isaikina, 2020).

4. Removal of Chloride from Water and Wastewater through Membrane Separation

4.1 Diffusion Dialysis

4.2 Nanofiltration

4.3 Reverse Osmosis

4.4 Electrodialysis

5. Conclusion and Outlook

Chloride removal is usually based on a single removal mechanism (e.g., chemical precipitation or
oxidation alone). A simultaneous chemical precipitation and oxidation process is a new strategy to
remove chloride. There are two approaches to achieve the combination of chemical precipitation
and oxidation. One approach is designing a chemical precipitation system that can oxidize Cl− to Cl·.
 Iron:

Iron is one of the most abundant elements in the Earth’s crust. It is an important part of different
enzymes and plays many roles in the proper functioning of human body. The metal is found in large
quantities in rocks and soil systems around the world. It reaches the water bodies through geogenic
sources as well as dumping of industrial effluents and domestic wastes into the water bodies. The
surface water receives iron via effluents from iron and steel industries, mining as well as metal
corrosion. The groundwater also receives iron through iron bearing rocks and minerals. According to
WHO standards, iron content in drinking water is permitted only up to the concentration of 0.3 mg/L.
However, the elevated levels of iron in water have been reported in different areas around the world
due to increasing water pollution. High iron content in water is associated with various aesthetic
concerns such as metallic taste, odor, discoloration, turbidity and stains on laundry. Apart from this,
various health issues are also linked with elevated levels of iron in water. Different strategies
discussed in this review have been adapted for removing the high iron content from water. Among
the conventional strategies used, oxidation-precipitation-filtration process, calcium carbonate based
minerals, separation through filter media and electrocoagulation showed high iron removal efficiency
above 90%. Similar kind of efficiency was also observed with the biological treatment of water as
well as with membrane technology-based and nanotechnologybased strategies. All these techniques
were able to remove almost all forms of iron from different types of water samples, viz. groundwater,
industrial wastewater, drinking water, lake water and wastewater from landfills. Methods such as ion
exchange, supercritical fluid extraction, adsorption, wetland treatment, aeration and sequestration
were less effective in the removal of iron from the water samples. Their iron removal efficiency was
in the range of 40–80%. The iron removal method involving Vyredox technology exhibited lowest iron
removal efficiency (3.12%). As far as economy of iron removal is concerned, most of the conventional
techniques have shown cost effective removal of iron from aqueous system except removal through
supercritical fluid and Vyredox technology. Involvement of costly ligands and instrumentation for
supercritical fluid-based iron removal and high capital investment in Vyredox technology have limited
the use of these techniques for iron remediation. On the other hand, methods such as oxidation-
precipitation-filtration, filter media separation, EC & ECFs and CCBMs have emerged as most suitable,
cost effective techniques with excellent iron removal efficiencies for removing iron from water. Other
cost effective methods such as zeolite softening, adsorption, wetlands, aeration and sequestration
have shown comparatively less removal efficiencies. Biological strategy has also emerged as an
economic and suitable alternative to conventional techniques. Methods based on membrane
technology have high cost, which can be reduced with further advancements in module design and
membrane production. The higher cost associated with fabrication of nanomaterials in
nanotechnology based approach can be reduced by using naturally available nanomaterials such as
HNTs along with green synthesis of nanomaterials with biological extracts, which significantly cuts
down the use of costly and toxic chemicals. In the coming future, the advent of newer technologies
such as nanotechnology will enhance the removal of elevated levels of iron from different water
sources. The only nanotechnology-based approach discussed in this review utilized carbon
nanotubes for iron removal and the process displayed an efficiency of 99%. Such efficiencies can also
be achieved by utilizing the potential of other nanoparticles and nanomaterials. Various clay-based
nanomaterials and metal nanoparticles have been utilized by different researchers for the removal of
nitrate, sulphate, fluoride and heavy metals from water with great removal efficiencies. Such
materials can also be utilized with slight modification in their surface chemistry for the removal of
iron from different water sources. Combination of these newer technologies with conventional
techniques may become the silver bullet needed for the removal of iron from water.

