ASSIGNMENT #1

Biochar/nano-zerovalent zinc-based materials for arsenic removal

from contaminated water

COURSE CODE: CHM-313

COURSE TITLE: INORGANIC CHEMISTRY-III

SUBMITTED BY: NIMRAH ZAMEER

ROLL NO. 21112041013

DEPARTMENT OF CHEMISTRY

SEMESTER 6TH ‘A’

SUBMITTED TO: DR. TUNZEEL

Table of Contents
Biochar/Nano-Zerovalent Zinc-Based Materials For Arsenic Removal From
Water ............................................................................................................................. 2
Absract ....................................................................................................................................2
Introduction........................................................................................................................3
Arsenic Contamination ................................................................................................ 4
Arsenic Sorption ....................................................................................................................4
Materials.............................................................................................................................5
Preparation…………………………………………………………………………………………………………………5

Methods…………………………………………………………………………………………………………………..6

Results and Discussion………………………………………………………………………………………….7

Applications…………………………………………………………………………………………………..…8

Conclusion……………………………………………………………………………………………………..8

Reference…………………………………………………………………………………………………..9

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Title: BIOCHAR BASED NANOMATERIALS SYNTHESIS AND
THEIR APPLICATIONS IN REMOVAL OF METAL
CONTAMINANTS FROM SOIL AND WATER

GENERAL NAME: Biochar/Nano-Zerovalent Zinc-Based Materials

For Arsenic Removal From Water

 Authors:
Israr Mehmood ul Hassan, Haram Javed, Muhmmad Mehroz Hussain,
Muhammad Bilal Shakoor, Irshad Bhatti, Muhammad Shahid, Farwa,
Nengneng Xu, Qunshan Wei,and Nabeel Khan Niazi.
 Citations:
Masood ul Hasan, I. Javed, H. Hussain, M. M., Shakoor, M. B. Bibi, I.,Shahid,
Niazi N. K. (2023). Biochar/nano-zerovalent zinc-based materials for arsenic
removal from contaminated water. International journal of phytoremediation,
25(9), 1155-1164.
Masood ul Hasan, Israr
 Year: 2023
 Page # : 1155-1164
 Volume: 25,2023
 Issue: 9th

Abstract:

The paper compares the performance of three different sorbents for arsenic removal:
nZVZn, BC/nZVZn, and BC/HA-alginate. nZVZn is a nano-material that can reduce
arsenic to less toxic forms and adsorb it on its surface. BC/nZVZn is a composite of
biochar and nZVZn, where biochar provides a porous and carbon-rich matrix for
nZVZn to disperse and interact with arsenic. BC/HA-alginate is another composite of
biochar and hydroxyapatite-alginate, where hydroxyapatite is a calcium phosphate
mineral that can bind arsenic through ion exchange and precipitation, and alginate is a
biopolymer that can enhance the stability and reusability of the sorbent.

The paper investigates the effects of various factors on the arsenic removal efficiency,
such as pH, initial arsenic concentration, contact time, and sorbent dosage. The paper

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finds that the optimal pH for nZVZn is 3.4, while for BC/nZVZn and BC/HA-alginate
is 7.2. The paper also finds that the arsenic removal efficiency increases with
increasing contact time and sorbent dosage, but decreases with increasing initial
arsenic concentration. The paper explains these results based on the sorption
mechanisms and the availability of active sites on the sorbents.

The paper evaluates the sorption kinetics, isotherms, and thermodynamics of the
sorbents using various models and equations. The paper determines that the sorption
process follows the pseudo-second order kinetic model and the Freundlich isotherm
model for all the sorbents, indicating that the sorption is controlled by chemisorption
and involves heterogeneous and multilayer sorption. The paper also calculates the
thermodynamic parameters and concludes that the sorption is spontaneous, feasible,
and endothermic for all the sorbents.

The paper performs the desorption and regeneration experiments to assess the stability
and reusability of the sorbents. The paper reports that nZVZn and BC/HA-alginate
show higher desorption efficiency and lower arsenic leaching than BC/nZVZn,
suggesting that they are more stable and reusable. The paper also finds that the
sorption capacity of the sorbents decreases slightly after three cycles of
sorption/desorption, indicating that they can be used for multiple times without
significant loss of performance.

This paper is the first study to explore the potential of newly prepared sugarcane
bagasse biochar/nano-zerovalent Zinc based composite for Arsenic removal from
water.