Electro coagulation: Electrocoagulation (EC) is a method to destabilize the dissolved or suspended

pollutants present in water by the application of electric current in the contaminated water. The
pollutant gets removed from water due to the neutralization of its electric charge [89]. The technique
has been widely used for the removal of diverse contaminants from water. The advantages of the
process include no use of chemicals, less production of sludge and easy operation [90]. The
technique is often combined with electroflotation and termed as electrocoagulation/ flotation (ECF)
process. EC as well as ECF have been widely used for the removal of iron from aqueous systems.
Electrodes of aluminum have been employed during the EC process for the effective remediation of
iron tap water. The amorphous aluminum hydroxide complexes formed during the process showed
high sorption capacity. The iron removal process involved the oxidation of Fe (II) to Fe (III) followed
by removal of Fe (III) by the aluminum hydroxide complexes through adsorption and precipitation.
The initial concentration of iron was 25 mg/L. The technique showed 99.2% iron removal efficiency at
the end of 35 min of operation. It was observed that the iron removal increased upon increasing the
current density [91]. The technique has also utilized magnesium and galvanized iron electrodes (as
anode and cathode respectively) for the removal of iron from drinking water.
 Lead

The most common methods for removing lead ions from water and wastewater include precipitation,
coagulationfocculation, ion exchange, adsorption, and membrane separation. Precipitation and
coagulation-focculation techniques produce large amounts of sludge (Crini and Lichtfouse 2019). In
addition, these techniques are unlikely to reduce the lead ions to below the guideline value. Ion-
exchange is expensive and requires pretreatment for wastewater as the exchanger matrices get
clogged by the organics in the wastewater (Chowdhury et al. 2016; Yuan and Wood 2018).
Membrane distillation (MD), a thermally driven membrane separation process, ofered high removal
of heavy metals from highly concentrated solutions (Lou et al. 2020; Alkhudhiri et al. 2020). The
maximum removal of lead ions was 98% using the air gap MD process (Alkhudhiri et al. 2020). In
addition, MD efectively removed coexisting metal ions Fig. 1 A schematic of the study process
Applied Water Science (2022) 12:185 1 3 Page 3 of 33 185 from an aqueous solution (Lou et al. 2020;
Alkhudhiri et al. 2020). The limitations of membrane separation include membrane fouling, low
membrane durability, high operating cost, high equipment cost, and low permeation flux. Adsorption
has been chosen as the most suitable technology due to its low cost, easy to use, and excellent
removal efciency. The diferent groups of adsorbents were investigated and compared. The
advantages and disadvantages of these adsorbents were highlighted. The adsorption capacity and
removal efciency of the adsorbents were in the ranges of 0.7–2079 mg/g and 13.6–100%,
respectively. Among the low-cost adsorbents, the adsorption capacity of carboxylated jute stick
activated carbon, rice husk nanocomposite, Viscum album leaves, and activated aloji clay was
2079 mg/g, 1665 mg/g, 769.2 mg/g, and 333.3 mg/g, respectively. The corresponding removal
efciencies were 99.8%, 96.8%, 92.2%, and 97.3%, respectively

Inductively Coupled Argon Plasma Emission Spectroscopy coupled with a Mass Spectrometer
detector (ICP/MS). ICP/MS technology provides a very efficient and cost effective means of producing
data for municipalities, school districts, and other large sources of samples.

What is Mass Spectrometry?

Mass spectrometry is an analytical method useful for calculating the mass-to-charge ratio ( m / z) of
one or more molecules in the sample. Such measurements may also often be used to determine the
precise molecular weight of the sample components. Mass spectrometry is an analytical method to
find the molecular mass of a compound and indirectly helped to prove the identity of isotopes.

1. Principle of Mass Spectrometry

Based on Newton’s second law of motion and momentum, a mass spectrometer uses this property of
matter to plot ions of varying masses on a mass spectrum. From the law, we infer how much mass is
relevant to the inertia and acceleration of a body. This principle is applied to the aspect where ions
with different mass to charge ratios are deflected by different angles in an electric or magnetic field.

2. Mass Spectrum

A mass spectrum is a graph obtained by performing mass spectrometry. It is a relation between the
mass to charge ratio and ion signal.