Introduction:

The Earth’s water resources consist of 2.5% of freshwater, of which about 30% is
groundwater, which is used for drinking, irrigation and industrial purpose globally.
Unfortunately, the increasing industrialization and urbanization has posed a serious
threat for groundwater quality. Among the various sources of contamination,
groundwater contamination with geogenically released toxic arsenic (As) is
considered to be a potential environmental and public health issue to millions of
people worldwide

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Arsenic Contamination: Arsenic contamination in water is a global concern,
affecting millions of people. Chronic exposure to arsenic can lead to serious health
issues, including cancer, skin lesions, and cardiovascular diseases. In contrast to
organic As species, inorganic As species especially Arsenite (As (III)) and arsenate
(As(V)) are more toxic and mobile than the organic ones. Groundwater is considered
as the primary source of drinking water in many countries around the world. For
maintaining resource sustainability, clean and safe groundwater is a priority for water
authorities worldwide. Unfortunately, groundwater resources are susceptible to
various types of pollution, with arsenic (As) being a major pollutant in certain areas
due to natural or anthropogenic activities. Due to its adverse health effects, As, a
class-1 carcinogen, has been a topic of intense research. The technical difficulty and
high cost incurred by conventional treatment systems for As removal have led many
researchers to work on developing efficient, eco-friendly, and cost-effective
technologies for the treatment of groundwater sources. Biochar has been widely used
as an adsorbent for the decontamination of groundwater. High As removal rates have
been achieved following metal (Fe, Zn, Mn) impregnation and magnetic modification
to biochar. Need for effective remediation developing efficient methods for arsenic
removal from water is crucial to safeguard public health and ensure safe drinking
water. Biochar is the lightweight black residue, made of carbon and ashes,
remaining after the pyrolysis of biomass, and is a form of charcoal. Biochar is
defined by the International Biochar Initiative as "the solid material obtained from
the thermochemical conversion of biomass in an oxygen-limited environment.

The study focuses on three materials:

 Nano-zerovalent zinc (nZVZn): A nanoscale material with high reactivity.

 Biochar (BC): A carbon-rich material derived from biomass.
 BC/hydroxyapatite-alginate (BC/HA-alginate) composite: A hybrid
material combining biochar with hydroxyapatite and alginate.

Arsenic Sorption Experiments:

The researchers conducted batch sorption experiments using these materials.

They exposed the materials to arsenic-contaminated water and measured the extent of
arsenic removal.

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Materials Synthesis and Preparation:

Chemicals and Reagents:

Following materials were used:

 Zinc Chloride ZnCl2

 Sodium borohydride NaBH4
 Calcium Chloride CaCl2
 Hydroxyapetite HA

Preparation of Sorbents:

 Nano-Zerovalent Zinc (nZVZn) Synthesis:

The nZVZn was prepared by using NaBH4 as reductant

Zn2+ + 2BH4- + 6H2O → Zn0 + 2B(OH)3 + 7H2

The researchers prepared nZVZn using a reduction method. Zinc salts (e.g., Zinc
Chloride or Zinc Sulfate) were reduced using a reducing agent (e.g., Sodium
borohydride) to form nanoscale zerovalent zinc particles.

Characterization:

The size, morphology, and crystalline structure of nZVZn were analyzed using
techniques such as transmission electron microscopy (TEM) and X-ray diffraction
(XRD). The results of the techniques confirmed the production of nZVZn.

 Biochar (BC):

Biochar is derived from biomass (e.g., agricultural residues, wood, or organic waste).
BC is produced through pyrolysis (thermal decomposition in the absence of oxygen)
of the biomass.The biomass is heated at high temperatures (typically 300–700°C) in a
controlled environment. Pyrolysis converts the organic matter in the biomass into
carbon-rich biochar.

 Preparation of biochar/hydroxyapatite-alginate (BC/HA-

alginate)

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Sugarcane bagasse (SCB) residue was collected from local market, sun-dried, oven
dried, ground and sieved using a 2 mm mesh sieve. Sugarcane bagasse biochar (SCB-
BC) was prepared by pyrolysis at 500 °C at a residence time of 2 h under partially
anoxic conditions. BC was combined with hydroxyapatite (HA) and alginate to form a
multifunctional composite.HA provides additional adsorption sites, and alginate
enhances stability.

Activation (Optional):

Some biochars undergo activation (e.g., steam activation) to enhance their surface
area and porosity.Activated biochar has increased adsorption capacity.

Characterization:

The composite’s structure and composition were analyzed using techniques like
Fourier-transform infrared spectroscopy (FTIR).

 BC/nZVZn Composite:

The biochar/nZVZn composite was prepared by adding HA (2.5 g), Na-alginate (1.5
g), SCB-BC (1 g) and nZVZn (1 g) in a similar order as it was done for BC/HA-
alginate using a beaker in 25 mL deionized water. The mixture was continuously
stirred to make it homogeneous and the slurry was transferred into 300 mL of 3 M
CaCl2 drop wise using a syringe to make BC/nZVZn/HA- alginate composite. The
prepared composite was left overnight in CaCl2 solution. Afterwards, the solid
martial was separated through filtration and oven dried at 40oC for 24 h. BC and
nZVZn were mixed together to form a composite material.The mixing can be
achieved through physical blending or impregnation methods.

Characterization:

The composite’s properties (surface area, pore size distribution, etc.) were
characterized using techniques like Brunauer–Emmett–Teller (BET) analysis.

Methods:

 Batch sorption experiments

A method to study how arsenic interacts with these materials in a liquid solution. It
involves adding a known amount of arsenic to a fixed amount of the material in a

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container, and shaking or stirring them for a certain time to reach equilibrium. Then,
the concentration of arsenic in the liquid phase is measured, and the amount of arsenic
that is adsorbed on the solid phase is calculated. This is called the sorption
experiment. The sorption experiment can be repeated with different initial
concentrations of arsenic to obtain a sorption isotherm, which is a curve that shows
the relationship between the equilibrium concentration and the adsorbed amount.

 Desorption batch experiments

The desorption experiment is similar to the sorption experiment, but in reverse. It

involves adding a known amount of arsenic that is already adsorbed on the material to
a fresh liquid solution, and shaking or stirring them for a certain time to reach
equilibrium. Then, the concentration of arsenic in the liquid phase is measured, and
the amount of arsenic that is desorbed from the solid phase is calculated. The
desorption experiment can also be repeated with different initial concentrations of
arsenic to obtain a desorption isotherm, which may differ from the sorption isotherm
due to hysteresis effects.

Results and Discussion:

Arsenite removal by nZVZn, BC/HA-alginate and BC/nZVZn composite was found

to be pH dependent. nZVZn exhibited the highest percentage removal of both As(III)
and As(V) at pH 3.4:

As(III): 96%

As(V): 94%

BC/nZVZn and BC/HA-alginate also showed good removal rates:

BC/nZVZn: BC/HA-alginate:

As(III): 90% As(III): 88%

As(V): 88% As(V): 80%

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Sorption Models:

The Freundlich model provided the best fit for As(III) and As(V) sorption data,
particularly for nZVZn (R² up to 0.98).The pseudo-second order model described the
kinetics of As(III) and As(V) sorption well (R² = 0.99).

Desorption Efficiency:

Over three sorption/desorption cycles, the order of As removal efficiency was:

nZVZn > BC/HA-alginate > BC/nZVZn

Applications:

The paper reports that nano-zerovalent zinc was the most effective material for
arsenic removal, and that the sorption and desorption behavior of arsenic was
influenced by the pH, initial concentration, and type of material.

The synthesized materials (nZVZn, BC/nZVZn, and BC/HA-Alginate) were tested for
their ability to remove inorganic arsenic species (As(III) and As(V)) from
contaminated water.

Conclusion:

In summary, the study employed a combination of reduction methods, pyrolysis, and

composite formation to create effective materials for arsenic removal. These materials
hold promise for addressing water contamination challenges. Nano-zerovalent zinc is
a nanoscale material that consists of metallic zinc particles that can reduce arsenic to a
less soluble and less toxic form. Biochar is a carbon-rich material that is produced by
pyrolysis of biomass, such as crop residues, wood, or animal manure. Biochar can
adsorb arsenic through various mechanisms, such as electrostatic attraction, surface
complexation, and ion exchange. Hydroxyapatite is a mineral that contains calcium
and phosphate, and can form complexes with arsenic. Alginate is a natural polymer
that can bind with hydroxyapatite and enhance its stability.The paper concludes that
the biochar and nano-zerovalent zinc-based materials have potential applications for
the remediation of arsenic-contaminated water, and suggests some future research
directions, such as optimizing the material synthesis, testing the materials in real
water samples, and evaluating the environmental and economic feasibility of the

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materials. The paper also highlights the advantages of using these materials, such as
their low cost, high efficiency, easy availability, and environmental friendliness.

Reference:

 Biochar/nano-zerovalent zinc-based materials for arsenic removal from

contaminated water

https://www.tandfonline.com/doi/full/10.1080/15226514.2022.2140778

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